638-94599F
Sep. 2014
TOTAL ORGANIC CARBON ANALYZER
TOC-LCSH/CSN
USER'S MANUAL
Read the instruction manual thoroughly before you use the product.
Keep this instruction manual for future reference.
This page is intentionally left blank.
0
0
0
Introduction
Read this Instruction Manual thoroughly before using the product.
Thank you for purchasing this product. This USER'S MANUAL describes how to use this
product in addition to any accessories and options related to this product. Read this manual
thoroughly before using the product and operate the product in accordance with the
instructions in this manual.
Also, keep this manual for future reference.
IMPORTANT
•
If the user or usage location changes, ensure that this Instruction Manual is
always kept together with the product.
If this manual or a product warning label is lost or damaged, immediately contact
your Shimadzu representative to request a replacement.
To ensure safe operation, read all Safety Instructions before using the product.
To ensure safe operation, contact your Shimadzu representative if product
installation, adjustment, or re-installation (after the product is moved) is required.
•
•
•
Notice
•
•
•
•
•
Information in this manual is subject to change without notice and does not represent a commitment on the
part of the vendor.
Any errors or omissions which may have occurred in this manual despite the utmost care taken in its
production will be corrected as soon as possible, although not necessarily immediately after detection.
All rights are reserved, including those to reproduce this manual or parts thereof in any form without
permission in writing from Shimadzu Corporation.
PALAFILM are registered trademarks of American National Can.
Other company names and product names mentioned in this manual are trademarks or registered trademarks
of their respective companies.
© 2011-2014 Shimadzu Corporation. All rights reserved.
Original version is approved in English.
Indications Used in This Manual
Cautions and Notes are indicated using the following conventions:
Precautionary Conventions Used in this Manual
The following precautionary conventions are used in this manual.
Convention
Description
CAUTION
Indicates a potentially hazardous situation which, if not avoided, may result in
minor to moderate injury or equipment damage.
Note:
Emphasizes additional information that is provided to ensure the proper use of
this product.
Other Conventions Used in this Manual
Instrument Model Names
Descriptions in this documentation pertain to two models of the TOC-L Total Organic
Carbon Analyzer, namely the TOC-LCSH and TOC-LCSN. These models will be referred to
in relevant descriptions as the H Type and N Type, respectively.
Supplementary Conventions
In addition to the precautionary conventions, the "Tip" and "Reference" conventions are
used to supply additional information.
Convention
ii
TOC-LCSH/CSN
Description
TIP »
Indicates a particular technique, alternative means of operation, or useful advice.
Reference:
Indicates a reference location in the manual where more detailed information can
be found.
Safety Instructions
To ensure safe product operation, read these important safety instructions carefully before
use and follow all CAUTION instructions given in this section.
Product Applications
This instrument is a total organic carbon analyzer.
Use this instrument ONLY for the intended purpose.
Using this instrument for any other purpose could cause accidents.
Installation Site
Do not install this product at a site where fire is prohibited.
Installation
To ensure safe operation, contact your Shimadzu representative if product installation,
adjustment, or re-installation (after the product is moved) is required.
When lifting the instrument, lift from the bottom and at both sides of the instrument.
Do not lift it by the front access door, as this may cause instrument damage.
Operation
The contents of the hard disk of the personal computer may be lost as the result of an
unforeseen accident.
Always create a backup to protect critical data from such accidents.
Do not measure or inject explosive, ignitable, or flammable materials into the instrument.
TOC-LCSH/CSN
iii
In an Emergency
In an emergency, turn OFF the main power switch on the left side towards the top of the
TOC-L. Also, turn OFF the power switch on the left side of the ASI-L.
Also, when the product is used again, inspect the product and, if necessary, contact your
Shimadzu representative to request servicing.
Emergency Stop Procedure
1.
2.
Close the main valves on the gas cylinders.
3.
Unplug the power cable.
Turn OFF the main power switch on the left side towards the top of the TOC-L. Also,
turn OFF the power switch on the left side of the ASI-L.
During a Power Outage
Take the following measures in the event of a power outage.
1.
Turn OFF the main power switch on the left side towards the top of the TOC-L. If the
main power switch is not turned OFF, the instrument automatically restarts when
power is restored. The power switch on the ASI-L does not need to be turned OFF.
2.
After power is restored, turn ON the main power switch on the left side towards the
top of the TOC-L. Confirm that the instrument operates properly before use.
Warning Labels
High Temperature Warning
The area near the center of the electric furnace becomes extremely hot when the furnace is
heating up and when the furnace has reached operating temperature (680 °C or 720 °C). Do
not touch the electric furnace as this could result in burns. Allow the furnace to cool before
performing any maintenance on the combustion tube or catalyst.
iv
TOC-LCSH/CSN
Electric Shock Warning
Do not remove this panel, as there is danger of electric shock.
TOC-LCSH/CSN
v
Injury Warning
During operation, the pressure in the CO2 absorber of the gas purifier is about 200kPa. To
prevent injuries, turn off the carrier gas and switch off power to the TOC main unit. Wait
until the pressure inside the container and the instrument flow lines return to normal
atmospheric pressure before performing any maintenance.
Corrosion Warning
Acid and other corrosive substances are present in the liquid waste drained from this
instrument. Be careful not to touch or spill the liquid waste.
Liquid waste may have a pH level less than 2.0 depending on measurement conditions.
Liquid waste with a pH less than 2.0 is classed as industrial waste subject to special control.
Request transfer by an authorized industrial waste transporter to an authorized industrial
waste processing facility to process any industrial waste subject to special control. If you
wish to perform deacidification on your own premises, contact the environmental agency in
your jurisdiction.
vi
TOC-LCSH/CSN
The soda lime in the CO2 absorber of the carrier gas purifier is a corrosive chemical
substance. Be careful not to touch or spill this substance.
TOC-LCSH/CSN
vii
The liquid discharged from the drain tube connected to the TC injector contains acid and
other corrosive substances. Verify that the tip of the drain tube is securely inserted into the
Y-shaped fitting when connecting the combustion tube and sample injector.
The IC reaction solution is acidic. Be careful not to touch or spill the IC reaction solution.
viii
TOC-LCSH/CSN
Hydrochloric acid is a corrosive chemical substance. Be careful not to touch or spill the
hydrochloric acid.
TOC-LCSH/CSN
ix
Warranty
Shimadzu provides the following warranty for this product.
Period:
Please contact your Shimadzu representative for information about the period of this
warranty.
Description:
If a product/part failure occurs for reasons attributable to Shimadzu during the warranty
period, Shimadzu will repair or replace the product/part free of charge. However, in the
case of products which are usually available on the market only for a short time, such as
personal computers and their peripherals/parts, Shimadzu may not be able to provide
identical replacement products.
Limitation of Liability:
(1)
(2)
In no event will Shimadzu be liable for any lost revenue, profit or data, or for special,
indirect, consequential, incidental or punitive damages, however caused regardless of
the theory of liability, arising out of or related to the use of or inability to use the
product, even if Shimadzu has been advised of the possibility of such damage.
In no event will Shimadzu's liability to you, whether in contract, tort (including
negligence), or otherwise, exceed the amount you paid for the product.
Exceptions:
Failures caused by the following are excluded from the warranty, even if they occur during
the warranty period.
1)
Improper product handling
2)
Repairs or modifications performed by parties other than Shimadzu or Shimadzu
designated companies
3)
Product use in combination with hardware or software other than that designated by
Shimadzu
4)
Computer viruses leading to device failures and damage to data and software,
including the product's basic software
5)
Power failures, including power outages and sudden voltage drops, leading to device
failures and damage to data and software, including the product's basic software
6)
Turning OFF the product without following the proper shutdown procedure leading
to device failures and damage to data and software, including the product's basic
software
7)
Reasons unrelated to the product itself
8)
Product use in harsh environments, such as those subject to high temperatures or
humidity levels, corrosive gases, or strong vibrations
x
TOC-LCSH/CSN
9)
Fires, earthquakes, or any other act of nature, contamination by radioactive or
hazardous substances, or any other force majeure event, including wars, riots, and
crimes
10) Product movement or transportation after installation
11) Consumable items
Note: Recording media such as floppy disks and CD-ROMs are considered
consumable items.
* If there is a document such as a warranty provided with the product, or there is a
separate contract agreed upon that includes warranty conditions, the provisions of those
documents shall apply.
TOC-LCSH/CSN
xi
After-Sales Service and Availability of Replacement Parts
After-Sales Service
If any problem occurs with this product, perform an inspection and take appropriate
corrective action as described in this manual's troubleshooting section. If the problem
persists, or the symptoms are not covered in the troubleshooting section, contact your
Shimadzu representative.
Replacement Parts Availability
Replacement parts for this product will be available for a period of seven (7) years after the
product is discontinued. Thereafter, such parts may cease to be available.
Note, however, that the availability of units or parts not manufactured by Shimadzu shall be
determined by the relevant manufacturers. If Shimadzu receives notice of the
discontinuation of units or parts, the necessary quantity for the above period is immediately
calculated and secured. However, such units or parts may cease to be available within seven
years after the discontinuation of the product, depending on individual manufacturer
conditions and on changes in the quantity required.
Maintenance, Inspections, and Adjustment
In order to maintain the instrument's performance and obtain accurate measurement data,
daily inspection and periodic inspection are necessary.
•
•
xii
For daily maintenance and periodic inspection, see "4 Maintenance".
For consumable parts and maintenance parts, see "5 Reference Materials".
The replacement cycle for each part is given at a rough estimate.
Replacement may be required earlier than the replacement cycle depending on the
environment and frequency of usage.
TOC-LCSH/CSN
Disposal Precautions
•
•
•
•
•
•
Dispose of this instrument according to local regulations for the relevant area and
request processing by an industrial waste disposal company. Gather and seal insulation
material waste into plastic bags and request disposal by an industrial waste disposal
company licensed to process glass, concrete, and ceramic waste.
All used catalyst should be sent to a licensed industrial waste disposal company.
All used CO2 absorbers should be sent to a licensed industrial waste disposal company.
All used halogen scrubbers should be sent to a licensed industrial waste disposal
company.
All used catalyst from the ozone treatment unit should be sent to a licensed industrial
waste disposal company.
The optional measurement circuit for purgeable organic carbon (POC) uses a CO2
absorber filled with lithium hydroxide to remove carbon dioxide. All used lithium
hydroxide crystals should be sent to a licensed industrial waste disposal company.
TOC-LCSH/CSN
xiii
Electromagnetic Compatibility
This instrument complies with European standard EN50011 class A for electromagnetic
emission and EN61326-1 for electromagnetic immunity.
EN55011 Emissions (Electromagnetic Interference)
This instrument complies with European EMI (Electro Magnetic Interference) standard
EN55011 class A equipment. This instrument can be used in any environment except in the
home.
Note:
When an electromagnetic disturbance occurs due to nearby this instrument, provide an
appropriate distance between instruments to eliminate the disturbance.
In addition, please connect this instrument to a large power supply of the capacity as much
as possible.
EN61326-1 Immunity (Electromagnetic Susceptibility)
This instrument complies with European standard EN61326-1 for electromagnetic
immunity.
Stated below are the test conditions.
IEC 61000-4-2 Electrostatic Discharge
Air: 8 kV, Direct: 4 kV
IEC 61000-4-3 Radiated, Radio-Frequency,
10 V/m (0.08-1 GHz), 3 V/m (1.4-2 GHz),
Electromagnetic Field
1 V/m (2-2.7 GHz)
IEC 61000-4-4 Transient/Burst
2.0 kV to AC power line and ground
(Electrical Fast Transients)
IEC 61000-4-5 Voltage Surge
1.0 kV line to line, 2 kV line to ground
IEC 61000-4-6 Conducted RF Immunity
3 Vrms (150 kHz-80 MHz)
IEC 61000-4-11 Voltage Variations/Dips/Interrupts
0 % UT 1 cycles (20 ms),
70 % UT 25 cycles (500 ms),
0 % UT 250 cycles (5000 ms)
Note:
Compliance to the standard does not ensure that the instrument can work with any level of
Electromagnetic interference stronger than the level tested.
Interference greater than the value specified in the condition above may cause malfunction
of the instrument.
To above electromagnetic disturbances, follow the recommendations below.
(1)
(2)
xiv
TOC-LCSH/CSN
Before touching the instrument, discharge the electro static charged in operator's body
to ground touching metallic structure connected to ground.
Do not install this instrument in such environment where strong electromagnetic
fields are generated near by.
Contents of This Manual
Chapter 1 - Overview
This chapter provides an overview of the instrument, as well as safety precautions to be
taken while using the instrument.
Chapter 2 - System Description
This chapter identifies and describes the system components and provides a brief
description of optional accessories.
Chapter 3 - Operation
This chapter provides detailed descriptions of the instrument functions, typical preparation
procedures, basic operation procedures such as calibration curve generation, and
application operations such as using optional features.
Chapter 4 - Maintenance
This chapter details the typical maintenance items and periodic checks required to ensure
that the instrument provides consistently high accuracy analyses. Also included is a
description of the error messages and troubleshooting procedures.
Chapter 5 - Reference Information
This chapter provides a detailed description of the analysis principles on which the
instrument is based, specifications, standard and optional accessories, the various screens
displayed on the LCD, as well as the specialized terms associated with this instrument. The
installation procedure is also provided in the event that instrument is moved to another
installation site.
TOC-LCSH/CSN
xv
This page is intentionally left blank.
xvi
TOC-LCSH/CSN
Table of Contents
Introduction................................................................................................................ i
Indications Used in This Manual....................................................................................
Precautionary Conventions Used in this Manual ...................................................
Other Conventions Used in this Manual ................................................................
Safety Instructions..........................................................................................................
Product Applications..............................................................................................
Installation Site.......................................................................................................
Installation..............................................................................................................
Operation................................................................................................................
In an Emergency ....................................................................................................
During a Power Outage..........................................................................................
Warning Labels ......................................................................................................
Warranty.........................................................................................................................
After-Sales Service and Availability of Replacement Parts...........................................
After-Sales Service.................................................................................................
Replacement Parts Availability..............................................................................
Maintenance, Inspections, and Adjustment....................................................................
Disposal Precautions ......................................................................................................
Electromagnetic Compatibility.......................................................................................
Contents of This Manual ................................................................................................
1
1Overview ...................................................................................................................
1.1
1.2
2
1
Overview ........................................................................................................................ 2
Operational Precautions ................................................................................................. 3
2System
2.1
ii
ii
ii
iii
iii
iii
iii
iii
iv
iv
iv
x
xii
xii
xii
xii
xiii
xiv
xv
Description ................................................................................................... 7
TOC-LCSH/CSN Construction .........................................................................................
2.1.1
Front View .............................................................................................................
2.1.2
Right Side View .....................................................................................................
2.1.3
Left Side View .......................................................................................................
2.1.4
Rear View...............................................................................................................
2.1.5
Front Internal View (Left Diagonal) ......................................................................
2.1.6
Top Internal View (Left Diagonal) ........................................................................
2.1.7
Keyboard Layout....................................................................................................
2.1.8
Flow Diagrams .......................................................................................................
2.2
Autosampler (Option).....................................................................................................
2.2.1
Front View (Left Diagonal) ...................................................................................
2.2.2
Rear View (Left Diagonal).....................................................................................
2.3
8-Port Sampler OCT-L (Option) ....................................................................................
2.3.1
Front View (Left Diagonal) ...................................................................................
2.3.2
Rear View (Right Diagonal) ..................................................................................
2.4
TN Unit (Option)............................................................................................................
2.4.1
Front View (Right Diagonal) .................................................................................
2.4.2
View Inside the Door on the Right Side ................................................................
2.4.3
Rear View...............................................................................................................
8
8
8
9
10
11
12
12
14
19
19
19
20
20
20
21
21
21
22
TOC-LCSH/CSN
xvii
Table of Contents
3
3Operation..................................................................................................................
3.1
Analysis Preparation .......................................................................................................
3.1.1
Catalyst Filling .......................................................................................................
3.1.1.1
Catalyst for TOC Analysis ...........................................................................
3.1.1.2
TOC/TN Catalyst (Option) ..........................................................................
3.1.2
Installing the Cooling Tube Unit (H Type Only) ...................................................
3.1.3
Connecting the Combustion Tube ..........................................................................
3.1.4
Connecting the Halogen Scrubber..........................................................................
3.1.5
Installing the Syringe..............................................................................................
3.1.6
Water Supply to the Dehumidifier Drain Vessel....................................................
3.1.7
Filling the Humidifier with Water..........................................................................
3.1.8
Preparation of Dilution Water ................................................................................
3.1.9
Acid Preparation.....................................................................................................
3.1.10 Installation of the CO2 Absorber............................................................................
3.1.11 Printer Preparation..................................................................................................
3.1.12 Installing the Suspended Solids Kit........................................................................
3.1.13 IC Analysis Preparations ........................................................................................
3.1.14 Preparation for POC Analysis ................................................................................
3.1.15 TN Analysis Preparations (When Using the Optional TN Unit)............................
3.1.15.1
NOx Absorber ..............................................................................................
3.1.16 B-Type Halogen Scrubber
(When Using the Optional B-Type Halogen Scrubber) .........................................
3.1.17 Instrument Parameters ............................................................................................
3.1.17.1
Buzzer ..........................................................................................................
3.1.17.2
Date and Time ..............................................................................................
3.1.17.3
Catalyst Type ...............................................................................................
3.1.17.4
Concentration Unit .......................................................................................
3.1.17.5
Printer Setup.................................................................................................
3.1.17.6
Suspended Solids Analysis ..........................................................................
3.1.17.7
Syringe Washes............................................................................................
3.1.17.8
Automatically Change the Injection Volume...............................................
3.1.17.9
Automatically Change Dilution Factor ........................................................
3.1.17.10 Multiple Injections .......................................................................................
3.1.17.11 Setting Conversion Equation........................................................................
3.1.17.12 Automatic Regeneration of IC Reagent (H Type) .......................................
3.1.17.13 Analysis Span...............................................................................................
3.1.17.14 Counter Limit Values...................................................................................
3.1.17.15 Screen Saver.................................................................................................
3.1.18 Preparation and Storage of Standard Solutions ......................................................
3.1.18.1
Preparation of Standard Solutions................................................................
3.1.18.2
Storage of Standard Solutions......................................................................
3.1.19 Sample Preparation.................................................................................................
3.1.19.1
High Sensitivity Analysis.............................................................................
3.1.19.2
TC Blank Check Analysis............................................................................
3.1.19.3
Pretreatment for IC Removal (Sparging) .....................................................
3.1.19.4
Analysis of Samples Containing Suspended Solids.....................................
3.1.19.5
Handling Samples Containing Acids, Bases or Salts...................................
3.2
Analysis ..........................................................................................................................
3.2.1
Starting Up the Instrument .....................................................................................
xviii
TOC-LCSH/CSN
23
24
24
25
27
28
29
38
39
41
42
43
44
45
45
46
48
50
52
52
53
55
55
56
58
59
60
62
62
64
65
66
67
68
70
71
72
73
73
75
76
76
79
81
82
83
85
85
Table of Contents
3.2.1.1
3.2.1.2
3.2.1.3
Turning the Power ON.................................................................................
Setting the Carrier Gas Supply Pressure......................................................
Setting the Carrier Gas Supply Pressure
(When Using the Carrier Gas Regulator Option) ........................................
3.2.1.4
Setting the Flow Rate of Carrier Gas...........................................................
3.2.1.5
Setting the Sparge Gas Flow Rate
(When Using the Optional External Sparge Kit) .........................................
3.2.1.6
Electric Furnace ...........................................................................................
3.2.1.7
Turning On Power to the TNM-L (Option) .................................................
3.2.1.8
Setting the TNM-L Ozone Air Flow Rate (Option) ....................................
3.2.2
Calibration Curve Analysis ....................................................................................
3.2.2.1
Single-point Calibration Curve....................................................................
3.2.2.2
Multi-point Calibration Curve Analysis ......................................................
3.2.2.3
Multi-point Calibration Curve Analysis with Diluted Solution...................
3.2.2.4
Changing Parameters for a Generated Calibration Curve ...........................
3.2.3
Sample Analysis....................................................................................................
3.2.3.1
Single-mode Analysis ..................................................................................
3.2.3.2
Multi-mode Analysis ...................................................................................
3.2.3.3
Multi-mode Analysis - Simultaneous Analysis ...........................................
3.2.3.4
Multi-mode Analysis - Common Injection Analysis...................................
3.2.4
Creating a Method..................................................................................................
3.2.5
Stopping Analysis ..................................................................................................
3.2.6
Discarding Data......................................................................................................
3.2.7
Ending Analysis .....................................................................................................
3.3
Analysis with the Autosampler ......................................................................................
3.3.1
Sample Preparation for Autosampler Measurement ..............................................
3.3.1.1
Vial Types....................................................................................................
3.3.1.2
Filling Vials with Sample ............................................................................
3.3.1.3
Placing Vials in the Vial Rack.....................................................................
3.3.1.4
Rinse Water Preparation ..............................................................................
3.3.1.5
High Sensitivity ASI-L Analysis .................................................................
3.3.1.6
Acid Addition in NPOC Analysis................................................................
3.3.1.7
Sparging in NPOC Analysis ........................................................................
3.3.1.8
Stirrer Preparation........................................................................................
3.3.2
Setting General Measurement Conditions .............................................................
3.3.3
Setting Analysis Parameters...................................................................................
3.3.3.1
Calibration Curve Analysis..........................................................................
3.3.3.2
Single-point Calibration Curve Analysis.....................................................
3.3.3.3
Multi-point Calibration Curve Analysis ......................................................
3.3.3.4
Multi-point Calibration Curve Analysis with Diluted Solution...................
3.3.3.5
Sample Analysis Settings.............................................................................
3.3.3.6
Single-mode Analysis ..................................................................................
3.3.3.7
Multi-mode Analysis ...................................................................................
3.3.3.8
Multi-mode Analysis - Simultaneous Analysis ...........................................
3.3.3.9
Multi-mode Analysis - Common Injection Analysis...................................
3.3.3.10
Editing the ASI Schedule Settings...............................................................
3.3.4
Analysis..................................................................................................................
3.3.4.1
Starting Analysis..........................................................................................
3.3.4.2
Interrupting Analysis ...................................................................................
3.4
Analysis with the 8-Port Sampler...................................................................................
85
86
86
87
89
90
91
91
92
92
99
103
111
112
112
121
124
127
132
135
136
137
140
140
140
142
143
144
145
146
146
147
149
152
152
153
157
159
161
163
166
168
170
173
176
176
178
179
TOC-LCSH/CSN
xix
Table of Contents
3.4.1
Preparation for Sample Analysis Using the OCT-L 8-Port Sampler .....................
3.4.1.1
Sample Container .........................................................................................
3.4.1.2
Loading the Sample......................................................................................
3.4.1.3
High Sensitivity Using the OCT-L ..............................................................
3.4.2
Setting Analysis Parameters ...................................................................................
3.4.2.1
Calibration Curve Analysis ..........................................................................
3.4.2.2
Single-point Calibration Curve Analysis .....................................................
3.4.2.3
Multi-point Calibration Curve Analysis.......................................................
3.4.2.4
Multi-point Calibration Curve Analysis with Diluted Solution...................
3.4.2.5
Sample Analysis Settings.............................................................................
3.4.2.6
Single-mode Analysis ..................................................................................
3.4.2.7
Multi-mode Analysis....................................................................................
3.4.2.8
Multi-mode Analysis - Simultaneous Analysis............................................
3.4.2.9
Multi-mode Analysis - Common Injection Analysis ...................................
3.4.2.10
Editing the ASI Schedule Settings ...............................................................
3.4.3
Analysis ..................................................................................................................
3.4.3.1
Starting Analysis ..........................................................................................
3.4.3.2
Interrupting Analysis....................................................................................
3.5
Data Review....................................................................................................................
3.5.1
Reviewing Calibration Curve List..........................................................................
3.5.2
Reviewing the Method List ....................................................................................
3.5.3
Reviewing Data Reports.........................................................................................
3.6
Outputting Data to a USB Memory Device....................................................................
3.7
Applications Operations (H Type Only).........................................................................
3.7.1
Manual Injection Analysis......................................................................................
3.7.2
Gas Sample Analysis (When Using the Optional Manual Injection Kit)...............
4
4
Maintenance ............................................................................................................ 233
4.1
234
234
234
234
235
235
236
236
237
240
242
242
242
242
244
245
247
247
250
251
Daily Inspection..............................................................................................................
4.1.1
Checking Dilution Water........................................................................................
4.1.2
Checking Acid ........................................................................................................
4.1.3
Checking Drain Vessel Water Level ......................................................................
4.1.4
Checking Humidifier Water Level .........................................................................
4.1.5
Inspecting the Liquid in the B-Type Halogen Scrubber (Option)..........................
4.2
Periodic Inspections........................................................................................................
4.2.1
Catalyst Regeneration.............................................................................................
4.2.2
Washing or Replacing Catalyst ..............................................................................
4.2.3
Replacing the Carrier Gas Purification Tube and Catalyst ....................................
4.2.4
Washing / Replacing the Combustion and Carrier Gas Purification Tubes ...........
4.2.5
Replacing the High-Purity Air Cylinder.................................................................
4.2.6
Replacing the CO2 Absorber..................................................................................
4.2.7
Replacing the Halogen Scrubber ............................................................................
4.2.8
Syringe Replacement..............................................................................................
4.2.9
Replacing the Syringe Plunger Tip.........................................................................
4.2.10 Replacing The Sliding Sample Injector O-Rings ...................................................
4.2.11 Replacing the Syringe Pump 8-port Valve Rotor...................................................
4.2.12 Replacing the CO2 Absorber for the Optional Carrier Gas Purifier.......................
4.2.13 Replenishing IC Reaction Solution ........................................................................
xx
179
179
179
180
181
181
182
186
188
191
191
195
196
199
201
204
204
206
207
207
211
213
216
219
219
227
TOC-LCSH/CSN
Table of Contents
4.2.14 Replacing the Pump Head of the IC Reaction Solution Pump...............................
4.2.15 Replacing the Filler of the Optional POC Analysis CO2 Absorber .......................
4.2.16 Replacing the Liquid in the B-Type Halogen Scrubber (Option) ..........................
4.3
Autosampler (ASI-L) Maintenance................................................................................
4.3.1
Rinse Bottle Inspection ..........................................................................................
4.3.2
Sample Catcher Inspection.....................................................................................
4.3.3
Replacing the Pump Head of the Rinse Pump .......................................................
4.4
8-Port Sampler (OCT-L) Maintenance...........................................................................
4.4.1
Replacing the 8-Port Valve Rotor ..........................................................................
4.5
TN Unit (TNM-L) Maintenance.....................................................................................
4.5.1
Replacing the Catalyst in the Ozone Treatment Unit.............................................
4.5.2
Inspecting the Chemiluminescence Detector
and Replacing the Ozone Generator ......................................................................
4.5.3
Replacing the NOx Absorber .................................................................................
4.6
Troubleshooting..............................................................................................................
4.6.1
Error Messages.......................................................................................................
4.6.2
Troubleshooting .....................................................................................................
4.6.2.1
TOC-L..........................................................................................................
4.6.2.2
ASI-L ...........................................................................................................
4.6.2.3
8-Port Sampler OCT-L ................................................................................
4.6.2.4
Remedial Actions for Poor Repeatability ....................................................
4.6.2.5
Corrective Action for Combustion Tube Breakage
Inside the Electric Furnace ..........................................................................
5
252
253
253
254
254
254
255
256
256
258
258
260
260
261
261
267
267
272
273
274
276
5
Reference Materials ................................................................................................ 277
5.1
278
278
279
280
281
282
282
283
283
283
284
284
285
286
286
288
288
289
290
290
291
292
Principles of Analysis.....................................................................................................
5.1.1
Principle of TC (Total Carbon) Analysis ...............................................................
5.1.2
Principles of IC (Inorganic Carbon) Analysis........................................................
5.1.3
Principle of NPOC (Non-Purgeable Organic Carbon) Analysis............................
5.1.4
Principle of POC (Purgeable Organic Carbon) Analysis.......................................
5.1.5
Principles of Measuring TOC ................................................................................
5.1.6
Principles of Measuring TN (Total Nitrogen)........................................................
5.2
Analysis-Related Technical Information........................................................................
5.2.1
Peak Area Analysis ................................................................................................
5.2.2
Peak Shape .............................................................................................................
5.2.3
Calibration Curves .................................................................................................
5.2.3.1
Types of Calibration Curves ........................................................................
5.2.3.2
Shifting of Calibration Curves.....................................................................
5.2.4
Sparging During Standard Solution Analysis ........................................................
5.2.5
Automatic Selection of the Optimal Calibration Curve.........................................
5.2.6
Automatically Changing the Injection Volume .....................................................
5.2.7
Automatically Changing the Dilution Factor.........................................................
5.2.8
Multiple Injections .................................................................................................
5.3
Screen Descriptions ........................................................................................................
5.3.1
"Initial Display" .....................................................................................................
5.3.2
"Background Monitor" Screen ...............................................................................
5.3.3
"Conditions" Screen ...............................................................................................
TOC-LCSH/CSN
xxi
Table of Contents
5.3.4
"Maintenance" Screen ............................................................................................
5.3.5
"Data Report - Measurement Log" Screen .............................................................
5.3.6
"Data Report - Calibration Curves" Screen............................................................
5.3.7
"Calibration Settings" Screen .................................................................................
5.3.8
Calibration Curve Generation.................................................................................
5.3.8.1
"Calibration" Screen.....................................................................................
5.3.8.2
During Analysis ...........................................................................................
5.3.8.3
Completion of Analysis Point ......................................................................
5.3.8.4
Analysis Completion....................................................................................
5.3.8.5
Calibration Curve Protection........................................................................
5.3.9
"Measurement Parameters" Screen ........................................................................
5.3.9.1
Calibration Curve List..................................................................................
5.3.10 Analysis ..................................................................................................................
5.3.10.1
During Analysis ...........................................................................................
5.3.10.2
Viewing the Analysis Parameters ................................................................
5.3.10.3
Viewing the Ready Parameters ....................................................................
5.3.10.4
Analysis Completion....................................................................................
5.3.11 "Method Store" Screen ...........................................................................................
5.3.11.1
Loading a Method ........................................................................................
5.3.12 "ASI Schedule - Settings" Screen...........................................................................
5.3.12.1
"ASI Calibration Settings" Screen ...............................................................
5.3.12.2
"ASI Measurement Settings" Screen ...........................................................
5.3.12.3
ASI Schedule - Starting Analysis.................................................................
5.3.12.4
ASI Schedule - During Analysis ..................................................................
5.3.12.5
ASI Schedule - Viewing the Schedule .........................................................
5.3.12.6
ASI Schedule - Viewing the Calibration Curve Generation Parameters .....
5.3.12.7
ASI Schedule - Viewing Analysis Parameters.............................................
5.3.12.8
ASI Schedule - Viewing the Ready Parameters...........................................
5.4
Specifications..................................................................................................................
5.4.1
TOC-LCSH/CSN .......................................................................................................
5.4.2
ASI-L......................................................................................................................
5.4.3
OCT-L 8-Port Sampler ...........................................................................................
5.4.4
TNM-1....................................................................................................................
5.4.5
POC Measurement Kit ...........................................................................................
5.4.6
Carrier Gas Purifier Kit ..........................................................................................
5.4.7
Manual Injection Kit (Gas Sample Injection Kit) ..................................................
5.4.8
B-Type Halogen Scrubber......................................................................................
5.4.9
External Sparge Kit ................................................................................................
5.4.10 LAN Output............................................................................................................
5.4.10.1
Communication Specifications ....................................................................
5.4.10.2
Connection Cable .........................................................................................
5.4.10.3
Transmission Content...................................................................................
5.5
Standard Accessories ......................................................................................................
5.6
Special Accessories ........................................................................................................
5.7
Consumable Parts List ....................................................................................................
5.7.1
Consumable Parts List............................................................................................
5.7.2
Recommended Consumable Part Replacement Period ..........................................
5.8
Maintenance Parts List ...................................................................................................
xxii
TOC-LCSH/CSN
297
299
301
304
307
307
308
310
310
312
313
317
318
320
321
322
323
324
325
326
328
329
330
332
333
334
335
336
337
337
338
338
339
339
339
340
340
340
341
341
341
341
347
349
351
351
354
355
Table of Contents
5.9
Installation ......................................................................................................................
5.9.1
Before Installation..................................................................................................
5.9.1.1
Parts Inspection............................................................................................
5.9.2
Installation Site.......................................................................................................
5.9.2.1
Installation Site Selection ............................................................................
5.9.2.2
Installation Site Conditions..........................................................................
5.9.3
Installation Procedure.............................................................................................
5.9.3.1
Connecting Power Supply and Ground .......................................................
5.9.3.2
Changing the Power Supply Voltage...........................................................
5.9.3.3
Connecting Gas............................................................................................
5.9.3.4
Installing the Drain Container......................................................................
5.9.4
Installing the ASI-L................................................................................................
5.9.5
OCT-L Installation .................................................................................................
5.9.6
Installing the TNM-L .............................................................................................
5.9.6.1
TNM-L TN Unit Installation .......................................................................
5.9.6.2
Connecting Ozone Source Air .....................................................................
5.9.6.3
Connecting Gas Exhaust Tubing .................................................................
5.10 Safety Data Sheets..........................................................................................................
5.10.1 Hydrochloric Acid (HCl) .......................................................................................
5.10.2 Phosphoric Acid .....................................................................................................
5.10.3 IC Reagent..............................................................................................................
5.10.4 CO2 Absorber, Ca(OH)2, KOH, NaOH: Soda Lime..............................................
5.10.5 Ceramic Fiber.........................................................................................................
5.10.6 Catalyst Platinum Black.........................................................................................
357
357
357
357
357
359
360
360
361
361
364
365
371
374
374
374
376
377
377
380
383
386
389
391
TOC-LCSH/CSN
xxiii
Table of Contents
This page is intentionally left blank.
xxiv
TOC-LCSH/CSN
1
1
Overview
This chapter provides an overview of the instrument and the operational precautions for
instrument use.
1.1
Overview
Provides and overview of this instrument.
1.2
Operational Precautions
Details precautions necessary to ensure that the instrument is used correctly.
1
1
1.1
Overview
1.1
Overview
The TOC-LCSH/TOC-LCSN (hereinafter referred to as TOC-L) is an instrument that
measures the amount of total carbon (TC), inorganic carbon (IC) and total organic carbon
(TOC) in water. Purgeable organic carbon (POC) can also be measured when that accessory
is installed. "Oxidative combustion-infrared analysis" is a widely used TOC measurement
method that has been adopted by the JIS1 and other international standards. By installing
the optional TN unit, it is also possible to measure total water-borne nitrogen (TN) using
the principles of "oxidative combustion-chemiluminescence."
Moreover, when the ASI-L Autosampler or OCT-L 8-Port Sampler is used in combination
with the main unit, a fully automatic system is created, allowing automatic analysis of
multiple samples.
This instrument is a qualified product in Shimadzu's ecolabel program.
The power consumption of this instrument has been reduced by 36 % for a
supply voltage of 100 V and 43 % for a supply voltage of 200 V compared
to previous TOC-V models. (Usage conditions: (8 hours of operation per
day) × (5 hours of operation per week))
CAUTION
Safety may be compromised if the instrument is used in a fashion other than that
indicated in this USER'S MANUAL. Pay particular attention to the CAUTION
sections to ensure safety when using the instrument.
1. JIS K-0102 "Industrial Waste Water Testing", JIS K-0551: "Total organic carbon (TOC) testing methods
for ultra-pure water", U.S.Pharmacopoeia, EPA 415.1, EPA 9060A, ASTM D7573-09, Standard Methods
for Examination of Water and Waste Water 5310B
2
TOC-LCSH/CSN
1.2
1.2
Operational Precautions
Operational Precautions
Take the following precautions when using this instrument.
CAUTION
•
This instrument is used for measuring the amount of organic and nitrogenous substances
in water (additional options allow gaseous and solid sample measurement). Do NOT
measure liquids other than water samples. <Part damage prevention>
•
Do not touch the electric furnace while it is heating. The center of the electric furnace
(near the combustion tube insertion opening) reaches very high temperatures, and burns
may result. <Burn prevention>
•
To prevent high sensitivity catalyst from being forced upward in the combustion tube,
verify that carrier gas is flowing when heating the electric furnace. <Prevents the
floating of high sensitivity catalyst>
•
Allow the electric furnace to cool to room temperature for at least six hours after
switching off the power supply by shutting down the instrument before removing or
exchanging the combustion tube. Burns may result if this procedure is attempted when
the furnace is at a high temperature. <Burn prevention>
•
Do not heat the electric furnace without the combustion tube installed. The parts of the
TC injection port will be exposed to radiant heat from the center of the electric furnace
and may become deformed. If the furnace must be heated without the combustion tube
installed, either remove the TC injection port parts from the instrument in advance to
prevent deformation or cover the furnace core opening with quartz wool or another
suitable insulator. <Part damage prevention>
•
To reduce back pressure, verify that the external drain tubing connected to the waste
port on the right side of the instrument does not touch the surface of the liquid in the
waste container. The height of the external tube must always be lower than the height of
the drain port. Note that excessive back pressure will prevent sufficient drainage and
cause overflowing from the drain pot. <Part corrosion prevention>
TOC-L
Drain discharge tubing (Avoid
installing the tubing as shown
by the dotted line.)
Drain container (Prepare a
suitable drain container.)
Figure 1.1
TOC-LCSH/CSN
3
1.2
Operational Precautions
•
Hand tighten the various connectors to the 8-port valve. Use of a tool may cause
deformation and leakage in the valve. <Part damage prevention>
•
Stop operation of the instrument when performing maintenance on any of the drive
components, such as connecting lines to the 8-port valve, or connecting/ disconnecting
lines on the sample injector. If these parts are manipulated or if the lines are
disconnected during operation, the drive component could move, causing injury or
discharge of liquid. <Injury prevention, corrosion prevention>
•
Specify the Shut down instrument option in the Shutdown window to shut down the
instrument. The electric furnace turns OFF and the power supply shuts off after 30
minutes except for a minimum amount of power necessary to keep the software
running. This shutdown process extends the life of the TC injection port parts by
preventing unnecessary wear. This procedure does not apply to emergency shutdown.
<Maintaining durability of TC injection port parts>
•
Turn the lever of the 3-way valve at the bottom of the IC reaction vessel to the left
position. The lower position allows carrier gas to flow at a pressure of 200kPa upstream
from the 3-way valve, causing possible disconnection of joints and damage to parts such
as the combustion tube.
Carrier gas is discharged
to the front of the IC
reaction vessel. (Turn
the lever to this position
only when detaching an
IC reaction vessel that
contains liquid.)
Never turn the lever
to this position.
Figure 1.2 Lever Position of 3-Way Valve on the IC Reaction Vessel
4
•
Always verify that the ozone air source is supplying air at a rate of 0.5 L/min when
using the TNM-L. This helps to prevent ozone leaks and line corrosion. <Ozone leak
prevention, line corrosion prevention>
•
If an ozone odor is detected while using the TNM-L, immediately stop the current
measurement (without turning off the gas supply) and contact your Shimadzu
representative to request maintenance. Ozone can cause respiratory organ injury and
equipment damage. <Prevention of respiratory organ injury and equipment damage>
•
The optional POC measurement circuit incorporates a carbon dioxide (CO2) absorber
packed with lithium hydroxide for removal of carbon dioxide gas. Misuse of lithium
hydroxide can cause bodily harm. During packing or replacing the CO2 absorber
container, exercise adequate precaution. After use, treat the material as industrial waste.
The properties and handling guidelines for lithium hydroxide are described in the
material safety data sheets (MSDS) in Section 5.10 "Safety Data Sheets" on page 377.
TOC-LCSH/CSN
1.2
Operational Precautions
•
To clean the instrument, wipe the surface with a soft cloth moistened with water. Do not
use chemicals.
•
Keep samples and chemicals away from the PC and printer.
•
Repairs to the inside of this instrument can be dangerous. Contact your Shimadzu
representative to have a trained service engineer perform any repairs.
•
Do not disassemble or modify this instrument beyond the scope of the maintenance
procedures in this manual as safety may be compromised.
•
Do not use the instrument in hazardous areas (where fire is prohibited) because the
construction of the instrument is not explosion-proof. Also, the instrument cannot be
used in cleanroom environments.
•
Select an installation site with a stable ambient temperature and clean surroundings free
from corrosive gas, organic gas, and dust. Dirty surroundings in particular can cause
measurement errors when performing high sensitivity measurements. Install the
instrument on a sturdy, horizontal bench free from vibrations and physical impacts.
•
In order to obtain favorable measurement values, do not install the instrument near
windows subject to direct sunlight, other sources of heat, or locations directly subject to
cool air from air conditioning, or near equipment that generates strong magnetic fields,
electric fields, or high frequency waves.
•
Use the instrument with a grounded power supply of AC 100 ± 10 V.
•
Do not use the following characters when naming files or systems to be saved:
/ , . \ (back slash) : ; (these are all normal-width characters), space (normal width, em
width)
•
Hand-tighten the connectors to the 8-port valve of the OCT-L. Over-tightening with a
tool may exert excessive force to the internal valve body, causing deformation and
internal leakage. <Part damage prevention>
•
Shut down the instrument before connecting or disconnecting tubing to the 8-port valve
or performing maintenance to the drive parts. Liquid may be discharged from tubes
during operation. <Part corrosion prevention>
•
Do not write on the periphery of the vial rack or stick adhesive tape onto the vial rack. If
aluminum foil or water droplets are adhered to the periphery of the vial rack, remove
them. These may prevent the vial rack from rotating correctly.
•
At the start of measurement, the ASI-L rotates the vial rack by one revolution to detect
its home position and performs initialization. In order to perform measurement
correctly, the ASI-L may also detect shift in the vial rack position during measurement
and perform correction by rotating the vial rack by one revolution. This does not mean
that an abnormality has occurred.
TOC-LCSH/CSN
5
1.2
Operational Precautions
This page is intentionally left blank.
6
TOC-LCSH/CSN
2
System Description
2
This chapter identifies the components of the TOC-LCSH/CSN, autosampler and the TN
unit.
2.1
TOC-LCSH/CSN Construction
This section shows the construction of the TOC-L main unit using front, right,
left, rear, and internal front and top views depicted diagonally from the left of the
instrument, as well as flow diagrams.
2.2
Autosampler (Option)
This section shows the construction of the ASI-L unit using front and rear views
depicted diagonally from the left.
2.3
8-Port Sampler OCT-L (Option)
This section shows the construction of the OCT-L unit using front and rear views
depicted diagonally from the left and right.
2.4
TN Unit (Option)
This section shows the construction of the TNM-L unit using a front view
depicted diagonally from the right, a right view showing inside the door, and a
rear view.
2
2
2.1
TOC-LCSH/CSN Construction
2.1
TOC-LCSH/CSN Construction
2.1.1 Front View
Power switch (with
LED)
Indicators
Front door
Figure 2.1 Front View
2.1.2 Right Side View
Main power switch
Front door
Figure 2.2 Right Side View
8
TOC-LCSH/CSN
2.1
TOC-LCSH/CSN Construction
2.1.3 Left Side View
Sampling tubing
Front door
IC reagent
Drain pot
Dilution water bottle
Drain tubing
Hydrochloric acid
Figure 2.3 Left Side View
TOC-LCSH/CSN
9
2.1
TOC-LCSH/CSN Construction
2.1.4 Rear View
AC cord socket
Carrier gas inlet
Dip switches for various settings
Standalone/PC control switch
Printer connection socket
PC connection socket
ASI-L/OCT-L connection socket
Figure 2.4 Rear View
10
TOC-LCSH/CSN
Extension board slot cover
2.1
TOC-LCSH/CSN Construction
2.1.5 Front Internal View (Left Diagonal)
Sparge gas flow meter
(option)
Sliding IC sample injector
(H Type only)
Sparge gas flow adjustment
knob (option)
IC reaction vessel
(H Type only)
Carrier gas pressure
adjustment knob (option)
3-way tap
Halogen scrubber
8-port valve
Humidifier
5 mL syringe
may giu am
Cooling tubing unit
Solenoid valve (for IC drain discharge)
(H Type only)
Pump (for supplying IC reagent)
(H Type only)
Figure 2.5 Front Internal View (Left Diagonal)
TOC-LCSH/CSN
11
2.1
TOC-LCSH/CSN Construction
2.1.6 Top Internal View (Left Diagonal)
Motor for driving the slider
Sample injector block
Cooling fan for the sample injector block
Figure 2.6 Top Internal View (Left Diagonal)
2.1.7 Keyboard Layout
Function keys
ABC key
MEAS key
NEXT key
ASI key
CAL key
BS key
METHOD key
SAVE METHOD
key
Arrow keys
Power switch
START key
PRINT key
STOP key
CE key
Numeric keypad
ENTER key
Figure 2.7 Keyboard Layout
12
TOC-LCSH/CSN
2.1
TOC-LCSH/CSN Construction
Entering English Characters
Pressing the [ABC] key allows entry of English characters and symbols using the numeric
keys. Each English letter is assigned to a key, and each time the key is pressed, the letter
changes as indicated in the following table.
Numeric Key
1
2
3
4
5
6
7
8
9
0
.
TIP »
Corresponding English Letter / Symbol
.#/
ABC
DEF
GHI
JKL
MNO
PQRS
TUV
WXYZ
Moves cursor left
Moves cursor right
Moving the Cursor
After displaying the character you wish to enter, pressing another key automatically
moves the cursor to the right, allowing entry of the next character. In addition, if the
next character to be entered is assigned to the same numeric key, first press "." to move
the cursor right.
Example: Entering "ABC"
1.
Press the [ABC] key.
The [ABC] key illuminates.
2.
Press "2" once.
The letter A is entered.
3.
Press ".".
The cursor moves one space to the right.
4.
Press "2" twice.
The letter B is entered.
5.
Press ".".
The cursor move one space to the right.
6.
Press "2" three times.
The letter C is entered.
7.
Press the [Enter] key to confirm the entry.
TIP »
Deleting Characters
To delete one character, press the [BS] key (the character at which the cursor is
positioned is deleted.) To delete all of the entered characters, press the [CE] key.
TIP »
Inserting Characters
Move the cursor using the "0" key or ".", as appropriate, and then enter the
appropriate character.
TOC-LCSH/CSN
13
2.1
TOC-LCSH/CSN Construction
TIP »
Adjusting the Screen Contrast
While keeping the ABC key in the "Initial Display" ON, adjust the contrast with the ↑ ↓
keys.
2.1.8 Flow Diagrams
Diluent
IC Reaction
Vessel
Backflow
Prevention Trap
IC Reagent
Supply Pump
Acid
Solenoid
Valve 3
(To Drain)
Light Source
Sample
Backflow
Prevention
Valve
Sliding TC
Sample
Injector
Phosphoric
Acid
IC Reagent
CO2 Absorber
NDIR Tandem Cell
(Sample Cell)
Halogen Scrubber
5 mL Syringe
Dehumidifier
(Electronic Cooler)
Membrane Filter
Detector
Pure Water Trap
TC Combustion
Tube
Pressure Sensor PS3
Proportional Valve 2
Drain Pot
Cooling Tubing
Solenoid Valve 1
Pressure
Proportional
Sensor PS1
Valve 1
Pressure
Sensor PS2
Humidifier
Carrier Gas Inlet
Figure 2.8 Flow Diagram (TOC-LCSH)
Diluent
IC Reaction
Vessel
Backflow
Prevention Trap
IC Reagent
Supply Pump
Acid
Solenoid
Valve 3
(To Drain)
Light Source
Sample
Backflow
Prevention
Valve
Sliding TC
Sample
Injector
Chemiluminescence
Detector
Phosphoric
Acid
IC Reagent
NDIR Tandem
Cell (Sample
Cell)
Ozone
Generator
Halogen Scrubber
5 mL Syringe
Dehumidifier
(Electronic Cooler)
Membrane
Filter
Detector
Pure Water Trap
Pressure Sensor PS3
Exhaust
Pressure
Sensor PS5
TC Combustion
Tube
Proportional Valve 2
Drain Pot
Solenoid
Valve 1
Pressure
Proportion Pressure
Sensor PS1 al Valve 1 Sensor PS2
Carrier
Gas Inlet
Cooling Tubing
NOx Absorber
Regulator
Humidifier
Solenoid
Valve
Sample or ASI
Flow Meter
with Valve
Solenoid
Valve 6
External Sparge Kit
Figure 2.9 Flow Diagram (TOC-LCSH + TNM-L + External Sparge Kit)
14
Ozone
Treatment
Unit
TOC-LCSH/CSN
Gas Inlet
2.1
Diluent
TOC-LCSH/CSN Construction
IC Reaction
Vessel
IC Reagent
Supply Pump
Backflow
Prevention Trap
Acid
Solenoid
Valve 3
(To Drain)
Light Source
Sample
Backflow
Prevention
Valve
Sliding TC
Sample Injector
Phosphoric
Acid
IC Reagent
CO2 Absorber
NDIR Tandem
Cell (Sample
Cell)
CO2 Absorber
Halogen Scrubber
5 mL Syringe
Dehumidifier
(Electronic Cooler)
Oxygen Permeation
Tubing
N2 Carrier Gas Kit
Membrane Filter
Detector
Pure Water Trap
TC Combustion
Tube
Pressure Sensor PS3
Drain Pot
Cooling Tubing
Proportional Valve 2
Pressure
Sensor PS1
Solenoid Valve 1
Proportional
Valve 1
Pressure
Sensor PS2
Humidifier
Carrier Gas Inlet
Figure 2.10 Flow Diagram (TOC-LCSH + N2 Carrier Gas Kit)
Acid
3
4
5
1
8
IC Reagent
Supply Pump
P
Solenoid Valve 4
6
2
Sample or ASI
IC Reaction
Vessel
Backflow
Prevention Trap
Diluent
Solenoid
Valve 3
(To Drain)
7
Solenoid Valve 2
(For Sparging)
CO2
Absorber
Light Source
IC Reagent
Sliding TC
Backflow Sample
Prevention Injector
Valve
Phosphoric
Acid
CO2 Absorber
NDIR Tandem
Cell (Sample
Cell)
Halogen Scrubber
5 mL Syringe
Dehumidifier
(Electronic Cooler)
Membrane Filter
Detector
Pure Water Trap
Pressure Sensor PS3
TC Combustion
Tube
Proportional Valve 2
Solenoid Valve 1
Pressure Sensor
PS1
Drain Pot
Proportional
Valve 1
Pressure
Sensor PS2
Humidifier
Cooling Tubing
Carrier Gas Inlet
Figure 2.11 Flow Diagram (TOC-LCSH + POC Kit)
TOC-LCSH/CSN
15
2.1
TOC-LCSH/CSN Construction
Manual IC
Gas Injector
Diluent
IC Reaction
Vessel
Backflow
Prevention Trap
IC Reagent
Supply Pump
Acid
Manual TC
Gas Injector
Solenoid
Valve 3
(To Drain)
Light Source
Sample
Backflow
Prevention
Valve
Sliding TC
Sample
Injector
IC Reagent
Phosphoric
Acid
CO2 Absorber
NDIR Tandem
Cell (Sample
Cell)
Halogen Scrubber
5 mL Syringe
Dehumidifier
(Electronic Cooler)
Membrane Filter
Detector
Pure Water Trap
TC Combustion
Tube
Pressure Sensor PS3
Proportional Valve 2
Drain Pot
Cooling Tubing
Pressure
Proportional
Sensor PS1
Valve 1
Solenoid Valve 1
Pressure
Sensor PS2
Humidifier
Carrier Gas Inlet
Figure 2.12 Flow Diagram (TOC-LCSH + Manual Injection Kit)
Diluent
Acid
Light Source
Sample
Solenoid Valve 2
(For Sparging)
Backflow
Prevention
Valve
Sliding TC
Sample
Injector
CO2 Absorber
Halogen Scrubber
NDIR Tandem
Cell (Sample
Cell)
5 mL Syringe
Membrane Filter
Dehumidifier
(Electronic Cooler)
Pure Water Trap
Pressure Sensor PS3
TC Combustion
Tube
Proportional Valve 2
Drain Pot
Solenoid Valve 1
Pressure
Sensor PS1
Proportional
Valve 1
Pressure
Sensor PS2
Humidifier
Cooling Tubing
Carrier Gas Inlet
Figure 2.13 Flow Diagram (TOC-LCSN)
16
TOC-LCSH/CSN
Detector
2.1
TOC-LCSH/CSN Construction
Diluent
Acid
Light Source
Sample
Solenoid Valve 2
(For Sparging)
Chemiluminescence
Detector
Sliding TC
Sample
Injector
Backflow
Prevention
Valve
NDIR Tandem
Cell (Sample
Cell)
Ozone
Generator
Halogen Scrubber
5 mL Syringe
Dehumidifier
(Electronic Cooler)
Membrane
Filter
Detector
Ozone
Treatment
Unit
Pure Water Trap
Pressure Sensor PS3
Exhaust
TC Combustion
Tube
Proportional Valve 2
Pressure
Proportion Pressure
Sensor PS1 al Valve 1 Sensor PS2
Solenoid Valve 1
Carrier
Gas Inlet
Cooling Tubing
Pressure
Sensor PS5
NOx Absorber
Drain Pot
Regulator
Humidifier
Solenoid
Valve
Sample or ASI
Flow Meter
with Valve
Gas Inlet
Solenoid
Valve 6
External Sparge Kit
Figure 2.14 Flow Diagram (TOC-LCSN + TNM-L + External Sparge Kit)
Solenoid
Valve 4
Diluent
Acid
Light Source
Sample
Solenoid Valve 2
(For Sparging)
CO2
Absorber
Backflow
Prevention
Valve
Sliding TC
Sample
Injector
CO2 Absorber
NDIR Tandem
Cell (Sample Cell)
Halogen Scrubber
5 mL Syringe
Membrane Filter
Detector
Dehumidifier
(Electronic Cooler)
Pure Water Trap
Pressure Sensor PS3
TC Combustion
Tube
Proportional Valve 2
Drain Pot
Solenoid Valve 1
Pressure
Sensor PS1
Proportional
Valve 1
Pressure
Sensor PS2
Humidifier
Cooling Tubing
Carrier Gas Inlet
Figure 2.15 Flow Diagram (TOC-LCSN + POC Kit)
TOC-LCSH/CSN
17
2.1
TOC-LCSH/CSN Construction
Diluent
Acid
Light Source
Sample
Backflow
Prevention
Valve
Solenoid Valve 2
(For Sparging)
Chemiluminescence
Detector
Sliding TC
Sample
Injector
NDIR Tandem
Cell (Sample
Cell)
Pure Water Trap
Halogen Scrubber
Ozone
Generator
5 mL Syringe
Membrane
Filter
Detector
Dehumidifier
(Electronic Cooler)
Ozone
Treatment
Unit
Exhaust
Pressure Sensor PS3
L-Shaped
Combustion
Tube
Pressure
Sensor PS5
TC
Combustion
Tube
Proportional Valve 2
Cooling Tubing
Solenoid Valve 1
Drain Pot
NOx Absorber
Regulator
Solenoid
Valve
Pressure
Proportional Pressure
Sensor PS1
Valve 1 Sensor PS2
Humidifier
Carrier Gas Inlet
Gas Inlet
Carrier Gas Purification Kit
CO2 Absorber
Figure 2.16 Flow Diagram (TOC-LCSN + TNM-L + Carrier Gas Purification Kit)
18
TOC-LCSH/CSN
2.2
2.2
Autosampler (Option)
Autosampler (Option)
2.2.1 Front View (Left Diagonal)
Sparging tubing (option)
Sampling tubing
Door for needle replacement
Power switch
Sample cover
Figure 2.17 Front View (Left Diagonal)
2.2.2 Rear View (Left Diagonal)
Rinse bottle
Stirrer rotation speed
adjustment dial (option)
Drain tubing
Tubing to supply rinse water
Connection cable
Figure 2.18 Rear View (Left Diagonal)
TOC-LCSH/CSN
19
2.3
8-Port Sampler OCT-L (Option)
2.3
8-Port Sampler OCT-L (Option)
2.3.1 Front View (Left Diagonal)
8-port valve
Figure 2.19 Front View (Left Diagonal)
2.3.2 Rear View (Right Diagonal)
Connection cable
Connection cable
(for linking two OCT-L units)
Figure 2.20 Rear View (Right Diagonal)
20
TOC-LCSH/CSN
2.4
2.4
TN Unit (Option)
TN Unit (Option)
2.4.1 Front View (Right Diagonal)
TNM-L
TNM-L maintenance door
Figure 2.21 Front View (Right Diagonal)
2.4.2 View Inside the Door on the Right Side
Flow rate adjustment knob
for the ozone air source
Figure 2.22 View Inside the Door on the Right Side
TOC-LCSH/CSN
21
2.4
TN Unit (Option)
2.4.3 Rear View
Ozone air source inlet
Figure 2.23 Rear View
22
TOC-LCSH/CSN
3
3
Operation
This chapter describes pre-analysis preparations, parameter entry procedures and
operation procedures for calibration curve generation and sample analysis.
3.1
Analysis Preparation
This section describes catalyst filling, combustion tube connection, syringe
installation and other procedures used for actual sample analysis.
3.2
Analysis
This section describes procedures from instrument start-up to calibration curve
generation. These procedures include sample analysis, method development,
halting of analysis and instrument shutdown.
3.3
Analysis with the Autosampler
This section describes the procedure for performing analysis using the
autosampler.
3.4
Analysis with the 8-Port Sampler
This section describes the procedure for performing analysis using the 8-port
sampler.
3.5
Data Review
Procedures for reviewing the calibration curve list, method list and data reports
are described here.
3.6
Outputting Data to a USB Memory Device
This section describes how to output data to a USB memory device.
3.7
Applications Operations (H Type Only)
The procedures for performing manual injection analysis and gas sample
analysis are described in this section.
33
3.1
Analysis Preparation
3.1
Analysis Preparation
3.1.1 Catalyst Filling
There are three types of catalyst: TOC standard catalyst, TOC high sensitivity catalyst (H
Type only), and TOC/TN catalyst (option). For TOC analysis, fill the combustion tube with
catalyst as described in Section 3.1.1.1 "Catalyst for TOC Analysis" on page 25. For TN
analysis, refer to Section 3.1.1.2 "TOC/TN Catalyst (Option)" on page 27.
CAUTION
Exercise caution when handling the combustion tube to prevent breakage as it is
constructed from quartz glass.
Note:
When filling the combustion tube, verify that the catalyst does not become
contaminated. Contamination will cause high blank values and abnormal analysis
values.
Using New Catalyst
Broad blank peaks are associated with the initial use of new catalyst. These blank peaks
become progressively smaller with repeated injections, and the peak size becomes stable.
This tendency is more obvious with high sensitivity TC analysis. If calibration or analysis
is performed while the blank peaks are large, the measurements are altered with the
changing magnitude of the blank peaks, resulting in errors in the analysis values.
TC Analysis Using New Catalyst
Catalyst regeneration should be conducted 1-2 times for TC analysis using new catalyst.
This reduces the size of the blank peaks. Use continuous injections of pure water until the
blank peak area becomes small and stable. Refer to Section 3.2.3.1 "Single-mode Analysis"
on page 112 step " (2) Continuous Measurement in Same Mode". The blank peak
magnitude depends on the quality of the water (TC impurity concentration) and the TC
range used for analysis. For analysis of concentrations 100mg/L or greater, a blank peak of
1mg/L will have little influence on the results. However, analysis of concentrations around
10mg/L must have stable blank peaks of 0.5mg/L or less.
In addition, measure the NPOC of the sample using the calibration curve created in the
previous section when using TOC high sensitivity catalyst. Measure the sample using the
same method used to measure standard solution, as described in (2) in the previous section.
Be aware that when sparging is performed using the optional external sparging kit and
repeated analysis of the same sample results in gradually decreasing values, the sparging
time may be too short. In this case, extend the sparging time. The required sparging time
depends on the shape of the sample container, sample volume, sparge gas volume, and
amount of IC in the sample. Determine a suitable sparging time according to each of these
conditions.
Perform the procedure described in Section 3.1.19.2 "TC Blank Check Analysis" on page
79.
24
TOC-LCSH/CSN
3.1
Analysis Preparation
TN Analysis Using New Catalyst
Blank peak magnitude poses no practical problems for TN analysis using new catalyst. The
blank peaks are fairly small and stable. Perform analysis with distilled or deionized water to
confirm the blank peak size.
3.1.1.1 Catalyst for TOC Analysis
Either standard TOC catalyst or optional TOC high sensitivity catalyst can be used for TOC
analysis. The furnace temperature is set to 680°C for TOC analysis.
TOC Standard Catalyst
The commonly used standard TOC catalyst is appropriate for both the TC-IC method and
NPOC method of analysis.
Note:
Analyze TOC high precision samples of about 1mg/L using the TOC high
sensitivity catalyst because smaller blank peaks are generated.
Filling Combustion Tube with TOC Standard Catalyst
1.
2.
3.
Insert two sheets of platinum mesh into the combustion tube.
Layer about 5mm of quartz wool onto the platinum mesh using the catalyst filling rod.
Fill the TOC standard catalyst to a height of about 100mm.
Combustion Tube
Standard TOC Catalyst
100mm
Len thach anh
Quartz Wool
Platinum Mesh
luoi thep platium
Figure 3.1 Combustion Tube with Standard TOC Catalyst
CAUTION
Take care not to inhale any quartz wool when filling the combustion tube.
TOC-LCSH/CSN
25
3.1
Analysis Preparation
TOC High Sensitivity Catalyst (H Type only)
Use the TOC high sensitivity catalyst is for low level TC analysis. The blank values are
controlled to negligible levels, and analysis is performed primarily for trace TOC in pure
water (1mg/L or less).
Samples containing IC in excess of 5mg/L
The detection rate for IC decreases with increasing concentration, therefore, when IC is
contained in the sample in excess of 5mg/L, use the NPOC method instead of the TC-IC
method.
Filling Combustion Tube with TOC High Sensitivity Catalyst
Two cylindrical containers of catalyst are required for a single load. The procedure is as
follows.
1.
2.
Place two sheets of platinum mesh in the combustion tube.
3.
Use the catalyst filling rod to push catalyst into the combustion tube from the other
opened end of the cylindrical catalyst container.
4.
Transfer the contents of the two cylindrical catalyst containers to achieve a catalyst
layer of 110 mm in the combustion tube.
Fit together the combustion tube opening and the opened end of the cylindrical
catalyst container.
Combustion Tube
TOC High Sensitivity
Catalyst
110 mm
Platinum Mesh
Figure 3.2 Filling of TOC Combustion Tube with High Sensitivity Catalyst
26
TOC-LCSH/CSN
3.1
Analysis Preparation
3.1.1.2 TOC/TN Catalyst (Option)
TOC/TN catalyst is used for TN analysis and TN/TOC simultaneous analysis. TOC/TN
catalyst is not applicable for TC-IC analysis because the detection rate for the IC
component in excess of 10mg/L is low. Use the NPOC method for TOC analysis in these
situations. The furnace temperature is set to 720°C.
Filling Combustion Tube with Catalyst for TN Analysis
1.
2.
3.
Insert two sheets of platinum mesh into the combustion tube.
4.
5.
Introduce 0.2 (± 0.1) g of ceramic fiber to cover the catalyst.
Layer about 5mm of quartz wool onto the platinum mesh using the catalyst filling rod.
Introduce the standard TOC catalyst into the combustion tube to 140mm from the top
end of the combustion tube.
Lightly press down on the ceramic fiber using the catalyst filling rod to attain a
thickness of 10 mm.
Note: • The thickness of the ceramic fiber must be uniform, covering the entire
surface of the catalyst, or a poor TN detection rate may result.
• The filling heights of the catalyst and ceramic fiber influence the TN
detection rate, so it is important that the dimensions are close to those
indicated below.
Catalyst: 140mm from the top end of the combustion tube
Ceramic fiber: 10mm
Combustion Tube
Ceramic Fiber
10mm
140mm
Standard TOC Catalyst
Quartz Wool
Platinum Mesh
Figure 3.3 Filling Combustion Tube with Catalyst for TOC/TN Analysis
TOC-LCSH/CSN
27
3.1
Analysis Preparation
CAUTION
Take care not to inhale any quartz wool or ceramic fiber when filling the
combustion tube.
3.1.2 Installing the Cooling Tube Unit (H Type Only)
Install the cooling tube unit to the outlet of the combustion tube.
CAUTION
•
•
The cooling tube unit is made of hard glass. Handle the unit with care to prevent
breakage.
Tighten the hexagon cap nut while holding the PTFE coupling in place with your
finger when connecting the outlet tube to the cooling tube. The cooling tube with
break if the hexagon nut is tightened without holding the PTFE coupling in place.
1.
Open the front door on the instrument and connect the PTFE tube attached to the pure
water trap to the outlet of the cooling tube unit (the smaller PTFE coupling). At this
point, carefully tighten the hexagon cap nut while holding the PTFE coupling in place
with your finger.
2.
Loosen and remove the two fastening screws on the cooling tube unit located on the
lower section of the electric furnace and insert the screws into each of the two holes
on the upper section of the cooling tube unit and tighten them.
To the pure water trap
Cooling tube unit outlet
(PTFE coupling)
Fastening
screws
Cooling tubing unit
Figure 3.4 Installing the Cooling Tube Unit
28
TOC-LCSH/CSN
3.1
Analysis Preparation
3.1.3 Connecting the Combustion Tube
The procedure for installing the combustion tube differs depending on whether the
instrument is the H Type or the N Type.
CAUTION
•
•
•
Due to the potential for burns, maintenance of the combustion tube and catalyst
should be performed after the electric furnace temperature has cooled to room
temperature.
When connecting the combustion tube, handle it carefully to avoid breaking it.
The combustion tube is constructed of quartz glass, and injury is possible.
Do not use a wrench or other tool. Injury could result if the combustion tube
breaks.
Installation for the H Type
1.
Open the door on top of the instrument, remove the slider retaining screws (knurled
screws) from the sample injector, and pull the slider towards you and out of the
sample injector.
2.
Loosen the hexagon cap nut that joins the carrier gas introduction tubing (PTFE
tubing) to the right side of the sample injector and then remove the tubing.
3.
Loosen the two knurled screws on the sample injector and remove the sample injector
in the upward direction.
Slider retaining
screw
Slider
Carrier gas
introduction tubing
Sample injector retaining screws
(two)
Hexagon cap nut
Sample injector
Drain tubing
4.
Figure 3.5 Sample Injector
Securely insert the top end of the combustion tube filled with catalyst into the hole on
the bottom of the sample injector.
TOC-LCSH/CSN
29
3.1
Analysis Preparation
5.
Fit the combustion tube into the hole in the center of the electric furnace and then
insert the bottom end of the combustion tube into the PTFE coupling of the cooling
tubing inlet. At this point, securely connect the drain tubing, which protrudes out of
the sample injector, to the Y-shaped fitting.
Sample injector
Drain tubing
Combustion
tube
Y-shaped fitting
6.
7.
Figure 3.6 Installing the Combustion Tube
Secure the sample injector to the instrument body using the knurled screws.
Reattach the slider and carrier gas introduction tubing to their original positions.
Sample injector
Drain tubing
Sample injector retaining screws
Figure 3.7 Securing the Sample Injector to the Instrument Body
30
TOC-LCSH/CSN
3.1
Note:
8.
Analysis Preparation
Do not allow organic substances, such as grease or oil, to contaminate any parts
exposed to gas including the inner surfaces on the tip of the combustion tube as
well as joints. This is especially important for high sensitivity measurement.
Connect the bottom of the combustion tube to the PTFE coupling of the cooling
tubing inlet. Carefully tighten the hexagon cap nut while holding the PTFE coupling
in place with your finger.
Combustion tube
Cooling tubing unit
PTFE coupling
(cooling tubing inlet)
Figure 3.8 Connecting the Combustion Tube and Cooling Tubing
Bottom end of the
combustion tube
Hexagon cap nut
PTFE coupling
Cooling tubing inlet
Figure 3.9 Connecting the Bottom End of the Combustion Tube to the PTFE Coupling
CAUTION
The quartz glass combustion tube will break if the hexagon cap nut is
overtightened.
Tightening the PTFE coupling without holding it in place will break the cooling
tubing because it is made of hard glass.
TOC-LCSH/CSN
31
3.1
Analysis Preparation
9.
In order to prevent heat from escaping from the furnace, use the provided quartz wool
to fill the gap between the bottom of the electric furnace and the combustion tube as
well as the two notches in the insulator on top of the electric furnace.
CAUTION
Take care not to inhale any quartz wool when filling the combustion tube.
Combustion tube
Electric furnace
Quartz wool
Figure 3.10 Filling With Quartz Wool (Bottom of the Electric Furnace)
Fill with quartz wool
Insulator
Figure 3.11 Filling With Quartz Wool (Top of the Electric Furnace)
32
TOC-LCSH/CSN
3.1
Analysis Preparation
Installation for the N Type
1.
Open the door on top of the instrument, remove the slider retaining screws (knurled
screws) from the sample injector, and pull the slider towards you and out of the
sample injector.
2.
Loosen the hexagon cap nut that joins the carrier gas introduction tubing (PTFE
tubing) to the right side of the sample injector and then remove the tubing.
3.
Loosen the two knurled screws on the sample injector and remove the sample injector
in the upward direction.
Slider retaining
screw
Slider
Carrier gas
introduction tubing
Sample injector retaining screws
(two)
Hexagon cap nut
Sample injector
Drain tubing
4.
Figure 3.12 Sample Injector
Securely insert the top end of the combustion tube filled with catalyst into the hole on
the bottom of the sample injector.
TOC-LCSH/CSN
33
3.1
Analysis Preparation
5.
Fit the combustion tube into the hole in the center of the electric furnace and then
insert the bottom end of the combustion tube into the PTFE coupling of the cooling
tubing inlet. At this point, securely connect the drain tubing, which protrudes out of
the sample injector, to the Y-shaped fitting.
Sample injector
Drain tubing
Combustion
tube
Y-shaped fitting
6.
7.
Figure 3.13 Installing the Combustion Tube
Secure the sample injector to the instrument body using the knurled screws.
Reattach the slider and carrier gas introduction tubing to their original positions.
Sample injector
Drain tubing
Sample injector retaining screws
Figure 3.14 Securing the Sample Injector to the Instrument Body
34
TOC-LCSH/CSN
3.1
Note:
Analysis Preparation
Do not allow organic substances, such as grease or oil, to contaminate any parts
exposed to gas including the inner surfaces on the tip of the combustion tube as
well as joints. This is especially important for high sensitivity measurement.
CAUTION
The quartz glass combustion tube will break if the compression fitting is overtightened.
8.
Connect the bottom of the combustion tube to the PTFE coupling of the cooling
tubing inlet. Carefully tighten the hexagon cap nut while holding the PTFE coupling
in place with your finger.
Cooling tubing
PTFE coupling (Connects to the
bottom end of the combustion tube.)
Figure 3.15 Connecting the Combustion Tube and Cooling Tubing
TOC-LCSH/CSN
35
3.1
Analysis Preparation
9.
In order to prevent heat from escaping from the furnace, use the provided quartz wool
to fill the gap between the bottom of the electric furnace and the combustion tube as
well as the two notches in the insulator on top of the electric furnace.
CAUTION
Take care not to inhale any quartz wool when filling the combustion tube.
Combustion tube
Electric furnace
Quartz wool
Figure 3.16 Filling With Quartz Wool (Bottom of the Electric Furnace)
Fill with quartz wool
Insulator
Figure 3.17 Filling With Quartz Wool (Top of the Electric Furnace)
36
TOC-LCSH/CSN
3.1
Analysis Preparation
CAUTION
When installing or moving the instrument, insulation material powder may drop
under the electric furnace. Since insulation material contains ceramic fibers,
follow these precautions:
• When cleaning dust under the electric furnace, wipe with dampened cloths to
prevent dust or powder from being dispersed.
• Ceramic fibers are contained in the material used inside the electric furnace.
Never dismantle the electric furnace.
Refractory ceramic fibers (RCF) are fire-resistant inorganic fibers mainly consisting of alumina (Al2O3)
and silica (SiO2). This material is chemically stable and can be used as insulation material in a high
temperature range exceeding 1000 °C.
With this instrument, the dispersibility of fibrous mineral under normal conditions of use is measured and
is proven to be sufficiently low with respect to the maximum permissible dust concentration level.
TOC-LCSH/CSN
37
3.1
Analysis Preparation
3.1.4 Connecting the Halogen Scrubber
Connection Procedure
1.
Remove the film at both ends of the new halogen scrubber and connect it to the Viton
connectors.
2.
Secure the halogen scrubber with two white plastic clamps.
Gas Flow Direction
Replace Scrubber When
Discoloration Band Reaches
this Point
Dehumidifier
To Sample
Cell Inlet
Halogen Reactant-filled Cylinder
Figure 3.18 Halogen Scrubber
The baseline may fluctuate immediately after connection. Allow the instrument to run for a
short time until the baseline stabilizes. Stabilization normally occurs within one hour.
Halogen scrubber
(take note of the
arrow direction)
Figure 3.19 Halogen Scrubber Connection
38
TOC-LCSH/CSN
3.1
Analysis Preparation
3.1.5 Installing the Syringe
This section describes how to install the syringe into the instrument.
Each port of the 8-port valve for the syringe pump type sample injector is connected to
certain streams depending on the state of the instrument. Installing and removing the
syringe without following the correct procedure may cause acid and other substances to be
discharged from the syringe connection port. Always follow the procedure described
below.
CAUTION
•
•
•
If the syringe is installed using a procedure other than that described below, there
is a danger that acid, or other solutions may leak from the syringe connection
port. Ensure that the syringe is installed according to the procedure below.
To avoid injury, keep hands away from the sample injector during operation of
the syringe pump sample injector.
The syringe barrel is made of glass, handle it carefully to avoid breakage.
Syringe Replacement Procedure
1.
In the "Initial Display", press the F5 [Maintenance] key.
The "Maintenance" screen is displayed.
2.
3.
Using the ↓ key, move the cursor to the "Replace Syringe" item.
Press the [NEXT] key.
When the preparations for syringe replacement are completed, the message "Syringe
exchange. Exchange syringe now." is displayed.
TOC-LCSH/CSN
39
3.1
Analysis Preparation
4.
Attach the syringe to the syringe connection port (downward facing port) of the 8-port
valve and then connect the sparge gas line. At this point, the plunger retaining screw
is not completely tightened. Tighten the retaining screw so that the plunger can still be
slightly moved forwards and backwards as well as left and right.
Note: Do not use tools when replacing the syringe, hand tighten only.
Over-tightening can deform the resin components of the 8-port
valve, resulting in leaks. As a guide, tighten the screw until it stops
snugly and make one quarter turn further.
The plunger is secured to the plunger holder with the plunger
retaining screw through a spring washer. Be careful not to lose the
spring washer.
5.
Press the F4 [Move test Up & Down] key.
The plunger holder will rise.
6.
Once the syringe reaches the top position, hold the plunger vertical and tighten the
plunger retaining screw to secure it to the plunger holder.
7.
8.
Connect the sparge gas line to the syringe using the bushing and spacer.
9.
Press the F1 [Return] key.
The display returns to the "Initial Display".
Press the F6 [End] key.
The operation finishes, and the display returns to the "Maintenance" screen.
8-port valve
Syringe
Plunger
Plunger retaining screw
Plunger holder
Figure 3.20 Replacing the Syringe
40
TOC-LCSH/CSN
3.1
Analysis Preparation
3.1.6 Water Supply to the Dehumidifier Drain Vessel
The drain container must be filled with water to prevent carrier gas release from the drain
tubing.
Procedure
1.
Remove the cooler drain vessel from the mounting clip and then remove the rubber
cap from the vessel.
2.
Using a wash bottle, pour pure water (deionized water is acceptable) into the cooler
drain vessel up to the level of the drain discharge tubing on the side of the drain
vessel.
3.
Reattach the rubber cap onto the cooler drain vessel and return the vessel to its
position in the mounting clip.
4.
Verify that the cooler drain tubing is inserted straightly in the drain vessel without
being bent.
CAUTION
Do not bend drain tubing, as this may prevent drain discharge.
Rubber cap
Drain discharge tube
Cooler drain vessel
Figure 3.21 Filling the Dehumidifier Drain Vessel with Water
TOC-LCSH/CSN
41
3.1
Analysis Preparation
3.1.7 Filling the Humidifier with Water
It is necessary to humidify the carrier gas for high sensitivity analysis, to ensure high
analysis precision. Water is supplied to the humidifier using the following procedure.
Procedure
1.
2.
Remove the cap from the water supply port at the top of the humidifier.
Introduce water through the water supply port to the "Hi" marking on the side of the
humidifier.
Note: Use pure water containing as little TC as possible for high
sensitivity analysis.
Water supply port
Humidifier
Figure 3.22 Filling the Humidifier with Water
42
TOC-LCSH/CSN
3.1
Analysis Preparation
3.1.8 Preparation of Dilution Water
This section describes how to prepare the dilution water required to automatically dilute the
sample inside the instrument.
Filling Procedure
1.
Wash the provided dilution water bottle (2 L capacity) with laboratory detergent, rinse
well with tap water and then a number of times with pure water.
2.
3.
4.
Fill the dilution water bottle with pure water and place it to the left of the instrument.
5.
Place the cap on the dilution water bottle.
Note: Verify that the tip of the intake tubing nearly reaches the bottom of
the container.
Pass the dilution water intake tubing, labeled DILUTION, through the hole in the cap.
Attach a wiring band about 250 mm from the end of the dilution water intake tubing
to prevent the tubing from separating from the cap.
Dilution water
intake tubing
Dilution water bottle
Figure 3.23 Preparing Dilution Water
Note:
Pure Water
• Use the purest water that can be obtained.
• Refer to Section 3.1.18.1 "Preparation of Standard Solutions" on page 73
for details on the degree of purity of "pure water".
TOC-LCSH/CSN
43
3.1
Analysis Preparation
3.1.9 Acid Preparation
This section describes the preparation of acid used for IC removal in NPOC measurement
and IC measurement with the N Type instrument.
Although the concentration of hydrochloric acid is normally 1 mol/L as described below,
adjust the concentration according to the properties of the sample.
Preparation Procedure
1.
Dilute commercially available special grade concentrated hydrochloric acid
(12 mol/L) with 12 parts pure water to prepare 1 mol/L hydrochloric acid. A
concentration accuracy of approximately ±2 % is acceptable.
The pure water used as the diluent must have a TOC concentration no greater than
0.5 mg/L. Since the TOC value of the diluent pure water can have a large effect on the
analysis result with high sensitivity analysis (low TOC concentrations), it is necessary
to use pure water having a very low TOC concentration.
CAUTION
Hydrochloric acid is a hazardous chemical. Use precautions to avoid contact
when handling this substance. For details, refer to Section 5.10 "Safety Data
Sheets" on page 377.
2.
Pour the prepared acid into the 250 mL acid container provided standard with the
instrument, and secure the acid container in the mounting clip on the left side of the
instrument.
3.
4.
Pass the acid intake tubing through the hole in the cap.
5.
Place the cap on the container.
Note: Verify that the tip of the acid intake tubing nearly reaches the
bottom of the container.
Secure the tubing, using a wire clamp about 100 mm from the end of the tubing, to
prevent the tubing and cap from separating.
Acid intake tubing
Acid container (250 mL capacity)
Figure 3.24 Acid Preparation
44
TOC-LCSH/CSN
3.1
Analysis Preparation
3.1.10 Installation of the CO2 Absorber
A CO2 absorber is required to remove CO2 from carrier gas because carrier gas is used to
purge the optical system of the detector. Install the CO2 absorber by following the
procedure described below.
Procedure
1.
2.
Cut the tips of the rigid tubes (2) in the lid of the CO2 absorber with a knife.
3.
Place the CO2 absorber in the holder on the upper rear of the instrument.
Connect the flexible tubing that exits the rear panel of the instrument near the top as
described below.
Tubing labeled "L": Connect to tube labeled "L" on CO2 absorber.
Tubing labeled "S": Connect to tube labeled "S" on CO2 absorber.
Note: The flexible tubing should not be bent.
Connect to
the absorber
CO2 absorber
Figure 3.25 Installation of the CO2 Absorber
3.1.11 Printer Preparation
Printers having the following control codes can be connected to the TOC-L.
ESC/P-Raster (some models)
ESC/P-9
ESC/P-24 (ESC/P-J84 or ESC/P Super (ESC/P emulations))
PCL (PCL3, PCL5, PCL5e)
Printer Connection Procedure
1.
Connect the printer by plugging the USB cable into the printer connection terminal on
the rear of the TOC-L.
2.
See Section 3.1.17.5 "Printer Setup" on page 60 and set up the printer.
TOC-LCSH/CSN
45
3.1
Analysis Preparation
3.1.12 Installing the Suspended Solids Kit
To analyze samples containing suspended solids, the sample flow line diameter can be
increased from 0.5mm to 0.8mm by installing the optional Suspended Solids Kit.
This section describes the installation of the Suspended Solids Kit.
There are two kits available:
1)
For TOC-L (TOC-L main unit only)
2)
For TOC-L+ASI-L (used with TOC-L and ASI-L)
CAUTION
Switch OFF the TOC-L before attempting to install the Suspended Solids kit.
Replacing the Flow Line Parts and Slider
This procedure is used for both kits.
Procedure
1.
Remove the bushing from port 7 of the 8-port syringe pump valve, and disconnect the
TC injection tubing. For the H-type, remove the bushing from port 5, and disconnect
the IC injection tubing.
2.
Remove the slider mounting screws from the TC and IC injection blocks, and detach
the sliders.
3.
Remove the slider bushings and replace the sample injection tubing with the 0.8 mm
diameter sample injection tubing provided in the kit.
4.
5.
Re-install the sliders on the sample injection blocks.
Connect the TC injection tubing and the IC injection tubing to port 7 and port 5,
respectively.
Note: During analysis, verify that the sample flow is normal. Refer to
Section 4.6.2.4 "Remedial Actions for Poor Repeatability" on page
274.
If the sample flow is not normal, the tip of the PTFE tube may be deformed
or scratched. Use a knife to cut off a portion of the tube.
Replacing Sample Aspiration Tubing
For TOC-L (main unit only)
46
1.
Remove the bushing from port 1 of the 8-port syringe pump valve, and replace the
sample aspiration tubing with the 0.8mm diameter tubing provided in the kit.
2.
Connect the new sample aspiration tubing to the 8-port valve in the original position.
TOC-LCSH/CSN
3.1
Analysis Preparation
For TOC-L+ASI-L (TOC-L and ASI-L)
Refer to Section 5.9.4 "Installing the ASI-L" on page 365, to remove the autosampler
sample needle and sample aspiration tubing. Replace these with the sample needle and
aspiration tubing provided in the Suspended Solids kit.
Precautions for Measuring Suspended Solids
When performing measurement of solid samples using the Suspended Solids
Measurement kit, follow the precautions below to ensure the best possible
conditions for measurement. Refer to Section 3.1.19.4 "Analysis of Samples
Containing Suspended Solids" on page 82.
1) Before measurement, use a homogenizer, etc. to make the sample as uniform as
possible. After homogenizing the sample, depending on the type of suspended
substance, precipitation and coagulation may occur after a period of time. Prior
to measurement, mix the sample again using a magnetic stirrer to ensure that
precipitated/coagulated material is well dispersed throughout the sample.
2) If the suspended material is present in large quantities, clumping of the material
and obstruction may occur inside the sample flow line even if the particles are of
smaller diameter that the sample flow line diameter. Take measures such as
sample dilution to prevent flow line obstruction,
3) The suspended solids measurement kit employs a 0.8 mm PTFE tubing for
sample injection. Diminished reproducibility may occur with small sample
injection volumes. Make injection volumes as large as possible.
4) When conducting IC measurement of suspended solid samples using the H type
instrument, obstruction of the IC measurement flow line drain tube may occur.
Sufficiently pulverize the suspended particles to allow free flow through the
drain tube.
TOC-LCSH/CSN
47
3.1
Analysis Preparation
3.1.13 IC Analysis Preparations
Certain preparations are necessary for the H Type instrument. These include installing and
replenishing the IC reagent in the IC reaction vessel. This section describes the procedures
for installing and replenishing the IC reagent.
CAUTION
The IC reagent contains phosphoric acid, use care while handling to prevent
contact or spills. For details refer to Section 5.10 "Safety Data Sheets" on page
377.
Installing the IC Reagent
Procedure
48
1.
Prepare the IC reagent by diluting 50mL of commercial 85% phosphoric acid (ACS
Reagent grade) to a final volume of 250mL with pure water.
Note: Since the specific gravity of 85% phosphoric acid is about 1.7, the
concentration of the phosphoric acid is about 25% (weight%) in the
prepared IC reagent. A final concentration accuracy of ±2% is
acceptable.
2.
Pour the prepared IC reagent into the 250 mL container provided standard with the
instrument and secure the container with the mounting clip on the left side of the
instrument.
3.
4.
Pass the tip of the IC reagent tubing through the hole in the cap.
5.
Replace the cap on the container.
TOC-LCSH/CSN
Secure the tubing, using a wire clamp at a point about 100mm from the end of the
tubing tip, to prevent the tubing and cap from separating.
3.1
Analysis Preparation
Replenishing IC Reaction Vessel with IC Reagent
Use the following procedure to replenish the IC reagent.
Procedure
1.
Verify that the lever of the 3-way valve at the bottom of the IC reaction vessel is
positioned to the left as shown in Figure 3.26 "Lever Position of IC Reaction Vessel 3Way Valve".
Figure 3.26 Lever Position of IC Reaction Vessel 3-Way Valve
2.
Press the F5 [Maintenance] key in the "Initial Display".
The "Maintenance" screen is displayed.
3.
Place the cursor at the IC Reagent Automatic Regeneration (Auto IC regeneration)
item, and press the [NEXT] key.
The IC reagent will be delivered to the IC reagent vessel by the liquid delivery pump.
4.
Repeat step 3 until the IC reagent reaches the level of the IC reagent drain tubing
(bottom of branch).
TOC-LCSH/CSN
49
3.1
Analysis Preparation
3.1.14 Preparation for POC Analysis
POC (purgeable organic carbon) analysis can be performed if the optional POC analysis kit
is installed on this instrument. This section describes preparations required for POC
analysis.
Installation of the CO2 Absorber for POC Analysis
1.
Remove the CO2 absorber.
CO2 absorber for
POC analysis
Figure 3.27 CO2 Absorber Container for POC Analysis
50
2.
3.
Insert about 5mm of quartz wool into the bottom of the container.
4.
5.
6.
Place about 5mm of quartz wool on top of the lithium hydroxide.
TOC-LCSH/CSN
Add commercially available anhydrous lithium hydroxide to the container on top of
the quartz wool until it reaches just below the screw threads of the container.
Note: About 6g of lithium hydroxide crystals is required for a single load.
Attach the O-ring and nipple to the top of the container, and firmly tighten the cap.
Install the CO2 absorber for POC analysis in the original position.
3.1
Analysis Preparation
CAUTION
•
•
•
Lithium hydroxide is available in anhydrous and hydrated forms. Since the
ability of the hydrated form to absorb carbon dioxide is slightly inferior to that of
the anhydrous form, use anhydrous lithium to fill the CO2 absorber container.
When introducing the quartz wool and lithium hydroxide into the container, do
not pack too tightly.
The CO2 absorber container is constructed of glass. Handle carefully to prevent
breakage.
Cap
Nipple
O-Ring
Lithium Hydroxide
Quartz Wool
Figure 3.28 Preparing the CO2 Absorber for POC Analysis
TOC-LCSH/CSN
51
3.1
Analysis Preparation
3.1.15 TN Analysis Preparations (When Using the Optional TN Unit)
TN analysis is possible if the optional TN unit is installed with this instrument. The NOx
absorber must also be connected to perform TN analysis.
3.1.15.1 NOx Absorber
The CO2 absorber (soda lime) is used as the NOx absorber. Connect it to the instrument
using the following procedure.
Procedure
1.
2.
Cut the tips of the rigid tubes (2) in the lid of the CO2 absorber with a knife.
3.
Once connected, place the NOx absorber at the back right of the instrument.
Connect the Viton tubing to the 2 rigid tubes as described below.
Tubing labeled "L": Connect to tube labeled "L" on the CO2 absorber.
Tubing labeled "S": Connect to tube labeled "S" on the CO2 absorber.
Note:
Make sure there are no kinks in the flexible tubing.
L
S
L
S
Connect to the absorber
NOx absorber
Figure 3.29 Connecting the NOx Absorber
52
TOC-LCSH/CSN
3.1
Analysis Preparation
3.1.16 B-Type Halogen Scrubber (When Using the Optional B-Type Halogen Scrubber)
The optional B-type halogen scrubber can help protect the NDIR cell from corrosion when
analyzing samples that contain a high amount of salt (concentration up to about 3 %). The
B-type halogen scrubber connects to the IC reaction vessel outlet (downstream of the
carrier gas flow) on the H Type instrument and to the pure water trap outlet (downstream of
the carrier gas flow) on the N Type instrument.
Follow the procedure described below to introduce the stainless mesh for absorption and
dilute hydrochloric acid into the B-type halogen scrubber.
The B-type halogen scrubber is filled with 0.05 mol/L hydrochloric acid. The liquid level
of hydrochloric acid gradually decreases when the instrument is waiting for analysis to start
(and the carrier gas is flowing), the sample injection volume is small, or the interval
between analyses is large during analysis. Always verify that the liquid level is up to the
height of the branching tube in the vessel of the B-type halogen scrubber before starting
analysis. If the liquid level is lower than the branching tube, fill the vessel to the correct
height with 0.05 mol/L hydrochloric acid (this is important when performing continuous
analysis over an extended period of time using the autosampler).
Note:
The ability to absorb halogen stops if the amount of liquid in the B-type halogen
scrubber decreases enough to prevent the carrier gas from bubbling or if the
stainless mesh for absorption dissolves completely. Before starting analysis,
always verify that the liquid level is up to the height of the branching tube in the
vessel of the B-type halogen scrubber and the scrubber contains stainless mesh
for absorption.
Preparation Procedure
1.
Prepare 0.05 mol/L hydrochloric acid by either diluting 1 mol/L hydrochloric acid
with 20 parts pure water or diluting concentrated hydrochloric acid (12 mol/L) with
240 parts pure water. A concentration accuracy of approximately ±2 % is acceptable.
As a guide, the TOC value of the pure water used for dilution should be less than
0.5 mg/L.
TOC-LCSH/CSN
53
3.1
Analysis Preparation
2.
Release the clamps that secure the B-type halogen scrubber in place, remove the Btype halogen scrubber from the instrument, and open the screw cap.
B-type halogen
scrubber
Figure 3.30 Removing the B-Type Halogen Scrubber
3.
Insert a stainless mesh for absorption into the B-type halogen scrubber and then fill
the vessel with 0.05 mol/L hydrochloric acid up to the height of the branching tube.
Screw cap
0.05 mol/L hydrochloric acid
Stainless mesh for absorption
Figure 3.31 Preparing the B-Type Halogen Scrubber
54
TOC-LCSH/CSN
3.1
4.
Analysis Preparation
Close the screw cap and return the B-type halogen scrubber to its original position in
the instrument.
CAUTION
Hydrochloric acid is a deleterious substance and must always be handled with
care to prevent spills and contact with the skin. For details, refer to Section 5.10
"Safety Data Sheets" on page 377.
The vessel of the B-type halogen scrubber is made of glass. Handle the vessel
with care to prevent breakage due to impact with other objects.
3.1.17 Instrument Parameters
Various parameters must be set to operate TOC-L.
3.1.17.1 Buzzer
This section describes the method for setting the ON/OFF status of the buzzer sound
accompanying operation of the keypad.
Procedure
1.
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
TOC-LCSH/CSN
55
3.1
Analysis Preparation
2.
Press the F4 [Meas. Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
3.
4.
Move the cursor to Misc. - Buzzer item using the arrow keys.
5.
Press the F1 [Return] key.
The display returns to the "Initial Display".
Set the buzzer to ON/OFF.
Use the [ENTER] key to toggle between ON and OFF.
3.1.17.2 Date and Time
This section describes the procedure for setting the date and time.
Procedure
1.
56
TOC-LCSH/CSN
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
3.1
TIP »
Analysis Preparation
2.
Press the F4 [Meas. Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
3.
4.
Move the cursor to Misc. - Current Date and Time item using the arrow keys.
5.
Press the F1 [Return] key.
The display returns to the "Initial Display".
Set the date and time in order of month, day, year, hour, minute.
Note: To set each item, enter a numerical value, and then press the [Enter]
key to confirm the entry.
The cursor moves to the next subsequent item until finishing the minute
setting.
Inputs from January 1, 2000 to December 31, 2099 are possible.
Use the → key to move the cursor to the right, and use the ← key to move the cursor to the
left.
TOC-LCSH/CSN
57
3.1
Analysis Preparation
3.1.17.3 Catalyst Type
The procedure for choosing the type of catalyst to be used for TC or TN analysis is as
follows.
Procedure
lua chon loai catalyst
TIP »
1.
Press the F4 [Conditions] key.
The "Conditions - Unit Management" screen is displayed.
2.
Move the cursor to the Basic Unit-Catalyst section using the arrow keys.
The current type of catalyst is displayed here.
3.
Press the [ENTER] key.
All the catalyst types will be shown.
4.
Use the ↑ ↓ keys to select the appropriate catalyst for the analysis mode and sample
concentration.
• Regular: TC/NPOC analysis (0.5mg/L or greater)
• High:
TC/NPOC analysis (less than 0.5mg/L)
• TC/TN: TN analysis
• TC analysis using the combustion tube for high salt samples (option): Saline + TC
• TN analysis using the combustion tube for high salt samples (option): Saline + TN
Press the [ENTER] key when finished. The status returns to step 2.
Note:
• Match the catalyst type entered to the type actually being used in the
combustion tube.
• If TC/TN is selected, the furnace temperature is automatically set to
720°C.
5.
6.
58
TOC-LCSH/CSN
Press the [Enter] key to confirm the catalyst choice.
Press the F1 [Return] key.
The display returns to the "Initial Display".
3.1
Analysis Preparation
3.1.17.4 Concentration Unit
This section describes the procedure for choosing the concentration unit.
Procedure
1.
Press the F4 [Conditions] key.
The "Conditions - Unit Management" screen is displayed.
2.
Press the F4 [Meas. Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
Lua chon don vi
3.
4.
Use the arrow keys to move the cursor to the Output - Unit: Liquid Sample item.
5.
Use the ↑ ↓ keys to select the concentration unit.
• mg/L
• µg/L
• ppm
Press the [ENTER] key.
All of the concentration units are displayed.
•
TIP »
ppb
Press the [ENTER] key to cancel.
The screen returns to the status in step 3.
6.
7.
Press the [Enter] key to confirm the concentration unit choice.
Press the F1 [Return] key.
The display returns to the "Initial Display".
TOC-LCSH/CSN
59
3.1
Analysis Preparation
3.1.17.5 Printer Setup
This section describes the procedure for setting up the printer.
Set the printer model and paper size to use.
Printer model and paper size setting procedure
1.
Press the F4 [Conditions] key on the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
2.
3.
4.
5.
6.
Use the arrow keys to move to the cursor to Printer type.
Press the [Enter] key.
Use the up and down arrow keys to select the printer model.
Press [Enter] to set the printer model.
Set the paper size using Paper size in the same manner.
The following two printout methods are available.
• Runtime Report: Automatically prints the analysis results (data only), after calibration
curve analysis and sample analysis are complete.
• Screen Print: Press the [PRINT] key when it is illuminated to print out the contents of
the screen (no settings necessary, printing possible only when [PRINT] key is
illuminated)
Note that printing does not occur while the information for printing does not satisfy the
specified paper size requirements. To eject paper, press the [ABC] key and then the
[PRINT] key.
60
TOC-LCSH/CSN
3.1
Analysis Preparation
Runtime Report
When "ON" is selected for Runtime Report, analysis results are automatically printed after
calibration curve analysis and sample analysis are completed. The following two settings
may also be selected.
•
•
Peak Print: Prints the peaks in the analysis results.
Print Calibration Curve Graph (Cal. Grap. Print): Prints the calibration curve graph
generated following calibration curve analysis.
Procedure
1.
Press the F4 [Conditions] key.
The "Conditions - Unit Management" screen is displayed.
2.
3.
Use the arrow keys to move the cursor to the Printer - Runtime Report item.
Select ON/OFF for Runtime Report.
Use the [ENTER] key to toggle between ON/OFF.
Turning Runtime Report "ON"
1.
2.
3.
Use the arrow keys to move the cursor to the Peak Print item.
4.
Use the [ENTER] key to toggle between ON/OFF for Print Calibration Curve Graph
(Cal. Grap. Print).
5.
Press the F1 [Return] key.
The display returns to the "Initial Display".
Use the [ENTER] key to toggle between ON/OFF for Peak Print.
Use the arrow keys to move the cursor to the Print Calibration Curve Graph (Cal.
Grap. Print) item.
TOC-LCSH/CSN
61
3.1
Analysis Preparation
3.1.17.6 Suspended Solids Analysis
When samples containing suspended solids are measured, the optional Suspended Solids
kit can be used.
This section describes the procedure for using the Suspended Solids kit once it has been
installed.
Procedure
1.
Press the F4 [Conditions] key.
The "Conditions - Unit Management" screen is displayed.
2.
3.
Use the arrow keys to move the cursor to the SP Kit item.
4.
Press the F1 [Return] key.
The display returns to the "Initial Display".
Use the [ENTER] key to Enable/Disable this function based on whether the SP kit is
installed.
Press the [ENTER] key to toggle to YES.
3.1.17.7 Syringe Washes
Setting the number of time the syringe is washed with sample is described in this section. If
the optional POC analysis kit is installed or the N Type instrument is used, the item # of
Syringe Wash (sp) is also displayed. # of Syringe Wash sets the number of time the syringe
is washed for TC, IC (H Type), NPOC and TN analysis. # of Syringe Wash (sp) sets the
number of times washing is performed for POC and IC analysis using the N Type
instrument.
62
TOC-LCSH/CSN
3.1
Analysis Preparation
Procedure
1.
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
2.
Press the F4 [Meas.Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed with the cursor at the
Meas. - # of Syringe Wash item. Move the cursor to the Meas.- # of Syringe Wash
(sp) item to set the number of washes for POC analysis or IC (N Type) analysis.
3.
Use the numeric keys to enter the number of times the syringe is to be washed with
sample.
Note: Syringe wash frequency range: 0 - 9 (times)
4.
Press the [Enter] key to confirm the entry.
The cursor moves to the next item.
5.
Press the F1 [Return] key.
The display returns to the "Initial Display".
TOC-LCSH/CSN
63
3.1
Analysis Preparation
3.1.17.8 Automatically Change the Injection Volume
When the Automatically Change Injection Volume function is used, the instrument will
automatically change the injection volume and analyze the sample again if the sample's
peaks exceed the full scale. If the Automatically Change Dilution Factor function is also
being used, the injection volume is changed first and then the dilution factor is changed.
However, depending on the analysis parameters, the dilution factor may be changed
without automatically changing the injection volume.
Note:
This function cannot be used when performing simultaneous analysis or common
injection in multi-mode analysis.
Procedure
64
1.
Press the F4 [Conditions] key.
The "Conditions - Unit Management" screen is displayed.
2.
Press the F4 [Meas. Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
3.
Use the arrow keys to move the cursor to the Automatically Change Injection Volume
(Auto Inj. Vol. Change) item.
4.
Set the Automatically Change Injection Volume function ON / OFF with the
[ENTER] key.
5.
Press the F1 [Return] key.
The display returns to the "Initial Display".
TOC-LCSH/CSN
3.1
Analysis Preparation
3.1.17.9 Automatically Change Dilution Factor
If the samples peaks exceed the full scale, the instrument has the ability to automatically
dilute the sample with dilution water and analyze it again. This section describes the
procedure for using this function.
Note:
• Dilution precision may be poor when the dilution factor is high (20 times or
greater).
• This function cannot be used when performing simultaneous analysis or
common injection in multi-mode analysis.
Procedure
1.
Press the F4 [Conditions] key.
The "Conditions - Unit Management" screen is displayed.
2.
Press the F4 [Meas. Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
3.
Use the arrow keys to move the cursor to the Automatically Change Dilution Factor
(Auto Dil change) item.
4.
Set the Automatically Change Dilution Factor function to ON / OFF with the
[ENTER] key.
5.
Press the F1 [Return] key.
The display returns to the "Initial Display".
TOC-LCSH/CSN
65
3.1
Analysis Preparation
3.1.17.10 Multiple Injections
When the Multiple Injections function is used, a single sample in the syringe is discharged
in multiple injections. Using this function means that a smaller sample volume is required
for analysis.
Note:
• The repeatability may be inferior to that in normal analysis.
• If automatic change functions, such as the Automatically Select Optimal
Calibration Curve function, the Automatically Change Injection Volume
function, or the Automatically Change Dilution Factor function are used,
the analysis may have to be restarted from the point of drawing in the
sample again.
Procedure
66
1.
Press the F4 [Conditions] key.
The "Conditions - Unit Management" screen is displayed.
2.
Press the F4 [Meas. Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
3.
4.
5.
Use the arrow keys to move the cursor to the Multiple Injection item.
TOC-LCSH/CSN
Set the Multiple Injection functions ON / OFF with the [ENTER] key.
Press the F1 [Return] key.
The display returns to the "Initial Display".
3.1
Analysis Preparation
3.1.17.11 Setting Conversion Equation
This section describes the procedure for entering the conversion equation used for
converting analysis results to COD (chemical oxygen demand) or BOD (biochemical
oxygen demand) values, etc. The converted values will be displayed to the right of the
measured values when a conversion equation is entered. To enter the conversion equation,
enter the following items.
•
•
•
Name of the conversion value
Conversion target
First order equation values
Procedure
1.
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
2.
Press the F4 [Meas.Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
3.
4.
Use the ↓ key to move the cursor to the Output - Name of Convert Val. item.
5.
Press the [Enter] key to confirm.
The cursor will move to Output - Object for Conversion.
6.
Press the [ENTER] key.
All the conversion targets will be displayed.
Enter the name of the conversion value.
Note: Use up to 10 characters.
TOC-LCSH/CSN
67
3.1
Analysis Preparation
7.
Use the ↓ ↑ arrow keys to select the desired conversion target.
• NONE
• TC
• IC
• TOC (TC-IC)
• POC
• NPOC
• TOC (POC+NPOC)
• TN
8. Press the [Enter] key to confirm.
9. Use the arrow keys to move the cursor to the Output - Equation (y=Ax+B) item.
10. Enter the values for A and B for the conversion equation y=Ax+B.
11. After entering the various numeric values, press [Enter] to confirm the values.
12. Press the F1 [Return] key.
The display returns to the "Initial Display".
3.1.17.12 Automatic Regeneration of IC Reagent (H Type)
Over time the acidity of the IC solution gradually decreases as the acid is used to convert
the IC components in samples into carbon dioxide. Unless the IC solution is periodically
regenerated, it eventually loses its ability to fully convert IC into carbon dioxide, which can
affect the accuracy of analysis.
When the auto regeneration option is selected, the volume of the IC solution and pH are
automatically maintained at appropriate levels. The instrument automatically pumps IC
solution from the IC reagent reservoir in the following cases:
•
•
•
When the instrument is turned on
Prior to the initial IC measurement, following a preset number of injections and preset
volume of injected samples
If peak tailing is observed during an IC measurement.
Procedure
1.
68
TOC-LCSH/CSN
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
3.1
Analysis Preparation
2.
Press the F4 [Meas. Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
3.
Move the cursor to the IC Reagent Automatic Regeneration (Auto IC regenerate) item
using the arrow keys.
4.
Set the IC Reagent Automatic Regeneration function to ON or OFF with the
[ENTER] key.
5.
Press the F1 [Return] key.
The display returns to the "Initial Display".
TOC-LCSH/CSN
69
3.1
Analysis Preparation
3.1.17.13 Analysis Span
The time interval from the end of one analysis (sample injection) to the start of the next
analysis (sample injection) is called the "Analysis Span." The procedure for setting that
analysis span is described here.
Procedure
70
1.
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
2.
Press the F4 [Meas.Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
3.
For TC, NPOC Analysis
Use the arrow keys to move the cursor to the Meas. - Min.Mes.Span[TC/NPOC] item.
For IC, POC Analysis
Use the arrow keys to move the cursor to the Meas. - Min.Mes.Span[IC/POC] item.
4.
Enter the analysis span value using the numeric keys.
Note: Analysis Span Input Range: 0 - 9999 (seconds)
5.
Press the [Enter] key to confirm the analysis span value.
The cursor moves to the next item.
6.
Press the F1 [Return] key.
The display returns to the "Initial Display".
TOC-LCSH/CSN
3.1
Analysis Preparation
3.1.17.14 Counter Limit Values
A message is displayed on the screen whenever a counter limit value is exceeded. Counter
limit values may be set for the following items.
•
•
•
•
•
•
•
•
•
•
•
•
Instrument running time in hours
Hours of operation for the ozone generator
CO2 absorber
Number of 8-port valve rotor operations
Sample injection volume to the combustion tube
Volume of acid
Number of syringe strokes
Hours of operation for the IC tubing pump (Recommended value: 300 hours)
Hours of operation for the ASI tubing pump (Recommended value: 300 hours)
Hours of operation for stirrer motors (1) through (8)
Number of OCT1 8-port valve operations
Number of OCT2 8-port valve operations
Procedure
TIP »
1.
Press the F5 [Maintenance] key.
The "Maintenance" screen is displayed.
2.
Move the cursor to the Counter - Limit to be set, and input a value using the number
keys.
By setting values slightly smaller than the residual volumes for the dilution water and acid,
the alarm will be generated while there is some liquid remaining. This can prevent
disruption or errors in analysis due to depletion of these liquids.
TOC-LCSH/CSN
71
3.1
Analysis Preparation
3.1.17.15 Screen Saver
If the Screen Saver function is set to ON, the screen display is turned off after 10 minutes
has passed without keyboard operation. The procedure for using this function is described
here.
Procedure
72
1.
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
2.
Press the F4 [Meas.Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
3.
4.
5.
Use the arrow keys to move the cursor to the Misc. - Screen Saver (Scrn off) item.
TOC-LCSH/CSN
Set the Screen Saver to ON or OFF using the [ENTER] key
Press the F1 [Return] key.
The display returns to the "Initial Display".
3.1
Analysis Preparation
3.1.18 Preparation and Storage of Standard Solutions
3.1.18.1 Preparation of Standard Solutions
Zero Water
Zero water refers to a standard solution with zero concentration of TC, IC or TN, or the
water used to prepare these standard solutions. Water that is in theory absolutely free of
carbon (TC) or nitrogen (TN) is used as zero water. It is difficult, in practice, to obtain this
type of water. Even ultra-pure water obtained using a high-performance membrane
technique or water that has been repeatedly distilled will have a TC content of about
10μg/L. This value is measured directly after manufacture, and increases when the water is
stored in a container. Carbon dioxide is contained in the atmosphere at 300-500ppm. The
CO2 content is higher in a room with many people, or where combustion equipment is
used. This carbon dioxide dissolves in the water and is present as IC. The dissolved amount
is generally about 0.2mg/L, but is dependent on the water temperature and carbon dioxide
content of the air in contact with the water. Refer to "Table 5.2 • CO2 Content (ppm) in
Distilled Water Equilibrated with Atmosphere Temperature (°C)". Instruments that prevent
contact with air are not incorporated in water up-take, retention or storage during common
distillation and purification of water. For this reason, IC is present in most distilled or
purified water. There are cases where the TC content in distilled water commercially
available in plastic or glass containers is 1ppm.
Note:
The purity of water required for zero water varies depending on the analysis
range. There would be no problems using commercially available purified water
when a 100ppm sample is measured. The quality of the zero water should be
considered along with the analysis range.
Preparation of TC Standard Solutions
1.
2.
3.
Accurately weigh 2.125 g of reagent grade potassium hydrogen phthalate.
4.
Accurately dilute this standard stock solution with zero water to prepare standard
solutions at the required concentrations.
Note: • The TC standard solution reagent need not be potassium hydrogen
phthalate. Other substances (such as sucrose) are also acceptable
depending on the application.
• Although this example describes the preparation of a 1000 mgC/L
standard stock solution, the standard stock solution may be prepared at
other concentrations within the range of solubility.
• A variety of official drying methods for standard substances are defined.
Use a suitable method for drying, if required.
Transfer the weighed amount into a 1 L volumetric flask.
Add zero water to the 1 L mark, and stir the solution.
The carbon concentration of the solution is 1000 mgC/L (1000 mgC/L = 1000 ppmC).
This solution is the standard stock solution.
Note: • The standard stock solution may be prepared at other concentrations.
• Although this example describes the preparation of a 1000 mgC/L
standard stock solution, the standard stock solution may be prepared at
other concentrations within the range of solubility.
TOC-LCSH/CSN
73
3.1
Analysis Preparation
Preparation of the IC Standard Solution
1.
Accurately weigh 3.497 g of reagent grade sodium hydrogen carbonate and 4.412 g of
sodium carbonate.
2.
3.
Transfer the weighed amount into a 1 L volumetric flask.
Add zero water up to the 1 L marker and mix well.
The carbon concentration of this liquid solution is equivalent to 1000 mgC/L
(1000 mgC/L = 1000 ppmC). Keep this solution as a standard stock solution.
The following procedure is the same as for preparing TC standard solution.
Preparation of TN Standard Solution
1.
2.
3.
Accurately weigh 7.219 g of reagent grade potassium nitrate.
Transfer the weighed material to a 1 L volumetric flask.
Add zero water up to the 1 L marker and mix well.
The nitrogen concentration of this liquid solution is equivalent to 1000 mgN/L
(1000 mgN/L = 1000 ppmN). Keep this solution as a standard stock solution.
The following procedure is the same as for preparing TC standard solution.
Preparation of POC Standard Solution (using the optional POC analysis kit)
IC standard solution is used as the POC standard solution with this instrument for the
following reasons.
• In POC analysis, the measured substance is an organic material that is volatile and
poorly soluble in water (for example, benzene or chloroform). Preparing a
standard solution at an appropriate concentration using these types of organic
substances is difficult.
• Volatile and poorly soluble organic substances tend to undergo changes in
concentration during storage or handling after preparation.
• Standard solutions that are produced using volatile and poorly soluble organic
substances are difficult to use.
Consequently, the IC standard solution is used for this instrument. The preparation
method is listed above.
TC/TN Mixed Standard Solution Preparation Procedure
When TC (or NPOC) and TN analyses are performed simultaneously, a mixed TC and
TN standard solution is prepared.
The mixed standard solution is prepared by mixing the TC standard solution and TN
standard solution. The mixed standard solution must contain 0.05 M hydrochloric
acid.
74
TOC-LCSH/CSN
3.1
Analysis Preparation
Preparation of 100 mgC/L TC - 100 mgN/L TN Mixed Standard Solution
1.
Prepare 1 L of 1000 mgC/L TC standard solution using the preparation method
described above.
2.
Prepare 1 L of 1000 mgN/L TN standard solution using the preparation method
described above.
3.
Introduce 100 mL of each of the prepared standard solutions into a 1 L volumetric
flask.
4.
5.
Add 50 mL of 1 M hydrochloric acid to the flask.
Add zero water up to the 1 L marker and mix well.
The hydrochloric acid concentration will be about 0.05 M after dilution.
3.1.18.2 Storage of Standard Solutions
The standard solutions undergo concentration changes, particularly when lowconcentration solutions are stored even for short periods. As a result, high-concentration
standard stock solutions (for example, 1000 mgC/L) should be stored in airtight containers
in a cool, dark place. Glass bottles are suitable storage containers. Dilute the stock solution
prior to each use.
Storage Time
The limitation on storage of standard solutions is about 2 months for 1000 mgC/L standard
stock solutions and about 1 week for diluted standard solutions (for example, 100 mgC/L).
The limitations are for cold storage in sealed containers.
Note:
IC standard solution absorbs atmospheric carbon dioxide and undergoes
concentration changes. As a result, it is particularly important to store IC
standard solution in a sealed container.
Prepare fresh standard solutions:
•
•
If reproducibility of analysis values is poor or concentration fluctuates.
If contaminants, including even small amounts of dust, are present in the standard
solution.
TOC-LCSH/CSN
75
3.1
Analysis Preparation
3.1.19 Sample Preparation
3.1.19.1 High Sensitivity Analysis
High sensitivity analysis refers to use of the high sensitivity analysis kit to measure trace
amounts (commonly 0.5ppm or less) of TOC in samples such as ultra-pure water. The
precautions described in the sections below should be followed when conducting trace
analysis on the order of 10 - 100ppb.
Precautions for High Sensitivity Analysis
•
Use TOC high sensitivity catalyst.
Carefully fill the combustion tube with high sensitivity catalyst to prevent
contamination of the combustion tube. Measuring high-concentration samples using
TOC high sensitivity catalyst that is intended for the analysis of ultra-pure water will
influence the results of subsequent analyses on ultra-pure water samples. This is
primarily caused by remaining sample residue. The residue may be removed by running
repeated analyses of zero water.
Since removal is difficult with residual salt, alkali, or highly acidic samples, a separate
combustion tube containing TOC high sensitivity catalyst should be prepared for use
with ultra-pure water samples only.
Verify that both ends of the combustion tube are sealed when storing catalyst that is to
be used only for ultra-pure water samples.
•
Measure samples immediately
Samples containing trace carbon such as ultra-pure water should be measured
immediately after collection. If analysis cannot be performed immediately, store the
sample in a dark location without freezing at 0-10°C, and perform analysis as soon as
possible.
To collect the water, introduce water into a well-washed container, leaving no
headspace, and seal the container.
•
Use glass sample containers
Glass containers are optimal for use as sample containers. 500mL - 1L commercially
available glass screw-lid jars with PTFE seals (generally referred to as heat-resistant
screw-top jars or hermetic jars) are appropriate for use as water collection and transport
containers.
Note:
76
TOC-LCSH/CSN
Exercise caution with plastic containers as the elution of TOC components can
occur.
3.1
•
Analysis Preparation
Use NPOC analysis for analysis of ultra-pure water.
Use the NPOC method for analysis of ultra-pure water samples. TOC determination
using the difference between TC and IC is prone to large analysis errors for the
following reasons.
•
•
•
•
•
The TOC value is significantly affected since a large portion of TC often comprises
IC. Errors in TC analysis and IC analysis are additive.
Carbon dioxide is adsorbed from the atmosphere during sample collection and
analysis. During the elapsed time between TC analysis and IC analysis, the sample
absorbs more carbon from the atmosphere causing the IC result to be higher than the
IC content in the TC result. Therefore subtracting the elevated IC result from the TC
yields a biased TOC value.
The TOC value can also be greatly influence if standard solutions are not prepared
and measured carefully. Errors are compounded since two calibration curves must be
generated for TC and IC.
The calibration curves are used in sample analysis by extending a two-point
calibration curve to the origin.
In NPOC analysis, purgeable organic carbon may be volatilized from the sample
during sparging for IC removal. This is not a problem since the ultra-pure water
contains practically no POC.
Cautions in Calibration Curve Generation and Sample Analysis in High
Sensitivity Analysis
The case below describes the generation of a 2-point calibration curve shifted to the origin.
The concentrations used are 0ppb and 400ppb.
Preparation of Standard Solutions
A 2-point calibration curve using 0ppb and 400ppb is generated. Correction for the TC
contained in the purified water used for preparation of the standard solutions is achieved by
shifting this curve to the origin.
Preparation of the 0ppb and 400ppb TC standard solutions should be performed at the same
time using the same purified water.
For example, prepare two 250mL volumetric flasks by washing well with purified water
(preferably water containing low TC concentration). Carefully introduce 1mL of 100ppm
TC standard stock solution (for a 400ppb solution) into one of the volumetric flasks.
Distilled water is introduced up to the graduation line in both volumetric flasks.
These procedures should be performed as quickly as possible using caution to avoid
external contaminants. If a water purification apparatus is the source of purified water,
allow the water to flow for a few minutes prior to use, as the initial water will have a higher
TC concentration. In addition, alternate the flasks a number of time while filling them with
water to make the TC concentration of the purified water as equal as possible.
Do not use wash bottle water that has been standing for a long period to add water to the
graduation line of the volumetric flask. Use fresh purified water since the concentration of
the water in the wash bottle has been continually increasing.
TOC-LCSH/CSN
77
3.1
Analysis Preparation
Instrument Preparation
The blank peaks present at the start of high sensitivity analysis will become progressively
smaller and gradually stabilize. As a result, calibration curves generated too soon after the
start of analysis may be inaccurate because they contain data collected during unstable
conditions. For this reason, perform NPOC analysis at least five times on pure water using
the same measurement parameters (injection volume, sparge time) to be used for analyzing
the sample prior to analyzing the standard solution, and verify that the peaks have
stabilized.
Calibration Curve Analyses
Calibration curves are generated using the following two methods.
(1)
(2)
Using standard solution in a 250mL volumetric flask
The sample aspiration tubing is inserted directly into the volumetric flask until it
reaches the bottom of the flask. Analyses are performed quickly. Four to five repeated
analyses can be made with almost no effects from the absorption of atmospheric
carbon dioxide.Cover the opening of the volumetric flask with sealing film or paraffin
to prevent contamination.Use this method when the IC value of the purified water
used for standard solution preparation (specifically, 0ppb standard solution) is about
50ppb or less.
Sparging of Standard Solution
To sparge within the sample injection syringe, set the acid addition ratio to 0.5%, and
the sparge time to 2 minutes.To sparge using the optional external sparge kit, transfer
about 60mL of the standard solution to a clean sample container, add 1-2 drops of 1M
hydrochloric acid sparge for 10 minutes and analyze.
Cover the sample container with paraffin or sealing film to prevent contamination. A
glass container with an external diameter of 24-25mm and a height of 200-250mm is
appropriate. There are test tubes, stopper-equipped test tubes and chromatography
tubes of suitable size available commercially. If the outer diameter of the container is
too large, the air - water contact efficiency is decreased, requiring a longer sparge
time. Ensuring that the tip of the sparge tubing is near the bottom of the container will
improve the sparging efficiency.
Sample Analysis
Use the standard curve generated in the previous section and measure the NPOC of the
sample. Measure the sample using the same method used for the standard solutions. If the
values gradually decrease with each repeated analysis using the optional external sparge
kit, extend the sparge time to ensure sufficient sparging. The shape of the sample container,
sample amount, amount of sparge gas and IC content of the sample all have a bearing on
the required sparge time. Determine the appropriate sparge time in accordance with these
parameters.
78
TOC-LCSH/CSN
3.1
Analysis Preparation
3.1.19.2 TC Blank Check Analysis
A TOC system invariably contains substances in the instrument flow lines that produce
peaks. These peaks are referred to as blank values or system blank values, and are present
even in water samples containing absolutely no carbon. The magnitude of peaks in the
blanks differs based on various factors such as system construction and the catalyst used.
For the TOC-L, every effort has been made to minimize these peaks, which can affect the
accuracy of TC analyses. Accuracy is particularly affected when trace TOC is measured
(such as in high sensitivity analysis of ultra-pure water samples); for this type of analysis,
the blank peaks must be small and stable. To check and correct for the magnitude of the
system blank peaks, use the TOC-Control L Blank Check procedure described below.
When using high-sensitivity TOC catalyst with this instrument, blank check measurement
is conducted using blank check water which is produced within the instrument itself.
Note:
Practically no blank peaks are generated in the IC measurement. Also, because
the IC value will become zero for water that has been acidified and sparged, this
phenomenon can be easily verified by analyzing such water in the IC
measurement. However, normally, such a procedure is not necessary. For this
reason, a special program similar to the TC blank measurement is not provided
for IC measurement.
Blank Check Analysis Procedure
1.
In the "Maintenance" screen, move the cursor to TC Blank Checking, and press the
[NEXT] key.
The following is displayed: "TC Blank Check Input injection volume [500 - 2000]
___μL Press NEXT Key."
2.
Enter a value using the number keys, and press the [NEXT] key.
The following is displayed: "Set Sample and press START button".
TOC-LCSH/CSN
79
3.1
Analysis Preparation
3.
Dilution water is used for blank check analysis. Fill the Dilution water bottle with
pure water and place it in the specified position. Although only 200mL of pure water
is required for the blank check, fill the dilution water bottle to capacity before starting
the blank check procedure.
4.
Press the [Start] button.
Blank check analysis begins.
"Blank Check" Screen Description
Function Keys
Item
Description
F1 [Return]
Returns to "Maintenance" screen
F3 [Zoom In]
Magnifies the peaks by decreasing the viewable range of the y-axis.
F4 [Zoom Out]
Reduces the peaks by increasing the viewable range of the y-axis.
Analysis Result List
Item
Description
Number
Number of the set (5 injections per set) measured
Area value
Average area value for 5 injections
SD
Standard deviation for 5 injections
CV%
Coefficient of area value variation for injections
Peak Area
Displays peaks during blank check analysis.
Result List for Each Injection
80
Item
Description
Inj #
Displays the number of the injection
Area value
Area value for each peak
Remark
T: Tailing
H: Over-scale
TOC-LCSH/CSN
3.1
Analysis Preparation
Description of the TC Blank Check Operation
(1)
Washing the inside of the trap
First, the blank check ultra-pure water trap is washed with water from the dilution
water bottle. A 6 mL aliquot of dilution water is drawn into and then expelled from
the ultra-pure water trap (twice), leaving the trap nearly empty. Then 2 mL of dilution
water is injected into the TC injector Finally, the remaining water in the trap is drawn
into the syringe and expelled (4 times).
(2) Preparation of ultra-pure water for blank check
Six separate 2 mL aliquots of dilution water bottle are injected into the TC injector.
Then, the water in the trap is injected into the TC injector five more times in 2 mL
aliquots.
(3) Blank check analysis
The ultra-pure water collected in the trap for blank check analysis is used to conduct 5
repeat TC analyses at the set injection volume. Steps 2 and 3 are then repeated 9
times. The measurement result for each analysis is displayed, enabling assessment of
the magnitude and stability of the system blank value from the area values. If the
magnitude of the blank value must be read in terms of concentration, compare these
area values with those obtained through calibration curve measurement.
Note:
If the flow lines, syringe pump or catalyst is contaminated with foreign
substances, the blank values may not become small until the blank check
procedure is repeated multiple times.
3.1.19.3 Pretreatment for IC Removal (Sparging)
Errors for TC and IC analyses are additive. For samples that have a comparatively high IC
content relative to the TOC content, the TOC analysis error will be large if it is determined
by the difference between TC and IC results. Samples of this type include samples from the
natural environment such as rivers, lakes, swamps, oceans and ground water, or samples
from water treatment facilities.
Using the difference between TC and IC to determine TOC is not appropriate for purified
water or ultra-pure water samples. This is because the CO2 in air dissolves in the sample
and is measured as IC; and this concentration tends to vary.
In such cases, the sample is pretreated with aeration or sparging before analysis to remove
the IC. The sample is then subjected to TC analysis, immediately followed by TOC
analysis using the NPOC method.
Sparge Sequence
There are two methods for sparging with this instrument.
(1)
Sparging within the sample injector syringe
This is performed only when the instrument is set for automatic sparging before
analysis.
The sparge gas flow rate is variable for sample measurement on the H Type
instrument and fixed to 80 mL/min on the N Type instrument as well as for calibration
curve creation on the H Type instrument. Set the sparge gas flow rate for sample
measurement on the H Type instrument via the "Measurement Parameters" screen or
"Measurement - Method Store" screen ("ASI Schedule - Settings" screen when using
the ASI-L). A flow rate of 80 to 100 mL/min is appropriate for normal measurement.
TOC-LCSH/CSN
81
3.1
Analysis Preparation
(2)
Independent sparging of sample using the optional external sparge kit
A glass container with an external diameter of 24-25 mm and a height of 200-250 mm
is appropriate for use as the sample container. Test tubes, stopper-equipped test tubes
and chromatography tubes of suitable size are available commercially. If the outer
diameter of the container is too large, the air to water contact efficiency is decreased,
requiring a longer sparge time. As a guide, the sparge time should be about 5 to
10 minutes for a sample of 20 to 40 mL.
Sparge Procedure
1.
Section 3.2.1.5 "Setting the Sparge Gas Flow Rate (When Using the Optional
External Sparge Kit)" for the sparge gas delivery procedure.
2.
3.
Add 1 to 2 drops of 1M hydrochloric acid to the sample to adjust the pH to 2-3.
Insert the sparge tubing into the sample.
To improve the sparging efficiency, the tip of the sparge tubing should be as close to
the bottom of the sample container as possible.
Note:
In this method, sparge gas can be used independently, and while the first sample
is being measured, another sample can be sparged, thereby improving analysis
efficiency.
3.1.19.4 Analysis of Samples Containing Suspended Solids
Effect on Analysis
Large variations sometimes occur in TOC analyses of samples containing suspended solids.
TOC is often contained in the suspended material. This is evident when the same sample is
analyzed on two different TOC instruments. Good results are not obtained if the suspended
solids are handled differently in the gathering of BOD (biochemical oxygen demand) and
TOC correlative data.
The suspended solids described here are primarily considered impurities contained in the
sample that will pass through a 50 mesh strainer (openings of approximately 0.28mm).
Analysis should not be performed for samples containing suspended solids that are too
large to pass through a 50 mesh strainer.
The procedure described below is for TOC analysis, but is also valid for TN analysis.
Analysis Restrictions
Since PTFE tubing with an inner diameter of about 0.5mm is used in the instrument for
injecting the sample, suspended solids that do not pass through cannot be measured.
Analysis reproducibility is poor for samples that do not uniformly contain such solids even
if they should pass through the tubing.
Solids that are heavy and readily form sediment, such as silt, can accumulate at the bottom
of the syringe. This can scratch the rotor of the sample injector 8-port valve, causing leaks.
Therefore, sedimentation and separation should be performed to as great an extent as
possible prior to analysis.
82
TOC-LCSH/CSN
3.1
Analysis Preparation
Countermeasures
When measuring samples containing suspended solids, the following types of processing
operations are normally used.
(1)
(2)
(3)
(4)
TOC Analysis of Supernatant
When the suspended solids are of no great concern, sedimentation is effected in the
sample container, and the supernatant sample is used. With this method, results
depend on the sedimentation and separation properties of the suspended solids, but
primarily the dissolved TOC (DOC: dissolved organic carbon) is measured.
TOC Analysis of Filtrate
The suspended solids are removed using glass fiber filter paper or a membrane filter,
and only the dissolved TOC is measured. Because the filter paper or filter itself is
likely to contain TOC, thorough washing with water or sample is performed prior to
use until no TOC is present in the eluate. Heat the glass fiber filter paper prior to use.
TOC Analysis of Stirred Samples
To perform analysis while intentionally drawing suspended solids into the syringe, the
sample can be stirred during analysis with a magnetic stirrer or other instrument.
However, simple stirring can lead to extreme variation in analyses because the
suspended material contained in the sample may not be distributed uniformly
throughout the suspension.
TOC Analysis after Homogenization of the Sample
If the application requires that the suspended solids be included in the analysis, it is
critical that the solids are as fine as possible and distributed uniformly throughout the
suspension. Analysis results that accurately reflect the amount of TOC with good
reproducibility can be obtained when the sample is highly homogenized to form
uniform micro-size particles.
Homogenizing systems may include a mixer to perform high-speed stirring or an
ultrasonic system. Only use homogenizers with outputs of 150-300W. Typical
washing sonicators do not have sufficient output for this use. Ultrasonic systems are
generally more powerful, although performance varies with the type of suspended
solid.
Uniform suspension cannot always be achieved with all types of suspended solids.
Sludge-like materials are comparatively easy to process while fibrous materials are
more difficult.
3.1.19.5 Handling Samples Containing Acids, Bases or Salts
There are various problems associated with measuring samples that contain acids, bases or
salts. Corrosion of the NDIR analysis cell, detrimental effects on analysis values, and
reduced life of the combustion tube and catalyst are some of these problems. If corrosion of
the inner surface of the NDIR cell occurs, baseline stability will decline and noise will
increase. Therefore, samples containing acids, bases or salts should be handled as described
below.
The concentration at which adverse effects are produced will vary depending on the type of
acid or salt and the TOC or TN concentration. Prior to analysis, the sample is diluted so that
the acid, base or salt concentration is reduced to 1000mg/L or less. Neutralization is also
required for bases. The TOC-L is equipped with an automatic dilution function to perform
these dilutions.
TOC-LCSH/CSN
83
3.1
Analysis Preparation
Acid
Dilution to a concentration of 1000 mg/L or less is desirable for acids. Concentrations up to
5000 mg/L can be used if this level of dilution cannot be attained. Note that there are also
methods to reduce the acidity of hydrochloric acid or sulfuric acid to a more neutral pH of 2
to 3 using potassium hydroxide or sodium hydroxide. This process produces thermally
stable sodium chloride or sodium sulfate, which prevent the generation of acidic gas during
sample combustion. Acid neutralization should be stopped at a pH of about 2 to 3 and TOC
direct analysis (NPOC analysis) should then be performed after sparging to remove any IC.
It is necessary to consider the TOC associated with impurities contained in the alkali
reagents used for neutralization. All salts of nitric acid generate acidic gas under thermal
decomposition; as a result, neutralization is ineffective. When the sample contains
hydrochloric or hypochlorous acid, hydrochloric acid gas is generated from salts that are
readily subject to thermal decomposition, such as ammonium chloride, calcium chloride
and magnesium chloride. The instrument is equipped with a halogen scrubber; however, the
scrubber's main function is absorb hydrochloric acid gas generated by corrosion of the gold
plating on the internal surface of the NDIR cell.
Alkaline Samples
When performing TC analysis on alkaline samples, the following types of problems can
arise.
•
•
•
Rapid decrease in sensitivity and loss of reproducibility.
Rapid degradation of catalyst or wear of the combustion tube.
Likelihood that IC will be high due to absorption of carbon dioxide.
For these reasons, the NPOC analysis is suitable for alkaline samples.
In NPOC analysis, dilute hydrochloric acid is added to adjust the solution to a weakly
acidic pH of 2-3, thus forming a salt. For example, calcium chloride will be formed as a salt
if the sample contains calcium hydroxide as the base. Since it is preferable for this salt
concentration to be low, alkaline samples should be diluted as much as possible.
Salt Accumulation
Samples should be diluted as much as possible to reduce the salt concentration and extend
the life of the combustion tube and catalyst. Conducting a large number of analyses on
samples containing salts will allow the salts to accumulate in the combustion tube,
gradually increasing resistance to the flow of carrier gas. This results in decreased analysis
reproducibility. When this happens, perform the combustion tube maintenance procedure
described in Section 4.2.4 "Washing / Replacing the Combustion and Carrier Gas
Purification Tubes" on page 242.
Identifying Salt Accumulation
The following situations arise when salts accumulate and clog the catalyst.
•
•
The sound of gas release is heard when the slider moves during analysis.
A dramatic fluctuation in carrier gas flow is noticed after the sample is injected.
1 dao dong dang ke cu dong khi mang sau khi mau duoc bom vao
84
tieng cua dong khi nghe
duoc khi con lan di chuyen
TOC-LCSH/CSN
3.2
3.2
Analysis
Analysis
3.2.1 Starting Up the Instrument
3.2.1.1 Turning the Power ON
To perform analysis, turn on the power to the instrument as follows.
The TOC-L has two power switches: a power switch for everyday use (on the left side of
the front door of the instrument), and a main power switch (on the right side towards the
top of the instrument) for turning off power to the instrument over extended idle periods.
With the exception of extended idle periods, leave the main power switch turned on and use
the power switch on the front of the instrument start and stop the instrument on a daily
basis. The instrument consumes the minimum amount of energy required to keep the
software running (about 15 W) when the main power switch is left on.
When using the ASI-L or OCT-L, connect these units to the TOC-L using the
corresponding connection cables before turning on the main power switch on the TOC-L
main unit. Leave the power switch on the ASI-L turned on at all times.
Turning on Power to the Instrument
TIP »
1.
Turn on the main power switch on the left side towards the top of the TOC-L. The
power switch on the left of the front door of the TOC-L lights up orange.
2.
Turn on the power switch on the left of the front door of the TOC-L. The power
switch lights up green and the instrument starts up. The display lights up at the same
time.
Electric furnace heating and carrier gas supply will not start until the power switch on the
left of the front door of the TOC-L is turned on and lights up green.
The lit states of the power switch and the indicator in the middle of the TOC-L front door
represent the instrument states shown in Table 3.1.
Table 3.1 Relationship Between Power Switch and Indicator Lit States and
Instrument State
Instrument State
tinh trang san sang
chua duoc thiet lap
Indicator in the Middle of
Power switch
the Front Door
Ready condition not established
Lit orange
Lit green
Ready condition established
Lit green
Lit green
Measurement in progress
Lit blue
Lit green
In editing mode
Flashing orange
Lit green
Sleep state
Flashing blue
Lit green
Firmware update in progress
Flashing green
Lit green
Error occurred
Flashing red
Lit green
Warning occurred
Lit red
Lit green
TOC-LCSH/CSN
85
3.2
Analysis
Table 3.1 Relationship Between Power Switch and Indicator Lit States and
Instrument State
Instrument State
Indicator in the Middle of
Power switch
the Front Door
Shutting down
Off
Flashing orange
Shut down
Off
Lit orange
Main power switch OFF
Off
Off
The "Initial Display" is displayed.
Note:
Press the power switch again to turn OFF power to the instrument.
3.2.1.2 Setting the Carrier Gas Supply Pressure
Setting Procedure
1.
Set the supply pressure of the carrier gas to 200 ± 10 kPa (29PSI).
Note: • Never allow the carrier gas supply pressure to exceed 250 kPa.
• Always keep the carrier gas tubing exclusive to this instrument.
Branching the tubing and connecting it to other equipment may
adversely affect measurement performance due to fluctuations in supply
pressure.
• If the carrier gas supply pressure drops below 170 kPa, a warning
message is displayed.
If a warning message is displayed, verify the carrier gas supply source.
3.2.1.3 Setting the Carrier Gas Supply Pressure
(When Using the Carrier Gas Regulator Option)
Setting Procedure
1.
86
TOC-LCSH/CSN
Set the supply pressure of the carrier gas to 300 ± 10 kPa (44PSI).
3.2
Analysis
2.
Press the F3 [Background Monitor] key on the "Initial Display".
The "Background Monitor" screen is displayed.
3.
Turn the carrier gas pressure adjustment knob while watching the supply gas pressure
display on the "Background Monitor" screen and set the carrier gas supply pressure to
200 kPa (29PSI).
Carrier gas pressure
adjustment knob
4.
Figure 3.32 Carrier Gas Pressure Settings
Press the F1 [Return] key.
The screen returns to the "Initial Display".
3.2.1.4 Setting the Flow Rate of Carrier Gas
This section describes how to set the flow rate of the carrier gas.
Setting Procedure
1.
Press the F4 [Conditions] key on the "Initial Display".
The "Conditions" screen is displayed.
TOC-LCSH/CSN
87
3.2
Analysis
2.
Press the F5 [Others] key.
The "Conditions - Others" screen is displayed.
3.
Check that the carrier gas flow rate is 150 mL/min (default value).
Do not change the carrier gas flow rate during analysis. This may cause errors in
analysis precision because the peak area changes virtually inversely proportional
to the carrier gas flow rate.
4.
Press the F1 [Return] key.
The screen returns to the "Initial Display".
Note:
88
TOC-LCSH/CSN
3.2
Analysis
3.2.1.5 Setting the Sparge Gas Flow Rate (When Using the Optional External Sparge
Kit)
This section describes how to set the sparge gas flow rate when using the external sparge
kit.
Setting Procedure
1.
Press the F5 [Maintenance] key on the "Initial Display".
The "Maintenance" screen is displayed.
2.
3.
Use the down arrow key to move to the cursor to Sparge Gas.
4.
Turn the sparge gas flow adjustment knob to adjust the flow rate.
Press the [Next] key.
The solenoid valve for sparge gas opens.
Sparge gas flow meter
Sparge gas flow
adjustment knob
Figure 3.33 Adjusting the Sparge Gas Flow Rate
TOC-LCSH/CSN
89
3.2
Analysis
Note:
5.
Adjust the flow rate to suit the size and shape of the sample
container. A flow rate of about 100 mL/min is appropriate.
Press the F1 [Return] key.
The screen returns to the "Initial Display".
3.2.1.6 Electric Furnace
The electric furnace power needs to be turned on for TC, TOC, NPOC, POC and TN
analyses. The electric furnace does not need to be turned on when performing IC analysis
only.
Turn On Power to the Electric Furnace
1.
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed. Move the cursor to the
Basic Unit - Furnace Power item.
2.
Set the electric furnace power to ON.
Toggle the setting to ON using the [ENTER] key.
3.
Press the F1 [Return] key.
The display returns to the "Initial Display".
Note:
90
TOC-LCSH/CSN
It takes 30-40 minutes after the electric furnace power is turned ON for the
temperature to reach the set value. To turn OFF the instrument, refer to Section
3.2.7 "Ending Analysis" on page 137
3.2
Analysis
3.2.1.7 Turning On Power to the TNM-L (Option)
This section describes how to turn On the power to the TNM-L when using the optional
TNM-L TN unit.
Turning On Power to the TNM-L
1.
Press the F4 [Conditions] key on the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
2.
The TN power can be set to either ON or OFF.
Press the [ENTER] key to set the power ON.
3.
Press the F1 [Return] key.
The screen returns to the "Initial Display".
3.2.1.8 Setting the TNM-L Ozone Air Flow Rate (Option)
This section describes how to set the ozone air flow rate for supplying ozone when using
the optional TNM-L TN unit.
Setting Procedure
1.
Set the air supply pressure for ozone to 200 to 300 kPa.
Note: Never allow the air supply pressure for ozone to exceed 300 kPa.
2.
Press the F3 [Background Monitor] key on the "Initial Display".
The "Background Monitor" screen is displayed.
3.
After displaying the [TN] tab on the "Background Monitor" screen, turn the
adjustment knob located inside the door on the right side of the TNM-L while
watching the O3 gas pressure display and set the O3 gas pressure to 200 kPa.
TOC-LCSH/CSN
91
3.2
Analysis
3.2.2 Calibration Curve Analysis
There are two methods of performing calibration curve analysis, one for generating a
single-point calibration curve and the other for generating a multi-point calibration curve.
Each of these methods is described here.
TC analysis using a concentration unit of mg/L is used for the example, but the methods are
the same for IC, POC and TN analysis.
Procedure
1.
TIP »
Press the [CAL] key while viewing the "Initial Display".
The "Calibration Settings" screen is displayed.
To cancel settings, press the [CAL] key.
3.2.2.1 Single-point Calibration Curve
The procedure for generating a single-point calibration curve consists of the following five
general steps.
92
Step 1
Set the Analysis Mode
Step 2
Set the Parameters for Generating the Calibration Curve
Step 3
Set the Standard Solution
Step 4
Press the [START] Key
Step 5
Finish the Analysis
TOC-LCSH/CSN
3.2
Step 1
1.
TIP »
Analysis
Set the Analysis Mode
Press the F2 [TC] key.
The parameters box for TC analysis is displayed. The calibration curves that are
currently stored are displayed at the top of the screen.
To cancel settings, press the [CAL] key.
Note: • For IC analysis: Press the F3 [IC] key.
• For POC* analysis: Press the F4 [POC] key.
• For TN* analysis: Press the F5 [TN] key.
"*" denotes optional, and is displayed only if the optional settings have
been made.
Step 2
Set the Parameters for Generating the Calibration Curve
The following 12 items determine the parameters for generating the calibration curve.
(1) Calibration Curve Number: Sets the calibration curve number.
(2) Standard Solution Concentration: Sets the concentration of the injected standard
solution.
(3) Number of Injections (default: 1): Sets the number of injections for standard solution
analysis.
(4) Maximum Number of Injections (default: 1): Sets the maximum number of injections
(analysis injections + additional injections).
(5) SD (Default: 0.1): Sets the standard deviation.
(6) CV% (Default: 2.0): Sets the CV% value.
(7) Dilution Factor: Sets the dilution factor.
(8) Injection Volume: Sets the standard solution injection volume.
(9) Acid Addition Ratio: Sets the ratio of acid added to sample for IC analysis.
(10) Sparge Time: Sets the length of time sparging will be performed.
(11) Curve Type: Sets the type of calibration curve to be used (point-to-point or least
squares linear regression curve).
(12) Curve Shift: Sets the shift of the calibration curve toward the zero point (no shift, shift
to zero point or shift to TC blank point)
The procedures for setting these parameters are described below.
(1) Calibration Curve Number
1.
Enter the calibration curve number.
A list of previously generated calibration curves is presented at the top of the screen.
Referring to this list, enter a number that is not yet used.
2.
Press the [Enter] key.
The calibration curve number is confirmed.
TOC-LCSH/CSN
93
3.2
Analysis
(2) Standard Solution Concentration
1.
Move the cursor to the Standard Solution Concentration (STD Conc.) item using the ↓
key.
2.
Enter the concentration of the standard solution for TC analysis. (Refer to Section
3.1.17.4 "Concentration Unit" on page 59.)
3.
Press the [Enter] key.
The optimal injection volume is examined, and displayed.
(3) Number of Injections
1.
Move the cursor to the Number of Injection (Inj #) item using the ↓ key.
2.
Set the number of injections of standard solution to be made, and press the [Enter]
key.
(4) Maximum Number of Injections
94
1.
Move the cursor to the Maximum Number of Injection (Max # of Inj) item using the ↓
key.
2.
Set the maximum number of injections of standard solution to be made, and press the
[Enter] key.
Note: Maximum Number of Injections
The maximum number of injections refers to repeat analysis with the automatic
additional analysis function in use. Whether automatic additional analyses are
performed is determined by the settings for standard deviation (SD) and
coefficient of variation (CV%). When the analyses using the set number of
injections are complete, the SD and CV% for those results are compared to the
SD and CV% limits. If both of the actual values exceed the set limits, the
automatic additional analysis function is activated.
3.
Press the [Enter] key.
TOC-LCSH/CSN
3.2
Analysis
(5) SD
This parameter is only available if the Number of Injections is less than the Maximum
Number of Injections.
1.
Move the cursor to the SD item using the ↓ key.
2.
Enter the standard deviation value, and press the [Enter] key.
(6) CV%
This parameter is only available if the Number of Injections is less than the Maximum
Number of Injections.
1.
Move the cursor to the CV% item using the ↓ key.
2.
Enter the CV% value, and press the [Enter] key.
(7) Dilution Factor
The optimal dilution factor is automatically displayed when the concentration of the
standard solution is entered.
1.
Move the cursor to the Dilution Factor (Dil. Factor) item using the ↓ key.
2.
Enter the dilution factor, and press the [Enter] key.
Note: In analyses using dilution, the minimum injection volume is 40 uL.
Dilution is performed if the concentration is greater than:
• TC
2500mg/L
• IC (H Type) 3000mg/L
• TN
200mg/L.
(8) Injection Volume
The optimal injection volume is automatically displayed when the concentration of the
standard solution is entered.
1.
Move the cursor to the Injection Volume (Inj. Volume) item using the ↓ key.
2.
Enter the injection volume, and press the [Enter] key.
TOC-LCSH/CSN
95
3.2
Analysis
(9) Acid Addition Ratio
Enter only when acid is to be added to the standard solution.
1.
Move the cursor to the Acid Addition Ratio (Acid ratio) item using the ↓ key.
2.
Enter the amount (%) of acid to be added, and press the [Enter] key.
(10) Sparge Time
Enter only if the standard solution is to be sparged.
1.
Move the cursor to the Sparge Time item using the ↓ key.
2.
Enter the sparge time, and press the [Enter] key.
(11) Curve Type
This parameter is used to select whether a least squares linear regression curve or a pointto-point calibration curve (where a straight line connects the individual calibration points)
will be generated using 3 or more points.
1.
Move the cursor to the Curve Type item using the arrow keys.
2.
Set the curve type.
Toggle the parameter settings using the [ENTER] key.
dich chuyen song song (12) Curve Shift
cua duong chuan de
Three types of shift are available.
no di qua diem goc
• Parallel shift of the calibration curve so that it passes through the origin (zero point.)
(diem 0)
•
Buoc duong chuan
di qua diem trong
duoc xac dinh boi
blank
96
•
Force the calibration curve to pass through the blank point determined by the TC Blank
Check value.
No shift of the calibration curve at all.
Note:
TOC-LCSH/CSN
The calibration curve will not shift to the blank point unless the injection volume
is the same as that used in the TC Blank Check analysis.
3.2
TIP »
1.
Move the cursor to the Curve Shift item using the arrow keys.
2.
Set the Curve Shift.
Toggle the parameter settings using the [ENTER] key.
Analysis
To change the parameters of the calibration curve, press the F1 [Return] key. The display
returns to the "Settings" screen.
To exit without performing calibration curve analysis, press the [Cal] key.
To Exit, press the F6 [Yes] key. The display returns to the "Initial Display".
To cancel exiting, press the F1 [No] key.
Step 3
Set the Standard Solution
Procedure
1.
Press the [NEXT] key.
The "Calibration Setting - Calibration" screen is displayed.
2.
Set the standard solution.
When the instrument enters the standby state, the Ready lamp illuminates and the
[START] key begins blinking.
Note: • To change the parameters of the calibration curve, press the F1 [Return]
key. The display returns to the "Settings" screen.
• To exit without performing calibration curve analysis, press the [CAL]
key.
• To Exit, press the F6 [Yes] key. The display returns to the "Initial
Display".
• To cancel exiting, press the F1 [No] key.
TOC-LCSH/CSN
97
3.2
Analysis
Step 4
Press the [START] Key
Procedure
1.
2.
Verify that the Ready lamp has illuminated and the [START] key is blinking.
Press the [START] key.
The [START] key is illuminated, the "Calibration Setting - Calibration" screen is
displayed, and calibration curve analysis begins. The instrument status is displayed at
the upper right portion of the screen. The status changes as follows:
Washing → Sampling → Sparging → Injecting → Detecting Peak
TIP »
Graph Scale
The graph scale (ordinate) is displayed using the auto-ranging function. The range can be
changed (enlarged / reduced) within the range of 10 - 1000mV.
To enlarge the scale, press the F3 key.
To reduce the scale, press the F4 key.
Each time the F3 or F4 key is pressed, the range changes 10mV for the range of 10 100mV, and 100mV for the range of 100 - 1000mV.
TIP »
If additional analyses are to be performed using the same standard solution, press the F1
[Additional Analyses] key, and follow the on-screen directions.
To nullify the measured data and remeasure, press the F2 [Remeasure Point] key.
Then continue by pressing the F6 [Yes] key, and follow the on-screen directions.
Step 5
Finish the Analysis
Procedure
1.
Press the F6 [Exit Measurement] key.
Note: • To protect the results: Press the F6 [Yes] key.
The analysis results are automatically printed if Runtime Report was set
to "ON" in the "Conditions - Unit" screen. The display returns to "Initial
Display".
• If results are not to be protected: Press the F4 [No] key. The analysis
results are automatically printed if Runtime Report was set to "ON" in
the "Conditions - Unit" screen. The display returns to "Initial Display".
• To return to the analysis screen without exiting: Press the F1 [Cancel]
key. The display returns to the "Calibration Setting - Calibration" screen.
Reference: To change calibration curve parameters after completion of the calibration curve analysis,
refer to Section 3.5.1 "Reviewing Calibration Curve List" on page 207.
98
TOC-LCSH/CSN
3.2
Analysis
3.2.2.2 Multi-point Calibration Curve Analysis
A multi-point calibration curve can be generated with a maximum of 10 points. Set the
concentrations of the standard solutions to be measured using the procedure described
below.
The procedure for generating a multi-point calibration curve consists of the following five
general steps.
Step 1
Set the Parameters for the 1st Point of the Calibration Curve
Step 2
Set Parameters for the 2nd and Subsequent Points of the Calibration Curve
Step 3
Set the Standard Solution
Step 4
Press the [START] Key
Step 5
Finish the Analysis
Step 1
Set the Parameters for the 1st Point of the Calibration Curve
Refer to Section 3.2.2.1 "Single-point Calibration Curve" on page 92, "Step 1 Set the
Analysis Mode" and "Step 2 Set the Parameters for Generating the Calibration Curve".
Step 2
Set the Parameters for the 2nd and Subsequent Points of the
Calibration Curve
Procedure
1.
Use the ↑ ↓ keys to move the cursor to the parameters boxes.
TOC-LCSH/CSN
99
3.2
Analysis
2.
Press the → key.
The parameters box for the 2nd point is displayed.
3.
Set the parameters for generating the calibration curve for the 2nd point.
The injection volume displayed is for the highest concentration among the set of
standard solutions.
4.
Repeat steps 2 and 3 above to set the calibration curve parameters for the 3rd and
subsequent points. The display moves to the "Next" screen for setting the 6th and
subsequent points.
Reference: Refer to Section 3.2.2.1 "Single-point Calibration Curve" on page 92"Step 2 Set the
Parameters for Generating the Calibration Curve", steps (2) - (7).
Displaying the Previous Page (points 1-5)
1.
Move the cursor to the parameters box for Point-6.
2.
Press the ← key.
The screen for the previous page is displayed.
Displaying the Following Page (Points 6 - 10)
1.
Move the cursor to the parameters box for Point-5.
2.
Press the → key.
Discarding a Point (Point-n)
1.
2.
100
TOC-LCSH/CSN
Move the cursor to the parameters box for Point-n.
Press the F6 [Delete Point] key.
The parameters box for Point-n will be deleted. (If the F6 key is pressed at Point-1,
the parameters box is not deleted, however, the default display is reinstated.)
3.2
Analysis
Step 3 Set the Standard Solution
Procedure
1.
Press the [NEXT] key.
The "Generate Calibration Curve - Measuring" screen is displayed.
2.
Set the standard solution.
When the instrument enters the standby state, the Ready lamp illuminates and the
[START] key begins blinking.
Note: • To change the parameters of the calibration curve, press the F1 [Return]
key. The display returns to the "Settings" screen.
• To exit without performing calibration curve analysis, press the [CAL]
key.
• To Exit, press the F6 [Yes] key. The display returns to the "Initial
Display".
• To cancel exiting, press the F1 [No] key.
Step 4 Press the [START] Key
Procedure
1.
2.
Verify that the Ready lamp has illuminated and the [START] key is blinking.
Press the [START] key.
The [START] key illuminates, the "Calibration Setting - Calibration" screen is
displayed, and calibration curve analysis begins. The instrument status is displayed at
the upper right portion of the screen. The status changes as follows:
Washing → Sampling → Sparging → Injecting → Detecting Peak
When calibration curve analysis is complete for the 1st point, the analysis result is
displayed and the [START] key goes out.
TIP »
Graph Scale
The graph scale (ordinate) is displayed using the auto-ranging function. The range can be
changed (enlarged / reduced) within the range of 10 - 1000mV.
To enlarge the scale, press the F3 key.
To reduce the scale, press the F4 key.
Each time the F3 or F4 key is pressed, the range changes 10mV for the range of 10 100mV, and 100mV for the range of 100 - 1000mV.
Performing Additional Analyses Using the Same Standard Solution
1.
Press the F1 [Add Injection] key, and follow the on-screen directions.
Nullifying Measured Data and Re-analyzing
1.
2.
Press the F2 [Remeasure Point] key.
Continue by pressing the F6 [Yes] key, and follow the on-screen directions.
TOC-LCSH/CSN
101
3.2
Analysis
Starting Calibration Curve Analysis for the 2nd and Subsequent Points
1.
2.
3.
Press the F6 [Go to Next Cal. Point] key.
Set the standard solution for the next point.
Press the [START] key.
CAUTION
Confirm that the ready lamp has illuminated, and that the [START] key is
blinking. Press the [START] key.
Reference: The parameter settings for generating the calibration curve can be changed during
calibration curve analysis in the "Calibration Setting - Calibration" screen and after
completion of calibration curve analysis in the "Calibration Setting - Calibration" screen.
Refer to Section 3.2.2.4 "Changing Parameters for a Generated Calibration Curve" on
page 111.
Step 5 Finish the Analysis
"Exit Cal. Measurement" is displayed for the F6 key when analyses for all of the points are
complete.
Procedure
1.
Press the F6 [Exit Cal. Measurement] key.
Note: • To protect the results: Press the F6 [Yes] key.
The analysis results are automatically printed if Runtime Report was set
to "ON" in the "Parameter Settings - Unit" screen. The display returns to
"Initial Display".
• If results are not to be protected: Press the F4 [No] key. The analysis
results are automatically printed if Runtime Report was set to "ON" in
the "Conditions - Unit" screen. The display returns to "Initial Display".
• To return to the analysis screen without exiting: Press the F1 [Cancel]
key. The display returns to the "Calibration Setting - Calibration" screen.
Reference: To change the calibration curve parameter settings after completion of the calibration
curve analyses, refer to Section 3.5.1 "Reviewing Calibration Curve List" on page 207.
102
TOC-LCSH/CSN
3.2
Analysis
3.2.2.3 Multi-point Calibration Curve Analysis with Diluted Solution
It is possible to generate a multi-point calibration curve using a single standard solution.
Enter the concentrations in the order of the standard solutions to be analyzed.
The procedure for generating a multi-point calibration curve with diluted solution consists
of the following six general steps.
Step 1
Select the Mode.
Step 2
Set the Parameters for Generating the Calibration Curve for the First Point.
Step 3
Set the Parameters for Generating the Calibration Curve for the Second Point.
Step 4
Set the Standard Solution.
Step 5
Press the [START] key.
Step 6
Finish the Analysis.
Step 1 Select the mode.
Procedure
1.
Press the F1 [Dil. for Std. Sol. ON/OFF] key.
The concentration of the undiluted solution (Org Conc.) and the dilution factor (Dil.
Factor) are displayed in the POINT-1 box.
Step 2 Set the parameters for generating the calibration curve for the first
point.
This involves making the following twelve settings.
(1)
(2)
Calib.#:
STD Conc.:
Sets the calibration curve number.
Sets the concentration of the injected standard
solution obtained by dilution.
(3) Org Conc.:
Sets the concentration of the undiluted solution.
(4) Inj # (default = 1):
Sets the number of injections for analysis of the
standard solution.
(5) Max # of Inj (default = 1):
Set the number of injections for the standard
solution (analysis injections + additional
analysis).
(6) SD (default = 0.1):
Sets the standard deviation.
(7) CV% (default = 2.0):
Sets the CV value.
(8) Inj. Volume:
Sets the volume of the standard solution injected.
(9) Acid Ratio:
Sets the ratio of acid added to the sample (make
this setting for IC analysis).
(10) Sparge Time:
Set the duration of sparging.
(11) Curve Type:
Set the type of calibration curve (point-to-point
or least squares linear regression curve).
(12) Curve Shift:
Sets the shift of the calibration curve toward the
zero point (no shift, shift to zero point or shift to
blank point).
The procedures for setting these parameters are described below.
TOC-LCSH/CSN
103
3.2
Analysis
(1) Calibration Curve Number
1.
Enter the calibration curve number.
A list of previously generated calibration curves is presented at the top of the screen.
Referring to this list, enter a number that is not yet used.
2.
Press the [Enter] key.
The calibration curve number is confirmed.
(2) Standard Solution Concentration
1.
Move the cursor to the Standard Solution Concentration (STD Conc.) item using the ↓
key.
2.
Enter the injection concentration of the standard solution for TC analysis.
The previously set concentration units will be shown on the screen (refer to Section
Section 3.1.17.4 "Concentration Unit" on page 59.)
Press the [Enter] key.
(3) Undiluted Solution Concentration
104
1.
Move the cursor to the Undiluted Solution Concentration (Org Conc.) item using the
↓ key.
2.
Enter the concentration of the undiluted solution.
The previously set concentration units will be shown on the screen (refer to Section
Section 3.1.17.4 "Concentration Unit" on page 59.)
3.
Press the [Enter] key. The optimum injection volume will be confirmed and
displayed.
Note: When the standard solution concentration and undiluted solution
concentration are set, the dilution factor is calculated automatically.
Set values that ensure the dilution factor is greater than 1.25. If the
dilution factor is less than 1.25, the dilution factor precision of the
instrument may be impaired.
TOC-LCSH/CSN
3.2
TIP »
Analysis
To change the parameters of the calibration curve, press the F1 [Return] key. The display
returns to the "Settings" screen.
To exit without performing calibration curve analysis, press the [CAL] key.
To Exit, press the F6 [Yes] key. The display returns to the "Initial Display".
To cancel exiting, press the F1 [No] key.
(4) Number of Injections
1.
Move the cursor to the Number of Injections (Inj #) item using the ↓ key.
2.
Set the number of injections of standard solution to be made, and press the [Enter]
key.
(5) Maximum Number of Injections
1.
Move the cursor to the Maximum Number of Injection (Max # of Inj) item using the ↓
key.
2.
Set the maximum number of injections of standard solution to be made, and press the
[Enter] key.
Note: Maximum Number of Injections
The maximum number of injections refers to repeat analysis with the
automatic additional analysis function in use. Whether automatic additional
analyses are performed is determined by the settings for standard deviation
(SD) and coefficient of variation (CV%). When the analyses using the set
number of injections are complete, the SD and CV% for those results are
compared to the SD and CV% limits. If both of the actual values exceed the
set limits, the automatic additional analysis function is activated.
3.
Press the [Enter] key.
(6) SD
This parameter is only available if the Number of Injections is less than the Maximum
Number of Injections.
1.
Move the cursor to the SD item using the ↓ key.
2.
Enter the standard deviation value, and press the [Enter] key.
TOC-LCSH/CSN
105
3.2
Analysis
(7) CV%
This parameter is only available if the Number of Injections is less than the Maximum
Number of Injections.
1.
Move the cursor to the CV% item using the ↓ key.
2.
Enter the CV value, and press the [Enter] key.
(8) Injection Volume
The optimal injection volume is automatically displayed when the concentration of the
standard solution is entered.
1.
Move the cursor to the Injection Volume (Inj. Volume) item using the ↓ key.
2.
Enter the injection volume, and press the [Enter] key.
(9) Acid Addition Ratio
Enter only when acid is to be added to the standard solution.
1.
Move the cursor to the Acid Addition Ratio (Acid Ratio) item using the ↓ key.
2.
Enter the amount (%) of acid to be added, and press the [Enter] key.
(10) Sparge Time
Enter only if the standard solution is to be sparged.
1.
Move the cursor to the Sparge Time item using the ↓ key.
2.
Enter the sparge time, and press the [Enter] key.
(11) Curve Type
This parameter is used to select whether a least squares linear regression curve or a pointto-point calibration curve will be generated using 3 or more points.
106
TOC-LCSH/CSN
3.2
1.
Move the cursor to the Curve Type item using the arrow keys.
2.
Set the curve type.
Toggle the parameter settings using the [ENTER] key.
Analysis
(12) Curve Shift
Three types of shift are available.
•
•
•
Parallel shift of the calibration curve so that it passes through the origin (zero point).
Force the calibration curve to pass through the blank point determined by the TC Blank
Check value.
No shift of the calibration curve at all.
Note: The calibration curve will not shift to the blank point unless the
injection volume is the same as that used in the TC Blank Check
analysis.
1.
Move the cursor to the Curve Shift item using the arrow keys.
2.
Set the Curve Shift.
Toggle the parameter settings using the [ENTER] key.
Step 3 Set the Parameters for Generating the Calibration Curve for the
Second Point.
Procedure
1.
Move the cursor to the parameter setting box for the first point using the ↑ and ↓ keys.
TOC-LCSH/CSN
107
3.2
Analysis
2.
Press the → key.
The parameter setting box for the second point will be displayed.
3.
Now set the parameters for generating the curves for the second and subsequent
points.
The injection volume corresponding to the standard solution with the highest
concentration among those set is displayed.
4.
Set the parameters for generating the calibration curves for the third and subsequent
points by repeating operations 2. and 3. in the procedure above.
For the sixth and later points, the screen shifts to the next page.
Reference: For the setting method, refer to (2) to (7) of Step 2 "Set the Parameters for Generating the
Calibration Curve for the First Point".
To display the first page (parameters for generating calibration curves for points
up to the fifth point) in this case:
1.
Move the cursor to the parameter setting box for Point-6.
2.
Press the ← key.
The first page will be displayed.
To display the second page (parameters for generating calibration curves for the
sixth and later points):
108
1.
Move the cursor to the parameter setting box for Point-5.
2.
Press the → key.
TOC-LCSH/CSN
3.2
Analysis
To delete any particular point (point n):
1.
2.
Move the cursor to the parameter setting box for Point-n.
Press the F6 [Delete Point] key.
The Point-n parameter setting box is deleted. (If the F6 key is pressed for Point-1, the
parameter setting box is not deleted and the default display is reinstated.)
Step 4 Set the Standard Solution
Procedure
1.
Press the [NEXT] key.
The "Calibration Setting - Calibration" screen is displayed.
2.
Set the standard solution.
When the instrument enters the standby state, the Ready lamp illuminates and the
[START] key begins blinking.
Note: • To change the parameters of the calibration curve, press the F1 [Return]
key. The display returns to the "Settings" screen.
• To exit without performing calibration curve analysis, press the [CAL]
key.
• To Exit, press the F6 [Yes] key. The display returns to the "Initial
Display".
• To cancel exiting, press the F1 [No] key.
Step 5 Press the [START] Key
Procedure
1.
2.
Verify that the Ready lamp has illuminated and the [START] key is blinking.
Press the [START] key.
The [START] key illuminates, the "Calibration Setting - Calibration" screen is
displayed, and calibration curve analysis begins. The instrument status is displayed at
the upper right portion of the screen. The status changes as follows:
Washing → Sampling → Sparging → Injecting → Detecting Peak
When calibration curve analysis is complete for the 1st point, the analysis result is
displayed and the [START] key goes out.
TIP »
Graph Scale
The graph scale (ordinate) is displayed using the auto-ranging function. The range can be
changed (enlarged / reduced) within the range of 10 - 1000mV.
To enlarge the scale, press the F3 key.
To reduce the scale, press the F4 key.
Each time the F3 or F4 key is pressed, the range changes 10mV for the range of 10 100mV, and 100mV for the range of 100 - 1000mV.
TOC-LCSH/CSN
109
3.2
Analysis
Performing Additional Analyses Using the Same Standard Solution
1.
Press the F1 [Add Injection] key, and follow the on-screen directions.
Nullifying Measured Data and Re-analyzing
1.
2.
Press the F2 [Remeasure Point] key.
Continue by pressing the F6 [Yes] key, and follow the on-screen directions.
Starting Calibration Curve Analysis for the 2nd and Subsequent Points
1.
2.
3.
Press the F6 [Go to Next Cal. Point] key.
Set the standard solution for the next point.
Press the [START] key.
CAUTION
Confirm that the ready lamp has illuminated, and that the [START] key is
blinking. Press the [START] key.
Reference: The parameter settings for generating the calibration curve can be changed during
calibration curve analysis in the "Calibration Setting - Calibration" screen and after
completion of calibration curve analysis in the "Calibration Setting - Calibration" screen.
Refer to Section 3.2.2.4 "Changing Parameters for a Generated Calibration Curve" on
page 111.
Step 6 Finish the Analysis
"Exit Cal. Measurement" is displayed for the F6 key when analyses for all of the points are
complete.
Procedure
1.
Press the F6 [Exit Cal. Measurement] key.
Note: • To protect the results: Press the F6 [Yes] key.
The analysis results are automatically printed if Runtime Report was set
to "ON" in the "Parameter Settings - Unit" screen. The display returns to
"Initial Display".
• If results are not to be protected: Press the F4 [No] key. The analysis
results are automatically printed if Runtime Report was set to "ON" in
the "Conditions - Unit" screen. The display returns to "Initial Display".
• To return to the analysis screen without exiting: Press the F1 [Cancel]
key. The display returns to the "Calibration Setting - Calibration" screen.
Reference: To change the calibration curve parameter settings after completion of the calibration
curve analyses, refer to Section 3.5.1 "Reviewing Calibration Curve List" on page 207.
110
TOC-LCSH/CSN
3.2
Analysis
3.2.2.4 Changing Parameters for a Generated Calibration Curve
The following 3 calibration curve parameters can be changed either during or after analysis
for a calibration curve.
(1)
(2)
(3)
Protect
This selects whether to protect the stored calibration curve data. Protecting the data
prevents its deletion.
Curve Type
This selects which method of generation will be used to generate the calibration curve
using 3 or more points. Choose point-to-point (where straight lines are connected) or
least squares linear regression.
Zero Point Shift
This selects whether to perform a parallel shift of the calibration curve so that it
passes through the origin (zero point), through the blank point determined by the TC
Blank Check value, or not to shift the calibration curve at all. Note that unless the
injection volume is the same as that used in the TC Blank Check analysis, the
calibration curve will not shift to the blank point.
Procedure
1.
2.
Press the F5 [Browse Cal. Curves] key.
Change the calibration curve parameter.
• Protect: Press the F2 key to toggle between ON and OFF.
• Curve Type: Press the F3 key to toggle between Point-to-Point and Least Squares
Linear Regression.
•
Curve Shift: Press the F4 key to toggle through the following selections:
none → Origin → Blank
Note:
The default parameters for generating calibration curves are as
follows.
• Protect: Protect OFF
• Curve Type: Least Squares Linear Regression
• Curve Shift: none
TOC-LCSH/CSN
111
3.2
Analysis
3.2.3 Sample Analysis
It is possible to measure samples using only one mode of analysis or to measure samples
using multiple modes of analysis. Sample measurement is classified into the following 4
types:
1)
Single-mode Analysis (for example TC, IC, POC, NPOC, or TN)
2)
Multi-Mode Analysis (for example TC/IC)
3)
Multi-Mode - Simultaneous Analysis (for example TN/TC or TN/NPOC)
4)
Multi-Mode - Common Injection Analysis (for example POC/NPOC))
Descriptions of each are included at this point.
Procedure
1.
TIP »
Press the [MEAS] key while viewing the "Initial Display".
The "Measurement Parameters" screen is displayed.
To terminate the settings while in progress, press the [MEAS] key.
3.2.3.1 Single-mode Analysis
This section describes the procedure for conducting analyses using a single analysis mode.
TC analysis using a concentration unit of mg/L is used for the example, but the methods are
the same for IC, NPOC, POC and TN analyses.
The following five steps are used for measuring samples using Single-mode Analysis.
112
Step 1
Set the Analysis Mode
Step 2
Set the Analysis Parameters
Step 3
Set the Sample
Step 4
Press the [START] Key
Step 5
Finish the Analysis
TOC-LCSH/CSN
3.2
Step 1
1.
Analysis
Set the Analysis Mode
Press the F2 [TC] key.
The parameters box for TC analysis is displayed.
Note:
Step 2
•
•
•
•
For IC analysis: Press the F3 [IC] key.
For POC* analysis: Press the F4 [POC] key.
For NPOC analysis: Press the F5 [NPOC] key.
For TN* analysis: Press the F6 [TN] key.
"*" denotes optional, and is shown for optional settings.
Set the Analysis Parameters
The analysis parameters can be set by entering new settings or from a previously stored
method.
1)
New Setting: Sets analysis parameters for the first time.
2)
Loading Method: Loads a previously stored method file. For details on Methods,
refer to Section 3.2.4 "Creating a Method" on page 132.
TOC-LCSH/CSN
113
3.2
Analysis
New Setting
The analysis parameters consist of the following 10 items.
(1)
(2)
Sample Name: Sets the sample name.
Continuous Measurement in Same Mode: Toggles Continuous Measurement in Same
Mode ON or OFF.
(3) Calibration Curve: Sets the calibration curve to be used.
(4) Number of Injections (Default value: 1): Sets the number of sample injections.
(5) Maximum Number of Injections (Default value 1): Sets the maximum number of
injections (sample injections + additional injections).
(6) SD (Default value 0.1): Sets the Standard Deviation value.
(7) CV% (Default value 2.0): Sets the Coefficient of Variation value.
(8) Dilution Factor: Sets the dilution factor.
(9) Acid addition ratio: Sets the ratio of acid added to sample. (Use with IC and NPOC
analysis).
(10) Sparge Time: Sets the time sparging will be performed. (Use with IC and NPOC
analysis).
The procedures for setting the various analysis parameters are described below.
(1) Sample Name
1.
Enter the sample name. (Maximum number of characters: 16)
2.
Press the [Enter] key.
Confirms the sample name entry.
(2) Continuous Measurement in Same Mode
Select ON for this item to conduct continuous sample measurements using the same
analysis mode. This mode is used during processing to stabilize the catalyst and decrease
the size of blank peaks.
114
1.
Use the → key to move the cursor to the Continuous Measurement in Same Mode
(Same Mode Contin. Meas.) item.
2.
Toggle ON/OFF using the [ENTER] key.
TOC-LCSH/CSN
3.2
Analysis
(3) Calibration Curve
1.
Use the ↓ key to move cursor to the First Calibration Curve (Calib. (1st)) item.
A TC analysis calibration curve list is displayed at the top of the screen.
2.
Choose the calibration curve to be used.
Two procedures are available for setting the calibration curve.
• Using the "Measurement Parameters" screen
•
Using the "Calibration Curve Information" screen
Using the "Measurement Parameters" Screen
1.
Enter the calibration curve number to be used from among those listed at the top of
the screen.
2.
Press the [Enter] key.
The calibration curve number, concentration and injection volume are displayed.
Using the "Calibration Curve Information" Screen
1.
Press the F1 [Calibration Curve] key.
The "Calibration Curve Information" screen is displayed.
2.
From the calibration curves listed at the top of the screen, select the calibration curve
information to be viewed using the ↑ ↓ keys.
3.
Press the F6 [Select] key.
The display returns to the "Measurement Parameters" screen, and the selected
calibration curve number, concentration and injection volume are displayed.
4.
Select the second and third calibration curves using the procedure in step 2 above.
Refer to Section 5.2.5 "Automatic Selection of the Optimal Calibration Curve" on
page 286 for using multiple calibration curves.
TOC-LCSH/CSN
115
3.2
Analysis
(4) Number of Injections
1.
Use the ↓ key to move the cursor to the Number of Injections (Inj #) item.
2.
Enter the number of sample analysis injections to be performed, and press the [Enter]
key.
(5) Maximum Number of Injections
1.
Use the ↓ key to move the cursor to the Maximum Number of Injections (Max # of
Inj) item.
2.
Enter the maximum number of sample analysis injections to be performed.
Note: The maximum number of injections refers to repeat analysis with
the automatic additional analysis function in use. Whether
automatic additional analyses are performed is determined by the
settings for standard deviation (SD) and coefficient of variation
(CV%). When the analyses using the set number of injections are
complete, the SD and CV% of those results are compared to the SD
and CV% limits. If both of the actual values exceed the set limits,
the automatic additional analysis function is activated.
3.
Press the [Enter] key.
(6) SD
This parameter is only available if the Number of Injections is less than the Maximum
Number of Injections.
116
1.
Move the cursor to the SD item using the ↓ key.
2.
Enter the standard deviation value, and press the [Enter] key.
TOC-LCSH/CSN
3.2
Analysis
(7) CV%
This parameter is only available if the Number of Injections is less than the Maximum
Number of Injections.
1.
Move the cursor to the CV% item using the ↓ key.
2.
Enter the CV% value, and press the [Enter] key.
(8) Dilution Factor
After the calibration curve is set, the dilution factor used is displayed.
1.
Move the cursor to the Dilution Factor (Dil. Factor) item using the ↓ key.
2.
Enter the dilution factor, and press the [Enter] key.
(9) Acid Addition Ratio
1.
Move the cursor to the Acid Addition Ratio (Acid ratio) item using the ↓ key.
2.
Enter the acid addition ratio (%), and press the [Enter] key.
(10) Sparge Time
1.
Move the cursor to the Sparge Time item using the ↓ key.
2.
Enter the sparge time, and press the [Enter] key.
TOC-LCSH/CSN
117
3.2
Analysis
(11) Sparge Gas Flow Rate
1.
Use the down arrow key to move to the cursor to [sparge gas flow].
2.
Enter the sparge gas flow rate and then press [Enter].
Loading Method
1.
Press the [METHOD] key.
The "Method Select" screen is displayed.
2.
The stored Methods are listed at the top of the screen. Select the desired method group
using the appropriate function key (F2 - F6).
3.
Select the Method to load using the ↑ ↓ keys.
The analysis parameters for the selected method are displayed on the screen.
4.
Press the [NEXT] key.
The Method is loaded, and the display returns to the "Measurement Parameters"
screen.
Reference: To change the analysis parameters, refer to procedure (1) - (11) of Step 2, New Setting,
above.
118
TOC-LCSH/CSN
3.2
Step 3
Analysis
Set the Sample
Procedure
1.
Press the [NEXT] key.
The "Measurement Parameters" screen is displayed.
2.
Set the sample.
When the instrument enters the standby state, the Ready indicator illuminates and the
[START] key starts blinking.
Note: • To change or re-enter the sample analysis parameters, press the F1
[Return] key. The display returns to the "Settings" screen.
• To finish without performing sample analysis, press the [MEAS] key.
The display returns to the "Initial Display".
Step 4
Press the [START] Key
Procedure
1.
2.
Confirm that the Ready lamp is lit and the [START] key is blinking.
Press the [START] key.
The [START] key illuminates, and the "Measurement" screen is displayed. Sample
analysis starts. The instrument status will be displayed in the upper right part of the
screen, and the status will change as indicated below:
Washing → Sampling → Sparging → Injecting → Detecting Peak
TOC-LCSH/CSN
119
3.2
Analysis
TIP »
Graph Scale
The graph scale (ordinate) is displayed using the auto-ranging function. The range can be
changed (enlarged / reduced) within the range of 10 - 1000mV.
To enlarge the scale, press the F3 key.
To reduce the scale, press the F4 key.
Each time the F3 or F4 key is pressed, the range changes 10mV for the range of 10 100mV, and 100mV for the range of 100 - 1000mV.
Upon completing analysis, the results are displayed and the [START] key goes out.
If Continuous Measurement in Same Mode was set to ON...
Analyses will repeat until the [STOP] key is pressed. For details on the [STOP] key, refer to
Section 3.3.4.2 "Interrupting Analysis" on page 178.
If Continuous Measurement in Same Mode was set to OFF...
To perform additional analyses press the F1 [Add Injection] key, and follow the on-screen
directions.
To discard measured data and reanalyze the points from the start, press the F2 [Remeasure
point] key. After pressing the F6 [Yes] key, follow the on-screen instructions.
Step 5
Finish Analysis
To stop analysis when the Continuous Measurement in the Same Mode is set to ON, press
the STOP key.
Procedure
1.
Press the F6 [Exit Measurement] key.
The display returns to the "Initial Display", and analysis information is stored in the
data report.
Reference: For details on the Data Report, refer to Section 3.5.3 "Reviewing Data Reports" on page
213.
120
TOC-LCSH/CSN
3.2
Analysis
3.2.3.2 Multi-mode Analysis
This section describes the procedures used when measurements are performed using
multiple analysis modes. Use these procedures when analyzing TC-IC and POC + NPOC
using TOC analysis.
The sample analysis procedure consists of the following 5 general steps.
Step 1
Set the Parameters for the First Analysis Mode
Step 2
Set the Parameters for the Second and Subsequent Analysis Modes
Step 3
Set the Sample
Step 4
Press the [START] Key
Step 5
Finish the Analysis
Step 1
Set the Parameters for the First Analysis Mode
Refer to Section 3.2.3 "Sample Analysis" on page 112, "Step 1 Set the Analysis Mode" and
"Step 2 Set the Analysis Parameters".
Note:
Because measurements will be conducted using multiple analysis modes, set
Continuous Measurement in the Same Mode to OFF.
Step 2
Set the Parameters for the Second and Subsequent Analysis Modes
Procedure
1.
Select the parameters for the 2nd analysis mode.
• For TC analysis: Press the F2 [TC] key.
• For IC analysis: Press the F3 [IC] key.
• For POC* analysis: Press the F4 [POC] key.
• For NPOC analysis: Press the F5 [NPOC] key.
• For TN* analysis: Press the F6 [TN] key.
"*" denotes optional, and is displayed only if optional settings have been made.
The parameters box for the type of analysis selected is displayed. In addition, the
Continuous Measurement in Same Mode item changes to Continuous Measurement.
TOC-LCSH/CSN
121
3.2
Analysis
2.
3.
TIP »
Move the cursor to the parameters box for IC analysis using the → key.
Set the second analysis mode.
Refer to Section 3.2.3 "Sample Analysis" on page 112,"Step 2 Set the Analysis
Parameters" If continuous measurement is to be performed using multiple analysis
modes, set the Continuous Measurement item to ON.
Display at the Top of the Screen
If the cursor is on TC analysis mode, a list of calibration curves for TC analysis is
displayed at the top of the screen. Similarly, if the cursor is on IC analysis mode, a list of
calibration curves for IC analysis is displayed at the top of the screen.
4.
For the 3rd and subsequent analysis modes, repeat sequence steps 1, 2 and 3, above.
For the setting procedures, refer to Section 3.2.3 "Sample Analysis" on page 112 Step
2, Item" (2) Continuous Measurement in Same Mode". To cancel the settings of the
analysis mode, press the function key corresponding to the analysis mode. The setting
screen will be closed.
 Step 3
Set the Sample
Procedure
1.
Press the [NEXT] key.
The "Analysis- Setting" screen is displayed.
2.
Set the sample. If continuous measurement has been turned ON, set all the samples.
When the instrument enters the standby state, the Ready lamp illuminates and the
[START] key begins blinking.
Note: • To re-set the sample analysis parameters, press the F1 [Return] key. The
display returns to the "Settings" screen.
• To finish without performing sample measurement, press the [MEAS]
key. The display returns to the "Initial Display".
Step 4
Press the [START] Key
Procedure
1.
2.
Verify that the Ready lamp has illuminated and the [START] key is blinking.
Press the [START] key.
The [START] key illuminates, the "Generate Calibration Curve - Measuring" screen is
displayed, and calibration curve analysis begins. The instrument status is displayed at
the upper right portion of the screen. The status changes as follows:
Washing → Sampling → Sparging → Injecting → Detecting Peak
TIP »
Graph Scale
The graph scale (ordinate) is displayed using the auto-ranging function. The range can be
changed (enlarged / reduced) within the range of 10 - 1000mV.
To enlarge the scale, press the F3 key.
To reduce the scale, press the F4 key.
122
TOC-LCSH/CSN
3.2
Analysis
Each time the F3 or F4 key is pressed, the range changes 10mV for the range of 10 100mV, and 100mV for the range of 100 - 1000mV.
Upon completing measurement, the results are displayed and the [START] key goes out.
If Continuous Measurement in Same Mode was set to ON...
Analyses will repeat until the STOP key is pressed. For details on the STOP key, refer to
Section 3.3.4.2 "Interrupting Analysis" on page 178.
If Continuous Measurement in Same Mode was set to OFF...
To perform additional analyses press the F1 [Add Injection] key, and follow the on-screen
directions.
To discard measured data and reanalyze the points from the start, press the F2 [Remeasure
point] key. After pressing the F6 [Yes] key, follow the on-screen instructions.
To start analysis using the next mode:
1.
2.
TIP »
Press the F6 [Go to Next Meas. Type] key.
Press the [START] key.
Note: Press the [START] key after confirming that the Ready lamp has
illuminated and that the [START] key is blinking.
Printing Data
If the Runtime Report item was set to ON in the "Conditions - Unit" screen, the analysis
results are automatically printed out for each analysis mode. For example, if measurements
are being performed in both TC and IC modes, the results from the TC analysis mode are
printed out when the analysis changes from the TC to the IC mode.
Step 5
Finish the Analysis
When measurements for all the modes are complete, the F6 key indication will display
Finish Measurement.
Procedure
1.
Press the F6 [Finish Measurement] key.
The display returns to the "Initial Display", and the analysis information is stored in
the data report.
Reference: For details on the data report, refer to Section 3.5.3 "Reviewing Data Reports" on page
213.
TOC-LCSH/CSN
123
3.2
Analysis
3.2.3.3 Multi-mode Analysis - Simultaneous Analysis
Simultaneous analysis measures TN as well as TC or NPOC.
Two types of simultaneous analysis are possible. Each has the option of utilizing
Continuous Measurement and incorporating other modes of analysis.
(1) TN and TC analysis
(2) TN and NPOC analysis
The sample analysis procedure consists of the following 7 general steps.
Step 1
Set the Parameters for TC or NPOC Analysis
Step 2
Set the Parameters for TN Analysis
Step 3
Set Simultaneous Analysis to ON
Step 4
Set the Analysis Parameters for any Modes Not Already Set in Steps 1 and 2
Above
Step 5
Set the Sample
Step 6
Press the [START] Key
Step 7
Finish the Analysis
Step 1
Set the Parameters for TC or NPOC Analysis
Refer to Section 3.2.3 "Sample Analysis" on page 112, "Step 1 Set the Analysis Mode" and
"Step 2 Set the Analysis Parameters".
Note:
Since analyses will be conducted using multiple analysis modes, set Continuous
Measurement in Same Mode to OFF.
Step 2
Setting the Parameters for TN Analysis
Procedure
1.
124
TOC-LCSH/CSN
Select the TN analysis mode. Press the F6 [TN] key.
The TN analysis parameters box is displayed. The Simultaneous Analysis item is
displayed. The Continuous Measurement in Same Mode item changes to display
Continuous Measurement.
3.2
TIP »
Analysis
Display at the Top of Screen
If the cursor is on TC analysis mode, a list of calibration curves for TC analysis is
displayed at the top of the screen. Similarly, if the cursor is on TN analysis mode, a list of
calibration curves for TN analysis is displayed at the top of the screen.
2.
3.
Move the cursor to the parameters box for TN analysis using the →key.
Set the TN analysis mode parameters.
Refer to Section 3.2.3 "Sample Analysis" on page 112, "Step 1 Set the Analysis
Mode" and "Step 2 Set the Analysis Parameters". Cancel setting parameters for an
analysis mode by pressing the corresponding function key. The parameter screen
closes.
Step 3
Set Simultaneous Analysis to ON
Procedure
1.
Move the cursor to the Calibration Curve (1st) item of the TN analysis parameters
box.
2.
3.
Use the ↑ key to move the cursor to the Simultaneous Analysis (+TN) item.
Toggle the setting to ON using the [ENTER] key.
To perform continuous measurement, set Continuous Measurement to ON. For the
procedure to make this setting, refer to Section 3.2.3 "Sample Analysis" on page 112
Step 2, Item" (2) Continuous Measurement in Same Mode".
Step 4
Set the Analysis Parameters for any Modes Not Already Set in Steps 1
and 2 Above
Proceed to Step 5 when only TN and TC or NPOC analysis will be used. Refer to Section
3.2.3 "Sample Analysis" on page 112,"Step 2 Set the Analysis Parameters".
Step 5
1.
Set the Sample
Press the [NEXT] key.
The "Measurement" screen is displayed.
TOC-LCSH/CSN
125
3.2
Analysis
2.
Set the sample.
If Continuous Measurement has been turned ON, set all the samples.
When the instrument enters the standby state, the Ready lamp illuminates and the
[START] key begins blinking.
Note: • To re-set the sample analysis parameters, press the F1 [Return] key. The
display returns to the "Settings" screen.
• To finish without performing sample analysis, press the [MEAS] key.
The display returns to the "Initial Display".
Step 6
Press the [START] Key
Procedure
1.
2.
Verify that the Ready lamp has illuminated and that the [START] key is blinking.
Press the [START] key.
The [START] key illuminates, the "Measurement Parameters" screen is displayed,
and sample analysis begins. The instrument status is displayed at the upper right
portion of the screen. The status changes as follows:
Washing → Sampling → Sparging → Injecting → Detecting Peak
TIP »
Graph Scale
The graph scale (ordinate) is displayed using the auto-ranging function. The range can be
changed (enlarged / reduced) within the range of 10 - 1000mV.
To enlarge the scale, press the F3 key.
To reduce the scale, press the F4 key.
Each time the F3 or F4 key is pressed, the range changes 10mV for the range of 10 100mV, and 100mV for the range of 100 - 1000mV.
Upon completing analysis, the results are displayed and the [START] key goes out.
TIP »
Profile
The TC and TN profile can be observed during analysis. The TC profile is the NPOC
profile. The TN profile is displayed as the default. To display the TC profile, press the F4
key.
If Continuous Measurement was set to ON...
Analysis continues automatically using the next analysis mode.
If Continuous Measurement was set to OFF...
To perform additional analyses, press the F1 [Add Injection] key, and follow the on-screen
directions.
To start analysis using the next mode:
1.
126
TOC-LCSH/CSN
Press the F6 [Go to Next Meas. Type] key.
3.2
2.
TIP »
Analysis
Press the [START] key.
Note: Confirm that the Ready lamp has illuminated and the [START] key
is blinking. Then press the [START] key.
Printing Data
Analysis results are automatically printed out for each analysis mode when the Runtime
Report item is set to ON in the "Conditions - Unit" screen.
To discard the measured data and perform the analysis over again, press the F2 [Remeasure
Point] key. Continue by pressing the F6 [Yes] key, and follow the on-screen directions.
Step 7
Finish the Analysis
When analyses for all the modes are complete, the F6 key will indicate Exit Measurement.
Procedure
1.
Press the F6 [Exit Measurement] key.
The display returns to the "Initial Display", and the analysis information is stored in
the data report.
Reference: For details on the data report, refer to Section 3.5.3 "Reviewing Data Reports" on page
213.
3.2.3.4 Multi-mode Analysis - Common Injection Analysis
Common Injection Analysis measures POC and NPOC using the same injection.
Continuous measurement may be utilized and other modes of analysis may be incorporated.
The sample analysis procedure consists of the following 7 general steps.
Step 1
Set the Parameters for POC Analysis
Step 2
Set the Parameters for NPOC analysis
Step 3
Set Common Mode Injection to ON
Step 4
Set the Parameters for Modes Other than POC and NPOC
Step 5
Set the Sample
Step 6
Press the [START] Key
Step 7
Finish the Analysis
Step 1 Set the Parameters for POC Analysis
Refer to Section 3.2.3 "Sample Analysis" on page 112, "Step 1 Set the Analysis Mode" and
"Step 2 Set the Analysis Parameters".
Note:
Since analyses are conducted using multiple analysis modes, set Continuous
Measurement in Same Mode to OFF.
TOC-LCSH/CSN
127
3.2
Analysis
Step 2
Setting the parameters for NPOC analysis.
Procedure
TIP »
1.
Select the NPOC analysis mode. Press the F5 [NPOC] key.
The NPOC analysis parameters box, and the Common Injection Analysis item are
displayed. The Continuous Measurement in Same Mode item changes to Continuous
Measurement.
2.
3.
Move the cursor to the parameters box for NPOC analysis using the → key.
Set the parameters for NPOC analysis.
Refer to Section 3.2.3 "Sample Analysis" on page 112, "Step 2 Set the Analysis
Parameters".
Display at the Top of Screen
If the cursor is on POC analysis mode, a list of calibration curves for POC analysis is
displayed at the top of the screen. Similarly, if the cursor is on NPOC analysis mode, a list
of calibration curves for NPOC analysis is displayed at the top of the screen.
Note:
Note:
128
TOC-LCSH/CSN
Set Continuous Measurement to ON to perform continuous
measurement. For the setting procedure, refer to Section 3.2.3
"Sample Analysis" on page 112, Step 2, " (2) Continuous
Measurement in Same Mode".
Cancel setting the parameters for analysis by pressing the
corresponding function key. The "Settings" screen closes.
3.2
Step 3
Analysis
Set Common Injection Analysis to ON
Procedure
1.
Move the cursor to the Calibration Curve (1st) item of the NPOC analysis parameters
screen.
2.
3.
Use the ↑ key to move the cursor to the Common Injection (POC+NPOC) item.
Toggle the setting to ON using the [ENTER] key.
To perform continuous measurement, set Continuous Measurement to ON. For the
procedure to make this setting, refer to Section 3.2.3 "Sample Analysis" on page 112,
Step 2, " (2) Continuous Measurement in Same Mode".
Step 4
Set the Parameters for Other Modes of Analysis
Refer to Section 3.2.3 "Sample Analysis" on page 112, "Step 2 Set the Analysis
Parameters".
Proceed to Step 5 when only POC and NPOC modes of analysis are used.
TIP »
If TN analysis is to be conducted, simultaneous analysis is possible. Refer to Section 3.2.3.3
"Multi-mode Analysis - Simultaneous Analysis" on page 124.
TOC-LCSH/CSN
129
3.2
Analysis
Step 5
Set the Sample
Procedure
1.
Press the [NEXT] key.
The "Measurement" screen is displayed.
2.
Set the sample.
When the instrument enters the standby state, the Ready lamp illuminates and the
[START] key begins blinking.
Note: • To re-set the sample analysis parameters, press the F1 [Return] key. The
display returns to the "Settings" screen.
• To finish without performing sample analysis, press the [MEAS] key.
The display returns to the "Initial Display".
Step 6
Press the [START] Key
Procedure
1.
2.
Verify that the Ready lamp has illuminated and that the [START] key is blinking.
Press the [START] key.
The [START] key illuminates, the "Analysis - Measuring" screen is displayed, and
sample analysis begins. The instrument status is displayed at the upper right portion of
the screen. The status changes as follows:
Washing → Sampling → Sparging → Injecting → Detecting Peak
TIP »
Graph Scale
The graph scale (ordinate) is displayed using the auto-ranging function. The range can be
changed (enlarged / reduced) within the range of 10 - 1000mV.
To enlarge the scale, press the F3 key.
To reduce the scale, press the F4 key.
Each time the F3 or F4 key is pressed, the range changes 10mV for the range of 10 100mV, and 100mV for the range of 100 - 1000mV.
Upon completing analysis, the results are displayed and the [START] key goes out.
130
TOC-LCSH/CSN
3.2
Analysis
If Continuous Measurement was set to ON...
Analysis continues automatically using the next analysis mode.
If Continuous Measurement was set to OFF...
To perform additional analyses press the F1 [Add Injection] key, and follow the on-screen
directions.
To start analysis using the next mode:
1.
2.
TIP »
Press the F6 [Go to Next Meas. Type] key.
Press the [START] key.
Note: Confirm that the Ready lamp has illuminated and the [START] key
is blinking, then press the [START] key.
Printing Data
Analysis results are automatically printed out for each analysis mode if the Runtime Report
item was set to ON in the "Conditions - Unit" screen.
To discard the measured data and perform the analysis over again, press the F2
[Remeasure Point] key. Continue by pressing the F6 [Yes] key, and follow the onscreen directions.
Step 7
1.
Finish Analysis
Press the F6 [Exit Measurement] key.
The display returns to the "Initial Display", and the analysis information is stored in
the data report.
Reference: For details on the data report, refer to Section 3.5.3 "Reviewing Data Reports" on page
213.
TOC-LCSH/CSN
131
3.2
Analysis
3.2.4 Creating a Method
The measurement condition parameters for sample analysis can be set and stored as a
"Method." Subsequent use of the parameters can be accomplished by merely retrieving the
stored method. A method can be stored in a method group according to a specified
classification. To delete a method, refer to Section 3.5.2 "Reviewing the Method List" on
page 211.
The procedure for creating a method consists of 2 general steps.
Step 1
Set the Method Group Name
Step 2
Create a Method
1)
Set the Analysis Method Parameters
2)
Saving the Method
Step 1
Set the Method Group Name
A method group can be set up in a 5-step procedure.
Procedure
1.
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
2.
Press the F4 [Meas. Cond.] key.
The "Conditions - Measurement Conditions" screen is displayed.
3.
Using the ↓ key, move the cursor to the "Name of Method Group - F #" item.
• GROUP #: # is a user selected number from 1 - 5.
•
132
TOC-LCSH/CSN
Maximum number of characters: 10 characters.
3.2
4.
5.
Analysis
Enter the GROUP name, and press the [Enter] key.
Press the F1 [Return] key.
The display returns to the "Initial Display".
Step 2
Create a Method
The procedure described below is for TC single-mode analysis.
1) Set the Analysis Method Parameters
1.
Press the [MEAS] key in the "Initial Display".
The "Measurement Parameters" screen is displayed.
2.
Press the F2 [TC] key.
The parameters box for TC analysis is displayed.
Note: • For IC analysis: Press the F3 [IC] key.
• For POC* analysis: Press the F4 [POC] key.
• For TN* analysis: Press the F5 [TN] key.
"*" denotes optional, and is displayed only if option settings are made.
3.
Enter the analysis parameters.
TOC-LCSH/CSN
133
3.2
Analysis
Analysis Parameters Items
•
•
•
•
•
•
•
•
•
Continuous Measurement in Same Mode
Calibration curve
Injection volume
Number of Injections
Maximum Number of Injections
SD
CV%
Acid Addition Ratio
Sparge Time
Reference: Refer to Section 3.2.3.1 "Single-mode Analysis" on page 112, "Step 2 Set the Analysis
Parameters".
2) Save the Method
134
1.
Press the [SAVE METHOD] key.
The "Method Store" screen is displayed.
2.
3.
Select the method group to be registered using keys F2-F6.
4.
Press the [Enter] key.
This confirms the method name.
5.
Press the [NEXT] key.
"Stored" is displayed, and the "Measurement Parameters" screen returns to the
display.
TOC-LCSH/CSN
Enter the method name.
Maximum number of characters: 16
3.2
TIP »
Analysis
To delete a method that is already registered, use the following procedure.
1. Use the ↑ key to move the cursor to the upper section of the screen.
2. Select the method to be deleted using ↓ ↑ keys.
3. Press the [CE] key.
To delete: press the F6 [Yes] key.
To cancel deletion: press the F1 [No] key.
3.2.5 Stopping Analysis
If it becomes necessary to interrupt an analysis in progress, any of the following three
methods may be used.
(1)
HALT
Immediately interrupts analysis. All data acquired during analysis is lost.
(2) STOP
Analysis continues until acquisition of the current peak is complete, at which time
analysis stops.
(3) Peak Stop
Peak analysis stops at that point. The peak area is displayed and analysis stops.
Procedure
1.
•
•
•
•
2.
Press the STOP key during analysis.
The following function keys are enabled.
F1: [Cancel] (cancels analysis stop)
F3: [HALT]
F4: [STOP]
F6: [Peak Stop]
Press the appropriate function key.
TOC-LCSH/CSN
135
3.2
Analysis
3.2.6 Discarding Data
To create a calibration curve or measure a sample identical samples are typically measured
multiple times to increase the reliability of the measured results. If there is great variance in
the resulting analysis data, the abnormal values may be discarded. However, once analysis
of a sample is completed and the analysis screen is closed, data can no longer be discarded.
Procedure
1.
Confirm that analysis is complete and that the analysis results are displayed to the
right side of the screen in a tabular format.
2.
3.
Using the ↑ ↓ keys, move the cursor to the data that you wish to discard.
Press the [CE] key.
The data is discarded, and "Exc" (Exclude) is displayed in front of the associated Inj#.
The values for Average Area, SD, and CV% at the top of the screen will change.
Canceling the Discard Data Operation
1.
2.
136
TOC-LCSH/CSN
Using the ↑ ↓ keys, move the cursor to the discarded data item.
Press the [CE] key.
The "Exc" indication is removed, and the values for Average Area, SD, and CV% at
the top of the screen change.
3.2
Analysis
3.2.7 Ending Analysis
Analysis can be ended using the following two methods.
•
•
Powering Down (Shutdown): Switches off the instrument.
Sleep: The instrument is left running until the preset time for the next analysis.
Powering Down (Shutdown)
The procedure for shutting down the instrument by switching the power OFF is described
below.
Procedure
1.
Press the F1 [Standby Option] key in the "Initial Display".
The "Standby Option - Sleep" screen is displayed.
2.
Press the F5 [Power OFF] key.
The message "Automatic Shutdown" is displayed.
3.
Press the F6 [Execute] key.
"Do you want to stop this process?" is displayed.
TOC-LCSH/CSN
137
3.2
Analysis
TIP »
If the F1 [No] key is pressed, the screen returns to the parameter at step 2. If the F6
[Execute] key is pressed, the electric furnace is automatically turned off, and 30 minutes
later, the instrument power is turned off and carrier gas flow is stopped (although the main
power remains on).
4.
If the analysis session is to be ended, press the F6 [Yes] key.
TIP »
To cancel the instrument shutdown, press the F1 [Cancel] key, and the display returns to
the "Initial Display".
TIP »
If the power switch is held down for three seconds, the procedure from 1 to 4 can be skipped
to turn the power off (shutdown).
TIP »
The instrument can be restarted by holding down the power switch for three seconds during
a shutdown (while the power switch's LED is flashing orange) before the power to the
instrument is switched off.
Sleep
The instrument remains powered up until the date and time of the next analysis. Since the
instrument was kept in an operating condition, at the set time, analysis can be performed.
During the sleep period, the electric furnace power and carrier gas are turned off until the
analysis time. About 1 hour prior to the set time, the electric furnace turns on, the
temperature rises as the carrier gas flow is started. This allows the instrument to achieve the
analysis ready state at the set time.
Procedure
TIP »
138
1.
Press the F1 [Standby Option] key in the "Initial Display".
The "Standby Option" screen is displayed.
2.
Press the F4 [Sleep] key. The "Sleep" screen is displayed.
Enter the date and time for the next start-up.
Move the cursor in sequence from month to day, year, hour and minute, entering
values appropriately.
After entering the values, press the [Enter] key to confirm the values.
Entries are possible from the current date and time to 12/31/2099.
Use the → key to move the cursor right, and the ← key to move it left.
TOC-LCSH/CSN
3.2
3.
Set the states of the displayed items to ON / OFF.
1) Use the ↓ key to move cursor to the item to be set.
2)
Use the [ENTER] key to toggle ON /OFF.
Note:
4.
Analysis
Use the same procedure for all the items.
Press the F6 [Execute] key.
The items that have been set to OFF will automatically be switched off. About one
hour prior to the set time, these units will be switched back on, allowing analysis to
begin at the set time.
TIP »
To cancel the power shutdown procedure, press the F1 [Return] key.
TIP »
Holding down the power switch can cancel the sleep mode and restart the instrument.
Note:
When a carrier gas purification kit is used, if the power switch is turned OFF or
the instrument is shut down or put into the sleep state, an air hissing sound may
be heard from the inside of the instrument at the time of carrier gas stopping. This
is the sound of releasing residual pressure of carrier gas from within the CO2
absorber and is normal.
TOC-LCSH/CSN
139
3.3
Analysis with the Autosampler
3.3
Analysis with the Autosampler
3.3.1 Sample Preparation for Autosampler Measurement
3.3.1.1 Vial Types
The three types of ASI-L vial are 9 mL, 24 mL, and 40 mL vials. There are two models of
ASI-L unit, one is dedicated to 24 mL vials and the other supports both 9 mL and 40 mL
vials. The sample volume associated with each vial type is shown below. Introduce the
specified volume of sample into each vial to basically attain the sample volume shown in
Table 3.2. When using the external sparge kit to sparge ASI-L vials in NPOC analysis,
reduce the sample volume to minimize contact between sample droplets and the vial cap
caused by sparging.
Table 3.2 • Sample Volume for Each Vial Type
Vial Type
Sample Volume
Sample Volume When Sparging ASI-L Vials
with the External Sparge Kit
Note
9 mL
8.5 mL2
6.4 mL1
24 mL
22 mL4
20 mL3
40 mL
38 mL4
35 mL3
• Note 1: Sample volume when sample is introduced up to about 17 mm from
the top of the vial.
• Note 2: Sample volume when sample is introduced up to about 10 mm
from the top of the vial.
• Note 3: Sample volume when sample is introduced to about 10 mm from
the bottom of vial cap.
• Note 4: Sample volume when sample is introduced to about 5 mm from
the bottom of vial cap.
The following restrictions apply when using 9 mL vials.
•
•
•
•
This vial size is not suited to high sensitivity analysis, such as pure water analysis,
because the maximum sensitivity range becomes 0 to 1 mg/L (analysis using a
calibration curve full scale of 1 mg/L).
Commercially available aluminum foil should be used to seal the vial because dedicated
septums are not provided.
The magnetic stirrer cannot be used.
TC-IC analysis and NPOC+POC analysis cannot be performed.
Note:
140
TOC-LCSH/CSN
Wash any new vials using laboratory glassware detergent and then rinse them
thoroughly with water before use.
3.3
Analysis with the Autosampler
Maximum Number of Measurements by Vial Type
The tables below indicate the full scale values of the calibration curve and the maximum
number of measurements possible under those conditions for the 24 mL and 40 mL vials,
respectively, when they are filled with the specified volume of sample. This assumes use of
the software-recommended injection volume, and the default 2 washes. As for TC-IC
measurement, the calibration curve full scale is the same for both TC and IC.
When TC measurement, TC-IC measurement and NPOC measurement are all performed
from a 40 mL vial, the maximum number of measurements is shortened by 1 – 3
measurements.
Table 3.3 • 24 mL Vials
Calibration Full Scale
Maximum Number of Measurements
NPOC Analysis
TC Analysis
TC-IC Analysis
100 µg/L
2
3
1
500 µg/L
4
5
1
1 mg/L
5
6
2
5 mg/L
6
7
3
10 mg/L
More than 6
More than 7
More than 3
Table 3.4 • 40 mL Vials
Calibration Full Scale
Note:
Maximum Number of Measurements
NPOC Analysis
TC Analysis
TC-IC Analysis
100 µg/L
2
3
1
500 µg/L
4
5
1
1 mg/L
5
6
2
5 mg/L
6
7
3
10 mg/L
More than 12
More than 17
More than 8
When using a TOC-LCSN, perform measurement using a calibration curve full
scale greater than 1 mg/L.
The target measurement range for three repeated measurements using 9 mL vials is shown
in Table 3.5.
The table indicates the maximum number of measurements when using TOC standard
catalyst, the automatic setting for the sample injection volume, and stream washing is set to
once only. If residual removal is insufficient between vial usages when washing is set to
once only, performing analysis with vials of pure water placed between every other vial can
improve residual problems.
Table 3.5 • Maximum Number of Measurements Using 9 mL Vials
Analyte
Measurement Range
Maximum Number of Measurements
NPOC
Range over 0 to 1 mg/L
When sparging with the sample injector syringe: 3
When sparging with the ASI-L vials: 2
TC
Range over 0 to 1 mg/L
3
IC
Range over 0 to 2 mg/L
3
TN
All ranges
3
TOC-LCSH/CSN
141
3.3
Analysis with the Autosampler
3.3.1.2 Filling Vials with Sample
In most cases, vials can be placed in the ASI-L turntable and analyzed without being
sealed. Vials must be sealed in the following situations:
(1) sparging with the ASI-L for NPOC analysis
(2) measuring acidic samples
(3) IC analysis
(4) POC analysis
(5) low-concentration samples (as a guideline, less than 10 mg/L)
(6) alkaline samples (pH 7 or higher)
(7) samples that contain volatile organic hydrocarbon components
(8) a large number of samples to be measured
(9) standard solutions
In situations (1) and (2) above, corrosion of the instrument may occur due to spattering of
sample, which contains acid.
In situations (3) through (9), results may be affected by either volatilization of the TOC
components in the sample or contamination from substances that absorb CO2 from the
atmosphere. If aluminum foil is used to cap the sample vial for NPOC or acidic sample
measurement, there is a danger of acid volatilization through the hole caused by insertion of
the needle. Do not use aluminum foil to cap the vials.
Sealing Sample Vials
There are two acceptable methods for sealing vials: (1) using the caps provided with the
vials, or (2) using aluminum foil or commercially available sealing material.
However, because the airtightness of aluminum foil seals are poor, their use may cause
corrosion inside the ASI-L due to the vaporization of acid in NPOC analysis and acidic
sample measurement, which both use the ASI-L to perform sparging. For these types of
measurements, use seals that are airtight.
Note that Shimadzu does not recommend using Parafilm seals because pieces of this seal
can become attached to the needle and prevent normal sample extraction.
Note:
Regardless of the type of seal used, always use vials after washing them with
water or laboratory glassware detergent and then rising them thoroughly with
water.
Using Caps
For 24 mL and 40 mL vials
Caps and seals are provided with these vials.
1.
2.
142
TOC-LCSH/CSN
Place a seal over the vial opening.
Cap the vial over the seal.
Note: Because the seals are perforated during injection, discard the seals
after use.
3.3
Analysis with the Autosampler
3.3.1.3 Placing Vials in the Vial Rack
Remove the vial rack from the ASI-L before inserting the sample vials. There are three
different types of vial racks, each accommodating a different vial size.
The ASI-L permits random access of vials in the vial rack. Vials are measured according to
the sequence set in the Sample Table Editor, thus enabling analysis to start from any
position number in the vial rack, and for analysis to occur in non-sequential vial positions.
Ensure that the vials are placed into the vial rack vertically and that they remain straight
during analysis.
TIP »
When samples are to be sparged using the optional external sparge kit, analysis is
performed more efficiently if the vials are placed in sequential rack positions without gaps.
This allows a vial to be sparged while an adjacent vial is being measured.
Installing the Vial Rack
Install the rack using the following procedure.
1.
2.
Insert the vials into the vial rack and place the rack on the ASI-L turntable.
Place the cover over the turntable.
Note: • During analysis, the turntable must be covered. The ASI-L will not
operate if the turntable cover is not detected.
• Do not write on the periphery of the vial rack or stick adhesive tape onto
the vial rack. If aluminum foil or water droplets are adhered to the
periphery of the vial rack, remove them. These may prevent the vial rack
from rotating correctly.
TOC-LCSH/CSN
143
3.3
Analysis with the Autosampler
3.3.1.4 Rinse Water Preparation
Replenishing the Rinse Water
Replenish the rinse water in the rinse bottle. Ensure that the rinse water level reaches above
the 2 L indication on the rinse bottle.
Inserting the Rinse Tubing
Insert the rinse tubing as shown in Figure 3.34 "Rinse Tubing Placement". Place the
provided tubing ring-band over the end of the tubing, and slide the ring band up the tubing
until it reaches the bottle cap and about 200 mm of the tubing extends into the rinse bottle.
Verify that the end of the rinse tubing descends to a point just above the bottom of the
bottle.
Note:
Rinse water will not flow properly if the rinse tube is not inserted correctly, and
measurement values may be adversely affected.
Use the provided tubing
ring-band to adjust the
tubing insertion depth.
Ensure that the tubing
reaches nearly to the
bottom of the rinse bottle.
Figure 3.34 Rinse Tubing Placement
Rinse Water Usage
The required volume of rinse water will vary depending on the measurement parameters.
The information in Table 3.6 • "Rinse Water Usage Examples" can serve as a guide, ensure
that there is always a sufficient volume of rinse water. If the capacity of the provided 2 L
bottle is insufficient, use a container with greater capacity.
Table 3.6 • Rinse Water Usage Examples
Flowline
Flowline
Rinse Water
wash A
wash B
Usage
1
1
Approx.1.3 L
Analyzing 93 samples with standard model.
Approx.2.3 L
Conducting NPOC analysis of 93 samples with
external sparge kit.
Approx.2.6 L
Analyzing 93 samples with standard model.
Approx.3.6 L
Conducting NPOC analysis of 93 samples with
external sparge kit.
2
144
TOC-LCSH/CSN
2
Remarks
3.3
Analysis with the Autosampler
3.3.1.5 High Sensitivity ASI-L Analysis
If samples with TOC concentrations of 100 µg/L or less (such as purified water or ultrapure water) are measured using an ASI-L, the following precautions associated with high
sensitivity analysis must be considered. Refer to Section 3.1.19.1 "High Sensitivity
Analysis" on page 76 for additional information.
(1)
NPOC analysis is recommended. TOC (TC-IC) analysis tends to have a greater
variation in measured values than the NPOC analysis because IC often accounts for a
significant portion of the TC, and the errors in the two values are additive, which
significantly affects TOC analysis.
(2) To generate a calibration curve, fill well-washed vials with standard solutions to about
5-10 mm from the top of the vial, and immediately seal each vial.
Use a cap that has been washed with purified water prior to use.
When placing the vial in the rack, handle the vial carefully to avoid contact between
the standard solution and the cap.
Low-concentration standard solutions must be prepared each time they are used.
(3) To stabilize the peaks, perform 4 to 5 injections using the same analysis parameters
prior to analyzing the calibration standard solutions. For example, to generate a
400 µg/L calibration curve, set 400 µg/L as the 1st standard solution concentration,
and enter 1 as the vial number. Actually place a 0 µg/L solution in vial position 1. The
objective at this point is not to generate a calibration curve, but to inject water using
the same injection volume used for the calibration curve that is to be generated. This
not only stabilizes peaks but also thoroughly washes the sample needle and sparge
needle with purified water.
After the stabilizing injections are complete, place the 0 µg/L and 400 µg/L
calibration standard solutions in vial positions 2 and 3, insert the calibration standards
into the Sample Table Editor, and start measurement.
(4) Acid addition for NPOC analysis can be performed automatically using the ASI-L. It
is best to perform manual addition of hydrochloric acid for NPOC analysis on the
order of 10 µg/L. This is because, automatic acid addition pierces the vial seal and
allows CO2 contamination from the air.
(5) Select [No] in the "Conditions - Unit Management" screen for [Needle Rinse] to
prevent washing of the needle.
Even if ultra-pure water is used as rinse water, the TOC concentration of the rinse
water will increase during the time it is exposed. For best results, do not rinse the
needle for analyses on the order of 100 µg/L.
(6) Do not use the analysis value acquired from the first sample vial. In sample analysis,
particularly analysis on the order of 10 µg/L, the first sample measured may yield
high results.
(7) When using the optional external sparge kit, use the standard sparge gas flow rate of
100 mL/min. The recommended sparging times are displayed as 3 minutes for 9 mL
vials, 6 minutes for 24 mL vials, and 10 minutes for 40 mL vials. If sparging is
insufficient, increase the gas flow rate or the sparging time accordingly.
TOC-LCSH/CSN
145
3.3
Analysis with the Autosampler
3.3.1.6 Acid Addition in NPOC Analysis
Installation of the optional external sparge kit allows sample acidification/sparging to be
conducted in the ASI-L during NPOC measurement. In this case, acid addition for
acidification can be performed automatically in the ASI-L.
To perform acid addition using the ASI-L, first enter a value for the acid addition amount
on the "Measurement Parameters" screen.
When analysis starts, acid is first drawn from the acid bottle into the syringe and then the
set amount of acid is added from the sample water sampler needle into all vials designated
for acid addition. Use 1 mol/L hydrochloric acid as the standard acid for addition. While
the acid addition ratio (ratio of acid with respect to the sample) should normally be set to
about 1 to 3%, purified water analysis can use a ratio as low as about 0.5%.
The hydrochloric acid concentration or amount added should be adjusted in accordance
with the sample pH or buffering strength to bring the sample pH to 2-3. Prior to analysis,
verify that the pH is 2-3 using pH paper. The pH need not be checked each time if the same
type of sample is routinely measured.
CAUTION
Hydrochloric acid is a hazardous chemical. Exercise caution when handling to
prevent contact and spills. For details, refer to Section 5.10 "Safety Data Sheets"
on page 377.
If the sample pH does not reach a value between 2 and 3, increase the acid addition ratio or
the acid concentration. Excessively increasing the acid addition ratio will result in dilution
of the sample. On the other hand, if the acid amount is too small, the size of the acid droplet
on the tip of the needle will not be large enough to drop from the needle.
Visually observe the process through the glass vial to determine if the acid droplet is
actually added to the sample.
The needle will be washed every time acid is added if [ON] is selected for [Needle Rinse
after acid add] in the "Conditions - Unit Management" screen. To save time during the
analysis sequence, washing of the needle is unnecessary if the variation in NPOC content
among the samples is not large.
3.3.1.7 Sparging in NPOC Analysis
Installation of the optional external sparge kit allows sparging to be performed on samples
in vials in the ASI-L. This allows sparging of the next sample while the sample in the vial at
the sampling position is being analyzed. The recommended sparging time settings are
displayed as 3 minutes for 9 mL vials, 6 minutes for 24 mL vials, and 10 minutes for 40 mL
vials. If sparging is insufficient, increase the gas flow rate or the sparging time accordingly.
The standard sparge gas flow rate is 100 mL/min. If the sparge gas flow rate is set too high,
sample will be spattered onto the cap seal. Adjust the sparge gas flow rate to avoid
spattering.
To verify that enough IC is removed during sparging using the ASI-L to enable unhindered
NPOC analysis, perform IC analysis on the remaining sample following NPOC analysis.
146
TOC-LCSH/CSN
3.3
Analysis with the Autosampler
CAUTION
When the vials are capped and sparging is performed without automatic acid
addition via ASI-L, pierce the caps before analysis by using the tip of a provided
needle or other instrument. This allows the sparge gas to vent. If sparge gas is
not vented from the vials, pressure will build inside the vials and prevent
effective sparging.
Note that the inside surfaces of the sparging needle may corrode due to
unwanted sample entry when conducting measurements other than NPOC
measurement that involve acidification and sparging of vials in the ASI-L
(including TC measurement, IC measurement, and NPOC measurement that
performed acidification and sparging within the TOC-L) over long periods of
time. For this reason, Shimadzu recommends removing the sparging needle
when performing these types of measurements.
3.3.1.8 Stirrer Preparation
When using the optional magnetic stirrer on the ASI-L, perform the following procedure to
enable the magnetic stirrer. After attaching the optional magnetic stirrer, use the following
procedure to enable use of the stirrer.
The rotation speed can also be set as necessary.
Procedure
1.
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
2.
3.
4.
Using the arrow keys, move the cursor to the "ASI - Stirrer" item.
Set the magnetic stirrer to ON using the [ENTER] key.
Press the F1 [Return] key.
The display returns to the "Initial Display".
TOC-LCSH/CSN
147
3.3
Analysis with the Autosampler
Adjusting the Rotation Speed
Adjust the rotation speed by turning the stirrer rotation speed adjustment dial at the bottom
of the right side of the ASI-L.
Precautions for Using an ASI-L Equipped with a Magnetic Stirrer
Follow these precautions when using an ASI-L equipped with a magnetic stirrer.
(1)
When conducting measurement of a sample containing suspended solids, perform
pretreatment homogenization of the sample to obtain a uniform distribution of the
smallest possible particles. Apply a powerful enough homogenization process such
as, ultrasonication, to crush the suspended particles as much as possible. The
magnetic stirrer is not designed to perform such homogenization.
Stirring a non-homogeneous sample will not provide a uniform suspension. This will
result in poor measurement reproducibility.
(2) Depending on the characteristics of the suspended particles such as, shape, specific
gravity, size, strength and degree of cohesion, the stirrer bar may not be able to
sufficiently agitate the sample. For example, solid particles with a high specific
gravity sink to the bottom and prevent formation of a good mixture.
Magnetic Stirrer Operation
•
•
Two types of magnetic stirrers are available, one for the 24 mL and one for the 40 mL
size vials. 9 mL vials cannot be used.
Only the outermost four rows of the vial tray are accessible to the magnetic stirrer.
Note:
•
•
•
•
148
When using 24 mL vials, the innermost row of vials are inaccessible to the stirrer.
When using 40 mL vials, all vials are accessible to the stirrer.
The magnetic stirrer only agitates vials in the current sampling position and the next
sampling position. Proper mixing is not performed even if the stirrer bar can rotate at
other vial positions. For example, if vial number 20 is selected, stirring is performed for
vial 20 (sampling position) and vial 21 (next sampling position).
Depending on the shape of the vial bottom, the stirrer bar rotation axis may shift.
However this has almost no effect on the effectiveness of the stirring.
Adjust the stirrer rotation speed according to the sample properties. Use the stirrer speed
control dial on the right side of the ASI-L. Be careful not to increase the speed
excessively, as this can cause the stirrer bar to jump around instead of rotate.
Turning the stirrer on and off repeatedly while the stirrer is set at the lowest speed may
cause fluctuations to occur in the motor speeds. This is due to the relationship between
the resistance values inside the motor and the impressed voltage, and only occurs when
the motor voltage is small. If this occurs, readjust the rotation speed using the following
procedure.
TOC-LCSH/CSN
3.3
Analysis with the Autosampler
3.3.2 Setting General Measurement Conditions
Settings are made for the following 7 items when using the ASI-L.
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Vial
Needle Set
Needle Rinse
Needle Rinse After Acid Addition
Stirrer
Flowline Wash A
Flowline Wash B
Note:
The general analysis parameters for the ASI must be set after performing settings
for all of the items in Section 3.3.2 "Setting General Measurement Conditions"
on page 149.
Procedure
1.
Press the F4 [Conditions] key in the "Initial Display".
The "Conditions - Unit Management" screen is displayed.
2.
Perform settings for items (1)-(7), as described below.
(1) Vial
This sets the size of the ASI-L vial to be used.
Procedure
1.
2.
Use the arrow keys to move the cursor to the Vial item.
Press the [ENTER] key to display all the vial types.
• 9mL
• 24mL
•
3.
4.
40mL
Use the ↓ ↑ keys to select the vial size to be used.
Press the [Enter] key to confirm the vial size.
TOC-LCSH/CSN
149
3.3
Analysis with the Autosampler
(2) Needle Set
This selects the needles to be used for analysis.
Description of Needles
Sample:
Uses only the sample needle.
Sample + sparge:
Uses of a total of two needles, a sample needle and a sparge
needle.
Note:
The instrument cannot detect the type of needle installed. Therefore, it is
necessary to enter the needle type according to needle actually installed.
Procedure
1.
2.
Use the arrow keys to move the cursor to the Needle Set item.
3.
4.
Use the ↓ ↑ keys to select the needle actually installed.
Press the [ENTER] key.
All the needle types are displayed.
• Sample
• Sample + sparge
Press the [Enter] key to confirm the needle type.
(3) Needle Rinse
This sets whether or not the outside of the sample needle (and sparge needle if installed)
will be washed following analysis.
Washing the outside of the needle prevents contamination of the next sample with sample
adhering to the needle from the previous analysis. If there is not a large difference in
concentration among all of the samples placed in the autosampler, washing can be omitted.
If analysis on the order of 100ppb is to be performed, the concentration in the wash water
will increase during the time it is exposed, even if ultra-pure water is used. Better results
are obtained in this situation if the needle is not washed.
Procedure
1.
2.
Use the arrow keys to move the cursor to the Needle Rinse item.
Set needle rinse to ON/OFF using the [ENTER] key to toggle through the settings.
(4) Needle Rinse After Acid Addition
This sets whether or not the outside of the needle is washed after each acid addition.
Needle washing can be performed after each acid addition. To save time during the analysis
sequence, washing of the needle may be unnecessary if the variation in the NPOC content
is small.
Procedure
1.
2.
150
TOC-LCSH/CSN
Use the arrow keys to move the cursor to the Needle Rinse after acid add item.
Set needle rinse to ON/OFF using the [ENTER] key to toggle through the settings.
3.3
Analysis with the Autosampler
(5) Stirrer
Determines whether the sample will be stirred with an optional magnetic stirrer. Analysis
can be performed while stirring the sample, enabling sample of suspended solids. This
prevents sedimentation and aggregation of suspended solids.
Procedure
1.
2.
Use the ↓ key to move the cursor to the ASI Magnetic Stirrer item.
Set the stirrer option to ON/OFF using the [ENTER] key to toggle through the
settings.
(6) Flowline Wash A
Sets the number of times the flow line is washed after each sample injection (0-3 times).
After sample injection, the injection flow line that was utilized is washed with wash water.
This is to prevent deterioration of the injector due to the build-up of salts at the tip of the
injection tubing when measuring samples containing a high salt content (1000ppm or
greater).
Note:
This wash operation is unnecessary with samples having low salt content. Set this
value to 3 when sample salt content is 1% or greater.
Procedure
1.
2.
Use the arrow keys to move the cursor to the Flowline wash A item.
Enter the number of washes, and press the [Enter] key.
(7) Flowline Wash B
Sets the number of times the flow line is washed after the analysis sequence is complete (05 times).
After all the sample analyses are complete, all of the flow lines that were used are washed
with wash water. If automatic acid addition has been selected, washing is performed after
acid has been added to all the samples, thereby eliminating the remaining acid in the
sample needle and flow line.
Note:
Typically, a setting of 2 is used, however, if the samples to be measured contain
acid, base or salt, a setting of 3 - 4 is used.
Procedure
1.
2.
3.
Use the arrow keys to move the cursor to the Flowline wash B item.
Enter the number of washes, and press the [Enter] key.
After all of the above settings are complete, press the F1 [Return] key.
The display returns to the "Initial Display".
TOC-LCSH/CSN
151
3.3
Analysis with the Autosampler
3.3.3 Setting Analysis Parameters
To use the autosampler for calibration curve analysis and sample analysis the analysis
sequence and schedule must first be determined.
Displaying the "ASI Schedule Settings" Screen
1.
Press the [ASI] key while viewing the "Initial Display".
The "ASI Schedule Settings" screen is displayed.
The procedures for performing the calibration curve analysis and sample analysis are
described separately.
3.3.3.1 Calibration Curve Analysis
Single-point and multi-point calibration curve settings are both available for calibration
curve analysis.
Each is described here.
TC analysis with a concentration unit of mg/L is used for the example, but the methods are
the same for IC, POC and TN analysis.
Procedure for Displaying "Calibration Setting" Screen
1.
Move the cursor to an empty row in the "ASI Schedule" screen.
Reference: Press the [MEAS] key to display the "Sample Analysis Setting" screen. Refer to Section
3.3.3.5 "Sample Analysis Settings" on page 161.
152
TOC-LCSH/CSN
3.3
2.
Analysis with the Autosampler
Press the [CAL] key.
The "ASI Calibration Settings" screen is displayed.
3.3.3.2 Single-point Calibration Curve Analysis
The procedure for generating a single-point calibration curve consists of two steps.
Step 1
Set the Parameters for the Calibration Curve
Step 2
End the Calibration Curve Analysis
Step 1
Set the Parameters for the Calibration Curve
The following 14 items comprise the parameters needed for generating the calibration
curve.
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
Analysis Mode: Sets the type of analysis that will be performed (i.e. TC, IC, POC and
TN Analysis).
Calibration Curve Number: Sets the number assigned to the calibration curve.
Vial Number: Sets the vial number used by the ASI.
Standard Solution Concentration: Sets the concentration of the injected standard
solution.
Number of Injections (default: 1): Sets the number of injections for standard solution
analysis.
Maximum Number of Injections (default: 1): Sets the maximum number of injection
(analysis injections + additional injections).
SD (Default: 0.1): Sets the standard deviation limit.
CV% (Default: 2.0): Sets the CV% limit value.
Dilution Factor: Sets the dilution factor.
Injection Volume: Sets the injection volume of the standard solution.
Acid Addition Ratio: Sets the ratio of acid added to sample (IC analysis).
Sparge Time: Sets the length of time sparging is to be performed.
Curve Type: Sets the type of calibration curve (i.e. point-to-point or least squares
linear regression curve).
TOC-LCSH/CSN
153
3.3
Analysis with the Autosampler
(14) Curve Shift: Sets the shift of calibration curve towards the zero point (i.e. no shift,
shift to zero point or shift to the TC blank point).
(1) Analysis Mode
1.
TIP »
Press the F2 [TC] key.
The TC parameters box is displayed as the default. The currently stored calibration
curves are displayed at the top of the screen.
Note: • For IC analysis: Press the F3 [IC] key.
• For POC* analysis: Press the F4 [POC] key.
• For TN* analysis: Press the F5 [TN] key.
"*" denotes optional, and is displayed only if optional settings have been
made.
To cancel the analysis mode setting, press the function key corresponding to the analysis
mode. The parameters box closes.
(2) Calibration Curve Number
1.
Enter the calibration curve number.
A list of the previously generated calibration curves is presented at the top of the
screen.
Referring to this list, enter a number that has not yet been used.
2.
Press the [Enter] key.
Confirms the calibration curve number setting.
(3) Vial Number
1.
2.
154
TOC-LCSH/CSN
Use the ↓ key to move the cursor to the Vial # item.
Enter a vial number, and press the [Enter] key.
Note: Setting the vial number to 0 causes sample from the No. 1 port of
the 8-port valve.
3.3
Analysis with the Autosampler
(4) Standard Solution Concentration
1.
Move the cursor to the Standard Solution Concentration (STD Conc.) item using the
↓ key.
2.
Enter the concentration of the standard solution to be injected for TC analysis. Refer
to Section 3.1.17.4 "Concentration Unit" on page 59.
3.
Press the [Enter] key.
The optimal injection volume is checked, and displayed.
(5) Number of Injections
1.
2.
Move the cursor to the Number of Injections (Inj #) item using the ↓ key.
Set the number of injections of standard solution to be made for analysis, and press
the [Enter] key.
(6) Maximum Number of Injections
1.
Move the cursor to the Maximum Number of Injections (Max # of Inj) item using the
↓ key.
2.
Set the maximum number of injections of standard solution to be made for analysis,
and press the [Enter] key.
Note: Maximum Number of Injections
Maximum number of injections refers to the number of injections in repeat
analysis if the automatic additional analysis function is used. Whether
automatic additional analyses are performed is determined by the settings
for standard deviation (SD) and coefficient of variation (CV%). After
analysis using the set number of injections is complete, the SD and CV%
values for those results are compared to the limits for SD and CV%. If both
of the actual values are greater than the limits, the automatic additional
analysis function is activated.
3.
Press the [Enter] key.
(7) SD
This setting is only available when the Number of Injections is less than the Maximum
Number of Injections.
1.
2.
Move the cursor to the SD item using the ↓ key.
Enter the standard deviation value, and press the [Enter] key.
(8) CV%
This setting is only available when the Number of Injections is less than the Maximum
Number of Injections.
1.
2.
Move the cursor to the CV% item using the ↓ key.
Enter the CV% value, and press the [Enter] key.
TOC-LCSH/CSN
155
3.3
Analysis with the Autosampler
(9) Dilution Factor
The optimal dilution factor is automatically displayed when the concentration of the
standard solution is entered.
1.
2.
Move the cursor to the Dilution Factor (Dil. Factor) item using the ↓ key.
Enter the dilution factor, and press the [Enter] key.
(10) Injection Volume
The optimal injection volume is automatically displayed when the concentration of the
standard solution is entered.
1.
2.
Move the cursor to the Injection Volume (Inj. Volume) item using the ↓ key.
Enter the injection volume, and press the [Enter] key.
(11) Acid Addition Ratio
Entered only when acid is to be added to the standard solution.
1.
2.
Move the cursor to the Acid Addition Ratio (Acid ratio) item using the ↓ key.
Enter the amount of acid to be added, and press the [Enter] key.
(12) Sparge Time
Entered only if the standard solution is to be sparged.
1.
2.
Move the cursor to the Sparge Time item using the ↓ key.
Enter the sparge time, and press the [Enter] key.
(13) Curve Type
This parameter selects which curve type is generated for a calibration curve using 3 or more
points. The choices are point-to-point calibration curve, where a straight line connects the
individual points or least squares linear regression curve.
1.
2.
Move the cursor to the Curve Type item using the arrow keys.
Set the curve type.
Toggle between the settings using the [ENTER] key.
(14) Curve Shift
This parameter selects whether to shift the calibration curve through the origin (zero point),
force the calibration curve to pass through the blank point determined by the TC Blank
Check value, or not to shift the calibration curve at all.
Note:
1.
156
TOC-LCSH/CSN
The calibration curve will not shift to the blank point unless the injection volume
is the same as that used in the TC Blank Check analysis.
Move the cursor to the Shift item using the arrow keys.
3.3
2.
Analysis with the Autosampler
Set the curve shift.
Toggle through the settings using the [ENTER] key.
Step 2
End the Calibration Curve Analysis
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Schedule Settings" screen. In the row that was just set,
"α-n" is displayed. (α: Analysis mode, n: Calibration curve number)
Example: TC - 1.
3.3.3.3 Multi-point Calibration Curve Analysis
A multi-point calibration curve can be generated with a maximum of 10 points. Set the
concentrations of the standard solutions to be measured using the procedure described
below.
The procedure for generating a multi-point calibration curve consists of the following three
general steps.
Step 1
Set the Parameters for the 1st Point
Step 2
Set the Parameters for the 2nd and Subsequent Points
Step 3
End the Calibration Curve Analysis
Step 1 Set the Parameters for the 1st Point
Refer to Section 3.2.2.1 "Single-point Calibration Curve" on page 92, "Step 1 Set the
Analysis Mode".
Step 2 Set the Parameters for the 2nd and Subsequent Points
Procedure
1.
Use the ↓ ↑ keys to move the cursor to the parameters box for the 1st point.
TOC-LCSH/CSN
157
3.3
Analysis with the Autosampler
2.
Press the → key.
The parameters box for the 2nd point is displayed.
3.
Set the parameters for the 2nd point.
The injection volume displayed is that for the highest concentration among the
standard solutions entered.
4.
Repeat steps 2 and 3 above to set the calibration curve parameters for the 3rd and
subsequent points. The display moves to the next screen for setting the 6th and
subsequent points.
Reference: For the setting procedure, refer to operations (3) to (8) of Step 1 "Set the Parameters for
the Calibration Curve" of Section 3.3.3.2 "Single-point Calibration Curve Analysis" on
page 153.
Displaying the Previous Page (points 1 to 5)
1.
Move the cursor to the parameters box for Point-6.
2.
Press the ← key.
The screen for the previous page is displayed.
Displaying the Following Page (points 6-10)
158
1.
Move the cursor to the parameters box for Point-5.
2.
Press the → key.
TOC-LCSH/CSN
3.3
Analysis with the Autosampler
Discarding a Point (n point)
1.
Move the cursor to the parameters box for Point-n.
2.
Press the F6 [Delete Point] key.
The parameters box for Point-n is deleted. If the F6 key is pressed at Point-1, the
parameters box is not deleted; the default display is reinstated.
Step 3 End Calibration Curve Analysis
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Schedule Settings" screen. In the row that was just set,
"α-n" is displayed. (α: Analysis mode, n: Calibration curve number)
Example: TC - 1
3.3.3.4 Multi-point Calibration Curve Analysis with Diluted Solution
It is possible to generate a multi-point calibration curve using a single standard solution.
Set the concentrations in the order of the standard solutions to be analyzed.
The procedure for generating a multi-point calibration curve with diluted solution consists
of the following three general steps.
Step 1
Set the Parameters for Generating the Calibration Curve for the First Point.
Step 2
Set the Parameters for Generating the Calibration Curve for the Second and
Subsequent Points.
Step 3
Finish Calibration Curve Analysis Setting.
Step 1 Set the Parameters for Generating the Calibration Curve for the First
Point.
For the setting procedure, refer to Step 1 "Select the Mode." and Step 2 "Set the Parameters
for Generating the Calibration Curve for the First Point." of Section 3.2.2.3 "Multi-point
Calibration Curve Analysis with Diluted Solution" on page 103.
Step 2 Set the Parameters for Generating the Calibration Curve for the
Second and Subsequent Points.
TOC-LCSH/CSN
159
3.3
Analysis with the Autosampler
Procedure
1.
Move the cursor to the parameter setting box for the first point with the ↓ ↑ keys.
2.
Press the → key.
The parameter setting box for the second point will be displayed.
3.
Set the parameters for generating the calibration curve for the second point.
The injection volume corresponding to the standard solution with the highest
concentration among those set is displayed.
4.
Set the parameters for generating the calibration curves for the third and subsequent
points by repeating operations 2. and 3. in the procedure above.
For the sixth and later points, the screen shifts to the next page.
Reference: For the setting procedure, refer to operations (3) to (8) of Step 2 "Set the Parameters for
Generating the Calibration Curve for the First Point." of Section 3.2.2.3 "Multi-point
Calibration Curve Analysis with Diluted Solution" on page 103.
To display the first page (parameters for generating calibration curves for points
up to the fifth point) in this case:
1.
160
TOC-LCSH/CSN
Move the cursor to the parameter setting box for Point-6.
3.3
2.
Analysis with the Autosampler
Press the ← key.
The first page will be displayed.
To display the second page (parameters for generating calibration curves for the
sixth and later points):
1.
Move the cursor to the parameter setting box for Point-5.
2.
Press the → key.
To delete any particular point (point n):
1.
Move the cursor to the parameter setting box for Point-n.
2.
Press the F6 [Delete Point] key.
The Point-n parameter setting box is deleted. (If the F6 key is pressed for Point-1, the
parameter setting box is not deleted and the default display is reinstated.)
Step 3 Finish Calibration Curve Analysis Setting.
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Schedule - Settings" screen.
[α-n] is displayed in the set line. (α: analysis mode, n: calibration curve number)
Example: [TC-1]
3.3.3.5 Sample Analysis Settings
It is possible to measure samples using only one mode of analysis or to measure samples
using multiple modes of analysis. Sample measurement is classified into the following 4
types:
(1) Single-mode Analysis (for example TN, IC, NPOC, POC or TN)
(2) Multi-mode Analysis (for example TC/IC)
(3) Multi-mode Analysis - Simultaneous Analysis (for example TN/TN or TN/NPOC)
TOC-LCSH/CSN
161
3.3
Analysis with the Autosampler
(4) Multi-mode Analysis - Common Injection Analysis (for example POC/NPOC))
Descriptions of each are included at this point.
Procedure
1.
2.
Move the cursor to an empty row in the "ASI Schedule Settings" screen.
Press the [MEAS] key.
Reference: Press the [CAL] key to display the "Calibration Settings" screen. Refer to Section 3.2.2
"Calibration Curve Analysis" on page 92.
162
TOC-LCSH/CSN
3.3
Analysis with the Autosampler
3.3.3.6 Single-mode Analysis
This section describes the analysis parameters used in single-mode analysis.
TC analysis using concentration units of mg/L is the example, but the same method is used
for IC, NPOC, POC and TN analysis.
The parameters for sample analysis are entered in 2 steps.
Step 1
Set the Sample Analysis Parameters
Step 2
End Sample Analysis
Two methods are available for setting the analysis parameters.
New Setting:
Sets analysis parameters for the first time.
Load Method:
Loads a stored method file. Refer to Section 3.2.4 "Creating
a Method" on page 132 for details on methods.
The procedure for each is described below.
Step 1
Set the Sample Analysis Parameters
1. New Setting
The analysis parameters consist of the following 11 items.
(1)
(2)
(3)
(4)
(5)
(6)
Analysis Mode: Sets the type of analysis (i.e. TC, IC, POC, NPOC and TN Analysis).
Sample Name: Sets the sample name.
Vial Number: Sets the vial numbers used by the ASI.
Calibration Curve: Sets the calibration curve to be used.
Number of Injections (default: 1): Sets the number of injections.
Maximum Number of Injections (default: 1): Sets the maximum number of injection
(analysis injections + additional injections).
(7) SD (Default: 0.1): Sets the standard deviation limit.
(8) CV% (Default: 2.0): Sets the CV% limit value.
(9) Dilution Factor: Sets the dilution factor.
(10) Acid Addition Ratio: Sets the ratio of acid added to sample (IC and NPOC analysis).
TOC-LCSH/CSN
163
3.3
Analysis with the Autosampler
(11) Sparge Time: Sets the length of time sparging is to be performed (IC and NPOC
analysis).
The procedures for setting the various analysis parameters are described below.
(1) Analysis Mode
1.
Press the F2 [TC] key.
The TC parameters box is displayed.
Note: • For IC analysis: Press the F3 [IC] key.
• For POC* analysis: Press the F4 [POC] key.
• For NPOC analysis: Press the F5 [NPOC] key.
• For TN* analysis: Press the F6 [TN] key.
"*" denotes optional, and is shown for optional settings.
(2) Sample Name
1.
2.
Enter the sample name.
Press the [Enter] key.
Confirms the sample name entry.
Note: Maximum number of characters: 16
(3) Vial Number
1.
Move the cursor to the Vial Number (Vial #) item.
If the cursor is at the Continuous Measurement in Same Mode item, press the ↓ key.
2.
Enter the vial numbers indicated in the ASI, and press the [Enter] key.
The vial number is confirmed.
Note: Setting the vial number to 0 causes sample from the No. 1 port of
the 8-port valve.
(4) Calibration Curve
1.
Enter the calibration curve number.
A list of previously generated calibration curves is presented at the top of the screen.
Referring to this list, enter a number that has not been used.
2.
Press the [Enter] key.
This confirms the setting of the calibration curve number.
(5) Number of Injections
1.
2.
164
TOC-LCSH/CSN
Use the ↓ key to move the cursor to the Number of Injections (Inj #) item.
Enter the number of sample analysis injections to be performed, and press the [Enter]
key.
3.3
Analysis with the Autosampler
(6) Maximum Number of Injections
1.
Use the ↓ key to move the cursor to the Maximum Number of Injections (Max # of
Inj) item.
2.
Enter the maximum number of sample injections to be performed.
Note: Maximum Number of Injections
The maximum number of injections refers to the number of injections when
the automatic additional analysis function is used. Whether automatic
additional analyses are performed is determined by the limits for standard
deviation (SD) and coefficient of variation (CV%). When the set number of
injections are complete, the SD and CV% for those results are compared to
the set SD and CV% limits. If both of the actual values are greater than the
set values, the automatic additional analysis function is activated.
3.
Press the [Enter] key.
(7) SD
This setting is only available when the Number of Injections is less than the Maximum
Number of Injections.
1.
2.
Move the cursor to the SD item using the ↓ key.
Enter the standard deviation value, and press the [Enter] key.
(8) CV%
This setting is only available when the Number of Injections is less than the Maximum
Number of Injections.
1.
2.
Move the cursor to the CV% item using the ↓ key.
Enter the CV% value, and press the [Enter] key.
(9) Dilution Factor
The optimal dilution factor is automatically displayed when the concentration of the
standard solution is entered.
1.
2.
Move the cursor to the Dilution Factor (Dil. Factor) item using the ↓ key.
Enter the dilution factor, and press the [Enter] key.
(10) Acid Addition Ratio
1.
2.
Move the cursor to the Acid Addition Ratio (Acid ratio) item using the ↓ key.
Enter the acid addition ratio, and press the [Enter] key.
(11) Sparge Time
1.
2.
Move the cursor to the Sparge Time item using the ↓ key.
Enter the sparge time, and press the [Enter] key.
TOC-LCSH/CSN
165
3.3
Analysis with the Autosampler
2. Load Method
1.
Press the [METHOD] key.
The "Measurement - Load Method" screen is displayed.
2.
Select the method group to load using the appropriate function key (F2 - F5).
The stored methods are listed at the top of the screen.
3.
Select the method to load using the ↓ ↑ keys.
To display the analysis parameters of the selected method, press the [Enter] key.
4.
Press the [NEXT] key.
The method is loaded, and the display returns to the "Measurement Parameters"
screen.
To change the analysis parameters, refer to Step 1- procedures (1) - (11) above.
Step 2
End the Sample Analysis
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Measurement Settings" screen. The sample name and
analysis mode are displayed in the row that was just set.
3.3.3.7 Multi-mode Analysis
This section describes the procedures for using more than one analysis mode.
Setting the sample analysis parameters consists of 3 steps.
Step 1
Set the Parameters for the First Mode
Step 2
Set the Parameters for the Second and Subsequent Modes
Step 3
End Sample Analysis
Step 1
Set the Parameters for the First Mode
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, "Step 1 Set the Sample
Analysis Parameters".
Note:
166
TOC-LCSH/CSN
Because analyses are conducted using multiple analysis modes, set Continuous
Measurement in Same Mode to OFF.
3.3
Step 2
Analysis with the Autosampler
Set the Parameters for the Second and Subsequent Modes
Procedure
1.
Select the 2nd analysis mode.
For IC analysis, press the F3 [IC] key. The IC analysis screen is displayed.
Note:
2.
3.
4.
•
•
•
•
For IC* analysis: Press the F3 [IC] key.
For POC* analysis: Press the F4 [POC] key.
For NPOC analysis: Press the F5 [POC] key.
For TN* analysis: Press the F6 [TN] key.
"*" denotes optional, and is displayed only if optional settings have been
made.
Move the cursor to the parameters box for IC analysis using the → key.
Set the IC analysis parameters.
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, items (4) - (11) of
"Step 1 Set the Sample Analysis Parameters".
Note: Display at the Top of the Screen
If the cursor is on Calibration Curve of TC Analysis Mode, a list of
calibration curves for TC analysis is displayed at the top of the screen.
Similarly, if the cursor is on Calibration Curve of IC Analysis Mode, a list
of calibration curves for IC analysis is displayed at the top of the screen.
For the 3rd and subsequent analysis modes, repeat sequence steps 1, 2 and 3, above.
Note: To cancel the settings of an analysis mode, press the function key
corresponding to the analysis mode. The parameters box closes.
Step 3
End Sample Analysis
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Measurement Settings" screen. The sample name and
analysis mode are displayed in the row that was just set.
TOC-LCSH/CSN
167
3.3
Analysis with the Autosampler
3.3.3.8 Multi-mode Analysis - Simultaneous Analysis
Simultaneous analysis is a method whereby TN and TC or NPOC are measured using a
single injection. Both types of simultaneous analysis can be performed using multiple
modes and/or continuous measurement.
(1) TN and TC analysis
(2) TN and NPOC analysis
The sample analysis procedure consists of 5 steps.
Step 1
Set the Parameters for Either TC or NPOC Analysis
Step 2
Set the Parameters for TN Analysis
Step 3
Set Simultaneous Analysis to ON
Step 4
Set the Parameters for Modes Other than TC or NPOC and TN Parameters
Step 5
End Sample Analysis
Step 1
Set the Parameters for Either TC or NPOC Analysis
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, "Step 1 Set the Sample
Analysis Parameters".
Step 2
Set the Parameters for TN Analysis
Procedure
168
1.
Press the F6 [TN] key.
The TN parameters box is displayed, along with the Simultaneous Analysis item.
2.
3.
Move the cursor to the parameters box for TN analysis using the → key.
TOC-LCSH/CSN
Set the TN analysis mode parameters.
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, items (3) - (11) of "Step
1 Set the Sample Analysis Parameters".
3.3
Note:
Analysis with the Autosampler
• Display at the Top of the Screen
If the cursor is on TC analysis mode, a list of calibration curves for TC
analysis is displayed at the top of the screen. Similarly, if the cursor is on
TN analysis mode, a list of calibration curves for TN analysis is
displayed at the top of the screen.
• Canceling Mode Settings
To cancel the setting of analysis mode parameters, press the function
key corresponding to the analysis mode. The settings screen will be
closed.
Step 3
Set Simultaneous Analysis to ON
Procedure
1.
Move the cursor to the Calibration Curve (1st) item of the TN parameters box.
2.
3.
Use the ↑ key to move the cursor to the Simultaneous Analysis (+TN) item.
Toggle the Simultaneous Analysis setting to ON using the [ENTER] key.
For continuous measurement set the Continuous Measurement item to ON.
Step 4
Set the Parameters for Modes Other than TC or NPOC and TN
Parameters
Proceed to Step 5 when only TC (or NPOC) and TN analysis are to be performed.
Procedure
1.
2.
3.
Select the analysis mode parameters using the function key.
Using the → key, move the cursor to the selected parameters box.
Set the parameters for the analysis mode.
For details on the setting procedure, refer to Section 3.3.3.6 "Single-mode Analysis"
on page 163, items (3) - (11) of "Step 1 Set the Sample Analysis Parameters".
Simultaneous analysis can be used for TN analysis. Refer to Section 3.3.3.8 "Multimode Analysis - Simultaneous Analysis" on page 168.
TOC-LCSH/CSN
169
3.3
Analysis with the Autosampler
Step 5
End Sample Analysis
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Schedule Settings" screen. The sample name and
analysis modes are displayed in the row that was just set.
3.3.3.9 Multi-mode Analysis - Common Injection Analysis
If POC analysis and NPOC analysis were set as multi-mode analysis parameters, these
analyses can be performed using the same injection.
In Common Injection Analysis, the sample is drawn into the syringe, and then sparged
inside the syringe. First POC analysis is performed, and then NPOC analysis is performed.
The sample analysis procedure consists of 5 steps.
Step 1
Set the POC Parameters
Step 2
Set the NPOC Parameters
Step 3
Set Common Injection Mode to ON
Step 4
Set Any Analysis Mode Parameters Other than POC and NPOC
Step 5
End Sample Analysis
Step 1
Set the POC Parameters
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, "Step 1 Set the Sample
Analysis Parameters".
170
TOC-LCSH/CSN
3.3
Step 2
Analysis with the Autosampler
Set the NPOC Parameters
Procedure
1.
Select the NPOC analysis mode. Press the F5 [NPOC] key.
The NPOC analysis parameters box and the Common Injection Analysis (POC &
NPOC) item are displayed.
2.
3.
Move the cursor to the parameters box for NPOC using the → key.
Set the NPOC analysis mode parameters.
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, item (3) - (11) of "Step
1 Set the Sample Analysis Parameters".
Note: • Display at the Top of the Screen
If the cursor is on TC analysis mode, a list of calibration curves for TC
analysis is displayed at the top of the screen. Similarly, if the cursor is on
TN analysis mode, a list of calibration curves for TN analysis is
displayed at the top of the screen.
• Canceling Mode Settings
To cancel the setting of analysis mode parameters, press the function
key corresponding to the analysis mode. The settings screen will be
closed.
TOC-LCSH/CSN
171
3.3
Analysis with the Autosampler
Step 3
Set Common Injection Analysis to ON
Procedure
1.
Move the cursor to the Calibration Curve (1st) item of the NPOC analysis parameters
screen.
2.
Use the ↑ key to move the cursor to the Common Injection Analysis (POC & NPOC)
item.
3.
Toggle the setting to ON using the [ENTER] key.
Step 4
Set Any Analysis Mode Parameters Other than POC and NPOC
Procedure
Proceed to Step 5 if only POC and NPOC analysis will be used.
Reference: Simultaneous analysis is possible for TN analysis. Refer to Section 3.2.3.3 "Multi-mode
Analysis - Simultaneous Analysis" on page 124.
1.
2.
3.
Select the analysis mode parameters using the function key.
Using the → key, move the cursor to the selected parameters box.
Set the parameters.
For details, refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, item (3) (11) of "Step 1 Set the Sample Analysis Parameters".
Step 5 End Sample Analysis
Procedure
1.
172
TOC-LCSH/CSN
Press the [NEXT] key.
The display returns to the "ASI Measurement Settings" screen. The sample name and
analysis modes are displayed in the row that was just set.
3.3
Analysis with the Autosampler
3.3.3.10 Editing the ASI Schedule Settings
After creating an analysis schedule, it can be edited by re-ordering the schedule sequence,
deleting schedules, etc.
F1
[Insert all Cal. Curve]: Creates a calibration curve analysis schedule for all
curves required for the sample analyses registered in the schedule.
F2
[Insert Cal. Curve]: Prior to sample analysis of a selected row, this function
creates the calibration curve required for sample analysis.
F3
[Switch Line]: A selected group exchanges rows with another row. Movement
is limited to one row up or one row down.
F4
[Delete Schedule]: Deletes the selected group.
F5
[Edit]: Enables editing of the analysis parameters of the selected group.
F6
[Reset status]: Changes the status of the message to "Not Measured" or "Not
Meas. (Acid)".
(1) Insert All Calibration Curves
This function inserts the calibration analysis parameters for all of the calibration curves
required for the analysis of the samples in the schedule.
Note:
1.
2.
This function key is displayed only when the cursor is in the first row.
Move the cursor to the first row.
Press the F1 [Insert all Cal. Curve] key.
The analysis parameters of all the calibration curves required for sample analysis are
inserted at the start of the schedule.
(2) Insert Calibration Curves Row-by-Row
This function inserts the calibration curve analysis parameters required for analysis of the
selected sample group.
This function is displayed only when the cursor is positioned in a sample analysis row.
TOC-LCSH/CSN
173
3.3
Analysis with the Autosampler
1.
Move the cursor to the sample group for which the calibration curve is to be
recalibrated.
2.
Press the F2 [Insert Cal. Curve] key.
The analysis parameters for the calibration curve are inserted in the row directly
above the selected sample group.
(3) Switch Line
1.
2.
Move the cursor to the row you wish to move.
Press the F3 [Switch Lines] key.
The contents of the row are moved.
Note: • To exchange the row with the one above it; press the F3 [Switch with
Upper Line] key.
• To exchange the row with the one below it; press the F2 [Switch with
Lower Line] key.
(4) Delete Schedule
To delete any required schedule:
1.
2.
3.
Press the F4 [Delete Schedule] key.
Move the cursor onto the group to be deleted and press the F4 [Delete Line] key.
Press the F6 [Yes] key.
Note: To cancel deletion, press the F1 [No] key.
To delete a specified schedule range:
1.
2.
Press the F4 [Delete Schedule] key.
3.
Specify the range and press the F6 [Delete] key.
Press the F5 [Delete Area] key. A dialog box in which you can select the required
range appears.
Note:
To cancel deletion, press the F1 [Cancel] key.
To delete all schedules:
1.
2.
3.
174
TOC-LCSH/CSN
Press the F4 [Delete Schedule] key.
Press the F6 [Delete All] key.
Press the F6 [Yes] key.
Note: To cancel deletion, press the F1 [No] key.
3.3
Analysis with the Autosampler
(5) Edit
1.
2.
Move the cursor to the group for which you wish to edit the measurement conditions.
3.
Edit the measurement conditions.
Note: • If the selected group is for calibration curve measurement, refer to
Section 3.3.3.1 "Calibration Curve Analysis" on page 152.
• If the selected group is for sample measurement, refer to Section 3.3.3.5
"Sample Analysis Settings" on page 161.
4.
Press the [NEXT] key to confirm the changes.
Press the F5 [Edit] key.
Note: • If the selected group is for calibration curve measurement, the "ASI
Calibration Settings" screen is displayed.
• If the selected group is for sample measurement, the "ASI Measurement
Settings" screen is displayed.
(6) Reset Status
To reset the status of any required schedule to "Not Meas. (Acid)":
1.
2.
Press the F6 [Reset status] key.
Move the cursor to the group whose status is to be changed. Press the F3 [One Line
Acidified] key.
To change the status of any required schedule to "Not Measured":
1.
2.
Press the F6 [Reset status] key.
Move the cursor to the group whose status is to be changed. Press the F4 [One Line]
key.
To change the status of all schedules to "Not Meas. (Acid)":
1.
2.
Press the F6 [Reset status] key.
Press the F5 [All Lines Acidified] key.
To change the status of all schedules to "Not Measured":
1.
2.
Press the F6 [Reset status] key.
Press the F6 [All Lines] key.
TOC-LCSH/CSN
175
3.3
Analysis with the Autosampler
3.3.4 Analysis
3.3.4.1 Starting Analysis
Prior to starting analysis, settings are made to determine the status of the instrument at
completion.
The instrument status can be set to one of three states.
(1)
Power OFF
After analysis, the instrument power is switched OFF (although the main power
remains on).
(2) Sleep
After analysis, the instrument is stopped temporarily, and is started up again at a
specified date and time.
(3) Waiting
The instrument remains in an analysis ready state.
A detailed description of each follows.
(1) Power OFF
After analysis, the instrument power is switched OFF (although the main power remains
on).
1.
After setting up the schedule in the "ASI Schedule Settings" screen, press the [NEXT]
key.
The "ASI Meas. Option" screen is displayed.
2.
3.
Press the F3 [Power OFF] key.
Verify that the [START] key is blinking, and press the [START] key.
Analysis starts according to the ASI schedule. When the analyses are complete, power to
the electric furnace is automatically switched OFF, and the temperature drops. After 30
minutes, carrier gas flow is stopped and power to the instrument is switched OFF.
176
TOC-LCSH/CSN
3.3
Analysis with the Autosampler
(2) Sleep
After analysis, the instrument is stopped temporarily or placed in the Sleep mode, and
started up again at the specified date and time.
1.
After setting up the schedule in the "ASI Schedule Settings" screen, press the [NEXT]
key.
The "ASI Meas. Options" screen is displayed.
2.
3.
Press the F4 [Sleep] key.
4.
Select the unit status.
This selects the status of the instrument during the sleep state.
Enter the date and time for the instrument to start up again for analysis.
Note: After entering the appropriate number values; press the [Enter] key
to confirm.
Electric Furnace Shutdown
(1) Use the ↓ key to move the cursor to the Furnace item.
(2) Use the [ENTER] key to toggle between ON and OFF.
Select the other item settings in the same way.
5.
Verify that the [START] key is blinking, and press the [START] key.
Analysis is started according to the ASI schedule. After analysis, the instrument
enters the state specified in step 4 above.
At the specified date and time, instrument completes the startup procedures, placing the
instrument back into the analysis ready state.
(3) Waiting
In waiting, the instrument maintains the status existing at the completion of analysis.
1.
After setting up the schedule in the "ASI Schedule Settings" screen, press the [NEXT]
key.
The "ASI Meas. Options" screen is displayed.
2.
3.
Press the F5 [Waiting] key.
Verify that the [START] key is blinking, and press the [START] key.
Analysis is started according to the ASI schedule.
TOC-LCSH/CSN
177
3.3
Analysis with the Autosampler
3.3.4.2 Interrupting Analysis
Three methods are available for interrupting analysis.
(1)
HALT
This stops analysis immediately. In this case, data acquired in the current analysis is
lost.
(2) STOP
This stops analysis following analysis of the current peak. The analysis results up to
that point are preserved.
(3) Stop After Current Vial
This stops analysis following analysis of the current sample. The analysis results up to
that point are preserved.
Analysis Interruption Procedure
178
1.
Press the [STOP] key while analysis is in progress.
The following Function keys are enabled.
• F1: [Cancel] (Cancels the interruption selection process)
• F3: [HALT]
• F4: [STOP]
• F6: [Stop After Current Vial]
2.
Press the appropriate function key.
TOC-LCSH/CSN
3.4
3.4
Analysis with the 8-Port Sampler
Analysis with the 8-Port Sampler
3.4.1 Preparation for Sample Analysis Using the OCT-L 8-Port Sampler
3.4.1.1 Sample Container
There are no restrictions on the type of sample containers that can be used with the OCT-L.
It is only necessary that the containers be placed so the sample tubing from the various
ports can be inserted directly into the containers.
Note:
Wash all sample containers with an appropriate laboratory detergent, and rinse
them thoroughly with water before using them for the first time.
3.4.1.2 Loading the Sample
Open sample containers can be used to perform sample measurement with the OCT-L.
However, in the following situations, it is necessary to seal the sample container.
(1)
(2)
(3)
(4)
(5)
when performing IC measurement
when performing POC measurement
when performing measurement of low concentration samples (e.g., 10 mg/L)
when performing measurement of alkali samples of pH 7 or higher
when performing measurement of samples containing volatile organic carbon
compounds
(6) when the number of samples is so great as to require a long measurement time
(7) when performing measurement of standard solutions
Note:
If the sample container openings are not sealed in the situations listed above,
measurement values may be influenced by such factors as absorption of
atmospheric CO2, contamination with carbon containing substances, and
evaporation of TOC constituents from the samples.
Sealing the Sample Containers
Sample containers may be sealed using commercial sealing films such as Parafilm. It is also
possible to pierce the lid of the container and insert the sample tubing into the container
through this opening.
Note:
In either case, wash the container with a laboratory detergent, and rinse it
thoroughly with water before use.
Sealing the Container with Parafilm
1.
2.
Cut a piece of Parafilm to size according to the size of the sample vessel opening.
Insert the tip of the sampling tube into the vessel, cover the opening with the prepared
Parafilm, and seal the opening of the vessel, stretching the Parafilm over the edges. Be
sure that a very small gap in the seal is formed to prevent creation of negative pressure
inside the vessel.
TOC-LCSH/CSN
179
3.4
Analysis with the 8-Port Sampler
3.
Press the overlapping portions of the Parafilm around the neck of the opening.
Parafilm
Figure 3.35 Sealing the Container
3.4.1.3 High Sensitivity Using the OCT-L
If samples such as purified water or ultra-pure water, having a TOC concentration of
100ppb or less, are to be measured using the OCT-L, it is necessary to consider the
following precautions associated with high sensitivity analysis. Refer to Section 3.1.19.1
"High Sensitivity Analysis" on page 76 in the TOC-LCSH/CSN USER'S MANUAL for more
information.
1)
2)
3)
180
TOC-LCSH/CSN
NPOC analysis is recommended because TOC (TC-IC) analysis tends to have a
greater variation in measured values than NPOC. This is because IC often
accounts for a significant portion of the TC, and the errors in the two values are
additive using TOC (TC-IC) analysis. This affect significantly influences TOC
analysis.
For calibration measurement of standard solutions, fill well-washed containers
with standard solutions to about 5-10 mm from the top of the container, and
immediately seal each container. When placing the container below the OCT-L,
handle it carefully to avoid the standard solution contacting the sealing surface.
Low-concentration standard solutions must be prepared each time they are used.
To ensure that the peaks are stable for generating the calibration curve, perform
4-5 injections using the same analysis parameters prior to performing the
calibration curve analysis. For example, to generate a 400 ppb calibration curve,
set 400 ppb as the 1st standard solution concentration, and enter 1 as the
container number. Actually place a 0 ppb solution in the container for port No. 1.
The objective at this point is not to generate a calibration curve, but to inject
water using the same injection volume that will be used to generate the
calibration curve. This not only stabilizes the instrument but also thoroughly
washes the sampling needle with purified water.
In the 2nd row of the settings screen and using the same calibration curve number
as above, set the analysis parameters for 0 ppb and 400 ppb. When sample
measurement starts, the calibration curve to be used will be created with the
correct standard solutions.
3.4
Analysis with the 8-Port Sampler
3.4.2 Setting Analysis Parameters
In order to perform analysis using the OCT-L, first determine the order of analysis and the
analysis schedule before performing calibration curve analysis and sample analysis.
Displaying the "ASI Schedule Settings" Screen
1.
Press the [ASI] key while viewing the "Initial Display".
The "ASI Schedule Settings" screen is displayed.
The procedures for performing the calibration curve analysis and sample analysis are
described separately.
3.4.2.1 Calibration Curve Analysis
Single-point and multi-point calibration curve settings are both available for calibration
curve analysis.
Each is described here.
TC analysis with a concentration unit of mg/L is used for the example, but the methods are
the same for IC, POC and TN analysis.
Procedure for Displaying "Calibration Setting" Screen
1.
Move the cursor to an empty row in the "ASI Schedule" screen.
Reference: Press the [MEAS] key to display the "Sample Analysis Setting" screen. Refer to Section
3.3.3.5 "Sample Analysis Settings" on page 161.
TOC-LCSH/CSN
181
3.4
Analysis with the 8-Port Sampler
2.
Press the [CAL] key.
The "ASI Calibration Settings" screen is displayed.
3.4.2.2 Single-point Calibration Curve Analysis
The procedure for generating a single-point calibration curve consists of two steps.
Step 1
Set the Parameters for the Calibration Curve
Step 2
End the Calibration Curve Analysis
Step 1
Set the Parameters for the Calibration Curve
The following 14 items comprise the parameters needed for generating the calibration
curve.
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
182
TOC-LCSH/CSN
Analysis Mode: Sets the type of analysis that will be performed (i.e. TC, IC, POC and
TN Analysis).
Calibration Curve Number: Sets the number assigned to the calibration curve.
Vial Number: Sets the port number used by the OCT-L.
Standard Solution Concentration: Sets the concentration of the injected standard
solution.
Number of Injections (default: 1): Sets the number of injections for standard solution
analysis.
Maximum Number of Injections (default: 1): Sets the maximum number of injection
(analysis injections + additional injections).
SD (Default: 0.1): Sets the standard deviation limit.
CV% (Default: 2.0): Sets the CV% limit value.
Dilution Factor: Sets the dilution factor.
Injection Volume: Sets the injection volume of the standard solution.
Acid Addition Ratio: Sets the ratio of acid added to sample (IC analysis).
Sparge Time: Sets the length of time sparging is to be performed.
Curve Type: Sets the type of calibration curve (i.e. point-to-point or least squares
linear regression curve).
3.4
Analysis with the 8-Port Sampler
(14) Curve Shift: Sets the shift of calibration curve towards the zero point (i.e. no shift,
shift to zero point or shift to the TC blank point).
(1) Analysis Mode
1.
TIP »
Press the F2 [TC] key.
The TC parameters box is displayed as the default. The currently stored calibration
curves are displayed at the top of the screen.
Note: • For IC analysis: Press the F3 [IC] key.
• For POC* analysis: Press the F4 [POC] key.
• For TN* analysis: Press the F5 [TN] key.
"*" denotes optional, and is displayed only if optional settings have been
made.
To cancel the analysis mode setting, press the function key corresponding to the analysis
mode. The parameters box closes.
(2) Calibration Curve Number
1.
Enter the calibration curve number.
A list of the previously generated calibration curves is presented at the top of the
screen.
Referring to this list, enter a number that has not yet been used.
2.
Press the [Enter] key.
Confirms the calibration curve number setting.
(3) Vial Number
1.
2.
Use the ↓ key to move the cursor to the Vial # item.
Enter the port number indicated in the OCT-L, and press the [Enter] key.
Note: Setting the vial number to 0 causes sample from the No. 1 port of
the 8-port valve.
TOC-LCSH/CSN
183
3.4
Analysis with the 8-Port Sampler
(4) Standard Solution Concentration
1.
Move the cursor to the Standard Solution Concentration (STD Conc.) item using the
↓ key.
2.
Enter the concentration of the standard solution to be injected for TC analysis. Refer
to Section 3.1.17.4 "Concentration Unit" on page 59.
3.
Press the [Enter] key.
The optimal injection volume is checked, and displayed.
(5) Number of Injections
1.
2.
Move the cursor to the Number of Injections (Inj #) item using the ↓ key.
Set the number of injections of standard solution to be made for analysis, and press
the [Enter] key.
(6) Maximum Number of Injections
1.
Move the cursor to the Maximum Number of Injections (Max # of Inj) item using the
↓ key.
2.
Set the maximum number of injections of standard solution to be made for analysis,
and press the [Enter] key.
Note: Maximum Number of Injections
Maximum number of injections refers to the number of injections in repeat
analysis if the automatic additional analysis function is used. Whether
automatic additional analyses are performed is determined by the settings
for standard deviation (SD) and coefficient of variation (CV%). After
analysis using the set number of injections is complete, the SD and CV%
values for those results are compared to the limits for SD and CV%. If both
of the actual values are greater than the limits, the automatic additional
analysis function is activated.
3.
Press the [Enter] key.
(7) SD
This setting is only available when the Number of Injections is less than the Maximum
Number of Injections.
1.
2.
Move the cursor to the SD item using the ↓ key.
Enter the standard deviation value, and press the [Enter] key.
(8) CV%
This setting is only available when the Number of Injections is less than the Maximum
Number of Injections.
1.
2.
184
TOC-LCSH/CSN
Move the cursor to the CV% item using the ↓ key.
Enter the CV% value, and press the [Enter] key.
3.4
Analysis with the 8-Port Sampler
(9) Dilution Factor
The optimal dilution factor is automatically displayed when the concentration of the
standard solution is entered.
1.
2.
Move the cursor to the Dilution Factor (Dil. Factor) item using the ↓ key.
Enter the dilution factor, and press the [Enter] key.
(10) Injection Volume
The optimal injection volume is automatically displayed when the concentration of the
standard solution is entered.
1.
2.
Move the cursor to the Injection Volume (Inj. Volume) item using the ↓ key.
Enter the injection volume, and press the [Enter] key.
(11) Acid Addition Ratio
Entered only when acid is to be added to the standard solution.
1.
2.
Move the cursor to the Acid Addition Ratio (Acid ratio) item using the ↓ key.
Enter the amount of acid to be added, and press the [Enter] key.
(12) Sparge Time
Entered only if the standard solution is to be sparged.
1.
2.
Move the cursor to the Sparge Time item using the ↓ key.
Enter the sparge time, and press the [Enter] key.
(13) Curve Type
This parameter selects which curve type is generated for a calibration curve using 3 or more
points. The choices are point-to-point calibration curve, where a straight line connects the
individual points or least squares linear regression curve.
1.
2.
Move the cursor to the Curve Type item using the arrow keys.
Set the curve type.
Toggle between the settings using the [ENTER] key.
(14) Curve Shift
This parameter selects whether to shift the calibration curve through the origin (zero point),
force the calibration curve to pass through the blank point determined by the TC Blank
Check value, or not to shift the calibration curve at all.
Note:
1.
The calibration curve will not shift to the blank point unless the injection volume
is the same as that used in the TC Blank Check analysis.
Move the cursor to the Shift item using the arrow keys.
TOC-LCSH/CSN
185
3.4
Analysis with the 8-Port Sampler
2.
Set the curve shift.
Toggle through the settings using the [ENTER] key.
Step 2
End the Calibration Curve Analysis
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Schedule Settings" screen. In the row that was just set,
"α-n" is displayed. (α: Analysis mode, n: Calibration curve number)
Example: TC - 1.
3.4.2.3 Multi-point Calibration Curve Analysis
A multi-point calibration curve can be generated with a maximum of 10 points. Set the
concentrations of the standard solutions to be measured using the procedure described
below.
The procedure for generating a multi-point calibration curve consists of the following three
general steps.
Step 1
Set the Parameters for the 1st Point
Step 2
Set the Parameters for the 2nd and Subsequent Points
Step 3
End the Calibration Curve Analysis
Step 1 Set the Parameters for the 1st Point
Refer to Section 3.2.2.1 "Single-point Calibration Curve" on page 92, "Step 1 Set the
Analysis Mode".
Step 2 Set the Parameters for the 2nd and Subsequent Points
Procedure
1.
186
TOC-LCSH/CSN
Use the ↓ ↑ keys to move the cursor to the parameters box for the 1st point.
3.4
2.
Analysis with the 8-Port Sampler
Press the → key.
The parameters box for the 2nd point is displayed.
Missing Graphic
3.
Set the parameters for the 2nd point.
The injection volume displayed is that for the highest concentration among the
standard solutions entered.
4.
Repeat steps 2 and 3 above to set the calibration curve parameters for the 3rd and
subsequent points. The display moves to the next screen for setting the 6th and
subsequent points.
Reference: For the setting procedure, refer to operations (3) to (8) of Step 1 "Set the Parameters for
the Calibration Curve" of Section 3.3.3.2 "Single-point Calibration Curve Analysis" on
page 153.
Displaying the Previous Page (points 1 to 5)
1.
Move the cursor to the parameters box for Point-6.
2.
Press the ← key.
The screen for the previous page is displayed.
Displaying the Following Page (points 6-10)
1.
Move the cursor to the parameters box for Point-5.
2.
Press the → key.
TOC-LCSH/CSN
187
3.4
Analysis with the 8-Port Sampler
Discarding a Point (n point)
1.
Move the cursor to the parameters box for Point-n.
2.
Press the F6 [Delete Point] key.
The parameters box for Point-n is deleted. If the F6 key is pressed at Point-1, the
parameters box is not deleted; the default display is reinstated.
Step 3 End Calibration Curve Analysis
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Schedule Settings" screen. In the row that was just set,
"α-n" is displayed. (α: Analysis mode, n: Calibration curve number)
Example: TC - 1
3.4.2.4 Multi-point Calibration Curve Analysis with Diluted Solution
It is possible to generate a multi-point calibration curve using a single standard solution.
Set the concentrations in the order of the standard solutions to be analyzed.
The procedure for generating a multi-point calibration curve with diluted solution consists
of the following three general steps.
Step 1
Set the Parameters for Generating the Calibration Curve for the First Point.
Step 2
Set the Parameters for Generating the Calibration Curve for the Second and
Subsequent Points.
Step 3
Finish Calibration Curve Analysis Setting.
Step 1 Set the Parameters for Generating the Calibration Curve for the First
Point.
For the setting procedure, refer to Step 1 "Select the Mode." and Step 2 "Set the Parameters
for Generating the Calibration Curve for the First Point." of Section 3.2.2.3 "Multi-point
Calibration Curve Analysis with Diluted Solution" on page 103.
188
TOC-LCSH/CSN
3.4
Analysis with the 8-Port Sampler
Step 2 Set the Parameters for Generating the Calibration Curve for the
Second and Subsequent Points.
Procedure
1.
Move the cursor to the parameter setting box for the first point with the ↓ ↑ keys.
2.
Press the → key.
The parameter setting box for the second point will be displayed.
3.
Set the parameters for generating the calibration curve for the second point.
The injection volume corresponding to the standard solution with the highest
concentration among those set is displayed.
4.
Set the parameters for generating the calibration curves for the third and subsequent
points by repeating operations 2. and 3. in the procedure above.
For the sixth and later points, the screen shifts to the next page.
Reference: For the setting procedure, refer to operations (3) to (8) of Step 2 "Set the Parameters for
Generating the Calibration Curve for the First Point." of Section 3.2.2.3 "Multi-point
Calibration Curve Analysis with Diluted Solution" on page 103.
TOC-LCSH/CSN
189
3.4
Analysis with the 8-Port Sampler
To display the first page (parameters for generating calibration curves for points
up to the fifth point) in this case:
1.
Move the cursor to the parameter setting box for Point-6.
2.
Press the ← key.
The first page will be displayed.
To display the second page (parameters for generating calibration curves for the
sixth and later points):
1.
Move the cursor to the parameter setting box for Point-5.
2.
Press the → key.
To delete any particular point (point n):
190
1.
Move the cursor to the parameter setting box for Point-n.
2.
Press the F6 [Delete Point] key.
The Point-n parameter setting box is deleted. (If the F6 key is pressed for Point-1, the
parameter setting box is not deleted and the default display is reinstated.)
TOC-LCSH/CSN
3.4
Analysis with the 8-Port Sampler
Step 3 Finish Calibration Curve Analysis Setting.
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Schedule - Settings" screen.
[α-n] is displayed in the set line. (α: analysis mode, n: calibration curve number)
Example: [TC-1]
3.4.2.5 Sample Analysis Settings
It is possible to measure samples using only one mode of analysis or to measure samples
using multiple modes of analysis. Sample measurement is classified into the following 4
types:
(1) Single-mode Analysis (for example TN, IC, NPOC, POC or TN)
(2) Multi-mode Analysis (for example TC/IC)
(3) Multi-mode Analysis - Simultaneous Analysis (for example TN/TN or TN/NPOC)
(4) Multi-mode Analysis - Common Injection Analysis (for example POC/NPOC))
Descriptions of each are included at this point.
Procedure
1.
2.
Move the cursor to an empty row in the "ASI Schedule Settings" screen.
Press the [MEAS] key.
Reference: Press the [CAL] key to display the "Calibration Settings" screen. Refer to Section 3.2.2
"Calibration Curve Analysis" on page 92.
3.4.2.6 Single-mode Analysis
This section describes the analysis parameters used in single-mode analysis.
TC analysis using concentration units of mg/L is the example, but the same method is used
for IC, NPOC, POC and TN analysis.
The parameters for sample analysis are entered in 2 steps.
Step 1
Set the Sample Analysis Parameters
Step 2
End Sample Analysis
Two methods are available for setting the analysis parameters.
New Setting:
Sets analysis parameters for the first time.
Load Method:
Loads a stored method file. Refer to Section 3.2.4 "Creating
a Method" on page 132 for details on methods.
The procedure for each is described below.
TOC-LCSH/CSN
191
3.4
Analysis with the 8-Port Sampler
Step 1
Set the Sample Analysis Parameters
1. New Setting
The analysis parameters consist of the following 11 items.
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
Analysis Mode: Sets the type of analysis (i.e. TC, IC, POC, NPOC and TN Analysis).
Sample Name: Sets the sample name.
Vial Number: Sets the port numbers used by the OCT-L.
Calibration Curve: Sets the calibration curve to be used.
Number of Injections (default: 1): Sets the number of injections.
Maximum Number of Injections (default: 1): Sets the maximum number of injection
(analysis injections + additional injections).
SD (Default: 0.1): Sets the standard deviation limit.
CV% (Default: 2.0): Sets the CV% limit value.
Dilution Factor: Sets the dilution factor.
Acid Addition Ratio: Sets the ratio of acid added to sample (IC and NPOC analysis).
Sparge Time: Sets the length of time sparging is to be performed (IC and NPOC
analysis).
The procedures for setting the various analysis parameters are described below.
(1) Analysis Mode
1.
192
TOC-LCSH/CSN
Press the F2 [TC] key.
The TC parameters box is displayed.
Note: • For IC analysis: Press the F3 [IC] key.
• For POC* analysis: Press the F4 [POC] key.
• For NPOC analysis: Press the F5 [NPOC] key.
• For TN* analysis: Press the F6 [TN] key.
"*" denotes optional, and is shown for optional settings.
3.4
Analysis with the 8-Port Sampler
(2) Sample Name
1.
2.
Enter the sample name.
Press the [Enter] key.
Confirms the sample name entry.
Note: Maximum number of characters: 16
(3) Vial Number
1.
Move the cursor to the Vial Number (Vial #) item.
If the cursor is at the Continuous Measurement in Same Mode item, press the ↓ key.
2.
Enter the port numbers indicated in the OCT-L, and press the [Enter] key.
The vial number is confirmed.
Note: Setting the vial number to 0 causes sample from the No. 1 port of
the 8-port valve.
(4) Calibration Curve
1.
Enter the calibration curve number.
A list of previously generated calibration curves is presented at the top of the screen.
Referring to this list, enter a number that has not been used.
2.
Press the [Enter] key.
This confirms the setting of the calibration curve number.
(5) Number of Injections
1.
2.
Use the ↓ key to move the cursor to the Number of Injections (Inj #) item.
Enter the number of sample analysis injections to be performed, and press the [Enter]
key.
(6) Maximum Number of Injections
1.
Use the ↓ key to move the cursor to the Maximum Number of Injections (Max # of
Inj) item.
2.
Enter the maximum number of sample injections to be performed.
Note: Maximum Number of Injections
The maximum number of injections refers to the number of injections when
the automatic additional analysis function is used. Whether automatic
additional analyses are performed is determined by the limits for standard
deviation (SD) and coefficient of variation (CV%). When the set number of
injections are complete, the SD and CV% for those results are compared to
the set SD and CV% limits. If both of the actual values are greater than the
set values, the automatic additional analysis function is activated.
3.
Press the [Enter] key.
TOC-LCSH/CSN
193
3.4
Analysis with the 8-Port Sampler
(7) SD
This setting is only available when the Number of Injections is less than the Maximum
Number of Injections.
1.
2.
Move the cursor to the SD item using the ↓ key.
Enter the standard deviation value, and press the [Enter] key.
(8) CV%
This setting is only available when the Number of Injections is less than the Maximum
Number of Injections.
1.
2.
Move the cursor to the CV% item using the ↓ key.
Enter the CV% value, and press the [Enter] key.
(9) Dilution Factor
The optimal dilution factor is automatically displayed when the concentration of the
standard solution is entered.
1.
2.
Move the cursor to the Dilution Factor (Dil. Factor) item using the ↓ key.
Enter the dilution factor, and press the [Enter] key.
(10) Acid Addition Ratio
1.
2.
Move the cursor to the Acid Addition Ratio (Acid ratio) item using the ↓ key.
Enter the acid addition ratio, and press the [Enter] key.
(11) Sparge Time
1.
2.
Move the cursor to the Sparge Time item using the ↓ key.
Enter the sparge time, and press the [Enter] key.
2. Load Method
1.
Press the [METHOD] key.
The "Measurement - Load Method" screen is displayed.
2.
Select the method group to load using the appropriate function key (F2 - F5).
The stored methods are listed at the top of the screen.
3.
Select the method to load using the ↓ ↑ keys.
To display the analysis parameters of the selected method, press the [Enter] key.
4.
Press the [NEXT] key.
The method is loaded, and the display returns to the "Measurement Parameters"
screen.
To change the analysis parameters, refer to Step 1- procedures (1) - (11) above.
194
TOC-LCSH/CSN
3.4
Step 2
Analysis with the 8-Port Sampler
End the Sample Analysis
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Measurement Settings" screen. The sample name and
analysis mode are displayed in the row that was just set.
3.4.2.7 Multi-mode Analysis
This section describes the procedures for using more than one analysis mode.
Setting the sample analysis parameters consists of 3 steps.
Step 1
Set the Parameters for the First Mode
Step 2
Set the Parameters for the Second and Subsequent Modes
Step 3
End Sample Analysis
Step 1
Set the Parameters for the First Mode
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, "Step 1 Set the Sample
Analysis Parameters".
Note:
Because analyses are conducted using multiple analysis modes, set Continuous
Measurement in Same Mode to OFF.
Step 2
Set the Parameters for the Second and Subsequent Modes
Procedure
1.
Select the 2nd analysis mode.
For IC analysis, press the F3 [IC] key. The IC analysis screen is displayed.
TOC-LCSH/CSN
195
3.4
Analysis with the 8-Port Sampler
Note:
2.
3.
4.
•
•
•
•
For IC* analysis: Press the F3 [IC] key.
For POC* analysis: Press the F4 [POC] key.
For NPOC analysis: Press the F5 [POC] key.
For TN* analysis: Press the F6 [TN] key.
"*" denotes optional, and is displayed only if optional settings have been
made.
Move the cursor to the parameters box for IC analysis using the → key.
Set the IC analysis parameters.
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, items (4) - (11) of
"Step 1 Set the Sample Analysis Parameters".
Note: Display at the Top of the Screen
If the cursor is on Calibration Curve of TC Analysis Mode, a list of
calibration curves for TC analysis is displayed at the top of the screen.
Similarly, if the cursor is on Calibration Curve of IC Analysis Mode, a list
of calibration curves for IC analysis is displayed at the top of the screen.
For the 3rd and subsequent analysis modes, repeat sequence steps 1, 2 and 3, above.
Note: To cancel the settings of an analysis mode, press the function key
corresponding to the analysis mode. The parameters box closes.
Step 3
End Sample Analysis
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Measurement Settings" screen. The sample name and
analysis mode are displayed in the row that was just set.
3.4.2.8 Multi-mode Analysis - Simultaneous Analysis
Simultaneous analysis is a method whereby TN and TC or NPOC are measured using a
single injection. Both types of simultaneous analysis can be performed using multiple
modes and/or continuous measurement.
(1) TN and TC analysis
(2) TN and NPOC analysis
The sample analysis procedure consists of 5 steps.
Step 1
Set the Parameters for Either TC or NPOC Analysis
Step 2
Set the Parameters for TN Analysis
Step 3
Set Simultaneous Analysis to ON
Step 4
Set the Parameters for Modes Other than TC or NPOC and TN Parameters
Step 5
End Sample Analysis
Step 1
Set the Parameters for Either TC or NPOC Analysis
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, "Step 1 Set the Sample
Analysis Parameters".
196
TOC-LCSH/CSN
3.4
Step 2
Analysis with the 8-Port Sampler
Set the Parameters for TN Analysis
Procedure
1.
Press the F6 [TN] key.
The TN parameters box is displayed, along with the Simultaneous Analysis item.
2.
3.
Move the cursor to the parameters box for TN analysis using the → key.
Set the TN analysis mode parameters.
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, items (3) - (11) of "Step
1 Set the Sample Analysis Parameters".
Note: • Display at the Top of the Screen
If the cursor is on TC analysis mode, a list of calibration curves for TC
analysis is displayed at the top of the screen. Similarly, if the cursor is on
TN analysis mode, a list of calibration curves for TN analysis is
displayed at the top of the screen.
• Canceling Mode Settings
To cancel the setting of analysis mode parameters, press the function
key corresponding to the analysis mode. The settings screen will be
closed.
TOC-LCSH/CSN
197
3.4
Analysis with the 8-Port Sampler
Step 3
Set Simultaneous Analysis to ON
Procedure
1.
Move the cursor to the Calibration Curve (1st) item of the TN parameters box.
2.
3.
Use the ↑ key to move the cursor to the Simultaneous Analysis (+TN) item.
Toggle the Simultaneous Analysis setting to ON using the [ENTER] key.
For continuous measurement set the Continuous Measurement item to ON.
Step 4
Set the Parameters for Modes Other than TC or NPOC and TN
Parameters
Proceed to Step 5 when only TC (or NPOC) and TN analysis are to be performed.
Procedure
1.
2.
3.
Select the analysis mode parameters using the function key.
Using the → key, move the cursor to the selected parameters box.
Set the parameters for the analysis mode.
For details on the setting procedure, refer to Section 3.3.3.6 "Single-mode Analysis"
on page 163, items (3) - (11) of "Step 1 Set the Sample Analysis Parameters".
Simultaneous analysis can be used for TN analysis. Refer to Section 3.3.3.8 "Multimode Analysis - Simultaneous Analysis" on page 168.
Step 5
End Sample Analysis
Procedure
1.
198
TOC-LCSH/CSN
Press the [NEXT] key.
The display returns to the "ASI Schedule Settings" screen. The sample name and
analysis modes are displayed in the row that was just set.
3.4
Analysis with the 8-Port Sampler
3.4.2.9 Multi-mode Analysis - Common Injection Analysis
If POC analysis and NPOC analysis were set as multi-mode analysis parameters, these
analyses can be performed using the same injection.
In Common Injection Analysis, the sample is drawn into the syringe, and then sparged
inside the syringe. First POC analysis is performed, and then NPOC analysis is performed.
The sample analysis procedure consists of 5 steps.
Step 1
Set the POC Parameters
Step 2
Set the NPOC Parameters
Step 3
Set Common Injection Mode to ON
Step 4
Set Any Analysis Mode Parameters Other than POC and NPOC
Step 5
End Sample Analysis
Step 1
Set the POC Parameters
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, "Step 1 Set the Sample
Analysis Parameters".
Step 2
Set the NPOC Parameters
Procedure
1.
Select the NPOC analysis mode. Press the F5 [NPOC] key.
The NPOC analysis parameters box and the Common Injection Analysis (POC &
NPOC) item are displayed.
2.
3.
Move the cursor to the parameters box for NPOC using the → key.
Set the NPOC analysis mode parameters.
Refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, item (3) - (11) of "Step
1 Set the Sample Analysis Parameters".
TOC-LCSH/CSN
199
3.4
Analysis with the 8-Port Sampler
Note:
• Display at the Top of the Screen
If the cursor is on TC analysis mode, a list of calibration curves for TC
analysis is displayed at the top of the screen. Similarly, if the cursor is on
TN analysis mode, a list of calibration curves for TN analysis is
displayed at the top of the screen.
• Canceling Mode Settings
To cancel the setting of analysis mode parameters, press the function
key corresponding to the analysis mode. The settings screen will be
closed.
Step 3
Set Common Injection Analysis to ON
Procedure
1.
Move the cursor to the Calibration Curve (1st) item of the NPOC analysis parameters
screen.
2.
Use the ↑ key to move the cursor to the Common Injection Analysis (POC & NPOC)
item.
3.
Toggle the setting to ON using the [ENTER] key.
Step 4
Set Any Analysis Mode Parameters Other than POC and NPOC
Procedure
Proceed to Step 5 if only POC and NPOC analysis will be used.
Reference: Simultaneous analysis is possible for TN analysis. Refer to Section 3.2.3.3 "Multi-mode
Analysis - Simultaneous Analysis" on page 124.
1.
2.
3.
200
TOC-LCSH/CSN
Select the analysis mode parameters using the function key.
Using the → key, move the cursor to the selected parameters box.
Set the parameters.
For details, refer to Section 3.3.3.6 "Single-mode Analysis" on page 163, item (3) (11) of "Step 1 Set the Sample Analysis Parameters".
3.4
Analysis with the 8-Port Sampler
Step 5 End Sample Analysis
Procedure
1.
Press the [NEXT] key.
The display returns to the "ASI Measurement Settings" screen. The sample name and
analysis modes are displayed in the row that was just set.
3.4.2.10 Editing the ASI Schedule Settings
After creating an analysis schedule, it can be edited by re-ordering the schedule sequence,
deleting schedules, etc.
F1
[Insert all Cal. Curve]: Creates a calibration curve analysis schedule for all
curves required for the sample analyses registered in the schedule.
F2
[Insert Cal. Curve]: Prior to sample analysis of a selected row, this function
creates the calibration curve required for sample analysis.
F3
[Switch Line]: A selected group exchanges rows with another row. Movement
is limited to one row up or one row down.
F4
[Delete Schedule]: Deletes the selected group.
F5
[Edit]: Enables editing of the analysis parameters of the selected group.
F6
[Reset status]: Changes the status of the message to "Not Measured" or "Not
Meas. (Acid)".
TOC-LCSH/CSN
201
3.4
Analysis with the 8-Port Sampler
(1) Insert All Calibration Curves
This function inserts the calibration analysis parameters for all of the calibration curves
required for the analysis of the samples in the schedule.
Note:
1.
2.
This function key is displayed only when the cursor is in the first row.
Move the cursor to the first row.
Press the F1 [Insert all Cal. Curve] key.
The analysis parameters of all the calibration curves required for sample analysis are
inserted at the start of the schedule.
(2) Insert Calibration Curves Row-by-Row
This function inserts the calibration curve analysis parameters required for analysis of the
selected sample group.
This function is displayed only when the cursor is positioned in a sample analysis row.
1.
Move the cursor to the sample group for which the calibration curve is to be
recalibrated.
2.
Press the F2 [Insert Cal. Curve] key.
The analysis parameters for the calibration curve are inserted in the row directly
above the selected sample group.
(3) Switch Line
1.
2.
Move the cursor to the row you wish to move.
Press the F3 [Switch Lines] key.
The contents of the row are moved.
Note: • To exchange the row with the one above it; press the F3 [Switch with
Upper Line] key.
• To exchange the row with the one below it; press the F2 [Switch with
Lower Line] key.
(4) Delete Schedule
To delete any required schedule:
1.
2.
3.
Press the F4 [Delete Schedule] key.
Move the cursor onto the group to be deleted and press the F4 [Delete Line] key.
Press the F6 [Yes] key.
Note: To cancel deletion, press the F1 [No] key.
To delete a specified schedule range:
202
1.
2.
Press the F4 [Delete Schedule] key.
3.
Specify the range and press the F6 [Delete] key.
TOC-LCSH/CSN
Press the F5 [Delete Area] key. A dialog box in which you can select the required
range appears.
3.4
Note:
Analysis with the 8-Port Sampler
To cancel deletion, press the F1 [Cancel] key.
To delete all schedules:
1.
2.
3.
Press the F4 [Delete Schedule] key.
Press the F6 [Delete All] key.
Press the F6 [Yes] key.
Note: To cancel deletion, press the F1 [No] key.
(5) Edit
1.
2.
Move the cursor to the group for which you wish to edit the measurement conditions.
3.
Edit the measurement conditions.
Note: • If the selected group is for calibration curve measurement, refer to
Section 3.3.3.1 "Calibration Curve Analysis" on page 152.
• If the selected group is for sample measurement, refer to Section 3.3.3.5
"Sample Analysis Settings" on page 161.
4.
Press the [NEXT] key to confirm the changes.
Press the F5 [Edit] key.
Note: • If the selected group is for calibration curve measurement, the "ASI
Calibration Settings" screen is displayed.
• If the selected group is for sample measurement, the "ASI Measurement
Settings" screen is displayed.
(6) Reset Status
To reset the status of any required schedule to "Not Meas. (Acid)":
1.
2.
Press the F6 [Reset status] key.
Move the cursor to the group whose status is to be changed. Press the F3 [One Line
Acidified] key.
To change the status of any required schedule to "Not Measured":
1.
2.
Press the F6 [Reset status] key.
Move the cursor to the group whose status is to be changed. Press the F4 [One Line]
key.
To change the status of all schedules to "Not Meas. (Acid)":
1.
2.
Press the F6 [Reset status] key.
Press the F5 [All Lines Acidified] key.
To change the status of all schedules to "Not Measured":
1.
2.
Press the F6 [Reset status] key.
Press the F6 [All Lines] key.
TOC-LCSH/CSN
203
3.4
Analysis with the 8-Port Sampler
3.4.3 Analysis
3.4.3.1 Starting Analysis
Prior to starting analysis, settings are made to determine the status of the instrument at
completion.
The instrument status can be set to one of three states.
(1)
Power OFF
After analysis, the instrument power is switched OFF (although the main power
remains on).
(2) Sleep
After analysis, the instrument is stopped temporarily, and is started up again at a
specified date and time.
(3) Waiting
The instrument remains in an analysis ready state.
A detailed description of each follows.
(1) Power OFF
After analysis, the instrument power is switched OFF (although the main power remains
on).
1.
After setting up the schedule in the "ASI Schedule Settings" screen, press the [NEXT]
key.
The "ASI Meas. Option" screen is displayed.
2.
3.
Press the F3 [Power OFF] key.
Verify that the [START] key is blinking, and press the [START] key.
Analysis starts according to the ASI schedule. When the analyses are complete, power to
the electric furnace is automatically switched OFF, and the temperature drops. After 30
minutes, carrier gas flow is stopped and power to the instrument is switched OFF.
204
TOC-LCSH/CSN
3.4
Analysis with the 8-Port Sampler
(2) Sleep
After analysis, the instrument is stopped temporarily or placed in the Sleep mode, and
started up again at the specified date and time.
1.
After setting up the schedule in the "ASI Schedule Settings" screen, press the [NEXT]
key.
The "ASI Meas. Options" screen is displayed.
2.
3.
Press the F4 [Sleep] key.
4.
Select the unit status.
This selects the status of the instrument during the sleep state.
Enter the date and time for the instrument to start up again for analysis.
Note: After entering the appropriate number values; press the [Enter] key
to confirm.
Electric Furnace Shutdown
(1) Use the ↓ key to move the cursor to the Furnace item.
(2) Use the [ENTER] key to toggle between ON and OFF.
Select the other item settings in the same way.
5.
Verify that the [START] key is blinking, and press the [START] key.
Analysis is started according to the ASI schedule. After analysis, the instrument
enters the state specified in step 4 above.
At the specified date and time, instrument completes the startup procedures, placing the
instrument back into the analysis ready state.
(3) Waiting
In waiting, the instrument maintains the status existing at the completion of analysis.
1.
After setting up the schedule in the "ASI Schedule Settings" screen, press the [NEXT]
key.
The "ASI Meas. Options" screen is displayed.
2.
3.
Press the F5 [Waiting] key.
Verify that the [START] key is blinking, and press the [START] key.
Analysis is started according to the ASI schedule.
TOC-LCSH/CSN
205
3.4
Analysis with the 8-Port Sampler
3.4.3.2 Interrupting Analysis
Three methods are available for interrupting analysis.
(1)
HALT
This stops analysis immediately. In this case, data acquired in the current analysis is
lost.
(2) STOP
This stops analysis following analysis of the current peak. The analysis results up to
that point are preserved.
(3) Stop After Current Vial
This stops analysis on completion of the analysis at the port currently used. The
analysis results up to that point are preserved.
Analysis Interruption Procedure
206
1.
Press the [STOP] key while analysis is in progress.
The following Function keys are enabled.
• F1: [Cancel] (Cancels the interruption selection process)
• F3: [HALT]
• F4: [STOP]
• F6: [Stop After Current Vial]
2.
Press the appropriate function key.
TOC-LCSH/CSN
3.5
3.5
Data Review
Data Review
Data that is already stored (calibration curve list, method list, data reports) can be reviewed,
and the parameters can be changed.
3.5.1 Reviewing Calibration Curve List
The calibration curve parameters (Protect, Curve Type, Curve Shift) can be changed,
referring to the details in the stored calibration curve list.
Review and modification of the calibration curve parameters can also be performed during
calibration curve analysis. Refer to Section 3.2.2 "Calibration Curve Analysis" on page 92.
Stored calibration curve details can be reviewed when setting up a sample analysis. Refer to
Section 3.2.3 "Sample Analysis" on page 112.
The example presented here describes the review of calibration curve for TC analysis,
however the same procedure is used for IC analysis, POC analysis, NPOC analysis, and TN
analysis.
(1) Reviewing Calibration Curve Details
1.
Press the F6 [Data Report] key in the "Initial Display".
The "Data Report - Measurement Log" screen is displayed.
TOC-LCSH/CSN
207
3.5
Data Review
2.
Press the F6 [Cal. Curves list] key.
The "Data Report - Calibration Curves" screen is displayed.
3.
Press the F2 [TC] key.
As the default, the stored TC analysis calibration curves are displayed.
Note: • For IC analysis calibration curves: Press the F3 [IC] key.
• For POC* analysis calibration curves: Press the F4 [POC] key.
• For TN* analysis calibration curves: Press the F5 [TN] key.
"*" denotes optional, and is displayed only if option settings have been
made.
4.
Use the ↑ ↓ keys to select the calibration curve that you wish to review.
The calibration curve graph and details are displayed.
5.
Press the F1 [Return] key.
The display returns to the "Initial Display".
(2) Changing Calibration Curve Parameters
The following calibration curve parameters can be changed.
•
•
•
Protect
Curve Type
Curve Shift
Procedure
208
1.
Press the F6 [Data Report] key.
The "Data Report - Measurement Log" screen is displayed.
2.
Press the F6 [Cal. Curves list] key.
The "Data Report - Calibration Curves" screen is displayed.
3.
Press the F2 [TC] key.
As the default, the stored TC analysis calibration curves are displayed.
TOC-LCSH/CSN
3.5
Note:
Data Review
• For IC analysis calibration curves: Press the F3 [IC] key.
• For POC* analysis calibration curves: Press the F4 [POC] key.
• For TN* analysis calibration curves: Press the F5 [TN] key.
"*" denotes optional, and is displayed only if option settings have been
made.
4.
Use the ↑ ↓ keys to select the calibration curve that you wish to modify.
The calibration curve graph and details are displayed.
5.
Press the F6 [Edit] key.
The "Data Report - Calibration Curves" screen is displayed.
6.
Change the calibration curve parameters.
• Protect: Press the F2 key to toggle between Protect/Remove Protect.
• Curve Type: Press the F3 key to toggle between Least Squares and Pt-to-Pt.
•
TIP »
Curve Shift: Press the F4 key to toggle through none, Origin and Blank.
Press the F1 [Cancel] key to cancel the parameter changes.
7.
Press the F6 [OK] key.
The operational status returns to step 3 above.
8.
Press the F1 [Return] key.
The display returns to the "Initial Display".
(3) Deleting Calibration Curves
1.
Press the F6 [Data Report] key in the "Initial Display".
The "Data Report - Measurement Log" screen is displayed.
2.
Press the F6 [Cal. Curves list] key.
The "Data Report - Calibration Curves" screen is displayed.
3.
Press the F2 [TC] key.
The stored TC analysis calibration curves are displayed by default.
TOC-LCSH/CSN
209
3.5
Data Review
Note:
• For IC analysis calibration curves: Press the F3 [IC] key.
• For POC* analysis calibration curves: Press the F4 [POC] key.
• For TN* analysis calibration curves: Press the F5 [TN] key.
"*" denotes optional, and is displayed only if optional settings have been
made.
4.
Use the ↑ ↓ keys to select the calibration curve to delete.
The calibration curve graph and details are displayed.
5.
Press the [CE] key.
• Press the F6 key to delete the curve.
• Press the F1 key to cancel curve deletion.
When Calibration Curves Cannot be Deleted
The calibration curve cannot be deleted if any of the letters S, M, A or P are displayed in
the Status field. An error message is displayed after pressing the [CE] key. Delete the
calibration curve using one of the following procedures, as appropriate.
"S" in the Status field: The calibration curve is currently displayed in the "Measurement
Parameters" screen. Press the [MEAS] key to close the parameters box or cancel the
calibration curve indicated at the Calibration Curve item.(Refer to Section 3.2.3.1
"Single-mode Analysis" on page 112.)
"M" in the Status field: The calibration curve is being used by a method. Delete the
method that is using that calibration curve. (Refer to the TIP in Section 3.5.2 "Reviewing
the Method List" on page 211.)
"A" in the Status field: The calibration curve is being used by a schedule in the "ASI
Schedule Settings" screen. Delete the appropriate schedule. (Refer to Section 3.3.3.10
"Editing the ASI Schedule Settings" on page 173, Section 3.4.2.10 "Editing the ASI
Schedule Settings" on page 201.)
"P" in the Status field: The calibration curve is protected. Remove the Protect status.
(Refer to " (2) Changing Calibration Curve Parameters".)
6.
210
TOC-LCSH/CSN
Press the F1 [Return] key.
The display returns to the "Initial Display".
3.5
Data Review
3.5.2 Reviewing the Method List
Described below is the procedure for reviewing the method data used for sample analysis.
Procedure
1.
Press the [MEAS] key.
The "Measurement Parameters" screen is displayed.
2.
Press the [METHOD] key.
The "Method Select" screen is displayed.
3.
Use the F2 - F6 keys to select the method group to review.
A list of saved methods is displayed at the top of the screen.
TOC-LCSH/CSN
211
3.5
Data Review
4.
212
Use the ↑ ↓ keys to select the name of the method to be reviewed.
The details of the method are displayed.
TIP »
Deleting a Method
Select the method to delete and press the [CE] key.
Press the F6 [Yes] key to delete the method.
Press the F1 [No] key to cancel deletion of the method.
TIP »
After step 4 above, press the [NEXT] key to use a reviewed method for sample analysis.
The display returns to the "Measurement Parameters" screen, and the method is loaded.
5.
Press the [METHOD] key.
The display returns to the "Measurement Parameters" screen.
6.
Press the [MEAS] key.
The display returns to the "Initial Display".
TOC-LCSH/CSN
3.5
Data Review
3.5.3 Reviewing Data Reports
Described below are the procedures for reviewing, deleting and printing measured sample
data.
Reviewing Data
1.
Press the F6 [Data Report] key.
The "Data Report - Measurement Log" screen is displayed.
Searching for Data
1.
Press the F3 [Data Search] key to search for data.
The "Data Search" screen is displayed.
TOC-LCSH/CSN
213
3.5
Data Review
2.
Set "Enable" for [Date], specify the date and time for searching, and press the F6
[Search] key to display the data corresponding to the specified date around the middle
of the screen.
Setting [Keyword] to "Enable" allows searching according to sample name,
measurement date, and measurement mode.
Setting [SampleName] to "Enable" allows you to specify the sample name to look for
during the search. Sample names that include all the specified characters are targeted
during the search.
3.
The data that matches the search conditions is displayed.
Deleting Data
TIP »
1.
Specify and highlight the data for deletion using the up and down arrow keys (↑ ↓)
and then press the [ENTER] key to select the data. Alternatively, press the F5 [All
Select/All Clear] key to select all the data on the currently displayed page. Note that
the selection can be cleared by pressing the F5 [All Select/All Clear] key when all the
displayed data is selected. Data selection can be performed across multiple pages.
2.
Press the F5 [All Select/All Clear] key.
The message "YES to delete?" is displayed.
3.
Press the F6 [Yes] key.
The selected data is deleted (and removed from the data display).
Press the F1 [No] key to cancel the operation. The screen returns to the "Data ReportMeasurement Log" screen.
4.
214
TOC-LCSH/CSN
Press the F1 [Return] key.
The screen returns to the "Initial Display".
3.5
Data Review
Printing Data
A report of the selected data can be printed.
TIP »
1.
Specify and highlight the data for printing using the up and down arrow keys (↑ ↓)
and then press the [ENTER] key to select the data.
2.
Press the PRINT key.
The print sheet will not be discharged while the data to print is less than the specified
sheet size. To discharge a print sheet forcibly, press the ABC key and then press the
PRINT key.
If the PRINT key is pressed without data selection, a list of "Data Report - Measurement
Log" will be printed.
TOC-LCSH/CSN
215
3.6
Outputting Data to a USB Memory Device
3.6
Outputting Data to a USB Memory Device
Data selected on the "Data Report" screen can be output to a USB memory device in CSV
format.
Outputting Data
216
1.
Press the F6 [Data Report] key on the "Initial Display".
The "Data Report - Measurement Log" screen is displayed.
2.
Specify and highlight the data for output using the up and down arrow keys and then
press the [ENTER] key to select the data.
3.
Press the F2 [Data Save] key.
The selected data is output to the USB memory device. The directory "DataReport" is
created in the root directory of the USB memory device and data is output to file in
the created directory in CSV format.
Note: • The message "Please wait for a while." is displayed while the data is
being saved. Do NOT remove the USB memory device while this
message is displayed. Verify that the access light on the USB memory
device is not lit before removing the device from the instrument.
• The USB port on the front door of the instrument is only intended for
use with USB memory devices. Do NOT connect other types of devices
to the USB port.
TOC-LCSH/CSN
End of peak data
for injection 3
Start of peak data
for injection 3
End of peak data
for injection 2
Start of peak data
for injection 2
End of peak data
for injection 1
Maximum value
100 msec × 10 entries
(in units of 1 second)
Peak data for injection 3
Peak data for injection 2
Peak data for injection 1
The standard sample concentration is
only output for calibration curve data.
Only output
when data exists.
1.
Start of peak data
for injection 1
Measurement result
for each injection
The calibration curve number and sample data
sample name is only output for calibration curve data.
3.6
Outputting Data to a USB Memory Device
Output File Format
Data is output to file in CSV (Comma Separated Value) format.
The contents of this file is shown below in Figure 3.36 and Figure 3.37. In addition to
concentrations and area values that can be referenced in the data report, peak profile
data (intensity data every second) for each injection is also output. Spreadsheet
software can be used to create peak graphs from this data.
Figure 3.36 Details of Data Output to a USB Memory Device (For Water Sample Measurement)
TOC-LCSH/CSN
217
218
TOC-LCSH/CSN
End of peak data
for injection 3
Start of peak data
for injection 3
End of peak data
for injection 2
Start of peak data
for injection 2
End of peak data
for injection 1
Start of peak data
for injection 1
Measurement result
for each injection
Maximum value
100 msec × 10 entries
(in units of 1 second)
Peak data for injection 3
Peak data for injection 2
Peak data for injection 1
The calibration curve number and sample data
sample name is only output for calibration curve data.
The standard sample concentration is
only output for calibration curve data.
Only output
when data exists.
3.6
Outputting Data to a USB Memory Device
Figure 3.37 Details of Data Output to a USB Memory Device
(For Solid Sample Measurement (Using the SSM-5000A))
3.7
3.7
Applications Operations (H Type Only)
Applications Operations (H Type Only)
3.7.1 Manual Injection Analysis
To perform analysis without using the equipped sample injector syringe, samples can be
drawn into the syringe and injected manually with a gas-tight syringe when the optional
manual injection kit is installed.
Analysis Preparation
1. Installation of the Manual Injection Kit
1.
Remove the knurled thumbscrew that secures the slider then remove the TC/TN
injector slider.
Knurled Thumbscrew
2.
Figure 3.38 Removing the Slider
Install the TC/TN block provided in the kit.
TC/TN Block
Figure 3.39 Installing the TC/TN Block
TOC-LCSH/CSN
219
3.7
Applications Operations (H Type Only)
3.
Remove the slider of the IC injector in the same manner and install the IC block
provided with the manual injection kit.
IC Block
Figure 3.40
Note:
When installing the block, be sure that it is aligned with the
injection port.
2. Screen Settings
1.
In the "Conditions - Unit" screen, toggle to the 'Enable' setting for the Manual
Injection Kit (Manual Inj).
Note: The 'Enable' setting disables operation of the TOC-L injector
syringe.
Analysis
The procedure for performing these settings is briefly described here. Refer to Section 3.2.2
"Calibration Curve Analysis" on page 92 and Section 3.2.3 "Sample Analysis" on page 112
for further details.
220
TOC-LCSH/CSN
3.7
Applications Operations (H Type Only)
1. Calibration Curve Analysis
1.
Press the [CAL] key while viewing the "Initial Display" to display the "Calibration
Settings" screen.
2.
Depending on the analysis mode to be used, press the F2 [TC], F3 [IC] or F5 [TN]
key, as appropriate.
3.
Refer to the following items.
• Calibration Curve Number:
Enter the calibration curve number.
• Standard Concentration:
Enter the concentration of the standard
solution.
• Dilution Factor:
Set this to "1".
• Number of Injections:
Set this to "1".
• Maximum Number of Injections: Set this to "1".
• SD:
Use the default value.
• CV%:
Use the default value.
• Injection Volume:
Set the sample injection volume.
• Acid Addition Ratio:
Enter "0".
• Sparge Time:
Enter "0".
Note:
When the standard concentration is set, the injection volume is
displayed. This is the automatic value calculated for use with the
instrument-equipped sample injector. This value can be changed as
necessary.
TOC-LCSH/CSN
221
3.7
Applications Operations (H Type Only)
4.
Press the [NEXT] key.
The "Calibration" screen is displayed.
5.
Fill the syringe with the sample.
Note: Wash the syringe 3 or 4 times with the sample.
6.
Verify that the Ready lamp has illuminated and that the [START] key is blinking, and
then press the [START] key.
The [START] key illuminates and analysis begins.
7.
For TC or TN analysis, open the injection port valve, and insert the syringe into the
injection port.
For IC analysis, insert the syringe into the injection port septum.
Note: When inserting the needle into the injection port, insert the needle
all the way. Maintain a consistent injection speed for all the
injections to obtain good reproducibility.
8.
Withdraw the syringe from the injection port.
For TC or TN analysis, close the injection port valve.
9.
When analysis is complete, the results are displayed and the [START] key goes out.
Note: For repeat analysis:
Press the F1 [Add Injection] key. Follow the on-screen directions, repeating
steps 5 - 9 above.
10. To end analysis, press the F6 [End Measurement] key.
The display returns to the "Initial Display".
222
TOC-LCSH/CSN
3.7
Applications Operations (H Type Only)
2. Sample Analysis
1.
Press the [MEAS] key.
The "Measurement Parameters" screen is displayed.
2.
Depending on the analysis mode used, press the F2 [TC], F3 [IC], F5 [NPOC] or F6
[TN] key, as appropriate.
3.
Refer to the following items.
• Sample Name:
Set the sample name.
• Calibration Curve:
Enter the number of the calibration curve to be
used.
• Injection Volume:
The injection volume used for generating the
calibration curve is displayed and can be
changed.
• Number of Injections:
Set this to "1".
• Maximum Number of Injections: Set this to "1".
• SD:
Use the default value.
• CV%:
Use the default value.
• Acid Addition Ratio:
Enter "0".
• Sparge Time:
Enter "0".
TOC-LCSH/CSN
223
3.7
Applications Operations (H Type Only)
4.
Press the [NEXT] key.
The "Measurement" screen is displayed.
5.
Fill the syringe with the sample.
Note: If the sample is to be drawn into the syringe, wash the syringe 3 or
4 times with the sample to be measured.
6.
Verify that the Ready lamp has illuminated and that the [START] key is blinking, and
then press the [START] key.
The [START] key illuminates and analysis begins.
7.
For TC or TN analysis, open the injection port valve, and insert the syringe into the
injection port.
For IC analysis, insert the syringe into the injection port septum.
Note: When inserting the needle into the injection port, insert the needle
all the way. Maintain a consistent injection speed for all the
injections to obtain good reproducibility.
8.
Withdraw the syringe from the injection port.
For TC or TN analysis, close the injection port valve.
9.
When the analysis is complete, the results are displayed and the [START] key goes
out.
Note: For repeat analysis:
Press the F1 [Add Injection] key. Follow the on-screen directions, repeating
steps 5 - 9 above.
10. To end analysis, press the F6 [End Measurement] key.
11. The display returns to the "Initial Display".
Reference: To create a method, refer to Section 3.2.4 "Creating a Method" on page 132.
224
TOC-LCSH/CSN
3.7
Applications Operations (H Type Only)
Precautions for Low Concentration Samples
In manual injections of sample concentrations lower than 1 mg/L, it is necessary to take the
following precautions to prevent contamination of the sample and the measurement
process.
•
Injecting Sample into the Injection Port
Use a separate micro syringe (500 µL) for high sensitivity measurement. Any
contamination on the sample injection port may affect the result for high sensitivity
measurement.The inside of the injection port can be contaminated by sample solution
that adheres to the tip of the micro syringe needle. When inserting the micro syringe
into the injection port, use extreme care to avoid touching the tapered portion of the
inside of the sample injection port. After filling the syringe, wipe the excess solution
from the needle surface with soft tissue paper. Prevent excess drops of solution from
forming on the tip of the needle by gently pulling back on the plunger.
•
Cleaning the Sample Injection Port
Under normal operating conditions, fill a 500 µL micro syringe with pure water and
insert it into the injection port. Keep the bottom of the syringe barrel 8-10 mm above the
injection port. Under normal operation, the bottom of the syringe barrel is inserted until
it comes into contact with the injection port allowing the needle tip to protrude from the
needle guide pipe by about 5-6 mm. With the needle 8-10 mm higher than normal
operation, the tip of the needle inside the needle guide pipe. Slowly dispense the pure
water. The pure water does not flow into the combustion tube. It is driven out of the
injection port by the carrier gas flowing through the needle guide pipe. Wipe off the
water coming out of the injection tube with soft tissue paper. The internal injection port
and inside of the needle guide pipe are now clean.
•
Measurement of service water or contamination free environmental water, such as river
water, often reveals that IC is the major part of TC when the TOC content is around
1 mg/L. For these types of samples it is preferable to remove the IC content before
measuring TOC through the TC channel.
Errors for TC and IC analyses are additive. For samples that have a comparatively high
IC content relative to the TOC content, the TOC analysis error will be large if it is
determined by the difference between TC and IC results.
Maintenance
Replacing the IC Injection Port Septum (Cushion O-Ring)
The septum used with the IC injection port is a consumable item. It typically can be used
for 200 or more injections; however, it should be replaced if there is deterioration in
reproducibility or peak shapes.
Replacement cushion o-ring (20 pcs.): P/N S630-01559-01
Replacement Procedure
1.
2.
3.
Loosen and remove the injection port bushing.
Remove the old septum, and insert a new one.
Replace the bushing and tighten it.
TOC-LCSH/CSN
225
3.7
Applications Operations (H Type Only)
CAUTION
IC reaction solution may spatter close to the injection port septum and injection
port; however this poses no problem during analysis. When replacing the
septum, wipe away any liquid, taking care to avoid contact.
Gas-tight Syringe
For analysis, use a needle length of 50mm, or a 2-inch gas-tight syringe. The following gastight syringes are available from Shimadzu. Order, as necessary.
Table 3.7 • Gas-Tight Syringes
Part Name
P/N
Capacity
Gas-tight syringe set 25µL
S638-60733-02
25µL*
Gas-tight syringe set 50µL
-03
50µL*
Gas-tight syringe set 100µL
-04
100µL*
Gas-tight syringe set 250µL
-05
250µL*
Gas-tight syringe set 500µL
-06
500µL*
Gas-tight syringe 1mL
S046-00026-02
1mL
Gas-tight syringe set 5mL
-03
5mL
Gas-tight syringe set 10mL
-04
10mL
* This set includes one replacement gas-tight syringe needle and one plunger tip.
226
TOC-LCSH/CSN
3.7
Applications Operations (H Type Only)
3.7.2 Gas Sample Analysis (When Using the Optional Manual Injection Kit)
If the optional manual injection kit is installed, analysis of TC and IC in gas samples can be
performed by using gas-tight syringes or other applicable injectors to inject the gas
samples.
Precautions for Gas Sample Analysis
CAUTION
•
•
•
•
•
•
Use caution when measuring combustible or explosive gases.
Do not inject more than 10mL of sample when measuring combustible or
explosive gases. The combustion tube could break.
Do not analyze samples that can release toxic substances during combustion. The
exhaust gas released due to analysis passes through the CO2 detector to the CO2
absorber, after which it is used as NDIR purge gas, and then vented inside the
instrument. Take appropriate countermeasures if there is a possibility that toxic
substances could be included in the exhaust gas. If appropriate countermeasures
cannot be taken, do not perform such analyses.
Sample analysis results are displayed according to the gas concentration used in
calibration. For example, if CO2 is used to generate the calibration curve, the
sample analysis result is displayed based on a conversion using the CO2 gas
concentration.
Gas samples have certain properties such as adsorption, condensation, and
reactivity. Some gas samples are partially liquid or contain a solid component.
Depending upon the properties, certain conditions that cannot be ignored may
occur, such as residual substances and contamination in the flow line. These
conditions may result in peak tailing, carryover, baseline fluctuation, etc.
High concentrations of NOx or SOx in the sample or in the post combustionoxidized sample could interfere with the NDIR activity. To evaluate the degree of
the interference, combine the analysis of the base gas without the TOC
component and the sample analysis.
Analysis Preparation
1. Installation of the Manual Injection Kit
1.
Install the manual injection kit by referring to Section 3.7.1 "Manual Injection
Analysis" on page 219.
2. Screen Settings
1.
In the "Conditions - Unit Management" screen, toggle Manual Injection Kit to Enable.
Note: The Enable setting disables operation of the TOC-L injector
syringe.
TOC-LCSH/CSN
227
3.7
Applications Operations (H Type Only)
Analysis
The procedure for setting the various parameters is the same as described in Section 3.2.2
"Calibration Curve Analysis" on page 92 and Section 3.2.3 "Sample Analysis" on page 112.
1. Calibration Curve Analysis
228
1.
Prepare a standard gas containing a known concentration of carbon.
For IC (carbon dioxide) analysis, prepare a standard gas with a known carbon dioxide
concentration. For TC analysis, other organic gases (such as methane) of known
concentration can also be used.
2.
Press the [CAL] key while viewing the "Initial Display" to display the "Calibration
Settings" screen.
3.
Depending on the analysis mode to be used, press the F2 [TC], F3 [IC] of F5 [TN]
key, as appropriate.
TOC-LCSH/CSN
3.7
4.
Refer to the following items.
• Calibration Curve Number:
Applications Operations (H Type Only)
Enter the calibration curve number.
• Standard Concentration:
Enter the carbon concentration (or gas
concentration) of the standard gas.
• Dilution Factor:
Set this to "1".
• Number of Injections:
Set this to "1".
• Maximum Number of Injections: Set this to "1".
• SD:
Use the default value.
• CV%:
Use the default value.
• Injection Volume:
Set the sample injection volume.
• Acid Addition Ratio:
Enter "0".
• Sparge Time:
Enter "0".
Note:
The injection volume is displayed when the standard concentration
is set assumes an aqueous sample. Determine the actual injection
volume referring to "Table 3.9 • Relationship Between Appropriate
Peak Height and (CO2) Gas Concentration / Injection Volume". The
values indicated in this table are reference values only.
5.
Press the [NEXT] key.
The "Calibration" screen is displayed.
6.
Fill the gas-tight syringe with the sample.
Note: If the analysis gas is to be drawn into the syringe, replace the gas in
the gas-tight syringe 3 or 4 times with the analysis gas.
7.
Verify that the Ready lamp has illuminated and that the [START] key is blinking, and
then press the [START] key.
The [START] key illuminates and analysis begins.
TOC-LCSH/CSN
229
3.7
Applications Operations (H Type Only)
8.
For TC or TN analysis, open the injection port valve, and insert the syringe into the
injection port.
For IC analysis, insert the syringe into the injection port septum.
Note: When inserting the needle into the injection port, insert the needle
all the way. Maintain a consistent injection speed for all the
injections to obtain good reproducibility.
9.
For TC or TN analysis, close the injection port valve.
Withdraw the syringe from the injection port.
10. When complete, the results are displayed and the [START] key goes out.
For Repeat Analysis
Press the F1 [Add Injection] key. Follow the on-screen directions, repeating steps 6 - 9
above.
11. To end analysis, press the F6 [End Measurement] key.
The display returns to the "Initial Display".
2. Sample Analysis
1.
Press the [MEAS] key.
The "Measurement Parameters" screen is displayed.
2.
Depending on the analysis mode to be used, press the F2 [TC], F3 [IC] or F4 [TN]
key, as appropriate.
3.
Refer to the following items.
• Sample Name:
Set the sample name.
• Calibration Curve:
Enter the number of the calibration curve to be
used.
• Injection Volume:
The injection volume used for generating the
calibration curve is displayed (can be
changed).
• Number of Injections:
Set this to "1".
• Maximum Number of Injections: Set this to "1".
230
• SD:
Use the default value.
• CV%:
Use the default value.
• Acid Addition Ratio:
Enter "0".
• Sparge Time:
Enter "0".
4.
Press the [NEXT] key.
The "Measurement" screen is displayed.
5.
Fill the gas-tight syringe with the sample.
Note: If the analysis gas is to be drawn into the syringe, replace the gas in
the gas-tight syringe 3 or 4 times with the analysis gas.
6.
Verify that the Ready lamp has illuminated and that the [START] key is blinking, then
press the [START] key.
The [START] key illuminates, and analysis begins.
TOC-LCSH/CSN
3.7
Applications Operations (H Type Only)
7.
For TC or TN analysis, open the injection port valve, and insert the syringe into the
injection port.
For IC analysis, insert the syringe into the injection port septum.
Note: When inserting the needle into the injection port, insert the needle
all the way. Maintain a consistent injection speed for all the
injections to obtain good reproducibility.
8.
Withdraw the syringe from the injection port.
For TC or TN analysis, close the injection port valve.
9.
When complete, the results are displayed and the [START] key goes out.
Note: For repeat analysis:
Press the F1 [Add Injection] key. Follow the on-screen directions, repeating
steps 6 - 9 above.
10. To end analysis, press the F6 [End Measurement] key.
The display returns to the "Initial Display".
Reference: To create a method, refer to Section 3.2.4 "Creating a Method" on page 132.
Maintenance
Replacing the IC Injection Port Septum (Cushion O-Ring)
The septum used with the IC injection port is a consumable item. It typically can be used
for 200 or more injections; however, it should be replaced if there is deterioration in
reproducibility or peak shapes.
Replacement cushion o-rings (20 pcs.): P/N S630-01559-01
Replacement Procedure
1.
2.
3.
Loosen and remove the injection port bushing.
Remove the old septum, and insert a new one.
Replace the bushing and tighten it.
CAUTION
IC reaction solution may spatter close to the injection port septum and injection
port; this however poses no problem during analysis. When replacing the
septum, wipe away any liquid, taking care to avoid contact.
TOC-LCSH/CSN
231
3.7
Applications Operations (H Type Only)
Gas-tight Syringe
For analysis, use a needle length of 50mm or a 2-inch gas-tight syringe. The following gastight syringes are available from Shimadzu.
Table 3.8 • Gas-Tight Syringes (Option)
Part Name
P/N
Capacity
Gas-tight syringe set 25µL
S638-60733-02
25µL*
Gas-tight syringe set 50µL
-03
50µL*
Gas-tight syringe set 100µL
-04
100µL*
Gas-tight syringe set 250µL
-05
250µL*
Gas-tight syringe set 500µL
-06
500µL*
Gas-tight syringe 1mL
S046-00026-02
1mL
Gas-tight syringe set 5mL
-03
5mL
Gas-tight syringe set 10mL
-04
10mL
* Set comprises one replacement gas-tight syringe needle and one plunger.
Table 3.9 • Relationship Between Appropriate Peak Height and (CO2) Gas
Concentration / Injection Volume
Gas Concentration (CO2)
TC
IC
Gas Injection Volume*
100ppm
10mL
1000ppm
1mL
1%
500µL
10%
300µL
100%
30µL
100ppm
6µL
1000ppm
600µL
1%
300µL
10%
200µL
100%
20µL
* The values, indicated in this table, are reference values only. Data will vary slightly among
instruments.
232
TOC-LCSH/CSN
4
4
4
Maintenance
Inspection and maintenance of the TOC-L instrument are very important to ensure
normal instrument operation and reliable and accurate data acquisition.
4.1
Daily Inspection
Details the daily inspection procedures that should be performed before
instrument startup.
4.2
Periodic Inspections
Describes the periodic inspection procedures.
4.3
Autosampler (ASI-L) Maintenance
Describes periodic inspection procedures for the ASI-L.
4.4
8-Port Sampler (OCT-L) Maintenance
Describes periodic inspection procedures for the OCT-L.
4.5
TN Unit (TNM-L) Maintenance
Describes periodic inspection procedures for the TNM-L.
4.6
Troubleshooting
Describes the content of error messages and troubleshooting procedures.
4
4
4.1
Daily Inspection
4.1
Daily Inspection
Check the levels of dilution water, acid, drain vessel water, humidifier water, and the
amount of printer chart paper before starting the instrument for the day's operations.
4.1.1 Checking Dilution Water
Verify that there is sufficient dilution water for analysis. If necessary, replenish the dilution
water referring to Section 3.1.8 "Preparation of Dilution Water" on page 43.
4.1.2 Checking Acid
Inspect the remaining quantity of acid before using the instrument. If the quantity of acid is
low, refill the acid container according to the procedure described in Section 3.1.9 "Acid
Preparation" on page 44. A container with a capacity appropriate to the required amount of
acid, such as a narrow-mouthed glass bottle (1 L), can also be used.
4.1.3 Checking Drain Vessel Water Level
Verify that the water level in the drain vessel inside the instrument is within 10mm of the
overflow tube on the side of the drain vessel. If the level is lower replenish using purified
water (ion-exchange water).
Reference: For details on adding purified water, refer to Section 3.1.6 "Water Supply to the
Dehumidifier Drain Vessel" on page 41.
Confirm that carrier gas does not leak from the tip of the drain tubing when the flow rate is
150mL/min.
Rubber cap
Drain discharge tube
Cooler drain vessel
Figure 4.1 Drain Vessel Water Level
234
TOC-LCSH/CSN
4.1
Daily Inspection
4.1.4 Checking Humidifier Water Level
Verify that the water level in the humidifier is above the "Lo" mark. If the level is below the
"Lo" mark, replenish using purified water via the water supply port at the top of the vessel.
Add enough water so the level reaches the "Hi" mark.
Water supply port
Humidifier
Figure 4.2 Filling the Humidifier with Water
4.1.5 Inspecting the Liquid in the B-Type Halogen Scrubber (Option)
Check the level of liquid (0.05 mol/L hydrochloric acid) in the B-type halogen scrubber
and amount of remaining stainless mesh before using the instrument, and if necessary, top
up the liquid or replace the stainless mesh.
The liquid level in the B-type halogen scrubber decreases over time when the instrument is
waiting for analysis to start (and the carrier gas is flowing), the sample injection volume is
small, or the interval between analyses is large during analysis. Always check the liquid
level before starting analysis and, if necessary, refill the vessel with 0.05 mol/L
hydrochloric acid (this is important when performing continuous analysis over an extended
period of time using the autosampler). Although the liquid color turns blue or brown with
use, this is normal.
CAUTION
Hydrochloric acid is a deleterious substance and must always be handled with
care to prevent spills and contact with the skin. For details, refer to Section 5.10
"Safety Data Sheets" on page 377.
The vessel of the B-type halogen scrubber is made of glass. Handle the vessel
with care to prevent breakage due to impact with other objects.
The ability to absorb halogen stops if the amount of liquid in the B-type halogen
scrubber decreases enough to prevent the carrier gas from bubbling or if the
stainless mesh for absorption dissolves completely. Before starting analysis,
always verify that the liquid level is up to the height of the branching tube in the
vessel of the B-type halogen scrubber and the scrubber contains stainless mesh
for absorption.
TOC-LCSH/CSN
235
4.2
Periodic Inspections
4.2
Periodic Inspections
To maintain the performance of the instrument, perform periodic checks of the items listed
in this section.
4.2.1 Catalyst Regeneration
Inorganic substances contained in the samples accumulate in the catalyst as salts and
oxides. Buildup of these residues decreases the sensitivity and repeatability of analyses.
Catalyst performance can be checked by measuring a standard solution.
This type of catalyst contamination occurs when measuring alkaline samples and samples
that contain high concentrations of IC compounds. In these cases, performance can be
restored by injecting dilute hydrochloric acid onto the catalyst. (This will have little effect
on TN analysis.)
Higher-than-normal values are obtained for standard solutions or zero water measured
using new catalyst or catalyst that has not been used for a long time. These values will
gradually decrease. Regeneration is also an effective procedure in these cases.
Catalyst regeneration is performed using the 1M hydrochloric acid stored in the instrument
for removal of IC in NPOC measurement. The process is the same for both TOC standard
catalyst and TOC high sensitivity catalyst. If performance is not restored after the
regeneration process, replace the catalyst. See Section 4.2.2 "Washing or Replacing
Catalyst" on page 237.
Regeneration Procedure
The procedure for regenerating the catalyst follows.
1.
236
TOC-LCSH/CSN
Press the F5 [Maintenance] key in the "Initial Display".
The "Maintenance" screen appears.
4.2
Periodic Inspections
2.
Move the cursor to the Regenerate TC Catalyst item, and press the [NEXT] key.
The message "TC Catalyst regeneration in progress. Please wait." will be displayed on
screen, as regeneration is executed.
3.
The message box closes when the regeneration process is complete.
CAUTION
Use the dilute hydrochloric acid for catalyst regeneration. DO NOT use IC
reaction solution (phosphoric acid).
4.2.2 Washing or Replacing Catalyst
Large quantities of salts accumulate in the catalyst when measuring samples with high salt
concentrations. If sensitivity and reproducibility do not improve after catalyst regeneration,
wash or replace the catalyst. Refer to Section 4.2.1 "Catalyst Regeneration" on page 236.
Note that TOC high sensitivity catalyst cannot be washed or reused.
Removing the Combustion Tube
Remove the combustion tube according to the following procedure.
For details on installing the combustion tube, refer to Section 3.1.3 "Connecting the
Combustion Tube" on page 29.
TOC-LCSH/CSN
237
4.2
Periodic Inspections
CAUTION
•
•
•
Allow the electric furnace to cool to room temperature for at least six hours after
switching off the power supply by shutting down the instrument before
performing maintenance on the combustion tube or catalyst. Burns may result if
this task is attempted when the furnace is at a high temperature.
Combustion tubes are made of quartz glass. Always wear protective leather
gloves when handling combustion tubes to prevent injuries due to breakage.
Do not use wrenches or other such tools. Doing so could break the combustion
tube and cause injury.
Removal Procedure
1.
Open the door on top of the instrument, remove the slider retaining screws (knurled
screws) from the sample injector, and pull the slider towards you and out of the
sample injector.
Slider retaining
screw
Slider
Carrier gas
introduction tubing
Sample injector retaining screws
(two)
Hexagon cap nut
Sample injector
Drain tubing
Figure 4.3 Sample Injector
238
2.
Loosen the hexagon cap nut that joins the carrier gas introduction tubing (PTFE
tubing) to the right side of the sample injector and then remove the tubing.
3.
Loosen the hexagon cap nut on the PTFE coupling located on the cooling tubing inlet
at the bottom end of the combustion tube.
TOC-LCSH/CSN
4.2
4.
Periodic Inspections
Loosen the two knurled screws on the sample injector and remove the sample injector
together with the combustion tube in the upward direction.
Sample injector
Drain tubing
Combustion
tube
Y-shaped fitting
Figure 4.4 Removing the Combustion Tube
Washing Catalyst
Standard catalyst can be washed and reused several times using the following procedure.
High sensitivity catalyst cannot be washed and reused.
CAUTION
Allow the electric furnace to cool to room temperature for at least six hours after
switching off the power supply by shutting down the instrument before
performing maintenance on the combustion tube or catalyst. Burns may result if
this task is attempted when the furnace is at a high temperature.
Washing Procedure
1.
2.
3.
4.
Thoroughly wash the catalyst with tap water to remove any accumulated salts.
Neutralize the alkalis with dilute hydrochloric acid (5:1).
Thoroughly wash the catalyst with tap water to remove the hydrochloric acid.
Rinse with pure water (ion exchange water acceptable) and then dry.
TOC-LCSH/CSN
239
4.2
Periodic Inspections
CAUTION
•
•
Dry the catalyst at a temperature lower than 700°C to avoid the degradation of
catalyst activity that occurs at higher temperatures.
A large quantity of steam is produced when the regenerated catalyst is placed in
the oven and heated. Due to the danger of burn injury, leave the outlet of the
combustion tube open until no more steam is released.
Replacing Catalyst
If performance is not restored, after the above washing process, replace the catalyst with
new platinum catalyst (alumina spherical support). Always have spare platinum catalyst on
hand for such a contingency. One bottle of platinum catalyst is enough for one replacement.
Use the following procedure to replace the platinum catalyst.
Procedure
1.
Wash the platinum mesh and the inside of the combustion tube with (1:2)
hydrochloric acid (1 part concentrated HCl and 2 parts water). Rinse with water.
2.
3.
Dry, and reuse these items.
Fill the combustion tube as described in Section 3.1.1 "Catalyst Filling" on page 24.
TOC High Sensitivity Catalyst
TOC high sensitivity catalyst cannot be washed and reused like standard catalyst. If
analysis sensitivity and/or repeatability are not restored after catalyst regeneration, replace
the deteriorated high sensitivity catalyst with new high sensitivity catalyst. The platinum
mesh and combustion tube, however, can be reused. Wash them with hydrochloric acid as
with normal catalyst.
Disposal of Catalyst
Used catalyst should be disposed of according to local industrial waste disposal regulations.
It must be clearly disclosed (using an industrial waste manifest) that the catalyst contains
platinum.
4.2.3 Replacing the Carrier Gas Purification Tube and Catalyst
The carrier gas purification tube burns the carrier gas and oxidizes carbon-based impurities,
converting them to carbon dioxide. The carbon dioxide is absorbed and eliminated by the
CO2 absorber. The carrier gas purification tube is filled with oxidation catalyst (same as
TOC standard catalyst).
The procedure for replacing the purification tube and catalyst is as follows.
240
TOC-LCSH/CSN
4.2
Periodic Inspections
Removal of Carrier Gas Purification Tube
CAUTION
Allow the electric furnace to cool to room temperature for at least six hours after
switching off the power supply by shutting down the instrument before
performing maintenance on the combustion tube or catalyst. Burns may result if
this task is attempted when the furnace is at a high temperature.
Removal Procedure
1.
Remove the combustion tube together with the TC sample injector from the electric
furnace.
2.
Release the swage locks on the top and bottom of the carrier gas purification tube.
Refer to Section 3.1.3 "Connecting the Combustion Tube" on page 29.
3.
Extract the carrier gas purification tube from the electric oven by pulling upward.
Replacing Catalyst
CAUTION
The top nut of the Swage lock joint is hand-tightened. Do not use any tools
(wrench, etc.) to tighten or loosen this nut. Because the tube is constructed of
quartz glass, over-tightening or aggressive handling may result in damage.
Procedure
1.
Remove the catalyst from the carrier gas purification tube through the opening at the
top.
2.
3.
Remove the quartz wool using a thin tube, etc.
4.
Pack a small amount of quart wool into the tube from the bottom.
Note: The quartz wool is inserted to prevent the catalyst from falling out
of the bottom. Packing too much quartz wool into the tube will
greatly impede airflow, so do not use too much quartz wool. To
prevent contamination of the catalyst or the inclusion of foreign
particles, use the same precautions used when filling the
combustion tube with TOC platinum catalyst.
5.
Insert the straight end of the carrier gas purification tube down into the front 8mmdiameter hole in the oven.
6.
7.
Using the Swage lock joints restore the tubing connections to their original condition.
Insert a small amount of new TOC standard catalyst into the combustion tube from
the bottom (straight end).
Return the combustion tube and the TC sample injector to their original positions on
the electric furnace.
TOC-LCSH/CSN
241
4.2
Periodic Inspections
4.2.4 Washing / Replacing the Combustion and Carrier Gas Purification Tubes
When the inner surface of the combustion tube reacts with salts contained in the samples,
the inner surface devitrifies, or becomes crystalline in texture and turns white. The tube can
continue to be used in this condition until it breaks or cracks, causing gas leaks.
During washing or replacing of the catalyst, wash the interior of the combustion tube and
carrier gas purification tube with (1:2) hydrochloric acid (1 part concentrated HCl and 2
parts water) to remove the contaminants and accumulated salts. Rinse with water, dry, and
then reuse the tube(s).
4.2.5 Replacing the High-Purity Air Cylinder
A 47-liter cylinder of high-purity air used as the carrier gas will last for approximately three
months using the H Type instrument, and two months using the N Type.
Note:
• Replace the cylinder when the residual pressure diminishes to a few hundred
kPa (~40PSI). Do not wait until it is completely empty.
• When connecting a new cylinder, clean the connections thoroughly and, after
connecting the cylinder, do not allow any dust, etc. from entering the
instrument.
• It is recommended that a spare cylinder is always kept available.
4.2.6 Replacing the CO2 Absorber
Once a year, replace each of the CO2 absorbers installed behind the instrument.
CO2 Absorber Disposal Procedure
Used CO2 absorbers should be disposed of according to local industrial waste disposal
regulations. It must be clearly disclosed (using an industrial waste manifest) that the CO2
absorber contains soda lime.
Reference: For details on replacing the CO2 absorbers, refer to Section 3.1.10 "Installation of the CO2
Absorber" on page 45.
4.2.7 Replacing the Halogen Scrubber
The absorbent inside the halogen scrubber turns black as it absorbs chlorine; this
discoloration band advances toward the outlet as the amount of chlorine absorbed
increases. Replace the scrubber with a new halogen scrubber when the front of the
discoloration band reaches the position shown in Figure 4.5 "Halogen Scrubber" on page
243.
Replacement Procedure
1.
2.
242
TOC-LCSH/CSN
Unclip the upper and lower clips securing the halogen scrubber.
Disconnecting the Viton connectors remove the halogen scrubber.
4.2
Periodic Inspections
3.
Remove the film at both ends of the new halogen scrubber and connect it to the Viton
connectors.
4.
Secure the halogen scrubber with the two clips in its original position.
Gas Flow Direction
Replace Scrubber When
Discoloration Band Reaches
this Point
Dehumidifier
To Sample
Cell Inlet
Halogen Reactant-filled Cylinder
Figure 4.5 Halogen Scrubber
The baseline may fluctuate immediately after replacement. Allow the instrument to run for
a short time until the baseline stabilizes. Stabilization normally occurs within one hour.
Used halogen scrubbers should be disposed of according to local industrial waste disposal
regulations. It must be clearly disclosed (using an industrial waste manifest) that the
halogen scrubber contains copper.
Halogen scrubber
(take note of the
arrow direction)
Figure 4.6 Halogen Scrubber Replacement
TOC-LCSH/CSN
243
4.2
Periodic Inspections
4.2.8 Syringe Replacement
Use the procedure below to replace the syringe.
CAUTION
•
•
•
Install the syringe according to the procedure to avoid the danger of acid leaking
from the syringe connection port.
Keep hands away from the sample injector during operation of the syringe pump
sample injector.
The syringe barrel is made of glass, handle it carefully to avoid breakage.
Procedure
244
1.
Press the F5 [Maintenance] key on the "Initial Display".
The "Maintenance" screen is displayed.
2.
3.
Use the arrow keys to move to the cursor to Replace Syringe.
4.
Disconnect the sparge gas line from the syringe, remove the plunger retaining screw,
and remove the syringe.
5.
Reverse the above procedure to install the new syringe and connect the sparge gas
line. At this point, the plunger retaining screw is not completely tightened. Tighten the
retaining screw so that the plunger can still be slightly moved forwards and
backwards as well as left and right.
6.
7.
Press the F4 [Move test Up & Down] key to move the syringe to its upper limit.
TOC-LCSH/CSN
Press the [Next] key.
Once preparation for syringe replacement is complete, the message "Syringe
exchange. Exchange syringe now." is displayed.
Once the syringe reaches the top position, hold the plunger vertical and tighten the
plunger retaining screw to secure it to the plunger holder.
4.2
Periodic Inspections
8.
Click Finish Replacement. The syringe pump zero point detection operation is
executed automatically.
9.
Press the F6 [End] key.
The display returns to the "Maintenance" screen.
10. Press the F1 [Return] key.
The screen returns to the "Initial Display".
8-port valve
Syringe
Plunger retaining screw
Plunger
Plunger holder
Figure 4.7 Plunger Retaining Screw
CAUTION
Hand-tighten only. Do not use a tool tighten the plunger retaining screw. Overtightening may deform the resin components of the 8-port valve and cause leaks.
4.2.9 Replacing the Syringe Plunger Tip
The syringe plunger tip is constructed of fluororesin and wears with use. Gaps will
eventually form between the plunger and the inner wall of the syringe barrel (glass tube)
causing leaks. When leaks occurs, bubbles are produced near the syringe tip while the
sample is being drawn into the syringe or sample may leak from the bottom of the barrel
when the sample is discharged. At this time, replace the plunger tip.
Replacement Procedure
1.
2.
First remove the syringe referring to Section 3.1.5 "Installing the Syringe" on page 39.
Use a sharp knife to make two or three incisions at the bottom of the plunger tip, as
shown in Figure 4.8 "Removing the Old Plunger Tip" on page 246.
TOC-LCSH/CSN
245
4.2
Periodic Inspections
3.
Grasp the plunger tip with a pair of pliers and remove it from the plunger. The O-ring
that is held in place by the plunger tip also comes off (DO NOT reuse this O-ring).
Figure 4.8 Removing the Old Plunger Tip
4.
Pushing down on the plunger, press the leading edge of the new plunger tip, straight
into the plunger tip seat, see Figure 4.9 "Installing the New Plunger Tip (crosssection)" on page 246. Save the syringe for future use since the plunger tip seat is
enclosed inside the syringe.
Plunger Tip
Plunger Tip Seat
Figure 4.9 Installing the New Plunger Tip (cross-section)
Note:
• Do not to scratch the perimeter of the plunger tip. This could cause
leaks.
• Use only Shimadzu-specified plunger tips. Use of unspecified parts may
result in malfunction and/or diminished performance.
246
TOC-LCSH/CSN
4.2
Periodic Inspections
4.2.10 Replacing The Sliding Sample Injector O-Rings
In the sliding sample injector, two types of O-rings are stacked between the injection block
and the slider below. Replace both O-rings periodically referring to Table 5.15 •
"Recommended Consumable Part Replacement Period".
•
•
White Upper O-ring: O-ring, PTFE (P/N S638-15025).
Black Lower O-ring: O-ring, 4DP10A (P/N S036-11209-84).
White O-ring
Top
Rounded
side
Bottom
Black O-ring
Figure 4.10 Replacing the Sliding Sample Injector O-rings
In addition, the O-ring between the injection block and the combustion tube must be
replaced periodically referring to "O-ring 4DP20" in Table 5.15 • "Recommended
Consumable Part Replacement Period".
CAUTION
Do not scratch the O-rings or the O-ring seat when replacing the O-rings.
To prevent gas leaks, install the o-rings (PTFE) in the correct orientation as
shown in Figure 4.10 when replacing the O-rings.
4.2.11 Replacing the Syringe Pump 8-port Valve Rotor
The fluororesin rotor of the syringe pump 8-port valve gradually becomes worn and
scratched after prolonged use, due to suspended particles in the samples. This wear
eventually causes leaks from the 8-port valve.
The following symptoms are associated with leaks from the 8-port valve and indicate that it
is necessary to replace the rotor.
•
•
•
Droplets of liquid around the 8-port valve (especially around the upper shaft).
Decreased analysis reproducibility.
Presence of bubbles in the syringe.
If the leakage is great, sample remaining in the tubing after being filling the syringe may
flow back into the sample container. This phenomenon is most likely due to a sample
tubing, flange connection problem.
TOC-LCSH/CSN
247
4.2
Periodic Inspections
CAUTION
Switch OFF the instrument before replacing the 8-port valve rotor.
Procedure
1.
The
mark on the 8-port valve interrupt plate indicates the orientation of the rotor
hole (stream direction). Take note of which port number the
mark is pointing
towards.
2.
Remove the nut using the provided wrench.
Rotor drive
component
mark
Interrupt plate
8-port valve
Wrench
Figure 4.11 Removing the Nut
3.
248
TOC-LCSH/CSN
Pull up to remove the rotor drive component. Hang it on the screw on the right side of
the plunger.
4.2
4.
Periodic Inspections
Loosen the retaining nut using the provided wrench.
Retaining nut
Wrench
Figure 4.12 Removing the Retaining Nut
5.
6.
Remove the spring-equipped rod.
Grasp the rotor with pliers and pull it out.
Rotor
Figure 4.13 Removing the Rotor
7.
8.
9.
Insert a new rotor, taking care that the rotor hole matches original orientation.
Reinsert the spring-equipped rod and tighten the retaining nut.
Replace the rotor drive component, and tighten the nut.
Note: Perform the syringe pump zero detection procedure before analysis.
Refer to Section 5.3.4 ""Maintenance" Screen" on page 297.
TOC-LCSH/CSN
249
4.2
Periodic Inspections
4.2.12 Replacing the CO2 Absorber for the Optional Carrier Gas Purifier
The NDIR baseline becomes unstable with a decrease in the carbon dioxide absorption in
the CO2 absorber for the carrier gas purifier. In addition, the baseline position rises and
reproducibility diminishes, making analysis impossible. It is necessary to replace the soda
lime when this occurs.
The soda lime replacement frequency depends on the frequency of analyses, quantity of
organic impurities in the carrier gas, and the TOC content of the samples. It is
recommended that the soda lime be replaced once every four months.
Soda Lime Replacement Procedure
CAUTION
The carrier gas pressure applied to the carrier gas purifier, CO2 absorber is
approximately 200kPa (29PSI). It is dangerous to perform this maintenance
procedure under these conditions. Lower the carrier gas pressure in the
instrument to atmospheric conditions before replacing the soda lime as follows.
• Turn the supply valve of carrier gas source OFF.
• Switch OFF the instrument.
Procedure
1.
Remove the elbow joints on the CO2 absorber for carrier gas purification, which is
located in the holder on top of the instrument.
2.
3.
4.
Invert the CO2 absorber and remove the screw cap.
Remove the used soda lime.
Refill the absorber container with about 500g of new soda lime, to reach about 5mm
from the interior screw threads.
CAUTION
Do not allow any soda lime to enter the tube in the center of the container when
refilling the CO2 absorber.
5.
Fill the hollow in the screw cap with quartz wool and screw the cap back on the
container.
CAUTION
To maintain an airtight seal, a rubber O-ring is placed between the container and
the screw cap. Inspect the O-ring to verify that it is not scratched or twisted, then
attach the cap.
250
TOC-LCSH/CSN
4.2
6.
Periodic Inspections
Using the elbow joints, connect the carrier gas purifier CO2 absorber to the two tubes
exiting the back of the instrument as follows.
• Tubing labeled "L": Affixed to the connection port of CO2 absorber container
labeled "L".
• Tubing labeled "S": Affixed to the connection port of CO2 absorber container
labeled "S".
CAUTION
Only tighten the nuts on the elbow joints by hand. Do not use tools.
7.
Place the CO2 absorber for carrier gas purification in the holder on top of the
instrument.
Note: Dispose of the used soda lime according to local industrial waste disposal
regulations (using an industrial waste manifest disclosing that the material
contains soda lime).
CAUTION
Soda lime is a corrosive chemical substance. Be careful not to touch it with bare
hands. For details, refer to Section 5.10 "Safety Data Sheets" on page 377.
4.2.13 Replenishing IC Reaction Solution
For the H Type, verify that there is sufficient IC reaction solution in the IC reaction solution
vessel before performing IC analysis. If not, replenish the IC reaction solution referring to
Section 3.1.13 "IC Analysis Preparations" on page 48.
CAUTION
The IC reaction solution is acidic. Use care not to spill or touch the fluid when
handling it. For details, refer to Section 5.10 "Safety Data Sheets" on page 377.
TOC-LCSH/CSN
251
4.2
Periodic Inspections
4.2.14 Replacing the Pump Head of the IC Reaction Solution Pump
The IC reaction solution pump is a roller type pump that uses a rotating roller to flatten the
rubber tube carrying the IC reaction solution, thereby feeding solution into the system. This
rubber tubing gradually deteriorates, requiring periodic replacement of the pump head.
The life of the rubber tube is generally about 300 hours of pump operation. It is
recommended that 300 hours be entered as the respective warning value in the
"Maintenance" screen.
CAUTION
The pump head and rubber tubing inside the IC reagent pump are filled with IC
reagent solution. This solution is acidic. Use care to avoid touching or spilling
the solution when changing the pump heads. For details refer to Section 5.10
"Safety Data Sheets" on page 377.
Replacement Procedure
Use the following procedure to replace the rubber tubing of the pump head.
1.
Grasp the front and rear stops of the pump head by hand. Pull the pump head (white
resin) from the pump body (black resin).
2.
Disconnect both of the yellow rubber tubes on the left side of the pump head from the
PTFE tubes.
3.
4.
Connect the new rubber tubing to the PTFE tubes of the pump head.
Re-place the pump head following the above procedure in reverse.
IC reagent
delivery pump
Pump head
Figure 4.14 Replacing the Pump Head of the IC Reaction Solution Pump
252
TOC-LCSH/CSN
4.2
Periodic Inspections
4.2.15 Replacing the Filler of the Optional POC Analysis CO2 Absorber
The CO2 absorber for POC analysis is filled with about 6 grams of lithium hydroxide
crystals, which has sufficient carbon dioxide gas absorbency for several hundred analyses
under normal conditions. Airflow resistance gradually increases with use and may become
excessive irrespective of adequate carbon dioxide absorbency.
Replace the lithium hydroxide crystals in the CO2 absorber with a new batch if analysis
values become unstable, or carrier gas flow becomes difficult. For the procedure on filling
the CO2 absorber with lithium hydroxide crystals, refer to section pertaining to placement
of the CO2 absorber for POC analysis in Section 3.1.14 "Preparation for POC Analysis" on
page 50.
CAUTION
•
•
•
Lithium hydroxide is a corrosive (strongly alkali) powder, use care not to spill or
touch it during handling.
Used lithium hydroxide crystals should be disposed of by a certified industrial
waste handler according to local industrial waste disposal regulations. It must be
clearly disclosed (using an industrial waste manifest) that the waste is lithium
hydroxide.
There are both anhydrous and hydrated forms of lithium hydroxide crystal.
Since the hydrated form is slightly inferior in carbon dioxide gas absorbency
than the anhydrous form, use anhydrous lithium hydroxide crystals to fill the
CO2 absorber.
The life of the CO2 absorber will be shortened by performing POC analysis on
samples with high concentrations of IC.
4.2.16 Replacing the Liquid in the B-Type Halogen Scrubber (Option)
Replace the liquid in the B-type halogen scrubber every three months with 0.05 mol/L
hydrochloric acid.
The stainless mesh for absorption can be used until it dissolves. Note that the ability to
absorb halogen stops after the stainless mesh for absorption has dissolved completely.
CAUTION
Hydrochloric acid is a deleterious substance and must always be handled with
care to prevent spills and contact with the skin. For details, refer to Section 5.10
"Safety Data Sheets" on page 377.
The vessel of the B-type halogen scrubber is made of glass. Handle the vessel
with care to prevent breakage due to impact with other objects.
The ability to absorb halogen stops if the amount of liquid in the B-type halogen
scrubber decreases enough to prevent the carrier gas from bubbling or if the
stainless mesh for absorption dissolves completely. Before starting analysis,
always verify that the liquid level is up to the height of the branching tube in the
vessel of the B-type halogen scrubber and the scrubber contains stainless mesh
for absorption.
TOC-LCSH/CSN
253
4.3
Autosampler (ASI-L) Maintenance
4.3
Autosampler (ASI-L) Maintenance
Maintenance of the ASI-L includes periodic inspection of the rinse bottle, sample catcher
and rinse pump.
4.3.1 Rinse Bottle Inspection
Perform the following inspections before conducting analysis with the ASI-L. If the
following inspections are not properly conducted, air will be drawn into the ASI-L injection
pump, preventing the delivery of rinse water.
•
Check the rinse water level
Verify that the rinse water in the rinse bottle is above the 2-liter level mark. Add water if
it is below this level.
•
Check the rinse tubing
Verify that the tip of the rinse tubing reaches nearly to the bottom of the rinse bottle.
Adjust the tubing depth if necessary.
Rinse Tubing
Rinse Bottle
Figure 4.15 Rinse Bottle Inspection
4.3.2 Sample Catcher Inspection
CAUTION
Corrosion of the instrument may occur if spilled sample is allowed to remain in
the sample catcher. Keep the sample catcher clean.
Examine the turntable (black plate) and the sample catcher tray below the turntable when
installing or removing the ASI-L vial rack. If they are wet or dirty, wipe them clean.
254
TOC-LCSH/CSN
4.3
Autosampler (ASI-L) Maintenance
4.3.3 Replacing the Pump Head of the Rinse Pump
The rinse pump is located inside the ASI-L and supplies rinse water to the rinse port. The
rinse pump is a roller type pump where a rotating roller flattens the rubber tubing carrying
the rinse water. This rubber tubing gradually deteriorates requiring periodic replacement.
The life of the rubber tubing is generally about 300 hours of pump operation.
Replacement Procedure
Use the following procedure to replace the rubber tubing on the pump head.
1.
2.
Remove the rectangular pump access cover on the back left side of the ASI-L.
3.
On the left side of the pump head, disconnect both of the yellow rubber tubes from the
PTFE tubes.
4.
5.
Connect the new rubber pump head tubing to the PTFE tubes.
Grasp the stops on the pump head by hand and pull the white resin, pump head from
the black resin, pump body.
Re-place the pump head following the above procedure in reverse and the replace the
pump access cover.
Pump Head
Pump Head
Figure 4.16 Replacing the Pump Head of the Rinse Pump
TOC-LCSH/CSN
255
4.4
8-Port Sampler (OCT-L) Maintenance
4.4
8-Port Sampler (OCT-L) Maintenance
4.4.1 Replacing the 8-Port Valve Rotor
The OCT-L uses a fluororesin 8-port valve rotor. The valve rotor may become worn or
scratched after prolonged use due to the suspended particles in the samples. This wear
eventually causes leaks from the 8-port valve.
The following symptoms are associated with leaks from the 8-port valve and indicate
that it is necessary to replace the rotor.
•
•
•
Droplets of liquid around the 8-port valve (especially, around the upper shaft)
Decreased analysis reproducibility.
Presence of bubbles in the TOC-L syringe.
If the leak is large, sample remaining in the tubing after the syringe has been filled may
flow back into the sample container. This is most likely due to a sample tubing or
flange connection problem.
CAUTION
Switch OFF the power before replacing to the 8-port valve rotor.
Replacement Procedure
1.
2.
Remove the 4 screws at the top of the OCT-L, and take off the cover.
Verify that the
Note:
3.
mark on the 8-port valve cover is directed toward port No.1.
If the mark is not directed toward port No.1, the instrument was not
shut down properly. If this is the case, turn the TOC-L on again, and
shut it down properly.
Remove the nut using the wrench supplied with the TOC-L.
Cover
Nut
8-port valve
Wrench
Figure 4.17 Removing the Nut
256
TOC-LCSH/CSN
4.4
4.
5.
8-Port Sampler (OCT-L) Maintenance
Remove the 8-port valve by pulling it downward.
Loosen the retaining nut using the provided wrench.
Retaining Nut
Figure 4.18 Removing the Retaining Bracket
6.
Note the orientation (toward port No. 1) of the flat surface of the spring-equipped rod.
Remove the spring-equipped rod and retaining nut.
7.
Note the orientation of the rotor hole position. Grasp the rotor with forceps, and
remove by pulling upwards.
Rotor
Figure 4.19 Removing the Rotor
8.
9.
Insert a new rotor, positioning the rotor hole to the original position.
Reinsert the spring-equipped rod and retaining nut with the flat surface directed
toward port No. 1. Tighten the retaining nut.
10. Replace the 8-port valve in its original position, and secure it using the nut.
11. Replace the cover of the OCT-L and secure it with four screws.
TOC-LCSH/CSN
257
4.5
TN Unit (TNM-L) Maintenance
4.5
TN Unit (TNM-L) Maintenance
Maintenance of the TNM-L includes periodic inspection of the ozone treatment unit
catalyst, chemiluminescence detector and ozone generator.
4.5.1 Replacing the Catalyst in the Ozone Treatment Unit
The ozone treatment unit breaks down ozone gas produced by the ozone generator. The
catalyst inside the ozone treatment unit must periodically be replaced.
Perform maintenance to the ozone treatment unit after stopping the instrument according to
Section 3.2.7 "Ending Analysis" on page 137.
CAUTION
The interior of the ozone treatment unit is heated to 50°C. Perform maintenance
only after cooling for at least two hours.
Replacement Procedure
Use the following procedure to replace the catalyst in the ozone treatment unit.
1.
Disconnect the tubing (Viton tubing) from each end of the ozone treatment unit and
pull out the ozone treatment unit in the upward direction.
Ozone exhaust
tubing
Ozone treatment
unit (right side of
the electric furnace)
Figure 4.20 Removing the Ozone Treatment Unit
258
TOC-LCSH/CSN
4.5
TN Unit (TNM-L) Maintenance
2.
Remove the larger diameter fluoro rubber plug and take out the used catalyst and
polypropylene packing material.
3.
Insert a small amount of new polypropylene packing material at the bottom of the
vessel and then fill with catalyst to about 2 cm below where the vessel hollows. Insert
another small amount of polypropylene packing material on top of the catalyst and
then reattach the fluoro rubber plug. (The amount of catalyst is about 150 g.)
About 2 cm
Gas inlet
Polypropylene
packing material
Catalyst
Wiring bands
Fluoro rubber plug
Gas outlet
Ozone treatment unit
Filling with catalyst
Figure 4.21 Filling the Ozone Treatment Unit with Catalyst
4.
Remove the ozone exhaust tubing that connects the detector exhaust port and the
ozone treatment unit inlet.
CAUTION
The ozone exhaust tubing must be replaced with a new one each time the
catalyst is replaced.
5.
Return the ozone treatment unit to its original position in the instrument and reconnect
the tubing to each end of the unit.
CAUTION
Used catalyst should be disposed of according to local industrial waste disposal
regulations. It must be clearly disclosed (using an industrial waste manifest) that
the catalyst contains manganese dioxide.
TOC-LCSH/CSN
259
4.5
TN Unit (TNM-L) Maintenance
4.5.2 Inspecting the Chemiluminescence Detector and Replacing the Ozone
Generator
The light receiving window of the chemiluminescence detector may become dirty with
components of the sample for measurement. Inspect the window contamination and
packing at least once a year.
Replace the ozone generator with a new one after the operation time exceeds 8000 hours.
Replacement of these parts must be carried out by an authorized Shimadzu service
engineer, or someone who has been properly trained in the procedure. Contact your
Shimadzu representative to request replacement.
Checking the Operation Time of the Ozone Generator
The operation time is displayed in the field to the right of the [O3 Generator] counter on the
"Maintenance" screen.
CAUTION
If the ozone generator is used after 8000 hours of operation, ozone generation
may not be sufficient for analysis or ozone may leak from inside the generator.
Replace the ozone generator without fail.
4.5.3 Replacing the NOx Absorber
The NOx absorber is used to absorb NOx gas generated by the TNM-L. Although the CO2
absorber used to purge the optical system of the NDIR detector is used in the NOx absorber
(the spent absorber from Section 4.2.6 "Replacing the CO2 Absorber" on page 242), this
CO2 absorber is still effective for NOx absorption.
During the annual replacement of the CO2 absorber used to purge the optical system of the
NDIR detector, replace the NOx absorber for the TNM-L with the used CO2 absorber from
the TOC-L.
Reference: Refer to Section 3.1.15 "TN Analysis Preparations (When Using the Optional TN Unit)" on
page 52 for the procedure of NOx absorber replacement.
Discarding the NOx Absorber (CO2 Absorber)
Place a request to an authorized industrial waste disposal service for disposal of the used
NOx absorber (CO2 absorber). Clearly indicate in the industrial waste material manifest
that the absorber contains soda lime.
260
TOC-LCSH/CSN
4.6
4.6
Troubleshooting
Troubleshooting
This section describes the error messages displayed on the TOC-L and the actions to
resolve the underlying causes.
4.6.1 Error Messages
The following error messages are presented as a blinking display in the title line, at the top
of the screen. The red LED Warning lamp also illuminates. Take the corrective actions
indicated in the table below.
Table 4.1• Error Message List 1
Error Message
Description
Remedial Action
Counter Over- Dilution Water
Volume
Actual amount of dilution water used
exceeds value set in "Maintenance"
screen.
Replenish the water in the dilution water
container. Then clear the Dilution Water Usage
Volume counter in the "Maintenance" screen.
Counter Over- Acid Volume
Actual amount of hydrochloric acid
used exceeds value set in
"Maintenance" screen.
Replenish the hydrochloric acid in the acid
container. Then clear the Acid Usage Volume
counter in the "Maintenance" screen.
Counter Over- Combustion
Tube Sample Injection
Volume
Actual volume of sample injected into
combustion tube exceeds value set in
"Maintenance" screen.
Either perform catalyst regeneration or replace
the catalyst and combustion tube. Then clear the
Combustion Tube Sample Injection Volume
counter in the "Maintenance" screen.
Counter Over- Syringe Stroke
Number
Actual number of syringe strokes
performed exceeds value set in
"Maintenance" screen.
Replace the plunger tip. Then clear the Syringe
Stroke Number counter in the "Maintenance"
screen.
ASI cover is open. Please
close the cover
The ASI-L sample cover is not installed
correctly.
Correctly install the ASI-L sample cover.
Close the ASI needle cover.
The ASI-L needle cover is open.
Counter Over- IC tubing
pump
The operation time of the tubing pump
for supplying IC reagent has exceeded
the value set on the "Maintenance"
screen.
Replace the tubing pump. After replacement,
reset the [IC tubing pump] counter on the
"Maintenance" screen.
Counter Over- ASI tubing
pump
The operation time of the ASI tubing
pump has exceeded the value set on the
"Maintenance" screen.
Replace the tubing pump. After replacement,
reset the [ASI tubing pump] counter on the
"Maintenance" screen.
Counter Over- 8-Port Valve
Operation Time
The number of operations of the 8-port
valve rotor has exceeded the value set
on the "Maintenance" screen.
Replace the 8-port valve rotor. After
replacement, reset the [8PV Ope. Counts.]
counter on the "Maintenance" screen.
Counter Over- O3 Generator
Operation Time
The operation time of the ozone
generator has exceeded the value set on
the "Maintenance" screen.
Perform maintenance on the ozone generator.
After maintenance is complete, reset the [O3
Generator] counter on the "Maintenance" screen.
TOC-LCSH/CSN
261
4.6
Troubleshooting
Table 4.1• Error Message List 1
Error Message
Description
Remedial Action
Counter Over- CO2 Absorber
The usage time for the CO2 absorber
has exceeded the value set on the
"Maintenance" screen.
Replace the CO2 absorber. After replacement,
reset the [CO2 Absorber] counter on the
"Maintenance" screen.
Counter Over- Stirrer Motor 1
(-8)
The operation time of the stirrer motor
has exceeded the value set on the
"Maintenance" screen.
Replace the stirrer motor. After replacement,
reset the corresponding [Stirrer] counter on the
"Maintenance" screen.
Counter Over- OCT1 8-Port
Valve Operation Time
The number of operations of the 8-port
valve for OCT-L (1) has exceeded the
value set on the "Maintenance" screen.
Replace the 8-port valve rotor for OCT-L (1).
After replacement, reset the [OCT-1 8PV Ope.
time] counter on the "Maintenance" screen.
Counter Over- OCT2 8-Port
Valve Operation Time
The number of operations of the 8-port
valve for OCT-L (2) has exceeded the
value set on the "Maintenance" screen.
Replace the 8-port valve rotor for OCT-L (2).
After replacement, reset the [OCT-2 8PV Ope.
time] counter on the "Maintenance" screen.
Carrier Gas Pressure is out of
range
The carrier gas supply pressure has
decreased below 170 kPa.
Check the carrier gas supply source (gas
cylinder) and tubing.
Unable to access the USB
storage.
A USB memory error has occurred.
Reinsert the USB memory. If the same error still
persists, replace the USB memory device with
another one.
8-Port Valve Operation Retry
has occurred.
A problem has occurred during 8-port
valve operation.
Servicing is required if this problem occurs
frequently, so contact your Shimadzu
representative.
Exchange the back-up battery.
The battery used in memory backup has
depleted.
Contact your Shimadzu representative as this
problem requires servicing.
There is a possibility that the
ASI Cover Sensor doesn't
work.
If the vial cover opened state is not
recognized although measurement has
been conducted for more than 200 vials,
the sensor may be faulty. This error may
also occur due to false recognition when
vials are changed while the power is
off.
Before starting measurement based on a
schedule, open the vial cover once and check that
an error message is displayed, to ensure that the
sensor is working correctly.
The CF Card is full
There is insufficient free space on the
built-in CF card used for storing data.
Export the analysis data on the CF card to an
external memory device because there is
insufficient free space remaining on the card.
Unable to access the CF card.
A problem has occurred with the builtin CF card used for storing data.
Contact your Shimadzu representative as this
problem requires servicing.
If the sensor is not working correctly, contact
your Shimadzu representative as this problem
requires servicing.
The following error messages are displayed in the middle of the screen. Take the corrective
actions indicated in the following table.
Table 4.2 • Error Message List 2
Error Message
Syringe Zero Point Correction
failed.
262
TOC-LCSH/CSN
Description
Syringe zero point correction could
not be performed. Syringe is not
properly installed.
Remedial Action
Properly install the syringe. Then execute
Syringe Zero Point Correction in the
"Maintenance" screen.
4.6
Troubleshooting
Table 4.2 • Error Message List 2
Error Message
Description
Remedial Action
Oven temperature too low.
The temperature of the electric
furnace has not risen sufficiently.
Wait for the oven temperature to rise before
executing the catalyst regeneration procedure.
No vial rack
Operation cannot continue because
there is no vial rack in the turntable.
Install a vial rack, and then execute the
operation.
Vial type mismatch.
The vial rack type set in the
parameters does not match the type
actually installed.
Verify the type of vial rack installed in the ASIL, and then set the vial rack type in the
"Parameters" screen.
The following error messages are displayed in the middle of the screen. The red LED
Warning lamp also starts blinking. Analysis cannot continue when these error messages are
generated. Take the appropriate corrective actions as indicated in the following table.
If the cause of the problem cannot be discovered, or if the same error message appears after
taking the indicated corrective actions, contact your Shimadzu representative.
When the following errors are generated, power to the instrument oven is automatically
stopped. When power to the oven is switched on again, wait until the temperature rises
before starting analyses
Displaying and Removing an Error Message
Table 4.3 • Error Message List 3
Error Message
Error!! FLASH ROM
Error!! Furnace Overheating
Error!! Furnace Temperature
Sensor
Error!! Carrier Gas
Error!! Syringe Position
Error!! Syringe Operation
Error!! Syringe zero point
detection
Error!! 8-Port Valve Position
Detection
Description
Remedial Action
An error occurred while writing to the Switch off power to the instrument. Contact your
memory circuit.
Shimadzu representative.
The oven became overheated.
With the power ON, wait approximately 20
minutes for the oven temperature to decrease then
switch OFF the instrument. After switching on the
power and running the instrument again, see if the
same error is generated.
The oven temperature does not rise. Switch off power to the instrument. After
switching on the power and running the
The carrier gas has stopped. (Causes instrument again, see if the same error is
may include a defective solenoid
generated.
valve or stoppage at the carrier gas
source.)
The syringe is not operating normally.
The syringe is not operating normally Switch off the instrument, and remove any foreign
due to clogging of the tubing
particles from the line, etc. After switching on the
connected to the 8-port valve, etc.
power and running the instrument again, see if the
same error is generated.
The syringe is not operating normally. Switch off the instrument. After switching on the
power and running the instrument again, see if the
same error is generated.
Switch off the instrument, and remove the rotor
The 8-port valve is not operating
normally due to clogging inside of the from the 8-port valve. Remove any particles
sample injector 8-port valve, etc.
found in the 8-port valve and wash valve.
TOC-LCSH/CSN
263
4.6
Troubleshooting
Table 4.3 • Error Message List 3
Error Message
Error!! TC Slider
Description
The TC slider is not operating
normally due to particles wedged
between the moving parts, etc.
Error!! IC Slider
The IC slider is not operating
normally due to particles wedged
between the moving parts, etc.
Error!! ASI Arm Vertical Position The ASI-L arm is not operating
Detection
normally in the vertical direction.
Error!! ASI Arm Vertical
The ASI-L arm is not operating
Movement
normally in the vertical direction.
Error!! ASI Arm Horizontal
The ASI-L arm is not operating
Position Detection
normally in the horizontal direction.
Error!! ASI Arm Horizontal
The ASI-L arm is not operating
Movement
normally in the horizontal direction.
Remedial Action
Switch off the instrument, inspect the slider and
remove any foreign particles from the slider
mechanism. Then switch on the power again.
Switch off power to the TOC-L instrument. After
switching on the power and running the
instrument again, see if the same error is
generated.
Since the problem is unrelated to the TOC-L main
unit, remove the ASI-L from the main unit, and
perform operations using the TOC-L main unit
alone until normal operation of the ASI-L is
restored.
Error!! ASI Turntable Position
The ASI-L turntable position could Switch off power to the TOC-L main unit. Make
Detection
not be detected. Either the turntable is sure the ASI-L is properly seated in the rack, and
not properly seated in the rack, or
remove any objects that may be blocking the
some object may be blocking a
position detection notch on the periphery of the
position detection notch on the
rack. After eliminating the cause of the problem,
periphery of the rack.
place the cover on the ASI-L, and switch on the
power to the instrument again.
Error!! TN Reactor Temperature The TNM-1 reactor temperature does Switch off power to the TOC-L main unit. After
not rise.
switching on the power and running the
instrument again, see if the same error is
generated.
Switch off the instrument, remove the rotor from
Error!! 8port Sampler -1
The OCT-L (1) is not operating
the 8-port valve in the OCT-L (1), remove any
Movement
normally due to entry of foreign
Error!! 8port Sampler -1 Position particles in the 8-port valve, etc.
particles found in the 8-port valve and wash the
Detection
valve.
Error!! 8port Sampler -2
The OCT-L (2) is not operating
Switch off the instrument, remove the rotor from
the 8-port valve in the OCT-L (2), remove any
Movement
normally due to entry of foreign
Error!! 8port Sampler -2 Position particles in the 8-port valve, etc.
particles found in the 8-port valve and wash the
Detection
valve.
Error!! Cooler Fan Stop
The cooling fan on the electronic
Switch off the instrument. Turn on the power
cooler has stopped.
again, operate the instrument, and verify whether
the same error occurs again.
Error!! ASI Emergency Stop
An ASI-L emergency stop occurred Switch off the instrument. Deactivate the ASI-L
(due to pressing of the emergency
emergency stop button and then turn on power to
stop button).
the instrument again.
264
TOC-LCSH/CSN
4.6
Troubleshooting
Table 4.3 • Error Message List 3
Error Message
Description
Remedial Action
Error!! Main Fan Stop
Error!! Defect safety relay of
Furnace
Error!! Furnace Power
The TOC-L exhaust fan has stopped. Switch off the instrument. Turn on the power
The electric furnace safety relay is
again, operate the instrument, and verify whether
not operating normally.
the same error occurs again.
The power supply of the electric
furnace is not operating normally.
Error!! Cooler Temp. Control
The electronic cooler temperature
control is not operating normally.
Error!! TOC Detector Temp.
The NDIR temperature control is not
Control
operating normally.
Error!! TOC Detector Motor
The NDIR motor is not operating
normally.
Error!! TOC Detector Memory
The NDIR memory is not operating
normally.
Error!! TOC Detector Connection A problem has occurred with the
NDIR connection.
Error!! TN Detector Temp.
The chemiluminescence detector
Control
temperature control is not operating
normally.
Error!! TN Detector Memory
The memory of the
chemiluminescence detector is not
operating normally.
Error!! TN Detector Connection A problem has occurred with the
chemiluminescence detector
connection.
Error!! TN Detector Fan Stop
The cooling fan of the
chemiluminescence detector is not
operating normally.
Error!! O3 Gas Flow Line Sensor The pressure sensor for the ozone
stream is not operating normally.
Error!! Sparge Gas Flow Line
A problem has occurred in the sparge
gas stream (pressure error).
Error!! Pressure Sensor 1
A problem with the pressure sensor
(for supply pressure) of the carrier
gas control unit was detected.
Error!! Pressure Sensor 2
A problem with the pressure sensor
(for carrier gas) of the carrier gas
control unit was detected.
Error!! Pressure Sensor 3
A problem with the pressure sensor
(for sparge gas) of the carrier gas
control unit was detected.
TOC-LCSH/CSN
265
4.6
Troubleshooting
When an error is generated, item and the date and time of its occurrence are displayed in
the Error Log. Error messages associated with Error List 1 and 2 are displayed in the Error
Status field. Displayed errors are removed from the screen by clearing them from this field.
Displaying the Error Log and Error Status
1.
Press the F5 [Maintenance] key in the "Initial Display" to display the "Maintenance"
screen.
2.
Press the F6 [Error Status] key in the "Maintenance" screen to display the Error Log
and Error Status.
Removing Error Status Items
Press the F6 [Clear Error] key to clear the error. The items in the Error Status field are
removed, along with the error message displayed at the top of the screen.
Clearing the Error Status field does not affect the Error Log, where a record of the errors
remains.
Deleting Error Log Items
Press the F3 [Clear Error Log] key to clear all of the items from the Error Log.
266
TOC-LCSH/CSN
4.6
Troubleshooting
4.6.2 Troubleshooting
4.6.2.1 TOC-L
(1)
An error message is displayed.
→Refer to error message.
(2) The Ready lamp will not light.
→ Refer to the "Background Monitor" screen to see which parameters are not
satisfied.
(3) The baseline remains over the auto zero range. Baseline position is "NO GOOD".
Does carrier
gas flow normally
to the analysis
cell?
NO
Carrier gas leak.
Repair the leak.
YES
Is dehumidifier
within the specified
temperature?
NO
The dehumidifier temperature
setting is bad.
YES
The infrared gas
detector (NDIR) is bad.
Contact a Shimadzu
representative.
Contact a Shimadzu
representative.
TOC-LCSH/CSN
267
4.6
Troubleshooting
(4)
The baseline is unstable.
Is carrier gas
flowing normally?
NO
Carrier gas leak.
YES
Was
the catalyst
replaced?
Repair the leak.
NO
Accumulated obstructing
substance.
YES
Is the
dehumidifier
operating
normally?
Replace the catalyst.
NO
The dehumidifier is bad.
YES
Are
surrounding
parameters (vibration,
temperature, power
voltage)
normal?
YES
The infrared gas
detector (NDIR) is bad.
Contact a Shimadzu
representative.
268
TOC-LCSH/CSN
Contact a Shimadzu
representative.
NO
External conditions are
adverse.
Eliminate the adverse
element.
4.6
(5)
Troubleshooting
Poor repeatability with standard solution.
Is the
standard solution
normal?
NO
Bad standard solution.
Prepare new standard
solution.
YES
Is the
sample injected
normally from injection
tube?
NO
Poor injection condition.
YES
Do
bubbles remain
in syringe? (especially
in dilution
analysis)
Adjust injector (*Section 3.1)
YES
Poor injection volume
repeatability.
Eliminate bubbles
(Section 4.5.2.3)
NO
Was plunger tip
replaced recently?
NO
Backlash of plunger tip.
YES
Does
carrier gas
sometimes leak from
the drain
bottle?
Replace plunger tip.
(Section 4.5.2.3)
YES
Low water level.
NO
Does the
poor repeatability
occur in the
TC or IC
circuit?
Replenish the water.
IC
IC reaction solution has
deteriorated.
Regenerate the IC reaction
solution.
TC
Was the
TC catalyst
regenerated?
NO
Insufficient regeneration of
theTC catalyst .
YES
Regenerate the TC catalyst.
TC catalyst deteriorated.
Replace the TC catalyst.
TOC-LCSH/CSN
269
4.6
Troubleshooting
(6)
No peaks appear after sample injection.
Is
sample
injected into TC
combustion tube or IC
reaction vessel?
NO
(confirm
Poor injection.
visually)
Correct the injection
condition.
YES
Is carrier gas
always flowing from
the drain
bottle?
YES
Is the
level of the water
normal in the
drain bottle?
NO
NO
Low water level.
YES
Was membrane filter
replaced?
Replenish water.
NO
Clogged membrane filter.
YES
Bad infrared gas
detector (NDIR).
Replace the membrane filter.
Large resistance downstream
of dehumidifier.
Contact a Shimadzu
representative.
Contact a Shimadzu
representative.
Reference
The following procedure can be used to check whether carrier gas is flowing to the infrared
gas analyzer. However, this procedure cannot determine the existence of minute gas leaks.
Note that checks using this procedure cannot be performed when the TNM-L is connected
to the instrument.
Procedure
270
1.
Block the carrier gas flow by firmly folding over the flexible tubing labeled with an
"L" that is connected to the CO2 absorber, which is located in the holder on top of the
instrument.
2.
If carrier gas bubbles out from the bottom of the drain tubing inside the drain
container, which is located on the left side of the instrument, this means that carrier
gas is flowing to the infrared gas analyzer.
For the H Type instrument, whether carrier gas is flowing to the IC reaction vessel can
be determined by visually checking for bubbling of IC reagent in the IC reaction
vessel.
TOC-LCSH/CSN
4.6
Troubleshooting
Reference
When using a TOC high sensitivity catalyst, peaks will not be output or the peak shape will
deteriorate if the catalyst filling in the combustion tube becomes loose (rises up). In this
case, remove the combustion tube from the instrument and check the filling state of the
catalyst. If the filling height is more than 110 mm, use the catalyst filling rod to push the
catalyst down from the top of the combustion tube to a height of 110 mm.
(7) If the NPOC measurement value is higher than anticipated
When performing sample acidification and sparging in NPOC measurement using the
syringe pump type sample injector in the TOC-L, the acid used for sample acidification
must completely fill the PTFE tubing used to supply the acid. If bubbles are present in the
tube, acid addition with respect to the sample will not occur properly and will lead to only
partial IC removal. This will result in a higher NPOC measurement value than anticipated.
This problem will occur noticeably if the connection between the PTFE tubing for
supplying acid and the 8-port valve decreases in airtightness. If this is the suspected cause,
executing the stream bubble removal function, retightening the bush on the connection of
the PTFE tubing for supply acid, and replacing the rotor in the 8-port valve are all effective
methods to resolve this problem.
In addition, it is possible to check whether any sample has acidified inside the syringe by
measuring the pH level of discharge from the TOC-L drain tubing with pH test paper.
TOC-LCSH/CSN
271
4.6
Troubleshooting
4.6.2.2 ASI-L
(1)
The ASI-L does not operate.
Is the connection
cable connected
properly?
NO
Incorrectly connected cable
Properly connect the cables
YES
Bad electrical system
Contact a Shimadzu
representative.
(2)
Rinse water is not delivered from the rinse port.
Is there
sufficient
rinse water in rinse
NO
water bottle?
Insufficient rinse water
YES
Is the
rinse tubing
properly inserted into
the rinse water
bottle?
YES
The rinse pump is bad
Contact a Shimadzu
representative.
272
TOC-LCSH/CSN
Replenish the rinse water.
NO
The rinse tubing is not properly
inserted into rinse water bottle.
Properly insert the tubing into
the rinse water bottle.
4.6
(3)
Troubleshooting
Repeatability is poor.
Is there
any material
adhering to the
sample
needle?
YES
Deteriorated reproducibility
due to contaminants
NO
Is there
a leak at the
connection of sample
needle and ASI
sample
tubing?
Remove the obstruction from
the opening at the tip of the
sample needle.
YES
Air is drawn in at the
connection.
NO
Properly reconnect the tubing.
Poor reproducibility caused
by the TOC-L
Refer to Troubleshooting
4.6.2.1 TOC-L, item (5).
4.6.2.3 8-Port Sampler OCT-L
(1)
OCT-L does not operate.
Is the connection
cable connected
properly?
NO
Incorrectly connected cable
YES
Connect the cables properly.
Electrical system is defective.
Contact your Shimadzu
representative.
TOC-LCSH/CSN
273
4.6
Troubleshooting
(2)
Repeatability is poor.
Is any foreign
material adhering to
the sample tubing?
YES
Deteriorated reproducibility
due to contaminants
Eliminate blockage at the tip of
the sample tubing.
NO
Is the leakage
present at the 8-port valve
and sample tubing
connection?
YES
Connection is leaking.
Connect the tubing properly.
NO
Poor reproducibility caused
by the TOC-L
Refer to Troubleshooting
4.6.2.1 TOC-L, item (5).
4.6.2.4 Remedial Actions for Poor Repeatability
Remedial Action for Poor Sample Injection
The status of the sample discharge from the TC or IC sample injection tubing has a large
influence on repeatability. The sample should be injected as vertically as possible onto the
TC catalyst or into the IC reaction vessel. If the sample is scattered or injected obliquely,
detach the sample injection tubing from the slider, and remove any obstruction that may be
adhering to the opening at the tip of the sample tubing.
Appropriate
Unacceptable
(oblique spray)
Unacceptable
(scattered spray)
Figure 4.22 Sample Injection Patterns from Sample Tube
Ensure that the tip of the tubing does not protrude beyond the bottom surface of the slider.
The O-ring or other seal parts will be scratched if the tubing protrudes, resulting in gas
leaks. The sample is not properly injected unless the tip of the tubing extends into the
depression in the bottom of the slider.
Check the state of the injection for TC analysis by looking through the TC combustion
tubing while it is attached to the instrument. The sample injection tubing can be detached
from the slider, and water can be injected for inspection using the operation check mode in
the "Maintenance" screen.
274
TOC-LCSH/CSN
4.6
Troubleshooting
Salt or other substances adhering to the tip of the tubing after rinsing can allow large
droplets of sample to remain on the tip of the tubing after injection. A deformed tip on the
sample injection tubing (a beard-like protrusion for example) may cause the sample to be
injected obliquely. In either case, repeatability is adversely affected and it is recommended
that the sample injection tubing be replaced. Another option available only if there is
sufficient length of tubing remaining, is to use a sharp cutting tool, at a 90° angle, to cut off
2 - 3mm from the tip of the currently used sample injection tubing.
Tube
Bushing
Packing (spacer,
washer, gasket)
Approximately
2 - 2.5mm
Figure 4.23 Slider Assembly
Remedial Action to Eliminate Bubbles Inside the Syringe
Small bubbles that adhere to the inside of the syringe by the plunger tip will have little
effect on analysis values. Larger bubble inside the syringe however, will affect values,
normally resulting in poor repeatability. Large bubbles are easily formed inside of a dirty
syringe. This is evident when sample is mixed with dilution water in the syringe and when
sparging with carrier gas inside the syringe for IC removal pretreatment for NPOC analysis.
In this case, detach the syringe from the syringe pump. Repeatedly fill the syringe and
discharge laboratory glassware detergent to wash the inside of the syringe. Then draw in a
full-stroke volume of the cleaning agent and let it sit for about 20 minutes (overnight if it is
extremely dirty). Thoroughly rinse away all of the detergent and reattach the syringe to the
syringe pump.
Decreased Repeatability Due to Plunger Tip Backlash
The plunger tip, as a consumable item, and as it is used, it wears in the following ways.
(1) The surface of plunger tip becomes worn, and the seal between plunger tip and the
inside of the glass syringe barrel deteriorates, allowing slight amounts of water to leak
out with vertical movements of the plunger.
(2) The contact site of the plunger tip and plunger becomes loose, causing a slight
backlash with vertical movement of the plunger.
As the above conditions start to occur, repeatability of sample injection volume decreases,
resulting in diminished analysis repeatability. Item (2) above, rapidly leads to decreased
repeatability. Since it is very difficult to determine backlash by inspecting movement of the
plunger tip, inspect as follows.
Before sample injection, observe the wash injection used to replace the previous sample in
the syringe and flow line with the new sample. After injection, if a droplet forms at the tip
of the injection tubing and increases in size, there is a strong possibility that backlash has
increased. The remedial action in this case is to replace the plunger tip.
Note: The effect of backlash increases with smaller sample injection volumes. Poor results
might be obtained with a sample injection volume of 10µL, while the effect might be
negligible with a 100µL sample injection volume.
TOC-LCSH/CSN
275
4.6
Troubleshooting
4.6.2.5 Corrective Action for Combustion Tube Breakage Inside the Electric Furnace
Allow the electric furnace to cool to room temperature for at least six hours after switching
off the power supply by shutting down the instrument and then perform corrective
measures according to the following procedure.
1.
By reversing the procedure described in "Connecting the Combustion Tube" (Section
3.1.3), remove the sample injector from the instrument together with the broken upper
end of the combustion tube.
2.
With the utmost care to avoid injury, remove the broken upper end of the combustion
tube from the sample injector.
3.
Remove the bottom end of the combustion tube from the cooling tube coupling,
loosen the two screws that secure the cooling tubing unit, and remove the cooling
tubing unit from the instrument.
4.
With the utmost care to avoid injury, remove any catalyst and broken pieces of
combustion tube that have fallen inside the instrument.
CAUTION
Allow the electric furnace to cool to room temperature for at least six hours after
switching off the power supply by shutting down the instrument before
performing maintenance on the combustion tube or catalyst. Burns may result if
this task is attempted when the furnace is at a high temperature.
Combustion tubes are made of quartz glass. Always wear protective leather
gloves when handling combustion tubes to prevent injuries due to breakage.
276
TOC-LCSH/CSN
5
5
Reference Materials
This chapter provides technical information related to the principles of analysis, screen
descriptions, standard accessories, specifications and installation instructions for
relocating the instrument.
5.1
Principles of Analysis
The analysis principles for TC, IC, POC, NPOC, TOC and TN analysis are
described in this section.
5.2
Analysis-Related Technical Information
Summarizes technical information related to analysis, including peak area
analysis, calibration curves, etc.
5.3
Screen Descriptions
Describes the items displayed in the "Initial Display", "Background Monitor"
screen, "Maintenance" screen, etc.
5.4
Specifications
Specifications for the TOC-LCSH/CSN main unit, autosampler, TN unit and the
various optional kits are listed here.
5.5
Standard Accessories
The standard accessories list is contained in this section.
5.6
Special Accessories
The optional accessories list is contained in this section.
5.7
Consumable Parts List
The consumable parts are listed in this section.
5.8
Maintenance Parts List
The maintenance parts are listed in this section.
5.9
Installation
The installation site requirements and installation procedure for relocating the
instrument are described here.
5.10 Safety Data Sheets
55
Material Safety Data Sheets are included for hydrochloric acid, phosphoric acid,
IC regent, the CO2 absorber, ceramic fiber and catalyst platinum black.
5.1
Principles of Analysis
5.1
Principles of Analysis
There are two types of carbon present in water: organic carbon and inorganic carbon.
Organic carbon (TOC) bonds with hydrogen or oxygen to form organic compounds.
Inorganic carbon (IC or TIC) is the structural basis for inorganic compounds such as gas
carbonates and carbonate ions. Collectively these are referred to as total carbon (TC) and
have the relationship TOC=TC-IC.
Nitrogen is also found in water in two types: Organic and inorganic. The sum of these is
referred to as total nitrogen (TN).
The principles underlying TOC and TN analysis are explained in the following sections.
5.1.1 Principle of TC (Total Carbon) Analysis
In the TOC-L, carrier gas is controlled using a pressure regulator and mass flow controller.
Carrier gas flows at 150mL/min to the combustion tube, which has been filled with an
oxidation catalyst and heated to 680°C. The TC of a sample is burned in the combustion
tube to form carbon dioxide. The carrier gas, containing the carbon dioxide and other
combustion products, flows from the combustion tube to a dehumidifier (electronic
dehumidifier), where it is cooled and dehydrated. Then it passes through a halogen
scrubber before it reaches the cell of a non-dispersive infrared NDIR gas analyzer, where
the carbon dioxide is detected. The analog detection signal of the NDIR forms a peak, and
the area of this peak is measured by a data processor.
The peak area is proportional to the TC concentration of the sample. Therefore, when a TC
standard solution has been analyzed to create a calibration curve equation expressing the
relationship between TC concentration and peak area, the TC concentration in the sample
can be calculated.
278
TOC-LCSH/CSN
5.1
Principles of Analysis
5.1.2 Principles of IC (Inorganic Carbon) Analysis
There are two methods available for measuring IC with the TOC-L, analysis within the
injection syringe and using the optional IC reactor. In either case, the IC comprises the
carbon within carbonates, hydrogen carbonates and in dissolved carbon dioxide.
Defining IC
The IC (inorganic carbon) in TOC analysis refers to carbon contained in the carbon dioxide
dissolved in water and that found in carbonates. By acidifying the sample with a small
amount of hydrochloric acid to obtain a pH less than 3, all the carbonates produce carbon
dioxide (CO2) according to the following reaction.
Me2CO3 + 2HCl --> CO2 + 2MeCl + H2O
MeHCO3 + HCl --> CO2 + MeCl + H2O
The carbon dioxide and dissolved carbon dioxide in the sample are volatilized by bubbling
(sparging) air or a gas that does not contain nitrogen or carbon dioxide through the sample.
Analysis Using the IC Reaction Vessel (H Type and N Type with Optional IC
Reactor Kit)
The TOC-L IC reactor kit allows for sparging the IC reaction solution (acidified reaction
liquid) with carrier gas. Only the IC of the sample, injected into the IC reaction vessel, is
converted to carbon dioxide and detected by the NDIR.
Analysis Within the Syringe (N Type)
The sample is acidified to pH 3 or lower with HCl inside the syringe. The sample is sparged
with carrier gas and only the IC in the sample is converted to carbon dioxide, and detected
by the NDIR.
TOC-LCSH/CSN
279
5.1
Principles of Analysis
5.1.3 Principle of NPOC (Non-Purgeable Organic Carbon) Analysis
After acidifying the sample by adding acid to pH 2 to 3, sparge gas is bubbled through the
sample to eliminate the IC component. The TC remaining in the sample after sparging is
measured to determine total organic carbon, and the result is generally referred to as TOC.
However, in the TOC-L, this analysis value is referred to NPOC to distinguish it from the
TOC value obtained by the difference between TC and IC. NPOC stands for non-purgeable
organic carbon and refers to the non-volatile organic carbon contained in a sample.
NPOC and TOC (obtained by IC elimination) described in the TOC-related standard
methods and referred to in water quality-related test methods (JIS, ASTM, EPA, EN) are
identical. If the sample contains purgeable organic substances, this component can be lost
during the sparging process. Consequently, when the sample contains purgeable organic
substances, TOC should not be measured by the NPOC method. If the dissolved purgeable
organic component in the water sample is large, the amount volatilized during sparging is
relatively small. Generally, the amount of purgeable organic substances in natural
environmental water, public water and purified water is small, so NPOC is referred to as
TOC.
Table 5.1 • Residual Rate of Volatile Organic Substances using Sparging
(Nitrogen Gas)
Organic Substance
280
Pre-Sparging Conc.
Post-Sparging
(ppm)
Conc. (ppm)
Methanol
117. 5
116
98.6
Ethanol
106.5
105
98.5
Isopropyl alcohol
129
127
98.5
n-butyl alcohol
117
115
98.3
Acetone
106
101
95.3
Acetaldehyde
130
117
90.0
Ethyl acetate
102
88
86.3
Tyrosine
117
116.5
99.5
Benzene
85
2.5
2.9
Cyclohexane
79
2
2.5
TOC-LCSH/CSN
Residual Rate (%)
5.1
Principles of Analysis
5.1.4 Principle of POC (Purgeable Organic Carbon) Analysis
POC analysis refers to the analysis of the organic component of the TOC that is volatilized
during the sample sparging for NPOC analysis. Accordingly, NPOC+POC is equivalent to
TOC. POC analysis is performed as follows.
The sparge gas containing the volatilized CO2 and POC component of the sample is
directed to the lithium hydroxide-filled CO2 absorber to eliminate the CO2 that was
converted from the IC in the sample. The gas that still contains the POC component of the
sample then passes through the combustion tube to be oxidized. CO2 is released during
oxidation and is detected in the NDIR. Data processing is conducted in the same manner as
for TC.
POC is not precisely defined. Factors that determine whether or not, or to what degree a
volatile organic carbon is volatilized during sparging include the type of organic
compound, the gas/liquid contact with the sparge gas as well as the ambient temperature
during sparging. Since the organic component in the aqueous solution is the target of
analysis, an organic compound that is highly soluble in water, for example methanol and
ethanol, is not easily volatilized by sparging, almost no peak is generated.
Organic compounds with little solubility in water, such as methylene chloride and
chloroform, generate a sharp peak for POC analysis. There are also compounds such as
acetone and methyl isobutyl ketone which over a long period, generate extremely broad
peaks with tailing and no specific end time.
The lithium hydroxide-filled CO2 absorber eliminates the carbon dioxide that was
generated along with the POC substances. Therefore, POC components, such as esters, that
are easily caught in the CO2 absorber show low values. POC results obtained using this
technique are not absolute. The user should take all the above factors into consideration
when analyzing for POC using this instrument.
TOC-LCSH/CSN
281
5.1
Principles of Analysis
5.1.5 Principles of Measuring TOC
The TOC-L employs the following 3 methods for TOC analysis.
•
TC-IC Method
•
NPOC Method
•
POC+NPOC Method
TC-IC Method
In this method, TOC is determined by the difference between the TC and IC analysis
values. NPOC analysis is generally used and is recommended for samples that contain
more IC than TOC (samples where TC consists almost entirely of IC). The TOC value
determined by difference includes errors associated with both the TC and IC analyses,
resulting in a large error in the TOC value. It is recommended that the NPOC analysis
method be used in these instances.
Since detection accuracy decreases, it is also advisable to use the NPOC method if the IC
concentration in the sample exceeds 10ppm for TOC/TN catalyst and 5ppm for high
sensitivity catalyst.
NPOC Method
This is the most widely used method of TOC analysis. There is a tendency for samples that
become foamy during sparging to partially form bubbles and flow out of the syringe, along
with the concentrated TOC content of the sample, thus leaving a smaller concentration of
TOC in the syringe. The TC-IC method is recommended for samples that would foam
during the sparging process.
Moreover, since TOC cannot be correctly measured in samples that coagulate or precipitate
when acidified, use the TC-IC method.
POC+NPOC Method
This method is used when the amount of POC existing in the sample cannot the
disregarded.
5.1.6 Principles of Measuring TN (Total Nitrogen)
When a sample is introduced into the combustion tube (furnace temperature 720°C), the
TN in the sample decomposes to become nitrogen monoxide. Nitrogen gas does not
become nitrogen monoxide at this time. The carrier gas, which contains the nitrogen
monoxide, is cooled and dehumidified by the dehumidifier (electronic dehumidifier). Then
it enters a chemiluminescence gas analyzer, where the nitrogen monoxide is detected. The
detection signal from the chemiluminescence gas analyzer generates a peak and the TN
concentration in the sample can then be measured.
Note:
TN Detection Rate
In TN analysis, the state (crystalline state) in which TN exists in the sample
greatly affects the TN detection rate. Nitrogen contained in nitrates, nitrites,
ammonia and the majority of organic nitrogen compounds exhibit high detection
rates. Conversely, some organic nitrogen such as the nitrogen contained in
hydrazines, pyrazolones, and azide compounds, have detection rates ranging
from 10% to 60%, depending on the concentration.
282
TOC-LCSH/CSN
5.2
5.2
Analysis-Related Technical Information
Analysis-Related Technical Information
5.2.1 Peak Area Analysis
When a sample is introduced, the TOC-L automatically detects the beginning and end of
each peak produced and calculates the peak areas. Detection of the beginning and end of
each peak is based on the slope of the tangent, which changes moment to moment. Peak
detection begins when that slope exceeds a predetermined value and ends when a negative
slope falls below a specified value.
Note:
• Separated Peaks: In TC analysis, multiple peaks may occur when a large
quantity of sample is injected. Only the end of the last peak is detected. Total
area of the multiple peaks is calculated.
• Baseline Correction: Baseline correction is performed for peaks produced
with fluctuating baseline to obtain the correct peak area.
Figure 5.1 Determining Peak Area
5.2.2 Peak Shape
Multiple peaks are especially noticeable using the high sensitivity catalyst with sample
injections greater than 100µL.
As sample is injected onto the catalyst, the easily volatilized organic substances and the
crystalline organic substances are combusted at different rates. This causes carbon dioxide
to be generated multiple times, resulting in the formation of multiple peaks. Easily
volatilized organic substances are organic compounds that are volatilized with water when
an aqueous solution of the compounds is heated. Ethanol is an example of such a
compound. Crystalline organic compounds remain in a solid form following the heating of
an aqueous solution of the compound. An example of such a compound is glucose.
The injection state of the sample also has an effect on peak shape. If a portion of the sample
is injected into the center of the combustion tube while another portion is injected at the
periphery, combustion may occur at different times, resulting in multiple peaks.
Peak shape does not affect the analysis results. Even if multiple peaks do occur due to the
type of organic substance or injection location mentioned above, the TOC-L calculates the
total area of the peaks generated to determine the TOC (or TC) accordingly.
TOC-LCSH/CSN
283
5.2
Analysis-Related Technical Information
5.2.3 Calibration Curves
5.2.3.1 Types of Calibration Curves
1-point and 2-point Calibration Curves
The output signals of the TOC-L are linearized. There are almost no factors in the reaction
systems of the TC/TN combustion and IC reaction components that might cause the
concentration-output characteristic to deviate from linearity. Consequently, calibration
curves are normally generated as 1-point curves consisting of 1 span point, or 2-point
curves consisting of 1 span point and the zero point.
The concentration of TC and IC, or of TN vary with standard solutions prepared with pure
water. A calibration curve generated using concentrations greater than 50 - 100mg/L will
pass very close to the zero point. Thus, it is practical to generate a 1-point calibration curve
in this case.
Use a 2-point calibration curve when the concentration TC and IC or TN in the pure water
used to prepare the standard solutions cannot be disregarded with respect to the standard
solution concentration. For information on handling of this type of curve, refer to Section
5.2.3.2 "Shifting of Calibration Curves" on page 285.
Multi-point Calibration Curves
Calibration curves can be generated using up to 10 points. Calibration curves consisting of
3 or more points can be generated as a point-to-point curve or as a regression line using the
least squares method. With the least squares regression curve, a correlation coefficient is
displayed.
Multi-point Calibration Curve with Diluted Solution
This is a function for generating multi-point calibration curves by diluting the standard
solution. Using this function enables the generation of a multi-point calibration curve with
a single standard solution. For details on the setting method, refer to the calibration curve
generation screen.
The multi-point calibration curve with diluted solution can be used with the TC, IC (CSH
only), and TN analysis types.
284
TOC-LCSH/CSN
5.2
Analysis-Related Technical Information
5.2.3.2 Shifting of Calibration Curves
Shift to Origin
This function is used when the amount of TC and IC or TN in the pure water used for
standard solution preparation cannot be ignored with respect to the standard solution
concentration. A correction must be made by shifting the calibration curve in a parallel
fashion so that it passes through the origin. This accounts for the TC and IC, or TN
concentration in the water used for standard solution preparation.
When water containing 0.5mg/L TC is used to prepare a 10mg/L TC standard solution
(actually 10 + 0.5mg/L TC), a 2-point calibration curve appears as shown by the solid line
in Figure 5.2. If this curve is used as is, the sample analysis values will always show a value
0.5mg/L less than the true value. By shifting the calibration curve so that it passes through
the origin, as shown by the broken line in Figure 5.2 "Shifting of Calibration Curve" on
page 285, the calibration curve deviation is effectively corrected.
When there is a system blank, the measured value is greater by the amount of the system
blank. In most cases, analysis error due to the TC or TN content in the water used in
preparing standard solutions is much greater than the system blank value. Correction of the
curve according to the TC/TN content in the standard solution, preparation water produces
satisfactory analyses. By this method, the analysis value obtained for a system blank, would
be greater than zero by the amount of this blank value.
The system blank refers to the peak obtained by measuring water that contains absolutely
no carbon (water with zero TC). This instrument allows shifting of calibration curves only
to the extent of the system blank value. The system blank peak height varies with such
factors as the system configuration and the type of catalyst.
Shift to Blank Point
This shift procedure is performed in high sensitivity analysis where the system blank value
could have an effect on the analysis value.
Peak Area Value
By selecting the shift-to-blank point option, a TC blank check analysis is performed using
the same injection volume that will be used in the analysis. The calibration curve zero point
is shifted to the TC blank check value.
0
(0.5)
TC Concentration (mg/L)
10
(10+0.5)
Figure 5.2 Shifting of Calibration Curve
TOC-LCSH/CSN
285
5.2
Analysis-Related Technical Information
5.2.4 Sparging During Standard Solution Analysis
For standard solutions that have a TC concentration so low as to be affected by the amount
of dissolved carbon dioxide in the standard solution, perform analysis of the standard
solution after it has been sparged with carrier gas. The dissolved carbon dioxide is
eliminated by sparging and will no longer affect the concentration of the standard solution.
The amount of dissolved carbon dioxide in the water used for standard solution preparation
is affected by factors such as water purification method, length and condition of storage,
and the concentration of carbon dioxide in the atmosphere. Even if the dissolved carbon
dioxide concentration in the water is low, the process of preparing the standard solution it
may expose it to the atmosphere. Refer to "Table 5.2 • CO2 Content (ppm) in Distilled
Water Equilibrated with Atmosphere Temperature (°C)" which presents the dissolution
rates of atmospheric carbon dioxide in water.
In any case, both the concentration of the standard solution and the concentration of TOC
contained in the water must be taken into consideration when deciding whether to use the
sparging function. Use of sparging is indicated if the TOC contained in the water is low
enough to not substantially affect the standard solution concentration, but not low enough
to be ignored.
Note:
Do not use sparging with IC standard solutions as sparging decreases the IC
concentration.
Table 5.2 • CO2 Content (ppm) in Distilled Water Equilibrated with Atmosphere
Temperature (°C)
Atmospheric CO2
0
5
10
15
20
25
30
0.030
1.00
0.83
0.79
0.59
0.51
0.44
0.38
0.033
1.10
0.91
0.76
0.65
0.56
0.48
0.42
0.044
1.47
1.22
1.02
0.87
0.74
0.64
0.56
(vol%)
The above CO2 content can be converted to IC using the following equation.
IC (ppm) = CO2 (mg/L) x 0.27
5.2.5 Automatic Selection of the Optimal Calibration Curve
The TOC-L has the ability to automatically select which calibration curve will be used to
determine the sample value. Up to 3 calibration curves can be specified in the
"Measurement Parameters" screen. If more than one calibration curve is listed, the TOC-L
uses the following scenarios to determine the optimum calibration curve for analysis.
Procedure
1.
286
TOC-LCSH/CSN
Analysis is performed using the calibration curve designated as Calib. (1st).
5.2
Analysis-Related Technical Information
Selection Result
(1)
If the sample value is less than the concentration of Calib. (1st), and greater than the
conc of Calib (2nd), the first calibration curve is used:
Conc. of 1st Calibration Curve > Measured Value > Conc. of 2nd Calibration Curves →
First calibration curve is used.
(2)
When the concentration of Calib (2nd) is less than Calib. (1st), a sample value that is
less than both will be calculated using the lower concentration of Calib. (2nd):
Conc. of 1st Calibration Curve > Conc. of 2nd Calibration Curve > Measured Value →
2nd Calibration Curve is used.
(3)
When three calibration curves are specified in the "Measurement Parameters" screen,
the calibration curve that is closest to the sample value without being less will be the
one used for calculation of the result.
Conc. of 1st Calibration Curve > Conc. of 2nd Calibration Curve > Measured Value >
Conc. of 3rd Calibration Curve → 2nd Calibration Curve is used.
Conc. of 1st Calibration Curve > Conc. of 2nd Calibration Curve >
Conc. of 3rd Calibration Curve > Measured Value → 2nd Calibration Curve is used.
(4)
If the sample value is greater than the concentration of Calib. (1st), and the
concentration of Calib. (2nd or 3rd) is greater than the concentration of Calib. (1st):
Conc. of 2nd or 3rd Calibration Curve > Measured Value > Conc. of 1st Calibration Curve →
2nd or 3rd Calibration Curve is used.
(5)
If the measured value is greater than the concentration of the first calibration curve
and the concentrations of the other two calibration curves (2nd or 3rd) are greater than
the concentration of the first calibration curve:
Analysis is first performed using the calibration curve with the lower concentration of
the other two.
Measured Value > Conc. of 2nd or 3rd Calibration Curve > Conc. of 1st Calibration Curve →
2nd or 3rd Calibration Curve is used.
Note:
By setting the concentration ratio between calibration curves to a factor of
approximately 10, this function can be effectively utilized to enable analyses
covering a wide range of concentrations.
Example: Calib. (1st): 10ppm, Calib. (2nd): 100ppm, Calib. (3rd): 1000ppm
Considerations for Auto-select Function
•
•
•
•
The above processing does not change even if multi-point calibration curves are
included.
When the number of analyses is set to more than one, the above determination is
made using the measured value of the first analysis.
Since analysis always begins from the first calibration curve, set the most-used
calibration curve in this position.
The priority of the second and third calibration curves is determined on the basis of
the calibration curve concentrations and the sample concentration.
TOC-LCSH/CSN
287
5.2
Analysis-Related Technical Information
5.2.6 Automatically Changing the Injection Volume
If Automatically Change Injection Volume (Auto Inj. Vol. Change) item is set to ON on the
"Conditions - Measurement Conditions" screen, the Automatically Change Injection
Volume function is activated.
Automatically Change Injection Volume Function
If the analysis results exceed the concentration of the calibration curve, the injection
volume is automatically changed so that, based on the analysis results, the peak area value
corresponds to around 80% of the calibration curve, then analysis is performed again.
Points to Note about the Automatically Change Injection Volume Function
•
•
•
•
If multiple analyses have been set, the judgment described above is made based on
the results of the first analysis.
When TN simultaneous analysis or POC/NPOC common injection analysis is ON,
this function is not used.
If the Automatically Select Optimal Calibration Curve function is used, it is that
function that has priority.
If the automatic injection volume change function is executed, the analysis
parameters are changed and analysis is started again with the data prior to that point
excluded. Since counting of the number of injections is started again from the point
where the analysis parameters are changed, the analysis takes some time.
5.2.7 Automatically Changing the Dilution Factor
If automatic changing of the dilution factor is set to ON on the "Conditions - Measurement
Conditions" screen, the Automatically Change Dilution Factor function operates.
Automatically Dilution Factor Change Function
If the analysis results exceed the concentration of the calibration curve, the dilution factor
(integer) is automatically changed so that, based on the analysis results, the peak area value
corresponds to around 80% of the calibration curve, then analysis is performed again.
Points to Note about the Automatically Change Dilution Factor Function
•
•
•
•
•
288
If multiple analyses have been set, the judgment described above is made based on
the results of the first analysis.
When TN simultaneous analysis or POC/NPOC common injection analysis is ON,
this function is not used.
If the Automatically Select Optimal Calibration Curve function or Automatically
Change Injection Volume function is used, it is that function that has priority.
As a consequence of rounding the dilution factor off to an integral value, in some
cases the ratio may only be 80% accurate.
When the Automatically Change Dilution Factor function is executed, the analysis
parameters are changed and analysis is started again with the data prior to that point
excluded. Since counting of the number of injections is started again from the point
where the analysis parameters are changed, the analysis takes some time.
TOC-LCSH/CSN
5.2
Analysis-Related Technical Information
5.2.8 Multiple Injections
If Multiple Injection item is set to ON on the "Conditions - Measurement Conditions"
screen, the Multiple Injections function is activated.
Multiple Injections Function
This is a function whereby a sample sufficient for multiple injections is drawn into the
syringe in one go, then the sample is dispensed in a number of injections and analysis is
performed each time. Since the acid addition that is done inside the cylinder and dilution
can be performed at the same time, analysis can be accomplished quickly. This function can
only be used with the following types of analysis:
TC, IC (CSH only), NPOC, TN
Multiple Injections Function
•
•
The repeatability may become lower than that in normal analysis.
If automatic condition change functions such as the Automatically Select Optimal
Calibration Curve function, the Automatically Change Injection Volume function, or
the Automatically Change Dilution Factor function are used, the analysis may have
to be restarted from sampling.
TOC-LCSH/CSN
289
5.3
Screen Descriptions
5.3
Screen Descriptions
5.3.1 "Initial Display"
The "Initial Display" is the screen displayed when the instrument is turned on.
1
2
4
3
Screen Items
(1) Screen title "Initial Display"
(2) Instrument model name "TOC-LCSH"
(3) Current date and time
(4) ROM version number
Function Keys
290
Function Key
Function
F1 [Standby Option]
Displays the "Standby Option" screen.
F3 [Background Monitor]
Displays the "Background Monitor" screen.
F4 [Conditions]
Displays the "Conditions" screen.
F5 [Maintenance]
Displays the "Maintenance" screen.
F6 [Data Report]
Displays the "Data Report" screen.
TOC-LCSH/CSN
5.3
Screen Descriptions
5.3.2 "Background Monitor" Screen
The "Background Monitor" screen is displayed when the F3 [Background Monitor] key is
pressed in the "Initial Display".
Screen When F5 [TOC] is Selected
1
3
4
5
6
2
7
Screen Items
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Screen title "Background Monitor"
Baseline is displayed.
Furnace temperature. OK or NG is displayed.
Dehumidifier temperature. OK or NG is displayed.
NDIR detector temperature. OK or NG is displayed.
Baseline position, fluctuation, and noise. OK or NG is displayed for each of these
properties.
The carrier gas flow rate and supply gas pressure to the instrument are displayed.
Function Keys
Function Key
Function
F1 [Return]
Returns to the "Initial Display".
F3 [Zoom In]
Magnifies the peaks by decreasing the viewable range of the
y-axis.
TOC-LCSH/CSN
291
5.3
Screen Descriptions
Screen When F6 [TN] is Selected
7
Screen Item
(8)
Reactor temperature. OK or NG is displayed when the optional TN accessory is
installed.
5.3.3 "Conditions" Screen
The "Conditions" screen is displayed when the F4 [Conditions] key is pressed in the "Initial
Display".
The "Conditions" screen is comprised of two screens, the "Unit Management" screen and
the "Measurement Conditions" screen.
"Conditions - Unit Management" Screen
When the F3 [Unit Management] key is pressed, the following screen is displayed.
1
5
2
3
4
292
TOC-LCSH/CSN
6
5.3
Screen Descriptions
Item Descriptions
[***-***]: Displays the numeric range for the current cursor item.
(1)
Basic Unit
Item
Description
Furnace Power
Sets the furnace power to ON/OFF.
Temp.
Sets the furnace temperature.
Catalyst Type
Sets the type of catalyst (Regular, High, TC/TN, Saline)
(2) TN
This item is displayed when the TN unit is connected.
Item
Description
Power
Sets the TN unit power to ON/OFF.
(3) SSM
This item is displayed when the optional SSM unit is installed.
Item
Description
SSM Measurement
Sets whether the Solid Sample Module will be used in the
analysis.
SSM-TC Furnace
Sets the TC furnace ON/OFF.
SSM-IC Furnace
Sets the IC furnace ON/OFF.
Cell Length
Determines which NDIR cell is utilized.
(4)
Other Units
Item
Description
SP Kit
Sets whether or not the optional Suspended Solids kit is
installed (Enable/Disable).
Small Syringe
Sets whether the small syringe kit is installed (Enable/
Disable)
Manual Inj
Sets whether the optional manual injection kit is installed
(Enable/Disable)
(5)
Printer
Item
Description
Runtime Report
Sets whether or not to print runtime reports (ON/OFF).
Peak Print
Sets whether or not to print the peak profiles in runtime
reports (ON/OFF).
Cal.Grap.Print
Sets whether or not to print the calibration curve graph(s) in
runtime reports (ON/OFF).
Printer type
Sets the printer model (HP, EPSON)
Paper size
Sets the paper size for printing (US Letter, A4)
TOC-LCSH/CSN
293
5.3
Screen Descriptions
(6) ASI
This item is displayed when the autosampler is connected.
Item
Description
Vial
Sets the vial type (9mL, 24mL, 40mL).
Needle Set
Sets the needle type (Sample, Sample + Sparge, Combi,
Combi + Sparge).
Needle Rinse
Sets whether or not to rinse the needle after every sample
analysis (ON/OFF).
Needle Rinse after acid add
Sets whether or not to rinse the needle after each addition of
acid to a vial (ON/OFF).
ASI Magnetic Stirrer
Sets whether or not the autosampler magnetic stirrer is
installed (ON/OFF).
Flowline Wash A
Sets the number of times (0 - 3) the flow line is rinsed after
each sample analysis.
Flowline Wash B
Sets the number of times (0 - 5) the flow line is rinsed after
all the sample analyses, acid additions and calibration curve
analyses.
"Conditions - Measurement Conditions" Screen
When the F4 [Meas. Cond.] is key is pressed, the following screen is displayed.
3
1
2
294
TOC-LCSH/CSN
4
5.3
Screen Descriptions
Item Descriptions
[***-***]: Displays the numeric range for the current cursor item.
(1)
Meas.
Item
Description
# of Syringe Wash
Sets the number of times the syringe is washed with sample.
# of Syringe Wash (sp)
Sets the number of times the syringe is washed with sample
when the optional POC analysis or IC analysis with the N
Type is performed.
Auto Inj. Vol. Change
Sets whether or not to use the Automatically Change
Injection Volume function (ON/OFF).
Auto Dil change
Sets whether or not to use the Automatic Dilution Factor
Change function (ON/OFF).
Multiple Injection
Sets whether or not to use the Multiple Injections function
(ON/OFF).
Auto IC regenerate
Sets whether or not to use the automatic regeneration of IC
reagent function (ON/OFF).
Min.Mes.Span[TC/NPOC]
In TC and NPOC analysis, this sets the time from the end of
analysis (sample injection) to the beginning of the next
analysis (sample injection).
Min.Mes.Span[IC/POC]
In IC and POC analysis, this sets the time from the end of
analysis (sample injection) to the beginning of the next
analysis (sample injection).
SS Meas. Sequence
Sets whether to use the function that agitates the contents of
the syringe by sparging immediately prior to injecting sample
from the water sampling syringe into the combustion tube
when measuring samples that contain suspended solids (ON/
OFF).
(2)
(3)
Name of Method Group
Sets the name of the method group.
Output
Item
Description
Unit
Sets the unit of concentration.
Name of Convert.Val.
Sets the conversion value name.
Object for Conversion
Sets the conversion analysis mode (NONE, TC, IC, TOC
(TC-IC), POC, NPOC, TOC (POC+NPOC), TN)
Equation (y=Ax+B)
•
A: Sets the A value or slope.
•
B: Sets the B value or intercept.
(4)
Misc.
Item
Description
Date
Sets the date and time.
Buzzer
Sets the buzzer sound to ON or OFF.
Scrn off
Sets the screen saver function to ON or OFF.
TOC-LCSH/CSN
295
5.3
Screen Descriptions
"Conditions - Others"
The following screen is displayed when the F5 [Others] key is selected.
Item Descriptions
[***-***]: Displays the numeric range for the current cursor item.
296
Item
Description
Carrier Gas
Sets the type of carrier gas (Air, N2, O2)
Carrier Gas Flow
Sets the carrier gas flow rate
Ext. Sparge Time
Sets the sparge gas flow rate when using the optional external
sparge kit.
TOC-LCSH/CSN
5.3
Screen Descriptions
5.3.4 "Maintenance" Screen
This section describes the "Maintenance" screen.
Item Descriptions
Item
Description
Sparge Gas
Starts the flow of sparge gas. (Displayed during sparging)
Disable Rdy. Chk
Disables the ready check function. When set to ON, the
instrument is considered to be in the READY state at all
times.
Rotate Rack of ASI
Rotates the autosampler turntable 1/3 of a complete rotation.
TC Blank Checking
Executes the TC blank check analysis.
Flow Line Wash
Executes washing of the flow line with dilution water.
Bubble Removal
Executes removal of bubbles in the acid channel and the
dilution water channel.
Replace Syringe
Used when detaching the syringe.
Syringe Zero Point detect
Detects the zero point of the sample injection syringe.
Regeneration TC Catalyst
Executes regeneration of the TC catalyst.
IC regeneration
Executes regeneration of the IC Reaction Solution.
Mechanical Check
Used to check each operation function. Mainly for Service.
Input Check
Checks the key input status. Mainly for Service.
Install Printer Driver
Installs any required printer drivers.
LAN Parameter setup
Sets any required LAN parameters. (When the LAN card is
installed as an option.)
TOC-LCSH/CSN
297
5.3
Screen Descriptions
Counters
Counter values are set and displayed with the actual values. They can be set to generate a
warning for the following items.
•
•
•
•
•
•
•
•
•
•
•
Running Time
O3 Generator
CO2 Absorber
Number of 8 port rotor operations
Total Injection Volume
Acid Usage Volume
Number of Syringe Strokes
IC Tubing Pump
ASI Tubing Pump
Hours of operation for stirrer motors (1) through (8)
Number of OCT1 (OCT2) 8-port valve operations
Function Keys
Function Key
Function
F1 [Return]
Returns to the "Initial Display".
F4 [Clear Counter]
Clears the current counter values.
F5 [Operation Log]
Displays the "Operation Log" screen.
F6 [Error Status]
Displays the "Error Log / Error Status" screen.
Displaying "Error Log / Error Status" Screen
In the "Maintenance" screen, press the F6 [Error Status] key to display the "Error Log /
Error Status" screen.
Function Keys
298
Function Key
Function
Save
Outputs the contents of the error log to a USB memory
device.
TOC-LCSH/CSN
5.3
Screen Descriptions
Function Key
Function
F3 [Clear Error Log]
Deletes the contents of the Error Log.
F6 [Clear Error]
The errors are released, and the error message in Error Status
are deleted.
5.3.5 "Data Report - Measurement Log" Screen
This section describes the "Data Report - Measurement Log" screen. This screen is used to
check the history of analysis results up to the present. Each analysis type item in the history
is displayed on a single line. The history can retain up to 1000 items and the oldest data is
removed first when this limit is exceeded. In addition, up to 25 items can be displayed on a
single page.
1
2
3
4
5
6
7
8
9
Item Descriptions
Item
Description
(1)
Sample Name
Name of measured sample.
(2)
V#
Measured vial number.
(3)
Date & Time
Date and time of analysis.
(4)
Type
Analysis mode.
(5)
Conc.
Concentration value of analysis result.
(6)
SD
Standard deviation.
(7)
CV%
Percent coefficient of variation of analysis result.
(8)
TOC
TOC value calculated as TOC=TC-IC or TOC=POC +NPOC
Displayed when TC and IC or POC and NPOC analyses have
been performed. This value is displayed for IC or NPOC.
TOC-LCSH/CSN
299
5.3
Screen Descriptions
Item
(9)
Description
Page Display
The number before the "/" represents the current page, while the
number following the "/" is the total number of pages. To change
the page, move the cursor to the bottom or to the top of the
current page, and then press the down or up cursor key,
respectively, to display the next or previous page, respectively.
Function Keys
300
Function Key
Function
F1 [Return]
Returns the display to the "Initial Display" screen.
F2 [Data Save]
Outputs the selected data to a USB memory device.
F3 [Data Search]
Opens the "Data Search" screen.
F4 [Clear Select]
Deletes the selected data.
F5 [All Select/All Clear]
Selects or deselects all of the displayed data.
F6 [Cal. Curves List]
Opens the "Data Report - Calibration Curves" screen.
TOC-LCSH/CSN
5.3
Screen Descriptions
5.3.6 "Data Report - Calibration Curves" Screen
This section describes the "Data Report - Calibration Curves" screen.
Screen Displayed in Reference Mode
2
3
4
5
6
7
8
1
10
11
9
12
13
14
15
16
17
Screen Displayed in Edit Mode
This screen is used to verify the calibration curve data or to edit the data.
2
3
4
5
6
7
8
1
10
11
9
12
13
14
15
16
17
TOC-LCSH/CSN
301
5.3
Screen Descriptions
Item Descriptions
(1) Calibration curve list display field
A list of calibration curves is displayed based upon the type of analysis selected.
Item
Description
(2)
Analysis Type
Displays the analysis type selected using the function keys.
(3)
#
Calibration curve number. This is highlighted only when
analysis is not performed by the conditions.
(4)
Conc.
Displays the calibration curve analysis scale.
(5)
DL
Displays the dilution factor used in calibration curve analysis.
(6)
Inj Vol
Displays the injection volume used in calibration curve analysis.
(7)
Catalyst Type
(8)
Status
Displays the catalyst type used in generating calibration curve.
•
C-R: Regular catalyst
•
C-H: High sensitivity catalyst
•
C/N: TC/TN catalyst
•
Saline: Catalyst for high salt samples
•
---: Displayed when combustion tube was not used.
Displays the calibration curve usage status. If this item is
marked, the calibration curve cannot be deleted. The various
marks are as follows.
S: Used via sample measurement.
M: Used via method data.
A: Used via ASI schedule sample analysis.
P: Protected.
(9)
Calibration curve data display field
This displays the data of the calibration curve selected by cursor positioning.
Item
Description
(10) Graph
Displays the graph of the selected calibration curve. This
graph changes automatically according to editing changes of
graph type and curve shift selections.
•
(11) Display of each point
302
TOC-LCSH/CSN
Abscissa: Concentration
•
Ordinate: Area value
•
n: Displays each measured point. (Discarded points are
not included.)
Displays the analysis result for each point of the selected
calibration curve.
•
#: Displays point number.
•
STD Conc.: Displays the standard solution concentration
for each point.
•
Area: Displays the analysis result area value for each
point.
•
SD: Displays the area value standard deviation for each
point.
•
CV%: Displays the coefficient of variation in area values
for each point.
5.3
Screen Descriptions
Item
Description
(12) R2
Displays the graph coefficient of determination (R2) used
when generating the currently selected calibration curve. This
is displayed when the least squares method is used for a
calibration curve having 3 or more points.
(13) Catalyst Type
Displays the type of catalyst used when generating the
currently selected calibration curve.
•
Regular: Regular catalyst.
•
High: High sensitivity catalyst.
•
TC/TN: TC/TN catalyst.
•
Saline: Combustion tube for high salt samples
•
---: Displayed when combustion tube was not used.
(14) Date
Displays the date and time that the curve was last updated.
(15) Protect
Displays the Protect status of the curve.
(16) Curve Type
(17) Shift
•
OFF: Not protected.
•
ON: Protected.
Displays the curve type.
•
Least squares: Concentration calculated using straight
line based on least squares method.
•
Pt-to-Pt: Concentration calculated based on point-topoint graph.
Displays curve shift status with respect to graph origin point.
•
none: No shift to zero point.
•
Origin: Shift to zero point.
•
Blank: Curve shifted to the blank analysis value.
Function Keys (For Reference Mode)
Function Key
Function
F1 [Return]
Returns to the "Data Report - Measurement Log" screen.
F2, [TC] F3, [IC] F4, [POC], Switches the Calibration Curve Type.
F5 [TN]
F6 [Edit]
Switches to Edit mode for the currently selected calibration
curve.
Function Keys (For Edit Mode)
Function Key
Function
F1 [Cancel]
Returns to the Reference mode, canceling all edits that were
made.
F2 [Protect ON/OFF]
Changes the Protect status.
F3 [Cal. Curve Type]
Changes the type of curve.
F4 [Zero Shift Status]
Changes the shift status of the curve.
F6 [OK]
Confirms any changes, and returns to Reference mode.
TOC-LCSH/CSN
303
5.3
Screen Descriptions
5.3.7 "Calibration Settings" Screen
The "Calibration Settings" screen is displayed by pressing the [Cal] key while viewing the
"Initial Display".
1
2
4
8
3
9
5
6
7
Item Descriptions
(1)
Screen title
Calibration Settings
(2) Displays calibration curve information set for the selected analysis type.
Item
304
Description
TC, IC, POC, TN
Calibration curve type.
#
The calibration curve number. Calibration curve numbers for
curves that have not yet been generated are displayed using
highlighted characters.
Conc.
Highest concentration of standard solution to be used for
generating the calibration curve.
DL
Displays dilution factor used for calibration curve analysis.
Inj Vol
Injection volume used when generating a calibration curve.
Catalyst Type
Displays the type of catalyst when the calibration curve type
is TC or TN (C-R: regular catalyst, C-H: high sensitivity
catalyst, C/N: TN catalyst, Saline: catalyst for high salt
samples). If the calibration curve type is IC or POC, "---" is
displayed.
Status
Calibration curve status.
TOC-LCSH/CSN
•
S: Used for sample analysis.
•
M: Used in method.
•
A: Used in ASI analysis.
•
P: Protected.
5.3
Screen Descriptions
(3)
Calib #
Calibration curve number (0 - 9). The setting information associated with that
calibration curve is displayed when an existing calibration curve number is entered.
(4) Contin.Meas
Turn the continuous analysis status ON or OFF using the selection key.
(5) [***-***]
Displays the setting range for the item that the cursor is currently on.
(6) POINT 1 - 10
The point number. To add a point to the calibration curve, position the cursor in the
solid-line frame below the point number, and press the right arrow key. To delete a
calibration curve point, position the cursor in the solid-line frame below the point
number, and press the F6 [Delete Point] key.
(7) Calibration curve settings
Item
Description
Vial #
Vial number. If the ASI or 8-port sampler is used, set the vial
number position of the standard solution. If the calibration
curve is to be generated off-line, set "0".
STD Conc.
Set the concentration of the standard solution.
Org Conc.
Set the concentration of the standard solution before dilution
when generating a multi-point calibration curve with diluted
solution here. (When generating a standard calibration curve,
this item and the next one, Dil. Factor, are not displayed.)
Dil. Factor
The dilution factor when generating multi-point calibration
curve with diluted solution is displayed here. This item is
automatically calculated provided the concentration of the
standard solution and the concentration of the undiluted
solution are set.
Note:
Set values that ensure the dilution factor is greater
than 1.25. If the dilution factor is less than 1.25,
the dilution factor precision of the instrument may
be impaired.
Inj #
Set the number of injections (1 - 20) to be used for generating
the calibration curve.
Max # of Inj
When the number of injections is 2 or more, and the
maximum number of injections is greater than the number of
injections, set the SD and CV% values to determine whether
to perform additional analyses.
SD, CV%
Dil. Factor
When the concentration of the standard solution is set, the
optimum value is automatically determined. The value can
also be entered manually as long as it is within the setting
range. If the dilution factor for sample analysis and the
dilution factor for generating the calibration curve do not
match, the analysis result may be affected.
Inj. Volume
When the concentration of the standard solution is set, the
optimum value is automatically determined. The value can
also be entered manually as long as it is within the setting
range.
Acid ratio
Always set an acid ratio when the calibration curve type is N
Type IC or NPOC.
TOC-LCSH/CSN
305
5.3
Screen Descriptions
Item
Description
Sparge Time
Always set a sparge time when the calibration curve type is N
Type IC or NPOC.
(8)
(9)
Curve Type
The calibration curve type setting (Least Squares / Point to Point). Choose the
calibration curve type using the [Select] key.
Curve Shift
The calibration curve shift setting (none / Origin / Blank.) Choose the curve shift
using the [Select] key.
Function Keys
Function Key
Function
F1 [Dil. for Std. Sol.
ON/OFF]
Selects whether a standard calibration curve or a multi-point
calibration curve with diluted solution is to be generated. If
the selection is for a multi-point calibration curve with
diluted solution, the undiluted concentration and dilution
factor are displayed under the concentration of the standard
solution, and the dilution factor under CV% is given as "- -".
F2 [TC]
Selects the calibration curve type TC.
F3 [IC]
Selects the calibration curve type IC.
F4 [POC]
Selects the calibration curve type POC.
F5 [TN]
Selects the calibration curve type TN.
F6 [Delete Point]
Deletes the point where the cursor is positioned.
Other Keys
306
Key
Function
[Cal]
Returns to the "Initial Display".
[Next]
Starts generating the calibration curve.
TOC-LCSH/CSN
5.3
Screen Descriptions
5.3.8 Calibration Curve Generation
5.3.8.1 "Calibration" Screen
When the [Next] key is pressed in the "Calibration Settings" screen, the "Calibration"
screen for generating the calibration curve is displayed.
1
2
3
4
5
7
6
8
9
10
11
Item Descriptions
Item
(1)
Description
Screen Title
Calibration
(2)
Calib. #
Calibration curve number.
(3)
Continuous Meas.
Continuous measurement setting status (ON/OFF.)
(4)
STD Conc., Mean
Area, SD, CV%
The standard solution concentration and analysis value are
displayed for each calibration curve point. The point that is
being measured is displayed within a solid-line frame.
(5)
STD Solution
The concentration of the standard solution to be measured is
displayed.
(6)
Graph
The peak output for the peak being detected is displayed in a
graph.
(7)
Inj #, Area, Remarks
The area value for each peak and remarks associated with the
current analysis are displayed.
Remarks •
T: Detector output is tailing.
•
H: Detector output is off scale.
•
F: Furnace temperature is out of range.
•
S: IC reaction solution was automatically regenerated.
(8)
Date & Time
The current date and time are displayed.
(9)
Protect
Displays the Protect status of the calibration curve.
TOC-LCSH/CSN
307
5.3
Screen Descriptions
Item
Description
(10) Curve Type
(11) Shift
•
OFF: Unprotected
•
ON: Protected
Displays the type of calibration curve.
•
Least Squares: The Least Squares method is used as the
calibration curve determination method.
•
Pt-to-Pt: The calibration curve is generated as a point-topoint curve.
Displays the shift status of the calibration curve.
•
none: Curve is not shifted to zero point.
•
Origin: The standard solution concentration, 0 area value,
is adjusted to 0.
•
Blank: The standard solution concentration, 0 area value,
is adjusted to the blank check analysis result value.
Function Keys
Function Key
Function
F1 [Return]
Returns to "Calibration Settings" screen.
F3 [Zoom In]
Magnifies the peaks by decreasing the viewable range of the
y-axis.
F4 [Zoom Out]
Reduces the peaks by increasing the viewable range of the
y-axis.
Place the standard solution and press the [Start] key.
5.3.8.2 During Analysis
Once the standard solution is set and the [Start] key is pressed, calibration curve analysis
begins.
1
2
3
4
5
7
6
8
9
308
TOC-LCSH/CSN
10
11
5.3
Screen Descriptions
Item Descriptions
Item
Description
(1)
Screen Title
Calibration
(2)
Current Operation
Displays the operation currently being performed.
(3)
Calib. #
Calibration curve number.
(4)
Continuous Meas.
Continuous measurement setting status (ON/OFF.)
(5)
STD Conc., Mean
Area, SD, CV%
The standard solution concentration and analysis value are
displayed for each calibration curve point. The point that is
being measured is displayed within a solid-line frame.
(6)
Graph
The peak output for the peak being detected is displayed in a
graph.
(7)
Inj #, Area, Remarks
The area value for each peak and remarks associated with the
current analysis are displayed.
Remarks •
T: Detector output is tailing.
•
H: Detector output is off scale.
•
F: Furnace temperature is out of range.
•
S: IC reaction solution was automatically regenerated.
(8)
Date and Time
The current date and time are displayed.
(9)
Protect
Displays the protect status of the calibration curve.
(10) Curve Type
(11) Shift
•
OFF: Unprotected.
•
ON: Protected.
Displays the type of calibration curve.
•
Least Squares: The Least Squares method is used as the
calibration curve determination method.
•
Pt-to-Pt: The calibration curve is generated as a point-topoint curve.
Displays the shift status of the calibration curve.
•
none: Curve is not shifted to zero point.
•
Origin: The standard solution concentration, 0 area value,
is adjusted to 0.
•
Blank: The standard solution concentration, 0 area value,
is adjusted to the blank check analysis result value.
Function Keys
Item
Description
F1 [Measurement Conditions]
Displays the analysis parameters.
F2 [Ready Status]
Displays the ready parameters. Can also be used to clear
counters.
F3 [Zoom In]
Magnifies the peaks by decreasing the viewable range of the
y-axis.
F4 [Zoom Out]
Reduces the peaks by increasing the viewable range of the
y-axis.
F5 [Browse Cal. Curves]
Displays a graph of the calibration curve.
To cancel generation of the calibration curve, press the [STOP] key.
TOC-LCSH/CSN
309
5.3
Screen Descriptions
5.3.8.3 Completion of Analysis Point
If Continuous Measurement is OFF, the function key assignments change at the completion
of each point as follows.
Function Keys
Item
Description
F1 [Add Injection]
Additional analysis is performed for the current point.
F2 [Remeasure Point]
The current point is measured again from the beginning.
F3 [Zoom In]
Magnifies the peaks by decreasing the viewable range of the
y-axis.
F4 [Zoom Out]
Reduces the peaks by increasing the viewable range of the yaxis.
F5 [Browse Cal. Curves]
Displays a graph of the calibration curve standard solution
concentrations and area values.
F6 [Exit Cal. Measurement]
Starts analysis of the next point.
5.3.8.4 Analysis Completion
1
2
3
4
6
5
7
8
9
10
Item Descriptions
Item
310
Description
(1)
Screen Title
Calibration
(2)
Calib. #
Calibration curve number.
(3)
Continuous Meas.
Continuous measurement setting status (ON/OFF).
(4)
STD Conc., Mean
Area, SD, CV%
The standard solution concentration and analysis value are displayed
for each calibration curve point. The point that is being measured is
displayed within a solid-line frame.
(5)
Graph
The peak output for the peak being detected is displayed in a graph.
TOC-LCSH/CSN
5.3
Item
(6)
Description
Inj #, Area, Remarks The area value for each peak and remarks associated with the
current analysis are displayed.
Remarks •
(7)
Date and Time
(8)
Protect
(9)
Screen Descriptions
Curve Type
(10) Shift
T: Detector output is tailing.
•
H: Detector output is off scale.
•
F: Furnace temperature is out of range.
•
S: IC reaction solution was automatically regenerated.
The current date and time are displayed.
Displays the protect status of the calibration curve.
•
OFF: Unprotected.
•
ON: Protected.
Displays the type of calibration curve.
•
Least Squares: The Least Squares method is used as the
calibration curve determination method.
•
Pt-to-Pt: The calibration curve is generated as a point-to-point
curve.
Displays the shift status of the calibration curve.
•
none: Curve is not shifted to zero point.
•
Origin: The standard solution concentration, 0 area value, is
adjusted to 0.
•
Blank: The standard solution concentration, 0 area value, is
adjusted to the TC blank value.
After completion of the calibration curve, the function key assignments change as follows.
Function Keys
Function Key
Function
F1 [Add Injection]
Additional analysis is performed for the current point.
F2 [Remeasure Point]
The current point is measured again from the beginning.
F3 [Zoom In]
Magnifies the peaks by decreasing the viewable range of the
y-axis.
F4 [Zoom Out]
Reduces the peaks by increasing the viewable range of the yaxis.
F5 [Browse Cal. Curve]
Displays a graph of the calibration curve standard solution
concentrations and area values.
F6 [Exit Cal. Measurement]
Ends calibration curve generation.
TOC-LCSH/CSN
311
5.3
Screen Descriptions
5.3.8.5 Calibration Curve Protection
After pressing F6 [Exit Cal. Measurement], the following message box is displayed to
enable protection for the generated calibration curve.
Function Keys
312
Function Key
Function
F1 [Cancel]
Returns to the "Calibration" screen.
F4 [No]
The generated calibration curve will not be protected, and the
display returns to the "Initial Display".
F6 [Yes]
The generated calibration curve will be protected, and the
display returns to the "Initial Display".
TOC-LCSH/CSN
5.3
Screen Descriptions
5.3.9 "Measurement Parameters" Screen
To perform sample analysis, press the [Measure Sample] key while viewing the "Initial
Display". This opens the "Measurement Parameters" screen.
1
2
15
17
4
16
5
6
8
10
12
14
7
9
11
13
3
Item Descriptions
Item
Description
(1)
Sample Name
Enter the sample name. The sample name may be entered
using the alphabet key, numerical keys 0 -9, and the special
symbol keys. The sample name is displayed on printouts and
other data output.
(2)
Vial #
Specifies the vials containing the samples to be measured.
For example, if the setting is 1 - 10, analysis is conducted
successively on samples in vials 1 - 10. Note that if this
function is used, vial numbers within the specified range
cannot be skipped, and the analysis sequence cannot be
changed. A setting of 0 indicates the off-line sampling port
Number 1. This item can be set only when the ASI is
connected.
(3)
(4)
[TC] F2 Selects the type of analysis to be performed for this sample.
[IC] F3 When the function key corresponding to the desired analysis
[POC] F4 type is pressed, the field for that analysis type is displayed for
entering the associated settings, and this is selected as the
[NPOC] F5
analysis type for settings hereafter. Pressing this function key
[TN] F6
again closes this setting field, and cancels the selection of this
analysis type. Actual analysis is conducted using analysis
types from left to right. Depending on the options and kits in
the system configuration, some function keys (analysis types)
may not be displayed.
Input range display
Displays the setting range for the item at which the cursor is
positioned.
TOC-LCSH/CSN
313
5.3
Screen Descriptions
Item
Description
(5)
Calib.
(6)
Inj. Volume
Sets the sample volume for analysis. The volume used for
generating the calibration curve is automatically entered. The
injection volume can be changed and the concentration result
in that case is determined using a correction calculation. If
multiple calibration curves are selected, the injection volume
cannot be changed.
(7)
Inj #
Sets the number of sample injections to be used to obtain a
analysis result. If the number of injections differs from the
maximum number of injections, the automatic additional
analysis function is implemented.
(8)
Maximum Number of
Injections
If the automatic additional analysis function is implemented,
the maximum number of injections to be performed is set
here. The conditions that regulate the maximum number of
injections are defined using the SD and CV% parameters.
(9)
SD
Sets the standard deviation value used for judging whether or
not additional analyses are automatically performed. The
automatic additional analysis function operates when both
the SD value and the CV% value are not satisfied.
(10) CV%
314
TOC-LCSH/CSN
(1st) Enters the calibration curve number for the curve to be
(2nd) generated. When the cursor is positioned in the calibration
(3rd) curve field, a list of calibration curves is displayed in the
upper portion of the screen. When the 1st calibration curve is
entered, the injection volume and dilution factor used in
generating the 1st calibration curve are automatically entered.
If 2nd and subsequent calibration curves are entered, the
optimum calibration curve auto-selection function is
implemented and the injection volume / dilution factor
cannot be changed. If an unfinished calibration curve
(highlighted) is used in actual analysis, analysis is performed.
Only the area value appears for the result and the
concentration value is 0. When the cursor is in the calibration
curve field, the F1 (View Calibration Curve Details) function
key is enabled.
Sets the coefficient of variation value used for judging
whether or not additional analyzes are automatically
performed. The automatic additional analysis function
operates when both the SD value and the CV% value are not
satisfied.
5.3
Screen Descriptions
Item
Description
(11) Dil. Factor
Sets the dilution factor to be used in analysis. When the 1st
calibration curve is entered, the dilution factor used in
generating that calibration curve is automatically entered.
This dilution factor can be changed, and the actual analysis
range that is possible is displayed in the 1st calibration curve
field. The concentration result using a dilution factor
different than that used for the calibration curve is determined
using a correction calculation. The dilution factor that can be
entered differs according to the analysis type. A dilution
factor cannot be used in POC analysis. If multiple calibration
curves are selected, the dilution factor cannot be changed.
(12) Acid ratio
Enters the percentage of acid to be added at the time of
analysis. In NPOC and IC (without IC reaction kit), a value
must be entered here. Values can be entered in 0.5%
increments.
(13) Sparge Time
Sparging can be performed as a sample pretreatment process.
This value cannot be entered for TC, POC and IC (with IC
reaction kit).
(14) Sparge Gas Flow
Sets the sparge gas flow rate when performing sparging.
(15) Same Mode Contin.
Meas. / Continuous
Meas.
The Same Mode Continuous Measurement switch is
displayed only when a single type of analysis is selected. If it
is switched ON, an unlimited number of analyses are
repeated using a singe analysis mode. This is used after
replacing the catalyst to reduce the blank value associated
with the new catalyst. If multiple types of analysis are
selected, the Continuous Measurement switch is displayed.
When this switch is OFF, the analysis can be stopped and
additional analyses can be performed before moving to a
different type of analysis. If this switch is ON, analysis is
performed continuously without stopping until all of the
appropriate samples have been measured.
(16) POC & NPOC
When this is switched ON, NPOC analysis is performed
using the same sample that was used for POC analysis. Since
the sample need not be drawn into the syringe again for the
NPOC analysis, just a small amount of sample is consumed.
However, in NPOC analysis, the number of injections is
limited to 1 injection, and there is also an upper limit imposed
on the sample volume. This switch is only displayed when
both POC and NPOC are selected as analysis types.
TOC-LCSH/CSN
315
5.3
Screen Descriptions
Item
Description
(17) +TN
When this switch is ON, TN analysis can be performed at the
same time as TC (or NPOC). Since the sample need not be
drawn into the syringe again for the TC analysis, just a small
amount of sample is required. The TN analysis injection
volume and dilution factor, can all be applied to the TC
(NPOC) analysis, and the result obtained by correction
calculation. To maintain analysis accuracy, it is
recommended to use a calibration curve generated
beforehand based on the injection volume and dilution factor
used in TC (NPOC) analysis. The optimum calibration curve
auto-selection function cannot be used with Simultaneous
Analysis. This switch is only available when TN has been
selected along with TC or NPOC.
Function Keys
Function Key
Function
F1 [Calibration Curve]
Only available when the cursor is on the Calib. # item. It
opens the calibration curve details screen.
F2 [TC]
Selects TC as the analysis type, and opens up the
corresponding analysis settings field.
F3 [IC]
Selects IC as the analysis type, and opens up the
corresponding analysis settings field.
F4 [POC]
Selects POC as the analysis type, and opens up the
corresponding analysis settings field.
F5 [NPOC]
Selects NPOC as the analysis type, and opens up the
corresponding analysis settings field.
F6 [TN]
Selects TN as the analysis type, and opens up the
corresponding analysis settings field.
Other Keys
316
Key
Function
[Next]
Press the [Next] key after entering all of the analysis
parameters. The analysis screen opens if the analysis settings
are consistent and complete.
TOC-LCSH/CSN
5.3
Screen Descriptions
5.3.9.1 Calibration Curve List
When the F1 [Calibration Curve] key is pressed in the "Measurement Parameters" screen,
the following "Measurement Parameters - Calibration Curve List" screen is opened.
1
Item Description
Item
(1)
Description
Calibration Curve #
Use the arrow keys to indicate the calibration curve number,
and the related information.
Function Keys
Function Key
Function
F1 [Cancel]
Returns to the "Measurement Parameters" screen, without
entering a calibration curve number.
F6 [Select]
Returns to the "Measurement Parameters" screen, and the
highlighted calibration curve is selected, and entered in the
calibration curve field of the "Measurement Parameters"
screen.
TOC-LCSH/CSN
317
5.3
Screen Descriptions
5.3.10 Analysis
After setting the sample, pressing the [Start] key will start the analysis.
1
3
2
6
8
10
5
7
4
9
12
11
Item Descriptions
Item
Description
(1)
Vial #
Displays the vial number of the sample currently being
measured. Only displayed when the ASI is used.
(2)
Sample Name
Displays the sample name of the sample currently being
measured.
(3)
Vial #
Displays the range of vial numbers currently being measured
using the same analysis conditions. Only displayed when the
ASI is connected. If the ASI is not connected, Continuous
Measurement ON/OFF is displayed.
(4)
Analysis Result
Display Field
The results are displayed by analysis type.
(5)
Area
The average area (for multiple injections) is displayed. If the
injection volume and dilution factor are different from those
used for the calibration curve, the average of the corrected
areas are displayed.
(6)
Conc.
When multiple injections are used for analysis, the average
concentration is displayed.
(7)
SD
Displays the standard deviation of the concentration value.
(8)
CV%
Displays the coefficient of variation of the concentration
value.
(9)
TOC Conc.
When TC and IC have been selected as the analysis types, the
TOC value is automatically calculated. This is also true if
NPOC and POC have been selected.
(10) CNV
318
TOC-LCSH/CSN
Displayed below the analysis item selected for conversion if
it was set in "Conditions - Measurement Conditions". The
character string "CNV" can be arbitrarily set using
"Conditions -Measurement Conditions".
5.3
Screen Descriptions
Item
Description
(11) Graph
Displays the peak profile of the sample being measured.
(12) Injection Result
Display Field
The area value, concentration value and remark are displayed
for each injection. The displayed remarks are as follows.
•
h: Exceeds calibration curve range.
•
H: Detector output is off scale.
•
D**: Automatic dilution factor change was performed.
The new factor is indicated by **.
•
T: Tailing occurred.
•
S: IC reaction solution was automatically regenerated
(when IC reaction kit is equipped).
Function Keys
Function Key
Function
F1 [Return]
If analysis has not yet started, pressing this key returns to the
"Measurement Parameters" screen.
F3 [Zoom In]
Magnifies the peaks by decreasing the viewable range of the
y-axis.
F4 [Zoom Out]
Reduces the peaks by increasing the viewable range of the
y-axis.
F6 [Go to Next Meas. Type]
This function key is displayed if another type of analysis was
set. Pressing this key causes analysis to proceed to the next
type specified. If analysis of another type was not set, or if
analysis for the last type is complete, this function key
displays [Exit Cal. Measurement]. Press the [Exit Cal.
Measurement] key to return to the "Initial Display".
TOC-LCSH/CSN
319
5.3
Screen Descriptions
5.3.10.1 During Analysis
When analysis is started the screen shown below is displayed.
Function Keys
320
Function Key
Function
F1 [Measurement
Conditions]
Displays the analysis parameters.
F2 [Ready Status]
Displays the ready parameters. Can also be used to clear
counters.
F3 [Zoom In]
Enlarges the scale of the peak graph.
F4 [Zoom Out]
Reduces the scale of the peak graph.
TOC-LCSH/CSN
5.3
Screen Descriptions
5.3.10.2 Viewing the Analysis Parameters
Pressing the F1 [Measurement Conditions] key during analysis displays the screen shown
below.
On this screen only the number of injections and the maximum number of injections can be
changed.
Item Descriptions
For details on the displayed items, refer to Section 5.3.9 ""Measurement Parameters"
Screen" on page 313 Screen.
Function Keys
Function Key
Function
F1 [Return]
Redisplays the analysis in progress screen.
TOC-LCSH/CSN
321
5.3
Screen Descriptions
5.3.10.3 Viewing the Ready Parameters
Pressing the F2 [Ready Status] key during analysis displays the screen shown below.
2
1
3
4
8
5
6
7
Item Descriptions
Item
Description
(1)
Oven
The furnace temperature and its OK/NG status are displayed
here.
(2)
Dehumidifier
The temperature of the dehumidifier (electronic cooler) and
its OK/NG status are displayed here.
(3)
NDIR Temp
The temperature of the NDIR detector and its OK or NG
status are displayed here.
(4)
TOC
The OK or NG status of the TOC detector's baseline position,
fluctuation, and noise are displayed here.
(5)
TN
The OK or NG status of the TN detector's baseline position,
fluctuation, and noise are displayed here.
(6)
TNM-1 Temp.
The temperature of the TN detector's reactor and its OK/NG
status are displayed here.
(7)
SSM
The OK or NG statuses of the SSM-5000A TC furnace
temperature and IC furnace temperature are displayed here.
(8)
Counters
The current values and warning values of the various
counters are displayed here.
The current values can be zeroed by clearing the individual
counters.
(9)
Sparge gas flow
(10) Carrier Gas Flow
Displays the sparge gas flow rate.
Displays the carrier gas flow rate.
Function Keys
322
Function Key
Function
F1 [Return]
Redisplays the analysis in progress screen.
TOC-LCSH/CSN
5.3
Function Key
Function
F4 [Clear Counter]
Clears the counter at the cursor position.
Screen Descriptions
5.3.10.4 Analysis Completion
When Continuous Measurement is set to OFF in the "Measurement Parameters" screen, the
displays changes to the following screen at the completion of one type of analysis.
1
Item Descriptions
Item
(1)
Description
Exclusion Setting
Specific data associated with each injection can be selected
for exclusion. Move the cursor using the ↑ ↓ keys, and
exclude or include (EXC / INC) the highlighted data using
the [CE] toggle key.
Function Keys
Function Key
Function
F1 [Add Injection]
Press this key to perform additional same type analyses.
F6 [Exit Measurement]
Magnifies the peaks by decreasing the viewable range of the
y-267
axis.
F4 [Zoom Out]
Reduces the peaks by increasing the viewable range of the
y-axis.
F6 [Go to Next Meas. Type]
This function key is displayed if another type of analysis was
set. Pressing this key causes analysis to proceed to the next
type specified. If analysis of another type was not set, or if
analysis for the last type is complete, this function key
displays [Exit Measurement]. Press the [Exit Measurement]
key to return to the "Initial Display".
TOC-LCSH/CSN
323
5.3
Screen Descriptions
5.3.11 "Method Store" Screen
This function is used for saving often-used analysis settings such as methods. Up to 5
groups of methods can be saved, each consisting of 5 methods, for a total of 25 methods. To
perform "Method Store", press the [Measure Sample] key while viewing the "Initial
Display" Fill in the appropriate parameters and press the [Save Method] key.
1
2
3
Item Descriptions
Item
Description
(1)
Method List
Displays all of the methods registered in the selected method
group.
(2)
Method Name
Enters a method name to identify the method. The method
name differs from the sample name and is used to identify the
method. The characters that can be used for entering a
method name include the numbers 0-9, the letters A-Z, and
the special symbols.
(3)
Measurement
Conditions
After performing the sample analysis settings in the
"Measurement Parameters" screen, press the [Save Method]
key to open the "Measurement - Method Store" screen. The
conditions set in the "Measurement Parameters" screen are
displayed.
Function Keys
324
Function Key
Function
F1 [Cancel]
Cancels the method registration, and returns to the
"Measurement Parameters" screen.
TOC-LCSH/CSN
5.3
Screen Descriptions
Function Key
Function
F2 - F6
Used for selecting the method groups. When a group is
selected, the methods stored in that group are displayed in the
Method List. The displayed names "GROUP-1" - "GROUP5" in the figure are the default group names, and can be
changed in the "Conditions - Measurement Conditions"
screen.
5.3.11.1 Loading a Method
A stored method can be loaded into the "Measurement Parameters" screen. The method is
loaded by pressing the [Method] key in the "Measurement Parameters" screen.
1
2
Item Descriptions
Item
Description
(1)
Method List
Select the method using the ↑ ↓ keys. Pressing the [Enter]
key displays the analysis conditions in that method. Pressing
the [Next] key selects the method and copies it into the
"Measurement Conditions" screen.
(2)
Analysis Conditions
Display
At method list, press [Enter] to display the analysis
conditions of the registered method.
Function Keys
Function Key
Function
F1 [Cancel]
Cancels loading of the method, and returns to the
"Measurement Parameters" screen.
TOC-LCSH/CSN
325
5.3
Screen Descriptions
Function Key
Function
F2 - F6
Used for selecting the method registration groups. The
methods already registered in a group are displayed in the
Method List when that group is selected. The displayed
names "GROUP-1" - "GROUP-5" in the figure are the
default group names, and can be changed in the "Conditions Measurement Conditions" screen.
5.3.12 "ASI Schedule - Settings" Screen
When the [ASI] key is pressed while viewing the "Initial Display", the following screen is
displayed.
Item Descriptions
326
Item
Description
Line
This line number provides the sequence of analysis for each
sample group.
Group Name [Calib. #]
The name of each sample group or the name of each
calibration curve to be measured.
Vials
The range of sample vials indicating which samples are to be
analyzed.
Meas. mode
Analysis mode of the sample group.
Message
Indicates the sample status, as follows.
TOC-LCSH/CSN
•
Not Measured: Unmeasured sample.
•
Not Meas. (Acid): Sample has had acid added but has not
been analyzed.
•
Measuring: Sample is currently being measured.
•
Measure End: Measured sample.
•
Meas. Interrupted: Analysis of the sample has been
cancelled part way through.
5.3
Note:
Screen Descriptions
At the start of analysis, any schedule of which status is "Not Measured" or "Not
Meas. (Acid)" is analyzed.
Function Keys
Function Key
Function
F1 [Recalibrate All
Calibration Curves]
At the start of the schedule, inserts all the calibration curves
required for sample analysis. Displayed only when the cursor
is positioned in the first line.
F2 [Insert Cal. Curve]
Enters the calibration curve required for analysis one line
before the selected sample. Displayed only when a sample is
selected.
F3 [Switch Line]
Changes the analysis sequence of the selected sample group.
F4 [Delete Schedule]
•
F1 [Return]: Returns to the first screen of "ASI Analysis
Schedule - Settings".
•
F2 [Switch with Upper Line]: The selected line is
switched with the line above it in the schedule.
•
F3 [Switch with Lower Line]: The selected line is
switched with the line below it in the schedule.
Deletes a sample group.
•
F1 [Return]: Redisplays the initial "ASI Schedule Settings" screen.
•
F4 [Delete Line]: Deletes the schedule in the selected
line.
•
F5 [Delete Area]: Deletes a specified range of schedule
data.
•
F6 [Delete All]: Deletes all schedules.
F5 [Edit]
Enables editing of the analysis conditions for the selected
sample group and calibration curve. Pressing this key when a
sample is selected displays the "ASI Measurement Settings"
screen. Pressing this key when a calibration curve is selected
displays the "ASI Calibration Settings" screen.
F6 [Reset status]
Changes the status indicated in the "Message" to "Not
Measured" or "Not Meas. (Acid)".
•
F1 [Return]: Redisplays the initial "ASI Schedule Settings" screen.
•
F3 [One Line Acidified]: Changes the message for the
schedule in the specified line to "Not Meas. (Acid)"
•
F4 [One Line]: Changes the message for the schedule in
the specified line to "Not Measured".
•
F5 [All Lines Acidified]: Changes the messages for all
schedules to "Not Meas. (Acid)".
•
F6 [All Lines]: Changes the messages for all lines to "Not
Measured".
TOC-LCSH/CSN
327
5.3
Screen Descriptions
Other Keys
Key
Function
[Cal]
The display changes to the "ASI Calibration Settings" screen,
and the calibration curve is inserted in the line just before the
cursor. For an explanation of the "ASI Calibration Settings"
screen, refer to the "Calibration Settings" screen.
[Measure Sample]
The display changes to the "ASI Measurement Settings"
screen, and the sample is inserted in the line just before the
cursor.The Group Name is also entered. For further
description of the "ASI Measurement Settings" screen, refer
to the "Measurement Parameters" screen.
5.3.12.1 "ASI Calibration Settings" Screen
Item Descriptions & Function Keys
For details on the displayed items, refer to Section 5.3.7 ""Calibration Settings" Screen" on
page 304.
Other Keys
328
Key
Function
Cal
Redisplays the initial "ASI Schedule - Settings" screen.
Next
Redisplays the initial "ASI Schedule - Settings" screen, and
saves the parameters in the schedule.
TOC-LCSH/CSN
5.3
Screen Descriptions
5.3.12.2 "ASI Measurement Settings" Screen
Item Descriptions & Function Keys
For details on the displayed items, refer to Section 5.3.9 ""Measurement Parameters"
Screen" on page 313.
Other Keys
Key
Function
Next
When you have entered all the analysis parameters, press the
Next key. Provided there is no omission or contradiction in
the measurement parameters, the "ASI Schedule - Settings"
screen is redisplayed and the parameters are saved in the
schedule.
TOC-LCSH/CSN
329
5.3
Screen Descriptions
5.3.12.3 ASI Schedule - Starting Analysis
When the [Next] button on the instrument is pressed, the message "Set sample and press
START button." is displayed.
Function Keys
330
Function Key
Function
F1 [Return]
Returns to the "ASI Schedule Settings" screen.
F3 [Shutdown]
After the analyses are complete, this switches off power to
the instrument.
F4 [Sleep]
After the analyses are complete, this switches off power to
the instrument. The next time the instrument is automatically
turned on.
F5 [Waiting]
When the analyses are complete, this maintains the
instrument in a waiting state.
TOC-LCSH/CSN
5.3
Screen Descriptions
Item Descriptions
Item
Description
Next reboot
This sets the date and time for automatic instrument startup.
Unit Condition
Instrument settings for automatic instrument startup.
Furnace
•
ON: Switches the instrument furnace ON.
•
OFF: Keeps the instrument furnace OFF.
Carrier Gas
•
ON: Starts the flow of carrier gas to the instrument.
•
OFF: Carrier gas flow to the instrument is not started.
TN Unit
•
ON: Switches power to the TN unit ON.
•
OFF: Power is not supplied to the TN unit.
Other Keys
Key
Function
[Start]
Analysis starts, and the display changes to the "ASI Analysis
- Vial #" screen. If the [View Schedule] button is pressed the
display returns to the first screen of "ASI Schedule Settings".
TOC-LCSH/CSN
331
5.3
Screen Descriptions
5.3.12.4 ASI Schedule - During Analysis
When analysis is started the screen appears as shown below.
Item Descriptions
For details on the displayed items, refer to Section 5.3.10 "Analysis" on page 318.
Function Keys
Function Key
Function
F1 [Schedule]
Displays the ASI schedule.
F2 [Ready Status]
Displays the ready parameters. Can also be used to clear
counters.
F3 [Zoom In]
Selects the full scale for the peak profile display. The full
scale is automatically set and displayed on the "ASI Analysis
Settings" screen (using the auto-ranging function), but the
full scale can be changed as required by using this key. Note
that the full scale set using this function is also applied when
printing.
F4 [Zoom Out]
332
TOC-LCSH/CSN
5.3
Screen Descriptions
5.3.12.5 ASI Schedule - Viewing the Schedule
Pressing the F1 [Schedule] key during analysis displays the screen shown below.
On this screen, schedules can be added.
Item Descriptions
For details on the displayed items, refer to Section 5.3.12 ""ASI Schedule - Settings"
Screen" on page 326.
Function Keys
Function Key
Function
F1 [Return]
Redisplays the analysis in progress screen.
F2 [Measurement
Conditions]
Displays the analysis parameters for the specified line.
TOC-LCSH/CSN
333
5.3
Screen Descriptions
5.3.12.6 ASI Schedule - Viewing the Calibration Curve Generation Parameters
On the ASI schedule reference screen during analysis, move the cursor to the line of the
calibration curve and press the F2 [Measurement Conditions] key to display the screen
shown below.
On this screen, only the number of injections and maximum number of injections can be
changed.
Item Descriptions
For details on the displayed items, refer to Section 5.3.7 ""Calibration Settings" Screen" on
page 304.
Function Keys
334
Function Key
Function
F1 [Return]
Redisplays "ASI Schedule - Viewing the Schedule" screen.
TOC-LCSH/CSN
5.3
Screen Descriptions
5.3.12.7 ASI Schedule - Viewing Analysis Parameters
On the ASI schedule reference screen during analysis, move the cursor to the line of the
sample setting and press the F2 [Measurement Conditions] key to display the screen shown
below.
On this screen, only the number of injections and maximum number of injections can be
changed.
Item Descriptions
For details on the displayed items, refer to Section 5.3.9 ""Measurement Parameters"
Screen" on page 313.
Function Keys
Function Key
Function
F1 [Return]
Redisplays "ASI Schedule - Viewing the Schedule" screen.
TOC-LCSH/CSN
335
5.3
Screen Descriptions
5.3.12.8 ASI Schedule - Viewing the Ready Parameters
Pressing the F2 [Ready Status] key during analysis displays the screen shown below.
Item Descriptions
For details on the displayed items, refer to Section 5.3.10.3 "Viewing the Ready
Parameters" on page 322.
Function Keys
336
Function Key
Function
F1 [Return]
Redisplays the analysis in progress screen.
F4 [Clear Counter]
Clears the counter at the cursor position.
TOC-LCSH/CSN
5.4
5.4
Specifications
Specifications
5.4.1 TOC-LCSH/CSN
Analyte
TC, IC, TOC (TC-IC), NPOC
Measurement principle
680°C catalytically-aided combustion oxidation/non-dispersive
infrared detection (NDIR)
Measuring range
TC: 0 - 30000mg/L
IC:
• TOC-LCSH: 0 - 35000mg/L
• TOC-LCSN: 0 - 3000mg/L
Detection limits
TC:
• TOC-LCSH: 4µg/L
• TOC-LCSN: 50µg/L
IC: 4µg/L
Measurement time
TC: Approx. 3min
IC:
• TOC-LCSH: Approx. 3min
• TOC-LCSN: Approx. 4min
Repeatability
TOC-LCSH:
TC, IC, NPOC
(Option: TN
TOC-LCSN:
TC, NPOC
IC
(Option: TN:
CV 1.5 % or ±4 μg/L max.
CV 3.0 % or ±5 μg/L max.)
CV 1.5 % or ±50 μg/L max.
CV 1.5 % or ±4 μg/L max.
CV 3.0 % or ±20 μg/L max.)
Sample introduction
Auto injection using syringe pump/slider
Sample injection volume
TC:
• TOC-LCSH: 10 to 2000 μL (variable)
• TOC-LCSN: 10 to 150 μL (variable)
IC:
• TOC-LCSH: 10 to 2000 μL (variable)
• TOC-LCSN: 10 to 4500 μL (variable)
Sample dilution function
Dilution within syringe, dilution factor 2 - 50 times
Pretreatment for IC
Automatic acid addition and sparging
Carrier gas
High purity air (from cylinder)
High purity nitrogen (with addition of the N2 carrier gas kit)
Pressurized air (with addition of the carrier gas purification kit (only
applicable to the TOC-LCSN))
Carrier gas pressure
Approx. 200 ± 10 kPa (300 to 600 kPa when using the carrier gas
regulator option)
Carrier gas flow rate
TOC-LCSH: 150 mL/min (230 to 250 mL/min when sparging)
TOC-LCSN: 230mL/min
Display
7.5" TFT (LED-backlit color liquid crystal display) VGA (640 ×
480)
TOC-LCSH/CSN
337
5.4
Specifications
Printer
Thermal type, 40 columns, 240 dot (graphic), chart width 110mm
Ambient temperature
5 - 35°C
Power requirements
AC100-120V or 220-240V (±10%), 600 VA, 50/60Hz
Fuse
10A LAG x 2, Interrupting capacity: 100A
Approximate dimensions
(W) 340 x (D) 660 x (H) 480mm (excluding projections)
Weight
Approx. 35kg
Sample containers
9 mL vial rack: 9 mL (External diameter 13 x Height 100 mm),
100 vials
5.4.2 ASI-L
24 mL vial rack: 24 mL (External diameter 23 x Height 85 mm),
100 vials, 100 septum-equipped caps
40 mL vial rack: 40 mL (External diameter 27 x Height 95 mm),
72 vials, 72 septum-equipped caps
Vial rack capacity
9 mL vial rack: 93 vials
24 mL vial rack: 93 vials
40 mL vial rack: 68 vials
Sample pretreatment
•
•
•
Acid addition and sparging possible for NPOC analysis (with
addition of the external sparge kit)
Needle rinse possible
Stirring with magnetic stirrer (with addition of the magnetic
stirrer, excluding 9 mL vials)
Ambient temperature
5 - 35°C
Approximate dimensions
(W) 370 x (D) 540 x (H) 490 mm (excluding projections)
Weight
Approx. 14 kg
5.4.3 OCT-L 8-Port Sampler
338
No. of sample containers
accommodated
8 containers
Ambient temperature
10 - 35°C
External dimensions
Approx. (W) 245 x (D) 245 x (H) 440mm
(excluding protruding parts)
Weight
Approx. 3.5kg
TOC-LCSH/CSN
16 containers (using 2 OCT-L units)
5.4
Specifications
5.4.4 TNM-1
Analyte
TN (total nitrogen)
Measurement principle
Thermal decomposition / NO detection (chemiluminescence
method)
Measuring range
0 - 10000mg/L
Detection limit
•
•
Measurement time
Approx. 4min
Repeatability
Higher value of within CV3 % or ± 5 μg/L
Sample injection volume
•
•
Ambient temperature
5 - 35°C
Approximate dimensions
(W) 270 x (D) 240 x (H) 160mm (excluding projections)
Weight
Approx. 6kg
TOC-LCSH: 5 μg/L
TOC-LCSN: 20 μg/L
TOC-LCSH: 10 to 300 μL (variable)
TOC-LCSN: 10 to 150 μL (variable)
5.4.5 POC Measurement Kit
Analyte
POC (volatile organic carbon)
Measurement method
Sparging / CO2 removal / 680 °C combustion oxidation / nondispersive infrared detection (NDIR)
CO2 removal method
Absorption via lithium hydroxide, removal
Measuring range
0 - 500mg/L
Measurement time
Approx. 4min
Repeatability
CV within 5%
5.4.6 Carrier Gas Purifier Kit
Gas purification method
Combustion oxidation / CO2 removal
Carrier gas supply
Pressurized air or oxygen (free of dust, oil mist, water droplets, etc.)
Carrier gas supply pressure
200 ± 10 kPa
TOC-LCSH/CSN
339
5.4
Specifications
5.4.7 Manual Injection Kit (Gas Sample Injection Kit)
Analyte
Liquid samples: TC, IC, TOC (TC-IC)
Gas samples: TC, carbon dioxide
TOC (TC, carbon dioxide) (carbon monoxide and other inorganic
carbon containing gases aside from carbon dioxide are also
measured as TOC)
(Measurement of IC, TOC and carbon dioxide possible using the
TOC-LCSH or TOC-LCSN with equipped IC reactor kit.)
Measurement principle
Measuring range
680°C catalytically-aided combustion oxidation/non-dispersive
infrared detection (NDIR)
Liquid sample:
•
•
TC: 0 - 20000mg/L
IC: 0 - 20000mg/L
Gas sample:
6ppm - 100% CO2
Sample injection volume
Liquid sample: 1 - 150µL
Gas sample: 20µL - 10mL
Measuring time
Liquid sample:
•
•
TC: Approx. 3min
IC: Approx. 3min
Gas sample: 2 - 4min
Repeatability
Liquid sample: CV within 2% (when sample concentration is
8000mg/L or greater, CV is within 3%.)
Gas sample: CV within 2%.
Sample introduction
Manual injection using microsyringe
5.4.8 B-Type Halogen Scrubber
Detection limit
TC: 60 μg/L
IC: 4 μg/L
TN: 30 μg/L
Sample injection volume
TC: 10 to 150 μL
IC:
•
•
Repeatability
TOC-LCSH: 10 to 2000 μL (variable)
TOC-LCSN: 10 to 4500 μL (variable)
CV within 3 %
5.4.9 External Sparge Kit
Flow rate adjustment range
340
TOC-LCSH/CSN
0 to 300 mL/min
5.4
Specifications
5.4.10 LAN Output
Installation of the optional LAN card to the rear of the instrument enables consecutive
output of results for calibration curve analysis, sample analysis, and blank check analysis.
Connect the PC to receive data one-to-one with the TOC-L. Do not connect the TOC-L to
computer networks.
5.4.10.1 Communication Specifications
Communications Protocol
TCP/IP
IP Address
192.168.1.1 (customizable)
Subnet Mask
255.255.255.0 (customizable)
Port Number
1400 (customizable)
5.4.10.2 Connection Cable
100Base-TX Category 5 crossover cable
5.4.10.3 Transmission Content
Transmission data is output in a specified data (byte) number which is dependant on the
type of data. Numeric data is right-aligned, and non-numeric data is left-aligned. If the data
is shorter than the allotted number of bytes, the empty bytes are output as spaces. These
spaces are designated with an underscore mark "_" in the following tables. All data items
are separated by a comma except for the line feed code (ending data). The comma is not
included in the following tables. Items unrelated to an analysis are output as spaces.
Calibration Curve Measurement Results
These data are output following completion of calibration curve measurement.
Output
Number
Order
of Bytes
1
12
Identifier
CALIB_RESULT
2
21
Measurement time
Example: 04 (APR)01-2003_09:00
3
5
Measurement type
TC_ _ _
IC_ _ _
POC_ _
TN_ _ _
SSMTC
SSMIC
4
1
Calibration curve number
0–9
5
2
Number of points
_1–10
6
1
Failed calibration curve generation
F
Description
Output
TOC-LCSH/CSN
341
5.4
342
Specifications
Output
Number
Order
of Bytes
7
6
Maximum standard solution concentration
Data
8
4
Concentration unit
ppm_
ppb_
g/L_
mg/L
ug/L
g_ _ _
mg_ _
ug_ _
%_ _ _
9
2
Dilution factor
Data
10
4
Injection volume [μL]
Data
11
4
Sparge time [min]
Data
12
4
Acid addition ratio [%]
Data
13
3
Persulfate volume [mL]
Data
14
1
Number of washes
Data
15
3
Furnace temperature value [°C]
Data
16
7
Catalyst type
HIGH_ _ _
REGULAR
TC/TN_ _
17
3
Continuous measurement
ON_ OFF
18
3
Standard solution dilution function
ON_ OFF
19
5
SSM average sample amount
Data
20
2
SSM sample amount unit
mg
ug
21
4
SSM sample density
Data
22
9
SSM maximum absolute carbon amount [μg C]
Data
23
5
SSM cell length
LONG_
SHORT
24
1
Calibration curve type
0: least squares
1: point-to-point
25
1
Zero point shift
0: none
1: origin
2: blank
26
3
Protect
ON_
OFF
27
6
Calibration curve slope
Data
28
7
Calibration curve intercept
+or - and 6 digits
29
6
Correlation coefficient
Data
*30
2
Calibration curve point number
_1-10
*31
6
Standard solution concentration
Data
*32
7
Source solution concentration
Data
*33
4
Source solution dilution factor
Data
*34
4
Additional measurements SD value
Data
TOC-LCSH/CSN
Description
Output
5.4
Specifications
Output
Number
Order
of Bytes
*35
4
Additional measurements CV value
Data
*36
3
Vial number or port number
Data
*37
5
SSM sample amount value
Data
*38
2
SSM sample amount unit
mg
*39
2
Number of measurements value
Data
*40
2
Maximum number of additional measurements value
Data
*41
5
Area average value
Data
*42
4
Area value SD
Data
*43
4
Area value CV
Data
*44
5
SSM sample amount average value
Data
*45
2
Total number of measurements
Data
*46
1
Discard point information
_
Description
Output
uL
E
*47
2
Number of measurements
*48
5
Area value
*49
5
SSM sample amount corrected area value
*50
5
SSM sample amount
*51
1
Discard information
_1
_2...
_
E
*52
7
Remark
Remark
*53
2
Line feed code
CR(0D)
LF(0A)
*30 to *53, output is repeated following completion of each calibration point.
*48 to *53, output is repeated following each measurement for all calibration curve points.
TOC-LCSH/CSN
343
5.4
Specifications
Sample Measurement Result
These data are output following completion of sample measurement.
Output
Number
Order
of Bytes
1
12
Identifier
MEAS_RESULT
2
21
Measurement time
Example: 04 (APR)01-2003_09:00
3
16
Sample name or group name
Sample or group
name
4
1
Vial number or port number
Data
5
4
Concentration unit
ppm_
ppb_
g/L_
mg/L
ug/L
g_ _ _
mg_ _
ug_ _
%_ _ _
6
2
SSM sample amount unit
mg
ug
7
6
TOC (TC-IC) concentration value
Data
8
4
TOC (TC-IC) concentration unit
ppm_
Description
Output
ppb_
g/L_
mg/L
ug/L
g_ _ _
mg_ _
ug_ _
%_ _ _
9
8
TOC (TC-IC) conversion value name
Conversion name
10
6
TOC (TC-IC) concentration conversion value
Data
11
6
TOC (TOC + NPOC) concentration value
Data
12
4
TOC (TOC + NPOC) concentration unit
ppm_
ppb_
g/L_
mg/L
ug/L
g_ _ _
mg_ _
ug_ _
%_ _ _
344
13
8
TOC (TOC + NPOC) conversion value name
Conversion name
14
6
TOC (TOC + NPOC) concentration conversion value
Data
TOC-LCSH/CSN
5.4
Output
Number
Order
of Bytes
15
5
Specifications
Description
Measurement type
Output
TC_ _ _
IC_ _ _
POC_ _
TN_ _ _
SSMTC
SSMIC
16
4
Injection volume [μL]
17
5
SSM average sample amount
Data
18
1
Calibration curve number used
Data
19
2
Dilution factor
Data
20
4
Sparge time [min]
Data
21
4
Sparge gas flow rate [mL/min]
Data
22
4
Acid addition ratio [%]
Data
23
3
Persulfate volume [mL]
Data
24
2
Number of washes
Data
25
2
Number of measurements
Data
26
5
Area average value
Data
27
5
Sample volume corrected area average value
Data
28
6
Concentration average value
Data
29
4
Area value SD
Data
30
4
Concentration value SD
Data
31
4
Area value CV
Data
32
4
Concentration value CV
Data
33
6
Injection volume corrected concentration value
Data
34
6
Dilution factor corrected concentration value
Data
Conversion name
Data
35
8
Conversion value name
*36
6
Concentration conversion value
Data
*37
2
Number of measurements
_1
*38
6
Concentration value
Data
*39
5
Area value
Data
*40
5
Injection volume corrected area value
Data
*41
4
Injection volume [μL]
Data
*42
5
SSM sample amount
Data
*43
1
Calibration curve number used
Data
*44
2
Auto dilution factor
Data
*45
1
Discard information
_
_2...
E
*46
7
Remark
Remark
47
2
Discard point information
_
48
2
E
Line feed code
CR(0D)
LF(0A)
*37 to *46, output is repeated following each measurement.
TOC-LCSH/CSN
345
5.4
Specifications
TC Blank Check Result
These data are output following completion of the TC Blank Check measurement.
Output
Number
Order
of Bytes
1
12
Identifier
BLANK RESULT
2
21
Measurement time
Example: 04 (APR)01-2003_09:00
3
4
Injection volume [μL]
Data
4
3
Persulfate volume [mL]
Data
5
5
Area value
Data
*6
2
Set number of times
_1 _2...10
*7
5
Area average value
Data
*8
4
Area value SD
Data
*9
4
Area value CV
Data
*10
1
Number of measurements
_1 _2...5
*11
5
Area value
Data
*12
1
Discard point information
_
Description
Output
E
*13
7
Remark
Remark
14
2
Line feed code
CR(0D)
LF(0A)
*6 to *13, output is repeated following completion of each set (set number of times).
*10 to *13, output is repeated following each measurement.
346
TOC-LCSH/CSN
5.5
5.5
Standard Accessories
Standard Accessories
Table 5.3 • Standard Accessories List 1 (TOC-LCSH/CSN)
Part Number
Part Name
TOC-LCSH
TOC-LCSN
S638-41323
Combustion tube, in case
2
1
S638-92069-02
TOC regular catalyst set
1
1
S638-92070-01
TOC high sensitivity catalyst set
1
-
638-42100-01
Cooling tubing unit
1
-
S638-16023
Catalyst filling rod
1
1
S071-60821-08
Power cord set (100-127V)
1
1
S071-60814-06
Power cord set (220-240V)
1
1
S638-59296-01
Plunger tip
1
1
S638-59296
Syringe
1
1
S072-60359-01
Wiring band
2
2
S072-02004-26
Fuse (100-127V)
2
2
S072-02004-27
Fuse (220-240V)
2
2
S631-78002
Wrench (for 8-port valve)
1
1
S638-53152
Rinse water bottle
1
1
S638-20072
Cap
2
1
S638-64091-91
DVD ROM "TOC-Control L"
1
1
S038-00292-04
Plastic bottle
2
1
S630-00992
Halogen scrubber
1
1
S630-00557
Quartz wool, 1g
1
1
S638-94599
USER'S MANUAL
1
1
Table 5.4 • Standard Accessories List 2 (ASI-L Autosampler)
Part Number
Part Name
9 mL
24mL
40mL
S638-52337
Rinse water bottle
1
1
1
S072-60310-03
Wiring band, TM-53M
2
2
2
S631-51869-20
Name plate, SAMPLE
1
1
1
S631-51869-21
Name plate, GAS
1
1
1
S072-60301
Wiring band, Nylon TY-23M
1
1
1
S638-74492
Connection cable
1
1
1
S638-41472-01
Water sampling needle
1
1
1
TOC-LCSH/CSN
347
5.5
Standard Accessories
Table 5.5 • Standard Accessories List 3 (OCT-L 8-Port Sampler)
Part Number
Part Name
OCT-L OCT-L
(1)
(2)
1
S638-56251-01
8-port valve rotor
1
S638-42106-01
Flared tubing set C
1*
S638-42106-02
Flared tubing set C2
S638-74492-01
Connection cable
S638-74476-02
Second unit
connection cable
Details
Rotor (for replacement maintenance)
8 sample tubes, 1 tube for connection to
main unit.**
1*
8 sample tubes, 1 tube for connection to
main unit. ***
Cable for connection to the main unit
1
1
Cable for connecting OCT-L (1) to OCTL (2)
* Flanged tubing in C sets have an inner diameter of 1.0mm.
** Connect this tubing to the common (COM) port of the 8-Port Sampler and port No. 2 on
the TOC-L unit.
*** Connect this tubing to the common (COM) port of the 8-Port Sampler and port No. 1 on
the TOC-L unit.
348
TOC-LCSH/CSN
5.6
5.6
Special Accessories
Special Accessories
Table 5.6 • Special Accessories List
Part Number
Part Name
Comment
S638-93199-58
Auto Sampler ASI-L
Dedicated 24 mL vial model
S638-93200-58
Auto Sampler ASI-L
Common 9 mL/40 mL vial model
S638-92327-58
ASI Accessories (9 mL)
S638-92325-58
ASI Accessories (24 mL)
S638-92326-58
ASI Accessories (40 mL)
S638-53044-06
9 mL vial rack set for ASI
9 mL vial rack + 9 mL vial set
S638-53044-04
24 mL vial rack set for ASI
24 mL vial rack + set of 24 mL vials,
caps and septums
S638-53044-05
40 mL vial rack set for ASI
40 mL vial rack + set of 40 mL vials,
caps and septums
S638-67099-41
Stirrer (for 24 mL vials)
Autosampler for 24 mL vials
S638-67100-41
Stirrer (for 40 mL vials)
Autosampler for 40 mL vials
S046-00617-02
Stirring bar (for 24 mL vials)
1 stirring bar for 24 mL vials, 1 is
required for sample measurement
S046-00617-03
Stirring bar (for 40 mL vials)
1 stirring bar for 40 mL vials, 1 is
required for sample measurement
S638-53096
9 mL ASI vial
100 pcs.
S638-41462
24 mL ASI vial
100 pcs.
S038-00158-11
40 mL ASI vial
72 pcs.
Includes caps and septums
S638-20074-01
Cap (for 24 mL vials)
100 pcs.
S038-00165-61
Septum (for 24 mL vials)
100 pcs.
S638-93201-58
8-Port sampler OCT-L (first unit)
S638-93202-58
8-Port sampler OCT-L (second
unit)
S638-91108-58
TN unit TNM-L
S638-93210-41 or
S638-93210-58
SSM-5000A Solid Sample
Module for Total Organic Carbon
Analyzer
-41: For AC 100 ~ 120 V
S638-56239-41
Cell switching valve set
Option for SSM-5000A
S638-42101-01, 02
POC measurement kit
"-01" is for N Type, "-02" is for H Type
S638-41447-03
Carrier gas purifier kit
S638-77183-40
External sparge kit
Only when using TOC-L
S638-77183-41
External sparge kit (with ASI-L)
When using ASI-L Autosampler
S638-93149-03
Manual injection kit
For expanding to a second unit
-58: For AC 220 ~ 240 V
TOC-LCSH/CSN
349
5.6
Special Accessories
Table 5.6 • Special Accessories List
Part Number
Part Name
Comment
S638-41586
Suspended solids kit (when used
with TOC-L alone)
Only when using TOC-L
S638-93151-04
Suspended Solids Kit (when ASIL is used)
When using ASI-L Autosampler
S638-42054-02
Nitrogen currier gas kit
Enables use of high purify nitrogen gas
with less than 1 ppm each of CO, CO2
and HC as carrier gas.
TN measurement cannot be performed
when using this kit with the TNM-L.
350
S638-52572-03
B-type halogen scrubber
S638-59328
Small syringe kit
S638-93176-01,-02
Combustion tube kit for high salt
samples
"-01" is for N Type, "-02" is for H Type
S630-08585-05
Cylinder pressure regulator
User can provide this item.
S638-41204
Air supply tubing set (with 20
meters of tubing)
User can provide this item.
S638-52344
Drain bottle (for ASI)
S638-56255-41
Carrier gas regulator
TOC-LCSH/CSN
Use this regulator when the pressure
from the carrier gas supply source cannot
be stably maintained at 200 ± 10 kPa.
5.7
5.7
Consumable Parts List
Consumable Parts List
5.7.1 Consumable Parts List
Table 5.7 • Consumable Parts List 1 (TOC-LCSH)
Part Number
Part Name
Comment
S638-41323
Combustion tube, in case
S638-60116
TOC regular catalyst
S630-00105-01
Platinum mesh
To support catalyst, 2 included
S630-00557
Quartz wool
To support catalyst, 1 g
S630-00996
TOC high sensitivity catalyst
S630-00999
CO2 absorber
S630-00992
Halogen scrubber
S036-11209-84
O-ring, 4D P 10A
For slider, 5 pcs.
S638-15025
O-ring, PTFE
For slider, 1 pc.
S036-11222-84
O-ring, 4D P22
For IC reaction tube, 5 pcs.
S036-11219-84
O-ring, 4D P20
For TC reaction tube, 5 pcs.
S042-00405-11
IC reaction solution supply pump head
S046-00044-12
Membrane filter
S638-56251-01
8-port valve rotor
S638-59296-01
Plunger tip
S638-92206-04
TOC-LCSH consumable parts set
Type name: Plug, XT24-197-1-4
Refer to "Table 5.9 • TOC-LCSH, CSN
Consumable Parts Set Breakdown" for
an itemized list
Table 5.8 • Consumable Parts List 2 (TOC-LCSN)
Part Number
Part Name
Comment
S638-41323
Combustion tube, in case
S638-60116
TOC regular catalyst
S630-00105-01
Platinum mesh
To support catalyst, 2 included
S630-00557
Quartz wool
To support catalyst, 1 g
S630-00999
CO2 absorber
Contains 500 mL
S630-00992
Halogen scrubber
S036-11209-84
O-ring, 4D P 10A
For slider, 5 pcs.
S638-15025
O-ring, PTFE
For slider, 1 pc.
TOC-LCSH/CSN
351
5.7
Consumable Parts List
Table 5.8 • Consumable Parts List 2 (TOC-LCSN)
Part Number
Part Name
Comment
S036-11219-84
O-ring, 4D P20
For TC reaction tube, 5 pcs.
S046-00044-12
Membrane filter
S638-56251-01
8-port valve rotor
S638-59296-01
Plunger tip
S638-92206-05
TOC-LCSH consumable parts
set
Refer to "Table 5.9 • TOC-LCSH, CSN
Consumable Parts Set Breakdown" for
contents
Table 5.9 • TOC-LCSH, CSN Consumable Parts Set Breakdown
Part No.
Description
Qty
Remark
TOC-LCSH TOC-LCSN
S638-41323
Combustion tube (in case)
2
2
S638-60116
TOC regular catalyst
2
2
S630-00996
TOC high sensitive catalyst
1
0
S630-00557
Quartz wool
1
1
S630-00992
Halogen scrubber
2
2
S036-11209-84
O-ring, 4D P 10A
1
1
5 pcs.
S638-15025
O-ring, PTFE
2
1
1 pc.
S036-11219-84
O-ring, 4DP 20
1
1
5 pcs.
S042-00405-11
IC reagent supply pump head
1
0
S638-56251-01
8-port valve rotor
1
1
S638-59296-01
Plunger tip
2
2
Table 5.10 • Consumable Parts List 3 (ASI-L Autosampler)
Part Number
352
Part Name
Comment
S038-00158-11
40 mL vial set
40 mL, 72 vials, septa and caps
S638-41462
24 mL vial
24 mL, 100 pcs.
S638-53096
9 mL vial
9 mL, 100 pcs.
S038-00165-61
Septum
24 mL, 100 pcs.
S038-00165-50
Septum
40 mL, 100 pcs.
S638-20074-01
Cap
24 mL, 100 pcs.
S038-00165-40
Cap
40 mL, 200 pcs.
S042-00405-11
Rinse pump head
TOC-LCSH/CSN
5.7
Consumable Parts List
Table 5.11 • Consumable Parts List 4 (8-Port Sampler OCT-L)
Part Number
S638-56251-01
Part Name
Comment
8-Port valve rotor
Table 5.12 • Consumable Parts List 5 (TNM-L TN Unit)
Part Number
Part Name
S638-65232
Ozone treatment - catalyst
S638-60074
Ceramic fiber
S638-42127
Ozone exhaust tubing
Comment
300 g included
Table 5.13 • Consumable Parts List 6 (Carrier Gas Purifier Kit)
Part Number
Part Name
S630-00556
CO2 absorber, absorbent
S638-60116
TOC regular catalyst
Comment
500 g included
Table 5.14 • Consumable Parts List 7 (B-Type Halogen Scrubber)
Part Number
S631-60069
Part Name
Comment
Stainless mesh for absorption
TOC-LCSH/CSN
353
5.7
Consumable Parts List
5.7.2 Recommended Consumable Part Replacement Period
Table 5.15 indicates the guidelines for the major recommended consumable part
replacement periods when NPOC measurement is performed on samples that are
comparatively as clean as tap water, using TOC standard catalyst and at a rate of about
500 samples per month (operating five days a week).
Note that these are not guaranteed values and the replacement period changes according to
instrument usage. In particular, measuring samples that contain salt, acid, or alkalis may
shorten the replacement period of parts such as the combustion tube, catalyst, and halogen
scrubber.
Table 5.15 • Recommended Consumable Part Replacement Period
Part Number
354
Part Name
Comment
S638-41323
Combustion tube (in case)
6 months
S638-60116
TOC standard catalyst
6 months
S630-00557
Quartz wool
1 year
S630-00999
CO2 absorber
1 year
S630-00992
Halogen scrubber
6 months
S638-15025
O-ring, PTFE (1 pc.)
1 year
S036-11209-84
O-ring, 4D P10 A (5 pcs.)
1 year
S036-11219-84
O-ring, 4D P20 (5 pcs.)
6 months
S638-56251-01
8-port valve rotor
1 year
S638-59213-01
Plunger tip
6 months
TOC-LCSH/CSN
5.8
5.8
Maintenance Parts List
Maintenance Parts List
Table 5.16 • Maintenance Parts List 1 (TOC-LCSH/CSN)
Part Number
Part Name
Comment
S638-56251
8-port valve
S638-59296
Syringe
S638-42119-01
Tube 1
For port number 1 on the 8-port valve
S638-42029-07
Tube set (sampling)
For port number 2 on the 8-port valve
(for ASI connection)
S638-42119-03
Tube 3
For port number 3 on the 8-port valve
S638-42119-04
Tube 4
For port number 4 on the 8-port valve
S638-42119-05
Tube 5
For port number 5 on the 8-port valve
S638-42119-06
Tube 6
For port number 6 on the 8-port valve
S638-42119-07
Tube 7
For port number 7 on the 8-port valve
S638-42119-08
Tube 8
For port number 8 on the 8-port valve
Table 5.17 • Maintenance Parts List 2 (ASI-L Autosampler)
Part Number
Part Name
Comment
S638-41472-01
Water sampling needle
The sparging needle is identical to this
part.
S638-41450-01
Needle for suspended solids
kit
For use with 24 mL and 40 mL vials and
the suspended solids kit, 0.8 mm, 1
included
S638-42029-07
Tube set
1 tube, retainer, and tube seal for both
sampling and sparging
S638-42029-04
Tube set (sampling for the
suspended solids kit)
1 sampling tube for the suspended solids
kit, with retainer and tube seal
S638-67095-41
Motor (for 24 mL vials)
For stirrer 24 mL vials
S638-67095-42
Motor (for 40 mL vials)
For stirrer 40 mL vials
S638-67099-41
Stirrer (for 24 mL vials)
For autosampler 24 mL vials
S638-67100-41
Stirrer (for 40 mL vials)
For autosampler 40 mL vials
TOC-LCSH/CSN
355
5.8
Maintenance Parts List
Table 5.18 • Maintenance Parts List 3 (OCT-L 8-Port Sampler)
Part Number
Part Name
Comment
S638-56251-01
8-port valve rotor
Spare rotor
S638-42119-01
Water sampling tubing
Water sampling tubing for TOC-L
S638-42119-21
OCT connection tubing
TOC-L to OCT-L connection tubing
Table 5.19 • Maintenance Parts List 4 (Manual Injection Kit)
Part Number
356
Part Name
Comment
S630-02621
Open / Close valve, TC
injection port
S638-60733-01
Microsyringe, MANU10
10 µL
S638-60733-02
Microsyringe, MANU25
25 µL
S638-60733-03
Microsyringe, MANU50
50 µL
S638-60733-04
Microsyringe, MANU100
100 µL
S638-60733-05
Microsyringe, MANU250
250 µL
S638-60733-06
Microsyringe, MANU500
500 µL
TOC-LCSH/CSN
5.9
5.9
Installation
Installation
5.9.1 Before Installation
5.9.1.1 Parts Inspection
Confirm that all of the components listed in Section 5.5 "Standard Accessories" on page
347 are included in the shipping package.
5.9.2 Installation Site
Be sure to take into account the size of the instrument, how it will be used, and the
installation conditions indicated below when selecting an installation site. Instrument
damage or errors in results may occur depending on the conditions of the installation site.
5.9.2.1 Installation Site Selection
This instrument is designed for use on a desk or bench, allowing the operator to use the
operation keys while viewing the LCD screen.
The external dimensions of the instrument are shown in Figure 5.3 "External Dimensions
of Instrument with ASI-L" on page 357. A space of at least 200mm (8 inches) is required
on either side of and behind the instrument to enable unhindered operation and
maintenance. In order to prevent any interference during operation, be aware that the main
power switch of the TOC instrument is located on the right side of the main unit and the
power switch of the ASI-L is located on the left side of the device.
TOC-L
main
unit
TOC-L
main
unit
Figure 5.3 External Dimensions of Instrument with ASI-L
TOC-LCSH/CSN
357
5.9
Installation
TOC-L
main
unit
TOC-L
main
unit
Figure 5.4 External Dimensions of the Instrument with the OCT-L 8-Port Sampler
and TNM-L TN Unit (Units: mm)
CAUTION
When lifting the instrument, lift from the bottom and at both sides of the
instrument.
Do not lift it by the front access door, as this may cause instrument damage.
358
TOC-LCSH/CSN
5.9
Installation
5.9.2.2 Installation Site Conditions
The ambient temperature specification for this instrument is 5 to 35 °C (10 to 35 °C for the
OCT-L). Install the instrument in an environment that can maintain this temperature range
in order to obtain stable measurement results.
Prevent condensation from occurring due to changes in ambient temperature and humidity.
Select an installation site that complies with the following conditions.
•
A clean environment, free of corrosive gases, organic gases, and dusts.
Note: Contamination in the atmosphere will cause analysis errors, especially in high
sensitivity analyses.
•
•
•
•
•
•
A strong, level bench, free of vibration and shock.
An indoor location with a stable ambient temperature.
A location with access to a completely grounded, stable power supply.
Installation category: II
Pollution degree: 2
Altitude: up to 2000 m
CAUTION
Avoid locations where flames are prohibited. Some internal parts reach high
temperatures and could cause a fire hazard.
Due to the possibility of analysis error, avoid the following kinds of locations.
•
•
Locations close to heat sources or windows in direct sunlight, or in direct contact with
drafts from air conditioning vents.
Near equipment that generates intense magnetic fields, electrical fields, or high
frequency waves.
TOC-LCSH/CSN
359
5.9
Installation
5.9.3 Installation Procedure
5.9.3.1 Connecting Power Supply and Ground
Connecting Power Supply
Connect the instrument to a stable, AC100-120V (100V system) or AC220-240V (200V
system), 50Hz or 60Hz (single phase) power supply with sufficient capacity to
accommodate 600 VA or greater current.
CAUTION
The instrument may not operate properly if the power supply voltage exceeds
the range of 100-120V or 220-240V. Unstable voltage may cause problems
during high sensitivity analysis.
Note:
Since this instrument is compatible with both 50Hz and 60Hz power supplies, it
can be used with either frequency. Use only Shimadzu-specified or the supplied
power cable. Do not use unspecified power cables.
Grounding
The included power cord is a three-conductor cable including a ground wire and a 2P plug
(with ground) at the end.
The voltage terminals (AC) and ground terminal (ACC) on the power plug of this
instrument are arranged as shown in Figure 5.5 "Power Plug" on page 360. Connect them
so that they match the power outlet being used.
Voltage terminal (AC)
Ground terminal (ACC)
Ground terminal (G)
(Be sure to ground completely.)
Figure 5.5 Power Plug
CAUTION
•
•
360
TOC-LCSH/CSN
In addition to the consideration of safety, complete grounding of the instrument is
very important and necessary in order to prevent malfunctions due to the
interference of signal noise in the instrument's electrical circuitry. A Type-3
ground (ground resistance: 100Ω or less, see Electrical Facilities Engineering
Standards for details) is recommended.
Perform grounding separately and avoid contact with water supply pipes, gas
pipes, and lightning rods, etc.
5.9
Installation
5.9.3.2 Changing the Power Supply Voltage
The instrument was set up when it was shipped to match the power supply voltage in the
locale where it will be used. In the event that it becomes necessary to change the power
supply voltage, please contact your Shimadzu representative. Depending on the voltage
change, an authorized Shimadzu service engineer may be required to rewire connections to
the terminal block to change the power supply voltage and/or perform changes to the main
board.
5.9.3.3 Connecting Gas
Use one of the following as the carrier gas supply for this instrument.
•
•
•
Cylinders filled with high purity air
Compressed air or instrumentation air (requires the optional carrier gas purification kit
on the N Type instrument)
Gas cylinder filled with high purity nitrogen or instrumentation high purity nitrogen
(requires the optional N2 carrier gas kit)
High Purity Air Cylinders
High purity air is synthetic air manufactured from pure nitrogen and pure oxygen. It must
be guaranteed to contain less than one 1ppm each of carbon dioxide, carbon monoxide, and
hydrocarbons as impurities.
The cylinder must be equipped with a pressure regulator to supply it at 200 ± 10 kPa
(29PSI) to the gas connection inlet of the instrument.
Note:
If the carrier gas contains excessive impurities, analysis accuracy is diminished
and good results will not be obtained.
Precautions for Handling Gas Cylinders
•
•
•
•
•
•
The handling and safety management of high-pressure gases is strictly regulated
by high-pressure gas control laws, general high-pressure gas safety codes, and
fire laws.
The gas used in this instrument itself is not dangerous, but mistakes in the
handling of high-pressure gas cylinders can be extremely hazardous. Please
carefully read and obey the following precautions.
Place gas cylinders in a well-ventilated location out of direct sunlight.
Ensure that gas cylinders never reach temperatures higher than 40°C.
Make sure there are no open flames anywhere within 2 meters of a gas cylinder.
Secure cylinders with bands or other fasteners to prevent tipping and falling.
When finished using gas, immediately and completely turn OFF all valves on the
cylinder.
Inspect the operation of the pressure gauge at least once every three (3) months.
TOC-LCSH/CSN
361
5.9
Installation
Compressed Air or Instrument Air Purified with the Carrier Gas Purification
Kit
Using the carrier gas purification kit on the N Type instrument enables the use of
compressed air, instrumentation air, and air from gas cylinders that is generally impure.
Since there are limits to the capabilities of the Carrier Gas Purification Kit, the following
conditions must be met when supplying compressed air. This kit cannot be used with the H
Type instrument.
•
Provide an air filter in the supply line to remove dust, oil mist, and water drops, etc.
Place an air filter in the tubing near the gas connection inlet of the instrument when a
compressor is used.
• If you intend to use an air compressor, select an oilless air compressor. Shimadzu offers
the SLP5D-2SV oilless and silent air compressor (P/N S638-59203) and AW30-02BGN filter regulator (P/N S040-82112-43) as options.
• There are cases where the organic gas concentration is too high to be removed
completely by the gas purifier. Analysis accuracy is poor in atmospheres containing
high concentrations of volatile gases from exposed organic solvents and gasoline, etc.,
or high concentrations of automobile and diesel engines exhaust.
If the presence of these kinds of gases cannot be avoided, use a filter to remove organic
particles and/or gases.
Using Gas Cylinder High Purity Nitrogen or Instrumentation High Purity
Nitrogen
High purity nitrogen gas must be guaranteed to contain less than 1 ppm of each of the
following impurities: carbon dioxide, carbon monoxide, and hydrocarbons.
Install a pressure regulator on the cylinder and supply gas to the gas connection inlet on the
instrument at 200 ± 10 kPa.
These specifications limit the upper measurement concentration to 100 mg/L for TC and
NPOC. For sample measurements that exceed this concentration, measurement is possible
using the automatic dilution function if the concentration of the sample is less than
100 mg/L after dilution. Also note that TN measurement cannot be performed using the
TNM-L with these specifications.
Note:
Excessive impurities in the carrier gas will diminish analysis accuracy and
prevent the acquisition of sound measurement results.
Gas Supply Pressure
Ensure that the gas supplied to the gas inlet connection of the instrument maintains a
constant, stable pressure of 200 ± 10 kPa (29PSI).
Use the optional carrier gas regulator if pressure cannot be stably supplied at 200 ± 10 kPa.
In this case, set the carrier gas supply pressure to 300 ± 10 kPa.
Note:
362
TOC-LCSH/CSN
Never allow the carrier gas supply pressure to exceed 600 kPa when using the
optional carrier gas regulator.
5.9
Installation
Gas Tubing Connections
The special accessory Air Supply Tubing Set includes nylon tubing and connectors (two [2]
half unions).
Procedure
Half union
Nylon tubing
Figure 5.6 Gas Tubing Connection
1.
Connect the half unions to the carrier gas inlet on the instrument and the connection
outlet (NPT ¼") of the gas supply source.
2.
Connect the nylon tubing (4mm OD, 2.5mm ID) between the gas supply source and
the instrument.
Note: The nylon tubing can be connected simply by firmly inserting it
into the half union. To disconnect the tubing, pull the tubing off
while pushing down firmly on the green-colored ring of the half
union with a screwdriver.
3.
After connection, verify that there are no gas leaks.
CAUTION
•
•
•
•
Do not allow any acute bends in the tubing.
Clean the tubing and connectors to remove any oils or other contaminants on
their inner surfaces.
Copper tubing or stainless steel tubing may also be used.
Always keep the tubing exclusive to this instrument. Branching the tubing and
connecting it to other equipment may adversely affect measurement performance
due to fluctuations in supply pressure.
TOC-LCSH/CSN
363
5.9
Installation
5.9.3.4 Installing the Drain Container
Place the drain container under the bench on which the TOC-L is installed. A suitable drain
container is a plastic container with a 10 to 20 L capacity. The drain tubing from the TOCL is inserted into this drain container. Take note of the following precautions.
•
As the flow resistance of the drain is low, lead the drain tubing from the instrument in
such a way that prevents any part of the tubing from pointing upwards and do not allow
the end of the drain tubing to become submerged in the drain container. Exposing the
drain tubing to atmospheric pressure near the TOC-L is also effective. Note that high
flow pressure in the drain may inhibit drain discharge and cause an overflow within the
TOC-L.
TOC-L
Drain discharge tubing (Avoid
installing the tubing as shown
by the dotted line.)
Drain container (Prepare a
suitable drain container.)
Figure 5.7 How to Lead the Drain Tubing from the Instrument to the Drain Container
CAUTION
•
•
364
TOC-LCSH/CSN
Drain discharge contains acids and other corrosive substances so always handle it
with care to prevent spills and contact with the skin.
Depending on measurement conditions, drain discharge may have a pH level less
than 2.0. Drain discharge with a pH less than 2.0 is classed as industrial waste
subject to special control. Request transfer by an authorized industrial waste
transporter to an authorized industrial waste processing facility to process any
industrial waste subject to special control. If you wish to perform deacidification
on your own premises, contact the environmental agency in your jurisdiction.
5.9
Installation
5.9.4 Installing the ASI-L
This section describes procedures for installing the ASI-L autosampler.
Positioning the ASI-L
Place the autosampler about 100 mm to the left of the TOC-L, as shown in Figure 5.8.
Figure 5.8 Installing the ASI-L
Note:
If the distance from the instrument is more than 100 mm, the water sampling tube
may impede the movement of the ASI-L arm resulting in operation errors or
damage to the instrument.
Removing the Shipping Screw
The ASI-L arm is secured with a shipping screw to prevent damage during shipment.
Before connecting power to the instrument, remove the ASI-L cover to access the shipping
screw, which is located on the retaining bracket. Remove the shipping screw and replace
the cover. Label the shipping screw and store it for future use.
CAUTION
To prevent instrument damage, verify that the ASI-L arm is firmly attached to
the retaining bracket with the shipping screw before shipping the instrument or
moving it to another location.
Connecting Cables
The TOC-L and ASI-L are connected using cables, as described below.
CAUTION
Verify that the TOC-L is switched OFF before performing the following
procedure.
TOC-LCSH/CSN
365
5.9
Installation
Procedure
1.
Connect the provided cable to the connectors on the rear of the ASI-L and rear of the
TOC-L.
Connection cable
Figure 5.9 Connecting the Cables (TOC-L to ASI-L)
Connecting the Sample Tubing and Sparge Tubing (External Sparge Kit)
The procedure for connecting the ASI-L sample tubing and sparge tubing for the External
Sparge Kit is as follows.
Procedure
1.
Attach the bush on the end of the water sampling tubing to port number 2 on the 8port valve of the sample injector on the TOC-L.
2.
If using the external sparge kit, attach the sparging tubing for ASI-L.
Sparging tubing for ASI-L
Sparging tubing if not using the ASI-L
ASI-L sparging
needle
Sparge gas flow meter
Figure 5.10 Attaching the Sparging Tubing for ASI-L
Note:
366
TOC-LCSH/CSN
Do not use the flow meter knob to turn off the sparge gas flow.
The sparge gas flow meter may break if the flow adjustment knob is
overtightened.
5.9
Installation
Installing the Needle
The water sampling needle and sparging needle (for use with the external sparge kit) are of
the same type. Insert the sparging needle into the opening on the right side of the needle
holder.
CAUTION
Verify that the TOC-L is switched OFF before performing the following
procedure.
Installing the Water Sampling Needle and Sparging Needle
1.
2.
Open the needle cover door towards the left.
Remove the needle holder retaining screw and then remove the needle holder from the
arm.
Needle retaining
bracket
Needle holder
retaining screw
Needle holder
Needle cover
Water sampling needle
Sparging needle
Figure 5.11 Inside the Needle Cover
3.
Insert the needle into the opening in the needle holder.
TOC-LCSH/CSN
367
5.9
Installation
4.
Secure the needle by turning the retaining bracket and tightening the screw at the top
of the needle holder.
Note: There are two openings; the left opening is for the sample tubing
and the right opening is for the sparge tubing.
Retaining bracket
Needle holder
Sample needle
Figure 5.12 Installing the Needle
5.
Feed the water sampling tubing through the hole in the needle cover and pull it inside
the needle cover. When using the external sparge kit, pull the sparging tubing inside
the needle cover in the same manner.
6.
Fit the water sampling tubing or sparging tubing to the top of the needle and attach a
retainer.
7.
Insert the bottom of the needle into the needle guide hole, run the needle holder
through the arm pin, and then secure the needle holder with the retaining screw.
8.
Close the needle cover door.
Installing the Turntable, Vial Rack and Cover
Installing the Turntable
1.
368
TOC-LCSH/CSN
Place the turntable on the ASI-L.
Note: There is no distinction between front and rear of the turntable, so
placement orientation is irrelevant.
5.9
2.
Installation
Place the turntable so that the 3 guides on the ASI-L pass through the 3 holes at the
center of the turntable.
Turntable
Figure 5.13 Installing the Turntable
Installing the Vial Rack
1.
2.
Place the vial rack on top of the turntable.
Rotate the vial rack until the guides of the turntable fit into the vial rack. This secures
the vial rack in place.
Installing the Cover
1.
Place the cover on the ASI-L.
Note: There is a magnet at the left rear of the cover. Verify that the cover
and ASI-L are in contact via the magnet.
Install the Rinse Bottle and Drain Tank
Installation of the rinse bottle and drain tank is explained below.
Rinse and drain tubing are attached to the autosampler, and are respectively labeled
"RINSE" and "DRAIN." Use the rinse water tubing as it is, and cut the drain tubing to an
appropriate length.
Preparation
•
•
The rinse bottle is provided as a standard accessory.
The drain bottle (P/N S638-52344) is provided as a special accessory. A suitable
substitute may be used as the drain container. For the latter, use a plastic container with
a 10 to 20 L capacity. For details on installation and precautions, refer to Section 5.9.3.4
"Installing the Drain Container" on page 364. Such a container of sufficient capacity can
be used in conjunction with the drain container for TOC-L.
TOC-LCSH/CSN
369
5.9
Installation
Installation Procedure
1.
2.
Place the rinse bottle on the same table or bench as the TOC-L and ASI-L.
Insert the rinse tubing from the ASI-L into the rinse bottle.
CAUTION
Do not allow any slack or bends in the tubing that could cause a buildup of water
pressure.
Before Starting Analysis
Check the following before starting analysis.
•
•
The rinse water bottle is filled to above the 2L mark on the bottle.
The tip of the rinse tube reaches nearly to the bottom of the rinse water bottle.
CAUTION
Rinse water will not be delivered and air may be taken into the TOC-L injection
pump if the above checks are not made.
370
TOC-LCSH/CSN
5.9
Installation
5.9.5 OCT-L Installation
The OCT-L is installed as described below.
Installation Procedure
Place the 8-port sampler about 50 mm to the left of the TOC-L main unit, as shown in
Figure 5.14.
The unit is set up to the left of the TOC-L main body as shown in Figure 5.3"External
Dimensions of Instrument with ASI-L".
TIP »
When 2 OCT-L 8-Port Samplers are to be used, place both units to the left of the TOC-L
main unit as shown in the overhead view of Figure 5.3"External Dimensions of Instrument
with ASI-L".
Figure 5.14 Installation of the OCT-L
Cable Connections
The cable is connected between the main unit of the TOC-L and the OCT-L.
CAUTION
Confirm that the power to the TOC-L main unit is switched OFF before
performing this procedure.
Connection Procedure
1.
2.
3.
Remove the 4 screws at the top of the OCT-L, and take off the cover.
Connect the power and signal cable to the circuit board of the OCT-L.
Feed the cable under the rear cover as shown in Figure 5.15 and then reattach the
cover to its original position.
TOC-LCSH/CSN
371
5.9
Installation
4.
Connect the other end of the OCT-L cable to the OCT-L connector on the rear of the
TOC-L main unit.
Cover
Connection cable
Figure 5.15 Cable Connections (TOC-L and OCT-L)
Installing Two OCT-L Units
When installing two OCT-L units, a signal cable (standard accessory) is connected between
OCT-L (1) and OCT-L (2).
Installation Procedure
1.
2.
Remove the covers from both OCT-L units.
Connect the signal cable exiting OCT-L (2) to the connector of OCT-L (1).
Connection cable
Figure 5.16 Connecting Two OCT-L Units
372
TOC-LCSH/CSN
5.9
Installation
3.
Remove the port number label from the OCT-L (2) unit and replace it with the port
number label provided with the unit.
Note: The port that was originally labeled as port No. 1 should be labeled
as port No. 9.
4.
Replace the covers on both of the OCT-L units.
Connecting the Water Sampling Tubing
Connect the water sampling tubing according to the procedure described below.
Connection Procedure
1.
Connect the bushing on the end of provided tubing (tubing with bushes on both ends)
to the common (COM) port on the OCT-L.
2.
Feed the bushing on the other end of the tubing through the hole in the left side of the
TOC-L main unit and connect it to port number 2 (or port number 1 for OCT-L (2)) on
the 8-port valve of the syringe pump type sample injector.
3.
Connect the bushing on the ends of the water sampling tubing to ports 1 to 8 on the
OCT-L (or ports 9 to 16 for OCT-L (2)).
Water sampling
tubing
Water sampling
tubing
COM port
Figure 5.17 COM Port and Water Sampling Tubing Connections
Note:
Connection to the TOC-L Main Unit
• OCT-L (1)
Connect the COM tubing to the common (COM) port of OCT-L (1) and port No.
2 on the TOC-L unit.
• OCT-L (2)
Connect the COM tubing to the common (COM) port of OCT-L (2) and port No.
1 on the TOC-L unit
TOC-LCSH/CSN
373
5.9
Installation
5.9.6 Installing the TNM-L
5.9.6.1 TNM-L TN Unit Installation
A technician from Shimadzu or designated by Shimadzu will install this unit.
5.9.6.2 Connecting Ozone Source Air
The TNM-L incorporates an internal ozone generator, requiring a source of air gas
(supplied at about 500 mL/min) separate from the carrier gas supplied to the TOC-L. While
it is possible to use TOC-L high purity carrier gas by providing branch tubing, the
consumption of the combined-use carrier gas would increase to about 150 - 250 mL/min.
Assuming operation at the rate of 8 hours/day, 5 days/week, the 47 L, 12 MPa air cylinder
would require monthly replacement (as compared to every 3 months when used for carrier
gas alone).
Because air gas for ozone generation is not required to be the high purity air used as carrier
gas, it is recommended to use instrumentation air or compressor-supplied air for ozone
generation, separate from the carrier gas.
Using Compressor Air or Instrumentation Air
When using compressor air or instrumentation air for generation of ozone, be sure that the
following conditions are satisfied.
•
•
Install an air filter in the air supply line to eliminate dust, oil mist and water droplets
from the air. If a compressor is used, install the air filter (equipped with drain separation
and discharge branch) close to the tubing connection at the instrument.
If a compressor is used, select an oil-less type air compressor. Shimadzu offers the
SLP5D-2SV oilless and silent air compressor (P/N 638-59203) and AW30-02BG-N
filter regulator (P/N 040-82112-43) as options.
Using a High Purity Air-Filled Cylinder (Via Branch Tubing from Carrier Gas)
High purity air is synthesized air using pure nitrogen and pure oxygen. Ensure that
contaminants, including carbon dioxide, carbon monoxide and total hydrocarbons, are
guaranteed not to exceed 1 ppm each.
Install a pressure regulator on the gas cylinder and supply gas to the instrument so that the
pressure is 300 kPa at the instrument gas connection port.
Note:
374
TOC-LCSH/CSN
If there are excessive contaminants in the carrier gas, measurement results will be
adversely affected due to low measurement reproducibility, etc.
5.9
Installation
Precautions in Handling Gas Cylinders
•
•
•
•
•
•
The handling and safety management of high-pressure gases is strictly regulated
by high-pressure gas control laws, general high-pressure gas safety codes, and
fire laws.
The gas used in this instrument itself is not dangerous, but mistakes in the
handling of high-pressure gas cylinders can be extremely hazardous. Carefully
read and obey the following precautions.
Place gas cylinders in a well-ventilated location out of direct sunlight.
Ensure that gas cylinders never reach temperatures higher than 40°C.
Make sure there are no open flames anywhere within 2 meters of a gas cylinder.
Secure cylinders with bands or other fasteners to prevent tipping and falling.
When finished using gas, immediately and completely turn OFF all valves on the
cylinder.
Inspect the operation of the pressure gauge at least once every three (3) months.
Gas Supply Pressure
Supply gas at a constant, stable pressure of 300 to 600 kPa (44 PSI) at the gas inlet
connection of the TNM-L.
Note:
If a supply pressure higher than 300 kPa is required when using compressed air
or instrument air, always keep it at 600 kPa or less.
Gas Tubing Connections
The special accessory Air Supply Tubing Set includes nylon tubing and connectors (two (2)
half unions).
Half union
Nylon tubing
Figure 5.18 Gas Tubing Connection
Procedure
1.
Connect the half unions to the carrier gas inlet on the instrument and the connection
outlet (¼" NPT) of the gas supply source.
2.
Connect the nylon tubing (4 mm O.D., 2.5 mm I.D.) between the gas supply source
and the instrument.
TOC-LCSH/CSN
375
5.9
Installation
Note:
3.
The nylon tubing can be connected simply by firmly inserting it
into the half union. When disconnecting the tubing, pull off the
tubing while pushing down firmly on the green-colored ring of the
half union using a screwdriver.
After connection, check to see that there are no gas leaks.
CAUTION
•
•
•
Do not allow any acute bends in the tubing.
When tubing and connectors are prepared by the user, be sure to use clean
components that are free of oils or other contaminants on their inner surfaces.
Copper tubing or stainless steel tubing may also be used.
Low Ozone Air Supply Pressure Safety Mechanism
As a safety measure, the TNM-L is equipped with an ozone air gas pressure sensor that will
automatically switch off the ozone generator if the ozone air gas pressure decreases below
the prescribed level. If an error message is displayed indicating this problem, perform an
inspection of the ozone air gas supply.
5.9.6.3 Connecting Gas Exhaust Tubing
Since this system uses a chemiluminescence system for the detection of TN components, it
contains an internal ozone generator. The ozone and NOx generated here are removed by
the action of an ozone treatment unit and a NOx absorber, and are then exhausted. However,
in the event that the performance of the ozone treatment catalyst and NOx absorber
deteriorate, ozone and NOx gas may be exhausted in the exhaust gas. Be sure to discharge
exhaust gas to the outdoors or to an exhaust pit, using a 5mm I.D. flexible vinyl hose.
CAUTION
To minimize resistance, leave the exhaust gas tubing open to the atmosphere.
Be sure to connect the gas exhaust tubing to the instrument and discharge the
exhaust gas to the outdoors or an exhaust pit.
If the gas exhaust tubing is not connected, ozone and NOx gas may be exhausted
from the instrument, causing harm to the respiratory organs, etc. of individuals
in the vicinity.
Note:
376
TOC-LCSH/CSN
Leave the end of the exhaust tubing open to the atmosphere to reduce resistance
in the tubing.
5.10
5.10
Safety Data Sheets
Safety Data Sheets
5.10.1 Hydrochloric Acid (HCl)
Shimadzu Scientific Instruments, Inc.
7102 Riverwood Drive Columbia, MD 21046
Tel: 1(800) 477-1227
Revised Date: 2008/06/12
SECTION I
IDENTIFICATION OF THE SUBSTANCE OR MIXTURE
PRODUCT IDENTIFIER :
Hydrochloric Acid
SECTION II
HAZARDS IDENTIFICATION
GHS CLASSIFICATION :
Skin corrosion/irritation:
Serious eye damage/eye irritation:
Acute toxicity-Oral:
Acute toxicity-Inhalation:
Sensitization-Respiratory:
Specific target organ systemic toxicity Single exposure:
Specific target organ systemic toxicity Repeated exposure:
Hazardous to the aquatic environment -Acute hazard:
Category 1A
Category 1
Category 4
Category 1
Category 1
Category 1
Category 1
Category 1
HAZARD SYMBOL :
DANGER
Causes severe skin burns and eye damage
Causes serious eye damage
Harmful if swallowed
Fatal if inhaled
May cause allergy or asthma symptoms or breathing difficulties if inhaled.
Causes damage to organs
Causes damage to organs through prolonged or repeated exposure
Very toxic to aquatic life
PRECAUTIONARY STATEMENTS : <Prevention>
Avoid breathing dust/fume/gas/mist/vapours/spray.
Avoid release to the environment if this is not the intended use.
Do not eat, drink or smoke when using this product.
In case of inadequate ventilation wear respiratory protection as specified by the manufacturer/supplier or the competent
authority.
Use only outdoors or in a well-ventilated area.
Wash thoroughly after handling.
Wear protective gloves and eye/face protection as specified by the manufacturer/supplier or the competent authority.
Wear respiratory protection as specified by the manufacturer/supplier or the competent authority.
<Resoponse>
Collect spillage.
Get medical attention/advice if you feel unwell.
If experiencing respiratory symptoms call a POISON CENTER or doctor/physician.
IF exposed: Call a POISON CENTER or doctor/physician.
IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue
rinsing.
IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing.
IF ON SKIN (or hair): Remove/Take off immediately all contaminated clothing. Rinse skin with water/shower.
IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
IF SWALLOWED: Call a POISON CENTER or doctor/physician if you feel unwell.
Rinse mouth.
Specific treatment is urgent (see ... on this label) .. reference to supplemental first aid instruction if immediate
administration of antidote is required.
Wash contaminated clothing before reuse.
<Storage>
Store container tightly closed in well-ventilated place -if product is as volatile as to generate hazardous atmosphere.
Store locked up.
<Disposal>
Dispose of contents/container to a located point (in accordance with local/regional/national/international regulation).
HAZARD STATEMENTS :
TOC-LCSH/CSN
377
5.10
Safety Data Sheets
SECTION III
COMPOSITION/INFORMATION ON INGREDIENTS
CHEMILCAL IDENTITY :
SYNONYMS :
FORMULA :
MOLECULAR WEIGHT :
CAS NUMBER :
TSCA INVENTORY :
EINECS No. :
EC INDEX NUMBER :
Hydrochloric acid (36 %)
Muriatic acid
HCl
36.46
7647-01-0
Listed
231-595-7
017-002-00-2
SECTION IV
FIRST AID MEASURES
GENERAL ADVICE :
Wash off immediately with soap and plenty of water. In the case of respirable dust and/or fumes, use self-contained
breathing apparatus and dust impervious protective suit. Use personal protective equipment.
Move victim to fresh air. If breathing is difficult, give oxygen. If breathing has stopped, administer artificial respiration.
Maintain normal body temperature with a blanket. If irritation persists, transport to a hospital immediately.
Remove contaminated clothes and shoes, rinse skin with plenty of water or shower. Use soap to help assure removal. If
irritation persists, transport to a hospital immediately.
Remove any contact lenses at once. Flush eyes well with flooding amounts of running water for at least 15 minutes.
Assure adequate flushing by separating the eyelids with sterile fingers. If irritation persists, transport to a hospital
immediately.
Rinse mouth, give plenty of water to dilute the substance. Never give anything by mouth to an unconscious person.
Transport to a hospital immediately.
INHALATION :
SKIN CONTACT :
EYE CONTACT :
INGESTION :
SECTION V
FIRE FIGHTING MEASURES
EXTINGUISHING MEDIA :
FIRE & EXPLOSION HAZARDS :
Carbon dioxide, dry chemical powder, foam, water
Toxic and irritating fumes or smoke may be emitted. Explosive hydrogen gas is released upon contact with common
metals.
SPECIAL PROTECTIVE EQUIPMENT FOR FIREFIGHTERS :
Firemen should wear normal protective equipment (full bunker gear) and positive-pressure self-contained breathing
apparatus.
SECTION VI
ACCIDENTAL RELEASE MEASURES
PERSONAL PRECAUTIONS :
Remove ignition sources and ventilate the area. In case of insufficient ventilation, wear suitable respiratory equipment.
Avoid contact with skin and eyes.
ENVIRONMENTAL PRECAUTIONS :
Prevent spills from entering sewers, watercourses or low areas.
METHODS FOR CLEANING UP :
Do not touch spilled material without suitable protection (See section 8). Take up spilled material with ashes or other
incombustible absorbents and dilute it with plenty of water and neutralize with soda ash. After material is completely
picked up, wash the spill site with soap and water and ventilate the area. Put all wastes in a plastic bag for disposal and
seal it tightly. Remove, clean, or dispose of contaminated clothing.
SECTION VII
HANDLING AND STORAGE
PRECAUTION FOR SAFE HANDLING :
Avoid contact with eyes, skin and clothing. Avoid prolonged or repeated exposure. Handle material with suitable
protection.
CONDITIONS FOR SAFE STORAGE :
Store away from sunlight in well-ventilated dry place at room temperature. Keep container tightly closed.
INCOMPATIBILITIES :
Strong oxidizers, alkalis, amines, metals
SECTION VIII
EXPOSURE CONTROLS/PERSONAL PROTECTION
ENGINEERING MEASURES :
VENTILATION :
Use exhaust ventilation to keep airborne concentrations below exposure limits. Use only with adequate ventilation.
Local Exhaust ; Necessary, Mechanical (General) ; Necessary
Special; Closed system is recommended.
INDIVIDUAL PROTECTION MEASURES ;
Respiratory protection : NIOSH/MSHA or European Standard EN149 approved respirator
Hand protection :
Impervious gloves
Eye protection :
Safety glasses (goggles)
Skin protection :
Protective clothing
CONTROL PARAMETER :
as Hydrogen chloride
OSHA Final Limits :
Ceiling = 5 ppm, 7 mg/m3; STEL = 2 ppm
ACGIH TLV(s) :
Ceiling = 5 ppm, 7.5 mg/m3
SECTION IX
APPEARANCE :
ODOUR :
pH :
FREEZING POINT :
INITIAL BOILING POINT :
FLASH POINT :
FLAMMABILITY (solid, gas) :
EXPLOSIVE LIMITS :
VAPOR PRESSURE :
VAPOR DENSITY :
RELATIVE DENSITY :
SOLUBILITY IN ;
PHYSICAL AND CHEMICAL PROPERTIES
Colorless clear liquid
Irritating odor
Not available
-46.2 °C = -51.2 °F (31.24 %)
108.58 °C = 227.44 °F
Not available
----Not available
Not available
1.3 (air = 1)
1.180 (35.39 %)
WATER :
Miscible
ETHANOL, ETHL ETHER : Miscible
PARTITION COEFFICIENT :
0.25
DECOMPOSITION TEMPERATURE : Not available
378
TOC-LCSH/CSN
5.10
SECTION X
Safety Data Sheets
STABILITY AND REACTIVITY
CHEMICAL STABILITY :
Will not occur.
CONDITIONS TO AVOID :
Sunlight, heat
INCOMPATIBILE MATERIALS :
Strong oxidizers, alkalis, amines, metals
HAZARDOUS DECOMPOSITION PRODUCTS :
Hydrogen chloride gas may be formed.
SECTION XI
TOXICOLOGICAL INFORMATION
as Hydrogen chloride;
ACUTE TOXICITY (oral/dermal/inhalation) :
LDLo (orl,woman): 420 μL/kg (JJTOEX 9,351,1996)
LC50 (ihl,rat): 7004 mg/m3/30M (VCVN5* -, 383, 1989)
TCLo (ihl,human): 50 mg/m3 (VCVN5* -, 383, 1989)
SKIN CORROSION/IRRITATION :
Skin; human; 4 %/24H; Mild (BJDEAZ 68,192,1988)
EYE DAMAGE/EYE IRRITATION : Eye; rabbit, rinsed; 5 mg/30S; Mild (TXCYAC 23,281,1982)
RESPIRATORY OR SKIN SENSITIZATION :
Not available
GERM CELL MUTAGENICITY :
Cytogenetic analysis; hamster; ovary; 8 mmol/L (MUREAV 225,55,1989)
DNA repair; E.coli; 25 μg/well (ENMUDM 3, 429, 1981)
TOXIC TO REPRODUCTION :
STOST-SINGLE EXPOSURE :
STOST-REPEATED EXPOSURE :
ASPIRATION TOXICITY :
CARCINOGENICITY :
ADDITIONAL INFORMATION ;
TCLo (ihl,rat): 450 mg/m3/1H (female 1D pre): Effects on Embryo or Fetus - fetotoxicity (AKGIAO 53 (6), 69,1977)
Not available
Not available
Not available
Not available
NTP :
Not listed
IARC :
Not Classifiable as to Carcinogenicity to Humans (Group 3)
OSHA :
Not listed
ACGIH :
Not listed
EPA GENETOX PROGRAM 1988, Negative: Cell transform.-SA7/SHE
SECTION XII
ECOLOGICAL INFORMATION
ECOTOXICITY :
LC50 (starfish): 100 to 330 ppm (as Hydrogen chloride)
PERSISTENCE AND DEGRADABILITY :
Not available
BIOACCUMULATION POTENTIAL : Not available
MOBILITY IN SOIL :
Not available
OTHER ADVERSE EFFECTS :
WGK; 1
SECTION XIII
DISPOSAL CONSIDERATION (INCLUDING CONTAINER)
Cautiously add to a large stirred excess of water. Adjusting the pH to neutral, separate any insoluble solids or liquids and
package them for hazardous-waste disposal. Flush the aqueous solutions down the drain with plenty of water. Any
disposal practice must be in compliance with country, local, state, and federal laws and regulations (contact country, local
or state environmental agency for specific rules).
SECTION XIV
TRANSPORT INFORMATION
IATA :
UN NUMBER :
UN PROPER SHIPPING NAME :
CLASS or DIVISION :
PACKING GROUP :
MARINE POLLUTANT :
DOT (Department of Transportation) : IDENTIFICATION NUMBER :
PROPER SHIPPING NAME :
HAZARD CLASS :
UN1789
Hydrochloric acid
Corrosives. (Class 8)
PG II
Yes
UN1789
Hydrochloric acid
Corrosive material (Class 8)
SECTION XV
REGULATORY INFORMATION
US REGULATIONS ;
CAA/112 1990 Amend., CAA/122(r) Acci. Release Pre. Subst., CERCLA Haz. Subst., DOT Haz. Mat., DOT Haz. Sub.
and Rep. Quant., Mass. Subst. List , New Jers. RTK Haz. Subst. List , Penn. Haz. Subst. List
EPA :
CERCLA RQ= 5000 lb
EPCRA TPQ= Not listed
EPA FIFRA 1998 STATUS OF PESTICIDES: Red Completed
OSHA :
TQ= Not listed
SECTION XVI
OTHER INFORMATION INCLUDING INFORMATION ON PREPARATION AND REVISION
OF THE SDS
No specific notes
The above information is believed to be correct to be the best of our knowledge and information but does not purport to be all inclusive and shall be used only as a
guide. This product is intended to be used by expert persons having chemical knowledge and skill, at their own discretion and risk and Wako shall not be held
liable for any damage resulting from handling or from contact with the above material.
TOC-LCSH/CSN
379
5.10
Safety Data Sheets
5.10.2 Phosphoric Acid
Shimadzu Scientific Instruments, Inc.
7102 Riverwood Drive Columbia, MD 21046
Tel: 1(800) 477-1227
SECTION I
Revised Date: 2009/06/18
IDENTIFICATION OF THE SUBSTANCE OR MIXTURE
PRODUCT IDENTIFIER :
Phosphoric Acid
SECTION II
HAZARDS IDENTIFICATION
GHS CLASSIFICATION :
Skin corrosion/irritation:
Serious eye damage/eye irritation:
Acute toxicity-Oral:
Acute toxicity-Dermal:
Specific target organ systemic toxicity Single exposure:
Category 1A
Category 1
Category 4
Category 5
Category 3 <the respiratory tract irritation>
HAZARD SYMBOL :
DANGER
Causes severe skin burns and eye damage
Causes serious eye damage
Harmful if swallowed
May be harmful in contact with skin
May cause respiratory irritation; or May cause drowsiness and dizziness <the respiratory tract irritation>
PRECAUTIONARY STATEMENTS : Do not eat, drink or smoke when using this product.
Wash thoroughly after handling.
Get medical attention/advice if you feel unwell.
IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue
rinsing.
IF ON SKIN: Gently wash with plenty of soap and water.
IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
Store container tightly closed in well-ventilated place -if product is as volatile as to generate hazardous atmosphere.
Dispose of contents/container to a located point (in accordance with local/regional/national/international regulation).
EU CLASSIFICATIONS:
according to EC Directives
SYMBOL :
C
HAZARD STATEMENTS, including R-phrase :
R34 Causes burns.
HAZARD STATEMENTS :
SECTION III
COMPOSITION/INFORMATION ON INGREDIENTS
CHEMILCAL IDENTITY :
SYNONYMS :
FORMULA :
MOLECULAR WEIGHT :
CAS NUMBER :
TSCA INVENTORY :
EINECS No. :
EC INDEX NUMBER :
Phosphoric acid (min.85.0 %)
Orthophosphoric acid, Hydrogen phosphate ; Phosphoric Acid, Ortho
H3PO4
98.00
7664-38-2
Listed
231-633-2
015-011-00-6
SECTION IV
FIRST AID MEASURES
GENERAL ADVICE :
Wash off immediately with soap and plenty of water. In the case of respirable dust and/or fumes, use self-contained
breathing apparatus and dust impervious protective suit. Use personal protective equipment.
Move victim to fresh air. If breathing is difficult, give oxygen. If irritation persists, consult a physician.
Remove contaminated clothes and shoes, rinse skin with plenty of water or shower. Use soap to help assure removal. If
irritation persists, transport to a hospital immediately.
Remove any contact lenses at once. Flush eyes well with flooding amounts of running water for at least 15 minutes.
Assure adequate flushing by separating the eyelids with sterile fingers. If irritation persists, transport to a hospital
immediately.
Rinse mouth, give plenty of water to dilute the substance. Never give anything by mouth to an unconscious person.
Transport to a hospital immediately.
INHALATION :
SKIN CONTACT :
EYE CONTACT :
INGESTION :
SECTION V
FIRE FIGHTING MEASURES
EXTINGUISHING MEDIA :
Carbon dioxide, dry chemical powder, foam, water
FIRE & EXPLOSION HAZARDS :
Toxic, irritating fumes or smoke may be emitted. Explosive hydrogen gas is released upon contact with common metals.
SPECIAL PROTECTIVE EQUIPMENT FOR FIREFIGHTERS :
Firemen should wear normal protective equipment (full bunker gear) and positive-pressure self-contained breathing
apparatus.
SECTION VI
PERSONAL PRECAUTIONS :
ACCIDENTAL RELEASE MEASURES
Remove ignition sources and ventilate the area. In case of insufficient ventilation, wear suitable respiratory equipment.
Avoid contact with skin and eyes.
ENVIRONMENTAL PRECAUTIONS :Prevent spills from entering sewers, watercourses or low areas.
METHODS FOR CLEANING UP :
Do not touch spilled material without suitable protection (See section 8). Take up spilled material with ashes or other
incombustible absorbents and dilute it with plenty of water and neutralize with soda ash. After material is completely
picked up, wash the spill site with soap and water and ventilate the area. Put all wastes in a plastic bag for disposal and
seal it tightly. Remove, clean, or dispose of contaminated clothing.
380
TOC-LCSH/CSN
5.10
SECTION VII
Safety Data Sheets
HANDLING AND STORAGE
PRECAUTION FOR SAFE HANDLING :
Avoid contact with eyes, skin and clothing. Avoid prolonged or repeated exposure. Handle material with suitable
protection. This material is hygroscopic.
CONDITIONS FOR SAFE STORAGE :
Store away from sunlight in well-ventilated dry place at room temperature. Keep container tightly closed.
INCOMPATIBILITIES :
Oxidizers, alkalis, metals
SECTION VIII
EXPOSURE CONTROLS/PERSONAL PROTECTION
ENGINEERING MEASURES :
VENTILATION :
Use exhaust ventilation to keep airborne concentrations below exposure limits. Use only with adequate ventilation.
Local Exhaust ; Necessary, Mechanical (General) ; Necessary
Special; Closed system is recommended.
INDIVIDUAL PROTECTION MEASURES ;
Respiratory protection : Use a NIOSH/MSHA or European Standard EN149 approved respirator
Hand protection :
Impervious gloves
Eye protection :
Safety glasses (goggles)
Skin protection :
Protective clothing
CONTROL PARAMETER :
OSHA Final Limits :
TWA = 1 mg/m3
ACGIH TLV(s) :
TWA = 1 mg/m3; STEL = 3 mg/m3
SECTION IX
PHYSICAL AND CHEMICAL PROPERTIES
APPEARANCE :
ODOUR :
pH :
MELTING POINT :
INITIAL BOILING POINT :
FLASH POINT :
FLAMMABILITY (solid, gas) :
EXPLOSIVE LIMITS :
VAPOR PRESSURE :
VAPOR DENSITY :
SPECIFIC GRAVITY :
SOLUBILITY IN ;
Colourless clear liquid
Odourless
Not available
Not available
213 °C = 415 °F
Not available
----Not available
4.0 Pa (at 20 °C = 68 °F)
3.4 (Air = 1)
1.685
WATER :
Freely soluble (670 g/100 mL at 25 °C = 77 °F)
ETHANOL :
Freely soluble
PARTITION COEFFICIENT :
Not available
DECOMPOSITION TEMPERATURE : Not available
SECTION X
STABILITY AND REACTIVITY
CHEMICAL STABILITY :
May occur. Violent polymerization can occur with epoxides, azo compounds, and polymerizable compounds.
CONDITIONS TO AVOID :
Sunlight, heat, moisture
INCOMPATIBILE MATERIALS :
Oxidizers, alkalis, metals
HAZARDOUS DECOMPOSITION PRODUCTS :
Phosphorous oxide may be formed.
SECTION XI
TOXICOLOGICAL INFORMATION
ACUTE TOXICITY (oral/dermal/inhalation) :
LD50 (orl, rat) :
1.25 gm/kg (RTECS)
LD50 (orl, mouse) :
1.25 gm/kg (RTECS)
LC50 (ihl, rat) :
25.5 mg/m3 (RTECS)
LD50 (orl, rat) :
1530 mg/kg (IUCLID, 2000) (HSDB, 2006)
LD50 (skin, rabbit) :
2740 mg/kg (IUCLID, 2000) (HSDB, 2006)
SKIN CORROSION/IRRITATION :
Skin; rabbit; 595 mg/24H; Severe (RTECS)
Skin; rabbit; 75-85 %/24H; Irritation (IUCLID, 2000)
EYE DAMAGE/EYE IRRITATION : Eye; rabbit; 119 mg; Severe (RTECS)
RESPIRATORY OR SKIN SENSITIZATION :
Not available
GERM CELL MUTAGENICITY :
Not available
TOXIC TO REPRODUCTION :
Not available
STOST-SINGLE EXPOSURE :
Human; mist, irritation of the upper respiratory tract (ACGIH 7th, 2001)
STOST-REPEATED EXPOSURE :
Not available
ASPIRATION TOXICITY :
Not available
CARCINOGENICITY :
Not available
ADDITIONAL INFORMATION ;
NTP :
Not listed
IARC :
Not listed
OSHA :
Not listed
ACGIH :
Not listed
EPA GENETOX PROGRAM 1988, Negative: Cell transform.-SA7/SHE
TOC-LCSH/CSN
381
5.10
Safety Data Sheets
SECTION XII
ECOLOGICAL INFORMATION
ECOTOXICITY :
Not available
PERSISTENCE AND DEGRADABILITY :
Not available
BIOACCUMULATION POTENTIAL : Not available
MOBILITY IN SOIL :
Not available
OTHER ADVERSE EFFECTS :
WGK; 1
SECTION XIII
DISPOSAL CONSIDERATION (INCLUDING CONTAINER)
Cautiously add to a large stirred excess of water. Adjusting the pH to neutral, separate any insoluble solids or liquids and
package them for hazardous-waste disposal. Flush the aqueous solutions down the drain with plenty of water.
Any disposal practice must be in compliance with country, local, state, and federal laws and regulations (contact country,
local or state environmental agency for specific rules).
After contents are completely removed, dispose of its container at hazadous or special waste collection point. (in
accordance with local/regional/ national/international regulation).
SECTION XIV
TRANSPORT INFORMATION
IATA :
UN NUMBER :
UN PROPER SHIPPING NAME :
CLASS or DIVISION :
PACKING GROUP :
MARINE POLLUTANT :
DOT (Department of Transportation) : IDENTIFICATION NUMBER :
PROPER SHIPPING NAME :
HAZARD CLASS :
SECTION XV
UN1805
Phosphoric acid
Corrosives. (Class 8)
PG III
No
UN1805
Phosphoric acid
Corrosive material (Class 8)
REGULATORY INFORMATION
US REGULATIONS ;
as Phosphoric acid;
CWA/311 Haz., NIOSH Recommend. Subst., CERCLA Haz. Subst., SARA III/313 Tox. Chem., DOT Haz. Mat., DOT
Haz. Sub. and Rep. Quant., Mass. Subst. List , New Jers. RTK Haz. Subst. List , Penn. Haz. Subst. List , Canad. WHMIS
IDL 1 % conc.
EPA :
CERCLA RQ= 1000 lb
EPCRA SECTION 313 de minimis concentration is 1.0 %.
FIFRA 1988 PESTICIDE SUBJECT TO REGISTRATION OR RE-REGISTRATION
FIFRA 1998 ; RED Completed
OSHA : TQ= Not listed
NFPA : HR= health-2, flam.-0, react.-0
EU REGULATIONS:
according to EC Directives
SYMBOL :
C
HAZARD STATEMENTS, including R-phrase :
R34 Causes burns.
ADDITIONAL HAZARD STATEMENTS :
Harmful if inhaled and ingested. React with most metals to form flammable hydrogen gas.
PRECAUTIONARY STATEMENTS, including S-phrase :
S26 In case of contact with eyes, rinse immediately with plenty of water and seek medical advice.
S45 In case of accident or if you feel unwell, seek medical advice immediately
SECTION XVI
OTHER INFORMATION INCLUDING INFORMATION ON PREPARATION AND REVISION
OF THE SDS
No specific notes
The above information is believed to be correct to be the best of our knowledge and information but does not purport to be all inclusive and shall be used only as a
guide. This product is intended to be used by expert persons having chemical knowledge and skill, at their own discretion and risk and Wako shall not be held
liable for any damage resulting from handling or from contact with the above material.
382
TOC-LCSH/CSN
5.10
Safety Data Sheets
5.10.3 IC Reagent
Shimadzu Scientific Instruments, Inc.
7102 Riverwood Drive Columbia, MD 21046
Tel: 1(800) 477-1227
SECTION I
Revised Date: 2009/09/24
PRODUCT AND COMPANY INFORMATION
PRODUCT NAME :
IC reagent
COMPANY NAME :
Shimadzu Corporation
ADDRESS :
1, Nishinokyo-Kuwabara-cho, Nakagyo-ku, Kyoto, Japan
DEPARTMENT :
Analytical and Measuring Instruments Department, Environmental Business Unit
TELEPHONE NUMBER :
075-823-1207
FAX NUMBER :
075-823-4614
EMERGENCY CONTACT NUMBER :075-823-1207, Analytical and Measuring Instruments Department, Environmental Business Unit
SECTION II
COMPOSITION/INFORMATION ON INGREDIENTS
SINGLE PRODUCT OR COMPOUND CLASSIFICATION :
Single product
CHEMICAL OR GENERIC NAME : Phosphoric acid
CONTENT :
Phosphoric acid, 25% aqueous solution
CHEMICAL PROPERTIES (CHEMICAL FORMULA)
H3PO4
OFFICIAL GAZETTE REFERENCE NUMBER (CSCL/ISHL) :
1-422
CAS NO. :
7664-38-2
HAZARDOUS COMPONENTS :
Phosphoric acid
SECTION III
SUMMARY OF HAZARDOUS PROPERTIES
PRIMARY HAZARDOUS PROPERTY :
Corrosive to skin.
HAZARDS :
Strongly acidic liquid that causes irritation and inflammation to the eyes, skin, and mucous membrane.
Contact with the eyes causes irritation and may cause blindness.
In a mist or vapor state, causes irritation to the eyes, skin, mucous membrane, respiratory tract, and lungs.
Oral ingestion may cause nausea, vomiting, abdominal pain, and bloody diarrhea.
ENVIRONMENTAL IMPACT :
Hazardous to aquatic organisms due to strong acidity.
PHYSICAL AND CHEMICAL HAZARDS :
Contact with alkaline substances generates heat.
Reacts with many types of metals to produce hydrogen gas that mixes with air to form a flammable and explosive gas.
CLASSIFICATION NAME :
Corrosive substance
SECTION IV
FIRST AID MEASURES
INHALATION :
Immediately move the affected person to a location with fresh air. Calm them and cover their body with a blanket or
similar material to keep them warm. Instruct them to blow their nose and gargle their throat.
If breathing is difficult, give oxygen. If breathing stops, loosen clothing, secure the respiratory tract, and perform artificial
respiration. Transport to a hospital immediately.
SKIN CONTACT :
Remove contaminated clothes and shoes and rinse the affected area of skin with plenty of water. Do NOT neutralize using
alkaline solutions. Do NOT apply any type of oil or ointment to the affected area without specific instruction from a
physician.
If the appearance of the skin changes or irritation and pain persist, transport to a hospital immediately.
EYE CONTACT :
Immediately flush the affected eye with clean, running water for at least 15 minutes and promptly consult an eye
physician. Ensure adequate rinsing by separating the eyelids with sterile fingers and flushing the eyeball and all parts of
the eyelid with water.
Do NOT apply any type of oil or ointment without specific instruction from a physician.
Always perform first aid measures immediately because a delay in eye flushing or insufficient flushing may cause
permanent damage to the affected eye. Continue flushing the affected eye if medical attention from a physician is
delayed.
INGESTION :
Calm the affected person and cover their body with a blanket or similar material to keep them warm.
Reassure the affected person if conscious. Rinse out their mouth and give milk or water dispersed with magnesium oxide
in small amounts. If these measures cannot be taken immediately, give large amounts of water.
NEVER induce vomiting as this may have the opposite effect of damaging the stomach wall due to the corrosive nature of
the material. Never give anything by mouth to an unconscious person.
Transport to a hospital immediately.
PROTECTION FOR THE GIVER OF FIRST AID:
The person who provides first aid should wear protective equipment including protective eyewear and protective gloves to
avoid contact with the hazardous substance.
SECTION IV
FIRE FIGHTING MEASURES
EXTINGUISHING MEDIA :
This product does not ignite on its own.
Use a suitable extinguishing media for the other materials caused to ignite by this product.
SPECIFIC EXTINGUISHING METHOD :
Prohibit unauthorized personnel from entering the area where fire has broken out and direct them to a safe location.
While this substance is noncombustible, immediately transfer the container to a safe location if fire breaks out.
If the container cannot be transferred to another location, cool the container and immediate area by spraying water.
Take suitable measures to prevent the runoff of substances when extinguishing the fire that may adversely affect the
environment.
SPECIFIC HAZARDS :
The molecules that comprise this substance contain phosphorus. Avoid inhaling any smoke produced due to contact with
fire as it contains irritants, toxic fumes and gas.
PROTECTION FOR FIREFIGHTERS :
Always wear suitable protective equipment due to the strong acidity of the liquid.
Perform firefighting from an up wind position as mush as possible. Wear protective equipment that covers the eyes, nose,
and mouth to prevent exposure and inhalation of smoke that contains toxic gas.
TOC-LCSH/CSN
383
5.10
Safety Data Sheets
SECTION V
ACCIDENTAL RELEASE MEASURES
PERSONAL PRECAUTIONS :
Cordon off the area of spilled material with rope, sound an alarm or similar warning, and prohibit unauthorized personnel
from entering the area.
Sufficiently ventilate the area and perform cleanup work from an up wind position. Do not perform any work down wind
from the spilled material.
Always wear protective equipment (protective eyewear, protective gloves, protective shoes, protective clothing, and a gas
mask for acidic gases) during cleanup work due to the strongly acidity and corrosive nature of the substance.
ENVIRONMENTAL PRECAUTIONS :Take measures to prevent the discharge of this product into rivers that will adversely affect the environment.
When this substance is diluted with large amounts of water, do not allow the discharge of contaminated water into the
environment without suitable treatment. Do not discharge spilled material directly into rivers or the sewage system.
CLEANUP METHOD :
SMALL SPILLS : Clear away any spilled material after soaking it up with dry sand or earth. Alternatively, dilute the
spilled material with water, neutralize it with lime hydrate or soda ash, and then wash the material
away with a large amount of water.
LARGE SPILLS : Enclose the spilled material with earth fill to prevent run off and allow absorption and then collect the
material in a sealable, empty container. Alternatively, gradually dilute the spilled material with water
from a safe location at a distance, neutralize the spilled material with lime hydrate or soda ash, and
then wash the material away with a large amount of water.
Rapid contact with water during dilution or the neutralizing agent generates heat and may cause acid
to splatter. For this reason, take care when performing dilution and always be careful when
performing gradual neutralization after dilution.
If gas is produced during neutralization, spray the gas with water mist to absorb it.
Do not allow the discharge of concentrated liquid into rivers.
SECTION VI
HANDLING AND STORAGE
HANDLING :
TECHNICAL MEASURES :
• Avoid contact with eyes, skin, and clothes due to the strongly acidity of the substance.
• Avoid inhalation of mist and vapor.
• Always wear suitable protective equipment when working with this substance. (Protective eyewear or face shield,
protective gloves, protective shoes, protective clothing (all of which are acid resistant), and protective breathing
equipment such as a gas mask for acidic gases.)
• Always handle this material in well ventilated areas.
• Avoid inhalation of mist or vapor in insufficiently ventilated areas.
• Prevent the generation of mist and vapor as much as possible and keep the work environment within exposure limits.
• In order to prevent the accumulation of mist and vapor in locations that generate these states, implement measures to
seal up instruments or remove contaminated air using exhaust equipment.
• Always seal the container opening to prevent airborne droplets entering from clothing and openings in footwear.
• Install facilities for emergency eye and body washing near the area of handling and clearly indicate the position of
such facilities.
• Handle the container with care to prevent breakage. Do not hold the container by the plug or mouth.
• Do not topple over, shock, drag, or handle the container in a similarly rough manner.
• Directly mixing neutralizing agent with this material generates heat and bubbles and may cause the material to
splatter. Always perform neutralization after dilution with water.
• Always perform dilution with water carefully as this can generate heat.
• Handle alkaline substances, cyanide compounds, and metal powder at removed locations.
• Always wash your hands and eyes and gargle after handling this material. Always wash any used protective
equipment with water and allow to dry. Change your clothing immediately if it comes into contact with the material.
Wash the contaminated clothing with water and allow to dry.
PRECAUTIONS :
If there is a risk that mist or vapor may be generated, handle the material
within local ventilation or at a location with general ventilation equipment.
PRECAUTIONS FOR SAFE HANDLING : Avoid contact with alkaline substances due to the material's strongly acidity.
As this liquid reacts with metals, select a suitable material for handling.
As this material will cause metals such as iron to rust, relevant facilities
require anti-rust treatment.
CONDITIONS FOR SAFE STORAGE :
• Store away from sunlight in a dry, well-ventilated location at room temperature.
• Keep container tightly sealed.
• Construct the floor of the storage location with acid resistant material to prevent any spillages from penetrating
underground.
• Install drainage prevention facilities to prevent the material from flowing out of the storage location.
• Do not store in underground rooms or locations with sources of heat, such as boilers.
• Store away from alkaline substances, cyanide compounds, and metal powder.
SAFE CONTAINERS AND PACKAGING MATERIAL :
Due to a strong corrosive reaction with metals, select a suitable material to handle this liquid.
Cast iron containers cannot be used.
Resin-based materials such as polyethylene, PTFE, and FRP as well as glass are resistant to this liquid.
STORAGE
SECTION VII
FACILITY MEASURES :
EXPOSURE CONTROL AND PERSONAL PROTECTION
In handling locations that generate mist or vapor, seal the generation source or use local ventilation equipment.
Install facilities for emergency eye and body washing near the area of handling and clearly indicate the position of such
facilities.
CONTROL CONCENTRATION :
Not set.
ACCEPTABLE CONCENTRATION : Japan Society for Occupational Health
1 mg/m3
ACGIH1mg/m3 (TLV-TWA)
3 mg/m3 (TLV-STEL)
*) TWA : Time-weighted average value,
STEL : Short-term exposure limit
PROTECTIVE EQUIPMENT
RESPIRATORY PROTECTION :
Gas mask for acidic gases
HAND PROTECTION :
Protective gloves (impervious and acid resistant)
EYE PROTECTION :
Protective eyewear (normal glasses with side protection, goggles)
SKIN PROTECTION :
Protective clothing (long-sleeved work clothes), protective shoes, apron
384
TOC-LCSH/CSN
5.10
SECTION VIII
PHYSICAL AND CHEMICAL PROPERTIES
PHYSICAL PROPERTIES
FLASH POINT :
DENSITY (SPECIFIC GRAVITY) :
SOLUBILITY
SHAPE :
Viscous liquid
COLOR :
Clear and colorless
ODOR :
Odorless
pH :
Strongly acidic
Nonflammable.
1.15 g/cm3 (20 °C)
SOLUBILITY WITH RESPECT TO SOLVENT:
SECTION IX
STABILITY AND REACTIVITY
Safety Data Sheets
Freely mixes with water.
Soluble in ethyl alcohol.
CHEMICAL STABILITY :
CHEMICAL REACTIVITY :
Stable under normal handling conditions.
Violently generates heat when material comes into contact with alkaline substances due to strong acidity.
Very stable at room temperature, does not change state due to oxidizing or reducing agents, and generally resists reduction
by carbon and hydrogen under 350 to 400 °C.
Generates toxic phosphorus oxide when heated to the point of decomposition.
While a comparatively weak acid as an aqueous solution, it will react with iron, aluminum, and zinc to produce hydrogen
and generate each type of salt.
While the action of highly concentrated phosphorus acid with respect to most metals around room temperature is weak, it
reacts violently with many types of metals and their oxides at high temperatures.
CONDITIONS TO AVOID :
Direct sunlight, heat
INCOMPATIBLE MATERIALS :
Metals, alkaline substances
HAZARDOUS DECOMPOSITION PRODUCTS :
Phosphorus oxide, hydrogen gas
SECTION X
TOXICOLOGICAL INFORMATION
ACUTE TOXICITY :
Oral ingestion may cause nausea, vomiting, abdominal pain, and bloody diarrhea.
Rat, oral
LD50 1,530 mg/kg
Rabbit, skin
LD50 2,740 mg/kg
Human, inhalation
TCL0 100 mg/m3
IRRITATION (SKIN, EYES) :
Contact with the eyes causes irritation and may cause conjunctival
hyperemia, corneal impairment, and iritis.
Contact with the skin and mucous membrane causes itching and pain
and may cause soreness and inflammation.
In a mist or vapor state, causes irritation to the eyes, skin, mucous
membrane, respiratory tract, and lungs.
CHRONIC AND LONG-TERM TOXICITY :
Repeated inhalation of mist or vapor may cause bronchitis.
CARCINOGENICITY :
Not included on IARC and NTP lists.
MUTAGENICITY :
Not available
TERATOGENICITY :
Not available
REPRODUCTIVE TOXICITY :
Not available
LOCAL EFFECTS
SECTION XI
ENVIRONMENTAL INFORMATION
MOBILITY :
From its physicochemical properties, this material has the potential to move into atmospheric, aquatic, and soil
environments.
RESIDUAL/RESOLVABILITY :
Not available
BIOACCUMULATION POTENTIAL : Not available
ECOTOXICITY
TOXICITY TO FISH : Hazardous to aquatic organisms.
LD50 over 96 hours is 100-10 mg/L.
The fatal dose for fish is 135 mg/L.
SECTION XII
DISPOSAL CONSIDERATIONS
RESIDUAL WASTE :
CONTAINER :
Dilute with a large amount of water before carefully neutralizing with an aqueous solution of lime hydrate (calcium
hydroxide) or soda ash (sodium carbonate). Separate from any generated precipitates and discharge the supernatant liquid
according to wastewater standard restrictions.
Rapid contact with water during dilution or the neutralizing agent generates heat and may cause acid to splatter. For this
reason, take care when performing dilution and always be careful when performing gradual neutralization after dilution.
Always wear protective equipment suitable to the task at hand.
Protective equipment : Protective eyewear or face shield, impervious protective gloves, protective shoes, protective
clothing (impervious, long-sleeved work clothes), gas mask for acidic gases (for sulfurous gas),
apron
Dispose of material according to local regulations for the relevant area and request processing by an industrial waste
disposal company.
Dispose of containers after completely removing their contents.
SECTION XIII
TRANSPORTATION INFORMATION
UN CLASSIFICATION :
Class 8 (Corrosives), PG III
UN NUMBER :
1805
SPECIFIC SAFETY MEASURES AND CONDITIONS FOR TRANSPORTATION :
Check that containers are not broken or leaking. Pack containers to prevent shocks, toppling over, falling, or breaking.
Take measures to prevent the cargo from collapsing. Cover containers with a light-shielding cloth to avoid exposure to
direct sunlight. Prevent containers from becoming wet with rain.
Carefully handle containers to prevent breakage, leakage, or splattering due to shocks, toppling over, or falling.
Always wear the required protective equipment when performing loading, unloading, transport, and filling tasks.
Avoid contact and mixed loading with metals, alkaline substances, and cyanide compounds.
The above information is believed to be correct to the best of our knowledge and according to the information available but does not purport to be all inclusive and
should only be used as a guide.
While the above stated precautions only describe normal handling procedures, users should implement safety measures that apply to any new applications that
necessitate special handling requirements.
All chemicals require handling with utmost care as there is always the possibility of unknown hazards and toxicity. This product is intended for use at your own
discretion and risk and we request that you implement any necessary conditions for safe use.
TOC-LCSH/CSN
385
5.10
Safety Data Sheets
5.10.4 CO2 Absorber, Ca(OH)2, KOH, NaOH: Soda Lime
Shimadzu Scientific Instruments, Inc.
7102 Riverwood Drive Columbia, MD 21046
Tel: 1(800) 477-1227
SECTION I
Revised Date: 2010/03/19
IDENTIFICATION OF THE SUBSTANCE OR MIXTURE
PRODUCT IDENTIFIER :
Soda Lime
SECTION II
HAZARDS IDENTIFICATION
GHS CLASSIFICATION :
HAZARD SYMBOL :
Skin corrosion/irritation:
Category 1B
DANGER
HAZARD STATEMENTS :
Causes severe skin burns and eye damage
PRECAUTIONARY STATEMENTS : <Prevention>
Wear protective gloves and eye/face protection.
Wash thoroughly after handling.
Do not breathe dust
<Response>
IF ON SKIN (or hair): Remove/Take off immediately all contaminated clothing. Rinse skin with water/shower.
IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue
rinsing.
IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing.
Immediately call a POISON CENTRE or doctor/physician.
Wash contaminated clothing before reuse.
Specific measures (see MSDS).
<Storage>
Store locked up.
<Disposal>
Dispose of contents/container to a located point.
EU CLASSIFICATION:
according to Directive 67/548/EEC.
SYMBOL :
C
R-phrase :
R34 Causes burns.
S-phrase :
S26 In case of contact with eyes, rinse immediately with plenty of water and seek medical advice.
S36/37/39 Wear suitable protective clothing, gloves and eye/face protection.
S45 In case of accident or if you feel unwell, seek medical advice immediately.
SECTION III
COMPOSITION/INFORMATION ON INGREDIENTS
CHEMILCAL IDENTITY :
FORMULA :
MOLECULAR WEIGHT :
CAS NUMBER :
TSCA INVENTORY :
EINECS No. :
EC INDEX NUMBER :
Soda lime
--------8006-28-8
Not listed (See Section 15)
Not listed
Not listed
SECTION IV
FIRST AID MEASURES
GENERAL ADVICE :
Wash off immediately with soap and plenty of water. In the case of respirable dust and/or fumes, use self-contained
breathing apparatus and dust impervious protective suit. Use personal protective equipment.
Move victim to fresh air. If breathing is difficult, give oxygen. If breathing has stopped, administer artificial respiration.
Maintain normal body temperature with a blanket. If irritation persists, transport to a hospital immediately.
Remove contaminated clothes and shoes, rinse skin with plenty of water or shower. Use soap to help assure removal. If
irritation persists, transport to a hospital immediately.
Remove any contact lenses at once. Flush eyes well with flooding amounts of running water for at least 15 minutes.
Assure adequate flushing by separating the eyelids with sterile fingers. If irritation persists, transport to a hospital
immediately.
Rinse mouth, give plenty of water to dilute the substance. Do not induce vomiting. Never give anything by mouth to an
unconscious person. Transport to a hospital immediately.
INHALATION :
SKIN CONTACT :
EYE CONTACT :
INGESTION :
SECTION V
FIRE FIGHTING MEASURES
EXTINGUISHING MEDIA :
Not combustible. Use extinguisnig media appropriate to the surrounding fire.
FIRE & EXPLOSION HAZARDS :
Toxic and irritating dust, fumes or smoke may be emitted.
SPECIAL PROTECTIVE EQUIPMENT FOR FIREFIGHTERS :
Firemen should wear normal protective equipment (full bunker gear) and positive-pressure self-contained breathing
apparatus.
SECTION VI
PERSONAL PRECAUTIONS :
ACCIDENTAL RELEASE MEASURES
Remove ignition sources and ventilate the area. In case of insufficient ventilation, wear suitable respiratory equipment.
Avoid raising dust and avoid contact with skin and eyes.
ENVIRONMENTAL PRECAUTIONS : Prevent spills from entering sewers, watercourses or low areas.
METHODS FOR CLEANING UP :
Do not touch spilled material without suitable protection (See section 8). After material is completely picked up, wash the
spill site with soap and water and ventilate the area. Put all wastes in a plastic bag for disposal and seal it tightly. Remove,
clean, or dispose of contaminated clothing.
386
TOC-LCSH/CSN
5.10
SECTION VII
Safety Data Sheets
HANDLING AND STORAGE
PRECAUTION FOR SAFE HANDLING :
Avoid contact with eyes, skin and clothing. Avoid prolonged or repeated exposure. Handle material with suitable
protection.
This material is hygroscopic.
CONDITIONS FOR SAFE STORAGE :
Store away from sunlight in well-ventilated dry place at room temperature. Keep container tightly closed.
INCOMPATIBILITIES :
Strong acids
SECTION VIII
EXPOSURE CONTROLS/PERSONAL PROTECTION
ENGINEERING MEASURES :
VENTILATION :
Use exhaust ventilation to keep airborne concentrations below exposure limits. Use only with adequate ventilation.
Local Exhaust ; Necessary, Mechanical (General) ; Necessary
Special; Closed system is recommended.
INDIVIDUAL PROTECTION MEASURES ;
Respiratory protection : NIOSH/MSHA approved respirator
Hand protection :
Impervious gloves
Eye protection :
Safety glasses (goggles)
Skin protection :
Protective clothing
CONTROL PARAMETER :
OSHA Final Limits :
None established
ACGIH TLV(s) :
None established
SECTION IX
PHYSICAL AND CHEMICAL PROPERTIES
APPEARANCE :
White - slightly brown, shot
ODOUR :
Odorless
pH :
Not available
MELTING POINT :
Not available
INITIAL BOILING POINT :
Not available
FLASH POINT :
Not available
FLAMMABILITY (solid, gas) :
Not available
EXPLOSIVE LIMITS :
Not available
VAPOR PRESSURE :
Not available
SPECIFIC GRAVITY :
2.1
SOLUBILITY IN ;
WATER : Practically insoluble
PARTITION COEFFICIENT :
Not available
DECOMPOSITION TEMPERATURE : Not available
SECTION X
STABILITY AND REACTIVITY
CHEMICAL STABILITY :
Stable under recommended storage conditions.
CONDITIONS TO AVOID :
Sunlight, heat, moisture
INCOMPATIBILE MATERIALS :
Strong acids
HAZARDOUS DECOMPOSITION PRODUCTS :
Not available
SECTION XI
TOXICOLOGICAL INFORMATION
ACUTE TOXICITY (oral/dermal/inhalation) :
Not available
TOXICITY DATA :
Harmful if inhaled and ingested.
SKIN CORROSION/IRRITATION :
May be harmful if absorbed through skin. Causese skin burns.
EYE DAMAGE/EYE IRRITATION : Causes burns.
RESPIRATORY OR SKIN SENSITIZATION :
Not available
GERM CELL MUTAGENICITY :
Not available
TOXIC TO REPRODUCTION :
Not available
STOST-SINGLE EXPOSURE :
Not available
STOST-REPEATED EXPOSURE :
Not available
ASPIRATION TOXICITY :
Not available
CARCINOGENICITY :
Not available
ADDITIONAL INFORMATION ;
NTP :
Not listed
IARC :
Not listed
OSHA :
Not listed
ACGIH :
Not listed
SECTION XII
ECOLOGICAL INFORMATION
ECOTOXICITY :
Not available
PERSISTENCE AND DEGRADABILITY :
Not available
BIOACCUMULATION POTENTIAL : Not available
MOBILITY IN SOIL :
Not available
OTHER ADVERSE EFFECTS :
Not available
SECTION XIII
DISPOSAL CONSIDERATION (INCLUDING CONTAINER)
Cautiously add to a large stirred excess of water. Adjusting the pH to neutral, separate any insoluble solids or liquids and
package them for hazardous-waste disposal. Flush the aqueous solutions down the drain with plenty of water.
Any disposal practice must be in compliance with country, local, state, and federal laws and regulations (contact country,
local or state environmental agency for specific rules).
After contents are completely removed, dispose of its container in accordance with local/regional/national/international
regulation.
TOC-LCSH/CSN
387
5.10
Safety Data Sheets
SECTION XIV
TRANSPORT INFORMATION
IATA :
UN NUMBER :
UN PROPER SHIPPING NAME :
CLASS or DIVISION :
PACKING GROUP :
MARINE POLLUTANT :
DOT (Department of Transportation) : IDENTIFICATION NUMBER :
PROPER SHIPPING NAME :
HAZARD CLASS :
UN3262
Corrosive solid, basic, inorganic, n.o.s. (Soda lime)
Corrosives. (Class 8)
PG III
No
UN3262
Corrosive solid, basic, inorganic, n.o.s.
Corrosive material (Class 8)
SECTION XV
REGULATORY INFORMATION
US REGULATIONS ;
New Jers. RTK Haz. Subst. List
EPA :
CERCLA RQ= Not listed
EPCRA TPQ= Not listed
OSHA : TQ= Not listed
NFPA : HR= health-2, flam.-0, react.-1
HMIS : HR= health-2, flam.-0, react.-1
TSCA : Use of this product must be restricted to research or analysis for the development of a product in accordance
with the Act.
SECTION XVI
OTHER INFORMATION INCLUDING INFORMATION ON PREPARATION AND REVISION
OF THE SDS
No specific notes
The above information is believed to be correct to be the best of our knowledge and information but does not purport to be all inclusive and shall be used only as a
guide. This product is intended to be used by expert persons having chemical knowledge and skill, at their own discretion and risk and Wako shall not be held
liable for any damage resulting from handling or from contact with the above material.
388
TOC-LCSH/CSN
5.10
Safety Data Sheets
5.10.5 Ceramic Fiber
Shimadzu Scientific Instruments, Inc.
7102 Riverwood Drive Columbia, MD 21046
Tel: 1(800) 477-1227
SECTION I
Refractory ceramic fiber
Alternative names:
Trade Name:
Product:
Chemical composition:
SECTION II
PRODUCT IDENTIFICATION
Polycrystalline alumino-silicate fiber, ceramic fiber
FIBERMAX
Bulk fiber
Al2O3 72-97, SiO2 3-28
HAZARDOUS INGREDIENTS / IDENTITY INFORMATION
INGREDIENT
Alumina Ceramic Fiber
[CAS# 675106-31-7]
Diameter about 3 μm
Hazard Data Source:
Revised Date: 2005/04
%
100
HAZARD DATA TLV-TWA
3
0.2 f/cm
[Notice of Intended Changes on ACGIH]
REMARK S
Counting fibers;
Longer ≥ 5 μm
Diameter < 3 μm
Length/Diameter ≥ 3
ACGIH Threshold Limit Values for 2002
SECTION III
PHYSICAL/CHEMICAL CHARACTERISTICS
Boiling Point:
Melting Point:
Evaporation Rate:
Density (kg/m3):
No data
No data
N/A
-
Solubility in Water:
Appearance:
Odor:
Service Temperature (°C):
SECTION IV
FIRE AND EXPLOSION HAZARD DATA
Flash Point (Method used):
Explosion Point (Method used):
Extinguishing Media:
This product is not flammable.
N/A
N/A
SECTION V
REACTIVITY DATA
Stability:
Incompatibility (Materials to avoid):
Stable
None
SECTION VI
HEALTH HAZARD DATA
N/A
White, loose wool
No odor1,300 - 1,700
Special Fire and Fighting Procedures:
Unusual Fire and Explosion Hazards:
None
None
Hazardous Decomposition or By-products:
Conditions to Avoid:
None
None
Acute Hazard:
Skin Contact: May cause irritation.
Eye Contact: May cause irritation, inflammation and rash.
Chronic Hazard:
Repeated, prolonged or excessive inhalation of fiber may cause respiratory disease.
At this time there are no known published reports demonstrating negative health outcomes of workers exposed to ceramic fiber.
Other Precautions on Health Hazard:
1. Perform periodic medical examination by X-ray of the lung function of the workers who handle this product.
2. Perform periodic monitoring of individual exposure of workers who handle this product to check if exposure level is in compliance
with TLV.
3. Record details of operation and arrange training/education of workers.
4. Workers should wash hand and rinse mouth after use.
Emergency and First Aid Procedures:
Inhalation:
First aid procedure is not necessary for respiratory tract. May cause cough, phlegm, etc., in case continue to inhale more
than acceptable level as described below. Get medical attention in such case.
Ingestion:
Ingestion is unlikely. If ingested, drink sufficient water and vomit and get medical attention.
Skin Contact: Flush with water or slightly warm water and wash with soap. Get medical attention if pain and inflammation.
Eye Contact:
Flush eyes with water for a least 15 minutes. Abrasive action may cause damage to the outer surface of the eye. Get
medical attention if irritating.
Carcinogenicity (Refractory Ceramic Fiber):
NTP:
B2 - Reasonably anticipated to be a carcinogen
IARC Monographs: 2B - Possibly carcinogenic to humans
EU:
2 - Probably carcinogenic to humans
Data of Experiments of Refractory Ceramic Fiber on Animals:
Result of experiments depends on kinds of experimental animals, volume/size distribution/process of exposure etc. of fiber dosed to
experimental animals and therefore a number of experiments are necessary.
1. There is a report that increase of lung tumor has been observed in rats exposed to the inhalation of 8.4 mg/m3 of Alumina Silicate
Ceramic Fiber (RCF) into lung for twelve months.
2. There is a report that pleural sarcoma has been frequently observed in rats exposed to the dose of ceramic fiber into pleural cavity,
especially be diameter less than 0.25 mm and length more than 8 μm (8 μm exclusive).
3. There is a report that pleural interstitial fibrosis has been observed in 3 rats out of 36 rats exposed to one dose of 20 mg RCF into
pleura.
4. There is a report that one % of interstitial fibrosis has been observed in hamsters exposed to the inhalation of 12 mg/m3 RCF with
1.8 mm for 24 months (6 hours per day, 5 days per week) not in rats.
Also there is a report that peritoneal interstitial fibrous has been observed in hamsters and rats exposed to one dose of same 25 mg/
m3 into pleural cavity.
5. There is a report that tumor has been observed in 2.6-14.5% of rats exposed to the inhalation of RCF 3-30 mg/m3 with kaolin as raw
materials for 24 months (6 hours per day, 5 days per week).
TOC-LCSH/CSN
389
5.10
Safety Data Sheets
SECTION VII
PRECAUTION FOR SAFE HANDLING AND USE
Step to be taken in case material is released or spilled:
Use vacuum suction with HEPA filters to clean up spilled material suppressing generations of airborne dust. Wear air purifying respirator
or mask when clean up.
Precaution on waste disposal:
Disposal of this waste material must be by plastic bag with minimum 0.05mm thickness to prevent generations of airborne dust.
The transportation, storage, treatment and disposal of this waste material must be conducted in compliance with all applicable local
regulations.
Precaution on transportation:
Avoid generations of airborne dust by breakage of package during transportation. Repair broken part of package by adhesive tape and
also arrange new packing in case of breakage.
Refer "Step to be taken in case material is released or spilled" in this MSDS for treatment of spilled material.
SECTION VIII
CONTROL MEASURES
Suppressive procedure: Restrict and separate areas where this product is used.
Close up tight and/or install/provide proper general and/or local ventilation at the places where dust concentrations exceeds TLV. Inspect
regularly such ventilation to maintain initial functions.
Respiratory Protection (Specify Type):
Respiratory protection must be selected/used according to airborne concentrations as described below.
Respiratory protection must be checked for fitness to face and also arranged proper maintenance on filter in case use Half-Face air
purifying respirator.
Concentration (8-hours TWA) Minimum Acceptable Respirator Type
0.1- 1 f/cm3
Disposable dust respirator.
1- 5 f/cm3
Half-Face, air-purifying respirator equipped with high-efficiency particulate air (HEPA) filter cartridges.
5-25 f/cm3
Full-Face, air purifying respirator with high-efficiency particulate air (HEPA) filter cartridges or
powered air-purifying respirator equipped with HEPA filter cartridges.
3
Greater than 25f/cm
Full-Face, positive pressure supplied air respirator.
Eye Protection:
Wear proper eye protection such as chemical goggles, safety glasses with side seal.
Other Protective Clothing or Equipment:
Wear gloves and long-sleeve work clothes to prevent skin irritation as necessary. Remove materials from area of contact of clothes by
vacuum suction with HEPA filter or adhesive tape avoiding generations of airborne dust.
Recommended workers who may be sensitive to a fiber not to engage in handling this product.
SECTION IX
SPECIAL PRECAUTIONS
Avoid smoking at the workplace.
Preparations containing RCF should not be sprayed.
This product does not contain crystalline silica. However product which has been in service at elevated temperatures (greater than 1,000 °C) may undergo partial
conversion to cristobalite, a form of crystalline silica. Cristobalite is classified as a GROUP 1 by IARC and by definition the agent of GROUP 1 is carcinogenic to
humans. So special caution must be taken.
The information provided on this Material Safety Data Sheet is based on ACGIH Threshold Limit Values 2002 as of the date of issuance of the sheets. The
purchaser shall follow the up-to-date rules and also your local rules, laws, regulations, etc.
Obey up-to-date local rules, laws, regulations, etc.
NOTICE:
390
The information presented herein is based on data considered to be accurate as of date of preparation of this Material Safety Data Sheet.
However, no warranty or representation, express or implied, is made as to the accuracy or completeness of the foregoing data and safety
information, nor is any authorization given or implied to practice any patented invention without a license. In addition, no responsibility
can be assumed by vendor for any damage or injury resulting from abnormal use, from any failure to adhere to recommended practices,
or from any hazards inherent in the nature of the product.
TOC-LCSH/CSN
5.10
Safety Data Sheets
5.10.6 Catalyst Platinum Black
Shimadzu Scientific Instruments, Inc.
7102 Riverwood Drive Columbia, MD 21046
Tel: 1(800) 477-1227
Control No.
Date
MATERIAL SAFETY DATA SHEET
SECTION I
CHEMICAL PRODUCT AND COMPANY IDENTIFICATION
Commercial Name:
General Use:
Manufacturer’s Name:
Address:
Emergency Phone:
Emergency Fax:
CATALYST PLATINUM BLACK ST type (Parts No. 017-42801)
Industrial Catalyst
SHINWA CHEMICAL INDUSTRIES, LTD.
50-2 Kagekatsu-cho, Fushimi-ku, Kyoto 612-8307 Japan
81(75)621-2360
81(75)602-2660
SECTION II
COMPOSITION/INFORMATION ON INGREDIENTS
Component
CAS No.
Platinum
7440-06-4
0.5 %
Aluminum Oxide
1344-28-1
98.5 %
7732-18-5
1.0 %
Water
SECTION III
Content (%)
HAZARDS IDENTIFICATION
Emergency overview:
Black or Gray sphere
Odorless
Flash point: Not applicable
Dust may cause mechanical eye irritation.
Prolonged or excessive inhalation may cause respiratory tract irritation.
Harmful if large amounts are swallowed. May cause gastrointestinal tract irritation.
Contact with organic vapors may cause a vigorous reaction with possible fire.
Potential health effects
Eye contact: Causes eye irritation.
Skin contact: May cause skin irritation.
Ingestion: No information on significant adverse effects.
Inhalation: may cause irritation, metal fume fever, difficulty breathing.
Carcinogenicity
Ingredient
Content (%)
NTP
IRAC
OSHA
ACGIH
Platinum
0.5
N
N
N
N
Aluminum Oxide
98.5
N
N
N
N
Chronic health hazards: None known.
Medical conditions generally aggravated by exposure: None known
SECTION IV
FIRST AID MEASURES
Eye contact:
Flush eyes with plenty of water. If irritation develops, call a physician.
Skin contact:
Immediately wash skin with soap and plenty of water. If irritation persists, call a physician.
Ingestion:
Procedures normally not needed. If large quantities are ingested, seek medical advice.
Inhalation:
Procedures normally not needed. If exposed to excessive levels of dust or fumes, remove to fresh air seek medical attention.
SECTION V
FIRE-FIGHTING MEASURES
Extinguishing Media: Use water, carbon dioxide or form.
Auto ignition Temperature: Not available.
Explosion Limits, lower: N/A
Explosion Limits, upper: N/A
Special fire Fighting procedures: Wear positive-pressure self-contained breathing apparatus.
Unusual fire and explosion hazards:
Contact with organic vapors may cause a vigorous reaction with possible fire.
SECTION VI
ACCIDENTAL RELASE MEASURES
Vacuum or scoop the spilled material into a container for reclamation or disposal.
Avoid dusting.
Note: In the event of an accidental release of this material, the above procedures should be followed.
Additionally, proper exposure controls and personal protection equipment should be used, and disposal of the material should be in accordance with Section XIII
Disposal Considerations.
SECTION VII
HANDLING AND STORAGE
Keep away from heat sparks and flame.
Store in a cool, dry location away from incompatible materials.
Store in tightly closed container.
Wash thoroughly after handling.
TOC-LCSH/CSN
391
5.10
Safety Data Sheets
Avoid contact with eyes, skin and clothing.
Avoid generating or breathing dust.
SECTION VIII
EXPOSURE CONTROLS, PERSONAL PROTECTION
Exposure Limit:
Platinum
1mg/m3 OSHA PEL TWA
1mg/m3 ACGIH TWA
1mg/m3 NIOSH recommended TWA 10 hours
Aluminium oxide
15mg/m3 (Total dust) OSHA PEL 8H TWA
5mg/m3 (Respirable dust) OSHA PEL 8H TWA
10mg/m3 ACGIH TLV
Ventilation:
General; Local exhaust ventilation as necessary to control dust.
Protective Equipment:
Safety glasses (With side shields) as necessary.
Impervious gloves, apron, boots.
Respiratory Protection: Filter respirator.
SECTION IX
PHYSICAL AND CHEMICAL PROPERTIES
Appearance: Black or Gray Sphere
Odor: Odorless.
Bulk Density: 710-770 (g/L)
Boiling Point: Not Applicable
Melting Point: Not Applicable
Vapor Pressure: Not Applicable
Solubility in water: insoluble
SECTION X
STABILITY AND REACTIVITY
Chemical Stability:
Stable at normal temperatures in closed containers under normal storage and handling conditions.
Incompatibility (Materials to avoid):
Strong oxidizers.
Acids, Alkalies.
Hazardous Decomposition or By-Products: Not applicable
Polymerization: Polymerization is not expected to occur.
SECTION XI
TOXICOLOGICAL INFORMATIO
Ingredient
LD50
LC50
None Established
None Established
None Established
None Established
None Established
None Established
Platinum
CAS No. 7440-06-4
9100 mg/kg/26 weeks intermittent oral-rat TDLo
Tumorigenic data: 5250 mg/kg implant-rat-TDLo.
Aluminium oxide
CAS No. 1344-28-1
Tumorigenic data: 90 mg/kg intrapleural-rat-TDLo.
Water
CAS No. 7732-18-5
SECTION XII
ECOLOGICAL INFORMATION
Ecotoxicity: Not data available.
Environmental Fate: Not data available.
SECTION XIII
DISPOSAL CONSIDERATION
Observe all federal, state and local regulations when disposing of this material.
This material should be recovered for recycling.
SECTION XIV
TRANSPORT INFORMATION
UN Number: Not Regulated
Avoid: Keep away from oxidizing materials and source of ignition.
Avoid rough handling or dropping.
SECTION XV
REGULATORY INFORMATION
Follow all regulation in your country.
SECTION XVI
OTHER INFORMATION
The information herein is given in good faith, but no warranty.
The above information is believed to be correct to be the best of our knowledge and information but does not purport to be all inclusive and shall be used only as a
guide. This product is intended to be used by expert persons having chemical knowledge and skill, at their own discretion and risk and Shinwa shall not be held
liable for any damageresulting from handling or from contact with the above material.
392
TOC-LCSH/CSN