Standard Operation Procedure of
Total Organic Carbon Analyzer
In Prof. Wyman’s Laboratory 701
This is a simplified instruction of the operation when the catalyst and others work well.
More detailed instruction and troubleshooting could be found in the User’s Manual.
** The liquid sample TOC ranges from 0-400ppm; solid sample (dry weight) 0-100 mg
with TOC 40-60% currently. To quantify samples out of this range, further equilibrium of
the catalyst and new calibration will be needed.
0. The check list for both liquid and solid samples analysis before you
start:
a. To fill the Cooler Drain Container with Water. (Do not bend drain tubing, as this
may prevent drain discharge.)
b. To fill the Humidifier with Water
c. To prepare Dilution Water and needle rinsing water
d. To prepare Hydrochloric acid (2N for NPOC and TC)
e. To empty waste container
f. To check Oxygen pressure (at least 100 psi)
Figure 1. Humidifier, Dilution Water and needle rinsing water, and waste container from
left to right
Prepared by Taiying Zhang
in August 2010
Page 1
1. Liquid sample analysis
I.
Standard and Sample preparation
a. Make the standard glucose solution with TOC 400 ppm. This could be prepared
with 0.1% glucose standard solution by dilution number 10.
b. Estimate the carbon content in the liquid solution based on the amount of biomass
dissolved in the solution and determine the dilution number.
c. Use DI water to dilute the solution with pipet and balance into the dry and clean
sample vials with the volume of 40 ml.
d. Load the samples into the autosampler as shown in middle of Figure 1.
II.
Sample Analysis
a. Start.
Start TOC-Control V from the Windows Start menu, and click the Sample
Table Editor button. (The Sample Table Editor can also be started directly from the
Windows Start menu and from the shortcut icon created on the desktop.)
The Sample Table Editor application starts up.
Prepared by Taiying Zhang
in August 2010
Page 2
b. Creating a Sample Table.
1. Click in the Sample Table tab of the file viewer, or click on the toolbar.
The Select H/W Settings window is displayed.
2. Select the System to be used and enter a comment if necessary.
3. Click OK. A new Sample Table is created, and opened in the Sample
Table Editor.
c. Creating a Calibration Curve File.
A calibration curve file is created to set the analysis parameters for measuring
known standard solutions and generating a calibration curve.
Prepared by Taiying Zhang
in August 2010
Page 3
1
Click New in the Calibration Curve tab of the file viewer.
(The Calibration Curve Wizard (Page 1) System Information page can
also be displayed by selecting File – New – Calibration Curve.
The Calibration Curve Wizard (Page 1) System Information page is displayed.
2
Select the system configuration to be used.
3
Click Next. The Calibration Curve Wizard (Page 2) Calibration Curve
Type page is displayed.
Prepared by Taiying Zhang
in August 2010
Page 4
4
Enter the type of calibration curve. Note: Dilution cannot be performed for IC
measurement with the TOCVCPN. Since Div. Standard Solutions / Fixed Dilution and
Div.Standard Solutions (auto correction of dilution factor) are not enabled, select
Dilution from Standard Solution.
5
Click Next.
The Calibration Curve Wizard (Page 3) Analysis Information page is
displayed. Analysis type shall be the same as that of the samples to be
Prepared by Taiying Zhang
in August 2010
Page 5
analyzed.
6
Enter the basic analysis parameters.
7
Click Next. The Calibration Curve Wizard (Page 4) Calibration
Measurement Parameters page is displayed (default settings).Suggested
No. of injection is 3/5 for higher accuracy. The unit shall be the same as
Prepared by Taiying Zhang
in August 2010
Page 6
that of the samples to be analyzed. Suggested unit is ppm.
8
Enter the advanced parameters. Depending on the Analysis type, some
items may not be displayed.
Note: Refer to the following table to ensure that the concentration does not
exceed the maximum concentration specified for the respective analysis
type. If the concentration exceeds the maximum value, the instrument
performance may be adversely affected.
Prepared by Taiying Zhang
in August 2010
Page 7
Prepared by Taiying Zhang
in August 2010
Page 8
9
Click Next. The Calibration Curve Wizard (Page 5) Calibration Points
List page is displayed.
10 Enter the advanced parameters for each calibration point. Depending on
the settings, some items may not be displayed.
11 Change the calibration point parameters as necessary using the Edit
Calibration Point Parameters dialog box. Depending on the settings in the
Calibration Curve Wizard (Page 2) Calibration Curve Type page, the
contents of the Edit Calibration Point Parameters dialog box may differ.
Dilution from Standard Solution is the suggested method.
Prepared by Taiying Zhang
in August 2010
Page 9
The Edit Calibration Point Parameters dialog box is displayed as follows if
the dilution setting is Div. Standard Solutions (auto correction of dilution
factor).
12 Click OK. The Calibration Curve Wizard (Page 5) Calibration Points List
page is displayed.
13 Click Next
Prepared by Taiying Zhang
in August 2010
Page 10
14 Enter the remaining parameters. Suggest to use the default settings.
15 Click Finish. The calibration curve file is saved.
d. Creating a Method.
1 Click New in the Method tab of the file viewer. The Method Wizard (Page 1)
System Information page is displayed. The Method Wizard (Page 1) System
Information page can also be displayed by selecting File – New – Method.
Prepared by Taiying Zhang
in August 2010
Page 11
2
Select the system to be used.
3
Click Next.
The Method Wizard (Page 2) Analysis Information page is displayed.
4
Enter the basic method information.
Prepared by Taiying Zhang
in August 2010
Page 12
5
Click Next. The Method Wizard (Page 3) Calibration Curves page is displayed.
6
Select the calibration curve files that will be incorporated into the method. Up to 3
calibration curve files can be selected. If multiple calibration curve files are
selected, the software selects the most suitable calibration curve during the
analysis. For information on this function, refer to the following page.
7
Click Next.
Prepared by Taiying Zhang
in August 2010
Page 13
8
Set the advanced analysis parameters. Depending on the Analysis type setting,
some items may not be displayed.
Prepared by Taiying Zhang
in August 2010
Page 14
9
Click Next. The Method Wizard (Page 5) Peak Time Parameters page is
displayed.
10 Enter the peak detection parameters.
11 If there is a Next button at the bottom of the page, click it and repeat this
procedure from step 6. Note: If the Analysis type is one of the following TC, IC,
NPOC, POC or TN, a Finish button will be displayed at the bottom of the page. In
this case, proceed to step 12. The other analysis types consist of combinations of
the above five types. For example, TOC is a combination of TC and IC. If there
are any analysis types for which the parameters have not been set, the parameters
pages are displayed so the items can be set. When all of the parameters are
entered for all of the analysis types, the Finish button is displayed at the bottom of
the page.
12 Click Finish. The method file is saved.
Prepared by Taiying Zhang
in August 2010
Page 15
e. Editing the Sample Table.
1. Insert the calibration curve (standard solutions) into the Sample Table. Drag the
calibration curve file from the Calibration Curve tab of the file viewer.
2. Insert the unknown samples into the Sample Table. Drag the method file from the
Method tab of the file viewer.
When analyzing multiple samples using the same conditions, the inserted sample
can be reproduced by copying and pasting. Select the inserted sample, right-click
in the cell at the left end of the row, and click Copy.
Select the rows in the Sample Table corresponding to the number of samples to
Prepared by Taiying Zhang
in August 2010
Page 16
set, right-click in the cell at the left end of the row, and click Paste.
Prepared by Taiying Zhang
in August 2010
Page 17
3. Click Vial number in the Sample Table.
4. Enter the vial numbers. Enter a number in a Vial column cell, click on the lower
right part of the cell, and drag downward to enter a series of sample vial numbers
all at once.
5. Click OK to close the window and automatically set all of the vial numbers in the
Sample Table.
f. Run the Samples Analysis
1 Open the Sample Table, and connect to the Instrument by clicking Connect.
Turn on carrier gas (oxygen 40 psi)
The ready state of the instrument is shown at the right end of the toolbar.
Approximately 30 - 40 minutes are required for the temperature of the furnace to
rise and the baseline to stabilize.
Prepared by Taiying Zhang
in August 2010
Page 18
2 Check the background.
3 Run the analysis by clicking Start.
Select the procedure to be performed when the analysis sequence is complete.
• Keep running: The instrument remains in the Ready state at the completion of
the analysis sequence even after analysis is completed.
• Shut down instrument: The instrument automatically turns off at the completion
of the analysis sequence.
• Sleep: The instrument enters the sleep state, and restarts at a specified date and
time.
Suggest to keep running.
4 Click Start to begin the analysis sequence.
5 View and Output the Analysis Results: after a peak appears, click to open the
Sample window.
Prepared by Taiying Zhang
in August 2010
Page 19
The sample window is displayed. Each of the sample analyses can be reviewed.
6 Output to a File. Click File – Ascii Export – ASCII Export Norm(Meas Data Only) to output
the contents of the Sample Table in text format. The file that is output can be opened in a text
editor or Microsoft Excel to view the content
7 Ending Analysis
Click Shutdown.
Prepared by Taiying Zhang
in August 2010
Page 20
Select the appropriate shutdown process.
• Shut down instrument: The instrument power turns off after about 30 minutes.
• Sleep: The instrument enters a sleep state, and restarts automatically at a specified date and
time.
Suggested to leave it on unless it will be idle for longer than two weeks or power
outage.
Prepared by Taiying Zhang
in August 2010
Page 21
1I. Solid sample analysis
** Solid sample analysis includes two modules: TC and IC, which require different
treatments of sample boats and Quartz-glass filter paper.
Note: Due to the potential loss of crystal solid during the combustion, recommend to use
the standard solution other than solid, especially without Quartz-glass filter paper. The
stand used to hold sample boats during analysis should be made of an inorganic material,
such as ceramic, glass, or metal, with a surface free from contamination.
a. Sample Boats, Measurement Tools, and Quartz-glass Filter Paper
Heat the sample boats in a furnace to oxidize any carbon content. Use an electric furnace
of the type normally used in a laboratory.
Note: Tweezers are supplied to handle sample boats. Heat the tip of the tweezers that
contacts the sample boat to red hot in the furnace or with gas burner to oxidize any
attached carbon
Procedure for TC Analysis
1. Heat the sample boat in the furnace at approximately 900°C for 20 minutes. Heat
the quartz-glass filter paper in the furnace at approximately 600°C for 20 minutes.
2. Store the heat-treated sample boat, quartz glass filter paper and tweezers in a
clean container or case.
a. Sample Preparation
Using a new sample boat for each sample is recommended. However, a sample boat may be
reused if the sample analyzed does not contaminate, modify, or degrade the sample boat material.
Do not reuse the quartz-glass filter paper.
Sample Boat Cleaning Procedure (TC)
1. Remove as much of the sample remaining in the used sample boat as possible.
2. Use a brush or the tip of a scraper to scrape off pieces adhering to the bottom of the
sample boat.
3. Soak the boat in approximately 2M sulfuric acid or hydrochloric acid for about 10
minutes.
4. Wash under running tap water for several minutes.
5. Rinse the tap water off the boat with de-ionized or distilled water. Dry the boat.
6. Bake the dried sample boat in a furnace at approximately 900°C for 20 minutes.
Note: • Evaluate whether a sample boat can be reused by running a blank test (an analysis with
no sample in the boat) to determine the amount of residual carbon.
• For some samples, it may not be possible to reuse the sample boat even after performing the
above treatment procedure. In these cases, use a more appropriate method to remove the residual
material from the sample boat or use a new sample boat.
Ceramic Fiber
Ceramic fiber can be reused in cases where a pure product, such as glucose, is measured as the
standard.
Although ceramic fiber can be treated according to the above method to remove any
contamination, the use of new ceramic fiber is recommended because it is relatively
The combustion-oxidation reaction (TC analysis) and the carbonate acidification reaction (IC
analysis) are more efficient when the sample particles are smaller in size.
Prepared by Taiying Zhang
in August 2010
Page 22
Drying the Sample
Solid samples may be weighed and measured directly after sampling or they can be dried before
they are weighed and measured.
The following three methods are used to dry samples before weighing.
1) heating with an electric isothermal dryer
2) air-drying over a spread-out sample
3) freeze drying
Select the appropriate method for the analytical objectives.
Note: Volatile organic components contained in a sample may be lost during drying.
Solid Samples
Weighing accuracy is directly reflected in the accuracy of the analysis results. To reduce errors
associated with weighing, use an analytical balance or microbalance to carefully weigh the
sample directly into a tared heat-treated sample boat.
Note: • Reduce the effects of poor distribution, which commonly occur with solid samples.
• Reduce the weighing error.
• Reduce the impact of external contamination, by choosing a sample amount that will
produce a result close to the upper limit of the instrument (about 30mg C).
Note: Consider the combustion characteristics of each individual sample when determining the
amount of sample. Due to a lack of oxygen during combustion, samples that burn
extremely rapidly tend to burn less completely with increasing sample size.
Analyzing Crystalline Samples Such as Oxalic Acid or Glucose
Cover the sample boat because these samples may scatter during combustion. If part of the
sample scatters out of the sample boat during combustion, artificially low and inaccurate results
will be obtained.
Use the supplied ceramic fiber to cover the sample. Ceramic fiber allows good ventilation and is
unaffected by heat and oxygen.
Fashion a long, thin cover from ceramic fiber to roughly cover the opening of the sample boat,
and place it over the sample.
Do not cover the sample boat for IC analyses.
Liquid Samples
The following two sampling methods are available for liquid samples:
1) Weighing the sample with a balance
2) Measuring the volume of the sample with a microsyringe or pipette
Note • The maximum measurable mass of a liquid sample is 0.5g for TC and 0.3g for IC.
Prepared by Taiying Zhang
in August 2010
Page 23
b. Sample table and analysis
To edit the sample table is the same as the liquid sample with ASL except the test is with SSM
other than ASL and there is no vial number involved.
With SSM, the sample could be loaded one by one manually as shown in the following figures.
Note • The O-ring is easy to pull out when the lid is pushed too closely, so the nut shall be loosen
enough before sliding the lid.
Figure 2.Solid sample module close (left) and open (right)
The injection number and sample amount are not shown in the sample table, which was input as
selecting repeat or next sample during the test.
Prepared by Taiying Zhang
in August 2010
Page 24
The review and output of the results could be performed in the same way as the ASL.
IC process need be developed later since we have not tested it yet.
Procedure for IC Analysis.
1. Soak the sample boat in 2 or 3M hydrochloric acid for about 10 minutes.
2. Rinse well with purified water and dry in an oven.
Preparing the Ceramic Fiber
When analyzing a sample that may scatter during combustion, cut off a suitable amount
of supplied ceramic fiber and cover the sample with it. Heat the ceramic fiber in the
furnace, as described for the sample boat.
Heat the Ceramic Fiber
1. Cut off a suitable amount of ceramic fiber for a single analysis (approx. 40 to
60mg).
2. Shape the ceramic fiber to about 35mm long x 10mm wide.
3. Heat the ceramic fiber, as described for the sample boat.
4. Use the heat-treated tweezers to insert the heat-treated ceramic fiber into a
clean container or case for storage.
Prepared by Taiying Zhang
in August 2010
Page 25
IC Analysis of Carbonates
Adding phosphoric acid to a carbonate during IC analysis will cause a violent reaction that may allow
part of the sample to scatter outside the sample boat. Pre-moisten this type of sample with a small
amount of water.
Prepared by Taiying Zhang
in August 2010
Page 26
List of Authorized Users of TOC
If you name is not on this list, please contact responsible user to set up a training.
ID User name (please type)
Signature
Date authorized Note
1
Taiying Zhang
8-23-2010
responsible user
2
Hongjia Li
8-23-2010
responsible user
3
Deepti Tanjore(?)
8-23-2010
4
Qing Qing
8-23-2010
5
6
7
8
9
10
11
12
13
Responsible users:
Taiying Zhang, 951-781-5780(o), 319-541-3484(cell), taiying@cert.ucr.edu
Hongjia Li,
To book any spot to use the TOC, please do it by google calender. If you have no access
to it, please email Taiying.
Prepared by Taiying Zhang
in August 2010
Page 27