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ChemicalorSensor
Agilent
4440B
Introducing the Chemical Sensor
Agilent 4440B
Chemical Sensor with
Pirouette ® Chemometric
Software
Autosampler
Headspace 44 Pos
Mass detector
2-800 amu
Designed both for Method Developers and QA/QC laboratories, the HP4440 performs
chemical integrity measurements.
Chemical integrity testing is a determination of whether the sample fits the specifications
compared to predefined standards, or does the sample match grade A, B or C ?
Combining the proven technologies of Headspace, Mass sensor and Chemometrics, the
4440B "digitizes" the volatile fingerprint of samples to assess their chemical integrity
and/or conformity in about 4 minutes. A fraction of the headspace is transferred
quantitatively without GC separation to the Mass Detector. A total mass spectra is
generated and converted into a spreasheet on which powerful pattern recognition
techniques are applied.
Speed, Productivity and Ease of use are the main strengths of the Chemical Sensor.
Due to the cost and the analysis workload, laboratories must limit the number of controls
made on raw materials or finished products. The 4440B allows to significantly increase the
number of controls (screening) without extra workload.
Conventional techniques like GC/MS will be performed only on “positive” samples when
further investigations are required. HP4440 data are correlated with GC/MS and help
reduce identification work.
ChemSensor 4440B Principle
A Brief Reminder...
45
55
Quadrupole
Total Mass
Spectrum
Fragmentation
Detector
A fraction of the headspace is transferred
quantitatively without GC separation to the
Mass Detector. A global mass spectra is
generated and converted into a spreasheet
on which powerful pattern recognition
techniques are applied.
69
81
91
115 141169191 220
105124152 179202 235
250
Mass
Fingerprint
Headspace
Date
Report HP4440
Method : Coffee Blends
VIAL
SAMPLE N°
5
171
Sumatra
CLASS
Excellent
FIT TO MODEL
6
196
Sumatra
Excellent
7
217
Guatemala
Excellent
8
495
Ethiopia
Good
non conforme
non conforme
9
513
French roast
Excellent
10
192
Unclassified
Not a Match
11
277
French roast
Good
12
315
Italian roast
Excellent
13
168
In Progress
14
219
Waiting
15
333
Waiting
16
456
Waiting
17
567
Waiting
conforme
Automated
Interpretation
and
Prediction
Multivariate
Analysis
(PCA)
Advantages of MS Based Sensor
45
55
69
81
Proven technology
Stable
No problems with water
No problems with alcohols
Scan range determines # sensors
No poisoning
Linear to 104
Correlation with GC/MS
91
115
105 124 141
152 169179 191202 220 235 250
What is CHEMOMETRY ? What is Multivariate
Analysis ?
The field of extracting easily interpretable information
from
complex multivariate chemical data using tools
of statistics and mathematics
Want to learn more…? Visit Infometrix WEB site :
www.infometrix.com
The realms of Chemometry
1. Exploratory Data Analysis
Recognizes patterns of association in multivariate data sets. Designed to reduce large and
complex data sets into a set of best views of the data. Mostly used are PCA (Principal
Component Analysis) and HCA (Hierarchical Cluster Analysis)
2. Classification Analysis
Allows user to build models to compare unknown samples to previously analyzed experience
set. Models mostly used are
SIMCA (Soft Independent Modeling Class Analogy) and KNN (K-Nearest Neighbours)
3. Regression Analysis
A calibration model that can be used to predict the value of a property based on related
properties which are easier to measure.
Typical SIMCA Model
•
Category 1
Category 2
InfoMetrix
®
How To Operate the 4440B ?
Example : “sniffing” Essential Oils …
2 Main Steps :
Step 1. Set up Method Parameters and Run
in TRAINING MODE with
Reference Samples to build MODELS
Step 2. Analyse Unknown Samples in
PREDICTION MODE
the 4440B
4440B
1
How does it work ?
TRAIN
2
Pirouette
Headspace of
M/Z
M/Z
M/Z
M/Z
M/Z
M/Z
Standards
BUILD MODEL
Mass Sensor
+
Headspace of
Unknowns
PREDICT
3
-
-
COMPARE
InStep
+
4
ANSWERS
InfoMetrix
®
Step 1 : Set Up the Headspace and MS
Method Parameters (Developer Mode)
… And Run the 4440B inTraining Mode...
...How the Data Provided by the Mass
Sensor Look Like in the ChemStation...
Sample ‘Profile’ of Orange oil 0.591 to 0.649 min
... And How Special Macros Convert The
Raw Data Into A Pirouette File (.DAT)...
Sensor response
at mass 37 for Sample C
The Total Mass Spectra is converted
in Line Plot Format...
m/z
m/z
Many overlaid spectra
m/z
m/z
Overlaid “fingerprints” can be
easily displayed in Pirouette...
 Bergamot Oil
 Clemetine Oil
 Orange Oil
 Lemon Oil
One of the most popular representation of
Data is PCA (Principal Component Analysis)
 Bergamot Oil
 Clemetine Oil
 Orange Oil
 Lemon Oil
HCA (Hierarchical Cluster Analysis)
gives also valuable informations about
samples classes and similarities...
Step 2 : Run System in Predict Mode
to analyze unknown samples
Demonstration of the New 4440B
ChemSensor Sofware
To Start the Demo, Please
CLICK HERE
(The Demo will start
automatically
Press ESC to abort)
And Display or Print the Final Report
(= Get the Answer )
InfoMetrix
®
A Wide Range of Applications
Plastics and Packaging
Paper and Textiles
Foods
Consumer Products
Beverages
APPLICATION TO SPICES AND HERBS
Paper presented at Forum Labo, Paris, March 2000
by CNRS, Vernaison, France
There are various genotypes of thymes and it is sometimes necessary to classify
them in order to determine what category fits better to specific needs : food
industry (aromatic power), pharmaceutical (active ingredient concentration).
The Chemsensor was successfully used to :
a) Determine the Thyme genotype (thymol, citral, thujanol, wild thyme…).
b) Classify the Thymes according their concentration in Thymol and paraCymene.
c) Avoid time consuming extraction of essential oils and GC separation
d) Find out what are the discriminating ions specific of each genotype.
APPLICATION TO SPICES AND HERBS (follow ’d)
HCA
(Hierarchical
Cluster Analysis)
of Thyme samples
showing
the genotype
classification
by the 4440
93
119
MASS FINGERPRINTS OF THE VARIOUS135THYMES
91
69
77
79
121
150
71
115
111
PURPLE : citral GREEN : thujanol
136
BLUE : thymol
ORANGE : wild thyme
154
PCA (PRINCIPAL COMPONENT ANALYSIS)
OF THYMES SHOWING THE VARIOUS GENOTYPES
DISCRIMINATING IONS
APPLICATION TO FRAUD DETECTION
ON FRUIT JUICES
Paper presented at Forum Labo, Paris, March 2000
by CNRS, Vernaison, France
Pure juices and concentrates were analyzedwith the Chemical Sensor.
For juices labelled « Pure Fruit Juice », a common fraud is the additionof synthetic aromas
to pure juices to increase the pleasantness and reduce the amount of fruits used to
manufacture the product.
The main molecules responsible for the pineapple aroma are :
Ethyl 2-Methyle butyrate (present in fruit)
ions : 85 & 102
Ethyl hexanoate (not naturally in fruit)
ions : 88 & 99
Propyl hexanoate (not naturally in fruit)
ions : 71 & 117
Allyl hexanoate (absent du fruit)
ions : 71 & 99
The Chemical sensor made obvious that natural and non natural juices could be separated.
Simulated frauds and several commercial products were identified in minutes thanks to the
mapping (in SCAN mode).
In order to improve the detection sensitivity, Chemical Sensor was used in SIM (Selected
Ions Mode). Results show that additions over 10 ppb of unauthorized molecules are
detected and frauded commercial products can be highlighted
Overlaid MASS FINGERPRINTS OF THE PINEAPPLE JUICES
71
99
RED : PURE JUICE
117
GREEN : COMMERCIAL
FRAUDED
88
77
BLUE : SPIKED JUICE
91
SCREENING RESULTS (PCA) OF PINEAPPLE JUICES
(SCAN MODE)
Commercial (frauded)
Spiked Pineapple Juices
Pure pineapple juices
APPLICATION TO DETECTION AND SEMI QUANTITATION
OF TRACE BENZENE ANALYSIS IN SOFT DRINKS
Paper published in PEAK
by Leatherhead Food RA, UK, April 2000
In 1998, there was an alert in the UK concerning a possible contamination of soft
drinks with benzene (caused by contaminated carbon dioxide). Because
established methods of trace benzene analysis can be
time-consuming and laborious, there was a need to investigate a rapid method for
soft drinks screening, in order to analyse trace levels of benzene. This work was an
initial feasibility study to show how the HP4440A could be applied to a relevant
industrial issue.
DETECTION AND SEMI QUANTITATION OF
TRACE BENZENE ANALYSIS IN SOFT DRINKS
PCA view
mass 78, abundance
PLS MODEL
6000
4000
2000
2
R = 0.9968
0
0
10
20
30
40
50
benzene concentration in water (µg/kg, ppb)
HP 4440A in SIM mode - PCA and PLS Model
for unknown samples prediction
DETECTION AND SEMI QUANTITATION OF
TRACE BENZENE ANALYSIS IN SOFT DRINKS
4440A in SIM mode - Line plot of mass abundance for replicates of m/z for
benzene 8.8 ppb (lowest lines), 22 ppb (middle lines) and 44 ppb (highest lines)
APPLICATION TO SPOILAGE DETECTION IN MEAT
Paper published in PEAK
by Leatherhead Food RA, UK, April 2000
There is currently no quick reliable method for the determination of the freshness
or rancidity of minced beef in a meat factory. Currently, time-consuming methods
are used such as microbiological plate counts after incubation and extraction of
the fat and subsequent chemical measurement; and sensory tests, particularly
concentrating on appearance and odour. Buyers and sellers of minced beef and
meat in general therefore require a rapid technique that could assess the age,
freshness and organoleptic appeal of meat in order that assessment can be made as
to its quality and likely shelf-life.
Leatherhead investigated the possibility of detecting spoilage in meat using the
4440 Chemsensor.
APPLICATION TO SPOILAGE DETECTION IN MEAT
Factor 1 vs Sample #
Minced-meat storage trial HP 4440A in scan mode (25-150 m/z),
excluding fragments 28, 32, 40 and 44; PCA of modified-atmospherepacked minced meat analysed on days 0, 4, 8, 11, 14, and 17 (averaged
data).
APPLICATION TO SPOILAGE DETECTION IN MEAT
PLS Model for Automated Prediction
Minced-meat storage trial HP 4440A in scan mode (25-150 m/z),
excluding fragments 28, 32, 0 and 44;
PLS of modified-atmosphere-packed minced meat analysed on days 0,
4, 8, 11, 14, and 17, without data preprocessing
4440B PCA of Diesel
Hydro
 Hydro R/D Diesel
 Gasoil R/D Diesel
 Pump Diesel
Pump
Gasoil
4440B PCA of Surfactants
728-36
602-184
MISK-033041
360-154
4440B PCA of Gasoline-Oxygenates
MTBE+R
 Ethanol + Reference
 ETBE + Reference
ETBE+R
EtOH+R
REF
 MTBE + Reference
 Reference
4440B PCA of Cola Sodas
 Regular Cola 1
 Diet Cola 1
 Regular Cola 2
 Diet Cola 2
4440B PCA of Orange Juices
 Premium Juice,
Manufacturer 1
 Premium Juice,
Manufacturer 2
4440B Mass Sensor Response for
Paper Samples
Overlaid responses for
24 samples of 4 types
m/z =83
m/z
Red =
A
Green =
B
Blue =
C
Lavender = D
4440B Distinguishing Wines
 Notaresco, Italy
 Chianti, Italy
 Sauvignon Blanc, CA
 Mediterranean
4440B PCA of Chardonnays
 94 Vineyard 1
 94 Vineyard 2
 95 Vineyard 2
4440B PCA of Coffee Samples
 Anniversary Blend
 Ethiopia
 French Roast
 New Italian Roast
 Old Italian Roast
4440B PCA of Fragrances
Chemical Sensor 4440B Benefits
Benefit N°1
Fast : Provides Qualitative or SemiQuantitative Informations in
3-4 minutes
No Sample Preparation required
ChemSensor AGILENT 4440B
A High Productivity Screening Tool for
QA/QC Laboratories
Much more controls per day
with no extra work
reduces the risk
to miss critical
informations
High Speed Analysis
(2 to 4 minutes)
allowing fast decisions
GC ou GC/MS
Conventional
analysis
20 tests/day
ChemSensor : 200 +
tests/day
GC ou GC/MS
Conventional
analysis only when
necessary
Fast Analysis : Timely decisions
With conventional GC Based techniques
Analysis
Interpretation
Decision !
With the HP4440 ChemSensor
Automated Diagnosis
Analysis
Decision !
Reduce the delay
for critical decisions !
Chemical Sensor 4440B Benefits
Benefit N°2
A New, Very Friendly Graphical
User Interface
Allows the use of the 4440B even
by non-specialized operators
A New Friendly Graphical User Interface for QA/QC
Applications
Red/Green output for instant
verification of sample status
Total Ion Chromatogram
for signal intensity
monitoring
Sum of Mass Spectrum
for key ion
identification
Graphical PCA
representation
of fit to model
Chemical Sensor 4440B Benefits
Benefit N°3
The Instrument tells the analysts
where the differences are and help
them save valuable time
Morton Seasoning Salt
PCA Plot
1 - Morton Nature’s Seasons
Seasoning Blend—Old
2 - Morton Nature’s Seasons
Seasoning Blend—New
Conditions:
2 grams/10-mL vial,
20 min @ 70 ºC, no shake
Old
New
Morton Seasoning Salt : 4440B can
provide GC/MS correlated informations
about differences between samples
NEW
Old
93
67
136
m/z
Shredded Parmesan Cheese
Analysis: PCA Plot
Maggio
Kraft
Sargento
Using SIMCA to Identify m/z Values that
Are Different between Cheese Samples
40
45
55
60
73
Maggio
Sargento
Extract
these ions
from GC/MS
TIC to help
identify
differences.
44
m/z
Chemical Sensor 4440B Benefits
Benefit N°4
Full Correlation of ChemSensor
results with GC/MS is a key benefit
when identification of differences is
required.
Correlation with GC/MS
Incoming
material
4440B
QA/QC
BAD sample
HELP!!!
PCA plot of Fragrance Samples
4 Standards
(14 runs)
“Out-of-spec”
product (4 replicates)
Quality control lab
SIMCA Is Used to Determine
Which Ions are Different Between the
Good & Bad Samples...
Discriminating
Power
137
152
m/z
…Select Ions and
Run GC-MS in SIM Mode...
…And Perform a Library Search
Chemical Sensor 4440B Benefits
Benefit N°5
ACT (Automated Calibration Transfer)
for models long term stability
and instrument to instrument method
transfer
These 16 Months Data indicate that MS Detector is
inherently the most stable sensor used in e-nose
technologies
InterClass Distances
Heterocycles
( 16 months ).
2,3-dimethylpyrazine
2-methylpyrazine
2-methylpyrazine
2,3-dimethylpyrazine
2,5-dimethylpyrazine
2-MP
(original)
Model
2,3-DMP
(original)
Model
2,5-DMP
(original)
Model
29
261
303
300
10
192
990
629
15
However, tuning operations or instrument
specific settings may influence model
consistency over time
2,5-dimethylpyrazine
PCA on 16 mo data
New ACT (Automated Calibration Transfer)
feature allows long term stability of models
Before ACT
After ACT ( calibrant per class )
InterClass Distances
PCA Plot Unit 2 Pre+Post Tune Data
Citrus Oil
(UNIT 3)
Valencia
Unit 1
Model
Valencia
Tangerine
Mandarin
Lemon
0.5
72
165
207
Tangerine Mandarin
Unit 1
Unit 1
Model
Model
62
0.3
111
148
163
126
0.5
79
Lemon
Unit 1
Model
144
117
57
0.5
New ACT (Automated Calibration Transfer)
allows also instrument to instrument method
transfer
Before ACT
After ACT (calibrant per class))
UNIT 1
Unit to Unit Shift Eliminated
UNIT 3
Chemical Sensor 4440B Benefits
Benefit N°6
Models Fine-Tuning
With Pirouette, it is possible to select the
discrimination parameters and adapt the models
to the user needs.
For instance, we can easily “exclude” specific
masses in order to better separate samples
and/or eliminate undesired factors. The
following example shows how we can
discriminate wines without taking into account
the ethanol mass...
Wine sample clustering before exclusion
of ethanol mass
1 = Monthaven
2 = Cedar Grove
3 = Hahn
4 = Sonoma Station
5 = Louis Martini
Wine sample clustering after exclusion
of ethanol mass
1 = Monthaven
2 = Cedar Grove
3 = Hahn
4 = Sonoma Station
5 = Louis Martini
The Agilent 4440B Chemical Sensor
Industry examples
•
•
•
•
•
•
•
•
Food - cheese, cookies, vinegar, additives, seafood
Flavor & Fragrance - essential oils, perfumes
Polymer - beads, films, molded parts, coatings
Consumer products - paper, tobacco,
sweeteners, toothpaste, fabrics
Chemicals - wastewater monitoring, latex paints, carpets,
polyols, surfactants, teak oils
Pharmaceutical - residual solvents, flavors
Automobile parts - rubber, boards
Petroleum/Petrochemical - well contamination monitoring,
fuels, feedstock characterization
The Agilent 4440B Chemical Sensor
Typical Applications
• Incoming raw material inspection
• Assess product quality: Good or Bad,
Grade A, B, or C?
Toothpastes
• Point of origin characterization
• Fraud - adulteration, dilution and substitution
• Objective sensory evaluation
• Product stability
and consistency
• Reaction end point
Kerosene and Diesel mixture
Semi-quantitative model
Classification model
The Agilent 4440B Chemical Sensor
Conclusions
•
•
•
•
•
•
Fast - 2 to 4 minutes per analysis
Easy to use
Provides answers, not more data
Little or no sample prep
Unit-to-Unit Model Transfer with ACT
Correlates with
GC/MS for further
investigation
Agilent 4440B How to contact us...
For more information regarding the 4440B in your country, please contact your local
HP Sales Representative, or directly :
Rest Of Europe
Germany
USA/Canada
Yann FILAUDEAU
Agilent Techn ESMC
Tel +33 1 69 82 63 48
yann_filaudeau@agilent.com
Gerhard TRESSL
Mona Burke
Agilent Techn GmbH
Agilent Techn Inc
Tel +49 7243 602 596
gerhard_tressl@agilent.com mona_burke@agilent.com
®