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Emerging Hyphenated and Comprehensive Multi-Dimensional Techniques for the Measurement of
POPs in Food
J.-F. Focant
Mass Spectrometry LaboratoryBiological and Organic Analytical Chemistry
Persistent Organic Pollutants
9 agrochemicals:-Aldrin -Chlordane-DDT -Dieldrin-Endrin -Heptachlor-HCB -Mirex-Toxaphene
3 industrial substances:-PCBs-PCDDs-PCDFs
POPs
Target Analytes2,3,7,8-substituted PCDDs (7)2,3,7,8-substituted PCDFs (10)Non-ortho PCBs (4)Mono-ortho PCBs (8)EU marker ‘Tracer’ PCBs (6)‘Biomonitoring’ PCBs (30)Selected OCPs (12)Selected PBDEs ? (8)
… Σ = 80+
TEFs
Contributors to human intake
FishMeatMilk
PCDD/Fs + NO-PCBs
35 %32 %
33 %
Target Matrices
Animal feedingstuffsHuman specimen
Belgium 2001 (Focant et al., 2002)
EU Directive 1881/2006 ECEU Directive 1883/2006 EC EURACHEM Guide ‘The fitness for purpose of analytical methods’
QA/QC Guidelines
Requirements for analytical procedures:-Sensitivity (LOQs) -Selectivity-Accuracy -Trueness-Robustness -13C-labeled IS-Recovery rates -Separation: ’should be sufficient’
Requirements for analytical procedures– High sensitivity: low MDLs– High selectivity: distinction for PCDDs, PCDFs and
DL-PCBs from co-extracted and interfering compounds
– High accuracy: provide a valid estimate of the true concentration
– Trueness: +/- 20 % and CV< 15%– 13C-labeled IS: addition of PCDD/F and DL-PCB– Recovery rates: 60-120 % (30 - 140 %)– GC separation: “should be sufficient”– Lower - Upperbound: 20 % difference (in the
range of 1 pg/g fat for food)
EU Directive 1883/2006 EC
The Dream
Time Cost Problems
0 0 0
0€101h
Sample
Congener-specific Results
Dreams Sometimes Come True
1886
1970’s
Area of EffortsReducing manual handlingIncreasing sample throughput (# analytes)Increasing analytical speedDecreasing blank levels (improve LOQs)Get a better position in The Triangle
Speed(Low cost)
Selectivity
Sensitivity
POP Analysis SkeletonLLE, Soxhlet, SFE, MAE, SPME,SPE, MSPD, SBSE, PLE, …Extraction
Prep. LC (Silica), HPLC, SEC (GPC), …
Florisil, Alumina, Carbon, PYE, …
GC, GC-GC, GCxGC, …
Sector HRMS, QISTMSn, TOFMS, µECD,EIAs, RBAs, …
Clean-up
Fractionation
Separation
Measurement
Coupling (Instrumental)SPME-GC-MS SBSE-GC-MSSFE-GC-MS
Limited efficiencyfor Dioxins
SPE(or PLE)-Prep.LC-GC-IDMS(or RBA)
Liquids Solids SilicaAluminaCarbon
Automated
ECF Integrated Approach
Time Cost Problems
0 0 0
0.5€4000.5dayGC-MS
AutomatedSPE or PLE
Automated MCLCClean-up System
Samples
Batches of 5-10 samples
Fluid Samples
Sample homogenisation
Spiking, proteins precipitation, ...
SPE (C18) extraction
Side ‘lipid percent’ determination
Clean-up
Reverse Phase
Non-polar phase (C18)Polar solvent (MeOH, …)
Selective retention of the analytes
SPE SchematicSolvated bonded silica
SiO
SiO
Si
O OH O
C18 C18
Solvated bonded silica
SiO
SiO
Si
O OH O
C18 C18
PumpGauge
Nitrogentank
C18
Silica
Aqueous waste
1 2 3 4
Sample
1. Hexane2. Hexane-Dichloromethane (1:1)3. Ethyl acetate-Toluene (1:1)4. Toluene
1 2 3 4
1. Water2. Acetonitrile3. Hexane-Dichloromethane (1:1)4. Air
Carbon
Organic waste
1
1. PCDD/Fs & cPCBs
ECF Integrated System (liquids)
GC-MSIn parallel, 2 h/batch
SPE
Si Al
C
Milk
Extractfor GC-MS
0.0
0.5
1.0
1.5
2.0
2.5
3.0
2,3,7,
8 TCDD
1,2,3,
7,8 PeC
DD1,2
,3,4,7
,8 HxC
DD
1,2,3,
6,7,8
HxCDD
1,2,3,
7,8,9
HxCDD
2,3,7,
8 TCDF
1,2,3,
7,8 PeC
DF2,3
,4,7,8
PeCDF
1,2,3,
4,7,8
HxCDF
1,2,3,
6,7,8
HxCDF
2,3,4,
6,7,8
HxCDF
pg g
-1 m
ilk p
owde
r
SoxhletManual SPEIntegrated SPE
Accuracy (milk CRM)
Serum QC Chart
0.15
0.17
0.19
0.21
0.23
0.25
0.27
0.29
0.31
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Run number
Con
cent
ratio
n (p
gTEQ
/g)
PCDD/FsManual SPEIntegrated SPE
(semi)Solid Samples
Sample homogenisation (liquid N2)
Freeze-drying (overnight)
Grinding
Spiking, PLE extraction
Side ‘lipid percent’ determination
Clean-up
Pressurized Liquid Extraction
Na2SO4
Cryo-homogenizationDrying (lyoph, …)120°C, 1500 psiHexane (others)Static and/or dynamic
10-30 min/sample
Na2SO4
Z
PLE Options Z Fat retainer (H2SO4-Si)
Several groups reported the use of H2SO4-Si to remove part of the lipids directly inside the extraction cell.
BUT:- Restricted to few extraction solvents- H2SO4-Si very ‘strong’ in conditions
like 120°C/1500 psi
100ml &nitrogen
On-lineevaporation
20mlsharp pulse
ECF Integrated System (solids)
In parallel, 1.5 h/batch (5-10)
CARP-1 CRM
PCDD/F concentrations
I-PCB concentrations0
2
4
6
8
10
12
14
16
2,3,7,
8-TeC
DD1,2
,3,7,8
-PeC
DD1,2
,3,4,7
,8-HxC
DD1,2
,3,6,7
,8-HxC
DD1,2
,3,7,8
,9-HxC
DD1,2
,3,4,6
,7,8-HpC
DD
OCDD2,3
,7,8-T
eCDF
1,2,3,
7,8-P
eCDF
pg /g
fw
ReferenceMeasured n=2
0
20000
40000
60000
80000
100000
120000
140000
160000
180000
200000
PCB 52
PCB 101/90
PCB 105
PCB 118PCB 138
/163/16
4
PCB 153
PCB 180
pg/g
fwReferenceMeasured n=2(Sample size = 4g)
Referen
ceMea
sured
Truen
ess (
%)
SUM PCDD/Fs 13.3 12.6 -5.3SUM PCBs 60.3 66.2 9.8SUM PCDD/Fs+PCBs 73.6 78.8 7.1pgTEQ/g f.w.
How to Measure ?SPE(or PLE)-Prep.LC ??
Liquids Solids Si, Al, C
On-line and Automated
One needs extra dimensionsChromatography, Spectroscopy, …
GC & MS
Sample Dimensionality System Dimensionality
Reference Method(HR)GC-IDHRMS ISO-17025 PTV-LVI-GC-IDQISTMS/MS alternative method
Thermo MAT95 XP Micromass AuSpec Ultima
Could we better match sample dimensionality ?
Separate injectionsDifferent GC phases- PCDD/Fs [RTX-5MS] - PCBs [HT-8]- PBDEs [STX-500]
Thermo Polaris Q
Dimensionality
GC-µECD
GCxGC-µECDGCxGC-TOFMS
GCxGC
Comprehensive two-dimensionnal gas chromatography
Peak capacity enhancer
“Two-dimensional (2D) separations are those techniques in which a sample is subject to two independent (orthogonal) displacement processes”
J. C. Giddings, Anal. Chem. 56 (1984) 1258A-1270A.
Definition of ‘Two-dimensional’
Definition of ‘Comprehensive’
A two-dimensional separation can be called comprehensive if:
1. Every part of the sample is subjected to two independent separative displacements.
Orthogonality rule
2. The separation (resolution) obtained in the first dimension is preserved throughout the process.
Conservation rule
Orthogonality Rule
VolatilityPolarity
OK KO
Conservation Rule
Peak capacity = = 50 peaks
Classical GC
… …
Injector Detector
30m x 0.25mm x 0.25µm
Injector
1st dimension 2nd dimension
Detector
GCxGC
Column 1 Column 230m x 0.25mm x 0.25µm 2m x 0.25mm x 0.25µm
GCxGC (2 columns)… …
1D = 30 m2D = 2 m
Peak capacity = 1Dnc x 2Dnc= 50 x 19 = 950 peaks
[tTOT GCxGC = tTOT classical GC]
Splitless
1D RTX-500 40m0.18mm ID x 0.11µm df
2D BPX-50 1.5m0.10mm ID x 0.10µm df
LN2-Quad-jetsModulator
TOFMS
1TtR ~ 50 min
PM = 4 sec
Instrumental Setup
Injector
1st dimension
LN2 supplier
Trapping
Detector
1st Oven
2nd dimension2nd Oven
Detector
1st dimension
LN2 supplier
Releasing
2nd dimension2nd Oven
1st Oven
Injector
1st dimension
LN2 supplier
Refocusing
Detector
2nd dimension2nd Oven
1st Oven
Injector
1st dimension
LN2 supplier
Injection into second dimension
Detector
1st Oven
2nd dimension2nd Oven
Injector
2nd Oven
Modulator
Modulation ProcessSampling rate 0.25 Hz
1st Dim tR
2nd Dim tR
4 seconds
Each ‘ slice ’ is a separate seconddimension chromatogram
Signal at the Detector
Signal4 sec
Time15222
15200
15240
15262
15280
15302
15320
15342
15360
Displaying the Data
Contour Plot
2nd Dim tR (4 sec)
1st Dim tR
Signal
3D Plot
3D Plot
1st Dim tR
2nd Dim tR
Contour Plot
1st Dim tR
2nd Dim tR
Why TOFMS ?
ScanningMS
SIM
Full Scan
–Comprehensive mass analysis–Slow
–Selective mass analysis–Fast
TOFNon-scanningMS
–Comprehensive mass analysis–Fast
(HRMS, QISTLRMS²)
Simultaneous samplingIon ratio remains constant across peaksSpectral continuity
Deconvolution
Specific Identification
Brunnée, Int. J. Mass Spectrom. (1987) 76 (2) 125.
Ideal Mass Analyzer ?
Time Compression
10 scans/s
TOF up to 500 scans per sec Scanning quad 2-5 scans per sec...
200 scans/s
200 ms peak
Coelution Solving Power
GCxGC TOFMS
Coelution
Peak capacity Deconvolution
Separation
Chromatographicresolution
Analyticalresolution
Symbiotic Relation
- TOFMS is the detector of choice to describe narrow 2D GCxGC peaks
&
- GCxGC zone compression enhances TOFMSsensitivity
Comprehensive Multidimensionality
1st Dim.GC
2nd Dim.GC
3rd Dim.TOFMS
ThermalModulation
IonisationModulation
Volatility Polarity Mass
OrthogonalityMinutes Seconds MilisecondsTime
scale
PCDD/PCDFs and Planar-PCBs
1tR (s)CB-80
CB-77
CB-81
CB-126
CB-169
12378-PeCDD
12378-PeCDF23478-PeCDF
123478-HxCDF
123678-HxCDF
234678-HxCDF
123789-HxCDF
123478-HxCDD
123678-HxCDD123789-HxCDD
1234678-HpCDF
1234789-HpCDF
1234678-HpCDD
OCDF
OCDD
2378-TCDF
2378-TCDD
1234-TCDD
2tR (s)
WHO and Tracer PCBs
2tR (s)
1tR (s)
CB-123
CB-118
CB-114
CB-105
CB-167
CB-156CB-157
CB-189
CB-170
CB-101
CB-28
CB-52
CB-153
CB-138 CB-180
2000 4000 6000 80000
1
2
3
1tR
2tR
2000 4000 6000 80000
1
2
3
1tR
2tR
C12H9ClC12H9ClC12H8Cl2C12H8Cl2
C12H7Cl3C12H7Cl3C12H6Cl4C12H6Cl4
C12H5Cl5C12H5Cl5
C12H4Cl6C12H4Cl6
C12H3Cl7C12H3Cl7
C12H2Cl8C12H2Cl8
C12HCl9C12HCl9
209 PCBs (HT-8/BPX-50 Set)
C12Cl10
1tR (s)
2tR (s)
196 congeners separatedin 150 min
The 3 Dimensions are Needed2Intensity
CB-132
CB-179
CB-1612IntensityIntensity
CB-132
CB-179
CB-161
CB-161CB-179
CB-132
1tR
2tRCB-161CB-179
CB-132
1tR
CB-161CB-179
CB-132
1tR1tR
2tR C
B
A
B
C
D
E
Isotope Dilution (13C12-Labels)Area = 1+2+3+4 (12C & 13C)
1
2
3
4
NativeLabeled
23478-PeCDF
PCDD/F Calibration
Standard Area Certified Calculated Response Expected Calculated Ion Ratio Concentration Concentration Factor Ion Ratio Ion Ratio Result
CDC-07:1 6078 5 4.8 0.97 0.654 0.615 PassedCDC-08:1 9121 7.5 7.5 1.01 0.654 0.643 PassedCDC-06:1 3005 2 2.0 1.01 0.654 0.717 PassedCDC-05:1 1420 1 1.0 0.98 0.654 0.663 PassedCDC-04:1 218 0.5 0.5 0.99 0.654 0.612 PassedCDC-03:1 379 0.2 0.3 1.59 0.654 0.649 Passed
0.20 pg 12C-2,3,7,8-TCDF
50 pg 13C-2,3,7,8-TCDF
Sensitivity
1 µl injected SL
Quan S/N = 10Area = 350
Quality Control Charts
BDE-47
BDE-100
CB-153
‘Cleaned’ Fish Extract
CB-80 recovery std (0.5 ng)
Tracer PCBs in Fish
1.5g sample sizeRSD GCxGC-TOFMS: 1-14%RSD GC-HRMS: 3-5%RSD GC-MS/MS: 2-5%
N = 6
0
1000
2000
3000
4000
5000
6000
7000
TriCB-28 TeCB-52 PeCB-101 HxCB-138 HxCB-153 HpCB-180
pg/g
fw
GCxGC-TOFMSGC-HRMSGC-MS/MS
Non- and Mono-ortho PCBs in Fish
N = 6
15g sample size
0
500
1000
1500
2000
2500
PeC
B-1
05
PeC
B-1
18
pg/g
fw
0
50
100
150
200
250
300
PeC
B-1
14
PeC
B-1
23
HxC
B-1
56
HxC
B-1
57
HxC
B-1
67
HpC
B-1
89
TeC
B-77
GCxGC-IDTOFMSGC-IDHRMSGC-IDQISTMS/MS
0
2
4
6
8
10
12
14
16
TeC
B-81
PeC
B-1
26
HxC
B-1
69
0
500
1000
1500
2000
2500
PeC
B-1
05
PeC
B-1
18
pg/g
fw
0
50
100
150
200
250
300
PeC
B-1
14
PeC
B-1
23
HxC
B-1
56
HxC
B-1
57
HxC
B-1
67
HpC
B-1
89
TeC
B-77
GCxGC-IDTOFMSGC-IDHRMSGC-IDQISTMS/MS
0
2
4
6
8
10
12
14
16
TeC
B-81
PeC
B-1
26
HxC
B-1
69
RSD GCxGC-TOFMS: 2-17% (33%)RSD GC-HRMS: 4-8% (34%)RSD GC-MSMS: 6-22%
PCDD/Fs in Fish
N = 6
15g sample size RSD GCxGC-TOFMS: 12-60% (95%)RSD GC-HRMS: 4-32% (64%)RSD GC-MSMS: 5-30% (44%)
0
0.5
1
1.5
2
2.5
3
3.5
4
2,3,7,
8-TeC
DD
1,2,3,
7,8-P
eCDD
1,2,3,
4,7,8-
HxCDD
1,2,3,
6,7,8-
HxCDD
1,2,3,
7,8,9-
HxCDD
1,2,3,
4,6,7,
8-HpC
DDOCDD
2,3,7,
8-TeC
DF
1,2,3,
7,8-P
eCDF
2,3,4,
7,8-P
eCDF
1,2,3,
4,7,8-
HxCDF
1,2,3,
6,7,8-
HxCDF
1,2,3,
7,8,9-
HxCDF
2,3,4,
6,7,8-
HxCDF
1,2,3,
4,6,7,
8-HpC
DF
1,2,3,
4,7,8,
9-HpC
DFOCDF
pg/g
fwGCxGC-IDTOFMSGC-IDHRMSGC-IDQISTMS/MS
0
1000
2000
3000
4000
5000
1547 1549 1551 1553 1555 1557 1559
Cou
nts
0
50
100
150
200
1547 1549 1551 1553 1555 1557 1559
Cou
nts
Labels(~85pg)
Natives(~1pg)
1tR
PM = 4s RIC
1,2,3,7,8-PeCDF
29002400190014009000
1
2
3
1tR (s)
2tR (s)
‘Cleaned’ Milk Extract
Analytes of interest
Matrix interferences
Non- and Mono-ortho PCBs in Milk
N = 6
RSD GCxGC-TOFMS: 5-20% (46%)RSD GC-HRMS: 2-10%RSD GC-MSMS: 7-15%
120g sample size
0
20
40
60
80
100
120P
eCB-
118
pg/g
fw
0
5
10
15
20
25
30
35
PeC
B-1
05
PeC
B-1
14
PeC
B-1
23
HxC
B-1
56
HxC
B-1
57
HxC
B-1
67
HpC
B-1
89
TeC
B-7
7
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
TeC
B-8
1
PeC
B-12
6
HxC
B-16
9
GCxGC-IDTOFMSGC-IDHRMSGC-IDQISTMS/MS
0
20
40
60
80
100
120P
eCB-
118
pg/g
fw
0
5
10
15
20
25
30
35
PeC
B-10
5
PeC
B-11
4
PeC
B-12
3
HxC
B-15
6
HxC
B-15
7
HxC
B-16
7
HpC
B-18
9
TeC
B-7
7
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
TeC
B-8
1
PeC
B-12
6
HxC
B-16
9
0
20
40
60
80
100
120P
eCB-
118
pg/g
fw
0
5
10
15
20
25
30
35
PeC
B-10
5
PeC
B-11
4
PeC
B-12
3
HxC
B-15
6
HxC
B-15
7
HxC
B-16
7
HpC
B-18
9
TeC
B-7
7
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
TeC
B-8
1
PeC
B-12
6
HxC
B-16
9
GCxGC-IDTOFMSGC-IDHRMSGC-IDQISTMS/MS
PCDD/Fs in Milk
RSD GCxGC-TOFMS: 9-55% (75%)RSD GC-HRMS: 7-14% (34%)RSD GC-MSMS: 5-30%
N = 6
120g sample size
0
0.05
0.1
0.15
0.2
0.25
2,3,7,
8-TeC
DD
1,2,3,
7,8-P
eCDD
1,2,3,
4,7,8-
HxCDD
1,2,3,
6,7,8-
HxCDD
1,2,3,
7,8,9-
HxCDD
1,2,3,
4,6,7,
8-HpC
DDOCDD
2,3,7,
8-TeC
DF
1,2,3,
7,8-P
eCDF
2,3,4,
7,8-P
eCDF
1,2,3,
4,7,8-
HxCDF
1,2,3,
6,7,8-
HxCDF
1,2,3,
7,8,9-
HxCDF
2,3,4,
6,7,8-
HxCDF
1,2,3,
4,6,7,
8-HpC
DF
1,2,3,
4,7,8,
9-HpC
DFOCDF
pg/g
fwGCxGC-IDTOFMSGC-IDHRMSGC-IDQISTMS/MS
0.87±0.18
0.85±0.05
0.95±0.05
Mono-ortho PCBs in Pork
RSD GCxGC-TOFMS: 4-22%RSD GC-HRMS: 3-17%RSD GC-MS/MS: 9-18%
30g sample size
N = 6
0
20
40
60
80
100
PeCB-11
8PeC
B-105
PeCB-11
4PeC
B-123
HxCB-15
6HxC
B-157
HxCB-16
7HpC
B-189
pg/g
fw
GCxGC-TOFMSGC-HRMSGC-MS/MS
241.3 ± 28.3297.9 ± 8.09
268.8 ± 25.6
PCDD/Fs in Pork
30g sample size
0
0.2
0.4
0.6
0.8
1
1.2
2,3,7,8-TeCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDDOCDD
2,3,7,8-TeCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDFOCDF
pg/g
fw
GCxGC-TOFMSGC-HRMSGC-MS/MS
RSD GCxGC-TOFMS: 15-71%RSD GC-HRMS: 4-16%RSD GC-MS/MS: 8-35%
N = 6
Comparison in terms of TEQs
Use of physico-chemical congener-specific dataand WHO-1998 TEFs to estimate the sum ofPCDD/F and PCB TEQs.
Parallel measurement of sample toxicities usingthe DR-CALUX assay on sub-samples.
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
Pork Milk
pg/g
fw
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
Pork Milk
pg/g
fw
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
Fish
pg/g
fw
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
Fish
pg/g
fwGCxGC-IDTOFMS GC-IDHRMS GC-IDQISTMS/MS DR-CALUX
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
Pork Milk
pg/g
fw
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
Pork Milk
pg/g
fw
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
Fish
pg/g
fw
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
Fish
pg/g
fwGCxGC-IDTOFMS GC-IDHRMS GC-IDQISTMS/MS DR-CALUX GCxGC-IDTOFMS GC-IDHRMS GC-IDQISTMS/MS DR-CALUX
Bottom: PCDD/F TEQTop: PCB TEQ
Comparison in terms of CostBased on 1,000 samples/year over 5 years(including employment, purchases, paying-off,maintenance, licensing, etc…)
GC-IDHRM
S
GCxGC-ID
TOFMS
GC-IDQIS
TMS/M
S
DR-CALUX
Scientist employment 23% 35% 35% 36%Extraction 11% 8% 11% 7%Clean-up 28% 27% 33% 29%Measurement 38% 30% 21% 8%Licensing and royalties - - - 20%
Cost per sample (Euros) 500 500 420 270
GCxGC-TOFMS using ID works fine.
QA/QC criteria of ‘reference method’ can beapplied PLUS 2 tR available for specificity.
TOFMS is a robust instrument.
Integration of peaks requires more work.
A sensitivity improvement is still welcome.
MS-based alternative methods not to beassimilated to biological screening methods.
Take Home Message #1
Speed(Low cost)
Selectivity
Sensitivity
Political, economical, …
Real life Pyramid
GC-QISTLRMS²
GC-TOFMS
GCxGC-TOFMS
EIAs, RBAs
GC-HRMS
Trend
Take Home Message #2
1.85
2.05
2.25
2.45
2.65
2.85
3.05
700 1200 1700 2200 2700
1tR (s)
2tR (s)
1
2 3
4
5
6
7
8
10
9
11 12
13
14
1516
17
18
19
20
21
24
22
23
25
2627
28
29
30
31
32
3334
35
36
37
35 analyte/45min0.8 analyte/minOne single injection
Multi-Group Analyte Measurement
GCxGC-IDTOFMS
Source tracking (pattern recognition)
144x4 158x10 172x18 TICx-0.5
Metabolite Screening
GCxGC-LRTOFMS
Focant, Sjödin, Patterson Jr., unpublished data.
Sensitivity Backup GCxGC-IDHRMS
Sectors
Selective MSLow data densityTarget analytes
R>10,000
GCxGC-HR(sector)MSCryogenic zone compression on sector HRMS
- Attogram (10-18g)detection level…
- Not much ions inthe MS anymore…
313ag 2,3,7,8-TCDD(S/N=890)
Quantity Number of moles Number of molecules
1 microgram (µg) or 10-6 g 3 nanomoles or 3.10-9 2,000,000,000,000,000 (2.1015)1 nanogram (ng) or 10-9 g 3 picomoles or 3.10-12 2,000,000,000,000 (2.1012)1 picogram (pg) or 10-12 g 3 femtomoles or 3.10-15 2,000,000,000 (2.109)1 femtogram (fg) or 10-15 g 3 attomoles or 3.10-18 2,000,000 (2.106)1 attogram (ag) or 10-18 g 3 zeptomoles or 3.10-21 2,000 (2.103)1 zeptogram (zg) or 10-21 g 3 yaktomoles or 3.10-24 2 (2.100)
1 yaktogram (yg) or 10-24 g Phantom moles 0
Quantity Number of moles Number of molecules
1 microgram (µg) or 10-6 g 3 nanomoles or 3.10-9 2,000,000,000,000,000 (2.1015)1 nanogram (ng) or 10-9 g 3 picomoles or 3.10-12 2,000,000,000,000 (2.1012)1 picogram (pg) or 10-12 g 3 femtomoles or 3.10-15 2,000,000,000 (2.109)1 femtogram (fg) or 10-15 g 3 attomoles or 3.10-18 2,000,000 (2.106)1 attogram (ag) or 10-18 g 3 zeptomoles or 3.10-21 2,000 (2.103)1 zeptogram (zg) or 10-21 g 3 yaktomoles or 3.10-24 2 (2.100)
1 yaktogram (yg) or 10-24 g Phantom moles 0
Patterson Jr., Welch , Turner , Focant, Organohalogen Compds 67 (2005) 107.
Report with undesirable ‘not detected’Report with NO ‘not detected’
Sensitivity not a Dimension…Low level sample
Sample preparation
GCxGC-IDHRMS(Selected Descriptors)
GC-IDHRMS(Multi-Group)
2,3,7,8-TCDD… 17 PCDD/Fs + NO-PCBs
- D. Patterson Jr., W. Turner, A. Sjödinand Lab. staff at CDC
- G. Eppe, C. Pirard, M.-L. Scippo andLab. staff in Liège
- Fluid Management Systems Inc.- Leco Corp.
Thanks to
Related papers (i)• J.-F. Focant, A. Sjödin, D.G. Patterson Jr., 2006. Human Biomonitoringof Persistent Toxicants using Comprehensive Two-Dimensional Gas Chromatography and Time-of-Flight Mass Spectrometry. In: W.M.A.Niessen (Eds.). The Encyclopedia of Mass Spectrometry, Volume 8, Hyphenated Methods. ElsevierAmsterdam, The Netherlands, pp. 553-564.
• G. Eppe, E. De Pauw, J.-F. Focant, 2006. High-Resolution GC Coupled to High-Resolution MS in the Analysis of Dioxins and Related Substances, Principles and Applications. In: W.M.A. Niessen (Eds.). The Encyclopedia of Mass Spectrometry, Volume 8, Hyphenated Methods. ElsevierAmsterdam, The Netherlands, pp. 531-541.
•J.-F. Focant, G. Eppe, M.-L. Scippo, A.-C. Massart, C. Pirard, G. Maghuin-Rogister, E. De Pauw, Comprehensive two-dimensional gas chromatography isotope dilution time-of-flight mass spectrometry for the measurement of dioxins and PCBs in foodstuffs: comparison against other methods, J. Chromatogr. A. 1086 (2005) 45-60. .
Related papers (ii)• J.-F. Focant, C. Pirard, G. Eppe, E. De Pauw, Recent advances in mass spectrometric measurement of dioxins, J. Chromatogr. A. 1067 (2005) 265-275.
• J.-F. Focant, A. Sjödin, W.E. Turner, D.G. Patterson Jr., Measurement of Selected Polybrominated Diphenyl ethers, Polybrominated and Polychlorinated Biphenyls, and Organochlorine Pesticides in Human Serum and Milk using Comprehensive Two-Dimensional Gas Chromatography Isotope Dilution Time-of-Flight Mass Spectrometry, Anal. Chem. 76 (2004) 6313-6320.
• G. Eppe, J.-F. Focant, C. Pirard, E. De Pauw, PTV-LV-GC/MS/MS as screening and complementary method to HRMS for the monitoring ofdioxin levels in food and feed, Talanta 63 (2004) 1135-1146.
• J.-F. Focant, C. Pirard, E. De Pauw, Automated sample preparation-fractionation for the measurement of dioxins and related compounds in biological matrices: A review. Talanta 63 (2004) 1161-1113.
Related papers (iii)• J.-F. Focant, E. Reiner, K. MacPherson, J. Cochran, F. Dorman, A. Sjödin, D.G. Patterson Jr., Measurement of PCDDs, PCDFs, and non-ortho-PCBs by Comprehensive Multi-Dimensional Gas Chromatography-Isotope Dilution Time-of-Flight Mass Spectrometry (GCxGC-IDTOFMS), Talanta 63 (2004) 1231-1240.
• J.-F. Focant, A. Sjödin, D.G. Patterson Jr., Improved Separation of the 209 Polychlorinated Biphenyl Congeners Using Comprehensive Two-Dimensional Gas Chromatography-Time-of-Flight Mass Spectrometry, J. Chromatogr. A. 1040 (2004) 227-238.
• J.-F. Focant, J.W. Cochran, J.-M.D. Dimandja, E. De Pauw, A. Sjödin, W.E. Turner, D.G. Patterson Jr., High throughput analysis of selected polychlorinated biphenyls (PCBs) in human serum by gas chromatography/isotope dilution time-of-flight mass spectrometry (GC/IDTOFMS), Analyst 129 (2004) 331-336.
Related papers (iv)•J.-F. Focant, A. Sjödin, D.G. Patterson Jr., Qualitative evaluation of thermal desorption-programmable temperature vaporization-comprehensive multi-dimensional gas chromatography-time-of-flight mass spectrometry for the analysis of selected halogenated contaminants. J. Chromatogr. A 1019 (2003) 143-156.
• C. Pirard, E. De Pauw, J.-F. Focant, A new strategy for comprehensive analysis of polybromodiphenylethers (PBDEs), polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs) and polychlorobiphenyls (PCBs) by gas chromatography coupled with mass spectrometry (GC/MS). J. Chromatogr. A 998 (2003) 169-181.
• J.-F. Focant, E. De Pauw, Fast automated extraction and clean-up of biological fluids for polychlorinated dibenzo-p-dioxins, dibenzofuransand coplanar polychlorinated biphenyls analysis. J. Chromatogr. B 776 (2002) 199-212.
• J.-F. Focant, H. Shirkhan, E. De Pauw, On-line automated pPLE andmulti-column clean-up system for PCDD/F and PCB analysis in foodstuffs. Organohalogen Compds 55 (2002) 33-36.
• C. Pirard, J.-F. Focant, E. De Pauw, An improved clean-up strategy for simultaneous analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in fatty food samples. Anal. Bioanal. Chem. 372 (2002) 373-381.
•J.-F. Focant, C. Pirard, G. Eppe, E. De Pauw, Fast Clean-up for polychlorinated dibenzo-p-dioxins, dibenzofurans and coplanar polychlorinated biphenyls analysis of high fat content biological samples. J. Chromatogr. A 925 (2001) 207-221.
• J.-F. Focant, G. Eppe and E. De Pauw, Optimisation and Use of Tandem Mass Spectrometry in Comparison with Immunoassay and HRGC/HRMS for PCDD/Fs Screening, Chemosphere 43 (2001) 417-424.
Related papers (v)
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