emerging hyphenated and comprehensive multi-dimensional … · 2020. 6. 13. · 23478-pecdf pcdd/f...
TRANSCRIPT
![Page 1: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/1.jpg)
Emerging Hyphenated and Comprehensive Multi-Dimensional Techniques for the Measurement of
POPs in Food
J.-F. Focant
Mass Spectrometry LaboratoryBiological and Organic Analytical Chemistry
![Page 2: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/2.jpg)
Persistent Organic Pollutants
9 agrochemicals:-Aldrin -Chlordane-DDT -Dieldrin-Endrin -Heptachlor-HCB -Mirex-Toxaphene
3 industrial substances:-PCBs-PCDDs-PCDFs
POPs
![Page 3: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/3.jpg)
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
![Page 4: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/4.jpg)
Contributors to human intake
FishMeatMilk
PCDD/Fs + NO-PCBs
35 %32 %
33 %
Target Matrices
Animal feedingstuffsHuman specimen
Belgium 2001 (Focant et al., 2002)
![Page 5: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/5.jpg)
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’
![Page 6: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/6.jpg)
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
![Page 7: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/7.jpg)
The Dream
Time Cost Problems
0 0 0
0€101h
Sample
Congener-specific Results
![Page 8: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/8.jpg)
Dreams Sometimes Come True
1886
1970’s
![Page 9: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/9.jpg)
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
![Page 10: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/10.jpg)
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
![Page 11: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/11.jpg)
![Page 12: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/12.jpg)
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
![Page 13: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/13.jpg)
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
![Page 14: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/14.jpg)
Fluid Samples
Sample homogenisation
Spiking, proteins precipitation, ...
SPE (C18) extraction
Side ‘lipid percent’ determination
Clean-up
![Page 15: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/15.jpg)
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
![Page 16: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/16.jpg)
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
![Page 17: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/17.jpg)
SPE
Si Al
C
Milk
Extractfor GC-MS
![Page 18: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/18.jpg)
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)
![Page 19: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/19.jpg)
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
![Page 20: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/20.jpg)
(semi)Solid Samples
Sample homogenisation (liquid N2)
Freeze-drying (overnight)
Grinding
Spiking, PLE extraction
Side ‘lipid percent’ determination
Clean-up
![Page 21: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/21.jpg)
Pressurized Liquid Extraction
Na2SO4
Cryo-homogenizationDrying (lyoph, …)120°C, 1500 psiHexane (others)Static and/or dynamic
10-30 min/sample
![Page 22: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/22.jpg)
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
![Page 23: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/23.jpg)
![Page 24: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/24.jpg)
100ml &nitrogen
On-lineevaporation
20mlsharp pulse
ECF Integrated System (solids)
In parallel, 1.5 h/batch (5-10)
![Page 25: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/25.jpg)
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.
![Page 26: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/26.jpg)
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
![Page 27: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/27.jpg)
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
![Page 28: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/28.jpg)
Dimensionality
GC-µECD
GCxGC-µECDGCxGC-TOFMS
![Page 29: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/29.jpg)
GCxGC
Comprehensive two-dimensionnal gas chromatography
Peak capacity enhancer
![Page 30: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/30.jpg)
“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’
![Page 31: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/31.jpg)
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
![Page 32: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/32.jpg)
Orthogonality Rule
VolatilityPolarity
![Page 33: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/33.jpg)
OK KO
Conservation Rule
![Page 34: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/34.jpg)
Peak capacity = = 50 peaks
Classical GC
… …
Injector Detector
30m x 0.25mm x 0.25µm
![Page 35: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/35.jpg)
Injector
1st dimension 2nd dimension
Detector
GCxGC
Column 1 Column 230m x 0.25mm x 0.25µm 2m x 0.25mm x 0.25µm
![Page 36: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/36.jpg)
GCxGC (2 columns)… …
1D = 30 m2D = 2 m
Peak capacity = 1Dnc x 2Dnc= 50 x 19 = 950 peaks
[tTOT GCxGC = tTOT classical GC]
![Page 37: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/37.jpg)
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
![Page 38: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/38.jpg)
Injector
1st dimension
LN2 supplier
Trapping
Detector
1st Oven
2nd dimension2nd Oven
![Page 39: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/39.jpg)
Detector
1st dimension
LN2 supplier
Releasing
2nd dimension2nd Oven
1st Oven
Injector
![Page 40: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/40.jpg)
1st dimension
LN2 supplier
Refocusing
Detector
2nd dimension2nd Oven
1st Oven
Injector
![Page 41: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/41.jpg)
1st dimension
LN2 supplier
Injection into second dimension
Detector
1st Oven
2nd dimension2nd Oven
Injector
![Page 42: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/42.jpg)
![Page 43: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/43.jpg)
2nd Oven
Modulator
![Page 44: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/44.jpg)
![Page 45: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/45.jpg)
Modulation ProcessSampling rate 0.25 Hz
1st Dim tR
2nd Dim tR
4 seconds
Each ‘ slice ’ is a separate seconddimension chromatogram
![Page 46: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/46.jpg)
Signal at the Detector
Signal4 sec
Time15222
15200
15240
15262
15280
15302
15320
15342
15360
![Page 47: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/47.jpg)
Displaying the Data
Contour Plot
2nd Dim tR (4 sec)
1st Dim tR
Signal
3D Plot
![Page 48: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/48.jpg)
3D Plot
1st Dim tR
2nd Dim tR
Contour Plot
1st Dim tR
2nd Dim tR
![Page 49: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/49.jpg)
![Page 50: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/50.jpg)
![Page 51: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/51.jpg)
![Page 52: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/52.jpg)
![Page 53: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/53.jpg)
![Page 54: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/54.jpg)
![Page 55: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/55.jpg)
![Page 56: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/56.jpg)
![Page 57: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/57.jpg)
![Page 58: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/58.jpg)
![Page 59: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/59.jpg)
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
![Page 60: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/60.jpg)
Specific Identification
Brunnée, Int. J. Mass Spectrom. (1987) 76 (2) 125.
Ideal Mass Analyzer ?
![Page 61: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/61.jpg)
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
![Page 62: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/62.jpg)
Coelution Solving Power
GCxGC TOFMS
Coelution
Peak capacity Deconvolution
Separation
Chromatographicresolution
Analyticalresolution
![Page 63: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/63.jpg)
Symbiotic Relation
- TOFMS is the detector of choice to describe narrow 2D GCxGC peaks
&
- GCxGC zone compression enhances TOFMSsensitivity
![Page 64: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/64.jpg)
Comprehensive Multidimensionality
1st Dim.GC
2nd Dim.GC
3rd Dim.TOFMS
ThermalModulation
IonisationModulation
Volatility Polarity Mass
OrthogonalityMinutes Seconds MilisecondsTime
scale
![Page 65: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/65.jpg)
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)
![Page 66: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/66.jpg)
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
![Page 67: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/67.jpg)
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
![Page 68: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/68.jpg)
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
![Page 69: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/69.jpg)
Isotope Dilution (13C12-Labels)Area = 1+2+3+4 (12C & 13C)
1
2
3
4
NativeLabeled
![Page 70: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/70.jpg)
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
![Page 71: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/71.jpg)
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
![Page 72: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/72.jpg)
Quality Control Charts
BDE-47
BDE-100
CB-153
![Page 73: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/73.jpg)
‘Cleaned’ Fish Extract
CB-80 recovery std (0.5 ng)
![Page 74: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/74.jpg)
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
![Page 75: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/75.jpg)
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%
![Page 76: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/76.jpg)
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
![Page 77: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/77.jpg)
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
![Page 78: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/78.jpg)
29002400190014009000
1
2
3
1tR (s)
2tR (s)
‘Cleaned’ Milk Extract
Analytes of interest
Matrix interferences
![Page 79: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/79.jpg)
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
![Page 80: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/80.jpg)
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
![Page 81: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/81.jpg)
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
![Page 82: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/82.jpg)
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
![Page 83: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/83.jpg)
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.
![Page 84: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/84.jpg)
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
![Page 85: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/85.jpg)
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
![Page 86: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/86.jpg)
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
![Page 87: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/87.jpg)
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
![Page 88: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/88.jpg)
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
![Page 89: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/89.jpg)
Source tracking (pattern recognition)
![Page 90: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/90.jpg)
144x4 158x10 172x18 TICx-0.5
Metabolite Screening
GCxGC-LRTOFMS
Focant, Sjödin, Patterson Jr., unpublished data.
![Page 91: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/91.jpg)
Sensitivity Backup GCxGC-IDHRMS
Sectors
Selective MSLow data densityTarget analytes
R>10,000
![Page 92: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/92.jpg)
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.
![Page 93: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/93.jpg)
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
![Page 94: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/94.jpg)
- 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
![Page 95: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/95.jpg)
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. .
![Page 96: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/96.jpg)
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.
![Page 97: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/97.jpg)
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.
![Page 98: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/98.jpg)
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.
![Page 99: Emerging Hyphenated and Comprehensive Multi-Dimensional … · 2020. 6. 13. · 23478-PeCDF PCDD/F Calibration Standard Area Certified Calculated Response Expected Calculated Ion](https://reader033.vdocuments.us/reader033/viewer/2022060916/60a956c058b05c4c0b16a865/html5/thumbnails/99.jpg)
• 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)