Environmental forensics with
GCxGC TOFMS analysis

Prof Robert M Kalin
Robert.Kalin@strath.ac.uk
Today’s Agenda
• A n introduction to GCxGC TOFMS
• B iphenyl (PCBs) Environmental Forensics
• C oal Tar Environmental Fore...
GCxGC TOFMS
Comprehensive 2D GC-TOFMS
How does it work?

Modulator
Why 2 Columns?

Modulator
Why 2 Columns?
GCxGC surface plot
2D Chromatogram of
a DNAPL sample
from a FMGP
GCxGC contour plot
2D Chromatogram of
a DNAPL sample
from a FMGP
GCxGC contour plot
2D Chromatogram of
a DNAPL sample
from a FMGP

≈ 2500 visible peaks
GCxGC contour plot
2D Chromatogram of
a DNAPL sample
from a FMGP
GCxGC: PCB Example

Storm Petrel
Identifying the provenance of Leach’s storm petrels in the North Atlantic using polychlor...
GCxGC: PCB Example

Plotted peak apexes representing the two-dimensional
retention times for all 209 PCB congeners
Summary of congeners that could not
be resolved by chromatography are
presented as contour plots along with
their document...
PCB signature in whiting and guillemot liver. One hundred and twelve PCBs were resolved by
GCxGC-TOFMS in both samples. PC...
GCxGC: PCB Example
• Analysis of 25 wrecked storm petrels by
GCxGC-ToFMS found 83 specific PCB
congeners present in >60% o...
Sources of Coal Tar
May have been in ground >100 years
Who’s problem is it?

Environmental
Forensic
Analysis
Coal Tars
GC x GC TOF Mass Spec

Key
PRB9
PRB11
BH102

Traditional GC Mass Spectrometry
GCxGC TOFMS
Unique Separation of 1,000’s of Compounds
GCxGC TOFMS
Unique Separation of 1,000’s of Compounds
GCxGC TOFMS
Unique Separation, Identification and
Quantification of 1,000’s of Compounds
Phenanthrene and Anthracene are two important PAHs that can be
used in order to assess if material is petrogenic or pyroge...
Phenanthrene and Anthracene are two important PAHs that can be
used in order to assess if material is petrogenic or pyroge...
Phenanthrene and Anthracene are two important PAHs that can be
used in order to assess if material is petrogenic or pyroge...
Isolation of individual fragments, in this case looking for
Fluoranthene and Pyrene at mass 202, allow for evaluation via
...
Isolation of individual fragments, in this case looking for
Fluoranthene and Pyrene at mass 202, allow for evaluation via
...
Isolation of individual fragments, in this case looking for
Fluoranthene and Pyrene at mass 202, allow for evaluation via
...
Sources of Coal Tar
May have been in ground >100 years
Who’s problem is it?

Environmental
Forensic
Analysis
Coal Tars
Doe...
Different Chemical Engineering Methods of Tar Distillation results
in variable concentration of PAH production.

Is this v...
Multi-Variate Statistical
Methods using large
number (156) ClassRepresentative target
compounds
Multi-Variate Statistical
Methods using 156
Class-Representative
target compounds

Is this variation
conservative in the ‘...
Sources of Coal Tar
Research undertaken on sites from the UK and Europe
What about N. America???

Environmental
Forensic
A...
Suspected
Oil-Based
Retort
produced
the Coal
Tar,
supported
by PCA

CO- Coke oven,

HR- Horizontal Retort,

LTHR – Low Tem...
Environmental forensics with
GCxGC TOFMS analysis
Simple as ‘ABC’

Questions?

Prof Robert M Kalin
Robert.Kalin@strath.ac....
Upcoming SlideShare
Loading in …5
×

Kalin

583 views

Published on

Published in: Education
0 Comments
2 Likes
Statistics
Notes
  • Be the first to comment

No Downloads
Views
Total views
583
On SlideShare
0
From Embeds
0
Number of Embeds
4
Actions
Shares
0
Downloads
0
Comments
0
Likes
2
Embeds 0
No embeds

No notes for slide

Kalin

  1. 1. Environmental forensics with GCxGC TOFMS analysis Prof Robert M Kalin Robert.Kalin@strath.ac.uk
  2. 2. Today’s Agenda • A n introduction to GCxGC TOFMS • B iphenyl (PCBs) Environmental Forensics • C oal Tar Environmental Forensics University of Strathclyde would like to acknowledge Funding and support provided by : British Gas, Parsons Brinkerhoff, EPSRC Dr. Laura McGregor, Chris Gallagher (PhD student), David Megan (PhD Student)
  3. 3. GCxGC TOFMS
  4. 4. Comprehensive 2D GC-TOFMS
  5. 5. How does it work? Modulator
  6. 6. Why 2 Columns? Modulator
  7. 7. Why 2 Columns?
  8. 8. GCxGC surface plot 2D Chromatogram of a DNAPL sample from a FMGP
  9. 9. GCxGC contour plot 2D Chromatogram of a DNAPL sample from a FMGP
  10. 10. GCxGC contour plot 2D Chromatogram of a DNAPL sample from a FMGP ≈ 2500 visible peaks
  11. 11. GCxGC contour plot 2D Chromatogram of a DNAPL sample from a FMGP
  12. 12. GCxGC: PCB Example Storm Petrel Identifying the provenance of Leach’s storm petrels in the North Atlantic using polychlorinated biphenyl signatures derived from comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry David Megson a*, Thomas A. Brown a, Glenn W. Johnson b, Gwen O’Sullivan c, Anthony W. J. Bicknell d, Stephen C. Votier d, Maeve C. Lohan a, Sean Comber a, Robert Kalin e, Paul J. Worsfold a a Biogeochemistry Research Centre, SoGEES, Plymouth University, Plymouth, Devon, PL4 8AA, UK Energy & Geoscience Institute, 423 Wakara Way Suite 300, Salt Lake City, UT 84108, USA c Department of Environmental Science, Mount Royal University, 4825 Mount Royal Gate SW, Calgary, Alberta, T3E 6K6, Canada d Environment and Sustainability Institute, University of Exeter, Penryn Campus, Penryn, Cornwall, TR10 9EZ, UK e Department of Civil and Environmental Engineering, University of Strathclyde, Glasgow G1 1XQ, UK b
  13. 13. GCxGC: PCB Example Plotted peak apexes representing the two-dimensional retention times for all 209 PCB congeners
  14. 14. Summary of congeners that could not be resolved by chromatography are presented as contour plots along with their documented retention times and percentage abundance in the five main Aroclor. Unresolved chromatographic peaks were deconvoluted using Mass Spectra and computer software.
  15. 15. PCB signature in whiting and guillemot liver. One hundred and twelve PCBs were resolved by GCxGC-TOFMS in both samples. PCBs are arranged by elution order on the first dimension column (Rtx-PCB 60 m x 0.18 mm x 0.18 µm).
  16. 16. GCxGC: PCB Example • Analysis of 25 wrecked storm petrels by GCxGC-ToFMS found 83 specific PCB congeners present in >60% of samples. • Analysis of different organs from the same bird showed that the PCB signature did not vary greatly in samples obtained from the gut, heart, liver and stomach. • PCB signatures were different for birds recovered from Canada and the UK. • Differences in PCB signatures believed to be primarily due to different food chains.
  17. 17. Sources of Coal Tar May have been in ground >100 years Who’s problem is it? Environmental Forensic Analysis Coal Tars
  18. 18. GC x GC TOF Mass Spec Key PRB9 PRB11 BH102 Traditional GC Mass Spectrometry
  19. 19. GCxGC TOFMS Unique Separation of 1,000’s of Compounds
  20. 20. GCxGC TOFMS Unique Separation of 1,000’s of Compounds
  21. 21. GCxGC TOFMS Unique Separation, Identification and Quantification of 1,000’s of Compounds
  22. 22. Phenanthrene and Anthracene are two important PAHs that can be used in order to assess if material is petrogenic or pyrogenic in origin. Selecting mass 178 which is the molecular mass of the PAHs in question using the software allows isolated assessment
  23. 23. Phenanthrene and Anthracene are two important PAHs that can be used in order to assess if material is petrogenic or pyrogenic in origin. Selecting mass 178 which is the molecular mass of the PAHs in question using the software allows isolated assessment Anthracene Phenanthrene
  24. 24. Phenanthrene and Anthracene are two important PAHs that can be used in order to assess if material is petrogenic or pyrogenic in origin. Selecting mass 178 which is the molecular mass of the PAHs in question using the software allows isolated assessment
  25. 25. Isolation of individual fragments, in this case looking for Fluoranthene and Pyrene at mass 202, allow for evaluation via structural similarities
  26. 26. Isolation of individual fragments, in this case looking for Fluoranthene and Pyrene at mass 202, allow for evaluation via structural similarities Pyrene Fluoranthene Acephenanthrylene
  27. 27. Isolation of individual fragments, in this case looking for Fluoranthene and Pyrene at mass 202, allow for evaluation via structural similarities
  28. 28. Sources of Coal Tar May have been in ground >100 years Who’s problem is it? Environmental Forensic Analysis Coal Tars Does it work in the….. REAL WORLD
  29. 29. Different Chemical Engineering Methods of Tar Distillation results in variable concentration of PAH production. Is this variation conservative in the ‘REAL’ world? Is this variation conservative for samples that may have been in the ground for decades or centuries? Many publications studied via GC-MS – What is better using GCxGC ToFMS?
  30. 30. Multi-Variate Statistical Methods using large number (156) ClassRepresentative target compounds
  31. 31. Multi-Variate Statistical Methods using 156 Class-Representative target compounds Is this variation conservative in the ‘REAL’ world? YES Is this variation conservative for samples that may have been in the ground for decades or centuries? YES Can Unknowns be Identified? YES
  32. 32. Sources of Coal Tar Research undertaken on sites from the UK and Europe What about N. America??? Environmental Forensic Analysis Coal Tars
  33. 33. Suspected Oil-Based Retort produced the Coal Tar, supported by PCA CO- Coke oven, HR- Horizontal Retort, LTHR – Low Temperature Horizontal retort VR – Vertical Retort, D – Diesel, P:D – 50:50 petrol diesel mixture, P – petrol CWG/CR – Carbureted water gas/Creosote
  34. 34. Environmental forensics with GCxGC TOFMS analysis Simple as ‘ABC’ Questions? Prof Robert M Kalin Robert.Kalin@strath.ac.uk

×