1. Environmental forensics with
GCxGC TOFMS analysis
Prof Robert M Kalin
Robert.Kalin@strath.ac.uk

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. GCxGC TOFMS

4. Comprehensive 2D GC-TOFMS

5. How does it work?
Modulator

6. Why 2 Columns?
Modulator

7. Why 2 Columns?

8. GCxGC surface plot
2D Chromatogram of
a DNAPL sample
from a FMGP

9. GCxGC contour plot
2D Chromatogram of
a DNAPL sample
from a FMGP

10. GCxGC contour plot
2D Chromatogram of
a DNAPL sample
from a FMGP
≈ 2500 visible peaks

11. GCxGC contour plot
2D Chromatogram of
a DNAPL sample
from a FMGP

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. GCxGC: PCB Example
Plotted peak apexes representing the two-dimensional
retention times for all 209 PCB congeners

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. 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. 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. Sources of Coal Tar
May have been in ground >100 years
Who’s problem is it?
Environmental
Forensic
Analysis
Coal Tars

18. GC x GC TOF Mass Spec
Key
PRB9
PRB11
BH102
Traditional GC Mass Spectrometry

19. GCxGC TOFMS
Unique Separation of 1,000’s of Compounds

20. GCxGC TOFMS
Unique Separation of 1,000’s of Compounds

21. GCxGC TOFMS
Unique Separation, Identification and
Quantification of 1,000’s of Compounds

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. 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. 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. Isolation of individual fragments, in this case looking for
Fluoranthene and Pyrene at mass 202, allow for evaluation via
structural similarities

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. Isolation of individual fragments, in this case looking for
Fluoranthene and Pyrene at mass 202, allow for evaluation via
structural similarities

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. 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. Multi-Variate Statistical
Methods using large
number (156) ClassRepresentative target
compounds

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. Sources of Coal Tar
Research undertaken on sites from the UK and Europe
What about N. America???
Environmental
Forensic
Analysis
Coal Tars

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. Environmental forensics with
GCxGC TOFMS analysis
Simple as ‘ABC’
Questions?
Prof Robert M Kalin
Robert.Kalin@strath.ac.uk