environmental forensics - dioxin conference plenary 2011
DESCRIPTION
This presentation was a plenary talk on environmental forensics delivered at the 2011 Dioxin Conference in Brussels (www.dioxin2011.org). The presentation focused on the topic of environmental forensics investigations and techniques and their application to the field of persistent organic pollutants (POPs).TRANSCRIPT
Court D. Sandau, PhDChemistry Matters
Dioxin 2011 – Plenary – August 21, 2011
Environmental Forensics and POPs – Merging Fields of Expertise
Plenary Presentation at Dioxin 2011
• Honoured to be presenting a plenary talk at Dioxin 2011 in Belgium.
• Pictures from the talk below.
Dioxin 2011 Plenary - August 22nd, 2011, Belgium 2
Environmental Forensics
• What is it?
• Types of Environmental Forensics investigations
• Techniques used in EFIs
• POPs and EFIs
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Environmental Forensic InvestigationThe systematic examination of environmental information, which may be used in litigation, to allocate responsibility for contamination
Success relies on an understanding of a variety of disciplines and knowing which tools are best suited for a particular case
“The application of scientific methods used to identify the origin and timing of a contaminant release”
Dioxin 2011 Plenary - August 22nd, 2011, Belgium 4www.chemistry-matters.com
What do POP researchers have to offer?
- Leading edge research- Finding compounds since
PCBs were discovered- Knowledge of contaminants
- biotransformation, air dispersion, multi-component mixtures, impurities in mixtures
- Breadth of knowledge of analytical and environmental chemistry (and related sciences)
After discovering PCBs because they were interfering with his DDT chromatograms….Methyl-sulphonyl metabolites of PCBs discovered by leaving GC on, chart recorder kept reading all night, caught late eluting chemicals. Soren Jensen. 1976.
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Birthplace of Environmental Forensics
Exxon Valdez 1989Term “Environmental Forensics” coined in Dr. Robert Morrison’s first books since it was used in a peer reviewed publication.
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Crime Scene Investigations
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Environmental Forensic Investigation
Heisenberg is out for a drive when he's stopped by a police officer. The cop says: " Do you know how fast you were going? Heisenberg replies: "No, but I know where I am".
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Two Categories of EFIs
Academic & Research
Liability Driven
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Litigation and Liability Driven EFIs
• Adversarial process• Goal – make you look bad or incompetent while
making themselves look good/sympathetic• They are trying to tell if you are telling the truth or not• Good science does not necessarily prevail• Unfortunately, science is complicated (scientific
literacy 28% in 2007)• Need to prove it beyond a reasonable doubt
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Differences Between Legal and Research
• Documentation, Documentation, Documentation
Project id.
Address
Project id.DateDate
Date
Notes and pictures/videos
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Differences Between Legal and Research
• Documentation• Sample Handling• Chain of Custody
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Differences Between Legal and Research
• Documentation• Sample Handling• Chain of Custody• Laboratory Competence• Standard Procedures• Communicating Results
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Carpet Dust Sampling
• Must follow standardized procedures where available
• Difficult to change approaches
• Validation required if methodology changes
HVS-3 Vacuum Cleaner
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Contaminants where Environmental Forensics has been used
• Petroleum Hydrocarbons (refined/unrefined)…• PAHs• Chlorinated solvents (PERC)• PCBs/PCDDs/PCDFs• Metals (selected)• VOCs• Methane (coal bed methane)• Pesticides (persistent/non-persistent)• Other persistent organic pollutants – soon…
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Chemical Fingerprinting
Retention Time
Relative Response
S
S
Molecular fingerprint
=
Chemical Signature
DNA
Isotope Profiling=
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Chemical Fingerprinting
Retention Time
Relative Response
S
S
Molecular fingerprint
=
Chemical Signature
Chemical Profiles
Marker compounds
- additives, indicator compounds, impurities
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Marker Compounds in Petroleum Hydrocarbons
Note that the sample is severely
weathered.
Biomarkers have become the
predominant peaks
Isoprenoid / Hopane
Petroleum Biomarker
Standard
Site Sample
Soil samples from boggy areas have phytogenic
hydrocarbons
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
• Proprietary additives are compounds added to hydrocarbon products for specific purposes.
• Additives often have discrete time intervals during which they were introduced into a formulation.
Additives to Gasolines
Type of Additive Examples
Antiknock Alkyl Leads
Antioxidants p-phenylenediamine; alkyl-substituted phenols
Metal Deactivators Disalicylpropanediamine
Corrosion Inhibitors Carboxylic acids and diimides
Anti-icers Short-chained n-alcohols (freeze point depressants); amines and ethoxylated alcohols with long hydrocarbon chains.
Oxygenates Methanol, methyl-tertiary butyl ether (MTBE)
Lead Scavengers Ethylene dibromide, Ethylene dichloride
1980s62%
18%
2%
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Dating with Additives
Historical trend in lead usage in gasoline
Phased out
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Formulations of Aroclor 1254
- Dated Aroclor production changes
- Late production Aroclor - 1972
- Gives potential dating mechanism of PCB sources (unweathered)
G. Frame (1999) Improved Procedure for Single DB-XLB Column GC-MS-SIM Quantitation of PCB Congener Distributions and Characterization of Two Different Preparations Sold as “Aroclor 1254”Journal of High Resolution Chromatography 22:10, 533–540.
Johnson, G.W. et al (2007). Chapter 6: Principal components analysis and receptor models in environmental forensics. In: An Introduction to Environmental Forensics. 2nd Edition. (R. Morrison and B. Murphy, eds.). Elsevier. Amsterdam. pp. 207-272.
Dr. Glenn Johnson, Energy & Geoscience InstituteUniversity of Utah
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Chemical Fingerprinting
Retention TimeRelative Response
S
S
Molecular fingerprint
=
Chemical Signature
Chemical Profiles
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Limitations of Standard Practices
• Dioxin analyses focus on the dirty 17 congeners– Health driven, not forensically driven– PCBs went differently
• 193 other congeners to elucidate patterns of contamination
• More data is better for fingerprinting• Not limited to 2378 congeners• The other peaks are integrated for total
homologues
Dr. Walt Shields (Exponent) and Dr. Yves Tondeur (Analytical Perspectives) havepresented on patterns of dioxins (all congeners). Dioxin 2010.
- QA-QC of other congeners (standards!)
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Dioxin Fingerprinting
Unstandardized Fingerprint
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Normalizing Data
2378-Sum Relative Homologue
Relative TEQ Total Homologue
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
From Literature
Ba
rre
l B
urn
ing
Die
se
l F
ue
led
Tru
ck
Cre
ma
tori
um
2,3,7,8 SumRelative
Homologue Relative TEQTotal
Homologue
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Case Studies
Inci
nera
tor
Unk
now
nC
reos
ote2,3,7,8 Sum
Relative Homologue Relative TEQ Total Homologue
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Interpretation and Visualization
Stout et al. 2002, Intro to Enviro Forensics
Courtesy of ALS Laboratories, Edmonton
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
PCB Case Study
• PCBs measured in sediments from a man-made lake in USA
• Local authorities insisted that source was from my client
*13 sediments samples were analyzed for PCBs (congener specific analysis)
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Measuring PCBs
• First measured on packed GC columns – Aroclor pattern analysis– Limited or no standards
• High resolution GC coupled with mass spectrometry (low / high resolution)– surrogates / isotope labels
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Aroclor Differences
• Degree of chlorination shifts chromatogram to the right
• Most extensively used mixture was 1254– Two different formulations
• Weathering will also shift chromatogram to right
• Less time in environment = looks more like the source pattern and closer to the source
1242
1254
1260
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Cosine Theta Analysis
• An analysis of the matrix of similarity coefficients between two different samples
• Compared each lake sediment sample congener pattern to each of the Aroclor patterns
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Cosine Theta Analysis
Aroclor 12420.08, 85o
Sample X
Aroclor 1254
Aroclor 12480.20, 78o
Aroclor 12620.68, 47o
Aroclor 1260
0.91, 25o
0.75, 41o
Ort
hog
onal
Dis
sim
ilar
Co-linear, similar compositions Theoretical Vector1.00, 0o
Theoretical Vector0.00, 90o
• Normalize data into vectors
• Angles between the vectors are calculated
• Cosines of these angles represent the proportional similarity between the samples
• Nearest to one is closest resemblance
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Sediment Pattern Similarity to Aroclor 1254
• Sediments were most similar to Aroclor 1254
• Aroclor 1254 most likely source
• Very little difference between early and late production Aroclor 1254 for cosine theta
• Closest to one is more resemblance to Aroclor 1254
Dam
0.63
0.64
0.670.67
0.75
0.780.77
0.76
0.740.67
0.790.85
0.86
0.89
Outfall
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Chemical Fingerprinting
DNA
Isotope Profiling=
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Isotopes
What is an isotope? - has same number of protons and electrons,
but different number of neutrons.
Protium Deuterium Tritium
Proton
Electron
Neutron
1H (99.98%) 2H (0.015%) 3H T1/2 = 12.32 years
Stable UnstableRadioactive3He
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Common Stable Isotopes Used in EFIs
Hydrogen 1H, 2H
Carbon 12C, 13C
Nitrogen 14N, 15N
Oxygen 16O, 17O, 18O
Sulfur 32S, 34S
Chlorine 35Cl, 37Cl
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Bacterial MF
Clarke Diagram for 2D Fingerprinting
2H-CH4 (‰)
13C
-CH
4 (
‰)
Bacterial Carbonate Reduction
Bacterial
Mix
and
Tr
ansi
tion
Early Mature
Thermogenic
after Whiticar, M.J., 1999 Organic matter
Stable Isotope Analysis
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O’Sullivan, G, et al. (2010) Methane forensic geo-gas investigation: building an urban reference library. Environmental Forensics 11:1, 1-9.
www.chemistry-matters.comDioxin 2011 Plenary - August 22nd, 2011, Belgium
Stable Isotopes
-40
-35
-30
-25
-20
-15
δ 1
3 C (
‰)
Compound
• Stable isotope data gives a “signature” to samples
• Samples may be linked or differentiated
O
AWMA – Vapour Intrusion 2007
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Radiocarbon Isotope 14C
Naturally occurring isotope with a half life of 5730 yrs
Measure in Percent Modern Carbon (pMC)
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Radiocarbon Dating
Relies on the radioactive nature and influence of events such as nuclear testing and fossil fuel burning
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Carbon 14 and Natural Brominated Compounds
Compound Δ14C (pMC)
MeO-BDE47 +103
MeO-BDE68 +119
Bromkal 70 -998
Aroclor 1260 -999
Teuten et al (2005) Two Abundant Bioaccumulated Halogenated Compounds Are Natural Products, Science, 307 (5711) p.917-920.
Can use natural abundance 14C measurements to uncover the relative contribution of industrial and natural sources of halogenated organic compounds to a variety of environ- mental media
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Pushing Environmental Forensics Forward
What are the limits?
• How low can you go?• Complex mixtures?
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
m/z 321.8936 [M+2]
12C-2378-TCDD
in Serum
Using cryo-focusing and HRMS, can achieve 540 ag 2378-TCDD, assuming 70 % recoveryS/N 474 (4 Sigma)
m/z 319.8965 [M]
How Low Can We Go?
Dr. Donald G. Patterson, Jr and Wayman Turner
Zoex - loopmodulator
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Extreme Sensitivity(2,3,7,8-TCDD)
Weight Moles MoleculesMicrogram (10-6) 3 Nanomoles (10-9) 2,000,000,000,000,000
Nanogram (10-9) 3 Picomoles (10-12) 2,000,000,000,000
Picogram (10-12) 3 Femtomoles (10-15) 2,000,000,000
Femtogram (10-15) 3 Attomoles (10-18) 2,000,000
Attogram (10-18) 3 Zeptomoles (10-21) 2,000
Zeptogram (10-21) 3 Yaktomoles (10-24) 2
Yaktogram (10-24) 3 Fantomoles (10-27) 0.002
Currently at the attogram level with high resolution mass spectrometry
Dr. Donald G. Patterson, Jr.
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
One part-per-quadrillion(ppq or ag/µL)
is like measuring 1 second in 1 x 1015 seconds
… or 1 second in 32,000,000 years
One part-per-quadrillion(ppq or ag/µL)
is like measuring 1 second in 1 x 1015 seconds
… or 1 second in 32,000,000 years
Wayman Turner 46www.chemistry-matters.com
Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Complexity?Conventional GC Analysis
Unresolved Complex Matter
Nelson et al. Environmental Forensics, 7:33–44, 2006
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Two-Dimensional Gas Chromatography
Nelson et al. Environmental Forensics, 7:33–44, 2006
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
β-HCCH
γ-HCCH
HCBPCB-18
PCB-28
PCB-52
PCB-49
PCB-44
PCB-74+
HeptachlorEpoxide
Oxychlordane
PCB-101
PCB-66
DDE
PCB-99
t-Nonachlor
PCB-87
Dieldrin
PCB-110
PCB-151
PCB-149
PCB-146
PCB-153
o,pDDT
p,pDDT
PCB-118
BDE-28
PCB-105
PCB-138
PCB-158
PCB-178
PCB-183
PCB-187
PCB-177
PCB-172
PCB-180
PCB-128
PCB-167
PCB-156
PCB-157
BDE-47
BDE-66
Mirex
PCB-201
PCB-196+
PCB-203
PCB-170
PCB-195
PCB-194
PCB-206
PCB-209
BDE-99
BDE-100
PCB-189
BDE-153
BDE-154
BDE-85 BB-153
β-HCCH
γ-HCCH
HCBPCB-18
PCB-28
PCB-52
PCB-49
PCB-44
PCB-74+
HeptachlorEpoxide
Oxychlordane
PCB-101
PCB-66
DDE
PCB-99
t-Nonachlor
PCB-87
Dieldrin
PCB-110
PCB-151
PCB-149
PCB-146
PCB-153
o,pDDT
p,pDDT
PCB-118
BDE-28
PCB-105
PCB-138
PCB-158
PCB-178
PCB-183
PCB-187
PCB-177
PCB-172
PCB-180
PCB-128
PCB-167
PCB-156
PCB-157
BDE-47
BDE-66
Mirex
PCB-201
PCB-196+
PCB-203
PCB-170
PCB-195
PCB-194
PCB-206
PCB-209
BDE-99
BDE-100
PCB-189
BDE-153
BDE-154
BDE-85 BB-153
59 Analytes
Dr. Jef Focant
Separation Power of GCxGC – POPs
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Dust Extract D/F Fraction by GCxGC-TOFMS
TIC
Dr. Donald G. Patterson, Jr and Dr. Jef Focant
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Local Supply of Diesel Fuel
Dr. Ralph Ruffolo
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Comparison of Gasolines
Gas Station 1
Gas Station 2
Dr. Ralph Ruffolo
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Concluding an EFI
*Communicating the results becomes the focus of most EFIs
*Complicated methodologies, analytical techniques and results of the data interpretation must be easy to understand
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3D-GIS Movie
Removed for smaller file size
www.chemistry-matters.comDioxin 2011 Plenary - August 22nd, 2011, Belgium
Environmental Forensics Resources
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Societies and Organizations
• International Network of Environmental Forensics (INEF)
• Association for Environmental Health & Sciences (AEHS) Foundation
• International Society of Environmental Forensics (ISEF)
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
University Degrees and Training
• Masters degree – University of Strathclyde• Bachelor Degree – Bangor University• University of Florida – Certificate program
• Many courses on Environmental Forensics offered at Universities
• Environmental Forensics certification coming soon (AEHS Foundation)
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium
Acknowledgements
Contact Info:
Chemistry Matters Inc.
Court Sandau
www.chemistry-matters.com
Twitter – Chem_Matters
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Dioxin 2011 Plenary - August 22nd, 2011, Belgium