Environmental Forensics - Brussels Dioxin Conference Plenary 2011

Environmental Forensics and POPs –
Merging Fields of Expertise
Court D. Sandau, PhD
Chemistry Matters
Dioxin 2011 – Plenary – August 21, 2011

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
3
www.chemistry-matters.com
Dioxin 2011 Plenary - August 22nd, 2011, Belgium

Environmental Forensic Investigation
The 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 4

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.
5

Birthplace of Environmental Forensics
Exxon Valdez 1989
Term “Environmental
Forensics” coined in Dr. Robert
Morrison’s first books since it
was used in a peer reviewed
publication.
6

Crime Scene Investigations
7

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".
8

Two Categories of EFIs
Academic & Research
Liability Driven
9

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
10

Differences Between Legal and
Research
• Documentation,
Documentation,
Documentation
Date Project id.
Date Project id.
Address
Date
Notes and pictures/videos
11

Research
• Documentation
• Sample Handling
• Chain of Custody
12

Research
• Documentation
• Sample Handling
• Chain of Custody
• Laboratory Competence
• Standard Procedures
• Communicating Results
13

Carpet Dust Sampling
• Must follow
standardized
procedures where
available
• Difficult to change
approaches
• Validation required if
methodology changes
Designation: D 5438 – 05
Standard Practice for
Collection of Floor Dust for Chemical Analysis1
This standard is issued under the fixed designation D 5438; the number immediately following the designation original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1 This practice covers a procedure for the collection of a
sample of dust from carpets and bare floors that can be
analyzed for lead, pesticides, or other chemical compounds and
elements.
1.2 This practice is applicable to a variety of carpeted and
bare floor surfaces. It has been tested for level loop and plush
pile carpets and bare wood floors, specifically.
1.3 This practice is not intended for the collection and
evaluation of dust for the presence of asbestos fibers.
1.4 The values stated in SI units are to be regarded as the
standard.
1.5 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-priate
larger, embedded in carpet household vacuum cleaners.
3.1.2 surface dust—soil 5-μm equivalent adhering to floor surfaces and vacuum cleaners.
4. Summary of Practice
4.1 The sampling method from work published in Roberts, (4).
4.2 Particulate matter is floor by means of vacuum-through a sampling nozzle Designation: D 422 – 63 (Reapproved 2002)e 1
and the particles are separated safety and health practices and determine the applica-bility
cyclone is designed to efficiently of regulatory limitations prior to use.
approximately 5-μm mean However, much smaller particles 2. Referenced Documents
efficiencies. The sampling 2.1 ASTM Standards: 2
and suction adjustments to D 422 Test Method for Particle-HVS-Size Analysis 3 Vacuum of Soils
air velocity Cleaner
for the removal D 1356 Terminology Relating to Sampling and Analysis of
and bare floor surfaces, so Atmospheres
be repeated.
E 1 Specification for ASTM Thermometers
NOTE 1—Side-by-side comparison E 337 Test Method for Measuring Humidity with a Psy-chrometer
upright vacuum cleaner revealed (the Measurement of Wet- and Dry-Bulb Tem-peratures)
least 0.2 μm and that the HVS3 smaller than 20 μm than conventional Standard Test Method for
Particle-Size Analysis of Soils1
This standard is issued under the fixed designation D 422; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
e1 NOTE—Adjunct references were corrected editorially in July 2006.
14

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…
15

Chemical Fingerprinting
Molecular fingerprint
Retention Time
Relative Response
S
S
=
Chemical Signature
DNA
= Isotope Profiling
15

Retention Time
Relative Response
S
S
=
Chemical Signature
Chemical Profiles
Marker compounds
- additives, indicator compounds, impurities
16

Marker Compounds in Petroleum
Hydrocarbons
Note that the
sample is severely
weathered.
Biomarkers have
become the
predominant peaks
Site
Sample
Isoprenoid /
Hopane
Petroleum
Biomarker
Standard
Soil samples
from boggy
areas have
phytogenic
hydrocarbons
18

Additives to Gasolines
• Proprietary additives are compounds added to hydrocarbon
products for specific purposes.
Type of Additive Examples
62% 1980s
Antiknock Alkyl Leads
Antioxidants p-phenylenediamine; alkyl-substituted
phenols
2%
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)
18%
Lead Scavengers Ethylene dibromide, Ethylene dichloride
• Additives often have discrete time intervals during which they
were introduced into a formulation.
18

Dating with Additives
Historical trend in lead usage in gasoline
Phased
out
20

Formulations of Aroclor 1254
- Dated Aroclor production
changes
- Late production Aroclor
- 1972
- Gives potential dating
mechanism of PCB
sources (unweathered)
Dr. Glenn Johnson, Energy & Geoscience Institute
University of Utah
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.
21

Retention Time
Relative Response
S
S
=
Chemical Signature
Chemical Profiles
21

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) have
presented on patterns of dioxins (all congeners). Dioxin 2010.
- QA-QC of other congeners (standards!)
23

Dioxin Fingerprinting
Unstandardized Fingerprint
24

Normalizing Data
2378-Sum Relative Homologue
Relative TEQ Total Homologue
25

From Literature
Barrel Burning
Diesel Fueled
Crematorium Truck
2,3,7,8 Sum
Relative
Homologue Relative TEQ
Total
Homologue
26

Case Studies
Creosote Unknown Incinerator
2,3,7,8 Sum
Relative
Homologue Relative TEQ Total Homologue
27

Interpretation and Visualization
Stout et al. 2002, Intro to Enviro Forensics
Courtesy of ALS Laboratories, Edmonton
28

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)
29

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
30

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
31

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
32

Cosine Theta Analysis
Aroclor 1242
0.08, 85o
Aroclor 1254
Sample X
Aroclor 1248
0.20, 78o
Aroclor 1262
0.68, 47o
Aroclor 1260
0.75, 41o
0.91, 25o
Orthogonal
Dissimilar
Co-linear, similar compositions
Theoretical Vector
1.00, 0o
Theoretical Vector
0.00, 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
33

Sediment Pattern Similarity to Aroclor
1254
0.63
0.64
0.67 0.67
• Sediments were most similar to Aroclor
1254•
Aroclor 1254 most likely source
0.75
0.78
0.77
0.76
0.89
0.86
0.85
0.79
• Very little difference between early and late
production Aroclor 1254 for cosine theta
0.67
• Closest to one is more resemblance to
0.74
Dam
Aroclor 1254 Outfall
34

DNA
= Isotope Profiling
34

Isotopes
What is an isotope?
- has same number of protons and electrons,
but different number of neutrons.
Protium Deuterium Tritium
Electron
Proton
Neutron
Stable Unstable
3He Radioactive
1H (99.98%) 2H (0.015%) 3H T1/2 = 12.32 years
36

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
37

Stable Isotope Analysis
Clarke Diagram for 2D Fingerprinting
after Whiticar, M.J., 1999 Organic matter
Bacterial MF
d2H-CH4 (‰)
d13C-CH4 (‰)
Bacterial
Carbonate
Reduction
Bacterial
Mix and
Transition
Early Mature
Thermogenic
38
O’Sullivan, G, et al. (2010) Methane forensic geo-gas investigation: building an urban reference library.
Environmental Forensics 11:1, 1-9.

Stable Isotopes
-15
-20
-25
-30
-35
-40
δ 13C (‰)
• Stable isotope data gives a “signature” to samples
• Samples may be linked or differentiated
O
Compound
AWMA – Vapour Intrusion
2007 38

Radiocarbon Isotope 14C
Naturally occurring isotope
with a half life of 5730 yrs
Measure in Percent
Modern Carbon (pMC)
40

Radiocarbon Dating
Relies on the radioactive nature and
influence of events such as nuclear
testing and fossil fuel burning
41

Carbon 14 and Natural Brominated
Compounds
Compound Δ14C (pMC)
MeO-BDE47 +103
MeO-BDE68 +119
Bromkal 70 -998
Aroclor 1260 -999
Can use natural abundance 14C
measurements to uncover the relative
contribution of industrial and natural
sources of halogenated organic
compounds to a variety of environmental
media
Teuten et al (2005) Two Abundant Bioaccumulated Halogenated Compounds Are Natural
Products, Science, 307 (5711) p.917-920.
42

Pushing Environmental Forensics
Forward
What are the limits?
• How low can you go?
• Complex mixtures?
43

How Low Can We Go?
Using cryo-focusing and HRMS, can achieve
540 ag 2378-TCDD, assuming 70 % recovery
S/N 474 (4 Sigma)
m/z 321.8936 [M+2]
12C-2378-
TCDD
in Serum
m/z 319.8965 [M]
Dr. Donald G. Patterson, Jr and Wayman Turner
Zoex - loop
modulator
44

Extreme Sensitivity
(2,3,7,8-TCDD)
Weight Moles Molecules
Microgram (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.
44

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 Dioxin 2011 Plenary - August 22nd, 2011, Belgium
46

Complexity?
Conventional GC Analysis
Unresolved Complex
Matter
Nelson et al. Environmental Forensics, 7:33–44, 2006
47

Two-Dimensional
Gas Chromatography
Nelson et al. Environmental Forensics, 7:33–44, 2006
48

Separation Power of GCxGC – POPs
β-HCCH
γ-HCCH
PCB-74
+
Heptachlor
Epoxide
PCB-44
PCB-28
HCB PCB-18
PCB-87
PCB-66
PCB-49
PCB-52
PCB-101
Oxychlordane
PCB-158
PCB-138
DDE
PCB-99
t-Nonachlor
Dieldrin
PCB-110
PCB-151
PCB-156
PCB-167
o,pDDT
PCB-149
PCB-177
PCB-153
PCB-146
p,pDDT
PCB-118
BDE-28
PCB-105
PCB-178
BDE-66
BDE-85 BB-153
PCB-189
PCB-172
BDE-100
PCB-194
PCB-183
PCB-187
PCB-180
PCB-128
PCB-157
BDE-47
Mirex
PCB-201
PCB-196
+
PCB-203
PCB-170
PCB-195
PCB-206
PCB-209
BDE-99
BDE-153
BDE-154
59
Analytes
Dr. Jef Focant
49

Dust Extract D/F Fraction by
GCxGC-TOFMS
TIC
Dr. Donald G. Patterson, Jr and Dr. Jef Focant
50

Local Supply of Diesel Fuel
Dr. Ralph Ruffolo
51

Comparison of Gasolines
Gas Station 1
Gas Station 2
Dr. Ralph
Ruffolo
52

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
53
3D-GIS Movie
Removed for
smaller file size

Environmental Forensics
Resources
54

Societies and Organizations
• International Network of
Environmental Forensics (INEF)
• Association for Environmental Health
& Sciences (AEHS) Foundation
• International Society of
Environmental Forensics (ISEF)
55

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)
56

Acknowledgements
Contact Info:
Chemistry Matters Inc.
Court Sandau
csandau@chemistry-matters.com
Twitter – Chem_Matters
57

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