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Applied Environmental Forensics
Technical Considerations For Legal, Insurance,
and Real Estate Decisions
Environmental Federation of Oklahoma
26th Annual Meeting
October 2017
Contact:
Tom Fort, MS, PG
[email protected] • 610-722-9050
Agenda – Environmental Forensics
▪ Common Applications
▪ Techniques
▪ Presenting Results
▪ Details on Several Methods
▪ Case Histories
o Petroleum, Creosote, or Coal Tar?
o Solvents
o Stray Methane in Buildings
▪ Basic Tips for Technical/Legal Interaction
About Me – Tom Fort
▪ Principal Forensic Scientist – Apex Companies, LLC
▪ Developed & applied techniques for >30 years
o Former COO of Boutique Forensics Firm - IST , Inc.
o Former Corporate Environmental Director – Sunoco/Chevron (20 yrs)
▪ Hydrogeologist & geological engineer
▪ Thousands of remediation sites/Hundreds of claims
▪ Managed corporate remediation and 3rd party claim reserves
▪ Risk manager and principal spill responder
▪ Environmental insurance claims expert
▪ Remedial cost estimator
▪ Expert witness
Apex Quick Facts
• Privately-held company with nearly three decades of
customer satisfaction
• 700+ employees in 60+ offices nationwide
• Full suite of professional and field environmental services
serving over 2,000 clients across the US each year
Forensics and Environmental Forensics
Forensics: Using science to establish facts
▪ Who? What? When? Where? How?
▪ “A technical investigation that produces hard
evidence useful in crafting a theory or in
supporting or refuting a position”
Environmental Forensics
▪ Highly site-specific
▪ Multidisciplinary approach
▪ Data sources
▪ Lines of evidence
Typical Applications
▪ Contaminated industrial and
commercial properties
▪ Cleanups, refinancing, or real
estate transactions
▪ Post-closing responsibility
for discovered contamination
▪ Applying buyer/seller
indemnities
▪ Source ID / Cost allocation
▪ Insurance claims
▪ 3rd party claims (e.g. trespass,
toxic tort, value diminution)
▪ Contribution claims – other
Responsible Parties
Common Questions
▪ Source of the release?
▪ When did the release happen?
▪ How did the release happen?
▪ Single release or more than one?
▪ Contribution from neighbors?
Prior owners? Tenants?
▪ Cost of cleanup?
▪ Will insurance pay?
▪ If I have to sue for damages, what
do I have to prove?
▪ How to prepare in case I am sued?
Direct Business Applications
Contaminated property cleanups
▪ ID Responsible Parties (RP)/RPs
▪ Allocate remediation cost or 3rd party damages
Insurance or 3rd Party Funding – Environmental policies
▪ Covered or not covered?
• Release source and timing
• Sudden and accidental vs. intentional or operational
• Consistency with policy terms
• Policy exclusions (possible pre-policy,
other excluded conditions)
Litigation – as plaintiff or defendant (burden of proof)
▪ Apply technical reasoning to legal case strategy
Real estate transactions - Other
Methods for Useful Conclusions
▪ Setting
o A dispute usually exists (Symptom = Failure to Act)
o Virtually guaranteed findings will be challenged
o Vigorous defense of conclusions required
• Worthless unless defended
▪ Methods
o Purposeful approach
o Attention to detail
o Zero reliance on speculation
o High quality data – collected with case objectives in mind
o Prove your point AND disprove alternative explanations
o Convincing and understandable presentation
o Robust conclusions crafted with challenge in mind
Cost = Where “Data Impact the Deal”
Always: find ways to express technical answers in dollars.
Remember: You may need to close data gaps and retain
a testifying expert to defend claimed costs.
Approach: Closely target any new data collection, build
a defensible technical basis for cost or allocation, and
prepare for rigorous challenge.
The most useful forensics practitioner is not just a
scientist, but also a remedial cost estimator and
potential testifying expert to defend the results.
Useful Tactic - Translate Conclusions Into Dollars
Petroleum Chemistry – Three Controls
1) Crude oil genesis
▪ Crudes are vastly different mixtures with unique
attributes, some of which are conserved through refining
2) Refining processes
▪ Refining processes used at different facilities for different
periods leave recognizable signatures on fuel products
3) Environmental weathering
▪ The environment alters petroleum in predictable ways
allowing trend recognition and comparisons
▪ Preferential loss of light ends and easily biodegraded
alkanes
Chemistry Approach and Types of Comparison
For Unknowns – Follow a Tiered Analytical Approach
▪ Direct comparison – field sample with a tank sample
▪ Quantitative comparison – field samples from the
same site to each other
▪ Reference comparison – field sample to a lab
standard reference
▪ Fuel type ID – Fuel ID (e.g. diesel, gasoline) with
history of products handled or stored
▪ Changing tank contents over time
Gas Chromatograph Basics
SAMPLE
BCA
A n aly s is : s a07 37,17 ,1 P ro jec t : h y droc arbons
In s t ru m ent : c han l_ 08 M ethod : m a0 814
" hy droc a rb ons ,c han l_0 8.s a0 737,17 ,1,1; "
C G 05 C oa l Tar D is t i lla te
A c qu is i t io n Tim e : 0 2 O c t 19 97 at 10:5 2.49
R es pons e(m V )
T im e (m inute s )
5 0
1 00
1 50
2 00
2 50
3 00
3 50
4 00
4 50
5 00
5 50
6 00
6 50
7 00
7 50
0 5 10 15 20 25 30 3 5 4 0 4 5 50 55
OT
P
AN
DR
OS
TA
NE
SAMPLE
INJECTOR
ANALYTE
DETECTOR
CARRIER
GAS
GC
OVEN/
COLUMN
DATA
SYSTEM
AC
B
CA
RR
IER
GA
S
TEMPERATURE IS GRADUALLY
RAMPED UP
LIGHT, VOLATILE COMPOUNDS
ELUTE FIRST (A), FOLLOWED
BY HEAVIER COMPOUNDS (B/C)
CAPILLARY COLUMN SLOWS DOWN HEAVIER
HYDROCARBON MOLECULES, ALLOWING LIGHTER
ONES TO HIT THE ANALYTE DETECTOR FIRST
DIFFERENT TYPES OF ANALYTE
DETECTORS ARE USED
(FID / MS / ECD / OTHER)
Different Crudes. Different GC/FID Signatures
Alaska North Slope Crude
After: Wang and Stout, 2007
Nigerian Crude
Different Products. Different Signatures
Arthur D. Little Inc., EM&A Laboratory
Injection: [SHC1996] 1 0412961,30,1
Acquired on 14-Apr-96 at 12:55:47 Reported on 18-Apr-97 at 17:34:34
0 10 20 30 40 50 60 70 80mins
0
200
400
600
800
1000
mV
Arthur D. Little Inc., EM&A Laboratory
Injection: [SHC1996] 4 0422964,10,1
Acquired on 23-Apr-96 at 00:58:38 Reported on 17-Apr-97 at 10:26:19
0 10 20 30 40 50 60 70 80mins
0
200
400
600
800
1000
mV
Arthur D. Little Inc., EM&A Laboratory
Injection: [SHC1996] 1 0412961,3,1
Acquired on 12-Apr-96 at 20:36:42 Reported on 18-Apr-97 at 15:35:02
0 10 20 30 40 50 60 70 80mins 0
50
100
150
200
250
mV
Gasoline
Diesel Fuel
Lube OilUCM
UCM
n-C8 n-C20 n-C30 n-C44
Retention Time Minutes
0 . 0 0 1 0 . 0 0 2 0 . 0 0 3 0 . 0 0 4 0 . 0 0 5 0 . 0 0 6 0 . 0 0 7 0 . 0 0 8 0 . 0 0
0
5 0 0 0
1 0 0 0 0
1 5 0 0 0
2 0 0 0 0
2 5 0 0 0
3 0 0 0 0
3 5 0 0 0
4 0 0 0 0
4 5 0 0 0
5 0 0 0 0
5 5 0 0 0
6 0 0 0 0
6 5 0 0 0
7 0 0 0 0
7 5 0 0 0
8 0 0 0 0
8 5 0 0 0
9 0 0 0 0
9 5 0 0 0
T i m e
R e s p o n s e _
0 2 1 0 9 8 1 0 . D \ F I D 1 A
0 . 0 0 1 0 . 0 0 2 0 . 0 0 3 0 . 0 0 4 0 . 0 0 5 0 . 0 0 6 0 . 0 0 7 0 . 0 0 8 0 . 0 0
0
2 0 0 0
4 0 0 0
6 0 0 0
8 0 0 0
1 0 0 0 0
1 2 0 0 0
1 4 0 0 0
1 6 0 0 0
1 8 0 0 0
2 0 0 0 0
T i m e
R e s p o n s e _
0 2 1 0 9 8 3 1 . D \ F I D 1 A
Spilled Oil
Weathered Oil
IS IS IS
nC17
nC34
IS IS IS
nC17 nC34
Over-reliance on GC-FID can be problematic
?
UCM
Weathering Changes Fingerprint with Time
Sulfur and Dyes in Distillate Fuels
▪ Distillates include heating oil, kerosene, & diesel fuel
o Heating Oil #2 is similar to Diesel #2 except for sulfur restrictions, cetane no., and dye mandate.
o Jet Fuel (Jet A), kerosene, and Diesel #1 are also similar.
▪ Sulfur content has been regulated over time and provides useful criteria to date distillate releases.
o 1920s #2 Heating Oil (Diesel) (1.5% Sulfur)
o 1980s Diesel Fuel (0.18% Sulfur)
o ~1998 Low Sulfur Diesel Fuel (0.04% Sulfur)
o 2006 Ultra Low Sulfur Diesel Fuel (0.0015% or 15ppm)
▪ Dyes added to heating oil and aviation fuels over time (tax and safety reasons) can be useful.
Although the average lead concentration in gasoline has
changed with time, wide regional variations are documented
0
0.5
1
1.5
2
2.5
Le
ad
C
on
c g
ra
ms
p
er
g
allo
n
1920 1925 1930 1935 1940 1945 1950 1955 1960 1965 1970 1975 1980 1985 1990 1993
DATE
Gasoline Lead Content – Age Dating
Average Lead Content of the US Gasoline Supply Over Time
Note: Gasoline evaporation over time in the environment concentrates lead in the remaining fuel, and must be considered in age determinations.
Gasoline Additives – Age Dating
Chronology of Selected Gasoline Additives
Gasoline hydrocarbons with10+ carbon atoms
Mixed Alkyl Leads
Lead
1960 1965 1970 1975 1980 1985 1990 1995 2000
Year
>1.1 g/gal
<1.1 g/gal
<0.1 g/gal
> n-Propylbenzene = n-Propylbenzene
MtBE, western United States
Methyl tert-butyl ether (MtBE), eastern United States
Tetraethyl lead only
Ethylene dibromide and ethylene dichloride
Toluene/benzene ratio > 2.5 - 4
Manganese (MMT)
Lead Phase
Down
ETH
AN
OL
Gasoline additives provide a means to date gasoline
Note: Numerous other oxygenates have been used in gasoline (not shown), principally associated with 1990 Clean Air Act compliance.
Diagnostic Ratios – A Basic Example
Time, Water Contact or Microbial Degradation
n-C
17/P
rista
ne
Weathering IndicatorPristane and Phytane are
Isoprenoid Hydrocarbons that
elute adjacent to the C17 and C18
normal alkanes.
Isoprenoids are branched chain
unsaturated hydrocarbons
Isoprenoids are resistant to
weathering; normal alkanes
degrade more quickly.
As normal alkanes degrade over
time, Isoprenoids become more
dominant in the petroleum
mixture.
Note: This relationship is not recommended for precise age dating of releases without careful, site-specific calibration.
Normal Alkane / Isoprenoid Ratio
Weathering Trends and Source Identification
X
O
n-C17 /Pristane = High - Not Weathered
n-C17/Pristane = Low - Weathered
Break in
Weathering
Trend Indicates
New Source
Ongoing
Source
Other Diagnostic Biomarkers
▪ Biomarker presence and relative quantities
are unique to particular crude oils
▪ Some biomarkers are conserved in the
refining process
▪ Some biomarkers persist in the environment
making them useful in forensics
Crude Oil Biomarkers – Source Oil Indicator
The Biomarker TriterpaneThe Biomarker Hopane The Biomarker Sterane
Stable Carbon Isotope Ratios – Source Profile
-20
-25
-30
-35
-23.27
-25.66
-30.06
-29.52 -29.50
-23.45
-29.68
Monterey
Crude
Katalla Crude Cook Inlet
Crude
North Slope
Crude
Unknown
Source
Monterey
Source
NSC Source
Petroleum Source
d13C
Every Crude Oil Has a Diagnostic 13C/12C Ratio Depending on When/How it Formed
Hydrocarbon Molecules in Fuels Refined from the Crudes Tend to Retain Diagnostic 13C/12C Ratios
13C/12C Ratios Remain Generally Stable Even in Instances of Extreme Weathering
Note: δ13C expressed relative to the PDB reference standard
Stable Carbon Isotope Application
X
O
-29.60
-25.66
Source 1
Source 2
Impacted
Domestic
Well-29.52
Buried
Utility
Conclusion: δ13C Shows Source 1 is Impacting the Domestic Well
Methane Identification with Isotopes
▪ Methane can seep into structures or water wells
▪ Creates aesthetic problems and at high concentrations
(>5%) may be a safety concern
▪ A natural condition in many areas of the U.S.
▪ Often blamed on energy production or ”fracking”
Methane Identification with Isotopes
▪ Methane Isotope Analysis – Is energy production at fault?
o The chemical formula for Methane is CH4
o Carbon and Hydrogen in the Methane have isotopic signatures
▪14C is Radioactive with a Half Life of 5,730 Years
o Methane in gas reservoirs is millions of years old, so: Only
modern Methane has significant 14C
o If 14C is abundant, Methane is not from gas production
▪ Varying Amounts of 12C and 13C stable isotopes indicate
how the methane formed
o Thermogenic (gas reservoir) or Biogenic (organic decay)
Case History – Hospital Construction
▪ During construction of a new
hospital wing in New York City,
black sticky soil contamination
was encountered.
▪ The site’s 150-year-old history
included fuel storage, wood
preserving, steam ship fueling,
and manufactured
gas production.
▪ The developer was facing $1.2M in remedial cost.
▪ Historic site industries had successors with insurance.
▪ How to get responsible parties to pay?
Comparison of
an Unknown
Soil Sample
to a Gasoline
Standard
No Match – The gasoline
standard is much too
light. It contains none of
the heavier hydrocarbons
found in the site pail
sample.
Light
Heavy
Internal
Standard
Case History – GC/FID – Hospital Construction
Comparison of
an Unknown
Soil Sample to
a Fuel Oil #6
Standard
(Bunker Fuel)
No Match – The hydrocarbon
range is close, but the normal
alkane profiles are different.?
Internal
Standard
?
Case History – GC/FID – Hospital Construction
Comparison of
an Unknown
Soil Sample
to a Creosote
Standard
No Match - Light ends in
the field sample are
missing; the field sample
also extends into heavier
compounds than the
creosote standard – “tail”.
The normal alkane profile is
also different.
Internal
Standard
Heavy
Tail
Case History – GC/FID – Hospital Construction
Comparison of
an Unknown
Soil Sample to a
Coal Tar Standard
A Match – After accounting for
weathering
Letters help connect compound
peaks between chromatograms.
“a” is Naphthalene and relatively
weathered in the pail excavation
sample (Expected).
Note also the Unresolved
Complex Mixture (UCM) “Hump”
in the pail sample indicative of
weathering.
UCM
Case History – GC/FID – Hospital Construction
GC/MS With
Selected Ion
Monitoring
(SIM)
Parent and Alkylated
PAH Distribution
Histograms
Note the patterns of
substituted vs. parent
PAHs (Red Envelopes).
This is a classic Petrogenic
vs. Pyrogenic PAH pattern
comparison.
Case History – GC/MS (SIM) – Hospital Construction
Site Soil Samples and Various Hydrocarbon Standards are Shown
Fluoranthene/Pyrene vs. Dibenzofuran/Fluorine
Data Clusters Identify
Like Sources Mystery Solved–
The sample is a
Carbureted Water
Gas (CWG) coal tar.
Case History– PAH Source Ratio– Hospital Construction
Lab A
Lab BLab B
Case History – Chlorinated Solvents
▪ Chlorinated solvent releases from a large
filtration manufacturer
o Other sources suspected up-gradient
o Both sites used TCE and PCE
o Multiple aquifers with natural artesian/upward flow
▪ Forensics evaluation confirmed up-gradient source
impacting client’s property
o Highest total VOC concentration on client = 7,445ug/l
o Highest total VOC Concentration up-gradient = 47,900ug/l
o Contaminant flow in deeper aquifer not the shallow aquifer
o Local pumping of groundwater from production wells pulled
contamination down
▪ Conclusion: site should be remediated on a regional basis vs. site
basis
▪ Up-gradient property owner required to cooperate & remediate
Case History – Chlorinated Solvents
Client
Up-Gradient Source
Case History – Chlorinated Solvents
Client Property Up-Gradient Source
Case History – Beer Warehouse with Methane
▪ A beer warehouse is located
next to a Superfund Site.
▪ Extremely high concentrations
of Methane beneath the
warehouse floor
(Methane >50%, ~10x the LEL).
▪ A 6-foot thick oil plume from
Superfund Site was floating on water table beneath
the building.
▪ PRPs took responsibility for oil plume, but not for
Methane, stating it was naturally-occurring.
▪ Methane abatement estimated to cost >$1M.
▪ Isotope testing of the Methane determined its source.
Case History – Beer Warehouse with Methane
Diagram After: Isotech - Coleman, Liu, Hackley, and Pelphrey, 1995
Carbon-14 – Radioactive Carbon Testing
Only 11% of the carbon is modern, 89% is radiocarbon “dead.”
Case History – Beer Warehouse with Methane
Diagram After: Isotech - Coleman, Liu, Hackley, and Pelphrey, 1995
Stable Isotope Plot
Stable isotopes show the site methane was produced by the near- surface microbial fermentation pathway.
Stable Carbon Isotope Domains for Common Sources of Methane
Sub-Surface Microbial Gas via CO2 Reduction. Found in Glacial Drift Deposits.
Shallow Microbial Gas Typical of Swamp Gas or Landfill Gas.
Gas from Energy Reservoirs.
Technical / Legal Interaction to Win
▪ Lawyers: “Involve your technical expert EARLY”
▪ Scientists: “Understand and CONTRIBUTE to the legal
case strategy”
▪ Develop sampling plans to close data gaps
oPoorly constructed field sampling misses critical info.
oNot all data are forensics quality – QA/QC critical
oCollection of unnecessary “new” data may be risky
▪ Prepare for challenge – play “devil’s advocate”
▪ Tell a technically correct story at the 3rd grade level
▪ Appeal to common sense of judge and jury
o “Like water, contamination flows downhill.”
▪ Use Visuals and memorable sound bites for key points
o “If the Glove Doesn’t Fit, You Must Acquit.”
Wrap-Up – The Need for Good Data
Groundwater
Flow
Gas Station Known Leaks and
Contaminated Wells
Neighborhood with
Contaminated Wells
?
Historic Bulk Plant – No
Known Leaks, No
Wells
?
• Data Trends?
• Other Sources?
• Spatial Relationships?
• Migration Dynamics?
• Flow Divides?
