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NAPL Source Chasing – A Forensics Evaluation
Frank
Ricciardi, Weston & Sampson Engineers, Inc., Peabody,
MA
Kelley Race, Weston & Sampson Engineers, Inc.,
Peabody, MA
Using
Isoprenoid Hydrocarbon Ratios to Calculate Percentage
Mixing Different Distillate Fuels in the Subsurface
Environment
Michael J. Wade, Wade Research, Inc., Marshfield, MA
Combining
Passive Soil Gas Sampling, GC/MS Analysis, and
Non-Conventional Interpretation to Identify Fuel Sources
Joseph
Wilson, URS Corporation, Morrisville, NC
James E. Whetzel, W. L. Gore and Associates, Elkton,
MD
Wayne W. Wells, W. L. Gore and Associates, Elkton, MD
Fingerprinting
Dioxin-Furan Contamination in the Lower Roanoke River
Basin
Russell
H. Plumb Jr., Lockheed Martin, Las Vegas, NV
Beth Walden, U.S. EPA Region 4, Atlanta, GA
Applications
of Forensic Chemistry for Contaminant Identification In
Sediments Near an MGP Site, Wisconsin
Diane
L. Saber, Gas Technology Institute, Des Plaines, IL
David Mauro, META Environmental, Inc., Watertown,
The
Application of the Federal On Road Diesel Fuel Sulfur
Reduction Act of 1993 to the Age Dating of Diesel Fuels:
A Case Study
Gregory
S. Douglas, NewFields Environmental Forensics Practice,
Rockland, MA
Scott Ziegler, Atlantic Richfield Company, Austintown, OH
Charles Pinzone, BP America Inc., Cleveland, OH
Jeff Hardenstine, NewFields Environmental Forensics
Practice, Rockland, MA
Kevin McCarthy, NewFields Environmental Forensics
Practice, Rockland, MA
NAPL Source Chasing – A Forensics Evaluation
Frank
Ricciardi, P.E.,
Weston & Sampson Engineers, Inc. 5 Centennial
Drive, Peabody, MA 01906, Tel: 978-532-1900, Fax:
978-977-0100, Email: ricciarf@wseinc.com
Kelley Race, P.G., LSP, Weston & Sampson Engineers,
Inc. 5 Centennial Drive, Peabody, MA 01906, Tel:
978-532-1900, Fax: 978-977-0100, Email: racek@wseinc.com
During
a routine site investigation, greater than ½ inch of
light non-aqueous phase liquid (LNAPL) was detected in a
site monitoring well. Investigation activities were
implemented to evaluate the source of free-phase petroleum
product in the subsurface beneath a maintenance bay of a
bus maintenance garage. Product samples were submitted for
petroleum fingerprint analysis (modified EPA method 8015B)
to compare product detected in the monitoring well to
waste oil from a historic overfill of an underground
storage tank located nearby. The analytical results of the
LNAPL samples contained different petroleum constituents
and LNAPL sources may have commingled.
The
subsurface investigation and forensic activities utilized
to evaluate the source and extent of petroleum in the
subsurface included:
·
Abandoning
the monitoring well and excavating the soil around the
well to observe if well drilling activities breached the
floor drain system
·
Dye
testing and water flushing the floor drain system and
assessing the excavation area and nearby monitoring wells
for the presence of dye/water
·
Evaluating
the floor drainage system within the maintenance bays
including piping materials, drainage plans, and integrity
·
Advancement
of monitoring wells surrounding the well containing
product
·
Evaluation
of groundwater flow direction to observe downgradient
wells for LNAPL
·
Evaluating
oil/water separator connections associated with the garage
and
·
Confirmatory
soil sampling from the sidewall and bottom of the
excavation area associated with the well containing LNAPL
·
Delineation
of LNAPL extent
The
results of the site investigation activities and floor
drain system assessments revealed that the LNAPL areas had
not commingled, the floor drain was not breached and
excavation activities had removed the extent of LNAPL
associated with the release.
Using
Isoprenoid Hydrocarbon Ratios to Calculate Percentage
Mixing Different Distillate Fuels in the Subsurface
Environment
Michael
J. Wade, Wade Research, Inc. 110 Holly Road, Marshfield,
MA 02105-1724
Subsurface
mixing of a Jet A fuel/kerosene component with a No. 2
fuel oil/diesel fuel component presents a particular
problem for the environmental forensics community.
Determining the percent contribution of a lighter
distillate fuel component such as Jet A/kerosene mixed
with a heavier distillate fuel component such as No. 2
fuel oil/diesel fuel can be important in apportioning
recovery costs and cleanup among different potentially
responsible parties. The fact that different types of
distillate fuels are deliberately formulated to have
different physical parameters can prove useful in the
determining percent contributions to subsurface plumes
using chemical data from gas chromatographic analyses. Gas
chromatographic analysis of subsurface aqueous phase
liquid (NAPL) samples collected from a series of
groundwater monitoring wells at a large fuels storage
facility revealed a chronic leak of a jet fuel tank into a
surrounding plume of No. 2 fuel oil/diesel fuel. Initial
chemical analysis revealed complicated chromatograms.
However, numerical analysis of the chromatographic data
resulted in a clear picture of mixing of different
distillate fuels in the immediate vicinity of a jet fuel
storage tank. Percent contributions of jet fuel were
calculated for each monitoring well, showing a clear trend
toward a jet fuel composition the closer the monitoring
well was to the jet fuel storage tank. Percent
calculations were facilitated by taking advantage of the
inherent differences in the early to later isoprenoid
hydrocarbon in different fuel types. A two end-member
mixing model was developed that allowed the percent
calculation of both distillate fuel end members regardless
of the extent of environmental weathering of each separate
distillate fuel. The mixing model can be applied to any
mixed component plume to calculate amounts of different
distillate fuels present in a combined subsurface plume.
Combining
Passive Soil Gas Sampling, GC/MS Analysis, and
Non-Conventional Interpretation to Identify Fuel Sources
Joseph
Wilson, URS Corporation, 1600 Perimeter Park Drive,
Morrisville, NC 27560, Tel: 919-461-1288, Fax:
919-461-1415, Email: joseph_wilson@urscorp.com
James E. Whetzel, W. L. Gore and Associates, 100
Chesapeake Blvd, Elkton, MD 21922, Tel: 410-506-4779, Fax:
410-506-4780, Email: jwhetzel@wlgore.com
Wayne W. Wells, W. L. Gore and Associates, 100 Chesapeake
Blvd, Elkton, MD 21922, Tel: 410-506-4778, Fax:
410-506-4780, Email: wwells@wlgore.com
Passive
soil gas technology is proven to be a useful tool for
identifying source areas and the extent of soil and/or
ground water impact following fuel releases. Property
owners facing the prospect of expensive cleanup operations
do not want to be responsible for contamination from
offsite sources. Due to inherent biases in soil gas toward
the more volatile components, linking observed
contamination with the actual fuel source(s) is difficult
to begin with, and becomes more complex when multiple fuel
types are present. A non-conventional interpretation of
soil gas data, collected with the GORE™ Module, was able
to yield significant information regarding the actual
source determination for fuel releases at a facility in
the southeastern US. This presentation will discuss how
the soil gas data, fuel samples, and GC/MS analysis were
used to link the signal observed in the passive soil gas
survey to the fuel sources, when conventional soil gas
data interpretation did not accomplish this goal
adequately.
Fingerprinting
Dioxin-Furan Contamination in the Lower Roanoke River
Basin
Russell
H. Plumb Jr., Ph. D., Lockheed Martin, 1994 Abarth Street,
Las Vegas, NV, 89142, Tel:
702-431-9608, Email: COGIT8R@aol.com
Beth Walden, Remedial Project Manager, U.S. EPA Region 4,
Atlanta Federal Center, 61 Forsyth Street, Atlanta, GA
30303-3104, Tel: 404-562-8814, Fax: 404-562-8787,
Email: walden.beth@epa.gov
Previous
investigations of sediments and wetland soils in the lower
Roanoke River Basin reported measurable dioxin-furan
concentrations in the range of 5,000 to 12,000 ng/kg.
Using the FALCON fingerprinting process (Fingerprint
Analysis of Leachate CONtaminants), it was possible to
identify two distinctive dioxin-furan fingerprint patterns
based on graphical pattern recognition and regression
analysis. One pattern, associated with a pulp and paper
mill facility, was characterized by a major peak for
2378-TCDF and progressively smaller peaks for
1234678-HpCDF, OCDF, 2378-TCDD, and 1234678-HpCDF. This
pattern had an estimated reproducibility of 90 percent. A
second pattern associated with sources up river from the
pulp and paper mill was characterized by a dominant peak
for 1234678-HpCDD, and smaller peaks for OCDF and
1234789-HpCDF. This fingerprint had an estimated
reproducibility of 99 percent.
The
two identified fingerprints were used to characterize the
dioxin-furan contamination of the lower Roanoke basin in a
two step process. The first step consisted of calculating
dioxin-furan fingerprints for various binary mixtures of
the two source patterns. The second step consisted of
statistically comparing the actual dioxin-furan
distribution in down river sediments with the calculated
fingerprint patterns. This assessment indicated that 35 to
40 percent of the down river dioxin contamination could be
attributed to the pulp and paper mill and the remainder
was due to up river source(s). However, because the pulp
and paper mill dioxin had a relative toxicity that is more
than five times greater than the up river source(s), it
represents 75 to 79 percent of the dioxin TEQ risk in the
lower river basin.
Applications
of Forensic Chemistry for Contaminant Identification In
Sediments Near an MGP Site, Wisconsin
Diane
L. Saber, Ph.D, Gas Technology Institute, 1700 Mount
Prospect Road, Des Plaines, IL
60018, Tel: 847-768-0538, Fax: 847-768-0546, Email:
diane.saber@gastechnology.org
David Mauro, META Environmental, Inc., 49 Clarendon
Street, Watertown, MA
02472, Tel: 617-923-4662, Fax: 617-923-4610, Email:
dmauro@metaenv.com
A
survey of Duluth-Superior harbor materials identified the
presence of concentrations of PAHs in the sediments. The
Wisconsin Department of Natural Resources (WDNR) assumed
that the source of the PAHs was a nearby former
manufactured gas plant (MGP) site.
Forensic chemistry, both “chemical
fingerprinting” (GC/MS) and “isotopic
fingerprinting” (GC/IRMS) was conducted on sediment and
former MGP soil samples, in order to determine the origin
of the contamination.
Environmental forensic chemistry involves specific
analytical testing in order to decipher the exact mixture
of organics and, in some instances, determine their age,
fate in the environment and source(s).
These analytical techniques have been increasingly
applied to the analysis of former MGP site wastes,
particularly tars, for comparison to low-level
concentrations of PAHs present in “urban background”
samples from the surrounding vicinity, including
sediments. Analysis
of samples using forensic chemistry techniques generates
unique “fingerprints” of the sample, depending upon
the method used. The
fingerprints may then be compared; in order to identify
the source of the waste. Locations impacted with tar
materials from a variety of sources are problematic in
legal disputes for ownership or liability for cleanup. This is particularly relevant in cases involving
contamination resulting from typical urban activities
(“urban background” wastes). Low-level urban
background contamination can be often misinterpreted as
MGP waste. Using
a new technique of compound-specific, isotope ratio (CSIR)
analysis, urban background concentrations may be discerned
from specific source material.
This is highly useful in the identification of
wastes in sediments. In this study, soil samples from the
former MGP site, sediment samples from the boat slip and
storm sewer samples were subjected to forensic analysis.
The fingerprinting results were used to determine if PAH
in the boat slip was derived from the known MPG or from
other sources.
The
Application of the Federal On Road Diesel Fuel Sulfur
Reduction Act of 1993 to the Age Dating of Diesel Fuels:
A Case Study
Gregory
S. Douglas, Ph.D., NewFields Environmental Forensics
Practice, 100 Ledgewood Place, Rockland, MA 02370, Tel:
781-681-5040
Scott Ziegler, Atlantic Richfield Company, An Affiliate of
BP Products North America, Inc., 633 Wyndclift
Circle, Austintown, Ohio 44515, Tel: 330-792-9484
Charles Pinzone, BP America Inc., 4850 East 49th
Street, MBC3, Cleveland, OH
44125
Jeff Hardenstine, NewFields Environmental Forensics
Practice, 100 Ledgewood Place, Rockland, MA 02370, Tel:
781-681-5040
Kevin McCarthy, NewFields Environmental Forensics
Practice, 100 Ledgewood Place, Rockland, MA 02370, Tel:
781-681-5040
Accurately
determining the age of environmental contamination is an
inherently difficult process due to the number of critical
variables that are often undefined at a site (e.g.,
degradation rates). For
example some age dating methods rely on the relative
degradation of two hydrocarbons (e.g., n-C17/pristane) compared to a linear degradation
pathway/rate to estimate time of release. These methods
are often oversimplified or depend upon assumptions about
preexisting site-specific conditions and as a result they
are frequently challenged.
The
defensibility of NAPL age-dating approaches increases
dramatically when concentrations of product additives
(e.g., tetraethyl lead or MTBE) or naturally occurring
compounds within the products (e.g., sulfur) are regulated
by federal or state environmental protection agencies.
In some cases, the regulations provided a broad
transition period for the petroleum industry to retool its
operations in order to achieve the desired results (e.g.,
removal of tetraethyl lead from gasoline).
However, in other cases, order of magnitude
reductions in fuel components were legislated with well
defined dates. These
large changes in product composition, combined with strict
monitoring and enforcement by federal and state agencies,
provide the forensic chemist a scientifically defensible
approach for product age-dating investigations.
This
work discuses the application of the Federal On-Road
Diesel Fuel Sulfur Reduction Act of October 1, 1993 to the
age dating of diesel fuel at retail sites.
A case study will be presented that combines
traditional GC/MS and GC/FID fingerprinting tools with
total sulfur data to conclusively differentiate a recent
release of diesel fuel at a large highway fuel dispensing
site from a prior release of diesel fuel at the same
facility. This data was then used to conclusively identify
the principal responsible party for the recent release. A novel approach to estimating product total sulfur content
in soils and sheens using dibenzothiophene/phenanthrene
ratios will also be discussed.
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