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A Forensic Approach to Evaluation of Co-mingled Aircraft
Deicing Fluids and Jet Fuel
Eric M. Cherry,
Hull & Associates, Inc.
Heidi Pruess, Cleveland Hopkins International Airport
Loretta Snider, Hull & Associates, Inc.
Kevin C. Valentine,
Parsons Corp.
Surface
Water Sheen Source Investigation at a Petroleum Product
Terminal
Julie
K. Sueker, Blasland, Bouck & Lee, Inc
Caron Koll, Blasland, Bouck & Lee, Inc.
Rebecca Countway, Blasland, Bouck & Lee, Inc.
Pat Hughes, ChevronTexaco Energy Research and Technology
Company
Peter L. Kasbohm, ChevronTexaco Products Company
Helder Costa, Blasland, Bouck & Lee, Inc.
Bill McCune, Blasland, Bouck & Lee, Inc.
Forensic
Electronic File Review
David
R. Blye, Environmental Standards, Inc.
Rock J. Vitale, Environmental Standards, Inc.
Ruth L. Forman, Environmental Standards, Inc.
Distinguishing
PAH Background and MGP Residues in a Freshwater Creek
Helder J. Costa, Blasland, Bouck & Lee, Inc.
Keith A. White, Blasland, Bouck & Lee, Inc.
John J. Ruspantini, New York State Electric & Gas
New
Bedford Harbor Data Interpretation
John F. Ehret, PG., Tetra Tech FW, Inc., Boston, MA
Ronald J. Marnicio, Tetra Tech FW, Inc., Boston, MA
Douglas K. Stout, Foster Wheeler Inc., Clinton, NJ
Diamondoid
Hydrocarbons – Application in the Chemical
Fingerprinting of Gas Condensate and Gasoline
Scott
A. Stout, Edward M. Healey, and Gregory S. Douglas,
Battelle Memorial Institute
Chemical
Characterization of Potential Pyrogenic Sources
Shan-Tan
Lu, ZymaX Forensics
Robert I. Haddad, ZymaX Forensics
Issac R. Kaplan, ZymaX Forensics
A
Forensic Approach to Evaluation of Co-mingled Aircraft
Deicing Fluids and Jet Fuel
Eric
M. Cherry, Senior Project Manager, Hull & Associates,
Inc., 6397 Emerald Parkway, Dublin, Ohio 43016, Tel:
614-793-8777, Email:
echerry@hullinc.com
Heidi Pruess,
Environmental Manager, City of Cleveland, Department of
Port Control, Cleveland Hopkins International Airport,
19501 Five Points Road, Cleveland, OH 44135, Tel:
216-898-5126
, Email: hpruess@clevelandairport.com
Loretta Snider, P.E. Project Manager, Hull &
Associates, Inc., 6161 Cochran Road, Solon, Ohio 44139 Tel: 440-519-2555, Email:
lsnider@hullinc.com
Kevin C. Valentine, PG, CHMM, Parsons Corp., 19101
Villaview Rd., Cleveland, Ohio 44119
Tel:
216-486-9005, Email: Kevin.Valentine@parsons.com
Long-term use of aircraft and pavement deicing fluids
and intermittent releases of jet fuel can impact
subsurface soil and water at airport facilities.
Parent compounds in these mixtures can degrade
rapidly to daughter compounds that are not typically
included on standard USEPA analyte lists, potentially
resulting in false negative results when trying to
identify areas of soil or water contamination and
evaluating ecological and human health risk. Identification of these compounds can, even when present in
concentrations below risk levels, present operational or
nuisance problems to potential receptors if impacted areas
are exposed to ambient conditions.
Therefore, a forensic approach must be developed to
identify the daughter compounds and subsequently evaluate
potential risks and nuisance for operations and
construction planning.
Soil,
water and air samples were collected from potentially
impacted areas at a municipal airport, with subsequent
analysis for VOCs, SVOCs, ammonia, aldehydes, glycols, and
sulfur compounds. Analyses were conducted using USEPA or ASTM methods with
tentatively identified compounds (TICs).
A total of 164 different compounds were detected in
one or more of the sample media.
Chemical constituents from the source materials
(deicing fluids and jet fuel) tended to be present in
relatively low concentrations; however, a wide range of
daughter products were detected.
A comparison of chemical concentrations to
promulgated standards or risk-based target concentrations
suggests that the greater proportion of allocation of risk
is due to non-target list daughter compounds relative to
the parent compounds evaluated by the standard target list
approach. The
forensic evaluation of the distribution of constituents
can be used to estimate the relative contribution of
various parent products to the final mixture of chemicals
identified in impacted areas.
The
findings of this assessment have broad implications for
identifying appropriate chemicals of concern for settings
where deicing fluids and/or jet fuel may be present, such
as civil or military aviation facilities.
Surface
Water Sheen Source Investigation at a Petroleum Product
Terminal
Julie
K. Sueker, Blasland, Bouck & Lee, Inc., 14142 Denver
West Parkway, Suite 350, Denver, CO, 80401
Tel:
303-231-9115, Fax: 303-231-9571
Caron Koll, Blasland, Bouck & Lee, Inc., 6723
Towpath Road, Syracuse, NY, 13214-0056, Tel: 315-446-2570
, Fax: 315-446-8053
Rebecca Countway, Blasland, Bouck & Lee,
Inc., 301 East Ocean Blvd, Suite 1530, Long Beach, CA,
90802
, Tel: 562-628-1176, Fax: 562-628-1196
Pat Hughes, ChevronTexaco Energy Research and Technology
Company, 100 Chevron Way, Richmond, CA, 94802, Tel:
510-242-5952, Fax: 510-242-1380
Peter L. Kasbohm, ChevronTexaco Products Company, 2300
Windy Ridge Parkway, Suite 800S, Atlanta, GA 30339, Tel:
770-984-3145, Fax: 770-984-4107
Helder Costa, Blasland, Bouck & Lee, Inc.,
174 Union Street, Suite 300, New Bedford, MA, 02740
, Tel: 508-992-3609, Fax: 508-997-5520
Bill McCune, Blasland, Bouck & Lee, Inc., 6723 Towpath
Road, Syracuse, NY, 13214, Tel: 315-446-2570, Fax: 315-446-8053
An investigation was undertaken to identify the
source of a sheen that emanates at low tide from a
petroleum product terminal bulkhead into a
tidally-influenced river.
The presence of sheens drives regulatory cleanup
requirements at the site, thus sheen source identification
is required to target appropriate remedial action.
Forensic profiling techniques (fingerprinting)
employed in this investigation include molecular and
isotopic composition analyses and fuel fluorescence
detection (FFD) soil screening.
Product (NAPL) samples were collected from a
monitoring well approximately 200 feet upgradient from the
bulkhead and an oil-water separator located further
inland. NAPL
samples exhibited carbon ranges from C5 through
C28 and appeared to be a mixture of gasoline
and middle distillate hydrocarbons such as diesel/fuel oil
#2. Soil samples were collected at several locations and depths
between the monitoring well and the bulkhead.
C8 to C23 carbon ranges were
identified for petroleum hydrocarbons in the soils.
Middle distillate range hydrocarbons were present
in all samples (expect one sample with low TPH
concentration) with some samples containing gasoline range
hydrocarbons. Molecular
and bulk hydrogen isotopic composition data indicated that
samples were progressively more weathered towards the
bulkhead. Alkylated
PAH data indicated the presence of at least two middle
distillate hydrocarbons sources.
Sheen samples were collected from the river during
low tide. Sheens
featured an unresolved complex mixture in the C15
to C28 range.
Although this carbon range overlapped with that of
the NAPL samples, the absence of lighter hydrocarbons in
the sheen and the absence of heavier hydrocarbons in the
soils suggested that upgradient NAPL and residual
petroleum hydrocarbons in sampled soils are not sheen
sources. Compound-specific
carbon isotopic analyses of select NAPL, soil, and sheen
samples are currently underway to provide further
characterization of potential source materials and sheen.
Collection of soil samples from within five feet of
the bulkhead was not practical due to suspected structural
instability of the bulkhead.
Sheen generating materials may be limited to
near-bulkhead soils.
Forensic
Electronic File Review
David
R. Blye, B.S., CEAC, Environmental Standards, Inc., 1140
Valley Forge Road, Valley Forge, PA 19482, Email: DBlye@EnvStd.com
Rock J. Vitale, B.S., CEAC, CPC, Environmental Standards,
Inc., 1140 Valley Forge Road, Valley Forge, PA 19482,
Email: RVitale@EnvStd.com
Ruth L. Forman, B.S. CEAC, Environmental Standards, Inc.,
1140 Valley Forge Road, Valley Forge, PA 19482, Email:
RForman@EnvStd.com
Data
users have historically assumed that laboratory-reported
results are absolute, accurate, and reliable.
This assumption has proven time and time again to
be a costly mistake.
Although data validation (and to a lesser extent
data verification) can determine if an analysis conforms
to client, method, and regulatory agency specification and
if the results are usable for their intended purpose, data
validation is dependent upon the hard copy data package
provided.
Laboratories use software to process electronic
data output from instrumentation
and to prepare hard copy data packages.
If a laboratory has manipulated its electronic data
files so that the data conform to client, method, and
agency specifications prior to the laboratory’s
preparation of the hard copy data package utilized for
data validation, the data validator would have no way of
knowing that electronic data manipulation had occurred.
A
forensic review of processed data files advances data
validation past paper auditing.
This electronic file review allows the auditor to
assess issues such as the integrity of manual
integrations, qualitative identification, accuracy of
results and presence and identification of non-target
compounds. Using
the same software as
that used by the laboratory allows data reviewers to take
the laboratory’s original organic electronic data files,
to reprocess these data files, and to compare the
laboratory’s final result records to those records that
the data reviewed reprocessed.
Thus, an independent reviewer can determine if the
electronic data files have been manipulated or altered.
Examples of how examination of organic electronic
data files can benefit data review will be presented.
Distinguishing
PAH Background and MGP Residues in a Freshwater Creek
Helder J. Costa, Blasland,
Bouck & Lee, Inc., 174 Union St., Suite 300, New
Bedford, MA 02740, Tel:
508-992-3609, Fax: 508-997-5520
Keith A. White, Blasland, Bouck & Lee, Inc., 6723
Towpath Rd., P.O. Box 66, Syracuse, NY 13214
, Tel:
315-446-2570, Fax: 315-446-8053
John J.
Ruspantini, New York State Electric & Gas, Corporate
Drive, Kirkwood Industrial Park, P.O. Box 5224,
Binghamton, NY 13902-5224, Tel:
607-762-8787, Fax: 607-762-8451
Polycyclic
aromatic hydrocarbons (PAHs) are ubiquitous in the
environment from a variety of sources: atmospheric soot
residues from burning petroleum/wood/coal, surface runoff,
urban/industrial outfalls, petroleum uses and releases,
and others. In
aquatic environments, sediments are a primary sink for
hydrophobic compounds, such as PAHs.
PAHs also constitute the predominant hydrocarbon
fraction in MGP by product tars.
Due to the proximity of many former MGP sites to
streams, delineating the extent of PAHs in sediments is a
common component of many MGP remedial investigations.
Because of the compositional similarity of
weathered/degraded MGP residues to background PAHs, it is
often difficult to accurately determine the local PAH
background in sediments in aquatic systems near former MGP
sites. In the
context of a remedial investigation, uncontrolled
background sources constitute a potential for
post-remedial recontamination, limiting the feasibility of
some remedial options.
A case study is presented for a creek flowing
adjacent to a former MGP where an elevated PAH background
was observed upstream of any suspected releases.
Relatively simple interpretative techniques were
applied to PAH delineation data generated using
conventional analytical methods.
The preliminary evaluation identified two
potentially distinct PAH signatures, representing
site-related sources and local PAH background.
PAH fingerprinting was performed on selected
samples to confirm source identifications and refine the
conceptual site model.
Data will be presented illustrating a phased
approach to distinguishing site-related and local
background PAHs, and the implications for sediment
remediation.
New
Bedford Harbor Data Interpretation
John F. Ehret, PG, Tetra
Tech FW, Inc., 133 Federal Street, 6th Floor,
Boston, MA 02110, Tel: 617-457-8205, Email:
jehret@ttfwi.com
Ronald J. Marnicio, Ph.D., PE, Tetra Tech FW, Inc., 133
Federal Street, 6th Floor, Boston, MA 02110,
Tel: 617-457-8262, Email: rmarnicio@ttfwi.com
Douglas K. Stout, Foster Wheeler Inc., Perryville I –
Law Department, Perryville Corporate Park, Service Road
173, Clinton, NJ 08809, Tel: 908-730-4104, Email: dstout@ttfwi.com
Electric capacitor plants
released PCBs into New Bedford Harbor from the 1940s to
the 1970s. Sediment
PCB characterization data was collected and analyzed by
geostatistically modeling portions of the harbor to define
the horizontal extent and removal depths required to
achieve compliance with the mandated clean-up goals. The
results of this data interpretation are currently being
used to specify the dredging or excavation design for the
removal of over 500,000 cubic yards of contaminated
sediments.
Each sediment sampling
location was classified on the basis of the pattern of PCB
concentrations measured throughout the sediment column
with depth. Systematic rules for assigning a projected
compliance depth (referred to as Z*) for each
characteristic pattern of sample results in the sediment
column were defined in consideration of the sampling
protocols used, sediment type and stratigraphy, field
information, and other site knowledge. The projected
compliance depths for each location were compiled,
documented, and used as input to the geostatistical
modeling effort.
Geostatistical modeling was
used to predict compliance depths between sample
locations, drawing on spatial correlations observed in the
data set. The
input compliance depth data were evaluated using a suite
of statistical diagnostic techniques to establish the
parameters needed to perform the detailed 2-dimensional
spatial modeling of the depth of sediment removal required
to achieve compliance.
The Harbor was modeled as six separate domains,
which were defined based on topography, hydrology, and
patterns of PCB concentration levels. Final Z* projections
were developed for each domain, along with corresponding
estimates of the precision associated with these results.
This allowed data users to assess the confidence of
the results for any area of the harbor and to determine
where additional sampling may be necessary. The results
have been used to guide dredging design, estimate removal
volumes, and aid in restoration planning.
Diamondoid
Hydrocarbons – Application in the Chemical
Fingerprinting of Gas Condensate and Gasoline
Scott
A. Stout, Edward M. Healey, and Gregory S. Douglas,
Battelle Memorial Institute, 397 Washington St., Duxbury,
MA 02332,
Tel: 781-934-0571, Fax: 781-934-2124
Detailed
chemical fingerprinting of lower boiling petroleum liquids
(e.g., natural gas condensates), intermediate petroleum
distillates (e.g., naphthas or straight run gasolines),
and finished petroleum products (e.g., automotive
gasoline) is a common need in environmental forensic
investigations. Commonly
employed fingerprinting techniques rely upon the detailed
analysis of hydrocarbons and non-hydrocarbons, including
gasoline additives, using purge-and-trap or direct
injection gas chromatographic/mass spectrometric (GC/MS)
methods.
The hydrocarbon classes commonly targeted in these
analyses include the so-called “PIANO” groups, an
acronym for paraffins, iso-paraffins, aromatics,
naphthenes, and olefins.
The naphthenes are cyclic aliphatic compounds that
occur naturally in petroleum.
Heretofore, chemical fingerprinting of the
naphthenes in lower boiling petroleum has utilized
numerous single-ring compounds, viz., cyclopentanes
and cyclohexanes.
In this paper, a class of multi-ring naphthenes in
lower boiling petroleum known as diamondoids is
described and the potential application of these compounds
in the chemical fingerprinting of lower boiling petroleum
is demonstrated.
Diamondoids
are a class of saturated hydrocarbons that consist of
three or more fused cyclohexane rings, which results a
‘cage-like’ structure.
The diamondoids that can be found in light
petroleum liquids (e.g., natural gas condensates),
intermediate petroleum distillates (e.g., naphthas), and
finished petroleum products (e.g., automotive gasoline)
include adamantane (B.P. ~190oC) and diamantane
(B.P. ~272oC) and their various substituted
equivalents. These
naturally occurring compounds are thermodynamically stable
and extremely resistant to weathering.
As such, their distribution and relative abundance
in environmental samples can be useful in the chemical
fingerprinting of light petroleum and gasoline.
In this study, the chromatographic and mass
spectral characteristics of diamondoids in various
petroleum products are demonstrated.
Shan-Tan
Lu, Ph.D., ZymaX Forensics, 71 Zaca Ln., San Luis Obispo,
CA 93401, Tel: 805-544-4696, Fax:805-544-8226, Email:
shantan@zymaxusa.com
Robert I. Haddad, Ph.D., ZymaX Forensics, 71 Zaca Ln., San
Luis Obispo, CA 93401, Tel: 805-544-4696,
Fax:805-544-8226, Email: rhaddad@charter.net
Issac R. Kaplan, Ph.D., ZymaX Forensics, 71 Zaca Ln., San
Luis Obispo, CA 93401, Tel: 805-544-4696,
Fax:805-544-8226, Email: irk@zymaxusa.com
Chemical
analyses of polycyclic aromatic hydrocarbons (PAHs) can be
used to differentiate between pyrogenic and petrogenic
sources in environmental media.
Based on the relative stability of non-alkylated
(or parent) PAHs associated with hydrocarbon mixtures
derived from high temperature reactions.
It is increasingly desirable not only to
differentiate between pyrogenic and petrogenic sources,
but also between different types of pyrogenic sources.
In this study, chemical characterization of
petroleum and coal-derived lampblack and coal oil tar was
investigated and compared.
Additionally, petroleum cokes (green and calcined)
were analyzed to assess the potential for these high
temperature products for providing
chemical signatures commonly associated with
pyrogenic sources. The
samples were analyzed using GC/MS both in the full scan
and single ion monitoring modes. Results show that the hydrocarbon compositions of the cokes
differ substantially from the coal tar and the lampblack
samples. Specifically,
the alkylated PAH distribution measured on the coke
samples do not show the common parent-dominance often
associated with pyrogenic sources measured in the coal tar
and coal-derived lampblack samples.
Differences were also noted in the chemical
compositions of the two coke samples, with the green coke
having a higher relative abundance of aromatic compounds
relative to the calcined coke.
Finally, comparison of the two lampblack samples,
showed substantial differences in the PAH and aromatic and
saturate biomarker composition.
These data provide new insights on the application
of PAH chemistry to forensic source identification and
ultimately liability allocation at environmental sites.
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