Environmental Forensics (2000) 1, 310

doi:10.1006/enfo.1998.0002, available online at http://www.idealibrary.com on

Soil Gas Methane at Petroleum Contaminated Sites: Forensic

Determination of Origin and Source
Paul D. Lundegard*, Robert E. Sweeney and G. Todd Ririe
Unocal Corporation, 376 S. Valencia Avenue, Brea, California 92823, U.S.A.

(Received 24 August 1998, revised manuscript accepted 6 November 1998)

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a signicant
health and safety risk. While petroleum products do not contain a signicant amount of methane (CH4), high CH4
contents in soil gas near petroleum spills have been reported. While CH4 is nontoxic, its accumulation in shallow soil gas
represents a potential explosion and asphyxiation hazard, especially in conned spaces. Identifying the source and
origin of shallow CH4 accumulations is an important part of evaluating potential exposure pathways, selecting
appropriate remedial measures, and determining environmental liability. This paper discusses the potential nature and
anthropogenic sources for shallow CH4 and how integration of geological, geochemical, and land use data can be used
to determine its origin and identify its source. Two case studies are presented, one where CH4 associated with a gasoline
spill is shown to be derived from a natural source rather than the gasoline, and a second where CH4 associated with
spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil. # 2000 AEHS

Introduction Naturally occurring CH4 can be classied, based on the

Methane (CH4) is a colorless, odorless gas, and the
simplest of all hydrocarbon molecules. In the Earth's
atmosphere CH4 is ubiquitously present at approxi-
mately 2 parts per million by volume ( ppmv) and is of
considerable environmental concern because it is a
greenhouse gas and is increasing in concentration
(Khalil and Rasmussen, 1990). Even though CH4 is
nontoxic, its presence in soil gas creates environmental
concern because it can act as an asphyxiant and is an
explosion hazard when present at between 5 and 15
volume percent concentration in air. Recognizing the
potential hazards associated with near-surface CH4 ,
some municipalities have even included assessment and
mitigation procedures in their building codes (City of
Los Angeles, 1996). Determining the source and origin
of CH4 associated with a petroleum spill is important
in the determination of environmental liability, and to
the selection of appropriate mitigation measures
because naturally occurring CH4 cannot be eliminated
by cleanup of the petroleum.
While petroleum products seldom contain signicant
amounts of CH4 , anecdotal accounts of high CH4
content in soil gas near petroleum spills are common.
In addition, several well documented soil gas studies
have shown elevated concentrations of carbon dioxide
(CO2) and CH4 in association with subsurface hydro-
carbon contamination (Marrin, 1987, 1991; Kerfoot
et al., 1988; Robbins et al., 1990; Deyo, Robbins and
Binkhorst, 1993; Ririe and Sweeney, 1995). In some
investigations, CO2 and CH4 concentrations have been
shown to correlate with the distribution of soil
contamination, for both volatile and semi-volatile
hydrocarbons (Marrin, 1987, 1989, 1991).
Methane in the environment can have a variety of
sources and origins (Schoell, 1988; Kaplan, 1994).
* Author for correspondence: E-mail: pdlundeg@unocal.com
3
1527-5922/00/010003+08 $35.00/00
predominant process by which it formed, as either
thermogenic ( produced by abiotic processes) or
biogenic ( produced by biological processes). Thermo-
genic CH4 is produced at depth within sedimentary
basins by the thermal degradation of organic matter,
and is commonly associated with coal and accumu-
lations of oil and natural gas. Thermogenic CH4 , while
typically generated at depths of several thousand feet
within sedimentary basins, commonly migrates upward
to escape to the land surface or accumulate in shallow
geologic structures bounded by low-permeability
strata. Biogenic CH4 is produced under anaerobic,
near-surface conditions by microbial degradation of
organic matter. Such microbially-produced CH4 occurs
widely in association with organic-rich sediments and
materials, including marine, lake, and river sediments;
marshes and swamps; glacial drift; and in landlls and
sewers (Schoell, 1988; Coleman et al., 1995). There are
two principal enzymatic pathways by which biogenic
CH4 is produced (Schoell, 1980): (1) acetic acid
fermentation; and (2) carbon dioxide reduction.
1 acetic acid fermentation: CH3 COOH ! CH4 CO2
2 CO2 reduction: CO2 4H2 ! CH4 2H2 O
The fermentation pathway involves the production
of short-chain organic acid precursors (commonly
acetic acid) from the source organic matter. Sub-
sequently, methanogenic bacteria disproportionate the
acids into CO2 and CH4 . The CO2 reduction pathway
involves reduction of CO2 by molecular hydrogen.
Biogenic CH4 formed in near-surface, nonmarine
environments (e.g. marshes, swamps, and landlls) is
primarily formed by acetic acid fermentation (Coleman
et al., 1995).
From the standpoint of environmental liability, it is
useful to separate near surface CH4 occurrences into
# 2000 AEHS
4 P.D. Lundegard, R.E. Sweeney and G.T. Ririe
those with natural and anthropogenic origins. Natural
occurrences include: (1) seeps originating from natural
gas accumulations; (2) coal-bed gas; and (3) gas
produced by biodegradation of indigenous sedimen-
tary organic matter (e.g. organic-rich shales or marsh
deposits). Anthropogenic CH4 occurrences are caused
by human activities and therefore are associated with
potential environmental liability. Anthropogenic CH4
can be derived from: (1) gas pipelines; (2) oil and gas
wells; (3) sewer pipes and septic systems; (4) buried
compost; (5) landlls; and (6) spilled petroleum.
While correlation between CH4 concentration in soil
gas and petroleum contaminated soil have led some
environmental scientists to infer a direct causal
relationship, the process by which carbon in petroleum
would be converted to CH4 is not clear. Methanogen-
esis requires (1) strict anaerobic conditions (i.e. an
absence of oxygen); and (2) either molecular hydrogen
and CO2 or certain oxygen-bearing precursor com-
pounds (e.g. organic acids). Petroleum does not
contain signicant amounts of the short-chain pre-
cursor compounds necessary for direct fermentation
reactions. However, under certain conditions, petrol-
eum degradation can generate the necessary precursor
compounds for methanogenesis by fermentation
(Eganhouse et al., 1993; Revesz et al., 1995). Though
less understood, some groups of bacteria produce H2
under anerobic conditions (Claypool and Kaplan,
1974). The molecular H2 is then available for meth-
anogenesis by CO2 reduction (Whiticar, Faber and
Schoell, 1986). Elevated H2 concentrations have been
found in contaminated groundwater (Lovely, Chapelle
and Woodward, 1994), and soil gas associated with
petroleum contamination (Ririe and Sweeney, 1995).
While these studies indicate that generation of CH4
from petroleum by indirect processes can occur, the
abundance of other anthropogenic and natural sources
of CH4 require that the possible causal relationship
between petroleum and elevated CH4 concentrations be
evaluated on a site specic basis.
Types of Forensic Data
Rarely is a single type of data sucient to resolve an
environmental forensics question. More often, it is the
integration of several types of information that leads to
an eective resolution. In the two case studies
presented here it will be evident that it is the synthesis
of geological, geochemical, and historical land use data
that leads to a credible interpretation of the origin and
source of the soil gas CH4 . Spatial relationships and
trends in the data are particularly important. Below, we
briey discuss several types of geochemical data that
can have value in investigations of soil gas CH4 .
Soil gas compositional analysis is generally the
starting point for most investigations, since one rst
needs to determine the abundance of CH4 and its
spatial variation. We are strong advocates of real-time,
gas chromatographic analysis in the eld so that the
quality of soil gas samples can be assured and the
sampling locations can be properly selected. In some
instances, gas compositional data alone allow dierent
potential gas sources to be distinguished (Schoell,
1980). For example, the content of higher molecular
weight hydrocarbon gases (ethane, propane, butane,
and pentane) relative to CH4 may be used. Biogenic
gases (e.g. landll gas) consist predominantly of CH4
and CO2 and do not typically contain signicant
concentrations of C2 through C5 hydrocarbons (C1/
[C1C5] 4 0.98) (Rice and Claypool, 1981). In con-
trast, most thermogenic gases (e.g. from natural gas
pipelines) do contain signicant concentrations of C2
through C5 hydrocarbons (C1/[C1C5] 0.6 to 1.0).
Carbon and hydrogen isotope data have been
successfully used to discriminate natural gases (includ-
ing CH4) of various origins (Figure 1; Schoell, 1988;
Suchomel, Kreamer and Long, 1990; Coleman et al.,
1995; Baldassare and Laughrey, 1997). Carbon iso-
topic data are reported using the normal delta (d)
notation relative to the PDB (Belemnites in the PeeDee
Formation) international standard. Similarly, hydro-
gen isotopic data are reported using the delta (d)
notation relative to the SMOW (Standard Mean Ocean
Water) international standard.
Rsample Rstandard
X per mil  103
Rstandard
where X refers to either 13C or D (D represents
deuterium, 2H) and R refers to either 13C/12C or D/H
isotopic ratio.
Microbial methanogenesis yields CH4 that is highly
depleted in 13C relative to the organic matter from
which it is formed. Once formed, however, most
geochemical and transport processes in shallow subsur-
face settings (except for bacterial oxidation), do not
signicantly alter the stable isotopic composition of
CH4 (Coleman et al., 1995), which makes the isotope
ratios useful for tracing the origin of CH4 . Biogenic
CH4 produced by acetic acid fermentation is more
enriched in 13C and more depleted in deuterium than
CH4 produced by the reduction of carbon dioxide
(Whiticar, Faber and Schoell, 1986). Furthermore,
isotope studies have shown that methanogenesis by
acetic acid fermentation predominates in near-surface
freshwater environments (Whiticar, Faber and Schoell,
1986).
Carbon-14 analysis has forensic value because of the
information it provides about the age of the organic
carbon source. Carbon-14 is present in all living things.
It is a naturally occurring isotope of carbon that is
formed in the upper atmosphere by the reaction of
cosmic-ray neutrons with nitrogen (Faure, 1977).
Plants extract CO2 from the atmosphere, thereby
incorporating a 14C concentration in their cells that
reects the 14C concentration in atmospheric CO2 .This
14
C concentration is passed up the food chain. In most
environmental investigations the 14C concentration in a
sample is reported in terms of percent modern carbon
( pMC), where 100 pMC is dened as the ``normal'' 14C
concentration in atmospheric CO2 prior to anthro-
pogenic disturbances such as nuclear bomb testing and
extensive burning of fossil fuels (Stuiver and Polach,
1977).
The time signicance of 14C concentrations comes
from two factors. The rst is the natural decay of this
radioactive isotope (Figure 2(a)). When a plant or
animal dies the 14C concentration in its tissue gradually
decreases as the 14C undergoes radioactive decay with a
half-life of 5730 years. After approximately 50,000
 Soil Gas Methane at Petroleum Contaminated Sites 5

Figure 1. Hydrogen and carbon isotopic elds for CH4 of dierent origins. Fields after Coleman et al. (1995). Solid circles are data from a
service station site. Open circles are data from an industrial site.

years, the remaining 14C is too dilute to detect by

standard methods. Organic matter greater than 50,000
years old, and CH4 derived from such organic matter,
will have a 14C concentration of 0 pMC. This would
include CH4 formed from coal, oil, kerogen, and
petroleum products made from these materials (e.g.
gasoline, kerosene, and diesel fuel). Methane formed
from organic matter less than 50,000 years old will
have detectable 14C (greater than 0 pMC) and can be
``dated''. A 14C ``date'' obtained on CH4 reects, not
the time of methanogenesis, but the age of the carbon
source from which CH4 formed.
The second factor giving time signicance to 14C
concentrations is the enormous increase in 14C result-
ing from atmospheric testing of nuclear bombs during
the 1950s and 1960s (Figure 2(b); Levin, Munnich and
Weiss, 1980). Consequently, organic material formed
since this time has an elevated 14C concentration.
Methane produced by bacterial degradation of such
young organic matter will also contain so-called
``bomb carbon'', and have a 14C concentration greater
than 100 pMC. This is typically the case for landll
and sewage gases since they are largely produced from
organic material less than a few decades in age
(Coleman et al., 1995).
Much like 14C, tritium has forensic value in
identifying CH4 produced from modern carbon
sources. Tritium is a naturally occurring radioactive
isotope of hydrogen (3H), and has a half-life of 12.3
years. Its content in the atmosphere and hydrosphere Figure 2. Temporal changes in 14C concentrations: (a) changes related
to radioactive decay of 14C; and (b) changes in 14C concentrations in
was also markedly increased by atomic bomb testing in atmospheric CO2 related to nuclear bomb testing in the 1950s and
the 1950s and 1960s. Consequently, an elevated tritium 1960s. Note that CH4 derived from very old (450,000 years) carbon
content in soil gas CH4 could indicate that the CH4 was sources like petroleum will have a 14C concentration of 0 pMC.
6 P.D. Lundegard, R.E. Sweeney and G.T. Ririe
produced from organic matter no more than a few
decades in age. Methane in some landll gases is very
high in tritium (Coleman et al., 1995).
Case Studies
The following two case studies were selected to
illustrate the application of the forensic tools discussed
above.
Service station site
A service station, located in an urban area near a large
lake, was the site of a large accidental release of
gasoline in 1980. An estimated 303 m3 (80,000 gallons)
of leaded, premium gasoline were released. Light non-
aqueous phase liquid (LNAPL) gasoline eventually
covered an area roughly the size of a city block
(2 acres; Figure 3). During subsequent operation of a
soil vapor extraction system, it was noticed that CH4
comprised a substantial percentage of the inuent
vapor. The concentration of CH4 in the SVE inuent
was greater on average than the concentration of total
volatile hydrocarbons, and reached values greater than
10% (by volume). The CH4 was initially attributed
to bacterial degradation of the spilled gasoline.
However, the persistence of high CH4 concentrations
over time raised new questions about its origin and led
to further investigation (Lundegard, Haddad and
Brearley, 1998).
Exploratory borings and review of historical land
use records revealed that the site vicinity was underlain
by other carbon sources, including ll material and
abundant zones of sawdust and wood, as well as
historical lake sediments. Forensic investigations
focused on whether gasoline or these other carbon
sources could be the source of the CH4 .
Figure 3. Service station site map showing original liquid gasoline plume and CH4 concentrations measured in monitoring wells sampled in
this study.
Soil gas was collected from 23 monitoring wells
within the limits of the original gasoline spill and
beyond. Gas compositional analysis was conducted in
the eld with a portable gas chromatograph. Samples
were also collected for subsequent isotopic analysis in
the laboratory.
Methane content of soil gas samples varied by
several orders of magnitude, from 0.002 to 26% (by
volume), and exceeded to the lower explosive limit
(5%) in about half the samples (Figure 3). Carbon
dioxide concentrations ranged from 0.265 to 27% (by
volume). The observed CH4 concentrations were
somewhat higher than values typically reported for
soil gas associated with petroleum contamination at
other sites (Marrin, 1989, 1991). High CH4 and CO2
concentrations were not restricted to the original area
of contaminated soil and LNAPL, as is the case at
other contaminated sites (Marrin, 1987, 1989, 1991;
Suchomel, Kreamer and Long, 1990). Elevated CH4
concentrations were encountered upgradient, down-
gradient, and cross-gradient of the original LNAPL
plume (Figure 3). The occurrence of high CH4 con-
centrations well beyond the limits of the original
gasoline spill suggested that, perhaps, gasoline is not
the sole source of the CH4 .
Within the limits of the gasoline spill some C2 C6
gasoline constituents were observed using gas chroma-
tographic techniques. However, in high-CH4 samples
well beyond the limits of the original gasoline spill, less
than 0.01% C2 hydrocarbons (ethane and heavier)
were observed. Low concentrations of C2 C6 alkanes
are characteristic of biogenic gas accumulations.
Methane from the site had an average carbon iso-
topic composition of 49.5- (s 4.8), and average
hydrogen isotopic composition of 310- (s 7.5).
Carbon dioxide from the site had an average carbon
isotopic composition of 17.1- (s 7.7). The stable
isotope and chemical data indicate the CH4 was

produced microbially by fermentation (Figure 1), as is
most landll gas, and rule out a thermogenic origin for
the CH4 . Sources of thermogenic gas would include
natural seepage from subsurface oil and gas deposits,
and leaking gas pipelines. However, these stable
isotope data alone did not resolve whether the source
of the CH4 was the spilled gasoline or the other carbon
sources in the environment (e.g. woody ll debris or
lake sediments). Carbon isotopic analysis of wood
from the ll beneath the site and of gasoline from a
monitoring well indicated that the wood and gasoline
were essentially indistinguishable (d 13C wood
25.95-; d 13C gasoline 25.83-). Therefore,
stable isotope analyses, while identifying the predomi-
nant mechanism for CH4 formation (acetic acid
fermentation), were unable to uniquely identify the
carbon source for the CH4 .
When potential carbon sources have very similar
stable isotopic compositions, or when bacterial oxi-
dation has occurred, the source and origin of near-
surface CH4 is more dicult to determine. Under these
conditions, 14C (or tritium) data can be a powerful
supplement to stable isotope data.
Five high-CH4 samples were selected for 14C analy-
sis. Included were two samples more than 160 feet
(49 m) beyond the limits of the original spill, on both
the upgradient and downgradient sides (Figure 4). The
14
C concentrations in the CH4 in the ve samples were,
60, 87, 92, 96, and 97 pMC, respectively. The two
samples farthest from the original gasoline spill had the
highest 14C concentrations. If CH4 were derived wholly
from the spilled gasoline its 14C concentration would
be 0.0 pMC. It is clear, therefore, that the CH4 in these
samples is not derived predominantly from gasoline.
By considering mathematical mixing relationships,
further understanding of the 14C results can be
achieved. In a two component mixture, the percentage
of methane derived from gasoline can be calculated
from the measured 14C concentration of the methane,
Figure 4. Map showing methane 14C results for the service station site. Note that CH4 derived from gasoline would have a 14C concentration of
0 pMC. High values indicate little input from gasoline.
Soil Gas Methane at Petroleum Contaminated Sites 7
the gasoline, and the second carbon source for the
methane as follows:
14

CCH4 14 Csource 2
%gasoline 14
 100
Cgasoline 14 Csource 2
where %gasoline is the percentage of gasoline-derived
methane in the methane sample, and 14 CCH4 ,
14
Ggasoline , 14Csource 2 , are the 14C concentrations in
the methane sample, the gasoline (0 pMC), and the
second carbon source, respectively.
The sample with a CH4 14C concentration of
60 pMC came from a well within the original extent
of the gasoline plume. The 14C concentration of this
sample could be explained by formation solely from
organic matter approximately 4000 years old. Alter-
natively, it could represent a mixture of two or more
carbon sources. For example, if a two component
mixture involved contributions from the woody ll
material (estimated 14C concentration of 97 pMC) and
the gasoline (14C concentration of 0 pMC), 38% of the
CH4 could theoretically have been produced from
gasoline. Any contribution of CH4 from organic
matter older than the wood ll, such as the underlying
lake sediments, would reduce the calculated percentage
of gasoline-derived CH4 . The 14C concentration in the
other four samples suggests that the actual contri-
bution of CH4 from gasoline is probably much lower
than 38%.
The CH4 in the other four samples, with 14C
concentrations of 87, 92, 96, and 97 pMC, could be
produced entirely from organic matter with an average
age of between 200 and 1100 years. While the precise
age of lake sediments underlying the site is not known,
their age could plausibly lie within this range.
Derivation of CH4 exclusively from the wood ll
beneath the site (estimated age of 150250 years)
would yield a CH4 14C concentration of approximately
97 pMC. One of these four methane samples, there-
8 P.D. Lundegard, R.E. Sweeney and G.T. Ririe
fore, could be completely derived from the wood ll. A
two component mixture calculation for these four
samples, assuming the two sources are the gasoline
(0 pMC) and the wood ll debris (97 pMC), indicates
that the maximum contribution from gasoline ranges
from 0 to 10%. Contributions of methane from
organic matter in the lake sediments would reduce
the calculated contribution from gasoline. With the
knowledge that two of these four samples came from
well beyond the limits of the original gasoline spill, it is
very unlikely that more than a few percent of the CH4
in these samples was derived from the gasoline spilled
at the site. The 14C data indicate that the primary
sources of the methane are the woody debris within the
ll material and the underlying lake sediments.
Industrial facility
The second investigation was conducted at a large
industrial facility where crude oil was stored. A number
of accidental releases of the crude oil were known to
have occurred. Natural seeps of liquid and gaseous
hydrocarbons from underlying petroleum reservoirs
are also well known in the region surrounding the
facility. Numerous pipelines and utility corridors exist
in the area. In an area of the site where the soils were
substantially impacted by spilled crude oil, high
concentrations of combustible hydrocarbons were
detected in soil gas. As a result of a property trans-
action, the source of the vapors was a liability issue and
an important factor in determining the suitability of
the area for construction. There was also interest in the
fate of the CH4 and whether there was signicant
upward transport towards the ground surface.
Initially, shallow soil gas samples were collected in
the area of the spilled crude oil. Driven soil probes were
used to obtain samples at 2 feet below grade. Gas
chromatographic analysis revealed that the soil gas
contained up to 24% (by volume) CH4 as the pre-
dominant hydrocarbon. C2 to C5 hydrocarbons were
Figure 5. Detailed vertical prole of soil gas composition at industrial facility. Carbon isotopic results for CH4 and CO2 are posted next to data
points. Entire soil column is contaminated with crude oil.
present in low concentrations, from a few ppmv to over
1000 ppmv (C1/[C1 C5] 4 0.98). Having identied
areas of very high CH4 concentrations, vertical prol-
ing to a depth of 20 feet was conducted in order to
understand better the occurrence and source of the
CH4 . The soils throughout the proled depth range
contained substantial amounts of crude oil.
Carbon and hydrogen isotopic data on CH4 in
selected samples conrmed that the CH4 is biogenic
rather than thermogenic in origin (Figure 1). This
origin is also consistent with the low concentrations of
C2 to C5 hydrocarbons. Carbon-14 analysis indicated
that the CH4 and associated carbon dioxide contained
no detectable 14C, indicating that these components
were derived from a carbon source greater than 50,000
years in age. Together, this information rules out
several possible sources for the CH4 . The 14C data
rules out ``modern'' carbon sources such as buried
refuse, compost, and sewer gas. The stable isotope data
excludes sources of thermogenic gas such as leaking
gas pipelines and natural seepage from reservoired
thermogenic gas in the underlying sedimentary basin.
Based on these geochemical data, the CH4 could be
produced in the near-surface soil environment from
biogenic degradation of the spilled crude oil, or
produced biogenically at greater depth from naturally
occurring, old (450,000 years) organic matter and
transported to the near-surface soil environment.
A detailed vertical prole of soil gas composition
was developed by careful sampling at dierent depths
within the zone of contaminated soil from 0.5 to 20 feet
below ground surface. The observed variation in gas
composition sheds light on both the source and fate of
the CH4 . In the upper 5 feet the CH4 concentration
increased dramatically with increasing depth, leveling
o at between 70 and 75% (by volume) at 5 feet and
greater (Figure 5). These are the highest concentrations
we have ever observed in the shallow vadose zone.
Oxygen showed the opposite depth-trend in concen-
tration, decreasing sharply in the upper 2 feet and

Figure 6. Carbon isotopic composition of CH4 and associated CO2 at industrial facility. The positive carbon isotopic composition of CO2 in the
anaerobic zone of the soil column is evidence of methanogenesis by CO2 reduction. Fields are modied slightly from Whiticar et al. (1980).
reaching zero at 3 feet and greater, indicating the
occurrence of anaerobic conditions. Carbon dioxide
concentrations varied in a manner similar to CH4 ,
increasing rapidly with increasing depth to about 23%
at 7 feet and greater. However, in the aerobic zone of
the soil column (upper 3 feet) the CO2/CH4 ratio is
signicantly greater than it is below. This observation,
together with the fact that CH4 in the upper 3 feet has a
heavier (more positive) carbon isotopic composition,
and the CO2 has a lighter (more negative) carbon
isotopic composition than deeper samples, is evidence
that CH4 oxidation is occurring near the ground
surface (Coleman, Risatti and Schoell, 1981). In
general, the presence of oxygen in soil gas will indicate
that CH4 oxidation is likely to be occurring.
The vertical trend in H2 concentration was found to
be particularly important to understanding the source
and origin of the CH4 (Figure 5). From 0.5 to 3 feet in
depth H2 concentration increased more than 2 orders
of magnitude from 41 ppm to 15,378 ppm (1.5%).
Below 3 feet, the H2 concentration decreases sharply to
less than 100 ppm by 7 feet depth, indicating that H2
utilization is occurring within the anaerobic zone of the
soil column. In addition, the heavy carbon isotopic
composition of CO2 in the anaerobic zone (greater
than 10-) is evidence of CO2 reduction (Figure 6).
These geochemical depth trends and isotopic data
strongly suggest that CH4 is being generated from
petroleum contamination in the interval from 3 to 7 feet
by the reduction of CO2 with molecular H2 . Thus,
while the compositional and isotopic data indicate a
biogenic origin for the CH4 at this industrial facility, it
is the detailed depth trends that identify the crude oil
contamination as the source of the CH4 .
Soil Gas Methane at Petroleum Contaminated Sites 9
Summary
Determining the origin and source of near-surface CH4
is very important in the determination of environmen-
tal liability. As demonstrated by the case studies
presented, CH4 associated with spilled petroleum is
derived from the petroleum in some cases, but not in
others. There are a variety of potential sources for
vadose zone accumulations of CH4 . The various
natural and anthropogenic sources should be carefully
evaluated, along with the possible origin from
petroleum contamination. Importantly, hazards associ-
ated with CH4 derived from sources other than spilled
petroleum will not be eliminated by cleanup of the
petroleum contamination. The source and genesis of
CH4 can be eectively investigated by integrating site
specic geological, land use, and forensic geochemical
data. Spatial trends in geochemical data (vertically and
laterally) are especially important.
Acknowledgements
The authors would like to thank Dennis Coleman and
two anonymous reviewers for their very constructive
comments on the manuscript.
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