Soil Gas Methane at Petroleum Contaminated Sites: Forensic Determination of Origin and Source

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a significant health and safety risk. While petroleum products do not contain a significant amount of methane (CH₄), high CH₄contents in soil gas near petroleum spills have been reported. While CH₄is nontoxic, its accumulation in shallow soil gas represents a potential explosion and asphyxiation hazard, especially in confined spaces. Identifying the source and origin of shallow CH₄accumulations 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 CH₄and 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 CH₄associated with a gasoline spill is shown to be derived from a natural source rather than the gasoline, and a second where CH₄associated with spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil.     

A Strategy and Methodology for Defensibly Correlating Spilled Oil to Source Candidates

The source of crude oils and petroleum products released into navigable waterways and shipping lanes is not always known. Thus, the defensible identification of spilled crude oils and petroleum products and their correlation to suspected sources is a critical part of many oil spill assessments. Quantitative "fingerprinting" analysis, when evaluated using straightforward statistical and numerical analyses, provides a defensible means to differentiate among qualitatively similar oils and provides the best assessment of the source(s) for spilled oils. Polycyclic aromatic hydrocarbon (PAH) and petroleum biomarker concentration data are a particularly useful quantitative measure that can benefit most oil spill investigations. In this paper the strategy and methodology for correlation analysis that relies upon quantitative gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM) is demonstrated in a case study involving 66 candidate sources for a heavy fuel oil spill of unknown origin. The strategy includes identification of 19 chemical indices (out of 45 evaluated) based upon PAH's and biomarkers that were (1) independent of weathering; and (2) precisely measured, both of which are determined by statistical analysis of the data. The 19 chemical indices meeting these criteria are subsequently analysed using principal component analysis (PCA), which helps to determine defensibly the "prime suspects" for the oil spill under investigation. The strategy and methodology described, which combines statistical and numerical analysis of quantitative chemical data, can be adapted and applied to other environmental forensic investigations with the objective of correlating any form of contamination to its suspected sources.     

A Strategy and Methodology for Defensibly Correlating Spilled Oil to Source Candidates

The source of crude oils and petroleum products released into navigable waterways and shipping lanes is not always known. Thus, the defensible identification of spilled crude oils and petroleum products and their correlation to suspected sources is a critical part of many oil spill assessments. Quantitative “fingerprinting” analysis, when evaluated using straightforward statistical and numerical analyses, provides a defensible means to differentiate among qualitatively similar oils and provides the best assessment of the source(s) for spilled oils. Polycyclic aromatic hydrocarbon (PAH) and petroleum biomarker concentration data are a particularly useful quantitative measure that can benefit most oil spill investigations. In this paper the strategy and methodology for correlation analysis that relies upon quantitative gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM) is demonstrated in a case study involving 66 candidate sources for a heavy fuel oil spill of unknown origin. The strategy includes identification of 19 chemical indices (out of 45 evaluated) based upon PAH's and biomarkers that were (1) independent of weathering; and (2) precisely measured, both of which are determined by statistical analysis of the data. The 19 chemical indices meeting these criteria are subsequently analysed using principal component analysis (PCA), which helps to determine defensibly the “prime suspects” for the oil spill under investigation. The strategy and methodology described, which combines statistical and numerical analysis of quantitative chemical data, can be adapted and applied to other environmental forensic investigations with the objective of correlating any form of contamination to its suspected sources.     

加油站场地油品渗漏探测及土壤污染评估

用洛阳铲采集某地区10座地下贮罐罐龄接近或超过10年的典型加油站场地不同深度土样,并分别用吹脱/捕集/热脱附/气相色谱法和快速溶剂萃取/硅酸镁净化/气相色谱法分析样品中的挥发性和萃取性石油烃,发现2座加油站疑似油品渗漏,其中1座为柴油渗漏,地下贮罐附近1.2 ～3.0 m深度土壤总石油烃含量16.1 ～24.6 g/kg,均超过荷兰土壤清除标准,另1座为汽油和柴油混合渗漏,其地下贮罐附近2.4m深度土壤总石油烃含量较高,但未超标.个别加油站场地较高的土壤天然有机物背景值可能计入EPH的分析结果,但其色谱指纹明显不同于石油烃.     

Applications of Anthropogenic Lead ArchaeoStratigraphy (ALAS Model) to Hydrocarbon Remediation

A model, which employs the use of high precision stable lead isotopic analyses, has been developed to estimate the age of hydrocarbon releases. The ALAS Model (Anthropogenic Lead ArchaeoStratigraphy) is based on calibrated, systematic increases in lead isotope ratios of gasolines caused by shifts in sources of lead ores used by the U.S. lead industry, including manufacturers of alkylleads, to more radiogenic Mississippi Valley Type (MVT) deposits. Acquisition of high quality samples (free product, gasoline-impacted soil and groundwater) of known age and subsequent analyses of the hydrocarbon component by high precision lead isotopic analyses by thermal ionization mass spectrometry (TIMS) have produced the ALAS Model calibration curve. Age uncertainties range from - 1 to 2 years for gasoline releases which occurred between 1965 and 1990, the major era of leaded gasoline usage. Analytical methods required to measure lead isotope ratios on ~5 nanograms of lead with precisions and accuracy of < - 0.1% (2 SEM ) are discussed in detail. Published lead isotopic measurements of gasoline-derived anthropogenic lead of samples throughout the United States are used to demonstrate the wide geographic range over which the ALAS Model may be applied. Two representative case studies involving an early 1970s free product release in California and the discrimination of a 1970s from modern unleaded gasoline release in Florida demonstrate the use of the model on single and multiple hydrocarbon releases, respectively, in different geographic regions of the United States. A third investigation focuses on the use of lead isotopes to correlate dissolved phase hydrocarbons with their source, in this case, unleaded (aka low lead) gasoline releases in New Jersey. Dissolved phase hydrocarbons (BTEX/MTBE) are shown to carry the lead isotopic signature of the unleaded gasoline into groundwater, allowing the specific source of the release to be identified. Investigations of lead isotopes as tracers of MTBE in groundwater are ongoing. However, both laboratory and field data indicate MTBE carries the lead isotopic signature of its unleaded gasoline source into groundwater, demonstrating the potential of the lead isotopic system as a discriminant of MTBE sources. Although developed to estimate the age of leaded gasoline releases, the ALAS Model has been successfully applied in studies requiring age dating of jet-A, diesel, kerosene, motor oil, and heating oil. These petroleum distillates are suspected of accidentally acquiring small, yet significant quantities of alkylleads during refining, allowing accurate ALAS Model ages to be determined. When lead levels in these petroleum distillates are within their normal range, typically tens to hundreds of ppb lead, it is possible to use lead isotopic ratios to correlate environmental releases of these products to their source or other releases.     

Development and verification of a screening model for surface spreading of petroleum

Overflows and leakage from aboveground storage tanks and pipelines carrying crude oil and petroleum products occur frequently. The spilled hydrocarbons pose environmental threats by contaminating the surrounding soil and the underlying ground water. Predicting the fate and transport of these chemicals is required for environmental risk assessment and for remedial measure design. The present paper discusses the formulation and application of the Oil Surface Flow Screening Model (OILSFSM) for predicting the surface flow of oil by taking into account infiltration and evaporation. Surface flow is simulated using a semi-analytical model based on the lubrication theory approximation of viscous flow. Infiltration is simulated using a version of the Green and Ampt infiltration model, which is modified to account for oil properties. Evaporation of volatile compounds is simulated using a compositional model that accounts for the changes in the fraction of each compound in the spilled oil. The coupling between surface flow, infiltration and evaporation is achieved by incorporating the infiltration and evaporation fluxes into the global continuity equation of the spilled oil. The model was verified against numerical models for infiltration and analytical models for surface flow. The verification study demonstrates the applicability of the model.     

膨胀石墨在环境污染治理中的应用

膨胀石墨是一种新型的多孔碳质吸附材料.它具有发达的孔结构,对于大分子的物质具有超大的吸附能力.膨胀石墨作为新型纳米功能材料,广泛应用于石油、化工、冶金、机械和环保等领域.在概述膨胀石墨的吸附性能和机理的基础上,介绍了其在海洋溢油污染、水中微量油污染、印染废水和有毒气体治理等方面的应用,并对膨胀石墨的最新合成方法和应用发展趋势进行了展望和预测.     

Mitigating nitrous oxide and methane emissions from soil in rice-wheat system of the Indo-Gangetic plain with nitrification and urease inhibitors

Mitigation of methane (CH4) and nitrous oxide (N2O) emissions from soil is important to reduce the global warming. Efficacy of five nitrification inhibitors, i.e. neem (Azadirachta melia) cake, thiosulphate, coated calcium carbide, neem oil coated urea and dicyandiamide (DCD) and one urease inhibitor, hydroquinone, in mitigating N2O and CH4 emissions from fertilized soil was tested in rice-wheat system in the Indo-Gangetic plains. The closed chamber technique was used for the collection of gas samples, which were analyzed using gas chromatography. Reduction in N2O emission on the application of nitrification/urease inhibitors along with urea ranged from 5% with hydroquinone to 31% with thiosulphate in rice and 7% with hydroquinone to 29% with DCD in wheat crop. The inhibitors also influenced the emission of CH4. While application of neem coated urea, coated calcium carbide, neem oil and DCD reduced the emission of CH4; hydroquinone and thiosulphate increased the emission when compared to urea alone. However, the global warming potential was lower with the inhibitors (except hydroquinone) as compared to urea alone, suggesting that these substances could be used for mitigating greenhouse gas emission from the rice-wheat systems.     

Effect of hydrocarbon pollution on the microbial properties of a sandy and a clay soil

The aim of this work was to ascertain the effects of different types of hydrocarbon pollution on soil microbial properties and the influence of a soil's characteristics on these effects. For this, toxicity bioassays and microbiological and biochemical parameters were studied in two soils (one sandy and one clayey) contaminated at a loading rate of 5% and 10% with three types of hydrocarbon (diesel oil, gasoline and crude petroleum) differing in their volatilisation potential and toxic substance content. Soils were maintained under controlled conditions (50-70% water holding capacity, and room temperature) for six months and several microbiological and toxicity parameters were monitored 1, 60, 120 and 180 days after contamination. The toxic effects of hydrocarbon contamination were greater in the sandy soil. Hydrocarbons inhibited microbial biomass, the greatest negative effect being observed in the gasoline-polluted sandy soil. In both soils crude petroleum and diesel oil contamination increased microbial respiration, while gasoline had little effect on this parameter, especially in the sandy soil. In general, gasoline had the highest inhibitory effect on the hydrolase activities involved in N, P or C cycles in both soils. All contaminants inhibited hydrolase activities in the sandy soil, while in the clayey soil diesel oil stimulated enzyme activity, particularly at the higher concentration. In both soils, a phytotoxic effect on barley and ryegrass seed germination was observed in the contaminated soils, particularly in those contaminated with diesel or petroleum.     

Petroleum and hazardous chemical spills in Newark Bay, New Jersey, USA from 1982 to 1991

Newark Bay, New Jersey, is particularly vulnerable to ecological damage from petroleum and chemical spills, as a result of the enclosed nature and shallow depth of the bay, the high frequency of shipping traffic, and the numerous chemical and petroleum transfer terminals located alongs its shores. To evaluate the potential impacts to the natural resources of this coastal estuarine ecosystem, chemical and petroleum accidents reported to the US Coast Guard (USCG) between 1982 and 1991 were compiled to determine the frequency and volume of these incidents in Newark Bay and in each of its major tributaries. Records obtained from the USCG National Response Center's computerized database indicated that more than 1453 accidental incidents, resulting in the release of more than 18 million US gallons of hazardous materials and petroleum products, occurred throughout Newark Bay during this period of time. The bulk of the materials released to the aquatic environment consisted of petroleum products, specifically No. 6 Fuel Oil (103 spills, 12 829 272 US gal) and gasoline (207 spills, 48 816 US gal). The majority of the reported incidents occurred in the Arthur Kill and its tributaries, as well as in the Kill Van Kull and the Passaic River. The results of this study indicated that the accidental discharge of petroleum and hazardous chemicals represents a significant source of chemical pollution in Newark Bay. Based on the frequency of spills and the volume of materials released to the aquatic environment, it is likely that these events are having a deleterious effect on the Newark Bay ecosystem.     

Applications of Anthropogenic Lead ArchaeoStratigraphy (ALAS Model) to Hydrocarbon Remediation

A model, which employs the use of high precision stable lead isotopic analyses, has been developed to estimate the age of hydrocarbon releases. The ALAS Model (Anthropogenic Lead ArchaeoStratigraphy) is based on calibrated, systematic increases in lead isotope ratios of gasolines caused by shifts in sources of lead ores used by the U.S. lead industry, including manufacturers of alkylleads, to more radiogenic Mississippi Valley Type (MVT) deposits. Acquisition of high quality samples (free product, gasoline-impacted soil and groundwater) of known age and subsequent analyses of the hydrocarbon component by high precision lead isotopic analyses by thermal ionization mass spectrometry (TIMS) have produced the ALAS Model calibration curve. Age uncertainties range from  ± 1 to 2 years for gasoline releases which occurred between 1965 and 1990, the major era of leaded gasoline usage. Analytical methods required to measure lead isotope ratios on ∼5 nanograms of lead with precisions and accuracy of < ± 0.1% (2_SEM) are discussed in detail. Published lead isotopic measurements of gasoline-derived anthropogenic lead of samples throughout the United States are used to demonstrate the wide geographic range over which the ALAS Model may be applied. Two representative case studies involving an early 1970s free product release in California and the discrimination of a 1970s from modern unleaded gasoline release in Florida demonstrate the use of the model on single and multiple hydrocarbon releases, respectively, in different geographic regions of the United States. A third investigation focuses on the use of lead isotopes to correlate dissolved phase hydrocarbons with their source, in this case, unleaded (aka low lead) gasoline releases in New Jersey. Dissolved phase hydrocarbons (BTEX/MTBE) are shown to carry the lead isotopic signature of the unleaded gasoline into groundwater, allowing the specific source of the release to be identified. Investigations of lead isotopes as tracers of MTBE in groundwater are ongoing. However, both laboratory and field data indicate MTBE carries the lead isotopic signature of its unleaded gasoline source into groundwater, demonstrating the potential of the lead isotopic system as a discriminant of MTBE sources. Although developed to estimate the age of leaded gasoline releases, the ALAS Model has been successfully applied in studies requiring age dating of jet-A, diesel, kerosene, motor oil, and heating oil. These petroleum distillates are suspected of accidentally acquiring small, yet significant quantities of alkylleads during refining, allowing accurate ALAS Model ages to be determined. When lead levels in these petroleum distillates are within their normal range, typically tens to hundreds of ppb lead, it is possible to use lead isotopic ratios to correlate environmental releases of these products to their source or other releases.     

Determination of the applicability of CERCLA's petroleum exclusion at contaminated sites – focus on metals

Areas impacted by petroleum refining and handling operations may become subject to CERCLA enforcement. Because of CERCLA's petroleum exclusion clause, determining whether contamination in a CERCLA Site originated from petroleum products or hazardous wastes becomes important. Because certain metals are typically enriched in wastes relative to petroleum products and background soils, knowledge of metal contents in these potential end member metal sources is an important step towards contaminant source identification in soils and sediments. In LNAPL plumes, metal content, particularly lead, may be claimed to be the result of wastes mishandling and not due only to the presence of leaded gasoline in the plume. Analysis of the percent gasoline in the plume and accounting for weathering are steps to determining whether the lead content in an LNAPL plume is within the historical lead concentration ranges in gasolines. In addition to metals analyses, understanding of operational parameters such as the history of petroleum refining and handling operations, leaks, spills, and cleanup activities are needed for successful conclusion of the applicability of the petroleum exclusion.     

Alkytcyclohexanes in Environmental Geochemistry

The n -alkylated cyclohexanes (CHs) are a homologous series of hydrocarbon compounds that are commonly present in crude oil and refinery products such as diesel fuel. These compounds exhibit specific distribution patterns for different fuel types, providing useful fingerprints for characterizing petroleum products, especially after degradation of n -alkanes has occurred. However, there are no published data to show how these compounds are altered in the environment after long-term spillage of petroleum products. This paper presents two case studies of oil spills that demonstrate the changing distribution patterns resulting from long-term anaerobic microbial degradation. These spills are the 1979 crude-oil spill in Bemidji, Minnesota, and a chronic diesel-fuel spillage from 1953-1991 at Mandan, North Dakota. The alkyl CHs in both spilled oil products are affected by similar biodegradative processes in which the compounds undergo a consistent pattern of loss from the high molecular weight end of the homolog distribution. Degradation results in a measurable increase in the concentrations of the homologs in the lower molecular weight range, a gradual lowering in carbon number of the homolog maximum, and a gradual decrease of the total homolog range from the high molecular weight end. This pattern is the opposite of low-end loss expected with weathering and aerobic biodegradation. The enhancement of the low molecular mass alkyl CH homologs, if not recognized as a degradative pathway of diesel fuel in an anaerobic environment, can potentially be misinterpreted in fuel-oil fingerprinting as deriving from lower distillation-range fuels or admixture of diesel with other fuels.     

Alkylcyclohexanes in Environmental Geochemistry

The n -alkylated cyclohexanes (CHs) are a homologous series of hydrocarbon compounds that are commonly present in crude oil and refinery products such as diesel fuel. These compounds exhibit specific distribution patterns for different fuel types, providing useful fingerprints for characterizing petroleum products, especially after degradation of n -alkanes has occurred. However, there are no published data to show how these compounds are altered in the environment after long-term spillage of petroleum products. This paper presents two case studies of oil spills that demonstrate the changing distribution patterns resulting from long-term anaerobic microbial degradation. These spills are the 1979 crude-oil spill in Bemidji, Minnesota, and a chronic diesel-fuel spillage from 1953–1991 at Mandan, North Dakota. The alkyl CHs in both spilled oil products are affected by similar biodegradative processes in which the compounds undergo a consistent pattern of loss from the high molecular weight end of the homolog distribution. Degradation results in a measurable increase in the concentrations of the homologs in the lower molecular weight range, a gradual lowering in carbon number of the homolog maximum, and a gradual decrease of the total homolog range from the high molecular weight end. This pattern is the opposite of low-end loss expected with weathering and aerobic biodegradation. The enhancement of the low molecular mass alkyl CH homologs, if not recognized as a degradative pathway of diesel fuel in an anaerobic environment, can potentially be misinterpreted in fuel-oil fingerprinting as deriving from lower distillation-range fuels or admixture of diesel with other fuels. Published by Elsevier Science Ltd on behalf of AEHS.     

Agricultural opportunities to mitigate greenhouse gas emissions

Agriculture is a source for three primary greenhouse gases (GHGs): CO(2), CH(4), and N(2)O. It can also be a sink for CO(2) through C sequestration into biomass products and soil organic matter. We summarized the literature on GHG emissions and C sequestration, providing a perspective on how agriculture can reduce its GHG burden and how it can help to mitigate GHG emissions through conservation measures. Impacts of agricultural practices and systems on GHG emission are reviewed and potential trade-offs among potential mitigation options are discussed. Conservation practices that help prevent soil erosion, may also sequester soil C and enhance CH(4) consumption. Managing N to match crop needs can reduce N(2)O emission and avoid adverse impacts on water quality. Manipulating animal diet and manure management can reduce CH(4) and N(2)O emission from animal agriculture. All segments of agriculture have management options that can reduce agriculture's environmental footprint.     

Enhancing bioremediation of diesel oil and gasoline in soil amended with an agroindustry sludge

This paper presents a study of the bioremediation of diesel oil and gasoline by a series of controlled laboratory tests. Sludge from an agroindustry was used to enhance bioremediation of both gasoline and diesel oil mixed with a soil mass to compare its efficiency with that of a mineral fertilizer. Effects of soil microbiology and soil mixtures were investigated by means of evolution of CO2, microorganism populations at 90 days, pH at 65 and 95 days, mineral nitrogen, and gas chromatographic analysis of the benzene, toluene, methyl tertiary butyl ether, C8, and C9+total aromatics at the end of the experiments. Treatments containing sludge showed better soil conditions after 170 days of treatment (inorganic nitrogen and microbiota activity) compared with gasoline and diesel oil without amendments. Samples had no detectable traces of the measured hydrocarbons at 170 days of treatment.     

Brazilian Oil Spills Chemical Characterization--Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds--benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

A Chemical Mass Balance for Volatile Organics in Chicago

Increasing attention to the presence of atmospheric volatile organic compounds has focused interest on the sources and fate of organics in ambient air. The purpose of this study was to develop a chemical mass balance receptor model (CMB) to determine the contributions of major organic pollution source types to ambient pollution levels. Twenty mid-day ambient air samples were analyzed for the presence of volatile hydrocarbons by gas chromatographlc procedures. Based on these measurements, contributions from vehicles, gasoline vapor emissions, and petroleum refineries to ambient organic concentrations were estimated. For the receptor site studied, vehicles were the dominant source type and accounted for 60.8 percent of the organics evaluated. Contributions from refineries, gasoline vapor, and all other sources were 10.1, 11.1, and 17.9 percent, respectively. Validation of the predictions showed that the model is sensitive to the effect of overall upwind emissions. The CMB model was shown to produce reasonable predictive results for vehicles, gasoline vapor, and refinery contributions to ambient non-methane organic concentrations.     

Brazilian Oil Spills Chemical Characterization—Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds—benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O(2) to waters otherwise depleted in O(2). Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH(4) partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.