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USGS2004

Composition, dynamics, and fate of leached dissolved organic matter in terrestrial ecosystems: Results from a decomposition experiment

Fluxes of dissolved organic matter (DOM) are an important vector for the movement of carbon (C) and nutrients both within and between ecosystems. However, although DOM fluxes from throughfall and through litterfall can be large, little is known about the fate of DOM leached from plant canopies, or from the litter layer into the soil horizon. In this study, our objectives were to determine the importance of plant-litter leachate as a vehicle for DOM movement, and to track DOM decomposition [including dissolve organic carbon (DOC) and dissolved organic nitrogen (DON) fractions], as well as DOM chemical and isotopic dynamics, during a long-term laboratory incubation experiment using fresh leaves and litter from several ecosystem types. The water-extractable fraction of organic C was high for all five plant species, as was the biodegradable fraction; in most cases, more than 70% of the initial DOM was decomposed in the first 10 days of the experiment. The chemical composition of the DOM changed as decomposition proceeded, with humic (hydrophobic) fractions becoming relatively more abundant than nonhumic (hydrophilic) fractions over time. However, in spite of proportional changes in humic and nonhumic fractions over time, our data suggest that both fractions are readily decomposed in the absence of physicochemical reactions with soil surfaces. Our data also showed no changes in the δ 13 C signature of DOM during decomposition, suggesting that isotopic fractionation during DOM uptake is not a significant process. These results suggest that soil microorganisms preferentially decompose more labile organic molecules in the DOM pool, which also tend to be isotopically heavier than more recalcitrant DOM fractions. We believe that the interaction between DOM decomposition dynamics and soil sorption processes contribute to the δ 13 C enrichment of soil organic matter commonly observed with depth in soil profiles.

Ecosystems↗

USGS2016

The removal kinetics of dissolved organic matter and the optical clarity of groundwater

Concentrations of dissolved organic matter (DOM) and ultraviolet/visible light absorbance decrease systematically as groundwater moves through the unsaturated zones overlying aquifers and along flowpaths within aquifers. These changes occur over distances of tens of meters (m) implying rapid removal kinetics of the chromophoric DOM that imparts color to groundwater. A one-compartment input-output model was used to derive a differential equation describing the removal of DOM from the dissolved phase due to the combined effects of biodegradation and sorption. The general solution to the equation was parameterized using a 2-year record of dissolved organic carbon (DOC) concentration changes in groundwater at a long-term observation well. Estimated rates of DOC loss were rapid and ranged from 0.093 to 0.21 micromoles per liter per day (μM d −1 ), and rate constants for DOC removal ranged from 0.0021 to 0.011 per day (d −1 ). Applying these removal rate constants to an advective-dispersion model illustrates substantial depletion of DOC over flow-path distances of 200 m or less and in timeframes of 2 years or less. These results explain the low to moderate DOC concentrations (20–75 μM; 0.26–1 mg L −1 ) and ultraviolet absorption coefficient values ( a 254 < 5 m −1 ) observed in groundwater produced from 59 wells tapping eight different aquifer systems of the United States. The nearly uniform optical clarity of groundwater, therefore, results from similarly rapid DOM-removal kinetics exhibited by geologically and hydrologically dissimilar aquifers.

California, Colorado, Connecticut, Georgia, Illino↗

USGS2000

Microbial degradation of chloroethenes in groundwater systems

The chloroethenes, tetrachloroethene (PCE) and trichloroethene (TCE) are among the most common contaminants detected in groundwater systems. As recently as 1980, the consensus was that chloroethene compounds were not significantly biodegradable in groundwater. Consequently, efforts to remediate chloroethene-contaminated groundwater were limited to largely unsuccessful pump-and-treat attempts. Subsequent investigation revealed that under reducing conditions, aquifer microorganisms can reductively dechlorinate PCE and TCE to the less chlorinated daughter products dichloroethene (DCE) and vinyl chloride (VC). Although recent laboratory studies conducted with halorespiring microorganisms suggest that complete reduction to ethene is possible, in the majority of groundwater systems reductive dechlorination apparently stops at DCE or VC. However, recent investigations conducted with aquifer and stream-bed sediments have demonstrated that microbial oxidation of these reduced daughter products can be significant under anaerobic redox conditions. The combination of reductive dechlorination of PCE and TCE under anaerobic conditions followed by anaerobic microbial oxidation of DCE and VC provides a possible microbial pathway for complete degradation of chloroethene contaminants in groundwater systems.

Hydrogeology Journal↗

USGS2005

Part 1: Vadose-zone column studies of toluene (enhanced bioremediation) in a shallow unconfined aquifer

The objectives of the laboratory study described in this paper were (1) to determine the effectiveness of four nutrient solutions and a control in stimulating the microbial degradation of toluene in the unsaturated zone as an alternative to bioremediation methodologies such as air sparging, in situ vitrification, or others (Part I), and (2) to compare the effectiveness of the addition of the most effective nutrient solution from Part I (modified Hoagland type, nitrate-rich) and hydrogen peroxide (H 2 O 2 ) on microbial degradation of toluene for repeated, simulated spills in the unsaturated zone (Part II). For Part 1, fifteen columns (30-cm diameter by 150-cm height), packed with air-dried, 0.25-mm, medium-fine sand, were prepared to simulate shallow unconfined aquifer conditions. Toluene (10 mL) was added to the surface of each column, and soil solution and soil gas samples were collected from the columns every third day for 21 days. On day 21, a second application of toluene (10 mL) was made, and the experiment was run for another 21 days. Solution 4 was the most effective for microbial degradation in Part I. For Part II, three columns were designated nutrient-rich 3-day toluene columns and received toluene injections every 3 days; three columns were designated as nutrient-rich 7-day columns and received toluene injections every 7 days; and two columns were used as controls to which no nutrient was added. As measured by CO 2 respiration, the initial benefits for aerobic organisms from the O 2 enhancement were sustained by the bacteria for only a short period of time (about 8 days). Degradation benefits from the nutrient solution were sustained throughout the experiment. The O 2 and nutrient-enhanced columns degraded significantly more toluene than the control columns when simulating repeated spills onto the unsaturated zone, and demonstrated a potentially effective in situ bioremediation technology when used immediately or within days after a spill. The combined usage of H 2 O 2 and nitrate-rich nutrients served to effectively maximize natural aerobic and anaerobic metabolic processes that biodegrade hydrocarbons in petroleum-contaminated media. Applications of this technology in the field may offer economical advantages to other, more intrusive abatement technologies.

Water, Air, & Soil Pollution↗

USGS2005

Part 2: A field study of enhanced remediation of Toluene in the vadose zone using a nutrient solution

The objective of this study was to test the effectiveness of a nitrate-rich nutrient solution and hydrogen peroxide (H 2 O 2 ) to enhance in-situ microbial remediation of toluene in the unsaturated zone. Three sand-filled plots were tested in three phases (each phase lasting approximately 2 weeks). During the control phase, toluene was applied uniformly via sprinkler irrigation. Passive remediation was allowed to occur during this phase. A modified Hoagland nutrient solution, concentrated in 150 L of water, was tested during the second phase. The final phase involved addition of 230 moles of H 2 O 2 in 150 L of water to increase the available oxygen needed for aerobic biodegradation. During the first phase, measured toluene concentrations in soil gas were reduced from 120 ppm to 25 ppm in 14 days. After the addition of nutrients during the second phase, concentrations were reduced from 90 ppm to about 8 ppm within 14 days, and for the third phase (H 2 O 2 ), toluene concentrations were about 1 ppm after only 5 days. Initial results suggest that this method could be an effective means of remediating a contaminated site, directly after a BTEX spill, without the intrusiveness and high cost of other abatement technologies such as bioventing or soil-vapor extraction. However, further tests need to be completed to determine the effect of each of the BTEX components.

Water, Air, & Soil Pollution↗

USGS2015

Spatial and temporal migration of a landfill leachate plume in alluvium

Leachate from unlined or leaky landfills can create groundwater contaminant plumes that last decades to centuries. Understanding the dynamics of leachate movement in space and time is essential for monitoring, planning and management, and assessment of risk to groundwater and surface-water resources. Over a 23.4-year period (1986–2010), the spatial extent of the Norman Landfill leachate plume increased at a rate of 7800 m 2 /year and expanded by 878 %, from an area of 20,800 m 2 in 1986 to 203,400 m 2 in 2010. A linear plume velocity of 40.2 m/year was calculated that compared favorably to a groundwater-seepage velocity of 55.2 m/year. Plume-scale hydraulic conductivity values representative of actual hydrogeological conditions in the alluvium ranged from 7.0 × 10 −5 to 7.5 × 10 −4 m/s, with a median of 2.0 × 10 −4 m/s. Analyses of field-measured and calculated plume-scale hydraulic conductivity distributions indicate that the upper percentiles of field-measured values should be considered to assess rates of plume-scale migration, spreading, and biodegradation. A pattern of increasing Cl − concentrations during dry periods and decreasing Cl − concentrations during wet periods was observed in groundwater beneath the landfill. The opposite occurred in groundwater downgradient from the landfill; that is, Cl − concentrations in groundwater downgradient from the landfill decreased during dry periods and increased during wet periods. This pattern of changing Cl − concentrations in response to wet and dry periods indicates that the landfill retains or absorbs leachate during dry periods and produces lower concentrated leachate downgradient. During wet periods, the landfill receives more recharge which dilutes leachate in the landfill but increases leachate migration from the landfill and produces a more concentrated contaminant plume. This approach of quantifying plume expansion, migration, and concentration during variable hydrologic conditions provides increased understanding of plume behavior and migration potential and may be applied at less monitored landfill sites to evaluate potential risks of contamination to downgradient receptors.

Water, Air, & Soil Pollution↗

USGS2016

Transport of atrazine versus bromide and δO18 in sand

The objective of this research was to determine the process of atrazine transport compared to bromide and δO 18 transport in sands near Denver. Three 1.5 × 2 × 1.5-m plots were installed and allowed to equilibrate for 2 years before research initiation and were instrumented with 1.5 × 2-m zero-tension pan lysimeters installed at 1.5-m depths. Additionally, each plot was instrumented with suction lysimeters, tensiometers, time domain reflectometry (TDR) moisture probes, and thermocouples (to measure soil temperature) at 15-cm depth increments. All plots were enclosed with a raised frame (of 8-cm height) to prevent surface runoff. During the 2-year period before research began, all suction and pan lysimeters were purged monthly and were sampled for fluids immediately prior to atrazine and KBr application to obtain background concentrations. Atrazine illustrated little movement until after a significant rainfall event, which peaked concentrations at depths of about 90 to 135 cm. Both Br − and δO 18 moved rapidly through the soil, probably owing to soil porosity and anion exclusion for Br − . Concentrations of atrazine exceeding 5.0 μL −1 were observed with depth (90 to 150 cm) after several months. It appears that significant rainfall events were a key factor in the movement of atrazine in the sand, which allowed the chemicals to move to greater depths and thus avoid generally found biodegradation processes.

Water, Air, & Soil Pollution↗

USGS1990

Movement and fate of atrazine and bromide in central Kansas croplands

Two flooding experiments were conducted at two sites with different soils to study the transport and fate of the commonly used herbicide atrazine and inorganic chemicals in the Great Bend Prairie croplands of south-central Kansas. The instantaneous profile method supplemented by the use of an organic (atrazine) and an inorganic (bromide) tracer chemical was used to characterize in situ the hydraulic and chemical properties of the appropriately instrumented field sites. Atrazine readily degraded to hydroxyatrazine and biodegradation by-products and was not detected deeper in the soil profile and underlying shallow aquifer. The classical processes of chemical movement based on porous media-equilibrium-diffuse flow did not fit the data well at either site. Incompletely mixed, slug flow appeared to predominate at one of the sites and preferential flow at the other. The slug movement caused 'piston-type' displacement of more saline solutions in the soil profile to the shallow water table. Recommendations for conducting related field studies based on our sampling experience are given.

Kansas↗

USGS1993

Geochemical evaluation of upper cretaceous fruitland formation coals, San Juan Basin, New Mexico and Colorado

Geochemical analyses of coal samples from the Upper Cretaceous Fruitland Formation in the San Juan Basin of New Mexico and Colorado were used to determine thermal maturity, type of kerogen, and hydrocarbon generation potential. Mean random vitrinite reflectance (% R m ) of the Fruitland coal ranges from 0.42 to 1.54%. Rock-Eval pyrolysis data and saturated to aromatic hydrocarbon ratio indicate that the onset of thermal hydrocarbon generation begins at about 0.60% R m and peak generation occurs at about 0.85% R m . Several samples have hydrogen index values between 200 and 400, indicating some potential for liquid hydrocarbon generation and a mixed Type III and II kerogen. Pentacyclic and tricyclic terpanes, steranes, aromatic steroids and methylphenanthrene maturity parameters were observed through the complete range of thermal maturity in the Fruitland coals. Aromatic pentacyclic terpanes, similar to those found in brown coals of Australia, were observed in low maturity samples, but not found above 0.80% R m . N -alkane depleted coal samples, which occur at a thermal maturity of approx. 0.90% R m , paralleling peak hydrocarbon generation, are fairly widespread throughout the basin. Depletion of n -alkanes in these samples may be due to gas solution stripping and migration fromthe coal seams coincident with the development of pressure induced fracturing due to hydrocarbon generation; however, biodegradation may also effect these samples.

Colorado, New Mexico↗

USGS1993

Modeling steady-state methanogenic degradation of phenols in groundwater

Field and microcosm observations of methanogenic phenolic compound degradation indicate that Monod kinetics governs the substrate disappearance but overestimates the observed biomass. In this paper we present modeling results from an ongoing multidisciplinary study of methanogenic biodegradation of phenolic compounds in a sand and gravel aquifer contaminated by chemicals and wastes used in wood treatment. Field disappearance rates of four phenols match those determined in batch microcosm studies previously performed by E.M. Godsy and coworkers. The degradation process appears to be at steady-state because even after a sustained influx over several decades, the contaminants still are disappearing in transport downgradient. The existence of a steady-state degradation profile of each substrate together with a low biomass density in the aquifer indicate that the bacteria population is exhibiting no net growth. This may be due to the oligotrophic nature of the biomass population in which utilization and growth are approximately independent of concentration for most of the concentration range. Thus a constant growth rate should exist over much of the contaminated area which may in turn be balanced by an unusually high decay or maintenance rate due to hostile conditions or predation.

Journal of Contaminant Hydrology↗

USGS1993

Crude oil in a shallow sand and gravel aquifer—I. Hydrogeology and inorganic geochemistry

Changes in the distribution of inorganic solutes in a shallow ground water contaminated by crude oil document a series of geochemical reactions initiated by biodegradation of the oil. Upgradient of an oil body floating on the water table, oxidation of oil to carbonic acid dissolves carbonate minerals in the aquifer matrix. In this oxidized zone pH is depressed &sim;1 pH unit, and the concentrations of Ca, Mg and HCO 3 − increase to more than twice that of the native ground water. In the anoxic zone beneath the oil body concentrations of dissolved SiO 2 , Sr, K, Fe and Mn increase significantly. Here, Fe is mobilized by microbial reduction, pH is buffered by the carbonate system, and silicates weather via hydrolysis and organic-acid-enhanced dissolution. Farther down-gradient the ground water is reoxygenated and Fe precipitates from solution, possibly as iron hydroxide or iron carbonates, while SiO 2 precipitates as amorphous silica. Other solutes, such as Mg, are transported more conservatively down-gradient where contaminated and native ground water mix. The observed changes in inorganic aqueous chemistry document changes in water-mineral interactions caused by the presence of an organic contaminant. These organic-initiated interactions are likely present in many contaminated aquifers and may be analogous to interactions occurring in other organic-rich natural waters.

Minnesota↗

USGS2014

Fate of injected CO2 in the Wilcox Group, Louisiana, Gulf Coast Basin: Chemical and isotopic tracers of microbial–brine–rock–CO2 interactions

The “2800’ sandstone” of the Olla oil field is an oil and gas-producing reservoir in a coal-bearing interval of the Paleocene–Eocene Wilcox Group in north-central Louisiana, USA. In the 1980s, this producing unit was flooded with CO 2 in an enhanced oil recovery (EOR) project, leaving &sim;30% of the injected CO 2 in the 2800’ sandstone post-injection. This study utilizes isotopic and geochemical tracers from co-produced natural gas, oil and brine to determine the fate of the injected CO 2 , including the possibility of enhanced microbial conversion of CO 2 to CH 4 via methanogenesis. Stable carbon isotopes of CO 2 , CH 4 and DIC, together with mol% CO 2 show that 4 out of 17 wells sampled in the 2800’ sandstone are still producing injected CO 2 . The dominant fate of the injected CO 2 appears to be dissolution in formation fluids and gas-phase trapping. There is some isotopic and geochemical evidence for enhanced microbial methanogenesis in 2 samples; however, the CO 2 spread unevenly throughout the reservoir, and thus cannot explain the elevated indicators for methanogenesis observed across the entire field. Vertical migration out of the target 2800’ sandstone reservoir is also apparent in 3 samples located stratigraphically above the target sand. Reservoirs comparable to the 2800’ sandstone, located along a 90-km transect, were also sampled to investigate regional trends in gas composition, brine chemistry and microbial activity. Microbial methane, likely sourced from biodegradation of organic substrates within the formation, was found in all oil fields sampled, while indicators of methanogenesis (e.g. high alkalinity, δ 13 C-CO 2 and δ 13 C-DIC values) and oxidation of propane were greatest in the Olla Field, likely due to its more ideal environmental conditions (i.e. suitable range of pH, temperature, salinity, sulfate and iron concentrations).

Louisiana↗

USGS2018

Regional patterns in the geochemistry of oil-field water, southern San Joaquin Valley, California, USA

Chemical and isotopic data for water co-extracted with hydrocarbons in oil and gas fields are commonly used to examine the source of the formation water and possible impacts on groundwater in areas of oil and gas development. Understanding the geochemical variability of oil-field water could help to evaluate its origin and delineate possible contamination of shallow aquifers in cases where oil-field water is released to the environment. Here we report geochemical and multiple isotope (H, C, O, Sr, Ra) data from 22 oil wells, three sources of produced water that are disposed of in injection wells, and two surface disposal ponds in four oil fields in the southern San Joaquin Valley, California (Fruitvale, Lost Hills, North and South Belridge). Correlations between Cl and δ 18 O, as well as other ions, and gradual increases in salinity with depth, indicate dilution of one or more saline end-members by meteoric water. The saline end-members, represented by deep samples (610 m–2621 m) in three oil-bearing zones, are characterized by Na Cl composition, near-seawater Cl concentrations (median 20,000 mg/L), enriched δ 18 O H 2 O (median 3.4‰), high ammonium(up to 460 mg-N/L), and relatively high radium activity ( 226 Ra+ 228 Ra = 12.3 Bq/L). The deepest sample has low Na/Cl (0.74), high Ca/Mg (5.0), and low 87 Sr/ 86 Sr (0.7063), whereas the shallower samples have higher Na/Cl (0.86–1.2), Ca/Mg near 1, and higher 87 Sr/ 86 Sr (∼0.7083). The data are consistent with an original seawater source being modified by various depth and lithology dependent diagenetic processes. Dilution by meteoric water occurs naturally on the east side of the valley, and in association with water-injectionactivities on the west side. Meteoric-water flushing, particularly on the east side, results in lower solute concentrations (minimum total dissolved solids 2730 mg/L) and total radium (minimum 0.27 Bq/L) in oil-field water, and promotes biodegradation of dissolved organic carbon and hydrocarbon gases like propane. Acetate concentrations and δ 13 C of dissolved inorganic carbon indicate biogenic methane production occurs in some shallow oil zones. Natural and human processes produce substantial variability in the geochemistry of oil-field water that should be considered when evaluating mixing between oil-field waters and groundwater. The variability could result in uncertainty as to detecting the potential source and impact of oil-field water on groundwater.

California↗

USGS2013

Long-term groundwater contamination after source removal—The role of sorbed carbon and nitrogen on the rate of reoxygenation of a treated-wastewater plume on Cape Cod, MA, USA

The consequences of groundwater contamination can remain long after a contaminant source has been removed. Documentation of natural aquifer recoveries and empirical tools to predict recovery time frames and associated geochemical changes are generally lacking. This study characterized the long-term natural attenuation of a groundwater contaminant plume in a sand and gravel aquifer on Cape Cod, Massachusetts, after the removal of the treated-wastewater source. Although concentrations of dissolved organic carbon (DOC) and other soluble constituents have decreased substantially in the 15 years since the source was removed, the core of the plume remains anoxic and has sharp redox gradients and elevated concentrations of nitrate and ammonium. Aquifer sediment was collected from near the former disposal site at several points in time and space along a 0.5-km-long transect extending downgradient from the disposal site and analyses of the sediment was correlated with changes in plume composition. Total sediment carbon content was generally low (< 8 to 55.8 μmol (g dry wt)− 1) but was positively correlated with oxygen consumption rates in laboratory incubations, which ranged from 11.6 to 44.7 nmol (g dry wt)− 1 day− 1. Total water extractable organic carbon was < 10–50% of the total carbon content but was the most biodegradable portion of the carbon pool. Carbon/nitrogen (C/N) ratios in the extracts increased more than 10-fold with time, suggesting that organic carbon degradation and oxygen consumption could become N-limited as the sorbed C and dissolved inorganic nitrogen (DIN) pools produced by the degradation separate with time by differential transport. A 1-D model using total degradable organic carbon values was constructed to simulate oxygen consumption and transport and calibrated by using observed temporal changes in oxygen concentrations at selected wells. The simulated travel velocity of the oxygen gradient was 5–13% of the groundwater velocity. This suggests that the total sorbed carbon pool is large relative to the rate of oxygen entrainment and will be impacting groundwater geochemistry for many decades. This has implications for long-term oxidation of reduced constituents, such as ammonium, that are being transported downgradient away from the infiltration beds toward surface and coastal discharge zones.

Massachusetts↗

USGS2014

Presence of the Corexit component dioctyl sodium sulfosuccinate in Gulf of Mexico waters after the 2010 Deepwater Horizon oil spill

Between April 22 and July 15, 2010, approximately 4.9 million barrels of oil were released into the Gulf of Mexico from the Deepwater Horizon oil well. Approximately 16% of the oil was chemically dispersed, at the surface and at 1500 m depth, using Corexit 9527 and Corexit 9500, which contain dioctyl sodium sulfosuccinate (DOSS) as a major surfactant component. This was the largest documented release of oil in history at substantial depth, and the first time large quantities of dispersant (0.77 million gallons of approximately 1.9 million gallons total) were applied to a subsurface oil plume. During two cruises in late May and early June, water samples were collected at the surface and at depth for DOSS analysis. Real-time fluorimetry data was used to infer the presence of oil components to select appropriate sampling depths. Samples were stored frozen and in the dark for approximately 6 months prior to analysis by liquid chromatography/tandem mass spectrometry with isotope-dilution quantification. The blank-limited method detection limit (0.25 μg L −1 ) was substantially less than the U.S. Environmental Protection Agency’s (USEPA) aquatic life benchmark of 40 μg L −1 . Concentrations of DOSS exceeding 200 μg L −1 were observed in one surface sample near the well site; in subsurface samples DOSS did not exceed 40 μg L −1 . Although DOSS was present at high concentration in the immediate vicinity of the well where it was being continuously applied, a combination of biodegradation, photolysis, and dilution likely reduced persistence at concentrations exceeding the USEPA aquatic life benchmark beyond this immediate area.

Gulf Of Mexico↗

USGS2022

Enhanced bioremediation of RDX and co-contaminants perchlorate and nitrate using an anaerobic dehalogenating consortium in a fractured rock aquifer

The potential neurotoxic and carcinogenic effects of the explosives compound RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) on human health requires groundwater remediation strategies to meet low cleanup goals. Bioremediation of RDX is feasible through biostimulation of native microbes with an organic carbon donor but may be less efficient, or not occur at all, in the presence of the common co-contaminants perchlorate and nitrate. Laboratory tests compared biostimulation with bioaugmentation to achieve anaerobic degradation of RDX, perchlorate, and nitrate; a field pilot test was then conducted in a fractured rock aquifer with the selected bioaugmentation approach. Insignificant reduction of RDX, perchlorate, or nitrate was observed by the native microbes in microcosms, with or without biostimulation by addition of lactate. Tests of the RDX-degrading ability of the microbial consortium WBC-2, originally developed for dehalogenation of chlorinated volatile organic compounds, showed first-order biodegradation rate constants ranging from 0.57 to 0.90 per day (half-lives 1.2 to 0.80 days). WBC-2 sustained degradation without daughter product accumulation when repeatedly amended with RDX and lactate for a year. In microcosms with groundwater containing perchlorate and nitrate, RDX degradation began without delay when bioaugmented with 10% WBC-2. Slower RDX degradation occurred with 3% or 5% WBC-2 amendment, indicating a direct relation with cell density. Transient RDX daughter compounds included methylene dinitramine, MNX, and DNX. With WBC-2 amendment, nitrate concentrations immediately decreased to near or below detection, and perchlorate degradation occurred with half-lives of 25 to 34 days. Single-well injection tests with WBC-2 and lactate showed that the onset of RDX degradation coincided with the onset of sulfide production, which was affected by the initial perchlorate concentration. Bioegradation rates in the pilot injection tests agreed well with those measured in the microcosms. These results support bioaugmentation with an anaerobic culture as a remedial strategy for sites contaminated with RDX, nitrate, and perchlorate.

New Mexico↗

USGS2008

Biogenic origin of coalbed gas in the northern Gulf of Mexico Coastal Plain, U.S.A

New coal-gas exploration and production in northern Louisiana and south-central Mississippi, Gulf of Mexico Basin, is focused on the Wilcox Group (Paleocene–Eocene), where the depth to targeted subbituminous C to high volatile C bituminous coal beds ranges from 300 to 1680 m, and individual coal beds have a maximum thickness of about 6 m. Total gas content (generally excluding residual gas) of the coal beds ranges from less than 0.37 cm 3 /g (as-analyzed or raw basis; 1.2 cm 3 /g, dry, ash free basis, daf) at depths less than 400 m, to greater than 7.3 cm 3 /g (as-analyzed basis; 8.76 cm 3 /g, daf) in deeper (> 1,500 m) parts of the basin. About 20 Wilcox coal-gas wells in northern Louisiana produce from 200 to 6485 m 3 of gas/day and cumulative gas production from these wells is approximately 25 million m 3 (as of December, 2006). U.S. Geological Survey assessment of undiscovered, technically recoverable gas resources in the Gulf of Mexico Coastal Plain, including northern and south-central Mississippi, indicates that coal beds of the Wilcox Group contain an estimated mean total 109.3 million m 3 (3.86 trillion ft 3 ) of producible natural gas. To determine the origin of the Wilcox Group coal gases in northern Louisiana, samples of gas, water, and oil were collected from Wilcox coal and sandstone reservoirs and from under- and overlying Late Cretaceous and Eocene carbonate and sandstone reservoirs. Isotopic data from Wilcox coal-gas samples have an average δ 13 C CH4 value of − 62.6‰ VPDB (relative to Vienna Peedee Belemnite) and an average δ D CH4 value of − 199.9‰ VSMOW (relative to Vienna Standard Mean Ocean Water). Values of δ 13 C CO2 range from − 25.4 to 3.42‰ VPDB. Produced Wilcox saline water collected from oil, conventional gas, and coalbed gas wells have δ D H2O values that range from − 27.3 to − 18.0‰ VSMOW. These data suggest that the coal gases primarily are generated in saline formation water by bacterial reduction of CO 2 . Shallow (< 150 m) Wilcox coal beds containing freshwater have little or no biogenic gas. Molecular and isotopic analyses of gas samples collected from conventional gas and oil wells suggests that both biogenic and thermogenic gases are present in and adjacent to the Wilcox intervals that contain biogenic coal gases. Oil, probably sourced from thermally mature, down-structural-dip parts of the Wilcox Group, is produced from sandstones within the coal-bearing interval. Gas chromatograms of C 10+ saturated hydrocarbons from Wilcox oils show a depletion of n -alkanes probably resulting from biodegradation of the oil. Isotopic composition of the gases associated with the oils is of mixed themogenic and biogenic origin (average δ 13 C CH4 = − 44.4‰ VPDB, and average δ D CH4 = − 182.4‰ VSMOW).

International Journal of Coal Geology↗

USGS2013

Evaluation of the rhenium-osmium geochronometer in the Phosphoria petroleum system, Bighorn Basin of Wyoming and Montana, USA

Rhenium-osmium (Re-Os) geochronometry is applied to crude oils derived from the Permian Phosphoria Formation of the Bighorn Basin in Wyoming and Montana to determine whether the radiogenic age reflects the timing of petroleum generation, timing of migration, age of the source rock, or the timing of thermochemical sulfate reduction (TSR). The oils selected for this study are interpreted to be derived from the Meade Peak Phosphatic Shale and Retort Phosphatic Shale Members of the Phosphoria Formation based on oil-oil and oil-source rock correlations utilizing bulk properties, elemental composition, δ 13 C and δ 34 S values, and biomarker distributions. The δ 34 S values of the oils range from -6.2‰ to +5.7‰, with oils heavier than -2‰ interpreted to be indicative of TSR. The Re and Os isotope data of the Phosphoria oils plot in two general trends: (1) the main trend (n = 15 oils) yielding a Triassic age (239 ± 43 Ma) with an initial 187 Os/ 188 Os value of 0.85 ± 0.42 and a mean square weighted deviation (MSWD) of 1596, and (2) the Torchlight trend (n = 4 oils) yielding a Miocene age (9.24 ± 0.39 Ma) with an initial 187Os/188Os value of 1.88 ± 0.01 and a MSWD of 0.05. The scatter (high MSWD) in the main-trend regression is due, in part, to TSR in reservoirs along the eastern margin of the basin. Excluding oils that have experienced TSR, the regression is significantly improved, yielding an age of 211 ± 21 Ma with a MSWD of 148. This revised age is consistent with some studies that have proposed Late Triassic as the beginning of Phosphoria oil generation and migration, and does not seem to reflect the source rock age (Permian) or the timing of re-migration (Late Cretaceous to Eocene) associated with the Laramide orogeny. The low precision of the revised regression (±21 Ma) is not unexpected for this oil family given the long duration of generation from a large geographic area of mature Phosphoria source rock, and the possible range in the initial 187 Os/ 188 Os values of the Meade Peak and Retort source units. Effects of re-migration may have contributed to the scatter, but thermal cracking and biodegradation likely have had minimal or no effect on the main-trend regression. The four Phosphoria-sourced oils from Torchlight and Lamb fields yield a precise Miocene age Re-Os isochron that may reflect the end of TSR in the reservoir due to cooling below a threshold temperature in the last 10 m.y. from uplift and erosion of overlying rocks. The mechanism for the formation of a Re-Os isotopic relationship in a family of crude oils may involve multiple steps in the petroleum generation process. Bitumen generation from the source rock kerogen may provide a reset of the isotopic chronometer, and incremental expulsion of oil over the duration of the oil window may provide some of the variation seen in 187 Re/ 188 Os values from an oil family.

Montana, Wyoming↗