Geology topics

Barbara A. Bekins

Publications and source records attributed to Barbara A. Bekins.

At least 37 records · Page 2Linked to original sources

USGS2017

Field-scale observations of a transient geobattery resulting from natural attenuation of a crude oil spill

We present evidence of a geobattery associated with microbial degradation of a mature crude oil spill. Self-potential measurements were collected using a vertical array of nonpolarizing electrodes, starting at the land surface and passing through the smear zone where seasonal water table fluctuations have resulted in the coating of hydrocarbons on the aquifer solids. These passive electrical potential measurements exhibit a dipolar pattern associated with a current source. The anodic and cathodic reactions of this natural battery occur below and above the smear zone, respectively. The smear zone is characterized by high magnetic susceptibility values associated with the precipitation of semiconductive magnetic iron phase minerals as a by-product of biodegradation, facilitating electron transfer between the anode and the cathode. This geobattery response appears to have a transient nature, changing on a monthly scale, probably resulting from chemical and physical changes in subsurface conditions such as water table fluctuations.

Journal of Geophysical Research G: Biogeosciences↗

USGS2017

Extent and persistence of secondary water quality impacts after enhanced reductive bioremediation

Electron donor (ED) addition can be very effective in stimulating enhanced reductive bioremediation (ERB) of a wide variety of groundwater contaminants. However, ERB can result in Secondary Water Quality Impacts (SWQIs) including decreased levels of dissolved oxygen (O 2 ), nitrate (NO 3- ), and sulfate (SO 4 2- ), and elevated levels of dissolved manganese (Mn 2+ ), dissolved iron (Fe 2+ ), methane (CH 4 ), sulfide (S 2- ), organic carbon, and naturally occurring hazardous compounds (e.g., arsenic). Fortunately, this ‘plume’ of impacted groundwater is usually confined within the original contaminant plume and is unlikely to adversely impact potable water supplies. This report summarizes available information on processes controlling the production and natural attenuation of SWQI parameters and can be used as a guide in understanding the magnitude, areal extent, and duration of SWQIs in ERB treatment zones and the natural attenuation of SWQI parameters as the dissolved solutes migrate downgradient with ambient groundwater flow. This information was compiled from a wide variety of sources including a survey and statistical analysis of SWQIs from 47 ERB sites, geochemical model simulations, field studies at sites where organic-rich materials have entered the subsurface (e.g., wastewater, landfill leachate, and hydrocarbon plumes), and basic information on physical, chemical, and biological processes in the subsurface. This information is then integrated to provide a general conceptual model of the major processes controlling SWQI production and attenuation.

Technical Report↗

USGS2016

Crude oil metabolites in groundwater at two spill sites

Two groundwater plumes in north central Minnesota with residual crude oil sources have 20 to 50 mg/L of nonvolatile dissolved organic carbon (NVDOC). These values are over 10 times higher than benzene and two to three times higher than Diesel Range Organics in the same wells. On the basis of previous work, most of the NVDOC consists of partial transformation products from the crude oil. Monitoring data from 1988 to 2015 at one of the sites located near Bemidji, MN show that the plume of metabolites is expanding toward a lakeshore located 335 m from the source zone. Other mass balance studies of the site have demonstrated that the plume expansion is driven by the combined effect of continued presence of the residual crude oil source and depletion of the electron accepting capacity of solid phase iron oxide and hydroxides on the aquifer sediments. These plumes of metabolites are not covered by regulatory monitoring and reporting requirements in Minnesota and other states. Yet, a review of toxicology studies indicates that polar metabolites of crude oil may pose a risk to aquatic and mammalian species. Together the results suggest that at sites where residual sources are present, monitoring of NVDOC may be warranted to evaluate the fates of plumes of hydrocarbon transformation products.

Minnesota↗

USGS2015

Organic contaminant transport and fate in the subsurface: evolution of knowledge and understanding

Toxic organic contaminants may enter the subsurface as slightly soluble and volatile nonaqueous phase liquids (NAPLs) or as dissolved solutes resulting in contaminant plumes emanating from the source zone. A large body of research published in Water Resources Research has been devoted to characterizing and understanding processes controlling the transport and fate of these organic contaminants and the effectiveness of natural attenuation, bioremediation, and other remedial technologies. These contributions include studies of NAPL flow, entrapment, and interphase mass transfer that have advanced from the analysis of simple systems with uniform properties and equilibrium contaminant phase partitioning to complex systems with pore-scale and macroscale heterogeneity and rate-limited interphase mass transfer. Understanding of the fate of dissolved organic plumes has advanced from when biodegradation was thought to require oxygen to recognition of the importance of anaerobic biodegradation, multiple redox zones, microbial enzyme kinetics, and mixing of organic contaminants and electron acceptors at plume fringes. Challenges remain in understanding the impacts of physical, chemical, biological, and hydrogeological heterogeneity, pore-scale interactions, and mixing on the fate of organic contaminants. Further effort is needed to successfully incorporate these processes into field-scale predictions of transport and fate. Regulations have greatly reduced the frequency of new point-source contamination problems; however, remediation at many legacy plumes remains challenging. A number of fields of current relevance are benefiting from research advances from point-source contaminant research. These include geologic carbon sequestration, nonpoint-source contamination, aquifer storage and recovery, the fate of contaminants from oil and gas development, and enhanced bioremediation.

Water Resources Research↗

USGS2015

Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

Anaerobic biodegradation of organic amendments and contaminants in aquifers can trigger secondary water quality impacts that impair groundwater resources. Reactive transport models help elucidate how diverse geochemical reactions control the spatiotemporal evolution of these impacts. Using extensive monitoring data from a crude oil spill site near Bemidji, Minnesota (USA), we implemented a comprehensive model that simulates secondary plumes of depleted dissolved O 2 and elevated concentrations of Mn 2+ , Fe 2+ , CH 4 , and Ca 2+ over a two-dimensional cross section for 30 years following the spill. The model produces observed changes by representing multiple oil constituents and coupled carbonate and hydroxide chemistry. The model includes reactions with carbonates and Fe and Mn mineral phases, outgassing of CH 4 and CO 2 gas phases, and sorption of Fe, Mn, and H + . Model results demonstrate that most of the carbon loss from the oil (70%) occurs through direct outgassing from the oil source zone, greatly limiting the amount of CH 4 cycled down-gradient. The vast majority of reduced Fe is strongly attenuated on sediments, with most (91%) in the sorbed form in the model. Ferrous carbonates constitute a small fraction of the reduced Fe in simulations, but may be important for furthering the reduction of ferric oxides. The combined effect of concomitant redox reactions, sorption, and dissolved CO 2 inputs from source-zone degradation successfully reproduced observed pH. The model demonstrates that secondary water quality impacts may depend strongly on organic carbon properties, and impacts may decrease due to sorption and direct outgassing from the source zone.

Minnesota↗

USGS2015

Relating subsurface temperature changes to microbial activity at a crude oil-contaminated site

Crude oil at a spill site near Bemidji, Minnesota has been undergoing aerobic and anaerobic biodegradation for over 30 years, creating a 150–200 m plume of primary and secondary contaminants. Microbial degradation generates heat that should be measurable under the right conditions. To measure this heat, thermistors were installed in wells in the saturated zone and in water-filled monitoring tubes in the unsaturated zone. In the saturated zone, a thermal groundwater plume originates near the residual oil body with temperatures ranging from 2.9 °C above background near the oil to 1.2 °C down gradient. Temperatures in the unsaturated zone above the oil body were up to 2.7 °C more than background temperatures. Previous work at this site has shown that methane produced from biodegradation of the oil migrates upward and is oxidized in a methanotrophic zone midway between the water table and the surface. Enthalpy calculations and observations demonstrate that the temperature increases primarily result from aerobic methane oxidation in the unsaturated zone above the oil. Methane oxidation rates at the site independently estimated from surface CO 2 efflux data are comparable to rates estimated from the observed temperature increases. The results indicate that temperature may be useful as a low-cost measure of activity but care is required to account for the correct heat-generating reactions, other heat sources and the effects of focused recharge.

Minnesota↗

USGS2015

High-rate injection is associated with the increase in U.S. mid-continent seismicity

An unprecedented increase in earthquakes in the U.S. mid-continent began in 2009. Many of these earthquakes have been documented as induced by wastewater injection. We examine the relationship between wastewater injection and U.S. mid-continent seismicity using a newly assembled injection well database for the central and eastern United States. We find that the entire increase in earthquake rate is associated with fluid injection wells. High-rate injection wells (>300,000 barrels per month) are much more likely to be associated with earthquakes than lower-rate wells. At the scale of our study, a well’s cumulative injected volume, monthly wellhead pressure, depth, and proximity to crystalline basement do not strongly correlate with earthquake association. Managing injection rates may be a useful tool to minimize the likelihood of induced earthquakes.

Science↗

USGS2014

Decadal surface water quality trends under variable climate, land use, and hydrogeochemical setting in Iowa, USA

Understanding how nitrogen fluxes respond to changes in agriculture and climate is important for improving water quality. In the midwestern United States, expansion of corn cropping for ethanol production led to increasing N application rates in the 2000s during a period of extreme variability of annual precipitation. To examine the effects of these changes, surface water quality was analyzed in 10 major Iowa Rivers. Several decades of concentration and flow data were analyzed with a statistical method that provides internally consistent estimates of the concentration history and reveals flow-normalized trends that are independent of year-to-year streamflow variations. Flow-normalized concentrations of nitrate+nitrite-N decreased from 2000 to 2012 in all basins. To evaluate effects of annual discharge and N loading on these trends, multiple conceptual models were developed and calibrated to flow-weighted annual concentrations. The recent declining concentration trends can be attributed to both very high and very low discharge in the 2000s and to the long (e.g., 8 year) subsurface residence times in some basins. Dilution of N and depletion of stored N occurs in years with high discharge. Reduced N transport and increased N storage occurs in low-discharge years. Central Iowa basins showed the greatest reduction in flow-normalized concentrations, likely because of smaller storage volumes and shorter residence times. Effects of land-use changes on the water quality of major Iowa Rivers may not be noticeable for years or decades in peripheral basins of Iowa, and may be obscured in the central basins where extreme flows strongly affect annual concentration trends.

Iowa↗

USGS2014

A mass balance approach to investigating geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

Secondary water quality impacts can result from a broad range of coupled reactions triggered by primary groundwater contaminants. Data from a crude-oil spill research site near Bemidji, MN provide an ideal test case for investigating the complex interactions controlling secondary impacts, including depleted dissolved oxygen and elevated organic carbon, inorganic carbon, CH 4 , Mn, Fe, and other dissolved ions. To better understand these secondary impacts, this study began with an extensive data compilation of various data types, comprising aqueous, sediment, gas, and oil phases, covering a 260 m cross-sectional domain over 30 years. Mass balance calculations are used to quantify pathways that control secondary components, by using the data to constrain the sources and sinks for the important redox processes. The results show that oil constituents other than BTEX (benzene, toluene, ethylbenzene, o -, m - and p -xylenes), including n -alkanes and other aromatic compounds, play significant roles in plume evolution and secondary water quality impacts. The analysis underscores previous results on the importance of non-aqueous phases. Over 99.9% of the Fe 2+ plume is attenuated by immobilization on sediments as Fe(II) and 85–95% of the carbon biodegradation products are outgassed. Gaps identified in carbon and Fe mass balances and in pH buffering mechanisms are used to formulate a new conceptual model. This new model includes direct out-gassing of CH 4 and CO 2 from organic carbon biodegradation, dissolution of directly produced CO 2 , and sorption with H + exchange to improve pH buffering. The identification of these mechanisms extends understanding of natural attenuation of potential secondary impacts at enhanced reductive dechlorination sites, particularly for reduced Fe plumes, produced CH 4 , and pH perturbations.

Minnesota↗

USGS2014

Comparison of surficial CO2 efflux to other measures of subsurface crude oil degradation

At a spill site near Bemidji, Minnesota, crude oil at the water table has been undergoing anaerobic biodegradation for over 30 years. Previous work at this site has shown that methane produced from biodegradation of the oil migrates upward and is oxidized in a methanotrophic zone midway between the water table and the surface. To compare microbial activity measurement methods from multiple locations in the oil body, surficial carbon dioxide efflux, methanogen and methanotroph concentrations, and oil degradation state were collected. Carbon dioxide effluxes over the oil body averaged more than four times those at the background site. Methanotrophic bacteria concentrations measured using pmoA were over 10 5 times higher above the oil-contaminated sediments compared with the background site. Methanogenic archaea measured using mcrA ranged from 10 5 to over 10 7 in the oil and were below detection in the background. Methanogens correlated very well with methanotroph concentrations (r = 0.99), n-alkylcyclohexane losses as a proxy for degradation state (r = − 0.96), and somewhat less well with carbon dioxide efflux (r = 0.92). Carbon dioxide efflux similarly correlated to methanotroph concentrations (r = 0.90) and n-alkylcyclohexane losses (r = − 0.91).

Minnesota↗

USGS2014

Sharp increase in central Oklahoma seismicity 2009-2014 induced by massive wastewater injection

Unconventional oil and gas production provides a rapidly growing energy source; however high-producing states in the United States, such as Oklahoma, face sharply rising numbers of earthquakes. Subsurface pressure data required to unequivocally link earthquakes to injection are rarely accessible. Here we use seismicity and hydrogeological models to show that distant fluid migration from high-rate disposal wells in Oklahoma is likely responsible for the largest swarm. Earthquake hypocenters occur within disposal formations and upper-basement, between 2-5 km depth. The modeled fluid pressure perturbation propagates throughout the same depth range and tracks earthquakes to distances of 35 km, with a triggering threshold of ~0.07 MPa. Although thousands of disposal wells may operate aseismically, four of the highest-rate wells likely induced 20% of 2008-2013 central US seismicity.

Oklahoma↗

USGS2013

Impacts of an ethanol-blended fuel release on groundwater and fate of produced methane: simulation of field observations

In a field experiment at Vandenberg Air Force Base (VAFB) designed to mimic the impact of a small-volume release of E10 (10% ethanol and 90% conventional gasoline), two plumes were created by injecting extracted groundwater spiked with benzene, toluene, and o-xylene, abbreviated BToX (No-Ethanol Lane) and BToX plus ethanol (With-Ethanol Lane) for 283 days. We developed a reactive transport model to understand processes controlling the fate of ethanol and BToX. The model was calibrated to the extensive field dataset and accounted for concentrations of sulfate, iron, acetate, and methane along with iron-reducing bacteria, sulfate-reducing bacteria, fermentative bacteria, and methanogenic archaea. The benzene plume was about 4.5 times longer in the With-Ethanol Lane than in the No-Ethanol Lane. Matching this different behavior in the two lanes required inhibiting benzene degradation in the presence of ethanol. Inclusion of iron reduction with negligible growth of iron-reducers was required to reproduce the observed constant degradation rate of benzene. Modeling suggested that vertical dispersion and diffusion of sulfate from an adjacent aquitard were important sources of sulfate in the aquifer. Matching of methane data required incorporating initial fermentation of ethanol to acetate, methane loss by outgassing, and methane oxidation coupled to sulfate and iron reduction. Simulation of microbial growth using dual Monod kinetics, and including inhibition by more favorable electron acceptors, generally resulted in reasonable yields for microbial growth of 0.01-0.05.

California↗

USGS2013

Petroleum fingerprinting with organic markers

Petroleum fingerprinting is an invaluable tool in forensic geochemistry. This article summarizes applications of fingerprinting in several oil spills and natural oil seepages that we have studied during the last 25 years. It shows how each unique chemical fingerprint can be used to correlate or differentiate oils. Fingerprints can provide information about processes in the environment that impact oils such as weathering and microbial degradation. They can be used to evaluate organic matter that contributed to oils, and classify oils with regard to the geological framework of their source, such as evaluating geological facies, age, lithology, and depositional environment.

Environmental Forensics↗

USGS2012

Book review: Earthquakes and water

It is really nice to see assembled in one place a discussion of the documented and hypothesized hydrologic effects of earthquakes. The book is divided into chapters focusing on particular hydrologic phenomena including liquefaction, mud volcanism, stream discharge increases, groundwater level, temperature and chemical changes, and geyser period changes. These hydrologic effects are inherently fascinating, and the large number of relevant publications in the past decade makes this summary a useful milepost. The book also covers hydrologic precursors and earthquake triggering by pore pressure. A natural need to limit the topics covered resulted in the omission of tsunamis and the vast literature on the role of fluids and pore pressure in frictional strength of faults. Regardless of whether research on earthquake-triggered hydrologic effects ultimately provides insight into the physics of earthquakes, the text provides welcome common ground for interdisciplinary collaborations between hydrologists and seismologists. Such collaborations continue to be crucial for investigating hypotheses about the role of fluids in earthquakes and slow slip. Review info: Earthquakes and Water. By Wang, C.-Y. and Manga, M., 2010. ISBN: 9783642008092, 218 pp.

Geofluids↗

USGS2012

Factors controlling nitrate fluxes in groundwater in agricultural areas

The impact of agricultural chemicals on groundwater quality depends on the interactions of biogeochemical and hydrologic factors. To identify key processes affecting distribution of agricultural nitrate in groundwater, a parsimonious transport model was applied at 14 sites across the U.S. Simulated vertical profiles of NO 3 - , N 2 from denitrification, O 2 , Cl - , and environmental tracers of groundwater age were matched to observations by adjusting the parameters for recharge rate, unsaturated zone travel time, fractions of N and Cl - inputs leached to groundwater, O 2 reduction rate, O 2 threshold for denitrification, and denitrification rate. Model results revealed important interactions among biogeochemical and physical factors. Chloride fluxes decreased between the land surface and water table possibly because of Cl - exports in harvested crops (averaging 22% of land-surface Cl - inputs). Modeled zero-order rates of O 2 reduction and denitrification were correlated. Denitrification rates at depth commonly exceeded overlying O 2 reduction rates, likely because shallow geologic sources of reactive electron donors had been depleted. Projections indicated continued downward migration of NO 3 - fronts at sites with denitrification rates <0.25 mg-N L -1 yr -1 . The steady state depth of NO 3 - depended to a similar degree on application rate, leaching fraction, recharge, and NO 3 - and O 2 reaction rates. Steady state total mass in each aquifer depended primarily on the N application rate. In addition to managing application rates at land surface, efficient water use may reduce the depth and mass of N in groundwater because lower recharge was associated with lower N fraction leached. Management actions to reduce N leaching could be targeted over aquifers with high-recharge and low-denitrification rates.

Water Resources Research↗

USGS2011

Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

High resolution direct-push profiling over short vertical distances was used to investigate CH 4 attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH 4 and CO 2 , and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in δ 13 C CH4 from an average of − 57.6‰ (± 1.7‰) in the methanogenic zone to − 39.6‰ (± 8.7‰) at 105 m downgradient, strongly suggest CH 4 attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5 m below the water table suggesting that transport of O 2 across the water table is leading to aerobic degradation of CH 4 at this interface. Dissolved N 2 concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O 2 through aerobic degradation of CH 4 or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O 2 rich recharge water were important O 2 transport mechanisms.

Journal of Contaminant Hydrology↗

USGS2011

Loss of volatile hydrocarbons from an LNAPL oil source

The light nonaqueous phase liquid (LNAPL) oil pool in an aquifer that resulted from a pipeline spill near Bemidji, Minnesota, was analyzed for volatile hydrocarbons (VHCs) to determine if the composition of the oil remains constant over time. Oil samples were obtained from wells at five locations in the oil pool in an anaerobic part of the glacial outwash aquifer. Samples covering a 21-year period were analyzed for 25 VHCs. Compared to the composition of oil from the pipeline source, VHCs identified in oil from wells sampled in 2008 were 13 to 64% depleted. The magnitude of loss for the VHCs analyzed was toluene ≫ o-xylene, benzene, C 6 and C 10–12 n-alkanes > C 7 –C 9 n-alkanes > m-xylene, cyclohexane, and 1- and 2-methylnaphthalene > 1,2,4-trimethylbenzene and ethylbenzene. Other VHCs including p-xylene, 1,3,5- and 1,2,3-trimethylbenzenes, the tetramethylbenzenes, methyl- and ethyl-cyclohexane, and naphthalene were not depleted during the time of the study. Water–oil and air–water batch equilibration simulations indicate that volatilization and biodegradation is most important for the C 6 –C 9 n-alkanes and cyclohexanes; dissolution and biodegradation is important for most of the other hydrocarbons. Depletion of the hydrocarbons in the oil pool is controlled by: the lack of oxygen and nutrients, differing rates of recharge, and the spatial distribution of oil in the aquifer. The mass loss of these VHCs in the 5 wells is between 1.6 and 7.4% in 29 years or an average annual loss of 0.06–0.26%/year. The present study shows that the composition of LNAPL changes over time and that these changes are spatially variable. This highlights the importance of characterizing the temporal and spatial variabilities of the source term in solute-transport models.

Minnesota↗

USGS2011

Role of back diffusion and biodegradation reactions in sustaining an MTBE/TBA plume in alluvial media

A methyl tert-butyl ether (MTBE) / tert-butyl alcohol (TBA) plume originating from a gasoline spill in late 1994 at Vandenberg Air Force Base (VAFB) persisted for over 15 years within 200 feet of the original spill source. The plume persisted until 2010 despite excavation of the tanks and piping within months after the spill and excavations of additional contaminated sediments from the source area in 2007 and 2008. The probable history of MTBE concentrations along the plume centerline at its source was estimated using a wide variety of available information, including published details about the original spill, excavations and monitoring by VAFB consultants, and our own research data. Two-dimensional reactive transport simulations of MTBE along the plume centerline were conducted for a 20-year period following the spill. These analyses suggest that MTBE diffused from the thin anaerobic aquifer into the adjacent anaerobic silts and transformed to TBA in both aquifer and silt layers. The model reproduces the observation that after 2004 TBA was the dominant solute, diffusing back out of the silts into the aquifer and sustaining plume concentrations much longer than would have been the case in the absence of such diffusive exchange. Simulations also suggest that aerobic degradation of MTBE or TBA at the water table in the overlying silt layer significantly affected concentrations of MTBE and TBA by limiting the chemical mass available for back diffusion to the aquifer.

California↗