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Results for “Journal of Contaminant Hydrology”

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At least 73 records · Page 4Linked to original sources
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↗
USGS2012

Time series geophysical monitoring of permanganate injections and in situ chemical oxidation of PCE, OU1 area, Savage Superfund Site, Milford, NH, USA

In situ chemical oxidation (ISCO) treatment with sodium permanganate, an electrically conductive oxidant, provides a strong electrical signal for tracking of injectate transport using time series geophysical surveys including direct current (DC) resistivity and electromagnetic (EM) methods. Effective remediation is dependent upon placing the oxidant in close contact with the contaminated aquifer. Therefore, monitoring tools that provide enhanced tracking capability of the injectate offer considerable benefit to guide subsequent ISCO injections. Time-series geophysical surveys were performed at a superfund site in New Hampshire, USA over a one-year period to identify temporal changes in the bulk electrical conductivity of a tetrachloroethylene (PCE; also called tetrachloroethene) contaminated, glacially deposited aquifer due to the injection of sodium permanganate. The ISCO treatment involved a series of pulse injections of sodium permanganate from multiple injection wells within a contained area of the aquifer. After the initial injection, the permanganate was allowed to disperse under ambient groundwater velocities. Time series geophysical surveys identified the downward sinking and pooling of the sodium permanganate atop of the underlying till or bedrock surface caused by density-driven flow, and the limited horizontal spread of the sodium permanganate in the shallow parts of the aquifer during this injection period. When coupled with conventional monitoring, the surveys allowed for an assessment of ISCO treatment effectiveness in targeting the PCE plume and helped target areas for subsequent treatment.

New Hampshire↗
USGS2013

Electrical signatures of ethanol-liquid mixtures: implications for monitoring biofuels migration in the subsurface

Ethanol (EtOH), an emerging contaminant with potential direct and indirect environmental effects, poses threats to water supplies when spilled in large volumes. A series of experiments was directed at understanding the electrical geophysical signatures arising from groundwater contamination by ethanol. Conductivity measurements were performed at the laboratory scale on EtOH–water mixtures (0 to 0.97 v/v EtOH) and EtOH–salt solution mixtures (0 to 0.99 v/v EtOH) with and without a sand matrix using a conductivity probe and a four-electrode electrical measurement over the low frequency range (1–1000 Hz). A Lichtenecker–Rother (L–R) type mixing model was used to simulate electrical conductivity as a function of EtOH concentration in the mixture. For all three experimental treatments increasing EtOH concentration resulted in a decrease in measured conductivity magnitude (|σ|). The applied L–R model fitted the experimental data at concentration ≤ 0.4 v/v EtOH, presumably due to predominant and symmetric intermolecular (EtOH–water) interaction in the mixture. The deviation of the experimental |σ| data from the model prediction at higher EtOH concentrations may be associated with hydrophobic effects of EtOH–EtOH interactions in the mixture. The |σ| data presumably reflected changes in relative strength of the three types of interactions (water–water, EtOH–water, and EtOH–EtOH) occurring simultaneously in EtOH–water mixtures as the ratio of EtOH to water changed. No evidence of measurable polarization effects at the EtOH–water and EtOH–water–mineral interfaces over the investigated frequency range was found. Our results indicate the potential for using electrical measurements to characterize and monitor EtOH spills in the subsurface.

Journal of Contaminant Hydrology↗
USGS2013

Complex resistivity signatures of ethanol in sand-clay mixtures

We performed complex resistivity (CR) measurements on laboratory columns to investigate changes in electrical properties as a result of varying ethanol (EtOH) concentration (0% to 30% v/v) in a sand–clay (bentonite) matrix. We applied Debye decomposition, a phenomenological model commonly used to fit CR data, to determine model parameters (time constant: τ, chargeability: m, and normalized chargeability: m n ). The CR data showed a significant (P ≤ 0.001) time-dependent variation in the clay driven polarization response (~ 12 mrad) for 0% EtOH concentration. This temporal variation probably results from the clay–water reaction kinetics trending towards equilibrium in the sand–clay–water system. The clay polarization is significantly suppressed (P ≤ 0.001) for both measured phase (ϕ) and imaginary conductivity (σ″) with increasing EtOH concentration. Normalized chargeability consistently decreases (by up to a factor of ~ 2) as EtOH concentration increases from 0% to 10% and 10 to 20%, respectively. We propose that such suppression effects are associated with alterations in the electrical double layer (EDL) at the clay–fluid interface due to (a) strong EtOH adsorption on clay, and (b) complex intermolecular EtOH–water interactions and subsequent changes in ionic mobility on the surface in the EDL. Changes in the CR data following a change of the saturating fluid from EtOH 20% to plain water indicate strong hysteresis effects in the electrical response, which we attribute to persistent EtOH adsorption on clay. Our results demonstrate high sensitivity of CR measurements to clay–EtOH interactions in porous media, indicating the potential application of this technique for characterization and monitoring of ethanol contamination in sediments containing clays.

Journal of Contaminant Hydrology↗
USGS2013

Complex resistivity signatures of ethanol biodegradation in porous media

Numerous adverse effects are associated with the accidental release of ethanol (EtOH) and its persistence in the subsurface. Geophysical techniques may permit non-invasive, real time monitoring of microbial degradation of hydrocarbon. We performed complex resistivity (CR) measurements in conjunction with geochemical data analysis on three microbial-stimulated and two control columns to investigate changes in electrical properties during EtOH biodegradation processes in porous media. A Debye Decomposition approach was applied to determine the chargeability ( m ), normalized chargeability ( m n ) and time constant ( τ ) of the polarization magnitude and relaxation length scale as a function of time. The CR responses showed a clear distinction between the bioaugmented and control columns in terms of real ( σ′ ) and imaginary ( σ″ ) conductivity, phase ( ϕ ) and apparent formation factor ( F app ). Unlike the control columns, a substantial decrease in σ′ and increase in F app occurred at an early time (within 4 days) of the experiment for all three bioaugmented columns. The observed decrease in σ′ is opposite to previous studies on hydrocarbon biodegradation. These columns also exhibited increases in ϕ (up to ~ 9 mrad) and σ″ (up to two order of magnitude higher) 5 weeks after microbial inoculation. Variations in m and m n were consistent with temporal changes in ϕ and σ″ responses, respectively. Temporal geochemical changes and high resolution scanning electron microscopy imaging corroborated the CR findings, thus indicating the sensitivity of CR measurements to EtOH biodegradation processes. Our results offer insight into the potential application of CR measurements for long-term monitoring of biogeochemical and mineralogical changes during intrinsic and induced EtOH biodegradation in the subsurface.

Journal of Contaminant Hydrology↗
USGS2014

Integration of stable carbon isotope, microbial community, dissolved hydrogen gas, and 2 H H 2 O tracer data to assess bioaugmentation for chlorinated ethene degradation in fractured rocks

An in situ bioaugmentation (BA) experiment was conducted to understand processes controlling microbial dechlorination of trichloroethene (TCE) in groundwater at the Naval Air Warfare Center (NAWC), West Trenton, NJ. In the BA experiment, an electron donor (emulsified vegetable oil and sodium lactate) and a chloro-respiring microbial consortium were injected into a well in fractured mudstone of Triassic age. Water enriched in 2 H was also injected as a tracer of the BA solution, to monitor advective transport processes. The changes in concentration and the δ 13 C of TCE, cis-dichloroethene (cis-DCE), and vinyl chloride (VC); the δ 2 H of water; changes in the abundance of the microbial communities; and the concentration of dissolved H2 gas compared to pre- test conditions, provided multiple lines of evidence that enhanced biodegradation occurred in the injection well and in two downgradient wells. For those wells where the biodegradation was stimulated intensively, the sum of the molar chlorinated ethene (CE) concentrations in post-BA water was higher than that of the sum of the pre-BA background molar CE concentrations. The concentration ratios of TCE/(cis-DCE + VC) indicated that the increase in molar CE concentration may result from additional TCE mobilized from the rock matrix in response to the oil injection or due to desorption/diffusion. The stable carbon isotope mass-balance calculations show that the weighted average 13 C isotope of the CEs was enriched for around a year compared to the background value in a two year monitoring period, an effective indication that dechlorination of VC was occurring. Insights gained from this study can be applied to efforts to use BA in other fractured rock systems. The study demonstrates that a BA approach can substantially enhance in situ bioremediation not only in fractures connected to the injection well, but also in the rock matrix around the well due to processes such as diffusion and desorption. Because the effect of the BA was intensive only in wells where an amendment was distributed during injection, it is necessary to adequately distribute the amendments throughout the fractured rock to achieve substantial bioremediation. The slowdown in BA effect after a year is due to some extend to the decrease abundant of appropriate microbes, but more likely the decreased concentration of electron donor.

New Jersey↗
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

High-resolution delineation of chlorinated volatile organic compounds in a dipping, fractured mudstone: depth- and strata-dependent spatial variability from rock-core sampling

Synthesis of rock-core sampling and chlorinated volatile organic compound (CVOC) analysis at five coreholes, with hydraulic and water-quality monitoring and a detailed hydrogeologic framework, was used to characterize the fine-scale distribution of CVOCs in dipping, fractured mudstones of the Lockatong Formation of Triassic age, of the Newark Basin in West Trenton, New Jersey. From these results, a refined conceptual model for more than 55 years of migration of CVOCs and depth- and strata-dependent rock-matrix contamination was developed. Industrial use of trichloroethene (TCE) at the former Naval Air Warfare Center (NAWC) from 1953 to 1995 resulted in dense non-aqueous phase liquid (DNAPL) TCE and dissolved TCE and related breakdown products, including other CVOCs, in underlying mudstones. Shallow highly weathered and fractured strata overlie unweathered, gently dipping, fractured strata that become progressively less fractured with depth. The unweathered lithology includes black highly fractured (fissile) carbon-rich strata, gray mildly fractured thinly layered (laminated) strata, and light-gray weakly fractured massive strata. CVOC concentrations in water samples pumped from the shallow weathered and highly fractured strata remain elevated near residual DNAPL TCE, but dilution by uncontaminated recharge, and other natural and engineered attenuation processes, have substantially reduced concentrations along flow paths removed from sources and residual DNAPL. CVOCs also were detected in most rock-core samples in source areas in shallow wells. In many locations, lower aqueous concentrations, compared to rock core concentrations, suggest that CVOCs are presently back-diffusing from the rock matrix. Below the weathered and highly fractured strata, and to depths of at least 50 meters (m), groundwater flow and contaminant transport is primarily in bedding-plane-oriented fractures in thin fissile high-carbon strata, and in fractured, laminated strata of the gently dipping mudstones. Despite more than 18 years of pump and treat (P&T) remediation, and natural attenuation processes, CVOC concentrations in aqueous samples pumped from these deeper strata remain elevated in isolated intervals. DNAPL was detected in one borehole during coring at a depth of 27 m. In contrast to core samples from the weathered zone, concentrations in core samples from deeper unweathered and unfractured strata are typically below detection. However, high CVOC concentrations were found in isolated samples from fissile black carbon-rich strata and fractured gray laminated strata. Aqueous-phase concentrations were correspondingly high in samples pumped from these strata via short-interval wells or packer-isolated zones in long boreholes. A refined conceptual site model considers that prior to P&T remediation groundwater flow was primarily subhorizontal in the higher-permeability near surface strata, and the bulk of contaminant mass was shallow. CVOCs diffused into these fractured and weathered mudstones. DNAPL and high concentrations of CVOCs migrated slowly down in deeper unweathered strata, primarily along isolated dipping bedding-plane fractures. After P&T began in 1995, using wells open to both shallow and deep strata, downward transport of dissolved CVOCs accelerated. Diffusion of TCE and other CVOCs from deeper fractures penetrated only a few centimeters into the unweathered rock matrix, likely due to sorption of CVOCs on rock organic carbon. Remediation in the deep, unweathered strata may benefit from the relatively limited migration of CVOCs into the rock matrix. Synthesis of rock core sampling from closely spaced boreholes with geophysical logging and hydraulic testing improves understanding of the controls on CVOC delineation and informs remediation design and monitoring.

New Jersey, New York, Pennsylvania↗
USGS2015

Peclet number as affected by molecular diffusion controls transient anomalous transport in alluvial aquifer-aquitard complexes

This study evaluates the role of the Peclet number as affected by molecular diffusion in transient anomalous transport, which is one of the major knowledge gaps in anomalous transport, by combining Monte Carlo simulations and stochastic model analysis. Two alluvial settings containing either short- or long-connected hydrofacies are generated and used as media for flow and transport modeling. Numerical experiments show that 1) the Peclet number affects both the duration of the power-law segment of tracer breakthrough curves (BTCs) and the transition rate from anomalous to Fickian transport by determining the solute residence time for a given low-permeability layer, 2) mechanical dispersion has a limited contribution to the anomalous characteristics of late-time transport as compared to molecular diffusion due to an almost negligible velocity in floodplain deposits, and 3) the initial source dimensions only enhance the power-law tail of the BTCs at short travel distances. A tempered stable stochastic (TSS) model is then applied to analyze the modeled transport. Applications show that the time-nonlocal parameters in the TSS model relate to the Peclet number, P e . In particular, the truncation parameter in the TSS model increases nonlinearly with a decrease in P e due to the decrease of the mean residence time, and the capacity coefficient increases with an increase in molecular diffusion which is probably due to the increase in the number of immobile particles. The above numerical experiments and stochastic analysis therefore reveal that the Peclet number as affected by molecular diffusion controls transient anomalous transport in alluvial aquifer–aquitard complexes.

Journal of Contaminant Hydrology↗
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

Non-invasive flow path characterization in a mining-impacted wetland

Time-lapse electrical resistivity (ER) was used to capture the dilution of a seasonal pulse of acid mine drainage (AMD) contamination in the subsurface of a wetland downgradient of the abandoned Pennsylvania mine workings in central Colorado. Data were collected monthly from mid-July to late October of 2013, with an additional dataset collected in June of 2014. Inversion of the ER data shows the development through time of multiple resistive anomalies in the subsurface, which corroborating data suggest are driven by changes in total dissolved solids (TDS) localized in preferential flow pathways. Sensitivity analyses on a synthetic model of the site suggest that the anomalies would need to be at least several meters in diameter to be adequately resolved by the inversions. The existence of preferential flow paths would have a critical impact on the extent of attenuation mechanisms at the site, and their further characterization could be used to parameterize reactive transport models in developing quantitative predictions of remediation strategies.

Colorado↗
USGS2017

The role of alluvial aquifer sediments in attenuating a dissolved arsenic plume

In a crude-oil-contaminated sandy aquifer at the Bemidji site in northern Minnesota, biodegradation of petroleum hydrocarbons has resulted in release of naturally occurring As to groundwater under Fe-reducing conditions. This study used chemical extractions of aquifer sediments collected in 1993 and 2011–2014 to evaluate the relationship between Fe and As in different redox zones (oxic, methanogenic, Fe-reducing, anoxic-suboxic transition) of the contaminated aquifer over a twenty-year period. Results show that 1) the aquifer has the capacity to naturally attenuate the plume of dissolved As, primarily through sorption; 2) Fe and As are linearly correlated in sediment across all redox zones, and a regression analysis between Fe and As reasonably predicted As concentrations in sediment from 1993 using only Fe concentrations; 3) an As-rich “iron curtain,” associated with the anoxic-suboxic transition zone, migrated 30 m downgradient between 1993 and 2013 as a result of the hydrocarbon plume evolution; and 4) silt lenses in the aquifer preferentially sequester dissolved As, though As is remobilized into groundwater from sediment after reducing conditions are established. Using results of this study coupled with historical data, we develop a conceptual model which summarizes the natural attenuation of As and Fe over time and space that can be applied to other sites that experience As mobilization due to an influx of bioavailable organic matter.

Journal of Contaminant Hydrology↗
USGS2017

Porosity and pore size distribution in a sedimentary rock: Implications for the distribution of chlorinated solvents

Characterizing properties of the rock matrix that control retention and release of chlorinated solvents is essential in evaluating the extent of contamination and the application of remediation technologies in fractured rock. Core samples from seven closely spaced boreholes in a mudstone subject to trichloroethene (TCE) contamination were analyzed using Mercury Intrusion Porosimetry to investigate porosity and pore size distribution as a function of mudstone characteristics, and depth and lateral extent in the aquifer; organic carbon content was also evaluated to identify the potential for adsorption. Porosity and retardation factor varied over two orders of magnitude, with the largest porosities and largest retardation factors associated with carbon-rich mudstone layers. Larger porosities were also measured in the shallow rock that has been subject to enhanced groundwater flow. Porosity also varied over more than an order of magnitude in spatially continuous mudstone layers. The analyses of the rock cores indicated that the largest pore diameters may be accessible to entry of the nonaqueous form of TCE. Although the porosity associated with the largest pore diameters is small (~ 0.1%), that volume of TCE can significantly affect the total TCE that is retained in the rock matrix. The dimensions of the largest pore diameters may also be accessible to microbes responsible for reductive dechlorination; however, the small percentage of the pore space that can accommodate microbes may limit the extent of reductive dechlorination in the rock matrix.

Journal of Contaminant Hydrology↗
USGS2018

Relative contributions of microbial and infrastructure heat at a crude oil-contaminated site

Biodegradation of contaminants can increase the temperature in the subsurface due to heat generated from exothermic reactions, making temperature observations a potentially low-cost approach for determining microbial activity. For this technique to gain more widespread acceptance, it is necessary to better understand all the factors affecting the measured temperatures. Biodegradation has been occurring at a crude oil-contaminated site near Bemidji, Minnesota for 39 years, creating a quasi-steady-state plume of contaminants and degradation products. A model of subsurface heat generation and transport helps elucidate the contribution of microbial and infrastructure heating to observed temperature increases at this site. We created a steady-state, two-dimensional, heat transport model using previous-published parameter values for physical, chemical and biodegradation properties. Simulated temperature distributions closely match the observed average annual temperatures measured in the contaminated area at the site within less than 0.2 °C in the unsaturated zone and 0.4 °C in the saturated zone. The model results confirm that the observed subsurface heat from microbial activity is due primarily to methane oxidation in the unsaturated zone resulting in a 3.6 °C increase in average annual temperature. Another important source of subsurface heat is from the active, crude-oil pipelines crossing the site. The pipelines impact temperatures for a distance of 200 m and contribute half the heat. Model results show that not accounting for the heat from the pipelines leads to overestimating the degradation rates by a factor of 1.7, demonstrating the importance of identifying and quantifying all heat sources. The model results also highlighted a zone where previously unknown microbial activity is occurring at the site.

Minnesota↗
USGS2018

Variability of organic carbon content and the retention and release of trichloroethene in the rock matrix of a mudstone aquifer

Contaminants diffusing from fractures into the immobile porosity of the rock matrix are subject to prolonged residence times. Organic contaminants can adsorb onto organic carbonaceous materials in the matrix extending contaminant retention. An investigation of spatial variability of the fraction of organic carbon ( f oc ) is conducted on samples of rock core from seven closely spaced boreholes in a mudstone aquifer contaminated with trichloroethene (TCE). A total of 378 samples were analyzed at depths between 14 and 36 m below land surface. Mudstone units associated with deep water deposition have the largest f oc , with a maximum value of 0.0396, and units associated with shallow water deposition have the smallest f oc . Even though f oc correlates with depositional conditions, f oc still varies over more than an order of magnitude in continuous mudstone layers between boreholes, and there is large variability in f oc over short distances perpendicular to bedding. Simulations of diffusion and linear equilibrium adsorption of TCE using spatially variable f oc in the rock matrix show order of magnitude variability in the adsorbed TCE over short distances in the matrix and residence times extending to hundreds of years following remediation in adjacent fractures. Simulations using average values of f oc do not capture the range of TCE mass that can be retained in a rock matrix characterized by spatially variable f oc . Bounds on TCE mass within the rock matrix can be obtained by simulations with spatially uniform values of f oc equal to the maximum and minimum values of f oc for a given mudstone unit.

New Jersey↗
USGS2019

The complex spatial distribution of trichloroethene and the probability of NAPL occurrence in the rock matrix of a mudstone aquifer

Methanol extractions for chloroethene analyses are conducted on rock samples from seven closely spaced coreholes in a mudstone aquifer that was subject to releases of the nonaqueous phase liquid (NAPL) form of trichloroethene (TCE) between the 1950's and 1990's. Although TCE concentration in the rock matrix over the length of coreholes is dictated by proximity to subhorizontal bedding planefractures, elevated TCE concentrations in the rock matrix are not continuous along the most permeable bedding plane fractures. A complex configuration of subvertical and subhorizontal fractures appears to be responsible for the TCE distribution from prior TCE releases at land surface. Phase partitioning calculations of TCE in the rock matrix show that most TCE is adsorbed to solid surfaces because of the large fraction of organic carbon ( f oc ) in the mudstone. Large TCE content in some cores indicate the likely presence of the NAPL form of TCE in the rock matrix. Using average values of porosity ( n ) and f oc in phase partitioning calculations identifies a number of locations of possible NAPL occurrence in the rock matrix. Samples of mudstone analyzed for n and f oc show variability in these properties over several orders of magnitude. Accounting for this variability in phase partitioning calculations identifies a probability of NAPL occurrence, P NAPL . The spatial variability of P NAPL along coreholes identifies a configuration that may be attributed to a TCE source zone that has evolved after emplacement due to NAPL dissolution, adsorption, and matrix diffusion.

New Jersey↗