An evaluation of permeable reactive barrier projects in California

Permeable reactive barriers made of zero‐valent iron (ZVI PRBs) have become a prominent remediation technology in addressing groundwater contamination by chlorinated solvents. Many ZVI PRBs have been installed across the United States, some as research projects, some at the pilot scale, and many at full scale. As a passive and in situ remediation technology, ZVI PRBs have many attractive features and advantages over other approaches to groundwater remediation. Ten ZVI PRBs installed in California were evaluated for their performance. Of those ten, three are discussed in greater detail to illustrate the complexities that arise when quantifying the performance of ZVI PRBs, and to provide comment on the national debate concerning the downgradient effects of source‐zone removal or treatment on plumes of contaminated groundwater. © 2009 Wiley Periodicals, Inc.     

Chloroethene dechlorination in acidic groundwater: Implications for combining fenton's treatment with natural attenuation

A sulfuric acid leak in 1988 at a chloroethene‐contaminated groundwater site at the Naval Air Station Pensacola has resulted in a long‐term record of the behavior of chloroethene contaminants at low pH and a unique opportunity to assess the potential impact of source area treatment technologies, which involve acidification of the groundwater environment (e.g., Fenton's‐based in situ chemical oxidation), on downgradient natural attenuation processes. The greater than 75 percent decrease in trichloroethene (TCE) concentrations and the shift in contaminant composition toward predominantly reduced daughter products (dichloroethene [DCE] and vinyl chloride [VC]) that were observed along a 30‐m groundwater flow path characterized by highly acidic conditions (pH = 3.5 ± 0.4) demonstrated that chloroethene reductive dechlorination can continue to be efficient under persistent acidic conditions. The detection of Dehalococcoides‐type bacteria within the sulfuric acid/chloroethene co‐contaminant plume was consistent with biotic chloroethene reductive dechlorination. Microcosm studies conducted with ¹⁴C‐TCE and ¹⁴C‐VC confirmed biotic reductive dechlorination in sediment collected from within the sulfuric acid/chloroethene co‐contaminant plume. Microcosms prepared with sediment from two other locations within the acid plume, however, demonstrated only a limited mineralization to ¹⁴CO₂ and ¹⁴CO, which was attributed to abiotic degradation because no significant differences were observed between experimental and autoclaved control treatments. These results indicated that biotic and abiotic mechanisms contributed to chloroethene attenuation in the acid plume at NAS Pensacola and that remediation techniques involving acidification of the groundwater environment (e.g., Fenton's‐based source area treatment) do not necessarily preclude efficient chloroethene degradation. © 2007 Wiley Periodicals, Inc.     

Biochemical Treatment of Hydraulically Complex Hexavalent Chromium and Chlorinated Volatile Organic Plumes

Groundwater contaminated with hexavalent chromium (Cr⁺⁶) and chlorinated volatile organic compounds (cVOCs) presents unique in situ remedial challenges in an oxygen‐rich environment. On one hand, chemical oxidation would be effective in treating the cVOCs; however, it would not be appropriate to treat Cr⁺⁶. Biological treatment may be appropriate to treat the Cr⁺⁶; however, the cVOC degradation pathway within these mixed plumes is currently following an abiotic pathway with little to no daughter‐product production. Thus, a blended approach was needed to treat both constituents in situ in an effort to avoid a long‐term, costly pump‐and‐treat solution. This article evaluates an in situ biogeochemical stabilization/reduction strategy by injecting an inorganic carbon‐based remedial additive into the geologic and hydrogeologic environment to decrease concentrations within the commingled Cr⁺⁶ and cVOC plume. The concept involves creating favorable redox reducing conditions to shift the groundwater geochemical equilibrium from the more toxic Cr⁺⁶ to the less toxic trivalent chromium (Cr⁺³), with the final outcome being a conversion to chrome oxide that molecularly fixes to the soil grains. In addition, reducing conditions developed for chromium reduction should result in an increase in the available natural formation iron that should further enhance the natural abiotic reduction of cVOCs. © 2013 Wiley Periodicals, Inc.     

An In Situ Bioreactor for the Treatment of Petroleum Hydrocarbons in Groundwater

Two pilot tests of an aerobic in situ bioreactor (ISBR) have been conducted at field sites contaminated with petroleum hydrocarbons. The two sites differed with respect to hydrocarbon concentrations. At one site, concentrations were low but persistent, and at the other site concentrations were high enough to be inhibitory to biodegradation. The ISBR unit is designed to enhance biodegradation of hydrocarbons by stimulating indigenous microorganisms. This approach builds on existing Bio‐Sep^® bead technology, which provides a matrix that can be rapidly colonized by the active members of the microbial community and serves to concentrate indigenous degraders. Oxygen and nutrients are delivered to the bioreactor to maintain conditions favorable for growth and reproduction, and contaminated groundwater is treated as it is circulated through the bed of Bio‐Sep^® beads. Groundwater moving through the system also transports degraders released from Bio‐Sep^® beads away from the bioreactor, potentially increasing biodegradation rates throughout the aquifer. Groundwater sampling, Bio‐Traps, and molecular biological tools were used to assess ISBR performance during the two pilot tests. Groundwater monitoring indicated that contaminant concentrations decreased at both sites, and the microbial data suggested that these decreases were due to degradation by indigenous microorganisms rather than dilution or dispersion mechanisms. Taken together, these lines of evidence showed that the ISBR system effectively increased the number and activity of indigenous microbial degraders and enhanced bioremediation at the test sites. © 2013 Wiley Periodicals, Inc.     

Bioremediation of Chlorobenzene-Contaminated Groundwater on Granular Activated Carbon Barriers

During the past decade, various promising technologies have been developed for the decontamination of groundwater insitu which do not require long-term pumping or high energy consumption. One approach is to use funnel and gate technology. In the case described here, the combination of adsorption of contaminants on granular activated carbon (GAC) and its biodegradation is applied to considerably extend the operating time of the filling material in the barrier system. Monochlorobenzene (MCB), a recalcitrant groundwater contaminant under anaerobic conditions, undergoes high-capacity adsorption on GAC up to about 450 mg per gram. Aerobic enrichment cultures, obtained from a contaminated aquifer, were able to mineralize initially adsorbed MCB. In respirometer experiments the rate of carbon dioxide formation was dependent on the equilibrium concentration of MCB. The oxygen consumption of activated carbon by means of autoxidative reactions may delay aerobic biodegradation in GAC filters. The oxygen uptake of pristine activated carbon amounted to 5.6 mg per gram GAC in laboratory column experiments. When GAC was pre-loaded with MCB, autoxidation rates were considerably reduced. Hence, it is advisable not to stimulate the biodegradation of MCB by oxygen supply in GAC biobarriers until after an initial period of solely sorptive MCB removal from the groundwater flow.     

1,4‐Dioxane Treatment Technologies

The chlorinated solvent stabilizer 1,4‐dioxane (DX) has become an unexpected and recalcitrant groundwater contaminant at many sites across the United States. Chemical characteristics of DX, such as miscibility and low sorption potential, enable it to migrate at least as far as the chlorinated solvent from which it often originates. This mobility and recalcitrance has challenged remediation professionals to redesign existing treatment systems and monitoring networks to accommodate widespread contamination. Furthermore, remediation technologies commonly applied to chlorinated solvent co‐contaminants, such as extraction and air stripping or in situ enhanced reductive dechlorination, are relatively ineffective on DX removal. These difficulties in treatment have required the industry to identify, develop, and demonstrate new and innovative technologies and approaches for both ex situ and in situ treatment of this emerging contaminant. Great strides have been made over the past decade in the development and testing of remediation technologies for removal or destruction of DX in groundwater. This article briefly summarizes the fate and transport characteristics of DX that make it difficult to treat, and presents technologies that have been demonstrated to be applicable to groundwater treatment at the field scale.  ©2016 Wiley Periodicals, Inc.     

Evidence for biodegradation and volatilisation of dissolved petroleum hydrocarbons during in situ air sparging in large laboratory columns

Laboratory column experiments run for up to 13 days compared air sparging of groundwater contaminated by dissolved petroleum hydrocarbons in sterile and non-sterile aquifer sediments as well as uncontaminated sediments and groundwater. Loss of dissolved BTEX compounds in the contaminated columns was very rapid, occurring through volatilisation. The majority of the dissolved total organic carbon (TOC) persisted for much longer periods however. A direct comparison between losses from sterile and non-sterile columns suggested a negligible contribution of biodegradation to the removal of TOC. This was difficult to confirm through examination of O₂ utilisation because oxidation of a small amount of reduced sulphur in the aquifer materials was the dominant sink for O₂. Despite this, it was possible to conclude that less than 22% of the removal of TOC was through biodegradation during the first three days of air sparging.     

Utilisation of Supernatants of Pure Cultures of Streptomyces thermocarboxydus NH50 to Reduce Chromium Toxicity and Mobility in Contaminated Soils

Chromium is a heavy metal used in various industrial sectors. Improper handling and storage of chromium-laden effluents or wastes can lead to the pollution of the environment. The most toxic form is the more mobile one: hexavalent chromium Cr(VI). The reduction of Cr(VI) results in the immobilisation of chromium into its less toxic trivalent form Cr(III). This phenomenon may prevent the contamination of groundwater when the soil in the vadose zone is contaminated. Many bacteria have been isolated from contaminated soils and described to reduce Cr(VI) into Cr(III). A new Cr(VI)-reducing strain, identified as a Streptomyces thermocarboxydus,has been isolated and studied in our laboratories for its ability to reduce Cr(VI). This aerobic bacterium, in contrast to other genera described which mediate reduction via enzymes, produces reducing agents into the culture supernatants. Cr(VI) reduction by these substances is accelerated by the presence of small concentration of cupric ions (Cu²⁺). The reducing agent(s) can be easily recovered from the bacterial cultures and used as cell-free solution to treat contaminated soils by an in situ or ex situ processes.     

In situ biofilm barriers: Case study of a nitrate groundwater plume,Albuquerque, New Mexico

A new use for biofilm barriers was developed and successfully applied to treat nitrate‐contaminated groundwater down to drinking water standards. The barrier was created by stimulating indigenous bacteria with injections of molasses as the carbon donor and a combination of yeast extract and trimetaphosphate as nutrients. This injection of amendments results in bacterial growth in the aquifer, which attaches to the sand grains to create a reactive semipermeable biofilm. The biofilm barrier presented in this article reduced the migration of contaminants and provided an active zone for remediation. The cylindrical biobarrier was constructed using eight wells on the perimeter forming a 60‐foot‐diameter reactive biodenitrification region. Another well at the center was installed to continuously extract the treated water. The intent was to produce a continuous source of nitrate‐free water. The system operated for over one year, and during this period, the biobarrier was revived multiple times by reinjecting molasses in the perimeter wells. Nitrate concentrations of treated water decreased from 275 mg/L (as nitrogen) to < 1 mg/L. © 2005 Wiley Periodicals, Inc.     

Groundwater geochemistry diagnostics during in situ ERH remediation

In situ remediation represents a series of challenges in interpreting the monitoring data on remedial progress. Among these challenges are problems in determining the progress of the remediation and the mechanisms responsible, so that the process can be optimized. The release of organic pollutants to groundwater systems and in situ remediation technologies alter the groundwater chemistry, but outside of natural attenuation studies using inorganic chemical analyses as indicators of intrinsic biodegradation, typically little attention has been paid to the changes in inorganic groundwater chemistry. Smith (2008) noted that during an electrical resistance heating remediation that took place at a confidential site in Chicago, a two‐orders‐of‐magnitude increase in chloride concentrations occurred during the remediation. This increase in chloride resulted in a corresponding increase in calcium as a result of what is known as the common ion effect. Carbon dioxide is the gas found in highest concentrations in natural groundwater (Stumm & Morgan, 1981), and its fugacity (partial pressure) corresponds directly with calcium concentrations. Carbon dioxide at supersaturation in groundwater is capable of dissolving organic compounds, such as trichloroethene, facilitating removal of nonaqueous‐phase liquids at temperatures below the boiling point of water. One means of diagnosing these reactions is through the use of compound‐specific isotopic analysis, which is capable of distinguishing between evaporation, biodegradation, and differences in sources. The appropriate diagnosis has the potential to optimize the benefits from these reactions, lower energy costs for removal of nonaqueous‐phase liquids, and direct treatment where it is needed most. © 2010 Wiley Periodicals, Inc.     

Managing the negative impacts of groundwater flow on electrothermal remediation

Rapid groundwater fluxes often influence subsurface temperature distributions during in situ thermal remediation using electrothermal or conduction heating technologies. This study used a numerical approach to evaluate the impact of groundwater flow on electrothermal heating, as well as the effectiveness of several upgradient heat loss management strategies, in a hypothetical treatment volume. Design alternatives using upgradient (i) hydraulic barriers, (ii) physical barriers, and (iii) increased energy input are evaluated. Results indicate that target temperatures can be achieved, despite the presence of local groundwater flow velocities greater than 0.3 m/day, through the careful design and implementation of the alternatives evaluated. However, physical barriers need to be designed to prevent groundwater flow through the heated volume to be effective. Field data from an electrothermal application are also presented, where boiling temperatures were achieved after steam injection and upgradient pumping wells were implemented.     

Assessment of Bacterial Degradation of Aromatic Hydrocarbons in the Environment by Analysis of Stable Carbon Isotope Fractionation

¹³C/¹²C stable carbon isotope fractionation was used to assess biodegradation in contaminated aquifers with toluene as a model compound. Different strains of anaerobic bacteria (Thauera aromatica, Geobacter metallireducens, and the sulfate-reducing strain TRM1) showed consistent ¹³C/¹²C carbon isotope fractionation with fractionation factors between C = 1.0017 and 1.0018. In contrast, three cultures of aerobic organisms, using different mono- and dioxygenase enzyme systems to initiate toluene degradation, showed variable isotope fractionation factors of C = 1.0027 (Pseudomonasputida strain mt-2), C = 1.0011 (Ralstonia picketii), andC = 1.0004 (Pseudomonas putida strain F1). The great variability of isotope fractionation between different aerobic bacterial strains suggests that interpretation of isotope data in oxic habitats can only be qualitative. A soil column was run as a model system for contaminated aquifers with toluene as the carbon source and sulfate as the electron acceptor and samples were taken at different ports along the column. Microbial toluene degradation was calculated based on the ¹³C/¹²C isotope fractionation factors of the batch culture experiments together with the observed ¹³C/¹²C isotope shifts of the residual toluene fractions. The calculated percentage of biodegradation, B, correlated well with the decreasing toluene concentrations at the sampling ports and indicated the increasing extent of biodegradation along the column. The theoretical toluene concentrations as calculated based on the isotope values matched the measured concentrations at the different sampling ports indicating that the Rayleigh equation can be used to calculate biodegradation in quasi closed systems based on measured isotope shifts. A similar attempt was performed to assess toluene degradation in a contaminated, anoxic aquifer. A transect of groundwater wells was monitored along the main direction of the groundwater flow and revealed decreasing concentrations accompanied with an increase in the ¹³C/¹²C stable carbon isotope ratio of the residual toluene. Calculation of the extent of biodegradation based on the isotope values and laboratory derived isotope fractionation factors showed that the residual toluene was degraded to more than 99% by microbial activity. Calculation of the theoretical residual toluene concentrations based on the measured isotope values described the strongly decreasing concentrations along the plume. Other aromatic hydrocarbons like benzene and naphthalene which were analysed in the same course also showed decreasing concentrations along the groundwater flow path accompanied by increasing ¹³C values indicating biodegradation.     

Synthetic Media: A Promising New Treatment Technology for 1,4‐Dioxane

1,4‐Dioxane (14DX) is classified as a probable human carcinogen by the US Environmental Protection Agency (EPA), and it has toxic effects on the kidney and liver. EPA's Health Advisory Level (HAL) for 14DX is 0.35 micrograms per liter (μg/L). Accordingly, several states have lowered their drinking water advisory levels and site cleanup levels. The widespread occurrence of 14DX in contaminated groundwater has contributed to a growing demand for remediation services. Treating 14DX is a challenge due to its very low Henry's law constant, low sorption potential, and strong ether linkages. The primary solution for 14DX remediation has been various forms of advanced oxidation processes (AOP), namely pump and treat followed by ex situ treatment with catalyzed ultraviolet light oxidation or ozone‐peroxidation. Many of the available advanced oxidation systems are complex, requiring careful monitoring and maintenance to adjust for variable source water and operating conditions. Synthetic media is a relatively new 14DX treatment technology that overcomes many of the operating challenges faced by existing technologies. AMBERSORB? 560 (AMBERSORB) has recently demonstrated the effective removal of 14DX over a wide range of concentrations and operating conditions, including those created by in situ thermal remediation. Consistent and reliable treatment down to sub‐0.3 μg/L levels differentiates synthetic media technology from other 14DX treatment technologies. AMBERSORB provides a solution to the problem of “stranded capital” by offering a 14DX treatment system capable of meeting regulatory standards today and in the foreseeable future. © 2014 Wiley Periodicals, Inc.     

The in situ treatment of TCE and PFAS in groundwater within a silty sand aquifer

Chlorinated ethenes such as trichloroethene (TCE), cis‐1,2‐dichloroethene (cis‐1,2‐DCE), and vinyl chloride along with per‐ and polyfluoroalkyl substances (PFAS) have been identified as chemicals of concern in groundwater; with many of the compounds being confirmed as being carcinogens or suspected carcinogens. While there are a variety of demonstrated in‐situ technologies for the treatment of chlorinated ethenes, there are limited technologies available to treat PFAS in groundwater. At a former industrial site shallow groundwater was impacted with TCE, cis‐1,2‐DCE, and vinyl chloride at concentrations up to 985, 258, and 54 µg/L, respectively. The groundwater also contained maximum concentrations of the following PFAS: 12,800 ng/L of perfluoropentanoic acid, 3,240 ng/L of perfluorohexanoic acid, 795 ng/L of perfluorobutanoic acid, 950 ng/L of perfluorooctanoic acid, and 2,140 ng/L of perfluorooctanesulfonic acid. Using a combination of adsorption, biotic, and abiotic degradation in situ remedial approaches, the chemicals of concern were targeted for removal from the groundwater with adsorption being utilized for PFAS whereas adsorption, chemical reduction, and anaerobic biodegradation were used for the chlorinated ethenes. Sampling of the groundwater over a 24‐month period indicated that the detected PFAS were treated to either their detection, or below the analytical detection limit over the monitoring period. Postinjection results for TCE, cis‐1,2‐DCE, and vinyl chloride indicated that the concentrations of the three compounds decreased by an order of magnitude within 4 months of injection, with TCE decreasing to below the analytical detection limit over the 24‐month monitoring period. Cis‐1,2‐DCE, and vinyl chloride concentrations decreased by over 99% within 8 months of injections, remaining at or below these concentrations during the 24‐month monitoring period. Analyses of Dehalococcoides, ethene, and acetylene over time suggest that microbiological and reductive dechlorination were occurring in conjunction with adsorption to attenuate the chlorinated ethenes and PFAS within the aquifer. Analysis of soil cores collected pre‐ and post‐injection, indicated that the distribution of the colloidal activated carbon was influenced by small scale heterogeneities within the aquifer. However, all aquifer samples collected within the targeted injection zone contained total organic carbon at concentrations at least one order of magnitude greater than the preinjection total organic carbon concentrations.     

Detecting and quantifying reductive dechlorination under monitored natural attenuation conditions

Field sampling and testing were used to investigate the relationship between baseline geochemical and microbial community data and in situ reductive dechlorination rates at a site contaminated with trichloroethene (TCE) and carbon tetrachloride (CTET). Ten monitoring wells were selected to represent conditions along groundwater flow paths from the contaminant source zone to a wetlands groundwater discharge zone. Groundwater samples were analyzed for a suite of geochemical and microbial parameters; then push‐pull tests with fluorinated reactive tracers were conducted in each well to measure in situ reductive dechlorination rates. No exogenous electron donors were added in these tests, as the goal was to assess in situ reductive dechlorination rates under natural attenuation conditions. Geochemical data provided preliminary evidence that reductive dechlorination of TCE and CTET was occurring at the site, and microbial data confirmed the presence of known dechlorinating organisms in groundwater. Push‐pull tests were conducted using trichlorofluoroethene (TCFE) as a reactive tracer for TCE and, in one well, trichlorofluoromethane (TCFM) as a reactive tracer for CTET. Injected TCFE was transformed to cis‐ and trans‐dichlorofluoroethene and chlorofluoroethene, and, in one test, injected TCFE was completely dechlorinated to fluoroethene (FE). In situ TCFE transformation rates ranged from less than 0.005 to 0.004/day. In the single well tested, injected TCFM was transformed in situ to dichlorofluoromethane and chlorofluoromethane; the TCFM transformation rate was estimated as 0.001/day. The results indicate that it is possible to use push‐pull tests with reactive tracers to directly detect and quantify reductive dechlorination of chlorinated ethenes and ethanes under monitored natural attenuation conditions, which has not previously been demonstrated. Transformation rate estimates obtained with these techniques should improve the accuracy of contaminant transport modeling. © 2012 Wiley Periodicals, Inc.     

In situ bioremediation of an aniline spill in an industrial setting

In situ remediation of aniline from soils and groundwater using biological and physical treatments was conducted at the BASF Corporation facility in Geismar, Louisiana. To mitigate the migration of aniline, remediate contaminated soil and groundwater, and determine concentrations, 24 immobilized microbe bioreactors were fixed in the subsoil, and a horizontal recovery well and 7 monitoring wells were installed. Soil and monitoring wells were sampled quarterly to assess bioplug impact on the aniline concentrations. The recovery well was sampled monthly to estimate the pounds of aniline removed from groundwater. Soil pH, composition, and microbial counts were used to estimate the fate and transport. Aniline levels were lowered significantly after remediation and total cancer risk was below levels for industrial sites, as established by State of Louisiana Risk Evaluation/Corrective Action Program guidelines. © 2010 Wiley Periodicals, Inc.     

Treatment of an explosives plume in groundwater using an organic mulch biowall

A field demonstration of a mulch permeable reactive barrier (PRB), or “biowall,” as an in situ treatment technology for explosives in groundwater is summarized. Organic mulch consists of insoluble carbon biopolymers that are enzymatically hydrolyzed during decomposition to release aqueous total organic carbon (TOC). The released TOC is then available for microorganisms to use as an electron donor to transform electrophilic contaminants via reductive pathways. A 100‐foot‐long and 2‐foot‐thick mulch biowall was installed at the Pueblo Chemical Army Depot in Colorado to treat a shallow groundwater plume containing hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). To discourage groundwater flow bypassing around and under the biowall in this highly permeable formation, a hydraulic control was installed and the PRB was keyed into the bedrock. Technology performance was monitored using a monitoring well network to establish the development and extent of the downgradient treatment zone. Performance objectives of the field demonstration were: (1) greater than 90 percent removal of RDX across the PRB and the treatment zone; (2) an RDX concentration of less than 0.55 μg/L in the treatment zone; and (3) cumulative toxic intermediate concentration (nitroso intermediates of RDX, MNX, DNX, and TNX) of less than 20 percent of the upgradient RDX concentration. All performance objectives were met within seven months after installation once the system reached a pseudo‐steady state. By this point, a sustained reducing/treatment zone had been created downgradient of the mulch PRB that showed greater than 93 percent RDX removal, RDX concentrations less than 0.55 μg/L, and no accumulation of toxic intermediates. The mulch biowall implemented during this demonstration was successful at meeting performance objectives while addressing the majority of potential concerns of the technology. © 2009 Wiley Periodicals, Inc.     

Integration of the Pesticide Impact Rating Index with a Geographic Information System for the Assessment of Pesticide Impact on Water Quality

The pesticide impact rating index (PIRI) has been integrated with a Geographic Information System (GIS) to enable regional assessment of pesticide impact on groundwater and surface water resources. The GIS version of PIRI (PIRI-GIS) was used to assess the impact of pre-planting atrazine use in the pine plantations on the Gnangara Mound, Western Australia. The impact on groundwater was found to be spatially variable, mainly dependent on soil type and depth to groundwater, because land use variables were spatially constant. Areas with the greatest impact on groundwater were those where the soil had a low sorption capacity for atrazine. Knowledge of the spatial distribution of the sorption coefficient based on organic carbon (K _oc) for atrazine was found to significantly improve the results from PIRI-GIS. Average values for K _oc (i.e. based on overseas data) were too low for most of the local soil types, resulting in a general overestimation of pesticide impact on groundwater resources, but an underestimation of impact in areas that should be of greatest concern (i.e. where the soil has a low sorption capacity for atrazine).     

Estimated trichloroethene transformation rates due to naturally occurring biodegradation in a fractured rock aquifer

Rates of trichloroethene (TCE) mass transformed by naturally occurring biodegradation processes in a fractured rock aquifer underlying a former Naval Air Warfare Center (NAWC) site in West Trenton, New Jersey, were estimated. The methodology included (1) dividing the site into eight elements of equal size and vertically integrating observed concentrations of two daughter products of TCE biodegradation—cis‐dichloroethene (cis‐DCE) and chloride—using water chemistry data from a network of 88 observation wells; (2) summing the molar mass of cis‐DCE, the first biodegradation product of TCE, to provide a probable underestimate of reductive biodegradation of TCE, (3) summing the molar mass of chloride, the final product of chlorinated ethene degradation, to provide a probable overestimate of overall biodegradation. Finally, lower and higher estimates of aquifer porosities and groundwater residence times were used to estimate a range of overall transformation rates. The highest TCE transformation rates estimated using this procedure for the combined overburden and bedrock aquifers was 945 kg/yr, and the lowest was 37 kg/yr. However, hydrologic considerations suggest that approximately 100 to 500 kg/yr is the probable range for overall TCE transformation rates in this system. Estimated rates of TCE transformation were much higher in shallow overburden sediments (approximately 100 to 500 kg/yr) than in the deeper bedrock aquifer (approximately 20 to 0.15 kg/yr), which reflects the higher porosity and higher contaminant mass present in the overburden. By way of comparison, pump‐and‐treat operations at the NAWC site are estimated to have removed between 1,073 and 1,565 kg/yr of TCE between 1996 and 2009. © 2012 Wiley Periodicals, Inc.*     

Chlorinated Hydrocarbon–Contaminated Site Investigation With Optimized 3D‐CSIA Approach

An optimized “Three‐Dimensional Compound Specific Isotope Analysis (3D‐CSIA)'' investigation was conducted at a chlorinated hydrocarbon–contaminated site in order to (1) determine if multiple onsite sources of groundwater contamination existed and (2) demonstrate the cost‐effectiveness of applying isotope fingerprinting at such a complex contaminated site. Previous groundwater investigations identified chlorinated hydrocarbons at levels that significantly exceed drinking‐water standards but failed to determine the source(s) of contamination due to the lack of vadose‐zone contamination and the absence of groundwater contaminants in shallow portions of the surficial aquifer. To better understand the contaminant source(s), groundwater samples were taken and tested for both the presence of chlorinated hydrocarbons and their isotopic signatures of ¹³C/¹²C, ³⁷Cl/³⁵Cl, and ²H/¹H. A site investigation with an optimized 3D‐CSIA approach revealed multiple chlorinated hydrocarbon releases from different sources, which was also cost‐effective considering the new lines of evidence of target contaminants obtained with the 3D‐CSIA approach instead of any traditional fingerprinting approaches. In addition, the 3D‐CSIA results inferred in situ bioremediation of chlorinated hydrocarbons would be feasible at the site. © 2013 Wiley Periodicals, Inc.