Biostimulation and Bioaugmentation to Enhance Reductive Dechlorination of TCE in a Long‐Term Flow Through Column Study

Large laboratory columns (15.2 cm diameter, 183 cm long) were fed with groundwater containing trichloroethylene (TCE), were biostimulated and bioaugmented, and were monitored for over 7.5 years. The objective of the study was to observe how the selection of the carbon and energy source, i.e., whey, Newman Zone^® standard surfactant emulsified oil and Newman Zone nonionic surfactant emulsified oil, affected the rate and extent of dechlorination. Column effluent was monitored for TCE and its degradation products, redox indicators (nitrate‐N, Fe(II), sulfate), and changes in iron mineralogy. Total bacteria and Dehalococcoides mccartyi strains were quantified using q‐PCR. Complete dechlorination was only observed in the whey treated columns, occurring 1 year after bioaugmentation with addition of a culture known to dechlorinate TCE to ethene, and 3 years later in the non‐bioaugmented column. The addition of the emulsified oils with or without bioaugmentation resulted in dechlorination only through cis‐DCE and vinyl chloride. While Dehalococcoides mccartyi strains are the only known bacteria that can fully dechlorinate TCE, their presence, either natural or augmented, was not the sole determiner of complete dechlorination. The establishment of a supporting microbial community and biogeochemistry that developed with continuous feeding of whey, in addition to the presence of D. mccartyi, were necessary to support complete reductive dechlorination. Results confirm that careful selection of a biostimulant is critical to the success of TCE dechlorination in complex soil environments.     

Arsenic Cycling in Hydrocarbon Plumes: Secondary Effects of Natural Attenuation

Monitored natural attenuation is widely applied as a remediation strategy at hydrocarbon spill sites. Natural attenuation relies on biodegradation of hydrocarbons coupled with reduction of electron acceptors, including solid phase ferric iron (Fe(III)). Because arsenic (As) adsorbs to Fe‐hydroxides, a potential secondary effect of natural attenuation of hydrocarbons coupled with Fe(III) reduction is a release of naturally occurring As to groundwater. At a crude‐oil‐contaminated aquifer near Bemidji, Minnesota, anaerobic biodegradation of hydrocarbons coupled to Fe(III) reduction has been well documented. We collected groundwater samples at the site annually from 2009 to 2013 to examine if As is released to groundwater and, if so, to document relationships between As and Fe inside and outside of the dissolved hydrocarbon plume. Arsenic concentrations in groundwater in the plume reached 230 µg/L, whereas groundwater outside the plume contained less than 5 µg/L As. Combined with previous data from the Bemidji site, our results suggest that (1) naturally occurring As is associated with Fe‐hydroxides present in the glacially derived aquifer sediments; (2) introduction of hydrocarbons results in reduction of Fe‐hydroxides, releasing As and Fe to groundwater; (3) at the leading edge of the plume, As and Fe are removed from groundwater and retained on sediments; and (4) downgradient from the plume, patterns of As and Fe in groundwater are similar to background. We develop a conceptual model of secondary As release due to natural attenuation of hydrocarbons that can be applied to other sites where an influx of biodegradable organic carbon promotes Fe(III) reduction.     

Factors Controlling In Situ Biogeochemical Transformation of Trichloroethene: Column Study

In situ biogeochemical transformation involves biological formation of reactive minerals in an aquifer that can destroy chlorinated solvents such as trichloroethene (TCE) without accumulation of intermediates such as vinyl chloride. There is uncertainty regarding the materials and geochemical conditions that are required to promote biogeochemical transformation. The objective of this study was to identify amendments and biogeochemical conditions that promote in situ biogeochemical transformation. Laboratory columns constructed with plant mulch were supplemented with different amendments and were operated under varying conditions of water chemistry and hydraulic residence time. Four patterns of TCE removal were observed: (1) no removal, (2) biotic transformation of TCE to cis‐1,2‐dichloroethene (cis‐1,2‐DCE), (3) biogeochemical transformation of TCE without accumulation of reductive dechlorination products, and (4) mixed behavior where a combination of patterns was observed either simultaneously or over time. Principal coordinates analysis and analysis of variance (ANOVA) identified factors that promoted biogeochemical transformation: (1) high influent sulfate concentration, (2) relatively high hydraulic retention time, (3) supplementation of mulch with vegetable oil, and (4) addition of hematite or magnetite. The combination of the first three factors promoted complete sulfate reduction and a high volumetric sulfate consumption rate. The fourth factor provided a source of ferrous iron and/or a surface to which sulfide could react to form reactive iron sulfides. Many columns demonstrated either no TCE removal or a biotic TCE transformation pattern. Modification of column operation to include all four factors identified above promoted biogeochemical transformation in these columns. These results support the importance of the factors in biogeochemical transformation.     

Long‐Term Impacts on Groundwater and Reductive Dechlorination Following Bioremediation in a Highly Characterized Trichloroethene DNAPL Source Area

High‐resolution soil and groundwater monitoring was performed to assess the long‐term impacts of bioremediation using bioaugmentation with a dechlorinating microbial consortium (and sodium lactate as the electron donor) in a well‐characterized trichloroethene (TCE) dense nonaqueous phase liquid (DNAPL) source area. Monitoring was performed up to 3.7 years following active bioremediation using a high‐density monitoring network that included several discrete interval multi‐level sampling wells. Results showed that despite the absence of lactate, lactate fermentation transformation products, or hydrogen, biogeochemical conditions remained favorable for the reductive dechlorination of chlorinated ethenes. In locations where soil data showed that TCE DNAPL sources persisted, local contaminant rebound was observed in groundwater, whereas no rebound or continuous decreases in chlorinated ethenes were observed in locations where DNAPL sources were treated. While ethene levels measured 3.7 years after active treatment suggested relatively low (2 to 30%) dechlorination of the parent TCE and daughter products, carbon stable isotope analysis showed that the extent of complete dechlorination was much greater than indicated by ethene generation and that the estimated first‐order rate constant describing the complete dechlorination of TCE at 3.7 years following active bioremediation was approximately 3.6 y–1. Overall, results of this study suggest that biological processes may persist to treat TCE for years after cessation of active bioremediation, thereby serving as an important component of remedial treatment design and long‐term attenuation.     

Potentially Bioavailable Natural Organic Carbon and Hydrolyzable Amino Acids in Aquifer Sediments

This study evaluated the relationship between concentrations of operationally defined potentially bioavailable organic ‐carbon (PBOC) and hydrolyzable amino acids (HAAs) in sediments collected from a diverse range of chloroethene‐‐contaminated sites. Concentrations of PBOC and HAA were measured using aquifer sediment samples collected at six selected study sites. Average concentrations of total HAA and PBOC ranged from 1.96 ± 1.53 to 20.1 ± 25.6 mg/kg and 4.72 ± 0.72 to 443 ± 65.4 mg/kg, respectively. Results demonstrated a statistically significant positive relationship between concentrations of PBOC and total HAA present in the aquifer sediment (p < 0.05). Higher levels of HAA were consistently observed at sites with greater levels of PBOC and first‐order decay rates. Because amino acids are known to be readily biodegradable carbon compounds, this relationship suggests that the sequential chemical extraction procedure used to measure PBOC is a useful indicator of bioavailable carbon in aquifer sediments. This, in turn, is consistent with the interpretation that PBOC measurements can be used for estimating the amount of natural organic carbon available for driving the reductive dechlorination of chloroethenes in groundwater systems.     

Bioremediation in Fractured Rock: 1. Modeling to Inform Design,Monitoring, and Expectations

Field characterization of a trichloroethene (TCE) source area in fractured mudstones produced a detailed understanding of the geology, contaminant distribution in fractures and the rock matrix, and hydraulic and transport properties. Groundwater flow and chemical transport modeling that synthesized the field characterization information proved critical for designing bioremediation of the source area. The planned bioremediation involved injecting emulsified vegetable oil and bacteria to enhance the naturally occurring biodegradation of TCE. The flow and transport modeling showed that injection will spread amendments widely over a zone of lower‐permeability fractures, with long residence times expected because of small velocities after injection and sorption of emulsified vegetable oil onto solids. Amendments transported out of this zone will be diluted by groundwater flux from other areas, limiting bioremediation effectiveness downgradient. At nearby pumping wells, further dilution is expected to make bioremediation effects undetectable in the pumped water. The results emphasize that in fracture‐dominated flow regimes, the extent of injected amendments cannot be conceptualized using simple homogeneous models of groundwater flow commonly adopted to design injections in unconsolidated porous media (e.g., radial diverging or dipole flow regimes). Instead, it is important to synthesize site characterization information using a groundwater flow model that includes discrete features representing high‐ and low‐permeability fractures. This type of model accounts for the highly heterogeneous hydraulic conductivity and groundwater fluxes in fractured‐rock aquifers, and facilitates designing injection strategies that target specific volumes of the aquifer and maximize the distribution of amendments over these volumes.     

Delineation of spatial redox zones using discriminant analysis and geochemical modelling in arsenic‐affected alluvial aquifers

This study characterized the redox conditions in arsenic‐affected groundwater aquifers of the Lanyang plain, Taiwan. Discriminant analysis was adopted to delineate three redox zones (oxidative, transitional and reductive zones) in different aquifers and yielded 92·3% correctness on groundwater quality data. Arsenic is mainly distributed in the reductive zone, and arsenic distribution in the shallow aquifer is mainly affected by surface activities. According to PHREEQC modelling results, possible mechanisms for arsenic release to groundwater in Lanyang plain are explored. Arsenic released to groundwater in the oxidative zone (zone 1) is primarily caused by the oxidations of arsenic‐bearing pyrite minerals, and arsenate is the predominant species. While the reductive dissolution of Fe‐oxides are responsible for the high arsenic concentration found in the transitional and reductive zones (zones 2 and 3), arsenite is the predominant species. The reduction potential of groundwater rises as the depths and zones increase. Some sulphates may be reduced to form sulphide ions, which then react with arsenic to form arseno‐sulphide deposits (such as realgar, orpiment) and then slightly lower groundwater arsenic concentrations. A conceptual diagram which summarized the possible release processes of arsenic in different redox zones along groundwater flow in Lanyang plain is postulated. Arsenic‐bearing pyrite and arsenopyrite (FeAsS) are oxidized as they are exposed to the infiltrated oxygenated rainwater, releasing soluble arsenate Fe(II) and SO₄^2? into zone 1. The dissolution of arsenic‐rich Fe‐oxides due to the onset of reducing conditions in zones 2 and 3 is responsible for the mobility of arsenic and likely to be the primary mechanism of arsenic release to groundwater in the Lanyang plain Copyright © 2007 John Wiley & Sons, Ltd.     

Long-term changes in ground water chemistry at a phytoremediation demonstration site

A field-scale demonstration project was conducted to evaluate the capability of eastern cottonwood trees (Populus deltoides) to attenuate trichloroethene (TCE) contamination of ground water. By the middle of the sixth growing season, trees planted where depth to water was <3 m delivered enough dissolved organic carbon to the underlying aquifer to lower dissolved oxygen concentrations, to create iron-reducing conditions along the plume centerline and sulfate-reducing or methanogenic conditions in localized areas, and to initiate in situ reductive dechlorination of TCE. Apparent biodegradation rate constants for TCE along the centerline of the plume beneath the phytoremediation system increased from 0.0002/d to 0.02/d during the first six growing seasons. The corresponding increase in natural attenuation capacity of the aquifer along the plume centerline, from 0.0004/m to 0.024/m, is associated with a potential decrease in plume-stabilization distance from 9680 to 160 m. Demonstration results provide insight into the amount of vegetation and time that may be needed to achieve cleanup objectives at the field scale.     

Injection of Zero‐Valent Iron into an Unconfined Aquifer Using Shear‐Thinning Fluids

Approximately 190 kg of 2 μm‐diameter zero‐valent iron (ZVI) particles were injected into a test zone in the top 2 m of an unconfined aquifer within a trichloroethene (TCE) source area. A shear‐thinning fluid was used to enhance ZVI delivery in the subsurface to a radial distance of up to 4 m from a single injection well. The ZVI particles were mixed in‐line with the injection water, shear‐thinning fluid, and a low concentration of surfactant. ZVI was observed at each of the seven monitoring wells within the targeted radius of influence during injection. Additionally, all wells within the targeted zone showed low TCE concentrations and primarily dechlorination products present 44 d after injection. These results suggest that ZVI can be directly injected into an aquifer with shear‐thinning fluids to induce dechlorination and extends the applicability of ZVI to situations where other emplacement methods may not be viable.     

A Tracer Test to Characterize Treatment of TCE in a Permeable Reactive Barrier

A tracer test was conducted to characterize the flow of groundwater across a permeable reactive barrier constructed with plant mulch (a biowall) at the OU‐1 site on Altus Air Force Base, Oklahoma. This biowall is intended to intercept and treat groundwater contaminated by trichloroethylene (TCE) in a shallow aquifer. The biowall is 139‐m long, 7.3‐m deep, and 0.5‐m wide. Bromide was injected from an upgradient well into the groundwater as a conservative tracer, and was subsequently observed breaking through in monitoring wells within and downgradient of the biowall. The bromide breakthrough data demonstrate that groundwater entering the biowall migrated across it, following the slope of the local groundwater surface. The average seepage velocity of groundwater was approximately 0.06 m/d. On the basis of the Darcy velocity of groundwater and geometry of the biowall, the average residence time of groundwater in the biowall was estimated at 10 d. Assuming all TCE removal occurred in the biowall, the reduction in TCE concentrations in groundwater across the biowall corresponds to a first‐order attenuation rate constant in the range of 0.38 to 0.15 per d. As an independent estimate of the degradation rate constant, STANMOD software was used to fit curves through data on the breakthrough of bromide and TCE in selected wells downgradient of the injection wells. Best fits to the data required a first‐order degradation rate constant for TCE removal in the range of 0.13 to 0.17 per d. The approach used in this study provides an objective evaluation of the remedial performance of the biowall that can provide a basis for design of other biowalls that are intended to remediate TCE‐contaminated groundwater.     

Determination of longitudinal dispersivity in an unconfined sandy aquifer

Study of the mobility of contaminants in an aquifer is an important issue for the proper remediation of contaminated groundwater. Determination of associated solute transport parameters therefore is essential for investigation of the extent to which groundwater can be contaminated. This study aimed at determining solute transport parameters for an unconfined sandy aquifer at a laboratory scale through various tracer tests using a conservative solute as a tracer. Tracer tests consisted of both well‐tracer tests (single and double wells) and an aquifer tracer test using a plume‐capturing device such as time domain reflectometry (TDR). The results showed that longitudinal dispersivities estimated from the single and double well‐tracer tests were 2·2 cm and 13·5 cm for a travel distance of 9·3 cm and 13·5 cm from the injection point respectively. These results agreed reasonably well with the results of the aquifer tracer test. The solute transport parameters obtained at multiple points in the aquifer through the aquifer tracer test revealed that the dispersivity length was proportional to the travel distance by a factor of 0·3, which was moderately higher than the value of 0·1 given in the literature. Copyright © 2002 John Wiley & Sons, Ltd.     

Anaerobic biodegradation of TCE in laboratory columns of fractured saprolite

An experiment was conducted to determine if biodegradation of trichloroethylene (TCE) can occur in previously uncontaminated ground water in saturated fractured saprolite (highly weathered material derived from sedimentary rocks). Two undisturbed columns (0.23 m diameter by 0.25 m long) of fractured saprolite were collected from approximately 2 m depth at an uncontaminated site on the Oak Ridge Reservation, Oak Ridge, Tennessee. Natural, uncontaminated ground water from the site, which was degassed and spiked with dissolved phase TCE, was continuously pumped through one column containing the natural microbial communities (the biotic column). In a second column, the microorganisms were inhibited and the dissolved phase TCE was added under aerobic conditions (dissolved oxygen conditions > 2 ppm). In effluent from the biotic column, reducing conditions rapidly developed and evidence of anaerobic biodegradation of TCE, by the production of cDCE, first appeared approximately 31 days after addition of TCE. Reductive dechlorination of TCE occurred after iron-reducing conditions were established and about the same time that sulfate reduction began. There was no evidence of methanogenesis. Analyses using polymerase chain reaction with specific primers sets detected the bacteria Geothrix, Geobacter, and Desulfococcus-Desulfonema-Desulfosarcina in the effluent of the biotic column, but no methanogens. The presence of these bacteria is consistent with iron- and sulfate-reducing conditions. In the inhibited column, there were no indicators of TCE degradation. Natural organic matter that occurs in the saprolite and ground water at the site is the most likely primary electron donor for supporting reductive dechlorination of TCE. The relatively rapid appearance of indicators of TCE dechlorination suggests that these processes may occur even in settings where low oxygen conditions occur seasonally due to changes in the water table.     

Dissolved Hydrogen Dynamics Associated with Emulsified Vegetable Oil Bioremediation of Chloroethenes

Emulsified vegetable oil (EVO) is widely used as a fermentable substrate to enhance the reductive dechlorination of chlorinated ethenes (CEs) in groundwater systems. The fermentation of EVO by naturally occurring bacteria produces molecular hydrogen (H₂) which acts as an electron donor driving microbially mediated reductive dechlorination. While dissolved H₂ drives much of the dechlorination associated with CE bioremediation, the dynamics of H₂ production and consumption associated with EVO addition to groundwater systems is seldom documented. The present study shows how H₂ concentrations changed over a 4-year period following EVO addition to a sandy coastal plain aquifer underlying Naval Air Station Pensacola, Florida, USA. Prior to EVO addition, H₂ concentrations at the site were in the range characteristic of Fe(III)-reducing conditions (0.2–0.6 nM). Following EVO addition, H₂ concentrations increased exponentially, peaking at approximately 25,000 nM. Hydrogen concentrations then began decreasing exponentially, and by 4 years after EVO addition had stabilized at 4.0 nM. That pattern suggests symbiotic cross-feeding between fermentative and respirative microbial populations resulting in a Gaussian rise and fall of H₂ concentrations. That, in turn, suggests while EVO biostimulation can temporarily increase H₂ concentrations to very high levels, those higher concentrations are unlikely to be sustained indefinitely.     

Carbon Isotope Fractionation of PCE and TCE During Dechlorination by Vitamin B12

Reductive dechlorination of perchloroethylene (PCE) and trichloroethylene (TCE) by vitamin B12 is an analogue of the microbial reductive dechlorination reaction and is presently being applied as a remediation technique. Stable carbon isotopic analysis, an effective and powerful tool for the investigation and monitoring of contaminant remediation, was used to characterize the isotopic effects of reductive dechlorination of PCE and TCE by vitamin B12 in laboratory microcosms. In laboratory experiments, 10 mg/L vitamin B12 degraded >90% of the initial 20 mg/L PCE with TCE, the primary product of PCE degradation, accounting for between 64% and 72% of the PCE degraded. In experiments with TCE, 147 mg/L vitamin B12 degraded >90% of the initial 20 mg/L TCE with cis -dichloroethene ( c DCE), the primary product of degradation accounting for between 30% and 35% of the TCE degraded. Degradation of both PCE and TCE exhibited first-order kinetics. Strong isotopic fractionation of the reactant PCE and of the reactant TCE was observed over the course of degradation. This fractionation could be described with a Rayleigh model using enrichment factors of −16.5%o and −15.8%o for PCE, and −17.2%o and −16.6%o for TCE. Fractionation was similar in all experiments, with a mean enrichment factor of −16.5%o ± 0.6%o. The occurrence of such large enrichment factors indicates that isotopic analysis can be used to monitor the dechlorination of PCE and TCE by vitamin B12 and remediation of ground water plumes. Evidence indicates that isotopic fractionation is taking place during complexation of the chlorinated ethenes to vitamin B12, as has been suggested for reductive dechlorination by zero valent iron. The differences between e values for this reaction and those observed for anaerobic biodegradation of the chlorinated ethenes suggest that there may be differences in the rate-determining step for these two processes.     

Using principal component analysis in the investigation of groundwater hydrochemistry of Upper Jezireh Basin,Syria

Principal component analysis (PCA) was applied to hydrochemical and isotopic data of 34 groundwater samples. This allowed the reduction of 20 variables to four significant PCs that explain 81.9% of the total variance; F1 (47.1%) explains the groundwater mineralization, whereas F2 (17%) shows isotopic enrichment and nitrate pollution. Based on an iso-factor scores map of F1, three water zones were delineated: Zone A (F1 < ?1), with fresh groundwater from the unconfined aquifer; Zone B (1 > F1 > ?1), with moderate mineralization from the confined–unconfined aquifer boundary; and Zone C (F1 > 1), with the most mineralized hot water from the confined aquifer. The iso-factor scores map of F2 delineates positive values representing samples from the unconfined aquifer, with freshwater and nitrate contamination associated with stable isotope enrichment, whereas negative values represent samples from the confined aquifer. The results clearly demonstrate the usefulness of PCA in groundwater hydrochemistry investigations.     

Chemical and isotopic methods for management of artificial recharge in Mazraha Station (Damascus Basin,Syria)

Artificially enhancing recharge rate into groundwater aquifer at specially designed facilities is an attractive option for increasing the storage capacity of potable water in arid and semi‐arid region such as Damascus basin (Syria). Two dug wells (I and II) for water injection and 24 wells for water extraction are available in Mazraha station for artificial recharge experiment. Chemical and stable isotopes (δ²H and δ¹⁸O) were used to evaluate artificial recharge efficiency. 400 to 500*10³ m³ of spring water were injected annually into the ambient shallow groundwater in Mazraha station, which is used later for drinking purpose. Ambient groundwater and injected spring water are calcium bicarbonate type with EC about 880 ± 60 μS/cm and 300 ± 50 μS/cm, respectively. The injected water is under saturated versus calcite and the ambient groundwater is over saturated, while the recovered water is near equilibrium. It was observed that the injection process formed a chemical dilution plume that improves the groundwater quality. Results demonstrate that the hydraulic conductivity of the aquifer is estimated around 6.8*10^?4 m/s. The effective diameter of artificial recharge is limited to about 250 m from the injection wells. Mixing rate of 30% is required in order to reduce nitrate concentration below 50 mg/l which is considered the maximum concentration limit for potable water. Deuterium and oxygen‐18 relationship demonstrates that mixing line between injected water and ambient groundwater has a slope of 6.1. Oxygen‐18 and Cl^? plot indicates that groundwater salinity origin is from mixing process, and no dissolution and evaporation were observed. These results demonstrate the efficiency of the artificial recharge experiments to restore groundwater storage capacity and to improve the water quality. Copyright © 2011 John Wiley & Sons, Ltd.     

Field-Scale Evaluation of Bioaugmentation Dosage for Treating Chlorinated Ethenes

A field demonstration was performed to evaluate the impacts of bioaugmentation dosage for treatment of chlorinated ethenes in a sandy-to-silty shallow aquifer. Specifically, bioaugmentation using a commercially available Dehalococcoides (DHC)-containing culture was performed in three separate groundwater recirculation loops, with one loop bioaugmented with 3.9 × 10¹¹ DHC, the second loop bioaugmented with 3.9 × 10¹² DHC, and the third loop bioaugmented with 3.9 × 10¹³ DHC. Groundwater monitoring was performed to evaluate DHC growth and migration, dechlorination rates, and aquifer geochemistry. The loop inoculated with 3.9 × 10¹² DHC showed slower dechlorination rates and DHC migration/growth compared with the other loops. This relatively poor performance was attributed to low pH conditions. Results for the loops inoculated with 3.9 × 10¹¹ and 3.9 × 10¹³ DHC showed similar timeframes for dechlorination, as evaluated at a monitoring well approximately 10 feet downgradient of the DHC injection well. Application of a recently developed one-dimensional bioaugmentation fate and transport screening model provided a reasonable prediction of the data in these two loops. Overall, these results suggest that increasing bioaugmentation dosage does not necessarily result in decreased dechlorination timeframes in the field. The ability to predict results suggests that modeling potentially can serve as an effective tool for determining bioaugmentation dosage and predicting overall remedial timeframes.     

222Rn as Natural Tracer for LNAPL Recovery in a Crude Oil‐Contaminated Aquifer

The objective of this study was to investigate whether ²²²Rn in groundwater can be used as a tracer for light non‐aqueous phase liquid (LNAPL) quantification at a field site treated by dual‐phase LNAPL removal. After the break of a pipeline, 5 ha of soil in the nature reserve Coussouls de Crau in southern France was contaminated by 5100 m³ of crude oil. Part of this oil seeped into the underlying gravel aquifer and formed a floating oil body of about 3.9 ha. The remediation consists of plume management by hydraulic groundwater barriers and LNAPL extraction in the source zone. ²²²Rn measurements were performed in 21 wells in and outside the source zone during 15 months. In uncontaminated groundwater, the radon activity was relatively constant and remained always >11 Bq/L. The variability of radon activity measurements in wells affected by the pump‐and‐skim system was consistent with the measurements in wells that were not impacted by the system. The mean activities in wells in the source zone were, in general, significantly lower than in wells upgradient of the source zone, owing to partitioning of ²²²Rn into the oil phase. The lowest activities were found in zones with high non‐aqueous phase liquid (NAPL) recovery. LNAPL saturations around each recovery well were furthermore calculated during a period of high groundwater level, using a laboratory‐determined crude oil–water partitioning coefficient of 38.5 ± 2.9. This yielded an estimated volume of residual crude oil of 309 ± 93 m³ below the capillary fringe. We find that ²²²Rn is a useful and cheap groundwater tracer for finding zones of good LNAPL recovery in an aquifer treated by dual‐phase LNAPL removal, but that quantification of NAPL saturation using Rn is highly uncertain.     

Characterization of Flow Dynamics and Vulnerability in a Coastal Aquifer System

Traditional aquifer vulnerability techniques primarily rely on spatial property data for a region and are limited by their ability to directly or indirectly assess flow and transport processes occurring from the surface to depth within an aquifer system. The main objective of this study was to investigate groundwater vulnerability in terms of aquifer interconnectivity and flow dynamics. A combination of stable isotopes, groundwater age‐dating (radiocarbon), and geomorphic/geogenic spatial analyses was applied to a regional, highly developed coastal aquifer to explain the presence of nitrate at depth. The average δ¹³C value (?17.3 ± 2‰ VPDB, n = 27) is characteristic of groundwater originating from locally infiltrated precipitation through extensively cultivated soils. The average δ¹⁸O and δD values (?4.0 ± 0.1‰ VSMOW, n = 27; δD: ?19.3 ± 1‰ VSMOW, n = 27, respectively) are similar to precipitation water derived from maritime sources feeding the region's surface water and groundwater. Stable and radioactive isotopes reveal significant mixing between shallow and deep aquifers due to high velocities, hydraulic connection, and input of local recharge water to depths. Groundwater overdevelopment enhances deeper and faster modern water downward flux, amplifying aquifer vulnerability. Therefore, aquifer vulnerability is a variable, dependent on the type and degree of stress conditions experienced by a groundwater system as well as the geospatial properties at the near surface.     

Push‐Pull Tests for Estimating RDX and TNT Degradation Rates in Groundwater

In situ bioremediation is being considered to optimize an existing pump‐and‐treat remedy for treatment of explosives‐contaminated groundwater at the Umatilla Chemical Depot. Push‐pull tests were conducted using a phased approach to measure in situ hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and 2,4,6‐trinitrotoluene (TNT) degradation rates associated with various carbon substrates. Phase I included short‐duration transport tests conducted in each well to determine dilution rates and retardation factors for RDX and TNT. Phase II included aquifer “feedings” conducted by injecting 150 gallons of treated site groundwater amended with ethanol, corn syrup, lactose or emulsified oil (concentrations 10, 25 and 27 mM, respectively; 12% by volume for emulsified oil). Wells received up to 6 substrate “feedings” over the course of 3 months followed by monitoring dissolved oxygen, nitrate, Fe(II), and sulfate to gauge in situ redox conditions as indicators of anaerobic microbial activity. Phase III included push‐pull tests conducted by injecting 150 gallons of site groundwater amended with approximately 1000 µg/L RDX, 350 µg/L TNT, carbon substrate and a conservative tracer, followed by sampling over 8 d. Corn syrup resulted in the best RDX removal (82% on average) and the largest RDX degradation rate coefficient (1.4 ± 1.1 d^?1). Emulsified oil resulted in the best TNT removal (99%) and largest TNT degradation rate coefficient (5.7 × 10^?2 d^?1). These results will be used to simulate full‐scale in situ bioremediation scenarios at Umatilla and will support a go/no‐go decision to initiate full‐scale bioremediation remedy optimization.