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.     

Chlorinated Solvent Source‐Zone Remediation via ZVI‐Clay Soil Mixing: 1‐Year Results

ZVI‐Clay is an emerging remediation approach that combines zero‐valent iron (ZVI)‐mediated degradation and in situ stabilization of chlorinated solvents. Through use of in situ soil mixing to deliver reagents, reagent‐contaminant contact issues associated with natural subsurface heterogeneity are overcome. This article describes implementation, treatment performance, and reaction kinetics during the first year after application of the ZVI‐Clay remediation approach at Marine Corps Base Camp Lejeune, North Carolina. Primary contaminants included trichloroethylene, 1,1,2,2‐tetrachloroethane, and related natural degradation products. For the field application, 22,900 m³ of soils were treated to an average depth of 7.6 m with 2% ZVI and 3% sodium bentonite (dry weight basis). Performance monitoring included analysis of soil and water samples. After 1 year, total concentrations of chlorinated volatile organic compounds (CVOCs) in soil samples were decreased by site‐wide average and median values of 97% and >99%, respectively. Total CVOC concentrations in groundwater were reduced by average and median values of 81% and >99%, respectively. In several of the soil and groundwater monitoring locations, reductions in total CVOC concentrations of greater than 99.9% were apparent. Further reduction in concentrations of chlorinated solvents is expected with time. Pre‐ and post‐mixing average hydraulic conductivity values were 1.7 × 10^?5 and 5.2 × 10^?8 m/s, respectively, indicating a reduction of about 2.5 orders of magnitude. By achieving simultaneous contaminant mass depletion and hydraulic conductivity reduction, contaminant flux reductions of several orders of magnitude are predicted.     

Demonstration of Enhanced Bioremediation in a TCE Source Area at Launch Complex 34, Cape Canaveral Air Force Station

The ability of bioremediation to treat a source area containing trichloroethene (TCE) present as dense nonaqueous phase liquid (DNAPL) was assessed through a laboratory study and a pilot test at Launch Complex 34, Cape Canaveral Air Force Center. The results of microcosm testing indicate that the indigenous microbial community was capable of dechlorinating TCE to ethene if amended with electron donor; however, bioaugmentation with a dechlorinating culture (KB-1; SiREM, Guelph, Ontario, Canada) significantly increased the rate of ethene formation. In microcosms, the activity of the dechlorinating organisms in KB-1 was not inhibited at initial TCE concentrations as high as 2 mM. The initially high TCE concentration in ground water (1.2 mM or 155 mg/L) did not inhibit reductive dechlorination, and at the end of the study, the average concentration of ethene (2.4 mM or 67 mg/L) was in stoichiometric excess of this initial TCE concentration. The production of ethene in stoichiometric excess in comparison to the initial TCE concentration indicates that the bioremediation treatment enhanced the removal of TCE mass (either sorbed to soil or present as DNAPL). Detailed soil sampling indicated that the bioremediation treatment removed greater than 98.5% of the initial TCE mass. Confirmatory ground water samples collected 22 months after the bioremediation treatment indicated that chloroethene concentrations had continued to decline in the absence of further electron donor addition. The results of this study confirm that dechlorination to ethene can proceed at the high TCE concentrations often encountered in source areas and that bioremediation was capable of removing significant TCE mass from the test plot, suggesting that enhanced bioremediation is a potentially viable remediation technology for TCE source areas. Dehalococcoides abundance increased by 2 orders of magnitude following biostimulation and bioaugmentation.     

Identification of Multiple Sources of Groundwater Contamination by Dual Isotopes

Chlorinated solvents are one of the most commonly detected groundwater contaminants in industrial areas. Identification of polluters and allocation of contaminant sources are important concerns in the evaluation of complex subsurface contamination with multiple sources. In recent years, compound‐specific isotope analyses (CSIA) have been employed to discriminate among different contaminant sources and to better understand the fate of contaminants in field‐site studies. In this study, the usefulness of dual isotopes (carbon and chlorine) was shown in assessments of groundwater contamination at an industrial complex in Wonju, Korea, where groundwater contamination with chlorinated solvents such as trichloroethene (TCE) and carbon tetrachloride (CT) was observed. In November 2009, the detected TCE concentrations at the study site ranged between nondetected and 10,066 µg/L, and the CT concentrations ranged between nondetected and 985 µg/L. In the upgradient area, TCE and CT metabolites were detected, whereas only TCE metabolites were detected in the downgradient area. The study revealed the presence of separate small but concentrated TCE pockets in the downgradient area, suggesting the possibility of multiple contaminant sources that created multiple comingling plumes. Furthermore, the variation of the isotopic (δ¹³C and δ³⁷Cl) TCE values between the upgradient and downgradient areas lends support to the idea of multiple contamination sources even in the presence of detectable biodegradation. This case study found it useful to apply a spatial distribution of contaminants coupled with their dual isotopic values for evaluation of the contaminated sites and identification of the presence of multiple sources in the study area.     

Modeling metabolic reductive dechlorination in dense non-aqueous phase liquid source-zones

Recent laboratory experimental evidence has suggested that bioremediation may be an attractive management strategy for dense non-aqueous phase liquid (DNAPL) source-zones. In particular, metabolic reductive dechlorination has been shown to reduce aqueous phase chlorinated ethene contaminant concentrations and enhance DNAPL dissolution, reducing source longevity. Transitioning this technology from the laboratory to the field will be facilitated by tools capable of simulating bioenhanced dissolution. This work presents a mathematical model for metabolic reductive dechlorination in a macroscale two-phase (aqueous-organic) environment. The model is implemented through adaptation of an existing multi-phase compositional simulator, which has been modified to incorporate eight chemical components and four microbial populations: a fermentative population, two dechlorinating populations, and a competitor population (e.g., methanogens). Monod kinetics, modified to incorporate electron donor thresholds, electron acceptor competition, and competitor inhibition, are used to simulate microbial growth and component degradation. The developed model is numerically verified and demonstrated through comparisons with published column-scale dechlorination data. Dechlorination kinetics, electron donor concentrations, and DNAPL saturation and distribution are all found to affect the extent of dissolution enhancement, with enhancements ranging from 1.0 to ∼1.9. Comparison of simulation results with those from a simplified analytic modeling approach suggest that the analytical model may tend to over-predict dissolution enhancement and fail to account for the transient nature of dissolution enhancement, leading to significant (70%) under-prediction of source longevity.     

Integrity of Clay Till Aquitards to DNAPL Migration: Assessment Using Current and Emerging Characterization Tools

Field investigations were carried out to determine the occurrence of tetrachloroethene (PCE) dense nonaqueous phase liquid (DNAPL), the source zone architecture and the aquitard integrity at a 30‐ to 50‐year old DNAPL release site. The DNAPL source zone is located in the clay till unit overlying a limestone aquifer. The DNAPL source zone architecture was investigated through a multiple‐lines‐of‐evidence approach using various characterization tools; the most favorable combination of tools for the DNAPL characterization was geophysical investigations, membrane interface probe, core subsampling with quantification of chlorinated solvents, hydrophobic dye test with Sudan IV, and Flexible Liner Underground Technologies (FLUTe) NAPL liners with activated carbon felt (FACT). While the occurrence of DNAPL was best determined by quantification of chlorinated solvents in soil samples supported by the hydrophobic dye tests (Sudan IV and NAPL FLUTe), the conceptual understanding of source zone architecture was greatly assisted by the indirect continuous characterization tools. Although mobile or high residual DNAPL (S _t > 1%) only occurred in 11% of the source zone samples (intact cores), they comprised 86% of the total PCE mass. The dataset, and associated data analysis, supported vertical migration of DNAPL through fractures in the upper part of the clay till, horizontal migration along high permeability features around the redox boundary in the clay till, and to some extent vertical migration through the fractures in the reduced part of the clay till aquitard to the underlying limestone aquifer. The aquitard integrity to DNAPL migration was found to be compromised at a thickness of reduced clay till of less than 2 m.     

Bioremediation of Chlorinated Pesticides in Field‐Contaminated Soils and Suitability of Tenax Solid‐Phase Extraction as a Predictor of Its Effectiveness

Bioremediation is intensively studied today as a treatment method for soil contaminated with chlorinated pesticides, chemicals counted among persistent organic pollutants. In the presented work, results of desorption kinetics study using consecutive Tenax TA solid phase extraction (SPE) were tested as predictors of 3‐wk anaerobic soil bioremediation effectiveness for chlorinated pesticides γ‐HCH, DDT, and methoxychlor. Field‐contaminated samples were used in these experiments, and conditions of bioremediation tests were based on previous research. Amounts of pesticides removed during bioremediation (43–98% of initial concentrations) were in most cases much larger (average ratio 1.37) than rapidly desorbing fractions estimated in SPE using two‐compartment model of desorption kinetics. The scatter of results was also considerable (standard deviation 0.45). However, there was a statistically significant correlation between amounts removed and rapidly desorbing fractions (R² = 0.64), indicating a relationship between degradability and desorbability. Nonetheless, determination of rapidly desorbing fractions was considered rather a poor indicator of soil bioremediation efficiency for chlorinated pesticides. The total amounts of pesticides desorbed by Tenax in 72 h performed better in this respect (R² = 0.73, fraction removed/desorbed = 1.10 ± 0.20, average ± standard deviation). Disappearance of DDT during bioremediation was accompanied by DDD formation but this was considerably lower than results expected from stoichiometry.     

Performance of Full‐Scale Enhanced Reductive Dechlorination in Clay Till

At a low permeability clay till site contaminated with chlorinated ethenes (Gl. Kongevej, Denmark), enhanced reductive dechlorination (ERD) was applied by direct push injection of molasses and dechlorinating bacteria. The performance was investigated by long‐term groundwater monitoring, and after 4 years of remediation, the development of degradation in the clay till matrix was investigated by high‐resolution subsampling of intact cores. The formation of degradation products, the presence of specific degraders Dehalococcoides spp. with the vinyl chloride (VC) reductase gene vcrA, and the isotope fractionation of trichloroethene, cis‐dichloroethene (cis‐DCE), and VC showed that degradation of chlorinated ethenes occurred in the clay till matrix as well as in sand lenses, sand stringers, and fractures. Bioactive sections of up to 1.8 m had developed in the clay till matrix, but sections, where degradation was restricted to narrow zones around sand lenses and stringers, were also observed. After 4 years of remediation, an average mass reduction of 24% was estimated. Comparison of the results with model simulation scenarios indicate that a mass reduction of 85% can be obtained within approximately 50 years without further increase in the narrow reaction zones if no donor limitations occur at the site. Long‐term monitoring of the concentration of chlorinated ethenes in the underlying chalk aquifer revealed that the aquifer was affected by the more mobile degradation products cis‐DCE and VC generated during the remediation by ERD.     

Microbial Mineralization of Dichloroethene and Vinyl Chloride under Hypoxic Conditions

Mineralization of ¹⁴C‐radiolabled vinyl chloride ([1,2‐¹⁴C] VC) and cis‐dichloroethene ([1,2‐¹⁴C] cis‐DCE) under hypoxic (initial dissolved oxygen (DO) concentrations about 0.1 mg/L) and nominally anoxic (DO minimum detection limit = 0.01 mg/L) was examined in chloroethene‐exposed sediments from two groundwater and two surface water sites. The results show significant VC and dichloroethene (DCE) mineralization under hypoxic conditions. All the sample treatments exhibited pseudo‐first‐order kinetics for DCE and VC mineralization over an extended range of substrate concentrations. First‐order rates for VC mineralization were approximately 1 to 2 orders of magnitude higher in hypoxic groundwater sediment treatments and at least three times higher in hypoxic surface water sediment treatments than in the respective anoxic treatments. For VC, oxygen‐linked processes accounted for 65 to 85% of mineralization at DO concentrations below 0.1 mg/L, and ¹⁴CO₂ was the only degradation product observed in VC treatments under hypoxic conditions. Because the lower detection limit for DO concentrations measured in the field is typically 0.1 to 0.5 mg/L, these results indicate that oxygen‐linked VC and DCE biodegradation can be significant under field conditions that appear anoxic. Furthermore, because rates of VC mineralization exceeded rates of DCE mineralization under hypoxic conditions, DCE accumulation without concomitant accumulation of VC may not be evidence of a DCE degradative “stall” in chloroethene plumes. Significantly, mineralization of VC above the level that could reasonably be attributed to residual DO contamination was also observed in several nominally anoxic (DO minimum detection limit = 0.01 mg/L) microcosm treatments.     

Removal of PCE DNAPL from Tight Clays Using In Situ Thermal Desorption

This paper presents a full‐scale thermal remediation of a brownfields site near San Francisco, California. In Situ Thermal Desorption (ISTD) was used for treatment of chlorinated solvents in a tight clay below the water table. The site had contaminants in concentrations indicating that a tetrachloroethene (PCE)‐rich DNAPL was present. A target volume of 5097 m³ of subsurface material to a depth of 6.2 m was treated for a period of 110 d of heating. Energy was delivered through 126 thermal conduction heater borings, and vapors were extracted from a combination of vertical and horizontal vacuum wells. Approximately 2540 kg of contaminants were recovered in the extracted vapors by the end of treatment. The PCE concentration in the clay was reduced from as high as 2700 mg/kg to an average concentration of 0.012 mg/kg within 110 d of heating (a reduction of >99.999%). Similar effectiveness was documented for TCE, cis‐1,2‐DCE, and vinyl chloride. A total of 2.2 million kWh of electric power was used to heat the site. Approximately 45% of this energy was used to heat the subsurface to the target temperature. Another 53% was necessary to boil approximately 41% of the groundwater within the treatment zone, creating approximately 600 pore volumes of steam by the end of the 110‐d heating and treatment period. Steam generation thus occurred within the clay. Partitioning of the contaminants into the steam and its removal comprised the dominant remedial mechanism. The steam migrated laterally toward the ISTD heaters, where it encountered a small dry region adjacent to each of the heaters, which served as a preferential pathway allowing the steam to migrate upward along the heaters to the more permeable vadose zone. There the steam was captured by a system of vertical and horizontal vacuum extraction wells. This vapor removal strategy facilitated effective thermal treatment of the tight clays located below the water table. Features of a robust design are extension of the heaters at least 1.2 m deeper than the treatment depth, and the installation of shallow horizontal vapor collection wells which allow for establishment of pneumatic control.     

Use of LIF for Real-Time In-Situ Mixed NAPL Source Zone Detection

The site characterization and analysis cone penetrometer system (SCAPS), equipped with realtime fluorophore detection capabilities, was used to delineate subsurface contaminant releases in an area where plating shop waste was temporarily stored. Records indicated that various nonaqueous phase liquids (NAPLs) were released at the site. The investigators advanced the SCAPS laser-induced fluorescence (LIF) sensor to depths beneath the water table of the principal water-bearing zone. The water table was located approximately 6 feet (1.8 m) below ground surface (bgs) across the site. Fluorescence, attributed to fuel compounds commingled with chlorinated solvents, was observed at depths ranging from 4.0 to 11.5 feet (1.2 to 3.5 m) bgs. Fluorescence, attributed to naturally occurring organic materials (by process of elimination and spectral characteristics) commingled with chlorinated solvent constituents, was observed at depths ranging from approximately 13 to 40 feet (4.0 to 12.2 m) bgs. Fluorescence responses from compounds confirmed to be commingled with chlorinated solvents indicates that the SCAPS fluorophore detection system is capable of indirectly delineating vadose zone and subaqueous chlorinated solvents and other dense nonaqueous phase liquids (DNAPLs) at contaminant release sites. This confirmation effort represents the first documented account of the successful application of LIF to identify a mixed DNAPL/LNAPL source zone.     

Comparison of Line-Drive and Push-Pull Flushing Schemes

The performance of cyclodextrin (CD)‐enhanced push‐pull (PP) and line‐drive (LD) approaches to remediation of a site contaminated with a multicomponent dense nonaqueous phase liquid (DNAPL) present in a surficial sandy aquifer was evaluated in this field study. The treatment techniques were compared to each other and to the projected performance of a conventional water‐flushing system. Performance was assessed based on contaminant mass removed per unit volume of extraction solution and per unit time of operation. As expected, the CD‐enhanced LD and PP approaches to remediation were more efficient than conventional flushing with water. Between the two techniques, the PP approach performed 1.5 to 2 times better than the LD approach, particularly for higher DNAPL saturation of the source zone. This result suggests that forcing the flushing solution directly into and through the DNAPL source zone minimized flow bypassing and consequently resulted in a more efficient transfer of contaminant mass between the DNAPL phase and the flushing solution. Nonuniform treatment zone contaminant concentrations and changes in contaminant composition influenced the treatment performances, but these effects were small and still permitted the comparison of successive tests. Although CD was used as the solubility‐enhancing flushing agent in this study, it is likely that the results can be transferred to other chemically enhanced flushing technologies that use, for example, surfactants or alcohols.     

ISCO for Groundwater Remediation: Analysis of Field Applications and Performance

A critical analysis of in situ chemical oxidation (ISCO) projects was performed to characterize situations in which ISCO is being implemented, how design and operating parameters are typically employed, and to determine the performance results being achieved. This research involved design of a database, acquisition and review of ISCO project information, population of the database, and analyses of the database using statistical methods. Based on 242 ISCO projects included in the database, ISCO has been used to treat a variety of contaminants; however, chlorinated solvents are by far the most common. ISCO has been implemented at sites with varied subsurface conditions with vertical injection wells and direct push probes being the most common delivery methods. ISCO has met and maintained concentrations below maximum contaminant levels (MCLs), although not at any sites where dense nonaqueous phase liquids (DNAPL) were presumed to be present. Alternative cleanup levels and mass reduction goals have also been attempted, and these less stringent goals are met with greater frequency than MCLs. The use of pilot testing is beneficial in heterogeneous geologic media, but not so in homogeneous media. ISCO projects cost $220,000 on average, and cost on average $94/yd³ of target treatment zone. ISCO costs vary widely based on the size of the treatment zone, the presence of DNAPL, and the oxidant delivery method. No case studies were encountered in which ISCO resulted in permanent reductions to microbial populations or sustained increases in metal concentrations in groundwater at the ISCO-treated site.     

Modeling Dehalococcoides sp. Augmented Bioremediation in a Single Fracture System

A numerical reactive transport model was developed to simulate the bioremediation processes in a perchloroethene (PCE) contaminated single fracture system augmented with Dehalococcoides sp. (DHC). The model describes multispecies bioreactive transport processes that include bacterial growth and detachment dynamics, biodegradation of chlorinated species, competitive inhibition of various reactive species, and the loss of daughter products because of back‐partitioning effects. Two sets of experimental data, available in the study by Schaefer et al. (2010b) , were used to calibrate and test the model. The model was able to simulate both datasets. The simulation results indicated that the yield coefficient and the DHC maximum utilization rate coefficient were the two important process parameters. A detailed sensitivity study was completed to quantify the sensitivity of the model to variations in these two parameter values. The results show that an increase in yield coefficient increases bacterial growth and thus expedites the dechlorination process, whereas an increase in maximum utilization rate coefficient greatly increased dechlorination rates. The proposed model provides a mathematical framework for simulating remediation systems that employ DHC bioaugmentation for restoring chlorinated‐solvent contaminated groundwater aquifers.     

Response Surface Analysis to Improve Dispersed Crude Oil Biodegradation

In this research, the bioremediation of dispersed crude oil, based on the amount of nitrogen and phosphorus supplementation in the closed system, was optimized by the application of response surface methodology and central composite design. Correlation analysis of the mathematical‐regression model demonstrated that a quadratic polynomial model could be used to optimize the hydrocarbon bioremediation (R² = 0.9256). Statistical significance was checked by analysis of variance and residual analysis. Natural attenuation was removed by 22.1% of crude oil in 28 days. The highest removal on un‐optimized condition of 68.1% were observed by using nitrogen of 20.00 mg/L and phosphorus of 2.00 mg/L in 28 days while optimization process exhibited a crude oil removal of 69.5% via nitrogen of 16.05 mg/L and phosphorus 1.34 mg/L in 27 days therefore optimization can improve biodegradation in shorter time with less nutrient consumption.     

A Practical Measurement Strategy to Estimate Nonlinear Chlorinated Solvent Sorption in Low foc Sediments

In this study, we tested a practical strategy useful for accurate chlorinated volatile organic compound (cVOC) sorption prediction. Corresponding to the feature of the superposition of adsorption due to thermally altered carbonaceous matter (TACM) with organic carbon‐water partitioning, a nonlinear Freundlich sorption isotherm covering a wide range of aqueous concentrations was defined by equilibrium sorption measurement at one or a few low concentration points with extrapolation to the empirical organic carbon‐water partition coefficient (K_oc,e) near compound solubility. We applied this approach to obtain perchloroethene equilibrium sorption isotherm parameters for TACM‐containing glacial sand and gravel subsoil samples from a field site in New York. Sorption and associated K_oc,c applicable to low (5–500 µg/L) and high (>100,000 µg/L) aqueous concentrations were determined in batch experiments. (The K_oc,c is the organic carbon‐normalized sorption partition coefficient corresponding to aqueous concentration C_w.) The K_oc,c measurements at low concentration (~5 µg/L) were 6 to 34 times greater than the K_oc,e. The importance of this type of data is illustrated through presentation of its substantial impact on the site remedy. In so doing, we provide an approach that is broadly applicable to cVOC field sites with similar circumstances (low carbon content glacial sand and gravel with TACM).     

Field Study of Enhanced TCE Reductive Dechlorination by a Full‐Scale Whey PRB

This study evaluates the efficiency of a full‐scale, 81 m‐wide permeable reactive barrier (PRB) configured by injection of dairy whey in the downgradient region of a contaminant source zone to enhance the in situ biodegradation of high concentrations (10² to 10³μg/L) of chlorinated ethenes (CEs). Ten biannual whey injections were completed in a 3.5‐year pilot phase and 1.5‐year operational phase. Improved and sustained dechlorination was observed at extraction/injection and downgradient wells in the fully‐operational phase, when dried whey masses were increased from 13.6 kg to 230–360 kg, whey slurry volumes were increased from 2300 L to 307,000–480,000 L, and extraction/injection well loops were employed for the application of whey. At extraction/injection wells, CEs decreased to low (≤10 μg/L) or undetectable levels. At downgradient wells, average trichloroethene concentrations decreased, by as much as 100% (from ≤384.2 during the pilot phase to ≤102.6 μg/L during the operational phase), while average cis‐dichloroethene concentrations decreased by as much as 57.5% (from ≤6466.1 to ≤4912.2 μg/L). Downgradient vinyl chloride averages either increased by as much as 63.8% (from ≤859.6 to ≤1407.9 μg/L) or decreased by 64.0% (from 1375.4 to 880 μg/L). Downgradient ethene + ethane averages increased by as much as 73.2% (from ≤1145.3 to ≤1347.1 μg/L). On the basis of the 2008 average market price, the estimated material cost of whey is $1.96/kg organic carbon or, for the configuration of an 81 m PRB by biannual application of 300 kg whey, $325/year. Carbon substrate cost comparisons and implications for efficient in situ treatment design are discussed.     

Biological reduction of chlorinated solvents: Batch-scale geochemical modeling

Simulation of biodegradation of chlorinated solvents in dense non-aqueous phase liquid (DNAPL) source zones requires a model that accounts for the complexity of processes involved and that is consistent with available laboratory studies. This paper describes such a comprehensive modeling framework that includes microbially mediated degradation processes, microbial population growth and decay, geochemical reactions, as well as interphase mass transfer processes such as DNAPL dissolution, gas formation and mineral precipitation/dissolution. All these processes can be in equilibrium or kinetically controlled. A batch modeling example was presented where the degradation of trichloroethene (TCE) and its byproducts and concomitant reactions (e.g., electron donor fermentation, sulfate reduction, pH buffering by calcite dissolution) were simulated. Local and global sensitivity analysis techniques were applied to delineate the dominant model parameters and processes. Sensitivity analysis indicated that accurate values for parameters related to dichloroethene (DCE) and vinyl chloride (VC) degradation (i.e., DCE and VC maximum utilization rates, yield due to DCE utilization, decay rate for DCE/VC dechlorinators) are important for prediction of the overall dechlorination time. These parameters influence the maximum growth rate of the DCE and VC dechlorinating microorganisms and, thus, the time required for a small initial population to reach a sufficient concentration to significantly affect the overall rate of dechlorination. Self-inhibition of chlorinated ethenes at high concentrations and natural buffering provided by the sediment were also shown to significantly influence the dechlorination time. Furthermore, the analysis indicated that the rates of the competing, nonchlorinated electron-accepting processes relative to the dechlorination kinetics also affect the overall dechlorination time. Results demonstrated that the model developed is a flexible research tool that is able to provide valuable insight into the fundamental processes and their complex interactions during bioremediation of chlorinated ethenes in DNAPL source zones.     

Dissolved Organic Carbon in Groundwater Overlain by Irrigated Sugarcane

Elevated dissolved organic carbon (DOC) has been detected in groundwater beneath irrigated sugarcane on the Burdekin coastal plain of tropical northeast Australia. The maximum value of 82 mg/L is to our knowledge the highest DOC reported for groundwater beneath irrigated cropping systems. More than half of the groundwater sampled in January 2004 (n = 46) exhibited DOC concentrations greater than 30 mg/L. DOC was progressively lower in October 2004 and January 2005, with a total decrease greater than 90% indicating varying load(s) to the aquifer. It was hypothesized that the elevated DOC found in this groundwater system is sourced at or near the soil surface and supplied to the aquifer via vertical recharge following above average rainfall. Possible sources of DOC include organic‐rich sugar mill by‐products applied as fertilizer and/or sugarcane sap released during harvest. CFC‐12 vertical flow rates supported the hypothesis that elevated DOC (>40 mg/L) in the groundwater results from recharge events in which annual precipitation exceeds 1500 mm/year (average = 960 mm/year). Occurrence of elevated DOC concentrations, absence of electron acceptors (O₂ and NO₃^–) and both Fe²⁺ and Mn²⁺ greater than 1 mg/L in shallow groundwater suggest that the DOC compounds are chemically labile. The consequence of high concentrations of labile DOC may be positive (e.g., denitrification) or negative (e.g., enhanced metal mobility and biofouling), and highlights the need to account for a wider range of water quality parameters when considering the impacts of land use on the ecology of receiving waters and/or suitability of groundwater for irrigated agriculture.     

Effects of In Situ Remediation Using Oxidants or Surfactants on Subsurface Organic Matter and Sorption of Trichloroethene

In situ remediation technologies have the potential to alter subsurface properties such as natural organic matter (NOM) content or character, which could affect the organic carbon‐water partitioning behavior of chlorinated organic solvents, including dense nonaqueous phase liquids (DNAPLs). Laboratory experiments were completed to determine the nature and extent of changes in the partitioning behavior of trichloroethene (TCE) caused by in situ chemical oxidation or in situ surfactant flushing. Sandy porous media were obtained from the subsurface at a site in Orlando, Florida. Experiments were run using soil slurries in zero‐headspace reactors (ZHRs) following a factorial design to study the effects of porous media properties (sand vs. loamy sand with different total organic carbon [TOC] contents), TCE concentration (DNAPL presence or absence), and remediation agent type (potassium permanganate vs. activated sodium persulfate, Dowfax 8390 vs. Tween 80). Results revealed that the fraction of organic carbon (f_oc) of porous media after treatment by oxidants or surfactants was higher or lower relative to that in the untreated media controls. Isotherm experiments were run using the treated and control media to measure the distribution coefficient (K_d) of TCE. Organic carbon‐water partitioning coefficient values (K_oc) calculated from the experimental data revealed that K_oc values for TCE in the porous media were altered via treatment using oxidants and surfactants. This alteration can affect the validity of estimates of contaminant mass remaining after remediation. Thus, potential changes in partitioning behavior should be considered to help avoid decision errors when judging the effectiveness of an in situ remediation technology.