Compound‐Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis‐DCE compound‐specific isotope analysis of carbon and chlorine collected over a 16‐month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis‐DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ³⁷Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis‐DCE. Carbon isotopic values range between ?28.9 and ?20.7‰ VPDB for TCE, and ?26.5 and ?11.8‰ VPDB for cis‐DCE. In most wells, isotopic values remained steady over the 15‐month study. Isotopic enrichment from TCE to cis‐DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine‐carbon isotopic enrichment ratios (?_Cl/?_C) were 0.18 for TCE and 0.69 for cis‐DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume.     

Evaluating TCE Abiotic and Biotic Degradation Pathways in a Permeable Reactive Barrier Using Compound Specific Isotope Analysis

A pilot‐scale zero valent iron (ZVI) Permeable Reactive Barrier (PRB) was installed using an azimuth‐controlled ‐vertical hydrofracturing at an industrial facility to treat a chlorinated Volatile Organic Compound (VOC) plume. Following ZVI injection, no significant reduction in concentration was observed to occur with the exception of some multilevel monitoring wells, which also showed high levels of total organic carbon (TOC). These patterns suggested that the zero valent iron was not well distributed in the PRB creating leaky conditions. The geochemical data indicated reducing conditions in these areas where VOC reduction was observed, suggesting that biotic processes, associated to the guar used in the injection of the iron, could be a major mechanism of VOC degradation. Compound‐Specific Isotope Analysis (CSIA) using both carbon and chlorine stable isotopes were used as a complementary tool for evaluating the contribution of abiotic and biotic processes to VOC trends in the vicinity of the PRB. The isotopic data showed enriched isotope values around the PRB compared to the isotope composition of the VOC source confirming that VOC degradation is occurring along the PRB. A batch experiment using site groundwater collected near the VOC source and the ZVI used in the PRB was performed to evaluate the site‐specific abiotic isotopic fractionation patterns. Field isotopic trends, typical of biodegradations were observed at the site and were different from those obtained during the batch abiotic experiment. These differences in isotopic trends combined with changes in VOC concentrations and redox parameters suggested that biotic processes are the predominant pathways involved in the degradation of VOCs in the vicinity of the PRB.     

Fingerprinting TCE in a bedrock aquifer using compound-specific isotope analysis

A dual isotope approach based on compound-specific isotope analysis (CSIA) of carbon (C) and chlorine (Cl) was used to identify sources of persistent trichloroethylene (TCE) that caused the shut-down in 1994 of a municipal well in an extensive fractured dolostone aquifer beneath Guelph, Ontario. Several nearby industrial properties have known subsurface TCE contamination; however, only one has created a comprehensive monitoring network in the bedrock. The impacted municipal well and many monitoring wells were sampled for volatile organic compounds (VOCs), inorganic parameters, and CSIA. A wide range in isotope values was observed at the study site. The TCE varies between -35.6‰ and -21.8‰ and from 1.6‰ to 3.2‰ for δ(13) C and δ(37) Cl, respectively. In case of cis-1,2-dichloroethene, the isotope values range between -36.3‰ and -18.9‰ and from 2.4‰ to 4.7‰ for δ(13) C and δ(37) Cl, respectively. The dual isotope approach represented by a plot of δ(13) C vs. δ(37) Cl shows the municipal well samples grouped in a domain clearly separate from all other samples from the property with the comprehensive well network. The CSIA results collected under non-pumping and short-term pumping conditions thus indicate that this particular property, which has been studied intensively for several years, is not a substantial contributor of the TCE presently in the municipal well under non-pumping conditions. This case study demonstrates that CSIA signatures would have been useful much earlier in the quest to examine sources of the TCE in the municipal well if bedrock monitoring wells had been located at several depths beneath each of the potential TCE-contributing properties. Moreover, the CSIA results show that microbial reductive dechlorination of TCE occurs in some parts of the bedrock aquifer. At this site, the use of CSIA for C and Cl in combination with analyses of VOC and redox parameters proved to be important due to the complexity introduced by biodegradation in the complex fractured rock aquifer. It is highly recommended to revisit the study when the municipal well is back into full operation.     

Determination of the 13C/12C Isotope Ratio of Organic Compounds for the Biological Degradation of Tetrachloroethene (PCE) and Trichloroethene (TCE)

With the method used here, it was possible to determine the isotope content of both the initial compounds and their metabolites formed due to microbial degradation. The chemical analysis showed that the dominating degradation metabolite for both PCE and TCE degradation was cis-1,2-dichloroethene (cis-1,2-DCE). Apart from this, the formation of TCE, trans-1,2-DCE, 1,1-DCE, chloroethene (VC), ethene and ethane was observed. The isotope analysis showed no measurable fractionation of stable carbon isotopes, for the microbial degradation of PCE and TCE to cis-1,2-DCE. There was a small effect for trans-1,2-DCE and a stronger one for VC as metabolite of TCE.     

Vitamin B12 and Reduced Titanium for Remediation of Residual Chlorinated Solvents: Field Experiment

A first pilot-scale field experiment using vitamin B₁₂ and reduced titanium was conducted in an in situ vertical circulation column at CFB Borden. The objective of the experiment was to test the applicability of the technology for restoring aquifer source zones contaminated by chlorinated solvents—tetrachloroethene (PCE) and 1,1,1-trichloroethane (1,1,1-TCA)—in a mixture of dense nonaqueous phase liquids (DNAPLs). Vitamin B₁₂ promotes the reductive dechlorination of chlorinated organics. A highly reducing and slightly alkaline environment must be maintained (Eh < - 480 mV and 7 < pH < 9) to maximize the rate of degradation. In this field test, PCE and 1,1,1-TCA degraded to a limited extent under experimental conditions, with 1,1,1-TCA degrading more readily. Indigenous bacteria were found to metabolize citrate, which caused titanium to precipitate, limiting degradation. The addition of glucose at the end of a second field season effectively limited citrate degradation and helped recover the optimal redox potential by keeping reduced titanium in solution. A laboratory column was used to confirm field results. The column also produced a significant biomass, which provided an additional source of organic carbon onto which the solvents sorbed.     

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.     

Sulfate Land Application Enhances Biodegradation in a Petroleum Hydrocarbon Smear Zone

Delivery of sulfate to petroleum hydrocarbons (PHCs) source zones and groundwater plumes is desirable to enhance biodegradation rates when treatment has become limited due to depletion of sulfate. Sulfate land application involves spreading sulfate salts on ground surface and allowing their dissolution and infiltration of sulfate into subsurface. The objectives of this pilot-scale investigation were to capture the vertical transport of sulfate beneath an application area, confirm that sulfate reduction was occurring, and explore how the added sulfate affected biodegradation of benzene and toluene. Approximately 4000 kg of gypsum was spread over a 30 m × 30 m study area above a smear zone located approximately 2 m below-ground surface. Precipitation was augmented by two irrigation events. Groundwater samples, collected over 1058 days from multilevel wells and a conventional long-screened monitoring well, were analyzed for benzene, toluene, ethylbenzene, and xylenes (BTEX), sulfate, bromide, dissolved inorganic carbon (DIC) and methane. Compound-specific isotope analyses (CSIA) for benzene and toluene, and isotope analyses of ¹³C-DIC and ³⁴S-SO₄²⁻ were performed. Following application, an increase in sulfate concentration was noted in the smear zone. ³⁴S-SO₄²⁻ enrichment and ¹³C-DIC depletion indicated that sulfate reduction and mineralization of PHCs were enhanced. CSIA results provided unequivocal evidence of anaerobic biodegradation of benzene and toluene. After 1058 days when sulfate was depleted, methane concentrations were about three times greater than baseline conditions suggesting syntrophic benefit of the delivered sulfate. Observations from this investigation support the viability of sulfate land application to enhance biodegradation rates in shallow PHC smear zones.     

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.     

Laboratory,field, and modeling studies of bioaugmentation of butane-utilizing microorganisms for the in situ cometabolic treatment of 1,1-dichloroethene, 1,1-dichloroethane,and 1,1,1-trichloroethane

A series of laboratory, field, and modeling studies were performed evaluating the potential for in situ aerobic cometabolism of chlorinated aliphatic hydrocarbon (CAH) mixtures, including 1,1,1-trichloroethane (1,1,1-TCA), 1,1-dichloroethane (1,1-DCA) and 1,1-dichloroethene (1,1-DCE) by bioaugmented microorganisms that grew on butane. A butane-grown bioaugmentation culture, primarily comprised of a Rhodococcus sp., was developed that effectively transformed mixtures of the three CAHs, under subsurface nutrient conditions. Microcosm experiments and modeling studies showed rapid transformation of 1,1-DCE with high transformation product toxicity and weak inhibition by butane, while 1,1,1-TCA was much more slowly transformed and strongly inhibited by butane. Field studies were conducted in the saturated zone at the Moffett Field In-Situ Test Facility in California. In the bioaugmented test leg, 1,1-DCE was most effectively transformed, followed by 1,1-DCA, and 1,1,1-TCA, consistent with the results from the laboratory studies. A 1-D reactive/transport code simulated the field responses during the early stages of testing (first 20 days), with the following extents of removal achieved at the first monitoring well; 1,1-DCE (∼97%), 1,1-DCA (∼77%), and 1,1,1-TCA (∼36%), with little or no CAH transformation observed beyond the first monitoring well. As time proceeded, decreased performance was observed. The modeling analysis indicated that this loss of performance may have been associated with 1,1-DCE transformation toxicity combined with the limited addition of butane as a growth substrate with longer pulse cycles. When shorter pulse cycles were reinitiated after 40 days of operation, 1,1-DCE transformation was restored and the following transformation extents were achieved; 1,1-DCE (∼94%), 1,1-DCA (∼8%), and 1,1,1-TCA (∼0%), with some CAH transformation occurring past the first monitoring well. Modeling analysis of this period indicated that the bioaugmented culture was likely not the dominant butane-utilizing microorganism present. This was consistent with observations in the indigenous leg during this period that showed effective butane utilization and the following extents of transformation: 1,1-DCE (∼86 %), 1,1-DCA (∼5%), and 1,1,1-TCA (∼0%). The combination of lab and field scale studies and supporting modeling provide a means of evaluating the performance of bioaugmentation and the cometabolic treatment of CAH mixtures.     

Numerical simulation of transport and sequential biodegradation of chlorinated aliphatic hydrocarbons using CHAIN_2D

Microbiological degradation of perchloroethylene (PCE) under anaerobic conditions follows a series of chain reactions, in which, sequentially, trichloroethylene (TCE), cis‐dichloroethylene (c‐DCE), vinylchloride (VC) and ethene are generated. First‐order degradation rate constants, partitioning coefficients and mass exchange rates for PCE, TCE, c‐DCE and VC were compiled from the literature. The parameters were used in a case study of pump‐and‐treat remediation of a PCE‐contaminated site near Tilburg, The Netherlands. Transport, non‐equilibrium sorption and biodegradation chain processes at the site were simulated using the CHAIN_2D code without further calibration. The modelled PCE compared reasonably well with observed PCE concentrations in the pumped water. We also performed a scenario analysis by applying several increased reductive dechlorination rates, reflecting different degradation conditions (e.g. addition of yeast extract and citrate). The scenario analysis predicted considerably higher concentrations of the degradation products as a result of enhanced reductive dechlorination of PCE. The predicted levels of the very toxic compound VC were now an order of magnitude above the maximum permissible concentration levels. Copyright © 1999 John Wiley & Sons, Ltd.     

Thinking Outside the Boxcar: Effective and Sustainable Combined Remedies Using Single Application of Multifunctional Amendments

The combined remedy approach to groundwater remediation optimizes contaminated site cleanup as measured by technical efficacy and sustainability. Regardless of the potential for improving site cleanups, there are several obstacles limiting the implementation of combined remedies. The obstacles primarily stem from an inability of liability owners to easily determine if economic costs are synergistic or additive and from regulatory hesitancy to codify needed timing and technology sequencing flexibility within design documents. These obstacles can often be circumvented by employing multicomponent and multifunctional remedial amendment formulations delivered with a single application. Case studies are presented that demonstrate efficacy of this combined remedies approach. The sustainability of the approach is also assessed by evaluation of economic viability, social productivity, and environmental protection. The case studies include combined abiotic and biotic degradation of chlorinated ethene and ethane compounds, combined reductive, and microaerophilic treatment of chlorinated benzenes, and combined chemical oxidation and biodegradation of petroleum compounds. Case studies are supported with conventional concentration trends and advanced diagnostics including compound specific isotope analysis (CSIA) and genetic‐based molecular biological tools (MBTs).     

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.     

Quantification of TCE Co‐Oxidation in Groundwater Using a 14C–Assay

Bacteria that degrade natural organic matter in groundwater contain oxygenase enzymes that can co‐oxidize trichloroethene (TCE). This degradation pathway is promising for large dilute plumes, but its evaluation is limited because the density of the bacteria with oxygenase enzymes has not been correlated to field scale rates of degradation. A ¹⁴C–TCE assay was developed to determine pseudo first‐order rate constants for the aerobic co‐oxidation of TCE in groundwater. The assay involved incubating ¹⁴C–TCE in samples of groundwater contained in 160 mL serum bottles, and monitoring the accumulation of radiolabel in degradation products. A first‐order rate constant for co‐oxidation was extracted from the rate of accumulation of ¹⁴C in products, accounting for volumetric changes in the serum bottles due to sampling and subsequent changes to the distribution of TCE between the aqueous and gaseous phases. Of the groundwater samples evaluated from 19 wells at five sites, eight samples at three sites had ¹⁴C product accumulation rates that exceeded the accumulation rate in filter‐sterilized groundwater controls. First‐order rate constants ranged from 2.65 to 0.0066 year^?1, which is equivalent to half‐lives of 0.26 to 105 years. Groundwater samples from a few of the wells in which co‐oxidation occurred had volatile organic contaminants in addition to TCE; their presence may have induced the oxygenase enzymes that are needed for TCE co‐oxidation. ¹⁴CO₂ represented ~37% to 97% of the ¹⁴C products that accumulated; the balance of the products was soluble and non‐volatile.     

Bioaugmentation and Propane Biosparging for In Situ Biodegradation of 1,4‐Dioxane

Propane biosparging and bioaugmentation were applied to promote in situ biodegradation of 1,4‐dioxane at Site 24, Vandenberg Air Force Base (VAFB), CA. Laboratory microcosm and enrichment culture testing demonstrated that although native propanotrophs appeared abundant in the shallow water‐bearing unit of the aquifer (8 to 23 ft below ground surface [bgs]), they were difficult to be enriched from a deeper water‐bearing unit (82 to 90 feet bgs). Bioaugmentation with the propanotroph Rhodococcus ruber ENV425, however, supported 1,4‐dioxane biodegradation in microcosms constructed with samples from the deep aquifer. For field testing, a propane‐biosparging system consisting of a single sparging well and four performance monitoring wells was constructed in the deep aquifer. 1,4‐dioxane biodegradation began immediately after bioaugmentation with R. ruber ENV425 (36 L; 4 × 10⁹ cells/mL), and apparent first‐order decay rates for 1,4‐dioxane ranged from 0.021 day^?1 to 0.036 day^?1. First‐order propane consumption rates increased from 0.01 to 0.05 min^?1 during treatment. 1,4‐dioxane concentrations in the sparging well and two of the performance monitoring wells were reduced from as high as 1090 µg/L to <2 µg/L, while 1,4‐dioxane concentration was reduced from 135 µg/L to 7.3 µg/L in a more distal third monitoring well. No 1,4‐dioxane degradation was observed in the intermediate aquifer control well even though propane and oxygen were present. The demonstration showed that propane biosparging and bioaugmentation can be used for in situ treatment of 1,4‐dioxane to regulatory levels.     

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.     

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.     

Numerical Analysis of Thermal Remediation in 3D Field‐Scale Fractured Geologic Media

Thermal methods are promising for remediating fractured geologic media contaminated with volatile organic compounds, and the success of this process depends on the coupled heat transfer, multiphase flow, and thermodynamics. This study analyzed field‐scale removal of trichloroethylene (TCE) and heat transfer behavior in boiling fractured geologic media using the multiple interacting continua method. This method can resolve local gradients in the matrix and is less computationally demanding than alternative methods like discrete fracture‐matrix models. A 2D axisymmetric model was used to simulate a single element of symmetry in a repeated pattern of extraction wells inside a large heated zone and evaluate effects of parameter sensitivity on contaminant recovery. The results showed that the removal of TCE increased with matrix permeability, and the removal rate was more sensitive to matrix permeability than any other parameter. Increasing fracture density promoted TCE removal, especially when the matrix permeability was low (e.g., <10^?17 m²). A 3D model was used to simulate an entire treatment zone and the surrounding groundwater in fractured material, with the interaction between them being considered. Boiling was initiated in the center of the upper part of the heated region and expanded toward the boundaries. This boiling process resulted in a large increase in the TCE removal rate and spread of TCE to the vadose zone and the peripheries of the heated zone. The incorporation of extraction wells helped control the contaminant from migrating to far regions. After 22 d, more than 99.3% of TCE mass was recovered in the simulation.     

Factors Controlling In Situ Biogeochemical Transformation of Trichloroethene: Field Survey

We have previously defined in situ biogeochemical transformation as the biogenic formation of reactive minerals that are capable of abiotically degrading chlorinated solvents such as trichloroethene without accumulation of degradation products such as vinyl chloride (AFCEE et al. 2008 ). This process has been implemented in biowalls used to intercept contaminated groundwater. Abiotic patterns of contaminant degradation were observed at Altus Air Force Base (AFB) and in an associated column study, but not at other sites including Dover AFB. These abiotic patterns were associated with biogenic formation of reactive iron sulfide minerals. Iron sulfides in the form of small individual grains, coatings on magnetite, and sulfur‐deficient pyrite framboids were observed in samples collected from the Altus AFB biowalls and one of the EPA columns. Larger iron sulfide grains coated with oxide layers were observed in samples collected from Dover AFB. Altus AFB and the EPA column differed from Dover AFB in that groundwater flow at Dover AFB was relatively slow and potentially reversing. High volumetric sulfate consumption rates, an abiotic pattern of trichloroethene (TCE) degradation, and the formation of small, high surface area iron sulfide particles were associated with relatively high rates of TCE removal via an abiotic pattern. Geochemical modeling demonstrated that iron monosulfides such as mackinawite were near saturation, and iron disulfides such as pyrite were supersaturated at all sites. This environmental condition can be supportive of nucleation of small particles rather than crystal growth leading to larger particles. When nucleation is dominant, small, high surface area, and reactive particles result. When crystal growth dominates the crystals are larger and have lower specific surface area and reactivity. These results taken together suggest that creation of a dynamic environment can promote biogeochemical transformation based on generation of reactive iron sulfides.     

Bioremediation of Phenanthrene by Mycoplana sp. MVMB2 Isolated from Contaminated Soil

The effect of nutrient and surfactant addition on the biodegradation of phenanthrene was studied in a batch scale soil–slurry system using isolated Mycoplana sp. MVMB2strain. The study was conducted using an artificially phenanthrene spiked and as well as contaminated soil from petrochemical industrial site. Maximum phenanthrene degradation and subsequent high microbial growth were observed at optimum pH (pH 6) and C/N/P ratio (100:20:3). To investigate maximum substrate degradation potential of Mycoplana sp. MVMB2, very high concentrations of phenanthrene (50–200 mg/kg soil) were used. The organism was capable of degrading >60% for a concentration below 20 mg/kg soil and >40% for concentrations up to 200 mg/kg within 8 days. Further the influence of five different surfactants namely Span 80, Tween 20, Triton X‐100, cetyl trimethyl ammonium bromide, and sodium dodecyl sulfate were tested at their critical micelle concentration (CMC) levels for phenanthrene degradation in the soil. The addition of surfactant enhanced the biodegradation and a maximum of 84.49% was obtained for Triton X‐100. Complete phenanthrene degradation by Mycoplana sp. MVMB2 was observed at 3 CMC concentration of Triton X‐100. The optimized parameters obtained were used for the degradation of phenanthrene present in the contaminated soil and 98.6% biodegradation was obtained. Thus, the results obtained in the study suggested that biodegradation of phenanthrene by Mycoplana sp. MVMB2 appeared to be feasible to remediate phenanthrene rich contaminated sites.     

Multi-factors on biodegradation kinetics of polycyclic aromatic hydrocarbons (PAHs) by Sphingomonas sp. a bacterial strain isolated from mangrove sediment

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) in contaminated sediment is an attractive remediation technique and its success depends on biodegradation kinetics, and the optimal condition for the PAH-degrading isolates; however, information on this aspect is still scarce. The effects of multi-factors on biodegradation of phenanthrene, a 3-ring model PAH, in contaminated sediment slurry by Sphingomonas sp. a bacterial strain isolated from surface mangrove sediment, were investigated using the orthogonal experimental design (form L₁₆(4⁵)). The most significant factors were salinity and inoculum size, while the effects of phenanthrene concentrations, nutrient addition and temperatures were insignificant. The optimal biodegradation condition in contaminated mangrove sediment slurry was 30 °C, 15 ppt salinity, a carbon/nitrogen ratio of 100:1 (the background ratio in sediment) and an inoculum size of 10⁶ most probable number g⁻¹ sediment. The phenanthrene biodegradation could be best described by the first order rate model, C = C₀e^−kt, where k (the rate constant) is equaled to 0.1185, under the optimal condition. The kinetic model was verified and its validity in predicting biodegradation by Sphingomonas sp. at various phenanthrene concentrations was proved by experimental data.