Evaluation of soil solid amendments for TCE biodegradation in a biobarrier system

Permeable biobarrier systems (PBSs) are being recognized as low‐cost passive bioremediation technologies for chlorinated organic contamination. This innovative technology can play a crucial and effective role in site restorations. Laboratory‐scale experiments were conducted to investigate the biodegradation of trichloroethylene (TCE) to ethylene in shallow groundwater through the use of a PBS enhanced by bioaugmentation at the U.S. Department of Energy's Savannah River Site (SRS). Two composts and two plant amendments, eucalyptus mulch (EM) and corncobs (CC), were examined for their effectiveness at creating and maintaining conditions suitable for TCE anaerobic dechlorination. These materials were evaluated for their (1) nutrient and organic carbon content, (2) TCE sorption characteristics, and (3) longevity of release of nutrients and soluble carbon in groundwater to support TCE dechlorination. Native bacteria in the columns had the ability to convert TCE to dichloroethenes (DCEs); however, the inoculation with the TCE‐degrading culture greatly increased the rate of biodegradation. This caused a significant increase in by‐product concentration, mostly in the form of DCEs and vinyl chloride (VC) followed by a slow degradation to ethylene. Of the tested amendments, eucalyptus mulch was the most effective at supporting the reductive dechlorination of TCE. Corncobs created a very acidic condition in the column that inhibited dechlorination. © 2007 Wiley Periodicals, Inc.     

Successful full‐scale enhanced anaerobic dechlorination at a NAPL strength 1,1,1‐TCA source area

Bioremediation of 1,1,1‐trichloroethane (TCA) is more challenging than bioremediation of other chlorinated solvents, such as tetrachloroethene (PCE) and trichloroethene (TCE). TCA transformation often occurs under methanogenic and sulfate‐reducing conditions and is mediated by Dehalobacter. The source area at the project site contains moderately permeable medium sand with a low hydraulic gradient and is approximately 0.5 acre. TCA contamination generally extended to 35 feet, with the highest concentrations at approximately 20 feet. The concentrations then decreased with depth; several wells contained 300 to 600 mg/L of TCA prior to bioremediation. The area of treatment also contained 2 to 30 mg/L of TCE from an upgradient source. Initial site groundwater conditions indicated minimal biotic dechlorination and the presence of up to 20 mg/L of nitrate and 90 mg/L of sulfate. Microcosm testing indicated that TCA dechlorination was inhibited by the site's relatively low pH (5 to 5.5) and high TCA concentration. After the pH was adjusted and TCA concentrations were reduced to less than 35 mg/L (by dilution with site water), dechlorination proceeded rapidly using whey (or slower with sodium lactate) as an electron donor. Throughout the remediation program, increased resistance to TCA inhibition (from 35 to 200 mg/L) was observed as the microbes adapted to the elevated TCA concentrations. The article presents the results of a full‐scale enhanced anaerobic dechlorination recirculation system and the successful efforts to eliminate TCA‐ and pH‐related inhibition. © 2012 Wiley Periodicals, Inc.     

ERD of Residual TCE DNAPL Achieving Nondetect from a Single Injection of Food‐Grade Waste

Residual dense nonaqueous phase liquid (DNAPL) composed of trichloroethene (TCE) was identified in a deeper interval of an overburden groundwater system at a manufacturing facility located in northern New England. Site hydrostratigraphy is characterized by two laterally continuous and transmissive zones consisting of fully‐saturated fine sand with silt and clay. The primary DNAPL source was identified as a former dry well with secondary contributions from a proximal aboveground TCE storage tank. A single additive‐injection mobilization in 2001 utilizing a food‐grade injectate formulated with waste dairy product and inactive yeast enhanced residual TCE DNAPL destruction in situ by stimulating biotic reductive dechlorination. The baseline TCE concentration was detected up to 97,400 μg/L in the deeper interval of the overburden groundwater system, and enhanced reductive dechlorination (ERD) achieved >99 percent reduction in TCE concentrations in groundwater over nine years with no evidence of sustained rebound. TCE concentrations have remained nondetect below 2.0 μg/L for the last five consecutive sampling rounds between 2013 and 2015. ERD utilizing a food‐grade injectate is a green remediation technology that has destroyed residual DNAPL at the site and achieved similar results at other residual DNAPL sites during both pilot‐ and full‐scale applications. ©2016 Wiley Periodicals, Inc.     

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

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

Detecting and quantifying reductive dechlorination under monitored natural attenuation conditions

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

Improvements to TCE Microcosm Protocols for Biostimulation in Bedrock Aquifers

In this study, a factorial‐designed experiment of biostimulated trichloroethene (TCE) dechlorination in fractured bedrock aquifers using microcosms evaluated several potential biostimulants (i.e., nutrients, vitamins, and sterile groundwater). Substantial cost savings and resource efficiency can be provided by this approach because: factorial designs require relatively few microcosms per factor; the interpretation of the observations can proceed largely by common sense, simple arithmetic, and computer graphics; the observations can indicate promising directions for further experimentation and causative relationships; and designs can be suitably augmented when a more in‐depth exploration is needed. TCE degradation was evaluated using three methods of data analysis: (1) analysis of covariance (ANCOVA) between biotic and abiotic treatment trend‐line slopes; (2) calculation of biodegradation half‐life; and (3) effects screening by model fitting. Microcosm preparation with crushed rock in groundwater was found to more closely match the previously observed field rates than the preparation with only groundwater. Injection of nutrient and vitamin mixtures was made into microcosms that were previously aged to obtain consistent conditions, and the TCE concentration measured after incubating for 45 days. Comparison of results indicated that the nutrient mixture slows or inhibits the degradation of TCE compared to the sterile groundwater; however, the vitamin mixture offsets and nearly compensates for the inhibitory effect of the nutrient mixture. It is recommended that this factorial experiment be augmented with additional studies of individual or groups of compounds from the vitamin mixture using this methodology to isolate and identify the specific factor or interaction responsible for the inhibitory compensation. © 2013 Wiley Periodicals, Inc.     

Chlorinated Solvent Treatment Wetland

A first‐of‐its‐kind wetland restoration project was completed in October 2000 to treat trichloroethene‐(TCE‐)impacted groundwater from a former manufacturing facility prior to discharge into a highly valued recreational surface water body in the upper Midwest. This article summarizes the design, construction, operation, and effectiveness of the restored wetland. The groundwater‐surface water discharge zone at the site was restored as a wetland to improve the natural degradation of TCE and subsequent degradation by‐products. For the past 11 years, the treatment wetland performance was evaluated by monitoring the wetland vegetation, wetland hydraulics, and water chemistry. Water quality data have been used to assess the wetland geochemistry, TCE and TCE‐degradation by‐product concentrations within the wetland, and the surface water quality immediately downgradient of the wetland. The treatment wetland has been performing according to design, with TCE and TCE‐degradation by‐products not exceeding surface water criteria. The monitoring results show that TCE and TCE‐degradation by‐products are entering the treatment wetland via natural hydraulic gradients and that the geochemistry of the wetland supports both reductive dechlorination (anaerobic degradation) and cometabolic degradation (aerobic degradation) of TCE and TCE‐degradation by‐products: cis‐ and trans‐1,2‐dichloroethene and vinyl chloride. © 2013 Wiley Periodicals, Inc.     

Field‐scale evaluation of a biobarrier for the treatment of a trichloroethene plume

In the 1960s, trichloroethene (TCE) was used at what is now designated as Installation Restoration Program Site 32 Cluster at Vandenberg Air Force Base to flush missile engines prior to launch and perhaps for other degreasing activities, resulting in releases of TCE to groundwater. The TCE plume extends approximately 1 kilometer from the previous launch facilities beyond the southwestern end of the site. To limit further migration of TCE and chlorinated degradation by‐products, an in situ, permeable, reactive bioremediation barrier (biobarrier) was designed as a cost‐effective treatment technology to address the TCE plume emanating from the source area. The biobarrier treatment would involve injecting carbon‐based substrate and microbes to achieve reductive dechlorination of volatile organic compounds, such as TCE. Under reducing conditions and in the presence of certain dechlorinating microorganisms, TCE degrades to nontoxic ethene in groundwater. To support the design of the full‐scale biobarrier, a pilot test was conducted to evaluate site conditions and collect pertinent design data. The pilot test results indicated possible substrate delivery difficulties and a smaller radius of influence than had been estimated, which would be used to determine the final biobarrier well spacing. Based on these results, the full‐scale biobarrier design was modified. In January 2010, the biobarrier was implemented at the toe of the source area by adding a fermentable substrate and a dechlorinating microbial culture to the subsurface via an injection well array that spanned the width of the TCE plume. After the injections, the groundwater pH in the injection wells continued to decrease to a level that could be detrimental to the population of Dehalococcoides in the SDC‐9^TM culture. In addition, 7 months postinjection, the injection wells could not be sampled due to fouling. Cleaning was required to restore their functions. Bioassay and polymerase chain reaction analyses were conducted, as well as titration tests, to assess the need for biobarrier amendments in response to the fouling issues and low pH. Additionally, slug tests were performed on three wells to evaluate possible localized differences in hydraulic conductivity within the biobarrier. Based on the test results, the biobarrier was amended with sodium carbonate and inoculated a second time with SDC‐9^TM. The aquifer pH was restored, and reductive dechlorination resumed in the treatment zone, evidenced by the reduction in TCE and the increase in degradation products, including ethene. © 2011 Wiley Periodicals, Inc.     

Successful application of monitored natural attenuation in a surficial aquifer

Groundwater investigations conducted since 1988 at a Tennessee Department of Environment and Conservation (TDEC) Voluntary Oversight and Assistance Program (VOAP) site located in Millington, Tennessee, have defined the lateral and vertical extent of site chemicals of concern (COCs) consisting of tetrachloroethene (PCE), trichloroethene (TCE), and associated degradation products. Results of a groundwater remedial investigation determined that aquifer conditions were favorable for anaerobic degradation of COCs through reductive dechlorination. A subsequent groundwater feasibility study determined that monitored natural attenuation (MNA) coupled with long‐term groundwater monitoring was the most effective and suitable remedial option for the site. A Record of Decision was issued by the TDEC VOAP approving MNA and long‐term groundwater monitoring as the remedial option for the site, a first for such a site in Tennessee involving chlorinated organics. A groundwater fate and transport model (the 1998 model) developed during the RI was used as the basis for the MNA remedy. Analytical data from 1998 to 2008 indicate COCs in former high‐concentration areas continue to degrade at rates consistent with or ahead of the 1998 model predictions. Evidence of reductive dechlorination is also supported by the continued presence of breakdown products—specifically, vinyl chloride and ethene (terminal endpoint of PCE breakdown through reductive dechlorination). The continued detection of breakdown products along the flow‐path wells also confirms the effectiveness of the MNA remedy at the site. Current analytical data indicate that COC plumes beneath the site are not migrating and are actually retracting. © 2010 Wiley Periodicals, Inc.     

Enhanced anaerobic bioremediation of a TCE source at the Tarheel Army Missile Plant using EOS

EOS, or emulsified oil substrate, was used to stimulate anaerobic biodegradation of trichloroethene (TCE) and tetrachloroethene (PCE) at a former Army‐owned manufacturing facility located in the Piedmont area of North Carolina. Previous use of chlorinated solvents at the facility resulted in soil and groundwater impacts. Ten years of active remediation utilizing soil vacuum extraction and air sparging (SVE/AS) were largely ineffective in reducing the TCE/PCE plume. In 2002, the Army authorized preparation of an amended Remedial Action Plan (RAP) to evaluate in situ bioremediation methods to remediate TCE in groundwater. The RAP evaluated eight groundwater remediation technologies and recommended EOS as the preferred bioremediation alternative for the site. Eight wells were drilled within the 100 × 100 feet area believed to be the primary source area for the TCE plume. In a first injection phase, dilute EOS emulsion was injected into half of the wells. Distribution of the carbon substrate through the treatment zone was enhanced by pumping the four wells that were not injected and recirculating the extracted water through the injection wells. The process was repeated in a second phase that reversed the injection/extraction well pairs. Overall, 18,480 pounds of EOS were injected and 163,000 gallons of water were recirculated through the source area. Anaerobic groundwater conditions were observed shortly after injection with a corresponding decrease in both PCE and TCE concentrations. Dissolved oxygen, oxidation‐reduction potential, and sulfate concentrations also decreased after injection, while TCE‐degradation products, ferrous iron, and methane concentrations increased. The reduction in TCE allowed the Army to meet the groundwater remediation goals for the site. Approximately 18 months after injection, eight wells were innoculated with a commercially prepared dechlorinating culture (KB‐1) in an attempt to address lingering cis‐1,2‐dichloroethene (cis‐DCE) and vinyl chloride (VC) that continued to be observed in some wells. Dehalococcoides populations increased slightly post‐bioaugmentation. Both cis‐DCE and VC continue to slowly decrease. © 2007 Wiley Periodicals, Inc.     

The effect of solvent concentration on the use of palladized-iron for the step-wise dechlorination of polychlorinated biphenyls in soil extracts

This report describes the application of palladized iron (Pd/Fe) to the dechlorination of polychlorinted biphenyls (PCBs) at ambient temperature. Experiments supported by congener-specific analyses demonstrated that dechlorination occurs in a step-wise fashion with the meta-chlorines being more reactive than ortho-chlorines. Over the course of the laboratory experiments, complete conversion to biphenyl was observed. The process was also tested with PCBs dissolved in high (40-60%) concentrations of ethanol and isopropanol as a means of simulating solutions generated by commercial soil and solid waste extraction processes. The reaction rate was sensitive to the percentage of solvent but complete dechlorination was still indicated. Tests with soil extracts from a contaminated site demonstrated that there were no apparent interferences from asphalt and other miscellaneous debris. Short-duration tests with highly contaminated PCB solutions from a hazardous waste site demonstrated efficient dechlorination although there was a reduction in reaction rate with time.     

Spatial Distribution of Geobacteraceae and Sulfate‐Reducing Bacteria During In Situ Bioremediation of Uranium‐Contaminated Groundwater

Analysis of the physiological status of subsurface microbial communities generally relies on the study of unattached microorganisms in the groundwater. These approaches have been employed in studies on bioremediation of uranium‐contaminated groundwater at a study site in Rifle, Colorado, in which Geobacter species typically account for over 90 percent of the microbial community in the groundwater during active uranium reduction. However, to develop efficient in situ bioremediation strategies it is necessary to know the status of sediment‐associated microorganisms as well. In order to evaluate the distribution of the natural community of Geobacter during bioremediation of uranium, subsurface sediments were packed into either passive flux meters (PFMs) or sediment columns deployed in groundwater monitoring wells prior to acetate injection during in situ biostimulation field trials. The trials were performed at the Department of Energy's (DOE's) Rifle Integrated Field Research Challenge site. Sediment samples were removed either during the peak of Fe(III) reduction or the peak of sulfate reduction over the course of two separate field experiments and preserved for microscopy. Direct cell counts using fluorescence in situ hybridization (FISH) probes targeting Geobacter species indicated that the majority of Geobacter cells were unattached during Fe(III) reduction, which typically tracks with elevated rates of uranium reduction. Similar measurements conducted during the sulfate‐reducing phase revealed the majority of Geobacter to be attached following exhaustion of more readily bioavailable forms of iron minerals. Laboratory sediment column studies confirmed observations made with sediment samples collected during field trials and indicated that during Fe(III) reduction, Geobacter species are primarily unattached (90 percent), whereas the majority of sulfate‐reducing bacteria and Geobacter species are attached to sediment surfaces when sulfate reduction is the predominant form of metabolism (75 percent and 77 percent, respectively). In addition, artificial sediment experiments showed that pure cultures of Geobacter uraniireducens, isolated from the Rifle site, were primarily unattached once Fe(III) became scarce. These results demonstrate that, although Geobacter species must directly contact Fe(III) oxides in order to reduce them, cells do not firmly attach to the sediments, which is likely an adaptive response to sparsely and heterogeneously dispersed Fe(III) minerals in the subsurface. © 2013 Wiley Periodicals, Inc.     

Threshold amounts of organic carbon needed to initiate reductive dechlorination in groundwater systems

Aquifer sediment and groundwater chemistry data from 15 Department of Defense facilities located throughout the United States were collected and analyzed with the goal of estimating the amount of natural organic carbon needed to initiate reductive dechlorination in groundwater systems. Aquifer sediments were analyzed for hydroxylamine and NaOH‐extractable organic carbon, yielding a probable underestimate of potentially bioavailable organic carbon (PBOC). Aquifer sediments were also analyzed for total organic carbon (TOC) using an elemental combustion analyzer, yielding a probable overestimate of bioavailable carbon. Concentrations of PBOC correlated linearly with TOC with a slope near one. However, concentrations of PBOC were consistently five to ten times lower than TOC. When mean concentrations of dissolved oxygen observed at each site were plotted versus PBOC, it showed that anoxic conditions were initiated at approximately 200 mg/kg of PBOC. Similarly, the accumulation of reductive dechlorination daughter products relative to parent compounds increased at a PBOC concentration of approximately 200 mg/kg. Concentrations of total hydrolysable amino acids (THAA) in sediments also increased at approximately 200 mg/kg, and bioassays showed that sediment CO₂ production correlated positively with THAA. The results of this study provide an estimate for threshold amounts of bioavailable carbon present in aquifer sediments (approximately 200 mg/kg of PBOC; approximately 1,000 to 2,000 mg/kg of TOC) needed to support reductive dechlorination in groundwater systems. © 2012 Wiley Periodicals, Inc.     

Pilot scale testing composite swellable organosilica nanoscale zero‐valent iron—Iron‐Osorb®—for in situ remediation of trichloroethylene

Iron‐Osorb^® is a solid composite material of swellable organosilica with embedded nanoscale zero‐valent iron that was formulated to extract and dechlorinate solvents in groundwater. The unique feature of the highly porous organosilica is its strong affinity for chlorinated solvents, such as trichloroethylene (TCE), while being impervious to dissolved solids. The swellable matrix is able to release ethane after dechlorination and return to the initial state. Iron‐Osorb^® was determined to be highly effective in reducing TCE concentrations in bench‐scale experiments. The material was tested in a series of three pilot scale tests for in situ remediation of TCE in conjunction with the Ohio Environmental Protection Agency at a site in central Ohio. Results of these tests indicate that TCE levels were reduced for a period of time after injection, then leveled out or bounced back, presumably due to depletion of zero‐valent iron. Use of tracer materials and soil corings indicate that Iron‐Osorb^® traveled distances of at least 20 feet from the injection point during soil augmentation. The material appears to remain in place once the injection fluid is diluted into the surrounding groundwater. Overall, the technology is promising as a remediation method to treat dilute plumes or create diffuse permeable reactive barriers. Keys to future implementation include developing injection mechanisms that optimize soil distribution of the material and making the system long‐lasting to allow for continual treatment of contaminants emanating from the soil matrix. © 2011 Wiley Periodicals, Inc.     

Reductive dechlorination of a chlorinated solvent plume in Houston,Texas

Chlorinated solvents such as tetrachloroethene (perchloroethene, PCE) and trichloroethene (TCE) have been extensively used in various industrial applications for many years. Because neither are typically consumed through their various uses, they are often released to the environment through industrial application or disposal. Once released, PCE and TCE tend to migrate downward into groundwater, where they persist. In the current case study, cheese whey was used as a groundwater amendment to facilitate the reductive dechlorination of a chlorinated solvent plume underlying an auto dealer/repair shop in Harris County, Texas. From September 2010 to January 2014, over 32,000 gallons of cheese whey were injected into the subsurface resulting in a marked reduction in oxidation–reduction potential (ORP) and nitrate concentrations, coupled with an increase in ferrous iron concentrations. Statistical trend analyses indicate the primary contaminants, PCE and TCE, as well as the daughter product cis‐1,2‐dichloroethene (cDCE), all exhibited a positive response, as evidenced by statistically decreasing trends, and/or reversal in concentration trends, subsequent to cheese whey injections. Maximum concentrations of PCE and TCE in key test wells decreased by as much as 98.97 percent and 99.17 percent, respectively. In addition, the bacterial genus Dehalococcoides, capable of complete reduction of PCE to non‐toxic ethene, was found to be more abundant in the treatment area, as compared to background concentrations. Because cheese whey is a by‐product of the cheese making process, the cost of the product is essentially limited to transport. This study demonstrates cheese whey to be an effective groundwater amendment at a cost which is orders of magnitude lower than popular industry alternatives.     

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

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

Stimulation of aerobic degradation of chlorinated ethenes in soil by microbial inoculation

Degradation of chlorinated ethenes under aerobic conditions has been reported using a cometabolic pathway. A site in Illinois had shallow contamination and sandy soils, which in combination created aerobic conditions. The aerobic conditions prevented the degradation of chlorinated ethenes by reductive dechlorination. Biodegradation of chloroethenes under aerobic conditions does not occur naturally at all sites; however, it can be enhanced if microorganisms capable of cometabolic degradation are introduced into the soil. In this study, trichloroethene (TCE) removal in the soil was enhanced by the injection of a commercially available microbial inoculum (CL‐OUT® inoculum, CL‐Solutions, Cincinnati, OH) and nutrients and was compared to chlorinated ethene removal in soil that had received nutrients only and soil that had received activated sludge and nutrients. Trichloroethene removal was measured after one week, seven weeks, and eleven weeks. After one week, no significant TCE removal had occurred in any of the test microcosms. After seven weeks, a slight decrease in TCE levels accompanied by an increase in cis‐1,2‐dichloroethene (cis‐1,2‐DCE) was seen in the microcosms that had received CL‐OUT®. After 11 weeks, a marked decrease in TCE levels was observed in the microcosms that had received CL‐OUT®. No significant TCE decrease was observed in any of the other microcosms. These data suggest that organisms capable of aerobic TCE degradation were not present at the site; however, the addition of an inoculum containing such organisms enabled aerobic degradation to occur. © 2008 Wiley Periodicals, Inc.     

Ensuring the continued success of a mulch biowall at a trichloroethylene-contaminated superfund site: Lessons learned

Trichloroethylene (TCE) is a toxic organic compound, which can adversely affect human health. The chemical is one of the most frequently found contaminants in groundwater in the United States and around the world. A landfill in Maryland contaminated with high levels of TCE decades ago was added to the U.S. Environmental Protection Agency's National Priority List (NPL) in 1994. A biowall was installed on the site in 2013 to promote the bioremediation of TCE and subsequently of its degradation products. Six-year monitoring data indicated a steady removal of >99% groundwater TCE at the wall since installation. However, a concurrent buildup of intermediate byproducts was observed downgradient of the wall. An examination of the entire system was necessary to find the reason behind the inefficiency of the biowall. In this study, the background of the site, remediation plan, and installation were assessed. Monitoring data, including the concentration of TCE and its degradation byproducts, and geochemical and physical characteristics were evaluated to understand the conditions and challenges facing decision-makers of this project and possible options to improve biowall efficacy.     

Remediation of a Former Dry Cleaner Using Nanoscale Zero Valent Iron

Nanoscale zero valent iron (nZVI) was evaluated in a laboratory treatability study and subsequently injected as an interim measure to treat source area groundwater impacts beneath a former dry cleaner located in Chapel Hill, North Carolina (the site). Dry cleaning operations resulted in releases of tetrachloroethene (PCE) that impacted site soil at concentrations up to 2,700 mg/kg and shallow groundwater at concentrations up to 41 mg/L. To achieve a design loading rate of 0.001 kg of iron per kilogram of aquifer material, approximately 725 kg of NanoFe? (PARS Environmental) was injected over a two‐week period into a saprolite and partially weather rock aquifer. Strong reducing conditions were established with oxidation–reduction potential (ORP) values below –728 mV. pH levels remained greater than 8 standard units for a period of 12 months. Injections resulted in near elimination of PCE within one month. cis‐1,2‐Dichloroethene accumulated at high concentrations (greater than 65 mg/L) for 12 months. MAROS software (Version 2.2; AFCEE, 2006 ) was used to calculate mass reduction of PCE and total ethenes at 96 percent and 58 percent, respectively, compared to baseline conditions. Detections of acetylene confirmed the presence of the beta‐elimination pathway. Detections of ethene confirmed complete dechlorination of PCE. Based on hydrogen gas generation, iron reactivity lasted 15 months. © 2013 Wiley Periodicals, Inc.     

Geochemistry of Iron and Sulfur in the Zone of Microbial Sulfate Reduction in Mine Tailings

The cycling of iron and sulfur in mine tailings depends on various chemical and microbial reactions. The present study was undertaken in order to assess the role played by populations of sulfate-reducing bacteria (SRB) on the fate of Fe and SO₄ ^2- in Cu–Zn and Au tailings. Samples were taken along a 50-cm deep profile at all sites and analyzed for SRB populations, solid-phase mineralogy and porewater geochemistry. Results indicated that the Cu–Zn tailings were highly oxidized near the surface, as shown by the very low pH, high redox potential, large concentrations of soluble Cu, Zn and sulfate in the porewaters, and the depletion of pyrite. On the other hand, Au tailings were more pH neutral, slightly anoxic, and showed low concentrations of Fe and SO₄ ^2- in the porewaters and very little pyrite oxidation. SRB populations in the Cu–Zn tailings increased with depth, just below the oxic/anoxic interface and were linked to a decline of sulfate and DOC concentrations around the same depths. However, large concentrations of dissolved Fe were also observed around the same depth intervals. Our results suggest that SRB could be involved in sulfate reduction in the Cu–Zn tailings, because the solubility of sulfate was not controlled by the precipitation of sulfate-rich minerals. However, the presence of soluble Fe in the reduced portion of the tailings was also indicative of the presence of iron reducing bacteria (IRB). These bacteria were not enumerated in the present study, but their co-occurrence with SRB has been reported in the past in similar mining environments. The decline of sulfate and the release of soluble iron into the porewaters were also paralleled by a pH increase and the generation of alkalinity. In the Au tailings, SRB populations were generally constant throughout the depth profile and could not be ascribed to sulfate reduction in the porewaters. The solubilities of sulfate and iron in these tailings were partially controlled by jarosite and Fe-oxide minerals. It is then clear that SRB populations could be recovered from various mining sites, but their activity cannot be ascertained based on microbial enumeration and geochemical data.