Chemical and Biological Reduction of PCE by Pneumatic Fracturing and Injection of ZVI in Saprolite

This article presents a case study of the source‐area treatment of tetrachloroethene (PCE) in a low‐permeability formation using zero‐valent iron (ZVI). Evidence of the stimulation of biological reduction processes within the treatment zone occurred. Pneumatic fracturing and injection of microscale ZVI slurry in the overburden and weathered bedrock zones was performed at a commercial brownfields redevelopment site in Maryland. A 20,000‐square‐foot source area impacted with PCE at concentrations greater than 15,000 µg/L was treated at depths ranging from 10 to 70 feet bgs. An average ZVI dosage of 0.0024 iron‐to‐soil mass ratio within the overburden zone led to a 75 percent decrease in PCE mass in less than one year. For the weathered bedrock zone, an average 0.0045 iron‐to‐soil mass ratio resulted in a 92 percent decrease in PCE mass during the same period. The reducing environment and hydrogen generated by the ZVI may have stimulated Dehalobacter populations, as evidenced by concentrations up to 10⁴ cells per milliliter measured within the treatment area despite a groundwater pH as high as 9. The biological reductive dechlorination of the chlorinated ethenes explains the temporary increase in trichloroethene and cis‐1,2‐dichloroethene concentrations. © 2013 Wiley Periodicals, Inc.     

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.     

Performance evaluation of an in situ source area combined remedy for the remediation of commingled chlorinated ethanes and ethenes

The chlorinated volatile organic compounds (CVOCs), tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA), often found as commingled contaminants of concern (COCs) in groundwater, can degrade via a variety of biotic and abiotic reductive pathways. In situ remediation of a groundwater contaminant source area containing commingled 1,1,1‐TCA, PCE, and TCE was conducted using a combined remedy/treatment train approach. The first step was to create geochemically reducing conditions in the source area to degrade the CVOCs to lesser chlorinated CVOCs (i.e., 1,1‐dichloroethane [1,1‐DCA], 1,1‐dichlorethene [1,1‐DCE], cis‐1,2‐dichoroethene [cis‐1,2‐DCE], and vinyl chloride [VC]) via enhanced reductive dechlorination (ERD). Carbon substrates were injected to create microbial‐induced geochemically reducing conditions. An abiotic reductant (zero‐valent iron [ZVI]) was also used to further degrade the CVOCs, minimizing the generation of 1,1‐DCE and VC, and co‐precipitate temporarily mobilized metals. An in situ aerobic zone was created downgradient of the treatment zone through the injection of oxygen. Remaining CVOC degradation products and temporarily mobilized metals (e.g., iron and manganese) resulting from the geochemically reducing conditions were then allowed to migrate through the aerobic zone. Within the aerobic zone, the lesser chlorinated CVOCs were oxidized and the solubilized metals were precipitated out of solution. The injection of a combination of carbon substrates and ZVI into the groundwater system at the site studied herein resulted in the generation of a geochemically reducing subsurface treatment zone that has lasted for more than 4.5 years. Mass concentrations of total CVOCs were degraded within the treatment zone, with near complete transformation of chlorinated ethenes and a more than 90 percent reduction of CVOC mass concentrations. Production of VC and 1,1‐DCE has been minimized through the combined effects of abiotic and biological processes. CVOC concentrations have declined over time and temporarily mobilized metals are precipitating out of the dissolved phase. Precipitation of the dissolved metals was mitigated using the in situ oxygenation system, also resulting in a return to aerobic conditions in downgradient groundwater. Chloroethane (CA) is the dominant CVOC degradation product within the treatment zone and downgradient of the treatment zone, and it is expected to continue to aerobically degrade over time. CA did not accumulate within and near the aerobic oxygenation zone. The expectations for the remediation system are: (1) the concentrations of CVOCs (primarily in the form of CA) will continue to degrade; (2) total organic carbon concentrations will continue to decline to pre‐remediation levels; and, (3) the groundwater geochemistry will experience an overall trend of transitioning from reducing back to pre‐remediation mildly oxidizing conditions within and downgradient of the treatment zone.     

Optimizing remediation strategies for a former dry‐cleaner site

Residual tetrachloroethene (PCE) contamination at the former Springvilla Dry Cleaners site in Springfield, Oregon, posed a potential risk through the vapor intrusion, direct contact, and off‐site beneficial groundwater uses. The Oregon Department of Environmental Quality utilized the State Dry Cleaner Program funds to help mitigate the risks posed by residual contamination. After delineation activities were complete, the source‐area soils were excavated and treated on‐site with ex situ vapor extraction to reduce disposal costs. Residual source‐area contamination was then chemically oxidized using sodium permanganate. Dissolved‐phase contamination was subsequently addressed with in situ enhanced reductive dechlorination (ERD). ERD achieved treatment goals across more than 4 million gallons of aquifer impacted with PCE concentrations up to 7,800 micrograms per liter prior to remedial activities. The ERD remedy introduced electron donors and nutrient amendments through groundwater recirculation and slug injection across two aquifers over the course of 24 months. Adaptive and mass‐targeted strategies reduced total remedy costs to approximately $18 per ton within the treatment areas. © 2010 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.     

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.     

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.     

Conceptual Site Model Development and Phased Remedy Implementation to Achieve Vapor Screening Goals at a Former Dry Cleaner

Tetrachloroethene (PCE) releases at a former dry cleaner resulted in impacts to soil and shallow groundwater beneath and adjacent to the building. Subsurface impacts led to vapor intrusion with PCE concentrations between 900 and 1,200 micrograms per cubic meter (μg/m³) in indoor air. The migration pathways of impacted soil vapor were evaluated through implementation of a helium tracer test and vapor sampling of an exterior concrete block wall. Results confirmed that the concrete block wall acted as a conduit for vapor intrusion into the building. A combination of remediation efforts focused on mass reduction in the source area as well as mitigation efforts to inhibit vapor migration into the building. Excavation of soils beneath the floor slab and installation of a spray‐applied vapor barrier resulted in PCE concentrations in indoor air decreasing by over 97.9 percent. Operation of an active ventilation system installed under the floor slab and groundwater remediation via injections of nano‐scale zero valent iron (nZVI) further reduced PCE concentrations in indoor air by over 99.8 percent compared to baseline conditions. While significant reductions of PCE concentrations in groundwater were observed within two months after injection, maximum reductions to PCE concentrations in indoor air were not observed for an additional 12 months. © 2014 Wiley Periodicals, Inc.     

Impact of iron concentration and ph on zero‐valent iron dechlorination of DDT for brownfields

Soil contamination with persistent pesticides such as dichloro‐diphenyl‐trichloroethane (DDT) is a major issue at many brownfield sites. A technology that can be used to treat DDT‐contaminated soil using surfactants is to enhance the migration of the contaminants from the soil phase to the liquid phase, followed by the dechlorinating of the mobilized DDT in the liquid phase using zero‐valent iron (ZVI). The DDT degradation using ZVI occurs under anaerobic conditions via reductive reactions. The effect of the iron concentration on the dechlorination rate is assessed in the range of 1 to 40 percent (weight to volume) for remediation of a DDT‐contaminated site in Ontario, Canada. The optimum percentage of iron is found to be 20 percent at which the dechlorination rates of DDT and 1,1‐dichloro‐2,2‐bis(p‐chlorophenyl)ethane (DDD) were 4.5 and 0.6 mg/L/day, respectively. While mixing of the reaction solution is shown to be important in providing the iron surface available for the dechlorination reaction throughout the reaction solution, there is no significant difference between batch and fed‐batch mode of adding iron to the dechlorination process. Low pH values (pH = 3) increased the dechlorination rates of DDT and DDD to 6.03 and 0.75 mg/L/day, respectively at a 20 percent iron concentration, indicating increased dechlorination rates in acidic conditions. © 2010 Wiley Periodicals, Inc.     

Successful unsaturated zone treatment of PCE with sodium permanganate

In situ chemical oxidation (ISCO) with permanganate has been widely used for soil and groundwater treatment in the saturated zone. Due to the challenges associated with achieving effective distribution and retention in the unsaturated zone, there is a great interest in developing alternative injection technologies that increase the success of vadose‐zone treatment. The subject site is an active dry cleaner located in Topeka, Kansas. A relatively small area of residual contamination adjacent to the active facility building has been identified as the source of a large sitewide groundwater contamination plume with off‐site receptors. The Kansas Department of Health and Environment (KDHE) currently manages site remedial efforts and chose to pilot‐test ISCO with permanganate for the reduction of perchloroethene (PCE) soil concentrations within the source area. KDHE subsequently contracted Burns & McDonnell to design and implement an ISCO pilot test. A treatability study was performed by Carus Corporation to determine permanganate‐soil‐oxidant‐demand (PSOD) and the required oxidant dosing for the site. The pilot‐test design included an ISCO injection approach that consisted of injecting aqueous sodium permanganate using direct‐push technology with a sealed borehole. During the pilot test, approximately 12,500 pounds of sodium permanganate were injected at a concentration of approximately 3 percent (by weight) using the methods described above. Confirmation soil sampling conducted after the injection event indicated PCE reductions ranging from approximately 79 to more than 99 percent. A follow‐up treatment, consisting of the injection of an additional 6,200 pounds of sodium permanganate, was implemented to address residual soil impacts remaining in the soil source zone. Confirmation soil sampling conducted after the treatment indicated a PCE reduction of greater than 90 percent at the most heavily impacted sample location and additional reductions in four of the six samples collected. © 2009 Wiley Periodicals, Inc.     

Pilot‐scale evaluation using bioaugmentation to enhance PCE dissolution at dover AFB national test site

An Interstate Technology and Regulatory Council (ITRC) forum was recently held that focused on six case studies in which bioremediation of dense nonaqueous‐phase liquids (DNAPLs) was performed; the objective was to demonstrate that there is credible evidence for bioremediation as a viable environmental remediation technology. The first two case studies from the forum have been previously published; this third case study involves a pilot‐scale demonstration that investigated the effects of biological activity on enhancing dissolution of an emplaced tetrachloroethene (PCE) DNAPL source. It used a controlled‐release test cell with PCE as the primary DNAPL in a porous media groundwater system. Both laboratory tests and a field‐scale pilot test demonstrated that bioaugmentation can stimulate complete dechlorination to a nontoxic end product and that the mass flux from a source zone increases when biological dehalorespiration activity is enhanced through nutrient (electron donor) addition and bioaugmentation. All project goals were met. Important achievements include demonstrating the ability to degrade a PCE DNAPL source to ethene and obtaining significant information on the impacts to the microbial populations and corresponding isotope enrichments during biodegradation of a source area. © 2007 Wiley Periodicals, Inc.     

Remediation of chlorinated ethenes,ethanes, and methanes in groundwater using carbon‐ and iron‐based electron donor

Field‐scale pilot tests were performed to evaluate enhanced reductive dechlorination (ERD) of dissolved chlorinated solvents at a former manufacturing facility located in western North Carolina (the site). Results of the site assessment indicated the presence of two separate chlorinated solvent–contaminated groundwater plumes, located in the northern and southern portions of the site. The key chlorinated solvents found at the site include 1,1,2,2‐tetrachloroethane, trichloroethene, and chloroform. A special form of EHC^® manufactured by Adventus Americas was used as an electron donor at this site. In this case, EHC is a pH‐buffering electron donor containing controlled release carbon and ZV Iron MicroSphere 200, a micronscale zero‐valent iron (ZVI) manufactured by BASF. Approximately 3,000 pounds of EHC were injected in two Geoprobe^® boreholes in the saprolite zone (southern plume), and 3,500 pounds of EHC were injected at two locations in the partially weathered rock (PWR) zone (northern plume) using hydraulic fracturing techniques. Strong reducing conditions were established immediately after the EHC injection in nearby monitoring wells likely due to the reducing effects of ZV Microsphere 200. After approximately 26 months, the key chlorinated VOCs were reduced over 98 percent in one PWR well. Similarly, the key chlorinated solvent concentrations in the saprolite monitoring wells decreased 86 to 99 percent after initial increases in concentrations of the parent chlorinated solvents. The total organic carbon and metabolic acid concentrations indicated that the electron donor lasted over 26 months after injection in the saprolite aquifer. © 2009 Wiley Periodicals, Inc.     

Field Evidence of Dissolution and Degradation Rates Enhancement During ISCR and ENA Treatments of Chlorinated Solvents

This article presents field tests comparing two methods of treatment of chlorinated solvents undertaken at the same site. The site is an automobile factory where two chlorinated solvents (CS) plumes were identified. At the first source, in situ chemical reduction (ISCR) was applied, while at the second one, enhanced natural attenuation (ENA) was used. A set of specific multilevel sampling wells were installed approximately 20 m downgradient of the sources to estimate the efficiency of the treatments. The presence of a low‐permeability layer (source 1) or a thick oil lens (source 2) in the top part of the aquifer prevented the CS from reaching the bottom of the aquifer. These layers led to difficulties treating the contamination. At the ISCR and ENA treatment zones, the concentrations of tetrachloroethene (PCE) and trichloroethene (TCE) did not change significantly, while the concentration of metabolites (cis‐1,2‐DCE, vinyl chloride, and ethene) significantly increased 50 to 150 days after treatment. Due to high concentration of CS in the source zone, a mass balance calculation, including chlorine, was possible. It showed that around 1 to 2 percent of the injected products were used to reduce the CS. A detailed analysis and 1D analytical modeling of CS concentrations showed that the treatment led to a large (two to three times) increase in dissolution of the organic phase. This explains why, despite an efficient treatment, the PCE and TCE concentrations remained virtually unchanged. Degradation rates also increased due to the treatment. Due to some differences in the source‐zone chemistry, it was not possible to differentiate between the ISCR and ENA efficiencies. © 2013 Wiley Periodicals, Inc.     

Successful combination of remediation techniques at a former silver factory

A residential area that was formerly part of a silver factory site severely contaminated with chlorinated solvents was remediated using an in situ electro‐bioreclamation technique. Electro‐bioreclamation is a method for heating soil and groundwater combined with soil vapor and low‐yield groundwater extraction and enhanced reductive dechlorination (ERD). During the first two years of remediation in the source area (the intensive phase), a total of 80 kg of volatile organic compounds (VOCs) was removed by heating combined with ERD. After another two years of ERD in the source and plume areas (the attenuation phase), the VOC concentrations were reduced to a level below 100 μg/L in groundwater. Given these satisfying results, electro‐reclamation in combination with ERD turned out to be a successful in situ remediation technique for removing VOCs. © 2006Wiley Periodicals, Inc.     

Utilization of nanoscale zero‐valent iron for source remediation—A case study

A pilot‐scale study was performed using a palladium‐catalyzed and polymer‐coated nanoscale zero‐valent iron (ZVI) particle suspension at the Naval Air Station in Jacksonville, Florida. A total of 300 pounds of nanoscale ZVI particle suspension was injected via a gravity feed and recirculated through a source area containing chlorinated volatile organic compounds (VOCs). The recirculation created favorable mixing and distribution of the iron suspension and enhanced the mass transfer of sorbed and nonaqueous constituents into the aqueous phase, where the contaminants could be reduced. Between 65 and 99 percent aqueous‐phase VOC concentration reduction occurred, due to abiotic degradation, within five weeks of the injection. The rapid abiotic degradation processes then yielded to slower biological degradation as subsequent decreases in ‐elimination parameters were observed—yet favorable redox conditions were maintained as a result of the ZVI treatment. Post‐treatment analyses revealed cumulative reduction of soil contaminant concentrations between 8 and 92 percent. Aqueous‐phase VOC concentrations in wells side gradient and downgradient of the source were reduced up to 99 percent and were near or below applicable regulatory criteria. These reductions, coupled with the generation of innocuous by‐products, indicate that nanoscale ZVI effectively degraded contamination and reduced the mass flux from the source, a critical metric identified for source treatment. A summary of this project was recently presented at the US EPA Workshop on Nanotechnology for Site Remediation in Washington, D.C., on October 21–22, 2005. This case study supplied evidence that nanoscale zero valent iron, an emerging remediation technology, has been implemented successfully in the field. More information about this workshop and this presentation can be found at www.frtr.gov/nano/index.htm. © 2006 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.     

Bioremediation of a former dry cleaner using potassium lactate

Chlorinated solvents were released to the surficial groundwater underneath a former dry cleaning building, resulting in a groundwater plume consisting of high concentrations of trichloroethene (TCE) and cis‐1,2‐dichloroethene (cis‐1,2‐DCE) and low concentrations of tetrachloroethene (PCE) and vinyl chloride. The initial remedial action included chemical oxidation via injection of 14,400 gallons of Fenton's Reagent in March 2002, and an additional 14,760 gallons in April 2002. A sharp reduction of contaminant concentrations in groundwater was observed the following month; however, rebound of contaminant concentrations was evident as early as October 2002. A source area of PCE‐impacted soils was excavated in June 2004. Following the excavation, Golder Associates Inc. (2007) implemented a biostimulation plan by injecting 55 gallons of potassium lactate (PURASAL® HiPure P) in September 2005, and again in February 2006. Comparing the preinjection and postinjection site conditions, the potassium lactate treatments were successful in accomplishing a 40 to 70 percent reduction in mass within four months following the second injection. Elevated vinyl chloride concentrations have persisted through both injection events; however, significant vinyl chloride reduction has been observed in one well with the highest total organic carbon (TOC) concentrations following each injection. © 2008 Wiley Periodicals, Inc.     

Remedial options for chlorinated volatile organics in a partially anaerobic aquifer

A laboratory study was conducted for the selection of appropriate remedial technologies for a partially anaerobic aquifer contaminated with chlorinated volatile organics (VOCs). Evaluation of in situ bioremediation demonstrated that the addition of electron donors to anaerobic microcosms enhanced biological reductive dechlorination of tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA) with half‐lives of 20, 22, and 41 days, respectively. Nearly complete reductions of PCE, TCE, 1,1,1‐TCA, and the derivative cis‐dichloroethene were accompanied by a corresponding increase in chloride concentrations. Accumulation of vinyl chloride, ethene, and ethane was not observed; however, elevated levels of ¹⁴CO₂ (from ¹⁴C‐TCE spiked) were recovered, indicating the occurrence of anaerobic oxidation. In contrast, very little degradation of 1,2‐dichloropropane (1,2‐DCP) and 1,1‐dichlorethane (1,1‐DCA) was observed in the anaerobic microcosms, but nutrient addition enhanced their degradation in the aerobic biotic microcosms. The aerobic degradation half‐lives for 1,2‐DCP and 1,1‐DCA were 63 and 56 days, respectively. Evaluation of in situ chemical oxidation (ISCO) demonstrated that chelate‐modified Fenton's reagent was effective in degrading aqueous‐phase PCE, TCE, 1,1,1‐TCA, 1,2‐DCP, etc.; however, this approach had minimal effects on solid‐phase contaminants. The observed oxidant demand was 16 g‐H₂O₂/L‐groundwater. The oxidation reaction rates were not highly sensitive to the molar ratio of H₂O₂:Fe²⁺:citrate. A ratio of 60:1:1 resulted in slightly faster removal of chemicals of concern (COCs) than those of 12:1:1 and 300:1:1. This treatment resulted in increases in dissolved metals (Ca, Cr, Mg, K, and Mn) and a minor increase of vinyl chloride. Treatment with zero‐valent iron (ZVI) resulted in complete dechlorination of PCE, and TCE to ethene and ethane. ZVI treatment reduced 1,1,1‐TCA only to 1,1‐DCA and chloroethane (CA) but had little effect on reducing the levels of 1,2‐DCP, 1,1‐DCA, and CA. The longevity test showed that one gram of 325‐mesh iron powder was exhausted in reaction with > 22 mL of groundwater. The short life of ZVI may be a barrier to implementation. The ZVI surface reaction rates (k_sa) were 1.2 × 10^?2 Lm^?2h^?1, 2 × 10^?3 Lm^?2h^?1, and 1.2 × 10^?3 Lm^?2h^?1 for 1,1,1‐TCA, TCE, and PCE, respectively. Based upon the results of this study, in situ bioremediation appeared to be more suitable than ISCO and ZVI for effectively treating the groundwater contamination at the site. © 2004 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.     

Optimal Treatment Zone Moves During Enhanced Reductive Dechlorination in Fractured Bedrock

An enhanced bioremediation pilot test was implemented to study the efficacy of enhancing in situ reductive dechlorination of tetrachloroethene (PCE) in shallow bedrock where some intrinsic degradation to cis‐1,2‐dichloroethene (cis‐1,2‐DCE) was observed without further degradation to vinyl chloride or nontoxic ethene. Limited Dehalococcoides spp. cell concentrations were present within the study area prior to the gravity‐fed injection of an injectate of fermentable carbon substrates in native anaerobic groundwater. Direct connectivity between the injection well screen and performance monitoring well was evidenced and resulted in the degradation of nearly all PCE to cis‐1,2‐DCE, significant decrease in pH, and apparent inhibited Dehalococcoides spp. growth in the study area groundwater in the first six months. After 24 months, nearly all cis‐1,2‐DCE had degraded to nontoxic ethene, pH rebounded to more optimal levels, and abundant growth of Dehalococcoides spp. (6.8E05 cells/mL) and its functional gene expressions responsible for complete dechlorination were evident. The observations indicated initial poor dechlorination within the injection zone did not preclude effective treatment, allowing sufficient monitoring time showed the effective treatment zone (or more‐optimal fringe) first moved outward from the injection zone beyond the monitoring point and then receded back toward the point of injection over a period of two years. ©2015 Wiley Periodicals, Inc.