Characterization and pilot‐scale studies for chemical oxidation remediation of fractured shale

The distribution of volatile organic compounds (VOCs) in fractured shale overlain by thin (< 10 feet) overburden at the Watervliet Arsenal near Albany, New York, was initially determined by sampling water from the fracture network using packer systems in boreholes and also using conventional monitoring wells. Furthermore, short‐term pumping and injection tests were conducted and the boreholes were logged using a variety of geophysical and hydrophysical tools. Tetrachloroethene is the dominant VOC in the groundwater, with lesser concentrations of trichloroethene and degradation products (cis‐1,2‐dichloroethene, trans‐1,2‐dichloroethene, and vinyl chloride). The vertical VOC distributions in the rock matrix were obtained from continuous‐cored holes from which small rock samples, collected at many depths between 18 and 150 feet below ground surface, were analyzed. The rock core VOC concentrations were determined by methanol extraction of crushed rock followed by direct methanol injection onto a gas chromatograph and subsequent estimation of rock porewater VOC concentrations. The rock core data support the concept that diffusion‐driven mass transfer has caused nearly all the VOC mass initially present in the fractures to now reside in the rock matrix, which has a porosity three or four orders of magnitude larger than the bulk fracture porosity. The results of the site characterization indicate that an effective site investigation strategy in fractured shale must include characterization of both the fracture and matrix contaminant distribution. These results also indicate that the most favorable remediation technologies for this fractured shale are those that will destroy VOCs in the rock matrix, particularly contaminants in the sorbed phase, and also destroy the VOC mass in the fractures including both dissolved and immiscible phases. The site characterization resulted in the selection of potassium permanganate for an in situ chemical oxidation pilot study. © 2004 Wiley Periodicals, Inc.     

Pilot Scale Demonstration of the Electrochemical Peroxidation Process at a Petroleum Spill Site

In a pilot test experiment involving approximately 200,000 gallons of groundwater, Electrochemical Peroxidation (ECP) was used to degrade aqueous phase volatile organic compounds (VOCs) including benzene, toluene, ethylbenzene, and xylene (BTEX) compounds and methyl tertbutyl ether (MTBE) from a petroleum spill. ECP involves a form of the Fenton's Reagent reaction, which uses electrochemically generated iron and dilute hydrogen peroxide (<30 mg/L) to break down organic molecules through oxidation to carbon dioxide and water. This article discusses a pilot scale demonstration of the ECP technology and its application to aqueous phase organic contaminants. The remedial approach used at the pilot test site involves three phases: (1) ex‐situ chemical oxidation, (2) in‐situ oxidation by reinjection of treated effluent near the plume origin, and (3) reestablishment of aerobic biodegradation as the residual hydrogen peroxide discharged to a series of upgradient wells degrades to oxygen. Analytical results of the pilot demonstration indicate that the ex‐situ chemical oxidation reduced total BTEX concentrations in groundwater from over 1,000 ppb to undetectable concentrations (<1 ppb). © 2000 John Wiley & Sons, Inc.     

ART in‐well technology proves effective in treating 1,4‐dioxane contamination

A common industrial solvent additive is 1,4‐dioxane. Contamination of dissolved 1,4‐dioxane in groundwater has been found to be recalcitrant to removal by conventional, low‐cost remedial technologies. Only costly labor and energy‐intensive pump‐and‐treat remedial options have been shown to be effective remedies. However, the capital and extended operation and maintenance costs render pump‐and‐treat technologies economically unfeasible at many sites. Furthermore, pump‐and‐treat approaches at remediation sites have frequently been proven over time to merely achieve containment rather than site closure. A major manufacturer in North Carolina was faced with the challenge of cleaning up 1,4‐dioxane and volatile organic compound–impacted soil and groundwater at its site. Significant costs associated with the application of conventional approaches to treating 1,4‐dioxane in groundwater led to an alternative analysis of emerging technologies. As a result of the success of the Accelerated Remediation Technologies, LLC (ART) In‐Well Technology at other sites impacted with recalcitrant compounds such as methyl tertiarybutyl ether, and the demonstrated success of efficient mass removal, an ART pilot test was conducted. The ART Technology combines in situ air stripping, air sparging, soil vapor extraction, enhanced bioremediation/oxidation, and dynamic subsurface groundwater circulation. Monitoring results from the pilot test show that 1,4‐dioxane concentrations were reduced by up to 90 percent in monitoring wells within 90 days. The removal rate of chlorinated compounds from one ART well exceeded the removal achieved by the multipoint soil vapor extraction/air sparging system by more than 80 times. © 2005 Wiley Periodicals, Inc.     

Remedial Process Optimization and Ozone Sparging for Petroleum Hydrocarbon‐Impacted Groundwater

A former natural gas processing station is impacted with total petroleum hydrocarbons (TPH) and benzene. Remedial process optimization (RPO) was conducted to evaluate the effectiveness of the historical air sparging/soil vapor extraction (AS/SVE) system and the current groundwater extraction and treatment system. The RPO indicated that both remedial activities offered no further benefit in meeting remediation goals. Instead, an in situ chemical oxidation (ISCO) system was recommended. Ozone was selected, and the results of a bench test indicated that the ozone demand was 8 to 12 mg ozone/mg TPH and that secondary by‐products would include hexavalent chromium and bromate. A capture zone analysis was conducted through groundwater flow modeling (MODFLOW) to ensure containment of the injected oxidant using the existing groundwater extraction system. Results of a pilot study indicated that the optimum frequency of ozone sparging is 60 minutes in order to reach a maximum radius of influence of 20 feet. TPH concentrations within the treatment zone decreased by 97 percent over two months of ozone sparging. Concentrations of hexavalent chromium and bromate increased from nondetect to 44 and 110 mg/L, respectively, during the ozone sparging but attenuated to nondetectable concentrations within three months of system shut down. ©2016 Wiley Periodicals, Inc.     

The ART In‐Well Technology test at a chlorinated solvent site in central Iowa

An Accelerated Remediation Technologies (ART) In‐Well Technology pilot test was performed to evaluate the removal of chlorinated volatile organic compounds (VOCs) from groundwater. The ART In‐Well Technology was installed in one well located in the source area where dense nonaqueous‐phase liquid has been identified and VOC concentrations exceed 140,000 μg/L. Monitoring wells at the site were positioned between 10 and 170 feet from the ART test well. Overall, VOC concentrations from samples collected from the groundwater monitoring wells and in the vapors extracted for discharge from the ART treatment well were analyzed over the testing period. Monitoring results showed that concentrations of perchloroethylene were reduced in the closest monitoring well to nondetectable concentrations within 90 days. The cumulative removal of chlorinated VOCs from the ART test well over the six‐month pilot test period exceeded 9,500 pounds based on air monitoring data. The ART technology proved effective and cost‐efficient in reducing contaminant concentrations and removing a large mass of contamination from the subsurface in a short period of time. The radius of influence of the ART technology at the site was estimated to range between 65 and 170 feet. © 2007 Wiley Periodicals, Inc.     

Re‐evaluation of treatment approach for a site contaminated with Freon‐113 and 1,1,1‐trichloroethane

This study demonstrates a remedial approach for completing the remediation of an aquifer contaminated with 1,1,2‐trichlorotrifluoroethane (Freon‐113) and 1,1,1‐trichloroethane (TCA). In 1987, approximately 13,000 pounds of Freon‐113 were spilled from a tank at an industrial facility located in the state of New York. The groundwater remediation program consisted of an extraction system coupled with airstripping followed by natural attenuation of residual contaminants. In the first phase, five recovery wells and an airstripping tower were operational from April 1993 to August 1999. During this time period over 10,000 pounds of CFC‐13 and 200 pounds of TCA were removed from the groundwater and the contaminant concentrations decreased by several orders of magnitude. However, the efficiency of the remediation system to recover residual Freon and/or TCA reduced significantly. This was evidenced by: (1) low levels (< 10 ppb) of Freon and TCA captured in the extraction wells and (2) a slight increase of Freon and/or TCA in off‐site monitoring wells. A detailed study was conducted to evaluate the alternative for the second‐phase remediation. Results of a two‐year groundwater monitoring program indicated the contaminant plume to be stable with no significant increase or decrease in contaminant concentrations. Monitored geochemical parameters suggest that biodegradation does not influence the fate and transport of these contaminants, but other mechanisms of natural attenuation (primarily sorption and dilution) appear to control the fate and transport of these contaminants. The contaminants appear to be bound to the soil matrix (silty and clay units) with limited desorption as indicated by the solid phase analyses of contaminant concentrations. Results of fate and transport modeling indicated that contaminant concentrations would not exceed the action levels in the wells that showed a slight increase in contaminant concentrations and in the downgradient wells (sentinel) during the modeled timeframe of 30 years. This feasibility study for natural attenuation led to the termination of the extraction system and a transaction of the property, resulting in a significant financial benefit for the original site owner. © 2003 Wiley Periodicals, Inc.     

Best Available Treatment Technologies Applied to Groundwater Circulation Wells

Groundwater circulation wells (GCWs) are a quasi‐in‐situ method for remediating groundwater in areas where remediation techniques that limit the water available for municipal, domestic, industrial, or agricultural purposes are inappropriate. The inherently resource‐conservative nature of groundwater circulation wells is also philosophically appealing in today's culture, which is supportive of green technologies. Groundwater circulation wells involve the circulation of groundwater through a dual‐screen well, with treatment occurring between the screens. The wells are specifically designed so that one well screen draws in groundwater and the second returns the groundwater after it has been treated within the well. Historically, the treatment has been performed with specialized equipment proprietary to GCW vendors. Two full‐scale pilot systems at a formerly used Defense Superfund site in Nebraska used best available technologies for treatment components. A multiple‐tray, low‐profile air stripper typically used for pump‐and‐treat remediation systems was successfully adapted for the GCW pilot system located in a trichloroethylene (TCE) hot spot. An ultraviolet water disinfection system was successfully adapted for the GCW pilot system located in a hot spot contaminated with the explosive compound hexhydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). The pilot systems showed that GCW technology is competitive with a previously considered pump‐and‐treat alternative for focused extraction, and the regulatory community was supportive of additional GCW applications. A remedial design for the site includes 12 more GCW systems to complete focused remediation requirements. © 2002 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.     

The in situ treatment of BTEX,MTBE, and TBA in saline groundwater

A pilot‐scale test was conducted in a saline aquifer to determine if a petroleum hydrocarbon (PHC) plume containing benzene (B), toluene (T), ethylbenzene (E), xylenes (X), methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) could be treated effectively using a sequential treatment approach that employed in situ chemical oxidation (ISCO) and enhanced bioremediation (EBR). Chemical oxidants, such as persulfate, have been shown to be effective in reducing dissolved concentrations of BTEX (B + T + E + X) and additives such as MTBE and TBA in a variety of geochemical environments including saline aquifers. However, the lifespan of the oxidants in saline environments tends to be short‐lived (i.e., hours to days) with their effectiveness being limited by poor delivery, inefficient consumption by nontargeted species, and back‐diffusion processes. Similarly, the addition of electron acceptors has also been shown to be effective at reducing BTEX and associated additives in saline groundwater through EBR, however EBR can be limited by various factors similar to ISCO. To minimize the limitations of both approaches, a pilot test was carried out in a saline unconfined PHC‐impacted aquifer to evaluate the performance of an engineered, combined remedy that employed both approaches in a sequence. The PHC plume had total BTEX, MTBE, and TBA concentrations of up to 4,584; 55,182; and 1,880 μg/L, respectively. The pilot test involved injecting 13,826 L of unactivated persulfate solution (19.4 weight percent (wt.%) sodium persulfate (Na₂S₂O₈) solution into a series of injection wells installed within the PHC plume. Parameters monitored over a 700‐day period included BTEX, MTBE, TBA, sulfate, and sulfate isotope concentrations in the groundwater, and carbon and hydrogen isotopes in benzene and MTBE in the groundwater. The pilot test data indicated that the BTEX, MTBE, and TBA within the PHC plume were treated over time by both chemical oxidation and sulfate reduction. The injection of the unactivated persulfate resulted in short‐term decreases in the concentrations of the BTEX compounds, MTBE, and TBA. The mean total BTEX concentration from the three monitoring wells within the pilot‐test area decreased by up to 91%, whereas MTBE and TBA mean concentrations decreased by up to 39 and 58%, respectively, over the first 50 days postinjection in which detectable concentrations of persulfate remained in groundwater. Concentrations of the BTEX compounds, MTBE, and TBA rebounded at the Day 61 marker, which corresponded to no persulfate being detected in the groundwater. Subsequent monitoring of the groundwater revealed that the concentrations of BTEX continued to decrease with time suggesting that EBR was occurring within the plume. Between Days 51 and 487, BTEX concentrations decreased an additional 84% from the concentration measured on Day 61. Mean concentrations of MTBE showed a reduction during the EBR phase of remediation of 33% while the TBA concentration appeared to decrease initially but then increased as the sulfate concentration decreased as a result of MTBE degradation. Isotope analyses of dissolved sulfate (³⁴S and ¹⁸O), and compound‐specific isotope analysis (CSIA) of benzene and MTBE (¹³C and ²H) supported the conclusions that ISCO and EBR processes were occurring at different stages and locations within the plume over time.     

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.     

Remediating TCE‐contaminated groundwater in low‐permeability media using hydraulic fracturing to emplace zero‐valent iron/organic carbon amendment

A field pilot test in which hydraulic fracturing was used to emplace granular remediation amendment (a mixture of zero‐valent iron [ZVI] and organic carbon) into fine‐grained sandstone to remediate dissolved trichloroethene (TCE)‐contaminated groundwater was performed at a former intercontinental ballistic missile site in Colorado. Hydraulic fracturing was used to enhance the permeability of the aquifer with concurrent emplacement of amendment that facilitates TCE degradation. Geophysical monitoring and inverse modeling show that the network of amendment‐filled fractures extends throughout the aquifer volume targeted in the pilot test zone. Two years of subsequent groundwater monitoring demonstrate that amendment addition resulted in development of geochemical conditions favorable to both abiotic and biological TCE degradation, that TCE concentrations were substantially reduced (i.e., greater than 90 percent reduction in TCE mass), and that the primary degradation processes are likely abiotic. The pilot‐test data aided in re‐evaluating the conceptual site model and in designing the full‐scale remedy to address a larger portion of the TCE‐contaminated groundwater plume. © 2012 Wiley Periodicals, Inc.     

Challenges of soil mixing using catalyzed hydrogen peroxide with rotating dual axis blending technology

Although known to be one of the most effective oxidants for treatment of organic contaminants, catalyzed hydrogen peroxide (CHP) is typically not used for soil mixing applications because of health and safety concerns related to vapor generation and very rapid rates of reaction in open excavations. In likely the first large‐scale in situ CHP soil mixing application, an enhanced CHP, modified Fenton's reagent (MFR), was applied during soil mixing at the Kearsarge Metallurgical Superfund Site in New Hampshire. An innovative rotating dual‐axis blender (DAB) technology was used to safely mix the MFR into low‐plasticity silt and clay soils to remediate residual 1,1,1‐trichloroethane (111TCA); 1,1‐dichloroethene (11DCE); and 1,4‐dioxane (14D). It was expected that the aggressive treatment approach using relatively “greener” hydrogen peroxide (HP) chemistry would effectively treat Site contaminants without significant byproduct impacts to groundwater or the adjacent pond. The remediation program was designed to treat approximately 3,000 cubic yards of residual source area soil in situ by aggressively mixing MFR into the soils. The subsurface interval treated was from 7 to 15 feet below ground surface. To accurately track the soil mixing process and MFR addition, the Site was divided into 109 10‐foot square treatment cells that were precisely located, dosed, and mixed using the DAB equipped with an on‐board GPS system. The use of stabilizing agents along with careful calculation of the peroxide dose helped to ensure vapor‐free conditions in the vicinity of the soil mixing operation. Real‐time sampling and monitoring were critical in identifying any posttreatment exceedences of the cleanup goals. This allowed retreatment and supplemental testing to occur without impacting the soil mixing/in situ chemical oxidation (ISCO) schedule. Posttreatment 24‐hr soil samples were collected from 56 random locations after ensuring that the HP had been completely consumed. The posttreatment test results showed that 111TCA and 11DCE concentrations were reduced to nondetect (ND) or below the cleanup goals of 150 μg/kg for 111TCA and 60 μg/kg for 11DCE. Supplemental posttreatment soil samples, collected six months after treatment, showed 100 percent compliance with the soil treatment goals. Groundwater samples collected one year after the MFR soil mixing treatment program showed either ND or low concentrations for 111TCA, 11DCE, and 14D. Successful stabilization and site restoration was performed after overcoming considerable challenges associated with loss of soil structure, high liquid content, and reduced bearing capacity of the blended soils.     

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.     

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.     

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.     

Nanotechnology and groundwater remediation: A step forward in technology understanding

Nanotechnology application to contaminated site remediation, and especially the use of nanoscale zero‐valent iron particles to treat volatile organic compound (VOC)‐impacted groundwater, is now recognized as a promising solution for cost‐effective in situ treatment. Results obtained during numerous pilot tests undertaken by Golder Associates between 2003 and 2005 in North America (United States and Canada) and Europe have been used to present a synthetic cross‐comparison of technology dynamics. The importance of a comprehensive understanding of the site‐specific geological, hydrogeological, and geochemical conditions, the selection of appropriate nanoscale particles, the importance of monitoring geochemical parameters during technology application, and the potential of nanoparticle impact on microbial activity are discussed in this article. The variable technology dynamics obtained during six pilot tests (selected among numerous other tests) are then presented and discussed. © 2006 Wiley Periodicals, Inc.     

Chemical Oxidation Performance in High Temperature,Saline Groundwater Impacted With Hydrocarbons

A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for in situ chemical oxidation (ISCO) of aromatic hydrocarbons and methyl tertiary butyl ether (MTBE), a common oxygenate additive in gasoline, in saline, high temperature (more than 30 °C) groundwater. Groundwater samples from a site in Saudi Arabia were amended in the laboratory portion of the study with the chemical oxidants, sodium persulfate (Na₂S₂O₈) and sodium percarbonate (Na₂(CO₃)₂), to evaluate the changes in select hydrocarbon and MTBE concentrations with time. Almost complete degradation of the aromatic hydrocarbons, naphthalene and trimethylbenzenes (TMBs), was found in the groundwater sample amended with persulfate, whereas the percarbonate‐amended sample showed little to no degradation of the target hydrocarbon compounds in the laboratory. Isotopic analyses of the persulfate‐amended samples suggested that C‐isotope fractionation for xylenes occurred after approximately 30 percent reduction in concentration with a decline of about 1 percent in the δ¹³C values of xylenes. Based on the laboratory results, pilot‐scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of chemical oxidation using nonactivated persulfate on a high temperature, saline petroleum hydrocarbon plume. Approximately 1,750 kg of Na₂S₂O₈ was delivered to the subsurface using a series of injection wells over three injection events. Results obtained from the pilot test indicated that all the target compounds decreased with removal percentages varying between 86 percent for naphthalene and more than 99 percent for the MTBE and TMBs. The benzene, toluene, ethylbenzene, and xylene compounds decreased to 98 percent on average. Examination of the microbial population upgradient and downgradient of the ISCO reactive zone suggested that a bacteria population was present following the ISCO injections with sulfate‐reducing bacteria (SRB) being the dominant bacteria present. Measurements of inorganic parameters during injection and postinjection indicated that the pH of the groundwater remained neutral following injections, whereas the oxidation–reduction potential remained anaerobic throughout the injection zone with time. Nitrate concentrations decreased within the injection zone, suggesting that the nitrate may have been consumed by denitrification reactions, whereas sulfate concentrations increased as expected within the reactive zone, suggesting that the persulfate produced sulfate. Overall, the injection of the oxidant persulfate was shown to be an effective approach to treat dissolved aromatic and associated hydrocarbons within the groundwater. In addition, the generation of sulfate as a byproduct was an added benefit, as the sulfate could be utilized by SRBs present within the subsurface to further biodegrade any remaining hydrocarbons. ©2015 Wiley Periodicals, Inc.     

Laboratory validation study of new vapor‐phase‐based approach for groundwater monitoring

Recent improvements in field‐portable analytical equipment allow accurate on‐site measurement of VOCs present in air at concentrations of less than 0.1 parts per million volume (ppmv). The objective of this project is to determine if the use of these instruments for vapor‐phase measurements of headspace in a monitoring well can serve as a reliable and accurate method for monitoring volatile organic compound (VOC) concentrations in groundwater under equilibrium conditions. As part of a comprehensive research project investigating the utility of this proposed monitoring method, the authors have completed a laboratory validation study to identify instruments and sample‐collection methods that will provide accurate measurement of VOC concentrations in groundwater. This laboratory validation study identified two field‐portable instruments (a gas chromatograph and a photoionization detector) with sufficient sensitivity to measure VOCs in groundwater at concentrations below typical monitoring standards (i.e., 1 to 5 μg/L). The accuracy and precision of these field instruments was sufficient to satisfy typical data‐quality objectives for laboratory‐based analysis. In addition, two sample‐collection methods were identified that yield vapor‐phase samples in equilibrium with water: direct headspace sampling and passive diffusion samplers. These sample‐collection methods allow the field instruments (which measure VOC concentrations in vapor‐phase samples) to be used to measure VOC concentrations in water. After further validation of these sample‐collection methods in the field, this monitoring method will provide a simple way to obtain accurate real‐time measurements of VOC concentrations in groundwater using inexpensive field‐portable analytical instruments. © 2009 Wiley Periodicals, Inc.     

Limitations on infiltration and reinjection of treated groundwater to remove trace amounts of pesticides in groundwater and soil

Infiltration and reinjection of treated groundwater have been used to increase the recovery of pesticide-related constituents at a pesticide formulation plant that produces consumer pesticide products. The stratigraphy at the site consists of silty and sandy clay deposits overlying a shallow silt, sand, and gravel aquifer. The groundwater and soils in two areas in the northwest portion of the property have been identified as being significantly affected by pesticide and pesticide-related compounds. An integrated system of soil removal, recovery wells, injection wells, an infiltration gallery, and a cut-off wall was selected as the best remedial alternative. Groundwater modeling, column tests, biological jar tests, and a pilot test demonstrated the feasibility of the system. The affected groundwater is treated to drinking-water quality by a system of filtering and carbon adsorption. Approximately 75 percent of the treated water is reinjected or allowed to infiltrate through the vadose zone, and the remainder is discharged to the local sewer system. Initially, the system was effective in removing the dissolved, suspended, and weakly adsorbed constituents. Subsequently, the recovery rate of the chemical constituents became dependent on chemical and physical processes related to the presence of residual amounts of dense, nonaqueous phase liquids and the clay content of the strata. The rate of pesticide recovery has decreased because of the retarding effect of the clay and the low solubility of the pesticides.     

Enhanced bioremediation using whey powder for a trichloroethene plume in a high‐sulfate,fractured granitic aquifer

An in situ bioremediation (ISB) pilot study, using whey powder as an electron donor, is being performed at Site 19, Edwards Air Force Base, California, to treat groundwater contaminated with trichloroethene (TCE) via anaerobic reductive dechlorination. Challenging site features include a fractured granitic aquifer, complex geochemistry, and limited biological capacity for reductive dechlorination. ISB was conducted in two phases with Phase I including one‐and‐a‐half years of biostimulation only using whey powder and Phase II including biostimulation with buffered whey powder and bioaugmentation. Results of Phase I demonstrated effective distribution of whey during injections resulting in depletion of high concentrations of sulfate and methanogenesis, but acid production due to whey fermentation and limited buffering capacity of the aquifer resulted in undesirable impacts to pH. In addition, cis‐1,2‐dichloroethene (cis‐1,2‐DCE) stall was observed, which correlated to the unsuccessful growth of native Dehalococcoides populations. Therefore, Phase II included the successful buffering of whey powder using bicarbonate, which mitigated negative pH effects. In addition, bioaugmentation resulted in successful transport of Dehalococcoides populations to greater than 50 feet away from the injection point four months after inoculation. A concomitant depletion of accumulated cis‐1,2‐DCE was observed at all wells affected by bioaugmented Dehalococcoides. © 2008 Wiley Periodicals, Inc.