Soil Vapor Extraction and Chemical Oxidation to Remediate Chlorinated Solvents in Fractured Crystalline Bedrock: Pilot Study Results and Lessons Learned

A pilot study was completed at a fractured crystalline bedrock site using a combination of soil vapor extraction (SVE) and in‐situ chemical oxidation (ISCO) with Fenton's Reagent. This system was designed to destroy 1,1,1‐trichloroethane (TCA) and its daughter products, 1,1‐dichloroethene (DCE) and 1,1‐dichloroethane (DCA). Approximately 150 pounds of volatile organic compounds (VOCs) were oxidized in‐situ or removed from the aquifer as vapor during the pilot study. Largely as a result of chemical oxidation, TCA concentrations in groundwater located within a local groundwater mound decreased by 69 to 95 percent. No significant rebound in VOC concentration was observed in these wells. Wells located outside of the groundwater mound showed less dramatic decreases in VOC concentration, and the data show that vapor stripping and short‐term groundwater migration following the oxidant injection were the key processes at these wells. Although the porosity of the aquifer at the site is on the order of 2 percent or less, the pilot study showed that SVE could be an effective remedial process in fractured crystalline rock. © 2002 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.     

Chemical oxidation of tetrachloroethene in a fractured saprolite/bedrock aquifer

Two chemical oxidizers, Fenton's Reagent (FR) and sodium permanganate (NaMnO₄), were used to remediate groundwater contaminated by tetrachloroethene (PCE) in a fractured saprolite and bedrock aquifer in Rockville, Maryland. Initial PCE concentrations ranged from 11 to 25,000 μg/L, averaging 8,684 μg/L in March 2000. A total of 28,256 pounds of hydrogen peroxide (as 35 percent solution) and iron catalyst were injected during the FR treatment program. The FR failed to achieve the desired clean‐up goal, after which 11,114 pounds of NaMnO₄ (as 40 percent solution) were diluted to a 20 percent solution and injected into the aquifer. An additional 855 pounds of dilute NaMnO₄ was later injected, which ultimately reduced the original PCE mass by an estimated 95 percent through November 2001. © 2003 Wiley Periodicals, Inc.     

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.     

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.     

The Hidden Potential of Mass‐based Treatment: A Method for Preventing Rebound

A major challenge for in situ treatment is rebound. Rebound is the return of contaminant concentrations to near original levels following treatment, and frequently occurs because much of the residual nonaqueous phase liquid (NAPL) trapped within the soil capillaries or rock fractures remains unreachable by conventional in situ treatment. Fine‐textured strata have an especially strong capacity to absorb and retain contaminants. Through matrix diffusion, the contaminants dissolve back into groundwater and return with concentrations that can approach pretreatment levels. The residual NAPL then serves as a continuing source of contamination that may persist for decades or longer. A 0.73‐acre (0.3‐hectare) site in New York City housed a manufacturer of roofing materials for approximately 60 years. Coal tar served as waterproofing material in the manufacturing process and releases left behind residual NAPL in soils. An estimated 47,000 pounds (21,360 kg) of residual coal tar NAPL contaminated soils and groundwater. The soils contained strata composed of sands, silty sands, and silty clay. A single treatment using the RemMetrik^® process and Pressure Pulse Technology^® (PPT) targeted the contaminant mass and delivered alkaline‐activated sodium persulfate to the NAPL at the pore‐scale level via in situ treatment. Posttreatment soil sampling demonstrated contaminant mass reductions over 90 percent. Reductions in posttreatment median groundwater concentrations ranged from 49 percent for toluene to 92 percent for xylenes. Benzene decreased by 87 percent, ethylbenzene by 90 percent, naphthalene by 80 percent, and total BTEX by 91 percent. Mass flux analysis three years following treatment shows sustained reductions in BTEX and naphthalene, and no rebound. ©2015 Wiley Periodicals, Inc.     

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.     

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.     

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.     

Modified Fenton's processes for effective in‐situ chemical oxidation—Laboratory and field evaluation

Fenton's reagent in its conventional form, although effective for contaminant treatment, is impractical from an in‐situ field application perspective due to low pH requirements (i.e., pH 3‐4), and limited reagent mobility when introduced into the subsurface. Modified Fenton's processes that use chelated‐iron catalysts and stabilized hydrogen peroxide have been developed with the goal of promoting effective in‐situ field application under native pH conditions (i.e., pH 5‐7), while extending the longevity of hydrogen peroxide. Laboratory experiments conducted in soil columns packed with organic soil to compare modified Fenton's catalysts with conventional catalysts (acidified iron [II]) indicated superior mobility and sorption characteristics for modified Fenton's catalysts. Furthermore, the acidic pH of a conventional catalyst was buffered to the native soil range, leading to increased iron precipitation/adsorption following permeation through the soil column. The chelates present within the modified Fenton's catalyst showed greater affinity toward iron compared with the native soil and, hence, minimized iron loss through adsorption during the permeation process even at pH 5‐7. Field effectiveness of the modified Fenton's process was demonstrated at a former dry‐cleaning facility located in northeast Florida. Preliminary laboratory‐scale experiments were conducted on soil‐slurry and groundwater samples to test the process efficacy for remediation of chlorinated solvents. Based on successful experimental results that indicated a 94 percent (soil slurry) to 99 percent (groundwater) reduction of cis‐1,2‐DCE, PCE, and TCE, a field‐scale treatment program was initiated utilizing a plurality of dual‐zone direct push injection points installed in a grid fashion throughout the site. Results of treatment indicated a 72 percent reduction in total chlorinated contamination detected in the site groundwater following the first injection event; the reduction increased to 90 percent following the second injection event. © 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.     

Rapid Cleanup of Chlorinated Solvent Source Zones: Synergies Between Chemical and Biological Degradation

A chlorinated volatile organic compound (cVOC) source area approximately 25 by 100 ft in a heavily industrialized urban area was characterized with groundwater tetrachloroethene (PCE) concentrations up to 9,180 μg/L. This is approximately 6 percent of PCE's aqueous solubility, indicative of the presence of residual dense, nonaqueous phase liquid. The resulting dissolved‐phase plume migrated off‐site. Biotic and abiotic dechlorination using a combination of a food‐grade organic carbon‐based electron donor and zero‐valent iron suspended in a food‐grade emulsifying agent reduced the source area PCE concentrations by 98 percent within 27 weeks, with minimal downgradient migration of daughter products dichloroethene and vinyl chloride. Combining biological dechlorination with iron‐based chemical dechlorination is synergistic, enhancing treatment aggressiveness, balancing pH, and optimizing degradation of both DNAPL and dissolved‐phase cVOCs. © 2013 Wiley Periodicals, Inc.     

Estimating the total oxidant demand for in situ chemical oxidation design

Analytical techniques for designing of in situ chemical oxidation (ISCO) to treat organics in soil and groundwater are emerging. There are several issues that need to be resolved prior to adopting a standard analytical technique. Some of the more salient issues are discussed. In addition, currently practiced analytical techniques for estimating the oxidant demand for the oxidants permanganate and persulfate are provided. In the absence of analytical measurements, rules of thumb can be used with caution to estimate the overall oxidant demand. © 2003 Wiley Periodicals, Inc.     

Surfactant‐Oxidant Co‐Application for Soil and Groundwater Remediation

In situ chemical oxidation (ISCO) typically delivers oxidant solutions into the subsurface for contaminant destruction. Contaminants available to the oxidants, however, are limited by the mass transfer of hydrophobic contaminants into the aqueous phase. ISCO treatments therefore often leave sites with temporarily clean groundwater which is subject to contaminant rebound when sorbed and free phase contaminants leach back into the aqueous phase. Surfactant Enhanced In situ Chemical Oxidation (S‐ISCO^®) uses a combined oxidant‐surfactant solution to provide optimized contaminant delivery to the oxidants for destruction via desorption and emulsification of the contaminants by the surfactants. This article provides an overview of S‐ISCO technology, followed by an implementation case study at a coal tar contaminated site in Queens, New York. Included are data points from the site which demonstrate how S‐ISCO delivers desorbed contaminants without uncontrolled contaminant mobilization, as desorbed and emulsified contaminants are immediately available to the simultaneously injected oxidant for reaction. ©2016 Wiley Periodicals, Inc.     

Constant Head Injection for Enhanced In Situ Chemical Oxidation

With the successful implementation of in situ chemical oxidation (ISCO) programs to remediate contaminated soil and groundwater aquifers worldwide, ISCO has become established as a traditional remediation technique. On the basis of historical success, expanded ISCO practices are now routinely applied to increasingly difficult geologic environments, including formerly problem locations such as those containing nonaqueous‐phase liquid, fractured bedrock, low‐conductivity media, and highly layered and/or heterogeneous aquifers. Effective delivery of amendment, however, remains the single most important aspect of successful remediation, particularly given the range of potentially applicable delivery methods and site complexities. Selecting the most appropriate technique for any specific site depends upon a clear understanding of the variety of site constraints, including factors such as site conditions, underlying geology, contaminant distribution, technology limitations, and other project‐specific factors. Because the injection program is often the largest cost associated with implementation of an ISCO project, it is critical to develop a cost‐effective injection method for each site. Constant head injection provides a cost‐effective alternative for sites with low‐conductivity lithology(ies). Constant head injection employs a continuous low‐pressure application method to deliver ISCO agents over a long period of time. This synergistic method complements the existing site conditions and heterogeneity, working with the natural conditions, rather than trying to overcome or destroy the site geology using highly aggressive delivery techniques. © 2014 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.     

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.     

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.     

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.     

有机污染土壤原位化学氧化药剂投加方式的综述

原位化学氧化技术是修复有机污染土壤最经济有效的技术之一。药剂的投加与分散技术是原位化学氧化修复技术的核心。药剂投加与分散方式的选择与污染场地的土壤渗透性、特征水平、污染深度、氧化剂性质、修复费用等相关。阐述了直压式注射法、注射井法、土壤置换法和高压-旋喷注射法等药剂投加与分散技术的适用性、控制参数及优缺点等,引用工程实例对药剂投加与分散技术在原位化学氧化修复过程中的应用情况进行了论证。