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.     

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.     

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.     

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.     

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.     

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.     

Use of Large‐Scale Electrokinetic and ZVI Treatment for Chlorinated Solvent Remediation at an Active Industrial Facility

The combination of electrokinetic and zero‐valent iron (ZVI) treatments were used to treat soils contaminated with chlorinated solvents, including dense nonaqueous phase liquid (DNAPL), at an active industrial site in Ohio. The remediation systems were installed in tight clay soils under truck lots and entrances to loading docks without interruption to facility production. The electrokinetic system, called Lasagna^TM, uses a direct current electrical field to mobilize contaminant via electroosmosis and soil heating. The contaminants are intercepted and reduced in situ using treatment zones containing ZVI. In moderately contaminated soils around the Lasagna^TM‐treated source areas, a grid of ZVI filled boreholes were emplaced to passively treat residual contamination in decades instead of centuries. The remediation systems were installed below grade and did not interfere with truck traffic during the installation and three years of operation. The Lasagna^TM systems removed 80 percent of the trichloroethylene (TCE) mass while the passive ZVI borings system has reduced the TCE by 40 percent. The remediation goals have been met and the site is now in monitoring‐only mode as natural attenuation takes over. © 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.     

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.     

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.     

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.     

Field and laboratory evaluation of the treatment of DNAPL source zones using emulsified zero‐valent iron

Emulsified zero‐valent iron (EZVI) is a surfactant‐stabilized, biodegradable emulsion that forms droplets consisting of a liquid‐oil membrane surrounding zero‐valent iron (ZVI) particles in water. This article summarizes the results obtained during the first field‐scale deployment of EZVI at NASA's Launch Complex 34 (LC34) located on Cape Canaveral Air Force Station, Florida, in August 2002 and presents the results of recent follow‐on laboratory tests evaluating the mechanisms, which contribute to the performance of the technology. The field‐scale demonstration evaluated the performance of EZVI containing nanoscale zero‐valent iron (NZVI) when applied to dense, nonaqueous phase liquid (DNAPL) trichloroethylene (TCE) in the saturated zone. Results of the field demonstration indicate substantial reductions in TCE soil concentrations (greater than 80 percent) at all but two soil boring locations and significant reductions in TCE groundwater concentrations (e.g., 60 percent to 100 percent) at all depths targeted with EZVI. Laboratory tests conducted in 2005 suggest that both NZVI particles and EZVI containing NZVI can provide significant reductions in TCE mass when used to treat TCE DNAPL in small test reactors. However, EZVI was able to reduce TCE concentrations to lower levels than were obtained with NZVI alone, likely as a result of the combined impact of sequestration of the TCE into the oil phase and degradation of the TCE with the NZVI. © 2006 Wiley Periodicals, Inc.     

An evaluation of permeable reactive barrier projects in California

Permeable reactive barriers made of zero‐valent iron (ZVI PRBs) have become a prominent remediation technology in addressing groundwater contamination by chlorinated solvents. Many ZVI PRBs have been installed across the United States, some as research projects, some at the pilot scale, and many at full scale. As a passive and in situ remediation technology, ZVI PRBs have many attractive features and advantages over other approaches to groundwater remediation. Ten ZVI PRBs installed in California were evaluated for their performance. Of those ten, three are discussed in greater detail to illustrate the complexities that arise when quantifying the performance of ZVI PRBs, and to provide comment on the national debate concerning the downgradient effects of source‐zone removal or treatment on plumes of contaminated groundwater. © 2009 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.     

Interactions between biological and abiotic pathways in the reduction of chlorinated solvents

While biologically mediated reductive dechlorination continues to be a significant focus of chlorinated solvent remediation, there has been an increased interest in abiotic reductive processes for the remediation of chlorinated solvents. In situ chemical reduction (ISCR) uses zero‐valent iron (ZVI)–based technologies, such as nanoscale iron and bimetallic ZVI, as well as naturally occurring reduced minerals incorporating dual‐valent iron (DVI), such as magnetite, green rust, and iron sulfides that are capable of dechlorinating solvents. A more recent area of development in ISCR has been in combining biological and abiotic processes. There are several ways in which biological and abiotic processes can be combined. First, the interaction between the two may be “causative.” For example, the Air Force Center for Engineering and the Environment's biogeochemical reductive dechlorination (BiRD) technology combines a mulch barrier with hematite and gypsum to create an iron‐sulfide‐based reducing zone. Biodegradation under sulfate‐reducing conditions produces sulfide that combines with the hematite to form iron sulfides. As such, the BiRD technology is “causative”; the biological processes create reducing minerals. The biological generation of other reducing minerals such as magnetite, siderite, and green rust is feasible and is, with magnetite, observed in nature at some petroleum sites. A second type of interaction between abiotic and biotic processes is “synergistic.” For example, biological processes can enhance the activity of reduced metals/minerals. This is the basis of the EHC® ISCR technologies, which combine ZVI with a (slowly) degradable carbon substrate. This combination rapidly creates buffered, strongly reducing conditions, which result in more complete solvent degradation (i.e., direct mineralization). The extent and level of reducing activity commonly observed are much greater when both the carbon substrate and the ZVI are present. When the carbon substrate is expended, the reducing activity due to ZVI alone is much less. The understanding of biogeochemical processes and their impact on abiotic processes is still developing. As that understanding develops, new and improved methods will be created to enhance volatile organic compound destruction. © 2009 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.     

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.     

Seven‐year performance evaluation of a permeable reactive barrier

In June and July 2001, the Massachusetts Department of Environmental Protection (MassDEP) installed a permeable reactive barrier (PRB) to treat a groundwater plume of chlorinated solvents migrating from an electronics manufacturer in Needham, Massachusetts, toward the Town of Wellesley's Rosemary Valley wellfield. The primary contaminant of concern at the site is trichloroethene (TCE), which at the time had a maximum average concentration of approximately 300 micrograms per liter directly upgradient of the PRB. The PRB is composed of a mix of granular zero‐valent iron (ZVI) filings and sand with a pure‐iron thickness design along its length between 0.5 and 1.7 feet. The PRB was designed to intercept the entire overburden plume; a previous study had indicated that the contaminant flux in the bedrock was negligible. Groundwater samples have been collected from monitoring wells upgradient and downgradient of the PRB on a quarterly basis since installation of the PRB. Inorganic parameters, such as oxidation/reduction potential, dissolved oxygen, and pH, are also measured to determine stabilization during the sampling process. Review of the analytical data indicates that the PRB is significantly reducing TCE concentrations along its length. However, in two discrete locations, TCE concentrations show little decrease in the downgradient monitoring wells, particularly in the deep overburden. Data available for review include the organic and inorganic analytical data, slug test results from nearby bedrock and overburden wells, and upgradient and downgradient groundwater‐level information. These data aid in refining the conceptual site model for the PRB, evaluating its performance, and provide clues as to the reasons for the PRB's underperformance in certain locations. © 2008 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.     

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.