Modeling of water quality downgradient of a mulch biowall

Groundwater treatment biowalls may be located close to a surface water body to prevent contaminant discharge from a groundwater plume into the surface water. Groundwater contaminants passing through the biowall are treated within the biowall or immediately downgradient of the biowall. Biowalls designed and constructed for the treatment of chlorinated solvents typically contain either a solid and/or liquid source of organic carbon to promote contaminant degradation by enhanced anaerobic reductive dechlorination. Common solid organic materials in biowalls include wood mulch or similar waste plant material, and common liquid organic materials are vegetable oil (possibly emulsified) or other long‐chain fatty acids. Such biowalls then develop anaerobic conditions in the constructed biowall volume, and potentially downgradient, as dissolved oxygen originally present in the aquifer is consumed. This groundwater condition can lead to the appearance of sulfide if groundwater influent to the biowall contains moderate to high sulfate concentrations. Other researchers have presented evidence for groundwater conditions downgradient of a biowall or a permeable reactive barrier (PRB) that are altered in relation to groundwater quality, besides the desired effect of contaminant degradation or removal by precipitation. The objective of this work was to investigate with modeling the changes in downgradient groundwater species chemistry as a result of a constructed biowall. This was accomplished with a chemical species model to predict levels of sulfate and sulfide present in groundwater in close downgradient proximity to the biowall. The results indicate that downgradient chemical changes could impact a surface water body to which groundwater discharges. The model described could be enhanced by incorporating additional design variables that should be considered in biowall feasibility assessments.     

Considerations for the design of organic mulch permeable reactive barriers

Organic mulch consists of insoluble carbon biopolymers that are enzymatically hydrolyzed during decomposition to release aqueous total organic carbon (TOC). The released TOC is utilized by microorganisms as an electron donor to transform electrophilic contaminants via reductive pathways. Over the last decade, organic mulch permeable reactive barriers (PRBs), or biowalls, have received increased interest as a relatively inexpensive slow‐release electron donor technology for addressing contaminated groundwater. To date, biowalls have been installed to enhance the passive bioremediation of groundwater contaminated with a variety of electrophilic compounds, including chlorinated solvents, explosives, and perchlorate. In addition, several mulch biowall projects are currently under way at several U.S. Department of Defense facilities. However, at the present time, the guidelines available for the design of mulch PRBs are limited to a few case studies published in the technical literature. A biowall design, construction, and operation protocol document is expected to be issued by the Air Force Center for Environmental Excellence in 2007. In this publication, three technical considerations that can have a significant impact on the design and performance of mulch PRBs are presented and discussed. These technical considerations are: (1) hydraulic characteristics of the mulch bed; (2) biochemical characteristics of different types of organic amendments used as mulch PRB fill materials; and (3) a transport model that can be used to estimate the required PRB thickness to attain cleanup standards. © 2007 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.     

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.     

Complete Degradation of Hexahydro‐1,3,5‐Trinitro‐1,3,5‐Triazine (RDX) by a Co‐Culture of Gordonia sp. KTR9 and Methylobacterium sp. JS178

The presence of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) in soil and groundwater is a major contamination issue at many military facilities around the world. Gordonia sp. KTR9 metabolizes RDX as a nitrogen source for growth producing 4‐nitro‐2,4‐diazabutanal (NDAB) as a dead‐end product. Methylobacterium sp. strain JS178 degrades NDAB as a sole source of nitrogen for growth. A mixed culture of strains KTR9 and JS178 was able to completely degrade RDX. There was no difference in rate of RDX degradation by KTR9 alone or in co‐culture with JS178. The first‐order degradation coefficients of RDX and NDAB in the co‐culture were 0.08 hr^?1 and 0.002 hr^?1, respectively. In the co‐culture that initially contained RDX plus NDAB, strain JS178 degraded the NDAB that was produced by KTR9 as shown by a decrease in the molar yield of NDAB (from RDX) from 1.0 to –0.11. Co‐cultures of strains KTR9 and JS178 could be used to promote complete degradation of RDX in soils or groundwater. ©2016 Wiley Periodicals, Inc.     

Iron‐mediated abiotic degradation of RDX in a contaminated aquifer

The influence of aqueous‐ and mineral‐phase iron on royal demolition explosive (RDX) destruction has been previously investigated in theoretical settings and bench‐scale tests by various practitioners. The feasible use of in situ redox manipulation to create reactive Fe(II) is contingent upon the aquifer containing enough iron oxides and iron‐bearing clay minerals for the treated zone to remain effective. The following is a summary of a bench‐scale assessment of this relationship using aquifer material from an ongoing groundwater remediation effort at the Iowa Army Ammunition Plant (IAAP). A bench‐scale study was designed to determine the relative contributions of the biotic and iron‐mediated abiotic degradation processes to the net decrease in RDX observed at the site using saturated aquifer samples collected from within the RDX plume. Sterilized samples with a sufficient stoichiometric excess of both soluble and mineral‐phase iron reduced concentrations of RDX in both the soil and water fractions to the same extent as the samples containing native biota. These results indicate that in situ, abiotic degradation of RDX is feasible in areas unsuitable to biotic degradation processes, yielding an additional alternative for in situ RDX remediation. © 2012 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.     

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

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

Aerobic Biodegradation of Hydrocarbons in High Temperature and Saline Groundwater

A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for aerobic biodegradation of aromatic hydrocarbons and methyl tert‐butyl ether (MtBE; a common oxygenate additive in gasoline) in saline, high temperature (>30° C) groundwater. Aquifer, sediment, and groundwater samples from two sites, one in Canada and another in Saudi Arabia, were incubated for 106 days to evaluate the changes in select hydrocarbon and MtBE concentrations and microbial community structure. Almost complete biodegradation of the aromatic hydrocarbons was found in the Saudi Arabian microcosm samples whereas the Canadian microcosm samples showed no significant biodegradation during the laboratory testing. MtBE degradation was not observed in either set of microcosms. Denaturing gradient gel electrophoresis analyses showed that, while the Canadian microorganisms were the most diverse, they showed little response during incubation. The microbial communities for the Saudi Arabian sample contained significant numbers of microorganisms capable of hydrocarbon degradation which increased during incubation. Based on the laboratory results, pilot‐scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of enhanced aerobic biodegradation on a high temperature, saline petroleum hydrocarbon plume. Dissolved oxygen was delivered to the subsurface using a series of oxygen diffusion emitters installed perpendicular to groundwater flow, which created a reactive zone. Results obtained from the seven‐month field trial indicated that all the target compounds decreased with removal percentages varying between 33 percent for the trimethylbenzenes to greater than 80 percent for the BTEX compounds. MtBE decreased 40 percent on average whereas naphthalene was reduced 85 percent on average. Examination of the microbial population upgradient and downgradient of the emitter reactive zone suggested that the bacteria population went from an anaerobic, sulfate‐reducing dominated population to one dominated by a heterotrophic aerobic bacteria dominant population. These studies illustrate that field aerobic biodegradation may exceed expectations derived from simple laboratory microcosm experiments. Also, high salinity and elevated groundwater temperature do not appear to inhibit in situ aerobic biorestoration. © 2014 Wiley Periodicals, Inc.     

Full‐scale bioremediation of a dilute 50‐acre plume

Enhanced anaerobic dechlorination is being conducted to remediate a 50‐acre groundwater area impacted with chlorinated volatile organic compounds (CVOCs). The plume, which is over 3,000 feet (ft) long, initially contained tetrachloroethene and breakdown products at concentrations of 2 to 3 milligrams per liter. The site's high groundwater flow velocity (greater than 1,000 ft per year) was incorporated into the design to help with amendment distribution. Bioaugmentation was conducted using a mixed culture containing Dehalococcoides ethenogenes. There is evidence that it has migrated to distances exceeding 600 ft. The major benefit of the high groundwater flow velocity is greater areal coverage by the remediation system, but the downside is the difficulty in delivering sufficient donor to create the required anaerobic conditions. Overall performance has been excellent with total CVOC reductions and conversion to ethene of 98 percent within a 25‐acre area downgradient of the treatment transect that has operated the longest. © 2011 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.     

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

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

Phytoremediation of a Petroleum‐Hydrocarbon Contaminated Shallow Aquifer in Elizabeth City,North Carolina,USA

A former bulk fuel terminal in North Carolina is a groundwater phytoremediation demonstration site where 3,250 hybrid poplars, willows, and pine trees were planted from 2006 to 2008 over approximately 579,000 L of residual gasoline, diesel, and jet fuel. Since 2011, the groundwater altitude is lower in the area with trees than outside the planted area. Soil‐gas analyses showed a 95 percent mass loss for total petroleum hydrocarbons (TPH) and a 99 percent mass loss for benzene, toluene, ethylbenzene, and xylenes (BTEX). BTEX and methyl tert‐butyl ether concentrations have decreased in groundwater. Interpolations of free‐phase, fuel product gauging data show reduced thicknesses across the site and pooling of fuel product where poplar biomass is greatest. Isolated clusters of tree mortalities have persisted in areas with high TPH and BTEX mass. Toxicity assays showed impaired water use for willows and poplars exposed to the site's fuel product, but Populus survival was higher than the willows or pines on‐site, even in a noncontaminated control area. All four Populus clones survived well at the site. © 2014 Wiley Periodicals, Inc.*     

Long‐term evaluation of an EHC injection permeable reactive barrier in a sulfate‐rich,high‐flow aquifer

Permeable reactive barriers (PRBs) have traditionally been constructed via trenching backfilled with granular, long‐lasting materials. Over the last decade, direct push injection PRBs with fine‐grained injectable reagents have gained popularity as a more cost‐efficient and less‐invasive approach compared to trenching. A direct push injection PRB was installed in 2005 to intercept a 2,500 feet (760 meter) long carbon tetrachloride (CT) groundwater plume at a site in Kansas. The PRB was constructed by injecting EHC^® in situ chemical reduction reagent slurry into a line of direct push injection points. EHC is composed of slow‐release plant‐derived organic carbon plus microscale zero‐valent iron (ZVI) particles, specifically formulated for injection applications. This project was the first full‐scale application of EHC into a flow‐through reactive zone and provided valuable information about substrate longevity and PRB performance over time. Groundwater velocity at the site is high (1.8 feet per day) and sulfate‐rich (~120 milligrams per liter), potentially affecting the rate of substrate consumption and the PRB reactive life. CT removal rates peaked 16 months after PRB installation with >99% removal observed. Two years post‐installation removal rates decreased to approximately 95% and have since stabilized at that level for the 12 years of monitoring data available after injection. Geochemical data indicate that the organic carbon component of EHC was mostly consumed after 2 years; however, reducing conditions and a high degree of chloromethane treatment were maintained for several years after total organic carbon concentrations returned to background. Redox conditions are slowly reverting and have returned close to background conditions after 12 years, indicating that the PRB may be nearing the end of its reactive life. Direct measurements of iron have not been performed, but stoichiometric demand calculations suggest that the ZVI component of EHC may, in theory, last for up to 33 years. However, the ZVI component by itself would not be expected to support the level of treatment observed after the organic carbon substrate had been depleted. A longevity of up to 5 years was originally estimated for the EHC PRB based on the maximum expected longevity of the organic carbon substrate. While the organic carbon was consumed faster than expected, the PRB has continued to support a high degree of chloromethane treatment for a significantly longer time period of over 12 years. Recycling of biomass and the contribution from a reduced iron sulfide mineral zone are discussed as possible explanations for the sustained reducing conditions and continued chloromethane treatment.     

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.     

Air Sparging Pilot Testing Including In-Well Temperature Measurement

Air sparging was pilot tested at a site where a groundwater plume containing cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC) and arsenic resulted from landfill operations. In addition to the commonly used methods for estimating air sparging zone of influence (ZOI), in-well temperature was monitored using sensitive thermocouples and data loggers at several monitoring wells of various screened intervals during the test. Following 42 days of pilot testing, the downgradient monitoring well samples were below maximum contaminant levels (MCLs)for all contaminants of concern, VC and dissolved arsenic were below detection limits (0.5 and 10 milligrams per liter [μg/L], respectively) in all of the downgradient monitoring wells. The ZOI monitoring results indicated that at some locations use of mounding data may overestimate the ZOI when the temperature data suggest that no sparged air was entering the well screen. Therefore, monitoring in-well temperature may provide additional useful information for estimating air sparging ZOI and is more indicative of air pathways than other monitoring methods. In addition, the temperature data were valuable for selecting a pulse frequency and duration to optimize groundwater mixing.     

Successful ISCR‐enhanced bioremediation of a TCE DNAPL source utilizing EHC® and KB‐1®

Remediation of chlorinated solvent DNAPL sites often meets with mixed results. This can be attributed to the diametrically opposed nature of the impacts, where the disparate dissolved‐phase plume is more manageable than the localized, high‐concentration source area. A wide range of technologies are available for downgradient plume management, but the relative mass of contaminants in a DNAPL source area generally requires treatment for such technologies to be effective over the long term. In many cases, the characteristics of DNAPL source zones (e.g., depth, soil heterogeneity, structural limitations) limit the available options. The following describes the successful full‐scale implementation of in situ chemical reduction (ISCR) enhanced bioremediation of a TCE DNAPL source zone. In this demonstration, concentrations of TCE were rapidly reduced to below the maximum contaminant level (MCL) in less than six months following implementation. The results described herein suggest that ISCR‐enhanced bioremediation is a viable remedial alternative for chlorinated solvent source zones. © 2010 Wiley Periodicals, Inc.     

Stable Isotope Probing to Confirm Field‐Scale Co‐Metabolic Biodegradation of 1,4‐Dioxane

1,4‐Dioxane, a common co‐contaminant with chlorinated solvents, is present in groundwater at Site 24 at Vandenberg Air Force Base in California. Historical use of chlorinated solvents resulted in concentrations of 1,4‐dioxane in groundwater up to approximately 2,000 μg/L. Starting in 2013, an in situ propane biosparge system operation demonstrated reductions in 1,4‐dioxane concentrations in groundwater. The work detailed herein extends the efforts of the first field demonstration to a second phase and confirms the biodegradation mechanism via use of stable isotope probing (SIP). After two months of operation, 1,4‐dioxane concentrations decreased approximately 45 to 83 percent at monitoring locations in the test area. The results of the SIP confirmed ¹³C‐enriched 1,4‐dioxane was transformed into dissolved inorganic carbon (suggesting mineralization to carbon dioxide) and incorporated into microbial biomass (likely attributed to metabolic uptake of biotransformation intermediates or of carbon dioxide).  ©2016 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.     

Six pilot‐scale studies evaluating the in situ treatment of PFAS in groundwater

Per‐ and polyfluoroalkyl substances (PFAS) have been identified by many regulatory agencies as emerging contaminants of concern in a variety of media including groundwater. Currently, there are limited technologies available to treat PFAS in groundwater with the most frequently applied approach being extraction (i.e., pump and treat). While this approach can be effective in containing PFAS plumes, previous studies of pump and treat programs have met with limited remedial success. In situ treatment studies of PFAS have been limited to laboratory and a few field studies. Six pilot‐scale field studies were conducted in an unconfined sand aquifer coimpacted by petroleum hydrocarbon along with PFAS to determine if a variety of reagents could be used to attenuate dissolved phase PFAS in the presence of petroleum hydrocarbons. The six reagents consisted of two chemical oxidants, hydrogen peroxide (H₂O₂) and sodium persulfate (Na₂S₂O₈), and four adsorbents, powdered activated carbon (PAC), colloidal activated carbon (CAC), ion‐exchange resin (IER), and biochar. The reagents were injected using direct push technology in six permeable reactive zone (PRZ) configurations. Groundwater concentrations of various PFAS entering the PRZs ranged up to 24,000 µg/L perfluoropentanoic acid, up to 6,200 µg/L pentafluorobenzoic acid, up to 16,100 µg/L perfluorohexanoic acid, up to 6,080 µg/L perfluoroheptanoic acid, up to 450 µg/L perfluorooctanoic acid, and up to 140 µg/L perfluorononanoic acid. Performance groundwater sampling within and downgradient of the PRZs occurred for up to 18 months using single and multilevel monitoring wells. Results of groundwater sampling indicated that the PFAS were not treated by either the persulfate nor the peroxide and, in some cases, the PFAS increased in concentration immediately following the injection of peroxide and persulfate. Concentrations of PFAS in groundwater sampled within the PAC, CAC, IER, and biochar PRZs immediately after the injection were determined to be less than the method detection limits. Analyses of groundwater samples over the 18‐month monitoring period, indicated that all the PRZs exhibited partial or complete breakthrough of the PFAS over the 18‐month monitoring period, except for the CAC PRZ which showed no PFAS breakthrough. Analysis of cores for the CAC, PAC, and biochar PRZs suggested that the CAC was uniformly distributed within the target injection zone, whereas the PAC and biochar showed preferential injection into a thin coarse‐sand seam. Similarly, analysis of the sand packs of monitoring wells installed before the injection of the CAC, PAC, and biochar indicated that the sand packs of the PAC and biochar preferentially accumulated the reagents compared with the reagent concentrations within the surrounding aquifer by up to 18 times.