Spatial Distribution of Geobacteraceae and Sulfate‐Reducing Bacteria During In Situ Bioremediation of Uranium‐Contaminated Groundwater

Analysis of the physiological status of subsurface microbial communities generally relies on the study of unattached microorganisms in the groundwater. These approaches have been employed in studies on bioremediation of uranium‐contaminated groundwater at a study site in Rifle, Colorado, in which Geobacter species typically account for over 90 percent of the microbial community in the groundwater during active uranium reduction. However, to develop efficient in situ bioremediation strategies it is necessary to know the status of sediment‐associated microorganisms as well. In order to evaluate the distribution of the natural community of Geobacter during bioremediation of uranium, subsurface sediments were packed into either passive flux meters (PFMs) or sediment columns deployed in groundwater monitoring wells prior to acetate injection during in situ biostimulation field trials. The trials were performed at the Department of Energy's (DOE's) Rifle Integrated Field Research Challenge site. Sediment samples were removed either during the peak of Fe(III) reduction or the peak of sulfate reduction over the course of two separate field experiments and preserved for microscopy. Direct cell counts using fluorescence in situ hybridization (FISH) probes targeting Geobacter species indicated that the majority of Geobacter cells were unattached during Fe(III) reduction, which typically tracks with elevated rates of uranium reduction. Similar measurements conducted during the sulfate‐reducing phase revealed the majority of Geobacter to be attached following exhaustion of more readily bioavailable forms of iron minerals. Laboratory sediment column studies confirmed observations made with sediment samples collected during field trials and indicated that during Fe(III) reduction, Geobacter species are primarily unattached (90 percent), whereas the majority of sulfate‐reducing bacteria and Geobacter species are attached to sediment surfaces when sulfate reduction is the predominant form of metabolism (75 percent and 77 percent, respectively). In addition, artificial sediment experiments showed that pure cultures of Geobacter uraniireducens, isolated from the Rifle site, were primarily unattached once Fe(III) became scarce. These results demonstrate that, although Geobacter species must directly contact Fe(III) oxides in order to reduce them, cells do not firmly attach to the sediments, which is likely an adaptive response to sparsely and heterogeneously dispersed Fe(III) minerals in the subsurface. © 2013 Wiley Periodicals, Inc.     

Field‐scale uranium (VI) bioimmobilization monitored by lipid biomarkers and 13C‐acetate incorporation

At the Old Rifle uranium mill‐tailing site in eastern Colorado, a test of subsurface amendment with acetate to stimulate the reductive immobilization of uranium was monitored by using lipid biomarker analysis and incorporation of ¹³C‐labeled acetate into lipid biomarkers. Both sediment and groundwater samples were analyzed. Within 7 days of acetate addition, groundwater microbial biomass increased by a factor of 5, and remained higher than control values in most samples for the 28 days sampled. At 29 days after the beginning of acetate amendment, 4 of 12 sediment samples had microbial biomass greater than the 95 percent confidence interval of controls. The mole percents of the phospholipid fatty acids 16:1ω7c and 16:1ω5c increased over control values upon acetate amendment, and incorporated high levels of ¹³C from labeled acetate in groundwater and sediment samples. 16:1ω7c is a biomarker for Geobacter, and evidence is provided that 16:1ω5c represents an unidentified iron‐reducing bacterium, probably a member of the Desulfobulbaceae. Biomarkers for organisms other than iron‐reducing bacteria, iso‐ and anteiso‐branched fatty acids and 18:1ω9c, decreased upon acetate amendment, and had their highest stable isotope incorporation at least 4 days after labeled acetate amendment ended, evidence for carbon‐sharing between iron‐reducers and other microorganisms. © 2011 Wiley Periodicals, Inc.     

Microbial cycling of iron and sulfur in acidic coal mining lake sediments

Lakes caused by coal mining processes are characterized by low pH, low nutrient status, and high concentrations of Fe(II) and sulfate due to the oxidation of pyrite in the surrounding mine tailings. Fe(III) produced during Fe(II) oxidation precipitates to the anoxic acidic sediment, where the microbial reduction of Fe(III) is the dominant electron-accepting process for the oxidation of organic matter, apparently mediated by acidophilic Acidiphilium species. Those bacteria can reduce a great variety of Fe(III)-(hydr)oxides and reduce Fe(III) and oxygen simultaneously which might be due to the small differences in the redox potentials under low pH conditions. Due to the absence of sulfide, Fe(II) formed in the upper 6 cm of the sediment diffuses to oxic zones in the water layer where itcan be reoxidized by Acidithiobacillus species. Thus, acidic conditions are stabilized by the cycling of iron which inhibits fermentative and sulfate-reducing activities. With increasing sediment depth, the amount of reactive iron decrease, the pH increases above 5, and fermentative and as yet unknown Fe(III)-reducing bacteria are also involved in the reduction of Fe(III). Sulfate is reduced apparently by the activity of spore-forming sulfate reducers including new species of Desulfosporosinus that have their pH optimum similar to in situconditions and are not capable of growth at pH 7. However, generation of alkalinity via sulfate reduction is reduced by the anaerobic reoxidation of sulfide back to sulfate. Thus, the microbial cycling of iron at the oxic-anoxic interface and the anaerobic cycling of sulfur maintains environmental conditions appropriate for acidophilic Fe(III)-reducing and acid-tolerant sulfate-reducing microbial communities.     

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.     

Demonstrating Contaminant Degradation at an MGP Site With Metabolic Gas Flux and Radio Carbon Dating

Obtaining lines of evidence indicating that contamination in sediment environments is degrading and being transformed to less toxic forms is an important component of building support for a monitored natural recovery remedy for contaminated sediments. This project was a field demonstration of manufactured gas plant contaminant degradation in river sediments using metabolic gas flux and was performed in an urban area section of a river in northeastern Indiana. CO₂ sorbent traps were deployed to measure CO₂ flux from the river sediments. Sediment samples were collected and analyzed for polycyclic aromatic hydrocarbon (PAH) concentrations and for microbial community composition using molecular techniques. The results showed that the deployment was successful, measuring CO₂ flux at all sediment locations and demonstrating that microbial contaminant degrading activity was occurring in the sediments. Radio carbon dating showed a significant portion of the CO₂ being generated (approximately 19–27 percent) was the result of fossil fuel degradation. Molecular results showed that the microbial community consisted of phylotypes known to be associated with monocyclic aromatic and PAH degradation. ©2017 Wiley Periodicals, Inc.     

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.     

Concurrent and Complete Anaerobic Reduction and Microaerophilic Degradation of Mono‐, Di‐, and Trichlorobenzenes

Bio‐Trap^®–based in situ microcosm studies were conducted to evaluate EHC‐M^® stimulated degradation of mono‐, di‐, and trichlorobenzenes in anaerobic groundwater at a site in Michigan. The data show that the EHC‐M^® amendment stimulated an overall increase in microbial activity and a shift in the microbial community structure, indicating more reduced conditions. Stable isotope probing with ¹³C₆‐chlorobenzene demonstrated attenuation of chlorobenzene and subsequent separation and characterization of the ¹²C‐ and ¹³C‐deoxyribonucleic acid (DNA) fractions were used to identify the attenuating microbes. These data clearly show the participation of an obligate aerobe in the chlorobenzene biodegradation process. Decreases in concentrations of trichlorobenzenes were also observed in comparison to a control. Due to the thermodynamically favorable reducing conditions stimulated by EHC‐M^®, the mechanism of degradation of the trichlorobenzenes is presumed to be reductive dehalogenation. However, on the strength of the DNA‐based analysis of microbial community structure, concurrent microaerophilic degradation of chlorobenzene or its metabolites was definitively demonstrated and cannot be ruled out for the other chlorobenzenes. © 2013 Wiley Periodicals, Inc.     

Microbial responses to in situ chemical oxidation,six‐phase heating,and steam injection remediation technologies in groundwater

The evaluation of microbial responses to three in situ source removal remedial technologies—permanganate‐based in situ chemical oxidation (ISCO), six‐phase heating (SPH), and steam injection (SI)—was performed at Cape Canaveral Air Station in Florida. The investigation stemmed from concerns that treatment processes could have a variety of effects on the indigenous biological activity, including reduced biodegradation rates and a long‐term disruption of community structure with respect to the stimulation of TCE (trichloroethylene) degraders. The investigation focused on the quantity of phospholipid fatty acids (PLFAs) and its distribution to determine the immediate effect of each remedial technology on microbial abundance and community structure, and to establish how rapidly the microbial communities recovered. Comprehensive spatial and temporal PLFA screening data suggested that the technology applications did not significantly alter the site's microbial community structure. The ISCO was the only technology found to stimulate microbial abundance; however, the biomass returned to predemonstration values shortly after treatment ended. In general, no significant change in the microbial community composition was observed in the SPH or SI treatment areas, and even small changes returned to near initial conditions after the demonstrations. © 2004 Wiley Periodicals, Inc.     

DOE genomics: Applications to in situ subsurface bioremediation

Microbial communities can greatly affect the mobility and fate of subsurface contaminants, yet relatively little is known about the functioning of microorganisms in subsurface environments. Major advances in DNA sequencing capability and the advent of genome‐enabled studies have produced key insights into how microorganisms adapt to environmental conditions and/or biotransform subsurface contaminants starting from analyses of genome content. These techniques enable the researcher to detect how an organism responds to its environment and, potentially, to devise better methods to promote specific microbial activity in subsurface environments. The U.S. Department of Energy sponsors genome research through the Genomics:GTL program. One of the applications of this research is to better understand and control biological processes influencing the mobility of contaminants of concern to DOE such as metals and radionuclides. Genome and gene expression techniques have led to new insights into the functioning of subsurface microbial communities, but the true potential of these techniques is still to be revealed. As genome‐enabled science progresses, techniques for evaluating gene expression patterns of whole communities will advance the understanding and development of optimized in situ bioremediation and more realistic simulations of microbial contaminant biotransformation. © 2006 Wiley Periodicals, Inc.*     

Nanoremediation and International Environmental Restoration Markets

Nanoscale zero‐valent iron (nZVI) is the most commonly used nanoremediation material. While there has been a reasonable level of application of nZVI technologies for in situ remediation in the United States, its utilization across Europe has been much more limited. There has been significant uncertainty about the balance between deployment risks and benefits for nanoparticles (NPs), which has affected the regulatory position in several countries. Some member states of the European Union (EU) take a strong precautionary view of the risks from the deployment of NPs into the subsurface, preventing the adoption of the technology. This article provides a risk–benefit assessment for nZVI based on published information and describes the steps that will be taken by a major European research project (NanoRem), as part of its work to provide a basis for better informed decision making in European environmental restoration markets. A key part of this process is dialogue between practitioners and researchers. NanoRem therefore has an active process of communication with different stakeholder networks (regulators, service providers, and site owners). NanoRem hopes to stimulate a consensus on appropriate use of nanoremediation and thereby stimulate effective technology transfer to the European remediation market. ©2015 The Authors     

Bench‐ and pilot‐scale applications of electrochemical peroxidation: A new remedial concept

Electrochemical peroxidation (ECP) is a proprietary process that utilizes sacrificial iron electrodes and stochiometrically balanced applications of hydrogen peroxide to efficiently destroy aqueous phase contaminants. In laboratory trials it has been successful in reducing, often to non‐detectable levels, BTEX, fuel additives, chlorinated solvents, and polychlorinated biphenyls in ground waters. The process has also been found effective in reducing the chemical and biological oxygen demand of industrial waste water. Agency‐approved pilot tests will be conducted at two gasoline spill sites during 2000 where traditional pump and treat methods have proven ineffectual because of ground water chemistry or subsurface hydrologic conditions. The ECP process utilizes a tripartite treatment strategy consisting of 1) ex situ chemical oxidation; 2) in situ oxidation by reinjection of treated water with residual oxidants at the head of the plume; and 3) reestablishment of aerobic biodegradation by alteration of subsurface redox conditions. In contrast to other in situ oxidation treatment methods, dissolved iron is derived electrochemically, negating the need for ferrous salt addition. Dilute hydrogen peroxide (3 percent) is incrementally added to maximize oxidation efficiency and eliminate safety and environmental concerns accompanying the use of highly concentrated solutions. Results of laboratory trials and the geological and geochemical considerations of upcoming pilot‐scale applications are presented. Other potential applications currently under investigation include combination with other remedial processes (e.g. permeable barriers and hydrogen release compounds) to insure complete and rapid contaminant mineralization.     

Potential and Limitations of Microbial Reductive Dechlorination for Bioremediation Applications

Current knowledge and recent advances in the area of microbial reductive dechlorination of polychlorinated organic compounds are summarized. Factors which may limit the efficacy of the dechlorination process for the in situ bioremediation of contaminated soil and sediment systems are identified. Results of recent studies on the anaerobic biotransformation of soil-sorbed chlorinated ethenes and sediment-sorbed chlorinated benzenes are provided to illustrate how low contaminant bioavailability may control the rate and extent of dechlorination in subsurface systems, especially those with long-term contamination. Use of nonionic, polysorbate surfactants as the sole electron donors of a mixed, methanogenic culture supported the microbial sequential reductive dechlorination of either free or sediment-bound hexachlorobenzene (HCB) to primarily 1,3-dichlorobenzene, but did not enhance the bioavailability of sediment-bound HCB as compared to microcosms, which used glucose. Because current knowledge on the interactions of dechlorinating populations with other microbial populations in the presence of alternative terminal electron acceptors (e.g., nitrate, Fe³⁺ , Mn⁴⁺) is limited, such interactions and their effect on the dechlorination process in subsurface systems need to be further explored to improve our understanding of the reductive dechlorination process in complex environmental systems and lead to the development of more efficient in situ bioremediation technologies and strategies.     

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.     

Detecting and quantifying reductive dechlorination under monitored natural attenuation conditions

Field sampling and testing were used to investigate the relationship between baseline geochemical and microbial community data and in situ reductive dechlorination rates at a site contaminated with trichloroethene (TCE) and carbon tetrachloride (CTET). Ten monitoring wells were selected to represent conditions along groundwater flow paths from the contaminant source zone to a wetlands groundwater discharge zone. Groundwater samples were analyzed for a suite of geochemical and microbial parameters; then push‐pull tests with fluorinated reactive tracers were conducted in each well to measure in situ reductive dechlorination rates. No exogenous electron donors were added in these tests, as the goal was to assess in situ reductive dechlorination rates under natural attenuation conditions. Geochemical data provided preliminary evidence that reductive dechlorination of TCE and CTET was occurring at the site, and microbial data confirmed the presence of known dechlorinating organisms in groundwater. Push‐pull tests were conducted using trichlorofluoroethene (TCFE) as a reactive tracer for TCE and, in one well, trichlorofluoromethane (TCFM) as a reactive tracer for CTET. Injected TCFE was transformed to cis‐ and trans‐dichlorofluoroethene and chlorofluoroethene, and, in one test, injected TCFE was completely dechlorinated to fluoroethene (FE). In situ TCFE transformation rates ranged from less than 0.005 to 0.004/day. In the single well tested, injected TCFM was transformed in situ to dichlorofluoromethane and chlorofluoromethane; the TCFM transformation rate was estimated as 0.001/day. The results indicate that it is possible to use push‐pull tests with reactive tracers to directly detect and quantify reductive dechlorination of chlorinated ethenes and ethanes under monitored natural attenuation conditions, which has not previously been demonstrated. Transformation rate estimates obtained with these techniques should improve the accuracy of contaminant transport modeling. © 2012 Wiley Periodicals, Inc.     

In situ remediation of arsenic in contaminated soils

In situ chemical fixation represents a promising and potentially cost‐effective treatment alternative for metal‐contaminated soils. This article presents the findings of the use of iron‐bearing soil amendments to reduce the leachability and bioaccessibility of arsenic in soils impacted by stack fallout from a zinc smelter. The focus of this investigation was to reduce the lead bioaccessibility of the soils through addition with phosphorus‐bearing amendments. However, as phosphorus addition was expected to increase arsenic mobility, the fixation strategy also incorporated use of iron‐bearing amendments to offset or reverse these effects. The findings of this investigation demonstrated that inclusion of iron‐bearing chemicals in the amendment formulation reduced arsenic leachability and bioaccessibility without compromising amendment effectiveness for reducing lead bioaccessibility. These results suggest that in situ chemical fixation has the potential to be an effective strategy for treatment of the impacted soils. © 2003 Wiley Periodicals, Inc.     

Functions of Straw for In Situ Remediation of Acidic Mining Lakes

The addition of straw in combination with Carbokalk, a by-product from the sugar-industry, was successfully used to stimulate microbial alkalinity generation in an acidic mining lake. To get detailed information about functions of straw, anenclosure experiment was carried out. Straw bundles were placedat the sediment surface of an acidic mining lake (ML 111) and thephysiochemical conditions and the microbiology of the sediment-water contact zone were studied. Straw was degraded by anaerobic microorganisms and dissolved organic carbon (DOC) leached from straw bundles. Pigmented flagellates responded to the DOC supply in the water column anda considerable amount of algal carbon was transported to the sediment. Straw addition led to microbial reduction of iron andsulfate in the sediment. Sulfate reduction was observed at a pHof 5.5. The pH, however, was not high enough to precipitate H₂S completely. Thus, some H₂S diffused into the watercolumn, where it was reoxidized. Straw did not create orstabilize an anoxic water body above the sediment. Microbial sulfate reduction and pyrite formation only took place in the sediment,whereas iron reduction also took place in the straw. Straw, however, altered the flow conditions above the sediment surfaceand prevented complete mixing of the profundal water. Straw didnot serve as a substratum for a reactive biofilm. We conclude that the most important function of straw for mining lake remediation is to be a long-term nutrient source for microbialalkalinity generation in the sediment.     

Biochemical Treatment of Hydraulically Complex Hexavalent Chromium and Chlorinated Volatile Organic Plumes

Groundwater contaminated with hexavalent chromium (Cr⁺⁶) and chlorinated volatile organic compounds (cVOCs) presents unique in situ remedial challenges in an oxygen‐rich environment. On one hand, chemical oxidation would be effective in treating the cVOCs; however, it would not be appropriate to treat Cr⁺⁶. Biological treatment may be appropriate to treat the Cr⁺⁶; however, the cVOC degradation pathway within these mixed plumes is currently following an abiotic pathway with little to no daughter‐product production. Thus, a blended approach was needed to treat both constituents in situ in an effort to avoid a long‐term, costly pump‐and‐treat solution. This article evaluates an in situ biogeochemical stabilization/reduction strategy by injecting an inorganic carbon‐based remedial additive into the geologic and hydrogeologic environment to decrease concentrations within the commingled Cr⁺⁶ and cVOC plume. The concept involves creating favorable redox reducing conditions to shift the groundwater geochemical equilibrium from the more toxic Cr⁺⁶ to the less toxic trivalent chromium (Cr⁺³), with the final outcome being a conversion to chrome oxide that molecularly fixes to the soil grains. In addition, reducing conditions developed for chromium reduction should result in an increase in the available natural formation iron that should further enhance the natural abiotic reduction of cVOCs. © 2013 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.     

Abiotic/biotic degradation and mineralization of N‐nitrosodimethylamine in aquifer sediments

The N‐nitrosodimethylamine (NDMA) degradation rate and mineralization rate were measured in two aquifer sediments that received treatments to create oxic, reducing, and sequential reducing/oxic environments. Chemically reduced sediments rapidly abiotically degraded NDMA to nontoxic dimethylamine to parts per trillion levels, then degraded to further products. NDMA was partially mineralized in reduced sediments (6 to 28 percent) at a slow rate (half‐life 3,460 h) by an unknown abiotic/biotic pathway. In contrast, NDMA was mineralized more rapidly (half‐life 342 h) and to a greater extent (30 to 81 percent) in oxic sediments with propane addition, likely by a propane monooxygenase pathway. NDMA mineralization in sequential reduced sediment followed by oxic sediment treatment did result in slightly more rapid mineralization and a greater mineralization extent relative to reduced systems. These increases were minor, so aerobic NDMA mineralization with oxygen and propane addition was the most viable in situ NDMA mineralization strategy. © 2008 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.