Reductive dechlorination of a chlorinated solvent plume in Houston,Texas

Chlorinated solvents such as tetrachloroethene (perchloroethene, PCE) and trichloroethene (TCE) have been extensively used in various industrial applications for many years. Because neither are typically consumed through their various uses, they are often released to the environment through industrial application or disposal. Once released, PCE and TCE tend to migrate downward into groundwater, where they persist. In the current case study, cheese whey was used as a groundwater amendment to facilitate the reductive dechlorination of a chlorinated solvent plume underlying an auto dealer/repair shop in Harris County, Texas. From September 2010 to January 2014, over 32,000 gallons of cheese whey were injected into the subsurface resulting in a marked reduction in oxidation–reduction potential (ORP) and nitrate concentrations, coupled with an increase in ferrous iron concentrations. Statistical trend analyses indicate the primary contaminants, PCE and TCE, as well as the daughter product cis‐1,2‐dichloroethene (cDCE), all exhibited a positive response, as evidenced by statistically decreasing trends, and/or reversal in concentration trends, subsequent to cheese whey injections. Maximum concentrations of PCE and TCE in key test wells decreased by as much as 98.97 percent and 99.17 percent, respectively. In addition, the bacterial genus Dehalococcoides, capable of complete reduction of PCE to non‐toxic ethene, was found to be more abundant in the treatment area, as compared to background concentrations. Because cheese whey is a by‐product of the cheese making process, the cost of the product is essentially limited to transport. This study demonstrates cheese whey to be an effective groundwater amendment at a cost which is orders of magnitude lower than popular industry alternatives.     

Monitoring parameters and statistics: A land treatment unit monitoring case study

Statistical evaluation procedures for monitoring data at facilities permitted under the Resource Conservation and Recovery Act (RCRA) are frequently established before monitoring begins. Selecting the statistical method before background data have been collected often leads to the use of statistical procedures that are inappropriate for the actual monitoring data. Such was the case for unsaturated zone monitoring at a permitted land treatment unit in the Gulf Coast area of Texas. Due to the large number of “not detected” results in the background database for lysimeters, statistical evaluation procedures specified in the original RCRA permit yielded an artificially low standard deviation, resulting in background values that were strongly biased on the low side. An alternate statistical procedure based on probability plots was developed and was accepted by the state environmental regulatory agency. This technique, which has wide applicability for many types of environmental monitoring data, significantly reduced the chasing of false positives, thus saving potentially expensive investigations and remediations.     

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.     

In‐well sediment incubators to evaluate microbial community stability and dynamics following bioimmobilization of uranium

An in‐well sediment incubator (ISI) was developed to investigate the stability and dynamics of sediment‐associated microbial communities to prevailing subsurface oxidizing or reducing conditions. Herein we describe the use of these devices at the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site. During a seven‐month period in which oxidized Rifle Aquifer background sediment (RABS) were deployed in previously biostimulated wells under iron‐reducing conditions, cell densities of known iron‐reducing bacteria, including Geobacteraceae, increased significantly, showing the microbial community response to local subsurface conditions. Phospholipid fatty acid (PLFA) profiles of RABS following in situ deployment were strikingly similar to those of adjacent sediment cores, suggesting ISI results could be extrapolated to the native material of the test plots. Results for ISI deployment with laboratory‐reduced sediments showed only slight changes in community composition and pointed toward the ability of the ISI to monitor microbial community stability and response to subsurface conditions. © 2009 Wiley Periodicals, Inc.     

In situ bioremediation of an aniline spill in an industrial setting

In situ remediation of aniline from soils and groundwater using biological and physical treatments was conducted at the BASF Corporation facility in Geismar, Louisiana. To mitigate the migration of aniline, remediate contaminated soil and groundwater, and determine concentrations, 24 immobilized microbe bioreactors were fixed in the subsoil, and a horizontal recovery well and 7 monitoring wells were installed. Soil and monitoring wells were sampled quarterly to assess bioplug impact on the aniline concentrations. The recovery well was sampled monthly to estimate the pounds of aniline removed from groundwater. Soil pH, composition, and microbial counts were used to estimate the fate and transport. Aniline levels were lowered significantly after remediation and total cancer risk was below levels for industrial sites, as established by State of Louisiana Risk Evaluation/Corrective Action Program guidelines. © 2010 Wiley Periodicals, Inc.     

Matrix Diffusion Modeling Applied to Long‐Term Pump‐and‐Treat Data: 1. Method Development

Despite the installation in the 1980s and 1990s of hydraulic containment systems around known source zones (four slurry walls and ten pump‐and‐treat systems), trichloroethene (TCE) plumes persist in the three uppermost groundwater‐bearing units at the Middlefield‐Ellis‐Whisman (MEW) Superfund Study Area in Mountain View, California. In analyzing TCE data from 15 recovery wells, the observed TCE mass discharge decreased less than an order of magnitude over a 10‐year period despite the removal of an average of 11 pore volumes of affected groundwater. Two groundwater models were applied to long‐term groundwater pump‐and‐treat data from 15 recovery wells to determine if matrix diffusion could explain the long‐term persistence of a TCE plume. The first model assumed that TCE concentrations in the plume are controlled only by advection, dispersion, and retardation (ADR model). The second model used a one‐dimensional diffusion equation in contact with two low‐permeability zones (i.e., upper and lower aquitard) to estimate the potential effects of matrix diffusion of TCE into and out of low‐permeability media in the plume. In all 15 wells, the matrix diffusion model fit the data much better than the ADR model (normalized root mean square error of 0.17 vs. 0.29; r² of 0.99 vs. 0.19), indicating that matrix diffusion is a likely contributing factor to the persistence of the TCE plume in the non‐source‐capture zones of the MEW Study Area's groundwater‐extraction wells. © 2013 Wiley Periodicals, Inc.     

Remediating Contaminated Groundwater With Low‐Capacity Injection and Nonpumped Wells

This modeling study evaluated the capability of low‐capacity wells injecting clean water and nonpumped wells equipped with filter media for containing and removing a contaminant plume in groundwater. Outcomes were compared for configurations of: (1) nonpumped wells, (2) nonpumped wells and injection wells (injecting less than 1 m³/d), and (3) no wells (baseline scenario). Results suggest that hybrid configurations featuring both types of wells can be an effective, low‐cost strategy for containing and remediating contaminated groundwater. Strategically positioned injection wells funnel contaminant plumes toward nonpumped wells, thus requiring fewer nonpumped wells to contain and remove a contaminant plume. © 2013 Wiley Periodicals, Inc.     

CSIA of TCE and Daughter Products With Multiple Sources,Multiple Attenuation Mechanisms,and Low Ethene

One of the most often asked questions from regulators considering monitored natural attenuation (MNA) for a site is if there are mechanisms in situ that can completely detoxify the contaminant of concern. This article describes a method that uses data derived from compound‐specific isotope analysis (CSIA) to investigate if complete in situ degradation of trichloroethene (TCE) has occurred. MNA was the selected remediation strategy at the former England Air Force Base (fEAFB) in Louisiana. Previously declining concentrations of TCE, 1,2‐cis‐dichloroethene, and vinyl chloride had increased in selected wells, and less ethene was observed than expected on the basis of mass balance. Reductive dechlorination, partial or otherwise, could not explain observed trends, so the question at fEAFB had become: Was there an in situ mechanism for complete TCE detoxification (i.e., complete degradation to innocuous end products) at the site? CSIA was used for investigating this question at fEAFB. A previously developed formalism was adapted to interpret the CSIA data to answer the question. Standard interpretation assuming only reductive dechlorination demonstrated detoxification in 9 of the 15 contaminated wells, whereas the interpretation developed here did so in 14. © 2014 Wiley Periodicals, Inc.     

Characteristics of azaarenes and dioxins in gases emitted from waste incinerators

In this study, we propose an analytical method to determine the fourteen of azaarenes present in flue gas samples collected according to Japanese Industrial Standard K 0311, which designates the method for the determination of dioxins in flue gas. Azaarenes can be analyzed using the acidic water phase after shaking extraction with dichloromethane, which is unnecessary for dioxin analysis. Flue gas samples were obtained from 24 waste incinerators in Japan, and azaarenes were detected in all the flue gas samples (0.21–3800 μg/m³ _N). The most abundant of the detected compounds were quinoline and isoquinoline. The concentration of azaarenes had a tendency to increase with that of polychlorinated dibenzo-p-dioxins and dibenzofurans. The isomer distribution of heptachloro-dibenzofurans (HpCDFs) was calculated using the computed Gibbs energy of formation (ΔG _f ) obtained by the semiempirical molecular orbital method at various temperatures. The calculated isomer distribution was fitted to the measured value of HpCDFs. It seems that the temperature obtained from the fitting calculations is an indicator of the cooling capacity of the combustion gas in an incinerator. The computed ΔG _f also explained the measured isomer distributions of azaarenes. It is suggested that the isomer distribution of azaarenes in the combustion process is thermodynamically controlled. This work was presented in part at the International Conference on Combustion, Incineration/Pyrolysis, and Emission Control, 2006, Kyoto     

Incorporating Bioavailability Considerations Into the Evaluation of Contaminated Sediment Sites

In March 2011, the Interstate Technology & Regulatory Council (ITRC) Contaminated Sediments Team published a web‐based Technical and Regulatory Guidance on the concepts, processes, and uses of bioavailability in a risk decision‐making framework at a contaminated sediment site. Bioavailability processes, as defined by the National Research Council (NRC; 2003), are the “individual physical, chemical, and biological interactions that determine the exposure of plants and animals to chemicals associated with soils and sediments.” Bioavailability assessment tools aid in the assessment of human and ecological exposure and development of site‐specific remedial objectives. The guidance provides information on the processes that may affect contaminant bioavailability within sediments to understand exposure within ecological and human receptors; supports the development of conceptual site models (CSMs); and describes available tools (biological, chemical, and physical) and models that are used to measure and characterize the fate and transport and potential bioavailability of contaminants. Case studies, referenced throughout the document, demonstrate the practical application of bioavailability measures. The guidance will describe the proper application of traditional and emerging sediment remediation technologies to support the selection of a remedy that is protective of human health and the environment. © 2013 Wiley Periodicals, Inc.     

Pilot‐scale evaluation of in situ cometabolic bioremediation of TCE in groundwater using PHOSter® technology

A study was conducted to evaluate the efficacy of PHOSter® technology for treating groundwater contaminated with trichloroethene (TCE) at Edwards Air Force Base, California. The technology consists of injecting a gaseous mixture of air, methane, and nutrients into groundwater with the objective of stimulating the growth of methanotrophs, a naturally occurring microbial group that is capable of catalyzing the aerobic degradation of chlorinated solvents into nontoxic products. Injection operations were performed at one well for a period of three months. Six monitoring wells were utilized for groundwater and wellhead vapor monitoring and for groundwater and microbial sampling. In the five monitoring wells located within 44 feet of the injection well, the following results were observed: dissolved oxygen concentrations increased to a range between 6 and 8 milligrams per liter (μg/L); the biomass of target microbial groups increased by one to five orders of magnitude; and TCE concentrations decreased by an average of 92 percent, and to below the California primary maximum contaminant level (MCL; 5 micrograms per liter [µg/L]) in the well closest to the injection well. © 2008 Wiley Periodicals, Inc. *

1 This article is a U.S. Government work and, as such, is in the public domain of the United States of America.

     

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.     

Overview of state approaches to vapor intrusion: 2018

Regulatory requirements for the evaluation of vapor intrusion vary significantly among states. For site owners and responsible parties that have sites in different regulatory jurisdictions, one challenge is to know and understand how the requirements or expectations for vapor intrusion differ from one jurisdiction to the next. Differences in requirements can make it difficult to manage sites in a consistent manner across jurisdictions. Eklund, Folkes, et al. (2007, February, Environmental Manager, 10–14) published an overview of state guidance for vapor intrusion in 2007 that provided a detailed summary of pathway screening values and other key vapor intrusion policies. An update by Eklund, Beckley, et al. (2012, Remediation, 22, 7–20) was published in 2012, which expanded the evaluation to additional states. Since that time, numerous states have substantially revised their guidance and some states that did not have vapor intrusion‐specific guidance have issued new guidance. This article provides an update to the 2012 study. For each state, the review includes tabulations of the types of screening values included (e.g., groundwater, soil, soil gas, indoor air) and the screening values for selected chemicals that commonly drive vapor intrusion investigations (i.e., trichloroethylene [TCE], tetrachloroethylene, and benzene) along with other compounds of potential interest. In addition, for each state, the article summarizes a number of key policy decisions that are important for the investigation of vapor intrusion including: distance screening criteria, default subsurface to indoor air attenuation factors, mitigation criteria, and policies for evaluation of short‐term TCE exposure.     

Development of a site‐specific cleanup goal for PAHs in soil based on anthropogenic background levels

During removal of an industrial landfill in Folsom, California, fill material was excavated and processed through a mechanical screening plant to segregate soil from construction and demolition debris. The segregated soil was stockpiled and analyzed for a wide range of chemical groups to determine if the soil could be backfilled on‐site. The analytical results indicated many of the stockpiles had concentrations of polycyclic aromatic hydrocarbons (PAHs) that exceeded US EPA Regional Screening Levels, and a large quantity of soil was initially classified as requiring off‐site disposal at considerable cost. Because PAHs are ubiquitous in urban settings and the landfill did not contain a significant source of PAHs, development of a site‐specific PAH cleanup goal was proposed to regulators. Cal/EPA guidance for using on‐site data to develop a background threshold for metals was applied to the development of the PAH cleanup goal. The Cal/EPA approach involves demonstrating whether the data belong to a single population or multiple populations based on data distribution tests and probability plots. This article explains the statistical and graphical methods that were used to demonstrate that the Cal/EPA approach was valid for PAHs and that the calculated cleanup level was consistent with published anthropogenic background levels of PAHs in California and across the United States. The site‐specific PAH cleanup goal enabled most of the soil to be backfilled on‐site, saving about $227,000 in transportation and disposal costs, and regulators subsequently approved unrestricted future use of the property. © 2010 Wiley Periodicals, Inc.     

Integrated approach to PCE‐impacted site characterization,site management,and enhanced bioremediation

Tetrachloroethene (PCE)‐ and trichloroethene (TCE)‐impacted sites pose significant challenges even when site characterization activities indicate that biodegradation has occurred naturally. Although site‐specific, regulatory, and economic factors play roles in the remedy‐selection process, the application of molecular biological tools to the bioremediation field has streamlined the assessment of remedial alternatives and allowed for detailed evaluation of the chosen remedial technology. The case study described here was performed at a PCE‐impacted site at which reductive dechlorination of PCE and TCE had led to accumulation of cis‐dichlorethene (cis‐DCE) with concentrations ranging from approximately 10 to 100 mg/L. Bio‐Trap® samplers and quantitative polymerase chain reaction (qPCR) enumeration of Dehalococcoides spp. were used to evaluate three remedial options: monitored natural attenuation, biostimulation with HRC®, and biostimulation with HRC‐S®. Dehalococcoides populations in HRC‐S‐amended Bio‐Traps deployed in impacted wells were on the order of 10³ to 10⁴ cells/bead but were below detection limits in most unamended and HRC‐amended Bio‐Traps. Thus the in situ Bio‐Trap study identified biostimulation with HRC‐S as the recommended approach, which was further evaluated with a pilot study. After the pilot HRC‐S injection, Dehalococcoides populations increased to 10⁶ to 10⁷ cells/bead, and concentrations of cis‐DCE and vinyl chloride decreased with concurrent ethene production. Based on these results, a full‐scale HRC‐S injection was designed and implemented at the site. As with the pilot study, full‐scale HRC‐S injection promoted growth of Dehalococcoides spp. and stimulated reductive dechlorination of the daughter products cis‐DCE and vinyl chloride. © 2008 Wiley Periodicals, Inc.     

Application of source removal and natural attenuation remediation strategies at MGP sites in Wisconsin

This article presents site closure strategies of source material removal and dissolved‐phase groundwater natural attenuation that were applied at two manufactured gas plant (MGP) sites in Wisconsin. The source removal actions were implemented in 1999 and 2000 with groundwater monitoring activities preceding and following those actions. Both of these sites have unique geological and hydrogeological conditions. The article briefly presents site background information and source removal activities at both of these sites and focuses on groundwater analytical testing data that demonstrate remediation of dissolved‐phase MGP‐related groundwater impacts by natural attenuation. A statistical evaluation of the data supports a stable or declining MGP parameter concentration trend at each of the sites. A comparison of the site natural attenuation evaluation is made to compare with the requirements for site closure under the Wisconsin Department of Natural Resources regulations and guidance. © 2003 Wiley Periodicals, Inc.     

Estimated trichloroethene transformation rates due to naturally occurring biodegradation in a fractured rock aquifer

Rates of trichloroethene (TCE) mass transformed by naturally occurring biodegradation processes in a fractured rock aquifer underlying a former Naval Air Warfare Center (NAWC) site in West Trenton, New Jersey, were estimated. The methodology included (1) dividing the site into eight elements of equal size and vertically integrating observed concentrations of two daughter products of TCE biodegradation—cis‐dichloroethene (cis‐DCE) and chloride—using water chemistry data from a network of 88 observation wells; (2) summing the molar mass of cis‐DCE, the first biodegradation product of TCE, to provide a probable underestimate of reductive biodegradation of TCE, (3) summing the molar mass of chloride, the final product of chlorinated ethene degradation, to provide a probable overestimate of overall biodegradation. Finally, lower and higher estimates of aquifer porosities and groundwater residence times were used to estimate a range of overall transformation rates. The highest TCE transformation rates estimated using this procedure for the combined overburden and bedrock aquifers was 945 kg/yr, and the lowest was 37 kg/yr. However, hydrologic considerations suggest that approximately 100 to 500 kg/yr is the probable range for overall TCE transformation rates in this system. Estimated rates of TCE transformation were much higher in shallow overburden sediments (approximately 100 to 500 kg/yr) than in the deeper bedrock aquifer (approximately 20 to 0.15 kg/yr), which reflects the higher porosity and higher contaminant mass present in the overburden. By way of comparison, pump‐and‐treat operations at the NAWC site are estimated to have removed between 1,073 and 1,565 kg/yr of TCE between 1996 and 2009. © 2012 Wiley Periodicals, Inc.*     

A Slice of Guidance Provides Some Insight to Addressing Contaminated Sediments

The U.S. Environmental Protection Agency (EPA) has issued guidance to improve cleanup risk management decisions at sites involving contaminated sediments. The guidance is titled Principles for Managing Contaminated Sediment Risks at Hazardous Waste Sites and is important because sediment cleanup decisions are often very technical and complex. While the guidance is not a step‐by‐step “how to” document, it does provide the framework for risk‐based decision making and national consistency. Although it does not answer the more technical questions associated with remediation, it will likely provide site managers with greater certainty related to their decisions and help determine what questions need to be asked for many complex issues. Additional and forthcoming EPA reports, seminars, and products will be useful in building upon this framework. This article provides an overview of the risk management principles presented in the guidance. © 2002 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.     

Biosynthesis and Characterization of Laccase Catalyzed Poly(Catechol)

Enzymatic polymerization of catechol was conducted batch-wise using laccase enzyme produced by the culture Trametes versicolor (ATCC 200801). The polymerization reaction was carried out in 1:1 (v/v) aqueous-acetone solution, buffered at pH 5.0 with sodium acetate (50 mM) in a sealed, temperature-controlled reactor at 25°C. The molecular weight of the produced polymer was determined with GPC. FT-IR, DSC, and TGA were employed to investigate the structure and thermal behavior of synthesized poly(catechol). It was found that catechol units were linked together with ether bonds and thermal stability of the catechol increased in the poly(catechol) polymeric structure effectively. The number average molecular weight of poly(catechol) was found as 813 ± 3 Da with a very narrow polydispersity value of 1.17 showing selective polymerization of catechol by the enzyme.