A Multiple Lines of Evidence Framework to Evaluate Intrinsic Biodegradation of 1,4‐Dioxane

Development of a multiple lines of evidence (MLOE) framework to evaluate the intrinsic biodegradation potential of 1,4‐dioxane is vital to implementing management strategies at groundwater sites impacted by 1,4‐dioxane. A comprehensive MLOE approach was formed to provide significant evidence of natural degradation of 1,4‐dioxane comingled with tetrahydrofuran (THF) within a large, diffuse plume. State‐of‐the art molecular biological analyses and compound‐specific isotope analysis (CSIA) were employed to support more traditional approaches for data analysis (concentration trend analyses, spatial distribution, temporal changes, geochemical biodegradation attenuation indicators, plume mass estimates, and fate and transport modeling). The molecular analyses demonstrated that microorganisms capable of both metabolic and cometabolic degradation of 1,4‐dioxane were present throughout the groundwater plume, whereas the CSIA data provided supporting evidence of biodegradation. 1,4‐Dioxane biomarkers were present and abundant throughout the 1,4‐dioxane plume, and our biomarkers tracked the plume with reasonable accuracy. Evidence also suggests that THF‐driven cometabolic biodegradation as well as catabolic 1,4‐dioxane biodegradation were active at this site. These data supplemented the traditional lines of evidence approaches, which demonstrated that 1,4‐dioxane attenuation was occurring across the groundwater plume and that nondestructive physical processes alone did not account for the observed 1,4‐dioxane attenuation. This MLOE framework combining new and traditional analyses demonstrates that this site has a significant capacity for intrinsic biodegradation of 1,4‐dioxane. ©2016 Wiley Periodicals, Inc.     

Laboratory validation study of new vapor‐phase‐based approach for groundwater monitoring

Recent improvements in field‐portable analytical equipment allow accurate on‐site measurement of VOCs present in air at concentrations of less than 0.1 parts per million volume (ppmv). The objective of this project is to determine if the use of these instruments for vapor‐phase measurements of headspace in a monitoring well can serve as a reliable and accurate method for monitoring volatile organic compound (VOC) concentrations in groundwater under equilibrium conditions. As part of a comprehensive research project investigating the utility of this proposed monitoring method, the authors have completed a laboratory validation study to identify instruments and sample‐collection methods that will provide accurate measurement of VOC concentrations in groundwater. This laboratory validation study identified two field‐portable instruments (a gas chromatograph and a photoionization detector) with sufficient sensitivity to measure VOCs in groundwater at concentrations below typical monitoring standards (i.e., 1 to 5 μg/L). The accuracy and precision of these field instruments was sufficient to satisfy typical data‐quality objectives for laboratory‐based analysis. In addition, two sample‐collection methods were identified that yield vapor‐phase samples in equilibrium with water: direct headspace sampling and passive diffusion samplers. These sample‐collection methods allow the field instruments (which measure VOC concentrations in vapor‐phase samples) to be used to measure VOC concentrations in water. After further validation of these sample‐collection methods in the field, this monitoring method will provide a simple way to obtain accurate real‐time measurements of VOC concentrations in groundwater using inexpensive field‐portable analytical instruments. © 2009 Wiley Periodicals, Inc.     

Examining the concept of convenient collection: An application to extended producer responsibility and product stewardship frameworks

Increasingly, Extended Producer Responsibility (EPR) and Product Stewardship (PS) frameworks are being adopted as a preferred policy approach to promote cost-effective diversion and recovery of post-consumer solid waste. Because the application of EPR/PS generally requires the creation of a separate and often parallel collection and/or management system, key to increasing the amount of waste recovered is to maximize the convenience of the collection system to maximize consumer participation. Convenient collection is often mandated in EPR/PS laws, however it is not defined. Convenience is a subjective construct rendering it extremely difficult to define. However, based on a dissection of post-consumer collection efforts under a generic EPR/PS system, this paper identifies and examines five categories of convenience – knowledge requirements, proximity to a collection site, opportunity to drop-off materials, the draw of the collection site, and the ease of the process—and the various factors of convenience within each of these categories. By using a simplified multiple criteria decision analysis, this paper proposes a performance matrix of criteria of convenience. Stakeholders can use this matrix to assist in the design, assessment, and/or implementation of a convenient post-consumer collection system under an EPR/PS framework.     

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

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

Triad case study: Marine Corps Base Camp Pendleton

The U.S. Navy Public Works Center (PWC) Environmental Department, San Diego, California, is home to the Navy West Coast Site Characterization and Analysis Penetrometer System (SCAPS). SCAPS has been extensively used at several Navy sites since 1995 to provide real‐time, high‐density data sets. The U.S. Environmental Protection Agency's Triad approach provided an ideal framework for optimizing the use of the Navy SCAPS during a volatile organic compound (VOC) source investigation at Installation Restoration Site 1114 at Marine Corps Base Camp Pendleton. All three elements of Triad—systematic planning, dynamic work strategy, and use of real‐time measurement tools—were implemented to manage decision uncertainty and expedite the site management process. The investigation was conducted using the Navy SCAPS, outfitted with a cone penetrometer, membrane interface probe, and a direct sampling ion trap mass spectrometry detector, which allowed for real‐ time collection of over 690 feet of continuous lithologic information and VOC concentration data. These data were used collaboratively with 24‐hour turnaround US EPA 8260B VOC groundwater results from temporary direct‐ push wells to support the conclusion of a limited source area. Implementation of the Triad approach for this investigation provided an expedited high‐density data set and a refined conceptual site model (CSM) in real time that resulted in cost savings estimated at $2.5M and reduction of the site characterization and cleanup schedule by approximately three years. This project demonstrates how the US EPA's Triad approach can be applied to streamline the site characterization and cleanup process while appropriately managing decision uncertainty in support of defensible site decisions. © 2004 Wiley Periodicals, Inc.     

Characterization and pilot‐scale studies for chemical oxidation remediation of fractured shale

The distribution of volatile organic compounds (VOCs) in fractured shale overlain by thin (< 10 feet) overburden at the Watervliet Arsenal near Albany, New York, was initially determined by sampling water from the fracture network using packer systems in boreholes and also using conventional monitoring wells. Furthermore, short‐term pumping and injection tests were conducted and the boreholes were logged using a variety of geophysical and hydrophysical tools. Tetrachloroethene is the dominant VOC in the groundwater, with lesser concentrations of trichloroethene and degradation products (cis‐1,2‐dichloroethene, trans‐1,2‐dichloroethene, and vinyl chloride). The vertical VOC distributions in the rock matrix were obtained from continuous‐cored holes from which small rock samples, collected at many depths between 18 and 150 feet below ground surface, were analyzed. The rock core VOC concentrations were determined by methanol extraction of crushed rock followed by direct methanol injection onto a gas chromatograph and subsequent estimation of rock porewater VOC concentrations. The rock core data support the concept that diffusion‐driven mass transfer has caused nearly all the VOC mass initially present in the fractures to now reside in the rock matrix, which has a porosity three or four orders of magnitude larger than the bulk fracture porosity. The results of the site characterization indicate that an effective site investigation strategy in fractured shale must include characterization of both the fracture and matrix contaminant distribution. These results also indicate that the most favorable remediation technologies for this fractured shale are those that will destroy VOCs in the rock matrix, particularly contaminants in the sorbed phase, and also destroy the VOC mass in the fractures including both dissolved and immiscible phases. The site characterization resulted in the selection of potassium permanganate for an in situ chemical oxidation pilot study. © 2004 Wiley Periodicals, Inc.     

Breakthrough in 2D‐CSIA Technology for 1,4‐Dioxane

A dual isotope technology based on compound‐specific stable isotope analysis of carbon and hydrogen (2D‐CSIA) was recently developed to help identify sources and monitor in situ degradation of the contaminant 1,4‐dioxane (1,4‐D) in groundwater. Site investigation and optimized remediation have been the focus of thousands of CSIA applications completed for volatile organic contaminants (VOCs) worldwide. CSIA for the water miscible 1,4‐D, however, has been technically challenging. The most commercially available sample preparation settings “Purge and Trap” for VOC could not efficiently extract 1,4‐D out of water for a reliable CSIA measurement, especially when the concentration is below 100 μg/L. Such a high reporting limit has prevented CSIA from being used for effective site investigation and remediation monitoring at most 1,4‐D contaminated sites, where 1,4‐D is often present at very low ppb levels. This article outlines the recent breakthrough in 2D‐CSIA technology for 1,4‐D in water, reported down to ～1 μg/L for carbon, and ～10 μg/L to 20 μg/L for hydrogen using solid‐phase extraction based on EPA Method 522, and its benefit is highlighted through a case study at a 1,4‐D contaminated site. ©2016 Wiley Periodicals, Inc.     

Nanotechnology and groundwater remediation: A step forward in technology understanding

Nanotechnology application to contaminated site remediation, and especially the use of nanoscale zero‐valent iron particles to treat volatile organic compound (VOC)‐impacted groundwater, is now recognized as a promising solution for cost‐effective in situ treatment. Results obtained during numerous pilot tests undertaken by Golder Associates between 2003 and 2005 in North America (United States and Canada) and Europe have been used to present a synthetic cross‐comparison of technology dynamics. The importance of a comprehensive understanding of the site‐specific geological, hydrogeological, and geochemical conditions, the selection of appropriate nanoscale particles, the importance of monitoring geochemical parameters during technology application, and the potential of nanoparticle impact on microbial activity are discussed in this article. The variable technology dynamics obtained during six pilot tests (selected among numerous other tests) are then presented and discussed. © 2006 Wiley Periodicals, Inc.     

The Application of Stable Isotopes for Assessing the Hydrological, Sulfur, and Iron Balances of Acidic Mining Lake ML 111 (Lusatia, Germany) as a Basis for Biotechnological Remediation

Stable isotope (¹⁸O–H₂O, ²H–H₂O ³⁴S–SO₄ ^2-) andhydrochemical data (SO₄ ^2-, Fe-concentrations) have beenused to estimate the annual groundwater inflow and outflow of mining lake ML 111 and to calculate the total amount of dissolvedsulfate and iron that is carried into the lake by groundwater. The hydrological balance suggests an annual groundwater inflow of 23 700 m³ and an annual groundwater outflow of 15 700 m³. The calculation of the sulfur and iron balances yielded an annual sulfate input of 37 800 kg and an annual iron input of 7000 kg with the groundwater inflow. Furthermore it was shown that significant fluxes of these elements go into the lake sediments which results in continuous release of acidity in the lake water.     

Before‐after control‐impact paired modeling of groundwater bentazon treatment at a phytoremediation site

A Before‐ After Control‐ Impact Paired (BACIP) model was used to evaluate the effectiveness of phytoremediation treatment on reduction of bentazon concentrations in shallow groundwater at a study site in Louisiana. Two different statistical approaches were made to evaluate the impact to this test site from the remediation program through time. Data were evaluated by Bayesian analysis of variance test methods. Data sets were unique in that the control data used for impact evaluation, as compared to before and after data, were compiled from groundwater upgradient monitoring wells existing prior to remediation. The statistical model supports the hypothesis that the phytoremediation program has positively impacted groundwater at the study site. © 2006 Wiley Periodicals, Inc.     

USING ISOTOPIC AND MOLECULAR DATA TO MODEL LANDFILL GAS PROCESSES

Using a large data set, a preliminary investigation has been made to evaluate the usefulness of stable isotope ratios for improving our understanding of methane and carbon dioxide generation in landfills. Included are approximately 130 landfill gas samples from across the U.S.A., and 18 recent samples from: (1) an Argonne Laboratory study area in the Brea-Olinda Landfill, Orange County, California (U.S.A); and (2) several Los Angeles County landfills, California (U.S.A). The following isotope ratios were examined: δ¹³C for methane, δ¹³C for carbon dioxide and δD for methane. Using simple ratio plots supplemented by mass-balance calculations, these data show promise for indicating the relative contributions of the four major carbon cycle processes in landfills, namely: (1) direct oxidation of organic material to carbon dioxide; (2) methane generation from fermentation (acetate cleavage); (3) methane generation from carbon dioxide reduction; and (4) methane oxidation to carbon dioxide by methanotrophic bacteria. Both the methane generation and oxidation reactions are central to an explanation of the trends discussed herein. The data also suggest that direct oxidation of organic matter in the refuse may be contributing to the observed isotopic ratios in some cases. The trends observed at the Brea-Olinda site were similar to trends using the large U.S. database, suggesting that isotopic techniques may be useful to better constrain carbon cycle processes common to all landfill settings.     

Assessing cleanup levels for industrial sites under state risk reduction programs

Many states are promoting the cleanup and reuse of industrial sites. The reasons stem from the need to implement cost-effective risk reduction programs that show reasonable progress in the cleanup of contaminated sites and from the need to make effective use of industrial sites instead of abandoning them and making use of greenfield sites for new industrial facilities. The industrial land-use cleanup criteria developed by states are primarily risk-based. Several EPA regional offices also have developed similar risk-based cleanup criteria. This article addresses methodologies employed for assessing and evaluating the level of cleanup at several industrial sites in Texas, Michigan, and Ohio. This includes defining the regulatory framework, estimating the level and extent of contamination of soil and groundwater, assessing migration pathways, performing health risk assessments, and estimating cleanup requirements and associated costs. The implications associated with the various types of risk reduction options available for these states also are addressed.     

Evolution of predictive tools for in situ bioremediation and natural attenuation evaluations

Proving the viability of in situ bioremediation technologies and gathering data for its full‐scale implementation typically involves collecting multiple rounds of data and often completing microcosm studies. Collecting these data is cumbersome, time‐consuming, costly, and typically difficult to scale. A new method of completing microcosm studies in situ using an amendable sampling device deployed and incubated in groundwater monitoring wells provides actionable data to expedite site cleanup. The device, referred to as a Bio‐Trap® sampler, is designed to collect actively colonizing microbes and dissolved organic compounds from groundwater for analysis using conventional analytical techniques and advanced diagnostic tools that can answer very specific design and viability questions relating to bioremediation. Key data that can be provided by in situ microcosm studies using Bio‐Trap® samplers include definitively demonstrating contaminant destruction by using compound‐specific isotope analysis and providing data on the mechanism of the degradation by identifying the responsible microbes. Three case studies are presented that demonstrate the combined flexibility of Bio‐Trap® samplers and advanced site diagnostics. The applications include demonstrating natural attenuation of dissolved chlorinated solvents, demonstrating natural attenuation of dissolved petroleum compounds, and using multiple Bio‐Trap® samplers to comparatively assess the viability of bioaugmentation at a chlorinated solvent release site. At each of these sites, the in situ microcosm studies quickly and cost‐effectively answered key design and viability questions, allowing for regulatory approval and successful full‐scale implementation. © 2010 Wiley Periodicals, Inc.     

Look at groundwater quality to set VOC cleanup levels

In 1981, the Arizona Department of Health Services (ADHS) discovered groundwater contamination by solvents and chromium at the Phoenix Goodyear Airport (PGA), just outside the city of Phoenix. ADHS and the U.S. EPA sampled the site for the next two years, finding that eighteen of their wells were contaminated with trichloroethene (TCE), six exceeding ADHS's action level of five micrograms per liter (μg/l). In 1983, the PGA site was added to the National Priorities List, and, in 1984, EPA began a $3 million remedial investigation, focusing on soils and groundwater. This article discusses how that investigation inspired the authors to develop a stream-lined evaluation method for PGA's volatile organic compounds (VOCs), the process for establishing VOC cleanup levels, and the $26 million of remediation work needed to be done at the site. The heart of this effort is a computer program called VLEACH, loosely standing for VOC-LEACHing, which anticipates the influence of VOCs on PGA's groundwater, even as remediation proceeds.     

Migration of VOC Plume in the Subsurface Domain at the Y‐12 National Security Site

During the production of thermonuclear fusion weapons at the Y‐12 National Security Complex (Y‐12 NSC) in Oak Ridge, Tennessee, between 1950 and 1963, the regional environment was extensively contaminated by volatile organic compounds (VOCs). Old Salvage Yard (OSY) on the western side of the site has been characterized as the major source of VOCs. In order to analyze the long‐term fate and transport of chlorinated VOC sources, an integrated surface and subsurface flow and transport model was developed for the Y‐12 NSC using the hydrodynamic and transport numerical package MIKE‐SHE. The model was developed considering the recent hydrogeological investigations on preferential flow and transport pathways at the site. The model was calibrated using the recorded groundwater flow and water‐quality data. The modeling simulated migration of the VOC plume for the next 100 years. Considering a range of hydrogeological and transport parameters, uncertainty of the results is discussed. The modeling predicted that tetrachloroethene, trichloroethene, and 1,2‐dichloroethene may exceed human health–related risk levels for the next 10 to 20 years. However, the contamination is unlikely to migrate to surface water under the current hydrogeological conditions and will decay below acceptable risk levels within approximately 20 years. © 2013 Wiley Periodicals, Inc.     

δ13C of Tree-Ring Lignin as an Indirect Measure of Climate Change

High-resolution paleoclimatic data are an essential requirement for testing numerical models of climate change and the global carbon cycle. If the long tree-ring chronologies, originally established for the purpose of dendrochronology, are to be fully exploited as an indirect measure of past climatic variability, additional techniques are required to obtain this information. The determination of the δ¹³C value of tree-ring cellulose has been used successfully to reconstruct past climates. However, under both aerobic and anaerobic conditions, the polysaccharide components of vascular plants (mainly cellulose and hemicelluloses) are more prone to rapid degradation than lignin. This has serious implications for the use of carbon isotope values of tree-ring cellulose as an indirect measure of past climates. An absolutely dated ring-width chronology was established for oaks (Quercus robur L.) growing at Sandringham Park in eastern England. Carbon isotope values were determined on α-cellulose and `Klason' lignin isolated from annual latewood samples over the period AD 1895–1999. The carbon isotope values of earlywood lignin are correlated with the latewood carbon isotope values of the previous year, supporting the theory that some of the carbon utilised in earlywood synthesis is assimilated in the previous year. The high-frequency variance in the carbon isotope indices of latewood lignin and cellulose is highly correlated with combined July and August environmental variables, indicating that they were formed at similar times. There was no evidence of secondary lignification. These resultsdemonstrate that the determination of carbon isotope values of latewood lignin offers the potential to obtain unambiguous proxy climatic data covering several millennia.     

Successful combination of remediation techniques at a former silver factory

A residential area that was formerly part of a silver factory site severely contaminated with chlorinated solvents was remediated using an in situ electro‐bioreclamation technique. Electro‐bioreclamation is a method for heating soil and groundwater combined with soil vapor and low‐yield groundwater extraction and enhanced reductive dechlorination (ERD). During the first two years of remediation in the source area (the intensive phase), a total of 80 kg of volatile organic compounds (VOCs) was removed by heating combined with ERD. After another two years of ERD in the source and plume areas (the attenuation phase), the VOC concentrations were reduced to a level below 100 μg/L in groundwater. Given these satisfying results, electro‐reclamation in combination with ERD turned out to be a successful in situ remediation technique for removing VOCs. © 2006Wiley Periodicals, Inc.     

A decision support system for assessing landfill performance

Designing environmentally sound landfills is a challenging engineering task due to complex interactions of numerous design variables; such as landfill size, waste characteristics, and site hydrogeology. Decision support systems (DSS) can be utilized to handle these complex interactions and to aid in a performance-based landfill design by coupling system simulation models (SSM). The aim of this paper is to present a decision support system developed for a performance-based landfill design. The developed DSS is called Landfill Design Decision Support System – LFDSS. A two-step DSS framework, composed of preliminary design and detailed design phases, is set to effectively couple and run the SSMs and calculation modules. In preliminary design phase, preliminary design alternatives are proposed using general site data. In detailed design phase, proposed design alternatives are further simulated under site-specific data using SSMs for performance evaluation. LFDSS calculates the required landfill volume, performs landfill base contour design, proposes preliminary design alternatives based on general site conditions, evaluates the performance of the proposed designs, calculates the factor of safety values for slope stability analyses, and performs major cost calculations. The DSS evaluates the results of all landfill design alternatives, and determines whether the design satisfies the predefined performance criteria. The DSS ultimately enables comparisons among different landfill designs based on their performances (i.e. leachate head stability, and groundwater contamination), constructional stability and costs. The developed DSS was applied to a real site, and the results demonstrated the strengths of the developed system on designing environmentally sound and feasible landfills.     

Innovative applications of subgrade biogeochemical reactors: Three case studies

Subgrade biogeochemical reactors (SBGRs) are an in situ remediation technology shown to be effective in treating contaminant source areas and groundwater hot spots, while being sustainable and economical. This technology has been applied for over a decade to treat chlorinated volatile organic compound source areas where groundwater is shallow (e.g., less than approximately 30 feet below ground surface [ft bgs]). However, this article provides three case studies describing innovative SBGR configurations recently developed and tested that are outside of this norm, which enable use of this technology under more challenging site conditions or for treatment of alternative contaminant classes. The first SBGR case study addresses a site with groundwater deeper than 30 ft bgs and limited space for construction, where an SBGR column configuration reduced the maximum trichloroethene (TCE) groundwater concentration from 9,900 micrograms per liter (μg/L) to <1 μg/L (nondetect) within approximately 15 months. The second SBGR is a recirculating trench configuration that is supporting remediation of a 5.7‐acre TCE plume, which has significant surface footprint constraints due to the presence of endangered species habitat. The third SBGR was constructed with a new amendment mixture and reduced groundwater contaminant concentrations in a petroleum hydrocarbon source area by over 97% within approximately 1 year. Additionally, a summary is provided for new SBGR configurations that are planned for treatment of additional classes of contaminants (e.g., hexavalent chromium, 1,4‐dioxane, dissolved explosives constituents, etc.). A discussion is also provided describing research being conducted to further understand and optimize treatment mechanisms within SBGRs, including a recently developed sampling approach called the aquifer matrix probe.     

Arsenic and thallium data in environmental samples: Fact or fiction?

Matrix effects may increasingly lead to erroneous environmental decisions as regulatory limits or risk‐based concentrations of concern for trace metals move lower toward the limits of analytical detection. A U.S. Environmental Protection Agency Office of Technical Standards Alert estimated that environmental data reported using inductively coupled plasma spectrometry (ICP‐AES) has a false‐positive rate for thallium of 99.9 percent and for arsenic of 25 to 50 percent. Although this does not seem to be widely known in the environmental community, using three case studies, this article presents data in environmental samples that demonstrate severe matrix effects on the accuracy of arsenic and thallium results. Case Study 1 involves soil results with concentrations that approached or exceeded the applicable regulatory soil cleanup objectives of 13 mg/kg for arsenic and 2 mg/kg for thallium. Reanalysis using ICP coupled with a mass spectrometer (ICP‐MS) confirmed all thallium results were false positives and all arsenic results were biased high, concluding no action was required for soil remediation. Case Study 2 involves groundwater results for thallium at a Superfund site, where thallium was detected in groundwater up to 21.6 μ g/L using ICP‐AES. Reanalysis by ICP‐MS reported thallium as nondetect below the applicable regulatory level in all samples. ICP‐MS is usually a more definitive and accurate method of analysis compared to ICP‐AES; however, this is not always the case, as we demonstrate in Case Study 3, using data from groundwater samples at an industrial site. Through a weight‐of‐evidence approach, it is demonstrated that although method quality control results were acceptable, interferences in some groundwater samples caused biased high results for arsenic using ICP‐MS, which were significantly lower when reanalyzed using hydride generation atomic fluorescence spectrometry. Causes of these interference effects and conclusions from the three case studies to obtain accurate metal data for site assessment, risk characterization, and remedy selection are discussed. © 2010 Wiley Periodicals, Inc.