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.     

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.     

Lead in soil by field‐portable x‐ray fluorescence spectrometry—an examination of paired In Situ and laboratory ICP‐AES results

A major aspect of lead hazard control is the evaluation of soil lead hazards around housing coated with lead‐based paint. The use of field‐portable X‐ray fluorescence (FPXRF) to do detailed surveying, with limited laboratory confirmation, can provide lead measurements in soil (especially for planning abatement activities) in a far more cost‐efficient and timely manner than laboratory analysis. To date, one obstacle to the acceptance of FPXRF as an approved method of measuring lead in soil has been a lack of correspondence between field and laboratory results. In order to minimize the differences between field and laboratory results, RTI International (RTI) has developed a new protocol for field drying and sieving soil samples for field measurement by FPXRF. To evaluate this new protocol, composite samples were collected in the field following both U.S. Department of Housing and Urban Development (HUD) guidelines and ASTM International (ASTM) protocols, measured after drying by FPXRF, and returned to the laboratory for confirmatory inductively coupled plasma atomic emission spectroscopy (ICP‐AES) analysis. Evaluation of study data from several diverse sites revealed no statistical difference between paired FPXRF and ICP‐AES measurements using the new method. © 2008 Wiley Periodicals, Inc.     

Field Performance of Point Velocity Probes at a Tidally Influenced Site

Conventional methods to estimate groundwater velocity that rely on Darcy's Law and average hydrogeologic parameter values are insensitive to local‐scale heterogeneities and anisotropy that control advective flow velocity and direction. Furthermore, at sites that are tidally influenced or have extraction wells with variable pumping schedules, infrequent water‐level measurements may not adequately characterize the range and significance of transient hydraulic conditions. The point velocity probe (PVP) is a recently developed instrument capable of directly measuring local‐scale groundwater flow velocity and direction. In particular, PVPs may offer distinct advantages for sites with complex groundwater–surface water interactions and/or with spatially and temporally variable groundwater flow conditions. The PVP utilizes a small volume of saline tracer and inexpensive sensors to directly measure groundwater flow direction and velocity in situ at the centimeter‐scale and discrete times. The probes are installed in conventional direct‐push borings, rather than in wells, thus minimizing the changes and biases in the local flow field caused by well installation and construction. Six PVPs were installed at a tidally influenced site in North Carolina to evaluate their implementability, performance, and potential value as a new site characterization tool. For this study, a new PVP prototype was developed using a rapid prototyping machine (i.e., a “three‐dimensional printer'') and included both horizontally and vertically oriented tracer detectors. A site‐specific testing protocol was developed to account for the spatially and temporally variable hydraulic conditions and groundwater salinity. The PVPs were tested multiple times, and the results were compared to the results of several different groundwater flux and velocity estimation tools and methods, including a heat‐pulse flowmeter, passive flux meters, single‐well tracer tests, and high‐resolution hydraulic gradient analysis. Overall, the results confirmed that the PVP concept is valid and demonstrated that reliable estimates of groundwater velocity and direction can be obtained in simple settings. Also, PVPs can be successfully installed by conventional methods at sites where the formation consists primarily of noncohesive soils and the water table is relatively shallow. Although some PVP tests yielded consistent and reliable results, several tests did not. This is likely due to the highly transient flow conditions and limitations associated with the PVP design and testing procedures. PVPs offer particular advantages over, and can effectively complement, other groundwater flow characterization techniques for certain conditions, and objectives may be useful for characterizing complex flow patterns under steady conditions; however, this study suggests that PVPs are best suited for conditions where the flow hydraulics are not highly transient. For sites where the hydraulic conditions are highly transient, the most reliable approach for understanding groundwater flow behavior and groundwater–surface water interactions would generally involve both a high‐resolution hydraulic gradient analysis and another local‐scale method, such as tracer testing. This study also highlighted some aspects of the current PVP design and testing protocol that can be improved upon, including a more robust connection between the PVP and injection line and further assessment of tracer solution density effects on vertical flow. © 2013 Wiley Periodicals, Inc.     

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.     

The ART In‐Well Technology test at a chlorinated solvent site in central Iowa

An Accelerated Remediation Technologies (ART) In‐Well Technology pilot test was performed to evaluate the removal of chlorinated volatile organic compounds (VOCs) from groundwater. The ART In‐Well Technology was installed in one well located in the source area where dense nonaqueous‐phase liquid has been identified and VOC concentrations exceed 140,000 μg/L. Monitoring wells at the site were positioned between 10 and 170 feet from the ART test well. Overall, VOC concentrations from samples collected from the groundwater monitoring wells and in the vapors extracted for discharge from the ART treatment well were analyzed over the testing period. Monitoring results showed that concentrations of perchloroethylene were reduced in the closest monitoring well to nondetectable concentrations within 90 days. The cumulative removal of chlorinated VOCs from the ART test well over the six‐month pilot test period exceeded 9,500 pounds based on air monitoring data. The ART technology proved effective and cost‐efficient in reducing contaminant concentrations and removing a large mass of contamination from the subsurface in a short period of time. The radius of influence of the ART technology at the site was estimated to range between 65 and 170 feet. © 2007 Wiley Periodicals, Inc.     

Chemical Oxidation Performance in High Temperature,Saline Groundwater Impacted With Hydrocarbons

A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for in situ chemical oxidation (ISCO) of aromatic hydrocarbons and methyl tertiary butyl ether (MTBE), a common oxygenate additive in gasoline, in saline, high temperature (more than 30 °C) groundwater. Groundwater samples from a site in Saudi Arabia were amended in the laboratory portion of the study with the chemical oxidants, sodium persulfate (Na₂S₂O₈) and sodium percarbonate (Na₂(CO₃)₂), to evaluate the changes in select hydrocarbon and MTBE concentrations with time. Almost complete degradation of the aromatic hydrocarbons, naphthalene and trimethylbenzenes (TMBs), was found in the groundwater sample amended with persulfate, whereas the percarbonate‐amended sample showed little to no degradation of the target hydrocarbon compounds in the laboratory. Isotopic analyses of the persulfate‐amended samples suggested that C‐isotope fractionation for xylenes occurred after approximately 30 percent reduction in concentration with a decline of about 1 percent in the δ¹³C values of xylenes. Based on the laboratory results, pilot‐scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of chemical oxidation using nonactivated persulfate on a high temperature, saline petroleum hydrocarbon plume. Approximately 1,750 kg of Na₂S₂O₈ was delivered to the subsurface using a series of injection wells over three injection events. Results obtained from the pilot test indicated that all the target compounds decreased with removal percentages varying between 86 percent for naphthalene and more than 99 percent for the MTBE and TMBs. The benzene, toluene, ethylbenzene, and xylene compounds decreased to 98 percent on average. Examination of the microbial population upgradient and downgradient of the ISCO reactive zone suggested that a bacteria population was present following the ISCO injections with sulfate‐reducing bacteria (SRB) being the dominant bacteria present. Measurements of inorganic parameters during injection and postinjection indicated that the pH of the groundwater remained neutral following injections, whereas the oxidation–reduction potential remained anaerobic throughout the injection zone with time. Nitrate concentrations decreased within the injection zone, suggesting that the nitrate may have been consumed by denitrification reactions, whereas sulfate concentrations increased as expected within the reactive zone, suggesting that the persulfate produced sulfate. Overall, the injection of the oxidant persulfate was shown to be an effective approach to treat dissolved aromatic and associated hydrocarbons within the groundwater. In addition, the generation of sulfate as a byproduct was an added benefit, as the sulfate could be utilized by SRBs present within the subsurface to further biodegrade any remaining hydrocarbons. ©2015 Wiley Periodicals, Inc.     

Enhanced anaerobic bioremediation of chlorinated solvents utilizing vegetable oil emulsions

The use of vegetable oil as an electron donor to enhance the reductive dechlorination of chlori‐nated solvents as an in situ remediation technology is gaining significant traction. Vegetable oil is a cost‐effective slow‐release electron donor with greater hydrogen‐release efficiency than other electron‐donor products. However, neat vegetable oil can inhibit distribution in aquifers due to the oil droplets blocking the flow of groundwater through the smaller pore spaces in the aquifer materials. This issue has been partially overcome by applying the vegetable oil as an oil‐water emulsion, which typically is created in the field. However, the field preparation results in a mixture of droplet sizes, including larger droplets that can make the emulsions unstable and reduce the soil permeability by blocking soil‐pore throats with oil. RNAS, Inc., has developed a kinetically sta‐ble soybean oil emulsion (“Newman Zone”) consisting of submicron droplets with less droplet‐size variation than field‐prepared emulsions. This product is composed of a blend of fast‐release (sodium lactate) and slow‐release (soybean oil) electron donors. The emulsion is produced in a stable factory environment in which it is pasteurized and packaged in sterile packaging. This ma‐terial can be utilized as an electron donor without further treatments or amendments in the field. This article discusses factors associated with selecting electron donors and the development of vegetable oil–based products. A case study of an application of Newman Zone at a former adhe‐sives manufacturing facility is then presented. The case study demonstrates the effect of Newman Zone in reducing chlorinated solvent concentrations in groundwater by both rapidly stimulating initial microbial activity and supporting long‐term reductive dechlorination with a slow‐release electron donor. © 2006 Wiley Periodicals, Inc.     

Experimental and numerical analysis of metal leaching from fly ash-amended highway bases

A study was conducted to evaluate the leaching potential of unpaved road materials (URM) mixed with lime activated high carbon fly ashes and to evaluate groundwater impacts of barium, boron, copper, and zinc leaching. This objective was met by a combination of batch water leach tests, column leach tests, and computer modeling. The laboratory tests were conducted on soil alone, fly ash alone, and URM-fly ash-lime kiln dust mixtures. The results indicated that an increase in fly ash and lime content has significant effects on leaching behavior of heavy metals from URM-fly ash mixture. An increase in fly ash content and a decrease in lime content promoted leaching of Ba, B and Cu whereas Zn leaching was primarily affected by the fly ash content. Numerically predicted field metal concentrations were significantly lower than the peak metal concentrations obtained in laboratory column leach tests, and field concentrations decreased with time and distance due to dispersion in soil vadose zone.     

The horizontal reactive media treatment well (HRX Well®) for passive in situ remediation: Design,implementation, and sustainability considerations

A new in situ remediation concept termed a Horizontal Reactive Media Treatment Well (HRX Well^®) is presented that utilizes a horizontal well filled with reactive media to passively treat contaminated groundwater in situ. The approach involves the use of a large‐diameter directionally drilled horizontal well filled with solid reactive media installed parallel to the direction of groundwater flow. The engineered contrast in hydraulic conductivity between the high in‐well reactive media and the ambient aquifer hydraulic conductivity results in the passive capture, treatment, and discharge back to the aquifer of proportionally large volumes of groundwater. Capture and treatment widths of up to tens of feet can be achieved for many aquifer settings, and reductions in downgradient concentrations and contaminant mass flux are nearly immediate. Many different types of solid‐phase reactive treatment media are already available (zero valent iron, granular activated carbon, biodegradable particulate organic matter, slow‐release oxidants, ion exchange resins, zeolite, apatite, etc.). Therefore, this concept could be used to address a wide range of contaminants. Laboratory and pilot‐scale test results and numerical flow and transport model simulations are presented that validate the concept. The HRX Well can access contaminants not accessible by conventional vertical drilling and requires no aboveground treatment or footprint and requires limited ongoing maintenance. A focused feasibility evaluation and alternatives analysis highlights the potential cost and sustainability advantages of the HRX Well compared to groundwater extraction and treatment systems or funnel and gate permeable reactive barrier technologies for long‐term plume treatment. This paper also presents considerations for design and implementation for a planned upcoming field installation.     

Groundwater geochemistry diagnostics during in situ ERH remediation

In situ remediation represents a series of challenges in interpreting the monitoring data on remedial progress. Among these challenges are problems in determining the progress of the remediation and the mechanisms responsible, so that the process can be optimized. The release of organic pollutants to groundwater systems and in situ remediation technologies alter the groundwater chemistry, but outside of natural attenuation studies using inorganic chemical analyses as indicators of intrinsic biodegradation, typically little attention has been paid to the changes in inorganic groundwater chemistry. Smith (2008) noted that during an electrical resistance heating remediation that took place at a confidential site in Chicago, a two‐orders‐of‐magnitude increase in chloride concentrations occurred during the remediation. This increase in chloride resulted in a corresponding increase in calcium as a result of what is known as the common ion effect. Carbon dioxide is the gas found in highest concentrations in natural groundwater (Stumm & Morgan, 1981), and its fugacity (partial pressure) corresponds directly with calcium concentrations. Carbon dioxide at supersaturation in groundwater is capable of dissolving organic compounds, such as trichloroethene, facilitating removal of nonaqueous‐phase liquids at temperatures below the boiling point of water. One means of diagnosing these reactions is through the use of compound‐specific isotopic analysis, which is capable of distinguishing between evaporation, biodegradation, and differences in sources. The appropriate diagnosis has the potential to optimize the benefits from these reactions, lower energy costs for removal of nonaqueous‐phase liquids, and direct treatment where it is needed most. © 2010 Wiley Periodicals, Inc.     

1,4‐Dioxane: Emerging technologies for an emerging contaminant

The synthetic chemical, 1,4‐dioxane, is classified by the U.S. Environmental Protection Agency (EPA) as a probable human carcinogen. Between 2013 and 2015, the EPA detected 1,4‐dioxane in public drinking water supplies in 45 states at concentrations up to 33 µg/L and in groundwater from releases at hazardous waste sites across the United States. Although a Federal maximum contaminant level drinking water standard has not yet been proposed, state‐specific standards and criteria are as low as 0.3 µg/L. 1,4‐Dioxane is a recalcitrant chemical in that applications of conventional treatment technologies have had limited success in reducing concentrations in water to meet current and proposed health‐protective levels. Although mainly used as a stabilizer for the solvent 1,1,1‐trichloroethane, it has been used in other industrial processes and has been detected in a variety of consumer products, such as foods, pharmaceuticals, cosmetics, and detergents. The high aqueous solubility of 1,4‐dioxane coupled with limited solubility of chlorinated solvents typically found in conjunction with 1,4‐dioxane contamination is the primary reason for its treatment challenges. In the last several years, an alternative, cost‐effective technology has been developed that has demonstrated treatment to levels significantly lower than the Federal and state‐specific goals. This article provides a Federal and state‐by‐state summary of 1,4‐dioxane‐specific drinking water and groundwater concentration criteria and qualitative comparison of the effectiveness of conventional treatment technologies compared to the effectiveness of an alternative treatment technology. A case study is also provided to present details regarding the application of an alternative treatment technology at an active groundwater remediation site in California.     

Nuclear magnetic resonance logging: Example applications of an emerging tool for environmental investigations

Nuclear magnetic resonance (NMR) geophysical tools have been widely used in the petroleum exploration industry since the 1960s and have improved significantly in the last two decades. These tools can provide estimates of bulk porosity and fluid content, quantification of bound versus mobile fluids, and estimates of hydraulic conductivity (K). Although the size and cost of oil‐field tools historically limited their use for near‐surface applications, smaller and more economical downhole NMR logging tools are now available for detecting and characterizing the formation water content and K to support environmental and groundwater resource investigations. These tools can be deployed using direct‐push drilling techniques or they can be lowered into existing open borings or wells with nonconductive polyvinyl chloride casings and screens. In many cases, using the tool in existing wells offers a safer and more cost‐effective alternative compared to drilling new boreholes. For environmental investigations, NMR can provide useful high‐resolution quantitative hydrostratigraphic information that can provide additional valuable data to further inform and refine the conceptual site model. This paper highlights several NMR field investigations that demonstrate the viability of this technology as a site characterization tool for near‐surface investigations. NMR measurements were compared to data from lithologic logs, cone penetrometer testing data, and prior field hydraulic tests. Use of NMR to detect vadose zone water, including previously unidentified perched groundwater zones, provided hydrostratigraphic details that could not be gleaned from historical well drilling logs and were used to evaluate drainable pore water versus pore water bound in small pores by capillary forces or electrochemically clay‐bond water. NMR also produced K estimates similar to those from conventional hydraulic tests, but the improved vertical resolution from NMR provided additional information regarding the vertical heterogeneity of the formation along the entire length of the well or borehole. Additionally, bench‐scale tests are presented that confirm the capability for NMR to reliably detect and quantify light nonaqueous phase liquid saturation (specifically diesel fuel and weathered gasoline) in situ. The field tests combined with bench‐scale testing results affirm the applicability and potential for NMR as a practical characterization tool that should increasingly be utilized in environmental investigations.     

Methane generation in tropical landfills: simplified methods and field results

This paper deals with the use of simplified methods to predict methane generation in tropical landfills. Methane recovery data obtained on site as part of a research program being carried out at the Metropolitan Landfill, Salvador, Brazil, is analyzed and used to obtain field methane generation over time. Laboratory data from MSW samples of different ages are presented and discussed; and simplified procedures to estimate the methane generation potential, Lo, and the constant related to the biodegradation rate, k are applied. The first order decay method is used to fit field and laboratory results. It is demonstrated that despite the assumptions and the simplicity of the adopted laboratory procedures, the values Lo and k obtained are very close to those measured in the field, thus making this kind of analysis very attractive for first approach purposes.     

Web‐based automated remediation performance monitoring and visualization of contaminant mass flux and discharge

Environmental monitoring, data processing, and reporting methods are expensive, labor‐ and resource‐intensive, time‐consuming, and often inaccurate. An innovative project management platform was developed for integrating environmental monitoring sensors, telemetry, geographical information systems, models, and geostatistical algorithms for automatically generating contour maps and time‐stamped renderings of sensor attributes and multivariate analyses. More specifically, algorithms converting sensor‐derived head and solute concentration values allow for automated monitoring of mass flux and discharge to evaluate groundwater remediation system performance and contaminant discharges from aquifers to surface‐water receptors. Life‐cycle costs and carbon footprints were reduced due to the elimination of energy and labor expenditures associated with transportation, data collection, laboratory efforts, report generation, and information dissemination. A brief summary of two demonstrations of this sensor‐based water resources management application is presented. © 2011 Wiley Periodicals, Inc.     

Improving the detection of fluorescent tracer dyes in groundwater investigations

Groundwater tracing with fluorescent tracer dyes is a valuable tool in many remediation projects. Three of four common dyes can be used concurrently, effectively separated, and their concentrations quantified if modern laboratory instruments and appropriate protocols are used. Unfortunately, investigators often overestimate the amount of introduced dye likely to be detected, use too little dye because of these estimates and concern that colored water might be detectable off‐site, and place sampling reliance solely on grab samples of water. The common result is flawed studies that identify only some of the points to which the dyed water flows. Results are quantitatively compared for monitoring sites during periods where both water samples and granular activated carbon samplers (referred to as carbon samplers) were used. The results demonstrate that carbon samplers are superior to water samples for detecting the presence of the fluorescent tracer dyes evaluated. A technically sound and cost‐effective strategy is to place primary sampling reliance on carbon samplers for detecting the presence of the dyes and secondary reliance on grab samples of water for determining dye concentrations when they are greater than the detection limits.     

Triad case study: Former small arms training range

The U.S. Army Corps of Engineers (US ACE) used the Triad approach to expedite site characterization of contaminated soil at the Former Small Arms Evergreen Infiltration Training Range in Fort Lewis, Washington. The characterization was designed to determine if surface soils contain significant concentrations of metals, with the focus on collecting sufficient data for determining appropriate future actions (i.e., risk analysis or soil remediation). A dynamic sampling and analytical strategy based on rapid field‐based analytical methods was created in order to streamline site activities and save resources while increasing confidence in remediation decisions. Concurrent analysis of soil samples during the demonstration of method applicability (DMA) used both field portable X‐ray fluorescence (FPXRF) and laboratory methodologies to establish a correlation between FPXRF and laboratory data. Immediately following the DMA, contaminated soil from the impact berm was delineated by collecting both FPXRF data and fixed laboratory confirmation samples. The combined data set provided analytical results that allowed for revisions to the conceptual site model for the range and directed additional sample collection activities to more clearly determine the extent and distribution of soil contamination. © 2004 Wiley Periodicals, Inc.     

Leaching standards for mineral recycling materials--a harmonized regulatory concept for the upcoming German Recycling Decree

In this contribution we give a first general overview of results of recent studies in Germany which focused on contaminant leaching from various materials and reactive solute transport in the unsaturated soil zone to identify the key factors for groundwater risk assessment. Based on these results we developed new and improved existing methods for groundwater risk assessment which are used to derive a new regulatory concept for the upcoming “Decree for the Requirements of the Use of Alternative Mineral Building Materials in Technical Constructions and for the Amendment of the Federal Soil Protection and Contaminated Sites Ordinance” of the German Federal Ministry of Environment.The new concept aims at a holistic and scientifically sound assessment of the use of mineral recycling materials (e.g., mineral waste, excavated soils, slag and ashes, recycling products, etc.) in technical constructions (e.g., road dams) and permanent applications (e.g., backfilling and landscaping) which is based on a mechanistic understanding of leaching and transport processes. Fundamental for risk assessment are leaching standards for the mineral recycling materials.For each application of mineral recycling materials specific maximum concentrations of a substance in the seepage water at the bottom of an application were calculated. Technical boundary conditions and policy conventions derived from the “German precautionary groundwater and soil protection policy” were accounted to prevent adverse environmental effects on the media soil and groundwater. This includes the concentration decline of highly soluble substances (e.g., chloride and sulphate), retardation or attenuation of solutes, accumulation of contaminants in sub-soils and the hydraulic properties of recycling materials used for specific applications. To decide whether the use of a mineral recycling material is possible in a specific application, the leaching qualities were evaluated based on column percolation tests with various samples and compared with application-specific maximum concentrations.In the upcoming federal decree this simplified concept is realized using detailed tables which classify the leaching quality of mineral recycling materials and demonstrate potential application. A quality assurance system will be mandatory which defines specific testing programs (material properties and limit concentrations to be tested, number and schedule of testing) for the different mineral recycling materials using standardized methods (column percolation test).     

Vapor Intrusion Monitoring Method Cost Comparisons: Automated Continuous Analytical Versus Discrete Time‐Integrated Passive Approaches

Vapor intrusion characterization efforts are challenging due to complexities associated with indoor background sources, preferential subsurface migration pathways, indoor and shallow subsurface concentration dynamics, and representativeness limitations associated with manual monitoring and characterization methods. For sites experiencing trichloroethylene (TCE) vapor intrusion, the potential for acute risks poses additional challenges, as the need for rapid response to acute toxicity threshold exceedances is critical in order to minimize health risks and associated liabilities. Currently accepted discrete time‐integrated vapor intrusion monitoring methods that employ passive diffusion–adsorption and canister samplers often do not result in sufficient temporal or spatial sampling resolution in dynamic settings, have a propensity to yield false negative and false positive results, and are not able to prevent receptors from acute exposure risks, as sample processing times exceed exposure durations of concern. Multiple lines of evidence have been advocated for in an attempt to reduce some of these uncertainties. However, implementation of multiple lines of evidence do not afford rapid response capabilities and typically rely on discrete time‐integrated sample collection methods prone to nonrepresentative results due to concentration dynamics. Recent technology innovations have resulted in the deployment of continuous monitoring platforms composed of multiplexed laboratory grade analytical components integrated with quality control features, telemetry, geographical information systems, and interpolation algorithms for automatically generating geospatial time stamped renderings and time‐weighted averages through a cloud‐based data management platform. Automated alerts and responses can be engaged within 1 minute of a threshold exceedance detection. Superior temporal and spatial resolution also results in optimized remediation design and mitigation system performance confirmation. While continuous monitoring has been acknowledged by the regulatory community as a viable option for providing superior results when addressing spatial and temporal dynamics, until very recently, these approaches have been considered impractical due to cost constraints and instrumentation limitations. Recent instrumentation advancements via automation and multiplexing allow for rapid and continuous assessment and response from multiple locations using a single instrument. These advancements have reduced costs to the point where they are now competitive with discrete time‐integrated methods. In order to gain more regulatory and industry support for these viable options, there is an immediate need to perform a realistic cost comparison between currently approved discrete time‐integrated methods and newly fielded continuous monitoring platforms. Regulatory support for continuous monitoring platforms will result in more effectively protecting the public, provide property owners with information sufficient to more accurately address potential liabilities, reduce unnecessary remediation costs for situations where risks are minimal, lead to more effective and surgical remediation strategies, and allow practitioners to most effectively evaluate remediation system performance. To address this need, a series of common monitoring scenarios and associated assumptions were derived and cost comparisons performed. Scenarios included variables such as number of monitoring locations, duration, costs to meet quality control requirements, and number of analyses performed within a given monitoring campaign. Results from this effort suggest that for relatively larger sites where five or more locations will be monitored (e.g., large buildings, multistructure industrial complexes, educational facilities, or shallow groundwater plumes with significant spatial footprints under residential neighborhoods), procurement of continuous monitoring services is often less expensive than implementation of discrete time‐integrated monitoring services. For instance, for a 1‐week monitoring campaign, costs‐per‐analysis for continuous monitoring ranges from approximately 1 to 3 percent of discrete time‐integrated method costs for the scenarios investigated. Over this same one‐week duration, for discrete time‐integrated options, the number of sample analyses equals the number of data collection points (which ranged from 5 to 30 for this effort). In contrast, the number of analyses per week for the continuous monitoring option equals 672, or four analyses per hour. This investigation also suggests that continuous automated monitoring can be cost‐effective for multiple one‐week campaigns on a quarterly or semi‐annual basis in lieu of discrete time‐integrated monitoring options. In addition to cost benefits, automated responses are embedded within the continuous monitoring service and, therefore, provide acute TCE risk‐preventative capabilities that are not possible using discrete time‐integrated passive sampling methods, as the discrete time‐integrated services include analytical efforts that require more time than the exposure duration of concern. ©2016 Wiley Periodicals, Inc.     

In‐Situ and Ex‐Situ Bioremediation Options for Treating Perchlorate in Groundwater

Perchlorate has been identified as a water contaminant in 14 states, including California, Nevada, New Mexico, Arizona, Utah, and Texas, and current estimates suggest that the compound may affect the drinking water of as many as 15 million people. Biological treatment represents the most‐favorable technology for the effective and economical removal of perchlorate from water. Biological fluidized bed reactors (FBRs) have been tested successfully at the pilot scale for perchlorate treatment at several sites, and two full‐scale FBR systems are currently treating perchlorate‐contaminated groundwater in California and Texas. A third full‐scale treatment system is scheduled for start‐up in early 2002. The in‐situ treatment of perchlorate through addition of specific electron donors to groundwater also appears to hold promise as a bioremediation technology. Recent studies suggest that perchlorate‐reducing bacteria are widely occurring in nature, including in groundwater aquifers, and that these organisms can be stimulated to degrade perchlorate to below the current analytical reporting limit (< 4 μg/l) in many instances. In this article, in‐situ and ex‐situ options for biological treatment of perchlorate‐contaminated groundwater are discussed and results from laboratory and field experiments are presented. © 2002 Wiley Periodicals, Inc.