Chlorinated Solvent Contamination Research Articles

3D GeoRemediation: A Digital Hydrogeophysical–Chemical Clone and Virtual Hydraulic Barrier with Groundwater Circulation Wells (GCWs) for Groundwater Remediation

Identification of contamination sources and delineation of plumes in the geological environment stand as pivotal elements in reconstructing the conceptual site model (CSM) and devising remediation strategies tailored to specific physicochemical traits. This study endeavors to showcase the capabilities of a 3D digital interface, seamlessly integrating multi-source data, to elucidate site-specific contamination dynamics and steer the implementation of remediation strategies harmoniously aligned with the ethos of remediation geology. In a site historically marred by chlorinated solvent contamination, the digitization of stratigraphic, piezometric, chemical, and membrane interface probe (MIP) data underpins geomodeling endeavors and yields a meticulously crafted, data-driven CSM. The hydrogeochemical and hydrogeophysical data were interpolated to build a volumetric, digital 3D model illustrating data-driven elements. The comprehensive 3D clone adeptly delineates secondary contamination sources and renders visible the contamination plume within a georeferenced framework, mirroring the nuanced interplay of stratigraphic nuances and groundwater path. A data-centric approach to modeling facilitates the design of the first hydraulic virtual barrier leveraging groundwater circulation well (GCW) technology, its geometry finely attuned to intercept the contamination plume originating from source dissolution and aligning with preferential groundwater flow trajectories. Conventional hydrochemical monitoring and multilevel sampling substantiate the discernible reduction in chlorinated solvent concentrations across various depths within the aquifer horizon, affirming the efficacy of GCWs in their virtual barrier configuration. The findings highlight the effectiveness and limited groundwater consumption of the virtual barrier compared to the on-site pump-and-stock system. This research underscores the potency of a multi-faceted evidence-driven puzzle in conceptualizing contamination mechanisms within the geological milieu, thereby fostering the application of cutting-edge, effective, and sustainable remediation strategies.

Processes governing treatment of contaminants in low permeability zones

Herein we embrace the premise that aquifers are commonly composed of transmissive and low k (permeability) zones. Contaminants stored and subsequently released from low k zones sustain aqueous phase plumes for problematic periods. Processes governing the occurrence and treatment of contaminants in low k zones are advanced via conceptual models and a laboratory tank study. A two-dimensional sand tank with interbedded low k clay layers is flushed for 92 days with water spiked with 100 mg/L fluorescein, a proxy for chlorinated solvent contamination, and 67 mg/L bromide, a conservative tracer. Given active sources, fluorescein and bromide diffuses into the clay layers. Subsequently, the tank is flushed with water for 38 days. Water only flushing illustrates how the release of contaminants stored in low k zones sustains downgradient plumes. Next, an alkaline persulfate solution (40,000 mg/L persulfate at pH 11) is delivered to the tank for eight days. A fiber optic cable, placed on the glass wall of the sand tank, and a spectrometer with an ultraviolet light source are used to track depletion of fluorescein in transmissive sand and low k clay zones through time. Lastly, the tank is flushed with water only for 69 days to evaluate the efficacy of treatment with respect to mitigating releases from low k zones. Results indicate that flushing the tank with an alkaline persulfate solution, at a laboratory-scale, was effective in depleting fluorescein in both the transmissive and low k zones. Novelly, results capture concurrent transport of reactants and contaminants in domains governed by advection in transmissive zones and diffusion in low k zones.

Understanding contaminant transport in Chalk from petroleum hydrocarbon and chlorinated solvent contamination investigations

AbstractThe Chalk is a strategically important aquifer in the UK, but it is at risk of contamination, with impacts on abstractions, because of extensive outcrop. Assessments of the risk of contamination impacting water supply are commonly based on bulk aquifer parameters, usually reported for abstraction wells, and do not consider the macro- and micro-scale variation at the site and within the Chalk succession. The presence of less permeable layers is significant in restricting contaminant entry into the aquifer, pushing the contaminants into fractures and voids, where their flow is limited by density differences that cause hydrocarbons to smear into micro-fractures. Dense solvents flowing to depth are further impacted by the presence of lower permeability layers within the Chalk, while horizontal flow is affected by fractures and faults. Porewater concentrations of contaminants are limited, by pore throat size and limited connectivity, to low concentrations of the most soluble compounds, but are characterized by electron acceptors that are observed as reduced and oxidized species.The combination of macro- and micro-scale physical structures, combined with natural attenuation, means that initial risk assessments for hydrocarbons and solvents in Chalk can be highly conservative and should be supported by further targeted investigation.

Key factors controlling microbial distribution on a DNAPL source area

Chlorinated solvents are among the common groundwater contaminants that show high complexity in their distribution in the subsoil. Microorganisms play a vital role in the natural attenuation of chlorinated solvents. Thus far, how the in situ soil microbial community responds to chlorinated solvent contamination has remained unclear. In this study, the microbial community distribution within two boreholes located in the source area of perchloroethene (PCE) was investigated via terminal restriction fragment length polymorphism (T-RFLP) and clone library analysis. Microbial data were related to the lithological and geochemical data and the concentration and isotopic composition of chloroethenes to determine the key factors controlling the distribution of the microbial communities. The results indicated that Proteobacteria, Actinobacteria, and Firmicutes were the most abundant phylums in the sediment. The statistical correlation with the environmental data proved that fine granulometry, oxygen tolerance, terminal electron-acceptor processes, and toxicity control microbial structure. This study improves our understanding of how the microbial community in the subsoil responds to high concentrations of chlorinated solvents.

Electrokinetically-enhanced emplacement of lactate in a chlorinated solvent contaminated clay site to promote bioremediation

Bioremediation through the injection of electron donors and bacterial cultures is effective at treating chlorinated solvent contamination. However, it has had limited application in low permeability zones where amendments cannot be delivered successfully. This field-scale study investigated the application of electrokinetics to enhance the delivery of lactate at a clay site contaminated with chlorinated solvents. Groundwater and soil samples were collected before, during and for 1 year after the 71-day field test and analyzed for a wide suite of chemical and biological parameters. Lactate was successfully delivered to all monitoring locations. Lactate emplacement resulted in the stimulation of bacterial populations, specifically within the phylum Firmicutes, which contains fermenters and strict anaerobes. This likely led to biodegradation, as the field trial resulted in significant decreases in both soil and aqueous phase chlorinated solvent concentrations. Contaminant decreases were also partially attributable to dilution, given evidence of some advective lactate flux. This research provides evidence that electrokinetically-enhanced bioremediation has potential as a treatment strategy for contaminated low permeability strata.

Bioremediation Strategies Aimed at Stimulating Chlorinated Solvent Dehalogenation Can Lead to Microbially-Mediated Toluene Biogenesis.

In situ bioremediation practices that include subsurface addition of fermentable electron donors to stimulate reductive dechlorination by anaerobic bacteria have become widely employed to combat chlorinated solvent contamination in groundwater. At a contaminated site located near Baton Rouge, Louisiana (USA), toluene was transiently observed in groundwater at concentrations that sometimes far exceeded the US drinking water maximum contaminant level (MCL) of 1 mg/L after a fermentable substrate (agricultural feed grade cane molasses) was injected into the subsurface with the intent of providing electron donors for reductive dechlorination. Here, we present data that demonstrate that indigenous microorganisms can biologically produce toluene by converting phenylacetic acid, phenylalanine, phenyllactate, and phenylpyruvate to toluene. When grown in defined medium with phenylacetic acid at concentrations ≤350 mg/L, the molar ratio between toluene accumulated and phenylacetic acid supplied was highly correlated ( R2 ≥ 0.96) with a toluene yield exceeding 0.9:1. Experiments conducted using 13C labeled compounds (phenylacetic acid-2-13C and l-phenylalanine-3-13C) resulted in production of toluene-α-13C, confirming that toluene was synthesized from these precursors by two independently developed enrichment cultures. Results presented here suggest that monitoring of aromatic hydrocarbons is warranted during enhanced bioremediation activities where electron donors are introduced to stimulate anaerobic biotransformation of chlorinated solvents.

How to describe organic contamination in soils: A model comparison for chlorinated solvent concentrations at industrial site scale

The heavy-tailed distribution of the data of organic pollution in soils can raise specific problems in estimating and mapping the concentrations. Some high values often highly impact the sample variogram and extend the pollution hot-spots on the estimation maps.Non-linear geostatistical models, such as the anamorphosed Gaussian model, have been proposed in the 70's. They allow a consistent estimate of the concentrations and the probability that the concentrations exceed a cut-off. These well-founded methods are rarely used by environmental consultants, mainly because of time constraints and because the hypotheses of the models are not always satisfied.To estimate the concentrations, an empirical method widely used by environmental consultants consists of truncating the high values to gain robustness in the variogram analysis. The truncation value is arbitrary, even if it has a strong influence on the estimates of the concentrations. Proposed to handle heavy-tailed distributions of ore grades, the top-cut model (Rivoirard et al., 2013) justifies the use of truncated values but corrects the underestimation of the mean caused by truncation.In this model, the decomposition of the variable into three components (the truncated value, a weighted indicator at the top-cut threshold and a residual) makes the variographic study more robust and guides choosing the top-cut threshold.In the case of a chlorinated solvent contamination, a detailed comparison between several estimation methods is performed: ordinary kriging, kriging after truncation of the highest concentrations and estimation within the top-cut model, with structured or pure nugget residual. A sensitivity study to the top-cut threshold is realized. The results of two implementations of the cross-validation are compared.The top-cut model with nugget residual appears to be robust, even if the hypotheses of the model are not perfectly satisfied.

Characterization of chlorinated solvent contamination in limestone using innovative FLUTe® technologies in combination with other methods in a line of evidence approach

Characterization of dense non-aqueous phase liquid (DNAPL) source zones in limestone aquifers/bedrock is essential to develop accurate site-specific conceptual models and perform risk assessment. Here innovative field methods were combined to improve determination of source zone architecture, hydrogeology and contaminant distribution. The FACT™ is a new technology and it was applied and tested at a contaminated site with a limestone aquifer, together with a number of existing methods including wire-line coring with core subsampling, FLUTe® transmissivity profiling and multilevel water sampling. Laboratory sorption studies were combined with a model of contaminant uptake on the FACT™ for data interpretation. Limestone aquifers were found particularly difficult to sample with existing methods because of core loss, particularly from soft zones in contact with chert beds. Water FLUTe™ multilevel groundwater sampling (under two flow conditions) and FACT™ sampling and analysis combined with FLUTe® transmissivity profiling and modeling were used to provide a line of evidence for the presence of DNAPL, dissolved and sorbed phase contamination in the limestone fractures and matrix. The combined methods were able to provide detailed vertical profiles of DNAPL and contaminant distributions, water flows and fracture zones in the aquifer and are therefore a powerful tool for site investigation. For the limestone aquifer the results indicate horizontal spreading in the upper crushed zone, vertical migration through fractures in the bryozoan limestone down to about 16–18m depth with some horizontal migrations along horizontal fractures within the limestone. Documentation of the DNAPL source in the limestone aquifer was significantly improved by the use of FACT™ and Water FLUTe™ data.

Quantifying Global Impacts to Society from the Consumption of Natural Resources during Environmental Remediation Activities

SummaryEnvironmental remediation activities often require the management of large volumes of water and the consumption of significant amounts of local natural resources, including energy and fossil fuels. Traditionally, proposed remedial approaches for a specific cleanup scenario are evaluated by overall project implementation cost, time frame of the cleanup, and effectiveness to meet cleanup goals. A new paradigm shift, referred to as sustainable remediation, has influenced the remediation industry to consider environmental, social, and economic impacts from cleanup activities. An environmental footprint analysis is the most common method to evaluate environmental implications of cleanup approaches. Presently, these footprint tools do not associate the environmental implications with global impacts. In this article, the method has been extended to integrate the social cost of carbon emissions to quantify global impacts. The case study site is a former aircraft parts manufacturing facility that caused chlorinated solvent contamination in soil and groundwater beneath the building. A groundwater pump‐and‐treat system was initially installed, followed by its gradual phase‐out with concurrent phase in of in situ bioremediation. The case study evaluates the monetized societal benefits from quantifying carbon emission impacts of the proposed cleanup approaches and alternative scenarios. Our results suggest that societal impacts based on monetized carbon emissions can be reduced by 27% by optimizing the remediation processes. The sensitivity analysis results elucidate how variation in carbon prices and social discount rates can influence cleanup decisions for remediation projects.

Inferential monitoring of chlorinated solvents through Raman spectroscopic observation of the vibrational modes of water

Recent improvements in diode laser, fiber optic, and data acquisition technology have rejuvenated interest in field applications of Raman spectroscopy in a wide range of settings. One such application involves the observation of chlorinated solvents to facilitate the practice of "monitored natural attenuation." In this context, this manuscript focuses on means to improve the sensitivity of in-situ Raman analysis of chlorinated solvents. In particular, the work explores the performance limits of a Time-Resolved Raman Spectroscopy (TRRS) system employed to observe chlorinated solvents in aqueous samples via laboratory tests conducted on both liquid standards of trichloroethylene (TCE) and simulated biodegraded field samples. Quantitative assessment of TCE in solution is carried out through both direct observation of TCE Raman functional groups (381cm−1 (δ skeletal), 840cm−1 (νCCl) and 1242cm−1 (δCH)) and indirect observation of the broad OH stretching (2700–3800cm−1) Raman modes of water. Results from tests on simple solutions show that the TRRS system can detect TCE at aqueous concentrations as low as 70ppm by directly monitoring the 381cm−1 TCE line, whereas observation of the OH stretching line of water (3393cm−1) provides an indirect indication of TCE presence with nearly a 9× improvement in detection level. This unique and counterintuitive mechanism to detect the presence of chlorinated compounds in solution takes advantage of the influence of chlorine on the vibrational modes of water. This influence, which is believed to be attributed to the formation of hydrogen bonds and their resultant interactions with the solvation shell, may serve as a more sensitive and robust indication of the presence of aggregate chlorinated solvent contamination in aqueous systems. Tests performed on simulated biodegraded field samples demonstrate that the indirect detection mechanism is apparent even in complex samples representative of typical field conditions.

A study of chlorinated solvent contamination of the aquifers of an industrial area in central Italy: a possibility of bioremediation.

Perchloroethene, trichloroethene, and other chlorinated solvents are widespread groundwater pollutants. They form dense non-aqueous phase liquids that sink through permeable groundwater aquifers until non-permeable zone is reached. In Italy, there are many situations of serious contamination of groundwater that might compromise their use in industry, agriculture, private, as the critical case of a Central Italy valley located in the province of Teramo (“Val Vibrata”), characterized by a significant chlorinated solvents contamination. Data from the various monitoring campaigns that have taken place over time were collected, and new samplings were carried out, resulting in a complete database. The data matrix was processed with a multivariate statistic analysis (in particular principal component analysis, PCA) and was then imported into geographic information system (GIS), to obtain a model of the contamination. A microcosm anaerobic study was utilized to assess the potential for in situ natural or enhanced bioremediation. Most of the microcosms were positive for dechlorination, particularly those inoculated with a mineral medium. This indicate the presence of an active native dechlorinating population in the subsurface, probably inhibited by co-contaminants in the groundwater, or more likely by the absence or lack of nutritional factors. Among the tested electron donors (i.e., yeast extract, lactate, and butyrate) lactate and butyrate enhanced dechlorination of chlorinated compounds. PCA and GIS studies allowed delimiting the contamination; the microcosm study helped to identify the conditions to promote the bioremediation of the area.

Combined MODFLOW‐FRACTRAN Application to Assess Chlorinated Solvent Transport and Remediation in Fractured Sedimentary Rock

AbstractDetailed field investigations and numerical modeling were conducted to evaluate transport and fate of chlorinated solvent contamination in a fractured sedimentary bedrock aquifer (sandstone/siltstone/mudstone) at a Superfund site in central New Jersey. Field investigations provided information on the fractured rock system hydrogeology, including hydraulic gradients, bulk hydraulic conductivity, fracture network, and rock matrix, and on depth discrete contaminant distribution in fractures (via groundwater sampling) and matrix (via detailed subsampling of continuous cores). The numerical modeling endeavor involved application of both an equivalent porous media (EPM) model for flow and a discrete fracture network (DFN) model for transport. This combination of complementary models, informed by appropriate field data, allowed a quantitative representation of the conceptual site model (CSM) to assess relative importance of various processes, and to examine efficacy of remedial alternatives. Modeling progressed in two stages: first a large‐scale (20 km x 25 km domain) 3‐D EPM flow model (MODFLOW) was used to evaluate the bulk groundwater flow system and contaminant transport pathways under historic and current aquifer stress conditions and current stresses. Then, results of the flow model informed a 2‐D DFN transport model (FRACTRAN) to evaluate transport along a 1,000‐m flowpath from the source represented as a 2‐D vertical cross‐section. The combined model results were used to interpret and estimate the current and potential future extent of rock matrix and aqueous‐phase contaminant conditions and evaluate remedial strategies. Results of this study show strong effects of matrix diffusion and other processes on attenuating the plume such that future impacts on downgradient well fields under the hydraulic stresses modeled should be negligible. Results also showed futility of source remediation efforts in the fractured rock, and supported a technical impracticability (TI) waiver for the site. © 2013 Wiley Periodicals, Inc.

A Revised Conceptual Model to Reproduce the Distribution of Chlorinated Solvents in the Rho Aquifer (Italy)

AbstractTo make cost‐effective decisions regarding aquifer protection against chlorinated solvent contamination, a conceptual site model explaining the hydrodynamic behavior of these solvents needs to account for soil heterogeneities in sufficient detail. Among the key requirements, it is necessary to perform site‐specific characterization of (1) the architecture and type of chlorinated solvent sources, (2) the architecture, nature, and distribution of aquitards (bodies of low permeability), and (3) local groundwater dynamics. Local‐scale data are often lacking and regional descriptions are therefore adopted with the consequence of losing small‐scale features that control local chlorinated solvent migration which, in turn, limits the effectiveness of safeguard facilities. This article addresses these arguments, focusing on the Rho aquifer (Italy). We show that the local conceptual model must integrate small‐scale architectural and hydrodynamic anomalies of the aquifers and aquitards with regional trends and the sedimentary origin of the aquifers. New evidence was found by processing stratigraphic logs, piezometric heads and solute concentrations from local wells. The revised conceptual model should account for the occurrence of secondary chlorinated solvent sources located in depressions on the aquitard surface separating the two upper and most contaminated Rho aquifers. While the spatial distribution of depressions is in accordance with regional sedimentological dynamics, the direction of local groundwater flow at various levels within the main hydrogeological unit is remarkably opposite to the regional groundwater flow direction. These findings, along with evidence of vertical heterogeneous soil texture and stratification of chlorinated solvents in various phases, are supported by a simple particle‐tracking model and suggest how to redefine the conceptual model and, consequently, how to design safeguard facilities to effectively prevent further plume migration.

Online methodology for determining compound‐specific hydrogen stable isotope ratios of trichloroethene and 1,2‐cis‐dichloroethene by continuous‐flow isotope ratio mass spectrometry

Carbon and chlorine compound-specific isotope analysis (CSIA) is utilized in chlorinated solvent contamination studies of soil and groundwater contaminated sites. However, in field studies, hydrogen CSIA has been used only in non-chlorinated volatile organic compound (VOC) investigations, due to low conversion yields into hydrogen gas and poor reproducibility. Therefore, it is important to develop hydrogen CSIA methodology for soil and subsurface contamination studies. A new analytical method for determining compound-specific hydrogen stable isotope ratios is presented. The isotopic ratios were measured by gas chromatography/isotope ratio mass spectrometry (GC/IRMS) coupled with a chromium reduction system. The method was used to determine the δ(2) H values of trichloroethene (TCE) and 1,2-cis-dichloroethene (cis-DCE). The accuracy of the method was verified by conducting comparison measurements of standards by the conventional offline technique and the new method. The precision of the new analytical method (better than ±7 ‰) is better than that obtained from the offline method. The quantification limits of the headspace-solid-phase microextraction (SPME) are 400 µg/L and 200 µg/L for TCE and cis-DCE, respectively. The quantification limits can be improved by adopting a more efficient pre-concentration system such as purge-and-trap or thermal adsorption. This analytical method will facilitate the use of hydrogen CSIA on chlorinated solvents, which can be beneficial in multi-isotope approaches (coupling δ(2)H values with δ(13)C and/or δ(37)Cl values) in field site investigations where source identifications and contaminant behaviours are questioned.

Diversity of reductive dehalogenase genes from environmental samples and enrichment cultures identified with degenerate primer PCR screens

Reductive dehalogenases are the critical enzymes for anaerobic organohalide respiration, a microbial metabolic process that has been harnessed for bioremediation efforts to resolve chlorinated solvent contamination in groundwater and is implicated in the global halogen cycle. Reductive dehalogenase sequence diversity is informative for the dechlorination potential of the site or enrichment culture. A suite of degenerate PCR primers targeting a comprehensive curated set of reductive dehalogenase genes was designed and applied to 12 DNA samples extracted from contaminated and pristine sites, as well as six enrichment cultures capable of reducing chlorinated compounds to non-toxic end-products. The amplified gene products from four environmental sites and two enrichment cultures were sequenced using Illumina HiSeq, and the reductive dehalogenase complement of each sample determined. The results indicate that the diversity of the reductive dehalogenase gene family is much deeper than is currently accounted for: one-third of the translated proteins have less than 70% pairwise amino acid identity to database sequences. Approximately 60% of the sequenced reductive dehalogenase genes were broadly distributed, being identified in four or more samples, and often in previously sequenced genomes as well. In contrast, 17% of the sequenced reductive dehalogenases were unique, present in only a single sample and bearing less than 90% pairwise amino acid identity to any previously identified proteins. Many of the broadly distributed reductive dehalogenases are uncharacterized in terms of their substrate specificity, making these intriguing targets for further biochemical experimentation. Finally, comparison of samples from a contaminated site and an enrichment culture derived from the same site 8 years prior allowed examination of the effect of the enrichment process.

The legacy of chlorinated solvents in the Birmingham aquifer, UK: Observations spanning three decades and the challenge of future urban groundwater development

Licensed abstraction well data collected during 1986–2008 from a total of 77 wells mainly located at industrial sites combined with historic land use data from 1975 has allowed insight into the legacy of chlorinated solvent contamination in the Birmingham aquifer that underlies the UK's second largest city. This legacy, expected to be reasonably symptomatic of those occurring in other urban aquifers, was characterised by: dominance of parent solvents, particularly TCE (trichloroethene) that widely exceeded drinking-water quality criteria; greater TCE occurrence in wells in proximity to increased historic land use by the metal/engineering solvent-user industry (the relationship providing a first-pass indicator of future resource development potential); regional groundwater vulnerability controls; well abstraction changes (over months to decades) influential of observed concentration transients and anticipated plume capture or release; persistence of contamination over decades (with less soluble PCE (perchloroethene) showing increased persistence relative to TCE) that was reasonably ascribed to slow contaminant release from DNAPL (dense non-aqueous phase liquid) sources and, or low permeability layers; presence of dechlorination products arising from solvent (bio)degradation, although this key attenuation process appeared to have moderate to weak influence regionally on plumes; and, inadvertent, but significant solvent mass removal from the aquifer by industrial abstractions. Key challenges to realising future urban groundwater development were identified based on the observed legacy and well capture zone simulations. Despite the extensive contamination of the aquifer, it should still be possible to develop wells of high (several megalitres per day) capacity for drinking water supply (or other lower grade uses) without the requirement for solvent treatment. In those areas with higher risk of contamination, our dataset, together with application of emergent risk assessment approaches (that our dataset may serve to validate), could be used to inform potential abstractors as to whether solvent treatment is likely to be required at a particular abstraction site with time. Challenges identified that were relevant to the future development of Birmingham and urban aquifers more generally include the adequacy of groundwater quality monitoring data and uncertainties in contaminant source terms, abstraction well capture zone predictions and plume natural attenuation, in particular degradation rates. The study endorses that despite significant solvent contamination encountered, strategies can, and need, to be increasingly found to reclaim urban aquifer resources and more sustainably meet urban water demands.

Co‐occurrence of 1,4‐dioxane with trichloroethylene in chlorinated solvent groundwater plumes at US Air Force installations: Fact or fiction

Increasing regulatory attention to 1,4-dioxane has prompted the United States Air Force (USAF) to evaluate potential environmental liabilities, primarily associated with legacy contamination, at an enterprise scale. Although accurately quantifying environmental liability is operationally difficult given limited historic environmental monitoring data, 1,4-dioxane is a known constituent (i.e., stabilizer) of chlorinated solvents, in particular 1,1,1-trichloroethane (TCA). Evidence regarding the co-occurrence of 1,4-dioxane and trichloroethylene (TCE), however, has been heavily debated. In fact, the prevailing opinion is that 1,4-dioxane was not a constituent of past TCE formulations and, therefore, these 2 contaminants would not likely co-occur in the same groundwater plume. Because historic handling, storage, and disposal practices of chlorinated solvents have resulted in widespread groundwater contamination at USAF installations, significant potential exists for unidentified 1,4-dioxane contamination. Therefore, the objective of this investigation is to determine the extent to which 1,4-dioxane co-occurs with TCE compared to TCA, and if these chemicals are co-contaminants, whether or not there is significant correlation using available monitoring data. To accomplish these objectives, the USAF Environmental Restoration Program Information Management System (ERPIMS) was queried for all relevant records for groundwater monitoring wells (GMWs) with 1,4-dioxane, TCA, and TCE, on which both categorical and quantitative analyses were carried out. Overall, ERPIMS contained 5788 GMWs from 49 installations with records for 1,4-dioxane, TCE, and TCA analytes. 1,4-Dioxane was observed in 17.4% of the GMWs with detections for TCE and/or TCA, which accounted for 93.7% of all 1,4-dioxane detections, verifying that 1,4-dioxane is seldom found independent of chlorinated solvent contamination. Surprisingly, 64.4% of all 1,4-dioxane detections were associated with TCE independently. Given the extensive data set, these results conclusively demonstrate for the first time that 1,4-dioxane is a relatively common groundwater co-contaminant with TCE. Trend analysis demonstrated a positive log-linear relationship where median 1,4-dioxane levels increased between approximately 6% and approximately 20% of the increase in TCE levels. In conclusion, this data mining exercise suggests that 1,4-dioxane has a probability of co-occurrence of approximately 17% with either TCE and/or TCA. Given the challenges imposed by remediation of 1,4-dioxane and the pending promulgation of a federal regulatory standard, environmental project managers should use the information presented in this article for prioritization of future characterization efforts to respond to the emerging issue. Importantly, site investigations should consider 1,4-dioxane a potential co-contaminant of TCE in groundwater plumes.

A Comparison Between Field Applications of Nano-, Micro-, and Millimetric Zero-Valent Iron for the Remediation of Contaminated Aquifers

In the last 10 years, the number of field applications of zero-valent iron differing from permeable reactive barrier has grown rapidly and at present are 112. This study analyzes and compares such field applications. By using statistical analysis, especially ANOVA and principal component analysis, this study shows that chlorinated solvent contamination can be treated efficiently by using zero-valent iron material singly or associated with other technologies. In the analyzed sample of case studies, the association with microbial dechlorination increased significantly the performances of nanoscale iron. This is likely due to the synergistic effect between the two processes. Millimetric iron was always used in association with source zone containment; therefore, it is not possible to distinguish the contributions of the two techniques. The comparison also shows that catalyst addition seems to not dramatically improve treatment efficiency and that such improvement is not statistically significant. Finally, the injection technology is correlated to the type of iron and to the soil permeability.

Evaluation of air permeability in layered unsaturated materials

Field estimation of air permeability is important in the design and operation of soil-vapor extraction systems. Previous models have examined airflow in homogenous soils, incorporating leakage through a low-permeability cap either as a correction to the airflow equation or as a boundary condition. The dual leakage model solution developed here improves upon the previous efforts by adding a leaky lower boundary condition, allowing for the examination of airflow in heterogeneous layered soils. The dual leakage model is applied to the evaluation of pump tests at a pilot soil-vapor extraction system at the Savannah River Site in South Carolina. A thick, low-permeability, stiff clay layer divides the stratigraphy at the site into two units for evaluation. A modified version of the previous model, using the water table as the impermeable lower boundary, is used to evaluate the permeability of the low-permeability stiff clay layer (3.2 × 10 − 10 cm 2) and permeable sand (7.2 × 10 − 7 cm 2) beneath it. The stiff clay permeability estimate is used in the evaluation of the shallow unit. Permeability estimates of the shallow sand (3.8 × 10 − 7 cm 2) and kaolin cap (1.5 × 10 − 9 cm 2) were obtained with the dual leakage model. The shallow unit was evaluated using the previous model for comparison. The effects of anisotropy were investigated with a series of model simulations based on the shallow unit solution. The anisotropy sensitivity analysis suggests that increased anisotropy ratio or decreased axial permeability has a significant impact on the velocity profile at the lower boundary, especially at high values of the anisotropy ratio. This result may increase estimates of SVE removal rates for contaminants located at the interface of the lower boundary, typical of chlorinated solvent contamination.

Pump-and-Treat Remediation of Chlorinated Solvent Contamination at a Controlled Field-Experiment Site

Pump-and-treat (P&T) remediation and associated concentration tailing are investigated at the field scale in a mildly heterogeneous sandy aquifer through the extraction of dissolved chlorinated solvent plumes that had developed over 475 d from a multicomponent dense nonaqueous-phase liquid (DNAPL) source intentionally emplaced in the aquifer at the Borden (ON) research site. Extraction was accomplished via a source-containment well located 25 m from the source and two further downgradient plume-centerline wells to remove the advancing high-concentration dissolved plumes. The 550 days of detailed P&T field data demonstrated the following: remediation, albeit slowly, of the leading 25-60 m plume section to around typical drinking water standard concentrations; concentration tailing (reduction) over 4 orders of magnitude in the plume; a steady-state concentration "plateau" in the source-containment well capturing the steadily dissolving DNAPL source; influences of extraction rate changes (concentration rebounds); and, lengthy tailing from inter-well stagnation-zone areas. Much of the contaminant behavior during the P&T appeared to be "ideal" in the sense that with appropriate specification of the source term and pumping regime, it was reasonably predicted by 3-dimensional numerical model (HydroGeoSphere) simulations that assumed ideal (macrodispersion, linear sorption, etc.) transport. Supporting lab studies confirmed nonideal sorption was, however, important at the point sample scale with enhanced PCE (tetrachloroethene) sorption to low- and high-permeability strata and moderate nonlinear and competitive sorption influences. Although there was limited evidence of nonideal tailing contributions to the field data (underprediction of some tailing curve gradients), such contributions to P&T tailing were not easily discerned and appeared to play a relatively minor role within the mildly heterogeneous aquifer studied.