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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 16–18 m 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. [ABSTRACT FROM AUTHOR]

A permeable reactive barrier, consisting of both zero valent iron (ZVI) and a biodegradable organic carbon, was evaluated for the remediation of 1,1,2-trichloroethane (1,1,2-TCA) contaminated groundwater. During an 888 day laboratory column study, degradation rates initially stabilized with a degradation half-life of 4.4 ± 0.4 days. Based on the accumulation of vinyl chloride (VC) and limited production of 1,1-dichloroethene (1,1-DCE) and 1,2-dichloroethane (1,2-DCA), the dominant degradation pathway was likely abiotic dichloroelimination to form VC. Degradation of VC was not observed based on the accumulation of VC and limited ethene production. After a step reduction in the influent concentration of 1,1,2-TCA from 170 ± 20 mg L − 1 to 39 ± 11 mg L − 1 , the degradation half-life decreased 5-fold to 0.83 ± 0.17 days. The isotopic enrichment factor of 1,1,2-TCA also changed after the step reduction from − 14.6 ± 0.7‰ to − 0.72 ± 0.12‰, suggesting a possible change in the degradation mechanism from abiotic reductive degradation to biodegradation. Microbiological data suggested a co-culture of Desulfitobacterium and Dehalococcoides was responsible for the biodegradation of 1,1,2-TCA to ethene. [ABSTRACT FROM AUTHOR]

A sustainable in-well vapor stripping system is designed as a cost-effective alternative for remediation of shallow chlorinated solvent groundwater plumes. A solar-powered air compressor is used to inject air bubbles into a monitoring well to strip volatile organic compounds from a liquid to vapor phase while simultaneously inducing groundwater circulation around the well screen. An analytical model of the remediation process is developed to estimate contaminant mass flow and removal rates. The model was calibrated based on a one-day pilot study conducted in an existing monitoring well at a former dry cleaning site. According to the model, induced groundwater circulation at the study site increased the contaminant mass flow rate into the well by approximately two orders of magnitude relative to ambient conditions. Modeled estimates for 5 h of pulsed air injection per day at the pilot study site indicated that the average effluent concentrations of dissolved tetrachloroethylene and trichloroethylene can be reduced by over 90% relative to the ambient concentrations. The results indicate that the system could be used cost-effectively as either a single- or multi-well point technology to substantially reduce the mass of dissolved chlorinated solvents in groundwater. [ABSTRACT FROM AUTHOR]

A detailed field-scale investigation of processes controlling the architecture, persistence and dissolution of a 20 to 45 year old trichloroethene (TCE) dense non-aqueous phase liquid (DNAPL) source zone located within a heterogeneous sand/gravel aquifer at a UK industrial site is presented. The source zone was partially enclosed by a 3-sided cell that allowed detailed longitudinal/fence transect monitoring along/across a controlled streamtube of flow induced by an extraction well positioned at the cell closed end. Integrated analysis of high-resolution DNAPL saturation ( S n ) (from cores), dissolved-phase plume concentration (from multilevel samplers), tracer test and permeability datasets was undertaken. DNAPL architecture was determined from soil concentration data using partitioning calculations. DNAPL threshold soil concentrations and low S n values calculated were sensitive to sorption assumptions. An outcome of this was the uncertainty in demarcation of secondary source zone diffused and sorbed mass that is distinct from trace amounts of low S n DNAPL mass. The majority of source mass occurred within discrete lenses or pools of DNAPL associated with low permeability geological units. High residual saturation ( S n > 10–20%) and pools ( S n > 20%) together accounted for almost 40% of the DNAPL mass, but only 3% of the sampled source volume. High-saturation DNAPL lenses/pools were supported by lower permeability layers, but with DNAPL still primarily present within slightly more permeable overlying units. These lenses/pools exhibited approximately linearly declining S n profiles with increasing elevation ascribed to preferential dissolution of the uppermost DNAPL. Bi-component partitioning calculations on soil samples confirmed that the dechlorination product cDCE (cis-dichloroethene) was accumulating in the TCE DNAPL. Estimated cDCE mole fractions in the DNAPL increased towards the DNAPL interface with the uppermost mole fraction of 0.04 comparable to literature laboratory data. DNAPL dissolution yielded heterogeneous dissolved-phase plumes of TCE and its dechlorination products that exhibited orders of magnitude local concentration variation. TCE solubility concentrations were relatively localised, but coincident with high saturation DNAPL lens source areas. Biotic dechlorination in the source zone area, however, caused cDCE to be the dominant dissolved-phase plume. The conservative tracer test usefully confirmed the continuity of a permeable gravel unit at depth through the source zone. Although this unit offered significant opportunity for DNAPL bypassing and decreased timeframes for dechlorination, it still transmitted a significant proportion of the contaminant flux. This was attributed to dissolution of DNAPL–mudstone aquitard associated sources at the base of the continuous gravel as well as contaminated groundwater from surrounding less permeable sand and gravel horizons draining into this permeable conduit. The cell extraction well provided an integrated metric of source zone dissolution yielding a mean concentration of around 45% TCE solubility (taking into account dechlorination) that was equivalent to a DNAPL mass removal rate of 0.4 tonnes per annum over a 16 m 2 cell cross sectional area of flow. This is a significant flux considering the source age and observed occurrence of much of the source mass within discrete lenses/pools. We advocate the need for further detailed field-scale studies on old DNAPL source zones that better resolve persistent pool/lens features and are of prolonged duration to assess the ageing of source zones. Such studies would further underpin the application of more surgical remediation technologies. [ABSTRACT FROM AUTHOR]

Abstract: The long-term impact of source-zone remediation efforts was assessed for a large site contaminated by trichloroethene. The impact of the remediation efforts (soil vapor extraction and in-situ chemical oxidation) was assessed through analysis of plume-scale contaminant mass discharge, which was measured using a high-resolution data set obtained from 23years of operation of a large pump-and-treat system. The initial contaminant mass discharge peaked at approximately 7kg/d, and then declined to approximately 2kg/d. This latter value was sustained for several years prior to the initiation of source-zone remediation efforts. The contaminant mass discharge in 2010, measured several years after completion of the two source-zone remediation actions, was approximately 0.2kg/d, which is ten times lower than the value prior to source-zone remediation. The time-continuous contaminant mass discharge data can be used to evaluate the impact of the source-zone remediation efforts on reducing the time required to operate the pump-and-treat system, and to estimate the cost savings associated with the decreased operational period. While significant reductions have been achieved, it is evident that the remediation efforts have not completely eliminated contaminant mass discharge and associated risk. Remaining contaminant mass contributing to the current mass discharge is hypothesized to comprise poorly accessible mass in the source zones, as well as aqueous (and sorbed) mass present in the extensive lower-permeability units located within and adjacent to the contaminant plume. The fate of these sources is an issue of critical import to the remediation of chlorinated-solvent contaminated sites, and development of methods to address these sources will be required to achieve successful long-term management of such sites and to ultimately transition them to closure. [Copyright &y& Elsevier]

Abstract: The effectiveness of permanganate for in situ chemical oxidation of organic liquid (trichloroethene) trapped in lower-permeability (K) zones located within a higher-permeability matrix was examined in a series of flow-cell experiments. The permanganate solution was applied in both continuous and pulsed-injection modes. Manganese-oxide precipitation, as confirmed by use of SEM-EDS, occurred within, adjacent to, and downgradient of the lower-K zones, reflective of trichloroethene oxidation. During flow interruptions, precipitate formed within the surrounding higher-permeability matrix, indicating diffusive flux of aqueous-phase trichloroethene from the lower-K zones. The impact of permanganate treatment on mass flux behavior was examined by conducting water floods after permanganate injection. The results were compared to those of water-flood control experiments. The amount of water flushing required for complete contaminant mass removal was reduced for all permanganate treatments for which complete removal was characterized. However, the nature of the mass-flux-reduction/mass-removal relationship observed during water flooding varied as a function of the specific permanganate treatment. [ABSTRACT FROM AUTHOR]

Abstract: An extensive site-characterization project was conducted at a large chlorinated-solvent contaminated Superfund site in Tucson, AZ. The project consisted of several components, including traditional site-characterization activities, tracer tests, laboratory experiments conducted with core material collected from the site, and mathematical modeling. The primary focus of the work presented herein is the analysis of induced-gradient contaminant elution tests conducted in a source zone at the site, investigation of the potential occurrence of immiscible liquid in the saturated zone, characterization of the relationship between mass flux reduction and mass removal, and evaluation of the impact of source-zone management on site remediation. The results of the present study, along with those of prior work, indicate that immiscible liquid is likely present in the saturated zone at the site source zones. Extensive tailing and rebound was observed for the contaminant-elution tests, indicating nonideal transport and mass-transfer behavior. The elution data were analyzed with a source-zone-scale mathematical model, and the results indicated that nonideal immiscible-liquid dissolution was the primary cause of the observed behavior. The time-continuous relationship between mass flux reduction and mass removal associated with the plume-scale pump-and-treat operation exhibited an initial large drop in mass flux with minimal mass removed, followed by a period of minimal mass flux reduction and a second period of large reduction. This behavior reflects the impact of both source-zone and aqueous-plume mass removal dynamics. Ultimately, a greater than 90% reduction in mass flux was achieved for a mass removal of approximately 50%. The influence of source-zone management on site remediation was evaluated by conducting two predictive simulations, one for which the source zones were controlled and one for which they were not. A plume-scale model was used to simulate the composite contaminant concentrations associated with groundwater extracted with the pump-and-treat system, which were compared to measured data. The information generated from this study was used to enhance the site conceptual model, help optimize operation of the pump-and-treat system, and evaluate the utility of source-zone remediation. [Copyright &y& Elsevier]