Search

Published literature for reported sorption coefficients (K(d)) of eight anionic per- and polyfluoroalkyl substances (PFAS) in soil was reviewed. K(d) values spanned three to five log units indicating that no single value would be appropriate for use in estimating PFAS impacts to groundwater using existing soil-water partition equations. Regression analysis was used to determine if the soil or solution parameters might be used to predict K(d) values. None of the 15 experimental parameters collected could individually explain variability in reported K(d) values. Significant associations between K(d) and soil calcium and sodium content were found for many of the selected PFAS, suggesting that soil cation content may be critical to PFAS sorption, as previously noted in sources like Higgins and Luthy (2006), while organic carbon content was significant only at elevated levels (>5%). Unexplained discrepancies between the results from studies where PFAS were introduced to soil and desorbed in the laboratory and those that used material from PFAS-impacted sites suggest that laboratory experiments may be overlooking some aspects critical to PFAS sorption. Future studies would benefit from the development and use of standardized analytical methods to improve data quality and the establishment of soil parameters appropriate for collection to produce more complete data sets for predictive analysis.

Hexavalent chromium Cr(VI) is toxic and can be highly mobile in many aquifer systems. Redox reactions with naturally occurring minerals and organic compounds can reduce Cr(VI) to Cr(III), forming labile Cr(III) oxyhydroxide precipitates, which is a natural attenuation process. In fractured bedrock aquifers, reduction of Cr(VI) in the rock matrix can enhance attenuation beyond that from matrix diffusion only, and potentially reduce back diffusion if concentrations in fractures decline following source reduction via natural processes or engineered remediation. In this study, we develop an extraction method for labile Cr(III) precipitates from Cr(VI) reduction using 5% hydrogen peroxide (H 2 O 2 ). Combining Cr(III) extractions with an established sodium hydroxide (NaOH) method for determination of Cr(VI) concentrations in rock porewater, a measure of the labile Cr(III) and Cr(VI) fractions in geologic samples is achieved. The methods were applied to cores from a contaminated groundwater system in fractured porous bedrock in order to assess the effectiveness of natural attenuation and whether Cr(VI) mass that diffused into the bedrock matrix was undergoing reduction. Detailed vertical distributions display two depth intervals with corresponding elevated concentrations of Cr(VI) in the porewater and extractable total Cr. The correspondence of Cr(VI) and labile Cr(III) provides evidence for reduction of Cr(VI) contamination in the bedrock matrix. Mineralogical analysis suggests that Fe(II)-bearing minerals, chlorite and biotite are the most likely candidates for natural reductants. This study provides evidence for the natural attenuation of anthropogenic Cr(VI) contamination in the porewater of a fractured bedrock aquifer, and it outlines a quantitative method for evaluating the effectiveness of natural attenuation in groundwater systems.

This study uses a combination of conventional and high resolution field and laboratory methods to investigate processes causing attenuation of a hexavalent chromium (Cr(VI)) plume in sedimentary bedrock at a former industrial facility. Groundwater plume Cr(VI) concentrations decline by more than three orders of magnitude over a 900 m distance down gradient from the site. Internal plume concentrations generally exhibit stable to declining trends due to diffusive and reactive transport in the low permeability matrix as fluxes from the contamination source dissipate due to natural depletion processes and active remediation efforts. The strong attenuation is attributed to diffusion from mobile groundwater in fractures to immobile porewater in the rock matrix, and reactions causing transformation of aqueous Cr(VI) to low-solubility Cr(III) precipitates, confirmed by high spatial resolution rock matrix contaminant concentrations and comparisons with groundwater concentrations from multi-level sampling within the plume. Field characterization data for the fracture network and matrix properties were used to inform 2-D discrete-fracture matrix (DFM) numerical model simulations that quantify attenuation due to diffusion and reaction processes, which show consistency with field datasets, and provide insights regarding future plume conditions. The combination of field, laboratory and modeling evidence demonstrates effects of matrix diffusion and reaction processes causing strong attenuation of a Cr(VI) plume in a sedimentary bedrock aquifer. This approach has important implications for characterization of sites with Cr(VI) contamination for improved site conceptual models and remediation decision-making.

A new method for quantification of hexavalent chromium (Cr(VI)) in the porewater of rock core samples from contaminated sedimentary bedrock has been developed here. The method combines alkaline extraction with cation exchange column separation followed by determination of Cr concentrations by inductively coupled plasma mass spectrometry (ICP-MS). A porewater detection limit of 45 μg/L was determined by performing extractions on uncontaminated samples, and accounts for dilution of porewater volumes by the extraction solution. Recoveries of Cr(VI) in quality control (QC) samples were greater than 90% and there was no significant interference from Cr(III). Relative standard deviations (RSD) were less than 10% for QC samples spiked with Cr(VI), and 2 to 47% (average of 21%) for replicate analyses of core samples. Cr(VI) analyses were conducted on depth-discrete core samples collected at intervals of

Detailed 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.