The low concentrations (ppm to ppb) typical of organic pollutants dissolved in groundwater have been a major factor limiting the application of stable isotope tracing techniques at contaminated field sites. In this study, pentane extraction of benzene, toluene, ethylbenzene, and the xylene isomers (BTEX) from water is shown to be an excellent means of resolving this problem and preparing low concentration samples for carbon isotope analysis using high sensitivity gas chromatograph/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Pentane extraction provides accurate, reproducible, and linear isotopic results for dissolved BTEX in water with concentrations ranging from 0.1 to 100 ppmsa range typically found in contaminated field settings. It is a rapid and flexible technique for extracting the monoaromatics from water and can readily be adapted to extract other organic contaminants. Demonstration of the feasibility of this technique for sparingly soluble BTEX compounds paves the way for applications of δ 13 C analysis of dissolved contaminants in both laboratory and field scenarios. GC/C/IRMS analysis of pure phase BTEX obtained from different manufacturers shows that the δ 13 C values of these compounds are resolvably different for each producer. These results suggest that isotope analysis may be a valuable tool for identification of contaminant origin in well-constrained field situations.

This paper describes some of the results from a field experiment at the Canadian Forces Base Borden, Ontario, Canada. Five liters of a chlorinated solvent mixture (2.0 L of trichloroethylene, 0.5 L of chloroform, and 2.5 L of tetrachloroethylene) was released into a sandy aquifer to create a heterogeneously distributed source. The dissolution and dissolved-phase plume development from this source were studied in detail along a crosssection downgradient of the source for a period of approximately 1 yr. At the conclusion of the experiment, the site was excavated to map the actual distribution of solvent residuals in the subsurface. Dissolved-phase concentrations exceeded 10% of the effective solubility of the individual components in the portion of the plume directly downgradient of the source, providing a strong indication of the presence of dense nonaqueous-phase liquids (DNAPLs). Dissolved-phase concentrations in several sampling points exceeded 50% of the effective solubility. However, even with detailed groundwater monitoring, it was not possible to determine the small-scale distribution of the DNAPL source. Lower dissolved concentrations occurred deeper than the DNAPL source zone, likely as a result of vertical groundwater flow caused by fluctuations in the water table elevation. Spatial delineation of the dissolvedphase plume downgradient of the source correlated generally to the lateral and vertical location of the DNAPL source. The distance between the DNAPL source and the downgradient sampling cross section could be determined from breakthrough curves for some of the sampling points but not for others because slow expansion of the DNAPL zone continued for some time during the dissolution experiment.

No abstract

Field-scale dissolution of a multicomponent DNAPL (dense nonaqueous-phase liquid) source intentionally emplaced below the water table is evaluated in a well-characterized natural aquifer setting. The block-shaped source contained 23 kg of a trichloromethane, trichloroethene, and perchloroethene mixture homogeneously distributed at 5% saturation of pore space. Dissolution was monitored for 3 yr via down-gradient samplers (1-m fence) and occasional intra-source sampling. Although intra-source equilibrium dissolution was shown and endorsed by supporting modeling and literature lab data, less than equilibrium concentrations were predominantly monitored in the 1-m fence. This was ascribed to significant by-passing of the source by groundwater flow due to its low permeability relative to the aquifer and associated dilution of concentrations emitted from the source. Heterogeneous source dissolution occurred despite the relative homogeneity of the source and aquifer and was ascribed to dissolution fingering, which has not been previously field-demonstrated. Bulk bypass of groundwater flow around the source zone caused slow dissolution rates, with 77% of the source remaining after 3 yr and a projected longevity of approximately 25 yr. Observed dissolution fingering would have significantly increased longevity as it increasingly caused intra-source bypass of remaining DNAPL. Our dissolution interpretations were endorsed by additional data collected after 6 yr during source remediation via permanganate oxidation.

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.

No abstract

A chlorinated solvent mixture (2.0 L of trichloroethylene, 0.5 L of chloroform, and 2.5 L of tetrachloroethylene) was released into a sandy aquifer to create a heterogeneously distributed DNAPL (dense nonaqueous-phase liquid) source. The dissolution and dissolved-phase plume development from this source were studied in detail along a cross-section downgradient of the source for a period of approximately 1 year. At the conclusion of the experiment, the site was excavated to map the actual distribution of solvent residuals in the subsurface. Multiple-component dissolution theory provides a tool for the estimation of the mass of a multiple-component DNAPL source present in the groundwater. Concentration ratios between the compounds change with time, and those changes can be used to estimate the mass of DNAPL upgradient of the monitoring point(s) or well(s). The method is independent of the dilution occurring in the groundwater and only requires observations of time series of the contaminants in one or more monitoring points. For the field experiment, the method was applied using the measured concentrations of individual sampling points, the depth-integrated concentrations, the area-integrated concentrations, and the effluent concentrations of the cell. The experiment showed that multiple-component dissolution theory may be a valuable tool for the estimation of the mass of multiplecomponent DNAPL residuals in the saturated zone.

In this study, we tested a practical strategy useful for accurate chlorinated volatile organic compound (cVOC) sorption prediction. Corresponding to the feature of the superposition of adsorption due to thermally altered carbonaceous matter (TACM) with organic carbon‐water partitioning, a nonlinear Freundlich sorption isotherm covering a wide range of aqueous concentrations was defined by equilibrium sorption measurement at one or a few low concentration points with extrapolation to the empirical organic carbon‐water partition coefficient (Koc,e) near compound solubility. We applied this approach to obtain perchloroethene equilibrium sorption isotherm parameters for TACM‐containing glacial sand and gravel subsoil samples from a field site in New York. Sorption and associated Koc,c applicable to low (5–500 µg/L) and high (>100,000 µg/L) aqueous concentrations were determined in batch experiments. (The Koc,c is the organic carbon‐normalized sorption partition coefficient corresponding to aqueous concentration Cw.) The Koc,c measurements at low concentration (~5 µg/L) were 6 to 34 times greater than the Koc,e. The importance of this type of data is illustrated through presentation of its substantial impact on the site remedy. In so doing, we provide an approach that is broadly applicable to cVOC field sites with similar circumstances (low carbon content glacial sand and gravel with TACM).