Isotherm ranking and selection using thirteen literature datasets involving hydrophobic organic compounds.

Numerous isotherm expressions have been developed for describing sorption of hydrophobic organic compounds (HOCs), including "dual-mode" approaches that combine nonlinear behavior with a linear partitioning component. Choosing among these alternative expressions for describing a given dataset is an important task that can significantly influence subsequent transport modeling and/or mechanistic interpretation. In this study, a series of numerical experiments were undertaken to identify "best-in-class" isotherms by refitting 10 alternative models to a suite of 13 previously published literature datasets. The corrected Akaike Information Criterion (AICc) was used for ranking these alternative fits and distinguishing between plausible and implausible isotherms for each dataset. The occurrence of multiple plausible isotherms was inversely correlated with dataset "richness", such that datasets with fewer observations and/or a narrow range of aqueous concentrations resulted in a greater number of plausible isotherms. Overall, only the Polanyi-partition dual-mode isotherm was classified as "plausible" across all 13 of the considered datasets, indicating substantial statistical support consistent with current advances in sorption theory. However, these findings are predicated on the use of the AICc measure as an unbiased ranking metric and the adoption of a subjective, but defensible, threshold for separating plausible and implausible isotherms.

Heterogeneous carbonaceous matter in sedimentary rock lithocomponents causes significant trichloroethylene (TCE) sorption in a low organic carbon content aquifer/aquitard system.

This study evaluated the effects of heterogeneous thermally altered carbonaceous matter (CM) on trichloroethylene (TCE) sorption for a low fraction organic carbon content (foc) alluvial sedimentary aquifer and aquitard system (foc=0.046-0.105%). The equilibrium TCE sorption isotherms were highly nonlinear with Freundlich exponents of 0.46-0.58. Kerogen+black carbon was the dominant CM fraction extracted from the sediments and accounted for >60% and 99% of the total in the sands and silt, respectively. Organic petrological examination determined that the kerogen included abundant amorphous organic matter (bituminite), likely of marine origin. The dark calcareous siltstone exhibited the greatest TCE sorption among aquifer lithocomponents and accounted for most sorption in the aquifer. The results suggest that the source of the thermally altered CM, which causes nonlinear sorption, was derived from parent Paleozoic marine carbonate rocks that outcrop throughout much of New York State. A synthetic aquifer-aquitard unit system (10% aquitard) was used to illustrate the effect of the observed nonlinear sorption on mass storage potential at equilibrium. The calculation showed that >80% of TCE mass contained in the aquifer was sorbed on the aquifer sediment at aqueous concentration <1000 µgL(-1). These results show that sorption is likely a significant contributor to the persistence of a TCE groundwater plume in the aquifer studied. It is implied that sorption may similarly contribute to TCE persistence in other glacial alluvial aquifers with similar geologic characteristics, i.e., comprised of sedimentary rock lithocomponents that contain thermally altered CM.

Distribution of carbonaceous matter in lithofacies: impacts on HOC sorption nonlinearity.

Both the composition and distribution of the lithocomponents within an aquifer impact hydrophobic organic compound (HOC) transport. Using samples from the sandy, low fraction organic carbon content (f(oc)~0.02%) Borden aquifer, we demonstrate how HOC sorption is controlled by the carbonaceous matter (CM) associated with calcareous sedimentary lithocomponents. Two-point isotherms using perchloroethene (PCE) as a sorbate showed that medium-grained lithofacies have a broader range of K(f) (Freundlich coefficient), 1/n (Freundlich parameter) and f(oc) than fine-grained facies. Dual-mode (linear+Freundlich) sorption modeling, fraction inorganic carbon (f(ic)) and laboratory analyses confirm that both the magnitude and variability of PCE K(d) (sorption distribution coefficient) in the Borden aquifer are controlled by the presence of heterogeneous CM in dark and very dark carbonate lithocomponents. Laboratory analyses and model results confirmed that the CM type controlling PCE sorption behavior in the Borden aquifer is in a condensed form, likely kerogen, contained within the carbonate matrix of the grains. The dark carbonate grains comprise a small proportion of the aquifer sediment (≪1%) and are found predominantly in medium-grained lithofacies in the Borden aquifer. These results show that increased heterogeneity, HOC mass storage and sorption nonlinearity associated with medium-grained lithofacies impact HOC transport in historically contaminated sedimentary aquifers.

Can chlorofluorocarbon sorption to black carbon (char) affect groundwater age determinations?

Although adsorption is not generally considered important in low f(oc) (fraction organic carbon) aquifers, we show that chlorofluorocarbon (CFC) adsorption to black carbon (BC) is sufficiently large to retard transport and affect groundwater ages obtained with CFCs. Sorption isotherms of CFC-11, -12, and -113 to synthetic wood char were nonlinear (Freundlich n = 0.71-0.94) while humic acid isotherms were linear. Moreover, sorption to char was 10-1000 times greater than to humic acid for all three CFCs at the lowest observed concentrations, C(w)/S approximately 10(-8)-10(-7). We used the observed isotherms for char and humic acid to represent sorption to BC and amorphous organic matter, respectively, in a dual mode model to estimate retardation factors for a low f(oc) aquifer (= 0.06% gC g(-1)). The estimated retardation factors for the char-containing aquifer (presumed BC fraction = 9% of f(oc)) were approximately 6.8-10.6 at C(w)/S = 10(-8) and >5 times those estimated assuming amorphous organic matter partitioning only. The results indicate that unless CFC adsorption to BC is evaluated in transport, the groundwater age determined may be biased toward older than true ages. The CFC data archived in BC-containing aquifers may contain information about its adsorbent properties that could be useful to predict retardation of other chlorinated organic contaminants.

Enhancing the ecological risk assessment process.

The Ecological Processes and Effects Committee of the US Environmental Protection Agency Science Advisory Board conducted a self-initiated study and convened a public workshop to characterize the state of the ecological risk assessment (ERA), with a view toward advancing the science and application of the process. That survey and analysis of ERA in decision making shows that such assessments have been most effective when clear management goals were included in the problem formulation; translated into information needs; and developed in collaboration with decision makers, assessors, scientists, and stakeholders. This process is best facilitated when risk managers, risk assessors, and stakeholders are engaged in an ongoing dialogue about problem formulation. Identification and acknowledgment of uncertainties that have the potential to profoundly affect the results and outcome of risk assessments also improves assessment effectiveness. Thus we suggest 1) through peer review of ERAs be conducted at the problem formulation stage and 2) the predictive power of risk-based decision making be expanded to reduce uncertainties through analytical and methodological approaches like life cycle analysis. Risk assessment and monitoring programs need better integration to reduce uncertainty and to evaluate risk management decision outcomes. Postdecision audit programs should be initiated to evaluate the environmental outcomes of risk-based decisions. In addition, a process should be developed to demonstrate how monitoring data can be used to reduce uncertainties. Ecological risk assessments should include the effects of chemical and nonchemical stressors at multiple levels of biological organization and spatial scale, and the extent and resolution of the pertinent scales and levels of organization should be explicitly considered during problem formulation. An approach to interpreting lines of evidence and weight of evidence is critically needed for complex assessments, and it would be useful to develop case studies and/or standards of practice for interpreting lines of evidence. In addition, tools for cumulative risk assessment should be developed because contaminants are often released into stressed environments.

Nitrate in tile drainage of the semiarid Palouse Basin.

Topographically heterogeneous agricultural landscapes can complicate and accelerate agrochemical contamination of streams due to rapid transport of water and chemicals to poorly drained lower-landscape positions and shallow ground water. In the semiarid Palouse region, large parts of these landscapes have been tile drained to enhance crop yield. From 2000-2004 we monitored the discharge of a tile drain (TD) and a nearby profile of soil water for nitrate concentration ([NO(3)]), electrical conductivity level (EC), and water content to develop a conceptual framework describing soil nitrate occurrence and loss via subsurface pathways. Tile-drain baseflow [NO(3)] was consistently 4 mg N L(-1) and baseflow EC was 200 to 300 microS cm(-1). Each year sudden synoptic increases in TD discharge and [NO(3)] occurred in early winter following approximately 150 mm of fall precipitation, which saturated the soil and mobilized high-[NO(3)] soil water throughout the profile. The greatest TD [NO(3)] (20-30 mg N L(-1)) occurred approximately contemporaneous with greatest TD discharges. The EC decrease each year (to approximately 100 microS cm(-1)) during high discharge, a dilution effect, lagged approximately 1 mo behind the first appearance of high [NO(3)] and was consistent with advective transport of low-EC water from the shallow profile under saturated conditions. Water-budget considerations and temporal [NO(3)] patterns suggest that these processes deliver water to the TD from both lower- and upper-slope positions, the latter via lateral flow during the high-flow season. Management practices that reduce the fall reservoir of soil nitrate might be effective in reducing N loading to streams and shallow ground water in this region.

Reactive oxygen species responsible for the enhanced desorption of dodecane in modified Fenton's systems.

The enhanced treatment of sorbed contaminants has been documented in modified Fenton's reactions; contaminants are desorbed and degraded more rapidly than they desorb by fill-and-draw or gas-purge desorption. The reactive species responsible for this process was investigated using dodecane as a model sorbent. Hydroxyl radical, hydroperoxide anion, and superoxide radical anion were generated separately to evaluate their roles in enhanced dodecane desorption. Dodecane desorption from silica sand over 180 minutes was negligible in gas-purge systems and in the hydroxyl radical and hydroperoxide anion systems. In contrast, enhanced desorption of dodecane occurred in superoxide systems, with >80% desorption over 180 minutes. Scavenging of superoxide eliminated the enhanced desorption of dodecane in both superoxide and modified Fenton's systems, confirming that superoxide is the desorbing agent in modified Fenton's reactions. Conditions that promote superoxide generation in Fenton's reactions may enhance their effectiveness for in situ subsurface remediation of sorbed hydrophobic contaminants.

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.

Bench-scale investigation of permanganate natural oxidant demand kinetics.

A vital design parameter for any in situ chemical oxidation system using permanganate (MnO4-) is the natural oxidant demand (NOD), a concept that represents the consumption of MnO4- by the naturally present reduced species in the aquifer solids. The data suggest that the NOD of the aquifer material from Canadian Forces Base Borden used in our study is controlled by a fast or instantaneous reaction captured by the column experiments, and a slower reaction as demonstrated by both column and batch test data. These two reaction rates may be the result of the reaction of MnO4- with at least two different reduced species exhibiting widely different rates of permanganate consumption (fast rate >7 g of MnO4- as KMnO4/kg/day and slow rate of approximately 0.005 g/kg/day), or a physically/chemically rate-limited single species. The slow NOD reaction prevented fulfillment of the ultimate NOD during the days- to months-long batch experiments and allowed significant early MnO4- breakthrough (>98%) during transport in the column experiments. A large fraction of the organic carbon resisted oxidation over the 21-week duration of the batch experiments. This result demonstrates that NOD estimated from total organic carbon measurements can significantly overpredict the NOD value required in the design of an in situ chemical oxidation application.

Effects of particulate carbonaceous matter on the bioavailability of benzo[a]pyrene and 2,2',5,5'-tetrachlorobiphenyl to the clam, Macoma balthica.

We investigated the bioavailability via diet of spiked benzo[a]pyrene (BaP) and 2,2',5,5'-tetrachlorobiphenyl (PCB-52) from different carbonaceous (non-carbonate, carbon containing) particle types to clams (Macoma balthica) collected from San Francisco Bay. Our results reveal significant differences in absorption efficiency between compounds and among carbonaceous particle types. Absorption efficiency for PCB-52 was always greater than that for BaP bound to a given particle type. Among particles, absorption efficiency was highest from wood and diatoms and lowest from activated carbon. Large differences in absorption efficiency could not be simply explained by comparatively small differences in the particles' total organic carbon content. BaP and PCB-52 bound to activated carbon exhibited less than 2% absorption efficiency and were up to 60 times less available to clams than the same contaminants associated with other types of carbonaceous matter. These results suggest that variations in the amount and type of sediment particulate carbonaceous matter, whether naturally occurring or added as an amendment, will have a strong influence on the bioavailability of hydrophobic organic contaminants. This has important implications for environmental risk assessment, sediment management, and development of novel remediation techniques.

A controlled field experiment on groundwater contamination by a multicomponent DNAPL: dissolved-plume retardation.

A natural gradient emplaced-source (ES) controlled field experiment was conducted at the Borden aquifer research site, Ontario, to study the transport of dissolved plumes emanating from residual dense nonaqueous-phase liquid (DNAPL) source zones. The specific objective of the work presented here is to determine the effects of solute and co-solute concentrations on sorption and retardation of dissolved chlorinated solvent-contaminant plumes. The ES field experiment comprised a controlled emplacement of a residual multicomponent DNAPL below the groundwater table and intensive monitoring of dissolved-phase plumes of trichloromethane (TCM), trichloroethylene (TCE), and perchloroethylene (PCE) plumes continuously generated in the aquifer down gradient from gradual source dissolution. Estimates of plume retardation (and dispersion) were obtained from 3-D numerical simulations that incorporated transient source input and flow regimes monitored during the test. PCE, the most retarded solute, surprisingly exhibited a retardation factor approximately 3 times lower than observed in a previous Borden tracer test by Mackay et al. [Water Resour. Res. 22 (1986) 2017] conducted approximately 150 m away. Also, an absence of temporal trend in PCE retardation contrasted with the previous Borden test. Supporting laboratory studies on ES site core indicated that sorption was nonlinear and competitive, i.e. reduced sorption of PCE was observed in the presence of TCE. Consideration of the effects of relatively high co-solute (TCE) concentration (competitive sorption) in addition to PCE concentration effects (nonlinear sorption) was necessary to yield laboratory-based PCE retardation estimates consistent with the field plume values. Concentration- and co-solute-based sorption and retardation analysis was also applied to the previous low-concentration pulse injection test of Mackay et al. [Water Resour. Res. 22 (1986) 2017] and was able to successfully predict the temporal field retardation trends observed in that test. While it is acknowledged that other "nonideal transport" effects may contribute, our analysis predicts differences in the PCE retardation magnitude and trend between the two experiments that are consistent with field observations based on the marked solute concentration differences that resulted from contrasting source conditions. Solute and co-solute concentration effects have heretofore received little attention, but may have wide significance in aquifers contaminated by point-source pollutants because many plumes contain mixed solutes over wide concentration ranges in strata that are likely subject to nonlinear sorption.