Effects of initial solute distribution on contaminant availability, desorption modeling, and subsurface remediation

Low permeability regions in which solute movement is governed by diffusion reduce the availability of pollutants for remediation and can function as long-term sources of groundwater contamination. The inherent difficulty in understanding mass transfer from these regions of sequestered contamination is further complicated by unknown solute distributions within the low-permeability regions (sequestering regions). When models are calibrated to reproduce temporal histories of solute release from a sequestering region (desorption), the fitted parameter values are used to infer the physical or chemical characteristics of the media; however, the calibrated parameters also reflect the case-specific initial conditions (i.e., the solute distribution within the sequestering region domain at the onset of desorption). This phenomenon is demonstrated using model simulations of solute diffusion from hypothetical solids with characteristics similar to those of the well studied Borden, Ontario aquifer system. Solute release from the solids is simulated using a batch diffusion model under different initial solute distributions within the solids. The results of these model simulations are used to calibrate parameters of a multiple first-order rate desorption model (MRM) to illustrate how the fitted MRM parameters increase or decrease depending on the initial "aging" of the solids. Further numerical simulations are conducted for a one-dimensional flow system under steady-state and variable-rate hydraulic flushing. These simulations show that although aging reduces desorptive mass flux during early stages of flushing, aged sites have greater desorptive mass flux (greater solute availability) than "freshly" contaminated media during the later stages of remediation. Overall, the results demonstrate why the physicochemical meaning of observed desorption rates cannot be accurately deduced without first understanding the initial solute distribution within the media.     

Modeling and interpreting bioavailability of organic contaminant mixtures in subsurface environments

Bioavailability often controls the fate of organic contaminants in surface and subsurface aquatic environments. Bioavailability can be limited by sorption, mass transfer, and intrinsic biodegradation potential and can be further altered by the presence of other compounds. This paper reviews current perspectives on the processes influencing subsurface contaminant bioavailability, how these processes are modeled, and how the relative role of the various processes can be assessed through bioavailability indices. Although these processes are increasingly well understood, the use of sophisticated models and indices often are precluded by an inability to estimate the many parameters that are associated with complex models. Nonetheless, the proper representation of sorption, mass transfer, biodegradation, and co-solute effects can be critical in predicting bio-attenuation. The influence of these processes on contaminant fate is illustrated with numerical simulations for the simultaneous degradation of toluene (growth substrate) and trichloroethylene (nongrowth cometabolite) in hypothetical, aerobic, solid-water systems. The results show how the relative impacts on contaminant fate of the model's various component processes depends upon system conditions, including co-solute concentrations. Slow biodegradation rates increase the inhibition effects of a cometabolite and suppress the rate enhancement effects of a growth substrate. Irrespective of co-solute effects, contaminant fate is less sensitive to biodegradation processes in systems with strong sorption and slow desorption rates. Bioavailability indices can be used to relate these findings and to help identify appropriate modeling simplifications. In general, however, there remains a need to redefine such indices in order that bioavailability concepts can be better incorporated into site characterization, remediation design, and regulatory oversight.     

Variability of aquifer sorption properties in a field experiment on groundwater transport of organic solutes: Methods and preliminary results

Methods to characterize the organic solute sorption distribution coefficient, organic carbon content, and specific surface area of aquifer solids from the site of a field experiment on solute transport in groundwater were refined for application to small subsamples of 10-cm depth increments taken from 5-cm diameter cores. Initial results indicate that the average sorption characteristics of the Borden aquifer do not vary appreciably along the trajectory of the solute plumes. However, the sorption distribution coefficient of tetrachloroethylene varied over nearly an order of magnitude among 10-cm depth increments in one core sample. Preliminary evidence suggests that the sorption distribution coefficients for four halogenated organic solutes vary proportionally among core strata. However, the distribution coefficients for sorption of tetrachloroethylene on various depth increments are not well correlated with either organic carbon content or specific surface area, suggesting that as yet unidentified mineral phases may play a significant role in sorption of such solutes by the sandy aquifer solids.     

An assessment of lead absorption from soil affected by smelter emissions

The purpose of this study was to assess the oral bioavailability of lead in soil collected from a former smelter site in Sandy, Utah, USA. Sprague-Dawley rats (approximately 4 weeks of age, 5 of each sex in group) were given either soil lead or lead acetate mixed in a purified diet (AIN-93G ) at four different concentrations for 31 consecutive days. Food consumption measurements were used to compute mean daily lead exposures for the soil lead and lead acetate groups. The lead acetate treatment yielded higher concentrations of lead in the blood and bone than the soil lead treatment. Mean blood lead values ranged from below the detection limit (3 g dL^–1) to 27.25 g lead dL^–1 for the lead acetate groups at dose levels of 0.10–2.91 mg lead kg body weight^–1 and from below the detection limit to 8.8 g lead dL^–1 for the soil lead groups at doses of 0.11–3.43 mg lead kg body weight^–1. At these same doses, mean bone values ranged from 0.52 to 26.92 g lead g^–1 for the lead acetate groups and from 0.64 to 13.1 g lead g^–1 for the soil lead groups. Relative per cent bioavailability was estimated by modelling the dose-blood concentration curves for the lead acetate treatment and the dosed soil lead treatment, and then comparing doses that produce an equivalent blood lead concentration. The ratio of the doses of lead acetate and soil lead that produced the same tissue response (i.e., concentration) provided an index of relative bioavailability. For lead, the bioavailability of soil lead relative to lead acetate was 41% at a blood concentration of 6 g lead dL^–1.     

A framework of connections between soil and people can help improve sustainability of the food system and soil functions

Globally soil quality and food security continue to decrease indicating that agriculture and the food system need to adapt. Improving connection to the soil by knowledge exchange can help achieve this. We propose a framework of three types of connections that allow the targeting of appropriate messages to different groups of people. Direct connection by, for example, handling soil develops soil awareness for management that can be fostered by farmers joining groups on soil-focused farming such as organic farming or no-till. Indirect connections between soil, food and ecosystem services can inform food choices and environmental awareness in the public and can be promoted by, for example, gardening, education and art. Temporal connection revealed from past usage of soil helps to bring awareness to policy workers of the need for the long-term preservation of soil quality for environmental conservation. The understanding of indirect and temporal connections can be helped by comparing them with the operations of the networks of soil organisms and porosity that sustain soil fertility and soil functions.