Development of a Dynamic Pharmacokinetic Model to Estimate Bioconcentration of Xenobiotics in Earthworms

A simple and dynamic pharmacokinetic model was developed to predict bioconcentration of organic contaminants in earthworms. The model was parameterized experimentally by placing Lumbricus terrestris in soil contaminated with 200 μg/cm² of malathion. The toxicokinetics of malathion uptake, depuration, and degradation in soil is measured. After parameterization, the model was able to accurately predict the bioconcentration factor of malathion at steady state. Sensitivity analyses were performed and the rate of absorption was determined to be the most sensitive parameter. Varying the rate of malathion elimination from earthworm tissues, malathion degradation, and the amount of malathion applied to the soil by 25-fold did not result in the bioconcentration of malathion. An increase in the rate of malathion absorption into earthworm tissues by 25-fold did result in bioconcentration. Previously published pharmacokinetic studies on xenobiotics with log K _ow values ranging up to 8.05 were used to test the predictive capacity of the model. The model was able to predict from 83% to 105% of the experimentally derived bioconcentration factors.     

Metolachlor dechlorination by zerovalent iron during unsaturated transport

Permeable zerovalent iron (Fe0) barriers have become an established technology for remediating contaminated ground water. This same technology may be applicable for treating pesticides amenable to dehalogenation as they move downward in the vadose zone. By conducting miscible displacement experiments in the laboratory with metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide; a chloroacetanilide herbicide] under unsaturated flow, we provide proof-of-concept for such an approach. Transport experiments were conducted in repacked, unsaturated soil columns attached to vacuum chambers and run under constant matrix potential (-30 kPa) and Darcy flux (approximately 2 cm d(-1)). Treatments included soil columns equipped with and without a permeable reactive barrier (PRB) consisting of a Fe0-sand (50:50) mixture supplemented with Al2(SO4)3. A continuous pulse of 14C-labeled metolachlor (1.45 mM) and tritiated water (3H2O) was applied to top of the columns for 10 d. Results indicated complete (100%) metolachlor destruction, with the dehalogenated product observed as the primary degradate in the leachate. Similar results were obtained with a 25:75 Fe0-sand barrier but metolachlor destruction was not as efficient when unannealed iron was used or Al2(SO4)3 was omitted from the barrier. A second set of transport experiments used metolachlor-contaminated soil in lieu of a 14C-metolachlor pulse. Under these conditions, the iron barrier decreased metolachlor concentration in the leachate by approximately 50%. These results provide initial evidence that permeable iron barriers can effectively reduce metolachlor leaching under unsaturated flow.     

Field-scale remediation of a metolachlor-contaminated spill site using zerovalent iron

Pesticide spills are common occurrences at agricultural cooperatives and farmsteads. When inadvertent spills occur, chemicals normally beneficial can become point sources of ground and surface water contamination. We report results from a field trial where approximately 765 m3 of soil from a metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] spill site was treated with zerovalent iron (Fe0). Preliminary laboratory experiments confirmed metolachlor dechlorination by Fe0 in aqueous solution and that this process could be accelerated by adding appropriate proportions of Al2(SO4)3 or acetic acid (CH3COOH). The field project was initiated by moving the stockpiled, contaminated soil into windrows using common earth-moving equipment. The soil was then mixed with water (0.35-0.40 kg H2O kg(-1)) and various combinations of 5% Fe0 (w/w),2% Al2(SO4)3 (w/w), and 0.5% acetic acid (v/w). Windrows were covered with clear plastic and incubated without additional mixing for 90 d. Approximately every 14 d, the plastic sheeting was removed for soil sampling and the surface of the windrows rewetted. Metolachlor concentrations were significantly reduced and varied among treatments. The addition of Fe0 alone decreased metolachlor concentration from 1789 to 504 mg kg(-1) within 90 d, whereas adding Fe0 with Al2(SO4)3 and CH3COOH decreased the concentration from 1402 to 13 mg kg(-1). These results provide evidence that zerovalent iron can be used for on-site, field-scale treatment of pesticide-contaminated soil.     

Bioremediation of 3,4-dichloroaniline and 2,4,6-trinitrotoluene in soil in the presence of natural adsorbents

The use of some adsorbents may decrease the toxicity of organic pollutants to microbes and plants during soil bioremediation. Experiments were conducted with 3,4-dichloroaniline (DCA) and 2,4,6-trinitrotoluene (TNT). Here we demonstrate that activated carbon can reduce the toxicity of readily available chemicals in soil by transferring them to a less available fraction. This process results in accelerated biodegradation of dichloroaniline by the inoculated Paracoccus denitrificans st. 3XA. In the case of TNT, activated carbon promotes strong binding through accelerated microbial reduction of its nitro-groups and catalytic chemical oxidation of the methyl-group and polymerisation or binding of the products formed.     

Mobility of aniline, benzoic acid, and toluene in four soils and correlation with soil properties

Soil properties and retention mechanisms affecting the relative mobility of aniline, benzoic acid, and toluene in Cecil sandy loam (clayey, kaolinitic, thermic Typic Hapludults), Holdredge silt loam (fine-silty, mixed, mesic Typic Argiustolls), Sharpsburg silty clay loam (fine, montmorillonitic, mesic Typic Argiudolls), and Valentine fine sand (mixed, mesic Typic Ustipsamments) were delineated in laboratory studies. The effect of the synthetic organic compounds (SOCs) was also determined on effective organic campounds (SOCs) was also determined on effective cation exchange capacity (ECEC) of the soils. Benzoic acid was most mobile of the SOCs but was retained in the Cecil soil by hydrogen bonds to Fe oxides. Toluene was least mobile and probably was hydrophobically sorbed to all soils. Aniline was electrostatically retained in protonated form to organic and inorganic exchange sites of the soils and reduced the ECEC of aniline-treated Holdredge and Sharpsburg soils.     

Relationship between land use classification and grass shrimp Palaemonetes spp. population metrics in coastal watersheds

Estuaries in the southeastern USA have experienced increased loading of contaminants from nonpoint source runoff as well as changes in habitat (e.g., loss of wetlands) due to urbanization. These changes may pose significant risks to estuarine fauna, including crustaceans. Several studies have shown relationships between land use classification and levels of stress in estuarine populations. The grass shrimp of the genus Palaemonetes is one of the dominant species found in estuarine tidal creeks, accounting for more than 50 % of all macropelagic fauna. Grass shrimp populations were sampled monthly for 3 years at six estuarine creeks on Kiawah Island, SC. Creek watersheds were estimated using National Aerial Photograph Program color infrared and low-altitude true color aerial photography combined with in situ differentially corrected global positioning system mapping of engineered features. Land classifications delineated included water, marsh, buildings, roads, and lawns. Pairwise comparisons for grass shrimp densities among sites showed significant differences on an annual and seasonal basis. Significant relationships (p?<?0.05) between land class variables and grass shrimp density were identified both annually and seasonally. These findings suggest an influence of land use on Palaemonetes spp. populations.     

Removal of TNT and RDX from water and soil using iron metal

Contaminated water and soil at active or abandoned munitions plants is a serious problem since these compounds pose risks to human health and can be toxic to aquatic and terrestrial life. Our objective was to determine if zero-valent iron (Fe(0)) could be used to promote remediation of water and soil contaminated with 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). As little as 1% Fe(0) (w/v) removed 70 mg TNT litre(-1) from aqueous solution within 8 h and removed 32 mg RDX litre(-1) within 96 h. Treating slurries (1:5 soil:water) of highly contaminated soil (5200 mg TNT and 6400 mg RDX kg(-1) soil) from the former Nebraska Ordnance Plant (NOP) with 10% Fe(0) (w/w soil) reduced CH(3)CN-extractable TNT and RDX concentrations below USEPA remediation goals (17.2 mg TNT and 5.8 mg RDX kg(-1)). Sequential treatment of a TNT-contaminated solution (70 mg TNT litre(-1) spiked with (14)C-TNT) with Fe(0) (5% w/v) followed by H(2)O(2) (1% v/v) completely destroyed TNT and removed about 94% of the (14)C from solution, 48% of which was mineralized to (14)CO(2) within 8 h. Fe(0)-treated TNT also was more susceptible to biological mineralization. Our observations indicate that Fe(0) alone, Fe(0) followed by H(2)O(2), or Fe(0) in combination with biotic treatment can be used for effective remediation of munitions-contaminated water and soil.     

Quantification of ontogenetic discontinuities in three species of oegopsid squids using model II piecewise linear regression

Growth trajectories of morphological characters may change during ontogeny, but this change is often overlooked or, at best, is estimated visually. An objective method was developed for determining discontinuities in morphological measurements of three species of oceanic squids: Chtenopteryx sicula (Vérany, 1851), Mastigoteuthis magna Joubin, 1913, and Brachioteuthis sp. 3. The specimens were collected on the Amsterdam Mid North Atlantic Plankton Expeditions (1980-1983) along a transect from 55°N to 25°N along 30°W. Discontinuities were quantified via an iterative, model II, piecewise linear regression (PLR) analysis, whereby the regression model incorporated a fixed breakpoint that was increased in each iteration across the range of dorsal mantle lengths (DMLs). The iteration with the lowest LOSS value was selected as the best estimate of the breakpoint. In C. sicula, 7 of 10 measured characters had a single breakpoint, and 5 of these occurred at 7-9 mm DML. In M. magna, only 4 of 12 characters had breakpoints, 3 of which occurred at 4-7 mm DML. More, larger specimens would likely yield additional breakpoints. In Brachioteuthis sp. 3, 12 of 14 characters had discernable breakpoints; 3 characters had 2 breakpoints. Most breakpoints occurred at 11-12 mm DML, and all were found at larger sizes than in the other species. This clustering of breakpoints into discrete size ranges may be considered an allomorphosis, and this rapid morphological change may correlate with rapid ecological change.     

A Chemical Mass Balance for Volatile Organics in Chicago

Increasing attention to the presence of atmospheric volatile organic compounds has focused interest on the sources and fate of organics in ambient air. The purpose of this study was to develop a chemical mass balance receptor model (CMB) to determine the contributions of major organic pollution source types to ambient pollution levels. Twenty mid-day ambient air samples were analyzed for the presence of volatile hydrocarbons by gas chromatographlc procedures. Based on these measurements, contributions from vehicles, gasoline vapor emissions, and petroleum refineries to ambient organic concentrations were estimated. For the receptor site studied, vehicles were the dominant source type and accounted for 60.8 percent of the organics evaluated. Contributions from refineries, gasoline vapor, and all other sources were 10.1, 11.1, and 17.9 percent, respectively. Validation of the predictions showed that the model is sensitive to the effect of overall upwind emissions. The CMB model was shown to produce reasonable predictive results for vehicles, gasoline vapor, and refinery contributions to ambient non-methane organic concentrations.