Modeling of sorption and biodegradation of parathion and its metabolite paraoxon in soil

To investigate the distribution of parathion [O,O-diethyl O-(4-nitrophenyl) phosphorothioate] and its highly toxic metabolite paraoxon [O,O-diethyl O-(4-nitrophenyl)phosphate] between the soluble and sorbed pools in the soil, batch experiments were conducted to evaluate the rate of adsorption and desorption of 14C-labeled parathion and paraoxon in soil. The mineralization and degradation of these products were also investigated during a 56-d experiment under controlled laboratory conditions. Adsorption patterns indicated initial fast adsorption reactions occurring within 4 h for both parathion and paraoxon. We also observed the formation of nonextractable residues. The paraoxon was more intensively degraded than the parathion, and production of p-nitrophenol and other metabolites was observed. A kinetic model was developed to describe the sorption and biodegradation rates of parathion, taking into account the production, retention, and biodegradation of paraoxon, the main metabolite of parathion. After fitting the parameters of the model we made a simulation of the kinetics of the appearance and disappearance of paraoxon. From the simulation we predicted a quantity of metabolite in the liquid phase amounting to 1% of the quantity of parathion initially applied. This is in agreement with the experimental data.     

Measuring sorption of hydrophilic organic compounds in soils by an unsaturated transient flow method

Determination of sorption of hydrophilic, weakly sorbing organic compounds in soil by conventional batch methods using a slurried suspension is often prone to considerable errors because small changes in the solution concentration on equilibration must be accurately determined. This difficulty is exacerbated for compounds susceptible to degradation, which also decreases the solution concentration. The objective of this study was to determine sorption of hydrophilic pesticides by applying an unsaturated transient flow method, which enables determination of sorption at sufficiently small solution to soil ratios. The method makes use of piston-like displacement of the antecedent solution in equilibrium with sorbed phase when pesticide-free water is infiltrated into a soil column spiked with a pesticide. Pesticide sorption and the solution concentration are inferred from a plot of total pesticide content per unit mass of soil vs. water content in a region where the antecedent solution is accumulated. Thus, extraction of solution from relative dry soil is unnecessary. We tested this method for two hydrophilic pesticides, monocrotophos [dimethyl (E)-1-methyl-2-(methyl-carbamoyl) vinyl phosphate] and dichlorvos (2,2-dichlorovinyl dimethyl phosphate). The sorption coefficient, K(d), obtained for monocrotophos was slightly lower than that by batch method (K(d) = 0.10 vs. 0.19 L kg(-1)), whereas for dichlorvos, a compound highly susceptible to degradation, the unsaturated flow method yielded a much smaller K(d) (0.19 vs. 3.22 L kg(-1)). The K(d) values for both compounds were consistent with the observed retardation in the pesticide displacement in the columns. The proposed method is more representative of field conditions and particularly suitable for weakly sorbing organic compounds in soils.     

Sorption of atmospheric ammonia by soil and perennial grass downwind from two large cattle feedlots

Livestock manure in feedlots releases ammonia (NH3), which can be sorbed by nearby soil and plants. Ammonia sorption by soil and its effects on soil and perennial grass N contents downwind from two large cattle feedlots in Alberta, Canada were investigated from June to October 2002. Atmospheric NH3 sorption was measured weekly by exposing air-dried soil at sampling points downwind along 1700-m transects. The amount of NH3 sorbed by soil was 2.60 to 3.16 kg N ha(-1) wk(-1) near the source, declining to about 0.25 kg N ha(-1) wk(-1) 1700 m downwind, reflecting diminishing atmospheric NH3 concentrations. Ammonia sorption at a control site away from NH3 sources was much lower: 0.085 kg N ha(-1) wk(-1). Based on these rates, about 19% of emitted NH3 is sorbed by soil within 1700 m downwind of feedlots. Field soil and grass samples from the transect lines were analyzed for total N (TN) and KCl-extractable N content (soil only). Nitrate N content in field soil followed a trend similar to that of atmospheric NH3 sorption. Soil TN contents, because of high background levels, showed no clear pattern. The TN content of grass, downwind of the newer feedlot, followed a pattern similar to that of NH3 sorption; downwind of the older feedlot, grass TN was correlated to soil TN. Our results suggest that atmospheric NH3 from livestock operations can contribute N to local soil and vegetation, and may need to be considered when determining fertilizer rates and assessing environmental impact.     

Review of Pesticide Retention Processes Occurring in Buffer Strips Receiving Agricultural Runoff1

Arora, Kapil, Steven K. Mickelson, Matthew J. Helmers, and James L. Baker, 2010. Review of Pesticide Retention Processes Occurring in Buffer Strips Receiving Agricultural Runoff. Journal of the American Water Resources Association (JAWRA) 46(3):618-647. DOI: 10.1111/j.1752-1688.2010.00438.x Abstract: Review of the published results shows that the retention of the two pesticide carrier phases (runoff volume and sediment mass) influences pesticide mass transport through buffer strips. Data averaged across different studies showed that the buffer strips retained 45% of runoff volume (ranging between 0 and 100%) and 76% of sediment mass (ranging between 2 and 100%). Sorption (soil sorption coefficient, K_oc) is one key pesticide property affecting its transport with the two carrier phases through buffer strips. Data from different studies for pesticide mass retention for weakly (K_oc < 100), moderately (100 < K_oc < 1,000), and strongly sorbed pesticides (K_oc > 1,000) averaged (with ranges) 61 (0-100), 63 (0-100), and 76 (53-100) %, respectively. Because there are more data for runoff volume and sediment mass retention, the average retentions of both carrier phases were used to calculate that the buffer strips would retain 45% of weakly to moderately sorbed and 70% of strongly sorbed pesticides on an average basis. As pesticide mass retention presented is only an average across several studies with different experimental setups, the application of these results to actual field conditions should be carefully examined.     

Sorption of trace metals by standard and micro suction cups in the absence and presence of dissolved organic carbon

Both the bioavailability of a trace metal (TM) in a soil and the risk of leaching to the ground water are linked to the metals concentration in the soil solution. Sampling soil solution by tension lysimetry with suction cups is a simple and established technique that is increasingly used for monitoring dissolved TM in soils. Of major concern, however, is the sorption of TM by the walls of the samplers. Metal sorption by different materials used in suction cups can vary widely, depending also on the chemistry of the soil solution. We compared the sorption of Cu, Zn, Cd, and Pb by different standard-size and micro suction cups in the laboratory at two pH values (4.5 and 7.5 or 8.0) in absence and presence of dissolved organic carbon (DOC). In addition, we investigated the sorption of DOC from different origins by the cup materials. At both pH values, the weakest sorption of all four TMs was exhibited by standard-size suction cups based on nylon membranes and by hollow fibers made from polyvinyl alcohol (PVA). At alkaline pH, borosilicate glass, ceramic materials, and polytetrafluorethylene (PTFE) mixed with silicate were characterized by generally strong sorption of all investigated TMs. In addition, Cu and Pb were strongly sorbed at low pH by PTFE-silicate and a ceramic material used for the construction of standard-size suction cups. On the other hand, sorption of Cu, Zn, and Cd by ceramic capillaries produced from pure aluminum oxide was negligible at low pH. Micro suction cups made of an unknown polymerous tube sorbed Cu strongly, but were well suited to monitor Zn, Cd, and Pb at low pH, and, in the presence of DOC, also at high pH. Major cations (Na+, Mg2+, K+, Ca2+) and anions (Cl-, NO3-, SO4(2-)) were not or very weakly sorbed by all cup materials, except for Mg2+, K+, and Ca2+ by borosilicate glass at pH 7.5. Trace metal sorption by suction cups was generally greatly reduced in the presence of DOC, especially at alkaline pH. The sorption of DOC itself depended on its source. Dissolved organic carbon from leaf litter extracts with a probably large hydrophobic fraction was sorbed more strongly than mainly hydrophilic DOC from a mineral soil solution.     

Regional assessment of herbicide sorption and degradation in two sampling years

Sorption and degradation of the herbicide 2,4-D [2,4-dichlorophenoxyacetic acid] were determined for 123 surface soils (0 to 15 cm) collected in 2002 and in 2004 between 49 degrees to 60 degrees north longitude and 110 degrees to 120 degrees west latitude in Alberta, Canada. The soils were characterized by soil organic carbon content (SOC), pH, electrical conductivity, soil texture, cation exchange capacity, carbonate content, and total soil microbial activity. The 2,4-D sorption coefficients, Kd and Koc, were highly variable with coefficients of variation of 89 and 59%, respectively, at the provincial scale. Both Kd and Koc were well described by regression models with SOC and soil pH as variables, regardless of scale. Surprisingly, variations in 2,4-D mineralization were much smaller than variations in sorption. Variability in total 2,4-D mineralization was particularly low, with a coefficient of variation of only 7% at the provincial scale. Average 2,4-D half-lives in ecoregions ranged from 1.7 to 3.5 d, much lower than the field dissipation half-life of 10 d reported for 2,4-D in general pesticide property databases. Regression models describing degradation parameters were generally poor or not significant because 2,4-D mineralization was only weakly associated with measured 2,4-D sorption parameters and soil properties. As such, regional variations in herbicide sorption coefficients should be measured or calculated based on soil properties, to assign distinct pesticide fate model input parameters when estimating 2,4-D off-site transport at the provincial scale. Spatial variations in herbicide degradation appear less important for Alberta as 2,4-D half-lives were similar in soils across the province. The rapid mineralization of 2,4-D is noteworthy because 2,4-D is widely used in Alberta and perhaps adaptation of soil microbial communities allowed for accelerated degradation regardless of soil properties or the extent of 2,4-D sorption by soil.     

Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils

Reactions of heavy metals with soil are important in determining metal fates in the environment. Sorption characteristics of two heavy metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) from Puerto Rico were assessed at varying metal concentrations (0 to 1.2 mM) and pH values (approximately 2 to 7). All soils sorbed more Pb than Cd. Sorption maxima were obtained for each metal for the Oxisol and Ultisol soils, but not the Mollisol. Sorption appeared to depend more on soil mineralogy than organic matter content. Sorption isotherms were linear within the sorption envelope with similar slopes for each soil-metal curve, when plotting metal sorption as a function of pH. Cadmium and Pb isotherms yielded average slopes of approximately 36+/-1 and 28+/-1 units (percent increase in metal sorption per 1-unit increase in pH), respectively. Metal sorption depended more on metal type than soil composition. Cadmium sorption displayed a greater pH dependence than Pb. Cadmium sorption was less than or equal to the amount of negative surface charge except at pH values greater than the point of zero net charge (PZNC). This suggests that Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere complexation at pH > 3.7. However, the amount of Pb sorbed by the Oxisol was greater than the amount of negative surface charge, suggesting that Pb participates in inner-sphere surface reactions. Lead was sorbed more strongly than Cd in our soils and poses less of a threat to underlying ground water systems due to its lower mobility and availability.     

MODEL FOR PREDICTING TRANSPORT OF PESTICIDES AND THEIR METABOLITES IN THE UNSATURATED ZONE1

ABSTRACT: A finite element model based on Galerkin's upstream weighted residual technique was developed to predict the simultaneous convective-dispersion transport and transformations of pesticides and their metabolites in the unsaturated zone. Transformations of the parent compound and its metabolites were assumed to be first-order reactions for oxidation and hydrolysis, while adsorption of the pesticide species (parent compound and metabolites) to the soil components was assumed to be represented by a linear equilibrium (Freundlich type) isotherm. Volatilization and plant root uptake of pesticides in the solution phase were neglected in the analysis. The proposed model was used to simulate the transport and transformation of aldicarb and its metabolites, aldicarb sulfoxide and aldicarb sulfone, in the soil profile. Several examples are used to demonstrate the accuracy, validity, and applicability of the proposed model. Simulated results indicate that the proposed model can potentially be used to estimate the mass flux of water, and pesticide and pesticide metabolite concentrations in the subsurface environment. However, further verification of the model against actual field data is needed to fully demonstrate the model's potential.     

Bioaccessibility of lead sequestered to corundum and ferrihydrite in a simulated gastrointestinal system

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of Pb-contaminated soil. Lead was sorbed to model oxide minerals of corundum (alpha-Al(2)O(3)) and ferrihydrite (Fe(5)HO(8).4H(2)O). The Pb-sorbed minerals were placed in a simulated gastrointestinal tract (in vitro) to simulate ingestion of Pb-contaminated soil. The changes in Pb speciation were determined using extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES). Both corundum (sorption maximum of 2.13 g kg(-1)) and ferrihydrite (sorption maximum of 38.6 g kg(-1)) have been shown to sorb Pb, with ferrihydrite having a very high affinity for Pb. The gastric bioaccessible Pb for corundum was >85% for corundum when the concentration of Pb was >200 mg kg(-1). Bioaccessible Pb was not detectable at 4. However, much of the sorbed Pb will become bioaccessible under gastric conditions (pH 1.5-2.5) if this soil is ingested. Caution should be used before using these materials to remediate a soil where soil ingestion is an important exposure pathway.     

Sorption, mobility, and transformation of estrogenic hormones in natural soil

Potent estrogenic hormones are consistently detected in the environment at low concentration, yet these chemicals are strongly sorbed to soil and are labile. The objective of this research was to improve the understanding of the processes of sorption, mobility, and transformation for estrogens in natural soils, and their interaction. Equilibrium and kinetic batch sorption experiments, and a long-term column study were used to study the fate and transport of 17beta-estradiol and its primary metabolite, estrone, in natural soil. Kinetic and equilibrium batch experiments were done using radiolabeled 17beta-estradiol and estrone. At the concentrations used, it appeared that equilibrium sorption for both estrogens was achieved between 5 and 24 h, and that the equilibrium sorption isotherms were linear. The log K(oc) values for 17beta-estradiol (2.94) and estrone (2.99) were consistent with previously reported values. Additionally, it was found that there was rate-limited sorption for both 17beta-estradiol (0.178 h(-1)) and estrone (0.210 h(-1)). An approximately 42 h long, steady-flow, saturated column experiment was used to study the transport of radiolabeled 17beta-estradiol, which was applied in a 5.00 mg L(-1) solution pulse for 44 pore volumes. 17beta-estradiol and estrone were the predominant compounds detected in the effluent. The effluent breakthrough curves were asymmetric and the transport modeling indicated that sorption was rate-limited. Sorption rates and distributions of the estrogens were in agreement between column and batch experiments. This research can provide a better link between the laboratory results and observations in the natural environment.     

Estimating soil phosphorus requirements and limits from oxalate extract data

Excessive fertilizer and manure phosphorus (P) inputs to soils elevates P in soil solution and surface runoff, which can lead to freshwater eutrophication. Runoff P can be related to soil test P and P sorption saturation, but these approaches are restricted to a limited range of soil types or are difficult to determine on a routine basis. The purpose of this study was to determine whether easily measurable soil characteristics were related to the soil phosphorus requirements (P(req), the amount of P sorbed at a particular solution P level). The P(req) was determined for 18 chemically diverse soils from sorption isotherm data (corrected for native sorbed P) and was found to be highly correlated to the sum of oxalate-extractable Al and Fe (R2 > 0.90). Native sorbed P, also determined from oxalate extraction, was subtracted from the P(req) to determine soil phosphorus limits (PL, the amount of P that can be added to soil to reach P(req)). Using this approach, the PL to reach 0.2 mg P L(-1) in solution ranged between -92 and 253 mg P kg(-1). Negative values identified soils with surplus P, while positive values showed soils with P deficiency. The results showed that P, Al, and Fe in oxalate extracts of soils held promise for determining PL to reach up to 10 mg P L(-1) in solution (leading to potential runoff from many soils). The soil oxalate extraction test could be integrated into existing best management practices for improving soil fertility and protecting water quality.     

Size distribution of organic matter and associated propiconazole in agricultural runoff material

Sorption and desorption characteristics of propiconazole (1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole) to different particle/aggregate-size fractions of agricultural runoff material were investigated. Emphasis was put on clay and colloidal size fractions to evaluate their role as potential sorbents and carriers for this pesticide. The runoff material was separated into size fractions ranging from 2 mm to ca. 15 nm by wet sieving, sedimentation, centrifugation, and membrane ultrafiltration. Each fraction was characterized by its organic C content and C/N ratio. Distinctive sorption properties of clay-sized particles and colloids were investigated. The obtained size fractions differed significantly in their organic C concentration, C/N ratio, and sorption properties to propiconazole. Organic matter was mainly associated in aggregates >2 microm. Binding of propiconazole to this coarse fraction made up 80% of the sorbed propiconazole. The distribution coefficient between solid and aqueous phases increased with decreasing particle size. The colloidal fraction (<0.16 microm) exhibited the highest sorbtivity, with a distribution coefficient of 113 L kg(-1), which was more than four times higher than that in the bulk sample (27 L kg(-1)). The fraction <2 microm represented 8% of the total sample weight, but contributed to 20% of the sorbed propiconazole. Strong hysteresis was observed for the sorption-desorption of propiconazole on the runoff material. Under dilution very little sorbed propiconazole will be released into the water phase. Due to its high sorbtivity and mobility and the strong sorption-desorption hysteresis, particles in the fraction <2 microm can be important carriers of propiconazole in runoff suspensions with high sediment load.     

Sorption and degradation of pesticides in nursery recycling ponds

Knowledge of pesticide distribution and persistence in nursery recycling pond water and sediment is critical for preventing phytotoxicity of pesticides during water reuse and to assess their impacts to the environment. In this study, sorption and degradation of four commonly used pesticides (diazinon, chlorpyrifos, chlorothalonil, and pendimethalin) in sediments from two nursery recycling ponds was investigated. Results showed that diazinon and chlorothalonil were moderately sorbed [K(OC) (soil organic carbon distribution coefficient) from 732 to 2.45 x 10(3) mL g(-1)] to the sediments, and their sorption was mainly attributable to organic matter content, whereas chlorpyrifos and pendimethalin were strongly sorbed (K(OC) > or = 7.43 x 10(3) mL g(-1)) to the sediments, and their sorption was related to both organic matter content and sediment texture. The persistence of diazinon and chlorpyrifos was moderate under aerobic conditions (half-lives = 8 to 32 d), and increased under anaerobic conditions (half-lives = 12 to 53 d). In contrast, chlorothalonil and pendimethalin were quickly degraded under aerobic conditions with half-lives < 2.8 d, and their degradation was further enhanced under anaerobic conditions (half-lives < 1.9 d). The strong sorption of chlorpyrifos and pendimethalin by the sediments suggests that the practice of recycling nursery runoff would effectively retain these compounds in the recycling pond, minimizing their offsite movement. The prolonged persistence of diazinon and chlorpyrifos, however, implies that incidental spills, such as overflows caused by storm events, may contribute significant loads of such pesticides into downstream surface water bodies.     

Sensitivity and first-step uncertainty analyses for the preferential flow model MACRO

Sensitivity analyses for the preferential flow model MACRO were carried out using one-at-a-time and Monte Carlo sampling approaches. Four different scenarios were generated by simulating leaching to depth of two hypothetical pesticides in a sandy loam and a more structured clay loam soil. Sensitivity of the model was assessed using the predictions for accumulated water percolated at a 1-m depth and accumulated pesticide losses in percolation. Results for simulated percolation were similar for the two soils. Predictions of water volumes percolated were found to be only marginally affected by changes in input parameters and the most influential parameter was the water content defining the boundary between micropores and macropores in this dual-porosity model. In contrast, predictions of pesticide losses were found to be dependent on the scenarios considered and to be significantly affected by variations in input parameters. In most scenarios, predictions for pesticide losses by MACRO were most influenced by parameters related to sorption and degradation. Under specific circumstances, pesticide losses can be largely affected by changes in hydrological properties of the soil. Since parameters were varied within ranges that approximated their uncertainty, a first-step assessment of uncertainty for the predictions of pesticide losses was possible. Large uncertainties in the predictions were reported, although these are likely to have been overestimated by considering a large number of input parameters in the exercise. It appears desirable that a probabilistic framework accounting for uncertainty is integrated into the estimation of pesticide exposure for regulatory purposes.     

Surfactant-soil interactions during surfactant-amended remediation of contaminated soils by hydrophobic organic compounds: a review

Surfactants are amphiphilic molecules that reduce aqueous surface tension and increase the solubility of hydrophobic organic compounds (HOCs). Surfactant-amended remediation of HOC-contaminated soils and aquifers has received significant attention as an effective treatment strategy - similar in concept to using soaps and detergents as washing agents to remove grease from soiled fabrics. The proposed mechanisms involved in surfactant-amended remediation include: lowering of interfacial tension, surfactant solubilization of HOCs, and the phase transfer of HOC from soil-sorbed to pseudo-aqueous phase. However, as with any proposed chemical countermeasures, there is a concern regarding the fate of the added surfactant. This review summarizes the current state of knowledge regarding nonionic micelle-forming surfactant sorption onto soil, and serves as an introduction to research on that topic. Surfactant sorption onto soil appears to increase with increasing surfactant concentration until the onset of micellization. Sorbed-phase surfactant may account for the majority of added surfactant in surfactant-amended remediation applications, and this may result in increased HOC partitioning onto soil until HOC solubilization by micellar phase surfactant successfully competes with increased HOC sorption on surfactant-modified soil. This review provides discussion of equilibrium partitioning theory to account for the distribution of HOCs between soil, aqueous phase, sorbed surfactant, and micellar surfactant phases, as well as recently developed models for surfactant sorption onto soil. HOC partitioning is characterized by apparent soil-water distribution coefficients in the presence of surfactant.     

Simulating pesticide leaching and runoff in rice paddies with the RICEWQ-VADOFT model

There is a current need to simulate leaching and runoff of pesticide from rice (Oryza sativa L.) paddies for assessing environmental impacts on a valuable agricultural system. The objective of this study was to develop a model for determining predicted environmental concentration (PEC) in soil, runoff, and ground water through the linkage of two models, rice water quality model (RICEWQ) and vadose zone transport model (VADOFT), to simulate pesticide fate and transport within a rice paddy and underlying soil profile. Model performance was evaluated with a field data set obtained from a 2-yr field experiment in 1997 and 1998 in northern Italy. The predictions of amount of pesticide running off from the paddy field and accumulating in the paddy sediment were in agreement with measured values. Leaching into the vadose zone accounted for approximately 19% of the applied dose, but only a small amount of chemical (<0.1%) was predicted to reach ground water at a 5-m depth due to sorption and transformation in the soil. The permeability of the soil and the water management practices in the paddy field were shown to have a strong influence on pesticide fate. These factors need to be well characterized in the field if model predictions are to be successful. The combined model developed in this work is an effective tool for exposure assessments for soil, surface water, and ground water, in the particular conditions of rice cultivation.     

Sorption of hydrophobic pesticides on a Mediterranean soil affected by wastewater, dissolved organic matter and salts

Irrigation with treated wastewaters as an alternative in countries with severe water shortage may influence the sorption of pesticides and their environmental effects, as wastewater contains higher concentrations of suspended and dissolved organic matter and inorganic compounds than freshwater. We have examined the sorption behaviour of three highly hydrophobic pesticides (the herbicide pendimethalin and the insecticides α-cypermethrin and deltamethrin) on a Mediterranean agricultural soil using the batch equilibration method. We considered wastewater, extracts from urban sewage sludge with different dissolved organic carbon contents, and inorganic salt solutions, using Milli Q water as a control. All pesticides were strongly retained by soil although some sorption occurred on the walls of the laboratory containers, especially when wastewater and inorganic salt solutions were used. The calculation of distribution constants by measuring pesticide concentrations in soil and solution indicated that pendimethalin sorption was not affected whereas α-cypermethrin and deltamethrin retention were significantly enhanced (ca. 5 and 2 times, respectively) when wastewater or salt solutions were employed. We therefore conclude that the increased sorption of the two pesticides caused by wastewater cannot be only the result of its dissolved organic carbon content, but also of the simultaneous presence of inorganic salts in the solution.     

Bioremediation of atrazine-contaminated soil by forage grasses: transformation, uptake, and detoxification

A sound multi-species vegetation buffer design should incorporate the species that facilitate rapid degradation and sequestration of deposited herbicides in the buffer. A field lysimeter study with six different ground covers (bare ground, orchardgrass, tall fescue, timothy, smooth bromegrass, and switchgrass) was established to assess the bioremediation capacity of five forage species to enhance atrazine (ATR) dissipation in the environment via plant uptake and degradation and detoxification in the rhizosphere. Results suggested that the majority of the applied ATR remained in the soil and only a relatively small fraction of herbicide leached to leachates (<15%) or was taken up by plants (<4%). Biological degradation or chemical hydroxylation of soil ATR was enhanced by 20 to 45% in forage treatment compared with the control. Of the ATR residues remaining in soil, switchgrass degraded more than 80% to less toxic metabolites, with 47% of these residues converted to the less mobile hydroxylated metabolites 25 d after application. The strong correlation between the degradation of N-dealkylated ATR metabolites and the increased microbial biomass carbon in forage treatments suggested that enhanced biological degradation in the rhizosphere was facilitated by the forages. Hydroxylated ATR degradation products were the predominant ATR metabolites in the tissues of switchgrass and tall fescue. In contrast, the N-dealkylated metabolites were the major degradation products found in the other cool-season species. The difference in metabolite patterns between the warm- and cool-season species demonstrated their contrasting detoxification mechanisms, which also related to their tolerance to ATR exposure. Based on this study, switchgrass is recommended for use in riparian buffers designed to reduce ATR toxicity and mobility due to its high tolerance and strong degradation capacity.     

Sorption of iron-cyanide complexes on goethite in the presence of sulfate and desorption with phosphate and chloride

Soils are contaminated with potentially toxic iron-cyanide complexes by some industrial activities. The influence of sulfate on the sorption of the iron-cyanide complexes ferricyanide, [Fe(CN)6]3-, and ferrocyanide, [Fe(CN)6]4-, on goethite was investigated in batch experiments. The experiments were conducted as influenced by pH and varying sulfate/iron-cyanide complex concentration ratios. Furthermore, the desorption of iron-cyanide complexes sorbed on goethite was studied using phosphate and chloride solutions as influenced by pH and anion concentration. Over the whole pH range (pH 3.5 to 8), ferricyanide and sulfate showed similar affinities for the goethite surface. The extent of ferricyanide sorption strongly depended on sulfate concentrations and vice versa. In contrast, ferrocyanide sorption was only decreased (approximately 12%) by sulfate additions at pH 3.5. Ferricyanide was completely desorbed by 1 M chloride, ferrocyanide not at all. Unbuffered phosphate solutions (pH 8.3) desorbed both iron-cyanide complexes completely. Even in 70-fold excess, pH-adjusted phosphate solutions could not desorb ferrocyanide completely at pH 3.5. For ferricyanide we propose a sorption mechanism that is similar to the sulfate sorption mechanism, including outer-sphere and weak inner-sphere surface complexes on goethite. Ferrocyanide appears to form inner-sphere surface complexes. Additionally, we assume that ferrocyanide precipitates probably as a Berlin Blue-like phase at pH 3.5. Hence, ferrocyanide should be less mobile in the soil environment than ferricyanide or sulfate.     

Contamination time effect on lead and cadmium fractionation in a tropical coastal clay

The capability of a tropical coastal clay to immobilize lead (Pb) and cadmium (Cd) was investigated in laboratory batch sorption tests conducted under acidic, neutral, and slightly alkaline conditions. The contact time was extended to 65 d. The distribution of Pb and Cd among various sorbed phases was examined using a sequential extraction technique. The sorbed phases were fractionated into the exchangeable, carbonate, reducible, organic, and residual fractions. There were only small changes in the total Pb and Cd sorption beyond a 1-d sorption period. The metal fractionation results show that the amount of Pb and Cd in various fractions changed with sorption time, and the changes were pH-dependent. These changes could be attributed to mineral dissolution and transformation or redistribution of the sorbed phases. Transformation of the sorbed phases resulted in increasing Pb and Cd retention in the more persistent fractions with time, at the expense of reductions in the loosely bound fractions. Nevertheless, Pb and Cd fractionation in the solid phase appeared to reach equilibrium within the 65-d sorption period. These Pb and Cd fractionation results reflect the effect of contamination time on the heavy metal lability and bioavailability in the subsurface environment.