The effect of five forage species on transport and transformation of atrazine and isoxaflutole (balance) in lysimeter leachate

A field lysimeter study with bare ground and five different ground covers was established to evaluate the effect of forage grasses on the fate and transport of two herbicides in leachate. The herbicides were atrazine (ATR; 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) and isoxaflutole [IXF; 5-cyclopropyl-4-(2-methylsulfonyl-4-trifluormethyl-benzoyl)isoxazole], which has the commercial name Balance (Aventis Crop Science, Strasbourg, France). The ground covers included orchardgrass (Dactylis glomerata L.), smooth bromegrass (Bromus inermis Leyss.), tall fescue (Festuca arundinacea Schreb.), timothy (Phleum pratense L.), and switchgrass (Panicum virgatum L.). The results suggested that the total IXF (parent + metabolites) showed higher mobility than ATR and its metabolites. Differences in the timing of transport reflected the rapid degradation of IXF to the more soluble, stable, and biologically active diketonitrile (DKN) metabolite in the system. Although grass treatments did not promote the hydrolysis of DKN, they significantly reduced its transport in the leachate through enhanced evapotranspiration. Grass treatments significantly enhanced ATR degradation in the leachates and soils, especially through N dealkylation, but they did not reduce total ATR transported in the leachate. Leachate from the orchardgrass lysimeters contained the highest proportion of ATR metabolites (64.2%). Timothy and smooth bromegrass treatments also displayed a significant increase in ATR metabolites in leachate. Grass-treated lysimeters showed higher microbial biomass carbon than bare ground. For ATR treatments, the proportion of metabolites in the leachate strongly correlated with the elevated soil microbial biomass carbon in forage treatments. In contrast, DKN degradation was poorly correlated with soil microbial biomass carbon, suggesting that DKN degradation is an abiotic process.     

Using nonequilibrium thin-disc and batch equilibrium techniques to evaluate herbicide sorption

Nonequilibrium disc-flow techniques may better reproduce dynamic soil-pesticide interactions than traditional batch sorption studies. Batch kinetic and equilibrium experiments and dual-label thin-disc flow experiments were conducted with atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazine-2,4-diamine) and imazaquin [2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-3-quinolinecarboxylic acid] using a Demopolis silt loam (loamy-skeletal, carbonatic, thermic, shallow Typic Udorthent; 8% clay, 62 g kg(-1) organic matter, 7.6 pH). Batch kinetic studies with both herbicides revealed an almost instantaneous rapid phase and a much slower gradual phase. The rapid phase was complete after 5 min and equilibrium was reached at 24 h. The rapid phase accounted for 74% and 12 to 30% of the total amounts adsorbed for atrazine and imazaquin, respectively. The sorption of both the rapid and 24-h isotherms for each herbicide best fit the Freundlich equation. The rapid and 24-h K(f) values of atrazine were 1.38 and 2.41, respectively, and the N value of both phases was approximately 0.93. For imazaquin, the rapid and 24-h K(f) values were 0.056 and 035, respectively, and the N value for the rapid phase of imazaquin was 0.71, compared with 0.86 for the 24-h isotherm. In the dual-label thin-disc flow experiments, the average partition coefficient for atrazine at the peak soil concentration point was 1.54. This value closely agreed with the observed rapid-phase K(f) value of 1.38. In contrast, the thin-disc flow experiments failed to detect any imazaquin retention. The thin-disc flow method can allow for a greater resolution of rapid sorption kinetics, which is impractical with batch studies. Along with dynamic partitioning data, the thin-disc flow method may provide kinetics data that may better complement environmental models than coefficients generated with batch techniques.     

Biogeochemistry of fluoride in a plant-solution system

Fluoride (F-) pollutants can harm plants and the animals feeding on them. However, it is largely unknown how complexing and chelating agents affect F bioavailability. Two studies were conducted that measured F- bioavailability and uptake by rice (Oryza sativa L.). In the first study, rice was grown in solution culture (pH 5.0) with 0, 2, or 4 mM F- as KF to compare the interaction of F- with humic acid (HA) and with a conventional chelating agent, N-hydroxyethylenthylenediaminetriacetic acid (HEDTA). In the second study, F was supplied at 0, 0.5, 1.0, and 2.0 mM KF with an additional 2 mM F- treatment containing solution Ca at 2x (2 mM Ca) the level used in the first study, to test the effect added Ca had on F- availability and uptake. Total biomass was greatest with HEDTA and F- < 1 mM. Leaf and stem F concentrations increased exponentially as solution F- increased linearly, with nearly no F partitioning into the seed. Results suggest that F was taken up as HF0 while F- uptake was likely restricted. Additionally, F- competed with HA for Ca, thus preventing the formation of Ca-HA flocculents. The addition of soluble Ca resulted in the precipitation of CaF2 solids on the root surface, as determined by tissue analysis and energy dispersive X-ray spectroscopy.     

Integrated BIosphere Simulator (IBIS) yield and nitrate loss predictions for Wisconsin maize receiving varied amounts of nitrogen fertilizer

Agriculture in the U.S. Midwest faces the formidable challenge of improving crop productivity while simultaneously mitigating the environmental consequences of intense management. This study examined the simultaneous response of nitrate nitrogen (NO3-N) leaching losses and maize (Zea mays L.) yield to varied fertilizer N management using field observations and the Integrated BIosphere Simulator (IBIS) model. The model was validated against six years of field observations in chisel-plowed maize plots receiving an optimal (180 kg N ha(-1)) fertilizer N application and in N-unfertilized plots on a silt loam soil near Arlington, Wisconsin. Predicted values of grain yield, harvest index, plant N uptake, residue C to N ratio, leaf area index (LAI), grain N, and drainage were within 20% of observations. However, simulated NO3-N leaching losses, NO3-N concentrations, and net N mineralization exhibited less interannual variability than observations, and had higher levels of error (20-65%). Potential effects of 30% higher (234 kg N ha(-1)) and 30% lower (126 kg N ha(-1)) fertilizer N use (from optimal) on NO3-N leaching loss and maize yield were simulated. A 30% increase in fertilizer N use increased annual NO3-N leaching by 56%, while yield increased by only 1%. The NO3-N concentration in the leachate solution at 1.4 m below the soil surface was 30.7 mg L(-1). When fertilizer N use was reduced by 30% (from optimal), annual NO3-N leaching losses declined by 42% after seven years, and annual average yield only decreased by 8%. However, NO3-N concentration in the leachate solution remained above 10 mg L(-1) (11.3 mg L(-1)). Clearly, nonlinear relationships existed between changes in fertilizer use and NO3-N leaching losses over time. Simulated changes in NO3-N leaching were greater in magnitude than fertilizer N use changes.     

Effects of organic amendments on the reduction and phytoavailability of chromate in mineral soil

In this study, seven organic amendments (biosolid compost, farm yard manure, fish manure, horse manure, spent mushroom, pig manure, and poultry manure) were investigated for their effects on the reduction of hexavalent chromium [chromate, Cr(VI)] in a mineral soil (Manawatu sandy soil) low in organic matter content. Addition of organic amendments enhanced the rate of reduction of Cr(VI) to Cr(III) in the soil. At the same level of total organic carbon addition, there was a significant difference in the extent of Cr(VI) reduction among the soils treated with organic amendments. There was, however, a significant positive linear relationship between the extent of Cr(VI) reduction and the amount of dissolved organic carbon in the soil. The effect of biosolid compost on the uptake of Cr(VI) from the soil, treated with various levels of Cr(VI) (0-1200 mg Cr kg(-1) soil), was examined with mustard (Brassica juncea L.) plants. Increasing addition of Cr(VI) increased Cr concentration in plants, resulting in decreased plant growth (i.e., phytotoxicity). Addition of the biosolid compost was effective in reducing the phytotoxicity of Cr(VI). The redistribution of Cr(VI) in various soil components was evaluated by a sequential fractionation scheme. In the unamended soil, the concentration of Cr was higher in the organic-bound, oxide-bound, and residual fractions than in the soluble and exchangeable fractions. Addition of organic amendments also decreased the concentration of the soluble and exchangeable fractions but especially increased the organic-bound fraction in soil.     

A two-dimensional model for simulating the transport and fate of toxic chemicals in a stratified reservoir

A two-dimensional reservoir toxics model is essential to establishing effective water resources management and protection. In a reservoir, the fate of a toxic chemical is closely connected with flow regimes and circulation patterns. To better understand the kinetic processes and persistence and predict the dissipation of toxic contaminants in the reservoir during a spill or storm runoff event, a toxics submodel was developed and incorporated into an existing laterally integrated hydrodynamics and transport model. The toxics submodel describes the physical, chemical, and biological processes and predicts unsteady vertical and longitudinal distributions of a toxic chemical. The two-dimensional toxicant simulation model was applied to Shasta Reservoir in California to simulate the physico-chemical processes and fate of a volatile toxic compound, methyl isothiocyanate (MITC), during a chemical spill into the Sacramento River in 1991. The predicted MITC concentrations were compared with those observed. The effect of reservoir flow regimes on the transport and fate of the toxic substance was investigated. The results suggested that the persistence of MITC is significantly influenced by different flow regimes. Methyl isothiocyanate is more persistent in the reservoir under an interflow condition due to reduced volatilization from deep layers than under an overflow condition. In the overflow situation, the plume moved more slowly toward the dam and experienced greater dissipation. This analysis can assist in toxic spill control and reservoir management, including field sampling and closure of water intakes.     

Relationship between water repellency and native and petroleum-derived organic carbon in soils

Some soils develop severe and persistent water repellency following contamination with crude oil. This study was conducted to characterize and compare the spatial distribution of soil water repellency and residual oil contamination at 12 such sites. The molarity of ethanol droplet (MED) test was used to assess soil water repellency and the content of dichloromethane-extractable organics (DEO) was used to quantify residual oil in soil. We found a relatively strong positive correlation between MED and DEO in soil (r2 = 0.74). Both variables tended to decrease abruptly with depth at 11 of the 12 study sites. Dichloromethane-extractable organics similarly decreased with depth in control adjacent soil (MED = 0 M), but from an average concentration one to two orders of magnitude lower than in water-repellent soil. Using data from corresponding control adjacent and water-repellent soils, we determined that approximately 29 and 10% of measured total organic carbon in water-repellent A- and B-horizon soil, respectively, consists of dichloromethane-insoluble organic carbon of petroleum origin. We propose that this fraction contains most of the causative agents of soil water repellency at the studied sites.     

Nitrogen removal and nitrate leaching for two perennial,sod-based forage systems receiving dairy effluent

In northern Florida, year-round forage systems are used in dairy effluent sprayfields to reduce nitrate leaching. Our purpose was to quantify forage N removal and monitor nitrate N (NO3(-)-N) concentration below the rooting zone for two perennial, sod-based, triple-cropping systems over four 12-mo cycles (1996-2000). The soil is an excessively drained Kershaw sand (thermic, uncoated Typic Quartzip-samment). Effluent N rates were 500, 690, and 910 kg ha(-1) per cycle. Differences in N removal between a corn (Zea mays L.)-bermudagrass (Cynodon spp.)-rye (Secale cereale L.) system (CBR) and corn-perennial peanut (Arachis glabrata Benth.)-rye system (CPR) were primarily related to the performance of the perennial forages. Nitrogen removal of corn (125-170 kg ha(-1)) and rye (62-90 kg ha(-1)) was relatively stable between systems and among cycles. The greatest N removal was measured for CBR in the first cycle (408 kg ha(-1)), with the bermudagrass removing an average of 191 kg N ha(-1). In later cycles, N removal for bermudagrass declined because dry matter (DM) yield declined. Yield and N removal of perennial peanut increased over the four cycles. Nitrate N concentrations below the rooting zone were lower for CBR than CPR in the first two cycles, but differences were inconsistent in the latter two. The CBR system maintained low NO3(-)-N leaching in the first cycle when the bermudagrass was the most productive; however, it was not a sustainable system for long-term prevention of NO3(-)-N leaching due to declining bermudagrass yield in subsequent cycles. For CPR, effluent N rates > or = 500 kg ha(-1) yr(-1) have the potential to negatively affect ground water quality.     

Chemical extraction methods to assess bioavailable arsenic in soil and solid media

Soil ingestion by children is an important pathway in assessing public health risks associated with exposure to arsenic-contaminated soils. Soil chemical methods are available to extract various pools of soil arsenic, but their ability to measure bioavailable arsenic from soil ingestion is unknown. Arsenic extracted by five commonly used soil extractants was compared with bioavailable arsenic measured in vivo by immature swine (Sus scrofa) dosing trials. Fifteen contaminated soils that contained 233 to 17 500 mg kg(-1) arsenic were studied. Soil extractants were selected to dissolve surficially adsorbed and/or readily soluble arsenic (water, 1 M sodium acetate, 0.1 M Na2HPO4/0.1 M NaH2PO4) and arsenic in Fe and Mn oxide minerals (hydroxylamine hydrochloride, ammonium oxalate). The mean percent of total arsenic extracted was: ammonium oxalate (53.6%) > or = hydroxylamine hydrochloride (51.7%) > phosphate (10.5%), acetate (7.16%) > water (0.15%). The strongest relationship between arsenic determined by soil chemical extraction and in vivo bioavailable arsenic was found for hydroxylamine hydrochloride extractant (r = 0.88, significant at the 0.01 probability level). Comparison of the amount of arsenic extracted by soil methods with bioavailable arsenic showed the following trend: ammonium oxalate, hydroxylamine hydrochloride > in vivo > phosphate, acetate > water. The amount of arsenic dissolved in the stomach (potentially bioavailable) is between surficially adsorbed (extracted by phosphate or acetate) and surficially adsorbed + nonsurficial forms in Fe and Mn oxides (extracted by hydroxylamine hydrochloride or ammonium oxalate). Soil extraction methods that dissolve some of the amorphous Fe, such as hydroxylamine hydrochloride, can be designed to provide closer estimates of bioavailable arsenic.