Simulating endosulfan transport in runoff from cotton fields in Australia with the GLEAMS model

Endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9methano-2,4,3-benzodioxathiepin 3-oxide), a pesticide that is highly toxic to aquatic organisms, is widely used in the cotton (Gossypium hirsutum L.) industry in Australia and is a risk to the downstream riverine environment. We used the GLEAMS model to evaluate the effectiveness of a range of management scenarios aimed at minimizing endosulfan transport in runoff at the field scale. The field management scenarios simulated were (i) Conventional, bare soil at the beginning of the cotton season and seven irrigations per season; (ii) Improved Irrigation, irrigation amounts reduced and frequency increased to reduce runoff from excess irrigation; (iii) Dryland, no irrigation; (iv) Stubble Retained, increased soil cover created by retaining residue from the previous crop or a specially planted winter cover crop; and (v) Reduced Sprays, a fewer number of sprays. Stubble Retained was the most effective scenario for minimizing endosulfan transport because infiltration was increased and erosion reduced, and the stubble intercepted and neutralized a proportion of the applied endosulfan. Reducing excess irrigation reduced annual export rates by 80 to 90%, but transport in larger storm events was still high. Reducing the number of pesticide applications only reduced transport when three or fewer sprays were applied. We conclude that endosulfan transport from cotton farms can be minimized with a combination of field management practices that reduce excess irrigation and concentration of pesticide on the soil at any point in time; however, discharges, probably with endosulfan concentrations exceeding guideline values, will still occur in storm events.     

Endosulfan transport: I. Integrative assessment of airborne and waterborne pathways

To reduce endosulfan (C9H6O3Cl6S; 6,7,8,9,10,10-hexachloro-1,5, 5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3-oxide) contamination in rivers and waterways, it is important to know the relative significances of airborne transport pathways (including spray drift, vapor transport, and dust transport) and waterborne transport pathways (including overland and stream runoff). This work uses an integrated modeling approach to assess the absolute and relative contributions of these pathways to riverine endosulfan concentrations. The modeling framework involves two parts: a set of simple models for each transport pathway, and a model for the physical and chemical processes acting on endosulfan in river water. An averaging process is used to calculate the effects of transport pathways at the regional scale. The results show that spray drift, vapor transport, and runoff are all significant pathways. Dust transport is found to be insignificant. Spray drift and vapor transport both contribute low-level but nearly continuous inputs to the riverine endosulfan load during spraying season in a large cotton (Gossypium hirsutum L.)-growing area, whereas runoff provides occasional but higher inputs. These findings are supported by broad agreement between model predictions and observed typical riverine endosulfan concentrations in two rivers.     

Atrazine, isoproturon, mecoprop, 2,4-D, and bentazone adsorption onto iron oxides

Iron oxides are important components influencing the adsorption of various inorganic and organic compounds in soils and sediments. In this study the adsorption on iron oxides of nonionic and ionic pesticides was determined as a function of solution pH, ionic strength, and pesticide concentration. The investigated iron oxides included two-line ferrihydrite, goethite, and lepidocrocite. Selected pesticides comprised atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea)], mecoprop [(RS)-2-(4-chloro-2-methylphenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide]. The adsorption of the nonionic pesticides (atrazine and isoproturon) was insignificant, whereas the adsorption of the acidic pesticides (mecoprop, 2,4-D, and bentazone) was significant on all investigated iron oxides. The adsorption capacity increased with decreasing pH, with maximum adsorption reached close to the pKa values. The addition of CaCl2 in concentrations from 0.0025 to 0.01 M caused the adsorption capacity to diminish. The adsorption of bentazone was significantly lower than the adsorption of mecoprop and 2,4-D, illustrating the importance of a carboxyl group in the pesticide structure. The adsorption capacity on the iron oxides increased in the order: lepidocrocite < goethite < two-line ferrihydrite. The maximum adsorption capacities of meco-prop and 2,4-D on goethite were found to be equivalent to the site density of singly coordinated hydroxyl groups on the faces of the dominant (110) form, suggesting that singly coordinated hydroxyl groups are responsible for adsorption. Differences in adsorption capacities between iron oxides can be explained by differences in the surface site density of singly coordinated hydroxyl groups. The maximum measured adsorption capacity of mecoprop on two-line ferrihydrite was equivalent to 0.2 mol/mol Fe.     

Removal of uranium(VI) from contaminated sediments by surfactants

Uranium(VI) sorption onto a soil collected at the Melton Branch Watershed (Oak Ridge National Laboratory, TN) is strongly influenced by the pH of the soil solution and, to a lesser extent, by the presence of calcium, suggesting specific chemical interactions between U(VI) and the soil matrix. Batch experiments designed to evaluate factors controlling desorption indicate that two anionic surfactants, AOK and T77, at concentrations ranging from 60 to 200 mM, are most suitable for U(VI) removal from acidic soils such as the Oak Ridge sediment. These surfactants are very efficient solubilizing agents at low uranium concentrations: ca. 100% U(VI) removal for [U(VI)]o,sorbed = 10(-6) mol kg-1. At greater uranium concentrations (e.g., [U(VI)]o,sorbed = ca. 10(-5) mol kg-1), the desorption efficiency of the surfactant solutions increases with an increase in surfactant concentration and reaches a plateau of 75 to 80% of the U(VI) initially sorbed. The most probable mechanisms responsible for U(VI) desorption include cation exchange in the electric double layer surrounding the micelles and, to a lesser extent, dissolution of the soil matrix. Limitations associated with the surfactant treatment include loss of surfactants onto the soil (sorption) and greater affinity between U(VI) and the soil matrix at large soil to liquid ratios. Parallel experiments with H2SO4 and carbonate-bicarbonate (CB) solutions indicate that these more conventional methods suffer from strong matrix dissolution with the acid and reduced desorption efficiency with CB due to the buffering capacity of the acidic soil.     

Tillage, intercrop, and controlled drainage-subirrigation influence atrazine, metribuzin, and metolachlor loss

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] have been found with increasing occurrence in rivers and streams. Their continued use will require changes in agricultural practices. We compared water quality from four crop-tillage treatments: (i) conventional moldboard plow (MB), (ii) MB with ryegrass (Lolium multiflorum Lam.) intercrop (IC), (iii) soil saver (SS), and (iv) SS + IC; and two drainage control treatments, drained (D) and controlled drainage-subirrigation (CDS). Atrazine (1.1 kg a.i. ha-1), metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazine-5(4H)-one] (0.5 kg a.i. ha-1), and metolachlor (1.68 kg a.i. ha-1) were applied preemergence in a band over seeded corn (Zea mays L.) rows. Herbicide concentration and losses were monitored from 1992 to spring 1995. Annual herbicide losses ranged from < 0.3 to 2.7% of application. Crop-tillage treatment influenced herbicide loss in 1992 but not in 1993 or 1994, whereas CDS affected partitioning of losses in most years. In 1992, SS + IC reduced herbicide loss in tile drains and surface runoff by 46 to 49% compared with MB. The intercrop reduced surface runoff, which reduced herbicide transport. Controlled drainage-subirrigation increased herbicide loss in surface runoff but decreased loss through tile drainage so that total herbicide loss did not differ between drainage treatments. Desethyl atrazine [6-chloro-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine] comprised 7 to 39% of the total triazine loss.     

The relationship between microbial carbon and the resource quality of soil carbon

The biological health of soil is an important aspect of soil quality because of the many critical functions performed by organisms in soil. Various indicators of soil quality have been proposed, but measurements of microbial biomass are most commonly used. During decomposition of plant residues in soil the relative intensities of the O-alkyl-C signal decreases and the alkyl-C signal increases in nuclear magnetic resonance (NMR) spectra. This leads to the suggestion that the alkyl-C to O-alkyl-C ratio of a soil may indicate the degree of decomposition. Consequently, the overall resource quality of soil C as a substrate for heterotrophic microorganisms may be inversely related to the alkyl-C to O-alkyl-C ratio. Our hypothesis is that a relationship exists between the size of the soil microbial community (microbial biomass) and the quality of soil carbon as a resource for microorganisms. New data have been combined with previously published data to show that there was a significant, negative correlation between the biomass C to total C (Cmic, to Corg) ratio and the alkyl-C to O-alkyl-C ratio (p < 0.01), which supports our hypothesis.     

Copper and calcium transport through an unsaturated soil column

To determine the relative importance of the physical and chemical factors that influence the movement of heavy metals through soils, leaching experiments were carried out under conditions of constant molarity during unsaturated steady-state water flow through a Manawatu fine sandy loam (a Dystric Fluventic Eutochrept). The movement and exchange of copper was studied in a binary Cu-Ca system. The movement of the associated anions, namely chloride and sulfate, was also monitored. The measurements were compared with predictions from the convection-dispersion equation (CDE), linked with cation exchange theory. The agreement between the measured and predicted breakthrough of sulfate and copper was good. This indicates that copper retardation in the Manawatu soil is closely related to the cation exchange capacity, and that exchange between Ca and Cu is the main process of Cu retardation in the Manawatu soil. However, copper appeared slightly later in the effluent than predicted, indicating that non-exchange processes are also involved in copper transport. Measurements of suction cups could also be used to obtain the parameters for the CDE to describe sulfate movement through the soil. Time domain reflectometry (TDR) measurements of the bulk-soil electrical conductivity could be used to monitor the movement of both sulfate and copper. This indicates that TDR can also be used to monitor cation transport and exchange through the soil, provided the percolating solution causes a sufficient change in the electrical conductivity.     

Vertical Distribution of Atmospheric Pollution Lead in Swedish Boreal Forest Soils

In order to understand the fate of anthropogenic lead (Pb)pollution in boreal forest soils, and to predict future trends, it is important to know where in the soil the pollution Pb is accumulated and how large the pollution and natural Pb inventories are in different soil horizons. We combined stable Pb isotope (²⁰⁶Pb/²⁰⁷Pb ratios) and concentration analyses to study Pb in podzol profiles and mor samples from old-growth forest stands at seven sites distributed from southern to northern Sweden. Additional samples were taken from managed forests, and from an agricultural field, to give some idea of the effects of land-use. Pb concentrations are typically 60–100 g g^-1 dry mass in the mor layer in southern Sweden and about 30 g g^-1 in northern Sweden. Pb isotope analyses show that virtually all of this Pb is pollution Pb. The isotope composition also shows that pollution Pb has penetrated downwards between 20–60 cm in the forest soils. The total pollution Pb inventories vary between 0.7–3.0 g m^-2 ground surface, with larger inventories in southern compared to northern Sweden. Although the highest Pb concentrations occur in the mor layer, the largest inventories of pollution Pb are found in the Bs-horizon. The limited investigation of Pb distribution and inventories in soils from managed forests did not point to any major difference compared to the old-growth forests. The agricultural field revealed, however, a completely deviating Pb profile with all pollution Pb evenly distributed in the 20 cm thick top-soil.     

Alfalfa rapidly remediates excess inorganic nitrogen at a fertilizer spill site

By 19%, standard remediation techniques had significantly reduced the concentration of nitrate nitrogen (NO3- -N) in local ground water at the site of a 1989 anhydrous ammonia spill, but NO3- -N concentrations in portions of the site still exceeded the public drinking water standard. Our objective was to determine whether local soil and ground water quality could be improved with alfalfa (Medicago sativa L.). A 3-yr study was conducted in replicated plots (24 by 30 m) located hydrologically upgradient of the ground water under the spill site. Three alfalfa entries ['Agate', Ineffective Agate (a non-N2-fixing elite germplasm similar to Agate), and MWNC-4 (an experimental germplasm)] were seeded in the spring of 1996. Corn (Zea mays L.) or wheat (Triticum aestivum L.) was seeded adjacent to the alfalfa each year. Crops were irrigated with N-containing ground water to meet water demand. During the 3-yr period, about 540 kg of inorganic N was removed from the aquifer through irrigation of 4.9 million L water. Cumulative N removal from the site over 3 yr was 972 kg N ha(-1) in Ineffective Agate alfalfa hay, compared with 287 kg N ha(-1) for the annual cereal grain. Soil solution NO3- concentrations were reduced to low and stable levels by alfalfa, but were more variable under the annual crops. Ground water quality improved, as evidenced by irrigation water N concentration. We do not know how much N was removed by the N2-fixing alfalfas, but it appears that either fixing or non-N2-fixing alfalfa will effectively remove inorganic N from N-affected sites.