Influence of fly ash on soil physical properties and turfgrass establishment

A field study (1993-96) assessed the benefits of applying unusually high rates of coal fly ash as a soil amendment to enhance water retention of soils without adversely affecting growth and marketability of the turf species, centipedegrass [Eremochloa ophiuroides (Munro) Hack.]. A Latin Square plot design was employed that included 0 (control, no ash applied), 280, 560, and 1120 Mg ha-1 application rates of unweathered precipitator fly ash. The fly ash was spread evenly over each plot area, rototilled, and allowed to weather under natural conditions for 8 mo before seeding. High levels of soluble salts, indicated by the electrical conductivity (EC) of soil extracts, in tandem with an apparent phytotoxic effect from boron (B), apparently inhibited initial plant establishment as shown by substantially lower germination counts in treated soil. However, plant height and rooting depth were not adversely affected, as were the dry matter (DM) yields throughout the study period. Ash treatment did not significantly influence water infiltration rate, bulk density, or temperature of the soil, but substantially improved water-holding capacity (WHC) and plant-available water (PAW). Enhanced water retention capacity improved the cohesion and handling property of harvested sod.     

Temporal changes in soil partitioning and bioaccessibility of arsenic, chromium, and lead

The hazard imposed by trace element contaminants within soils is dependent on their ability to migrate into water systems and their availability for biological uptake. The degree to which a contaminant may dissociate from soil solids and become available to a target organism (i.e., bioaccessibility) is therefore a determining risk factor. We used a physiologically based extraction test (PBET) to estimate the bioaccessible fraction of arsenic-, chromium-, and lead-amended soil. We investigated soils from the A and B horizons of the Melton Valley series, obtained from Oak Ridge National Laboratory site, to address temporal changes in bioaccessibility. Additionally, common extractions that seek to define reactive pools of metals were employed and their correlation to PBET levels evaluated. With the exception of Pb amended to the A horizon, all other treatments exhibited an exponential decrease in bioaccessibility with incubation time. The bioaccessible fraction was less than 0.2 mg kg(-1) within 30 d of incubation for As and Cr in the A horizon and for As and Pb within the B horizon; Cr in the B horizon declined to nearly 0.3 mg kg(-1) within 100 d of aging. The exchangeable fraction declined with incubation period and, with the exception of Pb, was highly correlated with the decline in bioaccessibility. Our results demonstrate limited bioaccessibility in all but one case and the need to address both short-term temporal changes and, most importantly, the soil physiochemical properties. They further reveal the importance of incubation time on the reactivity of such trace elements.     

Papermill biosolids effect on soil physical and chemical properties

Papermill biosolids (PB) can provide multiple benefits to the soil system. The purpose of this study was to quantify the effects of a high C/N ratio (C/N = 100) de-inked PB on soil physical and chemical properties, including soil bulk density, infiltration rates, wet aggregate stability, total soil carbon, and heavy metal concentrations. Four rates of PB (0, 50, 100, and 150 Mg ha(-1)) were applied annually, for up to 3 yr, on four agricultural soils in Ontario, Canada. Decreases in soil bulk density between 0.27 and 0.35 g cm(-3), relative to the nonamended treatment, were observed in soils receiving PB treatments over 3 yr. Total soil carbon increased within 1 yr on PB-amended soils planted to soybeans but not on soils planted to corn. Hydraulic conductivities (K fs) were greater in all soils receiving PB amendments relative to the nonamended treatment throughout the study. Other properties measured, such as pH and electrical conductivity, were relatively unchanged after 2 yr of PB applications. While some increases in heavy metal accumulation occurred, there were no clear trends observed at any of the sites related to PB rates. The results of this study provide support to the idea that annual applications of PB can add significantly to the stability of soil structure.     

Light-catalyzed chromium(VI) reduction by organic compounds and soil minerals

Detoxification of Cr(VI) through reduction has been considered an effective method for reclaiming Cr-contaminated soil, sediment, and waste water. Organic matter is widely distributed in soil and aquatic systems; however, low Cr(VI) reduction rates inhibit the adoption of Cr reduction technologies by industry. Scientists have been aware of Cr(VI) reduction catalyzed by soil minerals; however, most of the studies focused on using semiconductors as catalysts with UV irradiation to accelerate the redox reactions. The objective of this study was to evaluate the rates of Cr(VI) reduction by fluorescence light in the presence of organic materials with or without specific soil minerals. Experimental results showed that dissolved organic compounds reduced Cr(VI) slowly under laboratory light; however, Cr(VI) reduction was greatly enhanced when growth chamber light was applied. Low photon flux (i.e., laboratory light) only enhanced Cr(VI) reduction by organics when Fe(III) was also present, because the Fe(II)-Fe(III) redox couple accelerated electron transfer and decreased electrostatic repulsion between reactants. Laboratory light was required to initiate Cr(VI) reduction catalyzed by TiO2; nonetheless, light-catalyzed Cr(VI) reduction by smectite and ferrihydrite could occur only when greater light energy was provided with a growth chamber light. Our results suggest a potential pathway for Cr(VI) reduction using naturally occurring organic compounds and colloids in acidic water systems or in surface soils when light is available.     

Use of modified hydroxy-aluminum bentonites for chromium(III) removal from solutions

The retention of chromium(III) from a 2000ppm chromium basic sulfate and tannery waste solution at pH 4.5 using modified hydroxy-aluminum bentonites (OH-Al bentonites) as adsorbents was studied. OH-Al bentonite was prepared by mixing clay with a hydrolyzed commercial chlorohydroxy Al solution. The modified Al bentonites were obtained by (a) a treatment with 0.5M sodium chloride and (b) a treatment with a Na-hexametaphosphate solution (HMP) after adding sodium chloride. The effect of heating the adsorbents at 100, 500, 700 and 800 degrees C on Cr retention as a function of time was also analyzed. Cr retention by modified OH-Al bentonite with HMP increased with time (up to 100mgCr/g) where modified OH-Al bentonite was twice that of untreated bentonite. The relatively high uptake of metal from the salt solution by modified OH-Al bentonite treated at 800 degrees C, in which a complete interlayer collapse occurred, indicated the importance of the contribution of external surface sites to the retention capacity. The maximum Cr uptake from a water waste was 24mg/g, due to interferences and different chromium species in the industrial solution.     

Low-temperature chromium(VI) biotransformation in soil with varying electron acceptors

Effective and low-cost strategies for remediating chromium (Cr)-contaminated soil are needed. Chromium(VI) leaching from contaminated soil into ground water and surface water threatens water supplies and the environment. This study tested indigenous Cr(VI) microbial transformation in batch systems at 10 degrees C in the presence of various electron acceptors. The effects of carbon addition, spiked Cr(VI), and mixing highly contaminated soil with less contaminated soil were investigated. The results indicated that Cr(VI) can be biotransformed in the presence of different electron acceptors including oxygen, nitrate, sulfate, and iron. Sugar addition had the greatest effect on enhancing Cr(VI) removal. Less dissolved organic carbon (DOC) was consumed per amount of Cr(VI) transformed under anaerobic conditions [0.8-93 mg DOC/mg Cr(VI)] compared with aerobic conditions [1.4-265 mg DOC/mg Cr(VI)]. Toxicity of high concentrations (< 160 mg/L) of spiked Cr(VI) were not evident. At Cr(VI) concentrations > 40 mg/L, aerobic conditions promoted faster Cr(VI) reduction than anaerobic conditions with nitrate or sulfate present. Biotransformation of Cr(VI) in highly contaminated soil (22,000 mg Cr/kg) was facilitated by mixing with less-contaminated soil. The study results provide a framework for evaluating indigenous Cr(VI) microbial transformation and enhance the ability to develop strategies for soil treatment.     

Paper mill residuals and compost effects on soil carbon and physical properties

Use of organic by-products as soil amendments in agricultural production exemplifies a strategy for converting wastes to resources. The overall objective of this research was to evaluate the short- and intermediate-term effects of repeatedly amending sandy soil with paper mill residuals (PMR) and composted PMR in a vegetable rotation in Wisconsin's Central Sands. Specifically, we investigated the effects of PMR and composted PMR on total soil C and related these to changes in water-holding capacity and plant-available water (PAW). Amendment effects on irrigation requirements were estimated with a simple soil water balance model. The experimental design was replicated five times as a randomized complete block with four organic amendments: raw PMR, PMR composted alone (PMRC), PMR composted with bark (PMRB), and peat applied at two rates and a non-amended control. All amended treatments significantly increased total soil C relative to the nonamended control following applications in 1998 and 1999. One year following the second serial amendment, all PMR treatments increased PAW by 5 to 45% relative to the control. There was a significant positive linear relationship between total soil C and PAW. All amended treatments reduced the average amount of irrigation water required for potato production by 4 to 30% and the number of irrigation events by 10 to 90%. There was a clear trend of greater reduction in irrigation requirements with more carbon added. The cumulative effects of repeated additions of PMRB suggest that certain composts might sustain elevated PAW and reduce irrigation requirements beyond one year.     

Herbicide sorption coefficients in relation to soil properties and terrain attributes on a cultivated prairie

The sorption of 2,4-D and glyphosate herbicides in soil was quantified for 287 surface soils (0-15 cm) collected in a 10 x 10 m grid across a heavily eroded, undulating, calcareous prairie landscape. Other variables that were determined included soil carbonate content, soil pH, soil organic carbon content (SOC), soil texture, soil loss or gain by tillage and water erosion, and selected terrain attributes and landform segments. The 2,4-D sorption coefficient (Kd) was significantly associated with soil carbonate content (-0.66; P < 0.001), soil pH (-0.63; P < 0.001), and SOC (0.47; P < 0.001). Upper slopes were strongly eroded and thus had a significantly greater soil carbonate content and less SOC compared with lower slopes that were in soil accumulation zones. The 2,4-D Kd was almost twice as small in upper slopes than in lower slopes. The 2,4-D Kd was also significantly associated with nine terrain attributes, particularly with compounded topographic index (0.59; P < 0.001), gradient (-0.48; P < 0.001), mean curvature (-0.43; P < 0.001), and plan curvature (-0.42 P < 0.001). Regression equations were generated to estimate herbicide sorption in soils. The predicted power of these equations increased for 2,4-D when selected terrain attributes were combined with soil properties. In contrast, the variation of glyphosate sorption across the field was much less dependent on our measured soil properties and calculated terrain attributes. We conclude that the integration of terrain attributes or landform segments in pesticide fate modeling is more advantageous for herbicides such as 2,4-D, whose sorption to soil is weak and influenced by subtle changes in soil properties, than for herbicides such as glyphosate that are strongly bound to soil regardless of soil properties.     

Influence of decomposition on chemical properties of plant- and manure-derived dissolved organic matter and sorption to goethite

Sorption of dissolved organic matter (DOM) plays an important role in maintaining the fertility and quality of soils in agricultural ecosystems. Few studies have examined the effects of decomposition on DOM sorption and chemical characteristics. This study investigated the sorption to goethite (alpha-FeOOH) of fresh and decomposed hydrophilic (HPL) and hydrophobic (HPB) DOM fractions extracted from the shoots and roots of crimson clover (Trifolium incarnatum L.), corn (Zea mays L.), soybean [Glycine max (L.) Merr.], hairy vetch (Vicia villosa L.), and dairy and poultry manures. Sorption was positively related to apparent molecular weight (MWAP), aromaticity as measured by absorptivity at 280 nm, and phenolic acid content. A 10-d laboratory microbial decomposition of the source organic matter generally increased the sorption of the extracted DOM onto goethite. The decomposition effect on sorption was greater for the HPL fractions than for the HPB fractions. There was a decrease in the MWAP values of the DOM samples following sorption to goethite. In many cases the reduction in MWAP was large, indicating a strong preference by goethite for the higher MWAP DOM fractions. The results of this laboratory-based research demonstrate that microbial processes affect the chemical characteristics of DOM which may affect the distribution of soil organic C pools.     

Field-scale variation in microbial activity and soil properties in relation to mineralization and sorption of pesticides in a sandy soil

Pesticides applied to agricultural soils are subject to environmental concerns because leaching to groundwater reservoirs and aquatic habitats may occur. Knowledge of field variation of pesticide-related parameters is required to evaluate the vulnerability of pesticide leaching. The mineralization and sorption of the pesticides glyphosate and metribuzin and the pesticide degradation product triazinamin in a field were measured and compared with the field-scale variation of geochemical and microbiological parameters. We focused on the soil parameters clay and organic carbon (C) content and on soil respiratory and enzymatic processes and microbial biomass. These parameters were measured in soil samples taken at two depths (Ap and Bs horizon) in 51 sampling points from a 4-ha agricultural fine sandy soil field. The results indicated that the spatial variation of the soil parameters, and in particular the content of organic C, had a major influence on the variability of the microbial parameters and on sorption and pesticide mineralization in the soil. For glyphosate, with a co-metabolic pathway for degradation, the mineralization was increased in soils with high microbial activity. The spatial variability, expressed as the CV, was about five times higher in the Bs horizon than in the Ap horizon, and the local-scale variation within 100 m(2) areas were two to three times lower than the field-scale variation within the entire field of about 4 ha.     

A spatially explicit investigation of phosphorus sorption and related soil properties in two riparian wetlands

Soils of riparian wetlands are highly effective at phosphorus (P) sorption. However, these soils exhibit extreme spatial variability across riparian zones. We used a spatially explicit sampling design in two riparian wetlands in North Carolina to better understand the relationships among P sorption, soil properties, and spatial variability. Our objectives were to quantify patterns of spatial variability of P sorption and related soil properties, and to determine which soil properties best explained the variability in P sorption after accounting for the effects of spatial autocorrelation. We measured bulk density, moisture, pH, soil organic matter (SOM), texture (percent clay, silt, and sand), oxalate-extractable aluminum (Al(ox)), iron (Fe(ox)), and the phosphorus sorption index (PSI). Due to differences in texture, Al(ox), and Fe(ox), the two sites had substantially different mean PSIs. At each site, we found considerable differences in the spatial variability of soil properties. For example, semivariance analysis and kriging illustrated that soil properties at Site 1 varied at smaller scales than those at Site 2. At both sites, after accounting for the effects of spatial autocorrelation and all other soil properties, we determined that Al(ox) had the highest Mantel correlation with PSI. We believe this geostatistic and Mantel approach is robust and could serve as a model for research on other biogeochemical processes such as denitrification.     

Influence of soil properties and aging on the toxicity of copper on compost worm and barley

Influence of soil properties and aging on Cu partitioning and toxicity was assessed on 10 artificial soils constituted using a statistical design considering pH (5.5 and 7.5), organic matter (1-30% [w/w]), and clay content (5-35% [w/w]). Total Cu as well as water-, CaCl2-, and diethylene triamine pentaacetic acid (DTPA)-extracted Cu fractions were determined for each soil mixture. Ecotoxic effect was assessed by determining growth inhibition of barley (Hordeum vulgare L.) and compost worm (Eisenia fetida) mortality. Analyses were repeated after a 16-wk aging period of the soils at pH 7.5 (8 x 2-wk wetting and drying cycle). Results indicated that pH was the main factor controlling Cu partitioning, ahead of organic matter and clay content. Calcium chloride (0.5 M)-extracted Cu fractions showed the best correlation with toxic responses (r = 0.55-0.66; p < 0.05), while total and DTPA-extracted Cu concentrations could not explain differences in toxicity. Direct regressions between toxicity and soil properties (pH, organic matter, and clay content) provided better explanation of variance: r2= 0.50 (p = 0.00006) for compost worm mortality, r2= 0.77 (p < 0.00001) for barley shoot inhibition, and r2= 0.92 (p < 0.00001) for barley root inhibition. Copper toxicity was mainly influenced by pH and, to a lesser extent, by organic matter and clay content. Aging in organic soils revealed a slight reduction in ecotoxicity while an increase was observed in soils with low organic matter content. Further investigation using longer aging periods would be necessary to assess the significance of this observation.     

Role of soil sorption and microbial degradation on dissipation of mesotrione in plant-available soil water

Mesotrione is a carotenoid biosynthesis-inhibiting herbicide labeled for pre-emergence and postemergence weed control in corn production. Understanding the factors that influence the dissipation of mesotrione in soil and in the plant-available water (PAW) is important for the environmental fate assessment and optimal weed management practices. The present research investigated the role of soil properties and microbial activities on the interrelated sorption and degradation processes of mesotrione in four soils by direct measurements of PAW. We found that mesotrione bound to the soils time dependently, with approximately 14 d to reach equilibrium. The 24-h batch-slurry equilibrium experiments provided the sorption partition coefficient ranging from 0.26 to 3.53 L kg(-1), depending on soil organic carbon and pH. The dissipation of mesotrione in the soil-bound phase was primarily attributed to desorption to the PAW. Degradation in the PAW was rapid and primarily dependent on microbial actions, with half-degradation time (DT(50)) <3 d in all four soils tested. The rapid degradation in the PAW became rate limited by sorption as more available molecules were depleted in the soil pore water, resulting in a more slowed overall process for the total soil-water system (DT(50) <26 d). The dissipation of mesotrione in the PAW was due to microbial metabolism and time-dependent sorption to the soils. A coupled kinetics model calibrated with the data from the laboratory centrifugation technique provided an effective approach to investigate the interrelated processes of sorption and degradation in realistic soil moisture conditions.     

Predicting physical and chemical water properties from relationships with watershed soil characteristics

The Surface Waters component of the Environmental Monitoring and Assessment Program (EMAPSW) was developed by the USEPA to evaluate the extent and condition of lakes and streams over national and regional scales. Realistically, chemical or physical water properties (WPs) such as acidity or turbidity can be field-sampled for only a small portion of all lakes and streams. However, soil characteristics (SCs) affect WPs and broad-scale soil survey data have become available in the State Soil Geographic Data Base (STATSGO). We developed models relating observed WPs to SCs to extrapolate the sampled WPs to a region, potentially reducing extensive monitoring needs. Our study region consisted of 13 northeastern and Mid-Atlantic states and contained 882 STATSGO soil map units. We used map units as the spatial component of WP analysis. The WPs were sampled in 721 randomly selected EMAPSW study sites. The watersheds of these sites represent 7.1% of the region's total area and spatially intersect 400 of its soil map units. Each intersected map unit was assigned the weighted average WPs from the corresponding watersheds. Conditional expectation models were used to extrapolate sampled WPs to 882 map units. The relative standard errors ranged from low for pH (0.8%), intermediate for total P (12.1%), and very high for chloride (54.8%). The high extrapolation errors indicate outlier conditions from natural, non-soil, or anthropogenic sources.     

Long-term effect of a single application of organic refuse on carbon sequestration and soil physical properties

Restoration of degraded lands could be a way to reverse soil degradation and desertification in semiarid areas and mitigate greenhouse gases (GHG). Our objective was to evaluate the long-term effects of a single addition of organic refuse on soil physical properties and measure its carbon sequestration potential. In 1988, a set of five plots (87 m(2) each) was established in an open desert-like scrubland (2-4% cover) in Murcia, Spain, to which urban solid refuse (USR) was added in a single treatment at different rates. Soil properties were monitored over a 5-yr period. Sixteen years after the addition, three of the plots were monitored again (P0: control, P1: 13 kg m(-2), P2: 26 kg m(-2) of USR added) to assess the lasting effect of the organic addition on the soil organic carbon (SOC) pools and on the physical characteristics of the soil. The SOC content was higher in P2 (16.4 g kg(-1)) and in P1 (11.8 g kg(-1)) than in P0 (7.9 g kg(-1)). Likewise, aerial biomass increased from 0.18 kg m(-2) in P0 up to 0.27 kg m(-2) in P1 and 0.46 kg m(-2) in P2. This represents a total C sequestration of 9.5 Mg ha(-1) in P2 and 3.4 Mg ha(-1) in P1, most of the sequestered C remaining in the recalcitrant soil pool. Additionally, higher saturated hydraulic conductivity, aggregate stability, and available water content values and lower bulk density values were measured in the restored plots. Clearly, a single addition of organic refuse to the degraded soils to increase the potential for C sequestration was effective.     

A comparative study for the sorption of Cd(II) by K-feldspar and sepiolite as soil components, and the recovery of Cd(II) using rhamnolipid biosurfactant

This study investigated the sorption characteristics and recovery of selected heavy metal Cd(II) from K-feldspar and sepiolite, representative soil components, using rhamnolipid biosurfactant. Although the proposed technique was classified as a soil bioremediation process, it can also be applied to treatment of waste waters containing Cd(II) ions with minor modifications. The effect of initial Cd(II) concentration on sorption capacity was characterized by determining the sorption isotherms. Of the four models examined, the Freundlich model showed the best fit for the sorption of Cd(II) on K-feldspar, whereas the Langmuir-model was used successfully to characterize the sorption of Cd(II) on sepiolite. Although a high Cd(II) uptake of 7.49 mmol/kg by K-feldspar was obtained, sepiolite was a superior Cd(II) accumulater, with a maximum Cd(II) uptake of 24.66 mmol Cd(II)/kg. The presence of Cd(II) in the sepiolite or K-feldspar prior to addition of the rhamnolipid generally resulted in less rhamnolipid sorption to sepiolite or K-feldspar. The maximum Cd(II) desorption efficiency by rhamnolipid from K-feldspar was substantially higher than that of sepiolite and determined to be 96% of the sorbed Cd(II), whereas only 10.1% of the sorbed Cd(II) from sepiolite was recovered by rhamnolipid solution.     

Effects of dissolved organic carbon on sorption and mobility of imidacloprid in soil

To evaluate the effects of dissolved organic carbon on sorption and mobility of the insecticide imidacloprid [1-(6-chloro-3-pyridinyl) methyl-N-nitro-2-imidazolidinimine] in soils, adsorption and column experiments were performed by using a typical calcareous soil from southeastern Spain and two different types of dissolved organic carbon, that is, dissolved organic carbon extracts from a commercial peat (DOC-PE) and high-purity tannic acid (DOC-TA). The experiments were carried out from a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results obtained from the sorption experiments show that the presence of both DOC-PE and DOC-TA, over a concentration range of 15 to 100 mg L(-1), produces in all cases a decreasing amount of imidacloprid adsorbed in the soil studied. From the column experiments the retardation coefficients (RC) were calculated for imidacloprid by using either 0.01 M CaCl2 aqueous solution (RC = 2.10), 0.01 M CaCl2 DOC-PE solution (RC = 1.65), or 0.01 M CaCl2 DOC-TA solution (RC = 1.87). The results indicate that mobility of imidacloprid is increased 21.4 and 11.0% in the presence of DOC-PE and DOC-TA solutions, respectively. Dissolved organic carbon reduces imidacloprid sorption by competing with the pesticide molecules for sorption sites on the soil surface, allowing enhanced leaching of imidacloprid and potentially increasing ground water contamination.     

Distribution of chromium contamination and microbial activity in soil aggregates

Biogeochemical transformations of redox-sensitive chemicals in soils can be strongly transport-controlled and localized. This was tested through experiments on chromium diffusion and reduction in soil aggregates that were exposed to chromate solutions. Reduction of soluble Cr(VI) to insoluble Cr(II) occurred only within the surface layer of aggregates with higher available organic carbon and higher microbial respiration. Sharply terminated Cr diffusion fronts develop when the reduction rate increases rapidly with depth. The final state of such aggregates consists of a Cr-contaminated exterior, and an uncontaminated core, each having different microbial community compositions and activity. Microbial activity was significantly higher in the more reducing soils, while total microbial biomass was similar in all of the soils. The small fraction of Cr(VI) remaining unreduced resides along external surfaces of aggregates, leaving it potentially available to future transport down the soil profile. Using the Thiele modulus, Cr(VI) reduction in soil aggregates is shown to be diffusion rate- and reaction rate-limited in anaerobic and aerobic aggregates, respectively. Thus, spatially resolved chemical and microbiological measurements are necessary within anaerobic soil aggregates to characterize and predict the fate of Cr contamination. Typical methods of soil sampling and analyses that average over redox gradients within aggregates can erase important biogeochemical spatial relations necessary for understanding these environments.     

Effect of dissolved organic matter from sludge and sludge compost on soil copper sorption

Interaction of Cu with dissolved organic matter (DOM) is an important physicochemical process affecting Cu mobility in soils. The aim of this study was to investigate the effects of DOM from anaerobically digested dewatered sludge and sludge compost on the sorption of Cu on an acidic sandy loam and a calcareous clay loam. In the presence of DOM, Cu sorption capacity decreased markedly for both soils, especially for the calcareous soil. The Cu sorption isotherms could be well described by the Freundlich equation (r2 = 0.99), and the binding intensity parameter of soils in the presence of sludge DOM was lower than compost DOM. An increase in DOM concentration significantly reduced the sorption of Cu by both soils. Within the Cu and DOM concentration range studied, the decrease in Cu sorption caused by sludge DOM was consistently greater than that of compost DOM. This might be attributed to the greater amount of hydrophobic fraction of DOM in the compost. Moreover, the reduction of Cu sorption caused by DOM was more obvious in the soil with higher pH. In addition, the sorption of Cu increased with an increase in pH for both soils without the addition of DOM, while Cu sorption in the presence of DOM was unexpectedly decreased with an increase in pH at a pH >6.8. This implied that DOM produced by sludge or other C-enriched organic wastes heavily applied on calcareous soils might facilitate the leaching loss of Cu because of the formation of soluble DOM-metal complexes.     

Degradation and sorption of metribuzin and primary metabolites in a sandy soil

Leaching to the ground water of metabolites from the herbicide metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5-one] has been measured in a Danish field experiment in concentrations exceeding the European Union threshold limit for pesticides at 0.1 microg/L. In the present work, degradation and sorption of metribuzin and the metabolites desamino-metribuzin (DA), diketo-metribuzin (DK), and desamino-diketo-metribuzin (DADK) were studied in a Danish sandy loam topsoil and subsoil from the field in question, using accelerated solvent extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. Fast dissipation of metribuzin and the metabolites was observed in the topsoil, with 50% disappearance within 30 to 40 d. A two-compartment model described degradation of metribuzin and DA, whereas that of DADK could be described using first-order kinetics. Part of the dissipation was probably due to incorporation into soil organic matter. Degradation in subsoil occurred very slowly, with extrapolated half-lives of more than one year. Sorption in the topsoil followed the order DA > metribuzin > DK > DADK. Subsoil sorption was considerably lower, and was hardly measurable for metribuzin and DK. Abiotic degradation was considerably higher in the topsoil than the subsoil, especially concerning the de-amination step, indicating that organic matter may be related to the degradation process. The present results confirm observations of metribuzin and transformation product leaching made in the field experiment and demonstrate the need for knowledge on primary metabolites when assessing the risk for pesticide leaching.