Influence of biochar amendments on the sorption-desorption of aminocyclopyrachlor, bentazone and pyraclostrobin pesticides to an agricultural soil.

The many advantageous properties of biochar have led to the recent interest in the use of this carbonaceous material as a soil amendment. However, there are limited studies dealing with the effect of biochar on the behavior of pesticides applied to crops. The objective of this work was to determine the effect of various biochars on the sorption-desorption of the herbicides aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinacarboxylic acid) and bentazone (3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide) and the fungicide pyraclostrobin (methyl 2-[1-(4-chlorophenyl) pyrazol-3-yloxymethil]-N-methoxycarbanilate) to a silt loam soil. Aminocyclopyrachlor and bentazone were almost completely sorbed by the soils amended with the biochars produced from wood pellets. However, lower sorption of the herbicides was observed in the soils amended with the biochar made from macadamia nut shells as compared to the unamended soil, which was attributed to the competition between dissolved organic carbon (DOC) from the biochar and the herbicides for sorption sites. Our results showed that pyraclostrobin is highly sorbed to soil, and the addition of biochars to soil did not further increase its sorption. Thus, addition of biochars to increase the retention of low mobility pesticides in soil appears to not be necessary. On the other hand, biochars with high surface areas and low DOC contents can increase the sorption of highly mobile pesticides in soil.

Impacts of woodchip biochar additions on greenhouse gas production and sorption/degradation of two herbicides in a Minnesota soil.

A potential abatement to increasing levels of carbon dioxide (CO(2)) in the atmosphere is the use of pyrolysis to convert vegetative biomass into a more stable form of carbon (biochar) that could then be applied to the soil. However, the impacts of pyrolysis biochar on the soil system need to be assessed before initiating large scale biochar applications to agricultural fields. We compared CO(2) respiration, nitrous oxide (N(2)O) production, methane (CH(4)) oxidation and herbicide retention and transformation through laboratory incubations at field capacity in a Minnesota soil (Waukegan silt loam) with and without added biochar. CO(2) originating from the biochar needs to be subtracted from the soil-biochar combination in order to elucidate the impact of biochar on soil respiration. After this correction, biochar amendments reduced CO(2) production for all amendment levels tested (2, 5, 10, 20, 40 and 60% w/w; corresponding to 24-720 tha(-1) field application rates). In addition, biochar additions suppressed N(2)O production at all levels. However, these reductions were only significant at biochar amendment levels >20% w/w. Biochar additions also significantly suppressed ambient CH(4) oxidation at all levels compared to unamended soil. The addition of biochar (5% w/w) to soil increased the sorption of atrazine and acetochlor compared to non-amended soils, resulting in decreased dissipation rates of these herbicides. The recalcitrance of the biochar suggests that it could be a viable carbon sequestration strategy, and might provide substantial net greenhouse gas benefits if the reductions in N(2)O production are lasting.

Linuron sorption-desorption in field-moist soils.

Pesticide sorption or binding to soil is traditionally characterized using batch slurry techniques. The objective of this study was to determine linuron sorption in field-moist or unsaturated soils. Experiments were performed using low-density (i.e., 0.25 g mL(-)(1)) supercritical carbon dioxide to remove linuron from the soil water phase, thus allowing calculation of sorption coefficients (K(d)) at low water contents. Both soil water content and temperature influenced sorption. K(d) values increased with increased water content, if less than saturated. K(d) values decreased with increased temperature. K(d) values for linuron sorption on silty clay and sandy loam soils at 12% water content and 40 degrees C were 3.9 and 7.0 mL g(-)(1), respectively. Isosteric heats of sorption (DeltaH(i)) were -41 and -35 kJ mol(-)(1) for the silty clay and sandy loam soils, respectively. The sorption coefficient obtained using the batch method was comparable (K(f) for sandy loam soil = 7. 9 microg(1)(-)(1/)(n)() mL(1/)(n)() g(-)(1)) to that obtained using the SFE technique. On the basis of these results, pesticide sorption as a function of water content must be known to more accurately predict pesticide transport through soils.

LC/MS analysis of cyclohexanedione oxime herbicides in water.

A multiresidue method for the determination of alloxydim (methyl 2, 2-dimethyl-4, 6-dioxo-5-[1-[2-propenyloxy)amino]butylidene]cyclohexanec arb oxylate), clethodim (E, E)-(+/-)-2-[1-[[3-chloro-2-propenyl)oxy]imino]propyl]-5-[2-(ethylthio )propyl]-3-hydroxy-2-cyclohexen-1-one), sethoxydim ((+/-)-2-[1-(ethoxyimino)butyl]-5-[2-ethylthio)propyl]-3-hydroxy-2 -cy clohexen-1-one), and two metabolites, clethodim sulfoxide ((E, E)-(+/-)-2-[1-[[3-chloro-2-propenyl)oxy]imino]propyl]-5-[2-(ethylsulf inyl)propyl]-3-hydroxy-2-cyclohexen-1-one) and sethoxydim sulfoxide ((+/-)-2-[1-(ethoxyimino)butyl]-5-[2-ethylsulfinyl)propyl]-3 -hydroxy- 2-cyclohexen-1-one), in water by high-performance liquid chromatography/electrospray/mass spectrometry (LC/ES/MS) is reported. River water and distilled water were spiked at 0.08 and 0.8 microgram L(-1) with all three herbicides, which were then extracted from the water by C(18)-SPE (SPE = solid-phase extraction). The herbicides and metabolites were quantified and confirmed using selected ion monitoring. The percent recoveries of the herbicides from water spiked at 0.8 microgram L(-1) were as follows: alloxydim, 117 +/- 11%; clethodim, 96 +/- 14%; sethoxydim, 89 +/- 13%. There was no evidence of oxidation of clethodim and sethoxydim during the extraction to their respective sulfoxides. The limit of quantitation was <0.1 microgram L(-1). We have shown that we can analyze and confirm three cyclohexanedione oxime herbicides and two metabolites in water by LC/ES/MS. This multiresidue method should also be appropriate for other cyclohexanedione oximes.

Influence of soil pH-sorption interactions on imazethapyr carry-over.

Soil pH affects imazethapyr sorption-desorption, which in turn can affect persistence and bioavailability. Long-term imazethapyr carry-over has been observed in soil that is below pH 6.5, resulting in significant sugarbeet damage. Imazethapyr concentration decreased rapidly in field soil, regardless of pH. Despite similar amounts of imazethapyr remaining in aged soils at different pH levels, there were differences in bioavailability, which can be explained by sorption-desorption. At low pH more imazethapyr was sorbed than at high pH, but it readily desorbed. At high pH less imazethapyr was sorbed initially, but it did not readily desorb. Thus, after 3 months, the remaining imazethapyr in low-pH soil was desorbable and bioavailable, resulting in injury to canola and sugarbeet. Liming aged, low-pH soil released bound imazethapyr residues, which would then be degraded and result in less carry-over.

Sorption of imidacloprid and its metabolites on tropical soils.

The sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolid-inimine ) (IMI) and its metabolites imidacloprid-urea (1-[(6-chloro-3-pyridinyl)-methyl]-2-imidazol-idinone) (IU), imidacloprid-guanidine (1-[(6-chloro-3-pyridinyl)-methyl]-4,5-dihydro-1H-imidazol-2-amine) (IG), and imidacloprid-guanidine-olefin (1-[(6-chloro-3-pyridinyl)methyl]-1H-imidazol-2-amine) (IGO) was determined on six typical Brazilian soils. Sorption of the chemicals on the soil was characterized using the batch equilibration method. The range and order of sorption (Kd) on the six soils was IG (4.75-134) > or = IGO (2.87-72.3) > IMI (0.55-16.9) > IU (0.31-9.50). For IMI and IU, Kd was correlated with soil organic carbon (OC) content and CEC, the latter due to the high correlation between OC and cation exchange capacity (CEC) (R2 = 0.98). For IG and IGO, there was no correlation of sorption to clay, pH, OC or CEC due to the high sorption on all soils. Average Koc values were IU = 170, IMI = 362, IGO = 2433, and IG = 3500. Although Kd and Koc values found were consistently lower than those found in soils developed in non-tropical climates, imidacloprid and its metabolites were still considered to be slightly mobile to immobile in Brazilian soils.

Sorption and desorption of triadimefon by soils and model soil colloids.

Sorption-desorption of the azole fungicide triadimefon [1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2, 4-triazol-1-yl)-2-butanone] on eight soils and a series of single, binary, and ternary model soil colloids was determined using the batch equilibration technique. Regression analysis between Freundlich sorption coefficients (K(f)) and soil properties suggested that both clay and organic C (OC) were important in triadimefon sorption by soils, with increasing importance of clay for soils with high clay and relatively low OC contents. Triadimefon sorption coefficients on soil were not significantly affected by the concentration of electrolyte or the presence of soluble soil material in solution, but they were highly dependent on the soil:solution ratio due to the nonlinearity of triadimefon sorption on soil. Freundlich sorption isotherms slopes were very similar for all soils (0.75 +/- 0.02). Desorption did not greatly depend on the concentration at which it was determined and showed higher hysteresis for more sorptive soils. Results of triadimefon sorption on model sorbents supported that both humic acid and montmorillonite-type clay constituents contribute to triadimefon retention by soil colloids.

An isotopic exchange method for the characterization of the irreversibility of pesticide sorption-desorption in soil.

An isotopic exchange method is presented that characterizes the irreversibility of pesticide sorption-desorption by soil observed in batch equilibration experiments. The isotopic exchange of (12)C- and (14)C-labeled triadimefon [(1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1, 2,4-triazol-1-yl)-2-butanone] and imidacloprid-guanidine [1-[(6-chloro-3-pyridinyl)methyl]-4,5-dihydro-1H-imidazol-2-amine] in Hanford sandy loam soil indicated that these systems can be described by a two-compartment model in which about 90% of sorption occurs on reversible, easily desorbable sites, whereas 10% of the sorbed molecules are irreversibly sorbed on soil and do not participate in the sorption-desorption equilibrium. This model closely predicted the hysteresis observed in the desorption isotherms from batch equilibration experiments. The isotopic exchange of triadimefon and imidacloprid-guanidine in Drummer silty clay loam soil indicated that there was a fraction of the sorbed (14)C-labeled pesticide that was resistant to desorption, which increased as pesticide concentration decreased and was higher for triadimefon than for imidacloprid-guanidine. In contrast, the batch equilibration method resulted in ill-defined desorption isotherms for the Drummer soil, which made accurate desorption characterization problematic.

Factors affecting atrazine fate in north central U.S. soils.

Atrazine persistence and fate are influenced by many factors, the interactions of which are difficult to predict. Several models, such as LEACHP (Wagenet and Hutson 1989), have been used as tools to estimate losses and identify variables that will impact the magnitude of loss. The LEACHP model was evaluated for predicting atrazine movement in sandy loam, silt loam, and clay loam soils during three consecutive years (two dry and one wet) in Minnesota (Khakural et al. 1995). Considering the broad range in soil properties and climatic conditions used in testing, the model performed well. However, these are only estimates, and additional field studies need to be conducted to verify model results. In a report by Fausey et al. (1995), the amount of atrazine found in groundwater throughout the Midwestern region was reported to be much below the MCL. However, specific sites in the Midwest may struggle with atrazine problems from both point and nonpoint sources of contamination. Some states, such as South Dakota, have created groundwater protection areas that alert growers and the public to sensitive areas where contamination may occur because of soil type, depth to groundwater, and distance to public wellheads. Wisconsin has developed a tiered managerial strategy, or zoning approach, in which restrictions are matched to pollution detections (Wolf and Nowak 1996). The USEPA has mandates for states to implement generic management plans to prevent pesticide contamination of groundwater. Chemical-specific plans by states will be required for at least five pesticides, one of which will be atrazine. Best management practices have been and are continuing to be developed to aid the grower in lessening the adverse impacts of atrazine. With continuing research into understanding the problem and developing solutions, and with adaptation of these recommendations by growers, the use of effective, inexpensive herbicides may continue with minimal off-site environmental effects.

Mineralization of alachlor by lignin-degrading fungi.

White rot fungi were able to mineralize the aromatic ring carbon of alachlor to CO2. After 122 days, 14 and 12% of the alachlor that was initially present in malt extract cultures supplemented with a wood substrate was mineralized at room temperature by Ceriporiopsis subvermispora and Phlebia tremellosa, respectively. Although Phanerochaete chrysosporium mineralized alachlor at 25 degrees C, it did so more slowly than the other two white rot fungi. The brown rot fungus Fomitopsis pinicola did not mineralize alachlor.

Tellurium and Selenium Resistance in Rhizobia and Its Potential Use for Direct Isolation of Rhizobium meliloti from Soil.

Forty-eight Rhizobium and Bradyrhizobium strains were screened for resistance to tellurite, selenite, and selenate. High levels of resistance to the metals were observed only in Rhizobium meliloti and Rhizobium fredii strains; the MICs were 2 to 8 mM for Te(IV), >200 mM for Se(VI), and 50 to 100 mM for Se(IV). Incorporation of Se and Te into growth media permitted us to directly isolate R. meliloti strains from soil. Mutant strains of rhizobia having decreased levels of Se and Te resistance were constructed by Tn5 mutagenesis and were found to have transposon insertions in DNA fragments of different sizes. Genomic DNAs from Te rhizobium strains failed to hybridize with Te determinants from plasmids RP4, pHH1508a, and pMER610.

Plasmids pJP4 and r68.45 Can Be Transferred between Populations of Bradyrhizobia in Nonsterile Soil.

IncP plasmid r68.45, which carries several antibiotic resistance genes, and IncP plasmid pJP4, which contains genes for mercury resistance and 2,4-dichlorophenoxyacetic acid degradation, were evaluated for their ability to transfer to soil populations of rhizobia. Transfer of r68.45 was detected in nonsterile soil by using Bradyrhizobium japonicum USDA 123 as the plasmid donor and several Bradyrhizobium sp. strains as recipients. Plasmid transfer frequencies ranged up to 9.1 x 10 in soil amended with 0.1% soybean meal and were highest after 7 days with strain 3G4b4-RS as the recipient. Transconjugants were detected in 7 of 500 soybean nodules tested, but the absence of both parental strains in these nodules suggests that plasmid transfer had occurred in the soil, in the rhizosphere, or on the root surface. Transfer of degradative plasmid pJP4 was also evaluated in nonsterile soil by using B. japonicum USDA 438 as the plasmid donor and several Bradyrhizobium sp. strains as recipients. Plasmid pJP4 was transferred only when strains USDA 110-ARS and 3G4b4-RS were the recipients. The plasmid transfer frequency was highest for strain 3G4b4-RS (up to 7.4 x 10). Mercury additions to soil, ranging from 10 to 50 mug/g of soil, did not affect population levels of parental strains or the plasmid transfer frequency.