Impacts of biochar on bioavailability of the fungicide azoxystrobin: a comparison of the effect on biodegradation rate and toxicity to the fungal community.

There is great interest in using biochar (BC) as a soil amendment to provide a long-term repository of carbon to mitigate climate change. BC can have major impacts on soil biogeochemical cycling processes, largely by the sorption and protection of organic matter from microbial turnover. Application of BC to agricultural soil could also affect the efficacy, fate and environmental impact of pesticides. In the current study we investigated the effect of BC on bioavailability of the fungicide azoxystrobin in soil. We found that application of BC had no effect on sorption or degradation of azoxystrobin, even at a rate of 2% w/w. While azoxystrobin reduced dehydrogenase activity, BC addition greatly increased dehydrogenase, although the inhibitory effect of azoxystrobin was still evident in BC amended soil. Using Terminal Restriction Fragment Length Polymorphism of fungal SSU rRNA gene ITS regions it was found that azoxystrobin altered the structure of the soil fungal community, although this effect was dampened by BC addition. BC application had minor effects on fungal community structure. We conclude that measurement of the effect of BC on pesticide bioavailability by analysis of biodegradation rate and non-target effects on fungal community structure gave contrasting conclusions.

Assessing the chemical and biological accessibility of the herbicide isoproturon in soil amended with biochar.

There is considerable current interest in using biochar (BC) as a soil amendment to sequester carbon to mitigate climate change. However, the implications of adding BC to agricultural soil for the environmental fate of pesticides remain unclear. In particular, the effect of biochars on desorption behavior of compounds is poorly understood. This study examined the influence of BC on pesticide chemical and biological accessibility using the herbicide isoproturon (IPU). Soils amended with 1% and 2% BC showed enhanced sorption, slower desorption, and reduced biodegradation of IPU. Addition of 0.1% BC had no effect on sorption, desorption or biodegradation of IPU. However, the mineralization of (14)C-IPU was reduced by all BC concentrations, reducing by 13.6%, 40.1% and 49.8% at BC concentrations of 0.1%, 1% and 2% respectively. Further, the ratio of the toxic metabolite 4-isopropyl-aniline to intact IPU was substantially reduced by higher BC concentrations. Hydroxypropyl-ß-cyclodextrin (HPCD) extractions were used to estimate the IPU bioaccessibility in the BC-amended soil. Significant correlations were found between HPCD-extracted (14)C-IPU and the IPU desorbed (%) (r(2)=0.8518, p<0.01), and also the (14)C-IPU mineralized (%) (r(2)=0.733; p<0.01) for all BC-amended soils. This study clearly demonstrates how desorption in the presence of BC is intimately related to pesticide biodegradation by the indigenous soil microbiota. BC application to agricultural soils can affect the persistence of pesticides as well as the fate of their degradation products. This has important implications for the effectiveness of pesticides as well as the sequestration of contaminants in soils.

Photostabilization of the herbicide norflurazon microencapsulated with ethylcellulose in the soil-water system.

Ethylcellulose-microencapsulated formulations (ECFs) of norflurazon have been shown to reduce leaching, maintaining a threshold concentration in the topsoil than the commercial formulation (CF). Since photodegradation contributes to field dissipation of norflurazon, the objective of the present work was to study if such formulations can also protect from its photodescomposition. For this purpose, aqueous solutions of CF and ECFs, containing the most important soil components (goethite, humic and fulvic acids and montmorillonite) were tested. To get a more realistic approach, studies in soil were also performed. The results were well explained by a simple first order model. DT(50) value was 3h for CF under irradiation, which was considerably lower than those corresponding to the systems where ECF was used (35 h for ECF; 260 h for ECF-goethite; 53 h for ECF-humic acids; 33 h for ECF-montmorillonite; and 28 h for ECF-fulvic acids). ECF protected against photodegradation in both aqueous solution and soil due to the gradual release of the herbicide, which reduced the herbicide available to be photodegraded. These lab-scale findings proved that ECF could reduce the herbicide dosage, minimizing its photolysis, which would be especially advantageous during the first hours after foliar and soil application.

Formulation affecting alachlor efficacy and persistence in sandy soils.

BACKGROUND: The development of controlled-release formulations of alachlor to extend the period of weed control was studied. This extended duration reduces the need for high herbicide application rates that could lead to environmental contamination. For this purpose, the influence of formulation, as well as the influence of soil characteristics, on alachlor efficacy and persistence in soil of a commercial formulation (CF) and different ethylcellulose microencapsulated formulations (MEFs) was evaluated. RESULTS: Higher alachlor rates yielded an enhanced initial herbicidal activity. The prolonged release of alachlor provided by the MEFs resulted in a higher herbicidal efficacy and a longer period of weed control compared with the effects of CF in the two soils tested (at 40 days after treatment, oat growth inhibition for CF and MEFs was 1.96% and 93.5% respectively). Soil characteristics strongly influenced alachlor efficacy and weed control by MEFs. The highest alachlor efficacy and persistence were observed in the soil with lowest microbial activity and clay and organic matter content. CONCLUSIONS: The use of MEFs can be advantageous because they permit the maintenance of the desired concentration of the herbicide in the soil for longer periods of weed control.

Effects of soil characteristics on metribuzin dissipation using clay-gel-based formulations.

Metribuzin (MTB) is a herbicide widely used for weed control in growing soybeans and other crops and has been identified in many parts of the world as a groundwater contaminant. To prepare controlled-release formulations (CRFs) of MTB, it was entrapped within a sepiolite-gel-based matrix with one of two proportions of clay/herbicide and used as either a gel or powder after freeze-drying. To determine how its persistence in soil is affected by formulation and soil type, MTB was applied as a CRF or commercial formulation (CM) to soils with different properties. MTB dissipation in all soils investigated was reduced when the herbicide was applied as CRFs, especially in the case of sandy soil and the freeze-dried formulations, with DT(50) values of 57.5 and 104.1 days, respectively, versus 24.8 days for CM. A positive relationship between degradation rates, bioactivity, and soil pH was found. MTB adsorption-desorption studies on these soils were also performed, and no relationship between adsorption-desorption and the degradation rate of MTB was found, possibly because of the low adsorption capacity of the studied soils. MTB when applied as a CRF remains active longer than CM, avoiding the need to use more frequently herbicide applications.

Novel system for reducing leaching of the herbicide metribuzin using clay-gel-based formulations.

Metribuzin is an herbicide widely used for weed control that has been identified as a groundwater pollutant. It contaminates the environment even when it is used according to the manufacturer's instructions. To reduce herbicide leaching and increase weed control, new controlled release formulations were developed by entrapping metribuzin within a sepiolite-gel-based matrix using two clay/herbicide proportions (0.5/0.2 and 1/0.2) (loaded at 28.6 and 16.7% a.i.) as a gel (G28, G16) or as a powder after freeze-drying (LF28, LF16). The release of metribuzin from the control released formulations into water was retarded, when compared with commercial formulation (CF) except in the case of G28. The mobility of metribuzin from control released formulations into soil columns of sandy soil was greatly diminished in comparison with CF. Most of the metribuzin applied as control released formulations (G16, LF28 and LF16) was found at a depth of 0-8 cm depth. In contrast, residues from CF and G28 along the column were almost negligible. Bioassays from these control released formulations showed high efficacy at 0-12 cm depth. The use of these novel formulations could minimize the risk of groundwater contamination while maintaining weed control for a longer period.

Ethylcellulose formulations for controlled release of the herbicide alachlor in a sandy soil.

The development of controlled-release formulations of alachlor to diminish its leaching in sandy soils, avoiding groundwater contamination and maintaining its efficacy, was studied. For this purpose, ethylcellulose (EC) microencapsulated formulations (MEFs) of alachlor were prepared under different conditions and applied to soil columns to study their mobility. The results show that in all cases the release into water of alachlor from MEFs was retarded when compared with commercial formulation. Total leaching losses in soil columns were reduced to 59% from 98%. The mobility of alachlor from EC microspheres into soil columns has been greatly diminished in comparison with its current commercial formulation (CF), above all with increasing EC/herbicide ratios. Distribution of alachlor applied as MEFs at different depths in the soil was higher in the soil surface (66.3-81.3% of herbicide applied at the first 12 cm). In contrast, the residues from CF along the complete soil column were only 20.4%. From the results of bioassays, MEFs showed a higher efficacy than CF at 30 days after the treatment. The use of ME formulations could provide an advantage in minimizing the risk of groundwater contamination by alachlor and reducing the application rates, as a result of maintaining the desired concentration of the herbicide in the top soil layer, obtaining longer periods of weed control.

Norflurazon mobility, dissipation, activity, and persistence in a sandy soil as influenced by formulation.

Five ethylcellulose (EC) microencapsulated formulations (MEFs) of norflurazon were prepared and applied in soil to study their mobility, dissipation, activity, and persistence. The results show that the release into water of norflurazon from EC microspheres was retarded when compared with that of commercial herbicide. The mobility of norflurazon from MEFs into soil columns has been greatly diminished in comparison with that of its current commercial formulation (CF). Norflurazon distribution at different depths in the soil was higher in the upper ring (up to 50% of the initial application). In contrast, the residues from commercial norflurazon along the complete soil column were only about 2%. Degradation and bioassay experiments showed that the MEFs had greater persistence (t1/2 values were 7.72 and 30.83 weeks for CF and MEFs, respectively) and herbicidal activity than the commercial formulation. The use of these formulations can be advantageous, because they can minimize the risk of groundwater contamination and permit herbicide use at reduced rates, maintaining the desired concentrations of herbicide in the topsoil layer for longer periods of weed control.

Controlled release of the herbicide norflurazon into water from ethylcellulose formulations.

The herbicide norflurazon was encapsulated in ethylcellulose (EC(40)) microspheres by the solvent evaporation technique to obtain controlled release formulations. The kinetics of release of the active ingredient into the aqueous solution from different preparations was determined. It was found that the percentage release of the incorporated herbicide was a function of the composition and formation conditions of the formulations (amount of emulsifying agent, EC(40)/herbicide ratio, stirring speed, and percentage of pore-forming agent). The percentage of the herbicide release was related to the properties of the different microspheres obtained, such as particle size distribution, herbicide loading, or surface morphology. The release percentage depended inversely on the particle size of the microspheres and directly on the content of active ingredient and emulsifying and pore-forming agents. An empirical equation was used to fit the herbicide release data, indicating that the release of norflurazon from the various formulations is controlled by a diffusion mechanism. The time taken for 50% of the active ingredient to be released into water (T(50)) was calculated, showing a wide variation among the different preparations (0.95-16.4 days).