Biotransformation of atrazine and metolachlor within soil profile and changes in microbial communities

Biotransformation studies of atrazine, metolachlor and evolution of their metabolites were carried out in soils and subsoils of Northern Greece. Trace atrazine, its metabolites and metolachlor residues were detected in field soil samples 1 year after their application. The biotransformation rates of atrazine were higher in soils and subsoils of field previously exposed to atrazine (maize field sites) than in respective layers of the field margin. The DT₅₀ values of atrazine ranged from 5 to 18 d in the surface layers of the adapted soils. DT₅₀ values of atrazine increased as the soil depth increased reaching the value of 43 d in the 80-110 cm depth layer of adapted soils. Metolachlor degraded at slower rates than atrazine in surface soils, subsoils of field and field margins with the respective DT₅₀ values ranging from 56 to 72 d in surface soils and from 165 to 186 d in subsoils. Hydroxyatrazine was the most frequently detected metabolite of atrazine. The maximum concentrations of metolachlor-OXA and metolachlor-ESA were detected in the soil layers of 20-40 cm depth after 90 d of incubation. Principal Component Analysis (PCA) of soil Phospholipid Fatty Acids (PLFAs), fungal/bacterial and Gram-negative/Gram-positive ratios of the PLFA profiles revealed that the higher biotransformation rates of atrazine were simultaneously observed with the abundance of Gram-negative bacteria while the respective rates of metolachlor were observed in soil samples with abundance of fungi.     

Determination of acibenzolar-S-methyl and its acidic metabolite in soils by HPLC-diode array detection

A simple and accurate method for the analysis of acibenzolar-S-methyl (benzo[1,2,3]thiadiazole-7-carbothioic acid-S-methyl ester; CGA 245 704; ASM) and its major conversion product, benzo[1,2,3]thiadiazole-7-carboxylic acid (CGA 210 007; BTC), in soils is presented. ASM extraction from soil samples was performed using acetonitrile and BTC was extracted with a mixture of potassium phosphate buffer (0.5 M, pH 3) and acetonitrile (70:30 %, v/v). Both extracts were directly analyzed in a high-performance liquid chromatography-diode array detection (HPLC-DAD) system. Pesticide separation was achieved on a C18 (4.6 mm × 150 mm, 5 μm) analytical column with a isocratic elution of acetonitrile:water 40:60 % (v/v) with 0.6 mL L?1 acetic acid at a flow rate of 1 mL min?1. Linear regression coefficients (r (2)) of the external calibration curves were always above 0.9997. The limits of detection (LOD) and quantification (LOQ) of the method were 0.005 and 0.02 mg kg?1 for ASM, and 0.01 and 0.05 mg kg?1 for BTC, respectively. Recoveries were investigated at six fortification levels and were in the range of 90-120 % for ASM and 74-96 % for BTC with relative standard deviations (RSDs) below 11 % in all cases. The method was also validated by analyzing freshly spiked soil samples with 2.7% organic matter content at 0.5 mg kg?1 level, with slightly lower recovery values only for ASM. Moreover, recoveries for intermediate aged residues of the analytes were similar to fresh residues. This method was also applied to determine ASM half-life (t(?) = 8.7 h) and the rate of the acidic metabolite formation.     

Fluopyram removal from agricultural equipment rinsing water using HSF pilot-scale constructed wetlands

Fluopyram is a novel broad-spectrum fungicide with nematocidal activity, and as an extensively used pesticide, it could cause toxicity in nontarget organisms. The aim of this study was to explore the efficiency of five horizontal subsurface flow (HSF) constructed wetlands (CWs) to remove fluopyram from rinsing water produced during the cleaning of pesticide spraying equipment. Four CWs, namely WG-R, WG-R-P, WG-C, and WG-U, contained fine gravel as porous media. WG-R and WG-R-P were planted with Phragmites australis, WG-C with Typha latifolia, and WG-U was left unplanted. Bioaugmentation with plant growth-promoting rhizobacteria was conducted in WG-R-P unit. The fifth unit (WGZ-R) planted with Phragmites australis and contained gravel and zeolite as porous media. All of CWs were loaded on a daily basis from December 2019 to January 2021 with water fortified with fluopyram. The removal rate follows the pattern of WG-R-P (70.67%) > WGZ-R (62.06%) > WG-C (59.98%) > WG-R (36.10%) > WG-U (25.09%). The most important parameters affecting the fluopyram removal were bioaugmentation, zeolite presence in porous media, and plant species. The WG-R-P unit showed higher fluopyram removal in comparison to the WG-R (increase about 96%), the zeolite increased the fluopyram removal by 72%, and the WG-C unit showed 66% higher fluopyram removal than the WG-R unit.