Blame It on the Metabolite: 3,5-Dichloroaniline Rather than the Parent Compound Is Responsible for the Decreasing Diversity and Function of Soil Microorganisms.

Pesticides are key stressors of soil microorganisms with reciprocal effects on ecosystem functioning. These effects have been mainly attributed to the parent compounds, while the impact of their transformation products (TPs) has been largely overlooked. We assessed in a meadow soil (soil A) the transformation of iprodione and its toxicity in relation to (i) the abundance of functional microbial groups, (ii) the activity of key microbial enzymes, and (iii) the diversity of bacteria, fungi, and ammonia-oxidizing microorganisms (AOM) using amplicon sequencing. 3,5-Dichloroaniline (3,5-DCA), the main iprodione TP, was identified as a key explanatory factor for the persistent reduction in enzymatic activities and potential nitrification (PN) and for the observed structural changes in the bacterial and fungal communities. The abundances of certain bacterial (Actinobacteria, Hyphomicrobiaceae, Ilumatobacter, and Solirubrobacter) and fungal (Pichiaceae) groups were negatively correlated with 3,5-DCA. A subsequent study in a fallow agricultural soil (soil B) showed limited formation of 3,5-DCA, which concurred with the lack of effects on nitrification. Direct 3,5-DCA application in soil B induced a dose-dependent reduction of PN and NO3--N, which recovered with time. In vitro assays with terrestrial AOM verified the greater toxicity of 3,5-DCA over iprodione. "Candidatus Nitrosotalea sinensis" Nd2 was the most sensitive AOM to both compounds. Our findings build on previous evidence on the sensitivity of AOM to pesticides, reinforcing their potential utilization as indicators of the soil microbial toxicity of pesticides in pesticide environmental risk analysis and stressing the need to consider the contribution of TPs in the toxicity of pesticides on the soil microbial community.IMPORTANCE Pesticide toxicity on soil microorganisms is an emerging issue in pesticide risk assessment, dictated by the pivotal role of soil microorganisms in ecosystem services. However, the focus has traditionally been on parent compounds, while transformation products (TPs) are largely overlooked. We tested the hypothesis that TPs can be major contributors to the soil microbial toxicity of pesticides using iprodione and its main TP, 3,5-dichloroaniline, as model compounds. We demonstrated, by measuring functional and structural endpoints, that 3,5-dichloroaniline and not iprodione was associated with adverse effects on soil microorganisms, with nitrification being mostly affected. Pioneering in vitro assays with relevant ammonia-oxidizing bacteria and archaea verified the greater toxicity of 3,5-dichloroaniline. Our findings are expected to advance environmental risk assessment, highlighting the potential of ammonia-oxidizing microorganisms as indicators of the soil microbial toxicity of pesticides and stressing the need to consider the contribution of TPs to pesticide soil microbial toxicity.

Laboratory and field dissipation of penoxsulam, tricyclazole and profoxydim in rice paddy systems.

Rice cultivation relies on pesticide applications to ensure high yields. However, the regular use of pesticides seriously affects the quality of neighboring surface water systems. Thus complete knowledge of the environmental fate and dissipation of pesticides in the paddy rice environment should become available. So far only a few studies have provided comprehensive assessment of the dissipation of pesticides under the submerged cultivation conditions followed in rice. Thus, laboratory and 2-year field studies were performed to assess the dissipation of two new generation rice herbicides (penoxsulam and profoxydim) and one of the most important rice fungicides (tricyclazole). A good agreement between laboratory and field experiments was observed with a faster dissipation of penoxsulam and tricyclazole under field conditions. Profoxydim was the least persistent chemical (DT50 soil<1d; DT50 water 0.5-1.2d), followed by penoxsulam which persisted for longer particularly in the water compartment (DT50water=3.8-5.9d). Tricyclazole was the most persistent pesticide, especially in the soil compartment with DT50 values of 44.5-84.6 (field) and 197d (laboratory). These results could be utilized for the assessment of the environmental risk associated with the use of those pesticides in rice cultivation and the determination of potential mitigation measures for minimizing the risk for contamination of neighboring natural water resources.

Hypervalent iodine compounds as potent antibacterial agents against ice nucleation active (INA) Pseudomonas syringae.

Twenty-three hypervalent iodine compounds belonging to aryliodonium salts, 1, aryliodonium ylides, 2, and (diacyloxyiodo)arenes, 3, were tested for their antibacterial activities against ice nucleation active (INA) Pseudomonas syringae, and the MIC and EC(50) values were determined. All of the compounds examined caused a dose-dependent decrease in bacterial growth rates. Aryliodonium salts, especially those with electron-withdrawing groups, exhibit higher antibacterial activities with MIC = 8-16 ppm, whereas the nature of the anion does not seem to affect the activities of the diaryliodonium salts.

Study of tau-fluvalinate persistence in honey.

The persistence of the acaricide tau-fluvalinate with time and the factors that can affect its degradation in honey were investigated. Two honey types of extreme pH values (3.85 and 5.40) were spiked with tau-fluvalinate at two levels (50 and 200 micrograms kg-1) and incubated at 35 degrees C. Samples were analyzed in duplicate at various time intervals for up to 248 days. A simple, rapid and accurate method for the determination of tau-fluvalinate residues in honey is proposed. Tau-fluvalinate extraction and sample cleanup was carried out using C8 SPE cartridges with dichloromethane as the elution solvent. Analysis of samples was accomplished using gas chromatography with electron-capture detection (GC-ECD). The overall recovery of the method was 90.25 (+/- 0.85)% and the limit of determination 1 microgram kg-1. The results showed that tau-fluvalinate stays stable in honey for more than 8 months, even at 35 degrees C. The effect of higher temperatures, similar to those used for honey packing, on tau-fluvalinate persistence in honey was also studied. Honey samples fortified with 20 and 200 micrograms kg-1 tau-fluvalinate were subjected to heat treatment similar to that in the honey blending and packing process. No degradation of tau-fluvalinate due to the heat treatment was recorded. This long persistence increases the risk of honey contamination due to repeated and/or extended tau-fluvalinate applications.

Determination of fluvalinate residues in beeswax by gas chromatography with electron-capture detection.

A simple, rapid, and accurate method is described for the determination of residual fluvalinate in beeswax. The procedure consists of partitioning on a disposable column of diatomaceous earth (Extrelut), followed by chromatographic cleanup on a Florisil cartridge. The final extract is analyzed by capillary gas chromatography with electron-capture detection (GC-ECD). Briefly, wax samples were dissolved in n-hexane, and the solutions were sonicated and transferred to Extrelut columns. The fluvalinate was extracted with acetonitrile, and a portion of the extract was cleaned up on a Florisil cartridge. The fluvalinate was eluted with diethyl ether-n-hexane (1 + 1) and directly determined by GC-ECD. Recoveries from wax samples spiked at 5 fortification levels (100-1500 microg/kg) ranged from 77.4 to 87.3%, with coefficients of variation of 5.12-8.31%. The overall recovery of the method was 81.4 +/- 3.2%, and the limit of determination was 100 microg/kg.

Determination of malathion, coumaphos, and fluvalinate residues in honey by gas chromatography with nitrogen-phosphorus or electron capture detectors.

A rapid, reliable, and inexpensive extraction method was developed to determine acaricide residues in honey by gas chromatography (GC) with nitrogen-phosphorus (NP) or electron capture (EC) detectors. Because of the high selectivity of the NP detector, no interfering peaks were present and no cleanup was necessary. A simple cleanup step is proposed for the GC-ECD analysis. Recoveries from spiked honey samples ranged from 79 to 94.4%, with coefficients of variation of 0.3-18.5%. The quantitation limit obtained was 0.015 mg/kg for malathion, 0.020 mg/kg for coumaphos, and 0.005 mg/kg for fluvalinate. The method was used to determine the disappearance of malathion and coumaphos residues from honey samples collected from beehives treated with these acaricides. The disappearance of both acaricides was rapid and followed a first-order model for the duration of the experiment.