Chiral Herbicide 2,4-D Ethylhexyl Ester: Absolute Configuration, Stereoselective Herbicidal Activity, Crop Safety, and Metabolic Behavior on Maize and Flixweed.

This study represents the initial examination of the herbicidal efficacy, crop safety, and degradation patterns of 2,4-D ethylhexyl ester (2,4-D EHE) at the enantiomeric level. Baseline separation of 2,4-D EHE enantiomers was achieved using a superchiral R-AD column, with their absolute configurations determined through chemical reaction techniques. Evaluation of weed control efficacy against sensitive species such as sun spurge and flixweed demonstrated significantly higher inhibition rates for S-2,4-D EHE compared to R-2,4-D EHE. Conversely, no stereoselectivity was observed in the fresh-weight inhibition rates of both enantiomers on crops or nonsensitive weeds. A sensitive HPLC-MS/MS method was developed to simultaneously detect two enantiomers and the metabolite 2,4-D in plants. Investigation into degradation kinetics revealed no substantial difference in the half-lives of R- and S-2,4-D EHE in maize and flixweed. Notably, the metabolite 2,4-D exhibited prolonged persistence at elevated levels on flixweed, while it degraded rapidly on maize.

Active ingredient identification and purification of organosilicon spray adjuvant and its uptake and translocation in rice (Oryza sativa L.).

The assessment of residue, absorption, conduction, and degradation of agricultural organosilicon surfactants in the environment is hindered by the lack of information on active ingredients and corresponding quantitative standards for organosilicon spray adjuvants. The spray adjuvant 'Jiexiaoli,' a primary organosilicon spray agent in China, was identified as hydroxy (polyethylene) propyl-heptamethyl trisiloxane (TSS-H) with 3-15 ethoxy (EO) groups. Purification of TSS-H was achieved through semi-preparative separation using high-performance liquid chromatography (HPLC), resulting in TSS-H purity exceeding 96%. An accurate residual detection method for nine oligomers (4-12 EO) of TSS-H in rice roots, stems, leaves, and culture solution samples was developed using HPLC tandem high-resolution mass spectrometry (HPLC-HRMS). Recoveries for nine oligomers of TSS-H in the four matrices ranged from 80.22% to 104.01%. Foliar application experiments demonstrated that TSS-H did not transfer from the upper to the lower parts of the rice plant. The half-lives of each oligomer (4-12 EO) in leaves were less than 3.21 days. Root application experiments revealed a root concentration factor (RCF) ranging from 0.20 to 0.56, a biological enrichment factor (BCF) ranging from 0.36 to 0.68, a transpiration factor (TSCF) ranging from 0.069 to 0.086, and a transport factor (TF) ranging from 0.08 to 0.43. These results indicated that TSS-H could be absorbed by rice roots and conducted to the above-ground parts of rice plants. This study fills the data gap in the environmental risk and food safety assessment of agricultural silicone spray adjuvants. © 2024 Society of Chemical Industry.

Degradation dynamics, residues, processing factors, and dietary risk assessment of bisultap in citrus by LC-MS/MS.

BACKGROUND: Citrus leaf miners are a common pest harming citrus production and quality during citrus planting. During the citrus plant's growth phase, bisultap formulation was frequently used to boost yield and produce fruit of high quality. However, research on citrus's dietary risk assessment for bisultap residues, dissipation and residues is lacking. RESULTS: Liquid chromatography-tandem mass spectrometry was used to develop an accurate and sensitive analytical method for derivatizing bisultap into nereistoxin in whole fruit, pulp and peel. At various levels of addition, the mean recovery of bisultap ranged from 84.64% to 111.09% with a reasonable relative RSD (< 20%). The half-lives in Guangxi and Guizhou were 3.96 and 6.03 days, respectively. After 14-21 days of bisultap application, total residues (bisultap and its metabolite nereistoxin) in the whole fruit were from < 0.02 to 0.228 mg kg-1 in the four experiment sites. Total residue (bisultap and nereistoxin, expressed by bisultap) in whole fruit was approximately 1.05-7.23 times that of pulp. The washing process with tap water removed 85.71% to 98.78% of the bisultap residue in the whole fruit. Bisultap's risk assessment value in citrus was in the range 0.16-1.28%. CONCLUSION: In the whole citrus fruit, bisultap degrades rapidly. Bisultap residues primarily accumulate on citrus peels, and so washing and peeling citrus may effectively remove bisultap residues. For various age groups, the chronic dietary risk of bisultap was acceptable. © 2023 Society of Chemical Industry.

Comparative analysis of toxicity and metabolomic profiling of rac-glufosinate and L-glufosinate in zebrafish.

Glufosinate is a chiral pesticide, with commercial formulations such as racemic glufosinate (rac-glufosinate) and pure L-glufosinate enantiomer (L-glufosinate) on the market. There has been little research on the difference in toxicity to non-target organisms between these two main ingredients. The effects of rac-glufosinate and L-glufosinate on glutathione reductase (GR), catalase (CAT), superoxide dismutase (SOD), and malondialdehyde (MDA) levels in zebrafish were investigated in this study. The effect of two glufosinate agents at low concentrations (0.01 and 0.1 mg/L) on these four oxidative indicators was found to be significantly lower than that of high concentrations (1 and 10 mg/L). L-glufosinate had a stronger enhancing effect on CAT, GR, and MDA content than rac-glufosinate and a stronger inhibitory effect on SOD activity than rac-glufosinate. The researchers used ultra-high-performance liquid chromatography coupled with high-resolution mass spectroscopy metabolomics to compare rac-glufosinate and L-glufosinate for metabolic disorders in adult zebrafish. Stable and obvious metabolic maps of the two agents were obtained using multivariate statistical results, such as principal component analysis and orthogonal partial minimum discriminant analysis. Compared to the control group, the rac-glufosinate and L-glufosinate treatment groups shared 151 differential metabolites, which primarily affected zebrafish energy metabolism, amino acid metabolism, and other metabolic pathways. Caffeine metabolism and biotin metabolism were among the unique pathways disrupted in rac-glufosinate-exposed zebrafish. Contrarily, L-glufosinate treatment primarily affected eight metabolic pathways, including arginine biosynthesis, melanogenesis, and glutathione metabolism. These findings may provide more detailed information on the toxicity of rac-glufosinate and L-glufosinate in zebrafish, as well as some context for assessing the environmental risk of the two glufosinate agents to aquatic organisms.

Degradation Dynamics and Residue Analysis of Four Propiconazole Stereoisomers in "Fengtang" Plum during Storage by LC-MS/MS.

Herein, an accurate and sensitive method was developed for detecting four stereoisomers of propiconazole in "Fengtang" plum by LC-MS/MS. The mean recovery of four propiconazole stereoisomers ranged from 79.42 to 104.10% at three adding levels with reasonable RSD of 1.54-11.68%, and the LOD and LOQ of the four stereoisomers was 0.0005 mg/kg and 0.004 mg/kg, respectively. In addition, the residue and selective degradation of propiconazole stereoisomers in plums were investigated by storage at 20 °C and 4 °C. The half-lives of propiconazole stereoisomeric during storage were 9.49-15.40 d at 20 °C, and 21.00-28.88 d at 4 °C. The degradation of (2R,4R)-propiconazole and (2R,4S)-propiconazole in stored plums was slightly slower than that of the corresponding enantiomers (2S,4S)-propiconazole and (2S,4R)-propiconazole. The total residues of propiconazole were 0.026-0.487 mg/kg in the plum storage period, and the water washing could remove 49.35% to 54.65% of the propiconazole residue in plum. The hardness of plums treated with propiconazole was generally higher than that of control in the middle and late stages of storage. The effects of propiconazole on the total soluble solid content of plums were different at 20 °C and 4 °C. This study provides a scientific reference for the food safety evaluation of the "Fengtang" plum after the application of propiconazole during the storage period.

Enantioselectivity of indoxacarb enantiomers in Bombyx mori larvae: toxicity, bioaccumulation and biotransformation.

BACKGROUND: Indoxacarb is a chiral insecticide with excellent insecticidal activity against lepidopterous insects. Because of their enantioselectivity, chiral pesticides' environmental behavior at the enantiomeric level has been highlighted. The chiral stability, enantioselective bioaccumulation, biotransformation behavior of indoxacarb to a non-target insect silkworm are still unclear. RESULTS: A chiral analysis method for indoxacarb and its metabolite DCJW in silkworm was developed using liquid chromatography and high-resolution mass spectrometry (HPLC/HRMS). In silkworms, the recoveries of indoxacarb and DCJW were 86.06%-104.52% with relative standard deviation (RSD) < 9.01%. The 96-h lethal concentration (LC50 ) values of R-indoxacarb, S-indoxacarb, and enriched S-indoxacarb (2.333 S/1R) were 1.08 × 102 , 1.92, and 6.89 mg a.i. L-1 , respectively, according to the acute toxicity test results. When silkworm larvae were exposed to 1/50 of the LC50 concentration, the bioconcentration factor (BCF) of R-indoxacarb was 0.0296-0.318, and the BCF of S-indoxacarb was 0.0125-0.211. In silkworm larvae, the amount of R-DCJW produced by R-indoxacarb was 0.00610 to 2.34 times that of the parent R-indoxacarb, and the amount of S-DCJW produced by S-indoxacarb was 0.125-36.9 times that of the parent S-indoxacarb. CONCLUSION: There was no chiral transition from S-indoxacarb to R-indoxacarb or a transformation from R-indoxacarb to S-indoxacarb. Indoxacarb was preferentially bioaccumulated in silkworm larva, while S-indoxacarb bioconversion into the metabolite S-DCJW was much greater than R-indoxacarb bioconversion into R-DCJW. This study could improve understanding of the indoxacarb accumulation and transformation process in insects, as well as provide more scientific data for indoxacarb environmental and ecological risk assessment. © 2023 Society of Chemical Industry.

Identification and Quantification of Dimethachlon Degradation Products in Soils and Their Effects on Soil Enzyme Activities.

In this study, high-performance liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS, Q-Exactive Orbitrap) and Compound Discoverer 3.3 were used to screen dimethachlon degradation products in soils. Four metabolites 4-(3,5-dichloroanilino)-4-oxobutanoic acid (DCBAA), 3,5-dichloroaniline (3,5-DCA), succinic acid, and muconic acid were confirmed by primary and secondary ion mass spectrometry comparisons between standards and samples. A quantitative analysis method of dimethachlon residues and four metabolites in soils was developed using HPLC-HRMS. Dimethachlon degradation in agricultural soil indoor unsterilized, sterilized, and field environments in three typical areas was measured. Dimethachlon degraded fast with a half-life of less than 1 day in three nonsterile soils. The maximum DCBAA and 3,5-DCA residues during degradation could reach 22.5-35.2% of the initial concentration of the parent dimethachlon. The metabolite DCBAA had a greater impact on soil enzyme activity than the parent dimethachlon.