Non-targeted impact of cyantraniliprole residues on soil quality, mechanism of residue degradation, and isolation of potential bacteria for its bioremediation.

Cyantraniliprole (CY), an anthranilic diamide insecticide widely used in grape farming for controlling various sucking pests, poses ecological concerns, particularly when applied as soil drenching due to the formation of more toxic and persistent metabolites. This study established the dissipation and degradation mechanisms of CY in grape rhizosphere soil using high-resolution Orbitrap-LC/MS analysis. The persistence of CY residues beyond 60 days was observed, with dissipation following biphasic first + first-order kinetics and a half-life of 15 to 21 days. The degradation mechanism of CY in the soil was elucidated, with identified metabolites such as IN-J9Z38, IN-JCZ38, IN-N7B69, and IN-QKV54. Notably, CY was found to predominantly convert to the highly persistent metabolite IN-J9Z38, raising environmental concerns. The impact of CY residues on soil enzyme activity was investigated, revealing a negative effect on dehydrogenase, alkaline phosphatase, and acid phosphatase activity, indicating significant implications for phosphorous mineralization and soil health. Furthermore, bacterial isolates were obtained from CY-enriched soil, with five isolates (CY3, CY4, CY9, CY11, and CY20) demonstrating substantial degradation potential, ranging from 66 to 92% of CY residues. These results indicate that the identified bacteria hold potential for commercial use in addressing pesticide residue contamination in soil through bioremediation techniques.

Non-target influence of imidacloprid residues on grape global metabolome and berry quality with the identification of metabolite biomarkers.

This paper illustrates the non-target impact of imidacloprid (IM) residues on the grape global metabolome and biomarker identification with high-resolution mass spectrometry. IM was applied at the recommended dose (SD), and ten times SD (10 RD). The global metabolome analysis revealed that 21 metabolites were up- and down-regulated with IM SD treatment. In 10 RD, 9 metabolites were upregulated, and 28 were downregulated. Pathway enrichment analysis revealed the primary and secondary pathway disruption in grapes. Berry quality was affected with decrease in flavonoids by 32.97% in 10 RD; phenols were reduced by 53.93 in SD, 50.8% in 10 RD. The non-target and target study revealed the degradation of IM in grapes to desnitro-IM and IM-urea which were identified as a potential biomarker for IM residues in grapes, which would benefit the authentication of organic product. Overall, imidacloprid showed a significant impact on the grape metabolome and quality.

Assessment of degradation mechanism of imidacloprid residues in grape rhizosphere soil by UHPLC-Orbitrap™-MS and its residual impact on soil enzyme activity.

Imidacloprid (IM) is a systemic insecticide persistent in the environment and possesses a negative impact on the non-targeted ecosystem. The objective of the present study was to evaluate the dissipation and degradation mechanism of IM residues in grape rhizosphere soil and to investigate its residual effect on soil enzyme activity at different IM spiking levels. The half-life of IM residue in soil was 27, 36, and 43.5 days at a spiking level of 1, 10, and 50 mg kg-1, respectively following a bi-phasic first + first-order dissipation kinetics. UHPLC-Orbitrap™-MS analysis by targeted metabolomics approach revealed that IM metabolites such as IM-amine analogue, guanidine (reduction), 5-hydroxy IM (hydroxylation), IM-Urea (oxidation), reduced NO analogue of IM (oxidation), and olefin of guanidine IM (dehydrogenation) were identified and proposed the degradation mechanism in grape rhizosphere soil. Toxicity of IM residues on five extracellular enzymes, viz., dehydrogenase, acid phosphatase, alkaline phosphatase, ß-glucosidase, and urease revealed that activity of dehydrogenase, acid phosphatase, and alkaline phosphatase remained unaffected at 60th day of sampling. The ß-glucosidase and urease were negatively affected throughout the incubation period indicating the influence of IM residues on carbon and nitrogen mineralization in soil. Thus, long-term exposure of IM to grape rhizosphere through soil drenching could affect soil enzyme activity which has a negative effect on the soil nutrient cycle and soil microbiome.

Residue dissipation, evaluation of processing factor and safety assessment of hexythiazox and bifenazate residues during drying of grape to raisin.

An analytical method for the simultaneous analysis of hexythiazox and bifenazate residues in grape and raisin was validated by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. The extraction method involved liquid-liquid extraction with ethyl acetate and dSPE cleanup with primary secondary amine (PSA). The drying of grape to raisin may increase or decrease residues of pesticides. During the raisin making process, the dissipation of residue was evaluated and the processing factor (PF) was established for drying. Dissipation data were best fitted to 1st + 1st-order kinetics with a half-life ranging between 6-10 days for hexythiazox and 5-6 days for bifenazate. The PF value for overall raisin making was found to be 0.20-0.36 for hexythiazox and 0.14-0.15 for bifenazate indicating degradation of the residues. However, the PF value varies between 1.13-1.64 for hexythiazox and 0.94-1.12 for bifenazate during the drying process indicating concentration of the residues in drying. The dietary exposure on each sampling day was less than the respective maximum permissible intake (MPI). The residues in market samples of raisins were devoid of any risk of acute toxicity related to dietary exposure. The PF value generated will be useful for the field level management of residues in grape intended for raisin preparation.

Multiresidue Method for Targeted Screening of Pesticide Residues in Spice Cardamom (Elettaria cardamomum) by Liquid Chromatography with Tandem Mass Spectrometry.

A QuEChERS technique-based sample preparation method was optimized and validated in small cardamom to monitor the residues of 154 pesticides by LC with tandem MS. The proposed multiresidue method involved soaking powdered cardamom (2 g) in water (8 mL) for 30 min, followed by extraction with acetonitrile (10 mL). Cleanup by dispersive SPE was performed using primary secondary amine (25 mg/mL), C18 (25 mg/mL), and anhydrous magnesium sulfate (150 mg/mL). The method was validated as per the SANTE/11945/2015 guidelines at 5, 10, 50, and 100 ng/g spiking levels, and most of the analytes showed recoveries between 70 and 120% (with RSDs ≤20%). The LOQ of ≤10 ng/g was achieved for almost 90% of the target pesticides. The measurement uncertainties were evaluated at 100 ng/g, and the global uncertainty values were below 22% for all the analytes.

Optimization and Validation of a Residue Analysis Method for Glyphosate, Glufosinate, and Their Metabolites in Plant Matrixes by Liquid Chromatography with Tandem Mass Spectrometry.

A sensitive and accurate LC with tandem MS (MS/MS)-based method was developed and validated for the analysis of the herbicide glyphosate, its metabolite aminomethylphosphonic acid (AMPA), and glufosinate after derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) in various plant matrixes. The method also covers direct analysis of the glufosinate metabolites 3-methylphosphinicopropionic acid (3-MPPA) and N-acetyl-glufosinate (NAG). The homogenized samples were extracted with 0.1% formic acid in water-dichloromethane (50 + 50). The aqueous layer was derivatized with FMOC-Cl, cleaned through an HLB SPE cartridge, and determined by LC-MS/MS. The sample size, extraction solvent, sample-to-solvent ratio, derivatization conditions, and cleanup procedure were thoroughly optimized, the LOQs of glyphosate, glufosinate, and AMPA were 0.5 ng/g in grape, corn (leaf and seed), and cotton (leaf, seed, and oil) and 2 ng/g in soybean and tea. The LOQs of NAG and 3-MPPA were 50 ng/g in all the test matrixes, except tea and soybean, for which the LOQ was 100 ng/g. In all cases, average recoveries were >80%. The method successfully performed the estimation of glyphosate in incurred corn and cotton leaf samples collected from supervised field trials.