Development, validation and a GAPI greenness assessment for the determination of 103 pesticides in mango fruit drink using LC-MS/MS.

A robust method was developed using LC-ESI-MS/MS-based identification and quantification of 103 fortified pesticides in a mango fruit drink. Variations in QuEChERS extraction (without buffer, citrate, and/or acetate buffered) coupled with dispersive clean-up combinations were evaluated. Results showed 5 mL dilution and citrate buffered QuEChERS extraction with anhydrous (anhy) MgSO4 clean-up gave acceptable recovery for 100 pesticides @ 1 µg mL-1 fortification. The method was validated as per SANTE guidelines (SANTE/11813/2021). 95, 91, and 77 pesticides were satisfactorily recovered at 0.1, 0.05, and 0.01 µg mL-1 fortification with HorRat values ranging from 0.2-0.8 for the majority. The method showed matrix enhancement for 77 pesticides with a global uncertainty of 4.72%-23.89%. The reliability of the method was confirmed by real sample analysis of different brands of mango drinks available in the market. The greenness assessment by GAPI (Green Analytical Procedure Index) indicated the method was much greener than other contemporary methods.

Degradation of co-applied Atrazine and Fipronil in Phanerochaete Chrysosporium Augmented Biobeds.

White rot fungi possess an enzymatic system that is non-specific to any pesticide and can be used for pesticide detoxification in biobeds. The present study evaluated potential of Phanerochaete chrysosporium to degrade co-applied atrazine and fipronil in ash or biochar biomixtures. Five biomixtures were prepared by partially replacing compost in rice straw-compost biomixture (BM) with 10% rice husk ash (RHA), 10% sugarcane bagasse ash (SBA), and 1 and 5% wheat straw biochar (WBC). Results suggested that after 30 days P. chrysosporium augmented biobeds resulted in 60.52-72.72% atrazine and 69.57-72.52% fipronil degradation. Hydroxyatrazine and fipronil sulfone were detected as the only metabolite of atrazine and fipronil, respectively, and were further degraded. Although, SBA significantly enhanced atrazine degradation, RHA or SBA had no significant effect on fipronil degradation. WBC (5%) slowed down degradation of both pesticides.

Quantification of field-incurred residues of cyantraniliprole and IN-J9Z38 in cabbage/soil using QuEChERS/HPLC-PDA and dietary risk assessment.

Cyantraniliprole is an anthranilic diamide insecticide used for the effective management of diamondback moth in cabbage. Dietary risk assessment of pesticides in food is a major concern now. This study developed a QuEChERS/HPLC-PDA-based highly efficient and reliable method, registering 89.80-100.11% recoveries of cyantraniliprole and its metabolite IN-J9Z38 from cabbage and soil with a relative standard deviation of 0.43-5.77%. Field experiment was conducted to study the residue dissipation of cyantraniliprole in cabbage and soil. Two foliar treatments of 10.26% formulation (Benevia) at 60 (T1 ) and 120 (T2 ) gram active ingredient/hectare were applied. The dissipation half-lives of cyantraniliprole in cabbage and soil were determined to be 3.5-4.2 and 3.8-5.3 days at T1 and 3.9-4.8 and 4.1-4.7 days at T2 , respectively. The maximum concentrations of IN-J9Z38 at T1 and T2 were 0.819 and 1.061 mg/kg, respectively, on the fifth day. A risk quotient value of <1 indicates no dietary risk to the consumers. The residues in the harvested cabbage were below the tolerance level of 2.0 mg/kg established by the regulatory body in India.

Linear and Nonlinear Isotherm Models and Error Analysis for the Sorption of Kresoxim-Methyl in Agricultural Soils of India.

Kresoxim methyl sorption in soils of five agro-climatic zones of India varied from 41.6% to 84.7%. Highest sorption was recorded in organic carbon rich Almora soil. Isotherm parameters for linear and non-linear Freundlich and Temkin models were almost same, whereas Langmuir parameter Q0, for linear (1.60 to 9.434 µg g-1) and non-linear (8.48 to 17.129 µg g-1) models were quite different. For isotherms optimization different error functions such as sum of squares error (SSE), root mean square error (RMSE), Chi square error, hybrid fractional error (HYBRID) and average relative error (ARE) were calculated. Lowest error function values were obtained for Freundlich isotherm in all the soils except inceptisol (Kolkata) for which Langmuir isotherm gave the best fit. Statistical analysis using SAS 9.3 software and Tukey's HSD test revealed the significant effect (p < 0.001) of soil type on sorption. Sorption correlated positively with the organic carbon and clay contents of the soil.

LC-MS/MS method optimization and validation for trace-level analysis of 71 crop protection chemicals in pulses.

An analytical method involving modified QuEChERS (quick, easy, cheap, effective, rugged and safe) technique coupled with LC-MS/MS (liquid chromatography-tandem mass spectroscopy) has been developed for simultaneous identification and quantification of 71 pesticides (insecticides/acaricides/nematicides (32), fungicides (12), herbicides (26), plant growth regulator (1)) in different pulses (edible seeds of leguminous plants), namely gram, lentil, black gram and pea. The analysis was done using Shimadzu LC-MS/MS-8030 instrument equipped with Zorbax Eclipse Plus C-18 column operating under electrospray ionization (ESI) in positive and negative modes. Validation of method was done as per a single laboratory validation approach. Nine-point linear calibration curves for each pesticide were obtained in the range of 0.005 to 2 µg/g with correlation coefficient of ≥ 0.98. Limit of detection (LOD) for all the pesticides was achieved in the range of 0.001-0.015 µg/g, whereas the limit of quantification (LOQ) were found in the range of 0.01-0.05 µg/g. Recovery studies were conducted at 0.01- and 0.05-µg/g level of fortification using modified buffered QuEChERS method standardized for low moisture foods. It was observed that due to matrix interference, only around 75% of the pesticides were recovered in an acceptable range of 70-120% when compared against the solvent standard. With matrix-matched standards, 95% of the recovery results came within acceptable range with highly acceptable HorRat ratio (between 0.2 and 0.8) indicating satisfactory precision. The global and expanded uncertainties for estimation of each pesticide in above-mentioned pulse matrices were calculated to evaluate the suitability of the developed method for quantification of pesticides in pulse matrices.

Application of magnetic molecularly imprinted polymers for extraction of imidacloprid from eggplant and honey.

A magnetic molecularly imprinted polymer (MMIP) adsorbent for imidacloprid was prepared using non-covalent approach with functionalized nano Fe3O4 particles (magnetic cores), imidacloprid (template), acrylic acid (functional monomer), ethylene glycol dimethacrylate (cross linker) and azobisisobutyronitrile (initiator) and used for selective separation of imidacloprid from honey and vegetable samples. The polymers were characterized using FT-IR spectroscopy, SEM and TEM images. For analysis of imidacloprid LC-MS/MS equipment was used. Adsorption kinetics was best explained by pseudo-second-order kinetic model. Adsorption data fitted well into linearized Freundlich equation (R2 > 0.98). Scatchard plot analysis indicates the presence of two classes of binding sites in the MMIPs with the Cmax of 1889.6 µg g-1 and 65448.9 µg g-1, respectively. MMIPs demonstrated much higher affinity for imidacloprid over structurally similar analogues acetamiprid (α = 23.59) and thiamethoxam (α = 17.15). About 87.1 ±â€¯5.0% and 90.6 ±â€¯5.6% of the added imidacloprid was recovered from MMIPs in case of fortified eggplant and honey samples, respectively.

Optimization of isotherm models for pesticide sorption on biopolymer-nanoclay composite by error analysis.

A carboxy methyl cellulose-nano organoclay (nano montmorillonite modified with 35-45 wt % dimethyl dialkyl (C14-C18) amine (DMDA)) composite was prepared by solution intercalation method. The prepared composite was characterized by infrared spectroscopy (FTIR), X-Ray diffraction spectroscopy (XRD) and scanning electron microscopy (SEM). The composite was utilized for its pesticide sorption efficiency for atrazine, imidacloprid and thiamethoxam. The sorption data was fitted into Langmuir and Freundlich isotherms using linear and non linear methods. The linear regression method suggested best fitting of sorption data into Type II Langmuir and Freundlich isotherms. In order to avoid the bias resulting from linearization, seven different error parameters were also analyzed by non linear regression method. The non linear error analysis suggested that the sorption data fitted well into Langmuir model rather than in Freundlich model. The maximum sorption capacity, Q0 (µg/g) was given by imidacloprid (2000) followed by thiamethoxam (1667) and atrazine (1429). The study suggests that the degree of determination of linear regression alone cannot be used for comparing the best fitting of Langmuir and Freundlich models and non-linear error analysis needs to be done to avoid inaccurate results.