Determination of antifungal efficacy and phytotoxicity of a unique silica coated porous zinc oxide nanocomposite medium for slow-release agrochemicals.

AIMS: In this study the antifungal efficacy and phytotoxicity of silica coated porous zinc oxide nanoparticle (SZNP) was analyzed as this nanocomposite was observed to be a suitable platform for slow release fungicides and has the promise to bring down the dosage of other agrochemicals as well. METHODS AND RESULTS: Loading and release kinetics of tricyclazole, a potent fungicide was analyzed by measuring surface area (SBET) using Brunauer-Emmett-Teller (BET) isotherm and LC-MS/MS respectively. The antifungal efficacy of ZnO nanoparticle (ZNP) and SZNP was investigated on two phytopathogenic fungi (Alternaria solani and Aspergillus niger). The morphological changes to the fungal structure due to ZNP and SZNP treatment were studied by field emission-scanning electron microscopy (FESEM). Nanoparticle mediated elevation of reactive oxygen species in fungal samples was detected by analyzing the level of superoxide dismutase, catalase, thiol content, lipid peroxidation and by 2,7-dichlorofluorescin diacetate (DCFH-DA) assay. The phytotoxicity of these two nanostructures was assessed in rice plants by measuring primary plant growth parameters. Further, the translocation of the nanocomposite in the same plant model system was examined by checking the presence of Fluorescein isothiocyanate (FITC) tagged SZNP within the plant tissue. CONCLUSIONS: ZNP had superior antifungal efficacy than SZNP and caused generation of more reactive oxygen species (ROS) in the fungal samples. Even then SZNP was preferred as an agrochemical delivery vehicle because unlike ZNP alone it was not toxic to plant system. Moreover, as silica in nano form is entomotoxic in nature and nano ZnO has antifungal property, both the cargo (agrochemical) and the carrier system (silica coated porous nano zinc oxide) will have a synergistic effect in crop protection.

Sorption and mobility assessment of tembotrione in soils of upper, trans and middle Gangetic plain zones of India.

The presence of undesired agrochemicals residues in soil and water poses risks to both human health and the environment. The behavior of pesticides in soil depends both on the physico-chemical properties of pesticides and soil type. This study examined the adsorption-desorption and leaching behavior of the maize herbicide tembotrione in soils of the upper (UGPZ), trans (TGPZ) and middle Gangetic plain zones of India. Soil samples were extracted using acetone followed by partitioning with dichloromethane, whereas liquid-liquid extraction using dichloromethane was used for aqueous samples. Residues of tembotrione and its metabolite TCMBA, {2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluoroethoxy) methyl] benzoic acid}, were quantified using liquid chromatography-tandem mass spectrometry. The data revealed that tembotrione adsorption decreased with increasing pH and dissolved organic matter but increased with salinity. The maximum adsorption occurred at pH 4, 0.01 m sodium citrate and 4 g/L NaCl, with corresponding Freundlich constants of 1.83, 2.28 and 3.32, respectively. The hysteresis index <1 indicated faster adsorption than desorption. Leaching studies under different flow conditions revealed least mobility in UGPZ soil and high mobility in TGPZ soil, consistent with groundwater ubiquity scores of 4.27 and 4.81, respectively. Soil amendments decreased tembotrione mobility in the order: unamended > wheat straw ash > wheat straw > farm yard manure > compost. The transformation of tembotrione to TCMBA and its mobility in soil columns were also assessed.

Bioaerosol emissions from wastewater treatment process at urban environment and potential health impacts.

The inlet of wastewater treatment plants (WWTPs) contains pathogenic microorganisms which during aeration and by mechanical mixing through wind typically aerosolized microbes into ambient air. Bioaerosol emission and its characterization (bacterial and fungal) was investigated considering low-flow and high-flow inlet of wastewater treatment plant. Generation of bioaerosols was found influenced by prevailing seasons while both during summer and winter, fungal concentration (winter: 1406 ± 517; summer: 1743 ± 271 CFU/m3) was higher compared to bacterial concentration (winter: 1077 ± 460; summer: 1415 ± 588 CFU/m3). Bioaerosols produced from WWTPs were predominately in the size range of 2.1-4.7 µm while fraction of fungal bioaerosols were also in ultra-fine range (0.65 µm). Bioaerosols reaching to the air from WWTPs varied seasonally and was calculated by aerosolization ratio. During summer, aerosolization of the bioaerosols was nearly 6 times higher than winter. To constitute potential health effects from the exposure to these bioaerosols, biological characterization, antibiotics resistance and the health survey of the nearby area were also performed. The biological characterization of the bioaerosols samples were done through metagenomic approach using 16s and ITS metagenomic sequencing. Presence of 167 genus of bacteria and 41 genus of fungi has been found. Out of this, bacillus (73%), curtobacterium (21%), pseudomonas, Exiguo bacterium, Acinetobacter bacillaceae, Enterobacteriaceae and Prevotella were the dominant genus (top 10) of bacteria. In case of fungi, xylariales (49%), Hypocreales (19%), Coperinopsis (9%), Alternaria (8%), Fusarium (6%), Biopolaris, Epicoccum, Pleosporaceae, Cladosporium and Nectriaceae were dominant. Antibiotics like, Azithromycin and cefixime were tested on the most dominant bacillus showed resistance on higher concentration of cefixime and lower concentration of azithromycin. Population-based health survey in WWTP nearby areas (50-150 m periphery) found several types of diseases/symptoms including respiratory problem, skin rash/irritation, change in smell and taste, eye irritation within the resident population and workers.

Novel moisture retaining dustable powder containing Steinernema abbasi effectively controls damage of subterranean termite in wheat and chickpea.

The application of biocontrol agents in farm operations for pest control programs is gaining priority and preference globally. Effective delivery, infectivity of the biocontrol agents, and quality shelf-life products containing these bioagents are vital parameters responsible for the success of biopesticides under field conditions. In the present study, moisture-retaining bio-insecticidal dustable powder formulation (SaP) of Steinernema abbasi (Sa) infective juveniles (IJs) was developed and assessed for its shelf life, physicochemical profile, and bio-efficacy against subterranean termite under field conditions. Formulation exhibited free-flowing character, with pH of 6.50-7.50, and apparent density in the range 0.50-0.70 g cm-3. The bioefficacy study for two rabi seasons (2020-2021, and 2021-2022) in wheat and chickpea grown in an experimental farm heavily infested with subterranean termites (Odontotermes obesus) revealed a significant reduction in plant damage due to pest attack in formulation-treated plots, monitored in terms of relative number of infested tillers in wheat and infested plants in chickpea fields. The reduced damage to the crop caused by termite was reflected in the relative differences in the growth and yield attributes as well. The study establishes the potential of the developed product as a biopesticide suitable for organic farming and integrated pest management operations.

Determination of quizalofop-p-ethyl in onion: residual dissipation pattern, weed control efficiency, and food safety assessment under field conditions.

Monitoring pesticide residue levels becomes crucial to maintain quality and guarantee food safety as the consumption of onion green leaves and immature and mature bulbs (either raw or processed) rises. A field experiment was conducted for two consecutive seasons with quizalofop-p-ethyl (5% EC) at 50 and 100 g a.i. ha-1 to evaluate weed control efficiency and to determine terminal residues. Post-emergence application of fop herbicide at 100 g a.i. ha-1 kept the weed density and dry weight reasonably at a lower level and enhanced the productivity of onion with higher economic returns. A rapid, sensitive, and analytical method was developed using high-performance liquid chromatography (HPLC) with excellent linearity (r2 > 0.99). The limit of quantification for quizalofop-p-ethyl was established at 0.04 mg kg-1 with signal to noise (S/N) ratio ≥ 10. The method was successfully applied and initial quantified residues were in the range of 2.5-4.4 mg kg-1 irrespective of seasons and doses. Finally, the presence of targeted herbicide residues in harvested samples was confirmed by liquid chromatography tandem mass spectrometry (LC-MS/MS) under optimized operating conditions. Dietary risk assessment assured harvested onions were safe for consumption at the recommended dose. It also can be concluded that quizalofop ethyl did not adversely influence soil micro-organisms at standard rates of application.

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.

Persistence and transformation of flucetosulfuron herbicide in soil as affected by biotic and abiotic factors.

Effect of biotic and abiotic factors of soil on persistence and transformation of flucetosulfuron was studied in three soils from paddy growing zones of India. Herbicide residues in three soils dissipated with half-life ranging from 1.41 to 8.38 and 0.58 to 1.14 days under sterile and non-sterile conditions, respectively. Acidic pH and soil microbial activity contributed more toward the degradation of flucetosulfuron in soil. Under flooded soils, dissipation was bit slower than under field capacity moisture level. Five transformation products were identified with LC-MS/MS analysis. Ester hydrolysis and sulfonyl urea bridge cleavage seems to be the major transformation pathways for flucetosulfuron in soil.

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.

Development of a QuEChERS-LCMS/MS method for simultaneous estimation of tebuconazole and chlormequat chloride in wheat crop.

Tebuconazole (TBZ) and Chlormequat chloride (CCC) combination has been established as highly effective in reducing plant height of lodging prone wheat varieties. In this work, a novel analytical method employing the quick, easy, cheap, effective, rugged and safe (QuEChERS) cleanup technique and LC-MS/MS (liquid chromatography-tandem mass spectroscopy) was developed for simultaneous estimation of TBZ and CCC in wheat grains and harvest stage plant leaves. A total of 10 mL of acetonitrile and 50 mg of primary secondary amine (PSA) sorbent was consumed in the optimized QuEChERS process for leaves and grain samples. The LC-MS/MS analysis was performed using a C-18 column operating under electrospray ionization in positive mode. The QuEChERS approach achieved extraction recoveries in the acceptable range of 70%-120%, for both the compounds and was validated in terms of accuracy, precision, sensitivity and linearity. Persistence study was conducted using Lihocin (CCC 50% SL), Folicur (TBZ 25.9% EC) and their combination tank mix (Lihocin + Folicur-50% SL + 25.9% EC) applied as foliar spray twice in wheat crop (tester tall variety C-306). The results demonstrated that the developed QuEChERS-LCMS/MS is rapid and confirmatory for simultaneous quantification of both the test analytes in wheat crop.

Estimation of High-Resolution PM2.5 over the Indo-Gangetic Plain by Fusion of Satellite Data, Meteorology, and Land Use Variables.

Very high spatially resolved satellite-derived ground-level concentrations of particulate matter with an aerodynamic diameter of less than 2.5 µm (PM2.5) have multiple potential applications, especially in air quality modeling and epidemiological and climatological research. Satellite-derived aerosol optical depth (AOD) and columnar water vapor (CWV), meteorological parameters, and land use data were used as variables within the framework of a linear mixed effect model (LME) and a random forest (RF) model to predict daily ground-level concentrations of PM2.5 at 1 km × 1 km grid resolution across the Indo-Gangetic Plain (IGP) in South Asia. The RF model exhibited superior performance and higher accuracy compared with the LME model, with better cross-validated explained variance (R2 = 0.87) and lower relative prediction error (RPE = 24.5%). The RF model revealed improved performance metrics for increasing averaging periods, from daily to weekly, monthly, seasonal, and annual means, which supported its use in estimating PM2.5 exposure metrics across the IGP at varying temporal scales (i.e., both short and long terms). The RF-based PM2.5 estimates showed high PM2.5 levels over the middle and lower IGP, with the annual mean exceeding 110 µg/m3. As for seasons, winter was the most polluted season, while monsoon was the cleanest. Spatially, the middle and lower IGP showed poorer air quality compared to the upper IGP. In winter, the middle and lower IGP experienced very poor air quality, with mean PM2.5 concentrations of >170 µg/m3.

Rolled Up or Crumpled: Phases of Asymmetric Tethered Membranes.

We show that inversion-asymmetric tethered membranes exhibit a new double-spiral phase with long range orientational order not present in symmetric membranes. We calculate the universal algebraic spiral shapes of these membranes in this phase. Asymmetry can trigger the crumpling of these membranes as well. In vitro experiments on lipid membranes, red blood cell membrane extracts, and on graphene coated on one side, could test these predictions.

Persistence, dissipation, and risk assessment of a combination formulation of trifloxystrobin and tebuconazole fungicides in/on tomato.

Multi-locational supervised field trials were conducted in different agro-climatic regions in India to study dissipation of trifloxystrobin and tebuconazole in tomato after spraying a combination formulation (trifloxystrobin 25% + tebuconazole 50%, 75WG) at recommended doses: (i) single (trifloxystrobin 87.5 g a.i. ha-1 + tebuconazole 175 g a.i. ha-1) and (ii) double (trifloxystrobin 175 g a.i. ha-1 + tebuconazole 350 g a.i. ha-1). Fruit samples were extracted with ethyl acetate using a modified QuEChERS method. The residues (parent fungicides + metabolite) were analyzed and confirmed by GC-ECD and GC-MS, respectively. The half-life (t1/2) of trifloxystrobin and tebuconazole in tomato varied from 1.08 to 1.72 and 1.13 -to 1.64 days at single; and 1.27 to 2.13 and 1.24 to 1.96 days at double dose, respectively. Since maximum residue limit (MRL) at pre-harvest interval (PHI) of 5 days is impractical, as tomato is usually harvested and consumed almost everyday after the last spray, the risk assessment was performed at minimum PHI of 1 day. Accordingly, on the basis of supervised field trial data and using OECD MRL calculator, MRL of 0.5 and 1.5 mg kg-1 at single dose were proposed for trifloxystrobin and tebuconazole in/on tomato, respectively.

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.

Temporal evolution of submicron particles during extreme fireworks.

Evolution of submicron particles in terms of particle number concentration and mobility-equivalent diameter was measured during Diwali festival-specific intensive pyrotechnic displays in Varanasi over central Indo-Gangetic Plain (IGP). A scanning mobility particle sizer coupled with an optical particle sizer was used to fit in an overlapping size range, and particle number concentration was analyzed to have an insight into the new particle formation and subsequent evolution of particles from nucleation to accumulation mode. Further, variation in black carbon (BC) concentration and aerosol ionic composition was measured simultaneously. Frequent fluctuation in particle number concentration in and around Diwali festival was evidenced, primarily influenced by local emission sources and meteorology, with three distinct peaks in number concentrations (dN/dlogDp, 3.1-4.5 × 104 cm3) coinciding well with peak firework emission period (18:00-23:00 h). Submicron particle size distribution revealed a single peak covering a size range of 80-130 nm, and for all instances, number concentration maximum coincided with geometric mean minimum, indicating the emission primarily in the ultrafine range (< 0.1 µm). Interestingly, during peak firework emissions, besides rise in accumulation mode, an event of new particle formation was identified with increase in nucleation and small Aitken mode, before being dispersed to background aerosols. On an integral scale, a clear distinction was noted between a normal and an episodic event, with a definite shift in the formation of ultrafine particles compared with the accumulation mode. The BC diurnal profile was typical, with a prominent nocturnal peak (12.0 ± 3.9 µg m-3) corresponding to a decrease in the boundary layer height. A slight variation in maximum BC concentration (16.8 µg m-3) was noted in the night of the event coinciding well with firework emissions. An increase in some specific ionic species was also noted in combination with an increase in the overall cation to anion ratio, which was explained in terms of heterogeneous transformation of NOx and catalytic conversion of SO2. Graphical abstract Time-resolved evolution of particle size distribution during normal and episodic events.

Chemical Degradation of Sulfosulfuron in Aqueous Suspension of Rice and Wheat Straw Ashes.

Burning of wheat and rice straw on field, after crop harvest, is a quick, cheap and an easy way for land clearing. The ashes generated after burning are mixed with soils and due to their alkaline nature, they may affect the degradation of applied herbicides. Therefore, present paper reports degradation of sulfosulfuron in aqueous suspension of the wheat (WSA) and rice (RSA) straw ashes. The results suggested that both ashes significantly enhanced sulfosulfuron dissipation in water and effect was more with the RSA. The solution pH affected sulfosulfuron dissipation and in control buffers (no ash) herbicide degradation followed the order: acidic > alkaline > neutral. Addition of the RSA significantly increased sulfosulfuron degradation in buffers, but effect was more evident at neutral and alkaline pH. The study has relevance in assessing degradation of sulfosulfuron in soils where crop residues are burned for land clearing.

Airborne particulate in Varanasi over middle Indo-Gangetic Plain: variation in particulate types and meteorological influences.

The variation in particulate mass and particulate types (PM2.5 and PM10) with respect to local/regional meteorology was analyzed from January to December 2014 (n = 104) for an urban location over the middle Indo-Gangetic Plain (IGP). Both coarser (mean ± SD; PM10 161.3 ± 110.4 µg m-3, n = 104) and finer particulates (PM2.5 81.78 ± 66.4 µg m-3) revealed enormous mass loading with distinct seasonal effects (range: PM10 12-535 µg m-3; PM2.5 8-362 µg m-3). Further, 56% (for PM2.5) to 81% (for PM10) of monitoring events revealed non-attainment national air quality standard especially during winter months. Particulate types (in terms of PM2.5/PM10 0.49 ± 0.19) also exhibited temporal variations with high PM2.5 loading particularly during winter (0.62) compared to summer months (0.38). Local meteorology has clear distinguishing trends in terms of dry summer (March to June), wet winter (December to February), and monsoon (July to September). Among all the meteorological variables (average temperature, rainfall, relative humidity (RH), wind speed (WS)), temperature was found to be inversely related with particulate loading (rPM10 -0.79; rPM2.5 -0.87) while RH only resulted a significant association with PM2.5 during summer (rPM10 0.07; rPM2.5 0.55) and with PM10 during winter (rPM10 0.53; rPM2.5 0.24). Temperature, atmospheric boundary layer (ABL), and RH were cumulatively recognized as the dominant factors regulating particulate concentration as days with high particulate loading (PM2.5 >150 µg m-3; PM10 >260 µg m-3) appeared to have lower ABL (mean 660 m), minimum temperature (<22.6 °C), and high RH (∼79%). The diurnal variations of particulate ratio were mostly insignificant except minor increases during night having a high wintertime ratio (0.58 ± 0.07) over monsoon (0.34 ± 0.05) and summer (0.30 ± 0.07). Across the region, atmospheric visibility appeared to be inversely associated with particulate (rPM2.5 -0.84; rPM10 -0.79) for all humid conditions, while at RH ≥80%, RH appeared as the most dominant factor in regulating visibility compared to particulate loading. The Lagrangian particle dispersion model was further used to identify possible regions contributing particulate loading through regional/transboundary movement.

Eco-friendly PEG-based controlled release nano-formulations of Mancozeb: Synthesis and bioefficacy evaluation against phytopathogenic fungi Alternaria solani and Sclerotium rolfsii.

Controlled release (CR) nano-formulations of Mancozeb (manganese-zinc double salt of N,N-bisdithiocarbamic acid), a protective fungicide, have been prepared using laboratory-synthesized poly(ethylene glycols) (PEGs)-based functionalized amphiphilic copolymers without using any surfactants or external additives. The release kinetics of the developed Mancozeb CR formulations were studied and compared with that of commercially available 42% suspension concentrate and 75% wettable powder. Maximum amount of Mancozeb was released on 42nd day for PEG-600 and octyl chain, PEG-1000 and octyl chain, and PEG-600 and hexadecyl chain, on 35th day for PEG-1000 and hexadecyl chain, on 28th day for PEG-1500 and octyl chain, PEG-2000 and octyl chain, PEG-1500 and hexadecyl chain, and PEG-2000 and hexadecyl chain in comparison to both commercial formulations (15th day). The diffusion exponent (n value) of Mancozeb in water ranged from 0.42 to 0.62 in tested formulations. The half-release (t1/2) values ranged from 17.35 to 35.14 days, and the period of optimum availability of Mancozeb ranged from 18.54 to 35.42 days. Further, the in vitro bioefficacy evaluation of developed formulations was done against plant pathogenic fungi Alternaria solani and Sclerotium rolfsii by poison food technique. Effective dose for 50% inhibition in mgL-1 (ED50) values of developed formulations varied from 1.31 to 2.79 mg L-1 for A. solani, and 1.60 to 3.14 mg L-1 for S. rolfsii. The present methodology is simple, economical, and eco-friendly for the development of environment-friendly CR formulations of Mancozeb. These formulations can be used to optimize the release of Mancozeb to achieve disease control for the desired period depending upon the matrix of the polymer used. Importantly, the maximum amount of active ingredient remains available for a reasonable period after application. In addition, the developed CR formulations were found to be suitable for fungicidal applications, allowing use of Mancozeb in lower doses.

Multilocation field trials for risk assessment of a combination fungicide Fluopicolide + Propamocarb in tomato.

Dissipation kinetics of two systemic fungicides, namely fluopicolide and propamocarb used as a combination formulation (Infinito 68.75 SC), were studied on tomato at four different locations by the All India Network Project on Pesticide Residues to recommend their pre-harvest interval (PHI) and to propose the maximum residue limits (MRL) for the two fungicides based on chronic hazard exposure assessment. The combination fungicide was sprayed thrice at the recommended dosage of 93.75 g a.i./ha fluopicolide and 937.50 g a.i./ha propamocarb as well as at double the recommended dosage of 187.50 g a.i./ha fluopicolide and 1875.0 g a.i./ha propamocarb on tomato crops and the residues were monitored periodically by GC-MS. The fungicides dissipated to below the limit of quantification (LOQ) within 10 to 15 days, with a half-life of 2-4 days for fluopicolide and 1-2 days for propamocarb. Taking into consideration the MRLs of codex and calculations made using the method of MRL fixation of the Food Safety and Standard Authority of India (FSSAI) as well as the Organization for Economic Co-operation and Development (OECD) calculator, MRL of 5 mg/kg is proposed for fluopicolide and 15 mg/kg for propamocarb, following critical exposure of the commodity considering PHI of 1 day.

Persistence and risk assessment of spiromesifen on tomato in India: a multilocational study.

Supervised field trials were conducted at four different agro-climatic locations of India to evaluate the dissipation pattern and risk assessment of spiromesifen on tomato. Spiromesifen 240 SC was sprayed on tomato at 150 and 300 g a.i. ha(-1). Samples of tomato fruits were drawn at 0, 1, 3, 5, 7, 10 and 15 days after treatment and soil at 15 days after treatment. Quantification of residues was done on gas chromatograph-mass spectrophotometer in selective ion monitoring mode in the mass range of 271-274 (m/z). The limit of quantification of the method was found to be 0.05 mg kg(-1), while the limit of determination was 0.015 mg kg(-1). Residues were found below the LOQ of 0.05 mg kg(-1) in 10 days at both the doses of application at all the locations. Spiromesifen dissipated with a half-life of 0.93-1.38 days at the recommended rate of application and 1.04-1.34 days at the double the rate of application. Residues of spiromesifen in soil were detectable level (<0.05 mg kg(-1)) after 15 days of treatment. A preharvest interval (PHI) of 1 day has been recommended on tomato on the basis of data generated under All India Network Project on Pesticide Residues. Spiromesifen 240 SC has been registered for its use on tomato by Central Insecticide Board and Registration Committee, Ministry of Agriculture, Government of India. The maximum residue limit (MRL) of spiromesifen on tomato has been fixed by Food Safety Standard Authority of India, Ministry of Health and Family Welfare, Government of India as 0.3 µg/g after its risk assessment.

Development and validation of LC-MS/MS method for trace analysis of acrylamide, acrylic acid and N, N-methylene bis acrylamide in sandy loam soil.

Acrylamide and N, N-methylene bis acrylamide are most commonly used monomer and crosslinker compounds employed in synthesis of super absorbent hydrogels. When applied as soil conditioners, there are apprehensions that these hydrogels degrade over time and thus may release the toxic monomers in the soil. A method was thus developed using Liquid Chromatography tandem mass spectrometry (LC-MS/MS) for the trace level quantification of acrylamide (AD), acrylic acid (AA) and N,N-methylene-bis-acrylamide (MBA) in sandy loam soil amended by two test hydrogels the Pusa Hydrogel and SPG 1118 hydrogel prepared using AD and MBA. The MRM (multiple reaction monitoring) transitions were optimized for both the compounds. Soil samples were extracted using dispersive solid-phase extraction (dSPE) with a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) technique, employing acetonitrile. All analytes were quantified at trace levels within a five-minute run using UHPLC equipped with a C-18 column. Single laboratory validation of the developed method in soil matrix was conducted based on specificity, linearity, sensitivity, accuracy, precision, matrix effect and measurement of uncertainty. LC-MS/MS exhibited a linear response in the concentration range of 0.001 to 1 µg mL-1, with correlation coefficient >+0.99. Acceptable recovery (within 70-120 %) with repeatability (%RSD ≤20 %) was obtained at 0.01 to 1 µg g-1 fortification levels. LOQ (Limit of quantification) of the method for AD, AA and MBA in soil matrix were 0.05, 1 and 0.01 µg g-1, respectively. Both intra-laboratory repeatability and intermediate precision at LOQ suggested well acceptable precise (HorRat≈ 0.3) method for quantification. Matrix enhancement effect was observed in the order: AA>AD>MBA. The Expanded Uncertainty (EU) in soil matrix at LOQ was 21.64 %, 28 % and 19 % for AD, AA and MBA respectively. Groundnut and wheat grown with application of the hydrogels showed no detectable residues of monomers in soil samples (total n = 60) near the root zone at the time of crop harvesting.