Harnessing the Carrier Solvent Complexity of Crop Biostimulant Liquid Formulations Using Locally Available Transesterified Waste Cooking Oil: Economic Recycling, Solvent Performance, and Bioefficacy Evaluation.

Locally sourced waste cooking oil (WCO) was successfully base-catalyzed and transesterified with methanol into biodiesel to produce biostimulant (nitrobenzene) formulations and replace high-risk carrier solvents. Ideal synthesis conditions were composed of 1% NaOH, MeOH/oil molar ratio (6:1), reaction temperature (65 °C), a 3 h mixing rate, and 97-98% yields. Gas chromatography-mass spectrometry (GC-MS) analysis identified five fatty acid methyl esters (FAMEs) including palmitic, linoleic, oleic, stearic, and eicosenoic acids with high solubilization and olfactory characteristics. Using anionic and nonionic emulsifiers in conjunction with recycled biodiesel, a stable emulsifiable concentrate (NB 35% EC) was created with greater storage stability, wettability, and spreading capabilities than those of organic solvent-based ones. The highest counts of fruits per plant (35.80), flowers per plant (60.00), yield per plant (3.56 kg), and yield per hectare (143.7 quintals) were recorded in treatments with 4 mL/L biodiesel-based EC in field bioassays. In addition to having superior biosafety, FAME-based EC exhibits minimal phytotoxicity and is less harmful to aquatic creatures. It was discovered that the average cost-effectiveness was 5.49 times less expensive than solvent-based EC. In order to utilize waste oils as a locally obtained, sustainable alternative solvent with a wide solubilization range, low ecotax profile, circular economy, and high renewable carbon index, this integrative technique was expanded.

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.

Eco-Oriented Formulation and Stabilization of Oil-Colloidal Biodelivery Systems Based on GC-MS/MS-Profiled Phytochemicals from Wild Tomato for Long-Term Retention and Penetration on Applied Surfaces for Effective Crop Protection.

Vegetable oils as hydrophobic reserves in oil dispersions (OD) provide a practical approach to halt bioactive degradation for user and environment-efficient pest management. Using biodegradable soybean oil (57%), castor oil ethoxylate (5%), calcium dodecyl benzenesulfonates as nonionic and an-ionic surfactants, bentonite (2%), and fumed silica as rheology modifiers, we created an oil-colloidal biodelivery sytem (30%) of tomato extract with homogenization. The quality-influencing parameters, such as particle size (4.5 µm), dispersibility (97%), viscosity (61 cps), and thermal stability (2 years), have been optimized in accordance with specifications. Vegetable oil was chosen for its improved bioactive stability, high smoke point (257 °C), coformulant compatibility, and as a green build-in-adjuvant by improving spreadability (20-30%), retention and penetration (20-40%). In in vitro testing, it efficiently controlled aphids with 90.5% mortalities and 68.7-71.2% under field-conditions without producing phytotoxicity. Wild tomato-derived phytochemicals can be a safe and efficient alternative to chemical pesticides when combined wisely with vegetable oils.

Review of extraction and detection techniques for the analysis of pesticide residues in fruits to evaluate food safety and make legislative decisions: Challenges and anticipations.

Fruits are vital parts of the human diet because they include necessary nutrients that the body needs. Pesticide use has increased dramatically in recent years to combat fruit pests across the world. Pesticide usage during production, on the other hand, frequently results in undesirable residues in fruits after harvest. Consumers are concerned about pesticide residues since most of the fruits are directly consumed and even recommended for the patients as dietary supplements. As a result of this worry, pesticide residues in fruits are being randomly monitored to re-assess the food safety situation and make informed legislative decisions. To assess the degree of pesticide residues in fruits, a simple and quick analytical procedure is usually required. As a result, pesticide residue detection (using various analytical techniques: GC, LC and Biosensors) becomes critical, and regulatory directives are formed to regulate their amounts via the Maximum Residue Limit (MRL). Over the previous two decades, a variety of extraction techniques and analytical methodologies for xenobiotic's efficient extraction, identification, confirmation and quantification have been developed, ranging from traditional to advanced. The goal of this review is to give readers an overview of the evolution of numerous extraction and detection methods for pesticide residue analysis in fruits. The objective is to assist analysts in better understanding how the ever-changing regulatory landscape might drive the need for new analytical methodologies to be developed in order to comply with current standards and safeguard consumers.

Simultaneous Monitoring and Decontamination of Pesticide Residues in Phytomedicine-Enriched Betel Leaf Utilizing QuEChERS-GC-MS/MS Technology to Safeguard Public Health.

BACKGROUND: The presence of undesirable substances, including pesticides (xenobiotics) in betel leaf (Piper betel), is a great concern for consumers because it is chewed and consumed directly. To protect the consumer's health, a modified QuEChERS method for monitoring purposes and subsequent decontamination process has been developed. OBJECTIVE: The goal of this work was to establish a multi-residue analytical method for monitoring nonpermitted organophosphorus pesticide residues in betel leaf, as well as cost-effective cleaning strategies. METHOD: The homogenized 15 g samples (20 betel leaf samples collected in West Bengal, India) were extracted with a modified QuEChERS method using acetonitrile, reconstituted to acetone, and finally analyzed by GC-MS/MS. Possible decontamination techniques (such as tap water washing, 2% saltwater washing, and lukewarm water washing) were evaluated. RESULTS: The limit of detection ranged from 0.003 to 0.005 mg/kg, and limit of quantification was 0.01 mg/kg. Recoveries ranged from 80 to 120% with RSDr 9%. One sample was found to contain three pesticides 4 to 7 times higher than MRLs. Suggested decontamination methods allowed reducing toxic traces below European limits. CONCLUSIONS: The suggested approach is useful for determining pesticide residues in betel leaves quickly. Traditional techniques of processing betel leaves may reduce pesticide residues below regulatory limits. HIGHLIGHTS: A multi-residue method and decontamination of pesticides in betel leaf using QuEChERS-GC-MS/MS technology with satisfactory method performance was achieved. Domestic decontamination techniques have a high efficacy in reducing pesticide residues from betel leaves, making them safe for human consumption.

Long-term profound investigation of Fenoxaprop-p-ethyl and indirect pesticide pollution in jute-cropped environmental ecosystem for dietary and ecological risk assessment.

Jute is a healthy vegetable due to its high content of carotenoids, vitamins, and minerals, in addition to its industrial utility. The purpose of this study was to look into the dissipation of fenoxaprop-p-ethyl and to track indirect sources of pesticide accumulation in jute ecosystems for three years in a row during tropical monsoon seasons. To avoid the intake of residues over approved limits, a rapid extraction technique was developed to evaluate the residues of this herbicide (Whip-Super 9% EC) in jute leaves, fiber, cropped soil, and water. A modified QuEChERS approach based on liquid chromatography and ultraviolet-visible (UV-VIS) detection was developed and successfully validated in accordance with SANCO requirements. Gas chromatography mass spectrometer (GC-MS) was used to examine fish and water samples from jute fields and retting pond for twenty widely-used multi-class pesticide contaminations from indirect sources. Relative standard deviations (RSD) (≤ 20) and recoveries (100-115%) are observed to be within acceptable ranges. In edible jute leaves, independent of season, first-order kinetics of dissipation was recorded, with half-lives ranging from 0.61 to 0.68 days. Based on the findings of the risk assessment, it is feasible to conclude that the consumer health risks of ingesting jute leaves are insignificant, even on day zero, when used at the recommended amount, and that using jute bags for food packaging and storage is safe. But jute field water was found to be less polluted with indirect pesticides than water from a nearby jute retted pond. Fish samples from this jute retted pond were also analyzed and found to be 26% contaminated. The presence of quinalphos and chlorpyriphos in jute retting water and fish might pose a concern to consumer health and environmental ecosystems.

Selection of green carrier solvent for the effective creation of bio-inspired liquid formulation and anti-fungal potency evaluation.

Existing pesticide formulation solvents generate volatile organic compounds (VOCs), are combustible, and are classed as hazardous air pollutants (HAPs), meaning they are detrimental to users and phytotoxic to crops. Green solvents are required in formulations due to regulations, health, and environmental concerns. In emulsifiable concentration (EC) formulations, the "green chemistry" movement has led to the use of less harmful solvents. After a detailed and comparative fungal growth inhibition assessment, the least harmful carrier solvent among four regularly used organic solvents [dimethyl sulfoxide (DMSO), dimethylformamide (DMF), aromatic hydrocarbon (C9), and methyl oleate] was chosen in this study. We employed methyl oleate (cis-9-Octadecenoic acid methyl ester) as a bio-based green reserver (60%) to create effective bioinspired EC formulations (30%) of Pongamia pinnata L extract utilising emulsifier blends (10 percent) based on the known toxicity order (DMF > DMSO > C9 > methyl oleate). EC1 outperformed the other thirteen formulations (EC1-EC13) in terms of emulsion stability, cold test, accelerated storage stability, flash point, and other metrics, proving its suitability for commercial production. Using four therapeutically appropriate concentrations of agricultural usage, in-vitro fungicidal effects against Alternaria solani and Phytophthora spp. were examined.A. solani (EC50 = 0.08 percent) showed the greatest growth suppression (87.4 percent) at the maximum dosage (1 percent), followed by Phytophthora sp. (71.1 percent) (EC50 = 0.49 percent). The study proved its utility in the production of environmentally acceptable green solvent-based herbal formulations as a long-term crop protection alternative to harmful chemical pesticides.

Bioengineering of neem nano-formulation with adjuvant for better adhesion over applied surface to give long term insect control.

Although safe and eco-friendly botanical pesticides have been intensively promoted to combat pest attacks in agriculture, but their stability and efficacies remain an issue for their wide acceptability as sustained and effective approaches. The purpose of this work was to develop stable neem oil based nano-emulsion (NE) formulation with enhanced activity employing suitable bio-inspired adjuvant. So, Neem NEs (with and without) natural adjuvants (Cymbopogon citratus and Prosopis juliflora) in different concentrations were prepared and quality parameters dictating kinetic stability, acidity/alkalinity, viscosity, droplet size, zeta potential, surface tension, stability and compatibility were monitored using Viscometer, Zetasizer, Surface Tensiometer, High Performance Liquid Chromatography (HPLC) and Fourier Transform Infrared Spectroscopy (FTIR). Nano-emulsion biosynthesis optimization studies suggested that slightly acidic (5.9-6.5) NE is kinetically stable with no phase separation; creaming or crystallization may be due to botanical adjuvant (lemongrass oil). Findings proved that Prosopis juliflora, acted as bio-polymeric adjuvant to stabilize NE by increasing Brownian motion and weakening the attractive forces with smaller droplets (25-50 nm), low zeta potential (-30 mV) and poly-dispersive index (<0.3). Botanical adjuvant (30%) based NE with optimum viscosity (98.8cPs) can give long term storage stability and improved adhesiveness and wetting with reduced surface tension and contact angle. FT-IR analysis assured azadirachtin's stability and compatibility with adjuvant. With negligible degradation (1.42%) and higher half-life (t1/2) of 492.95 days, natural adjuvant based NE is substantially stable formulation, may be due to presence of glycosidic and phenolics compounds. Neem 20NE (with 30% adjuvant) exhibited remarkable insecticidal activity (91.24%) against whitefly (Bemisia tabaci G.) in brinjal (Solanum melongena) as evidenced by in-vivo assay. Results thus obtained suggest, bio-pesticide formulation may be used as safer alternative to chemical pesticides to minimize pesticide residues and presence of natural adjuvant may improves the stability and efficacy of biopesticides for safe crop protection in organic agriculture and Integrated Pest Management.

Method development, validation, monitoring, seasonal effect and risk assessment of multiclass multi pesticide residues in surface and ground water of new alluvial zone in eastern India.

A liquid-liquid extraction (LLE) method was validated as per SANTE/12682/2019 guidelines for gas chromatography-mass spectrometric (GC-MS) determination of thirty-six multiclass pesticides in environmental waters. Seasonal (summer, monsoon, and winter) effects on the magnitude of pesticide residues in environmental water (river, pond, and tube well) of six different urban areas of Nadia and North 24 Parganas districts (New alluvial zone, Eastern India) was monitored for subsequent risk assessment. Total 288 water samples (96 each of river, pond, and tube-well) irrespective of locations and seasons were monitored for multiclass multi pesticide residues during the experiment. Each sample (750 mL) was extracted with ethyl acetate/dichloromethane (8:2) liquid-liquid partitioning and filtration (0.22 µm nylon filter paper) and total residue was reconstituted in acetone (1 mL) for GC-MS analysis with developed and validated method resulting satisfactory recovery percentages (77.84-118.15%). The maximum no. of organochlorine (OC) and organophosphorus (OP) pesticide residues were dominated in river and pond water irrespective of seasons and monitoring sites. About 74% of river water samples were found to be contaminated with concerned pesticides in variable magnitudes. Monsoon (July to October) season was highly alarming with the highest presence of total pesticide residues in different types of environmental waters. Risk quotient (RQ) [acute and chronic] was also evaluated in pond and river water as sometimes used for drinking purposes. RQ value (5900) of total endosulfan indicates the highest risk of chronic toxicity to river fishes. Seven water samples from tube-wells were also monitored and found to be contaminated with butachlor and chlorpyriphos in non-significant amounts (< 0.1 ng mL-1), irrespective of seasons and sites, thus safe for consumption.

Bioefficacy, residue dynamics and dietary risk assessment of gibberellic acid in improving the potential yield of tomato (Solanum lycopersicum L.).

The increasing use of gibberellic acid (GA3) to promote fruit growth and yield has necessitated research into its trace level determination and estimation in harvested product. The phytohormone has increased the tomato yield (tonne ha-1) up to 24.7% with uniform fruit shape, size colour and lustre. A fast, simple, high-throughput analytical method was standardised based on electrospray ionisation - liquid chromatography-tandem mass spectrometry (LC-MS/MS). The samples were extracted using acidified (1% formic acid) methanol. The method was validated as per the SANTE/12682/2019 guidelines. The limits of detection (LOD) and quantification (LOQ) were 0.01 and 0.05 mg kg-1. The average recoveries at LOQ and higher levels were in the range of 86-108% with relative standard deviation (RSD) < 20%. The validated method was successfully applied under field condition by following first-order kinetics with half-lives (T1/2) 1.76 days (recommended dose) and 1.99 days (double dose). The estimated pre-harvest intervals (PHIs) were 6 days (recommended dose) and 8 days (double dose). Studies on dietary risk assessment concluded that even after spray of GA3 at recommended dose, the harvested produce (tomato) could be consumed safely.

Encapsulation, release and insecticidal activity of Pongamia pinnata (L.) seed oil.

Pongamia pinnata (L.) seed oil is effective for its insecticidal and larvicidal activities. However, its low aqueous solubility, high photosensitivity, and high volatility restrict its application for the control of agricultural pests. Encapsulation can be an effective technique to overcome such hindrances. Therefore, P. pinnata oil (PO) was extracted from its seeds and analyzed for karanjin content (3.18%) by GC-MS/MS as the marker compound. Micro-encapsulation (MC) of PO was prepared by interfacial polymerization between isocyanates and polyamine and tested for insecticidal and larvicidal activities. Bioassay of the developed formulations was tested in-vitro against 2nd instar larvae of Bombyx mori (Bivoltine hybrid) and in-vivo insecticidal bio-efficacy was tested against aubergine aphid (Aphis gossypii G.) and whitefly (Bemisia tabaci G.). Various properties of micro-capsules viz., stability, size, oil content and release kinetics were examined. Average diameter of capsules (1 µm) with Zeta potential (-16 mV) was indicated by the Dynamic Light Scattering (DLS) instrument. Existence of PO in the microcapsules was confirmed by an optical microscopic study. Spectroscopic analysis revealed 87.4% of PO was encapsulated in polyurea shell. The shelf-life (T 10 ), half-life (T 50 ), and expiry-life (T 90 ) of polyurea coated capsules were 11.4, 75.3 and 250.0 h, respectively. Polyurea coated PO capsule formulation showed evidence of in-vitro toxicity against 2nd instar larvae of B. mori (LC 50 = 1.1%; LC 90 = 5.9%). The PO formulation also exhibited 67.0-71.8% and 62.4-74.8% control of aphid and whitefly population in aubergine at 4.0% dose following 7-14 days after application. The study unveiled its significance in developing controlled release herbal formulations of P. pinnata as an alternative to harmful conventional synthetic insecticides for crop protection.

Method validation, persistence, and safety evaluation of 2,4-D in tea (Camellia sinensis) by LC-MS/MS.

An analytical method was developed by using LC-ESI(-ve)-MS/MS to investigate the residue dynamics of 2,4-D (2,4-dichlorophenoxyacetic acid) in green tea leaves, processed tea, tea liquor, and tea-cropped soil at Singhiajhora Tea Estate and Putinbari Tea Estate at Terai Region, Darjeeling District, West Bengal, India. In this method, an acidified methanol was used for extraction and subsequent clean-up was done by HLB (hydrophilic lipophilic balanced) cartridges. The method was validated as per SANTE guideline (SANTE/11813/2017). The limit of quantification (LOQ) of 2,4-D was 0.05 mgkg-1 and average % recoveries were in the range from 88.05 to 113.28 with relative standard deviation (RSD) 3.46 to 6.43. The dissipation of 2,4-D followed the 1st-order reaction kinetics with a half-life (T1/2) of 1.51-1.61 day at the recommended dose and 2.50-2.72 day for doubled recommended dose in tea for both locations. This method can be applied successfully for the determination of 2,4 D residues in/on tea matrix and subsequent studies on safety evaluation showed that the use of 2,4-D in tea is safe.

Method Validation for Quantitative Analysis of Metribuzin in Wheat by Liquid Chromatography-Tandem Mass Spectrometry.

A high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated for the accurate determination of metribuzin levels in wheat. The widespread use of this herbicide in the production of wheat is of concern and could follow as well as the need for methodology, which required simple sample preparation being needed. Validation of method was done as per single laboratory validation approach. Samples were extracted through a modified quick, cheap, effective, rugged and safe technique. Sample preparation includes extraction by acetonitrile solvent and cleans up by C18, primary secondary amine and anhydrous MgSO4 for dispersive solid-phase extraction. LC-MS/MS was calibrated at 5 calibration levels with high correlation coefficients (r2) >0.995. Limit of detection and limit of quantitation of metribuzin were 0.01 and 0.03 µg/g, respectively. The mean recovery percentages lie in the range of 87-97 with standard deviation for repeatability (RSDa) <10% at three spiking levels (0.03, 0.15 and 0.30 µg/g). Combined uncertainty (U = 0.0017) and expanded uncertainty (2U = 0.0033) were fairly consequential. The method may successfully be applied to other cereals samples for determination of metribuzin.

Multiclass Multipesticide Residue Analysis in Fish Matrix by a Modified QuEChERS Method Using Gas Chromatography with Mass Spectrometric Determination.

BACKGROUND: Pesticide residue in fish is a global food safety concern. However, very few validated methods are available targeting simultaneous analysis of multiple classes of pesticides. OBJECTIVE: The aim of this study was to validate a quick, easy, cheap, effective, rugged, and safe workflow-based method for the quantitative determination of multiclass pesticides in fish matrix using GC-MS determination. METHOD: The sample was extracted with acetonitrile, and the cleanup method involved dispersive solid-phase extraction with C-18 sorbent, which effectively scavenged the coextracted matrix components and removed those from the extract. The data on recovery and precision of the method satisfied the criteria of SANTE/11813/2017 guidelines. Average recoveries of pesticides were in the range of 80-120% with precision RSDs ≤20%. The LOD and LOQ were in the ranges of 0.001-0.029 and 0.005-0.125 µg/mL, respectively, for all pesticides. The expanded uncertainty was in the range of 14-20%, based on the single-laboratory validation data (coverage factor, k = 2, confidence level, 95%). CONCLUSIONS: The validation data prove that the method is convenient and acceptable for the routine analysis of multiclass pesticide residues in fish matrices for regulatory compliance. HIGHLIGHTS: The study achieves multiresidue analysis of pesticides in fish matrix with MS-based confirmation. The method combines the advantages of nontarget analysis based on National Institute of Standards and Technology library matching in full scan mode with selected-ion monitoring-based sensitivity.