Determination of Multi-pesticides Residues in Jasmine Flower and Its Scented Tea.

For minor crops such as jasmine, the lack of pesticide registration and maximum residue limits are important issues that need to be solved in order to facilitate trading and ensure food safety. Meanwhile, reliable and quick analytical methods for multi-pesticide residues in these commodities are few, but required by various stakeholders. In this study, a method for detecting twenty-five most frequently used pesticides in jasmine flower and its scented tea by multi-plug filtration cleanup and ultra-high-performance liquid chromatography-tandem mass spectrometry was developed and validated. The cleanup process was optimized and compared with the dispersive solid phase extraction procedure. The method was validated, showing that except for methomyl, recoveries of twenty-five pesticides were 64%-108%, with relative standard deviations (n = 5) of 0.33%-10%. The method was successfully applied to detect pesticide residues in marketed samples. The results showed that some flower and tea samples contained a combination of different pesticide residues.

Nano-selenium enhances the antioxidant capacity, organic acids and cucurbitacin B in melon (Cucumis melo L.) plants.

Pesticides are widely used in melon production causing safety issues around the consumption of melon and increasing pathogen and insect tolerance to pesticides. This study investigated whether a nano-selenium (Nano-Se) spray treatment can improve resistance to biological stress in melon plants, reducing the need for pesticides, and how this mechanism is activated. To achieve this, we examine the ultrastructure and physio-biochemical responses of two melon cultivars after foliar spraying with Nano-Se. Nano-Se treatment reduced plastoglobulins in leaf mesophyll cells, thylakoid films were left intact, and compound starch granules increased. Nano-Se treatment also increased root mitochondria and left nucleoli intact. Nano-Se treatment enhanced ascorbate peroxidase, peroxidase, phenylalanine ammonia lyase, ß-1,3-glucanase, chitinase activities and their mRNA levels in treated melon plants compared to control plants (without Nano-Se treatments). Exogenous application of Nano-Se improved fructose, glucose, galactitol, stachyose, lactic acid, tartaric acid, fumaric acid, malic acid and succinic acid in treated plants compared to control plants. In addition, Nano-Se treatment enhanced cucurbitacin B and up-regulated eight cucurbitacin B synthesis-related genes. We conclude that Nano-Se treatment of melon plants triggered antioxidant capacity, photosynthesis, organic acids, and up-regulated cucurbitacin B synthesis-related genes, which plays a comprehensive role in stress resistance in melon plants.

Development and application of a numerical dynamic model for pesticide residues in apple orchards.

BACKGROUND: Limited understanding of the fate of pesticides in apple orchards may lead to recurring pests or pose risks to food safety. In this study, through a field experiment conducted in an apple orchard, a dynamic plant uptake model, coupled with a soil water model, was developed to simulate measured pesticide concentrations in soil and different plant compartments. RESULTS: Results showed that the overall model could adequately describe the data set of four pesticides in the apple orchard. An estimated 15%-24.7% of applied pesticides were deposited on leaves and 0.37%-0.58% on fruits. Decreasing pesticide concentrations in fruits were observed after pesticide application, with 9.6%-64.8% of this decrease explained by biodegradation, 29.8%-75.8% by fruit growth dilution and 11.3%-47.6% by wash-off. Furthermore, a first estimation of dietary risks indicated that ingestion of the apples may not represent an acute or chronic risk to human health. CONCLUSION: The dynamic plant uptake model, coupled with the tipping buckets soil water model, could successfully be fitted to describe to the data set for the fate of four pesticides applied in an apple orchard. The contribution of different pathways to pesticide concentration was highly influenced by precipitation, fruit growth dilution and the characteristics of different pesticides. This model can improve our understanding of pesticide fate in apple orchards and has great potential for supporting food safety assessment and decision-making to minimize impacts arising from pesticide applications. © 2022 Society of Chemical Industry.

Dissipative behavior, residual pattern, and risk assessment of four pesticides and their metabolites during tea cultivation, processing and infusion.

BACKGROUND: In recent years, metabolic products of pesticides have gained much attention due to their substantial characteristics as organic pollutants. So far, the behavior and metabolite levels of pesticide metabolites in crops have not been characterized well. In the present study, four registered pesticides (imidacloprid, diafenthiuron, malathion and chlorothalonil) were applied on tea plants in Fujian and Sichuan to characterize their metabolites residue pattern and dietary risk. RESULTS: Four pesticides dissipated first-order kinetics in the fresh tea leaves with the half-lives of 1.4-3.8 days. Nine metabolites were detected in the fresh tea leaves and green tea after processing. The metabolites residues showed an increasing trend first and then declined after treatment, and reached the maximum near the half-lives of pesticide. Compared with the parent pesticide, the total residue and acute risk (included the metabolites) increased by 1.7-105.2 times. Some metabolites, especially those whose parent pesticides have high water solubility and low Log Kow, will be more easily transferred to tea infusion. CONCLUSION: Pesticides were metabolized rapidly on tea plants after application, but the production of metabolites increased the health risk of tea consumption. These results could provide insights to use the pesticides in tea gardens and risk monitoring after application. © 2022 Society of Chemical Industry.

Nanoselenium integrates soil-pepper plant homeostasis by recruiting rhizosphere-beneficial microbiomes and allocating signaling molecule levels under Cd stress.

Most studies have focused on regulation in a metabolic pathway in response to exogenous selenium under cadmium stress, rather than the change of key factors in soil and pepper plants. In this study, the correlations in environmental variables, microorganisms, metabolic pathways, Se and Cd morphology under nano-Se intervention were examined using metabolomics and microbial diversity in rhizosphere soil and pepper plants. The principal forms of Se in the soils were Se (VI) and SeCys, while SeMet and MeSeCys were the main components in the root, stem, leaves, and fruits in the treatment of nano-Se (5 and 20 mg/L) relative to the control. Soil enzymes,metabolites (fluorescein diacetate, urease, brassinolide, and p-hydroxybenzonic acid), and plant metabolites (rutin, luteolin, brassinolide, and abscisic acid) were remarkably enhanced by nano-Se fortification. The bio-enhancement of nano-Se can boost the beneficial microorganisms of Gammaproteobacteria, Alphaproteobacteria, Bacteroidia, Gemmatimonadetes, Deltaproteobacteria, and Anaerolineae in rhizosphere soil. Changes in microbial community were found to be strongly linked to the environment index, enzymes, soil metabolites, Se forms, which reduced Cd bioavailability and Cd accumulation in pepper plants. In conclusion, the nano-Se application integrates soil-plant balance by improving soil qualities and assigning signaling molecule levels in rhizosphere soil and pepper plants.

Multi-residue analytical method development and risk assessment of 56 pesticides and their metabolites in tea by chromatography tandem mass spectroscopy.

A modified QuEChERS method coupled to chromatography tandem mass spectroscopy was established and used to identify 56 pesticides and 21 metabolites residues in tea samples. The average recoveries for the target compounds ranged from 71% to 109% with RSDs of 1-17%. Pesticides and metabolites residues in 248 tea samples from China were investigated by the developed method, and the dietary intake risk for consumers was estimated. The results showed that 36 pesticides and 14 metabolites were detected with concentrations of 0.0050-7.7 mg/kg. There are unlikely to present a public health concern for Chinese consumers. The acute risk of pesticides would be exaggerated when calculated by the residue level in tea instead of tea infusion. The unauthorized and banned pesticide contributed to the chronic and acute hazard index by 68% and 36%, respectively. The cumulative risk of residual pesticides and their metabolites on human health deserve further attention.

Nanoselenium Enhanced Wheat Resistance to Aphids by Regulating Biosynthesis of DIMBOA and Volatile Components.

The mechanism of nanoselenium (nano-Se) improving the resistance induced by plant components to aphids is unclear. In this study, foliar sprayed nano-Se (5.0 mg/L) could significantly reduce the Sitobion avenae number (36%) compared with that in the control. Foliar application of nano-Se enhanced the antioxidant capacity by reducing malondialdehyde (MDA) and increasing GSH-Px, CAT, GSH, Pro, and VE concentrations in wheat seedlings. The phenylpropane pathway was activated by nano-Se biofortification, which increased apigenin and caffeic acid concentrations. The high-level expression of the related genes (TaBx1A, TaBx3A, TaBx4A, TaASMT2, and TaCOMT) induced the promotion of melatonin (88.6%) and 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA) (64.3%). Different ratios of the secondary metabolites to nano-Se were taken to examine the effects on resistance of wheat to S. avenae. The results revealed that the combination of nano-Se and melatonin could achieve the best overall performance by reducing the S. avenae number by 52.2%. The study suggests that the coordinated applications of nano-Se and melatonin could more effectively improve the wheat resistance to aphids via the promotion of volatile organic compound synthesis and modulation in phenylpropane and indole metabolism pathways.

Nanoselenium transformation and inhibition of cadmium accumulation by regulating the lignin biosynthetic pathway and plant hormone signal transduction in pepper plants.

Selenium (Se) can promote the growth and resistance of agricultural crops as fertilizers, while the role of nano-selenium (nano-Se) against Cd remains unclear in pepper plants (Capsicum annuum L.). Biofortification with nano-Se observably restored Cd stress by decreasing the level of Cd in plant tissues and boosting the accumulation in biomass. The Se compounds transformed by nano-Se were primarily in the form of SeMet and MeSeCys in pepper tissues. Differential metabolites and the genes of plant signal transduction and lignin biosynthesis were measured by employing transcriptomics and determining target metabolites. The number of lignin-related genes (PAL, CAD, 4CL, and COMT) and contents of metabolites (sinapyl alcohol, phenylalanine, p-coumaryl alcohol, caffeyl alcohol, and coniferaldehyde) were remarkably enhanced by treatment with Cd1Se0.2, thus, maintaining the integrity of cell walls in the roots. It also enhanced signal transduction by plant hormones and responsive resistance by inducing the biosynthesis of genes (BZR1, LOX3, and NCDE1) and metabolites (brassinolide, abscisic acid, and jasmonic acid) in the roots and leaves. In general, this study can enable a better understanding of the protective mechanism of nano-Se in improving the capacity of plants to resist environmental stress.

Nanoselenium foliar application enhances biosynthesis of tea leaves in metabolic cycles and associated responsive pathways.

An emerging stress of pesticides in plant and soil is closely watched as it affects crop antioxidant systems, nutritional quality, and flavor. Although selenium (Se) can enhance the resistance of plants, the protective mechanism of nanoselenium is still not known under the long-term pesticide stress in tea trees. In this study, we investigated the potential effects of foliar application of nanoselenium for a two-year field experiment on tea plants under pesticide-induced oxidative stress. Compared to control, nano-Se (10 mg/L) markedly enhanced the protein, soluble sugar, carotenoid, tea polyphenols, and catechins contents. High levels of theanine, glutamic acid, proline, and arginine were found to be induced most likely by adjusting the GS-GOGAT cycle. Se-supplementation may promote tea leaves' secondary metabolism, thus increasing the accumulation of total phenols and flavonoids (apigenin, kaempferol, quercetin, myricetin, and rutin). It also minimized the accumulation of malondialdehyde, hydrogen peroxide, and superoxide anion by activating the antioxidants enzymes including in the AsA-GSH cycle. Selenium-rich tea also showed better fragrance and flavor. In summary, nano-Se can ameliorate the nutrients quality and abiotic stresses resistance of crops.

Exogenous salicylic acid alleviates the accumulation of pesticides and mitigates pesticide-induced oxidative stress in cucumber plants (Cucumis sativus L.).

Salicylic acid (SA) is an important signal molecule, regulating oxidative stress response in plants. In this study, we evaluated the influences of SA (1 mg L-1, 10 mg L-1 and 50 mg L-1) on the accumulation of clothianidin (CLO), dinotefuran (DFN) and difenoconazole (DFZ) (5 mg L-1) and pesticide-induced (CLO-10 mg L-1, DFN-20 mg L-1, and DFZ-10 mg L-1) oxidative stress in cucumber plants. Exogenous SA at 10 mg L-1 significantly reduced the half-lives of three pesticides in nutrient solution and prevented the accumulation of pesticides in roots and leaves. And the role of SA in reducing residues was related to the major accumulation sites of pesticides. By calculating the root concentration factor (RCF) and translocation factor (TF), we found that SA at 10 mg L-1 reduced the ability of roots to absorb pesticides and enhanced the translocation ability from roots to leaves. Roots exposed to high concentrations of three pesticides could reduce biomass, low chlorophyll content, increase the accumulation of reactive oxygen species (ROS) and proline, promote lipid peroxidation, and alter the activities of a range of antioxidant enzymes, respectively. Exogenous SA at low concentrations (1 mg L-1 and 10 mg L-1) significantly mitigated these negative effects. Hence, application of exogenous SA at 10 mg L-1 could effectively alleviate the accumulation of pesticides and induce stress tolerance in cucumber planting systems.

Nanoselenium Foliar Applications Enhance the Nutrient Quality of Pepper by Activating the Capsaicinoid Synthetic Pathway.

Increasing the crop quality through enhancement of plant health is a challenging task. In this study, nanoselenium (nano-Se) was sprayed on pepper leaves, and the pepper components were compared to those of selenite. It was found that nano-Se (20 mg/L) resulted in a greater performance of plant health. It increased the chlorophyll and soluble sugar levels, which could activate phenylpropane and branched-chain fatty acid pathways, as well as AT3-related enzymes and gene expressions. These led to an enhancement for the synthesis of capsaicinoids, flavonoids, and total phenols. The nano-Se treatment also significantly promoted the expression of phyto-hormones synthesis genes, and consequently increased jasmonic, abscisic, and salicylic acid levels. Proline pathway-related compounds were increased, which could decrease the malondialdehyde and hydroxyl radical levels in crops. This study shows that nano-Se activated capsaicinoid pathways by enhancing photosynthesis and raising soluble sugar levels. The capsaicinoid contents in peppers were then increased, which consequently promoted the accumulation of secondary metabolites and antioxidants.

Comparison of Sin-QuEChERS Nano and d-SPE Methods for Pesticide Multi-Residues in Lettuce and Chinese Chives.

In this study, a new rapid cleanup method was developed for the analysis of 111 pesticide multi-residues in lettuce and Chinese chives by GC-MS/MS and LC-MS/MS. QuEChERS (quick, easy, cheap, effective, rugged and safe)-based sample extraction was used to obtain the extracts, and the cleanup procedure was carried out using a Sin-QuEChERS nano cartridge. Comparison of the cleanup effects, limits of quantification and limits of detection, recoveries, precision and matrix effects (MEs) between the Sin-QuEChERS nano method and the classical dispersive solid phase extraction (d-SPE) method were performed. When spiked at 10 and 100 µg/kg, the number of pesticides with recoveries between 90% to 110% and relative standard deviations < 15% were greater when using the Sin-QuEChERS nano method. The MEs of Sin-QuEChERS nano and d-SPE methods ranged between 0.72 to 3.41 and 0.63 to 3.56, respectively. The results verified that the Sin-QuEChERS nano method was significantly more effective at removing pigments and more convenient than the d-SPE method. The developed method with the Sin-QuEChERS nano cleanup procedure was applied successfully to determine pesticide residues in market samples.

Deposition and distribution of myclobutanil and tebuconazole in a semidwarf apple orchard by hand-held gun and air-assisted sprayer application.

BACKGROUND: Sprayers have been shown in numerous reports to influence pesticide deposition and distribution significantly, and public concern for their potential risk has been increasing in recent years. In this study, a hand-held gun sprayer and two air-assisted sprayers (a conventional axial fan air-blast sprayer and a tower sprayer) were used to apply myclobutanil and tebuconazole, and their influence on pesticide distribution and deposition in a semidwarf apple orchard was systematically investigated. RESULTS: The coefficients of variation of different canopy zones associated with the tower sprayers were 38.9-41.9% for leaves and 35.5-36.4% for fruit, generally lower than the coefficients of variation related to the other two sprayers. Tests conducted using the air-assisted sprayers recorded an overall higher drift on the adjacent rows than experiments carried out with the hand-held gun sprayer. The results of drift in soil indicated that pesticide was mainly distributed within 5 m downwind of the treated area, and the distribution pattern was influenced by sprayer design. The total pesticide concentration deposited in soil within 5 m during application by the tower sprayer was 0.28 m mg kg-1 for myclobutanil and 0.90 m mg kg-1 for tebuconazole, much lower than that of the hand-held gun sprayer and the conventional axial fan air-blast sprayer. CONCLUSION: The results indicate that the tower sprayer gives a more uniform distribution and guarantees better effectiveness for the phytosanitary treatment. The tower sprayer also protected the soil better and reduced environmental pollution due to its scientific structural design. © 2020 Society of Chemical Industry.

Development and evaluation of an automated multi-channel multiplug filtration cleanup device for pesticide residue analysis on mulberry leaves and processed tea.

An automated multi-channel multiplug filtration cleanup (m-PFC) device was designed and developed. m-PFC columns were suitably installed in the device. The cycle times, speed and nitrogen pressure parameters of the m-PFC column were optimized. The device was utilized to analyze the 82 pesticide residues in fresh mulberry leaves and processed tea with GC-MS/MS detection. Method validation was performed on 82 pesticide residues in fresh mulberry leaves and processed tea at spiked levels of 0.01, 0.05 and 0.5 mg kg-1. The fortified recoveries of 82 pesticides were 72-115% and the relative standard deviations were 1-15%, except for diniconazole and clodinafop-propargyl in mulberry leaves. The automated multi-channel m-PFC device was successfully applied to detect the pesticide residues in fresh mulberry leaves and processed tea samples. With comparison to the conventional QuEChERS method, the current method using this device did not need additional vortex or centrifugation steps, and could process 48-64 samples in about one hour. The automated m-PFC method saved labor and improved the precision and was shown to be efficient and practical in pesticide residue analysis.

Comparison of Different Home/Commercial Washing Strategies for Ten Typical Pesticide Residue Removal Effects in Kumquat, Spinach and Cucumber.

Home processing can reduce pesticide residues in agricultural products, and the common forms of treatment include washing, peeling, blanching, and cooking. In this study, the removal effects of tap water, micron calcium solution, alkaline electrolyzed water (AlEW), ozone water, active oxygen, and sodium bicarbonate on 10 typical pesticide residues in kumquat, cucumber, and spinach were investigated. The residue magnitudes were determined by chromatography⁻tandem mass spectrometry (GC-MS/MS, LC-MS/MS), combined with the QuEChERS pretreatment method. The model tests showed that the results of soaking and greenhouse were close. The removal effects of pesticide residues in kumquat and cucumber washing by alkaline electrolyzed water with a high pH value, micron calcium, and active oxygen solution were better than other washing solutions. The sodium bicarbonate solution, ozone water, and active oxygen solution were more effective in reducing pesticide residues in spinach than others. Active oxygen solution showed a better removal efficiency for the 10 pesticides than other treatments because of its alkalinity and oxidizability. Among the ten pesticides, pyrethroid pesticides had a higher removal rate. Additionally, chlorpyrifos were the most difficult to remove. For the majority of pesticides, the pesticide residue magnitudes showed a gradual reduction when increasing the washing time. The results indicated that alkaline solutions were effective for the reduction of pesticide residues when the washing time was longer than 15 min.

Removal of six pesticide residues in cowpea with alkaline electrolysed water.

BACKGROUND: Reduction of six pesticide residues (isoprocarb, chlorpyrifos, bifenthrin, beta-cypermethrin, difenoconazole and azoxystrobin) in cowpea by alkaline electrolysed water (AlEW) solutions with different pH was investigated. The commonly used washing treatments in household processing were used for comparison. RESULTS: The residue magnitudes were determined by gas chromatography coupled with tandem mass spectrometry (GC-MS/MS). Results showed that the removal effect of AlEW solution on the six pesticides was superior to tap water, 5% sodium chloride, 5% sodium carbonate and 5% acetic acid solution. AlEW with pH 12.2 had more potential to eliminate the six pesticides in cowpeas. Moreover, the reduction of pesticide residues gradually increased with the increase of washing time. CONCLUSION: This study demonstrated that AlEW solution with pH of 12.2 could be used to reduce pesticide residues on fresh cowpea samples. © 2016 Society of Chemical Industry.