Dissipation behaviours, residues, and health risk of six herbicides in sugar beets under field conditions.

This study established a residue detection method based on the QuEChERS pre-treatment method and combined it with high-performance liquid chromatography-tandem mass spectrometry to test six herbicides (metamitron, clopyralid, desmedipham, phenmedipham, ethofumesate, and haloxyfop-p-methyl) in sugar beet plants, soil, and roots. The degradation dynamics and terminal residues of each herbicide in sugar beets were analysed. Finally, the dietary risks of various herbicides in sugar beets were evaluated based on the dietary structure of Chinese people, and the risk quotient values were below 100%. Using this detection method, all reagents exhibited good linearity (0.9724 ≤ R2 ≤ 0.9998), The limit of quantification (LOQ) ranged from 0.01 to 0.05 mg/L, the matrix effect ranged from -1.2% to -50%, the addition recovery rate ranged from 77.00% to 103.48%, and the relative standard deviation ranged from 1.61% to 16.17%; therefore, all indicators of this method met the residue detection standards. Under field conditions, the half-lives (t1/2) ranged about 0.65 ∼ 2.96 d and 0.38 ∼ 27.59 d in sugar beet plants and soil, respectively. All herbicides were easily degraded in sugar beet plants and soil (t1/2 < 30 d). The terminal residue amounts in the beet plants, soil, and roots ranged from < LOQ to 0.243 mg/kg. The dietary risk assessment of each pesticide was conducted based on the residual median of the terminal residues and the highest residual values on the edible part of the beetroot. The chronic exposure risk quotient (RQc) and acute exposure risk quotient (RQa) values were < 100%, indicating that the residue of each pesticide in beetroot posed low risks to consumers in China at the recommended dosage.

Synergistic mechanism and environmental behavior of tank-mix adjuvants to topramezone and atrazine.

An effective way to reduce herbicide quantity is to use adjuvants in order to optimize the amount of herbicide and improve its control efficiency. In order to screen for efficient herbicide tank-mix adjuvants, improve the control of weeds in maize fields, reduce the amount of effective ingredients, and improve the adsorption and digestion behavior of herbicides in soil, this study evaluated the synergistic effects and soil behavior of four types of tank-mix adjuvants combined with herbicides. Different types of adjuvants can enhance herbicide production. Surface tension was significantly reduced by 13% after the pesticide solution was applied with AgroSpred™ Prime. The contact angle with the foliar surface was significantly reduced and solution wettability improved using Atp Lus 245-LQ-(TH). The permeability of topramezone and atrazine in leaves of Amaranthus retroflexus L. and Digitaria sanguinalis (L.) Scop. was increased by 22-96% after adding either tank-mix adjuvant. The solution drying time and maximum retention on leaves were not affected by the tank-mix adjuvants. Ethyl and methylated vegetable oils can reduce the adsorption of topramezone in the soil, thus reducing its half-life in soil. The tank-mix adjuvants had no significant effect on soil dissipation or adsorption of atrazine. AgroSpred™ Prime and Atp Lus 245-LQ-(TH) have the best synergistic effect on topramezone and atrazine in the control of A. retroflexus L. and D. sanguinalis (L.) Scop. in maize fields.

Impact of landscape composition on honey bee pollen contamination by pesticides: A multi-residue analysis.

The honey bee is the most common and important managed pollinator of crops. In recent years, honey bee colonies faced high mortality for multiple causes, including land-use change and the use of plant protection products (hereafter pesticides). This work aimed to explore how contamination by pesticides of pollen collected by honey bees was modulated by landscape composition and seasonality. We placed two honey bee colonies in 13 locations in Northern Italy in contrasting landscapes, from which we collected pollen samples monthly during the whole flowering season in 2019 and 2020. We searched for almost 400 compounds, including fungicides, herbicides, insecticides, and acaricides. We then calculated for each pollen sample the Pollen Hazard Quotient (PHQ), an index that provides a measure of multi-residue toxicity of contaminated pollen. Almost all pollen samples were contaminated by at least one compound. We detected 97 compounds, mainly fungicides, but insecticides and acaricides showed the highest toxicity. Fifteen % of the pollen samples had medium-high or high levels of PHQ, which could pose serious threats to honey bees. Fungicides showed a nearly constant PHQ throughout the season, while herbicides and insecticides and acaricides showed higher PHQ values in spring and early summer. Also, PHQ increased with increasing cover of agricultural and urban areas from April to July, while it was low and independent of landscape composition at the end of the season. The cover of perennial crops, i.e., fruit trees and vineyards, but not of annual crops, increased PHQ of pollen samples. Our work highlighted that the potential toxicity of pollen collected by honey bees was modulated by complex interactions among pesticide category, seasonality, and landscape composition. Due to the large number of compounds detected, our study should be complemented with additional experimental research on the potential interactive effects of multiple compounds on honey bee health.

Kinetics of glyphosate and aminomethylphosphonic acid sorption onto montmorillonite clays in soil and their translocation to genetically modified corn.

The co-occurrence of glyphosate (GLP) and aminomethylphosphonic acid (AMPA) in contaminated water, soil, sediment and plants is a cause for concern due to potential threats to the ecosystem and human health. A major route of exposure is through contact with contaminated soil and consumption of crops containing GLP and AMPA residues. However, clay-based sorption strategies for mixtures of GLP and AMPA in soil, plants and garden produce have been very limited. In this study, in vitro soil and in vivo genetically modified corn models were used to establish the proof of concept that the inclusion of clay sorbents in contaminated soils will reduce the bioavailability of GLP and AMPA in soils and their adverse effects on plant growth. Effects of chemical concentration (1-10 mg/kg), sorbent dose (0.5%-3% in soil and 0.5%-1% in plants) and duration (up to 28 days) on sorption kinetics were studied. The time course results showed a continuous GLP degradation to AMPA. The inclusion of calcium montmorillonite (CM) and acid processed montmorillonite (APM) clays at all doses significantly and consistently reduced the bioavailability of both chemicals from soils to plant roots and leaves in a dose- and time-dependent manner without detectable dissociation. Plants treated with 0.5% and 1% APM inclusion showed the highest growth rate (p ≤ 0.05) and lowest chemical bioavailability with up to 76% reduction in roots and 57% reduction in leaves. Results indicated that montmorillonite clays could be added as soil supplements to reduce hazardous mixtures of GLP and AMPA in soils and plants.

Simultaneous determination of three strong polarity herbicides in tea by ion chromatography-triple quadrupole mass spectrometry.

Due to lack of chromogenic groups and fluorescence groups, high boiling point, high polarity, low volatility, and small molecular weight of glyphosate, glufosinate and bentazone, the detection of three analyses were limited in all kinds of food. Herein, a method for the simultaneous determination of glyphosate, glufosinate and bentazone in tea by ion chromatography tandem triple quadrupole mass spectrometry (IC-MS) was developed, which is without organic solvent and complex derivatization. The recoveries of three compounds in different teas (black tea, green tea, white tea) ranged from 80.40 % to 107.00 %, and the intraday precision (n = 6) ranged from 0.57 % to 9.90 %, the daytime precision ranged from 1.00 % to 5.30 %, the quantitative limit (LOQ) ranged from 0.36 to 1.30 µg/L, and the detection limit (LOD) ranged from 0.11 to 0.39 µg/L. Furthermore, the detection limit and quantitative limit of glyphosate, glufosinate and bentazone by this method are lower than other methods in real samples. Meanwhile, the established method was successfully applied to determine the terminal residues of the three analytes in twelve tea samples from commercial market. Therefore, this method can provide reliable technical support for the study of residue status in vegetables and fruits.

Capability of phytoremediation of glyphosate in environment by Vulpia myuros.

Glyphosate is an herbicide extensively used worldwide that can remain in the soil. Phytoremediation to decontaminate polluted water or soil requires a plant that can accumulate the target compound. Vulpia myuros is an annual fescue that can be used as a heavy mental phytoremediation strategy. Recently, it has been used to intercrop with tea plant to prohibit the germination and growth of other weeds in tea garden. In order to know whether it can be used an decontaminating glyphosate' plant in water or soil, in this study, glyphosate degradation behavior was investigated in Vulpia myuros cultivated in a hydroponic system. The results showed that the concentration of glyphosate in the nutrient solution decreased from 43.09 µg mL-1 to 0.45 µg mL-1 in 30 days and that 99% of the glyphosate molecules were absorbed by V. myuros. The contents of glyphosate in the roots reached the maximum (224.33 mg kg-1) on day 1 and then decreased. After 3 days, the content of glyphosate in the leaves reached the highest value (215.64 mg kg-1), while it decreased to 156.26 mg kg-1 in the roots. The dissipation dynamics of glyphosate in the whole hydroponic system fits the first-order kinetic model C = 455.76e-0.21 t, with a half-life of 5.08 days. Over 30 days, 80% of the glyphosate was degraded. The contents of the glyphosate metabolite amino methyl phosphoric acid (AMPA), ranged from 0.103 mg kg-1 on day 1-0.098 mg kg-1 on day 30, not changing significantly over time. The Croot/solution, Cleaf/solution and Cleaf/root were used to express the absorption, transfer, and distribution of glyphosate in V. myuros. These results indicated that glyphosate entered into the root system through free diffusion, which was influenced by both the log Kow and the concentration of glyphosate in the nutrient solution, and that glyphosate was either easily transferred to the leaves through the transpiration stream, accumulated, or degraded. The degradation of glyphosate in V. myuros indicated that it has potential as a remediating plant for environmental restoration.

Occurrence and fate characteristics of isoproturon from garlic cultivation to household processing: Implication for human exposure.

The fate characteristics of isoproturon (IPU) from garlic cultivation to household processing was elucidated by a tracing UHPLC-MS/MS based on the favorable storage stability. The occurrence, pharmacokinetics dissipation and terminal magnitude of IPU were reflected by parameters including original deposition of 31-170 µg kg-1, half-lives of 11.5-19.4 d, and final concentrations of <1.0-250.6 µg kg-1. The processing factors of IPU were further clarified in terms of washing, stir-frying and pickling, with processing factors of 0.008-0.828. The chronic dietary risks (%ADI) were assessed as 1.516-5.242 %, whereas the short-term exposures from green garlic should be continuously emphasized over 99th percentile with unacceptable %ARfD of 147.144-5074.018 %. The acute and chronic risk magnitude significantly decreased by a factor 2.0-125.0 and 2.2-3.3 from raw garlic crops to processed products, respectively. What was noteworthy was the unacceptable acute risks of IPU from green garlic at 99.9th percentile even after a series of processing procedures.

Dissipation kinetics of co-formulation with two herbicides, clodinafop-propargyl and oxyfluorfen, in/on onion (Allium cepa) samples.

Supervised field trail on dissipation of co-formulation with herbicides clodinafop-propargyl and oxyfluorfen in spring onion showed similar pattern of dissipation during two different seasons. Residues of clodinafop-propargyl reached ≤ limit of quantitation (LOQ, 0.05 mg kg-1) on 3rd day after application at both standard and double dose during both the seasons. Oxyfluorfen residues followed first-order kinetics in both the doses during first season with half-life of 0.81 to 3.14 days. The residues of clodinafop-propargyl were detected in soil at both the doses during first season. However, residues were ≤ LOQ (0.05 mg kg-1) during second season. The residues of oxyfluorfen were detected only in double dose during first season in soil. In all other cases and in onion bulb, residues were ≤ LOQ (0.05 mg kg-1) at the time of harvest. As the residues were either ≤ LOQ (0.05 mg kg-1) on 3rd day or have a half-life of 3.14 days, the co-formulation can be used safely, provided a pre harvest interval (PHI) of 3 days is followed. On the basis of maximum residue limits (MRLs) in other commodities and from the data of present study, a default MRL of 0.05 mg kg-1 is proposed for both the pesticides.

Mitigation of atrazine-induced oxidative stress on soybean seedlings after co-inoculation with atrazine-degrading bacterium Arthrobacter sp. DNS10 and inorganic phosphorus-solubilizing bacterium Enterobacter sp. P1.

Atrazine toxicity is one of the limiting factors inhibiting sensitive plant growth. Previous studies showed that atrazine-degrading bacteria could alleviate atrazine toxicity. However, there is limited information on how atrazine-degrading bacteria and plant growth-promote bacteria alleviate atrazine toxicity in soybeans. Therefore, the current study aimed to explore the atrazine removal, phosphorus utilization, and the oxidative stress alleviation of atrazine-degrading bacterium Arthrobacter sp. DNS10 and/or inorganic phosphorus-solubilizing bacterium Enterobacter sp. P1 in the reduction of atrazine toxicity in soybean. The results showed that atrazine exposure to soybean seedlings led to significant inhibition in growth, atrazine removal, and phosphorus utilization. However, the co-inoculatied strains significantly increased seedlings biomass, chlorophyll a/b contents, and total phosphorus in leaves accompanied by great reduction of the atrazine-induced antioxidant enzymes activities and malonaldehyde (MDA) contents, as well as atrazine contents in soil and soybeans under atrazine stress. Furthermore, transcriptome analysis highlighted that co-inoculated strains increased the expression levels of genes related to photosynthetic-antenna proteins, carbohydrate metabolism, and fatty acid degradation in leaves. All the results suggest that the co-inoculation mitigates atrazine-induced oxidative stress on soybean by accelerating atrazine removal from soil and phosphorus accumulation in leaves, enhancing the chlorophyll contents, and regulating plant transcriptome. It may be suggested that co-inoculation of atrazine-degrading bacteria and inorganic phosphorus-solubilizing bacteria can be used as a potential method to alleviate atrazine toxicity to the sensitive crops.

Application of supramolecular solvent based on the surface-active ionic liquid in dispersive liquid-liquid microextraction of triazine herbicides in tea samples.

In this study, a novel supramolecular solvent based on surface-active ionic liquid was prepared and used as an extraction solvent for dispersive liquid-liquid microextraction of four triazine herbicides in tea samples. The formation mechanism, microstructure and physicochemical properties of supramolecular solvent were studied. Some parameters, including the molar ratio of surface-active ionic liquid to tetrahydrofuran, volume of supramolecular solvent, vortex time, pH of sample solution, type and amount of salt, were investigated and optimized. The good linearities (r > 0.9990) for the analytes were obtained. The limits of detection and quantification for triazine herbicides were in the range of 1.7-2.1 µg kg-1 and 5.6-7.1 µg kg-1, respectively. The spiked recoveries were 80.0-119.9 %. The supramolecular solvent prepared in this study has the advantages of simple preparation process, low viscosity and good dispersibility. It can be used for the extraction and enrichment of trace triazine herbicides in tea samples.

Aryl ketones-derived porous organic polymer for enrichment and sensitive detection of phenylurea herbicides in water, tea drink and mushroom samples.

Three aryl ketones-derived porous organic polymers (ATP-POPM, ATP-POPP and ATP-POPO) were fabricated through the aldol condensation reaction of acetylated triphenylsilane precursor (ATP) with different aromatic aldehydes for the first time. The ATP-POPM exhibited superior extraction capacity toward phenylurea herbicides (PUHs). A sensitive method for the simultaneous determination of six PUHs in water, tea drink and mushroom samples was developed with ATP-POPM as solid phase extraction adsorbent prior to high performance liquid chromatography ultraviolet detection. Under the optimized conditions, the linear response of PUHs was 0.09-80.0 ng mL-1 for water, 0.18-100.0 ng mL-1 for tea drinks and 4.50-200.0 ng g -1 for mushroom samples. The detection limits (S/N=3) of the method were 0.03-0.10 ng mL-1, 0.06-0.18 ng mL-1, 1.50-4.50 ng g -1 for water, tea drink and mushroom, respectively. The method recoveries for spiked samples were in the range of 80.7%-116.0%, with relative standard deviations less than 10.3%. The results proved that the established method was sensitive and suitable to detect PUHs with acceptable accuracy and precision. This work provided a powerful tool to synthesize promising adsorbent by aldol condensation reaction for detecting six PUHs simultaneously in real samples.

Assessment of bioaccumulation of glyphosate and aminomethylphosphonic acid in marine mussels using capillary electrophoresis with light-emitting diode-induced fluorescence detection.

Glyphosate or N-(phosphonomethyl)glycine, widely used as herbicide in agriculture to control weeds and to facilitate harvesting, has been included in Group 2A pollutants (probably carcinogenic to humans) by the International Agency for Research on Cancer (IARC). In intensive agricultural areas, runoff and soil leaching are likely to drive glyphosate to surface waters, where the compound is often detected together with its main microbial metabolite, aminomethylphosphonic acid (AMPA). In the present study a method based on capillary electrophoresis coupled with light-emitting diode-induced fluorescence detection has been developed and validated for the determination of the two compounds in whole soft mass of marine mussels (Mytilus galloprovincialis). The method is based on the acidic hydrolysis of lyophilized tissue using 6 M HCl (oven at 110 °C for 22 h) to release the target analytes; their subsequent derivatization using 4-fluoro-7-nitro-2,1,3-benzoxadiazole, was found to be suitable for the sensitive fluorescence detection. To achieve optimum separation of the analytes from the matrix and degradation reagent interferences, the background electrolyte constituted by borate buffer (pH 9.2, 30 mM) was supplemented with 10 mM heptakis(2,6-di-O-methyl)-ß-cyclodextrin. The method was validated for linearity, precision, accuracy, robustness and sensitivity showing LOQ of 0.2 and 1.0 µg/g in fresh tissues, for AMPA and glyphosate, respectively; the recovery values ranged within 88.5 - 94.6% for glyphosate and 70.4 - 76.6% for AMPA. Experimental samples of Mediterranean mussels M. galloprovincialis treated with 100 µg/L or 500 µg/L of both glyphosate and AMPA, showed a dose dependent bioaccumulation of the compounds reaching maximum level of 77.0 µg/g and 11.3 µg/g of AMPA and glyphosate, respectively. The study demonstrates for the first time M. galloprovincialis as potential sentinel organisms for the environmental occurrence of these small amphoteric pollutants.

Residue Behavior of Clopyralid Herbicide in Soil and Sugar Beet Crop under Subtropical Field Conditions.

ABSTRACT: Sugar beet is a major crop for the sugar industry. With growing awareness of unsystematic use of pesticides, health problem, and environmental issues, assessment of pesticide residues in soil and crops has become necessary. Studies of subtropical conditions on dissipation and residue analysis of clopyralid have not yet been reported. Therefore, dissipation kinetics and terminal residues of clopyralid for two cropping seasons in the soil and the sugar beet crop were studied under field conditions. An experiment was laid out in a randomized block design, and a herbicide was applied as a postemergent. Clopyralid was extracted from the matrix by basic water, subjected to solid phase extraction cleanup, and quantified by high-pressure liquid chromatography-UV. The method was validated, and recovery percentage of pesticide ranged from 81 to 88, 77 to 85, 78 to 86, and 89 to 94% in the soil, sugar beet roots, sugar beet leaves, and water, respectively. After application in the soil, clopyralid dissipated rapidly following monophasic first-order kinetics, with a half-life of 13.39 days. Limits of detection and quantitation were 0.007 and 0.02 µg g-1, respectively. Clopyralid does not persist long in soil, and residues were below the European Union's maximum residue levels (0.5 mg kg-1) in the roots and leaves of sugar beet. Residues were also not detected in the groundwater. It can be concluded that clopyralid could be considered a safe herbicide from the environmental aspect due to its nonpersistence and that it would not have an adverse effect on human or animal health.

Establishment of a HPLC-MS/MS Detection Method for Glyphosate, Glufosinate-Ammonium, and Aminomethyl Phosphoric Acid in Tea and Its Use for Risk Exposure Assessment.

The tea shrub is grown in long-standing orchards, an environment that is suitable for persistent weed growth, which is increasingly controlled by herbicides. Therefore, there is increasing concern that tea consumers may be exposed to herbicide residues. In this study, the levels of glufosinate-ammonium (GLU), glyphosate [N-(phosphonomethyl) glycine; PMG], and its metabolite aminomethyl phosphoric acid (AMPA) were determined in tea samples by HPLC-MS/MS using several current purification methods and a new method that we developed herein. The matrix effect of our proposed method was between -27.3 and 27.7%, which was lower than that in other methods, indicating that this method effectively reduced the interference of tea matrix in the mass spectrometry process. This method was used to determine the levels of PMG, GLU, and AMPA in 780 samples, including six traditional Chinese teas (green tea, black tea, oolong tea, dark tea, white tea, and yellow tea) and a floral tea, from 14 provinces of China. Probability estimates showed that the 95th percentile risk entropy values of the three pesticide residues were far below the acceptable risk level. The risk assessment results showed that exposure to PMG, GLU, and AMPA caused by drinking tea beverages poses no significant risk to human health.

Dissipation, residue, dietary, and ecological risk assessment of atrazine in apples, grapes, tea, and their soil.

Atrazine is one of the most used herbicides in China. It is a persistent organic pollutant but has been widely used on Chinese farmlands for a long time. To assess its dietary and ecological risks to human and environment, in this study, atrazine residues were extracted with acetonitrile and then plant samples were detected with gas chromatography coupled with mass spectrometry (GC-MS) and soil samples were determined with gas chromatography coupled with nitrogen-phosphorus detector (GC-NPD). The limit of quantification (LOQ) of the method was 0.01 mg/kg for all matrices. The recoveries ranged from 82.0 to 105.4% for plant samples and 75.6 to 85.6% for soil samples. The final residues of atrazine in all plant samples were lower than LOQ. Dietary risk assessment suggested that under good agricultural practices (GAP) conditions, intake of atrazine from apples, grapes, and tea would exhibit an acceptably low health risk on consumers. However, the final residues of atrazine in soil samples were <0.01-9.2 mg/kg, and the half-lives were 2.0-9.1 days. Based on the species sensitivity distribution (SSD) model, the potential affected fraction (PAF) of atrazine in soil samples ranges from 0.01 to 65.8%. Atrazine residues in 43.1% soil samples were higher than 0.11 mg/kg, which was the hazardous concentration for 5% of species (HC5) of atrazine in soil. These results suggested that the ecological risks of atrazine in apples, grapes, and tea garden soil would exhibit a high risk on environmental species even under the same GAP conditions. This study could provide guidance for comprehensive risk assessment of atrazine properly used in apple, grape, and tea gardens.

Title: Low concentrations of glyphosate in water and sediment after direct over-water application to control an invasive aquatic plant.

When an invasive wetland grass degrades a Ramsar wetland and Important Bird Area, decisive management action is called for. To limit the extent and spread of European Phragmites australis, the Ontario government began the first, large-scale application of glyphosate (Roundup CustomⓇ) over standing water to control an invasive species in Canadian history. Between 2016 and 2018, over 1000 ha of marsh were treated. To assess the concentration, movement and longevity of this herbicide in treated marshes, we measured the concentration of glyphosate, its primary breakdown product aminomethylphosphonic acid (AMPA), and the alcohol ethoxylate-based adjuvant AquasurfⓇ in water and sediments in areas of the highest exposure and up to 150 m into adjacent bays. The maximum observed concentration of glyphosate in water was 0.320 mg/L, occurring within 24 hr of application. The maximum glyphosate concentration in sediment was 0.250 mg/kg, occurring within about 30 days of application. AMPA was detectable in water and sediment, indicating microbial breakdown of glyphosate in the marsh, but at low concentrations (maxwater = 0.025 mg/L, maxsed = 0.012 mg/kg). The maximum distance from the point of application that glyphosate was detected in the water was 100 m, while AMPA was detectable only at the edge of where glyphosate was applied (0 m). Concentrations in water returned to pre-treatment levels (0.005 mg/kg) for over one year but less than two years. Concentrations of alcohol ethoxylates were variable in space and time, following a pattern that could not be attributed to AquasurfⓇ use. The direct, over-water application of Roundup CustomⓇ with AquasurfⓇ to control invasive P. australis did not reach concentrations deemed to pose toxicological concern to aquatic biota by the Canadian Council of Ministers of the Environment.

Direct Analysis of Glyphosate, Glufosinate, and Their Metabolites in Palm Oil Using Liquid Chromatography with Tandem Mass Spectrometry.

BACKGROUND: Glyphosate and glufosinate are broad-spectrum herbicides which are frequently used in palm oil plantations for weed control. Metabolites of these herbicides are known to have environmental and food safety implications. As there is no validated method for multiresidue testing of these herbicides and their metabolites in palm oil products, a new method was needed for the purpose of regulatory analysis. OBJECTIVE: In this study, we endeavored to develop a rapid method for multiresidue analysis of glyphosate (+aminomethylphosphonic acid) and glufosinate (+3-methylphosphinicopropionic acid and N-acetyl-glufosinate) in refined and crude palm oil matrices using liquid chromatography (LC) tandem mass spectrometry (MS/MS). METHOD: The optimized sample preparation workflow included extraction of refined or crude palm oil (10 g) with acidified water (0.1 M HCl), cleanup by phase separation with dichloromethane, and analysis by LC-MS/MS with multiple reaction monitoring. RESULTS: The use of a Torus-DEA LC column ensured simultaneous analysis of these compounds within a runtime of 10 min. The LOQ of these analytes was 0.01 mg/kg, except that of aminomethylphosphonic acid which was 0.02 mg/kg. The method sensitivity complied with the national maximum residue limits of Malaysia and the European Union. Also, the method selectivity, sensitivity, accuracy, and precision were aligned with the SANTE/12682/2019 guidelines of analytical quality control. CONCLUSIONS: The potentiality of the optimized method lies in a high throughput direct analysis of glyphosate and glufosinate with their metabolites in a single chromatographic run. The method is fit for purpose for regulatory testing of these residues in a broad range of palm oil matrices. HIGHLIGHTS: The study reports for the first time a validated method for simultaneous analysis of glyphosate, glufosinate, and their metabolites in a range of palm oil products. The method did not require a derivatization step and provided a high throughput analysis of these compounds with satisfactory selectivity, sensitivity, accuracy, and precision.

Effect of Shading on the Sesquiterpene Lactone Content and Phytotoxicity of Cultivated Cardoon Leaf Extracts.

The work described here follows on from a previous study focused on the influence of the genotype and harvest time on the sesquiterpene lactone (STL) profile of Cynara cardunculus L. leaf extracts. The aim of this study was to investigate the effect that 60% plant shading in cultivated cardoon (C. cardunculus var. altilis) leaf extracts harvested in winter and spring had on the composition of STLs and the phytotoxicity. The phytotoxicity of leaf extracts was evaluated by assessing wheat coleoptile elongation along with seed germination and the root and shoot length of the weeds Amaranthus retroflexus L. and Portulaca oleracea L. Shading increased the production of STLs in spring, and this effect correlated positively with the phytotoxic activity. The induction of shading can therefore be used to modulate STL concentrations and their phytotoxic potential in cultivated cardoon leaves for industrial applications.

Residue Behavior and Risk Assessment of Rimsulfuron and Quizalofop-P-ethyl in Potato Under Field Conditions.

A method for simultaneous quantitation of rimsulfuron, quizalofop-P-ethyl and quizalofop-P in potato plant, soil and potato tuber samples was established. The mean recoveries of rimsulfuron, quizalofop-P-ethyl and quizalofop-P in different matrices spiked with them were 81.4%-101.1%, 76.1%-99.0% and 77.4%-106.4% with relative standard deviations (RSDs) of 2.7%-13.3%, 0.9%-5.5%, 1.7%-11.3%, respectively. The open-field trials in China were conducted in potato cultivation system of Changchun and Jinan. The results indicated that the half-lives of rimsulfuron and quizalofop-P-ethyl were 0.04-13.1 days. The residues of quizalofop-P during the harvest time in Jinan soil were < 0.01-0.044 mg kg-1, while there was no residue of target herbicides detected in all other samples. The risk assessment results demonstrated that the risk quotients (RQs) of rimsulfuron and quizalofop-P-ethyl were 7.857 × 10-5 and 8.730 × 10-3, respectively, which exhibited an acceptable dietary risk to Chinese consumers.

Residue and Dissipation Kinetics of Metsulfuron-Methyl Herbicide in Soil: A Field Assessment at an Oil Palm Plantation.

A field trial experiment was conducted to investigate the degradation of metsulfuron-methyl at two application dosages, 15 g a.i/ha and 30 g a.i/ha, at an oil palm plantation. Soil samples were collected at ‒1, 0, 1, 3, 7, 14, and 21 days after treatment (DAT) at the following depths: 0-10, 10-20, 20-30, 30-40, and 40-50 cm. The results showed rapid degradation of metsulfuron-methyl in the soil, with calculated half-life (t½) values ranging from 6.3 and 7.9 days. The rates of degradation of metsulfuron-methyl followed first-order reaction kinetics (R2 = 0.91-0.92). At the spray dosage of 15 g a.i/ha, metsulfuron-methyl residue was detected at up to 20-30 cm soil depth, at 3.56% to 1.78% at 3 and 7 DAT, respectively. Doubling the dosage to 30 g a.i/ha increased the metsulfuron-methyl residue in up to 30-40 cm soil depth at 3, 7, and 14 DAT, with concentrations ranging from 1.90% to 1.74%. These findings suggest that metsulfuron-methyl has a low impact on the accumulation of the residues in the soil at application dosages of 15 g a.i/ha and 30 g a.i/ha, due to rapid degradation, and the half-life was found to be 6.3 to 7.9 days.