Monitoring residue levels and dietary risk assessment of thiamethoxam and its metabolite clothianidin for Chinese consumption of Chinese kale.

BACKGROUND: Thiamethoxam is widely used to control pests in Chinese kale, popularly consumed leafy vegetables. The potential risk to the environment and human health has aroused much public concern. Therefore, it is important to investigate the degradation behavior, residue distribution and dietary risk assessment of thiamethoxam in Chinese kale. RESULTS: A sensitive analytical method for determination of thiamethoxam and its metabolite clothianidin residue in Chinese kale was established and validated through a quick, easy, cheap, effective, rugged, and safe (QuEChERS) technique with ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). The recoveries were 85.4-101.2% for thiamethoxam and 79.5-108.1% for clothianidin, with the relative standard deviations (RSDs) of 0.9-10.2% and 1.8-6.0%, respectively. For the dissipation kinetics, the data showed that thiamethoxam in Chinese kale was degraded with the half-lives of 4.1 to 4.5 days. In the terminal residue experiments, the residues of thiamethoxam were 0.017-0.357 mg kg-1 after application 2-3 times with a preharvest interval (PHI) of 7 days under the designed dosages. The chronic and acute dietary exposure assessment risk quotient (RQ) values of thiamethoxam in Chinese kale for different Chinese consumers were 0.08-0.19% and 0.05-0.12%, respectively, and those of clothianidin were 0.01-0.04% and 0.02-0.04%, respectively, all of the RQ values were lower than 100%. CONCLUSION: Thiamethoxam in Chinese kale was rapidly degraded following first-order kinetics models. The dietary risk of thiamethoxam and clothianidin through Chinese kale was negligible to consumers. The results from this study are important reference for Chinese governments to developing criteria for the safe and rational use of thiamethoxam, setting maximum residue levels (MRLs), monitoring the quality safety of agricultural products and protecting consumer health. © 2021 Society of Chemical Industry.

Residue behavior, transfer and risk assessment of tolfenpyrad, dinotefuran and its metabolites during tea growing and tea brewing.

BACKGROUND: Tolfenpyrad and dinotefuran are two representative pesticides used for pest control in tea gardens. Their application may bring about a potential risk to the health of consumers. Therefore, it is essential to investigate the residue behavior, transfer and risk assessment of tolfenpyrad, dinotefuran and metabolites from tea garden to teacup. RESULTS: An effective analytical method was established and validated to simultaneously determine tolfenpyrad, dinotefuran and its metabolites (DN and UF) in tea. The average recoveries of tolfenpyrad, dinotefuran, DN and UF were in the range 72.1-106.3%, with relative standard deviations lower than 11.8%. On the basis of the proposed method, the dissipation of tolfenpyrad and dinotefuran in fresh tea leaves followed first-order kinetics models with half-lives of 4.30-7.33 days and 4.65-5.50 days, respectively. With application amounts of 112.5-168.75 g a.i. ha-1 once or twice, the terminal residues of tolfenpyrad and total dinotefuran in green tea were lower than 19.6 and 7.13 mg kg-1 , respectively, and below their corresponding maximum residue limits . The leaching rates of tolfenpyrad and total dinotefuran during the tea brewing were in the ranges 1.4-2.3% and 93.7-98.1%, respectively. CONCLUSION: Tolfenpyrad and dinotefuran in tea were easily degraded. The RQc and RQa values for tolfenpyrad were 37.6% and 5.4%, which were much higher than for dinotefuran at 24.7% and 0.84%, respectively. The data indicated that there was no significant health risk in tea for consumers at the recommended dosages. The results provide scientific data regarding the reasonable use of tolfenpyrad and dinotefuran aiming to ensure safe tea consuption. © 2021 Society of Chemical Industry.

Determination, dissipation dynamics, terminal residues and dietary risk assessment of thiophanate-methyl and its metabolite carbendazim in cowpeas collected from different locations in China under field conditions.

BACKGROUND: Thiophanate-methyl and its metabolite carbendazim are broad-spectrum fungicides used on many crops. The residues of these chemicals could result in potential environmental and human health problems. Therefore, investigations of the dissipation and residue behaviors of thiophanate-methyl and its metabolite carbendazim on cowpeas and associated dietary risk assessments are essential for the safety of agricultural products. RESULTS: A simple analytical approach using liquid chromatography with tandem mass spectrometry was developed and validated for the determination of thiophanate-methyl and carbendazim concentrations in cowpeas. Good linearity (R2 > 0.998) was obtained, and the recoveries and relative standard deviations were 80.0-104.7% and 1.4-5.2%, respectively. The dissipation rates of thiophanate-methyl, carbendazim and total carbendazim were high (half-lives of 1.61-2.46 days) and varied in the field cowpea samples because of the different weather conditions and planting patterns. Based on the definition of thiophanate-methyl, the terminal residues of total carbendazim in cowpea samples were below the maximum residue limits set by Japan for other legumes. The acute and chronic risk quotients of three analytes were 0.0-27.6% in cowpea samples gathered from all terminal residue treatments, which were below 100%. CONCLUSION: An optimized approach for detecting thiophanate-methyl and carbendazim in cowpeas was applied for the investigation of field-trial samples. The potential acute and chronic dietary risks of thiophanate-methyl, carbendazim and total carbendazim to the health of Chinese consumers were low. These results could guide the safe and proper use of thiophanate-methyl in cowpeas and offer data for the dietary risk assessment of thiophanate-methyl in cowpeas. © 2021 Society of Chemical Industry.

Residual behavior and dietary intake risk assessment of flonicamid, dinotefuran and its metabolites on peach trees.

BACKGROUND: Flonicamid and dinotefuran are widely applied to control pests and diseases in various economic crops arousing much public concerns about the potential risk to human health. In this study, the multi-determination and residual behavior of flonicamid-dinotefuran mixture on peach trees were investigated. The chronic risk of long-term dietary intake for Chinese consumers was evaluated. RESULTS: An optimized QuEChERS method combined with ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) analysis for simultaneous determination of flonicamid, dinotefuran and its metabolites was established to analyze the residual dissipation and terminal residues in peach matrices. The results demonstrated that (i) a satisfactory linearity relationship with the detector response and the correlation coefficient R2 > 0.999, the average recoveries of these four analytes ranged from 94 to 108%, the relative standard deviation was between 1.0% and 8.8%, and the limit of the quantitation was 0.02 mg kg-1 ; (ii) the dissipation behaviors of flonicamid and dinotefuran followed with the first-order dynamic kinetics model, and the half-lives were 6.9-12.4 days and 8.1-15.1 days, respectively; (iii) the recommended preharvest interval (PHI) was 21 days, the risk quotient (RQ) values of flonicamid and dinotefuran were 16.6 and 20.7%, respectively, which were significantly less than 100%. CONCLUSION: The established analytical method met the detection requirement in terms of sensitivity, accuracy, and precision. Additionally, the results indicated that the potential dietary intake risk of the flonicamid-dinotefuran mixture on peach trees was negligible. This work can be utilized in the safe and responsible use of flonicamid-dinotefuran mixture and provide guidance for establishing its maximum residue limit (MRL) in China. © 2021 Society of Chemical Industry.

Residue Monitoring and Risk Assessment of Cyazofamid and Its Metabolite in Korean Cabbage Under Greenhouse Conditions.

The residual characteristics and risk assessment with respect to cyazofamid and its metabolite 4-chloro-5-p-tolylimidazole-2-carbonitrile were monitored in case of Korean cabbage at different preharvest intervals during a greenhouse trial. The 0.02 kg a.i/ha of cyazofamid was sprayed twice on seven-day intervals (i.e., on day 0, 7, 14, and 21 before harvest). The liquid chromatography-tandem mass spectrometry analysis was used to monitor the residual amount of fungicide. The matrix-matched calibration curves with respect to the cyazofamid in Korean cabbage exhibited good linearity (R2 ≥ 0.999) and acceptable recoveries of 84.1%-114.9%. The biological half-life of cyazofamid in Korean cabbage was 3.18 days. During the treatment, the preharvest residue of cyazofamid in Korean cabbage 14 days before harvest (0.80 mg/kg) was lower than that specified by the MFDS-MRL (Ministry of Food and Drug Safety-Maximum Residue Limit, 2.0 mg/kg) and should be recommended as the safe preharvest-interval application limit. The hazard quotient showed low toxicity (70.58%) during the risk assessment study of cyazofamid.

Residue Analysis and Risk Assessment of Oxathiapiprolin and Its Metabolites in Cucumbers under Field Conditions.

In this study, a rapid, sensitive, and selective method was established for the detection of oxathiapiprolin and the metabolite IN-E8S72, as well as its glucose conjugate IN-SXS67 in cucumber using modified QuEChERS procedure combined with HPLC-MS/MS. The LOQs for all compounds were 0.02 mg kg-1, and the average recoveries were 77.4-111.3% with RSDs of 1.0-8.5%. Under the optimized conditions, the established method was successfully used to determine field samples in dissipation and terminal residue studies. The dissipation study results showed that oxathiapiprolin dissipated rapidly in cucumber with half-lives of 2.4-4.0 days. On the basis of the terminal residue results, the risk assessment was conducted, and both the international estimated daily intake (IEDI) or national estimated daily intake (NEDI) of oxathiapiprolin were much less than 100% which indicate a low health risk to consumers. This work provides guidance for establishing MRL of oxathiapiprolin in China and is of great significance for evaluating its dietary risk in cucumber.

Residue behavior and dietary risk assessment of chlorothalonil and its metabolite SDS-3701 in water spinach to propose maximum residue limit (MRL).

Dietary risk assessment generally combines food consumption data and the concentration of pesticide by using the risk quotient (RQ) method. Chlorothalonil is the second popular fungicide in the world, and its residue and risk assessment in water spinach remain unknown. In this paper, the field trials of chlorothalonil in water spinach were operated under good agricultural practice (GAP) in China to human health protective. The dissipation experiments demonstrated that chlorothalonil was rapidly degraded in water spinach, with the half-lives of 1.8-3.2 days, and the amount of its metabolite SDS-3701 (4-hydroxy-2,5,6-trichloroisophthalonitrile) taken up through the water spinach roots from the soil was minor. The terminal experiments disclosed that the average residues of chlorothalonil and SDS-3701 in water spinach were below 6.59 mg/kg and 0.01 mg/kg, respectively. The results suggested the chronic dietary risk probability of chlorothalonil was 51.95-59.15% in terms of all registered crops, and the acute dietary risk probability of chlorothalonil was 12.30%-63.01% in water spinach, highlighting that the dietary risk of chlorothalonil in water spinach under GAP was acceptable. MRL of chlorothalonil was proposed as 7 mg/kg for water spinach and 5 days was recommended as a safe pre-harvest interval (PHI) for chlorothalonil application in water spinach field.

Assessing in vitro dermal absorption of dry residues of agrochemical sprays using human skin within OECD TG 428.

We describe a novel experimental method that mimics exposure to dried agrochemical residues on contact surfaces during re-entry into crops. It includes the creation of dry dislodgeable residues and subsequent transfer to human skin for in vitro measurement of dermal absorption within a standard Organisation for Economic Co-operation and Development test guideline (OECD TG) 428 study. A pre-determined volume of spray containing 14C-labelled active substance is transferred onto a polytetrafluorethylene-coated septum and air-dried. The septum is then gently placed onto the pre-wetted skin mounted in a flow-through Franz diffusion chamber. The septum is gently rotated thrice to transfer the dose. Preliminary tests determined transfer efficiency to ensure the appropriate test concentration on the skin. Then, a standard dermal absorption study is performed according to OECD TG 428. Results from 10 compounds indicate that the methodology can be robustly incorporated into a standard TG study. These data show that the dermal absorption from a dry dislodgeable residue is lower than that from the equivalent dose of the aqueous spray, regardless of formulation type or active substance. Studies following the scenario described above can be a suitable tool to better estimate dermal absorption from dry residues in re-entry worker and resident exposure assessment for agrochemicals.

Buprofezin dissipation and safety assessment in open field cabbage and cauliflower using GC/ITMS employing an analyte protectant.

An analytical method for the determination of buprofezin residues in cabbage and cauliflower was developed and validated using gas chromatography with ion trap mass spectrometry. The analyte protectant d-sorbitol was used at a concentration level of 0.5 mg mL-1 in acetonitrile instead of in matrix for constructing the calibration curves of the buprofezin standard. The average recoveries ranged from 91.3 to 96.8%, with an RSD of ≤2.7%. The limits of detection and quantitation of the method in cabbage and cauliflower were 1.3, 1.7 and 4.3, 6.2 µg kg-1 , respectively. The residual levels and dissipation kinetics of buprofezin 25% wettabe powder in cabbage and cauliflower cultivated under open field conditions was investigated at the single (T1) and double (T2) recommended rates of application. Half-life periods were found to be 1.73 and 2.1 days in cabbage, whereas in cauliflower, these values were 1.85 and 2.36 days at T1 and T2, respectively. Based on the dissipation study, and the maximum residue limit value of 0.05 mg kg-1 , the proposed pre-harvest interval of buprofezin in cabbage was 3-6 days and that in cauliflower was 4-10 days. The results showed that buprofezin is safe for application at both recommended application rates.

Residue behaviors and risk assessment of flonicamid and its metabolites in the cabbage field ecosystem.

Flonicamid, a novel selective systemic pesticide, can effectively control a broad range of insect pests. However, the dissipation behaviors and the terminal residues of flonicamid and its metabolites in some crops and soils remain unclear. Herein, an easy, sensitive and reliable method using a modified QuEChERS extraction coupled with LC-MS/MS for the simultaneous analysis of flonicamid and its metabolites in cabbage and soil was developed. Based on this method, the dissipation behaviors of flonicamid and its metabolites as well as their persistence in cabbage and soil during harvest were investigated. Flonicamid degraded rapidly, and the half-lives of flonicamid only and total residues (the sum of flonicamid and its metabolites) were 1.49-4.59 and 1.97-4.99 days in cabbage, and 2.12-7.97 and 2.04-7.62 days in soil, respectively. When 50% flonicamid WG was sprayed once or twice at the recommended dose and 1.5-fold the recommended dose, the highest residues of total flonicamid in cabbage and soil from different pre-harvest intervals (3, 7 and 14 days) were 0.070 and 0.054 mg kg-1, respectively. The risk quotient (RQ) of flonicamid based on the consumption data from China was below 16.84%, indicating that the use of flonicamid is non-hazardous to humans. These results could not only guide the safe and responsible use of flonicamid in agriculture but also help the Chinese government establish the maximum residue level (MRL) for flonicamid in cabbage.

Dissipation behaviour and dietary risk assessment of boscalid, triflumizole and its metabolite (FM-6-1) in open-field cucumber based on QuEChERS using HPLC-MS/MS technique.

BACKGROUND: To resist plant diseases, boscalid and triflumizole have been applied to cucumbers frequently. However, the residue and dietary risk assessment of these fungicides in cucumber should be given attention for food safety. RESULTS: An effective and highly sensitive method based on the liquid chromatography-tandem mass spectrometry technique for simultaneous multidetermination of boscalid, triflumizole and its metabolite (FM-6-1) in a cucumber ecosystem was established and validated. Field experiments were conducted in three different locations, where boscalid and triflumizole (35% suspension concentration) were applied at 253 g of active ingredient (a.i.) per hectare (the recommended high dosage) and 379.5 g a.i. ha-1 (1.5 times the recommended high dosage) in each location. The limits of quantification and the limits of detection of the proposed method ranged from 0.01 to 0.05 mg kg-1 and 3.9 × 10-5 to 7.5 × 10-4 mg L-1 respectively. The mean recoveries and relative standard deviations of these compounds were 80-105% and 1.0-6.1% respectively. The dissipation dynamics of compounds followed pseudo-first-order kinetic models remarkably, with a half-value period of 2.3-40.8 days. The residues of boscalid and triflumizole in cucumber at harvest were below 0.66 mg kg-1 and 0.07 mg kg-1 respectively. The results of the dietary risk assessments have shown a low dietary risk of compounds in cucumber with hazard ratios <1 and hazard index <1. CONCLUSION: These results from the experiments are the most important for putting a guide on reasonable usage of these fungicides under the open-field conditions in China. © 2018 Society of Chemical Industry.

Liquid chromatography-mass spectrometry method for evaluating the dissipation dynamics of cyromazine and its metabolite in Agaricus bisporus and dietary risk assessment.

Providing guidance on the reasonable use of pesticide in agricultural production is of particular importance for ensuring food safety. In the present study, a field trial was performed to study the dissipation and accumulative pattern of cyromazine (CA) and its metabolite in Agaricus bisporus (A. bisporus) cultivation. An ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was first developed and validated for the determination of CA and melamine (MEL) in the casing soil and fruiting body. During the cultivation period, the dissipation rates of CA in the casing soil were between 51.57 and 63.48% at three dose groups. The fruiting body presented higher accumulation ability for MEL compared with CA. The terminal residues of MEL never exceeded the maximum residue limits (MRLs) in food. In addition, the intake health risk from the CA and MEL residues in the fruiting body were negligible to humans. This study will help to provide valuable guidance on the application strategies of CA in A. bisporus cultivation.

Residual behavior and risk assessment of tridemorph in banana conditions.

An efficient method has been developed for determining tridemorph in banana using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The dissipation and terminal residue of tridemorph in banana fields were carried out at good agricultural practice (GAP) conditions. The average recoveries ranged from 84.4% to 90.0% with relative standard deviations (RSDs) of 3.0%-7.0% at three different spiking levels. The results indicated that the tridemorph dissipated quickly in banana with half-lives of 7.0-7.7days. The results of residual distribution ranged from 0.01 to 0.26mg/kg, 0.01-0.62mg/kg and <0.01mg/kg in whole banana, peel and pulp, respectively. The relationship between application factor and residue was discussed. The results of risk assessment showed that the risk quotient (RQ) value was all below RQ=1. Given that China has not set an maximum residue limit (MRL) value for tridemorph in banana, this study could provide guidance for the reasonable use of tridemorph.

Dissipation, residues and risk assessment of spirotetramat and its four metabolites in citrus and soil under field conditions by LC-MS/MS.

A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for the simultaneous determination of spirotetramat and its four metabolite residues in citrus, peel, pulp and soil was developed and validated by liquid chromatography with tandem mass spectrometry (LC-MS/MS). The samples were extracted with acetonitrile (1%, glacial acetic acid, v/v) and purified using primary secondary amine and octadecylsilane. The limit of detection was 0.01-0.13 mg/kg, whereas that of quantification was 0.02-0.40 mg/kg for spirotetramat and its metabolites. The average recoveries of spirotetramat, spirotetramat-enol, spirotetramat-mono-hydroxy, spirotetramat-enol-glucoside and spirotetramat-ketohydroxy in all matrices were 73.33-107.91%, 75.93-114.85%, 76.44-100.78%, 71.46-103.19% and 73.08-105.27%, respectively, with relative standard deviations < 12.32%. The dissipation dynamics of spirotetramat in citrus and soil followed first-order kinetics, with half-lives of 2.3-8.5 days in the three sampling locations. The terminal residues of spirotetramat in four matrices at the three locations were measured below the 1.0 mg/kg maximum residue limit set by China, and residues were found to be concentrated on the peel. The risk assessment of citrus was evaluated using risk quotients. The risk quotient values were found to be significantly <1, suggesting that the risk to human health was negligible when using the recommended doses of spirotetramat in citrus. These results could provide guidance for the safe and proper application of spirotetramat in citrus in China.

Residue analysis and risk assessment of pyrethrins in open field and greenhouse turnips.

A sensitive and selective method was developed and validated for the determination of pyrethrin residues in turnips (turnip leaves, turnip tubers, and the whole of plant) and cultivated soil using gas chromatography coupled with mass spectrometry (GC-MS). Six major components of pyrethrins (pyrethrin I and II, cinerin I and II, and jasmolin I and II) were separated and identified. The method involving solid-phase extraction (SPE) cleanup led to satisfactory average recoveries (88.1-104%) with limits of quantification (LOQs) of 0.05 mg/kg. The dissipation and final residue of pyrethrins in six provinces (among these places, two experiments were conducted in greenhouse and other four experiments in open filed) in China were studied. The trial results suggested that the half-lives of pyrethrins in the whole of turnips and soil were 0.5-1.6 and 1.0-1.3 days, respectively, and the degradation of pyrethrins in the greenhouse was quicker than that in open fields. The final residues of pyrethrins in turnip leaves and tubers were all below the maximum residue limit (MRL) established by the EU (1.0 mg/kg). A pre-harvest interval of 2 days and MRL of 1.0 mg/kg are recommended to ensure food safety standards for pyrethrins in turnips. Long-term risk assessment and short-term risk assessment of turnip tubers were evaluated. Hazard quotient (HQ) and acute hazard index (aHI) were significantly less than 100%, indicating negligible risk for consumption of turnip tubers.

Decline patterns and risk assessment of 10 multi-class pesticides in young sprout amaranth (Amaranthus mangostanus) under greenhouse growing conditions.

The present study was designed to investigate the residual decline pattern and the risk assessment of 10 different class pesticides, namely azoxystrobin, boscalid, diazinon, diethofencarb, difenoconazole, etofenprox, flubendiamide, paclobutrazol, and pyraclostrobin in young vegetative amaranth (Amaranthus mangostanus) sprayed once or twice under greenhouse growing conditions. Field-incurred samples, collected at 3, 7, or 10 days after application of both treatments, were extracted and purified with the quick, easy, cheap, effective, rugged, and safe "QuEChERS" citrate-buffered method and analyzed with liquid chromatography-electrospray ionization tandem mass spectrometry (LC-MS/MS) in positive ion mode. The linearity was satisfactory with determination coefficients (R 2) falling between 0.9817 and 0.9999 and limits of detection (LOD) and quantification (LOQ) values of 0.0007 and 0.002 mg/kg, respectively. The mean recovery rate at four spiking levels (equivalent to 5, 10, 50, and 100 × LOQ) ranged from 78.1 to 131.6% with a relative standard deviation (RSD) of < 11%. Substantial differences in the initial deposit between the tested analytes were observed and clearly indicated that the structure, as well as the initial concentration of applied products, greatly affected the residue deposit. From the obtained residual data, the provisional marginal maximum residue limits (MRLs) and the pre-harvest intervals (PHI) were proposed. Risk assessment was evaluated by comparing the theoretical maximum daily intake (TMDI) with the acceptable daily intake (ADI). Herein, the TMDI was lower than the ADI (TMDI/ADI ratio ≤ 80% set by the Korean Ministry of Food and Drug Safety) except for difenoconazole (80.92%, marginally higher), indicating that the vegetative amaranth is not hazardous and can be consumed safely by Korean consumers.

Measurement of pyrethroids and their environmental degradation products in fresh fruits and vegetables using a modification of the quick easy cheap effective rugged safe (QuEChERS) method.

Pyrethroid insecticides are used extensively in agriculture, and they, as well as their environmental degradates, may remain as residues on foods such as fruits and vegetables. Since pyrethroid degradates can be identical to the urinary markers used in human biomonitoring, it is important to understand the contribution of these degradates when studying sources of human pyrethroid exposure. We modified the widely used Quick Easy Cheap Effective Rugged Safe (QuEChERS) method to measure several current-use pyrethroids (cis/trans-permethrin, cypermethrin, deltamethrin, esfenvalerate, bifenthrin, cyfluthrin, and cyhalothrin) and their environmental degradation products (3-PBA, cis/trans-DCCA, 4-F-3-PBA, DBCA, and MPA) in selected fresh fruits and vegetables. Using fortified samples, we determined extraction efficiencies from: tomatoes, oranges (whole, peeled, and rind), grapes, apples, bananas (peeled and rind only), onions, lettuce, green peppers, carrots and broccoli. For a subset of these food items (apples, grapes, tomatoes, lettuce and banana peel), we also established limits of detection (MDLs) and quantitation (MQLs). Each sample was homogenized (1kg) then spiked with the target pyrethroids and their degradation products. Sub-samples (15g) were extracted with acetonitrile, then salted out and partitioned with NaCl and MgSO4. The extract was divided and further cleaned using solid phase extraction (SPE) cartridges containing either graphitized non-porous carbon (pyrethroids) or C18 (degradation products). Sample analysis was via liquid chromatography/tandem mass spectrometry (LC-MS/MS). Considering the mean recoveries each of the 14 analytes in all 13 matrices: 42% of the recoveries were ≥90%, 70% were ≥80%, and 90% were ≥70%. All MDL's were less than 100ng/kg, except 3-PBA (132ng/kg, tomato), MPA (129ng/kg, tomato), and trans-permethrin (141ng/kg, banana peel). We then applied the method to non-spiked samples (subset of 5 for which the MDLs/MQLs had been determined) collected weekly for four weeks from local supermarkets. At least one pyrethroid was present in measureable concentrations in all matrices except banana peels. In contrast, the only degradation products detected were cis/trans-DCCA, in one lettuce sample.

The influence of effective microorganisms (EM) and yeast on the degradation of strobilurins and carboxamides in leafy vegetables monitored by LC-MS/MS and health risk assessment.

The aim of this study was to determine the behaviour of strobilurin and carbocyamides commonly used in chemical protection of lettuce depending on carefully selected effective microorganisms (EM) and yeast (Y). Additionally, the assessment of the chronic health risk during a 2-week experiment was performed. The statistical method for correlation of physico-chemical parameters and time of degradation for pesticides was applied. In this study, the concentration of azoxystrobin, boscalid, pyraclostrobin and iprodione using liquid chromatography-mass spectrometry (LC-MS/MS) in the matrix of lettuce plants was performed, and there was no case of concentration above maximum residues levels. Before harvest, four fungicides and their mixture with EM (1 % and 10 %) and/or yeast 5 % were applied. In our work, the mixtures of 1%EM + Y and 10%EM + Y both stimulated and inhibited the degradation of the tested active substances. Adding 10%EM to the test substances strongly inhibited the degradation of iprodione, and its concentration decreased by 30 %, and in the case of other test substances, the degradation was approximately 60 %. Moreover, the addition of yeast stimulated the distribution of pyraclostrobin and boscalid in lettuce leaves. The risk assessment for the pesticides ranged from 0.4 to 64.8 % on day 1, but after 14 days, it ranged from 0.0 to 20.9 % for children and adults, respectively. It indicated no risk of adverse effects following exposure to individual pesticides and their mixtures with EM and yeast.

Assessment of pesticide residues and gene expression in common carp exposed to atrazine and chlorpyrifos: Health risk assessments.

This study assessed the impacts of atrazine (ATR), chlorpyrifos (CPF) and combined ATR/CPF exposure on the kidney of common carp (Cyprinus carpio L.). The carp were sampled after a 40-d exposure to CPF and ATR, individually or in combination, followed by a 40-d recovery to measure the expression levels of heat shock proteins genes (HSP60, HSP70 and HSP90) and pesticide residues in the kidney tissue. The results revealed that the mRNA and protein levels of HSP60, HSP70 and HSP90 were induced in the kidney of common carp by ATR, CPF, and ATR/CPF mixture. The accumulated amounts of ATR, CPF, and their metabolites in the kidney tissues exhibited dose-dependency. These results exhibited that increasing concentration of ATR and CPF in the environment causes considerable stress for common carp, suggesting that the expression levels of HSP60, HSP70 and HSP90 may act as potential biomarkers for assessing the environmental ATR and CPF risk for carp.

Degradation pattern and risk assessment of chlorantraniliprole on berseem (Trifolium alexandrinum L.) using high performance liquid chromatography.

The persistence pattern of chlorantraniliprole on berseem leaves and its risk assessment for the safety of cattle were studied. QuEChERS method was used for the extraction and cleanup of samples and the residues of chlorantraniliprole were estimated using high performance liquid chromatography (HPLC) and confirmed by Liquid Chromatograph-Mass Spectrometer (LCMS-MS). The dissipation studies on berseem were carried out by application of chlorantraniliprole at five different dosages i.e. 11.6, 17.1, 23.1, 34.7 and 46.2 g a.i. ha(-1). Average initial deposits of chlorantraniliprole were found to be 0.47, 0.61, 0.78, 1.15 and 1.31 mg kg(-1), respectively. The residues reached below determination limit (BDL) of 0.01 mg kg(-1) in 5, 7, 7, 10 and 10 days for 11.6, 17.1, 23.1, 34.7 and 46.2 g a.i. ha(-1) dosages, respectively. Half-life (t1/2) of chlorantraniliprole on berseem was observed to be 0.93, 1.14, 1.06, 1.00 and 1.33 days, respectively, at 11.6, 17.1, 23.1, 34.7 and 46.2 g a.i. ha(-1). It was found that the theoretical maximum residue contributions (TMRC) values reached below maximum permissible intake (MPI) on 0 day in berseem samples treated with chlorantraniliprole. These studies, therefore suggest that the use of chlorantraniliprole formulation at different dosages does not seem to pose any hazards to the consumers and a waiting period of one day is suggested to reduce the risk before consumption of berseem leaves. These data could provide guidance for the proper and safe use of this pesticide on berseem in India.