Residue behavior and dietary risk assessment of six pesticides in pak choi using QuEChERS method coupled with UPLC-MS/MS.

A reliable and simple modified QuEChERS method with UPLC-MS/MS was developed for the simultaneous determination of six pesticides (dimethomorph, imidaclothiz, lufenuron, methoxyfenozide, pyridaben, spinetoram) and their metabolites in pak choi. Method validation indicated good linearity (R2 ≥ 0.99), accuracy (recoveries of 75%-112%), sensitivity (limits of quantification, 0.002-0.01 mg kg-1), and precision (relative standard deviations ≤ 21%), and matrix effects were -36-28%. The half-lives of the six pesticides in pak choi were 2.2-12 d under open field and greenhouse conditions. Considering the short growth cycle of pak choi, the terminal residue levels (0.046-7.8 mg kg-1) and the relevant maximum residue limits (MRLs) of some countries, 5 d was recommended as the pre-harvest interval for the six pesticides on pak choi. Dietary risk assessment revealed that the risk quotients were 3.1%-58% for different gender and age groups in China, indicating none unacceptable public health risk for general population. The results showed that all the six pesticides degraded faster and the terminal residues were much lower under open field conditions than those under greenhouse conditions, which was mainly due to the influence of rainfall, sunlight and other environmental factors. This work was thus significant in assessing the dissipation fate and food safety risks of the six pesticides on pak choi and facilitated the establishment of maximum residue limits.

Dissipation rates and residue levels of diflubenzuron and difenoconazole on peaches and dietary risk assessment.

The dissipation kinetics, residue levels, and potential risks of diflubenzuron and difenoconazole on peaches were investigated under open field conditions. Two years of field trials were carried out in Shanghai, China, and the half-lives of diflubenzuron and difenoconazole on peaches ranged from 4.4 to 25d. Their terminal residue concentrations on peaches were 0.022-5.7 mg/kg after three of the tested sampling intervals. Based on the maximum residue levels (MRLs) of difenoconazole on peaches, a preharvest interval (PHI) of 14 d was proposed. A PHI of 10 d was proposed for diflubenzuron after a dietary safety assessment. During the safety assessment, the hazard quotient (HQ) and risk quotient (RQ) on peaches were determined. The results showed that the HQs (3.6-8.3%) and RQs(51-55%) of diflubenzuron were acceptable, proving that diflubenzuron poses no potential health risks. For difenoconazole, the HQs (0.027-0.071%) were satisfactory, but the RQs (115-116%) exceeded 100%, which indicated potential risk.

Determination of type A trichothecenes in coix seed by magnetic solid-phase extraction based on magnetic multi-walled carbon nanotubes coupled with ultra-high performance liquid chromatography-tandem mass spectrometry.

Magnetic solid-phase extraction (m-SPE) is a promising sample preparation approach due to its convenience, speed, and simplicity. For the first time, a rapid and reliable m-SPE approach using magnetic multi-walled carbon nanotubes (m-MWCNTs) as the adsorbent was proposed for purification of type A trichothecenes including T-2 toxins (T2), HT-2 toxins (HT-2), diacetoxyscirpenol (DAS), and neosolaniol (NEO) in coix seed. The m-MWCNTs were synthesized by assembling the magnetic nanoparticles (Fe3O4) with MWCNTs by sonication through an aggregation wrap mechanism, and characterized by transmission electron microscope. Several key parameters affecting the performance of the procedure were extensively investigated including extraction solutions, desorption solvents, and m-MWCNT amounts. Under the optimal sample preparation conditions followed by analysis with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), high sensitivity (limit of quantification in the range of 0.3-1.5 µg kg(-1)), good linearity (R (2) > 0.99), satisfactory recovery (73.6-90.6 %), and acceptable precision (≤2.5 %) were obtained. The analytical performance of the developed method has also been successfully evaluated in real coix seed samples. Graphical Abstract Flow chart of determination of type A trichothecenes in coix seed by magnetic solid-phase extraction coupled with ultra-high performance liquid chromatography-tandem mass spectrometry.

Analysis of amicarbazone and its two metabolites in grains and soybeans by liquid chromatography with tandem mass spectrometry.

A sensitive, simple and reliable analytical method based on a modified quick, easy, cheap, effective, rugged, safe sample preparation and liquid chromatography with tandem mass spectrometry detection was developed for the simultaneous determination of amicarbazone and its two major metabolites desamino amicarbazone and isopropyl-2-hydroxy-desamino amicarbazone residues in grains (rice, wheat, corn, buckwheat) and soybean. Several parameters, including liquid chromatography and tandem mass spectrometry conditions, extraction approaches and the adsorbents for clean-up, which might influence the accuracy of the method, were extensively investigated. The established method was further validated by determining the linearity (R(2) > 0.99), fortified recovery (79-118%), precision (1-12%) and sensitivity (limit of quantification, 5 µg/kg for amicarbazone and desamino amicarbazone, and 10 µg/kg for isopropyl-2-hydroxy-desamino amicarbazone). Finally, the established method was successfully applied to determine the residues of amicarbazone and its metabolites in 49 real samples of grain and soybean.

Development of a UPLC-MS/MS-based method for simultaneous determination of advanced glycation end products and heterocyclic amines in stewed meat products.

A novel analytical strategy was proposed to simultaneously quantify two advanced glycation end products (AGEs) including Nε-(Carboxymethyl)lysine (CML), Nε-(Carboxyethyl)lysine (CEL) and eight heterocyclic amines (HAs) including IQ, MeIQ, MeIQx, 4,8-DiMeIQx, 7,8-DiMeIQx, PhIP, Harman, and Norharman. The procedure was based on a two-step extraction, solid phase extraction (SPE) purification followed by ultra performance liquid chromatography tandem mass spectrometry. The established method showed a good linearity (R2 ≥ 0.9950), rapid processing time (8 min per sample), satisfactory recoveries (matrix spiked recoveries range from 72.2% to 119.6%) and precision (intra-day and inter-day RSDs were <19.3%). The limit of quantification (LOQ) and limit of detection (LOD) resulted to be between 0.05-15 ng/g and 0.2-50 ng/g, respectively. The validated technique was further applied to determine HAs and AGEs in eight stewed meat product samples consumed in Shanghai, with the amount of HAs and AGEs ranging from 2.851 to 18.289 ng/g and 118.158-543.493 ng/g, respectively.

Effect of acrolein on the formation of harman and norharman in chemical models and roast beef patties.

Harman and norharman were the most abundant ß-carboline-type heterocyclic amines (HCAs) detected in various foodstuffs. Unsaturated fatty acids in foods may undergo rapid oxidative deterioration during transportation, storage and heat treatment, forming reactive carbonyl species (RCS). This work studied the effects of acrolein, a highly reactive RCS, on the formation of harman and norharman in the tryptophan model system. Results showed that 0.005, 0.01, 0.015, 0.02, 0.05, 0.1 and 0.2 mmol of acrolein led to harman production increased by 528 %, 752 %, 981 %, 1172 %, 1375 %, 1288 % and 768 % respectively, and led to norharman formation increased by 116 %, 129 %, 152 %, 169 %, and 197 %, 185 % and 157 %, respectively. Furthermore, acrolein addition reduced the residue of tryptophan (up to 63.19 %), but increased the level of the intermediates including formaldehyde (up to 352 %), acetaldehyde (up to 491 %), (1S,3S)-1-Methyl-1,2,3,4-tetrahydro-ß-carboline-3-carboxylic acid (MTCA, up to 1936 %), and 1,2,3,4-tetrahydro-ß-carboline-3-carboxylicacid (THCA, up to 2142 %) in the tryptophan model system. Acrolein might react with tryptophan, harman and norharman to eliminate them directly. These data suggested that acrolein may contribute to harman and norharman formation through participating in the above complex chemical reactions. In addition, the content of harman and norharman produced in roast beef patties made of minced beef oxidized for 2, 4, 6, 8, and 10 days increased by 118 %, 188 %, 267 %, 137 %, and 48 %, respectively, and led to norharman formation increased by 140 %, 132 %, 90 %, 86 %, and 74 %, respectively compared with those made of fresh minced beef, which further illustrated that lipid oxidation products potentially contributed to harman and norharman formation.

Fluorescent labeling and tracing of immobilized efficient degrading bacterium DNB-S1 and its remediation efficiency of DBP contaminated soil.

Dibutyl phthalate (DBP) is an organic pollutant frequently detected in soil, and is a reproductive poison that harms animals both before and after birth and has mutagenic, teratogenic, and carcinogenic effects. DBP removal from farmland has been the subject of extensive research in recent years. Efficient DBP degrading bacterial strains were screened in the laboratory. GFP (Green fluorescent protein) labeled degradation strain GFP-DNB-S1 was analyzed for its activity and dynamics. Using sodium alginate (SA) and nano-hydroxyapatite (n-HAP) as carrier materials and CaCl2 as a cross-linking agent, the immobilized microbial agent n-HAP/SA + DNB-S1 was prepared by embedding cross-linking immobilization technology to study the remediation effect of DBP contaminated soil. The best formation effect of immobilized materials (n-HAP/SA) was found when the SA to n-HAP ratio was 3:2. When compared to single SA immobilized bacteria, n-HAP/SA immobilized bacteria improved the surface roughness and porosity of the microspheres. After 70 days, LED light revealed that the immobilized bacteria's GFP green fluorescent protein expression was stable. At 70 days, the initial DBP concentration of 500 mg ∙ L-1 degraded at a rate of 69.9%. The degrading bacteria had no effect on DBP degradation before and after being labeled with GFP. The n-HAP/SA immobilized bacteria offered a better living environment for microorganisms due to their rougher surface and a greater number of pores. This protected the microorganisms and increased the efficiency of DBP degradation. When the concentration of DBP in contaminated soil was set to 20 mg ∙ kg-1 and the n-HAP/SA + DNB-S1 immobilized bacterial agent was applied to the soil, the rate of DBP degradation was determined to be 93.34%. The degradation process followed First-order degradation kinetics, which improved the physical and chemical properties of the soil as well as its fertility.

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.

Development of Acid Hydrolysis-Based UPLC-MS/MS Method for Determination of Alternaria Toxins and Its Application in the Occurrence Assessment in Solanaceous Vegetables and Their Products.

In this work, we proposed an acid hydrolysis-based analytical method for the detection of Alternaria toxins (ATs) in solanaceous vegetables and their products with solid-phase extraction (SPE) and ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). This study was the first to reveal that some compounds in the eggplant matrix bind to altenusin (ALS). Validation under optimal sample preparation conditions showed that the method met the EU criteria, exhibiting good linearity (R2 > 0.99), matrix effects (-66.6--20.5%), satisfying recovery (72.0-107.4%), acceptable precision (1.5-15.5%), and satisfactory sensitivity (0.05-2 µg/kg for limit of detection, 2-5 µg/kg for limit of quantification). Out of 393 marketed samples, only 47 samples were detected, ranging from 0.54-806 µg/kg. Though the occurrence ratio (2.72%) in solanaceous vegetables could be negligible, the pollution status in solanaceous vegetable products was much more serious, and the incidences were 41.1%. In the 47 contaminated samples, the incidences were 4.26% for alternariol monomethyl ether (AME), 6.38% for alternariol (AOH) and altenuene (ALT), 42.6% for tentoxin (TEN), and 55.3% for tenuazonic acid (TeA).

Oxic effects of Pb-Ce compound pollution on Chinese cabbage and programmed cell death in root tip cells.

Heavy metal pollution is increasing, and rare earth elements (REE) play an important role in the environmental impact of heavy metals. Mixed heavy metal pollution is a major issue with complex effects. Despite substantial research on single heavy metal pollution, relatively few studies have focused on pollution from rare earth heavy metal composites. We studied the effects of different concentrations of Ce-Pb on the antioxidant activity in root tip cells and biomass of Chinese cabbage. We also used the integrated biomarker response (IBR) to evaluate the toxic effects of rare earth-heavy metal pollution on Chinese cabbage. We used programmed cell death (PCD) for the first time to reflect the toxicological effects of heavy metals and rare earths and studied the interaction between Ce and Pb in root tip cells in depth. Our results showed that Ce-Pb compound pollution can induce PCD in the root cells of Chinese cabbage, and the toxicity of compound pollutants is greater than that of single pollutants. Our analyses also provide the first evidence that Ce and Pb exert interaction effects in the cell. Ce induces Pb transfer in plant cells. The Pb content in the cell wall decreases from 58% to 45%. Additionally, Pb induced Ce valence changes. Ce (III) decreased from 50% to 43%, while Ce (IV) increased from 50% to 57%, directly resulting in PCD in the roots of Chinese cabbage. These findings improve our understanding of the harmful effects of compound pollution with rare earth metals and heavy metals on plants.

Residue behaviors, degradation, processing factors, and risk assessment of pesticides in citrus from field to product processing.

Pesticide residues in citrus may cause health risks in related juice products, and bring much uncertainty during the processing procedures. In this study, based on the dispersive solid-phase extraction (d-SPE) and UPLC-MS/MS, the residual levels of ten analytes in citrus and its processed products were monitored. The results showed that dissipation of the pesticides followed the first-order kinetics and the half-lives in citrus varied greatly, ranging from 6.36 to 63.0 days. The terminal residues of the five pesticides at harvest time were <0.01-0.302 and <0.01-0.124 mg/kg in raw citrus and citrus flesh, respectively, all of which were lower than the corresponding maximum residue limits (MRLs) of 0.5-1 mg/kg. In the processing experiments, the residues of ten analytes in sterilized juice, concentrated juice, and citrus essential oil were in the range of <0.01 to 0.442 mg/kg, <0.01 to 1.16 mg/kg, and <0.01 to 44.0 mg/kg, respectively, and the corresponding processing factors (PFs) were 0.127-1.00, 0.023-3.06, and 0.006-39.2. Particularly, in citrus essential oil, the PFs of etoxazole, fluazinam, lufenuron and spirotetramat-keto-hydroxy were 1.68-39.2, exhibiting obvious enrichment effects. By integrating the residue data of the field trials and the PFs, the acute and chronic dietary risks of the target pesticides in citrus juice were 0.031-1.83 % and 0.002-2.51 %, respectively, which were far lower than 100 %, demonstrating no unacceptable risk to human health. This work provides basic data for the establishment of the MRLs and dietary exposure risk assessment for processed citrus products.

[Determination of disulfoton and its metabolites in agricultural products by dispersive soild phase extraction-ultra high performance liquid chromatography-tandem mass spectrometry].

Disulfoton, an organophosphorus pesticide, is used to control cotton, beet, potato, and other seedling period aphids, leaf moths, underground pests, etc., with internal absorption, killing, gastric poisoning, and fumigation. Disulfoton is a highly toxic organophosphate pesticide, which can inhibit cholinesterase activity, resulting in neurophysiological disorders by inhalation, feeding, and transdermal absorption. Disulfoton is difficult to degrade in the environment, which leads to enrichment in organisms and interference with endocrine. This compound is harmful to the ecological environment and human health. To ensure the quality and safety of food, it is important to develop a detection method for disulfoton and its metabolites in agricultural products. A reliable method based on dispersive solid phase extraction (d-SPE) with ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed for the determination of disulfoton and its metabolites (disulfoton sulfone, disulfoton sulfoxide, demeton-S, demeton-S sulfone, and demeton-S sulfoxide) in agricultural products (pea, asparagus, wheat, coffee bean, and peanut). The optimal extraction method was as follows: 5.0 g the samples were extracted with acetonitrile (wheat, coffee bean, and peanut presoaked in 5 mL water) in a 50 mL centrifuge tube, followed by 10 min vortex. Before 30 s vortex, 4 g NaCl was added. After 5 min centrifugation, 1.5 mL of the supernatant was cleaned up with 50 mg octadecylsilane bonded silica (C18), 50 mg primary secondary amine (PSA), and 50 mg aminopropyl (NH2) adsorbents. The analytes were separated on a Thermo Syncronis C18 column (150 mm×2.1 mm, 5 µm) with gradient elution using water and acetonitrile at a column temperature of 40 ℃. The injection volume was 2 µL. Disulfoton and its metabolites were analyzed in multiple reaction monitoring (MRM) mode with positive electrospray ionization (ESI+) for the selective quantification. Qualitative and quantitative analyses were accorded to the retention times and characteristic ion pairs with one parent ion and two fragment ions. Quantitative analysis was performed by an external standard method using matrix-matched calibration curves. All the parameters that affected the extraction efficiencies were optimized. C18, PSA, and NH2 gave good recoveries of 87.9%-109.0%. Other adsorbents, multiwalled carbon nanotubes (MWCNTs), hydroxylated multiwalled carbon nanotubes (OH-MWCNTs), carboxylated multiwalled carbon nanotubes (COOH-MWCNTs), octylsilane bonded silica (C8), strong cation exchange (SCX) and neutral alumina (N-Al2O3), led to recoveries below 56.2%. The combination of adsorbents was also considered. Seven different combinations of 50 mg C18, 50 mg PSA, and 50 mg NH2 were chosen for the optimization experiments. There were no obvious differences in these combinations, and the target analytes recoveries ranged from 81.0% to 109.3% with relative standard deviations (RSDs) between 0.6% and 12.5%. The matrix effect could affect the extraction efficiency. The adsorbents of 50 mg C18, 50 mg PSA, and 50 mg NH2 showed weaker matrix effects as compared with other combinations of adsorbents in the instrument. The results for the matrix effect showed that peanuts and asparagus exceeded 20%, requiring matrix-matched calibration curves. Under the optimized conditions, disulfoton and its metabolites showed good linearities (R2≥0.9981) in the range of 2.0-200.0 µg/L. The average spiked recoveries of disulfoton and its metabolites in peas, asparagus, wheat, peanuts, and coffee beans ranged from 75.0% to 110.0%, with RSDs of 0.7% to 14.9%. The limits of detection (LODs) were between 0.02 and 2.0 µg/kg, and the limits of quantification (LOQs) were 5.0 µg/kg. The method was applied for the detection of 80 commercial productions, and neither disulfoton nor its metabolites were found. The proposed method is rapid, accurate, highly selective, and sensitive, and it is suitable for the simultaneous determination of disulfoton and its metabolites in grain, oil crops, vegetables, and other matrices.

Analysis of the performance of the efficient di-(2-ethylhexyl) phthalate-degrading bacterium Rhodococcus pyridinovorans DNHP-S2 and associated catabolic pathways.

The widespread use of plastic has led to the global occurrence of phthalate esters (PAEs) pollution. PAEs can be effectively removed from polluted environments by microbe-mediated degradation. Di-(2-ethylhexyl) phthalate (DEHP) has the highest residual concentration in agricultural soil-contaminated areas compared to other PAEs in most of China. The Rhodococcus pyridinovorans DNHP-S2 microbial isolate identified was found to efficiently degrade DEHP. Within a 72 h period, the bacteria were able to degrade 52.47% and 99.75% of 500 mg L-1 DEHP at 10 °C and 35 °C, respectively. Dimethyl phthalate (DMP) was first identified as an intermediate metabolite of DEHP, which is different from the previously reported DEHP catabolic pathway. Genomic sequencing of DNHP-S2 identified benzoate 1,2-dioxygenase and catechol 2,3/1,2-dioxygenase as potential mediators of DEHP degradation, consistent with the existence of two downstream metabolic pathways governing DEHP degradation. Three targets DEHP metabolism-related enzymes were found to be DEHP-inducible at the mRNA level, and DNHP-S2 was able to mediate the complete degradation of DEHP at lower temperatures, as confirmed via RT-qPCR. DNHP-S2 was also found to readily break down other PAEs including DMP, di-n-butyl phthalate (DBP), di-n-octyl phthalate (DnOP), and n-butyl benzyl phthalate (BBP). Together, these results thus highlight DNHP-S2 as a bacterial strain with great promise as a tool for the remediation of PAE pollution. In addition to providing new germplasm and genetic resources for use in the context of PAE degradation, these results also offer new insight into the potential mechanisms whereby PAEs undergo catabolic degradation, making them well-suited for use in PAE-contaminated environments.

Interference between di(2-ethylhexyl) phthalate and heavy metals (Cd and Cu) in a Mollisol during aging and mobilization.

Diffuse pollution of the soil by phthalates and heavy metals causes numerous concerns. Their respective fates when coexisting require further investigation. In this study, di(2-ethylhexyl) phthalate (DEHP) and Cd/Cu were used as subjects, focusing on their behavior in Mollisols under combined pollution based on their concentration, fractionation, and leaching. The results indicated that when the two pollutants coexist, the dissipation rate of DEHP in the soil decreased, and its half-life was extended from 30.81 to 40.53 (Cd) and 35.40 d (Cu). DEHP altered the distribution of Cd and Cu in the soil, and this effect persisted after most of the DEHP had degraded. Leaching tests showed that the interaction of DEHP with Cd and Cu hindered leaching during the first rainfall event, but as DEHP degraded and Cd/Cu stabilized, the trapped pollutants were gradually released in subsequent rainfall events. Additionally, to investigate the partitioning of pollutants between soil water and solid surfaces, a diffusion model of DEHP and metal ions on the surface of montmorillonite (high specific surface area adsorbents abundant in soils) was built using molecular dynamics simulations. Simulations revealed their density distribution on the clay surface increased synergistically, whereas their diffusion was antagonistic. This study provides basic data and theoretical support concerning the ecological risk assessment of combined phthalate and heavy metals pollution in soil.

Determination of 1-methylcyclopropene residues in vegetables and fruits based on iodine derivatives.

An innovative method was established for the determination of 1-methylcyclopropene (1-MCP) in vegetables and fruits. Due to its small molecular weight and low boiling point, it was difficult to obtain quantitative analysis for 1-MCP, especially at the residual level. In this work, based on its iodine derivatives, 1-MCP was derived to 1,2-diiodo-1-methylcyclopropane, which was much easier for trace and accurate chromatographic analysis. During the method validation, the method validation results were satisfactory in terms of linearity (4 ~ 400 µg/L, and R2 ≥ 0.959), matrix effect (-89% ~ -13%), accuracy (80 ~ 100%), sensitivity (limits of quantification, 5 µg/kg) and precision (relative standard deviations ≤ 19%), which was in accordance with the Chinese guidelines for the testing of pesticide residues in crops. Finally, the proposed analytical method was used to monitor the 1-MCP residue levels in commercially available samples, and all the values were below 5 µg/kg, which satisfied the EU or Japan MRLs of 1-MCP.

Evaluation of cleanup procedures in pesticide multi-residue analysis with QuEChERS in cinnamon bark.

Cinnamon bark is a very complex spices matrix for pesticide residue analysis. In this study, two cleanup procedures, dispersive solid-phase extraction (d-SPE) and repetitive d-SPE, combined with Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction were both investigated and applied for the determination of 60 pesticide residues in cinnamon bark by liquid chromatography - tandem mass spectrometry (LC-MS/MS) detection. The extraction solvents, phase partition salts, and cleanup sorbents were optimized. The results showed that 150 mg MgSO4 + 50 mg C18 showed the best performance in d-SPE. The repetitive d-SPE achieved less matrix effects than d-SPE, but several high water-solubility analytes were lost during the cleanup, and also the 10 fold dilution compromised the sensitivities of analytes. With the validated QuEChERS-d-SPE method, 44 of 60 pesticides obtained satisfactory recoveries (71%-118%) and RSDs (2%-27%) at three to five spiking levels. The method was applied to monitor 15 market cinnamon samples.

Dissipation and safety evaluation of novaluron, pyriproxyfen, thiacloprid and tolfenpyrad residues in the citrus-field ecosystem.

The dissipations and residues of four pesticides in citrus, under field conditions, were measured using solid-phase extraction and LC-MS/MS. In the method validation, satisfactory results were obtained with fortified recoveries ranging from 80.6 to 113% and relative standard deviations ≤9.0%. In the dissipation test, the half-lives for the pesticides in citrus, according to first-order kinetics, ranged from 13.3 to 28.9 days. Based on the terminal residue test, two evaluation models (hazard quotient, HQ; risk quotient, RQ) were applied on citrus fruits for dietary exposure risk assessment. The results showed that HQs ranged from 0.0031 to 0.78%, and RQs from 7.3 to 57%, which are both acceptable for human consumption. Therefore, 14-day was proposed as a pre-harvest interval for the target compounds in citrus fruits. This work also contributes to residue data and, therefore, scientifically validated maximum residue limits in citrus, which are lacking in China currently.

Multi-walled carbon nanotubes as solid-phase extraction sorbents for simultaneous determination of type A trichothecenes in maize, wheat and rice by ultra-high performance liquid chromatography-tandem mass spectrometry.

A solid-phase extraction (SPE) procedure using multi-walled carbon nanotubes (MWCNTs) as sorbents coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed for simultaneous determination of four type A trichothecenes in maize, wheat and rice for the first time. Several key parameters including the composition of sample loading solutions, washing and elution solvents were thoroughly investigated to achieve optimal SPE recoveries and efficiency. Performance of the MWCNTs materials was significantly affected by pH, and after optimization, n-hexane and 5% methanol aqueous solution as the washing solutions and methanol containing 1% formic acid as the elution solvent presented an excellent purification efficiency for the four targets in the different matrices. The method was validated by determining the linearity (R(2)≥0.992), recovery (73.4-113.7%), precision (1.2-17.1%) and sensitivity (limit of quantification in the range of 0.02-0.10µg/kg), and was further applied for simultaneous determination of type A trichothecenes in 30 samples. Although low contamination levels of type A trichothecenes in wheat, maize and rice were observed revealing mitigated risks to consumers in Shanghai, China, the developed method has proven to be a valuable tool for type A trichothecenes monitoring in complex crop matrices.

Dissipation kinetics and degradation mechanism of amicarbazone in soil revealed by a reliable LC-MS/MS method.

A sensitive and reliable analytical method was developed for simultaneous determination of amicarbazone (AMZ) and its two major metabolites including desamino amicarbazone (DA) and isopropyl-2-hydroxy-DA-amicarbazone (Ipr-2-OH-DA-AMZ) in soil for the first time. Targeted analytes were extracted and purified using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure, and then analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a total run time of 9 min. The established approach was extensively validated by determining the linearity (R (2) ≥ 0.99), recovery (84-96 ), sensitivity (limits of quantification at 5-10 µg kg(-1)), and precision (RSDs ≤12 %). Based on the methodological advances, the subsequent dissipation kinetics and degradation mechanism of amicarbazone in soil were thoroughly investigated in an illumination incubator. As revealed, AMZ was easily degraded with the half-lives of 13.9-19.7 days in soil. Field trial results of AMZ (40 g a.i. ha(-1)) in Shanghai showed that the residues of AMZ and its metabolite Ipr-2-OH-DA-AMZ decreased from 0.505 mg kg(-1) (day 50) to 0.038 mg kg(-1) (day 365) and from 0.099 mg kg(-1) (day 50) to 0.028 mg kg(-1) (day 365), respectively, while the content of DA increased from 0.097 mg kg(-1) (day 50) to 0.245 mg kg(-1) (day 365). This study provided valuable data to understand the toxicity of AMZ and substantially promote its safe application to protect environment and human health.

Dissipation and residues of carfentrazone-ethyl in wheat and soil.

The purpose of this article was to study the dissipation rate of carfentrazone-ethyl in soil and its terminal residue in wheat field eco-system. The results showed that carfentrazone-ethyl dissipated rapidly in soil after application. Its half-lives in soil were 5.8 and 3.8 h in Beijing and Jilin, respectively. The terminal residues of carfentrazone-ethyl in soil samples were very low (around 0.003-0.005 mg/kg), and the residues in wheat grain were not detectable. The use of carfentrazone-ethyl in wheat could be considered to be safe.