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Highlights • A QuEChERS method was modified of carboxin and its metabolites in peanuts. • Supervised field trials were conducted of carboxin in peanuts. • The total carboxin in peanut samples from fields and markets were measured. • The carboxin-exposure risk by eating peanuts was evaluated via a probabilistic model. Abstract We developed an ultra-performance liquid chromatography-tandem mass spectral method to determine the fungicide carboxin and its metabolites, oxycarboxin and carboxin sulfoxide in peanut samples. The method was used to detect the concentration of the analytes in the samples from fields and markets. The total residue quantities in peanut kernels were used to evaluate the chronic dietary risk of total carboxin upon peanut consumption. The estimated dietary intake of carboxin from peanuts whose seeds had been treated with carboxin at the recommended dose was between 0.020% and 0.344% of acceptable daily intake and the risk was found to be negligible. The chronic dietary risk assessment from markets and commercial field samples for various groups of humans indicated that the group with the greatest degree of exposure was 45 to 75-year-old women who lived in rural areas. However, their acceptable daily intake percentage was 0.006%, meaning that their health risk was extremely small. [ABSTRACT FROM AUTHOR]

Abstract: An ultra high‐performance liquid chromatography with tandem triple quadrupole mass spectrometry residue method was developed and validated for the quantification and identification of dinotefuran and its main metabolites 1‐methyl‐3‐(tetrahydro‐3‐furylmethyl) urea and 1‐methyl‐3‐(tetrahydro‐3‐furylmethyl) guanidine in fruit (watermelon), vegetable (cucumber), cereal (rice), animal‐derived foods (milk, egg, and pork), soil, and water. The samples were extracted with acetonitrile containing 15% v/v acetic acid and purified with dispersive solid‐phase extraction with octadecylsilane, primary secondary amine, graphitized carbon black, or zirconia‐coated silica prior to analysis. The method had an excellent linearity (R2 ≥ 0.9942, 1–500 μg/L) and satisfactory recoveries (73–102%) at five spiked levels (0.001, 0.01, 0.05, 0.5, and 2 mg/kg) with intra‐ or interday precision in the range of 0.8–9.5% and 3.0–12.8% for the three compounds in the eight matrices. The limits of quantification were 10 μg/kg for 1‐methyl‐3‐(tetrahydro‐3‐furylmethyl) guanidine and 1 μg/kg for 1‐methyl‐3‐(tetrahydro‐3‐furylmethyl) urea and dinotefuran. The applicability of the developed method was demonstrated by determining the occurrence of dinotefuran, 1‐methyl‐3‐(tetrahydro‐3‐furylmethyl) guanidine, and 1‐methyl‐3‐(tetrahydro‐3‐furylmethyl) urea in various samples from plants, animal‐derived foods, and the environment. From 80 samples, 70 contained dinotefuran (0.8–11.7 μg/kg), among which six also contained 1‐methyl‐3‐(tetrahydro‐3‐furylmethyl) urea (water and rice, 0.5–0.9 μg/kg). [ABSTRACT FROM AUTHOR]

We have developed a rapid, multi-compound analytical method for measuring residues of the pesticides thiamethoxam and its metabolite, clothianidin; fipronil and its three metabolites, fipronil sulfone, fipronil sulfide, and fipronil desulfinyl; and pyraclostrobin in unprocessed foods (rice, corn, cucumbers, tomatoes, apples, and bananas) by ultra-performance liquid chromatography coupled to tandem mass spectrometry. Acetonitrile was used as the extraction solvent, and an octadecylsilane-dispersive SPE was used to clean up the analytes, which were then separated through a UPLC HSS T3 column connected to a tandem mass spectrometer via an electrospray ionisation source. The linearity of this method for the target analytes was excellent (R2 ≥0.990) in the concentration range of 5–1000 μg kg–1. The average recoveries of the seven compounds at concentrations of 10, 100, and 1000 μg kg–1from six spiked matrix samples ranged from 73.6 to 110.6%, all with RSD values of ≤19.7%. The limit of quantification was 10 μg kg–1. The method validated the effectiveness of the method for routine monitoring the residue of these pesticides and their metabolites in foods. [ABSTRACT FROM PUBLISHER]

In this study, an efficient and fast method for the determination of the herbicide mesotrione and its two metabolites [4-methylsulfonyl-2-nitrobenzoic acid (MNBA) and 2-amino-4-methylsulfonylbenzoic acid (AMBA)] in rice, rice plants, rice hulls, water, and soil was developed, using ultra performance liquid chromatography coupled with tandem quadrupole (Xevo TQ-S) mass spectrometry (UPLC-Xevo TQ-S-MS/MS). The recoveries of the compounds were 68.6%–108.4% at different levels. The intra-day relative standard deviation (RSD) ranged from 2.0% to 14.4%, and the inter-day RSD, from 1.9% to 11.4%. The limits of quantification (LOQ) were ranged from 0.146 to 4.545 μg kg −1 for mesotrione, MNBA and AMBA. Dissipation and residual assays with the commercial formulation were conducted at three locations. The dissipation rates of the compounds were fast in rice plants, soil, and water, and residues at harvest were not detected in any of the three localities. [ABSTRACT FROM AUTHOR]

A simple residue analytical method based on the QuEChERS approach and high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) detection was developed for the analysis of fipronil and its three metabolites in cottonseed, cotton plant and soil. The average recoveries of four test compounds from all three matrices were 78.6–108.9% at the level of 0.005 to 0.5 mg/kg, with an RSD in the range of 0.6 to 13.7%. The limit of quantification (LOQ) of the four test compounds ranged from 0.005 to 0.01 mg/kg. The results of the residual dynamics experiments showed that fipronil dissipated rapidly in cotton plants and soil and that oxidation and photolysis were the main degradation pathways. Moreover, the bi-exponential models demonstrated a good fit of the measured data for fipronil in cotton plants and soil, with R2 in the range of 0.8989 to 0.9989. Furthermore, a total of 40 samples of cottonseed from Shandong Province were analyzed, and all of the samples were free from the four test compound residues. [ABSTRACT FROM AUTHOR]

Highlights: [•] QuEChERS method was firstly used to extract oxathiapiprolin and its 2 metabolites. [•] UPLC–MS/MS was firstly used to determine oxathiapiprolin and its 2 metabolites. [•] Various solvents and sorbents were evaluated for the sample preparation. [•] The method exhibits acceptable recovery and high sensitivity. [•] Application of method validation showed good results. [ABSTRACT FROM AUTHOR]

A new analytical method using the quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure for simultaneous determination of afidopyropen and its metabolite M440I007 residues in tomato, watermelon, pepper, cucumber, pear, grape, cabbage and soil samples was developed using ultra-high performance liquid chromatography coupled with tandem mass spectrometry. The target compound was determined in less than 5.0 min using an electrospray ionisation source in positive mode (ESI+). The limit of quantification was 1 μg kg−1 in different matrices. Two sorbents primary secondary amine and graphitised carbon black were used in the QuEChERS procedure, and matrix-matched standards gave satisfactory recoveries and relative standard deviation (RSD) values in different matrices at three spiked levels (1, 10 and 500 μg kg−1). For afidopyropen, the recoveries ranged from 83% to 104% with an intra-day relative standard deviation (RSDr) of 1-8%, while they were from 80% to 103% with RSDr of 2-8% for M440I007. Reproducibility ranged between 1% and 19% for the three spiked levels. [ABSTRACT FROM AUTHOR]

Trace analysis method is a reliable basis for studying the translocation and metabolism of imidacloprid used as an insecticide in wheat, and it clarifies whether biologically active metabolites including residual imidacloprid, have long‐lasting insecticidal potency against wheat aphids under seed treatment during the entire growth period. In this study, a highly sensitive analytical method was established to determine the residues of imidacloprid and its six metabolites (5‐hydroxy imidacloprid, imidacloprid olefin, imidacloprid guanidine, imidacloprid urea, 6‐chloronicotinic acid, and imidacloprid nitrosimine) in wheat–soil systems, such as in wheat leaves, wheat ears, wheat grains, roots, and soil. All the compounds were extracted using an ACN:water (8:2, v/v) mixture and purified by dispersive solid‐phase extraction. The average recoveries ranged from 74.4% to 109.5% for all matrices, with intra‐ and inter‐day variations of less than 14.9%. The limit of quantitation was in the range of 0.001–0.005 mg/kg. The method is demonstrated to be sensitive and accurate for monitoring imidacloprid and its metabolites at trace levels during the entire growth period under field conditions. [ABSTRACT FROM AUTHOR]

An effective analytical method for the simultaneous determination of a novel insecticide flupyradifurone and its two metabolites was developed using ultra high performance liquid chromatography with tandem mass spectrometry coupled with a quick, easy, cheap, effective, rugged, and safe procedure. The three target compounds were extracted with acetonitrile and cleaned up with octadecylsilane, and were separated successfully between 1.9 and 3.1 min using an HSS T3 chromatographic column connected to an electrospray ionization source. All the matrix-matched samples at three fortified levels (0.01, 0.05, and 0.5 mg/kg) provided satisfactory recoveries in the range of 70.3-116.5% with relative standard deviations below 18.6%. The limits of quantitation were 10 μg/kg for flupyradifurone and difluoroethylamino-furanone and 100 μg/kg for 6-chloronicotinic acid. The limit of quantification of flupyradifurone was far below the maximum residue limit in the USA. The method is of great significance for establishing maximum residue limits in China. [ABSTRACT FROM AUTHOR]

A reliable and efficient method was firstly established for the simultaneous determination of saflufenacil and its metabolites (M800H02, M800H11 and M800H35) in cereals (soybean and corn) and fruits (apple, grape and orange), based on a triple quadrupole liquid chromatography mass spectrometer. The four target compounds were extracted with acetonitrile and purified by Florisil or Florisil with octadecylsilane from the cereals and fruits. Determination of the targets was achieved within 3.5 min by using Shim‐pack GIST C18 column connected to an electrospray ionization source (ESI‐ mode). The method showed excellent linearity (R2 > 0.9984), and the limits of quantitation were 1 µg/kg for all compounds. Average recoveries were in the range of 74.6%–108.1%, with an intra‐day relative standard deviation between 0.9% and 18.3%. The inter‐day relative standard deviation was less than 13.8%. The results demonstrate that this method is convenient for monitoring the residues of saflufenacil and its metabolites in food matrices. Practical applications: Saflufenacil controls many common annual broadleaf weed efficiently, it has been developed and launched into the market by domestic enterprises. Consequently, an analysis method for monitoring saflufenacil in food sample will be urgently needed in China over the next few years. This method provides separation with good specificity within 3.5 min, which is less than previous studies. For the five matrixes, the method presented satisfactory validation parameters in terms of good linearity, low limit of quantitations, and satisfactory accuracy and precision. Therefore, the method established in this study is a valuable tool to overcome gaps in determining saflufenacil and its metabolites in cereals and fruits, in order to accurate evaluation of risk and ensure food safety. [ABSTRACT FROM AUTHOR]

An efficient and sensitive analytical method for simultaneous determination of trace amounts of a new insecticide broflanilide and its metabolites (S(PFH‐OH)‐8007 and DM‐8007) residues in five typical Chinese soils (red soil, black soil, fluvo‐aquic soil, cinnamon soil and paddy soil) was developed. The samples were prepared by a modified quick, easy, cheap, effective, rugged, and safe method. The determination of broflanilide and its metabolites was conducted by ultra high performance liquid chromatography with tandem mass spectrometry with an electrospray ionization source in the positive ion mode. This is the first report for the determination of broflanilide and its metabolites in different soils. Broflanilide and its metabolites were extracted from all soils with acetonitrile and purified by a mixture of primary secondary amine and graphitized carbon black. The average recoveries of the three compounds in five types of soil ranged from 85.3 to 111.8% and the relative standard deviations were less than 13.6%. The limit of quantification was 0.1 μg/kg for all three compounds. This method was successfully used to determine broflanilide and its metabolites in five types of soil. The method was validated to be simple and effective for the determination of trace residual broflanilide and its metabolites in five types of soil. [ABSTRACT FROM AUTHOR]

Abstract: The dissipations of afidopyropen and its metabolite in wheat plant and soil were determined using a quick, easy, cheap, effective, rugged, and safe method with ultra‐high performance liquid chromatography and tandem mass spectrometry under a field ecosystem. The limits of quantification were estimated for both target compounds as 0.001 mg/kg. The recoveries of afidopyropen and its metabolite ranged from 94 to 114% (soil), 90 to 109% (wheat seed) and 81 to 91% (wheat straw) at levels of 0.001, 0.01, 0.1, and 2.0 mg/kg with relative standard deviations ≤7%. The results of the residual dynamics experiments showed that afidopyropen dissipated rapidly in wheat plant and soil. Its metabolite initially showed a tendency of rapid increase followed by a decrease in wheat plant but could not be detected in soil. The data showed that the first + first‐order model was more suitable for describing the decline of afidopyropen in wheat and soil. The half‐lives of afidopyropen in wheat plant and soil were 1.65 and 1.21 days, respectively. [ABSTRACT FROM AUTHOR]

Here, we developed a rapid and robust supercritical fluid chromatography–tandem mass spectrometry (SFC-MS/MS) method for simultaneous detection of fenbuconazole and its chiral metabolites in fruit, vegetable, cereal, and soil. Baseline separation of six stereoisomers was achieved on an amylose tris-(3,5-dimethylphenylcarbamate)-coated chiral column in 4.0 min using a mobile phase composed of CO 2 /ethanol (flow rate of 1.8 mL/min). Ionisation efficiency and sensitivity was optimized with a post-column compensation solvent (0.1% formic acid/methanol). Target analytes were extracted with acetonitrile and purified using dispersive solid phase extraction sorbents. Six stereoisomers at three concentrations (5, 50, and 250 µg/kg) achieved satisfactory recoveries (76.3–104.6%) with RSDs ≤ 11.5% Excellent linearities (R 2 ≥ 0.9963) and the limits of quantification (LOQs, 0.13–3.31 μg/kg) were established for all six stereoisomers. Results show that the proposed method is suitable for routine detection of six stereoisomers of fenbuconazole and its chiral metabolites in food and environmental samples. [ABSTRACT FROM AUTHOR]

Persistent use of the diphenyl ether herbicides oxyfluorfen may seriously increase the health risks and ecological safety problems. A newly bacterium R-21 isolated from active soil was able to degrade and utilize oxyfluorfen as the sole carbon source. R-21 was identified as Chryseobacterium aquifrigidense by morphology, physiobiochemical characteristics, and genetic analysis. Under the optimum cultural conditions (pH 6.9, temperature 33.4 °C, and inoculum size 0.2 g L), R-21 could degrade 92.1 % of oxyfluorfen at 50 mg L within 5 days. During oxyfluorfen degradation, six metabolites were detected and identified by atmospheric pressure gas chromatography coupled to quadrupole-time of flight mass spectrometry and ultra-performance liquid chromatography coupled to quadrupole-time of flight mass spectrometry, and a plausible degradation pathway was deduced. Strain R-21 is a promising potential in bioremediation of oxyfluorfen-contaminated environments. [ABSTRACT FROM AUTHOR]

A sensitive and effective method for the simultaneous determination of residues from a new fungicide, oxathiapiprolin, and its metabolites (IN-E8S72 and IN-WR791) in soil, water, and sediment, was developed using ultra high performance liquid chromatography with tandem mass spectrometry. Three compounds were extracted from water, soil, and sediment by using acetonitrile and different proportions of formic acid aqueous solution (1% v/v for water; 2% v/v for soil; and sediment), and were cleaned with octadecylsilane. The target compounds were determined within 5 min using an electrospray ionization source in the positive mode for oxathiapiprolin and in the negative mode for the two metabolites. The limits of quantification for all the three compounds were 0.1 µg/kg in water and 1 µg/kg in soil and sediment. Recovery studies were performed using three spiked levels (0.1, 1, and 10 µg/kg for water; 1, 10, and 50 µg/kg for soil and sediment). The overall average recoveries ranged from 64.8 to 112.7% with all intra- and interday relative standard deviation values below 19.4 and 19.1%, respectively. The method validation confirmed that the proposed method was convenient and reliable for determining residual oxathiapiprolin and its metabolites in soil, water, and sediments. [ABSTRACT FROM AUTHOR]