Bioavailability assessment of difenoconazole to earthworms (Eisenia fetida) in soil by oleic acid-embedded cellulose acetate membrane.

Passive sampling technology is widely used to evaluate the bioavailability of pollutants. However, relatively few studies have used passive sampling membranes (PSMs) to evaluate the environmental risks of pollutants in soil, particularly pesticides. Here, the bioavailability of difenoconazole to earthworms (Eisenia fetida) was evaluated using an oleic acid-embedded cellulose acetate membrane (OECAM) for the first time. Difenoconazole reached 94 % equilibrium (T94%) within 1 d in OECAM. For soil pore water, the freely dissolved concentration (Cfree) of difenoconazole was determined using OECAM (R2 = 0.969). In the soil system, a strong linear correlation between the difenoconazole concentration in OECAM and earthworms was observed (R2 = 0.913). The bioavailability of difenoconazole was affected by the soil type and biochar content. The higher the content of soil organic matter and biochar, the lower the concentration of difenoconazole in earthworms, OECAM, and soil pore water. The concentrations of difenoconazole in pore water, earthworms, and OECAM decreased by 65.3, 42.0, and 41.6 %, respectively, when 0.5 % biochar was added. Difenoconazole mainly enters OECAM and earthworms through passive diffusion with similar uptake pathways. Therefore, the bioavailability of difenoconazole to earthworms in different soils can be evaluated using the OECAM.

Photodegradation of the Novel Herbicide Pyraquinate in Aqueous Solution: Kinetics, Photoproducts, Mechanisms, and Toxicity Assessment.

Pyraquinate, a newly developed 4-hydroxyphenylpyruvate dioxygenase class herbicide, has shown excellent control of resistant weeds in paddy fields. However, its environmental degradation products and corresponding ecotoxicological risks after field application remain ambiguous. In this study, we systematically investigate the photolytic behaviors of pyraquinate in aqueous solutions and in response to xenon lamp irradiation. The degradation follows first-order kinetics, and its rate depends on pH and the amount of organic matter. No vulnerability to light radiation is indicated. Ultrahigh-performance liquid chromatography with quadrupole-time-of-flight mass spectrometry and UNIFI software analysis reveals six photoproducts generated by methyl oxidation, demethylation, oxidative dechlorination, and ester hydrolysis. Gaussian calculation suggests that activities due to hydroxyl radicals or aquatic oxygen atoms caused these reactions on the premise of obeying thermodynamic criteria. Practical toxicity test results show that the toxicity of pyraquinate to zebrafish embryos is low but increases when the compound is combined with its photoproducts.

Abiotic transformation of kresoxim-methyl in aquatic environments: Structure elucidation of transformation products by LC-HRMS and toxicity assessment.

In this study, abiotic transformation of an important strobilurin fungicide, kresoxim-methyl, was investigated under controlled laboratory conditions for the first time by studying its kinetics of hydrolysis and photolysis, degradation pathways and toxicity of possibly formed transformation products (TPs). The results indicated that kresoxim-methyl showed a fast degradation in pH9 solutions with DT50 of 0.5 d but relatively stable under neutral or acidic environments in the dark. It was prone to photochemical reactions under simulated sunlight, and the photolysis behavior was easily affected by different natural substances such as humic acid (HA), Fe3+and NO3-which are ubiquitous in natural water, showing the complexity of degradation mechanisms and pathways of this chemical compound. The potential multiple photo-transformation pathways via photoisomerization, hydrolyzation of methyl ester, hydroxylation, cleavage of oxime ether and cleavage of benzyl ether were observed. 18 TPs generated from these transformations were structurally elucidated based on an integrated workflow combining suspect and nontarget screening by high resolution mass spectrum (HRMS), and two of them were confirmed with reference standards. Most of TPs, as far as we know, have never been described before. The in-silico toxicity assessment showed that some of TPs were still toxic or very toxic to aquatic organisms, although they exhibit lower aquatic toxicity compared to the parent compound. Therefore, the potential hazards of the TPs of kresoxim-methyl merits further evaluation.

Occurrence and risk assessment of three chloroamide herbicides in water and soil environment in northeastern, eastern and southern China.

Chloroamide herbicides can cause adverse effects on nontarget organisms, but there is limited information about their occurrence in the environment of major cropland growing regions. In this study, a total of 1012 soil samples, 617 surface water samples and 737 groundwater samples were collected from 2020 to 2021 in three regions of China to evaluate the occurrence and risk of three important chloroamide herbicides alachlor, acetochlor and butachlor using the improved QuEChERS extraction method and high performance liquid chromatography-mass spectrometry. The results showed that residues of the three chloroamide compounds in surface water and groundwater ranged from 0.1 to 176.0 µg L-1, of which acetochlor was frequently detected from surface water (17.5%). As for the soil, mass fraction was varied between 1.0 and 1540.3 µg kg-1, similarly acetochlor had the highest detection frequency (49.6%). Timewise, the median mass fraction of selected chloroamide herbicides in soil in 2021 (7.8 µg kg-1) was significantly lower than that in 2020 (10.9 µg kg-1). Spatially, there were regional differences in the content of environmental residues, and the overall level of residues in the northeast was relatively high. The environmental risk assessment based on the improved Risk Quotient (RQ) method indicated that the selected herbicides were currently within an acceptable range for human health risks in the soil and water environment in various regions, but acetochlor and butachlor had contributed to the RQ values of fish and earthworms (0.01＜RQ＜0.1) in recent years, respectively, which might pose a certain risk of oral exposure to aquatic and terrestrial organisms. This study provides valuable data and ideas for the rational application, pollution control and environmental safety evaluation of chloroamide herbicides in China.

Assessment of the Therapeutic Potential of Melatonin for the Treatment of Osteoporosis Through a Narrative Review of Its Signaling and Preclinical and Clinical Studies.

Melatonin is a bioamine produced primarily in the pineal gland, although peripheral sites, including the gut, may also be its minor source. Melatonin regulates various functions, including circadian rhythm, reproduction, temperature regulation, immune system, cardiovascular system, energy metabolism, and bone metabolism. Studies on cultured bone cells, preclinical disease models of bone loss, and clinical trials suggest favorable modulation of bone metabolism by melatonin. This narrative review gives a comprehensive account of the current understanding of melatonin at the cell/molecular to the systems levels. Melatonin predominantly acts through its cognate receptors, of which melatonin receptor 2 (MT2R) is expressed in mesenchymal stem cells (MSCs), osteoblasts (bone-forming), and osteoclasts (bone-resorbing). Melatonin favors the osteoblastic fate of MSCs, stimulates osteoblast survival and differentiation, and inhibits osteoclastogenic differentiation of hematopoietic stem cells. Produced from osteoblastic cells, osteoprotegerin (OPG) and receptor activator of nuclear factor kappa B ligand (RANKL) critically regulate osteoclastogenesis and melatonin by suppressing the osteoclastogenic RANKL, and upregulating the anti-osteoclastogenic OPG exerts a strong anti-resorptive effect. Although the anti-inflammatory role of melatonin favors osteogenic function and antagonizes the osteoclastogenic function with the participation of SIRT signaling, various miRNAs also mediate the effects of the hormone on bone cells. In rodent models of osteoporosis, melatonin has been unequivocally shown to have an anti-osteoporotic effect. Several clinical trials indicate the bone mass conserving effect of melatonin in aging/postmenopausal osteoporosis. This review aims to determine the possibility of melatonin as a novel class of anti-osteoporosis therapy through the critical assessment of the available literature.

Degradation of difenoconazole in water and soil: Kinetics, degradation pathways, transformation products identification and ecotoxicity assessment.

Difenoconazole is a widely used triazole fungicide that has been frequently detected in the environment, but comprehensive study about its environmental fate and toxicity of potential transformation products (TPs) is still lacking. Here, laboratory experiments were conducted to investigate the degradation kinetics, pathways, and toxicity of transformation products of difenoconazole. 12, 4 and 4 TPs generated by photolysis, hydrolysis and soil degradation were identified via UHPLC-QTOF/MS and the UNIFI software. Four intermediates TP295, TP295A, TP354A and TP387A reported for the first time were confirmed by purchase or synthesis of their standards, and they were further quantified using UHPLC-MS/MS in all tested samples. The main transformation reactions observed for difenoconazole were oxidation, dechlorination and hydroxylation in the environment. ECOSAR prediction and laboratory tests showed that the acute toxicities of four novel TPs on Brachydanio rerio, Daphnia magna and Selenastrum capricornutum are substantially lower than that of difenoconazole, while all the TPs except for TP277C were predicted chronically very toxic to fish, which may pose a potential threat to aquatic ecosystems. The results are important for elucidating the environmental fate of difenoconazole and assessing the environmental risks, and further provide guidance for scientific and reasonable use.

Cumulative risk assessment of dietary exposure to triazole fungicides from 13 daily-consumed foods in China.

The agroeconomic benefits of the routine use of triazole fungicides on crops have been evident for more than 40 years. However, increasing evidence shows that residues of triazoles are ubiquitous in various foods and thus could pose a potential health risk to humans. We analyzed 3406 samples of 13 food commodities that were collected from markets in 9 regions across China, and assessed the health risk of both chronic and acute exposure to the triazoles for Chinese children (1-6 years old) and the general population. Among all samples, 55.52% had triazoles in concentrations of 0.10-803.30 µg/kg, and 29.77% of samples contained a combination of 2-7 triazoles. Tebuconazole and difenoconazole were the most commonly found triazoles in the foods, being detected in 33.44% and 30.45% of samples, respectively. Chronic and acute cumulative risk assessment for total triazoles based on a relative potency factor method revealed that exposure to triazoles from these particular commodities was below the levels that might pose a health risk (chronic hazard index range, 5.90×10-7 to 1.83×10-3; acute hazard index range, 7.77×10-5 to 0.39, below 1). Notably, dietary exposure risk for children was greater than that for the general population-particularly for the acute intake of mandarin, grape, and cucumber (acute hazard index values of 0.35-0.39). Despite the low health risk, the potential hazards of exposure to triazoles should raise public concern owing to their ubiquitous presence in common foods and potential cumulative effects.

Risk assessment for pesticide mixtures on aquatic ecosystems in China: a proposed framework.

BACKGROUND: With over 12 000 registered mixture formulations in China, environmental risk assessment of co-formulated pesticide mixtures to aquatic ecosystems is of increasing interest to scientists, risk assessors, and risk managers. This study proposed a pragmatic approach based on widely accepted scientific concepts and strategies. RESULTS: The proposed approach has three tiers, a preliminary Tier 0 stage, a Tier 1 stage, and a refinement stage as Tier 2, which are demonstrated with one case study. Because of the large number of co-formulated pesticide mixtures available in China, a unique Tier 0 stage is proposed with practicable criteria to identify mixtures requiring further evaluation. For Tier-1 assessment, exposure is assessed based on the application scheme and local scenarios in China. Hazard is evaluated using the concentration addition model as the default approach, which was developed a century ago and was adopted by the majority of the regulators globally. Given the unique characteristics of mixtures in the environment, data variability and ratio changes of active ingredients are also evaluated for hazard assessment. More accurate assessments with decreased uncertainties can be achieved by higher tier refinements in Tier-2, such as alternative models, consideration of co-formulants, and higher tier effect and exposure analyses. CONCLUSION: Widely accepted concepts, methodologies, and criteria should be used for aquatic risk assessment for pesticide mixtures in China. To avoid unnecessary workload and a more accurate assessment, unique perspectives such as local agricultural practice, local scenarios and a preliminary screening stage (Tier 0) should be implemented. © 2019 Society of Chemical Industry.

Impacts of six potential HONO sources on HOx budgets and SOA formation during a wintertime heavy haze period in the North China Plain.

The Weather Research and Forecasting/Chemistry (WRF-Chem) model updated with six potential HONO sources (i.e., traffic, soil, biomass burning and indoor emissions, and heterogeneous reactions on aerosol and ground surfaces) was used to quantify the impact of the six potential HONO sources on the production and loss rates of OH and HO2 radicals and the concentrations of secondary organic aerosol (SOA) in the Beijing-Tianjin-Heibei (BTH) region of China during a winter heavy haze period of Nov. 29-Dec. 3, 2017. The updated WRF-Chem model well simulated the observed HONO concentrations at the Wangdu site, especially in the daytime, and well reproduced the observed diurnal variations of regional-mean O3 in the BTH region. The traffic emission source was an important HONO source during nighttime but not significant during daytime, heterogeneous reactions on ground/aerosol surfaces were important during nighttime and daytime. We found that the six potential HONO sources led to a significant enhancement in the dominant production and loss rates of HOx on the wintertime heavy haze and nonhaze days (particularly on the heavy haze day), an enhancement of 5-25 µg m-3 (75-200%) in the ground SOA in the studied heavy haze event, and an enhancement of 2-15 µg m-3 in the meridional-mean SOA on the heavy haze day, demonstrating that the six potential HONO sources accelerate the HOx cycles and aggravate haze events. HONO was the key precursor of primary OH in the BTH region in the studied wintertime period, and the photolysis of HONO produced a daytime mean OH production rate of 2.59 ppb h-1 on the heavy haze day, much higher than that of 0.58 ppb h-1 on the nonhaze day. Anthropogenic SOA dominated in the BTH region in the studied wintertime period, and its main precursors were xylenes (42%), BIGENE (31%) and toluene (21%).

Carboxin and its major metabolites residues in peanuts: Levels, dietary intake and chronic intake risk assessment.

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.

Human health safety studies of a new insecticide: Dissipation kinetics and dietary risk assessment of afidopyropen and one of its metabolites in cucumber and nectarine.

To preliminarily study the law of natural dissipation and the relation to human health of a new insecticide (afidopyropen), the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method and a UHPLC-MS/MS system were used to extract and detect the afidopyropen and its metabolite (M440I007) from cucumber and nectarine. The limits of quantitation (LOQs) of both target compounds in two matrixes were reduced to 0.0001 mg/kg. Dissipative dynamics experiments indicated that afidopyropen residue dissipation is more consistent with a two-compartment kinetic model than a first-order kinetic model whether in cucumber or nectarine. The half-lives were less than 1.1 and 2.0 days in the distribution phase and up to 9.9 and 27.7 days in the elimination phase in cucumber and nectarine, respectively. The correlation coefficients were 0.9620, 0.9391, and 0.9923 for cucumber and 0.9676 and 0.9985 for nectarine from different locations. M440I007 initially increased rapidly, reached a maximum at 2 days, and then decreased gradually over time. Finally, dietary risk assessment indicated that the mixed residues of afidopyropen and M440I007 at the recommended dosage would not cause health concerns in population.

Bioavailability assessment of thiacloprid in soil as affected by biochar.

Biochars can significantly sorb pesticides, and reduce their bioavailability in agricultural soils. In this study, the effects of a type of biochar (BC500) on the sorption, degradation, bioaccumulation and bioavailability of thiacloprid, which is a commonly used insecticide, were investigated. The thiacloprid sorption constant (Kf values) increased by 14 times after 2% BC500 application, and the degradation of the insecticide decreased with increasing amounts of the biochars in the soil. Coupled with the exhaustive extraction and single-point Tenax method, the bioavailability of thiacloprid was predicted in the presence of the biochar. In soils amended with BC500, the thiacloprid concentrations accumulated in Tenax correlated well with those observed in earthworms (R2 = 0.887), whereas the concentrations extracted by exhaustive method followed a less significant relationship with those in earthworms (R2 = 0.624). The results of Tenax extractions and earthworm bioassays indicate that biochar reduces the bioavailability of thiacloprid in soil, but the delayed degradation and increased earthworm accumulation in aged biochar-amended soil imply that the environmental risks of biochar application to earthworms remain.

A statistical approach to determine fluxapyroxad and its three metabolites in soils, sediment and sludge based on a combination of chemometric tools and a modified quick, easy, cheap, effective, rugged and safe method.

An effective method for the quantification of fluxapyroxad and its three metabolites in soils, sediment and sludge was developed using ultrahigh performance chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). Both the extraction and clean-up steps of the QuEChERS procedure were optimised using a chemometric tool, which was expected to facilitate the rapid analysis with minimal procedures. Several operating parameters (MeCN/acetic acid ratio in the extraction solution (i.e., acetic acid percentage), water volume, extraction time, PSA amount, C18 amount, and GCB amount) were investigated using a Plackett-Burman (P-B) screening design. Afterward, the significant factors (acetic acid percentage, water volume, and PSA amount) obtained were optimised using central composite design (CCD) combined with the desirability function (DF) to determine the optimum experimental conditions. The optimised procedure provides high-level linearity for all studied compounds with correlation coefficients ranging between 0.9972 and 0.9999. The detection limits were in the range of 0.1 to 1.0µg/kg and the limits of quantitation (LOQs) were between 0.5 and 3.4µg/kg with relative standard deviations (RSD) between 2.3% and 9.6% (n=6). Therefore, the developed protocol can serve as a simple and sensitive tool for monitoring fluxapyroxad and its three metabolites in soil, sediment and sludge samples.

A quick, easy, cheap, effective, rugged, and safe method for the simultaneous detection of four triazolone herbicides in cereals combined with ultrahigh performance liquid chromatography with tandem mass spectrometry.

This paper describes a novel, rapid, and sensitive analytical method for monitoring four triazolone herbicides in cereals (wheat, rice, corn, and soybean), using a quick, easy, cheap, effective, rugged, and safe sample extraction procedure followed by ultrahigh performance liquid chromatography coupled with tandem mass spectrometry. The four triazolone herbicides (amicarbazone, carfentrazone-ethyl, sulfentrazone, and thiencarbazone-methyl) were extracted using acidified acetonitrile (containing 1% v/v formic acid) and subsequently purified with octadecylsilane (C18 ) prior to sample analysis. Ultrahigh performance liquid chromatography coupled with tandem mass spectrometry was operated in positive and negative ionization switching mode. Amicarbazone and carfentrazone-ethyl were detected in the positive mode (ESI+), while sulfentrazone and thiencarbazone-methyl were detected in the negative mode (ESI-). All compounds were successfully separated in less than 3.0 min. Further optimization achieved desired recoveries ranging from 74.5 to 102.1% for all analytes with relative standard deviation values ≤17.2% in all tested matrices at three levels (10, 100, and 500 µg/kg). The limits of detection for all compounds were ≤2.3 µg/kg, and the limits of quantitation did not exceed 7.1 µg/kg. The developed method showed excellent linearity (R(2) ≥ 0.994) and was proven to be highly efficient and reliable for the routine monitoring of triazolone herbicides in cereals.

Simultaneous determination of trifloxystrobin and trifloxystrobin acid residue in rice and soil by a modified quick, easy, cheap, effective, rugged, and safe method using ultra high performance liquid chromatography with tandem mass spectrometry.

A sensitive analytical method for the simultaneous determination of trifloxystrobin and its metabolite trifloxystrobin acid in rice including straw, bran, brown rice and soil was developed by using ultra high performance liquid chromatography coupled with tandem mass spectrometry. The fungicide trifloxystrobin and its metabolite trifloxystrobin acid were extracted using acetonitrile with 1% formic acid v/v and subsequently cleaned up by primary secondary amine, octadecylsilane or graphitized carbon black prior to ultra high performance liquid chromatography coupled with tandem mass spectrometry. The determination of two target compounds was achieved in less than 3 min using an electrospray ionization source in positive mode. The limits of detection were below 0.22 µg/kg and the limits of quantification did not exceed 0.74 µg/kg in all matrices, which were much lower than the maximum residue levels established by the Codex Alimentarius Commission. The overall average recoveries in four matrix at three levels (0.1, 1.0 and 5.0 mg/kg) ranged from 74.2 to 107.4% with a relative standard deviations of less than 7.8% (n = 5) for both analytes. The method was demonstrated to be convenient and reliable for the routine monitoring of trifloxystrobin and its metabolite. The developed method was validated and applied for the analysis of degradation study samples.

Simultaneous determination of oxathiapiprolin and two metabolites in fruits, vegetables and cereal using a modified quick, easy, cheap, effective, rugged, and safe method and liquid chromatography coupled to tandem mass spectrometry.

An effective and rapid analytical method for the simultaneous determination of a new fungicide oxathiapiprolin and its metabolites (IN-E8S72 and IN-WR791) residues in fruits (grape, watermelon, watermelon peel), vegetables (cucumber, tomato, potato) and cereal (wheat) was developed by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) using the modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction concept. Three target compounds were extracted from all matrices with 1% (V/V) formic acid aqueous solution and acetonitrile then cleaned by dispersive solid phase extraction (dSPE) with octadecylsilane (C18) and graphitized carbon black (GCB). The determination of the target compounds was achieved within a 5.1min run time by using an UPLC HSS T3 column connected to an electrospray ionization source (ESI, positive ion mode) for oxathiapiprolin and the negative mode for the two metabolites. The method showed excellent linearity (R(2)>0.9904) for target compounds. The limit of detection (LOD) for the three compounds ranged from 0.5µgkg(-1) to 7.5µgkg(-1) and the limits of quantitation (LOQ) were 1µgkg(-1) and 10µgkg(-1) for oxathiapiprolin and the metabolites, respectively. The mean recoveries from seven matrices ranged from 81.5 to 110.7%, with intra-day relative standard deviations (RSDr) in the range of 0.8-12.0% for all three test compounds. The inter-day RSDR were less than 14.5% for all of the recovery tests. The method was successfully applied for simultaneous analysis of oxathiapiprolin and its metabolites in actual trial samples, indicating its effectiveness in investigating oxathiapiprolin and its metabolites in the food.

Determination of cyflumetofen residue in water, soil, and fruits by modified quick, easy, cheap, effective, rugged, and safe method coupled to gas chromatography/tandem mass spectrometry.

A new, highly sensitive, and selective method was developed for the determination of the cyflumetofen residue in water, soil, and fruits by using gas chromatography quadruple mass spectrometry. The target compound was extracted using acetonitrile and then cleaned up using dispersive solid-phase extraction with primary and secondary amine and graphitized carbon black, and optionally by a freezing-out cleanup step. The matrix-matched standards gave satisfactory recoveries and relative standard deviation values in different matrices at three fortified levels (0.05, 0.5, and 1.0 mg kg(-1) ). The overall average recoveries for this method in water, soil, and all fruits matrix at three fortified levels ranged from 76.3 to 101.5% with relative standard deviations in the range of 1.2-11.8% (n = 5). The calculated limits of detection and quantification were typically below 0.005 and 0.015 µg kg(-1), which were much lower than the maximum residue levels established by Japanese Positive List. This study provides a theoretical basis for China to draw up maximum residue level and analytical method for cyflumetofen acaricide in different fruits.

Determination of nonylphenol ethoxylate metabolites in vegetables and crops by high performance liquid chromatography-tandem mass spectrometry.

A method has been developed for the simultaneous determination of the concentration of nonylphenol (4-NP), nonylphenol monoethoxylates (NP1EO) and nonylphenol diethoxylates (NP2EO) in vegetables and crops by liquid chromatography-tandem quadrupole mass spectrometry (HPLC-MS/MS). These target compounds were extracted from vegetable and crop samples with acetonitrile, and then the extracts were cleaned using solid phase extraction with graphitised carbon black tandem primary secondary amine (PSA) cartridges. The MS method enabled highly reliable identification by monitoring the corresponding ammonium adduct [M+NH4](+) in the positive mode for NP1EO and NP2EO, and the deprotonated molecule [M-H](-) in the negative mode for 4-NP. Recoveries for the spiked samples ranged from 65% to 118%. The limit of detection (LOD) of 4-NP, NP1EO and NP2EO was 3, 5 and 0.1µgkg(-1), respectively. This method would be useful for the quick and routine detection of the residues of 4-NP, NP1EO and NP2EO in vegetables and crops.

Residue analysis of four diacylhydrazine insecticides in fruits and vegetables by Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method using ultra-performance liquid chromatography coupled to tandem mass spectrometry.

The new analytical method using Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) procedure for simultaneous determination of diacylhydrazine insecticide residues in fruits and vegetables was developed using ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The four insecticides (tebufenozide, methoxfenozide, chromafenozide, and halofenozide) were extracted from six fruit and vegetable matrices using acetonitrile and subsequently cleaned up using primary secondary amine (PSA) or octadecylsilane (C18) as sorbent prior to UPLC-MS/MS analysis. The determination of the target compounds was achieved in less than 3.0 min using an electrospray ionization source in positive mode (ESI+) for tebufenozide, methoxfenozide, and halofenozide and in negative mode (ESI-) for chromafenozide. The limits of detection were below 0.6 µg kg(-1), while the limit of quantification did not exceed 2 µg kg(-1) in different matrices. The QuEChERS procedure by using two sorbents (PSA and C18) and the matrix-matched standards gave satisfactory recoveries and relative standard deviation (RSD) values in different matrices at four spiked levels (0.01, 0.05, 0.1, and 1 mg kg(-1)). The overall average recoveries for this method in apple, grape, cucumber, tomato, cabbage, and spinach at four levels ranged from 74.2% to 112.5% with RSDs in the range of 1.4-13.8% (n = 5) for all analytes. This study provides a theoretical basis for China to draw up maximum residue limits and analytical method for diacylhydrazine insecticide in vegetables and fruits.