Guojun Yao

Effervescence assisted dispersive liquid-liquid microextraction based on cohesive floating organic drop for the determination of herbicides and fungicides in water and grape juice

A novel effervescence assisted dispersive liquid-liquid microextraction method based on cohesive floating organic drop has been developed for simultaneous determination of triazine herbicides and triazole fungicides in aqueous samples followed by ultra-high pressure liquid chromatography tandem a triple quadrupole mass spectrometer. In this method, 1-undecanol as extractant was well dispersed by effervescence. In order to obtain relatively high extraction efficiency, the effects of salt, volume of effervescence mixture, volume of extraction solvent and temperature were investigated. Under the optimum conditions, the proposed method showed good linearity within the range of 0.05-10μgL-1 with correlation coefficients of 0.9987-0.9999. The recoveries of analytes were in the range of 72.4-101.5% with relative standard deviations ranging from 2.6% to 11.7%. The limits of detection were varied from 2.7 to 9.7ngL-1. This method has been successfully used to simultaneously analyze triazine herbicides and triazole fungicides in surface waters and grape juice.

Approach for Pesticide Residue Analysis for Metabolite Prothioconazole-desthio in Animal Origin Food

Food safety problems such as damage to immune, nervous, and endocrine systems leading to cancer and malformations have received increasing attention. To achieve the maximum residue limits, the most discussed method of high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) is widely used with a advantage of high precision and resolution. Prothioconazole is a broad-spectrum thiocarbamate fungicide. It can rapidly metabolize to prothioconazole-desthio in different matrixes. Rapid and effective methods for the determination of prothioconazole-desthio in five kinds of different animal food were developed. Samples were extracted with acetonitrile or acetonitrile/water and determined by HPLC-MS/MS. The limit of detection and limit of quantification values of prothioconazole-desthio were 0.015 and 0.05 mg/kg for porcine liver and kidney, 0.0015 and 0.005 mg/kg for pork, and 0.003 and 0.01 mg/kg for eggs, together with 0.0012 and 0.004 mg/kg for milk of the detected method, respectively. A good linear regression trend can be observed in a certain concentration range for all of the animal food. At fortified levels, recoveries were between 83.6 and 105%, with relative standard deviations of 1.5-10.3%. A sample survey of 150 samples with 30 samples for each kind of animal food across the country was conducted and found that there was no prothioconazole-desthio detected in all samples.

Environmental Fate of Chiral Herbicide Fenoxaprop-ethyl in Water-Sediment Microcosms

The environmental fate of the herbicide fenoxaprop-ethyl (FE) in water, sediment and water-sediment microcosm was studied and degradation products fenoxaprop (FA), ethyl-2-(4-hydroxyphenoxy)propanoate (EHPP), 2-(4-hydroxyphenoxy)propanoic acid (HPPA) and 6-chloro-2,3-dihydrobenzoxazol-2-one (CDHB) were monitored. FE, FA, EHPP and HPPA were chiral and the environmental behavior was investigated on an enantiomeric level. In water, sediment and water-sediment microcosms, fenoxaprop-ethyl degraded very fast with half-lives less than 1 day and it was found the herbicidally inactive S-enantiomer degraded faster. Fenoxaprop was the main primary degradation product which was quickly formed and the further degradation was relatively slow with half-lives of 6.4–12.4 days, and the S-enantiomer degraded faster too. EHPP, HPPA and CDHB could be found and S-EHPP and S-HPPA were degraded preferentially. The effects of microorganism and water content were investigated and it was found that the enantioselectivity was attributed to microorganisms. In sediment, the main degradation pathway of fenoxaprop-ethyl was hydrolysis and the degradation rate of fenoxaprop-ethyl increased with water content. The degradation products and enantioselectivity should be considered for the impact of fenoxaprop-ethyl on the aquatic system.

Effects of wastewater irrigation and sewage sludge application on soil residues of chiral fungicide benalaxyl

The effects of wastewater irrigation and sewage sludge on the dissipation behavior of the fungicide benalaxyl and its primary metabolite benalaxyl acid in soil were studied on an enantiomeric level during a 148-day exposure experiment. Chiral separation and analysis of the two pairs of enantiomers were achieved using HPLC-MS/MS with a chiralpak IC chiral column. Benalaxyl decreased with half-life of 16.1 days in soil under tap water irrigation with preferential residue of S-benalaxyl. Benalaxyl acid was formed with great preference of R-enantiomer before 21 days while enriched in S-enantiomer afterwards. The degradation of benalaxyl was restrained by both wastewater and treated wastewater irrigation, but the enantioselectivity in S-benalaxyl residue was enhanced. Benalaxyl acid was also formed with similar enantioselectivity as in tap water irrigation. Sewage sludge could accelerate benalaxyl degradation with shorter half-life. Surprisingly, the enantioselectivity with preference degradation of S-enantiomer in sewage sludge was opposite to that in soil. More benalaxyl acid was generated with EF values always lower than 0.5 and remained longer in sewage sludge than in soil. A sterilization experiment indicated that the conversion of benalaxyl to benalaxyl acid and the enantioselectivity were determined by the microorganisms in soil or sewage sludge. Farming practices like wastewater irrigation and sewage sludge application might not only influence the fate of pesticide, but also the enantioselectivity of chiral pesticide enantiomers and thus the risks of pesticide residues posed to the environment.

Minimizing geometric isomerization of α-cypermethrin in the residue analysis.

Isomerization of chiral pesticides in residue analysis has not drawn much attention which can cause wrong decisions on the enantioselective environmental behavior. A residue analysis method for α-cypermethrin and its three acid metabolites, cis/trans-3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropanecarboxylic acid (cis/trans-DCVA) and 3-phenoxybenzoic acid (3-PBA), in foods such as chicken, honey, milk and pork has been established, in which the isomerization of α-cypermethrin was minimized. The target compounds were determined by GC-ECD after a derivatization reaction with 1,1,1,3,3,3-hexafluoroisopropanol. The conditions of the method were optimized by Taguchi orthogonal experiment. Under the optimized conditions, good linearity was obtained with correlation coefficients ranging from 0.9964 to 0.9998. The limits of detection were 0.001-0.005 mg kg(-1). The recoveries were 70.9-114.9% with relative standard deviations of 0.6-15%. In addition, ratios of isomerization ranged only from 2.3% to 7.0%. This method was applied in commercial animal food products.

Enantioselective Characteristics and Montmorillonite-Mediated Removal Effects of α-Hexachlorocyclohexane in Laying Hens

α-Hexachlorocyclohexane (α-HCH) is a chiral organochlorine pesticide that is often ubiquitously detected in various environmental matrices and may be absorbed by the human body via food consumption, with serious detriments to human health. In this study, enantioselective degradation kinetics and residues of α-HCH in laying hens were investigated after a single dose of exposure to the pesticide, whereas enantioselectivity and residues of α-HCH in eggs, droppings, and various tissues were investigated after long-term exposure. Meanwhile, montmorillonite (MMT), a feed additive with high capacity of adsorption, was investigated for its ability to remove α-HCH from laying hens. Most non-brain tissues enantioselectively accumulated (-)-α-HCH, while (+)-α-HCH was preferentially accumulated in the brain. The enantiomer fractions (EFs) in most tissues gradually decreased, implying continuous depletion of (+)-α-HCH in laying hens. After 30 days of exposure and 31 days of elimination, the concentration of α-HCH in eggs and tissues of laying hens with MMT-containing feed was lower than that with MMT-free feed, indicating the removal effects of MMT for α-HCH in laying hens. The findings presented herein suggest that modified MMT may potentially be useful in reducing the enrichment of α-HCH in laying hens and eggs, thus lowering the risk of human intake of α-HCH.

Enantioselective Degradation and Chiral Stability of Metalaxyl-M in Tomato Fruits.

Metalaxyl is an important chiral acetanilide fungicide, and the activity almost entirely originates from the R-enantiomer. Racemic metalaxyl has been gradually replaced by the enantiopure R-enantiomer (metalaxyl-M). In this study a chiral residue analysis method for metalaxyl and the metabolite metalaxyl acid was set up based on high-performance liquid chromatography tandem mass spectroscopy (HPLC-MS/MS). The enantioselective degradation and chiral stability of metalaxyl-M in tomato fruits in two geographically distinct regions of China (Heilongjiang and Hunan Province) were evaluated and the enantioselectivity of metalaxyl acid was also investigated. Tomato plants grew under field conditions with a one-time spray application of metalaxyl-M wettable powder. It was found that R-metalaxyl was not chirally stable and the inactive S-metalaxyl was detected in tomato fruits. At day 40, S-metalaxyl derived from R-metalaxyl accounted for 32% and 26% of the total amount of metalaxyl, respectively. The metabolites R-metalaxyl acid and S-metalaxyl acid were both observed in tomato, and the ratio of S-metalaxyl acid to the sum of S- and R-metalaxyl acid was 36% and 28% at day 40, respectively. For both metalaxyl and metalaxyl acid, the half-life of the S-enantiomer was longer than the R-enantiomer. The results indicated that the enantiomeric conversion should be considered in the bioactivity evaluation and environmental pollution assessment. Chirality 28:382-386, 2016.

The enantioselective metabolic mechanism of quizalofop-ethyl and quizalofop-acid enantiomers in animal: protein binding, intestinal absorption, and in vitro metabolism in plasma and the microsome

To investigate the metabolic mechanism and enantioselectivity of the chiral herbicide quizalofop-ethyl and its primary chiral metabolite quizalofop-acid in animals by oral administration, the effects of the processes involved in digestion, absorption, transportation and metabolism, such as protein binding (pepsin, trypsin and serum albumin), intestinal absorption (everted gut sac), and degradation (plasma, liver microsome and cytosol) were studied in vitro. Protein binding experiments showed that quizalofop-ethyl interacted with pepsin, trypsin and serum albumin without enantioselectivity and the proteins did not stimulate metabolic processes that would produce quizalofop-acid. In the everted gut sac, quizalofop-ethyl was degraded rapidly to quizalofop-acid without enantioselectivity and the preferential absorption of (+)-quizalofop-acid was observed throughout the gut. In plasma, the metabolic process of quizalofop-ethyl was enantioselective with preferential degradation of (+)-quizalofop-ethyl and generation of (+)-quizalofop-acid. However there was no enantioselectivity in the degradation of quizalofop-ethyl or formation of quizalofop-acid in liver microsome. The metabolism of quizalofop-acid was nonenantioselective by liver microsome, sulfotransferase and glucuronosyltransferase. It could be inferred that the enzymes present in the lumen of intestine, blood and liver might facilitate the rapid transformation of quizalofop-ethyl to quizalofop-acid after oral administration, and the enantioselective absorption of quizalofop-acid enantiomers by intestine was the main reason for the enantioselectivity observed in rats in vivo.