Yanjie Li

The comparison of dispersive solid phase extraction and multi-plug filtration cleanup method based on multi-walled carbon nanotubes for pesticides multi-residue analysis by liquid chromatography tandem mass spectrometry

In this study, dispersive-Solid Phase Extraction (d-SPE) cleanup and multi-plug filtration cleanup (m-PFC) methods were compared for 25 representative pesticides in six matrices (wheat, spinach, carrot, apple, citrus and peanut) by QuEChERS-LC-ESI-MS/MS detection. The type of sorbents in dispersive-SPE (d-SPE) was optimized for the above matrices. Multi-walled carbon nanotubes (MWCNTs), which mixed other materials like PSA (Primary Secondary Amines), GCB (Graphitized Carbon Black) and C18 (Octadecyl-silica), showed brilliant cleanup performance in multi residue monitoring (MRM) pesticide residue analysis. Cleanup effects with d-SPE and m-PFC methods were examined. When spiked at 3 concentration levels of 10, 100, 500 μg/kg in above matrices, for both d-SPE and m-PFC methods, the recoveries ranged from 70 to 110% with relative standard deviations (RSDs) lower than 20%. Limits of quantification (LOQs) for both cleanup methods ranged from 1 to 25 μg/kg. Matrix-matched calibrations were performed with the coefficients of determination more than 0.99 between concentration levels of 10-1000 μg/kg. It was found that m-PFC was more convenient and effective than d-SPE with the same sorbents, due to the increased contact time and contact area between the extracts and compressed sorbents. The study demonstrated that m-PFC method could be used as a rapid, convenient and high-throughput cleanup method for analysis of pesticide residues.

Determination of Six Neonicotinoid Insecticides Residues in Spinach, Cucumber, Apple and Pomelo by QuEChERS Method and LC–MS/MS

A modified QuEChERS and LC–MS/MS method has been developed for the simultaneous determination of residues of six neonicotinoids in various crops, including spinach, cucumber, apple and pomelo. The method showed good linearity (R2xa0≥xa00.9995) and precision (RSDxa0≤xa014.0%). Average recoveries of the six neonicotinoids ranged between 73.7% and 103.8% at spiking levels 0.005, 0.1 and 1xa0mgxa0kg−1. The LODs and LOQs were in the ranges of 0.20–0.85xa0μgxa0kg−1 and 0.66–2.84xa0μgxa0kg−1, respectively. The method was satisfactorily validated for the analysis of 50 agricultural samples. Imidacloprid and imidaclothiz were detected at concentration levels ranging from 7 to 5.3xa0μgxa0kg−1.

Direct analysis in real time mass spectrometry for the rapid identification of four highly hazardous pesticides in agrochemicals

RATIONALEnDirect analysis in real time (DART) is a new ion source technique, which is conducted in the open air under ambient conditions, applied to the rapid and direct analysis of any material (gases, liquids, and solids) with minimal or no sample preparation. In order to take advantage of the capacity of DART mass spectrometry for the real-time analysis of hazardous ingredients in commercial agrochemicals, a pilot study of rapid qualitative determination of hazardous pesticides was performed.nnnMETHODSnHighly hazardous pesticides were identified by DART ionization coupled to a single-quadrupole mass spectrometer (DART-MS). Acetonitrile was chosen for dissolving samples prior to the analysis. Samples were analyzed by this technique in as little as 5 s.nnnRESULTSnPhorate, carbofuran, ethoprophos and fipronil were be detected directly from commercial agrochemicals. The ionization-related parameters (DART temperature, grid voltage and MS fragment) of these compounds were optimized to obtain highly response. Isotope patterns were taken into consideration for qualitative identification. Relative standard deviations (RSDs, nu2009=u20095) of 2.3-15.0% were obtained by measuring the relative abundance of selected isotopes.nnnCONCLUSIONSnThis study showed that DART-MS technology was able to qualitatively determine the existence of highly hazardous pesticides in commercial pesticide formulations. It is suggested that this technology should be applied for routine monitoring in the market.

Dissipation and residue behavior of emamectin benzoate on apple and cabbage field application

A LC-ESI-MS/MS method with QuEChERS for analysis of emamectin benzoate in cabbage, apple and soil was established. At fortification levels of 0.001, 0.01 and 0.1 mg/kg in cabbage, apple and soil, it was shown that recoveries ranged from 75.9 to 97.0 percent with relative standard deviation (RSD) of 4.4-19.0 percent. The limit of quantification (LOQ) was 0.001 mg/kg for cabbage, apple and soil. The dissipation half-lives of emamectin benzoate in cabbage, apple and soil were 1.34-1.72 day, 2.75-3.09 day and 1.89-4.89 day, respectively. The final residues of emamectin benzoate ranged from 0.001 to 0.052 mg/kg in cabbages, 0.003 to 0.090 mg/kg in apples and 0.001 to 0.089 mg/kg in soils, respectively. Therefore, it would be unlikely to cause health problems if emamectin benzoate was applied according to the use pattern suggested by the manufactures on the label.

Residue determination of glufosinate in plant origin foods using modified Quick Polar Pesticides (QuPPe) method and liquid chromatography coupled with tandem mass spectrometry

A sensitive and specific method for the determination of glufosinate in plant origin foods was developed. The method involves extraction using modified QuPPe method, clean-up by multi-walled carbon nanotubes (MWCNTs), derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) and detection with liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method was validated on twelve matrices spiked at 10 or 20, 100 and 500 μg/kg. The recovery ranged from 80% to 108% with intra-day RSDs (n=5) of 0.6-9.8% and inter-day RSDs (n=15) of 3.0-9.4%. Good linearities (R(2)⩾0.9991) were obtained for all matrices. The limit of detection (LOD) and limit of quantification (LOQ) for the selected matrices ranged from 0.3 to 3.3 μg kg(-1) and from 1 to 10 μg kg(-1), respectively. The method was demonstrated to be reliable and sensitive for the routine monitoring of glufosinate in plant origin foods.

Analytical method for 44 pesticide residues in spinach using multi‐plug‐filtration cleanup based on multiwalled carbon nanotubes with liquid chromatography and tandem mass spectrometry detection

Spinach is one of the most commonly planted vegetables worldwide. A high chlorophyll content makes spinach a complicated matrix in pesticide residue analysis. In this study, a rapid clean-up method was developed for the analysis of pesticide multi-residues in spinach followed by liquid chromatography with tandem mass spectrometry. A modified QuEChERS method with multiwalled carbon nanotubes and carbon material was adopted in the multi-Plug Filtration Cleanup procedure. This method was validated for 44 representative pesticides spiked at two concentration levels of 10 and 100 μg/kg. The pesticides of different physicochemical properties were registered on spinach in China. The recoveries were between 76 and 114% for major pesticides with relative standard deviations of less than 15%, except for quizalofop-P-ethyl, pyrimethanil, and carbendazim. Matrix-matched calibration curves were performed with the coefficients of determination higher than 0.995 for the studied pesticides for concentration levels of 10-500 μg/kg. The limits of quantitation ranged from 2 to 10 μg/kg. The developed method was successfully applied to determine pesticide residues in Chinese market spinach samples.

Coupling of multi-walled carbon nanotubes/polydimethylsiloxane coated stir bar sorptive extraction with pulse glow discharge-ion mobility spectrometry for analysis of triazine herbicides in water and soil samples

An analytical method based on stir bar sorptive extraction (SBSE) coupled with pulse glow discharge-ion mobility spectrometry (PGD-IMS) was developed for analysis of three triazine pesticide residues in water and soil samples. An injection port with sealing device and stir bars hold device were designed and constructed to directly position the SBSE fiber including the extracted samples into the heating device, making desorption and detection of analytes proceeded simultaneously. The extraction conditions such as SBSE solid phase material, extraction time, extraction temperature, pH value and salt concentration were optimized. Mixture of MWCNTs-COOH and PDMS were shown to be effective in enriching the triazines. The LODs and LOQs of three triazines were found to be 0.006-0.015μgkg(-1) and 0.02-0.05μgkg(-1), and the linear range was 0.05-10μgL(-1) with determination coefficients from 0.9987 to 0.9993. The SBSE-PGD-IMS method was environmentally friendly without organic solvent consumption in the entire experimental procedures, and it was demonstrated to be a commendable rapid analysis technique for analysis of triazine pesticide residues in environmental samples on site. The proposed method was applied for the analysis of real ground water, surface water and soil samples.

Analysis of sulfonamides, tilmicosin and avermectins residues in typical animal matrices with multi-plug filtration cleanup by liquid chromatography–tandem mass spectrometry detection

The frequent use of various veterinary drugs could lead to residue bioaccumulation in animal tissues, which could cause dietary risks to human health. In order to quickly analyze the residues, a liquid chromatography tandem mass spectrometry (LC-MS/MS) method was developed for detecting Sulfonamides, Tilmicosin and Avermectins (AVMs) residues in animal samples. For sample preparation, modified QuEChERS (quick, easy, cheap, effective, rugged and safe) and ultrasound-assisted extraction (UAE) methods were used. For sample cleanup, n-Hexane delipidation and multi-plug filtration cleanup (m-PFC) method based on primary-secondary amine (PSA) and octadecyl-silica (C18) were used, followed by LC-MS/MS analysis. It was validated on 7 animal matrices (bovine, caprine, swine meat and their kidneys, milk) at two fortified concentration levels of 5 and 100μg/kg. The recoveries ranged from 82 to 107% for all analytes with relative standard deviations (RSDs) less than 15%. Matrix-matched calibrations were performed with coefficients of determination above 0.998 for all analytes within concentration levels of 5-500μg/kg. The developed method was successfully used to analysis veterinary drugs of real animal samples from local markets.

Multiplug filtration cleanup method with multi-walled carbon nanotubes for the analysis of malachite green, diethylstilbestrol residues, and their metabolites in aquatic products by liquid chromatography–tandem mass spectrometry

AbstractThe food safety supervision in aquatic products has raised public concern in recent years. In this study, a liquid chromatographic–tandem mass spectrometric (LC-MS/MS) method for the simultaneous quantification and identification of four residues of the ever widely used analytes (including malachite green, leucomalachite green, diethylstilbestrol, and dienestrol) in aquaculture samples was developed. For sample preparation, a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was used, which was initially developed for pesticide residue analysis. For cleanup procedure, low-temperature cleanup method was combined with multiplug filtration cleanup (m-PFC) method based on multi-walled carbon nanotubes (MWCNTs). The volume of water, extraction solvent, cleanup sorbents, and m-PFC procedure were optimized for carp, striped bass, and giant salamander matrices. It was validated by analyzing four residues in each matrix spiked at three concentration levels of 0.5, 5, and 50xa0μg/kg (nu2009=u20095). The method was successfully validated according to the 2002/657/EC guidelines. After optimization, spike recoveries were within 73–106xa0% and <15xa0% relative standard deviations (RSDs) for all analytes in the tested matrices. Limits of quantification (LOQs) for the proposed method ranged from 0.10 to 0.50xa0μg/kg. Matrix-matched calibrations were performed with the coefficients of determination >0.998 between concentration levels of 0.5 and 200xa0μg/kg. The developed method was successfully applied to the determination of residues in market samples.n Graphical abstractFlow chart of multi-plug filtration cleanup combined with low-temperature cleanup method

Simultaneous determination of 124 pesticide residues in Chinese liquor and liquor-making raw materials (sorghum and rice hull) by rapid Multi-plug Filtration Cleanup and gas chromatography–tandem mass spectrometry

A multi-residue method was developed for the determination of 124 pesticide residues in Chinese liquor and liquor-making raw materials (sorghum and rice hull) by rapid Multi-plug Filtration Cleanup (m-PFC) and GC-MS/MS detection. Different combination and proportion sets of sorbents were initially optimized for each matrix with adispersive solid-phase extraction (d-SPE) procedure. Satisfactory linearity was obtained for the 124 pesticides with regression coefficients (R2) greater than 0.9901. Mean recoveries of 121 pesticides were in the range of 71-121% with Relative Standard Deviations (RSDs) lower than 16.8% except cyprodinil, diflufenican and prothioconazole. The Limit of Quantification (LOQs) was in the range of 1.0×10-4-5.0×10-3mgkg-1 and the Limit of Detection (LODs) ranged from 3.0×10-5 to 1.5×10-3mgkg-1 for the 124 pesticides in the matrices. It is demonstrated the m-PFC procedure is superior to the d-SPE method and it could be used to routinely monitor of pesticide residues in market samples.