Combination of a modified quick,easy, cheap,efficient, rugged,and safe extraction method with a deep eutectic solvent based microwave‐assisted dispersive liquid–liquid microextraction: Application in extraction and preconcentration of multiclass pesticide residues in tomato samples

In this study, a new two–step extraction procedure based on the combination of a modified quick, easy, cheap, effective, rugged, and safe extraction method with a deep eutectic solvent based microwave‐assisted dispersive liquid–liquid microextraction has been developed for the extraction of multiclass pesticides in tomato samples before their analysis by gas chromatography with flame ionization detection. In this method, initially, an aliquot of tomato is crushed and diluted with deionized water. The mixture is then passed through a filter paper and its residue and aqueous phase are separated. Afterwards, acetonitrile as an extraction/disperser solvent is passed through the filter paper containing the refuse. The analytes remained in the refuse are extracted into the acetonitrile and then the obtained extract is mixed with a deep eutectic solvent. The obtained mixture is injected into the tomato juice and placed in a microwave oven for 15 s. Consequently, a cloudy state is formed and the extractant containing the analytes are sedimented at the bottom of the tube after centrifugation. Finally, 1 μL of the sedimented phase is removed and injected into the separation system. Under the optimum conditions, limits of detection and quantification were in the ranges of 0.42–0.74 and 1.4–2.5 ng/g, respectively.     

A simple and efficient sample preparation for taxanes in Taxus chinensis needles with natural menthol‐based aqueous deep eutectic solvent

Taxanes are natural anticancer constituents, and the sample preparation from matrix normally depends on organochlorine solvents. In this study, green and natural menthol‐based aqueous deep eutectic solvent was synthesized and used for sample preparation for taxanes. Five key parameters were optimized and the optimal preparation conditions were as follows: menthol/1‐propanol ratio 1:1 (mol/mol), solid–liquid ratio 1:30 g/mL, extraction time 30 min, ultrasonic power 250 W, and water content 80%. Under the above conditions, the total extraction efficiency of seven main taxanes was 1.25‐ to 1.44‐fold to the conventional methods. In addition, a high‐performance liquid chromatography method with C₁₈ column was established for quantitation of seven main taxanes in <25 min, which had excellent linearity (R² > 0.9986), precision (relative standard deviation < 3.00%), repeatability (relative standard deviation < 3.69%), and recovery (90.26–109.00%). This method performed the extraction, and enrichment processes simultaneously, and it had advantages such as high extraction efficiency, simple operation, low cost, and eco‐friendliness. This work indicated that the natural menthol‐based deep eutectic solvent aqueous could be an excellent alternative to the sample preparation from Taxus or other plants.     

Development of a green miniaturized quick,easy, cheap,effective, rugged,and safe approach in tandem with temperature-assisted solidification of floating menthol droplet for analysis of multiclass pesticide residues in milk

A new green miniaturized quick, easy, cheap, effective, rugged, and safe approach was developed and used for the extraction of multiclass 16 pesticides in milk before gas chromatography analysis. The miniaturization of method reduced the consumption of chemical reagents and samples. Magnetic three-dimensional graphene was used as sorbent in the clean-up step. Choline chloride:lactic acid (1:2) natural deep eutectic solvent was used as desorption solvent. Temperature-assisted solidification of floating menthol drop was executed for preconcentration of analytes. The method parameters including sorbent, desorption solvent, sorption and desorption times, menthol amount, pH, and ionic strength were optimized. The limit of quantification and linear range were 0.03–0.38 and 0.03–250 μg/kg, respectively. The accuracy was assessed by recovery evaluation at the spike levels of 50 and 100 μg/kg, in the range of 61–119%, with relative standard deviations within 2.1–18.2%. The method was applied to the analysis of pasteurized low and high-fat bovine milk, and various pesticide residues were detected in the concentrations range of 1.24–4.68 μg/kg. Finally, the greenness of the procedure was evaluated using the Analytical Eco-Scale. This work represents the first application of hybrid miniaturized extraction/preconcentration using a natural deep eutectic solvent and menthol to analyze pesticides.     

Determination of phthalate esters in soil using a quick,easy, cheap,effective, rugged,and safe method followed by GC–MS

A quick, easy, cheap, effective, rugged, and safe procedure was designed to extract pesticide residues from fruits and vegetables with a high percentage of water. It has not been used extensively for the extraction of phthalate esters from sediments, soils, and sludges. In this work, this procedure was combined with gas chromatography with mass spectrometry to determine 16 selected phthalate esters in soil. The extraction efficiency of the samples was improved by ultrasonic extraction and dissolution of the soil samples in ultra‐pure water, which promoted the dispersion of the samples. Furthermore, we have simplified the extraction step and reduced the risk of organic solvent contamination by minimizing the use of organic solvents. Different extraction solvents and clean‐up adsorbents were compared to optimize the procedure. Dichloromethane/n‐hexane (1:1, v/v) and n‐hexane/acetone (1:1, v/v) were selected as the extractants from the six extraction solvents tested. C18/primary secondary amine (1:1, m/m) was selected as the sorbent from the five clean‐up adsorbents tested. The recoveries from the spiked soils ranged from 70.00 to 117.90% with relative standard deviation values of 0.67–4.62%. The proposed approach was satisfactorily applied for the determination of phthalate esters in 12 contaminated soil samples.     

A modified quick,easy, cheap,effective, rugged,and safe method for determination of by-products originating from ozonation of chlorpyrifos and diazinon spiked in cherry tomato and perilla leaf

In this study, sample pretreatment methods have been developed for the determination of chlorpyrifos, diazinon, and their by-products present in cherry tomato and perilla leaf using liquid chromatography-tandem mass spectrometry. To optimize a quick, easy, cheap, effective, rugged, and safe method, the recoveries at each step were evaluated. The steps improved the recoveries of chlorpyrifos, chlorpyrifos oxon, diazinon, diazoxon, and 2-isopropyl-6-methyl-4-pyrimidinol up to 80% or more by removing interferents, but diethyl phosphate was almost lost during the partition procedure, and the 3,5,6-trichloro-2-pyridinol recovery was below 65%. Therefore, the compounds were evaluated using different solvent compositions based on a quick polar pesticides method; note that 100% methanol showed acceptable extraction results. The optimized method provided method detection limits ranging from 0.03 to 1.22 ng/g and good linearities (R² > 0.996). The recovery values were between 82.1 and 113.3%. The intra- and interday reproducibility was evaluated to be within 8.6 and 9.9%, respectively. The method was applied to determine the degradation efficiency of chlorpyrifos and diazinon and their by-products formed during plasma treatment.     

Ethanol-ammonium sulfate system based modified quick,easy, cheap,effective, rugged,and safe method for the determination of four neonicotinoid pesticide and metabolite residues in two canned fruits

As the pesticide and its metabolite residues in processed fruits could become a significant route of human exposure. The work presented herein focuses on developing a feasible quick, easy, cheap, effective, rugged, and safe method with improved extraction and cleanup system for the determination of imidacloprid, acetamiprid, thiamethoxam, and clothianidin (a metabolite of thiamethoxam) in canned fruits. The low toxic solvent ethanol was used to extract the analytes, and ammonium sulfate was used to promote phase separation. Moreover, the carboxylated multi-walled carbon nanotube acted as the clean-up sorbent for the removal of high solubility impurities. The proposed method was validated with fortified real samples at different concentration levels (20–200 μg/kg). Recoveries obtained from three spiked levels (20, 50, and 200 μg/kg) ranged from 74.9 to 86.4% with relative standard deviations of the intra-day and inter-day in the range of 0.8–5.5 and 2.0–7.1%, respectively. The limits of detection ranged from 0.2 to 0.5 and 0.2 to 0.6 μg/kg for orange and peach, respectively. The results demonstrated that the proposed method could be considered appropriate, and comparatively lower toxic for the analysis of neonicotinoid pesticide residues in canned fruit.     

Simultaneous determination of flupyradifurone and its two metabolites in fruits,vegetables, and grains by a modified quick,easy, cheap,effective, rugged,and safe method using ultra high performance liquid chromatography with tandem mass spectrometry

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.     

Rapid screening of amitraz and its metabolite residues in honey using a quick,easy, cheap,effective, rugged,and safe extraction method coupled with UHPLC and Q Exactive

A method for determining amitraz and 2,4‐dimethylaniline in honey was established by using ultra‐high‐performance liquid chromatoghaphy and Q Exactive after applying quick, easy, cheap, effective, rugged, and safe extracting process. A suitable extraction method was designed to extract the amitraz and 2,4‐dimethylaniline after a suitable amount of honey samples was dissolved. A Thermo Syncronis C₁₈ column (100 × 2.1 mm, 1.7 μm) was used for chromatographic separation of the samples. Then the two compounds were quantitatively analyzed via a program of Q Exactive. The linearity of amitraz and 2,4‐dimethylaniline was good in the concentration range of 0.5–100 μg/L, and the correlation coefficient R² was >0.99. The average recovery and relative standard deviation of each component were 81.3–90.0% and 5.1–7.2%. The 24‐ and 48‐h test results showed that the sample needed to be tested within 24 h. The limit of detection was 0.1 μg/kg for amitraz and 2,4‐dimethylaniline, whereas for both the limit of quantitation was 0.3 μg/kg.     

Determination of hexabromocyclododecane enantiomers in chicken whole blood by a modified quick,easy, cheap,effective, rugged,and safe method with liquid chromatography and tandem mass spectrometry

A rapid and simple analytical method has been developed for the determination of hexabromocyclododecane enantiomers in chicken whole blood, based on a modified quick, easy, cheap, effective, rugged, and safe approach before liquid chromatography coupled with tandem mass spectrometry. The factors influencing performance of method were investigated by single factor experiment, and further optimized by the response surface methodology based on Box–Behnken design. The matrix effects were also evaluated by the isotopic dilution method. Under the optimal conditions, the proposed method showed good linearity within the range of 1–500 μg/L and good repeatability with relative standard deviation less than 9.5% (n = 5). The limits of detection (S/N = 3) were 0.03–0.19 μg/L. The developed method was successfully applied for the analysis of hexabromocyclododecane enantiomers in real chicken blood samples. The satisfactory recoveries ranging of 83.6–115.0% were obtained (at spiked levels of 5, 20, and 100 μg/L). The results demonstrated that the proposed method would be a practical value method for the determination of hexabromocyclododecane enantiomers in animal blood. It would be further developed with confidence to analyze other lipophilic organic pollutants in blood sample.     

Qualitative-quantitative analysis of multi-mycotoxin in milk using the high-performance liquid chromatography-tandem mass spectrometry coupled with the quick,easy, cheap,effective, rugged and safe method

High-performance liquid chromatography-tandem mass spectrometry coupled with the quick, easy, cheap, effective, rugged and safe method was established for the qualitative and quantitative detections of 20 mycotoxins in milk. The linear range of this method was 0.01–10 μg/L and the correlation coefficients were all greater than or equal to 0.9933. At three levels of addition, the spiked recoveries ranged from 80.00 to 112.50%, relative standard deviations were 2.67–14.97%, limits of quantitation were 0.02–4.00 μg/kg, and limits of detection were 0.007–1.300 μg/kg. This developed procedure for the identification and quantitation of mycotoxins provided prospective support for quality regulation.     

Multiresidue analysis of 36 pesticides in soil using a modified quick,easy, cheap,effective, rugged,and safe method by liquid chromatography with tandem quadruple linear ion trap mass spectrometry

A new method for simultaneous determination of 36 pesticides, including 15 organophosphorus, six carbamate, and some other pesticides in soil was developed by liquid chromatography with tandem quadruple linear ion trap mass spectrometry. The extraction and clean‐up steps were optimized based on the quick, easy, cheap, effective, rugged, and safe method. The data were acquired in multiple reaction monitoring mode combined with enhanced product ion to increase confidence of the analytical results. Validation experiments were performed in soil samples. The average recoveries of pesticides at four spiking levels (1, 5, 50, and 100 μg/kg) ranged from 63 to 126% with relative standard deviation below 20%. The limits of detection of pesticides were 0.04–0.8 μg/kg, and the limits of quantification were 0.1–2.6 μg/kg. The correlation coefficients (r²) were higher than 0.990 in the linearity range of 0.5–200 μg/L for most of the pesticides. The method allowed for the analysis of the target pesticides in the lower μg/kg concentration range. The optimized method was then applied to the test of real soil samples obtained from several areas in China, confirming the feasibility of the method.     

Determination of multiple antibiotics in agricultural soil using a quick,easy, cheap,effective, rugged,and safe method coupled with ultra-high performance liquid chromatography-tandem mass spectrometry

In this study, we combined ultra-high performance liquid chromatography with tandem mass spectrometry to establish a quick, easy, cheap, effective, rugged, and safe method of detecting 21 target antibiotics in agricultural soil samples. Antibiotics were extracted with mixed solvents consisting of ethylenediaminetetraacetic acid disodium salt dihydrate and phosphoric acid citric acid buffer and acetonitrile which were purified with octadecylsilyl as an adsorbent and anhydrous sodium sulfate as a desiccant. This method was able to effectively extract all of the target antibiotics from agricultural soils, with recovery efficiencies ranging from 55 to 108% and limits of detection between 0.09–0.68 μg/kg. We also validated this new method for selectivity, sensitivity, and reliability of detecting multiple antibiotics in 12 samples. Considering the potential environmental and public health effects of antibiotics in agricultural soils, our new method can help analyze the degree of antibiotic contamination and provide valuable information for soil quality and risk assessment.     

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.     

Rapid determination of residual pesticides in tobacco by the quick,easy, cheap,effective, rugged,and safe sample pretreatment method coupled with LC–MS

A quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample pretreatment method coupled with LC–MS was developed for the determination of 11 pesticides in tobacco. Sample pretreatment parameters and instrumental parameters of LC–MS were investigated, and the optimal conditions were selected. Under the optimized conditions, the 11 pesticides were detected simultaneously with a good linear relationship (r² = 0.9993–0.9999) and high precisions (less than 5% of the RSD of peak areas). The LODs were in the range of 0.1–5.0 μg/L. Compared with SPE clean‐up, QuEChERS greatly simplified the sample pretreatment with simple solvent extraction system. After QuEChERS pretreatment, no serious matrix effects were observed. Used for the analysis of real samples, metalaxyl was found in cigarette and tobacco samples at 63.47 and 132.27 ng/g, respectively. The recoveries for 11 pesticides were in the range of 70.03–118.69%, and RSDs were less than 10%. The proposed method is simple, low cost, and has good reproducibility.     

A quick,easy, cheap,effective, rugged,and safe sample pretreatment and liquid chromatography with tandem mass spectrometry method for the simultaneous quantification of 33 mycotoxins in Lentinula edodes

Lentinula edodes, one of the most cultivated edible fungi in the world, are usually neglected for mycotoxins contamination due to the initial thinking of its resistance to mycotoxingenic molds. In the present study, a sensitive and reliable liquid chromatography with tandem mass spectrometry method was developed for the simultaneous quantification of 33 mycotoxins in L. edodes. Targeted mycotoxins were extracted using a quick, easy, cheap, effective, rugged, and safe procedure without any further clean‐up step, and analyzed by liquid chromatography with tandem mass spectrometry on an Agilent Poroshell 120 EC‐C₁₈ column (100 × 3 mm, 2.7 μm) with a linear gradient elution program using water containing 5 mM ammonium acetate and methanol as the mobile phase. After validation by determining linearity (R² > 0.99), sensitivity (LOQ ≤ 20 ng/kg), recovery (73.6–117.9%), and precision (0.8–19.5%), the established method has been successfully applied to reveal the contamination states of various mycotoxins in L. edodes. Among the 30 tested samples, 22 were contaminated by various mycotoxins with the concentration levels ranging from 3.3–28 850.7 μg/kg, predicting that the edible fungus could be infected by the mycotoxins‐producing fungi. To the best of our knowledge, this is the first report about real mycotoxins contamination in L. edodes.     

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 (R² ≥ 0.994) and was proven to be highly efficient and reliable for the routine monitoring of triazolone herbicides in cereals.     

Simultaneous determination of florfenicol with its metabolite based on modified quick,easy, cheap,effective, rugged,and safe sample pretreatment and evaluation of their degradation behavior in agricultural soils

A simple and simultaneous method for the determination of florfenicol and its metabolite florfenicol amine in agricultural soils using modified quick, easy, cheap, effective, rugged, and safe sample pretreatment and reversed‐phase high‐performance liquid chromatography with tandem mass spectrometry is presented. Florfenicol and its metabolite florfenicol amine residues in agricultural soils were extracted with alkalized acetonitrile and an aliquot was cleaned up with Si(CH₂)₃NH (CH₂)₂NH₂ and C₁₈ sorbent, which were powder materials. High‐performance liquid chromatography with tandem mass spectrometry was applied to simultaneously determine the level of florfenicol and florfenicol amine in agricultural soils. Excellent linearity was achieved for florfenicol and florfenicol amine over a range of concentrations from 0.1–500 μg/L with coefficients more than 0.99. Average recoveries at four different levels (0.005, 0.05, 0.5, and 5.0 mg/kg) for florfenicol and florfenicol amine ranged from 73.6–94.9% with relative standard deviations of 2.9–12.5%. The limits of detection for florfenicol and florfenicol amine in agricultural soils were 2.0 μg/kg, and the limits of quantification were 6.0 μg/kg. Based on this method, the degradation behavior of florfenicol and its metabolite florfenicol amine in three soils (Nanchang, Hangzhou, and Changchun) under sterilized and native conditions was investigated and the transformation rate of florfenicol amine from florfenicol was evaluated.     

Simultaneous extraction and determination of antibiotics in soils using a method based on quick,easy, cheap,effective, rugged,and safe extraction and liquid chromatography with tandem mass spectrometry

The increasing use of antibiotics has caused substantial environmental problems, which are a matter of great concern. The aim of this work was to develop a quick, easy, cheap, effective, rugged, and safe method for 20 antibiotic residues in soil. The developed method is based on extraction with acetonitrile and phosphate buffer, clean up with dispersive solid‐phase extraction adsorbent using primary secondary amine, octadecylsilane, followed by liquid chromatography with tandem mass spectrometry determination. We optimized different extraction methods and the ratio of cleanup adsorbents to achieve good recoveries at seven spiking levels that ranged from 61.4 to 118.9% with a relative standard deviation below 20% (n  = 5). The method quantification limit was in the range of 2–5 μg/kg for most analytes. Good linear regression coefficients greater than 0.990 were obtained. This method was applied for the analysis of real agricultural soil samples, confirming the feasibility of the method.     

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 pyrametostrobin and its two metabolites in cucumber and soil using a quick,easy, cheap,effective, rugged,and safe method with HPLC–MS/MS

An easy, effective and sensitive analytical method for the simultaneous determination of a novel fungicide pyrametostrobin and its two metabolites pyrametostrobin‐M1 and pyrametostrobin‐M2 in cucumber and soil was developed using a quick, easy, cheap, effective, rugged, and safe method with high‐performance liquid chromatography and tandem mass spectrometry. The extraction solvent was acetonitrile, and cleanup sorbents were primary secondary amine and graphitized carbon black for cucumber samples and primary secondary amine for soil samples. The three target compounds were successfully separated between 3.2 and 3.9 min using a Waters CORTECS™ C₁₈ column connected to an electrospray ionization source. All the matrix‐matched samples at three fortified levels (10, 100 and 1000  μg/kg) provided satisfactory recoveries in the range of 78.8–93.8% with relative standard deviations below 6.9%. The limits of quantitation for the three compounds were below 0.183 μg/kg. The proposed method was validated by analyzing real samples.