QuEChERS Extraction Method Research Articles

The effect of different washing methods assisted by ultrasound on the removal of cypermethrin and spirotetramat residues in apples

AbstractThe simplest way to remove pesticide residues from fruits and vegetables is to wash them with tap water. However, this method is not effective enough. In this study, the effectiveness of different washing methods assisted by ultrasound on pesticide removal was investigated. For this purpose firstly, apples were soaked in a cypermethrin (CYP) and spirotetramat (SPI) solution, which are frequently used as insecticides. Subsequently, the apples were washed in solutions prepared with vinegar, lemon juice, and baking soda at different concentrations (0.5%, 1% and 2%) and assisted by ultrasound (2.5–5 min). The residues in the medicated and washed samples were analysed on an LC-MS/MS instrument after extraction using the QuEChERS extraction method. The results of the analysis showed that acidic vinegar and lemon juice were more effective than baking soda. Moreover, the application of ultrasound significantly increased this effect. When a 0.5% vinegar solution was assisted by ultrasound, 62% of the cypermethrin residue was removed and 82% of the spirotetramat residue was removed. These values were 51.5% and 49.6% higher than tap water, respectively. In conclusion, acidic solutions such as vinegar, which we can easily prepare at home, are highly effective in removing pesticide residues when assisted by ultrasound.

Monitoring of Polychlorinated biphenyls in Surface Water Using QuEChERS Extraction Method with Gas Chromatography-micro Electron Capture Detector

Monitoring of Polychlorinated biphenyls in Surface Water Using QuEChERS Extraction Method with Gas Chromatography-micro Electron Capture Detector

Dissecting the binding effect of Crocetin glucosyltransferase 2 in crocetin biotransformation in saffron (Crocus sativus L.) from different origins

Crocus sativus L. is a both medicinal and food bulbous flower whose qualities are geographically characterized. However, identification involving different places of origin of such substances is currently limited to single-omics mediated content analysis. Integrated metabolomics and proteomics, 840 saffron samples from six countries (Spain, Greece, Iran, China, Japan, and India) were analyzed using the QuEChERS extraction method. A total of 77 differential metabolites and 14 differential proteins were identified. The limits of detection of the method were 1.33 to 8.33 μg kg−1, and the recoveries were 85.56% to 105.18%. Using homology modeling and molecular docking, the Gln84, Lys195, Val182 and Pro184 sites of Crocetin glucosyltransferase 2 were found to be the targets of crocetin binding. By multivariate statistical analysis (PCA and PLS-DA), different saffron samples were clearly distinguished. The results provided the basis for the selection and identification of high quality saffron from different producing areas.

Development of a simple screening method for analyzing cereulide toxin in fried rice using liquid chromatography-tandem mass spectrometry.

The presence of cereulide, an emetic toxin produced by Bacillus cereus, in fried rice samples is critical evidence of food poisoning even in situations where B. cereus could not be detected. This study aims to develop a screening method for analyzing cereulide in fried rice using the QuEChERS procedure and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Cereulide was identified and quantified in fried rice samples using the QuEChERS extraction method and LC-MS/MS. The accuracies of the methods were determined by analyzing fortified blank samples at two concentrations (10 and 50µg/kg) conducted on three samples daily for five days. The QuEChERS procedure removed matrix compounds from fried rice. Characteristic MS/MS spectra enabled the identification of cereulide. As the matrix effects in seven fried rice samples were within ± 6%, an external solvent calibration curve could be used for quantification. This method exhibited good accuracy ranging from 88 to 89%. The relative standard deviations for both repeatability and intra-laboratory reproducibility were < 4%. These standard deviations satisfied the criteria of the Japanese validation guidelines for residues (MHLW 2010, Director Notice, Syoku-An No. 1224-1). The limit of quantification was 2μg/kg. The applicability of this method was confirmed using the analysis of cereulide in fried rice samples incubated with emetic Bacillus cereus. The QuEChERS extraction procedure described herein showed substantial promise as a reliable screening tool for cereulide in fried rice sample.

Optimization of an HPLC-MS/MS method to analyze chlordecone in bovine serum and correlations with levels in liver, muscle and fat

Chlordecone is an organochlorine pesticide used from 1972 to 1993 in the French West Indies. Its extensive use and high persistence in soils induced massive contamination of the environment and of the food chain, especially in cattle through contaminated soil ingestion. To ensure suitability for consumption of bovine meat, monitoring plans are set up based on perirenal fat concentrations after slaughtering. In the present study, we have investigated an in-vivo monitoring approach by measuring chlordecone levels in serum samples. For this purpose, a sensitive high-performance liquid-chromatography-tandem mass spectrometry (HPLC-MS/MS) method following a QuEChERS extraction method was successfully optimized and validated, reaching a limit of quantification of 0.05 ng g−1 fresh weight. This method was applied to 121 serum samples collected from bovines originating from contaminated areas of Martinique and Guadeloupe. Chlordecone was detected in 88% of the samples, and quantified in 77% of the samples, with concentrations ranging from 0.05 to 22 ng g−1. Perirenal fat, liver, and muscle were also sampled on the same animals and the measured concentrations of chlordecone were statistically correlated to the levels determined in serum. Mean concentration ratios of 6.5 for fat/serum, 27.5 for liver/serum, and 3.3 for muscle/serum were calculated, meaning that chlordecone was not only distribute in fat (as expected), muscle and liver, but also in serum. Good correlations were found to allow prediction of chlordecone concentrations in muscle based on concentrations measured in serum. This study opens the door to possible pre-control of bovines before slaughter. In cases of probable non-compliance with maximum residue levels (MRLs), farm management could proceed to allow for depuration under controlled conditions. This would have a strong impact on both economic and food safety management measures.

Target and suspect screening approaches for the identification of emerging and other contaminants in fish feeds using high resolution mass spectrometry

Fish feed is essential in aquaculture fish production because, along with beneficial nutrients and components, many suspected compounds can be transferred to fish and ultimately to humans. In this context, a comprehensive analysis was conducted to monitor various pesticides and pharmaceutical compounds in aquaculture fish feed through target analysis and many other groups of chemicals via suspect screening approaches. In this study, the QuEChERS extraction method was optimized, validated, and applied to fifty-four fish feed samples collected from different production batches. This was followed by liquid chromatography-high-resolution linear ion trap/Orbitrap mass spectrometry (LC-HR-IT/Orbitrap-MS) for targeted and suspect screening purposes. In general, pesticides provided satisfactory recoveries (70–105.5 %), with quantification limits lower than 5 ng g−1, whereas pharmaceuticals displayed recoveries ranging from 70.5 to 120.2 %, with quantification limits below 25 ng g−1. In addition, the matrix effects and measurement uncertainty were assessed to provide more accurate and high-confidence results. Pirimiphos-methyl was detected and quantified in 20 of 54 fish feed samples (37 %) at concentrations <77 ng g−1. Finally, suspect screening revealed the occurrence of 10 mycotoxins (e.g., citrinin, aflatoxin G2, zearalenone, and alternariol), two pesticides excluding the target pesticides (tebuconazole and fenazaquin), perfluorooctane sulfonic acid (PFOS) in almost 2 % of the samples, and ethoxyquin (antioxidant), with 12 of its Transformation Products (TPs). Finally, suspect analysis incorporated in routine analyses have proven to have great potential for complete monitoring.

Pesticide Residues and Associated Public Health Risks in Vegetables from Irrigated Farms Adjacent to Rift Valley Lake Ziway, Ethiopia

The overuse of pesticides has resulted in the accumulation of harmful residues in vegetables, which requires monitoring to assess the risks to human health. This article presents the levels of 35 pesticide residues in 15 composite vegetable samples from irrigated farmlands adjacent to Lake Ziway, Ethiopia, using the QuEChERS extraction method (Quick, Easy, Cheap, Effective, Rugged, and Safe) and then analyzes them using GC-MS. The study also estimated the health risks associated with the consumption of contaminated vegetables in children and adults, including carcinogenic and noncarcinogenic risks. The predominant pesticide residues found in tomatoes were α-endosulfan (0.58 mg/kg), β-BHC (0.04 mg/kg), heptachlor (0.02 mg/kg), and malathion (0.03 mg/kg), all of which were above the safety limits. Similarly, the mean concentration of heptachlor epoxide (0.04 mg/kg) and propargite (0.11 mg/kg) was higher than the allowed levels of the safety limits for onions. The concentration of pesticide residues detected in 10.6% and 7.9% of tomato and onion samples was above the maximum residual limits of the European Commission (EU-MRLs), respectively. Noncarcinogenic health risk estimates show that onion heptachlor epoxide had THQ &gt; 1, indicating the possibility of systemic health risk in both adult and child consumers. The carcinogenic health risk (CHR) showed that heptachlor epoxide in adults and children and only heptachlor in children had CHR &gt; acceptable limit (10−4) for tomato and onion. Therefore, it is critical to raise awareness among stakeholders while simultaneously implementing sound monitoring policy actions to protect the ecosystem and the health of the population in the study area and beyond.

Enhanced Matrix Removal-Lipid (EMR-L): a novel approach for efficient clean-up in systemic toxicological analysis of drugs and pesticides

ABSTRACT The QuEChERS extraction method was extensively modified and validated for effective screening of drugs and pesticides in diverse biological matrices, such as blood, urine, liver, and stomach contents. This method involved the extraction of 2 mL biological samples using acetonitrile as the solvent. To eliminate interferences, particularly lipids, a novel sorbent comprising a combination of C18 and specialized polymers called EMR-L (Enhanced Matrix Removal-Lipid) was employed. The extracted samples were then subjected to analysis using GCMS with a DB-5 MS column. The validation study encompassed various parameters including carryover, limit of detection (LOD), and interference investigation. LOD of analytes were ranged from 0.5 to 1.0 µg/mL. The validated method is known for its simplicity and effectiveness in conducting systemic toxicological analysis, covering a wide range of acidic, neutral, and basic analytes. Moreover, this method has the potential to detect additional drugs and pesticides not included in the validation study, provided they are compatible with gas chromatographic analysis. The modified method was successfully applied to real case samples, proving to be a valuable tool for systemic toxicological analysis. Its versatility allows for the screening of acidic, neutral, and basic drugs and pesticides in various biological matrices.

Evaluation of Alternaria toxins in fruits, vegetables and their derivatives marketed in China using a QuEChERS method coupled with ultra-high performance liquid chromatography-tandem mass spectrometry: Analytical methods and occurrence

Alternaria species are invasive fungi that infect fruits and vegetables and produce Alternaria toxins resulting in loss of commodity values and harmful effects on human health. To establish a reliable analytical method for Alternaria toxins in fruits, vegetables and their derivatives (e.g., fruit and vegetable juices, purees and jams; dried fruit and vegetables; fruit and vegetable powders), a QuEChERS extraction method was developed and validated for the determination of most reported Alternaria toxins (alternariol monomethyl ether [AME], alternariol [AOH], tentoxin [TEN], tenuazonic acid [TeA], and altenuene [ALT]). The limits of quantitation (LOQ) of the target analytes in food matrices were 1.0–5.0 μg/kg. The extraction recoveries were 73.0%–120%, with good repeatability (<12.9%) and within-laboratory repeatability (<14.7%). The developed method was applied to 270 fruits, vegetables, and their derivatives randomly collected from the market in China. Approximately 45.2% of the samples were contaminated with varying levels of Alternaria toxins. The lowest incidence of contamination by Alternaria toxins was detected in fruits and vegetables (3.6%), and the highest incidence was found in fruit and vegetable powders (60.6%). TeA exhibited the highest detection frequency (22.6%) and the highest level of occurrence level (639 μg/kg) among the tested samples, followed by AOH (14.1%), ALT (11.9%), AME (4.4%), and TEN (3.3%). Furthermore, the simultaneous co-presence of two to five Alternaria toxins was detected in 13.7% of the analyzed samples. The combination of AOH + TeA was the most predominant, accounting for 4.8% of samples. This study developed a reliable and sensitive analytical method and provided representative occurrence data to support the assessment of emerging mycotoxins, especially Alternaria toxins, in fruit and vegetable products.

Unwanted Ingredients—Highly Specific and Sensitive Method for the Extraction and Quantification of PFAS in Everyday Foods

Perfluorinated alkyl substances (PFAS) are anthropogenic substances and can only come from polluted sources. There are many classes of PFAS which can be transformed to perfluoalkyl carboxylic acids and perfluoroalkyl sulfonic acids in the environment. Once they are in this form, they are environmentally mobile and extremely stable with half-lives of decades. These compounds are not innocuous and are implicated in causing many different diseases. In this publication, a method for the extraction and quantitation of perflurocarboxylic acids and perfluorosulfonic acids, using high-resolution liquid chromatography mass spectrometry (HRMS), is evaluated. A QuEChERS extraction method was performed on tomatoes, strawberries and milk purchased from different supermarkets on different days. Recoveries from milk and tomatoes were between 80 and 120%. Matrix effects were significant for strawberries and tomatoes and stable isotope internal standards were required to compensate. PFBA was found in all 3 food types. The total PFAS was 0.68 ng g−1 in milk, 0.20 ng g−1 in strawberries and 0.36 ng g−1 in tomatoes. This study demonstrates the importance of using a robust analytical method to investigate the PFAS content of complex food matrices and in particular the contribution of short-chain PFAS to overall dietary consumption.

Polycyclic Aromatic Hydrocarbons (PAHS) Levels and Toxicity in Herbal Teas Marketed in Malaysia using Quechers and GC-FID

In line with the growing health trend in Malaysia, more consumers drink herbal tea for medicinal benefits. However, herbal tea products could be contaminated with polycyclic aromatic hydrocarbons (PAHs) from various production sources. There is a little study focused on the detection of PAHs in herbal tea species distributed in Malaysia. This study was performed to investigate PAHs content and toxicity in selected commercial herbal teas in Malaysia. A total of seven different Malaysian herbal tea samples were extracted using QuEChERS extraction method and the contamination level of PAHs were evaluated using gas chromatography (GC) with a flame ionization detector (FID). The total content of 10 PAHs (∑10PAHs) in the herbal tea samples ranged from 2.53 to 9.39 µg/kg. Acenaphthene, fluorene, phenanthrene and anthracene were the most abundant compounds with 53% contribution of all PAHs content. All tested herbal teas species showed low toxic equivalency (TEQ) values ranging from 0.0027 to 0.1148. The least contaminated samples were Strobilanthes crispus, Senna alata, Orthosiphon aristatus, Clinacanthus nutans, and Stevia rebaudiana.

Pesticide residues in commonly consumed food from five localities of Burkina Faso: occurrence and health risk assessment.

Monitoring data for pesticides are generally scarce in many countries of the world, especially in developing countries. In Burkina Faso, there are few scientific data on the occurrence and concentrations of pesticide residues in staple foods found in local markets. Using QuEChERS extraction method and gas chromatography-mass spectrometry, samples of commonly eaten foods from five localities of Burkina Faso were evaluated by targeting more than 40 pesticides. It appears that 58.1% of all the collected samples exhibited at least one or more pesticide residues. Among those, 36.5% of the samples had at least one pesticide with a concentration above the maximum residue level (MRL) value. Unfortunately, no MRL data was available for dried fish which is a widely consumed food in this part of Africa. Simazine was found in tomatoes, pyrethroids in cereals, while dried fish contained most of the pesticides detected. The assessment of long-term health risks revealed that dieldrin quantified in dried fish showed more than 250% of acceptable daily intake which was then labelled as unacceptable high risk. For hazardous foods, more sampling should be carried out for a better assessment of the health risks involved.

Development of a simple HPLC procedure for the determination of prochloraz residues in mushrooms

Abstract A simple HPLC-UV procedure is described in our paper which is suitable for the rapid and cost-efficient determination of prochloraz in mushrooms. Prochloraz is the only fungicide in EU which use is allowed in mushroom production. The aim of our work was the development of a simple method that is suitable for the control of this pesticide in everyday analyses during mushroom production. The procedure involves a simple sample preparation method based on solid-liquid extraction (modified QuEChERS extraction method EN 15662) followed by an HPLC-UV determination (recovery: 97–99%; limit of detection LOD: 0.01 mg/kg; limit of quantification LOQ: 0.05 mg/kg).

Development and Validation for Simultaneous Determination of Disulfoton and Its Five Metabolites in Seven Agro-Products Using Liquid Chromatography-Tandem Mass Spectrometry Combined with QuEChERS Extraction Method

Development and Validation for Simultaneous Determination of Disulfoton and Its Five Metabolites in Seven Agro-Products Using Liquid Chromatography-Tandem Mass Spectrometry Combined with QuEChERS Extraction Method

Pesticide residues in dates using a modified QuEChERS method and GC-MS/MS

ABSTRACT The aim of this study was to develop a convenient, fast, effective and safe analytical method (QuEChERS) to determine 198 pesticide residues in multi-source date palm fruits using gas chromatography-tandem mass spectrometry (GC-MS/MS). The calibration curves for most pesticides were linear in the range of 15–150 µg/kg, with r2 values higher than 0.9934 and the relative standard deviation for all pesticides was ≤20%. The mean recovery rate of pesticides was 70–120% and limits of detection (LODs) and limits of quantification (LOQs) were in the range of 5–14 µg/kg and 14–40 µg/kg, respectively. The validated procedure was used to monitor pesticide residues in 30 fresh date samples. It could be concluded that the modified QuEChERS extraction method was efficient in analysing pesticide residues in dates palm and none of the samples contained residues above the MRLs.

Seasonal and geographical variations in insecticide and miticide residues in hop samples produced across three hop-growing regions in the Czech Republic during the years 2018–2020

The aim of this study was to determine the presence of zoocide (insecticide and miticide) residues in hops collected in three hop-growing regions located in the Czech Republic, and to assess their zoocide profiles and residue levels in terms of variability in temperature and precipitation across the 2018–2020 seasons. Furthermore, the weather factors that influenced the occurrence of hop pests are described and discussed. During our 3-year survey, a total of 120 samples of whole-cone hops samples harvested in three hop-growing regions were analysed for the presence of 29 insecticides and miticides using the modified QuEChERS extraction method, followed by liquid chromatography-tandem mass spectrometry and gas chromatography-tandem mass spectrometry. A majority, 119 of 120 samples, contained a residue of at least one of the active substances surveyed in this study, and 34 analysed samples contained multiple residues with three to four zoocides presented. Concerning the most frequently detected zoocide residues, spirotetramat and/or its metabolites were found in 94.2% of the samples at levels ranging from 0.02 to 1.08 mg/kg. Of the other zoocides surveyed, residues of fenpyroximate, hexythiazox, bifenazate and lambda-cyhalothrin were routinely found in hop cone samples. Obtained data were then used for evaluating seasonal and geographical variations in the profile of zoocide residues among the hop-growing regions in the years 2018–2020, and the compliance with legal regulations concerning the use of zoocides on hops was ascertained. The results showed that (1) the profile and levels of zoocide residues found in the samples reflected seasonal prevalence of pest infestation on hop plants; (2) the strategy to control pests (especially aphids) used in most of hop yards was consistent across the seasons; and (3) a concentration of spirotetramat residues less than 1 mg/kg was typical for hops grown in the Czech Republic.

Neonicotinoids exposure assessment in Africanized honey bees (Apis mellifera L.) by using an environmentally-friendly sample preparation technique followed by UPLC-MS/MS

A miniaturized QuEChERS extraction method followed by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed to analyze thiamethoxam and imidacloprid in 0.3 g of lyophilized Africanized honey bees (Apis mellifera L.). The work aimed to estimate honey bees' exposure to pesticides at the nanogram/gram (ng g−1) levels, using small sample and reagent quantities. Low amounts of solvents and salts were employed – 15× less than used in traditional methods. Average recoveries ranged from 64.5% to 99.7%, with repeatability below 20% for samples spiked at 3 and 167 ng g−1. LOD and LOQ were 0.7, and 3 ng g−1 for both pesticides. Applying the proposed approach, honey bee samples from different apiaries from the State of São Paulo (Brazil) were analyzed. The pesticides were detected in concentrations between 7.0 and 27.0 ng g−1. Thus, the proposed method can be used as a greener alternative to analyze the two neonicotinoids at trace levels in small quantities of bees, consequently saving chemicals and waste.

Multi-Residue Analysis of Chemical Additives in Edible Vegetable Oils Using QuEChERS Extraction Method Followed by Supercritical Fluid Chromatography.

Since the quality and safety of food highly depend on its preservation and protection, the use of food packaging materials increases the risk of chemical contamination of the packaged food by migration. Herein, we focused on antioxidants, photoinitiators, UV absorbers and plasticizers which are extensive additives used in food packaging materials. In the present study, a rapid, simple, green and reliable method was developed and validated for the determination of twelve chemical additives in edible vegetable oils using SFC together with a modified QuEChERS procedure. Under the optimum conditions, twelve additives were separated within 10 min, and the consumption of the organic solvent was significantly reduced, which improved the environmentally friendliness. The performance of the developed method was evaluated. Good linearity (r > 0.999) was obtained in the range of 0.20–20.0 µg/mL and 0.50–20.0 µg/mL, respectively. The limits of detection and limits of quantification of the twelve additives in vegetable oils were 0.05–0.15 µg/mL and 0.15–0.50 µg/mL, respectively. Recoveries of all the chemical additives for the spiked samples were between 60.9% and 106.4%, with relative standard deviations (RSD) lower than 9.9%. The results demonstrated that the proposed method was efficient, reliable and robust for the routine analysis of additives in edible vegetable oils and can be an alternative to the multi-residue analysis of chemical additives for other packaged foods.

Investigation and probabilistic health risk assessment of pesticide residues in cucumber, tomato, and okra fruits from Khuzestan, Iran.

In this study, 30 pesticide residues in 45 fresh-eating cucumber, tomato, and okra fruit samples collected from the Khuzestan province as the main agricultural products in Iran using the QuEChERS extraction method were analyzed. In addition, noncarcinogen and carcinogen health risk assessments were evaluated. Results indicated that 93% of cucumber samples had at least one pesticide, of course, less than the maximum residue limit (MRL). All tomato and okra fruit samples were contaminated by diazinon. All pesticides detected in tomato samples were below national MRL except for thiamethoxam in four samples. In okra fruit samples, all detected diazinon and malathion, but only tebuconazole fungicide exceeded MRL. In addition, the hazard index (HI) was 0.23 and 1.06 in cucumber samples, 0.33 and 1.51 in tomato samples, and 5.5E-03 and 0.025 in okra fruit samples in adults and children, respectively. The use of cucumber and tomato may have notable risks in the short term in children group age. Ranking based on total CR was 1.2E-05 in tomato, 7.7E-06 for cucumber, and in okra 9.1E-11 because of the difenoconazole residue. However, significant carcinogenic risk threatens cucumber and tomato consumers.

Multi-residue analysis for the determination of pesticide residues in fruit and vegetables using liquid chromatography coupled with mass spectrometry

This article summarizes the results of validation studies of a multi-residue method for the determination of pesticide residues in fruits and vegetables. The results of some of the monitoring control programs carried out in Romania are also presented. Liquid chromatography coupled with mass spectrometry (LC-MS / MS) was used to assess pesticide residue levels. The QUECHERS extraction method was used to extract the compounds. To validate the method, the control samples were fortified with a solution of 74 pesticides for LC-MS / MS analyzes, at 3 levels.The validation study is based on the regulations in Document DG Nº SANTE / 12682/2019. The scope of validation included the following performance requirements: Limit of detection; Quantification limit; Recovery; Fidelity; Repeatability; Reproducibility; Recovery; Selectivity / Specificity; Stability / Robustness; Linearity; Matrix effect; Measuring the margin of error.