Analysis Of Food Residues Research Articles

Research Progress of Biosensor Based on Organic Photoelectrochemical Transistor.

In order to solve the food safety problem better, it is very important to develop a rapid and sensitive technology for detecting food contamination residues. Organic photoelectrochemical transistor (OPECT) biosensor rely on the photovoltage generated by a semiconductor upon excitation by light to regulate the conductivity of the polymer channels and realize biosensor analysis under zero gate bias. This technology integrates the excellent characteristics of photoelectrochemical (PEC) bioanalysis and the high sensitivity and inherent amplification ability of organic electrochemical transistor (OECT). Based on this, OPECT biosensor detection has been proven to be superior to traditional biosensor detection methods. In this review, we summarize the research status of OPECT biosensor in disease markers and food residue analysis, the basic principle, classification, and biosensing mechanism of OPECT biosensor analysis are briefly introduced, and the recent applications of biosensor analysis are discussed according to the signal strategy. We mainly introduced the OPECT biosensor analysis methods applied in different fields, including the detection of disease markers and food hazard residues such as prostate-specific antigen, heart-type fatty acid binding protein, T-2 toxin detection in milk samples, fat mass and objectivity related protein, ciprofloxacin in milk. The OPECT biosensor provides considerable development potential for the construction of safety analysis and detection platforms in many fields, such as agriculture and food, and hopes to provide some reference for the future development of biosensing analysis methods with higher selectivity, faster analysis speed and higher sensitivity.

Decagram-Scale Synthesis of N-{2-[4-(β-d-Glucopyranosyloxy)-2-methylphenyl]-1,1-dimethyl-2-oxoethyl}-3-methylthiophene-2-carboxamide (GPTC), a Metabolite of the Fungicide Isofetamid

AbstractA decagram-scale synthesis of N-{2-[4-(β-d-glucopyranosyloxy)-2-methylphenyl]-1,1-dimethyl-2-oxoethyl}-3-methylthiophene-2-carboxamide (GPTC), a metabolite of the fungicide isofetamid, has been achieved in a highly straightforward manner from the known compound 1-(4-hydroxy-2-methylphenyl)-2-methylpropan-1-one in eight steps with a 20% overall yield to provide a standard certified reference material for residue analysis in food.

Evaluation of the Results of Pesticide Residue Analysis in Food Sampled between 2017 and 2021

As mandated by the EU and the national risk management duties, pesticide residues were determined by four specialized laboratories in 9924 samples taken from 119 crops of economic importance in Hungary and imported foodstuffs during 2017–2021. The screening method applied covered 622 pesticide residues as defined for enforcement purposes. The limit of detection ranged between 0.002 and 0.008 mg/kg. The 1.0% violation rate concerning all commodities was lower than in the European Union. No residue was detectable in 45.9% of the samples. For detailed analyses, six commodities (apple, cherry, grape, nectarine/peach, sweet peppers, and strawberry) were selected as they were analyzed in over 195 samples and most frequently contained residues. Besides testing their conformity with national MRLs, applying 0.3 MRL action limits for pre-export control, we found that 73% of the sampled lots would be compliant with ≥90% probability based on a second independent sampling. Multiple residues (2–23) in one sample were detected in 36–50% of the tested lots. Considering the provisions of integrated pest management, and the major pests and diseases of selected crops, normally three to four and exceptionally, seven to nine active ingredients with different modes of action should suffice for their effective and economic protection within four weeks before harvest.

Development of a Pt-graphene nanocomposite-based solid-phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry for the determination of carbamate pesticides in fish.

In the present work, a potential solid-phase extraction (SPE) material based on graphene anchored with platinum nanoparticles (Pt-Graphene) was prepared and characterized by scanning electron micrographs and transmission electron micrograph. The carbamates residues in fish were enriched by SPE filled with Pt-Graphene and detected by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The proposed extraction protocol exhibited satisfactory recoveries (76.5-115.6%), low limit of quantitation values in μg kg-1 level, and good precision for the studied ten carbamates. These results demonstrated the feasibility of the proposed protocol. The developed Pt-Graphene nanoparticles showed excellent performance for extracting analytes at trace levels, indicating that it could be used as a potential SPE sorbent in food residue analysis.

Meeting nutritional adequacy in the Brazilian population increases pesticide intake without exceeding chronic safe levels

Achieving nutritional adequacy requires an increase in fresh foods consumption, which may increase pesticide intakes. This study aimed to identify required dietary modifications to achieve nutritional adequacy without exceeding the acceptable daily intake (ADI) for pesticides. Data from the National Dietary Survey 2017–2018 were linked to the pesticide database from the Program on Pesticide Residue Analysis in Food. We performed linear programming models to design nutritionally adequate diets constrained by food preferences for different constraints on pesticide intake at the least cost increment. Nutritional adequacy led to an increase in pesticide intakes without exceeding their ADI. Modifications in diets varied according to the model, but, in general, consisted in an increase in fruits and vegetables, dairy, and seafood, and a reduction in rice, red meat, and sugar-sweetened beverages quantities. In conclusion, meeting nutritional adequacy increases pesticide intake compared to the observed diets, without representing a health concern to consumers.

The poison is on the table: an analysis of the pesticides present in the food of Brazilians

Brazil is the world's largest consumer of pesticides. To monitor the quality of food sold in the country, the Program for Analysis of Pesticide Residues in Food (Programa de Análise de Resíduos de Agrotóxicos em Alimentos - PARA) was created, responsible for carrying out analyzes of these foods and providing annual reports. The objective of this study was to carry out a survey of the information contained in these reports on the residues of pesticides found on unsatisfactory samples (unauthorized pesticides and/or above the permitted limit). This is a descriptive documentary study, based on the reports available (2001 to 2018). Information was collected on the pesticides that most appeared among the samples considered unsatisfactory and their possible damage to human health. Strawberries, bell peppers, and cucumbers presented the largest numbers of samples unsatisfactory, mostly because of the presence of pesticides unauthorized. The pesticides that have been repeated the most irregularly were chlorpyrifos, carbendazim, acefate and metamidophos, the latter has been banned since 2011 in Brazil. Evidence show that such pesticides are toxic to the human organism. Measures are needed to better control and inspect food and pesticides sold in Brazil, also raise awareness among the population and rural producers.

Selective multiresidue determination of highly polar anionic pesticides in plant-based milk, wine and beer using hydrophilic interaction liquid chromatography combined with tandem mass spectrometry

In this work, an easy and fast procedure for the selective multiresidue determination of 14 highly polar pesticides (including glyphosate, glufosinate, ethephon and fosetyl) and metabolites in beverages is presented. After an initial sample dilution (1:1, v/v), the extract is shaken and centrifuged, further diluted and then injected directly into the LC-MS/MS system, using hydrophilic interaction liquid chromatography (HILIC) and tandem mass spectrometry. No clean-up procedure was needed. The method was validated according to the current European guidelines for pesticide residue analysis in food and feed and linearity, limits of detection and quantification, matrix effects, trueness and precision were assessed. For plant-based milk, wine and beer samples, 10, 11 and 12 analytes, respectively, out of 14 were fully validated at 10 µg kg−1, the lowest spike level tested. The matrix effect was negative in most of the cases, showing for some compounds, such as HEPA, up to 80% suppression when compared to the response from standards in solvent. The use of isotopically labelled internal standards is required for the optimal quantification, as it compensates for high and varying matrix effects and also for recovery losses during extraction.

Enantiomeric separation of malathion and malaoxon and the chiral residue analysis in food and environmental matrix.

Malathion is a widely used chiral phosphorus insecticide, which has a more toxic chiral metabolite malaoxon. In this work, the enantiomers of malathion and malaoxon were separated by high-performance liquid chromatography-mass/mass (HPLC-MS/MS) with chiral columns using acetonitrile/water or methanol/water as mobile phase, and the chromatographic conditions were optimized. Based on the chiral separation, the chiral residue analysis methods for the enantiomers in soil, fruit, and vegetables were set up. Two pairs of the enantiomers were better separated on CHIRALPAK IC chiral column, and baseline simultaneous separations of malathion and malaoxon enantiomers were achieved with acetonitrile/water (40/60, v/v) as mobile phase at a flow rate of 0.5 mL/min. The elution orders were -/+ for both malathion and malaoxon measured by an optical rotation detector. The chiral residue analysis in soil, fruit, and vegetables was validated by linearity, recovery, precision, limit of detection (LOD), and limit of quantification (LOQ). The LODs and LOQs for the enantiomers of malathion were 1 μg/kg and 3-5 μg/kg and 0.08 μg/kg and 0.20-0.25 μg/kg for malaoxon enantiomers. Good linear calibration curves for each enantiomer in the matrices were obtained within the concentration range of 0.02-12 mg/L. The mean recoveries of the enantiomers of malathion and malaoxon ranged from 82.26% to 109.04%, with RSDs of 0.71-8.63%.The results confirmed that this method was capable of simultaneously determining the residue of malathion and malaoxon in food and environmental matrix on an enantiomeric level.

Evaluation of supercritical fluid extraction for the determination of neonicotinoid pesticides in green onion

A supercritical fluid extraction (SFE) method was presented for the determination of neonicotinoid pesticides in green onion. We optimized the SFE parameters, namely the pressure, temperature, type and concentration of the modifier solvent, and extraction time, by testing on the incurred green onion applied with four commercial neonicotinoid formulations at the harvesting stage. The analytical values of the four neonicotinoids, obtained by 5 min dynamic SFE with a 25% (v/v) methanol/supercritical carbon dioxide mixture at 80 °C and 25 MPa, were in good agreement with those obtained by solid-liquid extraction using a homogenizer. This latter homogenization method is employed as a Japanese official method for the analysis of pesticide residues in food. The SFE-to-homogenization analytical value ratios were in the range 98.8–100.0%. Spike-and-recovery testing with spiked green onion was also performed by optimized SFE. The ratios of the analytical-to-spiked concentrations for six neonicotinoids obtained by the SFE method were 96.1–102.1% for 0.4 mg/kg and 93.9–104.1% for 4.0 mg/kg spiking levels. These values satisfied the Japanese validation guidelines for the testing method of pesticides in food. These results indicate that SFE is applicable for the analysis of neonicotinoids in green onion and enables automatic extraction with a small amount of solvent.

Evaluation of pressurized liquid extraction for the determination of neonicotinoid pesticides in green onion

A pressurized liquid extraction (PLE) method was presented for the determination of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam in green onion. The critical parameters of PLE, e.g. extraction solvent, temperature, pressure, number of cycles, and static extraction time, were optimized by test on the spiked green onion with six neonicotinoids and the incurred green onion applied with four commercial neonicotinoid insecticide formulations (acetamiprid, dinotefuran, imidacloprid, and thiamethoxam). As a result, the recoveries of six neonicotinoids obtained by one cycle PLE with acetonitrile at 140 °C and 50 bar for 10 min were 94.7–99.5%. These results were acceptable according to the validation guideline for testing method of agricultural chemicals in food by Ministry of Health, Labour, and Welfare in Japan. PLE was also validated by the test on the incurred green onion. The analytical values of four neonicotinoids obtained by PLE were good agreement with those obtained by solid–liquid extraction with homogenizer, which is employed for Japanese official method for the analysis of pesticide residues in food (the ratios of analytical values obtained by PLE to those obtained by solid–liquid extraction were 99.7–101.2%). These results indicate that PLE is applicable for the determination of neonicotinoids in green onion.

Food contaminated by pesticides: a Brazilian situation overview

Consumers are becoming increasingly demanding about products quality, including new decision variables at their purchases time. Information on nutritional aspects and the use of pesticides has changed consumer preferences. The new information strategies emerged in response to new consumer’s behavioral characteristics and new competition characteristics of the food market. These strategies privilege the use of quality signals, such as labeling, traceability, certification, brand names and adoption of minimum quality standards. The main feature of Brazilian markets is the lack of minimum standards and strong information asymmetries. The market for fresh food is affected by the indiscriminate use of pesticides. The information analysis gathered by the Program for Pesticide Residue Analysis in Food (PARA) found a very worrying situation in Brazil. In this sense, with this paper, our aim is to bring more information about the pesticides contamination in the fresh food markets in Brazil. Transaction Cost Economics is adopted as a theoretical framework to examine the coordination among the agents on the chain and seek sustainable alternatives to reduce the excessive use of pesticides in food production.

Further improvements in pesticide residue analysis in food by applying gas chromatography triple quadrupole mass spectrometry (GC-QqQ-MS/MS) technologies.

Nowadays, the control of pesticide residues in food is well established. The capacity of triple quadrupole technology to satisfy the current food regulations has been demonstrated. However, the permanent high demand of consumers for more sensitive and faster testing is driving the development of improved analytical methodologies that increase the performances of sensitivity and robustness and reduce the analysis time. In this work, the feasibility of decreasing the run time to 12.4min by modifying the oven temperature program, for a multiresidue method covering 203 pesticides, was evaluated. Satisfactory sensitivity results were achieved by reaching a limit of quantitation of 2μgkg-1 for a great variety of fruits and vegetables. The validated method based on updated GC-QqQ-MS/MS has confirmed the abovementioned challenges with adequate robustness by its application to routine analyses for 69 real samples. The proposed method can represent great benefit for laboratories as it allows increasing samples throughput. It is also very useful for risk assessment studies, where the needs of low reporting limits and very wide analytical scope are necessary.

Evaluation of nanoflow liquid chromatography high resolution mass spectrometry for pesticide residue analysis in food

This article reports on the evaluation of nanoflow liquid chromatography-mass spectrometry (LC–MS) for pesticide residue analysis in food. The approach is based on the use of reversed-phase C18nano columns with an integrated emitter, so that separation, ionization and detection are performed minimizing dead volumes. The use of nanoflow not only increases ionization efficiency and minimizes ionization suppression but also boost sensitivity compared to analytical-scale LC–MS methods. The nanoflow LC system was combined with full-scan high resolution mass spectrometry using a Q-Exactive Orbitrap instrument. The analytical performance was assessed for over 60 representative pesticides in five representative commodities (tomato, baby food, orange, fruit-based jam and olive oil). The sensitivity achieved with this configuration enables the implementation of high dilution factors (eg. 1:20, 1:50 or beyond) in pesticide residue workflows without compromising sensitivity, featuring limits of quantitation in the low ng kg−1 range. Using this dilution factors, signal suppression was found negligible in most cases (<10% in most cases, especially with 1:50 dilution), so that matrix-matched standards may be skipped, thus simplifying laboratory workflows. The robustness of the nanoflow LC system and its capability to withstand long analytical runs was also evaluated. Appropriate precision in terms of peak area and retention time was obtained at different concentration levels for over 125 injections without any instrument servicing. The main benefits of the nanoflow liquid chromatography approach are the high sensitivity gain and the outstanding reduction in matrix effects thanks to the high sample dilution factors that can be implemented, along with the substantial reduction in solvent usage.

Recent analysis of veterinary drug residues in food

Recent analysis of veterinary drug residues in food

Recent Trends in Sample Preparation and Liquid Chromatography/Mass Spectrometry for Pesticide Residue Analysis in Food and Related Matrixes.

A rising interest by consumers and various governmental organizations towards the quality of food has been continuously observed. Pesticide residue analysis has a significant role in assessing food safety and quality. This article reviews the new analytical approaches for efficient extraction and reliable identification and quantification of pesticides in foodstuffs and related matrixes. Emphasis is given to the new materials used for effective extract purification. We discuss the potential and pitfalls of the different LC/MS approaches, including application of high resolution mass spectrometry in the area of pesticide residue analysis. Untargeted and retrospective screening is outlined, highlighting prospects and achievements as well as its major drawbacks.

New Trends in Pesticide Residue Analysis in Food, Dietary Supplements, and Highly Processed Consumer Products.

New Trends in Pesticide Residue Analysis in Food, Dietary Supplements, and Highly Processed Consumer Products.

Alternative QuEChERS-based modular approach for pesticide residue analysis in food of animal origin.

The approach for pesticide residue analysis in food of animal origin differs strongly from the one established for food of plant origin, as laboratories mainly focus on conventional methods for the analysis of non-polar pesticides known to accumulate in fatty tissues. However, these group-specific methods are very laborious and cost intensive and typically require extraction of fat components followed by extensive clean-up steps to remove matrix constituents. This work highlights the development and validation of a straightforward QuEChERS-derived clean-up procedure enabling facile, precise, and reliable identification and quantitation of pesticide residues in food of animal origin, which can be extended to various other commodities with moderate fat content and applied to replace traditional group-specific methods. Two additional methods for lean and highly fatty commodities complete this well-established "simplified modular system". The proposed method was in-house validated in terms of accuracy and precision, recovery and linearity as well as specificity and sensitivity on two representative commodities for food of animal origin (egg and meat). For the majority of the more than 80 pesticides investigated, satisfactory results were obtained. Procedural matrix calibration was applied for screening purposes in conjunction with GC-MS/MS or LC-MS/MS as integral part of the approach. Apparent recoveries for most of the compounds ranged from 70 to 120 % (RSD < 20%) at spiking levels of 0.01 (LOQ level) and 0.05 mg/kg. Accuracy of the method has been demonstrated by application to reference material from previous EU proficiency tests. Only in case of positive screening results a standard addition approach was applied for precise quantitation.

Detecção de resíduos de enrofloxacina por ensaio imunoenzimático e cromatografia líquida acoplada à espectrometria de massas em ovos comerciais de galinha após tratamento

A enrofloxacina é um dos antimicrobianos mais utilizados na avicultura industrial, e a deposição de resíduos em produtos avícolas, como os ovos, são de grande importância para a saúde pública. Na legislação brasileira não existe padronização do período de carência para o seu uso na produção avícola e não há Limite Máximo de Resíduo (LMR) fixado para enrofloxacina em ovos. Neste estudo, foi utilizado o kit de ELISA comercial (Bioo Scientific(r)) e a LC-MS/MS na pesquisa de enrofloxacina em ovos de 30 galinhas tratadas previamente via água de bebida, com 10mg/kg de enrofloxacina, durante cinco dias. Seis ovos foram coletados diariamente e analisados durante o tratamento e após a sua suspensão, durante 15 dias. A deposição de resíduos obteve níveis máximos no quinto dia de tratamento das aves, declinando gradativamente até não ser detectada a partir do nono dia de suspensão do tratamento. Considerando como base o LMR de 100µg/kg fixado pelo Brasil para tecidos comestíveis de aves e pela União Europeia para músculo, gordura e pele, após seis dias de suspensão do tratamento, os níveis de resíduos foram inferiores a esse limite, tendo como médias 37,43µg/kg na LC-MS/MS e 14,731µg/kg no ELISA. Dentro das condições deste estudo, um período de carência de seis dias seria mais adequado para utilização dos ovos para consumo humano. Foram detectados valores de resíduos nos ovos menores no ELISA em relação à LC-MS/MS para a mesma amostra, mas os dois métodos apresentaram concordância estatística entre si. A LC-MS/MS é o teste recomendado pela legislação brasileira para a análise de resíduos em alimentos; entretanto, pelos resultados obtidos, o kit de ELISA utilizado também pode ser aplicado na detecção de resíduos de enrofloxacina em ovos, com as vantagens de rapidez e simplicidade.

Rapid and simple extraction of lipids from blood plasma and urine for liquid chromatography-tandem mass spectrometry

A simple and fast lipid extraction method from human blood plasma and urine is introduced in this study. The effective lipid extraction from biological systems with a minimization of the matrix effect is important for the successful qualitative and quantitative analysis of lipids in liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS). The method described here is based on the modification of the quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction method, which was originally developed for pesticide residue analysis in food, for the purpose of isolating lipids from biological fluids. Applicability of QuEChERS method for lipids was evaluated by varying organic solvents for the extraction/partitioning of lipids in MgSO4/CH3COONa for the removal of water and by varying sorbents (primary secondary amines, graphitized carbon black, silica, strong anion exchange resins and C18 particles) for the dispersive solid-phase extraction (dSPE) step. This study shows that 2:1 (v/v) CHCl3/CH3OH is effective in the extraction/partitioning step and that 50mg of C18 particles (for 0.1mL plasma and 1mL of urine) are more suitable for sample cleanup for the dSPE step of the QuEChERS method. Matrix effects were calculated by comparing the recovery values of lipid standards spiked to both plasma and urine samples after extraction with those of the same standards in a neat solution using nanoflow LC-ESI-MS/MS, resulting in improved MS signals due to the decrease of the ion suppression compared to the conventional Folch method. The modified QuEChERS method was applied to lipid extracts from both human urine and plasma samples, demonstrating that it can be powerfully utilized for high-speed (<15min) preparation of lipids compared to the Folch method, with equivalent or slightly improved results in lipid identification using nLC-ESI-MS/MS.

Reduction of matrix effects in pesticide residue analysis in food by programmable temperature vaporizer

Background: The phenomenon known as the “matrix-induced chromatographic response enhancement” commonly affects the sensibility, precision, and accuracy in pesticide residue analysis. The presence of matrix effects can be given by adsorption and/or thermal decomposition of pesticides on the gas chromatograph injection port. Objective: To reduce the matrix-induced chromatographic response enhancement on pesticide residues analysis in food through the use of several operational modes of programmable temperature vaporizer inlet. Methods: The analyses were carried out in potato (Solanum tuberosum) extracts by gas chromatography with mass spectrometry detector. In this study, four programmable temperature vaporizer splitless modes were investigated: hot, pulsed, cold and solvent vent. Another topic developed in this study has to do with the influence of injection volume, assessed for the matrix effects. Results: The analysis of variance (ANOVA) (α = 0.05) indicates that when the hot splitless is used most compounds are subjected to matrix-induced chromatographic response enhancement. Furthermore, with the pulsed splitless, a decrease in the number of compounds with matrix-induced chromatographic response enhancement was found, approximately 20% compared to the classic hot splitless. Finally, a remarkable decrease in matrix-induced effects was found when cold splitless mode was used, since there was up to 55% reduction in the compounds, relative to traditional hot splitless, that showed statistical differences between responses in matrix-free standards and matrix-matched standards. Conclusions: It was found that the use of conventional hot splitless and pulsed splitless modes caused matrix-induced effects in more than 70% of the studied compounds. In addition, the results indicate that for most compounds there is an inverse relationship between matrix-induced chromatographic response enhancement and the volume of injection.