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Given that the determination of biocides in food and feed is currently not routinely done, more information on these compounds is useful for consumer's safety. This work describes a sensitive and reliable method for quantitative analysis of a wide range of biocides in dairy products and slurry feed. The method comprises acetate-buffered QuEChERS extraction without clean-up. Analyses were performed by LC-Q-Orbitrap™-MS and a full-scan acquisition event without fragmentation was followed by five fragmentation events (data-independent acquisition-DIA). The quantitative validation was performed according to SANTE/11312/2021 at 10, 50 and 200 ng g -1 spiking levels, and the results showed that the vast majority of the compounds met the criteria for trueness and precision. The LOQ was 10 ng g -1 for the majority of biocides depending on the matrix. The method was successfully applied to quantify biocides in dairy products and feed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The use of medicinal herbs has increased significantly. However, the presence of pesticide residues and mycotoxins in medicinal herbs has generated constant discussion and concern among regulatory agencies. Developing and validating an analytical method for determining pesticides and mycotoxins in medicinal plants is challenging due to the naturally occurring substances in these plants. The purpose of this work was to develop and to optimize a sensitive, accurate, precise, effective QuEChERS method for simultaneous determination of over 160 pesticide and mycotoxin residues in complex medicinal plant matrices using LC-TQ-MS/MS. A comprehensive comparison of clean-up procedures and other parameters was conducted to achieve this goal. The validation procedure was performed according to SANTE 11312/2021. More polar analytes, such as acephate, methamidophos and omethoate, presented a higher negative matrix effect in both Melissa officinalis L. and Malva sylvestris L. However, other molecules, such as spirodiclofen, showed a 24% signal enhancement in M. officinalis and a 46% signal suppression in M. sylvestris , indicating that a representative matrix-matched calibration would lead to inaccurate quantification of the analyte. Accuracy and precision were satisfactory according to SANTE 11312/2021 for 157 pesticide residues and mycotoxins in M. officinalis and for 152 molecules in M. sylvestris . LOQs at 10 µg kg -1 were achieved for 117 pesticides in M. officinalis and 99 pesticides in M. sylvestris . Among the mycotoxins, all four aflatoxins (B1, B2, G1 and G2) presented LOQs of 5 µg kg -1 , and ochratoxin A had an LOQ of 10 µg kg -1 in M. officinalis . The same LOQ values were shown for these mycotoxins in M. sylvestris , except for aflatoxin B2 and ochratoxin A, which had LOQs of 20 µg kg -1 . Moreover, in Southern Brazil, there has been no previous study on mycotoxin and pesticide contamination in medicinal herbs. Therefore, the application of this method was assessed through the analysis of forty-two real samples. Imidacloprid was found in M. officinalis , and methyl pirimiphos was found in M. sylvestris . The proposed method not only serves as a helpful tool for routine monitoring but also offers a basis for further research on risk assessment and control in food safety.

Protein has become an increasingly valuable food component with high global demand. Consequently, unconventional sources, such as industrial and agroindustrial wastes and by-products, emerge as interesting alternatives to meet this demand, considering the UN Sustainable Development Goals and the transition to a circular economy. In this context, this work presents a review of the use of Steam Explosion (SE), a green technique that can be employed as a pretreatment for various waste materials, including bones, hide/leather, feathers, and wool, aimming the extraction of protein compounds, such as low molecular weight biopeptides, gelatin, and keratin, as well as to enhance the protein functionality of grains and meals. The SE technique and the main factors affecting the process's efficiency were detailed. Promising experimental studies are discussed, along with the mechanisms responsible for protein extraction and functionality improvement, as well as the main reported and suggested applications. In general, steam explosion favored yields in subsequent extraction processes, ranging from 27 to 95%, in addition to enhancing solubility and functional protein properties. Nonetheless, it is crucial to maintain the continuity of research on this topic to drive advancements in ensuring the safety of the extracted compounds for use in consumable products and oral ingestion., Competing Interests: Conflict of interestThe authors declare that they have no conflict of interest., (© Association of Food Scientists & Technologists (India) 2023. Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.)

This paper describes an extensive study in which a multiclass QuEChERS based approach was optimized for determination of 150 pesticides and 7 mycotoxins in table olives. Three versions of QuEChERS were evaluated and compared (unbuffered, citrate and acetate buffering). A combination of EMR-Lipid cartridges and liquid nitrogen or freezer freezing out were tested for clean-up of the oily olive extracts. Analysis of the extracts were performed by LC-MS/MS triple quadrupole. The best results were achieved using acetate QuEChERS with liquid nitrogen for clean-up. For validation, organic olives were ground and spiked at 4 concentrations with pesticides and mycotoxins ( n = 5). The linearity of the calibration curves was assessed by analyzing calibration standards of 7 concentrations which were prepared separately in acetonitrile and in blank olive extract ( n = 5). The validation study demonstrated that the calculated r 2 was ≥0.99 for 144 pesticides and 6 mycotoxins, when the calibration curves were prepared in matrix extract, showing satisfactory linearity. Matrix effects were within the range of ±20% for only 46 pesticides and one mycotoxin. Then, to ensure reliable quantification, calibration standards had to be matrix-matched. In accuracy experiments 138 pesticides and 6 mycotoxins presented recoveries from 70 to 120% and RSD ≤ 20% for at least 2 of the 4 spike concentrations evaluated, being successfully validated. The integrated QuEChERS and LC-MS/MS method meet MRL for 11 of the 21 pesticides regulated for olives in Brazil and for 132 pesticides which are regulated in the EU law. Eleven commercial table olive samples were analyzed and 4 of them tested positive for pesticides. All the positive samples violate the Brazilian law and one sample violates also the European law.

Gelatin is the product resulting from collagen denaturation, which, in addition to conventional sources of extraction, can be recovered from wastes and byproducts rich in collagen widely generated by the industrial activities of poultry and cattle slaughterhouses and the fishing industry. Given the properties of good film-forming ability, nontoxicity, and biocompatibility for the addition of other compounds to obtain composite materials, gelatin is a potential polymer for the production of biodegradable films and, if extracted from waste sources, can contribute to the reduction of environmental pollution and positively impact several of the Sustainable Development Goals from the United Nations Organization. The gelatins extracted from porcine, poultry, and fish skins and untanned bovine hide wastes, or by-products can be used for the production of packaging films or edible coatings, while chromium-tanned leather wastes can be applied with mulching films in agriculture aiming at greater crop yield for food production. Also, the crosslinking of gelatin protein chains and the addition of plasticizers and other additives have shown promising results in improving gelatin films' mechanical, barrier, and solubility properties. In this sense, this paper reviewed gelatin-based films from wastes, covering the main characteristics of gelatin, techniques for film production and characterization, and applications of obtained films for the food field, in addition to considerations about social, environmental, and economic aspects., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

This work presents an easy and quick miniaturized procedure for the analysis of dithiocarbamates fungicides (DTC), by GC-MS, in yerba mate, an important product in South America. The sample amount, the volume of extracting solvent and acid solution, and the time of hot bath shaking were minimized. A clean-up procedure based on PSA, GCB and MgSO4 was studied in order to improve analytical signal and reduce GC-MS system damage. Blank yerba mate samples were spiked with thiram at equivalent CS 2 concentrations of 0.1, 0.3, 0.5 and 1 mg kg -1 . The validated method at least 2 times faster than the traditional method and was according to the latest European guidelines for pesticide residue analysis. Linearity, limits of detection and quantification, matrix effects, trueness and precision were assessed. Sixty-five commercialized samples from southern Brazil and Argentina were analyzed; 14% of samples presented CS 2 concentration greater than LOQ (0.1 mg kg -1 )., (Copyright © 2022. Published by Elsevier Ltd.)

The objective of this study was to evaluate fungal and patulin contamination, together with its correlation with the volatile compounds (VCs), in 'Fuji Mishima' apples (up to 25% decayed) under controlled atmosphere (CA) and dynamic controlled atmosphere with respiratory quotient (DCA-RQ) of 1.3 combined with different partial pressures of carbon dioxide (0.8, 1.2, 1.6 and 2.0 pCO 2 ). Fruits were stored under the above conditions for 8 months at 0.5 °C plus 7 days shelf life at 20 °C. Toxigenic fungi and patulin accumulation were found in apples from all treatments. Penicillium expansum was the most prevalent species. For all storage conditions, patulin concentrations were above the maximum level allowed in Brazil (50  μg  kg -1 ) with an exception of DCA-RQ1.3 + 0.8 kPa CO 2 . This condition, with lower pCO 2 , showed the lowest patulin accumulation, below the legal limit. The CA provided the highest patulin concentration (166 μg  kg -1 ). It was observed that fungal growth could also contribute to changes in the volatile composition. Styrene and 3-methyl-1-butanol are considered P. expansum markers in some apple cultivars and were detected in the samples. However, it was not possible to identify volatile organic compounds (VOCs) that are biomarkers from P. expansum , because there were other fungi species present in all samples. In this study, styrene, n-decanoic acid, toluene, phenol and alpha-farnesene were the compounds that showed the most positive correlation with patulin accumulation. On the other hand, a negative correlation of patulin with acids has been shown, indicating that in treatments with a higher patulin concentration there were less acidic compounds.

Ruellia angustiflora (Acanthaceae) is known as flower-of-fire, and its leaves are traditionally employed to promote wound healing. This study was aimed at extracting and characterizing the chemical constituents of the extracts of R. angustiflora obtained by ultrasound-assisted and supercritical fluid extractions, and subsequently investigate their antioxidant potential and cyto-genotoxicity. The extract obtained by ultrasound (UAE-EtOH) was characterized by ultraperformance liquid chromatography-mass spectrometer (UPLC-MS), and the extract obtained via supercritical fluid (SFE-CO 2 ) by gas chromatograph-mass spectrometer (GC-MS). The antioxidant potential was verified by the antiradical activity against the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH), and the cyto-genotoxicity evaluation to test cell viability and DNA damage was performed in peripheral blood mononuclear cells (PBMC) cultures. The SFE-CO 2 extract presented some fatty acids, triterpenes, tetraterpenes, tocopherols and phytosterols. The UAE-EtOH extract contained phenolic acids and flavonoids, and showed the highest antioxidant capacity. Neither extract was genotoxic or cytotoxic at the tested concentrations.

Hesperozygis ringens is a plant of the Lamiaceae family which is restricted to the Southern region of Brazil. It is popularly used as an insecticide, but knowledge on it is very scarce. This study aimed to determine the chemical markers of H. ringens extracts obtained via ultrasound-assisted (UAE-EtOH) and supercritical fluid (SFE-CO 2 ) extractions. UAE-EtOH and SFE-CO 2 extracts were characterised by UPLC-MS and GC-MS, respectively. Both products had their antioxidant activity, cytotoxicity and genotoxicity evaluated. Twelve compounds were found in the UAE-EtOH extract, including phenolic acids and flavonoids; the SFE-CO 2 extract contained terpenes and phytosterols. The UAE-EtOH extract showed a greater antioxidant activity. Neither extract presented cytotoxicity or genotoxicity against human mononuclear blood cells.

Two simple and low-cost QuEChERS approaches were optimized and validated for multimycotoxin determination in grains by UPLC-MS/MS and applied to assess effectiveness of controlled atmosphere (CA) storage in preventing mycotoxin contamination. Common bean, soybean, and maize samples were stored for 6 months. CA treatments were conducted varying O 2 and CO 2 partial pressures, temperatures, and moisture contents of the chambers. In the validation study for common bean and maize, 8 out of 11 mycotoxins were successfully validated. For soybean, 10 out of 11 mycotoxins were validated. Aflatoxin B1 was detected in all commodities. Statistical tests suggest that storage temperature played a key role in aflatoxin B1 concentrations in common bean and soybean, but had no influence on maize. Maize was also positive for fumonisins B1 and B2. Differences in fumonisin concentrations were not significant among different treatments. Concentrations of aflatoxin B1 in some samples exceeded legislation's maximum levels. Thus, some of the CA treatments applied were effective in preventing mycotoxin contamination in common bean and soybean but were not effective for maize.

Food matrices consist of many components with different physical and chemical properties that may influence instrumental robustness. The soybean contains fatty coextractives which may have a deleterious effect on the gas chromatography (GC) system. In this study, the efficiencies of PSA, C 18 OH, C 18 , silica, aluminum oxide, and Florisil, as dSPE clean-up sorbents, were evaluated by the high-performance liquid chromatography (HPLC) diode-array detector and evaporative light-scattering detector analysis. The dithiocarbamates in soybean samples are determined as CS 2 using acidic hydrolysis and isooctane partitioning, followed by GC-PFPD and GC-ITD-MS analyses. The linearity of the analytical curves, the instrument limit of detection matrix effects, the trueness and precision, and the method limit of quantification (LOQ) were assessed in the validation study. Milled soybean was spiked with thiram solution at three concentration levels (corresponding to 0.05, 0.1, and 0.5 mg CS 2 kg -1 ) for recovery determination. Silica appeared to be an effective and cheap sorbent to remove coextracted matrix components without causing any CS 2 losses. Recoveries were in the range of 68-91%, with relative standard deviations ≤ 8.7%. The method LOQ was 0.05 mg CS 2 kg -1 , and both GC-ITD-MS and GC-PFPD systems appeared to be appropriate and complementary to determine dithiocarbamate residues in soybean extracts.

The goal of this survey was to evaluate the presence and concentration as well as the co-occurrence of legislated and non-legislated mycotoxins in wheat flour samples from Brazil. A total of 200 wheat flour samples were analysed by a validated multi-mycotoxins method. DON was the mycotoxin with the highest occurrence, being present in 100% of the analysed samples and showing contamination in both years and regions (53-2905 μg kg -1 ). ZEN was detected in 51% (-1 ) of the samples, while T-2 (not legislated in Brazil) was detected in 13.5% (-1 ) of all samples. Regarding co-occurrence, all samples were contaminated with two to three mycotoxins.

Persistent organic pollutants are characterised by their chemical structure, environmental persistence and toxicity to human and wildlife populations. The production of these chemicals is regulated and restricted. However, they continue to be detected in the environment. In this study, the occurrence of 11 congeners of polychlorinated biphenyls (PCBs 28, 52, 77, 81, 101, 118, 126, 138, 153, 169, and 180) was investigated in 90 honey samples produced in the Brazilian state of Rio Grande do Sul. The samples were from different municipalities, production systems and floral origins. Extraction was performed using the modified QuEChERS method (Quick, Easy, Cheap, Effective, Rugged and Safe) followed by gas chromatography with micro-electron capture detector. The results showed the presence of four congeners (PCBs 28, 77, 81, 101) in 15 honey samples confirming the environmental contamination in Southern Brazil. Among the contaminated samples, no significant differences were identified regarding the production system and floral origin.

A quick and efficient method was optimized and validated to determine chlorpyrifos in biobeds using ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS). Chlorpyrifos was extracted from the matrix with 30 mL of a mixture of acetone, phosphoric acid and water 98:1:1 (v/v/v). After homogenization, centrifugation and filtration, 125 µL of the extract was evaporated and reconstituted in 5 mL of methanol acidified with 0.1% acetic acid. Validation was performed by studying analytical curve linearity (r 2 ), estimated instrument and method limits of detection and limits of quantification (LOD i , LOD m , LOQ i and LOQ m , respectively), accuracy, precision (expressed as relative standard deviation, RSD), and matrix effect. Accuracy and precision were determined from the amount of pesticide recovered from biobed blank samples (i.e. without pesticide residue) spiked with chlorpyrifos at three different concentrations (2, 10 and 50 mg kg -1 ), with seven replicates at each concentration. For all three concentrations studied, the average recovery values obtained were between 96 and 115% with RSD values lower than 20%. The validated LOQ obtained was 2 mg kg -1 (from recovery studies) and the matrix effect observed was lower than ±20%, which demonstrated that there was neither considerable suppression nor enhancement of the analyte signal. The biobed system efficiently degraded chlorpyrifos in both 1) simulation of accidental spillage and 2) application of diluted pesticide solution. In the latter case, all the values obtained at the final sampling time (14 months) were below the validated LOQ m ., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A probabilistic dietary risk assessment on mycotoxins was conducted using the Monte Carlo Risk Assessment software, with consumption data from the 2008/2009 Brazilian Household Budget Survey for individuals who were at least 10 years old and occurrence data for 646 samples of rice, maize, wheat, and their products, collected in the Federal District and in the state of Rio Grande do Sul, Brazil. Processing factors were estimated and applied to concentration data. Chronic exposure was estimated for fumonisins (free and bound/hidden), deoxynivalenol (DON) (including the acetylated forms) and zearalenone (ZON) (including alfa-zearalenol) and acute exposure was estimated for DON. For the general population, the chronic exposure exceeded the safe exposure levels at the 95P for DON and at the 99P for fumonisins. Additionally, safe level exceedance occurred at the 97.5P for fumonisins and at the 95P for DON for teenagers, as well as at the 99P for fumonisins for women of child-bearing-age. No exceedances were found for chronic exposure to ZON and acute exposure to DON. Maize couscous contributed most of the total fumonisins (91%) and ZON intakes (~40%) and bread to total intake of DON (~30%). Further studies should be conducted with updated Brazilian consumption data, which should include information for individuals aged less than 10 years old., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Background: Common bean is a staple food in Latin America and Africa; however, studies about contamination of common bean with pesticides are rarely reported. So, the goals of this study were to validate a multiresidue method and apply it in monitoring of pesticides in common beans. Extraction was performed applying the QuEChERS (quick, easy, cheap, effective, rugged, and safe) approach to ground samples. Octadecylsilane and primary-secondary amine were used for clean-up, and a solvent exchange step was performed before injection for gas chromatography-tandem mass spectrometry analysis. Method validation was done analyzing blank samples spiked at 20, 30, 50, and 100 μg kg -1 (n = 5). Linearity and linear range were assessed by the analysis of standard solutions at concentrations of 5, 15, 25, 50, 75, 100, and 150 μg L -1 ., Results: The method was successfully validated for 91 (64.1%) of the 142 compounds studied (139 pesticides and three degradation products). Limits of quantification were equal to 20 μg kg -1 , 30 μg kg -1 , 50 μg kg -1 , and 100 μg kg -1 for 18 (12.7%), 17 (12.0%), 21 (14.8%) and 35 (24.6%) compounds respectively. Fifteen (10.6%) compounds were not detected at any level, and 36 (25.4%) did not fulfill the requirements for a quantitative method. Sixteen common bean samples of South of Brazil were analyzed. Two samples were positive: one for tebuconzole and a second for picoxystrobin, permethrin, and cyproconazole. Cyproconazole is not allowed for use in the common bean crop, its use being a violation., Conclusion: As demonstrated, the validated approach is suitable for pesticide residues determination in common bean. Results of the sample analysis show that the control of pesticide residues in common bean is necessary to ensure food safety. © 2020 Society of Chemical Industry., (© 2020 Society of Chemical Industry.)

A simple and rapid method for simultaneous determination of pesticides and mycotoxins in red wine is presented. Sample preparation approach, called direct injection, consists of a sequence of only three steps: centrifugation, dilution and filtration. The analysis of extracts were performed by UPLC-MS/MS for determination of pesticides and mycotoxins. The method was assessed for linearity, limits of detection and quantification, matrix effects, selectivity, accuracy and precision. For recovery experiments, mycotoxins were divided in two groups according to their sensitivity in the UPLC-MS/MS system. More than 80% of the mycotoxins were reliably quantified at the lowest spike level studied (1 μg kg -1 for group 1 and 50 μg kg -1 for group 2). From the 185 evaluated pesticides, 144 showed acceptable results at 10 μg kg -1 , the lowest spiked level. Matrix effects were, in most of the cases, negative, and that was observed for both pesticides and mycotoxins., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Abstract: The aim of this study was to evaluate the mycotoxicological quality of wheat flours used by bakeries from the North Region in Rio Grande do Sul state, Brazil, regarding the presence of mycotoxins. On collecting type-1 refined wheat flour, a conglomerate sampling from 13 cities and 3 bakeries per city (n = 39), selected from the defined region was performed. The mycotoxins analysis was using QuEChERS method and UPLC-MS/MS analysis. As a result, 100% of samples presented contamination by DON, with concentrations ranging from 76.7 to 3630.2 µg kg -1 and ZON was found in one sample (26.7 µg kg -1 ), which represented 2.6% of the analyzed wheat flours. Other mycotoxins (AFB1, AFB2, AFG1, AFG2, DAS, HT-2 toxin, OTA, FB1 and FB2) were not detected in the analyzed samples., Competing Interests: Compliance with ethical standardsThe authors declare no conflict of interest.

The goal of this study was to evaluate patulin contamination in 'Galaxy' and 'Fuji Kiku' apples subjected to controlled atmosphere (CA) and dynamic controlled atmosphere (DCA) conditions. Experiments were performed and fruit were stored for nine months under refrigeration plus 7 days shelf life at 20 °C. CA and DCA were not effective in preventing patulin production in either 'Galaxy' or 'Fuji Kiku' apples. Healthy fruit were not contaminated with patulin, even when stored together with decayed apples. For 'Galaxy' apples, application of 1-methylcyclopropene increased the percentage of fruit with decay and patulin contamination. Patulin concentrations were above the maximum limit (50 μg kg -1 ) established in the Brazilian legislation, meaning the use of CA and DCA conditions were not advantageous in preventing patulin accumulation. In 'Fuji Kiku' apples, there was no significant difference in patulin concentration among CA, DCA-CF and DCA-RQ 1.3 treatments, and all were below the maximum., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In order to evaluate the efficiency of biobeds on DTC degradation, the aim of this study was to apply, optimize and validate a method to determine dithiocarbamate (mancozeb) in biobeds using gas chromatography-tandem mass spectrometry (GC-MS). The DTC pesticide mancozeb was hydrolysed in a tin (II) chloride solution at 1.5% in HCl (4 mol L -1 ), during 1 h in a water bath at 80 °C, and the CS 2 formed was extracted in isooctane. After cooling, 1 mL of the organic layer was transferred to an auto sampler vial and analyzed by GC-MS. A complete validation study was performed and the following parameters were assessed: linearity of the analytical curve (r 2 ), estimated method and instrument limits of detection and limits of quantification (LODm, LODi, LOQm and LOQi, respectively), accuracy (recovery%), precision (RSD%) and matrix effects. Recovery experiments were carried out with a standard spiking solution of the DTC pesticide thiram. Blank biobed (biomixture) samples were spiked at the three levels corresponding to the CS 2 concentrations of 1, 3 and 5 mg kg -1 , with seven replicates each (n = 7). The method presented satisfactory accuracy, with recoveries within the range of 89-96% and RSD ≤ 11%. The analytical curves were linear in the concentration range of 0.05-10 µg CS 2 mL -1 (r 2 > 0.9946). LODm and LOQm were 0.1 and 0.5 mg CS 2 kg -1 , respectively, and the calculated matrix effects were not significant (≤ 20%). The validated method was applied to 80 samples (biomixture), from sixteen different biobeds (collected at five sampling times) during fourteen months. Ten percent of samples presented CS 2 concentration below the LOD (0.1 mg CS 2 kg -1 ) and 49% of them showed results below the LOQ (0.5 mg CS 2 kg -1 ), which demonstrates the biobeds capability to degrade DTC., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This paper describes the optimization and validation of an acetonitrile based method for simultaneous extraction of multiple pesticides and mycotoxins from raw coffee beans followed by LC-ESI-MS/MS determination. Before extraction, the raw coffee samples were milled and then slurried with water. The slurried samples were spiked with two separate standard solutions, one containing 131 pesticides and a second with 35 mycotoxins, which were divided into 3 groups of different relative concentration levels. Optimization of the QuEChERS approach included performance tests with acetonitrile acidified with acetic acid or formic acid, with or without buffer and with or without clean-up of the extracts before LC-ESI-MS/MS analysis. For the clean-up step, seven d-SPE sorbents and their various mixtures were evaluated. After method optimization a complete validation study was carried out to ensure adequate performance of the extraction and chromatographic methods. The samples were spiked at 3 concentrations levels with both mycotoxins and pesticides (with 6 replicates at each level, n = 6) and then submitted to the extraction procedure. Before LC-ESI-MS/MS analysis, the acetonitrile extracts were diluted 2-fold with methanol, in order to improve the chromatographic performance of the early-eluting polar analytes. Calibration standard solutions were prepared in organic solvent and in blank coffee extract at 7 concentration levels and analyzed 6 times each. The method was assessed for accuracy (recovery %), precision (RSD%), selectivity, linearity (r 2 ), limit of quantification (LOQ) and matrix effects (%)., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Mycotoxins occurrence in wheat grains impose risks to human and animal health. The southern Brazil has favorable weather conditions for Fusarium graminearum infections and consequently for mycotoxins accumulation on grains. The goal of this study was to evaluate the behavior of new wheat commercial genotypes to Fusarium Head Blight (FHB), to control performance of new fungicide formulations and their relationship with mycotoxins concentration in grains. The manly mycotoxin occurrence on wheat grains in southern Brazil was deoxynivalenol (DON). Two cultivars showed high DON concentration above the tolerance limits (>3000 μg kg -1 ). Many other mycotoxins monitored presented concentrations below method detection limit. Satisfactory levels of fungicide effectiveness were achieved against F. graminearum. Some fungicides promoted a satisfactory decrease on DON accumulation in grains. The best results were obtained when prothioconazole was present. SDHI (Succinate dehydrogenase inhibitors) + QoI (Quinone outside inhibitors) fungicides showed benefic effects at FHB control at field, but it did not promote satisfactory reduction on DON contamination. Fungicides can be used satisfactory for FHB control and reduce DON contamination in grains in southern Brazil. The presence of prothioconazole should be recommended. Some genotypes showed high DON concentration and it was not directly related with FHB severity at field.

This study describes the optimization and single-laboratory validation of a single residue method for determination of two bipyridylium herbicides, paraquat and diquat, in cowpeas by UPLC-MS/MS in a total run time of 9.3min. The method is based on extraction with an acidified methanol-water mixture. Different extraction parameters (extraction solvent composition, temperature, sample extract filtration, and pre-treatment of the laboratory sample) were evaluated in order to optimize the extraction method efficiency. Isotopically labeled internal standards, Paraquat-D6 and Diquat-D4, were used and added to the test portions prior to extraction. The method validation was performed by analyzing spiked samples at three concentrations (10, 20 and 50μgkg(-1)), with seven replicates (n=7) for each concentration. Linearity (r(2)) of analytical curves, accuracy (trueness as recovery % and precision as RSD%), instrument and method limits of detection and quantification (LOD and LOQ) and matrix effects were determined. Average recoveries obtained for diquat were between 77 and 85% with RSD values ⩽20%, for all spike levels studied. On the other hand, paraquat showed average recoveries between 68 and 103% with RSDs in the range 14.4-25.4%. The method LOQ was 10 and 20μgkg(-1) for diquat and paraquat, respectively. The matrix effect was significant for both pesticides. Consequently, matrix-matched calibration standards and using isotopically labeled (IL) analogues as internal standards for the target analytes are required for application in routine analysis. The validated method was successfully applied for cowpea samples obtained from various field studies., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The goal of this work was to evaluate the efficiency of several sorbents on removal fats from edible oils (olive, soya and sunflower) during the clean-up step for posterior determination of 165 pesticides by UHPLC-QqQ-MS/MS system. The extraction procedure employed in this work was the citrate version of QuEChERS method followed by a step of freezing out with dry ice and clean-up evaluation using i) PSA with magnesium sulfate (d-SPE); ii) magnesium sulfate and Z-sep sorbent (d-SPE); iii) Z-sep (column SPE) and iv) Agilent Bond Elut QuEChERS Enhanced Matrix Removal-Lipid (EMR-Lipid). After evaluation of the recovery results at 10, 20 and 50μgkg(-1), the EMR-Lipid showed important advantages comparing to the other sorbents evaluated, such as better recovery rates and RSD%. The method was validated at the three concentrations described above. Analytical curves linearity was evaluated by spiking blank oil samples at 10, 20, 50, 100 and 500μgkg(-1). The method demonstrated good recoveries values between the acceptable range of 70-120% and RSD%<20 for most of evaluated pesticides. In order to evaluate the performance of the method, this same procedure was employed to other oils such as soya and sunflower with very good results., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this study, a very sensitive method was validated to determine pesticides residues in fruit jams using micro flow liquid chromatography-tandem mass spectrometry (µLC-MS/MS). A slurry of the fruit jams and water was prepared to yield homogeneous samples. Because of the high sensitivity achieved with the µLC-MS/MS equipment and to minimize matrix effects, the QuEChERS extracts were diluted 30-fold before the analysis. The validation was performed analyzing spiked samples at 9 and 45 µg kg(-1) (n=5). The method met validation criteria of 70-120% recovery and RSD≤20% for 92% of the 107 pesticides evaluated. The reporting limit (RL) was 9 and 45 µg kg(-1) for respectively 66% and 26% of the analytes, 5% of the compounds did not fulfill the requirements for validation and 3% were not detected at the studied concentrations. The validated method was applied to the analysis of 51 different fruit jam samples from Brazil and Spain and pesticide residues were detected in 41 samples, 26 of which contained at least one pesticide at concentration >10 µg kg(-1)., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A fast and efficient multimethod for the determination of 36 mycotoxins in wine, using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), was developed, optimized, validated and implemented in routine analysis. A simplified, quick extraction was performed with acetonitrile, derived from the QuEChERS (quick, easy, cheap, effective, rugged and safe) approach, which was traditionally developed for pesticides analysis. This study aimed at a single extraction and chromatographic separation for 36 mycotoxins. Optimization tests were performed to find the proper ratio of wine: water and extraction solvent and the need for an additional buffering step with ammonium formate/formic acid and a dispersive SPE cleanup with various sorbents. The dSPE steps did not show significant improvement in analysis results, therefore, it was not applied in the final method to be validated. The mycotoxins were separated and detected on a UPLC-MS/MS system, used in the ESI positive ionization mode. The various mycotoxins were divided in three different concentration level groups, according to their sensitivity in UPLC-MS/MS. The validation was performed by analyzing recovery samples at three different spike levels with six replicates (n=6) at each level. Linearity (r(2)) of calibration curves, accuracy (recovery %), instrument limits of detection and method limits of quantification (LOD and LOQ), precision (RSD%) and matrix effects (%) were determined for each individual mycotoxin. From the 36 mycotoxins analyzed by UPLC-MS/MS (ESI+), 35 showed average recoveries in the range 70-120%, and 86% of these with a RSD≤20% at the lowest spike level (for Group I, II and III, respectively, 1, 50 and 10 µg kg(-1)). The higher spike levels showed even better results. Only nivalenol could not be quantified at any concentration level. The method LOQ for 86% of the mycotoxins studied was the lowest spike level tested. The matrix effect observed was low for most mycotoxins analyzed and had no significant influence on the analytical results obtained. The developed procedure was applied successfully in routine analysis in a survey of wine samples originating from different countries., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In this study, a new gas chromatography-mass spectrometry (GC-MS) method, using the very selective negative chemical ionization (NCI) mode, was developed and applied in combination with a modified acetonitrile-based extraction method (QuEChERS) for the analysis of a large number of pesticide residues (51 pesticides, including isomers and degradation products) in green coffee beans. A previously developed integrated sample homogenization and extraction method for both pesticides and mycotoxins analysis was used. An homogeneous slurry of green milled coffee beans and water (ratio 1:4, w/w) was prepared and extracted with acetonitrile/acetic acid (1%), followed by magnesium sulfate addition for phase separation. Aliquots from this extract could be used directly for LC-MS/MS analysis of mycotoxins and LC-amenable pesticides. For GC-MS analysis, a further clean-up was necessary. C18- and PSA-bonded silica were tested as dispersive solid-phase extraction (d-SPE) sorbents, separate and as a mixture, and the best results were obtained using C18-bonded silica. For the optimal sensitivity and selectivity, GC-MS detection in the NCI-selected ion monitoring (SIM) mode had to be used to allow the fast analysis of the difficult coffee bean matrix. The validation was performed by analyzing recovery samples at three different spike concentrations, 10, 20 and 50 μg kg(-1), with 6 replicates (n=6) at each concentration. Linearity (r(2)) of calibration curves, estimated instrument and method limits of detection and limits of quantification (LOD(i), LOD(m), LOQ(i) and LOQ(m), respectively), accuracy (as recovery %), precision (as RSD%) and matrix effects (%) were determined for each individual pesticide. From the 51 analytes (42 parent pesticides, 4 isomers and 5 degradation products) determined by GC-MS (NCI-SIM), approximately 76% showed average recoveries between 70-120% and 75% and RSD ≤ 20% at the lowest spike concentration of 10 μg kg(-1), the target method LOQ. For the spike concentrations of 20 and 50 μg kg(-1), the recoveries and RSDs were even better. The validated LOQ(m) was 10, 20 and 50 μg kg(-1) for respectively 33, 3 and 6 of the analytes studied. For five compounds, the European Union method performance requirements for the validation of a quantitative method (average recoveries between 70-120% and repeatability RSD ≤ 20%) were not achieved and 4 problematic pesticides (captan, captafol, folpet and dicofol) could not be detected as their parent compound, but only via their degradation products. Although the matrix effect (matrix-enhanced detector response) was high for all pesticides studied, the matrix interference was minimal, due to the high selectivity obtained with the GC-NCI-MS detection. Matrix-matched calibration for applying the method in routine analysis is recommended for reliable quantitative results., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Two simple and straightforward sample preparation methods were developed for the multiresidue analysis of post-emergence herbicides in loam soil that are commonly used in rice crop cultivation. A number of strategic soil extraction and cleanup methods were evaluated. The instrumental analysis was performed by HPLC with a diode array detector. The best compromise between the recoveries (69-98%) and good repeatability (RSD < 15%) was obtained using either methanol or methanol-ethyl acetate (70 + 30, v/v) as extraction solvents without any further cleanup. For the first time, residues of metsulfuron methyl, bensulfuron ethyl, bentazone, cyhalofop butyl, pyrazosulfuron ethyl, propanil, and clomazone were analyzed simultaneously. Quinclorac and bispyribac sodium were also assayed, but their recoveries were below 50%. Both methods had an LOD of 0.7 microg/kg and could accurately determine the residues at the 2 microg/kg level. These two methods could not be applied directly to other soil types as the recoveries strongly depended on the soil composition. The developed methodologies were successfully applied in monitoring 87 real-world soil samples, in which only propanil (6 to 12 microg/kg) and clomazone (15 to 20 microg/kg) residues could be detected.

An acetonitrile-based extraction method for the analysis of 169 pesticides in soya grain, using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in the positive and negative electrospray ionization (ESI) mode, has been optimized and validated. This method has been compared with our earlier published acetone-based extraction method, as part of a comprehensive study of both extraction methods, in combination with various gas chromatography-(tandem) mass spectrometry [GC-MS(/MS)] and LC-MS/MS techniques, using different detection modes. Linearity of calibration curves, instrument limits of detection (LODs) and matrix effects were evaluated by preparing standards in solvent and in the two soya matrix extracts from acetone and acetonitrile extractions, at seven levels, with six replicate injections per level. Limits of detection were calculated based on practically realized repeatability relative standard deviations (RSDs), rather than based on (extrapolated) signal/noise ratios. Accuracies (as % recoveries), precision (as repeatability of recovery experiments) and method limits of quantification (LOQs) were compared. The acetonitrile method consists of the extraction of a 2-g sample with 20 mL of acetonitrile (containing 1% acetic acid), followed by a partitioning step with magnesium sulphate and a subsequent buffering step with sodium acetate. After mixing an aliquot with methanol, the extract can be injected directly into the LC-MS/MS system, without any cleanup. Cleanup hardly improved selectivity and appeared to have minor changes of the matrix effect, as was earlier noticed for the acetone method. Good linearity of the calibration curves was obtained over the range from 0.1 or 0.25 to 10 ng mL(-1), with r(2)>or=0.99. Instrument LOD values generally varied from 0.1 to 0.25 ng mL(-1), for both methods. Matrix effects were not significant or negligible for nearly all pesticides. Recoveries were in the range 70-120%, with RSD

In this study, a new modulator that is simple, robust and presents low operation costs, was developed. This modulator uses compressed air to cool two small portions in the first centimeters of the second chromatographic column of a comprehensive multidimensional gas chromatography (GCxGC) system. The results show a variation in the peak area less than 3 and 5% to alkanes and pesticides, respectively. The standard deviations for the retention times in the first and second dimension are around 0.05 min and 0.05s for all the compounds. The system was optimized with n-alkanes. The GCxGC system proposed was applied in the determination of pyrethroid pesticides (bifenthrin, cypermethrin, deltamethrin, fenvalerate, esfenvalerate, cis- and trans-permethrin) in grape samples. Samples were extracted by the mini-Luke modified method and pesticides were quantified by comprehensive multidimensional gas chromatography with micro electron-capture detection (microECD). The values of method limit of quantification (LOQ) were 0.01-0.02 mg kg(-1) for all studied pyrethroid and the values of recovery were between 94.3 and 115.2%, with good precision (RSD<18.4%), demonstrating that the performance of the total method consisting of a modified Luke extraction method and determination by GCxGC-microECD are satisfactory. This study also showed that the system using a modulator with a double jet of compressed air has the potential for application in the analysis of a wider range of pesticide residues in other commodities since it provides low values of LOQ with acceptable accuracy and precision.

Part of a comprehensive study on the comparison of different extraction methods, GC-MS(/MS) and LC-MS/MS detection methods and modes, for the analysis of soya samples is described in this paper. The validation of an acetone-based extraction method for analysis of 169 pesticides in soya, using LC-MS/MS positive and negative electrospray ionisation (ESI) mode, is reported. Samples (5 g) were soaked with 10 g water and subsequently extracted with 100 mL of a mixture of acetone, dichloromethane and light petroleum (1:1:1), in the presence of 15 g anhydrous sodium sulphate. After centrifugation, aliquots of the extract were evaporated and reconstituted in 1.0 mL of methanol, before direct injection of the final extract (corresponding with 0.05 g soya mL(-1)) into the LC-MS/MS system. Linearity, r(2) of calibration curves, instrument limit of detection/quantitation (LOD/LOQ) and matrix effect were evaluated, based on seven concentrations measured in 6-fold. Good linearity (at least r(2)> or =0.99) of the calibration curves was obtained over the range from 0.1 or 0.25 to 10.0 ng mL(-1), corresponding with pesticide concentrations in soya bean extract of 2 or 5-200 microg kg(-1). Instrument LOD values generally were 0.1 or 0.25 ng mL(-1). Matrix effects were negligible for approximately 90% of the pesticides. The accuracy, precision and method LOQ were determined via recovery experiments, spiking soya at 10, 50, 100 microg kg(-1), six replicates per level. In both ESI modes, method LOQ values were mostly 10 or 50 microg kg(-1) and more than 70% of pesticides analysed by each mode met the acceptability criteria of recovery (70-120%) and RSD (< or =20%), at one or more of the three levels studied. A fast, easy and efficient method with acceptable performance was achieved for a difficult matrix as soya, without cleanup.