Determination of pesticides in fruit and fruit juices by chromatographic methods. An overview

In order to combat a variety of pests, pesticides are widely used in fruits. Several extraction procedures (liquid extraction, single drop microextraction, microwave-assisted extraction, pressurized liquid extraction, supercritical fluid extraction, solid-phase extraction, solid-phase microextraction, matrix solid-phase dispersion, and stir bar sorptive extraction) have been reported to determine pesticide residues in fruits and fruit juices. The significant change in recent years is the introduction of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods in these matrices analysis. A combination of techniques reported the use of new extraction methods and chromatography to provide better quantitative recoveries at low levels. The use of mass spectrometric detectors in combination with liquid and gas chromatography has played a vital role to solve many problems related to food safety. The main attention in this review is on the achievements that have been possible because of the progress in extraction methods and the latest advances and novelties in mass spectrometry, and how these progresses have influenced the best control of food, allowing for an increase in the food safety and quality standards

Validation and evaluation of selected organic pollutants in shrimp and seawater samples from the nw portuguese coast

Funding Information: Funding: This work was supported by UIDB/50006/2020 by the Fundação para a Ciência e a Tecnologia (FCT)/Ministério da Ciência, Tecnologia e Ensino Superior (MCTES) through national funds. The authors also thank FCT and the European Union’s H2020 Research and Innovation Program for funding through the project Systemic—An integrated approach to the challenge of sustainable food systems: adaptive and mitigatory strategies to address climate change and malnutrition. Maria Luz Maia is grateful to FCT) and ESF (European Social Fund) through POCH (Programa Operacional Capital Humano) for the PhD grant SFRH/BD/128817/2017. Funding Information: This work was supported by UIDB/50006/2020 by the Funda??o para a Ci?ncia e a Tecnologia (FCT)/Minist?rio da Ci?ncia, Tecnologia e Ensino Superior (MCTES) through national funds. The authors also thank FCT and the European Union?s H2020 Research and Innovation Program for funding through the project Systemic?An integrated approach to the challenge of sustainable food systems: adaptive and mitigatory strategies to address climate change and malnutrition. Maria Luz Maia is grateful to FCT) and ESF (European Social Fund) through POCH (Programa Operacional Capital Humano) for the PhD grant SFRH/BD/128817/2017. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.The development of coastal regions has contributed to the intensification of environmental contamination, which can accumulate in aquatic biota, such as shrimps. These crustaceans, besides being delicious and being a good source of nutrients, can also accumulate environmental pollutants. Amongst others, these include organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs), brominated flame retardants (BFRs), polychlorinated biphenyls (PCBs) and synthetic musks (SMs). These pollutants, classified as endocrine disruptors, are related to adverse effects in humans and since one of the major routes of exposition is ingestion, this is a cause for concern regarding their presence in food. The aim of the present study was to quantify the presence of environmental pollutants in shrimp samples and in the water from their habitat along the northwest Portuguese coast. In seawater samples, only two OCPs (lindane and DDD) and one BFR (BTBPE) were detected, and in shrimp samples, one OCP (DDD) and three SMs (HHCB, AHTN and ketone) were found. Bioaccumulation and the risk assessment of dietary exposure of SMs in shrimp samples were investigated. It was observed that all shrimp samples analyzed significantly presented bioaccumulation of the three SMs found. Concentrations of SMs detected in shrimp samples do not present a health risk for the adult Portuguese population.publishersversionpublishe

Assessment of synthetic musks, polychlorinated biphenyls and brominated flame retardants in adipose tissue of obese northern Portuguese women – Metabolic implications

Funding Information: This work was financially supported by Portuguese national funds through projects UIDB/50006/2020 , UIDP/50006/2020 , and LA/P/0008/2020 , from the Fundação para a Ciência e a Tecnologia (FCT)/ Ministério da Ciência, Tecnologia e Ensino Superior (MCTES). Funding Information: S. Sousa is grateful to FCT and ESF (European Social Fund) through POCH (Programa Operacional Capital Humano) for the Ph.D. grant ( SFRH/BD/137516/2018 and COVID/BD/153231/2023 ). The authors thank the General Surgery Department of Hospital de São João (Porto, Portugal) for the human adipose tissue samples and to all patients that consent to participate. Publisher Copyright: © 2023 Elsevier B.V.Obesity is a worldwide multifactorial disease linked to persistent pollutants exposure amongst other factors. Humans are daily exposed to an assort of pollutants, such as polychlorinated biphenyls, brominated flame retardants and synthetic musks. These, also known as endocrine disruptors, were all found in human adipose tissue, the preferable matrix for the assessment of long-time accumulation. There are several accounts of hazardous effects of polychlorinated biphenyls and brominated flame retardants on the human organism, whereas for synthetic musks little is still known. Hence, in this study, the levels of polychlorinated biphenyls, brominated flame retardants, and synthetic musks were measured in samples of adipose tissue from 188 Obese Portuguese Women (subcutaneous or scAT and visceral or vAT). After which, associations between pollutants levels and several biochemical parameters from assorted of metabolic processes were studied. Brominated flame retardants were not found in any sample analysed, synthetic musks were found in all the samples analysed (100 % detection frequency) with median levels of 0.4 ± 0.6 μg/g in scAT and 0.4 ± 0.7 μg/g in vAT and polychlorinated biphenyls were found in the majority of samples (<90 % detection frequency) with median levels of 0.1 ± 0.3 μg/g in both tissues. Median concentrations of synthetic musks and polychlorinated biphenyls were similar between scAT and vAT. In total 315 associations were achieved with pollutants levels in adipose tissue, including 273 Spearman's correlations (146 negative and 127 positive). Additionally, 3 multiple linear regressions were achieved. Synthetic musks behave differently than polychlorinated biphenyls and other well-known persistent pollutants in the human body. Synthetic musks behaviour is yet poorly known and their high levels and detection frequencies enforces the need for more studies about their impact on human health. Understanding how these chemicals alter the metabolism is crucial knowledge and hopefully will contribute to improving the treatment and follow-up of obesity in the female population.publishersversionpublishe

Implication of menopause and ageing

Funding Information: S. Sousa is grateful to FCT and European Social Fund through Programa Operacional Capital Humano for the Ph.D . grant ( SFRH/BD/137516/2018-COVID/BD/153231/2023 ). The authors thank the General Surgery Department of Hospital de São João (Porto, Portugal) and to all patients that consented to participate. Funding Information: This work was financially supported by Portuguese national funds through projects UIDB/50006/2020 , UIDP/50006/2020 , and LA/P/0008/2020 , from the Fundação para a Ciência e a Tecnologia (FCT)/Ministério da Ciência , Tecnologia e Ensino Superior . Funding Information: S. Sousa is grateful to Fundação para a Ciência e a Tecnologia and European Social Fund through Programa Operacional Capital Humano for the Ph.D . grant ( SFRH/BD/137516/2018-COVID/BD/153231/2023 ). Publisher Copyright: © 2023 Elsevier LtdFatty acids (FA) are biomarkers of metabolic dysfunction. Adipose tissue is the largest reservoir of FA and acts differently in obese individuals. Menopause by itself significantly alters metabolism, lipid metabolism dysregulation, and adipose tissue distribution. How adipose tissue FA alters an obese individual's metabolism depending on a female's menopausal status is yet poorly understood. Hence, the subcutaneous (scAT) and visceral adipose tissue (vAT) FA profile for 173 obese premenopausal and postmenopausal women was measured and associated with biochemical parameters. scAT and vAT FA profiles were distinct by themselves and in menopause. In total 816 associations were found with biochemical parameters, where only 58 were independent of the menopausal status. The associations found to emphasize the importance of assessing the adipose tissue FA profile and how their behavior changes with menopause. The FA are crucial in metabolic processes and can be helpful biomarkers in the prevention/treatment and follow-up of female obesity.publishersversionpublishe

Magnetic dispersive micro solid-phase extraction and gas chromatography determination of organophosphorus pesticides in strawberries

Magnetic nanoparticles (MNPs) with different sizes and characteristics were synthesized to be used as a QuEChERS sorbents for the determination of seven organophosphorus pesticides (OPPs) in strawberries by gas chromatography analysis with flame photometric and mass spectrometry detection. To achieve the optimum conditions of modified QuEChERS procedure several parameters affecting the cleanup efficiency including the amount of the sorbents and cleanup time were investigated. The results were compared with classical QuEChERS methodologies and the modified QuEChERS procedure using MNPs showed the better performance. Under the optimum conditions of the new methodology, three spiking levels (25, 50 and 100 μg kg-1) were evaluated in a strawberry sample. The results showed that the average recovery was 93% and the relative standard deviation was less than 12%. The enrichment factor ranged from 111 to 145%. The good linearity with coefficients of determination of 0.9904-0.9991 was obtained over the range of 25-250 μg kg-1 for 7 OPPs. It was determined that the MNPs have an excellent function as sorbent when purified even using less amount of sorbents and the magnetic properties allowed non-use of the centrifugation in cleanup step. The new methodology was applied in strawberry samples from conventional and organic farming. The new sorbents were successfully applied for extraction and determination of OPPs in strawberries.The authors would like to thank technical assistance of Rui Rocha from Centro de Materiais da Universidade do Porto (CEMUP) for the SEM images, Aurora Silva from REQUIMTE/LAQV and Instituto Superior de Engenharia/Instituto Politécnico do Porto for FTIR analysis and Paula Paíga from REQUIMTE/LAQV for the graphical abstracts design. This work received financial support from the European Union (FEDER funds through COMPETE) and National Funds (FCT) through project UID/QUI/50006/2013 from the European Union (FEDER funds) under the framework of QREN through Project Qualidade e Segurança Alimentar – Uma abordagem (nano)tecnológica”, reference NORTE-01-0145-FEDER- 000011. Virgínia Cruz Fernandes and Maria Freitas are grateful to FCT (Fundação para a Ciência e a Tecnologia) for the Postdoc grant (SFRH/BPD/109153/2015) and PhD grant (SFRH/BD/111942/2015) respectively.info:eu-repo/semantics/publishedVersio

Organochlorine pesticides, brominated flame retardants, synthetic musks and polycyclic aromatic hydrocarbons in shrimps. An overview of occurrence and its implication on human exposure

Shrimps are widely distributed in coastal areas, estuaries and rivers. Although this shellfish is a good source of nutrients, it can also accumulate environmental contaminants, such as organochlorine pesticides (OCPs), brominated flame retardants (BFRs), synthetic musks (SMs) and polycyclic aromatic hydrocarbons (PAHs). Due to their bioaccumulative properties, these pollutants are endocrine disruptors. In this review, an overview of the world's shrimp market, pollutants legislation and values found in shrimp samples will be discussed. Shrimps analysed from all continents showed the presence of contaminants, Asia being the continent with the highest values reported. The concentration values reached a maximum of 26100 ng/g wet weight (ww) for OCPs, of 226.45 ng/g ww for BFRs, of 12.1 ng/g ww for SMs and of 50650 ng/g ww for PAHs. Exposure data and risk, taken from different studies, are very variable and indicate that shrimp's consumption may represent a risk especially in certain geographic areas.publishersversionpublishe

Mass spectrometry parameters optimization for the 46 multiclass pesticides determination in strawberries with gas chromatography ion-trap tandem mass spectrometry

Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET),maximum excitation energy or “q” value (q), and isolationmass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit.Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples

Comparison of Disposable Pipette Extraction and Dispersive Solid-Phase Extraction in the QuEChERS Method for Analysis of Pesticides in Strawberries

In this study, we sought to assess the applicability of GC–MS/MS for the identification and quantification of 36 pesticides in strawberry from integrated pest management (IPM) and organic farming (OF). Citrate versions of QuEChERS (quick, easy, cheap, effective, rugged and safe) using dispersive solid-phase extraction (d-SPE) and disposable pipette extraction (DPX) for cleanup were compared for pesticide extraction. For cleanup, a combination of MgSO4, primary secondary amine and C18 was used for both the versions. Significant differences were observed in recovery results between the two sample preparation versions (DPX and d-SPE). Overall, 86% of the pesticides achieved recoveries (three spiking levels 10, 50 and 200 µg/kg) in the range of 70–120%, with <13% RSD. The matrix effects were also evaluated in both the versions and in strawberries from different crop types. Although not evidencing significant differences between the two methodologies were observed, however, the DPX cleanup proved to be a faster technique and easy to execute. The results indicate that QuEChERS with d-SPE and DPX and GC–MS/MS analysis achieved reliable quantification and identification of 36 pesticide residues in strawberries from OF and IPM

Analysis of pesticide residues in strawberries and soils by GC-MS/MS, LC-MS/MS and two-dimensional GC-timeof- flight MS comparing organic and integrated pest management farming

This study analysed 22 strawberry and soil samples after their collection over the course of 2 years to compare the residue profiles from organic farming with integrated pest management practices in Portugal. For sample preparation, we used the citrate-buffered version of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. We applied three different methods for analysis: (1) 27 pesticides were targeted using LC-MS/MS; (2) 143 were targeted using low pressure GC-tandem mass spectrometry (LP-GC-MS/MS); and (3) more than 600 pesticides were screened in a targeted and untargeted approach using comprehensive, two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Comparison was made of the analyses using the different methods for the shared samples. The results were similar, thereby providing satisfactory confirmation of both similarly positive and negative findings. No pesticides were found in the organic-farmed samples. In samples from integrated pest management practices, nine pesticides were determined and confirmed to be present, ranging from 2 μg kg−1 for fluazifop-pbutyl to 50 μg kg−1 for fenpropathrin. Concentrations of residues in strawberries were less than European maximum residue limits

Persistent organic pollutant levels in human visceral and subcutaneous adipose tissue in obese individuals - Depot differences and dysmetabolism implications

Background: The role of persistent organic pollutants (POPs) with endocrine disrupting activity in the aetiology of obesity and other metabolic dysfunctions has been recently highlighted. Adipose tissue (AT) is a common site of POPs accumulation where they can induce adverse effects on human health. Objectives: To evaluate the presence of POPs in human visceral (vAT) and subcutaneous (scAT) adipose tissue in a sample of Portuguese obese patients that underwent bariatric surgery, and assess their putative association with metabolic disruption preoperatively, as well as with subsequent body mass index (BMI) reduction. Methods: AT samples (n=189) from obese patients (BMI ≥35) were collected and the levels of 13 POPs were determined by gas chromatography with electron-capture detection (GC-ECD). Anthropometric and biochemical data were collected at the time of surgery. BMI variation was evaluated after 12 months and adipocyte size was measured in AT samples. Results: Our data confirm that POPs are pervasive in this obese population (96.3% of detection on both tissues), their abundance increasing with age (RS=0.310, p<0.01) and duration of obesity (RS=0.170, p<0.05). We observed a difference in AT depot POPs storage capability, with higher levels of ΣPOPs in vAT (213.9±204.2 compared to 155.1±147.4 ng/g of fat, p<0.001), extremely relevant when evaluating their metabolic impact. Furthermore, there was a positive correlation between POP levels and the presence of metabolic syndrome components, namely dysglycaemia and hypertension, and more importantly with cardiovascular risk (RS=0.277, p<0.01), with relevance for vAT (RS=0.315, p<0.01). Finally, we observed an interesting relation of higher POP levels with lower weight loss in older patients. Conclusion: Our sample of obese subjects allowed us to highlight the importance of POPs stored in AT on the development of metabolic dysfunction in a context of obesity, shifting the focus to their metabolic effects and not only for their recognition as environmental obesogens