Assessing human exposure to pesticides and mycotoxins: optimization and validation of a method for multianalyte determination in urine samples.

Humans are exposed to an increasing number of contaminants, with diet being one of the most important exposure routes. In this framework, human biomonitoring is considered the gold standard for evaluating human exposure to chemicals. Pesticides and mycotoxins are chemicals of special concern due to their health implications. They constitute the predominant border rejection notifications for food and feed in Europe and the USA. However, current biomonitoring studies are focused on a limited number of compounds and do not evaluate mycotoxins and pesticides together. In this study, an analytical method has been developed for the determination of 30 pesticides and 23 mycotoxins of concern in urine samples. A salting-out liquid-liquid extraction (SALLE) procedure was optimized achieving recoveries between 70 and 120% for almost all the compounds and limits as lower as when QuEChERS was applied. The compounds were then determined by liquid chromatography coupled to triple quadrupole mass spectrometry. Different chromatographic conditions and analytical columns were tested, selecting a Hypersild gold aQ column as the best option. Finally, the method was applied to the analysis of 45 urine samples, in which organophosphate and pyrethroid pesticides (detection rates (DR) of 82% and 42%, respectively) and ochratoxin A and deoxynivalenol (DR of 51% and 33%, respectively) were the most detected compounds. The proposed analytical method involves the simultaneous determination of a diverse set of pesticides and mycotoxins, including their most relevant metabolites, in human urine. It serves as an essential tool for biomonitoring the presence of highly prevalent contaminants in modern society.

Gastrointestinal bioaccessibility and fiber mitigation of tropane alkaloids assessed on tea and cookies by in vitro digestion.

BACKGROUND: Tropane alkaloids (TAs) are toxic compounds with a high anticholinergic effect. They have been widely analyzed in food samples, but their fate in the gastrointestinal tract has not been evaluated yet. RESULTS: In this study, static in vitro digestion was performed to assess gastrointestinal bioaccessibility of the most common TAs on tea and home-made cookies. Cookies enriched with dietary fiber (pectin, arabinogalactan, and κ-carrageenan) were also tested to evaluate their influence on TA bioaccessibility. Two extraction methods and a liquid chromatography-mass spectrometry method were optimized and validated. Bioaccessibility for tea (60-105%) was higher than for cookies (39-93%) (P = 0.001-0.002), which indicates TAs could be more easily absorbed when they are contaminating tea. Digestion of cookies enriched with 50 g kg-1 of different fibers showed that, although no significant changes were observed in the gastric phase (P = 0.084-0.920), duodenal bioaccessibility was significantly reduced (P = 0.008-0.039). Pectin was the fiber with a better mitigation effect for all the compounds. CONCLUSION: TAs bioaccessibility was determined after in vitro digestion of contaminated tea and cookies. Dietary fiber seems to be a promising mitigation strategy, significantly reducing TA bioaccessibility percentages. © 2023 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Cuff-assisted versus cap-assisted colonoscopy for adenoma detection: results of a randomized study.

BACKGROUND: The adenoma detection rate (ADR) is the most important marker of colonoscopy quality. Devices to improve adenoma detection have been developed, such as the Endocuff and transparent cap. The aim of the current study was to examine whether there was a difference in ADR between Endocuff-assisted (EAC) and cap-assisted colonoscopy (CAC). METHODS: A randomized prospective trial was conducted. Eligible patients included adults ≥ 18 years referred because of symptoms, surveillance, or colonoscopies as part of the Bowel Cancer Screening Programme (BCSP). The primary outcome measure was ADR. Secondary outcomes included mean number of adenomas, mean number of polyps, polyp detection rate, cecal intubation rate, and time to cecal intubation. Procedural measures, device removal rate, and adverse events were also recorded. RESULTS: A total of 711 patients (51.1 % men; median age 63 years) were included, of whom 357 patients were randomized to EAC and 354 patients to CAC. In the intention-to-treat analysis, the ADR was similar in both groups: EAC 50.4 % (95 % confidence interval [CI] 45.1 - 55.7) vs. CAC 50.6 % (95 %CI 45.2 - 55.9). Similar results were obtained in the per-protocol analysis: EAC 51.6 % (95 %CI 46.2 - 57) vs. CAC 51.4 % (95 %CI 46 - 56.8). There were no differences between the two devices in ADR according to the mean number of adenomas and polyps per procedure, polyp detection rate, cecal intubation rate, and time to cecal intubation. Device removal rate and adverse events were also similar. CONCLUSION: In this randomized study, no differences in ADR were found between Endocuff- and cap-assisted colonoscopy.

Accuracy for optical diagnosis of colorectal polyps in clinical practice.

BACKGROUND: Optical diagnostic involves predicting polyp histopathology from its endoscopic characteristics. It is only recommended for diminutive polyps ( < or = 5 mm) and for predictions made with high confidence. OBJECTIVES: To evaluate the accuracy of optical imaging in clinical practice and to assess if optical diagnosis is useful for predicting future colonoscopy surveillance intervals without waiting for histopathological analysis. METHODS: consecutive > 18 years patients were enrolled in this prospective study. Colonoscopies were performed by five expert endoscopists who previously participated in an ex-vivo training. Colonoscopes CF-H180AL and CF-Q180AL were used together with Exera II (Olympus Medical System, Tokyo, Japan) processors. Each polyp was characterized in real time using white light and Narrow Band Imaging. Accuracy of optical diagnosis (S, E, NPV, PPV) and correlation between surveillance interval based on optical diagnosis and histopathological analysis were calculated. RESULTS: 311 colon polyps < 10 mm (216 diminutive) in 195 patients were analyzed. Accuracy of optical diagnostics for predictions made with high confidence: Diminutive polyps(sensitivity 0.59, specificity 0.92, NPV 0.48); polyps < 10 mm (sensitivity 0.73, specificity 0.88, NPV 0.50). An optical diagnosis based surveillance recommendation was given to 90 patients. Concordance with histopathology based recommendation was 92.2% according to the European guideline and 93.3% according to the ESGE guideline. CONCLUSIONS: Optical diagnostics can be used to predict future surveillance intervals immediately after colonoscopy. However, in this study, based on clinical practice, the accuracy of optical imaging is below the recommended standards.

Factors related to the effectiveness of variable stiffness colonoscope: results of a multivariate analysis.

BACKGROUND: Various studies and two meta-analysis have shown that a variable stiffness colonoscope improves cecal intubation rate. However, there are few studies on how this colonoscope should be used. OBJECTIVE: The aim of this study was to identify factors related to the advancement of the colonoscope when the variable stiffness function is activated. METHODS: Prospective study enrolling consecutive patients referred for colonoscopy. The variable stiffness colonoscope (Olympus CF-H180DI/L®) was used. We performed univariate and multivariate analyses of factors associated with the success of the variable stiffness function. RESULTS: After the data inclusion period, 260 patients were analyzed. The variable stiffness function was used most in the proximal colon segments (ascending and transverse colon 85%; descending/sigmoid colon 15.2%). The body mass index was lower in patients in whom the endoscope advanced after activating the variable stiffness than those in which it could not be advanced (25.9 + or - 4.8 vs. 28.3 + or - 5.4 kg/m2, p = 0.009). The endoscope advanced less frequently when the stiffness function was activated in the ascending colon versus activation in other segments of the colon (25% vs. 64.5% ascending colon vs. other segments; p < 0.05). In the multivariate analysis, only the colon segment in which the variable stiffness was activated was an independent predictor of advancement of the colonoscope. CONCLUSIONS: The variable stiffness function is effective, allowing the colonoscope advancement especially when applied in the transverse colon, descending colon and sigmoid. However, when used in the ascending colon it has a lower effectiveness.

Tracing the dissipation of difenoconazole, its metabolites and co-formulants in tomato: A comprehensive analysis by chromatography coupled to high resolution mass spectrometry in laboratory and greenhouse trials.

The study evaluated Ceremonia 25 EC®, a plant protection product (PPP) containing difenoconazole, in tomato crops, to identify potential risks associated with PPPs, and in addition to this compound, known metabolites from difenoconazole degradation and co-formulants present in the PPP were monitored. An ultra high performance liquid chromatography coupled to quadrupole-Orbitrap mass analyser (UHPLC-Q-Orbitrap-MS) method was validated with a working range of 2 µg/kg (limit of quantification, LOQ) to 200 µg/kg. Difenoconazole degradation followed a biphasic double first-order in parallel (DFOP) kinetic model in laboratory and greenhouse trials, with high accuracy (R2 > 0.9965). CGA-205374, difenoconazole-alcohol, and hydroxy-difenoconazole metabolites were tentatively identified and semi-quantified in laboratory trials by UHPLC-Q-Orbitrap-MS from day 2 to day 30. No metabolites were found in greenhouse trials. Additionally, 13 volatile co-formulants were tentatively identified by gas chromatography (GC) coupled to Q-Orbitrap-MS, detectable up to the 7th day after PPP application. This study provides a comprehensive understanding of difenoconazole dissipation in tomatoes, identification of metabolites, and detection of co-formulants associated with the applied PPP.

Analytical challenges and opportunities in the study of endocrine disrupting chemicals within an exposomics framework.

Exposomics aims to measure human exposures throughout the lifespan and the changes they produce in the human body. Exposome-scale studies have significant potential to understand the interplay of environmental factors with complex multifactorial diseases widespread in our society and whose origin remain unclear. In this framework, the study of the chemical exposome aims to cover all chemical exposures and their effects in human health but, today, this goal still seems unfeasible or at least very challenging, which makes the exposome for now only a concept. Furthermore, the study of the chemical exposome faces several methodological challenges such as moving from specific targeted methodologies towards high-throughput multitargeted and non-targeted approaches, guaranteeing the availability and quality of biological samples to obtain quality analytical data, standardization of applied analytical methodologies, as well as the statistical assignment of increasingly complex datasets, or the identification of (un)known analytes. This review discusses the various steps involved in applying the exposome concept from an analytical perspective. It provides an overview of the wide variety of existing analytical methods and instruments, highlighting their complementarity to develop combined analytical strategies to advance towards the chemical exposome characterization. In addition, this review focuses on endocrine disrupting chemicals (EDCs) to show how studying even a minor part of the chemical exposome represents a great challenge. Analytical strategies applied in an exposomics context have shown great potential to elucidate the role of EDCs in health outcomes. However, translating innovative methods into etiological research and chemical risk assessment will require a multidisciplinary effort. Unlike other review articles focused on exposomics, this review offers a holistic view from the perspective of analytical chemistry and discuss the entire analytical workflow to finally obtain valuable results.

Simultaneous detection of mycotoxins and pesticides in human urine samples: A 24-h diet intervention study comparing conventional and organic diets in Spain.

Pesticides and mycotoxins, prominent chemical hazards in the food chain, are commonly found in plant-based foods, contributing to their pervasive presence in the human body, as evidenced by biomonitoring programs. Despite this, there is limited knowledge about their co-occurrence patterns. While intervention studies have demonstrated that organic diets can significantly reduce pesticide levels, their impact on mycotoxin exposure has been overlooked. To address this gap, this study pursued two objectives: first, to characterize the simultaneous presence of mycotoxins and pesticides in human urine samples by means of the control of the biomarkers of exposure, and second, to investigate the influence of consuming organic foods on these co-exposure patterns. A pilot study involving 20 healthy volunteers was conducted, with participants consuming either exclusively organic or conventional foods during a 24-h diet intervention in autumn 2021 and spring 2022 to account for seasonal variability. Participants provided detailed 24-h dietary records, and their first-morning urine samples were collected, minimally treated and analysed using LC-Q-ToF-MS by means of a multitargeted method in order to detect the presence of these residues. Results indicated that among the 52 screened compounds, four mycotoxins and seven pesticides were detected in over 25% of the samples. Deoxynivalenol (DON) and the non-specific pesticide metabolite diethylphosphate (DEP) exhibited the highest frequency rates (100%) and concentration levels. Correlations were observed between urine levels of mycotoxins (DON, ochratoxin alpha [OTα], and enniatin B [ENNB]) and organophosphate pesticide metabolites DEP and 2-diethylamino-6-methyl-4-pyrimidinol (DEAMPY). The pilot intervention study suggested a reduction in ENNB and OTα levels and an increase in ß-zearalenol levels in urine after a short-term replacement with organic food. However, caution is advised due to the study's small sample size and short duration, emphasizing the need for further research to enhance understanding of the human chemical exposome and refine chemical risk assessment.

Uncovering the Dissipation of Chlorantraniliprole in Tomatoes: Identifying Transformation Products (TPs) and Coformulants in Greenhouse and Laboratory Studies by UHPLC-Q-Orbitrap-MS and GC-Q-Orbitrap-MS.

The present study addressed the dissipation of the insecticide chlorantraniliprole in tomatoes treated with Altacor 35 WG under laboratory and greenhouse conditions, as well as the identification of transformation products (TPs) and coformulants, performing suspect screening analysis. Analyses were performed by ultra-high-performance liquid and gas chromatography coupled to quadrupole-Orbitrap high-resolution mass spectrometry (UHPLC-Q-Orbitrap-MS and GC-Q-Orbitrap-MS). In all cases, chlorantraniliprole was fitted to a biphasic kinetic model, with R2 values greater than 0.99. Dissipation was noticeably faster in greenhouse studies, in which even 96% dissipation was achieved over 53 days. One TP, IN-F6L99, was tentatively identified in both greenhouse and laboratory studies and was semiquantified by using chlorantraniliprole as the analytical standard, yielding a top value of 354 µg/kg for laboratory studies, whereas values for greenhouse studies fell under the limit of quantitation (LOQ). Finally, a total of 15 volatile coformulants were identified by GC-Q-Orbitrap-MS.

Comprehensive Dissipation of Azadirachtin in Grapes and Tomatoes: The Effect of Bacillus thuringiensis and Tentative Identification of Unknown Metabolites.

Neem oil is a biopesticide normally applied together with Bacillus thuringiensis (Bt). However, neither its dissipation nor the influence of Bt has been previously evaluated. In this study, dissipation of neem oil was investigated when it was applied alone or together with Bt at 3 and 22 °C. A methodology involving solid-liquid extraction and liquid chromatography-high-resolution mass spectrometry was developed for that purpose. The method was validated obtaining recoveries from 87 to 103%, with relative standard deviations lower than 19% and limits of quantification from 5 to 10 µg/kg. Azadirachtin A (AzA) dissipation was fit to a single first order, being faster when neem oil was applied together with Bt and at 22 °C (RL50 = 12-21 days) than alone and at 3 °C (RL50 = 14-25 days). Eight related compounds were found in real samples with similar dissipation curves compared to AzA, and five unknown metabolites were identified in degraded samples, with increasing concentrations during parent compound degradation.

Monitoring of Volatile Additives from Plant Protection Products in Tomatoes Using HS-SPME-GC-HRMS: Targeted and Suspect Approaches.

Additives present in plant protection products (PPPs) are normally not monitored after sample treatments. In this study, the fate of additives detected by targeted and nontargeted analysis in tomato samples treated with two PPPs was carried out. The study was carried out in a greenhouse for 12 days, in which two applications with each PPP were made. Compounds were extracted by applying a headspace solid phase microextraction (HS-SPME) and analyzed by gas chromatography coupled to high resolution mass spectrometry (GC-HRMS), performing targeted and suspect approaches. Three targeted and 15 nontargeted compounds were identified at concentration levels of up to 150 µg/kg. Compounds detected encompassed benzene, toluene, indene, and naphthalene derivatives, as well as conservatives and flavouring compounds. Most of them degraded in less than 7 days after the second application, following first-order kinetic. This study aims to reduce knowledge gaps regarding additives and their fate under real climatic conditions of greenhouses cultivations.

Critical Evaluation of Analytical Methods for the Determination of Anthropogenic Organic Contaminants in Edible Oils: An Overview of the Last Five Years.

Anthropogenic contaminants, as pesticides, polycyclic aromatic hydrocarbons (PAHs) and monochloropropanediols (MCPDs), have become important to be controlled in edible oils, since their regular occurrence. In fact, alerts from the Rapid Alert System for Food and Feed (RASFF) in oils normally include these compounds. From a critical point of view, tools used to control these compounds in the last 5 years will be discussed, including sample preparation, analysis and current regulations. Extraction and analysis methods will be discussed next, being liquid-liquid extraction (LLE) and QuEChERS, with or without clean-up step, as well as chromatographic methods coupled to different analyzers (mainly mass spectrometry), the most commonly used for extraction and analysis respectively. Occurrence in samples will also be reviewed and compared with the legal maximum residue limits (MRLs), observing that 4%, 20% and 60% of the analyzed samples exceed the legal limits for pesticides, MCPDs and PAHs respectively.

Investigating the Impact of Dietary Fibers on Mycotoxin Bioaccessibility during In Vitro Biscuit Digestion and Metabolites Identification.

Mycotoxins contamination is a real concern worldwide due to their high prevalence in foods and high toxicity; therefore, strategies that reduce their gastrointestinal bioaccessibility and absorption are of major relevance. The use of dietary fibers as binders of four mycotoxins (zearalenone (ZEA), deoxynivalenol (DON), HT-2, and T-2 toxins) to reduce their bioaccessibility was investigated by in vitro digestion of biscuits enriched with fibers. K-carrageenan is a promising fiber to reduce the bioaccessibility of ZEA, obtaining values lower than 20%, while with pectin a higher reduction of DON, HT-2, and T-2 (50-88%) was achieved. Three metabolites of mycotoxins were detected, of which the most important was T-2-triol, which was detected at higher levels compared to T-2. This work has demonstrated the advantages of incorporating dietary fibers into a biscuit recipe to reduce the bioaccessibility of mycotoxins and to obtain healthier biscuits than when a conventional recipe is performed due to its high content of fiber.

Real-time PCR for diagnosing Helicobacter pylori infection in patients with upper gastrointestinal bleeding: comparison with other classical diagnostic methods.

The aim of this study was to determine the diagnostic usefulness of quantification of the H. pylori genome in detection of infection in patients with upper gastrointestinal bleeding (UGB). A total of 158 consecutive patients with digestive disorders, 80 of whom had clinical presentation of UGB, were studied. The number of microorganisms was quantified using a real-time PCR system which amplifies the urease gene with an internal control for eliminating the false negatives. A biopsy sample from the antrum and corpus of each patient was processed. The rapid urease test, culture, histological study, stool antigen test, and breath test were done. The gold standard was a positive culture or positive results in at least two of the other techniques. When a positive result was defined as any number of microorganisms/human cell, the sensitivity of real-time PCR was greater in bleeding patients, especially in the gastric corpus: 68.4% (95% confidence interval [CI], 52.3 to 84.5%) in non-UGB patients versus 91.5% (95% CI, 79.6 to 97.6%) in UGB patients. When a positive result was defined as a number of microorganisms/human cell above the optimal value that maximizes the Youden index (>3.56 microorganisms/human cell in the antrum and >2.69 in the corpus), the sensitivity and specificity in UGB patients were over 80% in both antrum and corpus. Our findings suggest that some bleeding patients with infection caused by H. pylori may not be correctly diagnosed by classical methods, and such patients could benefit from the improved diagnosis provided by real-time PCR. However, the clinical significance of a small number of microorganisms in patients with negative results in classical tests should be evaluated.

Looking beyond the Active Substance: Comprehensive Dissipation Study of Myclobutanil-Based Plant Protection Products in Tomatoes and Grapes Using Chromatographic Techniques Coupled to High-Resolution Mass Spectrometry.

A comprehensive evaluation of the dissipation of a myclobutanil plant protection product was performed in tomato and grape samples. Different temperature conditions (3 and 22 °C) were evaluated. A biphasic kinetic model provided a suitable adjustment (R2 > 0.95), with persistence (residual level, RL50) lower than 24 days in all cases. Solid-liquid extraction and ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-Q-Orbitrap-HRMS) were used for metabolites' elucidation, identifying six myclobutanil metabolites, four out of them described for the first time and one of them confirmed using 1H, 13C, (1H-1H)-COSY, (1H-13C)-HMQC, and (1H-13C)-HMBC nuclear magnetic resonance (NMR). Their degradation curves were also evaluated, increasing their concentrations when the myclobutanil concentration decreases. Additionally, coformulants present in the commercial formulation were monitored employing headspace solid-phase microextraction method (HS-SPME)-gas chromatography coupled to HRMS (GC-Q-Orbitrap-HRMS). Seven coformulants were quantified in tomato samples. Their dissipation curves were studied, and it was observed that they were almost degraded 12 days after application.

Recent applications of chromatography for analysis of contaminants in cannabis products: a review.

In the last few years, the cultivation of cannabis has been increasing due to greater use in foods, recreational use, creams, oils, and other applications. Thus, analysis of contaminants (e.g. pesticides and mycotoxins) in cannabis products is necessary to ensure consumer safety. This review is focused on the analytical procedures, based on chromatographic techniques, used for the determination of contaminants in cannabis and related products, developed from 2015 to 2020. QuEChERS (acronym of quick, easy, cheap, effective, rugged and safe) was mainly used for the extraction of pesticides and other contaminants from cannabis because its versatility and capacity to extract a wide range of substances, and therefore, increasing the scope of the analysis. The most employed technique to determine pesticides and mycotoxins in cannabis products was liquid chromatography (LC) coupled to mass spectrometry (MS), although gas chromatography (GC) coupled to MS was also employed for the analysis of non-polar compounds, using triple quadrupole (QqQ) as mass analyzer. Nevertheless, new advances in cannabis analysis are also discussed, introducing techniques such as high-resolution mass spectrometry (HRMS), which allows for performing both targeted and untargeted (unknown and suspect) analyses. © 2021 Society of Chemical Industry.

In Vivo Characterization of the Toxicological Properties of DPhP, One of the Main Degradation Products of Aryl Phosphate Esters.

BACKGROUND: Aryl phosphate esters (APEs) are widely used and commonly present in the environment. Health hazards associated with these compounds remain largely unknown and the effects of diphenyl phosphate (DPhP), one of their most frequent derivatives, are poorly characterized. OBJECTIVE: Our aim was to investigate whether DPhP per se may represent a more relevant marker of exposure to APEs than direct assessment of their concentration and determine its potential deleterious biological effects in chronically exposed mice. METHODS: Conventional animals (FVB mice) were acutely or chronically exposed to relevant doses of DPhP or to triphenyl phosphate (TPhP), one of its main precursors. Both molecules were measured in blood and other tissues by liquid chromatography-mass spectrometry (LC-MS). Effects of chronic DPhP exposure were addressed through liver multi-omics analysis to determine the corresponding metabolic profile. Deep statistical exploration was performed to extract correlated information, guiding further physiological analyses. RESULTS: Multi-omics analysis confirmed the existence of biological effects of DPhP, even at a very low dose of 0.1mg/mL in drinking water. Chemical structural homology and pathway mapping demonstrated a clear reduction of the fatty acid catabolic processes centered on acylcarnitine and mitochondrial ß-oxidation in mice exposed to DPhP in comparison with those treated with vehicle. An interesting finding was that in mice exposed to DPhP, mRNA, expression of genes involved in lipid catabolic processes and regulated by peroxisome proliferator-activated receptor alpha (PPARα) was lower than that in vehicle-treated mice. Immunohistochemistry analysis showed a specific down-regulation of HMGCS2, a kernel target gene of PPARα. Overall, DPhP absorption disrupted body weight-gain processes. CONCLUSIONS: Our results suggest that in mice, the effects of chronic exposure to DPhP, even at a low dose, are not negligible. Fatty acid metabolism in the liver is essential for controlling fast and feast periods, with adverse consequences on the overall physiology. Therefore, the impact of DPhP on circulating fat, cardiovascular pathologies and metabolic disease incidence deserves, in light of our results, further investigations. https://doi.org/10.1289/EHP6826.

Fast analysis of glufosinate, glyphosate and its main metabolite, aminomethylphosphonic acid, in edible oils, by liquid chromatographycoupled with electrospray tandem mass spectrometry.

A method has been developed for the rapid, specific, accurate, precise and sensitive determination of glufosinate, glyphosate and its major metabolite, aminomethylphosphonic acid, in edible oils, by liquid chromatography coupled to tandem mass spectrometry. Oils were extracted with acidified water (1% formic acid), and the extracts were directly injected into an LC using a Hypercarb column as the stationary phase. The analytes were eluted by a mobile phase of methanol and water containing 1% acetic acid, and they were ionised by electrospray ionisation in negative ion mode. The method was validated and limits of quantification ranged from 5 µg kg-1 (aminomethylphosphonic acid) to 10 µg kg-1 (glyphosate and glufosinate). Three concentrations (10, 50 and 100 µg kg-1) were selected to perform recovery studies. Mean recoveries ranged from 81.4% to 119.4%. Intra and inter-day precision were lower than 19%. Different edible oils were analysed, and no residues of the studied herbicides were detected above limits of quantification.

Effect of tea making and boiling processes on the degradation of tropane alkaloids in tea and pasta samples contaminated with Solanaceae seeds and coca leaf.

In this study, the degradation of tropane alkaloids in pasta under boiling (100 °C during 10 min) and tea making (100 °C and let cool 5 min) conditions has been evaluated for the first time. Pasta and green tea were contaminated with Datura Stramonium and Brugmansia Arborea seeds (pasta and green tea), whereas coca leaf tea was directly analysed. The compounds were extracted using solid-liquid extraction coupled to a preconcentration stage (only for the cooking water), and the compounds were analysed by liquid chromatography coupled to mass spectrometry (Exactive-Orbitrap analyser). Degradation studies indicate that concentration of tropane alkaloids decreases, and it depends on the compound, observing the highest degradation for tropinone, tropane, cuscohygrine and tropine, as well as it was observed that compounds migrated to the aqueous phase during cooking step. Finally, post-targeted analysis was performed and other tropane alkaloids were found, as scopine, tigloidine or convolvine, showing a similar behaviour under cooking conditions.

Reliable determination of tropane alkaloids in cereal based baby foods coupling on-line spe to mass spectrometry avoiding chromatographic step.

Cereal based foods are a major part of the infant diet and they can be contaminated with Solanaceae and other plants containing tropane alkaloids. This study was focused on the optimisation of an extraction procedure based on a solid-liquid method and an online SPE system, directly coupled to different mass spectrometry analysers as Orbitrap and triple quadrupole (QqQ), removing the chromatographic separation step. Total running analysis time was 15.8 min (17.3 min in the QqQ system). The developed method was validated obtaining recoveries ranging from 66 to 98% and 68-97% for the Orbitrap and QqQ respectively (RSD lower than 14.3%) and limits of quantification from 0.5 to 5 µg kg-1 and 0.5-10 µg kg-1 for the QqQ and Orbitrap analyser respectively. The validated method was applied to several cereal based baby food samples, finding a positive sample containing atropine (11.5 µg kg-1), scopolamine (2.8 µg kg-1) and apoatropine (7.5 µg kg-1).