14 research outputs found

    Studying pyrolysis products of bottom-of-the-barrel fuel with Py-GCxGC- TOF/CSD/FID

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    Development and validation of analytical methods for the analysis of 3-MCPD (both in free and ester form) and glycidyl esters in various food matrices and performance of an ad-hoc survey on specific food groups in support to a scientific opinion on comprehensive risk assessment on the presence of 3-MCPD and glycidyl esters in food

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    3-Monochloropropane-1,2-diol (3-MCPD), and 2-monochloropropane-1,3-diol (2-MCPD), are substances that might be generated in the processing of food. EU legislation specifies maximum levels for 3-MCPD in hydrolysed vegetable proteins and soya sauce. However, besides the free forms of 2- and 3-MCPD high levels of esterified MCPD forms were found in fats and oils. Another group of substances identified in fats and oils are glycidyl esters (GE). In order to provide reliable occurrence data on the levels of both bound and free forms of those substances, the European Food Safety Authority (EFSA) requested the Joint Research Centre (JRC) to develop suitable analysis methods and test the analysis methods on different kinds of food. Consequently two analytical methods were developed. One of the developed methods allows the determination of ester-bound analytes, whereas the other analysis method is suitable to determine free 2-MCPD and free 3-MCPD. Reliability of analysis results and robustness of the analysis methods were the main focus during method development and optimisation. The analytes were extracted with organic solvents under mild conditions. GEs are converted to monobromopropanediol esters (MBPD esters) prior to transesterification. MCPD esters and MBPD esters were transesterified followed by derivatisation of the analytes with phenyl boronic acid (PBA) in organic solvent. The PBA derivatives were measured by gas chromatography mass spectrometry (GC-MS) applying stable isotope labelled analogues of the analytes for quantification. The performance of both analysis methods was compliant with criteria specified by EFSA. The analytical methods were applied for the analysis of breads and bread rolls, fine bakery wares, smoked fish and meat products, fried and roasted meat, potato-based snacks and fried potato products, cereal-based snacks, and margarines. Analysis results were compiled and reported to EFSA in standard sample description (SSD) format.JRC.D.5-Standards for Food Bioscienc

    Development of a method for the simultaneous determination of pharmaceuticals and endocrine disrupting compounds, study of their fate during wastewater treatment with emphasis on anaerobic digestion of sewage sludge

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    The aim of the present PhD thesis was the development of analytical methods for the simultaneous determination of pharmaceutical compounds and endocrine disrupting chemicals in wastewater and sewage sludge samples, in order to estimate their concentration levels in conventional Wastewater Treatment Plants (WWTPs), as well as the investigation of their fate in lab-scale anaerobic reactors. More precisely, this dissertation presents an analytical method based on solid-phase extraction (SPE) and gas chromatography coupled with mass spectrometry for the simultaneous determination of the most frequently used acidic pharmaceutical residues, ibuprofen (IBF), diclofenac (DCF), naproxen (NPX) and ketoprofen (KFN), and phenolic endocrine disruptors, bisphenol (BPA), triclosan (TCS), nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate NP2EO), in wastewater and sewage sludge samples. In the first phase of the study, each compound has been characterized individually as a trimethylsilyl derivative in order to identify the characteristic ions (m/z ratio) constituting the mass spectrum and to choose the ions for quantification and confirmation. Subsequently, derivatization was optimized by testing different variables such as the volume of the derivatization solvent bis(trimethylsilyl) trifluoroacetamide and the effect of each catalyst, pyridine and 1% trimethyl chlorosilane, in the derivatized solution. For the analysis of wastewater samples, two commercial SPE cartridges, C18 and Oasis HLB, were compared for their extraction efficiency of the target compounds. The key parameter of extraction procedure included the effect of pH (2.5, 5.3 and 7) of the loading solution. For solid samples, parameters such as the mass of extracted biomass, the volume of the extraction organic solvent and the effect of matrix interferences in chromatographic analysis were evaluated. The developed methods presented satisfactory repeatability and reproducibility with mean relative recoveries ranging from 91% (IBF) to 117% (NPX) for wastewater and 84% (NP2EO) to 107% (IBF) for sewage sludge samples. The limits of detection for the developed methods were ranged between 0.3 ng L-1 (KFN) to 14.8 ng L-1 (BPA) and 15.0 (TCS) ng g-1 to 32.9 ng g-1 (BPA) for wastewater and sewage sludge, respectively. The concentrations of the target nine emerging contaminants were determined in wastewater and sludge samples originating from two WWTPs in Greece. Average concentrations in raw and treated wastewater ranged from 0.39 μg L-1 (KFN) to 12.52 μg L-1 (NP) and from 80%) during anaerobic digestion, whereas removal of EDCs was lower, ranging up to 55% for NP1EO. During the last part of this PhD thesis the fate of the target compounds in lab-scale anaerobic digesters was investigated. For this reason, two single stage systems operating in mesophilic and thermophilic mode and one two-stage system (thermophilic-mesophilic bioreactor) were used. The performance of all digestion systems was monitored through various parameters such as pH, volatile suspended solids removal, total COD removal, concentrations of VFAs, and biogas daily production. Analysis of the results showed that the operation of all digestion systems remained stable and efficient throughout the entire period of the study. Regarding micropollutants, almost all of the investigated compounds removed significantly during sludge anaerobic digestion. The highest removal efficiency was calculated for diclofenac, naproxen, ibuprofen and ketoprofen (>80%), whereas lower removal efficiencies were observed for triclosan, bisphenol and nonylphenols (40-80%). On the other hand, the elimination of nonylphenol, nonylphenol monoethoxylate and nonylphenol diethoxylate was very low or even negative for some days, in mesophilic and thermophilic range, indicating their persistence during anaerobic sludge treatment or/and their formation during the process. In general, two-stage digestion showed slightly better performance for all tested compounds. Finally, none of the target compounds were totally eliminated by the applied treatment processes and, as a result, they were detected in most treated sludge samples. According to the above, a possible threat for the environment cannot be excluded, due to digested sludge disposal.Στα πλαίσια της παρούσας διδακτορικής διατριβής αναπτύχθηκαν αναλυτικές μέθοδοι για τον ταυτόχρονο ιχνοπροσδιορισμό τεσσάρων (4) φαρμακευτικών ουσιών και πέντε (5) ενδοκρινικών διαταρακτών σε δείγματα υγρών αποβλήτων και ιλύος. Οι συγκεκριμένες μέθοδοι χρησιμοποιήθηκαν για να εκτιμηθούν τα επίπεδα συγκεντρώσεων των υπό διερεύνηση μικρορύπων σε συμβατικές μονάδες επεξεργασίας υγρών αποβλήτων και ιλύος και για να μελετηθεί η τύχη τους σε εργαστηριακούς αντιδραστήρες αναερόβιας χώνευσης.Οι αναλυτικές μέθοδοι που αναπτύχθηκαν περιλάμβαναν προκατεργασία του διαλυτού κλάσματος των αποβλήτων με εκχύλιση στερεής φάσης (SPE) και χρήση υπερήχων για το σωματιδιακό κλάσμα των αποβλήτων και τα δείγματα ιλύος. Ο ποιοτικός και ποσοτικός προσδιορισμός των ουσιών πραγματοποιήθηκε με χρήση αέριας χρωματογραφίας συζευγμένης με φασματομετρία μάζας (GC-MS). Με τις συγκεκριμένες μεθόδους προσδιορίστηκαν ταυτόχρονα οι πιο διαδομένες στη χρήση όξινες φαρμακευτικές ουσίες; ibuprofen (IBF), diclofenac (DCF), naproxen (NPX), ketoprofen (KFN) και οι συνθετικοί ενδοκρινικοί διαταράκτες (synthetical EDCs); bisphenol A (BPA), triclosan (TCS), nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) και nonylphenol diethoxylate (NP2EO). Στην πρώτη φάση της ανάπτυξης των μεθόδων, κάθε ένωση αναλύθηκε μεμονωμένα -μετά από παραγωγοποίηση- προκειμένου να προσδιοριστεί το φάσμα μαζών της και να επιλεγούν τα χαρακτηριστικά ιόντα για τον ποιοτικό και ποσοτικό προσδιορισμό της. Στη συνέχεια, βελτιστοποιήθηκε η διαδιακασία της παραγωγοποίησης. Οι παράμετροι που εξετάστηκαν ήταν: ο όγκος του διαλύτη παραγωγοποίησης (Ν,Ο-δι-τριμεθυλο-σιλυλο-τριφθορο-ακεταμιδίου, BSTFA), η διάρκεια της αντίδρασης και η επίδραση των καταλυτών πυριδίνης και 1% τριμεθυλο-χλωροσιλάνιο (TMCS). Για την απομόνωση των ουσιών στόχων από τα δείγματα των υγρών αποβλήτων εξετάστηκαν δύο διαφορετικές φύσιγγες εκχύλισης (C18 και Oasis HLB) και μελετήθηκε η επίδραση του pH (2.5, 5.3 και 7) του δείγματος. Για την απομόνωση των ουσιών από τα στερεά δείγματα (σωματιδιακή φάση αποβλήτων και ιλύ) μελετήθηκε η επίδραση της ποσότητας της εκχυλιζόμενης βιομάζας και ο όγκος του οργανικού διαλύτη εκχύλισης. Οι μέθοδοι που αναπτύχθηκαν ήταν επαναλήψιμες και αναπαραγώγιμες με μέσες σχετικές ανακτήσεις (Rf) που κυμάνθηκαν από 91% (IBF) έως 117% (NPX) για τα υγρά απόβλητα και από 84% (NP2EO) έως 107% (IBF) για τα δείγματα ιλύος. Τα όρια ανίχνευσης που υπολογίστηκαν κυμάνθηκαν μεταξύ 0.3 ng L-1 (KFN) και14.8 ng L-1 (BPA) και 15.0 (TCS) έως 32.9 ng g-1 (BPA) για τα υγρά απόβλητα και την ιλύ, αντίστοιχα.Στη συνέχεια, προσδιορίστηκαν οι συγκεντρώσεις των υπό εξέταση ουσιών σε δείγματα ακατέργαστων και επεξεργασμένων υγρών αποβλήτων και σε δείγματα ιλύος προερχόμενα από δύο Ελληνικές Μονάδες Επεξεργασίας Υγρών Αποβλήτων (Μ.Ε.Υ.Α.). Οι μέσες συγκεντρώσεις στην είσοδο και την έξοδο των μονάδων, κυμάνθηκαν από 0.39 μg L-1 (KFN) έως 12.52 μg L-1 (NP) και από 80%) κατά τη διάρκεια της αναερόβιας χώνευσης, ενώ η απομάκρυνση των EDCs ήταν πολύ χαμηλότερη (έως 55% για την NP1EO).Στο τελευταίο μέρος της διατριβής μελετήθηκε η τύχη των ουσιών στόχων σε τρία διαφορετικά συστήματα αναερόβιας χώνευσης εργαστηριακής κλίμακας; ένα μονοβάθμιο μεσόφιλο χωνευτή, ένα μονοβάθμιο θερμόφιλο χωνευτή και ένα διβάθμιο συστήμα αποτελούμενο από θερμόφιλο και μεσόφιλο χωνευτή σε σειρά. Όλα τα συστήματα λειτούργησαν στον ίδιο συνολικό χρόνο παραμονής της ιλύος (Sludge Residence Time, SRT: 20 ημέρες). Η ικανοποιητική λειτουργία των χωνευτών εξασφαλίστηκε μέσω παρακολούθησης μίας σειράς παραμέτρων όπως του pH, της απομάκρυνσης των πτητικών αιωρουμένων στερεών, της απομάκρυνσης του ολικού COD, των συγκέντρωσεων των πτητικών λιπαρών οξέων, της αλκαλικότητας, και της παραγωγής του βιοαερίου. Η παρακολούθηση των παραπάνω παραμέτρων έδειξε ότι η λειτουργία όλων των συστημάτων χώνευσης παρέμεινε σταθερή και αποδοτική καθ' όλη τη διάρκεια της μελέτης. Όσον αφορά στους μικρορύπους, οι περισσότερες από τις εξεταζόμενες ενώσεις απομάκρυνθηκαν σε σημαντικό βαθμό κατά την αναερόβια επεξεργασία της ιλύος. Τα υψηλότερα ποσοστά απομάκρυνσης υπολογίστηκαν για τις ουσίες DCF, NPX, IBF και KFN (>80%), ενώ χαμηλότερα ποσοστά απομάκρυνσης παρατηρήθηκαν για τις TCS, ΒPA και NPs (40-80%). Οι NP, NP1EO και NP2EO ήταν οι μόνες ενώσεις για τις οποίες αρνητικά ποσοστά απομάκρυνσης υπολογίστηκαν σε ορισμένες ημέρες υπό συνθήκες θερμόφιλης και μεσόφιλης χώνευσης, υποδεικνύοντας την εμμονή τους κατά τη διάρκεια της αναερόβιας επεξεργασίας της ιλύος ή/και το σχηματισμό τους κατά τη διεργασία από πρόδρομες ενώσεις. Σε γενικές γραμμές, το διβάθμιο σύστημα χώνευσης παρουσίασε ελαφρώς καλύτερη απόδοση στα ποσοστά απομάκρυνσης των ουσιών στόχων σε σχέση με τα μονοβάθμια συστήματα. Καμία από τις υπό διερεύνηση ενώσεις δεν απομακρύνθηκε πλήρως με τις εφαρμοζόμενες μεθόδους επεξεργασίας και, κατά συνέπεια, ανιχνεύθηκαν στα περισσότερα δείγματα χωνευμένης ιλύος. Σύμφωνα με τα ανωτέρω, μια πιθανή απειλή για το περιβάλλον δεν μπορεί να αποκλειστεί λόγω της διάθεσης της επεξεργασμένης ιλύος στο έδαφος

    Analytical method for the trace determination of esterified 3- and 2-monochloropropanediol and glycidyl fatty acid esters in various food matrices

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    In 2014, the European Food Safety Authority (EFSA) requested the Institute for Reference Materials and Measurements (IRMM) of the Joint Research Centre (JRC) to develop a reliable analytical method for the determination of fatty acid esters of 3-monochloropropanediol (3-MCPDEs), of 2-monochloropropanediol (2-MCPDEs) and of glycidol (GEs) in a broad variety of food samples, and to test its applicability in routine on about 500 different food samples. The provision of an analytical method was urgently required within the scope of monitoring the occurrence of these substances in food, which is necessary for the exposure estimations. The lack of occurrence data was accompanied by concerns regarding the applicability and reliability of results obtained with the available methods for processed food. This article presents an indirect analytical procedure for the simultaneous determination of 3-MCPDEs, 2-MCPDEs and GEs in a wide variety of food products after extraction by pressurised liquid extraction (PLE) and gas chromatography mass-spectrometry (GC-MS) detection. For the differentiation of MCPDEs and GEs, GEs were first converted to monobromopropanediol esters (MBPDEs) in aqueous acid bromide solution. MCPDEs and MBPDEs were then hydrolysed under acidic conditions followed by derivatisation of the released free (non-esterified) form in ethyl acetate with phenyl boronic acid (PBA). Quantification of the analytes was carried out using the isotopic labelled analogues of both MCPDEs and GEs. Limits of detection (LODs) and limits of quantitation (LOQs) were, expressed on fat basis, in the range of 7 - 17 mg kg−1 and 13 - 31 mg kg−1 respectively, while the working range of the method was between LOQ and 1.850 mg kg-1 (expressed on fat basis). The performance characteristics of the proposed analytical method were compliant with the criteria specified by EFSA and the European Commission. The developed method was successfully applied for the analysis of the target compounds in more than 650 different food samples covering the following categories: bread and rolls, fine bakery wares, smoked fish products, fried and roasted meat, potato based snacks and fried potato products, cereal-based snacks and margarines.JRC.F.5-Food and Feed Complianc

    Relationship between Coronary Arterial Geometry and the Presence and Extend of Atherosclerotic Plaque Burden: A Review Discussing Methodology and Findings in the Era of Cardiac Computed Tomography Angiography

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    Coronary artery disease (CAD) represents a modern pandemic associated with significant morbidity and mortality. The multi-faceted pathogenesis of this entity has long been investigated, highlighting the contribution of systemic factors such as hyperlipidemia and hypertension. Nevertheless, recent research has drawn attention to the importance of geometrical features of coronary vasculature on the complexity and vulnerability of coronary atherosclerosis. Various parameters have been investigated so far, including vessel-length, coronary artery volume index, cross-sectional area, curvature, and tortuosity, using primarily invasive coronary angiography (ICA) and recently non-invasive cardiac computed tomography angiography (CCTA). It is clear that there is correlation between geometrical parameters and both the haemodynamic alterations augmenting the atherosclerosis-prone environment and the extent of plaque burden. The purpose of this review is to discuss the currently available literature regarding this issue and propose a potential non-invasive imaging biomarker, the geometric risk score, which could be of importance to allow the early detection of individuals at increased risk of developing CAD

    Innovation Management in Health & Social Care (2023).

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    Welcome to the inaugural volume of Innovation Academy: Innovation Management in Health & Social Care. This volume represents the culmination of rigorous research and practical insights derived from the efforts of our first cohort of postgraduate students enrolled on the MSc in MSc Advanced Health and Care Management (Health Innovation and Transformation) and the MSc Advanced Health and Care Management (Value Based) programs. At the heart of this repository are practitioner-focused projects, which address contemporary challenges within the realm of value-based healthcare, innovation, and transformation. These projects not only showcase the academic prowess of our students but also underscore their dedication to driving positive change within their respective industries and, importantly, impact. The diversity of backgrounds among our students - hailing from health, social care, the third sector, and the wider life sciences industry - enriches the breadth and depth of perspectives presented within this volume. Their collective expertise, coupled with a shared commitment to innovation, forms the bedrock upon which this publication stands. We extend our sincerest gratitude to the Welsh Government for their invaluable support of the Intensive Learning Academies, which have provided a fertile ground for knowledge exchange, collaboration, and the cultivation of innovative ideas. We extend our heartfelt appreciation to our curators of repository materials: Dr. James Bourne, Dr. Katie Gibbs, Hafwen Lewis, Harrison, Edward Miller, and Ram Gurumoorthy. Their diligent efforts in organizing and collating the wealth of knowledge presented within these pages have been instrumental in bringing this publication to fruition. "The Innovation Academy" series stands as a testament to Swansea University iLab Research & Innovation Center's commitment to fostering an environment of open-access and knowledge sharing
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