42 research outputs found

    Criteria and methods for microplastics monitoring in water to be used for human consumption within the new EU legislation framework

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    Microplastics are ubiquitous contaminants and their release into the environment has long been documented, especially in the last few years. Their widespread presence in several environmental and biological matrices, even in those usually less prone to contamination, have led the regulatory authorities, the scientific community and interested stakeholders to question about possible effects on human health. While the toxicity posed by plastics and microplastics (especially those > 300 ”m) to marine organisms seems evident, effects induced by smaller particles on humans are yet to be understood. The main challenge in the identification and toxicological assessments of microplastics rises from the complexity and heterogeneity of these compounds. Regarding microplastics analysis, several different approaches are available. However, the application of different sampling, pre-treatment and analytical methods has resulted in not directly comparable data. In addition, as a consequence of toxicological findings, analytical criteria and matrices investigated are changing. To deal with the increasing levels of plastics and microplastic pollution, the European Commission is adopting a number of actions under the European Green Deal and the Circular Economy Action Plan. In addition, in Directive (EU) 2020/2184 on the quality of water intended for human consumption microplastics appeared for the first time. Described as emerging compounds, microplastics have been related to the “watch list” mechanism introduced with Directive (EU) 2020/2184. The European Commission, by 2024, aims to adopt an analytical method to measure microplastics and, by 2019, to submit a report of risk analysis related to microplastics in drinking water. In order to identify a suitable analytical methodology, the European Commission's Joint Research Centre (JRC) launched a dedicated project in order to harmonize experience and knowledge about microplastic analysis in drinking water, requiring support from national technical-scientific representatives, industry experts and stakeholders. This project includes an online survey and a (series of) workshops designed to collect contribution from stakeholders and experts in microplastics analysis. It is within this complex framework that the present PhD project was structured. This project has multiple purposes, equally divided between the institutional and experimental activities. Institutional activities included the establishment of the Italian National working group on microplastics in drinking water and the discussion on data resulting from the first national survey, based on feedbacks by working group members. The Italian National working group which includes experts from the National Research Council (CNR), national and local environmental Authorities (SNPA: ISPRA and ARPA), Universities and Federation of water suppliers (Utilitalia). The group was designed to work on: (i) JRC and EC support on national expertise about microplastic monitoring in drinking water (ii) development of national analytical method for microplastic in drinking water to be presented to the JRC. From survey data, emerged that experts are flexibly adapting to new challenges posed by microplastics. Regarding experimental activities, specific aims were to develop a method for microplastic analysis suitable for both surface water and water to be used for human consumption, by comparing sampling and analytical techniques, in order to evaluate their pros and cons with a view to a routine approach. Surface water to be used for human for human consumption from the three longest Italian rivers (Po, Adige and Tiber) and water from Drinking Water Treatment Plants (DWTPs) were sampled. For microplastics sampling, a new sampling method, including 2-steps in situ filtration was developed in order to collect several litres of surface water. Assembled filtration system proved to be effective in filtering high volumes of surface water without clogging (average of 1.803,6 L). Tests to assess the goodness of this sampling method for drinking water were also carried out and an average of 2792,6 L litres was filtered without clogging. In order to compare sampling techniques, also water was collected by filling 2.5 L bottles (discrete sampling). Sample pre-treatment and Micro-FTIR analysis were carried out at Istituto di Scienze Polari – Consiglio Nazionale delle Ricerche (ISP-CNR) in Mestre while Micro-Raman analysis were carried out at Department of Chemistry of Padua University. Regarding sample pre-treatment, a “mild” oleo-extraction and purification method was employed. The method has been proved to be adaptable to surface water and efficient to extract microplastics, minimizing any interferers for the analysis. Abundance and polymer identifications were evaluated following the “semi-automated analysis: particle measuring” and “subsampling” approaches in Micro-FTIR. Each IR transmittance spectrum of suspected plastics was then compared with specific microplastics reference libraries. Microplastics were counted, identified and divided by size and shape. For particles between 20 and 100 ”m a size range distribution was also performed. Microplastics were observed in every surface water samples collected with both sampling methods, with the exception of the one performed at DWTP #1 with the filtration system, due to inability to properly apply particle measurement to the filters. Microplastics found greatly differed in type and number at each sampling site, while for size distribution and shape greater homogeneity was observed. In terms of polymer composition, heterogeneity was observed, probably due to differences between the various sampling sites. In samples from the filtration systems, polyester, fluorocarbon, polytetrafluoroethylene and acrylic were retrieved in both samples while, in their corresponding discrete samples, only fluorocarbon and polyolefin were common to all sites. Thus, only fluorocarbon was common to all surface water samples. A higher homogeneity was noted by comparing the composition of plastics in filtration system samples with the corresponding discrete samples of the same site. However, only 5 polymers out of 9 (approx. 56%) were common in DWTP #2 and only 5 polymers out of 12 (approx. 42%) were common in DWTP #3. These differences underline the necessity of performing also studies on sampling methods when developing protocols for microplastics analysis, as results may be very different by changing the sampling input. In terms of size, a higher homogeneity was observed. Only approximately 5% of particles found was bigger in size than 100 ”m (max 515,9 ”m) and approximately 95% of particle size varied between 20 and 100 ”m. In any case, particles between 7 ”m (LoD) and 20 ”m, potentially the most harmful ones, were not retrieved in any samples analyzed with Micro-FTIR. In addition, a detailed dimensional analysis of particles 20 – 100 ”m fraction was performed for each sample. Data showed that 40-50 ”m size cluster was the most populated for every sample. The 40-50 ”m size cluster remained the most populated even if stratifying by sampling techniques and assuming a 1000 L volume for filtration system samples. A general trend in which particles are more condensed in the region to the left of the 60-70 ”m cluster can be observed. In terms of shape, a high degree of homogeneity was observed among samples. Non-elongated particles were by far the most common particles (AR < 2) in all samples. The proportion of non-elongated particles over the total remained essentially the same stratifying data for sampling type (approx. 65% for filtration system samples assuming 1000 L as a reference volume and approx. 65% for discrete samples). Raman microscopy analysis was performed on two samples from DWTP #2 and DWTP #3 following the Point and Shoot and Imaging/Mapping approach. Several suspected microplastics were identified with Point and Shoot approach while in Imaging/Mapping a 50x50”m surface area with a 2 ”m-spaced grid was mapped. During the Imaging/Mapping, polyvinyl chloride and polyethylene signals (R = 0.53 and R = 0,69), were found in two different points, without any similar signals in the surrounding area. Thus, two suspected microplastics < 2 ”m were detected in the sample. Experimental showed that microplastics are present in surface water in significant amounts and have the opportunity to reach DWTPs. Each site showed different polymers composition but small microplastics (SMPs) (especially those non elongated and < 70 ”m) proved to be the most abundant group

    Physiothérapie et douleurs sexuelles chez la femme: impact d'un programme multidisciplinaire incluant la physiothérapie sur le vécu des femmes atteintes de vulvodynie provoquée : travail de Bachelor

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    Introduction. La vulvodynie est un inconfort vulvaire qui amĂšne une sensation brĂ»lure, se manifestant en l’absence de signe physique. Il s’agit d’une douleur chronique qui a des rĂ©percussions au niveau du bien-ĂȘtre que ce soit physique, mental et social. Objectifs. Évaluer l’impact de programmes multidisciplinaires incluant la physiothĂ©rapie sur le vĂ©cu des femmes atteintes de vulvodynie provoquĂ©e. MĂ©thode. Revue de littĂ©rature qualitative basĂ©e sur la sĂ©lection de deux articles qualitatifs comparables. La mĂ©thode utilisĂ©e a Ă©tĂ© l’analyse et la synthĂšse thĂ©matique des articles. RĂ©sultats. Cinq thĂšmes principaux sont ressortis de l’analyse thĂ©matique. La reconnaissance de la pathologie (connaĂźtre et ĂȘtre reconnue) est le premier pas vers l’acceptation et la prise de conscience. Dans la prise en charge multidisciplinaire, la femme apprend, grĂące aux diffĂ©rents professionnels, Ă  connaĂźtre ses besoins. Elle peut se sentir soutenue pour pouvoir s’ouvrir et dĂ©passer sa peur, ce qui l’amĂšne Ă  remonter la pente et enfin Ă  rallumer la flamme. Conclusion. La prise en charge multidisciplinaire se montre bĂ©nĂ©fique pour les femmes. Les points forts sont : l’élĂ©ment de choix, le respect des rythmes et des prĂ©fĂ©rences individuelles, l’éducation thĂ©rapeutique, le dĂ©veloppement de nouveaux outils. À travers un changement des croyances, la femme regagne le contrĂŽle et l’estime de soi en est amĂ©liorĂ©e; l’impact sur la qualitĂ© de la vie est positif. La physiothĂ©rapie touche la femme Ă  travers les cinq thĂšmes ressortis ; elle trouve donc sa place dans le programme

    Seeing into the past: integrating 3D documentation and non-invasive prospecting methods for the analysis, understanding and reconstruction of the ancient Pompeii. The case of the House of Obellio Firmo (IX, 14)

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    In 2015 the Department of History and Cultures of the Bologna University took part in the Grande Progetto Pompei - Piano della Conoscenza, with the task of providing a modern and complete documentation of the so-called Lotto 3 in Pompeii. The new survey was carried out by means of integrated innovative diagnostic survey techniques in order to provide a total documentary research of the whole sector. In 2016 a new project was started in agreement with the competent Superintendency, and focused on the study and preservation of the House of Obellio Firmo, included in the Lotto 3 of the Roman city. The new research contemplates an in-depth analysis of the building, employing systematic laser scanning and photogrammetry methods to generate an accurate 3D model of the house. This model is going to constitute the starting point for the further analysis of the wall stratigraphies and for the mapping and monitoring of the structures’ state of decay. The full-scale analytical documentation of the building also includes a detailed geophysical mapping of all the accessible domestic spaces, by using the ground penetrating radar technique. The preliminary results achieved by the non-invasive prospecting survey, integrated with the analysis of the surviving walls and building techniques, supply valid information for the archaeological interpretation of the house’s history. In order to allow the management and sharing of the information collected, the data are going to be organised within a building information model (BIM) with a triple objective: the reconstruction of a fragment of the ancient urban landscape in Pompeii during the oldest phase, with particular attention directed to the Samnitic period; the outlining of a precise strategy of intervention for the restoration and preservation of the House of Obellio Firmo; the re-opening of the building to sightseeing tours and its restitution to public use

    From A to Z: Using Alphabet Books as an instructional Tool with Older Readers

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    Alphabet books provide a literature source for teachers to use in the classroom that focuses on a common sequence of textual organization which upper elementary and middle school students have known since they were young children. These students most likely had in their repertoire of beginning to read activities, alphabet books using common symbols to match the letters such as A is for apple, B is for bear, C is for cat. The objects were selected to match the true sound of the letter with a single or small number of illustrations to demonstrate the concept. The alphabet book addresses the 26 letters in picture book format with typically 24 to 48 pages, illustrations on double pages, and brief text (Kormanski and Stevens, 1993)

    Non-Destructive Multi-Analytical Approach to Study the Pigments of Wall Painting Fragments Reused in Mortars from the Archaeological Site of Pompeii (Italy)

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    During the excavations carried out in Via di Mercurio (Regio VI, 9, 3) in Pompeii, in 2015, some red, green, black, and brown wall painting fragments were found in the preparatory layer of an ancient pavement which was probably built after the 62 AD earthquake. These fragments, derived from the rubble, were used as coarse aggregate to prepare the mortar for building the pavement. The wall painting fragments are exceptionally well preserved, which is an uncommon occurrence in the city of Pompeii. However, as they were enclosed in the mortar, the wall painting fragments were protected from the high temperatures (probably ranging between 180 ◩C and 380 ◩C) produced by the eruption in 79 AD. The pigmented outer surface of each sample was analyzed using a non-destructive multi-analytical approach, by combining spectrophotometric colorimetry and portable X-ray fluorescence with micro-Raman spectroscopy. The compositional characterization of the samples revealed the presence of cuprorivaite, goethite, and celadonite in the green pigments; hematite in the red pigments; goethite in the brown pigment; and charcoal in the black pigment. These data probably provide us with the most "faithful picture" of the various red, green, black, and brown pigments used in Pompeii prior to the 79 AD eruptio

    Elucidation of the chemical role of the pyroclastic materials on the state of conservation of mural paintings from Pompeii

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    Pyroclastic strata have always been thought to protect the archaeological remains of the Vesuvian area (Italy), hence allowing their conservation throughout the centuries. In this work, we demonstrate that they constitute a potential threat for the conservation state of the mural paintings of Pompeii. The ions that could be leached from them and the ion‐rich groundwater coming from the volcanic soil/rocks may contribute to salt crystallisation. Thermodynamic modelling not only allowed to predict which salts can precipitate from such leaching events but also assisted the identification of additional sources of sulfates and alkali metals to explain the formation of the sulfates identified in efflorescences from the mural paintings of Pompeii. For the future, fluorine, mainly related to a volcanic origin, can be proposed as a marker to monitor the extent of the impact in the mural paintings of Pompeii in situ

    Elucidation of the Chemical Role of the Pyroclastic Materials on the State of Conservation of Mural Paintings from Pompeii

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    Pyroclastic strata have always been thought to protect the archaeological remains of the Vesuvian area (Italy), hence allowing their conservation throughout the centuries. In this work, we demonstrate that they constitute a potential threat for the conservation state of the mural paintings of Pompeii. The ions that could be leached from them and the ion‐rich groundwater coming from the volcanic soil/rocks, may contribute to salt crystallisation. Thermodynamic modelling not only allowed to predict which salts can precipitate from such leaching events, but also assisted the identification of additional sources of sulfates and alkali metals, to explain the formation of the sulfates identified in efflorescences from the mural paintings of Pompeii. For the future, fluorine, mainly related to a volcanic origin, can be proposed as a marker to monitor in situ the extent of the impact in the mural paintings of Pompeii.The research leading to these results has received funding from “la Caixa” Foundation (Silvia PĂ©rez-Diez, ID 100010434, Fellowship code LCF/BQ/ES18/11670017). This work has been supported by the projects MADyLIN (Ministry of Economy, Industry and Competitiveness from Spain, Grant No. BIA2017‐87063‐P) funded by the Spanish Agency for Research AEI (MINECO-FEDER/UE) and MINECO-17-CTQ2016-77887-C2-1-R

    When Red Turns Black: Influence of the 79 AD Volcanic Eruption and Burial Environment on the Blackening/Darkening of Pompeian Cinnabar

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    It is widely known that the vivid hue of red cinnabar can darken or turn black. Many authors have studied this transformation, but only a few in the context of the archeological site of Pompeii. In this work, the co-occurrence of different degradation patterns associated with Pompeian cinnabar-containing fresco paintings (alone or in combination with red/yellow ocher pigments) exposed to different types of environments (pre- and post-79 AD atmosphere) is reported. Results obtained from the in situ and laboratory multianalytical methodology revealed the existence of diverse transformation products in the Pompeian cinnabar, consistent with the impact of the environment. The effect of hydrogen sulfide and sulfur dioxide emitted during the 79 AD eruption on the cinnabar transformation was also evaluated by comparing the experimental evidence found on paintings exposed and not exposed to the post-79 AD atmosphere. Our results highlight that not all the darkened areas on the Pompeian cinnabar paintings are related to the transformation of the pigment itself, as clear evidence of darkening associated with the presence of manganese and iron oxide formation (rock varnish) on fragments buried before the 79 AD eruption has also been found.The research leading to these results has received funding from “la Caixa” Foundation (Silvia PĂ©rez-Diez, ID 100010434, Fellowship code LCF/BQ/ES18/11670017). A.P.M. is a Serra HĂșnter fellow. A.P.M’s research was supported by a Beatriu de PinĂłs postdoctoral grant (2017 BP-A 00046) of the Government of Catalonia’s Secretariat for Universities & Research of the Ministry of Economy and Knowledge. This work has been supported by the project MADyLIN (BIA2017-87063-P) funded by the Spanish Agency for Research AEI (MINECO-FEDER/UE). The authors thank for the funding provided by University of the Basque Country through the Institutionally Sponsored Open Access

    In situ non-invasive multianalytical methodology to characterize mosaic tesserae from the House of Gilded Cupids, Pompeii

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    Mosaics, one of the most important decorative artworks in the Roman culture, were usually elaborated with a set of tesserae joined with lime or others binders to form geometric or figurative decorations. The identification of both substrate and colored compounds of the tesserae is a challenge for chemists and archaeologists. In this work, two mosaics present in the House of Gilded Cupids from the Archaeological Park of Pompeii were analyzed in situ by non destructive techniques. Raman and Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopies were used for the molecular and mineralogical characterization, and hand-held energy dispersive X-ray fluorescence (HH-EDXRF) spectrometry and Laser Induced Breakdown Spectroscopy (LIBS) for the elemental analysis. LIBS in-depth analysis was performed to obtain insights about the thickness of the pictorial layer determining that the thickness of red and orange pictorial layers was higher than 140 ÎŒm. The results showed that white tesserae were mainly composed by calcite, while local black colored volcanic rocks were used to manufacture black tesserae. Red and orange tesserae were composed by a calcite-based matrix with a hematite pictorial layer applied over it. Orange color was obtained by diluting hematite in the calcite matrix. Principal component analysis (PCA) of the XRF data was performed to observe differences and/or similarities between the analyzed mosaics; the samples projection of the PCA showed clear groupings.Iker Marcaida is grateful to the Basque Government who funded his predoctoral fellowship. This work has been supported by the project MADyLIN (BIA2017‑87063‑P) funded by the Spanish Agency for Research AEI (MINEICO‑FEDER/ UE)

    Chemometrics and elemental mapping by portable LIBS to identify the impact of volcanogenic and non-volcanogenic degradation sources on the mural paintings of Pompeii

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    Crystallization of soluble salts is a common degradation phenomenon that threatens the mural paintings of Pompeii. There are many elements that contribute to the crystallization of salts on the walls of this archaeological site. Notably, the leachates of the pyroclastic materials ejected in 79 AD by Mount Vesuvius and local groundwater, rich in ions from the erosion of volcanic rocks. Both sources could contribute to increase the concentration of halides (fluorides and chlorides) and other salts in these walls. The distribution of volcanogenic salts and their impact on the conservation of Pompeian mural paintings have however not yet been fully disclosed. In this work, an analytical methodology useful to determine the impact of the main sources of degradation affecting the mural paintings of Pompeii is presented. This methodology combines the creation of qualitative distribution maps of the halogens (CaF and CaCl) and related alkali metals (Na and K) by portable Laser Induced Breakdown Spectroscopy (LIBS) and a subsequent Principal Component Analysis of these data. Such maps, together with the in-situ identification of sulfate salts by portable Raman spectroscopy, provided information about the migration and distribution of volcanogenic halides and the influence of ions coming from additional sources (marine aerosol and modern consolidation mortars). Additionally, the thermodynamic modeling developed using the experimentally determined ionic content of Pompeian rain- and groundwater allowed to determine their specific role in the formation of soluble salts in the mural paintings of Pompeii.The research leading to these results has received funding from “la Caixa” Foundation (Silvia P erez-Diez, ID 100010434, Fellowship code LCF/BQ/ES18/11670017). This work has been supported by the Spanish Agency for Research AEI (MINECO- FEDER /UE) through the projects MADyLIN (BIA2017-87063-P) and MINECO-17-CTQ2016-77887-C2-1-R, and the Government of the Principality of Asturias (GRUPIN IDI/2018/000186). The authors thank for technical and human support provided by the laboratory Raman-LASPEA of SGIker (UPV/EHU/ ERDF, EU)
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