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41 páginas, 6 tablas y 2 figuras. ; The potential contribution to the local geochemical balance of five historical eruptions that occurred during the 20th Century has been investigated in the Southern Volcanic Zone (SVZ) of the Andean volcanic arc of South America (Lonquimay 1988, Hudson 1991, Copahue 2000, Llaima 2008, Chaitén 2008). These ashes were characterised by SEMEDX and XRD, and their potential released geochemical fluxes were examined using water and nitric acid batch leaching tests. Leachates were analysed by ICP-OES, ICP-MS and ISE. The major contents removed correspond to SO42– and Cl–. The potential toxic trace element (PTTE) content was highly variable among the ash samples following this order: Chaitén > Copahue > Hudson > Llaima > Lonquimay. The trace elements with significant load in water batch leaching tests include Fe > F > B > P > Zn > As > Mn > Sr > Ba > Ti > Cu > Ni > Li > Rb > Co > Cr > Cd > Sb. Some of these elements (As, Cu, F, Mo, Ni, Pb and Zn) are included in the drinking water guidelines due to their potential toxicity and must be especially monitored in the environmental assessment of these ashfall deposits. ; Acknowledgements to the technical support of ICTJA XRD Survey (J. Elvira) and 502 the Scientific-Technical Surveys of the University of Barcelona in the analytical 503 work. The sample from Chaiten volcano was supplied by Dr. A. Caselli from the 504 Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 505 Argentina. We are grateful to the anonymous reviewers for their truly helpful 506 comments. This study was carried out in the framework of the PEGEFA Working 507 Group (Catalonian Government "Grup de Recerca Consolidat" 2009-SGR-972), 508 and was funded by the Project ASH of the Spanish Ministry of Science and 509 Technology (CGL2008-00099) and the FPU Grant of the Spanish Ministry of 510 Education of one of the authors (F. Ruggieri, Ref. AP2006-04592). ; Peer reviewed

The environmental geochemical behaviour of the rhyolitic ashes from the 2008 eruption of Chaitén volcano, Southern Chile, has been studied. After the bulk characterisation, the potential contribution to the regional geochemical fluxes was examined using: i) single batch leaching tests to provide a rapid screening of the implied major and trace elements; and ii) column experiments to evaluate the temporal mobility of leached elements. The environmental concerns of these ashes are related to the fine grained component present in each sample (independent of distance from the source), in particular the presence of cristobalite, and the geochemical hazards posed by ash-water interaction. Leaching experiments show the fast dissolution of surface salts and aerosols, which dominate over glass dissolution during the first steps of the ash-water interaction. Chaitén ashes could transfer to the environment more than 1×10 10g or 10,000metric tonnes (mt) of Cl, S, Ca, Na, Si, and K; between 1000 and 10,000mt of F, Mg, and Al; between 100 and 1000mt of As, Pb, P, Fe, Sr, Zn, Mn, and Br; between 10 and 100mt of Ba, Li, Ti, Ni, Nb, Cu, Rb, Zr, V, Mo, Co, and Sc; and less than 10mt of Cr, Sb, Ce, Ga, Cs, and Y. These results show the fertilising potential of the ashes (e.g., providing Ca and Fe) but also the input of potentially toxic trace elements (e.g., F and As) in the regional geochemical mass balance. The Chaitén results evidence lower potentials for poisoning and fertilising than low silica ashes due to the lower contents released of practically all elements. © 2012 Elsevier B.V. ; We acknowledge the technical support of ICTJA-CSIC labGEOTOP and DRX Surveys (M. Rejas and J. Elvira) and the Scientific-Technical Surveys of the University of Barcelona in the analytical work. This study was carried out in the framework of the PEGEFA Working Group (Catalonian Government "Grup de Recerca Consolidat" 2009-SGR-972), and was partly funded by the Projects ASH and QUECA of the Spanish Ministry of Science and Technology (CGL2008-00099 and CGL2011-23307) and the FPU Grant of the Spanish Ministry of Education of one of the authors (F. Ruggieri, Ref. AP2006-04592). ; Peer Reviewed

A method to obtain robust information on short term leaching behaviour of volcanic ashes has been developed independently on the sample age. A mixed factorial design (MFD) was employed as a multivariate strategy for the evaluation of the effects of selected control factors and their interactions (amount of sample (A), contact time (B), and liquid to solid ratio or L/S (C)) on the leaching process of selected metals (Na, K, Mg, Ca, Si, Al, V, Mn, Fe, and Co) and anions (Cl - and SO 4 2-). Box plots of the data acquired were used to evaluate the reproducibility achieved at different experimental conditions. Both the amount of sample (A) and leaching time (B) had a significant effect on the element stripping whereas the L/S ratio influenced only few elements. The lowest dispersion values have been observed when 1.0g was leached with an L/S ratio equal to 10, shaking during 4h. The entire method is completed within few hours, and it is simple, feasible and reliable in laboratory conditions. © 2012 Elsevier B.V. ; This study was carried out in the framework of the PEGEFA Working Group (Catalonian Government "Grup de Recerca Consolidat" 2009-SGR-972), and was partly funded by the Project ASH of the Spanish Ministry of Science and Technology (CGL2008-00099) and the FPU Grant of the Spanish Ministry of Education of one of the authors (F. Ruggieri, Ref. AP2006-04592). ; Peer Reviewed

© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). ; The increasing number of human biomonitoring (HBM) studies undertaken in recent decades has brought to light the need to harmonise procedures along all phases of the study, including sampling, data collection and analytical methods to allow data comparability. The first steps towards harmonisation are the identification and collation of HBM methodological information of existing studies and data gaps. Systematic literature reviews and meta-analyses have been traditionally put at the top of the hierarchy of evidence, being increasingly applied to map available evidence on health risks linked to exposure to chemicals. However, these methods mainly capture peer-reviewed articles, failing to comprehensively identify other important, unpublished sources of information that are pivotal to gather a complete map of the produced evidence in the area of HBM. Within the framework of the European Human Biomonitoring Initiative (HBM4EU) initiative-a project that joins 30 countries, 29 from Europe plus Israel, the European Environment Agency and the European Commission-a comprehensive work of data triangulation has been made to identify existing HBM studies and data gaps across countries within the consortium. The use of documentary analysis together with an up-to-date platform to fulfil this need and its implications for research and practice are discussed. ; HBM4EU has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 733032. ; info:eu-repo/semantics/publishedVersion

The increasing number of human biomonitoring (HBM) studies undertaken in recent decades has brought to light the need to harmonise procedures along all phases of the study, including sampling, data collection and analytical methods to allow data comparability. The first steps towards harmonisation are the identification and collation of HBM methodological information of existing studies and data gaps. Systematic literature reviews and meta-analyses have been traditionally put at the top of the hierarchy of evidence, being increasingly applied to map available evidence on health risks linked to exposure to chemicals. However, these methods mainly capture peer-reviewed articles, failing to comprehensively identify other important, unpublished sources of information that are pivotal to gather a complete map of the produced evidence in the area of HBM. Within the framework of the European Human Biomonitoring Initiative (HBM4EU) initiative-a project that joins 30 countries, 29 from Europe plus Israel, the European Environment Agency and the European Commission-a comprehensive work of data triangulation has been made to identify existing HBM studies and data gaps across countries within the consortium. The use of documentary analysis together with an up-to-date platform to fulfil this need and its implications for research and practice are discussed. ; HBM4EU has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 733032. ; Sí

Funding Information: Funding: This research was conducted under the HBM4EU project and was funded by European Union's Horizon 2020 research and innovation program under grant agreement no. 733032 and received co-funding from the author's organizations and/or Ministries. Luxembourg entered the study at a later stage and thus financed the study at its own means. Publisher Copyright: © 2022 by the author. Licensee MDPI, Basel, Switzerland. ; Work-related exposures in industrial processing of chromate (chrome plating, surface treatment and welding) raise concern regarding the health risk of hexavalent chromium (Cr(VI)). In this study, performed under the HBM4EU project, we focused on better understanding the determinants of exposure and recognising how risk management measures (RMMs) contribute to a reduction in exposure. HBM and occupational hygiene data were collected from 399 workers and 203 controls recruited in nine European countries. Urinary total chromium (U-Cr), personal inhalable and respirable dust of Cr and Cr(VI) and Cr from hand wipes were collected. Data on the RMMs were collected by questionnaires. We studied the association between different exposure parameters and the use of RMMs. The relationship between exposure by inhalation and U-Cr in different worker groups was analysed using regression analysis and found a strong association. Automatisation of Cr electroplating dipping explained lower exposure levels in platers. The use of personal protective equipment resulted in lower U-Cr levels in welding, bath plating and painting. An effect of wearing gloves was observed in machining. An effect of local exhaust ventilation and training was observed in welding. Regression analyses showed that in platers, exposure to air level of 5 µg/m3 corresponds to U-Cr level of 7 µg/g creatinine. In welders, the same inhalation exposure resulted in lower U-Cr levels reflecting toxicokinetic differences of different chromium species. ; publishersversion ; published

Multicenter Study ; The EU human biomonitoring initiative, HBM4EU, aims to co-ordinate and advance human biomonitoring (HBM) across Europe. As part of HBM4EU, we presented a protocol for a multicentre study to characterize occupational exposure to hexavalent chromium (Cr(VI)) in nine European countries (HBM4EU chromates study). This study intended to collect data on current occupational exposure and to test new indicators for chromium (Cr) biomonitoring (Cr(VI) in exhaled breath condensate and Cr in red blood cells), in addition to traditional urinary total Cr analyses. Also, data from occupational hygiene samples and biomarkers of early biological effects, including genetic and epigenetic effects, was obtained, complementing the biomonitoring information. Data collection and analysis was completed, with the project findings being made separately available. As HBM4EU prepares to embark on further European wide biomonitoring studies, we considered it important to reflect on the experiences gained through our harmonised approach. Several practical aspects are highlighted for improvement in future studies, e.g., more thorough/earlier training on the implementation of standard operating procedures for field researchers, training on the use of the data entry template, as well as improved company communications. The HBM4EU chromates study team considered that the study had successfully demonstrated the feasibility of conducting a harmonised multicentre investigation able to achieve the research aims and objectives. This was largely attributable to the engaged multidisciplinary network, committed to deliver clearly understood goals. Such networks take time and investment to develop, but are priceless in terms of their ability to deliver and facilitate knowledge sharing and collaboration. ; Highlights: Feasibility of conducting harmonised Pan-European biomonitoring study on occupational exposure demonstrated; Developing a successful network and implementation of systematic methodology takes significant dedication from all involved; Methodological improvements were identified which will benefit future large-scale occupational biomonitoring campaigns; Developed multicentre network allows and promotes further opportunities for future research, knowledge sharing and collaboration; Data produced supports science to policy interface in the scope of REACH and occupational safety and health regulations. ; This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 733032 and received co-funding from the author's organizations and/or Ministries. ; info:eu-repo/semantics/publishedVersion

The EU human biomonitoring initiative, HBM4EU, aims to co-ordinate and advance human biomonitoring (HBM) across Europe. Within its remit, the project is gathering new, policy relevant, EU-wide data on occupational exposure to relevant priority chemicals and developing new approaches for occupational biomonitoring. In this manuscript, the hexavalent chromium [Cr(VI)] study design is presented as the first example of this HBM4EU approach. This study involves eight European countries and plans to recruit 400 workers performing Cr(VI) surface treatment e.g. electroplating or stainless steel welding activities. The aim is to collect new data on current occupational exposure to Cr(VI) in Europe and to test new methods for Cr biomonitoring, specifically the analysis of Cr(VI) in exhaled breath condensate (EBC) and Cr in red blood cells (RBC) in addition to traditional urinary total Cr analyses. Furthermore, exposure data will be complemented with early biological effects data, including genetic and epigenetic effects. Personal air samples and wipe samples are collected in parallel to help informing the biomonitoring results. We present standard operational procedures (SOPs) to support the harmonized methodologies for the collection of occupational hygiene and HBM samples in different countries. ; This work has received funding from the European Union's Horizon 2020 research and innovation program under grant agreement No 733032 and received co-funding from the author's organizations and/or Ministries. ; Sí

Exposure to hexavalent chromium [Cr(VI)] may occur in several occupational activities, e.g., welding, Cr(VI) electroplating and other surface treatment processes. The aim of this study was to provide EU relevant data on occupational Cr(VI) exposure to support the regulatory risk assessment and decision-making. In addition, the capability and validity of different biomarkers for the assessment of Cr(VI) exposure were evaluated. The study involved nine European countries and involved 399 workers in different industry sectors with exposures to Cr(VI) such as welding, bath plating, applying or removing paint and other tasks. We also studied 203 controls to establish a background in workers with no direct exposure to Cr(VI). We applied a cross-sectional study design and used chromium in urine as the primary biomonitoring method for Cr(VI) exposure. Additionally, we studied the use of red blood cells (RBC) and exhaled breath condensate (EBC) for biomonitoring of exposure to Cr(VI). Personal measurements were used to study exposure to inhalable and respirable Cr(VI) by personal air sampling. Dermal exposure was studied by taking hand wipe samples. The highest internal exposures were observed in the use of Cr(VI) in electrolytic bath plating. In stainless steel welding the internal Cr exposure was clearly lower when compared to plating activities. We observed a high correlation between chromium urinary levels and air Cr(VI) or dermal total Cr exposure. Urinary chromium showed its value as a first approach for the assessment of total, internal exposure. Correlations between urinary chromium and Cr(VI) in EBC and Cr in RBC were low, probably due to differences in kinetics and indicating that these biomonitoring approaches may not be interchangeable but rather complementary. This study showed that occupational biomonitoring studies can be conducted successfully by multi-national collaboration and provide relevant information to support policy actions aiming to reduce occupational exposure to chemicals. ; This work has received funding from the European Union's Horizon 2020 research and innovation program under grant agreement No 733032 and received co-funding from the author's organizations and/or Ministries. Luxembourg entered the study at a later stage and thus financed the study at its own means. ; Sí

Exposure to hexavalent chromium [Cr(VI)] may occur in several occupational activities, e.g., welding, Cr(VI) electroplating and other surface treatment processes. The aim of this study was to provide EU relevant data on occupational Cr(VI) exposure to support the regulatory risk assessment and decision-making. In addition, the capability and validity of different biomarkers for the assessment of Cr(VI) exposure were evaluated. The study involved nine European countries and involved 399 workers in different industry sectors with exposures to Cr(VI) such as welding, bath plating, applying or removing paint and other tasks. We also studied 203 controls to establish a background in workers with no direct exposure to Cr(VI). We applied a cross-sectional study design and used chromium in urine as the primary biomonitoring method for Cr(VI) exposure. Additionally, we studied the use of red blood cells (RBC) and exhaled breath condensate (EBC) for biomonitoring of exposure to Cr(VI). Personal measurements were used to study exposure to inhalable and respirable Cr(VI) by personal air sampling. Dermal exposure was studied by taking hand wipe samples. The highest internal exposures were observed in the use of Cr(VI) in electrolytic bath plating. In stainless steel welding the internal Cr exposure was clearly lower when compared to plating activities. We observed a high correlation between chromium urinary levels and air Cr(VI) or dermal total Cr exposure. Urinary chromium showed its value as a first approach for the assessment of total, internal exposure. Correlations between urinary chromium and Cr(VI) in EBC and Cr in RBC were low, probably due to differences in kinetics and indicating that these biomonitoring approaches may not be interchangeable but rather complementary. This study showed that occupational biomonitoring studies can be conducted successfully by multi-national collaboration and provide relevant information to support policy actions aiming to reduce occupational exposure to chemicals. ; This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 733032 and received co-funding from the author's organizations and/or Ministries. ; info:eu-repo/semantics/publishedVersion