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Abstract
Recent developments in the field of elemental spectroscopy suggest that the use of single particle inductively coupled plasma spectrometry (spICP-MS) might offer further information about exposure to a range of particles in the workplace. The technique detects individual elemental particles providing information about the size and number of particles present. There are many occupational settings where spICP-MS could be utilised to characterise exposure to particles better. It is possible to detect particles in a range of both environmental and biological samples and this could be especially useful where there are no well-established biological monitoring methods or where exposure is not fully understood. Results presented here will describe the spICP-MS method developed at HSE's laboratory where it has been possible to determine workers exposure to respirable crystalline silica. The measurements have been undertaken in exhaled breath condensate samples collected from workers and controls. Using the recently optimised method it has been possible to detect silicon-containing particles, across a size range of 100-2000 nm, in a one minute acquisition. Findings from recent analysis where it has been possible to detect titanium-containing particles in bulk environmental samples will also be shown. Additionally, from some preliminary work undertaken it might also be possible to detect metal particles from welding activities to help better capture daily exposures. This analytical technique shows promise for a range of workplace activities and has the potential to inform about the efficacy of control measures in the workplace, as well as specific information about the elemental particle exposures.
© Crown Copyright (2022)

Abstract
Biological monitoring is a useful way of determining overall exposures to chemical substances; however, in the case of respirable crystalline silica (RCS), this has not been possible in conventional biological matrices. Previous research at HSE has shown that it was possible to detect silicon-containing particles in exhaled breath condensate (EBC) samples using single particle inductively coupled mass spectrometry (spICPMS) in a small number of quarry workers, and at that time the method had a particle size detection limit of around 300 nm. In more recent work presented here we will describe the advances in the methodology and the results from exhaled breath condensate samples collected from a range of UK workers with potential RCS exposures. Control samples were also collected for comparison. Static air/bulk samples were also collected to allow the size distribution and concentration of RCS to be determined in each workplace. The analytical advances include moving to using an ICP tandem MS for better specificity with an improved sample introduction system. This has increased the size range detection of silicon-containing particles, allowing measurements in the size range of 100-2000 nm, in a one minute acquisition. We have also standardised the EBC sampling by collecting the same volume of exhaled air (50L) from each volunteer. This improved methodology offers a viable biomonitoring method for a range of workplaces and has the potential to inform information about the efficacy of respiratory protective equipment and control measures in the workplace, complementing occupational hygiene.

Abstract
Scientists from the Health and Safety Executive visited a manufacturing workplace where coatings are prepared by loading powders, frit and water into various sized mills. The aim of the visit was to determine potential worker exposures to dust and respirable crystalline silica by static air monitoring and exhaled breath condensate. Low-cost particle monitors were deployed alongside more established scientific equipment. Airborne dust concentrations were measured at three site locations using two photometers, an optical particle counter (OPC) and a respirable cyclone. The size distribution was measured in real-time using a low-cost OPC and by offline analysis of a polycarbonate membrane filter housed inside an inhalable sampler. Pre and post shift samples of exhaled breath condensate were collected from 6 workers, with samples analysed by single particle inductively coupled plasma mass spectrometry to measure the number and size of silicon containing particles present. The real-time air monitoring data at all three locations showed peaks in airborne concentrations corresponding to the loading activities and indicating the tasks most likely to contribute to worker exposure. The average concentration of respirable dust measured closest to the process was 0.13 mg.m-3 for the 8-hour shift. The low-cost monitors provided good information about the changes in concentration over time relating to worker activities.

This article belongs to the Special Issue 2nd Edition: Human Biomonitoring of Environmental and Occupational Exposures ; Study Protocol ; Workers involved in the processing of electronic waste (e-waste) are potentially exposed to toxic chemicals. If exposure occurs, this may result in uptake and potential adverse health effects. Thus, exposure surveillance is an important requirement for health risk management and prevention of occupational disease. Human biomonitoring by measurement of specific biomarkers in body fluids is considered as an effective method of exposure surveillance. The aim of this study is to investigate the internal exposure of workers processing e-waste using a human biomonitoring approach, which will stimulate improved work practices and contribute to raising awareness of potential hazards. This exploratory study in occupational exposures in e-waste processing is part of the European Human Biomonitoring Initiative (HBM4EU). Here we present a study protocol using a cross sectional survey design to study worker's exposures and compare these to the exposure of subjects preferably employed in the same company but with no known exposure to industrial recycling of e-waste. The present study protocol will be applied in six to eight European countries to ensure standardised data collection. The target population size is 300 exposed and 150 controls. Biomarkers of exposure for the following chemicals will be used: chromium, cadmium and lead in blood and urine; brominated flame retardants and polychlorobiphenyls in blood; mercury, organophosphate flame retardants and phthalates in urine, and chromium, cadmium, lead and mercury in hair. In addition, the following effect biomarkers will be studied: micronuclei, epigenetic, oxidative stress, inflammatory markers and telomere length in blood and metabolomics in urine. Occupational hygiene sampling methods (airborne and settled dust, silicon wristbands and handwipes) and contextual information will be collected to facilitate the interpretation of the biomarker results and discuss exposure mitigating interventions to further reduce exposures if needed. This study protocol can be adapted to future European-wide occupational studies. ; This work has received external 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. ; info:eu-repo/semantics/publishedVersion

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