Exposure assessment during paint spraying and drying using PTR-ToF-MS.

Spraying is a common way to distribute occupational products, but it puts worker's health at risk by exposing them to potentially harmful particles and gases. The objective of this study is to use time-resolved measurements to gain an understanding of spray applications at the process level and to compare them to predictions of exposure models. We used proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) at 1-s time resolution to monitor the gas phase concentration of the solvents acetone, ethanol, butyl acetate, xylene and 1-methoxy-2-propy acetate during outdoor spraying and indoor drying of metal plate under various conditions of outdoor air supply. We found that during spraying, gas-phase exposure was dominated by the more volatile solvents acetone and ethanol, which exhibited strong concentration variations due to the outdoor winds. During drying, exposure strongly depended on the strength of ventilation. Under conditions with high supply of outdoor air, our measurements show a near-exponential decay of the solvent concentrations during drying. Conversely, under conditions without outdoor air supply, the drying process required hours, during which the less volatile solvents passed through a concentration maximum in the gas phase, so that the exposure during drying exceeded the exposure during spraying. The concentrations measured during spraying were then compared for each of the substances individually with the predictions of the exposure models ECETOC TRA, Stoffenmanager, and ART using TREXMO. For these conditions, ECETOC TRA and Stoffenmanager predicted exposures in the measured concentration range, albeit not conservative for all solvents and each application. In contrast, ART largely overestimated the exposure for the more volatile solvents acetone and ethanol and slightly underestimated exposure to 1M2PA for one spraying. ECETOC TRA and ART do not have options to predict exposure during drying. Stoffenmanager has the option to predict drying together with spraying, but not to predict the drying phase independently. Our study demonstrates the importance of considering both the spray cloud and solvent evaporation during the drying process. To improve workplace safety, there is a critical need for enhanced exposure models and comprehensive datasets for calibration and validation covering a broader range of exposure situations.

A quantitative risk assessment for skin sensitizing plant protection products: Linking derived No-Effect levels (DNELs) with agricultural exposure models.

Chemical skin sensitizers produce allergic contact dermatitis, which is one of the most frequent occupational diseases associated with chemical exposures. Skin exposure is the major route of exposure when using plant protection products (PPPs). Therefore, skin sensitization is an important factor to be addressed during the regulatory risk assessment of PPPs. The main regulatory decision criterion considered when performing risk assessment for skin sensitizers is the dose applied. The equally important criteria "potency of the substance" is insufficiently considered by two potency categories as potency may vary up to five orders of magnitude. "Frequency of exposure" to the skin sensitizer is not considered at all. Consequently, an improved risk assessment methodology is essential to adequately assess health risks from skin sensitizers, especially for agricultural operators using PPPs. A quantitative risk assessment (QRA) approach for addressing PPPs sensitizing potential is proposed here. This QRA combines a methodology to derive a substance-specific threshold for skin sensitizers, a Derived No-Effect Level (DNEL), and an agricultural exposure model used for assessing chronic health risks of PPPs. The proposed QRA for skin sensitizing PPPs is a clear improvement over current risk assessment to ensure the safe use of skin sensitizers in an occupational context.

Occupational exposure to plant protection products and health effects in Switzerland: what do we know and what do we need to do?

AIMS: There is currently no centralised database on workers' exposures to plant protection products (PPPs) in Switzerland, nor a national register for negative health effects linking them to occupational PPP exposure. This lack of basic data makes it difficult to implement either epidemiological research or prevention campaigns for the agricultural sector. The first objective was to understand the level of information and flow of data on occupational PPP exposures and health effects in the Canton of Vaud, Switzerland. Then, to apply this information to develop recommendations for improving a vigilance system for occupational health effects related to PPP exposure. METHODS: A mapping study and semistructured stakeholder interviews were conducted to better understand the flow of data on occupational PPP exposures and health effects. A clinical records investigation of workers occupationally exposed to PPPs was undertaken to understand the magnitude of this potential problem. Finally, a workshop brought together relevant stakeholders to discuss recommendations for the way forwards. RESULTS: A lack of data on PPP exposures and associated health effects was revealed. This highlighted important knowledge gaps at different levels of the current institutional information flow system. We found that although there were numerous stakeholders that worked efficiently in their own mandate, there was a clear need for increased collaboration and coordination in order to make use of existing data to promote safer PPP use among agricultural workers in Switzerland. CONCLUSIONS: Due to increasing evidence of an association between PPP exposure and health effects, increased collaboration between stakeholders is necessary to develop links between the data sources that already exist. Our study was the first to investigate the health effects linked to PPP exposure among the Swiss agricultural population. The recommendations presented in this paper would help promote a safer and healthier agricultural workforce in Switzerland, as well as the population at large.

Research and development-where people are exposed to nanomaterials.

OBJECTIVES: Many nanomaterials (materials with structures smaller than 100 nm) have chemical, physical and bioactive characteristics of interest for novel applications. Considerable research efforts have been launched in this field. This study aimed to study exposure scenarios commonly encountered in research settings. METHODS: We studied one of the leading Swiss universities and first identified all research units dealing with nanomaterials. After a preliminary evaluation of quantities and process types used, a detailed analysis was conducted in units where more than a few micrograms were used per week. RESULTS: In the investigated laboratories, background levels were usually low and in the range of a few thousand particles per cubic centimeter. Powder applications resulted in concentrations of 10,000 to 100,000 particles/cm(3) when measured inside fume hoods, but there were no or mostly minimal increases in the breathing zone of researchers. Mostly low exposures were observed for activities involving liquid applications. However, centrifugation and lyophilization of nanoparticle-containing solutions resulted in high particle number levels (up to 300,000 particles/cm(3)) in work spaces where researchers did not always wear respiratory protection. No significant increases were found for processes involving nanoparticles bound to surfaces, nor were they found in laboratories that were visualizing properties and structure of small amounts of nanomaterials. CONCLUSIONS: Research activities in modern laboratories equipped with control techniques were associated with minimal releases of nanomaterials into the working space. However, the focus should not only be on processes involving nanopowders but should also be on processes involving nanoparticle-containing liquids, especially if the work involves physical agitation, aerosolization or drying of the liquids.

A preliminary comparison of three dermal exposure sampling methods: rinses, wipes and cotton gloves.

Several methods exist to estimate dermal exposure and it is unclear how comparable they are. These methods fall into three main categories: (i) removal techniques (such as wiping or rinsing); (ii) interception techniques (such as gloves, patches, or coveralls); and (iii) fluorescent tracer techniques. Controlled experiments were conducted to compare two removal methods for exposure to particulate, and a removal method with an interception method for exposure to liquids. Volunteers' hands were exposed to three liquid solutions (glycerol-water solutions of different concentrations) and three particulates (Epsom salts, calcium acetate and zinc oxide) in simulated exposure scenarios. Both hands were exposed and a different sampling method was used on each to allow comparison of methods. Cotton glove samplers and a cotton wipe sampling method were compared for exposure to liquids. For exposure to powders a cotton wipe sampling method was compared to rinsing the hands in deionised water. Wipe and rinse methods generally yielded similar results for Epsom salts and zinc oxide (geometric mean [GM] ratios of wipe-to-rinse measurements of 0.6 and 1.4, respectively) but they did not for calcium acetate (GM wipe-to-rinse ratio of 4.6). For glycerol solutions measurements from the glove samplers were consistently higher than wipe samples. At lower levels of exposure the relative difference between the two methods was greater than at higher levels. At a hand loading level of 24,000 µg cm(-2) (as measured by wiping) the glove-to-wipe ratio was 1.4 and at a hand loading of 0.09 µg cm(-2) the ratio was 42.0. Wipe and rinse methods may be directly comparable but the relationship between glove and wipe sampling methods appears to be complex. Further research is necessary to enable conversion of exposure measurements from one metric to another, so as to facilitate more reliable risk assessment.

Properties of liquids and dusts: how do they influence dermal loading during immersion, deposition, and surface contact exposure pathways?

BACKGROUND: Although dustiness and viscosity are potential determinants of dermal exposure, their effect on exposure is poorly understood. The goal of this study was to investigate the effect of dustiness and viscosity on dermal exposure by each of three dermal exposure pathways (deposition, surface contact, and immersion). METHODS: The hands of four volunteers were exposed to non-toxic substances: particulate with varying dustiness (calcium acetate, zinc oxide, and Epsom salt) and liquids of varying viscosity (three glycerol/water solutions containing 20, 50, or 85% glycerol) by each pathway. Dermal exposure was measured by a systematic wipe of the entire hand. Calcium acetate, zinc oxide, and Epsom salts were analysed on wipes by inductively coupled plasma/atomic emission spectrometry and glycerol was measured by gas chromatography with a flame ionization detector. The relationship between exposure and either dustiness or viscosity was examined using either parametric (analysis of variance) or non-parametric (Kruskal-Wallis) tests. RESULTS: Both viscosity and dustiness appeared to have an effect on dermal exposure. Increasing viscosity lead to higher exposures by the immersion pathway (P < 0.001) but lower exposures by the deposition pathway (although this relationship was not statistically significant: P = 0.19). Viscosity had no apparent effect on exposure from surface contact. Dustiness did not affect transfer of particulate to the skin by immersion (P = 0.403) but it did affect exposure by the surface transfer and deposition pathways. The dustiest substance (calcium acetate) transferred to skin more readily following contact with contaminated surfaces than zinc oxide or Epsom salts (P = 0.016). For the deposition pathway, the highest exposures were seen for the dustiest substance (calcium acetate) but statistical analysis was not conducted as 67% of measurements were below detection limits. CONCLUSION: The results suggest that both viscosity and dustiness can affect dermal exposure. They also show that the determinants of dermal exposure can be different for each of the dermal exposure pathways.

Nanoparticle usage and protection measures in the manufacturing industry--a representative survey.

Addressing the risks of nanoparticles requires knowledge about release into the environment and occupational exposure. However, such information currently is not systematically collected; therefore, this risk assessment lacks quantitative data. The goal was to evaluate the current level of nanoparticle usage in Swiss industry as well as health, safety, and environmental measures, and the number of potentially exposed workers. A representative, stratified mail survey was conducted among 1626 clients of the Swiss National Accident Insurance Fund (SUVA), which insures 80,000 manufacturing firms, representing 84% of all Swiss manufacturing companies (947 companies answered the survey for a 58.3% response rate). The extrapolation to all Swiss manufacturing companies results in 1309 workers (95% confidence interval [CI]: 1073 to 1545) potentially exposed to nanoparticles in 586 companies (95% CI: 145 to 1027). This corresponds to 0.08% of workers (95% CI: 0.06% to 0.09%) and to 0.6% of companies (95% CI: 0.2% to 1.1%). The industrial chemistry sector showed the highest percentage of companies using nanoparticles (21.2%). Other important sectors also reported nanoparticles. Personal protection equipment was the predominant protection strategy. Only a few applied specific environmental protection measures. This is the first nationwide representative study on nanoparticle use in the manufacturing sector. The information gained can be used for quantitative risk assessment. It can also help policymakers design strategies to support companies developing a safer use of nanomaterial. Noting the current low use of nanoparticles, there is still time to proactively introduce protective methods. If the predicted "nano-revolution" comes true, now is the time to take action.

Reviewing the environmental and human health knowledge base of carbon nanotubes.

Carbon nanotubes (CNTs) are one of the most promising materials in nanotechnology. The various synthesis, purification and postprocessing methods produce CNTs with diverse physical characteristics, appliable in many fields. Their extensive projected use makes it important to understand their potential harmful effects. Besides showing a notable range of results of some toxicology studies, this review concluded that: a) there are different types of CNTs; thus, they cannot be considered a uniform group of substances; and b) in environmental compartments, CNTs can be bioavailable to organisms. Their properties suggest a possible accumulation along the food chain and high persistence. In organisms, CNT absorption, distribution, metabolism, excretion and toxicity depend on the inherent physical and chemical characteristics (e.g., functionalization, coating, length and agglomeration state), influenced by external environmental conditions during CNT production, use, and disposal. Thus, characterized exposure scenarios could be useful in toxicology studies. However, upon reaching the lungs in enough quantity, CNTs produce a toxic response (time and dose-dependent). The risks to human health and environment should be identified for a successful introduction of CNTs in future applications.

Use of nanoparticles in Swiss Industry: a targeted survey.

A large number of applications using manufactured nanoparticles of less than 100 nm are currently being introduced into industrial processes. There is an urgent need to evaluate the risks of these novel particles to ensure their safe production, handling, use, and disposal. However, today we lack even rudimentary knowledge about type and quantity of industrially used manufactured nanoparticles and the level of exposure in Swiss industry. The goal of this study was to evaluate the use of nanoparticles, the currently implemented safety measures, and the number of potentially exposed workers in all types of industry. To evaluate this, a targeted telephone survey was conducted among health and safety representatives from 197 Swiss companies. The survey showed that nanoparticles are already used in many industrial sectors; not only in companies in the new field of nanotechnology, but also in more traditional sectors, such as paints. Forty-three companies declared to use or produce nanoparticles, and 11 imported and traded with prepackaged goods that contain nanoparticles. The following nanoparticles were found to be used in considerable quantities (> 1000 kg/year per company): Ag, Al-Ox, Fe-Ox, SiO2, TiO2, and ZnO. The median reported quantity of handled nanoparticles was 100 kg/year. The production of cosmetics, food, paints, powders, and the treatment of surfaces used the largest quantities of these nanoparticles. Generally, the safety measures were found to be higher in powder-based than in liquid-based applications. However, the respondents had many open questions about best practices, which points to the need for rapid development of guidelines and protection strategies.

Reviewing the environmental and human health knowledge base of carbon nanotubes / Revisão sobre a base de conhecimento de saúde ambiental e humana dos nanotubos de carbono

Carbon nanotubes (CNTs) are one of the most promising materials in nanotechnology. The various synthesis, purification and postprocessing methods produce CNTs with diverse physical characteristics, appliable in many fields. Their extensive projected use makes it important to understand their potential harmful effects. Besides showing a notable range of results of some toxicology studies, this review concluded that: a) there are different types of CNTs; thus, they cannot be considered a uniform group of substances; and b) in environmental compartments, CNTs can be bioavailable to organisms. Their properties suggest a possible accumulation along the food chain and high persistence. In organisms, CNT absorption, distribution, metabolism, excretion and toxicity depend on the inherent physical and chemical characteristics (e.g., functionalization, coating, length and agglomeration state), influenced by external environmental conditions during CNT production, use, and disposal. Thus, characterized exposure scenarios could be useful in toxicology studies. However, upon reaching the lungs in enough quantity, CNTs produce a toxic response (time and dose-dependent). The risks to human health and environment should be identified for a successful introduction of CNTs in future applications.

Os nanotubos de carbono(CNT)são um dos materiais mais promissores da nanotecnologia. Os métodos de síntese, purificação e pós-processamento produzem CNT com diversas características físicas e uso em várias áreas. A projeção de uso abrangente do CNT urge a compreensão de seus possíveis efeitos nocivos. Essa revisão mostra um leque de resultados de estudos toxicológicos e concluiu que: a) há diferentes tipos de CNT; portanto, não pode ser considerado um grupo uniforme de substâncias; e b) em compartimentos ambientais,o CNT pode ser biodisponível aos organismos. Suas propriedades sugerem possível acúmulo na cadeia alimentar e alta persistência. Em organismos, sua absorção, distribuição, metabolismo, excreção e toxicidade do dependem de características físicas e químicas inerentes (e.g., funcionalização, revestimento, comprimento e estado de aglomeração), influenciadas por condições ambientais externas durante a produção, uso e eliminação de CNT. Portanto, os cenários de exposição caracterizados podem ser úteis em estudos toxicológicos. Contudo, quando chega aos pulmões em quantidade suficiente, o CNT produz uma resposta tóxica (tempo e dose dependente). Os riscos à saúde humana e meio ambiente devem ser identificados para que o CNT possa ser usado com sucesso em futuras aplicações.

Reviewing the environmental and human health knowledge base of carbon nanotubes.

Carbon nanotubes (CNTs) are considered one of the most promising materials in nanotechnology, with attractive properties for many technologic applications. The different synthesis, purification, and postprocessing methods produce CNTs with different physical characteristics, which can be applied in different fields ranging from composite materials, medical applications, and electronics to energy storage. The widespread projected use of CNTs makes it important to understand their potential harmful effects. In this environmental health review we observed a remarkable range of results of some of the toxicology studies. The comparability should be improved by further standardization and introduction of reference materials. However, at present the findings of this review suggest several key points: a) there are different types of CNTs, and therefore they cannot be considered a uniform group of substances; and b) in environmental compartments, CNTs can be bioavailable to organisms. The properties of CNTs suggest a possible accumulation along the food chain and high persistence. In organisms the absorption, distribution, metabolism, excretion, and toxicity of CNTs depend on the inherent physical and chemical characteristics such as CNT functionalization, coating, length, and agglomeration state that are influenced by the external environmental conditions during CNT production, use, and disposal stages. Characterized exposure scenarios could therefore be useful when conducting toxicologic studies. However, CNTs produce a toxic response upon reaching the lungs in sufficient quantity; this reaction is produced in a time-and dose-dependent manner. The identification of possible risks to human health and environment is a prerequisite for a successful introduction of CNTs in future applications.