Ann. Occup. Hyg., Vol. 55, No. 9, pp. 980–988, 2011 Ó The Author 2011. Published by Oxford University Press on behalf of the British Occupational Hygiene Society doi:10.1093/annhyg/mer093 Advanced REACH Tool: Development and Application of the Substance Emission Potential Modifying Factor MARTIE VAN TONGEREN1*, WOUTER FRANSMAN2, SALLY SPANKIE1, MARTIN TISCHER3, DERK BROUWER2, JODY SCHINKEL2, JOHN W. CHERRIE1 and ERIK TIELEMANS2 1 Institute of Occupational Medicine, Research Avenue North, Riccarton, Edinburgh EH14 4AP, UK; Business Unit Quality and Safety, TNO Quality of Life, PO Box 360, 3700 AJ Zeist, The Netherlands; 3 Federal Institute for Occupational Safety and Health, Unit 4.1: Exposure Scenarios, 44149 Dortmund, Germany 2 Received 12 April 2011; in final form 22 August 2011 The Advanced REACH Tool (ART) is an exposure assessment tool that combines mechanistically modelled inhalation exposure estimates with available exposure data using a Bayesian approach. The mechanistic model is based on nine independent principal modifying factors (MF). One of these MF is the substance emission potential, which addresses the intrinsic substance properties as determinants of the emission from a source. This paper describes the current knowledge and evidence on intrinsic characteristics of solids and liquids that determine the potential for their release into workplace air. The principal factor determining the release of aerosols from handling or processing powdered, granular, or pelletized materials is the dustiness of the material, as well as the weight fraction of the substance of interest in the powder and the moisture content. The partial vapour pressure is the main intrinsic factor determining the substance emission potential for emission of vapours. For generation of mist, the substance emission potential is determined by the viscosity of the liquid as well as the weight fraction of the substance of interest in the liquid. Within ART release of vapours is considered for substances with a partial vapour pressure at the process temperature of 10 Pa or more, while mist formation is considered for substances with a vapour pressure £10 Pa. Relative multipliers are assigned for most of the intrinsic factors, with the exception of the weight fraction and the vapour pressure, which is applied as a continuous variable in the estimation of the substance emission potential. Currently, estimation of substance emission potential is not available for fumes, fibres, and gases. The substance emission potential takes account of the latest thinking on emissions of dusts, mists, and vapours and in our view provides a good balance between theory and pragmatism. Expanding the knowledge base on substance emission potential will improve the predictive power of occupational exposure models and thereby the accuracy and precision of the exposure estimates. Keywords: dust, dustiness; emission potential; exposure modelling; mist; vapour; volatility elled inhalation exposure with available exposure data using a Bayesian approach (Tielemans et al., 2011). The mechanistic model is based on nine independent principal modifying factors (MF) (Fransman et al., 2011). These include two source-related MF: (i) substance emission potential, which addresses how the intrinsic properties of the substance affect emission, and (ii) activity emission potential, which INTRODUCTION The Advanced REACH Tool (ART) is an exposure assessment tool that combines mechanistically mod*Author to whom correspondence should be addressed. Tel: þ44-131-449-8097; fax: +44-131-449-8084; e-mail: martie.van.tongeren@[email protected] 980 Substance Emission Potential addresses how the process or activity affects the emission of the substance. The latter is described by Marquart et al. (2011), while this paper describes the main intrinsic properties of substances in relation to emission. Depending on the type of product and the way it is handled, emission of a contaminant can result in several exposure forms. For instance, a solid object may result in inhalable dust exposure due to abrasion or fumes due to hot work. Table 1 provides a description of the various exposure forms. ART (version 1.0) estimates exposure for three of these exposure forms: vapour, mist, and dust; exposure to fumes, fibres, gases, and bioaerosols are presently excluded. Table 2 shows the different broad categories for modelling of ‘substance emission potential’ that are currently included in ART. For each category, a distinct set of underlying determinants is used for modelling the substance emission potential as the nature of the determinants across categories is very different. This paper describes the derivation of the factors that are used to model release of dust (from handling powders or abrasion of solid objects), along with mists and vapours (from handling liquids). These categories (Table 2) were also treated separately in the calibration of the mechanistic model as discussed by Schinkel et al. (2011). Further information on the mechanistic model is described by Fransman et al. (2011). 981 HANDLING POWDERS, GRANULES, AND PELLETS RESULTING IN DUST EXPOSURE The principal factor determining the release of aerosols from handling or processing powdered, granular, or pelletized materials is the dustiness of the material. Dustiness is characterized as the propensity of materials to produce airborne dust during handling (Mark, 2005). Dustiness can be tested by applying a standard type and amount of mechanical energy to a specified amount of test material for a specified time in order to overcome adhesive binding forces within the test material (Plinke et al., 1991) and thus disperse/release existing particles from the test material into the air (Lidén, 2006). For powders, dustiness can be estimated using several methods, but the two main methods are the rotating drum test and the continuous single-drop test (CEN, 2006). The rotating drum dustiness test involves the continuous multiple dropping of a sample of the material in a slow moving horizontal stream of air, while in the continuous single-drop method material falls through the air into an enclosed chamber. Both methods aim to reliably reproduce the generation of dust under standard conditions, mimicking different workplace powder handling scenarios (CEN, 2006). Unfortunately, the results of dustiness tests depend on various factors, including the apparatus used, the testing time, the mass of the chemical tested, the environmental conditions, and the dust fractions measured (Chung and Burdett, 1994; Table 1. Definitions of exposure forms Gas Vapour Dust Fume Mist Fibre Bioaerosol This is the airborne state of a chemical whose liquid is so volatile that its vapours cannot reach an equilibrium with its liquid. If such a chemical were present in an open container in a closed room, all the liquid would evaporate. This is the airborne state of a chemical, which, if a sufficiently large amount of liquid were released into a closed room at normal temperature, would not completely evaporate but rather would reach equilibrium with its liquid. Solid particles that are formed by aerosolization of already existing powders or by abrasion of solid objects. A broad range of diameters is possible but those larger than 100 lm in diameter will not stay airborne long. Solid particles that are formed by condensation from high temperature vapour, such as from molten metal or smoke. Fumes form at an initially very small diameter (ca. 0.01 lm), and although they will aggregate into larger particles, they still rarely get larger than 0.5 lm. Any airborne liquid particles. A water mist in the form of steam, fog, or a fine spray is a common example, but mists of an organic solvent or even mercury can be formed. Mists smaller than 1 lm are hard to generate, and mists larger than 100 lm will not stay airborne long. Elongated particles whose length-to-diameter ratio is at least 3:1. Particles of biologic origin (plants, food, etc.). Based on Popendorf (2006). Table 2. Overview of categories for modelling of ‘substance emission potential’ Categories for modelling substance emission potential Type of product Type of exposure Handling solid objects resulting in dust exposure Solid objects Dust Handling powders resulting in dust exposure Powders, granules, or pelletized material Dust Handling liquids resulting in vapour exposure Volatile liquids (vapour pressure .10 Pa) Vapour Handling liquid resulting in mist exposure Low-volatile liquids (vapour pressure 10 Pa) Mist 982 M. van Tongeren et al. Breum, 1999, Mark, 2005; CEN, 2006; Back and Schmidt, 2008; Pensis et al., 2010). Furthermore, the two test methods do not always rank materials in the same order (CEN, 2006, Pensis et al., 2010). Hence, dustiness is not a well-defined physical or chemical property of a product (Lidén, 2006). Using both the rotating drum and single-drop method, Heitbrink et al. (1990) found varying correlations between dustiness test results and exposure measurements at four workplaces with bag filling and dumping operations. On the other hand, simulations involving handling small volumes of powder showed that the dustiness index, measured using a single-drop method (Cowherd et al., 1989a), was one of five parameters significantly related to exposure (Cowherd et al., 1989b). Brouwer et al. (2006) showed that dustiness test results, obtained using a rotating drum method, explained 70% of the variance in personal dust exposure levels under controlled circumstances. However, they investigated only a limited number of substances. Intrinsic features of a product that are likely to be associated with the dustiness include the particle size distribution (of the product), the shape of particles, the bulk density, the moisture level, and the friability of the product. These factors give rise to considerable differences between materials. Hjemsted and Schneider (1996) measured the dustiness of 31 different products using the rotating drum method and observed a very wide range of results between the substances, with a factor 2000 difference between the highest and lowest dustiness level. In a project funded by the European Commission under the 6th Framework Programme, 12 different materials were tested using the rotating drum, which showed a 50fold difference in the inhalable dustiness mass fraction between the highest and the lowest results (Burdett et al., 2000). Quantitative dustiness information is generally not available and therefore existing exposure models that include a dustiness parameter tend to use dustiness categories (HSE, 1999; Marquart et al., 2008). COSHH Essentials uses three dustiness categories to estimate exposure (granules, coarse dust, and fine dust) (HSE, 1999), while CEN EN 15051 identifies four and Stoffenmanager uses five distinct dustiness categories (firm granules or flakes, granules or flakes, coarse dust, fine dust, and extremely dusty products) (Marquart et al., 2008). These qualitative categories may introduce operational difficulties for the user due to their fuzzy boundaries and broad dustiness categories. The categorization process may therefore raise difficulties and introduce ‘linguistic uncertainty’ (Morgan and Henrion, 1990), in particular if borderline cases have to be evaluated (Tischer et al., 2003). The ART mechanistic model adopted the classification scheme for the dustiness of materials from Stoffenmanager. The categories within this scheme are based on a qualitative description similar to that used in Stoffenmanager. In addition, measured Table 3. The classification scheme for dustiness categories and assigned values for powdered, granular, and pelletized material Category Description Relative multiplier Firm granules, flakes, or pellets Product does not result in dust emission without intentional breakage of products: e.g. firm polymer granules, granules covered with a layer of wax) 0.01 100 Granules, flakes, or pellets Granules or flakes may fall apart and crumble, resulting in only a very limited amount of fine particles. Handling the product does not result in a visible dust cloud; e.g. fertilizer, garden peat, animal pellets. 0.03 101–500 Coarse dust A powdered product containing coarse particles. Handling the product in its dry form results in a dust cloud that settles quickly due to gravity: e.g. sand. 0.1 501–2000 Fine dust A powdered product containing fine particles. This category may also contain products with a mixture of fine particles and large particles or granules. Handling the product in its dry form results in a dust cloud that is clearly visible for some time: e.g. talcum powder, carbon black. 0.3 2001–5000 Extremely fine and light powder A powdered product containing very fine, free flowing, light particles. This category may also contain products with a mixture of very fine particles and large particles or granules. Handling the product in its dry form results in a dust cloud that remains airborne for a long time. The product may be wind swept: e.g. magnesium stearate. 1.0 5000 As measured with rotating drum dustiness tester according to CEN (2006). Dustiness test level (mg kg1) Substance Emission Potential dustiness (inhalable fraction) in milligrams per kilogram are also provided, which can be used as indicative cut-off points (Table 3). A range of two orders of magnitude between lowest and highest dustiness class appears to be plausible given the total range in individual dustiness test results and the fact that only a limited number of classes are used in this scheme. Therefore, a relative multiplier was assigned to each category ranging from 0.01 for ‘firm granules, flakes, or pellets’ to 1 for ‘extremely fine and light powder’. We compared the assignment of dustiness category for 27 substances based on measured dustiness with the assignment by an expert panel of six occupational hygienists. The dustiness was measured using a rotating drum tester (EDT 38 L; JS Holdings, UK). Each member of the expert panel independently assigned a dustiness category to each substance, and subsequently one category was assigned to each substance based upon a consensus procedure. The median and range of the measured dustiness values for the dustiness categories are shown in Table 4. Unfortunately, there were no ‘firm granules or flakes’ materials included in this study. Comparing the assignment of dustiness category based on the measured dustiness with the expert panel assessment showed that there was agreement for 33% of the substances (Table 4). For nearly half the substances, the expert panel assigned a higher dustiness category, while for 20% of the substances the expert panel assigned a lower dustiness category. These results suggest that the qualitative assignment of dustiness category of a product appears to be broadly appropriate, albeit somewhat conservative. Increasing the moisture content or incorporating additives will generally reduce emission of dusts from powders, although the effect of moisture content on dustiness is complicated and varies for different types of products. Water can be added to the product before or during the activity. The latter case is treated as a control measure (‘wet suppression 983 techniques’) in the ART model and is therefore taken into account in the MF ‘localized control’ (Fransman et al., 2011), whereas the former is considered an intrinsic property of the material. Plinke et al. (1991) showed that for powders, increasing the moisture tended to reduce the dustiness by one order of magnitude or more. Three categories of moisture content of powders were adopted in the ART (Table 5), with multipliers used for powders ranging from 1 for dry powders (,5% moisture) to 0.01 for powders with .10% moisture content. Within ART, it is assumed that the emission of dust from handling powders or abrasion of solid materials is proportional to the weight fraction of the substance of interest. For example, if the weight fraction of the chemical in a powder is reduced from 10 to 1%, then the emission of the substance is reduced by a factor of 10 (all other factors being equal). The relative multiplier for the substance emission potential for powders is calculated as follows: ð1Þ E 5 DMW; where D is the relative dustiness multiplier, M is the relative multiplier for moisture content, and W is the weight fraction. HANDLING SOLID OBJECTS RESULTING IN DUST EXPOSURE Intrinsic characteristics of the solid materials, such as structure, friability, and hardness of the materials, are all important factors in the mass of aerosols emitted during abrasive activities and their particle size distribution. For example, grinding of wood clearly produced aerosols of a larger size distribution as compared to the other investigated (and harder) substrates (e.g. aluminium, steel, ceramic, granite) (Zimmer and Maynard, 2002). However, in particular within similar materials, the evidence for an association between the intrinsic characteristics Table 4. Comparison of the dustiness classification of 27 products based on qualitative and quantitative assessments Qualitative dustiness categories Nexpert panel Median (range) of Dustiness category based on measurements (mg kg1) measured dustiness 100 101–500 501–2000 2001–5000 .5000 (mg kg1) Firm granules, flakes, or pellets 0 Granules, flakes, or pellets 5 99 (25–1055) Coarse dust 9 588 (195–4762) 10 2933 (691–6526) 3 8176 (2703–9795) Fine dust Extremely fine dust — Nmeasured 0 3 1 1 4 2 4 3 5 7 3 4 2 1 2 8 4 Nexpert panel, Number of products assigned to each dustiness category by the expert panel; Nmeasured, Number of products assigned to each dustiness category based on the dustiness measurements. 984 M. van Tongeren et al. Table 5. The effect of moisture content on dustiness of powdered, granular, or pelletized products and solid objects Category Powders, granules, or pellets Solid objects Dry product (,5% moisture content) 1.0 1.0 5–10% moisture content .10% moisture content 0.1 0.01 0.3 0.03 and the emission rate is inconsistent. Alwis et al. (1999) found that hard wood produces more and finer dust than soft wood, although Thorpe and Brown (1995) showed that hardness of the wood was inversely associated with the dust production rate and aerodynamic diameter of dust emitted during sanding operations. Chung et al. (2000) did not find any significant differences in the quantity of dust generated from sawing hardwood, softwood, or medium-density fibre boards. According to Kalliny et al. (2008), processing of hardwood and mixed woods generally were associated with higher exposure than were softwood and plywood, although results may have been confounded by other unaccounted exposure determinants. Petavratzi et al. (2007) indicate that hardness of material could be an important factor in dust liberation mechanisms in quarry operations. Roberts (1997) evaluated the dustiness of sandstone and observed that hard sandstone resulted in higher exposures compared with stone with lower crushing strength. Due to the inconsistent results of studies investigating the impact of the intrinsic characteristic of solid substances on exposure levels during abrasive activities, it is currently difficult to develop a coherent, generic classification system across different materials. Instead, the effect of the intrinsic properties of solid materials is (at least partly) covered by the activity emission potential component of the model (Marquart et al., 2011). Similar to powders, the emission potential for solid objects is modified by the moisture content and the weight fraction of the chemical substance within the solid object and pre-existing moisture content of solid material is considered as part of the intrinsic emission potential. The relative multiplier for moisture content of the solid material is based on evidence of the effect of wet suppression techniques (used as localized control measure to reduce emission levels). Relatively low moisture content (5–10%) is assumed to reduce emission by about a factor 3 compared to dry material, based on median efficacy values obtained for ‘wet suppression’ (Fransman et al., 2008) and exposure reduction figures described for spraying of bricks with a fine water mist (Buringh et al., 1990). For solid materials with high moisture content, a reduction factor of 0.03 is applied. The relative multiplier for the substance emission potential for solid objects is calculated as follows: E 5 MW; ð2Þ where M is the relative multiplier for moisture content and W is the weight fraction. HANDLING (VOLATILITY) LIQUIDS RESULTING IN EXPOSURE TO VAPOURS Evaporation is the main process for emission for volatile liquids, with the rate of evaporation depending on the volatility of the liquid (vapour pressure or boiling point), the dimensions of the source (surface area), and the environmental conditions, such as air temperature, air velocity, direction, and turbulence. In 1916, Lewis demonstrated that the specific evaporation rate of a pure liquid is directly proportional to the vapour pressure (Nielsen et al., 1995). The vapour pressure of a pure substance at room temperature is readily available and the vapour pressure at higher liquid temperatures can either be assessed empirically, using so called Cox charts (after the engineer who developed it in the early 1920s), or estimated using, for example Trouton’s rule: TBP ln p 10:6 1 ; ð3Þ T where p is the vapour pressure (in atm), TBP is the boiling point temperature of the liquid (K), and T is the temperature of the liquid (K). Trouton’s rule, which is used in some regulatory exposure assessment models, assumes that the ratio between the enthalpy of vaporization and the normal boiling temperature (at a pressure of 1 atm) is close to 88 J K1 mol1 and that the change in the enthalpy is linearly related to temperature (between 298 K and the boiling point temperature). When estimating the vapour pressure for substances in a mixture, one needs to account for the fact that more than one substance will contribute to the overall vapour pressure. This is based on a fundamental thermodynamic relationship called Raoult’s law, which shows that the contribution of the partial vapour pressure of liquid component ‘i’ to the total vapour pressure of the mixture is reduced as the molar fraction of component i (xi) decreases. Substance Emission Potential pT 5 X xi pi ; ð4Þ i where pT is the vapour pressure of the mixture, xi is the molar fraction of component i in the liquid, and pi is the vapour pressure of the ith component. Raoult’s law relates the vapour pressure of the components to their composition in an ideal mixture. However in non-ideal mixtures, vapour pressures can be greater (positive deviations) or smaller (negative deviations) than is expected under conditions of an ideal mixture. When the attractive forces between the molecules in the solution are weaker than the attractive forces between the molecules of the individual components on their own, e.g. ethanol and benzene, there is a positive deviation from Raoult’s law. Negative deviations are found in solutions where the attractive forces between the molecules in solution are stronger than the forces between the molecules of the individual components on their own. For non-ideal mixtures, a correction factor (or activity coefficient, c) is introduced into Raoult’s law. X pT 5 ci xi pi ; ð5Þ i where ci is the activity coefficient of the ith component at a given molar fraction. The activity coefficients depend on both the concentration and the composition of the mixture (Maken et al., 2004). Generally, the activity coefficients are close to 1 where the interactions between the molecules in solution (solute and solvent) are almost the same as those for the molecules of the pure liquid. This is typical of non-polar hydrocarbon solutes mixed with a non-polar hydrocarbon solvent and polar solutes dissolving in polar solvents. The activity coefficient will increase with increasing difference in the polarity between the substance and the solvent (Popendorf, 2006). The activity coefficient of most hydrocarbons and other hydrophobic solutes in water will be greater than unity, while the activity coefficient for hydrophilic solutes in water (such as ammonia and formaldehyde) will be less than unity (Popendorf, 2006). If liquid components are only sparingly soluble in each other, then the activity coefficient ci is inversely related to the corresponding solubility of one solute in the solvent. The activity coefficient can be empirically derived. Alternatively, tools such as the UNIversal Functional Activity Coefficient (UNIFAC) method can be used. The UNIFAC method, which was orig- 985 inally developed by Fredenslund et al. (1975), considers molecules as assemblies of fractions of molecules (functional groups). The UNIFAC method for estimating the activity coefficients has several limitations. For example, the temperature of the mixture should be ,150°C and should not contain .10 functional groups. Furthermore, it relies on availability of information on exact molar fraction, which is generally not available for most liquid products. Within the ART, the user is requested to provide the vapour pressure at the process temperature. If this is unknown, then Trouton’s rule is applied to estimate the vapour pressure at the process temperature. Subsequently, the molar fraction or, if this is unknown, the weight fraction of the substance in the liquid mixture is requested and used to obtain the partial vapour pressure (pi,mix). The default value of the activity coefficient for a liquid mixture is set at 1. However, the user is encouraged to use the UNIFAC or other method to obtain the actual activity coefficient for the substance within the liquid mixture. The relative multiplier for the substance emission potential for a volatile substance (in a mixture) is then calculated as follows: pi;mix E5 : ð6Þ 30 000 Substances with a vapour pressure of equal or .30 000 Pa will evaporate almost immediately. The relative multiplier for the substance emission potential is therefore restricted to a maximum of E 5 1 when pi,mix 30 000 Pa. Substances with very high vapour pressures .100 000 Pa are formally considered gases and are outside the applicability domain of ART. The relative multiplier has been set at a minimum of E 5 3.33 104 when pi,mix ,10 Pa. HANDLING (LOW VOLATILITY) LIQUIDS RESULTING IN EXPOSURE TO MISTS Mists can be generated by a number of processes, such as by impaction of a liquid on a surface, by bubbling of gases through a liquid or by evaporation followed by condensation of the vapour. Within ART, we consider the potential for mist formation when handling of low-volatile liquids (i.e. with a vapour pressure 10 Pa). This category also includes powders suspended in a liquid (e.g. copper in antifouling paint) or substances dissolved in a liquid (biocides dissolved in water). The level of aerosol formation is mainly determined by the activity (activity emission potential) (Marquart et al., 2011). However, the viscosity of a liquid may also affect the potential for aerosol formation. Handling of 986 M. van Tongeren et al. liquids with low viscosity (like water) will result in more mist formation compared to handling of liquids with medium viscosity (like oil), with all other factors the same. Therefore, we have arbitrarily assigned relative weighting factors of 1 for lowviscosity liquids and 0.3 for medium-viscosity liquids in the ART. Highly viscous products like resin or paste have stronger binding forces and are therefore unlikely to form aerosols during handling. Similar to dust and solid object, the weight fraction of the chemical substance in the product will (proportionally) modify the emission of the chemical. The relative multiplier for the emission potential for low-volatile liquids resulting in mist formation is estimated as follows: E5 10 WV; 30 000 ð7Þ where W is the weight fraction and V is the relative modifier for viscosity. DISCUSSION This paper described the current knowledge and evidence on intrinsic characteristics of solids and liquids that determine the potential for their release into workplace air. The substance emission potential takes account of the latest thinking on emissions of dusts, mists, and vapours and in our view provides a good balance between theory and pragmatism. This approach has been applied in the ART mechanistic model development (Fransman et al., 2011). Obtaining reliable estimates for the emission potential for a substance and activity is critical in any mechanistic exposure model. The vapour pressure for liquids and dustiness for powders, pellets, and granules are believed to be good proxies for the intrinsic emission potential of a substance. However, use of the mechanistic model in ART requires knowledge of and experience in exposure assessment, in particular when deciding on the correct category for exposure determinants, such as the dustiness class. Consequently, we advise that the ART should only be used by exposure assessment experts. For powdered, granulated, and pelletized materials, the dustiness category will often need to be selected in the absence of actual dustiness information and is therefore subjective. More empirical data are required on the dustiness of materials. Manufacturers of these materials should be strongly encouraged to include such information in the safety data sheets, although this would require standardization of the methods for assessing the dustiness and the reporting of this information. Also, the impact of moisture content and environmental condi- tions such as humidity on the dustiness should be investigated further. It would also be worthwhile to investigate the dustiness of solid objects; standard protocols will need to be developed for this. This information could be used to estimate the release of dust during general handling of solid materials. For activities other than general handling, it is likely that the activity or process is much more important for estimating the release of dust than the intrinsic characteristics of the material. However, further experimental work is required to confirm this. For evaporation of volatile liquids, the prediction of the emission potential is relatively straightforward when dealing with a single, pure substance; mixtures are more complicated, especially if the exact composition of the mixture is unknown or is variable. The molar fraction of the constituents of the mixture should be known to estimate accurately the partial vapour pressure of the constituents and hence the emission potential. However, as this information is rarely accurately available, it was decided to use the weight fraction in the ART as a proxy for the molar fraction. If there are no large differences between the molecular weights of components within the mixture, then the weight fraction is a reasonably good proxy for the molar fraction. However, if there are large differences, for instance mixtures that contain polymers, the molar fraction and weight fraction can deviate substantially, and hence, the emission potential may be estimated with substantial error. Manufacturers should be encouraged to include information on the molar fraction of substances on the safety data sheets of liquid products. Clearly, accurate predictions of the partial vapour pressures for substances in mixtures of varying composition (i.e. products of which the exact composition will vary between different batches) are difficult. More detailed information on the composition is required, such as information on the distribution of the molar fraction of individual components, rather than just the range. For complex (liquid) mixtures with variable composition (e.g. oil distillate products), the exposure of interest may be the mixture itself rather than or in addition to the individual components. Generally, the vapour pressure and boiling point are provided as a range for such complex mixtures. Currently, we recommend that the maximum vapour pressure of the mixture is applied when using ART to estimate exposure, although this would probably lead to an overestimate of the actual exposure. If such liquid products are used above room temperature, then the vapour pressure range should be determined experimentally. Studies investigating the effect of temperature on the exposure to complex mixtures as Substance Emission Potential well as exposure studies in real exposure scenarios are needed to refine ART in this area. Currently, ART does not take into account the effect that other materials in the mixture may have on the emission (e.g. insoluble solids), as for example is the case in paints. The emission rate for volatile agents from a painted surface will be reduced by the formation of a drying layer on the surface of the paint. van Veen et al. (1999) developed a twocompartment model for emission of volatile agents from a painted surface to address the rate-limiting evaporation process during the drying of a painted surface. The current version of ART will overestimate emission for such mixtures and further refinement would be needed to provide a more realistic emission factor. The ART model is relatively unsophisticated for mists. We have assumed that the viscosity of the material may determine the mist generation. However, other issues that affect mist generation, such as surface tension, evaporation, and condensation, are not taken into account. A full review of the factors affecting mist generation during different tasks (e.g. cutting and grinding, electroplating, spraying, and carpet cleaning) will be necessary to ascertain what further refinements of the ART model would help to improve its accuracy and widen its applicability for assessing workplace exposures to mists. ART applies a strict dichotomy for generation of vapours, if the vapour pressure at the process temperature is .10 Pa, and generation of mist, if the vapour pressure is 10 Pa. This dichotomy might not be the most optimal solution for semi-volatile compounds. During activities with limited or no aerosol formation, evaporation may still be the dominant exposure generating process for semi-volatile compounds, even if vapour pressure is ,10 Pa. In order to avoid underestimation, it is therefore advised to use a vapour pressure of 11 Pa in ART for the following specific situations: The substance is a semi-volatile compound with a vapour pressure between 0.01 (which is arbitrarily chosen) and 10 Pa at the respective process temperature 987 aerosols, and gases. For fibres, there is evidence suggesting that the addition of oil to the fibres will reduce the emission (Cherrie et al., 1987; Class et al., 2001). In the case of metal fumes, we are aware that there are a vast amount of data and knowledge on welding fumes available in the literature, and therefore, we believe it is not necessary for a generic tool such as ART to include exposure to welding fumes. There is little evidence linking any of the intrinsic properties of the materials with the emission of fumes during other hot processes, although it is possible that the ratio of the process temperature of the metal or alloy and the boiling point temperature of the metal of interest may be related to the emission rate (Popendorf, 2006). For gases, it is unclear to what extent the intrinsic characteristics of the gas are important when estimating the release from a source. Clearly, gases need to be contained in closed vessels or tanks, although there may be release from small leaks and when connecting or disconnecting. However, the magnitude of these emissions will probably depend more on the integrity of the container seals and the pressure difference between the inside and outside of the container than the intrinsic substance characteristics of the gas. The model has been calibrated separately for the various exposure forms using actual exposure data (Schinkel et al., 2011). These results show that the model predicted 60% of the variance in results from dust and vapour measurements, although for mist exposure the explained variance was lower (30%). Occupational inhalation modelling could make significant further progress by improving our understanding of exposure determinants and by extending the conceptual basis to other emission forms, such as fumes, fibres, and gases. Expanding the knowledge base on characteristics that are closely linked to intrinsic emission potential and bridging some of the knowledge gaps described above will improve the predictive power of occupational exposure models and thereby the accuracy and precision of the exposure estimates. and The activity belongs to one of the following activity classes: (i) activities with open (undisturbed) liquid surfaces or open reservoirs, (ii) handling of contaminated objects, (iii) spreading of liquid products, and (iv) bottom loading. 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