CHEMICAL SAFETY REPORT

Transcription

1 CHEMICAL SAFETY REPORT Legal name of applicant(s): Praxair Surface Technologies Submitted by: Praxair Surface Technologies Substance: Chromium trioxide, EC and CAS Use title: Use-1: Industrial spraying or brush application of chromium trioxide mixtures for the coating of metallic articles subject to harsh environment, to ensure a high temperature corrosion & oxidation resistance, as well as anti-fouling properties or lubricity at high temperature, for automotive, aviation, power generation machinery, Oil and Gas and marine applications. Use-2: Industrial spraying of chromium trioxide mixtures for the coating of metallic articles subject to harsh environment to ensure either a low temperature-cured coating for corrosion protection, or a high temperature corrosion & oxidation resistance with reduction of surface roughness or with a high temperature adhesive, for aviation, power generation machinery, Oil and Gas and marine applications. Use number: Use-1; Use-2 1

2 9. EXPOSURE ASSESSMENT (AND RELA TED RISK CHARACTERISATION) 9.1. Introduction Praxair Surface technologies application for authorisation concerns the use of Chromium trioxide mixtures for the coating of metallic articles by spraying process. It takes place on 4 sites located in the EU. Company Site Country Use applied for Number of workers Lincoln United Kingdom Use-1 & Use-2 26 Southam United Kingdom Use-1 2 Monte Marenzo Italy Use-1 10 Fornovo Italy Use-1 5 workers using an automated process Table 7. Overview of the PST s Application for Authorisation This chemical safety report and exposure scenario deals with both uses (Use-1 & Use-2) of Chromium trioxide mixtures for the coating of metallic articles by spraying Overview of uses and Exposure Scenarios 27

3 Titles of identified uses Title of Exposure Scenario Use 1 Industrial spraying of chromium trioxide mixtures for the coating of metallic articles subject to harsh environment, to ensure a high temperature corrosion & oxidation resistance as well as anti-fouling properties or lubricity at high temperature for automotive, aviation, power generation machinery, Oil and Gas and marine applications. ES-1: Industrial spraying of chromium trioxide mixtures for the coating of metallic articles ES-2: Brush application of chromium trioxide mixtures for the coating of metallic articles Use 2 Industrial spraying of chromium trioxide mixtures for the coating of metallic articles subject to harsh environment to ensure either a Low Temperature-Cured Corrosion Protection or a high temperature corrosion & oxidation resistance with reduction of surface roughness or high temperature adhesive property for aviation, power generation machinery, Oil and Gas and marine applications. ES-1: Industrial spraying of chromium trioxide mixtures for the coating of metallic articles Table 8. Uses of the Application for Authorisation dossier and Exposure Scenarios Process explanation This CSR will discuss about the use of chromium trioxide and acids generated from chromium trioxide, for the spraying, or the brush application, on metallic articles to protect them against corrosion at high temperature. Use by spraying The two most important steps of this process involve the spraying of hexavalent chromium mixtures and the curing stage, to obtain the protective layer. The process starts with a non-exposing step regarding exposure to chromium trioxide. Surface preparation Before the spraying of hexavalent mixtures, parts are cleaned (degreasing) and an abrasive blasting step is then performed to facilitate the adhesion coating. No exposure to hexavalent chromium is considered 28

4 The steps described below are the exposing steps. Preparation of the coating Mixtures already formulated are re-mixed prior to spraying, using a paint shaker to ensure that pigment particles are well dispersed in the slurry. Mixture bottles are shaked and they are not opened during this step of the process. Consequently, there is no possibility of exposure. Then, the bottle is opened and the mixture is transferred into a small container, in a spraying room, and directly clipped to the spray gun. If there is a problem in the mixture consistence, during the transfer, the mixtures must be screened with a sieve, to remove oversized pigment agglomerates and any foreign contaminants (figure 2). This operation is performed in a separate room. Figure 2. Removing of oversized pigment agglomerates during the transfer The operating condition and risk management measures of the transfer, with or without using a sieve, are identical, except for the general ventilation. They will be considered in the same contributing scenario, and the lower air change per hour will be considered. In this contributing scenario, the applicant will consider that the exposure to hexavalent chromium happened during the transfer of the substance. This task is considered in the estimation of exposure to hexavalent chromium. It is treated in this CSR in the Worker Contributing Scenario 1 (WCS-1.1). Manual spraying 29

5 In the spray booth, the workers employ an air-supplied respirator (not simply a face shield)(en B) (figure 3). Fully covered head gear with a connection to supplied breathing air Full body suit Protective gloves Shoe covers Figure 3. Safety protection of the worker during the spraying step The small container containing the mixture is clipped to the spray gun recipient (directly locked on the spray gun) (figure 4). 30

6 Figure 4. Photo of the spray gun with its recipient for mixtures Then, the spraying of metallic articles is performed in a dedicated place of the spray booth with a fixed capturing hood (figure 5). Fixed capturing hood Figure 5. Spraying area with the capturing hood This task is considered in the estimation of exposure to hexavalent chromium. It is treated in this CSR in the Worker Contributing Scenario 2 (WCS-1.2). This step is considered as the most exposing step Automated spraying In one site (Fornovo), two workers perform the spraying by using an automated process. In this case, the preparation of the coating is performed as described above, and the mixture is then transferred to the robot spray gun recipient. Parts are sprayed and dried inside the spray cabin with automated process without exposure for the workers (figure 6) located outside the spraying cabin. 31

7 Figure 6. automated spraying cabin (left) with the automated spraying gun (right) This task is considered in the estimation of exposure to hexavalent chromium. It is treated in this CSR in the Worker Contributing Scenario 3 (WCS-1.3). Parts transportation After the coating, parts are transported in the shop, from the spraying room to the dryer (5 mins). After the drying step, the parts are transferred in the furnace for the curing step (5 mins). After the curing step, a near-complete conversion of hexavalent to trivalent chromium is observed, and the remaining hexavalent chromium is included in a matrix. The transportation and the manipulation of articles after the curing step create a negligible risk. This task is considered in the estimation of exposure to hexavalent chromium. It is treated in this CSR in the Worker Contributing Scenario 4 (WCS-1.4). Drying of the coating After the spraying, parts must be air dried at temperature between 65 and 95 C in a dedicated heat chamber (figure 8) to drive out all the water inside the coating (the door is not completely closed, but nobody is located near the heat drier). For the automated process, this step is performed directly in the automated spraying cabin. 32

8 Figure 7. Photo of a heat chamber example This task is considered in the estimation of exposure to hexavalent chromium. It is treated in this CSR in the Worker Contributing Scenario 5 (WCS-1.5). Curing of the coating Immediately after the drying, articles must be transferred to a furnace for the curing step. This step is performed at different temperature between 165 to 350 C, depending of curing time (curve linked between time and temperature of curing) and the metal base properties. This step is the most important step of the process because it allows the crosslink of the binder to obtain a corrosion protection. Moreover, during this step, a conversion of hexavalent to trivalent chromium happens. This conversion is complete or near-complete. Figure 8. Photo of a furnace example 33

9 Cure coating burnishing After the cooling of articles, articles are burnished to achieve the conductivity properties of the parts. To perform this step of the process, the cured articles are retransferred in a furnace for a new sub-curing step. In terms of exposure, the 2 previous steps described (Curing/burnishing) will be included in the same contributing scenario. These tasks are considered in the estimation of exposure to hexavalent chromium. It is treated in this CSR in the Worker Contributing Scenario 6 (WCS-1.6). Removal of the coating If necessary (e.g. defect on the coating ), the coating is removed, using a stripping process with alkali solution in bath at 80 C. Then, the process restarts normally as described above. This task is considered in the estimation of exposure to hexavalent chromium. It is treated in this CSR in the Worker Contributing Scenario 7 (WCS-1.7). Cleaning of the spraying room The workers clean the spraying room by removing solid (paperboard) protection and clean the spray gun and its recipient with water. At the end of the process, all these wastes are managed by a specialised waste company, which collects all the wastes (paper, PPE, waste water ). No waste water is released outside the shop. This task is considered in the estimation of exposure to hexavalent chromium. It is treated in this CSR in the Worker Contributing Scenario 8 (WCS-1.8). Use by brush application This process is performed exclusively in the Southam site. Moreover, this process is performed once a month for finishing works on blades. Preparation of the coating Mixtures already formulated are re-mixed prior to spraying, using a paint shaker to ensure that pigment particles are well dispersed in the slurry. Mixture bottles are shaked and they are not opened during this step of the process. Consequently, there is no possibility of exposure. Then, the bottle is opened only during the brush application step. No exposure to hexavalent chromium is considered Brush application 34

10 If touch-up paint is required, workers apply the paint with a brush (figure 9) in a dedicated area under extraction hood. Applicant HAND paint (Not spray) the nonabutment faces of the Pegasus HP2 turbine blade which are 1.5mm x 5mm in size x 4 area`s with Sermalloy J paint. Figure 9. Photos of the brush size This task is considered in the estimation of exposure to hexavalent chromium. It is analysed in this CSR in the Worker Contributing Scenario 1 (WCS-2.1). Parts transportation After the brush application, parts are transported in the shop, from the brushing room to the furnace for the curing step (5 mins). After the curing step, a nearcomplete conversion of hexavalent to trivalent chromium is observed, and the remaining hexavalent chromium is included in a matrix. The transportation and the manipulation of articles after the curing step present a negligible risk. This task is considered in the estimation of exposure to hexavalent chromium. It is treated in this CSR in the Worker Contributing Scenario 2 (WCS-2.2). Curing of the coating This step is performed at different temperatures (figure 10), from 165 to 350 C, depending on the curing time (curve linked between time and temperature of curing) and the metal base properties. This step is the most important step of the process because it allows the crosslink of the binder to obtain a corrosion protection. Moreover, during this step, a conversion of hexavalent to trivalent chromium happens. This conversion is complete or near-complete. 35

11 Figure 10. Photo of a furnace example Cure coating burnishing After the cooling of articles, articles are burnished to achieve the conductivity properties of the parts. To perform this step of the process, the cured articles are retransferred in a furnace for a new sub-curing step. In terms of exposure, the 2 previous steps described (Curing/burnishing) will be included in the same contributing scenario. These tasks are considered in the estimation of exposure to hexavalent chromium. It is treated in this CSR in the Worker Contributing Scenario 3 (WCS-2.3) Tonnage information / Number of workers exposed: Substance name EC Number CAS Number Chromium Trioxide Acids generated from chromium trioxide and their oligomers or or Intrinsic properties specified in annex XIV/recommendation Carcinogenic cat 1A Mutagenic cat 1B Carcinogenic cat 1B Tonnage band registered (t/y) 1,000-10,000 Table 9. Substances considered in the CSR The hexavalent chromium compounds were included in Annex XIV due to their carcinogenic properties. 36

12 As mentioned in section 5, this Chemical Safety Report focuses on the use of hexavalent chromium for their carcinogenic/mutagenic effects. Thus, exposures and risk characterisation (RCR) will be developed considering carcinogenic effects. Moreover, exposures and excess risk of cancer will be developed considering hexavalent chromium without making any difference between the uses of chromium trioxide and acids generated from chromium trioxide. Indeed, the SDS of the different mixtures used mention only chromium trioxide. Nevertheless, it should be noted that chromium trioxide is dissolved in acids generated from chromium trioxide and their oligomers during the process. Total tonnage of Chromium Trioxide Total tonnage of Acids generated from chromium trioxide and their oligomers Number of workers exposed Use kg 43 (including 5 workers using an automated Use-2 70kg process) Note: It should be noted that chromium trioxide is in anhydrous form and the aqueous form is chromic acids generated from chromium trioxide. As described in the Exposure Scenario, chromium trioxide is dissolved in a liquid form. Thus, for the final use, these two substances are considered as the same and the quantities as well. Table 10. Tonnage and number of workers exposed by use The assessed tonnage for Praxair Surface technologies is 470 kg / year based on the tonnage of Chromium trioxide used in 2014 for Use-1 & Use-2. This activity has been stable for several years but should decrease in the future. The Use-1 is divided in 2 exposure scenario, one for the spraying process (41 workers) and one for the brush application process (2 workers). Whereas the Use-2 is concerned by the same spraying exposure scenario. Moreover, in the spraying exposure scenario, two different spraying contributing scenarios, i.e. a manual one (36 workers) and an automated one (5 workers) will be described Overview of exposure scenarios The following table lists the exposure scenarios (ES) assessed in this CSR. Identifiers*) Market Sector Titles of exposure scenarios and the related contributing scenarios Tonnage of Chromium trioxide (tonnes per year) Comments 37

13 Identifiers*) Market Sector Titles of exposure scenarios and the related contributing scenarios Tonnage of Chromium trioxide (tonnes per year) Comments IW-1 IW-1.1 PC14 SU 3 SU 15 ES-1- Industrial spraying of chromium trioxide mixtures for the coating of metallic articles - Preparation of the coating (mixing and screening compound) (PROC 8b) IW Manual spraying (PROC 7) IW Automated spraying (PROC 7) IW Parts transportation (PROC 26) IW Drying of coating (PROC 21) IW Curing of coating (PROC 22) IW Removal of coating (PROC 13) IW Cleaning of the spraying room (PROC 21) - Industrial spraying of chromium trioxide mixtures for the coating of metallic articles (ERC 5) This is the quantity used by PRAXAIR for the 2 different uses and the 5 sites in Europe All these steps are conducted repeatedly and in a row by the same operator during a day of work so that each monitoring measure covers the full process. As a result, details of Chromium trioxide tonnage used at each step are not mentioned. Wastes resulting from the process are collected by a specialised waste management company. Air effluents are collected and filtered before being released outside. Liquid wastes are produced & collected without release, and solid wastes are stocked in a dedicated area and managed by a specialised waste company IW-2 PC14 SU 3 SU 15 ES-2- Industrial spraying of chromium trioxide mixtures for the coating of metallic articles <0.001 This is the quantity used by PRAXAIR for the 2 different uses and the 5 sites in Europe IW Brush application (PROC 10) IW Parts transportation (PROC 26) IW Curing of coating (PROC 22) All these steps are conducted repeatedly and in a row by the same operator during a day of work so that each monitoring measure covers the full process. As a result, details of Chromium trioxide tonnage used at each step are not mentioned. 38

14 Identifiers*) Market Sector Titles of exposure scenarios and the related contributing scenarios Tonnage of Chromium trioxide (tonnes per year) Comments Wastes resulting from the process are collected by a specialised waste management company. - Industrial spraying of chromium trioxide mixtures for the coating of metallic articles (ERC 5) <0.001 Air effluents are collected and filtered before being released outside. Liquid wastes are produced & collected without release, and solid wastes are stocked in a dedicated area and managed by a specialised waste company PW-1 PC 14 SU 22 ES-2- Professional use *) Manufacture: M-#, Formulation: F-#, Industrial end use at site: IW-#, Professional end use: PW-#, Consumer end use: C-#, Service life (by workers in industrial site): SL-IW-#, Service life (by professional workers): SL-PW-#, Service life (by consumers): SL-C-#.) Table 11. Overview of exposure scenarios and contributing scenarios Introduction to the assessment Environment The environmental assessment is not relevant for this CSR dedicated to the Application for Authorisation regarding the SVHC properties stated in column 2 of entry 16 in annex XIV of REACh (COMMISSION REGULATION (EU) No 125/2012). At the end of the process, wastes are managed by a specialised waste management company which collects all the wastes (liquid, paper, PPE ). Nevertheless, in the environmental contributing scenario 1, applicant will discuss the possible atmospheric release to establish the risk for general population Man via environment Risk analysis for man via environment will be performed according to the conclusions of the environmental release identified in the environment Workers 39

15 The excess risk calculation will be based on RAC/27/2013/06 Rev.1 which establishes a reference dose response relationship for carcinogenicity of hexavalent chromium. Regarding the advice of the RAC, no data clearly indicate that dermal exposure to Cr(VI) compounds creates a risk of cancer to human. As a consequence, the risk induced via dermal exposure will not be considered in what follows, especially taking into account the dermal protections used in the coating shops. Moreover, and since the size distribution of particles is not reliable, we will estimate the cancer risk mainly for lung cancer and maximize excess of cancer risk by not taking into account the small intestine cancer risk. Monitoring measurement campaign is planned several times by year for each site to assess the exposure during the entire process. For the description of each contributing scenario, we will use the ART 1.5 software to have an associated value of exposure. In the modelling process, we will use the Long-term value at 90 th percentile for the entire contributing scenario. ART modelling reports are given in Annex IV. Nevertheless, to calculate the excess risk of cancer (Chapter 10), we will use the combination of estimation and monitoring value to assess a quantitative analysis. In PST activities, the exposure concentration could vary from the less dangerous scenario (small amount of coating material, 0.5-1%; small part size ) to the worst case scenario (largest amount of coating material, 1-5%; largest part size.). In the description of the contributing scenario, we will describe the most representative exposure scenario (coating material, 1-5%; small part size...). Moreover, Praxair constrains its EU shops to monitoring value under the value of 5µg/m 3 even though, in the UK & Italy, exposure limits are 10 fold higher, at 50 µg/m Consumers This assessment is not relevant since no consumer will use the article produced. PST will advise its downstream supply chain (professional users) on the concentration of hexavalent chromium in the article coated. Moreover, this exposure will be described in the paragraph Exposure scenario 1: Industrial spraying of chromium trioxide mixtures for the coating of metallic articles Sector of use: Industrial uses, Uses of substances as such or in preparations at industrial sites (SU 3) Manufacture of fabricated metal products, except machinery and equipment (SU 15) 40

16 Environment contributing scenario(s): Industrial use resulting in inclusion into or onto a matrix (ERC 5) Worker contributing scenario(s): - Preparation of the coating (mixing and screening compound) (PROC 8b) - Manual spraying (PROC 7) - Automated spraying (PROC 7) - Parts transportation (PROC 26) - Drying of coating (PROC 21) - Curing of coating (PROC 22) - Removal of coating (PROC 13) - Cleaning of the spraying room (PROC 21) Risk Management Measures (RMM) are standardised by PRAXAIR corporate for all the sites in the world. Monitoring measurement campaigns are planned several times per year for each site so as to assess exposure during the process. Internal Praxair documents describe these RMMs. More precisely, Praxair safety standards define (see annex 1, 2 & 3): - The personal & general protection measures - The operating conditions and the process - The frequencies of monitoring sampling and the method to analyse the sample - The measure to set up in case of high monitoring values - The medical examination process All contributing scenarios for the exposure scenario are realised sequentially in the same shop, except for the automated spraying contributing scenario, which is specific to the site of Fornovo. Nevertheless, other contributing scenarios (preparation, drying, curing, burnishing, removal, cleaning) are applied similarly at Fornovo. Contributing scenario PROC / ERC ECS 1.1 ERC 5 WCS 1.1 Preparation of the coating (mixing and screening compound) PROC 8b Additional information Industrial spraying of chromium trioxide mixtures for the coating of metallic articles Mixtures already formulated are re-mixed prior to spraying using a paint shaker to ensure that Aluminium pigment particles are well dispersed in the slurry. After re-mixing, the mixtures must be screened to remove oversized pigment agglomerates and any foreign 41

17 WCS-1.2 Manual spraying WCS-1.3 Automated spraying WCS-1.4 Parts transportation WCS-1.5 Drying of coating WCS-1.6 Curing of coating WCS-1.7 Removal of coating WCS-1.8 Cleaning of the spraying room PROC 7 PROC 7 PROC 26 PROC 21 PROC 22 PROC 13 PROC 21 contaminants. The container is then transferred to the spray booth for use. In the spray booth, it should be emphasized that an air-supplied respirator (not simply a face shield)(en1941 TH3, EN A/3B) is employed during spraying. The mixture is transferred to the spray gun recipient (directly locked on the spray gun). Then, the spraying of metallic articles is realised in a dedicated place of the spray booth with fixed capturing hood. The mixture is transferred to the robot spray gun recipient. Parts are sprayed and dried inside the spray cabin with automated process without exposure for the worker. After the spraying, the parts are transferred to a heat chamber and then to a furnace for the curing step. Articles coated are transferred to heat chamber to be dried typically at temperature such as 80 C during 15 minutes. Immediately after the drying, articles must be transferred to furnace for the curing step. This step is realised at different temperature between 165 to 350 C, depending of curing time (curve linked between time and temperature of curing) and the metal base properties. After the cooling of articles, articles are burnished to achieve the conductivity properties of the parts. If necessary (e.g. defect on the coating ), the coating is removed by immersion using a stripping process with alkali solution in bath at 80 C. Then, the process restarts normally. The worker cleans the spraying room by removing solid (paperboard) protection and cleans the spray gun and its recipient with water. At the end of the process, all these wastes are managed by a specialised waste company which collects them (paper, PPE, waste water ). Table 12. Description of the activities and technical processes covered in the exposure scenario This ES assessment will be based on monitoring data and exposure modelling but also on management measures implemented to reduce workers exposure (description of collective and personal protective equipment). Modelling will be realised with the ART 1.5 (Tier 2) online software Environmental contributing scenario 1: Industrial use resulting in inclusion into or onto a matrix Conditions of use Parameter Information 42

18 Product characteristics Product Chromium trioxide solution or chromic acids and their oligomers Physical form Powders dissolved in a liquid or incorporated in a liquid matrix Amount 470 kg / year Weight fraction of the substance in the liquid mixture Small (1-5%) Viscosity of the liquid mixture Liquids with low viscosity (like water) Operational conditions Emission Sources Atmospheric emission Liquid effluents treatment Process not fully enclosed. A small amount of product is release by atmospheric emission Atmospheric emission can be considered from the air extracted at the workplace through general and local ventilations. Specific filter are used before the release in the atmospheric compartment. Atmospheric emissions are controlled annually No liquid effluents are released to water or soil compartment during this process. All the waste (liquid or solid) are collected and stocked in a dedicated room Waste management Wastes (liquid or article) are managed by a specialised company. Table 13. Environmental contributing scenario 1 conditions of use Waste management Releases Liquid effluents and solid wastes produced are stocked before being managed by a specialised waste company and are not released outside. The different specialised certified waste companies (each site has a dedicated company) are listed below: - The T.R.S. ECOLOGIA S.R.L. company is dedicated for Fornovo site (Italy) - The Zanetti Arturo & C.SRL company is dedicated for Monte Marenzo site (Italy) - The Forward Waste Management Ltd company is dedicated for Lincoln site & Southam site (UK) Atmospheric emission The release of the substance outside the industrial site is limited to the air via the stack extraction after filtration. 43

19 In several official reports on possible exposure to hexavalent chromium 8,9, experts consider that the possible risk will be in the local air compartment. Indeed, for water and soil, the hexavalent chromium will be transformed into trivalent chromium via redox reaction 9,10. Moreover, the EU RAR on hexavalent chromium compounds, regarding the release from use in metal treatment, does not consider any air release (except during formulation of products) 8. Because no release measurement is available, applicant estimates the release based on modelling exposure. The technical guidance document part II 11 provides estimated release factors depending on the activity type. - The associated release factor (IC 16 (Industry Categories), Solubility > 1g/L, Vapour pressure between 10 & 100 Pa, MC=2 (Main category: inclusion into or onto a matrix) for PST is For the assessment, we took the worst case (combined for each site), with the nearest house at 300m and located in a non-urban area. Based on this release estimation and the Doury abacus 12 (which estimates the dispersion speed), we calculated the exposure of the general population around the site and the associated risk. Release for a working day is estimated (considering 120 working days per year) at mg per 8h Release adjusted to a 24h day is: mg/24h (0.45 µg/s) Atmospheric transfer coefficient (at 300m) from Doury Abacus is: 2.97x10-4 s/m Exposure and risks for the environment and man via the environment The release in air adjusted on 24h is: Release (0.45 µg/s) X Atmospheric transfer coefficient (at 500m) from Doury Abacus (2.97x10-4 s/m 3 ) After calculation, the exposure for general population is 1x10-4 µg/m 3 per 24h and120 working days. A normal year is 365 days, so the adjusted exposure is 4.43x10-5 µg/m 3. 8 European Union Risk Assessment Report on hexavalent chromium substances (Volume 53 3 rd priority list) 9 INERIS - Fiche de données toxicologiques et environnementales du chrome et de ses dérivés 10 EPA Ground Water Issue, Natural Attenuation of Hexavalent Chromium in Groundwater and Soils, EPA , Technical Guidance Document on risk assessment, part II about environmental risk assessment 12 Abaques d'evaluation directe des transferts atmospheriques d effluents gazeux, Doury et al, February

20 Applicant will consider adjusting the general population exposure for each use: - 85% (400/470) of the time for the Use-1 (Total volume of 470 kg for the 2 uses and 400 kg for the Use-1 specific mixtures) - 15% (70/470) of the time for the Use-2 (Total volume of 470 kg for the 2 uses and 70 kg for the Use-2 specific mixtures) Use-1 general population adjusted exposure (µg/m 3 ) Use-2 general population adjusted exposure (µg/m 3 ) 3.76x x10-6 Table 14. General population adjusted exposure by Use The excess of risk of lung cancer for general population will be adjusted by the review period for the 2 uses. Weighted excess of lung cancer risk for general population Excess risk of lung cancer, per µg/m 3 of Cr(VI) based on 70 years, 365 days per year, 24h per day (RAC 2013) Value 2.9x10-2 Excess risk of lung cancer, per µg/m 3 of Cr(VI) based on 1 year, 365 days per year, 24h per day 4.1x10-4 Excess risk of lung cancer, per µg/m 3 of Cr(VI) based on 7 years (review period for the Use-1), 365 days per year, 24h per day Excess risk of lung cancer, per µg/m 3 of Cr(VI) based on 12 years (review period for the Use-2), 365 days per year, 24h per day 2.9x x10-3 Table 15. RAC adjusted excess of risk calculation for general population Use-1 risk for general population Use-2 risk for general population 1.09x x10-8 Table 16. Risk calculation by Use for general population 45

21 Conclusion: Compare to the worker s excess risk of lung cancer Considering the amount of substance used at the working place Considering the risk management measure implemented by PST Considering the hexavalent chromium atmospheric release by working days Considering that the decision point for acceptable lifetime cancer risk levels used for workers are generally around 10-5 * The risk for general population is considered as negligible. * This decision point is presented in the technical guidance of ECHA Worker contributing scenario 1: Preparation of the coating (mixing and screening compound) Conditions of use Parameter Information Product characteristics Product Physical form Weight fraction of the substance in the liquid mixture Chromium trioxide solution or chromic acids and their oligomers Powders dissolved in a liquid or incorporated in a liquid matrix Small (1-5%) Viscosity of the liquid mixture Liquids with low viscosity (like water) Operational conditions Duration of use 15 mins Primary emission source located in the breathing zone of the worker Yes, <1m Secondary Emission Source No Type of activity Falling liquids Transfer of liquid product with flow of l/minute Handling that reduces contact between product and 13 ECHA Guidance on information requirements and chemical safety assessment, chapiter R8, Appendix R page

22 adjacent air. Note: This does not include processes that are fully contained by localised controls Submerged loading, where the liquid dispenser remains below the fluid level reducing the amount of aerosol formation Site and room size of the work area Indoors, small workrooms only Risk Management measures Local exhaust ventilation (LEV) No localised control General ventilation in the work area 10 Air changes per hour (ACH) at least Fugitive Emission Sources Process not fully enclosed. Demonstrable and effective housekeeping practices in place. Version of modeling tool: ART (Advanced Reach Tool) version 1.5 Table 17. Condition of use for the contributing scenario 1, by a modelling approach The ART modelling tool doesn t take into account all the information required for the risk assessment of a chemical safety report. The table below gives complementary information that does not influence the modelling calculation. Parameter Information Personal protective Equipment Nitrile Gloves Safety clothing (Tyvek disposable suit with hood) Personal protective equipment The same PPE will be used for the others 47

23 contributing scenario Other parameter Amount 0,470 t / an Number of workers 41 Exposure value will be validated by working air measure campaign (monitoring). Exposure level lower than estimated level will confirm the risk assessment. Table 18. Other using condition of the contributing scenario Exposure and risks for workers Estimated exposures are listed in table 19 below. No respiratory protections are taken into account for this assessment. The ART exposure estimation is a predicted 90 th percentile long term exposure. Type of exposure Exposure concentration estimation (not adjusted to the time) Time duration ART estimation 0.34 µg/m 3 15 mins Table 19. Estimated raw exposure concentrations for contributing scenario 1 The exposure assessment will be carried out comparing the measured data (the measure corresponding to the complete exposure scenario) and the compilation of exposure estimate from modelling data Worker contributing scenario 2: Manual spraying Conditions of use Parameter Information Product characteristics Product Physical form Weight fraction of the substance in the liquid mixture Chromium trioxide solution or chromic acids and their oligomers Powders dissolved in a liquid or incorporated in a liquid matrix Small (1-5%) 48

24 Viscosity of the liquid mixture Liquids with low viscosity (like water) Operational conditions Duration of use 240 mins Primary emission source located in the breathing zone of the worker Yes, <1m Secondary Emission Source No Surface spraying of liquids Type of activity Moderate application rate (0.3-3l/minute) Only horizontal or downward Spraying with no or low compressed air use Site and room size of the work area Indoors, 300m 3 Risk Management measures Local exhaust ventilation (LEV) Other enclosing hoods (90% reduction) General ventilation in the work area Specialised room ventilation with more than 10 ACH Fugitive Emission Sources Process not fully enclosed. Demonstrable and effective housekeeping practices in place. Version of modeling tool: ART (Advanced Reach Tool) version 1.5 Table 20. Condition of use for the contributing scenario 2, by a modelling approach The ART modelling tool doesn t take into account all the information required for the risk assessment of a chemical safety report. The table below gives complementary information that does not influence the modelling calculation. Parameter Information Personal protective Equipment Respiratory protective equipment Respirator with full face shield (ref EN B) with associated protection factor to around 100 (depending of the country)(annex 7) 49

25 Gloves Other personal protective equipment Safety clothing Safety shoes Other parameter Amount 0,470 t / an Number of workers 36 Exposure value will be validated by working air measure campaign (monitoring). Exposure level lower than estimated level will confirm the risk assessment. Table 21. Other using condition of the contributing scenario Exposure and risks for workers The estimate exposures are listed in table 22 below. Respiratory protections are taken into account for this assessment. Regarding the respiratory protection, a protection factor of 100 will be considered for this assessment. The assigned protection factor is described for this type of respiratory protection in UK at 40 and in Italy at 100. Manufacturers give a nominal protection factor of 200 for this type of equipment. In this case to be representative of the different shops (UK & Italy) applicant will consider an APF of 100. Moreover, OSHA (Occupational Safety and Health Administration) in the US assigns a protection factor of 1000 for this respiratory protection. Despite, PST is an US company, a protection factor of 100 will be considered for this assessment as a realistic case scenario. 50

26 Type of exposure Exposure concentration estimation (not adjusted to the time) Time duration ART estimation 76 µg/m mins ART estimation adjusted by the use of respiratory protection factor during 240 mins (APF 100) 0.76 µg/m mins Table 22. Estimated raw exposure concentrations for contributing scenario 2 The exposure assessment will be carried out comparing the measured data (the measure corresponding to the complete exposure scenario) and the compilation of exposure estimate from modelling data Worker contributing scenario 3: Automated spraying Conditions of use Parameter Information Product characteristics Product Physical form Weight fraction of the substance in the liquid mixture Chromium trioxide solution or chromic acids and their oligomers Powders dissolved in a liquid or incorporated in a liquid matrix Small (1-5%) Viscosity of the liquid mixture Liquids with low viscosity (like water) Operational conditions Duration of use 240 mins Primary emission source located in the breathing zone of the worker No, >1m Secondary Emission Source No Type of activity Surface spraying of liquids Moderate application rate (0.3-3l/minute) 51

27 Only horizontal or downward Spraying with no or low compressed air use Site and room size of the work area Indoors, 300m 3 Risk Management measures Low level containment (90% reduction) Local exhaust ventilation (LEV) Complete segregation with ventilation and filtration of recirculated air (90% reduction) Complete personal enclosure with ventilation (90% reduction) General ventilation in the work area Specialised room ventilation with more than 10 ACH Fugitive Emission Sources Process not fully enclosed. Demonstrable and effective housekeeping practices in place. Version of modeling tool: ART (Advanced Reach Tool) version 1.5 Table 23. Condition of use for the contributing scenario 3, by a modelling approach The ART modelling tool doesn t take into account all the information required for the risk assessment of a chemical safety report. The table below gives complementary information that does not influence the modelling calculation. Parameter Information Personal protective Equipment Personal protective equipment Gloves Safety clothing Other parameter Amount 0,470 t / an Number of workers 5 Exposure value will be validated by working air measure campaign (monitoring). Exposure level lower than estimated level will confirm the risk assessment. Table 24. Other using condition of the contributing scenario Exposure and risks for workers Estimated exposures are listed in table 25 below. No respiratory protections are taken into account for this assessment. The ART exposure estimation is a predicted 90 th percentile long term exposure. 52

28 Type of exposure Exposure concentration estimation (not adjusted to the time) Time duration ART estimation µg/m mins Table 25. Estimated raw exposure concentrations for contributing scenario 3 The exposure assessment will be carried out comparing the measured data (the measure corresponding to the complete exposure scenario) and the compilation of exposure estimate from modelling data Worker contributing scenario 4: Parts transportation Conditions of use Parameter Information Product characteristics Product Physical form Weight fraction of the substance in the liquid mixture Chromium trioxide solution or chromic acids and their oligomers Powders dissolved in a liquid or incorporated in a liquid matrix Small (1-5%) Viscosity of the liquid mixture Liquids with low viscosity (like water) Operational conditions Duration of use 10 mins (2x5mins) Primary emission source located in the breathing zone of the worker Yes, <1m Secondary Emission Source No Handling of contaminated objects Type of activity Activities with treated/contaminated objects (surface 1-3m 2 ) Contamination >90% (The coated articles are transferred by the workers from the spraying room to a dedicated closed heat 53

29 chamber/pst Use) Site and room size of the work area Indoors, 3000m 3 Risk Management measures Local exhaust ventilation (LEV) No localised control General ventilation in the work area Mechanical ventilation giving at least 1ACH Fugitive Emission Sources Process not fully enclosed. Demonstrable and effective housekeeping practices in place. Version of modeling tool: ART (Advanced Reach Tool) version 1.5 Table 26. Condition of use for the contributing scenario 4, by a modelling approach The ART modelling tool doesn t take into account all the information required for the risk assessment of a chemical safety report. The table below gives complementary information that does not influence the modelling calculation. Parameter Information Personal protective Equipment Personal protective equipment Gloves Safety clothing Other parameter Amount 0,470 t / an Number of workers 41 Exposure value will be validated by working air measure campaign (monitoring). Exposure level lower than estimated level will confirm the risk assessment. Table 27. Other using condition of the contributing scenario Exposure and risks for workers Estimated exposures are listed in table 28 below. No respiratory protections are taken into account for this assessment. The ART exposure estimation is a predicted 90 th percentile long term exposure. Type of exposure Exposure concentration estimation (not adjusted to the time) Time duration 54

30 Type of exposure Exposure concentration estimation (not adjusted to the time) Time duration ART estimation 0.72 µg/m 3 10 mins Table 28. Estimated raw exposure concentrations for contributing scenario 4 The exposure assessment will be carried out comparing the measured data (the measure corresponding to the complete exposure scenario) and the compilation of exposure estimate from modelling data Worker contributing scenario 5: Drying of coating Conditions of use Parameter Information Product characteristics Product Physical form Weight fraction of the substance in the liquid mixture Chromium trioxide solution or chromic acids and their oligomers Powders dissolved in a liquid or incorporated in a liquid matrix Small (1-5%) Viscosity of the liquid mixture Liquids with low viscosity (like water) Operational conditions Duration of use 30 mins Primary emission source located in the breathing zone of the worker No, >1m Secondary Emission Source No Handling of contaminated objects Type of activity Activities with treated/contaminated objects (surface 1-3m 2 ) Contamination >90% Site and room size of the work area Indoors, 300m 3 The coated articles are in a dedicated a furnace for the oven dying 55

31 Risk Management measures Local exhaust ventilation (LEV) No localised control Segregation Personal enclosure Partial segregation with ventilation and filtration of recirculated air (70% reduction) Partial personal enclosure with ventilation (70% reduction) General ventilation in the work area 10 air changes per hour (ACH) Fugitive Emission Sources Process not fully enclosed. Demonstrable and effective housekeeping practices in place. Version of modeling tool: ART (Advanced Reach Tool) version 1.5 Table 29. Condition of use for the contributing scenario 5, by a modelling approach The ART modelling tool doesn t take into account all the information required for the risk assessment of a chemical safety report. The table below gives complementary information that does not influence the modelling calculation. Parameter Information Personal protective Equipment Other personal protective equipment Gloves Safety clothing Other parameter Amount 0,470 t / an Number of workers 36 Exposure value will be validated by working air measure campaign (monitoring). Exposure level lower than estimated level will confirm the risk assessment. Table 30. Other using condition of the contributing scenario Exposure and risks for workers Estimated exposures are listed in table 31 below. No respiratory protections are taken into account for this assessment. The ART exposure estimation is a predicted 90 th percentile long term exposure. Type of exposure Exposure concentration estimation (not adjusted to the time) Time duration 56

32 Type of exposure Exposure concentration estimation (not adjusted to the time) Time duration ART estimation µg/m 3 30 mins Table 31. Estimated raw exposure concentrations for contributing scenario 5 The exposure assessment will be carried out comparing the measured data (the measure corresponding to the complete exposure scenario) and the compilation of exposure estimate from modelling data Worker contributing scenario 6: Curing of coating Conditions of use Parameter Information Product characteristics Product Physical form Weight fraction of the substance in the liquid mixture Chromium trioxide solution or chromic acids and their oligomers Powders dissolved in a liquid or incorporated in a liquid matrix Small (1-5%) Viscosity of the liquid mixture Liquids with low viscosity (like water) Operational conditions Duration of use 120 mins Primary emission source located in the breathing zone of the worker No, >1m Secondary Emission Source No Handling of contaminated objects Type of activity Activities with treated/contaminated objects (surface 1-3m 2 ) Contamination >90% Site and room size of the work area Indoors, 300m 3 Risk Management measures Local exhaust ventilation (LEV) Partial segregation with ventilation and filtration of 57

33 recirculated air (70% reduction) Partial personal enclosure with ventilation (70% reduction) General ventilation in the work area 10 air changes per hour (ACH) Fugitive Emission Sources Process not fully enclosed. Demonstrable and effective housekeeping practices in place. Version of modeling tool: ART (Advanced Reach Tool) version 1.5 Table 32. Condition of use for the contributing scenario 6, by a modelling approach The ART modelling tool doesn t take into account all the information required for the risk assessment of a chemical safety report. The table below gives complementary information that does not influence the modelling calculation. Parameter Information Personal protective Equipment Other personal protective equipment Gloves Safety clothing Other parameter Amount 0,470 t / an Number of workers 41 Exposure value will be validated by working air measure campaign (monitoring). Exposure level lower than estimated level will confirm the risk assessment. Table 33. Other using condition of the contributing scenario Exposure and risks for workers Estimated exposures are listed in table 34 below. No respiratory protections are taken into account for this assessment. The ART exposure estimation is a predicted 90 th percentile long term exposure. Type of exposure Exposure concentration estimation (not adjusted to the time) Time duration ART estimation µg/m mins Table 34. Estimated and measured Exposure concentrations for contributing scenario 6 58

34 The exposure assessment will be carried out by comparing the measured data (the measure corresponding to the complete exposure scenario) and the compilation of exposure estimate from modelling data Worker contributing scenario 7: Removal of coating Conditions of use Parameter Information Product characteristics Product Physical form Weight fraction of the substance in the liquid mixture Chromium trioxide solution or chromic acids and their oligomers Powders dissolved in a liquid or incorporated in a liquid matrix Small (1-5%) (This is the concentration of the substance in the mixtures, because it too difficult to estimate the remaining quantities during the cleaning. Nevertheless, it is clear that the remaining proportion of the substance is clearly lower) Viscosity of the liquid mixture Liquids with low viscosity (like water) Operational conditions Duration of use 60 mins Primary emission source located in the breathing zone of the worker Yes, <1m Secondary Emission Source No Handling of contaminated objects Type of activity Activities with treated/contaminated objects (surface 1-3m 2 ) Contamination >90% Site and room size of the work area Indoors, 100m 3 Risk Management measures (Coating are remove from article via a stripping process / PST Use) Local exhaust ventilation (LEV) Other enclosing hoods (90% reduction) General ventilation in the work area 10 air changes per hour (ACH) 59

35 Fugitive Emission Sources Process not fully enclosed. Demonstrable and effective housekeeping practices in place. Version of modeling tool: ART (Advanced Reach Tool) version 1.5 Table 35. Condition of use for the contributing scenario 8, by a modelling approach The ART modelling tool doesn t take into account all the information required for the risk assessment of a chemical safety report. The table below gives complementary information that does not influence the modelling calculation. Parameter Information Personal protective Equipment Other personal protective equipment Gloves Safety clothing Other parameter Amount 0,470 t / an Number of workers 41 Exposure value will be validated by working air measure campaign (monitoring). Exposure level lower than estimated level will confirm the risk assessment. Table 36. Other using condition of the contributing scenario Exposure and risks for workers Estimated exposures are listed in table 37 below. No respiratory protections are taken into account for this assessment. The ART exposure estimation is a predicted 90 th percentile long term exposure. Type of exposure Exposure concentration estimation (not adjusted to the time) Time duration ART estimation µg/m 3 60 mins Table 37. Estimated raw exposure concentrations for contributing scenario 8 The exposure assessment will be carried out comparing the measured data (the measure corresponding to the complete exposure scenario) and the compilation of exposure estimate from modelling data. 60