CHEMICAL SAFETY REPORT

Transcription

1 CHEMICAL SAFETY REPORT Legal name of applicant(s): EURENCO Submitted by: EURENCO Substance: 1,2-Dichloroethane (EDC) EC number: CAS Number: Use title: Industrial use of 1,2-Dichloroethane as a solvent for the synthesis of Polyepichlorohydrin used as a precursor in the production of Glycidyl Azide Polymer, an energetic oligomer with hydroxyl terminations used to increase the energetic performance of propellants and explosives Use number: 1

2 9. EXPOSURE ASSESSMENT 9.1. Introduction Eurenco is a leading European company for military explosives, propellants and combustible items. 1,2-Dichloroethane (EDC) is used in the synthesis of Polyepichlorohydrin (PECH), a precursor subsequently used in the production of Glycidyl Azide Polymer (GAP). GAP is an energetic oligomer with hydroxyl terminations used to increase the energetic performance of propellants. EDC is thus used on the site of Sorgues in the polymerisation process of ECH. The use of 1,2-EDC concerns six workers. LEGAL ENTITY TYPE OF PROCESS SITE LOCATION TOTAL NUMBER OF WORKER INVOLVED EURENCO Polymerisation of ECH Sorgues, France 6 Table 8: EURENCO s AfA for Use-1 Exposure assessment (and related risk characterisation) is focused on the use of 1,2-Dichloroethane (EDC) Overview of uses and Exposure Scenarios Process description The present Chemical Safety Report covers the use of 1,2-EDC as a solvent in the process used for the synthesis of GAP Process overview The global chemical reaction is a two-stage process, involving polymerisation of Epichlorohydrin (ECH) to Polyepichlorohydrin (PECH) followed by the conversion of PECH to Glycidyl Azide Polymer (GAP)by nucleophilic substitution with chloride azide: - Step 1 : Polymerisation of ECH to PECH is carried out using 1,2-EDC as solvent. In the context of the GAP synthesis, the reaction was specifically developed in order to obtain PECH-diol. - Step 2 : GAP-diol possesses hydroxyl functional groups located at both ends of the chains and is synthesised via the nucleophilic reaction of its precursor, PECH, with sodium azide (NaN 3 ) 3. The global reaction is described below: 3 Eroglu, Network characterisation of energetic Poly(glycidyl azide), Tr. J. of Chemistry, 21 (1997), , 1997 Use-1 EURENCO 20

3 Figure 2. GAP-diol synthesis reaction. The use of 1,2-EDC is limited to Step 1 of the abovementioned reaction: the polymerisation of ECH to PECH. Sampling and laboratory testing demonstrate the absence of 1,2-EDC in the PECH at the end of the reaction, therefore eliminating any risk of exposure during the synthesis of GAP or during the manipulation of GAP by EURENCO s customers for their applications. Being focused on exposure to 1,2-EDC, the present CSR will therefore only detail the process stages described as Step 1. Synthesis of PECH is carried out in the Demi-Grand facility on the site of Sorgues, with the following steps: Use-1 EURENCO 21

4 Figure 3. PECH synthesis process Use-1 EURENCO 22

5 Figure 4. "Demi-Grand" facility Step 1, involving exposure to 1,2-EDC, is developed in what follows Lifecycle of 1,2-EDCin the synthesis of PECH 1 Supply and storage 1,2-EDC is supplied to EURENCO by Azelis in 200L hermetic tanks and stored on-site in a dedicated room. Upon receipt, 1,2-EDC is subject to sampling and laboratory control of key physico-chemical parameters in order to be validated for industrial use. The sampling is performed by opening the tank, and transferring a small amount of substance in a laboratory vessel by using a pipette. Laboratory testing is carried out in a semi-enclosed analysis fume cupboard. Except during the sampling operation, the tank is not opened, and no exposure to 1,2-EDC can occur. Use-1 EURENCO 23

6 Figure 5: sampling Sampling and laboratory testing are considered in the estimation of exposure to 1,2-EDC and are treated in this CSR in the Worker Contributing Scenarios 1 and 6 (WCS-1 & WCS-6). 2 Pre-production run The Demi-Grand facility is not used exclusively for the synthesis of PECH and GAP. At the beginning of each production campaign (i.e. once a year), a preproduction run is carried out with 200L of 1,2-EDC, in order to wash the overall piping and instrumentation. This pre-production run implies two potential exposures: - During the transfer of 1,2-EDC in the system. This transfer is performed in the same conditions than the next step: Offloading of EDC. The emission of substance generated during this transfer is considered in Contributing Scenarios 7 & 8 ; - During the recovery of the quantity of EDC used. It is pumped in all the piping in the same conditions than those described for the recovery of effluents from aqueous effluents. This task is considered in Contributing Scenarios 12 & 13. This step of the process involve two tasks: the transfer of 1,2-EDC is treated in Worker Contributing Scenarios 7 & 8 (WCS-7 & WCS-8) and the recovery of EDC is treated in the Worker Contributing Scenarios 12 & 13 (WCS-12 & WCS- 13). Use-1 EURENCO 24

7 3 Offloading of 1,2-EDC in the system Before being transferred in the reaction system, each 1,2-DEDC batch undergoes sampling and testing. As previously described, the sampling is performed by opening the tank, and transferring a small amount of substance in a laboratory vessel by using a pipette. Laboratory testing is carried out in a semi-enclosed analysis fume cupboard. The introduction of 1,2-EDC in the reaction system is made as presented in the Figure 6, by introducing a plunging cane in the 200L tanks and pumping its content to the reactor. Offloading of 1,2-EDC takes place outside of the Demi-Grand facility with a movable capturing hood as local exhaust ventilation. The operator wears a supplied-air respirator in continuous mode. Once the plunging cane is placed in the tank and the pumping is engaged, the operator remains at more than 1 meter from the tank opening during the rest of this operation. The operator wears a supplied-air respirator in continuous mode during the whole operation. Figure 6. Offloading of EDC After pumping, EDC is automatically transferred to the main reactor through a closed circuit. Consequently, two type of exposure are considered during this transfer, depending on the position of the worker at more or less than 1 meter from the tank. This task is considered in the estimation of exposure to 1,2-EDC. It is treated in this CSR in the two Worker Contributing Scenarios 7 & 8 (WCS-7 & WCS-8) for near-field and far-field exposures. Sampling and laboratory testing activities are considered in the Worker Contributing Scenarios 2 and 6 (WCS-2 & WCS-6). Use-1 EURENCO 25

8 4 Introduction of raw materials Raw materials are introduced in the main reactor containing 1,2-EDC via a hand-sized hole of approximately 7cm in diameter. The operator wears a supplied-air respirator in continuous mode. Figure 7. Introduction of raw materials The only potential exposure to 1,2-EDC can occur during the introduction of raw materials. During this operation, a movable capturing hood as local exhaust ventilation is placed above the hand-sized hole and the operator wears a supplied-air respirator in continuous mode. This task is considered in the estimation of exposure to 1,2-EDC. It is treated in this CSR in the Worker Contributing Scenario 9 (WCS-9). 5 Pouring of ECH ECH is automatically pumped and added in the main reactor through a completely closed system. ECH is channelled in a high integrity contained system where no potential exposure can occur. The main reactor is tightly closed during this operation. Consequently, no exposure can be considered during this stage of the process. No exposure to 1,2-EDC can occur during this stage of the process. It is therefore not considered in the next parts of this CSR. 6 Synthesis of PECH The synthesis of PECH is automatically controlled in the main reactor. During this synthesis, the reactor is tightly closed and there is no possibility of exposure. Consequently, no exposure can be considered during this stage of the process. No exposure to 1,2-EDC occurs during this stage of the process. Consequently, it Use-1 EURENCO 26

9 is not considered in the next parts of this CSR. 7 Introduction of bicarbonate, ph measurement and extraction of the aqueous phase After the PECH synthesis reaction, the content of the main reactor is transferred to an auxiliary reactor. This transfer is automatically performed through a completely closed circuit and does not involve manual operation. Consequently, there is no possibility of exposure during this stage of the process. The manhole (of approximately 20cm in diameter) of the auxiliary reactor is opened three times: - For the introduction of bicarbonate ; - For ph measurement ; - After rinsing the content of the reactor with water, an aqueous phase is formed and it is manually pumped through a closed and automated system. After the last rinsing step, the aqueous phase is then manually pumped with a plunging cane introduced in the reactor through the manhole. During all the operations performed at the manhole of this auxiliary reactor, a movable capturing hood as local exhaust ventilation is placed above the opening and the operator wears a supplied-air respirator in continuous mode. All these operation will be considered in this CSR in the Contributing Scenario 10 and Contributing Scenario 11. One sample is collected through the manhole and undergoes laboratory testing. Sampling and laboratory analysis are treated in this CSR in Contributing Scenarios 3 and 6. Figure 8. Loading of bicarbonate Use-1 EURENCO 27

10 This task is considered in the estimation of exposure to 1,2-EDC. It is treated in this CSR in the Worker Contributing Scenarios 10 and 11 (WCS-10 & WCS-11) for the activities at the manhole, and in the Worker Contributing Scenarios 3 and 6 (WCS-3 & WCS-6) for the sampling and laboratory analysis steps. 8 Distillation of the aqueous phase Distillation of the aqueous phase is carried out automatically in an hermetic enclosure. No exposure can therefore occur during this step. No exposure to 1,2-EDC occurs during this stage of the process. Consequently, it is not considered in the next parts of this CSR. 9 Recovery of 1,2-EDC from distillate 1,2-EDC collected after the distillation phase is recovered by pumping from a storage tank to a 1,000L bulk tank with a plunging cane. This step is performed once per campaign. This step is carried out outside and the operator wears a full face mask with filter ABEK2P3. It is considered in this CSR in Contributing Scenarios 8 and 9. Once the plunging cane is placed in the tank and the pumping is engaged, the operator remains at more than 1 meter from the tank opening during the rest of this operation. Consequently, two type of exposure are considered during this transfer, depending on the position of the worker at more or less than 1 meter from the tank. Use-1 EURENCO 28

11 This task is considered in the estimation of exposure to 1,2-EDC. It is treated in this CSR in the Worker Contributing Scenarios 12 and 13 (WCS-12 & WCS-13) 10 Discarding of residue from distillation The residue resulting from the distillation step contains trace levels of remaining 1,2-EDC. This residue is discharged in the nearby Rhône river. The concentration of 1,2-EDC is therefore very small in the release of residue, but it is still a possibility of release. The 1,2-EDC content of emissions to water are monitored in the context of the RSDE 4 plan based on Directive 2006/11/CE. This release is considered in the estimation of exposure to 1,2-EDC. It is treated in this CSR in the Environment Contributing Scenario 1 (ECS-1). 11Recovery of the organic phase and drying of PECH The PECH-containing aqueous phase pumped from the auxiliary reactor is then distilled. The drying process is completely closed and there is no possibility of exposure other than the sampling and laboratory analysis carried out to assess the compliance of PECH with its functional requirements. Laboratory testing is carried out in a semi-enclosed analysis fume cupboard. This sampling and laboratory analysis steps are considered in the estimation of exposure to 1,2-EDC and treated in this CSR in the Worker Contributing Scenarios 4 and 6 (WCS-4 & WCS-6). 12Recovery of effluents after drying The organic phase recovered and pumped from the auxiliary reactor is then dried by using a completely closed process. The effluents of the drying process are recovered by pumping from a storage tank to a 1,000L bulk tank with a plunging cane. The recovery of effluents after drying is carried out once per manufacturing operation. This step is carried out outside and the operator wears a full face mask with filter ABEK2P3. Once the plunging cane is placed in the tank and the pumping is engaged, the operator remains at more than 1 meter from the tank opening during the rest of this operation. Consequently, two type of exposure are considered during this transfer, depending on the position of the worker at more or less than 1 meter from the tank. A sampling of the effluent is carried out at the bulk tank, for archival, but does not undergo laboratory analysis. 4 In French : Recherche de Substances Dangereuses dans l Eau Use-1 EURENCO 29

12 This task is considered in the estimation of exposure to 1,2-EDC. It is treated in this CSR in the Worker Contributing Scenarios 12 and 13 (WCS-12 & WCS-13), and the sampling is treated in the Worker Contributing Scenario 5 (WCS-5). 13 Maintenance Piping and instrumentation may require maintenance intervention. First-level interventions are carried out by the internal maintenance staff (1 intervention in 2015 and 6 interventions in 2014 no exposure). Second-level interventions are carried out by an external service provider (1 intervention in 2015 with potential exposure). Potential exposure is encountered during maintenance but the inventory of maintenance interventions show no exposure for 2014 and Use-1 EURENCO 30

13 Synthesis of the process steps included in the CSR SYNTHESIS STEP 1 Supply and storage 2 Pre-production run 3 Offloading of 1,2-EDC in the system CONTRIBUTING SCENARIOS WCS-1 Sampling 1 WCS-6 Laboratory testing WCS-7 WCS-8 WCS-12 WCS-13 Offloading, near field Offloading, far field Recovery of effluents, near field Recovery of effluents, far field WCS-2 Sampling 2 WCS-6 WCS-7 WCS-8 Laboratory testing Offloading, near field Offloading, far field 4 Introduction of raw materials WCS-9 Introduction of raw materials 5 Pouring of ECH - No exposure 6 synthesis of PECH - No exposure 7 Introduction of bicarbonate, ph measurement and extraction of the aqueous phase WCS-3 Sampling 3 WCS-6 WCS-10 WCS-11 8 Distillation of the aqueous phase - No exposure 9 Recovery of 1,2-EDC from distillate 10 Discarding of distillate residues 11 Recovery of the organic phase and drying of PECH 12 Recovery of effluents after drying WCS-12 Laboratory testing Loading of bicarbonate & ph measurement Extraction of the aqueous phase Recovery of effluents, near field WCS-13 Recovery of effluents, far field ECS-1 Industrial use of 1,2-EDC as a solvent for the synthesis of PECH WCS-4 Sampling 4 WCS-6 Laboratory testing WCS-5 Sampling 5 WCS-12 WCS Maintenance - No exposure Recovery of effluents, near field Recovery of effluents, far field Table 9. Synthesis of the process steps included in the CSR Tonnage explanation / Number of workers exposed Batch synthesis of PECH is carried out by EURENCO in a single facility on the site of Sorgues (Vaucluse, France) for a total duration of less than one month per year (22 days in 2015, 15 days in 2014). Each production operation requires two operators for a total duration of two to three 8hr-shifts. A total of seven employees are currently mobilised in the production of PECH and are therefore potentially exposed to 1,2-EDC. EURENCO s use of 1,2-EDC for the synthesis of PECH amounts respectively to 1.0 and 2.6 tons for the two last campaigns of 2014 and Use-1 EURENCO 31

14 Overview of Exposure Scenarios IDENTIFIERS TITLES OF EXPOSURE SCENARIOS AND THE RELATED CONTRIBUTING SCENARIOS ES-1 ES1: Industrial use of 1,2-Dichloroethane as a solvent for the synthesis of Polyepichlorohydrin ECS-1 - Industrial use of 1,2-Dichloroethane as a solvent for the synthesis of Polyepichlorohydrin (ERC 6b) WCS-1 - Sampling 1 (PROC 9) WCS-2 - Sampling 2 (PROC 9) WCS-3 - Sampling 3 (PROC 9) WCS-4 - Sampling 4 (PROC 9) WCS-5 - Sampling 5 (PROC 9) WCS-6 - Laboratory analysis (PROC 15) WCS-7 - Offloading, near field (PROC 8a) WCS-8 - Offloading, far field (PROC 8a) WCS-9 - Introduction of raw materials (PROC 8a) WCS-10 - Introduction of bicarbonate & ph measurement (PROC 5) WCS-11 - Extraction of aqueous phase (PROC 8a) WCS-12 - Recovery of effluents, near field (PROC 8a) WCS-13 - Recovery of effluents, far field (PROC 8a) Table 10. Overview of exposure scenarios Introduction to the assessment Environment The environmental assessment is not the main consideration for this CSR dedicated to the Application for Authorisation regarding the SVHC properties stated in column 2 of entry 26 in annex XIV of REACh (Commission Regulation (EU) No 125/2012). Nevertheless, in the environmental contributing scenarios, applicant will analyse and discuss the possible release and 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 The final assessment of worker s exposures will be based on both measurement and modelling. The present document only details modelling results. Risk assessment is based on ECHA s Application for Authorisation: establishing a reference dose response relationship for carcinogenicity of 1,2- Dichloroethane publication of June 5 th, Use-1 EURENCO 32

15 Exposures and excess risk calculation will be developed considering only carcinogenic effects Inhalation For the description of each contributing scenario, applicant will use the ART 1.5 software to calculate 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. To calculate the excess risk of cancer due to inhalation exposure (Chapter 10), applicant will use the estimated value to assess a quantitative analysis Dermal For the description of each contributing scenario, we will use the ECETOC TRA software to calculate an associated value of dermal exposure. ECETOC TRA inputs for each contributing scenario are given in Annex. To calculate the excess risk of cancer due to dermal exposure (Chapter 10), applicant will use the estimated value to assess a quantitative analysis Consumers No consumer exposure is involved in this AfA Exposure Scenario 1: Synthesis of PECH Sector of use: Industrial use: Uses of substances as such or in preparations at industrial sites (SU 3) Environmental contributing scenario: - ECS-1 : Discarding of residue from distillation (ERC 6b) Worker contributing scenarios: - WCS-1: Sampling 1(PROC 9) - WCS-2: Sampling 2(PROC 9) - WCS-3: Sampling 3(PROC 9) - WCS-4: Sampling 4(PROC 9) - WCS-5: Sampling 5(PROC 9) - WCS-6: Laboratory sampling (PROC 15) - WCS-7: Offloading, near field (PROC 8a) - WCS-8: Offloading, far field (PROC 8a) - WCS-9: Introduction of raw materials (PROC 8a) - WCS-10: Introduction of bicarbonate & ph measurement (PROC 5) - WCS-11: Extraction of aqueous phase (PROC 8a) - WCS-12: Recovery of effluents, near field (PROC 8a) - WCS-13: Recovery of effluents, far field (PROC 8a) Use-1 EURENCO 33

16 The exposure scenario concerns the first step in the process of synthesis of GAP. Only the tasks leading to exposure to 1,2-EDC, as identified in section 9.1.1, are analysed as contributing scenarios. Efficiency of respiratory protective equipment In order to estimate exposure at the workplace, it is necessary to determine the effectiveness of the respiratory protection equipments used. It results in the Assigned Protection Factor (APF). The choice of this factor may vary, depending on the country for which it is used. Table 11 presents the various protective factors assigned to the breathing equipments used in the considered Exposure Scenarios. COUNTRY ASSIGNED PROTECTION FACTOR (APF) FULL FACE MASK WITH FILTER ABEK2P3 (EN 141) CONTINUOUS FLOW COMPRESSED AIRLINE BREATHING APPARATUS (EN 14594) 4A/4B Finland Germany Italy Sweden United Kingdom 40 - France Nominal protective factor 1,000 2,000 APF used in this CSR The applicant made the choice to use: Table 11: assigned protection factor 5,6 - An APF of 30 for the full mask with gas filter P3. The APF value of 30 indicated from UK for the full face mask is very low for precautionary reasons. The applicant made the choice to use this value; - An APF of 250 for the continuous flow compressed airline breathing apparatus, in line with INRS guidelines. 5 INRS, Les appareils de protection respiratoire, choix et utilisation, Ref : ED 6106, NF EN 529 standard, Annex C Use-1 EURENCO 34

17 Efficiency of the gloves equipment The applicant used a default assigned protection factor (APF) of 10 for the gloves in order to fit with a conservative approach for the estimation of dermal exposure, described in this CSR. Moreover, this default APF is suggested in the TGD on risk assessment part I (page 57 of the chapter 2): Until further data are available for the effectiveness of PPE, a pragmatic solution needs to be adopted of selecting realistic default values for properly selected coveralls and gloves, say 90% protection (=10% penetration), which can be revised as further evidence becomes available. Furthermore, most information on the effectiveness of protective clothing and gloves is obtained in studies with agricultural pesticides. From the available data, analysed in North America and by the EUROPOEM group in Europe, it appears that an estimate of 90% exposure reduction with proper materials and proper behaviour for registration purposes can be taken as a default value for gloves and for protective clothing. In addition, considering that: - these types of vinyl PVC gloves are recommended for hydrocarbon protection as oils, alkaline or acid solutions by the supplier, - the gloves are approved according to EN and thus tested to be relevant for the type and duration of activities as performed on the site of Eurenco, The passage of EDC through the glove leading to dermal exposure of workers appears to be not detectable. Consequently and in order to provide a quantitative assessment of dermal exposure, the applicant considered that an APF of 10 is a conservative value. Use-1 EURENCO 35

18 Environmental Contributing Scenario 1: Industrial use of 1,2- Dichloroethane as a solvent for the synthesis of Polyepichlorohydrin Conditions of use Parameter Information Product characteristics Product 1,2-dichloroethane liquid solution Physical form liquid Amount 2.6 t / year Weight fraction of the substance in the liquid mixture Concentration of substance in the different solutions is between and 1 Operational conditions Emission Sources Atmospheric emissions Liquid effluents Release is expected on the process, via: - Air - Liquid effluents at the end of the process The integrity of the process circuit is regularly monitored. The possibilities of release are detailed below. Air from local extraction systems is collected and evacuated through a chimney on the roof of the facility. The possible atmospheric emissions will be considered in the following part of the CSR. The liquid effluents containing EDC at the end of the process (low amount of the substance remaining (intermediates), are released outside the industrial site. Liquid effluents are regularly monitored Atmospheric releases The technical guidance document part II 7 depending on the activity type. proposes estimated release factor The associated release factor is determined by the following parameters: o IC 3/UC 33 (Chemical industry: Chemicals used in synthesis (intermediates), o o Vapor pressure <10000 Pa, MC=1a (Main category: Used in close system) 7 Technical Guidance Document on risk assessment, part II about environmental risk assessment Use-1 EURENCO 36

19 Thus, the release factor is determined at Based on this release estimation and the Doury abacus 8 (which estimates the dispersion speed), we calculated the exposure of the general population around the site for the Use-1 and the associated risks. Global (2.6 tons/600m): Release per working day is estimated (considering 365 working days per year): = 712 mg per day Global, release per day: 712mg/day (average of 8.24 µg/s on 24h) For the assessment, we took the nearest house at approximately 600m. Atmospheric transfer coefficient (at 600m) from Doury Abacus: 9.32x10-5 s/m 3 The release in air adjusted on 24h is: Release (8.24 µg/s) X Atmospheric transfer coefficient (at 600m) from Doury Abacus (9.32x10-5 s/m 3 ) = 7.68 x 10-4 µg/m Exposure and risks for the environment and man-viaenvironment via the atmospheric compartment The excess cancer risk via inhalation for the general population has been determined by the RAC. Weighted excess of lung cancer risk for general population Value Excess risk cancer via inhalation, per µg/m 3 of EDC (RAC 2015) 3.45x10-6 Table 12: RAC excess of risk calculation for general population Excess risk Value Final individual excess risk of cancer based on, 365 days per year, 24h per day 2.65x10-9 Table 13: Risk calculation for general population 8 Abaques d'evaluation directe des transferts atmospheriques d effluents gazeux, Doury et al, February 1980 Use-1 EURENCO 37

20 Conclusion: Compared to the worker s excess risk of cancer via inhalation Considering the risk management measures implemented by EURENCO Considering the level of containment of the process Considering the 1,2-dichloroethane atmospheric release by working days Considering the uncertainties which lead our calculation to an over-estimation Considering that the decision point for acceptable lifetime cancer risk levels used for general population 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 Aquatic releases The concentrations of EDC in liquid effluent on the site of Eurenco are measured. The exposure estimation for the general population due to release to water is based on the maximum concentration measured in the effluent on the site of Eurenco during an emission episode (the detailed measurements are given in the annex 12.4): C effluent of Eurenco s site = 7.2µg/L Exposure and risks for the environment and man-viaenvironment via the aquatic compartment Calculation of the PEC local surface water : According to the TGD methodology and considering the concentration measured in the effluent on the site of Eurenco (C effluent of Eurenco s site ), the PEC local surface water can be calculated as follow: And With : PEC local surface water = C effluent of Eurenco s site / Dilution factor Dilution factor = (Q E + Q R ) / Q R Q E = 13,647 m 3 /day Q R = 53,568,000 m 3 /day = Flow of the effluent of Eurenco s site (measured) = Flow of the local river (Rhône, France) Q R considered is the lowest mensual dry weather flow (or low-flow season) of the past 5 years. The Dilution factor is then calculated as follow: 9 ECHA Guidance on information requirements and chemical safety assessment, chapiter R8, Appendix R page 140. Use-1 EURENCO 38

21 Dilution factor = ( ,568,000) / 53,568,000 Dilution factor = 3, Consequently, PEC local surface water is calculated as follow: PEC local surface water = C effluent of Eurenco s site / Dilution factor PEC local surface water = 7.2 / 3, PEC local surface water = 1.83 x 10-3 µg/l Exposure of general population via drinking water: As indicated in the TGD document part I 10, drinking water is produced from surface water or groundwater. In this generic scenario, drinking water is considered as directly produced from the first aquatic compartment contaminated: the local surface water. Methodology According to the TGD methodology 10, dependent on the type of storage, two different water treatment systems for surface water can be distinguished: system 1 includes storage in open reservoir, system 2 includes dune recharge. Removal of the dissolved fraction of a xenobiotic from the surface water is modelled by means of purification factors. For the choice between the two systems and the choice between surface water or groundwater, a worst-case approach will be followed. The following table present the TGD criteria to be used for the determination of purification factor: Table 14: Purification factor, based on the methodology used in the TGD document Henry s law constant: The transfer of a substance from the aqueous phase to the gas phase (e.g.volatilisation from surface water) is estimated by means of its Henry's Law constant. As indicated in the TGD part II 11, if the value is not available in the input data set, the required Henry's Law constant can be estimated from the ratio of the vapour pressure to the water solubility. 10 Technical guidance document Part I, page Technical guidance document Part II, page 45, equation (21) Use-1 EURENCO 39

22 Following this calculation with the Physico-chemical properties indicated in section 1.3, the Henry's Law constant is estimated at 128 Pa.m 3.mol -1. Based on the information selected in the ATSDR report 12 the Henry's Law constant is 111 Pa.m 3.mol -1. Thus it is considered at higher than 100 Pa.m 3.mol -1 and the coefficient chosen is ½. Log Kow The Log Kow presented in section 1.3 is 1.45 at 20 C. Thus it is considered at lower than 4 and the coefficient chosen is 1. Final purification factor In order to tie in with a precautionary approach, the system 1 of the treatment process is considered by the applicant. Consequently the determination of the global purification factor can be as follow: The global purification (Fpur) is : Calculation of PEC drinking water Table 15: Determination of purification factor Fpur = 1 x ½ x 1 = 1/2 The standard default value of daily intake of drinking water for the calculation of indirect exposure of humans recommended in the TGD document Part I 13 is 2 L/day. PEC drinking water = PEC local surface water x Fpur x Daily intake of drinking water PEC drinking water = 1.83 x 10-3 µg/day 12 Toxicological profile for 1,2-dichloroethane, ATSD ; September Technical Guidance Document Part I, page 253, table 4 Use-1 EURENCO 40

23 Adjusted to a man of 70kg: PEC drinking water = 2.6 x 10-5 µg/kg bw/day Exposure and risks for the environment and man-viaenvironment via the aquatic compartment Risk of general population via the drinking water: The excess cancer risk via oral route for the general population has been determined by the RAC. Weighted excess of lung cancer risk for general population Value Excess risk cancer via oral route, per µg/kg bw/day of EDC (RAC ) 1.2x10-5 Table 16: RAC excess of risk calculation for general population Excess risk Value Final individual excess risk of cancer based on, 365 days per year, 24h per day 3.14x10-10 Conclusion: Table 17: Risk calculation for general population Compared to the worker s excess risk of cancer via oral route Considering the 1,2-dichloroethane aquatic release by working days Considering the uncertainties which lead our calculation to an over-estimation Considering that the decision point for acceptable lifetime cancer risk levels used for general population 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 RAC/33/2015/09 Application for authorisation: establishing a reference dose response relationship for carcinogenicity of 1,2-dichloroethane 15 ECHA Guidance on information requirements and chemical safety assessment, chapiter R8, Appendix R page 140. Use-1 EURENCO 41

24 Exposure and risk of general population via the food chain: Based on the registration dossier of EDC, the estimated BCF (calculation method) is approximately The ATSDR reports an experimental bioconcentration factor of 2. These two values indicates that 1,2-dichloroethane will not bioconcentrate in fish and aquatic organisms and is not expected to bioaccumulate in the food chain. Thus considering the low concentration in local surface water and the low BCF, the exposure via the food chain is considered negligible. Use-1 EURENCO 42

25 Worker Contributing Scenario 1: Sampling Conditions of use Characterisation of the exposures related to the different sampling operations PRODUCTS CHARACTERISTICS Physical form Vapour pressure Liquids 8600 Pa (Source: INRS) Liquid mole fraction 1 Activity coefficient 1 OPERATIONAL CONDITIONS Temperature Duration Activity class Transfer Loading Type Containment level Primary Emission Source Proximity (<1m?) Flow of transfer Secondary Emission Source RISK MANAGEMENT MEASURES Room temperature (15-25 C) 30 sec. Transfer of liquid products > Falling liquids Submerged loading, where the liquid dispenser remains below the fluid level reducing the amount of aerosol formation Handling that reduces contact between product and adjacent air Yes < 0.1L/minute No Primary localised controls Secondary localised controls Surface Contamination/Fugitive Emission Sources Dispersion Movable capturing hood No secondary localised controls General housekeeping: Yes Indoors > Room size: 1000m3 Ventilation rate: Only good natural ventilation Table 18. Conditions of use, WCS1 The ART modelling tool does not take into account all the necessary information for the risk assessment as required in the CSR. The table below presents the necessary information that do not affect the modelling results. Use-1 EURENCO 43

26 PERSONAL PROTECTIVE EQUIPMENT Respiratory protective equipment (RPE) Full mask with P3 filters (EN 141) Other personal protective equipment OTHER PARAMETERS Protective clothes Protective gloves Quantity 500 ml Number of workers (logistics workers) 1 Frequency 1 time per year Exposure value will be validated by working air measure campaign (monitoring). Level of exposure lower than the estimated level will confirm the risk assessment performed in this CSR. Table 19. Conditions of use, WCS Exposure and risks for workers The estimated inhalation exposure for this contributing scenario is presented in the table below. Exposures are presented with and without respiratory protective equipment (RPE). The description of the RPE used is given at the beginning of the section 9.2. ART ESTIMATION TYPE OF EXPOSURE RAW MODELLED EXPOSURE Without RPE (mg/m3) 7.2 Protection factor 30 With RPE (mg/m3) 0.24 Table 20.Exposure of workers, WCS1, for sampling steps The estimated raw dermal exposure for this contributing scenario, based on the RMM describe above and ECETOC input is the following: mg/kg/day Worker Contributing Scenario 2: Sampling Conditions of use Characterisation of the exposures related to the different sampling operations PRODUCTS CHARACTERISTICS Physical form Vapour pressure Liquids 8600 Pa (Source: INRS) Liquid mole fraction 1 Activity coefficient 1 OPERATIONAL CONDITIONS Temperature Duration Activity class Transfer Loading Type Containment level Room temperature (15-25 C) 30 sec. Transfer of liquid products > Falling liquids Submerged loading, where the liquid dispenser remains below the fluid level reducing the amount of aerosol formation Handling that reduces contact between product and Use-1 EURENCO 44

27 adjacent air Primary Emission Source Proximity (<1m?) Flow of transfer Secondary Emission Source RISK MANAGEMENT MEASURES Primary localised controls Secondary localised controls Surface Contamination/Fugitive Emission Sources Dispersion Yes < 0.1L/minute No Movable capturing hood No secondary localised controls General housekeeping: Yes Outdoors > Source located close to buildings Table 21. Conditions of use, WCS2 The ART modelling tool does not take into account all the necessary information for the risk assessment as required in the CSR. The table below presents the necessary information that do not affect the modelling results. PERSONAL PROTECTIVE EQUIPMENT Respiratory protective equipment (RPE) Other personal protective equipment OTHER PARAMETERS CONTINUOUS FLOW COMPRESSED AIRLINE BREATHING APPARATUS (EN 14594) 4A/4B Protective clothes Protective gloves Quantity mL Number of workers (laboratory) 1 Frequency 8 times per year Exposure value will be validated by working air measure campaign (monitoring). Level of exposure lower than the estimated level will confirm the risk assessment performed in this CSR. Table 22. Conditions of use, WCS Exposure and risks for workers The estimated inhalation exposure for this contributing scenario is presented in the table below. Exposures are presented with and without respiratory protective equipment (RPE). The description of the RPE used is given at the beginning of the section 9.2. ART ESTIMATION TYPE OF EXPOSURE RAW MODELLED EXPOSURE Without RPE (mg/m3) 9.4 Protection factor 250 With RPE (mg/m3) 0.04 Table 23.Exposure of workers, WCS2, for sampling steps The estimated raw dermal exposure for this contributing scenario, based on the RMM describe above and ECETOC input is the following: mg/kg/day Use-1 EURENCO 45

28 Worker Contributing Scenario 3: Sampling Conditions of use Characterisation of the exposures related to the different sampling operations PRODUCTS CHARACTERISTICS Physical form Vapour pressure Liquids 8600 Pa (Source: INRS) Liquid mole fraction 0.35 Activity coefficient 1 OPERATIONAL CONDITIONS Temperature Duration Activity class Transfer Loading Type Containment level Primary Emission Source Proximity (<1m?) Flow of transfer Secondary Emission Source RISK MANAGEMENT MEASURES Room temperature (15-25 C) 30 sec. Transfer of liquid products > Falling liquids Submerged loading, where the liquid dispenser remains below the fluid level reducing the amount of aerosol formation Handling that reduces contact between product and adjacent air Yes < 0.1L/minute No Primary localised controls Secondary localised controls Surface Contamination/Fugitive Emission Sources Dispersion Movable capturing hood No secondary localised controls General housekeeping: Yes Indoors > Room size: 1000m3 > Ventilation rate: No restriction on general ventilation Table 24. Conditions of use, WCS3 The ART modelling tool does not take into account all the necessary information for the risk assessment as required in the CSR. The table below presents the necessary information that do not affect the modelling results. PERSONAL PROTECTIVE EQUIPMENT Respiratory protective equipment (RPE) Other personal protective equipment OTHER PARAMETERS CONTINUOUS FLOW COMPRESSED AIRLINE BREATHING APPARATUS (EN 14594) 4A/4B Protective clothes Protective gloves Quantity ml Number of workers (laboratory) 1 Frequency Once per operation (23 operations per year) Use-1 EURENCO 46

29 Exposure value will be validated by working air measure campaign (monitoring). Level of exposure lower than the estimated level will confirm the risk assessment performed in this CSR. Table 25. Conditions of use, WCS Exposure and risks for workers The estimated inhalation exposure for this contributing scenario is presented in the table below. Exposures are presented with and without respiratory protective equipment (RPE). The description of the RPE used is given at the beginning of the section 9.2. TYPE OF EXPOSURE RAW MODELLED EXPOSURE ART ESTIMATION Without RPE (mg/m3) 2.5 Protection factor 250 With RPE (mg/m3) 0.01 Table 26.Exposure of workers, WCS3, for sampling steps The estimated raw dermal exposure for this contributing scenario, based on the RMM describe above and ECETOC input is the following: mg/kg/day Worker Contributing Scenario 4: Sampling Conditions of use Characterisation of the exposures related to the different sampling operations PRODUCTS CHARACTERISTICS Physical form Vapour pressure Liquids 8600 Pa (Source: INRS) Liquid mole fraction Activity coefficient 1 OPERATIONAL CONDITIONS Temperature Duration Activity class Transfer Loading Type Containment level Primary Emission Source Proximity (<1m?) Flow of transfer Secondary Emission Source RISK MANAGEMENT MEASURES Room temperature (15-25 C) 30 sec. Transfer of liquid products > Falling liquids Splash loading, where the liquid dispenser remains at the top of the reservoir and the liquid splashes freely Handling that reduces contact between product and adjacent air Yes < 0.1L/minute No Primary localised controls Secondary localised controls Movable capturing hood No secondary localised controls Use-1 EURENCO 47

30 Surface Contamination/Fugitive Emission Sources Dispersion General housekeeping: Yes Indoors > Room size: 1000m3 Ventilation rate: No restriction on general ventilation Table 27. Conditions of use, WCS4 The ART modelling tool does not take into account all the necessary information for the risk assessment as required in the CSR. The table below presents the necessary information that do not affect the modelling results. PERSONAL PROTECTIVE EQUIPMENT Respiratory protective equipment (RPE) Other personal protective equipment OTHER PARAMETERS CONTINUOUS FLOW COMPRESSED AIRLINE BREATHING APPARATUS (EN 14594) 4A/4B Protective clothes Protective gloves Quantity ml Number of workers (Laboratory) 1 Frequency Once per operation (23 operations per year) Exposure value will be validated by working air measure campaign (monitoring). Level of exposure lower than the estimated level will confirm the risk assessment performed in this CSR. Table 28. Conditions of use, WCS Exposure and risks for workers The estimated inhalation exposure for this contributing scenario is presented in the table below. Exposures are presented with and without respiratory protective equipment (RPE). The description of the RPE used is given at the beginning of the section 9.2. ART ESTIMATION TYPE OF EXPOSURE RAW MODELLED EXPOSURE Without RPE (mg/m3) Protection factor 250 With RPE (mg/m3) Table 29.Exposure of workers, WCS4, for sampling steps The estimated raw dermal exposure for this contributing scenario, based on the RMM describe above and ECETOC input is the following: mg/kg/day Use-1 EURENCO 48

31 Worker Contributing Scenario 5: Sampling Conditions of use Characterisation of the exposures related to the different sampling operations PRODUCTS CHARACTERISTICS Physical form Vapour pressure Liquids 8600 Pa (Source: INRS) Liquid mole fraction 0.9 Activity coefficient 1 OPERATIONAL CONDITIONS Temperature Duration Activity class Transfer Loading Type Containment level Primary Emission Source Proximity (<1m?) Flow of transfer Secondary Emission Source RISK MANAGEMENT MEASURES Room temperature (15-25 C) 30 sec. Transfer of liquid products > Falling liquids Submerged loading, where the liquid dispenser remains below the fluid level reducing the amount of aerosol formation Handling that reduces contact between product and adjacent air Yes < 0.1L/minute No Primary localised controls Secondary localised controls Surface Contamination/Fugitive Emission Sources Dispersion No localized controls No secondary localised controls General housekeeping: Yes Outdoors > Source not located close to buildings Table 30. Conditions of use, WCS5 The ART modelling tool does not take into account all the necessary information for the risk assessment as required in the CSR. The table below presents the necessary information that do not affect the modelling results. PERSONAL PROTECTIVE EQUIPMENT Respiratory protective equipment (RPE) Full mask with P3 filters (EN 141) Other personal protective equipment OTHER PARAMETERS Protective clothes Protective gloves Quantity ml Number of workers (Laboratory) 1 Frequency Once per operation (23 operations per year) Exposure value will be validated by working air measure campaign (monitoring). Level of exposure lower than the estimated level will confirm the risk assessment performed in this CSR. Table 31. Conditions of use, WCS5 Use-1 EURENCO 49

32 Exposure and risks for workers The estimated inhalation exposure for this contributing scenario is presented in the table below. Exposures are presented with and without respiratory protective equipment (RPE). The description of the RPE used is given at the beginning of the section 9.2. ART ESTIMATION TYPE OF EXPOSURE RAW MODELLED EXPOSURE Without RPE (mg/m3) 5.1 Protection factor 30 With RPE (mg/m3) 0.17 Table 32.Exposure of workers, WCS5, for sampling steps The estimated raw dermal exposure for this contributing scenario, based on the RMM describe above and ECETOC input is the following: mg/kg/day Worker Contributing Scenario 6: Laboratory testing Conditions of use CONDITIONS OF USE MODELLING PARAMETERS PRODUCTS CHARACTERISTICS Physical form Liquids Liquids Vapour pressure At room temperature 8600 Pa (Source: INRS) Liquid mole fraction Maximal EDC concentration 1 Activity coefficient Default value 1 OPERATIONAL CONDITIONS Temperature - Room temperature (15-25 C) Duration Detail testing operations: - Lab test 1 = 30 min; - Lab test 2 = 10 min; - La test 3 & 4 = 5 min each. Total testing duration: 50 min / operation 50 min Activity class - Primary Emission Source Proximity (<1m?) Open surface At arm's length Opening: less than 5 cm in diameter RISK MANAGEMENT MEASURES Activities with open liquid surfaces or open reservoirs. Activities with undisturbed surfaces (no aerosol formation) Yes < 0.1m2 Primary localised controls Work under ventilated hood Fume cupboard Use-1 EURENCO 50

33 Secondary localised controls - No secondary localised controls Surface Contamination/Fugitive Emission Sources - General housekeeping: Yes Dispersion Indoors work, room size between 100 and 300m3 Indoors > 100m3 Ventilation rate: No restriction on general ventilation Table 33. Conditions of use, WCS6 As it is described in the table above there are some differences between the exact parameter in EURENCO site and the modelling parameter available. Differences for which the impact on the exposure estimation with the modelling approach could be judged as a major uncertainty and need to be stress are the following: - The volume of the working room which lead to an overestimation of the workers exposure. - The open surface is less than 5cm of diameter, whereas the modeling take into account 0.1m 2 which lead to an overestimation The ART modelling tool does not take into account all the necessary information for the risk assessment as required in the CSR. The table below presents the necessary information that do not affect the modelling results. PERSONAL PROTECTIVE EQUIPMENT Other personal protective equipment OTHER PARAMETERS Protective clothes Protective gloves Quantity Few ml (from sampling steps) Number of workers (laboratory) 1 Frequency 1 per operation (23 operations per year) Exposure value will be validated by working air measure campaign (monitoring). Level of exposure lower than the estimated level will confirm the risk assessment performed in this CSR. Table 34. Conditions of use, WCS Exposure and risks for workers The estimated inhalation exposure for this contributing scenario is presented in the table below. Exposures are presented without respiratory protective equipment (RPE). TYPE OF EXPOSURE RAW EXPOSURE CONCENTRATION ESTIMATION ART estimation - without RPE 6.4 mg/m 3 Table 35. Exposure of workers, WCS6 Use-1 EURENCO 51

34 The estimated raw dermal exposure for this contributing scenario, based on the RMM describe above and ECETOC input is the following: mg/kg/day Worker Contributing Scenario 7: Offloading, near field Conditions of use CONDITIONS OF USE MODELLING PARAMETERS PRODUCTS CHARACTERISTICS Physical form Liquids Liquids Vapour pressure At room temperature 8600 Pa (Source: INRS) Liquid mole fraction Pure liquid 1 Activity coefficient Default value 1 OPERATIONAL CONDITIONS Temperature - Room temperature (15-25 C) Duration Activity class - Containment level Loading type Primary Emission Source Proximity (<1m?) RISK MANAGEMENT MEASURES Primary localised controls Secondary localised controls Surface Contamination/Fugitive Emission Sources Dispersion Pumping cane close in diameter to the tank opening Pumping cane submerged below liquid surface Operators remains <1m during insertion and removal of pumping cane Movable capturing hood above the opening 15 min Transfer of liquid product with flow of l/minute (falling liquid) Handling that reduces contact between product and adjacent air. Submerged loading, where the liquid dispenser remains below the fluid level reducing the amount of aerosol formation Yes Movable capturing hood No secondary localised controls - General housekeeping: Yes Outdoor operation Outdoors > Source located close to buildings: Yes Table 36. Conditions of use, WCS7 The ART modelling tool does not take into account all the necessary information for the risk assessment as required in the CSR. The table below presents the necessary information that do not affect the modelling results. Use-1 EURENCO 52

35 PERSONAL PROTECTIVE EQUIPMENT Respiratory protective equipment (RPE) Other personal protective equipment OTHER PARAMETERS CONTINUOUS FLOW COMPRESSED AIRLINE BREATHING APPARATUS (EN 14594) 4A/4B Protective clothes Protective gloves Quantity 2.6 tons Number of workers 6 Frequency Once per operation (23 operations per year) per 6 workers Exposure value will be validated by working air measure campaign (monitoring). Level of exposure lower than the estimated level will confirm the risk assessment performed in this CSR. Table 37. Conditions of use, WCS Exposure and risks for workers The estimated inhalation exposure for this contributing scenario is presented in the table below. Exposures are presented with and without respiratory protective equipment (RPE). The description of the RPE used is given at the beginning of the section 9.2. RAW EXPOSURE TYPE OF EXPOSURE CONCENTRATION ESTIMATION ART estimation - without RPE mg/m 3 ART estimation - with RPE (APF = 250) 0.38 mg/m 3 Table 38. Exposure of workers, WCS7 The estimated raw dermal exposure for this contributing scenario, based on the RMM describe above and ECETOC input is the following: mg/kg/day Worker Contributing Scenario 8: Offloading, far field Conditions of use CONDITIONS OF USE MODELLING PARAMETERS PRODUCTS CHARACTERISTICS Physical form Liquids Liquids Vapour pressure At room temperature 8600 Pa (Source: INRS) Liquid mole fraction Pure liquid 1 Activity coefficient Default value 1 OPERATIONAL CONDITIONS Temperature - Room temperature (15-25 C) Duration - 12 min Use-1 EURENCO 53