CHEMICAL SAFETY REPORT

Transcription

1 Industrial use of trichloroethylene (TCE) as a solvent as a degreasing agent in closed systems Substance Name: Trichloroethylene EC Number: CAS Number: Registrant's Identity: Chimcomplex SA Borzesti 1

2 Part A 1. SUMMARY OF RISK MANAGEMENT MEASURES The industrial use of trichloroethylene (TCE) as a degreasing fluid in closed systems has been assessed in part B of this chemical safety report. The lead dossier for trichloroethylene has been submitted by Dow Deutschland Anlagengesellschaft mbh, Registration Number Trichloroethylene is produced by Chimcomplex SA Borzesti and supplied to downstream users (DUs) via distributors. The DUs use TCE in surface degreasing applications in closed systems according to EN Revised health hazard assessment for workers: Deviating from the current lead dossier for TCE the applicant has established the most critical endpoint for health of workers being carcinogenicity (kidney cancer) without a safe threshold dose. To account for the cancer effects the applicant has adopted the dose-response relationship for TCE endorsed by the Committee for Risk Assessment (RAC 28/2014/07 dated 6 March 2014). Excess risk unit values for inhalation and dermal exposure have been used for the risk assessment following the RAC suggestions. The excess risk of cancer has been determined in part B of this document. A Socio-Economic Assessment as attached demonstrates sufficient benefit and confirms that the risk management measures described in part B chapter 9 are adequate and that they minimise exposure to an acceptable level. 2

3 2. DECLARATION THAT RISK MANAGEMENT MEASURES ARE IMPLEMENTED The risk management measures mentioned above are implemented by the downstream users (DUs). Trichloroethylene is delivered to downstream users for use as a degreasing agent in machines of type III or better (higher specification) as described in the ECSA paper Recommendations for Cleaning Machines for the use of Chlorinated Solvents in dry cleaning and surface cleaning, May A voluntary commitment is established by the ECSA Charter for the safe use of Trichloroethylene, which has been signed by the applicant. Although this commitment is voluntary, when this specific use of TCE is authorised, compliance with the commitment would become enforceable. Chimcomplex is applying for authorisation and is requesting a review period that would give time for all DUs to fully align themselves with the commitment. 3. DECLARATION THAT RISK MANAGEMENT MEASURES ARE COMMUNICATED The risk management measures mentioned above are communicated to the downstream user via the safety data sheet. 3

4 Part B 9. EXPOSURE ASSESSMENT 9.9a. Exposure scenario 9a: Industrial use of trichloroethylene (TCE) as a solvent as a degreasing agent in closed systems 9.9a.1. Exposure scenario This exposure scenario is based on a template for authorisation issued by the Eurochlor consortium (exposure scenario ES9.9 industrial use as process chemical - closed system). Section 1 Title Sector of Use Process Category Exposure Scenario Title Industrial use of trichloroethylene (TCE) as a solvent as a degreasing agent in closed systems SU3 PROC1, PROC2, PROC3, PROC8a, PROC8b, PROC15 Product Category Article Category Environmental release Category Specific environmental release category Processes, tasks, activities covered Section 2 Section 2.1 Product characteristics Physical form of product Volatility Concentration of substance in product Operational conditions Amounts used Frequency and duration of use n/a n/a ERC7 n/a Use as process chemical and for degreasing and cleaning of parts in closed systems. For the use of Trichloroethylene (TRI) in metal degreasing equipment, as described in the European Standard EN Type 1 and ECSA 2013 paper: Recommendations for Cleaning Machines for the use of Chlorinated Solvents in dry cleaning and surface cleaning Type III and higher, must be employed. Includes recycling / recovery, material transfers, storage, sampling, associated laboratory activities, maintenance and loading (including marine vessel/barge, road/rail car and bulk container). Operational conditions and risk management measures Control of worker exposure Liquid Medium volatility Up to 100% Not relevant for this scenario Covers daily exposures up to 8 hours (unless stated) 4

5 Human factors not influenced by risk management Other Operational Conditions affecting worker exposure None identified for this scenario. Apply LEV (local exhaust ventilation) as stated. Suitable LEV must take into account the high density of the TCE vapour. Assumes a good basic standard of occupational hygiene is implemented Assumes activities are at ambient temperature (unless stated differently) Identified uses and worker exposure Users operates an Occupational Health and Safety Management System: The degreasing process is described in operating instructions. Instructions concerning safety and exposure to TCE are trained at least annually. Employees receive regular practical instructions on how to use the personal protective equipment. Operators monitor the performance of the degreasing equipment during loading/unloading operations. Operating conditions which differ in individual tasks are described in the table below Contrib uting ES Identified uses* Process Category Operating Conditions affecting worker exposure 1 2 Continuous process; No sampling; Continuous process; With sample collection; 1 Continuous process; no sampling; e.g. Storage of TCE in closed drums and in a tank on site. 2 Degreasing and cleaning in continuous mode; In-line cleaning systems according to: EN Type I and ECSA (2013) Type III, IV and V W4 Use in contained batch processes; With sample collection. Degreasing and cleaning in a closed system according to EN Type I and ECSA (2013) Type III, IV and V Picture 1: Continuous degreasing of components in crates (example from company Hoeck Metall-Reinigungsanlagen GmbH, Neuenburg) 3 Use in contained batch processes with sample collection. The design of the samplers allows sampling without exposure to TCE vapours. 3 Degreasing and cleaning of parts in batch mode either manually or automatically loaded. Equipment used has manufacturer s CE certificate confirming compliance with standard EN Type I W5 Picture 2: Batch degreasing machine (example of company Pero AG, Königsbrunn) 5

6 W6 Bulk transfers; 8b Bulk transfers, e.g. from tank truck to stationary tank. Operation is done outdoors. Unloading is carried out in a closed system with TCE vapours back venting to the tanker. W7 W8 Drum/batch transfers; With local exhaust ventilation Drum/batch transfers 8b 8b Material transfers from drum/vessel to tank or mobile container. Operation is done outdoors or indoors with local exhaust ventilation (LEV) Material transfers from drum/vessel to tank or mobile container. Operation is done indoors without exhaust ventilation W9 Equipment cleaning and maintenance. 8a Cleaning and decontamination operations are done by production operators. Parts to be repaired by external (non-production) employees do not contain TCE residues. TCE waste is collected both as liquid or solid waste. 10 Equipment cleaning and maintenance; Elevated temperature 8a Cleaning and decontamination operations are done by production operators. Parts to be repaired by external (non-production) employees do not contain TCE residues. TCE waste is collected both as liquid or solid waste 11 Storage; (closed system) 1 Storage of TCE in closed drums and in a tank on site 12 Laboratory activities 15 All activities take place under a laboratory workbench with controlled air extraction. Trained personnel only. Risk Management Measures of Contributing Scenarios Identifier* Scenario description Process Risk Management Measures Categories W1 Continuous process; No sampling; 1 No other specific measures identified 2 Provide a good standard of general ventilation (not less W2 Continuous process; than 3-5 air changes per hour); or With sample collection; Ensure operation is undertaken outdoors W4 W5 W6 W7 W8 Use in contained batch processes; With sample collection. Degreasing and cleaning in a closed system according to: a) EN Type I or b) ECSA 2012 Type III, IV and V Bulk transfers; Drum/batch transfers; With local exhaust ventilation Drum/batch transfers 3 Provide extract ventilation to points where emissions occur 3 Employ and maintain equipment as laid out in EN Provide extra ventilation to points where emissions occur. 8b 8b 8b Ensure operation is undertaken outdoors. Avoid carrying out activities involving exposure for more than 1 hour. Wear suitable gloves tested to EN374. Ensure material transfers are under containment or extract ventilation. Wear suitable gloves tested to EN374. Provide a good standard of general ventilation (not less than 3-5 air changes per hour); or Ensure operation is undertaken outdoors. Avoid carrying out activities involving exposure for 6

7 W9 W10 W11 Equipment cleaning and maintenance. Equipment cleaning and maintenance; Elevated temperature Storage; 8a 8a more than 1 hour. Wear suitable gloves tested to EN374. Drain down system prior to equipment break-in or maintenance. Avoid carrying out activities involving exposure for more than 4 hours. Wear suitable gloves tested to EN374. Provide extract ventilation to points where emissions occur. Wear a respirator conforming to EN140 with Type A filter or better; Wear suitable gloves tested to EN No other specific measures identified. W12 Laboratory activities. 15 Provide a good standard of general ventilation (not less than 3-5 air changes per hour) *Identifier: each contributing scenario of the ES has been assigned a unique identifier which facilitates tracking all the information (exposure estimation, risk characterisation in chapter 9 and 10 and appendices) related to this contributing scenario of the ES Section 2.2 Identifier E1 Control of environmental exposure Contributing scenario Environmental Release Category Specific ERC Industrial use as process chemical ERC7 Assessment scenario copied from lead registrant CSR Section Operational Conditions Amounts used Amounts used in the EU (tonnes/year) 213 Fraction of EU tonnage used in region 1 Fraction of main source to local environment 0.1 Fraction of substance in end-use products Daily site tonnage Msperc (kg/day) 2100 Frequency and duration of use Type of release Emission days (days/year) 300 Site specific monitoring data results for surface water effluent Location of sample Environmental factors not influenced by risk management continuous Not applicable Local freshwater dilution factor Local marine water dilution factor Other given operational conditions affecting environmental exposure Risk Management Measures 10 (default) 100 (default) 7

8 Technical conditions and measures at process level (source) to prevent release Technical onsite conditions and measures to reduce or limit discharges, air emissions and releases to soil Treat air emissions to provide a typical removal efficiency of (%) ERMM1: Typical onsite wastewater treatment technology provides degradation efficiency of (%) Organizational measures to prevent/limit release from site Conditions and measures related to municipal sewage treatment plant ERMM2: Typical municipal wastewater treatment technology provides degradation efficiency of (%) Treat wastewater (prior to discharge to receiving water) to provide the required removal efficiency of (%) ETotal,RMM = 1 ((1 ERMM, 1) x (1 ERMM,2)) Conditions and measures related to external treatment of waste for disposal Closed machines. Only indirect cooling of parts or condensates should be employed. Not applicable Air stripping to reduce concentration to 5 ppm for all exhaust vents No onsite wastewater treatment. Periodic emissions to wastewater occur during rinsing and cleaning of the degreasing machine. Site should have a spill plan to ensure that adequate safeguards are in place to minimize the impact of episodic releases. STP: 3 Estimated substance removal from wastewater via domestic sewage treatment (%): 88.8 (default from Simple treat model) STP4: Total efficiency of removal from wastewater after onsite and offsite (domestic treatment plant) RMMs (%): 88.8 Dispose of waste solvent and used containers according to local regulations. Transfer and filling should be done over a secured surface Conditions and measures related to external recovery of waste Other environmental control measures additional to above 9.9a.2. Exposure Estimation 9.9a.2.1. Workers exposure The worker exposure estimates for the activities associated with this use of TCE have been assessed using ECETOC TRA v3, unless stated differently. Assessment parameter default values: Fugacity: medium Type of Use; industrial Concentration: > 25 % Local Exhaust Ventilation: none Duration of Exposure: > 4 hours/day Respiratory Protection Equipment: none The ECETOC TRA v3 estimates shown are representative for activities lasting up to 8 hours and for acute/short term exposure (15 minutes maximum): 8

9 Identifier * ES9-W1 ES9-W2 ES9-W4 ES9-W5 ES9-W6 ES9-W7 ES9-W8 ES9-W9 Contributing scenarios General exposures Continuous process No sampling Continuous process; With sample collection; Use in contained batch processes; With sample collection. Degreasing and cleaning in a closed system according to EN Type I and ECSA (2013) Type III, IV and V Bulk transfers; Drum/batch transfers; With local exhaust ventilation Drum/batch transfers Equipment cleaning and maintenance PROC Risk Management Measures 1 No other specific measures identified 2 Provide a good standard of general ventilation (not less than 3-5 air changes per hour); or ensure operation is undertaken outdoors. 3 Indoors with LEV - extract ventilation to points where emissions occur. 3 Employ EN Type I certified equipment. Indoors with LEV at points where emissions occur 8b Ensure operation is undertaken outdoors. Avoid carrying out activities involving exposure for more than 1 hour. 8b Ensure material transfers are under containment or LEV. Wear suitable gloves tested to EN374. 8b Provide a good standard of general ventilation (not less than 3-5 air changes per hour); or ensure operation is undertaken outdoors. Avoid carrying out activities involving exposure for more than 1 hour. Wear suitable gloves tested to EN374. 8a Drain down system prior to equipment break-in or maintenance. Indoors with enhanced general ventilation. Avoid Inhalation exposure (mg/m 3 ) Dermal exposure (mg/kg/day) Dermal exposure (mg/cm 2 ) Acute local Long Acute Long Acute term term systemic n.a n.a n.a n.a n.a n.a n.a n.a

10 ES9-W10 ES9-W11 ES9-W12 Equipment cleaning and maintenance; Elevated temperature Storage; carrying out activities involving exposure for more than 1 hour. Wear suitable gloves tested to EN374. 8a Indoor with LEV and good general ventilation. Wear a respirator conforming to EN140 with Type A filter or better (protection efficiency 90%). Wear suitable gloves tested to EN No other specific measures identified. Laboratory activities. 15 Indoor with LEV (laboratory fume hood) 9.60** 38.3** 2.74 n.a n.a n.a *Identifier: each contributing scenario of the ES has been assigned a unique identifier which facilitates tracking all the information (exposure estimation, risk characterisation in chapter 9 and 10 and appendices) related to this contributing scenario of the ES. ** elevated temperatures below boiling point: using a vapor pressure of TCE of 40 kpa at 60 C (David R. Lide, ed., CRC Handbook of Chemistry and Physics, Internet Version 2005) a conservative factor of 5 was employed to take into account higher volatility of TCE in this scenario. 9.9a.2.2. Consumer exposure Not applicable. 9.9a.2.3. Indirect exposure of humans via the environment (oral) (Reference: taken from lead registrant CSR Section 9.9.2) Several studies measured the whole body bioaccumulation factors for fish, the values ranged from 17 to 90. Studies with algae were also available. The log Kow (2.35), the bioconcentration factor (BCF=17) and the half-life in tissue which is less than 1 day indicate that trichloroethylene does not appear to accumulate to a significant extent. Nevertheless, TCE is not biodegradable and is classified as Carcinogen Category 1B (H350) and Mutagenic Category 2 (H341). Emissions identified for TCE in state-of-the-art degreasing equipment are now much lower than identified in the European Risk assessment Report (2004), which concluded that there is no risk for secondary poisoning. For this reason, indirect exposure of humans via the environment has not been further addressed in this report. 9.9a.2.4. Environmental exposure (Reference: taken from lead registrant CSR Section 9.9.2) The process operates in a closed system. All emissions to air are fed over activated carbon. A maximal air flow of 1000m 3 /h is treated to achieve a residual concentration of 20 mg/m 3, hence 160 g/d emitted to air. Residual trichloroethylene in water is either treated by air stripping or fed back over activated carbon filters. The residual concentration in water are 1-5 ppm after air stripping and <0.1 ppm after activated carbon treatment. The assessment will consider a worst case assumption of 200L of water treated per day with a residual concentration of 5ppm, hence 1g/d emitted to wastewater. 10

11 Periodic emissions to wastewater occur during rinsing and cleaning of the degreasing machines. These waste waters from the plant contain below 1000 ppm TCE for a maximum volume of waste water of 1 m3/d, which are discharged to an onsite waste water treatment plant. The maximal load emitted is 1 kg/d. Identifier Narrative Release fraction to air from process Release fraction to wastewater from process Release fraction to soil from process (regional only) Local release to air (kg/d) ES9-E1 Industrial use as process chemical Not applicable Not applicable Not applicable 1.60E-01 Local release to sewage (kg/d) 1. Local release to soil (kg/d) 0 Total efficiency of removal from wastewater after 88.8 onsite and offsite (domestic treatment plant) RMMs (%) Total efficiency of removal from air emissions (%) The maximum allowable site tonnage (M Safe ) based on removal from domestic sewage treatment (kg/d) Not applicable Not applicable 11

12 10. RISK CHARACTERISATION The risk characterisation of trichloroethylene has been conducted for workers (no consumer use) based on the hazards as determined in the main CSR and use data as described in the Analysis of Alternatives (AoA) and Socio- Economic Analysis (SEA). 10.9a. Exposure scenario 9a: Industrial use of trichloroethylene (TCE) as a solvent as a degreasing agent in closed systems 10.9a.1. Human Health 10.9a.1.1. Workers Trichloroethylene has been classified as Carcinogen Category 1B (H350) and Mutagenic Category 2 (H341). The applicant has established the most critical endpoint for health of workers being carcinogenicity (kidney cancer) without a safe threshold dose. To account for the cancer effects the applicant has adopted the dose-response relationship for TCE endorsed by the Committee for Risk Assessment (RAC 28/2014/07 dated 6 March 2014) for the subsequent risk assessment. A standard employee was defined in RAC 28/2014/07 as working 8hr/day, 5 days/week, 52 weeks/year and for 40 years. No off-work hours or vacation time was considered. The excess risk for occupational exposure to TCE has been taken from RAC 28/2014/07 as: 1. Inhalation risk At 33 mg/m 3 and above: Below 33 mg/m 3 : Excess risk = 1.3 x 10-4 (mg/m 3 ) -1 x concentration (mg/m 3 ) Excess risk = 1.2 x 10-5 (mg/m3) -1 x concentration (mg/m 3 ) No exposures above 33mg/m 3 have been determined in chapter 9 therefore the excess risk can be linearly calculated using the second formula from above. 2 Dermal exposure risk At 4.72 mg/kg bw/d and above: Excess risk = 9.09 x 10-4 (mg/kg bw/d) -1 x dose (mg/kg bw/d) Below 4.72 mg/kg bw/d: Excess risk = 8.4 x 10-5 (mg/kg bw/d) -1 x dose (mg/kg bw/d) No exposures above 4.72 mg/kg bw/day have been determined in chapter 9. Therefore the excess risk can be linearly calculated using the second formula from above. 12

13 Excess risks for contributing scenarios are calculated as follows: ES number W1 W2 W4 W5 W6 W7 W8 W9 W10 W11 W12 Identified uses Continuous process; No sampling; Continuous process; With sample collection; Use in contained batch processes; With sample collection. Degreasing and cleaning in a closed system according to EN Type I and ECSA (2013) Type III, IV and V Bulk transfers; Drum/batch transfers; With local exhaust ventilation Drum/batch transfers Equipment cleaning and maintenance. Equipment cleaning and maintenance; Elevated temperature Storage; Laboratory activities. Inhalatory Inhalation Dermal Dermal Total Excess exposure excess risk exposure Excess Risk Risk (mg/m3) 10-6 mg/kg/day Average Excess Risk from carcinogenicity The standard industrial downstream user (average worker) occupied with cleaning and degreasing operations is involved in all handling operations of TCE throughout the material flow of his facility. These operations can be described with two general activities: 1. Degreasing operation and 2. Maintenance. The lifetime Excess Risk for the average worker receives contributions from both activities as follows: 1. Degreasing equipment can be operated without maintenance for a couple of days. The average worker will therefore run the process for four days of the week with little repairs at elevated TCE temperature and be involved in laboratory activities, involving exposure scenarios ES 9a-W5, W10 and W12. The Excess Risk for this activity can be summarized by adding the corresponding risks from the above table. 13

14 ES number W5 W10 Identified uses Degreasing and cleaning in a closed system according to EN Type I and ECSA (2013) Type III, IV and V Equipment cleaning and maintenance; Elevated temperature Total Excess Risk W12 Laboratory activities. 72 Total excess Risk for the degreasing operation One day per week operators are assumed to conduct cleaning activities as well as replenishing the storage and removing waste TCE. As a worst case it is assumed that the most critical exposures W8 and W9 are applicable during this time: ES number W8 W9 Identified uses Drum/batch transfers Equipment cleaning and maintenance. Total Excess Risk 10-6 Total excess Risk for the degreasing operation Combining activities 1 (4 days with Excess Risk of 542 * 10-6 ) and activity 2 (1 day with Excess Risk of 520 * 10-6 ) will yield an overall long time worker risk level of : Excess Risk = (4 days * day * 520)* 10-6 / 5 = 5.4 * 10-4 cancer cases per worker. 10.9a.1.2. Consumers Not applicable. 10.9a.1.3. Indirect exposure of humans via the environment See chapter 9.9a Environment (Reference: taken from lead registrant CSR Section ) Compartments: Risk Characterisation Ratios ES9-E1 STP Freshwater Marine water Freshwater sediment Marine water sediment Soil

15 REFERENCES Chemical Safety Report Trichloroethylene (Lead Registrant DOW Deutschland Anlagengesellschaft GmbH) EU RAR (2004). European Union Risk Assessment Report - TRICHLOROETHYLENE European Standard EN :2005 A1:2008: Machines for surface cleaning and pretreatment of industrial items using liquids and vapours Part 4: Safety of machines using halogenated solvents Eurochlor / ECSA (European Chlorinated Solvent Association): 7. Recommendations for Cleaning Machines for the use of Chlorinated Solvents in dry cleaning and surface cleaning, July