ANNEX II for SDS (VERSION: 2.2 CREATED: 21/03/2012) EXPOSURE SCENARIOS. Tert-butyl methyl ether (Methyl tertiary butyl ether) EC #:

Transcription

1 ANNEX II for SDS (VERSION: 2.2 CREATED: 21/03/2012) EXPOSURE SCENARIOS Tert-butyl methyl ether (Methyl tertiary butyl ether) EC #: CAS #:

2 Table of Contents EXPOSURE ASSESSMENT Exposure Scenario 1: Manufacturing Exposure scenario Exposure estimation Manufacturing Worker exposure Consumer exposure Indirect exposure of humans via the environment Environmental exposure Environmental releases Exposure in the aquatic compartment Exposure in soils and sediments Atmospheric compartment Exposure relevant for the food chain (Secondary poisoning) Exposure Scenario 2: Formulation - industrial Exposure scenario Exposure estimation Formulation - industrial Worker exposure Consumer exposure Indirect exposure of humans via the environment Environmental exposure Environmental releases Exposure in the aquatic pelagic compartment Exposure in soils and sediments Atmospheric compartment Exposure relevant for the food chain (Secondary poisoning) Exposure Scenario 3: Use as an intermediate - industrial Exposure scenario Exposure estimation Use as intermediate - industrial Worker exposure Consumer exposure Indirect exposure of humans via the environment Environmental exposure Environmental releases Exposure in the aquatic pelagic compartment Exposure in soils and sediments Atmospheric compartment Exposure relevant for the food chain (Secondary poisoning) Exposure Scenario 4: Use as a process solvent and extraction agent - industrial Exposure scenario Exposure estimation Use as process solvent or extraction agent - industrial Worker exposure Consumer exposure Indirect exposure of humans via the environment Environmental exposure Environmental releases Exposure in the aquatic pelagic compartment Exposure in soils and sediments Atmospheric compartment Exposure relevant for the food chain (Secondary poisoning) Exposure Scenario 5: Transport and distribution industrial Exposure scenario Exposure estimation Transport and distribution industrial Workers exposure ii

3 Consumer exposure Indirect exposure of humans via the environment Environmental exposure Environmental releases Exposure in the aquatic pelagic compartment Exposure in soils and sediments Atmospheric compartment Exposure relevant for the food chain (Secondary poisoning) Exposure Scenario 6: Fuel use industrial Exposure scenario Exposure estimation Fuel Use industrial Workers exposure Consumer exposure Indirect exposure of humans via the environment Environmental exposure Environmental releases Exposure in the aquatic pelagic compartment Exposure in soils and sediments Atmospheric compartment Exposure relevant for the food chain (Secondary poisoning) Exposure Scenario 7: Fuel use professional Exposure scenario Exposure estimation Fuel Use - professional Workers exposure Consumer exposure Indirect exposure of humans via the environment Environmental exposure Exposure Scenario 8: Fuel use consumer Exposure scenario Exposure estimation Fuel Use consumer Workers exposure Consumer exposure Indirect exposure of humans via the environment Environmental exposure Environmental releases Exposure in the aquatic pelagic compartment Exposure in soils and sediments Atmospheric compartment Exposure relevant for the food chain (Secondary poisoning) RISK CHARACTERISATION Manufacture Human health Workers Consumers Indirect exposure of humans via the environment Environment Aquatic compartment (including sediment) Terrestrial compartment Atmospheric compartment Microbiological activity in sewage treatment plants Secondary poisoning Formulation Human health Workers Consumers Indirect exposure of humans via the environment Environment Aquatic compartment (including sediment) Terrestrial compartment Atmospheric compartment iii

4 Microbiological activity in sewage treatment plants Secondary poisoning Use as Intermediate Human health Workers Consumers Indirect exposure of humans via the environment Environment Aquatic compartment (including sediment) Terrestrial compartment Atmospheric compartment Microbiological activity in sewage treatment plants Secondary poisoning Use as a process solvent and extraction agent Human health Workers Consumers Indirect exposure of humans via the environment Environment Aquatic compartment (including sediment) Terrestrial compartment Atmospheric compartment Microbiological activity in sewage treatment plants Secondary poisoning Transport and distribution Human health Workers Consumers Indirect exposure of humans via the environment Environment Aquatic compartment (including sediment) Terrestrial compartment Atmospheric compartment Microbiological activity in sewage treatment plants Secondary poisoning Fuel use - industrial Human health Workers Consumers Indirect exposure of humans via the environment Environment Aquatic compartment (including sediment) Terrestrial compartment Atmospheric compartment Microbiological activity in sewage treatment plants Secondary poisoning Fuel use - professionals Human health Workers Consumers Indirect exposure of humans via the environment Environment Fuel use - consumers Human health Workers Consumers Indirect exposure of humans via the environment Environment Aquatic compartment (including sediment) Terrestrial compartment

5 Atmospheric compartment Microbiological activity in sewage treatment plants Secondary poisoning Overall exposure (combined for all relevant emission/release sources) Human health (combined for all exposure routes) ANNEX A: HUMAN EXPOSURE Assessment - Summary ANNEX B: 2 nd tier HUMAN EXPOSURE Assessment ANNEX C: Environmental Exposure Assessment Summary v

6 EXPOSURE ASSESSMENT The eight exposure scenarios are: 1. Manufacturing of MTBE 2. Formulation of MTBE 3. Use of MTBE as an intermediate 4. Use of MTBE as a process solvent and extraction agent 5. Storage, transport and delivery of MTBE and petrol 6. Use of fuels by industrial workers: fuelling of cars, boats, motorbikes 7. Use of fuels by professional workers: refuelling of cars, boats, motorbikes by service station attendants. Maintenance of fuel pumps at service stations is also included. 8. Use of fuels by consumers: use of vehicles and gasoline operated engines: Filling of engines (cars, bikes, boats, motor saws, etc) with petrol by professional users and by consumers, repair of engines. Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 6 of 148

7 Table 1: Overview on exposure scenarios and coverage of substance life cycle Life Cycle Stage(s) covered by the IU Number (IU) Short description of Identified Use Product Category (PC) Manufacture Formulation Industrial End Use Professional Consumer Service Life (for article) Sector of use (SU) Process Category (Proc) Article Category (AC) Environmental Release Category (ERC) ES1 Manufacturing 1 Industrial manufacturing (closed process) X SU3 PROC1 1 Industrial manufacturing (closed, continuous process) X SU3 PROC2 1 Industrial manufacturing (closed batch process) X SU3 PROC3 1 Industrial manufacturing (batch and other processes, SU3 X synthesis) PROC4 1 Transfer of MTBE (non-dedicated facilities) X SU3 PROC8a 1 Transfer of MTBE (dedicated facilities) X SU3 PROC8b 1 Sampling and associated laboratory activities X SU3 PROC15 ES2 Formulation 2 Formulation (closed process) X SU3 PROC1 2 Gasoline blending with MTBE (closed, continuous) X SU3 PROC2 2 Gasoline blending with MTBE (closed batch) X SU3 PROC3 2 Gasoline blending with MTBE (batch and other processes, SU3 X synthesis) PROC4 2 Mixing or blending of MTBE (batch process) X SU3 PROC5 2 Distribution of gasoline containing MTBE (non-dedicated SU3 X facilities) PROC8a 2 Distribution of gasoline containing MTBE (dedicated SU3 X facilities) PROC8b 2 Distribution of gasoline containing MTBE (small scale SU3 X dedicated filling line) PROC9 ERC1 ERC2

8 Life Cycle Stage(s) covered by the IU Number (IU) Short description of Identified Use Product Category (PC) Manufacture Formulation Industrial End Use Professional Consumer Service Life (for article) Sector of use (SU) Process Category (Proc) Article Category (AC) Environmental Release Category (ERC) 2 Sampling and associated laboratory activities X SU3 PROC15 ES3 Use as intermediate 3 Use as intermediate (closed process) X SU3 PROC1 3 Use of neat MTBE as intermediate (closed, continuous process) X SU3 PROC2 3 Use of neat MTBE as intermediate (closed batch process) X SU3 PROC3 3 Use of neat MTBE as intermediate (batch and other SU3 X processes, synthesis) PROC4 3 Transfer of MTBE (non-dedicated facilities) X SU3 PROC8a 3 Transfer of MTBE (dedicated facilities) X SU3 PROC8b 3 Sampling and associated laboratory activities X SU3 PROC15 ES4 Use as process solvent and extraction agent 4 Use of neat MTBE as process solvent and extraction SU3 X agent (closed process) PROC1 4 Use of neat MTBE as process solvent, extraction agent and in SU3 X enclosed cleaning systems (closed continuous) PROC2 4 Use as process solvent and extraction agent (closed batch SU3 X process) PROC3 4 Use of neat MTBE as process solvent and extraction SU3 X agent (batch and other processes, synthesis) PROC4 4 Transfer of MTBE (non-dedicated facilities) X SU3 PROC8a 4 Transfer of MTBE and draining equipment (dedicated SU3 X facilities) PROC8b 4 Quality control X SU3 PROC15 ES5 Industrial distribution of MTBE and gasoline containing ERC6a ERC4 Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 8 of 148

9 Life Cycle Stage(s) covered by the IU Number (IU) Short description of Identified Use Product Category (PC) Manufacture Formulation Industrial End Use Professional Consumer Service Life (for article) Sector of use (SU) Process Category (Proc) Article Category (AC) Environmental Release Category (ERC) MTBE 5 Transport of MTBE and distribution of gasoline containing SU3 X MTBE (closed process) PROC1 5 Transport of MTBE and distribution of gasoline containing SU3 X MTBE (closed continuous process) PROC2 5 Transport of MTBE and distribution of gasoline containing SU3 X MTBE (closed batch process) PROC3 5 Transport of MTBE and distribution of gasoline containing SU3 X MTBE (batch and other processes, synthesis) PROC4 Transport of MTBE and distribution of gasoline containing SU3 5 MTBE (non-dedicated facilities); includes exposure as result of X PROC8a cleaning of equipment Transport and distribution of neat MTBE and gasoline SU3 5 containing MTBE (dedicated facilities); includes exposure as X PROC8b result of cleaning of equipment 5 Transport of MTBE and distribution of gasoline containing SU3 X MTBE (small scale dedicated filling line) PROC9 5 Sampling and associated laboratory activities X SU3 PROC15 Fuel use - Industrial (GES: use as fuel additive and includes ES6 activities associated with its transfer, use, equipment maintenance and handling of waste) 6 Use of MTBE as fuel additive (closed process) X SU3 PROC1 6 Use of MTBE as fuel additive (closed, continuous process) X SU3 PROC2 6 Use of MTBE as fuel additive (batch process) X SU3 PROC3 6 Transfer of MTBE (non-dedicated); includes exposure as result X SU3 PROC8a ERC1, ERC2 ERC8b

10 Life Cycle Stage(s) covered by the IU Number (IU) Short description of Identified Use Product Category (PC) Manufacture Formulation Industrial End Use Professional Consumer Service Life (for article) Sector of use (SU) Process Category (Proc) Article Category (AC) Environmental Release Category (ERC) of cleaning of equipment 6 Transfer of MTBE (dedicated); includes exposure as result of cleaning of equipment X SU3 PROC8b 6 Using MTBE as fuel source, limited exposure to unburned product to be expected X SU3 PROC16 ES7 Fuel use Professional (Transport of MTBE and distribution of gasoline containing MTBE) 7 Use of MTBE as fuel additive (closed process) X SU22 PROC1 7 Use of MTBE as fuel additive (closed, continuous process) X SU22 PROC2 7 Use of MTBE as fuel additive (batch process) X SU22 PROC3 Transfer of MTBE (non-dedicated); includes exposure as result 7 of cleaning of equipment Maintenance and repair of fuel X SU22 PROC8a pumps; repair of engines ERC8b, ERC8e 7 Refuelling at service stations by attendants; includes exposure as result of cleaning of equipment X SU22 PROC8b 7 Filling of engines (motor saws, jet ski s etc) from cans X SU22 PROC9 7 Use of engines, including refuelling, by professional users of SU22 X vehicles PROC16 ES8 Fuel use - consumer 8 Use of engines, including refuelling of vehicles by consumers PC13 X SU21 ERC8e Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 10 of 148

11 The following information has been used for the exposure assessments: Substance MTBE CAS no. Vapour Pressure 330 hpa at 25 ºC TRA volatility range High Inherently biodegradable, not fulfilling Biodegradability criteria. But adapted sludge is assumed in industrial facilities. Henry's Law Constant 43.8 Pa/m3/mol at 25 ºC Molecular Weight g/mol Melting Point ºC Boiling Point 55.3 ºC Water solubility 41,850 mg/l at 25 ºC Log K OW 1.06 at 20 ºC Differences between degradation in STP between non-adapted and adapted sludge. Compartments n-adapted sludge (EU RAR) Adapted sludge Directed to air (%) 36.2 <2.29 Directed to water (%) 63.4 <2.55 Directed to sludge (%) >0.082 Degraded (%) 0 >95.1 A summary of the environmental and human expsosure assessment (input parameter and results) is given in Annex A, B (human exposure) and C (environmental exposure). Exposure scenarios for SDS (VERSION: 2.2 CREATED:11/04/2012)

12 1.1. Exposure Scenario 1: Manufacturing MTBE is manufactured in industrial manufacturing of bulk, large scale chemicals as fuel additive in fuels by use in closed, continuous process with occasional controlled exposure. MTBE is typically manufactured in petroleum refineries but also in plants manufacturing industrial organic chemicals. MTBE is prepared principally by reacting isobutene with methanol over an acidic ion-exchange resin catalyst at o C and psi. The manufacturing of MTBE is considered to be in an automated and principally closed outdoor system with a connection to central waste gas system Exposure scenario Section 1 Title Exposure Scenario Title Manufacture of MTBE; CAS RN Use Descriptor Sector of Use: Industrial (SU3) Process Categories: PROC1, PROC2, PROC3, PROC4, PROC8a, PROC8b, PROC15 Environmental Release Categories: ERC1 Specific Environmental Release Categories: ESVOC1 SpERC Processes, tasks, activities covered Manufacture of MTBE. Includes recycling/ recovery, material transfers, storage, sampling, associated laboratory activities, maintenance and loading (including marine vessel/barge, road/rail car and bulk container). Section 2 Operational conditions and risk management measures Field for additional statements to explain scenario if required. Section 2.1 Control of worker exposure Product characteristics Physical form of product Liquid, vapour pressure > 10 kpa [OC5]. Concentration of substance in product Covers percentage substance in the product up to 100 % (unless stated differently) [G13]. Amounts used t applicable Frequency and duration of use Covers daily exposures up to 8 hours (unless stated differently) [G2] Human factors not influenced by risk t applicable management Other Operational Conditions affecting worker exposure Contributing Scenarios General measures (skin irritants) [G19]. Assumes use at not > 20 C above ambient [G15]; Assumes a good basic standard of occupational hygiene is implemented [G1]. Risk Management Measures te: list RMM standard phrases according to the control hierarchy indicated in the ECHA template: 1. Technical measures to prevent release, 2. Technical measures to prevent dispersion, 3. Organisational measures, 4. Personal protection. Avoid all skin contact with product, clean up Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 12 of 148

13 [CS15]. [CS15]. With sample collection [CS56]. [CS15]. Use in contained batch processes [CS37]; With sample collection [CS56]. General exposures (open systems) [CS16]. Batch process [CS55]. With sample collection [CS56]; Filling / preparation of equipment from drums or containers. [CS45]. Process sampling [CS2]; Dedicated facility [CS81] Laboratory activities [CS36]. Cleaning [CS47] [wiping, brushing, flushing] bulk open loading and unloading [CS503]n-dedicated facility [CS82] bulk closed loading and unloading [CS501]Dedicated facility [CS81] Equipment cleaning and maintenance [CS39]. n-dedicated facility [CS82] Storage [CS67]; [CS15]. Storage [CS67]; [CS15]. With sample collection [CS56]. Section 2.2 Product characteristics Operational conditions contamination/spills as soon as they occur. Wear gloves (tested to EN374) if hand contamination likely, wash off any skin contamination immediately. Provide basic employee training to prevent / minimise exposures and to report any skin problems that may develop [E3]. specific measures identified [EI18]. Ensure operation is undertaken outdoors [E69]. Provide extract ventilation to points where emissions occur [E54]. Ensure material transfers are under containment or extract ventilation [E66]. Provide extract ventilation to points where emissions occur [E54]. Handle in a fume cupboard or under extract ventilation [E83]. Avoid carrying out activities involving exposure for more than 4 hours [OC28], or: Wear a respirator conforming to EN140 with Type A filter or better. [PPE22] Avoid carrying out activities involving exposure for more than 4 hours [OC28], or: Wear a respirator conforming to EN140 with Type A filter or better. [PPE22] Drain down and flush system prior to equipment breakin or maintenance [E55].Avoid carrying out activities involving exposure for more than 4 hours [OC28], or: Wear a respirator conforming to EN140 with Type A filter or better. [PPE22] specific measures identified [EI18]. Avoid carrying out activities involving exposure for more than 4 hours [OC28], or: Wear a respirator conforming to EN140 with Type A filter or better. [PPE22] Control of environmental exposure Substance is a unique structure [PrC1]. Predominantly hydrophobic [PrC4a]. Readily biodegradable [PrC5a]. Outdoor use [OOC1].

14 Amounts used Fraction of EU tonnage used in region 0.25 [A1]: Regional use tonnage (tonnes/year) [A2]: 669,175 Fraction of regional tonnage used locally [A3]: 0.4 Average local daily tonnage (kg/d) [A5]: 892,233 Annual site tonnage (tonnes/year) [A6] 267,670 Frequency and duration of use Type of release Continuous release [FD2]. Emission days (days/year) [FD4]: 300 Other Operational Conditions of use affecting environmental exposure Use in closed systems. Either wet or dry processes. 5.00E-03 Release fraction to air from process: Release fraction to wastewater from 0.01 process: Release fraction to soil from process 1.00E-03 (regional only): RMMs Technical conditions and measures at Common practices vary across sites thus conservative process level (source) to prevent process release estimates used [TCS 1]. release Technical onsite conditions and measures to reduce or limit discharges, air emissions and releases to soil Air: Wastewater: Soil: Organisation measures to prevent/limit release from site Conditions and measures related to municipal sewage treatment plant Conditions and measures related to external treatment of waste for disposal Conditions and measures related to external recovery of waste Other environmental control measures additional to above air emission controls required; required removal efficiency is 0% [TCR5]. Treat onsite wastewater (prior to receiving water discharge) to provide the required removal efficiency of >99% [TCR9]. soil emission controls required; required removal efficiency is 0% [TCR7]. Prevent discharge of undissolved substance to or recover from wastewater [OMS1]. Assumed industrial sewage treatment plant effluent flow is 2000 m 3 /d. t applicable t applicable ne Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 14 of 148

15 Exposure estimation Manufacturing Worker exposure The situations leading to exposure include the production of neat MTBE. The worker exposure estimates for the activities associated with the manufacture of MTBE have been assessed using ECETOC TRA version 2 (See Annex A1). In contrast to the default of the ECETOC TRA model, no influence of local exhaust ventilation (LEV) was taken into account for assessment of dermal exposure. In Annex A1.1 general information, including the DNELs, of the exposure scenario is presented. In Annex A1.2 the contributing scenarios with typical mapped operational conditions and Risk Management Measures are presented. Annex A1.3 is explained in the next section. When modeling resulted in risk characterization ratios above 1 exposure data was used to estimate exposure (tier-2). Only tier-2 data as presented in the EU RAR for MTBE (European Commission, 2002) was used (see Annex B1.2, containing a summary of data from the EU RAR of MTBE). The workers' exposure to MTBE may principally occur only during incidental leaks and spills from pipeline and valve connections (fugitive emissions) and maintenance operations. Sampling and laboratory work, handling products containing MTBE for analyses, lead to exposure of laboratory assistants. The mechanics are exposed daily during removal of pumps and repairing repellers. They are also doing maintenance on pipelines and vapour recovery equipment. The maintenance tasks are such that the workers are exposed to MTBE vapours and their hands are in contact with petrol products. Acute/Short term exposure Table A.1-3 contain the two subtables (1&2) describing the mapping of uses in the supply chain (contributing scenarios) (table 1) and the characterising of the risk, the Chemical Safety Assessment (table 2). This table, in the CEFIC-GES format, contains all operating conditions and the efficiencies of the exposure modifiers including RPE, PPE and LEV (efficiencies are from the ECETOC TRA model, version 2) choosen for estimation of worker exposure (long term and short term). When deviating from the standard ecetoc values or when tier 2 assessement (Annex B 1.2) is used, this is explained in the free text column of the table. The RMMs associated with the estimated exposure for each contributing scenario are presented in chapter Operational conditions and worker exposure data (short term and long term) corresponding with the handling of neat MTBE for inhalatory exposure as described in the EU RAR of MTBE (European Commission, 2002) are summarized in annex B1.1 and B1.2. Long-term exposure See references provided in chapter Justification for use of additional efficiency factors: - Draining prior to maintenance (Drain down and flush system prior to equipment break-in or maintenance [E55]) delivers a reduction of 90% of the exposure estimate. Reduction is based on comparison of CONCAWE data on exposures resulting from spills and those arising from same/similar task when SOP invoked (only applicable in industrial settings) Consumer exposure t applicable.

16 Indirect exposure of humans via the environment The human intake of MTBE from indirect exposure from production is presented in Table 1. All food products are considered to come from the vicinity of the point source. The estimations are results of EUSES (2008) calculations. Table 2: Local s for indirect exposure of humans via the environment Human intake media Local Regional Total Fish (mg/kg) 2.03E E E-03 Root crops (mg/kg) 1.69E E E-01 Leaf crops (mg/kg) 2.12E E E-02 Grass (mg/kg) 2.12E E E-02 Drinking water (mg/l) 1.57E E E-01 Meat (mg/kg) 3.47E E E-05 Milk (mg/l) 3.47E E E-04 Air (mg/m 3 ) 2.74E E Environmental exposure Environmental releases MTBE is produced in closed systems in either wet or dry processes. Atmospheric emissions are expected from both types of processes and release to water primarily from the wet process. In the wet process of manufacturing MTBE, water is used to wash a hydrocarbon-methanol stream to extract the methanol from the hydrocarbon stream and recycle it. In the dry process, there is no water wash used to extract the methanol. The excess methanol is extracted by other means and recycled to the feed. During the manufacturing process of MTBE, the product is never in direct contact with water. Water is used in some processes (the so called wet processes) to wash the methanol from the methanolhydrocarbon stream. The MTBE product is extracted before the wash. However, some traces of MTBE can be present in the MeOH-HC stream. To avoid of the water stream, a very small side stream is extracted from the water stream and led to the wastewater unit. This stream can contain MTBE in small amounts (<0.1 ppm) but these traces are removed in the wastewater unit to levels below detection. The default emission factors from the Technical Guidance Document (2003) for mineral oil and fuel Industry; fuel additives (IC9, UC28) are replaced by the emission factors from the ESVOC 1 SpERC. The release factor for air is set at 0.005, the release factor for waste water at 0.01, and the factor to soil at For the regional assessment it is assumed that all waste water is collected by industrial sewage treatment plants. The releases to the environment from production calculated with EUSES (2008) are listed in Table 3. Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 16 of 148

17 Table 3: Summary of the releases to the environment Compartment Local source release Regional source release Air (kg/d) 1.20E E+04 Waste water (kg/d) 3.87E E+04 Surface water (kg/d) Industrial soil (kg/d) E+03 Agricultural soil (kg/d) Exposure in the aquatic compartment The Predicted Exposure Concentrations (PEC) in the aquatic compartment for production calculated with EUSES (2008) are given in Table 4. For the determination of the Predicted Exposure Concentrations in the sewage treatment plant (PEC STP ), homogeneous mixing in the aeration tank is assumed. The PECstp is therefore equal to the dissolved of the substance. The PEC STP for production calculated with EUSES (2008) are listed in Table 4. Table 4: Predicted Exposure Concentrations (PEC) in the aquatic compartment Compartment Local Regional Total Surface water (mg/l) 1.46E E E-03 Marine water (mg/l) 1.58E E E-04 Surface water annual avg (mg/l) Marine water annual avg. (mg/l) 1.27E E E E-04 STP effluent (mg/l) 1.04E E Exposure in soils and sediments The exposure routes taken into account in PEC local calculations are application of sewage sludge in agriculture and dry and wet deposition from the atmosphere. Concentration in soil (Clocal soil ) can be estimated using the aerial deposition flux per kg of soil and the sludge (see Table 5). The of MTBE in groundwater is calculated for indirect exposure of humans through drinking water. As an indication for potential groundwater levels, the in porewater of agricultural soil is taken. This is a worst-case assumption, neglecting transformation and dilution in deeper soil layers. The Predicted Exposure Concentrations (PEC) in soil and groundwater for production calculated with EUSES (2008) are given in Table 5. The Predicted Exposure Concentrations (PEC) in sediment for production calculated with EUSES (2008) are given in Table 5.

18 Table 5: Predicted Exposure Concentrations (PEC) in soils and sediments Compartment Local Regional Total Freshwater sediment (mg/kg wwt ) 1.43E E E-03 Marine sediment (mg/kg wwt ) 1.55E E E-04 Agricultural soil 30 d (mg/kg wwt ) Agricultural soil 180 d (mg/kg wwt ) 4.56E E E E E E-02 Grassland 180 d (mg/kg wwt ) 4.65E E-02 Groundwater (mg/l) 1.57E E Atmospheric compartment The of the substance in air is estimated at a distance of 100 m from a point source (Reach Guidance R.16, 2008). In the calculation of PEC local for air, both emissions from a point source as well as the emissions from a STP are taken into account. The Predicted Exposure Concentrations (PEC) in air for production calculated with EUSES (2008) are given in Table 6. Table 6: Predicted Exposure Concentration (PEC) in air Local Regional Compartment Total Air episodic (mg/m 3 ) 3.34E E-01 Air annual avg (mg/m 3 ) 2.74E E E Exposure relevant for the food chain (Secondary poisoning) Exposure assessment through secondary poisoning has not been carried out for MTBE since it has low potential to accumulate to living organisms, and it is not classified as very toxic (T+), toxic (T) or harmful (Xn) according to mammalian toxicity data. Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 18 of 148

19 Exposure Scenario 2: Formulation - industrial Formulation of MTBE covers the blending of petrol with MTBE, both on site and off site. The formulation of MTBE into petrol is considered to be in an automated and principally closed outdoor system with a connection to central waste gas system Exposure scenario Section 1 Title Exposure Scenario Title Formulation of MTBE;CAS RN Use Descriptor Sector of Use: Industrial (SU3) Process Categories: PROC1, PROC2, PROC3, PROC4, PROC5, PROC8a, PROC8b, PROC9, PROC15 Environmental Release Categories: ERC2 Specific Environmental Release Categories: ESVOC4 SpERC Processes, tasks, activities covered Formulation, packing and re-packing of the substance and its mixtures in batch or continuous operations, including storage, materials transfers, mixing, large and small scale packing, maintenance and associated laboratory activities Section 2 Operational conditions and risk management measures Field for additional statements to explain scenario if required. Section 2.1 Control of worker exposure Product characteristics Physical form of product Liquid, vapour pressure > 10 kpa [OC5]. Concentration of substance in product Covers percentage substance in the product up to 100 % (unless stated differently) [G13]. Amounts used t applicable Frequency and duration of use Covers daily exposures up to 8 hours (unless stated differently) [G2] Human factors not influenced by risk t applicable management Other Operational Conditions affecting worker exposure Contributing Scenarios General measures (skin irritants) [G19]. Assumes use at not > 20 C above ambient [G15]; Assumes a good basic standard of occupational hygiene is implemented [G1]. Risk Management Measures te: list RMM standard phrases according to the control hierarchy indicated in the ECHA template: 1. Technical measures to prevent release, 2. Technical measures to prevent dispersion, 3. Organisational measures, 4. Personal protection. Avoid all skin contact with product, clean up contamination/spills as soon as they occur. Wear gloves (tested to EN374) if hand contamination likely, wash off any skin contamination immediately. Provide basic employee training to prevent / minimise exposures and

20 [CS15]. [CS15]; With sample collection [CS56]. [CS15]; Use in contained batch processes [CS37]; With sample collection [CS56]. General exposures (open systems) [CS16]. Batch process [CS55]. With sample collection [CS56]; Filling / preparation of equipment from drums or containers. [CS45]. [CS15]; Batch processes at elevated temperatures [CS136].With sample collection [CS56]. Process sampling [CS2]. Laboratory activities [CS36]. Cleaning [CS47] [wiping, brushing, flushing] bulk closed loading and unloading [CS501] Dedicated facility [CS81] Mixing operations (open systems) [CS30]. Batch process [CS55]. Manual [CS34]; Transfer from/pouring from containers [CS22]. n-dedicated facility [CS82] to report any skin problems that may develop [E3]. specific measures identified [EI18]. Provide a good standard of general ventilation (3 to 5 air changes per hour) [E40]. Provide extract ventilation to points where emissions occur [E54]. Provide extract ventilation to points where emissions occur [E54]. Formulate in enclosed or ventilated mixing vessels [E46].Provide extract ventilation to points where emissions occur [E54]. Provide extract ventilation to points where emissions occur [E54]. Handle in a fume cupboard or under extract ventilation [E83]. Provide extract ventilation to material transfer points and other openings [E82]. Provide extract ventilation to points where emissions occur [E54]. Ensure material transfers are under containment or extract ventilation [E66]. Drum/batch transfers [CS8]. Dedicated facility [CS81] Drum and small package filling [CS6]. Dedicated facility [CS81] Equipment cleaning and maintenance [CS39]. n-dedicated facility [CS82] Storage [CS67]; [CS15]. Storage [CS67]; [CS15]; With sample collection [CS56]. Section 2.2 Product characteristics Operational conditions Amounts used Fraction of EU tonnage used in region [A1]: 0.15 Use drum pumps [E53].Minimise exposure by partial enclosure of the operation or equipment and provide extract ventilation at openings [E60]. Fill containers/cans at dedicated fill points supplied with local extract ventilation [E51] Drain down and flush system prior to equipment breakin or maintenance [E55].Avoid carrying out activities involving exposure for more than 4 hours [OC28], or: Wear a respirator conforming to EN140 with Type A filter or better. [PPE22] specific measures identified [EI18]. Avoid carrying out activities involving exposure for more than 4 hours [OC28], or: Wear a respirator conforming to EN140 with Type A filter or better. [PPE22] Control of environmental exposure Substance is a unique structure [PrC1]. Predominantly hydrophobic [PrC4a]. Readily biodegradable [PrC5a]. Outdoor use [OOC1]. Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 20 of 148

21 Regional use tonnage (tonnes/year) [A2]: 100,376 Fraction of regional tonnage used locally 0.05 [A3]: Average local daily tonnage (kg/d) [A5]: 16,729 Annual site tonnage (tonnes/year) [A6] 5,019 Frequency and duration of use Type of release Continuous release [FD2]. Emission days (days/year) [FD4]: 300 Other Operational Conditions of use affecting environmental exposure Use in closed systems. Either wet or dry processes. Release fraction to air from process: Release fraction to wastewater from process: 5.00E-03 Release fraction to soil from process (regional only): RMMs Technical conditions and measures at process level (source) to prevent release 1.00E-04 Common practices vary across sites thus conservative process release estimates used [TCS 1]. Technical onsite conditions and measures to reduce or limit discharges, air emissions and releases to soil Air: air emission controls required; required removal efficiency is 0% [TCR5]. Wastewater: Treat onsite wastewater (prior to receiving water discharge) to provide the required removal efficiency of >99% [TCR9]. Soil: soil emission controls required; required removal efficiency is 0% [TCR7]. Organisation measures to prevent/limit Prevent discharge of undissolved substance to or recover release from site from wastewater [OMS1]. Conditions and measures related to Assumed industrial sewage treatment plant effluent flow municipal sewage treatment plant is 2000 m 3 /d. Conditions and measures related to t applicable external treatment of waste for disposal Conditions and measures related to t applicable external recovery of waste Other environmental control measures ne additional to above

22 Exposure estimation Formulation - industrial Worker exposure The situations leading to exposure include formulation (blending and storing): petrol blending with MTBE. The worker exposure estimates for the activities associated with formulation have been assessed using ECETOC TRA version 2. (See Annex A2). In contrast to the default of the ECETOC TRA model, no influence of local exhaust ventilation (LEV) was taken into account for assessment of dermal exposure. In Annex A2.1 general information, including the DNELs, of the exposure scenario is presented. In Annex A2.2 the contributing scenarios with typical mapped operational conditions and Risk Management Measures are presented. Annex A2.3 is explained in the next section. The workers' exposure to MTBE may principally occur only during incidental leaks and spills from pipeline and valve connections (fugitive emissions) and maintenance operations. In formulation (blending and storing) operations, exposure might either concern neat MTBE or blended fuel. Sampling and laboratory work, handling products containing MTBE for analyses, lead to exposure of laboratory assistants. The mechanics are daily exposed during removal of pumps and repairing repellers. They are also doing maintenance on pipelines and vapour recovery equipment. The maintenance tasks are such that the workers are exposed to MTBE vapours and their hands are in contact with petrol products. Acute/Short term exposure Table A.2-3 contain the two subtables (1&2) describing the mapping of uses in the supply chain (contributing scenarios) (table 1) and the characterising of the risk, the Chemical Safety Assessment (table 2). This table, in the CEFIC-GES format, contains all operating conditions and the efficiencies of the exposure modifiers including RPE, PPE and LEV (efficiencies are from the ECETOC TRA model, version 2) choosen for estimation of worker exposure (long term and short term). When deviating from the standard ecetoc values or when tier 2 assessement (Annex B 1.2) is used, this is explained in the free text column of the table. The RMMs associated with the estimated exposure for each contributing scenario are presented in chapter Operational conditions and worker exposure data (short term and long term) corresponding with the handling of neat MTBE for inhalatory exposure as described in the EU RAR of MTBE (European Commission, 2002) are summarized in annex B1.1 and B1.2. Long-term exposure See references provided in chapter Justification for use of additional efficiency factors: - Draining prior to maintenance (Drain down and flush system prior to equipment break-in or maintenance [E55]) delivers a reduction of 90% of the exposure estimate. Reduction is based on comparison of CONCAWE data on exposures resulting from spills and those arising from same/similar task when SOP invoked (only applicable in industrial settings) Consumer exposure t applicable Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 22 of 148

23 Indirect exposure of humans via the environment The human intake of MTBE from indirect exposure from formulation is presented in Table 7. All food products are considered to come from the vicinity of the point source. The estimations are results of EUSES (2008) calculations. Table 7: Local s for indirect exposure of humans via the environment Human intake media Local Regional Total Fish (mg/kg) 1.99E E E-03 Root crops (mg/kg) 3.80E E E-01 Leaf crops (mg/kg) 4.84E E E-02 Grass (mg/kg) 4.84E E E-02 Drinking water (mg/l) 3.54E E E-01 Meat (mg/kg) 7.90E E E-05 Milk (mg/l) 7.90E E E-04 Air (mg/m 3 ) 6.28E E Environmental exposure Environmental releases Formulation of MTBE covers the blending of petrol with MTBE. Emissions into environment are mainly atmospheric. There are two formulation techniques for blending petrol with MTBE, in-line blending and batch blending. In in-line blending the petrol components (including MTBE) are pumped from their storage tanks to a common line and pumped further through the common line to the product storage tank. The components are blended both during the pumping through the common line and in the product tank. In batch blending the petrol components are pumped through separate lines to the storage tank. The blending of the components hence takes place only in the product tank. When MTBE is blended in to petrol outside the refineries, e.g. in commercial terminals, both techniques can be used for the blending. Batch blending is however usually more used. There are 4-8 commercial terminals within the EU that do blending of petrol. Approximately 5% or less of the MTBE used in Europe are blended outside the refineries (Fortum, 2000a). It is expected that the MTBE emissions in these terminals should not differ from the emissions from blending activities in the refineries since the techniques used are similar. The default emission factors from the Technical Guidance Document (2003) for mineral oil and fuel Industry; fuel additives (IC9, UC28) are replaced by the emission factors from the ESVOC 4 SpERC. The release factor for air is set at 0.025, the release factor for waste water at 0.005, and the factor to soil at The default fraction of the main source is also replaced by specific data (fraction of the main source is For the regional assessment it is assumed that all waste water is collected by industrial sewage treatment plants. The releases to the environment from formulation calculated with EUSES (2008) are listed in Table 8.

24 Table 8: Summary of the releases to the environment Compartment Local source release Regional source release Air (kg/d) 2.75E E+04 Waste water (kg/d) 5.49E E+04 Surface water (kg/d) Industrial soil (kg/d) E+03 Agricultural soil (kg/d) Exposure in the aquatic pelagic compartment The Predicted Exposure Concentrations (PEC) in the aquatic compartment for formulation calculated with EUSES (2008) are given in Table 9. For the determination of the PEC STP, homogeneous mixing in the aeration tank is assumed. The PECstp is therefore equal to the dissolved of the substance. The PEC in the sewage treatment plant for formulation calculated with EUSES (2008) are listed in Table 9. Table 9: Predicted Exposure Concentrations (PEC) in the aquatic compartment Compartment Local Regional Total Surface water (mg/l) 1.43E E E-03 Marine water (mg/l) 1.56E E E-04 Surface water annual avg (mg/l) Marine water annual avg. (mg/l) 1.25E E E E-04 STP effluent (mg/l) 1.01E E Exposure in soils and sediments The exposure routes taken into account in PEC local calculations are application of sewage sludge in agriculture and dry and wet deposition from the atmosphere. Concentration in soil (Clocal soil ) can be estimated using the aerial deposition flux per kg of soil and the sludge (see Table 10). The of MTBE in groundwater is calculated for indirect exposure of humans through drinking water. As an indication for potential groundwater levels, the in porewater of agricultural soil is taken. This is a worst-case assumption, neglecting transformation and dilution in deeper soil layers. The Predicted Exposure Concentrations (PEC) in soil and groundwater for formulation calculated with EUSES (2008) are given in Table 10. The Predicted Exposure Concentrations (PEC) in sediment calculated with EUSES (2008) are given in Table 10. Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 24 of 148

25 Table 10: Predicted Exposure Concentrations (PEC) in soils and sediments Compartment Local Regional Total Freshwater sediment (mg/kg wwt ) 1.40E E E-03 Marine sediment (mg/kg wwt ) 1.53E E E-04 Agricultural soil 30 d (mg/kg wwt ) Agricultural soil 180 d (mg/kg wwt ) 9.94E E E E E E-02 Grassland 180 d (mg/kg wwt ) 1.06E E-01 Groundwater (mg/l) 3.54E E Atmospheric compartment The of the substance in air is estimated at a distance of 100 m from a point source (REACH Guidance R.16, 2008). In the calculation of PEC local for air, both emissions from a point source as well as the emissions from a STP are taken into account. The Predicted Exposure Concentrations (PEC) in air for formulation calculated with EUSES (2008) are given in Table 11. Table 11: Predicted Exposure Concentration (PEC) in air Compartment Local Regional Total Air episodic (mg/m 3 ) 7.64E E-01 Air annual avg (mg/m 3 ) 6.28E E E Exposure relevant for the food chain (Secondary poisoning) Exposure assessment through secondary poisoning has not been carried out for MTBE since it has low potential to accumulate to living organisms, and it is not classified as very toxic (T+), toxic (T) or harmful (Xn) according to mammalian toxicity data.

26 Exposure Scenario 3: Use as an intermediate - industrial MTBE is used as intermediate for isobutylene production Exposure scenario Section 1 Title Exposure Scenario Title Use MTBE as intermediate;cas RN Use Descriptor Sector of Use: Industrial (SU3) Process Categories: PROC1, PROC2, PROC3, PROC4, PROC8a, PROC8b, PROC15 Environmental Release Categories: ERC6a Specific Environmental Release Categories: ESVOC2 SpERC Processes, tasks, activities covered Use as intermediate. Includes recycling/ recovery, material transfers, storage, sampling, associated laboratory activities, maintenance and loading (including marine vessel/barge, road/rail car and bulk container). Section 2 Operational conditions and risk management measures Field for additional statements to explain scenario if required. Section 2.1 Control of worker exposure Product characteristics Physical form of product Liquid, vapour pressure > 10 kpa [OC5]. Concentration of substance in product Covers percentage substance in the product up to 100 % (unless stated differently) [G13]. Amounts used t applicable Frequency and duration of use Covers daily exposures up to 8 hours (unless stated differently) [G2] Human factors not influenced by risk t applicable management Other Operational Conditions affecting worker exposure Assumes use at not > 20 C above ambient [G15]; Assumes a good basic standard of occupational hygiene is implemented [G1]. Contributing Scenarios Risk Management Measures te: list RMM standard phrases according to the control hierarchy indicated in the ECHA template: 1. Technical measures to prevent release, 2. Technical measures to prevent dispersion, 3. Organisational measures, 4. Personal protection.. General measures (skin irritants) [G19]. Avoid all skin contact with product, clean up contamination/spills as soon as they occur. Wear gloves (tested to EN374) if hand contamination likely, wash off any skin contamination immediately. Provide basic employee training to prevent / minimise exposures and to report any skin problems that may Exposure scenarios for SDS (Version: 2.2 Created: 21/03/2012) Page 26 of 148

27 [CS15]. [CS15]; With sample collection [CS56]. develop [E3]. specific measures identified [EI18]. Ensure operation is undertaken outdoors [E69]. [CS15]; Use in contained batch processes [CS37]. With sample collection [CS56]. General exposures (open systems) [CS16]. Batch process [CS55]. With sample collection [CS56]; Filling / preparation of equipment from drums or containers. [CS45]. Process sampling [CS2]; Dedicated facility [CS81] Laboratory activities [CS36]. Cleaning [CS47] [wiping, brushing, flushing] bulk open loading and unloading [CS503]n-dedicated facility [CS82] bulk closed loading and unloading [CS501]Dedicated facility [CS81] Equipment cleaning and maintenance [CS39]. n-dedicated facility [CS82] Storage [CS67]; [CS15]. Storage [CS67]; [CS15]; With sample collection [CS56]. Section 2.2 Product characteristics Operational conditions Amounts used Fraction of EU tonnage used in region [A1]: 0.25 Regional use tonnage (tonnes/year) [A2]: 8,030 Fraction of regional tonnage used locally [A3]: 1 Average local daily tonnage (kg/d) [A5]: 26,767 Provide extract ventilation to points where emissions occur [E54]. Ensure material transfers are under containment or extract ventilation [E66]. Provide extract ventilation to points where emissions occur [E54]. Handle in a fume cupboard or under extract ventilation [E83]. Avoid carrying out activities involving exposure for more than 4 hours [OC28], or: Wear a respirator conforming to EN140 with Type A filter or better. [PPE22] Avoid carrying out activities involving exposure for more than 4 hours [OC28], or: Wear a respirator conforming to EN140 with Type A filter or better. [PPE22] Drain down and flush system prior to equipment break-in or maintenance [E55].Avoid carrying out activities involving exposure for more than 4 hours [OC28], or: Wear a respirator conforming to EN140 with Type A filter or better. [PPE22] specific measures identified [EI18]. Avoid carrying out activities involving exposure for more than 4 hours [OC28], or: Wear a respirator conforming to EN140 with Type A filter or better. [PPE22] Control of environmental exposure Substance is a unique structure [PrC1]. Predominantly hydrophobic [PrC4a]. Readily biodegradable [PrC5a]. Outdoor use [OOC1].