SAFETY DATA SHEET ACCORDING TO EC-REGULATIONS 1907/2006 (REACH) & 1272/2008 (CLP) SULPHUR DIOXIDE XXXX
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1 SAFETY DATA SHEET ACCORDING TO EC-REGULATIONS 1907/2006 (REACH) & 1272/2008 (CLP) 1. SECTION 1: IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING 1.1 Product identifier GHS Product Identifier SULPHUR DIOXIDE EC INDEX No Alternative names Sulphurous acid anhydride, Sulphurous oxide REACH Registration No XXXX 1.2 Relevant identified uses of the substance or mixture and uses advised against Identified use(s) Industrial use: production of foundry cores, paper, sugar, starch, pharmaceutical products, water treatment, glass coating & manufacture, metal casting/mining/purification. Professional use: winemaking, use in refrigeration equipment. The manufacture of bisulphite products using sulphur dioxide must only be conducted under strictly controlled conditions (SCC) as described in REACH. Uses advised against Only uses listed in Identified Use(s) are authorised. For a full list of identified uses see Section 16: Annex to the extended Safety Data Sheet (esds) 1.3 Details of the supplier of the safety data sheet Company Identification (competent person) INEOS Enterprises Group Limited Runcorn Site HQ South Parade, PO Box 9 Runcorn, Cheshire, WA7 4JE Tel : (01928) , Fax : (01928) msds.enterprises@ineos.com 1.4 Emergency telephone number IN AN EMERGENCY DIAL 999 (UK Only) or 112 (EU) For specialist advice in an emergency telephone Runcorn +44 (0) (24 hr) (24 hour) 2. SECTION 2: HAZARDS IDENTIFICATION 2.1 Classification of the substance or mixture Directive 67/548/EEC & Directive 1999/45/EC Regulation (EC) No. 1272/2008 (CLP). T: R23: Toxic by inhalation. C: R34: Causes burns. Liquefied gas, Acute Tox. 3, Skin Corr. 1B 2.2 Label elements Hazard statement(s) Signal word(s) H280: Contains gas under pressure; may explode if heated. H314: Causes severe skin burns and eye damage. H331: Toxic if inhaled. DANGER Hazard pictogram(s) Precautionary statement(s) P280: Wear protective gloves/protective clothing/eye protection/face protection. P304+P340: IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing. P305+P351+P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. P310: Immediately call a POISON CENTER or doctor/physician. P410+P403: Protect from sunlight. Store in a well-ventilated place. Additional label requirements None Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 1 of 22
2 2.3 Other hazards Liquid splashes or spray may cause freeze burns to skin and eyes. 3. SECTION 3: COMPOSITION/INFORMATION ON INGREDIENTS 3.1 Substances Hazardous ingredient(s) %(w/w) CAS No. EC No. H - Codes GHS Classification Sulphur Dioxide H280, H314, H331 Liquefied gas, Acute Tox. 3, Skin Corr. 1B 4. SECTION 4: FIRST AID MEASURES 4.1 Description of first aid measures Inhalation Skin Contact Remove patient from exposure, keep warm and at rest. Administer oxygen if necessary. Apply artificial respiration if breathing has ceased or shows signs of failing. Obtain medical attention. Following contact with vapour: Remove contaminated clothing. After contact with skin, wash immediately with plenty of water. If symptoms (irritation or blistering) occur obtain medical attention. Following contact with liquid: Thaw affected areas with water. Remove contaminated clothing. Caution: clothing may adhere to the skin in the case of freeze burns After contact with skin, wash immediately with plenty of water. Obtain medical attention. Eye Contact Ingestion Immediately irrigate with eyewash solution or clean water, holding the eyelids apart, for at least 15 minutes. Remove contact lenses, if present and easy to do. Continue rinsing. Obtain immediate medical attention. Do not induce vomiting. Provided the patient is conscious, wash out mouth with water and give ml (half a pint) of water to drink. Obtain medical attention. 4.2 Most important symptoms and effects, both acute and delayed Gas is irritant to the respiratory tract. Causes severe skin burns and eye damage. Fluid build up on the lung (pulmonary oedema) may occur up to 48 hours after exposure and could prove fatal. Some individuals with asthma may be particularly sensitive to the inhalation of low atmospheric concentrations of sulphur dioxide. 4.3 Indication of any immediate medical attention and special treatment needed Treat symptomatically. Following exposure the patient should be kept under medical review for at least 48 hours as delayed pulmonary oedema may develop. 5. SECTION 5: FIRE-FIGHTING MEASURES 5.1 Extinguishing media Suitable Extinguishing Media Unsuitable Extinguishing Media As appropriate for surrounding fire. Water spray should be used to knock down vapour and cool containers. As appropriate for surrounding materials/equipment. 5.2 Special hazards arising from the substance or mixture Non-flammable. Containers may burst if overheated. Fire water contaminated with this material must be contained and prevented from being discharged to any waterway, sewer or drain. 5.3 Advice for fire-fighters A self contained breathing apparatus and full protective clothing must be worn in fire conditions. 6. SECTION 6: ACCIDENTAL RELEASE MEASURES 6.1 Personal precautions, protective equipment and emergency procedures People dealing with major spillages should wear full protective clothing including respiratory protection. 6.2 Environmental precautions Avoid release to the environment. Provided it is safe to do so, isolate the source of the leak. Warn people downwind. Keep unnecessary personnel away. Evacuate if necessary. Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 2 of 22
3 6.3 Methods and material for containment and cleaning up Small spillages: Allow small spillages to evaporate provided there is adequate ventilation. Large spillages: Large spillages should be contained by covering with plastic sheeting. Recondensed sulphur dioxide, contained under sheeting, should be pumped away into containers for disposal. 6.4 Reference to other sections See Section: 8, Additional information In the event of spillages or uncontrolled discharges into watercourses, drains or sewers, the UK Environment Agency or other appropriate regulatory body must be informed immediately. 7. SECTION 7: HANDLING AND STORAGE 7.1 Precautions for safe handling Do not breathe gas. Avoid contact between the liquid and skin and eyes. Wherever possible should be handled in high containment systems. Provide adequate ventilation, including appropriate local extraction, to ensure that the occupational exposure limit is not exceeded. Showers and eye washing equipment must be provided at handling points. 7.2 Conditions for safe storage, including any incompatibilities Keep container tightly closed, in a cool, well ventilated place. Keep away from heat and direct sunlight. Keep only in original container. 7.3 Specific end use(s) Apart from uses mentioned in Section 1.2 and Annex, no other specific uses are stipulated. 8. SECTION 8: EXPOSURE CONTROLS/PERSONAL PROTECTION 8.1 Control parameters Atmospheric levels should be controlled in compliance with the occupational exposure limit. HAZARDOUS CAS No. LTEL 8 hr TWA LTEL 8 hr TWA STEL ppm STEL mg/m3 Note: INGREDIENT(S) ppm mg/m3 Sulphur Dioxide HSE GV DNEL / DMEL Oral Inhalation Dermal Industry - Long Term - Local effects mg/m³ (0.5 ppm) - Industry - Long Term - Systemic effects Industry - Short term - Local effects mg/m³ (1 ppm) - Industry - Short term - Systemic effects Consumer. - Long Term - Local effects mg/m³ (0.2 ppm) - Consumer. - Long Term - Systemic effects Consumer. - Short term - Local effects Consumer. - Short term - Systemic effects Environment Aquatic Compartment (including sediment) - Terrestrial Compartment - Atmospheric Compartment - PNEC 8.2 Exposure controls Appropriate engineering controls Wear suitable protective clothing, gloves and eye/face protection. Wear suitable respiratory protective equipment if exposure to levels above the occupational exposure limit is likely. Showers and eye washing equipment must be provided at handling points. Do not eat, drink or smoke at the work place. Wash hands and exposed skin after use. Personal Protection Eye/face protection Skin protection Respiratory protection Thermal hazards Goggles giving complete protection to eyes. Wear suitable protective clothing and gloves. Check with protective equipment manufacturer's data. The gloves type used must be chosen based on the work activity and duration as well as concentration/quantity of material being handled. Wear suitable respiratory protective equipment if exposure to levels above the occupational exposure limit is likely. A self contained breathing apparatus may be appropriate. Where a cartridge/canister respirator is suitable use: Type E Check with protective equipment manufacturer's data. Wear thermal insulating gloves when handling liquefied gases. Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 3 of 22
4 9. SECTION 9: PHYSICAL AND CHEMICAL PROPERTIES 9.1 Information on basic physical and chemical properties Molecular weight: Form gas Colour colourless Odour pungent Boiling Point (Deg C) Melting Point (Deg C) Vapour Pressure (Pascals) at 20 Deg C Density (g/ml) 1.43 at 0 Deg C Solubility (Water) soluble (114 g/l at 20 Deg C) Solubility (Other) soluble in: ethanol, methanol, acetic acid, chloroform, diethylether, polar solvents. Vapour Density (Air= 1) Other information None 10. SECTION 10: STABILITY AND REACTIVITY 10.1 Reactivity Hazardous polymerisation will not occur Chemical Stability Stable under normal conditions Possibility of hazardous reactions May react violently with: Acrolein, Ammonia, amines, acetylene, alkali metals, chlorine, butadiene, ethylene oxide 10.4 Conditions to avoid Keep away from moisture. Keep away from heat and direct sunlight. Heating of containers may cause pressure rise, with risk of bursting Incompatible materials Reacts with water to produce sulphurous acid. Sulphur dioxide can corrode zinc and most common metals if water is present Hazardous Decomposition Product(s) Oxides of sulphur 11. SECTION 11: TOXICOLOGICAL INFORMATION 11.1 Information on toxicological effects Test result / data Acute oral toxicity No data. Unlikely route of exposure. The substance is a gas. Acute inhalation toxicity LC50 ( Inhalation ) mg/m³ ( Value used for Chemical Safety Assessment ) Toxic if inhaled. Acute dermal toxicity Skin irritation. Serious eye damage/irritation Respiratory irritation Sensitisation Repeated dose toxicity Germ cell mutagenicity No data. The corrosive nature of the substance will predominate. Corrosive. Causes severe skin burns and eye damage. Liquid splashes or spray may cause freeze burns to skin and eyes. Corrosive. Causes severe skin burns and eye damage. Vapour is irritant to the respiratory tract. Some individuals with asthma may be particularly sensitive to the inhalation of low atmospheric concentrations of sulphur dioxide. There is no evidence that sulphur dioxide is a sensitiser of the skin or the respiratory tract. Studies in animals have shown that repeated exposure by inhalation may cause damage to the respiratory tract. LOAEC = 5ppm The material did not induce mutagenicity in in-vitro or in-vivo studies. Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 4 of 22
5 Carcinogenicity Reproductive toxicity Specific target organ toxicity single exposure (STOT SE) Specific target organ toxicity repeated exposure (STOT RE) Aspiration hazard Other effects Not classified. No evidence of carcinogenicity. Not classified. Studies in animals have shown that sulphur dioxide produces foetotoxic effects in the presence of maternal toxicity. Not classified. Not classified. Not an aspiration hazard None 12. SECTION 12: ECOLOGICAL INFORMATION 12.1 Toxicity Acute or chronic toxicity data for sulphur dioxide in the aquatic environment are not relevant as it does not exist in the aquatic phase Persistence and degradability Sulphur dioxide will react with water to produce sulphurous acid. Sulphur dioxide is oxidised to sulphur trioxide in the atmosphere, which in the presence of moisture is converted to sulphuric acid. Sulphuric acid eventually reaches ground by precipitation Bioaccumulative potential The product has no potential for bioaccumulation Mobility in soil Not relevant for this material Results of PBT and vpvb assessment Not classified as PBT or vpvb Other adverse effects None 13. SECTION 13: DISPOSAL CONSIDERATIONS 13.1 Waste treatment methods Disposal by release to atmosphere is not permitted Additional information Disposal should be in accordance with local, state or national legislation. 14. SECTION 14: TRANSPORT INFORMATION 14.1 Road/Rail UN No Proper Shipping Name Sulphur dioxide ADR/RID Class 2.3 Packing Group N/A Label Tunnel Restriction Code (C/D) 14.2 SEA UN No Proper Shipping Name Sulphur dioxide IMDG Class 2.3 Packing Group N/A Label Marine Pollutant Not classified as a Marine Pollutant. Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 5 of 22
6 14.3 Air ( ICAO/IATA ) UN No Proper Shipping Name Sulphur dioxide ICAO-TI Class 2.3 Packing Group N/A Label Additional Information Transport in bulk according to Annex II of MARPOL73/78 and the IBC Code Product Name: Sulphur dioxide Ship Type: 1G Pollution Category: Not applicable. 15. SECTION 15: REGULATORY INFORMATION 15.1 Safety, health and environmental regulations/legislation specific for the substance or mixture Control of Substances Hazardous to Health Regulations (COSHH) 2002 SI 2002/2677 and COSHH Essentials: Easy steps to control chemicals - Control of Substances Hazardous to Health Regulations HSG193. Wassergefährdungsklasse (Germany) : WGK class 1 (official). Inventory Status Listed in: Australia (AICS), Canada, China (IECSC), Japan (ENCS), European Union (EINECS/ELINCS), New Zealand Inventory (NZIoC), Philippines (PICCS), United States (TSCA), South Korea (KECI) Chemical Safety Assessment A Chemical Safety Assessment (CSA) has been completed for this substance. 16. SECTION 16: OTHER INFORMATION Indication of changes See Section: 1.3, 16 LEGEND WEL : Exposure Limit (UK HSE EH40) COM : The company aims to control exposure in its workplace to this limit TLV : The company aims to control exposure in its workplace to the ACGIH limit TLV-C: The company aims to control exposure in its workplace to the ACGIH Ceiling limit MAK : The company aims to control exposure in its workplace to the German limit Sk : Can be absorbed through skin Sen : Capable of causing respiratory sensitisation Bmgv : Biological monitoring guidance value (UK HSE EH40) ILV : Indicative Limit Value (UK HSE EH40) IOELV : Indicative Occupational Exposure Limit Value PBT Persistent, Bioaccumulative and Toxic vpvb very Persistent very Bioaccumulative Key literature references Chemical Safety Report: Sulphur dioxide 08/2010 GESTIS - database on hazardous substances Further information Information in this publication is believed to be accurate and is given in good faith, but it is for the Customer to satisfy itself of the suitability for its own particular purpose. Accordingly, INEOS Enterprises Group Limited gives no warranty as to the fitness of the Product for any particular purpose and any implied warranty or condition (statutory or otherwise) is excluded except to the extent that such exclusion is prevented by law. Freedom under Patent, Copyright and Designs cannot be assumed. INEOS is a trade mark, the property of INEOS Capital Limited. Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 6 of 22
7 Appendix: Exposure scenarios List of Exposure Scenarios 1: Production of sulphur dioxide 2: Discharging and filling operations for trading and distributing purposes 3: Industrial use of sulphur dioxide in the production of foundry cores (semi-closed process) 4: Industrial use of sulphur dioxide in closed or semi-closed 5: Professional use of sulphur dioxide in winemaking/refilling of refrigeration equipment Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 7 of 22
8 IU1: Production of sulfur dioxide Exposure Scenario Format (1) addressing uses carried out by workers 1. Title Free short title Production of sulfur dioxide (SO 2) Systematic title based on use descriptor Processes, tasks and/or activities covered SU3 (Industrial uses), SU8, SU9 PC19 (appropriate PROCs and ERCs are given in Section 2 below) Processes, tasks and/or activities covered are described in Section 2 below. 2. Operational conditions and risk management measures Involved tasks Involved PROCs Unloading of waste sulfuric acid/sulfur Furnace operations Adsorption / Desorption Filling of Filling of road or rail tank cars ERC Control of workers exposure discharging of waste H 2SO 4/sulfur from road and rail tank cars into closed system spraying for decomposition in rotary furnace, operations in the post-combustion chamber and/or burning of sulfur cooling, absorption, desorption, drying, compression, condensation connecting and disconnecting operations connecting and disconnecting operations Manufacture of substances Product characteristic According to the MEASE approach, the substance-intrinsic emission potential is one of the main exposure determinants. This is reflected by an assignment of a so-called fugacity class in the MEASE tool. For operations conducted with liquid or gaseous substances the fugacity is based on the vapour pressure of that substance. Content in Use in preparation Physical form Emission potential preparation Unloading of waste sulfuric acid/sulfur aqueous solution, liquid, massive 8b b 8b very low Furnace operations gaseous high Adsorption / Desorption not restricted liquefied gas / gaseous high Filling of liquefied gas high Filling of road or rail tank cars liquefied gas high Amounts used The actual tonnage handled per shift is not considered to influence the exposure as such for this scenario. Instead, the combination of the scale of operation (industrial vs. professional) and level of containment/automation (as reflected in the PROCs and technical conditions) is the main determinant of the process-intrinsic emission potential. Frequency and duration of use/exposure The exposure duration is not restricted for all applicable in this scenario. Human factors not influenced by risk management The safe use of the substance has been demonstrated by assuming a standard breathing volume of 10 m³/shift for workers. If doubts exist that the actual breathing volume exceeds this value on a regular basis, a refined exposure scenario may be required. Other given operational conditions affecting workers exposure Room volume Outdoors or indoors Process temperature Process pressure Unloading of waste sulfuric acid/sulfur delivery and storage in roofed outdoor workplace ambient not considered relevant for occupational exposure assessment of the conducted not considered relevant Furnace operations for occupational < 1,500 C not considered relevant Adsorption / exposure assessment for occupational up to 100 C Desorption of the conducted exposure assessment Filling of of the conducted ambient 3,000 4,000 hpa Filling of road or rail ambient 3,000 4,000 hpa Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 8 of 22
9 tank cars Technical conditions and measures at process level (source) to prevent release Level of containment Level of segregation Unloading of waste sulfuric acid/sulfur Furnace operations Adsorption / Desorption Filling of Filling of road or rail tank cars tight fitting connections closed system (furnace) closed system extracted (< 100 mbar) and tight fitting connections extracted (< 100 mbar) and tight fitting connections Technical conditions and measures to control dispersion from source towards the worker Level of separation Localised controls (LC) Specification of LC Unloading of waste sulfuric acid/sulfur not required na Furnace operations furnace extraction separation of workers device 10 mbar Adsorption / is generally not Desorption required in the not required na Filling of integrated extraction devices < 100 mbar Filling of road or rail tank cars integrated extraction devices segregation of the emission source is generally not required in the For pre-cautionary reasons, it is suggested that workers leave the workplace after connecting/disconnecting if appropriate according the mode of operation. As far as technically feasible, use should be made of automated filling stations. < 100 mbar Further information Organisational measures to prevent /limit releases, dispersion and exposure Avoid inhalation or ingestion. General occupational hygiene measures are required to ensure a safe handling of the substance. These measures involve good personal hygiene practices, no eating and smoking at the workplace, unless otherwise stated below the wearing of standard working clothes and shoes. It is noted that this exposure scenario does exclusively cover exposure to sulfur dioxide. However, during raw material handling, exposure to sulfuric acid may occur. Any existing occupational exposure level has to be maintained in parallel to this exposure scenario. Conditions and measures related to personal protection, hygiene and health evaluation Eye protection equipment (e.g. goggles or visors) must be worn, unless potential contact with the eye can be excluded by the nature and type of application (i.e. closed process). Additionally, face protection, protective clothing and safety shoes are required to be worn as appropriate. Since sulfur dioxide has corrosive properties, the use of protective gloves is mandatory for all process steps. Respiratory equipment is only required if workers may be exposed to sulfur dioxide during Filling of road or rail tank cars. For such situations an ABEK1 mask offering an assigned protection factor of 30 is required. Reference is given to the section Selection of appropriate respiratory equipment for a more detailed description of the requirements of personal protective equipment. 2.2 Control of environmental exposure Product characteristics Gas Amounts used 80,000 tonnes/year maximum local downstream use volume (local worst-case tonnage is set equal to regional tonnage) regional tonnage sites using SO2 are numerous and wide-spread throughout the EU - Frequency and duration of use 365 days Technical conditions and measures at process level (source) to prevent release All are strictly closed. Technical onsite conditions and measures to reduce or limit discharges, air emissions and releases to soil None if emission to air < 7 tonnes/year. If emission to air > 7 tonnes/year, air emission abatement system should be used (e.g. wet or dry scrubber ) No emissions to water. In case of emissions to water, ph impact on the receiving water should be avoided, e.g. by neutralizing the effluent. Conditions and measures related to municipal sewage treatment plant Not applicable Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 9 of 22
10 Conditions and measures related to external treatment of waste for disposal No solid waste Conditions and measures related to external recovery of waste No solid waste 3. Exposure estimation and reference to its source Occupational exposure For the assessment of inhalation exposure, measured data from the production of SO 2 and the exposure estimated from the MEASE tool were used. The risk characterisation ratio (RCR) is the quotient of the refined exposure estimate and the respective DNEL (derived no-effect level) and has to be below 1 to demonstrate a safe use. For inhalation exposure, the RCR is based on the DNEL for sulfur dioxide of 0.5 ppm (1.3 mg/m³). Unloading of waste sulfuric acid/sulfur Method used for inhalation exposure assessment Inhalation exposure estimate (RCR) not assessed as sulfur dioxide is not yet produced Furnace operations measured data 0.2 ppm (0.4) Adsorption / Desorption MEASE 0.01 ppm (0.02) Filling of measured data 0.2 ppm (0.4) Filling of road or rail tank cars measured data 0.03 ppm (0.07) Environmental emissions Method used for dermal exposure assessment Dermal exposure estimate (RCR) Since sulfur dioxide has corrosive properties, dermal exposure has to be minimised as far as technically feasible. A DNEL for dermal effects has not been derived. Thus, dermal exposure is not assessed in this exposure scenario. The predicted no effect concentration PNEC of SO 2 in air is 6.65 µg/m3. Following a PECregional air of µg/m3 and a maximum RCR of 0.95, 7 tonnes/year (PEC 5.28 µg/m3) is the maximum amount of SO2 that can be released. Consequently safe use can be demonstrated when emissions to air of SO 2 do not exceed 7 tonnes/year. 4. Guidance to DU to evaluate whether he works inside the boundaries set by the ES Occupational exposure The downstream user (DU) works inside the boundaries set by the ES if either the proposed risk management measures as described above are met or the DU can demonstrate on his own that his operational conditions and implemented risk management measures are adequate. This has to be done by showing that they limit the inhalation and dermal exposure to a level below the respective DNEL (given that the and activities in question are covered by the PROCs listed above) as given below. If measured data are not available, the DU may make use of an appropriate scaling tool such as MEASE ( to estimate the associated exposure. It is noted that any given RPE and corresponding APFs in MEASE are related to their efficiency for protection against particles. Thus, for the current scenarios, the specific protection factor of an ABEK1 respiratory mask of 30 has to be applied manually by the user. DNEL inhalation : 0.5 ppm (1.3 mg/m3) Important note: The DU has to be aware of the fact that apart from the long-term DNEL given above, a DNEL for acute effects exists at a level of 1 ppm (2.7 mg/m³). By demonstrating a safe use when comparing exposure estimates with the long-term DNEL, the acute DNEL is therefore also covered (according to R.14 guidance, acute exposure levels can be derived by multiplying long-term exposure estimates by a factor of 2). When using MEASE for the derivation of exposure estimates, it is noted that the exposure duration may not be reduced. Environmental emissions The downstream user (DU) works inside the boundaries set by the ES if emission to air < 7 tonnes/year. If emission to air > 7 tonnes/year, air emission abatement system should be used (wet or dry scrubber ). Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 10 of 22
11 IU2: Discharging and filling operations for trading and distributing purposes Exposure Scenario Format (1) addressing uses carried out by workers 1. Title Free short title Discharging and filling operations for trading and distributing purposes of sulfur dioxide (SO 2) Systematic title based on use descriptor Processes, tasks and/or activities covered SU3 (Industrial uses), SU10 PC19, PC21 (appropriate PROCs and ERCs are given in Section 2 below) Processes, tasks and/or activities covered are described in Section 2 below. 2. Operational conditions and risk management measures Involved tasks Involved PROCs Discharging and filling of road/rail tank cars discharging and filling operations (including formulation steps in closed systems) discharging and filling operations (including formulation steps in closed systems) 1, 8a, 8b, 9 1, 8a, 8b, 9 ERC 2 Formulation of preparations 2.1 Control of workers exposure Product characteristic According to the MEASE approach, the substance-intrinsic emission potential is one of the main exposure determinants. This is reflected by an assignment of a so-called fugacity class in the MEASE tool. For operations conducted with liquid or gaseous substances the fugacity is based on the vapour pressure of that substance. All relevant workplaces Amounts used Use in preparation Content in preparation Physical form Emission potential not restricted liquefied gas high The actual tonnage handled per shift is not considered to influence the exposure as such for this scenario. Instead, the combination of the scale of operation (industrial vs. professional) and level of containment/automation (as reflected in the PROCs and technical conditions) is the main determinant of the process-intrinsic emission potential. Frequency and duration of use/exposure The exposure duration is not restricted for all applicable in this scenario. Human factors not influenced by risk management The safe use of the substance has been demonstrated by assuming a standard breathing volume of 10 m³/shift for workers. If doubts exist that the actual breathing volume exceeds this value on a regular basis, a refined exposure scenario may be required. Other given operational conditions affecting workers exposure Room volume Outdoors or indoors Process temperature Process pressure All relevant workplaces not considered relevant for occupational exposure assessment of the conducted Technical conditions and measures at process level (source) to prevent release ambient Level of containment Level of segregation All relevant workplaces extracted (< 100 mbar) and tight fitting connections, closed system < 4,000 hpa For pre-cautionary reasons, it is suggested that workers leave the workplace after connecting/disconnecting if appropriate according the mode of operation. As far as technically feasible, use should be made of automated discharging respectively filling stations. Technical conditions and measures to control dispersion from source towards the worker Localised controls Level of separation Specification of LC Further information (LC) separation of workers is All relevant integrated extraction generally not required < 100 mbar - workplaces devices in the Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 11 of 22
12 Organisational measures to prevent /limit releases, dispersion and exposure Avoid inhalation or ingestion. General occupational hygiene measures are required to ensure a safe handling of the substance. These measures involve good personal hygiene practices, no eating and smoking at the workplace, unless otherwise stated below the wearing of standard working clothes and shoes. Conditions and measures related to personal protection, hygiene and health evaluation Eye protection equipment (e.g. goggles or visors) must be worn, unless potential contact with the eye can be excluded by the nature and type of application (i.e. closed process). Additionally, face protection, protective clothing and safety shoes are required to be worn as appropriate. Since sulfur dioxide has corrosive properties, the use of protective gloves is mandatory for all process steps. Respiratory equipment is only required if workers may be exposed to sulfur dioxide during Discharging and filling of. For such situations an ABEK1 mask offering an assigned protection factor of 30 is required. Reference is given to the section Selection of appropriate respiratory equipment for a more detailed description of the requirements of personal protective equipment. 2.2 Control of environmental exposure Product characteristics Gas Amounts used 80,000 tonnes/year maximum local downstream use volume (local worst-case tonnage is set equal to regional tonnage) regional tonnage sites using SO2 are numerous and wide-spread throughout the EU Frequency and duration of use 365 days Technical conditions and measures at process level (source) to prevent release All are strictly closed. Technical onsite conditions and measures to reduce or limit discharges, air emissions and releases to soil None if emission to air < 7 tonnes/year. If emission to air > 7 tonnes/year, air emission abatement system should be used (e.g. wet or dry scrubber ) No emissions to water. In case of emissions to water, ph impact on the receiving water should be avoided, e.g. by neutralizing the effluent. Conditions and measures related to municipal sewage treatment plant Not applicable Conditions and measures related to external treatment of waste for disposal No solid waste Conditions and measures related to external recovery of waste No solid waste 3. Exposure estimation and reference to its source Occupational exposure For the assessment of inhalation exposure, analogous data from the production of SO 2 were used. The risk characterisation ratio (RCR) is the quotient of the refined exposure estimate and the respective DNEL (derived no-effect level) and has to be below 1 to demonstrate a safe use. For inhalation exposure, the RCR is based on the DNEL for sulfur dioxide of 0.5 ppm (1.3 mg/m³). Method used for Method used for Inhalation exposure Dermal exposure inhalation exposure dermal exposure estimate (RCR) estimate (RCR) assessment assessment Discharging and filling of road/rail tank cars Environmental emissions analogous data 0.2 ppm (0.4) analogous data 0.03 ppm (0.07) Since sulfur dioxide has corrosive properties, dermal exposure has to be minimised as far as technically feasible. A DNEL for dermal effects has not been derived. Thus, dermal exposure is not assessed in this exposure scenario. The predicted no effect concentration PNEC of SO 2 in air is 6.65 µg/m3. Following a PECregional air of µg/m3 and a maximum RCR of 0.95, 7 tonnes/year (PEC 5.28 µg/m3) is the maximum amount of SO2 that can be released. Consequently safe use can be demonstrated when emissions to air of SO 2 do not exceed 7 tonnes/year. Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 12 of 22
13 4. Guidance to DU to evaluate whether he works inside the boundaries set by the ES Occupational exposure The downstream user (DU) works inside the boundaries set by the ES if either the proposed risk management measures as described above are met or the DU can demonstrate on his own that his operational conditions and implemented risk management measures are adequate. This has to be done by showing that they limit the inhalation and dermal exposure to a level below the respective DNEL (given that the and activities in question are covered by the PROCs listed above) as given below. If measured data are not available, the DU may make use of an appropriate scaling tool such as MEASE ( to estimate the associated exposure. It is noted that any given RPE and corresponding APFs in MEASE are related to their efficiency for protection against particles. Thus, for the current scenarios, the specific protection factor of an ABEK1 respiratory mask of 30 has to be applied manually by the user. DNEL inhalation : 0.5 ppm (1.3 mg/m3) Important note: The DU has to be aware of the fact that apart from the long-term DNEL given above, a DNEL for acute effects exists at a level of 1 ppm (2.7 mg/m³). By demonstrating a safe use when comparing exposure estimates with the long-term DNEL, the acute DNEL is therefore also covered (according to R.14 guidance, acute exposure levels can be derived by multiplying long-term exposure estimates by a factor of 2). When using MEASE for the derivation of exposure estimates, it is noted that the exposure duration may not be reduced. Environmental emissions The downstream user (DU) works inside the boundaries set by the ES if emission to air < 7 tonnes/year. If emission to air > 7 tonnes/year, air emission abatement system should be used (wet or dry scrubber ) Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 13 of 22
14 IU3: Industrial use of sulfur dioxide in the production of foundry cores (semi-closed process) Exposure Scenario Format (1) addressing uses carried out by workers 1. Title Free short title Systematic title based on use descriptor Processes, tasks and/or activities covered Industrial use of sulfur dioxide (SO 2) in the production of foundry cores (semi-closed process) SU3 (Industrial uses), SU14 PC19 (appropriate PROCs and ERCs are given in Section 2 below) Processes, tasks and/or activities covered are described in Section 2 below. 2. Operational conditions and risk management measures Involved tasks Involved PROCs Manufacture of foundry cores (semiclosed process) ERC 2 ERC 6d 2.1 Control of workers exposure discharging operations (including formulation and processing steps in closed systems) discharging operations (including formulation and processing steps in closed systems) manual operations at core shooting machines, and finishing of foundry cores 1, 8a, 8b, 9 1, 8a, 8b, 9 2, 3, 8b Formulation of preparation Industrial use of process regulators for polymerisation in produc-tion of resins, rubbers, polymers Product characteristic According to the MEASE approach, the substance-intrinsic emission potential is one of the main exposure determinants. This is reflected by an assignment of a so-called fugacity class in the MEASE tool. For operations conducted with liquid or gaseous substances the fugacity is based on the vapour pressure of that substance. Use in preparation Content in preparation Physical form Emission potential liquefied gas not restricted liquefied gas high Manufacture of foundry cores (semiclosed liquefied gas / gaseous process) Amounts used The actual tonnage handled per shift is not considered to influence the exposure as such for this scenario. Instead, the combination of the scale of operation (industrial vs. professional) and level of containment/automation (as reflected in the PROCs and technical conditions) is the main determinant of the process-intrinsic emission potential. Frequency and duration of use/exposure The exposure duration is not restricted for all applicable in this scenario. Human factors not influenced by risk management The safe use of the substance has been demonstrated by assuming a standard breathing volume of 10 m³/shift for workers. If doubts exist that the actual breathing volume exceeds this value on a regular basis, a refined exposure scenario may be required. Other given operational conditions affecting workers exposure Room volume Outdoors or indoors Process temperature Process pressure ambient < 4,000 hpa not considered relevant for occupational exposure assessment of the conducted Manufacture of ambient < 4,000 hpa foundry cores (semiclosed process) not restricted ambient Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 14 of 22
15 Technical conditions and measures at process level (source) to prevent release Level of containment Level of segregation Manufacture of foundry cores (semiclosed process) extracted (< 100 mbar) and tight fitting connections, closed system not required Technical conditions and measures to control dispersion from source towards the worker Manufacture of foundry cores (semiclosed process) Level of separation separation of workers is generally not required in the Localised controls (LC) integrated extraction devices integrated extraction devices local exhaust ventilation Organisational measures to prevent /limit releases, dispersion and exposure For pre-cautionary reasons, it is suggested that workers leave the workplace after connecting/disconnecting if appropriate according the mode of operation. As far as technically feasible, use should be made of automated discharging respectively filling stations. segregation of the emission source is not required at this workplace Specification / Efficiency of LC < 100 mbar < 100 mbar 90 % (ECETOC efficiency for PROC 2 & PROC 3) Further information Avoid inhalation or ingestion. General occupational hygiene measures are required to ensure a safe handling of the substance. These measures involve good personal hygiene practices, no eating and smoking at the workplace, unless otherwise stated below the wearing of standard working clothes and shoes. Conditions and measures related to personal protection, hygiene and health evaluation Eye protection equipment (e.g. goggles or visors) must be worn, unless potential contact with the eye can be excluded by the nature and type of application (i.e. closed process). Additionally, face protection, protective clothing and safety shoes are required to be worn as appropriate. Since sulfur dioxide has corrosive properties, the use of protective gloves is mandatory for all process steps. Respiratory equipment is required if workers may be exposed to sulfur dioxide during and Manufacture of foundry cores (semi-closed process). For such situations an ABEK1 mask offering an assigned protection factor of 30 is required. Reference is given to the section Selection of appropriate respiratory equipment for a more detailed description of the requirements of personal protective equipment. 2.2 Control of environmental exposure Product characteristics Gas Amounts used 80,000 tonnes/year maximum local downstream use volume (local worst-case tonnage is set equal to regional tonnage) regional tonnage sites using SO2 are numerous and wide-spread throughout the EU - Frequency and duration of use 365 days Technical conditions and measures at process level (source) to prevent release All are strictly closed. Technical onsite conditions and measures to reduce or limit discharges, air emissions and releases to soil None if emission to air < 7 tonnes/year. If emission to air > 7 tonnes/year, air emission abatement system should be used (e.g. wet or dry scrubber ) No emissions to water. In case of emissions to water, ph impact on the receiving water should be avoided, e.g. by neutralizing the effluent. Conditions and measures related to municipal sewage treatment plant Not applicable Conditions and measures related to external treatment of waste for disposal No solid waste Conditions and measures related to external recovery of waste No solid waste Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 15 of 22
16 3. Exposure estimation and reference to its source Occupational exposure For the assessment of inhalation exposure, measured data from the manufacture of foundry cores (semi-closed process) and analogous data from the production of SO 2 were used. The risk characterisation ratio (RCR) is the quotient of the refined exposure estimate and the respective DNEL (derived no-effect level) and has to be below 1 to demonstrate a safe use. For inhalation exposure, the RCR is based on the DNEL for sulfur dioxide of 0.5 ppm (1.3 mg/m³). Manufacture of foundry cores (semiclosed process) Method used for inhalation exposure assessment Inhalation exposure estimate (RCR) analogous data 0.2 ppm (0.4) analogous data 0.03 ppm (0.07) measured data 0.41 ppm (0.82) Method used for dermal exposure assessment Dermal exposure estimate (RCR) Since sulfur dioxide has corrosive properties, dermal exposure has to be minimised as far as technically feasible. A DNEL for dermal effects has not been derived. Thus, dermal exposure is not assessed in this exposure scenario. Environmental emissions The predicted no effect concentration PNEC of SO 2 in air is 6.65 µg/m3. Following a PECregional air of µg/m3 and a maximum RCR of 0.95, 7 tonnes/year (PEC 5.28 µg/m3) is the maximum amount of SO2 that can be released. Consequently safe use can be demonstrated when emissions to air of SO 2 do not exceed 7 tonnes/year. 4. Guidance to DU to evaluate whether he works inside the boundaries set by the ES Occupational exposure The downstream user (DU) works inside the boundaries set by the ES if either the proposed risk management measures as described above are met or the DU can demonstrate on his own that his operational conditions and implemented risk management measures are adequate. This has to be done by showing that they limit the inhalation and dermal exposure to a level below the respective DNEL (given that the and activities in question are covered by the PROCs listed above) as given below. If measured data are not available, the DU may make use of an appropriate scaling tool such as MEASE ( to estimate the associated exposure. It is noted that any given RPE and corresponding APFs in MEASE are related to their efficiency for protection against particles. Thus, for the current scenarios, the specific protection factor of an ABEK1 respiratory mask of 30 has to be applied manually by the user. DNEL inhalation : 0.5 ppm (1.3 mg/m3) Important note: The DU has to be aware of the fact that apart from the long-term DNEL given above, a DNEL for acute effects exists at a level of 1 ppm (2.7 mg/m³). By demonstrating a safe use when comparing exposure estimates with the long-term DNEL, the acute DNEL is therefore also covered (according to R.14 guidance, acute exposure levels can be derived by multiplying long-term exposure estimates by a factor of 2). When using MEASE for the derivation of exposure estimates, it is noted that the exposure duration may not be reduced. Environmental emissions The downstream user (DU) works inside the boundaries set by the ES if emission to air < 7 tonnes/year. If emission to air > 7 tonnes/year, air emission abatement system should be used (wet or dry scrubber ) Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 16 of 22
17 IU4-IU9: Industrial use of sulfur dioxide in closed or semi-closed Exposure Scenario Format (1) addressing uses carried out by workers 1. Title Free short title Systematic title based on use descriptor Industrial use of sulfur dioxide (SO 2) in the paper, sugar and starch industry, the production of pharmaceutical products, in industrial water treatment, glass coating/lubricate rollers in glass manufacture, in metal casting/mining/purification and as refrigerant agent SU3 (Industrial uses), SU4, SU6b, SU8, SU9, SU10, SU13, SU14, SU15 PC14, PC15, PC19, PC20, PC26, PC29, PC37 (appropriate PROCs and ERCs are given in Section 2 below) Processes, tasks and/or activities Processes, tasks and/or activities covered are described in Section 2 below. covered 2. Operational conditions and risk management measures Involved tasks Involved PROCs discharging operations 1, 8a, 8b, 9 discharging operations 1, 8a, 8b, 9 in closed maintenance and supervision activities at closed systems 1 in semi-closed such as: manual operations (e.g. sampling, additional dosing of fine chemicals), maintenance and use of sulfur dioxide as inert gas in metal alloy production and casting 2, 3, 4, 5, 8b, 22, 23 ERC 2 ERC 4 ERC 6a ERC 6b 2.1 Control of workers exposure Formulation of preparation Industrial use of processing aids in and products, not becoming part of articles Industrial use resulting in manufacture of another substance (use of intermediates) Industrial use of reactive processing aids Product characteristic According to the MEASE approach, the substance-intrinsic emission potential is one of the main exposure determinants. This is reflected by an assignment of a so-called fugacity class in the MEASE tool. For operations conducted with liquid or gaseous substances the fugacity is based on the vapour pressure of that substance. Use in preparation Content in preparation Physical form Emission potential liquefied gas liquefied gas not restricted liquefied gas / gaseous in closed high in semi-closed liquefied gas / gaseous Amounts used The actual tonnage handled per shift is not considered to influence the exposure as such for this scenario. Instead, the combination of the scale of operation (industrial vs. professional) and level of containment/automation (as reflected in the PROCs and technical conditions) is the main determinant of the process-intrinsic emission potential. Frequency and duration of use/exposure The exposure duration is not restricted for all applicable in this scenario. Human factors not influenced by risk management The safe use of the substance has been demonstrated by assuming a standard breathing volume of 10 m³/shift for workers. If doubts exist that the actual breathing volume exceeds this value on a regular basis, a refined exposure scenario may be required. Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 17 of 22
18 Other given operational conditions affecting workers exposure Room volume Outdoors or indoors Process temperature Process pressure in closed in semi-closed not considered relevant for occupational exposure assessment of the conducted Technical conditions and measures at process level (source) to prevent release ambient ambient not restricted not restricted Level of containment Level of segregation extracted (< 100 mbar) and tight fitting connections < 4,000 hpa < 4,000 hpa not restricted ambient For pre-cautionary reasons, it is suggested that workers leave the workplace after connecting/disconnecting if appropriate according the mode of operation. As far as technically feasible, use should be made of automated discharging respectively filling stations. in closed closed system not required in semi-closed not required not required Technical conditions and measures to control dispersion from source towards the worker in closed in semi-closed Level of separation separation of workers is generally not required in the Localised controls (LC) integrated extraction devices integrated extraction devices not required local exhaust ventilation Organisational measures to prevent /limit releases, dispersion and exposure Specification / Efficiency of LC < 100 mbar < 100 mbar na 90 % (ECETOC efficiency for PROC 2 & PROC 3) Further information Avoid inhalation or ingestion. General occupational hygiene measures are required to ensure a safe handling of the substance. These measures involve good personal hygiene practices, no eating and smoking at the workplace, unless otherwise stated below the wearing of standard working clothes and shoes. Conditions and measures related to personal protection, hygiene and health evaluation Eye protection equipment (e.g. goggles or visors) must be worn, unless potential contact with the eye can be excluded by the nature and type of application (i.e. closed process). Additionally, face protection, protective clothing and safety shoes are required to be worn as appropriate. Since sulfur dioxide has corrosive properties, the use of protective gloves is mandatory for all process steps. Respiratory equipment is required if workers may be exposed to sulfur dioxide during and in semi-closed. For such situations an ABEK1 mask offering an assigned protection factor of 30 is required. Reference is given to the section Selection of appropriate respiratory equipment for a more detailed description of the requirements of personal protective equipment. 2.2 Control of environmental exposure Product characteristics Gas, aqueous solution Amounts used 80,000 tonnes/year maximum local downstream use volume (local worst-case tonnage is set equal to regional tonnage) regional tonnage sites using SO2 are numerous and wide-spread throughout the EU - Frequency and duration of use 365 days Technical conditions and measures at process level (source) to prevent release All are strictly closed. Revision: GHS2 (UK02.1) Revision: Date: 07/2014 Page 18 of 22
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