1/44 Revision: SECTION 1: Identification of the substance/mixture and of the company/undertaking 1.1. Product identifier Substance international chemical identification: Sulphuric acid 15-99% CLP Annex VI index number: 16-2--8 EC/CAS number: 231-639-5 / 7664-93-9 REACH registration reference number: 1-2119458838-2-9 Product name/identification code: Sulphuric acid 38% / 26343 Sulphuric acid 6% / 26733 Sulphuric acid 96% / 267735 Sulphuric acid 98% / 263448 1.2. Relevant identified uses of the substance or mixture and uses advised against Relevant identified uses: Industrial uses: Intermediate in manufacture of inorganic and organic chemicals incl. fertilizers, Mixing, preparation and repackaging of sulphuric acid. Uses advised against: Not known. 1.3. Details of the supplier of the safety data sheet Manufacturer/Non-EU supplier: Petrokemija d.d., Aleja Vukovar 4, HR-4432 Kutina, Croatia Phone number: 385 44 647 122, e-mail: tmg@petrokemija.hr EU supplier (Only representative): Petrokemija d.o.o., Ljubljanska Cesta 8, SI-8 Novo Mesto, Slovenia. Phone number: 386 5 974 19, e-mail: damir.pirsic@petrokemija.si 1.4. Emergency telephone numbers Emergency (EU, Croatia): 112 Emergency health response (Croatia): 385 ()1 2348 342 SECTION 2: Hazards identification 2.1. Classification of the substance or mixture 2.1.1. Classification according to Regulation (EC) No 1272/28 [CLP/GHS] Concentration (% w/w) Hazard classes and Hazard categories Hazard Statements Full text of Hazard Statements 15 Skin Corr. 1 A H314 Causes severe skin burns and eye damage 2.1.2. Classification according to Directive 67/548/EEC [DSD] Concentration (% w/w) Classification R phrases Full text of R phrases 15 C; R35 Corrosive;. R35 Causes severe burns
2/44 Revision: 2.2. Label elements Labelling according to Regulation (EC) No 1272/28 [CLP/GHS] Hazard pictograms: GHS5: corrosion Signal word: Danger Additional labelling requirements (CLP supplemental hazard statement): EUH71: Corrosive to the respiratory tract. Hazard statements: H314: Causes severe skin burns and eye damage. Precautionary statements: P26 Do not breathe mist/fume/vapours P28 Wear protective gloves/protective clothing/eye protection/face protection. P31+P33+P331 IF SWALLOWED: rinse mouth. Do NOT induce vomiting. P33+P361+P353 IF ON SKIN (or hair): Remove/Take off immediately all contaminated clothing. Rinse skin with water/shower. P35+P351+P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. P39 If exposed or if you feel unwell: P31 Immediately call a poison center or doctor/physician. 2.3. Other hazards None. SECTION 3: Composition/information on ingredients 3.1. Substances Name CLP Annex VI Index number Degree of purity (w/w) Sulphuric acid % 16-2--8 > 98% Description of the substance: monoconstituent substance, industrial chemical, aqueous solution 15-99% IUPAC name: sulphuric acid Molecular formula: H 2 SO 4 SECTION 4: First aid measures 4.1. Description of first aid measures General notes: Give first aid and obtain medical attention immediately. First aiders should be adequately protected (see Section 7.Handling and storage ). Remove affected person from further exposure. Ensure that eyewash facility and safety showers are provided close to the work place.
3/44 Revision: Following extensive contamination, even in the case of dilute acid, use a deluge shower for decontamination if possible; otherwise rinse with copious amounts of water, using any means available. Lay the casualty down in a quiet place and protect him against hypothermia. Always take care for rapid medical treatment. Ingestion: Do not induce vomiting. If the person is conscious, wash out mouth with water and give 1-2 glasses water to drink. During spontaneous vomiting hold the head of the casualty low with the body in a prone position in order to avoid penetration of the vomit into the airways. Do not try to neutralize with bases and do not apply charcoal. Following ingestion of small amounts of the acid, immediate application of a liquid is recommended in order to achieve a rinsing effect. Obtain medical attention. Skin contact: Carry out the following measures as soon as possible: remove casualty's contaminated clothing, rinse skin areas affected under running water for 1 minutes, Seek medial assistance if irritation persists. Eye contact: Rinse the affected eye with widely spread lids for 1 minutes under running water whilst protecting the unimpaired eye. Point the mild water jet directly into the eye in order to remove the acid residues as soon and as completely as possible. Then immediately transport the casualty to an eye doctor. Continue rinsing during the transport. Inhalation: Move the injured person to fresh air, lay the casualty down in a quiet place and protect him against hypothermia. For difficulty in breathing have the casualty take a semi-upright position. As soon as possible repeatedly have the casualty deeply breath a glucocorticoid inhalation spray in. In serious cases it can be necessary. Administer oxygen if competent person is available. If the casualty has stopped breathing give mouth to nose resuscitation. If this is not possible use mouth to mouth resuscitation. In the case of cardiac arrest (lack of heart beat or pulse) immediately apply heart lung resuscitation. The protection of the vital functions (heartbeat and respiration without assistance) takes priority over every other activity. Call a physician to the site of the accident. Advice to first aid responders: First aid personnel must avoid contact with sulphuric acid. Personal protection equipment for first aid responders is recommended (see Section 7.1 and Section 8.2). Avoid skin contamination and breathing of sulphuric acid fumes or mist. Rinse contaminated clothes with plenty of water. 4.2. Most important symptoms and effects, both acute and delayed Ingestion: Painful chemical burns to the mucous membranes due to concentrated acid - dark discoloration of tissues contacted; mostly vomiting of dark masses; acute reactions to the heart/circulatory system as a consequence of chemical burns (collapse, shock, cardiac arrest); systemically possibly acidosis, lactacidosis -> hemolysis/ consequences of hemolysis -> disturbance of the kidney function, possible liver damage; late sequelae possibly even after weeks (in particular strictures and stenosis in the digestive system). Skin: Chemical burns to be expected at concentrations of more than 1 %; rapidly appearing corrosive injury like thermal burns (initially bleaching, then brown up to black discoloration, later ulceration, purulent inflammation); shock reaction. Eyes: Pain, blepharospasm; irritation up to serious chemical burns, dependent on the concentration: danger of permanent opacity and ulceration of the cornea, loss of the eyeball; serious damage to the cornea also possible by aerosols.
4/44 Revision: Inhalation: Burning in the nose and throat, sneezing, narrowness in the chest, substernal pain, coughing (blood), dyspnoea, danger of laryngeal spasm, glottic edema, function disturbances/damage to the lung (abscess formation possibly only after a delay of several days. 4.3. Indication of any immediate medical attention and special treatment needed Systemically possibly acidosis, lactacidosis, hemolysis. Consequences of hemolysis: disturbance of the kidney function, possible liver damage, late sequelae possibly even after weeks (in particular strictures and stenosis in the digestive system). Prophylaxis for shock and tetanus as needed, further treatment in hospital. In hospital, consideration should be given to drawing off content of the stomach via a thin, flexible tube (on an endoscopical base). The decision should be made dependent on the poisoning situation/findings (watch for a danger of perforation, no gastrolavage). Rest and medical observation are therefore essential. SECTION 5: Firefighting measures 5.1. Extinguishing media Suitable extinguishing Media: Substance is incombustible. Select fire fighting measures according to the surrounding conditions. Use dry chemical powder, carbon dioxide, sand. Extinguishing media not to be used : Do not use water. 5.2. Special hazards arising from the substance or mixture Ambient fire may liberate hazardous vapours or decomposition products - sulphuric oxides. 5.3. Advice for firefighters Fire fighting: Use water sprays to cool surrounding containers and structures. Avoid direct water impingement on strong acid. Avoid disposal of contaminated fire fighting water to the environment. Prevent spillage from entering drains or waterways. Equipment should be thoroughly decontaminated after use. Special protective equipment for firefighters: Wear acid-resistant complete protective clothing including selfcontained breathing apparatus. Fire fighter's clothing conforming to European standard EN469 provides a basic level of protection for chemical incidents. SECTION 6: Accidental release measures 6.1. Personal precautions, protective equipment and emergency procedures 6.1.1. For non-emergency personnel Protective equipment: Wear suitable protective equipment. Wear full protective clothing including respiratory protection. Emergency procedures: Avoid skin and eye contact and vapour inhalation. Ventilate the area to disperse vapour if necessary. Keep unprotected persons away. 6.1.2. For emergency responders Use personal protection equipment and respiratory protection. Portable safety shower and eyewash facilities may be needed. Use a neutralising agent or chemical absorbent and substantial amounts of water for large spill.
5/44 Revision: 6.2. Environmental precautions Contain spillage where possible and safe to do so. Avoid the contamination of watercourses. Prevent run-off into drains and waterways. Inform appropriate authority in case of accidental contamination of watercourses or drains (see 1.4.). 6.3. Methods and material for containment and cleaning up 6.3.1 For containment Absorb with liquid-binding material (sand, diatomite, acid binders, universal binders, sawdust). Use NaOH (lye, caustic soda), Na 2 CO 3 (sodium carbonate, soda ash) and NaHCO 3 (sodium bicarbonate, baking soda) as neutralising agents. 6.3.2 For cleaning up Large spill: Use a tool to scoop up solid or absorbed material and place into an appropriately labelled waste container. Pump large amounts of the spilled liquid into containers suitably labelled for disposal. Cautiously neutralize remainder with neutralizing agent. Then wash away with plenty of water. Small spill: Inorganic acids and their anhydrids are, if necessary, first dilute or hydrolised by stirring cautiously in ice water. Then are neutralised withneutralising agent; check ph value. Place in collecting containers for salt solutions, adjust for a ph value of 6-8. Collection vessels must be clearly labelled with a systematic description of their contents and with the hazard symbols. Store the vessels in a well-ventilated location. Entrust them to the appropriate authorities for disposal. 6.3.3 Other information Do not spray water directly on the leak or sulphuric acid container. Increase ventilation and allow fumes to vent to a safe area. 6.4 Reference to other sections For protective equipment see Section 8.2 Exposure controls and Exposure scenarios, section 3.1. SECTION 7: Handling and storage 7.1. Precautions for safe handling Protective measures: Avoid skin and eye contact and inhalation of vapours; Wear eye and hand protection.; Wear full protective equipment where there is a risk of leaks or splashes.; Use acid resistant utensils; Avoid splashing, Provide adequate ventilation; When diluting concentrated acid, allways add acid to water (not water to acid) slowly and with great care; When handling excessive amounts of the substance an emergency shower and an eye bath are required - these locations must be signposted clearly. Measures to prevent fire: Keep away from incompatible substances. Advice on general occupational hygiene: Take care to maintain clean working place; Do not permit smoking in the storage area; Contaminated clothes must be exchanged and cleaned carefully; Before cleaning clothes rinse thoroughly first in water. Reference to other sections: For protective equipment see Section 8.2 and Exposure scenarios, section 3.1.
6/44 Revision: 7.2. Conditions for safe storage, including any incompatibilities Technical measures and storage conditions: Store in cool, dry, well ventilated area, away from heat, ignition source and direct sunlight, separated from combustible and reducing substances, bases, organics food and feedstuffs; Keep away from incompatible substances; Keep container tightly closed.; Containers and pipelines have to be labelled clearly and permanently. Packaging materials: Generally resistant: Glass, Enamel. At lower temperatures: Polyethylene PE, Polyvinyl chloride, Polypropylene PP Unsuitable materials: Non-noble metals Requirements for storage rooms and vessels: Install sufficiently large collection rooms (depressions, walls, or stable freestanding walls), The floor must be acid resistant. Install a floor drain. Further information on storage conditions: Substance is hygroscopic. Exothermic reaction with water. The substance should not be stored with substances with which hazardous chemical reactions are possible (information on incompatible substances in section 1.5.). Avoid collocated storage with the following substances: pharmaceuticals, foods, and animal feeds including additives; infectious, radioactive und explosive substances; strongly oxidizing substances of storage class 5.1.; organic peroxides and self reactive substances; other explosive substances of storage class 4.1; spontaneously flammable substances; substances liberating flammable gases in contact with water; ammonium nitrate and preparations containing ammonium nitrate. 7.3. Specific end use(s) None. SECTION 8: Exposure controls/personal protection 8.1. Control parameters 8.1.1. Occupational exposure limits European Union Limit value - Eight hours Limit value - Short term ppm mg/m³ ppm mg/m³,5 thoracic fraction Legal basis Directives 91/322/EEC, 2/39/EC, 26/15/EC 8.1.2. DNEL/PNEC values DNELs workers Route of exposure Accute effects - local Accute effects - systemic Chronic effects - local Chronic effects - systemic Inhalation,1 mg/m³ No hazard identified,5 mg/m³ No hazard identified Dermal The substance is corrosive (corrosivity: > 15%). No hazard identified The substance is corrosive. Corrosivity: > 15%.. No hazard identified
7/44 Revision: DNELs general population (consumers) Route of exposure Accute effects - local Accute effects - systemic Chronic effects - local Chronic effects - systemic Oral No data No hazard identified No hazard identified No hazard identified Inhalation No hazard identified No hazard identified,65 mg/m³ No hazard identified Dermal Corrosivity: > 15% No hazard identified Corrosivity: > 15% No hazard identified Significant additional inhalation exposure (over and above background levels resulting from other sources including combustion of fossil fuels) of the general population is not predicted; DNEL/DMEL values are therefore not proposed. Dermal exposure of the general population is not predicted. Oral exposure of the general public is not relevant and in any case would be indistinguishable from naturally occurring ionic species. PNEC exposure route environmental protection target Fresh water Freshwater sediment Marine water Marine sediments Food chain Microorganisms in sediment treatment Soil (agricultural) Air,25 mg/l 2 x 1-3 mg/kg wwt.25 mg/l 2 x 1-3 mg/kg wwt No hazard identified 8,8 mg/l No hazard identified No hazard identified 8.2. Exposure controls The Exposure scenario containing that information is attached to this safety data sheet. 8.2.1. Key details of workers exposure control Suitable PPE that should be used to prevent dermal contact for workers would be acid resistant clothing, helmets, gloves, goggles and boots. Workers involved in use, handing, sampling and transfer of materials are trained in the procedures and protective equipment is intended to cope with the worst case scenario, in order to minimise exposure and risks. Skin protection: Depending on the risk, wear a tight, long apron and boots or suitable chemical protection clothing. The protection clothing should be acid resistant. Use protective gloves: Suitable materials for protective gloves (5% w/v sulphuric acid, permeation time 8 hours): Polychloroprene - CR (,5 mm); Nitrile rubber/nitrile latex - NBR (,35 mm); Butyl rubber - Butyl (,5 mm); Fluoro carbon rubber - FKM (,4 mm); Polyvinyl chloride - PVC (,5 mm). Unsuitable materials for protective gloves because of degradation, severe swelling or low permeation time: Natural rubber/natural latex NR. Textile or leather gloves are completely unsuitable. Suitable for protective gloves (96% w/v sulphuric acid, permeation time 8 hours): Fluoro carbon rubber - FKM (,4 mm). Protective gloves of the following materials should not be worn longer than 2 hours continually (Permeation time 2 hours): Butyl rubber - Butyl (,5 mm). Unsuitable materials for protective gloves because of degradation, severe swelling or low permeation time: Natural rubber/natural latex NR; Polychloroprene CR; Nitrile rubber/nitrile latex NBR; Polyvinyl chloride PVC.
8/44 Revision: Respiratory protection: Particle filter P2 or P3, colour code white. Use insulating device for concentrations above the usage limits for filter devices, for oxygen concentrations below 17% volume, or in circumstances which are unclear. Eye protection: Wear chemical safety goggles. If the face is at risk as well as the eyes, a protective shield must also be worn. Wear a full mask if vapours or aerosols that may injure the eyes arise. 8.2.2. Environmental exposure controls Any gas displaced from containers is conducted via pipeline to be processed i.e. removed and scrubbed and /or filtered. Waste gas emissions are scrubbed and may also then be diverted to the wastewater stream. Liquid wastes are treated (neutralisation to neutral ph) prior to emission to remove any sulphuric acid in the waste water and sludge from the waste water treatment plant is sent for incineration or landfill and is not used for agricultural spreading. This precludes any contamination of soil by sludge spreading. Waste water treatment is usually carried out by neutralisation followed by flocculation or decantation. SECTION 9: Physical and chemical properties 9.1. Information on basic physical and chemical properties Property Unit Value Reference conditions Appearance Odour colorless liquid odourless Odour threshold ppm Not applicable ph < 1 2 C Melting point / freezing point C Initial boiling point and boiling range Flash point C No data availlable Evaporation rate Flammability Upper/lower flammability or explosive limits Vapour pressure Vapour density C standard temperature (2 C) and pressure (113 hpa) 1.4 to 1.9 1% sulphuric acid -36,78 65% sulphuric acid 31-335 98% sulphuric acid,113 hpa 36 77% sulphuric acid,113 hpa No data availlable Non flammable % Non flammable Pa Inorganic substance, the flash point needs not to be determined. 6 9% sulphuric acid, 2 C 214 65% sulphuric acid, 2 C No data availlable Relative density g/cm 3 1.81-1.83 9-1% sulphuric acid, 2 C Solubility(ies) g/l Miscible Water, 2 C Partition coefficient: n-octanol/water No data availlable Not relevant for ionisable substances
9/44 Revision: Auto-ignition temperature C Not sensitive to self - ignition. Decomposition temperature C No data availlable The substance is a liquid and is nonflammable. Viscosity mpa s 22,5 95% sulphuric acid, 2 C Explosive properties Oxidising properties 9.2. Other information Dissociation constant: pka = 1,92 SECTION 1: Stability and reactivity 1.1. Reactivity Non explosive Does not meet the criteria as an oxidiser Dissociates if heated above boiling point. Decomposition products: sulphur trioxide, water. Aqueous solution reacts acidic. Acts oxidizing with increasing temperature. Concentrated sulphuric acid can destroy organic substances by dehydration under charring. 1.2. Chemical stability Non-combustible liquid. The substance is stable under normal ambient and anticipated storage and handling conditions. Mixable with water. 1.3. Posibility of hazardous reactions Dissociates if heated. Decomposition products: sulphur trioxide, water. Applies only to concentrated sulphuric acid: Risk of explosion in contact with combustible substances, bromates, carbides, chlorates; The substance can react dangerously with reducing agents, metals, highly flammable solvents, alkaline earth oxides, organic substances. 1.4. Conditions to avoid Direct heat and high temperature to avoid release of sulphuric acid oxides and damaging of container. Avoid contact with incompatible materials. Exothermic reaction with water. 1.5. Incompatible materials The substance can react dangerously with: combustible substances, bromates, carbides, chlorates, potassium, perchlorates, reducing agents, metals, metal carbides, highly flammable solvents, concentrated ammonia, alkaline earth oxides, organic substances. 1.6. Hazardous decomposition products When heated sulphuric oxide toxic gases may be released.
1/44 Revision: SECTION 11: Toxicological information 11.1. Information on toxicological effects 11.1.1. Acute toxicity Acute toxicity Routes of exposure Inhalation Oral/dermal OECD 41 Method/species Effective dose Results equivalent or similar to OECD Guideline 43 / rat (Fischer 344) male/female LC5 (inhalation): 375 mg/m³ air LD5 (oral): 214 mg/kg bw Reason for no classification: Conclusive but not sufficient for classification. 11.1.2. Skin corrosion/irritation Skin corrosion/irritation Routes of exposure Respiratory tract Skin Method/species Effective dose Results study scientifically unjustified study scientifically unjustified No data available No data available The classification criteria are not met. The effects of sulphuric acid following inhalation are entirely due to local irritation of the respiratory tract. REACH (column 2, Annex VIII, section 8.5): an acute toxicity test does not generally need to be conducted if the substance is classified as corrosive to the skin. Classification: Corrosive Classification: Corrosive Justification for classification: Sulphuric acid is listed on Annex VI of CLP regulation (Corrosive classification). 11.1.3. Serious eye damage/irritation Serious eye damage/irritation Routes of exposure Eye Method/species Effective dose Results study scientifically unjustified No data available Classification: Corrosive Reason for no classification: Sulphuric acid is listed on Annex VI of CLP regulation (Corrosive classification). Studies of eye irritation are therefore not justified scientifically and are precluded on grounds of animal welfare. Experience from human exposure also indicates that the substance is corrosive.
11/44 Revision: 11.1.4. Respiratory or skin sensitization Respiratory or skin sensitization Routes of exposure Skin Method/species Effective dose Results study scientifically unjustified No data available Inhalation No data available No data available Not sensitising Not sensitising. Corrosive to the skin. Extensive occupational exposure to sulphuric acid over many years has not resulted in any reports of skin sensitisation Reason for no classification: No classification is proposed for skin sensitisation or respiratory sensitisation based on theoretical considerations and in the absence of any findings in exposed humans following occupational use over a long period of time. 11.1.5. Germ cell mutagenicity Germ cell mutagenicity Routes of exposure Oral Method/species Effective dose Results AMES - test equivalent or similar to OECD471 Reason for no classification: conclusive but not sufficient for classification. 11.1.6. Carcinogenicity Justification for non classification: Inconclusive data for classification. 11.1.7. Reproductive toxicity Reproductive toxicity Routes of exposure Inhalation OECD 414 Method/species Effective dose Results Reason for no classification: conclusive but not sufficient for classification. 11.1.8. STOT-single exposure Reason for no classification: conclusive but not sufficient for classification. 11.1.9. STOT-repeated exposure Reason for no classification: inconclusive data for classification. 11.1.1. Aspiration hazard Reason for no classification: data lacking. No classification is proposed for genotoxicity. NOAEC: 19,3 mg/m 3 No classification is required
12/44 Revision: 11.1.11. Symptoms See subsection 4.2. SECTION 12: Ecological information 12.1. Toxicity 12.1.1. Toxicity to aquatic organisms Acute (short-term) toxicity Acute fish toxicity Acute aquatic invertebrate toxicity Acute algae toxicity Sediment organisms Effect dose (Exposure time) / Test material LC5 (96h): > 16 mg/l test mat. (nominal) EC5/LC5 for (48 h): > 1 mg/l test mat. (nominal) based on: mobility EC5 (72 h): > 1 mg/l test mat. (nominal) based on: growth rate No data Species / Method Lepomis macrochirus (bluegill sunfish) / freshwater static 96-hour LC5 Daphnia magna freshwater static OECD Guideline 22 Desmodesmus subspicatus (algae) freshwater static OECD Guideline 21 No data Evaluation The 96 hour LC5 for sulphuric acid to bluegill sunfish was determined to be between ph 3.25 and 3.5, equivalent to 16 to 28 mg/l. There were no observed toxic effects on Daphnia at the limit concentration of 1 mg/l after 48 hours. No terrestrial exposure is expected Results Sulphuric acid will not cause adverse effects to fish at ph range 3,5-9. Sulphuric acid will not cause adverse effects to daphnids at environmentally relevant ph values. Sulphuric acid will not cause adverse effects to algae. The CSA indicated no concern for the sediment compartment. Chronic (long-term) toxicity Fish Aquatic invertebrates Effect dose (Exposure time) / Test material EC1/LC1 or NOEC for freshwater fish:.25 mg/l EC1/LC1 or NOEC for freshwater invertebrates:.15 mg/l Species / Method Jordanella floridae/ flowthrough Tanytarsus dissimilis Evaluation The no-observed effect concentration for T. dissimilis (reproduction) exposed to sulphuric acid was observed to be ph 5.5, equivalent to.15 mg/l. Results Algae No data No data No data No data The CSA indicated no concern for fish. Reproduction and mortality were not impaired between ph 5,5 and 6,. Hazards to the aquatic environment - reason for no classification: conclusive but not sufficient for classification 12.1.2. Toxicity to terrestrial organisms No terrestrial exposure is expected.
13/44 Revision: 12.1.3. Toxicity to aquatic micro-organisms in sewage treatment systems Toxicity to aquatic micro-organisms Effect dose (Exposure time) / Test material Species / Method Evaluation Results Activated sludge - freshwater NOEC (37 d): ca. 26 g/l, test mat. (nominal) based on: respiration rate activated sludge, freshwater, static Non-standard study investigating effects on bacteria in sewage sludge Read across: The toxic effects of sulphuric acid will be driven by ph. Bacteria were shown to be relatively insensitive to the effects of acid ph under the conditions of this study (ph 5,34-6,61). Sulphate is inherently non-toxic to bacteria and is used by strains of anaerobic bacteria as an energy source. 12.2. Persistence and degradability Abiotic degradation Half-time Method Evaluation Remark Hydrolysis At a conc. of.1 mol/l in water, nitric acid is dissociated for about 93%. Study scientifically unjustified Biodegradation Degradation rate (%) Time (d) Method Evaluation Remark Inorganic substance (REACH Annex VII column 2). Study scientifically unjustified 12.3. Bioaccumulative potential Sulphuric acid is not considered to have bioaccumulative potential. Sulphuric acid dissociates readily to hydrogen (hydronium) ions and sulphate ions, both of which are ubiquitous in biological systems. 12.4. Mobility in soil As sulphuric acid is extremely soluble in water, exposure to soil is deemed irrelevant. 12.5. Results of PBT and vpvb assessment According to the results of its assessment, sulphuric acid is not a PBT or a vpvb. 12.6. Other adverse effects Not known.
14/44 Revision: SECTION 13: Disposal considerations 13.1. Waste treatment methods 13.1.1. Product/ packaging disposal Dispose of in accordance with relevant official national and local regulations. Final decisions on the appropriate waste management method, in line with regional, national and European legislation, and possible adaptation to local conditions, remains the responsibility of the waste treatment operator. Waste code/ waste designations according to LoW European waste code: 6 1 1* (sulphuric acid and sulphurous acid) 13.1.2. Waste treatment-relevant information Product waste: Mix and neutralize carrefully with lime and/or soda ash. Contaminated packaging: Dispose to an approved waste disposal facility. 13.1.3. Sewage disposal-relevant information Do not discharge into drains or sewage system. 13.1.4. Other disposal recommendations Do not dispose of with other industrial or household waste (see section 1.5). SECTION 14: Transport information 14.1. UN number Concentration (w/w) 51% 2796 > 51% 183 14.2. UN proper shipping name Concentration (w/w) 51% UN number UN proper shipping name with not more than 51% acid or BATTERY FLUID, ACID > 51% with more than 51% acid 14.3. Transport hazard class(es) ADR/RID/ADN/IMDG/ICAO/IATA: Class 8 14.4. Packing group ADR/RID/AND/IMDG/ICAO/IATA: PG II
15/44 Revision: 14.5. Environmental hazards ADR, RID, ADN, IMDG, ICAO/IATA It is not environmentally hazardous; ADN hazardous to the aquatic environment (N3); IMDG It is not marine pollutant. 14.6. Special precautions for user ADR Transport category: 2 Tunnel restriction code: (E) Label: 8 Classification code: C1 Hazard identification No.: 8 ADN Label: 8 Special equipment: PP, EP Classification code: C1 Dangers: 8+N3 Additional requirements/remarks: 8, 22, 3, 34 RID Transport category: 2 Label: 8 Classification code: C1 Hazard identification No.: 8 ICAO/IATA Label: 8 Cargo IMP Code: RCM Passenger and Cargo Aircraft: EQ: E2; Ltd Qty:,5 l/pkg; Pkg Inst: Y84 Max Net Qty/Pkg: 1 l; Pkg Inst: 851 Cargo Aircraft only: Pkg Inst: 855; Max Net Qty/Pkg: 3 l ERG Code: 8L IMDG Concentration (w/w) 51% > 51% Special precautions for user Ship stowage and segregation: Category B. EmS: F-A, S-B Segregation group 1: Acids Ship stowage and segregation: Category C. For steel drums, category B. EmS: F-A, S-B Segregation group 1: Acids 14.7. Transport in bulk according to Annex II of MARPOL 73/78 and the IBC Code: Product name: Sulphuric acid Pollution Category (according to MARPOL Annex II): Y Ship type (according to IBC Code): 3 Specific and operational requirements (according to IBC Code): 15.11, 15.16.2, 15.19.6 SECTION 15: Regulatory information 15.1. Safety, health and environmental regulations/legislation specific for the substance or mixture Regulation (EC) No 197/26; Commission regulation (EU) No 453/21, Annex I, amending Regulation (EC) No 197/26; Council Directive 67/548/EEC; Regulation (EC) No 1272/28; Commission directive 26/15/EC, Council directive 91/689/EEC; Directive 28/98/EC; Directive 98/24/EC; Recommendations on the transport of dangerous goods, Model Regulations: ADR, ADN, RID, IMDG, ICAO/IATA.
16/44 Revision: 15.2. Chemical safety assessment In accordance with Article 14 of Regulation EC No 197/26 a Chemical Safety Assessment has been carried out for sulphuric acid. Exposure scenarios are attached to the extended Safety data sheet. SECTION 16: Other information 16.1. Indication of changes to the previous revision First issue according to Regulation (EC) No 197/26; classification and labbelling according to CLP Regulation; REACH registration number. 16.2. Abbreviations and acronyms ADR - Accord européen sur le transport des marchandises dangereuses par Route (European Agreement concerning the International Carriage of Dangerous Goods by Road) CAS No - Chemical abstract service index number CLP - Calssification labelling and packaging CSA - Chemical safety assessment DMEL - Derived minimal effect level DNEL - Derived no effect level EEC - European Economic Community EC - European Commission EC No - European Commission number GHS - Globally harmonized system of classification and labelling of chemicals IMDG - International maritime code for dangerous goods IATA - International Air Transport Association ICAO - International Civil Aviation Organization IOEL - Indicative occupational exposure limit LC5 - Median lethal concentration LD5 - Median lethal dose NOAEC - No observed adverse effect concentration NOAEL - No observed adverse effect level. NOEC - No observed effect concentration OEL - Occupational exposure limit PBT - Persistent bioaccumulative and toxic PNEC - Predicted no effect concentration PPE - Personal protective equipment RCR Risk characterisation ratio REACH - Registration, evaluation authorisation and restriction of chemicals RID - Règlement international concernant le transport des marchandises dangereuses par chemin de fer (Regulations Concerning the International Transport of Dangerous Goods by Rail) STOT - Specific target organ toxicity vpvb - Very persistent and very bioaccumulative IUPAC The International union of pure and applied chemistry Sectors of Use: SU3: Industrial uses: Uses of substances as such or in preparation at industrial sites SU4: Manufacture of food products SU6b: Manufacture of pulp, paper and paper products SU8: Manufacture of bulk, large scale chemicals (including petroleum products) SU9: Manufacture of fine chemicals SU1: Formulation [mixing] of preparations and/or re-packaging (excluding alloys) SU14: Manufacture of basic metals, including alloys Product Categories: PC19: Intermediate Process Categories: PROC1: Use in closed process, no likelihood of exposure
17/44 Revision: PROC2: Use in closed, continuous process with occasional controlled exposure (including sampling and maintenance) PROC3: Use in closed batch process (synthesis or formulation) PROC4: Use in batch and other process (synthesis) where opportunity for exposure arises PROC5: Mixing or blending in batch processes for formulation of preparations and articles (multistage and/or significant con-tact) PROC8a: Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at non-dedicated facilities PROC8b: Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities PROC9: Transfer of substance or preparation into small containers (dedicated filling line, including weighing) Environmental Release Categories: ERC1: Manufacture of substances ERC2: Formulation of preparations ERC6a: Industrial use resulting in manufacture of another substance (use of intermediates) 16.3. Further information Safety phrases relevant to Sulphuric Acid 2-5%: S1/2 - keep locked up and out of reach of children S26 - in case of contact with eyes, rinse immediately with plenty of water and seek medical advice S3 - never add water to this product S45 - in case of accident or if you feel unwell, seek medical advice immediately (show the label where possible) contains: Exposure Scenario 1: Production of sulphuric acid Exposure Scenario 2: Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers Exposure Scenario 3: Mixing, preparation and repackaging of sulphuric acid Note: The data given here is based on current knowledge and experience. The purpose of this Safety Data Sheet is to describe the product in terms of their safety precautions. However, it shall not constitute or imply a guarantee concerning composition, properties of performance, and shall not establish a legally valid contractual relationship.
Exposure Scenario 1: Production of sulphuric acid 18/44 Revision: 1. Title of exposure scenario 1.1. Free short title Production of sulphuric acid. 1.2. Systematic title based on use descriptor Sectors of Use Product Categories Process Categories Environmental Release Category Not applicable Not applicable PROC1; PROC2; PROC3; PROC4; PROC8a; PROC8b; PROC9 ERC1 1.3. Description of activities and processes covered in the exposure scenario Sulphuric acid is most commonly manufactured from sulphur (obtained from refining of crude oil) or from sulphurcontaining gas released from high temperature processes such as metal smelting or burning fossil fuels. Sulphuric acid may also be manufactured as a result of sulphur-capture pollution control systems. Several processes may be used to produce sulphuric acid however, the most typical industrial process is the contact process. Though there are several other processes that are used to manufacture sulphuric acid the contact process is by far the most common. All of other processes are, like the contact process, highly contained, and are classed as PROC 1, ERC 1. As such the exposure assessment for the contact process will stand for the other processes also. The produced sulphuric acid may then be diluted with water or steam condensate to give a variety of commercial concentrations: 25% - 1%. 2. Operational conditions and risk management measures 2.1. Control of workers exposure 2.1.1. Product Characteristic Type of product Physical state of product Substance as such Liquid Concentration of substance in product 25-1% 2.1.2. Frequency, duration and amounts of use/exposure Use amount per worker [workplace] per day Duration per day at workplace [for one worker] No data The product is in liquid form in a sealed tank container. Worker exposure considered to be negligible due to the specialised systems and closed nature of the production process. 8 h/d Standard number of hours in one work day Frequency at workplace 22 d/y Standard number of work days per year
Exposure Scenario 1: Production of sulphuric acid 19/44 Revision: Other determinants related to duration, frequency and amount of use Intermittent contact is expected These tasks rarely take a full 8 hours per day so worst case is assumed. 2.1.3. Other given operational conditions affecting workers exposure Not known. 2.1.4. Workers exposure factors not influenced by risk management Respiration volume and skin contact under conditions of worker uses Respiration volume under conditions of use Skin contact area with the substance under conditions of use 1 m 3 /d Default value for a worker breathing for a 8 h work day in RIP 3.2. 48 cm 2 (ECETOC default) Due to the corrosive nature of sulphuric acid dermal exposure is not considered relevant for risk characterisation as it must be prevented in all cases. 2.1.5. Technical conditions and measures at process level (source) to prevent release Use of sulphuric acid involves special equipment and high integrity contained systems with little or no potential for exposure. Containment plus good work practice is required; handling of sulphuric acid involves special equipment and controlled systems with little or no potential for exposure. Pipelines and vessels are sealed. 2.1.6. Technical conditions and measures to control dispersion from source towards the worker Local exhaust ventilation if required. Facilities involved in the production and uses of sulphuric acid are usually housed outdoors. Any gas displaced from containers is conducted via pipeline to be processed i.e. removed and scrubbed and/or filtered. Containment and local exhaust ventilation Containment plus good work practice required Local exhaust ventilation if required Effectiveness: Unknown Effectiveness: Unknown 2.1.7. Organisational measures to prevent/limit releases, dispersion and exposure Production and handling of sulphuric acid involves special equipment and contained systems with little or no potential for exposure. Facilities involved in the production and uses of sulphuric acid are usually housed outdoors. Workers generally operate in a separate control room, with no direct contact to the installations housing the material. Workers involved in sampling and transfer of materials to road tankers are trained in the procedures and protective equipment is intended to cope with the worst case scenario, in order to minimise exposure and risks.
Exposure Scenario 1: Production of sulphuric acid 2/44 Revision: 2.1.8. Conditions and measures related to personal protection Workers wear protective chemical resistant clothing (face/eye protection, helmet, anti-acid gloves, boots and protective overall). Where required respiratory protection is worn (for example P3 filters). A safety shower is required nearby in case of accidental spillage. Personal protective equipment (PPE) Type of PPE (gloves, respirator, face-shield) 2.2. Control of environmental exposure 2.2.1. Product Characteristic Effectiveness: Unknown Production and handling of sulphuric acid involves special equipment and contained systems with little or no potential for exposure. Facilities involved in the production and uses of sulphuric acid are usually housed outdoors. Any gas displaced from containers is conducted via pipeline to be processed i.e. removed and scrubbed and /or filtered. Sulphuric acid may be diluted with water to produce a variety of concentrations for industrial use. The viscosity of sulphuric acid is dependent on concentration and temperature. A viscosity of 22.5 cp (.225 Pa s; 22.5 mpa s) is reported for 95% sulphuric acid at 2 degrees Celsius. 2.2.2. Frequency, duration and amounts of use/exposure Annual amount used per site 1 2 t/y Worst case for production site Emission days per site Up to 365 d/y Estimate number of emission days, based on continuous production For additional information see section 2.1.2. 2.2.3. Other given operational conditions affecting environmental exposure Not known 2.2.4. Environmental factors not influenced by risk management Conditions leading to dilution of initial release related to environment Discharge volume of sewage treatment plant Available river water volume to receive the emissions from a site 2 m 3 /d EUSES default value for standard local STP 2 m 3 /d Standard ERC flow rate leading to a 1 fold dilution in receiving waters.
Exposure Scenario 1: Production of sulphuric acid 21/44 Revision: 2.2.5. Technical conditions and measures at process level (source) to prevent/limit release environmental exposure Production and use of sulphuric acid may involve special equipment and high integrity contained systems with little or no potential for exposure. 2.2.6. Technical conditions and measures to control dispersion from source towards the environment Exhaust gasses can be filtered and scrubbed; typically this removes >99% of sulphur oxides. The outflow is continually analysed for SO 2 content. Environmental emissions are limited by designated waste treatment process designed to limit environmental exposure to all relevant compartments. Waste gas emissions are scrubbed and may also then be diverted to the wastewater stream. This significantly lessens the possible emission by atmospheric deposition to soil or surface waters. Liquid wastes are treated (neutralisation to neutral ph) prior to emission to remove any sulphuric acid in the waste water and sludge from the waste water treatment plant is sent for incineration or landfill and is not used for agricultural spreading. This precludes any contamination of soil by sludge spreading. Waste water treatment is usually carried out by neutralisation followed by flocculation or decantation. 2.2.7. Efficiency of RMMs and Calculation of Release factors Waste gas emissions are scrubbed and may be diverted to the wastewater stream. This significantly lessens the possible emission by atmospheric deposition to soil or surface waters. Typically this removes >99% of sulphur oxides. The outflow is continually analysed for SO 2 content. Typical daily average concentration of SO 2 : 625 (range 2 77) mg/nm 3. Flow through specific SO 2 : < 2 kg SO 2 /t H 2 SO 4. Risk management measures related to environmental emissions from industrial sites Onsite pre-treatment of waste water Resulting fraction of initially applied amount in waste water released from site to the external sewage system Air emission abatement Onsite waste treatment Effluent (of the waste water treatment plant) discharge rate Recovery of sludge for agriculture or horticulture Resulting fraction of initially applied amount in waste water released from site Chemical pretreatment or onsite STP. Varies depending on system. Effectiveness: Adequate measures in place Effectiveness: complete Waste waters are generally treated by on site WWTP which will be neutralised before it reaches the biological tower of the WWTP or will be treated on site by chemical neutralisation methods before release to the municipal STP or to the environment The neutralisation process is extremely efficient and ph monitors are in place to ensure that complete neutralisation and removal have taken place. Exhaust gases treated by scrubbers. The waste water neutralisation process is extremely efficient with almost total neutralisation achieved. ph alarms are in place to ensure that successful neutralisation has taken place. 2 m 3 /d Default: 2 m 3 /d No.1% All sludge is collected and incinerated or sent to landfill. In the second tier assessment removal by neutralization has been considered.
Exposure Scenario 1: Production of sulphuric acid 22/44 Revision: 2.2.8. Waste related measures Fractions of substance in waste and waste management measures Amount of substances in waste water resulting from identified uses covered in the exposure scenario Amount of substances in waste resulting from service life of articles Type of waste, suitable waste codes Type of external treatment aiming at recycling or recovery of substances Type of external treatment aiming at final disposal of the waste Fraction of substance released into the environment via air from waste handling 3. Exposure estimation 3.1. Occupational exposure estimation kg/d Not applicable Suitable EWC code(s) None Incineration or landfill. Not applicable Tier 2 value based on the specialised waste water treatment procedures. The assessment of worker exposure to sulphuric acid from production was carried for processes relevant to this use scenario as identified by PROC codes. Initially, a screening-level (Tier 1) assessment was carried out using the ECETOC Targeted Risk Assessment (TRA) model. A higher tier (Tier 2) refinement was carried out using the Advanced REACH Tool (ART). 3.1.1. Acute/short-term and long-term exposure The effects of sulphuric acid following dermal exposures are local irritation and corrosivity of the skin. The unsuitable Tier 1 assessment of inhalation exposures associated with ES 1 derived using the ECETOC TRA model was refined using the higher tier (Tier 2) inhalation model: the Advanced REACH tool (ART). The Tier 2 assessment was carried out using the parameters and assumptions in the tables below. The predicted 5 th and 9 th (worst case) percentile acute/short-term (e.g. exposure over a full-shift) and long-term inhalation exposure concentrations derived using these parameters for processes associated with ES are shown in the tables below. Tier 2 acute/short-term and long-term inhalation exposure concentrations derived using the ART model Description of activity Production (High integrity closed system, sampling via closed loop) Production and sampling (Occasional exposure system) PROC Physical state Estimated exposure (mg/m 3 ) 5 th percentile value Short-term Conc 9 th percentile value Estimated Exposure (mg/m 3 ) 5 th percentile value Long-term Conc. 9 th percentile value 1 Liquid 8.2 x 1-1 9.3 x 1-9 3.6 x 1-9 9.4 x 1-9 2 Liquid 8.2 x 1-9 9.2 x 1-8 3.6 x 1-8 9.2 x 1-8
Exposure Scenario 1: Production of sulphuric acid 23/44 Revision: Production, transfer and sampling Production, transfer and sampling (Exposure likely) 3 Liquid 3.7 x 1-5 4.2 x 1-4 1.6 x 1-4 4.2 x 1-4 4 Liquid 1.2 x 1-3 1.4 x 1-2 5.4 x 1-3 1.4 x 1-2 Loading/transfer 8a Liquid 2. x 1-3 2.3 x 1-2 8.8 x 1-2 2.3 x 1-2 Loading/transfer 8b Liquid 1.1 x 1-5 1.2 x 1-4 4.8 x 1-5 4.8 x 1-6 Loading/transfer (Small containers) 9 Liquid 8.1 x 1-4 3.2 x 1-3 3.2 x 1-3 2.8 x 1-3 3.1.2. Consumer exposure Consumers are not directly exposed to sulphuric acid during the processes associated with ES1 as this exposure scenario involves only closed industrial processes. 3.1.3. Indirect exposure of humans via the environment (oral) Indirect exposure of humans via the environment is expected to be negligible. Sulphuric acid is fully miscible in water and, as such, will not persist in any environmental compartment where indirect exposure of humans could occur. Furthermore none of the processes associated with sulphuric acid production involve any targeted environmental emissions or application and the primary receiving compartment is the on-site STP where rigorous neutralisations processes and employed. Removal in the STP is expected to be efficient and so secondary exposure of the other receiving compartments is expected to be minimal. Similarly contamination of food crops or animals used as human food sources is not envisaged. 3.1.4. Quantitative risk characterisation for workers Acutelocal effects Long-term local effects Route Inhalation Inhalation PROC Code Exposure conc. (mg/m 3 ) Leading toxic end point / Critical effect DNEL (mg/m 3 ) Risk characterisation ratio (RCR) PROC 1 9.3 x 1-9 Respiratory irritation and corrositivity.1 9.2 x 1-7 PROC 2 9.2 x 1-8 Respiratory irritation and corrositivity.1 4.2 x 1-3 PROC 3 4.2 x 1-4 Respiratory irritation and corrositivity.1 1.4 x 1-1 PROC 4 1.4 x 1-2 Respiratory irritation and corrositivity.1 2.3 x 1-1 PROC 8a 2.3 x 1-2 Respiratory irritation and corrositivity.1 1.2 x 1-3 PROC 8b 1.2 x1-4 Respiratory irritation and corrositivity.1 3.2 x-1-2 PROC 9 3.2 x 1-3 Respiratory irritation and corrositivity.1 9.2 x-1-7 PROC 1 9.4 x1-9 Respiratory irritation and corrositivity.5 1.8 x1-6 PROC 2 9.2 x1-8 Respiratory irritation and corrositivity.5 8.4 x 1-3 PROC 3 4.2 x 1-4 Respiratory irritation and corrositivity.5 2.8 x 1-1 PROC 4 1.4 x 1-2 Respiratory irritation and corrositivity.5 4.6 x 1-1 PROC 8a 2.3 x 1-2 Respiratory irritation and corrositivity.5 9.6 x 1-5 PROC 8b 4.8 x 1-6 Respiratory irritation and corrositivity.5 5.6 x1-2 PROC 9 2.8 x 1-3 Respiratory irritation and corrositivity.5 1.8 x1-6
Exposure Scenario 1: Production of sulphuric acid 24/44 Revision: 3.2. Environmental exposure estimation The environmental releases are determined primarily by tonnage and the ERC in the first tier with conservative estimations and defaults being implemented by terms of the REACH ERCs. For the second tier assessment in EUSES more appropriate details and inputs are chosen to best suit the description of the use sulphuric acid as an intermediate. Emission defaults are those specified by the ECHA Guidance on information requirements and chemical safety assessment: Chapter R.16: Environmental Exposure Estimation. Regional data and emission fractions were calculated using EUSES. Predicted Releases to the Environment Tier 2 ERC Compartments 1 Aquatic freshwater (after STP) Predicted releases Measured release Explanation / source of measured data kg/d No data Based on efficiency of neutralization process Release to air 33.3 kg/d No data Based on worst case measured production emissions. Soil (direct only) Agricultural soil 3.2.1. Exposure concentration in sewage treatment plants (STP) kg/d No data No directly loss to soil is expected for this ERC. On contact with water, sulphuric acid, as a strong mineral acid (pka = 1.92), dissociates readily to hydrogen ions and sulphate ions (at all environmentally relevant ph s) and is totally miscible with the water layer. At all environmentally relevant concentrations, the substance will therefore exist as the environmentally ubiquitous nonhazardous sulphate (SO 4 2- ) anion and hydronium (H 3 O + ) cation. Sulphuric acid is produced on a large scale, generally on major chemical sites, which will have dedicated effluent treatment facilities, involving both chemical and biological treatment, coping with many chemical substances. As such any emission to wastewater will be almost instantly hydrolysed before even reaching the STP. Neutralisation procedures are in place to ensure that the ph of receiving waters is not affected. Measured ph values have been provided that confirm the efficacy of the neutralization procedure. Tier 2 Concentrations in sewage ERC for Compartment Waste water before treatment Estimated exposure concentrations Measured exposure concentrations value unit value unit 12 mg/l NA mg/l Explanation / source of measured data Sewage (STP effluent) mg/l NA mg/l Complete removal due to the on-site treatment Local freshwater mg/l NA mg/l 1-fold dilution by receiving waters
Exposure Scenario 1: Production of sulphuric acid 25/44 Revision: 3.2.2. Exposure concentration in the aquatic compartment Tier 2 Local and Predicted Environmental Concentrations (PEC) in aquatic compartment Compartments Local conc. aquatic (mg/l) Justification PEC aquatic (local mg/l) Freshwater 7. x 1-7 Justification Marine water 1-fold dilution by receiving waters Intermittent releases to water NA Intermittent release not relevant NA 1. x 1-4 Intermittent release not relevant 3.2.3. Exposure concentration in sediments Sulphuric acid, as a strong mineral acid (pka = 1.92), dissociates rapidly and completely in water. At all environmentally relevant concentrations, the substance will therefore exist as the environmentally ubiquitous nonhazardous sulphate anion and hydronium cation and is not expected to reach or accumulate in sediment. The weight of evidence strongly indicates that sulphuric acid will not accumulate in sediments. Nevertheless PEC sediment values as calculated by EUSES are presented below. Tier 2 Local and predicted concentrations (PEC) in aquatic sediment compartment Compartments Local concentration PEC aquatic (local) Freshwater sediment (in mg/kg) 6.7 x 1-7 Marine sediment (in mg/kg) 8.2 x 1-8 3.2.4. Exposure concentrations in soil and groundwater Given the rapid breakdown in water of sulphuric acid and the very limited atmospheric emissions there is no significant exposure to soil or groundwater expected. Any sulphuric acid in the atmosphere will be converted to its ions on contact with atmospheric moisture. The hydrogen ions, although not degraded as such due to their elemental nature, contribute to the ph of the local environment. The sulphate ions are incorporated into the various mineral species present in the environment. Nonetheless calculated PECs for soil and groundwater are presented below. Tier 2 Local and predicted (PEC) concentrations in the soil and groundwater compartment Compartments Local concentration PEC (local) Agricultural soil (averaged over 3 days, in mg/kg) 3.5 x 1-5 4.7 x 1-5 Groundwater (mg/l) 3.5 x 1-4 3.5 x 1-4 3.2.5. Atmospheric compartment Emissions to the atmosphere are controlled by either the use of fully sealed systems or scrubbers, in which all sulphur containing gases are controlled. Furthermore the Tier 2 regional PEC in air for production of sulphuric is very low indicating minimal levels of exposure from the atmospheric compartment and negligible risk to the regional environment.
Exposure Scenario 1: Production of sulphuric acid 26/44 Revision: Tier 2 Predicted Exposure Concentration (PEC) in air ERC Local conc. PEC air (local+regional) Justification 1 Annual average PEC in air, total (mg/m 3 ).91.91 Estimated using EUSES 2.1. 3.2.6. Exposure concentration relevant for the food chain (Secondary poisoning) Sulphuric acid is fully miscible in water and so removal in all water systems and removal by STP is expected to be highly effective. Therefore it is considered unlikely that humans will be exposed indirectly either by way of direct contact with the air, surface waters or soils, or by way of drinking water, or through exposure in the food chain. 3.2.7. Risk characterisation for environment Risk characterisation for the aquatic compartment Compartments PEC, mg/l PNEC, mg/l PEC/PNEC Comments Tier 2 Freshwater 7. x 1-7.25 2.8 x 1-4 Safe use demonstrated in tier 2 Tier 2 Sediment 6.7 x 1-7.2 (EPM) 3.3 x 1-4 Safe use demonstrated in tier 2 Tier 2 Marine sediment 8.2 x 1-8.2 (EPM) 4.1 x 1-5 Safe use demonstrated in tier 2 Tier 2 Marine 1. x 1-7.25 4. x 1-4 Safe use demonstrated in tier 2 Risk characterisation for sewage treatment systems Compartments PEC, mg/l PNEC, mg/l PEC/PNEC Comments Tier 2 STP 8.8 In the second tier assessment all waste acid is neutralized and removed before it enters any biological phase of an STP. As such there is no exposure and no risk.
27/44 Revision: Exposure Scenario 2: Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers 1. Title of exposure scenario 1.1. Free short title Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers 1.2. Systematic title based on use descriptor Sectors of Use Product Categories Process Categories Environmental Release Category SU3; SU4; SU6b; SU8; SU9; SU14 PC19 PROC1; PROC2; PROC3; PROC4; PROC8a; PROC8b; PROC9 ERC6a 1.3. Description of activities and processes covered in the exposure scenario The use of sulphuric acid as an intermediate in the production of inorganic and organic chemicals including but not limited to the production of fertilizers includes the production of oils used for lipolysis, sulphates, nitrogen fertilizers, granulation of complex fertilizers, phosphoric acid (wet process), titanium dioxide (sulphate route), hydrofluoric acid, fine chemicals and speciality chemicals. In addition to these uses the exposure scenario for intermediate use also includes reactive use in water treatment, use as a granulating agent and use as a tanning agent whereas sulphuric acid is consumed in a chemical synthesis to form sulphate. The large size of the typical facility involved means that all vessels and reactors are housed out-doors, managed by a small number of operators working in a separate enclosed control room. Road/rail tanker connecting and disconnecting (loading and unloading) generally takes place in the open air. Loading and unloading of tankers with sulphuric acid is performed in the open air. 2. Operational conditions and risk management measures 2.1. Control of workers exposure 2.1.1. Product Characteristic Type of product Physical state of product Substance as such Liquid product in a sealed tank container. Liquid Concentration of substance in product N/A 2.1.2. Frequency, duration and amounts of use/exposure Sulphuric acid is used up in the process Use amount per worker [workplace] per day No data Duration per day at workplace [for one worker] Worker contact is generally very low as most operations are remotely controlled and sampling/analysis events are of short duration. 8 h/d Standard number of hours in one work day Frequency at workplace 22 d/y Standard number of work days per year
28/44 Revision: Exposure Scenario 2: Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers Other determinants related to duration, frequency and amount of use Intermittent contact is expected These tasks rarely take a full 8 hours per day so worst case is assumed. 2.1.3. Other given operational conditions affecting workers exposure Not known. 2.1.4. Workers exposure factors not influenced by risk management Respiration volume and skin contact under conditions of worker uses Respiration volume under conditions of use Skin contact area with the substance under conditions of use 1 m 3 /d Default value for a worker breathing for a 8hrs work day in RIP 3.2. 48 cm 2 (ECETOC default) Due to the corrosive nature of sulphuric acid dermal exposure is not considered relevant for risk characterisation as it must be prevented in all cases. 2.1.5. Technical conditions and measures at process level (source) to prevent release Use of sulphuric acid involves special equipment and high integrity contained systems with little or no potential for exposure. Containment plus good work practice required; handling of sulphuric acid involves special equipment and controlled systems with little or no potential for exposure. Pipelines and vessels are sealed and insulated. 2.1.6. Technical conditions and measures to control dispersion from source towards the worker Local exhaust ventilation if required. Facilities involved in the production and uses of sulphuric acid are usually housed outdoors.any gas displaced from containers is conducted via pipeline to be processed i.e. removed and scrubbed and /or filtered. Gas displacement lines are also used if filling of road tankers takes place under cover. Containment and local exhaust ventilation Containment plus good work practice required Local exhaust ventilation if required Effectiveness: Unknown Effectiveness: Unknown 2.1.7. Organisational measures to prevent /limit releases, dispersion and exposure Handling of sulphuric acid involves special equipment and controlled systems with little or no potential for exposure. Facilities involved in the production and uses of sulphuric acid are usually housed outdoors. Any gas displaced from containers is conducted via pipeline to be processed i.e. removed and scrubbed and /or filtered. Workers generally operate in a separate control room, with no direct contact to the installations housing the material. Workers involved in sampling and transfer of materials to road tankers are trained in the procedures and protective equipment is intended to cope with the worst case scenario, in order to minimise exposure and risks.
29/44 Revision: Exposure Scenario 2: Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers 2.1.8. Conditions and measures related to personal protection Workers wear protective clothing (face/eye protection, helmet, anti-acid gloves boots and protective overall). Where required respiratory protection is worn. Personal protective equipment (PPE) Type of PPE (gloves, respirator, face-shield) 2.2. Control of environmental exposure 2.2.1. Product Characteristic Effectiveness: Unknown Handling of sulphuric acid involves special equipment and controlled systems with little or no potential for exposure. Facilities involved in the production and uses of sulphuric acid are usually housed outdoors. Any gas displaced from containers is conducted via pipeline to be processed i.e. removed and scrubbed and /or filtered. Sulphuric acid may be diluted with water to produce a variety of concentrations for industrial use. The viscosity of sulphuric acid is dependent on concentration and temperature. A viscosity of 22.5 cp (.225 Pa s; 22.5 mpa s) is reported for 95% sulphuric acid at 2 degrees Celsius. 2.2.2. Frequency, duration and amounts of use/exposure Annual amount used per site 3 t/y Worst case for single site Emission days per site 365 d/y Estimate number of emission days, based on continuous production For additional information see section 2.1.2. 2.2.3. Other given operational conditions affecting environmental exposure Not known 2.2.4. Environmental factors not influenced by risk management Conditions leading to dilution of initial release related to environment Discharge volume of sewage treatment plant 2 m 3 /d EUSES default value for standard local STP Available river water volume to receive the emissions from a site 2 m 3 /d Standard ERC flow rate leading to a 1 fold dilution in receiving waters. 2.2.5. Technical conditions and measures at process level (source) to prevent/limit release environmental exposure Use of sulphuric acid may involve special equipment and high integrity contained systems with little or no potential for exposure.
3/44 Revision: Exposure Scenario 2: Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers 2.2.6. Technical conditions and measures to control dispersion from source towards the environment Waste gas emissions are scrubbed and may be diverted to the wastewater stream. The outflow is continually analysed for SO 2 content. Liquid wastes are treated (neutralisation to neutral ph) prior to emission to remove any sulphuric acid in the waste water and sludge from the waste water treatment plant is sent for incineration or landfill and is not used for agricultural spreading. This precludes any contamination of soil by sludge spreading. Waste water treatment is usually carried out by neutralisation followed by flocculation or decantation. 2.2.7. Efficiency of RMMs and Calculation of Release factors Waste gas emissions are scrubbed and may be diverted to the wastewater stream. This significantly lessens the possible emission by atmospheric deposition to soil or surface waters. Typically this removes >99% of sulphur oxides. The outflow is continually analysed for SO 2 content. Typical daily average concentration of SO 2 : 625 (range 2 77) mg / Nm 3. Flow through specific SO 2 : < 2 kg SO 2 / t H 2 SO 4. Risk management measures related to environmental emissions from industrial sites Onsite pre-treatment of waste water Resulting fraction of initially applied amount in waste water released from site to the external sewage system Air emission abatement Onsite waste treatment Effluent (of the waste water treatment plant) discharge rate Recovery of sludge for agriculture or horticulture Resulting fraction of initially applied amount in waste water released from site Chemical pretreatment or onsite STP. Varies depending on system. Effectiveness: Adequate measures in place Effectiveness: complete Waste waters are generally treated by on site WWTP which will be neutralised before it reaches the biological tower of the WWTP or will be treated on site by chemical neutralisation methods before release to the municipal STP or to the environment The neutralisation process is extremely efficient and ph monitors are in place to ensure that complete neutralisation and removal have taken place. Exhaust gases treated by scrubbers. 2 m 3 /d Default: 2. m 3 /d No Less than.1% The waste water neutralisation process is extremely efficient with almost total neutralisation achieved. ph alarms are in place to ensure that successful neutralisation has taken place. All sludge is collected and incinerated or sent to landfill. In the second tier assessment removal by neutralization has been considered.
31/44 Revision: Exposure Scenario 2: Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers 2.2.8. Waste related measures Fractions of substance in waste and waste management measures Amount of substances in waste water resulting from identified uses covered in the exposure scenario Amount of substances in waste resulting from service life of articles Type of waste, suitable waste codes Type of external treatment aiming at recycling or recovery of substances Type of external treatment aiming at final disposal of the waste Fraction of substance released into the environment via air from waste handling kg/d Not applicable Suitable EWC code(s) None Incineration or landfill. Not applicable Tier 2 value based on the specialised waste water treatment procedures. 3. Exposure estimation 3.1. Occupational exposure estimation The assessment of worker exposure to sulphuric acid from production was carried for processes relevant to this use scenario as identified by PROC codes. Initially, a screening-level (Tier 1) assessment was carried out using the ECETOC Targeted Risk Assessment (TRA) model. A higher tier (Tier 2) refinement was carried out using the Advanced REACH Tool (ART). 3.1.1. Acute/short -term and long-term exposure The effects of sulphuric acid following dermal exposures are local irritation and corrosivity of the skin. The Tier 1 assessment of inhalation exposures associated with ES 2 derived using the ECETOC TRA model was refined using the higher tier (Tier 2) inhalation model: the Advanced REACH tool (ART). The Tier 2 assessment was carried out using the parameters and assumptions in the tables below. The predicted 5 th and 9 th (worst case) percentile acute/short-term (e.g. exposure over a full-shift) and long-term inhalation exposure concentrations derived using these parameters for processes associated with ES are shown in the tables below. Tier 2 acute/short-term and long-term inhalation exposure concentrations derived using the ART model Description of activity Use in closed process, no likelihood of exposure PROC Estimated Exposure Physical (mg/m 3 ) state of material 5 th percentile value Short-term Conc. 9 th percentile value Estimated Exposure (mg/m 3 ) 5 th percentile value Long-term Conc. 9 th percentile value 1 Liquid 8.2 x 1-1 9.3 x 1-9 3.6 x 1-9 9.4 x 1-9
32/44 Revision: Exposure Scenario 2: Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers Use in closed, continuous process with occasional controlled exposure (including sampling and maintenance) Use in closed batch process (synthesis or formulation) Use in batch and other process (synthesis) where opportunity for exposure arises 2 Liquid 8.2 x 1-9 9.2 x 1-8 3.6 x 1-8 9.2 x 1-8 3 Liquid 3.7 x 1-5 4.2 x 1-4 1.6 x 1-4 4.2 x 1-4 4 Liquid 1.2 x 1-3 1.4 x 1-2 5.4 x 1-3 1.4 x 1-2 Loading/transfer 8a Liquid 2. x 1-3 2.3 x 1-2 8.8 x 1-2 2.3 x 1-2 Loading/transfer 8b Liquid 1.1 x 1-5 1.2 x 1-4 4.8 x 1-5 4.8 x 1-6 Loading/transfer (small containers) 9 Liquid 8.1 x 1-4 3.2 x 1-3 3.2 x 1-3 2.8 x 1-3 3.1.2. Consumer exposure Consumers are not directly exposed to sulphuric acid during the activities covered under this exposure scenario as they are purely industrial and there is no direct release to consumers. 3.1.3. Indirect exposure of humans via the environment (oral) Indirect exposure of humans via the environment is expected to be negligible. Sulphuric acid is fully miscible in water and, as such, will not persist in any environmental compartment where indirect exposure of humans could occur. Furthermore none of the processes associated with sulphuric acid production involve any targeted environmental emissions or application and the primary receiving compartment is the on-site STP where rigorous neutralisations processes and employed. Removal in the STP is expected to be efficient and so secondary exposure of the other receiving compartments is expected to be minimal. Similarly contamination of food crops or animals used as human food sources is not envisaged. 3.1.4. Quantitative risk characterisation for workers Route PROC Code Exposure conc. (mg/m 3 ) Leading toxic end point / Critical effect DNEL (mg/m 3 ) RCR PROC 1 9.3 x 1-9 Respiratory irritation and corrositivity.1 9.2 x 1-7 Acute-local effects Inhalation PROC 2 9.2 x 1-8 Respiratory irritation and corrositivity.1 4.2 x 1-3 PROC 3 4.2 x 1-4 Respiratory irritation and corrositivity.1 1.4 x 1-1 PROC 4 1.4 x 1-2 Respiratory irritation and corrositivity.1 2.3 x 1-1 PROC 8a 2.3 x 1-2 Respiratory irritation and corrositivity.1 1.2 x 1-3 PROC 8b 1.2 x1-4 Respiratory irritation and corrositivity.1 3.2 x-1-2 PROC 9 3.2 x 1-3 Respiratory irritation and corrositivity.1 9.2 x-1-7
33/44 Revision: Exposure Scenario 2: Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers PROC 1 9.4 x1-9 Respiratory irritation and corrositivity.5 1.8 x1-6 PROC 2 9.2 x1-8 Respiratory irritation and corrositivity.5 8.4 x 1-3 PROC 3 4.2 x 1-4 Respiratory irritation and corrositivity.5 2.8 x 1-1 Long-term local effects Inhalation PROC 4 1.4 x 1-2 Respiratory irritation and corrositivity PROC 8a 2.3 x 1-2 Respiratory irritation and corrositivity.5 4.6 x 1-1.5 9.6 x 1-5 PROC 8b 4.8 x 1-6 Respiratory irritation and corrositivity.5 5.6 x1-2 PROC 9 2.8 x 1-3 Respiratory irritation and corrositivity.5 1.8 x1-6 3.2. Environmental exposure estimation The environmental releases are determined primarily by tonnage and the ERC in the first tier with conservative estimations and defaults being implemented by terms of the REACH ERCs. For the second tier assessment in EUSES more appropriate details and inputs are chosen to best suit the description of the use sulphuric acid as an intermediate. Emission defaults are those specified by the ECHA Guidance on information requirements and chemical safety assessment: Chapter R.16: Environmental Exposure Estimation. Regional data and emission fractions were calculated using EUSES. Full EUSES inputs are shown below. Predicted Releases to the Environment Tier 2 ERC Compartments 6A Aquatic freshwater (after STP) Predicted releases (kg/d) Measured release Release to air 94.9 No data Soil (direct only) Agricultural soil Explanation / source of measured data No data Based on efficiency of neutralization process No data 3.2.1. Exposure concentration in sewage treatment plants (STP) Worst case measured emissions associated with intermediate use No directly loss to soil is expected for this ERC and no sludge spreading. On contact with water, sulphuric acid, as a strong mineral acid (pka = 1.92), dissociates readily to hydrogen ions and sulphate ions (at all environmentally relevant ph s) and is totally miscible with the water layer. At all environmentally relevant concentrations, the substance will therefore exist as the environmentally ubiquitous nonhazardous sulphate (SO 4 2- ) anion and hydronium (H 3 O + ) cation. As such any emission to wastewater will be almost instantly hydrolysed before even reaching the STP. Neutralisation procedures are in place to ensure that the ph of receiving waters is not affected. Measured ph values have been provided that confirm the efficacy of the neutralization procedure.
34/44 Revision: Exposure Scenario 2: Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers Tier 2 Concentrations in sewage ERC for Compartment Waste water before treatment Estimated exposure concentrations Measured exposure concentrations value unit value unit 1, mg/l NA mg/l Explanation / source of measured data Sewage (STP effluent) mg/l NA mg/l Complete removal due to the neutralization process Local freshwater mg/l NA mg/l 1-fold dilution by receiving waters 3.2.2. Exposure concentration in the aquatic compartment Tier 2 Local and Predicted Environmental Concentrations (PEC) in aquatic compartment Compartments Local conc. aquatic (mg/l) Justification PEC aquatic (local mg/l) Freshwater (mg/l) 8.8 x 1-4 Marine water (mg/l) Intermittent releases to water (mg/l) NA 1-fold dilution by receiving waters 1.2 x 1-4 Intermittent release not relevant NA Justification Intermittent release not relevant 3.2.3. Exposure concentration in sediments Sulphuric acid, as a strong mineral acid (pka = 1.92), dissociates rapidly and completely in water. At all environmentally relevant concentrations, the substance will therefore exist as the environmentally ubiquitous nonhazardous sulphate anion and hydronium cation and is not expected to reach or accumulate in sediment. The weight of evidence strongly indicates that sulphuric acid will not accumulate in sediments. Nevertheless PECsediment values as calculated by EUSES are presented below. Tier 2 Local and predicted concentrations (PEC) in aquatic sediment compartment Compartments Local concentration (local) PEC aquatic (local) Freshwater sediment (in mg/kg) 7.13 x 1-4 7.13 x 1-4 Marine sediment (in mg/kg) 1.3 x 1-4 1.3 x 1-4 3.2.4. Exposure concentrations in soil and groundwater Any sulphuric acid in the atmosphere will be converted to its ions on contact with atmospheric moisture. The hydrogen ions, although not degraded as such due to their elemental nature, contribute to the ph of the local environment. The sulphate ions are incorporated into the various mineral species present in the environment. Nonetheless calculated PECs for soil and groundwater are presented below.
35/44 Revision: Exposure Scenario 2: Use of sulphuric acid as an intermediate in manufacture of inorganic and organic chemicals including fertilizers Tier 2 Local and predicted (PEC) concentrations in the soil and groundwater compartment Compartments Local concentration (local) PEC (local) Agricultural soil (averaged over 3 days, in mg/kg) 1 x 1-4.149 Groundwater (mg/l).11.11 3.2.5. Atmospheric compartment Emissions to the atmosphere are controlled by either the use of fully sealed systems or scrubbers, in which all sulphur containing gases are controlled. Furthermore the Tier 2 regional PEC in air for production of sulphuric is very low indicating minimal levels of exposure from the atmospheric compartment and negligible risk to the regional environment. Tier 2 Predicted Exposure Concentration (PEC) in air ERC Tier 26A Annual average PEC in air, total (mg/m 3 ) Local concentration PEC air (local+regional) Justification.261.261 Estimated using EUSES 2.1. 3.2.6. Exposure concentration relevant for the food chain (Secondary poisoning) Sulphuric acid is fully miscible in water and so removal in all water systems and removal by STP is expected to be highly effective. Therefore it is considered unlikely that humans will be exposed indirectly either by way of direct contact with the air, surface waters or soils, or by way of drinking water, or through exposure in the food chain. 3.2.7. Risk characterisation for environment Risk characterisation for the aquatic compartment Compartments PEC mg/l PNEC mg/l PEC/PNEC Comments Tier 2 Freshwater 8.8 x 1-4.25.352 Safe use demonstrated in tier 2 Tier 2 Sediment 7.3 x 1-4.2 (EPM).365 Safe use demonstrated in tier 2 Tier 2 Marine sediment 1.3 x 1-4.2 (EPM).51 Safe use demonstrated in tier 2 Tier 2 Marine 1.2 x 1-4.25.48 Safe use demonstrated in tier 2 Risk characterisation for sewage treatment systems Compartments PEC (mg/l) Tier 2 STP 8.8 PNEC (mg/l) PEC/PNEC Comments In the second tier assessment all waste acid is neutralized and removed before it enters any biological phase of an STP. As such there is no exposure and no risk.
1. Title of exposure scenario 1.1. Free short title SAFETY DATA SHEET Exposure Scenario 3: Mixing, preparation and repackaging of sulphuric acid Mixing, preparation and repackaging of sulphuric acid 1.2. Systematic title based on use descriptor 36/44 Revision: Sectors of Use Product Categories Process Categories Environmental Release Category SU3; SU1 PC19 PROC1; PROC3; PROC5 ; PROC8a; PROC8b; PROC9 ERC2 1.3. Description of activities and processes covered in the exposure scenario ES14 encompasses the use sulphuric acid during mixing, repackaging, preparation and in the production of Oleum. Generally the production and manufacture process would be continuous with use levels ranging between 1 and 5 tonnes per day in a large facility. The large size of the typical facility involved means that all vessels and reactors are housed out-doors or indoors, managed by a small number of operators working in a separate enclosed control room. 2. Operational conditions and risk management measures 2.1. Control of workers exposure 2.1.1. Product Characteristic Type of product Physical state of product Substance as such Liquid Concentration of substance in product 98% 2.1.2 Frequency, duration and amounts of use/exposure Use amount per worker [workplace] per day No data The product is in liquid form in a sealed tank container. Worker exposure considered to be negligible due to specialised systems. Duration per day at workplace [for one worker] 8 h/d Standard number of hours in one work day Frequency at workplace 22 d/y Standard number of work days per year Other determinants related to duration, frequency and amount of use Intermittent contact is expected 2.1.3 Other given operational conditions affecting workers exposure Not known. These tasks rarely take a full 8 hours per day so worst case is assumed.
Exposure Scenario 3: Mixing, preparation and repackaging of sulphuric acid 2.1.4 Workers exposure factors not influenced by risk management Respiration volume and skin contact under conditions of worker uses Respiration volume under conditions of use 1 m 3 /d Skin contact area with the substance under conditions of use 48 cm 2 (ECETOC default) 37/44 Revision: Default value for a worker breathing for a 8hrs work day in RIP 3.2. Please note that due to the corrosive nature of sulphuric acid dermal exposure is not considered relevant for risk characterisation as it must be prevented in all cases. 2.1.5. Technical conditions and measures at process level (source) to prevent release Use of sulphuric acid during mixing, preparation, re-packaging or in the manufacture of oleum often involves specialised processes and high temperatures. High integrity contained systems are utilised with little or no potential for exposure. Pipelines and vessels are sealed and insulated. 2.1.6. Technical conditions and measures to control dispersion from source towards the worker Local exhaust ventilation if required. Facilities involved in the production and uses of sulphuric acid are usually housed outdoors.any gas displaced from containers is conducted via pipeline to be processed i.e. removed and scrubbed and /or filtered. Gas displacement lines are also used if filling of road tankers takes place under cover. Containment and local exhaust ventilation Containment plus good work practice required Local exhaust ventilation if required Effectiveness: Unknown Effectiveness : Unknown 2.1.7. Organisational measures to prevent /limit releases, dispersion and exposure Handling of sulphuric acid involves special equipment and controlled systems with little or no potential for exposure. Facilities involved in the production and uses of sulphuric acid are usually housed outdoors. Any gas displaced from containers is conducted via pipeline to be processed i.e. removed and scrubbed and /or filtered. Workers involved are generally separated from the production machinery and systems with no direct contact to the installations housing the material. Workers involved in sampling and transfer of materials to road or rail tankers are trained in the procedures and protective equipment is intended to cope with the worst case scenario, in order to minimise exposure and risks. 2.1.8. Conditions and measures related to personal protection Workers involved in use, handing, sampling and transfer of materials are trained in the procedures and protective equipment is intended to cope with the worst case scenario, in order to minimise exposure and risks. This may include chemical resistant clothing, goggles and respiratory equipment where required.
Exposure Scenario 3: Mixing, preparation and repackaging of sulphuric acid Personal protective equipment (PPE) Type of PPE (gloves, respirator, face-shield) 2.2. Control of environmental exposure 2.2.1. Product Characteristic Effectiveness: Unknown 38/44 Revision: Production and handling of sulphuric acid involves special equipment and high integrity contained systems with little or no potential for exposure. Facilities involved in the production and uses of sulphuric acid are usually housed outdoors. Workers involved in sampling and transfer of materials to road tankers are trained in the procedures and protective equipment is intended to cope with the worst case scenario, in order to minimise exposure and risks. Sulphuric acid may be diluted with water to produce a variety of concentrations for industrial use. The viscosity of sulphuric acid is dependent on concentration and temperature. A viscosity of 22.5 cp (.225 Pa s; 22.5 mpa s) is reported for 95% sulphuric acid at 2 degrees Celsius. 2.2.2. Frequency, duration and amounts of use/exposure Annual amount used per site 3 t/y Worst case for single site Emission days per site 365 d/y Estimate number of emission days, based on continuous production For additional information see section 2.1.2. 2.2.3. Other given operational conditions affecting environmental exposure Not known 2.2.4. Environmental factors not influenced by risk management Conditions leading to dilution of initial release related to environment Discharge volume of sewage treatment plant 2 m 3 /d EUSES default value for standard local STP Available river water volume to receive the emissions from a site 2 m 3 /d Standard ERC flow rate leading to a 1 fold dilution in receiving waters. 2.2.5. Technical conditions and measures at process level (source) to prevent/limit release environmental exposure High integrity contained systems are utilised with little or no potential for exposure. Pipelines and vessels are sealed and insulated.
Exposure Scenario 3: Mixing, preparation and repackaging of sulphuric acid 39/44 Revision: 2.2.6. Technical conditions and measures to control dispersion from source towards the environment Environmental emissions are limited by designated waste treatment processes designed to limit environmental exposure to all relevant compartments. Waste gas emissions are scrubbed and may also then be diverted to the wastewater stream. This significantly lessens the possible emission by atmospheric deposition to soil or surface waters. Liquid wastes are treated (neutralisation to neutral ph) prior to emission to remove any sulphuric acid in the waste water and sludge from the waste water treatment plant is sent for incineration or landfill and is not used for agricultural spreading. This precludes any contamination of soil by sludge spreading. Waste water treatment is usually carried out by neutralisation followed by flocculation or decantation. 2.2.7. Efficiency of RMMs and Calculation of Release factors Waste gas emissions are scrubbed and may be diverted to the wastewater stream. This significantly lessens the possible emission by atmospheric deposition to soil or surface waters. Typically this removes > 99% of sulphur oxides. The outflow is continually analysed for SO 2 content. Typical daily average concentration of SO 2 : 625 (range 2 77) mg / Nm 3. Flow through specific SO 2 : < 2 kg SO 2 /t H 2 SO 4. Risk management measures related to environmental emissions from industrial sites Onsite pre-treatment of waste water Resulting fraction of initially applied amount in waste water released from site to the external sewage system Air emission abatement Onsite waste treatment Effluent (of the waste water treatment plant) discharge rate Recovery of sludge for agriculture or horticulture Resulting fraction of initially applied amount in waste water released from site Chemical pretreatment or onsite STP. Varies depending on system. Measured emissions of waste gas Effectiveness: complete Waste waters are generally treated by on site WWTP which will be neutralised before it reaches th biological tower of the WWTP or will e be treated on site by chemical neutralisation methods before release to the municipal STP or to the environment The neutralisation process is extremely efficient and ph monitors are in place to ensure that complete neutralisation and removal have taken place. Exhaust gases treated by scrubbers. 2 m 3 /d Default: 2. m 3 /d No Less than.1% The waste water neutralisation process is extremely efficient with almost total neutralisation achieved. ph alarms are in place to ensure that successful neutralisation has taken place. All sludge is collected and incinerated and sent to landfill or recycled for reuse of recovered metals, if any. In the second tier assessment removal by neutralization has been considered.
2.2.8. Waste related measures SAFETY DATA SHEET Exposure Scenario 3: Mixing, preparation and repackaging of sulphuric acid Fractions of substance in waste and waste management measures: Amount of substances in waste water resulting from identified uses covered in the exposure scenario Amount of substances in waste resulting from service life of articles Type of waste, suitable waste codes Type of external treatment aiming at recycling or recovery of substances Type of external treatment aiming at final disposal of the waste Fraction of substance released into the environment via air from waste handling Fraction of substance released into the environment via waste water from waste handling Fraction of substance disposed of as secondary waste 3. Exposure estimation 3.1. Occupational exposure estimation kg/d Not applicable Suitable EWC code(s) None Incineration or landfill. Not applicable Not applicable Not applicable 4/44 Revision: Tier 2 value based on the specialised waste water treatment procedures. The assessment of worker exposure to sulphuric acid following mixing, preparation and repackaging of sulphuric acid was carried for processes relevant to this use scenario as identified by PROC codes. Initially, a screening-level (Tier 1) assessment was carried out using the ECETOC Targeted Risk Assessment (TRA) model. A higher tier (Tier 2) refinement of the Tier 1 assessment was carried out using the Advanced REACH Tool (ART). 3.1.1. Acute/short -term and long-term exposure The effects of sulphuric acid following dermal exposures are local irritation and corrosivity of the skin. There is no evidence of systemic effects following dermal exposures to sulphuric acid. Estimates of systemic dermal doses associated with acute/short-term and long-term exposures to sulphuric acid were not therefore derived. The Tier 1 assessment of inhalation exposures derived using the ECETOC TRA model was refined using the higher tier (Tier 2) inhalation model: the Advanced REACH tool (ART). In the ART model, a mechanistic model of inhalation exposure and expert judgement were used to predict more realistic estimates of inhalation exposure concentrations associated with processes involving sulphuric acid. The Tier 2 assessment was carried out using the parameters and assumptions in the tables below. The predicted 5 th and 9 th (worst case) percentile acute/short-term (e.g. exposure over a full-shift) and long-term inhalation exposure concentrations derived using these parameters for processes associated with ES 2 are shown in the tables below.
Exposure Scenario 3: Mixing, preparation and repackaging of sulphuric acid 41/44 Revision: Tier 2 acute/short-term and long-term inhalation exposure concentrations derived using the ART model Description of activity Use in closed process, no likelihood of exposure Use in closed batch process (synthesis or formulation) Mixing or blending in batch process for formulation of preparations or articles (multistage and/or significant contact) PROC Estimated Exposure Physical (mg/m 3 ) state of material 5 th percentile value Short-term Conc. 9 th percentile value Estimated Exposure (mg/m 3 ) 5 th percentile value Long-term Conc. 9 th percentile value 1 Liquid 8.2 x 1-1 9.3 x 1-9 3.6 x 1-9 9.4 x 1-9 3 Liquid 3.7 x 1-5 4.2 x 1-4 1.6 x 1-4 4.2 x 1-4 5 Liquid,45,18,63,16 Loading/transfer 8a Liquid 2. x 1-3 2.3 x 1-2 8.8 x 1-2 2.3 x 1-2 Loading/transfer 8b Liquid 1.1 x 1-5 1.2 x 1-4 4.8 x 1-5 4.8 x 1-6 Loading/transfer(Small containers) 9 Liquid 8.1 x 1-4 3.2 x 1-3 3.2 x 1-3 2.8 x 1-3 3.1.2. Consumer exposure Consumers are not directly exposed to sulphuric acid during the activities covered under this exposure scenario as they are purely industrial and there is no direct release to consumers. 3.1.3. Indirect exposure of humans via the environment (oral) Indirect exposure of humans via the environment is expected to be negligible. Sulphuric acid is fully miscible in water and, as such, will not persist in any environmental compartment where indirect exposure of humans could occur. Furthermore none of the processes associated with sulphuric acid production involve any targeted environmental emissions or application and the primary receiving compartment is the on-site STP where rigorous neutralisations processes and employed. Removal in the STP is expected to be efficient and so secondary exposure of the other receiving compartments is expected to be minimal. Similarly contamination of food crops or animals used as human food sources is not envisaged. 3.1.4. Quantitative risk characterisation for workers Acutelocal effects Route Inhalation PROC Code Exposure concentrations (mg/m 3 ) Leading toxic end point / Critical effect DNEL (mg/m 3 ) RCR PROC 1 9.3 x 1-9 Respiratory irritation and corrositivity.1 9.3 x 1-8 PROC 3 4.2 x 1-4 Respiratory irritation and corrositivity.1 4.2 x 1-3 PROC 5 1.8 x 1-2 Respiratory irritation and corrositivity.1 1.8 x 1-1 PROC 8a 2.3 x 1-2 Respiratory irritation and corrositivity.1 2.3 x 1-1 PROC 8b 1.2 x1-4 Respiratory irritation and corrositivity.1 1.2 x1-3 PROC 9 3.2 x 1-3 Respiratory irritation and corrositivity.1 3.2 x 1-2
Exposure Scenario 3: Mixing, preparation and repackaging of sulphuric acid 42/44 Revision: Longterm local effects Inhalation PROC 1 9.4 x1-9 Respiratory irritation and corrositivity.5 1.9 x1-7 PROC 3 4.2 x 1-4 Respiratory irritation and corrositivity.5 8.4 x 1-3 PROC 5 1.6 x 1-2 Respiratory irritation and corrositivity.5 3.2 x 1-1 PROC 8a 2.3 x 1-2 Respiratory irritation and corrositivity.5 4.6 x 1-1 PROC 8b 4.8 x 1-6 Respiratory irritation and corrositivity.5 9.6 x1-5 PROC 9 2.8 x 1-3 Respiratory irritation and corrositivity.5 5.6 x1-2 3.2. Environmental exposure estimation The environmental releases are determined primarily by tonnage and the ERC in the first tier with conservative estimations and defaults being implemented by terms of the REACH ERCs. For the second tier assessment in EUSES more appropriate details and inputs are chosen to best suit the description of the use sulphuric acid as an intermediate. Emission defaults are those specified by the ECHA Guidance on information requirements and chemical safety assessment: Chapter R.16: Environmental Exposure Estimation. Regional data and emission fractions were calculated using EUSES. Full EUSES inputs are shown below. Predicted Releases to the Environment Tier 2 ERC Compartments 6A Aquatic freshwater (after STP) Predicted releases Measured release Explanation / source of measured data kg/d - Based on efficiency of neutralization process Release to air 25 kg/d - Worst case measured emissions - intermediate use Soil (direct only) Agricultural soil kg/d - No directly loss to soil is expected for this ERC. 3.2.1. Exposure concentration in sewage treatment plants (STP) On contact with water, sulphuric acid, as a strong mineral acid (pka = 1.92), dissociates readily to hydrogen ions and sulphate ions (at all environmentally relevant ph s) and is totally miscible with the water layer. At all environmentally relevant concentrations, the substance will therefore exist as the environmentally ubiquitous nonhazardous sulphate (SO 4 2- ) anion and hydronium (H 3 O + ) cation. As such any emission to wastewater will be almost instantly hydrolysed before even reaching the STP. Neutralisation procedures are in place to ensure that the ph of receiving waters is not affected. Measured ph values have been provided that confirm the efficacy of the neutralization procedure. Tier 2 Concentrations in sewage ERC for Compartment Waste water before treatment Estimated exposure concentrations Measured exposure concentrations value unit value unit 13,2 mg/l NA mg/l Sewage (STP effluent) mg/l NA mg/l Local freshwater mg/l NA mg/l Explanation / source of measured data
Exposure Scenario 3: Mixing, preparation and repackaging of sulphuric acid 3.2.2. Exposure concentration in the aquatic compartment Tier 2 Local and Predicted Environmental Concentrations (PEC) in aquatic compartment Compartments Local aquatic concentration (local mg/l) Justification PEC aquatic (local mg/l) Freshwater (mg/l) 4.43 x 1-5 Marine water (mg/l) 1-fold dilution by receiving waters 6.42 x 1-6 Intermittent releases to water (mg/l) 3.2.3. Exposure concentration in sediments 43/44 Revision: Justification NA Intermittent release not relevant NA not relevant Sulphuric acid, as a strong mineral acid (pka = 1.92), dissociates rapidly and completely in water. At all environmentally relevant concentrations, the substance will therefore exist as the environmentally ubiquitous nonhazardous sulphate anion and hydronium cation and is not expected to reach or accumulate in sediment. The weight of evidence strongly indicates that sulphuric acid will not accumulate in sediments. Nevertheless PECsediment values as calculated by EUSES are presented below. Tier 2 Local and predicted concentrations (PEC) in aquatic sediment compartment Compartments Local concentration (local) PEC aquatic (local) Freshwater sediment (mg/kg) 3.56 x 1-5 3.56 x 1-5 Marine sediment (mg/kg) 5.16 x 1-6 5.16 x 1-6 3.2.4. Exposure concentrations in soil and groundwater Emissions to air are controlled and negligible, and therefore indirect emissions to soil (and groundwater) via atmospheric deposition are also negligible. Any sulphuric acid in the atmosphere will be converted to its ions on contact with atmospheric moisture. Tier 2 Local and predicted (PEC) concentrations in the soil and groundwater compartment Compartments Local concentration (local) PEC (local) Agricultural soil -averaged over 3 days (mg/kg) 9.42 x 1-4 9.42 x 1-4 Groundwater (mg/l).7 9.42 x 1-4 3.2.5. Atmospheric compartment With regards to the modelled Tier 1 data, REACH ERC predictions assume 5% of production is released to atmosphere, which for a fully sealed plant (as those dealing with sulphuric acid are) is highly unrealistic. Furthermore the Tier 2 regional PEC in air is very low indicating minimal levels of exposure from the atmospheric compartment and negligible risk to the regional environment. It should be noted that the PECs in air below do not take scrubbing into account and so can be considered very worst case.
Exposure Scenario 3: Mixing, preparation and repackaging of sulphuric acid 44/44 Revision: Tier 2 Predicted Exposure Concentration (PEC) in air ERC Local concentration PEC air (local+regional) Justification Tier 26A Annual average PEC in air, total (mg/m 3 ).261.261 Estimated using EUSES 2.1. 3.2.6. Exposure concentration relevant for the food chain (Secondary poisoning) Sulphuric acid is fully miscible in water and so removal in all water systems and removal by STP is expected to be highly effective. Therefore it is considered unlikely that humans will be exposed indirectly either by way of direct contact with the air, surface waters or soils, or by way of drinking water, or through exposure in the food chain. 3.2.7. Risk characterisation for environment Risk characterisation for the aquatic compartment Compartments PEC mg/l PNEC mg/l PEC/PNEC Comments Tier 2 Freshwater 4.43 x 1-5.25.1 Safe use demonstrated in tier 2 Tier 2 Sediment 3.56 x 1-5.2 (EPM).178 Safe use demonstrated in tier 2 Tier 2 Marine sediment 5.16 x 1-6.2 (EPM).25 Safe use demonstrated in tier 2 Tier 2 Marine 6.42 x 1-6.25.256 Safe use demonstrated in tier 2 Risk characterisation for sewage treatment systems Compartments PEC (mg/l) PNEC (mg/l) Tier 2 STP 8.8 PEC/PNEC Comments In the second tier assessment all waste acid is neutralized and removed before it enters any biological phase of an STP. As such there is no exposure and no risk.