I n t e r n a t i o n a l M a n g a n e s e I n s t i t u t e Association DISCLAIMER: The International Manganese Institute believes that the information presented is technically and scientifically correct. However, IMnI does not represent or warrant the accuracy of the information contained in this document or its suitability for any general or specific use. The material contained herein is by necessity general in nature; it should not be used or relied upon for any specific or general application without first obtaining competent advice. IMnI, its members, staff and consultants specifically disclaim any and all liability or responsibility of any kind for loss, damage, or injury resulting from the use of the information contained in this publication. MATERIAL SAFETY INFORMATION: PYROLUSITE ORE; NATURAL MANGANESE DIOXIDE ORE SECTION 1: IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING 1.1 Substance/Mixture Identification: Substance name: Pyrolusite ore Other names: MnO2 Ore, MnO2 mineral REACH Registration number: [If applicable] 1.2 Use of the Substance/Mixture: SU 14: Manufacture of basic metals including alloys–PC7: Base metals and alloys Add or delete the above to suit your company’s needs 1.2.2 Use advised against: No known uses advised against 1.3 Company/Undertaking identification/contact person’s: Complete as required 1.4 Emergency Telephone: Complete as required SECTION 2: HAZARD IDENTITIFCATION 2.1 Classification of the substance or mixture: This material is classified as eye Irritation Cat 2B Under the United Nations Globally Harmonised System of classification and labelling [UN GHS] Classified as an Eye irritant Category 2 according to Regulation (EC) No. 1272/2008 EU Classification Labelling and Packaging [CLP] No classification for transport under the IMSBC code 1 I n t e r n a t i o n a l M a n g a n e s e I n s t i t u t e Association 2.2 Labelling/Pictograms: Classification scheme EU Classification labelling & packaging Regulation Eye Irritation Category 2 Classification category Symbol UN GHS Eye Irritation cat 2B No symbol Signal word Hazard statement Precautionary statement Prevention Precautionary statement Response Warning Causes serious eye irritation P264, P280 Warning Causes eye irritation P264, P280 P305+ P351+P338, P337+P313 P305+ P351+P338, P337+P313 2.3 Other Hazards: It is advisable to avoid generating dust as all fine particles have the potential to explode. Include other hazards if known SECTION 3: COMPOSITION/INFORMATION ON INGREDIENTS 3.1 Substance(s) [Amend as appropriate] A naturally occurring UVCB - Unknown or Variable Composition, complex reaction products or Biological - substance with the following composition: Chemical composition Manganese oxide EC No. CAS number Nominal % w/w 215-695-8 1344-43-0 Aluminium oxide 215-691-6 1344-28-1 Silicon dioxide 231-545-4 7631-86-9 Iron oxide 215-168-2 1309-37-1 Potassium oxide 235-227-6 12136-45-7 Barium oxide 215-127-9 1304-28-5 Titanium dioxide 236-675-5 13463-67-7 Phosphorous pentaoxide Magnesium oxide 215-236-1 1314-56-3 215-171-9 1309-48-4 >50% ( Amend as appropriate) Complete as per your product Complete as per your product Complete as per your product Complete as per your product Complete as per your product Complete as per your product Complete as per your product Complete as per your product 2 I n t e r n a t i o n a l Several other metallic oxides - M a n g a n e s e - n s t i t u t e Association None of which is present at >0.1%w/w Mineral composition component status Pyrolusite Major Crytomelane Major Nsutite Minor Todorokite Minor Hollandite Minor Other trace minerals Trace SECTION 4: I Range in norminal % w/w Complete as per your product Complete as per your product Complete as per your product Complete as per your product Complete as per your product - FIRST AID MEASURES 4.1 Description of first aid measures: 4.1.1 General Information Not anticipated to cause any harm if in contact with clothing, skin or eye. However, in case of accident or unwellness, seek medical advice immediately 4.1.2 Following Inhalation: Do not inhale. Wear appropriate mask. Include other relevant information based on your company’s procedures 4.1.3 Following Skin Contact: Include information based on your company’s procedures 4.1.4 Following Eye Contact: Eye protection is a must. Include information based on your company’s procedures 4.1.5 Following Ingestion: Do not ingest. Include other relevant information based on your company’s procedures 4.1.6 Self protection of the first aider: Include information based on your company’s procedures 4.2 Most important symptoms and effects, both acute and delayed: Irritating to the eyes, eye protection is a must 4.3 Indication of any immediate medical attention and special treatment needed: Include information based on your company’s procedures SECTION 5: FIRE-FIGHTING MEASURES: 5.1 Suitable extinguishing media: Include information based on your company’s procedures 5.2 Special hazards arising from substance or preparation: The substance can produce decomposition products – mainly metal oxide/oxides. Include any other relevant information 5.3 Advice for fire-fighters: 3 I n t e r n a t i o n a l M a n g a n e s e I n s t i t u t e Association Include information based on your company’s procedures SECTION 6: ACCIDENTAL RELEASE MEASURES: 6.1 Personal precautions, protective equipment and emergency procedures: 6.1.1 For non-emergency personnel: Use personal protective equipment, see section 8 6.1.2 For emergency responders: Remove persons to safety. Isolate hazard area and deny entry. Ventilate closed spaces before entering. Use personal protective equipment, see section 8 6.2 Environmental precautions: The substance is not considered an environmental hazard based on the available studies. However it is advisable to keep away from drains as large quantities could clog drains. Include other information based on your company’s procedures 6.3 Methods and material for containment and Cleaning up: Collect contaminated material and put in appropriate containers for disposal. Dispose of as special waste in compliance with local and national regulations 6.3.1 For containment: Collect in closed and suitable containers for disposal. Include other information based on your company’s procedures. 6.3.2 For cleaning up: Clean contaminated objects and areas thoroughly observing environmental regulations 6.3.3 Other information: None 6.4 Reference to other sections: Personal protective equipment: see section Section 7: HANDLING AND STORAGE: 7.1 Precautions for safe handling: 7.1.1 Protective measures: Use only in well ventilated areas. Avoid generating dust as dust can easily enter the eyes. Wear personal protective clothing (see Section 8). Include other information based on your company’s procedures. 7.1.2 Measures to prevent fire: This substance is not flammable; however, avoid generating dust as very fine dust can lead to combustion. Include other information based on your company’s procedures. 7.1.3 Measures to prevent aerosol and dust generation: Include information based on your company’s procedures 7.1.4 Measures to protect the environment: Shaft and sewers must be protected from entry of the substance. Include information based on your company’s procedures 7.1.5 Advice on general occupational hygiene: Work in well-ventilated zones or use proper respiratory protection. Include other information based on your company’s procedures 7.2 Conditions for safe storage, including any incompatibilities: 7.2.1 Technical measures and storage conditions: Store at room temperature. 4 I n t e r n a t i o n a l M a n g a n e s e I n s t i t u t e Association 7.2.2 Requirement for storage rooms and vessels: Keep/store only in original container/packaging. Ensure adequate ventilation for the storage area. Include other information based on your company’s procedures 7.2.3 Further information on storage conditions: Protect container/packaging against damage 7.3 Specific end uses(s): Recommendations: Observe instructions for use SECTION 8: EXPOSURE CONTROLS/ PERSONAL PROTECTION: 8.1 Control Parameters: The EU SCOEL has recently recommended OEL values for Manganese and its inorganic compounds of 0.2mg/m3 – inhalable and 0.05mg/m3 respirable. Include other relevant workplace limits 8.2 Environmental exposure controls: Emissions from ventilation or work place process equipment should be checked to ensure they comply with the requirements of environmental protection legislation Include other information based your company’s procedures SECTION 9: PHYSICAL AND CHEMICAL PROPERTIES: [the information below is based on available literature and studies] 9.1 General information Appearance Odour Odour threshold pH Boiling point Melting point (Mpt) / Freezing point Flash Point Flammability of solids Explosive properties Oxidizing properties Vapour pressure Corrosion to metals Water Solubility Partition Coefficient Viscosity Self Ignition Black rock Odourless Does not apply, as substance is odourless Not applicable Melting pt >300°C, hence study not applicable >723 K (>450°C) Not required for inorganic substances Not flammable, Regulation (EC) No. 440/2008, Method A10 Predicted to be non-explosive Not oxidizing Study not conducted as Mpt >300°C Predicted not to corrode metals due to high melting point Predicted Insoluble Not applicable for inorganic substances No data available, testing not technically possible Not self-igniting 5 I n t e r n a t i o n a l M Dissociation constant Surface tension Stability in organic solvents and identity of relevant degradation groups 9.2 Other information a n g a n e s e I n s t i t u t e Association Cannot dissociate due to lack of relevant functional groups Substance is predicted not be surface active Not applicable for inorganic substances No additional information relevant to the safe use of the substance SECTION 10: STABILITY AND REACTIVITY: [Amend information below to conform to your company information] 10.1 Reactivity: No specific test data related to reactivity available for this substance. 10.2 Chemical stability: The substance is chemically stable under recommended conditions of storage, use and temperature. 10.3 Possibility of Hazardous reaction: No hazardous reaction when handled and stored according to provisions 10.4 Conditions to avoid: Include your company’s information 10.5 Incompatible Materials: Include your company’s information 10.6 Hazardous decomposition products: Does not decompose when used for intended uses. Include your company’s information SECTION 11: TOXICOLOGICAL INFORMATION: [The information in this section is from experimental data and other available literature] 11.1 Information on toxicological effects: Acute toxicity: Acute oral toxicity: No adverse effect observed (LD50 >2000 mg/kg bw) Acute dermal toxicity: No study available. No concerns predicted Acute inhalation toxicity: No adverse effects observed (LD50 >5000 mg/m3) Skin corrosion/irritation: Not corrosive and not irritating to the skin based on OECD 431 (In vitro skin corrosion: Reconstructed Human Epidermis (RHE) Test Method) and OECD 439 (In vitro skin irritation: Reconstructed Human Epidermis (RHE) Test Method) studies. Serious eye damage/irritation: Mildly irritating to the eye based on Bovine Corneal opacity and permeability test method for identifying chemical inducing serious eye damage and chemicals not requiring classification for eye irritation or serious eye damage and pH modeling. Respiratory or skin sensitization: No studies available. It is predicted not to be a respiratory sensitizer or skin sensitizer. Germ cell mutagenicity: Negative in all test conducted using a MnCl2 – a very soluble salt considered as a worse-case evaluation: 6 I n t e r n a t i o n a l - - - M a n g a n e s e I n s t i t u t e Association Ames test with S. typhimurium TA 98, TA 100, TA 1535, TA 1537, E coli WP2 uvrA (Met. act.: with and without) (OECD TG 471, EU method B13 and GLP); No toxicity was observed up a concentration of 5000 ug/plate. Mammalian cell gene mutation assay with mouse lymphoma L5178Y cells (met. act.: with and without) (OECD 476 and GLP); Negative for mouse lymphoma Cytoxicity: Yes, induced toxicity was not at the highest dose. In-vitro mammalian chromosome aberration test with human lymphocytes (Met. act.: with and without) (OECD guideline 473 and GLP). Negative for lymphocytes. Cytotoxicity: Yes Carcinogenicity: There are not specific studies on carcinogenicity for this substance. However, since all in-vitro genotoxicity test on a more bioavailable manganese salt were negative and an expert report (Jenkinson, 2009) as well as a literature review on carcinogenicity for Mn and its inorganic compounds concluded – no concerns, carcinogenicity in humans is not expected. Reproductive toxicity: Two Generation reprotoxicity study on the male/female rats using MnCL2 via inhalation (OECD guideline 416, GLP): Not toxic to reproduction Specific target organ toxicity (Single exposure): Based on available data the classification criteria are not met. Specific target organ toxicity (repeated exposure): Based on available literature, high dust exposure (from some mines – ore types unspecified/unclear) for long periods of time has led to neurotoxic effects in some workers. Dust exposure should therefore be kept to a minimum. Aspiration hazard: Data lacking SECTION 12: ECOLOGICAL INFORMATION: 12.1 Ecotoxicity: No environmental concerns expected from acute or chronic exposure to the environment as leaching to the environment based on transformation dissolution study confirmed <0.01% average manganese content release at pH 6 and 8 SECTION 13: DISPOSAL CONSIDERATIONS: Include your company’s information 13.1 Waste treatment methods: Waste disposal in accordance with local and national laws covering waste and dangerous waste. Include additional company specific information 13.1.1 Product/packaging disposal: Waste must be disposed of in line with local regulations. Waste codes should be assigned by the user, preferably in discussion with the waste authorities. 13.1.2 Waste treatment-relevant information: Include your company’s information. 7 I n t e r n a t i o n a l M a n g a n e s e I n s t i t u t e Association 13.1.3 Sewage disposal-relevant information: Include your company’s information. 13.1.4 Other disposal recommendations: Handle contaminated packages in the same way as the substance itself. Include other company specific information. SECTION 14: TRANSPORT INFORMATION: Transport may take place according to national regulations or land transport (ADR/RID), sea transport (IMDG) or Air transport (ICAO-TI/IATA-DGR). 14.1 UN Number: Include number or use not applicable if this is the case 14.2 UN proper shipping name: Include name or use not applicable if this is the case 14.3 Transport hazard class: Not hazardous 14.4 Packaging group: Include packaging group or use not applicable if this is the case 14.5 Environmental hazard: Not hazardous to the environment 14.6 Special precautions for users: Always transport in close containers, avoid generating dust [Amend as appropriate] 14.7 Transport in bulk according to Annex II of MARPOL73/78 and ISBC code: Eye irritation cat 2B is not covered under the MHB criteria. However, under the ISBC code, appropriate precautions shall be taken to protect machinery and accommodation spaces from the dust of the cargo. Bilge wells of the cargo spaces shall be protected from ingress of the cargo. Due consideration shall be paid to protect equipment from the dust of cargo. Persons, who may be exposed to the dust of the cargo, shall wear protective clothing, goggles or other equivalent dust eye-protection and dust filter masks, as necessary. Amend as appropriate or used not applicable if this is the case SECTION 15: REGULATORY INFORMATION: [Delete as appropriate and include regulatory information specific to your country...] 15.1 Safety, health and environmental regulations/legislation for the substance: UN GHS - UN Globally Harmonized System of Classification and Labeling of Chemicals (GHS): “According to Chapter 1.5.2 of the UN Globally Harmonized System of Classification and Labeling of Chemicals (GHS) safety data sheets (SDS) are only required for substances and mixtures that meet the harmonized criteria for physical, health or environmental hazards. This substance meets these criteria; hence a safety data sheet is required. EU REACH – Registration, Evaluation and Authorisation of Chemicals: REACH annex V, exempts the registration of naturally occurring, unmodified substances such as mineral ores. 8 I n t e r n a t i o n a l M a n g a n e s e I n s t i t u t e Association SECTION 16: OTHER INFORMATION: 16.1 Sources of key data: 1. Assem, F. L., et al, (2011); The Mutagenicity and carcinogenicity of inorganic manganese compounds: A synthesis of the evidence, Journal of toxicology and environment, part B 2. Brouwers T (2014) : Rhrodochrosite ore: 24 hour Transformation/Dissolution screening study in a standard aqueous medium at pH 6 and 8. Test Laboratory: ECTX Ecotoxicology and biodegradation, Belgium. Owner Company: International Manganese Institute, 17 Rue Duphot, 75001 Paris, France. 3. Flanders L (2009). MnCl2 (Eramet): L5178Y TK +/- Mouse Lymphoma Assay. Testing laboratory: Harlan Laboratories Ltd, Shardlow Business Park, Shardlow, Derbyshire, DE72 2GD, UK. Report no.: 2702-0037. Owner Company: International Manganese Institute, 17 Rue Duphot, 75001 Paris, FRANCE. Report date: 2009-11-17. 4. Griffiths DR (2013). Pyrolusite ore: Acute Inhalation Toxicity (Nose Only) Study in the Rat. Testing laboratory: Harlan Laboratories Ltd, Shardlow Business Park, Shardlow, Derbyshire, DE72 2GD, UK. Company: International Manganese Institute, 17 Rue Duphot, 75001 Paris, FRANCE. 5. Morris A & Durward R (2009). MnCl2 (Eramet): Chromosome Aberration Test in Human Lymphocytes In Vitro. Testing laboratory: Harlan Laboratories Ltd, Shardlow Business Park, Shardlow, Derbyshire, DE72 2GD, UK. Report no.: 2702-0036. Owner Company: International Manganese Institute, 17 Rue Duphot, 75001 Paris, FRANCE. Report date: 2009-11-23. 6. Pooles A (2013). Pyrolusite Ore: Acute Oral Toxicity in the Rat - Fixed Dose Method. Testing laboratory: Harlan Laboratories Ltd, Shardlow Business Park, Shardlow, Derbyshire, DE72 2GD, UK. Owner Company: International Manganese Institute, 17 Rue Duphot, 75001 Paris, FRANCE. 7. Scobie H (2014). Unmodified Pyrolusite ore: In vitro skin corrosion (OECD 431), In vitro skin irritation (OECD 439) and in vitro severe eye damage/irritation (OECD 437). Toxicology consultants – TOXICOS Report 8. SCOEL/SUM/127., (2011); EC recommendation from the scientific committee on occupational exposure limits for manganese and inorganic manganese compounds 9. Streicker MA (2009). In Vivo Micronucleus Assay of Manganese According to OECD 474 guideline. Testing laboratory: Integrated Laboratory Systems, Inc. 601 Keystone Park Drive, Suite 100, Durham, NC 27713. Report no.: C171-001. Owner Company: Manganese Research Health Project (MHRP) 10. Thompson PW & Bowles A (2009). MnCl2 (Eramet): Reverse Mutation Assay "Ames Test" Using Salmonella Typhimurium and Escherichia Coli. Testing laboratory: Harlan Laboratories Ltd, Shardlow Business Park, Shardlow, Derbyshire, DE72 2GD, UK. Report no.: 2702-0035. Owner Company: International Manganese Institute, 17 Rue Duphot, 75001 Paris, FRANCE. Report date: 2009-09-2 11. Tremain SP (2014). Pyrolusite ore: Hazadous physicho-chemical properties. Testing laboratory: Harlan Laboratories Ltd, Shardlow Business Park, Shardlow, Derbyshire, DE72 2GD, UK. Report no.: 2702-0061. Owner Company: International Manganese Institute, 17 Rue Duphot, 75001 Paris, FRANCE. Date: Sept 2015 Author: Dr Doreen McGough (Contact: OHES@manganese.org) 9