ZINC SULFATE Supersedes Rev

Code: FDS-15 SAFETY DATA SHEET Page 1 / 6 According Regulation (EC) 1907/2006 Revision Nº: 5

Date: 2016/12/14 ZINC SULFATE Supersedes Rev. Nº:4

SECTION 1: Identification of the substance/mixture and of the company/undertaking

1.1. Product identifier Product name: purified zinc sulphate solution Chemical name: Wastewater, zinc sulfate electrolytic, acid (purified zinc solution) Description: Electrolytic solution of zinc sulfate consisting primarily of zinc sulfate and possibly sulfuric acid Index-No: Not listed* CAS-No: 69012-24-4 EC-No: 273-723-4 REACH Pre-Registration – No: 05-2114522095-57-0000

*Zinc sulfate (hydrous) (mono-, hexa and hepta- hydrate): EC No.: 231-793-3, CAS No.: 7446-19-7, Index No.: 030- 006-00-9

1.2. Relevant identified uses of the substance or mixture and uses advised against Relevant identified uses: Production of Zinc metal or Zinc compounds. Used as reagent in paper industry. Uses advised against: No uses advised against have been identified

1.3. Details of the supplier of the safety data sheet Asturiana de Zinc, S.A.U. 33417-San Juan de Nieva, Castrillón ASTURIAS-ESPAÑA +34 985 128 100 [email protected]

1.4. Emergency telephone number Phone (24h): +34 985 128 100 Single emergency telephone number inside the EU: 112

SECTION 2: Hazards identification

2.1. Classification of the substance or mixture

Category Hazards statements Acute Tox. 4 (Hazard statement: H302: Harmful if Acute toxicity - oral: swallowed.) Eye Damage 1 (Hazard statement: H318: Causes serious Serious damage/eye irritation: eye damage.) STOT RE 2 (Hazard statement: H373 May cause damage to STOT repeated exposure: organs through prolonged or repeated exposure) Aquatic Acute 1 (Hazard statement: H400: Very toxic to aquatic life) Hazards to the aquatic environment: Aquatic Chronic 1 (Hazard statement: H410: Very toxic to aquatic life with long lasting effects.)

2.2. Label elements Hazard pictogram:

GHS08 GHS05 GHS09

Signal word: DANGER Hazard statements: H302: Harmful if swallowed. H318: Causes serious eye damage. H373: May cause damage to organs through prolonged or repeated exposure H410: Very toxic to aquatic life with long lasting effects.

This document is the property of Asturiana de Zinc, S.A.U Reproduction in whole or in part without written consent is not permitted. The information contained in this Product Safety Data Sheet is based on our current knowledge and does not represent a warranty of the properties described herein. The receiver of our product should observe, at his own responsibility, the applying rules and regulations. Only the electronic version is a controlled document, so that a paper copy is considered outdated. F-PG-001-13 Code: FDS-15 SAFETY DATA SHEET Page 2 / 6 According Regulation (EC) 1907/2006 Revision Nº: 5

Date: 2016/12/14 ZINC SULFATE Supersedes Rev. Nº:4

Precautionary statements: P301+P312: IF SWALLOWED: Call a POISON CENTER or doctor/physician if you feel unwell. P280: Wear protective gloves/protective clothing/eye protection/face protection. P305+P351+P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. P273: Avoid release to the environment. P391: Collect spillage. P501: Dispose of contents/container to hazardous wastes according to local, regional or national legislation

2.3. Other hazards No data available

SECTION 3: Composition/information on ingredients

Content Name Present as EINECS No. CAS No. Index No. (g/L) Zinc ZnSO4 334-395 231-793-3 7733-02-0 030-006-00-9 Magnesium MgSO4 < 100 231-298-2 7487-88-9 - Manganese MnSO4 < 30 232-089-9 7785-87-7 025-003-00-4 Sodium Na2SO4 < 25 231-820-9 7757-82-6 -

SECTION 4: First aid measures

4.1. Description of first aid measures. 4.1.1. General information: By the temperature of up to 80°C exists the danger of burns 4.1.2. After inhalation: The product is sold in liquid form. In case of inhalation of fumes or vapors remove the victim from exposure and bring to fresh air. If difficult breathing give oxygen. Get immediate medical attention. 4.1.3. After skin contact: Remove contaminated clothing. Rinse affected skin areas with cold running water for at least 15 minutes. If signs of burns, call a doctor 4.1.4. After contact with eyes: Rinse eyes with open lids with generous quantities of water for at least 15 minutes. Consult a physician. 4.1.5. After ingestion: After swallowing rinse the mouth with generous quantities of water. Obtain medical attention.

4.2. Most important symptoms and effects, both acute and delayed Possibility of irritation: eye (pain) and skin (redness) Ingestion: possibility of irritation of digestive tract. Nausea, vomiting, abdominal cramps, diarrhea. Liver and kidney damage.

4.3. Indication of any immediate medical attention and special treatment needed No data available

SECTION 5: Fire-fighting measures 5.1. Extinguishing media 5.1.1. Suitable fire extinguishing media: The product is not combustible. Use material that is appropriate for the surrounding fire. 5.1.2. Fire extinguishers that should not be used for safety reasons: none

5.2. Special hazards arising from the substance or mixture Particular danger from the substance: after evaporation of the liquid, sulfur trioxide is produced above 600°C

5.3. Advice for fire-fighters Special protective equipment for fire-fighting: use independent ventilated breathing protection if waste water, zinc sulfate electrolytic, acid can evaporate

SECTION 6: Accidental release measures 6.1. Personal precautions, protective equipment and emergency procedures Eating, drinking and smoking must be prohibited in areas where this material is handled and processed. Workers must wash hands and face before eating, drinking and smoking. See 8.2.1

6.2. Environmental precautions Do not permit the product to enter watercourses and reaching soil.

This document is the property of Asturiana de Zinc, S.A.U Reproduction in whole or in part without written consent is not permitted. The information contained in this Product Safety Data Sheet is based on our current knowledge and does not represent a warranty of the properties described herein. The receiver of our product should observe, at his own responsibility, the applying rules and regulations. Only the electronic version is a controlled document, so that a paper copy is considered outdated. F-PG-001-13 Code: FDS-15 SAFETY DATA SHEET Page 3 / 6 According Regulation (EC) 1907/2006 Revision Nº: 5

Date: 2016/12/14 ZINC SULFATE Supersedes Rev. Nº:4

6.3. Methods and material for containment and cleaning up Inside plant: recover by pumping and recycle to process Outside plant: dilute with water and collect in a convenient recycling container. If necessary neutralize residue with a diluted sodium carbonate solution. Wash down contaminated area. Collect water for recycling according to local and national regulations.

6.4. Reference to other sections Please refer to section 8 and 13 for more information

SECTION 7: Handling and storage 7.1. Precautions for safe handling Avoid contact with eyes, skin or clothes. Use safety gloves and safety glasses

7.2. Conditions for safe storage, including any incompatibilities Requirements for storage rooms and containers: Make only use of authorized containers. Observe elevate temperature of the material

7.3. Specific end use(s) No data available

SECTION 8: Exposure controls/personal protection 8.1. Control parameters Inorganic compounds of manganese, as manganese: VLA-ED®: 0.2 mg/m3 inhalable fraction VLA-ED®: 0.2 mg/m3 breathable fraction (2017)

8.2. Exposure controls 8.2.1. Occupational exposure controls a. Respiratory protection Not necessary in the case of product in supplied state (liquid) b. Hand protection Use protective gloves of nitrile rubber when exposed to the substance. Penetration time for the glove material can vary with the glove's thickness, usage and exposure. Ensure that the glove is intact, without holes or tears. c. Eye protection Use protective glasses. Eyewash should be available at the workplace. d. Skin protection. Wear suitable protective clothing. e. Hygiene measures Wash hands before eating, smoking etc. Change work clothes and shower after work.

8.2.2. Environmental exposure controls Use adequate local or general ventilation to maintain the concentration in the working environment well below recommended occupational exposure limits. Supply sufficient replacement air to make up for air removed by the exhaust system.

SECTION 9: Physical and chemical properties 9.1. Information on basic physical and chemical properties Appearance: clear to slightly opaque liquid Odor: odorless Physical State: liquid pH: 4.5-5.5 Relative density: 1.4 kg/L Water solubility: 960 g/L @ 20ºC Vapor pressure: 2890 Pa @ 25 °C

9.2. Other information No data available

SECTION 10: Stability and reactivity 10.1. Reactivity This product is stable and not considered reactive under normal temperatures and pressures.

10.2. Chemical stability Stable under normal conditions. Zinc sulfate decomposes above 600°C to zinc oxide and sulfur trioxide.

This document is the property of Asturiana de Zinc, S.A.U Reproduction in whole or in part without written consent is not permitted. The information contained in this Product Safety Data Sheet is based on our current knowledge and does not represent a warranty of the properties described herein. The receiver of our product should observe, at his own responsibility, the applying rules and regulations. Only the electronic version is a controlled document, so that a paper copy is considered outdated. F-PG-001-13 Code: FDS-15 SAFETY DATA SHEET Page 4 / 6 According Regulation (EC) 1907/2006 Revision Nº: 5

Date: 2016/12/14 ZINC SULFATE Supersedes Rev. Nº:4

10.3. Possibility of hazardous reactions Hazardous polymerization or runaway reactions will not occur.

10.4. Conditions to avoid Avoid heating above the decomposition point

10.5. Incompatible materials Strong oxidants. Acids.

This list of products is not exhaustive. Verify technical documents to determine any incompatibility

10.6. Hazardous decomposition products Zinc oxide and sulfur trioxide vapors.

SECTION 11: Toxicological information

11.1. Information on toxicological effects In the form in which this product is sold it is relatively non-toxic. The major route of exposure would be through the generation and inhalation of aerosol mist, or the generation of zinc oxide fume through welding or burning around dried residues.

SECTION 12: Ecological information

12.1. Toxicity

Aquatic invertebrates Method Results Remarks Reference Ceriodaphnia dubia EC50 (48 h): 413 μg/L 1 (reliable without restriction) Hyne R.V., Pablo freshwater dissolved (meas. key study F, Moreno J; , static (arithm. mean)) read accross of critical study record Markisch S.J. US EPA EPA 821-R-02- based on: mobility from specific substance (Zn) driving (2005) 012. Methods for EC50 (48 h): 200 μg/L classification measuring the acute dissolved (meas. Test material (IUPAC name): zinc toxicity of effluents and (arithm. mean)) receiving waters to based on: mobility freshwater and marine EC50 (48 h): 155 μg/L organisms, 5th Ed. (2002) dissolved (meas. (arithm. mean)) based on: mobility

Algae and aquatic plants

Method Results Remarks Reference Selenastrum IC50 (72 h): 136 μg/L 1 (reliable without restriction) Van Ginneken I. capricornutum (new name: dissolved (meas. (not key study (1994) Pseudokirchnerella specified)) based on: read accross of critical study record subcapitata) (algae) growth rate from specific substance (ZnO) freshwater NOEC (3 d): 24 μg/L driving classification static dissolved (meas. (not Test material (IUPAC name): zinc OECD Guideline 201 specified)) based on: oxide (Alga, Growth Inhibition growth rate Test)

12.2. Persistence and degradability According to Annex IX of REACH Regulation, information on hydrolysis is not required for inorganics. Also the other endpoints under IUCLID 5.1. e.g.; phototransformation in air, water and soil, are not applicable. Biodegradation is not applicable to metals/inorganics substances; study does not need to be conducted if substance is inorganic (Annex VII of REACH regulation)

This document is the property of Asturiana de Zinc, S.A.U Reproduction in whole or in part without written consent is not permitted. The information contained in this Product Safety Data Sheet is based on our current knowledge and does not represent a warranty of the properties described herein. The receiver of our product should observe, at his own responsibility, the applying rules and regulations. Only the electronic version is a controlled document, so that a paper copy is considered outdated. F-PG-001-13 Code: FDS-15 SAFETY DATA SHEET Page 5 / 6 According Regulation (EC) 1907/2006 Revision Nº: 5

Date: 2016/12/14 ZINC SULFATE Supersedes Rev. Nº:4

12.3. Bioaccumulative potential The studies on aquatic bioaccumulation and terrestrial are summarized in the chemical safety report, available under request. Zinc is an essential element which is actively regulated by organisms, so aquatic and terrestrial bioconcentration/ bioaccumulation is not considered relevant.

12.4. Mobility in soil For metals, the transport and distribution over the different environmental compartments e. g soil (fraction bound or complexed to the soil particles, fraction in the soil pore water...) is described and quantified by the metal partition coefficients between these different fractions. Information on these partition coefficients is given under IUCLID section 5.6. For soil, a solids-water partitioning coefficient of 158.5 l/kg (log value 2.2) was determined experimentally on 11 American soils. This value was used in the RA Zinc.

12.5. Results of PBT and vPvB assessment Zinc compounds are not PBT and vPvB

12.6. Other adverse effects No data available

SECTION 13: Disposal considerations

13.1. Waste treatment methods 13.1.1. Product/packaging disposal Waste should be recycled. If recycling is not possible, the waste is classified as hazardous waste: contact a certified contractor for treatment according to local and national regulations. Waste codes/waste designations according to EWC/AVV: EWC code 06 03 14 solid salts and solutions other than those mentioned in 06 03 11 and 06 03 13

Specification of the waste material number and EWC-code are for illustrative purposes only. Which waste catalogue number and code to use must be decided by the end user based on the actual use of the product.

Contaminated containers and packaging of dangerous substances or preparations must be treated in the same manner as the actual products contained in them.

Directive 2008/98/EC of the European Parliament and of the Council of 19 November 2008 on waste and repealing certain Directives.

2014/955/EU: Commission Decision of 18 December 2014 amending Decision 2000/532/EC on the list of waste pursuant to Directive 2008/98/EC of the European Parliament and of the Council

Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006

13.1.2. Waste treatment options On-site waste water treatment techniques can be applied to prevent releases to water e.g.: chemical precipitation, sedimentation and filtration

SECTION 14: Transport information 14.1. UN number 3082 14.2. UN proper shipping name Environmentally hazardous substance, liquid, n.o.s. (zinc sulfate)

14.3. Transport hazard class(es) 9

14.4. Packing group III

14.5. Environmental hazards: Hazardous to the aquatic environment: Aquatic Chronic 1 (H410: Very toxic to aquatic life with long lasting effects. According to GHS) This document is the property of Asturiana de Zinc, S.A.U Reproduction in whole or in part without written consent is not permitted. The information contained in this Product Safety Data Sheet is based on our current knowledge and does not represent a warranty of the properties described herein. The receiver of our product should observe, at his own responsibility, the applying rules and regulations. Only the electronic version is a controlled document, so that a paper copy is considered outdated. F-PG-001-13 Code: FDS-15 SAFETY DATA SHEET Page 6 / 6 According Regulation (EC) 1907/2006 Revision Nº: 5

Date: 2016/12/14 ZINC SULFATE Supersedes Rev. Nº:4

14.6. Special precautions for user: No data available

14.7. Transport in bulk according to Annex II of MARPOL 73/78 and the IBC Code This product is out of the scope of Annex II of MARPOL 73/78

SECTION 15: Regulatory information 15.1. Safety, health and environmental regulations/legislation specific for the substance or mixture Contains zinc sulfate (Index No.: 030-006-00-9): Seveso substance: yes Seveso category: E1

Contains manganese sulfate (Index No.: 025-003-00-4): Seveso substance: yes Seveso category: E2.

15.2. Chemical safety assessment A Chemical safety assessment has been carried out

SECTION 16: Other information 16.1 Indication of changes Information added, deleted or revised: 8.1 and 15.1

16.2 Key literature references and sources for data

 CHEMICAL SAFETY REPORT  IUCLID 5  www.echa.com  Límites De Exposición Profesional Para Agentes Químicos En España. (INSHT).  Commission Regulation (EU) No 453/2010 of 20 May 2010 amending Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH)  Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006  Commission Regulation (EC) No 790/2009 of 10 August 2009 amending, for the purposes of its adaptation to technical and scientific progress, Regulation (EC) No 1272/2008 of the European Parliament and of the Council on classification, labelling and packaging of substances and mixtures

16.3. Further information

List of uses for which a Generic Exposure Scenario (GES) is provided as annex:

1. GES ZnSO4 Bleed -0: Industrial isolation of the Intermediate ZnSO4 solution bleed (273-723-4) from Zinc- metallurgical leaching, gas-cleaning or electrolysis steps, by settling, filtering and other hydrometallurgical processes 2. GES ZnSO4 Bleed -2: Industrial use of the Intermediate ZnSO4 solution bleed (273-723-4) in the ultimate manufacturing of Zinc or Zinc compounds by several metallurgical processes.

End of safety data sheet