RISK ASSESSMENT REPORT ZINC SULPHATE CAS-No.: 7733-02-0 EINECS-No.: 231-793-3 GENERAL NOTE This document contains: - part I Environment (pages 41) - part II Human Health (pages 130) R076_0805_env RISK ASSESSMENT ZINC SULPHATE CAS-No.: 7733-02-0 EINECS-No.: 231-793-3 Final report, May 2008 PART 1 Environment Rapporteur for the risk evaluation of zinc sulphate is the Ministry of Housing, Spatial Planning and the Environment (VROM) in consultation with the Ministry of Social Affairs and Employment (SZW) and the Ministry of Public Health, Welfare and Sport (VWS). Responsible for the risk evaluation and subsequently for the contents of this report is the rapporteur. The scientific work on this report has been prepared by the Netherlands Organization for Applied Scientific Research (TNO) and the National Institute of Public Health and Environment (RIVM), by order of the rapporteur. Contact point: Bureau Reach P.O. Box 1 3720 BA Bilthoven The Netherlands R076_0805_env PREFACE For zinc metal (CAS No. 7440-66-6), zinc distearate (CAS No. 557-05-1 / 91051-01-3), zinc oxide (CAS No.1314-13-2), zinc chloride (CAS No.7646-85-7), zinc sulphate (CAS No.7733- 02-0) and trizinc bis(orthophosphate) (CAS No.7779-90-0) risk assessments were carried out within the framework of EU Existing Chemicals Regulation 793/93. For each compound a separate report has been prepared. It should be noted, however, that the risk assessment on zinc metal contains specific sections (as well in the exposure part as in the effect part) that are relevant for the other zinc compounds as well. For these aspects, the reader is referred to the risk assessment report on zinc. 2 CAS No.7733-02-0 R076_0805_env CONTENTS 0 OVERALL CONCLUSIONS/RESULTS OF THE RISK ASSESSMENT 6 1 GENERAL SUBSTANCE INFORMATION 8 2 GENERAL INFORMATION ON EXPOSURE 10 2.1 Production 10 2.2 Use pattern 10 3 ENVIRONMENT 12 3.1 General introduction 12 3.2 Exposure assessment 13 3.2.1 Exposure scenarios 14 3.2.1.1 General 14 3.2.1.2 Local exposure assessment 16 3.2.1.2.1 General 16 3.2.1.2.2 Production of zinc sulphate 16 3.2.1.2.3 General information on the use categories of zinc sulphate in the EU 19 3.2.1.2.4 Processing in agricultural pesticide industry 21 3.2.1.2.5 Formulation in agricultural fertiliser industry 22 3.2.1.2.6 Formulation in agricultural feed industry 24 3.2.1.2.7 Processing of zinc sulphate in the chemical industry 25 3.2.1.2.8 Measured local data in the environment 26 3.2.1.2.9 Summary of results for the local exposure assessment 26 3.3 Effects assessment 27 3.3.1 Aquatic and terrestrial compartment 27 3.3.2 Atmosphere 28 3.3.3 Secondary poisoning 28 3.4 Risk characterisation 29 3.4.1 General 29 3.4.2 Local risk characterisation 33 3.4.2.1 Aquatic compartment 33 3.4.2.1.1 STP effluent 33 3.4.2.1.2 Surface water (incl. sediment) 34 3.4.2.2 Terrestrial compartment 35 3.4.2.3 Atmospheric compartment 35 3.4.2.4 Secondary poisoning 35 3.4.3 Regional risk characterisation 37 APPENDIX 3.4 BIOAVAILABILITY CORRECTIONS 39 4 REFERENCES 41 3 CAS No.7733-02-0 R076_0805_env 4 CAS No.7733-02-0 R076_0805_env 5 CAS No.7733-02-0 R076_0805_env 0 OVERALL CONCLUSIONS/RESULTS OF THE RISK ASSESSMENT CAS No. 7733-02-0 EINECS No. 231-793-3 IUPAC Name Zinc Sulphate ( ) i) There is need for further information and/or testing (X) ii) There is at present no need for further information and/or testing and for risk reduction measures beyond those which are being applied already (X) iii) There is a need for limiting the risks; risk reduction measures which are already being applied shall be taken into account (X) iii*) A conclusion applied to local scenarios in which the local scenario merits conclusion (ii) but where (possibly) due to high regional background concentrations a local risk cannot be excluded. LOCAL Conclusion (ii) is drawn for all local scenarios, including secondary poisoning, except those listed below. Conclusion (iii) or (iii*) is drawn for the specified scenarios, because: STP • the PECSTP exceeds the PNECadd for microorganisms for three processing scenarios of zinc sulphate listed in Table 3.4.10 (conclusion iii). Surface water • the calculated Clocaladd in water is greater than the PNECadd in surface water for one processing scenario for zinc sulphate listed in Table 3.4.10 (conclusion iii). • the Clocaladd / PNECadd ratio is 1 (conclusion ii) for one other processing scenario for zinc sulphate listed in Table 3.4.10, but a potential risk at local scale cannot be excluded due to the possible existence of high regional background concentrations (conclusion iii*). Sediment • the Clocaladd in sediment exceeds the PNECadd in sediment for three processing scenarios listed in Table 3.4.10 (conclusion iii). • the Clocaladd / PNECadd ratio is 1 for the remaining scenarios for zinc sulphate listed in Table 3.4.10 (conclusion ii), but a potential risk at local scale cannot be excluded due to the possible existence of high regional background concentrations (conclusion iii*). 6 CAS No.7733-02-0 R076_0805_env Soil • PEClocaladd / PNECadd ratios >1 exist for the terrestrial compartment for three processing scenarios of zinc sulphate listed in Table 3.4.10 (conclusion iii). REGIONAL The regional risk characterisation is discussed in the RAR on Zinc Metal. 7 CAS No.7733-02-0 R076_0805_env 1 GENERAL SUBSTANCE INFORMATION Identification of the substance CAS-No.: 7733-02-0 EINECS-No.: 231-793-3 IUPAC name: zinc sulphate Synonyms: sulphuric acid-zinc salt; zincate; zincomed; white vitriol; zinc vitriol Molecular formula: ZnSO4 Structural formula: ZnSO4 Molecular weight: 161.4 Purity/impurities, additives Purity: no data Impurity: no data Additives: no data Physico-chemical properties In table 1A the physico-chemical properties are summarized. Table 1A Physico-chemical properties of zinc sulphate Property Result Comment Physical state solid * Melting point 600 ºC * Boiling point not applicable * Relative density 3.54 * Vapour pressure no data *** Surface tension no data *** Water solubility 220 g/l (20ºC) ** Solubility in other solvents slowly soluble in alcohol; * soluble in MeOH and glycerin Partition coefficient no data *** n-octanol/water(log value) Flash point not applicable *** Flammability not flammable *** Autoflammability temperature not applicable *** 8 CAS No.7733-02-0 R076_0805_env Property Result Comment Explosive properties not explosive *** Oxidizing properties not oxidizing *** * More than one apparently independent source. No methods are specified. ** One source. *** Conclusion based on theoretical and/or structural considerations. These data are mainly derived from CRC Handbook of Chemistry and Physics (1995), Sax’s Dangerous Properties of Industrial Materials (1984), Patty’s Industrial Hygiene and Toxicology (1981), Römpp Chemie Lexikon (1995), Ullmann’s Encyklopädie der Technischen Chemie (1983), and company information. For an extended description see HEDSET. Conclusion: Data on boiling point, vapour pressure, surface tension, and partition coefficient were not provided. In view of the nature of the substance determination of these parameters is considered to be irrelevant. Information on flammability, explosive properties and oxidizing properties is not available. However, on theoretical considerations the compound is concluded to be not flammable, not explosive and not oxidizing. All other required physico-chemical data were submitted. None of these data is based on test results, substantiated with reports. However, the data are considered as sufficiently reliable to fulfil the Annex VIIA requirements. Classification and labelling (human health, environment and physico-chemical) Annex 1 of Directive 67/548/EEC contains a list of harmonised classifications and labellings for substances or groups of substances, which are legally binding within the EU. For zinc sulphate the current Annex 1 classification and labelling (29th ATP, 2004) is as follows: Classification Xn; R22 R41 N; R50-53 Labelling Xn; N R: 22-41-50/53 S: (2-)22-26-39-46-60-61 The above classification and labelling is for hydrous forms of zinc sulphate (mono-, hexa-, and hepta-hydrate) and for anhydrous zinc sulphate. 9 CAS No.7733-02-0 R076_0805_env 2 GENERAL INFORMATION ON EXPOSURE 2.1 PRODUCTION Zinc sulphate is produced (>1000 t/y) at five known sites in the European Union (see Table 2.1.1) Table 2.1.1 Production sites of zinc sulphate (>1000 t/y) in the EU (Information from Industry) Company Location Floridienne Chimie S.A. Belgium Grillo Werke AG Duisburg, Germany Pasminco Budel Zink The Netherlands Eco-Zinder Trezzo, Italy I.C.A. SRL Arborio, Italy The total production volume of zinc sulphate in the EU for 1994 is confidential. The same is true for export figures outside the EU. Zinc sulphate was imported from outside the EU by at least one company. The import volume is unknown. Based on production, export and import data the total use volume within the EU is estimated to be circa 28,000 tonnes per year. 2.1.1 Production process Zinc sulphate is produced starting with zinc bearing material, as for instance zinc ashes, zinc carbonate or other zinc remains. Initially, zinc is leached from these materials with sulphuric acid, followed by various purification processes. Lead sulphate is precipitated and sold as secondary raw material. A reduction of pH to mildly acidic concentrations is affected by addition of zinc oxide, leading to a precipitation predominantly of manganese and iron hydroxide (jarosite sludge). Metallic zinc dust is added, which leads to the precipitation of other heavy metals such as copper, cadmium etc., which is sold as secondary raw material.