Safety Data Sheet. according to Regulation (EC) 1907/2006. Orthophosphoric Acid 52% P 2 O 5

Transcription

1 Zaklady Chemiczne Police S.A. Safety Data Sheet according to Regulation (EC) 1907/2006 Orthophosphoric Acid 52% P 2 O 5 SDS-ZChP- 004/10 version 05 The date of: compilation revision SECTION 1: Identification of the substance and of the company/undertaking 1.1. Product identifier Product name Orthophosphoric Acid Synonyms Technical phosphoric acid 72%, phosphoric acid technical min. 52% P 2O 5, wet process phosphoric acid, phosphoric(v) Molecular formula H 3PO 4 CAS Number EC Number Registration number Relevant identified uses of the substance or mixture and uses advised against Use of orthophosphoric acid: For production of mineral fertilizers, feed phosphates, phosphate coatings on metals, intermediate, laboratory chemicals, ph regulators, washing and cleaning products Details of the supplier of the safety data sheet A person responsible for Safety Data Sheet 1.4. Emergency telephone number Chief Dispatcher SECTION 2: Hazards identification Grupa Azoty Zaklady Chemiczne Police S.A. Internet: grupaazoty.com Kuznicka 1, Police, Poland Phone no: Tele-Fax no: Agnieszka Belcyr /MSc eng/ Phone no ; Tele-Fax: ; agnieszka.belcyr@grupaazoty.com Alarm telephone no: (24h) Telephone no: (24h) 2.1. Classification of the substance Hazard Class and Category Code Hazard Statement Explanation phrases in section 16. Skin Corr. 1B H290, H314 Note B Human Heath effects Skin effect Contact with skin causes redness and burning. Eyes effect Pouring the eyes can cause irritation and burns. Swallowing It can cause corrosion and damage to the gastrointestinal tract. Inhalation Acid mist can cause irritation of the throat and lungs.

2 Orthophosphoric Acid 52% P 2O 5 Safety Data Sheet Page 2 of 9 Long - term effects The severity of acute effects is so large that staying in the affected area for an extended period of time is impossible. Environmental effects Orthophosphoric acid is harmful to aquatic organisms, animals and plants Label elements Pictogram Signal Word Hazard Statement Precautionary Statement Explanation phrases in section 16. GHS05 Danger H290 H314 P280 P310 P301 + P330 + P331 P303 + P361 + P353 P305 + P351 + P338 P Other hazards Phosphoric acid in concentrations 20% w/w are classified as corrosive to metals (Met. Corr. 1, H290: May corrosive to metals). Phosphoric acid is neither a PBT nor a vpvb substance. SECTION 3: Composition/information on ingredients 3.1. Substances Dangerous ingredient % CAS number EC number Orthophosphoric Acid SECTION 4: First aid measures %H 3PO 4 (52-56% P 2O 5) Description of first aid measures Inhalation Breathe fresh air. If breathing discomfort occurs and persists after cessation of exposure, see a doctor. Remove injured from exposure area. Keep in peace and quiet, lay in a comfortable reclining or sitting position. Protect against warm loss. Give oxygen if difficulty in breathing occur. Skin contact Rinse with water and soap. Take off immediately all contaminated clothing. Consult a doctor if irritation persists. Put on the burn skin under sterile dressing. Eye contact In case of contact with eyes, flush with copious amounts of water for at least 15 minutes. Assure adequate flushing by separating the eyelids with fingers. Remove contact lenses, if present and easy to do - continue rinsing. Seek medical advice. Swallowing If swallowed, rinse mouth with water (only if the person is conscious) and then drink plenty of water. Do not induce vomiting. Seek medical advice.

3 Orthophosphoric Acid 52% P 2O 5 Safety Data Sheet Page 3 of Most important symptoms and effects, both acute and delayed Orthophosphoric acid causes irritation and corrosive burns if in contact with tissues. The vapour may also cause irritation to the eyes throat and skin. No delayed effects are noted Indication of any immediate medical attention and special treatment needed It can cause burns of mouth and throat, irritation of the stomach and intestines, or ulcers. There is a risk of perforation. It can cause sore throat and abdominal pain, difficulty in swallowing, thirst, nausea and vomiting and diarrhea. Severe burns can lead to collapse and death. Rinse immediately with plenty of water. Remove contaminated clothing and shoes. SECTION 5: Firefighting measures 5.1. Extinguishing media Suitable extinguishing media Unsuitable extinguishing media Put out the fire using appropriate agents against expanding fire. Fires in the presence of orthophosphoric acid: extinguish using media suitable for burning materials. Use water spray to cool fire-exposed tanks and containers. If possible remove them from the hazardous area. Wear breathing apparatus and full protective clothing. Not applicable 5.2. Special hazards arising from the substance or mixture Non-flammable. Fluorine compounds and/or hydrogen fluoride are evolved when heating wet process phosphoric acid. Thermal decomposition of phosphoric acid produces toxic phosphorus oxides. Hydrogen gas is released in contact with most metals Advice for firefighters Act according to the combustible substance involved. Protective clothing is required. Wear self-contained breathing apparatus, rubber boots and thick rubber gloves. Wear appropriate eye protection. See Section 8.2. Cool closed containers exposed to fire with water spray. SECTION 6: Accidental release measures 6.1. Personal precautions, protective equipment and emergency procedures Wear personal protective equipment. Depending on the level of risk in emergency situations need to use: anti-gas mask with canister type B, class P2 according to EN-141, personal protective equipment insulating body (tight suit combined with the equipment protecting respiratory tract), acid resistant clothes Environmental precautions Contain and collect spillage with non flammable absorbent material, (e.g. sand, earth, diatomaceus earth, vermiculite). Avoid undiluted spillage entering the sewers, basements or pits and watercourses. Inform appropriate authorities in the event of accidental water pollution Methods and material for containment and cleaning up Large Spill: Assembly embankment, pump spill out.

4 Orthophosphoric Acid 52% P 2O 5 Safety Data Sheet Page 4 of 9 Small Spill: Small amounts of spilled liquid cover up with non flammable and absorbing material (preferably ground limestone), collect into a closed container. Contaminated area should be neutralized with lime or soda and then washed. Use sand, fly ash and cement to absorb the spill. Neutralize with slaked lime (calcium hydroxide), sodium carbonate, calcium carbonate or sodium bicarbonate. Secure drains. If possible, stop the leak (close the flow of liquid, damaged container put in a tight protective container). Do not allow acid to come into contact with metals. Depending on the degree and type of product contamination transfer to specialized company in order to dispose it or after neutralization use as fertilizer on the farm Reference to other sections Information on personal precautions - see Section 8, waste disposal - see Section 13. SECTION 7: Handling and storage 7.1. Precautions for safe handling Store in cool, dry, clean, well ventilated areas, away from alkaline products and metals. Do not store under direct sun light.. Do not store at temperatures close to freezing point. Do not stack the containers Compatible materials: Stainless steel 316-L, high-density polyethylene, glass. When handling small quantities of acid wear goggles and chemical resistant gloves made of PVC. If there is a risk of spillage or leakage one should wear complete protective clothing Conditions for safe storage, including any incompatibilities Store in a cool, well ventilated area, away from potential sources of heat and fire, with an emergency mechanical ventilation, with non-absorbent, acid resistant and easily washable floor with the slope towards drains, separate sewers, internal water supply. Keep away from combustible materials, strong bases and metals. Large storage tanks should be walled and electrically grounded Specific end use(s) Exposure scenarios for identified uses are attached to this safety data sheet. SECTION 8: Exposure controls/personal protection 8.1. Control parameters Limit value Eight hours Limit value Short term mg/m³ mg/m³ European Union 1 2 France 1 (0.2 ppm) 2 (0.5 ppm) Germany 2 inhalable aerosol 4 inhalable aerosol Italy 1 2 Poland 1 2 Spain 1 2 Sweden 1 3 United Kingdom 1 2 Source of information:

5 Orthophosphoric Acid 52% P 2O 5 Safety Data Sheet Page 5 of 9 DNEL 1 for workers Long-term - local effects Inhalation 2.92 mg/m³ DNEL for the general population Long-term - local effects Inhalation 0.73 mg/m³ PNEC 2 The value is not calculated. Orthophosphoric acid will progressively dissociate in water to give H + and PO 4 3- ions. Due to its high water solubility and low vapour pressure it is predicted that any un-dissociated phosphoric acid will remain in the water phase and will not absorb onto particulate Exposure controls Exposure scenarios for identified uses are attached to this safety data sheet. Appropriate engineering controls: Ensure work area is well ventilated or exhausted (where appropriate and in line with the exposure scenarios). Emergency eye wash fountains and safety showers should be available in the immediate vicinity of any potential exposure. Personal protection measures. Eye protection Goggles protecting eyes against chemical products or a face protection shield. Hand protection Wear suitable gloves (Chloroprene, Neoprene or PVC gloves) Skin protection Use natural rubber boots. Use acid resistant protective clothing. made of coated materials (such as viton, butyl rubber, polyvinyl chloride, neoprene or Hypalon). Respiratory Not required for daily works. protection In case of mist or vapor use a mask hiding the whole face with the proper filter with an inorganic acid. A mask or a half mask completed with a filter class P2. In the event of oxygen deficiency (levels below 17% vol.). When the concentration of the compound is greater than 100 MAC, or if the concentration of substances in the air is not known, use the self-isolation equipment. SECTION 9: Physical and chemical properties 9.1. Information on basic physical and chemical properties Physical state at 20 C and 1013 hpa Solid / liquid ph <1 Melting / freezing point 41.1 C at 1013 hpa Boiling point C at 1013 hpa Relative density at 38 C Vapour pressure 4 Pa at 20 C Water solubility 1000 g/l at 20 C. Surface tension Not applicable Partition coefficient n-octanol/water Not applicable inorganic substance Flammability Non flammable Flash point Not applicable inorganic substance Self-ignition temperature Non flammable substance Explosive properties No explosive properties Oxidising properties No oxidizing properties Granulometry Not applicable liquid 1 DNEL Derived No-Effect Level 2 PNEC Predicted No-Effect Concentration

6 Orthophosphoric Acid 52% P 2O 5 Safety Data Sheet Page 6 of 9 Stability in organic solvents and identity Not applicable inorganic substance of relevant degradation products Dissociation constant pka1 = 2.1; pka2 = 7.2; pka3 = 12.3 at 20 C Viscosity 600 mpa.s at. 20 C (105%) 9.2. Other information No other information. SECTION 10: Stability and reactivity Reactivity Exothermic reaction with water Chemical stability The substance is stable in normal conditions of storage, use and handling Possibility of hazardous reactions Reacts violently with strong alkalis. In contact with reactive metals (aluminum) may produce hydrogen. At high temperature phosphorous oxides are formed Conditions to avoid High temperatures Incompatible materials Alkalis, aluminum, copper, mild steel, brass, bronze. Non-noble metals Hazardous decomposition products During heating of the acid obtained using wet process fluorine compounds are emitted. During thermal decomposition oxides of phosphorus are emitted. In reaction to the metals flammable hydrogen is separated. SECTION 11: Toxicological information Skin contact Eye contact Inhalation Swallowing Causes redness and burns, but it is not always immediate reaction. Pouring can cause irritation, conjunctivitis, burns. The risk of vision loss. Mists may irritate respiratory tract. It can cause burns of mouth and throat, irritation of the stomach and intestines or ulcers. There is a risk of perforation. Can cause sore throat and stomach, difficulty in swallowing, thirst, nausea and vomiting and diarrhea. Severe burns can lead to collapse and death Information on toxicological effects Acute toxicity Oral: LD50 3 = 1.7 ml / 100g bw/day, for a 10% solution of 75.4% phosphoric acid (equivalent to 2600 mg/kg bw). Not classified. Irritation/Corrosivity Skin: Corrosive Cat 1B (concentrations 25% w/w) Eye: Corrosive (concentrations 25% w/w) Eye irritant (concentrations 10% w/w < 25% w/w) Sensitization Not investigated substance is corrosive. Reproductive toxicity Not considered to be a reproductive or developmental toxicant NOAEL mg/kg bw/day Developmental toxicity: NOAEL (monosodium phosphate): 410 mg/kg bw/day Mutagenicity Not considered to be mutagenic. Carcinogenicity Not considered to be a carcinogen. 3 LD50 Lethal Dose 50% 4 NOAEL No Observed Adverse Effect Level

7 Orthophosphoric Acid 52% P 2O 5 Safety Data Sheet Page 7 of 9 STOT-single exposure all routes STOT-Repeated exposure - all routes No STOT SE classification however substance is corrosive and likely to cause respiratory irritation. Oral: NOAEL: 250 mg/kg bw/day Inhalation: no data Dermal: no data SECTION 12: Ecological information Toxicity Orthophosphoric acid does not fulfill the T criteria. Acute fish toxicity Acute toxicity Algal growth inhibition Median Lethal ph (96 hr): for Lepomis macrochirus. 48 h EC mg/l (nominal) (Daphnia) 72 h EC mg/l (nominal) 72 h NOEC 6 = 100 mg/l (nominal) Basis for effect: growth rate Persistence and degradability Orthophosphoric acid does not fulfill the P or vp criteria Bioaccumulative potential Orthophosphoric acid does not fulfil the B or vb criteria Mobility in soil Phosphoric acid is very soluble in water. Low volatile. Inorganic substance. Does not cause biological oxygen deficit. Phosphoric acid reacts with alkaline components of the soil producing phosphates with different degrees of solubility depending on soil ph. They are mainly of poorly soluble calcium compounds also found in mineral fertilizers. In anaerobic conditions, in the presence of certain micro-phosphates can be reduced to phosphine Results of PBT and vpvb assessment Orthophosphoric acid is neither a PBT nor a vpvb substance Other adverse effects No sediment or terrestrial toxicity data exists. Substance is not considered to be hazardous to sediment dwelling or terrestrial organisms. Increases in orthophosphoric acid concentrations may result in a decreased ph with may have a detrimental local effect on organisms. According to the criteria of the European classification and labeling system, the substance does not require classification as hazardous for the environment. SECTION 13: Disposal considerations Waste treatment methods Product remains, including packaging wastes, transfer to the specialized companies with an appropriate waste management permit. In case of leakage or spill of sulfuric acid, see - section 6 of the safety data sheet. European Waste Code: * phosphoric and phosphorous acid Regulation/legislation: Directive 2006/12/EC of the European Parliament and of the Council of 5 April 2006 on waste. (Official Journal of the European Union of , L114/9 with later changes) 5 EC50 Effective Concentration 50% 6 NOEC No Observed Effect Concentration

8 Orthophosphoric Acid 52% P 2O 5 Safety Data Sheet Page 8 of 9 Commission Decision 2000/532/EG establishing a list of wastes pursuant (Official Journal of the European Union of , L226/3 with later changes) SECTION 14: Transport information Transportation: road, car vehicles - orange, reflective warning boards, railway, cars - warning sticker No. 8, tankers and railway tankers - orange warning boards with identification numbers 80, 1805 warning label No UN number UN Number: 1805, hazard identification number: 80, Class 8, corrosive materials UN proper shipping name ORTHOPHOSPHORIC ACID, LIQUID Transport hazard class(es) ADR (roads transport): class 8, classification code C1, label 8 RID (railway): class 8, label 8 IMDG (see transport): class 8, kod IMDG 8204; label Packing group Packing group III Environmental hazards See section Special precautions for user As for hazardous materials. See section Transport in bulk according to Annex II of MARPOL 73/78 and the IBC Code Not applicable. SECTION 15: Regulatory information Safety, health and environmental regulations/legislation specific for the substance or mixture Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 18 th December 2006 concerning Registration, Evaluation, Authorization and Restriction of Chemicals (REACH), establishing a European Chemicals Agency, amending Directive 1999/45/EC and repealing Council Regulation (EEC) No 793/93 and Commission Regulation (EC) No 1488/94 as well as Council Directive 76/769/EEC and Commission Directives 91/155/EEC, 93/67/EEC, 93/105/EEC and 2000/21/EC. (Official Journal of the European Union of , L 396. with later changes)

9 Orthophosphoric Acid 52% P 2O 5 Safety Data Sheet Page 9 of 9 Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labeling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006 (Official Journal of the European Union of , L 353. with later changes) Chemical safety assessment The chemical safety assessment has been made. SECTION 16: Other information H phrases H290 - May corrosive to metals H314 - Causes severe skin burns and eye damage P phrases P280 - Wear protective gloves/protective clothing/eye protection/face protection. P310 - Immediately call a POISON CENTER or doctor/physician P301 + P330 + P331 - IF SWALLOWED: rinse mouth. Do NOT induce vomiting P303 + P361 + P353 - IF ON SKIN (or hair): Remove/Take off immediately all contaminated clothing. Rinse skin with water/shower P305 + P351 + P338 - IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing P406 - Store in corrosive resistant container with a resistant inner liner. Category Code Training Met. Corr. 1 - Substance or mixture corrosive to metals Skin Corr. 1B - Skin corrosion category 1B Employees should be trained in the scope of proper handling of the substance. Read the safety data sheet before use. Changes Section 2, 8, 9, 13, 15, 16. Attachments: ES02 ES03 ES04 Industrial use of phosphoric acid Professional use of phosphoric acid Consumer use of phosphoric acid

10 Zakłady Chemiczne Police S.A. EXPOSURE SCENARIO ES 02 Orthophosphoric Acid 52% P 2 O 5 ES-02/SDS-ZChP - 004/10 version 03 The date of: compilation revision ES 02 Industrial use of phosphoric acid 1. Short title of the exposure scenario: Industrial use of phosphoric acid. Sector of end use (SU): SU3 Industrial uses: Uses of substances as such or in preparations at industrial sites SU8 Manufacture of bulk, large scale chemicals (including petroleum products) SU9 Manufacture of fine chemicals SU10 Formulation [mixing] of preparations and/or repackaging (excluding alloys) SU14 Manufacture of basic metals, including alloys SU15 Manufacture of fabricated metal products, except machinery and equipment SU16 Manufacture of computer, electronic and optical products, electrical equipment SU17 General manufacturing, e.g. machinery, equipment, vehicles, other transport equipment SU19 Building and construction work SU20 Health services Product category (PC): PC0 Other: food and agro-food industry, farms and agro-industries, other industries. PC1 Adhesives, sealants PC7 Base metals and alloys PC8 Biocidal products (e.g. Disinfectants, pest control) PC9a Coatings and paints, thinners, paint removers PC9b Fillers, putties, plasters, modeling clay PC13 Fuels PC14 Metal surface treatment products, including galvanic and electroplating products PC15 Non-metal-surface treatment products PC19 Intermediate PC20 Products such as ph-regulators, flocculants, precipitants, neutralization agents PC21 Laboratory chemicals PC23 Leather tanning, dye, finishing, impregnation and care products PC24 Lubricants, greases, release products PC25 Metal working fluids PC26 Paper and board dye, finishing and impregnation products: including bleaches and other processing aids PC32 Polymer preparations and compounds PC33 Semiconductors PC34 Textile dyes, finishing and impregnating products; including bleaches and other processing aids PC35 Washing and cleaning products (including solvent based products)

11 EXPOSURE SCENARIO ES02 Orthophosphoric Acid 52% P 2O 5 Page 2 of 6 PC37 Water treatment chemicals PC39 Cosmetics, personal care products Process category (PROC): PROC 1 Use in closed process, no likelihood of exposure PROC 2 Use in closed, continuous process with occasional controlled exposure PROC 3 Use in closed batch process (synthesis or formulation) PROC 4 Use in batch and other process (synthesis) where opportunity for exposure arises PROC 5 Mixing or blending in batch processes for formulation of preparations and articles (multistage and/or significant contact) PROC 7 Industrial spraying PROC 8a Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at non dedicated facilities PROC 8b Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities PROC 9 Transfer of substance or preparation into small containers (dedicated filling line, including weighing) PROC 10 Roller application or brushing PROC 13 Treatment of articles by dipping and pouring PROC 14 Production of preparations or articles by tabletting, compression, extrusion, pelletisation PROC 15 Use as laboratory reagent PROC 21 Low energy manipulation of substances bound in materials and/or articles PROC 22 Potentially closed processing operations with minerals/metals at elevated temperature Industrial setting. PROC 23 Open processing and transfer operations with minerals/metals at elevated temperature PROC 24 High (mechanical) energy work-up of substances bound in materials and/or articles Environmental release category (ERC): ERC 1 Manufacture of substances ERC 2 Formulation of preparations ERC 3 Formulation in materials ERC 4 Industrial use of processing aids in processes and products, not becoming part of articles ERC 5 Industrial use resulting in inclusion into or onto a ma-trix ERC 6a Industrial use resulting in manufacture of another substance (use of intermediates) ERC 6b Industrial use of reactive processing aids ERC 6d Industrial use of process regulators for polymerization processes in production of resins, rubbers, polymers ERC 7 Industrial use of sub-stances in closed systems ERC 12a Industrial processing of ar-ticles with abrasive tech-niques (low release) Article category (AC): AC 1 Vehicles AC 2 Machinery, mechanical appliances, electrical/electronic articles AC 3 Electrical batteries and accumulators AC 4 Stone, plaster, cement, glass and ceramic articles AC 7 Metal articles

12 EXPOSURE SCENARIO ES02 Orthophosphoric Acid 52% P 2O 5 Page 3 of 6 2. Operational conditions 2. 1 Operational conditions related with frequency and quantities of use Duration of 8 hours/day exposure at workplace: Frequency of Once a day exposure at workplace: Annual amount The daily and annual amount/emission per site is not considered to be used per site: the main determinant for environmental exposure. 3.2 Operational conditions related with substance/ product Physical state Solid / Liquid (including aqueous solutions) Concentration of substance in mixture The concentration of phosphoric acid in industrial application ranges from 10 to 100% and worst case will be taken into account. 2.3 Other relevant operational conditions No information about frequency and duration of the various tasks is available. In the first-tier assessment of exposure a frequency of once a day and an exposure duration of 8 hours was considered. Workers are unlikely to be permanently subject to actual or potential exposure during the entire working shift. 3. Risk Management Measures 3.1 RMMs related to workers Organizational measures Technical measures Respiratory protection Hand protection Eye protection The employer must ensure that the required PPE is available and used according to instructions (provide training if necessary). PPE are required when breaching the system or handling the pure substance and concentrated solutions. Safety showers and eye washes are installed to be available in the case of accidental contact. Use closed/ automated systems or covering of open containers (e.g. screens) to avoid irritating mists, sprayings and potential splashes. (Good practice) Transport over pipes, technical barrel filling/emptying of barrel with automatic systems (suction pumps etc.) (Good practice) Use of pliers, grip arms with long handles with manual use to avoid direct contact and exposure by splashes (no working over one s head) (Good practice) Store in cool, dry, clean, well ventilate areas. (Good practice). Local exhaust / general ventilation should be present Respiratory protection: Personal Respiratory Equipment (PRE): In situations where aerosols, mists or fogs may be formed it is suggested to wear an all over facemask, containing an appropriate inorganic acid filter or an all-over face mask connected to a fresh air supply (PRE is not required when handling solid phosphoric acid). As modeling tools are likely to produce an over-estimate of the exposure to phosphoric acid, in instances where the company handling the phosphoric acid has workplace monitoring data to show that actual exposures are not a concern it is anticipated that personal respiratory equipment and /or LEV may not be necessary. Hand protection is required: Impervious chemical resistant protective gloves are required. Material of gloves. Chloroprene, Neoprene or PVC gloves Wearing of eye/face protection is required. Goggles or face protection shield should be consistent with EN 166 or equivalent.

13 EXPOSURE SCENARIO ES02 Orthophosphoric Acid 52% P 2O 5 Page 4 of 6 Skin and body Wearing of suitable protective clothing and rubber boots is required. protection Hygiene Keep away from foodstuffs, drinks and tobacco. Wash hands before measures breaks and at end of work. Keep work clothes separate. 3.2 RMMs related to the environment Organizational Emissions to the environment must meet the requirements of Council measures Directive 96/61/EC and national regulations concerning phosphate in industrial water. Regular control of the ph value previous to or during introduction of process wastewaters into open waters is required. In general, discharges should minimise ph changes in receiving surface Abatement measures related with wastewater Abatement measures waste air and solid waste waters. The efficiency of the process is maximized in such a way that minimal emission of phosphates into the wastewater will occur. In addition, phosphate can be precipitated from the wastewater by addition of metal ions. Phosphoric acid waste should be reused or discharged to the industrial wastewater and further neutralized if needed. Phosphoric acid is not expected to be found in the solid waste or to reach the air compartment, due to its low vapour pressure. Therefore, no specific risk management measures for air emissions are provided. 3.3 Waste related measures Type of waste Liquid waste, solid residues, packaging material Disposal technique Fraction released to environment during waste treatment The release of phosphates to wastewater is highly regulated, In addition ph changes in receiving waters should be minimised. The residue of the containers or the used container itself should be disposed in accordance with local and national requirements. See Section 13 of the SDS for more information. Not determined. The ph of wastewater released from manufacturing sites should be between ph Prediction of exposure and comparison of predicted exposure with DNELs (Risk Characterization) 4.1. Human exposure Exposure estimation tool(s) Workers (oral) Workers (inhalation) Workers, inhalation: MEASE The industrial use of orthophosphoric acid will not result in exposure via the oral route. It is assumed that workers in industrial settings adhere to the principles of good working practice and as such do not eat, smoke or drink near chemicals. Therefore no DNEL or assessment is required. Orthophosphoric acid is corrosive to the eyes. The use of safety goggles is compulsory. Further, some processes require the use of LEV and/or PRE (see below). As modeling tools are likely to produce an over-estimate of the exposure to phosphoric acid, in instances where the company handling the phosphoric acid has workplace monitoring data to show that actual exposures are not a concern it is anticipated that personal respiratory equipment and /or LEV may not be necessary. The risk characterization ratios (RCR) have only been derived for the long-term DNEL for inhalation. Any acute effects via inhalation are

14 EXPOSURE SCENARIO ES02 Orthophosphoric Acid 52% P 2O 5 Page 5 of 6 also covered with this risk characterization. Since phosphoric acid is corrosive to the skin, dermal exposure has been addressed qualitatively in the exposure scenarios and indications on the relevant and required RMM (PPE) have been given. Workers (dermal) Indirect exposure via the environment Consumers Phosphoric acid is a corrosive substance. For the handling of corrosive substances and formulations immediate dermal contact mainly occurs accidentally (splashes, etc) as wearing of gloves and skin protection is mandatory. Direct contact is forbidden and therefore it is assumed that on the basis of a qualitative assessment of potential dermal exposure that for the purpose of risk assessment dermal exposure can be discounted. Dermal exposure to > 25% phosphoric acid formulations is not quantitatively assessed as phosphoric acid is a very corrosive agent. No indirect exposure of humans via the environment is expected for orthophosphoric acid, as the substance can be effectively removed from the wastewater or neutralized. Thus, no assessment of indirect exposure of humans via the environment is performed. No direct consumer exposure is anticipated with the manufacture of orthophosphoric acid Environmental exposure (qualitative assessment) Environmental release Waste water treatment plants (WWTP) Aquatic pelagic compartment Sediments Soil and groundwater Atmospheric compartment The production of orthophosphoric acid can potentially result in aquatic emissions and locally increase the phosphate concentration while decreasing the ph in the aquatic environment. However, the ph of industrial effluents is normally measured frequently and can be neutralized easily. Not relevant. Orthophosphoric acid dissociates in H + and PO 3-4 and will be neutralized before reaching WWTP. The predominant adverse effects of orthophosphoric acid in aquatic systems are ph-related effects, as a result of the acidic nature of orthophosphoric acid. As phosphoric acid is a triprotic acid it will dissociate up to 3 times; releasing a phosphate anion (H 2PO - 4, HPO 2-4 or PO 3-4 ) and a H + ion at each dissociation. The fate of the H + ions (and subsequently the resultant ph) will depend on the chemical composition of the receiving water body; the higher the buffering capacity of the water, the lower the effect on ph will be. Not relevant. Orthophosphoric acid will progressively dissociate in water to give H + and PO 3-4 ions. Due to its high water solubility and low vapour pressure it is predicted that any un-dissociated phosphoric acid will remain in the water phase and will not absorb onto particulate. Not relevant. Orthophosphoric acid entering soil and ground water will be partially neutralized, dispersed and diluted. There will be no absorption of phosphoric acid on particulate matter or surfaces. The dissociation product of orthophosphoric acid, phosphate ions may absorb onto soil but will not result in toxicity as these are essential nutrients. Not relevant. Orthophosphoric acid release is negligible, due to its low vapour pressure.

15 EXPOSURE SCENARIO ES02 Orthophosphoric Acid 52% P 2O 5 Page 6 of 6 Secondary poisoning Bioaccumulation in organisms is not relevant for orthophosphoric acid.

16 Zakłady Chemiczne Police S.A. EXPOSURE SCENARIO ES 03 Orthophosphoric Acid 52% P 2 O 5 ES-03/SDS-ZChP - 004/10 version 03 The date of: compilation revision ES 03 Professional use of phosphoric acid 1. Short title of the exposure scenario: Professional use of phosphoric acid. Sector of end use (SU): SU22 Professional uses: Public domain (administration, education, entertainment, services, craftsmen) SU1 Agriculture, forestry, fishery SU14 Manufacture of basic metals, including alloys SU15 Manufacture of fabricated metal products, except machinery and equipment SU16 Manufacture of computer, electronic and optical products, electrical equipment SU17 General manufacturing, e.g. machinery, equipment, vehicles, other transport equipment SU19 Building and construction work SU24 Scientific research and development Product category (PC): PC8 Biocidal products (e.g. Disinfectants, pest control) PC9a Coatings and paints, thinners, paint removers PC9b Fillers, putties, plasters, modeling clay PC12 Fertilizers PC14 Metal surface treatment products, including galvanic and electroplating products PC15 Non-metal-surface treatment products PC20 Products such as ph-regulators, flocculants, pre-cipitants, neutralization agents PC21 Laboratory chemicals PC31 Polishes and wax blends PC35 Washing and cleaning products (including solvent based products) PC37 Water treatment chemicals PC38 Welding and soldering products (with flux coatings or flux cores.), flux products Process category (PROC): 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) PROC10 Roller application or brushing PROC11 Non industrial spraying PROC13 Treatment of articles by dipping and pouring

17 EXPOSURE SCENARIO ES03 Orthophosphoric Acid 52% P 2O 5 Page 2 of 5 PROC15 Use as a laboratory reagent PROC19 Hand-mixing with intimate contact and only PPE available PROC21 Low energy manipulation of substances bound in materials and/or articles PROC23 Open processing and transfer opera-tions with minerals/metals at elevated temperature PROC25 Other hot work operations with metals Environmental release category (ERC): ERC8a Wide dispersive indoor use of processing aids in open systems ERC8b Wide dispersive indoor use of reactive substances in open systems ERC8c Wide dispersive indoor use resulting in inclusion into or onto a matrix ERC8e Wide dispersive outdoor use of reactive substances in open systems Article category (AC): AC 1 Vehicles AC 2 Machinery, mechanical appliances, electrical/electronic articles AC 3 Electrical batteries and accumulators AC 4 Stone, plaster, cement, glass and ceramic articles AC 7 Metal articles 2. Operational conditions 2. 1 Operational conditions related with frequency and quantities of use Duration of exposure at workplace/ Frequency of exposure at workplace: Detergents and cleaning products: Phosphoric acid is used during the production phase of various cleaning products, although often the amount in the end products is limited due to its reactivity. The phosphoric acid that is used in professional formulation interacts with the other ingredients in the acid-base reactions. Therefore, free phosphoric acid left in the final product is limited. The amount used per professional workers varies from activity to activity. The operational conditions related to the frequency, duration and amount of use taken from the exposure scenarios provided by the International Association for Soaps, Detergents and Maintenance Products (AISE 2009) describe professional uses of phosphoric acid where duration is shorter than 4h. For professional use of cleaning agents, the AISE exposure scenario gives a frequency of 80 applications per day and a duration of 0.1 minutes per application for spraying and a frequency of 8 applications per day and a duration of 60 minutes per application for brushing. No information on the concentration of phosphoric acid in the final products is available; therefore a worst-case approach will be taken. The concentration of solid a phosphoric in detergent products is assumed to be >25% whereas the concentration in liquids products is assumed to be between 5 and 25%. Fertilizers: No information about the duration and frequency of tasks is available. In the first tier assessment a frequency of once per day with an exposure duration of >4 hours is considered as a worst case. No information on concentration is available; therefore a worst-case approach will be taken. The concentration of solid phosphoric in fertilizers products is assumed to be >25% whereas the concentration in liquids products is assumed to be between 5 and 25%. Construction and building applications: No information about the duration and frequency of tasks is available. In the first tier assessment a frequency of once per day with an exposure duration of >4 hours is considered as a worst case. No information on concentration is available; therefore a worst-case approach will be

18 EXPOSURE SCENARIO ES03 Orthophosphoric Acid 52% P 2O 5 Page 3 of 5 taken. The concentration of solid phosphoric in construction products is assumed to be >25% whereas the concentration in liquids products is assumed to be between 5 and 25%. Metal surface treatment and soldering flux: No information about the duration and frequency of tasks is available. In the first tier assessment a frequency of once per day with an exposure duration of >4 hours is considered as a worst case. No information on concentration is available; therefore a worst-case approach will be taken. The concentration of solid phosphoric in used in metal surface treatment is assumed to be >25%. The concentration in liquids products for metal surface treatment and soldering flux is assumed to be 5-25%. Annual amount used per site: 2.2 Operational conditions related with substance/ product Physical state Solid / Liquid The daily and annual amount/emission per site is not considered to be the main determinant for environmental exposure. Concentration of See above. substance in mixture 2.3 Other relevant operational conditions The amount used per professional workers varies from activity to activity. The maximum duration >4 h/day was considered as worst case assumption. 3. Risk Management Measures 3.1 RMMs related to workers Organizational measures Technical measures Respiratory protection Hand protection Eye protection Professional users should wear appropriate personal protection equipment, such as gloves and safety glasses during processes. The employer must ensure that the required PPE is available and used according to instructions (provide training if necessary). Safety showers and eye washes are installed to be available in the case of accidental contact. Use closed/ automated systems or covering of open containers (e.g. screens) to avoid irritating mists, sprayings and potential splashes. (Good practice) Store in cool, dry, clean, well ventilate areas. (Good practice). Personal respiratory equipment (PRE): In case of dust or aerosol formation (e.g. spraying): use respiratory protection with approved filter. Hand protection is required: Impervious chemical resistant protective gloves are required. Material of gloves. Chloroprene, Neoprene or PVC gloves Wearing of eye/face protection is required as substance is corrosive. Goggles or face protection shield should be consistent with EN 166 or equivalent. Skin and body Wearing of suitable protective clothing and rubber boots is protection recommended. Hygiene measures Keep away from foodstuffs, drinks and tobacco. Wash hands before breaks and at end of work. Keep work clothes separate. 3.2 RMMs related to the environment Organizational measures Procedural and/or control technologies are required to minimise emissions and the resulting exposure during cleaning and maintenance Abatement measures related to wastewater procedures. Different rules apply to professional users regarding control of their effluents. It is required that the flow of release to municipal wastewater or to surface water do not cause significant in ph changes. It is then dependant whether or not discharging is done to municipal

19 EXPOSURE SCENARIO ES03 Orthophosphoric Acid 52% P 2O 5 Page 4 of 5 wastewater equipped with sewage treatment plant or not. Abatement measures waste air and solid waste Orthophosphoric acid is not expected to be found in the solid waste nor to reach the air compartment, due to its low vapour pressure. Therefore, no specific risk management measures for air emissions are provided. For release to soil for fertilizer uses, the ph will be naturally neutralized by the medium before reaching the groundwater. 3.3 Waste related measures Type of waste Liquid waste, solid residues, packaging material Disposal technique Fraction released to environment during waste treatment The release of phosphates to wastewater is highly regulated, In addition ph changes in receiving waters should be minimized. The residue of the containers or the used container itself should be disposed in accordance with local and national requirements. See Section 13 of the SDS for more information. Not determined. The ph of wastewater released from manufacturing sites should be between ph Prediction of exposure and comparison of predicted exposure with DNELs (Risk Characterisation) 4.1. Human exposure Exposure estimation tool(s) Workers (oral) Workers, inhalation / dermal, TIER 1 (all uses): MEASE Workers, inhalation / dermal, TIER 2 (spray applications): UK POEM The professional uses of orthophosphoric acid will not notably contribute to the oral intake of phosphates. Workers No systemic toxicity effects are expected due to the inorganic nature of (dermal) the substance however local effects may occur but these effects will not be dose-dependent but will depend on the concentration of the substance present in the mixture/solution used in a specific application. It is therefore recommended that the appropriate PPE is used. Indirect No indirect exposure of humans via the environment is expected for exposure via the orthophosphoric acid. Thus, no assessment of indirect exposure of environment humans via the environment is required Environmental exposure (qualitative assessment) Environmental release Waste water treatment plants (WWTP) Aquatic pelagic compartment The production of orthophosphoric acid can potentially result in aquatic emissions and locally increase the phosphate concentration while decreasing the ph in the aquatic environment. However, the ph of industrial effluents is normally measured frequently and can be neutralized easily. Not relevant. Orthophosphoric acid dissociates in H+ and PO 3-4 and will be neutralized before reaching WWTP. The predominant adverse effects of orthophosphoric acid in aquatic systems are ph-related effects, as a result of the acidic nature of orthophosphoric acid. As phosphoric acid is a triprotic acid it will dissociate up to 3 times; releasing a phosphate anion (H 2PO 4 -, HPO 4 2- or PO 4 3- ) and a H + ion at each dissociation. The fate of the H + ions (and

20 EXPOSURE SCENARIO ES03 Orthophosphoric Acid 52% P 2O 5 Page 5 of 5 Sediments Soil and groundwater Atmospheric compartment Secondary poisoning subsequently the resultant ph) will depend on the chemical composition of the receiving water body; the higher the buffering capacity of the water, the lower the effect on ph will be. Not relevant. Orthophosphoric acid will progressively dissociate in water to give H + and PO 3-4 ions. Due to its high water solubility and low vapour pressure it is predicted that any un-dissociated phosphoric acid will remain in the water phase and will not absorb onto particulate. Not relevant. Orthophosphoric acid entering soil and ground water will be partially neutralized, dispersed and diluted. There will be no absorption of phosphoric acid on particulate matter or surfaces. The dissociation product of orthophosphoric acid, phosphate ions may absorb onto soil but will not result in toxicity as these are essential nutrients. Not relevant. Orthophosphoric acid release is negligible, due to its low vapour pressure. Bioaccumulation in organisms is not relevant for orthophosphoric acid.

21 Zakłady Chemiczne Police S.A. EXPOSURE SCENARIO ES 04 Orthophosphoric Acid 52% P 2 O 5 ES-04/SDS-ZChP - 004/10 version 03 The date of: compilation revision ES 04 Consumer use of phosphoric acid 1. Short title of the exposure scenario: Consumer Use of phosphoric acid. Sector of end use (SU): SU21 Consumer uses: Private households (= general public = consumers) Product category (PC): PC12 Fertilizers PC31 Polishes and wax blends PC35 Washing and cleaning products (including solvent based products) PC38 Welding and soldering products (with flux coatings or flux cores.), flux products Environmental release category (ERC): ERC8a Wide dispersive indoor use of processing aids in open systems ERC8b Wide dispersive indoor use of reactive substances in open systems ERC8d Wide dispersive outdoor use of processing aids in open systems ERC8e Wide dispersive outdoor use of reactive substances in open systems Process category (PROC): Not applicable Article category (AC): Not applicable 2. Operational conditions 2. 1 Operational conditions related with frequency and quantities of use Phosphoric acid is typically present in consumer products in low concentrations. The main uses are listed below and included in this exposure scenario. Use in polishes and waxes: use of polishes in spray, and waxes/cream for floor, furniture, shoes, where phosphoric acid is co-formulant Use as washing and cleaning agent: use of household washing and cleaning products containing phosphoric acid to remove mineral deposits and hard water stains (lime scale removers, typical concentration of phosphoric acid in the product: 5-15%) Use of household fertilizers containing phosphoric acid: use of liquid and soluble liquid or solid fertilizers. It includes transfer, loading, unloading, dilution operations and surface spreading of minor quantities for indoor/ outdoor home fertilizer use. Use phosphoric acid in batteries: electrolyte system, fuel cells and other closed systems. Use as additive in cosmetics and use as a food additive. These applications are not included in this exposure scenario as food/ feed applications are covered under Regulation (EC) N 1935/2004 and cosmetics under Directive 76/768/CEE. Phosphoric acid is not provided as such to consumers and general public. In addition, this scenario does not cover phosphoric acid present in consumer products at a concentration of >25%. 2.2 Operational conditions related with substance/ product

22 EXPOSURE SCENARIO ES04 Orthophosphoric Acid 52% P 2O 5 Page 2 of 3 Physical state Solid / Liquid Concentration See above. of substance in mixture 3. Risk Management Measures 3.1 RMMs related to Consumers Consumer products should be intrinsically safe, therefore products containing phosphoric acid should be designed to avoid accidents and in case an accident occurs, instructions should be available how to minimise the effects. Risk management measures in place relate to the design of the consumer product and to consumers use. Measures related to the design of the product It is required to use acid resistant labeling and packaging in order to avoid autodamage and loss of the label integrity, under normal use and storage of the product. The lack of quality of the package provokes the physical loss of information on hazards and use instructions. It is required that household chemicals, containing phosphoric acid at 10% should be provided with a child-resistant fastening (currently applied) and a tactile warning of danger (Adaptation to Technical Progress of the Directive 1999/45/EC, annex IV, Part A and Article 15(2) of Directive 67/548 in the case of, respectively, dangerous preparations and substances intended for domestic use). This would prevent accidents by children and other sensitive groups of society. It is required that recommended use instructions, and product information should always be provided to the consumers. This will considerably reduce the risk of misuse. For reducing the number of accidents in which (young) children or elderly people are involved, it should be advisable to use these products in the absence of children or other potential sensitive groups. To prevent improper use of phosphoric acid, instructions for use should contain a warning against dangerous mixtures. PPE required under regular conditions of consumer use. Protective equipment measures: product related design measures are required. These include specific dispensers and pumps specifically designed to prevent splashes/spills/exposure to occur. For consumer products containing phosphoric acid (concentration <10%) it is recommended to wear hand protection, long sleeves to prevent splashes and eye protection. 3.2 RMMs related to the environment There are no specific risk management measures related to environment. Abatement No specific abatement measures recommended. measures related to wastewater Abatement No specific abatement measures recommended. measures waste air and solid waste 3.3 Waste related measures It is anticipated that empty containers will end up in the municipal waste. Batteries: this material and its container must be disposed of in a safe way (e.g. by returning to a public recycling facility). Batteries should be recycled as much as possible (e.g. by returning to a public recycling facility). It is not anticipated that consumers will be exposed to phosphoric acid in batteries. 4. Prediction of exposure and comparison of predicted exposure with DNELs (Risk Characterization) 4.1. Human exposure Exposure Consumers, inhalation, TIER 2 (spray applications, fertilizers): UK POEM