Calcium Carbide Version Number: GHS 2.0 Revision: 2018-09-07

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Safety Data Sheet According to 1907/2006, article 31 as amended

Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07

SECTION 1: Identification of the substance/mixture and of the company/undertaking 1.1 Product identifier Identification of the substance Calcium carbide Registration number (REACH) 01-2119494719-18-0000 EC number 200-848-3 Index number in CLP Annex VI 006-004-00-9 CAS number 75-20-7 Product-ID: 120010, 120011, 120012 and 120020 1.2 Relevant identified uses of the substance or mixture and uses advised against Relevant identified uses Milling and formulation Chemical intermediate Use in metallurgy Formulation of industrial products Carbide lamps Carbide welding Laboratory and analytical use 1.3 Details of the supplier of the safety data sheet

Dr. Radtke CPM Chemical-Physical Measuring techniques Ltd. Laettichstreet 4a 6340 Baar / Schweiz

National contact +41 41 710 00 32 This number is only available during the following office hours. Mo - Fri 08:00 AM - 4:00 PM e-mail: [email protected] 1.4 Emergency telephone number

Poison centre

Country Name Postal code/city Telephone

United Kingdom Guy's & St Thomas' Poisons Unit London 0870 243 2241

United Kingdom National Poisons Information Service (Belfast Belfast 0870 600 6266 (UK only) Centre)

United Kingdom National Poisons Information Service (Cardiff Cardiff 0870 600 6266 (UK only) Centre)

United Kingdom Scottish Poisons Information Bureau Edinburgh 0870 600 6266 (UK only)

ENGLISH: en Page: 1 / 14 Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)

Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1)

SECTION 2: Hazards identification 2.1 Classification of the substance or mixture Classification according to Regulation (EC) No 1272/2008 (CLP)

Section Hazard class Cat- Hazard class Hazard state- egory and ment category 2.12 substance and mixture which, in contact with water, emits 1 Water-react. 1 H260 flammable gas

3.2 skin corrosion/irritation 2 Skin Irrit. 2 H315

3.3 serious eye damage/eye irritation 1 Eye Dam. 1 H318

3.8R specific target organ toxicity - single exposure (respiratory 3 STOT SE 3 H335 tract irritation)

For full text of abbreviations: see SECTION 16. The most important adverse physicochemical, human health and environmental effects In contact with water releases flammable gases which may ignite spontaneously. 2.2 Label elements Labelling according to Regulation (EC) No 1272/2008 (CLP) - Signal word danger - Pictograms GHS02, GHS05, GHS07

- Hazard statements H260 In contact with water releases flammable gases which may ignite spontaneously. H315 Causes skin irritation. H318 Causes serious eye damage. H335 May cause respiratory irritation. - Precautionary statements P223 Do not allow contact with water. P231+P232 Handle and store contents under inert gas/.... Protect from moisture. P261 Avoid breathing dust/fume/gas/mist/vapours/spray. P280 Wear protective gloves/protective clothing/eye protection/face protection. P302+P352 IF ON SKIN: Wash with plenty of water. P305+P351+P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. P370+P378 In case of fire: Use powder extinguisher to extinguish. P402+P404 Store in a dry place. Store in a closed container. P501 Dispose of contents/container in accordance with local/regional/national/international regula tions. 2.3 Other hazards Results of PBT and vPvB assessment According to the results of its assessment, this substance is not a PBT or a vPvB.

ENGLISH: en Page: 2 / 14 Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)

Calcium carbide

Version number: GHS 2.0 Revision: 2018-09-07

Replaces version of: 2018-05-09 (GHS 1)

SECTION 3: Composition/information on ingredients 3.1 Substances Name of substance Calcium carbide Identifiers REACH Reg. No 01-2119494719-18-0000 CAS No 75-20-7 EC No 200-848-3 Index No 006-004-00-9 SECTION 4: First aid measures 4.1 Description of first aid measures General notes Do not leave affected person unattended. Remove victim out of the danger area. Keep affected person warm, still and covered. Take off immediately all contaminated clothing. In all cases of doubt, or when symptoms persist, seek medical advice. In case of unconsciousness place person in the recovery position. Never give anything by mouth. Following inhalation Provide fresh air. In all cases of doubt, or when symptoms persist, seek medical advice. If breathing is irregular or stopped, immediately seek medical assistance and start first aid actions. In case of respiratory tract irritation, consult a physician. Following skin contact Brush off loose particles from skin. Rinse skin with water/shower. Wash with plenty of soap and water. If skin irritation or rash occurs: Get medical advice/attention. Following eye contact Irrigate copiously with clean, fresh water for at least 10 minutes, holding the eyelids apart. Remove contact lenses, if present and easy to do. Continue rinsing. Call a physician immediately. Following ingestion Do NOT induce vomiting. Call a physician immediately. 4.2 Most important symptoms and effects, both acute and delayed Symptoms and effects are not known to date. 4.3 Indication of any immediate medical attention and special treatment needed none SECTION 5: Firefighting measures 5.1 Extinguishing media Suitable extinguishing media D-Powder, Dry sand Unsuitable extinguishing media Water jet, Foam, Carbon dioxide (CO2) 5.2 Special hazards arising from the substance or mixture On contact with water highly flammable and explosive acetylene is generated. Hazardous combustion products Carbon monoxide (CO), Carbon dioxide (CO2) 5.3 Advice for firefighters In case of fire and/or explosion do not breathe fumes. Co-ordinate firefighting measures to the fire surroundings. Do not allow firefighting water to enter drains or water courses. Collect contaminated firefighting water separately. Fight fire with normal precautions from a reasonable distance. Special protective equipment for firefighters Chemical protective clothing, Wear self-contained breathing apparatus

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Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1)

SECTION 6: Accidental release measures 6.1 Personal precautions, protective equipment and emergency procedures For non-emergency personnel Remove persons to safety. Provision of sufficient ventilation. Wearing of suitable protective equipment (including personal protective equipment referred to under Section 8 of the safety data sheet) to prevent any contamination of skin, eyes and personal clothing. Removal of ignition sources. For emergency responders Wear breathing apparatus if exposed to vapours/dust/spray/gases. 6.2 Environmental precautions Keep away from drains, surface and ground water. Retain contaminated washing water and dispose of it. 6.3 Methods and material for containment and cleaning up Advices on how to contain a spill Covering of drains, Take up mechanically Advices on how to clean up a spill Take up mechanically. Other information relating to spills and releases Place in appropriate containers for disposal. Ventilate affected area. 6.4 Reference to other sections Hazardous combustion products: see section 5. Personal protective equipment: see section 8. Incompatible materials: see section 10. Disposal considerations: see section 13. SECTION 7: Handling and storage 7.1 Precautions for safe handling Recommendations - Measures to prevent fire as well as aerosol and dust generation Keep container tightly closed. Use local and general ventilation. Take precautionary measures against static discharge. Use only in well-ventilated areas. - Specific notes/details Dust deposits may accumulate on all deposition surfaces in a technical room. - Handling of incompatible substances or mixtures - Keep away from Acids, Water, Store separately from oxidising and spontaneously flammable substances. Advice on general occupational hygiene Take off immediately all contaminated clothing. Wash hands after use. Do not eat, drink and smoke in work areas. Remove contaminated clothing and protective equipment before entering eating areas. Never keep food or drink in the vicinity of chemicals. Never place chemicals in containers that are normally used for food or drink. Keep away from food, drink and animal feedingstuffs. Do not breathe gas/vapour/spray. Avoid contact with skin and eyes. 7.2 Conditions for safe storage, including any incompatibilities Managing of associated risks - Explosive atmospheres Removal of dust deposits. - Incompatible substances or mixtures Do not allow contact with water. - Do not mix with Acids, Caustic solutions, Alcohols, Water - Evaporative conditions Keep container tightly closed and in a well-ventilated place.

ENGLISH: en Page: 4 / 14 Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)

Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1)

Control of effects Protect against external exposure, such as Humidity - Ventilation requirements Use local and general ventilation. - Packaging compatibilities Only packagings which are approved (e.g. acc. to ADR) may be used. 7.3 Specific end use(s) See section 16 for a general overview. SECTION 8: Exposure controls/personal protection 8.1 Control parameters

Occupational exposure limit values (Workplace Exposure Limits)

Coun Name of agent CAS No Identi- TWA TWA STEL STEL Source try fier [ppm] [mg/m³] [ppm] [mg/m³]

GB dust WEL 10 EH40/2005 GB dust WEL 4 EH40/2005

Notation STEL short-term exposure limit: a limit value above which exposure should not occur and which is related to a 15-minute period (unless otherwise specified) TWA time-weighted average (long-term exposure limit): measured or calculated in relation to a reference period of 8 hours time- weighted average (unless otherwise specified)

8.2 Exposure controls Appropriate engineering controls General ventilation. Individual protection measures (personal protective equipment) Eye/face protection Use safety goggle with side protection.

Skin protection - Hand protection Chemical protection gloves are suitable, which are tested according to EN 374. Check leak-tightness/impermeability prior to use. In the case of wanting to use the gloves again, clean them before taking off and air them well. For special purposes, it is recommended to check the resistance to chemicals of the protective gloves mentioned above together with the supplier of these gloves.

- Type of material NBR: acrylonitrile-butadiene rubber - Other protection measures Take recovery periods for skin regeneration. Preventive skin protection (barrier creams/ointments) is recommended. Wash hands thoroughly after handling. Respiratory protection In case of dust formation: respiratory protection. Particulate filter device (EN 143).

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Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1)

Environmental exposure controls Use appropriate container to avoid environmental contamination. Keep away from drains, surface and ground water. SECTION 9: Physical and chemical properties 9.1 Information on basic physical and chemical properties Appearance Physical state solid

Colour dark grey

Odour characteristic

Other safety parameters pH (value) not applicable

Melting point/freezing point 2,160 °C

Initial boiling point and boiling range 2,300 °C

Flash point not applicable

Evaporation rate not determined

Flammability (solid, gas) substance which, in contact with water, emits flammable gases (in accordance with GHS criteria)

Explosion limits of dust clouds not determined

Vapour pressure not determined

g Density 2.22 /cm³

Vapour density this information is not available

Solubility(ies) not determined - Water solubility material hydrolyses (half-life < 12 hours)

Partition coefficient - n-octanol/water (log KOW) this information is not available

Auto-ignition temperature not determined

Viscosity not relevant (solid matter)

Explosive properties none

Oxidising properties none

9.2 Other Information there is no additional information

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Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1)

SECTION 10: Stability and reactivity 10.1 Reactivity Concerning incompatibility: see below "Conditions to avoid" and "Incompatible materials". It's a reactive substance. The mixture contains reactive substance(s). Reactivity with water. 10.2 Chemical stability See below "Conditions to avoid". 10.3 Possibility of hazardous reactions On contact with water highly flammable and explosive acetylene is generated. 10.4 Conditions to avoid Protect from moisture. Store separately from oxidising and spontaneously flammable substances. 10.5 Incompatible materials Water, Acids, Bases, Oxidisers, Silver, Copper Release of flammable materials with: Water 10.6 Hazardous decomposition products Reasonably anticipated hazardous decomposition products produced as a result of use, storage, spill and heating are not known. Hazardous combustion products: see section 5.

SECTION 11: Toxicological information 11.1 Information on toxicological effects Classification according to GHS (1272/2008/EC, CLP) Acute toxicity Shall not be classified as acutely toxic. GHS of the United Nations, annex 4: May be harmful if swallowed or in contact with skin.

Acute toxicity

Exposure route Endpoint Value Species Notes

mg oral LD50 >2,000 /kg rat mg dermal LD50 >2,500 /kg rabbit

Skin corrosion/irritation Causes skin irritation. Serious eye damage/eye irritation Causes serious eye damage. Respiratory or skin sensitisation Shall not be classified as a respiratory or skin sensitiser. Germ cell mutagenicity Shall not be classified as germ cell mutagenic. Carcinogenicity Shall not be classified as carcinogenic. Reproductive toxicity Shall not be classified as a reproductive toxicant. Specific target organ toxicity - single exposure May cause respiratory irritation. Specific target organ toxicity - repeated exposure Shall not be classified as a specific target organ toxicant (repeated exposure). Aspiration hazard Shall not be classified as presenting an aspiration hazard. ENGLISH: en Page: 7 / 14 Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)

Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1)

SECTION 12: Ecological information 12.1 Toxicity Shall not be classified as hazardous to the aquatic environment.

Aquatic toxicity (acute)

Endpoint Value Species Exposure time

mg LC50 >50 /l fish 96 h mg EC50 4.62 /l aquatic invertebrates 48 h

mg ErC50 46 /l algae 72 h mg LOEC >50 /l fish 96 h

mg NOEC 50 /l fish 96 h mg growth rate (ErCx) 10% 12 /l algae 72 h

mg growth (EbCx) 10% 2.7 /l algae 72 h

12.1 Persistence and degradability Data are not available. 12.2 Bioaccumulative potential Data are not available. 12.3 Mobility in soil Data are not available. 12.4 Results of PBT and vPvB assessment Data are not available. 12.5 Other adverse effects Endocrine disrupting potential Not listed. SECTION 13: Disposal considerations 13.1 Waste treatment methods This material and its container must be disposed of as hazardous waste. Waste treatment-relevant information Recycling/reclamation of other inorganic materials. Sewage disposal-relevant information Do not empty into drains. Avoid release to the environment. Refer to special instructions/safety data sheets. Waste treatment of containers/packagings It is a dangerous waste; only packagings which are approved (e.g. acc. to ADR) may be used. Completely emptied packages can be recycled. Handle contaminated packages in the same way as the substance itself. Relevant provisions relating to waste List of wastes Disposal code numbers according to the European Waste Catalogue are defined according to origin of the waste. As this product is used in several branches of industry, no disposal code number can be specified by the manufacturer. The waste code number must be determined in consultation with the disposal company or the competent authority. Remarks Please consider the relevant national or regional provisions. Waste shall be separated into the categories that can be handled separately by the local or national waste management facilities.

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Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1)

SECTION 14: Transport information 14.1 UN number 1402 14.2 UN proper shipping name CALCIUM CARBIDE 14.3 Transport hazard class(es) Class 4.3 (substances which, in contact with water, emit flammable gases)

14.4 Packing group I (substance presenting high danger) 14.5 Environmental hazards non-environmentally hazardous acc. to the dangerous goods regulations 14.6 Special precautions for user Provisions for dangerous goods (ADR) should be complied within the premises. 14.7 Transport in bulk according to Annex II of MARPOL and the IBC Code The cargo is not intended to be carried in bulk. Information for each of the UN Model Regulations Transport of dangerous goods by road, rail and inland waterway (ADR/RID/ADN) UN number 1402 Proper shipping name CALCIUM CARBIDE - Particulars in the transport document UN1402, CALCIUM CARBIDE, 4.3, I, (B/E) Class 4.3 Classification code W2 Packing group I Danger label(s) 4.3

Excepted quantities (EQ) E0 Limited quantities (LQ) 0 Transport category (TC) 1 Tunnel restriction code (TRC) B/E Hazard identification No X423 Emergency Action Code 4W International Maritime Dangerous Goods Code (IMDG) UN number 1402 Proper shipping name CALCIUM CARBIDE - Particulars in the shipper's declaration UN1402, CALCIUM CARBIDE, 4.3, I Class 4.3 Marine pollutant - Packing group I Danger label(s) 4.3

Special provisions (SP) 951 Excepted quantities (EQ) E0 Limited quantities (LQ) 0 EmS F-G, S-N Stowage category B

ENGLISH: en Page: 9 / 14 Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)

Calcium carbide

Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1)

International Civil Aviation Organization (ICAO-IATA/DGR) UN number 1402 Proper shipping name Calcium carbide - Particulars in the shipper's declaration UN1402, Calcium carbide, 4.3, I Class 4.3 Packing group I Danger label(s) 4.3

Excepted quantities (EQ) E0

SECTION 15: Regulatory information 15.1 Safety, health and environmental regulations/legislation specific for the substance or mixture Relevant provisions of the European Union (EU) Restrictions according to REACH, Annex XVII

Dangerous substances with restrictions (REACH, Annex XVII)

Name of substance Name acc. to inventory Restriction No

Calcium carbide this product meets the criteria for classific- R3 3 ation in accordance with Regulation No 1272/2008/EC

Calcium carbide flammable / pyrophoric R40 40

Legend R3 1. Shall not be used in: - ornamental articles intended to produce light or colour effects by means of different phases, for example in ornamental lamps and ashtrays, - tricks and jokes, - games for one or more participants, or any article intended to be used as such, even with ornamental aspects, 2. Articles not complying with paragraph 1 shall not be placed on the market. 3. Shall not be placed on the market if they contain a colouring agent, unless required for fiscal reasons, or perfume, or both, if they: - can be used as fuel in decorative oil lamps for supply to the general public, and, - present an aspiration hazard and are labelled with R65 or H304, 4. Decorative oil lamps for supply to the general public shall not be placed on the market unless they conform to the European Standard on Decorative oil lamps (EN 14059) adopted by the European Committee for Standardisation (CEN). 5. Without prejudice to the implementation of other Community provisions relating to the classification, packaging and labelling of dangerous substances and mixtures, suppliers shall ensure, before the placing on the market, that the following requirements are met: (a) lamp oils, labelled with R65 or H304, intended for supply to the general public are visibly, legibly and indelibly marked as follows: ‘Keep lamps filled with this liquid out of the reach of children’; and, by 1 December 2010, ‘Just a sip of lamp oil - or even sucking the wick of lamps - may lead to life-threatening lung damage’; (b) grill lighter fluids, labelled with R65 or H304, intended for supply to the general public are legibly and indelibly marked by 1 December 2010 as follows: ‘Just a sip of grill lighter may lead to life threatening lung damage’; (c) lamp oils and grill lighters, labelled with R65 or H304, intended for supply to the general public are packaged in black opaque containers not exceeding 1 litre by 1 December 2010. 6. No later than 1 June 2014, the Commission shall request the European Chance with Article 69 of the present Regulation with a view to ban, if appropriate, grill lighter fluids and fuel for decorative lamps, labelled R65 or H304, intended for supply to the general public. 7. Natural or legal persons placing on the market for the first time lamp oils and grill lighter fluids, labelled with R65 or H304, shall by 1 December 2011, and annually thereafter, provide data on alternatives to lamp oils and grill lighter fluids labelled R65 or H304 to the competent authority in the Member State concerned. Member States shall make those data available to the Commission.

ENGLISH: en Page: 10 / 14 Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)

Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1)

Legend

R40 1. Shall not be used, as substance or as mixtures in aerosol dispensers where these aerosol dispensers are intended for supply to the general public for entertainment and decorative purposes such as the following: - metallic glitter intended mainly for decoration, - artificial snow and frost,‘whoopee’ cushions, - silly string aerosols, - imitation excrement, - horns for parties, - decorative flakes and foams, - artificial cobwebs, - stink bombs. 2. Without prejudice to the application of other Community provisions on the classification, packaging and labelling of substances, suppliers shall ensure before the placing on the market that the packaging of aerosol dispensers referred to above is marked visibly, legibly and indelibly with: ‘For professional users only’. 3. By way of derogation, paragraphs 1 and 2 shall not apply to the aerosol dispensers referred to Article 8 (1a) of Council Dir- ective 75/324/EEC (2). 4. The aerosol dispensers referred to in paragraphs 1 and 2 shall not be placed on the market unless they conform to the requirements indicated.

List of substances subject to authorisation (REACH, Annex XIV) / SVHC - candidate list not listed Seveso Directive

2012/18/EU (Seveso III)

No Dangerous substance/hazard categories Qualifying quantity (tonnes) for the ap- Notes plication of lower and upper-tier requirements

O2 other hazards (Water-react., cat. 1) 100 500 59)

Notation 59) substances and mixtures which in contact with water emit flammable gases, category 1

Directive 2011/65/EU on the restriction of the use of certain hazardous substances in electrical and electronic equipment (RoHS) - Annex II not listed Regulation 166/2006/EC concerning the establishment of a European Pollutant Release and Transfer Register (PRTR) not listed Directive 2000/60/EC establishing a framework for Community action in the field of water policy (WFD) not listed Regulation 98/2013/EU on the marketing and use of explosives precursors not listed Regulation 111/2005/EC laying down rules for the monitoring of trade between the Community and third countries in drug precursors not listed

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Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1) National inventories

Country Inventory Status

EU REACH Reg. substance is listed AU AICS substance is listed

CA DSL substance is listed CN IECSC substance is listed

EU ECSI substance is listed JP CSCL-ENCS substance is listed

KR KECI substance is listed MX INSQ substance is listed

NZ NZIoC substance is listed PH PICCS substance is listed

TR CICR substance is listed TW TCSI substance is listed

US TSCA substance is listed

Legend AICS Australian Inventory of Chemical Substances CICR Chemical Inventory and Control Regulation CSCL-ENCS List of Existing and New Chemical Substances (CSCL-ENCS) DSL Domestic Substances List (DSL) ECSI EC Substance Inventory (EINECS, ELINCS, NLP) IECSC Inventory of Existing Chemical Substances Produced or Imported in China INSQ National Inventory of Chemical Substances KECI Korea Existing Chemicals Inventory NZIoC New Zealand Inventory of Chemicals PICCS Philippine Inventory of Chemicals and Chemical Substances REACH Reg. REACH registered substances TCSI Taiwan Chemical Substance Inventory TSCA Toxic Substance Control Act

15.2 Chemical Safety Assessment For this substance a chemical safety assessment has been carried out.

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Calcium carbide Version number: GHS 2.0 Revision: 2018-09-07 Replaces version of: 2018-05-09 (GHS 1)

SECTION 16: Other information Indication of changes (revised safety data sheet)

Section Former entry (text/value) Actual entry (text/value) Safety - relevant 1.1 Alternative name(s): Calcium yes acetylide

5.2 Special hazards arising from the substance or Special hazards arising from the substance or yes mixture: mixture: Product may release hydrogen gas. Increased On contact with water highly flammable and ex- storage temperatures will accelerate this pro- plosive acetylene is generated. cess. On contact with water highly flammable and explosive acetylene is generated. Abbreviations and acronyms

Abbr. Descriptions of used abbreviations

ADN Accord européen relatif au transport international des marchandises dangereuses par voies de navigation intérieures (European Agreement concerning the International Carriage of Dangerous Goods by Inland Waterways) ADR Accord européen relatif au transport international des marchandises dangereuses par route (European Agreement concerning the International Carriage of Dangerous Goods by Road)

CAS Chemical Abstracts Service (service that maintains the most comprehensive list of chemical substances) CLP Regulation (EC) No 1272/2008 on classification, labelling and packaging of substances and mixtures

DGR Dangerous Goods Regulations (see IATA/DGR)

EC No The EC Inventory (EINECS, ELINCS and the NLP-list) is the source for the seven-digit EC number, an identifier of substances commercially available within the EU (European Union)

EH40/2005 EH40/2005 Workplace exposure limits (http://www.nationalarchives.gov.uk/doc/open-government-li- cence/) EINECS European Inventory of Existing Commercial Chemical Substances

ELINCS European List of Notified Chemical Substances EmS Emergency Schedule

GHS "Globally Harmonized System of Classification and Labelling of Chemicals" developed by the United Nations

IATA International Air Transport Association

IATA/DGR Dangerous Goods Regulations (DGR) for the air transport (IATA) ICAO International Civil Aviation Organization

IMDG International Maritime Dangerous Goods Code

index No The Index number is the identification code given to the substance in Part 3 of Annex VI to Regulation (EC) No1272/2008

MARPOL International Convention for the Prevention of Pollution from Ships (abbr. of "Marine Pollutant") NLP No-Longer Polymer

PBT Persistent, Bioaccumulative and Toxic ppm Parts per million

REACH Registration, Evaluation, Authorisation and Restriction of Chemicals

RID Règlement concernant le transport International ferroviaire des marchandises Dangereuses (Regulations concerning the International carriage of Dangerous goods by Rail)

STEL Short-term exposure limit SVHC Substance of Very High Concern

ENGLISH: en Page: 13 / 14 Abbr. Descriptions of used abbreviations

TWA Time-weighted average vPvB Very Persistent and very Bioaccumulative

WEL Workplace exposure limit

Key literature references and sources for data Regulation (EC) No 1272/2008 on classification, labelling and packaging of substances and mixtures. Regulation (EC) No. 1907/2006 (REACH), amended by 2015/830/EU. Transport of dangerous goods by road, rail and inland waterway (ADR/RID/ADN). International Maritime Dangerous Goods Code (IMDG). Dangerous Goods Regulations (DGR) for the air transport (IATA).

List of relevant phrases (code and full text as stated in chapter 2 and 3)

Code Text

H260 In contact with water releases flammable gases which may ignite spontaneously. H315 Causes skin irritation.

H318 Causes serious eye damage. H335 May cause respiratory irritation.

Disclaimer This information is based upon the present state of our knowledge. This SDS has been compiled and is solely intended for this product.

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9 EXPOSURE ASSESSMENT Exposure scenarios are presented for the production of calcium carbide and the two identified uses described in Section 2: A) Use of calcium carbide in the production of acetylene and calcium cyanide. B) Use of calcium carbide in metallurgy. Any tonnages discussed in this document are generic and should not be taken as relating to any specific site. The scenarios and releases described in this chapter are written in accordance with the REACH Guidance and are taken mainly from or based on the following sources: • Reference Document on Best Available Techniques (BAT) for the Manufacture of Large Volume Inorganic Chemicals. • Information provided by calcium carbide consortium members. • Site visits to a calcium carbide production plant and industries making use of calcium carbide. The uses and relevant descriptor codes for each identified exposure scenario are summarised in Table 9.1. Exposure Scenario 1 describes the production of calcium carbide. Exposure Scenario 2 describes the milling/formulation of calcium carbide products. Exposure Scenario 3 describes the industrial use of calcium carbide as a process material or intermediate in the production of acetylene and calcium cyanide. Exposure Scenario 4 describes use of calcium carbide in metallurgy (use as a blast furnace hot metal desulfuriser, use as a foundry iron desulfuriser and use during steelmaking). Exposure Scenario 5 describes use of calcium carbide in Carbide Lamps. Exposure Scenario 6 describes use of calcium carbide in Carbide welding. Exposure Scenario 7 describes use of calcium carbide in humidity analyzers.

It should be noted that all concentrations in the soil compartment are upper limits; the significance of this is discussed in Section 10.1.

No calculation of regional releases is required, for reasons explained in Section 9.8.

Table 9.1, Overview on exposure scenarios and coverage of substance life cycle Resulting Identified life cycle uses stage

Linked to Preparation ES Process category Article category

Sector of Use (SU)

Identified Category

number (PROC) (AC)

Volume (f

us Use (PC)

ion

(tonnes)

lif

Manufacture

End use End Consumer Service articles) Wastesta Formulat Confidential SU 3 (main user group), ES 1 X - PROC 2, 8b - SU 8 (end-use)

Confidential SU 3 (main user group), ES 2 X PC 20 PROC 5, 8b - SU 10 (end-use) Confidential SU 3 (main user group), ES 3 X PC 19 PROC 2, 8b N/A SU 8 (end-use)

Confidential SU 3 (main user group), ES 4 X PC 20 PROC 221 N/A SU 14 (end-use)

Confidential X X Carbide ES 5 lamps SU 2a PC 19 PROC 3 N/A

Confidential X X Carbide ES 6 SU 19 PC 19 PROC 3 N/A welding

Confidential X Calcium carbide in ES 7 SU 24, 19 PC 19 PROC 3 N/A humidity analyzers Notes: 1Transfer of substance from/to vessels/large containers at dedicated facilities (PROC8b) is not applicable because high levels of containment are used in automated systems.

9.1 ES 1: Production of calcium carbide

9.1.1 Exposure scenario

9.1.1.1 Description of activities and processes covered in the exposure scenario This scenario covers the production of calcium carbide based on information provided by members of the calcium carbide consortium. It also includes information about risk management measures (RMM) in place during production. A site visit to a calcium carbide production facility showed that in some respects it is a typical chemical production plant with a roof covering an essentially open area. The electrothermal process is not typical of the chemical industry, with very high electrical power consumption as a means of performing the required process. Production takes place on not less than 200 days per year, and each furnace can produce several hundred tonnes of calcium carbide per day. Once the continuous process has started, production continues until essential maintenance is required. Due to the nature of the reaction and the hazards associated with acetylene, no water is used in the facility apart from a cooling jacket around the furnace crucible. There is no generation of wastewater in the production area. Signs saying “No water” are present throughout the facility.

9.1.1.2 Operational conditions related to frequency, duration and amount of use Table 9.2. Duration, frequency and amount

Information type Data field Explanation Assumption used in the exposure Used amount of substance per day 150 tonnes/day assessment Duration of exposure per day at Information provided by members of the >4 hours workplace [for one worker] calcium carbide consortium Frequency of exposure at workplace Once per day [for one worker] Assumption used in the exposure Annual amount used per site 150 000 tonnes/year assessment Information provided by members of the Emission days per site 200 days/year calcium carbide consortium

9.1.1.3 Operational conditions and risk management measures related to product1 characteristics Fehler! Verweisquelle konnte nicht gefunden werden.. shows the product characteristics. Manufacture of calcium carbide is a closed, controlled process with occasional controlled exposure. Transfer of calcium carbide to vessels or large containers takes place at dedicated facilities. Milling of calcium carbide is either carried out at a separate site or at the production sites.

1 “Product” includes substances, preparations and articles

3 Table 9.3: Characteristics of the substance

Information type Data field Explanation Formed in the liquid state at high Physical state Solid temperature, then allowed to cool and solidify The actual size of calcium carbide For solids: Categorisation of dust grades Low, medium, high supplied depends on the processing requirements of the downstream use Industrial-grade calcium carbide Purity of industrial-grade calcium 80% contains about 80% CaC , 15% CaO and carbide 2 5% other impurities in the raw material Risk management measures related to See text. the design of product

9.1.1.4 Operational conditions related to available dilution capacity and characteristics of exposed humans Table 9.4. shows the characteristics of exposed humans that are assumed for the exposure assessment. Table 9.4. Operational conditions related to respiration and skin contact

Information type Data field Explanation Respiration volume under conditions of Default worker respiration rate for light 10 m3/d use activity 50 000 m3 ; exchange Room size and ventilation rate approximately 5 times per hour ECETOC TRA model default: PROC2 non-dispersive use, no direct Area of skin contact with the substance 480 cm2 handling, palms of both hands. under conditions of use PROC8b: wide-dispersive use, direct handling, palms of both hands. Body weight 70 kg Default for workers

Environmental surroundings characteristics A dilution factor of 40 has been used, because calcium carbide production takes place at large industrial sites. This is taken from the Emission Scenario Document in part IV of the risk assessment guidance for new and existing substances. This scenario has a standard waste water treatment plant flow rate of 6 000 m3/day.

9.1.1.5 Other operational conditions of use Releases to air Emissions of dust can be encountered at various stages over the whole production process. The main source of dust emissions is the dust-laden furnace gas. Depending on the de-dusting system, dust emissions from the use of furnace gas are between <5 and 15 mg/Nm3. Diffuse emissions arising from the tapping of liquid CaC2 can be reduced by a fume extraction system and waste gas treatment to a large extent. The EU IPPC BREF document on Large Volume Inorganic Chemicals (EU BREF 2007) gives the emission factor to air, in furnace and tapping gas after the de-dusting process as <110 g/t CaC2 and < 15 mg/Nm3 (current state of the art) respectively (common de-dusting system for tapping and

4 furnace gas). Based on information from consortium members, a worst-case value for emissions to air is <166 g/t. Releases of calcium carbide dust or particulates to air during manufacturing would also occur at the crushing, sieving, screening and storage stages of production. Air pollution control devices such as fabric filters and scrubbers are usually in place during these operations. The EU IPPC BREF document on Large Volume Inorganic Chemicals (EU BREF 2007) gives the emission factor to air, during the crushing of calcium carbide (after dust abatement with fabric filter) as 1 g/t calcium carbide, which is 1E-4%. Dust content and emissions is largely dependent on the method of block crushing. The REACH default environmental release estimates as given in Table R.16-23 in Chapter R.16 (environmental exposure estimation) of the REACH guidance are very conservative. The estimated default release to air for production of chemicals (ERC1) is given as 5%. Such a default is not applicable to calcium carbide production, as evidenced by the BREF and the site visit made by one of the authors. It cannot be excluded that some dust will react with water vapour resulting in acetylene losses to air. For the purpose of this assessment the worst-case emission of 166 g/tonne of dust to air has been used to estimate emissions. This is assumed to include emissions from crushing, sieving, screening and storing where these are carried out on the production site. However, releases to the environment proper will be much lower than this because particles will be too small to travel into the wider environment. Therefore on the basis of the observed dust trapped in the work place the release to the wider local environment is considered to be less than 50% of the nominal amount. Releases to water Water is used for the indirect cooling of the furnace and other devices during calcium carbide manufacturing. The cooling water is not contaminated during this use (EU BREF 2007). Fabric filters are generally used for dust abatement during crushing of block calcium carbide2. Most of the calcium carbide dust generated during production and collected from off-gas, local exhaust ventilation and plant cleaning processes is reused or recycled. Some of the dust may however find its way to the wastewater stream during neutralisation in the drain. The main constituent (the carbide itself) will, however, react there therefore calcium hydroxide and acetylene could be present at low levels. The non-volatile impurities would remain and exposure to these impurities cannot be excluded. Table R.16-23 in Chapter R.16 (environmental exposure estimation) of the REACH guidance gives the default release estimate to wastewater for production of chemicals (ERC1) as 6%. This high default release estimate is not expected to be applicable to calcium carbide production, where no water is used during the actual production, apart from a cooling jacket around the reactor vessel. As a reasonable estimate perhaps 1% of the dust emissions reach water as fugitive loss. However, this will ultimately generate acetylene and the volatility of acetylene produced is such that all of it would evaporate before the waste stream reaches a wastewater treatment plant. Release of the impurities in commercial CaC2 could occur and the exposure of wastewater to these has been accounted for. Emission to soil No direct emissions to soil, although losses of dust to air followed by redeposition are included in the modelling.

9.1.1.6 Risk management measures Table 9.5 summarises the risk management measures in place during production of calcium carbide.

2 It might be important to consider the release route for CaC2 during cleaning of fabric filters.

5 Table 9.5. Risk management measures for industrial site

Information type Data field Explanation Containment and local exhaust ventilation Containment plus good work practice required Local exhaust ventilation required plus good work practise No

Personal protective equipment (PPE) Protective gloves and clothing Skin protection are used Information from production sites Eye protection Goggles are used Information from production sites Respiratory protection Respiration masks are used Information from production sites Others Skin protection creams Information from production sites Other risk management measures related to workers

Risk management measures related to environmental emissions from industrial sites Onsite pre-treatment of wastewater No measured data Resulting fraction of initially applied amount in wastewater released from site to the external sewage system 1.7x10-6kg/kg Air emission abatement Scrubbers, Fabric filters Information from production sites Value is fraction of tonnage produced, Resulting fraction of applied amount in expressed as calcium carbide, in the waste gas released to environment 1.7x10-4 kg/kg form of dust. Onsite waste treatment No measured data. Fraction of initially applied amount sent to external waste treatment. This is the sum of direct losses from processes to waste, and the residues from onsite wastewater and waste gas treatment. 1.7x10-4kg/kg Generic environmental surrounding characteristics considered covers both Municipal or other type of external on-site wastewater and municipal or wastewater treatment Yes external wastewater treatment Effluent (of the wastewater treatment 6 000 m3/day discharged to Standard size wastewater treatment plant) discharge rate wastewater treatment plant plant for highly industrial sites. The spreading of sludge is assumed in accordance with the default models, Recovery of sludge for agriculture or but is not believed to occur at every horticulture Yes location.

9.1.1.7 Waste related measures

Waste generated from calcium carbide production is mainly ferrosilicon (FeSi) with CaC2 and calcium carbide dust. CaC2 is separated from ferrosilicon and is reused, recycled or neutralised. Calcium Carbide dust from air emission abatement devices and cleaning operations is also reused, recycled or neutralised. Solid waste is handled differently across production sites. Some production sites recover dust into other production streams or convert it to hydrated lime in an acetylene generator.

6 Solid waste from the furnace off-gas scrubbing system is sent to an approved on-site settling lagoon at some production sites, while substances from filters are treated with small amounts of water to decompose carbide and then deposited in dedicated landfills.

9.1.2 Exposure estimation

9.1.2.1 Workers exposure

9.1.2.1.1 Acute/Short term exposure Workers at industrial sites are routinely involved with the same tasks; therefore it is more appropriate to consider long-term exposure.

9.1.2.1.2 Long-term exposure Human exposure from production and industrial use, based on the known work pattern, has been estimated using the ECETOC TRA screening tool and measured data. Table 9.1 shows the REACH process categories important for human exposure assessment for the life cycle and identified uses of calcium carbide. Predictions are retained for reference. In a typical calcium carbide production plant, molten calcium carbide from the reaction furnace is allowed to pour into iron trucks, which take around 300 kg each. These are placed under the reactor one after another on an automated rail system, and after filling they are moved into a storage area to cool, which takes around 24 hours. Workers are at least 3 m away behind screens, in full protective clothing and helmets. Additionally there is ventilation for dust and furnace gas to prevent workers from being exposed. Deposits of powder of calcium oxide /carbide are found on the floor in the production area. These vary from 1 mm on general floor areas to 5 cm in depth around less accessible areas. Exhaust systems are used to reduce the amount of dust in the air. Worker exposure to dust can occur and is monitored. It is estimated that around 166 g of dust are generated for each tonne of carbide produced. This is a consequence of the large scale handling of solids under conditions which are open at some stages in the processing. Measurements from a typical production site Maximum exposure levels occur in the vicinity of the silo automatic loading. The average exposure is 5.5 mg/m3. The maximum exposure occurs when depositions of dust are swirled up during operating mode, with a measured value of 54.7 mg/m3. This operation mode works three times a day for 30 minutes and workers' exposure time is approximately 10 minutes per 30 minutes' operation. These values are above the AUT Workplace Exposure Limits (WELs) for suspended matter therefore PPE in the form of respiratory protective equipment such as the mask FFP2 is required. Qualitative assessment indicates that use of PPE is sufficient to reduce exposure to an acceptable level. The AUT WEL for biologic inert dust suspended matter is 10 mg/m³ and for alviola is 5 mg/m3. These values are based on an 8-hour TWA reference period. Oral exposure Eating and drinking at the workplace is forbidden across production sites. Hence, workers’ exposure via ingestion of calcium carbide is not expected. Dermal exposure Risk management measures used to prevent dermal exposures at most production sites include gloves, protective clothing, goggles and skin protection creams (used during crushing operations). Inappropriate use of PPE can result in skin irritation and burns.

Tier 1 dermal exposure estimates based on the ECETOC TRA workers’ model have been estimated for the production of calcium carbide (PROC 2 and 8b) and milling/formulation of calcium carbide products (PROC 5). According to the ECETOC assumptions for these process categories, the exposed skin surface area (palms of both hands) is 480 cm2 and LEV is assumed to be present. For PROC 2 (use in closed, continuous process with occasional controlled exposure), non-dispersive use and no direct handling is assumed. For PROC 8b (transfer from/to large dedicated vessels), wide-dispersive use, direct handling and intermittent exposure is assumed. No modifying factor (e.g. use of personal protective equipments) has been applied, except the use of local exhaust ventilation. Human health exposures during production and industrial uses of calcium carbide have been considered for the neat substance. In cases where calcium carbide is formulated during milling and formulated products are used in metallurgy, it is important to consider exposure to calcium carbide preparations and the concentration of calcium carbide in such preparation. Inhalation exposure A limited amount of dust is always prevalent during production. Exposure of workers via inhalation is prevented by use of respirators. Dust concentration in the work place has been measured to be in the range 1 to 5 mg/m3, with calcium carbide content of 20 to 50%, in the areas of highest dust in the plant. Duration of workers exposure to dust is reported to be for 1-4 hours per shift. Tier 1 inhalation exposure estimates based on the ECETOC TRA workers’ model have been estimated for the production of calcium carbide (PROC 2 and 8b) and milling/formulation of calcium carbide products (PROC 5). Based on the use pattern information and fugacity banding of the ECETOC model, the availability of calcium carbide for inhalation exposures has been assumed to fall in the ‘medium’ fugacity band i.e. slightly dusty during production and industrial use in acetylene production; and the ‘high’ fugacity band i.e. highly dusty during milling; and industrial use in metallurgy and calcium cyanamide production. No modifying factor (e.g. use of respiratory protective equipments) has been applied, except the use of local exhaust ventilation. Human health inhalation exposures during production and industrial uses of calcium carbide have been considered for the whole substance. The inhalation exposure estimate of 2.5 mg/m3 from the ECETOC TRA model for the milling process falls in the range of measured workplace dust concentrations (1 to 5 mg/m3, with 20 to 50% calcium carbide concentration) specified by members of the calcium carbide consortium. An exposure time of 1-4 hours is should be assumed. In cases where calcium carbide is formulated during milling and formulated products are used in metallurgy, it is important to consider exposure to calcium carbide preparations and the concentration of calcium carbide in such preparation will be required. Table 9.6. Long-term exposure concentrations to workers

Estimated exposure Estimated exposure concentrations concentrations Explanation / source of measured data Routes of exposure value unit Value unit ECETOC TRA model prediction for 0.14 mg/kg/day - - PROC 2 (production)

ECETOC TRA model prediction for Dermal exposure 0.69 mg/kg/day - - PROC 8b (production)

ECETOC TRA model prediction for Inhalation exposure 0.25 mg/m3 0.036a mg/kg/day PROC 8b (production) ECETOC TRA model prediction for 2.5 mg/m3 0.36 mg/kg/day PROC 5 (milling) Notes: a Calculated assuming a default bodyweight of 70 kg for workers and a default respiratory volume of 10 m3, light activity, for an 8 hour work shift. Table 9.7. Summary of long-term exposure concentration to workers

Routes of exposure Concentrations Justification Dermal local exposure (in mg/cm2) Dermal systemic exposure 0.69 Worst case ECETOC TRA model prediction for PROC 8b (production) (in mg/kg bw/d) Inhalation exposure (in mg/m3)/8h 2.5 Worst case ECETOC TRA model prediction for PROC 5 (milling) workday3

9.1.2.2 Consumer exposure There is no consumer exposure from the production of calcium carbide.

9.1.2.3 Indirect exposure of humans via the environment (oral) There is no oral exposure of humans via the environment.

9.1.2.4 Environmental exposure Predicted Environmental Calculations (PECs) have been determined using EUSES 2.1.1. The EUSES program implements the environmental exposure models described in REACH Technical Guidance Chapter R16. Default model parameters have been used with the following exceptions: Lowest daily flow rate to WWTP – 6 000 m3/day Dilution factor – 40 (EU TGD Part IV, EC 2003) Local tonnage – 150 tonnes per day Number of days – 200 days There is only one site in the Region.

3 air concentration at the workplace

9.1.2.4.1 Environmental releases The release fractions are discussed in Section 9.1.1.5. From this, emissions to air as dust are 83.3 g/tonne, as calcium carbide. As discussed in Section 7 for the environment the assessment is considering the two impurities calcium cyanamide (as cyanamide) and calcium sulfide. The maximum content of calcium cyanamide in calcium carbide is 2% by weight (see Section 1.2), hence the emission factor is 1.65 g/tonne. For calcium sulfide, the maximum content is 2.5% by weight (see Section 1.2), hence the emission factor is 2.2 g/tonne. For water, the emissions are 1% of those to air, or 1.7 g/tonne as calcium carbide. The corresponding emission factors for the two impurities are 16.5 mg/tonne for calcium cyanamide and 22 mg/tonne for calcium sulfide. These factors are applied to a site producing 150 tonnes of calcium carbide per day. No measured values for released amounts are available, so the calculated values are used in the exposure estimation. These are summarised in Table 9.8 and Table 9.9. Table 9.8. Summary of the releases to the environment - cyanamide

Release1 from point source (kg/d) (local exposure Compartments estimation) Justification Aquatic (without 0.0044 Release calculated based on local tonnage STP) Air (direct + STP) 0.44 Point source release rate, direct only. Soil (direct releases None only) Notes: 1Releases converted to cyanamide basis.

Table 9.9. Summary of the releases to the environment – calcium sulfide

Release from point source (kg/d) (local exposure Compartments estimation) Justification Aquatic (without 0.011 Release calculated based on local tonnage STP) Air (direct + STP) 1.1 Point source release rate, direct only. Soil (direct releases None only)

9.1.2.4.2 Exposure concentrations in the environment Table 9.10 summarises the exposure concentrations for cyanamide calculated using EUSES 2.1.1. Table 9.10. Summary of exposure concentrations from production – cyanamide STP OUTPUT Value Unit Fraction of emission directed to air by STP 5.14E-06 [%] Fraction of emission directed to water by STP 12.7 [%] Fraction of emission directed to sludge by STP 0.037 [%]

Fraction of the emission degraded in STP 87.3 [%] Total of fractions 1.00E+01 [%] Local indirect emission to air from STP during episode 2.26E-10 [kg.d-1] Concentration in untreated wastewater 4.40E-04 [mg.l-1] Concentration of chemical (total) in the STP-effluent 5.56E-05 [mg.l-1] Concentration in dry sewage sludge 4.12E-04 [mg.kg-1] PEC for micro-organisms in the STP 5.56E-05 [mg.l-1]

LOCAL CONCENTRATIONS AND DEPOSITIONS Value Unit AIR Concentration in air during emission episode 1.22E-04 [mg.m-3] Annual average concentration in air, 100 m from point source 1.01E-04 [mg.m-3] Total deposition flux during emission episode 2.20E-04 [mg.m-2.d-1] Annual average total deposition flux 1.82E-04 [mg.m-2.d-1]

WATER, SEDIMENT Concentration in surface water during emission episode (dissolved) 1.39E-06 [mg.l-1] Concentration in surface water exceeds solubility No Annual average concentration in surface water (dissolved) 1.14E-06 [mg.l-1] Concentration in seawater during emission episode (dissolved) 4.40E-06 [mg.l-1] Annual average concentration in seawater (dissolved) 3.62E-06 [mg.l-1]

SOIL, GROUNDWATER Concentration in agric. soil averaged over 30 days 1.78E-05 [mg.kgwwt-1] Concentration in agric. soil averaged over 180 days 1.75E-05 [mg.kgwwt-1] Concentration in grassland averaged over 180 days 2.80E-05 [mg.kgwwt-1] Fraction of steady-state (agricultural soil) 1 [-] Fraction of steady-state (grassland soil) 1 [-]

LOCAL PECS [PRODUCTION] Value Unit AIR Annual average local PEC in air (total) 1.01E-04 [mg.m-3]

WATER, SEDIMENT Local PEC in surface water during emission episode (dissolved) 1.39E-06 [mg.l-1] Qualitative assessment might be needed (TGD Part II, 5.6) No Annual average local PEC in surface water (dissolved) 1.14E-06 [mg.l-1] Local PEC in fresh-water sediment during emission episode 1.21E-06 [mg.kgwwt-1] Local PEC in seawater during emission episode (dissolved) 4.40E-06 [mg.l-1] Qualitative assessment might be needed (TGD Part II, 5.6) No Annual average local PEC in seawater (dissolved) 3.62E-06 [mg.l-1] Local PEC in marine sediment during emission episode 3.82E-06 [mg.kgwwt-1]

SOIL, GROUNDWATER Local PEC in agric. soil (total) averaged over 30 days 1.78E-05 [mg.kgwwt-1] Local PEC in agric. soil (total) averaged over 180 days 1.75E-05 [mg.kgwwt-1] Local PEC in grassland (total) averaged over 180 days 2.80E-05 [mg.kgwwt-1] Local PEC in pore water of agricultural soil 9.38E-05 [mg.l-1] Local PEC in pore water of grassland 1.50E-04 [mg.l-1]

Local PEC in groundwater under agricultural soil 9.38E-05 [mg.l-1]

Table 9.11 summarises the exposure concentrations for calcium sulfide calculated using EUSES 2.1.1. Table 9.11. Summary of exposure concentrations from production – calcium sulfide

STP OUTPUT Value Unit Fraction of emission directed to air by STP 4.33E-10 [%] Fraction of emission directed to water by STP 6.51 [%] Fraction of emission directed to sludge by STP 0.0292 [%] Fraction of the emission degraded in STP 93.5 [%] Total of fractions 100 [%] Local indirect emission to air from STP during episode 4.77E-14 [kg.d-1] Concentration in untreated wastewater 1.10E-03 [mg.l-1] Concentration of chemical (total) in the STP-effluent 7.16E-05 [mg.l-1] Concentration in effluent exceeds solubility No Concentration in dry sewage sludge 8.12E-04 [mg.kg-1] PEC for micro-organisms in the STP 7.16E-05 [mg.l-1]

LOCAL CONCENTRATIONS AND DEPOSITIONS Value Unit AIR Concentration in air during emission episode 3.06E-04 [mg.m-3] Annual average concentration in air, 100 m from point source 2.51E-04 [mg.m-3] Total deposition flux during emission episode 0.011 [mg.m-2.d-1] Annual average total deposition flux 9.01E-03 [mg.m-2.d-1]

WATER, SEDIMENT Concentration in surface water during emission episode (dissolved) 1.79E-06 [mg.l-1] Concentration in surface water exceeds solubility No Annual average concentration in surface water (dissolved) 1.47E-06 [mg.l-1] Concentration in seawater during emission episode (dissolved) 1.10E-05 [mg.l-1] Annual average concentration in seawater (dissolved) 9.04E-06 [mg.l-1]

SOIL, GROUNDWATER Concentration in agric. soil averaged over 30 days 3.78E-05 [mg.kgwwt-1] Concentration in agric. soil averaged over 180 days 3.78E-05 [mg.kgwwt-1] Concentration in grassland averaged over 180 days 7.47E-05 [mg.kgwwt-1] Fraction of steady-state (agricultural soil) 1 [-] Fraction of steady-state (grassland soil) 1 [-]

LOCAL PECS [PRODUCTION] Value Unit AIR Annual average local PEC in air (total) 2.51E-04 [mg.m-3]

WATER, SEDIMENT Local PEC in surface water during emission episode (dissolved) 1.79E-06 [mg.l-1] Qualitative assessment might be needed (TGD Part II, 5.6) No Annual average local PEC in surface water (dissolved) 1.47E-06 [mg.l-1] Local PEC in fresh-water sediment during emission episode 1.52E-06 [mg.kgwwt-1]

Local PEC in seawater during emission episode (dissolved) 1.10E-05 [mg.l-1] Qualitative assessment might be needed (TGD Part II, 5.6) No Annual average local PEC in seawater (dissolved) 9.04E-06 [mg.l-1] Local PEC in marine sediment during emission episode 9.36E-06 [mg.kgwwt-1]

SOIL, GROUNDWATER Local PEC in agric. soil (total) averaged over 30 days 3.78E-05 [mg.kgwwt-1] Local PEC in agric. soil (total) averaged over 180 days 3.78E-05 [mg.kgwwt-1] Local PEC in grassland (total) averaged over 180 days 7.47E-05 [mg.kgwwt-1] Local PEC in pore water of agricultural soil 2.18E-04 [mg.l-1] Local PEC in pore water of grassland 4.31E-04 [mg.l-1] Local PEC in groundwater under agricultural soil 2.18E-04 [mg.l-1]

9.1.2.4.3 Exposure concentration relevant for the food chain (Secondary poisoning) Neither of the two impurities being considered accumulates in the food chain, so the assessment of secondary poisoning is not considered further.

9.2 ES 2: Milling/formulation of calcium carbide products

9.2.1.1 Description of activities and processes covered in the exposure scenario This scenario covers the milling of calcium carbide based on information provided by members of the calcium carbide consortium. Due to the hazards associated with acetylene, no water is used in the facility.

9.2.1.2 Operational conditions related to frequency, duration and amount of use Table 9.12. Duration, frequency and amount

Information type Data field Explanation Assumption used in the exposure Used amount of substance per day 150 tonnes/day assessment Duration of exposure per day at Information provided by members of the >4 hours workplace [for one worker] calcium carbide consortium Frequency of exposure at workplace Once per day [for one worker] Assumption used in the exposure Annual amount used per site 30 000 tonnes/year assessment Information provided by members of the Emission days per site 200 days/year calcium carbide consortium

9.2.1.3 Operational conditions and risk management measures related to product4 characteristics Table 9.13 shows the product characteristics. Milling or formulation of calcium carbide is either carried out at a separate site or at the production sites (mixing of blending in batch process).

4 “Product” includes substances, preparations and articles

Table 9.13. Characteristics of the substance

9.2.1.4 Operational conditions related to available dilution capacity and characteristics of exposed humans Table 9.14 shows the characteristics of exposed humans that are assumed for the exposure assessment. Table 9.14. Operational conditions related to respiration and skin contact

Information type Data field Explanation Respiration volume under conditions of Default worker respiration rate for light 10 m3/d use activity ECETOC TRA model default: PROC2 non-dispersive use, no direct Area of skin contact with the substance 480 cm2 handling, palms of both hands. under conditions of use PROC8b: wide-dispersive use, direct handling, palms of both hands. Body weight 70 kg Default for workers

Environmental surroundings characteristics Standard environment assumed.

9.2.1.5 Other operational conditions of use Releases to air Releases of calcium carbide dust or particulates to air will occur at the crushing, sieving, screening and storage stages. Air pollution control devices such as fabric filters and scrubbers are usually in place during these operations. The EU IPPC BREF document on Large Volume Inorganic Chemicals (EU BREF 2007) gives the emission factor to air, during the crushing of calcium carbide (after dust abatement with fabric filter) as 1 g/t calcium carbide, which is 1E-4%. Dust content and emissions is largely dependent on the method of block crushing. The REACH default environmental release estimates as given in Table R.16-23 in Chapter R.16 (environmental exposure estimation) of the REACH guidance are very conservative. The estimated default release to air for formulation of preparations (ERC2) is given as 2.5%. For the purpose of this assessment the worst-case emission of 1 g/tonne of dust to air has been used to estimate emissions. This is assumed to include emissions from crushing, sieving, screening and storing. Releases to water

Table R.16-23 in Chapter R.16 (environmental exposure estimation) of the REACH guidance gives the default release estimate to wastewater for formulation of preparations (ERC2) as 2%. As the substance reacts with water to produce acetylene, the use of water on such sites is avoided and therefore the default factor is an over-estimate. It has been assumed that the factor for production sites (1% of the dust emissions) is also reasonable here. Emission to soil

9.2.1.6 Risk management measures Table 9.15 summarises the risk management measures in place during the milling/formulation of calcium carbide. Table 9.15. Risk management measures for industrial site

Information type Data field Explanation Containment and local exhaust ventilation Containment plus good work practice required No measured data Local exhaust ventilation required plus good work practise

Personal protective equipment (PPE) Protective gloves and clothing Skin protection are used Company information Eye protection Goggles are used Company information Respiratory protection Respirators are used Company specific information Others Skin protection creams Company specific information Other risk management measures related to workers

Risk management measures related to environmental emissions from industrial sites Onsite pre-treatment of wastewater No measured data. Resulting fraction of initially applied amount in wastewater released from site to the external sewage system 1x10-8 kg/kg Air emission abatement No measured data. Resulting fraction of applied amount in waste gas released to environment 1x10-6 kg/kg Onsite waste treatment No measured data. Fraction of initially applied amount sent to external waste treatment. This is the sum of direct losses from processes to waste, and the residues from onsite wastewater and waste gas treatment. 1x10-6 kg/kg Generic environmental surrounding characteristics considered covers both Municipal or other type of external on-site wastewater and municipal or wastewater treatment Yes external wastewater treatment. Effluent (of the wastewater treatment 2 000 m3/d discharged to plant) discharge rate wastewater treatment plant Default. Recovery of sludge for agriculture or The spreading of sludge is assumed a horticulture Yes worst-case scenario.

9.2.2 Exposure estimation

9.2.2.1 Workers exposure

9.2.2.1.1 Acute/Short term exposure Workers at industrial sites are routinely involved with the same tasks; therefore it is more appropriate to consider long-term exposure.

9.2.2.1.2 Long-term exposure Human exposure from milling/formulation, based on the known work pattern has been estimated using the ECETOC TRA screening tool. Exposures as measured for the production scenario may also be relevant. Therefore personal protective equipment as described for ES 1 will also be needed if the limits are exceeded locally. An important consideration for human health exposure assessment is exposure to the impurities in calcium carbide that have been classified as harmful to human health Table 9.1 shows the REACH process categories, important for human exposure assessment, for the life cycle and identified uses of calcium carbide. Oral exposure Eating and drinking at the workplace is forbidden across sites. Hence, workers’ exposure via ingestion of calcium carbide is not expected. Dermal exposure Risk management measures used to prevent dermal exposures at most sites include gloves, protective clothing, goggles and skin protection creams (used during crushing operations). Inappropriate use of PPE can result in skin irritation and burns. Tier 1 dermal exposure estimates based on the ECETOC TRA workers’ model have been estimated for the milling/formulation of calcium carbide (PROC 5; mixing or blending in batch process). According to the ECETOC assumptions for this process category, the exposed skin surface area (palms of both hands) is 480 cm2 and LEV is assumed to be present. No modifying factor (e.g. use of personal protective equipments) has been applied, except the use of local exhaust ventilation. Human health exposures during milling/formulation of calcium carbide have been considered for the neat substance.

Inhalation exposure Tier 1 inhalation exposure estimates based on the ECETOC TRA workers’ model have been estimated for the milling/formulation of calcium carbide (PROC 5). In cases where calcium carbide is formulated during milling, it is important to consider exposure to calcium carbide preparations and the concentration of calcium carbide in such preparation is required. Table 9.16. Long-term exposure concentrations to workers

Estimated exposure Measured exposure concentrations concentrations Explanation / source of measured data Routes of exposure Value Unit Value Unit ECETOC TRA model prediction for Dermal exposurea 0.07 mg/kg/day - - PROC 5 (milling) Maximum value from industrial Inhalation exposure 2.5 mg/m3 3.8 - measurement Notes: a Calculated assuming a default bodyweight of 70 kg for workers and a default respiratory volume of 10 m3, light activity, for an 8 hour work shift.

Table 9.17: Summary of long-term exposure concentration to workers

Routes of exposure Concentrations Justification Dermal local exposure 0.01 ECETOC TRA model prediction for PROC 5 (milling) (in mg/cm2) Dermal systemic exposurea 0.07 ECETOC TRA model prediction for PROC 5 (milling) (in mg/kg bw/d) Inhalation exposurea 0.36 ECETOC TRA model prediction for PROC 5 (milling) (in mg/m3)/8h workday5 Notes: a Calculated assuming a default bodyweight of 70 kg for workers and a default respiratory volume of 10 m3, light activity, for an 8 hour work shift.

9.2.2.2 Consumer exposure There is no consumer exposure from the milling/formulation of calcium carbide.

9.2.2.3 Indirect exposure of humans via the environment (oral) There is no oral exposure of humans via the environment.

9.2.2.4 Environmental exposure Predicted Environmental Calculations (PECs) have been determined using EUSES 2.1.1. The EUSES program implements the environmental exposure models described in REACH Technical Guidance Chapter R16. Default model parameters have been used. Local tonnage – 150 tonnes per day Number of days – 200 days.

5 air concentration at the workplace

9.2.2.4.1 Environmental releases The release fractions are discussed in Section 9.2.1.5.) From this emissions to air as dust are 1 g/tonne, as calcium carbide. As discussed in Section 7 for the environment the assessment is considering the two impurities calcium cyanamide (as cyanamide) and calcium sulfide. The maximum content of calcium cyanamide in calcium cyanamide is 2% by weight (see Section Fehler! Verweisquelle konnte nicht gefunden werden..), hence the emission factor is 0.02 g/tonne. For calcium sulfide, the maximum content is 2.5% by weight (see Section Fehler! Verweisquelle konnte nicht gefunden werden..) The emission factor is 0.025 g/tonne. For water, the emissions are 1% of those to air, or 0.01 g/tonne as calcium carbide. The corresponding emission factors for the two impurities are 0.2 mg/tonne for calcium cyanamide and 0.25 mg/tonne for calcium sulfide. These factors are applied to a site handling 150 tonnes of calcium carbide per day. No measured values for released amounts are available, so the calculated values are used in the exposure estimation. These are summarised in Table 9.18 and Table 9.19. Table 9.18. Summary of the releases to the environment - cyanamide

Release1 from point source (kg/d) (local exposure Compartments estimation) Justification Aquatic (without 1.0E-04 Release calculated based on local tonnage STP) Air (direct + STP) 0.01 Point source release rate, direct only. Soil (direct releases None only) Note: 1 releases converted to cyanamide basis

Table 9.19. Summary of the releases to the environment – calcium sulfide

Release from point source (kg/d) (local exposure Compartments estimation) Justification Aquatic (without 0.0013 Release calculated based on local tonnage STP) Air (direct + STP) 0.0125 Point source release rate, direct only. Soil (direct releases None only)

9.2.2.4.2 Exposure concentration in the environment Table 9.20 summarises the exposure concentrations for cyanamide calculated using EUSES 2.1.1. Table 9.20. Summary of exposure concentrations from milling/formulation – cyanamide OUTPUT Value Unit Fraction of emission directed to air by STP 5.16E-06 [%] Fraction of emission directed to water by STP 12.7 [%] Fraction of emission directed to sludge by STP 0.037 [%]

Fraction of the emission degraded in STP 87.3 [%] Total of fractions 100 [%] Local indirect emission to air from STP during episode 6.70E-12 [kg.d-1] Concentration in untreated wastewater 6.50E-05 [mg.l-1] Concentration of chemical (total) in the STP-effluent 8.23E-06 [mg.l-1] Concentration in effluent exceeds solubility No Concentration in dry sewage sludge 6.09E-05 [mg.kg-1] PEC for micro-organisms in the STP 8.23E-06 [mg.l-1]

LOCAL CONCENTRATIONS AND DEPOSITIONS Value Unit AIR Concentration in air during emission episode 3.61E-06 [mg.m-3] Annual average concentration in air, 100 m from point source 2.97E-06 [mg.m-3] Total deposition flux during emission episode 6.53E-06 [mg.m-2.d-1] Annual average total deposition flux 5.37E-06 [mg.m-2.d-1]

WATER, SEDIMENT Concentration in surface water during emission episode (dissolved) 8.23E-07 [mg.l-1] Concentration in surface water exceeds solubility No Annual average concentration in surface water (dissolved) 6.76E-07 [mg.l-1] Concentration in seawater during emission episode (dissolved) 6.50E-07 [mg.l-1] Annual average concentration in seawater (dissolved) 5.34E-07 [mg.l-1]

SOIL, GROUNDWATER Concentration in agric. soil averaged over 30 days 5.73E-07 [mg.kgwwt-1] Concentration in agric. soil averaged over 180 days 5.31E-07 [mg.kgwwt-1] Concentration in grassland averaged over 180 days 8.31E-07 [mg.kgwwt-1] Fraction of steady-state (agricultural soil) 1 [-] Fraction of steady-state (grassland soil) 1 [-]

LOCAL PECS [INDUSTRIAL USE] Value Unit AIR Annual average local PEC in air (total) 2.97E-06 [mg.m-3]

WATER, SEDIMENT Local PEC in surface water during emission episode (dissolved) 8.23E-07 [mg.l-1] Qualitative assessment might be needed (TGD Part II, 5.6) No Annual average local PEC in surface water (dissolved) 6.76E-07 [mg.l-1] Local PEC in fresh-water sediment during emission episode 7.14E-07 [mg.kgwwt-1] Local PEC in seawater during emission episode (dissolved) 6.50E-07 [mg.l-1] Qualitative assessment might be needed (TGD Part II, 5.6) No Annual average local PEC in seawater (dissolved) 5.34E-07 [mg.l-1] Local PEC in marine sediment during emission episode 5.64E-07 [mg.kgwwt-1]

SOIL, GROUNDWATER Local PEC in agric. soil (total) averaged over 30 days 5.73E-07 [mg.kgwwt-1] Local PEC in agric. soil (total) averaged over 180 days 5.31E-07 [mg.kgwwt-1] Local PEC in grassland (total) averaged over 180 days 8.31E-07 [mg.kgwwt-1] Local PEC in pore water of agricultural soil 2.84E-06 [mg.l-1]

Local PEC in pore water of grassland 4.45E-06 [mg.l-1] Local PEC in groundwater under agricultural soil 2.84E-06 [mg.l-1]

Table 9.21 summarises the exposure concentrations for calcium sulfide calculated using EUSES 2.1.1. Table 9.21. Summary of exposure concentrations from milling/formulation – calcium sulfide

OUTPUT Value Unit Fraction of emission directed to air by STP 1.25E-10 [%] Fraction of emission directed to water by STP 6.51 [%] Fraction of emission directed to sludge by STP 0.0292 [%] Fraction of the emission degraded in STP 93.5 [%] Total of fractions 100 [%] Local indirect emission to air from STP during episode 1.57E-16 [kg.d-1] Concentration in untreated wastewater 6.25E-05 [mg.l-1] Concentration of chemical (total) in the STP-effluent 4.06E-06 [mg.l-1] Concentration in effluent exceeds solubility No Concentration in dry sewage sludge 4.62E-05 [mg.kg-1] PEC for micro-organisms in the STP 4.06E-06 [mg.l-1]

LOCAL CONCENTRATIONS AND DEPOSITIONS Value Unit AIR Concentration in air during emission episode 3.52E-06 [mg.m-3] Annual average concentration in air, 100 m from point source 2.90E-06 [mg.m-3] Total deposition flux during emission episode 1.27E-04 [mg.m-2.d-1] Annual average total deposition flux 1.04E-04 [mg.m-2.d-1]

WATER, SEDIMENT Concentration in surface water during emission episode (dissolved) 7.81E-07 [mg.l-1] Concentration in surface water exceeds solubility No Annual average concentration in surface water (dissolved) 6.44E-07 [mg.l-1] Concentration in seawater during emission episode (dissolved) 1.20E-06 [mg.l-1] Annual average concentration in seawater (dissolved) 9.87E-07 [mg.l-1]

SOIL, GROUNDWATER Concentration in agric. soil averaged over 30 days 8.42E-07 [mg.kgwwt-1] Concentration in agric. soil averaged over 180 days 8.40E-07 [mg.kgwwt-1] Concentration in grassland averaged over 180 days 1.66E-06 [mg.kgwwt-1] Fraction of steady-state (agricultural soil) 1 [-] Fraction of steady-state (grassland soil) 1 [-]

LOCAL PECS [INDUSTRIAL USE] Value Unit AIR Annual average local PEC in air (total) 5.58E-06 [mg.m-3]

WATER, SEDIMENT Local PEC in surface water during emission episode (dissolved) 7.81E-07 [mg.l-1] Qualitative assessment might be needed (TGD Part II, 5.6) No Annual average local PEC in surface water (dissolved) 6.44E-07 [mg.l-1] Local PEC in fresh-water sediment during emission episode 6.65E-07 [mg.kgwwt-1]

Local PEC in seawater during emission episode (dissolved) 1.20E-06 [mg.l-1] Qualitative assessment might be needed (TGD Part II, 5.6) No Annual average local PEC in seawater (dissolved) 9.87E-07 [mg.l-1] Local PEC in marine sediment during emission episode 1.03E-06 [mg.kgwwt-1]

SOIL, GROUNDWATER Local PEC in agric. soil (total) averaged over 30 days 8.42E-07 [mg.kgwwt-1] Local PEC in agric. soil (total) averaged over 180 days 8.40E-07 [mg.kgwwt-1] Local PEC in grassland (total) averaged over 180 days 1.66E-06 [mg.kgwwt-1] Local PEC in pore water of agricultural soil 4.85E-06 [mg.l-1] Local PEC in pore water of grassland 9.54E-06 [mg.l-1] Local PEC in groundwater under agricultural soil 4.85E-06 [mg.l-1]

9.2.2.4.3 Exposure concentration relevant for the food chain (Secondary poisoning) Neither of the two impurities being considered accumulates in the food chain, so the assessment of secondary poisoning is not considered further.

9.3 ES 3: Use as an intermediate in the production of acetylene and calcium cyanamide

9.3.1 Exposure scenario

9.3.1.1 Description of activities and processes covered in the exposure scenario This scenario covers the use of calcium carbide in the production of acetylene, based on information provided by members of the calcium carbide consortium. Calcium carbide is used as a process material or intermediate in the production of acetylene and calcium cyanamide. Releases can be estimated using the REACH or standard TGD defaults, once the tonnage in this use is known. Essentially, calcium carbide is transformed to other products during industrial use. However, exposure of soil and water (via raw material, process and product handling) to the impurities in commercial CaC2 would be expected during this use. Emissions to the environment of calcium carbide and impurities in raw materials handling are considered here. Emissions of the impurities in waste from the processes are considered to be addressed in the assessments of the production of acetylene and calcium cyanamide.

9.3.1.2 Operational conditions related to frequency, duration and amount of use A document (EIGA 2008) calculating emissions of acetylene to air from an acetylene production plant provides information on the amounts used per day at a typical site, and the number of days worked. These are included in Table 9.22. Table 9.22. Duration, frequency and amount

Information type Data field Explanation Used amount of substance per day 10.08 tonnes From EIGA (2008) Duration of exposure per day at 1-4 hours Information from industry workplace [for one worker] Frequency of exposure at workplace Once Information from industry [for one worker] Annual amount used per site 2520 tonnes From EIGA (2008) Emission days per site 250 From EIGA (2008)

9.3.1.3 Operational conditions and risk management measures related to product6 characteristics Table 9.23 shows the product characteristics. Industrial use of calcium carbide as an intermediate in the production of acetylene and calcium cyanamide takes place in a closed, controlled process with occasional controlled exposure. Transfer of calcium carbide to vessels or large containers takes place at dedicated facilities.

6 “Product” includes substances, preparations and articles

Table 9.23. Characteristics of the substance or preparation

Information type Data field Explanation Physical state solid Medium for acetylene production; high for calcium cyanamide For solids: Categorisation of dust grades production. Risk management measures related to Calcium carbide granules are used the design of product for the acetylene production

9.3.1.4 Operational conditions related to available dilution capacity and characteristics of exposed humans See Table 9.4. Environmental surroundings characteristics Standard environmental characteristics are appropriate for this scenario.

9.3.1.5 Other operational conditions of use The REACH default environmental release estimates for industrial use of intermediates (ERC6A) are: Release to air: 5 % Release to wastewater: 2% Releases to air Releases to air during production are controlled by dust or particulate matter control devices such as fabric filter, with a dust emission limit of 50 mg/m3. Release of calcium carbide dust to air during the production of acetylene occurs when calcium carbide is charged to the acetylene generation. However, this is only applicable to an open generator system and not a closed system (EIGA 2008). Calcium carbide dust emission to air (from a cyclone) at an open generator system acetylene production plant handling 2,520 t/year of calcium carbide has been estimated as 4 kg/yr (EIGA 2008), or 4/250 = 0.016 kg/d. This gives a release estimate of 0.00015% of calcium carbide dust to air. Release to wastewater Wastewater is generated from acetylene production process and will contain impurities from the calcium carbide used as well as by-products from the reaction. This is assumed to be dealt with in the CSR for acetylene production. Release to soil Releases to soil are assumed not to occur.

9.3.1.6 Risk management measures See Table 9.5.

9.3.1.7 Waste related measures Wastes are recycled into the processes.

9.3.2 Exposure estimation

9.3.2.1 Workers exposure

9.3.2.1.1 Acute/Short term exposure Workers at industrial sites are routinely involved with the same tasks; therefore it is more appropriate to consider long-term exposure.

9.3.2.1.2 Long-term exposure Exposures as measured for the production scenario may also be relevant. Therefore personal protective equipment as described for ES 1 will also be needed if the limits are exceeded locally. Duration of exposure (in the areas with the greatest dust) per personnel at most sites is reported to be for 1-4 hours per shift Oral exposure Eating and drinking at the workplace is forbidden across sites. Hence, workers’ exposure via ingestion of Calcium Carbide is not expected. Dermal exposure Risk management measures used to prevent dermal exposures at most sites include gloves, protective clothing and goggles. In appropriate use of PPE can result in skin irritation and burns. Inhalation exposure Exposure of workers via inhalation is prevented by air exhaustion and use of respirators. Table 9.24. Long-term exposure concentrations to workers Estimated Exposure Measured exposure Concentrations concentrations Explanation / source of measured data Routes of exposure Value Unit Value Unit ECETOC TRA model prediction for Dermal exposurea 0.14 mg/kg/day - - PROC 2 (acetylene and calcium cyanamide) ECETOC TRA model prediction for 0.05 mg/m3 - - PROC 2 (acetylene) Inhalation exposure ECETOC TRA model prediction for 0.1 mg/m3 - - PROC 2 (calcium cyanamide) Notes: a Calculated assuming a default bodyweight of 70 kg for workers and a default respiratory volume of 10 m3, light activity, for an 8 hour work shift.

Table 9.25. Summary of long-term exposure concentration to workers

Routes of exposure Concentrations Justification Dermal local exposure ECETOC TRA model prediction for PROC 2 (acetylene and 0.02 (in mg/cm2) calcium cyanamide) Dermal systemic exposurea ECETOC TRA model prediction for PROC 2 (acetylene and 0.14 (in mg/kg bw/d) calcium cyanamide) Inhalation exposurea 0.007 ECETOC TRA model prediction for PROC 2 (acetylene) (in mg/m3)/8h workday7 Inhalation exposurea 0.14 ECETOC TRA model prediction for PROC 2 (calcium cyanamide) (in mg/m3)/8h workday8 Notes: a Calculated assuming a default bodyweight of 70 kg for workers and a default respiratory volume of 10 m3, light activity, for an 8 hour work shift.

9.3.2.2 Consumer exposure None expected.

9.3.2.3 Indirect exposure of humans via the environment (oral) Neither of the two impurities being considered accumulates in the food chain, so the assessment of secondary poisoning is not considered further.

9.3.2.4 Environmental exposure Predicted Environmental Calculations (PECs) have been determined using EUSES 2.1.1. The EUSES program implements the environmental exposure models described in REACH Technical Guidance Chapter R16. Default model parameters have been used. Local tonnage – 10.08 tonnes per day Number of days – 250 days.

9.3.2.4.1 Environmental releases The release fractions are discussed in Section9.3.1.5). From this, emissions to air as dust are 0.016 kg/day, as calcium carbide from a representative plant. As discussed in Section 7 for the environment the assessment is considering the two impurities calcium cyanamide (as cyanamide) and calcium sulfide. The maximum content of calcium cyanamide in calcium cyanamide is 2% by weight (see Section 1.2)), hence the emission is 0.32 g/day. For calcium sulfide, the maximum content is 2.5% by weight (see Section 1.2)), hence the emission is 0.43 g/day. No measured values for released amounts are available, so the calculated values are used in the exposure estimation. These are summarised in Table 9.26.

7 air concentration at the workplace 8 air concentration at the workplace

Table 9.26. Summary of the releases to the environment

Release from point source (kg/d) (local exposure Compartments estimation) Justification Aquatic (without Not addressed here, but in acetylene CSR. STP) Aquatic (after STP) Not addressed here, but in acetylene CSR. 3.2E-04 cyanamide Air (direct + STP) 4.3E-04 calcium As dust, direct. sulfide Soil (direct releases Not addressed here, but in acetylene CSR. only)

9.3.2.4.2 Exposure concentrations in the environment The only relevant emissions are to air, therefore only concentrations in air and in soil through deposition have been calculated. The results are summarised in Table 9.27. Table 9.27. Summary of exposure concentrations from acetylene production - cyanamide

LOCAL CONCENTRATIONS AND DEPOSITIONS Value Unit AIR Concentration in air during emission episode 3.78E-08 [mg.m-3] Annual average concentration in air, 100 m from point source 2.59E-08 [mg.m-3] Total deposition flux during emission episode 6.84E-08 [mg.m-2.d-1] Annual average total deposition flux 4.68E-08 [mg.m-2.d-1]

SOIL, GROUNDWATER Concentration in agric. soil averaged over 30 days 4.48E-09 [mg.kgwwt-1] Concentration in agric. soil averaged over 180 days 4.48E-09 [mg.kgwwt-1] Concentration in grassland averaged over 180 days 7.20E-09 [mg.kgwwt-1] Fraction of steady-state (agricultural soil) 1 [-] Fraction of steady-state (grassland soil) 1 [-]

LOCAL PECS [ACETYLENE PRODUCTION] Value Unit AIR Annual average local PEC in air (total) 2.59E-08 [mg.m-3]

SOIL, GROUNDWATER Local PEC in agric. soil (total) averaged over 30 days 4.48E-09 [mg.kgwwt-1] Local PEC in agric. soil (total) averaged over 180 days 4.48E-09 [mg.kgwwt-1] Local PEC in grassland (total) averaged over 180 days 7.20E-09 [mg.kgwwt-1] Local PEC in pore water of agricultural soil 2.40E-08 [mg.l-1] Local PEC in pore water of grassland 3.85E-08 [mg.l-1] Local PEC in groundwater under agricultural soil 2.40E-08 [mg.l-1]

27 The exposure concentrations from acetylene production for calcium sulfide are summarised in Table 9.28. The only relevant emissions are to air, therefore only concentrations in air and in soil through deposition have been calculated. Table 9.28. Summary of exposure concentrations from acetylene production – calcium sulfide

LOCAL CONCENTRATIONS AND DEPOSITIONS Value Unit AIR Concentration in air during emission episode 9.10E-08 [mg.m-3] Annual average concentration in air, 100 m from point source 6.23E-08 [mg.m-3] Total deposition flux during emission episode 3.25E-06 [mg.m-2.d-1] Annual average total deposition flux 2.23E-06 [mg.m-2.d-1]

SOIL, GROUNDWATER Concentration in agric. soil averaged over 30 days 9.35E-09 [mg.kgwwt-1] Concentration in agric. soil averaged over 180 days 9.35E-09 [mg.kgwwt-1] Concentration in grassland averaged over 180 days 1.85E-08 [mg.kgwwt-1] Fraction of steady-state (agricultural soil) 1 [-] Fraction of steady-state (grassland soil) 1 [-]

LOCAL PECS [ACETYLENE PRODUCTION] Value Unit AIR Annual average local PEC in air (total) 6.23E-08 [mg.m-3]

SOIL, GROUNDWATER Local PEC in agric. soil (total) averaged over 30 days 9.35E-09 [mg.kgwwt-1] Local PEC in agric. soil (total) averaged over 180 days 9.35E-09 [mg.kgwwt-1] Local PEC in grassland (total) averaged over 180 days 1.85E-08 [mg.kgwwt-1] Local PEC in pore water of agricultural soil 5.38E-08 [mg.l-1] Local PEC in pore water of grassland 1.07E-07 [mg.l-1] Local PEC in groundwater under agricultural soil 5.38E-08 [mg.l-1]

9.3.2.4.3 Exposure concentration relevant for the food chain (Secondary poisoning) Neither of the two impurities being considered accumulates in the food chain, so the assessment of secondary poisoning is not considered further.

9.4 ES 4: Use of calcium carbide in metallurgy

9.4.1 Exposure scenario The REACH default release estimates for industrial use of reactive processing aids (ERC6B) are: Release to air: 0.1 % Release to wastewater: 5% These values are unrealistically high, and they may be ignored on the basis of a site visit to an iron foundry. This shows that at the worst there may be occasional losses of carbide from transfer lines,

28 but there is no carbide/oxide dust in the area. The entire facility is free from use of water. Losses will therefore be even lower than those estirnated for production of calcium carbide.

Exposures have been assessedas minimal, and less than those from production, based on site visits, and therefore do not need tobe quantified.

29 9.5 Carbide lamps (ES5)

9.5.1 Exposure scenario This exposure scenario is valid for professionals and consumers.

9.5.1.1 Description of activities and processes covered in the exposure scenario Granules of Ca-carbide are filled into an afterwards closed container in the carbide lamp. Water is dropped to the Ca-carbide to generate acetylene, which is inflamed to produce light.

9.5.1.2 Operational conditions related to frequency, duration and amount of use Duration, frequency and amount

Information type Data field Explanation Used amount of substance (as such or in preparation) per worker or consumer per day ca. 0.1 kg/d Typical data. Duration of the filling procedure, afterwards the container in the lamp is Duration of exposure per day <1 h/day closed.

Frequency of exposure 1 /day to 1 /month Annual amount used per site ca. 10 kg/y Emission days per site ca. 100 d/y

9.5.1.3 Operational conditions and risk management measures related to product characteristics Characteristics of the substance

Information type Data field Explanation Physical state solids Granules of 1 to 3 mm diameters are For solids: Categorisation of dust grades Low used. Concentration of substance in preparation - Substance is used as such. Concentration after dilution for use (if relevant) - Substance is used as such. Risk management measures related to Granules of 1 to 3 mm diameters are the design of product used.

9.5.1.4 Operational conditions related to available dilution capacity and characteristics of exposed humans Default data as in CHESAR are used.

30 9.5.1.5 Other operational conditions of use Technical fate of substance and losses from process, waste water and air

Information type Data field Explanation Fraction consumed in process/use 100 %

9.5.1.6 Risk management measures Risk management measures for wide dispersive use

Information type Data field Explanation Personal protective equipment (PPE) Gloves are recommended but, based on Gloves - experience, are not required.

9.5.1.7 Waste related measures Fractions of substance in waste and waste management measures

Information type Data field Explanation Amount of substances in waste resulting from identified uses covered The substance is consumed in the exposure scenario 0 kg/y during the process.

9.5.2 Exposure estimation

9.5.2.1 Workers exposure

9.5.2.1.1 Acute/Short term exposure Acute exposure concentrations to workers Estimated Measured exposure Exposure concentrations Concentrations Explanation / source of measured data Routes of exposure value unit Value unit Data estimated by TRA for workers, based on dust, mg/c 0.1 - m2 which is not present, as the substance is used in Dermal exposure granular form. - - -

mg/m Data estimated by TRA for workers, based on dust, 0.06 3 - which is not present, as the substance is used in Inhalation exposure granular form. - - -

31 Summary of acute exposure concentrations to workers

Routes of exposure Concentrations Justification Granules of 1 to 3 mm particle size are used, therefore no exposure to dust will occur. Only an accidentally dermal exposure, during the filling of the container, could occur. Dermal local exposure < 0.1mg/cm2 From experience it can be stated that no irritating effects were reported in the past when (in mg/cm2) handling the devices by professionals or consumers.

Dermal systemic No systemic but only local effects, if any, are expected due to the reactivity of Ca-carbide not relevant exposure with water. (in mg/kg bw/d) Granules of 1 to 3 mm particle size are used, therefore no exposure to dust will occur. The Inhalation exposure < 0.06 mg/m3 vapour pressure of Ca-carbide is extremely low, not leading to a relevant concentration in (in mg/m3) air.

9.5.2.1.2 Long-term exposure The same data as for acute exposure are applied, as the relevant toxic effects are the local irritating effects.

9.5.2.2 Consumer exposure The same data as for workers are applied as there are no different uses or operational conditions for consumers, compared to workers. An oral exposure is not relevant, except in casualties.

9.5.2.3 Indirect exposure of humans via the environment (oral) An indirect exposure of man via the environment can be excluded, as the substance rapidly decays in contact with water or humidity.

32 9.5.2.4 Environmental exposure

9.5.2.4.1 Environmental releases Releases to the environment Predicted Measured release Explanation / source of measured data Compartments releases (kg/d) (kg/d)

0 The substance decays within the device. No release is possible. Accidental spillage during filling the device is not relevant as the substance rapidly decays at the - Aquatic (without first contact with water. STP) - 0 The substance decays within the device. No release is possible. Accidental spillage during filling the device

Aquatic (after is not relevant as the substance rapidly decays at the STP) - first contact with water.

Air (direct + 0 The substance has an extremely low vapour pressure and no dust STP) - is produced in the device. 0 The substance decays within the device. No release is possible. Accidental spillage during filling the device is not relevant as the - substance rapidly decays at the first contact with water. Soil (direct only)

Summary of the releases to the environment

Release from Total release point source for regional (kg/d) (local exposure exposure estimation Compartments estimation) (kg/d) Justification

Aquatic (without 0 0 see above STP) Aquatic (after STP) 0 0 see above Air (direct + STP) 0 0 see above

Soil (direct releases 0 0 see above only)

9.5.2.4.2 Exposure concentration in sewage treatment plants (STP) Not relevant, see above.

9.5.2.4.3 Exposure concentration in aquatic pelagic compartment Not relevant, see above.

9.5.2.4.4 Exposure concentration in sediments Not relevant, see above.

33 9.5.2.4.5 Exposure concentrations in soil and groundwater Not relevant, see above.

9.5.2.4.6 Atmospheric compartment Not relevant, see above.

9.5.2.4.7 Exposure concentration relevant for the food chain (Secondary poisoning) Not relevant, see above.

9.5.2.5 Regional exposure concentrations Not relevant, as no local exposure is expected.

34 9.6 Carbide welding (ES6)

9.6.1 Exposure scenario This exposure scenario is valid for professionals and consumers.

9.6.1.1 Description of activities and processes covered in the exposure scenario Granules of Ca-carbide are filled into an afterwards closed container in the welding device. Water is dropped to the Ca-carbide to generate acetylene, which is used for welding.

9.6.1.2 Operational conditions related to frequency, duration and amount of use Duration, frequency and amount

Information type Data field Explanation Used amount of substance (as such or in preparation) per worker or consumer per day ca. 1 kg/d Typical data. Duration of the filling procedure, afterwards the container in the device is Duration of exposure per day <1 h/day closed.

Frequency of exposure 1 /day to 1 /month Annual amount used per site ca. 100 kg/y Emission days per site ca. 100 d/y

9.6.1.3 Operational conditions and risk management measures related to product characteristics Characteristics of the substance

9.6.1.4 Operational conditions related to available dilution capacity and characteristics of exposed humans Default data as in CHESAR are used.

35 9.6.1.5 Other operational conditions of use Technical fate of substance and losses from process, waste water and air

Information type Data field Explanation Fraction consumed in process/use 100 %

9.6.1.6 Risk management measures Risk management measures for wide dispersive use

Information type Data field Explanation Personal protective equipment (PPE) Gloves are recommended but, based on Gloves - experience, are not required.

9.6.1.7 Waste related measures Fractions of substance in waste and waste management measures

Information type Data field Explanation Amount of substances in waste resulting from identified uses covered The substance is consumed in the exposure scenario 0 kg/y during the process.

9.6.2 Exposure estimation

9.6.2.1 Workers exposure

9.6.2.1.1 Acute/Short term exposure Acute exposure concentrations to workers Estimated Measured exposure Exposure concentrations Concentrations Explanation / source of measured data Routes of exposure value unit Value unit Data estimated by TRA for workers, based on dust, mg/c 0.1 - m2 which is not present, as the substance is used in Dermal exposure granular form. - - -

mg/m Data estimated by TRA for workers, based on dust, 0.06 3 - which is not present, as the substance is used in Inhalation exposure granular form. - - -

36 Summary of acute exposure concentrations to workers

9.6.2.1.2 Long-term exposure The same data as for acute exposure are applied, as the relevant toxic effects are the local irritating effects.

9.6.2.2 Consumer exposure The same data as for workers are applied as there are no different uses or operational conditions for consumers, compared to workers. An oral exposure is not relevant, except in casualties.

9.6.2.3 Indirect exposure of humans via the environment (oral) An indirect exposure of man via the environment can be excluded, as the substance rapidly decays in contact with water or humidity.

37 9.6.2.4 Environmental exposure

9.6.2.4.1 Environmental releases Releases to the environment Predicted Measured release Explanation / source of measured data Compartments releases (kg/d) (kg/d)

Aquatic (after is not relevant as the substance rapidly decays at the STP) - first contact with water.

Summary of the releases to the environment

Release from Total release point source for regional (kg/d) (local exposure exposure estimation Compartments estimation) (kg/d) Justification

Aquatic (without 0 0 see above STP) Aquatic (after STP) 0 0 see above Air (direct + STP) 0 0 see above

Soil (direct releases 0 0 see above only)

9.6.2.4.2 Exposure concentration in sewage treatment plants (STP) Not relevant, see above.

9.6.2.4.3 Exposure concentration in aquatic pelagic compartment Not relevant, see above.

9.6.2.4.4 Exposure concentration in sediments Not relevant, see above.

38 9.6.2.4.5 Exposure concentrations in soil and groundwater Not relevant, see above.

9.6.2.4.6 Atmospheric compartment Not relevant, see above.

9.6.2.4.7 Exposure concentration relevant for the food chain (Secondary poisoning) Not relevant, see above.

9.6.2.5 Regional exposure concentrations Not relevant, as no local exposure is expected.

39 9.7 Calcium carbide in humidity analyzers (ES7)

9.7.1 Exposure scenario This exposure scenario is valid for professionals.

9.7.1.1 Description of activities and processes covered in the exposure scenario Granules of Ca-carbide, welded in a glass tube, are put into a container of the analyzer. The article to be analysed is added together with steal balls. The container is closed and the content is mixed. The humidity of the article reacts with Ca-carbide and generates acetylene, which increases the pressure inside the container. The pressure is a measure of the humidity of the article.

9.7.1.2 Operational conditions related to frequency, duration and amount of use Duration, frequency and amount

Information type Data field Explanation Used amount of substance (as such) per worker per day ca. 0.1 kg/d Typical data.

Duration of the filling procedure, afterwards the container in the device is closed. Ca-carbide is welded in glass Duration of exposure per day <1 h/day tubes.

Frequency of exposure 10 /day Annual amount used per site ca. 10 kg/y Emission days per site ca. 100 d/y

9.7.1.3 Operational conditions and risk management measures related to product characteristics Characteristics of the substance

9.7.1.4 Operational conditions related to available dilution capacity and characteristics of exposed humans Default data as in CHESAR are used.

9.7.1.5 Other operational conditions of use Technical fate of substance and losses from process, waste water and air

Information type Data field Explanation Fraction consumed in process/use 100 %

9.7.1.6 Risk management measures Risk management measures for wide dispersive use

Information type Data field Explanation Personal protective equipment (PPE) Gloves are recommended but, based on Gloves - experience, are not required.

9.7.1.7 Waste related measures Fractions of substance in waste and waste management measures

Information type Data field Explanation Amount of substances in waste The substance is consumed resulting from identified uses covered during the process. Residual in the exposure scenario 0 kg/y amounts are reacted with water.

9.7.2 Exposure estimation

9.7.2.1 Workers exposure

9.7.2.1.1 Acute/Short term exposure Acute exposure concentrations to workers Estimated Measured exposure Exposure concentrations Concentrations Explanation / source of measured data Routes of exposure value unit Value unit Data estimated by TRA for workers, based on dust, mg/c 0.1 - m2 which is not present, as the substance is used in Dermal exposure granular form and welded in glass tubes. - - -

mg/m Data estimated by TRA for workers, based on dust, 0.06 3 - which is not present, as the substance is used in Inhalation exposure granular form and welded in glass tubes. - - -

41 Summary of acute exposure concentrations to workers

9.7.2.1.2 Long-term exposure The same data as for acute exposure are applied, as the relevant toxic effects are the local irritating effects.

9.7.2.2 Consumer exposure The same data as for workers are applied as there are no different uses or operational conditions for consumers, compared to workers. An oral exposure is not relevant, except in casualties.

9.7.2.3 Indirect exposure of humans via the environment (oral) An indirect exposure of man via the environment can be excluded, as the substance rapidly decays in contact with water or humidity.

42 9.7.2.4 Environmental exposure

9.7.2.4.1 Environmental releases Releases to the environment Predicted Measured release Explanation / source of measured data Compartments releases (kg/d) (kg/d)

Aquatic (after is not relevant as the substance rapidly decays at the STP) - first contact with water.

Summary of the releases to the environment

Release from Total release point source for regional (kg/d) (local exposure exposure estimation Compartments estimation) (kg/d) Justification

Aquatic (without 0 0 see above STP) Aquatic (after STP) 0 0 see above Air (direct + STP) 0 0 see above

Soil (direct releases 0 0 see above only)

9.7.2.4.2 Exposure concentration in sewage treatment plants (STP) Not relevant, see above.

9.7.2.4.3 Exposure concentration in aquatic pelagic compartment Not relevant, see above.

9.7.2.4.4 Exposure concentration in sediments Not relevant, see above.

43 9.7.2.4.5 Exposure concentrations in soil and groundwater Not relevant, see above.

9.7.2.4.6 Atmospheric compartment Not relevant, see above.

9.7.2.4.7 Exposure concentration relevant for the food chain (Secondary poisoning) Not relevant, see above.

9.7.2.5 Regional exposure concentrations Not relevant, as no local exposure is expected.

9.8 Regional exposure concentrations Regional concentrations cannot be added to the exposure scenario because there is no realistic way to assess regional exposure for inorganic substances. The standard models, e.g. EUSES 2.1.1 are parameterised for organic substances. Furthermore, the ultimate degradation products in the environment are inorganic species already present in the environment at high concentration.

It is concluded that regional exposure assessment need not be performed.

44 10 RISK CHARACTERISATION It should be noted that no combined assessment of exposure from the different scenarios is necessary.

10.1 ES 1: Production of calcium carbide

10.1.1 Human health

10.1.1.1 Workers As discussed in section 9.1.2.1.2, exposure via ingestion is unlikely to occur. Inhalation exposure to dust from commercially produced calcium carbide occurs at levels that exceed the WEL for calcium dihydroxide, with high levels of exposure occurring for short periods. Use of PPE in the form of respiratory protective equipment such as the mask FFP2 is required. Qualitative assessment indicates that use of PPE is sufficient to reduce exposure to an acceptable level. Dermal exposure also occurs. The lead health effects are skin irritation and severe eye irritation. Risk management measures used to prevent dermal exposures at most production sites include gloves, protective clothing, goggles and skin protection creams (used during crushing operations). Appropriate use of PPE is sufficient to prevent skin irritation and burns.

10.1.1.2 Consumers There is no exposure of consumers from production.

10.1.2 Environment The EUSES 2.1.1 software has been used to calculate Risk Characterisation Ratios (RCRs) for cyanamide in water, sediment, soil and STP, which are summarised in Table 10.1 below. Table 10.1. Summary of risk characterisation ratios (RCRs) from production – cyanamide

COMPARTMENT RCR WATER RCR for the local fresh-water compartment 5.56E-04 Intermittent release No RCR for the local marine compartment 1.76E-02

SEDIMENT RCR for the local fresh-water sediment compartment 5.56E-04 Extra factor 10 applied to PEC/PNEC No RCR for the local marine sediment compartment 1.76E-02 Extra factor 10 applied to PEC/PNEC No

SOIL RCR for the local soil compartment 3.82E-02 Extra factor 10 applied to PEC/PNEC No

STP RCR for the sewage treatment plant 1.80E-05

46 The RCRs for calcium sulfide in water, sediment and soil calculated using EUSES 2.1.1 are given in Table 10.2 below. Table 10.2. Summary of risk characterisation ratios (RCRs) from production – calcium sulfide

COMPARTMENT RCR WATER RCR for the local fresh-water compartment 8.13E-03 Intermittent release No RCR for the local marine compartment 0.5

SEDIMENT RCR for the local fresh-water sediment compartment 8.13E-03 Extra factor 10 applied to PEC/PNEC No RCR for the local marine sediment compartment 0.5 Extra factor 10 applied to PEC/PNEC No

SOIL RCR for the local soil compartment <<0.99 Extra factor 10 applied to PEC/PNEC No

STP RCR for the sewage treatment plant

The RCRs for cyanamide and sulfide are considered separately as RCRs should be summed only if the mode of toxic action is the same. Calcium sulfide has a different mode of action from that of cyanamide, and so it is not appropriate to sum the RCRs. The RCR for cyanamide (soil) is the highest of the RCRs for this impurity, and is well below 1, and so the risks from cyanamide in commercially produced calcium carbide are acceptable. The highest RCR for sulfide is also for soil, and this value is still below 1. Analyses of commercially produced calcium carbide give a proportion of sulfur. In the highly reducing conditions of blocks of calcium carbide that are the initial product, it is reasonable to assume that the majority of the sulfur will be present as sulfide. However, in the fine dust that is present in the workplace, oxidation of sulfide to sulfate will occur very rapidly. The risk assessment has been based on the absolute worst case, as it assumes that all of the sulfur in the calcium carbide will be present as sulfide. From the expected rate of oxidation of sulfide in contact with air, it is anticipated that actual emission of sulfide will be far less than the extent modelled.

10.2 ES 2: Milling/formulation of calcium carbide products

10.2.1 Human health

10.2.1.1 Workers As discussed in section 9.2.2.1.2, exposure via ingestion is unlikely to occur. Inhalation exposure to dust from commercially produced calcium carbide occurs at levels that do not exceed the WEL for calcium dihydroxide, so no additional use of PPE is required, and the level of exposure is acceptable. Dermal exposure also occurs. The lead health effects are skin irritation and severe eye irritation. Risk management measures used to prevent dermal exposures at most production sites include gloves, protective clothing, goggles and skin protection creams (used during crushing operations). Appropriate use of PPE is sufficient to prevent skin irritation and burns.

10.2.1.2 Consumers There is no exposure of consumers from milling.

10.2.2 Environment The EUSES 2.1.1 software has been used to calculate Risk Characterisation Ratios (RCRs) for cyanamide in water, sediment, soil and STP, which are summarised in Table 10.3 below. Table 10.3. Summary of risk characterisation ratios (RCRs) from milling/formulation – cyanamide

COMPARTMENT RCR WATER RCR for the local fresh-water compartment 1.32E-04 Intermittent release No RCR for the local marine compartment 1.04E-03

SEDIMENT RCR for the local fresh-water sediment compartment 1.32E-04 Extra factor 10 applied to PEC/PNEC No RCR for the local marine sediment compartment 1.04E-03 Extra factor 10 applied to PEC/PNEC No

SOIL RCR for the local soil compartment 4.92E-04 Extra factor 10 applied to PEC/PNEC No

STP RCR for the sewage treatment plant 1.06E-06

The RCRs for calcium sulfide in water, sediment and soil calculated using EUSES 2.1.1 are given in Table 10.4 below. Table 10.4. Summary of risk characterisation ratios (RCRs) from milling/formulation – calcium sulfide

COMPARTMENT RCR

WATER RCR for the local fresh-water compartment 1.85E-03 Intermittent release No RCR for the local marine compartment 2.85E-02

SEDIMENT RCR for the local fresh-water sediment compartment 1.85E-03 Extra factor 10 applied to PEC/PNEC No RCR for the local marine sediment compartment 2.85E-02 Extra factor 10 applied to PEC/PNEC No

SOIL RCR for the local soil compartment <<1.2E-02 Extra factor 10 applied to PEC/PNEC No

STP RCR for the sewage treatment plant

10.3 ES 3: Use as an intermediate in the production of acetylene and calcium cyanamide

10.3.1 Human health

10.3.1.1 Workers As discussed in section 9.3.2.1.2, exposure via ingestion is unlikely to occur. Inhalation exposure to dust from commercially produced calcium carbide occurs at levels that do not exceed the WEL for calcium dihydroxide, so no additional use of PPE is required, and the level of exposure is acceptable. Dermal exposure also occurs. The lead health effects are skin irritation and severe eye irritation. Risk management measures used to prevent dermal exposures at most production sites include gloves, protective clothing, goggles and skin protection creams (used during crushing operations). Appropriate use of PPE is sufficient to prevent skin irritation and burns.

10.3.1.2 Consumers There is no exposure of consumers from use as an intermediate.

10.3.2 Environment The EUSES 2.1.1 software has been used to calculate Risk Characterisation Ratios (RCRs) for cyanamide, which are summarised in Table 10.5 below. The only relevant emissions are to air, therefore only concentrations in air and in soil through deposition have been calculated (see section 9.3.4.2)). Table 10.5. Summary of risk characterisation ratios (RCRs) from acetylene production – cyanamide

COMPARTMENT RCR WATER RCR for the local fresh-water compartment 0 Intermittent release No RCR for the local marine compartment 0

SEDIMENT RCR for the local fresh-water sediment compartment 0 Extra factor 10 applied to PEC/PNEC No RCR for the local marine sediment compartment 0 Extra factor 10 applied to PEC/PNEC No

SOIL RCR for the local soil compartment 9.6E-06 Extra factor 10 applied to PEC/PNEC No

STP RCR for the sewage treatment plant 0

The RCRs for calcium sulfide calculated using EUSES 2.1.1 are given in Table 10.6 below. The only relevant emissions are to air, therefore only concentrations in air and in soil through deposition have been calculated (see section 9.3.2.4.2)). Table 10.6. Summary of risk characterisation ratios (RCRs) from acetylene production – calcium sulfide

COMPARTMENT RCR WATER RCR for the local fresh-water compartment 0 Intermittent release No RCR for the local marine compartment 0

SEDIMENT RCR for the local fresh-water sediment compartment 0 Extra factor 10 applied to PEC/PNEC No RCR for the local marine sediment compartment 0 Extra factor 10 applied to PEC/PNEC No

SOIL RCR for the local soil compartment <<2.6E-04 Extra factor 10 applied to PEC/PNEC No

STP RCR for the sewage treatment plant

10.4 ES 4: Use of calcium carbide in metallurgy

As discussed in section 9.4, releases of commercially produced calcium carbide to the environment and exposure of workers have been assessed as minimal compared with ES 1. As no risk arises from production, quantification of risk from use of calcium carbide in metallurgy is unnecessary.

10.5 Carbide lamps ES 5 similar for ES 7 humidity analyzers

10.5.1 Human health

10.5.1.1 Workers Quantitative risk characterisation for workers

Route ES 5- exposure Leading toxic DN(M)EL Risk characterisation ratio concentrations end point / (EC) Critical effect Acute - Dermal not required N/A Not relevant - systemic Inhalation not required N/A Not relevant - effects Acute - local Dermal qualitative irritation Not quantifiable - effects Inhalation qualitative irritation 10 mg/m3 - Combined qualitative irritation Not quantifiable - routes Long-term - Dermal 0.343 mg/kg N/A Not relevant - systemic bw effects Inhalation qualitative N/A Not relevant - Combined qualitative N/A Not relevant - routes Long-term – Dermal 0.1 mg/cm2 irritation Not quantifiable - local effects Inhalation 0.06 mg/m3 irritation 10 mg/m3 0.006

Qualitative risk characterisation for workers

Route ES 5- exposure Leading toxic Qualitative risk characterisation concentrations end point / (EC) Critical effect Acute - Dermal not required N/A No systemic but only local effects, if any, are systemic expected due to the reactivity of Ca-carbide with effects water. Inhalation not required N/A No systemic but only local effects, if any, are expected due to the reactivity of Ca-carbide with water. Acute - local Dermal qualitative irritation Granules of 1 to 3 mm particle size are used, effects therefore no exposure to dust will occur. The filling of the devices occur only in intervals, from estimated once daily to once monthly. Only accidentally a short contact with skin could occur during the filling of the device. Afterwards the device is closed. From experience it can be stated that no irritating effects were reported in the past when handling the devices by professionals or consumers. No additional measures to prevent release or exposure are required, but gloves are recommended during the filling procedure. Inhalation qualitative irritation Granules of 1 to 3 mm particle size are used, therefore no exposure to dust will occur. The vapour pressure of Ca-carbide is extremely low,

53 not leading to a relevant concentration in air. The risk is low and acceptable. Combined qualitative irritation See the 2 lines above. routes Long-term - Dermal 0.343 mg/kg N/A No systemic but only local effects, if any, are systemic bw expected due to the reactivity of Ca-carbide with effects water. Inhalation qualitative N/A No systemic but only local effects, if any, are expected due to the reactivity of Ca-carbide with water. Combined qualitative N/A No systemic but only local effects, if any, are routes expected due to the reactivity of Ca-carbide with water. Long-term – Dermal 0.1 mg/cm2 irritation Granules of 1 to 3 mm particle size are used, local effects therefore no exposure to dust will occur. The filling of the devices occur only in intervals, from estimated once daily to once monthly. Only accidentally a short contact with skin could occur during the filling of the device. Afterwards the device is closed. From experience it can be stated that no irritating effects were reported in the past when handling the devices by professionals or consumers. No additional measures to prevent release or exposure are required, but gloves are recommended during the filling procedure. Inhalation 0.06 mg/m3 irritation Quantitative, see above.

10.5.1.2 Consumers

The same risks as for workers, see previous chapter, are assumed, as there are no different uses or operational conditions for consumers, compared to workers.

An oral exposure is not relevant, except in casualties.

10.5.2 Indirect exposure of humans via the environment

An indirect exposure and a risk for man via the environment can be excluded, as the substance rapidly decays in contact with water or humidity.

10.5.3 Environment

10.5.3.2 Aquatic compartment (including sediment and secondary poisoning) Risk characterisation for the aquatic compartment

Compartments PEC PNEC PEC/PNEC Discussion - Calcium carbide is unlikely to have direct toxic not toxicity is Freshwater effects on aquatic organisms. required unlikely No exposure is expected because of the rapid decay of Ca-carbide when coming in contact with

54 water. toxicity is - Calcium carbide is unlikely to have direct toxic unlikely effects on aquatic organisms. not Marine water No exposure is expected because of the rapid required decay of Ca-carbide when coming in contact with water. - Calcium carbide is unlikely to have direct toxic effects on aquatic organisms. toxicity is Sediment qualitative No exposure is expected because of the rapid unlikely decay of Ca-carbide when coming in contact with water. Aquatic freshwater not toxicity is - Calcium carbide does not have potential to food chain required unlikely bioaccumulate. Aquatic marine water not toxicity is - Calcium carbide does not have potential to food chain required unlikely bioaccumulate.

10.5.3.3 Terrestrial compartment (including secondary poisoning) Risk characterisation for the terrestrial compartment

Compartments PEC PNEC PEC/PNEC Discussion - It is unlikely that Ca-carbide could have toxic effects to terrestrial organisms. toxicity is qualitative No exposure is expected because of the rapid unlikely decay of Ca-carbide when coming in contact with Agricultural soil water or humidity. - It is unlikely that Ca-carbide could have toxic effects to terrestrial organisms. toxicity is qualitative No exposure is expected because of the rapid unlikely decay of Ca-carbide when coming in contact with Grassland water or humidity. - Calcium carbide does not have potential to toxicity is Terrestrial food not required bioaccumulate, and, therefore, secondary unlikely chain poisoning is not relevant.

10.5.3.4 Atmospheric compartment

It is unlikely that Ca‐carbide could have toxic effects on birds. Ca‐carbide is not volatile. No exposure is expected from dust because of the rapid decay of Ca‐carbide when coming in contact with humidity.

10.5.3.5 Microbiological activity in sewage treatment systems

Compartments PEC PNEC PEC/PNEC Discussion toxicity is - No exposure is expected because of the rapid not required unlikely decay of Ca-carbide when coming in contact with STP water.

55 10.6 Carbide welding ES 6

The risk assessment is the same as for ES 5 "Carbide lamps", see Chapter 10.1.

The risks for humans and the environment are acceptable also for the exposure scenario "Carbide welding".

10.7 Calcium carbide in humidity analyzers ES 6

The risk assessment is the same as for ES 5 "Carbide lamps", see Chapter 10.1.

The risks for humans and the environment are acceptable also for the exposure scenario "Calcium carbide in humidity analyzers".

10.8 Overall exposure (combined for all relevant emission/release sources)

It is unlikely that the 2 or 3 of the exposure scenarios take place at one site and/or are performed by the same person.

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