Safety Data Sheet: Calcium carbide - Radtke Messtechnik€¦ · Calcium carbide Revision: 2018 -09...
Transcript of Safety Data Sheet: Calcium carbide - Radtke Messtechnik€¦ · Calcium carbide Revision: 2018 -09...
ENGLISH: en Page: 1 / 14
Version number: GHS 2.0
Safety Data Sheet
According to 1907/2006, article 31 as amended
Calcium carbide
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 Centre)
Belfast 0870 600 6266 (UK only)
United Kingdom National Poisons Information Service (Cardiff Centre)
Cardiff 0870 600 6266 (UK only)
United Kingdom Scottish Poisons Information Bureau Edinburgh 0870 600 6266 (UK only)
ENGLISH: en Page: 2 / 14
Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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- egory
Hazard class and category
Hazard state- ment
2.12 substance and mixture which, in contact with water, emits flammable gas
1 Water-react. 1 H260
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 (respirat- ory tract irritation)
3 STOT SE 3 H335
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.
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Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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 irrita- tion 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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Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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 materi- als: 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 dis- charge. 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.
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Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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 try
Name of agent CAS No Identi- fier
TWA
[ppm]
TWA
[mg/m³]
STEL
[ppm]
STEL
[mg/m³]
Source
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 peri- od
(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 spe- cial purposes, it is recommended to check the resistance to chemicals of the protective gloves mentioned above to- gether 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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Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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 criter- ia)
Explosion limits of dust clouds not determined
Vapour pressure not determined
Density 2.22 g/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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SECTION 10: Stability and reactivity
Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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
oral LD50 >2,000 mg/kg rat
dermal LD50 >2,500 mg/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.
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Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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
LC50 >50 mg/l fish 96 h
EC50 4.62 mg/l aquatic invertebrates 48 h
ErC50 46 mg/l algae 72 h
LOEC >50 mg/l fish 96 h
NOEC 50 mg/l fish 96 h
growth rate (ErCx) 10% 12 mg/l algae 72 h
growth (EbCx) 10% 2.7 mg/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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Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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 dan- gerous 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
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Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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- ation in accordance with Regulation No
1272/2008/EC
R3 3
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 la-
belling of dangerous substances and mixtures, suppliers shall ensure, before the placing on the market, that the following re-
quirements 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.
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Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Legend
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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 re-
quirements 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- plication of lower and upper-tier require-
ments
Notes
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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National inventories
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
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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Version number: GHS 2.0
Replaces version of: 2018-05-09 (GHS 1)
Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)
Calcium carbide
Revision: 2018-09-07
SECTION 16: Other information
Indication of changes (revised safety data sheet)
Section Former entry (text/value) Actual entry (text/value) Safety- relev- ant
1.1 Alternative name(s): Calcium acetylide
yes
5.2 Special hazards arising from the substance or mixture:
Product may release hydrogen gas. Increased storage temperatures will accelerate this pro- cess. On contact with water highly flammable
and explosive acetylene is generated.
Special hazards arising from the substance or mixture:
On contact with water highly flammable and ex- plosive acetylene is generated.
yes
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: 14 / 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.
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.
1
Table 9.1, Overview on exposure scenarios and coverage of substance life cycle
stage
(PROC) (AC)
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.
2
ion e o
r
ge
ES
number
Volume (tonnes)
Man
ufa
ctu
re
Identified uses
Resulting
life cycle
Linked to
Identified
Use
Sector of Use (SU)
Preparation
Category
(PC)
Process category
Article category
us
e (f
Form
ula
t
End
use
Consu
mer
Serv
ice li
f
art
icle
s)
Wast
e s
ta
ES 1 Confidential
X SU 3 (main user group),
SU 8 (end-use) - PROC 2, 8b -
ES 2 Confidential
X SU 3 (main user group),
SU 10 (end-use) PC 20 PROC 5, 8b -
ES 3 Confidential
X SU 3 (main user group),
SU 8 (end-use) PC 19 PROC 2, 8b N/A
ES 4 Confidential
X SU 3 (main user group),
SU 14 (end-use) PC 20 PROC 221 N/A
ES 5 Confidential X X Carbide
lamps SU 2a PC 19 PROC 3 N/A
ES 6 Confidential X X Carbide
welding SU 19 PC 19 PROC 3 N/A
ES 7
Confidential X Calcium
carbide in
humidity
analyzers
SU 24, 19
PC 19
PROC 3
N/A
3
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
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
Information type Data field Explanation
Used amount of substance per day 150 tonnes/day Assumption used in the exposure assessment
Duration of exposure per day at workplace [for one worker]
>4 hours Information provided by members of the calcium carbide consortium
Frequency of exposure at workplace [for one worker]
Once per day
Annual amount used per site 150 000 tonnes/year Assumption used in the exposure assessment
Emission days per site 200 days/year Information provided by members of the calcium carbide consortium
4
Table 9.3: Characteristics of the substance
Information type
Data field
Explanation
Physical state
Solid Formed in the liquid state at high temperature, then allowed to cool and solidify
For solids: Categorisation of dust grades
Low, medium, high The actual size of calcium carbide supplied depends on the processing requirements of the downstream use
Purity of industrial-grade calcium
carbide
80% Industrial-grade calcium carbide contains about 80% CaC2, 15% CaO and 5% other impurities in the raw material
Risk management measures related to the design of product
See text.
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 use
10 m3/d Default worker respiration rate for light activity
Room size and ventilation rate 50 000 m3 ; exchange approximately 5 times per hour
Area of skin contact with the substance
under conditions of use
480 cm2
ECETOC TRA model default: PROC2 non-dispersive use, no direct handling, palms of both hands.
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/Nm
3 (current state of the art) respectively (common de-dusting system for tapping and
5
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.
6
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)
Skin protection Protective gloves and clothing 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
Resulting fraction of applied amount in
waste gas released to environment
1.7x10-4 kg/kg
Value is fraction of tonnage produced,
expressed as calcium carbide, in the 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
Municipal or other type of external
wastewater treatment
Yes
Generic environmental surrounding
characteristics considered covers both on-site wastewater and municipal or external wastewater treatment
Effluent (of the wastewater treatment plant) discharge rate
6 000 m3/day discharged to wastewater treatment plant
Standard size wastewater treatment plant for highly industrial sites.
Recovery of sludge for agriculture or
horticulture
Yes
The spreading of sludge is assumed in
accordance with the default models,
but is not believed to occur at every 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.
7
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.
8
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
Routes of exposure
Estimated exposure
concentrations
Estimated exposure
concentrations
Explanation / source of measured
data value unit Value unit
Dermal exposure
0.14 mg/kg/day - - ECETOC TRA model prediction for
PROC 2 (production)
0.69 mg/kg/day - - ECETOC TRA model prediction for
PROC 8b (production)
9
Routes of exposure
Estimated exposure
concentrations
Estimated exposure
concentrations
Explanation / source of measured
data value unit Value unit
0.07 mg/kg/day - -
ECETOC TRA model prediction for
PROC 5 (milling)
Inhalation exposure
0.05 mg/m3 0.007a mg/kg/day ECETOC TRA model prediction for
PROC 2 (production)
0.25 mg/m3 0.036a mg/kg/day ECETOC TRA model prediction for
PROC 8b (production)
2.5 mg/m3 0.36 mg/kg/day ECETOC TRA model prediction for
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
(in mg/kg bw/d)
0.69
Worst case ECETOC TRA model prediction for PROC 8b (production)
Inhalation exposure
(in mg/m3)/8h
workday3
2.5
Worst case ECETOC TRA model prediction for PROC 5 (milling)
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
10
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
Compartments
Release1 from
point source
(kg/d) (local
exposure
estimation)
Justification
Aquatic (without
STP) 0.0044 Release calculated based on local tonnage
Air (direct + STP) 0.44 Point source release rate, direct only.
Soil (direct releases only)
None
Notes: 1Releases converted to cyanamide basis.
Table 9.9. Summary of the releases to the environment – calcium sulfide
Compartments
Release from
point source
(kg/d) (local
exposure
estimation)
Justification
Aquatic (without STP)
0.011 Release calculated based on local tonnage
Air (direct + STP) 1.1 Point source release rate, direct only.
Soil (direct releases
only)
None
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 [%]
11
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]
12
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]
13
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.
14
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
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
Information type Data field Explanation
Used amount of substance per day 150 tonnes/day Assumption used in the exposure assessment
Duration of exposure per day at workplace [for one worker]
>4 hours Information provided by members of the calcium carbide consortium
Frequency of exposure at workplace [for one worker]
Once per day
Annual amount used per site 30 000 tonnes/year Assumption used in the exposure assessment
Emission days per site 200 days/year Information provided by members of the calcium carbide consortium
15
Table 9.13. Characteristics of the substance
Information type
Data field
Explanation
Physical state
Solid Formed in the liquid state at high temperature, then allowed to cool and solidify
For solids: Categorisation of dust grades
Low, medium, high The actual size of calcium carbide supplied depends on the processing requirements of the downstream use
Purity of industrial-grade calcium
carbide
80% Industrial-grade calcium carbide contains about 80% CaC2, 15% CaO and 5% other impurities in the raw material
Risk management measures related to the design of product
See text.
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 use
10 m3/d Default worker respiration rate for light activity
Area of skin contact with the substance
under conditions of use
480 cm2
ECETOC TRA model default: PROC2 non-dispersive use, no direct handling, palms of both hands.
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
16
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)
Skin protection Protective gloves and clothing 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
Municipal or other type of external
wastewater treatment
Yes
Generic environmental surrounding
characteristics considered covers both on-site wastewater and municipal or external wastewater treatment.
Effluent (of the wastewater treatment plant) discharge rate
2 000 m3/d discharged to wastewater treatment plant
Default.
Recovery of sludge for agriculture or horticulture
Yes The spreading of sludge is assumed a worst-case scenario.
17
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.
18
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
Routes of exposure
Estimated exposure
concentrations
Measured exposure
concentrations
Explanation / source of measured
data Value Unit Value Unit
Dermal exposurea 0.07 mg/kg/day - - ECETOC TRA model prediction for
PROC 5 (milling)
Inhalation exposure 2.5 mg/m3 3.8 - Maximum value from industrial
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
(in mg/cm2) 0.01 ECETOC TRA model prediction for PROC 5 (milling)
Dermal systemic exposurea
(in mg/kg bw/d) 0.07 ECETOC TRA model prediction for PROC 5 (milling)
Inhalation exposurea (in mg/m3)/8h workday5
0.36 ECETOC TRA model prediction for 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.
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
19
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
Compartments
Release1 from
point source
(kg/d) (local
exposure
estimation)
Justification
Aquatic (without
STP) 1.0E-04 Release calculated based on local tonnage
Air (direct + STP) 0.01 Point source release rate, direct only.
Soil (direct releases only)
None
Note: 1 releases converted to cyanamide basis
Table 9.19. Summary of the releases to the environment – calcium sulfide
Compartments
Release from
point source
(kg/d) (local
exposure
estimation)
Justification
Aquatic (without
STP) 0.0013 Release calculated based on local tonnage
Air (direct + STP) 0.0125 Point source release rate, direct only.
Soil (direct releases only)
None
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 [%]
20
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]
21
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]
22
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.
23
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 workplace [for one worker]
1-4 hours Information from industry
Frequency of exposure at workplace [for one worker]
Once Information from industry
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
24
Table 9.23. Characteristics of the substance or preparation
Information type
Data field
Explanation
Physical state solid
For solids: Categorisation of dust grades
Medium for acetylene production; high for calcium cyanamide production.
Risk management measures related to the design of product
Calcium carbide granules are used 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.
25
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
Routes of exposure
Estimated Exposure
Concentrations
Measured exposure
concentrations
Explanation / source of measured
data Value Unit Value Unit
Dermal exposurea
0.14
mg/kg/day
-
-
ECETOC TRA model prediction for
PROC 2 (acetylene and calcium
cyanamide)
Inhalation exposure
0.05 mg/m3 - - ECETOC TRA model prediction for
PROC 2 (acetylene)
0.1 mg/m3 - - ECETOC TRA model prediction for
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.
26
Table 9.25. Summary of long-term exposure concentration to workers
Routes of exposure Concentrations Justification
Dermal local exposure
(in mg/cm2) 0.02
ECETOC TRA model prediction for PROC 2 (acetylene and
calcium cyanamide)
Dermal systemic exposurea
(in mg/kg bw/d) 0.14
ECETOC TRA model prediction for PROC 2 (acetylene and calcium cyanamide)
Inhalation exposurea (in mg/m3)/8h workday7
0.007 ECETOC TRA model prediction for PROC 2 (acetylene)
Inhalation exposurea (in mg/m3)/8h workday8
0.14 ECETOC TRA model prediction for 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.
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
27
Table 9.26. Summary of the releases to the environment
Compartments
Release from point
source (kg/d) (local
exposure
estimation)
Justification
Aquatic (without
STP)
Not addressed here, but in acetylene CSR.
Aquatic (after STP) Not addressed here, but in acetylene CSR.
Air (direct + STP)
3.2E-04 cyanamide
4.3E-04 calcium
sulfide
As dust, direct.
Soil (direct releases only)
Not addressed here, but in acetylene CSR.
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]
28
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,
29
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.
30
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
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
For solids: Categorisation of dust grades
Low Granules of 1 to 3 mm diameters are 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 the design of product
Granules of 1 to 3 mm diameters are used.
9.5.1.4 Operational conditions related to available dilution capacity and characteristics of
exposed humans
Default data as in CHESAR are used.
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 exposure per day
<1 h/day
Duration of the filling procedure, afterwards the container in the lamp is 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
31
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
- Gloves are recommended but, based on 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 in the exposure scenario
0 kg/y
The substance is consumed
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
Routes of exposure
Estimated
Exposure
Concentrations
Measured exposure
concentrations
Explanation / source of measured data
value unit Value unit
Dermal exposure
0.1 mg/c m2
- Data estimated by TRA for workers, based on dust,
which is not present, as the substance is used in
granular form.
- - -
Inhalation exposure
0.06 mg/m 3
- Data estimated by TRA for workers, based on dust,
which is not present, as the substance is used in
granular form.
- - -
32
Summary of acute exposure concentrations to workers
Routes of exposure Concentrations Justification
Dermal local exposure
(in mg/cm2)
< 0.1mg/cm2
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.
From experience it can be stated that no irritating effects were reported in the past when
handling the devices by professionals or consumers.
Dermal systemic exposure (in mg/kg bw/d)
not relevant
No systemic but only local effects, if any, are expected due to the reactivity of Ca-carbide
with water.
Inhalation exposure
(in mg/m3)
< 0.06 mg/m3 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, not leading to a relevant concentration in
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.
33
9.5.2.4 Environmental exposure
9.5.2.4.1 Environmental releases
Releases to the environment
Summary of the releases to the environment
Compartments
Release from
point source
(kg/d) (local
exposure
estimation)
Total release
for regional
exposure
estimation
(kg/d)
Justification
Aquatic (without
STP) 0 0 see above
Aquatic (after STP) 0 0 see above
Air (direct + STP) 0 0 see above
Soil (direct releases only)
0 0 see above
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.
Compartments
Predicted
releases (kg/d)
Measured release
(kg/d) Explanation / source of measured data
Aquatic (without
STP)
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.
-
Aquatic (after
STP)
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.
Air (direct +
STP)
0 -
The substance has an extremely low vapour pressure and no dust
is produced in the device.
Soil (direct only)
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.
34
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.
35
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
9.6.1.3 Operational conditions and risk management measures related to product
characteristics
Characteristics of the substance
Information type
Data field
Explanation
Physical state solids
For solids: Categorisation of dust grades
Low Granules of 1 to 3 mm diameters are 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 the design of product
Granules of 1 to 3 mm diameters are used.
9.6.1.4 Operational conditions related to available dilution capacity and characteristics of
exposed humans
Default data as in CHESAR are used.
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 exposure per day
<1 h/day
Duration of the filling procedure, afterwards the container in the device is 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
36
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
- Gloves are recommended but, based on 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 in the exposure scenario
0 kg/y
The substance is consumed
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
Routes of exposure
Estimated
Exposure
Concentrations
Measured exposure
concentrations
Explanation / source of measured data
value unit Value unit
Dermal exposure
0.1 mg/c m2
- Data estimated by TRA for workers, based on dust,
which is not present, as the substance is used in
granular form.
- - -
Inhalation exposure
0.06 mg/m 3
- Data estimated by TRA for workers, based on dust,
which is not present, as the substance is used in
granular form.
- - -
37
Summary of acute exposure concentrations to workers
Routes of exposure Concentrations Justification
Dermal local exposure
(in mg/cm2)
< 0.1mg/cm2
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.
From experience it can be stated that no irritating effects were reported in the past when
handling the devices by professionals or consumers.
Dermal systemic exposure (in mg/kg bw/d)
not relevant
No systemic but only local effects, if any, are expected due to the reactivity of Ca-carbide
with water.
Inhalation exposure
(in mg/m3)
< 0.06 mg/m3 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, not leading to a relevant concentration in
air.
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.
38
9.6.2.4 Environmental exposure
9.6.2.4.1 Environmental releases
Releases to the environment
Summary of the releases to the environment
Compartments
Release from
point source
(kg/d) (local
exposure
estimation)
Total release
for regional
exposure
estimation
(kg/d)
Justification
Aquatic (without
STP) 0 0 see above
Aquatic (after STP) 0 0 see above
Air (direct + STP) 0 0 see above
Soil (direct releases only)
0 0 see above
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.
Compartments
Predicted
releases (kg/d)
Measured release
(kg/d) Explanation / source of measured data
Aquatic (without
STP)
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.
-
Aquatic (after
STP)
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.
Air (direct +
STP)
0 -
The substance has an extremely low vapour pressure and no dust
is produced in the device.
Soil (direct only)
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.
39
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.
40
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
9.7.1.3 Operational conditions and risk management measures related to product
characteristics
Characteristics of the substance
Information type
Data field
Explanation
Physical state solids
For solids: Categorisation of dust grades
Low Granules of 1 to 3 mm diameters are 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 the design of product
Granules of 1 to 3 mm diameters are used.
9.7.1.4 Operational conditions related to available dilution capacity and characteristics of
exposed humans
Default data as in CHESAR are used.
Information type Data field Explanation
Used amount of substance (as such) per worker per day
ca. 0.1 kg/d
Typical data.
Duration of exposure per day
<1 h/day
Duration of the filling procedure, afterwards the container in the device is closed. Ca-carbide is welded in glass tubes.
Frequency of exposure 10 /day
Annual amount used per site ca. 10 kg/y
Emission days per site ca. 100 d/y
41
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
- Gloves are recommended but, based on 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
resulting from identified uses covered in the exposure scenario
0 kg/y
The substance is consumed
during the process. Residual 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
Routes of exposure
Estimated
Exposure
Concentrations
Measured exposure
concentrations
Explanation / source of measured data
value unit Value unit
Dermal exposure
0.1 mg/c m2
- Data estimated by TRA for workers, based on dust,
which is not present, as the substance is used in
granular form and welded in glass tubes.
- - -
Inhalation exposure
0.06 mg/m 3
- Data estimated by TRA for workers, based on dust,
which is not present, as the substance is used in
granular form and welded in glass tubes.
- - -
42
Summary of acute exposure concentrations to workers
Routes of exposure Concentrations Justification
Dermal local exposure
(in mg/cm2)
< 0.1mg/cm2
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.
From experience it can be stated that no irritating effects were reported in the past when
handling the devices by professionals or consumers.
Dermal systemic exposure (in mg/kg bw/d)
not relevant
No systemic but only local effects, if any, are expected due to the reactivity of Ca-carbide
with water.
Inhalation exposure
(in mg/m3)
< 0.06 mg/m3 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, not leading to a relevant concentration in
air.
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.
43
9.7.2.4 Environmental exposure
9.7.2.4.1 Environmental releases
Releases to the environment
Summary of the releases to the environment
Compartments
Release from
point source
(kg/d) (local
exposure
estimation)
Total release
for regional
exposure
estimation
(kg/d)
Justification
Aquatic (without
STP) 0 0 see above
Aquatic (after STP) 0 0 see above
Air (direct + STP) 0 0 see above
Soil (direct releases only)
0 0 see above
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.
Compartments
Predicted
releases (kg/d)
Measured release
(kg/d) Explanation / source of measured data
Aquatic (without
STP)
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.
-
Aquatic (after
STP)
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.
Air (direct +
STP)
0 -
The substance has an extremely low vapour pressure and no dust
is produced in the device.
Soil (direct only)
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.
44
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.
46
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
47
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.
48
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
49
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
50
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
51
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
52
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.
53
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
concentrations
(EC)
Leading toxic
end point /
Critical effect
DN(M)EL Risk characterisation ratio
Acute -
systemic
effects
Dermal not required N/A Not relevant -
Inhalation not required N/A Not relevant -
Acute - local
effects
Dermal qualitative irritation Not quantifiable -
Inhalation qualitative irritation 10 mg/m3 -
Combined
routes
qualitative irritation Not quantifiable -
Long-term -
systemic
effects
Dermal 0.343 mg/kg
bw
N/A Not relevant -
Inhalation qualitative N/A Not relevant -
Combined
routes
qualitative N/A Not relevant -
Long-term –
local effects
Dermal 0.1 mg/cm2 irritation Not quantifiable -
Inhalation 0.06 mg/m3 irritation 10 mg/m3 0.006
Qualitative risk characterisation for workers
Route ES 5- exposure
concentrations
(EC)
Leading toxic
end point /
Critical effect
Qualitative risk characterisation
Acute -
systemic
effects
Dermal not required N/A No systemic but only local effects, if any, are
expected due to the reactivity of Ca-carbide with
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
effects
Dermal qualitative irritation Granules of 1 to 3 mm particle size are used,
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,
54
not leading to a relevant concentration in air.
The risk is low and acceptable.
Combined
routes
qualitative irritation See the 2 lines above.
Long-term -
systemic
effects
Dermal 0.343 mg/kg
bw
N/A No systemic but only local effects, if any, are
expected due to the reactivity of Ca-carbide with
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
routes
qualitative N/A No systemic but only local effects, if any, are
expected due to the reactivity of Ca-carbide with
water.
Long-term –
local effects
Dermal 0.1 mg/cm2 irritation Granules of 1 to 3 mm particle size are used,
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
Freshwater
not
required
toxicity is
unlikely
- Calcium carbide is unlikely to have direct toxic
effects on aquatic organisms.
No exposure is expected because of the rapid decay of Ca-carbide when coming in contact with
55
water.
Marine water
not
required
toxicity is
unlikely
- Calcium carbide is unlikely to have direct toxic
effects on aquatic organisms.
No exposure is expected because of the rapid
decay of Ca-carbide when coming in contact with
water.
Sediment
qualitative
toxicity is
unlikely
- Calcium carbide is unlikely to have direct toxic
effects on aquatic organisms.
No exposure is expected because of the rapid
decay of Ca-carbide when coming in contact with
water.
Aquatic freshwater
food chain
not
required
toxicity is
unlikely
- Calcium carbide does not have potential to
bioaccumulate.
Aquatic marine water
food chain
not
required
toxicity is
unlikely
- Calcium carbide does not have potential to
bioaccumulate.
10.5.3.3 Terrestrial compartment (including secondary poisoning)
Risk characterisation for the terrestrial compartment
Compartments PEC PNEC PEC/PNEC Discussion
Agricultural soil
qualitative
toxicity is
unlikely
- It is unlikely that Ca-carbide could have toxic
effects to terrestrial organisms.
No exposure is expected because of the rapid
decay of Ca-carbide when coming in contact with
water or humidity.
Grassland
qualitative
toxicity is
unlikely
- It is unlikely that Ca-carbide could have toxic
effects to terrestrial organisms.
No exposure is expected because of the rapid
decay of Ca-carbide when coming in contact with
water or humidity.
Terrestrial food
chain
not required
toxicity is
unlikely
- Calcium carbide does not have potential to
bioaccumulate, and, therefore, secondary
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
STP
not required
toxicity is
unlikely
- No exposure is expected because of the rapid
decay of Ca-carbide when coming in contact with
water.
56
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.
‐ . ‐