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)

mailto:%[email protected]



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

Safety Data Sheet acc. to Regulation (EC) No. 1907/2006 (REACH)

Calcium carbide


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 (respiratory 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.





Calcium carbide


SECTION 3: Composition/information on ingredients

3.1 Substances

Name of substance Calcium carbide

Identifiers

REACH Reg. No 01-2119494719-18-0000

CAS No 75-20-7

EC No 200-848-3

Index No 006-004-00-9

SECTION 4: First aid measures

4.1 Description of first aid measures

General notes

Do not leave affected person unattended. Remove victim out of the danger area. Keep affected person warm, still and covered. Take off immediately all contaminated clothing. In all cases of doubt, or when symptoms persist, seek medical advice. In case of unconsciousness place person in the recovery position. Never give anything by mouth.

Following inhalation

Provide fresh air. In all cases of doubt, or when symptoms persist, seek medical advice. If breathing is irregular or stopped, immediately seek medical assistance and start first aid actions. In case of respiratory tract irritation, consult a physician.

Following skin contact

Brush off loose particles from skin. Rinse skin with water/shower. Wash with plenty of soap and water. If skin irritation or rash occurs: Get medical advice/attention.

Following eye contact

Irrigate copiously with clean, fresh water for at least 10 minutes, holding the eyelids apart. Remove contact lenses, if present and easy to do. Continue rinsing. Call a physician immediately.

Following ingestion

Do NOT induce vomiting. Call a physician immediately.

4.2 Most important symptoms and effects, both acute and delayed

Symptoms and effects are not known to date.

4.3 Indication of any immediate medical attention and special treatment needed

none

SECTION 5: Firefighting measures

5.1 Extinguishing media

Suitable extinguishing media

D-Powder, Dry sand

Unsuitable extinguishing media

Water jet, Foam, Carbon dioxide (CO2)

5.2 Special hazards arising from the substance or mixture

On contact with water highly flammable and explosive acetylene is generated.

Hazardous combustion products

Carbon monoxide (CO), Carbon dioxide (CO2)

5.3 Advice for firefighters

In case of fire and/or explosion do not breathe fumes. Co-ordinate firefighting measures to the fire surroundings. Do not allow firefighting water to enter drains or water courses. Collect contaminated firefighting water separately. Fight fire with normal precautions from a reasonable distance.

Special protective equipment for firefighters

Chemical protective clothing, Wear self-contained breathing apparatus





Calcium carbide


SECTION 6: Accidental release measures

6.1 Personal precautions, protective equipment and emergency procedures

For non-emergency personnel

Remove persons to safety. Provision of sufficient ventilation. Wearing of suitable protective equipment (including personal protective equipment referred to under Section 8 of the safety data sheet) to prevent any contamination of skin, eyes and personal clothing. Removal of ignition sources.

For emergency responders

Wear breathing apparatus if exposed to vapours/dust/spray/gases.

6.2 Environmental precautions

Keep away from drains, surface and ground water. Retain contaminated washing water and dispose of it.

6.3 Methods and material for containment and cleaning up

Advices on how to contain a spill

Covering of drains, Take up mechanically

Advices on how to clean up a spill

Take up mechanically.

Other information relating to spills and releases

Place in appropriate containers for disposal. Ventilate affected area.

6.4 Reference to other sections

Hazardous combustion products: see section 5. Personal protective equipment: see section 8. Incompatible materials: see section 10. Disposal considerations: see section 13.

SECTION 7: Handling and storage

7.1 Precautions for safe handling

Recommendations

- Measures to prevent fire as well as aerosol and dust generation

Keep container tightly closed. Use local and general ventilation. Take precautionary measures against static discharge. Use only in well-ventilated areas.

- Specific notes/details

Dust deposits may accumulate on all deposition surfaces in a technical room.

- Handling of incompatible substances or mixtures

- Keep away from

Acids, Water, Store separately from oxidising and spontaneously flammable substances.

Advice on general occupational hygiene

Take off immediately all contaminated clothing. Wash hands after use. Do not eat, drink and smoke in work areas. Remove contaminated clothing and protective equipment before entering eating areas. Never keep food or drink in the vicinity of chemicals. Never place chemicals in containers that are normally used for food or drink. Keep away from food, drink and animal feedingstuffs. Do not breathe gas/vapour/spray. Avoid contact with skin and eyes.

7.2 Conditions for safe storage, including any incompatibilities

Managing of associated risks

- Explosive atmospheres

Removal of dust deposits.

- Incompatible substances or mixtures

Do not allow contact with water.

- Do not mix with

Acids, Caustic solutions, Alcohols, Water

- Evaporative conditions

Keep container tightly closed and in a well-ventilated place.





Calcium carbide


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 period

(unless otherwise specified) TWA time-weighted average (long-term exposure limit): measured or calculated in relation to a reference period of 8 hours time-

weighted average (unless otherwise specified)

8.2 Exposure controls

Appropriate engineering controls

General ventilation.

Individual protection measures (personal protective equipment)

Eye/face protection

Use safety goggle with side protection.

Skin protection

- Hand protection

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

- Type of material

NBR: acrylonitrile-butadiene rubber

- Other protection measures

Take recovery periods for skin regeneration. Preventive skin protection (barrier creams/ointments) is recommended. Wash hands thoroughly after handling.

Respiratory protection

In case of dust formation: respiratory protection. Particulate filter device (EN 143).





Calcium carbide


Environmental exposure controls

Use appropriate container to avoid environmental contamination. Keep away from drains, surface and ground water.

SECTION 9: Physical and chemical properties

9.1 Information on basic physical and chemical properties Appearance

Physical state solid

Colour dark grey

Odour characteristic

Other safety parameters

pH (value) not applicable

Melting point/freezing point 2,160 °C

Initial boiling point and boiling range 2,300 °C

Flash point not applicable

Evaporation rate not determined

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

Explosion limits of dust clouds not determined

Vapour pressure not determined

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


SECTION 10: Stability and reactivity




Calcium carbide


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.





Calcium carbide


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


12.3 Mobility in soil


12.4 Results of PBT and vPvB assessment


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.





Calcium carbide


SECTION 14: Transport information

14.1 UN number 1402

14.2 UN proper shipping name CALCIUM CARBIDE

14.3 Transport hazard class(es)

Class 4.3 (substances which, in contact with water, emit flammable

gases)

14.4 Packing group I (substance presenting high danger)

14.5 Environmental hazards non-environmentally hazardous acc. to the dangerous goods regulations

14.6 Special precautions for user

Provisions for dangerous goods (ADR) should be complied within the premises.

14.7 Transport in bulk according to Annex II of MARPOL and the IBC Code

The cargo is not intended to be carried in bulk.

Information for each of the UN Model Regulations

Transport of dangerous goods by road, rail and inland waterway (ADR/RID/ADN)

UN number 1402

Proper shipping name CALCIUM CARBIDE

- Particulars in the transport document UN1402, CALCIUM CARBIDE, 4.3, I,

(B/E) Class 4.3

Classification code W2

Packing group I

Danger label(s) 4.3

Excepted quantities (EQ) E0

Limited quantities (LQ) 0

Transport category (TC) 1

Tunnel restriction code (TRC) B/E

Hazard identification No X423

Emergency Action Code 4W

International Maritime Dangerous Goods Code (IMDG)

UN number 1402

Proper shipping name CALCIUM CARBIDE

- Particulars in the shipper's declaration UN1402, CALCIUM CARBIDE, 4.3, I

Class 4.3

Marine pollutant -

Packing group I

Danger label(s) 4.3

Special provisions (SP) 951


Limited quantities (LQ) 0

EmS F-G, S-N

Stowage category B





Calcium carbide


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


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 classification 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.




Legend


Calcium carbide


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 application 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




National inventories


Calcium carbide


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.





Calcium carbide


SECTION 16: Other information

Indication of changes (revised safety data sheet)

Section Former entry (text/value) Actual entry (text/value) Safety- relevant

1.1 Alternative name(s): Calcium acetylide

yes

5.2 Special hazards arising from the substance or mixture:

Product may release hydrogen gas. Increased storage temperatures will accelerate this process. 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 explosive 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

http://www.nationalarchives.gov.uk/doc/open-government-li-


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


SU 10 (end-use) PC 20 PROC 5, 8b -

ES 3 Confidential


SU 8 (end-use) PC 19 PROC 2, 8b N/A

ES 4 Confidential


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


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


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


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


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 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]


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 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





Total of fractions 100 [%]




Concentration in effluent exceeds solubility No




AIR



Total deposition flux during emission episode 0.011 [mg.m-2.d-1]


WATER, SEDIMENT






SOIL, GROUNDWATER






LOCAL PECS [PRODUCTION] Value Unit

AIR


WATER, SEDIMENT





13





SOIL, GROUNDWATER







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


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.




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).



Used amount of substance per day 150 tonnes/day Assumption used in the exposure assessment


>4 hours Information provided by members of the calcium carbide consortium


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


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


See text.


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


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


Standard environment assumed.


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


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


Containment and local exhaust ventilation

Containment plus good work practice required

No measured data

Local exhaust ventilation required plus good work practise


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







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.


Routes of exposure

Estimated exposure

concentrations

Measured exposure

concentrations


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


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)




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


There is no oral exposure of humans via the environment.




Guidance Chapter R16. Default model parameters have been used.

Local tonnage – 150 tonnes per day

Number of days – 200 days.


19


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.


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



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



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




20










AIR





WATER, SEDIMENT






SOIL, GROUNDWATER






LOCAL PECS [INDUSTRIAL USE] Value Unit

AIR


WATER, SEDIMENT









SOIL, GROUNDWATER





21



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













AIR





WATER, SEDIMENT






SOIL, GROUNDWATER






LOCAL PECS [INDUSTRIAL USE] Value Unit

AIR


WATER, SEDIMENT





22





SOIL, GROUNDWATER










23

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



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.


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.



Used amount of substance per day 10.08 tonnes From EIGA (2008)


1-4 hours Information from industry


Once Information from industry

Annual amount used per site 2520 tonnes From EIGA (2008)

Emission days per site 250 From EIGA (2008)


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.


24

Table 9.23. Characteristics of the substance or preparation

Information type

Data field

Explanation

Physical state solid


Medium for acetylene production; high for calcium cyanamide production.


Calcium carbide granules are used for the acetylene production


exposed humans

See Table 9.4.


Standard environmental characteristics are appropriate for this scenario.


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.


See Table 9.5.

25


Wastes are recycled into the processes.







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.


Routes of exposure

Estimated Exposure

Concentrations

Measured exposure

concentrations


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)



26

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



(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)


0.007 ECETOC TRA model prediction for PROC 2 (acetylene)


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.


None expected.







Guidance Chapter R16. Default model parameters have been used.

Local tonnage – 10.08 tonnes per day

Number of days – 250 days.


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.


exposure estimation. These are summarised in Table 9.26.



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.


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


AIR





SOIL, GROUNDWATER






LOCAL PECS [ACETYLENE PRODUCTION] Value Unit

AIR


SOIL, GROUNDWATER







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


AIR





SOIL, GROUNDWATER






LOCAL PECS [ACETYLENE PRODUCTION] Value Unit

AIR


SOIL, GROUNDWATER










9.4 ES 4: Use of calcium carbide in metallurgy


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)


This exposure scenario is valid for professionals and consumers.


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.


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


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)

-



Granules of 1 to 3 mm diameters are used.


exposed humans

Default data as in CHESAR are used.


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


Technical fate of substance and losses from process, waste water and air


Fraction consumed in process/use 100 %


Risk management measures for wide dispersive use



Gloves

- Gloves are recommended but, based on experience, are not required.


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.




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



granular form.

- - -

32

Summary of acute exposure concentrations to workers



(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.


The same data as for acute exposure are applied, as the relevant toxic effects are the local irritating

effects.


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.


An indirect exposure of man via the environment can be excluded, as the substance rapidly decays

in contact with water or humidity.

33



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


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


9.5.2.4.4 Exposure concentration in sediments


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

-





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


9.5.2.4.6 Atmospheric compartment




9.5.2.5 Regional exposure concentrations

Not relevant, as no local exposure is expected.

35

9.6 Carbide welding (ES6)


This exposure scenario is valid for professionals and consumers.


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.




characteristics


Information type

Data field

Explanation





-



-





exposed humans



Used amount of substance (as such or in preparation) per worker or consumer per day

ca. 1 kg/d

Typical data.


<1 h/day

Duration of the filling procedure, afterwards the container in the device is closed.

Frequency of exposure 1 /day to 1 /month



36









Gloves




Information type

Data field

Explanation

Amount of substances in waste resulting from identified uses covered in the exposure scenario

0 kg/y


during the process.





Routes of exposure

Estimated

Exposure

Concentrations

Measured exposure

concentrations



Dermal exposure

0.1 mg/c m2



granular form.

- - -

Inhalation exposure

0.06 mg/m 3



granular form.

- - -

37




(in mg/cm2)

< 0.1mg/cm2






not relevant


with water.

Inhalation exposure

(in mg/m3)


air.



effects.








38





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




0 0 see above







Compartments

Predicted

releases (kg/d)

Measured release


Aquatic (without

STP)

0

-





-

Aquatic (after

STP)

0

-





Air (direct +

STP)

0 -



Soil (direct only)

0

-


39









40

9.7 Calcium carbide in humidity analyzers (ES7)


This exposure scenario is valid for professionals.


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.




characteristics


Information type

Data field

Explanation





-



-





exposed humans



Used amount of substance (as such) per worker per day

ca. 0.1 kg/d

Typical data.


<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



41









Gloves




Information type

Data field

Explanation

Amount of substances in waste

resulting from identified uses covered in the exposure scenario

0 kg/y


during the process. Residual amounts are reacted with water.





Routes of exposure

Estimated

Exposure

Concentrations

Measured exposure

concentrations



Dermal exposure

0.1 mg/c m2



granular form and welded in glass tubes.

- - -

Inhalation exposure

0.06 mg/m 3



granular form and welded in glass tubes.

- - -

42




(in mg/cm2)

< 0.1mg/cm2






not relevant


with water.

Inhalation exposure

(in mg/m3)


air.



effects.








43





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




0 0 see above







Compartments

Predicted

releases (kg/d)

Measured release


Aquatic (without

STP)

0

-





-

Aquatic (after

STP)

0

-





Air (direct +

STP)

0 -



Soil (direct only)

0

-


44









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


SOIL

RCR for the local soil compartment 3.82E-02


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 marine compartment 0.5

SEDIMENT



RCR for the local marine sediment compartment 0.5


SOIL

RCR for the local soil compartment <<0.99


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


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


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




SEDIMENT





SOIL



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




SEDIMENT





SOIL

RCR for the local soil compartment <<1.2E-02


STP


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


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


for cyanamide, which are summarised in Table 10.5 below.


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


RCR for the local marine compartment 0

SEDIMENT

RCR for the local fresh-water sediment compartment 0


RCR for the local marine sediment compartment 0


SOIL



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.


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


RCR for the local marine compartment 0

SEDIMENT

RCR for the local fresh-water sediment compartment 0


RCR for the local marine sediment compartment 0


SOIL

RCR for the local soil compartment <<2.6E-04


STP


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


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,


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


water.

Inhalation qualitative N/A No systemic but only local effects, if any, are


water.

Combined

routes

qualitative N/A No systemic but only local effects, if any, are


water.

Long-term –

local effects

Dermal 0.1 mg/cm2 irritation Granules of 1 to 3 mm particle size are used,


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.


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



No exposure is expected because of the rapid

decay of Ca-carbide when coming in contact with

water.

Sediment

qualitative

toxicity is

unlikely





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


bioaccumulate.

10.5.3.3 Terrestrial compartment (including secondary poisoning)

Risk characterisation for the terrestrial compartment


Agricultural soil

qualitative

toxicity is

unlikely

- It is unlikely that Ca-carbide could have toxic

effects to terrestrial organisms.



water or humidity.

Grassland

qualitative

toxicity is

unlikely

- It is unlikely that Ca-carbide could have toxic

effects to terrestrial organisms.



water or humidity.

Terrestrial food

chain

not required

toxicity is

unlikely


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


STP

not required

toxicity is

unlikely

- No exposure is expected because of the rapid


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.

‐ . ‐

safety data sheet: calcium carbide - radtke messtechnik€¦ · calcium carbide revision: 2018 -09...

Documents