Chromium Incident management v2 - gov.uk...Incident management: Page 7 of 21 CHROMIUM – INCIDENT MANAGEMENT Risk phrases R45 May cause cancer R46 May cause heritable genetic damage

Chromium

Incident management

Key Points Fire

Chromium (VI) compounds: Flammable or may cause fire on contact with combustible material

Powerful oxidisers. Reacts with reducing agents to form chromium (III) Chromium (III) compounds: Some chromate and chromium (III) compounds emit toxic

fumes when heated

Health Chromium (VI) compounds: Highly toxic by inhalation, ingestion and skin contact Ingestion may cause abdominal pain, haematemesis and bloody diarrhoea with

circulatory collapse, and delayed onset of renal failure (12-24 hours after exposure), thrombocytopaenia and anaemia (after 3-7 days), liver failure, convulsions, coma and necrosis of the GI tract mucosal surfaces

Inhalation may cause irritation of the respiratory tract, cough, chest pain, chronic rhinitis, laryngitis, pharyngitis, lesions of the nasal mucosa and nasal septum perforation. Bronchial asthma and pulmonary oedema may occur up to 72 hours after exposure

Dermal exposure may result in irritation and burns Ocular exposure causes pain, blepharospasm, lacrimation, conjunctivitis, palpebral

oedema and photophobic Chromium (III) compounds: Low absorption, and relatively low toxicity Inhalation may cause pulmonary fibrosis and bronchial asthma Ocular exposure may cause a stinging and burning sensation with lacrimation

Environment

Dangerous for the Environment Inform Environment Agency of substantial release incidents

CRCE HQ, HPA 03/2012

Version 2

Incident management: Page 2 of 21

CHROMIUM – INCIDENT MANAGEMENT

Hazard Identification Standard (UK) Dangerous Goods Emergency Action Codes(a)

UN 1439 Ammonium dichromate

EAC 1Y

Use coarse water spray. Wear normal fire clothing in combination with breathing apparatus*. Spillages and decontamination run-off should be prevented from entering drains and watercourses. Danger that the substance can be violently or explosively reactive.

APP -

Hazards Class 5.1 Oxidising substance

Sub risks

-

HIN 50 Oxidising (fire-intensifying) effect

UN 1463 Chromium trioxide (anhydrous)

EAC 1W

Use coarse water spray. Wear liquid-tight chemical protective suit in combination with breathing apparatus**. Spillages and decontamination run-off should be prevented from entering drains and watercourses. Danger that the substance can be violently or explosively reactive.

APP -

Hazards

Class 5.1 Oxidising substance

Sub risks

6.1 Toxic substance

a Dangerous Goods Emergency Action Code List 2011. National Chemical Emergency Centre (NCEC). The Stationary Office, London.



8 Corrosive substance

HIN 568 Oxidising (fire-intensifying), toxic, corrosive

UN 1755 Chromic acid solution

EAC 2X

Use fine water spray. Wear liquid-tight chemical protective suit in combination with breathing apparatus**. Spillages and decontamination run-off should be prevented from entering drains and watercourses.

APP -

Hazards Class 8 Corrosive substance

Sub risks

-

HIN 80 Corrosive or slightly corrosive substance

UN 2720 Chromium (III) nitrate

EAC 1Z

Use coarse water spray. Wear normal fire clothing in combination with breathing apparatus*. Spillages and decontamination run-off should be prevented from entering drains and watercourses.

APP -

Hazards Class 5.1 Oxidising substance

Sub risks

-

HIN 50 Oxidizing (fire-intensifying) effect

UN – United Nations number; EAC – Emergency Action Code; APP – Additional Personal Protection; HIN - Hazard Identification Number



* Normal fire fighting clothing i.e. fire kit (BS EN 469), gloves (BS EN 659) and boots (HO specification A29 and A30) in addition to self-contained open circuit positive pressure compressed air breathing apparatus (BS EN 137). ** Liquid-tight chemical protective clothing (BS 8428 or EN 14605) in combination with self-contained open circuit positive pressure compressed air breathing apparatus (BS EN 137).



Chemical Hazard Information and Packaging for Supply Classification(a) Chromium (VI) compounds, with the exception of barium chromate

Classification

Carc. Cat. 2 Category 2 carcinogen

N Dangerous for the Environment

Risk phrases

R49 May cause cancer by inhalation

R43 May cause sensitisation by skin contact

R50/53 Very toxic to aquatic organisms, and may cause long-term adverse effects in the aquatic environment

Safety phrases

S53 Avoid exposure. Obtain special instructions before use

S45 In case of accident or if you feel unwell seek medical advice immediately (show the label where possible)

S60 This material and its container must be disposed of as hazardous waste

S61 Avoid release to the environment. Refer to special instructions/safety data sheet

a Annex VI to Regulation (EC) No 1272/2008 on Classification, Labelling and Packaging of Substances and Mixtures- Table 3.2. http://esis.jrc.ec.europa.eu/index.php?PGM=cla (accessed 03/2012)



Chromium (VI) trioxide

Classification

O Oxidising

Carc. Cat. 1

Category 1 carcinogen

Muta. Cat. 2

Category 2 mutagen

Repr. Cat. 3

Category 3 reproductive toxin

T+ Very toxic

T Toxic

C Corrosive




Risk phrases

R45 May cause cancer

R46 May cause heritable genetic damage

R9 Explosive when mixed with combustible material

R24/25 Toxic in contact with skin, toxic if swallowed

R26 Very toxic by inhalation

R35 Causes severe burns

R42/43 May cause sensitisation by inhalation, may cause sensitisation by skin contact

R48/23 Toxic by inhalation, danger of serious damage to health by prolonged exposure

R62 Possible risk of impaired fertility


Safety phrases





Specific concentration limits

Concentration Classification

C ≥ 10% C; R35

5 % ≤ C < 10 % C; R34

1 % ≤ C < 5 % Xi; R36/37/38



Dichromium tris(chromate); chromium III chromate; chromic chromate

Classification

O Oxidising

Carc. Cat. 2

Category 2 carcinogen

C Corrosive


Risk phrases

R45 May cause cancer

R8 Contact with combustible material may cause fire

R35 Causes severe burns

R43 May cause sensitisation by skin contact


Safety phrases







Globally Harmonised System of Classification and Labelling of Chemicals (GHS)(a) Chromium (VI) compounds, with the exception of barium chromate

Hazard Class and Category

Carc. 1B Carcinogenicity, category 1B

Skin Sens. 1 Skin Sensitizer

Aquatic Acute 1

Acute hazard to the aquatic environment, category 1

Aquatic Chronic 1

Chronic hazard to the aquatic environment, category 1

Hazard Statement

H350i May cause cancer by inhalation

H317 May cause an allergic skin reaction

H400 Very toxic to aquatic life

H410 Very toxic to aquatic life with long lasting effects

Signal Words DANGER

a Annex VI to Regulation (EC) No 1272/2008 on Classification, Labelling and Packaging of Substances and Mixtures- Table 3.1. http://esis.jrc.ec.europa.eu/index.php?PGM=cla (accessed 03/2012)



Chromium (VI) trioxide


Ox. Sol. 1 Oxidising solid, category 1

Carc. 1A Carcinogenicity, category 1A

Muta. 1B Germ cell mutagenicity, category 1B

Repr. 2 Toxic to reproduction, category 2

Acute Tox. 2 Acute toxicity (inhalation), category 2

Acute Tox. 3 Acute toxicity (oral, dermal), category 3

STOT RE 1 Specific target organ systemic toxicity following repeated exposure, category 1



Skin Corr. 1A

Skin corrosion, category 1A

Resp. Sens. 1

Respiratory sensitizer, category 1

Skin Sens. 1 Skin sensitizer, category 1

Aquatic Acute 1


Aquatic Chronic 1


Hazard Statement

H271 May cause fire or explosion; strong oxidiser

H350 May cause cancer

H340 May cause genetic defects

H361f Suspected of damaging fertility

H330 Fatal if inhaled

H311 Toxic in contact with skin

H301 Toxic if swallowed

H372 Causes damage to organs through prolonged or repeated exposure

H314 Causes severe skin burns and eye damage

H334 May cause allergy or asthma symptoms or breathing difficulties if inhaled






Signal Words DANGER

Specific concentration limits

Concentration Hazard Class and Category

Hazard Statement

C ≥ 1 % STOT SE 3 H335 May cause respiratory irritation

Dichromium tris(chromate); chromium III chromate; chromic chromate


Ox. Sol. 1 Oxidizing solid, category 1

Carc. 1B Carcinogenicity, category 1B

Skin Corr. 1A

Skin corrosion, category 1A

Skin Sens. 1 Skin sensitiser, category 1

Aquatic Acute 1




Aquatic Chronic 1


Hazard Statement

H271 May cause fire or explosion; strong oxidiser

H350 May cause cancer

H314 Causes severe skin burns and eye damage




Signal Words DANGER



Physicochemical Properties

References(a,b)

a HSDB: Hazardous Substances Data Bank. National Library of Medicine, Bethesda, Maryland (electronic version), RightAnswer.com, Inc., Midland, MI, USA, Available at: http://www.RightAnswerKnowledge.com (accessed 01/2012). b The Merck Index (14th Edition). Entry 2231: Chromium, 2006.

CAS number 7440-47-3

Atomic weight 52

Chemical symbol Cr

Common synonyms -

State at room temperature Solid

Volatility Non-volatile at 20°C

Vapour density 7.14 (elemental chromium) (air=1)

Flammability

Non-combustible, with the exception of ammonium dichromate, which is flammable and potassium chromate/dichromate and chromium trioxide which pose a fire risk on contact with organic/combustible material

Lower explosive limit Data not available

Upper explosive limit Data not available

Water solubility

Chromic (III) oxide is insoluble in water, acids and alkalis. Elemental chromium is insoluble in water, but soluble in acids (except nitric) and strong alkalis. Chromate and chromic (III) salts are generally soluble in water. Chromium (III) sulphate is practically insoluble in water and acid.

Reactivity

Chromate (VI) salts are powerful oxidisers. Chromium (VI) compounds react with reducing agents to form chromium (III). Chromate compounds are potentially explosive in combination with certain compounds e.g. sodium and potassium dichromate react explosively with hydrazine.

Reaction or degradation products

Sodium/potassium chromate/dichromate emits toxic fumes of sodium/potassium oxide on heating to decomposition. Chromium (III) sulphate decomposes to chromic acid when heated. Lead chromate emits highly toxic lead-containing fumes when heated.

Odour Odourless (elemental chromium, chromates and chromic compounds)



Threshold Toxicity Values

EXPOSURE VIA INHALATION / INGESTION

ppm mg m-3 SIGNS AND SYMPTOMS

- - Data not available



Published Emergency Response Guidelines Emergency Response Planning Guideline (ERPG) Values

Listed value

(ppm) Calculated value

(mg m-3) ERPG-1*

Data not available ERPG-2** ERPG-3***

* Maximum airborne concentration below which it is believed that nearly all individuals could be exposed for up to 1 hr without experiencing other than mild transient adverse health effects or perceiving a clearly defined, objectionable odour. ** Maximum airborne concentration below which it is believed that nearly all individuals could be exposed for up to 1 hr without experiencing or developing irreversible or other serious health effects or symptoms which could impair an individual's ability to take protective action. *** Maximum airborne concentration below which it is believed that nearly all individuals could be exposed for up to 1 hr without experiencing or developing life-threatening health effects. Acute Exposure Guideline Levels (AEGLs) mg m-3 10 min 30 min 60 min 4 hr 8 hr AEGL-1†

Data not available AEGL-2†† AEGL-3††† † The level of the chemical in air at or above which the general population could experience notable discomfort. †† The level of the chemical in air at or above which there may be irreversible or other serious long-lasting effects or impaired ability to escape. ††† The level of the chemical in air at or above which the general population could experience life-threatening health effects or death.



Exposure Standards, Guidelines or Regulations Occupational standards

WEL(a)

http://www.hse.gov.uk/

LTEL (8 hour reference period): 0.5 mg m-3 (0.24 ppm) Cr, Cr (II) and (III) compounds (as Cr), 0.05 mg m-3 (0.024 ppm) Cr (VI) compounds (as Cr)

STEL (15 min reference period): No guideline value specified

Public health guidelines DRINKING WATER QUALITY GUIDELINE AND REGULATIONS (b,c) http://dwi.defra.gov.uk/ http://www.who.int/en/

50 µg L-1 as Cr

AIR QUALITY GUIDELINE(d) http://www.who.int/en/

1 µg Cr (VI) m-3 equates to an estimated lifetime risk of 4 × 10-2

SOIL GUIDELINE VALUE No guideline values specified

HEALTH CRITERIA VALUES(e)

http://www.environment-agency.gov.uk/

Tolerable Daily Intakeoral

3 µg kg bw-1 day-1 (for Cr VI)

Mean Daily Intakeoral

13 µg day-1

Index dose inhalation

0.001 µg kg bw-1 day-1

WEL – Workplace exposure limit; LTEL - Long-term exposure limit; STEL – Short-term exposure limit

a EH40/2005 Workplace Exposure Limits (second edition, published 2011). http://www.hse.gov.uk/pubns/priced/eh40.pdf (accessed 01/2012) b The Water Supply (Water Quality) Regulations 2000 (England) and the Water Supply (Water Quality Regulations 2001 (Wales). c Guidelines for Drinking-Water Quality, Fourth Edition. WHO, Geneva. 2011. d Air Quality Guidelines for Europe. World Health Organization Regional Office for Europe, Copenhagen WHO Regional Publications, European Series, No. 91, Second Edition, 2000. e Department for Environment, Food and Rural Affairs (DEFRA).Contaminants in soil: Collation of Toxicological Data and Intake Values for Humans. Chromium. 2002.



Health Effects

Major route of exposure(a,b)

Chromium (VI) trioxide, chromates and dichromates are highly toxic by inhalation, ingestion, skin and eye exposure.

Chromium (III) salts are considered to have relatively low toxicity compared to chromates and dichromates, due to low absorption.

Immediate signs or symptoms of acute exposure(b-c) (c,d,e,f)

Chromium (VI) Initial signs of ingestion reflect corrosive damage to the gastrointestinal tract and

include nausea and vomiting, abdominal pain, haematemesis, bloody diarrhoea and circulatory collapse.

Acute kidney failure due to severe renal tubular necrosis may occur 12-24 hours after exposure. Hepatic dysfunction with prolonged INR and intravascular haemolysis may ensue and pulmonary oedema, convulsions, coma and encephalopathy may develop. Methaemoglobinaemia and pancreatitis have been reported.

Inhalation of chromium dust or mist can result in irritation of the respiratory tract, cough, chest pain, chronic rhinitis, laryngitis, pharyngitis,. Bronchial asthma and pulmonary oedema may occur up to 72 hours after exposure.

Dermal exposure may result in irritation, ulceration and burns. Systemic toxicity has occurred following partial thickness burns. Hexavalent chromium is a recognised cause of allergic contact (type IV) dermatitis.

Ocular exposure may result in pain, blepharospasm, lacrimation, conjunctivitis, palpebral oedema and photophobia.

Chromium (III) Inhalation can result in pulmonary fibrosis and bronchial asthma. Ocular exposure may be irritating to the eyes.

TOXBASE - http://www.toxbase.org (accessed 01/2012) a TOXBASE: Sodium chromate, 2011. b TOXBASE: Chromium metal and chromium salts, 2004 c TOXBASE: Chromates and dichromates, features and management, 2011



Decontamination and First Aid Important Notes

Ambulance staff, paramedics and emergency department staff treating chemically-contaminated casualties should be equipped with the Department of Health approved, gas-tight (Respirex) decontamination suits based on EN466:1995, EN12941:1998 and prEN943-1:2001, where appropriate.

Decontamination should be performed using local protocols in designated areas such as a decontamination cubicle with adequate ventilation.

Dermal exposure(a)

Remove patient from exposure. The patient should remove all clothing and personal effects. Double-bag soiled clothing and place in a sealed container clearly labelled as a

chemical hazard. Brush away any adherent solid particles from the patient. Wash hair and all contaminated skin with copious amounts of water (preferably warm)

and soap for at least 10-15 minutes. Decontaminate open wounds first and avoid contamination of unexposed skin.

Pay special attention to skin folds, axillae, ears, fingernails, genital areas and feet. Treat burns as thermal burns. Early aggressive excision of exposed skin is advocated in cases of severe burns to

decrease the systemic absorption.

Substantial disruption of the dermal barrier may allow systemic chromium uptake.

See ingestion for management of systemic uptake.

Other measures as indicated by the patient's clinical condition.

Ocular exposure

Remove patient from exposure. Remove contact lenses if present and immediately irrigate the affected eye

thoroughly with water or 0.9% saline for at least 10-15 minutes. Continue until the conjunctival sac pH is normal (7.5 - 8.0), retest after 20 minutes and use further irrigation if necessary.

Patients with corneal damage or those whose symptoms do not resolve rapidly should be referred for urgent ophthalmological assessment.

Inhalation

Remove patient from exposure. Ensure a clear airway and adequate ventilation. Give oxygen to symptomatic patients. Apply other supportive measures as indicated by the patient’s clinical condition.

TOXBASE - http://www.toxbase.org (accessed 01/2012) a TOXBASE: Chromates and dichromates, features and management, 2011.



Ingestion(a)

Maintain a clear airway and adequate ventilation. Gut decontamination is contraindicated.

Monitor pulse and blood pressure and urine output. Monitor patients for at least 12 hours after suspected ingestion. Apply other supportive measures as indicated by the patient’s clinical condition.

This document from the HPA Centre for Radiation, Chemical and Environmental Hazards reflects understanding and evaluation of the current scientific evidence as presented and referenced in this document.

TOXBASE - http://www.toxbase.org (accessed 01/2012) a TOXBASE: Chromates and dichromates, features and management, 2011.



Documents

Chromium Incident management v2 - gov.uk...Incident management: Page 7 of 21 CHROMIUM – INCIDENT MANAGEMENT Risk phrases R45 May cause cancer R46 May cause heritable genetic damage