Chromium

Incident management

Key Points

Fire  (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

CHROMIUM – INCIDENT MANAGEMENT

Hazard Identification

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

UN 1439 Ammonium dichromate Use coarse water spray. Wear normal fire clothing in combination with breathing apparatus*. Spillages and EAC 1Y decontamination run-off should be prevented from entering drains and watercourses. Danger that the substance can be violently or explosively reactive.

APP -

Class 5.1 Oxidising substance Hazards

Sub - risks HIN 50 Oxidising (fire-intensifying) effect

UN 1463 Chromium trioxide (anhydrous) Use coarse water spray. Wear liquid-tight chemical protective suit in combination with breathing apparatus**. Spillages and EAC 1W decontamination run-off should be prevented from entering drains and watercourses. Danger that the substance can be violently or explosively reactive.

APP -

Class 5.1 Oxidising substance

Hazards

Sub 6.1 Toxic substance risks

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

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8 Corrosive substance

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

UN 1755 solution Use fine water spray. Wear liquid-tight chemical protective 2X suit in combination with breathing apparatus**. Spillages and EAC decontamination run-off should be prevented from entering drains and watercourses.

APP -

Class 8 Corrosive substance Hazards

Sub - risks HIN 80 Corrosive or slightly corrosive substance

UN 2720 Chromium (III) nitrate Use coarse water spray. Wear normal fire clothing in 1Z combination with breathing apparatus*. Spillages and EAC decontamination run-off should be prevented from entering drains and watercourses.

APP -

Class 5.1 Oxidising substance Hazards

Sub - risks HIN 50 Oxidizing (fire-intensifying) effect UN – United Nations number; EAC – Emergency Action Code; APP – Additional Personal Protection; HIN - Hazard Identification Number

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* 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).

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Chemical Hazard Information and Packaging for Supply Classification(a)

Chromium (VI) compounds, with the exception of chromate

Carc. Cat. 2 Category 2

Classification

N Dangerous for the Environment

R49 May cause cancer by inhalation

Risk phrases R43 May cause sensitisation by skin contact Very toxic to aquatic organisms, and may cause long-term R50/53 adverse effects in the aquatic environment S53 Avoid exposure. Obtain special instructions before use In case of accident or if you feel unwell seek medical advice S45 immediately (show the label where possible) Safety phrases This material and its container must be disposed of as S60 hazardous waste Avoid release to the environment. Refer to special S61 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)

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Chromium (VI) trioxide

O Oxidising

Carc. Cat. Category 1 carcinogen 1

Muta. Cat. Category 2 mutagen 2

Repr. Cat. Category 3 reproductive toxin 3 Classification

T+ Very toxic

T Toxic

C Corrosive

N Dangerous for the Environment

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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 Risk phrases May cause sensitisation by inhalation, may cause R42/43 sensitisation by skin contact Toxic by inhalation, danger of serious damage to health by R48/23 prolonged exposure R62 Possible risk of impaired fertility Very toxic to aquatic organisms, and may cause long-term R50/53 adverse effects in the aquatic environment S53 Avoid exposure. Obtain special instructions before use In case of accident or if you feel unwell seek medical advice S45 immediately (show the label where possible) Safety phrases This material and its container must be disposed of as S60 hazardous waste Avoid release to the environment. Refer to special S61 instructions/safety data sheet

Specific concentration limits

Concentration Classification C ≥ 10% C; R35 5 % ≤ C < 10 % C; R34 1 % ≤ C < 5 % Xi; R36/37/38

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

O Oxidising

Carc. Cat. Category 2 carcinogen 2 Classification

C Corrosive

N Dangerous for the Environment

R45 May cause cancer R8 Contact with combustible material may cause fire

Risk phrases R35 Causes severe burns R43 May cause sensitisation by skin contact Very toxic to aquatic organisms, and may cause long-term R50/53 adverse effects in the aquatic environment S53 Avoid exposure. Obtain special instructions before use In case of accident or if you feel unwell seek medical advice S45 immediately (show the label where possible) Safety phrases This material and its container must be disposed of as S60 hazardous waste Avoid release to the environment. Refer to special S61 instructions/safety data sheet

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Globally Harmonised System of Classification and Labelling of Chemicals (GHS)(a)

Chromium (VI) compounds, with the exception of barium chromate

Carc. 1B Carcinogenicity, category 1B

Skin Sens. 1 Skin Sensitizer

Hazard Class and Category

Aquatic Acute hazard to the aquatic environment, Acute 1 category 1

Aquatic Chronic hazard to the aquatic Chronic 1 environment, category 1

H350i May cause cancer by inhalation

Hazard H317 May cause an allergic skin reaction Statement 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)

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Chromium (VI) trioxide

Ox. Sol. 1 Oxidising , category 1

Carc. 1A Carcinogenicity, category 1A

Muta. 1B Germ cell mutagenicity, category 1B

Hazard Class Repr. 2 Toxic to reproduction, category 2 and Category

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

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

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

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Skin Corr. Skin , category 1A 1A

Resp. Sens. Respiratory sensitizer, category 1 1

Skin Sens. 1 Skin sensitizer, category 1

Aquatic Acute hazard to the aquatic environment, Acute 1 category 1

Aquatic Chronic hazard to the aquatic Chronic 1 environment, category 1

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 Hazard Statement H301 Toxic if swallowed Causes damage to organs through prolonged or repeated H372 exposure H314 Causes severe skin burns and eye damage May cause allergy or asthma symptoms or breathing H334 difficulties if inhaled H317 May cause an allergic skin reaction H400 Very toxic to aquatic life

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H410 Very toxic to aquatic life with long lasting effects

Signal Words DANGER

Specific concentration limits

Hazard Class Concentration Hazard Statement and Category 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

Hazard Class Skin Corr. Skin corrosion, category 1A and Category 1A

Skin Sens. 1 Skin sensitiser, category 1

Aquatic Acute hazard to the aquatic environment, Acute 1 category 1

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Aquatic Chronic hazard to the aquatic Chronic 1 environment, category 1

H271 May cause fire or explosion; strong oxidiser H350 May cause cancer

Hazard H314 Causes severe skin burns and eye damage Statement 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

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Physicochemical Properties

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 7.14 (elemental chromium) (air=1)

Non-combustible, with the exception of ammonium dichromate, which is flammable and chromate/dichromate and Flammability 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

Chromic (III) is insoluble in water, acids and alkalis. Elemental chromium is insoluble in water, but soluble in acids Water (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.

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

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

Odourless (elemental chromium, chromates and chromic Odour compounds) 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.

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Threshold Toxicity Values

EXPOSURE VIA INHALATION / INGESTION ppm mg m-3 SIGNS AND SYMPTOMS

- - Data not available

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Published Emergency Response Guidelines

Emergency Response Planning Guideline (ERPG) Values

Listed value Calculated value

(ppm) (mg m-3) ERPG-1* ERPG-2** Data not available 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† AEGL-2†† Data not available 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.

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Exposure Standards, Guidelines or Regulations

Occupational standards

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

(a) WEL 0.05 mg m-3 (0.024 ppm) Cr (VI) compounds (as http://www.hse.gov.uk/ Cr)

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

Public health guidelines

DRINKING WATER QUALITY GUIDELINE AND

REGULATIONS (b,c) 50 µg L-1 as Cr http://dwi.defra.gov.uk/ http://www.who.int/en/

AIR QUALITY GUIDELINE(d) 1 µg Cr (VI) m-3 equates to an estimated lifetime http://www.who.int/en/ risk of 4 × 10-2

SOIL GUIDELINE VALUE No guideline values specified

Tolerable Daily Intakeoral 3 µg kg bw-1 day-1 (for Cr VI)

(e) HEALTH CRITERIA VALUES Mean Daily Intakeoral http://www.environment-agency.gov.uk/ 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.

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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.

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

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. 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: , 2011. b TOXBASE: Chromium metal and chromium salts, 2004 c TOXBASE: Chromates and dichromates, features and management, 2011

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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 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.

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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.

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