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HAFNIUM COMPOUNDS

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Classification   |    Detailed evidence-based information

Substances Included Synonyms

Therapeutic Toxic Class

    A) Hafnium is a metallic element found in the earth's crust with an abundance of 5 parts per million. It is found in all zirconium-containing metals, and has valences of 2, 3, and 4. There are six naturally-occurring isotopes and a variety of artificial isotopes. Hafnium resembles the metals zirconium and thorium. Hafnium is used in control rods for water-cooled nuclear reactors, in electric light bulb filaments, in electrodes, in glasses for special applications, and in vacuum tube anode elements. Processes that separate hafnium and zirconium may use or generate hafnium oxychloride and hafnium tetrachloride. An aquasol of hafnium dioxide has been used to study non-radiation effects of Thorotrast.
    B) While one minor isotope of hafnium is an alpha particle emitter, it accounts for only 0.163% of the naturally occurring isotopes. This review regards only non-radiation effects of hafnium exposure.

Specific Substances

    1) Hafnium
    2) Celtium
    3) Hafnium metal, powder, dry
    4) Hafnium metal, powder, wet
    5) Hafnium powder, wetted with not less than 25% water
    6) Hafnium, dry
    7) Hafnium, wet
    1.2.1) MOLECULAR FORMULA
    1) Hf

Available Forms Sources

    A) FORMS
    1) Hafnium is a grey, hard, ductile metal, with a shiny or brilliant silver-like luster: It occurs as hexagonal crystals or powder (Budavari, 1989; Sax & Lewis, 1989; Proctor et al, 1988; ACGIH, 1986).
    2) There are six naturally-occurring isotopes and a variety of artificial isotopes. While one minor isotope of hafnium is an alpha particle emitter, it accounts for only 0.163% of the naturally occurring isotopes (Budavari, 1989).
    3) Hafnium resembles both thorium and zirconium. Hafnium and zirconium are more closely identical in chemical properties than are any other pair in the periodic table (Budavari, 1989; HSDB , 1992).
    B) SOURCES
    1) Hafnium is found in the earth's crust with an abundance of 5 parts per million. It is found in all zirconium-containing metals (Budavari, 1989).
    a) Processes that separate hafnium and zirconium may use or generate hafnium oxychloride and hafnium tetrachloride (ACGIH, 1986).
    C) USES
    1) Hafnium is used in control rods for water-cooled nuclear reactors, in electric light bulb filaments, in electrodes, in glasses for special applications, and in vacuum tube anode elements (ACGIH, 1986; Sax & Lewis, 1987).

Overview

Life Support

    A) This overview assumes that basic life support measures have been instituted.

Clinical Effects

    0.2.1) SUMMARY OF EXPOSURE
    A) No human health hazards other than fire and explosion injuries have been reported from industrial hafnium metal exposure. Hafnium salts are irritants of eyes and skin. Experimental animals have sustained liver injury from hafnium exposure.
    0.2.4) HEENT
    A) Eye irritation may be seen.
    0.2.9) HEPATIC
    A) Mild hepatic injury has been described in experimental animals with chronic exposure.
    0.2.14) DERMATOLOGIC
    A) Irritation of unabraded skin occurs with direct contact.
    0.2.20) REPRODUCTIVE
    A) At the time of this review, no data were available to assess the potential effects of exposure to this agent during pregnancy or lactation.

Laboratory Monitoring

    A) Patients with significant exposure should have liver function tests monitored.

Treatment Overview

    0.4.2) ORAL/PARENTERAL EXPOSURE
    A) GASTRIC LAVAGE: Consider after ingestion of a potentially life-threatening amount of poison if it can be performed soon after ingestion (generally within 1 hour). Protect airway by placement in the head down left lateral decubitus position or by endotracheal intubation. Control any seizures first.
    1) CONTRAINDICATIONS: Loss of airway protective reflexes or decreased level of consciousness in unintubated patients; following ingestion of corrosives; hydrocarbons (high aspiration potential); patients at risk of hemorrhage or gastrointestinal perforation; and trivial or non-toxic ingestion.
    B) ACTIVATED CHARCOAL: Administer charcoal as a slurry (240 mL water/30 g charcoal). Usual dose: 25 to 100 g in adults/adolescents, 25 to 50 g in children (1 to 12 years), and 1 g/kg in infants less than 1 year old.
    0.4.3) INHALATION EXPOSURE
    A) INHALATION: Move patient to fresh air. Monitor for respiratory distress. If cough or difficulty breathing develops, evaluate for respiratory tract irritation, bronchitis, or pneumonitis. Administer oxygen and assist ventilation as required. Treat bronchospasm with an inhaled beta2-adrenergic agonist. Consider systemic corticosteroids in patients with significant bronchospasm.
    B) Administer 100% humidified supplemental oxygen with assisted ventilation as required if respiratory tract irritation is present.
    0.4.4) EYE EXPOSURE
    A) DECONTAMINATION: Remove contact lenses and irrigate exposed eyes with copious amounts of room temperature 0.9% saline or water for at least 15 minutes. If irritation, pain, swelling, lacrimation, or photophobia persist after 15 minutes of irrigation, the patient should be seen in a healthcare facility.
    0.4.5) DERMAL EXPOSURE
    A) OVERVIEW
    1) DECONTAMINATION: Remove contaminated clothing and jewelry and place them in plastic bags. Wash exposed areas with soap and water for 10 to 15 minutes with gentle sponging to avoid skin breakdown. A physician may need to examine the area if irritation or pain persists (Burgess et al, 1999).

Range Of Toxicity

    A) The maximum tolerated and minimum lethal human exposures have not been delineated.

Clinical Effects

Summary Of Exposure

    A) No human health hazards other than fire and explosion injuries have been reported from industrial hafnium metal exposure. Hafnium salts are irritants of eyes and skin. Experimental animals have sustained liver injury from hafnium exposure.

Heent

    3.4.1) SUMMARY
    A) Eye irritation may be seen.
    3.4.3) EYES
    A) CONJUNCTIVITIS - Direct eye contact with hafnium salts produces conjunctival irritation without corneal injury (Grant, 1986; Proctor & Hughes, 1978).

Hepatic

    3.9.1) SUMMARY
    A) Mild hepatic injury has been described in experimental animals with chronic exposure.
    3.9.2) CLINICAL EFFECTS
    A) LIVER DAMAGE
    1) Experimental animals chronically fed hafnium developed mild liver injury with coarse granulation of hepatocyte cytoplasm, and perinuclear vacuolization of parenchymal cells (Proctor & Hughes, 1978; ACGIH, 1986). These effects have not been reported in humans exposed to hafnium.

Dermatologic

    3.14.1) SUMMARY
    A) Irritation of unabraded skin occurs with direct contact.
    3.14.2) CLINICAL EFFECTS
    A) DERMATITIS
    1) Hafnium salts are mild irritants of unabraded skin, producing transient erythema and edema (Proctor & Hughes, 1978).

Reproductive

    3.20.1) SUMMARY
    A) At the time of this review, no data were available to assess the potential effects of exposure to this agent during pregnancy or lactation.
    3.20.2) TERATOGENICITY
    A) LACK OF INFORMATION
    1) At the time of this review, no data were available to assess the teratogenic potential of hafnium or its salts.
    3.20.3) EFFECTS IN PREGNANCY
    A) LACK OF INFORMATION
    1) At the time of this review, no data were available to assess the potential effects of exposure to hafnium or its salts during pregnancy or lactation.

Carcinogenicity

    3.21.1) IARC CATEGORY
    A) IARC Carcinogenicity Ratings for CAS7440-58-6 (International Agency for Research on Cancer (IARC), 2016; International Agency for Research on Cancer, 2015; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010a; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2008; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2007; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2006; IARC, 2004):
    1) Not Listed
    3.21.3) HUMAN STUDIES
    A) LACK OF INFORMATION
    1) At the time of this review, no data were available to assess the carcinogenic potential of hafnium or its salts.

Laboratory Monitoring

Monitoring Parameters Levels

    4.1.1) SUMMARY
    A) Patients with significant exposure should have liver function tests monitored.
    4.1.2) SERUM/BLOOD
    A) OTHER: Monitor liver function tests in patients with significant exposure to hafnium metal or its salts.

Treatment

Life Support

    A) Support respiratory and cardiovascular function.

Monitoring

    A) Patients with significant exposure should have liver function tests monitored.

Oral Exposure

    6.5.2) PREVENTION OF ABSORPTION
    A) GASTRIC LAVAGE
    1) INDICATIONS: Consider gastric lavage with a large-bore orogastric tube (ADULT: 36 to 40 French or 30 English gauge tube {external diameter 12 to 13.3 mm}; CHILD: 24 to 28 French {diameter 7.8 to 9.3 mm}) after a potentially life threatening ingestion if it can be performed soon after ingestion (generally within 60 minutes).
    a) Consider lavage more than 60 minutes after ingestion of sustained-release formulations and substances known to form bezoars or concretions.
    2) PRECAUTIONS:
    a) SEIZURE CONTROL: Is mandatory prior to gastric lavage.
    b) AIRWAY PROTECTION: Place patients in the head down left lateral decubitus position, with suction available. Patients with depressed mental status should be intubated with a cuffed endotracheal tube prior to lavage.
    3) LAVAGE FLUID:
    a) Use small aliquots of liquid. Lavage with 200 to 300 milliliters warm tap water (preferably 38 degrees Celsius) or saline per wash (in older children or adults) and 10 milliliters/kilogram body weight of normal saline in young children(Vale et al, 2004) and repeat until lavage return is clear.
    b) The volume of lavage return should approximate amount of fluid given to avoid fluid-electrolyte imbalance.
    c) CAUTION: Water should be avoided in young children because of the risk of electrolyte imbalance and water intoxication. Warm fluids avoid the risk of hypothermia in very young children and the elderly.
    4) COMPLICATIONS:
    a) Complications of gastric lavage have included: aspiration pneumonia, hypoxia, hypercapnia, mechanical injury to the throat, esophagus, or stomach, fluid and electrolyte imbalance (Vale, 1997). Combative patients may be at greater risk for complications (Caravati et al, 2001).
    b) Gastric lavage can cause significant morbidity; it should NOT be performed routinely in all poisoned patients (Vale, 1997).
    5) CONTRAINDICATIONS:
    a) Loss of airway protective reflexes or decreased level of consciousness if patient is not intubated, following ingestion of corrosive substances, hydrocarbons (high aspiration potential), patients at risk of hemorrhage or gastrointestinal perforation, or trivial or non-toxic ingestion.
    B) ACTIVATED CHARCOAL
    1) CHARCOAL ADMINISTRATION
    a) Consider administration of activated charcoal after a potentially toxic ingestion (Chyka et al, 2005). Administer charcoal as an aqueous slurry; most effective when administered within one hour of ingestion.
    2) CHARCOAL DOSE
    a) Use a minimum of 240 milliliters of water per 30 grams charcoal (FDA, 1985). Optimum dose not established; usual dose is 25 to 100 grams in adults and adolescents; 25 to 50 grams in children aged 1 to 12 years (or 0.5 to 1 gram/kilogram body weight) ; and 0.5 to 1 gram/kilogram in infants up to 1 year old (Chyka et al, 2005).
    1) Routine use of a cathartic with activated charcoal is NOT recommended as there is no evidence that cathartics reduce drug absorption and cathartics are known to cause adverse effects such as nausea, vomiting, abdominal cramps, electrolyte imbalances and occasionally hypotension (None Listed, 2004).
    b) ADVERSE EFFECTS/CONTRAINDICATIONS
    1) Complications: emesis, aspiration (Chyka et al, 2005). Aspiration may be complicated by acute respiratory failure, ARDS, bronchiolitis obliterans or chronic lung disease (Golej et al, 2001; Graff et al, 2002; Pollack et al, 1981; Harris & Filandrinos, 1993; Elliot et al, 1989; Rau et al, 1988; Golej et al, 2001; Graff et al, 2002). Refer to the ACTIVATED CHARCOAL/TREATMENT management for further information.
    2) Contraindications: unprotected airway (increases risk/severity of aspiration) , nonfunctioning gastrointestinal tract, uncontrolled vomiting, and ingestion of most hydrocarbons (Chyka et al, 2005).
    6.5.3) TREATMENT
    A) MONITORING OF PATIENT
    1) Monitor liver function tests in significant exposures. Should hepatic failure occur, supportive therapy should be provided.

Inhalation Exposure

    6.7.1) DECONTAMINATION
    A) Move patient from the toxic environment to fresh air. Monitor for respiratory distress. If cough or difficulty in breathing develops, evaluate for hypoxia, respiratory tract irritation, bronchitis, or pneumonitis.
    B) OBSERVATION: Carefully observe patients with inhalation exposure for the development of any systemic signs or symptoms and administer symptomatic treatment as necessary.
    C) INITIAL TREATMENT: Administer 100% humidified supplemental oxygen, perform endotracheal intubation and provide assisted ventilation as required. Administer inhaled beta-2 adrenergic agonists, if bronchospasm develops. Consider systemic corticosteroids in patients with significant bronchospasm (National Heart,Lung,and Blood Institute, 2007). Exposed skin and eyes should be flushed with copious amounts of water.
    6.7.2) TREATMENT
    A) IRRITATION SYMPTOM
    1) While respiratory tract irritation has not been described in humans exposed to hafnium dust, patients with such complaints should be moved to fresh air and administered 100% humidified supplemental oxygen with assisted ventilation as required.
    B) Treatment should include recommendations listed in the ORAL EXPOSURE section when appropriate.

Eye Exposure

    6.8.1) DECONTAMINATION
    A) EYE IRRIGATION, ROUTINE: Remove contact lenses and irrigate exposed eyes with copious amounts of room temperature 0.9% saline or water for at least 15 minutes. If irritation, pain, swelling, lacrimation, or photophobia persist after 15 minutes of irrigation, an ophthalmologic examination should be performed (Peate, 2007; Naradzay & Barish, 2006).

Dermal Exposure

    6.9.1) DECONTAMINATION
    A) DERMAL DECONTAMINATION
    1) DECONTAMINATION: Remove contaminated clothing and wash exposed area thoroughly with soap and water for 10 to 15 minutes. A physician may need to examine the area if irritation or pain persists (Burgess et al, 1999).
    6.9.2) TREATMENT
    A) IRRITATION SYMPTOM
    1) Dermal irritation from hafnium exposure should be treated with standard topical measures.
    B) Treatment should include recommendations listed in the ORAL EXPOSURE section when appropriate.

Enhanced Elimination

    A) EFFICACY
    1) No studies have addressed the use of extracorporeal elimination techniques in hafnium poisoning.

Range Of Toxicity

Summary

    A) The maximum tolerated and minimum lethal human exposures have not been delineated.

Minimum Lethal Exposure

    A) GENERAL/SUMMARY
    1) The minimum lethal human dose to this agent has not been delineated.
    B) ANIMAL DATA
    1) Hafnium chloride was fatal to cats in doses of 10 milligrams per kilogram (Proctor et al, 1988).

Maximum Tolerated Exposure

    A) GENERAL/SUMMARY
    1) The maximum tolerated human exposure to this agent has not been delineated.
    2) No systemic human toxicity from hafnium dust has been described (Proctor et al, 1988).
    B) ANIMAL DATA
    1) Rats fed a 1% hafnium-containing diet developed hepatotoxicity; some rats developed hepatotoxicity with a 90-day feeding of a 0.1% hafnium diet (ACGIH, 1986; Proctor et al, 1988).
    2) After estimating uptakes by various routes, it has been calculated that 0.7% hafnium per cubic meter of air corresponds to a borderline response rat dietary level of 0.01% (ACGIH, 1986).
    3) The application of 1 milligram of hafnium chloride to the eyes of rabbits produced transient irritation (Proctor et al, 1988).

Workplace Standards

    A) ACGIH TLV Values for CAS7440-58-6 (American Conference of Governmental Industrial Hygienists, 2010):
    1) Editor's Note: The listed values are recommendations or guidelines developed by ACGIH(R) to assist in the control of health hazards. They should only be used, interpreted and applied by individuals trained in industrial hygiene. Before applying these values, it is imperative to read the introduction to each section in the current TLVs(R) and BEI(R) Book and become familiar with the constraints and limitations to their use. Always consult the Documentation of the TLVs(R) and BEIs(R) before applying these recommendations and guidelines.
    a) Adopted Value
    1) Hafnium and compounds, as Hf
    a) TLV:
    1) TLV-TWA: 0.5 mg/m(3)
    2) TLV-STEL:
    3) TLV-Ceiling:
    b) Notations and Endnotes:
    1) Carcinogenicity Category: Not Listed
    2) Codes: Not Listed
    3) Definitions: Not Listed
    c) TLV Basis - Critical Effect(s): URT and eye irr; liver dam
    d) Molecular Weight: 178.49
    1) For gases and vapors, to convert the TLV from ppm to mg/m(3):
    a) [(TLV in ppm)(gram molecular weight of substance)]/24.45
    2) For gases and vapors, to convert the TLV from mg/m(3) to ppm:
    a) [(TLV in mg/m(3))(24.45)]/gram molecular weight of substance
    e) Additional information:

    B) NIOSH REL and IDLH Values for CAS7440-58-6 (National Institute for Occupational Safety and Health, 2007):
    1) Listed as: Hafnium and compounds (as Hf)
    2) REL:
    a) TWA: 0.5 mg/m(3)
    b) STEL:
    c) Ceiling:
    d) Carcinogen Listing: (Not Listed) Not Listed
    e) Skin Designation: Not Listed
    f) Note(s): [*Note: The REL and PEL also applies to other hafnium compounds (as Hf).]
    3) IDLH:
    a) IDLH: 50 mg Hf/m3
    b) Note(s): Not Listed

    C) Carcinogenicity Ratings for CAS7440-58-6 :
    1) ACGIH (American Conference of Governmental Industrial Hygienists, 2010): Not Listed ; Listed as: Hafnium and compounds, as Hf
    2) EPA (U.S. Environmental Protection Agency, 2011): Not Listed
    3) IARC (International Agency for Research on Cancer (IARC), 2016; International Agency for Research on Cancer, 2015; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010a; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2008; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2007; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2006; IARC, 2004): Not Listed
    4) NIOSH (National Institute for Occupational Safety and Health, 2007): Not Listed ; Listed as: Hafnium and compounds (as Hf)
    5) MAK (DFG, 2002): Not Listed
    6) NTP (U.S. Department of Health and Human Services, Public Health Service, National Toxicology Project ): Not Listed

    D) OSHA PEL Values for CAS7440-58-6 (U.S. Occupational Safety, and Health Administration (OSHA), 2010):
    1) Listed as: Hafnium
    2) Table Z-1 for Hafnium:
    a) 8-hour TWA:
    1) ppm:
    a) Parts of vapor or gas per million parts of contaminated air by volume at 25 degrees C and 760 torr.
    2) mg/m3: 0.5
    a) Milligrams of substances per cubic meter of air. When entry is in this column only, the value is exact; when listed with a ppm entry, it is approximate.
    3) Ceiling Value:
    4) Skin Designation: No
    5) Notation(s): Not Listed

Toxicity Information

    7.7.1) TOXICITY VALUES

Pharmacology Toxicology

Toxicologic Mechanism

    A) Hafnium and its salts are direct irritants of the conjunctiva and skin (Proctor & Hughes, 1978).
    B) The mechanism of hafnium hepatotoxicity in experimental animals has not been determined.

Physicochemical

Physical Characteristics

    A) Hafnium is a grey, hard, shiny or brilliant silvery-lustrous metal occurring as cubic crystals or powder (ITI, 1985; Proctor & Hughes, 1978; ACGIH, 1986). Hafnium is both malleable and ductile and has properties similar to those of thorium and zirconium (ITI, 1985; Proctor & Hughes, 1978).

Ph

    1) No information found at the time of this review.

Molecular Weight

    A) 178.49 (Budavari, 1989)

References

General Bibliography

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