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    IPCS INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY
    Health and Safety Guide No. 42

    VANADIUM and some vanadium salts
    HEALTH AND SAFETY GUIDE






    UNITED NATIONS ENVIRONMENT PROGRAMME

    INTERNATIONAL LABOUR ORGANISATION

    WORLD HEALTH ORGANIZATION




    WORLD HEALTH ORGANIZATION, GENEVA 1990

    This is a companion volume to Environmental Health Criteria 81:
    Vanadium

    Published by the World Health Organization for the International
    Programme on Chemical Safety (a collaborative programme of the United
    Nations Environment Programme, the International Labour Organisation,
    and the World Health Organization)

    This report contains the collective views of an international group of
    experts and does not necessarily represent the decisions or the stated
    policy of the United Nations Environment Programme, the International
    Labour Organisation, or the World Health Organization

    WHO Library Cataloguing in Publication Data

    Vanadium and some vanadium salts : health and safety guide.

    (Health and safety guide ; no. 42)

    1. Vanadium - standards  I. Series

    ISBN 92 4 151042 0          (NLM Classification: QV 290)
    ISSN 0259-7268

    (c) World Health Organization 1990

    Publications of the World Health Organization enjoy copyright
    protection in accordance with the provisions of Protocol 2 of the
    Universal Copyright Convention.  For rights of reproduction or
    translation of WHO publications, in part or  in toto, application
    should be made to the Office of Publications, World Health
    Organization, Geneva, Switzerland.  The World Health Organization
    welcomes such applications.

    The designations employed and the presentation of the material in this
    publication do not imply the expression of any opinion whatsoever on
    the part of the Secretariat of the World Health Organization
    concerning the legal status of any country, territory, city or area or
    of its authorities, or concerning the delimitation of its frontiers or
    boundaries.

    The mention of specific companies or of certain manufacturers'
    products does not imply that they are endorsed or recommended by the
    World Health Organization in preference to others of a similar nature
    that are not mentioned.  Errors and omissions excepted, the names of
    proprietary products are distinguished by initial capital letters.

    CONTENTS

    INTRODUCTION

    1. PRODUCT IDENTITY AND USES
         1.1. Identity
         1.2. Physical and chemical properties
         1.3. Analytical methods
              1.3.1. Atomic absorption analysis
              1.3.2. Spectrophotometric analysis
              1.3.3. Neutron activation analysis
              1.3.4. Electrochemical analysis
         1.4. Production and uses

    2. SUMMARY AND EVALUATION
         2.1. Human exposure
         2.2. Uptake, metabolism, and excretion
         2.3. Effects on organisms in the environment
         2.4. Effects on experimental animals and in vitro test systems
         2.5. Effects on human beings

    3. CONCLUSIONS AND RECOMMENDATIONS

    4. HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY ACTION
         4.1. Main human health hazards, prevention and protection, first
              aid
              4.1.1. Advice to physicians
                     4.1.1.1  Symptoms of poisoning
                     4.1.1.2  Medical advice
              4.1.2. Health surveillance advice
         4.2. Explosion and fire hazards
              4.2.1. Prevention
              4.2.2. Fire extinguishing agents
         4.3. Storage
         4.4. Transport
         4.5. Spillage and disposal
              4.5.1. Spillage
              4.5.2. Disposal

    5. HAZARDS FOR THE ENVIRONMENT AND THEIR PREVENTION

    6. SUMMARY OF CHEMICAL SAFETY INFORMATION

    7. CURRENT REGULATIONS, GUIDELINES, AND STANDARDS
         7.1. Exposure limit values
         7.2. Specific restrictions
         7.3. Labelling, packaging, and transport

    BIBLIOGRAPHY
    

    INTRODUCTION

    The Environmental Health Criteria (EHC) documents produced by the
    International Programme on Chemical Safety include an assessment of
    the effects on the environment and on human health of exposure to a
    chemical or combination of chemicals, or physical or biological
    agents.  They also provide guidelines for setting exposure limits.

    The purpose of a Health and Safety Guide is to facilitate the
    application of these guidelines in national chemical safety
    programmes. The first three sections of a Health and Safety Guide
    highlight the relevant technical information in the corresponding EHC. 
    Section 4 includes advice on preventive and protective measures and
    emergency action; health workers should be thoroughly  familiar with
    the medical information to ensure that they can act efficiently in an
    emergency.  Within the Guide is a Summary of Chemical Safety
    Information which should be readily available, and should be clearly
    explained, to all who could come into contact with the chemical.  The
    section on regulatory information has been extracted from the legal
    file of the International Register of Potentially Toxic Chemicals
    (IRPTC) and from other United Nations sources.

    The target readership includes occupational health services, those in
    ministries, governmental agencies, industry, and trade unions who are
    involved in the safe use of chemicals and the avoidance of
    environmental health hazards, and those wanting more information on
    this topic.  An attempt has been made to use only terms that will be
    familiar to the intended user.  However, sections 1 and 2 inevitably
    contain some technical terms.  A bibliography has been included for
    readers who require further background information.

    Revision of the information in this Guide will take place in due
    course, and the eventual aim is to use standardized terminology. 
    Comments on any difficulties encountered in using the Guide would be
    very helpful and should be addressed to:

    The Manager
    International Programme on Chemical Safety
    Division of Environmental Health
    World Health Organization
    1211 Geneva 27
    Switzerland

    THE INFORMATION IN THIS GUIDE SHOULD BE CONSIDERED AS A STARTING POINT
    TO A COMPREHENSIVE HEALTH AND SAFETY PROGRAMME

    1.  PRODUCT IDENTITY AND USES

    1.1 Identity


    Chemical    Name and synonyms          CAS No.       RTECS No.
    formula
                                                                         

    V           vanadium                   7440-62-2     YW1355000
    V2O5        vanadium pentoxide         1314-62-1     YW2450000 (dust)
                                                         YW2460000 (fume)
    V2O3        vanadium trioxide          1314-36-7     YW3050000
    NaVO3       sodium metavanadate        13718-26-8    YW1010000
    VCl4        vanadium tetrachloride     7632-51-1     YW2625000
    VCl3O       vanadium oxychloride       7727-18-6     YW2975000
                vanadium oxytrichloride
                vanadyl chloride
                vanadium trichlorooxo
    (NH4)3VO4   ammonium vanadate          11115-676     BT5140000
                ammonium vanadium
                  oxide
                vanadium monosulfide
                vanadium sulfide
                                                                         

     Chemical structure: 

    Vanadium pentoxide (V2O5): the structure depends on whether it is
    in a solid form or in solution;  if in solution, the structure depends
    on pH and other factors.  High relative molecular mass polymeric forms
    are common.

    Vanadium trioxide:        O = V - O - V = O


    Sodium metavanadate:      Na - O - V
                                     /  \
                                    O  -  O


    Vanadium tetrachloride:         Cl
                                     '
                                Cl - V - Cl
                                     '
                                    Cl


    Vanadium oxychloride:           Cl
                                     '
                                Cl - V = O
                                     '
                                    Cl


    Ammonium vanadate                O - NH4
                                     '
                           NH4 - O - V = O
                                     '
                                     O - NH4


    Vanadium monosulfide             V = S


    1.2  Physical and Chemical Properties

    Vanadium (V) is a greyish metal that occurs in two natural stable
    isotopes, 50V and 51V. It forms oxidation states -1, 0, +2, +3, +4
    (most stable), and +5. Vanadium pentoxide (V2O5) is the most
    common commercial form. It dissolves in water to form acidic solutions
    and dissolves in acids. It reacts with bases to form vanadates.
    Vanadium trioxide (V2O3) is basic in solution and dissolves in
    acids to give the green hexa-aquo ion (V(H2O)6)+++.  In
    solution, V+++ is a strong reducing agent and slowly attacks water
    with the production of hydrogen.

         2V+++ + 2H2O = 2V++++ + 2OH- + H2.

    Because of its numerous oxidation states, vanadium forms a great
    number of compounds.  Most of the organic vanadium compounds are
    unstable. Metallic vanadium reacts with oxygen, nitrogen, and carbon
    at relatively low temperatures (<300C). Vanadium is most commonly
    available as vanadium pentoxide and as ferrovanadium (an iron-vanadium
    alloy containing 40-80% vanadium by weight).  Some physical and
    chemical properties of vanadium and of some of its compounds are given
    in the Summary of Chemical Safety Information (section 6).

    1.3  Analytical Methods

    Atomic absorption and spectrophotometric assays are the most suitable
    methods for routine analysis.  Neutron activation analysis can be used
    for the determination of vanadium in serum and blood.

    1.3.1  Atomic absorption analysis

    The use of a high temperature nitrous oxide/acetylene flame improves
    the sensitivity of atomic absorption analysis.  Increased sensitivity
    can also be achieved using flameless electrothermal AAS assays with a
    graphite furnace (detection limits between 0.1 and 0.6 g vanadium). 
    Vanadium in air can be measured using direct current plasma atomic
    emission spectrometry (DCP-AES)  (vanadium detection limit of
    4.0 g/m3; practical working range 0.01-100mg/litre).

    Atomic absorption is widely used for the determination of vanadium in
    biological materials and in other media, such as crude petroleum
    (detection limit of 30 pg;  sensitivity of 65 pg with flameless
    apparatus and graphite tubes).

    1.3.2  Spectrophotometric analysis

    Emission spectral analysis is a selective method by which small
    amounts of vanadium can be determined in the presence of numerous
    other elements (relative sensitivity of 10-3-10-5%).  Sensitivity
    can be increased by prior separation of the vanadium to be determined. 
    Inductively coupled plasma optical emission spectrometry can be used
    for the simultaneous determination of several elements in aerosol
    samples collected with cascade impactors, and for the determination of
    vanadium in urine.

    Spark-source mass spectrometry is a sensitive method (sensitivity
    10-11-10-12g;  relative sensitivity 10-7 g-atom).  This method
    can be used for measuring vanadium in air and biological materials. 
    However, for biological materials, the ash must be completely free of
    organic mixtures to prevent vanadium binding.

    Organic reagents can be used to improve the specificity of
    spetrophotometric analysis.  The specificity of the organic reagents
    can be increased by the use of complexing agents to bind interfering
    ions.  Specificity and sensitivity are enhanced by prior separation of
    vanadium, usually by extraction.

    Spectrophotometric analysis, based on catalytic reactions, such as
    acceleration of the oxidation of aromatic amines and aminophenols with
    chlorates, bromates, periodates, and persulfates in the presence of
    pentavalent vanadium compounds, can be used to determine trace amounts
    of vanadium.

    1.3.3  Neutron activation analysis

    Neutron activation analysis is a rapid and accurate method
    (sensitivity 10-12g in air).  It can be used to determine vanadium
    in air, serum, and body tissues.

    Neutron activation determination of vanadium in biological material is
    interfered with by sodium and this must be eliminated before
    irradiation, normally by absorption on antimony pentoxide.

    1.3.4  Electrochemical analysis

    Vanadium can be determined electrochemically by volumetric titration
    with electrometric detection (potentiometry, amperometry), as well as
    by coulometric titrations, polarography, and coulometry.  Catalytic
    reactions with polarographic, potentiometric, or amperometric
    detection are also used.

    Stripping voltammetry and other modifications of polarography and
    electrometric methods based on catalytic reactions are highly
    sensitive, but are subject to interference.  Controlled potential
    coulometry is highly selective, making the separate determination of
    vanadium compounds of different valencies possible.  The introduction
    of differential techniques into both coulometric titration and
    controlled potential coulometry improves accuracy.

    1.4  Production and Uses

    Annual world production of vanadium is in the region of 45 million kg
    (V2O5 equivalent).  About 70% of the world production comes from
    South Africa and the USSR.  Some 85% of the world production is used
    in Europe, Japan, and the USA.  Three quarters of all vanadium
    produced is used in the metallurgical industry for the production of
    special steels. It is added as ferro-vanadium or vanadium carbide to a
    final concentration of up to 5%. Non-ferrous vanadium alloys are used
    in the nuclear and aerospace industries. Vanadium pentoxide and
    vanadates are used as catalysts in the production of sulfuric acid, in
    the oxidation of organic compounds, in petroleum cracking, and in
    catalytic converters for the exhaust gases of internal combustion
    engines. Vanadium compounds are used in glass, in glazes and enamels
    for porcelain and pottery, in lacquers and paints, as mordants in the
    dyeing of fabrics, and in photographic chemicals, luminescent
    chemicals, thermistors and cathode-ray tubes. They are also used as
    synthetic rubber additives and vanadium slags are used in the foundry
    to improve the quality of casting surfaces and to facilitate cleaning.

    2.  SUMMARY AND EVALUATION

    2.1  Human Exposure

    Vanadium is widely distributed in the earth's crust (around
    0.05 g/kg). Vanadium from all sources is ultimately deposited on soils
    or surface waters.  There is little migration of vanadium in soils,
    except via uptake by living organisms and redeposition. Vanadium tends
    to be trapped by, and move with, trivalent iron. Most vanadium in
    surface waters is suspended and becomes incorporated in sedimentary
    deposits in oceans.  Levels in surface waters range up to
    0.2 mg/litre, and those in airborne particulates from 0.1 to
    1.0 ng/m3 air (in the absence of industrial pollution).  Air levels
    of vanadium in industrial areas where high-vanadium fossil fuels are
    burnt may range up to 64 ng/m3, and air in the region of vanadium
    plants may contain 2 g vanadium/m3.  Water discharged from
    metallurgical plants may contain hundreds of mg vanadium/litre.

    Dietary intake of vanadium is generally in the range of 10-30 g/day. 
    In the USA, most drinking-water samples contained less than
    10 g/litre.

    Occupational exposure to vanadium in user and producer industries is
    variable.  Generally, exposure limits are measured and expressed as
    V2O5.  Most countries have occupational exposure limits of 0.05 or
    0.1 mg/m3 work-place air. However, concentrations of vanadium in air
    (measured as V2O5) may reach 10-100 mg/m3 in boiler-cleaning
    operations and 0.5-5 mg/m3 in catalyst production.  In many
    industrial operations, V2O5 is produced as a fume (condensation
    aerosol) consisting of small, respirable particles with a potential
    for over-exposure through inhalation.

    Occupational and other exposure limit values are given in the tables
    in section 7.

    2.2  Uptake, Metabolism, and Excretion

    Inhaled vanadium compounds persist in, and are absorbed from, the
    lungs to different extents, depending on their solubility.  Absorbed
    vanadium is distributed to all organs. Only a small amount (0.1-2%) of
    ingested vanadium is absorbed and most of this is excreted in the
    urine.  Dermal absorption of vanadium is not significant.

    Vanadium is detectable in most human organs at less than 1 g/kg wet
    weight.  The lungs contain 19-140 g/kg wet weight and blood serum,
    about 30 g/litre (most recent estimates). The distribution of
    vanadium after intravenous injection of vanadium compounds of
    different oxidation states (VOCl3, VOCl2, VCl3) was similar.

    Because of low intestinal absorption, most ingested vanadium is
    eliminated in the faeces. The urine is the principal means of
    eliminating absorbed vanadium compounds. There is evidence that
    urinary concentrations are about 12-13% of dietary concentrations. 
    Urinary vanadium concentrations are generally higher in those most
    heavily exposed, though correlations with measured exposure levels are
    poor. Urinary vanadium levels reflect both recent and past vanadium
    exposure. Vanadium in tissues, such as bone, is released slowly.

    2.3  Effects on Organisms in the Environment

    The growth of some aquatic plants is stimulated by trace quantities of
    vanadium (1-10 g/litre), but concentrations above 100 g/litre are
    toxic.  Some marine invertebrates, such as the tunicates, accumulate
    vanadium levels of up to 0.3% dry weight.  Invertebrates are generally
    less sensitive to vanadium (9-day LC50 values in the range
    10-65 mg/litre) than fish (4-6 day LC50 values in the range
    0.5-22 mg/litre).  The pH is an important modulator of vanadium
    toxicity.  Vanadium in soils at concentrations of 10 mg/kg or more is
    toxic for terrestrial plants.

    2.4  Effects on Experimental Animals and In Vitro Test Systems

    Vanadium compounds are acutely toxic by most routes of exposure, in
    most species. In general, the toxicity of vanadium compounds increases
    with the oxidation state. The rabbit and guinea-pig are more sensitive
    than the rat and mouse. Although intestinal absorption is low, where
    both oral and subcutaneous acute data have been available, toxicity
    has been shown to be much higher by the oral route (see table below).

    Acute toxicity of vanadium compounds by oral and sc routes


                                                                        

    Species   Compound                  Doses (mg/kg body weight)
                                     Subcutaneous      Intragastric
                                                                        

    Mouse     vanadium pentoxide     87.5-117.5 (LD)   23.4 (LD50)
    Rat       vanadyl sulfate        159-190 (LD)      10 (LD100)
    Rat       ammonium vanadate      5-3 (ED)          20 (ED)
                                                                        

    This may reflect the importance of the liver in determining the toxic
    effect. Inhalation exposure to condensation aerosols (fume) of
    vanadium pentoxide caused mild toxicity at 10 mg/m3  and lethal
    effects at 70 mg/m3.

    Repeated administration of vanadium compounds produces changes
    indicative of effects on protein metabolism, such as a decrease in
    serum albumin concentrations, increase in serum globulin, and changes
    in plasma amino acid concentrations.  Various changes in enzyme
    activities in blood have been described;  in particular, vanadium
    inhibits monoamine oxidase and some effects have been ascribed to
    elevated tissue serotonin levels, following this inhibition.  A
    decrease in plasma cholesterol levels and an increase in plasma
    triglycerides occur after both acute and long-term administration of
    vanadium compounds.  In  in vitro studies, vanadium has been shown to
    inhibit cholesterol biosynthesis in the liver. Other metabolic effects
    include reduced synthesis of cysteine and coenzyme A, uncoupling of
    oxidative phosphorylation in the liver mitochondria, and depletion of
    adenosine triphosphate (ATP) stores.  There is an increase in red cell
    count and, sometimes, in haemoglobin concentrations following vanadium
    administration.  Vanadate causes increased urinary flow and sodium
    loss in the rat, but not in the dog or cat.  Myocardial fatty changes
    and perivascular swelling were seen in rats and rabbits after
    inhalation exposure to 70 mg/m3 for 2 h per day for 9-12 months. 
    Though much is known of the metabolic effects of vanadium, it has not
    been possible to deduce its fundamental mode of action.

    Vanadium pentoxide dust (particle sizes mainly <10 m) produced
    deaths in rabbits after inhalation exposure to 205 mg/m3 for 7 h,
    but not after exposure to 77 mg/m3 for 7 h or to 525 mg/m3 for
    1 h.  There was marked inflammation of the whole respiratory tract
    with pulmonary oedema, and also conjunctivitis, enteritis, and fatty
    infiltration of the liver.  Vanadium pentoxide, administered as a
    condensation aerosol at 3-5 mg/m3 or as a dispersion aerosol at
    10-30 mg/m3, for 2 h on alternate days, for 3 months, produced
    pathological changes in the lung, particularly in its vasculature, but
    no other pathological effects.

    Doses of 0.05 mg vanadium/kg body weight per day (in the form of
    vanadium pentoxide or ammonium vanadate) produced functional
    neurological disturbance in rats, but doses of 0.005 mg/kg body weight
    per day did not. Inhalation exposure to a condensation aerosol of
    vanadium pentoxide at 0.027 or 0.006 (but not at 0.002) mg/m3 
    produced changes in the excitability of the tibial musculature in
    rats.

    Vanadium compounds appear to have significantly toxic effects on
    reproduction, when administered parenterally.  Low subcutaneous doses
    (0.85 mg/kg body weight) had an adverse effect on spermatogenesis in
    the rat and the same dose given to female rats on the fourth day of
    pregnancy resulted in increased mortality among the embryos.
    Parenteral administration of ammonium vanadate or vanadium pentoxide
    to pregnant Syrian golden hamsters and rats resulted in fetal deaths
    and in skeletal abnormalities in live-born pups.

    No clear pattern has emerged from genotoxicity tests. Some compounds
    gave weakly positive results in a bacterial mutagenicity assay on
    Bacillus subtilis, but the results of most bacterial mutagenicity
    tests were negative.

    The possible carcinogenicity of vanadium has not been determined.

    2.5  Effects on Human Beings

    Vanadium compounds have been used therapeutically in human beings for
    the treatment of various diseases.  Vanadium has been given orally in
    doses of 21-30 mg vanadium/day, as diammonium oxytartarovanadate, for
    6 weeks, in a study on its cholesterol-reducing effects. Vanadium
    compounds have been applied to the teeth to study their effectiveness
    in preventing dental caries.

    Inhalation exposure of human volunteers to vanadium pentoxide dust
    revealed that the principal symptom was cough, which began after 5 h
    exposure to 1 mg/m3 and after 20 h exposure to 0.2 mg/m3. Coughing
    persisted for about 1 week.  After exposure to a level of 0.1 mg/m3 
    for 8 h, cough developed after 24 h, progressed for 24 h, and then
    subsided, 72 h after exposure. In another study, 11/11 subjects
    reported irritation on inhalation exposure to vanadium pentoxide fumes
    at 0.4 mg/m3, 5/11 reported mild signs of irritation on exposure to
    0.16 mg/m3, but a level of 0.08 mg/m3 was not noticed by any of
    the 11 subjects.

    Acute inhalation over-exposure in mild cases causes sensory
    irritation, variable fever, conjunctivitis, and increased intestinal
    motility.  In moderate cases, there may be bronchospasm, cough, and
    vomiting and/or diarrhoea.  An eczematous rash is sometimes present. 
    In severe cases, there is bronchitis or bronchopneumonia and signs of
    systemic toxicity, including tremor and irreversible renal tubular
    damage.

    Long-term over-exposure to vanadium pentoxide causes wheezing, but
    without evidence of chronic bronchitis or emphysema; lung function and
    pulmonary radiography are usually normal.  Changes in the heart
    rhythm, right axis deviation, and P-wave changes in the
    electrocardiogram have been reported.

    There have been conflicting reports regarding elevation of vanadium
    levels in depressive illness and reductions associated with recovery.

    Vanadium poisoning in human beings can be diagnosed on the basis of a
    history of exposure, the clinical picture, a green tongue (due to the
    hexa-aquo ion), and measurements of vanadium levels in blood cells,
    plasma, and urine.  The value of various tests of the secondary
    metabolic effects of poisoning is disputed.  Dimercaprol (British
    anti-lewisite, BAL) and ascorbic acid may have value in the treatment
    of poisoning in human beings.

    Epidemiological studies of effects of various airborne metals on the
    general population have demonstrated weak correlations between
    vanadium levels in air and lung cancer and pneumonia, in one study,
    and between vanadium levels in air and cardiovascular disease, in
    other studies. These are not considered to indicate a causal
    relationship, because of methodological factors and disagreement with
    the results of studies of populations exposed occupationally to much
    higher levels.  There are no adequate epidemiological studies of
    mortality in occupationally-exposed populations.

    3.  CONCLUSIONS AND RECOMMENDATIONS

    There is no evidence that the general population is at risk, either
    through deficiency of, or over-exposure to, vanadium, despite the fact
    that atmospheric exposures may be high in the vicinity of
    metallurgical plants and installations burning high-vanadium fossil
    fuels.  Atmospheric exposure will exceed normal dietary exposure, or
    approach permitted occupational exposures, only very rarely.  A
    therapeutic role for vanadium has not been established.

    The potential for very high occupational exposures exists, and
    operations giving rise to them, such as boiler-cleaning, are difficult
    to control by engineering means. In such cases, respiratory protective
    equipment affording adequate protection will be required.  There is no
    evidence in human beings of the reproductive effects seen in animals
    at low doses.

    While vanadium is toxic for wildlife, only point-source emissions or
    accidental or deliberate deposits of vanadium compounds are likely to
    exert an effect.  Apart from such local effects, there is no increase
    in the amount of vanadium in the global environment, though its
    commercial uses may result in some redistribution, mainly from its
    sources on land-masses to continental shelf regions of oceans, as a
    result of the sedimentation of suspended material in surface waters.

    4.  HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY ACTION

    4.1  Main Human Health Hazards, Prevention and Protection, First Aid

    The main hazard is acute and long-term over-exposure to airborne
    vanadium particulates in an occupational setting. There is no evidence
    of hazard for the general population.  The effects of exposure to
    vanadium, their prevention, and first-aid recommendations are given in
    the Summary of Chemical Safety Information (section 6).

    4.1.1  Advice to physicians

    4.1.1.1  Symptoms of poisoning

    The most common presentation of vanadium over-exposure will be
    irritant effects on the conjunctivae and the respiratory tract. These
    may be mistakenly ascribed to upper respiratory tract infection,
    unless a proper occupational history is taken.  The severity of the
    conjunctivitis and nasal irritation can vary.  Nasal inflammation may
    be accompanied by a profuse and often blood-stained discharge and
    there may nose-bleeds.  Hyperplasia of the pharyngeal mucous membrane,
    with or without atrophic changes, has been described in relation to
    chronic vanadium poisoning.

    4.1.1.2  Medical advice

    Most cases will recover following removal from exposure and
    symptomatic treatment; the most important aspect will be the
    prevention of further excessive exposure. Cutaneous rashes will
    respond to simple topical treatments, including mild corticosteroid
    preparations, on areas other than the face. In the unlikely event of
    ingestion of vanadium compounds, in addition to treating local effects
    of mucosal irritation in the mouth and pharynx, the use of ascorbic
    acid in the acute phase or BAL (2,3-mercapto-1-propanol) in later
    stages could be considered. With reference to the more recent
    chelating agents, experimental studies have shown that
    diethylenetriaminepentaacetic acid (DTPA) and dimercaptosuccinic acid
    (DMSA) are not effective and there are no data on the use of
    2,3-dimercapto-1-propane sulfonic acid (DMPS).

    4.1.2  Health surveillance advice

    Proper systems for the control of exposure levels and the personal
    protection of workers, monitored by measurement of vanadium levels in
    air, are most important.  While urinary vanadium levels may be raised
    in acute or long-term over-exposure, they are not of value in
    quantifying exposure at levels complying with permitted vanadium
    concentrations in the work-place air. Early self-reporting of
    respiratory symptoms, and medically-directed enquiries about these
    symptoms, are probably the most sensitive indicators. Since the
    composition of many vanadium-containing dusts is complex, it may be

    prudent to include simple measures of pulmonary function, such as a
    forced expiratory spirogram, and, less frequently, chest radiographs,
    in surveillance programmes.

    4.2  Explosion and Fire Hazards

    Vanadium metal in powder form is combustible and may form explosive
    mixtures in air at concentrations in excess of 200 g/m3,  with an
    autoignition temperature of 500 C.  Some vanadium alloys are also
    combustible and explosive.

    However, most vanadium compounds are not combustible and, in general,
    they do not constitute a fire or explosion hazard.  Moreover,
    compounds in the lower oxidation states (for example, vanadium sulfide
    and vanadium carbide) may burn.  Many vanadium compounds react with
    water, sometimes with the production of toxic gases;  for example,
    both vanadyl chloride and vanadium trichloride will produce hydrogen
    chloride gas.

    4.2.1  Prevention

    Do not smoke or use open flames in areas where flammable vanadium
    compounds are handled.

    4.2.2  Fire-extinguishing agents

    Use dry powder, carbon dioxide, or halons to extinguish fires.  In
    general, do not use water, water spray, or water-based foams.

    4.3  Storage

    All vanadium compounds should be stored dry. Compounds with a low
    oxidation state that are combustible (e.g., vanadium sulfide) and
    vanadium metal should be stored away from oxidizing agents. Compounds
    that react with water, such as vanadyl chloride and vanadium
    trichloride, should be kept in sealed containers to prevent the
    ingress of moisture.

    4.4  Transport

    In case of accidents involving road transport, stop the engine and, as
    a general precaution, do not permit sources of ignition in the area. 
    In the case of fire or spillage, use the methods advised in sections
    4.2 and 4.5, respectively.  Notify the police and fire brigade
    immediately.

    4.5  Spillage and Disposal

    4.5.1  Spillage

    Powdered vanadium metal and powdered vanadium solids should be
    vacuumed up, using equipment designed for combustible powders.  The
    affected area should then be wet-mopped or flushed with water until no
    identifiable material remains.

    Liquid products should be absorbed in dry earth, sand, or other
    absorbent material to prevent spread, and shovelled into sealable
    containers for safe disposal (see section 4.5.2).  In the case of
    vanadium chloride or other halides, full protective clothing and
    respiratory protective equipment, effective against hydrogen halides,
    should be worn.  After absorption, small spillages of vanadium halides
    can be drenched with large quantities of water, providing that the
    spillage is sufficiently far away from any unprotected people or
    livestock. Occasionally, slow hydrolysis in atmospheric moisture may
    be acceptable, providing the spillage can be securely isolated.

    4.5.2  Disposal

    Waste material or material from spillages should be disposed of in a
    secure landfill, approved for chemical wastes.  The disposal of large
    quantities of unhydrolysed vanadium halides requires special
    conditions.

    5.  HAZARDS FOR THE ENVIRONMENT AND THEIR PREVENTION

    The reactive vanadium compounds, such as vanadium halides, will cause
    immediate local damage to the environment and high concentrations of
    vanadium in soils and surface waters will kill susceptible organisms.
    All vanadium is derived from the earth's crust and the net effect of
    its use is to transfer land-based deposits to ocean sediments. Soluble
    compounds will be widely dispersed and diluted.  Insoluble compounds
    will have little effect on the biosphere. Minimization of effluent
    streams, prevention of accidental losses and emissions, proper
    transport, storage, and waste disposal, and recovery of spent catalyst
    will minimize the environmental impact.

    6.  SUMMARY OF CHEMICAL SAFETY INFORMATION

     This summary should be easily available to all health workers
     concerned with, and users of, vanadium. It should be displayed at, or
     near, entrances to areas where there is potential exposure to
     vanadium, and on processing equipment and containers.  The summary
     should be translated into the appropriate language(s).  All persons
     potentially exposed to the chemical should also have the instructions
     in the summary clearly explained.

     Space is available for insertion of the National Occupational
     Exposure Limit, the address and telephone number of the  National
     Poison Control Centre, and for local trade names.


        VANADIUM AND SOME COMPOUNDS

                                                                                                                                         

    Compound              Form       Colour       MP      BP        Water          SG        RMMa     Other characteristics
                                                 (C)    (C)     solubility
                                                                   (g/litre)
                                                                                                                                         

    Vanadium              metal      grey         1890    3380      insolubleb     6.11c              Vanadium is combustible and may
                                                                                                      form explosive mixtures in air at
    Vanadium pentoxide    crystals   yellow/       690    1750      0.7            3.357     181.9    high concentrations (200g/m3);
                                     red                                                              vanadium trichloride
                                                                                                      and vanadyl oxychloride
    Vanadium trioxide     crystals   black        1970    no data   slight         4.87      149.9    react (violently)
                                                                                                      with water to form toxic
                                                                                                      and irritant hydrogen
    Sodium metavanadate   crystals   colourless/   630    no data   211            no data   194.0    chloride gas;  vanadium
                                     green                                                            pentoxide is used as a
                                                                                                      catalyst in many oxidation
    Vanadium              liquid     red/brown     -28     148.5    reacts         1.816     192.78   reactions and may be prepared in 
    tetrachloride                                                                                     special forms for this purpose;
                                                                                                      "spent" catalyst may contain 
    Vanadyl chloride   deliquescent  yellow        -77     126.7    reacts         3.00      173.32   acidic and other residues;
                          liquid                                                                      vanadium sulfide reacts with
                                                                                                      acids and water to produce
    Ammonium vanadate     crystals   colourless/     decomposes     5.2            2.326     117      toxic hydrogen sulfide gas;  it
                                     yellow                                                           reacts violently with oxidizing
                                                                                                      agents; on heating or burning
                                                                                                      in air, it releases irritant
                                                                                                      vanadium pentoxide and sulfur
    Vanadium sulfide      crystals   black           decomposes     reacts         4.2        83      oxides 


                                                                                                                                         

    HAZARDS/SYMPTOMS                        PREVENTION AND PROTECTION                    FIRST AID
                                                                                                                                         

    SKIN: Vanadium pentoxide and            Wear impermeable gloves;  skin               Wear gloves to remove contaminated 
    vanadium sulfide cause irritation;      irritation is particularly likely at         clothing;  brush powders off skin and wash
    vanadium halides cause skin burns;      the point of contact of dust masks;          well with water;  for vanadium halides, 
    ortho- and metavanadate salts have      control airborne dust levels, as far         wear gloves and (if possible)
    little effect                           as possible, by engineering means;           respiratory protection, remove
                                            wear goggles, a full-face visor, or a        contaminated clothing, without wetting, and
                                            respirator, when handling vanadium           throw down-wind or place in sealable 
                                            halides                                      container;  drench casualty under
                                                                                         emergency shower; obtain medical advice

    EYES: Vanadium powder acts as           Avoid generating dust;  wear chemical        Irrigate with potable water or sterile 
    a foreign body;  other compounds        goggles, a full-face visor, or a             eye-wash fluid for at least 15 minutes;
    cause various degrees of irritation     respirator, when handling vanadium           obtain medical attention, if symptoms
                                            halides                                      persist

    INHALATION: Vanadium pentoxide          Control dust, fume, and vapours, as far      Remove from exposure into fresh air;  if
    dust and particularly fume is           as possible, by engineering means;           breathing is difficult, keep patient
    an acute and chronic irritant;          where dust levels exceed occupational        seated at rest and give oxygen;  obtain
    vapours and hydrolytic products         exposure limits, wear respiratory            medical attention, if symptoms persist
    of vanadium halides and sulfides        protective equipment with a suitable
    are irritant; ortho- and                protection factor;  for boiler cleaning
    metavanadates are less irritant         operations, use compressed air 
                                            breathing apparatus (CABA);  for 
                                            vanadium halides wear CABA or use 
                                            canisters effective against HCl

                                                                                                                                         

    HAZARDS/SYMPTOMS                        PREVENTION AND PROTECTION                    FIRST AID
                                                                                                                                         

    INGESTION: Vanadium                     Do not eat, drink, or smoke where            Obtain medical attention
    compounds may cause signs and           chemicals are handled;  use good 
    symptoms of gastrointestinal            personal hygiene
    irritation and of systemic toxicity,
    particularly in the liver

                                                                                                                                         

    Ammonium polyvanadate, sodium metavanadate, vanadium pentoxide, trioxide, and sulfate are in United Nations
    Transport Class 6.1 (Toxic); vanadium trichloride and tetrachloride are in Class 9 (Corrosive)

              
    a RMM = Relative molecular mass.
    b "Cold" water.
    c At temperatures in the range 15-35C.
    

    7.  CURRENT REGULATIONS, GUIDELINES, AND STANDARDS

    The information given in this section has been extracted from the
    International Register of Potentially Toxic Chemicals (IRPTC) legal
    file. A full reference to the original national document from which
    the information was extracted can be obtained from IRPTC.  When no
    effective date appears in the IRPTC legal file, the year of the
    reference from which the data are taken is indicated by (r).

    The reader should be aware that regulatory decisions about chemicals,
    taken in a certain country, can only be fully understood in the
    framework of the legislation of that country.  Furthermore, the
    regulations and guidelines of all countries are subject to change and
    should always be verified with appropriate regulatory authorities
    before application.

    7.1  Exposure Limit Values

    Some occupational exposure and environmental limit values for vanadium
    and vanadium pentoxide are given in Tables 1A and 1B.

    7.2  Specific Restrictions

    In the United Kingdom, it is required that the "Best Practical Means"
    should be used in specified premises, to reduce emissions containing
    vanadium and to render them harmless and inoffensive. The EEC requires
    member states to limit the introduction of vanadium into ground water
    by prior investigation of all direct discharges and of any disposal or
    tipping that might lead to indirect discharge.  Member states are
    empowered to monitor vanadium in relation to discharges into fresh or
    estuarine waters from titanium dioxide plants or in relation to
    titanium dioxide dumps.  In the USA, the Environmental Protection
    Agency controls vanadium discharges by general regulations relating to
    point-source emissions into waters.  The measurement techniques for
    quantifying vanadium in discharges, as specified in US legislation,
    are: digestion followed by atomic-absorption spectrometry or
    colorimetry for total vanadium; dissolved vanadium is determined after
    0.45-m filtration.

    In the European Economic Community, vanadium waste is controlled to
    limit its introduction into surface, ground, or salt waters and levels
    may have to be monitored on a regular basis.  In the United Kingdom,
    waste containing vanadium or vanadium compounds is controlled as
    special waste.  In the USA, a permit is required for the discharge of
    vanadium waste into US waters, and vanadium pentoxide, and solutions
    and mixtures containing it, are designated as hazardous substances for
    the purposes of discharge.  Solid waste containing vanadium pentoxide
    is subject to control as a hazardous waste.  When the waste is a
    commercial product, it is identified as an acute hazardous waste.


        TABLE 1A. EXPOSURE LIMIT VALUES FOR VANADIUM

                                                                                                                                         

    Medium      Specification       Country/            Exposure limit description                   Value                Effective
                                    organization                                                                          date
                                                                                                                                         

    AIR         Occupational        Canada              Threshold limit value (TLV)                                       1980
                                                        Respirable dust and fume measured as
                                                        V2O5
                                                        - Time-weighted average (TWA)                0.05 mg/m3

                                    Czechoslovakia      Maximum allowable concentration (MAC)                             1985
                                                        Fume
                                                        - Time-weighted average (TWA)                0.1  mg/m3
                                                        - Ceiling value (CLV)                        0.3  mg/m3
                                                        Dust
                                                        - Time-weighted average (TWA)                0.5  mg/m3
                                                        - Ceiling value (CLV)                        1.5  mg/m3

                                    USSR                Maximum allowable concentration (MAC)                             1977
                                                        - Ceiling value (CLV)                        4.0  mg/m3
                                                        (cinder dust;  aerosol)

    AIR         Ambient             EEC                 Maximum limit (MXL)                                               1990
                                                        From combustion of waste oils in plants
                                                        with a thermal input of 3 megawatts (MW) 
                                                        or more

    AIR         Ambient             EEC                 - Sum of chromium, copper and vanadium       1.5  mg/m3
                                                        - Sum of chromium, copper, lead and 
                                                        vanadium

                                                                                                                                         

    Medium      Specification       Country/            Exposure limit description                   Value                Effective
                                    organization                                                                          date
                                                                                                                                         

    AIR         Ambient             Germany, Federal    Maximum limit                                                     1986
                                    Republic of         Total concentration of dusts of antimony,
                                                        lead, chromium, copper, manganese,
                                                        platinum, palladium, rhodium, vanadium, and
                                                        tin, as well as their inorganic compounds 
                                                        and soluble inorganic cyanides and fluorides,
                                                        may not exceed 5 mg/m3 at a mass flow of
                                                        25 g/h or more

    WATER       Surface             Czechoslovakia      Maximum allowable concentration (MAC)        0.05 mg/litre        1975

                                    USSR                Maximum allowable concentration (MAC)        0.1 mg/litre         1983
                                                        Vanadium and its compounds calculated
                                                        as vanadium

    WATER       Drinking-           Czechoslovakia      Maximum allowable concentration (MAC)        0.01 mg/litre        1982

    WATER       Drinking-water      Czechoslovakia      Maximum allowable concentration (MAC)        0.005 mg/litre       1975
                reserves

    SOIL        General             USSR                Maximum allowable concentration (MAC)        150 mg/litre         1982
                                                                                                                                         


    TABLE 1B. EXPOSURE LIMIT VALUES FOR VANADIUM AS VANADIUM PENTOXIDE (V2O5)

                                                                                                                                         

    Medium      Specification       Country/            Exposure limit description                   Value                Effective
                                    organization                                                                          date
                                                                                                                                         

    AIR         Occupational        Australia           Threshold limit value (TLV)                                       1985 (r)
                                                        - Time-weighted average (TWA)                0.05 mg/m3
                                                        Respirable dust and fume measured as
                                                        V2O5

                                    Belgium             Threshold limit value (TLV)                                       1987 (r)
                                                        - Time-weighted average (TWA) (as V)         0.05 mg/m3

                                    Bulgaria            Maximum permissible concentration (MPC)      0.5  mg/m3           1985 (r)
                                                        - Ceiling value (CLV)                        0.5  mg/m3

                                    German              Maximum allowable concentration (MAC)                             1988 (r)
                                    Democratic          - Short-term exposure limit (STEL)
                                    Republic            - Fume (as V205)                             0.1  mg/m3
                                                        - Dust (as V205)                             0.5  mg/m3

                                    Germany, Federal    Maximum allowable concentration (MAC)                             1985 (r)
                                      Republic of       - Time-weighted average (TWA) (fine dust)    0.05 mg/m3
                                                        - Short-term exposure limit (STEL)           2.5  mg/m3
                                                          (fine dust) (30 min;  twice per shift)

                                    Hungary             Maximum allowable concentration (MAC)                             1987 (r)
                                                        - Time-weighted average (TWA) (dust)         0.5  mg/m3
                                                        - Short-term exposure limit (STEL) (dust)    1    mg/m3

                                    Italy               Threshold limit value (TLV)                                       1985 (r)
                                                        - Time-weighted average (TWA)                
                                                          (sensitizer)                               0.05 mg/m3
                                                          (dust)                                     0.5  mg/m3
                                                                                                                                         

                                                                                                                                         

    Medium      Specification       Country/            Exposure limit description                   Value                Effective
                                    organization                                                                          date
                                                                                                                                         

    AIR         Occupational        Japan               Maximum allowable concentration (MAC)                             1988 (r)
                                                        - Time-weighted average (TWA)
                                                        - Fume                                       0.1  mg/m3
                                                        - Dust                                       0.5  mg/m3

                                    Sweden              Hygienic limit value (HLV)                                        1988
                                                        - Time-weighted average (TWA)                0.2  mg/m3
                                                         (total dust as V)
                                                        - Ceiling value (CLV)                        0.05 mg/m3
                                                         (respirable dust as V)

                                    United Kingdom      Recommended threshold limit (RECL)                                1987 (r)
                                                        - Time-weighted average (TWA) (dust)         1.5  mg/m3
                                                          (fume)                                     0.05 mg/m3
                                                        - Short-term exposure limit (STEL)           1.5  mg/m3
                                                          (10-min, TWA) (dust as V)                  0.5  mg/m3
                                                          (fume as V)

                                    USA (ACGIH)         Threshold limit value (TLV)                                       1988
                                                        - Time-weighted average (TWA), metal         0.05 mg/m3
                                                         (respirable dust and fume)

                                    USA (OSHA)          Permissible exposure limit (PEL)                                  1986 (r)
                                                        - Ceiling value (CLV)                        0.5  mg/m3
                                                        (V205 dust)                                  0.1  mg/m3
                                                        (V205 fume)

                                    USSR                Maximum allowable concentration (MAC)                             1984
                                                        - Ceiling value (CLV)                        0.5  mg/m3
                                                        (aerosol)

    AIR         Ambient             USSR                Maximum allowable concentration (MAC)        0.002mg/m3           1984

                                                                                                                                         
    


    7.3  Labelling, Packaging, and Transport

    The European Economic Community labels vanadium pentoxide as follows:

          Harmful;  harmful by inhalation;  do not breathe dust.

    BIBLIOGRAPHY

    ACGIH  (1986)   Documentation of the threshold limit values and
     biological exposure indices, Cincinnati, American Conference of
    Governmental Industrial Hygienists.

    CLAYTON, G.D. & CLAYTON, F.E.  (1981)  Patty's industrial hygiene and
     toxicology, Vol. 2A, New York, Wiley - Interscience, John Wiley &
    Sons.

    GOSSELIN, R.E., HODGE, H.C., SMITH, R.P., & GLEASON, M.N.  (1976)
     Clinical toxicology of commercial products, 4th ed., Baltimore,
    Maryland, Williams and Wilkins Company.

     Handling chemicals safely, 2nd ed. (1980). Dutch Association of
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    IARC (1974)  Monographs on the Evaluation of Carcinogenic risk of
     chemicals to man:  some aromatic amines, hydrazine and related
     substances, N-nitroso compounds and miscellaneous alkylatry agents,
    Vol.4, Lyon, International Agency for Research on Cancer.

    IRPTC (1988)  Data profile (legal file), Geneva, International
    Register of Potentially Toxic Chemicals.

    MATERIAL SAFETY DATA SHEETS COLLECTION PLUS UPDATING SERVICE (1984)
    New York, Genium Publishing Corporation.

    SAX, N.I.  (1984)  Dangerous properties of industrial materials, New
    York, Van Nostrand Reinhold Company.

    US NIOSH  (1976)  A guide to industrial respiratory protection,
    Cincinnati, Ohio, US National Institute for Occupational Safety and
    Health.

    US NIOSH/OSHA  (1981)  Occupational health guidelines for chemical
     hazards, Washington DC, US National Institute for Occupational
    Safety and Health, Occupational Safety and Health Administration,
    3 Vol. (Publication No. 01.123).

    US NIOSH/OSHA  (1985)  Pocket guide to chemical hazards, Washington
    DC, US National Institute for Occupational Safety and Health,
    Occupational Safety and Health Administration (Publication
    No. 85.114).

    US DHHS (NIOSH) (1987)  Registry of Toxic Effects of Chemical
     Substances, Washington DC, US Department of Health and Human
    Services, Public Health Service, Centers for Disease Control, National
    Institute for Occupational Safety and Health, 5 Vol. (DHSS/NIOSH:
    Publication No. 87-114)

    WHO (1988)  Environmental Health Criteria No.81: Vanadium.  Geneva,
    World Health Organization.

    


    See Also:
       Toxicological Abbreviations