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
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Universal Copyright Convention. For rights of reproduction or
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should be made to the Office of Publications, World Health
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welcomes such applications.
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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 (<300°C). 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 µg vanadium).
Vanadium in air can be measured using direct current plasma atomic
emission spectrometry (DCP-AES) (vanadium detection limit of
4.0 µg/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 µg 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 µg/day.
In the USA, most drinking-water samples contained less than
10 µg/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 µg/kg wet
weight. The lungs contain 19-140 µg/kg wet weight and blood serum,
about 30 µg/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 µg/litre), but concentrations above 100 µg/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 µm) 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 15-35°C.
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-µm 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.
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