SCIENTIFIC AND TECHNICAL
ASSESSMENT REPORT
ON VANADIUM
nvironmental Protection Agency
Office of Research and Development
Washington, D.C. 20460
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EPA-600/6-77-002
October 1977
SCIENTIFIC AND TECHNICAL
ASSESSMENT REPORT
ON
VANADIUM
Program Element No. 1AA601
Assembled by
Health Effects Research Laboratory
Environmental Research Center
Research Triangle Park, North Carolina
for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have
been grouped into scries. These broad categories were established to facilitate further development and
application of environmental technology. Elimination of traditional grouping Was consciously planned to
foster technology transfer and a maximum interface in related fields. These scries are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
9. Miscellaneous Reports
This report has been assigned to the SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS (STAR)
series. This series assesses the available scientific and technical knowledge on major pollutants that would be
helpful in possible EPA regulatory decision-making regarding the pollutant or assesses the state of
knowledge of a major area of completed study. The series endeavors to present an objective assessment of
existing knowledge, pointing out the extent to which it is definitive, the validity of the data on which it is
based, and uncertainties and gaps that may exist. Most of the reports will be multi-media in scope, focusing
on single media only to the extent warranted by the distribution of environmental insult.
EPA REVIEW NOTICE
This report has been reviewed by the Office of Research and Development, EPA, and approved for
publication. Mention of trade names or commercial products docs not constitute endorsement or
recommendation for use.
DISTRIBUTION STATEMENT
This report is available to the public from Superintendent of Documents, U.S. Government Printing Office,
Washington, D.C. 20402.
Report No. EPA-600/6-77-002
it
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PREFACE
Although this report is issued in the Scientific and Technical Assessment Report Series, it
differs in several respects from the comprehensive multimedia format that publications in this Series
usually have because it was nearly completed before the creation of the STAR series in August 1974.
This document was prepared by a task force convened under the direction of Dr. F. Gordon
Hueter, Director, Special Studies Staff, U. S. Environmental Protection Agency, Environmental
Research Center (ERC), Research Triangle Park (RTP), N. C. The Special Studies Staff assembled
and produced the report. The objective was to review and evaluate the current knowledge of vana-
dium in the environment as related to possible deleterious effects on human health and welfare.
Information from the literature and other sources has been considered generally through August
1973.
The primary reference for this report was a report prepared for the U. S. Environmental Pro-
tection Agency (EPA) by a National Academy of Sciences' Panel on Vanadium of the Committee
on Medical and Biological Effects of Environmental Pollutants.
The following persons served on the ERC/RTP Task Force on Vanadium:
Robert Horton, Chairman
Marijon Bufalini Sharon Long
Gary Evans Carol Sawicki
J.H.B. Garner Jack Suggs
Bruce Harris Elbert Tabor
James Homolya Michael Waters
Danyl von Lehmden Douglas Worf
The substance of this document was reviewed by the National Air Quality Criteria Advisory
Committee (NAQCAC) in public session on March 21, 1974. Members of NAQCAC were:
Arie J. Haagen-Smit, Chairman — California Institute of Technology
Mary O. Amdur — Harvard University
David M. Anderson — Bethlehem Steel Corporation
Anna M. Baetjer — Johns Hopkins University
Thomas D. Crocker — University of California
Samuel S. Epstein — Case Western Reserve University
C. C. Li — University of Pittsburgh
ill
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James McCarroll — University of Washington
Eugene P. Odum — University of Georgia
Elmer Robinson — Washington State University
Morton Sterling — Wayne County Michigan Health Department
Arthur C. Stern — University of North Carolina
Elmer P. Wheeler — Monsanto Company
John T. Wilson, Jr. — Howard University
Ernst Linde, Executive Secretary
The report was reviewed, under the supervision of Kenneth Cantor, by a task force composed
of members of EPA's Office of Research and Development.
Review copies of this document were also provided to other government agencies and to indus-
trial and public interest groups.
All comments and criticisms were reviewed and incorporated in the document where deemed
appropriate.
iv
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TABLE OF CONTENTS
Page
LIST OF FIGURES vi
LIST OF TABLES vii
LIST OF ABBREVIATIONS AND SYMBOLS ix
1. INTRODUCTION .... 1-1
2. SUMMARY AND CONCLUSIONS . 2-1
2.1 SUMMARY 2-1
2.2 CONCLUSIONS 2-4
3. CHEMICAL AND PHYSICAL PROPERTIES . 3-1
3.1 REFERENCE FOR SECTION 3 3-2
4. SAMPLING, PREPARATION, AND ANALYSIS . 4-1
4.1 INTRODUCTION 4-1
4.2 ENVIRONMENTAL SAMPLES 4-3
4.3 BIOLOGICAL MATERIALS 4-12
4.4 STATIONARY SOURCE SAMPLES 4-14
4.5 REFERENCES FOR SECTION 4 4-17
5. ENVIRONMENTAL APPRAISAL 5-1
5.1 OCCURRENCE 5-1
5.2 CONCENTRATIONS 5-9
5.3 TRANSPORT AND MODELING 5-35
5.4 REFERENCES FOR SECTION 5 5-41
6. EFFECTS OF VANADIUM 6-1
6.1 BIOMEDICAL EFFECTS 6-1
6.2 EFFECTS IN PLANTS AND MIROORGANISMS 6-23
6.3 EFFECTS IN ANIMALS 6-26
6.4 EFFECTS ON MATERIALS AND THE ENVIRONMENT . 6-27
6.5 REFERENCES FOR SECTION 6 6-30
7. CONTROL TECHNOLOGY 7-1
7.1 REFERENCES FOR SECTION 7 7-2
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LIST OF FIGURES
Figure Page
5.1 Histogram for NASN Urban Sites, 1965-1969 5-15
5.2 Histogram for NASN Nonurban Sites, 1965-1969 ... 5-16
5.3 Geographic Distribution of Vanadium Concentrations.
Generalized on Basis of 5-year (1965-1969) Averages for NASN Sites . . 5-17
5.4 Location of Fixed Sampling Stations in Kanawha River Valley. Average Vanadium
Concentrations (ng/m8) for the Study Period (1964-1965) Indicated for Selected
Sites . 5-20
5.5 Vanadium Concentrations for Chicago (24-hour averages, in ng/m3) .5-21
5.6 Monthly Variation of Vanadium Deposition, Helsinki, Finland, 1964-1965 . .5-25
5.7 Daily Variation of Total Paniculate and Vanadium Concentrations in Air of Oil-heat-
ing Area during Cold Period, Helsinki, Finland, 1964-1965 . 5-26
5.8 Biogeochemical Vanadium Cycle 5-39
5.9 Flow Diagram of Fate of Vanadium in an Urban Air Shed ... 5-40
6.1 Chemical Composition (Minor Elements) of Harbor Sediment and Fly Ash as Com-
pared with Sewage Sludges and Various Sediments and Soils . . . 6-29
6.2 Temporal Variations of Lead, Cadmium, Uranium, and Vanadium Concentrations in
Norwegian Glacier Ice . . . ...... 6-30
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LIST OF TABLES
Table Page
3.1 Some Physical Properties of Important Vanadium Compounds .. .. 3-1
3.2 Boiling Points of Vanadium Halides and Oxyhalides 3-2
4.1 Colorimetric Reagents for Detecting Vanadium ... 4-6
4.2 Analytical Results for "Standard" Rocks 4-12
5.1 Emissions of Vanadium by Source, 1968 . 5-2
5.2 Material Balance for Vanadium at a Coal-Fired Steam Power Plant . . . 5-3
5.3 Vanadium Concentration of Coal Fly Ash, by Particle Size . . . . ... 5-3
5.4 Vanadium Concentration in Gasoline, Fuel Additives, Motor Oil, Fuel Oil, Crude Oil,
and Coal . . . . . 5-4
5.5 Atmospheric Concentrations of Vanadium at Boundary of Typical Steel Plant, 1967 . . 5-5
5.6 Steels Containing Vanadium .... . . . 5-6
5.7 Metallurgical Uses of Vanadium in the United States . . . . . . 5-6
5.8 Concentrations of Vanadium Pentoxide in Air at Point Sources at a Steel Plant . . 5-8
5.9 Annual Average Vanadium Concentrations — NASN Urban Sites, 1965-1969 .5-11
5.10 Annual Average Vanadium Concentrations — NASN Nonurban Sites, 1965-1969 . .5-12
5.11 NASN Urban Sites Exceeding 100 ng/m8 and Nonurban Sites Exceeding 10 ng/m8,
1968 5-13
5.12 Vanadium Concentrations by Season, 1968 ... . . 5-14
5.13 Quarterly and Annual Size Distribution for Vanadium, 1970 . . .5-18
5.14 Vanadium Concentrations, Kanawha Valley Study .5-19
5.15 Seasonal Ambient Vanadium Concentrations — Birmingham, Alabama Area, 1964-
1965 5-20
5.16 Annual Average Vanadium Concentrations, New York City, 1968 ... 5-22
5.17 Annual Average Vanadium Concentrations, Helsinki, Finland, 1962-1963 5-22
5.18 Monthly Vanadium Deposition, Helsinki, Finland, 1964-1965 5-23
5.19 Vanadium Deposition at Various Investigation Points, Helsinki, Finland, 1964-1965 .5-23
5.20 Average Vanadium Concentrations, December to February 1965, Helsinki, Finland .5-24
5.21 Vanadium Concentrations in Food 5-28
5.22 Vanadium Concentrations in Animal Specimens .. 5-29
5.23 Vanadium Concentrations in Fruits and Vegetables .. 5-30
5.24 Vanadium Concentrations in Fats and Oils .. .5-31
5.25 Vanadium Concentrations in Plants and Animals 5-32
5.26 Vanadium Concentrations in Tissues of Wild Animals .... 5-33
5.27 Vanadium Concentrations in Human Tissues 5-36
5.28 Estimated Particle Size Distribution (weight percent) 5-40
6.1 Balance of Vanadium in Two Men ... 6-2
6.2 Vanadium Intake in Urban and Nonurban Areas 6-2
vii
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6.3 Excretion of Vanadium by Three Human Subjects 6-5
6.4 Thermal-Precipitator Samples Taken from Superheater during Cleaning Operation... 6-8
6.5 Analysis of Dust from Boiler during Cleaning 6-8
6.6 Symptoms in Vanadium Workers 6-9
6.7 Physical Findings in Vanadium Workers 6-9
6.8 Threshold Limit Values for Vanadium Compounds, 1961, 1971, 1972 6-10
6.9 Documentation of Threshold Limit Values: Outline of Literature Findings Cited on
Industrial Exposures to Vanadium 6-11
6.10 Comparison of 1972 TLV for Vanadium Pentoxide Dust and Fume with TLVs for
Other Metallic Oxides . . . 6-12
6.11 Toxicity of Vanadium Salts to Mammals . 6-15
6.12 Lethal Doses of Selected Vanadium Salts . . .6-16
6.13 Respiratory Effects of Vanadium Pentoxide in Experimental Animals 6-17
6.14 Vanadium in Ash of Above-Ground Parts of Plants Grown in Experimental Plots .6-25
6.15 Comparison of Vanadium in Ash of Tops and Roots of Plants Grown in Experimental
Plots 6-25
vlU
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LIST OF ABBREVIATIONS AND SYMBOLS
ADP
ATP
ASV
BOF
b.p.
°C
CaCO8
Ca8(P04)2
CaSO4
Ca(UO2)2(VO4)2.nH2O
CHESS
cm
EPA
ESP
Fe2O»
Ge(Li)
Hg
HSLA
kg
km
Ka(UOa)2(VO02.3H2O
Ib
LTA
m
m»
Mg
mg
MIBK
min
mm
MMD
MT
NaI(Tl)
Na2O
NASN
ERC/RTP
ng
ppb
ppm
psi
TLV
V
Adenosine diphosphate
Adenosine triphosphate
Anodic_ stripping voltammetry
Basic oxygen furnace
Boiling point
Degrees Celsius (centigrade)
Calcium carbonate
Calcium phosphate
Calcium sulf ate
The mineral tyuyamunite
Community Health and Environmental Surveillance System
Centimeter
U, S. Environmental Protection Agency
Electrostatic precipitator
Ferric oxide
Gram
Lithium-drifted germanium detector
Mercury
High-strength, low-alloy steel
Kilogram
Kilometer
The mineral carnotite
Pound
Low-temperature asher
Meter
Cubic meter
Megagram (metric ton, MT)
Milligram
Methyl isobutyl ketone
Minute
Millimeter
Mass median diameter
Metric ton (megagram, Mg)
Thallium-activated sodium iodide detector
Sodium oxide
National Air Sampling Networks
EPA Environmental Research Center,
Research Triangle Park, North Carolina
Nanogram
Parts per billion
Parts per million
Pounds per square inch
Lithium-drifted silicon detector
Threshold limit value
Vanadium
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VClg Vanadium trichloride
VOC12 Vanadyl dichloride
VOC18 Vanadyl trichloride
V2O8 Vanadium trioxide
V2O4 Vanadium tetroxide
V2O6 Vanadium pentoxide
yr Year
ftg Micrograra
Micrometer (micron)
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ABSTRACT
This report is a review and evaluation of the current knowledge of vanadium in the environment as
related to possible deleterious effects on human health and welfare. Sources, distribution, measure-
ment, and control technology are also considered. Vanadium is widely distributed in nature and is
usually present in small quantities in all media and living forms. The concentration of vanadium in
ambient air varies a great deal across the United States, with the highest levels — annual averages
exceeding 100 ng/m3 — occurring in metropolitan areas on the eastern seaboard.
The largest source of environmental contamination by vanadium is oil combustion. Vanadium par-
ticulate matter is small, well within the respirable range for human beings. Most information on hu-
man vanadium exposure is of occupational origin, principally exposure to dusts in metallurgical work
and boiler-cleaning operations. Respiratory absorption of vanadium appears to be very efficient, and
it is thought that prolonged, repeated exposure could produce chronic lung disease. High-level indus-
trial exposures of humans have shown evidence of complex internal injuries in the body, particularly
enzyme interference.
The small particle size of vanadium emissions makes complete control unlikely, but good particulate
•control measures can greatly reduce vanadium output from most sources.
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SCIENTIFIC AND TECHNICAL ASSESSMENT
REPORT ON VANADIUM
1. INTRODUCTION
The purposes of this document are to explore current knowledge regarding the sources and distribu-
tion of vanadium in the environment, to study its presence and role in living things, and to evaluate
its effects on human health and welfare. Particular attention is given to the air environment, its
pollution, and undesirable effects of such pollution. Interest in vanadium as a pollutant, particularly
in air, originates from its capacity to produce severe respiratory illness in workers exposed to vanadi-
um compound dusts and fumes. Human and experimental animal observations also indicate the
presence of metabolic changes in other organs resulting from vanadium overexposure, but these are
not as well understood as the respiratory effects.
1-1
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2. SUMMARY AND CONCLUSIONS
2.1 SUMMARY
Vanadium occurs commonly but not uniformly in the earth's crust. The average concentration is
about 150 milligrams per kilogram (mg/kg). It is extracted from ores usually containing 0.1 to 1.0
percent of vanadium compounds, with a maximum of 3.0 percent. It is frequently associated in
ores with uranium and titanium, and it is mined in conjunction with these metals. Vanadium is
also widely distributed in small amounts in living things. High concentrations are rare in nature,
but are sometimes produced by human activities.
Current measurement methods for vanadium are more sensitive and reliable than older methods,
which often produced erroneous data. Environmental and biologic information is still quite sparse
for this metal. No comprehensive comparative studies of analytical methods have yet been made; thus
no recommendations regarding a best method can be made at this time.
By far the largest source of environmental contamination with vanadium from human activity in this
country is from the burning of oil and, to a lesser extent, of coal. This pollution results mainly from
emissions into the air of very fine particles, but the ash from combustion of both types of fossil fuel
also contains the metal. Disposal of this ash may pollute soil or water. The vanadium content of coal
is moderately variable, but oils differ more widely. Venezuelan oil imported into the northeastern
part of the country has high vanadium content; other oils used in the United States are quite low in
vanadium. Refining processes virtually eliminate vanadium in kerosene, gasoline, diesel fuel, and
home heating oils. Vanadium is concentrated in the residual oils that are burned (along with crude
oil) in large heating and power units, petroleum refineries, and ships. Desulfurization of oil removes
vanadium in quantities proportional to the amount of removed sulfur.
Extraction and use of vanadium also produce some opportunities for environmental contamination.
Extraction of the metal from ores begins with sintering, which emits fine particulates to the air. Ex-
tracting is followed by leaching with water, which may produce contamination of soil or water. Initial
alloying into ferrovanadium in the few ferrovanadium plants in this country produces fume in large
quantities, which may produce air pollution. Use of the vanadium metal and compounds (particularly
the latter) is widespread. The iron and steel industry is the largest user of vanadium. The chemical
industry commonly uses vanadium catalysts, and there are some uses for vanadium hi the ceramic,
dye, and ink industries —• nearly all of which use very small quantities, which are then widely dis-
2-1
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persed. Opportunities for environmental contamination from use sources are presently thought to be
limited to recycling (for steel alloys) and disposal of spent catalysts and other products. The latter
groups present many uncertainties. In steel reclamation in basic oxygen furnaces, some of the alloy-
ing substances are driven off in fume. Local contamination may result, depending on the extent of
paniculate control used.
The concentration of vanadium in ambient air varies a great deal across the United States, with the
highest levels — annual averages exceeding 100 nanograms per cubic meter (ng/m3) — occurring
in a cluster of cities along the eastern seaboard. The primary source of airborne vanadium in that area
is the large quantity of fuel oil (much of which comes from the vanadium-rich crude oil of Venezu-
ela) used for generation of electricity and for space heating.
In spite of wide fluctuations from year to year, vanadium levels have been generally increasing in
recent years, probably in response to the increasing use of oil as a fuel. Winter averages are more
than 'triple summer averages, reflecting the seasonal pattern in fuel oil consumption for heating pur-
poses.
Studies of particle size distribution have shown that most vanadium-bearing paniculate matter is
very small — well within the respirable range for human beings.
A number of intensive air pollution studies in metropolitan areas have confirmed that maximum va-
nadium concentrations occur in areas of greatest population density during the coldest part of the
year and during the late evening hours.
Vanadium soil concentrations vary according to the type of rock or soil and are highest in shales and
clays. The estimated average concentration in the earth's crust is 150 mg/kg. The concentration of
vanadium in fresh water varies with the soil and rocks in the area of the water source being sampled.
Because of the presence of vanadium-containing uranium ores in the rocks, the rivers of the Colorado
Plateau have the highest vanadium levels. Vanadium concentrations in fresh water vary from below
detectable to 300 micrograms per liter (/tig/liter). Vanadium entering the ocean from fresh water
sources in usually deposited in sediments. Only about 0.001 percent of the vanadium entering the
oceans remains in soluble forms. The total amount of vanadium in the oceans is estimated to be 7.5
x 1012'kg.The concentration in sea water ranges from 0.2 to 29 /ig/liter.
Vanadium is ubiquitous at low levels in foods as far as is now known. However, data are meager and
unreliable because of the older, poorly developed methodology of some studies.
All plants contain vanadium. Concentrations of the element tend to be higher and related to soil
levels of vanadium in roots, and lower and independent of soil levels in leaves. The metal is essential
for production of soil and plant nitrate by the bacteria of the root nodules of legumes.
Small amounts of vanadium are present in most animal tissues. Levels are somewhat higher in fat
and in keratin-containing tissues such as hair, nails, and hooves. Accumulation with age in human
lungs has been noted, but this effect has not been seen in other animals. Data on this subject are
limited.
2-2 STAR —VANADIUM
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Information for modeling the movement of vanadium in the environment is grossly inadequate. This
applies even to air, where the largest body of data exists.
Most information on human vanadium exposure is of occupational origin. Vanadium exposure in
industry is principally from dusts in metallurgical work and boiler-cleaning operations. Nonindustrial
exposure is from foodstuffs, with small amounts coming from water and air. Gastrointestinal absorp-
tion of vanadium is poor, but respiratory absorption may be very efficient. The percentage of vana-
dium that enters the body through the lungs is high as compared to other metals, with vanadium
from contaminated air apparently accumulating in the lungs with age. Absorbed vanadium is trans-
ported in serum lipid fractions to the highly vascular organs and is excreted in the urine and to a
lesser extent in the feces. Retained vanadium is stored mainly in fat. Keratin may be a minor storage
depot.
Oxides and salts of vanadium are respiratory irritants at levels lower than those resulting in systemic
toxicity. Clinical symptoms of acute exposure to vanadium pentoxide aerosol at 0.1 to several mg/m3
consist of inflammation of eyes and throat, persistent cough, and tightness of the chest. The onset of
symptoms is often delayed by several hours, depending on the severity of the exposure; however,
symptoms may persist for a week or more. "Green tongue" results from the oral reduction of the
pentoxide to the trioxide. Some individuals may become sensitized to vanadium so that they exhibit
dermal and more severe respiratory symptoms on subsequent exposures at the same concentrations.
Chronic inhalation of vanadium pentoxide dusts in industry has resulted hi inflammation of the
respiratory tract, chronic productive cough, wheezing, shortness of breath, and fatigue. Pneumonia's
and bronchopneumonia have also been observed. Vanadium workers are probably predisposed to sec-
ondary respiratory infections, which may account for certain chronic changes in respiratory tract
tissues. Exposure to vanadium may be detected by elevated vanadium levels in urine and depressed
cystine content of fingernails.
It is unlikely that the positive correlations between vanadium content in urban air and mortality
from various causes in two exploratory statistical studies reflect a causal relationship. Excess mortality
for causes examined hi these studies has not been reported in vanadium workers, who are exposed
to higher levels of the metal and its compounds than are community residents. In addition, the studies
were incompletely adjusted for important, probably relevant factors.
Vanadium salts may reduce serum cholesterol levels in young men and animals, and they are not very
toxic when given orally. Fifty to 200 mg/day for many weeks have been administered without pro-
duction of symptoms. Vanadium salts are highly toxic when given intravenously; lethal doses range
from 1 to 20 mg/kg in lower animals and man.
The irritative respiratory effects of vanadium oxides and salts in experimental animals (rats, mice,
and rabbits) arc, in general, similar to those reported in man. However, the higher concentrations
employed in acute animal exposures have produced marked vascular injury in the lungs and in in-
ternal organs as well. It is believed that absorption of vanadium in severe acute exposure (tens of
mg/ma) is responsible for damage to the liver, kidney, heart, and brain by causing vascular constric-
tion, congestion, and hemorrhage. Intermittent exposure (for 1 to 2 hours daily or every other day)
at lower levels (3 to 5 mg/m3 vanadium pentoxide as condensation aerosol) produces hemorrhagic
inflammation only in the lungs. In one study, however, continuous exposure at very low levels (0.005
Summary and Conclusions 2-3
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to 0.027 mg V2O6 fume/m8) produced hemorrhagic respiratory inflammation as well as vascular
congestion and hemorrhage in other internal organs.
Biochemical alterations resulting from vanadium exposure include depression of synthesis or in-
creased destruction of cystine and cysteine with an overall lowering of serum protein sulfhydryl
groups. Serum levels of ascorbic acid are lowered (perhaps because of insufficient cysteine as
gluthathione to maintain the oxidized state) such that ascorbate no longer facilitates removal of iron
from ferritin. Hemoglobin synthesis is probably, therefore, reduced, and the lowered hemoglobin lev-
els and anemia that accompany severe chronic exposure to vanadium are manifested clinically.
The reduced hepatic levels of coenzyme A following exposure to vanadium may reflect the reduced
availability of cysteinc-a precursor in the biosynthesis of coenzyme A. Coenzyme A, in turn, plays a
central role in many biosynthetic and oxidative pathways. Several other enzyme disturbances have
also been observed in animal studies. Continued investigation may be expected to elucidate the in-
terrelated biochemical and physiological effects and cellular damage resulting from vanadium ex-
posure. Whether a mutagenic, carcinogenic, or teratogenic potential exists for vanadium remains
to be determined.
Vanadium has been shown to be an essential nutrient for chicks and rats. It is essential for soil ni-
trogen-fixing microorganisms. The nutritional requirement for vanadium has not been widely studied.
It is probable that vanadium is essential to many plants and animals, but its specific role has not been
determined. Spontaneous deficiency states have not been observed.
Vanadium has been found to accumulate to very high levels in sea squirts and in agaric mushrooms,
but these are rarely eaten. No other examples of this phenomenon are known. No reports of plant
damage from vanadium have been located. Only one episode of damage to animals was reported, and
this was caused by contamination of a cow pasture with soot that had been removed from a nearby
oil-fired boiler. No information has been found on damage to materials from airborne vanadium.
However, vanadium in fuels, particularly residual fuel oils, is very corrosive to boilers and piping.
This effect is apparently due to direct action and also to catalytic oxidation of sulfur dioxide to sul-
furic acid. Fuel additives are employed to counteract this damage, but their mechanism and effect
on emissions are not well understood.
Standard fine particulate control techniques, when properly applied, accomplish good control of va-
nadium emissions. These techniques are not at present widely applied to oil combustion or ferro-
vanadium production. Because die aerosol particle size is characteristically very small, high collec-
tion efficiency is important.
2.2 CONCLUSIONS
Vanadium is widely distributed in nature in the physical and biological environment. It is usually
present in small or very small quantities in all media and living forms.
Moderate quantities of vanadium are extracted for industrial use. Present uses are in small to very
small amounts in widely distributed products, mainly metal alloys.
2-4 STAR —VANADIUM
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Vanadium is present in significant amounts in coal and oil. Some oils, particularly those from Ven-
ezuela, have a high vanadium content. Refining produces light fuels — for example, gasoline, kero-
sene, and diesel oil — that are virtually free of vanadium. The vanadium is concentrated in the
residual fractions used for large heating and power plants. Desulfurization of oil reduces the vana-
dium proportionally to the sulfur reduction.
About 17,000 megagrams (metric tons) of vanadium are emitted to the atmosphere of this country
each year. Of this, 88 percent comes from oil, 9 percent from coal, and the remainder from indus-
trial sources. Owing to the uneven distribution of high-vanadium-content oils and to seasonal heat-
ing requirements, emissions resulting from oil combustion are higher hi the northeastern United
States and in the first and last quarters of the year.
Some of the sources and distributions mentioned provide opportunity for known or possible sources
of overexposure. The natural distribution is thought to be innocuous. Unless proper precautions
arc used, workers in ore extraction, ferrovanadium production, and the cleaning of oil ash from boil-
ers suffer severe injury to the eyes and the respiratory system. Local public exposures are possible
in the vicinity of extractive plants, ferrovanadium plants, and steel recovery plants. The extent of
environmental contamination in the neighborhood of such sources operating under current condi-
tions is not known. No reports of neighborhood injury have been found, but no careful studies have
been made. The fuel consumption sources produce lower community exposure levels over much
more extensive areas. These are, of course, highest hi large cities that have multiple large sources.
Epidemiologic studies for possible injury in these circumstances are meager and inconclusive. Dis-
posal of vanadium-containing products and wastes — for example, slags, ashes, and spent cat-
alysts — has been poorly evaluated for possible problems. As noted earlier, incidence of cattle poi-
soning from improper disposal of soot has been described. Contamination of air, water, and land
may also occur from these sources.
Good particulate control measures can greatly reduce vanadium output from most sources. The
very small particle size characteristic of vanadium emissions makes complete control unlikely. Oil
combustion emissions are not ordinarily controlled. Particulate emissions from the other sources,
including incineration, are being increasingly controlled. If desulfurization continues hi use or is in-
creased, it will decrease emissions further. The high vanadium content of spent catalyst, coal ash,
and oil ash (particularly the latter) as compared to low content in ores, has produced some interest
in recycling. If reclamation develops, it would reduce the danger inherent in unsupervised disposal.
Experimental human exposure to 0.1 mg/m8 vanadium pentoxide dust for 8 hours produced mild
excess mucus production and cough beginning the following day and lasting 8 days. No general
symptoms, fever, alteration of pulmonary function, or disability were present. Higher levels of ex-
posure produced more severe and longer lasting effects. Most or all of the effects produced are
reversible, but recovery from high-level exposure may take weeks or months. Prolonged repeated
exposure is thought to produce irreversible chronic lung disease and promote infection in the
lower respiratory tract. No well-designed studies have been carried out to confirm this clinical im-
pression. Long-term air vanadium levels reported by the National Air Sampling Networks (NASN)
do not exceed 1 /*g/m3, and most are far below this level. The maximum individual concentration
recorded is 2.5 /ng/ma for 24 hours, which is far below the lowest experimental dose described
above. Information on the extent of and effects from human exposure to air vanadium concentra-
tions between 1 and 100 /*g/m8 is needed to deter mine critical exposure levels. Laboratory exposure
experiments, industrial data, and field studies would all be helpful.
Summary and Conclusions 2-5
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High-level industrial exposures of men and experimental exposure of animals, unlike those describ-
ed above, have shown evidence of complex internal injury in the body, particularly interference
with a number of enzymes, hi addition to the local respiratory tract irritation. These phenomena
have not been adequately evaluated at lower exposure levels, nor are their interrelationships and
injury potential understood. Intestinal and digestive disturbances resulting from vanadium have
not been observed, possibly because of the very low rate of absorption.
The possibility of carcinogenesis, mutagenesis, or teratogenesis as a result of vanadium has not
been investigated.
Vanadium is known to be essential to rats, chicks, and nitrogen-fixing bacteria, and it may be
essential to many other living forms as well. Spontaneous deficiencies have not been reported. Al-
though there are no available data showing essentiality in man, animal data indicate that vanadium
is probably an essential element hi human nutrition.
Vanadium injury to animals or plants is rare or unknown. When present in fuel oils, it produces
considerable damage to boilers and other metal equipment.
Available data indicate hi general that vanadium in the concentrations found hi air, food, and water
is not a health hazard. A significant research effort to evaluate vanadium distribution hi the en-
vironment and its potential threat to health therefore does not appear to be warranted at this time.
Particular potential problem areas, however, should be monitored for environmental vanadium, and
the health status of persons residing or working in such areas should also be followed if evidence
of environmental contamination appears.
2-6 STAR —VANADIUM
-------
3. CHEMICAL AND PHYSICAL PROPERTIES
Pure vanadium (V) is a bright white, soft, ductile metal having the following properties: atomic
weight 50.942, atomic number 23, melting point 1890° ± 10 degrees Celsius CO, boiling point
3380°C at 760 millimeters of mercury (mm Hg), specific gravity 6.11 at 18.7°C, and valence 0, 2+,
3+,4-f-, or 5+. Placed in a simple aerated saline solution, vanadium has a high resistance to cor-
rosion — at least as high as stainless steel and probably as high as titanium. Vanadium is inferior
to stainless steel in its resistance to corrosion in concentrated alkaline solutions, but resistance is
good in dilute solutions of alkalies, sulfuric acid, and hydrochloric acid. Pure vanadium resists
oxidation up to about 690°C, but the oxidation rate of the metal is very rapid above that tempera-
ture. The melting point of vanadium is at least 400 °C higher than the melting point of most steels.
Some physical properties of important vanadium compounds are listed in Table 3.1.
Table 3.1. SOME PHYSICAL PROPERTIES OF IMPORTANT
VANADIUM COMPOUNDS1
Compound
Vanadium """
pentoxide
Vanadium
trioxide
Sodium
metavanadate
Vanadium
tetrachlorlde
Vanadium
oxychlorlde
Ammonium
vanadate
Melting
point, °C
—
690
1970
630
28 ±2
No data
200°
Boiling
point, °C
_. - ._ -
1750
No data
No data
148.5
126.7
No data
Solubility In water, g/100 cm3
Cold
— - - -
0.8
Slightly
soluble
21.1
Decomposes
Decomposes
0.52
Hot
• - —
No data
Soluble
38.8
No data
No data
6.95°
"Decomposes.
Vanadium exists in a number of valence states in a large variety of compounds. In general, the
halides are hygroscopic and hydrolyze in water. Both the halides and oxyhalides are volatile — as
indicated by their low boiling point (Table 3.2). Several oxides exist; V2O5 is sold commercially
and is formed when the vanadium oxides, chlorides, or oxychlorides are heated in air. The V2OB
dissociates into VO2 and oxygen at temperatures only slightly above its melting point (690°Q.
Numerous vanadates can be formed. Also, a variety of vanadium sulfates have been prepared.
Chemical and Physical Properties
3-1
-------
Table 3.2. BOILING POINTS OP VANADIUM
HALIDES AND OXYHALIDES1
Compound
Vanadium tetrachloride
Vanadium ox/chloride
Vanadium oxytrichloride
Vanadium trlfluorlde
Vanadium oxytrlfluoride
Vanadium pentafluoride
Formula
VCI4
VOC1
VOC1a
VF8
VOF8
VFB
Boiling point, °C
148.57a*nm
127
126.7
Sublimes
480
111.273>mm
3.1 REFERENCE FOR SECTION 3
1. CRC Handbook of Chemistry and Physics, 51st Ed. Weast, R. C. (ed.). Cleveland, Chemical Rubber Com-
pany. 1970.
3-2
STAR — VANADIUM
-------
4. SAMPLING, PREPARATION, AND ANALYSIS
4.1 INTRODUCTION
This section reviews the various analytical techniques that have been used to measure vanadium. It
is intended to be representative of recent trends in such analytical methodology. Some general com-
ments will also be given on quantitative aspects of procedures, which are related to accuracy. Ath-
anassiadis1 has collected relevant information on analytical methods for vanadium that will not be
repeated here.
The importance of accuracy in the measurement of pollution is apparent when one attempts to com-
pare analytical results among techniques and laboratories. Accuracy is critical if analyses are to be
interchangeable among laboratories. Interchangeability of results is essential in work concerned
with establishing threshold limits of pollutants, defining background concentrations, and defining
degrees of toxicity.
Few analytical procedures applied to trace metals in pollution materials have been subjected to
thorough or even adequate error analysis to permit rigorous definition of limits of accuracy. Al-
though the American Public Health Association publication Methods of Air Sampling and Analyst^
has a section entitled "Precision and Accuracy", for every method described, without exception, ac-
curacy is not delineated — precision is covered; accuracy is not.
Rigorously defined, accuracy requires not only that all sources of significant systematic error be
identified and quantitated, but also that the analytical system be in statistical control, as defined
by Natrella.3 Reasonable quantitative validation after the use of well-established procedures can re-
sult in useful comparison of analytical results among techniques and also among laboratories.
The more common methods for quantitative validation available to the analyst are listed below in
approximate order of preference (within one or two rank positions); that is, Method 1 is least
subject to inaccuracies, and Method 7 is most subject to inaccuracies.
1. Use of standard reference materials certified by a recognized standardizing agency or by in-
dustrial suppliers .of specific materials.
2. Cooperative analyses involving several laboratories and several techniques (round robin).
4-1
-------
3. Absolute analyses based on theoretical mathematical relations.
4. Method of standard additions using solutions.
5. Synthesized standards using solutions.
6. Same as Method 4, but using blended powders.
7. Same as Method 5, but using blended powders.
In addition to these seven, a family of radiochemical techniques' is in use — for example, the iso-
tope dilution method. Although these methods arc not truly quantitation procedures, they are im-
portant in this context because they provide highly useful means for minimizing some analytical
inaccuracies.
Lack of certified standard samples for trace metals in pollution materials precludes the use of
Method 1, standard reference materials, in many cases. The National Bureau of Standards either
has issued or is planning to prepare some biological materials certified for trace metal content, but
vanadium is not included. Furthermore, the availability and long-term preservation of standards ap-
plicable to the broad range of pollution samples will be very limited in the near future. Another
problem in calibration lies in obtaining a true blank wherein the component to be measured is
absent.
Method 2, cooperative analyses, requires a great deal of time, effort, and expense. This approach
provides an opportunity to establish error limits under more realistic conditions than is feasible in a
single laboratory. This cooperative work is not conducted primarily to establish accuracy. The round
robin approach is more often conducted to establish uniform operating practices in several labora-
tories and to minimize the bias between laboratories using specified analytical procedures. In
most cooperative work, the accuracy of the method is presumed to be established before distribu-
tion of samples to the cooperating laboratories. Nevertheless, a well-conducted round robin can re-
veal sources of analytical bias that bear on accuracy.
Method 3, absolute theoretical analyses, is exemplified by analyses based on the proved applicability
of such theoretical relations as Beer's Law in colorimetry or atomic absorption, the Nernst equa-
tion in electrochemical procedures, and the Ilkovic equation in polarography. Analytical procedures
that follow such relations are generally more amenable to good quantitation than completely em-
pirical methods, provided that interferences are carefully defined.
The method of standard additions, Method 4, is one of the more powerful techniques for minimiz-
ing systematic errors in analysis. Shatkay5-" has presented mathematical analyses of the method of
standard additions and of a similar technique, the method of successive dilutions, including a
discussion of the assumptions and limitations of these methods that are often overlooked in their
application.
Methods 4 through 7 involve synthesis of standards by blending either solutions or powders. Stand-
ards made from solutions are preferred over mixtures of solids. The achievable accuracy of this
procedure depends on the close simulation of the standards to the samples. The more accurately
the composition of the sample is known, the better its simulated composition can be. Synthesized
solid standards arc widely used, especially in emission spectroscopy and spark-source mass spec-
troscopy. This technique is subject to uncertainties that are exceedingly difficult to resolve. A
major problem with solid materials not previously treated by dissolution is that the physical forms
of the standard materials are not always identical with the form of the specific chemical element
4-2 STAR —VANADIUM
-------
sought in the unknown sample. Apparently, much greater discrepancies can occur because of chemi-
cal differences between standards and samples. Diluting the sample in a uniform matrix can reduce
some of the matrix (accompanying materials) effects. In spite of the highly utilitarian nature of these
dilution methods, it is questionable whether they can be classified as quantitative without consider-
able supporting evidence as to their accuracy and their sensitivity to variations in sample matrix.
Any cursory survey of published analytical techniques will reveal that most offer only minimal
evidence for inferring accuracy. Because this problem will undoubtedly persist, it is especially im-
portant for analysts and researchers concerned with the biological effects of atmospheric pollutants
to be aware of the problems of proving accuracy and thus avoid some of the pitfalls in regard to
quantitation. This is especially true in the interim before standardized procedures can be validated.
Inadequate control of blanks might be the most common cause of systematic errors when dealing
with nanogram concentrations. Robertson7 and other investigators have surveyed trace metal concen-
trations in glass and plastic containment materials, organic and inorganic reagents, wiping tissues,
and other materials. Vanadium has not been detected hi any of the commonly used reagents or plas-
tic containment materials by the most sensitive detection techniques. Thus, at present levels of de-
tectability, vanadium appears to be one of the least troublesome elements with respect to contami-
nation. However, vanadium is also among the least concentrated elements hi pollution materials.
In the interest of accuracy, therefore, careful control must be exercised to avoid contamination
from unsuspected sources.
4.2 ENVIRONMENTAL SAMPLES
4.2.1. Air
4,2.1.1. Sampling Particulate Matter—Among the major sampling techniques available for atmos-
pheric particulates are absorption by liquid impinger, electrostatic precipitation, and filtration. The
absorption method has pronounced drawbacks. Absorption may be far from complete, and many par-
ticulates, especially those of smaller diameters, may not be wetted and may pass out unabsorbed.
The greatest disadvantages of electrostatic precipitation are the need for electric power, which may
not always be available, the potential for formation of noxious gases, and the complexity and cost
of the equipment. In more recent years, filtration methods have been used because of ease of opera-
tion and the availability of a variety of pure filtering materials. The filtering materials must be
chosen with consideration for trace metal analysis of air samples, since elemental impurities may
influence analytical results and complicate sample preparation. A typical glass-fiber filter, such as
the type used routinely in the high-volume samplers, contains about 0.03 fig/cm2 of vanadium as
determined by atomic absorption spectroscopy8 and 0.025 fig/cm? as determined by emission spec-
troscopy.0 Because the blank value for any element may vary considerably with the batch, the filter
blanks should be determined regularly. For sampling by NASN, flash-fired, glass-fiber filters were
selected for low and uniform background.10 Ashless paper filters and organic membrane filters that
contain very small amounts of vanadium are available. Nevertheless, the size and nature of glass-
fiber filters have made it possible to use a high-volume sampler and sample at an airflow rate of
1.5 to 1.6 m8 per minute. When operating for 24 hours at this sampling rate, an adequate sample
will be obtained even in an atmosphere that has little suspended particulate matter.
Although the method of sampling is important, it is even more important that the sample collected
Sampling, Preparation, and Analysis 4-3
-------
be representative of the original atmosphere. Since some of the vanadium halides have low boiling
points, it is likely that there is some vanadium in the atmosphere in vapor form. Any sampling, there-
fore, should include atmospheric vapors.
4.2.1.2. Sample Preparation—Sample preparation affects both economy and accuracy of analyses.
The ideal approach is direct analysis with no pretreatment at all, as carried out in some of the ana-
lytical procedures to be discussed. However, direct analysis is not always possible and might even be
undesirable because of the difficulty in compensating for matrix effects through synthesis of stand-
ards.
Most analyses of participate matter collected on paper filters involve some sort of sample prepara-
tion, usually mineralization through ashing of the sample. This can be accomplished in a muffle
furnace11-" at temperatures between 400" and 650"C; by digesting in hot acid mixtures, such as
nitric and perchloric acids;14-1" or by ashing in an electrically excited oxygen atmosphere with a low-
tempcraturc asher (LTA).17-"0 The primary concerns in the ashing operations are the loss of metals
by volatilization, metal contamination, and convenience of the procedure.
In recent years, the LTA method has gained preeminence over other ashing procedures for organic
materials of all types."1— It is superior from the standpoints of minimal concentration and ease of
operation. Data reported for elements whose volatilities are comparable with those of vanadium
and vanadium compounds suggest that no significant loss of vanadium occurs under normal con-
ditions using the LTA.
4.2.1.3 Analysis by Atomic Absorption—The atomic absorption technique, although basically a
single-element method, is advantageous because it is available, simple, and inexpensive. Vanadium
forms thermally stable oxides that are only partially dissociated in the flame. Therefore, the hottest
flame in common use, the nitrous oxide-acetylene flame, is used for routine measurements. The
detection limit is 0.01 /ig/m3 for vanadium using the absorption mode, assuming a 2000-m3 ail
sample.20 Using the more sensitive emission mode, a detection limit of 0.005 fig/m3 would be ex-
pected.23 Although the lower detection limit is achieved in the emission mode, the absorption mode
has been applied more often in routine analysis.
The elements that cause interferences are aluminum and iron.24 Aluminum can be controlled by
adding an excess of aluminum (200 /xg/ml) to the samples and standards. The iron interference is
negligible in concentrations found in ambient air. The estimated accuracy of the method is ±4.5
percent.'-"
In an application of atomic absorption analysis to airborne particulates, Kneip et al.19 reported
vanadium concentrations of 0.115 /xg/m3 in a nonurban area of New York, and 1.46 /ig/m3 hi the
Bronx area. New York City. The detection limit for vanadium was reported as 0.094 /tig/m3 for a
total air volume of 5000 m3, which is equivalent to a relative detection limit of about 10 fig/ml. In
comparison, Morgan and Roman18 reported a detection limit for vanadium hi airborne particles
to be 0.0018 /tg/m3 for a total air volume of 500 m3 in 8.9 ml of solvent, or about 0.1 /ug/ml.
Atomic absorption spectroscopy25 has been used to measure trace levels of vanadium in the atmos-
phere of eastern Massachusetts.
Flamcless atomic absorption techniques that have received increasing attention are the tantalum
ribbon atomizer;8-26-28 heated graphite atomizer,2' carbon rod atomizer,30 and graphite furnace
4-4 STAR — VANADIUM
-------
technique.41-32 Advantages of these techniques are excellent sensitivity at nanogram and picogram
levels and the need for an extremely small amount of sample solution — 10 microliters or less for
a single measurement. Improvement of sensitivity over conventional flame mode by two or three
orders of magnitude is not unusual.
Quickert et al.32 and Hwang8 indicate that the use of the conventional flame mode of atomic
absorption spectroscopy is not sufficiently sensitive to measure many of the elements in atmos-
pheric paniculate matter, given a collection volume of 2000 m8 through a high-volume air sampler
and final elemental concentrations of 0.05 /ig/ml or less in solution. In measuring vanadium hi air-
borne paniculate matter using the flameless mode, Quickert et al.32 found the sensitivity to be
0.0004 ftg/m3; with the flame mode, the same test sample showed a sensitivity of 0.025 /tg/m3.
Atomic absorption analysis for metals is limited to those elements for which hollow cathode lamps
are available. The inability to measure more than one element at a time and the requirement that
the sample be in solution are more severe limitations. Because air pollution is the result of high-
temperature combustion, some of the paniculate matter may be quite refractory and difficult to
dissolve for atomic absorption analysis,
4.2.1.4 Analysis by Colorimetry — A variety of colorimetric methods are available for detection
of vanadium. They are generally applicable to pollution materials with the use of suitable masking
agents and extraction procedures to separate vanadium from interfering species. A number of
colorimetric reagents, not necessarily applied to pollution materials, are listed in Table 4.1.884*
A very simple, inexpensive, and specific method for determination of vanadium in air is the ring-
oven technique; it uses the reagents salicylideneanthranilic acid49 or 8-hydroxyquinoline48 with esti-
mation by eye.
4.2.1.5. Analysis by Electrometric Methods — Methods based on electrolytic phenomena are
highly diverse in application and include at least 13 distinct techniques. These methods have found
very limited use in the determination of vanadium hi pollution materials.
Currently, the area of most active investigation is that of anode stripping voltametry (ASV), which
provides the advantages of preconcentration, reasonably good specificity, sensitivity, and simplicity.
However, vanadium is one of the more difficult elements to determine by ASV because of the lack
of a suitable reversible reaction. Therefore, detection of vanadium hi the materials of interest by
this technique has not yet been reported.
A polarographic method has been described for determination of vanadium in the air of the working
environment in the alloy industry.54 The method is sensitive to 1.5 ftg of vanadium pentoxide per
ml.
Vanadium has also been detected by other electrometric techniques, including potentiometry,8*
amperometry,00-" and coulometry.88-8*
4.2.1.6. Analysis by Electron Optics — Tools for analysis by electron optics include the electron
microscope, the electron microprobe, and X-ray diffraction. These tools, supplemented by light
Sampling, Preparation, and Analysis 4-5
-------
Table 4.1. COLORIMETRIC REAGENTS FOR DETECTING VANADIUM
Reagent
5-Am i no-3-(3-ch loro-2-hyd roxy-5-
nitrophenylazo)-4-hydroxynaphthalene-
2,7-disulfonic acid (gallion)
5-Amino-4-hydroxy-3-(2-hydroxy-3,5-
dinitrophenylazo)naphthalene-2,7-
disulfonic acid (picraminazo N)
Unsaturated N-arylhydroxyamic acids"
(23 complexes studied)
Cyclo-tris-7-(1-azo-8-hydroxy)-
naphthalene-3,6-disulfonic acid
(calichrome)
Dlaminobenzidine
8-Hydroxyquinoline
Naphthalene-2,3-diol (2,3-dihydroxy-
naphthalene)
m-Nitro-N-phenylbenzoylhydroxyamic
acid
N-Phenylbenzoylhydroxyamic acid
Phenylhydrazine-p-sulfomc acidb
N-Phenyl-3-styrylaorylohydroxyamic
acid
2,6-Pyridinedicarboxylic acid
4-(2-Pyridylazo) resorclnol
Salicylideneanthranilic acid
N-o-Tolylbenzoylhydroxyamic acid
Tungstate
Reference
33
33
34
37
38
39-43
44
45
34
46
34
47
48
49
50
51-53
Remarks
6 as 8,700
£= 12,400
Nine complexes had e =1,500
Beer's Law followed from
0.2—11 fjug/g
e= 4,650
Beer's Law followed from 0.7 to
8.4 /u,g/g; sens. = 0.0068 /ng/cm2
Beer's Law followed up to
5 mg V/50 ml of solution
Can be determined between
0.1 and 3 //,g
Sensitivity, 5 fig V2Or,/5 ml
oSalicylhydroxyamlc
^Vanadium catalyzes the oxidation of phenylhydrazine-p-sulfonic acid by sodium chlorate. A diazonium salt Is
produced that couples with 1-naphthylamlne to form aaazo dye.
The 8-hydroxyqdinoline procedure80 was adapted to air-filtered materials and specified as a
tentative method by the Intersociety Committee on Methods of Air Sampling and Analysis. The
8-hydroxyquinoline reagent was also applied after extraction of vanadium with .-benzoin oxime
in chloroform." This reagent has been used to measure levels of vanadium pollution in the air of
Helsinki, Finland,40 and at various Japanese manufacturing sites.41
The salicylhydroxyamic acid reagent has been used in measurement of air in Germany.35-36
4-6 STAR — VANADIUM
-------
microscopy, allow characterization beyond elemental analysis and into the area of morphologic,
compound, and crystallographic identification, as described by Rhodes60 and Blosser.61 Although
no vanadium compounds have yet been identified with these techniques, vanadium distributions
within paniculate matter samples from the Washington, D. C., area have been reported.61
4.2.1.7. Analysis by Emission Spectroscopy — Emission spectrochemical methods are differentiated
on the basis of method of sample preparation, method of quantitation, and method of exciting the
atomic spectra. As with instrumental methods of analysis in general, a wide variety of experimental
procedures have been developed that represent trade-offs between simplicity and economy on the
one hand, and precision and accuracy on the other. One of the simplest methods of analyzing
filtered air samples by emission spectroscopy requires no pretreatment of the sample at all.82
Although the repeatability of the method is adequate for monitoring concentration trends of some
elements, its accuracy is unknown because calibration standards consisted of dried solutions of the
various elements on filter paper. Quantitation of the method using air-filtered specimens analyzed
by other means could also be used. Vanadium was not reported by this method.
A procedure has been reported for detecting vanadium and nine other elements in suspended par-
ticulatc matter."3 In this method, the chemical forms of the particles were destroyed by ashing and
then fusing the ash with lithium tetraborate. The ground fusion material was then pelleted with
graphite and subjected to a spark discharge. This technique tended to minimize inaccuracies caused
by differences in chemical form between unknown samples and standards, assuming that the com-
position of the major elements in the standards was approximately the same as that in the samples.
The mean vanadium concentration of 270 samples taken in metropolitan New York air was 0.17
/ttg/m3.
Possibly the most often used emission spectrometric procedure for detection of metals hi airborne
paniculate matter and in biological materials is a variation of the so-called universal method of
analysis.64 Many commercial laboratories use this general approach because it is economical. There
are many variations of this approach, which basically involves diluting the ashed sample in a rela-
tively pure powdered material in a sample: diluent ratio of about 1:10. Typical diluents are graphite,
lithium carbonate, and lithium fluoride. The dilution reduces all samples to a relatively common
matrix and therefore reduces some systematic errors caused by variation in sample composition.
However, a fundamental uncertainty remains concerning physical forms of the various chemical
species. Because it is not possible to place limits on this source of error, these methods require
quantitative validation by other means.
The emitted light from a sample that has undergone the prescribed processing can be received
either by a photographic plate00'60 or film, or by a photomultiplier tube.10-™ In the first method,
the plate is developed, and the spectral lines are investigated. The darkness of the lines is measured,
and the concentration of the element being analyzed is calculated. When measured by this tech-
nique, vanadium concentrations in Osaka, Japan,65 ranged from 0.05 to 0.55 /ng/m3 In another
study of 11 Japanese cities,07 the average concentrations ranged from 0.014 to 0.269 ftg/m8.67
Tabor and Warren68 measured 17 metals hi 20 U. S. communities by this technique. They
reported that a large percentage of samples contained less than the minimum detectable amount
of the metals, and they pointed out the need for a more sensitive method. Tani67 reported that the
photographic technique is time-consuming and not desirable for routine measurements. The data
obtained in recent years by NASN10-70 have been acquired through the use of a direct-reading
emission spectrometer. For 1970 NASN samples analyzed in 1972, duplicate measurements of
vanadium in 32 cities gave an average concentration of 0.096 /tig/m3, with a relative standard
deviation of 9.3 percent.70 Matrix effects from the widely varying samples were reduced by use
of a 2 percent lithium chloride buffer and an indium internal standard. The detection limit reported
Sampling, Preparation, and Analysis 4-7
-------
for vanadium*' is 0.01 /ig/m8 by atomic absorption spectroscopy and 0.003 fig/m3 by emission
spectrography.
Disadvantages in the use of emission spectroscopy for metals analysis include the complicated
methodology required to obtain reliable data and the detection limit, which prohibits analysis for
low-level concentrations of some metals.20 In addition, the instrument is expensive to buy and re-
quires highly trained technical personnel to operate.20 However, when samples are to be analyzed
routinely for more than six metals, the emission spectrograph saves tune and effort.
4.2.1.8. Analysis by Fluorimetry — For determination of vanadium in solution, a simple method
has been reported that measures the fluorescence intensity produced on reaction with benzoic acid
in the presence of zinc amalgam.71 The fluorescence intensity was a linear function of concentra-
tion for 0.0005 to 0.4 fig/ml of vanadium- Most common ions, except Fe^- and Ti4+, did not
interfere. Further studies are needed to devise better procedures for removal of the interferences.
No practical application to vanadium measurement was reported.
4.2.1.9 Analysis by Gas Chromatography — Hyperpressure gas-phase chromatographic separa-
tions of organic vanadium compounds and their later detection are emerging from the develop-
mental stage.72-73 The method has found practical application in detection of trace metals in bio-
logical materials,74 but no practical application has been reported for vanadium.
4.2.1.10. Analysis by Neutron Activation — Basically, neutron-activation analysis involves expos-
ing a sample to a source of neutrons and detecting nuclear radiation emitted by the isotope of the
element made radioactive by absorbing a neutron. For airborne paniculate analysis, it is essential
that samples be collected on filters low in trace elements. Filters found suitable for sampling
include Whatman,80 cellulose fiber paper,76 millipore filters,78 polystyrene filters,77 membrane fil-
ters,78 and ashless filter paper.
Radiation detection and measurement are by gamma-ray spectrometry, using either a thallium-
activated sodium iodide detector, NaI(Tl), or a lithium-drifted germanium detector, Ge(Li). In
samples that emit few gamma rays of different energies, the Nal(Tl) detector is sufficient for
quantitative determinations. This detector is relatively inexpensive ($5,000 to $6,000) and can be
operated at room temperature with 1.5 to 2 times the counting efficiency of the Ge(Li) detector.79
Resolution, however, is poor. In comparison, the Ge(Li) detector has excellent resolution, and
there are few effects of other nuclides present. However, its counting efficiency is low, it is costly
(more than $25,000),79 and it requires constant cooling.
Neutron activation can be considered either a destructive or nondestructive technique, depending
on whether the sample can be counted after irradiation and cooling or whether chemical separa-
tion of isotopes is required (because of overlapping peaks) before the sample is counted. The main
objective is isolation of the peaks. In some cases, separation is attempted before irradiation, but for
purposes of trace-element analysis in air pollution, the possibility of element losses prohibits using
such a measure.
In neutron activation of vanadium, the radioactive species is vanadium-52, with a half-life of 3.77
minutes and a gamma energy of 1.434 million electron volts80 — a so-called short-lived isotope.
The main interference in the analysis of vanadium is aluminum-28, which has a half-life of 2.27
4-8 STAR —VANADIUM
-------
minutes and is found in a ratio of 50'or more to 1 of vanadium in airborne particulates.76 Bando
and Imahashi76 estimated the vanadium in dustfall deposits in two Japanese cities using a NaI(Tl)
detector; they overcame the aluminum interference by extracting, by means of chloroform, the
vanadium from the irradiated sample as a 2-methyl-oxime complex. The extract was subjected to
gamma ray spectrometry, the absorbance was measured, and the vanadium was estimated by seeking
the chemical yield by photometry. The time required for analysis was 10 minutes, and the average
chemical yield was 95 percent. Concentrations of vanadium found in the two cities using this method
ranged from 0.13 to 0.98 jtig/m3.
Following irradiation of samples from northwest Indiana and counting with a Ge(Li) detector after
a 3-minute decay period, Dams et al.77 found the minimum concentration for vanadium in urban
air to be 0.002 /*g/m3 as compared to 0.0032 /ttg/m3 using emission spectrography. The sensi-
tivities obtained for nonurban samples were better than those obtained for urban samples with
either method. Rancitelli et al.81 studied air samples from 14 cities by neutron-activation analysis
using a 10-minutc decay period to remove the major interference (aluminum-28) before counting
on a Ge(Li) spectrometer, and compared the data with samples analyzed by X-ray fluorescence.
The authors report their accuracy and precision for a single determination to be better than 10 per-
cent for most elements in air filters. Using the Ge(Li) detector, Martens et al.78 found vanadium
concentrations in San Francisco to range from 0.0027 to 0.012 fig/m3. The effectiveness of this
method has also been demonstrated in studies of the Liverraore Valley, California, and of Niles,
Michigan.82-88
Neutron-activation analysis is most important in air pollution studies because of its high sensitivity
for many elements and the fact that 20 or more elements can be observed in a single sample.
However, this technique is inadequate for determining lead or phosphorus.84 In addition, to realize
the full capability of measuring 33 elements, total cooling periods of up to 30 days are required.77
This introduces a delay between receiving the sample and obtaining a complete elemental analysis.
4.2.1JL Analysis by Spark-Source Mass Spectrometry — The spark-source mass spectrometer has
been used for multielement analysis of both airborne particles and biological samples.12-14-17 The
sample preparation in all cases consisted of ashing the sample and pelletizing the ash with graphite
to achieve the necessary electric conductivity.
A more recent innovation is the use of electric detection with the spark-source mass spectrometer.
This new method promises to simplify the technique and to improve the detection repeatability.85
By the mass-spectrometric technique, the vanadium concentration in New York City air was deter-
mined11 to be 1.9 jug/m3. The particulate sample was collected on nitrocellulose filters that were
ashed at 450°C and pelleted with graphite. Relative sensitivity factors and metal losses in the ashing
step were not taken into account.
4.2.1.12. Analysis by X-Ray Fluorescence — X-Ray fluorescence is an attractive method for analy-
sis of air pollution particulate samples for a number of reasons. The technique is nondestructive
and the sample is thus retained for further analysis. Detectability is fairly uniform across the peri-
odic table; all elements from atomic number 11 upward can be analyzed, and 10 or 20 elements
can be analyzed simultaneously with commercially available equipment.
Sampling, Preparation, and Analysis 4-9
-------
Disadvantages of the X-ray fluorescence technique include the high initial cost — ($60,000 to $200,-
000) — of a fully automatic, computerized instrument. Cost can be cut in half if samples and data
are handled manually. There are problems in preparing calibration standards representative of
actual samples. Interelement effects may lead to complications.8 Errors as large as a factor of 2
can be introduced into the X-ray analytical result if a significant number of the particles collected
are larger than a few micrometers.86 At this time, the only solution to this problem is use of size-
fractionated samples.
The X-ray measurements for air pollution samples reported in the literature were obtained from
the use of ehher energy dispersion or wave length dispersion instruments. Several types of excitation
sources have been evaluated:
• Lithum-drifted silicon [Si(Li)] detector with radioisotopes81'87 or low-powered X-ray tube88
and fluorescer excitation for energy dispersion.80'90
• Radioisotope-fluorescer assembly with a solid-state detector.91
• Radioisotopes and a solid-state detector.92
• Proton03 or alpha particle04 excitation.
• Crystal spectrometers with X-ray tube excitation for wavelength dispersion9-93-97
Cooper0" has compared various methods of exciting samples for subsequent X-ray analysis.
Filter materials used to collect paniculate samples for analysis by X-ray must be as pure as possible
and, with the paniculate, constitute a sample that is easily penetrated by X-rays so that no matrix
effect will result. Certain types of millipore filters and Whatman filter paper have been found to
satisfy these requirements.
Birks et al.° used a crystal diffraction spectrometer and an analysis time of 100 seconds per ele-
ment in the determination of 12 elements from stationary source sites. The detection limit for
vanadium on Whatman 41 filters was reported as 0.029 fig/cm2, which corresponds to a detection
limit of 0.003 /xg/m3 for a 24-hour sampling period. Extensive measurements of suspended par-
ticulate matter were made at 38 stations in Texas by Rhodes et al.8T through the use of energy-
dispersion instrumentation consisting of three radioisotope sources for excitation and a Si(Li)
detector to receive the signal. Samples collected on Whatman 41 filters were analyzed for 900
seconds, and concentrations for 15 elements were given. Low values (less than 0.008 /*g/m3) were
reported for vanadium. For paniculate samples collected on 0.8 fim millipore filters and analyzed
for 900 seconds using an energy-dispersive system consisting of an X-ray tube90 with three
separate secondary fluorescers, Goulding and Jaklevic give the detection limit for vanadium as
0.006 /xg/m3. The authors mention that the sensitivity would be improved if the system were
optimized for each element by filtering the X-rays.
Future experimental studies of X-ray fluorescence are needed to overcome the inadequacies of this
technique and extend the application.
4.2.2. Water
Many laboratories use automated sampling techniques to determine metals in water by direct
aspiration. For trace-metals analysis, however, the direct aspiration method does not generally have
the required sensitivity; concentration of the metals is required.
4-10 STAR —VANADIUM
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One such method is based on complexing the metal with ammonium pyrrolidine dithiocarbamate
and extracting the complex with metyl isobutyl ketone (MIBK). The MIBK phase is then separ-
ated and aspirated into the flame of an atomic absorption spectrophotometer." Although Goulden
et al." report no values for vanadium using this technique, further studies could show it to be
valuable. Microgram quantities of vanadium in lake water (5 /ng/liter) have been detected by atomic
absorption after extraction with 5,7-dichloro-8-hydroxyquinoline.100 The flameless atomic absorp-
tion method has also been used for trace metals in water.28
A method with a sensitivity of 0.1 to 8 yxg/liter has been developed for analysis of vanadium in water
by measuring the catalytic effect it exerts on the rate of oxidation of gallic acid by persulfate in
acid solution.101 The extent of oxidation of gallic acid is proportional to the existing concentration
of vanadium. Vanadium is determined by measuring the absorbance of the sample at 415 nano-
meters and comparing it with standard solutions. Halide interference is reduced by dilution or com-
plexation with mercuric ion. The minimum detectable concentration is 0.025 fig.
Neutron-activation analysis102 has been applied to the determination of vanadium (1 to 10 /tg/liter)
in natural waters by collecting vanadium on an ion-exchange resin and later irradiating the nitric
acid eluate.
The previous section concerning methods for analysis of air for vanadium suggests that techniques
such as colorimetry, fluorimetry, and emission spectroscopy should provide further means of meas-
uring vanadium in water.
4.2.3. Soil
4.2.3.1 Soil Sampling — The method of sampling used in determining the vanadium content of
the soil, as with any other substance, is critical if an accurate appraisal is to be obtained. Random
sampling noting the type of rock or the composition of the soil is of extreme importance because
the vanadium content will vary according to the sample's makeup.108-10*
4.2.3.2. Analysis Procedures — Spectrochemical analysis, atomic absorption, and neutron activa-
tion have been the chief methods used in analyzing the soil for its vanadium content. The sensi-
tivity of the spectrographic method is 3 /tg/g; however, different analysts using the same material
have not always achieved the same results.105 Kemp and Smales105 have shown that through neu-
tron activation, it is much easier to duplicate results (Table 4.2). These three methods of analysis
have been discussed hi detail earlier. Sample preparation for soil analysis, however, differs from
the methods described for other media.
Spectrochemical analysis (emission spectroscopy) involves preparation of the samples by digestion
and then chemical pretreatment. The mixture thus prepared is used for arcing.109 During prepara-
tion of samples, extreme caution is necessary to prevent trace-element contamination. The proce-
dure as outlined by Shimp et al.loa is precise to ±10 percent. Preventing contamination of the ele-
ment being analyzed is of utmost importance if analysis is to be accurate.
Sampling, Preparation, and Analysis 4-11
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Table 4.2. ANALYTICAL RESULTS FOR "STANDARD" ROCKS105
0*9/9)
"Standard"
rock
G-1
W-1
Range of other
workers
8-38
120-340
"Recommended"
value
18
240
90%
confidence
interval
21 ±7
255 ± 55
This work
Individual
determinations
13.4, 13.2,
12.9, 13.1,
13.0, 13.0,
13.0, 12.7
250, 244, '
244, 244,
247, 244
Average
13
246
Atomic absorption analysis requires ashing and dissolving of samples. The flameless furnace-vapor-
ization technique is best for solid samples.107 The atomic absorption method detailed by Goeke108
for detecting vanadium in ores has a sensitivity of 0.2 ppm for 1 percent absorption.
Neutron activation has been used to determine the content of vanadium in rocks and meteorites.108
As indicated previously, Kemp and Smales105 have shown that, through use of neutron activation,
it is possible to come closer to duplicating results. They indicate that molybdenum and technetium
are the only interfering elements, and then only when the vanadium content of the sample is low.
The sensitivity of the methods for rocks and meteorites is not indicated; however, a vanadium con-
tent of less than 0.2 ftg/g average is listed in a table showing the vanadium content of meteorites.
4.3 BIOLOGICAL MATERIALS
4.3.1. Sampling
Studies arc underway for collecting biopsy and autopsy human tissue specimens for the purpose
of systematically determining baseline pollutant levels in different organs as a function of age, race,
smoking status, residence, and occupation.109-110 This program is an effort to determine the temporal
and geographic patterns for selected populations to enable assessment of pollutant body burdens
and to attempt to correlate these burdens with statistically observed disease patterns. These epi-
demiologic studies are based on a minimum of 1000 individuals in each area. Short- and long-term
health indicators are employed, such as frequency and aggravation of asthma attacks and other
evidence of illness or mortality that can be linked to pollutant exposures.110'111
Tissue sampling includes several steps: types of tissues (part of anatomy), size and amount, con-
tainment, transport, preparation for analysis, and short- or long-term storage.. Each step is part
of the overall analytical process and may affect the integrity of the trace elements in the sample.112
Written sampling protocols are available to ensure uniformity in collection by various field samp-
ling stations.ll0-"3-114
Easily collected tissue specimens such as blood, urine, and feces primarily reflect short-term expo-
4.12 STAR — VANADIUM
-------
sure changes and are incomplete indicators of total residue of vanadium in the body. These types
of samples are valuable in studying biological residence times of vanadium in the body.
In humans, vanadium accumulates in the lung. It also has an affinity for fatty tissues, bone, and
keratinous tissues such as hair and skin. The usefulness of hair as an indicator of both short-term
acute exposure and long-term chronic exposures to vanadium and other trace metals has been or
is being studied by several investigators.109-111'115-116 Hair has been established as a useful indicator
of acute exposures to mercury, lead, cadmium, and vanadium. At vanadium levels normally found
in urban and industrial areas, hair is of marginal value as an indicator of exposure or body burden
of vanadium.
Under the EPA CHESS (Community Health and Environmental Surveillance System) program,
arrangements are made with pathology departments of local hospitals for collecting autopsy and
biopsy tissues. Sampling protocols, which have been prepared for pathologists, include procedures
for collecting 19 different tissues. Surgical tools to be used are specified to avoid contamination
during excising. There is also a questionnaire to be completed for each set of autopsy tissues to
provide supporting information such as medical, occupational, and smoking history; unusual dietary
habits; medicinal intake; cause of death; and other information useful in assessing possible sources
of intake of a trace metal. Specific instructions are provided for container design, labeling, ship-
ping, and storage for tissue specimens.
Before a tissue specimen is contained, preserved, and stored, a decision must be made on whether
to homogenize, lyophilize, or otherwise preserve a whole organ or to select a particular area or
part of an organ or tissue. The latter would enable a more precise assessment of the site of resi-
dence of vanadium or other elements. If the tissue specimen is homogenized, it should be uniform.
This is important if the sample is analyzed by several laboratories. Inconsistent findings will result
if fragments of tissue, bone, etc. are dispersed or settle from a homogenized sample.
4.3.2. Analysis
The procedure used to prepare a tissue specimen for analysis depends on type of sample, element
to be determined, and analytical procedure or instrument to be used. Problems of analysis are
similar to those of other biological tissues (foods, plants, etc.) where other elements can interfere.
The multielement composition of biological tissues provides the analyst with technical problems.
Methods and instruments that are of major interest for analyzing tissues for vanadium include:
• Neutron-activation analysis — radiochemical and instrumental.
• Atomic absorption spectrophotometry — flame, graphite furnace, and flameless.
• Emission spectroscopy — dry ashing.
• Optical colorimetry.
These methods are applicable to the analysis of other biological materials.
Neutron activation is a rapid and sensitive technique for detection of vanadium in biological
materials. The rapid decay (half-life 3.8 minutes) of the induced radiovanadium, V-52, is a problem.
Sampling, Preparation, and Analysis 4-13
-------
Preparation of a hard tissue is particularly difficult in the short time available for counting radio-
vanadium.
Neutron-activation analysis of vanadium allows estimation on the order of 10"9 gram. This sensitive
technique is reduced by elapsed time between irradiating specimens in the reactor and counting.
Investigators have irradiated biological specimens prepared by acid digestion hi a reactor and made
counts in 8 to 10 minutes (two half-lives) of radiovanadium, V-52. This permitted measurement
of vanadium in biological materials within the range of ±5 percent.
Soremark117 similarly used neutron-activation analysis to determine vanadium content of biological
specimens. Generally, he reported lower values for vanadium than did Schroeder116 using emission
spectroscopy. Sdremark also employed autoradiography to determine distribution patterns hi fish.
Autoradiograms of whole-body sections were taken after fish were kept for 3 days in water con-
taining vanadium-48.
Hair and placental specimens collected under the CHESS program are analyzed by emission spec-
troscopy.1111 Atomic absorption scpectroscopy has been used to measure trace levels of vanadium
in a few urban woody plant species hi New Hampshire and Vermont.118
4.4 STATIONARY SOURCE SAMPLES
4.4.1. Sampling
No direct-reading instruments for field and continuous or semicontinuous application are available
for measuring vanadium hi stack emissions. Samples of dust or fumes are collected with filter
paper samplers, electrostatic precipitators, and/or impingers, and then analyzed hi the laboratory.
4.4.2. Analysis
Analytical techniques relying on instrumental methods have been applied to measure vanadium in
various media, including paniculate matter collected from ambient air. The predominantly used
techniques are colorimetry, atomic absorption spectrophotometry, atomic fluorescence, emission
spectroscopy, X-ray fluorescence, neutron-activation analysis, and mass spectrometry. Most of
these methods are based on analyses only of paniculate collected on filters (paper, organic mem-
brane, or glass fiber), as they suffer from potential sample loss by vaporizing volatile compounds
hi stack emissions when large volumes of air are drawn over the collected paniculate matter This
effect would be noticed readily when collecting compounds that are obviously volatile. The effect
also could occur in special cases — for example, the volatilization of chromic oxide can be
enhanced by forming chromium trioxide hi an oxygen atmosphere, particularly in a dynamic system
with a considerable flow of gas. Some of this loss can be minimized by a tandem arrangement of
filter and impinger containing a collecting liquid. The vaporization losses on filters could be
moderately high when sampling heated stack gases.
The following sections discuss technology related to analytical methods that can be applied to the
4-14 STAR —VANADIUM
-------
continuous or short-term measurement of metals from stack emissions. Although a variety of tech-
niques are presented, the most attractive methods for general application (vapor and paniculate),
based on selectivity and sensitivity, are atomic absorption and emission spectroscopy. Others, such
as X-ray fluorescence, may find application in measuring only paniculate matter.
4.4.2.1. Atomic Absorption Spectrophotometry — Because of moderately high sensitivity and
good specificity, atomic absorption spectropbotometry has been used to measure trace quantities of
metallic elements collected from ambient air after dissolution of the paniculate in acid. The major
problem in applying the technique to continuous monitoring of stack emissions for vanadium is
the inability to handle refractory compounds and elements that readily form stable compounds,
such as vanadium oxides, in the flame. Serious matrix and interelement effects are observed.
Matrix effects and compound formation are most common in air- or oxygen-acetylene flames. As
a consequence, direct aspiration of air-contaminated gas into the flame has not been used to any
large degree for continuous monitoring of metallic elements in air or stack emissions. Such a system
can be developed, but the estimated detection limit would only be about 1 mg/m3 without a pre-
concentration step.
A modified atomic absorption spectrophotometer for simultaneous determination of four selected
elements was described by Zwiebaum and Moorhead.110 The system was designed for continuous
monitoring of several elements concentrated from the atmosphere into a small-volume air stream.
The air stream with enriched sample content is fed directly and continuously into the burner nebu-
lizer. The highest sensitivity, minimal matrix, and minimal chemical interferences are attained with
nitrous oxide as the oxidant and with a nitrogen sheath gas to restrict interaction of ambient air
with the chemical species in the flame.
Interelement effects can also be eliminated by using a high-energy plasma to atomize the elements
being measured. The major problem hi applying this technique is to maintain high levels of ground-
state atoms but low ionization efficiencies in the plasma. Energy from the plasma may ionize the
element sought, thus reducing the population of ground-state atoms, which must be high to attain
high sensitivities for the atomic absorption phenomenon.
4.4.2.2. Emission Spectroscopy — Although emission spectroscopic techniques have been used
extensively to measure the metal content of particulates collected by NASN,120-121 no data are
available for continuous, flow-through emission spectroscopic studies on airborne or stack emissions
of vanadium. Section 4.2.1. outlines the uses of emission spectroscopy for the analysis of filtered
samples.
4.4.3. Evaluation
At this time, there is no continuous monitoring system for measuring vanadium from stationary
source emissions. A continuous monitoring system for vanadium in stack gas is possible if the ele-
ment is kept suspended in the gas and the gas is then introduced as pan of the oxidant or fuel in the
flame or high-energy discharge of the excitator source of the spectrometer. To date, most labora-
tory techniques have been applied to integrated samples of paniculate matter collected on filter
paper from ambient air.
Sampling, Preparation, and Analysis 4-15
-------
High sensitivities and the attendant low detection limits of atomic absorption and emission spec-
troscopy make these methods most attractive for continuous or short-term intermittent monitors.
With vanadium, the major problem in using the absorption or emission spectroscopic techniques is
the interelement or compound formation effects.
With atomic absorption spectrophotometry, the interelement or compound formation effects are
minimized or eliminated by using a nitrous oxide-acetylene flame. The best results are obtained
with a sheath gas, which is an inert gas such as nitrogen, to exclude oxygen from the flame. Obvi-
ously, in ambient air or stack emissions, elimination of the oxygen is extremely difficult. One pos-
sible way to eliminate the oxygen is to pass the stack gas or air over hot carbon to produce carbon
monoxide.
The use of an inert gas plasma as an atomization source for atomic absorption spectrophotometry
will also minimize interelement effects if a reducing atmosphere is maintained by introducing
hydrogen gas. An additional problem related to the use of a plasma to provide the atomization for
atomic absorption measurements is the possibility of overexciting the element sought and causing
its emission.
With a high-resolution semiconductor detector, X-ray emission techniques with conventional X-ray
target tubes and with radioisotope sources can be used on an intermittent basis to determine vana-
dium hi paniculate collected on filters. Care must be taken to measure thin film deposits so as to
minimize matrix effects. Also, the background of secondary emission of X-rays from the filter
media can be a major interference.
Radioisotope sources for X-ray emission measurements provide a high degree of portability and
simplicity of ancillary equipment. When applied to monitoring paniculate collected on filters,
good accuracy and repeatability of measurements are obtained. The major limitations in applying
the X-ray techniques are the time necessary to collect sufficient paniculate matter on the filter
and the potential loss of volatile emissions containing the element sought.
Nondestructive neutron-activation analysis for vanadium can be performed on paniculate matter.
The major problem is interference from radioactive isotopes of other elements.
Fast neutrons from an isotopic source give much shorter irradiating and cooling times, compared
to other neutron sources. There is some sacrifice of sensitivity, but the technique can detect vana-
dium hi approximately 30 minutes.
Continuous, on-stream (aqueous solutions), neutron-activation analyses for vanadium have been
performed with isotopic sources at the ^100 ppm level hi 5- to 10- minute cycles.
Any technique relying on collection of paniculate matter on filters from relatively large volumes
of air or stack gases risks the toss of volatile compounds.
Data are needed on the particle size distribution of vanadium emissions to supply input into air
modeling schemes designed to determine the fate of the emitted material.
4-16 STAR— VANADIUM
-------
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tolylhydroxylamine. Analyst. 96:127, 1971.
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52. Sherwood, R. M., and F. W. Chapman, Jr. New Techniques for Analyzing Mixtures of Trace Metals. AnaL
Chem. 27:88, 1955.
53. Sandell, E. B. Colorimetric Determination of Traces of Metals. New York, Interscience Publishers, Inc.,
1944.
54. Von Jermnn, L., and V. Tettmar. Polarographische Bestimmung von Vanadin in der Luft von Arbeit-
sraumen (Polurographic Determination of Vanad'um in Work Areas). Z. Hyg. (Leipzig) 14:12, 1968.
55. Cnssani, F. Determinazione Potenziometrica del Titanio e del Vanadio (Potentiometric Determination of
Titanium and Vanadium) Chem. Ind. (Praque) 57:1248, 1969.
56. Sierra, F., C. Sanchez-Pedrino, T. Perez-Riuz, and C. M. Lozano. Amperometric Determination of Vana-
dates (Spanish) An. Quim. (Madrid). 66:479, 1970.
Sampling, Preparation, and Analysis 4-19
-------
57. Singh, D. and S. Sharma. Amperometric Permanganometric Estimations at Low Concentrations in Stirred
Solutions. Ind. J. Chem. 5:192, 1970.
58. Kostromin. A. I., A. A. Akhmetov, and L. N. Orlova. Coulometric Determination of Manganese (II), Ce-
sium (III), and Vanadium (IV). (Russian) Zh. Anal. Khim. (Moscow) 25:195, 1970.
59. Rigdon, L. P., and J. E. Harrar. Determination of Vanadium by Controlled-Potential Coulometry. Anal.
Chem. 47:1673, 1969.
60. Rhodes, H. U. Analyses of Atmospheric Dust by Electron Optics. PHS Grant 2R01 AP 00372, active Feb-
ruary 1, 1966, to January 31, 1970. Terminal Report (unpublished). 27 p.
61. Blosser, E. R. Identification and Estimation of Ions, Molecules and Compounds in Particulate Matter Col-
lected from Ambient Air. U. S. Environmental Protection Agency, Research Triangle Park, N. C. APTD-
0705, 1971. 77 p.
62. Lander, D. W., R. L. Steiner, D. H. Anderson, and R. L. Dehm. Spectrographic Determination of Elements
in Airborne Dirt. Appl. Spectrosc. 25:270, 1971.
63. Morrow, N. L., and R. S. Brief. Elemental Composition of Suspended Particulate Matter in Metropolitan
New York. Environ. Sci. Technol. 5:786, 1971.
64. Boumans, P. W. J. M. Theory of Spectrochemical Excitation. New York, Plenum Press, 1966. p. 203-208.
65. Sugimae, A., and T. Hasegawa. Vanadium Concentrations in Atmosphere. Environ. Sci. Technol. 7:444,
1973.
66. Hnsegawa, T., and A. Sugimae. Heavy Metals in Atmospheric Particulates. Jap. Anal. 20:840, 1971.
67. Tani, M. Methods and Actual Techniques of Measuring Heavy Metals in the Environmental Atmosphere.
Kogai to taisaku. 5:551-556, 1972.
68. Tabor, E. C., and W. V. Warren. Distribution of Certain Metals in the Atmosphere of Some American
Cities. A.M.A. Arch. Ind. Health. 77:145, 1958.
69. Frigieri, P., R. Trucco, R. Anzani, and E. Caretta. Spectroscopic Analysis of Elements Present in Air-
borne Materials. Chim. Ind. 54:3, 1972.
70. Loseke, W. A., D. R. Scott, D. C. Hemphill, L. E. Holboke, R. J. Thompson, L. I. Pranger, and S. J. Long.
Analysis of National Air Surveillance Network Particulate Samples for Trace Elements by Emission Spec-
trometry. U. S. Environmental Protection Agency, Research Triangle Park, N. C. (Presented at American
Chemical Society Meeting, Chicago, August 27, 1973.)
71. Koh, K. I., and D. E. Ryan. Fluorescence and Metallic Valency States; Part VI. Determination of Vanadium
with Benzoic Acid. Anal. Chim. Acta. 57:295, 1971.
72. Karayannis, N. M., and A. H. Corwin. Volatilization and Separations of Metal Acetylacetonates at 115°C
by Hyperpressure Gas Chromatography. I. Chromatogr. Sci. 5:251, 1970.
73. Moshier, R. W., and R. E. Sievers. Gas Chromatography of Metal Chelates. New York, Pergamon Press,
1965. 163 p.
74. Taylor. M. I.. Gas-liquid Chromatography of Trace Elements. In: New Trace Elements in Nutrition,
Mertz, W. and W. E. Cornatzer (eds.). New York, Marcel Dekker, 1971. p. 363-389.
75. Martens, C. S., J. J. Wesolowski, R. Kaifer. and W. John. Sources of Vanadium in Puerto Rican and San
Francisco Bay Area Aerosols. Environ. Sci. Technol. 7:817, 1973.
76 Bando, S., and T. Imahashi. Activation Analysis of Vanadium in Deposits and Airborne Particulates. Jap.
Anal. 15:1477, 1969.
4.20 STAR —VANADIUM
-------
77. Dams, R., I. A. Robbins, K. A. Rahn, and J. W. Winchester. Nondestrucdve Neutron Activation Analysis of
Air Pollution Particulates. Anal. Chem. -#2:861, 1970.
78. McKown, D. M., D. H. Gray, M. E. Eichor, and J. R. Vogt. Neutron Activation Analysis in Environmen-
tal Chemistry. Amer. Lab. 7:39-44, July 1973.
79. Craft, C. North Carolina State University, Raleigh, N. C. Personal communication with C. Sawicki, Chem-
istry and Physics Laboratory, U. S. Environmental Protection Agency, Research Triangle Park, N. C.,
1973.
80. Livingston, H. D., and H. Smith. Estimation of Vanadium in Biological Material by Neutron Activation
Analysis. Anal. Chem. 57:1285, 1965.
81. Rancitelli, L. A., J. A. Cooper, and R. W. Perkins. Multielement Characterization of Atmospheric Aerosols
by Instrumental Neutron Activation Analysis and X-ray Fluorescence Analysis. U. S. Atomic Energy
Commission, Richland, Wash. Contract AT(45-1)-1830. 1973.
82. Rahn, K., J. J. Wesolowski, W. John, and H. R. Ralston. Diurnal Variation of Aerosol Trace Element Con-
centrations in Livermore, California. J. Air Pollut. Contr. Ass. 27:406, 1971.
83. Rahn, K. A., R. Dams, J. A. Robbins, and J. W. Winchester. Diurnal Variations of Aerosol Trace Element
Concentrations as Determined by Nondestructive Neutron Activation Analysis. Atomic Environ. 5:413, 1971.
84. Gordon, G. E., W. H. Toiler, E. S. Gladney, and A. G. Jones. Trace Elements in the Urban Atmosphere.
Nuclear Methods in Environmental Research, Topical Meeting Abstract, 1971.
85. Bingham, R. A. and R. M. Elliot. Accuracy of Analysis by Electrical Detection in Spark Source Mass
Spectrometry. Anal. Chem. 45:43, 1971.
86. Gilfrich, J. V., P. G. Burkhalter, and L. S. Birks. X-ray Spectrometry for Paniculate Air Pollution — A
Quantitative Comparison of Techniques. Anal. Chem. 45:2002, 1973.
87. Rhodes, J. R., A. H. Pradzynski, and C. B. Hunter. Energy Dispersive X-ray Fluorescence Analysis of Air
Particulates in Texas. Environ. Sci. Technol. (5:922, 1972.
88. Giaque, R. D., F. S. Goulding, J. M. Jaklevic, and R. H. Pehl. Trace Element Determination With Semi-
conductor Detector X-ray Spectrometers. Anal. Chem. 45:671, 1973.
89. Goulding, F. S., and J. M. Jaklevic. Trace Element Analysis by X-ray Fluorescence. Lawrence Berkeley
Laboratory, Berkeley, Calif., Report No. UCRL-20625, May 1971.
90. Goulding, F. S., and J. M. Jaklevic. X-ray Fluorescence Spectrometer for Airborne Particulate Monitoring.
U. S. Environmental Protection Agency, Office of Research and Monitoring, Washington, D. C. Publica-
tion No. EPA-R2-73-182, April 1973. 70 p.
91. Bowman, H. R.. J. G. Conway, and F. Asaro. Atmospheric Lead and Bromine Concentration in Berkeley,
Calif. Environ. Sci. Technol. 6:558, 1972.
92. Dittrich, T. R.. and C. R. Cothern. Analysis of Trace Metal Particulates in Atmospheric Samples Using X-
ray Fluorescence. J. Air Pollut. Contr. Ass. 27:716, 1971.
93. Johansson, T. B., R. Akelsson, and S. A. E. Johansson. X-ray Analysis: Elemental Trace Analysis at the
10-12g Level. Lund Institute of Technology, Lund, Sweden. Publication No. LUNP 7109, August 1971.
94. Watson. R. L., J. R. Sjurseth. and R. W. Howard. An Investigation of the Analytical Capabilities of X-ray
Emisiion Induced by High Energy Alpha Particles. Nucl. Instrum. Methods. 95:69, 1971.
95. Leroux, J.. and M. Mahmud. Flexibility of X-ray Emission Spectrography As Adapted to Microanalysis
of Air Pollutants. J. Air Pollut. Contr. Ass. 20:402. 7970.
96. Greenfelt, P., A. Akerstrom, and C. Grosset. Determination of Filter-Collected Airborne Matter by X-ray
Fluorescence. Atmos. Environ. 5:1, 1971.
Sampling, Preparation, and Analysis 4-21
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97. I.uke, C. L., T. Y. Kometani, J. E. Kessler, T. C. Loomis, J. L. Bove, and B. Nathanson. X-ray Spectrometric
Analysis of Air Pollution Dust. Environ. Sci. Tcchnol. 6:1105, 1972.
98. Cooper, J. Comparison of Particle and Photon Excited X-Ray Fluorescence Applied to Trace Element
Measurements of Environmental Samples. Nucl. Instrum. Methods. 106:525, 1973.
99. Goulden, P. D., P. Brooksbank, and J. F. Ryan. Automated Solvent Extraction for the Determination of
Trace Metals in Water by AAS. Amer. Lab. S:10-17, August 1973.
100. Chau, Y. K., and K. Lum-Shue-Chan. Complex Extraction of Vanadium for Atomic Absorption Spectro-
scopy; Determination of Microgram Quantities of Vanadium in Lake Waters. Anal. Chim. Acta. 50:201,
1970.
101. Fishman, M. J., and M. W. Skougstad. Catalytic Detection of Vanadium in Water. Anal. Chem. 56:1643,
1964.
102. Linstedt, K., and P. Kruger. Determination of Vanadium in Natural Waters by Neutron Activation Analy-
sis. Anal. Chem. 42:113, 1970.
103. Connor, J., N. F. Shimp, and J. C. F. Techow. A Spectrographic Study of the Distribution of Trace Ele-
ments in Some Podzolic Soils. Soil Sci. 5J:65-73, 1957.
104. Methods of Analysis of the Association of Official Agricultural Chemists (6th ed.). Association of Of-
ficial Agricultural Chemists, Washington, D. C., 1945.
105. Kemp, D. M.. and A. A. Smnles. Determination of Vanadium in Rocks and Meteorites by Neutron Activa-
tion Analysis. Anal. Chim. Acta. 2.7:297-410, 1960.
106. Shimp, N. F.. J. Connor, A. L. Prince, and F. E. Bear. Spectrochemical Analysis of Soils and Biological
Materials. Soil Sci. 83:51-64, 1957.
107. Vanadium. National Academy of Sciences, Committee on Biological Effects of Atmospheric Pollutants,
Washington, D. C., 1974.
108. Goeke, R. Determination of Vanadium in Ore Samples. Talanta. 15:871-873, 1968.
109. Hammer, D. I., I. Finklea, R. H. Hendricks, T. A. Hinners, W. B. Riggan, and C. M. Shy. Trace Metals
in Human Hair as a Simple Epidemiological Monitor of Environmental Exposure. In: Trace Substances in
Environmental Health Symposium, Hemphill, D.D. (ed.). U. of Missouri, Columbia, Mo., 1971.
110. Colucci, A., P. Brubaker, J. Bumgarner, J. Creason, E. Faeder, J. French, D. Hammer, T. Hinner, D. Hin-
ton, G. Love, C. Pinkerton, C. Sharp, W. Sovocool, W. TerriU, and M. Waters. Collection of Autopsy Tis-
sue Sets — CHESS Pollutant Burden Protocol. In-house report, U. S. Environmental Protection Agency,
National Environmental Research Center, Research Triangle Park, N. C., February 1973.
111. Gordos. A. A. U. of Michigan, Ann Arbor, Mich. Verbal communication on results of hair as an indi-
cator of trace metal body burden with D. Worf, Human Studies Laboratory, U. S. Environmental Protection
Agency, Research Triangle Park, N. C., June 1973.
112. Worf, D., A. Colucci, and C. Shy. National Tissue Specimen Bank. In-house report, U. S. Environmental
Protection Agency, National Environmental Research Center, Research Triangle Park, N. C., 1973.
113. Finklea, I. F., D. Hammer, T. Hinners, and C. Pinkerton. Human Pollutant Burdens. U. S. Environmental
Protection Agency, Research Triangle Park, N. C. (Presented at American Chemical Society Symposium,
Los Angeles. April 1-2, 1971.)
114. Colucci, A.. P. Brubaker, J. Bumgarner, J. Creason, E. Faeder, J. French, D. Hammer, T. Hinner, D. Hin-
ton, C. Love, C. Pinkerton, C. Sharp, W. Sovocool, W. Terrill, and M. Waters. Collection of Maternal-
Fetal Tissue Sets. CHESS Pollutant Burden Protocol. In-house report, U. S. Environmental Protection
Agency, National Environmental Research Center, Research Triangle Park, N. C., February, 1973.
4-22 STAR— VANADIUM
-------
115. Trace Metal Analysis of Maternal-Fetal Tissue Sets. Human Scalp Hair, and Housedust. Stewart Labs, Inc.,
KnoxviUe, Tenn. EPA Contract No. 68-02-0663, December 1972.
116. Schroeder, H. A. Air Quality Monographs, Monograph No. 70-13, Vanadium. American Petroleum Insti-
tute, Washington, D. C., 1970. 32 p.
117. Soremark, R. Vanadium in Some Biological Specimens. I. Nutr. 92:183-190, 1967.
118. Smith. W. H. Metal Contamination of Urban Woody Plants. Environ. Sci. Technol. 7:631, 1973.
119. Zweibaum. F., and J. Moorhead. A Multi-element Atomic Absorption Analyzer. Atomic Absorption News-
letter. 6(6) :137. 1967.
120. Air Pollution Measurements of the National Air Sampling Network, Analyses of Suspended Participates,
1957-1961. U. S. Department of Health, Education, and Welfare, Public Health Service, Washington, D. C.
Public Health Service Publication No. 968, 1962.
121. Air Quality Data from the National Air Surveillance Networks and Contributing State and Local Networks,
1966 Edition. U. S. Department of Health, Education, and Welfare, Public Health Service, National Air
Pollution Control Administration, Durham, N. C. NAPCA Publication No. APTD 68-9, 1968.
Sampling, Preparation, and Analysis 4-23
-------
5. ENVIRONMENTAL APPRAISAL
5.1 OCCURRENCE
.">. 1. J. Natural Sources
Vanadium is one of the more abundant trace elements. It is found in igneous rocks, shales, iron
meteorites and silicate meteorites, some phosphate deposits, uranium ore, and asphaltic deposits
on all continents.'•- It resembles phosphorus and titanium and, like these two elements, is concen-
trated in basic rocks. Titanium magnetites are high in vanadium. In general, vanadium concentra-
tions vary according to the type of rock or soil and are highest in shales and clays.3 Vanadium
occurs in the earth's crust as relatively insoluble salts, where it is commonly found in the trivalent
state. The geochemical as well as the biochemical behavior of vanadium is determined by the fact
that it may exist in three stable oxidation states: tri-, tetra-, and pentavalent forms.1 The natural
sources of airborne vanadium are believed to be marine aerosols and continental dust. Volcanic
action might also be a source, but its contribution is believed to be small.
5.1.2. Human Uses
Sources of vanadium emissions can be placed into two major categories: those processes that use
vanadium and its compounds as raw materials, and combustion processes with vanadium-contain-
ing fuel.
Combustion sources are by far the largest and the most widespread sources of vanadium air pollu-
tion, although other sources may have important local or regional significance. Coal and oil both
contain varying amounts of vanadium, and their combustion resulted in estimated emissions of
17,000 megagrams (Mg) [metric tons (MT)1 of vanadium into the air in 1968 (Table 5.1).4
5.7.2.7. Fueli — Crude oils vary greatly in their vanadium content. During the refining process,
nearly all of the vanadium present remains in the residual fractions. Thus, kerosene, gasoline, diesel
fuel, and home heating fuels contain relatively little of the metal, and the residual oils, which are
employed in large combustion units, contain nearly all of the vanadium originally present in the
crude oil. Information on the chemical form of airborne vanadium from oil combustion is limited.
Bowden ct al.5 have reported that fly ash from residual fuel oil combustion may contain a variety
of vanadium oxides such as V2Os, VaO.4, or V2OB; and double metal oxides such as Na2O
V3OB and Fe2(W:OR. However, V2O5 is thought to be the prevalent oxide cf vanadium emitted
into the atmosphere.6
Environmental Appraisal 5-1
-------
Table 5.1. EMISSIONS OF VANADIUM BY SOURCE, 19684
Source
Mining and processing
Metallurgical processing
Reprocessing
Steel:
Blast furnace
Open-hearth furnace
Basic oxygen furnace
Electric arc furnace
Cast iron
Nonferrous alloys
Chemicals and ceramics:
Catalysts
Glass and ceramics
Miscellaneous
Consumptive uses
Coal
Oil
Total
Emissions, MT (Mg)
Subtotal
n _ —
57
151
6
No
1
3
2
No
2
1,587
15,419
— —
Total
73
131
222
..
— —
— —
— _
17,006
17,432
oN-negllglble (less than 1 MT (Mg).
Power plants and utilities that burn residual and crude oil and coal and petroleum refineries that
burn crude oil or residuals emit vanadium compounds as inorganic paniculate and possibly as
organocomplexcs. The concentration of vanadium in fly ash collected downstream of the control
device in two coal-fired power plants was reported7 as 230 to 390 fig/m3 and 1,350 to 1,580
Of the approximately 17,000 MT of vanadium emitted to the atmosphere in the United States dur-
ing 1968 (about 0.28 percent of the total particulate matter emitted), over 80 percent came from
the combustion of residual fuels.4 Because of regulations that limit the sulfur content of fuel oils,
however, the vanadium emissions from this source are expected to decrease. The desulfurization
process coincidentally reduces significantly vanadium and other metallic impurities in the fuel oil.
Radford and Rigg8 found that the vanadium content of residual fuel oil made from a representa-
tive Venezuelan crude was reduced from 218 to 105 to 59 ftg/g as the sulfur content was reduced
from 2.6 to 1.0 to 0.5 percent. On this basis, it appears that there is an almost one-to-one relation-
ship between the vanadium reduction and the degree of desulfurization. The vanadium content of
fuel oil was variable, however, ranging from 0.1 to 500 fig/g in 100 samples analyzed.9
U. S. coal generally contains less than 35 fig/g of vanadium, with western coals containing about
one-half that value. Consumption of coal, especially western coal, is expected to increase. As par-
liculate control technology improves (see Section 7), the total amount of vanadium emitted to the
atmosphere may or may not significantly change.
Emission concentrations are dependent on several factors, including vanadium content of raw ma-
terial and/or fuel, process type, method of operation, and the efficiency of the particulate control
system.
5.2 STAR — VANADIUM
-------
Recently, coal-fired power plants have been the subject of several material balance studies for trace
metals. One of the most thorough material balance studies was done on the Allen Steam Plant at
Memphis, Tennessee, a 240-megawatt unit operated at 80 percent of full load.10 Based on the re-
sults from the electrostatic precipitator inlet and outlet, the efficiency for vanadium removal in the
plant is 99 percent (Table 5.2).
Table 5.2. MATERIAL BALANCE FOR VANADIUM AT A COAL-FIRED
STEAM POWER PLANT10
Vanadium collected, g/mln°
Run
No.
5
7
9
In
coal
26
87
26
In slag
tank
solids
13
57
14
In fit
At precipitator
Inlet
14
53
9.7
ash
At precipitator
outlet
0.75
0.12
Precipitator
efficiency, %
99
99
aSamples collected Isoklnetlcally using an alundum filter followed by a millipore filter, and analyzed by Instru-
mental neutron activation.
Considerable research is underway to determine trace element concentration by particle size. Anal-
ysis of fly ash from three coal-fired power plants indicates that much of the vanadium occurs in the
small particle sizes (Table 5.3).11 This concentration of vanadium in fine particles may be signifi-
cant. Even though an electrostatic precipitator may have an overall 99 percent removal efficiency,
the removal efficiency for small particles such as 1.3 /-im and smaller will be less. It is these par-
ticles that are respirable and therefore are of greatest concern as a possible health hazard.
Table 5.3. VANADIUM CONCENTRATION OF COAL FLY ASH,
BY PARTICLE SIZE" °
Particle size, /*m
1.3
2.0
4.6
8.5
13.
22.
33.
>33.
Concentration, /xg/g
Source A
345
277
240
201
207
199
197
193
Source B
260
382
265
193
188
193
181
157
Source C
183
182
282
204
154
136
135
138
°Fly ash sized using a Bahco classifier and analyzed by neutron activation.
As part of EPA's Nationwide Fuel Surveillance Network, gasoline is collected from the 10 EPA
Regions and analyzed for approximately 25 trace elements, including vanadium. Table 5.4 sum-
marizes vanadium concentrations found in gasolines collected in the spring of 1972 from retail
service station pumps.12
Table 5.4 also summarizes the vanadium content of selected residual fuel oils and crude oils.13 One
type of fuel oil, residual fuel oil No. 6, is the common fuel oil used for electric power generation
STAR —VANADIUM 5-3
-------
Table 5.4. VANADIUM CONCENTRATION IN GASOLINE, FUEL
ADDITIVES, MOTOR OIL, FUEL OIL, CRUDE OIL, AND COAL"-17
Source
Gasoline0
Premium
Regular
Low lead
Fuel additivesb
Motor oile
Residual fuel oild
Crude oild
Coal"
Number of
samples
22
22
6
18
4
20
20
24
Average
concentration
0.001 /tg/ml
< 0.007 /tig /ml
<0.003 /Ltg/ml
67 jitg/g
25 yu-g/g
33 ftg/g
Range
0.001 to 0.002 /-eg/ml
<0.001 to 0.031 fig/ml
<0.001 to 0.007 /tg/ml
0.38 to 230 /tg/g
<0.02to 140 /u,g/g
10 to 62 /u,g/g
aCollected in spring, 1972, from retail service station pumps.
bNeutron-activatlon analysis. Fuel additive samples included: gas treatment, fuel-mix tune-
up, engine tune-up, gas power booster, gasoline antifreeze, gas booster, and carburetor
tune-up.
'Neutron-activation analysis.
dNeutron-actlvatlon analysis. Samples represent 20 different oil fields, both domestic and
foreign. The residual fuel oil and crude oil are not necessarily from the same oil fields
but represent 20 oil fields for each.
•Coal samples from Illinois, West Virginia, and Utah. Each coal was analyzed by X-ray
fluorescence, optical emission-direct reading, and optical emission-photography; values
from these three methods were then used to determine the average and range.
plants and large industrial boilers. Crude oil is of concern since several power plants have shifted
from burning residual fuel oil to burning crude oil because of the increasing cost of low-sulfur re-
sidual fuel oil.14 As of February 1972, three East Coast utilities were burning a total of 5,400 m3/
day of crude oil. By 1975, crude consumption is expected to climb to 28,000 m3/day and will in-
volve at least nine utilities.14
The vanadium concentrations for coals mined in various areas of the United States are summarized
in Table 5.4 as well.18
5.1.2.2. Fuel Additives—In anticipation of regulations pursuant to Section 211 of the 1970 Clean
Air Act Amendments on registration of fuels and fuel additives, EPA is analyzing consumer-pur-
chased fuel additives for trace element content. As the first step of this surveillance effort, fuel
additives were purchased from retail stores in the Research Triangle Park, N. C., area and analyzed
for trace elements (Table 5.4)16
As part of EPA's Nationwide Fuel Surveillance Network, crankcase lubricating oils are also being
collected for trace element analysis. Initial results for vanadium are shown in Table 5.4 for several
grades of one brand of motor oil.17
5.7.2..?. Metallurgical Uses—The iron and steel industry has historically used the greatest tonnage
of vanadium. All common wrought forms — sheet, wire, and tube — have been used. One of the
commercial forms of vanadium that is added in steelmaking is ferrovanadium, an alloy consisting of
iron and 50 to 80 percent vanadium. Ferrovanadium is brittle but not friable. It is not as corrosion-
resistant as pure vanadium, but resists rusting in the normal open storage of a steel plant.
The ferrovanadium used for alloy additions in steelmaking is produced in electric arc furnaces- The
charge consists of scrap steel, fused sodium metavanadate, carbon with silicon, and aluminum, or a
5-4
STAR —VANADIUM
-------
combination of the two as a reducing agent. The furnace is not closed to the atmosphere. Most of
the charge exists as metal slag or carbonaceous gases, but a substantial amount evolves as fumes.
Emissions of vanadium into the atmosphere from the production of ferrovanadium totaled 131 Mg
(MT) during 1968. These emissions constitute a potentially serious problem in the vicinity of fer-
rovanadium-producing plants, of which there are few in the United States. The emissions were
mostly in the form of particles ranging from 0.1 to 1 pm in size.4
A large part of all the steel made finds its way back to steel-melting operations as scrap. In the re-
fining stage of such operations, the contained alloy metals are oxidized out of the liquid steel as
completely as possible. Vanadium from scrap steel is oxidized and discharged partly to air, and partly
into slag, which can be run off, granulated, and discarded with reasonable safety. Today, a very high
proportion of scrap steel is recycled by way of the basic oxygen furnace (BOF), which refines steel
with a high-pressure jet of pure oxygen. This injection produces large amounts of fume that con-
sist essentially of metallic oxides, which are normally collected by electrostatic precipitators. In re-
cycling of steel in this manner, vanadium accounted for an estimated 0.02 percent of the estimated
21 kg (46 Ib) of paniculate emitted from the BOF per ton of steel produced, with a 97 percent
emission control. During 1968, the BOF was used to produce 43.5 million Mg (MT) of steel.4 Based
on these production figures, an estimated 6.0 Mg (MT) of vanadium escaped into the atmosphere.
This estimate was calculated using an emission factor of 21 kg (46 Ib) of paniculate emitted per
ton of steel produced; 9 X 10-5 kg V/kg of paniculate emitted (2 X 10-* Ib V/lb); and 97 percent
emission control.
The site of particle deposition will depend largely on height of discharge and size of the particles.
Atmospheric concentrations of vanadium at the boundary of a steel plant averaged 0.072 /*g/m3
(Table 5.5).18 Additional data from this same plant indicate that its paniculate control equipment
is 99.5 percent efficient,19 and the plant would therefore produce lower emissions than those indi-
cated in the earlier calculations and in Table 5.1.
Table 5.5. ATMOSPHERIC CONCENTRATIONS OF VANADIUM
AT BOUNDARY OF TYPICAL STEEL PLANT, 196718°
Date of collection
Jan. 1
Feb. 1
Feb. 22
Apr. 30
May 16
May 31
June 7
June 29
Aug. 3
Aug. 18
Sept. 8
Sept. 21
Oct. 5
Average
Range
Concentration, ^fl/m3
0.054
0.063
0.040
0.090
0.082
0.105
0.098
0.040
0.040
0.107
0.092
0.081
0.040
0.072
0.040 to 0.107
"All samples were collected at the plant boundary In a community, but at an elevation of
about 15 m. The Staplex high-volume air sampler with 8-fjg, 25-cm glass fiber filters was
used for the sample collection. Air concentrations were calculated as vanadium rather
than vanadium pentoxlde.
Environmental Appraisal
5-5
-------
The high-cost tool and die steels are produced largely in vacuum-induction and vacuum arc-melt-
ing systems, in which vanadium carbides are added during the normal melting in a vacuum with
cold-mold arc-fusion furances. Because of the melting system is closed, no vanadium should be re-
leased in any form to the atmosphere. The vanadium carbides are produced by carbothermic reduc-
tion of sodium metavanadate in a closed vacuum system operation, and a negligible amount of
vanadium escapes into the atmosphere.
Vanadium is added to numerous steels in quantities from 0.2 to 4.5 percent (Table 5.6). Other tra-
ditional uses of vanadium in alloys are in welding rods, hard-facing alloys, magnetic alloys, high-
temperature alloys, wear-resistant alloys, and steel alloys used in automotive parts (bolts, springs,
engine valves, steam pipes and headers, and rotors). Good structural strength and a low-fission
cross section make vanadium useful in nuclear applications; it is applied as the basic alloy in fuel
cladding for advanced liquid-metal-cooled fast-breeder reactor.3 Consumption of vanadium by end
product is presented in Table 5-7.
Table 5.6. STEELS CONTAINING VANADIUM3
Type of steel
Vanadium content, %
Tool and die
High-speed tool
Cold
High carbon, high chromium
Hot
Stainless, Type 422
Carbon-vanadium
Chromium-vanadium
Manganese-vanadium
Vanadium-spring steels
0.2 to 4
1 to 4
0.2 to 4.5
1 to 4
0.3 to 0.5
0.3
0.1 to 0.2
0.05 to 0.5
0.05 to 0.2
0.08 to 0.2
Table 5.7. METALLURGICAL USES OF VANADIUM IN THE
UNITED STATES20
(Mg (MT) of contained vanadium)
End use
Steel (Ingots and castings):
High-speed and tool
Stainless
Alloy (excluding stainless and tool)
Carbon
Other steel
Cast irons
Cutting and wear-reslstarvt materials
Welding and hardfacing rods and materials
Magnetic alloys
Nonferrous alloys0
1967
678
35
1,910
746
5
49
12
11
4
557
1968
553
45
2,350
990
6
52
15
11
5
416
•Principally titanium-base alloys.
Two relatively young segments of the steel industry — high-strength, low-alloy steels (HSLA) and
continuous casting of steel slabs and billets — are expected to exceed all other cumulative uses of
5-6
STAR — VANADIUM
-------
vanadium.3 Vanadium in HSLA steels increases strength by substantially increasing the yield point.
The amount of vanadium used (approximately 0.1 percent) and the techniques employed are such
that other properties of the steels, particularly ductility and weldability, are not adversely affected.3
Aluminum has been used extensively as a deoxidant in slab casting and as a grain refiner in the
continuous casting of billets, but vanadium has been substituted to avoid nozzle clogging of the
tundish (caster feed pot) by alumina formed during use. Vanadium increases yield strength, increases
resistance to hot-tearing, and provides a cleaner steel surface. However, impact strength is reduced
somewhat, and a higher yield point makes bending more difficult.
Apart from its use in steels, vanadium is a major alloying element in high-strength titanium alloys.
Aluminothermic vanadium, an alloy of aluminum and vanadium (4 percent), is added to titanitum
as a master alloy. The effect of vanadium on titanium is strong beta stabilization, which promotes
good hot and cold workability.1'1 Because of their reactive nature, these alloys are melted under
vacuum in a closed system. During the processing of steel ingots to wrought shapes, the steel is
oxidized superficially, and thick oxide or mill scale is formed. Various grinding and machining
operations produce comminuted materials, most of which are not recycled; but the materials
themselves arc quite inert and do not become airborne. In preparation for cold finishing, steels
are pickled in baths of strong acids to remove surface defects. The spent acids contain a consider-
able volume of metal, along with a residue of sludge that is rich in halide salts of vanadium. Unless
treated properly, the large quantities of spent acids could be a potential source of pollution.
The many shapes in which common ferrous alloys containing vanadium are fabricated and used
require chemical treatment (such as pickling of scale) and high-temperature operations (such as
welding, flame cutting, and hot working). Four vanadium metal operations — furnace addition of
vanadium, tap of a furnace heat, oxyacetylene cutting, and arc-welding beams — would be expected
to produce the greatest amount of fume. Data from a steel plant show a minimum of exposure of
vanadium (Table 5.8).18 The coating on welding rods is considered a potential source of vanadium
fume, although little information exists on the toxic substances present as impurities or on their
concentrations in arc-welding fumes.
5.1.2.4. Chemical Uses — The following are some of the many unique uses of vanadium com-
pounds in the area of chemistry:
Manufacture of sulfuric acid.
Manufacture of phthalic anhydride.
Manufacture of maleic anhydride.
Manufacture of aniline black.
Oxidation of cyclohexane to adipic acid.
Oxidation of ethylene to acetaldehyde.
Oxidation of anthracene to anthraquinone.
Oxidation of toluene or xylene to aromatic acids.
Oxidation of furfural to fumaric acid.
Oxidation of hydroquinone to quinone.
Oxidation of butene-2 and 1,3-butadiene to maleic anhydride.
Ammonolysis oxidation of toluene, m-xylene, p-xylene, and propylene.
Manufacture of vinyl acetate from ethylene.
Manufacture of cyclohexylamine from cyclohexanol and ammonia.
Catalytic combustion of exhaust gases.
Catalytic synthesis of ethylene-propylene rubber.
Environmental Appraisal 5.7
-------
Table 5.8. CONCENTRATIONS OF VANADIUM PENTOXIDE IN AIR
AT POINT SOURCES AT A STEEL PLANT'8
Location
V-ton furnace
V-ton furnace
Press forge
Beam-yard
weld bed
Operation
Furnace addition
of vanadium
Tap of furnace heat
Oxyacetylene
cutting of
forging
Arc-welding
beams
Vanadium content
of steel, %
0.15 to 0.25
0.15 to 0.25
0.15 to 0.25
0.15 to 0.25
1.8 to 2.1
1.8 to 2.1
0.5 to 0.7
0.5 to 0.7
0.5 to 0.7
0.5 to 0.7
1.02
1.05
0.15 to 0.4
0.15 to 0.4
0.15 to 0.4
0.1 5 to 0.4
0.1 to 0.15
0.1 to 0.15
0.1 to 0.15
0.1 to 0.15
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
V2O5 concentration
in breathing zone,
mg/m3 of air0
0.006
0.007
0.078
0.007
0.019
0.013
0.004
0.011
0.004
0.02
0.002
0.008
0.004
0.015
0.003
0.011
0.01
0.002
0.005
0.001
0.003
0.006
0.002
0.002
0.004
0.004
0.003
0.005
0.004
0.005
"Threshold limit values for vanadium fume as vanadium pentoxlde: 0.05 mg/m', ceiling
value, in 1972. 21
Estimates of vanadium consumed by the chemical industry vary from 179 Mg (MT) in 1965 to 120
Mg (MT) in 1967, with projections of 182 to 227 Mg (MT) in 1976.3 The more important uses are
to catalyze the synthesis of sulfuric acid, the oxidation of hydrocarbons, and the polymerization of
mono- and diolefins.3
The oxidation of sulfur dioxide to sulfur trioxide in the production of sulfuric acid consumes by far
the greatest amount of vanadium — estimated at 69 Mg (MT) vanadium pentoxide in 1965 .'Vana-
dium-based catalysts (such as vanadium pentoxide on asbestos) are reported to be the preferred
catalysts for the reaction because of longer life, higher average efficiency, immunity to poisoning
by arsenic, chlorine, etc., and greater physical rujjgedness. A vanadium oxide catalyst is also used
in two closclv related processes — oxidation of aromatic hydrocarbons to phthalic anhydride, and
oxidation of bcn/cnc to maleic anhydride.
Vanadium compounds other than vanadium pentoxide are also used. For example, ammonium
metavanadate is mentioned in connection with the manufacture of adipic acid, vanadium oxytri-
5-8
STAR —VANADIUM
-------
chloride in connection with the production of ethylene-propylene synthetic rubber, and vanadium
trichloride in stereo-specific catalyst systems and as an intermediate in making high-purity metals
and intermetallies.3
In dye manufacture and dyeing, vanadium compounds are widely used in production of aniline
black. Vanadium salts are added as catalysts to a mixture of aniline hydrochloride and potassium or
sodium chlorate. Vanadium compounds are used as mordants in the dyeing and printing of cotton,
and particularly for fixing aniline black on silk. Ammonium metavanadate has been used as a cata-
lyst in the dyeing of leather and fur. Some modern quick-drying inks require addition of ammonium
metavanadate.3
Generally, total consumption of vanadium in these chemical processes is small; furthermore, its
principal use is as a catalyst, not as an ingredient. Potential hazards other than in point-source
industrial operations appear limited. But these uses of vanadium do leave two aspects for considera-
tion: first, vanadium compounds in the products will have very wide distribution; second, the spent
catalyst will be disposed of in some manner. Some spent catalysts are being reprocessed to vana-
dium products; however, the extent of this recycling has not been determined.
Closely allied to the chemical industry is polymer synthesis and processing. Total consumption of
vanadium in this industry, although small, is growing rapidly; 1975 levels may be 91 to 136 Mg
(MT).3 Polymer products such as packaging films are widely distributed, sometimes in connection
with food, and large quantities are incinerated. Questions have been raised regarding vanadium
extracted from polymers during food storage and from vanadium emission during incineration.
Fortunately, plastics have been found to contain only 1 ng/g or less of vanadium, which is not
considered hazardous.
5.1.2.5. Ceramics — The use of vanadium in the ceramic industry is on the decline. Vanadium
compounds are not currently used in the manufacture of glass fibers, frits, or refractories. Ammon-
ium metavanadate continues to play a primary role in various ceramic glazes, particularly the zircon
vanadium blues. These glazes are not used in dinnerware, but in such applications as wall tile.
Furthermore, the vanadium is tightly bound in substitutional solid solution in the zircon structure
and is therefore very stable.
5.1.2.6. Electronics Industry — The growth of the electronics industry, particularly the prolifera-
tion of solid-state devices, has emphasized the role of a number of transition elements, including
vanadium. Considerable research is underway, and it is likely that new applications will evolve.
For example, the insulator-to-metal transition in vanadium tetroxide at about 60°C is intriguing;
the resistance drops by several orders of magnitude over a very narrow temperature range.
5.2 CONCENTRATIONS
5.2.1. Air
Vanadium concentrations over relatively unpopulated areas of the earth range from 0.02 to 0.8
ng/m3 in the eastern Pacific Ocean22 and from 0.21 to 1.9 ng/m3 in remote northwestern Canada.23
In rural areas of the United States, values ranged from 0 to 13 ng/m3 for 1960 through 1965,
and from 1.0 to 64.6 ng/m3 for 1967-2 Although very few studies have been specifically designed
Environmental Appraisal 5-9
-------
to determine ambient concentrations of vanadium, the element has been included in the trace
metals analysis of several more general air pollution studies. For several years, NASN routinely
reported the vanadium content in the paniculate samples collected at its many monitoring sites
across the country. In addition, vanadium concentrations were determined in several short-term
monitoring projects aimed at establishing the overall air pollution pattern within a particular geo-
graphical area.
5.2.1.1. NASN Studies — Samples of suspended paniculate matter collected at the NASN sites
from 1957 to 1969 were analyzed for trace metals, including vanadium. The minimum level of
detection for the spectrographic analytical method is considered to be 3 ng/m3 for urban sites and
1 ng/m3 for nonurban sites (located in national parks or other remote areas). Concentrations fall-
ing below these threshold levels were entered at one-half the minimum level of detection for pur-
poses of computation. Additional statistics (maximum, minimum, etc.) are available for the year
1968, the only recent year in which the 24-hour paniculate samples were individually analyzed.
In other years, the individual samples were combined into quarterly composites.
5.2.1.1J. Long-term trends — Table 5.9 presents the annual average vanadium concentration for
urban NASN sites with complete data for the 5-year period of 1965 through 1969.24 Table 5.10
presents similar data for the nonurban sites.
The overall averages do not seem to reflect a clear pattern of increasing vanadium concentrations
over the period. Rather, it appears that there were considerable year-to-year fluctuations in
ambient levels, with substantially higher levels in 1967 and 1969 than in the other 3 years. This
observation seems consistent with the belief that the major source of vanadium emissions is the
combustion of fuel oil for power production and space heating, which, though generally increasing,
varies considerably from year to year in response to the severity of the winter season. Concentra-
tions at the nonurban sites seem to follow the basic trend of the urban sites at approximately
one-tenth the level.
Figures 5.1 and 5.2 present the annual averages for the 5-year period in the form of histograms for
the urban and nonurban sites, respectively. Although the distribution remains fairly stable from
year to year, in the high concentration year of 1969, much of the increase occurred at sites that
had traditionally exhibited very low ambient levels.
5.2.1.1.2. Geographic distribution — Ambient concentrations of vanadium are by no means geo-
graphically uniform (see Figure 5.3, based on Tables 5.9 and 5.10). Sites that have experienced
relatively high long-term vanadium concentrations occur in quite well-defined geographic clusters.
The highly urbanized region along the Atlantic coast from New England to Virginia is the nation's
leader in vanadium concentrations. In addition to being densely populated, this region is highly
dependent on fuel oil (much of it from vanadium-rich crude oil of Venezuela) for power pro-
duction, space heating, and industrial purposes.2 Also, almost all of the plants producing vanadium
chemicals in the United States are located within this region.29
Relatively high concentrations are also found in Puerto Rico and Hawaii (where fuel oil, rather
than coal, is the major source of energy), in the Chicago metropolitan area, and in the urban centers
along the Pacific Coast. The average vanadium levels throughout the remainder of the country
were generally less than 10 ng/m3 for the 5-year period. This undoubtedly reflects the availability
and use of coal, natural gas, and vanadium-poor fuel oil in those areas.
5-10 STAR —VANADIUM
-------
Table 5.9. ANNUAL AVERAGE VANADIUM CONCENTRATIONS — NASN
URBAN SITES, 1965-1969"
(ng/m3)
Site
AZ, Phoenix
Tucson
CA, Los Angeles
Oakland
San Diego
San Francisco
CN, New Haven
DE, Wilmington
DC, Washington
GA, Atlanta
HI, Honolulu
ID, Boise City
IL, Chicago
IN, Hammond
Indianapolis
South Bend
IA, Des Molnes
KN, Wichita
KY, Louisville
LA, New Orleans
MD, Baltimore
Ml, Detroit
MN, Minneapolis
St. Paul
MO, Kansas City
MT, Helena
NE, Omaha
NV, Las Vegas
NH, Concord
NJ, Glassboro
Annual avg.
68
5
b
11
19
28
24
377
149
128
b
38
b
83
33
13
131
4
b
7
14
71
11
9
9
. 14
b
3
b
37
72
66
b«
b
21
14
16
17
327
115
118
14
27
b
47
17
9
50
b
b
b
9
254
5
5
5
4
b
b
b
73
37
67
b
b
18
29
20
16
492
189
164
4
15
b
58
34
15
30
b
b
9
26
199
11
6
24
7
b
b
b
143
51
68
b
b
12
12
6
10
533
236
87
b
49
b
35
12
3
5
b
b
b
7
185
6
2
8
3
b
b
b
53
34
69
8
8
15
30
31
23
897
372
139
23
32
13
96
98
22
47
12
9
17
22
279
19
17
24
11
b
7
7
95
97
5-Yr.
avg.
4
3
15
21
20
18
525
212
127
9
32
3
64
29
10
53
4
3
7
16
198
10
8
14
8
b
3
b
80
58
SHe
Jersey City
Newark
Perth Amboy
NM, Albuquerque
NC, Charlotte
OH, Okron
Cincinnati
Cleveland
Columbus
Toledo
Youngstown
OK, Oklahoma City
Tulsa
OR, Portland
PA, Philadelphia
Pittsburgh
Reading
Warminster
PR, Bayomon
Catano
Rl, Providence
TN. Chattanooga
Memphis
TX, Houston
San Antonio
UT, Salt Lake City
VA, Norfolk
WA, Seattle
WV, Charleston
Wl, Milwaukee
Overall avg.
Annual avg.
65
319
349
267
b
23
4
8
4
5
7
3
b
b
46
398
b
87
58
41
105
256
5
b
b
b
7
76
39
17
7
51
66
262
257
202
b
19
b
b
b
b
b
4
b
b
30
133
b
92
94
62
67
341
4
b
b
b
b
32
28
14
b
48
67
487
344
390
b
18
6
8
4
b
5
4
b
b
37
263
16
81
98
131
55
271
5
b
b
b
4
50
22
15
4
65
68
355
265
104
b
14
b
b
b
b
b
b
b
b
41
358
3
96
37
78
80
389
3
b
b
b
b
57
19
16
b
54
69
202
146
123
8
38
10
12
14
10
7
9
5
4
54
434
15
141
59
70
212
607
13
7
6
b
b
131
37
33
18
81
5-jrr.
avg.
325
272
217
b
22
5
6
5
4
4
4
b
b
42
317
7
99
69
76
104
373
6
b
b
b
3
69
29
19
5
60
•b—below minimum dettctiblt Itvcl.
It is worth noting that even nonurban sites located along the eastern seaboard exhibit elevated vana-
dium concentrations, in marked contrast to the barely detectable levels observed at nonurban sites
throughout the rest of the country. This suggests that urban emisions of vanadium in the Northeast
are adversely affecting the air quality hi rural areas within the region.
Table 5.11 lists all urban sites that in 1968 exceeded an annual average vanadium concentration
of 100 ng/m3 and all nonurban sites that exceeded an annual average of 10 ng/m3. All sites are
located along the eastern seaboard, and in each case, the maximum vanadium concentrations
occurred during the peak period of fuel oil consumption for space heating.
5.2.1.1.3. Seasonal distribution — From what has preceded, it seems reasonable to suspect that
ambient concentrations of vanadium increase during the odder portion of the year as fuel oil con-
sumption increases to meet the space-heating demand. To test this hypothesis more formally, aver-
ago concentrations were calculated for the first and fourth quarters (combined) and the second and
Environmental Appraisal
5-11
-------
Table 5.10 ANNUAL AVERAGE VANADIUM CONCENTRATIONS — NASN
NONURBAN SITES, 1965-1969"
(ng/m8)
Site
AZ, Grand Canyon N.P.°
AR, Montgomery Co.
CA, Humboldt Co.
CO, Mesa Verde N.P.
IN, Parke Co.
ME, Acadia N.P.
MD, Calvert Co.
MO, Shannon Co.
MT, Glacier N.P.
NE, Thomas Co.
NV, White Pine Co.
NH, Coos Co.
NY, Jefferson Co.
NC, Cape Hatteras
OK, Cherokee Co.
OR, Curry Co.
PA, Clarion Co.
Rl, Washington Co.
SC, Richland Co.
SD, Black Hills
TX, Matagorda Co.
VT, Orange Co.
VA, Shenandoah N.P.
Overall average
Annual avg.
1965
1
b
b
b
1
8
6
b
b
b
2
2
5
2
b
b
1
24
1
b
1
13
1
3
1966
bb
b
b
b
1
11
24
b
b
b
b
9
6
5
b
b
1
31
2
b
b
28
1
5
1967
b
b
b
b
b
29
44
1
b
b
b
7
9
5
b
b
1
48
4
3
b
64
2
9
1968
b
b
b
b
b
4
19
b
b
b
b
5
5
4
b
b
b
33
2
b
b
41
1
5
1969
b
b
b
b
2
17
34
b
b
b
b
12
17
8
b
b
3
46
6
1
2
53
8
9
5-yr avg.
b
b
b
b
b
13.8
25.4
b
b
b
b
7.0
8.4
4.8
b
b
1.2
36.4
3.0
b
b
39.8
2.6
6.3
°N.P. National Park.
*>Below minimum detectable level.
third quarters (combined) for the year 1968 (Table 5.12). Nationwide, the average vanadium level
in the colder half of the year was more than triple the level of the wanner 6 months. This strongly
confirms the dominant role played by fuel oil combustion with regard to concentration of vanadium
in ambient air.
52.1.1,4. Size distribution of particulate vanadium — The size distribution of vanadium-bearing
particulate matter emitted to the atmosphere is of interest since it affects the proportion of the
emitted particulate. vanadium that will remain suspended and also the proportion that will be
respirable by human beings. Size distribution of trace metals was the subject of a special NASN
study26 conducted during 1970 (Table 5.13). Approximately 80 percent of the suspended vana-
dium particulate has a mass median diameter (MMD) of less than 2 /-tin. This means that virtually
all of the suspended vanadium particulate is below the upper limit of human respirability (gen-
erally considered to be 5 ftm). Lead was the only other trace metal evaluated in the study that was
associated with such small particles. The vanadium size distribution is quite uniform from site to
site, further evidence that most airborne vanadium may be traced to a common source, fuel oil
combustion.
5.2.1.2. Area Studies — Although no studies designed specifically to determine the influence of
vanadium sources on ambient concentrations have been reported, the metal has been included
among the trace metals determined in several special area studies of air pollution patterns.
5-12
STAR —VANADIUM
-------
Table 5.11 NASN URBAN SITES EXCEEDING 100 ng/m3 AND
NONURBAN SITES EXCEEDING 10 ng/m8, 1968"
-- Site
LUrban:
Boston, MA
New Haven, CT
Providence, Rl
Philadelphia, PA
Jersey City, NJ
Bayonne, NJ
Hartford, CT
Newark, NJ
Wilmington, DE
Camden, NJ
Paterson, NJ
Worcester, MA
Baltimore, MD
E. Providence, Rl
Harrisburg, PA
Perth Amboy, NJ
Nonurban:
Orange Co., VT
Washington Co., Rl
Calvert Co., MD
, Kent Co., DE
Annual avg.
617
533
389
358
355
285
269
265
236
215
210
198
185
126
105
104
41
33
19
18
Maximum quarterly
avg./flrst quarter
ofyr
1,102
1,134
944
846
994
731
661
649
591
408
651
523
530
226
288
247
96
46
36
39
Maximum 24-hr
avg./date and
month
1,600(2/28)
2,500(1/29)
1,600(2/15)
1,600(1/3)
2,300 (
930
1,700
1,400
1,100
1/2)
2/27)
1/3)
2/27)
2/18
770 (2/26
1,400(2/27
950 (2/5)
720
560
940
450
[2/27)
2/27)
1/28)
1/3)
180(1/29)
150 (4/12)
55 (3/26)
130(1/3)
5.2.1.2.1. Kanawha Valley — During 1964-1965, a comprehensive air pollution study was con-
ducted in the Kanawha Valley of West Virginia.27 Twenty-four-hour samples of suspended particu-
late matter were collected at 14 of the sampling sites (Table S.I4 and Figure S.4). Samples from
selected sites were composited on a seasonal basis and analyzed for trace metal content by the
NASN emission spectrographic method. In addition, monthly dustfall samples were collected at
several of the sampling sites.
Vanadium concentrations in the study are quite low (Table 5.14), averaging about one-tenth the
national average for urban areas. This is probably due to the abundance of coal and natural gas in
the area, which tends to minimize the use of fuel oil. (Both of the major power plants in the valley
are coal-fired, and an estimated 95 percent of the households are heated with natural gas). The
data do indicate, however, that maximum levels tend to occur during the fall and winter seasons
and in the areas of highest population density.
5.2.1.2.2. Birmingham — During 1964-1965, seasonal levels of trace metals were determined for
suspended paniculate samples collected at 10 Birmingham, Alabama, area sampling sites (Table
5.15).28 In Birmingham, as in West Virigina, the vanadium levels were quite low. Here, the
familiar seasonal pattern was not in evidence, and levels appeared fairly uniform throughout the
study area.
5.2.1.2.3. Chicago — Neutron-activation analysis was used to determine the trace metal content of
24-hour samples of paniculate matter collected on a single day (April 4, 1968) at 22 sampling
stations distributed over the Chicago metropolitan area (Figure 5.5).29 The vanadium concentra-
Environmental Appraisal
5-13
-------
Table 5.12. VANADIUM CONCENTRATIONS BY SEASON, 1968"
(ng/m3)
Site"
CA, Burbank
Long Beach
Oakland
San Diego
CN, Hartford
New Haven
DE, Kent Co.
Newark
Wilmington
DC, Washington
FL, Jacksonville
Tampa
HI, Honolulu
IL, Chicago
IN, Hammond
South Bend
LA, New Orleans
First and
fourth
quarter
19
18
18
11
449
867
26
52
395
133
51
30
86
62
18
6
9
ME, Acadia Nat'l Park 2
MD, Baltimore
Calvert Co.
263 •
24
MA, Boston 845
Worchester 341
Ml, Detroit 5
NV, Reno 24
NH, Concord 72
Coos Co. 6
NJ, Bayonne 432
Camden 285
Glassboro 44
Hamilton 102
Jersey City ;
Newark
Paterson
547
391
346
*
—•-
Second and
third
quarter
2
2
6
2
74
186
8
9
63
41
19
19
6
8
7
6
5
5
100
14
347
64
7
14
29
5
147
137
24
47
122
106
90
Ratio
9.5
9.0
3.0
5.5
6.1
4.7
3.3
5.8
6.3
3.2
2.7
1.6
14.3
7.8
2.6
1.0
1.8
0.4
2.6
1.7
2.4
5.3
0.7
1.7
2.5
1.2
2.9
2.1
1.8
2.2
4.5
3.7
3.8
Site
NJ, Perth Amboy
Trenton
NY, Jefferson Co
NC, Cape Hattera
Charlotte
Durham
OR, Portland
PA, Allentown
Bethlehem
Harrisburg
Johnstown
Philadelphia
Pittsburgh
Reading
Scranton
Warminster
West Chester
York
PR, Bayomon
Catano
Guayanillo
Ponce
Rl, E. Providence
Providence
Washington Co.
SC, Columbia
Greenville
VT, Burlington
Orange Co.
VA, Hampton
Norfolk
Richmond
WA, Seattle
WV, Charleston
Overall
*irst and
fourth
quarter
144
64
8
5
23
6
64
135
83
153
9
552
5
130
102
58
42
154
92
84
54
12
165
679
37
12
17
77
71
43
77
92
33
20
185
Second and
third
quarter
59
59
2
4
4
3
21
39
30
49
3
142
2
66
30
11
8
12
63
76
40
9
85
123
30
2
2
55
9
17
35
16
5
12
52
Ratio
2.4
1.1
4.0
1.3
5.8
2.0
3.0
3.5
2.8
3.1
3.0
3.9
2.5
2.0
3.4
5.3
5.3
12.8
1.5
1.1
1.4
1.3
1.9
5.5
1.2
6.0
8.5
1.4
7.9
2.5
2.2
5.8
6.6
1.7
3.6
«Sltes with more than one quarterly average below the minimum detectable level were not Included in the analysis.
The overall means differ significantly at the 99 percent confidence level (t-test).
-------
28
22
4 , 4
I I
« '
I i
1965
31
20
I I
1966
(A
111
V)
27
22
I I
1967
34
18
1968
IS
I 1
23.0
2.4
OVERALL
AVERAGE
10 10-89 100-199 200-299 300-399
VANADIUM CONCENTRATION INTERVAL, ng/m?
Figure 5.1. Histogram for NASN urban sites, 1965-1969,24
>400
Environmental Appraisal
5-15
-------
V)
9
12
11
14
10
11.2
12
7
8
*
6
7
'
8.0
1965
1 1
1966
1 2 1
• i I I i •
1967
3
. ' -, II
1 1 1 1
1968
1 1 1
1969
3 . :
1 1 ' i— * — r
OVERALL
AVERAGE
•
1.2 0.8 Q« 1J *
I 1 1 1 1 « • 1 1 — 1
5-16
<1 1-9 10-19 20-29 30-39
VANADIUM CONCENTRATION INTERVAL, ng/m3
Figure 5.2. Histogram for NASN nonurban sites, 1965-1969.24
/
STAR — VANADIUM
-------
NEW ENGLAND
AND MID-ATLANTIC
COAST (MAX. 525
>50 ng/m3
>20 TO 50 ng/m3
20 ng/m3
<10ng/m3
Figure 5.3. Geographic distribution of vanadium concentrations. Generalized on basis of 5-vear
(1965-1969} averages for NASN sites. 24 r
-------
Table 5.13. QUARTERLY AND ANNUAL SIZE DISTRIBUTION
FOR VANADIUM, 1970"
City
Chicago, III.:
No. of samples
Avg. cone., ng/m3
Avg. MMD, /tun
Percent particles < 2 /*m
Philadelphia, Penn.:
No. of samples
Avg. cone., ng/m3
Avg. MMD, /*m
Percent particles ^ 2/*m
Washington, D.C.:
No. of samples
Avg. cone., ng/fn3
Avg. MMD, /*m
Percent particles < 2/*m
Quarter
1
4
120
0.66
76
1
240
0.35
83
4
150
0.47
81
2
6
30
0.99
74
6
100
0.45
82
5
60
0.62
79
3
7
20
1.25
69
7
90
0.82
78
7
60
0.88
74
4
4
70
0.52
82
4
120
0.42
84
5
90
0.75
79
Year
21
60
0.72
76
18
140
0.45
82
21
90
0.61
79
tions exhibit a great deal of site-to-site variability, ranging from 2 ng/m3 at suburban Morton Grove
to 120 ng/m8 near the Loop in downtown Chicago.
5.2.1.2.4. New York City — In 1968, a study was conducted to determine the atmospheric burden
of trace metals in the New York City area and, if possible, to relate these concentrations to certain
meteorological parameters.30 Continual weekly paniculate samples were collected at sites located at
lower Manhattan and the Bronx, while simultaneous samples were collected in a rural area near
Tuxedo, New York (about 48 km northwest of New York City), to provide background informa-
tion. The analysis was done by atomic absorption.
Vanadium levels are abnormally high, reflecting the city's extreme population density and depend-
ence on vanadium-rich fuel oil for space heating (Table 5.16). Vanadium emissions in the city
apparently affect the atmosphere of rural areas as far as 48 km away.
Correlations between vanadium concentrations and meteorological data revealed a strong tend-
ency for vanadium levels to increase with decreasing temperature and increasing atmospheric
stability.
52.1.2.5. Helsinki — A trace metal investigation sponsored by the World Health Organization was
conducted in Helsinki, Finland, during 1962-1963 (Table 5.17).31 The results of the study prompted
the Institute of Occupational Health to investigate vanadium levels hi Helsinki. In this second
study,131 monthly dustfall samples were collected at 12 sites within the city from October 1964 to
September 1965. Vanadium content of the settled dust was determined by the spectrophotometric
technique. The results (Tables 5.18 and 5.19 and Figure 5.6) confirm the expected seasonal pat-
tern in vanadium prevalence. Oil-heating systems are predominant hi Helsinki, especially in the
center of the city. The vanadium deposition was heaviest in the business district of Aleksanterin-
katu, which is consistent with the earlier findings of the World Health Organization.
5-18
STAR —VANADIUM
-------
Tabte 5.14. VANADIUM CONCENTRATIONS, KANAWHA VALLEY STUDY24
Sampling site
and
number
Falls View (1)
Srmthers (5)
Montgomery (6)
Cedar Grove (7)
Marmet (11)
Kanawha City (13)
Charleston (15)
West Charleston (17)
North Cfiarleston-W (19)
South Charleston-E (20)
Dunbar (22)
St. Albans (24)
Nitro (25)
NKro-West (27)
Suspended particulates,
ng/m3
Seasonal averages
Fall
1964
b"
4
17
11
4
10
Winter
1964-65
b
b
b
7
6
8
8
5
b
4
5
7
8
Spring
1965
b
b
5
4
b
3
Summer
1965
b
7
9
5
b
5
Study period
average
b
3
9
5
2
6
Study period
average of
settled particulates,
mg/mVmo
0.35
0.91
0.56
0.39
0.31
0.23
0.21
0.32
0.70
0.94
0.26
0.25
0.28
0.25
«b—below minimum detectable level.
-------
WESTOFNITRO
NORTH CHARLESTON, WEST
\ V
OouNBAR
!
TINSTITUTE
24^^23.22
ST. ALBANS
i;/11Tnn
N%ITR°
SOUTH CHARLESTON. WEST
SOUTH CHARLESTON, EAST
NORTH CHARLESTON, EAST
CREDE
• 18 /
WEST CHARLESTON
//
CHARLESTON
KANAWHA CITY
* BELOW MINIMUM
• DETECTABLE
13 ?) 14 EAST CHARLESTON
/ T 12 SOUTH MALDEN
9
MARMET 11
CHESAPEAKE 10
BELLE { CEDAR GROVE
CHEYLAN 8
\.
MONTGOMERY 6
VKIMBERLY
SMITHERS
5
k4 BOOMER
ALLOY
MONTGOMERY
HEIGHTS
1 FALLS VIEW
Figure 5.4. Location of fixed sampling stations in Kanawha River Valley. Average vanadium
concentrations (ng/m3) for the study period (1964-1965) are indicated for selected sites.27
Table 5.15. SEASONAL AMBIENT VANADIUM CONCENTRATIONS-
BIRMINGHAM, ALABAMA, AREA, 1964-1965"
(ng/m3)
Place
Bessemer
Birmingham
Birmingham
Birmingham
Birmingham
Fairfield
Irondale
Mt. Brook
Tarrant
Vestavla
Area
Site
1
3
5
7
1
1
1
1
1
— —
Seasonal averages0
Spring
5
4
8
12
8
9
4
3
4
4
6
Summer
5
7 .
7
7
3
4
b
b
10
4
5
Fall
11
7
b
7
b
b
3
3
8
3
5
Winter
b
b
9
b
4
b
b
4
4
b
4
Study
•»«%»!«%«•
period
average
6
5
7
7
4
5
3
3
6
4
5
5-20
ob—below minimum detectable level
STAR — VANADIUM
-------
'EVANSTON
k %
i
JYJp-ICHICAGO CITY LIMITS
! PARK l7
] RIDGE _
I _ 16
IELMWOOD
J PARK
3.6
110
WSVWOOb
BERWIN
u
o
CO
NORTH
\
LAKE MICHIGAN
120
r---J
I MIDWAY),,
I AIRPORT
27
8.8 EVERGREEN
PARK
2
1
'6
_l_
i *• — —
kllomrten
RIVERDALE
Un
4.7
- I - 4£ -I
CALUMET CITY
Figure 5.5. Vanadium concentrations for Chicago (24-hour averages
in nanograms per cubic meter).29
Environmental Appraisal
5-21
-------
Table 5.16. ANNUAL AVERAGE VANADIUM CONCENTRATIONS,
NEW YORK CITY, 196830
(ng/m3)0
Site
Bronx
Lower Manhattan
Tuxedo
Minimum
600
310
40
Maximum
2790
2380
210
Annual average
1460
1190
120
"Continual weekly participate samples.
Table 5.17. ANNUAL AVERAGE VANADIUM CONCENTRATIONS,
HELSINKI, FINLAND, 1962-1963"
Site and type of area
Concentration, ng/m3
Sturenkatu (industrial area)
Pengerkatu (old residential area)
Aleksanterinkatu (business district)
Albertinkatu (residential area near a harbor)
Minna Canthinkatu (park and hospital area)
55
47
110
68
42
Six-hour samples of suspended participates were also collected at six of the sampling sites from
December 1964 to February 1965 (Table 5.20). Since the samples were obtained on a 6-hour basis,
it was possible to evaluate the diurnal pattern of vanadium concentrations (Figure 5.7). In con-
trast to particulate matter in general, vanadium levels increased in the evening and early morn-
ing hours during four 6-hour periods, apparently in response to diurnal heating patterns.
5.2.2. Water
The concentration of vanadium in fresh water is largely dependent on the amount leached from
the soil and rocks in the area of the stream, lake, or pond. Vanadium concentrations in water
differ geographically because not all soils or rocks contain the same concentrations. The range of
vanadium content in water is clearly demonstrated in a spectrographic analysis by Kopp and
Kroner32 of trace metals in rivers and lakes in the United States. The findings for vanadium
were summarized as follows:
5-22
Vanadium is not included in the Drinking Water Standards. It is included in the Criteria
for irrigation water, where the tentative limit is given as 10 mg/1 for continuous use on all
soils as well as for short-term use on fine textured soil. In the collection of data here
reported, this metal was observed with the greatest frequency in the Colorado River Basin
(9?f), where the range of concentration was 7 to 300 ftg/I with a mean of 105 /ag/1. It
was also observed in two samples from the Missouri River Basin at 158 and 184 /tg/1.
Vanadium has never been detected at measurable concentrations in the Tennessee River
Basin. Western Great Lakes Basin, or The Great Basin. It was observed in only 54 of the
more than 1,500 samples analyzed for a frequency of 3.4%.
STAR — VANADIUM
-------
Tflble 5.18.' MONTHLY VANADIUM DEPOSITION, HELSINKI, FINLAND, 1964-1965"
Level
Maximum
Minimum
Mean
Concentration by month and year, mg/nf-mo
10/64
3.61
0.49
1.77
11/64
7.78
0.62
2.20
12/64
6.96
0.10
1.63
8/65
11.97
0.19
2.45
2/65
9.20
0.30
2.33
3/65
8.11
0.66
2.64
4/65
7.59
1.11
2.37
5/65
6.88
0.93
2.03
6/65
3.10
0.47
1.31
7/65
2.45
0.44
1.29
8/65
3.72
0.65
1.66
9/65
3.17
0.50
1.61
Table 5.19. VANADIUM DEPOSITION AT VARIOUS INVESTIGATION
POINTS, HELSINKI, FINLAND, 1964-1965"
Level
Maximum
Minimum
Mean
Concentration at Investigation point, mg/nf-mo
1
2.06
0.59
1.25
2
1.28
0.19
0.57
3
1.84
0.33
0.93
4
1.83
0.24
1.03
5
2.63
0.46
1.29
6
1.40
0.10
0.72
7
4.01
0.94
2.33
8
2.43
0.84
1.64
9
4.08
1.25
2.28
10
4.26
1.52
2.62
11
1.97
2.45
6.19
12
5.05
1.47
2.39
-------
Table 5.20. AVERAGE VANADIUM CONCENTRATIONS, DECEMBER TO
FEBRUARY 1965, HELSINKI, FINLAND31
Investigation point
Railway station
Albert! nkatu
Al eksanteri'Rkatu
City Gardens
Hameentie
Institute of Occupa-
tional Health
Number of samples
15
12
13
12
13
10
Vanadium concentrations,
ng/m3
Maximum
1,085
1,180
675
930
700
249
Minimum
57
3
105
022
009
7
Arithmetic
mean
399
257
259
164
211
102
The average for the 54 positive samples in the study was 40 ^ig/liter, with a range of 2 to 300
p.g/liter. The Colorado Plateau is the principal commercial source of vanadium-bearing ores in the
United States. The vanadium content of waters draining this area has been studied by Linstedt and
Krugcr." They employed a more sensitive analytic method (neutron activation) for analysis of
their sample than did Kopp and Kroner. Their findings were summarized as follows:
Vanadium concentrations in samples throughout the Colorado River Basin varied between
0.2 and 49.2 /ig/1 over the 15-month period of the study. The lowest vanadium concen-
trations were found in samples from sites on the Animas and Green Rivers. Both these
sites arc upstream of any major industrial activity. Highest concentration values were found
at the sampling sites in the vicinity of the uranium-vanadium milling operations.
Flow levels in the streams and rivers sampled made a noticeable difference in the concentrations ob-
served. The water courses sampled flow into Lake Powell, where they are mixed. Using the data
collected and assuming that the vanadium remains in solution once it has entered the fresh water
course, the concentration in the lake was calculated to be 3.6 fig/liter. Measurements of the lake
effluent showed a level of 3.4 fig/liter, which is in good agreement with measurements from the
stream entering the lake.
In fresh waters, vanadium is usually in solution as a salt.3 Pentavalent vanadium compounds are the
most soluble. In going from the rocks and soil into the water, vanadium is oxidized from the tri-
vulcnt to the pcntavalcnt state. Microorganisms play a significant role in making it more soluble
and thus capable of transport.
Durfor and Becker34 included vanadium in their trace element analyses of drinking water supplies
in the United States. Of the samples analyzed, 91 percent were below 10 fig/liter; the maximum
level found was 70 /ng/liter, and the average was about 4.3 /tig/liter.
Much of the soluble vanadium in rivers is removed by precipitation when rivers reach the sea.3
Bowcn35 estimated that only about 0.001 percent of the vanadium entering the oceans is retained
in soluble form in sea water. The total amount of vanadium in the oceans is estimated3 to be 7.S X
1()12 kg. The concentration of vanadium in sea water ranged from 0.2 to 29 /*g/liter. Riley and
Taylor'1" made a detailed study of several metallic elements in waters off the African coast south
5-24
STAR — VANADIUM
-------
10
e
I
e
P
2
* R
U Q
e
u
0,
'
I I
J
'
1
1
1
1
r-j
1
1
I
i
1
"""/
/
/
-*-*^X. .
^ Xx
"T""XK..
10 fi iii;
1964
i i i i i i i i
t\
i \
r \ -
\ MAXIMUM
\
\
\
X
X
\
\
\
\
\
\ .
\ / Xx^
X^ / ^
i — _ -***^'^^%fc- ***/
^
MINIMUM ^^ •*. ^
4 — f^i_ _[ 1^-L--f-"l^
1 ,2 3 4 B 6 7 8 'I
1965
TIME, months
Figure 5.6. Monthly variation of vanadium deposition, Helsinki, Finland, 1964-1965.31
Environmental Appraisal
5-25
-------
0.6
0.5
0.4
3
u
S 0.3
0.2
0.1
0-6
0.3
0.2
0.1
18-24
5-26
6-12 12-18
TIME.houn
Figure 5.7. Daily variation of total participate and vanadium concentratignslh air
•heating area during cold period, Helsinki, Finland, 1964-1965.31 "7
STAR — VANADIUM
-------
of the Canary Islands. Their samples ranged in vanadium content from 0.2 to S.I /xg/ltter, with a
mean of 2.1 fig/liter. The standard deviation was large. No pattern of distribution was observed
that could be related to the physical variations in the ocean. A biological basis for the patchy dis-
tribution was postulated but could not be demonstrated in the study. Krauskopf87 also postulated
a biological basis for the removal of vanadium from ocean water. He found that vanadium was not
removed by precipitation as sulfide or other insoluble forms. Also, vanadium was insufficiently
removed by adsorption on substances such as manganese or ferric oxides to explain the low levels
encountered in the sea. The nature of the postulated organic mechanism of removal of the metal
to bottom sediments is not known.
5.2.3. Soil
Information on vanadium in soils, rocks, and sediments may be found in several reviews.3-38-*1 The
average concentration of vanadium in the earth's crust is estimated3 to be 150 mg/kg. The prin-
cipal source of soil vanadium is the parent rocks from which the soils are formed. Many studies
of soil composition have been conducted — so many that it is difficult to compile the data. Almost
all soils studied contain small amounts of vanadium; negative findings are thought to result from
inadequate methodology. Vanadium levels are reported in the literature to range from 3 to 300
/xg/g; concentrations in the United States are at the higher end of the range, those in Japan at the
median level, and concentrations hi Europe at the lower end of the range. Bertrand39 indicates that
soils originating from Tertiary rocks are lowest in vanadium, Mesozoic-derived soils are somewhat
higher, and those of Paleozoic origin are highest.
5.2.4. Food
Ingestion of food and water is the primary source of vanadium hi man. For urban populations, the
intake of vanadium from air is calculated to be, on the average, only 3 percent. This amount varies,
depending on natural concentrations present in water and soil and on degree of industrialization
and air pollution. For example, the polluted air of New York City may account for as much as 10
percent of the total intake of vanadium.42
Schroeder et al.43 measured concentrations of vanadium in various categories of foods. Their data
indicate that diets containing shellfish, prepared grams, legumes, and leafy vegetables are relatively
high in vanadium (Table 5.21). Sardines and herring have been shown to contain 20 /tg/100 g
when analyzed by colorimetric techniques. Meat and fruit contained little vanadium.
Studies on vanadium content of foodstuffs and its possible role in the etiology of endemic goiter
showed this metal to be fairly consistent in two regions sampled.44 Low levels of 1.46+ 0.13 and
0.88 ± 0.7 /ng/100 g and high levels of 19.40 ± 3.50 and 22.80 ± 5.75 fig/100 g raw weight
were found, respectively, in the two regions sampled. High values were obtained for carrots, cab-
bage, beans, and sunflowers in both regions.
Fresh milk samples from six locations, taken and analyzed by Soremark," contained about 0.1
ng/g vanadium. Calf liver and pork also had low levels, indicating that many of the most common
foods consumed by humans may be rather low in vanadium. The use of emission spectroscopy and
Environmental Appraisal 5-27
-------
Table 5.21. VANADIUM CONCENTRATIONS IN FOOD
Food
category
Seafood:
Shellfish
Fish
Meats
Dairy products
Grains:
Whole
Prepared
Vegetables:
Roots
Legumes
Leaves
Fruits
Nuts
Beverages
Condiments
No. of
foods per
category
4
2
8
8
14
6
8
9
9
8
8
1
5
Concentration (wet-weight basis), /xg/g
Mean
2.39
0.48
0.02
0.95
0.81
2.27
0.90
2.11
1.31
0.09
0.71
0.0
0.55
Range
0.11 to 5.1
0.0 to 0.96
0.0 to 0.14
0.0 to 6.52
0.0 to 2.30
0.07 to 6.03
0.0 to 3.02
0.0 to 6.00
0.55 to 2.53
0.0 to 0.36
0.0 to 1.96
0.06 to 1.36
neutron-activation analysis are improving accuracy and comparability of vanadium data on foods
and other biological materials.
Soremark'•"• analyzed various food items using neutron-activation analysis (Tables 5.22 and 5.23).
Parsley has an unusual affinity for vanadium, 29.5 /tg/g, followed by radishes, which averaged
7.9 /x.g/g in the 10 samples analyzed. The uptake of vanadium-48 from soil by several vegetables
also showed parsley and radishes to be high. Meat from North Sea lobsters had the highest level
of vanadium (16.1 //.g/g) followed by gelatin (2.5 /xg/g). All values were based on ash weight.
In the analysis of peas, Mitchell,46 using emission spcctroscopy, found low values for this vegetable,
nanograms per gram (wet basis) rather than micrograms per gram as reported by previous investi-
gators. These data, along with neutron-activation analyses by Soremark'15 and Lambert and Simp-
son'17 tend to support data showing low concentrations in foods.
Unrefined fats and oils, pressed soybeans,
the highest concentrations of vanadium
removes most, if not all, of the vanadium
fat from a person fed vanadium in soluble
times the amount of vanadium present in
showed no vanadium. Refined egg lecithin
hand, skim milk had 6.52 /*g/g, and egg
corn oil, margarine, pressed linseed, and olive oil showed
(Table 5.24.) The refining of fats and oils apparently
43 This was shown in the vanadium level in a sample of
form for a period of 18 months. His fat contained three
a person not fed this diet. Analyses of three refined fats
and butter also had no detectable vanadium. On the other
yolk had 0.68 /*g/g on a wet weight basis.43
Further evidence of vanadium removal by the refining process was shown with other vegetable oils.
All edible unrefined vegetable oils contained vanadium, as did cedar and crude linseed oil.
Refined castor oil had no vanadium; and pure vegetable lecithin had barely detectable amounts.
Half of the vanadium was lost by refining soybean oil. Extraction of iipid from whole rye flour
removed all traces of vanadium.
5-28
STAR — VANADIUM
-------
Table 5.22. VANADIUM CONCENTRATION IN ANIMAL SPECIMENS49
(/*g/g)
Specimen0
Calf liver, Stockholm
Calf liver, Boston
Calf flesh, Stockholm
Calf teeth, Stockholm
Calf 'bone, Stockholm
Pork, Stockholm
Fresh trout, soft tissues
Fresh mackerel, soft tissues
(North Sea)
Fresh mackerel, bone
Sardines, Sweden
Sardines, Norway
Sardines, Portugal
Fresh milk, Boston
Fresh milk, Chicago
Fresh milk, New York
Fresh milk, Stockholm
Fresh milk, Oslo
Fresh milk, Goeteborg
Dried skim milk:
Carnation (U.S.A.)b
Starlac1
Famon (Sweden)0"
Semper (Sweden)d
Lobster, meat (North Sea)
Gelatin (Sweden)
Mean,
ash-weight basic
0.51
0.11
< 0.0001
<0.0001
<0.0001
<0.0001
0.06
0.20
2.9
0.28
0.20
0.46
0.00024
0.00016
0.00013
0.00048
0.00020
<0.0001
0.005
0.00048
<0.0001
<0.0001
16.1
2.5
Mean,
wet-weight basis
0.01
0.0024
•
•
0.0024
0.0026
2.0
0.0086
0.0070
0.013
0.000084
0.000077
0.000074
0.00011
0.00008
0.00023
0.00019
0.043
0.044
"Ten samples were taken of each of the specimens listed.
^Carnation Food Company, Los Angeles, Calif.
cBorden's Food Products, New York, N.Y.
<>Semper Company, Stockholm, Sweeden.
The amounts of vanadium found in foods vary geographically. For example, vanadium has been
found in milk in Colorado Springs, Colo., but it was not found in milk from Rochester, New York.
Using neutron-activation analysis, vanadium was found at levels of 15 ng/g in random samples of
powdered milk taken in San Diego, Calif.45 Variations were found between milk sampled in Goten-
berg, Sweden «10'4 /ig/g), and Boston, Massachusetts (0.24 X 10"3 /*g/g).
For reasons not clear, institutional diets contained 10 times the levels of vanadium normally found
in foods.47 The use of insensitive colorimetric techniques in analyses of these diets may account
for this discrepancy and indicates a need to recheck these results.
The amount of vanadium in animal products is primarily from the feed and water ingested, although
un unknown amount, probably small, results from the absorption of vanadium from the lung. To
accurately assess the contribution that vanadium in food makes to the human body burden of
vanadium, comprehensive market basket and drinking water surveys are needed.
Environmental Appraisal
5-29
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Table 5.23. VANADIUM CONCENTRATIONS IN FRUITS AND
VEGETABLES45 (/ttg/g)
Specimen0
Dili
Lettuce
Parsley15
Cucumbers
Radisfiesb
Strawberries'"
Wild strawberries
Red whortleberries
Applesb
Tomatoes1'
Cauliflower
Potatoes''
Pears
f^n rr/vtch
Oxl 1 1 OLo
Common beets
Peas, frozen
Mean,
ash-weight basis
4.6
2.8
29.5
0.38
7.9
0.66
0.72
0.54
0.33
0.041
0.093
0.0093
-0.0001
,^n onni
*\ \j.\j\j\j i
-0.0001
< 0.0001
Mean,
dry-weight basis
0.84
0.58
4.52
0.056
1.26
0.031
0.041
0.0102
0.0086
0.00053
0.00109
0.0064
Mean,
wet-weight basis
0.14
0.021
0.79
0.0021
0.0521
0.0016
0.0011
0.000027
0.000077
0.00082
"Ten samples of each item were taken from the Stockholm area.
bFive samples of each grown in New Hampshire and five grown in Rhode Island were also
analyzed. Vanadium concentrations in these samples were, in general, somewhat lower
than those tabulated for the fruits and vegetables grown in Sweden.
Present data on vanadium levels in foods are sparse, and many of the available data may be ques-
tioned as to quality. Research is needed to develop reliable techniques for accurately and repro-
ducibly sampling and analyzing levels of vanadium in foods and other biological material and for
validating these techniques by actual field surveys.
5.2.5. Plaiils, Animals, and Man
5.2.5.7. Introduction — Vanadium is found throughout the biosphere. The content in plants,
animals, and humans is related to the vanadium in the physical environment on which the bio-
sphere is dependent. Vanadium occurs in a number of valence states and in a variety of materials.40
It is present in unrefined oils, in vegetable fats, and in many living organisms. Fatty tissues of
animals and humans appear to have an affinity for vanadium compounds. Vanadium apparently
forms ionic bonds with sulfhydryl groups, which could explain its relatively higher concentrations
in hair, keratin, and gelatin.
5.2.5.2. Plants — The concentration of vanadium in water and in soil appear to have the greatest
influence on the levels found in plants. Bertrand39 found vanadium in every sample of the 62 plant
species that he analyzed. The mean concentration in higher plants for fresh samples was 0.16 fig/g
fresh weight, 1.0 /*g/g dry weight, and 7 ftg/g in ash. The aerial portions of the plant had the
lowest vanadium content and the roots had nearly the same content as the soil in which the plant
was growing.
In a more recent study, Hanna and Grant48 analyzed the foliage of 12 different species of woody
ornamental plants to determine their mineral composition. Spcctrochcmical analyses of 43 different
5-30
STAR — VANADIUM
-------
Table 5.24. VANADIUM CONCENTRATIONS IN FATS AND OILS43-44
Fat or oil
Average concentration
(wet-weight basis), /tg/g
Animal fats
Mouse
Rat
Pig
Deer
Beef bone marrow
Chicken
Sperm oil
Human
Human (fed vanadium for 18 months)
Lard, refined
Butter
Cod liver, refined
Lecithin, bovine 90 percent
Egg lecithin, refined
Mean of fats, raw
Mean of fats, refined
Vegetable oils
Safflower, extracted
Cottonseed, extracted
Sunflower
Vegetable shortening
Cedar
Peanut, pressed
Corn, pressed
Linseed, crude, pressed
Olive, pressed
Soybean, pressed
Corn oil margarine
Mean
Castor, refined
Lecithin
Crude soy
Refined soy
Vegetable, pure
Rye seed flower
Extracted
Residue
Whole
3.06
0.06
6.76
6.82
3.17
13.85
12.67
1.62
5.13
0.0
0.0
0.0
1.28
0.0
6.00
0.0
2.85
3.02
6.95
7.49
8.98
10.87
11.05-15.80
11.76
15.23
43.53
21.75
14.77
0.0
2.45
1.19
0.58
5.50
0.0
1.24
leaf samples were made for 23 different minerals. The average concentration of vanadium in dry
samples was 1.2 fig/g. The authors state that the concentrations of some elements in plant tissue
vary with the time of the year, the climate, the soil, the organ sampled, and the position on the
plant. Further, they noted wide variations between species as well as within species. Illustrative
of this fact was the range of vanadium concentration in pin oak (Quercus pahistris Muench) —
0.06 to 4.8 /*g/g. The lowest and highest levels were found within this species.
Bertrand39 noted that the root nodules of legumes in which the symbiotic nitrogen-fixing bac-
terium, RMzobium, is growing contain from 3 to 4 /»g/g of vanadium in dry matter.
Environmental Appraisal
5-31
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Vinogradov38 studied marine organisms to determine a variety of metal concentrations (Table
5.25).
Table 5.25. VANADIUM CONCENTRATIONS IN PLANTS AND ANIMALS2
Plant
Plankton
Brown algae
Bryophytes
Ferns
Gymnosperms
Afigiosperms
Bacteria
Fungi
Average
concentration
(dry-weight bail*)
5
2
2.3
0.13
0.69
1.6
trace
0.67
Animal
Coelenterates
Annelids
Mollusks
Echinoderms
Crustaceans
Insects
Fish
Mammals
Average
concentration
(dry-weight basis)
2.3
1.2
0.7
1.9
0.4
0.15
0.14
<0.4
Cowgill49 analyzed aquatic plants in two freshwater lakes in Connecticut to determine their ele-
mental composition. She found that the vanadium concentration ranged from 0.4 to 80.0 ftg/g.
Ten specimens of each of six different species were analyzed. The rooted plant species contained
the highest vanadium concentrations. Pickerelweed (Pontedaria cordata L.) contained the highest
concentrations, 80.0 ftg/g. None of the other plants tested had levels higher than 5 ftg/g. The
author suggests that pickerelweed may be an accumulator of vanadium.
Amanita muscaria (L.) Fr., the fly agaric mushroom, is a known accumulator of vanadium. Ber-
trand39 noted that it contained approximately 100 times as much vanadium (16 to 181 ftg/g dry
weight) as other species of fungi.
Mosses have been mentioned as accumulators of vanadium as well as other metals. The concen-
tration of vanadium hi mosses, however, is not associated with uptake from the soil, but results
from deposition from the ah*.50
5.2.5.3. Animals — Vanadium is found in both terrestrial and aquatic animals (Table 5.26). Ber-
trand39 noted that concentrations in vertebrates were so low that it was often difficult to deter-
mine if vanadium was present at all.
The concentration of vanadium in sea weeds, mollusks, fishes, and sea water was determined by
Fukai and Meinke51 using neutron-activation analysis. The concentration of vanadium hi the soft
tissues of fish was determined to be 1,000 tunes that in sea weed and mollusks.
The highest concentrations of vanadium have been found in the blood of ascidians, certain holo-
tliurians, and in the mollusk, Pleurobranchus plumula. Concentrations in the ascidians ranged from
3 to 1,900 ftg/g, and even 42,000 ftg/g has been reported.52 The holothurian, Stichopus mobii, con-
tained 1,235 ftg/g, and the mollusk contained 150 ftg/g dry weight.92
5-32
STAR — VANADIUM
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Table 5.26. VANADIUM CONCENTRATIONS IN TISSUES OF
WILD ANIMALS2
-------
5.2.5.4. Humans — In humans, vanadium is one of the metals that accumulates in lung tissues
with age, an increase that is not evident in other body tissues. It can be inferred, therefore, that
vanadium is in the form of insoluble particulates in the lung. Over half of the 78 autopsied lungs
analyzed by Tipton and Shafer57 contained vanadium. Results varied from nondetectable to an
extreme of 68 /xg/g in dry ash of lung samples. Workers hi industry exposed to contaminated
dust excreted four times as much vanadium in their urine as did controls. This would indicate
that vanadium was absorbed from the lungs and intestines. In an extension of the above study, 168
human lung samples from adults hi the United States were analyzed for 24 trace and bulk ele-
ments found to increase up to the age of 40.57
Some indication that vanadium is absorbed into the blood via the lungs was reported hi animal
studies by Molfino.58 He observed that vanadium appeared in the urine shortly after rabbits were
exposed to vanadium oxide dust. Massmann59 also found that 7 days after injecting vanadium
pentoxide into rat's trachea, no vanadium remained hi the lung. Sj/Jberg60 hi an inhalation exposure
study of rabbits showed only slight retention of the metal hi the lungs.
Despite these animal studies showing rapid absorption and little retention of vanadium compounds
in the lung, the fact remains that with age, humans do accumulate this metal hi lung tissues.57
Autopsied lung tissues from persons aged 20 to 59 from Middle Eastern countries showed signifi-
cantly more vanadium than lung tissue taken from persons of similar age who resided hi the
United States, Africa, and the Far East. Differences hi the diets — particularly hi unrefined oils,
flour, and other foods — could account for these differences.61
Concentrations of vanadium and other metals were determined hi lung tissues of 65 deceased West
Virginia bituminous coal miners.62 The section of the upper lobe of the left lung closest to the rib
cage contained the greatest concentration of trace metals. Hilar lymph nodes of these miners had
a higher level of vanadium and free silica than did lung tissues. All trace elements were hi greater
concentration hi the miners than hi the same tissues of nonminers, based on values hi the litera-
ture. Reasonable correlation was shown between air concentrations of vanadium and vanadium con-
tent hi lungs.
Injection of vanadium-48 hi rats also resulted hi its accumulation hi lung tissues.53 In the Tipton
and Shafer57 study, paired rank correlation coefficients for concentrations of vanadium and 15
other trace metals with 28 different human body tissues other than lung were not significant. The
accumulation of vanadium hi the lungs and intestinal tract was similar to that for chromium and
manganese, both of which are biologically competitive with vanadium.
The small and large intestines were, next to lung tissues, highest hi levels of vanadium43 and hi
the frequency of occurrence. Vanadium has an apparent affinity for tissues with high sulfhydryl
and triphosphate polar groups. This is indicated by the high levels found hi samples of deer hoofs
(2.55 A*g/g), human hair (2.65 /tg/g), and gelatin (12.59 ftg/g). According to Schroeder et al.,43
storage of available vanadium hi humans is mainly hi fat and serum lipids. Their conclusions were
based on these findings: fatty muscle contained 1.2 /tig/g but contained none after fat was extracted;
human fat contained an average of 1.6 ftg/g, whereas fat from a patient receiving vanadium had
5.8 /*/g; and vanadium hi serum is removable by chloroform (a fat solvent) but not by trichloro-
acetic acid or acetone precipitation.
It has been estimated that the standard 70-kg man contains 25 mg of vanadium, with fat con-
5-34 STAR —VANADIUM
-------
taining 22.5 mg and serum, 1.3 rag. The high levels in serum and low levels in urine suggest that
either most of the serum is not filtered by the glomeruli or that renal reabsorption is efficient43
Gordos63 determined levels of vanadium in human hair samples. Depending on the frequency of
hair washings, the vanadium content ranged from a few nanograms per gram to 262 ng/g; the mean
was 60 ng/g. Older hair samples obtained from private museums dating as early as 1830 showed
generally lower values for vanadium. Whether the high levels found in contemporary hair specimens
are caused by increased industrial pollution or simply a change in external binding characteristics
of the hair specimens after long-term storage is not known. Infrequently washed hair gave higher
mean values, approximately 80 ng/g.
The low levels of vanadium detected in human tissues other than bone, skin, and lung indicate a
short residence time for the metal.
In the CHESS studies, the amount of vanadium was determined in maternal blood, cord blood,
scalp hair, pubic hair, and placenta.64 These data show low levels in all tissues analyzed. This
supports analyses made by other investigators on human tissue specimens from persons not subject
to high levels of vanadium exposure. Levels in hair are comparable to those found by Gordos.63
A number of studies 6W7 have been directed toward determining the effectiveness of vanadium
compounds in reducing cavities hi animal and human teeth. Analyses of teeth showed traces of
vanadium, with the largest quantity shown hi molars.
Table 5.27 presents a summary of vanadium levels determined by Tipton and Cook68 in human
tissue specimens.
5.3 TRANSPORT AND MODELING
5.3.1. Transport
An accurate description of the transformation and transport of pollutants emitted into the environ-
ment is needed so that the quality of the environment can be related to the sources of pollution and
so that predictions can be made on the emission control required under present and future condi-
tions. When particles are present, those processes that affect the size distribution spectrum in the
air parcel must be described. Processes affecting the aerosol spectrum near the earth's surface
include:69
Production of aerosols at the surface by natural and artificial sources.
Growth of particles by heterogeneous gas reactions on the surface of particles.
Production and growth of particles by homogeneous gas reactions and subsequent attachment
of reaction products to the aerosols.
Ciain or loss of particles entering by diffusion or convection from neighboring air.
Net change in particle concentrations by thermal (Brownian)coagulation.
Net change of particle concentrations by collisions between particles resulting from turbulent
velocity gradients.
Environmental Appraisal 5-35
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• Loss of particles by gravitational sedimentation.
• Loss of particles by impaotion on obstacles at the earth's surface.
• Loss of particles by washout under clouds.
• Loss of particles by rainout inside clouds.
Table 5.27. VANADIUM CONCENTRATIONS IN HUMAN TISSUES68
Tissue
Adrenal
Esophagus
Stomach
Duodenum
Jejunum
lleum
Cecum
Sigmoid colon
Rectum
Kidney
Liver
Heart
Lung
Omentum
Pancreas
Prostate
Spleen
Skin
Thyroid
Bladder
Uterus
Samples positive for W
samples analyzed
1/13
5/66
3/130
5/67
4/102
31/84
14/31
17/108
11/42
0/144
5/148
0/143
73/141
11/75
2/139
1/50
1/143
3/21
1/21
3/110
1/32
Concentration (ash weight), ^fl/fl
Median
<1
<1
<1
<1
<1
<1
<1
<1
<1
— —
<1
— —
<1
<1
<1
<1
<1
<1
<1
<1
<1
Maximum
<1
<1
<1
<1
<1
3
4
3
2
— —
<1
— — —
13
3
<1
<1
<1
<1
<1
<1
<1
Hidy70 has considered those processes that contribute directly to the aging (change in situ of physi-
cal or chemical properties) of aerosols in the atmosphere and has attempted to estimate the relative
importance of these mechanisms for three different particle size classes. From existing data, he
was unable to estimate the importance of heterogeneous gas-surface reactions and the formation
of particles by homogeneous gas reactions. His calculations demonstrate that thermal coagulation
and turbulent diffusion dominate the aging mechanism for particles near the ground. Gravitational
sedimentation is relatively unimportant for particles smaller than about 10 fjan radius but becomes
increasingly more significant as the particle radius increases.
Little information is available on the detailed mechanism by which airborne vanadium particles
participate in these processes. Furthermore, the ultimate fate of vanadium in the atmosphere is not
known. Vanadium residence time in the lower Delaware River Valley air shed, however, has been
roughly estimated to be 0.1 and 1 day.0
5.3.2. General Paniculate Modeling
Modeling efforts for particulates, including vanadium-containing particles, must consider the follow-
ing transport, transformation, and removal processes.
5-36
STAR —VANADIUM
-------
5.3.2.1. Sedimentation — Gravitational sedimentation, although relatively unimportant for parti-
cles less than 10 /xm radius, becomes increasingly more important as the particle size increases
above 10 ftm. Large vanadium particles emitted into the ambient air would be expected to fall out
in the near vicinity of their source.
5.3.2.2. Diffusion and Transport Processes — The transport of aerosol particles from one place
to another is controlled primarily by prevailing winds. Diffusion by Brownian motion is insignif-
icant when compared with the convection diffusion produced by turbulent air motion. Rural
areas on the eastern coast from Maine to South Carolina show a significantly higher concentration
of vanadium than other rural areas of the country. This finding suggests that vanadium emitted in
urban areas from the combustion of oil and coal is being transported to nonurban areas.
Little information is available on the transport of vanadium by groundwater. Although vanadium
pentoxide is not highly soluble in water (0.8 g/100 cm3 water at 20°C), its solubility would
probably increase significantly in an acid rain or if the oxide were converted to a sulfate such as
vanadyl sulfate. Microbial action is believed to assist in the conversion of vanadium into more solu-
ble forms for transport in groundwater.1
5.3.2.3. Coagulation Processes — Coagulation processes are known to affect aerosol distribution.
Hidy's calculation70 suggests that thermal coagulation is of primary importance for the smallest
particles near the ground. For particles larger than 0.5 fim radius, thermal coagulation decreases
in importance as the particle size increases. Turbulent coagulation is comparatively weak for particles
less than 0.5 /xm, but it becomes more significant for larger particles. However, near the ground,
where particle concentrations are high and turbulence intensity is great, turbulent coagulation may
provide an effective mechanism for growth between the range where thermal coagulation dominates
to the range where sedimentation dominates.
5.3.2.4. Heterogenous Gas Reactions on Surfaces of Particles — Particles in the atmosphere are
thought to be involved in many chemical reactions associated with photochemical smog. The oxida-
tion of gases such as sulfur dioxide is accelerated in the presence of particles; and the formation of
nitric acid, by the reaction of nitrogen pentoxide with water, is believed to be a surface reaction.
Although vanadium is frequently used as a catalyst in industrial applications, its catalytic reactivity
in the ambient air is unknown.
5.3.2.5. Scavenging — The scavenging of small particles by large particles falling through an air
parcel is thought to be negligible.
5.3.2.6. Washout and Rainout — Although the precipitation removal processes operate only inter-
mittently, they represent an important factor. Washout has been defined as the removal of particles
by sweepout by precipitation under clouds; whereas rainout refers to removal processes taking place
within clouds. Hidy's70 calculations suggest that washout may be less important than other removal
mechanisms near the ground, but that it becomes more significant at altitudes above 1 km.
5.3.2.7. Impaction and Dtffuslonal Deposition on Surfaces — Particles will be deposited on a sur-
face as a result of Brownian diffusion towards the surface and as a result of impaction. The larger,
heavier particles may be deposited on the surface; but smaller, lighter particles may not reach the
surface because they are dragged around by the deflected air before they contact the surface.
Environmental Appraisal 5-37
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5.3.2.8. Reentrainment — The possibility of reentrainment of particles located on surfaces must be
considered. The importance of this mechanism for reentrainment of vanadium from dust and soils
has not been assessed.
53.2.9. Microbial Action — Concentrations of vanadium in water and soil appear to have a large
influence on microbial action. Specific auxotrophic bacteria oxidize the reduced forms of vana-
dium to obtain a part or all of their energy for growth and multiplication.1 Goren71 has coupled
the iron-oxidizing bacteria with the oxidation of vanadium in acidic leaching solutions. The bio-
geochemical vanadium cycle in Figure 5.8 denotes these interrelationships.1 Thiobacillus ferrooxi-
dons and Fcrrobadllus thiooxidans catalyze the oxidation of iron, which in turn oxidizes vanadium.
The sulfate-reducing bacteria generate hydrogen sulfide and provide conditions for the reduction of
pentavalent vanadium and the formation of vanadium sulfides. Micrococcus lactilyticus catalyzes
the reduction of vanadium sulfide, and trivalent vanadium is formed. The mineral minasragrite is
probably formed by the microbial oxidation of vanadium sulfide.
5.3.3. Vanadium Model
Although development of a detailed model describing the mechanisms by which airborne vana-
dium particles precipitate hi the above process is beyond present capabilities, Tullar and Suffer6
have put forth an elementary model of the fate of vanadium in an urban air shed (Figure 5.9). The
shed covers an area approximately 40 km long, from Philadelphia to Delaware City, reaching 12
km on either side of the river for a 24-km width. An arithmetic mean vanadium concentration of
0.23 /ig/m3 is used for the model area for 1967.
The model assumed that the only significant emissions come from combustion of vanadium-rich
fuel oils in refineries, power plants, and other industrial sources. Approximately 3.8 X 106 Mg/yr
(MT/yr) of vanadium- rich oil were burned. Using an estimate of 1 Mg (MT) of particulates for
each 1,000 Mg (MT) of fuel oil and 5 percent vanadium content in the fly ash, they calculated
190 Mg (MT) of vanadium in the 1967 fly ash emissions in the model area. Approximately 4 X 10*
Mg (MT) of vanadium-rich crude were processed by fluid catalytic cracking units in the area dur-
ing 1967. Using an estimate of 190 X 10* Mg (MT) of paniculate emisions per Mg (MT) of
crude oil processed, and assuming a 5-percent vanadium content in the fly ash, 43 Mg (MT) were
added to the emission inventory. The total estimated vanadium emission from the model area was
then estimated to be 233 Mg (MT) for the year.
The size breakdown for the total emissions was estimated (Table 5.28). These results do not agree
with the 1970 NASN study (Table 5.13), which showed that approximately 80 percent of the sus-
pended vanadium participate had a MMD of less than 2 pm.
Consideration of the chemistry occurring within power plants indicated that the dominant vana-
dium compound in industrial emissions was paniculate V2OB.
An order of magnitude calculation of the residence time within the first kilometer of the atmosphere
was made. Using a mean vanadium concentration of 0.23 ftg/m3, the mass of vanadium hi the
1,000-km2 air shed was 0.23 Mg (MT). Dividing this value by a total emission of 233 Mg/yr
(MT/yr) gives a residence time of 0.36 day. Because of the approximate nature of the calculation,
it was concluded that the residence time was less than 1 day.
5-38 STAR —VANADIUM
-------
Based on these considerations, Tullar and Suffet6 have developed a diagram depicting the fate of
vanadium in an urban air shed (Figure 5.9).
(Ferrobacillus sp.)
V3+.
_^. v4+ + Fe2+
02,Fe3+
v5++Fe2+
MINERAL
VALENCY
FORMS
REDUCTION
H2
V2(OH)2(S04J3.16H20
(MINASRAGRITE)
o2
PORPHYR.NS,
EASILY
LEACHED
V2SS *
H2S
(V-COMPLEXES)
(M.laetilyticus) SULFATE-REDUCING BACTERIA
CALCITIC AND DOLOMITIC LIMESTONE
Figure 5.8. Biogeochemical vanadium cycle. 6
Environmental Appraisal
5-39
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Table 5.28. ESTIMATED PARTICLE SIZE DISTRIBUTION6
(weight percent)
Emissions
Catalytic cracking processes
Fuel oil combustion fly ash
Total emissions0
To atmosphere after dust collection
Particle size range, pm
<2
12
2
20
2-5
65
25
33
60
5-10
13
35
31
20
10-20
10
40
34
"Calculated based on 20 percent of total emission from catalytic cracking processing units
and 80 percent of total emission from fly ash from combustion of fuel oil.
BAND OF ATMOSPHERE: 1 km DEEP
AREA: 1000 km*
VANADIUM CONCENTRATION: 0.2
RESIDENCE TIME: 1 day
THIRD BODY
H2S04 AEROSOLS ON V205NUCLEI
43MT/yr(Mg/yr)
VANADIUM
(AS VzOs
PARTICULATE)
T
CATALYTIC
CRACKING
UNITS
AND S
ADSORPTION TO
REGENERATOR
FINES
S+02—^-804
CRUDE OIL
I
190 MT/yr (Mg/yr)
VANADIUM
(AS V205
PARTICULATE)
POWER PLANT AND
INDUSTRIAL
FURNACES
VANADIUM OXIDE
ANDSULFATE
REACTIONS
DOMINANT)
I I
AEROSOL
GRAVITY
DEPOSITION
RAINOUT
"
4x10«MT/yr(Mg/yr)
RESIDUAL FUEL OIL
3.8 x 106 MT/yr (Ms/yr)
Figure 5.9. Flow diagram of fate of vanadium in urban air.shed.6
5-40
STAR — VANADIUM
-------
5.4 REFERENCES FOR SECTION 5
1. Zajic, J. E. Microbial Biogeochemistry. New York, Academic Press, 1969. 345 p.
2. Schroeder, H. A. Air Quality Monograph, Monograph No. 70-13, Vanadium. American Petroleum Insti-
tute, Washington, D. C, 1970. 32 p.
3. Vanadium. National Academy of Sciences, Committee on Biologic Effects of Atmospheric Pollutants. Wash-
ington, D. C., June 1973.
4. National Inventory of Sources and Emissions: Arsenic, Beryllium, Manganese, Mercury and Vanadium; V.
Vanadium. W. E. Davis and Associates, Leawood, Kansas, June 1971.
5. Bowden, A. T., P. Draper, and H. Hassling. The Problem of Fuel Oil Deposition in Open-Cycle Gas Tur-
bines. Proc. (A), Inst. Mech. Eng. 767:291-312, 1953.
6. Tullar, I. V., and I. H. Suffet. The Fate of Vanadium in an Urban Air Shed, the Lower Delaware River
Valley. (Presented at the 66th Annual Meeting of the Air Pollution Control Association. Chicago, 111.,
June 24, 1973.) Paper 73-117.
7. Gerstle, R. W., S. T. Cuffe, A. A. Orning, and C. H. Schwartz. Air Pollutant Emissions from Coal-Fired
Power Plants, Report No. 2. J. Air Pollut. Contr. Ass. 75(2):59-64, 1965.
8. Radford, H. D., and R. C. Rigg. New Way to Desulfurize Residuals. Hydrocarbon Process. 49:187-191,
1970.
9. Lee, R. E., and D. J. von Lehmden. Trace Metal Pollution in the Environment. J. Air Pollut. Contr. Ass.
2J:853, October 1973.
10. Bolton, N. E., W. L. Lyon, R. I. Van Hook, A. W. Andren, W. Fulkerson, J. A. Carter, and J. F. Emery.
Trace Element Measurements at the Coal-Fired Allen Steam Plant, Progress Report June 1971-January
1973. Oak Ridge National Laboratory, Oak Ridge, Tennessee, ORNL-NSF-EP-43, March 1973. 83 p.
11. Von Lehmden, D. J. Unpublished data, U. S. Environmental Protection Agency, National Environmental
Research Center, Research Triangle Park, N. C., August 1973.
12. lungers. R. H. Unpublished data. U. S. Environmental Protection Agency, National Environmental Re-
search Center, Research Triangle Park, N. C., 1973.
13. Bryan, D. E., V. P. Gwinn, and H. R. Lukens. Development of Nuclear Analytical Techniques for Oil
Slick Identification. Phase 1. Gulf General Atomic. Report 9889, AEC Contract AT(04-3)-167, San Diego,
January 1970.
14. Van Dyke, L. F. U. S. Power Firms Begin Burning Crude. Oil and Gas. J. 70 (6):28-30, February, 1972.
15. Ruch, R. R., H. J. Gluskoter, and N. F. Shimp. Occurrence and Distribution of Potentially Volatile Trace
Elements in Coal-Interim Report, Illinois State Geological Survey. Environmental Geology Notes. No. 61,
April 1973.
16. lungers, R. H., R. E. Lee, and D. J. von Lehmden. The EPA National Fuels Surveillance Network. I. Trace
Constituents in Gasoline and Gasoline Fuel Additives. Environ. Sci. Health Perspectives Technol. (In
Press).
17. Jungers, R. H. Analysis of Vanadium in Fuels. U. S. Environmental Protection Agency, National Environ-
mental Research Center, Research Triangle Park, N. C. Unpublished, 1973.
18. Whitman, N. E. Unpublished data provided to the ERC Task Force on Vanadium. Bethlehem Steel Cor-
poration, Bethlehem, Pa., 1973.
Environmental Appraisal 5-41
-------
19. Anderson, D. M. Unpublished data provided to the ERC Task Force on Vanadium. Bethlehem Steel Cor-
poration, Bethlehem, Pa., 1973.
20. DeHuff, G. L. Vanadium. In: Minerals Yearbook, 1968. Department of Interior, Bureau of Mines, Wash-
ington, D. C., 1969. p. 1143.
21. Threshold Limit Values for Chemical Substances and Physical Agents in the Workroom Environment With
Intended Changes for 1972. American Conference of Governmental Industrial Hygienista, Cincinnati, 1972.
22. Hoffman, G. L., R. A. Duce, and W. H. Toiler. Vanadium, Copper, and Aluminum in the Lower Atmos-
phere between California and Hawaii. Environ. Sci. Techno). 5:1207-1210, November 1969.
23. Rhan, K. A. Sources of Trace Elements in Aerosols: An Approach to Clean Air. Department of Meteor-
ology, University of Michigan, Ann Arbor, Mich. U. S. Atomic Energy Commission Contract No. COO-
1705-9, 1971. 309 p.
24. NASN Vanadium Data Stored in the National Aerometric Data Bank. Unpublished data. U. S. Environ-
mental Protection Agency, National Environmental Research Center, Research Triangle Park, N. C. 1973.
25. Athanassiadis, Y. C. Preliminary Air Pollution Survey of Vanadium and Its Compounds; A Literature Re-
view. U. S. Department of Health, Education, Welfare, Public Health Service, National Air Pollution Con-
trol Administration, Raleigh, N. C. NAPCA Publication No. APTD 69-48, October 1969. 91 p.
26. Lee, R. E., S. S. Goranson, R. E. Enrione, and G. B. Morgan. National Air Surveillance Cascade Impactor
Network. II. Size Distribution Measurements of Trace Metal Components. Environ. Sci. Technol. 6:1025-
1030, 1972.
27. Kanawha Valley Air Pollution Study. U. S. Department of Health, Education, and Welfare. Public Health
Service. National Air Pollution Control Administration, Raleigh, N. C. NAPCA Publication No. APTD
70-1, March 1970.
28. Hauser, T. R., J. J. Henderson, and F. B. Benson. The Polynuclear Hydrocarbon and Metal Concentration
of the Air over the Greater Birmingham Area. In-house report. U. S. Environmental Protection Agency,
National Environmental Research Center, Research Triangle Park, N. C. April, 1971.
29. Brar, S. S., D. M. Nelson, E. L. Kanabrocki, C. E. Moore, C. D. Burham, and D. M. Holton. Thermal
Neutron Activation Analysis of Paniculate Matter in the Surface Air of the Chicago Metropolitan Area.
Environ. Sci. Technol. 4:5-54, 1970.
30. Kneip, T. J., M. Eisenbud, C. D. Strehlow, and P. C. Freundenthal. Airborne Particulates in New York
City. J. Air Pollut. Contr. Ass. 20(3): 144-149, 1970.
31. Laamanen, A., A. Lofgren, and L. Noro. Vanadium: A Specific Pollutant in Air of Helsinki. Institute of
Occupational Health. Helsinki, Finland, Report No. 40, March, 1966.
32. Kopp, J. F., and R. C. Kroner. Trace Metals in Water of the United States. Federal Water Pollution Con-
trol Administration, Cincinnati, Ohio. 1968.
33. Linstedt, K., and P. Kruger. Vanadium Concentrations in Colorado River Basin Waters. Amer. Water
Works Ass. J. 6/(2):85-88, 1969.
34. Durfor, C. N., and E. Becker. Public Water Supplies of the 100 Largest Cities in the U. S., 1962. Geo-
logical Survey, Washington, D. C. Water Supply Paper No-. 1812, 1963.
35. Bowen, H. J. M. Trace Elements in Biochemistry. London, Academic Press, 1966. 241 p.
36. Kiley, J. P., and D. Taylor. The Concentrations of Cadmium, Copper, Iron, Manganese, Molybdenum,
Nickel, Vanadium, and Zinc in Part of the Tropical North-East Atlantic Ocean. Deep Sea Res. 79:307-
317, 1972.
37. Krauskopf, K. B. Factors Controlling the Concentration of Thirteen Rare Metals in Sea Water. Geochlm.
Cosmochim. Acta. 9:1-32B, 1956.
5-42 STAR —VANADIUM
-------
38. Vinogradov, A. P. The Geochemistry of Rare and Dispersed Chemical Elements in Soils, 2nd Ed. Trans-
lated from Russian by Consultants Bureau, Inc., New York. 1959. 209 p.
39. Bertrand, D. Survey of Contemporary Knowledge of Biogeochemistry. 2. The Geochemistry of Vanadium.
Bull. Amer. Museum of Natural History. 94:403-455, 1950.
40. Cannon, H. L. The Biogeochemistry of Vanadium. Soil Sci. 96:196-204, 1963.
41. Pratt, P. F. Vanadium. In: Diagnostic Criteria for Plants and Soils. Chapman, H. D. (ed.), Riverside,
Calif.; University of California Press, 1966.
42. Tipton, I. H., P. L. Stewart, and J. Dickson. Patterns of Elemental Excretion in Long-Term Balance Studies.
Health Phys. 76:455, 1969.
43. Schroeder, H. A., J. Balassa, and I. H. Tipton. Abnormal Trace Metals in Man: Vanadium. J. Chron. Dis.
76:1407, 1963.
44. Barannik, P. I. et al. Levels of Trace Elements and Natural Radioactivity of Food Products of Some Areas
of the Kiev Region. (Translated from Russian). Vop. Pitan. (Moscow) 29(1):79-81, 1970.
45. Soremark, R. Vanadium in Some Biological Specimens. J. Nutr. 92:183-190, 1967.
46. Mitchell, P. L. Emission Spectrochemical Analysis. In: Determination of Trace Elements in Plants and
Other Biological Material. New York, John Wiley and vSons. Inc., 1957. p. 398-412.
47. Lambert, J. P. F., and R. E. Simpson. Determination of Vanadium by Neutron Activation Analysis at
Nanogram Levels to Formulate a Low-Vanadium Diet. J. Ass. Off. Anal. Chem., 55:1145-1150, 1970.
48. Hanna, W. J., and C. L. Grant. Spectrochemical Analyses of Certain Trees and Ornamentals for 23 Ele-
ments. Bull. Torrey Bot. Club. 59:293-302, 1962.
49. Cowgill, U. M. The Determination of All Detectable Elements in the Aquatic Plants of Linsley Pond
and Cedar Lake (N. Bradford, Conn.) by X-Ray Emission and Optical Emission Spectroscopy. Appl. Spec-
trosc. 27: 5-9, 1973.
50. Tyler, G. Heavy Metals Pollute Nature, May Reduce Productivity. Ambio. 7:52-59, 1972.
51. Fukai, R., and Meinke, W. W. Activation Analyses of Vanadium, Arsenic, Molybdenum, Tungsten,
Rhenium and Gold in Marine Organisms. Limnol. Oceanogr. 7:186, 1962.
52. Underwood, E. J. Trace Elements in Human and Animal Nutrition, 3rd Ed. New York, Academic Press,
1971.
53. Soremark, R., S. Ullberg, and L. E. Applegren. Autographic Localization of V-48 Labelled Vanadium
Pentoxide in Developing Teeth and Bones of Rats. Acta Odont. Scand. 20:225-232, 1963.
54. Strain, W. H., W. P. Berliner, C. A. Lankav, R. K. McEroy, W. J. Pories, and R. H. Greenlaw. Retention
of Radioisotopes by Hair, Bone and Vascular Tissue. J. Nucl. Med. 5:664674, 1964.
55. Wilson, H. B., H. E. Stokinger, and G. E. Sylvester. Acute Toxicity of Carnotite Ore Dust Arch. Ind.
Hyg. 7:301, 1963.
56. ter Heege, J. H. Een Intoxicate bij Runderen Door Opname van Stookolieroet (Poisoning of Cattle by In-
gestion of Fuel Oil) (Transl. from Dutch). Soot. Tijdschr. Diergenees (Rotterdam) S9( 18): 1300-1304,
1964.
57. Tipton, I. H. and J. I. Shafer. Statistical Analysis of Lung Trace Element Levels. Arch. Environ. Health.
*:58-67, 1964.
58 Molfino, F. Contributi Sperimentale AHo Studio dell'Intossicazione Professional da Vanadio (Experi-
ments on Occupational Vanadium Poisoning). Rass. Med. Industr. (Turin) 9:362, 1938. English abstract
inj. Ind. Hyg. 27:96, 1939.
Environmental Appraisal 5-43
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59. Massmann, W. Experimental Untersuchungen uber die biologische Wirkung von Vanadinverbindungen
(Experimental Investigations on the Biological Activity of Vanadium). Arch. Toxikol. (Berlin) 16:182,
1956.
60. Sjoberg, S. G. Vanadium Pentoxide Dust; A Clinical Experimental Investigation on Its Effects after Inhala-
tion. Acta. Med. Scand. (Suppl. 238) 755:1-188, 1950.
61. Tipton, I. H.. H. A. Schroeder, H. M. Perry, Jr., and M. J. Cook. Trace Elements in Human Tissue. Part
HI. Subjects from Africa, the Near and Far East and Europe. Health Phys. 77:403, 1965.
62. Carlberg. J. R., J. V. Crable, L. P. Limtiaca, Harold B. Morris, John L. Holtz, and F. R. Woolwicz. Total
Dust. Coal. Free Silica and Trace Metal Concentrations in Bituminous Coal Miners Lungs. Amer. Ind. Hyg.
Ass. J., .72:432-440, July 1971.
63. Gordos, A. A. University of Michigan, Ann Arbor, Mich. Verbal communication on results of hair as an
indicator of trace metal body burden, with D. Worf, Human Studies Laboratory, U. S. Environmental Pro-
tection Agency, Research Triangle Park, N. C., June 1973.
64. Trace Metal Analysis of Maternal-Fetal Tissue Sets, Human Scalp Hair, and Housedust. Stewart Labs.,
Inc. Knoxville, Tenn. Work performed under EPA Contract No. 68-02-0663, December, 1972.
65. Grippaudo, G. et al. Studies on Vanadium and Experimental Caries. Annal. di Stomatologia. (Rome)
75:87-94, 1966.
66. Lowater, F. Chemical Composition of Teeth. Biochem. J. 37:837, 1937.
67. Thomassen, P. R., and H. M. Leicester. Uptake of Radioactive Beryllium, Vanadium, Selenium, Cerium,
Yttrium in the Tissues and Teeth of Rats. J. Dent. Res. 43:346, 1964.
68. Tipton, I. H., and M. J. Cook. Trace Elements in Human Tissues. II. Adult Subjects from the U. S.
Health Phys. 9:103, 1963.
69. Junge, C. Comments on "Concentrations and Size Distribution Measurements of Atmospheric Aerosols and
a Test of the Theory of Self Preserving Size Distribution." J. Atmos. Sci. 26:603-608, May 1969.
70. Hidy, G. M. The Dynamics of Aerosols in the Lower Troposphere. In: Assessment of Airborne Particles.
Mercer, T. T. (ed.). Springfield, 111., C. C. Thomas, 1972. p. 81-115.
71. Goren, M. Oxidation and Recovery of Vanadium Values from Acidic Aqueous Media. U. S. Patent 3,
252. 756. 1966.
5-44 STAR— VANADIUM
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6. EFFECTS OF VANADIUM
6.1 BIOMEDICAL EFFECTS
6. L.I. General Introduction
Studies in animals and man have shown that the toxicity of vanadium compounds is principally a
function of the route of administration or exposure. Vanadium salts are considered highly toxic in
a number of species when given by intravenous or subcutaneous injection. Inhalation of vanadium
compounds produces moderate toxicity with marked irritation to the respiratory tract.1 Since most
vanadium compounds are poorly absorbed from the gastrointestinal tract, they exhibit a low order
of toxicity by the oral route.2 Reviews on the toxic and irritative properties of vanadium compounds
have been published by Symanski,3 Sjftoerg,4 Hudson,1 Stokinger,5 Athanassiadis,6 and Schroeder.7
The following is a limited survey of the more pertinent literature on routes of exposure to, metabo-
lism of, and health effects of vanadium in man and experimental animals.
6.1.2. Human Exposure
6.1.2.1. Industrial Exposure — Vanadium and its compounds possess many valuable chemical and
physical properties that have resulted in increased production and use in recent years. From the
point of view of industrial hygiene, the most important vanadium compounds are vanadium pent-
oxide, vanadium trioxide, ferrovanadium, vanadium carbide, and vanadium salts, such as sodium
and ammonium vanadate. The oxides and salts are commonly used in industry in the powder form,
which entails the possibility of dust and aerosol formation when the substances are crushed or
ground. Many metallurgical processes involve production of vapors containing vanadium pent-
oxide, whioh condense to form respirable aerosols. Boiler-cleaning operations generate dusts con-
taining the pentoxide and trioxide compounds. Combustion of residual fuels having a high vana-
dium content is likely to produce aerosols of the pentoxide as well as oxide complexes of vana-
dium with other metals. (Details on concentration and duration of industrial exposure are given
in Section 6.1.4.)
The portal of entry for vanadium in most industrial situations is the respiratory tract. The gastro-
intestinal tract is also an important portal of entry in the case of dusts and larger particles that
are coughed up and swallowed. Soluble forms of vanadium can penetrate the skin,5 although this
route of exposure appears to be of smaller significance industrially.
Effects of Vanadium 6-1
-------
6,1.2.2. Nonindustrial Exposure — The major route of nonindustrial exposure to vanadium is via
the gastrointestinal tract from food and water. Tipton et al.8 determined the intake for 347 days
of vanadium from food and water by two men aged 23 and 25 (Table 6.1). The calculated intake
of vanadium from water is 4 percent of that from food; whereas the intake from air is about 3
precent of that from food. The proportion of vanadium supplied in water varies from 0 to about 7
percent, depending on the water supply. Similarly, the proportion of the total vanadium intake
attributable to inhaled air varies from zero in most parts of the country to around 10 percent in
New York City.
Table 6.1. BALANCE OF VANADIUM IN TWO MEN7-8
Item
Input:
Dietb
Air
Total
Output:
Feces
Urine
Total
Balance
Concentration of vanadium,
fig/day (mean)
Subject C°
61
2
63
120
18
138
-75
Subject D
,
170
5
175
150
23
173
2
"Contribution of vanadium from seasoning In diet may have been omitted during first three-
fourths of the study.
bAbout 4 percent of vanadium In diet Is from drinking water.
clntake from air Is about 3 percent of that from food.
According to Schroeder,9 the average daily intake of vanadium from food and water is 116 /tg.
On the basis of 1966 NASN data, Schroeder9 calculated (Table 6.2) that the maximum intake of
vanadium from air in 58 cities of the United States and Puerto Rico is 9.16 /tg. Thus, in this
Table 6.2. VANADIUM INTAKE IN RESIDENTS OF URBAN AND NONURBAN
AREAS'"
Item
Amount
Cities studied
Nonurban areas studied
Range, urban, fig/m3
Range, nonurban, /*g/m3
In motor vehicle exhausts
Intake, /xg/day:
Air, maximum
Food and water
Total Intake, % from alrb
Retained In lung, /xg/yr
Maximum found -In lung, /&g
Minimum found In lung, /*g
Average total body content of V, /«g
Soil,
44
29
0.001 to 0.458
0.0005 to 0.024
Trace
9.16
116
7.9
1.3
680
22
100
6.2
•Principal source of vanadium Is petroleum combustion products.
>>At 20 m» Inspired per day. Actually, about 75 percent Is retained.
STAR — VANADIUM
-------
study, 7.9 percent of the daily intake of vanadium came from air at maximum urban levels. Among
the 27 metals listed by Schroeder,9 only mercury and lead showed a higher percentage intake via
air than vanadium.
6.12.3. Medicinal Use — In the past, vanadium compounds have been prescribed infrequently
for medicinal purposes. In the early 1900's, vanadium was used as a therapeutic agent for anemia,
chlorosis, tuberculosis, and diabetes. It was also used as an antiseptic, as a spirochetocide, and as
a tonic to improve appetite, nutrition, and general health. Sodium metavanadate was given by
mouth in doses of 1 to 8 mg, and sodium tartrate was injected intramuscularly at levels as high
as 150 mg. More recent studies on the effect of vanadium on blood cholesterol levels employed oral
doses of soluble diammonium oxytartarovanadate for long periods to determine whether or not
cholesterol levels could be lowered.10-11 (Additional material on this subject will be found in Section
6.1.4).
6.1.3. Metabolism
6.1.3.1. Gastrointestinal Absorption — Vanadium salts are, in general, poorly absorbed from the
human gastrointestinal tract. According to Curran et al.,10 from 0.1 to 1 percent of 100 mg of
vanadium in the form of the very soluble diammonium oxytartarovanadate was absorbed from the
human gut. Within 24 hours, 60 percent of the vanadium absorbed was excreted via the kidneys.
The remainder was retained in the liver and bone. It was mobilized rapidly from the liver and slowly
from the bone following cessation of oral therapy.
In an unpublished study by Mountain,5 vanadyl sulfate was fed to adult male rats in daily doses of
from 650 to 1,250 /*g (160 to 310 fig vanadium). The mean absorption in this case was about 0.5
percent, with considerable variation as judged by urinary values.
6.1.3.2. Respiratory Deposition and Absorption — No data could be found that specifically de-
scribe the deposition of vanadium in the respiratory tract following inhalation. As with other par-
ticulate matter, deposition would be expected to be greatest in the submicron particle size fraction.
There is little doubt that vanadium can be absorbed following inhalation and deposition in the lung.
However, the rates of pulmonary absorption have not been quantitatively determined, and no
estimate has been made of the amount of vanadium that is coughed up, swallowed, and then pos-
sibly absorbed through the gastrointestinal tract. Lewis12 reported that workers exposed to vana-
dium excreted four times as much vanadium in their urine as did controls.
Animal experiments have generally shown complete clearance of the relatively soluble vanadium
pentoxide from the lung within 1 to 3 days following acute exposure.4-13 Stokinger5 has demon-
strated, however, that some metal is present for a month or more following cessation of chronic
exposure.
Levina13 has reported that vanadium trioxide is cleared from the lung more rapidly than the pent-
oxide or ammonium vanadate following intratracheal instillation in rats. The fact that the pent-
oxide remains longest, he suggests, may be related to its "aggressiveness" or damage to the lung
tissue.
Effects of Vanadium 6-3
-------
In an autopsy study, Tipton and Shafer14 have shown that vanadium accumulates in the lungs of
the general population with age, reaching approximately 6.5 /tg/g wet weight of tissue hi those
over age 65. The accumulation of vanadium with age was not observed in organs other than the
lung.14 This is not surprising, since vanadium is poorly absorbed from the gastrointestinal tract;15
however, accumulation of vanadium in the lung suggests that some of the vanadium compounds
deposited in the lung are relatively insoluble forms from contaminated air.7
6.13.3. Absorption Through the Skin — Stokinger5 has reported that skin absorption occurs when
a nearly saturated solution (20 percent) of sodium metavanadate is applied to rabbit skin. The
dermal application of this compound on rabbits causes skin irritation. Human skin comes into
contact with vanadium salts in the industrial environment, and skin sensitivity does develop.4'16
However, the skin appears to be a minor route of uptake of the metal.
6.1.3.4. Transport — Although vanadium is transported in the serum, the carrier or "transvana-
din" has never been isolated. Serum values for vanadium in 13 normal individuals ranged from
0.35 to 0.48 /ig/ml (mean 0.42 /Kg/ml) in a study by Schroeder et al.2 The vanadium was carried hi
the lipid fraction with none in the serum proteins. Schroeder et al. have estimated that a total of
1,380 fig of vanadium was circulating hi the normal serum when samples were taken. They pointed
out that this was approximately equivalent to the daily intake of patients on an institutional diet.
This institutional diet apparently provided about ten times the usual dietary intake of vanadium.
Vanadium was not detected hi washed red cells from 19 control subjects, but five individuals tak-
ing diammonium oxytartarovanadate by mouth (4.5 mg V/day) had elevated vanadium levels hi
red cells (0.37 to 0.81 fig/ml, mean 0.48 /*g/ml) with equivalent amounts in serum (mean 0.47
/xg/ml). Thus it appears that excess vanadium in the serum spills over to be adsorbed or absorbed
by the red cells. The data of Schroeder et al.2 suggest that the serum carrier, if one exists, may be
saturated or near saturated at levels (approximately 0.5 fig/ml) that may occur hi the serum of
individuals on institutional diets.
The influence of the oxidation state of intravenously injected compounds of vanadium-48 on up-
take and distribution to selected organs and subcellular elements of liver in rats was studied by
Hopkins and Til ton.17 These investigators reported no significant differences hi rate or amount of
uptake of nanogram quantities of vanadium of three different oxidation states (VOC1S, VOC12,
and VCl-i). Hence, it appears that either oxidation state is not critical to transport, or that vanadium
is somehow converted to a common oxidation state in vivo. Roshchin et al.18 have found some
evidence for partial conversion of vanadium trioxide to the pentavalent form hi blood serum and
in weakly acidic and basic solutions in vitro.
6.1.3.5. Distribution and Storage — In the rat studies by Hopkins and Tilton,17 liver, kidney,
spleen, and testes accumulated intravenously injected vanadium-48 for up to 4 hours and retained
most of the radioactivity for up to 96 hours. By this time (96 hours), most other organs retained
only 14 to 84 percent of their 10-minute uptake. After 96 hours, 46 percent of the vanadium-48
had been excreted via the urine and 9 percent via the feces. Vanadium-48 that was retained hi
the liver was observed over the first 96 hours to decrease in the supernatant fraction of centri-
fuged liver homogenate from 57 to 11 percent of total liver radioactivity. Vanadium-48 in the
mitochondria! and nuclear fractions increased over the first 96 hours from 14 to 40 percent of the
total. Radioactivity in the microsomal fraction remained relatively constant.
Sorcmark ct al.19 reported highest uptake of vanadium-48 from 48V^O0 in young rats hi rapidly
mineralizing areas of dentin and bone. In pregnant females, they noted a concentration of radio-
6-4 STAR —VANADIUM
-------
vanadium in the fetus as well as in maternal bones and teeth. Thus it is important to note the
potential exposure of the unborn offspring to vanadium via the maternal-fetal circulation. In
another study, Soremark and Ollberg20 demonstrated high uptakes hi mice hi mammary glands,
liver, renal cortex, and lung.
In ^VOCU retention studies in rats, Strain et al.21 found that hair retention correlates with reten-
tion in aorta, bone, and liver, although levels in hair are much lower than in the three other
tissues. Hair retention did not correlate with blood retention. Blood levels were undetectable
after 20 days. Bone retention was highest in young rats of both sexes.
According to Schroeder et al.,2 storage of available vanadium in man is mainly in fat and serum
lipids (see Section 5.2.5 on body burdens and animal tissue levels). Large amounts of vanadium
are also reported in crude fat from beef, pork, and lamb. Keratin has been suggested as a minor
storage depot.2
•' ' f
In general, animal tissues are low in vanadium. None was found in lungs of several animals, in
contrast to the previously mentioned14 accumulation in the lungs of man. Soremark22 has reported
values ranging from less than 1 to several parts per billion (wet weight). Hopkins and Mohr23 found
similar levels in heart, kidney, and liver tissues from chicks on a vanadium-deficient diet. However,
on a normal, supplemental diet, vanadium levels were 10 times higher. The report by Hopkins
and Mohr23 indicated that vanadium is an essential element for chicks; its deficiency resulted hi
reduced feather growth and lowered blood cholesterol. Strasia24 and Schwarz and Milne25 also
found vanadium to be essential in the rat, with deficiency reducing growth rate. Amounts of vana-
dium required both for chicks and rats are those normally found in nutrients and tissues, however.
6.1.3.6, Excretion — Vanadium that is absorbed is excreted mainly in urine but also in feces. In
long-term balance studies, Tipton et al.8 demonstrated that 1 percent of dietary vanadium is
excreted in the urine (Table 6.3). Vanadium was not detected by two different methods of analysis
hi urines of 36 normal subjects.8 However, when 4.5 to 9.0 mg of vanadium as diammonium oxy-
tartarovanadate was fed daily to 16 elderly persons, urinary excretion, although quite variable,
amounted to a mean of 5.2 percent of the amount ingested.8
Table 6.3. EXCRETION OF VANADIUM BY THREE HUMAN SUBJECTS8,0
Excretion
route
Feces
Urine
Sweat, hair,
etc.b
Total
Subject C
/*fl
120 + 3.0
18 ± 0.2
140 ± 3.0
%of
Total
86
13
1
100
Subject D
V-9
150 ±2.0
23 ± 0.2
180 ±2.0
% of
Total
83
13
4
100
Subject E
/*g
37 ± 0.5
12 ± 0.2
49 ± 0.5
% of
Total
75
24
1
100
•"Mean values given. Subjects C and D were studied for 347 days; subject E for 70 days.
tlnferred values to yield 100%.
A study by Dimond et al.,26 in which ammonium vanadyl tartrate was fed to young and middle-
aged patients, demonstrated that urinary excretion was unpredictable relative to oral dosage.
These investigators suggested that variable absorption was the reason for wide fluctuations in
Effects of Vanadium
6-5
-------
urinary excretion. Jaraczewska and Jakubowski27 also concluded that concentrations of vanadium
pentoxide in air in industrial exposures could not, with certainty, be correlated with vanadium
concentrations in urine. However, the latter pointed out the similarity in urinary clearance of
intravenously injected and tracheobronchially administered sodium vanadate in guinea pigs.
Since most of the ingested vanadium is not absorbed, the preponderance of vanadium elimination
is via the fcces. Data from Tipton et al.8 on three normal individuals (Table 6.3) showed that
an average of 81 percent of ingested vanadium was excreted via the feces, compared to 17 per-
cent via the urine.
6.1.3.7. Homcoxtasis — The relatively high serum levels (0.35 to 0.48 /xg/ml) in normal indi-
viduals and low or undctectable urine levels reported by Schroeder et al.2 suggest that vanadium
in serum is not filtered by the renal glomeruli. Alternatively, renal tubular reabsorption may be
very efficient. Filtration or reduced reabsorption may function to eliminate vanadium when the
ability of serum lipids or lipoproteins to bind vanadium is exceeded. Estimates of intestinal absorp-
tion following the administration of soluble vanadium compounds seem to indicate a proportional
reduction in absorption with increasing dose. In any case, it appears that homeostatic mechanisms
are operative to maintain consistently low tissue levels of vanadium.
6.1.4. Human Health Effects
6.1.4.1. Respiratory Effects of Human Industrial Exposure — Most of the clinical symptoms ob-
served following industrial exposures to vanadium reflect its irritative effects on the upper respira-
tory tract. Dutton 28 is believed to be the first to have described the health effects of industrial
exposure to vanadium-bearing ores. Dutton reported a dry, paroxysmal cough with hemoptysis,
and irritation of the eyes, nose, and throat. A temporary increase in hemoglobin and red cells was
followed by a reduction in both and the onset of anemia. Vanadium was recovered in all bodily
secretions. Post mortem examination revealed highly congested lungs with destruction of the alveolar
epithelium, and congested kidneys with evidence of hcmorrhagic nephritis. Unfortunately, the
workers studied frequently suffered from pulmonary tuberculosis, which undoubtedly produced
many symptoms that were aggravated by vanadium exposure. Also, Dutton did not provide details
as to the number of workers examined or the incidence of the symptoms he described.
A subsequent observation by Symanski3 of relatively healthy metal workers exposed to vanadium
pentoxide dust revealed severe conjunctivitis, rhinitis, pharyngitis, chronic productive cough, and
tightness of the chest. X-Rays demonstrated bronchitis, and Symanski expected bronchiectasis with
longer exposure. Symanski's report differed from Dutton's28 in that the former found no evidence
for a generalized systemic action of vanadium.
Rundberg29 observed bronchitis with purulent sputum, general weakness, and skin irritation of the
face and hands of 20 men handling vanadium pentoxide .in a metallurgical works. Balestra and
Molfino10 reported productive cough, bronchitis, and shortness of breath in 25 workers exposed to
vanadium pentoxide dust from petroleum ash. Other substances were involved, but chest X-rays
showed definite lung markings suggesting pneumoconiosis. Bronchiectasis was suspected in two
cases.
Wycrs31-" described his supervision of 50 to 90 workers exposed to vanadium pentoxide as an oil
combustion residue and to slag from production of fcrrovanadium. Findings included bronchospasm,
STAR —VANADIUM
-------
often with elevated blood pressure and an accentuated pulmonary second sound, a paroxysmal
cough, dyspnea, skin pallor, tremor of fingers, palpitation, chest pains, and reticulation of the
lungs. Thus, Wyers emphasized the irritant effects of vanadium pentoxide on the respiratory tract
but also found some evidence of systemic toxicity. An indication of exposure to vanadium first
reported by Wyers was "green tongue," believed to result from reduction of vanadium pentoxide
to the trioxide in the mouth. Data in Wyers' report are limited to 10 case histories (that is, occur-
rence in one or two of 10 men observed), and no control group was examined.
In 1950, Sjjfoerg4 published an extensive report with data on the dust content of the air hi a metal-
lurgical plant producing vanadium pentoxide. The dust particles were relatively large in size —
39 percent less than 12 /xm, 22 percent less than 8 /u,m — and it was estimated that 6.5 mg
V:..O5/m3 represented the worst exposure condition. Of thirty-six men between 20 and 50 years of
age who had been employed in the plant 4 years, 22 had a dry cough, wheezing sounds could be
detected in 31, and 27 were short of breath. One man developed acute pneumonitis, and four others
developed bronchopneumonia. There was no concrete evidence of systemic toxicity.
A dry eczematous dermatitis developed in nine men in Sjpberg's4 study, but only one man showed
a positive patch test. Sj^berg and Ringer33-34 believed that allergy might play a role in the devel-
opment of eczema and pneumonitis following vanadium exposure. Zenz et al.35 also considered this
an explanation for more severe symptoms found on reexposure hi their study.
Six years later, in a follow-up to his 1950 study, Sj^berg34 reported that the 16 men most severely
affected still complained of shortness of breath, coughing, fatigue, and wheezing; two still had bron-
chitis. However, spirometric measurements, cardiac function tests, electrocardiograms, hemato-
logical .tests and urinalyses were essentially normal.
Bronchitis and conjunctivitis resulting from exposure to soot (containing 6 to 11 percent vanadium)
in cleaning the stacks of oil-fired boilers were first recognized by Frost.36 He reported no systemic
symptoms, but a subsequent report of a boiler-cleaning operation by Williams37 noted secondary
symptoms of lassitude and depression. Within 0.5 to 21 hours of exposure primary symptoms were
sneezing, nasal discharge, lacrimation, sore throat, and substernal pain. Within 6 to 24 hours,
secondary symptoms developed, consisting of dry cough, wheezing, labored breathing, lassitude,
and depression. In some cases, the cough became paroxysmal and productive. Symptoms lessened
only after removal from the working environment for 3 days. Air sampling showed that most dust
particles were smaller than 1 /tun. The vanadium concentration ranged from 17.2 mg/m3 in a
superheater chamber to 58.6 mg/m8 in a combustion chamber (Tables 6.4 and 6.5).
Other observations of boiler-cleaning operations were made by Fallentin and Frost,38 Sjjfoerg,39
Thomas and Stiebris,40 Hickling,41 Roshchin,42 and Troppens.16 The latter paper describes the
symptoms as a slight cold or flu condition that ended in bronchitis. Following recovery, the workers
were tired, debilitated, irritable, and without appetite They also complained of watery eyes such
as might occur with a slight case of conjunctivitis. Troppens10 describes the first symptoms as
swelling of face and eyes as early as 20 minutes after entering the boiler area. Removal from
exposure for 2 to 3 weeks results in disappearance of symptoms. Skin blemishes described as aller-
gic dermatoses were attributed to absorption of vanadium through sensitive skin. Vanadium in the
urine was elevated one-and-one-half to threefold. Mention was made of increased susceptibility of
the vanadium worker to asthmatic bronchitis and emphysema, twice as high as other workers
according to data derived from Koelsch and cited by Troppens.10
Effects of Vanadium 6-7
-------
Table 6.4. THERMAL-PRECIPITATOR SAMPLES TAKEN FROM
SUPERHEATER DURING CLEANING OPERATION37
Diameter of
particles, jam
0.1 5 to 1.0
1.1 to 5.5
5.5 to 11
No. of particles
per ml of air
3300
217
9
no %
93.6
6.14
0.26
Concentration of particles
mg/m3 of air
0.36
4.09
7.85
wt. %
2.9
33.3
63.8
Table 6.5 ANALYSIS OF DUST FROM BOILER DURING CLEANING87
Location
Superheater chamber
Superheater chamber
Combustion chamber
Dust
concentration,
mg/m" of air
659
239
489
Vanadium
concentration,
% of dust
6.1
7.2
12.7
Vanadium
concentration,
mg/m3 of air
40.2
17.2
58.6
With all reports of respiratory symptoms relating to boiler-cleaning operations it must be remem-
bered that sulfates and sulfuric acid are also present in boiler soot and may be in part respon-
sible for irritative effects. Hudson1 has suggested that quick onset of symptoms (lacrimation with
nose and throat irritation) with rapid recovery following removal from exposure is characteristic
of exposure to sulfur oxide gases. Dermatitis is said to be characteristic of exposure to acid sul-
fates. Response to vanadium exposure is characterized by some delay in the onset of irritative
symptoms (a few hours to several days), with persistence of symptoms following removal from
exposure.
Additional reports have appeared relating to the health effects of occupational handling of pure
vanadium pentoxide or vanadate dusts. Among them are reports by Pielsticker,43 Gulko,44 Matant-
seva,45 and Zenz ct al.35 Zenz et al.35 described a uniform acute illness that occurred in 18 workers
pellctizing pure vanadium pentoxide; it was characterized by a rapidly developing mild con-
juctivitis, severe pharyngeal irritation, a nonproductive persistent cough, diffuse rales, and broncho-
spasm. With severe exposure, four men complained of itching skin and sensation of heat in the face
and forearms. The symptoms became more severe after each exposure, which suggested a sensi-
tivity reaction; however, duration of symptoms was not prolonged by the subsequent exposures.
Studies concerned primarily with mining, milling, and smelting operations have been published by
Vintinner et al.,46 Lewis,12 Rajner,47 and Roshchin.48 The investigation of Lewis12 is particularly
significant in that the maximum exposure was only 0.925 mg V (as V2OB)/m3 of air, and in most
cases 0.3 mg V/m3 was the exposure level. More than 92 percent of dust particles were smaller
than 0.5 fim in every process area sampled. Symptoms' of cough with sputum production, eye,
nose, and throat irritation, and wheezing were related to physical findings of wheezes, rales, or
rhonchi, injected pharynx, and green tongue. All of these symptoms and physical findings were
statistically significant as compared to controls (Table 6.6 and 6.7). The report by Rajner*7 on
30 vanadium workers in a metallurgical plant in Czechoslovakia describes particularly severe
symptoms, but gives no estimates of exposure except in conjunction with urinary vanadium levels.
In acutely affected workers, vanadium values were about 4,000 /u-g/liter of urine. The average
values among permanent employees was 45 fig/liter, but among vanadium pentoxide smelter
workers, the average was 400 /tg/liter. When a new production process was introduced, symptoms
6-8
STAR — VANADIUM
-------
of acute vanadium intoxication occurred in these workers that included severe respiratory diffi-
culties, headaches, dejection, and loss of appetite after 16 hours of work. Acute inflammatory
changes of the upper respiratory tract with copious mucus production, edema of the vocal cords,
and profuse nose bleeding were reported. Workers who had been exposed for up to 22 years (27
of the workers), mostly in ferrovanadium and vanadium pentoxide smelting operations, complained
of coughing and eye, nose, and throat irritation (all 27 workers), breathing difficulties during
physical exertion (more than 14 cases), and headaches (12 cases). Clinical findings included inten-
sive hyperemia of the mucosa of the nasal septum in 20 workers and perforation of the nasal
septum in four workers. Intensive hyperemia of the mucosa of the throat and larynx with dilated
fine capillaries was found in half of the workers. Bronchoscopy indicated the presence of chronic
bronchitis, and bronchial smears revealed sloughed epithelium. "Slight (pulmonary) functional dis-
orders and beginning emphysema" were reported in five cases. Pneumoconiosis was not detected
on X-ray, and no heart changes or alterations in blood chemistry were reported.
Table 6.6. SYMPTOMS IN VANADIUM WORKERS
12
Symptom
Cough
Sputum
Exertional dyspnea
Eye, nose, throat irritation
Headache
Palpitations
Epistaxis
Wheezing
1 Incidence, %.
Control
33.3
13.3
24.4
6.6
20.0
11.1
0
0
Exposed
83.4
41.5
12.5
62.5
12.5
20.8
4.2
16.6
X2 value
13.71°
5.55b
5.592
23.17°
0.124
0.538
0.148
5.20b
«Signlfleant beyond p = 0.01.
^Significant at p = 0.02.
Table 6.7. PHYSICAL FINDINGS IN VANADIUM WORKERS1
Physical finding
Tremors of hands
Hypertension
Wheezes, rales, or rhonchi
Hepatomegaly
Eye irritation
Injected pharynx
Green tongue
Control
4.5
13.3
0.0
8.9
2.2
4.4
0.0
Incidence, % i >
Exposed
4.2
16.6
20.8
12.5
16.6
41.5
37.5
X2 value
0.320
0.0002
6.93°
0.003
2.94
12.62°
14.53°
"Significant beyond p =0.01.
Other occupational areas in which respiratory effects of vanadium exposure have been reported
include operations connected with the gasification of fuel oil (Fear and Tyrer49) and with the
maintenance of gas turbines (Browne50).
A recurrent inadequacy of all of these reports on industrial exposure to vanadium is the failure
to consider or evaluate the influence of smoking on the clinical findings.
Effects of Vanadium
6-9
-------
In summary, the consensus of industrial hygienists is that there is insufficient evidence to support
the view that vanadium, except at extremely high concentrations, causes generalized systemic
toxicity. However, extensive evidence exists that vanadium dust (usually the pentoxide) is severely
irritating to the mucous membranes of the eyes, nose, throat, and respiratory tract. Bronchitis
and bronchospasm are characteristic symptoms, and pneumonia occasionally develops. Chronic
productive cough and wheezing persist even after the subject is removed from exposure. Many
investigators have reported that vanadium workers are more susceptible to colds and other respir-
atory illnesses.16-18-51-52 Recent studies by Waters et al.53-54 have demonstrated that vanadium oxides
are very toxic for rabbit alveolar macrophages in vitro, Toxicity is related to the availability of sol-
uble vanadium. In view of the central role of the alveolar macrophage in pulmonary defense,
these studies suggest that exposure to vanadium may impair the lung's resistance to secondary
respiratory infection. Thus, an attractive hypothesis to account for these reports and for many of
the chronic respiratory symptoms is that vanadium exposure predisposes the individual to secondary
respiratory infection. However, though there is no evidence to the contrary, a chemico-bacterial
basis for the respiratory symptoms observed in industrial workers remains to be demonstrated.
6.1.4.2. Occupational Exposure Limits — As defined by The American Conference of Govern-
mental Industrial Hygienists,55 threshold limit values (TLVs) "refer to airborne concentrations of
substances and represents conditions under which it is believed that nearly all workers may be
repeatedly exposed day after day without adverse effect. . . . Threshold limit values refer to time-
weighted concentrations for a 7- or 8-hour workday and 40-hour workweek."
In 1961, the American Conference of Governmental Industrial Hygienists adopted TLVs for vana-
dium compounds. In 1971, on the basis of additional data, new TLVs were established.56 Finally,
in 1972, the TLVs were revised upward in that concentrations were expressed as vanadium rather
than vanadium pentoxide; however, the value for vanadium pentoxide fume was designated a
ceiling concentration. (A ceiling value should not be exceeded and is, in effect, a maximum allow-
able concentration.) Table 6.8 lists TLVs for vanadium compounds for 1961, 1971, and 1972.
An outline of the industrial hygiene literature cited in the Documentation of Threshold Limit
Values,5"1 is given in Table 6.9 These data, along with the experimental studies of Roshohin,60
Stokinger,61 and Zenz and Berg,62 constitute the scientific evidence upon which the TLVs were
based.
Table 6.8. THRESHOLD LIMIT VALUES FOR VANADIUM COMPOUNDS,
1961,1971,1972*56
Compound
1961:
Vanadium pentoxide (dust)
Vanadium pentoxide (fume)
Ferrovanadium (dust)
1971:
Vanadium pentoxide (dust) at V2Or,
Vanadium pentoxide (fume) V2Or,
1972:
Vanadium pentoxide (dust) as V
Vanadium pentoxide (fume) as V
Threshold limit value, mg/m3
0.5
0.1
1.0
0.5
0.05
0.5
0.05 (ceiling)
6.10 STAR —VANADIUM
-------
Table 6.9 DOCUMENTATION OF THRESHOLD LIMIT VALUES: OUTLINE OF LITERATURE FINDINGS ON INDUSTRIAL
EXPOSURES TO VANADIUM-
Industry
Vanadium refinery
Boiler cleaning
Boiler cleaning
Vanadium ore
mining and
processing
Boiler cleaning
V2O5 processing
Vanadium refinery
Phosphor plant
Vanadium refinery
Investigator and
reference
Sjtfberg*
Sftberg88
Williams87
Vintinner
et al.46
McTurk et al.M
Gulko"
Lewis12
Tebrock and
Machle89
Hudson1
Vanadium
compound
V2O5
V205(V203)
V205(V208)
V205
V205
(V205)
(V205)
Yttrium
europium
vanadate
V205 and
NH4V03
Concentration,
mg/m3
< 12
-2 to 85
30 to 104
3 to 100
99
0.5 to 2.2
0.2 to 0.5
1.5
(as V20B)
0.25
Symptoms
Mild respiratory
irritation
Respiratory irritation
Intoxication (used respi-
rators to some extent)
Local respiratory
effects, no systemic
poisoning
No intoxication (gauze
filters worn)
Eye and bronchial
irritation
Respiratory irritation
Conjunctivitis,
tracheobronchitis,
and dermatitis
Green tongue, metallic
taste, throat irritation
and cough
"Literature findings are cited in Documentation of Threshold Limit Values.*?
-------
The 1972 TLV for vanadium pentoxide dust and fume is compared with TLVs for some other
metallic oxides in Table 6.10.
Table 6.10. COMPARISON OF 1972 TLV FOR VANADIUM PENTOXIDE
DUST AND FUME WITH THRESHOLD LIMIT VALUES FOR OTHER
METALLIC OXIDES69
Compound
Boron oxide
Cadmium oxide (fume)
Calcium oxide
Iron oxide (fume)
Magnesium oxide (fume)
Osmium tetroxide
Vanadium.pentoxide (fume) as V2O5
Zinc oxide (fume)
Threshold limit value, mg/m3
10
0.1 (ceiling)
5
10
10
0.002
0.05 (ceiling)
5
The TLVs for vanadium have been established mainly on the basis of the irritative effects of
vanadium compounds on the respiratory mucosae. Schroeder,7 after Stokinger,5 has ascribed the irri-
tative effects of vanadium pentoxide to the acidity of its aqueous solutions. Vanadium trichloride
is perhaps the most potent irritant, followed by vanadium pentoxide, ammonium and sodium vana-
date, vanadium trioxide, and vanadium alloys, in that order. These irritative effects are tolerated
by workers since they are not accompanied by pain and, except in severe exposure, do not develop
rapidly.
6.1.4.3. Respiratory Effects of Human Experimental Exposure — The study of Zenz and Berg62
involved nine healthy volunteers, aged 27 to 44, who had previously submitted to lung function
tests for the purpose of developing baseline data. Two of the volunteers, exposed to vanadium
pentoxide dust at 1 mg/m3 for 8 hours, developed sporadic coughing after 5 hours and frequent
coughing near 7 hours. Coughing lasted 8 days, but lungs remained clear; and there were no other
signs of irritation. Lung function tests, complete blood counts, urinalyses, and nasal smears were
normal for up to 3 weeks. After this time, the same two volunteers were accidently exposed to a
"heavy cloud" of vanadium pentoxide dust for 5 minutes. A productive cough developed within
16 hours, and within 24 hours, rales and expiratory wheezes developed throughout the lung. Pul-
monary function remained normal. Isoproterenol (1:2000) relieved the symptoms for about an
hour. Then coughing began again and continued for 7 days. There were no other symptoms. Eosin-
ophils were not present hi nasal mucus.
In the next test, the exposure concentration was reduced to 0.2 mg/m3 (± 0.05 standard deviation)
for 8 hours. Light microscopy indicated that 98 percent of the particles were smaller than 5 j*m.
Again, by the following day, all five men exposed had-developed a loose cough. Coughing, with-
out other systemic symptoms, persisted for 7 to 10 days. Pulmonary function tests and differential
white blood counts remained normal. Vanadium in the urine was highest (0.013 mg/100 ml or
0.13 /fcg/ml) on the third day, with none detectable after 7 days. Maximal fecal vanadium was 3
/*g/g, with none detectable after 14 days.
Finally, two volunteers were exposed to 0.1 mg/m8 of vanadium pentoxide (0.056 mg V/m8) for 8
hours. Within 24 hours, considerable mucus had formed. The mucus was cleared by slight cough-
6.12 STAR —VANADIUM
-------
ing, which became more severe after 48 hours, subsided after 72 hours, and disappeared after
96 hours. Zenz and Berg described the symptoms as a "distinct clinical picture of pulmonary
irritation"62 despite the fact that pulmonary function tests and other clinical findings remained
normal. All of the individuals exposed in the study by Zenz and Berg developed acute symptoms
of marked pulmonary irritation upon initial exposure to vanadium pentoxide dust. Two individuals
exposed a second time to the dust at 0.1 mg/m3 (0.056 mg V/m3) developed the irritative symp-
toms. Hence, the TLV for vanadium pentoxide dust and fume was lowered to 0.05 mg V/m3. It is
likely, however, that even at the new TLVs healthy individuals will suffer symptoms of respiratory
irritation. Furthermore, individuals with a history of respiratory disorders may be expected to
experience distress before TLVs are reached.
6.1.4.4. Diagnoxis of Human Exposure — The respiratory symptoms resulting from vanadium
exposure are so similar to those of acute infection of the respiratory tract that unequivocal diagnosis
is difficult. Certain biochemical indices, along with evidence of probable exposure, can assist in
diagnosis, but no specific test is recommended. Determination of the vanadium content hi blood and
urine provides definitive qualitative documentation of exposure. In view of the work of Schroeder,7
it would seem desirable to measure the vanadium content of the serum separately from that of the
cellular elements, since the concentration of vanadium in the latter may be more indicative of
exposure levels. A decreased urinary output of ascorbic acid may be one characteristic of vana-
dium exposure as reported by Watanabe et al.,63 although differences from controls do not appear
great enough to make the test useful clinically.
The most sensitive test developed to date involves measurement of the cystine content of the finger-
nails. This test was correlated to vanadium exposure in workers and has provided a useful clinical
tool in the management of health of vanadium workers.64 A decrease hi cystine in fingernails was
demonstrated when urinary vanadium levels were only 0.02 to 0.03 /ig/ml. A similar reduction
in the cystine content of rat hair was also reported65 when vanadium in the diet ranged from 25 to
1,000 ppm. There is some evidence to suggest that vanadium may directly inhibit the synthesis of
cystine or cysteine.64-65 Also, these reductions in cystine content in nails and hair may be related to
excretion of cystine in the urine (cystinuria) since an increased neutral sulfur fraction which is
indicative of a cystinuria, is observed in the urine of rats fed vanadium.66 Cystinuria is known to
be associated with Wilson's disease, in which there is a genetically determined lack of the copper
transport protein, ceniloplasmin — a plasma globulin. A possible implication of increased cystine
excretion in the urine would be that vanadium somehow interferes with copper metabolism. Keenan67
noted that in spcctographic analyses of livers of animals exposed to vanadium, the intensity of
copper lines diminished as vanadium intensity increased. Conversely, deJorge et al.68 have
demonstrated decreased serum levels of vanadium and increased serum levels of copper and ceni-
loplasmin in Charcot-Marie muscular atrophy. These changes were proportional to symptom
severity.
6.1.4.5. Effects of Community Exposure — In 1960, Stocks69 reported the results of a statistical
study in which airborne concentrations of 13 trace elements were correlated with mortality from
lung cancer, pneumonia, and bronchitis in 23 localities in Great Britain. Beryllium and molyb-
denum proved to correlate best, whereas arsenic, zinc, and vanadium showed weak associations
with mortality from lung cancer. After eliminating beryllium, molybdenum, and social index
(taking into consideration population density, sex, and age), vanadium retained a coefficient of
correlation with lung cancer of 0.347. With regard to mortality from pneumonia in the localities
studied, beryllium was an important element in both sexes. Vanadium was also correlated with
mortality from pneumonia, but only in males. When social index and beryllium were held constant,
a significant coefficient of correlation with mortality from pneumonia (0.443) remained for vana-
Effecte of Vanadium 6-13
-------
dium. Molybdenum was strongly correlated with mortality involving bronchitis in both sexes.
When social index and molybdenum were eliminated, vanadium gave a coefficient of correlation
with mortality involving bronchitis of 0.563. Beryllium, molybdenum, and vanadium also showed
associations with mortality from cancers other than of the lungs in males, but not in females.
Another statistical study by Hickey et al.70 considered 10 metals in the air, including vanadium,
in 25 communities in the United States. Various techniques, including canonical analysis, were
used to correlate airborne metal concentrations with mortality indices (1962 and 1963) involving
eight disease categories. The incidence of several diseases, including "diseases of the heart," neph-
ritis, and "arteriosclerotic heart" could be correlated reasonably well with air levels of vanadium,
cadmium, zinc, tin, and nickel. The addition of vanadium to cadmium produced a reduction of
more than 10 percent (the greatest reduction) in the error of variance. A high intercorrelation
between vanadium and nickel was unexplained.
These studies of Stocks and of Hickey are exploratory in nature. The relationships disclosed can-
not be considered to be causal in nature without further study. The Hickey study is of a very pre-
liminary nature, with no adjustments for the basic pertinent variables normally employed. The
Stocks investigation is more extensive, considering a number of important adjustments (e.g., age,
sex) and various interactions such as other metals and social factors. Other pollutions — smoking,
for example — have not been examined. Interconnections were not fully explored. An additional
multivariatc analysis of air vanadium levels in relation to selected white male mortality levels is
contained in an unpublished EPA staff study by Pinkerton et al.71 Several categories of cardio-
vascular disease were used, and also influenza-pneumonia. Vanadium was not correlated with the
latter, but was with the cardiovascular categories. However, adjustments for population density pro-
duced considerable reduction in some of these relationships. The authors' comment was: "These
results suggest that the observed statistical associations of air manganese and air vanadium were not
causal associations, and represented either a reflection of other more directly associated causes or
statistical artifacts."71 Another difficulty with interpretation of these observations lies in their
differences from observations on health effects seen in vanadium workers. Additional occupational
and population studies on chronic illness in relation to vanadium exposure are needed to deter-
mine whether some consistency of findings and evidence of a dose-response relationship exist.
6.1.4.6. Other Effects of Human Exposure — As evidenced by the very high levels of vanadium
prescribed medicinally at the turn of the century (see Section 6.1.2.), it is well established that the
metal is not very toxic for man when ingested or when administered intramuscularly. No adverse
health effects have been reported from ingestion of vanadium at any levels normally found in food
or water. However, it has been estimated that a lethal dose for a 70-kg (154-lb) man would be
30 mg V2OB (0.43 mg V2OB/kg) if introduced directly into the circulation in soluble form.1
Vanadium has been prescribed in recent years only in experimental investigations of its effects on
circulating cholesterol levels. In 1959, Curran et al.'° cpnducted a clinical study in which five
normal adult males were fed 150 to 200 mg/day soluble diammonium oxytartarovanadate (21 to
30 mg V/day) for a 6-week period. At the end of this time, plasma cholesterol was significantly
reduced. Lewis72 conducted a study of 32 vanadium workers and 45 controls; ages were matched
in the two groups, and all persons were over 40 years old. The vanadium workers were observed
to excrete greater than normal amounts of vanadium and exhibited slightly lower serum choles-
terol levels than controls. Mean control cholesterol values were 230.9 and 226.7 mg/100 ml. Levels
in the vanadium workers were less by 26 and 20 mg/100 ml (p < 0.05). A clinical study by Som-
merville and Davics" of 12 patients (nine of whom were hypercholesterolemic) given diammon-
6-14 STAR — VANADIUM
-------
ium vanadotartrate showed no significant changes in serum cholesterol levels over 5.5 months. The
mean pretreatment control level of serum cholesterol was 411 mg/100 ml, and the mean age was
49.2 years. Hence, in addition to being hypercholesterolemic, these individuals were older than
those studied by Curran et al.10 Dimond et al.26 observed temporary drops (not statistically sig-
nificant) in cholesterol in two of six patients given ammonium vanadyl tartrate for several weeks
at levels of 50 to 100 mg/day. No statistically significant changes were observed in blood lipids,
phospholipids, triglycerides, 17-ketosteroids, or 17-hydroxycorticosteroids. The subjective symptoms
of fatigue and lethargy were present hi two patients while they were taking vanadium. All com-
plained of cramps and loosened stools, and all developed "green tongue." Schroeder et al.2 reported
that their findings were similar to those of Dimond et al.26 and expressed the view that the slight
effects of vanadium on serum cholesterol were pharmacological and not caused by correction of a
physiological deficiency. They pointed out that dietary regimens based on the consumption of
unsaturated fats, which lower plasma cholesterol in man, are associated with the intake of 1 to 4
mg vanadium per day and that the feeding of vanadium-poor, saturated fats raises cholesterol.
Hence, they note the interesting possibility that the ratio of vanadium to fat may be a factor in the
homeostasis of circulating cholesterol.
6.1.5. Effects on Experimental Animals
6.1.5.1. General Toxidty — The toxicity of vanadium salts varies among mammals and according
to routes of administration (Table 6.11).2-7-73 The smaller animals, including the rat and mouse,
tolerate the metal fairly well. The rabbit, horse, and man are^more sensitive.1 In general, toxicity
is low when the metal is given by the oral route, moderate by the respiratory route, and high by
injection. Lethal doses for various vanadium salts injected intravenously in rabbits and subcutane-
ously in guinea pigs, rats, and mice are shown in Table 6.12. The toxicity of vanadium also varies
considerably with the nature of the compound, although vanadium is toxic both as a cation and as
an anion. As a general rule, toxicity increases as valency increases, pentavalent vanadium being
the most toxic. Among the oxides of vanadium, the pentavalent vanadium pentoxide is more sol-
uble and more toxic than the less common trioxidc or dioxide.
Table 8.11. TOXICITY OF VANADIUM SALTS TO MAMMALS7'7'8
Method and duration
of administration
Oral (in diet), months
Oral (in diet), life
Oral (in water), life
Inhalation, 2 hr daily,
months
Parenteral
intraperiitioneal
Intravenous acute
Type of
mammal
Bat ~~"
Rat
Rat
Rat
Rabbit
Rat
Rabbit
Man
Man
Rat
Rat
Rabbit
Cat
Man
Valence
5
5
5
3
3
5
, 5
—
3
5
5
5
5
Amount
1,000 ppm
100 ppm
8 ppm
40 to 70 mg/
-------
Table 6.12. LETHAL DOSES OF SELECTED VANADIUM SALTS1
(mg V205/kg)
Vanadium salt
Colloidal vanadium
pentoxide
Ammonium
metavanadate
Sodium
orthovanadate
Sodium pyrovanadate
Sodium tetravanadate
Sodium hexavanadate
Vanadyl sulfate
Sodium vanadlte
Rabbit"
1 to 2
1.5 to 2.0
2 to 3
3 to 4
6 to 8
30 to 40
18 to 20
—
Guinea pig
20 to 28
1to2
1to2
1 to2
18 to 20
40 to 50
34 to 45
30 to 40
Rat
_
20 to 30
50 to 60
40 to 50
30 to 40
40 to 50
158 to 190
10 to 20
Mouse
87.5 to 11 7.5
25 to 30
50 to 100
50 to 100
25 to 50
100 to 150
125 to 150
100 to 150
"Rabbits were Injected Intravenously; other animals, subcutaneously.
According to Roshchin,51 the toxic effects of vanadium compounds in experimental animals are
highly specific; however, at the present time, the mechanisms of these effects are incompletely
defined. In the sections that follow, an attempt is made to integrate the experimental data presently
available so as to suggest plausible mechanism for the observed effects.
6.1.5.2. Respiratory Effects — A number of studies have dealt with respiratory exposure to vana-
dium pentoxide (Table 6.134-44-74'75). Sjjfoerg4 has reported in great detail experiments in which
rabbits were exposed to vanadium pentoxide dust particles, nearly all of which were smaller than
10 /urn in diameter. High concentrations over short periods of time were quite toxic; 205 mg
VoOfi/m3 (or 115 mg V/m8) was lethal in 7 hours. At these levels, tracheitis was marked and
was accompanied by pulmonary edema and bronchopneumonia. Conjunctivitis, enteritis, and fatty
infiltration of the liver were also observed. Vanadium was detected in ashed lung, liver, kidney,
and intestine.
Sj^berg4 also carried out long-term studies in which rabbits were exposed to 20 to 40 mg VaO6/m8
(or 11 to 22 mg V/m1) intermittently for 1 hour each day for several months. Upon sacrifice of
the animals, pathological changes observed included chronic rhinitis and tracheitis, emphysema,
patches of lung atelectasis, and bronchopneumonia. Pyelonephritis was seen in some cases. Vana-
dium was detected in ashed lung liver and kidney, but not, as with heavy exposure, in the intestine.
There were no fibrotic changes or specific chronic lesions in the lungs, nor was there a visible
accumulation of particles. These findings, plus the presence of vanadium in the liver and kidney,
were evidence of rapid clearance and/or absorption from the lung.
Gulko44 showed that continuous exposure of rabbits to 10 to 30 mg V2O5/m3 (5.6 to 16.8 mg V/m3)
was toxic to the animals and caused bronchitis, pneumonia, loss of weight, and bloody diarrhea.
Roshchin74 described the results of acute inhalation studies using rats. Vanadium pentoxide was ad-
ministered at 10 to 70 mg/m3 as the condensation aerosol (fume) or 80 to 700 mg/m3 as the
grinding aerosol (dust); ammonium vanadate was given (presumably as the grinding aerosol) at
1,000 mg/m"; and ferrovanadium was given as the grinding aerosol at 1,000 to 10,000 mg/m.3 The
minimum concentration of vanadium pentoxide (in the form of a condensation aerosol) that gave
rise to mild signs of acute poisoning was 10 mg/m3 of air. The obsolute lethal concentration for
the condensation aerosol was 70 mg/m.a Grinding aerosols (containing large particles) were only
one-fifth as toxic as condensation aerosols. Inhalation of grinding aerosols of ferrovanadium did
6-16
STAR — VANADIUM
-------
Table 6.13. RESPIRATORY EFFECTS OF VANADIUM PENTOXIDE IN
EXPERIMENTAL ANIMALS
Investigator
and reference
Sjjfberg4
Sjffberg*
Gulko"
Roshchin'4
Roshchin74
Pazynich™
Animal
Rabbit
Rabbit
Rabbit
Rat
Rat
Rat
Form
Dust
Dust
Dust
Dust,
fume
Dust,
fume
Fume
Concentration,
mg/m3
205
20 to 40
10 to 30
80 to 700
10 to 70
10 to 30
3 to 5
0.027
Exposure
time
7hr
1 hr/day, for
several months
Continuous,
acute
Continuous,
acute
2 hr/day, for
several months
Continuous,
70 days
Pathological findings
Conjunctivitis, tracheitis, plumonary
edema, bronchopneumonia, enteritis,
fatty liver, death
Chronic rhinitis, tracheitis, emphysema,
atelectasis, bronchopneumonia,
pyelonephritis
Bronchitis, pneumonia, weight loss, bloody
diarrhea
Hemorrhagic inflammation in lungs,
hemorrhage in internal organs, paralysis,
respiratory failure, death
Hemorrhagic inflammation in lungs,
purulent bronchitis, pneumonia
Hemorrhagic inflammation in lungs,
vascular congestion and hemorrhage in
liver, kidneys, and heart
s,
t
r
-------
not product acute toxicity, perhaps because particles were too large. Acute toxic effects, however,
were observed following intratracheal instillation of ferrovanadium, which may be related to its
biological solubility and degree of absorption.
Acute inhalation toxicity was characterized by irritation of the respiratory mucosa, with nasal dis-
charge, sometimes containing blood. Animals breathed with difficulty and with crepitations. Be-
havior was passive; the animals refused to eat and lost weight. Dysentery, paralysis of the hind
limbs, respiratory failure, and death ensued in cases of severe poisoning. Pulmonary abscesses
were found frequently in animals that recovered. Animals that died or were killed at various times
after exposure showed severe congestion, particularly in the capillaries, and tiny hemorrhages in
all internal organs. There was evidence of increased intracranial pressure. Livers and kidneys showed
fatty degeneration. Lungs showed capillary congestion, tiny hemorrhages, perivascular and focal
edema, bronchitis, and focal interstitial pneumonia. The bronchitis and bronchopneumonia were
often purulent, and the small bronchi were constricted. The severity of pathological changes could
be related to vanadium content in the air, and in the cases of slight toxicity, the pathological
changes were mainly observed in the lungs.
When rats were exposed intermittently to a condensation aerosol of vanadium pentoxide 2 hours
every other day for 3 months at 3 to 5 mg/m3 (or a grinding aerosol of V2O5 at 10 to 30 mg/m3
for 4 months), pathological changes were seen only in the lungs. Blood vessels of the lungs were
engorged with blood and showed a swollen endothelium; there were capillary congestion, perivas-
cular edema, lymphostasis, and tiny hemorrhages indicating altered vascular permeability and dis-
turbances of pulmonary blood and lymph circulation. Foci of edema were sometimes seen, and,
in some cases, there was desquamative bronchitis. Small bronchi were often constricted. Interstitial
tissue was infiltrated by lymphocytes and histiocytes. Connective tissue proliferation was sometimes
seen in the zone of lymphocytic infiltration. Some animals showed purulent bronchitis or pneu-
monia, and occasionally lung abscesses developed.
Similar effects were observed with vanadium trioxide and vanadium trichloride;51 the latter com-
pound, being more soluble, showed more marked histopathological effects on internal organs. Pen-
tavalent compounds of vanadium were three to five times more toxic than those of trivalent vana-
dium (in terms of median lethal concentration). Grinding aerosols of vanadium metal, vanadium
carbide, and ferrovanadium were not highly toxic; however, chronic exposure to them at high con-
centrations produced many of the same symptoms as described above for vanadium pentoxide.
In summary, the basic manifestations of vanadium exposure of the experimental animals were,
according to Roshchin:74
• Marked irritation of the respiratory mucosa.
• Vascular injury that resulted in capillary stasis, perivascular edema, and tiny hemorrhages,
i.e., a hemorrhngic inflammation process.
• A spastic effect on the smooth muscle of the bronchi that resulted in asthmatic-type bronchi-
tis and expiratory difficulty on acute exposure.
• .Vascular changes — resulting from absorption — in internal organs and brain, which in turn
cause neurological symptoms, toxic nephritis, and disorders of protein metabolism.
6-18 STAR —VANADIUM
-------
With respect to the respiratory tract in experimental animals, the major differences between acute
and chronic effects of vanadium relate to the development, with prolonged exposure, of chronic
inflammation in bronchi, accompanied by greater tendency to septic bronchopneumonia. Atelec-
tasis, interstitial infiltration and proliferation, and emphysema were also noted.
The histopathological changes observed in kidney and liver following acute exposure to vanadium
at high concentrations (tens of milligrams per cubic meter) are not usually seen with intermittent
low-level exposure.
Other physiological effects have been mentioned in cases of severe exposure of animals to oxides
and salts.51 These include disturbances of the central nervous system (impaired conditioned reflexes
and neuromuscular excitability) and cardiovascular changes (occurrence of arrhythmias and extra-
systole, prolongation of the Q-RST interval, and decrease in the height of the P and T waves of
the EKG). The significance of these findings with respect to human environmental exposure, if
any, is not clearly defined at the present time.
6.1.5.3. Metabolic Etfects — In the studies described above by Roshchin74 and in his subsequent
investigations,18 a number of metabolic alterations were observed. After exposure of rabbits to a
grinding aerosol of vanadium trioxide (40 to 75 mg/m3, 2 hours/day for up to 12 months), several
changes were reported: the test animals inhibited a progressive weight loss amounting to an average
of 4.6 percent at the termination of the experiment; whereas controls gamed weight by 12.3 per-
cent. The number of blood leucocytes declined after the fifth month from between 7,000 and
9,000/mm3 to 5,000/mm3 by the end of the test; whereas no change was noted in controls. Hemo-
globin levels in the test animals decreased from 75 to 68 percent. A normal rabbit hemoglobin is
8 to 15 g/100 ml, and a normal rabbit hematocrit is 30 to 50 percent. Serum ascorbate levels
in the blood progressively decreased to about 20 percent of control between 7 and 8 months. Pro-
tein sulfhydryl levels in the serum of exposed animals decreased by 30 percent as compared with
controls. Respiration in liver and brain tissue of test animals was reduced by one-half by the end
of the experiment as compared with controls, but the respiratory quotient was unchanged. Blood
cholinesterase in exposed rabbits increased by an average of 25 percent after the fifth month.
In these studies, the weight loss along with the depressions in the levels of white cells, hemoglobin,
and protein sulfhydryl groups in the blood and the decreased tissue respiration were taken as indi-
cators of the "general toxic effect" of vanadium. Increased cholinesterase activity was held to be
indicative of sensitization. Bronchial asthma was taken as a clinical symptom of sensitization.
Chronic poisoning from the inhalation of vtrivalent vanadium (V2O3 and VC18) resulted in blood
changes by the end of the second and third month. These changes were characterized by decreas-
ed albumin and increased globulins (mainly y globulins) such that the albumin-globulin ratio was
halved; and by an increase in serum concentrations of three amino acids—cystine, arginine, and
histidine. There was also a 10 precent increase in nucleic acid in the blood and a "considerable"
increase in blood chloride. Roshchin51 has said that the "effect of vanadium on the metabolism
of proteins and nucleic acids is responsible for the immunological and allergic reactions important
manifestations of vanadium poisoning." This suggests that vanadium can act as a hapten hi elict-
ing an immunological response, but no supportive evidence is available.
In an attempt to explain the mechanism of the initial nonspecific hematopoetic effect of vana-
dium and the subsequent anemia, Roshchin51 hypothesized that
... the rcdox system of hydrogen carriers is inhibited or blocked, and in response to the re-
sulting hypoxia, there is increased regeneration of the formed elements of the blood . . . Pos-
Effects of Vanadium 6-19
-------
sibly vanadium interferes with tissue respiration at the state of dehydrogenation effected by
coenzyme I* belonging to the group of dehydrases [sic]. By inhibiting this coenzyme, vana-
dium (similarly to lead) interferes with the incorporation of iron in the porphyrin complexes,
thereby retarding the synthesis of hemoglobin. The anti-vitamin C effect of vanadium is
closely related to the inhibition of hemoglobin synthesis. Vitamin C deficiency in the body
likewise inhibits the utilization of iron for hemoglobin synthesis, iron becoming accumulated •.
in the reticuloendothelial tissue... .
Roshchin also points out that vanadium is known to inhibit the activity of monoamine oxidase,
which catalyzes the conversion of serotonin to 5-hydroxyindoleacetic acid. In rabbits chronically
exposed to vanadium pentoxide dust for 3 months, Roshchin observed that urine levels of 5-hyd-
roxyindoleacetic acid had fallen to 33 percent below control values. He suggests, therefore, that
inhibition of monoamine oxidase may result in accumulation of serotonin in the central nervous
system, leading to functional disturbances. The sensitivity of smooth muscle to accumulation of
serotonin, he notes, could result in bronchospasm, diarrhea, and urinary incontinence. The dystro-
phic and necrotic process in the kidneys and the high permeability of the blood vessels could, hi
his opinion, also be explained by elevated serotonin levels.
Roshchin also suggests an interaction of vanadium with an unspecified enzyme to account for the
observed decrease in sulfhydryl groups in blood proteins and to explain the reduced cystine con-
tent of keratinized tissues.
Many of the clinical findings observed and interactions hypothesized by Roshchin and others can
be accounted for or amplified by examination of the rather fragmentary knowledge of biochemical
effects of vanadium exposure in experimental animals and in vitro.
Bergel et al.76 reported that the catabolism of cystine and cysteine is increased by exposure to
vanadium. In studies in vitro, Anbar and Inbar77 demonstrated that, in the presence of VO^+, pyri-
doxal 5-phosphatc induces the catabolism of sulfhydryl amino acids. They pointed out that the
activation of pyridoxal phosphate by vanadyl ions is rather specific to at-, ^-elimination, and it
strongly suggests a decrease of -SH groups in the organism.77 This observation provides a corollary
to the observed lowering of cystine levels in keratinized tissues.64-65 Decreased synthesis of cysteine
and cystine was thought to account for reduced levels of cystine in hair and nails. The essential
point, however, is that metabolic processes that depend on either of these amino acids may be de-
pressed in the presence of vanadium.
Cysteine is required in the biosynthesis of coenzyme A, being added to 4-phosphopantothenic acid
in the presence of adenosine triphosphate (ATP) to form the intermediate 4'-phosphopantothenyl
cystine. Coenzyme A plays a central role hi many biosynthetic and oxidative pathways.78 Masci-
telli-Coriandoli and Citterio79-80 have demonstrated that treatment with sodium metavanadate
lowers the content of coenzyme A in rat liver. (The administration of an antimetabolite of panto-
thenic acid, -methylpantothenic acid, to man results in a syndrome consisting of postural hypo-
tension, dizziness, tachycardia, fatigue, drowsiness, epigastric distress, anorexia, numbness and ting-
ling of hands and feet, and hyperactive deep reflexes. It is not known whether these symptoms
reflect an induced deficiency of pantothenic acid or the toxicity of the antimetabolite. The symp-
toms, however, are not unlike those resulting from exposure to high concentrations of vanadium.
'Coenzyme I was previously used to denote nicotinamide adenine dinucleotide (NAD).
6-20 STAR —VANADIUM
-------
The common denominator in both cases may be reduced hepatic coenzyme A levels.)
The requirement for coenzyme A in biochemical pathways where acetate is a starting material sug-
gests that these processes will be impaired by excessive exposure to vanadium. In 1954, Curran81
demonstrated that the synthesis of cholesterol from acetate-14C in rat liver was diminished in the
presence of vanadium. Subsequently, Azarnoff et al.81J.83 showed that one site of inhibitory action of
vanadium in the cholesterol biosynthetic pathway was at the level of squalene synthetase — the
enzyme that catalyzes the conversion of farnesyl pyrophosphate to squalene. Vanadium was also
shown to mobilize aortic cholesterol in atherosclerotic rabbits more rapidly than was the case in
controls.84 With respect to the observed81 effect of vanadium in lowering circulating cholesterol
levels, Curran and Burch15 recently suggested that a regulatory enzyme, acetoacetyl coenzyme A
deacylase, for the biosynthesis of cholesterol, is activated by vanadium in young animals but
inhibited by vanadium in older ones. This suggestion may explain the fact that cholesterol levels
appear to be lowered by vanadium in younger animals, including humans, and not in older ones.
Because acetyl coenzyme A is a precursor of fatty acids, it has been suggested that vanadium may
depress the synthesis of triglycerides and phospholipids. Levels of triglycerides were decreased in
livers of rats given vanadium;85 however, serum triglycerides in men were increased following
ingestion of vanadium.86 The incorporation of labeled phosphate into liver phospholipids was de-
creased following injection of vanadyl sulfate.87 This finding could have resulted from inhibition
of phospholipid biosynthesis or from increased oxidative degradation as suggested by the Bern-
heims.88-89
Coenzyme A is also required in the synthesis of coenzyme Q, or ubiquinone, of the mitochondrial
electron transport chain. Aiyar and Sreenivasan90 demonstrated that ubiquinone synthesis in iso-
lated mitochondria was reduced in the presence of vanadium. When cysteine was given with vana-
dium, the effect on ubiquinone synthesis was partially reversed. Further addition of ATP and co-
enzyme A completely prevented the inhibition of ubiquinone synthesis.
Coenzyme A is required in the biosynthesis of many other biochemicals; however, the effect of
vanadium on these biosynthetic processes has not been investigated.
Wright et al.91 have demonstrated that vanadium uncouples mitochondrial oxidative phosphoryla-
tion in liver homogenates in vitro, resulting in depletion of the ATP energy stores. The addition of
ammonium metavanadate to the diet at a level to supply 25 /tg/g vanadium also uncoupled oxida-
tive phosphorylation in liver mitochondria of young chicks.92 The mechanism of uncoupling has not
been delineated. Hathcock et al.92 suggest that vanadate may replace the phosphate ion in the re-
actions leading to the synthesis of ATP such that a vanadyl intermediate or an ADP-V is formed.
Aiyar and Sreenivasan90 have shown that vanadium salts inhibit succinic dehydrogenase, which
would also reduce ATP synthesis. Succinic dehydrogenase, a key enzyme of the citric acid cycle and
the electron transport system, is activated by sulf hydryl groups. Vanadium could inhibit this en-
zyme by mediating a decrease in available -SH groups. Sulfhydryl groups are also involved in
the regulation of the deiodination of thyroxine at the cellular level.77 Thyroxine, along with Ca2+
and perhaps other agents, acts through a so-called "U-factor" to cause swelling of mitochondria and
uncoupling of oxidative phosphorylation.78
Perry et al. M>94 have reported that, in the presence of vanadium, the oxidation of tryptamine by
monoamine oxidase from guinea pig liver and kidney was accelerated by 125 percent. Studies by
Effects of Vanadium 6-21
-------
Lewis,95 however, indicated that vanadium inhibited monoamine oxidase, because the urinary out-
put of 5-hydroxyindoleacetic acid was reduced in dogs injected with sodium metavanadate. De-
creased output of 5-hydroxyindoleacetic acid suggests the possibility of accumulation of serotonin
as previously found by Roshchin.51
Other health-related effects of vanadium have been noted in the literature. Vanadium has been
reported to decrease the incidence of dental caries when added to the diet of hamsters.96 Subse-
quent studies97'101 have failed to demonstrate a clearly beneficial effect with regard to dental caries
in humans, however. Vanadium in high concentration has been reported to reduce hemoglobin con-
tent and to produce anemia in experimental animals.51 However, when low levels of vanadium were
administered to men or animals with a normal hemoglobin level, little effect was observed.72'102
Further reports suggest beneficial effects of low-level vanadium in treating nutritional anemia.72-
100,103.104
In a study of goiter in two areas in the Kiev region of Russia, Barannik et al.105 found food levels
of vanadium and chromium to be higher in the goitrous area than in the comparison area. No
other similar observations have been reported.
No data were found on carcinogenic, mutagenic, or teratogenic effects of vanadium exposure in
humans or experimental animals.
6.1.5.4. Functional Effects — Two studies have reported changes in the functional state of mice
and rats following exposure to vanadium. In a series of studies by Selyankina,106 dissolved vana-
dium pentoxide or ammonium vanadate was administered orally to rats or mice in doses of 1 to
0.005 mg V/kg body weight/day for periods of from 21 days at the higher levels to 6 months at
the lower levels. The threshold dose causing functional disturbances of conditioned reflex activities
in mice and rats was 0.05 mg V/kg body weight. A dose of 0.005 mg V/kg body weight proved to
be inactive. On the basis of these experiments, a vanadium concentration of 0.1 mg/liter was
recommended as a maximum permissible concentration for water basins in Russia. This level was
calculated to permit an intake of 0.005 mg V/kg body weight/day by a 60-kg man consuming 3
liters of water.
A report by Pazynich75 involved continuous inhalation exposure of rats for 70 days to condensation
aerosols of vanadium pentoxide at levels of 0.027 ± 0.002 mg/m8 and 0.002 ± 0.00013 mg/m.8
Rats in both groups experienced normal gains in weight, as did the controls. After 30 days, in the
rats exposed at the higher level (0.027 mg/m)3, the motor chronaxy of the extensor muscles of the
tibia decreased by an average of 0.8 microsecond (p. <0.01), and the chronaxy of the correspond-
ing flexor muscles increased by an average of 4 microseconds (p. <0.001). Thus, the chronaxy ratio
of antagonistic muscles had fallen from 1.5 at the beginning of the experiments to 1.0 on the 20th
day (p. <0.02), to 0.5 on the 30th day (p. <0.01), and finally to a level of about 0.25. The
chronaxy ratio returned to normal (1.5) on the 70th day, about 18 days following cessation of ex-
posure. No changes were observed in motor chronaxy in controls or in rats exposed at the lower
level (0.002 mg/m8). Statistically signicant changes in other parameters observed at the high level
exposure (0.027 mg/m8), but not at the lower level, included depressed whole blood cholinester-
ase, decreased total scrum protein, depressed serum /3-gobulins, and decreased oxyhemoglobin con-
tent of venous blood. Also observed in the high level exposure group were elevated serum y-glo-
bulins; increased number of blood leucocytes showing yellow, orange, and red nuclear fluorescence
with acridine orange; and increased oxygen consumption as indicated by the minced livers. The
6-22 STAR —VANADIUM
-------
pattern of leucocyte nuclear fluorescence returned to normal 20 days following cessation of ex-
posure. Histopathological changes observed following high level exposure included marked lung
congestion, focal lung hemorrhages, and extensive bronchitis. Liver changes included central vein
congestion with scattered small hemorrhages, scattered infiltration between lobes, and granular de-
generation of hepatocytes. The kidneys showed marked granular degeneration of the epithelium of
the convoluted tubules. In the heart, myocardial vascular congestion was observed with focal peri-
vascular hemorrhages.
Because of the large differences hi concentrations employed in the first two experimental groups
(0.027 and 0.002 mg/m8), a second experiment was performed in which rats were exposed con-
tinuously to vanadium pentoxide at 0.006 ± 0.00056 mg/m3 for 40 days. During the first month of
exposure, no changes as compared to controls were observed in the parameters investigated — that
is, chronaxy of antagonistic muscles of the tibia and blood leukocyte nuclear fluorescence. After 30
days, there was a statistically significant decrease in chronaxy ratio. During the sixth week of
exposure, animals were stressed by receiving only water and no food. After 3.5 days of this treat-
ment, chronaxy ratios decreased to 0.92 as compared to 1.5 in controls, and the number of leuko-
cytes displaying altered nuclear fluorescence increased by a factor of 4.83. The overall results of
tlie study led Pazynich76 to recommend the no-effect level of 0.002 mg/mn as the mean daily max-
imum permissible concentration of vanadium pentoxide in the atmosphere. Such a direct extrapola-
tion of results from laboratory animal experiments to human community exposure is rarely, if ever,
appropriate. This is particularly true for aerosol exposures of rodents in chambers because they
constantly groom themselves with their tongues. They therefore obtain considerable doses of the
aerosol by mouth in addition to the amount inhaled.
6.2. EFFECTS IN PLANTS AND MICROORGANISMS
The effects of vanadium on plant growth are variable. Cannon,107 Allaway,108 and Pratt109 all
mention that studies by a number of different researchers have shown that, in general, low levels of
vanadium are beneficial to plant growth and that high levels are toxic. Vanadium has not been
proved to be essential for higher-plant growth.107-109
Warington110 studied the physiological effects of vanadium on plant growth. Apical iron-deficiency
chlorosis followed a preliminary deepening of color in the shoot when plants were grown in nu-
trient solutions. Cannon107 reports that reddening in plants similar to that mentioned by Waring-
ton had been observed around the uranium-vanadium deposits in Utah and Colorado. Geological
Survey personnel107 conducted experiments with sorghum and Astragalus preussi (a selenium-accum-
ulating legume). The plants were grown in nutrient solutions containing 1, 10, and 100 /tgV/g as
ammonium vanadate. No effect on growth of germinated seeds of sorghum was noted as 1 ftg/g; at
10 /tig/g, reddening first of the lower stems and later of the leaf tips was observed; at 100 /*g/g,
stunting and death occurred after 2 weeks. In the same experiment, A. preussi was not affected by
100 /*g/g and developed roots 50.8 cm long in 6 weeks.
A. preussi is an accumulator of vanadium as well as selenium. When growing in the same soil, A.
preussi showed a vanadium content of 400 /ug/g and A. pattersoni had 30 /tg/g. Cannon107 has sug-
gested that the difference in uptake is related to the high calcium levels in the latter species. A. patter-
soni contains nearly twice as much calcium as A. preussi. Vanadium, it was suggested, is precipitat-
ed by calcium to calcium vanadate in the roots of A. pattersoni, thus reducing its mobility.
Absorption of vanadium from carnotite, K2(UO2)a(VO4)2*3H2O, was compared with that from other
Effects of Vanadium 6-23
-------
types of deposits by analyzing the vegetation growing in the soil types mentioned.107 The ratio of
vanadium in the soil to vanadium in plant ash usually approximated 10 to 1. The absorption of
vanadium by plants was low. From rocks that contain large amounts of calcium — for example, ty-
uyamunite, Ca(UO2)2(VO4)2.nH20 — and also from sandstones containing calcium. Plant absorp-
tion was high on sandstones and shales that supported seleniferous vegetation.
Plot experiments set up to determine the effects of carnotite ore and some of its toxic components
(uranium, vanadium, and selenium) on plant life showed that plant growth was stimulated hi the
plots to which carnotite had been added.107 The relationship between absorption of vanadium and
pH was not consistent. In the plots in which CaSO4, CaCO3, and Ca3(PO4)2 were present, the vana-
dium content in the above-ground plant parts was low; but in plots containing selenium, vanadium
was high (Table 6.14). In calcium plots, the root-to-shoot ratio of vanadium was found to be greater
(Table 6.15). In general, the presence of calcium in the soil seems to lessen the vanadium uptake by
plants.107
Prince111 attempted to correlate the vanadium content of the soil with the concentration found in
corn plants grown in the soil. He found that the total supply of trace elements in the soil has a def-
inite bearing on the amount found hi the corn plant, but that factors that influence the availability
of the elements (the pH, mineral form, and solubility) are more important hi determining plant
uptake.
Molybdenum plays an essential role in assimilatory nitrate reduction. The metal is essential for
microbial growth with nitrate but not with ammonia.112 Vanadium may replace molybdenum hi
the nitrogen-fixing process mentioned above among certain strains of Azotobacter, a free-living,
nitrogen-fixing bacterium; "3.114 molybdenum, however, is more active. 115
Cannon107 suggests that vanadium may also stimulate nitrogen fixation by bacteria living hi the root
nodules of leguminous plants. Pratt109 cites the work of Nicholas116 who reported that vanadium
played a role in nitrogen fixation by microorganisms h'ving in root nodules. Pratt109 also mentions
studies in which the addition of ammonium metavanadate and calcium vanadate to soil resulted in
increased growth in red clover. Studies using plants other than legumes showed little or no growth
stimulation.109 Bertrand117 first noted that the root nodules of legumes contained higher concen-
trations of vanadium than the roots of other plants.
Cannon107 reported that vanadium in concentrations of 10 to 20 /*g/g in solution was toxic to
plants. Pratt,109 citing various studies, noted that vanadium added to nutrient solutions hi concentra-
tions of 0.5 ftg/g or greater is toxic to plants. Toxicity in a variety of crops has been produced by
adding vanadium to the soil. Toxicity symptoms were extreme dwarfing and chlorosis.
Vanadium as ammonium vanadate was found to be essential for the growth of the green alga, Scene-
desmus obllquus. The presence of vanadium hi the medium stimulated photosynthesis and growth of
the alga. It could not be replaced by molybdenum or other metals.118
Microbial action plays a strong role in determining the availability of vanadium hi the soil. The bi-,
tri-, and pentavalcnt states of vanadium make it susceptible to microbial attack. Specific autotro-
phic bacteria oxidize the reduced forms of vanadium to obtain part or all of their energy for growth
multiplication.119 Micrococcus lactilyticus in the presence of hydrogen is able to reduce vanadate,
6.24 STAR —VANADIUM
-------
Table 6.14. VANADIUM IN ASH OF ABOVE-GROUND PARTS OF
PLANTS GROWN IN EXPERIMENTAL PLOTS1"
0*9/9)
Plant and year
Grindelia aphanactis, 1954
Inscurainia obtusa, 1951
Eschscholtzia californica, 1954
Verbesina encclioides, 1954
Vanadium in plant ash0
Control
(son pH 6.6)
50
<15
<15
10
Camotite
[K2 (U02)2
(V04)3.3H.O]
(soil pH 7.3)
105
100
<15
25
Camotite +
CaSO4.H2O
(soil pH 7.0)
25
24
30
<15
Camotite -f
CaC03
(soil pH &9)
15
<15
<15
Camotite 4-
Ca,(P04)2
(son pH 6.5)
25
20
<15
10
Camotite +
Na2Se03
(Soil pH 7.7)
84
250
75
20
of each plot contained <6/Ltg/g water-soluble vanadium.
Table 6.15. COMPARISON OF VANADIUM IN ASH OF TOPS AND
ROOTS OF PLANTS GROWN IN EXPERIMENTAL PLOTS""
Plant and year
Verbesina, 1955
Stanleya, 1957
Grindelia, 1955
Grindelia, 1956
Astragalus preussi, 1956
Plot
Camotite plus calcium
phosphate
Calcium carbonate
Camotite plus gypsum
Camotite
Sodium selenite
PH
7.5
7.7
7.7
6.7
7.9
Vanadium concn., /ug/g
Tops
10
<10
35
50
50
Roots
1,500 *
70
500
150
150
Roots/
tops
150
>7
14
3
3
-------
molybdate, selenite, tellurite, and arsenate115 (Figure 5.8). Iron-oxidizing bacteria, such as Thioba-
cillus ferrooxidans and Ferrobacillus thiooxidans, oxidize vanadium and make it more soluble in aque-
ous solutions and, therefore, capable of transport in groundwater and of plant uptake. Sutfate-
reducing bacteria form hydrogen sulfide and provide reducing conditions for the reduction of pen-
tavalent vanadium and the formation of vanadium sulfides. The reduction of vanadium sulfide to
trivalent vanadium is catalyzed by Micrococcus lactilyticus under the above conditions.115
The mushroom, Amanita muscaria, is an accumulator of vanadium. Neither the significance of nor
the reasons for this accumulation are known;117 however, vanadium has been shown to be growth-
stimulating to amanitas. Bert rand117 noted that vanadium is not localized in any one part of the
mushroom. When eaten in small quantities, the mushroom is hallucinogenic; in large amounts, it
is poisonous. Much has been written about the properties of this mushroom and its use in orgias-
tic festivals by Siberian tribes.119 The hallucinogenic properties have been associated with mus-
carin, an alkaloid found in the mushroom. Muscarin does not have vanadium as a component.120
Vanadium toxicity in plants is not usually found in agricultural conditions.110 The primary consid-
eration is toxicity to humans and other animals through food ingestion.
6.3. EFFECTS IN ANIMALS
Vanadium has been found in the tissues of representative species from all animal phyla,107 and
the concentrations have been determined.7-117 Most studies dealing with physiology, metabolism,
and toxicity have used experimental animals.
Ascidians (sea squirts), which belong to the Notochordata, have high concentrations of vanadium
in their blood. The serum concentration often reaches 10,000 times that of sea water.7 The func-
tion of chromogen (trivalent vanadium complexed to pyrrole rings), in vanadocytes (green blood
cells containing hemovanadin or chromogen), is not known. It was once thought that chromogen
was an oxygen carrier in the blood, but it has since been shown that it acts as a reducing agent.107
Rock phosphates and colloidal clays are sometimes used as phosphate supplements for growing
chicks.121 These phosphates have been found to be high in vanadium and chromium. Experiments
showed that vanadium was the more significant of the two in its influence on chick growth. A
concentration of 30 /tg/g of vanadium as calcium salt depressed growth; over 200 ftg/g resulted
in mortality. Chromium at levels up to 100 jug/g caused no effect.121
Three commercial samples of tricalcium phosphate, two of dicalcium phosphate and one of bone
meal, were compared in chick diets by Berg.m A significant depression in growth was associated
with the two samples of tricalcium phosphate. The growth depression was associated with the
vanadium (ammonium metavanadate) content of the tricalcium phosphate.
Hathcock et al.m showed that levels as low as 25 fig/g of vanadium, as either ammonium
metavanudate or as vanadyl sulfate, were toxic to chicks. Disodium ethylenediaminetetraacetate,
when added to the diet, prevented vanadium toxicity.
The possibility that trace elements could be toxic when ingested at low levels over long periods of
time was studied by Schroeder and Balassa.124 Rats and mice showed no effects when fed
vanadyl sulfate over a lifetime, but vanadium did accumulate in some of the organs.124 The fact
that vanadium has been determined essential for growth in rats120 may explain the absence of
toxicity when it is fed to them.
6-26 STAR —VANADIUM
-------
Ter Heege126 reported an incident in which four milk cows were exposed to soot cleaned from
an oil-heated boiler. The soot, dumped near a pasture, was spread by the wind to the extent that
the pasture grass was covered with a film of soot. Of the animals exposed, one died, one became
very ill, and one showed no symptoms of illness. The quantity of vanadium consumed is not known.
The soot contained 1 /itg V/g. The animal that became very ill was slaughtered. Toxicological
examination showed 1.5 /ug V/g liver and 3 /tg V/g kidney (both wet weight) and 2.85 mg
V/liter of urine. Analysis on one of the animals that died of poisoning showed 2.4 fig V/g in
liver, 4.3 /*g V/g in renal cortex, and 4.7 /xg V/g in renal marrow. Pathological evidence ob-
tained by autopsy led to speculation that vanadium was the cause of illness and death in this inci-
dent.
6.4. EFFECTS ON MATERIALS AND THE ENVIRONMENT
6.4.1. Metal Corrosion
Vanadium dispersed in air, water, or soil has not been reported to produce or promote damage to
metals or other materials. High concentrations may cause damage in certain situations; however,
the most important and troublesome situation is caused by ash deposits in oil-fired heating and
power generating units that burn residual or crude oils. The problem is particularly acute with the
use of high-vanadium oils. The ash deposits remain on the metal surfaces for long periods and are
difficult to remove. Much of the vanadium in the fuels remains in this ash. Earner in this chap-
ter, the industrial hygiene aspects of vanadium exposure arc discussed. Removal of this ash is a
major source of injury from occupational exposure to vanadium. Major damage to boilers, pipes,
and other metal objects in these plants is also caused by vanadium in the ash. Direct contact with
vanadium corrodes the metals. Vanadium also catalyzes the oxidation of SO2 formed from sulfur
in the fuel to SO3, with subsequent formation of highly corrosive sulfuric acid. The usual methods
of dealing with these problems are cleaning periodically and using oils with low levels of vanadium
and sulfur.
During the last decade, efforts to find other means of dealing with the corrosion problem have in-
cluded the use of fuel additives. Metallic additives, particularly magnesium oxides and methyl
cyclopentadienyl manganese tricarbonyl, have been reported to be successful. The overall prob-
lem and the attempted solutions were described in an unsigned paper in Modern Power and Engin-
eering in 1971.127 Extey et al.128 described the use of magnesium oxide at the Long Island Lighting
Company. This fuel treatment, combined with low excess air, appears to have made considerable
improvement in plant operation. The resultant ash, which can be sold for vanadium recovery, is
less corrosive and more easily removed. Use of manganese as an additive is described by
Bclyea'-" and by Papamarcos.180 Low excess air is not used in this operation, but the effects
appear to be somewhat similar. The mechanisms involved in these empirical observations are not
entirely understood.131 Effects on emissions of vanadium, sulfur compounds, magnesium, man-
ganese, etc., are not known, but it appears that some alterations would be present.
6.4.2. Vanadium in Sludges and Other Wastes
Some information is available on concentrations of vanadium hi waste materials. Because these
wastes are disposed of in landfills, in the sea, or by incineration, some knowledge of the quantities
Effects of Vanadium 6-27
-------
of metals involved and their distribution is of interest and value. Occasionally, as with "oil ash,"
possibilities of valuable resource recovery are identified. Thompson et al.132 studied the metal con-
tent of sewage sludge from 12 urban plants in Oklahoma. Analyses were made by emission spec-
trography, and the results are given in percentage of air-dried sludge. Vanadium levels ranged
from 0.03 to 1.50 percent. One plant had 1.50 percent, two had 1.00 percent, and the remainder
had 0.10 percent or less. The higher levels were thought to be related to higher concentrations in
the local water supplies. Berrow and Webber133 performed similar studies on 42 sewage sludge
samples from a variety of urban and nonurban locations in England and Wales. Measurements
were compared with those of typical uncontaminated British soils. Vanadium concentrations in
sludge samples ranged from 20 to 400 ftg/g, with a mean of 75 /tg/g and a median of 60 /tg/g.
Soil levels, by comparison, were 20 to 500 fig/g, with a mean of 100 fig/g. Concentrations of
0.88 to 7.5 /»g/g with a mean of 3.0 ftg/g vanadium were extractable using a method employing
2.5 percent acetic acid. This is about 4.8 percent of the total vanadium present hi the sludge. Soils
gave <0.05 to 1.0 /ug/g extractable vanadium, with a mean of 0.5 /*g/g. Thus, fertilization with
such sludges would not increase soil vanadium content, but might increase the amount of soluble
metal.
Gross 134 has studied the composition of sewage sludges, coal ash, and other wastes that are dis-
posed of in New York harbor. Figure 6.1134-135 compares the levels in these wastes and hi existing
harbor sediments moved during channel dredging, and in some characteristic soils and rocks. Here
also the concentrations hi waste materials are close to those that occur naturally. The coal ash con-
tent is at the high end of the range, however.
6.4.3. Genera] Environmental Contamination
Under certain circumstances, information can be obtained on environmental contamination over
time — sometimes over periods of several centuries. Suitable material for such studies is found hi
old botanical collections, old bones, old wood and tree rings, ice and snow from glaciers and polar
areas, etc. Although it is rarely looked for hi these studies, vanadium is included hi a current
study of glacier ice by Jaworowski et al.188 Figure 6.2 is a graph from the first part of this study.
Vanadium levels are low, but they show a small increase hi the most recent decade. Lead and
cadmium levels, hi comparison, increased much earlier hi relation to the development of industry
in the 18th and 19th centuries.
6.2ft STAR —VANADIUM
-------
"I I I MIIIJ I I I I Mil] 1—I III ll|| 1 | I Illlll
RANGE
LEGEN°
—VH"- HARBOR SEDIMENT
MEDIAN
--«T SEWAGE SLUDGE
O SHALE
O SANDSTONE
A SOIL
• ASH
SILVER
BORON
BARIUM
COBALT
CHROMIUM
COPPER
MANGANESE
NICKEL
LEAD
TIN
VANADIUM
ZINC
?
10-B
10-1
A • • 0
V •
-*--•-
A O
••
a A o
i
mi
ii 111 i 111 imT*~i~T
10-4
1
10-3
10
10-2
102
10-1
1Q3
1 PERCENT
10* e/ton
CONCENTRATION (DRY-WEIGHT BASIS)
Figure 6.1. Chemical composition (minor elements) of harbor sediment and fly ash as
comnarad with sawaae sludaes and various sediments and soils. 134,135
compared with sewage sludges and various sediments
Effects of Vanadium
6.29
-------
CJ
a
a 8
O LEAD
O CADMIUM
URANIUM
VANADIUM
a
z
<
<
oc
0.6
0.4
0.1
1970
1965
1960
1955
1870 1570 1200
TIME
Figure 6.2. Temporal variations of lead, cadmium, uranium, and vanadium
concentrations in Norwegian glacier ice.136
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79. Mascitelli-Coriandoli, E., and C. Citterio. Effects of Vanadium Upon Liver Coenzyme A in Rats. Nature.
183:1527-1528, 1959.
80. Mascitelli-Coriandoli, E., and C. Citterio. Intracellulur Thioctic Acid and Coenzyme A Following Vana-
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81. Curran, G. L. Effect of Certain Transition Group Elements on Hepatic Synthesis of Cholesterol in the Rat
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82. Azarnoff, D. L., F. E. Brock, and G. L. Curran. A Specific Site of Vanadium Inhibition of Cholesterol Bio-
synthesis. Biochem. Biophys. Acta. 57:397-398, August 5, 1961.
83. Azarnoff, D. L.. and G. L. Curran. Site of Vanadium Inhibition of Cholesterol Biosynthesis. J. Amer.
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84. Curran, G. L. and R. L. Costello. Reduction of Excess Cholesterol in the Rabbit Aorta by Inhibition of En-
dogenous Cholesterol Synthesis. J. Exp. Med. 705:49-56, 1956.
85. Curran, G. L. Effect of Certain Transition Group Elements on Hepatic Synthesis of Cholestrol in the Rat
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86. Curran, G. L., D. L. Azarnoff, and R. E. Bolinger. Effect of Cholesterol Synthesis Inhibition in Normo-
cholesteremic Young Men. J. Clin. Invest. 55:1251-1261, 1959.
87. Snyder, F., and W. E. Cornatzer. Vanadium Inhibition of Phospholipid Synthesis and Sulphydryl Activity in
Rat Liver. Nature. 752:462, 1958.
88. Bernheim, F., and M. L. C. Bernheim. Action of Vanadium on Tissue Oxidations. Science. 55:481-482,
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89. Bernheim. F., and M. L. C. Bernheim. The Action of Vanadium on the Oxidation of Phospholipids by Cer-
tain Tissues. J. Biol. Chem. 727:353-360, 1939. •
90. Aiyar, A. S., and A. Sreenivasan. Effect of Vanadium Administration on Coenzyme Q Metabolism in Rats.
Proc. Soc. Exp. Biol. Med. 707:914-916, Aug.-Sept. 1961.
91. Wright, L. D., L .F. Li, and R. Trager. The Site of Vanadyl Inhibition of Cholesterol Biosynthesis in Liver
Homogenatcs. Biochem. Biophys. Res. Commun. 5:264-267, 1960.
92. Halhcock. J. N.. C. H. Hill, and S. B. Tove. Uncoupling of Oxidative Phosphorylation by Vanadate. Can.
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93. Perry, H. M., Jr., S. Teitlebaum, and P. L. Schwartz. Effect of Antihypcrtensive Agents on Amino Acid
Decarboxylation and A mine Oxidation. Fed. Proc. 74:113-114, 1955.
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95. Lewis, C. E. The Biological Actions of Vanadium. III. The Effect of Vanadium on the Excretion of 5-Hy-
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96. Geyer, C. F. Vanadium. A Caries Inhibiting Trace Element in the Syrian Hamster. J. Dent. Res. 55:590-
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i
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7. CONTROL TECHNOLOGY
Control strategy for vanadium emissions must be based on effective removal of paniculate material
from process exhaust streams. Technology exists for providing extremely good control of particu-
late emissions from industrial processes and combustion sources. The degree to which control of
vanadium emissions is achieved will be proportional to the extent of application of high-efficiency
particulate control devices.1
Many industries have applied effective control devices to their process stream. For example, Lee
et al.- have reported total removal of vanadium content of a steel mill process stream by a baghouse.
Although no data are available specifically for vanadium, high total mass collection efficiency has
been attained on metallurgical exhaust streams using electrostatic precipitators and wet scrubbers
as well as baghouses.3-4
Coal-fired power generating facilities have used electrostatic precipitators (ESPs) for a number of
years. Recent years have seen the installation of ESPs capable of removing more than 99.5 per-
cent of the particulate loading. fcee et al.2 reported on a precipitator that removes 99.85 percent
of the vanadium in the exhaust Iff earn. Some of the input vanadium is captured in the bottom slag
and open boiler surfaces, so that total removal is even better than this figure. Lee's data show that
most of the escaping vanadium is below 5 fjan in diameter, and almost half is less than 1 /tin.
McCain5 has reported removal efficiencies above 90 percent for particles as small as 0.06 /ttm by
ESPs on coal-fired boilers. A baghouse has proved effective on an anthracite coal-burning unit
with total collection efficiency greater than 99.5 percent. More effective control of vanadium from
utility coal-fired boilers can be expected as more high-efficiency units are installed to meet in-
creasingly stringent local emission laws.
Particulate control of oil-fired combustion sources has been practically nonexistent because total
mass emissions are usually less than local regulations require. Vanadium recovery has been re-
ported as a result of attempts to control boiler corrosion by means of magnesia-alumina fuel addi-
tive.6 Enough vanadium has been recovered to make the process economically attractive, with 75
percent of the input vanadium recoverable from the bottom slag. Control of the particulate emis-
sions may be enhanced if sulfur dioxide removal schemes such as the Chemico magnesium oxide
process are applied to oil-fired combustion sources. High removals of particulate have been reported
with this system.7
7-1
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The enormous volume of vanadium-containing fuel consumed means vast quantities will still be
emitted until even better devices are available. A high degree of control of vanadium may be ex-
pected from stationary sources as new paniculate or sulfur dioxide control devices are extended to
all possible sources.
7.1 REFERENCES FOR SECTION 7
1. Vanadium (Section V). In: National Inventory of Sources and Emissions: Arsenic, Beryllium, Manganese,
Mercury and Vanadium Emissions. W. E. Davis and Associates, Leawood, Kansas, 1971.
2. Lee, R. E., Jr., H. L. Crisp, A. E. Riley, and K. MacLeod. The Concentration and Size of Trace Metal
Emissions from a Power Plant, a Steel Plant, and a Cotton Gin. Environ. Sci. Technol. (In press).
3. Harris. D. B. and D. C. Drehmel. Fractional Efficiency of Metal Fume Control as Determined by Brink
Impactor. U. S. Environmental Protection Agency, National Environmental Research Center, Control Sys-
tems Laboratory, Research Triangle Park, N. C. (Presented at 66th Annual Meeting of the Air Pollution
Control Association, Chicago, June 24-28, 1973.)
4. Patched, G.. and R. N. Allen. Electric Furnace Testing — Particle Size Measurements. Resources Research,
Inc. Reston, Va. EPA Contract CPA 70-81, March 7972.
5. McCain, J. E. Particle Sizing Techniques for Control Device Evaluation. Southern Research Institute, Bir-
mingham, Ala. EPA Contract 68-02-0273, October 7973.
6. Lee, G. R., F. D. Friedrick, and F. D. Mitchell. Control of SO3 in Low Pressure Heating Boilers by an
Additive. J. Inst. Fuel. 42:67, 1961.
7. Statnick, R. M. U. S. Environmental Protection Agency, National Environmental Research Center, Con-
trol Systems Laboratory, Research Triangle Park, N C. Personal communication with Chemico Corp.
1973.
7.2 STAR —VANADIUM
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