U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
PB-245 989
PRELIMINARY INVESTIGATION OF EFFECTS ON THE ENVIRONMENT
OF BORON, INDIUM NICKEL SELENIUM, TIN, VANADIUM AND
THEIR COMPOUNDS
VOLUME VI - VANADIUM
VERSAR, INCORPORATED
PREPARED FOR
ENVIRONMENTAL PROTECTION AGENCY
AUGUST 1975
-------
KEEP UP TO DATE
Between the time you ordered this report—
which is only one of the hundreds of thou-
sands in the NTIS information collection avail-
able to you—and the time you are reading
this message, several new reports relevant to
your interests probably have entered the col-
lection.
Subscribe to the Weekly Government
Abstracts series that will bring you sum-
maries of new reports as soon as they are
received by NTIS from the originators of the
research. The WGA’s are an NTIS weekly
newsletter service covering the most recent
research findings in 25 areas of industrial,
technological, and sociological interest—
invaluable Information for executives and
professionals who must keep up to date.
The executive and professional informa-
tion service provided by NTIS in the Weekly
Government Abstracts newsletters will give
you thorough and comprehensive coverage
of government-conducted or sponsored re-
search activities. And you’ll get this Impor-
tant information within two weeks of the time
It’s released by originating agencies.
WGA newsletters are computer produced
and electronically photocomposed to slash
the time gap between the release of a report
and Its availability. You can learn about
technical Innovations immediately—and use
them in the most meaningful and productive
ways possible for your organization. Please
request NTIS-PR-205/PCW for more infor-
mation.
The weekly newsletter series will keep you
current. But learn what you have missed In
the past by ordering a computer P4TlSearch
of all the research reports In your area of
interest, dating as far back as 1964, if you
wish. Please request NTIS-PR-186/PCN for
more information.
WRITE: Managing Editor
5285 Port Royal Road
Springfield, VA 22161
This information product distributed by
mi_S U.S DEPARTMENT OF COMMERCE
National Technical Information Service
5285 Port Royal Road
Springfield, Virginia 22161
Keep Up To Date With SRIM
microfiched report. Your SRIM service begins
as soon as your order is received and proc-
essed and you will receive biweekly ship-
ments thereafter. If you wish, your service
will be backdated to furnish you microfiche
of reports issued earlier.
SRIM (Selected Research in Microfiche)
provides you with regular, automatic distri-
bution of the complete texts of NTIS research
reports only in the subject areas you select.
SAIM covers almost all Government re-
search reports by subject area and/or the
originating Federal or local government
agency. You may subscribe by any category
or subcategory of our WGA (Weekly Govern-
ment Abstracts) or Government Reports
Announcements and Index categories, or to
the reports issued by a particular agency
such as the Department of Defense, Federal
Energy Administration or Environmental
Protection Agency. Other options that will
give you greater selectivity are available on
request.
Because of contractual arrangements with
several Special Technology Groups, not all
NTIS reports are distributed in the SRIM
program. You wilt receive a notice in your
microfiche shipments IdentifyIng the excep-
tionally priced reports not available through
SRIM.
The cost of SAIM service Is only 45?
domestic (60? foreign) for each complete
A deposit account with NTIS is required
before this service can be initiated. if you
have specific questions concerning this serv-
ice, please call (703) 451-1558, or write NTIS,
attention SRIM Product Manager.
-------
lPA-SeO/2-7S-OOSF
PRELIMINARY INVESTIGATION OF
EFFECTS ON THE ENVIRONMENT OF BORON.
INDIUM NICKEL, SELENIUM. TIN. VANADIUM
AND THEIR COMPOUNDS
VOLUME VI
VANADIUM
OFFICE OF TOXIC SUBSTANCES
ENVIRONMENTAL PROTECTION AGENCY
ISHINGTON, D.C. 20490
AUGUST, 1976
-------
BIBLIOGRAPHIC DATA
MEET
1. Report No.
EPA-560/2-75-005f
3. Recipient's Accession No.
Title and Subtitle
Preliminary Investigation of Effects on the Environment
of Boron, Indium, Nickel, Selenium, Tin, Vanadium and
Their Compounds - Volume VI Vanadium
5. Report Date
August 1Q75
6.
Author(s)
8. Performing Organization Rept.
No.
. Performing Organization Name and Address
Versar Inc.
6621 Electronic Drive
Springfield, Virginia 22151
10. Proiect/Task/Work Unit No.
2LA328
11. Contract/Grant No.
68-01-2215
2. Sponsoring Organization Name and Address
Office of Toxic Substances
Environmental Protection Agency
Washington, D.C. 20460
13. Type of Report & Period
Covered
Final
14.
IS. Supplementary Notes
6. Abstracts
A comprehensive review of published literature was conducted to prepare
this preliminary investigation report on the physical and chemical properties
of vanadium, on the environmental exposure factors related to its consumption
and use, on the health and environmental effects resulting from exposure
to this substance, and on any applicable regulations and standards governing
its use.
7. Key Words and Document Analysis. 17o. Descriptors
Vanadium
17b. Identifiers/Open-Ended Terms
17c. COSATI F.eld/Group Q6/F, J,
07/B
18. Availability Statement
Release Unlimited
19. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
•UNCLASSIFIED
21. Np.of Pages
-------
EPA-560/2-75-005f
PRELIMINARY INVESTIGATION OF
EFFECTS ON THE ENVIRONMENT OF BORON, INDIUM
NICKEL, SELENIUM, TIN, VANADIUM AND THEIR COMPOUNDS
Volume VI
Vanadium
Contract No. 68-01-2215
Project Officer
Farley Fisher
Prepared for
Office of Toxic Substances
Environmental Protection Agency
Washington, D.C. 20460
August 1975
V A
-------
1 ERJAR Ixc.
VANADIUM
TABLE CF (Dfl S
Pa
I. VANADIUM N JSTR 1 IN UNI ) STh
A. Producers arid Sites .
B. sts . . . . . . .
C. PhysicaiProperties . . .
II. pa)1x1crIoN
A. Quantities .
1. Vanadji.un and Vanadiun Pentoxide
B. Process . . .
1. Vanadiun . . .
a. Calciun Reduction
b. Altnninot1 nnic Process
c. Electrotransport chniq
2. Vanadjijn Pen xide and Sodium and Antioniwn
\‘a.n ad ate . • , • • • •
3. Ferxovanad.itrn
C. Esti.nate of Yearly Vanadium Release
A. Vanadium and its ( npoumds
B. Qnsurption Trends and Potential
IV. QJR 2 Ir PR1C’rI S
A. Transportation and Handling
V. N N AL
A. O ral]. Appraisal
B. Franuse.
1. ?v tallurgical Uses
C. Fran Production and Disposal
1. Mining and Processing of Ore
2. Production of Ferrovanadiun
3. Fran Inad rtent Sources .
a. cc rb tionofOi1
b. Coirbustion of Coal
VI—1
VI—5
VI—5
VI—7
VI—7
VI—7
VI—8
• . . . . . . . VI—8
VI—8
VI—9
‘VI— 9
III. t.EES
• . . VI—9
\71—1O
VI—13
VI—14
Future USeS . • . . VI-17
VI— 19
/ VI—19
• . . VI—20
VI—20
VI—20
VI—20
\1I—21
VI—21
1I—22
1 /1 —22
VI—22
VI—24
-------
I 4 RJAR Ixc.
VANADIUsI
TABLE CF rr is
(ODn’t)
Table
VI. 14 JI’IORING AND ANALYSIS . . . . . . . .
A. Monitoring .
B. An.aly’ is . . . . . . . . . . .
1. Van 3.iuin (in air-borne materials)
2. Vanadli in Solution
VII . OiE 4ICAI. 1 ACrIV’I’ry . .
A. Ezwironxrent.a]. E acticns . . . . . .
VIII . BIOLCGY
A. ODntent, Absorption and E ccreticn .
1. ArJ.rnals
2 . Plants
B. Distribution
1. Animals
C. Grt th and Nutrition
D. Cytoxicity
E. b tabo1icEffects
]JC. EFFEC’IS . .
A. E wircriffental Caitent, Transportation, and
ntaini-riat,i i • • • •
B. Bioacc .zlation
x. ‘IOXICITI
A. H . nans
1. Occ .pational E çosux
2. Other Sttrlies
B . r4 Tuna1s
1. Acute ‘Ibxicity
2. ronic ‘Ibxicity
3. I rato nicity, Carcino nicity and
Mut enicity
C. B.ird.s
D. Plants
E. Microorganisms
F. F sults of Personal Ccntacts with M dical
:::::
VI—27
VI—27
VI—29
‘11—29
‘11—29
‘11—31
‘11—31
‘11—32
‘11—32
‘11—32
‘ 11—35
‘ 11—35
‘11—35
‘1 1—36
‘11—38
VI—42
‘11—49
• . . . . ‘11—49
‘ 11—60
‘11—63
‘11—63
VI—63
‘11—64
‘11—65
‘1 1—65
‘11—70
VI—71
• . . • . ‘11—71
‘11—72
VI—72
Personnel ‘11-72
ii.
-------
V RJAR JXC.
V NADIU4
TABLE OF CTJN ENIS
( n ‘ t)
Page
XI. STANDA S oJR r RE JIX IONS . . . ‘ 1 1—73
XIII. SU!4 RY AND Q1JSI S . . . ‘11—74
A. Sun1T ax ’ ‘11—74
B. ic1i.. ions \7I —75
C. Remrendaticns ‘ 11-76
iii.
-------
1’ RJAR JxC.
LIST OF ‘ BLES
Page
1. icals, Producers and Plant 1ocaticx s VI-l
2. 1972 Prices of Van .ii. n and Corrpounds ‘ 11-5
3. Physical Properties . . . . ‘11—6
4. Producers of Vanad.itnn Pentoxide ‘11-7
5. Vanadium Cbnsu ption . . VI—14
6. Table of Uses VI—15
7. Concentraticn of Vanadium in estic Coals ‘1 1-25
8. 1972 U.S. Ccns iptiai of Coal (thot and n tric tcns) . . ‘11-26
9. Vanadium O centrati in Atztospl re, g/m 3 . VI-28
10. vanadium Ca itent of Sc nicates VI-34
11. Grcwth I sponse of Rats to Varying Levels of Vanadium
Sipleirents ‘11—37
12. Concentrations of tallic Ions Ca thg F duction in
Viability to 50 Per Cent in Rabbit Alveolar Macro-
* a s and Htn n Lung Fibrthlasts ‘11-40
13. Concentrations of tallic Ions Causing Reduction in
Uptake of Thymidine, Uridine, and Leucine 50 Per
Cent in Htni n Lung Fibrthlasts ‘11-41
14. Predicted Vanadium Concentrations for Wirt ard Hawaii
fran Natural Sources ‘11-50
15. Predicted Vanadium Cancentraticns for .ira1 Canada fran
NaturalSourceS ‘11—51
16. Predicted Levels of A1 ospheric Vanadiizn Originating
from Natural Sources ‘11—52
17. Predicted Vanadium Contributions from Various Sources
iritheBostonArea . ‘11—54
18. Estimated Annual Rates of Global Injection of Vanadium
into t1 Atnosphere from Petroleunt and Natural Sources ‘11-55
19. Vanadium in Sone Water Sanpies ‘11—56
20. Vanadium in Sorre P nimal SpecilTens VI-57
iv.
-------
3’ RJAR INC.
LIST T1 BtES
(O n ‘t)
Table
2].. vanadi .un in Sane Fruits and Vegetables . VI-59
22. 1 Vanadium Cbntent of Sae Marine Organisirs VI-61
23. Effect of Valenos on Van .ium Toxicity th Rats . . . . VI-66
24. Acute ‘Ibxicity of Soire vanadium Cpo x ds. . VI-67
25. Lethal Doses, in ng V 2 0j1g . . . . VI 68
V.
-------
RJAR JXC.
Vo1ui VI
Preliirtinaxy In St19atLOfl of Effects
a Dwironirent of Van it u andy Its ai o ds
wJ
This is Volurre VI of a series of six reports on t ivironrrental
effects of bort , indian, nickel, seleniurT , tin, and vanadium and t Eir
cxJflpOUfldS. ‘fl infonnation is based an literature ieviews, direct —
tact with representati s of wn?anies invol d in t productiai or use
of the materials, and su1tation with n lad able is dividt1 1R f n
industry, academic institutions and the Fe ra1. Governnent.
-------
3’ RJAR JXC.
‘It.’
I. VANADIUM INDUSTRY IN THE UNITED STATES
A. Producers and Sites
Table 1 lists commercially prepared vanadiuirt compounds and
the companies which produce them. Only those chemicals whose pro-
duction exceeds 1/2 metric ton or $1000 are listed. Other materials
may also be mentioned in the discussion because of their unusual prop-
erties, such as toxicity, or their anticipated future significance.
Chemical
Lithium van-
adate
Anunoniuni van-
adate
Sodium van-
adate
Table 1
(1,2)
Chemicals, Producers and Plant Locations
Producer
Company, subordination ________
Gulf Resources & Chem. Corp.
Lithium Corp. of America
Kerr-McGee Chem. Corp.
Union Carbide Corp.
Mining and Minerals Div.
Var—Lac-Oid Chem. Corp.
Atomergic Chemetals Co.
Gallard-Schlesinger Chem.
Mfg. Corp.
Cerac, Inc.
Research Organic/Inorganic
Chem. Corp.
Var-Lac-Oid Chem. Co.
Atomergic Chemetals Co.
Gallard-Schiesinger Chem.
Mfg. Corp.
Cerac, Inc.
Electronic Space Products,
Inc.
Research Organic/Inorganic
Chem. Corp.
United Mineral & Chem. Corp.
Var-Lac-Oid Chern. Corp.
Ventron Corp, Alfa Prod. Div.
Urevan, Cob.
Hot Springs, Ark.
Elizabeth, N.J.
Cane Place, L.I., N.Y.
Belleville, N.J.
Sun Valley, Cal.
Elizabeth, N.J.
Cane Place, L.I., N.Y.
Belleville, N.J.
Sun Valley, Cal.
New York, N.Y.
Elizabeth, N.J.
Bradford, Pa.
Sunnyvale, Cal.
Location
Bess TTTer City, N.J.
Soda Springs, Idaho
Los Angeles, Cal.
Monomonee Falls, Wis.
Vanadium
metal
Los Angeles, Cal.
Menomonee Falls, Wis.
Los Angeles, Cal.
-------
VI-2
Y RJAR INC.
Table 1. (cont.)
Chemical
Vanadium ace-
tylacetonate
Vanadium
carbony 1
Van a di uin
chloride
producer
Company, subordination
MacKenzie Chem. Works, Inc.
The Shepherd Chem. Co.
Pressure Chem. Co.
Foote Mineral Co.
Location
Central Islip, N.Y.
Cincinnati, Ohio
Pittsburgh, Pa.
Cambridge, Ohio
Vanadium
diboride
Vanadium hex-
acarbonyl
Vanadium neo-
decanoate
U.S. Borax & Chem. Corp.
U.S. Borax Research Corp.,
subsid.
Ventron Corp.
Alfa Products Div.
Ventron Corp.
Alfa Products Div.
Mooney Cherns., Inc.
Anaheim, Calif.
Beverly, Mass.
Beverly, Mass.
Franklin, Pa.
Van ad i urn
oxide
Vanadium oxy-
trichioride
(vanadyl tn-
chloride)
Vanadium OXy-
tn fluoride
Vanadium pen-
tafluoride
Vanadium pen-
toxide (Vana-
dic anhydride)
Associated Metals & Miner-
als Corp.
Gulf Chem. & Metallurgical
Co . ., div.
Union Carbide Corp.
Mining and Minerals Div.
Foote Mineral Co.
Stauffer Chem. Co.
Specialty Chem. Div.
Union Carbide Corp.
Mining and Metals Div.
Qzark-Mahoniflg Co.
Ozark-Mahofling Co.
Fairmount Chem. Co., Inc.
Foote Mineral Co.
Kerr-McGee Corp.
Kerr-McGee Chem. Corp. subsid.
Freeport, Tex.
Texas City, Tex.
kict Springs, An’.
Niaqara Falls, N.Y.
Cambridge, Ohio
Weston, Mich.
Niagara Falls, N.Y.
Tulsa, Okia.
Tulsa, Okia.
Newark, N.J.
Cambridge, Ohio
Soda Springs, Idaho
-------
RJAR IxC.
VI—3
Chemical
Vanadium sul-
fate (Vanadic
sulfate) (Vana-
dyl sulfate)
Vanadium tetra-
chloride
Vanadium tetra-
fluoride
Vanadium
oxide
Vanadium
chloride
Vanadium
fluoride
te t ra -
tn-
tn—
Vanadium tn-
oxide
Vanadium tris
(acetylaceto—
nate)
Vanadyl ace-
tate
Vanadyl ace-
tylacetonate
Vanadyl naph-
thenate
Table 1. (cont.)
Producer
Company, subordination
Stauffer Chem. Co.
Indust. Chem. Div.
Susquehanna Corp.
Susquehanna-Westerfl Inc.,
subsid.
Union Carbide Corp.
Mining and Metals Div.
City Chem. Corp.
Fairmount Chem. Co., Inc.
Foote Mineral Co.
Foote Mineral Co.
Stauffer Chem. Co.
Specialty Chem. Div.
Union Carbide Corp.
Mining and Minerals Div.
Ozark-Mahoning Co.
City Chem. Corp.
Foote Mineral Co.
Foote Mineral Co.
Stauffer Chem. Co.
Specialty Chem. Div.
Ozark-Mahoning Co.
Foote Mineral Co.
Foote Mineral Co.
Stauffer Chem. Co.
Specialty Chem. Div.
City Chem. Corp.
MacKenzie Chem. Works, Inc.
The Shepherd Chem. Co.
Location
Manchester, Tex.
Edgemont, S.D.
Rifle, Cob.
ersey City, N.J.
Newark, N.J.
Cambridge, Ohio
Cambridge, Ohio
Weston, Mich.
Niagara Falls, N.Y.
Tulsa, Okia.
Jersey City, N.J.
Cambridge, Ohio
Cambridge, Ohio
Weston, Mich.
Tulsa, Okaa.
Cambridge, Ohio
Cambridge, Ohio
Weston, Mich.
Jersey City, N.J.
Central Islip, N.Y.
Cincinnati, Ohio
-------
RJAR Ixc.
Table 1
Producer
Chemical Company, subordination Location
Vanadyl phthal- The Shepherd Chem. Co. Cincinnati, Ohio
ocyanine
Vanadyl p-tol-
uene sulfonate The Shepherd Chemn. Co. Cincinnati, Ohio
-------
RJAR JXC.
B. Costs
All prices belcM are f.o.b. prcd er:
Table 2
1972 Prices of Vanadiim & O mpour 3s
Cost per Kilogram
AmTonuiin variadate $ 7.50
Sodium vanadate $ 7.18
Vanaditmi pentoxide $ 7.08
Vanadium r ta1 (83% V) $ 8.80 per kilogram cxntathed V
Ferrovanadium (70-75% V) $10.20 per kilogram contain&1 V
C. Physical Properties
Physical properties of vanadium arid iiiiportant vanadium xiupourxls
are tabulat i in Table 3.
-------
Table 3
(3)
Physical Properties
Melting Boiling Solubility
Specific Point Point Water
Chemical Gravity CC 0 C g/lOOcc OC Comments
Vanadium 5.96 1890 + 10 3O00 insoluble Malleable &
ductile (pure)
Vanadium 3•35718 690 d1750 o.R 20 Rhombic crystals
pentoxide
Z mmonium 2.326 d200 O.52 Slightly hydro—
vandate 6.95 scopic
Sodium 630 2l.l Crystalline
vandate 38.8 powder
Vanadium 1.829 77 + 2 126.7 s(d)
oxytrichioride
-------
_______ Source of ore, type
domestic-vanadium-
uranium from by-pro-
duct ferrophosphorus
obtained in elemental
phosphorus production
Ark. vanadium ore
domestic ores and/or
residues
domestic ores and/or
residues
domestic ores and/or
residues
taking over operation
from Rifle milling
operation. V liquor to
be processed at Rifle
to V 2 O 5
.• Vanadium and vanadium pentoxide (4)
The United States is the largest producer and consumer
of vanadium. The bulk of the output is a by—product of the accel-
erated uranium production program of 1952 to 1956. Vanadium con-
tinues to be a co-product of the carnotite ores mined for their
uranium content. With the exception of substantial imports of ferro-
vanadium, the 1972 U.S. vanadium production statistics are as follows:
1 RfAR Ixc. VI-7
II. PRODUCTION
A. Quantities
The U.S. vanadium industry (see Section l.A.) is depen-
dent on the extraction of the metal from domestic ores, with the
exception of ferrovanadiwn, which is imported. The available van-
adium is recovered as vanadium pentoxide usually with either ammon-
iuin or sodium vanadate acting as an intermediate. This activity is
given in Table 4 Table 4
Producers of Vanadium Pentoxide
(4)
Location
Rifle, Cob.
Soda Springs, Idaho
Hot Sprir gs, Ark.
Hot Springs, Ark.
Edgemont, S. Dakota
Wilmington, Del.
Texas City, Texas
Moab, Utah
Urevan, Cob.
Company
Union Carbide
Kerr-McGee Corp.
Union Carbide
Union Carbide
Susquehanna-Western
The Pyrites Co.
Gulf Chem. & Metal
Corp.
Atlas Corp.
Union Carbide
-------
VI—8
V RJAR IXC.
ore and concentrate—recoverable V - 4,430 metric tons V content
v 2 0 5 recovered. - 4 750 metric tons as V
This represents essentially all of the vanadium available to
u.s. industry, with the exception of imports of ferrovanadium. In
1972 ferrovanadiUlfl amounted to 525 metric tons of contained vanadium.
B. Process
1. Vanadium
Vanadium IS not found in the free state; however, it
is widely distributed throughout the earth in rather low abundance.
It ranks twenty-second among the elements of the earth’s crust. The
production of the metal involves manufactured compounds as a basis
rather than using the naturally occurring ores. Pure vanadium metal
is very difficult to prepare because it combines readily with carbon,
nitrogen, hydrogen, and oxygen and also forms solid solutions with
some of its productS. Much of the vanadium produced is, therefore,
not highly refined.
There are two commonly used methods for preparing van-
adium metal. One involves the reduction of vanadium chloride with
hydrogen or magnesium; the other involves the reduction of vanadium
oxide with calcium, aluminum, or carbon. The oldest and most widely
used method for producing vanadium metal on a commercial scale is
the reduction of V 2 O 5 with calcium. Recent developments include a
two-step process involving the alurninothermic reduction of vanadium
oxide combined with electronbeam melting. This method is capable
of producing a purer grade of vanadium metal, of the quality required
or the nuclear reactor program.
a. Calcium reduction
This method produces vanadium metal of about 99.5
per cent purity. Vanadium pentoxide and calcium are heated in a
sealed bomb using calcium chloride as a flux. The calcium oxide
formed serves as a thermal booster as well as a flux, resulting in
both liquid metal and slage products. (In a modified process, iodine
-------
All V.129
VERJAR Jxc.
is used as a flux.) This became the basis for the first large—scale
commercial process for producing vanadium. This process is rela-
tively inefficient with metal yields of only 75 to 80 per cent and
the amount of calcium reductant required 50-60 per cent over that
theoretically needed.
b. Aluminothermic process
Vanadium metal is under consideration as a fuel-
element cladding material for liquid-metal fast-breeder reactors.
To meet the more stringent requirements for this application the
U.S. Atomic Energy Commission developed the aluminothermic process.
This involves reacting vanadium pentoxide with high purity aluminum
in a bomb, forming vanadium-aluminum alloy. The alloyed aluminum and
dissolved oxygen are removed in a high-temperature, high vacuum pro-
cessing step to yield metal of greater than 99.9 per cent purity.
c. Electrotransport technique
The highest purity vanadium prepared to date is
prepared by an electrotransport technique. A high-density current
is passed through a small rod of electrolytically refined metal. At
1700-1850C, the interstitial solute atoms such as carbon, oxygen, and
nitrogen migrate to the negative end of the bar. Using this tech-
nique, vanadium with less than ten ppm of carbon, oxygen, and nitro-
gen has been prepared.
2. Vanadium pentoxide and sodium and ammonium vanadate 6
The first stage in processing of most vanadium ores
is the production of an oxide concentrate for all ore sources. The
vanadium—bearing ores are generally crushed, ground, screened and
mixed with a sodium salt such as NaC1 or Na 2 CO 3 . The mixture is
roasted at about 850C,, converting the oxides to a water soluble
sodium metavanadate, NaVO 3 . This i extractedby leaching with
water, the pH adjusted to between two and three with sulfuric acid
which precipitates sodium hexavanadate. Na 4 V 6 O 17 (red coke). The
mixture is fused at 700C to a dense black product that is sold as
technical grade vanadium pentoxide containing a minimum of 86 per cent
-------
3%RJA R INC VI-lO
v 2 0 5 . Further purification may be obtained by disgolving the
vanadium in an aqueous solution of sodium carbonate and precipita-
ting the iron, aluminum, and silicon impurities by pH adjustment.
Then NH 4 C1 is added to precipitate amrnoniUlfl rnetavanadate, which
is calcined to give v 2 0 5 greater than 99.8% purity.
In the case of carnotite, a uranium-vanadium ore,
sulfuric acid is used directly on the raw ore or the ore may be
given an initial roast followed by successive leaching with water
and dilute HC1 or 11 2 S0 4 . The uranium and vanadium are then separ-
ated by liquid-liquid extraction techniques. The p 1- I and oxidation
atates are carefufl -Y controlled during extraction and stripping.
3. FerroVafladiUi!L
The raw materials, either technical-grade V 2 0 5 , van-
adiurn ore, or slag, are reduced with carbon, ferrosilicon or alum-
inum to yield a product whose vanadium content may vary from 35 to
80 per cent. The grade of product desired and the consumer use deter-
mine the choice of reducing agent. (6)
The vanadium alloy can be purified and consolidated
by two different methods. In one procedure the brittle alloy is
crushed and heated in a vacuum at 1790C to sublime out most of the
aluminum, oxygen, and other impurities. The presence of aluminum
facilitates removal of the oxygen, making this process superior to
the calcium process. Electron-beam melting of pressed compacts of
the vanadium sponge produces further purification and consolidation
of the metal.
Th€ other procedure involves direct electroflbeam
melting,Of the vanadium aluminum alloy reguluS. Two melting steps
are required before the desired levels of aluminum and oxygen are
reached in the final ingot. These procedures produce comparable
puritieS. IngotS weighing up to 225 kilograms have been prepared
by this process, using dried electronbearI melting of the a.lloy.
-------
Y RJAR INc.
Refining of vanadium . Vanadium can be purified by
one of three methods: iodide refining (van Arkel-de Boer process)
electrolytic refining in a fused salt, or electrotransport. The
first method has produced metal of greater than 99.95 per cent pur-
ity. In this process an impure grade of vanadium is reacted with
iodine at 800-900C. to form vanadium diiodide.
“The volatized iodide is thermally decomposed and depos-
ited on a hot filament at about iJOOC. The refining step
is carried out in an evacuated and sealed tube. The major
impurities removed in the process are the gaseous elements
and those metals that form stable, nonvolatile iodides. Van-
adiunt metal containing five ppm nitrogen, 150 ppm carbon,
and 50 ppm oxygen has been prepared in this way.” 6
The U.S. Bureau of Mines has developed an electro-
lytic process for purifying “crude” vanadium involving the cathodic
deposition of vanadium from an electrolyte consisting of a solution
of VC1 2 in a fused KCL - NiC1 eutectic. The vanadium content of
the mixture is between two and five per cent; the operating temper-
ature of the cell is between 650 and 675C. This method has pro-
duced metal crystals or flakes of up to 99.95 per cent purity.
a. Reduction with carbon has been replaced by
other methods in recent years. In fact, vanadium carbide has replaced
ferrovanadiuin as the vanadium additive in steel. Union Carbide
Corp., for example, markets a product containing 85 per cent vana-
dium, 12 per cent carbon, and 2 per cent iron, called Carvan. Car-
van is produced by the solid state reduction of V 2 0 5 with carbon in
a vacuum furnace.
b. The production of ferrovanadiurn by reduction
with silicon is used to a limited extent. This is a two—stage pro-
cess where technical-grade V 2 0 5 , ferrosilicon, lime, and fluorspar
are heated in an electric furnace to produce an alloy with about 30
per cent vanadium, but undesirable large amounts of silicon. The
addition of more V O 5 and lime extracts most of the silicon or else
forms a vanadium-silicon alloy by reaction of V 2 0 5 , silica, and coke
in the presence of a flux in an arc furnace. The primary metal is
-------
/ VI—12
VERJAR INC.
then reacted with V 2 0 5 to produce ferrovanadium. A silicon process
recently developed by Foote Mineral Co. is now used commercially to
produce large quantities of ferrovanadiuin. A vanadium suicide alloy
with less than 20 per cent silicon is made in a submerged—arc elec-
tric furnace by reacting vanadium-bearing slags with silica, flux and
a carbonaceous reductant and then refining it with V 2 0 5 . This is
then reacted with a molten vanadiferous slag in the presence of lime
to produce a ferrovanadiurn alloy called Solvan.
c. Aluminum reduction for making ferrovanadium in-
volves a highly exotherrnic reaction. A mixture of technical-grade
V 2 0 5 , aluminum, iron scrap, and a flux are charged into an electric
furnace and the reaction between Al and V 2 0 5 is initiated by the
arc. The temperature is controlled by adjusting the size of the par-
ticles and the feed rate of the charge, by using reduced material, or
by replacing some of the aluminum with a milder reductant such as
calcium carbide, silicon or carbon ferrovanadium of up to 80 per cent.
The well-known thermite reaction may also be used to produce vana-
dium. Here, V 2 0 5 and iron oxide are reduced by aluminum granules in
a magnesite—lined steel vessel or in a water—cooaed copper crucible.
The reaction is initiated by use of a barium peroxide-aluminum icni-
tion charge. (6)
Ferrovanadium is a general class of alloys, the
composition of which depends on the intended application. The com-
positions of commercial grades of ferrovanadium are listed below. (20)
Product Grade % vanadium
Iron Foundry 38-42
Grade A, open-hearth 50-55
Grade B, crucible 50—55 and 70—80
Grade C, primos 50—55 and 70—80
uigh-speed 50—55 and 70—75
Special Grade 50—55 and 70—75
Open-hearth 5O— 5
Foundry 50—55
-------
/ VI—13
VERJAR Jxc.
C. Estimate of Yearly Vanadium Release
An estimate of the yearly rate of vanadium release to the
environment is presented below:
Yearly Rate
Source Of Release (kkg) Comments
Mining and Pro- 50 Mostly (90 per cent) to
cessing of Van- atmosphere
adium Ores
Combustion of 22,000 17,000 to atmosphere;
Fuel Oil 5,000 to landfill
Combustion of Coal 6,635 5,000 to landfill or
dump; 1,635 to atmos-
phere
Metallurgical Usage 1,535 Atmosphere
Other Mineral and 100 Rough estimate; most
Ore Mining and Pro- available for leachinq
cessing
Miscellaneous 25 Rough estimate
Total ______
30,345 Roughly 65 per cent to
atmosphere initially;
remainder to land;
essentially all soluble
oxides
Because of the solubility of the vanadium oxide in water,
most of the vanadium entering the environment can be expected to enter
the waters. This amount cannot be estimated at present due to lack
of knowledge concerning lifetimes of vanadium oxides in the air,
leaching from landfills and dumps, etc.
More detailed data on vanadium content of the atmosphere,
oceans, etc. may be found in Section IX. World-wide data and local-
ized U.S. data on vanadium emissions in Section IX appear to support
the estimations presented above.
-------
/ .
VERJAR JxC.
III. USES
A. Vanadium and its Compounds
The major use for vanadium and its compounds and alloys
is in various types of steels. The end use and consumption of van-
adium materials for 1972 are given below. Table 6 presents a de-
tailed summary of current vanadium usage.
Table 5
Van dium Consumption
End Use Vanadium Consumed, 1972 (metric tons )
Steel;
Carbon 572
Stainless & Heat Resisting 28
Full alloy 800
High-strength low alloy 1,873
Tool 563
Cast irons 55
Superalloys 15
Other alloys:
Welding & alloy hard-facing 10
rods and materials
Nonferrous alloys 321
Others (including magnetic) 18
Chemical & Ceramic Uses:
Catalysts 134
Miscellaneous and unspecified 1 171
Total 4,740
1 includes end uses not listed to avoid disclosing company confiden-
tial data.
-------
Table 6 Table of Uses
(4,7)
Compound Use Purpose Comments
Vanadium Nonferrous The titanium “6-4” alloy (6% Al-4%V) Vanadium and aluminum
alloys is becoming increasingly important impart high temperature
in supersonic aircraft where strength— strength to titanium
weight ratio is important
Vanadium foil can be used as a bonding
material in cladding titanium to steel
Other Small amounts used for experimental
and special purposes
Vanadium Catalyst V 2 0 is important to the manufacture of One of the most important
oxide for organic sul uric acid, conversion of naphthalene commercial compounds of
and morgan- to phthalic anhydride, propane to acrv- vanadium
ic compounds lonitrite, acetylene to phthalic anhydride
In 1972 consumed 44C
metric tons of vanadium
Potential Will reduce hydrocarbon content of the
use in exhaust
afterburn-
ers of auto-
mobiles
Vanadium Manufacture Catalyze the formation of resinous black Some of the quick drying
oxide & of printing pigments from tar oils inks use amnioniurn i eta-
metavana— inks vanadate
dates Important commercial com-
pound of vanadium
In 1972 ammonium vanadat
consumed 33 metric tons
of vanadium
U i
-------
Table 6 Table of Uses
(cont.)
Compound Use Purpose Comments
Vanadium Catalyst in VOCl. , VC1AI and VCl used in the Primary industrial use
halides olefin poly- copo1 ymeri ation of thy1ene and
merization propylene
Source of One of. the most important
other vana— commercial vanadium corn—
diurn corn— pounds
pounds
Ferrovana— Steelmaking Improves certain physical charac— Accounts for the bulk of
dium teristics of steel the vanadium compounds us
Refines the grain structure and In open-hearth steel,
increases the hardening range of added to ladle
low-alloy steels
In electric—furnace steel
added before tap or to
ladle
In 1972 contained 85% of
total vanadium consumed
in U.s., 4,050 metric ton
Other van- Special Ex: vanadium—aluminum
adiuin alloys steels alloy (85% V, 15% Al)
used in manufacture of
titanium metal alloy
Other
alloys
-------
/ VI— 17
YERJAR INC.
B. Consumption Trends and Potential Future Uses
Domestic demand for vanadium in 1972 was almost nine per
cent higher than demand in 1971, but still below the peak demand in
1969. Research is underway into the use of vanadium metal as a pos-
sible structural material for fast breeder reactors. Also under
study is an electrotransport technique for the extraction and purifi-
cation of vanadium from raw materials. This method may reduce inter-
stitial impurities to less than five ppm by weight. The outcome of
research into the use of vanadium pentoxide catalyst in an effort to
reduce the smog-contributing components of .automobile exhaust
fumes may be yet another factor in future vanadium
A modest rise is expected in the use of vanadium as a minor
additive in various types of steels, cast irons, and special alloys.
Substitutes for vanadium may be employed for practically every case,
but unless a severe vanadium shortage develops, this is not likely
to happen. An increase of greater proportions is predicted for two
comparitively new steel—industry uses: high-strength low—alloy steels
and the continuous casting of steel alloys and billets. Niohiufli
could be substituted for vanadium, but would not be preferred unless
costs or availability became factors. If increased use of these
applications reaches the predicted levels, the production of vanadi-
um may be taxed. (8)
A reliable estimate on the use of vanadium alloys as a
cladding for fuel elements in fast breeder reactors is not possible.
Molybdenum is also under consideration for this application. Neither
of these materials is ideal and each must also compete with auste-
nitic stainless steels. The final choice will be based on which has
the fewer number of undesirable features. Another factor which must
be considered is the position technologically, ecologically, and
politically of the breeder reactor itself. The final decision may be
more than ten years away. In anticipation of a favorable decision
for the use of vanadium, however, government stockpile of vanadium
pentoxide should be increased and upgraded to limit the contents of
deleterious elements such as hydrogen and boron. (8)
-------
I 4 RJAR INC. VI- 18
Vanadium sources are expected to change in the future.
The largest supplier may be the vanadium-bearing slags, a by-product
of the iron industry which uses iron ores with a small percentage of
vanadium. Thus the output of vanadium and the economics of iron
production could be inter-related. The economically attractive pro-
duction of vanadium as a co-product of uranium may play a large part
in future vanadium supply since increased prospecting activity is
expected in the search for new sources of uranium. (8)
-------
r
I 1 ERJAR INC.
IV. CURRENT PRACTICES
A. Transportation and Handling
1. Vanadium pentoxide and ainmonium-metavánadate are packaged
in standard 50 kg fiber drums or shipped in bulk. They should be
stored in a cool, dry location. A nose or mouth respirator should
be used when handling large quantities.
2. Vanadium oxytrichloride is shipped in tank cars, tank
trucks and cylinders. It must be stored in a cool, dry location.
Skin contact must be avoided and the fumes should be regarded as an
acid gas and respiratory system irritant. Vanadium triox ’ch1oride is
classified as a corrosive liquid by the Interstate Commerce Commis-
sion. This is the only commercially significant vanadium product
which requires special handling. In transport, the chemical is iden-
tified with a white label, is not accepted on passenger planes and no
more than one liter is permitted on cargo planes. (10)
-------
VI—20
VERJAR IXC.
V. ENVIRONMENTAL CONTAMINATION
A. Overall Appraisal
The potential sources of contamination from use, production,
disposal and other sources are discussed below. In most cases the
analyses suffer from the scarcity ofpertinent information.
The only environThet tal problem that could be discovered may be pro-
duced by the combustion of residual fuel oil, and possibly of coal.
Local potential problems around plants and in working areas are men-
tioned in the course of subsequent discussions. Environmental con-
tamination from vanadium has not appeared to be a serious problem.
B. From Use
1. Metallurgical Uses
Small quantities of vanadium are used in steelmaking pro-
cesses. The content in alloy steels normally ranges from 0.1 to
0.5 per cent, but in some cases may be as much as four or five per
cent. The high temperatures involved in these operations cause the
emission of some of the vanadium compounds into the atmosphere. The
amounts are small and easily controlled. The vanadium pentoxide is
melted before its use as additive or alloying agent, producing some
pentoxide vapors. The primary source of environmental contamination
from vanadium compounds is from emissions to the atmosphere. A rec-
ent study estimated emission factors based on observations, stack
samples, contacts with operating personnel, and chemical analysis
of particulates. (11) The following values were obtained:
vanadium emissiOns, kilograms
Steel furnaces
Blast furnace 0.7/1,000 metric tons of pig iron
produced
Open—hearth 2.5/1,000 metric tons of steel pro-
duced
Basic—oxygen 0.2/1,000 metric tons of steel pro-
duced
Cast iron 0.11 per metric ton of charge
Non-ferrous alloy 6.0 per metric ton of vanadium
processed
-------
/ -I—2i.
J’ERJAR INc.
A 1965 Russian article reports that in “vanadiuin”-pig iron
production a highly disperse aerosol contains among other disperse
phases, 0.5-0.6 per cent of trivalent vanadium. Other constituents
of the aerosol produce more harmful effects. Similarly, although
harmful aerosols are generated in pig—iron converters, the triva-
lent vanadium present is not the bad actor. (12)
C. From Production and Disposal
1. Minir g and processing of ore
Vanadium ore is usually mined in conjunction with the
mining of another metal. The primary metal involved has changed
over the years. Recent emphasis is on uranium recovery. This
has caused some shift in vanadium mining and processing techniques.
As a rule, drilling and blasting are required to loosen the ore
which is then loaded on trucks and conveyed to the mills. The
ores are normally subjected to dry grinding, mixed with lime and
salt, and roasted. The product from the roaster, sodium vanadate,
is leached out by a variety of methods and the vanadate precipita-
ted out and fused to yield vanadium pentoxide. During various sta-
ges of this processing vanadium, compoundS do escape into the atmos-
phere. Records of these are not available, so estimates must be
made where possible. Based on observations and consultations with
plant personnel, vanadium atmospheric emissions during mining and
processin are estimated at abou 4 .5 ,q mr metric ton of vanac iUIfl
handled. Since only overall vanadium production is available,
only the total emissions can be calculated. Spot contamination at
individual mining and processing sites was estimated at 45 metric
tons for 1972.
At various stages in the processing, material is often
left uncovered and exposed to the elements. Soluble vanadium com-
pounds leak into the environment as a result of rain or ground wat-
er: from the cornininuted mineral prior to extractive treatment;
from the hot water leaching process to remove sodium metavanate
which is about 90 per cent efficient leaving the residue with sol-
uble vanadium compounds; from residues from roasting and leaching
-------
/ VI—22
VERJAR JXC.
of carnotite ore, vanadiferous clays and vanadium enriched slags
when heaped on the ground or used as landfills. (2
2. Production of ferrovanadiuin
In the production of ferrovanadiuifl from vanadium pent-
oxide, high temperatures are required to melt the pentoxide for
either use in the electric reduction furnaces or in chemical reduc-
tion processes. A vapor is formed of vanadium metal. This is
primarily a problem in the working area rather than as a source of
environmental pollution.
3. From inadvertent sources
By far the greatest sources of environmental contam-
ination are inadvertarit ones. Specifically 1 the combustiOn of oil
and coal produce atmospheric emissions in the form of particulates.
These constitute the bulk of the vanadium that gets into the envir-
onment. The residues from coal and oil furnaces also contain con-
siderable vanadium.
a. Combustion of Oil
The largest single source of environmental vana-
diem contamination is atmospheric emissions from oil—fired furnaces.
The furnace residues contain some vanadium, but may not constitute a
significant source of environmental contamination since they are
insoluble. This, however, is a potential source of vanadium which
the U.S. is not expected to exploit.
Crude petroleum oils contain some vanadium, varying
from less than one up to le 400 ppm depending on the source of-the
crude oil. For domestic crude oils the extremes are 0.1 ppm vanad-
ium content for New Mexican oil to 78.0 ppm for Montanan crude oil.
The vanadium content of Venezuelan crude oil varies from 0.6 ppm
for that from San Joaquin in eastern Venezuela to 1400 ppm for Bos-
can crude from western Venezuela. ‘The vanadium content of crude oil
from the Middle East, the other significant source of crude oil used
in the U.S., varies from 3 ppm for that from Qatar to 114 ppm for
Iranian (Gach Saran) crudes.(h1
-------
/ VI—23
YERJAR Ixc.
The distillation and refining of the crude o.l
leaves practically all of the vanadium in the bottoms, where resid-
ual fuel oil is obtained. The distillates, which include aviation
and motor gasoline, jet fuels, automotive diesel fuels and home
heating oil, contain barely detectable amounts of vanadium. The
crude and product heavy fuel oils are the only significant petrol-
eum sources of vanadium as potential environmental pollutants. The
treatment of the heavy fuel oils to reduce the sulfur content does
produce some reduction of vanadium content. A specific case in
point is the tz-eatinent of a Venezuelan crude oil as indicated below:
Sulfur Content, % Vanadium, ppm
untreated 2.6 218
desulfurized 1.0 105
desulfurized 0.5 59
Vanadium emissions from the combustion of residual fuel oils should
decrease as fuel oils are desulfurized in accordance with regula-
tions that limit the sulfur content of fuel oils. (21)
A 1965 Soviet article states that workers cleaning
out the ash residues at power generating stations where heavy petro-
leum fuel is burned suffered from “severe poisoning.”
Power boilers designed to burn fuel oil are not usu-
ally equipped with air pollution control devices; however, combina-
tion coal—oil units utilize mechanical collectors and electrostatic
precipitators which greatly reduce the atmospheric emission. During
1968 a study was made of the vanadium emission to the atmosphere
caused by the combustion of fuel oil. The electric utilities used
28% of the total residual oil using 32% of air pollution control.
Emission control for the total residual fuel oil used was estimated
as only ten per cent. Based on ten per cent overall control, the
vanadium emissions to the atmosphere during 1968 amounted to 17,000
kkg. The situation in 1972 was different in the greater quantities
-------
/ VI—24
VERJAR IXC.
of fuel used, more use of air pollution control devices, and dif-
ferent mix of oil crude sources. These would tend to balance out
the effects on vanadium emissions from the combustion of residual
fuel oil. Consequently, the.1972 vanadium emissions are assumed to
be 17,000 tons. This is conservative, considering that the quantity
of residual fuel oil used has increased by eight per cent or more
every year since 1968. A current estimate would be further coinpli-
cated by the “energy crisis”.
Little is known about the composition or size range
of the qanadium compound particles emitted to the atmosphere. Accor-
ding to Davis, the particulateS are mixtures of various vanadium
oxides and mixed oxides of vanadium and scdium, nickel, and iron
with a relatively wide spectrum of particle sizes. h1)
The limited use of pollution control devices in oil-
fired furnaces was reported earlier, based on 1970 information.
This situation may have changed by now. A 1965 article reported a
technique which reduces stack emissions from an oil—fired steam gen-
erator through the addition of finely ground magnesium oxide to the
fuel oil. By operating at low excess air together with this addi-
tive, a significant reduction in stack emissions resulted. The reco-
vered boiler pit ash was rich in vanadium pentoxide. The residual
oil used contained 250 to 1,000 ppm vanadium pentoxide and the boil-
er ash had 32 to 43 per cent vanadium pentoxide. The use of the
additive increased boiler efficiency and reliability and reduced
maintenance costs. The extent to which the magnesium oxide additive
is used has not been determined however, the technique is apparent—
ly well-known. It was discussed again in a paper given at the tenth
meeting of the New England Air Pollution Control Association, Hart-
ford, Connecticut, ifl 1966. ( 17)
b. Combustion of coal
The combustion of coal presents a significant source
of environmental contamination from vanadium. In addition to the
atmospheric pollution, considerable vanadium remains in the bottom
-------
/
VERJAR Jxc.
ash. During the combustion of the coal about 35 per cent of the
total ash is bottom ash. Tests have shown that the vanadium compo-
sition in the fly and bottom ashes are about the same. The vanadium
content of domestic coals, as well as that in the resultant ash are
given in Table 7.
Table 7
(18)
Concentration of vanadium in domestic coals
Coal source V in ash, % V i-ri coaL. ppin
Northern Great Plains 0.001—0.058 16
Eastern Interior Region 35
Appalachian Region 21
Texas, Colorado, North
& South Dakota 0.01-. 01
West Virginia 0.018—0.039
Pennsylvania (anthra-
cite) 0.01—0.02
Back Mountain Bed 0.11 176
Diamond Bed 0.09 92
The consumption of coal in 1972 is shown in Table
8. Using these data an estimate is prepared of the amount of van-
adium entering the atmosphere with the fly ash and then rernaini g
with the bottom ash. The following assumptions were made in arriving
at this estimate:
Average vanadium content of coal-22.5 ppm
90 per cent application of control and 85 per
cent efficiency of control
The estimate of vanadium emissions resulting from the burning of
coal in the United States in 1972 was 1,635 metric tons.
-------
/ VI—26
VERJAR IXG.
Table 8
(9)
1972 U.S. ConswflPtiofl of Coal (thousand metric tons)
Other
ManufaC.
Type Utiliti MetallUrgiCai & Mining Heatiflg Misc. Total
BitUI1 i 314,000 83,300 60,600 8,060 466,000
nOUS &
Lignite
Anthra— 1,430 683 2,650 553 5,330
cite
Modern coal-fired power plants use efficient fly-ash
control equipment which reduces considerably the emission of parti-
culates. Cyclones and electrostatic precipitatOrs are the most com-
monly used control equipment. Cyclones are more economical than
electrostatic precipitatOrs when additives which cause the formatiOn
of larger ash particles are used. The performances of two coal-
fired power plants was compared with different fly-ash control equip-
ment. In one case a cyclone-type separator only was used with resul-
tant fly-ash recoverY efficiency of 45 per cent, increased to 82
per cent with fly-ash reinjectiofl. In another case a cyclone-type
separator followed by an electrostatic precipitator was used to in-
crease efficiency to 94 per cent.
-------
/ VI—27
YFRJAR INC.
VI. MONITORING AND ANALYSIS
A. Monitoring
The Quality Assurance and Environmental Monitoring Labora-
tory of the National Environmental Research Center, state, and local
organizations sample air in a systematic manner to obtain information
about air quality in the United States. The last comprehensive sur-
vey was carried out in 1968-1969. Vanadium present in suspended par-
ticulate matter was one of the twelve metals whose concentration was
checked. The analysis emphasized urban and rural differences. Spot
checks of the air quality have also been conducted in such extreme
regions as in highly industrialized areas and very remote regions
such as the Artic or Antarctic. Also, many state and local govern-
ment air pollution control organizations maintain some surveillance
of air quality.
Representative information from APTD-l4(i7 is given in Table
9. The data chosen was taken from a comparison of urban and rural
vanadium emission characteristics and the effect of the seasons.
Examination of the vanadium concentrations in the relative cold and
warm seasons indicate that power and heat production with residual
oil products and coal are responsible for the increased vanadium con-
centrations in northeastern cities and also possibly in rural areas.
Manufacturing processes do not appear to contribute to the major por-
tion of vanadium emissions.
Analysis of the air over relatively unpopulated areas of
the earth, such as the Pacific Ocean area between San Diego and Hon-
olulu, show some vanadium, but only about 1,000th of the amount found
over populated areas. The vanadium found over a remote area of north-
western Canada is almost ten times that cited above. This suggests
that in addition to vanadium particulates circulated through the air
by the wind, some is injected into the atmosphere by wind erosion of
rocks and soil. (12)
Monitoring of rivers and other waters for vanadium has not
been reported.
-------
Table 9
(19)
Vanadium Concentration in Atmosphere, pg/rn 3
Urban
Location
New Haven, Confl.
Wilmington, Del.
Oakland, Cal.
Mobile, Ala.
Los Angeles, Cal.
Baltimore, Md.
Maximum
2. 500
1. 100
0.064
0. 015
0. 130
0. 720
Yearly Averaq
0 . 897
0.372
0.030
0.024
0.015
0.280
Nonurban
Location
Orange Co., Ver.
Arith. mean
Quarterly Composite
ist ___ ___
4th
0.237
0.620
0.160
0.230
0.480
0.023
0.033
0.030
0.035
0.032
0.023
0.020
0.023
0.034
0.0
0.013
0.013
0.240
0.160
0.340
0.180
(highest)
0.041 0.074
0.027 0.020
0.035 0.035
0.093 0.053
0.026 o.034
Calvert Co., Md. 0.056
0.019 0.042
-------
/ VI—29
VERJAR Jxc.
B. Analysis
1. Vanadium (in air—borne materials )
a. A section of an air filter is rolled up into a cylin-
der and placed in a hollow graphited electrode, then enclosed in an
atmosphere of oxygen. A condensed spark discharges to burn the filter
sample and excite the spectra. An internal standard compensates for
the small pieces of paper and ash which may be ejected during the pro-
cess. The spectra are interpreted by using a photographic recording
and the line intensities are measured with a microphotometer to pro-
vide greater precision. The limits of detection varied from 0.1-1
micrograms; the results agreed favorable with the more conventional
technique of ashing the filter, mixing with a spectrographic buffer,
and exciting in a D.C. arc. (20)
b. Vanadium in compounds can be measured by irradiating
the samples with neutrons and counting the gamma rays emitted by the
neutron capture product, 3.8-minute vanadiuin-5 2 , (with lithium—drifted
germanium gamma ray detectors)withOUt prior chemical separation. In
some cases, particularly in marine environments, gamma rays from sod-
iuni and chlorine may obscure those of vanadium-5 2 , making it necessary
to add a chemical step before counting sensitivity of the method. Val-
ues as low as 7 x l0 .ig/m 3 have been observed in AntartiCa. Based
on the sensitivity of this method of analysis . vanadium can serve as
an indicator of wide-scale movement of particulates. (13)
2. Vanadium in solution
a. Atomic absorption spectroscopy in oxy-acetytefle or
nitric oxide-acetylene flames can be used for the analysis of vana-
dium in the range of 0.5-100 mg/i. With oxy—acetylene flames, vana-
dium is extracted as the cupferrate into a mixture of methyl iso-
butyl ketone and oleic acid and the organic phase aspirated tO the
flame. The sensitivity is 0.7 mg/i of vanadium in the organic phase.
An extraction procedure eliminates potential interferences from a
large number of both cations and anions. Excess cupferron must be
-------
RJAR IXC.
added if Fe 3 +, Sb 3 + or Zn 4 + are present since they are preferentially
complexed. When nitrous oxide-acetylene flaifles are used, an aqueous
solution of vanadium salts is aspirated directly and the sensitivity
is improved by the use of methyl isobuty]. ketone, A1 and diethy-
lene glycol or diethyl ether. (22)
-------
/ VI—31
1 1 ER/AR mc.
Vu. CHEMICAL REACTIVITY
A. Environmental Reactions
In the massive state, vanadium is not attacked by air. At
high temperatures it is oxidized via the lower oxides to form V 2 0 5 .
It also reacts with nitrogen to form VN. Vanadium is quite resistant
to corrosion from sea water. 6
The catalytic property of vanadium compounds to oxidize
sulfur dioxide to sulfur trioxide deserves mention. This property
could present some problems in the combusion products of high vana-
dium and high sulfur oils.
-------
/ VI—32
YERJAR INC.
VIII. BIOLOGY
A. Content, Absorption and Excretion
1. Animals
Vanadium levels in human tissues are less than one
microgram per gram sh 1 ex ept in the case of the lungs, in which lev-
els as high as 108 microgramS per gram asbed InateriFll have been
reported. (23) Vanadium pentoxide is readily absorbed from the lungs
into the bloodstream. Seven days after an intratracheal adzninistra-
tior. of vanadium pentoxide to rats, no vanadium remained in the lung.
In a long-term inhalation experiment with rabbits, vanadium was
detected not only in the lungs, but also in the liver and kidneys. (23)
The content of vanadium in the enamel and dentin of
incisors from horse, fowl, cow, calf, and pig, and canines of pig
and dog averaged 29.0 to 41.5 ppm. No significant species differ-
ences or differences between enamel and dentin were found. (24)
SubcutaneouslY injected vanadium 48 pentoxide depos-
ited in higher concentrations in the dentin than in the enamel of
developing rat teeth. The highest concentrations were found adja-
cent to ameloblastS. (25) Topical application of vanadium— 4 8 pent-
oxide penetrated mainly into the enamel of human teeth, with some
radioactivity reaching the cementuin and dentin. (26)
Dietary vanadium reduced caries incidence and sever-
jty in the Syrian hamster fed a cariogefliC diet. (27) A dose of ten
ppm vanadium in drinking water had a slight cario-prOteCtive effect
when administered to mother rats. 28 In another study, vanadium
pentoxide in the drinking water not only did not reduce caries inci-
dence in rats, but produced toxic symptoms and inhibition of growth. (29)
Strontium and vanadium fed together decreased caries
prevalence in the teeth of rats on a cariogeniC diet. Zinc plus
vanadium stimulated increased uptake of phosphorus3 2 into the teeth
(30)
of these rats.
-------
/ VI—33
YERJ AR INC.
In man, vanadium taken orally in the form of sodium
metavanadate was excreted in the feces largely unabsorbed. Within
twelve days, 87.6% of the ingested vanadium appeared in the feces,
and the remaining 12.4% was recovered in the urine. Rats receiving
intragastric radiovanadiuln absorbed only about 0.5% of the dose. (23)
Humans treated with oral doses of ammoniufli vanadyl
tartrate, 25 to 125 mg daily, excreted vanadium in their urine as
long as they were maintained on the drug. Patients continued to
excrete vanadium in their urine three weeks after the drug was with-
drawn, but four to five weeks later, vanadium was no longer detect-
able in the urine. Less than 0.5% of a daily dose was excreted in
a 24 hour urine specimen, except for one patient receiving 125 mq
per day. About 1.2% of the daily dosage was found in his urine.
Presumably the rest of the vanadium was not absorbed, and was, there-
fore, excreted in the feces. (31)
In rats receiving sodium metavanadate intraperitOfle
ally, and in rabbits receiving intravenous injection, most of the
vanadium was excreted by the kidneys. The ratio of renal to fecal
excretion was 5:1. Sixty-one per cent of the vanadium was excreted
by the kidneys within twenty—four hours. In two men injected intra-
venously with sodium metavanadate daily for six days, 81 per cent
of the injected vanadium was eliminated in the urine within seven
days after the last injection, nine per cent in the feces; ten per
cent was presumably retained in the body. (23)
The rapidity of vanadium excretion should be consid-
ered when deciding the best time for the collection of blood sam-
ples and urine specimens from industrial workers. The kidney and
bowel are apparently the only excr’etory pathways for vanaaium.
The vanadium content of some tunicates of the order
Phlebobranchia isihown in Table 10. The oocytes of Ascidia py-
m ea are invaded by so—called titestll cells which possess a vanadium
chrornogen and which are derived from ameboid blood cells. vana-
dium pigment is required for the synthesis of cellulose for the test
in Ascidiidae species.
-------
Table 10
(32)
Vanadium Content of some Tunicates
Source %Vanadiuifl Species
Centrifuged bloodcellS 1.45 Ascidia nigra
Eggs 0.017 Phalucia marnillata
Ash 0.19 Phalusia mamillata
U I
-------
/ \11—35
VERJAR INC.
The vanadium organelles in the test cells which in-
vade the embryo may serve as chromogen reserves. When the embryo
metamorphoses, large amounts of polysaccharide for the test must be
synthesized quickly. The stored chromogen provides the pigment nec-
essary for the cellulose synthesis. (33)
In the tunicate, Ciona intestinalis , the accumulation
of vanadium by the blood cells is preceded by a specific active
absorption process. The single-cell-layer epitheliurn is the site of
vanadium absorption. The absorption is highly temperature depen-
dent and is inhibited by ouabain, phosphate and arsenate but not
chromate, niobate, molybdate or iron.
2. Plants
In plants, vanadium is absorbed by the roots into
two compartments: a freely diffusible, exchangeable compartment
and a nonexchangeable compartment. In absorption experiments the
uptake of vanadium—48 as amxnonium vanadate was studied in excised
barley roots. Calcium was necessary for absorptic”n, which apparent-
ly is not an active process requiring metabolic energy. The rate of
absorption of vanadium was highest at pH 4.0, being twice the rate
at pH 5-8. At alkaline pH’s, less absorption was noted. The pre-
dominant ionic species of vanadate present at pH 4.0 are the van-
aditun (V) dioxide cation (V0 2 +) anr vanadic acir (H”fl 3 ). 1 ’! e nre-
sence of other anions at ten times the vanadate concentration pro-
duced no great inhibition of vanadium uptake. Dihydrogen phosphate,
which produced the maximum inhibition, inhibited vanadium uptake by
only 27 per cent.
B. Distribution
1. Animals
Ten to twelve per cent of the injected vanadium
was retained in rabbits after two weeks and 74 to 84 per cent of
that was detected in the skeleton. (23) Small quantities were also
present in the kidney, liver, blood, spleen, lungs, adrenals, bone
marrow, skin, and muscles.
-------
/ VI—36
3”LRJAR INC
In rats injected with radioactive vanadium-48, at
the end of four days, the tissues retaining the highest percentages
of the injected dose were:
bone (9.9%), liver (6.2%), muscle (5.0%)
kidney p4.4%), and blood (4.4%)
The amount of vanadium is sharply reduced in the
livers of patients who have died from tuberculosis. The van-
adium content of bone tumors of various types (osteoblastoclastoma,
sarcoma, fibrous osteodystrophy, bone cysts, osteochondromas) is
higher than in adjacent bone tissue. (36) Brain tumors will also
accumulate vanadium. (23)
Vanadium is present in high levels in the blood of
some tunicates in green blood cells called vanadocytes. The hemo-
vanadin pigment, which contains nearly ten per cent vanadium in
some species is thought to have an oxidation-reduction role, per-
haps functioning as an oxygen carrier. The sea cucumber, Sticopus
mobii , contains 1200 ppm vanadium as dried matter. A mol].usc, Pleur-
obranchia plumula contained 150 ppm. Vanadium is probably absorbed
from the sea water, plankton and from marine silts in these crea-
(23)
tures.
In higher plants, the average concentration of van—
adium in dried material was one ppm, with the roots containing hiqh-
er concentrations than the leaves. Root nodules of leguminous
plants contained up to four ppm. (23)
The mushroom, Amanita niuscaria , contains relatively
large amounts of vanadium. Azuavadin, a vanadium-containing com-
pound, was isolated from this mushroom.
C.. Gr th and Nutrition
Although the precise purpose of vanadium is not known,
the essentiality of vanadium for optimum growth in the rat has
been demonstrated as shown in Table (38) The addition of 10
to 50 micrograms vanadium as sodium orthovanadate per 100 grams of
-------
Table 11
(38)
Growth Response of Rats to Varying Levels of Vanadium Supplements
(The total increase is given as the percentage
gain over a 21—to 28—day period)
Vanadium
(pg/l00 g
of diet)
1
5
10
25
50
7
16
6
14
6
1.05 + 0.08
1.04 ÷ 0.08
1.02 + 0.14
0.87 -f 0.10
1.02 + 0.14
7
16
7
14
7
1.27 ± 0.10
1.38 + 0.08
1.38 ÷ 0.07
1.21 ÷ 0.09
1.49 + 0.12
21
33
35
41
46
t
£. 01
£ .05
.02
. .02
* A total of 37 rats served as controls in five successive experiments.
t Not significant.
I i
tinsupplemented Controls
Rats Average daily
(No.)* weight gain
Supplemented Animals Total
Rats Average daily increase
(No.) weight gain (%)
p
-------
VI— 38
RJAR INC.
feed in an “ultraclean”, vanadium-free environment enhanced growth
of rats by over 40 per cent. Other forms of vanadium had similar,
but not as pronounced, effects. The levels of vanadium required
for optimum growth effects are those normally found in the environ-
ment. In one study, a commercial laboratory ration contained 1.50
ppm fresh weight of vanadium. 39 A rat weighing 75 grams needs
one to two micrograms vanadium per day (25 micrograms per 100 grams
feed). A human with a weight of 75 kg has been estimated to con-
sume two mg of vanadium per day. (40) Guinea pigs apparently also
require vanadium in the diet. In guinea pigs fed a vanadium-free
diet, a 50 per cent drop in the calcium and phosphorus contents of
bone was observed. Also, an increase in the incidence of dental
‘23)
caries occurred.
No positive effects on the growth of chicks could be
demonstrated, but chicks tolerated 20 to 40 micrograms per cent van-
adium in their diet. (41)
The requirement for vanadium in plants has been studied
in many species, but its essentiality for growth in higher plants
has not been conclusively demonstrated. (23)
Vanadium has an essential role in the green algae,
Scenedesmus obliguies , where it stimulates photosynthesis and growth. (42)
Vanadium is about 50 per cent as effective as molybdenum
in stimulating the growth of cultures of Azotobacter spp. (42) The
iron requirement of Streptococcus cremoris can be satisfied with
vanadium, but not with molybdenum, cobalt, zinc, copper or mang n-
(43)
ese.
Vanadium is considered an indispensable trace element in
the growth of the fungus, Aspergillus niger . (23)
D. Cytoxicity
Since the most likely route of vanadium exposure is
through the lungs, the effects of particulates of various vanadium
compounds on laved alveolar macrophages from rabbits were investi-
(44,45,46,47)
gated n vitro. Cell viability after a 20 hour expo-
sure was reduced by 50 per cent at the following concentrations.
-------
VI— 39
V RJAR INC.
Vanadium Compound & (micrograms V per ml )
V 2 0 5 13
V 2 0 3 21
V0 2 33
Only about nine micrograms vanadium per ml as vanadium
pentoxide was required to reduce cell viability by 50 per cent and
to decrease total cell number by 70 per cent after 20 hours if
the compound was first dissolved in the medium. The phagocytosis
of polystyrene—latex spheres was reduced 50 per cent by six micro-
grams vanadium per ml as vanadium pentoxide.
xposure of cells or cell—free sonicates to dissolved
vanadium pentoxide at leve1 as high as 50 micrograms vanadium per
ml produced only small changes in the specific activities of lyso-
zyme or _glucuronidase. Acid phosphatase in the cell-free system
was 70 per cent inhibited by one microgram per ml.
In another study, cell viability was reduced 50 per
cent by 0.1 to 0.2 millimolar aminonium vanadate. Cadmiuin 3 and
vanadate were found to be 37 to 62 times more toxic for alveolar
(+2) (+2) . (+3) (45)
macrophages than nickel , manganese , or chromium
The cell surfaces of control alveolar macrophage cul-
tures and cultures exposed to 0.098 millirnolar amrnonium sranadate
(5.0 micrograms vanadium per ml) were examined by electron microsco-
py. (46) The control cells exhibited intricate surface structure
with numerous membrane processes extending upwards as well as at-
tached to the substrate, but the vanadium-treated cells showed se-
vere morphological damage. Most of the cells completely lost their
processes, becoming unusually smooth; some developed bleblike struc-
tures or appeared to have broken open. When the macrophages were
incubated with 0.20 millimolar vanadate (10 micrograms vanadium per
ml), cell viability was reduced to 10 per cent, and a great number
of cells were so completely destroyed that only remnants of their
plasma membrane were seen.
-------
Table 12
(47)
Concentrations of Metallic Ions Causing Reduction
in Viability to 50 Per Cent in Rabbit Alveolar
Macrophages and Human Lung Fibroblasts
(Strain WI—38) at 20 Hours
Concentration of Metal,
mM
Metallic
Rabbit
Alveol.ar
Human
Lung
Ion
Macrophages
Fibroblasts
Cd 2 0.099 (0.062 — O.151)* 0.126 (0.077 — 0.201)
v0 3 0.234 (0.169 — 0.428) 0.620 (0.481 — 0.842)
Ni 2
4.17 (3.74 — 4.71) 2.83 (1.45 — 4.75)
5.29 (4.46 — 6.35) 9.82 (7.37 — 14.7)
Cr 3 5.48 (4.49 — 6.77) 11.3 (Estimated)
* 95% Confidence Limits are Shown in Parentheses.
-------
Table 13
(47)
Concentrations of Metallic Ions Causing Reduction
in Uptake of Thymidine, Uridine,
and Leucine to 50 Per Cent in Human Lung
Fibroblasts (Strain WI-38) at 20 Hours
Concentration
of Metal, mM
Metallic
TdR-2- 14 C
UdR—2- 14 C
Leu-l- 14 C
Ion
Uptake
Uptake
Uptake
Cd 2 0.444 See Note* 0.373
V0 3 0.009 0.017 0.044
Ni 2 0.176 0.136 1.27
0.396 0.098 7.56
Cr 3 3.80 3.40 9.49
* A 50 Per Cent Response was not Observed over Concentration Range Studied, (0.004 - 0.089 mM).
-------
/ VI—42
VERJAR JxC.
In cultures of human lung fibroblasts, vanadium had ef-
fects on cell viability similar to the effects on rabbit alveolar
macrophages. 47 The LC 50 for the fibroblast cultures at 20 hours
was 0.620 millimolar vanadate. At much lower concentrations, in-
hibition of the uptake of precursors of DNA, RNA, and protein syn-
thesis were observed in the human lung fibroblasts. Tables 12 and
13 are summaries of viability dat a and effects on uptake.
E. Metabolic Effects
Vanadium apparently exerts effects on sulfur metabolism,
energy metabolism, and lipid metabolism, as well as on various en-
(23)
zymes.
In normal sulfur metabolism, cysteine, cystine, and meth-
ionine are the three sulfur—containing amino acids. Normal sulfur
excretion occurs as sulfate in the urine, taurine in the bile or
keratin in hair and nails. Two cysteines, with free thiol (—SM)
groups, are easily and reversibly oxidized to cystine, which can be
decarboxylated to beta-mercaPtoethYlamifle, a precursor of coenzyme
A. Methionifle can be converted to cysteine. Coenzyme A is important
in various transacetylation reactions in the body, including those
involved in lipid and sterol synthesis. (23)
Rats fed 25 to 1000 ppm vanadium pentoxide exhibit a
marked reduction in the cystine content in the hair. (48) Supple-
mentary feeding of methionifle somewhat alleviated the effects. The
cystine content of the fingernails of vanadium workers was signif-
icantly reduced compared with that of healthy people and people suf-
fering from a number of diseases. (23)
Significant reductions in Coenzyrne A in the livers of
rats injected or fed sodium metavanadate occurred. The mitochondri-
al fraction of rat liver homogenate contained only 52.5 per cent of the
normal amount of coenzyme A and 86 per cent of the normal amount of
thioctic acid, a precursor of a coenzy!fle necessary for pyruvic acid
decarboxylatiOn. (23)
Vanadium Chloride and sulfate activate pyridoxal phos-
phate and the enzyme, desuiphydrase, which converts cysteine to
-------
4/ 7I—43
VERJAR Ixc.
hydrogen u1fide, ammonia and pyruvic acid. Since cysteine is the
precursor of cystine and Coenzyme A, the vanadium stimulation of this
enzyme may account for these observed effects. (23)
The effects of vanadium on ho1estero1 and other lipid
metabolism are somewhat ambiguous, depending on the amount, com-
pound, and mode of vanadium administration. Vanadium sulfate intra-
peritoneally injected into rats reduced the incorporation of radio-
active acetate into liver cholesterol by more than 50 per cent both
in vivo and in i ’it ro. (49) A decrease in both liver cholesterol and
phospholipid content, but not serum cholesterol was observed in
rabbits fed 100 ppm vanadium pentoxide.
In rabbits, the addition of 100 ppm vanadium as vana-
dium pentoxide to the standard diet reduced liver-free cholesterol
and phospholipid content by 2/3 and 1/3 respectively. Plasma cho-
lesterol showed no significant changes. The addition of 50 ppm
vanadium to a one per cent cholesterol diet restricted the hyper-
cholesterolemia observed in the absence of vanadium. Vanadium feed--
ing after dietary hypercholestorOlemia promoted a faster return to
(50)
normal cholesterol levels compared with rabbits fed no vanadium.
In rabbits fed high—cholesterol diets, 50 per cent less
cholesterol was found in the aortas of rabbits subsequently fed a
diet containing 0.05% vanadium sulfate compared with rabbits main-
tained on standard laboratory rations. The serum cholesterol levels
in the two groups showed little difference. The almost complete
mobilization of cholesterol from tissues other than the aorta occurred
in both groups, which raised serum cholesterol levels and probably
reduced hepatic cholesterol synthesis. Cholesterol synthesis in
the controls probably returned to normal activity when serum cho-
lesterol levels approximated normal after non-aortic tissue clear-
ance was completed, resulting in only very slow mobilization of
aortic cholesterol. Since hepatic cholesterol synthesis is appar-
ently inhibited by vanadium, the aortic cholesterol in the vanadium-
treated rats would be mobilized more rapidly. Similar effects have
been observed in chickens. (23)
-------
/ VI—44
VERJAR INC.
Vanadium inhibits cholesterol synthesis at several
steps in the pathway. These steps involve Coenzylfle A transfer reac-
tions. (23)
Serum cholesterol levels in a group of middle-aged male
vanadium workers were significantly lower than those of a control
popUlation, 205 mg per 100 ml compared with 228 mg per 100 ml. The
vanadium workers excreted four times more vanadium in the urine as
(23)
did the controls.
Oral administration of vanadium as diaminonium oxytar-
trato-vanadate to five male medical students at a dosage of 100 to
125 mg daily rest!lted in reduced fecal sterol excretion, 20 per cent
lower free and total cholesterol, and a rise in serum triglycerides.
These effects returned to normal when vanadium was removed.
Somewhat different effects were observed in rabbits
which received an intragastric dose of cholesterol of 1 g per kg as
a five per cent solution in cholesterol together with vanadium sul-
fate injections. (52) Rabbits receiving a dose of 1 ing per kg van-
adiurn sulfate had much lower blood cholesterol levels at various
intervals after treatment than did animals receiving solely choles-
terol. With repeated daily injections of vanadium sulfate for five
days, a slight retardation in cholesterol level occurred after in-
jection, but the degree of hypercholesterOlemia subsequently reached
the control levels, and by 240 hours, when control cholesterols had
returned to normal, the cholesterol level in vanadium—injected ani-
mals was twice the control level. The injection of 2.5 mg per kg
of vanadium twice a day did not cause an initial decrease in blood
cholesterol. Rather, an increase began at 96 hours after injection,
peaking at 120 hours, and falling to normal after 14 days.
Several effects on lipids and metabolism were observed
after subcutaneous injection of 5 to 30 mg vanadium as aminonium van-
adate per kg. Liver and serum triglycerides increased promin-
ently 4 to 48 hours after injection, the increase depending upon
the dose. Serum total cholesterol fell, reaching a minimum 24 hours
-------
/ fI—45
3 1 ER/AR Jxc.
after injection. Serum free fatty acids decreased qrad ially from
4 to 72 hours after injection. The decreases in serum cholesterol
and free fatty acids did not correlate with dose of vanadium. The
activities of both serum glutamate x lcacetate transaminase and
serum glutai tate pyruvate transaminase both increased according to the
dose of vanadium. No distinct changes in serum total cholesterol,
phospholipids or triglycerides could be detected in patients receiving
(31)
25 to 125 mg of ammonium vanadyl tartrate daily for several weeks.
Vanadium exerts effects on various sites of energy rneta-
bolism. Hyperglycemia has been observed in dogs intravenously per-
fused with lethal amounts of sodium metavanadate. In yeast vana-
dium increases the hydrolysis of hexose diphosphates. In male rats
given carbon-14—labelled glucose orally and aminonium metavanadate
intraperitoneally, significantly reduced amounts of carbon-i 4 diox-
ide were collected compared with controls, reflecting reduced oxi-
(54) .
dation of glucose. The addition of sodium metavanadate to guinea
pig or rat liver suspensions increased the rate of oxygen consumption.
Vanadate apparently uncouples the oxidative phosphoryl-
ation by which ATP is produced via aerobic respiration and the elec-
(55) .
tron transport system. In the liver mitochondria of chicks fed
25 ppm vanadium as ammoniurn metavanadate, although the amount of
oxygen consumed increased slightly, the rate of ATP synthesis dropped
by 22 per cent and the P /O ration dropped by 31 per cent. In vitro
addition of vanadate (one millimolar) to liver mitochondria pro-
duced more pronounced decreases in ATP production and P /O ratio. The
use of intermediate substrates, succinate or -hydroxybutyrate, did
not prevent the uncoupling. ATPa5e activity was at the least twenty
times the control activity in the presence of vanadate. Both ATP- 14
C-ADP exchange and ATP- 32 phosphoruS exchange were inhibited by vana-
date, the latter being more sensitive.
-------
ERJAR Ixe.
Vanadium salts influence the oxidation of various tyro-
sine and tryptophan derivatives, including 5-hydroxytryptamifle 1 or
serOt’)flifl. (23) Serotonin has a variable effect on blood pressure
when administered to animals. Vanadium salts have been shown to
activate the oxidation of serotonin to 5-hydroxyindole acetic acid
(5-HIAA) by monoamine oxidase of guinea pig liver. In hypertensive
patients, excretion of vanadium was three times the average normal
level of 0.6 micrograms per liter. If serotonin and similar amines
are supposed to have a pressor effect, vanadium deficiency, result-
ing in decreased ,i onoaminO oxidase activity, may result in occasion-
al vasospasms being sustained.
The enzymatic oxidation of tyrosine to dopa is acceler-
ated by vanadium, copper, cobalt, and nickel. A auantitative rela-
tionship between metal concentration and tyrosine oxidation has
(56)
been found.
Vanadium plays a definite, but obscure role in hemo-
poiesis. (23) Anemic rats return to normal in one—third to one-half
the usual six weeks time after initiation of.iron supplementation
when 0.05 mg of vanadium was also given. Normal young rats fed
0.25 mg iron and 0.05 mg vanadium daily developed reticulocytOSis
and a faster increase in red blood cells and hemoglobin occurred
than with iron alone. Vanadium gluconate given to rabbits intra-
venously for 40 days also produced significant reticulocytoSiS and
slowly developing polycythemia. The stimulatory effect of vanadium
on human hemopoiesiS has not been demonstrated. Vanadium may func-
tion through the activation of pyridoxal phosphate since pyridoxine
deficiency may lead to a reduction in red blood cells and hemoglo-
bin.
Vanadium compounds inhibit the enzymes which catabolize
acetyicholine. One hundred ml of ten millornolar metavanadate
weakly inhibited the pseudocholiflesterase of horse serum. Van-
adyl sulfate significantly decreased cholinesterase activity in rat
brain tissue preparations. No accompanying changes in free or
bound acetylcholifle occurred at the same time. (58)
-------
/ VI—47
VFRJAR JJVC
Radioactive vanadium—48 uptake was studied in selected
organs and liver subcellular particles of rats. (23) No significant
difference was seen in the rate or amount of uptake by liver par-
ticles of the three oxidation states of vanadium during the first
four hours. This amount of radioactivity was retained by the par-
ticles up to 96 hours, at which time other organs contained 10 to
84 per cent of their ten minute contents. t 96 hours, 46 per cent
of the vanadium—48 had been excreted in the urine, and nine per
cent in the feces. The amount of radioactivity in the liver super-
natant fraction had decreased from 57 per cent to eleven per cent,
but the mitochondrial and nuclear fractions increased from approx-
Tnately 14 to 40 per cent. The microsoffial fraction changed little.
Doses of 0.03 to 10 mg per kg vanadyl sulfate did not
affect the liver’s ability to acetylate sulfanilamide, but doses of
15 to 20 mg per kg did. Phenylacetic, phenylethylacetic and diph-
enylacetic acids inhibit sulfanilamide acetylation to different
degrees. Small doses of vanadyl sulfate did not potentiate their
effects, but high doses strengthened the effects of phenylacetic
and diphenylacetic only.
In plants, vanadium a ears to participate in the absor-
ption and reduction of nitrogen. The addition.of vanadium (40 ppm)
to the nutritive solution on sand cultures enhanced the absor-
ption of nitrate nitrogen. (60) When vanadium and molybdenum were
present together, itrat reduction was increased, as was the free
amino acid content of the plants. (61) Vanadium, but not molybden-
um, enhanced nitrite reduction, thereby resulting in increased pro-
tein synthesis. (62) In aquatic cultures of the cucumber, Cucurnis
sativus , vanadium caused rapid reduction of nitrate in the leaves
and also stimulated the accumulation of chlorophyll and carotene. (63)
tn experiments conducted with the ribosomal fractions
of pea cotyledons, vanadium and molybdenum reduced ribonuclease
activity. (64) Stabilization of the ribosome structure may be
-------
/ VI—48
VERJAR JxC.
accomplished by these metal ions. The ribonucleic acid component
of the ribosomes contained most of the ions accumulated by the ribo-
nucleoprotein particles.
The mushroom, xnanita muscaria , accumulates vana-
dium and produces a vanadium-Containing compound named arnavadin. 37
The ability of vanadium to partially replace molybden-
um in stimulating nitrogen-fixation by Azotobacter strains may be
due to vanadium incorporation into the nitrogenase complex promo-
ting increased stability and more efficient utilization of molyb-
denum-Starved cells. (42)
Induction of the penicillinase of Bacillus licheniforrn-
is can apparently be achieved with vanadate’, as well as molybdate
— (65)
and tungstate.
Commercial PNA from yeast was examined by electron spin
resonance, and some of the spectral absorptions could be identified
as vanadium and iron. (65) Iron complexes tended to form with the
RNA molecules easily precipitable by ethyl alcohol, whereas the van-
adium complexes formed more readily with smaller RNA molecules and
surface groups on the macromolecules.
-------
/ ‘ 11-49
I’ERJAR INC.
IX. ENVIRONMENTAL EFFECTS
A. Environmental Content, Transportation, and Contamination
Natural and manmade sources contribute to the vanadium con-
tent of the atmosphere. (13) Natural sources of atmospheric vanadium
are marine aerosols, produced by the bursting of bubbles at the sea
surface, continental dust from wind erosion, and a small contribu-
tion from volcanic ash. The ash from the burning of fuel oil and
crude petroleum is the primary source of manmade vanadium atmospheric
pollution.
Assuming that no specific mechanism for vanadium enrich-
ment in marine aerosols or continental dust is operating, the amounts
of atmospheric vanadium arising from natural sources may be estima-
ted relative to the amounts of other elements known to arise from
those sources. (13) Thus, to estimate the upper limit of the marine
aerosol contribution of vanadi”m in a given location, one can mul-
tiply the observed sodium and chlorine concentrations in the atinos-
pheric particulate by the vanadium to sodium and vanadium to chlor-
ine ratios in sea water. Likewise, the upper limit of vanadium from
dust and volcanoes could be estimated by assuming all of the observed
iron arises from those sources, and multiplying the iron concentra-
tions by the vanadium to iron r atio. Other elements,such as mag-
nesium, can be used to check results obtained in this way.
Using this method for predicting vanadium in the air of
windward Hawaii, the conclusion reached was that only 31% of the air-
borne vanadium arose from natural sources. (13) The predicted vana-
dium from natural sources for rural Canada amounted to 100 per cent
of the vanadium present, as would be expected in an area far re-
moved from man’s activities. Tables 14 and 15 illustrate the calcu-
lations.
This technique has been applied to the atmospheric vanadium
in several U.S. cities using the continental dust component only. (13)
The results are summarized in Table 3 6.
-------
Table 14
(13)
Predicted Vanadium Concentrations for
Windward Hawaii from Natural Sources
Source
Marine aerosols
Continental dust
Element Used
as Basis
Na
Mg
Fe
Mn
Al
Concn of
Element,
ng/meter
5300
670
38
0.86
101
Predicted V
3
0 . oo lO}
0.0010
0.0010
0.0991
0.103)
0.114
Total 0.11
Observed Acid soluble
Insoluble
Total
Predicted natural/observed
0.24 + 0.10
0.11 0.08
0.35 • 0.13
31%
v i
0
-------
Table 15
(13)
Predicted Vanadium Concentrations for
Rural Canada from Natural Sources
Concn of
Element Used Element, 3 Predicted V
Source as Basis ng/meter Concn, ng/meter
Marine aerosols Na 44 0.0000085 0 000005
Cl 13 0.0000019
Continental dust Fe 210 0.55
Mn 6.7 0.80
Al 186 0.26 0.73
Sc 0.11 1.57
La 0.20 0.50
Zn 15.4 31 ..
Sb 0.25 251 Anomalous
Total 0.73
Observed 0.72 ÷ 0.50
Predicted natural/observed . 100%
L u
-------
rab1e 16
(13)
Predicted Levels of Atmospheric Vanadium
Originating from Natural Sources
V Concentration (nanograms per m 3 )
Number of % from
Localit Samples Predicted Observed Natural Sources
Honolulu 12 1.64 3.4 ÷ 2.3 47%
Los Angeles 18 5.2 12.5 + 8 42%
San Francisco 9 2.9 6.2 + 2.1 47%
Northwest Indiana 25 9.4 8.2 2.8 114%
New York City 270 3.9 170 2%
New York City 150 2.0 1190 2%
Boston numerous 0.4—3.0 600 0.07—0.5%
U i
t%)
-------
/ vr-53
VERJAR Ixc.
In the highly industrialized cities of the northeastern
United States, the apparent large contribution of man’s activities
to atmospheric vanadium can be explained by the combustion of resid-
ual fuel oil high in vanadium content. The contribution of coal and
residual fuel oil to atmospheric vanadium have been estimated using
the elemental ratios. Table 17 shows that the predicted ranges of
vanadium in the oil easily account for the observed concentration
of airborne vanadium in the Boston area.
An examination of the particle size distribution of vana-
dium in the Boston area supports the contention that most of the
atmospheric vanadium originates from fuel combustion. (13) Vanadium
is preferentially associated with the smallest particles collected,
as would be expected for the high GmPeratUre of oil combustion fol
lowed by condensation of the vaporized material. Elements such as
iron or aluminum arising principally from coal combustion and conti-
nent dust are found in highest concentrations on the largest partic-
ulates in air. In the Boston area, although 342,500 metric tons of
coal were burned in 1966, this represented only twelve metric tons
of vanadium. The 1386 million gallons of residual oil burned con-
tained 4100 metric tons of vanadium.
The estimated annual rates of global injection of vanadium
into the atmosphere from petroleum and natural sources are surnn ar-
ized in Table 18.
The amount of vanadium in sea water is about 5 x i0 8 per
cent. Industrial effluents may provide sources of vanadium for
water pollution. (15)
The amounts of vanadium in some water samples from various
parts of the world are shown in Table 19.
Vanadium is present in many foods. Values are given in
Tables 20 and 21.
-------
Table 17
(13)
Predicted Vanadium Contributions from
Various Sources in the Boston Area
Concn of
Element Used Element, 3 Predicted V Concn,
Source as Basis ng/meter ng/meter 3
Continental Fe 1400 3.6
Mn 30 0.4
Al 1430 2.0 0.4—3.0
Sc 0.29 4.1
Co 2.4 30
Coal Fe 1400 3.5
Mn 30 2.3 2—9
Al 1430 2.6
Co 2.4 8.6
Venezuelan Residual
Crude Oil
Residual oil Co 2.4 1,400 7,000
Zn 380 16,300 550,000
Sb 9 3,650 157,000
Se 4 1,210 11,600
Range of Predictions 1200—16,300 7,000550,00G
Observed Range 90-2400
Average 600
I - f l
-------
Table 18
(13)
Estimated Annual Rates of Global Injection of Vanadium
into the Atmosphere from Petroleum and Natural Sources
Total Amount
Injected or
Consumed Assumed V Total V
Annually, Concn, Injected,
Source 106 metric tons ppm metric tons
A. Natural 4
Soil and rock dust 200 135 2.7 x 10
Volcanic debris 50 200 io
Sea salt 80 0.15 12
4
Total natural 3.7 x 10
B. Petroleum 2000 50 2 X
&1 )
I -n
-------
Table 19
(16)
Vanadium in Some Water Samples
Vanadium in water samples
Range Average
ppm ppm
Water samples from:
Atlantic Ocean
Baltic Sea
Lake Maelar (Sweden)
Small Lake (Stockholm, Sweden)
x 1.1
x I.O 0.4
1.4
0.6
5.0
0.8
—4
x 10 8.5
x
x
Drinking water from
Boston
New York
Chicago
Oslo (Norway)
Stockholm (Sweden)
Kiruna (Sweden)
Trosa (Sweden)
4.6 x
4.0 x
0.1 x
0.46 x
5.0 x 10 —4.4 x
3.5 x l0 —5.0 x
0.12 x l0 —O.24
0.45 x 10 —O.48
0.9 l0 —l.3
0.3 x
0.8 x 1O —1.9 x
0.4 x 1O —0.7 x
4 .9 x l0 —5.0 x
0.7 10 —0.9 x
8.3 x
x
x l0
x
—4
x 10
- —4
x 10
x
x
-------
Table 20
(16)
Vanadium in Some Animal Specimens
Wet wt
Ash wt.
Specimen Mean Range Average
ppm
0.51
0.11
‘.
‘.
L
b l0
ppm
0.83 x 10_2_l.].8 x io_2
0.18 x 10_2_0.30 x io 2
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 (Norway)
Fresh milk, Goteborg (Swederil
ppm
1.0 x 102
0.24 x io_2
0.04 io2
0.03 1o2_o.o7
0.06
0.20
2.9
0.28
0.20
0.46
0.24
0.16
0.13
0.48
0.20
l0
0.15
x
1o_2_o.36
1.1
—4.1
0.40
x
10 2132
x
0.42
x
102_l.0
0.81
x
lo_2_l.8
x
l0
0.71
x
10 —0.94
x
l0
0.66
x
l0 —0.88
x
0.52
x
lo —o.96
x
l0
0.76
x
l0 —1.45
x
10
0.70
x
10 —0.92
—2
x 10
x 102
io _2
io _2
—2
10
x io
x
x io
x io
x io
0.26
2.0
0.86
0.70
1.3
0.84
0.77
0.74
1.1
0.80
x 102
io _2
—2
10
—4
x 10
x
—4
x 10
—4
x 10
x
-------
Dried skim milk:
Carnation 2 (U.S.A.)
Starlac 3 (U.S.A.)
Famos 4 (Sweden)
Semper 4 (Sweden)
Lobster, meat (North Sea)
Gelatin (Sweden)
0.50 x
0.48 x
L 1O
L
Averaqe
ppm
Lvaiues represent ten samples of each of the specimens listed.
2 Carnation Food Company, Los Angeles.
3 Borden’s Food Products, New York.
4 Semper Company, Stockholm, Sweden.
U I
Table 20
(16) (cont.)
Vanadium in Some Animal Specimens 1
Ash wt. Wet wt
Specimen Mean Range
ppm ppm
16 . 1
2.5
1.8 l0 —2.8 x
1.3 10 —2.3 x
3.2 x 1o_2_5.3 x io2
3.9 x io2_s.o x io_2
2.3 x
1.9 x
4.3 x io_ 2
4.4 x 10
-------
Table 21
(16)
Dill
Lettuce
Parsley 3
Cucuinbe rs
3
Radishes
.3
Strawberries
Wild strawberries
Red whortleberries
Apples 3
Tomatoes 3
Cauliflower
3
Potatoes
Pears
Carrots 3
Common beets
Peas, frozen
4.6
2.8
29.5
0.38
7.9
0.66
0.72
0.54
0.33
0.041
0.093
0.093 x 102
0.84
0.58
4.52
5.6 x io2
1.26
3.1 io_2
4.1 x i0 2
1.02 x
0.86 x io2
0.53 x
1.09 x io
0.64 x io 2
0.14
2.1 x 102
0.79
2.1 x l0
5.21 x io_2
1.6 x
1.10 x l0
0.27 x l0
0.77 x l0
0.82 x
‘Values represent 10 samples of each item.
2 All samples were taken from the Stockholm area.
3 0f these species five samples of each grown in New Hampshire (U.S.A.) and five samples
grown in Rhode Island (U.S.A.) were also analyzed. The results from these 70 samples were,
in general, somewhat lower than those tabulated for the fruits and veqetables grown in Sweden.
Vanadium in
Some Fruits and Vegetables ‘
ppm
Ash wt
Mean
Dry wt Wet wt
Mean Range Average
ppm ppm
ppm
0.12 —0.15
1.9 lo_2_2.3 x 1O
0.50 —1.11
1.6 x l0 —2.3 x l0
5.22 x 10 2521 x io2
1.5 x l0 —1.7 x l0
1.89 x l0 —l.25 x l0
0.16 x 10 —0.38 x
0.72 x 10 —0.83 x
0.75 lo —o.89 x l0
-------
/ VI—60
VERJAR JxC.
B. BioaccumulatiOfl
Vanadium is readily absorbed through the lungs, and to a
small extent, by the small intestine. (23) .nimals do not retain
vanadium for long periods of time. Doses of vanadium are rapidly
excreted in the urine and the feces, and complete clearance of the
vanadium from the animal usually occurs two to three weeks after
vanadium administration has ceased. Vanadium tends to accumulate in
the bones, perhaps substituting for phosphorus. In the adult red
tail swordfish, Xiphosphorus helleri , vanadium-48 accumulated in the
bones, fins, skin, and liver after a three day exposure to the radio-
active element.
Some marine organisms, notably the tunicates, accumulate
vanadium. Apparently they can concentrate vanadium from sea water
with the pharyngeal mucous sheath. Vanadium serves as the metallic
element in the tunicate blood, existing complexed to p irro1e rings
in a structure similar to bile salts. Small amounts of vanadium
have been found in other phyla of marine organisms as well. (14) The
percentage of vanadium of the dry weight is sunut arized in Table 22.
Assuming the dry weight is only one per cent of the weight, many of
the organisms still contain 10 to 100 times the vanadium concentra-
tion as that reported for sea water (5 x lo_8%).
Plants take up vanadium through the roots especially at
acidic pH’S. Toxic amounts can be accumulated if insufficient iron
is present. Some plants such as Cleomes spp. appear to be vanadium
accumulators. (67)
Radioactive vanadium-48 was taken up by some vegetables
grown in soil boxes containing vanadiuin48 trichioride and cold sodi-
um vanadate. Vanadium-48 was taken up into both leaf and root vege-
gables and into the leaves of root vegetables. (39)
-------
Table 22
(14)
The Vanadium Content of Some Marine Organisms
Group
Thai lophyta
Porifera
Coelenterata
Bryozoa
Echinodermata
Mollusca
Crustacea
Species
Marine algae
Halichondrja sp.
Choanites ficus
Cyanea capilluta
Metrjdjwn dianthus
Anemonia sulcata
Plumatella fungosa
Stichopus mobii
S. japonicus var. armatus
S. tremulus
Cucuinaria lefevrei
Asterias glacialis
A. rubens
Paracentrus lividus
Brissopis lyrifera (shell)
Sepia officinalis
Helix sp.
Loligo sp.
Mytilus edulis
Crassostrea sp.
Patella vulgata
Carcinus moenas
Lepas anatifera
Vanadium
( % in dry matter )
5 x 10 (dry ash)
3 x 10 3 _ dry ash)
1.7 x 10
—4
5 x 10
4 x io— 3
2.3 x 10-
1.68 x IO
0.123
trace
5.7 x 10
1 x
3 x i0
9 x io
8 x io— 5
9 x io-
trace
5 x 10
4 x l0 _
1.2 x 10
1.3 x i0
i io— 5
—5
4xl O
1.2 x 10
-------
Table 22
(14) (cont.)
The Vanadium Content of Some Marine Organisms
Species
Ascidia mammillata (England)
Ascidia mentula (England)
Ascidia mentula (Atlantic)
Ascidia mentula var. rudis (Fng.)
Ascidia aspersa scabra (England)
Ciona intestirialis (Sweden)
Ciona intestinalis (England)
Ciona intestinalis (Atlantic)
BotryllOides schiosseri (Atlantic)
Pyura savigni (Atlantic)
DendrodOa grossularia (Atlantic)
DistomuS varialosus (Atlantic)
Molgula manhattensis (Atlantic)
Didelnnulfl candidum (Atlantic)
Didemnuin maculosum (Atlantic)
Morchellium argus (Atlantic)
Parascidia turbinata (Atlantic)
Parascidia aureolata (Atlantic)
Aplidiuiu pallidum (Atlantic)
Clavelina lepadiformis (Atlantic)
Scyllium caniculata
Gadus merlangus
Scomber sp.
Trigla sp.
Van ad i urn
(% in dry matter )
Grou
Tun i cat a
Pisces
0.17
0.186
0.0982
0.145
0.112
0.062
0.040
0.0166
8 x 10
7 x i0—
1 x
6 x
3.2 x l0
2.6 x 1 —
3 x 10— —
3.7 x 10
8.3 x
3.9 x i0
4.3 x
7 x i0
4x
1.4
2.2
lx
—6
x 10
x i0 5
-------
/ VI—63
VEI?fAR JX(:.
X. TOXICITY
A. Humans
1. Occupational exposure
Many occupations involve exposure to aerosols and dusts
of vanadium compounds. (15,23) Mining and milling of vanadium-con-
taining ores such as patronite involve health risks from handling
of the “inactive” ore before roasting, the “active” ore after the
roast, and in the final processing. Atmospheres in a Peruvian oper-
ation contained 0.18 to 58.82 mg vanadium per cubic meter of air
in the active processing, the highest concentrations of 12.77 mg
per cubic meter occurring in the final stages of processing.
Dust concentrations in the production of vanadium pent-
oxide and vanadates at one time might have amounted to 6.5 mg van-
adium pentoxide per cubic meter. (23)
The production of ferrovanadiurn and other vanadium alloys,
vanadium catalysts, and pure vanadium compounds such as vanadium
trioxide, vanadium chloride, and vanadium carbide, also involve
high vanadium atmospheres.
Occupational exposure to vanadium is not limited to
production of vanadium compounds. (23) Since most crude oils con-
tain up to 0.072 per cent vanadium by weight, occupations involving
exposure to ash and fumes derived from these fuels may involve haz-
ardous vanadium levels. The ash of these oils is about 65 per
cent vanadium, with some ship’s boiler ash containing 82 per cent
vanadium. Men who clean such oil-fired burners are likely to be
exposed to rather high concentrations of vanadium dust containing
all valences of vanadium compounds.
The symptoms of exposure to vanadium-laden dusts are
generally acute; relief occurs promptly when the irritant is removed.
(23) Upper respiratory irritation characterized by bronchospasm,
paroxysmal cough, expectoration, chest constriction, and shortness
of breath is the most frequent symptom. Accompanying conjunctivi-
tis, rhinitis, soreness of pharynx, and puruflet t eye discharges
often occur.
-------
VI—64
I 1 ERJAR INC.
Persons suffering from these symptoms are particularly susceptible
to respiratory diseases such as pneumonia. Other symptoms reported
include a feeling of weakness, elevated blood pressure., palpitation,
skin pallor, tremor of fingers and arms, and irritation of face and
arms. Hypersensitivity to vanadium has been induced after acute
exposures. A greenish-black tongue, with septic teeth and lingual
furring, is indicative of vanadium exposure, but not necessarily
poisoning. The green color is believed to be due to the deposition
of quadrivalent vanadium in the tongue and gums. Systemic poison-
ing due to overexposure to vanadium dusts can occur. The symptoms
include nausea, vomiting and diarrhea, central nervous system dis-
turbances, cardiovascular disturbances, anemia, hysteria, melanchol-
ia, dimness of vision, and retinitis.
Recommended limits for maximum permissible concentra-
tions adopted at the American Conference of (overnmental Industri-
(23)
al Hygienists in 1961 are:
Maximum Permissible Con-
Contaminant centration (mg per m 3 )
Vanadium pentoxide (dust) 0.5
Vanadium pentoxide (fume) 0.1
FerrovanadiUrfl (dust) 1.0
Exposures lower than 0.5 mg per cubic meter of vana-
dium pentoxide may produce eye, nose and throat irritation.
2. Other studies
Human volunteers were exposed to vanadium pentoxide
dusts for eight hours. (68) The dust concentrations were 0.1 to
0.25 mg vanadium pentoxide per cubic meter of air, with 98 per cent
of the particles less than five microns in diameter. Considerable
mucus was formed in the airways within 24 hours, followed by cough-
‘ing lasting from 48 to 72 hours. A concentration of 1 mg per cubic
meter induced coughing after only five to seven hours exposure,
which persisted for eight days. No pathological changes were found
in the lungs, in blood chemistry or morphology, or in the cystine
content of hair and nail clippings.
-------
/ V.t—65
VERJAR mc.
Intravenous injection of sodium tetravanadate (20 mg
as vanadium pentoxide) into men produced,at various times, saliva-
tion, lacrimation, disappearance of the pulse, cessation of breath-
ing, diarrhea, and a fall of up to three degrees in body tempera-
ture. (23) It is believed that a 30 mg dose would kill a 70 kg man.
A well—tolerated dose of the hexavanadate was 60 mg vanadium pent-
oxide injected by any route, although intramuscular injection pro-
duced some pain and swelling. At a toxic intravenous dose of this
salt (100 to 125 mg vanadium pentoxide), nausea and vomitinq, with
albumin and cylindrical casts in the urine were produced.
In a study in which patients were treated with daily
oral doses of amrnonium vanadyl tartrate, 25 to 125 mg, the only
signs of toxicity were diarrhea and cramping when the large doses
were given. The small amounts of vanadium absorbed by the intes-
tine probably account for this, as well as man’s tolerance to van-
adiuin and rapid excretion. (31)
B. Mammals
1. Acute toxicity
The degree of exposure and the valence of the vanadium
compounds affect the severity of symptoms. (15) The median lethal
doses of vanadium compounds in relation to valency as determined
in rats are shown in Table 23. Toxicity of some vanadium compounds
is shown in Table 24.
The LD 50 for a single intraperitoneal injection of
sodium metavanadate was 0.29 mg per kg in the mouse, and 0.22 mg
per kg in the rat. (69)
The lethal doses of various vanadium compounds in var-
ious animals are sununarited in Table 25.
Symptoms of acute toxicity manifest two distinct modes
of action: first, a central effect on the nervous system causing
drowsiness with convulsions, followed by gradual paralysis of res-
piration and motion; second, an effect on the alimentary tract caus-
(23)
ing abdominal pain, with diarrhea and bloody stools.
-------
Vanadium Compound
ammonium vanadate (NH 4 VO 3 )
vanadium trichioride (VC1 3 )
vanadium diiodide (V1 2 )
Table 23
(15)
Effect of Valence on Vanadium Toxicity to Rats
Median Lethal Dose
Valence ( mg V/kg )
5
3
2
10
23
68
C•i
-------
Table 24
(70)
Acute Toxicity of Some Vanadium Compounds
Vanadium Compound
vanadjc acid, monosodium—
salt
vanadium dichlorjde
vanadium (II) oxide
vanadium pentoxide
vanadium tetrachioride
vanadium trichioride
trichiorooxo vanadium
(vanady ltrjch lorjde)
vanadyl chloride
rat
rat
mouse
human
rat
rat
rat
Mode of
Administration
intraperitonea].
oral
intraperitonea].
inhalation
oral
oral
oral
oral
Toxic dose
( mg per kg )
4 (LDLo)
540 (LD 50 )
9 (LD )
0.lmg/in 3 /8 hr (TCL0
160 (LD 50 )
350 (LD 50 )
140 (LD 50 )
140 (LD 50 )
lethal dose to 50 per cent of animals tested
minimum lethal dose
lowest toxic concentration
Animal
rat
LD 50 :
LDLo:
TCL0:
-------
Table 25
(23)
Lethal Doses, in mq V 2 O/kg
Rabbits were injected intravenously, other animals subcutaneously
Rabbit Guinea-pig Rat Mouse
Colloidal V 2 0 5 1—2 20—28 87.5—117.5
Ammonium metavanadate 1.5-2.0 1—2 29-30 25-30
Sodium orthovanadate 2—3 1-2 50-60 50—100
Sodium pyrovanadate 3-4 1-2 40—50 50—100
Sodium tetravanadate 6-8 18-20 30-40 25-50
Sodium hexavanadate 30-40 40-50 40—50 100—150
Vanadyl sulohate 18—20 35—45 158—190 125—150
Sodium vanadate 30—40 10—20 100—150
-------
RJAR IXC.
Peripheral vasoconstriction in the spleen, kidney,
and intestine occurs after sublethal doses of metavanadate. This
occurred in the intact animal, after cervical cord section or decap-
itation, and in isolated perfused organs illustrating that this was
a direct effect of the vanadium. (23)
Hyperperistalsis, bronchospasm, diuresis, hypothermia,
and hemorrhagic gastroenteritis are other acute symptoms.
Both kidney and liver damage are evident in vanadium
poisoning. Glomerular hyperemia and necrosis of the convoluted tub-
ules were observed; congested and fatty degeneration of the liver
occurred. Cortical and medullary hemorrhaging in the suprarenals
were seen. The nuclei of the cortical pyramidal cells in the brain
showed less distinctly on staining, indicating that the tigroid sub-
stance was diminished. (23)
Death in rabbits was due to respiratory failure, thought
to be due to the direct action of vanadium on the central respira-
tory center. (23)
Toxic effects of ingested vanadium occur in rats fed
25 ppm vanadium as sodium metavanadate. Animals receiving eleven
and 22.5 ppm for twelve weeks appeared normal throughout the test
period. A dose of 92 ppm was quite toxic and 368 ppm usually caused
death within 10 weeks. A dose of 6 mg of vanadium as meta-or ortho-
vanadate, administered by stomach tube as 2 mg per day, was lethal
to rats weighing less than 100 g. Bleeding from the nose and intes-
tine, marked diarrhea, dyspnea, and paralysis of the hind legs occurred
(23)
before death.
Vanadium apparently has no cumulative action, and daily
doses can be given indefinitely as long as the tolerance level is
not exceeded. Typical symptoms of acute vanadium poisoning were
observed in the autopsy of poisoned animals.
A lethal inhalation dose of 500 mg per cubic meter van-
adiuin pentoxide to cats caused death in 23 minutes. Approximately
205 mg per cubic meter vanadium pentoxide for seven hours was lethal
to rabbits. Seventy mg per cubic meter was lethal to rats if
-------
/ VI—70
I 1 ERJAR INC.
prolonged over 20 hours. Typical symptoms were gastroenteritis,
pneurnonitis and pulmonary edema. (23)
One of the mechanisms for detoxification of vanadium
compounds by the body may be acidification. The LD 85 dose (9.1 mg
vanadium per kg) of sodium vanadate for mice at pH 7 was reduced to
essentially zero when the pH of the injection was 1.8. Increasing
the injection pH to 12.5 did not increase the 85 per cent toxicity
(71)
level.
Alterations of bicarbonate reserve by injection of
aminoniurn chloride to cause acidosis, or sodium bicarbonate to pro-
duce alkalosis also affected vanadium toxicity. In arnmonium chlor-
ide treated mice, the lethality of a sodium vanadate injection was
reduced from 60 per cent to 25 per cent. The mortality was increased
from 40 per cent to 80 per cent in sodium—bicarbonate—treated mice. (71)
Ascorbic acid and calcium disodium EDTA injections
have been demonstrated to antagonize the toxic actions of vanadium
compounds. (72)
2. Chronic toxicity
Daily subdermal injections (0.6 to 1.0 mg per kg for
300 days) or oral doses (6 to 11 mg per kg) to rats produced chan-
ges in many organs. The lungs presented the picture of pneu-
monia and numerous macrophages appeared. In the liver, fatty degen-
eration, vacuolization, and reticular necrosis of liver cells were
observed. Vacuolization of the kidney tubules and thyroid epi—
thelial cells of the follicle was observed. The follicles of the
spleen were atrophied, with macrophages occurrinq in the organ. Fat-
ty degeneration of the adrenals and degeneration of the pancreatic
parenchyrna occurred in some animals. No changes occurred in the
0 varies, but the canal of the epididymis was dilated, with some flat-
tening of the epithelial cells.
Chronic poisoning by inhalation of trivalent vanadium
(40 to 70 mg per m 3 for two hours daily) resulted in a fall in hemo-
globin level from 75 per cent to 67 per cent, a 33 per cent drop in
white blood cells, a drop in albumin and increase in globulin, resul-
ting in a halving of the a1bumin globulin ratio, an increase in
-------
/ VI—71
YERJAR IxC.
amino acids cysteine, arginine, histidine) in the blood, a ten per
cent rise in nucleic acid and a 30 per cent decrease in serum suif-
hydryl groups over the eleven-month A
50 per cent fall in vitamin C in the blood also occurred. The symp-
toms described above were evident.
Vanadium trichioride proved to be more toxic than vana-
(15)
dium trioxide. Vanadium pentoxide was three to five times as toxic.
3. Teratogenicity, carcinogenicity and mutagenicity
No evidence of carcinogenicity, mutagenicity, or tera-
togenicity of vanadium compounds has been found. Some cases of appar-
ent allergic response after occupational exposures have been noted. (23)
C. Birds
Vanadium administered as calcium vanadate at a level of
(74)
30 ppm vanadium significantly depressed the growth of young chicks.
In one study, ten ppm vanadium in the feed reduced feed consumption,
but no differences in blood phosphorus or bone ash levels were
observed. No mortality occurred with 20 to 120 ppm vanadium as
calcium vanadate in the diet, but 30 per cent and 100 per cent mor-
(74)
tality occurred with 200 and 400 ppm, respectively.
In white Leghorn laying hens, a level of 30 ppm vanadium as
(76)
a onium vanadate depressed egg production. Egq hatchability was
depressed at levels of 50 ppm. Body weight tended to decrease as the
level of vanadium increased, and albumin quality in the eggs was
markedly depressed by 15 to 20 ppm in the diet.
A reduction in the toxic effects of 20 ppm vanadium as ammo-
nium vanadate fed Lo chicks was accomplished by the replacement of
five per cent sucrose in a sucrose-fish diet with degossypolized
cottonseed meal or the addition of five per cent dehydrated qrass. 77
The addition of 0.25-0.50 % ascorbic acid to the ration also reduced
the vanadium toxicity. Since vanadyl chloride (VOC1 2 ) with a val-
ence of four was as toxic as arnmonium vanadate, the ascorbic acid
effect is not likely to be a reduction in the oxidation state of van-
(74)
ad i urn.
-------
vi—7
I 4 RJAR INC.
D. Plants
Little information has been found on the toxicity of vana-
diurn to plants. Vanadium in sand culture of Medicago sativa at a
level of 500 ppm reduced plant growth. The effect on the roots was
particularly severe. (78)
Toxicity symptoms appear in soybean, flax and peas with 2.5
to 5 ppm vanadium in the nutrient solution. Vanadium did not count-
eract the symptoms of iron-deficiency chiorosis. The reduction of
the standard iron concentration by 1/3 to 1/2 accentuated the tox-
icity of vanadium. Raising the iron supply to 20 or 30 ppm reduced
the vanadium contents of the shoot and counteracted the vanadium tox-
i city.
When the iron supply was low, vanadium reduced the phosphor-
us content of the shoot in soybean and flax, but increased the phos-
phorus content in peas.
E. Microorganisms
The growth of cobacteriUm tuberculosis diminished when
the concentration of vanadium pentoxide in the medium was three micro-
grams per ml. An increase in vanadium from three to five micrograms
per ml reduced growth even more, and growth ceased with concentra-
tions over five micrograms per ml. (35,80)
Vanadyl sulfate has demonstrated therapeutic usefulness in
the treatment of tuberculOSiS in white mice and guinea pigs. (81)
F. Results of Personal Contacts with Medical personnel
A total of 74 toxicologists and medical examiners throughout
the United States were contacted by telephone or letter with regard
to their professional acquaiiitaflCe with incidenceS of accidental
poisoning attributed to vanadium or its compounds. None of the 31
responses cited such an incident.
-------
RJAR JxC.
XI. STANDARDS AND CURRENT RE(UL7 TIONS
Threshold Limit Values (TLV): (82) (recommended)
3
Vanadium pentoxide dust: 0.5 mg/rn as V 0
Vanadium pentoxide fume: 0.1 mg/rn as V 2 0 5
Based on German experience the recommended maximum concentration in
work areas are:
V dust (probably as V 0 ) - 0.5 mg/rn 3
V smoke (probably as V 0 ) - 0.1 mg/rn
ferrovanadium dust - 1 mg/rn
In the USSR, the maximum allowable concentrations adopt—
ed for occupational exposure to industrial hazards are:
V 2 0 5 “condensation” aerosol - 0.1 mg/rn 3
V 0 “comminution” aerosol - 0.5 mg/rn 3
Vanadates and vanadium chlorides - 0.5 mg/rn
Ferrovanadiujn and vanadium-aluminum alloys - 1.0 mg/rn 3
Vanadium carbide - 4.0 mg/rn 3
There is some difficulty, especially in foreign articles,
in distinguishing between “regulation” and “standard”. The foreign
regulations presented below must therefore be interpreted with res-
ervations.
One German articie’84) states that “ the maximum allowable
working place concentration of vanadium in air is uniform for all
industrial nations.” Maximum allowable emission concentrations, how-
ever, differ. In the USSR the maximum is 0.002 mg/rn 3 ; in the Fed-
eral Republic of Germany a maximum allowable emission concentration
of 0.001 mg vanadium/rn 3 is under discussion.
Only one article, a 1960 Russian piece, expressed con-
cern with the vanadium content of water. The writer suggested a
vanadium concentration of 0.1 mg/i as a maximum permissible limit
for water basins.
-------
/ \1I—74
VERJAR [ XC.
XIII. SUM 4AR1 ND X 4cWSIc S
A. Sumary
United States is the la.ngest producer and si.m r of vanaditm .
‘Itt material is produced at present mainly as a by-product of the urenium in-
dustxy. Hoc ’ er, this oculd cthange in the future as vanadium is available
from several other sources.
The release of vanadium to the envir irertt frcet man’s activities
is estimated to be over 30,000 netric tons per year, of which about 1 o-
thirds arises from the cxnTbustian of residual fuel oil. anount entering
the environnent from processing and use of vanadium material is small in
parison to the above. In view of the solubility of vanadium oxide, nud
of the van lium in wastes can be ctnsidered to enter the waters over a finite
period of the. Natural sources of vanadium inC1U wind erosion of rocks
and transport from soils.
‘Ibxicity of vanadium and its cenpounds to humans varies fran
noderate to acute. There has been little a arent alverse effect of the vana-
dium in the environrrent, but occupational hazards exist and are . ll-docunented.
Also, residi. from oil-fired furnaces often centai.ris dangerous levels of
vanadium c rpwnds. The Threshold Limiting Va1LE for a centration of vanadium
aiipounds has been set as follc is: vanadium pentoxide dt t, 1.5 rr /m 3 ; vanadium
pentoxide ftme, 0.1 ir /m 3 ; and ferrovanadium dust, 1.0 n j,kn 3 .
Vanadium has marked effects on hi n rretabolisrn in that it reduces
thioresterol production and affects production of various enzyires and sulfur-
o taining amino acids. Vanadium ingested by himens appears to be excreted
largely unabsorbed. evidence was found of terathgenicity, carcinogenicity
or nutagenicity occasioned by vanadium. Sone a .parent a11er ic response was
observed to develop after occupational exposures.
Vanadium cx pounds may be absorbed through the lungs and, to a snail
extent, by the intestine. ? bst of the orally ingested vanadium is excreted in
the feces. Elevated urinary vanadium levels reflect vanadium exposure, and systemic
vanadium is rapidly eliminated frat the body by the kic eys. Vanadium inter-
feres with sulfhydryl group rretabolism and reduces hypertho1esterol nia.
-------
Y’ERJAR Jxc.
¶lbxicity varies with valence state and nrxè of administration.
1 ft effects of vanadium on higher animals are qu.ite similar to
those on humans. In the case of rats, the need for vanadium for optimum
grcwth has been sh n. The effects of vanadium on animal rretabolisrn axe also
similar to that in humans. ‘It cicity in animals is greater than in humans and
greatly dependent on exposuxe and the valence of the vanadium ion. For the
latter, the order of toxicity is 5 + > 3 + > 2 +. The green blood pigrrent of
the t icates, a groi. of marine l er thordates, oontains vanadii.mi, and
these organi s effectively accuirLilate the eleirent fran sea water and silts.
Sare F lothurians (sea cucuthers) also oontaixi high levels of vanadium.
The essentiality of vanadium for gz th in higher plants has not
be anclusively derronstrated. It has been sha in that vanadium plays a role
in the absorption and reduction of nitrogen by plants. Information on the
toxicity of plants to vanadium is relatively limited, particularly informa-
tion on long-term toxicity effects.
Plants acctntulate and translocate vanadium, particularly at acidic pH.
Phytotaxicity may involve interferencE with iron take by plants.
B. Ccnclusions
The folicMing oonclusions are based on the information a tained
in th.LS report:
(1) Althouh a relatively large an umt of vanadium (on the order of
30,000 netric is per year) enters the envircxuiE.nt fran man ‘s activities, no
widespread detrizrental effects have been identified to date. Presumably, man
and the higher animals do not accuiailate vanadium in hazardous anDunts.
(2) latively little information is available x ceniing effects
of vanadium on plants, la r animals, and microorganisms. SincE sane of these
species accuimilate vanadium and sare exhibit detriirental effects for acute
exposure, potential environriental hazards fran vanadium may exist if environ-
rrental vanadium leve is increase.
-------
vI—76
V RJAR JXC.
(3) Use of van ium will pz:thably c x tini.e to increase, parti-
ilarly its use in steels and other alloys, but there is ro present indica-
tic that sudi usa increases will be rapid. Potaitial su lies are
available to nest si iifi cant increases in c xnand.
C. endatiCflS
¶1 fo1iø. ii-flg reccnEndatiC of further work axe based ai the
s zrinary and cx clusiQ S presented above:
(1) It is rea it nc d that further study of effects of vanadium,
specifically soluble vanadium oxides upon plants (and possibly lc er animals
and j oorgani as ell) be çerfoxT ed. Areas of high soil vanadititi perhaps
CX)Uld be useful to sudi a study.
-------
VI—77
VERJAR INC.
Re ferences
(1) Stanford Research Institute. U.S.A. Chemical Information Ser-
vices. Directory of Chemical Products. Vanadium Chpt. Menlo
Park, California, 1974.
(2) 1974 Buyers’ Guide Issue. Chemicals, Raw Materials and Spec-
ialties. Chemical Week. McGraw—Hill, New York, New York. p. 642
(October 31, 1973).
(3) Handbook of Chemistry and Physics 1971-1972. 52nd ed., Robert
C. Weast, ed. The Chemical Rubber Company. Cleveland, Ohio, 1971.
(4) Minerals Yearbook 1972, Vanadium Chpt. Bureau of Mines, U.S.
Dept. of the Interior. Washington, D.C., 1974.
(5) Clark, R.J.H. The Chemistry of Titanium and Vanadium. Elsevier
Publishing Company. Amsterdam/London/New York, 1968.
(6) Encyclopedia of Chemical Technology XXI. 2nd ed. R. Kirk and
D.F. Othiner, eds. John Wiley and Sons, Inc. New York, New York,
1968.
(7) Busch, Phillip. M. Vanadium, A Materials Survey. Bureau of
Mines, U.S. Department of the Interior. Washington, D.C. Infor-
mation Circular 8060, 1961.
(8) Trends in the Use of Vanadium. National Materials Advisory Board-
National Research Council, National Academy of Sciences, National
Academy of Engineering. Washington, D.C. NMAB-267, March, 1970.
(9) Technical Data. Foote Mineral Company, Eton, Pennsylvania. Nos.
138, 140, 141.
(10) Sax, Irving N. Dangerous Properties of Industrial Materials,
3rd ed. Van Nostrand Reinhold Company. New York, New York,
1968.
(11) Davis, W.E. and Associates. National Inventory of Sources and
Emissions: Vanadiwn-l968. Environmental Protection Agency.
Washington, D.C. NTIS no. PB-221-655, June, 1971.
(12) Roshchin, I.V. Metallurgiya vanadiya v svete gigieny truda i
voprosy profilaktiki professional’nykh zabolevanii i intok-
sikatsii. (Vanadium metallurgy in the light of labor hygiene:
problems of the prophylaxis of occupational diseases and poison-
ing). Gig Tr Prof Zabolevaniya (Moscow). 9. 3—10 (1964).
-------
V RJAR JxC. vI-78
References
(13) Zoller, W.H., G.E. Gordon, E.S. Gladney, and A.G. Jones. The
Sources and Distribution of Vanadium in the Atmosphere. Trace
Elements in the Environment. EvaldO L. Kothny, ed. Kothnig
Advances in Chemistry Series. American Chemical Society. Wash-
ington, D.C. no. 123, 1973.
(14) vinogradov, A.P. The Elementary Composition of Marine Organ-
isms. Sears Foundation for Marine Research, Yale University.
New Haven, ConnectiCUtt, 1953.
(15) RoshChifl, I.V. ToksikOlogiya soedinenii vanadiya , primenyaemykh
v sovremenflOi promyshlennoSti. (Toxicology of vanadium com-
pounds used in modern idustry). Gig Sanit (Moscow). 32(6):
26—32 (1967).
(16) Soremark, Rune. Vanadium in some biological specimens. J Nutr.
92(2): 183—190 (1967).
(17) AthanaSsiadis, y.c. Air Pollution Aspects of Vanadium and its
Compounds. Litton Industries. Bethesda, Maryland. NTIS: PB-
188—093, September, 1969.
(18) Abernsthy, R.F., et c ii. Rare Elements in Coal. u.s. Bureau of
Mines, u.s. Department of the Interior. Washington, D.C.
Information Circular 8163, 1913.
(19) Air Quality Data for Metals, 1968 and 1969 from the National
Air Surveillance Networks. U.S. Environmental Protection Agency.
Washington, D.C. APTD-1467, June, 1973.
(20) Webb, R.J. and M.S.W. Webb. A Rapid Emission SpectrograPhic
Method for the Analysis of Air Filters. Atomic Energy Research
Establishmefl€, A a1yticai Sciences Div. Harwell (England).
NTIS: AERER6966, 1971.
(21) Vanadium. Committee on Biological Effects of Atmospheric Pol-
lutantS, National Research Council, National Academy of Sciences,
National Academy of Engineering. Contract No. 6B-02-0 42. The
Environmental Protection Agency. Washington, D.C., 1973.
(22) Sachdav, S.L., j.w. Robinson, and P.W. West. Determination of
vanadium by atomic absorption. SpectrornetrY. Anal Chirrt ACTA
(Amsterdam) . 37: 9—12 (1967)
(23) Hudson, T.G. Faulkner. Vanadium. Toxicology and biological
significance. American Elsevier Publishing Company, Inc. New
York 17, 1964.
-------
vI-79
VERJ’A R Jxc.
References
(24) Durr, U. Uber den Spurenelementgehalt in Zahnen der 1-laustiere.
(Content of fluoride, manganese, molybdenum and vanadium of
the incisors of animals). Berlin Muenchen Tieraerztl Wochenschr
(Berlin). 82(17): 326—330 (1969).
(25) Soremark, R., S. [ Jllberg and L.A. Appeigren. Autoradiog. local-
ization of vanadium pentoxide (V2 48 05) in developing teeth arid
bones of rats. ACTA Odontol Scand (Turku). 20(3): 225—232
(1962)
(26) Soremark, Rune, and Nils Anderson. .Uptake and release of van-
adiuin from intact human enamel following V 2 48 0 5 application in
vitro. ACTA Odontol Scand (Turku). 20(1): 81—93 (1962).
(27) Geyer, Carlos F. Vanadium, a caries—inhibiting trace element in
the Syrian hamster. Jour Dental Res. 32(5): 590—595 (1953).
(28) Grippaudo, G., M. Cattabriga and F. Valfre. L’influenza degli
elementi traccia, Molibdeno, vanadio e stronzio sulla cane
sperimentale. (The influence of trace elements molybdenum, van-
adium and strontium on experimental caries). Ann Stomatol.
20(7/8): 223—236 (1971).
(29) Muhler, Joseph C. The effect of vanadium pentoxide, fluorides,
and tin compounds on the dental caries experience in rats. Jour
Dental Res. 36(5): 787—794 (1957).
(30) Foidvani, I.P., C. Simpson and P. Kertai. The effect of V 1 Sr
and Zn on retention of P by the teeth of rats on a cariogenic
diet and on caries prevalence. Fogorvosi Szemle (Budapest)
55(9): 267—271 (1962).
(31) Dimond, E. Grey, Josefina Caravaca, and Alberto Benchimol. Van-
adium. Excretion, toxicity, lipid effect in man. Amer Jour
Clin Nutrition. 12(1): 49—53 (1963).
(32) Ciereszko, L.S., E.M. Ciereszko, E.R. Harris and C.A. Lane. Van-
adium content of some tunicates. Camp Biochem Physiol (London).
8(2): 137—140 (1963).
(33) Kalk, Margaret. Cytoplasmic transmission of a vanadium compound
in a tunicate oocyte, visible with electronmicroscopy. ACTA
Embryol Morphol Exp (Palemo). 6(3) : 289-303 (1963).
(34) Rummel, W., H.J. Bielig, W. Forth, K. Pfleger, W. Rudiger, and
E. Seifen. Absorption and accumulation of vanac3iun by tuniOatës.
In: Proceedings of the fourteenth Colloquium on protides of the
biological fluids, 1966, Bruges, Belg., Elsevier Publishing Com-
pany: Amsterdam, London, and New Yor?. Protides Biol Fluids.
14. 205—210 (1967)
-------
ERJAR Jxc. V180
References
(35) Bala, Y.M., and L.M. Kopylova. Znachenie vanadiya pri tuber-
kuleze. (Vanadium in tuberculosis of the lungs). Probi Tuberk
(Moscow). 49(4): 63—67 (1971).
(36) Shevchenko, S.D. Soderzhanie vanadiya v kostnykh opukholyakh.
(The vanadium contents in bone tumors) . Ortop Travmatol Prot
(Moscow). 8. 7 3-74 (1965). From: Ref Zh Otd Vyp Obshch Vop
Patol Onkol, 1966, No. 5.53.326 (TranslatiOn).
(37) Bayer, E. and H. Kneifel. Isolation of amavadin, a vanadium
compound occurring in Amanita rnuscaria. Z NaturfOrSCh Teil B
(Tubingen). 27(2): 207 (1972).
(38) Schwarz, Klaus and David B. Mime. GrowtheffeCtS of vanadium
in the rat. Science (Wash). 174(4007): 426—428 (1971).
(39) soremark, Rune. Vanadium in some biological specimens.
3. Nutr. 92(2): 183—190 (1967).
.(40) Schroeder, Henry A., Marian Mitchener, and Alexis P. Nason.
Zirconium, niobium, dntimony, vanadium and lead in rats: Life
term studies. J Nutr. 100(1): 59—68 (1970).
(41) Nelson, T.S., M.B. Gillis, and H.T. Peeler. Studies of the
.effect of vanadium on chick growth. Poultry Sci. 41(2): 519-
522 (1962)
(42) Benemann, J.R., C.E. Mc Kenna, R.F. Lie, T.D. Traylor and M.D.
Kamen. The vanadium effect in nitrogen fixation by Azotobacter.
Biochim Biophys ACTA (Amsterdam). 264(1): 25—38 (1972).
(43) Reiter, B. and J.D. Oram. Iron and vanadium requirements of
lactic acid streptococci. J Dairy Res. 35(2): 67—69 (1968).
(44) Waters, Michael D., Donald E. Gardner, and David L. Coffin.
Vanadium: Cytoxic Effects on Rabbit Alveolar MacrophageS in
vitro. National Environmental. Research Center, u.s Environmental
Protection Agency. Research Triangle Park, North Carolina. In:
Twelfth Annual Meeting of the Society of Toxicology, March 18-
22, 1973.
(45) WaterS, Michael D., Donald E. Gardner, and David L. Coffin.
Metal Toxicity for Rabbit Alveolar Macrophaqes in vitro. I.
Effects on Cell viability, Cell Numbers and a Lysosomal HydrolaSe.
National Environmental Research Center, U.S. Environmental Pro-
tection Agency. Research Triangle Park, North Carolina. In:
Twelfth Annual Meeting of the Society of Toxicology, March 18-
22, 1973.
-------
34 RJI R Jxc.
References
(46) Aranyi, Catherine, Michael D. Waters, Donald E. Gardner, and
David L. Coffin. Metal Toxicity for Rabbit Alveolar Macrophaces
in vitro. II. Effects on Surface Morphology as Determined by
Scanning Electron Microscopy. National Environmental Research
Institute, U.S. Environmental Protection Agency. Research Tri-
angle Park, North Carolina, 1974.
(47) Waters, Michael D., D.E. Gardner, and D.L. Coffin. Metal Cyto-
toxicity: Comparative Studies with Rabbit Alveolar Macrophages
and Human Lung Fibroblasts (Strain WI-38). U.S. Environmental
Protection Agency. Research Triangle Park, North Carolina.
In: Thirteenth Annual Meeting of the Society of Toxicology,
March 10—14, 1974.
(48) Mountain, J.T., L.L. Delker, and H.E. Stokinger. Studies in van-
adium toxicology. Arch Indust Hyg and Occup Med. 8(5): 406-
411 (1953).
(49) Curran, George L. Vanadium and the biosynthesis of cholesterol
and other lipids. In: Seven and Johnson, Eds. Metal binding
in Medicine. J.B, Lippincott Company: Philadelphia. 5. pp. 216-
218, 1960.
(50) Mountain, John T., Fulton R. Stockell, Jr., and Herbert E. Stok-
inger. Effect of ingested vanadium on cholesterol and phospho-
lipid metabolsim in the rabbit. Proc Soc Exptl Biol and Med.
92(3): 582—587 (1956).
(51) Hudson, T.G. Faulkner. Vanadium. Toxicology and biological
significance. American Elsevier Publishing Company, Inc.
New York, New York, 1964.
(52) Kleinrok, Z. Ia., and N.G. Stroikova. Influence of Vanadium
Sulfate on Hypercholesterolemia Caused by a Single Administration
of Cholesterol (Russian). Byuli Eksper Biol Ned. 3(82-85),
1966.
(53) Kaku, S., H. Hoshide, S. Matsuo, et al. Experimental studies on
vanadium poisoning. I. Vanadium induced hepatic injuries in
rats. Jap J md FIlth. 13(4): 263—267 (1971).
(54) Meeks, Marion 3., Robert R. Landolt, Wayne V. Kessler, and (or-
don S. Born. Effect of vanadium on metabolism of glucose in the
rat. 3 Pharm Sci 60(3): 482—483 (1971).
-------
ERJAR INC. vI-82
References
(55) HathcOCk, John N., C.H. Hill, and .S.B. Tove. uncoupling of
oxidative phosphorylation by vanadate. Can J Biochem. 44(7):
983—988 (1966)
(56) Kertesz, Denis. TyrosinaSe and polyphenoloXidaSe. The role of
metallic ions in melcinogeneSiS. Biochim. et BiophyS. ACTA
(Amsterdam). 9(2): 170—179 (19S2).
(57) Pham-Huu-Chaflh. Action comparee du chromate, du molybdate, du
tungstate et du metavanadate de sodium sur la pseudocholiflester-
ase. (Comparative actions of sodium chromate, molybdate, tung-
state and metavanadate on pseudocholineStrase. AgressolOgle
(Paris) . 7(2) : 161—165 (1966)
(58) Lisunk]-fl, Yu. I. AtsetilkhOlinOVYi obmen v mozgu krys pri
sochetanflom vozdeistVii vanadil-Sul’fatom i nekotorYTni proiz-
vodnymi feniluksuSflOi kisloty. (AcetyichOlifle metabolism in the
rat brain when the action of vanadyl sulfate [ V2SO4] is combined
with certain derivatives of phenylacetic acid). Byul Eksp Biol
Med. 57(2): 80—83 (1964).
(59) Lisunkin, Yu. T. KombiniroVaflflOe deistvle vanadi i nekotorykh
proizvodnykh feniluksuSflOi kisloty na atsetiliruYuShchitY
sposobnoSt’PeCherli u krys. (Combined effect of vanadium and some
phenylacetic acid derivatives on the acetylating ability of the
liver in rats). Farmakol Toksikol (Moscow). 28(4): 450—454
(1965).
(60) Catalina, L. Vanadio y la reducciOn de nitratos en las plantas.
I. Influencia del vanadio en la absorciOn de nitratoS. (Van-
adium and nitrate reduction in plants. I. Influence of vanadiurr
in the absorption of nitrates). An Edafol Agrobiol. 25(11/12)
717—722 (1966)
(61) Cataline, L. Vanadio y la reduccion de nitratoS en las plantas.
II. Influencia del vanadiO en presencia del molibdeno en el con-
tenido de aminoacidOS fibres. (Vanadium and reduction of nitrates
in plants. II. The amino-acid content as influenced by vanadium
in the presence of molybdenum). An Edafol AgrobiOl. 25(11/12):
723—729 (1966)
(62) Catalina, L. Vanadio y la reducCion de nitratos en las plantas.
III. La activaCiOn en la reducciOn de los nitritoS por la pre—
sencia del vanadio. (Vanadium and nitrate i:eductiOfl in plants.
iii. Activation ifl nitrite reduction by the presence of vana-
dium). An Edafol Agrobiol. 25(11/12): 831—835 (1966).
(63) NicoloV, B.A., and A.A. PanajotOV. Influence des micro—elements
suivants: Molibdene, Vanadium et Manganese sur la teneur des
nitrates, de ch1orophy13 e et de carotine dans les feuilles de
concombre(CucumlS sativus L.). (Effect of trace elements molybdenum,
-------
J/ERJIAR Ixc. vI-83
Re ferences
vanadium, and manganese on the nitrate, chlorophyll, and carot’ n
content in leaves of the cucumber Cucunus sativus L.) . God
Sofiiskiya Univ Biol Fak Kn Z Bot Mikrobiol Fiziol Biokhim Rast.
60. 161—162 (1965/1966)
(64) Vlasyuk, P.A. and T.A. Kuznetsova. Ribonukleaznaya aktivnost’
ribosomal’noi fraktsii gorokha v prisutstvii molibdena i vanadiya
pri prorastanli. (Ribonuclease activity of ribosomal pea fraction
in the presence of ncilybdenum and vanadium during germination)
Fiziol Biokhirn Kul’T kast. 4(6): 57 3—583 (1972)
(65) Davies, J.W. and J.F. Collins. The induction of Bacillus lichen-
iformis penicillinase by vanadate, molybdate and tungstate anions.
Biochirn Biophys ACTA (Amsterdam). 217: 552-4 (October 15, 1970).
(66) Pezzano, Hilda, and Lidia Coscia. The presence of iron and van-
adium atoms in ribonucleic acid from yeast. ACTA Physiol Latino
Amer (Buenos Aires). 20(4): 402—420 (1970).
(67) Mountain, John T., Fulton R. Stockell, Jr., and Herbert E.
Stokinger. Effect of ingested vanadium on cholesterol and
phospholipid metabolism in the rabbit. Proc. Soc. Exptl. Biol.
and Med. 92(3): 582—587 (1956).
(68) Zenz, C. and B.A. Berg. Human responses to controlled vanadium
pentoxide exposure. Arch Environm. Hith. 14(5): 709-712 (1962)
(69) Phain-Huu--Chanh. The comparative toxicity of sodium chromate,
molybdate, tungstate and metavanad te. I. Experiments on mice
and rats. Arch mt PharmacQdyri. 154(1): 243—2’ 9 (1965)
(70) The Toxic Substances List, 1973 ed. Christensen, Herbert E.,
ed. National Institute for Occupational Safety and Health, U.S.
Dept. of Health, Education, and Welfare. Rockville, Maryland.
Contract Number HSM 99—72—42, June, 1973.
(71) Mitchell, Walter G. Influence Of pH on Toxicity of Vanadium in
mice. Proc Soc Exptl Biol and Med. 84(2): 404—405 (1953).
(72) Mitchell, Walter G., and Earl P. Floyd. Ascorbic acid and ethy-
lene diamine tetraacetate as antidotes in experimental vanadium
poisoning. Proc Soc Exptl Biol and Med. 85(2): 206—208 (1954).
(73) Yamada, Kimimasa. An experimental study of vanadium poisoning.
Igaku Kenkyu (Acta Medica) . 28(8): 2860—2880 (1958).
(74) Rornoser, G.L., W.A. Dudley, L.J. Machim, and Loveless. Toxicity
of vanadium and chromium for the growing chick. Poultry Sci.
40(5): 1171—1173 (1961)
-------
3’ RJAR INC. vI-84
Re ferences
(75) Summers, J.D. and E.T. Moran, Jr. Interaction of dietary van-
adium, calcium and phosphorus for the growing chicken. Poult
Sci. 51(5): 1760—1761 (1972).
(76) Berg, Lawrence I L, Gordon E. Bearse, and Louis H. Merrill. Van-
adiurn toxicity in laying hens. Poultry Sci. 42(6): 1407-1411
(1963).
(77) Berg, Lawrence R. and W.W. Lawrence. Chickenseed meal, dehydrated
grass and ascorbic acid as dietary factors concerning toxicity
of vanadium for the chick. Poult Sci. 50(5): 1399-1404 (1971).
(78) Jha, K.K. Effect of vanadium and tungsten on nitrogen fixation
and the growth of Medicago sativa. J Indian Soc Soil Sci. 17(1):
11—13 (1969)
(79) Warington, K. The influence of iron supply on toxic effects of
manganese, molybdenum and vanadium on soybean, peas and flax.
Ann. Appi. Biol (London). 41(1): 1—22 (1954).
(80) Kopylova, L.M. Vliyanie pyatiokisi vanadiya na rost kul’tury
mikobakterii tuberkuleza. (Effect of vanadium pentoxide on the
growth of a culture of Mycobacteriurn tyberculosis). \Toronezh Med
Inst. 58. 120—122 (1967).
(81) Bala, Y.M., V.1. Zavrazhnov, and L.M. Kopylova. 0 terapevti-
cheskoi aktivnosti vanadil—sul’fata pri eksperimental’nom tuber-
kuleze. (Therapeutic potency of vanadyl sulfate in experimental
tuberculosis). Farmakol Toksikol (Moscow). 34(3): 346-348
(1971)
(82) Documentation of the Threshold Limit Value for Substances in
Workroom Air. 3rd ed. American Conference of Government Indus-
trial Hygienists, 1971.
(83) Roskchin, IV. Toxicology of vanadium compounds used in modern
industry. Gig Sanit (Moscow). 32: 4—6 (1967).
(84) Michaels, Sabine. The biological effect of vanadium with respect
to a limitation of its emission. Staub Reinhaltung Luft.
33(7) : 276—279 (July, 1973)
------- |