U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
PB-251 438
Literature Study of Selected Potential
Environmental Contaminants, Antimony
and Its Compounds
Arthur D. Little, Inc.
Prepared For
Environmental Protection Agency
February 1976
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TABLE OF CONTENTS
Page
SUMMARY
PRELIMINARY INVESTIGATION REPORT
0. INTRODUCTION 1
A. History 1
B. Sources, Occurrence and Resources 3
I. PHYSICAL AND CHEMICAL DATA 5
A. Structure and Properties 5
II. ENVIRONMENTAL EXPOSURE FACTORS 15
A. Production and Consumption 15
B. Uses 38
C. Potential Sources of Environmental Contamination 48
and Control Practices
D. Analytical Methods 68
E. Monitoring 76
III. HEALTH AND ENVIRONMENTAL EFFECTS 80
A. Environmental Effects 80
B. Biological Effects 84
IV. REGULATIONS AND STANDARDS 132
V. EVALUATION AND COMMENTS 137
REFERENCES A-l
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LIST OF TABLES
Page
TABLE I
Properties of Antimony and Selected Antimony
TABLE II
TABLE III
TABLE IV
TABLE V
TABLE VI
TABLE VII
TABLE VIII
TABLE IX
TABLE X
TABLE XI
TABLE XII
TABLE XIII
TABLE XIV
TABLE XV
U.S. Production of Primary and Secondary Antimony
1959-1974 . . .
U.S. Production of Primary and Secondary Antimony
1974-1975 .
Manufacturers and Suppliers of Antimony Compounds . . .
Antimony Price
Industrial Consumption by Product ...
Current Handling Practices
Antimony in Urine 1962+
Antimony in Urine 1965-66 ...
Excretion of Antimony in Urine in First 24 Hours After
a Single Dose of Sodium Antimony Dimercaptosuccinate. .
Comparison of Electrocardiographic Changes in Tartar
Emetic and TWSb
Antimony Levels in Urine and Faeces of Mice After a
Single Oral Dose of Tartar Emetic
17
18
19
25
32
34
36
37
54
87
87
93
98
101
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SUMMARY
Antimony, a metallic element, was known and used in ancient times as a
metal in artifacts and jewelry. An antimony compound, antimony sulfide,
served the early Egyptians as a cosmetic and the ancient Romans used
antimony preparations as drugs. Although certain antimonials are still
used as medicinals, such use is relatively minor. The major use for
antimony metal is in antimonial lead, while its principal compound,
antimony oxide, finds increasing use in the preparation of flame-retar-
dant chemicals for plastics, textiles and other products.
Antimony, found primarily in mineral ores, is derived primarily from
stibnite (antimony trisulfide), a mineral rich in antimony. Other
natural sources of antimony are complex sulfide ore, which are ores of
stibnite containing chiefly lead, copper, silver, and mercury. China
has the world's largest antimony deposits, with known reserves amounting
to almost 4 million tons. U.S. resources are very small, approximating
100,000 tons in known reserves, but the U.S. may have another 100,000
tons in undiscovered resources. A new find of antimony ore in the U.S.
was reported in 1970, and the ore is currently being processed.
I. PHYSICAL AND CHEMICAL PROPERTIES
Metallic antimony is a hard, silver-white lustrous metal, which is
relatively inert and resistant to tarnish. Although it is too brittle
to be used as a pure metal, antimony alloys with lead and other metals,
imparting desirable hardness to them.
Numerous antimony compounds exist and they are used industrially in
storage batteries; miscellaneous chemical products; rubber and plastics;
industrial chemicals, including inorganic pigments; stone, clay, and
glass; power transmission, etc.
Antimony combines with sulfur to form antimony trisulfide or antimony
pentasulfide. It reacts with chlorine to form antimony chlorides.
Under controlled conditions it reacts with oxygen to form the oxides.
'•-£-.
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Antimony trioxide, known in the trade as antimony oxide, is the most
important oxide of antimony. A white or colorless powder, its ability
to suppress the chalking tendency of other white pigments makes it use-
ful as a pigment. Its flame-retardant properties have contributed to
its greatest commercial demand. Because it is insoluble, antimony
oxide is particularly useful as a flame retardant in the paper industry.
II. ENVIRONMENTAL EXPOSURE FACTORS
A. Production and Consumption
Although antimony and its compounds are industrially significant because
of their unique contribution to the manufacture of many commonly-used
products, such as alloys, paint, paper, plastics, and textiles, they
are not ranked among the biggest volume chemicals in the U.S. Total
production in 1974 of primary and secondary antimony was only about
41,000 tons, with the secondary production (i.e., antimony produced from
scrap rather than from its ores or as a by-product of lead smelting
operations) accounting for better than 50% of total production.
The United States mine production of antimony is a very small part of
world mine production. In 1974, the U.S. contributed only 661 short
tons to the total world mine production of 76,419 short tons. In
recent years, U.S. imports of antimony ores (Sb content) have been
about 17,000 tons.
There are no U.S. or world production figures available for antimony
oxide, but virtually all antimony oxide producers depend upon antimony
ores for their operations. The availability of these ores governs the
production of antimony oxide, as well as that of metallic antimony.
The two major producers of antimony in the U.S. are NL Industries, which
processes ores received from Mexico in its smelter at Laredo, Texas,
producing antimony and antimony oxide, and the Sunshine Mining Company
in Kellogg, Idaho, which produces antimony from its own silver-copper
ores by a process identified as leaching and electrolysis. Utilizing a
ii
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new entimony find, the United States Antimony Corporation converts
antimony sulfide concentrates to metallic antimony in a smelter at
Thompson Falls, Montana. .=.... ,«.•--.
V
I
Asarco, an established producer of antimony oxide derived as a by-product
in the smelting of lead ores, recently announced plans to build an
4
f
antimony plant in El Paso, Texas, that will have a capacity of 1,825-ton/year.
Other antimony oxide producers include Chemetron Co/rporation, Harshaw
Chemical Company, McGean Chemical Company, and M & (T Chemicals. In 1974,
Associated Metals and Minerals started operations in a new plant in
Texas City, Texas, believed to have a capacity of a't least 1.8 million
Ib/year.
i
I '
In the production of primary antimony (as metal, oxide, or sulfide) from
its ores the choice of production method depends upon the amount of
antimony present in the ores. High-grade ores contain 45 to 60% anti-
mony and these ores are usually processed by liquation. U.S. ores are
of a lower grade and are smelted in a blast furnacei, or are treated by
leaching (using sodium hydroxide) and then electrolyzed to produce a
93 to 99% pure antimony. Impure metal is also refined by an electrolysis
process to produce a 99.9% pure antimony metal.
I
In the smelting of antimony ores (and lead ores) the antimony sulfide
is converted to antimony oxide, which is volatile. This material,
generally impure, is captured in baghouses or other recovery devices
and is further smelted to produce a commercially acceptable oxide.
Antimony has been a cyclic marketplace performer, its price remaining
quite stable over the years. Its price rose sharply in recent years
because of tight supplies, but are now trending downward again. The
price drop is attributed to the depressed economy, particularly in the
automotive field (which cut down battery production) and to the use of
stockpiled antimony. Federal legislation requiring certain textiles
and other materials to be flame proofed is expected, however, to boost
the demand for antimony. Consumption should rise at an annual rate
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of 4% through 1985.
Antimony is used in metal and non-metal products. As a metal, it finds
a use in antimonial lead, solder type metals, ammunition (bullets)
storage batteries, and in cable coverings. As a non-metal, it is used
in glass and clay products in flameproofing chemicals and compounds,
in ammunition (primers), in fireworks, and in plastics and rubbers.
Antimony oxide as well as antimony pentasulfide and antimony trisulfide,
is used in various grades to impart flame resistance to many rubber,
plastic, textile, paint and paper products. The oxide is used as a
pigment, primarily in paints.. As a decolorizer, antimony oxide is
useful in glass, particularly optical glass. It is also used as an
opacifying agent in porcelainized enamel. The trifluoride is used in
the manufacture of pottery, while the tri- and pentasulfides are used
to make fireworks and matches.
Antimony oxide and other antimony compounds are also used as catalysts
in the manufacture of other chemicals, the oxide serving as a catalyst,
for instance in the production of polyester resins.
The medicinal use of antimony compounds has decreased in recent years,
primarily because of undesirable side effects of some of these compounds
or their toxicity, but also, because of the advent of new type drugs.
Antimony potassium tartrate is an effective emetic and has been used to
treat certain tropical diseases, but other less toxic antimony compounds
are replacing it. The barium, as well as the potassium tartrate, is
used as a veterinary medicinal.
Antimony is a significantly useful commercial product but it is not an
essential one. Although it has certain properties that promote its
use (e.g., solidified from the molten state, it expands on cooling; thus
it offers a unique property for type metal used in printing), antimony
can be replaced by other materials. Alternative compounds have been
used, when military needs required the major part of production or when
IV
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less expensive materials have been required.
In general, antimony is not present in significant amounts in air but,
\
when emitted from smeltering operations, it has been measured in concen-
trations higher than its permissible Threshold Value Limit. Antimony
emitted from smelters can, evidently, be carried for some distance by
the wind.
Antimony is present in sea water at a normal concentration of 4 yg/1,
but no excessive concentration of antimony in sea water (as the result
of extracting minerals from the seabed or from waste disposal) has
been reported. Because most salts of antimony are insoluble, there is
little chance that large concentrations of antimony will be found in
the ocean. Marine animals, however, do concentrate antimony in their
muscles, and several studies indicate that certain levels of antimony
have been toxic to some fish. Because of the possible consequences to
human health that could result from eating seafood contaminated with
high concentrations of antimony, it is advisable that any future large-
scale extraction of antimony from the seabed be closely monitored. As
little as 97 mg of antimony have been reported as lethal to humans.
The mining and crushing antimony ores offers potential for the generat-
tion of antimony dusts but, especially in recent years, carefully con-
trolled operations and the use of dust collecting systems have minimized
the dust hazards.
In the production of antimony metal from its ores, by-product dust and
antimony oxide fume can be generated. Again, however, most large
industries use local exhaust systems in the working areas and provide
a direct exhaust for the smelting furnace, thus minimizing hazards to
employees and controlling air emissions from the plant.
Air emissions at the antimony smelter in Laredo, Texas, were reported
to be higher than permissible in 1972, but the company has installed
additional baghouses, hoods and controls, which have helped to reduce
-------
these emissions considerably. This smelter produces only an insignifi-
cant amount of liquid effluent, but does generate about 44,000 tons of
solid waste (slag) each year. This slag, which contains 1% of antimony,
is stored outdoors on company property^
In Idaho, the leaching and electrolysis process used by one company to
produce antimony generates no air emissions or solid waste. A recycling
system installed a few years ago has reduced the antimony content of
the liquid to a very low amount. Currently, although antimony content
is only 1.0 to 1.3 ppm, it is still too high to meet the suggested EPA
proposed effluent limitations. The company is striving now to comply
with the EPA requirements. The antimony effluent has not had any dele-
terious effect on vegetation in the area, but fish have not been able to
survive in the local river. This effect, however, has not been attri-&
buted to the presence of antimony in the effluent.
In general, there is no evidence that antimony oxide is a harmful
pollutant. It is discarded into municipal systems.'
Exposure to antimony dust and its salts can cause dermatitis. Antimony
vapors, when inhaled, can cause respiratory and gastrointestinal problems,
Antimony dust or vapor, under certain conditions, can also be a fire
hazard. For these reasons, particular antimony compounds have to be
transported according to prescribed procedures. Storage areas should
be dry, well-ventilated, and protected from heat and sunlight. Fire
extinguishers should be kept in the storage area.
The potential dangers from excessive dust and fumes that exist in the
production of antimony also exist in those industries where antimony is
used. For example, antimony dust may be generated during the machining
and polishing of antimony-containing metal products. Antimony trioxide
dust may form when the oxide is used as a pigment in tha manufacture
of paints and other products; antimony pentoxide dust may be generated
in the making of glass and ceramics. Other hazards may exist from
skin contact with antimony trichloride solutions during the dyeing of
vi
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textiles or with antimony sulfide in rubber compounding operations.
Federal, state and local regulations govern the disposal of antimony
wastes. Landfill and smelter are the principal disposal methods now
used; ocean dumping has been practiced, but concern over the potential
hazard to the ecosystem has practically ruled out this method. Some
antimony compounds, such as antimony pentafluoride and antimony tri-
fluoride, must be pretreated chemically before being buried. Encap-
sulation of nickel antimonide before disposing of it in a chemical
waste landfill is recommended. Because the antimony halides, e.g.,
antimony trichloride can be decomposed by water to form toxic hydrogen
chloride, care must be exercised in their disposal.
Traditional laboratory analytical methods are used for determining the
concentration of antimony in ores, minerals and dusts. Trace analysis
of antimony and its compounds in air, in water and in biological speci-
mens requires the greater sensitivity of modern instruments, such as
atomic absorption spectroscopy.
Although there is an absence of environmental monitoring in operation
for heavy metals as marine pollutants, schemes for automated analysis
have been suggested using existing equipment. Minute amounts of
antimony in the air of a few urban and nonurban areas have been re-
corded by the National Air Sampling Network. Methods for determining
airborne particulate antimony are under development at Arthur D. Little
Inc., for NIOSH.
III. HEALTH AND ENVIRONMENTAL EFFECTS
Antimony is found only infrequently in air, but following emission from
an antimony (or copper or lead) smelter the antimony may be transported
for some distance. There is evidence that it is persistent in surface
soils following contamination. There is also abundant evidence of
antimony uptake in human and animal tissues and organs with exposure
to antimony, but some attempts to correlate tissue with age have been
unsuccessful. Thus, it is uncertain whether antimony is actually
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accumulated. There is currently no evidence of biomagnification.
Occupational exposures to antimony ore, pure antimony, and antimony
oxide have been implicated in increased incidence in workmen of pneumo-
coniosis, a disease of the lungs caused by the habitual inhalation of
irritant minerals or metallic particles. In animal studies acute and
subacute exposure to these forms of antimony resulted in a pulmonary
phagocytic response (cell engulfing of foreign material) generally
without any appreciable pneumonitis. With chronic exposure the macro-
phage (large phagocyte) response was more involved and there was an
increase in fibrous tissue. In contrast, occupational exposure to
antimony trisulfide has been associated with cardiovascular changes.
Experimental studies with this compound in rats, rabbits and dogs
confirmed the cardiovascular effects. Exposure to gaseous forms of
antimony produced more generalized systemic toxicity and, in the cases
of antimony trichloride in men and antimony pentafluoride in rodents,
the effects were probably attributable to both the antimony and the
halide components.
Trivalent antimonials are very effective therapeutic agents for treat-
ment of schistosomiasis. A major side effect of this use has been
cardiovascular changes which have been demonstrated electrocardiograph-
ically following administration of antimony dimercaptosuccinate (TWSb),
potassium antimony tartrate (tartar emetic), sodium antimony tartrate,
sodium antimony bis (pyrocatechol-2,4-disulfonate) and sodium antimonyl
gluconate. The EGG changes were more marked with TWSb than tartar
emetic in man. No similar changes have been reported following admini-
stration of pentavalent antimonials. The mechanism of the cardiovascular
effect has not been clearly defined. Trivalent antimonials have also
been demonstrated to reduce contractile force In intact and isolated
dog hearts with tartar emetic producing a more pronounced effect than
TWSb. At lower than therapeutic doses effects in animals were minimal.
There is currently no evidence of carcinogenic, mutagenic or teratogenic
effects, attributed directly to antimony or its compounds. Liver
toxicity does not appear to be prominent although the highest tissue
retention was found in liver in studies in animals.
viii
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In conclusion, the comparatively small annual production of antimony
and its compounds in the United States coupled with the relatively safe
history of the use of these materials indicates that they are not a
major environmental contamination hazard. No serious occupational
poisoning has been associated with the industrial use of antimony.
Although some antimony compounds are toxic, or give rise to toxic de-
composition products, many of them are used in small enough quantities
to preclude the possibility of any large-scale hazard. Industrial
safety measures imposed on industry by government regulations or adopted
by manufacturers for their own corporate protection, or the health and
safety of their employees, suggest that certain potential hazards are
being properly addressed. Antimony in the general air environment does
not appear to be a contaminant of great magnitude. Major U.S. rivers do
not have excessive concentrations of antimony, and ocean dumping restrict-
ions will curtail or eliminate the potential hazard to marine life, thus
protecting man from the possible ill effects of eating fish contaminated
with a concentration of antimony high enough to be hazardous or lethal.
Nevertheless, wherever large-scale operations involving antimony or its
products are conducted, careful monitoring of gaseous emissions and
water pollutants should be encouraged.
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PRELIMINARY INVESTIGATION REPORT
Q. INTRODUCTION
A. History
Antimony, the metallic element identified by the chemical symbol Sb, an
important industrial commodity in today's highly technical world, has
been known to man for 6000 or more years. The literature refers to the
early use of antimony and its sulfide as a cosmetic, a medicinal, and
as a metal in artifacts and jewelry. In early biblical times, for
instance, it was used as an eyebrow paint, and references to its use as
a cosmetic appear in early Chinese and Arabic writings. Egyptian copper
articles thinly coated with antimony have been traced back to around
2500 B.C. A cast antimony vase unearthed at Tello, Chaldea, is believed
to have been made in 4000 B.C. In another instance, bracelets and neck-
laces found in graves, dating back to the aeneolithic age, contained
almost 100% Sb. Another early use was as a pigment, when antimony com-
pounds were combined with lead to produce a yellow glass.
The ancient Romans used antimony preparations as drugs, and Stone Age
Egyptians used it to treat eye diseases. By the time of Pliny (~50 AD),
antimony was recognized as a medicinal and by the fifteenth century it
was widely used as such. Because of its observed toxic effects, however,
the Faculty of Physicians of Paris banned its use in the mid-sixteenth
century. Then, in 1657, this ban was lifted, when, all else having failed,
an antimony medicinal was given to the ailing King Louis XIV, who re-
covered from his illness. Antimony continued to be used medicinally,
then, until the nineteenth century, when it again fell into disfavor
(Harvey, 1960).
A century later, antimony compounds found another use — as parasiticides,
their use to control leishmaniasis representing a breakthrough in chemo-
therapy. Organic antimony compounds are still used as drugs today,
especially to combat worm infestations, e.g., schistosomiasis and filaria-
sis (Harvey, 1960).
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There is no record of who first added antimony to lead to produce a strong,
hard, anti-corrosive alloy, or when this occurred. In the mid-1500.'s,
however, Sb was used as an alloying agent in metal bells. At that time,
in addition to its use as an alloy, antimony was used as an ingredient for
making pewter, glass, and metal mirrors; as a pigment; and as an ulcer
drug.
The advent of the printing press may mark the beginning of antimony's
extensive use as an industrial material. Early cast type was made of
lead-antimony alloys, and antimony is still used in varying percentages in
current type metals. Antimony later achieved a reputation as a strategic
commodity, following the discovery in 1800 that it could be used to harden
the lead used for shrapnel bullets, producing a brittle bullet that frag-
mented when the shell burst. This function contributed to a tremendous
increase in the production of antimony during the period of World War I.
Another important industrial use for antimony dates from 1839, when Isaac
Babbitt used an alloy containing antimony for bearing metals. The develop-
ment of the lead storage battery in 1850 gave an added impetus to the use
of antimony. About a century later, antimony was used extensively as a
hardening agent in the lead sheath used on telephone and other cables.
More recently, antimony (particularly its oxides) has found an increasing
use as a fire-retarding agent.
As the demand for antimony increased, there have been developments in the
extraction of antimony from its ores. Crude antimony can be produced from
a rich ore (stibnite) by a liquation process or from the roasting of
sulfide ores and the liquation of antimony ores was evidently practiced
in the sixteenth century. The roast reduction process for producing the
metal was introduced in the 1700's. By 1830, the reverberatory furnace
was being used. Shortly before 1900, electrolytic antimony was first
produced, but the process only became commercially important after 1940.
The blast furnace smelting process was investigated about the time of
World War I, and since 1930 this method has been widely used to extract
metallic antimony from its concentrates.
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B. Sources, Occurrence, and Resources
From 0.2 to 0.5 parts per million (ppm) of antimony exist in the earth's
crust and from 0.1 to 1 ppm are found in igneous rock, while deep-sea clays
contain 1 ppm. Minute amounts of antimony are found in sedimentary rocks,
and the detection of small amounts of the element in marine animals in-
dicates its presence in sea water.
Native metallic antimony is seldom found. The element exists primarily
in mineral ores, over 100 of which are found in nature. Of these, the
most important is the antimony mineral stibnite, or antimony trisulfide
(Sb2S3), which is rich in antimony. Stibnite, when exposed to oxidation,
is converted to the oxide. Generally less important commercially than
the trisulfide, the oxides include stibiconite (the hydroxide), cervantite,
valentite, senarmontite, and kermasite (the oxysulfide ore). Of these,
however, kermasite and stibiconite have been worked in some world areas.
Other sources containing relatively large percentages of antimony are the
complex sulfide ores, which are ores of stibnite containing lead, copper,
silver, and mercury. Though these ores are lean in antimony, the metal
is usually recovered as a by-product element when the ores are smelted
for lead or copper. For example, tetrahedrite, the sulfide of copper and
antimony contains up to 29% Sb; jamesonite, the sulfide of lead and
antimony, contains 32-35%; and bournonite, the sulfide of copper, lead,
and antimony, contains 25%. For the most economic production of high
purity metal (99.6 %), ores containing minimum amounts of impurities (Pb,
As, Cu, Zn) are required.
The world's largest antimony resources are in China. Known deposits there
total 3.8 million short tons, but there are estimates of additional re-
sources that could increase China's total to 5.3 million tons. Bolivia's
known resources are estimated at 420,000 tons. The Republic of South
Africa and the USSR each have resources estimated at 300,000 tons. Other
identified resources include Mexico (200,000 tons), Australia (150,000 tons),
Turkey (120,000 tons), and Thailand (110,000 tons). Yugoslavia and the
United States each have 100,000 tons, but the U.S. may have an additional
-3-
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estimated 100,000 tons in undiscovered resources (Miller, 1973). About
50% of total U.S. reserves are low-grade ores because they are found in
complex lead-silver-copper and gold ores. In 1955, the only economic-
ally workable U.S. deposits were in Idaho, and in the last 40 or so years
about 80% of the U.S. mine production of antimony has been from Idaho,
where resources in the Coeur d'Alene district are believed to be adequate
for continuous operation for the long future. Other U.S. deposits that
have been worked are in the districts of Fairbanks and Kantishna in
Alaska, where resources are estimated at about 10,000 tons. Alaska's
antimony resources are low-grade types. Included among the estimated
U.S. resources are about 50,000 tons of antimony present in lead ores in
southeastern Missouri, the Tri-State District, and the Upper Mississippi
Valley (Miller, 1973). In 1970, Agau Mines, Inc. reported that it had
located a major antimony find with an estimated 330,000 tons of antimony
ore available in two veins. At that time, Agau expected to start pro-
cessing 100 tons/day of antimony ore in mid-August 1970 and anticipated
an eventual processing capability of 1,800 tons/days.
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I. PHYSICAL AND CHEMICAL DATA
A. Structure and Properties
1. Metallic Antimony
Antimony, Sb, is a hard silver-white lustrous, odorless metal with a scale-
like structure. In powder form it is a lustrous, dark gray. It is ordi-
narily quite stable and very resistant to tarnish since it does not oxi-
dize in dry air at room temperatures. Under controlled conditions it
will react with oxygen to form the oxides. It combines with sulfur in
all proportions to form the trisulfide or pentasulfide. Fluorides or
fluocomplexes are formed by the action of hydrofluoric acid on many in-
soluble antimony compounds. It reacts with chlorine to form the antimony
chlorides. It is insoluble in water and not affected by cold, dilute
acids. Antimony has very poor electrical and thermal conductance.
When antimony is in the molten state it will attack other metals. Antimony
is brittle and cannot be rolled, forged or drawn but must be cast. When
solidified from the molten state the metal will expand on cooling, a unique
property, which makes it very desirable for type metal used in printing.
While its brittle properties limit its uses as a pure metal, alloyed with
other metals it imparts such properties as improved hardness and lower
melting point. Sb alloys particularly with the metals lead (Pb),
bismuth (Bi), tin (Sn), copper (Cu), nickel (Ni), iron (Fe), and
cobalt (Co) and forms chemical compounds with the last four metals.
Table I shows the pertinent properties of antimony along with the names
and properties of its commercially important compounds. These data were
compiled from a review of such general references as the Merck Index,
8th edition, 1968; Kirk-Othmer, "Encyclopedia of Chemical Technology,"
2nd edition, Vol. 2, pp. 562-8, 1963; Gmelin's Handbuch der Anorganischen
Chemie; "Chemical Week," Buyers Guide Issue, 1976; American Conference of
Governmental Industrial Hygienists, "Threshold Limit Values—1971"; and
various manufacturers technical bulletins and catalogs.
-------
TABLE I
PROPERTIES OF ANTIMONY AND SELECTED ANTIMONY COMPOUNDS
COMPOUND
Ant imony ,
metallic
Ant imony
lactate
Ant imony
oxychloride
Ant imony
pentachloride
Ant imony
pentaf luoride
Ant imony
pentasulf ide
Antimony
pentoxide
Antimony
potassium
tartrate
SYNONYMS
Antimony regulus
Basic anti-
mony chloride
Powder of Al-
garoth
Mercurius vitae
Ant imonic
chloride
Ant imony
perchloride
Ant imony (V)
chloride
Ant imon ic
sulfide
Ant imony (V)
sulfide
Golden antimony
sulfide
Ant imony
persulf ide
Ant imony red
Ant imon i a 1
saffron
Ant imonic
oxide
Ant imony (V)
oxide
Stibic
anhydride
Antimonic acid
Tartar emetic
Tartrated
antimony
Potassium
ant imony 1
tartrate
FORMULA
Sb
Sb(C H 0 )
SbOCl
SbCl
SbF -
Sb S
Sb2°5
(SbO)KC H 0,
*
MOLE-
CULAR
WEIGHT
121.75
388.8
173.2
299.1
216.7
403.8
323.5
324.9
APPEARANCE
AND
ODOR
White to grey
solid
No odor
White solid
White solid
No odor
Pale brown
liquid
Acrid odor
Viscous liquid
Acrid odor
Yellow-orange
solid
No odor
Yellowish
solid
No odor
White solid
No odor
BOILING
POINT
°C
1 ATM
1635
± 8' *
140
143
MELTING
POINT,
°C
630
3.5
7.0
SPECIFIC
GRAVITY
6.6
2.35
3.15
3.78
3.78
2.6
SOLUBILITY
in WATER, %
Insoluble
Soluble
Reacts
Reacts
Insoluble
Reacts
slowly
0.087
8.3
LD50
1.5g/kg,
ip, rat
4g/kg
ip, rat
50mg/kg
ip, mice;
600rag/kg,
po, mice
DEGRADATION PRODUCTS
Sb 0
Sb203,C02,H20
Sb203,HCl(or salts)
Sb 0 ,HCl(or salts)
Sb205,HF(or salts)
Sb205>H2S(or salts)
Metal antimonates
Sb 0 , K salts, CO ,H20
PURITY
7,
99.8
99.0
99.0
99.9
PRINCIPAL IMPURITIES
As, Cu, Fe, Pb
As, Fe, Pb, SO
.
As, Pb
*Gmelin's Handbuch der Anorganischen Cheraie gives a boiling point
range of 1322-1635 i 8°C for antimony.
-------
TABLE I
PROPERTIES OF ANTIMONY AN"D SELECTED ANTIMONY COMPOUNDS (Cont'd)
COMPOUND
Ant Imony
sodium
tartrate
Ant imony
sulfate
Ant imony
tetroxide
Ant imony
tribromide
Antimony tri-n-
butylate
Ant imony
trichloride
Ant imony
triethoxide
Ant imony
trif luoride
Ant imony '
triiodide
SYNONYMS
Ant Imony ,
tartarized
Sodium anti-
monyl tartrate
Stibunal
Emeto-Na
Ant Imous
sulfate
Ant imony
trisulfate
Antimony(III)
sulfate
Ant imony
tributoxide
Tri-n-butyl
antiraonite
Butter of
ant imony
Ant imony (III)
chloride
Ant imonous
chloride
Ant imony
chloride
Ant imony
triethylate
Ant imonous
fluoride
Ant imony
fluoride
Antimony(III)
fluoride
Ant imony
iodide
Antimony(III)
iod ide
FORMULA
(SbO)NaC,H,0
Sb (SO,)
.
Sb2°4
SbBr3
(C H 0) Sb
SbCl
(C H 0) Sb
SbF
J
Sbl
MOLE-
CULAR
WEIGHT
308.8
531.7
307.5
361.5
341
228.1
256
178.8
502.5
APPEARANCE
AND
ODOR
White solid
No odor
White solid
White to
yellow solid
White solid
No odor
Colorless liquid
White solid
Acrid odor
Colorless
liquid
White solid
Red solid
BOILING
POINT
•c
1 ATM
288
223
95
(at
llmm)
376
401
MELTING
POINT,
'C
96
73
292
168
SPECIFIC
GRAVITY
3.62
5.8
4.15
1.28
3.14
1.52
4.38
4.92
SOLUBILITY
in WATER, %
62
Soluble
0.002
Reacts
Insoluble
Reacts;
very soluble
Insoluble
443
Reacts
LD50
25mg/kg,
iv, mice
Ig/kg,
ip, rat
.
DEGRADATION PRODUCTS
Sb20 ,Na salts, C02,H20
.
Sb.O .sulfate salts
SbjO ,HBr(or salts)
Sb-0 , C, H_OH(CO, , HO)
Sb^O ,HCl(or salts)
•
Sb-0 ,C H OH(CO- ,H_O)
Sb,00,HF(or salts)
L 3
SbjO ,HI(or salts)
PURITY,
%
98-101
99
99.9
99.9
99
99.5
98
PRINCIPAL IMPURITIES
As, Pb
As, Fe, Cu
-------
TABLE I
PROPERTIES OF ANTIMONY AND SELECTED ANTIMONY COMPOUNDS (Cont'd)
COMPOUND
Ant imony
trioxide
Ant imony
trisulfide
Ant imony -
zinc(oxide
mixture)
Sodium
antimonate
Stibine
SYNONYMS
Antimony oxide
Antiraony(III)
oxide
Di ant imony
trioxide
Antimony bloom
Flowers of
ant iraony
Stibnite
Ant imony
sulfide,
native
Ant imony
glance
Needle ant i
ant imony
Antimony gray
Ant imony
sesqui-sulf ide
Sodium
meta-
antimonate
Leukonin
Ant imony
hydride
FORMULA
Sb 0
L j
Sb S
Sb 0 (12.5%)
Zn6(I2.57.
NaSbO,
3
SbH
3
MOLE-
CULAR
WEIGHT
291.5
339.7
192.7
124.8
APPEARANCE
AND
ODOR
White solid
No odor
Gray, black
or red solid
No odor
White solid
No odor
White solid
Colorless gas
Characteristic
odor
BOILING
POINT
C
1 ATM
1550
1150
-17
MELTING
POINT
C
656
550
-88.5
SPECIFIC
GRAVITY
5.2
4 . 64
3.3
2.2
(liquid)
SOLUBILITY
in WATER, 7.
0.001
0.0017
Insoluble
Insoluble
0.5
LD50
>20g/kg
po, rat
Ig/kg,
ip, rat
DEGRADATION PRODUCTS
Metal antimonites
Insoluble antimony
salts
Metallic antimony
PURITY
7.
99
PRINCIPAL IMPURITIES
As, Fe, Pb
-------
The following table includes additional properties of antimony.
PHYSICAL PROPERTIES OF HIGH PURITY ANTIMONY (99.9999%)
Atomic Number
Molecular Weight
Melting Point
Boiling Point
Density (20°C)
Latent Heat of Fusion
Latent Heat of Vaporization
Specific Heat
Thermal Conductivity
Resistivity (0°C)
Standard Electrode Potential
Magnetic Susceptibility
Crystal Structure
Thermal Neutron Cross Section
Hardness, Moh's Scale
51
121.75
630.5°C
1635° + 8°C
6.618 g/cc
38.3 cal/g
16.1 cal/g
0.0494 cal/g/°C
0.045 cal/sq. cm./cm./°C/sec
39.1 microhm-cm
+0.1 v
0.87 cgs
Rhombohedral
5.7 barns
3.0
The principal contaminants of antimony are arsenic, copper, iron, and
lead. The amount of impurities present in high-purity antimony are
indicated below:
As
Fe
Pb
Cu
Bi
Others
TYPICAL ANALYSIS
99.9999%
<0.5 ppm
0.1 ppm
<0.3 ppm
99.999+%
2 ppm
1 ppm
<1 ppm
1 ppm
<1 ppm
<2 ppm
The commercial product is generally sold in the following standard forms:
semi-circular ingot, broken pieces, granules, and cast cake. Other forms
are: powder, ingot, shot, and single crystals.
2. Antimony Compounds
The formulas and properties of the antimony compounds considered of
commercial importance are listed in Table I.
Undoubtedly the most industrially important of these compounds is antimony
trioxide, commonly called antimony oxide. A white or colorless powder,
-9-
-------
antimony trioxide continues to be in demand as a flame-retarding agent
for many materials. Odorless, Sb»0, is only very slightly soluble in
water. It is soluble in aqueous hydrochloric acid, concentrated alkalies,
potassium hydroxide, and acetic acid.
Antimony trichloride, a white solid with an acrid odor, also exists as
colorless crystals or flakes that are hygroscopic. SbCl, fumes in air.
It is very soluble in water and in absolute ethanol, hydrochloric acid,
acetone, ether, benzene, chloroform, and tartaric acid. Hydrolysis
yields antimonyl chloride (SbOCl). A number of ethers, aldehydes, and
mercaptans will form one-to-one addition compounds with antimony chloride
to produce organic compounds of antimony.
Antimony pentachloride is manufactured as a colorless to yellow liquid,
which is soluble in hydrochloric acid, chloroform, and carbon tetrachloride.
It is corrosive and fumes in air. Hydrates are formed in the presence
of small amounts of water. Chlorine is readily lost from SbCl_, thus
making it useful as a chlorine carrier. Ethers, alcohols, aldehydes,
esters, and nitriles form one-to-one adducts with this compound. It is
a poor conductor of electricity. However, solutions of it in liquid
S0? are conductors.
Antimony potassium tartrate occurs as transparent, odorless crystals
(which effloresce on exposure to air) or a white crystalline powder. It
has a sweetish metallic taste and is poisonous. It is slightly soluble
in cold water, and readily soluble in hot water, but insoluble in alcohol.
Antimony pentoxide is produced in the form of a yellowish powder which is
slightly soluble in water but soluble in strong bases forming antimonates.
It dissolves slowly in warm hydrochloric acid or in warm potassium hy-
droxide solution. It reacts with hydrogen sulfide to form antimony(V)
sulfide.
-10-
-------
Antimony trisulflde occurs in nature as black crystalline stibnite but,
when manufactured, it is produced as a gray lustrous crystalline mass
or grayish black powder. There is also a red modification. It is in-
soluble in water but soluble in concentrated hydrochloric acid with the
evolution of hydrogen sulfide. It is soluble in solutions of alkali
hydroxides containing excess caustic.
Antimony pentasulfide, Sb^, is an orange-yellow odorless powder which
is insoluble in water but soluble in concentrated HCl with the evolution
of hydrogen sulfide. It is also soluble in solutions of alkali hydroxides
or sulfides, forming sulfantimonates. Known also as golden antimony sul-
fide, antimonic sulfide, antimonial saffron, antimony red, and antimony
persulfide, its density is 3.78; its molecular weight is 403.82; and it
has an LD _ of 1.5 g/kg, ip in rats.
Kirk-Othmer (1963) lists, in addition to antimony potassium tartrate, a
number of antimonials that have been used as medicinals. These include
the antimony (III) compounds: antimony sodium tartrate, stibophen, anti-
mony sodium thioglycollate, antimony thioglycollamide, antimony lithium
thiomalate, and the antimony (V) compounds: stibamine glucoside, ethyl-
stibamine, ureastibamine, stibenyl, stibosan, and antimony sodium glu-
conate.
Antimony sodium tartrate, (SbO)NaC.H.O,, whose synonyms and properties
are given in Table I, appears as transparent or whitish scales or powder,
is hygroscopic, and is much more soluble than antimony potassium tartrate.
Stibophen, C,2H,Na CX.-S.Sb. 7H.O, or sodium antimony(III)bis(pyrocatechol-
2,4-sodium disulfonate), is also known as Fuadin, Sodium Antimosan,
Neoantimosan, and Pyrostib. A colorless crystalline powder, it is soluble
in water, and insoluble in alcohol and other organic solvents. The aqueous
solution turns yellow and oxidizes in air. Stibophen has a molecular
weight of 895.27.
-11-
-------
Antimony sodium thioglycollate, NaSb(SCH«COO)7, or antimony sodium thio-
acetate, has a molecular weight of 324.96. Its hygroscopic crystals turn
pink in light. .
Antimony thioglycollamide, Sb(SCH CONH-K, with a molecular weight of
392.09, melts at 140°C.
Antimony lithium thiomalate is also known as anthiomaline.
Stibamine glucoside, also called Neostam stibamine glucoside, is an
impure or incompletely characterized .compound.
Ethylstibamine, or Neostibosan, is a mixture of p-aminobenzenestibonic
acid, p-acetamidobenzenestibonic acid, antimonic(V) acid, and diethyl-
amine.
Ureastibamine, also known as stiburea, is sometimes identified as
p-ureidobenzene-stibonic acid, but in reality it is a complex mixture
whose composition varies.
Stibenyl, CH.CONHC-H.SbO-HNa, is sodium 3-chloro-4-acetamidobenzenestibonate.
— j b ^ j
The antimony sodium gluconate, C,H0NaO_Sb, which is used medicinally, is
Do /
the pentavalent antimony compound also known as Solustibosan, Myostibin,
and Pentostam. It occurs as crystals and is freely soluble in water.
A trivalent antimony sodium gluconate, known as Triostam, also exists.
An amorphous powder, it is soluble in water; its molecular weight is
336.88.
Numerous other antimony compounds are mentioned in the literature, some
particularly in discussions of their environmental health effects. (See:
Section III). These include:
Antimony acetate, Sb(OOCCH )«, a crystalline material with a molecular
weight of 298.88 that decomposes on boiling.
-12-
-------
Antimony acetylacetonate, SbCCLHyD-K, more properly called antimony
acetonylacetate, whose molecular weight is 418.93.
Antimony aluminide, SbAl, an antimony alloy with a molecular weight of
418.93.
Antimony arsenide. Sb-As., (SbAs); molecular weight is 468.25.
Antimony barium tartrate, Ba[SbOC,H,0,]2, described as a white, fluffy
powder or precipitate.
Antimony djchlorotrifluoride, SbCl-F-, a viscous liquid with a molecular
weight of 249.67.
Antimony iodosulfide, SbIS, which has a molecular weight of 280.72.
Antimony orthophosphate. SbPO,, which has a molecular weight of 216.74.
Antimony pentaselenide, Sb.Se., has a molecular weight of 638.30.
Antimony phosphide, SbP, has a molecular weight of 152.72.
Antimony potassium oxalate, K_[Sb(OOCCOO)-], also identified as potassium
trioxalatoantimonate(III) or potassium oxalatoantimonate(III), is some-
times referred to as "antimony salt." A crystalline powder, soluble in
water, it has a molecular weight of 503.12.
Antimony silver selenide, AgSbSe , has a molecular weight of 387.56.
Antimony silver telluride, AgSbTe_, has a molecular weight of 484.86.
Antimony tartrate. SbCOO, has a molecular weight of 795.8.
-13-
-------
Antimony triselenide, Sb2Se3> is a gray powder with a melting point
ranging from 572-617°C and a molecular weight of 480.40. It is very
slightly soluble in water.
Antimony tritelluride, Sb.Te , has a molecular weight of 626.35.
Astiban, See: Stibocaptate.
Stibocaptate, C^^o^^^^^l' 2,3-Dimercaptosuccinic acid cyclic thio-
antimonate (III) S,S-diester with 2,3-dimercaptosuccinic acid tripo-
tassium salt; known also as "antimony dimercaptosuccinate", Astiban,
TWSb, is a crystalline powder with a molecular weight of 898.42. (The
Merck Index notes that Astiban was described as sodium antimony-2,3-raeso-
dimercaptosuccinate by Browne and Schulert in Am. J. Tropic Med. Hyg.
vol. 13, 558 (1964)).
Some compounds are apparently in use or at least are available for sale,
but there is no data on them. No data were found for such compounds as
antimony fluoroborate; antimony(III) methoxide; antimony tritungstate,
Sb(WO.) ; antimony oxalate; and piperazine diantimony tartrate. There
were also no data for tributyl antimony, (C^H ) Sb, or triphenyl antimony,
(C6H5)3Sb, but the Chemical and Process Technology Encyclopedia (1974)
lists triethyl antimony and trimethyl antimony with the following in-
formation. Triethyl antimony. Sb(C2H5)3> melts at -29°C, boils at 159°C,
and has a specific gravity of 1.3. Its formula weight is given as 208.88.
It is insoluble in water, but soluble in alcohol and ether. Trimethyl
antimony, Sb(CH ) , has a formula weight of 166.83, a specific gravity
of 1.5, and boils at 81°C. It is slightly soluble in water.
-14-
-------
II. ENVIRONMENTAL EXPOSURE FACTORS
A. Production, Consumption
1. Production
a. U.S. Production
In 1974, the United States produced 40,888 short tons (metal content) of
antimony, the second highest production in the last 16 years. From a
low of 29,469 short tons in 1959, production rose gradually to a peak of
39,724 short tons in 1966. Production then declined slightly from 1967
to a low of 33,316 short tons in 1971, rising to 36,261 short tons in
1972 and peaking again to a high of 41,813 short tons in 1973.
Antimony production falls into two categories, primary and secondary.
Sources of primary antimony include mine and smelter production. In 1974,
661 short tons (antimony content) were mined while primary smelter pro-
duction of antimony was 16,657 short tons. Secondary production accounted
for 23,570 short tons, virtually all of which was used with lead in bat-
teries and hard lead alloys. *n 1975, domestic mine output of antimony
totalled 950 short tons, or 44% above 1974, but primary smelter production
of antimony materials was about 13% below the 1974 level due to a shortage
in feed material from both reduced imports and lower secondary smelter
production from scrap.
Primary production includes antimony in the forms of the metal, oxide,
sulfide, and as a by-product in the manufacture of lead, plus the residual
unrecovered antimony in the processing of ores from antimonial minerals.
Secondary production accounts for over half of the industrial usage in the
United States and comes from scrap, drosses, and residues. Secondary
recovery in 1973 was 85% from old scrap and 15% from new scrap (Wyche,
1973) with the following breakdown reported:
-15-
-------
Sources of Secondary Antimony;
Old Scrap 85%
Batteries 66%
Type Metal 14%
Babbitt 12%
Others 8%
100%
New Scrap 15%
Drosses
Residues
100%
Table II shows the U.S. production of primary and secondary antimony from
1959 through 1974 and Table III shows the first three quarters of 1975
compared to 1974.
U.S. antimony mine production capacity is expected to increase toward 1980
with smelter production continuing at the same level (Wyche, 1975a)
b. Imports
The United States is one of the smallest producers of antimony in the
world with mine production 661 short tons (antimony content) in 1974 as
compared to a total world mine production of 76,419 short tons. Imports
into the U.S. make up the difference between domestic production and con-
sumption.
In the world market the major producers are the Peoples Republic of China,
the USSR, Bolivia and South Africa. The important small producers are
Canada, Mexico, Yugoslavia, and Thailand. The U.S. imports antimony ores
from several of these countries, with the leading suppliers including the
Republic of South Africa, Bolivia, Chile, and Mexico. Table IV shows the
principal sources and volumes of recent imports of antimony ore and
concentrate.
-16-
-------
TABLE II
U.S. PRODUCTION OF PRIMARY AND
(As reported by U.S. Bureau of Mines, in
1959
1960
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
19741
19752
Source
Mine
678
635
689
631
645
632
845
927
892
856
938
1130
1025
489
545
661
Metal
2,667
3,665
4,558
4,407
4,160
4,418
4,216
4,567
4,002
3,617
3,129
3,732
3,816
3,837
2,859
3,030
: Compiled from
PRIMARY
Oxide
4,411
5,188
4,609
4,788
5,983
6,748
6,485
7,791
6,612
6,518
7,746
8,261
6,272
8,343
11,273
10,445
data in U
Sulfide
70
60
84
53
76
53
94
126
71
133
95
23
18
232
92
54
. S . Bureau
Residues
430
385
355
366
392
447
205
219
249
417
330
384
136
201
1,839
2,066
SECONDARY ANTIMONY
short tons, antimony content)
Byproduct
Ant ' 1 Lead
1,170
656
1,723
2,113
1,506
1,692
1,389
1,833
1,532
1,801
1,903
981
1,132
731
1,143
1,062
of Mines Minerals Yearbook,
Total
Primary
9,426
10,589
12,018
12,358
12,762
13,990
13,234
15,466
13,358
14,345
14,141
14,511
12,399
13,833
17,751
17,318
1962-1973
Secondary
Antimony
Produced
from New and
Old Scrap
20,043
20,104
19,466
19,362
20,803
22,339
24,321
24,258
23,664
23,699
23,840
21,424
20,917
22,428
24,062
23,570
fm t^
Total
29,469
30,693
31,484
31,720
33,565
36,329
37,555
39,724
37,002
37,044
37,981
35,935
33,316
36,261
41,813
40,888
t a
1. 1974 figures compiled from
2. Table III contains figures
data in U.S. Bureau of Mines, Mineral Industry Surveys,
for the first three quarters of 1975.
Dec. 18, 1975.
-------
TABLE III
00
I
U.S. PRODUCTION
PRIMARY
PRIMARY 1974
Mine 661
Metal 3,030
Oxide 10,445
pj
H Sulfide 54
§ Residues 2,066
Antimonial lead 1,062
SECONDARY 23,570
TOTAL 40,888
of
AND SECONDARY ANTIMONY
(Short Tons)
First Quarter
1975
248
857
1,712
257
65
3,572
6,711
Second Quarter
1975
190
746
1,550
150
157
2,948
5,741
Third Quarter
1975
241
442
1,539
145
280
3,392
6,039
Source: Division of Nonferrous Metals, U.S. Bureau of Mines, Mineral Industry Surveys. December 18, 1975.
-------
1971
1,593
311
2,314
3,826
1,575
1972
2,562
1,722
2,217
10,160
551
1973
3,662
1,590
2,088
6,446
1,339
1,554
1974
2,669
2,283
1,629
4,739
201
3,134
TABLE IV
U.S. IMPORTS ANTIMONY ORE
General imports of antimony ore (metal content) by countries, as reported
by the U.S. Bureau of Mines, in short tons.
1970
Bolivia 2,162
Chile 42
Mexico 3,666
Rep. of South Africa 6,239
Turkey
Other Countries ... 1,711
Total 13,820 9,619 17,212 16,679 14,655
SOURCE: Compiled from U.S. Bureau of Mines Mineral Yearbook 1971-1973
and Division of Nonferrous Metals, Bureau of Mines, Mineral
Industry Surveys, Third Quarter 1975.
As shown in Table IV, imports of antimony ore and concentrate amounted to
14,655 short tons antimony content in 1974. Other imports in 1974 from a
number of other countries included 5,203 short tons (antimony content)
of antimony oxide; 2,203 short tons of antimony metal; and 58 short tons
of antimony as needle antimony or liquated antimony sulfide (crude antimony)
(Wyche, 1975b)
2. Producers/Distributors
The only U.S. mine that currently operates primarily for antimony is
owned by United States Antimony Corporation, a subsidiary of Agau Mines,
Inc., and is located southwest of Thompson Falls, Montana. In 1973,
the only other source of domestic antimony was the Antimony King Mine in
Nevada operated by Dowco Mining Company (Wyche, 1973).
For many years, NL Industries, Laredo, Texas, and the Sunshine Mining
Company, Kellogg, Idaho, have been the major producers of antimony. Since
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1973, however, United States Antimony Corporation has been converting
antimony sulfide concentrates to metallic antimony at its Thompson Falls,
Montana smelter. Annual capacity was estimated at 600 tons of the metal
in 1973, but the company at that time anticipated increasing its output
to 800 tons, and was weighing the possibility of producing antimony
trioxide (Wyche, 1973).
Antimony is also recovered in antimonial lead from domestic lead ores at
primary lead smelters. According to Wyche (1973), primary lead smelter
production of antimony in 1973 was 17,206 tons. Of this, 16% was produced
as metal, 65% as oxide, 7% as antimonial lead, 11% as ground residue,
and 1% as sulfide.
In October 1975, Asarco Incorporated announced that it will build a $7-
million, 1,825-ton/year antimony metal refinery at its El Paso plant in
Texas, which is expected to produce 99.5% pure antimony by the end of 1976.
Other companies listed as producers or suppliers of antimony, include
Atomergic Chemetals Co., New York; Richardson-Merrell, Inc., a subsidiary
of J.T. Baker Chemical Co., Phillipsburg, New Jersey; and Hooker Chemical
Corp., Niagara Falls N.Y.; Belmont Metals, Inc., a division of Belmont
Smelting and Refining Works, Inc., Brooklyn, New York, offers jewelry
.casting alloys, prototypes, and precision castings of Britannia (an alloy
chiefly of tin, copper and antimony).
Major producers of antimony oxide include NL Industries; Asarco, Inc.;
Chemetron Corp., Chicago; Harshaw Chemical Co., Gloucester City, N.J.;
McGean Chemical Co., Cleveland; and M & T Chemicals, Inc., Rahway, N.J.
In early 1974, Associated Metals and Minerals went on stream in Texas
City, Texas, with an antimony oxide plant having an initial capacity of
1.8 million Ib/year.
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Distributors of antimony oxide Include:
The Graymor Chemical Co., Clifton, N.J.
Helm New York Chem. Corp., New York and Chicago
ICC Solvent Chemical Sales Corp., New York
Koch Int'l Chemical Co., Inc., Wellesley Hills, Mass.
McKesson Chem. Co., San Francisco
Morgan Chemicals, Inc., Williamsville, N.Y.
Samincorp, Inc., New York
Whittaker, Clark & Daniels, Inc., South Plainfield, N.J.
Antimony pentasulfide is manufactured by or is available from Atomergic
Chemetals Co., New York; City Chemical Corp., Jersey City, N.J., and
Great Western Inorganics, Inc., Golden, Colorado. Antimony trisulfide
is manufactured by or is available from Atomergic Chemetals Co., New
York; Barium & Chems, Inc., Steubenville, Ohio; Belmont Metals, Inc., a
division of Belmont Smelting and Refining Works, Inc., Brooklyn, N.Y.;
Chemetron Corp., Cleveland, Ohio; Hummel Chemical Co., Inc., South Plain-
field, N.J.; McGean Chemical Co., Inc., Cleveland, Ohio; and Rare Metal
Products Co., Atglen, Pa.
Manufacturers and distributors of antimony compounds available commer-
cially are presented in Table V.
-21-
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TABLE V
COMPOUND
Antimony acetylacetonate
Antimony ammonium fluoride
Antimony arsenate
Antimony fluoborate
Antimony oxalate
Antimony oxychloride
Antimony oxysulfide
Antimony pentachloride
Antimony pentafluoride
Antimony pentasulfide
Antimony pentoxide
MANUFACTURERS AND SUPPLIERS OF ANTIMONY COMPOUNDS
COMPANY
MacKenzie Chemical Works, Inc.
City Chemical Corp.
City Chemical Corp.
Harstan Chemical Corp.
City Chemical Corp.
City Chemical Corp.
City Chemical Corp.
American Hoechst Corp.
Atomergic Chemetals Co.
Electronic Space Products, Inc.
Great Western Inorganics, Inc.
Hooker Chemical Corp.
Mallinckrodt Chemical Works
Richardson-Merrell, Inc.
Allied Chemical Corp.
American Hoechst Corp.
Electronic Space Products, Inc.
Great Western Inorganics, Inc.
City Chemical Corp.
Great Western Inorganics, Inc.
American Hoechst Corp.
Atomergic Chemetals Co.
Electronic Space Products, Inc.
Great Western Inorganics, Inc.
Harshaw Chemical Co.
LOCATION
Central Islip, N.Y.
Jersey City, N.J.
Jersey City, N.J.
Brooklyn, N.Y.
Jersey City, N.J.
Jersey City, N.J.
Jersey City, N.J.
Somerville, N.J.
New York, N.Y.
Los Angeles, Calif.
Golden, Colo.
Niagara Falls, N.Y.
St. Louis, Mo.
Phillipsburg, N.J.
Metropolis, 111.
Somerville, N.J.
Los Angeles, Calif.
Golden, Colo.
Jersey City, N.J.
Golden, Colo.
Somerville, N.J.
New York, N.Y.
Los Angeles, Calif.
Golden, Colo.
Gloucester City, N.J,
-------
TABLE V (cont'd)
COMPOUND
Antimony potassium tartrate
i
to
Antimony silico oxide
Antimony sulfate
Antimony tetroxide
Antimony tribromide
Antimony tri-n-butylate
Antimony trichloride
Antimony trifluoride
COMPANY
*Aceto Chemical Co., Inc.
*American Firstoline
*Browning Chemical Corp.
City Chemical Corp.
*McKesson Chemical Co.
Pfizer, Inc.
NL Industries
Apache Chemicals, Inc.
Apache Chemicals, Inc.
Atomergic Chemetals Co.
Cerac, Inc.
Metalsmart
Apache Chemicals, Inc.
Cerac, Inc.
City Chemical Corp.
Great Western Inorganics, Inc.
Stauffer Chemical
Apache Chemicals, Inc.
Cerac, Inc.
Chemetron Corp.
Electronic Space Products, Inc.
Mallincrockdt Chemical Works
McGean Chemical Co., Inc.
Richardson-Merrell, Inc.
Stauffer Chemical Co.
American Hoechst Corp.
Apache Chemicals, Inc.
Atomergic Chemetals Co.
Cerac, Inc.
Ozark-Mahoning Co.
LOCATION
Flushing, N. Y.
New York, N.Y.
New York, N.Y.
Jersey City, N.J.
San Francisco, Calif.
New York, N.Y.
Philadelphia, Pa.
St. Louis, Mo.
Seward, 111.
Seward, 111.
New York, N.Y.
Menomonee Falls, Wis.
Great Neck, N.Y.
Seward, 111.
Menomonee Falls, Wis.
Jersey City, N.J.
Golden, Colo.
Gallipolis Ferry, W. Va,
Seward, 111.
Menomonee Falls, Wis.
Cleveland, Ohio
Los Angeles, Calif.
St. Louis, Mo.
Cleveland, Ohio
Phillipsburg, N.J.
Weston, Mich.
Somerville, N.J.
Seward, 111.
New York, N.Y.
Menomonee Falls, Wis.
Tulsa, Okla.
-------
TABLE V (cont'd)
COMPOUND
Antimony triiodide
Antimony trioxide
Antimony trisulfide
Sodium antimonate
COMPANY
American Hoechst Corp.
Apache Chemicals, Inc.
Electronic Space Products, Inc.
Great Western Inorganics, Inc.
Asarco, Inc.
Associated Metals and Minerals Corp.
Chemetron Corp.
Electronic Space Products, Inc.
Harshaw Chemical Co.
*Helm New York Chemical Corp.
*ICC Solvent Chemical Sales Corp
*Koch International Chemical Co., Inc.
*Kraft Chemical Co.
M & T Chemicals, Inc.
McGean Chemical Co., Inc.
*McKesson Chemical Co.
NL Industries
Richardson-Merrell, Inc.
*Samincorp, Inc.
U.S. Borax Chemical Corp
*Whittaker, Clark and Daniels, Inc.
Apache Chemicals, Inc.
Barium and Chemicals, Inc.
Belmont Metals, Inc.
Cerac, Inc.
Chemetron Corp.
General Metallic Oxides Co.
Hummel Chemical Co., Inc.
McGean Chemical Co., Inc.
Rare Metal Products Co.
M&T Chemicals, Inc.
Chemetron Corp.
LOCATION
Somerville, N.J.
Seward, 111.
Los Angeles, Calif.
Golden, Colo.
New York, N.Y.
Texas City, Tex.
Cleveland, Ohio
Los Angeles, Calif.
Gloucester City, N.J.
New York, N.Y.
New York, N.Y.
Wellesley Hills, Mass,
Chicago, 111.
Baltimore, Md.
Cleveland, Ohio
San Francisco, Calif.
Highstown, N.J.
Phillipsburg, N.J.
New York, N.Y.
Los Angeles, Calif
South Plainfield, N.J,
Seward, 111.
Steubenville, Ohio
Brooklyn, N.Y.
Menomonee Falls, Wis.
Cleveland, Ohio
Jersey City, N.J.
South Plainfield, N.J,
Cleveland, Ohio
Atglen, Pa.
Baltimore, Md.
Cleveland, Ohio
Supplier
-------
3. Production Methods and Processes
a. Antimony
Antimony is extracted from its sulfide and oxide ores, or from mixed ores,
by volatilization, smelting, and liquation — the choice of method being
governed by the antimony content of the ore used. For low-grade ores,
carrying from 5 to 25% antimony, the volatilization process is used.
Medium-grade ores, containing 25 to 45% antimony, are smelted in a rever-
beratory furnace or a blast furnace. High-grade ores, containing 45 to
60% antimony, are liquated. Reverberatory furnaces or blast furnaces are
also used for the smelting of the products of liquation and volatilization,
and for the smelting of concentrated antimony ores. In addition, some
complex antimony ores are treated by electrolysis or by leaching and
electrolysis to recover the antimony. These various manufacturing pro-
cesses are described briefly below, although all are not used in the U.S.
NL Industries, one of the two U.S. major manufacturers, produces antimony
metal and antimony trioxide at its Laredo, Texas smelter. Primary
smelting of the metal is carried out in a blast furnace using ores imported
principally from Mexico, although not exclusively as other ore sources
from various parts of the world are used. For the most part, oxide-type
ores are used in the process. After smelting, the metal is further
refined and cast into ingots (Hornedo, 1976).
Since 1956, the other major U.S. producer, the Sunshine Mining Company
Kellogg, Idaho, has recovered antimony from its Ag-Cu ores by leaching
and electrolysis, yielding a metal with less than 0.05% impurity.
A reverberatory-type furnace is used in United States Antimony Corporation's
refining plant, which converts antimony sulfide ore into metallic antimony,
near Thompson Falls, Montana.
For its new plant in El Paso, Texas, Asarco will use one-third feed
material (copper-antimony-silver concentrates) from the Coeur d'Alene
mining district with the balance from their Galena Mine, both near
Wallace, Idaho. For this plant Asarco's central research laboratories
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developed a new process that will employ a reverberatory-type furnace
in which the concentrates will be melted and then tapped continuously
from the furnace for granulation. The resulting granules will be dis-
solved and an electrochemical process will be utilized for the removal
of antimony from solution. The remaining copper and other metals are
to be sent to the plant's, copper smelting section for processing into
99.5% pure anode copper (Asarco, 1975).
The Bunker Hill and Sullivan Mining and Concentrating Company, Idaho,
uses the electrolysis process to recover antimony.
In a pre-smelting process, antimony ores are first concentrated by the
flotation process. In this process, the ores are crushed and wet-ground
to particles ranging from 65 to 200 mesh and the resultant slurry is
conditioned with a collecting reagent (usually xanthates) and a frothing
agent (usually pine oil or a long-chain alcohol) and fed to the flotation
cells. In the cells, where air is added, antimony sulfide particles,
attached to the air bubbles, are removed as a concentrate in the froth.
The gangue, flowing through the flotation cells is removed as tailings.
The flotation concentrate is thickened and filtered and shipped to a
smelter for reduction to antimony metal.
In the antimony oxide volatilization process, low-grade (5 to 25% Sb)
sulfide ores are roasted with coke (or charcoal) and air (controlled
aeration) to form antimony trioxide.
Sb_S,. + 609 -*• Sb00 + 3SO
2. J L i o 2.
Furnaces used for the roasting are shaft type, rotary kiln, converters,
or blast roasters. Heat from the sulfide ore converts and volatilizes
the antimony sulfide to antimony trioxide, which is recovered in flues,
condensing pipes, baghouses, or Cottrell precipitators, or combinations
of these. The trioxide is generally impure and so is shipped (sometimes
after briquetting) to a smelter, where it is reduced to antimony metal.
In some instances, according to Kirk-Othmer (1963), a high-grade oxide,
identified as Stibhox in the trade, results from the oxide volatilization
process. This product requires a particular charge and special process
conditions.
-26-
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The reverberatory furnace smelting process handles medium-grade (25 to
40% Sb) antimony sulfide ores and flotation concentrates, antimony trioxide
from the volatilization process, or antimony sulfide from the liquation
process. In the furnace, the concentrates are mixed with charcoal, an
alkaline flux (e.g., of soda, potash, and sodium sulfate) and recycled
slag.
SbS3 + 502 -»• Sb204 + 3S02
Sb20, + 4C -> 2Sb + 4CO
The sulfide ores are converted to oxide ores, which are reduced to
metallic antimony. Flue gases are passed to baghouses or Cottrell preci-
pitators to minimize the loss of antimony from the charge by volatilization
and to recover the volatilized antimony oxides. The purpose of recycling
the slag is to recover antimony from it. The molten antimony drawn off
from this process is impure or crude antimony.
In the blast furnace smelting process, intermediate-grade (25 to 40% Sb)
antimony sulfide ores and flotation concentrates, antimony oxide concentrates,
liquation residues, mattes, rich slags, briquetted fines or flue dusts
are processed with coke.
SbS3 + 502 •*• Sb204 + 3S02
Sb204 + 4C -> 2Sb + 4CO
The furnaces, usually water-jacketed blast furnaces, use a high smelting
column, low air pressure, and separation of slag and metal in a forehearth
to reduce the charge to impure antimony metal, which is continuously
removed. A large amount of slag is generated but it serves the purpose
of reducing the loss of antimony by volatilization. This slag, generally
containing less than 1% of antimony, is dumped.
In the liquation process, high-grade (45 to 60% Sb) antimony sulfide ore is
Sb0S- + 600 -*• Sb-0, + 3SCL
/ J z / o I.
-27-
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heated to 550 to 600°C in a perforated pot to separate the antimony sulfide
(crude antimony) from the gangue. The molten sulfide is tapped and col-
lected in a lower container. When the heating is done in a reverberatory
furnace, the molten antimony sulfide is removed continuously. Although
this continuous collection method is more efficient, it involves the use
of a reducing atmosphere that will prohibit loss by volatilization.
Volatilized antimony oxides are recovered in baghouses or Cottrell pre-
cipitators. The residue from this process contains 12-30% antimony. The
residue is passed to a volatilizing furnace for recovery of its antimony
content as antimony oxides.
In the electrolysis process, impure metal is refined to an electrolytic
antimony that is at least 99.9% pure. Anodes of crude antimony are hung
on anode bars in an electrolytic cell alternately with starter cathodes
of 99.9+ antimony hung on cathode bars. For best results, an electrolyte
solution of antimony fluoride and sulfuric acid is used. The anodes
dissolve into the electrolyte and most of the anode impurities are removed
periodically as slimes from the bottom of the cell. The metallic antimony
is plated out of the electrolyte onto the high-purity antimony cathodes .
Leaching and electrolysis is a method used to recover antimony from its
complex ores. The ores are leached with a solution of sodium hydroxide.
+ 8S + ISNaOH -> 5NaSbS + 3NaSbC>
3 2
The leaching may be done directly or the concentrates may be converted into
a complex matte before leaching. The sodium thioantimonate leach solution
is electrolyzed in a diaphragm cell using an iron or lead anode and an
iron or mild-steel cathode. A 93 to 99% pure antimony is deposited on the
cathode. One disadvantage of this process is that the electrolyte be-
comes contaminated with thiosulfate, sulfates, and other compounds, nor.e
of which are solvents for the antimony sulfide. The contaminated electro-
lyte must, therefore, be changed. It is either discarded or reduced to
sodium sulfide, which can be reused as a leach liquor for antimony.
Primary antimony is also produced as a by-product of lead smelting and
-28-
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refining, if Sb is present in the Pb ores in a large enough quantity.
^
Then, the dust emissions, drosses and slags resulting from the smelting
and refining of these lead ores make the recovery of Sb feasible. 9This
by-product is obtained as metallic antimony or antimonial lead, which can
be processed to yield antimony oxide or sodium antimonate.
Undoubtedly, this is the method used by Asarco to produce its antimonial
lead and antimony oxide. Although Asarco buys all types of ore concen-
trates from the world market, its galena mine in Idaho may be the prime
source of Asarco 's antimony concentrates.
Additionally, much of the antimony consumed in the U.S. is secondary
antimony, which is recovered from antimony-containing scrap lead and tin,
such as battery plates, type metal, bearing metal, antimonial lead, etc.
b. Antimony Compounds
Stibine (hydrogen antimonide, antimony trihydride) , SbH_, is formed by
treating metal antimonides with acid, by the reduction of antimony com-
pounds from high oxidation states, or by the electrolysis of acid or
alkaline solutions using a metallic antimony cathode. In the classical
synthesis, a 33% Sb-67% Zn alloy is dissolved by hydrochloric acid to
form gaseous products containing up to 14% stibine. Stibine is also
formed by the reduction of trivalent Sb in acidic aqueous solutions.
According to Kirk-Othmer (1963), typical reactions include:
-»- 3Zn
3Zn -» SbH + 3Zn2+
Antimony pentachloride can be prepared by the action of chlorine on anti
mony, or by the action of excess chlorine on the trichloride, thus deep-
ening the color of antimony pentachloride. The excess chlorine is re-
moved by a stream of dry carbon dioxide.
-29-
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Antimony pentasulfide is made by converting the trisulfide to thioanti-
monate(V) by boiling with sulfur in alkaline solution. The resulting
mixture is decomposed with hydrochloric acid and the pentasulfide is
liberated.
Antimony pentoxide is an acidic oxide prepared by the action of concen-
trated nitric acid on the metal or the trioxide.
Antimony potassium tartrate is manufactured from potassium bitartrate
and metallic antimony in the presence of nitric acid or from potassium
bitartrate and solid antimony oxide.
Antimony trichloride is prepared by the reaction of chlorine on antimony.
Antimony trioxide is obtained during the smelting of antimony sulfide
for the production of antimony,
2Sb0SQ + 900 -*• Sb.O, + 6SO.
2. j / 40 /
It can also be prepared by combining antimony directly with air or oxygen,
Sb. + 300 -»• Sb.O,
4 2 46
Another method involves the alkaline hydrolysis of antimony trichloride,
bromide, or iodide followed by dehydration of the hydrous oxide obtained
(Kirk-Othmer, 1963).
Antimony trisulfide occurs in nature as black crystalline stibnite but
can be manufactured in several ways: (1) by treating the Sb trichloride
with hydrogen sulfide; (2) by treating the trichloride with sodium thio-
sulfate solution; (3) or by heating metallic antimony or the Sb trioxide
with sulfur.
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4. Market Price
The price of antimony from 1960-1975 (New York) is shown in Table VI.
From a low of about 31C/lb in 1960, Sb prices rose gradually through
1968 (when the price was almost 46
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TABLE VI
ANTIMONY PRICE
(NY, Cents per pound)
1960 31.30
1961 33.89
1962 34.75
1963 34.75
1964 42.22
1965 45.75
1966 45.75
1967 45.75
1968 45.75
1969 57.57
1970 144.19
1971 71.18
1972 59.00
1973 68.50
1974 181.76
(First Quarter) 1975 204.49
(Second Quarter) 1975 182.71
(Third Quarter) 1975 160.00
Source: Compiled from data in U.S. Bureau of Mines Minerals
Yearbook, 1962-1973 and from the Division of Non-ferrous
Metals, U.S. Bureau of Mines, Mineral Industry Surveys,
December 18, 1975.
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Therefore, producers and distributors who were stockpiling antimony oxide to
meet the expected demand did not find a ready market. This has produced
the ptice fluctuation in the first part of 1975, dropping from the highs
of a year or two ago.
In the fall of 1974, the price of antimony oxide reached a peak price
which was 180% over that one year earlier in 1973. Three months
later, M & T and NL Industries had dropped their price 60c, or
25% to make their product competitive with that of other suppliers
(Chem. Mkt. Kept., 1975), and Chemetron followed suit three months later
with a 20c, or 10.8% drop (Chem. Mkt. Kept., 1975). Harshaw had initiated
this price cutting in 1975 and McGean was expected to follow along with
the rest. All these firms were citing a lower cost of raw materials;
none suggested that the price had remained inflated from the previous
strong-demand year 1973 (Chem. Mkt. Kept., 1975). With inventories
being used up and with an anticipated 4% annual increase in demand to 1985,
the price of antimony is expected to resume its upward climb.
5. Consumption arid Market Trends
Forecasts of U.S. antimony demand, calculated from the U.S. twenty-year
primary demand trend of 21,000 tons for 1973, indicate a probable average
annual growth rate between 1973 and 2000 of 3.2 percent compared to 2.1
percent for the rest of the world. Over the same period secondary or
"old scrap", antimony demand is expected to grow at an annual average of
2.6 percent in the U.S. compared to 2.0 percent for the rest of the world.
Projections for end-use demand of antimony in the U.S. ranges between
65,000 and 112,000 short tons by 2000 as compared to 44,422 short tons
in 1973 for such applications as transportation, fire retardants, rubber
products, chemicals, ceramics and glass, machinery, etc. (Wyche, 1975a).
However, because of the general economic downturn in the last two years,
producers have been utilizing their stockpiled antimony. As these stock-
piles are depleted, the increasing need will urge the production upwards
(Wyche, 1973). Industrial stocks of primary antimony are shown in
Table VII.
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TABLE VII
INDUSTRY STOCKS OF PRIMARY ANTIMONY IN THE U.S.
(Short tons, antimony content)
(Third Quarter)
Stocks 1969 1970 1971 1972 1973 1974 19752
Ore and concentrate 2227 2973 3582 3562 5585 6275 11145
Metal 1273 1598 1367 1332 1540 809 1292
Oxide • 2053 2932 2697 3179 2074 3732 3326
Sulfide 108 39 22 182 31 35 32
Residues and slags 307 948 647 176 526 549 486
Antimonial lead1 371 357 322 191 322 294 521
TOTAL 6339 8847 8637 8622 10078 11694 16802
Inventories from primary sources at primary lead refineries only.
2
1975 figures are estimated 100% coverage based on reports from
respondents that held 90% of the total stocks of antimony at the
end of 1974.
Source: Wyche, 1973 and 1975b.
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Antimony metal and antimony oxide account for most of the tonnage, as
shown in Table VIII. The principal uses for the metal are in antimonial
lead, in bearings, and in ammunition. Industrial consumption of metal
for these and other uses are summarized in Table IX. Most of the second-
ary production goes into lead battery grids and other hard-lead alloys.
In 1974, antimony consumption was affected by the downturn in the auto-
motive market (Chem. Mkt. Kept., 1975) with a corresponding drop in use
of antimony for batteries and in use of antimony oxide in flameproofing
and flame retardants.
As previously mentioned, new laws and regulations concerning requirements
for fire retardancy have influenced the antimony market and will continue
to do so. In addition to the automotive industry, there will be a need
for flame retardants in television cabinets, particularly those made of
plastics. Also, fire laws pertaining to polyvinyl chloride, wallboard,
plastic floor coverings and ceiling materials necessitate the use of
flame retardants. Though product identification was diverse, about 70%
of all antimony oxide sold (in 1972) was for the flame-retardant market
(Chem. Wk., 1973). Despite attempts to find an alternative to antimony
oxide as a flame retardant (for example, borate compounds and chlorinated
paraffins), Finney (1975) reported that increased prices for substitute
materials helped keep antimony oxide competitive. The potential effect
of new U.S. regulations plus the established need for flame retardants
in construction (plastics) and home (fabric and plastics) are expected
to help stabilize the antimony market (Chem. Mkt. Rept., 1975).
It appears that the increase in flameproofing chemical usage in 1974 and
the drop in ceramic, plastic, pigments, and other products may indicate
a shift in reporting practice inasmuch as the use of antimony oxide in
these other areas is usually related to flameproofing or fire resistant
properties. The steadily declining use in type metal represents a major
shift in the printing industry from letterpress to other methods.
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TABLE VIII
INDUSTRIAL CONSUMPTION OF PRIMARY ANTIMONY
(Short tons antimony content)
1969
Ore and Concentrate 507
Byproduct
(Third Qu«
1970 1971 1972 1973 1974 19751
380 387 1226 582 1032
4989 5080 5473 5824 4362
7157 6944 8389 10970 9457
46 28 104 255 62
981 1132 731 1143 1062
13937 13707 16124 20613 18041
399
3233
4806
20
552
502
9512
Inventories from primary sources at primary lead refineries only.
Source: Wyche 1973 and 1975b .
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TABLE IX.
INDUSTRIAL CONSUMPTION BY PRODUCT
(Short tons antimony content)
Product
Metal products:
TOTAL METAL PRODUCTS
Nonmetal products:
Flameproof ing chemicals and compounds
TOTAL NON-METAL PRODUCTS
GRAND TOTAL—
1969
115
6723
758
55
33
56
105
242
541
137
8765
37
30
2096
2108
722
2558
433
1094
9078
17843
1970
102
5246
481
38
16
35
77
286
220
73
6574
27
17
1774
1820
610
1667
519
929
7363
13937
1971
67
5430
515
36
20
22
74
178
177
102
6621
23
4
1524
1840
592
1810
525
768
7086
13707
1972
64
6149
559
19
39
20
108
177
142
105
7382
23
4
2280
1695
644
2391
587
1118
8742
16124
1973
122
8027
527
12
65
12
97
191
134
104
9291
18
5
2906
1917
644
2920
693
2219
11322
20613
(Jan-Sept)
1974 1975
121
7251
476
16
31
18
69
205
107
135
8429
11
11
4383
1384
460
1431
664
1268
9612
18041
221
3314
233
23
1
7
39
52
37
28
3955
8
4
1617
741
142
298
192
415
3417
73721
1. Includes primary antimony content of antimonial lead produced at primary lead refineries.
2. 9512 short tons antimony content is estimated 100 percent coverage based on reports from
respondents that consumed 80 percent of the total antimony in 1974
SOURCE: Wyche, 1973 and 1975b.
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B. Uses
The applications to which antimony has been put are generally categorized
an metal and non-metal products. Overall use oi antimony hy these;
product groups has been somewhat evenly balanced with the proportionally
greater consumption shifting in the 1950's to the non-metal from the
metal products group. In 1974, however, the total market declined and
since then, figures show greater use in metallics. The U.S. industrial
consumption of antimony in the manufacture of these metal and nonmetal
products since 1969 is shown in Table VIII, p.36. In 1968, primary and
secondary antimony (in terms of Sb content) were consumed in the follow-
ing forms. Metal in solder, type metals, babbit metals, ammunition,
storage batteries, etc. used 6,561 short tons; oxide in glass and clay
products, rubber and plastics, pigments, textiles, chemicals, etc. used
9,363 short tons; sulfide in pigments and plastics used 75 short tons;
antimonial lead (primary antimony) and antimonial lead and other alloys
(secondary antimony) in storage batteries, cable covering, printing and
publishing, communications, ammunition, etc. used 2,222 short tons and
23,699 short tons respectively.
1. Major Uses
a. Metals and Alloy Products
Antimony is not easily fabricated, primarily due to its extreme brittle-
ness. As a result, it is rarely used as a pure metal, except perhaps in
a decorative function. However, its hardness and stiffness make it an
important alloying ingredient for metallurgical applications. The metal
products in which primary antimony is used include antimonial lead and
battery metal; bearing metals, bearings and type metal of antimony alloyed
with tin or lead; Britannia or babbitt metal; pewter; ammunition, e.g.,
bullets; castings; sheet and pipe; cable covering; collapsible tubes and
foils; solders (to add strength); etc. Very high-purity antimony has
several semiconductor applications. When alloyed with aluminum, indium,
gallium, cadmium, zinc, etc., it is used in infrared and Hall-effect
devices, in diodes, and in thermoelectric piles and thermoelectric
devices for cooling.
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Antimony is used to blacken iron and coat metals. Antimony trichloride,
in particular, has been used for bronzing iron, especially gun barrels,
and for coloring zinc black. Together with nitrocellulose lacquers,
antimony oxide (Sb203> yields films with excellent durability and chalking
resistance. The favorable polishing properties of Sb~0_ add to its
suitability for low-resin types of automotive finishes.
Antimony has been employed in metal finishing and electroplating. For
example, antimony potassium tartrate (tartar emetic) has been used in
electrolytic baths to deposit silver and antimony alloys on brass,
copper and steel surfaces.
b. Non-Metal Uses
Antimony is used in such non-metallic products as fire retardants and
flame-proofing chemicals; ceramics, enamels, and glass; plastics; pig-
ments; rubber products; ammunition primers and fireworks; and in the
manufacture of antimony compounds, such as antimony salts and antimonides.
(1) Flame Retardants for Plastics, Paint. Textiles. Rubbers and Paper
With the advent of regulations and requirements governing its applications,
the selection of the optimum fire-retarding chemical additive is critical-
The number and types of applications for antimony oxide compounds with
flame resistant properties is vast. Various grades of antimony oxide are
used for fire resistance in rubbers, plastics, textiles, paints and
paper depending on specific needs and requirements. Specific products
include: Acrylonitrile - Butadiene - Styrene (ABS)
Alkyd coating compositions
Chlorinated rubbers
Elastomers
- NR
- SBR
- Hypalon
- Neoprene
- ANB
Epoxies, e.g. epoxy printed circuits
Flberfill for nightrobes, sleeping bags,
quiltings and comforters
Polyesters
Polyethylene
Polyolefins
Polypropylene (PP)
Polystyrenes (general purpose and high impact polystyrene)
Polyurethane
Polyvinyl chloride, rigid and flexible (PVC)
Polyvinylidene chloride
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Special plasticized resin compositions
Textile coatings and finishes
- nylons
- cottons
- polyesters
- tent fabrics
- tarpaulins
- industrial curtains
- canvas
The chemistry which leads to a flame retardant antimony oxide is based
on the reaction of antimony and a halogen (usually chlorine) to form a
halogenated compound like antimony trichloride at a temperature over
600°F. It is the antimony chloride which is flame retardant and may
even be distilled into the substrate to give additional protection.
The addition of about 3% antimony oxide to chlorine-containing polyester
resins (with 25% chlorine) improves flame resistance. With lower chlo-
rine, content, more antimony oxide is necessary until the chlorine content
is less than about 20%, at which point additional amounts of antimony
oxide cannot compensate for deficiency in chlorine. (Robitschek and Bean,
1954)
Formulations for flame retarding vary considerably from material to
material. Each application has a specific set of requirements necessary
to meet the specific flame tests to which the products are subjected.
The American Society for Testing of Materials, Underwriters' Laboratories,
Inc. (UL), DOT, DOC, etc., all have special requirements, depending on the
end use of the material, for which specific modifications must be made.
In some cases flame retardants are applied to achieve a non-burning mate-
rial; in other instances, a self-extinguishing feature is necessary.
For flame retardants in plastics, the effective level of antimony oxide
(Sb_0_) used varies from as little as 2 to 5 parts per hundred parts to
about 10% loading. In rubbers, the application of Sb?0 may range from
&* J
5 to 30% levels of loading.
Treating fabrics for fire resistance is usually part of the finish and
typically includes a fire, water, weather, mildew resistant (FWWMR)
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application. For textiles in roll form, the yard goods are run over
rollers, down through a bath where the dry cloth becomes saturated with
the special solution, and through a dryer for water and solvent removal.
This is called a wet padding operation or water based treatment. Some
flame retardant emulsions for textile coatings are applied by spraying
or brushing them on the material being treated.
Antimony oxide is substituted for some of the pigment in the formulation
of fire resistant paints. In the flame retarding of paper, Sb^O, offers
the advantage over other flame retardants of not being soluble in water.
(2) Other Uses in Paints, Textiles, Plastics, Rubbers and Paper
Due to its varying tinctorial strengths, antimony oxide is used as a
mordant to achieve specific opacity ranges in paints and plastics.
Antimony potassium tartrate is used as a mordant in fixing basic colors
on cotton, leather and fur. Antimony potassium oxalate has been used in
place of the tartrate as a mordant in fabric dyeing and printing.
Antimony trichloride in solution is used as a mordant for patent leather
and in the manufacture of furniture polishes. Antimony trifluoride,
used as a mordant in dyeing, is usually in the form of double salts.
Antimony compounds used as pigments, primarily in paints, include antimony
pentasulfide, antimony trisulfide and antimony trioxide. Commercial
antimony oxide possesses valuable pigment properties and suppresses
chalking tendencies of other white pigments. Although antimony oxide of
the same volume has approximately half the opacity as rutile titanium
dioxide, its staining power is one third that of titanium dioxide, which
permits economies in using costly dyestuffs. (Paint Manufacture, 1964).
The incorporation of tartar emetic in vinyl chloride formulations assists
in inhibiting and retarding discoloration. Similarly, it provides fast-
ness to washing and light when used in textile printing.
The paint and plastics industries use Sb^Oo for its characteristic density
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and consequent covering ability or binding powers. Antimony pentasulfide
is used in vulcanizing and coloring rubber.
Insoluble starch coatings for imparting water resistance to paper can be
produced with antimony salts, particularly potassium pyroantimonate.
Satisfactory results can be obtained if high temperatures are used, but
the process is somewhat costly as are all other methods for making starch
water-resistant (Casey, 1966).
(3) Uses in Glass
For glass, particularly optical glass, antimony oxide is used as a deco-
lorizer and an antisolarant. During the decolorizing steps in glass-
making, the addition of sodium nitrate in combination with the SbjOo
changes the antimony to the pentavalent state. The addition of Sb20-i
prevents the glass from changing color when exposed to the sun and
imparts to the glass superior light-transmitting capabilities near the
infrared end of the spectrum.
Antimony trisulfide is used in the manufacture of ruby glass. As a
refining agent for optical glass and ruby red glass compositions, Sb-CL
assists in removing bubbles. It is a deodorizer in optical glass and a
stabilizer in emerald green glass.
(4) Uses in Ceramics
Antimony oxide is an opacifying ingredient for porcelainized enamel.
In addition, it contributes hardness and acid resistance to cast iron
enamels.
Sprayed on the surface of red burning clay either as a water or oil
suspension, Sb2C>3 is used as a brick colorant. It is also used in
ceramic pigments.
Antimony trifluoride is used in the manufacture of pottery and porcelains,
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(5) Use in Pyrotechnics, Matches and Explosives
Antimony trisulfide and antimony pentasulfide are used in the manufacture;
of fireworks and matches. Antimony pentasulfide is also used in explo-
sives and Bengal fires.
2. Minor Uses
a. Uses as a Catalyst or Chemical Agent
Antimony pentachloride is used as a chlorinating agent in organic synthesis,
in dye manufacture, and as a catalyst in the preparation of some organic
compounds. Antimony dichlorotrifluoride is used as a catalyst in the
manufacture cf organic fluorine compounds.
Antimony pentafluoride is a powerful oxidizing and fluorinating agent.
The SbF_-amine complexes are used as latent epoxy catalysts. In fluoro-
sulfuric acid, SbF forms a super acid system. These super acids are
used in protonating weak acids, for stabilizing carbonium ions, for the
preparation and investigation of new cationic inorganic species, and in
fluorination reactions, according to Ozark-Mahoning Company's Special
Chemicals Division.
Antimony oxide is used commercially as a catalyst in the production of
polyester resins for fibers and films. Antimony trifluoride is used to
catalyze fluorinations by HF and to manufacture chlorofluorides.
Antimony trichloride is used in making other antimony salts, in organic
synthesis and as a catalyst. It is also a reagent for chloral, aromatic
hydrocarbons, and vitamin A. In chemical microscopy, it is used for the
identification of drugs by forming adducts and addition compounds.
Tri-n-butyl antimonite is a crosslinking agent for elastomerics, a
catalyst for the production of polyesters, and an intermediate for other
antimony compounds and catalysts.
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b. Medicinal Uses
Antimony potassium tartrate is used medicinally as an emetic (tartar emetic)
and in small doses as an expectorant in cough syrups. For the most part,
treatment of parasitic infections with tartar emetic has been discontinued
due to side effects attributed to its use. It is still used, however, in
treating leishmaniasis and schistosomiasis. Because it is less toxic,
antimony sodium thioglycollate has generally replaced tartar emetic as a
medicinal. Antimony thioglycollamide has also been used instead of tartar
emetic for the same reason, although it is more toxic than antimony sodium
thioglycollate.
Although it also causes side effects, antimony sodium gluconate has been
used in treating larva migrans. The trivalent compound is used as a
schistosomicidal agent and the pentavalent compound as a leishmanicidal
agent. Antimony sodium tartrate is also used for these purposes.
c. Veterinary Uses
Antimony barium tartrate was developed by the Zoological Division of the
Bureau of Animal Industry, U.S. Department of Agriculture, and has been
used for grapeworm infection in birds.
Antimony potassium tartrate is used in various dosages as an expectorant
for the treatment of bronchitis in cattle, horses, sheep goats, swine
and dogs. It is also used to treat ascariasis, leishmaniasis, trypano-
somiasis and bilharziasis; as a ruminatoric in atony of cattle, sheep
and goats; as an anthelmintic for horses; and for impaction of rumen in
cattle.
Antimony trichloride has been employed as an escharotic in large-animal
veterinary practice.
3. Chemical Reactions Involved in Uses
Antimony can be used as a catalyst to bring about the halogen exchange in
the manufacture of chlorofluorohydrocarbons (Stephenson, 1966).
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As a catalyst, antimony is usually used commercially in either the tri-
valent or pentavalent state. Pentavalent antimony is the more active
catalyst but causes more side reactions. For this reason, trivalent
antimony may be of greater use in the easier exchange reactions; penta-
valent antimony may be used in particularly difficult reactions. A
typical reaction proceeds as:
CC1 + SbF •*• CC1 F + SbCIF
SbClF2 + HF ->• HC1 + SbF3
with antimony the probable fluorinating agent. In the manufacture of
fluorocarbons 11 and 12, the catalyst is SbF..; for fluorocarbons 113 and
114, it is SbCl2F3.
4. Discontinued Uses
Consumption of antimony for galvanizing metal products and non-metal toy
caps was reported for 1951 in the Minerals Yearbook of that date (Renick
and Wright, 1954). However, neither appeared in the 1951 column in the
comparable data in the Minerals Yearbook 1952 nor have they since.
Galvanizing metal products were not reported prior to 1951 either, but
non-metallic toy caps were previously included in other non-metal products.
Antimony potassium tartrate (tartar emetic) has been superseded by less
toxic forms of antimony (e.g., antimony sodium thioglycollate, antimony
thioglycollamide) for intravenous injections in treating tropical
infections. It is no longer used in the control of insects as it formerly
was.
5. Projected or Proposed Uses
A new low cost antimony stabilizer for the plastics industry, particularly
for PVC multiscrew DWV and conduit compounds, was announced recently by
Synthetic Products Company in Modern Plastics 5_2 (9), 147 (1975). Patented
SYNPRON 1033 , this new antimony stabilizer is reputed to have cost per-
formance advantages compared to organotin mercaptides at use levels of
0.2 to 0.5 phr.
Concern for product safety has brought about increased legislation and
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requirements for products with improved flame resistance. Some new
underwriter's standards are indicative of this concern and bear directly
on the increased use of flame retardants. For example, UL 492 is a
standard for TV cabinets, which alone is expected to increase by some
1000 tons the demand for antimony trioxide (Sb_0_.) in flame retardant
chemicals (Mod. Plastics, 1975b).
Other developments show potential uses for antimony oxide. A smoke-
inhibiting grade of antimony oxide is expected to be available in about
a year from Chemetron Claremont Polychemical's ultrafine antimony oxide
(at $2/lb).
6. Alternatives and Substitutes
Although antimony offers certain advantages in its many applications, it
is not considered essential. In general, its use in paints, pigments
and enamels can be substituted by mercury, titanium, lead, zinc, chromium,
tin and zirconium. Alternative materials to antimony compounds have
been used due to shortages in supply caused by military requirements.
Certain economies in manufacture, (e.g., pigments, fire-retardants, lead-
hardeners), have dictated replacing antimony with less expensive materials.
In some cases, special organic compounds have been employed for flame
proofing.
Alternatives for hardening lead with antimony include using tin,
calcium and dispersion-hardened lead. Gould Inc. has substituted calcium
for antimony in the lead alloys used for a heavy duty truck battery.
Gould claims that the new battery will retain energy up to eight times
longer than Sb-Pb batteries. Other advantages include consumption of
less electrolyte, limited vent openings, and less loss of power during
storage, according to Chem. Wk. 116 (19): 23 (7 May 1975).
Primarily for economic reasons, intumescent coatings may replace
flame retardants in many products. The Underwriters' .Laboratories (UL)
has approved the application of intumescent coatings to the interior of
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TV enclosures, thereby eliminating the need for modifying the cabinet
plastic with flame retardants (Mod. Plastics, 1975b). For instance,
lightweight magnesium oxychloride cement (Albi Duraspray), a product of
Cities Service Company's Albi Manufacturing Corp., has been demonstrated
as a thermal barrier when applied over exposed urethane foam (Mod. Plastics
1975a).
NL Industries' bimetallic smoke reducer, Ongard 1 (55
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C. Potential Sources of Environmental Contamination and Control Practices
1. General •
Included among the numerous organic and inorganic compounds, which man
inhales daily from our polluted air are 23 trace metals. Nine of these
are categorized as elements essential to life or health, seven are identi-
fied as nontoxic, and seven are metals with innate toxicities. Antimony
is classified among the toxic metals, but is rarely detected in the air
and, when it is, it is in minute concentrations, well below its threshold
3
limit value(TLV) of 0.5 mg/m . Unlike cadmium, lead, mercury and nickel,
antimony has not been categorized as a potential or actual public health hazard
2. Production
Most recorded instances of antimony toxicity have been connected with its
processing, handling, and use. The points of toxic exposure start with
the extraction of antimony ores from their mineral deposits and include
the subsequent beneficiation of the ores. Occupational exposure continues
during the production of metallic antimony, antimony alloys, and antimony
chemicals or intermediates, such as antimony oxide.
In the mining of antimony ores, mineral dust is released into the air from
the drilling, blasting, crushing, and hauling operations. Antimony ores
usually occur in the U.S. in vein type deposits in association with other
metals (lead, zinc, copper, gold, silver). The deposits can be found at
various depths and the underground mining procedures are those normally
used for vein type deposits. The mining technology is similar to that
used for hard rock minerals: drilling, blasting, loading and hauling the
ore away from the working face for hoisting to the surface. During all
of these procedures dust is liberated, but the highest concentration of
dust probably occurs during the blasting of the mine face. However,
since wet drilling is used and the mines are wet, the.dust problem is
not usually significant. Operating procedures keep men out of the mine
when blasting is carried out and adequate ventilation is provided to
remove any dusts generated.
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Mineral ores are beneficiated to remove undesirable gangue and to increase
their effective mineral content. Beneficiation usually involves crushing
and grinding the ore to small particle size, flotation to separate the
ore from the gangue, and roasting the separated ore to produce a product
for smelting or refining operations. These processing steps, if they were
performed in the dry state, would generate dust and, if they were not
enclosed, the dust would be liberated to the ambient environment.
However, crushing is usually done in a closed air system, thus minimizing
the amount of dust generated. Grinding and flotation are always carried
out using water and hence are not a source of dust. In the roasting of
ores, a flowing stream of air is used for combustion of the fuel. This
air stream and the gaseous exhaust products of the roasting process cap-
ture the process-generated fine particles and dust and carry them to and
through the exhaust stack of the roaster. Unless a proper dust collection
or precipitation system is installed to contain these emissions, the dust
will settle out of the exhaust plume and present a hazard to employees
in that area. However, dust collecting systems are used.
Following the roasting operation, the product is transferred to a stock-
pile. During this transfer, as well as during transfer between operations,
dust may be released to adjacent areas, unless it is properly contained.
In the beneficiation process, poorly maintained equipment or improperly
controlled processes provide opportunities for the release of potentially
hazardous dust.
Antimony, because its oxides have high vapor pressure, can be beneficiated
by volatilization. When lean antimony ores, even those with concentrations
of 1 or 2% are heated, the antimony oxide volatilizes from the ore matrix.
The fuming oxide condenses upon cooling and is collected in highly en-
riched condition. A properly maintained volatilizing furnace or collec-
tion system insures safe conditions. If, however, the furnace leaks and
releases the fine oxide' fumes to the ambient atmosphere, workers will be
exposed to a potential hazardous situation. For safety purposes, during
beneficiation local exhaust of working areas and direct exhaust of the
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roasting furnace are recommended.
In the production of antimony metal from its ores, the fossil fuel fired
reverberatory furnace has been widely used. When the ore is charged to
the smelting furnace with coke and an alkaline flux, a limited amount of.
antimony ore dust may be released. The charge is heated by the hot gas
combustion product from open flames located at various points around
the furnace hearth. Although at the start of the smelting operation
the flow of hot gas in the furnace hearth entrains dust from the ore,
the furnace is usually designed to carry this entrained dust to a gas
cleaning system, where the dust is removed and collected before the gas
is exhausted to the atmosphere. As smelting continues, the charge be-
comes molten. Then, antimony oxide fume is generated from the molten
metal by oxidation of the metallic vapor, which is present above the
surface of the bath. More fume is generated at the surface of the molten
metal. This fume, like the dust from the charge, is carried by the
furnace gas stream to the gas cleaning system for removal and collection.
Because the by-product dust and fume are relatively rich in commercially
valuable antimony oxide, the general practice is to maximize their col-
lection and recovery from the exhaust gas stream. Again, leaks in the
walls of poorly maintained furnaces will permit the antimony oxide dust
or fume to escape into the work area. For the protection of the workers,
recommended procedures include direct exhaust of the smelting furnace
and local exhaust of working areas.
Another potential source of contamination arises when the smelter is tapped.
During tapping, the ambient atmosphere in contact with the molten metal
surface gives rise to antimony oxide fume, which is dispersed over the
working area. Thus, workers near the smelter are exposed to the fume,
unless the emissions are controlled by forced ventilation of the area to
overhead canopy hoods that exhaust the fumes. If the molten metal tapped
from the smelter is cast directly to pigs for remelting, the molten metal
will not be in contact with the air and there will be one less possibility
of fume release. If, however, the tapped metal goes to a ladle, a separate
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casting step is required. Again, the interaction of molten metal with
the atmosphere will give rise to the release of antimony oxide fume at
that location. In a further step, the crushing of cast antimony, there
is less likelihood of significant dust release because the antimony does
not shatter into fine particles. During the tapping, ladling, and casting
operations, local exhaust of working areas is recommended.
Current regulations require the use of baghouses, electrostatic precipi-
tators, and other devices to control air emissions of hazardous or po-
tentially hazardous pollutants from smelters and other manufacturing plants.
Effluent limitations recently proposed by the EPA for the ore mining and
dressing industry suggest less than 0.5 of Ippm Sb from antimony mines.
These regulations are contained in the Clean Air Act (as amended), the
Federal Water Pollution Control Act (as amended), and the Marine Protection,
Research and Sanctuaries Act (as amended). Consequently, most large U.S.
industries are working to curtail the discharge of their hazardous pol-
lutants into our air and water.
Air emissions, solid wastes and effluents generated by the two major
producers of antimony in the U.S. can be characterized as follows. TRW (1973)
assumed annual production in 1968 of 5,500 tons of antimony by the Laredo,
Texas smelter of NL Industries. Although the smelter produced no signi-
ficant amount of liquid effluent, it produced 2833.56 tons/year of air-
borne wastes, including NO (10.30 tons/year), S02 (60.5 tons/year), hydro-
carbons (1.76 tons/year), CO (2.590 tons), and particulates (171 tons/year).
Sixty-two Ibs of particulates per ton of antimony were produced. The
antimony content of the particulates was not known, but TRW assumed that
it was 1%, and figured an airborne emission of approximately 28.1 g
Sb/ton Sb produced. A further assumption (based on available data for
the volume of stack gases produced as a function of the metal production
in a lead smelter) provided an estimate that the Sb particulate emissions
3
were 7.5 irig/m . If so, the emissions in 1972 were 15 times the accepted
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Threshold Limit Value, but represented a decrease over previous emissions
due to the installation in 1972 of four additional baghouses to collect
the smelter emissions. In this same report, the slag or solid waste
generated by the smelter is listed at 8,015 tons/ton Sb, or 44,000 tons
annually. The slag, described as an insoluble mixture of metals and
oxides, contains 1% Sb (60% metal, 40% oxides). NL Industries stores
this slag outdoors on its property. The current soft antimony market
precludes any immediate reworking of the slag.
In a recent discussion, a representative of NL Industries in Laredo
confirmed that since 1972 the company had added the new baghouses, plus
extra hoods and controls, and had succeeded in reducing the smelter
emissions "tremendously" but not completely (Hornedo, 1975). In a later
communication (Hornedo, 1976), NL Industries reported that its smelting
and refining operations are equipped with high efficiency (99+%) fabric
dust collectors. These collectors efficiently control particulate
emissions, which currently have been found to be within acceptable limits
and are not considered to be a problem. Blast furnace slag, containing
approximately 1% antimony (of which 60% is in the metal form with the
remainder in the form of silicates), is stock-piled in outdoor storage
for future reclamation. There is no liquid effluent of any consequence
emanating from the Laredo operations.
The Sunshine Mining Company, Kellogg, Idaho, in 1971 produced 854 short
tons of antimony by electrowinning from the NaOH leach of their Ag-Cu ore.
In 1971, the liquid effluent from this process contained 5 to 40 ppm Sb,
but a recycling system scheduled for 1972 was expected to recapture the
Sb in the effluent as soluble thioantimonate ion. As such it would be
recycled to the main plant, and mixed with the antimony plant influent,
the NaOH leach of Sunshine's Ag-Cu ore. Thus, the company planned to
recover the 40 Ib of Sb that it has been losing in its 9 to 12 tons/day
of liquid effluent. With the installation of the recycling system,
Sunshine expected to eliminate its settling ponds and stop the flow of
5 to 40 ppm of antimony pond effluent into the South Fork of the Coeur
d'Alene river (TRW, 1973).
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In a recent discussion, a representative of the Sunshine Mining Company
reported that the company had installed the recycling system for its
liquid effluent (Barr, 1975). Sunshine now discharges 900 gals/minute
of effluent containing antimony in the range of 1.0-1.3 ppm (actual for
the day of discussion was 1.26 ppm), which is a considerable decrease
compared to the 5 to 40 ppm Sb discharged in 1971. However, Sunshine is
still working to cut its antimony discharge in order to meet the EPA
proposed antimony mine effluent limitation of less than one-half of 1 ppm
Sb, and may have to go to acidification to do this. Because of the pro-
duction method used, Sunshine has no air emission problem and generates
no solid waste.
At this time, however, fish cannot survive in the river near the Sunshine
operations. The company blames this condition on the sewage, dumped
into the river by neighboring towns of 4-5000 population, which uses up
all the available oxygen making it impossible for fish to live in the
river. Before so much sewage was dumped into the river, the mine tailings
apparently neutralized the sewage that found its way into the river,
leaving enough dissolved oxygen for the fish to survive. In addition,
certain fish came yearly to the area to spawn in the river. Fishery
studies planned for 1976 are expected to make it possible for fish to
return to the river. There is apparently no damage to vegetation in the
area from the effluent discharged by the Sunshine Mining Company (Barr, 1975)
3. Transport and Storage
Table X summarizes current practices and procedures used by manufacturers
in handling, storage and transport of antimony and its compounds. The
information was culled from manufacturers' bulletins, materials safety
data sheets, and technical brochures.
The potential exists for the release of dust or oxide fumes in manu-
facturing plants, when molten antimony metal or its oxide products are
transported from one operating area to another, and in the transport of
antimony and its compounds during their shipment to warehouses, to users
and within the user's facilities. Cooper £t al, 1968 reported that
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TABLE X
CURRENT HANDLING PRACTICES
SUBSTANCE
Complex Antimony
compound
(One or 75RA)
and
Ant imony
Silico oxide
(Oncor 23A)
High purity Sb
Antimony trioxide
(Ant itnony ox ide)
(Sb2o3)
COMPANY
NL Industries
Atomergic
Chemetals Co.
American
Smelt ing and
Refining Co.
(Asarco)
J.T. Baker
Chemical Co.
STORAGE
AND
HANDLING
External:
Normal work day
accumulations can
be effect ively
cleansed with soap
and vater
Change work
Very prone to
surface contami-
nation
Good personal
be practiced to
avoid ingest ion
Wash thoroughly
after handling
FIRE AND EXPLOSION
HAZARD
No special fire
hazards are anti-
cipated but ex-
includes chemical ,
foam, CO , fog(water
on fires involving
Oncor 75RA
Not flammable
EMERGENCY 1st AID
Abnormal ingest ion : *
induce vomit ing ,
give milk and mag-
nes ium sulf ate
(Epsom salts)
Eyes:
use first aid proce-
Consult physician
if symptons of illness
*Call physician at once
if ant imony s il ico
oxide is ingested
Remove from exposure
call a physician in
the event of acute
s y rap t oms d u r i ng
exposure
If swallowed, if
conscious, induce
vomiting by giving
a tablespoon of salt
in a glass of warm
water. Repeat until
vomit is clear.
Give whites of eggs
beaten with water.
Keep patient warm
and quiet.
Call a physician
REACTIVITY
DATA
Hazardous de-
compos it ion
products include :
Sb^O,
24
Sb2o5
Oxidizes
readily when
melted in the
presence of air
May generate
reducing
conditions
Stable
Ignites and
burns when
heated in air
SPILL OR LEAK
PROCEDURES
Sweep carefully,
wear gloves,
goggles, and
re spirator
Sweep or
as possible into
closed containers.
Flush area with
water spray.
Wear approved
respiratory equip-
ment
SPECIAL PROTECTION
INFORMATION
SPECIAL PRECAUTIONS
Avoid dust ing- use
Bureau of Mines
approved dust and/
and goggles
quired to keep TLV
limits (for .example ,
25% Sb20 or 507.
Sb_0.-0.5mg/m ) .
f. b
Use Bureau of Mines
protection, protec-
ive gloves and eye
protection
Avoid breathing vapor
or dust . Use respira-
tor, local exhaust for
vent ilation, work in
hood, wear rubber
gloves , safety glasses
and approved working
clothes
WASTE DISPOSAL
Landfill and smelter
(Disposal must be
done in accordance
and federal
Surface contamination
may be removed by a
short treatment with
dilute aqua-regia (1:1)
or dilute HNO. plus a
small quant ity of HF
Dispose of materials
Be cognizant of
potential water pollution
problems
According to local
regulations
-------
TABLE X
CURRENT HANDLING PRACTICES (Cont'd)
SUBSTANCE
Antimony trioxide
(Antimony oxide)
-------
TABLE X
CURRENT HANDLING PRACTICES (Cont'd)
SUBSTANCE
Ant imony
trichloride
(Anhydrous)
(Sbci3)
COMPANY
Manufacturing
Chemists
Association
(MCA)
STORAGE
AND
HANDLING
Ventilate for drum
unloading
Contain in metal
drums and pails,
single trip, full
removable head ,
2 and 5 gallon
capacity
Box in glass
carboys-5 gallon
capacity, pharma-
ceutical grade .
Keep dry and cool,
protected from
rain and sunshine
Store in tightly
closed containers
out of contact
with moisture
FIRE AND EXPLOSION
HAZARD
Nonflammable
For fighting fires
use suitable self-
contained breathing
apparatus
EMERGENCY 1st AID
Skin contact and
Flush with large
quantities of
water and wash with
soap and water, re-
move contaminated
clothing and wash
Eye contact
Wash with copious
for at least 15
minutes
See physician at
once
Induce vomiting with
warm salt water
See physician at
once
i
1
1
REACTIVITY
DATA
of moisture,
lease hydrogen
chloride gas
SPILL OR LEAK
PROCEDURES
and flush with
hot)
Brush clothing
off, remove
clothing and wash
in water
SPECIAL PROTECTION
INFORMATION
SPECIAL PRECAUTIONS
steel work in exposure
area with acid resis-
tant paint
Handle in closed
system to avoid
atmospheric
moisture or de-
humidify room air.
Use local exhaust
or fume hood and
ventilate work and
storage areas
Eye protection:
Use chemical or
special- type safety
goggles and face
shields
Respiratory protec-
tion:
Use industrial
canister type gas
masks approved by
U.S. Bureau of Mines
or cartridge
respirators
Head protection:
Use safety or "hard"
hat where appropriate
otherwise- brimmed
felt hat
Foot protection:
Leather or rubber
safety shoes with
built in steel toe
caps recommended
Body, skin and hand
protection:
Use rubber aprons,
long rubber gloves,
sleeves of non-
porous protective
material
Removal of all con-
taminated clothing
immediately and
clean before reuse
Wash thoroughly
WASTE DISPOSAL
cr vast a by
flushing with hot
water
Seal large
amounts of
residues in con-
tainers and bury
;
-------
TABLE X
CURRENT HANDLING PRACTICES (Cont'd)
SUBSTANCE
Ant Imony
trichloride
(SbCl3)
and
Ant imony
pentachloride
(SbClj)
Antimony
pentachloride
(Ant imony
perchloride)
(SbCl )
•
Tartar Emetic
(Ant Imony
Pot as s iura
Tartrate)
COMPANY
J.T. Baker Chemical
Co.
Hooker Chemical
Corp.
Pfizer Chemicals
Division
STORAGE
AND
HANDLING
Keep in tightly
closed containers
in a dry place
Do not. get in eyes.
on skin, or on
clothing
Do not open unless
properly instructed
Do not clean or re-
use container
Shipped In 10-galloi
(non-returnable)
steel drum
FIRE AND EXPLOSION
HAZARD
If involved in
fire, water may be
used
EMERGENCY 1st AID
Internal :
If conscious, give
plenty of water, induce
vomiting until vomit
fluid is clear. Give
milk or egg whites
beaten with water
Keep warm and quiet
External:
Immediately flush area
with plenty of water
for at least 15 minutes
while removing contami-
nated clothing
If inhaled:
Move patient to fresh
air. Give artificial
respiration if breath-
ing has stopped
Call a physician
(As above under
external)
External
Flush skin with water.
If eye contact, flush
with water and seek
medical attention
Internal :
Call physician
immediately
Use plain, or soapy
water or water with
table salt or milk
(3-4 glasses) to
provoke vomiting
REACTIVITY
DATA
Stable
Do not add
water to con-
tents while in
a container
because of
violent re-
action
Stable
SPILL OR LEAK
PROCEDURES
If spilled,
dissolve in min-
imum hydro-
chloric acid
(concentrated
reagent)
Dilute with
water until white
precipitates form
Add just enough
6M-HC1 to redis-
solve >
Saturate with
hydrogen sulflde.
Filter wash the
precipitate, dry
and package
In case of spill-
age, flood care-
fully with large
volume of water
and provide
adequate ventila-
tion
Remove by scoop
or shovel
SPECIAL PROTECTION |WASTE DISPOSAL
INFORMATION :
SPECIAL PRECAUTIONS
Do not. breathe vapors May be disposed
Use respirator, local
exhaust for ventila-
tion, and work in fume
hood
Wear protective rubber
gloves, safety glasses,
and approved working
clothes
Wash clothing before
re-use
Use approved dust
respirator. Use dust
exhaust system at
point of use for
ventilation
Protect with rubber or
by .contacting, an
approved outside
waste disposal
service and/ or
according to
local regulations
Wash down and
flush to safe
area
plastic coated gloves; \
chemical goggles; ' ,
tightly woven, close- i
fitting clothes for
minimum exposure of skinf
to dust and frequent !
showers
i
-------
TABLE X
CURRENT HANDLING PRACTICES (Cont'd)
SUBSTANCE
Tri-n-butyl
antimonite
(Ant imony
tri-n-butylate)
(TNBA)
COMPANY
Stauffer Chemical
Co.
STORAGE
AND
HANDLING
Package and store
under nitrogen(or
an inert atmosphere)
Store in carbon steel
or brass cylinders of
the 55 gallon drum
16 gauge size. Small
quantities can be
shipped in glass or
high density poly-
ethylene containers
Remove and launder
clothes before
reuse
FIRE AND EXPLOSION
HAZARD
Flammable
To fight fires use
fog, CO- or dry
powder
EMERGENCY 1st AID
Inges tj.pn :
give large amounts
of warm or salty
water to induce vomit-
ing, until vomitus is
clear. Milk, eggs or
olive oil may be given
to sooth following
vomiting
Consult a physician
if abdominal dis-
Eye contact:
flush eyes immediately
with large quantities
of running water for a
minimum of 15 minutes
Consult a physician if
irritation persists
Skin contact:
flush affected area
with water
Consult a physician if
irritation persists
Inhalation:
Remove from contaminated
atmosphere
See a physician if
respiratory discomfort
persists
REACTIVITY D
DATA
Extremely air
and moisture
sensitive
Reacts rapidly
with water,
acids and bases
to liberate
antimony oxide
and butyl
alcohol
Product of
hydrolysis is
very toxic
SPILL OR LEAK
PROCEDURES
SPECIAL PROTECTION
INFORMATION
SPECIAL PRECAUTIONS
Avoid contact with skin,
eyes and clothing
Eye wash stations,
approved safety glasses
and approved chemical
rubber gloves are
recommended
WAS7Z ri5?OSAL
Cor.ts;- i he
5o«c ial^T
Che=tica;'
Divis ir- for
re ^ coze -cat ions
on unused
niacar ial
-------
concentrations of antimony in air, monitored in 1966 at 36 antimony
processing plant locations under varied environmental conditions, ranged
3
from 0.081 to 75 mg/m . Concentrations
in the area of the bagging operations.
3 3
from 0.081 to 75 mg/m . Concentrations as high as 138 mg/m were found
In addition, the dust or vapor, when exposed to heat or flame, is a
potential fire hazard. The dust, when exposed to flame, can be an explosion
hazard. Conditions contributing to the instability of antimony compounds
depend upon the specific compound of antimony involved. No generalization
can be made, but the reactivity of these substances is discussed in more
detail in Section IV.C.2, which covers current transport practices. Like-
wise, the incompatibility of antimony and its compounds, which also de-
pends on the specific compound involved, governs transport practices and
is discussed in Section IV.C.2. As an example, antimony metal in con-
tact with nascent hydrogen will react to form stibine (antimony hydride),
an extremely toxic compound.
Antimony and its compounds should be stored in dry, well-ventilated areas
away from rain (or other water), heat and sunlight. Dust and fumes from
leaky containers again are potential health, fire or explosive hazards.
Fire extinguishers are recommended for storage areas and employees should
not eat or smoke in these areas. Specific storage precautions are dis-
cussed in Section IV.C.2.
4. Uses
In addition to the contamination potentials that exist during the mining,
production, transport, and storage of antimony and its compounds, a
similar potential exists in those industries where antimony and its com-
pounds are used in the preparation of other products or exist as by-
products of other operations. Exposure can be by inhalation, skin contact,
or ingestion. Proper ventilation of the work areas, protective clothing
protective respiratory devices, and other protective equipment should be
used, depending on the specific compound involved. Individual procedures
are discussed in Section IV.B and IV.C.I.
-59-
-------
Some potential inhalation exposures occur during the production of lead/
antimony alloys (which include pewter, Britannia metal, type metal,
babbitt, and white metal) when antimony fumes and dust may be released.
During the welding of metal products of alloys containing antimony
(which include bearings, pipes, machine parts, and ornamental casting
solder) antimony oxide fume may be released. Antimony dust is a potential
hazard during the machining, grinding, buffing, and polishing of antimony-
containing metal products. The oxide fume and dust may also be released
during the casting, parting, and cleaning of battery grids and plates
made of lead/antimony alloy. The liberation of toxic stibine from
storage batteries may occur when nascent hydrogen reacts, in an acid
medium, with antimony present in the battery.
In various type-setting operations (linotype, monotype, steirotype),
antimony oxide vapors and dust may form. When antimony oxides are added to
paints, pigments, enamels and glasses, there is a chance that the trioxide
dust may form. In the manufacture of ceramics and glass, some antimony
pentoxide dust may be formed. Skin contact with antimony trichloride
solutions is a potential hazard during the dyeing and flameproofing of
textiles, while skin contact with antimony pentachloride may occur during
the manufacture of steel. Skin contact with and inhalation of sulfide
dust may result from rubber compounding operations.
Antimony trioxide is used primarily as a fireproofing additive in plastics,
textiles, and other products. During the blending and molding of flame
retardant plastics, for example, there is the potential for environmental
contamination.
In blending, dusting of the antimony oxide may cause direct atmospheric
contamination. In addition, since occasional washing down of the dusty
walls, floors, etc. is standard housekeeping practice, a smaller amount
of antimony oxide may find its way into the waste water drains. In the
molding of the flame retardant resins to produce finished goods, the
materials are commonly exposed to temperatures as high as 250°C. At
these temperatures, antimony oxide combines with the halogens in the
resin to form volatile antimony species such as antimony oxyhalide and
-60-
-------
antimony trihalide. These materials typically condense on the cooler
surfaces of the molds and ultimately must be removed by repolishing the
mold surfaces.
Because of the high boiling points of these antimony halides, it is un-
likely that a significant vapor concentration of these materials will be
present at room temperature. Hence, the possibility of atmospheric con-
tamination is remote.
Because very .little of the antimony trioxide is used in the finished
product (less than 2 to 3 parts/100 Ib of plastics), it is disposed of
as part of the plastic material. Antimony trioxide is discarded into
municipal systems. There is no evidence that it is a harmful pollutant.
5. Disposal
Waste disposal methods for antimony and its compounds are governed now
by local, state, and Federal ordinances. Permissible disposal methods
depend upon the type of antimony compound involved. Solubility in water
is an important factor.
Methods of waste disposal currently are landfill and smelter. Landfill
carries with it the potential for hazards due to the leaching of trace
metal into ground or surface waters. Smelting implies the possible
emission of trace metals, which can be inhaled by people in the vicinity,
or carried by the wind and deposited on soil or in waters. Because all
trace metals can be toxic in high enough doses, and because antimony is
identified as a trace metal with innate toxicity, its inhalation in high
concentrations could be a health hazard. Ocean dumping of antimony waste
has been practiced but ocean dumping of hazardous chemicals is under
fire now because of potential harmful effects on marine life and on the
marine ecosystem.
In mid-1974, five Gulf States protested EPA's granting of a permit to
DuPont to dump waste chemicals, including antimony compounds in aqueous
solutions or suspensions, in the Gulf of Mexico, some 230 miles south of
Pensacola, Florida. Wastes, from DuPont's plant near Belle, W. Virginia,
-61-
-------
have been barged to Weswego, La., and dumped into the Gulf since 1969.
The complainants emphasized the toxicity of antimony, which is used as a
catalyst in the production of polyesters and is retained in the spent
glycol recovered at the Belle plant. DuPont anticipates storing and
handling the questioned waste in its own facilities by mid-1977. If the
company cannot continue ocean dumping, storage and handling costs are
estimated at $10-$13 million (Chem. Eng. News, 1974).
As a result of current regulations, land disposal sites are used more
frequently for the disposal of sludges, slurries, and concentrated liquids.
Recommended methods for disposal of antimony compounds include disposal in
a chemical waste landfill, chemical pre-treatment before disposal by land
burial, and encapsulation followed by disposal in a chemical waste landfill
Chemical waste landfill can be used for the disposal of antimony penta-
sulfide, antimony sulfate, and antimony trisulfide. Chemical waste
landfill differs from conventional sanitary landfill in that it requires
the segregation of the wastes, the use of barriers to prevent leaching
of the wastes to groundwater and, in some instances, the pretreatment
(neutralization, chemical fixation, encapsulation, etc.) of the wastes.
In its 1974 Report to Congress on the Disposal of Hazardous Wastes
(EPA Publication SW-115), the U.S. EPA Office of Solid Waste Management
included antimony pentafluoride and antimony trifluoride in a list of
nonradioactive high hazard waste compounds. Compounds so classified are
considered unacceptable for normal disposal methods because of their
potential for causing adverse health or environmental effects.
The following method is recommended for the disposal of antimony penta-
fluoride and antimony trifluoride. Dissolve the compound in dilute HC1
and saturate with H.S. Filter, wash, and dry the antimony sulfide pre-
cipitate. Air strip the dissolved H~S from the filtrate and pass the
filtrate into an incineration device equipped with a lime scrubber. After
the stripped filtrate has reacted with excess lime, dispose of the preci-
pitate (CaF-CaCl mixture) by land burial.
-62-
-------
Nickel antimonide should be encapsulated before it is disposed in a
chemical waste landfill.
NL Industries, Inc., which lists the decomposition products of antimony
trioxide as Sb00. and Sb90e disposes its oxide waste by landfill and
24 ^ J»
smelter; Asarco advises disposing waste trioxide in closed containers,
being cognizant of water pollution problems.
To dispose of its antimony trichloride wastes, J.I. Baker Chemical Co.
contacts an approved outside waste disposal service.
Antimony pentachloride can be decomposed by water, forming toxic, corosive
hydrogen chloride. Hooker Chemical Co. decomposes its waste antimony
pentachloride by feeding it at a controlled rate into water in a retention
area, and adjusts its pH with lime or caustic before discharging the
effluent.
In what may be a procedure for handling spills, Pfizer Chemicals Division
reports that its antimony potassium tartrate (solubility in water =8.7
g/100 ml) should be washed down and flushed to safe area.
On p.258 of its "Proposed Criteria for Water Quality," Vol. I, Oct. 1973,
the EPA set the maximum acceptable concentration of antimony in marine
or estuarine waters at 1/50 (0.02) of the 96-hour LC5Q value determined,
using the receiving water and the most important sensitive species in
the locality as the test organism. Maximum allowable concentration of
antimony in marine or estuarine waters is 0.2 mg/1. Insufficient data
were available at that time to recommend a level that would present
minimal risk of deleterious effects.
However, on p.4, Vol. II, of that same publication, the EPA reports that
antimony in industrial effluents is rapidly removed by precipitation
and adsorption, and no antimony was detected in the principal rivers
of the U.S. in 1958-59. However, later information, as mentioned'pre-
viously, indicates the presence of antimony in the sediments of waters
in manufacturing areas.
-63-
-------
6. Potential Antimony Release from Other Products and Industrial Processes
A large copper smelter near Tacoma, Washington, operating since 1890,
produces as a by-product most of the arsenic trioxide used in the U.S.
In addition to the arsenic that it releases into the environment, this
smelter releases antimony in three ways: (1) as a stack gas into the
air, 2 x 10 kg/yr of antimony oxides; (2) as antimony species in liquid
3
effluent discharged directly into Puget Sound, 2 x 10 kg Sb/yr; (3) as
crystalline slag particles dumped directly into the Sound, 1.5 x 10 kg
Sb/yr. (Puget Sound also receives 250 kg of antimony/yr from sewage
treatment plants).
In a recent study of the hazardous waste generated by seven industrial
inorganic chemical industries — chlorine, titanium dioxide (manufactured
by the chloride process), chrome colors, mineral acids, aluminum compounds,
potassium and sodium compounds, and industrial inorganic compounds (not
elsewhere categorized) — antimony was included as a hazardous constituent
only in the waste streams generated by the production of titanium dioxide
(chloride process) (Morekas, 1975).
Waste streams from the production of titanium dioxide by the chloride
process contain a number of potentially hazardous constituents: antimony,
arsenic, cadmium, chromium, cyanide, lead, mercury, and zinc. The waste
discharge from one such titanium dioxide plant with an average wastewater
discharge of 112 millions of liters/day contains 300 kg of Sb/metric ton
of product. The raw material feed for this plant is over 95% TiO_ grades
of rutile and upgraded ilmenite (EPA, 1974).
Because many smelting and high-temperature combustion operations emit
particles containing antimony and other toxic elements into the air,
Davison et al (1974) measured the concentrations of 25 elements in the
fly ash from a coal-fired power plant. The concentrations of antimony
and nine other elements increased markedly.with decreasing particle size,
and in urban aerosols antimony is reported to have an equivalent mass median
diameter of the order of 1 pm or less. Elements with their mass concen-
trated in the particle size range 0.5-10.0 ym are inhaled and deposited in
the human respiratory tract.
-64-
-------
In a stUdy by the EPA National Fuels Surveillance Network, trace elements
in gasolines and commercial gasoline additives contained a number of
elements, including antimony. Concentrations of antimony in premium
gasoline ranged from <0.003-0.05; in regular gasoline, <0.007-0.5; and
in low lead gasoline were <0.10 yg/ml. In the additives, antimony con-
centrations ranged from <0.0005-0.0041 yg/ml. The presence of trace metals
in gasoline is of environmental concern, since some have suspected biolo-
gical toxicity, and they can be disseminated widely in the respirable
range, at ground level. Antimony, however, is not included in the list
of metallic elements (Ce, As, V, Ni, and Cr) cited as being suspect of
biological toxicity (Jungers e_t^ ad, 1975).
In mid-1971, several industrial companies, e.g., Dow Chemical, BASF
Wyandotte, Georgia-Pacific, Kaiser Aluminum and Chemical, and Weyerhaeuser,
were reported to have started company surveys to identify trace element
pollutants likely to be involved in their processes. Antimony was one
of 30 elements listed by Dow. On the basis of preliminary survey results,
Dow eliminated some metal compounds from its processes and made some
process and catalyst changes. Antimony, arsenic, beryllium, cadmium,
and lead have caused industrial deaths*
According to Dr. H.A. Schroeder of the Dartmouth medical school's trace
i
element laboratory, no metal is degradable and toxic metals in the environ-
ment pose a serious health hazard. He recommends the elimination of
cadmium by controlling zinc smelting emissions, and urges the control of
antimony and beryllium in the air by the reduction of particulate emissions
from coal smokes. The biggest, but not the sole, source of atmospheric
trace elements if probably the burning of fossil fuels, including gasoline
with additives (Chem. Eng. News, 1971).
-55-
-------
7. Chemical Reactions in the Environment
a. Hydrolysis
Because metallic antimony is a stable element, it does not readily react
with moisture. Stibine (SbH») may be formed, however, by the hydrolysis
of hydrochloric acid on Zn»Sb»or other metal antimonides.
In the presence of moisture the normal salts hydrolyze readily. Antimony
trichloride releases hydrogen chloride gas, which represents a hazard in
itself. Other antimony halides behave similarly. Antimony pentachloride
reacts with water in a 1:1 molar ratio to form SbCl,_.H90 and in a 4:1
*J £
molar ratio to form SbCl^.AH-O. Further dilution gives HC1 and hydrated
(V) antimony oxide.
Although there is no direct evidence that antimonic (III) acid is a definite
compound, antimony (III) oxide forms hydrates of indefinite composition
believed to be related to the hypothetical antimonic (III) acid.
With water, antimony pentafluoride forms a clear solution from which
SbF .2H 0 can be crystallized.
Antimony tri-n-butylate reacts rapidly with water (and with acids and bases)
to liberate antimony oxide and butyl alcohol. The combined products of
hydrolysis are very toxic.
b. Oxidation
Metallic antimony, because it is stable or inert, is not readily attacked
by air. Under controlled conditions, it will combine directly with air
or oxygen to form its oxides, Sb20., and Sb20,-. A tetroxide, Sb^, a
stoichiometric compound (Sb-O^.Sb-O ), is also formed.
Although antimony does not combine directly with hydrogen, antimony metal
reacts with oxidizing materials and acids to produce stibine (SbH~).
-66-
-------
Antimony reacts with nitric acid to form hydrated antimony pentoxide,
a gelatinous precipitate. An oxysulfate (undefined composition) results
when antimony reacts with sulfuric acid.
The reaction of antimony with hydrochloric acid is slow unless air is
present.
Oxiding agents react freely with stibine. Stibine, ignited in the presence
of air or oxygen, forms water and antimony trioxide. Both metallic anti-
mony and antimony trioxide will react with strong oxidizing agents to form
hydrated antimony pentoxide, a gelatinous precipitate sometimes called
antimonic acid.
In the absence of air, antimony trisulfide dissolves in alkaline sulfide
solutions to form the thioantimonate (III) ion. This ion is oxidized in
air to the thioantimonate (V) ion.
c. Photochemistry
In the presence of light and at 100°C, stibine reacts with sulfur to
form antimony (III sulfide; with selenium to form antimony (III) selenide.
Photochemical properties of antimony trioxide have been investigated by
Markham jejt a!L (1958), who reported darkening of Sb^Oo and the production
of peroxide under ultraviolet light. The reactions compared with those
of zinc oxide. (Although this property of zinc oxide finds use in some
copying papers, no equivalent use has been reported for the antimony
compounds.)
d. Other
Antimony reacts with chlorine to form antimony tri- and pentachloride, and
with sulfur to form antimony tri- and pentasulfide.
Some insoluble antimony compounds react with hydrofluoric acid to form
fluorides or fluocomplexes.
-67-
-------
D. Analytical Methods
1. Laboratory Standard Analytical Methods
Traditional analytical methods are available for determining the antimony
concentration in ores, minerals, and even rafter dusts, but the greater
precision and sensitivity offered by modern instrumental methods is
required for the trace analysis of this material and its compounds in
air, water, and in biological specimens. Colorimetric analysis of
antimony has been employed widely for many years with the tetraethyl-
rhodamine (Rhodamine B) method cited most frequently. The Rhodamine B
test has a sensitivity of 6y. In more recent years, such analytical
techniques as atomic absorption spectrophotometry (a.a.s.) and neutron
activation analysis (n.a.a.) have come into greater use.
In its Official Methods of Analysis for 1975, the Association of Official
Analytical Chemists (AOAC) describes the determination of pentavalent Sb
as residue in foods by means of an American Conference of Governmental
Industrial Hygienists (ACGIH) - AOAC method. In an aqueous hydrochloric
acid solution, antimony reacts with tetraethylrhodamine (Rhodamine B) and
forms a colored complex which can be extracted with organic solvents
such as benzene or toluene. The color intensity is measured at 565 nm
spectrophotometrically. This method resulted from the ACGIH-sponsored
collaborative tests on the Rhodamine B colorimetric method for antimony
which the AOAC (then the Association of Official Agricultural Chemists)
reported (Bartlett and Monkman, 1964).
The AOAC also reports the development of an atomic absorption method for
antimony in the food additive titanium dioxide (Hoffman, 1969). This
method is based on fusion with potassium hydrogen sulfate and extraction
with methyl isobutyl ketone.
Atomic absorption spectroscopy is widely used in determining the presence
of antimony. Data gathered with the Perkin-Elmer Model 303 instrument
at 2175 A wavelength with a 7 A slit show the detection limit of 0.2
yg/ml with a sensitivity of 1 yg/ml/6%.
-68-
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Determinations of antimony in air-acetylene flame show sensitivity at
o o
three wavelengths: 0.5 ug/ml/1% at both 2068.4 A and 2175.9 A and 1.2
o
pg/ml/1% at 2311.5 A. The 2175.9 line is the most commonly recommended
wavelength for antimony.
A similarity in sensitivity and detection limits for a.a.s. and atomic flame
spectroscopy (a.f.s.) for antimony is shown (Norris and West, 1974) in
various flames. The argon-hydrogen flame proved slightly superior to the
air-hydrogen flame in each instance, though interferences were greater in
the argon-hydrogen flame. In an atomic absorption spectroscopy study on
the determination of antimony utilizing the generation of covalent hydrides
(Thompson, Thomerson, 1974) data was obtained using a Shandon Southern
Instruments A3400 atomic-absorption spectrophotometer. A 1 ml sample of
acidified Sb111 treated with 2 ml sodium borohydride (1%) gave a detection
limit of 0.0005 (2a)/yg/ml at characteristic concentration at 1% ab-
sorption of 0.00061 yg/ml-
Flameless a.a.s. of antimony in metallurgical samples with a carbon rod
atomizer requires solvent extraction of the chloride complex from HC1
solution because of matrix effects of antimony adsorption (Yanagisawa
et_ al, 1973).
ASTM Tests
The American Society for Testing and Materials (ASTM) gives a standard
method for chemical analysis of antimony metal (E86-57) with a composition
of 99 to 99.9% antimony, where the antimony is determined by difference.
In ASTM E87-58, a photometric method for chemical analysis of antimony
metal is described. The sample is dissolved in a hydrobromic acid and
bromine mixture, distilled, and treated with perchloric acid. A portion
of the treated distillate is transferred to an absorption cell for photo-
metric analysis.
Other ASTM standards describe methods for the chemical analysis of
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antimony depending on where it is found:
• For the detection of antimony in copper (ASTM 54-72)
and in brasses (ASTM 36-45), the distillation-
iodimetric method is used;
• In copper and copper-base alloys (ASTM-62-72), the
method is iodoantimonite (photometric).
• In lead-base and tin-base solder metal bearing alloys
(ASTM E57-60) the standard method for chemical analysis
of antimony is the distillation-bromate method.
• In pig lead (ASTM E37-56), the method established for
determining antimony is manganese coprecipitation.
• In ferroalloys (ASTM E31-73) a gravimetric method is
described.
• In ASTM E396-72a, the Rhodamine B photometric method
of chemical analysis is the standard.
Spot Tests
Spot tests are used by chemists to indicate the presence or absence of
specific elements. Spot tests are not quantitative but they are frequent-
ly rated for the limits of concentration where they are effective. For
spot tests (Feigl and Anger, 1972) (see also: Feigl and Chan, 1967a,b) a
variety of analytical methods are offered for antimony.
• Metallic antimony forms a sublimate of volatile
antimony chloride by means of pyrolysis with an
excess of ammonium chloride.
• Elemental antimony can be detected to lOOy by a
reduction-oxidation reaction with alkaline mercury
cyanide solution. A strong alkaline solution of
mercuric cyanide reacts with other antimony
compounds, such as Sb2C>3 or SbUI salts, to form
black or gray, finely divided metallic mercury.
Salts of Sb^ must be reduced to Sb*** in acid medium
before this reaction can be obtained. A limit of
identification of 10y antimony has been obtained with
potassium antimonyl tartrate using this procedure.
• Phosphomolybdic acid is used to determine Sb2S.,.
• 9-methyl-2,3,7-trihydroxy-6-fluorone is used to
determine antimony**1.
• Gallein gives a violet color in acid solution in the
presence of antimony with a sensitivity of 0.005 .
• Rhodamine B, in tests similar to the ACGIH-AOAC method
mentioned above, can be used to identify pentavalent
antimony.
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• Diaminotriphenylmethane dyes (Malachite Green and
Brilliant Green) and triaminotriphenylmethane dyes
(Crystal Violet) form colored dye complexes when
used with antimony^ compounds in hydrochloric acid.
These complexes are soluble in toluene.
• Antimony pentbxide and tetroxide remain following
ignition of organic compounds containing antimony.
• Diphenylamine or N,N-diphenylbenzidine dissolved in
sulfuric acid imparts a blue color in the presence
of antimony to the limit of 5 antimony.
• Potassium antimony tartrate (tartar emetic of
potassium antimonyl tartrate) may be detected using
standard tests for trivalent antimony and tartrate.
Limits of identification are 2.5Y K(SbO)C4H406 by
forming antimony111 sulfide and 5.0 K(SbO)C^06
by silver oxide reduction.
By suitable selection of the concentrations of bromate, bromide and
hydrogen ions, a technique to determine antimony III is described and
compared to titrimetric and coulometric methods (Burgess and Ottaway,
1972).
A fluorometric method for the determination of submicrogram quantities of
antimony using 3,4',7-trihydroxyflavone is described as being 25 to 50
times more sensitive than the Rhodamine B method (Filer, 1971).
A new flame analytical technique, molecular emission cavity analysis
(MECA) , is described for the determination of antimony (Belcher e_t al,
1974).
Forensic Tests
Traces of antimony of the order of 0.2 yg are deposited on the back of the
hand from revolver ammunition each time the gun is fired, the source of
the antimony being in the primer. A neutron activation procedure has
been used (Ruch et al, 1964) to detect antimony after careful removal of
the residues from the hand.
The apparatus for Reinsch's test was modified for rapid identification of
antimony , arsenic, and mercury (Clarke et al, 1963).
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Gutzeit Test
The Gutzeit method traces back about a century to the silver nitrate test
for arsine. Mercuric chloride or bromide can be substituted for the
silver nitrate reagent. The procedure involves the reduction of arsenic
to arsine, using a few grains of zinc in a dilute sulfuric or hydrochloric
acid solution. The gases, which evolve, pass through cotton-wool or over
filter paper soaked in the reagent and result in a range of colored stains
depending on the quantity of arsenic present.
The Gutzeit name was given to this test in 1879, when H. Gutzeit (Pharm.
Zfg. 24, 263) devised a convenient apparatus for holding the filter paper
in the gas stream. In this test stibine, present in amounts less than
0.1 mg, does not react. The presence of somewhat more stibine, however,
causes the formation of a brown spot which is soluble in alcohol.
The so-called modified Gutzeit test, described in 1952 by V. Vasak and
V. Sedivec ("Colorimetric Determination of Arsenic", Chem. Listy 46, 341)
is similar to the ASTM method (ASTM D372-74) for testing arsenic in water.
Both methods use a solution containing silver diethyldithiocarbamate to
obtain a red compound with a maximum absorbance with a wavelength of
510 nm for antimony, when measured spectrophotometrically.
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a. Analysis in Air
In the "tentative" method of analysis for antimony content of the atmos-
phere (E.C. Tabor, Chairman, Subcommittee 7, 1970) (Also in: Methods of
Air Sampling and Analysis) the collected antimony must be oxidized to the
pentavalent state before analysis with Rhodamine B is possible. The
sensitivity of the antimony determination is 1.0 yg. In seven tests made,
recovery of antimony ranged from 95-102.5% of the 2-10 yg sample.
The Rhodamine B method is also recommended by the Analytical Chemistry
Committee of the American Industrial Hygiene Association and published by
the Intersociety Committee Methods for Ambient Air Sampling and Analysis.
The determination by this method is sensitive to 1 yg Sb in 10 ml solvent,
*i ^
or 0.05 yg/m in a 20 m air sample
Electroreducible cations of antimony can be determined by polarographic
methods of samples collected from air (Dubois and Monkman, 196A). When
there is little organic matter present and the sample is prepared carefully,
polarography is a precise technique with sensitivity in the range that is
adequate for industrial health purposes. The authors compare the method
to dithizone-antimony analyses.
b. Analysis in Water
Atomic absorption is recommended by the Methods Development and Quality
Assurance Research Laboratory (MDQARL) in the Methods for Chemical
Analysis of Water and Wastes under standard conditions. The precision
and accuracy reported by the MDQARL for a mixed industrial-domestic waste
effluent at concentrations of 5.0 and 15 mg Sb/1. were - 0.08 and - 0.1
standard deviations respectively with recoveries of 96% and 97% respec-
tively at these levels.
The test method for antimony listed in the Environmental Protection Agency
Regulations on Test Procedures for the Analysis of Pollutants (40CFR 136;
38 FR 28758, October 16, 1973) is atomic absorption. A special notation
refers to the MDQARL method.
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Neutron activation analysis of antimony in six different marine fuel
oils, before and after prolonged contact with seawater or fresh water,
was performed by Guinn and Bellance 1969 (Skrinde, 1971).
There is no standard method described by the American Public Health
Association (APHA), American Water Works Association (AWWA), and Water
Pollution Control Federation (WPCF), for the examination of antimony
in water and waste water in their joint publication.
c. Analysis in Biological Materials
A spectrochemical method was developed (Kinser et_ al, 1965) for detecting
antimony in biological materials, following exposure to indium antimonide,
the intermetallic compound, frequently used in electronic devices. At
o
spectral line 2877.9 A, concentrations as low as 0.1 yg of antimony can
be detected with a coefficient of variations of 9.9%. Gamma ray spec-
trophotometry can be used to determine antimony deposits in the lung with
a lithium drifted detector (Bloch, 1970).
Measurement of the quantity of antimony present is made by fractional
transmission of X-rays at two different energies through the lung, one
slightly less and the other slightly greater than the K shell binding
energy of antimony.
A method using neutron activation analysis was developed (Mansour et al,
1967) to quantify the levels of antimony in blood and urine of patients
treated with anti-bilharzial antimony drugs. This method was sensitive
to 0.002 mg for antimony In biological fluids.
Thermal neutron activation analysis was combined with a chemical separation
(Howie et^ al, 1965) to estimate antimony in small samples of biological
material with a sensitivity of 10 yg to within 5%.
Hair and nails are a readily available source of biological sampling
though the results require that many variables be considered (Hopps, 1974).
For determining antimony III in human hair, as well as in several standard
alloys, a method using forced-flow liquid chromatography and electrocata-
lyzed oxidation of Sb (III) in a platinum coulometic detector is described
(Taylor and Johnson, 1974). Analysis of hair samples from four subjects,
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engaged in research involving antimony, showed correlation relative to
exposure. .
A method for determining antimony in blood and liver tissue (Loh and
Cie, 1964) is described using Brilliant Green in a colorimetric analysis.
The method requires several steps, but no interference from ion is
reported.
2. Field Methods
A method for direct determination of antimony in sea water by anodic
stripping voltammetry at the mercury-coated graphite electrode was
developed especially for use on board ship (Gilbert and Hume, 1973).
Typical results for the determination of the antimony content of sea
water range from 0.18 to 0.48 ug Kg" , consistent with the values found
by others using neutron activation analysis of freeze-dried samples.
For monitoring purposes, the Canada Centre for Inland Waters developed
a method (Goulden and Brooksbank, 1974) for automated atomic absorption
determination of antimony in natural waters. When a tube furnace is
used as a covalent hydride decomposition device instead of a conventional
hydrogen argon-entrained air flame, sensitivity is improved considerably.
Forty samples can be analyzed in an hour with a limit of detection of 0.5
yg/1. at a wavelength of 217.6 nm.
In a discussion concerning automation of monitoring equipment for marine
pollution studies (Gafford, 1972), a method for automated analysis of
heavy metals and trace elements is suggested. When using atomic absorp-
tion to analyze for antimony, the detectability limit desired is 0.005
ppm. A fluctional concentration limit (FCL) of 2.2. ppm is recommended
with 15.4 as the practical lower limit of range for analysis (FCL X 7).
However, Halstead (1972) reports a virtual absence of environmental
monitoring operations for toxic heavy metals as marine pollutants.
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Analytical methods for determination of airborne particulate antimony
are currently being developed at Arthur D. Little, Inc. (ADL) in conjunc-
tion with Standards Completion Program, Analytical Methods Validation
for NIOSH. Methods are also being developed for stibine in air samples
collection medium and analytical methods are currently being tested.
E. Monitoring
Antimony derived from the weathering of rock, was found in concentrations
ranging from <0.0020 to 0.1 mg/1 in selected drinking supplies in 39 U.S.
states, listed on pp. 20-1 of EPA's "Water Quality Criteria Data Book,
Vol. 2, Inorganic Chemical Pollution of Freshwater," Water Pollution
Control Research Series, 18010 DPV 07, 71, July 1971. On p. 13 of this
publication, it is stated that antimony, if present in freshwater, would
ill II [ I i
exist as the stibous form, Sb , the stibic ion, Sb ; or as triethyl-
antimony,
Average values of antimony in the oceans have been estimated at 0.33 mg/1
or 0.2 ppb (by weight). Antimony concentration in soil has been estimated
at 4 ppm, while the concentration in the earth's crust is 0.2 ppb (by weight)
Portmann (1972) , who gives the normal concentration of antimony in sea
water as 4 Mg/1, believes that the current exploitation of seabed re-
sources will be expanded. In discussing the potential hazards from the
extraction of minerals from the seabed, he comments that, although it
appears unlikely that large concentrations of the element, antimony,
would occur in sea water close to extraction operations, direct ingestion
by marine animals cannot be ruled out. Because concentration factors of
more than 300 have been reported for some marine animals, and as little
as 97 mg have been reported lethal to humans, Portmann advises close
monitoring of antimony extraction operations.
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Antimony has also been detected in British waters. In a study prompted by
current concern about the effects on marine organisms from localized
inputs of heavy metals in domestic and industrial wastes, Leatherland and
Burton (1974) report on measurements, by neutron activation analysis, of
antimony and several other metals in organisms and bottom muds near
Southhampton, England. Antimony was found in concentrations of only 0.01
to 0.1 ppm and the values for fish muscle were at the lower end of the
eoncentration range. Concentrations of 0.2 ppm were found in two ascidians
(sea squirts), a species with outstanding capacity for concentrating such
trace metals as vanadium. Average concentration of antimony in bottom muds
from Southhampton Water were almost 1.0 ppm; a River Mersey sample con-
tained over 2 ppm.
Large amounts of wastes from mining and smelting operations, discharged
into the Coeur d'Alene river in northern Idaho for more than 80 years,
contain high levels of heavy metals. A recent study disclosed the
presence of high concentrations of antimony, cadmium, copper, lead, silver,
and zinc in the sediments of the delta area of the river, and it is
reported that the lake bottom within a 900 m radius from the mouth of
the river is covered with polluted sediments. Analysis of the top layer
of the dry sediments (mostly fine silt typical of mine tailings) collected
at the mouth of the river showed that antimony was present in a concen-
tration range of 270 to 900 ppm. Other metals present were cadmium
(16 to 75 ppm), copper (90 to 150 ppm), lead (3000 to 6300 ppm), manganese
(6200 to 12,500 ppm), silver (6 to 15 ppm), and zinc (3200 to 4700 ppm).
No toxicity attributable to antimony was mentioned, but earlier studies
showed the accumulation of fair-sized amounts of lead and zinc in the
tissues of some waterfowl and assumed that zinc was the lethal constituent
of the wastes that caused the death of certain river fish in 72 hours
(Maxfield et al, 1974).
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By means of nondestructive neutron activation analysis, concentrations
of antimony in the Sound surface sediments and at depths in cores range
from 0.3 to 1.0 ppm dry weight, compared to 3-15 ppm for arsenic. Within
8-15 km of the smelter, antimony concentrations are 2-3 times the back-
ground values. Within 1 km of the smelter, sediments containing slag
from the smelter contain up to 10,000 ppm of arsenic and antimony. Both
wind and water distribute these metals from the copper smelter, but since
the tidal current patterns do not transport the slag in the direction
of Vashon Island, near Quartermaster Harbor, where 400 ppm of arsenic
and 100 ppm of antimony have been found in the soil, they are evidently
carried on the wind and settle out in that area. Arsenic to antimony
ratios in the smelter stack dust are approximately 10:1; in the slag,
about 1:1. However, since the ratio in sediments of Quartermaster Harbor
is between 5:1 and 10:1, the slag is evidently not the major source of
arsenic and antimony in the area.
Moderate tidal currents prevent the slag and the atmospheric particles
from accumulating in the bottom sediment between the smelter and Vashon
Island. Tidal currents transport the slag or dust to other area. In
"noncontaminated" muds of Puget Sound about 50% of the Sb and most of the
arsenic seems to be bound to extractable iron and aluminum compounds.
Extractions of two contaminated sediments near the smelter indicated that
under 20% of the arsenic and antimony is bound to extractable iron and
aluminum. Most of the antimony appears to be bound in a relatively chemi-
cally stable form (Crecelius, 1975).
In September 1974, a NASA (Cleveland) news release indicated the presence
of trace amounts of antimony, cadmium and other materials in Cleveland
air. The levels found were not considered high enough to endanger human
health. However, under contract to NASA, biologists from Central State
University, will conduct a study to determine the potential long-term
inhalation effects on rats of trace elements and compounds found in
Cleveland's air.
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A number of reports indicate that antimony is one of 30 or more trace
elements, which may be emitted during the coal burning process. A redent
study by the EPA National Fuels Surveillance Network found antimony among
the trace elements in gasoline and in commercial gasoline fuel additives.
Antimony, however, was not listed among the metallic elements (Ce, As,
V, Ni, and Cr) in gasoline that are considered to have suspected biolo-
gical toxicity (Jungers et^ al, 1975) .
In 1966, the National Air Sampling Network recorded minute amounts of
antimony in the air of cities and nonurban areas. Four of the 58 cities
and three of the 29 urban areas analyzed showed antimony to be present
in ranges of 0.042-0.085 yg/m3 for urban and 0.001-0.002 yg/m3 for non-
urban air.
Efforts to obtain comparable data for more recent years have been un-
successful. The National Air Sampling Network originally mailed filters
from their headquarters in Cincinnati, Ohio to the some 200 to 250
volunteer workers who exposed the samples for the prescribed time and
mailed them back. For some years after its relocation to Durham, N.C.
more than five years ago, no filters were analyzed. Since then, the
air sampling activity has become decentralized into the ten EPA regions
and, in many cases, into state ambient air monitoring networks. Although
each region operates to some extent differently from the others, there
is a general effort to cooperate with the work in Durham. Apparently,
the 1974 and 1975 data analysis will be worked on in order to be current.
There will then be an attempt to analyze samples received but not
analyzed during the years of relocation and reorganization. It appears
that although some regional offices are running analysis of metals on
filters, there are no antimony data being recorded by them at this time.
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III. HEALTH AND ENVIRONMENTAL EFFECTS
A. Environmental Effects
1. Persistence and Environmental Accumulation
Antimony is found infrequently in air. Measurements of antimony in the
atmosphere by the National Air Sampling Network in 1966 showed fair-
sized concentrations in only six samples from 4 of 58 cities and in
3 of 29 nonurban areas in Arizona, Arkansas and New Mexico. The range of
antimony concentrations reported in the four urban areas was 0.042-0.085
3 3
yg/m and in the three nonurban areas was 0.001-0.002 Pg/m (Schroeder, 1970a;
Woolrich, 1973). It is doubtful that such small amounts of antimony repre-
sent a hazard to human health.
Schroeder (1965, 1970) notes that the concentration of antimony as pre-
viously reported in the literature is 4 ppm in soil, 0.2 ppm (by weight)
in the earth's crust and 0.2 ppb (by weight) in sea water.
Evidence for persistence of antimony in soil.has been reported by
Crecelius et^ a_l (1974) who showed that surface soil (upper 3 cm) samples
obtained from sites 10 kilometers downwind of a Tacoma, Washington copper
smelter contained 8-204 ppm Sb (dry weight). These levels were well above
natural levels of antimony in soils from Puget Sound which were considered
by the authors to be approximately 3-5 ppm.
Booz-Allen (1972) estimated that 500,000 tons of solid waste (mine waste
and mill tailings) from the antimony industry had accumulated through
1968. This waste covered a 20-acre land area in Idaho.
In another instance (Maxfield et al, 1974), antimony was measured in a
concentration range of 270 to 900 ppm in the fine silt collected at the
mouth of northern Idaho's Coeur d'Alene river into which for over 80 years
large amounts of wastes from mining and smelting operations have been
discharged.
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2. Bioaccumulation
Schroeder (1970a) has estimated that the daily human intake of antimony
from air, utilizing the highest reported atmospheric concentration, is
1.7 yg maximum, while that from food and water is less than 100 yg, as
reported by Howells in 1968. Murthy et al (1971) calculated a higher
daily antimony consumption in a group of institutionalized children, ages
9-12, in 28 U.S. cities. The intake values determined in this study were
Q.247-1.275 mg Sb/day. These levels were based on a weighted average
antimony content in the diet, exclusive of drinking water, of 0.361
(0.209-0.500) mg/kg. The data indicated that the amount of antimony
ingested varied significantly from one sampling period to another and
from one institution to another.
Schroeder (1965, 1970) also reported the average value of antimony in the
human body as less than 90 mg/70-kg man or less than 1.3 ppm by weight
(using data from the ICRP Committee Report, 1960) and the total bodily con-
tent as 7.9 mg (according to a written communication from I.H. Tipton, 1970)
Several authors have analyzed human tissues for the quantitative determina-
tion of nonessential trace element content. In a paper by Brune et al
(1963), the mean concentration of antimony in one sample of normal human
whole blood was determined as 0.0044 (± 0.0021) yg/gm using a chemical
separation technique with ion-exchangers combined with gamma-spectrometric
analysis.
Radioactivation analyses of 45 samples of lung tissue obtained from adults
of both sexes who resided within the Glasgow, Scotland area and who ranged
in age from 40-70 years showed a mean concentration of 0.095 (± 0.105)
ppm Sb wet weight. The maximum and minimum concentrations of antimony in
these analyses were 0.452 and 0.007 ppm, respectively. The distribution
was found to be log normal. Samples of 15 lung pairs showed that the
mean concentration of antimony was more than twice as high at the apex
of each lung as it was at the base, a finding which suggested that the
source of the accumulated material was airborne dust (Molokhia and Smith,
1967). In 24 patients with pulmonary disease, Kennedy (1966) reported
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antimony concentrations ranging from <0.005 to 0.87 yg/gm lung tissue
analyzed by neutron activation analysis.
The study by Molokhia and Smith (1967) also showed that in 15 tissue
samples the visceral pleura contained a mean concentration of 0.037 ppm
Sb (wet weight) or about the same amount of antimony as the base of the
lung. In contrast, the antimony level in the trachea, pulmonary artery
and vein, and tongue was very low (0.006-0.007 ppm) compared to that in
lung tissue. The lymph glands analyzed contained 0.258-0.429 ppm Sb or
about five to ten times more antimony than average lung tissue. The right
hilar group was slightly higher in content than the left, and both were
well above the paratracheal group.
Two investigators have analyzed involved and uninvolved lung tissue from
patients with malignant pulmonary disease for antimony content by neutron
activation analysis. The study by Kennedy (1966) indicated that the con-
centration of antimony was not increased in the involved and uninvolved
lung of these patients in comparison to patients with nonmalignant pul-
monary disease. In the other study (Molokhia and Smith, 1967), the con-
centration of antimony in tumor tissue was significantly less than that
in the involved or uninvolved lung.
Human heart tissue obtained from autopsies of twenty victims of traumatic
accidents showed a median concentration of antimony of 0.0015 yg/g wet tis-
sue using neutron activation analysis. The range in concentration varied
from 0.001 to 0.004 yg. The victims, who came from Stockholm and sur-
roundings, ranged in age from 4 1/2 to 65 years. No significant dif-
ferences in antimony concentration with age or sex were observed (Wester, 1965a)
Neutron activation analyses for antimony content were conducted by Hock et al
(1975) on tissue samples from eight defined regions of six brains of humans
aged from 5 hours to 74 years. The data were expressed in terms of element
weight per unit dry tissue. The mean absolute antimony concentration in
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the cerebral cortex ranged from 0.25 to 17.07 x 10 g per g dried tissue.
The mean absolute Sb concentration in the basal ganglia ranged from
1.58 to 18.71 x 10~ g per gram dried tissue. The variation in concentra-
tion of nonessential elements including antimony in the different brain
regions was found to be greater than the corresponding variations in the
concentration of essential elements.
In a paper by Wester (1965b), four beef hearts, analyzed by neutron acti-
vation analysis, showed somewhat increased concentrations of antimony in
the conductive tissue. Comparatively lower Sb concentrations were ob-
tained in the ventricular septum than in the right atrium and conductive
tissue. The concentrations of antimony, expressed in yg/gm wet tissue,
ranged from 0.005 to 0.01 in the atrioventricular node, 0.003 to 0.01 in
the bundle of His, 0.002 to 0.008 in the atrial tissue and 0.0007 to
0.002 in the ventricular tissue.
3. Biological Degradation
No information was found
4. Chemical Degradation
Chemical reactions of antimony compounds in the environment are discussed
in Section II.C.7. The chemical degradation products of selected antimony
compounds are given in Table I, pp. 6-8. For example, antimony trichloride
reacts with water to form antimony trioxide and hydrochloric acid. The
oxide may react with bases (in soil) to form metal antimonites, while the
hydrochloric acid will form chloride salts. Analogous products are formed
from other antimony halides. Antimony pentasulfide reacts with water to
form hydrogen sulfide that may escape as a toxic gas, or react with
bases to form sulfide salts. Other degradation products shown in Table I
are non-toxic and of little interest.
5. Environmental Transport
Crecelius et al (1974) have reported that HiVol air filter dust samples
collected in Seattle 40 km downwind of a Tacoma, Washington copper smelter
often have extremely high concentrations of Sb (>300 ppm).
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B. Biological Effects
1. Toxicity and Clinical Studies in Man
a. Occupational Studies
Industrial exposure to dusts of antimony oxides has been linked with an
increased incidence of pneumoconiosis, with and without associated pul-
monary dysfunction, among smelter workers processing antimony ore in
France (LeGall, 1969), in England (McCallum, 1963, 1967, 1970), in the
U.S. (Cooper £t ja, 1968) and in Yugoslavia (Karajcvic, 1958),
LeGall has reported six to seven cases of pneumoconiosis in 41 workers
(15-17% incidence) which occurred during the 1960's in a French foundry
manufacturing antimony and antimony oxide from imported ores containing
1-20% silica. The pneumoconioses were diagnosed by X-rays which revealed
moderately dense reticulo-micronodular foci in all pulmonary fields.
Clinical signs were minimal and included cough and prolonged expiration;
pulmonary function studies revealed a deficit. Antimony was not detected
in the urine of four workers studied.
/
Concentrations of antimony in samples collected at the roasting furnace
3
and at the furnace in which the fine oxide was produced were 0.30 mg/m .
After prolonged sampling at a roasting furnace without ventilation, anti-
3
mony concentrations ranged from 3.4-1A.7 mg/m <". Particle counts conducted
in the mixing and roasting areas and in an area of furnace charging showed
innumerable particles 1 3 microns in size. Duration of exposure of the
affected individuals varied from 6 to 40 years. The authors commented
that at certain points the concentration of S0_ was repeatedly excessive
(10 times higher than the admissible level) and that the fume deposits
consisted of 3% quartz. Antimony was considered the principal causal
agent of the lung changes although the intervention of silica and SO.
was not denied.
Radiographic lung changes resembling the simple pneumoconiosis of coal
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workers (Category 1-3) were observed in 9% of a group of process workers
involved in the production of antimony oxide and pure metal from sulfide
ore in the UK (McCallum, 1963, 1967). These changes generally appeared
**
to be symptomless, although one worker with penumoconiosis also had a
clinical picture of chronic bronchitis with respiratory obstruction.
Examination of spot samples of urine from three men with lung changes
showed excretion of 425, 480 and 680 yg Sb/liter. One furnace worker
with pneumoconiosis, who retired from his job at the normal age of 65,
showed urinary antimony levels of 55 yg and 28 yg/liter 7 months and
4 years, respectively, after leaving work. There was no detectable
diminution in the lung changes over this period.
Skin irritation affecting particularly the forearms,thighs and flexures,
where there was presumably chafing from clothing, was reported in warm
weather. The condition, which was termed "antimony spots", consisted of
papules and pustules around sweat and sebaceous glands. These spots
disappeared rapidly over a weekend or holiday, but reappeared on return
to work.
The atmospheric concentration of antimony determined at 10 sampling points
3
in the area of the furnaces ranged from 0.53 to 5.34 mg/m on several
days during the three-week sampling period. All but three sampling points
3
showed concentrations greater than 2 mg/m . The highest concentration
was measured in the vicinity of the tapping operation at the metal furnace
3
where a concentration of 36.7 mg/m was monitored. The tapping operation
was said to last for a relatively short period.
A follow-up study was conducted in the same plant in 1965-1966, three
years after the original investigation (McCallum, 1967). In this survey,
a more comprehensive radiological investigation revealed 26 new cases
of antimony pneumoconiosis out of a total of 274 workers examined. Another
18 workers with the same condition were already under clinical observation
as outpatients. The total incidence of pneumoconiosis diagnosed in this
survey was 18%. The author commented that material for histological exa-
mination had been scarce. However, micropathological examination of
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sections from the lungs of an antimony worker who died from pulmonary
carcinoma revealed an accumulation of dust particles and dust-laden macro-
phages lying in alveolar septa and in perivascular tissue without fibrosis
or an inflammatory reaction.
X-ray spectrophotometry determinations of lung antimony content were
carried out on 113 men who had been employed for 6 months or more in the
antimony process (McCallum £t al, 1970). The values obtained ranged from
2
nil to just over 11 mg Sb/cm of lung area in one worker with a total of
35 years employment. There was a significant association between length
of employment and the amount of lung antimony, particularly when only
the first 20 years of employment was considered. Radiographic category
of pneumoconiosis was also directly associated with the mean period of
employment and the mean direct lung antimony measurement, although in
each category there was a wide variation in lung antimony content. Fore-
men and baghouse workers had higher median antimony levels than furnace
workers while laborers and other workers had the least lung antimony.
In the report by Cooper et_ al_ (1968) the results of a study of antimony
intoxication in a U.S. antimony refining plant in which workers were
exposed to both the dust from antimony ore and antimony trioxide were
presented. Pulmonary function studies were performed on 14 workers who
had been exposed to antimony trioxide for periods of 1-15 years out of
a total exposure population of 28 workers. These studies included vital
capacity, lung volumes, minute ventilation, tidal volume, mixing effi-
ciency, maximum-mid expiratory flow rates (MMEFR) forced expiratory volume
in 1 second (FEV ), maximum breathing capacity (MBC) and diffusing capacity.
Of those individuals with pulmonary function abnormalities, one had definite
small opacities, one had very early changes, and two had negative chest
roentgenograms. The remaining three subjects with either suspicious or
definite roentgenographic abnormalities all had normal pulmonary studies.
Electrocardiograms were also monitored in seven workers, three of whom
had antimony pneumoconiosis. Six of these seven workers showed normal
tracings while one worker showed slight bradycardia.
Spot samples of urine were analyzed for antimony content in two surveys
of 17 workers conducted in 1962 and in surveys of 15 workers conducted
in 1965-1966. The results of these surveys together with roentgen
-------
findings from 13 of 28 workers are presented in Tables XI and XII. Antimony
excretion appeared variable and without correlation to the roentgen findings.
The authors commented that only one urine sample contained a level of
antimony greater than the quoted "safe" concentration of 1 mg/liter,
suggested by H.B. Elkins in The Chemistry of Industrial Toxicology, 2nd Ed.,
John Wiley & Sons Inc., New York, 1959, p. 246.
TABLE XI
ANTIMONY IN URINT.
TABLE'XII
Patient
i
2
{
4
5
7
8
9
10
1 1
12
l.t
'4
'5
\li
17
IS
1
n.,<;
450
IS
tfs
7"
' 425
12
S
9
1''
5<,o
• 7
i ,020
•j-
> ^
"75
I, i'/>5
800
617 128
V>
448 78
400 . i f>7
107 290
545 Uy
21
12.7
,;.(; .
\4'i
Ml
'i'1
1 2
• / *
, Roentgen'
I'liiilings
*
313 Suspicious
*
Positive
70 Suspicious
415 Suspicious
74 Positive
*
*
Positive
Negative
*
Negative
*
*
*
*
*
Patient
10
20
.21
22
-,'i
=4
25
2f>
- /
28
AVIIMON'V IN I'RINK .
i.^g. i .000 ml.f
, 1 c/'ifi 1 c/ifi
1 II
118 7-2 7.35
—
20
14 llfi
17'' 7^7 o(-)
4.;
222
•; ;•;
O
o
Roentgen
hmlinL!s
Negative
*
*
*
Negative
Suspicious
Negative-
Suspicious
*
*
* No roentgenographic examination.
Source: Cooper et al, p. 499 (1968)
Copyright© 1968, Charles C. Thomas,
Publisher. Reprinted by permission
of Charles C. Thomas, Publisher.
* Nn rnfnfi,'cn!>>ir:iphir rx:imin:ition.
Atmospheric concentrations of antimony monitored in 1966 at 36 locations
in the plant under different environmental conditions ranged from 0.081 to
75 mg/m . The bagging operations were associated with the highest ambient
Sb levels. Concentrations of antimony monitored in the area of these
3
operations were 138 mg/m •
Karajovic (1958) reported that the pneumoconioses observed among smelting
plant workers involved in the production of pure antimony in Yugoslavia
was different in character and slower in onset than the pneumoconiotic
changes from the mixed dust silicosis observed in mine workers. The
smelting plant workers were exposed to a mixed dust containing 35.72-89.66%
antimony trioxide and 1.26-6.20% antimony pentoxide. Other contaminants
in the dust consisted of 1.12-11.50% total silicon, including 0.6-6.7%
free Si02, 1.70-4.02% Fe^ and 0.32-9.16% As^.
-87-
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Out of a total population (160) at risk, 101 smelting plant workers
underwent on-site clinical examination. These workers, who were
considered poorly nourished, were employed at the most dangerous
positions for periods of more than 3 years. In addition to being exposed
to considerable quantities of dust, they were also required to perform
heavy physical work at varying temperature. The majority complained of
slightly difficult breathing, fatigue at work, myalgia, light cough and
slight dyspeptic discomfort without pain or diarrhea. In the summer,
these workers complained of itching of the skin attended by rash.
Sixty-two of these 101 workers underwent radiographical examination of
the lungs. The results were as follows: no pathological findings in 31
cases, 17 cases of type 'x', 14 cases of Pn. simplex and no cases of Pn.
progressiva. Emphysema with bronchitis was established in 22 cases, in
8 of which the worker was under 40. The pneumoconiotic changes in these
workers were limited mainly to the middle and lower sections, and nu-
merous, small (0.5-1.5 mm) sharply defined spotty shadows predominated
giving the lung fields a gravelly appearance. Emphysema was localized
in the upper sections and directly above the bases. In contrast, the
X-ray picture of the lungs of miners affected with mixed silicosis showed
larger (> 3 mm), poorly defined and sparsely disseminated spotty shadows
which were especially numerous in the intraclavicular sections. Symptoms
of emphysema were localized chiefly in the lower sections.
Fifty-one of the 62 workers examined showed catarrhal symptoms in the
upper respiratory passages. There were 16 cases of devatio septi nasi,
4 cases of tuberculosis secondary fibrosa, 12 cases of conjunctivitis and
16 cases of antimony dermatosis. Thirteen of these 16 cases involved
workers at the reverbatory furnaces. The dermatosis was manifested by
vesicular varioliform effluorescences which underwent necrosis in the
center and left behind slight scars with hyperpigmentation.
Pulmonary ventilation function studies (vital capacity, expiratory reserve
volume, maximal ventilation volume determined by the Kennedy and Tiffeneau
tests) showed signs of slight insufficiency in 4 of 7 workers with
-88-
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pneumoconiosis and associated emphysema and no insufficiency in the re-
maining workers. EGG findings were normal in these workers although
5 workers exhibited hypertension.
Twenty of the original 101 workers examined underwent more detailed clini-
cal examination in the hospital. Serological reactions (WR, Kahn, Meinicke)
were positive in two workers; the SE, hemogram (Hb, RBC, L, Rtc, BPE, Heinz),
hepatogram and proteirtogram were normal. Using the method of Gutzeit,
no antimony was found in the blood or urine; however, three workers showed
antimony in the amount of 25 ug/liter urine with the polarograph method.
Gravimetric analysis (with electroprecipitator) of the work positions ex-
3
posed to dust yielded values of 16-248 mg/m , and konimetric analysis (with
thermoprecipitator) showed the presence of 2150-12,800 dust particles/cm .
The particle sizes were predominantly under 0.5 microns. The authors
commented they were unable to determine whether the clinical findings
represented silicoantimoniosis or an accumulation of dust resulting in
pseudonodulation.
Bulmer and Johnston (1948) reported no toxic effects in two workers aged
51 and 60 years handling antimony trisulfide in a laboratory for a period
of six weeks or one year. The compound, which was considered exceptionally
pure and which contained 0.18% lead and <0.07% arsenic, was being crushed,
ground and screened to a desired particle size. Respirators were apparently
provided but the authors commented that they were not used.
No subjective complaints were registered by the workers handling antimony
trisulfide. Hemoglobin determinations and differential counts of the two
exposed workers did not vary materially from those of another 8 workers
who had no appreciable antimony exposure. Chest films of both men did
not suggest dust effects nor was antimony detectable by a modification of
Bamford's method in two urine samples taken from both workers. The anti-
mony content of urine samples from 6 other workers with no appreciable
exposure was also negligible.
-89-
-------
Atmospheric samples obtained between the furnace and screening machine,
and at the delivery end of the screening machine contained 42.0 mg and
3
52.0 mg antimony trisulfide/m , respectively. These concentrations we
said to be typical of the general exposure during processing.
The authors concluded that poor absorption of antimony trisulfide dust
of the particle size (unspecified) encountered in this study accounted
for the low toxicity observed.
In contrast, Brieger ^t al^ (1954) reported an increased incidence of
cardiovascular changes and ulcer among employees in a plant of the abra-
sives industry where resinoid grinding wheels were manufactured from
phenol formaldehyde resins and antimony trisulfide. The population at
risk consisted of 125 workmen who were exposed for periods of 8 months
to 2 years. During the exposure period, six employees died suddenly,
in addition to two other employees who died of chronic heart disease.
Four of the decedents were under 45 years of age. No autopsies were
performed, but in all but one case heart disease was implicated.
Since an occupational factor was suspected, a clinical examination was
conducted on 113 employees. Of all men examined, 14 had a blood pressure
of over 150/90 mm while 24 had a blood pressure of under 110/70 mm.
Thirty-seven of 75 workers examined showed changes in the electrocardiogram,
mostly of the T wave, which were considered significant. An X-ray study
was also conducted since a large number of employees complained about
GI disturbances. The study revealed an incidence of ulcer in 7 of 111
workers examined (63/1000) compared to 59 known cases of ulcer in the
total plant population of 3912 (15/1000). Urine samples collected at
random and examined by a procedure adapted from Frederick's method con-
tained 0.8-9.6 mg antimony/liter.
Air tests using Frederick's method revealed the presence of 0.58-5.55 mg
3 3
antimony trisulfide/m with the majority of findings over 3.0 mg/m .
After the use of antimony trisulfide was abandoned, no further deaths
-90-
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from heart disease or abnormal increase in cardiovascular disorders were
observed for several years. However, EGG changes in 12 of 56 reexamined
employees showed a tendency to persist.
Taylor (1966) described an episode of acute antimony intoxication in 7 men
after exposure to fumes containing antimony trichloride. The source of
antimony exposure was leaking pumps from an enclosed process in which
antimony trichloride was circulated at a high temperature and pressure as
a 98% solution in anhydrous hydrochloric acid.
All seven workers suffered upper respiratory tract irritation which was
attributed to hydrochloric acid. In addition, five of the men developed
gastrointestinal disturbances including abdominal pain and persistent
anorexia. These symptoms were slightly delayed in onset and were attri-
buted to the systemic action of antimony. Routine blood counts including
hemoglobin estimations and white cell counts were normal in four workers.
Chest radiographs of all seven workers were also normal.
Urinary antimony analyses revealed a concentration in excess of 1 ing/liter
in 5 of 7 exposed men,one or two days after exposure. The highest urine
antimony concentration observed was 5.1 mg/liter in one subject two days
after exposure. Intermittent analyses conducted on subsequent days showed
a rapid fall in urine antimony content suggesting that urinary excretion
of this element is relatively quick.
Subsequent environmental measurements taken 3 feet downwind from the
leaking pump suggested that these workers were briefly exposed to an
3 3
atmosphere containing up to 146 mg HCl/m and 73 mg Sb/m .
A higher than expected rate of cancer of the respiratory tract in uranium
workers of the Colorado Plateau was attributed to radioactivity in the
mines. To determine if mining exposures other than radioactivity may
have contributed to the genesis of the cancer, the mortality rates of
1759 miners exposed to low radiation levels were examined. Two cohort
-91-
-------
groups were studied. The 908 men in Cohort 1 had completed 15 years of
mine work before 1 January 1937, the 851 in Cohort 2 had completed 15 years
from 1 January 1937 through 31 December 1948. Both cohorts showed excess
mortality from lung and heart diseases. In Cohort 1, there was a three-
fold increase in cancer of the respiratory system. Cohort 2 showed a
statistically significant excess of cancers of the digestive system. Each
cohort experienced an excess of cancers involving all systems other than
the digestive and respiratory systems.
No obvious explanation could be drawn, except that a carcinogen was prob-
ably admixed in the air of the mines. The ore from the mines contained
silica plus (in order of diminishing quantities) sulfur, iron, copper,
zinc, manganese, lead, arsenic, calcium, fluorine, antimony, and silver.
Of these, only iron and arsenic were considered suspect occupational lung
carcinogens. Nickel was present only as a trace element; chromium and
asbestos were not detected (Wagoner et al^, 1963)
b. Epidemiology
No epidemiological studies were found in the literature reviewed.
c. Metabolic Effects Studies
Abdallah and Saif (1962) studied the effect of dosage route and regimen
on the excretion rate and tissue deposition of sodium antimony dimercapto-
succinate in a group of Egyptian patients. Five groups of patients with
124
five males each were given single doses of Sb-sodium antimony dimer-
captosuccinate at levels of 75, 100 or 125 rug Sb intramuscularly, or 75
or 100 mg Sb intravenously. These doses corresponded to an average con-
centration of 1.4, 1.7, or 2.1 mg Sb/kg body weight. Concentrations of
Sb were monitored in whole blood and urine using a scintillation
counter, and in the liver, heart and thyroid by surface body scanning with
a scintillation probe.
-92-
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The results of analyses for urinary excretion of antimony are presented
in Table XIII.
TABLE XIII
EXCRIitlON OF ANTIMONY IN URINE IN FIRST 24 HOURS AH lilt A SINGH; DOSli Of
SODIUM ANTIMONY DIMtRCAPTOSUCClNATl:
Source; Abdallah and
u^rs . • Saif, p. 291 (1962)-
D,w o-t 0-2 0-3 0-4 0-5 0-24 Copyright © 1962, Little,
<""'rt""t> Brown and Company. Re-
75 mg. mg. Sb 3-75 7-75 10-5 12-25 n 16-75 printed by permission of
'•'"• % 5 10-3 14 irt-.j 17-3 ^-4 Little Brown and Company
i.ni- /o 4'25 15-75 iS-j 19-25 jo 24-25
125 nig. mg. Sb 9-25 20-50 25-25 27-75 -') 35-75 Foundation, Churchill
i.m. '•;;, 7-4 ,6-4 20-2 --2. 23-2 *.(,' Press (London) and
75 mg. mg. Sb 15-75 23-25 24 29
i.v. % 21 31 32 38; 6
100 mg. mg. Sb 23-5 31-75 33-5 315-25
'•v- % -3'5 .U'75 33'5 3<"'-25
Dr. A. Abdallah
The urinary excretion of antimony was rather rapid during the first few
hours, whether the drug was administered intravenously or intramuscularly.
The total amount of antimony excreted in 24 hours increased with larger
doses administered by either route. However, with similar single doses,
larger amounts were excreted during the first 24 hours when the drug was
administered intravenously. Long-term follow-up showed that with single
intramuscular injections of 75, 100 and 125 mg Sb half the administered
dose was excreted in the urine within 26, 15 and 7 days, respectively.
With intravenous administration of 75 and 125 mg Sb, the 50% excretion
level was attained on the 5th and 4th day respectively. Successive
doses of antimony given intramuscularly or intravenously once weekly
resulted in a more rapid initial excretion rate with an increase in the
individual repeated dose, but only to a certain limit, after which any
further increase was accompanied by a phase of relatively delayed urinary
excretion.
Individual doses of 50 mg Sb (average 1 mg/kg body weight) were also ad-
ministered every other day, intravenously or intramuscularly, for a total
of five doses. With intramuscular injection, the urinary excretion rate
was rather steady and 50% of the total dose administered was excreted
-93-
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within 30 days from the start of the treatment. In contrast, there was
an initial rapid rise in excretion rate with intravenous therapy during
the period of administration of the doses which was followed by a rela-
tively slower excretion rate. Fifty percent of the total dose could not
be recovered in the urine in 34 days.
With single intramuscular doses, the initial maximum level of antimony
in the blood Was attained within one hour after injection. This level
had no correlation with the size of the administered dose. Another peak
also occurred 2, 3 or 4 hours later. The timing of this second peak was
apparently related to the decrease in blood concentration after the ini-
tial peak which it directly followed. The larger the individual dose, the
less apparent was the decrease in the initial concentration of antimony in
the blood in the first 5 hours. During the follow-up period of 28-50 days,
there were minor transient elevations in the Sb concentration in the blood
which did not represent any basal or critical level. With intravenous
injections, a maximum level was attained in the blood within fifteen
minutes after injection. This level did not appear to be correlated with
the size of the administered dose. The maximum level was followed by a
steep, then a steady step-wise decrease; no secondary peaks were observed.
With repeated doses, blood antimony levels were estimated one hour after
intravenous injection and two hours after intramuscular injections. There
was usually a tendency for the antimony blood levels accompanying suc-
cessive doses not to exceed or even approach the average peaks attained
by the first dose. Any intermittent rise was usually concommitant with
a change in gradient of the excretion rate. Whenever the excretion rate
changed to a slower gradient, the blood level rose then subsequently
decreased.
Organ retention of antimony was studied in one patient who received a
single intravenous dose of. 100 rag Sb and who was followed for a period of
23 days. The largest uptake of antimony occurred in the liver followed
by the thyroid and then the heart. The highest Sb level was attained in
the liver and in the heart on the second day, whereas the thyroid had the
-94-
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maximum concentration on the first day. Elimination of antimony from the
liver occurred rapidly, and markedly decreased around the llth day, when
it became approximately equal to the highest concentrations attained in
the heart or the.thyroid. Elimination of antimony from the heart appeared
to occur in shifts during the first week. Around the 10th day, concentra-
tion in the heart was higher than that in the thyroid. It then became
lower until the end of the follow-up period. In contrast, the retention
in the liver increased in amounts with repeated doses of 100 mg Sb ad-
ministered in three equal doses intramuscularly over a period of nine
days.
EGG changes in Egyptian adults, adolescents and children treated for
schistosomiasis with antimony dimercaptosuccinate (TWSb) have been reported
by Abdallah and Badran (1963) and Davis (1961). In the paper by Abdallah
and Badran, the course of treatment consisted of five daily intramuscular
injections of 6 mg TWSb/kg body weight (total dose 30 mg/kg or about
7.5 mg Sb/kg) administered to 25 adult patients with normal electrocardio-
gram prior to treatment. ECGs were monitored after the completion of the
treatment course. In five patients,ECGs were also performed half an hour
after the first injection and after the third and fourth injections.
In seven of 25 patients, there was a significant increase in heart rate
of 40 beats/minute or more. Only one patient showed tachycardia above
100 beats/minute. There was also a significant decrease in heart rate
in four patients, but none of these showed a rate slower than 60 beats/minute.
No changes in rhythm occurred.
There was a diminution in amplitude of the P wave, ranging between 25-50%
of the original amplitude, in twelve patients. In two patients there was
a prolongation of the PR interval to less than 25% of the original inter-
val. There was a significant decrease in PR interval in four patients.
A decrease in the amplitude of the QRS complex, ranging between 10 and 40%
of the original amplitude, occurred in 10 patients. In one patient there
-95-
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was an increase in amplitude of the QRS complex of 33%. Prolongation of
the QRS interval of 20-35% of the original duration was noted in four
patients.
In three patients there was a slight depression of the ST segment. A
variable degree of changes in T wave occurred in 24 patients. In three of
these patients the change consisted only in diminution of amplitude. In
21 patients there was inversion of the T wave in two to twelve leads. The
T wave inversion was most common in leads III and avf. Prolongation of
the Q-T interval not exceeding 25% of the original interval occurred in
10 patients.
A review of electrocardiograms showed that the changes were not due to acute
effect of TWSb as there was no change immediately or up to two hours
after the first injection. The effect of the drug on the myocardium was
cumulative since it started after the third dose and was more marked
after the 4th and 5th doses. Electrocardiograms reverted back to normal
within four to six weeks.
In the report by Davis (1961), 19 male African children or adolescents,
aged 11-20 years, weighing 26-57 kg, and with Schistosoma mansoni, S^.
haematobium or double infections, were treated with antimony dimercapto-
succinate intravenously. The total dosage ranged from 1.0 gm in 5 days
to 2.0 gm in three days. Electrocardiograms were monitored before treat-
ment, daily during treatment and for the first two or three days after
treatment.
All patients showed inverted T waves in one or more leads following
treatment. Those fifteen patients who had iso-electric or inverted
T waves before treatment showed the onset of frank inversion or an increase
in the amplitude of inversion following treatment. Inversion commenced
at different times during treatment, bore no relation to the amount of
antimony administered but was of maximal amplitude on the last day of
treatment or during the first three days after treatment. Inversion was
maximal in extent and amplitude in the right unipolar precordial leads.
-96-
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Follow-up ECGs showed no abnormality in one case at 18 days, persistent
abnormality in 7 of 12 cases at 28 to 33 days and in 2 of 5 cases at 54
days after treatment. This abnormality consisted of either persistent
inversion of the T wave in the right unipolar precordial leads or the
failure to regain their amplitude before treatment.
Prolongation of the QT interval was noted in nine of nineteen series of
recordings. This change appeared on the last day of treatment or during
the first three days after treatment. It was transitory, lasting about
2 days before reverting to normal.
The authors commented that the T wave inversion noted before treatment
occurs among Africans of all ages and is a common finding among children.
The changes observed following treatment did not differ from those pre-
viously described with the use of other therapeutic trivalent antimonials.
The time of occurrence of maximal EGG change and the fact that the changes
were largely reversible over a period of weeks, which roughly paralleled
the excretion rate of residual antimony, indirectly supported the concept
that the temporary myocardial damage resulted from accumulation of toxic
trivalent antimony.
Abdallah and Badran (1963) noted that the recommended course of treatment
with antimony dimercaptosuccinate (TWSb) produced more market electro-
cardiographic changes than the course of treatment with potassiura antimony
tartrate (tartar emetic), another trivalent antimony compound. (Abdallah
and Badran, 1961). In the latter study, 20 Egyptian males with schisto-
somiasis and aged 14 to 45 years were administered 1 grain per 30 kg body
weight intravenously every other day for a total of 12 treatments. The
EGG changes produced with both compounds are summarized in Table XIV.
It is apparent from the table that P wave changes and changes in PR
interval were more frequent following treatment with TWSb. While there
was no change in duration of the QRS complex with tartar emetic, a pro-
longation occurred in 16% of the cases receiving TWSb. ST segment de-
pression, not found with tartar emetic, occurred in 12% of the cases
treated with TWSb. T wave changes occurred slightly more frequently
with TWSb and the intensity of these changes were definitely greater
with this compound. Inversion of the T wave in more than six leads
-97-
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occurred in 10% of the cases receiving tartar emetic and in 32% of those
receiving TWSb. .
TABLE XIV
Comparison of clectrocardiographic changes in
tartar emetic and TWSb
Rate
P wave amp
PH interval
QKS amplitude
QRS duration
£T segment
T wave
Diminifthetl Ampli-
tude
Chtnfe
Increase
Decrease
Increase
Decrease
Increase
Decrease
Increase
Decrease
Increase
Decrease
Depression
Tartar
emetic
%
46
15
—
40
5
5
15
50
—
-
-
W
•JO
rwsb
%
44
36
—
48
8
16
4
•10
in
12
06
Source; Abdallah and Badran, p. 191
(1963). Copyright© 1963, The
American Journal of Tropical Medicine
and Hygiene. Reprinted by permission
of The American Journal of Tropical
Medicine and Hygiene
Invention 1 to 2 | | 32
lends I 25
Invention 'A to (i
leads
Invention more than ! 10 32
I) Iradu i I
Q-T interval prolnniia- , 50 : 40
I lion j '
Abnormal electrocardiograms have also been reported in groups of patients
with schistosomiasis following treatment with an intensive course of
sodium antimony bis(pyrocatechol-2,4-disulfonate), another trivalent
antimonial (O'Brien, 1959 and Zaki, 1955). In the paper by Zaki, 25
Egyptian patients received injections of the compound as a 6.3% aqueous
solution twice daily for four days. Five ml (42.5 mg Sb) were administered
per 60 kg body weight. The total dosage contained 340 mg antimony. EGG
tracings were performed before and one hour after each injection.
After the third or fourth injection, electrocardiogram changes usually
began to appear. TI and T4 become smaller in amplitude. These changes
were progressive during the course of treatment and became more progressive
in the few days immediately after the treatment course. In some cases
changes in the ST segment in L4 were found. This finding was observed
after the fifth injection. The changes in the ST segment were always in
the form of elevation above the usual level.
-98-
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In the report by O'Brien (1959), young, well-nourished West African
soldiers with schistosomiasis received an intensive course of treatment
with sodium antimony bis(pyrocatechol-2,4-disulfonate). A total of 95 ml
of the drug was administered intravenously over a period of 20 days.
After initial graded doses, five ml (42.5 mg Sb) were given daily. The
total dose of antimony was 807.5 mg.
During the course of treatment, one man developed multiple Stokes-Adams
attacks which were shown to be due to gross ventricular dysrhythmia by
electrocardiogram. The patient recovered completely after administration
of BAL (British Anti-Lewisite). Electrocardiograms recorded towards the
end of the course of treatment showed abnormalities in all 20 cases. The
abnormalities were remarkably constant and consisted of an elevation of
the ST segment followed by a sharp inversion of the T wave in the right
ventricular unipolar precordial leads. The T wave inversion sometimes
extended over into the left ventricular leads. These changes were con-
sidered those of underlying heart muscle damage, apparently of a tempo-
rary nature, since the EGG recordings three months later were normal.
Other toxic side effects of antimony administration such as anorexia,
nausea, vomiting, substernal constriction and dyspnea were also recorded.
Sapire and Silverman (1970) have classified EGG changes noted following
treatment with antimonials according to severity. These authors and
Woodruff (1969) have commented that the relationship of dosage to EGG
changes is unclear. Individual hypersensitivity to antimony and the type
of antimonial used are considered more important factors than the total
dose of antimony administered. In fact, the severest EGG changes have
been found to occur with the smallest doses.
No reports were available on EGG changes occurring after administration
of pentavalent antimonials. Davis (1961) has noted that electrocardio-
graph changes following treatment with pentavalent antimony compounds
are much less severe than with trivalent compounds, since the latter are
eliminated only slowly by the kidney. Pentavalent antimonials, in contrast,
are metabolized by the liver and are excreted more rapidly (Sapire and
Silverman, 1970)
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d. Poisoning Incidents and Case Histories
Sapire and Silverman (1970) have reported a case of severe myoc'ardial
involvement in a 10-year old Bantu who was being treated for a urinary
schiatosomiasis. This patient was inadvertently given an overdose of
sodium antimonyl gluconate in a dose of 300 mg daily for six days. After
completion of the course of treatment, the patient suddenly began to
convulse and severe vomiting ensued. During the convulsions, the heart
rate was found to be rapid and irregular and the pulse became feeble and
irregular. The EGG showed multiple ventricular extrasystoles with runs
of paroxysmal ventricular tachycardia. The diagnosis of acute antimony
poisoning with cardiotoxicity was made, the convulsions being due to
Stokes-Adams attacks associated with the paroxysmal ventricular tachy-
cardia. After initiation of chemotherapy, the EGG findings persisted
for 48 hours although to a markedly reduced degree, whereafter the patient
reverted to sinus rhythm. Subsequently his condition improved rapidly.
The authors noted that the principal effects appeared in the ST segment
and in the T wave with only occasional changes in the QRS axis being
noted.
Woodruff (1969) has reported the autopsy results of a Nigerian patient
who died following treatment with a standard course of sodium antimony
tartrate. The total dosage of drug was 1.38 gm. Autopsy findings re-
vealed an infarct of the posterior portion of the interventricular sep-
tum, with widely patent healthy coronary arteries. The infarct was inter-
preted as a result of transient coronary artery spasm, a pathology which
was in accord with the observed EGG changes in other patients.
Cordasco and Stone (1973) have reported a case of acute antimony intoxi-
cation in a 39-year old man exposed to an undisclosed amount of antimony
pentachloride following a gas leak from a reactor. The man suffered
second and third degree burns over most of his body. Twenty-four hours
after admission he became acutely ill with respiratory distress. Examina-
tion of the chest revealed marked moist rales in both basal and mid-lung
fields. His condition gradually worsened, with the development of pul-
monary edema and persistent progressive respiratory distress. At approxi-
mately six weeks postexposure, respiratory acidosis ensued. Subsequently
the patient improved following long-term intensive respiratory care and
repeated subglottic and tracheal dilatation.
-100-
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2. Effects on Mammals
a. Absorption, Excretion and Tissue Distribution Studies
(1) Absorption and Excretion
Waitz et_ al (1965) have studied the excretion of a trivalent antimonial,
tartar emetic, in mice and rats. Fourteen groups of 10 female Spartan or
124
Carworth CF-1 mice were given a single oral dose of Sb-labeled tartar
emetic at a level of 8, 16 or 32 mg Sb/kg. Antimony levels in the urine
and feces were determined at 1, 5 and 25 hours after treatment by scintil-
lation counting. The results, presented in Table XV show that the con-
centrations in the feces were always greater than in the urine. This
finding probably indicates incomplete absorption from the GI tract al-
though biliary excretion was not ruled out.
TABLE XV
ANTIMONY LEVELS IN URINE AND FAECES OF MICE AFTER A SINGLE ORAL DOSE OF TARTAR
EMETIC
D
Mice"
Normal
Normal
Normal
Infected
Normal
Normal
Normal
Normal
Normal
Normal
ose (mg/kg;
Sb
8.8
8.8
8.8
8.8
17
17
Collection
time
(hours)
0-1
0-5
0-25
0-5
0-1
0-5
17 0-25
37.7
37.7
37.7
0-1
0-5
0-25
Urine
CO Sb
0.3
12.5
169.0
0.5
1.5
56.9
216.0
0.1
38.7
429.0
% of dot*
0.01
0.6
7.9
0.05
0.04
1.4
5.3
0
0.4
4.6
Faeces
MO Sb
0.8
88.7
940.0
35.5
4.2
197.0
1804.0
10.7
95.7
1 827.0
% of dose
0.04
4.3
43.7
3.3
0.1
4.7
44.0
0.1
1.0
19.7
Total excreted
pg Sb
1.1
101.0
1 109.0
36.0
5.7
254.0
2 020.0
10.8
134.0
2 256.0
% of dose
0.05
4.9
51.6
3.4
0.1
6.1
49.3
0.1
1.4
24.3
" 10 mice per group.
Source; Waitz £t al, p. 538 (1965). Copyright© 1965, World Health
Organization. Reprinted by permission of the World Health Organi-
zation, Dr. J. Allan Waitz and Dr. R.E. Ober
-101-
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Wan-chu et al (1959) studied the gastrointestinal absorption and biliary
.excretion of antimonyl quinine hydrochloride, a trivalent antimonial,
after oral administration in rats. Following treatment, antimony disap-
peared very slowly from the GI tract with about 90% of the administered
Sb remaining after 8 hours. When the tract was ligated between the duo-
denum and pylorus prior to treatment, large amounts of antimony could be
recovered from the intestinal tract within a few hours. The bile also
contained antimony a few minutes after treatment. Sb excretion occurred
mainly in the feces with less than 1% present in the urine.
124
In contrast, a large proportion of a dose of Sb labeled tartar emetic
was excreted in the urine of rats following intravenous administration.
Six pairs of male Holtzman strain rats weighing approximately 200 gm were
injected with 2.2 mg Sb (approximately 11 mg Sb/kg). Urinalysis for
antimony content at 0.5, 2, 4, 8, 24 and 72 hours after treatment re-
vealed a rapid urinary excretion with 73% of the dose being eliminated
within the first 24 hours. Fecal excretion was 5.9% in 72 hours with
less than 1% excreted in any of the time periods between 0 and 24 hours
(Waitz et al, 1965).
Felicetti e£ al^ (1974a) have indicated a low gastrointestinal absorp-
tion of trivalent antimony in studies in hamsters. The radioactive
labeled antimony used in this study was generated from a starting solu-
124
tion of Sb-tartrate complex. Following oral administration to four
hamsters, antimony was retained with a half-life of less than one. day.
The two animals that received the larger amounts of the trivalent:
compound retained 15% and 19% of their initial body burdens on day 4, of
which 88% and 90%, respectively, were found in the GI tract. Low GI
absorption was also indicated in experiments with the pentavalent compound.
-102-
-------
The same authors studied the relative excretion of trivalent and penta-
124
valent aersols of Sb-tartrate following inhalation in hamsters. Both
124
aerosols were generated from a starting solution of Sb-tartrate complex
°
and passed through a heating column at 100 C before introduction into the
exposure chamber. The mean aerodynamic diameters of both aerosols were
1.6 microns with a geometric standard deviation of 1.7. Both exposures
were "nose only". Urine and feces samples were collected for 32 days
from seven hamsters in the pentavalent group and from seven animals for
15 days and five animals for 32 days in the trivalent group. Excreta
124
were analyzed for Sb content using deep-well liquid scintillation
detectors.
No statistically significant differences in the excretion patterns were
observed between the two aerosol groups. The inhaled trivalent and penta-
valent antimony were excreted both in the urine and feces. In the early
collections, more excreta activity was present in the feces than in the
urine. The authors considered that upper respiratory tract clearance
probably accounted for some fecal antimony in both cases.
Felicetti £t al (1974b) have also studied the excretion of inhaled 124Sb
in the beagle dog as a function of temperature of aerosol formation. In
this study three adult beagle dogs of approximately 15 months of age
124
were exposed to aerosols generated from a Sb-tartrate complex and
passed through a heating column maintained at 100, 500, or 1000°C. The
resulting particles had activity median aerodynamic diameters of 1.3
1.0 and 0.3 microns, with respective o s of 1.6, 1.6 and 1.3. The dogs
9
were anesthetized with pentobarbitol. The exposures were of a "head-only"
type. Urine and feces collections were made on three dogs, one at each
temperature of aerosol generation,for 32 days postexposure. Samples were
analyzed in a deep-well liquid scintillation counter.
-103-
-------
124
At least seven times as much Sb was excreted in the urine than in
the feces over the first 24 hours with the 100°C aerosol. In comparison,
a urine to feces ratio of 0.4 over the same period was obtained for the
500°C aerosol. From day 2 through day 32, however, the relative compart-
mentalization between the urine and feces for all three aerosols was
statistically the same. The mean urine to feces ratio for all the data
combined was 0.81 over this period, indicating a relatively greater ex-
cretion in the feces.
The effect of pretreatment on the excretion pattern of subsequent doses
1 r\ i
of Sb-labeled potassium antimony tartrate was investigated by Girgis et aJL
(1965) in mice. Male, albino mice of a homogeneous stock, 8 weeks in age
and weighing about 25 gm, were administered tartar emetic intraperitoneally.
In the first series of experiments, the test groups received 35 mg/kg of
124
unlabeled compound followed by 35 mg/kg of Sb-labeled tartar emetic,
124
whereas the control group received 35 mg/kg of Sb-labeled drug. In
the second series, the test group received 35 mg/kg of unlabeled tartar
124
emetic followed by 70 mg/kg of Sb-labeled drug, whereas the control
124
group received only 70 mg/kg of Sb-labeled drug. Urine and feces were
collected during the five hour period after treatment with labeled
compound and analyzed using a scintillation counter.
124
In the first series, excretion of Sb over the five-hour interval was
erratic, but fecal excretion in the test group greatly exceeded that of
the control group and amounted to 17% of the dose. In contrast, urinary
excretion of antimony was much higher in the test group in the second
series and consisted of 37.2% of the administered dose. The fecal ex-
cretion was again found to be increased, although in some cases no feces
were passed.
(2) Blood
124
The relationship between a single oral dose of Sb-labeled tartar emetic
and antimony blood levels in mice has been studied by Waitz ej^ a^L (1965).
The experimental procedure was described earlier (p. 101). The amount of
-104-
-------
antimony in the blood 1, 5 and 25 hours after treatment was linearly
related to the dose administered, and decreased both linearly and quadra-
tically with time. A significant interaction was found between dose and
time. Blood antimony levels were not significantly different in normal
and infected (with a Puerto Rican strain of S^. mansoni) mice.
Data from blood samples in rats injected intravenously with 2.2 mg Sb
i oy
(approximately 11 mg Sb/kg) as Sb-labeled tartar emetic showed a rapid
decline in antimony levels following treatment, a finding which supported
the excretion data described previously (p. 102) (Waitz e_t al_, 1965).
Banner (1954) has studied the localization of antimony in the red cell
fraction of rat blood. One male albino Wistar rat, weighing 386 gm, was
administered 1.2 ml of dilute solution of labeled antimony catechol di-
sulfonate complex (Fuadin) in 0.9% NaCl intravenously and sacrificed
after 10 days. A sample of blood was defribinated and centrifuged and
the hemoglobin isolated. The activity of the hemoglobin fraction was
sufficient to account for all the activity in the defribinated blood.
The author theorized that antimony was attached to the globin portion
of the hemoglobin, since hemin isolated from pooled blood of ten rats,
which had received intravenous injections of Fuadin 8 days previously,
showed low radioactivity counts.
Waitz e_t al (1965) also studied antimony blood levels in monkeys follow-
124
ing a single oral or intravenous dose of Sb-labeled tartar emetic. The
oral dose was administered at a level of 8 mg Sb/kg to five Rhesus female
monkeys weighing 2-3 kg. Blood samples were analyzed for antimony at
intervals of 0.5-144 hours following treatment. Average peak blood levels
of 0.175-0.180 pg Sb/ml were generally obtained 6-8 hours after dosing
and individual values were as high as 0.25 yg/ml. Low but detectable
blood levels of antimony were found 96-144 hours after dosing. The
authors commented that these findings were in good agreement with the
long period of urinary excretion of an intravenous dose in man.
Following intravenous injection of 1.28 mg Sb/kg to three monkeys, samples
-105-
-------
were taken at 0.25, 0.5, 1, 2, 4, 8 and 24 hours for blood antimony analy-
ses. In all monkeys, blood antimony dropped rapidly from a high of 1.25-
1.9 yg/ml at 0.25 hours, to 0.2-0.25 yg/ral at 8 hours, and to 0.1-0.2 yg/rol
at 24 hours. The blood antimony curve in these studies was considered
very similar to that described in man.
Blood antimony levels in mice and beagle dogs following inhalation of
1 O /
Sb aerosols generated at various temperatures has been studied. In
the first study (Thomas ejt al., 1973), three groups of 48 female Charles
River CD-I strain mice, 35 days of age, were exposed to aerosols generated
1 1 /
from a Sb-tartrate complex passed through a heating column maintained at
100, 500, or 1100°C. The respective mean aerodynamic diameters of the
particles generated were 1.6, 0.7 and 0.3 with as of 1.9, 1.8 and 1.3,
y
respectively. The exposures, which were about 10 minutes in duration,
were of a "head-only" type. Whole blood samples at 2 days postexposure
gave values of 0.43% of the adjusted body burden per ml for the 100°
aerosol, 1.2% per ml at 500° and 1.0% per ml at 1100°. All values were
essentially the same at 4 days postexposure.
Felicetti et al (1974b) exposed dogs In a similar manner (described
previously, p. 103), and a differential concentration of l^Sb in the RBC,
compared to the plasma, was maintained for the entire 21 days of sampling.
-» r\ i
Ratios of RBC to plasma Sb were generally similar for all aerosols,
with the possible exception of a lower ratio at 100° during the first 24
•I r\ I
hours. Beyond one day postexposure, the RBC concentrated Sb by an
average of 6.7 times that in the plasma throughout the sampling period.
The relative distribution of blood antimony between RBC and plasma follow-
ing inhalation of the trivalent and pentavalent aerosols has been studied
in hamsters (Felicetti et^ al, 1974a). The experimental procedure has been
described previously. Blood samples were obtained at 0, 1, 2, 5 and 8
days postexposure from at least one animal per group by heart puncture.
Distribution of blood antimony between RBC and plasma differed with the
two valence states at early sacrifice times. Trivalent antimony concentra-
-106-
-------
ted in the RBCs at all sacrifice times with maximum concentrations of 6 to
10 times plasma levels on day 1 postexposure (approximately 24 hours).
The pentavalent antimony group had plasma levels of about 3 times as great
as the RBC levels at 2 hours postexposure, although antimony was.concentra-
ted in the RBCs 24 hrs postexposure. After the day 1 sacrifice, activity
ratios from the two groups were similar. The "activity half-times in RBCs
were only a few days. The authors commented that establishment of a
concentration gradient in the pentavalent group at 24 hours postexposure
could have reflected some reduction to trivalent antimony in the blood and
subsequent accumulation in the RBC.
The effect of pretreatment on blood antimony levels of subsequent doses
of l^Sb-labeled potassium antimony tartrate was investigated by Girgis
et al. (1965) in mice. The experimental procedure was described previously
124
(p. 104). In the first series of experiments, the concentration of Sb
in the blood in animals which received a second dose of 35 rag/kg of labeled
tarter emetic was similar to that of the control animals,. When the second
dosage was increased to 70 rag/kg, the blood antimony levels in the test
group were found to be about 1/4 those in the control group. This differ-
ence was statistically significant.
(3) Whole-Body Retention And Tissue Distribution
Waitz et_ al^ (1965) measured concentrations of antimony in the liver of
normal mice or mice infected with a Puerto Rican strain of j>_. mansoni
following single or repeated oral doses of Sb-labeled tartar emetic.
The experimental procedure was described before (p. 101). Following a
single oral dose in normal mice, the amount of antimony in the liver was
found to increase linearly with the administered dose and quadratically
with time. There was a significant interaction between time and dose
which indicated that the relationship between liver antimony levels and
dose was not the same at 1, 5 and 25 hours after treatment. Normal mice
had significantly higher concentrations of antimony in the liver than
infected mice. Antimony levels in the liver of 5 groups of infected mice
given oral doses of 16 mg Sb/kg once daily for 2,4, 6, 8 or 10 days were
reasonably uniform from day to day and showed no persistent accumulation
of the drug.
-107-
-------
Molokhia and Smith (1969a) studied the tissue distribution of antimony in
mice following a single intraperitoneal injection of tartar emetic or TWSb
(identified by the authors as sodium antimony 2,3-mesodimercaptosuccinate;
Astiban). BSVS male mice weighing 25-30 gm were infected with an Egyptian
strain of _§_. mansoni. Fifteen mice were administered tartar emetic intra-
peritoneally in a dose of 5 mg/kg body weight. Fifteen other mice were
given TWSb intraperitoneally in a dose of 7.5 mg/kg body weight. Both of
these dosages contained the same amount of trivalent antimony. Two mice
from each group were sacrificed at 0.5, 8 and 24 hours and 2,4,7 and
15 days following injection. Tissue samples were analyzed for antimony
by neutron activation analysis.
The pattern of relative antimony uptake by the different mouse organs was
shown equally by both groups treated with TWSb and tartar emetic. The
highest antimony levels were recorded in the liver, GI tract, kidney and
urinary bladder during the first 48 hours. The antimony content of the
stomach and esophagus was significantly less than that of the duodenum
and colon. The difference was probably due to antimony excreted via the
bile into the duodenum. In the latter part of the experiment, the relative
antimony uptake by the flat bones of the skull and by the teeth increased
until it became higher than that of the other tissues. The brain, thyroid
and male reproductive organs contained the lowest antimony concentrations
throughout the experiment. The ventricular muscle of the heart, the tongue
and the adductor muscles of the thigh all gave nearly identical values,
and these were comparable to the antimony level in the blood. Skin levels
were usually higher than those of muscle tissue probably due to .binding
of antimony with sulfhydryl groups in the skin.
Whole body retention patterns and tissue distribution of antimony were
1 0 /
also studied in mice following inhalation of aerosols containing . Sb
(Thomas et al, 1973). The experimental procedure has been described
previously. Immediately following exposure and at intervals thereafter,
the animals were whole-body counted in a liquid scintillation well
detector. Serial sacrifices for tissue distribution were made at 0, 2,
4, 8, and 16 and 32 days postexposure.
-108-
-------
The serial whole-body counts showed an early period of rapid clearance
followed by a steady decrease in the rate of loss of * Sb. Retention
patterns for the more insoluble 500 and 1100° aerosols were nearly
similar, while the soluble 100° aerosol was cleared to a greater extent,
particularly at early times. The difference in retention half-lifes
(39 days at higher temperature vs. 29 days at 100°) was considered a
function of the differences in tissue distribution.
Data for tissue distribution showed an approximate order of magnitude
difference in lung tissue content between the 100° aerosol and those at
500 and 1100°. This difference was also reflected in the femur data and
data from the carcass, a reflection of skeletal deposition. At the lower
temperature aerosol, approximately 85% of the body burden at 52 days was
deposited in the skeleton. The data from liver analyses did not reflect
the pattern observed for skeleton.
The authors theorized that those particles at the lower temperature were
more soluble, leaving the lung very soon after deposition and transporting
in large degree to bone. The aerosol particles generated at the two
highest temperatures tended to remain much longer in the lung, with less
absolute accumulation in the skeleton, although a gradual buildup in the
skeleton was indicated at all temperatures studied. The authors concluded
that the overall retention, regardless of critical organ (lung or skeleton)
would tend to place antimony in the class of compounds that have a retention
time on the order of weeks.
Distribution of antimony in the liver and kidney following intravenous
124
administration of Sb-labeled tartar emetic has been studied in rats by
Waitz e£ al^ (1965). Six pairs of male Holtzman strain rats weighing approx-
imately 200 gm were injected with 2.2 mg Sb (approximately 11 mg Sb/kg).
One pair was sacrificed at 0.5, 2, 4, 8, 24 and 72 hours after treatment
and the liver and kidney analyzed with a scintillation counter. Kidney
antimony levels were found to be higher than those in the liver, a finding
which supported the rapid urinary excretion of antimony.
-109-
-------
Mathews and Molinarp (1963) have also shown elevated Sb levels in kidneys
of rats with a subcutaneous transplanted fibrosarcoma in a study which
monitored the uptake of various radioactive substances used for brain
tumor localization. Wistar-derived male and female rats, weighing 162 -
326 gm, were injected intravenously with 122SbOCl or Na Sb02. The
radioactive uptake in the brain, tumor and other organs was monitored at
1 or 4 hours, respectively, after injection. The results showed that the
distribution of 1 Sb was mainly extracellular since the blood concentre
tion was usually higher than the concentration in organs and organ concen-
tration was proportional to blood concentration. Exceptions were the
kidneys, bone and spleen. With these organs the concentration at some
199
time was greater than in the blood, and so presumably J"6'6Sb was taken up
by cells or was actively concentrated in these particular organs. The
kidneys of animals treated with 122SbOCl contained 3.90% of the dose/gm
while the kidneys of animals treated with Na 122Sb02 contained 1.31% of
the dose/gm.
In the study by Felicetti et^ al^ (1974b), the retention patterns for beagle
dogs exposed to Sb generated at various temperatures (described before
p. 103) showed initial clearance of the 100° aerosol to be the most
rapid, involving over 80% of the initially deposited material. The
average long-term biological half-lives were 100, 36 and 45 days for the
100, 500 and 1000°C aerosols, respectively.
One dog from each group was sacrificed at 32, 64 and 128 days postexposure
for tissue distribution studies. ^Sb concentrations were highest in the
124
lung, thyroid, liver and pelt. At 100°C the thyroid concentrated Sb to
a greater extent than any other tissue. With the 500 and 1000°C aerosols,
the lungs contained the highest concentration of ^ Sb followed by the
thyroid. The relatively larger contribution of the lung to the whole-body
retention with the higher temperatures and lower particle sizes was con-
.sidered indicative of the low upper respiratory tract deposition of the
smaller particles. Clearance of the lung burden was also considerably
-110-
-------
slower with particles generated at 50d or 1000°. This finding was con-
sidered to reflect a lesser solubility of the higher temperature aerosols.
The pelt concentrated "Agt to a rather larger extent and, because of its
size, contained a considerable proportion of the body burden at all sac-^
rifice times for all three aerosols. Skeleton and liver also concentrated
124Sb.
Felicetti et al^ (1974a) studied the comparative whole-body retention and
tissue distribution of trivalent and pentavalent aerosols in hamsters.
The experimental procedure-has been described previously. Whole-body
clearance of both aerosols following inhalation occurred in two phases.
The initial clearance was very rapid. The average body burdens at day 1
postexposure for the trivalent and pentavalent groups were 65% and 60%,
respectively, of the activity found in the day 0 sacrifice animals. Early
rapid clearance was followed by a slower clearance phase during which
the remaining antimony was eliminated with a biological half-life of about
16 days.
By two hours postexposure, less than 1% of the body burden of either
aerosol remained in the lungs. Tissue deposition patterns for the two
aerosol groups were similar with the greatest concentrations of antimony
occurring in the liver, skeleton and pelt. There was, however, signifi-
cantly greater deposition of activity in the liver with the trivalent
than with the pentavalent antimony. This difference was most pronounced
on day 5. By day 32 postexposure, the livers of the trivalent and penta-
valent groups contained 11 + 4% and 5.6 + 1.8%, respectively, of the
total tissue. Activity per gram in the femur was significantly greater
than the muscle. Skeletal values were higher in the pentavalent than in
the trivalent group, but differences were not significant until day 32
when the femur contained 3.4 + 1.4% of the total tissue activity/gm of
tissue in the trivalent group, and 6.0 + 1.8%/gm of tissue in the penta-
valent group. For both aerosol groups, a large percentage of the body
burden was contained within the pelt at all sacrifice times from day 1
through day 32.
-Ill-
-------
Valence state affected the relative distribution of antimony. In the
pentavalent group, mean activity concentrations in the femur exceeded
those of the liver at all sacrifice times. However, in the trivalent
group mean concentrations were greater in the liver than in the femur
until after day 15, when they were higher in the femur. The authors
considered that no extensive reduction of pentavalent to trivalent
antimony occurred, since a greater concentration of antimony in the
liver was observed in the group that inhaled trivalent antimony than in
the pentavalent group.
124
The effect of pretreatment of the subsequent tissue distribution of Sb-
labeled tartar emetic in mice was investigated in a study by Girgis et^ a_l
(1965). The experimental procedure has been previously described. At
the 35 mg/kg level, the concentration in the liver was similar to that in
the control group which had no antimony pretreatment. Sb concentrations
in the heart, spleen and kidney, however, were found to be significantly
lower in the test group than in the control. When the second dosage was
increased to 70 mg/kg, the tissue levels in the test group were about 1/4
those in the control group except for the liver, in which the concentration
was approximately 1/2 that of the control group.
b. Pharmacology
Antimony is an effective agent against such tropical infestations
as schistosomiasis and leishmaniasis with a rapidity of action indicative
of action beyond worm destruction alone. A study in young female CF
mice infected with schistosome eggs demonstrated that treatment with
potassium antimony tartrate (tartar emetic) i.p. at 20 mg/kg/day caused
marked suppression of the granulomatous response to the eggs. Treatment
also suppressed delayed foot pad swelling in response to soluble egg
antigens injected into mice presensitized with schistosome eggs (Mahmoud
& Warren, 1974).
A study of the specific effects on cardiac function in the intact dog
demonstrated a progressive decrease in contractile force and a fall in
blood pressure with death occurring within 120 minutes following an
-112-
-------
intravenous dose of 30 mg/kg body weight of potassium antimony tartrate
(Bromberger-Barnea and Stephens, 1965).
In another study in dogs (Cotton & Logan, 1966) 7.5 mg/kg/day of tartar
emetic or 10 mg/kg/day sodium antimony dimercaptosuccinate (TWSb) were
given intramuscularly daily until death. Neither drug had much effect
on diastolic blood but TWSb increased systolic pressure after 4-5 days
of treatment. Both drugs caused a marked progressive increase in heart
rate. There were no significant EGG changes during the first day of
treatment with either drug, but changes occurred on the second day with
tartar emetic and the third day with TWSb. The most consistent changes
were tenting of the T wave and depression of the ST segment. Death
occurred after 3-5 doses of tartar emetic or 5-7 doses of TWSb. When
geometrically increasing doses of the two drugs were given to anesthetized
mongrel dogs every 15 minutes doses of 1 mg/kg and 2 mg/kg had little
effect on heart rate, blood pressure, right ventricular contractile force
or hematocrit. With increasing doses blood pressure decreased progress-
ively. Ventricular contractile force decreased immediately after each
injection, but then slowly recovered. Deaths occurred after cumulative
doses of 31-63 mg/kg with tartar emetic and somewhat higher doses with
TWSb. Geometrically increasing doses of the two drugs given at 32 minute
intervals, progressively and markedly reduced pressor responses to 1 yg/kg
norepinephrine and progressively diminished reflex cardiac slowing, but
did not affect the cardiac contractile responses. Pressor responses to
100 yg/kg tetramethylammonium bromide (TMA.) were reduced progressively
by the antimonials, but the increase in contractile force and cardiac
slowing were relatively unaffected. Vasodilator effects of isoproterenol,
acetyl choline and histamine were reduced as was the change in heart rate
produced by isoproterenol, but cardiac contractile responses to isopro-
terenol were not affected.
In anesthetized dogs, electrical stimulation of the right vagus nerve was
carried out before and after administration of geometrically increasing
doses of tartar emetic and TWSb. There was no evidence of any significant
change in the sensitivity of the sinoatrial node to vagal stimulation.
-113-
-------
Heart rate was decreased somewhat only with the 64 mg/kg dose of tartar
emetic.
The effects of antimonials on the tracheobronchial tree were studied in
dogs by El-Hawey e* al_ (1971). The trachea of each chloralose-anesthetized
dog was surgically exposed and a Y-shaped cannula was fixed in the lumen.
The animals were artificially respirated while the intercostal muscles
and diaphragm were paralyzed with intramuscularly administered flaxedil.
The antimonials, antimony dimercaptosuccinate (astiban) and potassium
antimony tartrate (tartar emetic) were given intravenously at doses of
0.05-0.1 gm/kg and 0.4-0.6 ml 6% solution/kg, respectively, to 10 clogs
each. Astiban did not produce bronchodilation in any of the dogs, but
tartar emetic caused bronchospasm in 2 of the 10 dogs. From these re-
sults the authors conclude different modes of actions for the drugs:
astiban with a direct relaxant effect; tartar emetic with a central vagal
stimulatory effect.
c. Acute Toxicity
Parenteral - Studies of acute parenteral toxicity of trivalent antimony
compounds in mice (Ercoli, 1968, 1971) indicate that toxicity is depend-
ent on the chemical form of the compound administered. The LD values
50
of several antimony compounds administered subcutaneously were in mg/kg
(mg Sb/kg): potassium antimony tartrate 55 (20), sodium antimony tartrate
48 (19), sodium antimony tartrate-dimethyl cysteine chelate NAP 390 (57),
sodium antimony tartrate - dimethyl cysteine chelate TP15 350 (51), sodium
antimony tartrate-dimethyl cysteine chelate TP2 600 (73) , stibocaptate
2,000 (500) and stibophen 670 (110). Administration by other parenteral
routes did not greatly alter the toxicity: potassium antimony tartrate
had an LD5Q in mice of 49 mg/kg (18 mg Sb/kg) when administered intra-
peritoneally (Girgis et_ al, 1965) and 65 mg/kg (24 mg Sb/kg) when given
intravenously (Ercoli, 1968), sodium antimony tartrate administered intra-
peritoneally 60 mg/kg (24 mg Sb/kg), the chelate NAP given intramuscularly
325 mg/kg (48 mg Sb/kg) and intraperitoneally 450 mg/kg (66 mg Sb/kg).
Intravenously, the chelates TP15 and TP2 had LD 's Of 450 mg/kg (65 mg
Sb/kg) and 600 mg/kg (73 mg Sb/kg) Ercoli, 1968). With all compounds the
toxic signs preceding death were weakness and difficulty of ambulation
and respiration.
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When rats and mice were dehydrated by deprivation of .water for 48 hours
* • •
or by replacement of drinking water1 with 2% saline for two weeks, deaths
occurred more rapidly following intravenous injection of 1.0-1.5 mg/100 gm
body weight of potassium or sodium antimony tartrate and mortality was
significantly greater than in non-dehydrated animals. Both dehydration
and antimony produced a fall in blood pressure until an hour before death.
Blood transfusion preceding antimony injection did not counteract the
effects of dehydration (Baetjer, 1969, 1973).
Oral - The oral toxicity of antimony trioxide was studied in rats. A single
dose of 16 gm Sb20-j/kg produced no apparent ill effects during a 30-day
observation period. Rate of growth and food consumption were similar to
controls (Gross et al 1955a).
Inhalation - A single exposure of dogs and cats to 1 hour at 40-45 ppm
stibine, antimony hydride, was reported to be "dangerous" to most of the
animals. (Webster, 1946). Death generally occurred in less than 24
hours. Animals which succumbed showed pulmonary congestion and edema
accompanied by marked hemoconcentration. Guinea pigs were more resistant
with concentrations three to four times higher required to cause death
within 24 hours (Webster, 1946). Changes in morphology of erythrocytes
was observed rapidly with the appearance of spherical erythrocytes with
tiny spicules extending symmetrically around the periphery. Within 10-20
hours hemoglobinuria occurred in most guinea pigs exposed to 65 ppm stibine
for 1 hour. At sublethal doses, tolerance was apparently acquired rapidly.
In animals which showed marked responses, fatty metamorphosis of the liver
and splenomegaly appeared frequently.
In mice exposed in plastic chambers the LC__ of antimony pentafluoride was
0.27 mg/1 at both high and low humidity (Chekunova & Minkina, 1970). At
lethal concentrations, massive hemorrhages of the lungs and moderate de-
generative changes of the myocardium were observed. In mice dying 5-10
days after exposure, the changes observed were degenerative dystrophic
alterations of liver and kidneys, early signs of interstitial myocarditis,
pulmonary congestion and hyperplasia and partial desquamation of the
alveolar epithelium of the lung.
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In.a study by Gross e_t al^ (1969), pulmonary macrophage mobilization in rats
and hamsters in response to different dust burdens was determined quantita-
tively in the absence or presence of mineral oil. Two groups of rats with
60 animals each received 1200 mg Sb^./m by inhalation for a 12-hour
exposure period or 30 mg of an aqueous suspension of Sb20_ by intratra-
cheal instillation.. The average particle size of the dust was 1.1 microns.
In addition, one half of both experimental groups received a small amount
of mineral oil intratracheally (0.2-0.25 ml) in addition to the dust and
the remainder received an equal volume of water intratracheally in addi-
tion to the dust. Hamsters received Sb«0_ in the same manner in concen-
3
trations of 900 mg/m by inhalation or mg by intratracheal instillation.
Lung macrophage determinations were conducted on two animals from each
group at 0 hour, 1 day, 4 day, 1 week, 2 week and one month after treat-
ment .
The percentages of macrophages recovered from both treated and control .
animals were not only variable, but unpredictable, particularly in animals
that had been given a lung dust burden. Intratracheal injection of Sb?0_
dust into both hamsters and rats resulted in a significant increase in
the mean macrophage count as determined by the saline washout method,
Inhalation of Sb_0_ dust in rats and hamsters was also associated with
significant increase in the mean macrophage count; the inhalation of
Fe00, or SiO' dust did not result in a significant increase in either
4. J ^
species. In rats, no significant increase in the mean macrophage count
was observed when intratracheally injected Sb20« was associated with
mineral oil. In hamsters, the simultaneous presence of mineral oil with
Sb_0 in the lungs was associated with considerably greater increases in
*• J
the mean macrophage count than was found in this species with the dust
alone. Although the increase in mean macrophage count was more sustained
in the presence than in the absence of the mineral oil, there were fluc-
tuations of some magnitude in the counts over the one-month observation
period.
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Eye Irritation - Antimony trioxide with particle size 1.3 - 1.65 microns
instilled into the right eye of male albino rabbits caused no irritation
to conjunctive or cornea up to seven days after treatment (Gross et al,
1955a).
Cutaneous - An aqueous paste of 24 gm of antimony trioxide in methyl
cellulose was applied to denuded skin of albino rabbits over two thirds
of the torso, covered with an impervious membrane and allowed to remain
in contact with the skin for 1 week. No local or systemic effects were
noted (Gross et_ al, 1955a) .
Dry antimony trioxide powder packed into incisions on the shaved backs
of rabbits delayed healing to a degree expected with any nonspecific
foreign body, but did not have any specific untoward effects (Gross et al,
1955a).
Intradermal injection (dosage specified only as "various concentrations"
by the author) on the shaved back of rabbits of 6-8% water solutions of
antimony-dimethyl cysteino tartrates caused only slight hyperemic reac-
tions which disappeared within 24-48 hours (Ercoli, 1968). However,
intradermal injection of potassium antimony tartrate was irritant at a
concentration of 0.124% and at 0.5-1.0% produced intensive hyperemia
followed within 3-4 days with a necrotic ulcer which healed in 4-6
weeks (Ercoli, 1968).
d. Subacute Toxicity
Parenteral - In a study of the cumulative toxicity of trivalent antimony
(Ercoli, 1968) mice were treated subcutaneously for 10 days with 7.23
mg/kg of Sb as potassium antimony tartrate (tartar emetic) or 24.4 mg/kg
of Sb as the dimethylcysteine-potassium antimony tartrate chelate TP2.
Both groups survived treatment. All mice receiving tartar emetic were
reported to have cutaneous lesions, but these lesions were not described.
Mice receiving TP2 were reported to have had no signs of toxicity.
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In dogs injected intragluteally for 7-9 successive days with 6% TP2
solutions corresponding to single doses of 1.45-2.4 mg Sb/kg (total dose
of 10.2-14.5 mg Sb/kg), the drug was reported to be tolerated without
significant side effects or change in appetite or behavior. Hematological
examination revealed essentially normal results (Ercoli, 1968). One week
after completion of the above course of treatments the dogs were given
a second course of treatment which was continued until most of the dogs
died. The total amount of Sb received, considered by the investigator to
be the lethal dose, was 25 mg Sb/kg.
In a study of a pentavalent antimony drug, RL712, a stable non-ionic
complex of antimony hydroxide and a partially depolymerized dextran
glycoside, was given to female NMRL mice by intramuscular injection in
the right or left hind leg alternatively three times a week for 17 weeks
for cumulative doses of 28.2 or 80 mg Sb/mouse (Bou Casals, 1972). No
effect on growth was observed and histological examination two weeks
after the last injection of the higher level of Sb showed normal appear-
ance of the injected areas, heart, spleen, liver and kidneys. Mice
given the lower dose showed no signs of growth impairment or toxicity up
to 26 weeks after the last injection.
Inhalation - In a study of the inhalation toxicity of particulate antimony
trisulfide (particle size = 2 microns) male Wistar rats were exposed to
2
about 3.07 mg/m for 6 weeks, 5 days/week, 7 hours/day (Brieger et al
1954). All animals survived the exposure; appearance and weight gain
remained essentially normal throughout. However, definite and consistent
changes in EGG were observed in all exposed animals, chiefly elevation
of the RS-T segments of all leads, occasional low voltage of the QRS
complexes and frequent flattened T waves mostly in Lead I. These changes
were more pronounced on the last examination prior to termination of the
experiment than on interim examinations. At autopsy the hearts of two
rats were dilated due to flabbiness of the myocardium while the other
hearts appeared normal. The lungs of all animals showed mild congestion
and focal areas of hemorrhage. Histologically, all hearts showed slight
to moderate hyperemia and most showed parenchymatous degenerative changes.
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3
In rabbits exposed to about 5.6 rag/m of antimony trisulfide for 6 weeks,
5 days/week, 7 hours/day (Brleger e£ al, 1954), no effects were observed
on behaviour, survival, blood sugar and BUN levels, liver function tests,
hematology or blood pressure. ECG's indicated slight to moderate myocar-
dial damage with a tendency to progress. At autopsy there was marked
dilation of the heart; the myocardium was very flabby and red-brown.
Histologically there was swelling of the myocardial fibers and the pre-
sence of cytoplasmic granules.
Dogs exposed to about 5.32 mg/m3 of antimony trisulfide for 7 weeks,
5 days/week, 7 hours/day (Brieger et_ al, 1954) showed no definite or
consistent effects in clinical, biochemical, hematologic or electrocardio-
graphic parameters. However, dogs exposed to a concentration of about
5.55 mg/nr for 10 weeks, 5 days/week, 7 hours/day showed some changes in
EGG suggestive of myocardial injury. At autopsy there were no gross
pathological findings. Histologically there was occasional swelling of
myocardial fibers which possibly was associated with treatment.
Rabbits exposed to 27.8 mg/m for 5 days survived, but many had EGG
changes indicative of myocardial damage or coronary inadequacy. Slight
to moderate parenchymatous changes of the myocardium were evident histo-
logically. Slight degenenerative changes were also observed in liver
and kidney and inflammatory changes in the lung (Brieger et al, 1954).
In another study of inhalation toxicity, albino Sprague Dawley rats about
84 days old were exposed to aerosolized antimony as antimony trioxide or
powdered ore at a concentration of 1.7 gm/m in chambers in which only
the nose of the rats was in contact with the antimony. The animals
received 1 to 6 exposures of 1 hour each, every 2 months for 66 to 311
days in the case of the trioxide and 66 to 366 days for the powdered ore.
With the antimony ore, the lungs of some rats immediately after exposure
showed generalized pulmonary congestion with mild edema but this response
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was predominantly transitory and nonlethal. Most rats survived. Except
for the acute response pathology was similar in all animals exposed to
either the trioxide or the ore. At 66 days, the pulmonary pathology
consisted of a phagocytic response. Generally the dust-laden phagocytes
were lying free in the alveolar spaces. At more prolonged intervals after
exposures focalization of the dust into small deposits throughout the
lung became increasingly prominent. Even at 311 days for trioxide and 366
days for the ore the phagocytic response persisted without any appreciable
chronic pneumonitis. In the tracheobronchial lymph nodes there were
scattered deposits of intracellular antimony with mild hyperplasia but no
evidence of chronic inflammation (Cooper et al, 1968).
Exposure of rats to antimony pentafluoride gas for 2 hours/day for 3-1/2
months at a mean concentration of 0.015 - 0.0014 mg/1 SbF5 (0.0085 -
0.0008 mg Sb/1) caused no deaths or alterations in body weight or nervous
system function as medicated by summation threshold index. Liver function
was affected by the end of 3 months as indicated by decreased excretion
of hippuric acid. Bradycardia occurred periodically during treatment and
elevations of the ST and T waves of the EGG were noted. At autopsy an
increased heart/body weight ratio was noted and histologically there were
changes in the myocardial fibers. Histological changes were also observed
in lung, liver, kidney and thyroid tissues. These changes were considered
by the investigators to be related to both antimony and fluoride (Chekunova
and Minkina, 1970).
e. Other Chronic Effects Studies
In a study in rats (Gross et^ al, 1955a) the animals were fed a synthetic
basal diet to which 2% antimony trioxide had been added for about 34
weeks. These rats gained weight more slowly than pair-fed controls. At
autopsy no gross or microscopic abnormalities in tissues or organs were
observed.
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Addition of antimony as potassium antimony tartrate to the drinking water
of Long Evans strain rats at a concentration of 5 ppm for the lifetime of
the animals (Schroeder e£ a.1, 1970) caused no consistent effect on growth
or mature weights of either males or females but significantly, reduced
the longevity. Curiously, nonfasting serum glucose levels were lower than
fasting levels in both sexes. Serum cholesterol levels were higher in
males and lower in females than in controls. At autopsy heart weight was
somewhat higher than controls in males, but this was not considered to be
significant by the investigators. Antimony was found to accumulate in the
tissues with age.
In a similar study in mice (Schroeder et^ al, 1968), 5 ppm antimony as the
potassium tartrate in drinking water caused decreased medial life span
and longevity and some suppression of weight in older animals in females
only. There was no increase in hepatic fatty degeneration compared with
controls. Increased levels of antimony were found in the tissues.
In a study of chronic inhalation toxicity of antimony (Gross et^ al, 1955b),
rats and rabbits were exposed to air containing antimony trioxide (particle
size about 0.6y) at concentrations of 100-125 ppm and 85 ppm, respectively,
for 10 hours/month for 14.5 months and 10 months, respectively. Beginning
after 5 months exposure in rabbits and 9 months in rats the lungs showed
mottling with chalk-white foci 1-2 mm in diameter. The cut surfaces were
coarse-textured and dry. The mottling increased with longer exposure.
Microscopically, inhaled Sb20, dust was early associated with swelling,
proliferation and desquamation of alveolar macrophages. With longer
exposure fatty degeneration of the macrophages became prominent. At the
end of the experiment colorless needle-shaped crystals were observed in
the air spaces, possibly cholesterol, and fibrosis was evident. Antimony
accumulated in the lung tissues.
Implantation of irregularly shaped pellets (3-5 mm diameter) of pure
antimony metal into the superficial precentral motor cortex of the
cerebral hemispheres (right hemisphere or both) of three monkeys (Macaca
mulatta) caused spontaneous clinical seizures in all three monkeys and
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clinical seizures were also observed following challenge doses of penta-
methylene tetrazole (24 mg/kg) given intramuscularly and. picrotoxin (0.35
mg/kg) given intravenously. EEC showed persistent slowing in all three
monkeys. Two of the monkeys died after 2 months; the third survived for
a year. In all three there was a necrotizing foreign body reaction in
the brain with a grey-white necrotic soft spot of 5 mm diameter surround-
ing the metal fragment (Chusid and Kopeloff, 1962).
f. Tolerance - Repeated Doses
In a study in 8-week-old mice given potassium antimony tartrate by intra-
peritoneal injection (Girgis et_ al, 1965) , mice which survived single
high doses were markedly resistant to subsequent high doses. Maximum
tolerance was developed within one day after the first injection and was
reduced considerably after a week. However, some tolerance remained for
a long period. For example, a second dose of 56 mg/kg given 60 days after
a dose of 35 mg/kg caused death in 1/19 mice (single dose LD = 49 mg/kg).
Tolerance was found to be reactivated by administration of another large
dose.
g. Teratogenicity
In a study of the effects of a pentavalent antimony drug RL712 (Bou Casals,
1972) Wistar rats were given 125 or 250 mg Sb/kg body weight as an RL712
solution intramuscularly on five occasions between Day 8 and Day 14 of
gestation. No effects were noted on numbers of fetuses, resorptions or
implantations and no abnormalities were observed in the fetuses. Analysis
failed to detect any antimony in the fetal tissues.
o
In rats exposed to antimony trioxide dust at a concentration of 250 mg/ra
for 2 months (Belyaeva, 1967) reproductive funtion was impaired with
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sterility and reduced numbers of viable offspring. These effects were
reported to be the result of interference with ovigenesis. No abnormal-
ities were reported in the offspring.
In a study in sheep (James et_ A!_, • 1966) four ewes were given 2 mg/kg of
antimony potassium tartrate orally in a gelatin capsule daily from the
first day of gestation for 45 days (2 ewes) or 154-5 days (2 ewes). No
adverse effects were noted in the ewes and all gave birth to normal full
term lambs. No detectable amounts of Sb accumulated in the tissues of
ewes on lambs.
h. Mutagenicity
No information available.
i. Carcinogenicity
In a lifetime study in mice (Kanisawa and Schroeder, 1969) white Swiss
mice, Charles River strain (CD-I) were fed a diet low in trace metals
and were given deionized drinking water to which the essential trace
elements and 5 pg/ml antimony as the potassium tartrate had been added.
No significant difference from the controls was noted in tumor incidence.
In a similar study in rats (Schroeder et^ al^ 1970), random-bred Long
Evans strain rats were given 5 ppra antimony as potassium antimony tartrate
in drinking water. No increase in the incidence of tumors at any site
was observed.
The Russian researchers, E.I. Erusalimskii and G.A. Suspa, publishing
in Vop. Klin. Eksp. Onkol. 8.: 239-42 (1972) on the "Deposition of
3,4-Benzopyrene in Rat Lungs Under the Influence of Metallic Antimony,"
reported that 5 mg of metallic antimony administered to rats along with
4 mg of 3,4-benzopyrene given intratracheally potentiated benzopyrene
carcinogenicity in the rat lungs.
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3. Effects on Other Vertebrates
Halstead (1972) discusses the effects of chemical intoxicants (including Sb)
on the quality of marine products and possibly, as a consequence, on human
health. He cites various examples of cancerous growths, leukemia, genetic
changes and other effects of polluted waters on fish and shellfish, and
mentions the current concern about human poisonings associated with eating
contaminated seafoods. However, the likelihood of large concentrations
of antimony in the marine environment is slight because the few- antimony
salts that are soluble tend to precipitate from solution as Sb^ or Sb^.
In discussing automated monitoring for marine pollution studies,
Gafford (1972) suggests a classification scheme for minor elements
with respect to marine pollution, placing antimony in the category of
elements singled out for special interest because of their exceptional
toxicity or that of some of their elements .
a. Bioaccumulation
Average concentrations of antimony in the oceans are estimated at 0.33
mg/1. According to Goldberg, E.D. (1957), "Biogeochemistry of Trace Metals,"
in Treatise on Marine Ecology and Paleacology, J.W. Hedgpeth, ed., Geo-
logical Society of America Memoir 67, vol.1, pp. 345-57, and to Noddack,
I. and Noddack, W. (1939), "Die Haufigkeit der Schwermetalle in Meerestieren,"
Arkiv. Zool. 32A (4): 1-35, antimony can be concentrated by certain marine
forms (e.g., ascidian, sponge, acaleph, actinian, echinoid, asteroid) to
over 300 times the amount present in sea water.
Leatherland and Burton (1974) reported that when antimony was detected in
concentrations of 0.01 and 0.1 ppm in the bottom muds of waters near South-
hampton, England, the values for fish muscle were at the lower end of the
concentration range.
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As mentioned on p. 121» when potassium antimony tartrate was added to the
drinking water of rats at a concentration of 5 ppm for the lifetime of
the animals (Schroeder et^ a_l, 1970), antimony accumulated in the tissues
with age. In a similar study, increased levels of antimony were found in
the tissues of mice (Schroeder £t al, 1968) given 5 ppm of antimony
potassium tartrate in their drinking water. Gross j£ al (1955b) reported
an accumulation of antimony in the lung tissues of rats and rabbits ex-
posed to air containing antimony trioxide (particle size about 0.6 y) at
concentrations of 100-125 ppm and 85 ppm, respectively for 10 hours/month
for 14.5 months and 10 months, respectively. '.
b. Acute Toxicity
Antimony ions in soft water were toxic to fish (fathead minnows) at con-
centrations of 20 ppm. In hard water, the toxic concentration was somewhat
lower. The ratio of concentration in hard:soft water was 0.6, essen-
tially reducing the allowable concentration in hard water to 12 ppm. So
reports Schroeder (1965), using data from McKee, J.E. and Wolf, H.E.,
editors, Water Quality Criteria, 2nd ed., State Water Quality Control
Board, Sacramento, California, 1963.
Nine years later, apparently based on some of the same basic references
used for the above, the National Academy of Sciences (NAS) reports on
p. 243 of Water of Water Quality Criteria 1972 that although few anti-
monial salts have been tested on fish in bioassays, particularly in sea
water, in static acute bioassays on fathead minnows (Pimephales promelas)
antimony potassium tartrate gave a 96-hr LC as antimony of 20 mg/&
in soft water and 12 mg/£ in hard water; while antimony trichloride in
similar tests gave a 96-hr LC__ as antimony of 9 mg/£ in soft water and
(1)
17 mg/£ in hard water.
(1) Tarzwell, C.M. and Henderson, C. (1960), "The Toxicity of Some of the
Less Common Metals to Fishes," Transactions Seminar on Sanitary Engi-
neering Aspects of the Atomic Energy Industry (Robert A. Taft Sanitary
Engineering Center, TID-7517), and Tarzwell, C.M. and Henderson, C.
(1960), "Toxicity of less Common Metals to Fishes," Indust. Wastes 5: 12,
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Citing two other studies, the NAS also reports that at 5 mg/1 neither
SbCl3 nor SbCl5 had any effect on rainbow trout, bluegill sunfish, and sea
lamprey in Lake Huron water at 13°C, saturated with dissolved oxygen, and
pH 7.5 to 8.2,'1' but that projectile vomiting occurred in large mouth
bass exposed to 1.0 mg/1 of antimony as tartar emetic.(^)
c. Histochemistry
In a study to locate sites of ion transport, pieces of kidney from sea
lamprey, Petromyzon marinus, were fixed in a solution of potassium pyro-
antimonate which has been used to detect cations in tissue. The cells
of the proximal tubule apparently were the only epithelium within the
kidneys of both larvae and adults which possessed electron-dense deposits
of pyroantimonate within the cytoplasm of the cells and within the lateral
intercellular spaces. All cells within the kidneys contained deposits in
their nucleoplasm. The cells of the proximal tubule had large accumula-
tions of deposit in membranous vesicles concentrated near the plasma
membrane at all surfaces. With the exception of the Golgi apparatus
little or no precipitate was observed within cell organelles and, therefore,
there appeared to be little cell injury (Youson, 1973).
4. Effects on Invertebrates
Tissue Uptake - When host mice infected with an Egyptian strain of
Schistosoma mansoni were given intraperitoneal infection of 5 mg/kg of
potassium antimony tartrate, worms collected from the portal system showed
uptake of antimony one hour after injection. The uptake of Sb was higher
in females than in males but the range of concentrations was quite narrow.
The highest concentrations were found 2 hours after injection. In males
antimony concentrations were highest in worm segments containing testes
suggesting accumulation in that organ. No similar apparent accumulation
was found in the ovaries of females (Molokhia and Smith, 1968).
(1) Applegate, V.C., J.H. Howell, A.E. Hall and M.A. Smith (1957), "Toxicity
of 4,346 Chemicals to Larval Lampreys and Fishes," Fish and Wildlife
Service, Special Science Report Fish 207; 157
(2) Jernejcic, F. (1969), "Use of Emetic to Collect Stomach Contents of
Walleye and Large Mouth Bass," Transactions American Fisheries Society
98. (4): 698-702).
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Leatherland and Burton (1974) reported that concentrations of 0.2 ppm
antimony were found in two ascidians (sea squirts) in the bottom muds of
waters near Southharapton, England. Ascidians are identified as a species
having an outstanding capacity for concentrating such trace metals as
vanadium.
Toxicity - On p. 243 of its Water Quality Criteria 1972, the NAS reports
that (antimony) at 9 mg/1 retarded the movement of Daphnia, as recorded
by Bringmann, G. and R. Kuhn (1959), "The Toxic Effect of Waste water on
Aquatic Bacteria, Algae, and Small Crustaceans," Gesundh. Ing. 80; 115-20.
In a study in mice infected with Schistosoma mansoni, administration of
potassium antimony tartrate to the mice resulted in detectable damage to
the reproductive organs of female worms within 5 minutes. This effect
was reversed in the 5 months following treatment (Bourgeois, 1971).
Rogers and Hpwell (1971) have reported that antimony compounds adminis-
tered to the fowl tick, Argas radiatus, by in Vivo engorgement on
poisoned chicks, in vitro engorgement on preserved chicken blood, lanolin
inunctum or dipping of the ova in physiological saline containing antimony
compounds, significantly reduced survival in larvae, neonymphs, deuter-
nymphs and adults, fecundity in resulting females and fertility in
deposited ova. Histologically, gametic destruction was observed in
both sexes. Percent hatch was higher for ova dipped in saline contain-
ing potassium antimony tartrate than for those dipped in saline alone,
but was lower than for untreated ova.
5. Effects on Plants
On p.243 of its Water Quality Criteria 1972. the NAS again cites Bringmann
and Kuhn (ibid) as reporting that (antimony) at 3.5 mg/1 hindered the
cellular division of green algae.
6. Effects on Microorganisms
a. Toxicity and Pharmacology
In a study using five strains of Staphylocpccus aureus (phage types 7 US,
54, 71, 80 and 81) all of which were of human origin, hemolytic, coagulase
positive, and penicillin resistant neither antimony sodium thioglycollate
-127-
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or antimony thioglycollamide at concentrations up to 0.125 yg/ml had any
affect on the growth of the bacteria during an 18 hour incubation period
(Richtarik
-------
uptake occurred. With prolonged incubation the liver slices deteriorated
with dead-looking tissue sloughing off. This tissue, which microscopi-
cally appeared as undifferentiated necrotic tissue, contained 3 to 18
times as much antimony as healthy tissue (Smith, 1969).
Subcellular fractionation of the liver slices following incubation with
12^Sb-antimony potassium tartrate resulted in about 70% of the radio-
activity being recovered in the particulate fractions. The microsomal
fraction contained the highest concentrations in terms of both protein
and tissue weight (Smith, 1969).
Antimony uptake by liver slices incubated 1-8 minutes was unaffected
by absence of oxygen, presence of KC1, oubain, dinitrophenol or Na
arsenate, or by preincubation with unlabelled antimony potassium tartrate
for up to 60 minutes. Uptake was inhibited by dimercaprol, dithiothreitol
and Ellman's reagent. Uptake of antimony was associated with progressive
reductions in oxygen consumption (Smith, 1969).
Slices of other tissue were able to take up antimony but to a lesser extent
than liver. Accumulating ability decreased in order liver > kidney >
spleen > intestine > brain (Smith, 1969).
In a study of cardiac effects potassium antimony tartrate injected into
the coronary circulation of isolated spontaneously beating dog hearts
produced a progressive fall in myocardial contractile force which was not
reversible. Some bradycardia was observed but the degree was neither
consistent or remarkable. Post-stimulation potentiation of contractile
force which is usually seen was absent in a number of instances. However,
the magnitude of the percentage response to test doses of adrenalin was
essentially unchanged by antimony (Bromberger-Barnea and Stephens, 1965).
In isolated spontaneously beating guinea pig atria increasing concentra-
tions of potassium antimony tartrate (tartar emetic) and sodium antimony
dimercaptosuccinate (TWSb) had only a slight effect upon rate until a
concentration of 10~2M was reached. At this concentration both anti-
-129-
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monials caused substantial and significant reduction in contractile force.
Similar responses were observed in guinea pig ventricle strip preparations
(Cotton and Logan, 1966).
b. Effects on Cell Cultures
Incubation of horse blood with trivalent antimony as antimony potassium
tartrate (tartar emetic) or sodium antimony dimercaptosuccinate (Astiban)
resulted in increasing uptake of Sb by erythrocytes with time up to 8
hours. With pentavalent antimony as sodium stibogluconate (Pentostam)
very little uptake occurred regardless of incubation time. At all times
plasma concentrations were much higher than erythrocyte concentrations
(Molokhia and Smith, 1969b).
Erythrocytes labelled with trivalent antimony and incubated with normal
plasma for 1 hour lost antimony to the plasma. This was slightly more
pronounced with.tartar emetic than with Astiban. .More antimony was lost
from cells which had been incubated shorter periods during labelling
(Molokhia and Smith, 1969b).
In cultured human leukocytes, sodium antimony tartrate at a concentration
of 1.0 x 10~°M added to the culture during the last 48 hours of a 72 hour
culture period was toxic to the cells, causing a marked reduction in
-9
mitotic index. For chromosome studies a concentration of 2.3 x 10 M was
added to the leukocyte culture medium. Of a total of 100 metaphases
examined, 12% of the cells had chromatid breaks which was a statistically
significant (5% level) increase over the controls (Paton and Allison, 1972)
In human blood cells selective binding of pyroantimonate was observed in
the plasmalemma of developing and mature neutrophilic leukocytes, but
not in other forms of leukocytes. In the earliest stages of development
the plasmalemma is unreactive. Binding was first evident in young forms
of the midpromyelocyte and reached a peak during the latter half of the
promyelocytic stage. In the segmented neutrophil there were only a few
deposits of reactive product associated with the plasmalemma. Late
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developmental forms of nucleated erythrocytic cells and mature erythrocytes
also exhibited plasmalemmal pyroantimonate binding. The degree of binding
was related to the degree of maturation. These results indicate that
chemical distinctions between the plasmalemma of different types of cells
exist (Ackerman and Clark, 1972).
c. Effects on Isolated Organelles and Cell Homogenates
Rat liver mitochondria pre-incubated for 2 minutes with increasing amounts
of sodium antimony gluconate (Triostib, 30% trivalent antimony) showed
progressive inhibition of oxygen when ot-ketoglutarate was the substrate
indicating that oxidative phosphorylation was increasingly inhibited. The
same result was observed when the substrate was glutamate, but not when it
was succinate. Similar results were obtained in classical Warburg ex-
periments. Since it was the oxidation of NAD+ linked substrates that was
inhibited the investigators assumed that Triostib probably acted on the
NADH-oxidase segment of the chain. The inhibition of NADH oxidation was
reversed by the addition of methylene blue (Campello ej^ al_ 1970).
d. Effects on Enzyme Systems
In extracts from homogenized adult Schistosoma mansoni worms, lactic acid
production from glucose was markedly inhibited when stibophen or antimony
potassium tartrate was added. Both purified and crude glucokinase pre-
parations were relatively insensitive to high concentrations of anti-
monials indicating that phosphorylation of glucose to glucose-6-phosphate
(G-6-P) by ATP was not affected by Sb. Fructokinase and mannokinase were
also not affected. Neither antimony compound affected conversion of G-6-P
to fructose-6-phosphate (F-6-P) or lactic production from fructose-1,
6-diphosphate (HDP). However, lactic acid production from F-6-P was
inhibited indicating that the antimonials block the formation of HDP from
F-6-P by the enzyme phosphofructokinase. (Mansour and Bueding, 1954) .
In rat brain preparations, phosphofructokinase activity was much less
sensitive to the trivalent antimony compounds. Pentavalent antimony as
sodium stibogluconate had no effect on the activity of the worm enzyme.
e. Effects on Nucleic Acids and Proteins
There was no information in the literature.
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IV. REGULATIONS AND STANDARDS
A. Current Regulations
1. Food and Drug Authorities
The proportion of antimony in color additives is limited, according to
Part 8 of the CFR Title 21, Chapter 1 - Food and Drug Administration (FDA).
In Subpart D, the 8.300 series concerns diluents in color additive mix-
tures for food use exempt from certification, under which specifications
for antimony are listed in 8.316. This section states that the synthetic-
ally prepared color additive titanium dioxide (TiO^) shall conform to
the following:
Lead (as Pb), not more than 10 parts per million.
Arsenic (as As), not more than 1 part per million.
Antimony (as Sb), not more than 2 parts per million.
Mercury (as Hg), not more than 1 part per million.
Loss on ignition at 800°C. (after drying for 3 hours
at 105°C), not more than 0.5 percent.
Water soluble substances, not more than 0.3 percent.
Acid soluble substances, not more than 0.5 percent.
Ti02 not less than 99.0 percent after drying for 3 hours at 105°C.
2. Air and Water Limitations
The release into the environment of antimony and of such compounds of
antimony as antimony trioxide, antimony pentasulfide, antimony sulfate,
antimony trisulfide, antimony trifluoride, antimony pentafluoride and
potassium antimony tartrate is provisionally limited to contamination
levels of 0.005 ppm (mg/1) as Sb in air and 0.05 ppm (mg/1) as Sb in
water (TRW, 1973). These levels based on threshold limit values, were
calculated by TRW in a study for EPA on recommended methods for disposal
of hazardous waste. They are offered as provisional limiting concentra-
tions pending the development of ambient air quality standards that can
be based on extensive evaluation of acute and chronic dose response
criteria for exposure of all living and nonliving things.
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The,U.S. Environmental Protection agency in October 1975 issued its
"Development Document for Interim Final and Proposed Effluent Limitations
Guidelines and New Source Performance Standards for the Ore Mining and
Dressing Industry" (EPA 440/1-75/061, Vols. I and II). On p. 753 of
Vol. II, the effluent limitation for Sb (recommended for best practicable
control technology currently available (BPCTCA) — antimony mines) is
0.5 mg/£ Sb for a 30-day average and 1.0 mg/£ for a 24~hour maximum.
The EPA's National Interim Primary Drinking Water Regulations, published
in the Federal Register of 24 December 1975, are to be effective 24 June
1977. These regulations do not include antimony among the inorganic
chemicals for which maximum contaminant levels are given.
3. Wastes
Antimony pentafluorlde and antimony trifluoride are listed as nonradioactive
High hazard compounds by the EPA Office of Solid Waste Management Programs
in its 1974 Report to the Congress on the Disposal of Hazardous Wastes,
identified as EPA Publication SW-115. The Office of Solid Waste Manage-
ment Programs considers these two compounds of antimony unacceptable for
normal disposal methods.
4. Occupational Safety and Health Administration (OSHA)
Under the Occupational Safety and Health Standards, announced in 1974 by
OSHA, antimony and compounds (as Sb) are listed together as one entry in
a table of air contaminants for which employee exposure limits are given
as 8-hour time weighted averages. According to the OSHA standards, an
employee's exposure to antimony and compounds (as Sb) shall not exceed
3
the 8r-hour time weighted average of 0.5 mg/m , for any 8-hour work shift
of a 40-hour week. [Fed. Reg. ^9 (125), p.23540-1 (27 June 1974)]
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5. Transport Regulations
In the CFR 46 for Shipping, Chapter I - Coast Guard, Department of Trans-
portation, only antimony pentachloride and antimony pentafluoride are
included on the list of explosives and other dangerous articles and
combustible liquids. Antimony pentachloride may be shipped dry or in
solution but by cargo vessel only. It should be stored on deck, protected
from the weather or under cover and carry a white label for corrosive
liquid. Transport limits are given as follows:
• for metal barrels or drums - 55 or 110 gallon capacity
• for wooden barrels - 20016 net weight
• for wooden boxes - 20016 gross weight
• for portable tanks - 8,00016 gross weight
• for tank cars - must comply with DOT regulations
(trailerships only)
• for motor vehicle tank trucks - must comply with DOT
regulations (trailerships and trainships only)
The regulations for antimony pentachloride solution are the same as for
SbCl, in dry form except for very detailed specifications for containers.
Antimony pentafluoride is permitted to be transported by cargo vessel
only in steel cylinders containing 1, 5, 25 and 200 Ib SbF and stored
on deck protected from the weather or under cover. White labels are
required signifying corrosive liquid. Electric wet storage batteries
containing SbF5 are listed by DOT.
6. Other Federal
The U.S. Bureau of Mines has approved various types of respirators for
personal protection against antimony contamination, depending on the form
of contaminant.
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7. States
a. New Jersey
Chapter VII of the Code of New Jersey Air Pollution Control Commission,
New Jersey State Department of Health covers air pollution from solid
particles. Under Section 2.7 of this code antimony is listed with an
"effect factor" of 0.9 for fine solid particles. An effect factor in
this context is defined as a value assigned to an air contaminant in the
form of a numerical modifier which when multiplied by the basic emission
yields the allowable emission.
b. Pennsylvania
The Hygienic Information Guide No. 11 of Pennsylvania Department of Health,
Division of Occupational Health includes antimony. A Threshold Limit-
Value (acceptable atmospheric concentration for 8-hour work period) of
0.1 ppm of air is given for stibine and 0.5 mg/m of air for antimony
and its compounds (as Sb). This Guide states that inhalation of gases,
fumes and dusts of antimony and its compounds is the main source of
antimony poisoning and exposure to stibine concentrations of 100 ppm for
several hours may cause death.
Recommended exposure control includes maintaining atmospheric contamination
levels at less than Threshold Limit Value by enclosure and local exhaust
ventilation. Personal respiratory protection, approved by the U.S. Bureau
of Mines for protection against the form of antimony contamination
generated, is suggested. For prevention of skin contact suitable gloves,
aprons and fact shields should be used.
8. Foreign
The Inter-Governmental Maritime Consultative Organization (IMCO) lists
antimony lactate, antimony potassium tartrate, and antimony (inorganic,
not otherwise specified) in its International Maritime Dangerous Goods
Code. However, the provisions of this Code should not apply to antimony
sulfides and oxides free of arsenic.
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Antimony compounds, including antimony lactate and antimony potassium
tartrate, are classified as poisonous (toxic) substances which are liable
to cause death, or serious injury to human health if swallowed, inhaled,
or by skin contact. The container and package regulations are essentially
the same for the antimony compounds designated and a poison label must
be displayed. Size limits are stipulated for liquid and solid form and
vary depending upon whether the packing mode is glass bottles or cans,
or (in the case of solids only) paper or plastic bags in a wooden or
fibreboard box; a metal drum; or (in the case of solids only) a wooden
barrel, fibre or plywood drum. Storage on deck or under deck is required
with fibreboard boxes, in particular, stowed under deck and unexposed to
sea water. All storage is limited to cargo ships or passenger ships,
which are carrying not more than 25 passengers or 1 per 10 feet of length,
and separated from all foodstuffs in order to avoid contamination.
One study (Arzamastsev, 1964), performed at a Soviet institute for
community health, resulted in recommendations that the maximum permis-
sible concentration of trivalent and pentavalent antimony in water be
set at 0.05 mg/1. This investigation showed 0.0025 mg/kg had no effect
on warm-blooded animals and 0.6 mg/1 as the threshold values affecting
organoleptic properties of water for both trivalent and pentavalent
antimony. The LD_0 values for albino rats amounted to 675 mg/kg for
SbCl3 and 1115 mg/kg for SbCl .
B. Consensus and Similar Standards
The American Conference of Governmental Industrial Hygienists (ACGIH)
3
has adopted 0.5 mg/m as the Threshold Limit Value (TLV) for airborne
concentrations of antimony and compounds (as Sb)'. This TLV represents
conditions under which it is believed that nearly all workers may be
repeatedly exposed day after day without adverse effect.
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V. EVALUATION AND COMMENTS
Antimony has been manufactured in the U.S. for about 80 years. Although
there have been reported incidences of pneumoconiosis among workers,
and antimony compounds can be irritating to the skin and cause other
disorders, no epidemiological studies have appeared. There is no
evidence that antimony is a carcinogen, teratogen, or a mutagen.
A limited number of manufacturers produce antimony and/or its compounds
and production is comparatively small scale, being only about 41,000
tons/year.
The most serious potential problems associated with antimony wastes seem
to be related with their potential impact on the ecosystem, resulting
from disposal in fresh or sea waters. To date, however, no evidence
exists to indicate that antimony or its compounds in the amounts de-
tected in water have had any harmful effects on marine life.
While current knowledge does not permit ranking antimony and its com-
pounds as major environmental contaminants, antimony has innate toxicity
and inhalation of concentrations above its Threshold Limit Value could
be damaging. Careful control of antimony air emissions, careful monitor-
ing of antimony-containing effluents, and proper disposal of toxic anti-
mony compounds or those antimony compounds that degrade to form toxic
substances should be encouraged.
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