ANTIMONY TRIOXIDE AND ANTIMONY TRISULFIDE

1. ehemical and Physical Data

1.1 Synonyms

Anmony trxie

Chem. Abstr. Services Reg. No.: 130-6-4 - Antimony oxide1317-98-2 - Valentinite12412-52-1 - Senarmontite

Chem. Abstr. Name: Antimony oxideIUP AC Systemic Name: Diantimony trioxide

Synonym: Antimonious oxide; antimony (III) oxide; antimony sesquioxide; antimo-ny white; AP 50; flowers of antimony; CI 77052; CI Pigment White 11; senarmon-tite; valentinite

Anmony trsulje

Chem. Abstr. Services Reg. No.: 1345- - Antimony sulfide

1317-868 - StibniteChem. Abstr. Nam: Antimony sulfideIUP AC Systematic Name: Diantimony triulfide

Synonym: Antimonous sulfide; antimony glance; antimony needles; antimonyorange; antimony sesquisulfide; antimony triulfide colloid; antimony vermilion;black antimony; CI 7706; CI Pigment Red 107; crison antimony sulfide; needleantimony; stibnite

1.2 Molecular rormulae and molecular weights

Sb203

Sb2S3

antimony trioxide - MoL. wt: 291.50

antimony triulfide - MoL. wt: 339.68

Antimony trioxide is a dimorphic cistalline solid existing in an orthorhombic configu-ration as the minerai valentinite and in cubic form as senarmontite (Weast, 1985). Antimonytriulfide in its minera form, stihnite, is an orthorhombic-bipyramidal cistalline structure(Roberts et al., 1974).

-291-

292 IAC MONOGRAHS VOLUME 47

1.3 Chemical and physical properties of the pure substance

Antimony trxie

(a) Description: White, odourless, ciystalline powder (Asrco, Inc., 1988a)

(b) Melting-point: 656°C (Weast, 1985)

(c) Boiling-point: Sublimes (Weast, 1985)

(d) Density: Valentinite, 5.7 g/cm3; senarmontite, 5.2 g/cm3 (Weast, 1985)

(e) Reactivity: Reacts with strong alkalis to form antimonates (Mannsvile ChemicalProducts Corp., 1981)

if Solubility: Veiy slightly soluble in water; soluble in potassium hydroxide, hydro-

chloric acid and acetic acid (Weast, 1985); insoluble in organic solvents (Freedmanet al., 1978)

(g) Spectroscopy data: X-ray diffraction patterns for valentinite and senarmontite

have been reported (Roberts et al., 1974).

(h) Refractive index Valentinite: 2.18, 2.35, 2.35; senarmontite: 2.087 (Weast, 1985)

Antimony trsulfe

(a) Description: Puriied antimony trisulfide is usually a yellow-red amorphous pow-der (Weast, 1985). ln its natural form (stibnite), antimony triulfide is commonlyfound as well-formed ciystals, sometimes veiy large and solid and at other timesslender and fragile. The ciystals are often vertically strited, bent or twited.

They are pale to dark lead-grey, but may appear tarnished, irdescent, bluish orblackih (Roberts et al., 1974).

(b) Density: amorphous, 4.12 g/cm3; stibnite, 4.64 g/cm3 (Weast, 1985)(c) Solubility: Veiy slightly soluble in water; soluble in hydrochloric acid and ethanol

(Weast, 1985)

(d) Spectroscopy: The X-ray diffraction pattern for stibnite has been reported (Rob-erts et al., 1974)

(e) Refractive index Stibnite: 3.194, 4.06, 4.303 (Weast, 1985)

1.4 Technical products and impurities

Anmony trxie

Trade nams: Amspec-KR; Anzon-lMS; Asrco antimony oxide (L'l Hf VH; A1582; A 1588 LP; Blue Star; Dechlorane A-O; Extelite; Exrema; Laurel (formerly Chem-tron) Fire Shield; Thermoguard B; Thermoguard S; Twikling Star; White Star

Antimony trioxide is available in several product grades of varyg particle and tint. Ail

are of at least 99.0% purity. Lead, arsenic and iron are common contaminants of the productin quantities of ~2, ~0.5 and.: 0.01 wt%, respectively (Mansvle Chemical Products Corp.,1985; Anzon, Inc., 1988; Asrco, Ine., 1988,b).

ANIMONY TRIOXIDE AN ANIMONY TRISULFDE 293

Anmony trulfde

Trade name: LymphoscnNo data on technical-grade antimony trisulfide or its impurities were available to the

Workig Group.

2. Production, Use, Occurrence and Analysis

2.1 Production and use

(a) Production

Antimony trioxide is tyically produced by roasting stibnite ores, which are reported tocontain 55% antimony. The production of antimony trioxide ocurs as a vapour-phase reac-tion at temperatures in excess of 1550°C. The stoiehiometric addition of oxygen to the feedore produces the desired product. Tetra- and pentoxides produce precipitate from the va-pour as white and yellow powders, respectively. Antimony trioxide has also been isolated formany years as a by-product of lead smelting and production. Approxiately 10-15% of USproduction ocurs via this route. Antimony trioxide can be puriied through seriai vapourphase reciystalliztion (Freedman et al., 1978; Mannsvile Chemical Products Corp., 1981,1985; Asrco, Inc., 1988a).

The following countries produce antimony trioxide: Belgium, Bolivia, China, France,Guatemala, Mexico, South Africa, the UK, the USA and Yugoslavia. Total US productionhas tripled since 196 (Mannsvile Chemical Products Corp., 1981, 1985; Palencia & Mishra,1986) and was approxiately 19 00 tonnes in 1987 (Llewellyn & Isaac, 1988).

Antimony trisulfide pigment is prepared by the addition of soium thiosulfate solutionto a solution of antimony potassium tartrate (tartar emetic) and tartanc acid or to a solutionof another suitable antimony salt (LeSota, 1978).

(b) Use

The largest end use for antimony trioxide is as a fire retardant in plastics, rubbers, tex-tiles, paper and paints (Mannsvile Chemical Products Corp., 1981). This application repre-sents approxiately 6075% of total US consumption (Mannsvile Chemical Products

Corp., 1981, 1985; Llewellyn & Isaac, 1988).Antimony trioxide by itself is not a fire retardant. It is used as a syergist, tyicallyat

2-10% by weight, with organochlorie and brominated compounds to diminish the inam-mability of a wide range of plastics and textiles. Antimony trioxide also fiters ultraviolet radi-

ation which cause textile fibres to deteriorate (Drake, 1980; Lyons, 1980; Mannsvile Chemi-cal Products Corp., 1981, 1985).

When added to ceramic products, antimony trioxide imparts opacity, hardness and acidresistance, for instance, to sanitaiy ware and enamels. ln the preparation of optical and rubyglass, antimony trioxide is used as a bubble remover. ln other glasses, it is incorporated as a

294 IAC MONOGRAHS VOLUME 47

colour stabilizer to protect against the weatherig effects of the sun. Hs use as a stabilizerand as a catalyst accunted for an estimated 15% of total US consumption in 1980 (Manns-vile Chemical Products Corp., 1981; Windholz, 1983).

Antimony trioxide is used as a catalyst in the production of polyester resins and in thedecomposition of hydrogen bromide. When used with tin dioxide at 480°C, antimony triox-ide catalyses the partial oxidation of propylene (Samsonov, 1982).

Antimony triulfide is used as a prier in ammunition and smoke markers, in the pro-duction of vermilon or yellow pigment and antimony salts such as antimony oxide and chlo-ride, and in the manufacture of ruby glass (Mannsvle Chemical Products Corp., 1985; Pa-lencia & Mishra, 1986; Hawley, 1981).

(c) Regulatory status and guideline

An ocupational expsure limit of 0.5 mg/m3 as an 8-h time-weighted average (I A)

has been set for antimony and its compounds (measured as antimony) in many countries (Di-rektoratet for Areidstilsyet, 1981; Areidsinspectie, 1986; Institut National de Recherche

et de Sécurité, 1986; Health and Safety Directorate, 1987; National Swedish Board of Occu-pational Safety and Health, 1987; Työsuojeluhalltus, 1987; US Occupational Safety andHealth Administration, 1987; American Conference of Governmental Industril Hygienists,1988; Arejdstisyet, 1988; Deutsche Forschungsgemeinschaft, 1988). An expsure limit of

0.5 mg/m3 (8-h 1W A) has also been set specifically for the handling and use of antimonytrioxide (measured as antimony), in sorne cases with a carciogen or ski sensitivity notation

(International Labour Office, 1984; American Conference of Governmental Industrial Hy-gienists,1988). Lower expsure limits (0.05 mg/m3, or no permissible expsure) have beenset for the production of antimony trioxide because these compounds are classified as carCI-nogenic in several countries, e.g., Belgium, Finland, ltaly, Sweden and the USA (Interna-tional Labour Office, 1984; National Swedish Board of Occupational Safety and Health,1987; Työsuojeluhalltus, 1987; American Conference of Governmental Industril Hygie-nists, 1988).

2.2 Occurrence

(a) Natural occurrence

Antimony trioxide ocurs in nature as the minerais valentinite and senarmontite. Theorthorhombic valentinite and cubic senarmontite are secondaiy minerais formed by the geo-logic alteration of stibnite (Sb2S3) and other antimony minerais (Roberts et al., 1974).

Antimony triulfide ocurs in nature as the minerai stibnite. It is formed as a low tem-perature deposit from hot solutions often assoiated with arsenic minerais and cinnabar.

Significant deposits ocur in AIgeria, Borneo, Canada, China, Czechoslovakia, the FederalRepublic of Germany, France, Italy, Japan, Mexico and Peru (pough, 196; Roberts et al.,1974; Palencia & Mishra, 1986).

ANMONY TRIOXIDE AN ANMONY TRISULFDE 295

(b) Occupaiona exsure

On the basis of US National Occupational Exsure Surveys, the National Institute forOccupational Safety and Health (1974, 1983) estimated that 28 957 workers were potentiallyexpsed to antimony trioxide in the USA in 1972-74 and 85 650 in 1981-83.

ln a UK plant where antimony ore was procssed, levels of antimony oxide in the air ofwork areas were reported to be highest durig the short periods when tapping operations

(purig molten metal) at the furnace were under way; the mean value at these times was 37mg/m3. Ai levels in other areas of the plant were 0.53-5.3 mg/m3 (McCallum, 1963).

Personal ïW A expsure to antimony trioxide at a glass-producing factoiy in the Feder-al Republic of Germany ranged from less than 50 jlg/m3 to 84 jlg/m3, with correspondingbloo levels of 0.4-3.1 jlgll and a median of 1.0 jlgll (Lüdersdod et al., 1987).

A study of two major US antimony producing companies in which imported antimonysulfide ore was roasted to produce antimony trioxide showed personal ïWA expsures torange from 0.21 to 3.2 mg/m3 (mean, 1.32 mg/m3) and 2.7 to 8.7 mg/m3 (mean, 5.2 mg/m3;Donaldson & Cassady, 1979).

At a smelting plant in Yugoslavi, concentrations of dust consisting of 36-90% antimo-ny trioxide ranged from 16 to 248 mg/m3 (Krajovic et al., 196). At a plant in the USA whereantimony sulfide ore was smelted, persnal1W A airrne concentrations of antimony were0.92-70.7 mg/m3; the author postulated a predominance of antimony trioxide (Renes, 1953).At another US antimony smelting plant, workers were expsed to antimony ore dust contain-ing priariy antimony trioxide at concentrations (area samples) ranging from 0.08 to 138

mg/m3 (Cooper et al., 1968). ln a plant in the USA manufacturig resinoid griding wheels,ocupational expsures to antimony triulfide were reported to range from 0;6 to 5.5 mg/m3

(Brieger et al., 1954).

2.3 Analysis

No inormation was available to the Workig Group on standard methods for the quan-titative determination of antimony trioxide or antimony trisulfide in envionmental samples.Antimony can be quantified in envionmental matrices bya variety of methods, includingatomic absorption spectrophotometiy, inductively coupled plasma emission and X-rayfluorescence spectrometiy, neutron activation analysis, anodic stripping voltammetry andvarious titrietric and colorietric methods (Freedman et al., 1978; US Envionmental Pro-tection Agency, 1983; Eller, 1985; US Envionmental Protection Agency, 1986; Loge,1989).

296 !AC MONOGRAHS VOLUME 47

3. Biological Data Relevant to the Evaluation of

earcinogenic Risk to Humans

3.1 CarciDogeDicity studies iD aDimals1

Inhalation expsure

Rat: Groups of 49-51 female Fischer rats (CDF from Charles River), 19 weeks old,were exposed by inhalation to 0, 1.6:f 1.5, or 4.2 :f 3.2 mg/m3 commercial grade antimonytrioxide (measured as antimony; purity, 99.4%; arsenie, 0.02%; particle size, 0.4 llm :f 2.13(for the high concentration) and 0.44 llm:f 2.23 (for the lower concentration)) for 6 h per dayon five days per week for 13 months. Mean boy weights were increased in both treatedgroups durig the exposure period but did not differ significantly from that of controls at theend of the study. Groups of rats were sacriiced and examined histologically after three, six,nine and 12 months of expsure and two months after the end of treatment (numbers of ratssacriiced and numbers of early deaths for each period unspecified). At 12 months after theend of treatment, 13 control, 17low-dose and 18 high-dose rats were sacriiced and selectedtissues were examined. Lung tumours loclized in the bronchioloalveolar region ocurred in14/18 high-dose rats (three adenomas, nine scirhous carcinomas (p .c 0.01 (test unspeci-fiedD and two squamous-cell carcinomas). One bronchioloalveolar adenoma ocurred in alow-dose rat, and no lung tumour was observed in the control group at terminal sacriiee.Scirhous carcinomas were also observed in 5/7 and 1/9 high-dose rats that died or were sac-riieed between two months after the end of treatment and terminal sacriice or between theend of treatment and two months after the end of treatment. One bronchioloalveolar adeno-ma ocurred among six control rats that died or were sacriiced between two months after theend of treatment and terminal sacriice. There was no significant difference in the numberof other tumours ocurrg in treated and control groups (Watt, 1983).

Groups of 90 male and 90 female Wistar rats, eight months old, were expsed by inhala-tion to 0 or 45 mg/m3 (I A) antimony trioxide (purity, :;95%; arsenic, 0.00%; titanium,.c 3% ) for 7 h per day on five days per week for 52 weeks. Five males and females were kiledat six, nine and 12 months after exposure was initiated; the remainder of the animais werekiled 18-20 weeks after the end of the expsure period. There was no significant differencein survval between treated and control groups of either sex; 39 control and 31 treated fe-males survved until terminal sacriice (estimated survval in males was 21 and 21). Non-neo-plastic lesions (interstitial fibrosis, alveolar-cll hyperplasia and metaplasia) of the lung oc-curred with similar frequency in male and female rats but were slightly less severe in males.The first lung tumours were seen in two (one adenoma and one squamous-cell carcinoma )of

lThe Working Group was aware of a study in progr of intracheal administration of antimony trioxide to ham-

sters (IARC, 1988).

ANIMONY TRIOXIDE AN ANMONY TRISULFIDE 297

five treated female rats sacriieed at 53 weeks; 19170 (27%) treated females survvig at thetime the first tumour was observed developed lung tumours. No lung tumour was seen intreated males or in male or female controls. The lung tumours that were found in treatedfemales were nine squamous-cell carcinomas, five scirhous carcinomas and 11 bronchio-loalveolar adenomas or carcinomas (numbers of benign and malignant bronchioloalveolartumours not specified). The incidence of other tumours was not different between treatedand control rats (Groth et al., 1986).

Groups of 90 male and 90 female Wistar rats, eight months old, were expsed by inhala-tion to 0 or 36-4 mg/m3 (I A) antimony ore concentrate (containing 46% antimony, prici-pally as antimony trisulfide; titanium, .c 4%; aluminium, 0.5%; tin, 0.2%; lead, 0.3%; iron,0.3%; arsenic, 0.08% ) for 7 h per day on five days per week for up to 52 weeks. Five males andfive females were kiled six, nine and 12 months after expsure had been initiated; the re-mainder of the animais were kiled 18-20 weeks after the end of the expsure period. Therewas no significant difference in survval between treated and control groups of either sex; 39control and 33 treated females survived untIl terminal sacriice (estimated survval in maleswas 23 and 21). Non-neoplastic lesions (interstitial fibrosis, alveolar-cell hyperplasia andmetaplasia) of the lung ocurred at similar frequency in male and female rats but were slight-ly less severe in males. The first lung tumour was seen in a treated female that died 41 weeksafter the beginning of treatment; 17/68 (25% ) treated females survvig at the tIme the first

tumour was observed developed lung tumours. No lung tumour was se en in treated males orin male or female control rats, and there was no difference in the incidences of other tu-mours between treated and control groups of either sex. The lung tumours that ocurred intreated females were nine squamous-cell carcinomas, four scirhous carcinomas and sixbronchioloalveolar adenomas or carcinomas (numbers of benign and malignant bronchio-loalveolar tumours not specified) (Groth et al., 1986).

3.2 Other relevant data

The toxicology of antimony compounds has been reviewed (National Institute for Oc-cupational Safety and Health, 1978).

(a) Exrimental systems

(i) Absorption, distribution, exretion and metabolismAfter administration of 2% antimony trioxide to rats in the diet for eight months, very

high levels were found in the thyroid, while retention was much lower (in decreasing order)in the liver, spleen, kidney, heart and lungs (Gross et al., 1955a). After administration of 1 %antimony trioxide to rats in the diet for 12 weeks, the highest antimony concentrations werefound (in decreasing order) in the bloo, spleen, lungs, kidneys, hair, liver and heart; 12weeks after the end of treatment, levels in the bloo, lungs and kidneys had decreased toabout 50%, but the spleen stil contained about 75% of the concentration observed at termi-nation of expsure (Hiroka, 1986).

ln rats expsed for two to 14 months by inhalation to 100125 mg/m3 antimony trioxide,pulmonaiy retention increased with increasing length of expsure; followig cessation of

expsure, pulmonaiy levels declined slowly (Gross et al. 1955b).

298 IAC MONOGRAHS VOLUME 47

Expsure of rats by inhalation to 119 mg/m3 antimony trioxide dust (geometric meanparticle size, 1.3 J.m) for 80 h resulted in total uriaiy excretion of less than 40 J.g antimonytrioxide within four days (Gross et al., 1955a).

A single administration to rats by stomach tube of 0.2 g antimony trioxide suspended inwater resulted in total uriaiy excretion of 3.2% of the dose durig the subsequent eightdays. Faecal excretion was detected in rats for several weeks followig cessation of adminis-tration of 2% antimony trioxide in the diet; after three weeks, faecal excretion was lowerthan uriaiy excretion levels (Gross et aL., 1955a).

Exposure of female dogs by inhalation to about 5.5 mg/m3 animony tnsulfide dust froma smelter (particle size, -c 2 J.m) for ten weeks resulted in uriaiy excretion of up to 16-18mg/l antimony (Brieger et al., 1954).

(ü) Toxic effects

The oral LD~ for antimony tnoxide in rats is above 20 g/kg bw; however, reduced growthand other nonspecific effects were seen with 1 glkg bw (Smyth & Carpenter, 1948). ln con-trast, administration of 16 glkg bw antimony trioxide to rats by stomach tube resulted in noapparent il effects within a 30-day observation period (Gross et al., 1955a). Reduced weightgain, a slight reduction in absolute weight of the spleen and heart and a slight increase inabsolute and relative weight of the lungs were observed in rats given 1 % antimony trioxide inthe diet for 12 weeks (Hiraoka, 1986). Vomiting and gastrointestinal disturbances ocurredin dogs after daily ingestion of approxiately 0.15 glkg bw antimony trioxide or more; vomit-ing was induced by similar doses in a cat, and continued daily doses caused significant weightloss (Fuiy, 1927).

Intratracheal instilation of 50 mg antimony trioxide-cntaining smelter dust to rats didnot result in lung fibrosis, although thin argyophilc fibres were seen (potkonjak & Vishn-jich, 1983). No fibrosis was descnbed after long-term, repeated expsure of rats and rabbitsby inhalation to 100125 mg/m3 and 89 mg/m3 antimony trioxide (average particle size, 0.6J.m), respectively. However, at these dose levels, rapid mortlity ocurred, particularly in

rabbits, due priariy to pneumonia (Gross et al., 1955b).Increased lung weight, focl fibrosis, adenomatous hyperplasia, multinucleated giant

cells and pigmented macrophages were observed in female rats expsed to 1.6 and 4.2 mg/m3antimony trioxide (commercial grade; average paricle size, 0.4 J.m) for one year by inhala-tion. Similar doses caused no expsure-related change in miniature pigs (Watt, 1983). In-creased death rates due to pneumonia were observed in guinea-pigs followig inhalationexpsure to antimony trioxide; cloudy swelling of the liver cells ocurred in almost half of theanimais expsed, but there was no other indication of systemic toxicity (Dernehl et aL., 1945).

Rats expsed to 3.1 mg/m3 antimony trîulfide by inhalation for six weeks developedelectrocrdiographic changes, notably with flattened T -waves; on autopsy, the heart wasfound to be dilated, with signs of degenerative changes; focl haemorrhage and congestion inthe lungs were considered to be secondaiy to heart failure. Similar pathological effects wereseen in rabbits expsed to 5.6 mg/m3 for six weeks. Cardiotoxic changes were observed in twodogs expsed to 5.6 mg/m3 for ten weeks, but not in two dogs expsed to 5.3 mg/m3 for sevenweeks (Brieger et al., 1954).

ANIMONY TRIOXIDE AN ANIMONY TRISULFIDE 299

Degenerative changes in the liver and in the tubular epithelium of the kidney were ob-served in rabbits expsed to 27.8 mg/m3 antimony trisulfide for five days (Brieger et al., 1954).

(ii) Effects on reproduction an prenatal toxicityFemale rats were expsed by inhalation for 4 h per day for 1.5-2 months to 0 or 250

mg/m3 antimony trioxide. They were then mated, and expsures continued until days 3-5 be-fore expected delivery. Pregnancy was obtained in 16/24 treated females and in 10110 con-

troIs. Litter size and weight of offsprig at birh and weaning were not altered by expsure toantimony trioxid~ (Belyaeva, 1967).

Pregnant female rats (six to seven per group) were expsed by inhalation to 0,0.027,0.082 or 0.27 mg/m3 antimony trioxide for 24 h per day for 21 days. Fetal growth and viabilty

were assessed at the end of gestation. Maternai boy weight gain was not affected by exp-sure, but, at the high-dose level,increased pre- and postimplantation death of embiyos wasobserved. At the mid-dose level, preimplantation loss and fetal growth retardation wereevident (Gri et al., 1987).

No data on antimony trisulfide were available to the Workig Group.

(iv) Genetic and related effects

Antimony trioxide produced differential kiling in DNA repair-proficient compared torepair-deficient strains of Bacillus subtilis. ln a spot test, it was not mutagenic to Eschenchiacoli BIr WP2 or to Salmonella typhimurium TA1535, TA1537, TA1538, TA98 or TAUx) (detailsnot given) (Kanematsu et al., 1980).

No data on antimony trisulfide were available to the Working Group.

(b) Humans

(i) Absorption, distribution, exretion and metabolismThree workers with pulmonaiy changes related to expsure to antimony trioxide ex-

creted 425, 480 and 680 I-g/l antimony in urie, while another patient with antimony pneu-mocniosis had uriary levels of 55 and 281-g/i seven months and fouryears after retirement,respectively (McCallum, 1963). High levels (not given separately) of antimony were de-tected in the urie of workers exposed for several years to antimony trioxide; high excretionlevels were also found after one month's cessation of exposure (Klucík & Kemka, 196).High excretion levels were also seen in antimony production workers examined by Cooper etal. (1968). X-Ray spectrometiy has demonstrated that inhaled antimony dust may be re-tained in the lung for long periods (McCallum, 1967; McCallum et al., 1971). The amount ofantimony retained in the lungs tended to rise with duration of employment at an antimonysmelter, suggesting that accumulation may take place (McCallum et al., 1971).

Among antimony trisulfide workers expsed to antimony levels generally higher than 3mg/m3, uriaiy excretion of antimony was 0.8-9.6 mg/i (Brieger et al., 1954).

(ü) Toxic effects

Accidental oral intake of antimony trioxide leached from enamel or ceramic glaze intoacid beverages was reported to result in a burning sensation in the stomach, colic, nausea,vomiting and, ocsionally, collapse (Monier-Wiliams, 1934). Complete recoveiy ocursafter several days (Dunn, 1928).

300 lAC MONOGRAHS VOLUME 47

Smelter workers expsed to antimony trioxide frequently complained of syptoms re-lated to mucous membrane irtation, such as rhinitis (with cases of septal pedoration andloss of smell)J phaiygitis, laiygitis (sometimes with aphonia), gastroenteritis, bronchitisand pneumonitis. Other syptoms, less often encountered, included weight loss, nausea,vomiting, abdominal cramps and diarrhoea (Renes, 1953).

ln other studies, only ski irtation (Oliver, 1933) or no indication of systemic toxicity

(Potkonjak & Pavlovich, 1983) was found in sm el ter workers. Ski lesions ('antimony spts')

in workers exposed to antimony trioxide develop mainly in areas expsed to heat and wheresweating ocurs (Stevenson, 1965). Occsionally, positive patch tests with antimony trioxidehave been recorded (Pschoud, 196). Antimony triulfide has not been reported to causedermatitis (National Institute for Occupational Safety and Health, 1978).

Radiographic changes (rounded opacities) in smelter workers expsed to antimonytrioxide were first descnbed in 196 in Yugoslavi (Krajovic et al., 196). The smelter dustcontained antimony trioxide and some pentoxide, with low concentrations of silca and arse-nic oxide. ln a follow-up study of these smelter workers, the earliest changes were seen onlyafter at least nine years of expsure, and no evidence was round of progression after cessa-tion of expsure. Some evidence was found of mixed restrictive as well as obstructivechanges in bronchi and small airays (Potkonjak & Pavlovich, 1983).

McCallum (1963) also noted in the UK that sm el ter workers with pneumocniosis, acondition he termed 'antimony pneumocniosis', were generally syptomless. The degreeof radiographic abnormalities was correlated with the amount of antimony retained in thelungs and with duration of expsure; early changes were recorded in these workers after onlya fewyears of employment (McCallum et al., 1971). ln a cross-sectional study of 274 smelterworkers in 1965-, 26 new cases of antimony pneumocniosis were found and 18 were al-

ready under observation (McCallum, 1967). A subsequent study included 113 men, 46 ofwhom had radiographic abnormalities; six had severe abnormalities (McCallum et al., 1971).Additional cases of pneumocniosis with rounded opacities were se en in antimony smelterworkers in the USA; the radiographic abnormalities were not assoiated with changes in pul-monaiy function (Cooper et al., 1968). Possible antimony pneumocniosis has also been re-corded in two chemical workers expsed to antimony trioxide dust (Guzman et al., 1986).

Following several deaths, possibly related to heart disease, among workers expsed to0.6-5.5 mg/m3 antimony triulfide, a study revealed electrocrdiographic changes, mainly in

T -waves, in 37/75 workers; after cessation of expsure, the changes persisted in 12/56 work-ers who were re-examined. Gastrointestinal disturbances were also reported (Brieger et al.,1954). Electrocrdiographic changes were also observed in smelter workers by Klucík and

Ulrich (196).

(ii) Effects on fertilty and on pregnancy outcomeBelyaeva (1967) described the reproductive outcomes or 318 women in the USSR work-

ing with dusts containing metallc antimony, antimony trioxide and antimony pentasulfideand of 115 control women. The women expsed to antimony dusts more frequently had pre-mature birhs (3.4% versus 1.2%, respectively) and spontaneous abortions (12.5% versus4.1 %, respectively). The average birh weights of the 70 children of the expsed women were

ANMONY TRIOXIDE AN ANMONY TRISULDE 301

similar to those of the 20 children of the control women (336 g and 3350 g, respectively);however, at one year of age, the children of the expsed women were significantly lighterthan the control chidren (896 g and 10050 g, respectively). (Te Workig Group noted thatthe numbers of premature birhs and spntaneous abortions were not stated.)

(iv) Genetic an related effectsNo data were available to the Workig Group.

3.3 Case report~ and epidemiological studies or carcinogenicity to humans

ln a report whieh quoted an unpublished statement isued in 1973 that ten cases of lungcancer had ocurred among antimony process workers in the UK in 1969-71, with 8.0 ex-pected, it was stated that no data were given on smokig nor on the methods used to calcu-late expected rates (National Institute for Occupational Safety and Health, 1978).

4. Summary of Data Reported and Evaluation

4.1 Exposure data

Antimony trioxide is produced from stibnite ores (antimony triulfide) or as a by-prod-uct of lead smelting and production. It is used mainly in fire-retardant formulations for plas-tics, rubbers, textiles, paper and paints. It is also used as an additive in glass and ceramicproducts and as a catalyst in the chemical industiy. Occupational expsure may ocur durigmining, procssing and smelting of antimony ores, in glass and ceramics production, and dur-ing the manufacture and use of products containing antimony trioxide.

Antimony triulfide is used in the production of explosives, pigments, antimony saltsand ruby glass. Occupational expsure may ocur durig these processes and also durig themining, processing and smelting of ores containing antimony trisulfide.

4.2 Experimental carcinogenicity data

Antimony trioxide was tested for carcinogenicity by inhalation expsure in male andfemale rats of one strain and in female rats of another strain, producing a significant increasein the incidence of lung tumours (scirhous and squamous-cell carcinomas and bronchioloal-veolar tumours) in females in both studies. No lung tumour was se en in male rats.

Antimony ore concentrate (mainly antimony triulfde) was tested for carcinogenicityby inhalation expsure in male and female rats of one strain, producing a significant increasein the incidence of lung tumours (scirhous and squamous-cell carcinomas and bronchioloal-veolar tumours) in females. No lung tumour was se en in males.

4.3 "uman carcinogenicity data

The available data were inconclusive.

302 IAC MONOGRAHS VOLUME 47

4.4 Other relevant data

Antimony trioxide causes pneumocniosis in humans. One study of women exposed todusts containing metallc antimony, antimony trioxide and antimony pentasulfide suggestedthat they may have had an excess incidence of premature birhs and spontaneous abortionsand that their children's growth may have been retarded.

Antimony trioxide induced DNA da mage in bacteria. (See Appendix 1.)

4.5 Evaluation 1

There is inadequate evidence for the carcinogenicity of antimony trioxide and antimonytrisulfide in humans.

There is suffcient evidence for the carcinogenicity of antimony trioxide in experientalanimais.

There is limited evidence for the carcinogenicity of antimony trisulfide in experientalanimais.

Ove rail evaluationsAntimony trioxide is possibly carcinogenic to humans (Group 2E).Antimony trisulfide is not classifiable as to its carcinogenicity to humans (Group 3).

5. References

American Conference of Govemmental Industrial Hygienists (ACGIG) (1988) Threshold Limit Valuesand Biological Expsure Indices for 1988-1989, Cincinnati, OH, p. 11

Anzon, Inc. (1988) Product Bulletin: Antimony Trioxide, TMS, Philadelphia, PAArbeidsinspectie (Labour Inspection) (1986) De Nationale MAC-Lijst 1986 (National MAC-list 1986)

(P145), Voorburg, Ministry of Social Afairs, p. 7Arbejdstilsynet (Labour Inspection) (1988) Graensevaerdier for Stoffer og Materia/er rIimit Values for

Materials) (At-avisning No. 3.10.2), Copenhagen, p. 11Asarco, Inc. (1988a) Product Bulletin: Antimony Oxide, New York

Asarco, Inc. (1988b) Materia/ Data Safety Sheet: Antimony Oxide, New YorkBelyaeva, AP. (1967) The effect produced by antimony on the generative function (Russ.). Gig. Tr. prot

Zabol., 11, 32-37Brieger, H., Semisch, C. w., III, Stasney, J. & Piatnek, D.A (1954) Industrial antimony poisoning. Ind.

Med. Su~, 23, 521-523

lFor definitions of the italicized tenus, see Preamble, pp. 21-30.

ANIMONY TRIOXIDE AN ANIMONY TRISULFIDE303

Cooper, D.A., Pendergras, E.F., Vorwld, A.J., Mayock, RL & Brieger, H. (1968) Pneumocniosisamongworkers in an antimonyindustry. Am. 1 Rontgenol. Radium Ther. nucl. Med., 103,495-508

Demehl, Cu., Nau, CA. & Swets, H.H. (1945) Animal studies on the toxicity of inhaled antimonytrioxide. 1 ind. Ryg. Toxicol., 27,256-262

Deutshe Forshungsgemeinschaf (German Researeh Society) (1988) Maxmale Aritsplatzkonzentra-tionen und Biologiche Aritsstoffolerazwerte 1988 (Maxmal Concentrations in the Workplaceand Biological Tolerance Values for Working Materials 1988) (Report No. XX, Weinheim,VCH Verlagsgesllschaf mbH, p. 19

Direktoratet for Arbeidstilsynet (Direetorate for Labour Inspection) (1981) Administrative Nonner forForurensning i Aridsatmosfaere 1971 (Administrative Norms for Pollution in Work Atmosphere1981), (No. 361), Oslo, p. 7

Donaldson, H. & Casady, M. (1979) Environmental Exsure to Airbme Contaminants in the Antimonylndustry 1975-1976 (DREW (NlOSR) Publicaiion No. 79-140), Cincinnati, OH, National Insti-tute for Occpation al Safety and Health

Drake, G.J., Jr (1980) Flame retardants for textiles. ln: Mark, H.F., Othmer, D.E, Overberger, CG.,Seaborg, G.I & Graysn, N., eds, Kirk-OthmerEncyclopedia ofChemical Technology,3rd ed., Vol.10, New York, John Wiley & Sons, pp. 420

Dunn, J.1 (1928) A curious ca of antimony poisoning. Analyst, 53,532-533

ElIer, F.M., ed. (1985) NlOSR Manua of Analytical Methods, 3rd ed., lst Suppl. (DRRS (NIOSH) Publ.No. 84-100), Washington DC, US Govemment Prnting Offce, pp. 805-1-805-5

Flury, F. (1927) Toxicology of antimony (Ger.). Nauyn~Schmiedeberg's Arh. ex. Pathol. Phanakol.,126,87-103

Freedman, LD., Doak, G.O. & Long, G.G. (1978) Antimony compounds. ln: Mark, H.F., Othmer, D.F.,Overberger, CG., Seaborg, G.T & Graysn, N., eds,Kirk-OthmerEncyclopediaofChemical Tech-nology, 3rd ed., Vol. 3, New York, John Wiley & Sons, pp. 105-128

Grin, N. v., Govorunova, N.N., Bessmertny, A.N. & Pavlovieh, LV. (1987) Exprimental study of embry-otoxie effect of antimony oxide (Rus.). Gig. Sanit., 10, 85-86

Gros, F., Brown, J.H. u., Westriek, M.L, Srsic, RF., Butler, N.L & Hateh, IF. (1955a) Toxicologicstudyof calcium halophosphate phosphors and antimony trioxide. 1. Acute and ehronie toxieity andsorne pharacologie aspets. Anh. ind. Reath, 11, 473-478

Gros, F., Westriek, M.L, Brown, J.H.U., Srsie, RF., Schrenk, H.H. & Hateh, TF. (1955b) Toxicologiestudy of calcium halophosphate phosphors and antimony trioxide. II. Pulmonar studies. Arh.ind. Reath, 11, 479-4

Groth, D.H., Stettler, LE., Burg, J.R, Busey, WM., Grant, G.C & Wong, L (1986) Carcinogenie effectsof antimony trioxide and antimony ore concentrate in rats. 1 Toxicol. environ. Reath, 18, 607-626

Guzman, J., Costabel, u., Orlowska, M., Schmitz-Schumann, M. & Freudenberg; N. (1986) Lung fibro-sis afer expure to antimony trioxide dust (Abstract; Ger.). Zbl. allg. Pathol. Anat., 131, 278

Hawley, G.G. (1981) Condensed Chemical Dictiona, 10th ed., New York, Van Nostrand Reinhold Co.,

pp.81-82Health and Safety Exective (1987) Occupaional Exsure Limits 1987 (Guidance Note EH 40/87), Lon-

don, Her Majesty's Stationery Office, p. 9Hiraoka, N. (1986) The toxieity and organ-distribution of antimony afer ehronic administration to rats.

L Kyoto prel med. Coll., 95, 997-1017lARC (1988) lnjbnnion Bulletin on the Survey of Chemicals Being Tested for Carinogenicity, No. 13,

Lyon, p. 144

304 IAC MONOGRAHS VOLUME 47

Institut National de Recherche et de Sécrité (National Institute for Resarch and Safety) (1986) ValeursLimites pour les Concentrations des Substances Dangereuses Dan l'Air des Lieux de Traail (Limit

Values for Concentrations of Dangerous Substances in the Air of Work Places) (ND1609-125-86), Pars, p. 557

International Labour Offce (1984) Occupaiona Exsure Limits for Airbme Toxic Substances, 2nd rev.ed. (Occupational Safety and Health Series No. 37), Geneva, pp. 445

Kanematsu, N., Hara, M. & Kada, T (1980) Rec asay and mutagenicity studies on metal compounds.Muta!. Re., 77, 109-116

Karajovic, D., Potkonjak, V. & Gospavic, J. (1960) Silcoantimonosis (Ger.). Arh. Gewerbepathol. Gew-erbehyg., 17, 651-65

Klucík, 1. & Kemka, R (1960) The excretion of antimony in workers in antimony metallurgical works

(Czech.). Prac. Lek., 12, 133-138Klucík, 1. & Ulrich, L (1960) Electrocdiographie examinations of workers in an antimony metallurgi-

cal plant (Crech.). Pra. Lei., 12, 23243- LeSota, S. (1978)Paint/Coatingr Dîêtionai, Philadelphia, PA, Federation ofSocieties for Coatings Tech-

nology, p. 33

Llewellyn, TO. & Isaac, E. (1988) Antimony Quaierly, Minera lndustry SU/veys, Washington DC, USDepartment of the Interior, Bureau of Mines, pp. 1-5

Loge, J.P., Jr, ed. (1989) Methods of Air Sampling and Anysis, 3rd ed., Chelsea, MI, Lewis Publishers,pp. 83-92, 143-150, 226230, 357-360, 623-638

Lüdersorf, R, Fuchs, A., Mayers, P., Skulsuksai, G. & Schacke, G. (1987) Biological asssment of expsure to antimony and lead in the glas-producing industry. lnt. Arh. occup. environ. Heath, 59,

469-474Lyons, J.W (1980) Flame retardants. ln: Mark, H.P., Othmer, D.P., Overberger, CG., Seaborg, G:r. &

Graysn, N., eds, Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed., VoL. 10, New York,

John Wiley & Sons, pp. 348-354Mannsville Chemical Products Corp. (1981) Chemical Products Synopsis: Antimony Oxide, Cortland, NYMannsville Chemical Products Corp. (1985) Chemical Products Synopsi: Antimony Oxide, Cortland, NYMcCallum, RI. (1963) The work of an ocpation al hygiene servce in environmental control. Ann.

occup. Hyg., 6, 55-6McCallum, RI. (1967) Detection of antimony in procss workers' lungs by X-radiation. Tra. Soc. oc-

cup. Med., 17, 134-138McCallum, RI., Day, M.J., Underhil, J. & Aird, E.G.A. (1971) Measurement of antimony oxide dust in

human lungs in vivo by X-ray spetrophotometry. ln: Walton, WH., ed., lnhed Paiic/es III, Old

Woking, UK, Unwin Bros, pp. 611-619Monier-Wiliams, G. W (1934) Antimony in Enae1led Hollow-war, London, His Majestys Stationery

OffceNational Institute for Occpational Safety and Health (1974) US Nationa Occupaiona Exsure Survey

1972-74, Cincinnati, OHNational Institute for Ocpational Safety and Health (1978) Criteri for a Reommended Standad ...

Occupationa Exsure to Antimony, Cincinnati, OHNational Institute for Occpational Safety and Health (1983) US Nationa Occupaiona Exsure Survey

1981-1983, Cincinnati, OHNational Swedish Board of Occpation al Safety and Health (1987) Hygnska Grãärden (Hygienic

Umit Values) (Ordinace 1987:12), Solna, p. 12

ANIMONY TRIOXIDE AN ANMONY TRISULFIDE 305

Oliver, T (1933) The health of antimony oxide workers. Br. med. 1, i, 1094-1095Palencia, CM. & Mishra, CP (1986) Antimony Availability - Maret Economy Countries, A Minerals

Availability Appraisal (Bureau 0/ Mines In/onnation Circular 9098), Washington DC, US Depart-ment of the InteriOf

Pashoud, J.-M. (1964)Clinical notes on ocpation al contact eczemas from arnic and antimony (Fr.).l)ennatologica, 129, 410-15

Potkonjak, V. & Pavlovich, M. (1983) Antimonosis: a paricular fonn of pneumocniosis. I. Etiology,

c1inical and X-ray findings. Int. Arh. occup. environ. Health, 51, 199-207Potkonjak, V. & Vishnjich, V. (1983) Antimoniosis: a particular fonn of pneumocniosis. II. Exprimen-

tal investigation. Int. Arh. occup. environ. Health, 51,299-303Pough, EH. (1960) A Field Guide to Roks and Minerals, 3rd ed., Boton, MA, Houghton Miffin Co., p.

102

Renes, LE. (1953) Antimony poisoning in industry. Arh. ind. Hyg. occup. Med., 7,99-108Robert, WL, Rapp, G.R., Jr & Weber, J. (1974) Encyclopedia 0/ Minerals, New York, Van Nostrand

Reinhold Co., p. 582Samsonov, G.W, ed. (1982) The Oxide Handbok (Engl. Transl.), New York, IFIPlenum, p. 375Smyth, H.E, Jr & Carpnter, c.p (1948) Further exprience with the range finding test in the industrial

toxicology laboratory. 1 ind. Hyg. Toxicol., 30, 63-6Stevenson, CJ. (1965) Antimony spots. Tra. St Johns Hosp. dennatol. Soc., 51,4045Työsuojeluhalltus (National Finnish Board of Occpation al Safety and Health) (1987)HTP-A/ot 1987

(TLV Values 1987) (Sa/ety Bulletin 25), Helsinki, Valtion Painatuskeskus, p. 10US Environmental Protection Agency (1983) Methods for the Chemical Analysis o/Water and Wastes (US

EPA-600/4-79-020), Cincinnati, OH, Environmental Monitoring and Support LaboratoryUS Environmental Protection Agency (1986) Test Methods for Evaluating Solid Waste. Volume lA. Labo-

ratory Manual Physical/Chemical Methods (SW-846), 3rd ed., Washington, DC, Office of SolidWaste and Emergency Response

US Occpation al Safety and Health Administration (1987) Toxic and hazardous substances. US CodeFed. Regul. Tille 29, Part 1910.100, p. 677

Watt, WD. (1983) Chronic Inhalation Toxicity 0/ Antimony Trioxide: Validation o/the Threhold Limil Val-ue, Detroit, MI, Wayne State University, PhD Thesis

Weast, R.C, ed. (1985) CRe Handbok o/Chemistryand Physics, 66th ed., Cleveland, OH, CRC Press, p.B-74

Windholz, M., ed. (1983) The Merck Index, 10th ed., Rahway, NJ, Merck & Co., p. 104