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Antimony in the metallurgical industry: A review of its chemistry and
environmental stabilization options
PII: S0304-386X(16)30347-4
DOI: doi: 10.1016/j.hydromet.2016.06.014
Reference: HYDROM 4380
Please cite this article as: Multani, Ravinder S., Feldmann, Thomas, De-
mopoulos, George P., Antimony in the metallurgical industry: A review of its
chemistry and environmental stabilization options, Hydrometallurgy (2016), doi:
10.1016/j.hydromet.2016.06.014
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H3A 0C5
* Corresponding author. Tel: +1 514 398 2046; Fax: +1 514 398 4492
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E-mail address: george.demopoulos@mcgill.ca
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Abstract
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Antimony (Sb) is an impurity element that is increasingly encountered in the mineral
important one. During processing antimony is mobilized reporting to waste solid tailings or
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effluent streams. This becomes a matter of concern since antimony is similar to arsenic in many
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respects, both sharing similar chemical properties as well as toxicity and thus have negative
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environmental implications, especially in the context of industrial effluents and their treatment.
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This review summarizes the available literature on antimony in the environment and its removal
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with emphasis on effluent treatment. Antimony speciation as well as oxidation was presented at
various conditions (pH, Eh, temperature, and concentration) to provide a basis of its aqueous
behaviour, an important foundation for industrial effluent treatment. For immobilizing antimony
in the environment via precipitation from effluents several mineral candidates were identified of
which schafarzikite, FeSb2O4, and tripuhyite, FeSbO4, were proposed as very attractive due to
Contents
1. Introduction .............................................................................................................................. 1
2. Antimony in the environment .................................................................................................. 3
2.1 Air................................................................................................................................... 3
2.2 Soil.................................................................................................................................. 3
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2.3 Water .............................................................................................................................. 4
2.4 Environmental treatment ................................................................................................ 5
3. Industrial processing and treatment ......................................................................................... 7
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3.1 Antimony metallurgy ..................................................................................................... 7
3.2 Mineral processing ......................................................................................................... 7
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3.3 Pyrometallurgy ............................................................................................................... 8
3.4 Hydrometallurgy ............................................................................................................ 9
3.5 Industrial treatment and antimony recovery ................................................................. 11
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4. Antimony speciation .............................................................................................................. 12
4.1 The SbH2O system ..................................................................................................... 12
4.2 The SbSH2O system ................................................................................................. 13
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5. Antimony oxidation Sb(III) to Sb(V) ................................................................................. 15
5.1 Oxygen (O2) ................................................................................................................. 16
5.2 Hydrogen peroxide (H2O2) ........................................................................................... 16
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1. Introduction
Antimony (Sb, atomic number 51) is found in Group 15 of the Periodic Table directly
below arsenic and has a standard atomic weight of 121.76 gmol1. Its name is of Greek origin,
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anti plus monos, translating to a metal not found alone. This is accurate as native
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antimony metal is rarely found, it is usually discovered as a sulfide mineral, the most important
being stibnite, Sb2S3 (Lide et al. 2007). Antimony metal is silvery in colour, has a fairly low
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melting point for a metal, 630.6 oC, is very brittle and a poor conductor of heat and electricity.
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Similar to arsenic, it is typically found in four oxidation states: 3, 0, +3, and +5.
More than 200 antimony minerals are found in nature, common primary and secondary
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minerals are listed in Tables 1 and 2, respectively. Primary antimony minerals are typically
sulfides, mainly because antimony has a higher affinity for sulfur than oxygen (chalcophile).
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Under ambient pH and temperature, most primary antimony minerals are fairly stable and thus
are relatively insoluble, little to no dissolved antimony is found in the surrounding aqueous
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solutions. However, in oxygenrich environments the sulfide minerals react with oxygen to
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produce secondary minerals. These can become unstable and result in antimony release (Roper et
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al. 2012). Table 2 includes information on the frequency of occurrence of the secondary minerals
based on the number of localities it has been found in. Using this information, one may infer
Antimony and its various compounds have been known and used since ancient times,
dating back at least 6000 years. There is evidence dating to ancient Egypt, where synthetic
antimonate compounds were used as colorants for glass and as eye shadow, among other things
(Shortland 2002; Selim 2012). Various applications continued over the ages where it was also
used as material for ornaments, jewellery, and alloys. Antimony compounds also found use in
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known as tartar emetic. Its main use was as an emetic (inducing vomiting), however, also as a
laxative to purge the human body of illnesses and toxins (Lide et al. 2007). Currently, antimony
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compounds find a multitude of applications such as semiconductors for gas sensing applications
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(liquefied petroleum gas, hydrogen gas, carbon monoxide gas, butane gas, etc.), infrared
detectors, diodes, and much more (Tianshu and Hing 1999; Lide et al. 2007). Iron antimonates
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have been studied for at least thirty years and found to have specific catalytic properties, such as
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the ammoxidation of propylene (Teller et al. 1985). Inorganic ion exchangers such as iron
antimonates have also been found to be selective toward some alkali metals, said to be superior
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to ionexchange resins due to their thermal stability and differential selectivity (Rawat et al.
1976; Rawat et al. 1984). Although the aforementioned applications seem as though they would
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account for the bulk of antimony commodities in the market, a large portion of the manufactured
antimony compounds find their way into flame retardants, paints, glass, pottery, and as a
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hardening agent in lead bullets and ammunition (Lide et al. 2007; Anderson 2012).
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Antimony and arsenic are typically associated together due to their several similarities
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in chemical behaviour as they both fall in Group 15 of the Periodic Table, even where toxicity is
concerned. However, there are some noteworthy differences, the main being the degree of
toxicity and the availability of each element in the environment, which play a significant role on
its biological and ecological toxicity. Arsenic is likely more toxic than antimony, however, it is
also more abundant due to both natural and anthropogenic activities, making it even more likely
to be encountered than antimony. Arsenic has been proven to be a definite human carcinogen as
it has been the subject of numerous studies, affecting areas of the skin, lung, bladder, kidney and
liver (Gebel 1997). On the other hand, antimony has been much less studied and thus there is
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limited data on its toxicity. Most antimony studies normally include antimony trioxide, Sb2O3,
as their subject of toxicological tests since it is the most widely used antimony compound.
Although the results are slightly skewed to the behaviour of Sb2O3 in biological studies,
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nonetheless, antimony was found to be a possible human carcinogen (IARC 1980).
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2. Antimony in the environment
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2.1 Air
Antimony and its compounds, usually antimony trioxide, find their way into the
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atmosphere from several sources and exist as solid compounds suspended in air (Belzile et al.
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2011). Sources of atmospheric pollution can be separated into natural and anthropogenic, the
latter consists of mining, smelting and refining operations, fossil fuel combustion, and the
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areas is several ngm3, closer to anthropogenic regions (i.e. urban incinerators, mine sites, and
metal smelters) this value can increase to hundreds of ngm3 (Belzile et al. 2011). In China, the
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reported concentration in anthropogenic vicinities such as mining areas and waste incinerators
was as high as 575 mgm3 (He et al. 2012). Worldwide regulations on the allowable antimony
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industrial air emissions vary from country to country, however, in Canada and China, total
annual basis (Canadian Council of Ministers of the Environment 1999; He et al. 2012).
2.2 Soil
Antimonys concentration in the earths crust is approximately 0.2 to 0.3 mgkg 1 and is
typically found as the sulfide mineral stibnite (Sb2S3), sometimes as valentinite (Sb2O3). Due to
increased antimonybearing mineral mining/processing over the past few decades, there has been
increased deposition of antimony into the environment (Selim 2012). The anthropogenic sources,
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stated earlier, contribute to a significant portion of the pollution. Soil concentrations close to
these sources can reach values of 15,000 mgkg 1and even 80,200 mgkg 1, as were the cases in
southern Tuscany and a smelter site in New Zealand, respectively (Wilson 2004; Selim 2012).
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Table 3 gives examples of increased Sb contamination levels in soils surrounding anthropogenic
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sites such as mining, smelting and shooting range sites, the latter due to usage of leadantimony
ammunition. Industrial regulations on environmental solid waste releases are not widely adopted.
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Typically the waste is transferred to settling or tailings areas and subjected to wastewater
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treatment for release. The maximum allowable concentration into agricultural soils is 10 mgkg
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for antimony, which happens to be more stringent than arsenic (15 20 mgkg 1) (Kabata
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Pendias 2011).
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2.3 Water
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below 1 gL1. Most naturally occurring antimony in fresh waters is from rock weathering and
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soil runoffs (Filella et al. 2002a). One of few exceptions to low concentrations in natural waters
are hot springs where the concentrations can sometimes exceed 500 mgL1, although the
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likelihood of encountering this situation is low. In oceans, the concentration is even less than in
fresh waters, estimated to be 200 ngL1 (Filella et al. 2002a). Anthropogenic sites and their
vicinities typically have concentrations of one to two orders of magnitudes higher than natural
waters, in China, this was found to be as high as 263 gL1 in certain mine natural waters. Many
regulatory bodies worldwide place strict limits on antimony content in drinking water as it has
been labelled a hazardous substance. The World Health Organization, China, USEPA and
European Union drinking water standards are set to 20 gL1, 5 gL1, 6 gL1and 5 gL1,
respectively (Council of the European Union 1998; USEPA 1999; WHO 2006; He et al. 2012).
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Industrial environmental release regulation varies or is not specific for antimony and its
compounds, however, sometimes arsenic limits are associated to antimony due to their
similarities, which is 0.5 mgL1 (monthly average) and 1.0 mgL1 (for a grab sample) from the
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Canadian Metal Mining Effluent Regulation (Government of Canada 2014).
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The natural and anthropogenic concentration of antimony in the air, soil and water
systems have been shown to differ by at least one order of magnitude, however, the difference is
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typically larger (two orders) when approaching the anthropogenic sites and even more
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pronounced at the sites themselves. To reduce the concentration in these regions, extensive
Particulate and toxic substance releases such as antimony oxides are normally captured
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and subjected to subsequent treatment. They are collected in flues, condensing pipes, baghouses,
and electrostatic precipitators (Anderson 2012). Waste incineration is a prime example where
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municipal waste along with some landfill waste is burned, 20% of which becomes bottom ash
and 2 3% results in air pollution control residue (APC). Elemental antimony, which is fairly
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volatile at temperatures > 500 oC, only about half of it reports to the bottom ash while the other
half reports to the APC residue, which contains many other toxic substances and must be further
processed before moving into landfill (Cornelis et al. 2008; Okkenhaug et al. 2013). Since the
APC residue is very alkaline, the choice of treatment is neutralization with other industrial
wastes containing sulfuric acid and iron to yield a final pH between 8 and 9. Iron compounds
such as iron hydroxides and iron oxyhydroxides precipitate out of solution due to neutralization
and many metals either adsorb or coprecipitate with these compounds. The precipitate moves
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onto landfills, while the neutralized solution, which still contains trace metals, moves onto
There are extensive soil remediation methods to treat highly polluted soils, these include
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leaching, soil amendment (immobilization), biodegradation (microbial degradation of
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substances), phytoremediation (removal of metals by plant uptake), vitrification (immobilization
via melting into a glasslike solid), encapsulation, excavation (removed and placed in landfill),
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and isolation (placing subsurface barriers such as clay or plastic liners) (KabataPendias 2011).
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A common method appears to be soil amendment since the processing can take place onsite and
is relatively low cost. This is also the choice of treatment for antimony immobilization in many
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sites such as naturally polluted soils, industrial, and shooting range soils. Many materials have
been tested over the past several years, as noted by lvarezAyuso et al. (2013), which include
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phosphate and sulfurbased amendments, sodium humate, drinking water deironing sludge,
calcium hydroxide, green waste compost mulch, Portland cement, wood bark, and phosphate
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hydroxide, and Portland cement have proven to be effective. However, there is a lack of
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implementation of effective methods to treating mining derived wastes. From lab-scale tests
there are numerous metal oxides and oxyhydroxides such as iron and manganese oxyhydroxide
that have demonstrated high extraction of antimony from soils, however, largescale execution
wastewater treatment plants. A variety of methods are encompassed in treatment plants such as
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sedimentation (Gannon et al. 1986; Wu et al. 2010). Treatment of antimony aqueous waste
streams may be similar to arsenic, which has been studied extensively (Guo et al. 2009).
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3.1 Antimony metallurgy
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Worldwide antimony production statistics and ore body reserves are summarized in Table
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4, with China being the main producer, accounting for almost 80% of total production (U.S.
Geological Survey 2015). Antimony minerals are processed in many different ways and the
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proper method is chosen based on several factors, i.e. grade and type of antimony mineral in ore
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feed, presence of other metals, type of final product and product quality. Like most other
minerals, the processing of antimony can be reduced into three subindustries; mineral
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processing, pyrometallurgy, and hydrometallurgy. Alkaline sulfide leaching of stibnite from base
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metal and gold industries is presented due to the overwhelming number of plants operating under
Like most mineral processing, antimony ore processing consists of ore crushing,
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grinding, classification (gravity separation and cyclones) and flotation. The feed ore typically
contains stibnite along with other gangue minerals. In China, it is pyrite, quartz, calcite, barite,
kaolin, and gypsum. The feed grade is usually between 2 3% antimony and treated through
hand sorting, spiral concentration, and flotation. In depth reviews of antimony ore processing are
presented by Lager and Forssberg (1989 a,b), Solozhenkin and Alekseev (2010a), and Anderson
(2012). In the literature there are various flotation reagent schemes available for such ores and
concentrate (floated) or rejected to the tails (depressed). Aside from antimony ore grade, this
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decision falls on the minerals association with other metals, for e.g. lead, copper, iron, mercury,
arsenic, silver and gold, as well as other parameters such as ore matrix and type (sulfide or
oxide). For simple antimony ores (primarily stibnite with minimal impurities), stibnite is
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activated by lead ions (i.e. Pb(NO3)2) at natural pH and floated with an amyl xanthate collector
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and traditional frothers (e.g. methyl isobutyl carbinol) (Lager and Forssberg 1989 a,b). In cases
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appears to be more selective towards antimony. For more complex ores, intricate regent schemes
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are employed to recover antimony and precious metals into the concentrate or if it is a
contaminant, its rejection is accomplished by the use of depressants (e.g. K2Cr2O7) at high pH
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(alkaline conditions, pH > 10, are detrimental to antimony mineral flotation).
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3.3 Pyrometallurgy
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ores, however, the ore/concentrate antimony grade dictates the most suitable method. Feedstocks
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containing 5 25% antimony are volatized by roasting at ~ 1000 oC; this treatment removes
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sulfur as SO2 offgas and antimony trioxide, Sb2O3, is retrieved as flue dust which can then be
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reduced to antimony metal in reverberatory furnaces using carbon as the reductant (Hua et al.
2003; Anderson 2012; Qin et al. 2015). The reactions are presented in Equations (1) and (2):
Feedstocks with grades in the range of 25 40% are subjected to smelting in a blast furnace at
13001400 oC to yield pure antimony metal. Lastly, antimony raw materials, such as antimony
sulphideSb2S3 containing 45 60% antimony, are liquefied by heating at 550 600 oC after
which it is reduced to pure antimony metal. Historically, SO2 release has been a major concern
when smelting sulfidic ores, especially those containing antimony and arsenic as they are easily
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volatilized and become an environmental issue near smelting sites. Thus, more research has been
focused on reducing emissions all the while increasing metal production, a difficult task since
lower grade ore processing is becoming common practice and requires more ore to yield the
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same metal tonnage. This has prompted researchers to develop methods to reduce emissions
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while accommodating lowgrade ores, one of which includes the use of ZnO as sulfurfixing
agent in a carbonate melt (either Na2CO3 alone or Na2CO3/NaCl mixture) (Yang et al. 2011; Ye
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et al. 2015).
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3.4 Hydrometallurgy
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Many simple and complex lowgrade antimony sulfide ores can be processed through
hydrometallugical techniques, for both antimony and other valuable metals, some even
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Medvedeva 2001; Solozhenkin and Alekseev 2010b). Typically the main objective of the process
is to recover a desired metal associated with the antimony mineral, primarily gold. In some
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(Awe and Sandstrm 2010). In both cases, the most effective and widely used method is alkaline
sulfide leaching which is very selective for antimony, gold, arsenic, mercury, and tin minerals.
The other method is acidic chloride leaching (FeCl3 as leaching agent), however, it is much less
preferred due to chemical complexity, corrosion/acid mist issues, ferric ion accumulation, and
lower antimony/arsenic leaching rates (below 100 oC) as compared to alkaline sulfide leaching
(Yang et al. 2010; Awe and Sandstrm 2010; Anderson 2012). On the other hand, depending on
the ore/concentrate, alkaline sulfide leaching has its disadvantages as well such as high reagent
consumption and adverse effects on downstream metal recovery (i.e. gold), under such
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conditions researchers give preference to an optimized acidic chloride system (Kanarskii and
Adamov 2012). In recent years, a variation of the acidic chloride leaching using antimony
pentachloride (SbCl5) both as leaching agent and oxidant has also shown promise in yielding
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high purity antimony metal/powders while still being efficient. The method uses optimized
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parameters with circular leaching (recycling SbCl5), solution purification steps, and
electrowinning (Solozhenkin and Alekseev 2010b; Yang et al. 2010; Yang and Wu 2014).
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In alkaline sulfide leaching, the commonly used lixiviant to leach antimony and gold is
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a mixture of sodium sulfide and sodium hydroxide. The sodium hydroxide is used to ensure
alkalinity (normally above pH 12) and to prevent the hydrolysis of sodium sulfide and toxic
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hydrogen sulfide gas generation. These reactions are summarized in Equations (3) and (4):
(3)
NaHS + H2O H2S + NaOH (4)
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The presence of sodium hydroxide, i.e. external reagent addition, largely prevents the
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completion of reaction (1) and (2) (Ubaldini et al. 2000; Awe et al. 2013). During the leaching
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stage, stibnite reacts with sodium sulfide to form sodium thioantimonite, Na3SbS3, demonstrated
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chemistry can be more complex than reactions (5) and (6), involving several sulphur and Sb(V)
species such as sulfide, S2, metastable polysufide, Sx2, metastable thiosulfate, S2O32, and
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The antimonybearing solution is then passed to the electrowinning stage where solid
antimony metal is plated at the cathode; Equations (7), (8), and (9) display the primary cathode
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CATHODE: SbS33 + 3e Sbo + 3S2 (7)
4OH 4e + H2O + O2
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ANODE: (8)
2 o
ANODE: S 2e + S (9)
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3.5 Industrial treatment and antimony recovery
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Remediation efforts have increased over the years to recover antimony from a variety of
sources, primarily from intermediate smelter products such as anode slimes, slags, drosses, flue
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dusts, and residues from copper and lead smelters (Anderson 2001; Cornelis et al. 2008; Cao et
al. 2010; Liu et al. 2014). More specifically, these include leadsmelter speiss (containing
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precious metals), leadsoftening skims (common in lead refining), leadsmelter copper dross
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flue dust (common in lead processing), and pyrometallurgical plant antimony oxide residue
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(collected at the electrostatic precipitator). These antimony residues contain significant amounts
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of precious and base metals that must be recovered before recycling the antimony into the feed.
It can be treated in a number of ways, alkaline sulfide leaching being common, where at least
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90% antimony recovery is practised (Anderson and Twidwell 2008). An example of the
conditions yielding more than 99% of antimony removal is outlined by Anderson (2001) where
the pyrometallurgical antimony oxide residue was subjected to 6 hrs of leaching, at 105 oC,
sulfide and free hydroxide concentrations of 100 and 25 gL1, respectively. Other secondary
sources of antimony include recycled batteries, processed in a blast furnace to make lead
bullions, and spent antimony catalysts from the petrochemical industry. Treatment of aqueous
media (wastewater and leach solutions) was previously summarized in the environmental
treatment section (see Section 2.4), typically the residue (usually alkaline) is neutralized with an
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acidic waste solution after which the wastewater may be further treated to retrieve antimony and
precious metals.
4. Antimony speciation
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4.1 The SbH2O system
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Antimony can exist in four oxidation states, 3, 0, +3, and +5, however, in aqueous
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solutions, the predominant species exist in +3 and +5 oxidation states, Sb(III) and Sb(V).
Computer simulations of the relative abundance of both Sb(III) and Sb(V) species in oxic and
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anoxic waters, based on the best thermodynamic data currently available (Table 5), showed that
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Sb(OH)
6 is exclusively present in oxic waters, whereas, Sb(OH)3 is exclusively present in
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anoxic waters (Filella and May 2003). In reality, several sources have reported the presence of
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both Sb(III) and Sb(V) in both oxic and anoxic waters, which contradicts the calculated
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thermodynamic data (Andreae and Froelich 1984; Filella et al. 2009). Some researchers have
attributed this to the result of biological activity, however, others have indicated the more likely
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causes, slow oxidation kinetics between Sb(III) and oxygen in oxic waters and Sb(III) oxidation
to Sb(V) perhaps by polysulfide species (Quentel and Filella 2002; Helz et al. 2002; Leuz and
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Johnson 2005). Thermodynamic data for Sb(III) and Sb(V) is limited in literature as compared to
more common systems. According to the calculated Pourbaix diagram (Figure 1), the hydrolytic
values less than ~ 2, Sb(OH)o3 , at pH values between ~ 2 and 12, and Sb(OH)
4 , at pH values
higher than ~ 12 (Krupka and Serne 2002). For very dilute systems such as the one depicted in
Figure 1, < 0.001M Sb, the dominant species are said to be independent of antimony
concentrations. However, where more concentrated solutions are concerned, > 0.001M Sb, Sb(V)
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may form polynuclear species under acidic conditions (pH < 7). Sb(III) is insignificantly affected
by this at concentrations lower than 0.1M Sb (Krupka and Serne 2002). The polynuclear Sb(V)
5 6
species are Sb12 (OH)4 7
64 , Sb12 (OH)65 , Sb12 (OH)66 , and Sb12 (OH)67 (Accornero et al. 2008).
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Some stability diagrams for aqueous antimony species are presented as follows, although, it must
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be noted that the data relates to very dilute solutions and direct application to concentrated
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solutions may not be relevant.
Figure 2 displays the change in the EhpH diagram of Figure 1 when antimony
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concentrations are increased to 107 and 105 molL1, resulting in solid species (Sb2O3 and
Sb2O4). The solubility of the solid species was obtained from limited thermodynamic data and
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the results are qualitative at most, as stated by Krupka and Serne (2002).
Figure 3 displays the speciation of Sb(III) and Sb(V) as a function of pH in anoxic and
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Figure 4 displays the change in speciation of an Sb(III) aqueous system, studied over a
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large temperature range (25 300 oC) by ZakaznovaHerzog and Porkovski (2006). It can be
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seen that in the acidic region, there is a small change in speciation (relatively unchanged when
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comparing 25 oC and 300 oC). On the other hand, there is a significant decrease in the relative
especially alkaline, many studies have been carried out to understand the complex speciation of
the SbSH2O system. The results are quite varied and Filella et al. (2002b) have suggested
discrepancies may arise from variation in the concentrations of reagents (Na2S in particular) and
the crystallinity of stibnite, Sb2S3. Filella and May (2003) have compiled the best available
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conditions, the relative abundance of each depends on the redox condition of the solution (p). In
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the literature, redox values are stated as Eh (voltage in reference to the standard hydrogen
electrode) or to p, which is the negative log activity of the electron (log(e)), the two are
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(2.303)RT
related by the Nernst factor: Eh = p; where R is the gas constant (8.314 Jmol1K1), T
F
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is the absolute temperature (K), and F is the Faraday constant (96,485 Cmol1) At 25 oC, Eh
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(0.05916 p) V.
and temperatures. Sherman et al. (2000) studied the complexation of Sb(V) in alkaline sulfide
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solutions between 25 and 300 oC, and stated that the dominant species was Sb(HS)+
4 for all three
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o
solutions under 150 C, while higher temperatures yielded mixedligand species
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Sb(HS)4n (OH)+ o
n , which further polymerize past 250 C. The three solutions were: (1) 0.1M Sb
+ 1.15M Na2S; (2) 0.05M Sb + 0.2M NaHS + 0.06M NaOH; (3) 0.05M Sb + 0.2M NaHS +
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1M NaCl + 0.06M NaOH. The study incorporated the use of Xray absorption fine structure
spectra (EXAFS) to determine Sb(V) speciation in solution, which could not distinguish between
more likely species based on the higher presence of HS in the system. In another study,
antimony concentrated solutions and temperatures, ranging from 1100 mM Sb, 0.009 2.5 M
HS, and 193200 oC. Many of the solutions contained species of antimony bonded to four
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sulfur atoms, thus consistent with the SbS43 species, supporting the results of Sherman et al.
Thermodynamic data for the aqueous antimony system has been critically reviewed by
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the aforementioned authors (notably Filella and May 2003) and appears to model the real
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systems (SbH2O, SbClH2O, and SbSH2O) fairly well. Discrepancies with experimental
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data are attributed to kinetic factors that still require extensive study, especially where complex
environmental and biological systems are concerned. Dilute aqueous antimony systems (<
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o
0.001M Sb) are well characterized and are remarkably simple with Sb(OH)
6 and Sb(OH)3 as the
dominant species in oxidizing and reducing conditions, respectively, over the environmental pH
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range (5 9). For concentrated systems (> 0.001M Sb), possible formation of Sb(V) polynuclear
conditions and SbS2 (with Sb(OH)o3 ) in reducing conditions. Temperature effects on speciation
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have been much less studied and point to decreased stability of Sb(V) and Sb(III) species with
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Over the past decade, the oxidation of antimony (with different oxidants) in aqueous
solutions has received much interest in particular in relation to its adsorption onto iron and
manganese hydroxides and oxyhydroxides (Belzile et al. 2001; Leuz et al. 2006b). Another
interest has been the study of antimony oxidation, especially the kinetics, from +3 to +5 since it
plays a major role on the environmental speciation of antimony and thus greatly impacts its
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Leuz and Johnson (2005) studied the oxidation kinetics of Sb(III) via atmospheric
oxygen at 25 oC and concluded that there was no significant oxidation between the pH range 3.6
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to 9.8, even after 200 days. In the pH range of 10.9 to 12.9, they reported significant oxidation
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within 4 to 420 days, more so at pH 12.9. They credited the relative increase in oxidation at
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favourable to change from Sb(OH)
4 to Sb(OH)6 (+45.8 kJ/mol) than Sb(OH)3 to Sb(OH)6
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(+110.6 kJ/mol). At higher pH, the presence of Sb(OH)
4 is increased (Figure 3(a)), especially
past pH 12. Further, there is evidence that the oxidation kinetics can be increased due to
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hydrolysis, as noted by other researchers for cases of Fe(II) and Mn(II) oxidation (Leuz and
Johnson 2005).
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Hydrogen peroxide is a stronger oxidizing agent than oxygen and is present in surface
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waters between 108 and 106 M, which is why it is also considered in oxidation kinetic studies of
natural waters (Leuz and Johnson 2005). Only in the past decade has the influence of H2O2 on
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the oxidation kinetics been studied with effective results. Leuz and Johnson (2005) and Quentel
et al. (2004) both studied the oxidation kinetics of Sb(III) by hydrogen peroxide and determined
it was much faster than oxygen. The former researchers determined the reaction kinetics of
Sb(III) to be independent of pH after ~ 11.7, below this it is first order dependent on pH,
d[Sb(III)]tot
= [Sb(III)]tot [H2 O2 ]tot (k dependent on pH below 11.7) (1)
dt
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This pH dependence of oxidation was also validated by Quentel et al. (2004) in the pH range of 8
to 9.7 and stated that there was no detection of oxidation below pH 7, where the existence of
Sb(OH)o3 prevailed. Quentel et al. (2004) proposed the identical rate law for alkaline solutions,
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however, also elaborated on its ionic strength and temperature dependence, where an increase in
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both variables demonstrated linear increase in the oxidation rate:
d[Sb(III)]tot
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= [Sb(III)]tot [H2 O2 ]tot (2)
dt
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5.3 Trace metal effects on oxidation kinetics
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Due to the presence of trace metals in many aqueous solutions containing antimony,
especially seawaters, their effects on Sb(III) oxidation by hydrogen peroxide has been the focus
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of a few studies. The trace metals Cu(II), Mn(II), Zn(II), and Pb(II) were studied by Elleouet et
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al. (2005), while Fe(II) and Fe(III) effects were investigated by Leuz et al. (2006a). Elleouet et
al. (2005) concluded that the oxidation kinetics in the presence of most of the observed trace
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metals did indeed increase in the natural water pH range and concentrations. Zinc(II) had no
effect at all, whereas Cu(II), Mn(II), and Pb(II) did. Copper(II) accelerated the oxidation kinetics
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whereas the effect of Mn and Pb was not as pronounced. Leuz et al. (2006a) demonstrated the
effectiveness of ironassisted oxidation, where within the acidic pH range the cooxidation with
Sb(III) was similar for both Fe(II) and Fe(III). However, in the neutral to alkaline region, only
Based on these studies on Sb(III) oxidation, it was observed that at 25 oC oxygen was a
very poor oxidant in the pH range 3.6 9.8, it was determined to be significant in highly alkaline
solutions (pH > 12.9). Hydrogen peroxide was found to be a better oxidant than oxygen, where
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its oxidative influence was proportional to pH (after pH 11.7, oxidation rate of Sb(III) remained
constant). The presence of many trace metals (Cu(II), Mn(II), Pb(II)) was found to generally
increase Sb(III) oxidation (Zn(II) had no impact at all) where Cu(II) greatly accelerated the
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kinetics. Iron assisted oxidation was also confirmed, both Fe(II) and Fe(III) increased the rate in
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the acidic region, however, only Fe(II) remained effective in the neutral to alkaline pH, possibly
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6. Ultimate sinks of antimony in the environment
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6.1 Potential candidates immobilizing antimony
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Historically, secondary antimony minerals formed as a result of primary mineral
(especially Sb(V)) was largely mobile in the supergene environment. This perception was in part
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based on the fact that the end antimony member in oxidizing conditions, antimony pentoxide
(Sb2O5), was unstable and thus unable to immobilize antimony (Vink 1996; Diemar et al. 2009;
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Filella et al. 2009). Relatively recent studies, however, have correctly noted that Sb2O5 is
metastable and by no means should be considered as a candidate that can fix antimony. It is, on
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the contrary, antimony is actually quite immobile in the supergene environment and appears to
surroundings. In Tables 1 and 2, various primary and secondary antimony minerals along with
their respective occurrences were summarized. Using this information, some minerals
bindheimite Pb2Sb2O7, schafarzikite FeSb2O4, and tripuhyite FeSbO4,) have been identified
by several researchers (Diemar et al. 2009; Mitsunobu et al. 2011; Leverett et al. 2012; and
Roper et al. 2012) to serve as possible model compounds for fixing antimony that was mobilized
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as a result of mineral processing activities.. There is still a lack of reliable thermodynamic data,
however, relating to the formation of secondary minerals, especially Sb(V) precipitates from
aqueous solutions (Selim 2012; Roper et al. 2012). Furthermore, the kinetics of crystallization
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and transformation of secondary minerals into other ones still remains to be fully understood.
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Due to the abundance of calcium, magnesium, sodium and potassium in soils, antimony
compounds typically form precipitates with these elements. Many of these alkali metal
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hydroxyantimonate salts have a high solubility at ambient conditions: 0.4 gL1 for mopungite,
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Na[Sb(OH)6]; 0.5 gL1 for brandholzite, [Mg(H2O)6][Sb(OH)6]2; and 15 gL1 for potassium
such as shooting range and mine site soils, where antimony concentrations are extremely high
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(Okkenhaug et al. 2011). Many calcium antimonates such as Ca[Sb(OH)6]2 and Ca2Sb2O7 appear
to be among the most insoluble antimony compounds in soils, having a solubility of 0.016 gL1
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and 0.040 mgL1, respectively, although it is important to note that the former has yet to be
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confirmed to be a naturally occurring mineral (Diemar et al. 2009; Selim 2012). Furthermore, the
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latter compound romite, Ca2Sb2O7, as reported by Diemar et al. (2009) was shown to have a
solubility that was three orders of magnitude smaller than previously reported by other
researchers, which was attributed to the higher crystallinity of the compound. The synthesis pH
can also have a profound effect on the solubility of the mineral, Cornelis et al. (2011)
synthesized romite at pH 6.5 and 12 and showed that the resulting precipitate formula was
Ca1+xSb2O6OH22x. With increasing pH, the calcium content in the precipitate increased
(Ca(OH)2 was used to reach pH 12 while hydroxyl content decreased, reaching the ideal romite
formula (Ca2Sb2O7) at higher pH. The researchers concluded that calcium leached incongruently
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from the synthetic romites, however, antimonate was less soluble from those romites made in
alkaline conditions. Thus, conditions of mineral synthesis, mainly the ratio Sb:Ca and pH, can
influence the final crystalline structure and therefore its stability (Selim 2012).
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Antimony species, especially oxyanions, have shown to form precipitates in soils with
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heavy metals as well. Heavy metals normally include lead, nickel, and iron, and are usually more
plentiful in areas near anthropogenic sites. In particular, bindheimite, Pb2Sb2O7, and iron
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antimonates schafarzikite, FeSb2O4, and tripuhyite, FeSbO4, have demonstrated extremely low
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solubilities, up to 9.3 gL1 and a few gL1, respectively (Diemar et al. 2009; Selim 2012).
There is also ample evidence of adsorption of antimony onto iron and manganese oxyhydroxides
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that largely limit mobility in oxic environments (Belzile et al. 2001; Mitsunobu et al. 2010).
industrial applications, tripuhyite has been the subject of several studies. Only in the past decade
has it received more attention as a mineral that could limit the mobility of antimony. Its historic
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occurrences were likely overlooked because of its physical resemblance to goethite (Diemar et
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al. 2009; Leverett et al., 2012). Moreover, it has also been found in soils near antimony mine
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tailing sites. Mitsunobu et al. (2011) speculated that it likely formed in the aqueous wastewater
solution and subsequently adsorbed onto soil grains. If this was the case, then tripuhyite may
limit the mobility of antimony in both water and soil systems. Lastly, Leverett et al. (2012) have
associated both tripuhyite and schafarzikite as being ultimate sinks of antimony in the natural
environment because of their exceptional stabilities, likewise, Roper et al. (2012) concur and
state that these minerals are extraordinarily important with respect to immobilizing Sb under
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researchers have highlighted the large occurrences of tripuhyite and schafarzikite in the
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supergene environment, indicating minerals with reasonably high stabilities (Diemar et al. 2009;
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Mitsunobu et al. 2011; Leverett et al. 2012; and Roper et al. 2012). As such, preliminary stability
studies showed that these minerals can limit the mobility of antimony to a few gL1 in the soil
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environment (Selim, 2012). Thus far, indepth thermodynamic stability analyses of the two
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minerals are limited to a few reports in the literature. A detailed investigation of the stabilities of
tripuhyite and schafarzikite was conducted by Leverett et al. (2012) with important findings. The
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authors synthesized both minerals and conducted solubility tests, resulting in stability constants
of log K = 10.68 0.10 and Gfo = 836.8 2.2 kJ/mol for tripuhyite (25 oC, 0.195 M HNO3),
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and log K = 0.81 0.01 and Gfo = 959.4 4.3 kJ/mol for schafarzikite (25 oC, 0.1 M HNO3).
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They further extrapolated high temperature Gibbs free energies (from 771981 K) from
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relationships determined by Swaminathan and Sreedharan (2003) and found these calculated
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values in excellent agreement with theirs at 298 K, demonstrating the viability of the relationship
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over a very large temperature range. To illustrate the FeSbH2O behaviour for dilute systems at
ambient temperatures, a Pourbaix diagram (Figure 6) was developed based on reactions and log
K values outlined in Leverett et al. (2012), which could prove useful in tripuhyite synthesis from
schafarzikite as the former is stable over a larger pH range as well as residing in the oxic region,
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Since at least the 1980s, tripuhyite has received attention for its properties as a catalyst
for hydrocarbon (amm)oxidation and gas sensing technologies (Teller et al. 1985; Centi et al.
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1986; Tojo et al. 2008). There are a few methods of preparation, most of which consist of high
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temperature treatment rather than complete insolution crystallization. The traditional
methodology has been insolution precursor precipitation with subsequent high temperature
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calcination or solely high temperature calcination of iron and antimony compounds. The main
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reason for adopting this method was that the insolution precipitation method almost always
resulted in amorphous or poorly crystalline tripuhyite, not suitable for the intended application
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thus requiring high temperature treatments for inducing crystallinity. There are many research
papers that have followed this methodology and it appears to have been the accepted norm where
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these methods may not be necessarily suitable for direct application to treatment of effluents,
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metallurgical flue dusts or residues, nevertheless, they can provide useful insight, hence they are
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reviewed.
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Iron and antimony compounds (equimolar Fe and Sb, various initial concentrations,
some researchers used 0.2M) are introduced into an acidic medium (very acidic to mildly acidic),
ammonium hydroxide to neutral or alkaline pH (7 10) (Berry et al. 1987; Gadgil et al. 1995;
Tianshu and Hing 1999; Sasaki 2000; Huang et al. 2006, Nag et al. 2012). The reaction
mechanism is very complex and changes based on antimony (III,V) and iron (II,III) initial
oxidation states and whether a chloride or sulfate system is employed, generally, the assumption
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is that an amorphous tripuhyite precipitate eventually forms (although other competitive theories
also exist which state that iron hydroxides precipitate after which antimony ions subsequently
adsorb thereby creating an intermediate amorphous compound). This precursor precipitate is then
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filtered, washed, dried, ground and then calcined in an oven at varying temperatures (25 1000
o
C) and 3 8 hrs of time (Figure 7 and 8). An enhancement to this procedure was introduced by
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Nag et al. (2012) where prior to and after neutralization the solution was sonicated with
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ultrasound for 30 minutes, after which the precipitate was calcined at lower temperatures (300
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and 450 oC). The results indicate the presence of tripuhyite at lower temperatures in comparison
to historic results, and, increased crystallinity at higher calcination temperatures (Figure 8(b)).
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7.2 Grinding and/or calcination
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antimony trioxide, Sb2O3, followed by calcination was the method used in studies by Tianshu
and Hing (1999) and Huang et al. (2005). The results demonstrate the plausibility of producing
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tripuhyite in this fashion, however, due to the incongruent oxidation of both compounds, the
production of tripuhyite still takes place at fairly high calcination temperatures (> 800 oC) with
other species still present until ~ 1000 oC, the reactions are given in Equations (1) and (2):
1
Sb2 O3 + O2 Sb2 O4 (1)
2
1
Sb2 O4 + Fe2 O3 + O2 FeSbO4 (2)
2
calcination was studied by Berry and Ren (2004) and Tojo et al. (2008). Berry and Ren (2004)
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used mixtures of Fe2O3 and Sb2O3 at various grind times to determine phase changes of the
compounds and residence time requirements for tripuhyite synthesis. Their results are
summarized in Figure 9 where the onset of tripuhyite formation takes place at ~ 190 hours, after
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which its crystallinity increases with more grind time. Tojo et al. (2008) also performed
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mechanical milling at room temperature on iron and antimony powders, however, they chose
iron oxyhydroxide (goethite), FeOOH, and antimony pentoxide, Sb2O5, as their starting raw
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materials, the reaction given by Equation (3):
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2FeOOH + Sb2 O5 2FeSbO4 + H2 O (3)
As a result of the substitution, the residence time for tripuhyite synthesis was considerably
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reduced, where the onset of formation took place at ~ 1 hour after which subsequent grinding
resulted in increased crystallinity (Figure 10(a)). Moreover, the authors also varied the starting
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Fe:Sb ratio to determine its effect, the results in Figure 10(b) show the decreasing peak intensity
of tripuhyite with increasing Fe:Sb ratios, demonstrating the importance of initial Fe:Sb ratios on
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product crystallinity.
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waste disposal from these methods, whether calcination or grinding alone at room temperatures,
seems to be very energy intensive and therefore costly. A process that is cost effective and better
suited for large scale miningderived Sbbearing waste treatment is favoured. Although
attractive method considering that antimony is either in effluent solutions or previously dissolved
before being fixed in mineral processing applications. Historically, the very stable arsenic
compound scorodite, FeAsO42H2O, has been produced in solution to immobilize arsenic, either
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(< 100 oC), yielding highly crystalline products (Filippou and Demopoulos 1997; Fujita et al.
2009; Demopoulos 2009). Antimony, which has many similarities with arsenic, can likely be
treated in solution to yield highly crystalline tripuhyite. Mitsunobu et al. (2011) alluded to this
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methodology where tripuhyite was observed in mine soils, the authors believed its formation
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likely involved direct precipitation via neutralization from the acidic mine wastewater.
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8. Summary
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larger scale because of increased mining activities. As a result, there is a higher probability of
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encountering antimony in the supergene environment and since it is classified as a toxic
Its concentration in the air, water, and soil systems was reviewed and relevant
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worldwide limits on its disposal were given. Its industrial processing (mineral processing,
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pyrometallurgy, and hydrometallurgy) and treatments (direct recycling or leaching residues and
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speiss) were briefly mentioned. Antimony speciation was presented at various conditions (pH,
Eh, temperature, and concentration) to provide a basis of its aqueous behaviour, an important
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foundation for industrial effluent treatment. Information on oxidation kinetics was provided to
demonstrate the effects of common oxidants (O2, H2O2, trace metals Cu(II), Mn(II), Pb(II),
Zn(II), Fe(II), and Fe(III)). For immobilizing antimony in the environment several mineral
candidates were named, a few of which were very promising (romite, Ca2Sb2O7, bindheimite,
Pb2Sb2O7, schafarzikite, FeSb2O4, and tripuhyite, FeSbO4). Of these, tripuhyite was proposed as
the most attractive candidate as it limited antimony solubility to a few gL1 (lowest reported
relevant pH (5 9), and possible to synthesize from industrial effluents given the correct
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conditions (Fe:Sb ratio, pH, temperature). Further, it was demonstrated that with post
greatly increased (higher crystallinity was shown to correlate with increased mineral stability).
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The material presented in this review provides a general context of antimony in the
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metallurgical industry, its chemical behaviour in aqueous systems, and proposes a few minerals
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capable of effectively fixing antimony (with preference to tripuhyite). Such information should
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Acknowledgments
This work was supported by NSERCs Discovery Grant program.
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Boulangerite Pb5Sb4S11 Horsfordite Cu6Sb Stibioenargite Cu3(As,Sb)4
Bournonite PbCuSbS3 Jamesonite Pb4FeSb6S14 Stibioluzonite Cu3(As,Sb)S4
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Breithauptite NiSb Kermesite Sb2S2O Stibio-tellurobismutite (Bi,Sb)2Te3
Cervantite Sb2O4 Livingstonite HgSb4S7 Stibnite Sb2S3
Cylindrite Pb3Sn4Sb2S14 Meneghinite Pb4Sb2S7 Tetrahedrite Cu12Sb4S13
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Dyscrasite Ag3Sb Ramdohrite Ag2Pb3Sb3S9 Ullmannite NiSbS
Falkmanite Pb3Sb2S6 Romeite 5CaO3Sb2O5 Valentinite Sb2O3
Famatinite Cu3SbS4 Senarmontite Sb2O3 Zinckenite PbSb2S4
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Franckeite Pb5Sn3Sb2S14 Stenhuggarite CaFeSbAs2O7
Freibergite (Cu,Ag)12Sb4S13 Stephanite Ag5SbS4
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Table 1 Primary antimony minerals, adapted from Anderson (2012).
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Brandholzite Mg[Sb(OH)6]26H2O 4
Braithwaiteite NaCu5(Ti,Sb)2O2(AsO4)[AsO3(OH)]28H2O 1
Brizziite NaSbO3 1
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Bystrmite MgSb2O6 2
Camerolaite Cu4Al2(HSbO4,SO4)CO3(OH)102H2O 10
Sb3+Sb5+O4
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Cervantite 227
Cetineite (K,Na)6(Sb2O3)6(SbS3)2[(H2O)6 - x(OH)x](x - 0.5) 6
Clinocervantite Sb3+Sb5+O4 2
Coquandite Sb6O8SO4H2O 7
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Cualstibite Cu2Al[Sb(OH)6](OH)6 4
Cyanophyllite Cu2Al[Sb(OH)6](OH)6 8
Jolbruggerite Pb3Zn3Sb5+As2O13(OH) MA 1
Kelyanite Hg12Sb(Cl,Br)3O6 1
Kermesite Sb2S2O 201
Klebelsbergite Sb4O4SO4(OH)2 15
Mallestigite Pb3Sb(SO4)(AsO4)(OH)63H2O 2
Mammothite Pb6Cu4AlSbO2(SO4)2Cl4(OH)16 7
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Mopungite NaSb(OH)6 6
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Nadorite PbSbO2Cl 14
Onoratoite Sb8O11Cl2 2
Ordezite ZnSb2O6 2
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Ottensite (Na,K)3(Sb2O3)3(SbS3)3H2O 1
Partzite Cu2Sb2(O,OH)7 57
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Peretaite CaSb4O4(SO4)2(OH)22H2O 4
Richelsdorfite Ca2Cu5[Sb(OH)6](AsO4)4Cl6H2O 43
Romite Ca2Sb2O7 32
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Rosiaite PbSb2O6 8
Sabelliite Cu2Zn(AsO4,SbO4)(OH)3 3
Schafarzikite FeSb2O4 11
Snarmontite Sb2O3 147
Shakhovite Hg4SbO3(OH)3 6
Stetefeldtite Ag2Sb2(O,OH)7 23
Stibiconite Sb3+Sb5+2O6(OH) 373
Stibioclaudetite AsSbO3 1
Theisite Cu5Zn5(AsO4,SbO4)2(OH)14 45
Thorikosite Pb3(Sb,As)O3(OH)Cl2 4
Tungstibite Sb2WO6 1
Tripuhyite FeSbO4 48
Valentinite Sb2O3 296
Zincalstibite Zn2Al[Sb(OH)6](OH)6 3
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Soil Sb
concentration Contamination Source Comments
range (mgkg1)
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0 1,090 Area surrounding a goldantimony mine A horizon samples up to 7.5 km from tailing dam (in prevailing
wind direction)
11.9 710 Previous mining activities Low levels of watersoluble Sb
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27.7 15,100 Previous mining activities Shoots and leaf accumulation for 3 species of up to 1,160 and
1,370 mgkg1
2.5 237 Previous mining activities Soils classified as highly contaminated
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31 5,986 Abandoned mine area B horizon soils, Portugal
0.1 39.4 Antimony mine 300 km upstream Floodplain in NSW Australia, moderately contaminated with Sb
180 554 Antimony mine area approx. 2 km upstream Rhizosphere soil adjacent to contaminated creek, NSW
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7.4 13,610 Previous mining activities A horizon soils
26 1,150 Mining contaminated area, S. France Surface soils
35 17,500 Shooting range, Switzerland < 0.5 mm soil fraction. High concentrations associated with Sb in
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1,300 17,500 Shooting range 0 0.45 cm depth
629 8,230 Shooting range 0.2 10 cm depth Rhizosphere soil
Table 3 Antimony concentration in contaminated soils from anthropogenic activities, adapted from Wilson et al. (2010).
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United States -- -- --
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Table 4 Worldwide antimony production and ore body reserves from 2013 and 2014, U.S. Geological Survey (2015).
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Reaction log
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Sb(OH)o3 () () 0.2327
2Sb(OH)o3 3H2 O + (, ) 11.44
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2Sb(OH)o3 3H2 O + (, ) 10.00
Sb(OH)o3 H2 O + () 4.371
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2Sb(OH)o3 2H + + 2e + 2H2 O + () 1.680
4Sb(OH)o3 6H2 O + () 18.53
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2Sb(OH)o3 4H + + 4e + H2 O + () 37.26
4Sb(OH)o3 6H2 O + (, )
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4Sb(OH)o3 6H2 O + (, ) 17.71
Sb(OH)o3 + 3H + + 3e 3H2 O + () 12.26
Sb(OH)o3 + H + H2 O + ()+
1.371
Sb(OH)o3 + H2 O H + + ()
11.70
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Sb(OH)o3 + H2 O H + + 2e + ()+
24.61
Sb(OH)o3 + 2H2 O 2H + + 2e + () 22.33
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Sb(OH)o3 + 3H2 O 3H + + 2e + ()
25.15
Table 5 Best stability constant values for all acidbase and oxide antimony species are presented, adapted from
Filella and May (2003).
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Reaction log
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2Sb(OH)o3 + 4S 2 + 6H + 6H2 O + 90.94
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2Sb(OH)o3 + 2S 2 + 4H + 4H2 O + () 57.67
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Sb(OH)o3 + 3S 2 + 3H + 3H2 O + 46.80
Sb(OH)o3 + 2S 2 + 3H + 3H2 O + 47.92
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4Sb(OH)o3 + 7S 2 + 12H + 12H2 O + 183.2
Sb(OH)o3 + S 2 + H + H2 O + ()
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Table 6 Best stability constant values for all antimonysulfide species are presented, adapted from Filella and
May (2003).
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Figure 1 EhpH diagram for dilute aqueous antimony solutions, calculated at 25 oC, 1010 molL1 Sb using
HYDRA and MEDUSA (Puigdomenech 2009; Puigdomenech 2010).
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Figure 2 EhpH diagram for more concentrated aqueous antimony solutions, calculated at 25 oC using HYDRA
and MEDUSA (Puigdomenech 2009; Puigdomenech 2010): (a) 107 molL1 Sb, (b) 105 molL1 Sb.
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(a) (b)
Figure 3 Speciation diagram for (a) Sb(III), (b) Sb(V) in aqueous solutions as a function of pH, calculated at 25
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C using HYDRA and MEDUSA (Puigdomenech 2009; Puigdomenech 2010).
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Figure 4 Comparison of speciation of Sb(III) at 25 oC and 300 oC, 0.0001 molL1 Sb, reproduced from
ZakaznovaHerzog and Seward (2006).
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Figure 6 EhpH diagram for the FeSbH2O system, calculated at 25 oC and total dissolved Sb and Fe
concentrations of 106 molL1 using HYDRA and MEDUSA (Puigdomenech 2009; Puigdomenech 2010). Tripuhyite
(FeSbO4) and schafarzikite (FeSb2O4) reactions and log K values were obtained from Leverett et al. (2012).
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Figure 7 General flow sheet depicting the precipitation and calcination procedure to form crystalline tripuhyite,
FeSbO4.
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(a) (b)
Figure 8 (a) Xray diffraction patterns of coprecipitated powders calcined at room temperature to 1000 oC for 3
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hrs in air, reproduced from Tianshu and Hing (1999); (b) Xray diffraction patterns of coprecipitated powders, (1)
as prepared, (2) 300 oC calcined for 6 hrs, (3) 450 oC calcined for 6 hrs, Reprinted (adapted) with permission from
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[Nag, P., Banerjee, S., Lee, Y., Bumajdad, A., Lee, Y., & Devi, P.S. (2012). Sonochemical synthesis and properties of
nanoparticles of FeSbO4. Inorganic Chemistry, 51(2), 844 850]. Copyright [2012] American Chemical Society.
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Figure 9 Xray powder diffraction patterns of Fe2O3 and Sb2O3 mixtures (1:1 Fe:Sb molar ratio) at various
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(a) (b)
Figure 10 (a) Xray powder diffraction patterns of FeOOH and Sb 2O5 mixtures (1:1 Fe:Sb molar ratio) at various
mechanical milling times. (b) Xray powder diffraction patterns of FeOOH and Sb2O5 at different Fe:Sb ratios,
milled for 120 minutes, reproduced from Tojo et al. (2008).
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Highlights
Antimony in the environment and industrial processing/treatment was reviewed
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Antimony aqueous chemistry presented for different pH/Eh/temperature/concentrations
Most ideal candidate for antimony fixation from effluents was tripuhyite, FeSbO4
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With postprecipitation treatments mineral crystallinity/stability can be increased
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