Review
Antimony speciation in the environment: Recent advances in understanding the biogeochemical processes and ecological effects

https://doi.org/10.1016/j.jes.2018.05.023Get rights and content

Abstract

Antimony (Sb) is a toxic metalloid, and its pollution has become a global environmental problem as a result of its extensive use and corresponding Sb-mining activities. The toxicity and mobility of Sb strongly depend on its chemical speciation. In this review, we summarize the current knowledge on the biogeochemical processes (including emission, distribution, speciation, redox, metabolism and toxicity) that trigger the mobilization and transformation of Sb from pollution sources to the surrounding environment. Natural phenomena such as weathering, biological activity and volcanic activity, together with anthropogenic inputs, are responsible for the emission of Sb into the environment. Sb emitted in the environment can adsorb and undergo redox reactions on organic or inorganic environmental media, thus changing its existing form and exerting toxic effects on the ecosystem. This review is based on a careful and systematic collection of the latest papers during 2010–2017 and our research results, and it illustrates the fate and ecological effects of Sb in the environment.

Introduction

As a toxic element of growing environmental concern, antimony (Sb) is ubiquitous throughout the environment as a result of natural phenomena such as weathering, biological activity, and volcanic activity together with anthropogenic inputs, and it has been considered a priority pollutant by the United States Environmental Protection Agency and the European Union. Worldwide, Sb is the ninth-most mined metal, and it primarily occurs in nature as Sb2S3 and Sb2O3 (Filella et al., 2002a, He et al., 1992, Okkenhaug et al., 2011). Some records in peat bogs (Shotyk et al., 2005) and Arctic polar ice cores (Krachler et al., 2005) show a dramatic increase of Sb in the environment as a result of its rapid growth in industrial use. Mining and smelting operations, waste incineration, coal and petroleum combustion, and spent ammunition are all associated with elevated concentrations of Sb in the environment, e.g., abandoned and active Sb mines, mineral processing facilities and smelters, waste incinerators, power plants, polyethylene terephthalate (PET) esterification industries, battery factories, shooting ranges and highways (Okkenhaug et al., 2011, Reimann et al., 2010).

Most Sb is emitted as Sb2O3 into air, water and soil from pollution sources (He et al., 2012, Tian et al., 2012). Then, it dissolves and is released into environmental media (Hu et al., 2014), and its transformation affects its mobility and bioavailability. Sb can exist in four oxidation states (-III, 0, III, and V) with the III and V states being most frequently encountered in the environment (Filella et al., 2002a). Sb(V) is the predominant species, and it exists in the form of Sb(OH)6 in oxic environments; Sb(III) primarily occurs as Sb(OH)3, which is predominant under anoxic conditions. Sb(III) is more toxic than Sb(V) (Filella et al., 2002a, Filella et al., 2002b). In addition, Sb can also exist as organic compounds (methylated species) (Wilson et al., 2010). The mobility and toxicity of Sb strongly depend on its oxidation speciation (Kong et al., 2015). Similar to the metalloid As, Sb has no known biological function but is toxic. Therefore, it is significant to understand Sb speciation and transformation in the ecological environment to assess its fate and risk. In recent years, a series of studies on the occurrence of Sb, the solution (Hu et al., 2014, Hu et al., 2015a, Hu et al., 2015b, Hu et al., 2016, Hu et al., 2017, Hu and He, 2017) and transformation features associated with its chemistry (Kong and He, 2016, Kong et al., 2015, Kong et al., 2016), its interactions with microbiota (Abin and Hollibaugh, 2014, Kulp et al., 2014, Lehr et al., 2007, Li et al., 2015a), and its toxicity and biological effects on organisms (Corrales et al., 2014, Fu et al., 2010, Li et al., 2014, Sun et al., 2016a, Sun et al., 2017) have drawn the greater attention of the global scientific community on Sb contamination over different environmental, biological and geological fields.

In this paper, we attempt to review the biogeochemistry and ecological effect of Sb in environmental media and illustrate the key processes of the migration and transformation of Sb by combining the results of our research. The main topics of this review include the following: (1) pollution sources and emission characteristics; (2) distribution and speciation in different environmental media; (3) transformation processes associated with chemical and biological processes; and (4) toxicity to and bio-effects on different types of organisms. The main pollution source, environmental process and ecological effect of antimony in the environment are shown in Fig. 1.

Section snippets

Sb mining and smelting activities

China has the largest reserves of Sb in the world, and it also dominates Sb mining (about 78% of global production capacity) (Dupont et al., 2016). The Sb reserves are relatively concentrated, with 114 Sb mines located within 18 provinces or autonomous regions, most of which are located in southwestern China (He et al., 2012). Hence, China plays an important role in global anthropogenic Sb emissions (Tian et al., 2012, Tian et al., 2014), and it has relatively high background levels of Sb in

Antimony in the atmosphere

The spatial distribution and speciation of atmospheric Sb around the world have been studied. Beaudon et al. (2017) and Hong et al. (2012) investigated the distribution of atmospheric Sb over time by analyzing snowpacks or ice cores. An investigation of Antarctic ice found that considerably higher values of Sb concentrations and fluxes were observed during glacial maxima while lower values were found during intermediate and warm periods. The Sb content remained at a high level in rock and soil

Adsorption

The transformation of mobile forms of Sb is predominantly controlled by naturally occurring precipitation and adsorption processes. Oxyhydroxides of iron, manganese and aluminum minerals have been recognized as naturally occurring Sb-sequestering agents in the environment. Antimony is also immobilized in the natural environment via precipitation with alkali metals, resulting in extremely stable mineral phases, such as calcium antimonates (Herath et al., 2017).

The adsorbents of Sb are roughly

Microorganisms

The interactions of Sb with microbiota have consistently been an academic focus of attention. The microbial transformations of Sb can affect the environmental fate and toxicity of this metalloid; meanwhile, Sb in turn produces ecological effects (e.g., on biomass, basic respiration rate, enzyme activities, community structure and biochemical processes) on microbiota. However, detailed knowledge of the ecological effects of Sb on microbiota is still very limited compared with arsenic. Thus, this

Conclusions and perspectives

This review has focused on the recent advances of the biogeochemical cycles and ecological effect of Sb. Typically, Sb data are much more limited than other similar elements, e.g., arsenic, in the same group of the periodic table (Le, 2016, Cohen et al., 2016). Whereas many arsenic species have been synthesized (Cullen et al., 2016), very few standards of Sb species are available. In addition, the natural abundance of Sb is about one tenth of arsenic. The lack of Sb standard compounds and the

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Nos. 21477008, 21677014, U1706217), the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (No. 51721093) and the Interdiscipline Research Funds of Beijing Normal University (No. 312231103).

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