Antimony in the environment: a review focused on natural waters: I. Occurrence

https://doi.org/10.1016/S0012-8252(01)00070-8Get rights and content

Abstract

Antimony is ubiquitously present in the environment as a result of natural processes and human activities. It exists mainly as Sb(III) and Sb(V) in environmental, biological and geochemical samples. Antimony and its compounds are considered to be priority pollutants interest by the USEPA and the EU. In this first review paper on antimony occurrence in natural waters, 420 papers on freshwaters, marine waters, estuaries, soils, and sediments have been reviewed. All data are quoted from the original sources. Typical concentrations of total dissolved antimony are usually less than 1.0 μg/l in non-polluted waters. When redox speciation determinations are performed, most studies report the dominance of Sb(V) under oxic conditions. However, the presence of significant proportions of Sb(III) is sometimes detected. This is in contrast with thermodynamic equilibrium predictions and discrepancies are often attributed to biological activity or kinetic effects but proofs are lacking. Similarly, the existence of Sb(V), although not thermodynamically predicted, is often reported under anoxic conditions. Low concentrations of methylated antimony species are mentioned in a few studies. Antimony is not considered to be a highly reactive element in oceans, with concentrations of the order of 200 ng/l. In estuarine waters, both conservative and non-conservative behaviours are reported depending on the estuaries' characteristics. Elevated concentrations of antimony in soils and sediments are either related to anthropogenic sources or associated with high arsenic concentrations in sulfidic ores. Antimony appears to be highly unreactive in soils. Low accumulation factors are reported in algae. Airborne supply of antimony to aquatic and terrestrial systems seems to be important in systems far from direct pollution sources. However, the limited available data do not allow firm conclusions to be drawn on the reactivity and cycling of the element in natural systems and a list of research priorities is given.

Introduction

A good deal of research on geochemical and biogeochemical processes in natural waters has been, and continues to be, devoted to trace elements, particularly transition metals. Rather less attention has been focused on the so-called metalloid elements. Among them, antimony is the one that has received the scantiest attention.

Antimony is a naturally occurring element. It belongs to the group 15 of the Periodic Table of the Elements. Antimony can exist in a variety of oxidation states (−III, 0, III, V) but it is mainly found in two oxidation states (III and V) in environmental, biological and geochemical samples. The relative abundance of antimony in different terrestrial systems is given in Table 1.

According to the classical classification of Goldschmidt, antimony is a strong chalcophile element and as such mainly occurs in nature as Sb2S3 (stibnite, antimonite) and Sb2O3 (valentinite), which is a transformation product of stibnite. These compounds of antimony are commonly found in ores of copper, silver, and lead. Antimony is also a common component of coal and petroleum.

Little information is available on the transformation and transport of antimony in the different environmental compartments. Even information on antimony speciation and total content in the various media is scarce and often contradictory. This lack of understanding of antimony behaviour and fate in the environment hinders further research. In this series of papers, we have launched an exhaustive review of the scientific literature in order to identify and evaluate all sources of information related to antimony. In this first paper, we have attempted to include all studies devoted to freshwaters, marine waters, and estuaries. To illustrate key aspects of antimony occurrence in nature, some selected information on sediments and soils is also included. Values quoted come from the original sources. Multireferencing has been avoided. In the very few cases where it has been used, the origin of the reference is given. A total of 420 papers have been reviewed. Other studies on subjects such as relevant aquatic chemistry, antimony in biota, etc., will follow.

Section snippets

Uses

Antimony was already known to the ancients. Since it can dissolve many other metals including gold, this property was used for purifying gold from copper and silver up to the 18th century. A peat core from an ombrotrophic Swiss bog revealed significant enrichments of antimony extending back to Roman times, indicating that the anthropogenic fluxes of this metal have exceeded natural ones for more than 2000 years. The present day enrichment factor (relative to the element/Sc ratios of typical

Toxicity

Antimony and its compounds were considered as pollutants of priority interest by the Environmental Protection Agency of the United States (USEPA, 1979) and the European Union (Council of the European Communities, 1976). The USEPA drinking water standards are: maximum contaminant level goal (MCLG) and maximum contaminant level (MCL), both 6 μg/l (USEPA, 1999). The European Union established a maximum admissible concentration of antimony in drinking water of 5 μg/l (Council of the European Union,

Occurrence in natural waters

Antimony is present in the aquatic environment as a result of rock weathering, soil runoff and anthropogenic activities. Typical concentrations of dissolved antimony in unpolluted waters are less than 1 μg/l. However, in the proximity of anthropogenic sources, concentrations can reach up to 100 times natural levels.

Antimony is present in substantial concentrations in precipitates from hot springs and boreholes and in geothermal waters. Concentrations ranging from 500 mg/l up to 10 wt.% have

Occurrence in sediments and soils

Antimony concentrations in sediments and soils are of the order of a few μg/g Table 6, Table 7. Higher concentrations are directly related to anthropogenic sources, mainly proximity to smelting plants O'Toole et al., 1971, Crecelius et al., 1974, Cawse et al., 1975, Ragaini et al., 1977, Ainsworth et al., 1990a, Asami et al., 1992. Elevated concentrations in sediments near the outfalls of sewage and fertiliser facilities have also been reported Papakostidis et al., 1975, Grimanis et al., 1977.

Reference materials

In comparison with other trace elements, reference materials (RM) with certified antimony contents are scarce. The most often used and easily available environmental reference materials containing antimony are given in Table 8. Data quoted in Table 3, Table 4, Table 5, Table 6, Table 7 do not contain any published result for this type of samples. However, the reader can find complementary information on the use of these reference materials in the following selection of recent papers where these

Occurrence in biota

There is no evidence of bioconcentration of antimony in aquatic algae Bonotto et al., 1983, Mann and Fyfe, 1988, Mann et al., 1988. Reported concentrations for antimony in freshwater and marine algae are 0.1–0.2 μg/g dry weight (range from 0.02 to 1 μg/g dry weight) Leatherland and Burton, 1974, Strohal et al., 1975, Payer et al., 1976, Bowen, 1979, Abu-Hilal and Riley, 1981, Kantin, 1983, Andreae and Froelich, 1984, Maher, 1986, Djingova et al., 1987, Mann and Fyfe, 1988, Mann et al., 1988,

Speciation in natural waters

It is nowadays well recognised that the understanding of biogeochemical processes depends upon the knowledge of the chemical forms, or species, that are present in the natural environment. Despite this well-known requirement, the speciation of many elements in the natural environments is not adequately known. Antimony is not an exception.

Antimony occurs in two oxidation states in natural waters and, thus, its behaviour can be affected by changes in the redox status of the aquatic environment.

Importance of atmospheric input

Airborne supply to aquatic and terrestrial systems is important for the environmental fate of some elements. Although existing data are sparse, this seems to be the case for antimony in systems far from direct pollution sources Payer et al., 1976, Andreae and Froelich, 1984, Austin and Millward, 1986, Van der Weijden et al., 1990, Cutter, 1993, Guieu et al., 1993, Cutter et al., 2001.

Atmospheric emission values for antimony, as estimated by Nriagu and Pacyna (1988) and Nriagu, 1989, Nriagu, 1990

Conclusions

This extensive review on the occurrence of antimony in the environment presents most of the information available on the distribution and speciation of antimony in aquatic systems in a condensed format. More importantly, it has identified several important biogeochemical aspects of the element for which further research is still needed, namely:

  • •

    speciation of antimony in natural waters and its partition among dissolved and solid phases in both oxic and anoxic systems,

  • •

    kinetics of oxidation for

Acknowledgements

The support from the Agence Universitaire de la Francophonie (Programme d'invitation de professeur/chercheur) is acknowledged by one of the authors (MF). This work was also supported by the Natural Sciences and Engineering Research Council of Canada and the Elliot Lake Research Field Station of Laurentian University.

References (252)

  • C. Brihaye et al.

    Determination of traces of metals by anodic stripping voltammetry at a rotating glassy carbon ring-disc electrode: Part 3. Evaluation of linear anodic stripping voltammetry with ring collection for the determination of cadmium, lead and copper in pure water and high-purity sodium chloride, and of cadmium, lead, copper, antimony and bismuth in sea water

    Anal. Chim. Acta

    (1983)
  • P. Buat-Menard et al.

    Variable influence of atmospheric flux on the trace metal chemistry of oceanic suspended matter

    Earth Planet. Sci. Lett.

    (1979)
  • J.T. Byrd

    Comparative geochemistries of arsenic and antimony in rivers and estuaries

    Sci. Total Environ.

    (1990)
  • F. Cabrera et al.

    Heavy metal pollution of soils affected by the Guadiamar toxic flood

    Sci. Total Environ.

    (1999)
  • G. Capodaglio et al.

    Determination of antimony in seawater by cathodic stripping voltammetry

    J. Electroanal. Chem.

    (1987)
  • C.-S. Chen et al.

    Determination of As, Sb, Bi and Hg in water samples by flow-injection inductively coupled plasma mass spectrometry with an in-situ nebulizer/hydride generator

    Spectrochim. Acta

    (1996)
  • A.H. Cornfield

    Effects of addition of 12 metals on carbon dioxide release during incubation of an acid sandy soil

    Geoderma

    (1977)
  • E.A. Crecelius

    The solubility of coal fly ash and marine aerosols in seawater

    Mar. Chem.

    (1980)
  • G.A. Cutter

    Dissolved arsenic and antimony in the Black Sea

    Deep-Sea Res.

    (1991)
  • G.A. Cutter

    Kinetic controls on metalloid speciation in seawater

    Mar. Chem.

    (1992)
  • G.A. Cutter et al.

    Behaviour of dissolved antimony, arsenic, and selenium in the Atlantic Ocean

    Mar. Chem.

    (1995)
  • G.A. Cutter et al.

    Metalloids in the high latitude North Atlantic Ocean: sources and internal cycling

    Mar. Chem.

    (1998)
  • G.A. Cutter et al.

    Antimony and arsenic biogeochemistry in the western Atlantic Ocean

    Deep-Sea Res., Part II

    (2001)
  • M.B. de la Calle Guntiñas et al.

    Flow-injection and continuous-flow systems to determine antimony(III) and antimony(V) by hydride generation atomic absorption spectrometry

    Anal. Chim. Acta

    (1991)
  • C.B. Dissanayake et al.

    The abundance of some major and trace elements in highly polluted sediments from the Rhine River near Mainz, West Germany

    Sci. Total Environ.

    (1983)
  • E.M. Donaldson

    Determination of antimony in ores and related materials by continuous hydride-generation atomic-absorption spectrometry after separation by xanthate extraction

    Talanta

    (1990)
  • C.M. Elson et al.

    Determination of arsenic and antimony in geological materials and natural waters by coprecipitation with selenium and neutron activation—γ-spectrometry

    Anal. Chim. Acta

    (1982)
  • J.E. Fergusson et al.

    The elemental composition and sources of house dust and street dust

    Sci. Total Environ.

    (1986)
  • S.L. Friant et al.

    Use of an in situ artificial substrate for biological accumulation and monitoring of aqueous trace metals. A preliminary field investigation

    Water Res.

    (1981)
  • S. Garboś et al.

    Preconcentration of inorganic species of antimony by sorption on Polyorgs 31 followed by atomic spectrometry detection

    Anal. Chim. Acta

    (1997)
  • P.N. Gates et al.

    Sudden infant death syndrome and volatile antimony compounds

    Lancet

    (1995)
  • P.N. Gates et al.

    Can microorganisms convert antimony trioxide or potassium antimonyl tartarte to methylated stibines?

    Sci. Total Environ.

    (1997)
  • T. Gebel

    Arsenic and antimony: comparative approach on mechanistic toxicology

    Chem.-Biol. Interact.

    (1997)
  • S.A. Abbasi

    Sub-microdetermination of antimony (III) and antimony (V) in natural and polluted waters and total antimony in biological materials by flameless AAS following extractive separation with N-p-methoxy-phenyl-2-furylacrylohydroxamic acid

    Anal. Lett.

    (1989)
  • L.H. Ahrens

    Distribution of the Elements in Our Planet

    (1965)
  • R.O. Allen et al.

    Contribution from long-range atmospheric transport to the heavy metal pollution of surface soil

  • R.O. Allen et al.

    A contribution to the geochemistry of lakes in Norway

    Nor. Geol. Unders., Bull.

    (1987)
  • K.A. Anderson et al.

    Determination of antimony in environmental samples by hydride generation-inductively coupled plasma spectrometry

    J. AOAC Int.

    (1994)
  • K.A. Anderson et al.

    Simultaneous determination of arsenic, selenium, and antimony in environmental samples by hydride generation for inductively coupled plasma atomic emission spectrometry

    J. AOAC Int.

    (1995)
  • M.O. Andreae

    The determination of the chemical species of some of the “hydride elements” (arsenic, antimony, tin and germanium) in seawater: methodology and results

  • M.O. Andreae et al.

    Arsenic, antimony, and germanium biogeochemistry in the Baltic Sea

    Tellus

    (1984)
  • M.O. Andreae et al.

    Determination of antimony(III), antimony(V), and methylantimony species in natural waters by atomic absorption spectrometry with hydride generation

    Anal. Chem.

    (1981)
  • M.O. Andreae et al.

    Arsenic, antimony, germanium, and tin in the Tejo Estuary, Portugal: modelling a polluted estuary

    Environ. Sci. Technol.

    (1983)
  • P. Andrewes et al.

    Arsenic and antimony biomethylation by Scopulariopsis brevicaulis: interaction of arsenic and antimony compounds

    Environ. Sci. Technol.

    (2000)
  • S.C. Apte et al.

    Determination of dissolved inorganic antimony(V) and antimony(III) species in natural waters by hydride generation atomic absorption spectrometry

    J. Anal. At. Spectrom.

    (1986)
  • R. Arimoto et al.

    Trace elements in the atmosphere over the North Atlantic

    J. Geophys. Res.

    (1995)
  • T. Asami et al.

    Natural abundance of cadmium, antimony, bismuth and some other heavy metals in Japanese soils

    Jpn. J. Soil Sci. Plant Nutr.

    (1988)
  • T. Asami et al.

    Simultaneous determination of antimony and bismuth in soils by continuous hydride generation—atomic absorption spectrometry

    Water, Air, Soil Pollut.

    (1992)
  • C. Barghigiani et al.

    Distribution of As, Sb, Se, Te and Hg in some sediments of the Venice Lagoon

  • Barnard, D., 1947. Studies on the metabolism of certain Aspergilli and Penicillia. PhD Thesis, University of Leeds,...
  • Cited by (0)

    View full text