Applied Geochemistry 25 (2010) 175–198
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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem
Review
Antimony in the environment: Lessons from geochemical mapping
Clemens Reimann a,*, Jörg Matschullat b, Manfred Birke c, Reijo Salminen d
a
Geological Survey of Norway, 7491 Trondheim, Norway
Interdisciplinary Environmental Research Centre (IÖZ), TU Bergakademie Freiberg, Brennhausgasse 14, 09599 Freiberg, Germany
c
Bundesanstalt für Geowissenschaften und Rohstoffe (BGR), Postfach 510153, 30631 Hannover, Germany
d
Geological Survey of Finland, P.O. Box 96, 02151 Espoo, Finland
b
a r t i c l e
i n f o
Article history:
Received 3 August 2009
Accepted 20 November 2009
Available online 26 November 2009
Editorial handling by R. Fuge
Keywords:
Exploration
Contamination
Background
Soil
Sediment
Biogeochemistry
a b s t r a c t
The distribution of Sb in a variety of sample materials, including soils, plants and surface water, was studied at different scales, from continental to local, combining published data sets with the aim of delineating the impact and relative importance of geogenic vs. anthropogenic Sb sources. Geochemical mapping
demonstrates that variation is high at all scales – from the detailed scale with sample densities of many
sites per km2 to the continental-scale with densities of 1 site per 5000 km2. Different processes govern
the Sb distribution at different scales. A high sample density of several samples per km2 is needed to reliably detect mineralisation or contamination in soil samples. Median concentrations are so low for Sb in
most sample materials (below 1 mg/kg in rocks and soils, below 0.1 mg/kg in plants, below 0.1 lg/L in
surface water) that contamination is easier to detect than for many other elements. Distribution patterns
on the sub-continental to continental-scale are, however, still dominated by natural variation. Given that
the geochemical background is characterised by a high variation at all scales, it appears impossible to
establish a reliable single value for ‘‘good soil quality” or a ‘‘natural background concentration” for Sb
for any sizeable area, e.g., for Europe. For such a differentiation, geochemical maps at a variety of scales
are needed.
Different sample materials can reflect different geochemical sources and processes, even when collected from the same survey area. Weathering (soil formation) leads to an increased Sb concentration
in soils compared to rocks. Organic soils are highly enriched (factor 5–10 compared to mineral soils)
in Sb. Soils and stream sediments return comparable median Sb concentrations. Plants are usually well
protected against Sb uptake. There exist, however, plant species that can accumulate Sb to values of more
than 1000 mg/kg. Antimony concentrations in the marine environment are not sufficiently well-documented. High Sb concentrations, related to hydrothermal and volcanic processes may have been previously underestimated.
Ó 2009 Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1.
General properties, production and use of antimony . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Regional bedrock geochemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mineral exploration and contamination – variability of Sb in soils at the local scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Mineral exploration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.
Mineral exploration in the Forssa area, Finland . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.2.
Mineral exploration and contamination: the Walchen Valley, Austria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.3.
Contamination: urban geochemistry, Berlin, Germany . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Impact of metal mining and smelting on a variety of sample materials at the regional scale – the Kola Ecogeochemistry Project . . . . . . . . . .
Continental-scale geochemical mapping. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
The Barents project . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
The Baltic Soil Survey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.
The FOREGS (EuroGeoSurveys) geochemical atlas of Europe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
* Corresponding author. Tel.: +47 73 904 307.
E-mail address: [email protected] (C. Reimann).
0883-2927/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2009.11.011
176
179
180
180
180
181
182
183
185
187
187
189
190
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6.
7.
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1.
Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.2.
Sample preparation and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.3.
Grain-size. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.4.
Soil horizon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.5.
Vegetation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.6.
Freshwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.7.
Marine environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.8.
Contamination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
The distribution, speciation, biogeochemistry and ecotoxicity of
Sb in the environment has been poorly documented until quite recently (‘‘Our knowledge of Sb behaviour in soil is nil”; ‘‘In general
little is known about plant uptake of Sb and its phytotoxicity” –
both from Adriano, 1986). This is partly due to the fact that it
was difficult (expensive) to analyse Sb with a sufficiently low
detection limit. Recently, an EU-Risk Assessment report on Diantimony Trioxide has become publicly available (EU, 2008), which
substantially expands present knowledge.
Many studies on Sb in environmental samples have focussed on
known contamination sources and their near surroundings such as
ancient and modern mines, mineral processing facilities and smelters, waste incinerators, power plants, battery factories, shooting
ranges and highways. It is rarely realised that such studies can provide a strongly biased impression of the sources and relative impact
of an element in the terrestrial environment if the regional- to continental-scale geochemistry of that element has never been studied
(Reimann et al., 2009b) and understood. The natural background
variation (Reimann and Garrett, 2005) for Sb in a variety of sample
materials at different scales thus needs to be established in order to
understand and judge the relative impact of anthropogenic sources
on the natural environment. Antimony is one of the elements
known to be enriched in the surface environment for purely natural
reasons – due to a strong tendency to organic binding (e.g., Reimann
et al., 2009a). Filella et al. (2002a,b, 2007) recently published a review of Sb in natural waters; a study on the solubility and toxicity
of Sb2O3 in soil is available from Oorts et al. (2008); Koch et al.
(2000) studied Sb species in environmental samples, while a
review of analytical methods for Sb was published by Nash et al.
(2000).
According to many authors (e.g., Lantzy and Mackenzie, 1979;
Heinrichs and Brumsack, 1997) the unusually high atmospheric
enrichment factors (EFs) obtained for Sb in various studies suggest
a strong anthropogenic signal. This observation is in contrast to the
limited production and use of Sb and the related emissions (EU,
2008). If anthropogenic sources dominated global Sb fluxes, this
impact should be rather easy to detect on a regional scale due to
the low natural Sb concentrations in most earth-surface materials.
However, distribution patterns delineated by regional- and continental-scale geochemical mapping projects (e.g., Birke and Rauch,
1997; Reimann et al., 1998, 2003b; Salminen et al., 2004, 2005;
Siewers and Herpin, 1998; Suchara and Sucharova, 2000; Sucharova and Suchara, 2004) invariably show a limited local-scale impact due to contamination from known sources and a broaderscale influence from natural processes. The concept of calculating
EFs based on continental crust or even local, mineral-soil-‘‘background” element ratios has been criticised by Reimann and Caritat
(2000, 2005). These authors demonstrated that what may work on
a local, source-related scale will not work on the regional and con-
191
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192
192
192
193
193
194
194
195
195
tinental-scale and recommended the use of EFs to demonstrate
anthropogenic impact in the absence of a defined source should
be discontinued.
Theobald et al. (1991) discuss the effect of scale on the interpretation of geochemical anomalies. Bølviken et al. (1992) provided an
interesting discussion of the fractal nature of geochemical patterns,
quite important for choosing the correct sample density at any one
scale. Salminen (1992) used the terms ‘‘reconnaissance, regional
and local” to define different scales of geochemical surveys. Xie
and Yin (1993) tried to classify geochemical patterns from local
to global according to size. Darnley et al. (1995) pointed out that
geochemical mapping can be carried out at a variety of scales –
from a single mineral grain to the globe. In this paper, data from
geochemical surveys covering areas from 5,000,000 km2 down to
1 km2 will be presented and compared. For the purpose of this paper the following definitions of scale are used:
– global scale: >50 million km2 – suggested sample density < 1
site/5000 km2;
– continental scale: 0.5–50 million km2 – sample density between
1 site/5000 km2 and 1 site/500 km2;
– regional scale: 500–500,000 km2 – sample density between 1
site/500 km2 and 1 site/km2;
– local scale: 0.5–500 km2 – sample density between 1 site/km2
and > 100 sites/km2;
– detailed scale: <0.5 km2 – sample density usually >100 sites/km2
or detailed scientific investigations on some few samples (no
geochemical mapping).
Only data from geochemical mapping projects can be used to
answer successfully the question of whether natural or anthropogenic element sources dominate the regional distribution of an element. Using such data, this paper will attempt to answer the
following questions:
– What is the local- vs. the regional-scale variation of Sb concentrations in different sample materials?
– What effect does sample preparation (grain-size, extraction)
have on Sb concentrations in a variety of sample materials?
– Is Sb preferentially enriched in certain sample materials?
– What causes local- or regional-scale Sb anomalies in different
sample materials?
– Are geogenic or anthropogenic sources dominant in the regional-scale Sb distribution in different sample materials?
– Can a useful Sb ‘‘background” value (Reimann and Garrett, 2005)
be established for a variety of sample materials at the continental-scale?
The natural variation of Sb in a variety of sample materials
needs to be documented and considered in order to establish reliable Sb background values. In addition, the possible effects of dif-
177
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
Table 1
Median Sb concentration and range (minimum–maximum) in a variety of different sample materials. Median values in mg/kg (lg/L for water) if not differently stated.
Provenance, remarks
Analytical details
Sb median
(range) mg/kg
Source, remarks
Crust
Bulk continental
Upper continental
Total, estimate
Total, estimate
0.3
0.3
Wedepohl (1995)
Wedepohl (1995)
Rocks
Sandstone
Ultramafic
Mafic
Limestone
Granite
Shale
Total,
Total,
Total,
Total,
Total,
Total,
0.05
0.1
0.2
0.15
0.3
1
Koljonen
Koljonen
Koljonen
Koljonen
Koljonen
Koljonen
Coal
World
Appalachian basin, USA
Interior province, USA
Gulf coast lignites, USA
Fort union lignites, USA
Powder river basin, USA
US coal
Total, estimate
(N = 4700)
(N = 800)
(N = 200)
(N = 350)
(N = 800)
(N = 7372)
2
1.4
1.5
1
0.69
0.57
0.72 (0.01–70)
Tauber (1988)
Finkelman et al. (1994)
Finkelman et al. (1994)
Finkelman et al. (1994)
Finkelman et al. (1994)
Finkelman et al. (1994)
Bragg et al. (1998)
<2 mm, total, estimate
<2 mm, total, (N = 354 out of 1257)
<2 mm, multi-acid, ICP-MS (N = 840)
<2 mm, multi-acid, ICP-MS (N = 172)
<2 mm, multi-acid, ICP-MS (N = 216)
<2 mm, multi-acid, ICP-MS
<2 mm, multi-acid, ICP-MS (N = 172)
<2 mm, multi-acid, ICP-MS (N = 216)
<2 mm, aqua regia (N = 743)
<2 mm, aqua regia (N = 746)
<2 mm, HF (N = 747)
<2 mm, HF (N = 747)
<2 mm, XRF (N = 748)
<2 mm, XRF (N = 747)
<2 mm, 4-acid, ICP-MS (N = 1310)
<2 mm, total (N = 1273 from 850,000 km2)
<2 mm, total (INAA) (N = 1076)
<2 mm, total (INAA) (N = 1076)
<2 mm total (INAA) (N = 294)
<2 mm total (INAA) (N = 295)
<0.063 mm, total (N = 1057)
0.45–2 mm, total
Milled to <0.75 um, HNO3–HClO4–HCl–HF
<2 mm, ground, 4-acid (N = 180)
0.5
<1 (<1–8.8)
0.6 (0.02–31.1)
0.22 (0.02–2.18)
0.88 (0.08–31)
0.47 (<0.02–30.3)
0.19 (<0.02–2.86)
0.83 (0.09–30)
<10 (<10–<10)
<10 (<10–10)
0.24 (<0.1–3.2)
0.19 (<0.1–1.41)
<5 (<5–9.0)
<5 (<5–12)
0.53 (<0.05–5.29)
0.6
0.5 (<0.05–1.6)
0.7 (0.05–3.3)
0.3 (<0.1–1.4)
0.2 (<0.1–3.1)
0.3
<0.5
0.5 (<0.1–47.5)
0.44 (0.09–7.95)
Koljonen (1992)
Shacklette and Boerngen (1984)
Salminen et al. (2005)
Salminen et al. (2005)
Salminen et al. (2005)
Salminen et al. (2005)
Salminen et al. (2005)
Salminen et al. (2005)
Reimann et al. (2003b)
Reimann et al. (2003b)
Reimann et al. (2003b)
Reimann et al. (2003b)
Reimann et al. (2003b)
Reimann et al. (2003b)
Zhang et al. (2008)
Garrett (1994), Garrett et al. (2008)
Garrett (2009), pers. comm.
Garrett (2009), pers. comm.
Garrett (2009), pers. comm.
Garrett (2009), pers. comm.
Koljonen (1992)
Smith et al. (1992)
Cornelius et al. (2007)
Smith (2009), pers. comm.
<2 mm, ground, 4-acid (N = 172)
0.47 (<0.05–15.1)
Smith (2009), pers. comm.
<2 mm, ground, 4-acid (N = 172)
0.28 (<0.05–6.29)
Smith (2009), pers. comm.
<2 mm, 4-acid (N = 275)
<2 mm, 4-acid (N = 254)
<2 mm, 4-acid (N = 263)
<2 mm, conc. HNO3 (N = 617)
<2 mm, aqua regia (N = 609)
<2 mm, aqua regia (N = 605)
<2 mm, total INAA (N = 605)
<2 mm, conc. HNO3 (N = 1357)
<2 mm, total (N = 1342)
<2 mm, aqua regia (N = 1342)
<0.125 mm, HG-AAS (N = 5189)
<0.125 mm, HG-AAS (N = 5190)
<0.18 mm, total INAA (N = 772)
<0.18 mm, aqua regia, ICP-MS (N = 85)
<0.06 mm, aqua regia, GFAAS (N = 1318)
(N = 300)
(N = 300)
<2 mm, total (N = 50)
<2 mm, HNO3–HF–HCl, ICP-MS (N = 448)
<2 mm, total (XRF) (N = 3747)
<2 mm, total (XRF) (N = 2182)
0.52 (0.06–2.4)
0.6 (0.14–2.3)
0.53 (0.05–2.3)
0.18 (0.016–0.96)
<0.01 (<0.01–1.33)
<0.01 (<0.01–1.42)
<0.1 (<0.1–3.0)
0.17 (<0.02–27.2)
0.18 (<0.1 –1.23)
0.024 (<0.01–0.66)
0.7 (<0.1–247)
0.5 (<0.1–1165)
2.7 (0.4–44)
2 (<0.2–15.5)
0.08 (?–2.4)
0.17 (<0.02–1.16)
0.16 (<0.02–0.29)
0.46 (0.15–1.95)
0.15 (0.02–3.2)
2.4 (0.7–454)
2.7 (0.7–153
Smith et al. (2005)
Smith et al. (2005)
Smith et al. (2005)
Reimann et al. (1998)
Reimann et al. (1998)
Reimann et al. (1998)
Reimann et al. (1998)
Salminen et al. (2004)
Salminen et al. (2004)
Salminen et al. (2004)
Čurlík and Šefčík (1999)
Čurlík and Šefčík (1999)
Reimann (1989)
Göd (1994)
Kärkkäinen et al. (2007)
Tarvainen et al. (2006)
Tarvainen et al. (2006)
Bradford et al. (1996)
Chen et al. (1999)
Birke and Rauch (1997)
Birke and Rauch (1997)
Soils
World
Conterminous US, soil, 20 cm depth
European Union, Topsoil (0–20 cm)
Northern Europe, Topsoil (0–20 cm)
Southern Europe, Topsoil (0–20 cm)
European Union, C-horizon
Northern Europe, C-horizon
Southern Europe, C-horizon
Northern Europe, agric. soil 0–25 cm
Northern Europe, agric. soil 50–75 cm
Northern Europe, agric. soil 0–25 cm
Northern Europe, agric. soil 50–75 cm
Northern Europe, agric. soil 0–25 cm
Northern Europe, agric. soil 50–75 cm
Ireland, surface soil, 0–10 cm (71,000 km2)
Canada, Ap-horizon
Canada, Prairie surface soil
Canada, Prairie soil C-horizon
Canada, S.-Ontario surface soil
Canada, S.-Ontario soil C-horizon
Till, Finland, C-horizon
Laterite Australia
Laterite, Yilgarn Craton, Australia
NE-US (Maine, New Hamshire, Vermont,
Massachusetts, Rhode Island, New York),
Topsoil 0–5 cm
NE-US (Maine, New Hamshire, Vermont,
Massachusetts, Rhode Island, New York),
A-horizon
NE-US (Maine, New Hamshire, Vermont,
Massachusetts, Rhode Island, New York),
C-horizon
N-America transect, Topsoil 0–5 cm
N-America transect, A-horizon
N-America transect, C-horizon
Kola, O-horizon
Kola, B-horizon
Kola, C-horizon
Kola, C-horizon
Barents Region, O-horizon
Barents Region, C-horizon
Barents Region, C-horizon
Slovak Republic, A-horizon
Slovak Republic, C-horizon
Austria, Walchen, B-horizon (100 km2)
Austria, Saualpe, B-horizon
Finland, Pirkanmaa region, Till
Finland, Helsinki region (3000 km2), Topsoil
Finland, Helsinki region (3000 km2), sub-soil
California, soil 0–50 cm
Florida, surface soil
Berlin, topsoil, 0–20 cm, all
Berlin, tosoil, 0–20 cm, inner city
estimate
estimate
estimate
estimate
estimate
estimate
(1992)
(1992)
(1992)
(1992)
(1992)
(1992)
(continued on next page)
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C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
Table 1 (continued)
Provenance, remarks
Analytical details
Sb median
(range) mg/kg
Source, remarks
Berlin, topsoil, 0–20 cm, surroundings
Trondheim, topsoil, 0–2 cm
Naples, topsoil, 0–15 cm
<2 mm, total (XRF) (N = 1562)
<2 mm, aqua regia (N = 314)
<0.15 mm, aqua regia, ICP-MS
(N = 794)
<2 mm, total (XRF) (N = 531)
<2 mm, total (XRF) (N = 1381)
<2 mm, total (XRF) (N = 216)
<2 mm, total (XRF) (N = 257)
<2 mm, total (XRF) (N = 575)
<2 mm, total (XRF) (N = 409)
<2 mm, total (XRF) (N = 500)
<2 mm, 4-acid, ICP-MS (N = 498)
<0.25 mm, 4-acid, ICP-MS
(N = 498)
2.1 (0.8–454)
<7 (<7–18)
0.7 (0.21–42.8)
Birke and Rauch (1997)
Ottesen et al. (1995)
De Vivo et al. (2006)
9.0 (0.5–42.0)
1.3 (<1–173.5)
<1 (<1–100)
2 (<1–35)
3 (<1–47)
1 (<1–73)
0.9 (0.1–8.6)
0.72 (0.1–14.5)
0.91 (0.19–15.1)
Bityukova et al. (2000)
Fordyce et al. (2009)
O’Donnell (2005)
Freestone et al. (2004a)
Freestone et al. (2004b)
O’Donnell et al. (2004)
Duris (1999, 2000)
Kilburn et al. (2007)
Kilburn et al. (2007)
0.64 (<0.02–34.1)
de Vos et al. (2006)
0.34 (<0.02–9.7)
0.96 (<0.02–15)
<5 (<5–20)
0.82 (0.12–15.2)
de Vos et al. (2006)
de Vos et al. (2006)
Birke et al. (2006)
Birke et al. (2006)
0.93 (<0.5–21)
4 (<1–350)
<2 (<2–66.5)
0.6 (<0.1–88)
0.3 (<0.1–170)
1.2 (0.05–140)
0.6 (0.07–123)
0.49 (0.09–123)
0.74 (<0.02–99)
Schedl et al. (2009)
Weaver et al. (1983)
BGS (1993)
O’Connor and Gallagher (1994)
Garrett (2009), pers. comm.
Garrett (2009), pers. comm.
Imai et al. (2004)
Ohta et al. (in press)
de Vos et al. (2006)
0.35 (<0.02–3.73)
de Vos et al. (2006)
Tallinn, topsoil, 0–20 cm
Glasgow, topsoil 5–20 cm
Lincoln, topsoil, 5–20 cm
Mansfield, topsoil, 5–20 cm
Sheffield, topsoil, 5–20 cm
Kingston-upon-Hull, topsoil, 5–20 cm
Prag, topsoil
Denver, Colorado, topsoil 0–15 cm
Denver, Colorado, topsoil 0–15 cm
Fluvial sediments
Stream sediment, Europe
Stream
Stream
Stream
Stream
sediment,
sediment,
sediment,
sediment,
Northern Europe
Southern Europe
Germany
Germany
Stream sediment, Austria, Styria
Stream sediment, Alaska
Stream sediment, S.-Scotland
Stream sediment, Ireland (Leinster)
Stream sediment, Canada
Stream sediment, Yukon
Stream sediment, Japan
Stream sediment, Japan, Hokkaido
Floodplain sediments, Europe
Floodplain sediments, Northern Europe
Floodplain sediments, Southern Europe
Floodplain sediments, Svalbard
Organic stream sediment, Finland
<0.15 mm, aqua regia, ICP-MS
(N = 848)
<0.15 mm, aqua regia (N = 174)
<0.15 mm, aqua regia (N = 271)
<0.15 mm, total (XRF) (N = 946)
<0.15 mm, HF–HNO3 (ICP-MS)
(N = 946)
<0.18 mm (N = 845)
<0.2 mm (-100 mesh), total INAA
<0.10 mm, total (XRF) (N = 9865)
0.125 mm, total (INAA) (N = 1194)
<0.177 mm, total (N = 50,434)
<0.177 mm, total (N = 13,942)
<0.15 mm, total (4-acid), (N = 3024)
<0.15 mm, total (4-acid), (N = 798)
<2 mm, ground to <0.063 mm, aqua regia
(N = 743)
<2 mm, ground to <0.063 mm, aqua regia,
(N = 137)
<2 mm, ground to <0.063 mm, aqua regia,
(N = 265)
<0.063 mm, total (INAA), (N = 650)
<2 mm, conc. HNO3 (N = 1166)
0.97 (<0.02–39)
de Vos et al. (2006)
0.8 (<0.4–5.5)
0.052 (<0.02–0.18)
Ottesen et al. (1988)
Lahermo et al. (1996),
(range: 2nd and 98th percentile)
Marine sediments
Gulf of Finland (c. 30,000 km2),
uppermost 1 cm
Coastal sea sediments off Hokkaido, Japan
(115,000 km2)
Multi-acid extraction, ICP-MS (N = 57)
0.52 (0.12–3.32)
Henry Vallius (2009), pers. comm.
Ground, 0–3 cm, HF–HClO4–HNO3, ICP-MS
(N = 1406)
0.58 (0.05–1.69)
Ohta et al. (in press)
Plants
Terrestrial
World
Moss, Kola
Moss, Barents
Moss, Germany
Moss, Czechia
Lichen, Canada, Cetraria cucullata
Lichen, Canada, Cetraria nivalis
Lichen, Canada, Cladina stellaris
Lichen, Canada, Xanthoria elegans
Lichen, Germany, Lecanora muralis
Dandelion, Europe
Moss, Oslo transect
Fern, Oslo transect
Mountain Ash leaves, Oslo transect
Birch leaves, Oslo transect
Birch bark, Oslo transect
Birch wood, Oslo transect
Spruce needles, Oslo transect
Spruce wood, Oslo transect
Birch leaves, S-Norway transect
Willow leaves, S-Norway transect
Heather leaves & twigs, S-Norw. tran.
Juniper needles, S-Norway transect
Pinus sylvestris, Germany, inner bark
Ectomycorrhizal fungi, background area
Ectomycorrhizal fungi, mining area
Terrestrial saprobes, background area
‘‘Reference plant”
Conc. HNO3 (N = 593)
Conc. HNO3 (N = 1346)
Conc. HNO3 + H2O2
Conc. HNO3 + H2O2 (N = 280)
Total, mean, (N = 26, all Canada)
Total, mean, (N = 25, all Canada)
Total, mean, (N = 13, all Canada)
Total (N = 9, Ontario)
Total (N = 42, all Germany)
Total, INAA, few samples, geom. mean
Conc. HNO3, HNO3–HCl (N = 40)
conc. HNO3, HNO3–HCl (N = 33)
Conc. HNO3, HNO3–HCl (N = 38)
Conc. HNO3, HNO3–HCl (N = 40)
Conc. HNO3, HNO3–HCl (N = 40)
Conc. HNO3, HNO3–HCl (N = 40)
Conc. HNO3, HNO3–HCl (N = 40)
Conc. HNO3, HNO3–HCl (N = 40)
Conc. HNO3, HNO3–HCl (N = 41)
conc. HNO3, HNO3–HCl (N = 41)
Conc. HNO3, HNO3–HCl (N = 41)
Conc. HNO3, HNO3–HCl (N = 41)
Conc. HNO3, HF–HNO3 (N = 29)
Total, INAA (N = 67)
Total, INAA (N = 32)
Total, INAA (N = 38)
0.10
0.04 (<0.02–0.64)
0.04 (<0.02–2.8)
0.17 (0.04–3.1)
0.16 (0.04–1.73)
0.08
0.09
0.13
<0.04 (<0.04–0.21)
1.0 (0.2–7.3)
0.08
0.13 (0.05–1.48)
0.04 (<0.02–1.2)
0.02 (<0.02–0.49)
0.03 (0.02–0.33)
<0.02 (<0.02–0.09)
<0.02 (<0.02–0.02)
<0.02 (<0.02–0.16)
<0.02 (<0.02– < 0.02)
0.05 (0.02–0.09)
0.04 (0.02–0.10)
0.05 (<0.02–0.10)
(<0.02–0.10)
0.0132 (<0.01–0.039)
0.035 (<0.005–11.8)
0.434 (0.030–1423)
0.055 (< 0.01–0.440)
Markert (1992)
Reimann et al. (1998)
Salminen et al. (2004)
Siewers and Herpin (1998)
Sucharova and Suchara (2004)
Puckett and Finegan (1980)
Puckett and Finegan (1980)
Puckett and Finegan (1980)
Matschullat et al. (1999)
Matschullat et al. (1999)
Djingova and Kuleff (1993)
Reimann et al. (2006)
Reimann et al. (2007a)
Reimann et al. (2007a)
Reimann et al. (2007c)
Reimann et al. (2007c)
Reimann et al. (2007c)
Reimann et al. (2007c)
Reimann (unpublished data)
Reimann (unpublished data)
Reimann (unpublished data)
Reimann (unpublished data)
Reimann (unpublished data)
Birke et al. (2009)
Borovicka et al. (2006)
Borovicka et al. (2006)
Borovicka et al. (2006)
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C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
Table 1 (continued)
Provenance, remarks
Analytical details
Sb median
(range) mg/kg
Source, remarks
Terrestrial saprobes, mining area
Marine
Brown algae
Red algae
Green algae
Total, INAA (N = 15)
0.3 (0.05–3.22)
Borovicka et al. (2006)
Total, INAA (N = 14)
Total, INAA (N = 15)
Total, INAA (N = 6)
0.121 (0.056–0.192)
0.141 (0.075–0.307)
0.138 (0.037–0.310)
Hou and Yan (1998)
Hou and Yan (1998)
Hou and Yan (1998)
Estimate
Filtered <0.45 mm (N = 807)
Filtered <0.45 mm (N = 173)
(lg/L)
0.10
0.07 (<0.002–2.91)
0.03 (<0.002–2.91)
Koljonen (1992)
Salminen et al. (2005)
Salminen et al. (2005)
Filtered <0.45 mm (N = 253)
0.07 (<0.002–0.98)
Salminen et al. (2005)
Filtered
Filtered
Filtered
Filtered
0.022
0.092
0.012
0.028
Salminen et al. (2004)
Birke et al. (2006)
Hall (1997)
Lahermo et al. (1996)
(range: 2nd–98th percentile)
Siewers (1997)
Konhauser et al. (1997)
Roostai (1997)
National Research Council of Canada
international river water standard see:
http://inms-ienm.nrc-cnrc.gc.ca/
calserv/crm_files_e/SLRS-4_e.pdf
Fresh water, surface
World average
European Union
Northern Europe
(Finland, Norway, Sweden)
Southern Europe
(France, Italy, Spain)
Barents region
Germany
Nova Scotia
Finland
Romania
Eastern India
Harz, Germany
SLRS-4, River water
<0.45 mm
<0.45 mm
<0.45 mm
<0.45 mm
(N = 1365)
(N = 944)
(N = 513)
(N = 1167)
(<0.002–10.3)
(0.007–2.09)
(<0.004–0.105)
(<0.02–0.093)
Unfiltered (N = 113)
<0.20 mm (N = 31)
Unfiltered
0.14 (0.02–0.89)
0.1 (<0.1–1)
0.13 (<0.01–1.8)
0.23
Precipitation
Erzgebirge, Germany, rain water (bulk)
Kola Peninsula, rain water (bulk)
Filtered <0.45 lm (N = 24)
Filtered <0.45 lm (N = 45)
0.17 (0.06–0.48)
<0.025 (<0.025–0.36)
Matschullat et al. (2000b)
Reimann et al. (1997c)
Groundwater
Norway, private bedrock wells
Norway, water works, bedrock
Norway, water works, quaternary aqu.
Finland, shallow groundwater (dug wells)
Finland, bedrock wells (drilled)
Ethiopia, Bedrock
Germany, groundwater
Slovakia
Geothermal water, Yellowstone, USA
Unfiltered (N = 476)
Unfiltered (N = 137)
Unfiltered (N = 189)
(N = 739)
(N = 263)
Unfiltered (N = 138)
(N = 295)
Filtered <0.45 mm (N = 16,359)
(N = 23)
0.03 (<0.002–8)
0.04 (0.003–0.75)
0.027 (<0.02–0.79)
0.03 (<0.02–0.82)
0.02 (<0.02–1.46)
0.028 (<0.002–1.78)
0.09 (<0.05–1.1)
<0.2 (<0.2–2350)
66 (9–166)
Frengstad et al. (2000)
Frengstad (2009), pers. comm.
Frengstad (2009), pers. comm.
Lahermo et al. (2002)
Lahermo et al. (2002)
Reimann et al. (2003a)
Plessow et al. (1997)
Rapant et al. (1996)
Stauffer and Thompson (1984)
Estimate
Surface water
Surface water
Surface water,
transect Uruguay-Barbados
Surface water
Surface water
ICPMS (N = 16)
0.20
(0.09–0.14)
0.21
0.13
Lide (1996)
Donat and Bruland (1995)
Donat and Bruland (1995)
Cutter et al. (2001)
0.15
0.25
0.227 (0.190–0.264)
Cutter and Cutter (1995)
Cutter and Cutter (1998)
Garbe-Schönberg (2009),
pers. comm.
Garbe-Schönberg (2009),
pers. comm.
Garbe-Schönberg (2009),
pers. comm.
Garbe-Schönberg (2009),
pers. comm.
Garbe-Schönberg (2009),
pers. comm.
Garbe-Schönberg (2009),
pers. comm.
Garbe-Schönberg (2009),
pers. comm.
Marine water
World
North Pacific
North Atlantic
Western Atlantic Ocean
Eastern Atlantic Ocean
High latitude North Atlantic
IAPSO, seawater
NASS-5, North Atlantic seawater, 10 m
(NRCC)
North Atlantic, Kolbeinsey, 150 m
ICPMS (N = 17)
0.207 (0.184–0.230)
ICPMS (N = 2)
0.21
SW Pacific, Monowai
ICPMS (N = 2)
0.212
Mediterranean sea, Palinuro Smt., 500 m
ICPMS (N = 2)
0.226
Hydrothermal fluid, Tonga Island Arc,
Volcano 19
Hydrothermal fluid, Mid Atlantic Ridge,
Logatchev
ICPMS, Endmember
120
ICPMS, Endmember
3
ferent extraction methods, grain-size of soil or sediment samples
used for analyses, soil horizon and plant species collected all
need to be compared. This paper collects Sb data from the literature and from various geochemical mapping projects covering substantial areas at scales that vary from local to continental. The
surveys from which examples are drawn were carried out in Europe during the last 5–20 a (e.g., Birke and Rauch, 1997; Reimann,
1986, 1988, 1989; Reimann et al., 1998, 2003b; Salminen et al.,
2004, 2005).
1.1. General properties, production and use of antimony
Antimony, atomic number 51 (atomic mass: 122), is a trace
element and the 63rd most abundant of the 92 naturally occurring
elements in the Earth’s crust. Its chemical properties are said to be
quite similar to As (this paper will demonstrate that its chemical
behaviour in the surface environment may actually be different),
but its crustal abundance is about one order of magnitude lower.
While often referred to as a heavy metal in the environmental
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C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
literature, it is chemically a non-metal. It occurs in four oxidation
states ( 3,+3,+4 and +5). The two oxidation states +3 and +5 predominate in environmental samples. Antimony has two naturally
occurring stable isotopes (121Sb and 123Sb) with abundances of
57.21% and 42.79%, respectively. There are 42 unstable isotopes
with rather short half-lives (max. 2.76 a). Antimony is a chalcophile
element. More than 100 minerals are known to contain Sb (mostly
complex Cu–Pb- and Sb–Hg-sulfides). It forms a number of distinct
ore minerals (stibnite – Sb2S3, kermesite – Sb2S2O, valentinite
– Sb2O3, cervantite – Sb2O4) which occur in ore deposits but are not
found in normal bedrock (in contrast to the As-mineral arsenopyrite, FeAsS, and As-rich pyrites, which are widespread trace constituents of many rocks). The element may also – though rarely – occur
in native form. Traces of Sb can enter the lattices of silicates like
Mg-olivine and ilmenite, and those of the common ore minerals
galena, sphalerite and the ubiquitously present pyrite. In regional
geochemistry Sb has been predominantly used as a pathfinder for
Au deposits (Hawkes and Webb, 1962; Levinson, 1974,1980).
In the secondary environment, Sb has a strong tendency to sorb
to hydrous oxides, organic residues and clay minerals (Ure and Berrow, 1982). In the terrestrial environment, Sb is considered to be
rather immobile (Ainsworth et al., 1990, 1991; Flynn et al.,
2003). Antimony is enriched in top soil material due to chelation
with organic matter, but an enrichment in the soil B-horizon due
to strong Sb sorption by hydrous Fe-oxides, clay minerals and
Mn- oxides/hydroxides can also be expected (Boyle and Jonasson,
1984). The redox speciation data available for surface waters and
soils generally confirm that Sb(V) dominates over Sb(III) (Belzile
et al., 2001; Filella et al., 2002b; Koch et al., 2000). Antimony is
one of the elements for which microbial methylation has been observed in nature (Bentley and Chasteen, 2002).
The world production of Sb has only increased slightly during
the last 10–15 a (119,000 t in 1995: Berner, 1997 – see Reimann
and Caritat, 1998; ca. 134,000 t in 2006, see http://www.indexmundi.com/en/commodities/minerals/antimony/antimony_t1.html).
At present (2008), more than 90% of world mine production comes
from China (Carlin, 2009).
Most of the Sb mined is used to produce Diantimony Trioxide
(Sb2O3), which is used as a catalyst in the production of polyethylene terephthalate (PET), as a flame retardant in the production of
plastic, textiles and rubber, in pigments, paints, coatings and
ceramics and in the production of crystal glass. Antimony is an
important component for a number of alloys, especially in the production of ammunition and batteries. Antimony is a typical contaminant on shooting ranges and at military installations. The
element is also used in the treatment of leishmaniasis and bilharziosis. About 40% of the 2008 United States Sb consumption went
into flame retardants, 22% into transportation including batteries,
4% into chemicals, 11% into ceramics and glass and 3% to ‘‘other”
uses (Carlin, 2009). Anthropogenic emissions to the atmosphere
can be predominately expected from metal smelting and refining
activities. Another possible source of anthropogenic Sb emissions
to the atmosphere is oil and coal combustion (e.g., Mukherjee
et al., 2008). The mean Sb concentration of coal is given as 2 mg/
kg (Tauber, 1988). The data from the US Geological Survey coal
data base (Bragg et al., 1998) suggest that 1 mg/kg may be a more
realistic value. Other high-temperature processes like waste incineration will also release Sb to the atmosphere. Due to the use of Sb
in brake linings (the use of Sb2O3 was discontinued in 2005, but
there are still other Sb compounds used in the manufacture of
brakes) and in rubber (vehicle tyres, Sb pentasulphide is used in
vulcanising rubber), traffic must be considered as a source of Sb
emissions along roads and generally in the urban environment
(Heinrichs et al., 1997).
Antimony is considered to be a non-essential element. Sb(III)
compounds may be somewhat more toxic than Sb(V) compounds
(e.g., Bencze, 1994; He and Yang, 1999). The European Union has
set an action level of 5 lg/L for Sb in drinking water (Council of
the European Union, 1998 – under revision), the United States
Environmental Protection Agency (USEPA) suggests a ‘‘maximum
contaminant level” in drinking water of 6 lg Sb/L (USEPA, 1999).
The new EU risk assessment report for Diantimony Trioxide (EU,
2008) provides the following predicted no effect concentration
(PNEC) values for a variety of environmental media:
PNECsurface water = 113 lg Sb/L
PNECsediment = 11.2 mg Sb/kgdry weight (7.8 mg Sb/kgwet weight)
PNECmicroorganisms = 2.55 mg Sb/L
PNECsoil = 37 mg Sb/kgdry weight
PNECmarine water = 11.3 lg Sb/L
PNECmarine sediment = 2.24 mg Sb/kgdry weight (1.6 mg Sb/kgwet weight)
PNECsecondary poisoning = 374.8 mg/kg food
A PNEC is derived based on the results of reliable toxicity studies and represents the concentration that should not be exceeded
in order to avoid adverse effects.
Information on Sb concentrations in a wide variety of sample
materials is provided in Table 1. When selecting the data for this
table, the focus was on large datasets, covering substantial areas
and providing Sb analyses for a large enough number of samples
to be representative. Sample sets in which different analytical
techniques were used on the same set of samples, different
grain-size fractions of soil and sediment samples were studied in
parallel, or a variety of different sample materials were collected
from the same locations were preferentially chosen for inclusion
in this table.
2. Regional bedrock geochemistry
Variation in the median values in the different rock types provided in Table 1 covers between one and two orders of magnitude
(0.05–1 mg/kg). The data in Table 1 are all for rocks visually unaffected by ore-forming processes. Differences between the various
rock types are, in general, surprisingly low. This may in part be
due to the rather limited data on Sb in rocks. Fine-grained sedimentary rocks (shales) show approximately a 20-fold increase in
Sb values as compared to coarse-grained ones such as sandstones.
This may be either a direct reflection of grain-size or of the depositional environment.
There are few limited representative datasets on bedrock geochemistry at the regional scale. One exception is the Slovak rock
geochemistry atlas (Marsina, 1999). These data indicate that rock
age can result in significant differences in the median Sb concentration for the same bedrock type. In Slovakia, Palaeozoic rocks
are especially enriched in Sb. An enrichment of Sb (W and Hg) in
Palaeozoic rocks was originally described more than 40 a ago
(Maucher, 1965). The maximum value reported in the Slovak rock
geochemistry atlas for Sb is 12 mg/kg Sb in a Late Palaeozoic
metapsammite (Marsina, 1999).
Near mineralisation, rock samples can contain up to several
hundred mg/kg Sb (Reimann, 1980).
3. Mineral exploration and contamination – variability of Sb in
soils at the local scale
3.1. Mineral exploration
For mineral exploration projects, stream sediment and soil samples are usually collected at a high density. Densities of one sample
per 1–5 km2 in the reconnaissance phase (e.g., stream sediments)
and up to several hundred samples per km2 in the follow-up and
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
target phases (most often soils) are routinely used (e.g., Levinson
1974, 1980; Rose et al., 1979). The reason for these high densities
is that a mineral deposit is usually a small target, and many regularly spaced samples are needed in order to locate it precisely.
Until quite recently, it has been rather difficult and expensive to
analyse Sb with sufficiently low detection limits to be of use in routine geochemical exploration programs. Antimony was known to
form rather limited dispersion halos and thus small anomalies
around mineral occurrences (Jarusevskij et al., 1961; Terechova,
1961, 1966).
The element has nevertheless been used successfully to find and
delineate Sb mineralisation. For example, Reimann (1980) presented results from a Sb exploration project using soil samples in
the Kreuzeck Mountains, Austria. Values up to 3700 mg Sb/kg in
B-horizon soils were observed near massive Sb ore lenses (>20%
Sb) in meta-sediments. Major anomalies were observed directly
on top of the ore lenses; Sb concentrations disappeared in the
background variation at a distance of 10–50 m from the
mineralisation.
3.1.1. Mineral exploration in the Forssa area, Finland
The Tampere As province in SW Finland covers an area of about
20,000 km2. This province includes several small Au deposits
including three mines from which Au has been one of the main
products. The area has been a target for mineral exploration for
more than 20 a. The first indications of Au were recently detected
in the Forssa area in the southern part of the Tampere province
(Kärkkäinen et al., 2008).
181
The bedrock in the Forssa area consists of zones of Palaeoproterozoic Svecofennian volcanic rocks with granitoid complexes intersecting the volcanic zones. Mafic intrusions are sometimes found
in the contact zones between the volcanites and granitoids. Arsenic
is a common trace element in shear and alteration zones where the
Au mineralisation normally occurs. Bismuth, Sb and Te minerals
are common constituents accompanying the Au mineralisation
(Kärkkäinen et al., 2008).
Geochemical till sampling was carried out in the area from
2003–2007. The average sample density was four samples per
km2, and 600 km2 were covered. Samples were taken from the bottom part of the till cover by motor-driven drilling devices. For the
example discussed here, 1604 samples were collected. The
<0.063 mm fraction was used for analyses. Antimony was determined by graphite furnace AAS, following an aqua regia extraction
at 20 °C and precipitation with Hg.
The distribution of Sb shows a compact anomaly pattern in the
north-eastern part of the study area. Though the values can often
be connected to the occurrence of volcanic rocks, they do not correlate exactly with any of the bedrock units nor with the metamorphic zones. The main anomaly shows a clear orientation, but the
reasons for this are still unknown (Fig. 1). It is currently assumed
that the entire large area of Sb anomalies in this region is due to
widespread postorogenic hydrothermal activity in the crust
(Kärkkäinen et al., 2008). Drilling of several targets is in progress
and Au mineralisation has been detected (e.g., 9 m of drill core
yielding 4.3 mg/kg Au and 1 m drill core yielding 23.5 mg/kg Au).
The example demonstrates the variation that natural Sb concentra-
Fig. 1. Geochemical exploration in Finland: Sb concentration in the <0.063 mm fraction of glacial till in the Forssa area. Lithological units: 1. Mafic volcanite, 2. Intermediate
and acid volcanite, 3. Mica schist, 4. Granodiorite, 5. Diorite, 6. Granite. Modified from Kärkkäinen et al. (2008).
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C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
Fig. 2. Cumulative probability diagram for Sb in the soil B-horizon, Walchen,
Austria, size fraction <0.177 mm, total concentrations (INAA).
tions can show in soils (till) over short distances, anomalies are
pronounced, but localized (on a detailed scale) (Fig. 1).
3.1.2. Mineral exploration and contamination: the Walchen Valley,
Austria
A total of 772 soil B-horizon samples were collected at an average density of eight samples per km2 over a 100 km2 area in the
surroundings of the Walchen Mine, Austria (Reimann, 1986,
1988, 1989; Weinzierl and Wolfbauer, 1991). The purposes of the
study were: (1) to document the environmental impact of the ancient mining and smelting activities; and (2) to estimate the potential for further ore bodies in the same setting. All the soil samples
were air dried, sieved to 80 mesh (<0.177 mm) and analysed for
total Sb concentrations by instrumental neutron activation analysis (INAA). Further details about the project and quality-control results can be found in Reimann (1986, 1988, 1989). An in-depth
description of the local geology is provided in Peer (1988, 1989).
The Walchen Mine was originally opened around 1450 AD and
more recently operated sporadically from 1858 until 1947. Almost
300,000 t of Cu ore were produced during the main production
period from 1696 to 1858 (Redlich, 1903; Weinzierl and Wolfbauer, 1991). The average ore contained 1.53% Cu, 2.1% Pb, 2.75%
Zn, 31.84% S, 30.6% Fe and 0.45% As (Unger, 1968).
Compared with the suggested world average value for Sb in
soils (0.5 mg/kg, see Table 1; Koljonen, 1992), the median Sb concentration in the soils from the Walchen area is high: 2.7 mg/kg.
The statistical distribution of the Sb analyses from the Walchen
area is presented in a cumulative probability plot (Fig. 2) and their
spatial distribution in a regional map (Fig. 3). These suggest that no
more than the uppermost 5% of the distribution is influenced by
the following factors: (1) the mine in the centre of the Walchen
Valley, (2) the mineralised horizon running in an east–west direction through the centre of the map and (3) possible short-range
atmospheric contamination from the old roasting and smelting
activities in the valley. Antimony anomalies towards the eastern
Fig. 3. Antimony concentrations in soil B-horizon samples, size fraction <0.177 mm, total concentrations (INAA), Walchen area, Austria. Each grid cell has a size of 1 km2
(1 1 km). EDA symbols (with accentuated upper outlier symbol) and boxplot classes (Reimann et al., 2008) used for mapping.
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
and western map boundary mark the continuation of the mineralised horizon. No mining was ever attempted there; these values
are natural Sb anomalies. Previously unknown massive sulfide
mineralisation was discovered during a follow-up survey of the
highest anomaly (44 mg/kg) in the neighbouring valley. The linear
anomaly in the centre of the Walchen Valley delineates the known
extent of the ore body. Geochemical background values are
reached at much less than 1 km from the ore horizon (Fig. 3). Even
with hundreds of years of ongoing mining and smelting activities
in this valley, the sample density is just high enough to successfully mark the location of the mine, the old smelter and the ore
horizon.
In general, slightly higher Sb concentrations mark the soils in
the northern half of the survey area. Peer (1988, 1989) has shown
that an important geological boundary occurs between the ‘‘Ennstaler Phyllites” in the north and the ‘‘Wölzer Mica Schists” in the
south (see Fig. 3, the ore horizon occurs close to this boundary).
The ore horizon is situated in the Wölzer Mica Schists (Peer,
1988, 1989). Soils on top of the Ennstaler Phyllites show a median
value of 2.9 mg/kg Sb and the soils on top of the Wölzer Mica
183
Schists show a median value of 2.2 mg/kg Sb. The slightly enhanced median value on top of the Ennstaler Phyllites probably
indicates different geochemical background ranges for Sb in these
rocks. A geochemical map of a much larger area would be required
to establish the general background variation of Sb for the two geological units. A database of Sb concentrations in the different rock
types and geological units occurring in Austria would also help to
answer this question. The Walchen data clearly demonstrate the
local scale of the impact of mineralisation and mining-related soil
contamination – at least on the soil B-horizon. A considerably higher sample density, than the chosen eight samples per km2, would
be needed to reliably document contamination. Interestingly, some
follow-up targets for a possible extension of the mineralised horizon could still be identified, even though Sb is known to form only
limited ore-related anomalies.
3.1.3. Contamination: urban geochemistry, Berlin, Germany
Birke and Rauch (1997) published geochemical maps of the
greater Berlin area. An area of 4000 km2, including and surrounding the German capital, is represented by 3756 topsoil (0–20 cm)
Fig. 4. Antimony concentration in Berlin top soils (0–20 cm), <2 mm fraction, total concentrations (XRF). Numbers in the map refer to anomalies explained in the text. The
line defines the Berlin city limit.
Fig. 5. Cumulative probability plot (left) and boxplot comparison (right) of Sb in the four main sample materials used for the Kola Project, moss and soil O-horizon conc.
HNO3-extraction, soil B- and C-horizon aqua regia extraction. Soil samples: <2 mm fraction.
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C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
Fig. 6. Regional distribution of Sb in moss and soil O- and C-horizon samples in the Kola Project area and location map. Moss and soil O-horizon: conc. HNO3-extraction, soil
C-horizon aqua regia extraction, soil samples <2 mm fraction. C1–C8: locations of catchments for catchment study phase.
Table 2
Kola Ecogeochemistry Project, catchment stage. Antimony concentrations in topsoil (Niskavaara et al., 1997; Reimann et al., 1997a,c), overbank sediments (Volden et al., 1997),
organic stream sediments (unpublished data), moss (Niskavaara et al., 1996), stream water (Caritat et al., 1996), rain (Reimann et al., 1997c) and snow (Reimann et al., 1996;
Caritat et al., 1998). C1: 10 km from Nikel/Zapoljarnij near coast of Barents Sea, C2: 5 km S Monchegorsk, C3: Apatity, C4: 20 km S Monchegorsk; C5 Svanhovd, Norway, C6–C8:
background catchments in Finland.
Antimony – median
N
Kola Ecogeochemistry – catchment study
Topsoil 0–5 cm
534
Overbank sediments
38
Organic stream sediments
102
Moss
80
Stream water
130
Rain
109
Snow
79
Unit
mg/kg
mg/kg
mg/kg
mg/kg
lg/L
lg/L
lg/L
C1
0.08
<0.2
<0.2
<0.02
<0.02
<0.03
C2
0.7
0.16
<0.2
0.07
0.32
0.06
C3
C4
0.14
0.21
<0.2
<0.2
0.02
0.03
<0.03
<0.2
<0.2
<0.02
0.09
<0.03
N: number of samples.
No value: no samples collected in this catchment.
Topsoil and Overbank sediments: aqua regia extraction, GF-AAS.
Organic stream sediments and moss: conc. HNO3-extraction, ICP-MS.
Water samples: ICP-MS.
*
A value <detection limit was replaced by 1/2 of the detection limit for the calculations.
C5
0.1
0.02
<0.2
<0.2
<0.02
<0.02
<0.03
C6
0.04
<0.2
<0.2
<0.02
<0.02
<0.03
C7
0.1
0.01
<0.2
<0.2
<0.02
<0.02
<0.03
C8
0.1
<0.2
<0.2
<0.02
<0.02
<0.03
C2/(median C6–C8)*
7
16
32
4
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
samples. Sample density was >1 site per km2 in the urbanised areas
and decreases to 1 site per 4 km2 in the surrounding agricultural
areas. The <2 mm fraction of the topsoil samples was analysed by
XRF, providing total Sb concentrations. To provide a better detection limit, all samples at the lower end of the distribution were also
analysed by AAS following a near-total acid extraction. The median
concentration for Sb in the Berlin soils is 2.4 mg/kg. Compared to
data from other urban geochemical mapping projects, this is a normal median value for Sb in urban soils (see Table 1). The variation,
however, is large – more than three orders of magnitude for the
relatively small survey area.
The map (Fig. 4) shows generally increased Sb concentrations in
the central urban area – the geochemical map could almost be used
to outline the border of urbanisation. Local variation is, in general,
high. Background variation, with low Sb concentrations, is reached
at the city border. Background is also commonly reached within
metres of an obvious contamination source as indicated in the
map by numbers – (1): landfill of combustible waste materials,
maximum Sb concentration 454 mg/kg; (2): crematorium, maximum Sb concentration 22.2 mg/kg; (3): old industrial area and
old waste deposits, maximum Sb concentration 31.7 mg/kg; (4):
former steel mill Hennigsdorf, maximum Sb concentration
35 mg/kg; (5): industrial area Berlin Schöneweide (non-ferrous
smelters, storage of chemicals), maximum Sb concentration
122 mg/kg; (6): chemical industry (asphalt coating and production), maximum Sb concentration 153 mg/kg; (7): former military
training camp, maximum Sb concentration 11.4 mg/kg; (8): former
military training camp, maximum Sb concentration 35.7 mg/kg;
(9): scrap yard, maximum Sb concentration 7.6 mg/kg; (10): sewage farm areas and landfills, maximum Sb concentration
10.9 mg/kg; (11): waste deposit sites, maximum Sb concentration
41.6 mg/kg; (12): former military training camp, maximum Sb
concentration 13 mg/kg; (13): Werder city area, maximum Sb concentration 5.7 mg/kg; and (14): Potsdam city area, maximum Sb
concentration 5.3 mg/kg.
The main message to be taken from this map is that even large
contamination sources (e.g., the former steel mill Hennigsdorf,
point 4 in Fig. 4) cause only local anomalies. Low background Sb
values are documented in the topsoil samples all around the city.
Maps from all other urban geochemical mapping projects (see Table 1) return the same message: for point source contamination, a
high local variability is observed and background is reached immediately at the city borders. The Berlin example demonstrates that it
is informative to continue geochemical mapping into the surroundings of a city in order to establish the local geochemical background and its variation, as well as to directly visualize transport
distances from the contamination sources. Serious soil contamination is limited to the local scale, the immediate vicinity of any one
185
source, and a high sample density is needed to reliably outline its
presence.
4. Impact of metal mining and smelting on a variety of sample
materials at the regional scale – the Kola Ecogeochemistry
Project
The Kola Ecogeochemistry project covered an area of
188,000 km2 in Finland, Norway, and Russia (see insert in Fig. 6).
The project area extended from the Arctic Circle northwards to
the Barents Sea coast. The area includes almost pristine (N-Finland,
N-Norway) as well as highly contaminated areas (Russian Ni industry at Monchegorsk and Nikel/Zapoljarniy). The project was carried
out in three stages:
(1) a pilot project in the border area between Finland, Norway
and Russia (e.g., Äyräs et al., 1995; Niskavaara et al., 1996;
Reimann et al., 1996),
(2) a detailed catchment study in eight catchments spread
across the region (e.g., Caritat et al., 1996, 1998; Chekushin
et al., 1998; Niskavaara et al., 1997; Reimann et al.,
1997a,c; Volden et al., 1997), and
(3) a low density mapping of the whole area (e.g., Reimann
et al., 1997b, 1998; http://www.ngu.no/Kola; this website
provides an up-dated list of the more than 50 project
publications).
The Kola geochemical atlas (Reimann et al., 1998) provides all
the background information on the project, the project area, climate, industry, geology, soils and vegetation zones. For this paper,
results from a variety of publications from the catchment study
and from regional geochemical mapping are combined. The project
is of special interest because it provides directly comparable data
for a variety of sample materials at both a local, high-density, sampling scale (catchment studies: 1 site per km2 over ca. 30 km2) and
at a regional scale (regional mapping: 1 site per 300 km2 over
200,000 km2).
Data from the catchment study (Table 2) can be used to examine the impact of contamination on a variety of sample materials.
The catchments were selected to reflect natural conditions as well
as the anthropogenic impact in the survey area. C1–C4 are located
at varying distances from industry in Russia (C2 in the immediate
vicinity of the Ni refinery in Monchegorsk is the most seriously
contaminated catchment). C5 is located in Norway, about 30 km
from the smelter at Nikel and off the prevailing wind tracks. C6–
C8 are background catchments in Finland (see location map in
Fig. 6 lower right and Caritat et al., 1996, 1998 or Reimann et al.,
1997a,c for detailed catchment descriptions).
Fig. 7. North–south transect for Sb from the coast of the Barents Sea to the Arctic Circle (left) (data from Reimann et al., 1998) and from south-north transect showing Sb
concentrations in O-horizon soils (<2 mm, conc. HNO3-extraction) from the southern tip of Norway 200 km inland (right) (data from Reimann et al., 2009a).
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C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
Table 2 demonstrates that the detection limits for Sb were, in
most cases, not sufficiently low to obtain useful median values
for any of the catchments, not even catchment 2 in the vicinity
of the Monchegorsk refinery. Antimony is not usually one of the
main elements emitted by a Ni–Cu smelter. Nevertheless, emission
estimates from NILU (1984) assigned 14 t Sb emissions/a to the
Kola smelters. Boyd et al. (2009) have demonstrated that the total
yearly input of Sb to the Kola smelters is in the range of 4–5 t Sb
and that the likely emissions are well below 2 t/a. Thus, no major
Sb signal should be expected in the area. Still, a Sb signal in C2 is
visible in rain, snow, topsoil and overbank sediments. Compared
to the background values (C6–C8), rain (bulk precipitation) provides the strongest contamination signal.
Fig. 5 compares the Sb concentration as observed during the regional mapping phase of the project in moss and the O-, B- and Chorizon of podzols from the Kola area in a cumulative probability
plot and using box plots. More than 50% of the Sb data for the minerogenic soils (B- and C-horizon) are below the detection limit.
Both moss and, especially, the soil O-horizon show much higher
Sb values than the minerogenic soils. For moss, the distribution
as displayed in the cumulative probability plot shows an inflection
at about 90% and for the O-horizon an upper inflection occurs at
about 96%. There is also a clear lower inflection on the data for
the O-horizon, indicating an unusual process causing low Sb values
in the survey area. The box plots demonstrate that the soil O-horizon is strongly enriched in Sb when compared to the C-horizon,
which displays the greatest variation. The soil O-horizon is characterised by remarkably little variation and, by far, the highest median value of all media. Contamination is indicated by some upper
outliers; the box is symmetric about the median, indicating that
this reflects undisturbed, natural background variation. The high
number of lower outliers in the O-horizon is remarkable. The lows
in the Sb map thus deserve special attention. The box for moss is
also symmetrical, and a number of upper outliers indicate the presence of a contamination source. However, the overall distribution
of Sb in moss is not influenced by that source.
When directly comparing the regional distribution maps for
moss, and soil O- and C-horizon (Fig. 6), it is clear that moss provides an excellent visualisation of contamination from industry
at Nikel/Zapoljarnij and Monchegorsk. Furthermore the major city
in the area, Murmansk, is marked by a separate Sb anomaly, as is
the town of Kandalaksha. Two further unexplained Sb anomalies
occur in the Russian project area (to the SW of Nikel). The high val-
ues in the moss map are thus predominantly directly related to
known contamination sources. The Sb anomaly in the soil C-horizon along the Norwegian coast (continuing into Russia) reflects
the distribution of Neoproterozoic sediments in the survey area.
Several small anomalies indicate alkaline intrusions (e.g., at Apatity) with enhanced Sb concentrations. The major anomaly in the
central Finnish part of the project area is related to a highly prospective area containing Au mineralisation and can be seen as an
indication of late-stage hydrothermal activity on a regional scale
(Reimann and Melezhik, 2001).
Contamination from Monchegorsk and the towns of Murmansk
and Kandalaksha is still clearly visible in the soil O-horizon map,
but on a much more local scale than in the moss map. Other processes begin to play an important role. The geogenic anomaly as
displayed in the soil C-horizon in the centre of the Finnish project
area is visible. A feature that is hardly visible in the moss map however, dominates the O-horizon map: a clear north–south gradient.
Antimony values near the coast are much lower than Sb values further inland. Judging by the moss map, this feature cannot be
caused by atmospheric input from hypothetical sources in central
or western Europe (long-range transport). This gradient reflects
the vegetation zones in the area and is directly influenced by bioproductivity (Reimann et al., 2001a). The sub-arctic tundra is
marked by especially low Sb values. This effect causes the lower
outliers in the boxplot as well as the lower inflection in the CP-plot
in Fig. 5.
This becomes clearly visible when plotting a north–south transect along the western border of the survey area, farthest away
from any anthropogenic sources in the area (Fig. 7). There is a clear
relationship between Sb concentrations in the O-horizon soils and
climate and related vegetation zones. The climate is quite wet
(>500 mm annual precipitation) in the tundra along the coast (first
50–60 km), and organic material builds up. Organic soils can be up
to 20 cm thick here. Further inland (60–200 km), the climate gets
much drier (<350 mm yearly precipitation) and organic soils are
thin (2–3 cm). The tundra and sub-arctic birch tundra zones recede
ca. 250 km from the coast and pine and spruce forests start to dominate. At the end of the transect (from 400 km), boreal forests dominate and precipitation increases again to 400–>500 mm/a. These
changes are directly reflected by the Sb concentrations observed
in the O-horizon (Fig. 7, left). Reimann et al. (2000) describe these
climate and bioproductivity related changes in element concentrations in the O-horizon for over 20 elements. A similar observation
Table 3
Barents Project, catchment stage, Sb concentration in a variety of sample materials collected at a high density (1 site per km2) in nine catchments spread over the 1.1 million km2
project area. Data from Chekushin et al., 2000; Tenhola et al., 2000; Reimann et al., 2001b.
Antimony
(mg/kg; lg/L)
C1
Vorkuta
C2
Narjan Mar
C3
Archangelsk
C4
Korjazhma
C5
Kingisepp
C6
Monchegorsk
0.036
<0.01
<0.01
<0.01
0.056
<0.01
<0.01
0.079
0.011
<0.01
<0.01
0.012
<0.01
0.063
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.015
<0.01
<0.1
0.14
<0.1
0.03
<0.1
0.12
<0.1
0.18
<0.1
0.09
<0.1
0.32
0.4
0.1
0.06
0.17
0.02
0.03
0.22
0.04
0.07
0.19
0.01
0.05
0.26
0.06
0.06
0.05
0.01
0.01
0.042
0.014
0.028
0.035
0.049
0.019
C7
Berlevåg
C8
Kuhmo
C9
Urjala
ALL
0.027
<0.01
<0.01
<0.01
0.031
<0.01
<0.01
<0.01
<0.01
<0.01
0.079
<0.01
<0.01
<0.01
0.01
0.061
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
Plants
Moss
Blueberry
Cowberry
Crowberry
Birch
Willow
Pine
Spruce
O-Horizon
Amm. ac
Conc. HNO3
C-Horizon
<2 mm Total
<2 mm Aqua regia
<0.06 mm Total
Stream water
Filtered <0.45 lm
0.164
0.012
0.024
<0.01
<0.01
<0.01
0.012
0.032
0.142
0.027
0.024
0.059
0.032
<0.01
<0.01
<0.01
0.012
<0.01
<0.1
0.28
<0.1
0.26
1.55
0.49
0.32
0.11
0.01
0.01
0.17
0.04
0.05
0.2
0.03
0.04
0.048
0.029
0.028
0.0297
<0.1
0.1
<0.1
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
has recently been made by Reimann et al. (2009a) at the southern
tip of Norway for 22 elements. Along a 200 km transect inland
from the coast, Sb concentrations in the O-horizon change considerably (factor 10), while six vegetation zones (from dense deciduous forest at the coast to mountain tundra at the northern end;
Moen, 1998) are crossed (Fig. 7 right). Values at the end of this
transect are quite like those observed in the tundra at the northern
end of Norway in the Kola Project area, more than 2000 km further
north, but in a comparable vegetation zone.
5. Continental-scale geochemical mapping
5.1. The Barents project
The Barents project mainly followed the Kola Project design but
covered a much larger area (1.55 million km2). Again, detailed
studies of nine catchments at the local scale (20–50 km2), carefully
187
chosen to reflect different natural and anthropogenic conditions
throughout the whole area (e.g., Reimann et al., 2001b), were combined with low density (1 site per 1000 km2) multi-media geochemical mapping of the entire survey area (Salminen et al., 2004).
Table 3 summarises results from the catchment stage of the
project, in which methods were still being tested and many different sample materials were collected. Here, C6 is the catchment that
is most influenced by anthropogenic activities. It is the same catchment, near the Ni refinery in Monchegorsk, that was also sampled
during the Kola Project (C2 in the Kola Project – see above). Though
many values for the plant samples are below the detection limit in
C6, the different plant species show a substantial variation in Sb
concentrations. Moss was not available to be sampled in the Monchegorsk catchment (C6), but shows by far the highest median Sb
concentration of all plants in all other catchments. The moss median for all catchments is more than an order of magnitude higher
than for all other plants (Table 3). The evergreen crowberry shows
Fig. 8. Barents project, Sb in stream water (filtered at 0.45 lm, ICP-MS) and the soil O-horizon (<2 mm, conc. HNO3-extraction; modified from Salminen et al., 2004).
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C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
by far the highest Sb values in C6. The ratio between contaminated
material (C6) and background (e.g., C2, C7, C8) is remarkably different from species to species: 28 for crowberry but only 2.4 for blueberry (calculated with half the value of the detection limit for the
background catchments), although these plants grow at exactly the
same sites with the same soil Sb concentration and the same atmospheric input.
The soil O-horizon samples were analysed using ammonium
acetate and HNO3-extractions. All values for the ammonium acetate extraction are below the detection limit, even in the contaminated catchment C6. This catchment shows the highest median
value in the HNO3-extraction, but values reported from several
background catchments (e.g., C8 and C9) come close to the median
observed in C6. When comparing to a catchment within a more
similar vegetation zone (e.g., C7), the contamination-related anomaly in C6 is more clearly visible (0.32 mg/kg vs. 0.1 mg/kg).
The <2 mm-fraction of the soil C-horizon samples was analysed
for ‘‘total” Sb and for Sb following an aqua regia extraction (two
different grain-size fractions). The results from the two extractions
differ strongly for Sb; the total values are between 4 and 19 times
higher than those for the aqua regia extraction (median: 5 mg/kg).
In contrast, the values between the two grain-size fractions
(<2 mm and <0.063 mm) determined following aqua regia extraction are more comparable (0.2–1.7). Values in the coarse fraction
are higher in C1, C5, C6, C7 and C8 and lower in C2, C3, C4 and
C9 (Table 3). This difference is not directly related to soil parent
material. C1, C2, C4 and parts of C5 are formed on sorted fluvial
sediments and the soils consist almost exclusively (>80%) of quartz
and some feldspar. In contrast to C3, parts of C5, C6, C8 and C9 soils
have developed on till, while in C7 soils have developed on local
bedrock (regolith) – (Salminen et al., 2008).
Concentrations of Sb in the stream water samples are considerably below the published ‘‘world average”, but within the expected
range when compared to values from other investigations (Table 1).
Interestingly, contamination in C6 (Monchegorsk, Ni-refinery) is
not reflected in stream water; instead one of the lowest Sb concentrations was observed. The highest Sb values in stream water were
found in C5, without any apparent contamination source.
The Barents Atlas regional data (Salminen et al., 2004) are well
suited for studying the influence of Quaternary deposit type and
lithological structure on the Sb concentration in the four sample
materials (moss, soil O- and C-horizon, stream water). The atlas
provides the median values (and range) for the different soil types
and Quaternary deposits in the area, as well as the main lithological structures and vegetation zones. The observed differences suggest that there is a clear climatic/vegetation zone influence on the
Sb values in plants, the soil O-horizon and surface waters that is
not related to the substrate (C-horizon, bedrock geology).
In the regional maps, moss predominantly reflects contamination from major cities in the area (Murmansk, Vorkuta, Arkhangelsk, St. Petersburg). All the anomalies disappear in the
background variation within <100 km of urbanization. There is a
general increase in Sb concentrations from the north to the south.
The southern tip of Finland shows some of the highest values on
the regional scale. The impact of the Kola smelters (see above) is
minor at the scale of this survey and compared to the major cities.
The soil O-horizon (Fig. 8) shows some surprising patterns. Some,
but not all of the major cities are indicated by local Sb anomalies
(Murmansk, Arkhangelsk, St. Petersburg, Helsinki). The Kola smelters cause a restricted anomaly on the Kola Peninsula. The whole of
southern Finland and parts of Karelia are marked by rather high Sb
values, which are clearly not linked to any of the known contamination sources. In general, the map suggests that there are higher
Sb concentrations in the south than in the north (Fig. 8) of the survey area. Geogenic sources dominate the mapped patterns, e.g.,
elevated Sb values in southern Finland indicate the mineralised
Tampere Schist Belt (see above, Forssa) rather than the higher population density in southern Finland or long-range transport from
central Europe.
The patterns for stream water (Fig. 8) are especially interesting.
Industrial contamination, e.g., in the surroundings of the Kola smelters, is not observed. The main anthropogenic anomalies occur near
the cities Murmansk, Archangelsk, Vorkuta, St. Petersburg and Helsinki and are limited in size. A strong increase of Sb in stream water
from north to the south is visible in the western part of the survey
area. The somewhat higher values in the north-eastern part of the
survey area (too high for the climatic/vegetation zone) mark a major
lithological break (Baltic Shield in the west vs. younger sedimentary
basins towards the east) and indicate an area with a high potential
for the occurrence of oil and gas fields (Salminen et al., 2004).
Fig. 9. Baltic Soil Survey, Sb in the <2 mm fraction of agricultural soils (HF–HCLO4–HNO3-extraction), TOP (0–25 cm) and BOT (50–75 cm) (from Reimann et al., 2003b).
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
5.2. The Baltic Soil Survey
Agricultural soils from 10 northern European countries (western Belarus, Estonia, Finland, northern Germany, Latvia, Lithuania,
Norway, Poland, western Russia and Sweden) were collected during 1996/97 at 748 sites from the Ap- (0–25 cm, ‘‘TOP”-sample)
and B-/C-horizon (50–75 cm, ‘‘BOT”-sample). The sample sites
were spread over 1,800,000 km2, at an average sample density of
1 site per 2500 km2. The <2 mm-fraction of all 1500 samples was
analysed for up to 62 chemical elements following ammonium acetate-, aqua regia- and HF-extractions and for total element concenTable 4
Antimony and loss on ignition (LOI) in agricultural soils from 10 northern countries
(Reimann et al., 2003b). TOP: 0–25 cm, Ap-horizon; BOT: 50–75 cm, B-/C-horizon.
BSS (mg/kg)
Belarus
Estonia
Finland
Germany
Latvia
Lithuania
Norway
Poland
Russia
Sweden
Sb, mg/kg
LOI, wt.%
TOP
BOT
TOP/BOT
TOP
BOT
TOP/BOT
0.16
0.22
0.24
0.30
0.18
0.21
0.20
0.28
0.19
0.31
0.15
0.16
0.16
0.22
0.19
0.16
0.17
0.22
0.17
0.30
1.1
1.4
1.5
1.4
0.9
1.3
1.2
1.3
1.1
1.0
4.7
6.5
24.6
4.0
4.9
6.1
8.7
3.8
8.1
7.3
2.2
3.8
4.0
2.5
5.3
5.4
5.0
2.9
2.9
4.0
2.1
1.7
6.2
1.6
0.9
1.1
1.7
1.3
2.8
1.8
189
trations by X-ray fluorescence (XRF). Antimony was determined
following an aqua regia extraction by graphite furnace atomic
absorption spectroscopy (GF-AAS), following an HClO4–HF–
HNO3-extraction by inductively coupled plasma mass spectrometry (ICP-MS) and total concentrations were determined on pressed
powder pellets by XRF. All values received for the aqua regia
extraction and from the XRF suffered from high detection limits;
thus only the HF-extraction resulted in a useful dataset. For further
details see Reimann et al. (2003b). Three features dominate the
maps shown in Fig. 9.
(1) A strong Sb anomaly occurs in central Sweden, covering an
area of more than 150,000 km2. Interestingly, Sb is not visibly enriched in the top layer in this area. A comparable
anomaly was observed for several additional elements,
including As (Reimann et al., 2009b). The general area is well
known for its mineral potential, but there is no anthropogenic source that could explain such a sizeable Sb anomaly
at this location. Many Sb values are higher in the BOT sample
than in the TOP samples – another argument against contamination causing the pattern. The anomaly cannot, however, be easily explained by known geological features, e.g.,
bedrock. No rock types expected to be enriched in Sb occur
in this area. The Sb anomaly in Central Sweden cuts the
boundary between rocks of the Baltic Shield in Sweden
and the Caledonian fold belt in Norway. However, the Sb
anomaly is underlain by a heat flow anomaly (Hurter and
Fig. 10. FOREGS project: antimony in top soil (0–20 cm, organic layer removed, <2 mm fraction, 4-acid extraction, ICP-MS) in Europe (modified from: Salminen et al., 2005).
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C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
Haenel, 2002). This soil Sb anomaly may thus be an expression of crustal degassing of Sb on a large regional scale. It is
an interesting thought that such an anomaly would easily be
overlooked in mapping at a more detailed, local scale as
compared to the sub-continental approach used for the Baltic Soil Survey project. It is also noteworthy that no less than
11 ore deposits have been found in recent years in the area
delineated by the highest values in the sub-soils.
(2) The second feature is a Sb anomaly towards the southern
project boundary in Poland (Fig. 9). This anomaly marks
the highly industrialised area of Upper Silesia as well as
the known ore deposits of the Polish Kupferschiefer. It is
thus very tempting to explain this anomaly with anthropogenic activities (mining and metal industry), although the
size of the anomaly is rather large for indicating ore deposits
(which occur at 800 m depth), or mining and smelting activities (see Walchen, Kola or Berlin examples). At the time of
the BSS-project, this anomaly could not be sufficiently
explained – a further step back to obtain a larger view was
needed – to map all of Europe – to find the explanation,
see Section 5.3 below.
(3) The third feature is an almost general enrichment of Sb in
the top soil (Table 4), visible over large parts of the survey
area, but especially in Poland, Germany, and southern Finland. Antimony is generally slightly enriched in the top layer
(overall median TOP 0.24 mg/kg vs. 0.19 mg/kg in BOT),
except for the samples from Latvia. The median values vary
by a factor of about two between the countries, with the
highest median value occurring in both horizons in Sweden
(Table 4). Except for Latvia, the TOP/BOT ratio is above 1 in
all countries, the strongest relative enrichment of Sb in the
top layer is observed in Finland. The soils from Finland show
at the same time the highest loss on ignition, which can be
taken as a proxy for the content of organic material, while
the samples from Latvia show as the one exception a higher
loss on ignition at depth than in the top layer. The overall
enrichment of Sb in the top layer is thus rather an indication
of the element’s strong affinity for organic material rather
than of contamination throughout northern Europe. However, the relatively strong enrichment of Sb in the top soils
of Poland and, especially, Germany look suspiciously like
contamination. These are the areas with the highest traffic
density in the survey area. It cannot be excluded that the
maps indicate a general build-up of Sb in the top soils of this
area due to traffic-related emissions, though total trafficrelated emissions of Sb in the European Union are estimated
at less than 5 t/a (EU, 2008).
5.3. The FOREGS (EuroGeoSurveys) geochemical atlas of Europe
The Forum of European Geological Surveys (FOREGS), now
EuroGeoSurveys (EGS), has produced a geochemical atlas of Europe, using stream water and sediments, overbank (floodplain) sediments, top soil (0–20 cm; organic part removed), and C-horizon
soil (a 25-cm layer within a depth of 50–200 cm) at an average
sample density of 1 site per 5000 km2 (De Vos et al., 2006; Salminen et al., 2005). All materials were prepared and analysed for each
set of parameters/elements in a single laboratory. The EuroGeoSurveys database is the best available source for studying the variation
of chemical elements in a variety of sample materials at the continental-scale. When studying the maps as displayed in the atlas
(Salminen et al., 2005, also downloadable from the internet at:
http://www.gtk.fi/publ/foregsatlas/) the most stunning feature is
the clear break in concentration between southern (high Sb) and
northern Europe (low Sb; Fig. 10).
This is the same phenomenon as observed in the BSS-data (see
above, Fig. 9). When considering the BSS survey area alone, it was
tempting to interpret the anomaly in southern Poland as anthropogenic. However, taking a step back to see the entire continent, the
maps for all Europe demonstrate that this phenomenon reflects an
important geological process. The border between low and high Sb
exactly follows the border that marks the extent of glaciation in
central Europe. The younger coarse-grained soils in northern Europe have low Sb concentrations, while the much older, more
weathered and finer grained soils in southern Europe contain much
higher Sb values.
The prominent Sb anomaly in central Scandinavia, as displayed
in Fig. 9, appears considerably less prominent in Fig. 10. This is a
statistical artefact and due to the dominance of high Sb in the
southern European soils. It is interesting to note the distinct difference (factor four) in soil Sb concentrations between southern Europe (Spain, France, Italy) and Scandinavia (Finland, Norway,
Sweden) (Table 1).
The dominating feature in the continental-scale maps of the Sb
distribution in Europe in a variety of sample materials is this difference between northern and southern Europe. This difference is not
related to anthropogenic activities. When studying the Sb top soil
map in more detail, and investigating the possible causes for some
of the anomalies, it becomes clear that contamination is probably
the cause of some of the hotspots. Note, for example, the rather
small and limited anomaly related to the ore deposits and mining
district of the Erzgebirge at the German/Czech border (Fig. 10), representing a major industrial centre with many well-documented
examples of local contamination. However, one could still discuss
whether the anomaly is due to nature, the occurrence of mineralisation, or rather due to the anthropogenic exploitation of the mineralisation. Several examples, as shown above, have demonstrated
that anthropogenic sources will usually result in rather local
anomalies and not in large-scale regional patterns. In contrast,
the occurrence of a geochemical province (Reimann and Melezhik,
2001) is characterised by a rather large area with enhanced concentrations of certain elements. High Sb values in Hungary in the
top soil map are most likely related to the rather recent (in geological terms) volcanic activity in that area. The anomaly in the RheinRuhr valley can, in contrast, be due to contamination, but may just
as well be related to the Tertiary volcanic activities of the Rhein
graben; similar to those anomalies in France (Rhone valley and
Massif Central). Areas where local, much higher density geochemical surveys are justified to explain the presence of an anomaly can
now be easily selected based on the continental-scale maps.
Clearly, it will be impossible to define one ‘‘good soil quality” or
Sb background value in soils for all of Europe, even though values
remain within one order of magnitude. It is also not possible to
automatically assign all high values to anthropogenic sources, because equally high or higher Sb values in soils can occur for a variety of natural reasons. Thus, statistics alone will not provide an
answer to the contamination question; it is obvious that geochemical maps are needed to identify the source (e.g., Matschullat et al.,
2000a; Reimann and Garrett, 2005). As already observed for the
Baltic Soil Survey, the top soil is slightly enriched in Sb when compared to the sub-soil, the average top/sub-soil ratio is 1.18 (De Vos
et al., 2006) and many areas displaying a strong enrichment do not
show any obvious connection with known anthropogenic sources
(see map in De Vos et al., 2006, p. 321).
Median value and range of Sb in stream sediments are quite
comparable to the values from soils (Table 1). Again, there is a major difference between concentrations in northern (low) and southern (high) Europe. An interesting feature is a distinct positive Sb
anomaly in stream sediments at the southern tip of Sweden, indicating an area of mineralised shear zones (De Vos et al., 2006).
Many ore deposits and mineralised areas show up as Sb anomalies
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
in the stream sediment map. One could discuss at length whether
these anomalies represent contamination (i.e., are caused or enhanced by human activities) or are natural anomalies related to
the occurrence of ore bodies.
Floodplain sediments show the same general patterns as the
stream sediments, including the concentration difference between
northern and southern Europe. The Sb median value for floodplain
sediments is slightly higher than for stream sediments (0.74 mg/kg
vs. 0.64 mg/kg). This may be an indication of the generally finer
grain-size of floodplain sediments when compared to stream sediments or of the higher sensitivity of floodplain sediments to contamination. The median concentration of Sb in floodplain
sediments from southern Europe is almost three times higher than
the median value for Sb in floodplain sediments from northern Europe (0.97 vs. 0.35 mg/kg, Table 1).
The pronounced difference between northern and southern Europe, as observed for the soil, stream- and floodplain-sediment results, is also reflected in stream water. The median of Sb in
stream water from southern Europe is more than a factor of two
higher than the median for northern Europe (0.07 vs. 0.03 lg/L, Table 1). The distinction between higher and lower levels again
marks the location of the extent of the last glaciation in central
Europe and is not related to anthropogenic activities.
6. Discussion
6.1. Background
The term ‘‘background” has been frequently used throughout
this paper. The definition of the term ‘‘background” is, however,
somewhat unclear. Recently Reimann and Garrett (2005) provided
a review of the terms background and threshold (the upper limit of
background variation) showing that more than 10 quite different
definitions are in use in the scientific literature. There also exist
different techniques for the statistical calculation of the background (e.g., Matschullat et al., 2000a; Reimann et al., 2005). The
term ‘‘background” is often used for a single (relatively low) value
thought to represent the natural concentration of an element in a
sample material, e.g., ‘‘the median concentration of Sb in soils”.
However, ‘‘background” in its true sense is never a single value
but rather a range of values (from-to). This range of background
concentrations will always change from area to area and with
the number of samples taken in each area (Reimann and Garrett,
2005). Establishing ‘‘action” levels or ‘‘remediation” values based
on a range of concentrations that vary with location has proven
very difficult for regulatory decision makers, which is one of the
reasons for the existing confusion.
Due to this unsatisfactory situation the Diantimony Trioxide
risk assessment document of the EU, 2008 actually defines three
different terms for ‘‘background”:
(1) Natural background concentration: ‘‘The natural concentration
of an element in the environment reflects the situation before
any human activity disturbed the natural equilibrium. As a
result of historical and current anthropogenic input from diffuse sources the direct measurement of natural background
concentration is not possible in the European environment”.
(2) Baseline background concentration: ‘‘The baseline background
concentration is the concentration of an element corresponding to very low anthropogenic pressure (i.e., close to
the natural background concentration but not identical).”
(3) Ambient concentration: ‘‘The ambient concentration is the
sum of the natural background concentration of an element
and diffuse anthropogenic input in the past or present (i.e.,
influence of point sources not included).”
191
However, are these terms and definitions really helpful, correct
and needed in the light of the results presented above? Reimann
and Garrett (2005) have shown that the definition of a background
for a large area is fraught with problems. Fig. 10 indicates that
there are at least two different Sb ‘‘background regimes” in Europe:
northern Europe with generally low Sb values and southern Europe
with clearly higher Sb values (see Table 1) in topsoil (the same pattern is visible for all sample materials collected during the FOREGS
project (see Salminen et al., 2005). These results also demonstrate
that it is quite possible to establish a ‘‘natural background variation” and likely ‘‘natural” Sb concentrations in a variety of sample
materials even in Europe. The additional anthropogenic input is so
low that it does not influence the geochemical patterns delineated
at the continental-scale. Anthropogenic input can, but does not
necessarily play an important role at the local and detailed scale.
Definitions (2) and (3) are more confusing than helpful (see Forssa,
Walchen and Berlin examples).
The results presented above illustrate that the natural processes
acting at continental-scale (e.g., weathering, climate and geology)
dominate the distribution of Sb (e.g., Fig. 10). Even the natural
equilibrium implied in definition (1) is not static in that it is influenced by natural changes in climate, operative on time-scales
down to 100 a, plus factors such as volcanic eruptions or changes
in wind patterns, which may have a shorter time impact. Natural
variation is so large that a possible diffuse anthropogenic addition
of an element (definition 3) is not observed in the patterns and
cannot even be determined in most instances. At the local and,
especially, the detailed scale, unusual natural features (e.g., mineralisation or certain rock types with distinctive chemical composition) or anthropogenic influences (e.g., the presence of a smelter)
can seriously disturb the ‘‘geochemical background” and cause local anomalies i.e., deviations from the background variation. Finding such patterns needs geochemical mapping at a variety of scales
and not statistical exercises to calculate a ‘‘background” based on a
multitude of different and scientifically unsound definitions. These
anomalies may need regulatory attention. In the urge to blame
somebody for high element values (e.g., humanity at large or a specific industry, as reflected in the above definitions) in, for example,
present-day soils, it is almost completely neglected in the scientific
literature that element deficiency (concentrations that are too low)
for the majority of elements may present a much greater health
threat to humanity than element toxicity (concentrations that
are too high) (Reimann and Garrett, 2005).
Once PNEC values exist for an element, all of the above terms,
and even the background, are no longer of real importance – it does
not matter whether high values that may represent a health risk
are caused by nature or by human activities. It remains, of course,
an open question whether the same PNEC values should be applied
to areas with low geochemical background and areas with high
geochemical background – organisms may have adapted to the
background and even definition of toxicological thresholds may require consideration of a spatial component (Reimann and Garrett,
2005).
The definition of the background should thus be kept as simple
as possible to represent ‘‘the normal geochemical variation of an
element in a certain sample material within a certain area”. Concentrations above background can be caused by natural sources
(mineralisation, unusual rocks, a variety of climate-driven processes) or by anthropogenic interference with the natural element
cycles (e.g., mines, smelters, fertilisers, traffic).
6.2. Sample preparation and analysis
Many analytical methods have been used to determine Sb concentrations in the different sample materials (Table 1). Data for
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true ‘‘total” Sb concentrations (XRF and INAA analyses), near-total
acid extractions like a 4-acid extraction, including HF, as well as
values derived from a variety of different acid extractions, often
deviate strongly. Thus differences in the digestion and analytical
method clearly have an effect on the analytical results. Antimony
can be volatilised and lost in a variety of acid extractions. Such
Sb losses are well-documented for methods using HCl and HClO4,
and can also be expected for HF (e.g., Bock, 2001). It is thus likely
that many results from environmental chemistry, based on a variety of acid mixes containing HCl, HClO4 and/or HF, are in fact too
low.
Some surveys provide data for total (XRF, INAA, 4-acid-extraction) and acid extraction (e.g., aqua regia) analyses on the same
set of soil samples (e.g., Barents project: Salminen et al., 2004). Values from an aqua regia extraction are a factor of 4–19 lower than
those from a 4-acid near-total extraction on the same samples (Table 3). This effect may explain some of the striking differences in
the median values reported for Sb from different surveys in Table 1.
It must be noted that XRF and INAA are both plagued with rather
high detection limits (around 1–2 mg/kg). This may lead to many
values ‘‘ <DL” at the lower end of the distribution, and thus to less
reliable results as compared to a technique with a detection limit
several orders of magnitude lower.
6.3. Grain-size
The chosen grain-size fraction can have an important influence
on the analytical results for soil and sediment samples, since many
metals tend to be enriched in the fine (<0.063 mm) grain-size fractions (Förstner and Müller, 1974). Traditionally, exploration geochemists have used fine grain-size fractions (e.g., <0.177–
<0.063 mm) in their search for mineral deposits, while soil scientists preferred a comparatively coarse grain-size fraction
(<2 mm). To make the issue even more complicated, the sieved
samples can be analysed as is, or ground to a fine powder prior
to analysis to improve the reproducibility of the analytical results
(representativeness of the usually small amounts used for analyses) and to liberate trace elements bound in mineral lattices or
inclusions in silicate minerals – which can again result in higher
analytical results.
Results in Tables 1 and 3 indicate that grain-size may play an
important role. Several of the surveys, in which a fine grain-size
fraction (e.g.,<0.177 mm or finer) was used, show higher concentrations than those surveys, in which the <2 mm-fraction was used.
Without directly comparable samples from the same area it is difficult to judge whether such differences are due to grain-size fraction or rather an effect of a different survey area (location). In the
Barents project, the results from the fine fraction of the C-horizon
soils (<0.063 mm) were, in most catchments, almost the same as
the results from the coarse (<2 mm) fraction (Table 3). In contrast,
Tarvainen et al. (2006) have analysed top- and sub-soil samples
from the Helsinki region. These authors observed a consistent increase in Sb concentrations from sandy/gravelly soil via till to
clayey soil samples (0.08–0.11–0.17 mg/kg Sb in top soils).
6.4. Soil horizon
Few datasets exist with directly comparable data from rock
samples and the different soil horizons developed on these rocks.
One such study was published by Reimann et al. (2007b) from a
transect in southern Norway (40 sample sites spread over
120 km). Here, the Sb median concentration increases by a factor
of six from rocks to mineral soils (soil C- and B-horizon) due to
weathering processes and the tendency of Sb to accumulate with
Fe-/Mn-oxides and -hydroxides, and organic material. The tendency of Sb to be enriched in soils that are high in organic matter
is clearly the strongest, with a 7-fold increase in the median values
from the soil C- to the O-horizon. This enrichment is not related to
any known contamination sources along the transect (Reimann
et al., 2007b).
6.5. Vegetation
Antimony is not essential in plants and they generally show low
Sb concentrations, about a factor 5–10 below those of the supporting
soils. The suggested value for the world reference plant (Markert,
1992) of 0.1 mg/kg Sb may even be at the high end for Sb in plants
(see Table 1) and 0.05 mg/kg may be a more realistic value (but note
that the majority of analytical results provided in Table 1 are from
Northern European plants). In the immediate vicinity of a major
contamination source, different plants react differently to increased
levels of airborne Sb in their environment (e.g., blueberry vs. crowberry, Table 3). In general, it is noteworthy that variation between
the plant species and between the samples from different surveys
is surprisingly low. These are clear indications that the majority of
plants have mechanisms for avoiding excessive Sb uptake. However,
plants do take up Sb, and a radiological assessment of Sb distribution
in plants showed elevated concentrations of the element in roots,
older leaves and the lower parts of the shoots (Coughtrey et al.,
1983). Moss (and lichen) consistently show higher Sb values than
other terrestrial plants (e.g., directly comparable Barents data, Table 3). The highest Sb concentrations in the Barents region are observed in the soil O-horizon (see Fig. 5 from the Kola project as an
example). The high Sb concentrations in moss are probably caused
by adhering soil dust from the O-horizon (Reimann et al., 2006).
No specific plants are documented as Sb accumulators for mineral exploration purposes in Dunn (2007). This is most likely due to
limited knowledge (because Sb is rarely analysed in plants) rather
than to the non-existence of Sb accumulators (see below). Plants
can be used as indicators of mineralisation (Dunn, 2007), e.g.,:
(1) ‘‘Thola” vegetation (Baccharis spp.) has been used in Bolivia
at the Chilcobija mine and values in Thola foliage ranged
from 330 to 540 mg/kg Sb (these extremely high values
may be partly due to contamination – Dunn, 2007).
(2) Bark of Lodgepole pine (Pinus contora) contained up to
0.1 mg/kg Sb over known mineralisation at the pristine Mt.
Milligan (British Columbia) Au deposit (Dunn et al., 1996).
(3) Black spruce twigs (Picea mariana) contained up to 1 mg/kg
Sb near Au mineralisation at the Rambler Au deposit, Newfoundland (Dunn et al., 1995).
(4) Twigs of Mountain hemlock (Tsuga mertensiana) taken over
the unmined Mt. Washington epithermal Au deposit on Vancouver Island contained up to 0.6 mg/kg Sb (Dunn, 2009,
pers. comm.).
Results from the Eden Project (Dunn, 2007) show that plants
from Mediterranean regions yield higher Sb concentrations than
those from the tropics, reaching a maximum of 7 mg/kg Sb in
leaves from the South African Cape Myrtle and 5 mg/kg in heather,
although the soils from the two biomes have similar and considerably lower Sb concentrations. These findings indicate that climate
may play an important role in the Sb uptake of plants.
Borovicka et al. (2006) have identified a mushroom as a hyperaccumulator of Sb. One of their samples of ectomycorrhizal fungi
(Peppery Bolete – Chalciporus piperatus) from the Pribřam mining
district in the Czech Republic contained 1423 mg/kg Sb. This is
one of the most extreme Sb values so far reported in a plant.
Baroni et al. (2000) report Achillea ageratum, Plantago lanceolata
and Silene vulgaris as Sb accumulators. They found values of up to
1367 mg/kg Sb in A. ageratum leaves, 1150 mg/kg in P. lanceolata
roots and 1164 mg/kg in S. vulgaris shoots for plants growing in
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
an old Sb mining and smelting area. Surprisingly, Sb uptake from
the soil into the plants was most efficient when the availability
of Sb in the soil was low to intermediate.
Hammel et al. (2000) investigated Sb concentrations in a large
variety of edible plants grown on soils that have been contaminated by residues from a historical mining area in Germany. Antimony concentrations in these soils ranged from 8 to 266 mg/kg.
Plants grown on these soils showed highly variable Sb values. Concentrations in carrot, red beet, onion, potato, sugar beet, tomato,
wheat, barley, rye, oat and maize (corn) were all at or below the
detection limit (0.02 mg/kg) and showed a maximum value of
0.09 mg/kg in red beet. Antimony values in leaves and shoots of
vegetables, grain and herbage (N = 9–17 per species) were, in contrast, often considerably higher (0.08–2.20 mg/kg), with the maximum median value (0.63 mg/kg) in carrot leaves and the highest
value of all samples in endive lettuce.
In contrast, data reported on Sb levels in grass collected
100 m from an active Sb smelter were not caused by soil uptake
but rather by atmospheric input (Ainsworth et al., 1990). Antimony reached values up to 336 mg/kg in Agropyron repens,
152 mg/kg in Dactylis glomerata and 232 mg/kg in Festuca rubra
100 m from the smelter and declined to 24, 30 and 28 mg/kg
in the same three grass species at a distance of only 250 m from
the smelter.
Due to their generally low natural concentrations of Sb, plants
may hold promise as biomonitors for anthropogenic derived Sb.
In a transect study through the city of Oslo, in which one sample
site was chosen within 20 m of a major highway and another
one is on top of Pb mineralisation, all soil samples (soil O-, B, Chorizon) show their maximum Sb value on top of the mineralisation, while the plant samples (moss, fern, European mountain
ash leaves, birch leaves and bark, spruce needles) show the
maximum Sb value at the highway site (Reimann et al.,
2007a,b,c). Moss (Hylocomium splendens) and fern (Pteridium aquilinum) show by far the highest concentration of Sb in any of the
plant materials collected at the highway site (1.48 and 1.2 mg/
kg), birch bark (Betula pubescens) and spruce needles (Picea abies)
have the lowest values (0.09 and 0.16 mg/kg) at the same site.
The ground vegetation (moss, fern) is most vulnerable to dust contamination from a highway. In the plant materials the Pb mineralisation is only indicated via the second highest Sb value in spruce
needles.
6.6. Freshwater
Median values for Sb in freshwater resources appear to peak
around a median of 0.03–0.07 lg/L in natural surface water. Variation between results from the different surveys is low when compared to soils (Table 1). In groundwater, the Sb median values from
the included surveys are again low. Due to the low background
concentrations of Sb in natural waters, extreme care must be taken
that the samples are not contaminated with Sb. Diantimony Trioxide is used as a catalyst in plastic production and substantial leaching (up to 2 lg/L, far above the expected natural concentrations) of
Sb from polyethylene terephthalate bottles to water has been demonstrated by Shotyk and Krachler (2007). Even though these values
are under the EU action level for drinking water (5 lg/L, Council of
the European Union, 1998) they indicate that there is a risk that
background Sb values in water samples may still be overestimated
in many, if not all, studies.
Several extensive groundwater aquifers throughout the world
have been shown to have extreme As concentrations (Smedley
and Kinniburgh, 2002), but similar provinces are not documented
for Sb. Antimony is not, however, an element that has been routinely analysed in groundwater surveys, so surprises are still possible. The extremely high values in some groundwater samples
193
reported from Slovakia (up to 2350 lg/L Sb; Rapant et al., 1996 –
Table 1) are directly related to ore deposits and mining areas. Wolkersdorfer and Wackwitz (2004) observed values of up to 1768 lg/
L Sb in mine waters dewatering a Medieval fahlore mine in Tyrol,
Austria. Their investigation demonstrated that natural springs in
this area contain high Sb concentrations as well; the highest concentrations observed (several hundred lg/L Sb) are clearly related
to a specific geological unit (Schwazer Dolomite), hosting the fahlore deposits. Comparable observations were reported by Wilson
et al. (2004) from New Zealand. Water samples collected near adits
in a historic Sb mine contained up to 791 lg/L. The main stream in
the area showed Sb concentrations of 14–30 lg/L. However, due to
high flow rates, the metalloid fluxes from the river are several orders of magnitude higher than the fluxes of metalloids from the
adits. Wilson et al. (2004) thus concluded that the adits are contributing a negligible amount of Sb to the environment; the vast
majority is naturally derived because the drainage of the river runs
parallel to the mineralised shear zone.
The occurrence of Sb in geyser fields was described as early as
1912 (Jones, 1912). Landrum et al. (2009) recently reported values
from 1123–4185 lg/L Sb (median 2470 lg/L Sb) in the waters from
the El Tatio Geyser field in Chile. High Sb values (up to the mg/L
range in water) have been reported earlier from a number of geysers (e.g., Stauffer and Thompson, 1984; Smith et al., 1987; Sakamoto et al., 1988; Krupp and Seward, 1990; Pope et al., 2004). At the
Champagne pool, North Island, New Zealand, Pope et al. (2004) observed that diurnal geochemical processes are especially important
for Sb dispersal from the spring environment. As a curiosity, stibnite (Sb2S3) precipitation in the heat exchangers of geothermal
power stations can actually represent a challenging problem. Wilson et al. (2007) report that 15.8 kg stibnite forms daily in the heat
exchangers at the Ngawha power station in New Zealand.
6.7. Marine environment
Unfortunately, in terms of number of samples taken and area
covered very few representative datasets on background Sb concentrations in the marine environment exist. Many individual
studies are published based on very few samples (see review papers by Filella et al. (2002a,b, 2007)), the majority focussing on
known contamination problems on a local scale. One representative study was carried out in the Gulf of Finland (see Table 1, Vallius, 2009, Pers. comm.). It resulted in a median value and variation
that is quite comparable with many of the soil survey results on
land. The extent to which the Gulf of Finland represents a truly
marine environment, however, is debatable. The most representative dataset the authors are aware of was recently published by
Ohta et al. (in press). These authors present a direct comparison
of Sb in 798 stream sediments collected on land (representing
96,300 km2) to 1406 coastal sea sediments covering an area of
115,000 km2 collected off the coast of northern Japan. The median
values of the two datasets suggest a slight overall enrichment from
land to sea (stream sediments: 0.49 mg/kg, coastal sea sediments:
0.58 mg/kg), the maximum concentration observed in the coastal
sediments (1.69 mg/kg) is, however, much lower than the maximum concentration found on land (123 mg/kg) (see Table 1). Ohta
et al. (in press) also describe a tendency of Sb to especially enrich at
the top of fine sediments in deep water, an enrichment that is not
caused by contamination but rather by early diagenetic processes
where Sb (together with Mn, Cu, Mo, Pb and Bi) is dissolved at
greater depth under reducing conditions and precipitated with
Mn oxides under oxic conditions at the top of the sediment
column.
It is especially surprising that Sb in the marine environment is
almost totally neglected by the larger scientific community in the
light of extreme Sb concentrations reported from geysers in differ-
194
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
ent parts of the world (see above) and the existence of the extensive Mid Ocean Rifts (see also Table 1, data for ‘‘Tonga Island Arc”
and ‘‘hydrothermal fluid, Mid Atlantic Ridge). Median Sb concentrations in ocean water cluster around 0.2 lg/L (Table 1); higher
by a factor of 3–4 than the Sb concentrations usually reported from
freshwater. This value is used as ‘‘background concentration” in
marine water in the risk assessment report for Diantimony Trioxide (EU, 2008). More data are provided in Filella et al. (2002a)
and fall into the same range as those shown in Table 1. However,
it must again be noted that all these values are based on few samples which may not be representative.
Antimony has been determined in marine plants, especially algae, and a review can be found in Filella et al. (2007). Results fall
generally into the range 0.1–0.2 mg/kg Sb dry weight (Filella
et al., 2007). Many of the data are rather old and again, only a
few samples (1–5) from limited geographical areas have been analysed. However, the general statement that the Sb concentrations
observed in marine plants in the absence of contamination are
quite close to the value provided for the ‘‘reference plant” of Markert (1992) appears justified.
The regional Sb distributions displayed in all maps do not support the hypothesis that the dispersal of Sb in the environment is
dominated or even noticeably influenced by anthropogenic sources.
Geology provides the primary control for Sb concentrations observed in all compartments of the ecosystem (e.g., soil, stream sediments, plants, water). Large variations are present in the observed
natural concentrations at all scales, caused by a large variety of natural processes, including non-geological influences such as climate
and vegetation. Climatic factors have a strong influence on Sb concentrations in the different sample materials. These natural variations must be documented and the processes causing them
understood, before reliable estimates of the anthropogenic impact
on the natural environment can be made. Evidence for anthropogenic impact can usually only be gained from carefully constructed
geochemical maps, where the samples were collected at a suitable
density over a large enough area around known sources. Serious
contamination of soils, plants or water with Sb still occurs at a detailed to local scale. Antimony can be used advantageously to detect
contamination due to its low natural concentrations.
6.8. Contamination
7. Conclusions
Up to 176,700 mg/kg Sb were reported as the analytical result of
‘‘surface materials” from the site of an historic smelter (Wilson
et al., 2004). However, even in such an extreme situation there
was no detectable loss of Sb from the smelter site into the adjacent
river, <50 m away. Antimony is not easily mobilised from soils, and
only a detailed-scale study allows detection of such extreme
values.
Different sample materials reflect the presence of contamination differently. In sample materials representing the atmosphere
(e.g., rain, snow), which have low natural background concentrations of most elements, contamination will create a clear signal
(Reimann et al., 1996, 1997b; Matschullat et al., 2000b). In other
materials, collected from the same area at the same time, an
anthropogenic influence may be hardly noticeable. Due to the
low element concentrations in atmospheric media when compared
to soils, the impact of airborne pollution on soil chemistry is usually not observed in geochemical maps at a distance of some
metres to a few km from even major contamination sources.
Although natural Sb concentrations in all sample materials are
low, which is an ideal situation for detection of contributions from
anthropogenic sources, most of the major Sb anomalies in the local-scale to continental scale geochemical maps presented, can
be explained by natural processes. Some clearly reflect anthropogenic sources. The contamination-related signal disappears, however, in the background noise over a rather short distance. The
natural variation in Sb concentrations in the different sample
materials is large (2–3 orders of magnitude). Top soils tend to be
enriched in Sb when compared to the deeper soil layers or rocks.
The enrichment is especially large in organic soils. This implies that
minerogenic soils (or the Earth’s crust) do not provide a background value of Sb for organic soils, the biosphere or the atmosphere. The observed distribution patterns in the maps cannot be
explained by anthropogenic input. Contamination at this scale is
of such minor importance that it is hardly noticeable in the regional maps. The enrichment of Sb at the Earth’s surface is due to natural processes and appears strongly influenced by climate. The
regional distribution patterns in practically all examples presented
above are governed by natural variation and natural processes.
High variability at all scales is the main message that can be taken
from geochemical mapping of Sb. It is important to note that different processes become visible in the maps at different scales and
sample densities. Detailed-scale high-density sampling is needed
in order to map contamination.
Results from the geochemical mapping projects presented
above indicate that Sb world-average values provided in the literature (Table 1) appear to be quite realistic for rocks (0.3 mg/kg),
soils (0.5 mg/kg), and sediments (0.6 mg/kg). Literature values for
plants (0.1 mg/kg) and surface water (0.1 lg/L) may be at the high
end (by a factor of two too high, 0.05 mg/kg for plants and 0.05 lg/
L for surface water may be more realistic). Urban soils commonly
show the highest median Sb values of any soils (around 2 mg/
kg), an indication for Sb contamination of the urban environment.
A number of analytical problems exist for Sb (volatilisation in a
number of acid extractions, generally low values close to the detection limits of some standard techniques) that make it difficult to
directly compare values derived from different investigations.
Mineralisation, as well as contamination, can cause high Sb concentrations in a number of sample materials. Antimony anomalies
occur most commonly at the detailed scale. Statistics alone will not
help to differentiate between natural anomalies, related to mineralisation or hydrothermal activity, and contamination. Geochemical maps are needed to differentiate between the sources. In
terms of geochemical exploration, Sb can be viewed as a target related indicator element forming more local anomalies than many
other elements.
Weathering and soil forming processes lead to a general enrichment of Sb from bedrock through the soil profile to top (O-horizon,
litter). This is a natural process that is not related to human activities. Neither the soil C-horizon nor the ‘‘average Earth Crust” provide a viable background value for topsoils, the soil O-horizon, the
biosphere or the atmosphere.
Vegetation does not usually accumulate much Sb from the soils.
However, plants have been successfully used in the search for
deep-seated mineralisation, demonstrating that they do take up
Sb. Some plants growing on contaminated soil can exhibit Sb concentrations up to 1400 mg/kg. Different species will react quite differently to the same Sb concentrations in their surroundings (soil
or even atmospheric input) and 2–3 orders of magnitude differences in Sb concentration have been observed between plant species growing under exactly the same natural conditions.
Antimony appears to be slightly enriched in the marine environment when compared to terrestrial data. Good and representative (in terms of number of samples and area covered) datasets on
Sb in marine sediments, ocean water or marine plants are, however, scarce to non-existent. Most investigations, so far, have focussed on substantiating contamination instead of documenting
C. Reimann et al. / Applied Geochemistry 25 (2010) 175–198
natural variation. Regional-scale data would be needed in the light
of the strong enrichment of Sb in hydrothermal systems and the
existence of thousands of vents at the Mid Oceanic rift zones.
Continental-scale mapping, using a variety of different sample
materials, shows about three orders of magnitude of natural variation in Sb concentrations for each of the sample materials studied.
All observed large (regional- to continental-scale) distribution patterns are invariably related to natural processes, most often climate or soil age and weathering but also areas of hydrothermal
activity in the crust. Mapping at the continental-scale is needed
to detect and understand such processes. When only working at
the detailed scale, the most common scale for academic studies
of trace elements in the environment, these might easily be overlooked. It is sometimes necessary to take the famous step back to
obtain an unbiased overview. The fact that so much scientific work
has been carried out at a detailed scale can lead to severe misconceptions about the importance of certain processes for the distribution of an element at the continental or global scale. It is impossible
to judge the anthropogenic impact on the terrestrial ecosystem
reliably without knowing the continental-scale Sb distribution patterns in a variety of different sample materials. Given the large natural variation of Sb in all sample materials, it is not possible to
establish reliable Sb background values for any large area based
on statistics alone and without geochemical mapping.
Acknowledgements
We would like to thank the many people who worked to create
the datasets used for writing this paper, especially the Kola, the
Barents, the BSS and the FOREGS teams. Prof. Peter Filzmoser, Vienna University of Technology, provided the R-script to plot Fig. 5.
Rognvald Boyd, NGU, reviewed the manuscript internally and
checked the English language. We also thank Anja Hlade of i2a
for providing us with important hints and many useful references.
Two reviewers provided us with many helpful hints and suggestions to improve the clarity of the text.
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