Applied Geochemistry 27 (2012) 517–531

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Applied Geochemistry
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Review

Selenium in volcanic environments: A review

Geerke H. Floor a,b,⇑, Gabriela Román-Ross a,1
a
Department of Chemistry, University of Girona, Campus de Montilivi s/n, 17071 Girona, Spain
b
Department of Meteorology, Monitoring and Analysis, BRGM, 3 Avenue Claude-Guillemin, BP 36009, 45060 Orléans Cedex 2, France

a r t i c l e i n f o a b s t r a c t

Article history: Selenium is a chemical element with major environmental implications, due to the extremely narrow
Received 9 December 2010 range between essential and toxic concentrations. Volcanoes emit significant amounts of Se, which has
Accepted 20 November 2011 an enormous impact on the Se cycle and potentially human and animal health. This paper presents a
Available online 28 November 2011
broad overview of the current state of knowledge of major aspects of volcanic derived Se, focussing on
Editorial handling by R. Fuge
the processes in soils and aquifers.
Volcanic soils, formed when volcanic products weather rapidly, display peculiar characteristics. Sele-
nium contents can be relatively high (1–2 orders of magnitude higher) compared to the worldwide aver-
age (0.4 mg/kg), but often with low mobility. The soils can be impacted by local deposition of volcanic
emissions, which are enriched in Se due to volatilization in the magma chamber. It seems that the chem-
ical fate of Se in volcanic soils is controlled by sorption processes on poorly crystalline phases, which
presence depends on the parental materials and weathering. These sorption processes also determine
leaching to groundwaters. Some volcanic aquifers have Se concentrations above the WHO guideline of
10 lg/L. This might also be related to geothermal activity.
In spite of the well documented interest on Se during the last decades a significant number of uncer-
tainties exist on the behavior of this fascinating element. A preliminary model of the Se cycle around vol-
canoes can be constructed, but the well-known analytical problems associated with Se determinations
have produced a lack of reliable information on some processes involved in the chemical interaction
between soils and water. This review, therefore, also aims to identify the processes where new efforts
are needed to produce good quality data to be compared and integrated in global models.
Ó 2011 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
2. Properties of selenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
2.1. Selenium and health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
2.2. Geochemistry of selenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 520
3. Selenium in volcanic soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
3.1. Role of soils in selenium cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
3.2. Parent materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
3.2.1. Types of parental materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
3.2.2. Volcanic rock. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
3.2.3. Volcanic ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
3.3. Atmospheric deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
3.3.1. Volcanoes as a source of selenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
3.3.2. Atmospheric processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
3.4. Soil sorption processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
4. Selenium in volcanic waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
4.1. Processes influencing Se contents in groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
4.2. Hydrothermal activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526

⇑ Corresponding author. Present address: Institute of Reference Materials and Measurements, Joint Research Centre – European Commission, 111 Retieseweg, 2440 Geel,
Belgium.
E-mail address: geerke.floor@aquatrain.eu (G.H. Floor).
1
Present address: Amphos 21 Consulting S.L., Passeig de Garcia i Faria, 49-51, 08019 Barcelona, Spain

0883-2927/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2011.11.010
518 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531

4.3. Substrate interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526

5. Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528

1. Introduction
Volcanic eruptions are the clear and dramatic expression of dy-
namic processes in planet Earth. The majority of them occur at
plate boundaries. Volcanoes at diverging plate boundaries (e.g.
Mid Oceanic Ridges) predominantly occur on the seafloor.
Although submarine volcanism accounts for a significant amount
of the total global volcanic output (Rubin, 1997), it has little direct
impact on human lives. Subaerial volcanism is mainly concen-
trated along subduction zones at convergent plate boundaries
(e.g. the so-called Ring of Fire around the Pacific Ocean basin).
Moreover, these eruptions are normally more explosive than the
effusive lavas at divergent plate boundaries (e.g. Iceland) and intra-
plate settings (e.g. Hawaii). Volcanoes are well known for the
immediate destructive behavior during eruptions, due to lava
flows, ash falls and pyroclastic flows. However, even in the absence
of obvious volcanic activity, many volcanoes emit significantly
amounts of potentially toxic elements, including Se, As, Pb, Hg
and Cd (Oppenheimer, 2003).
In this work Se cycling in volcanic environments will be re-
viewed. There are several reasons for this review. Firstly, Se is a
chemical element with great environmental implications.
Although Se is an essential element for animals including humans,
ingestion of an excess amount of Se can produce adverse effects.
Secondly, volcanic areas are densely populated: 9% of the world’s
population (455 million) lives within 100 km of a historically ac-
tive volcano and up to 12% lives within 100 km of volcanoes with
Holocene eruptions (Small and Naumann, 2001). Thirdly, Se is be-
low S and next to As within the periodic table, implying some sim-
ilarities in their geochemical behavior (Section 2). Sulfur is one of
the most important elements within volcanic systems (Bluth
et al., 1993), while As geochemistry has received significant atten-
tion due to the associated health problems (Plant et al., 2003).
Fourthly, volcanic settings provide a dynamic environment with
steep pH and Eh gradients in space and time depending on the vol-
canic activity. For example, the rainwater pH at Mount Etna varies
between 2 and 6 in less than 10 km or within several months at
one location (Calabrese et al., 2011). This is expected to change
the Se speciation and thereby Se mobility. Lastly, there is increased
scientific interest in both Se and the potential effects of volcanic
activity on the environments (Fig. 1). The attention on Se grew
due to both the changing perspective of the role of Se in health
and the appearance of new analytical techniques, such as ICP-MS,
which opened possibilities to accurately determine Se at trace lev-
els in environmental samples (D’Ulivo, 1997). The awareness of the
environmental impact of volcanoes was triggered by major erup-
tions such as Mount St Helens in 1980, El Chicón in 1982, Galung-
gung in 1982 and especially Pinatubo in 1991, even though the
potential contamination by volcanoes had already been described
for the 1783 Laki eruption (Thordarson and Self, 2003; Witham
and Oppenheimer, 2004). Concern about the negative effects of
volcanoes keeps growing due to recent eruptions, including the
Chilean volcano Chaiten in 2008 (Martin et al., 2009), the Icelandic
volcano Eyjafjallajökull in 2010 (Gertissen, 2010) and the Chilean
Puyehue-Cordon Caulle in 2011.
Despite this enhanced scientific concern for both topics, no
work exists in which the available Se data within volcanic environ-
ments are compiled. Therefore, this work aims to summarize cur-
rent understanding of the Se cycle in volcanic settings and its
environmental impact. A schematic overview of Se transport paths
in volcanic environments is given in Fig. 2. Volcanoes can emit
three different products: gases, volcanic ash and lava, forming vol-
canic rock. The gases are enriched in Se due to the volatilization
processes and can be either emitted to the atmosphere or interact
with groundwater. Volcanic ash and rocks can weather to fertile
volcanic soils, forming the base for food production. There are
different pathways for volcanic activity to impact human health:
either intake by drinking water and food or direct exposure by

Volcanic eruptions Agung Fuego St Helen El Chicón Pinatubo Eyjafjallajökull

View on Se + health
Toxicity in Keterson
Se toxic Reservoir, USA
Essential Anti carcinogen Essential for metabolism +
thyroid hormone
4000
Scientific awareness
Selenium
3000 ICP-MS
volcanoes + environment (x10)

2000

1000

0
1945 1950 1955 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010

Fig. 1. Number of publications per year for different topics with important volcanic eruptions and changing view on effect of Se on health indicated. Data on number of
publications: ISI web of knowledge.
 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531
Fig. 2. Selenium transport pathways in volcanic environments.
inhalation, digestion or dermal exposure (e.g. during bathing in
geothermal waters). Drinking water and food are traditionally con-
sidered as the most important sources of trace elements for hu-
mans (Hartikainen, 2005). For this reason, the processes affecting
Se behavior in soils (Section 3) and groundwater (Section 4) are
the main focus of this article. The compilation of the available data
can be used to improve understanding of the Se cycle around vol-
canoes and at the same time indentify important gaps in current
knowledge.
2. Properties of selenium
2.1. Selenium and health
Of all trace elements, Se has one of the narrowest range be-
tween dietary deficiency (<40 lg/day) and toxic levels (>400 lg/
day for adults). The link between Se biogeochemistry and health
has been documented for many years and numerous papers on this
topic exist (Foster and Sumar, 1995, 1997; Rayman, 2000; Brown
and Arthur, 2001; Hartikainen, 2005; Fordyce, 2005). The perspec-
tive of Se and its health effects has an interesting history (Fig. 1).
The first case of Se toxicity was reported by Marco Polo during
his travels in China in the 13th century. However, it took until
1930 until the link with Se was made (Hartikainen, 2005). At
around the same time the occurrence of ´ alkali disease was re-
ported, which produced necrotic and sloughed hoofs, hair loss,
poor growth and reproduction problems in cattle (Rosenfeld and
Beath, 1964). From that moment Se was considered a dangerous
substance. This changed around 1957, when it was discovered that
trace amounts of Se protect against liver necrosis in vitamin E
deficient rats (Schwarz and Foltz, 1957). In 1966 it was revealed
that Se is an anti-carcinogen and in 1990 that it is essential for
519
metabolism and thyroid hormone synthesis (Arthur et al., 1993).
Nowadays, Se receives a lot of attention in veterinary science, be-
cause Se deficiency causes skeletal muscle calcification in sheep
and cattle, known as white muscle disease, which can be easily
prevented by Se supplementation (Brown and Arthur, 2001). Sele-
nium supplementation has also been proven to be useful to avoid
Kashin-Beck and Keshan diseases in humans (Moreno-Reyes
et al., 2003; Xia et al., 2005). However, the death of aquatic birds,
malformation of bird embryos and poisoning of fish in Kesterson
Wildlife Refuge in the 1980s served as a reminder to the danger
of environmental Se excess (Presser, 1994). In Hubei Province in
China a human disease characterized by loss of hair and nails with
a peak prevalence in the 1960s was also linked to Se toxicity (Yang
et al., 1983). As a result, at the present time Se receives extensive
attention in medical studies and is famous as a so-called double-
edged sword. Another reason for the interest in Se is that it influ-
ences the toxicity of other elements, such as As and Hg (Yang
et al., 2002; Gailer, 2007; Huang et al., 2008; Ralston and Raymond,
2010; Wang and Guo, 2011). This is important in volcanic environ-
ments too, as these elements are also emitted in significant amount
by volcanoes (Oppenheimer, 2003).
Nevertheless, it remains unclear how volcanic derived Se im-
pacts the vast populations around volcanoes. There is some evi-
dence of a higher cancer risk in volcanic areas, such as increased
incidence rates of thyroid cancer (Kung et al., 1981; Arnbjornsson
et al., 1986; Goodman et al., 1988; Bates et al., 1998; Amaral et al.,
2006; Truong et al., 2007; Duntas and Douman, 2009; Pellegriti
et al., 2009). It has been shown that Se plays a central role in cancer
development (Patrick, 2004; Rayman, 2005) and that cases with
thyroid cancer have lower Se serum levels compared to a control
group (Glattre et al., 1989). Therefore, the low Se mobility in
combination with high intake of other trace elements has been
suggested as a potential factor in the development of thyroid can-
520 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531
cer in volcanic areas (Duntas and Douman, 2009). On the other
hand, a high incidence of thyroid cancer has also been reported
in the Etna area (Pellegriti et al., 2009), while Se levels in the drink-
ing water in this area are high (Aiuppa et al., 2000a, Section 4). To
constrain the role of volcanic derived Se on human health, the geo-
chemical distribution of Se in these surroundings should be known.
Therefore, in this review the available geochemical data of Se in
volcanic environments are discussed, focusing on soils and
aquifers.
2.2. Geochemistry of selenium
Selenium is a non-metal of group 16 in the periodic table having
an atomic number of 34. The impact of Se on the surrounding envi-
ronment cannot be predicted by the total concentration. This is be-
cause only a part of the total concentration has the potential to
leach (towards aquifers) or be taken up by plants (to enter the food
chain). The amount of potentially mobilized Se varies, wherein the
Se speciation is an important factor (Cutter, 1982; Hartikainen,
2005). In natural settings, Se can be found in +6, +4, 0, and 2 va-
lences and in a variety of organic compounds (Cutter, 1982: Elrash-
idi et al., 1987).
Chemically Se is often compared to S, which is immediately
above it in the periodic table. Selenium forms similar compounds
to S. For instance, Se2 substitutes for S2 in minerals like sphaler-
ite ((Zn, Fe)S) due to comparable elemental ionic radii of 184 and
170 pm (a difference of <10%) and similar electronegativities of
2.45 and 2.48. However, several chemical dissimilarities exist be-
tween Se and S. The electronegativities and ionic radii vary much
more for other redox states and, therefore, substitution between
S and Se is not favored (Shannon, 1976). Other disparities can be
observed comparing the Eh–pH stability diagrams for the aqueous
speciation of Se and S (Fig. 3). The biggest differences in the ther-
modynamically stable redox species occur under moderately
reducing conditions when Se is stable as Se(IV) or as Se(0).
However, S(IV) is not a thermodynamically stable species and
pH range volcanic waters
Crater Geothermal waters
lake
lake
Rain
Rain
Aquifer
0 2 4 6 8 10 12
pH
1.0 As
H3AsO4
H 2AsO4-
0.5
Eh(V)
(As O HAsO42-
2 3)
HA
0.0 3 sO
3 0.0
H2AsO3-
As
-0.5
HAsO 32-
Fig. 3. Se, S and As speciation in aqueous solutions at 25 °C (Brookins, 1988) and pH range for different types of volcanic waters.
S(0) is only stable at restricted settings. As a result, the behavior
of Se during oxidation and reduction processes is more compli-
cated compared to S. In strongly reducing circumstances Se(-II)
and HSe chemically resemble sulfide. Under oxidizing conditions,
Se(VI) is thermodynamically favored and will form selenate ions
(SeO24 ), which are chemically similar to SO24 .
The geochemical behavior of Se is also often compared to that of
As. Both are oxyanion-forming elements present at trace concen-
trations in the environment. However, As is in its oxidized form,
As(V), over a much wider pH and Eh range compared to Se
(Fig. 3). Moreover, As(V) is more prone to adsorption than As(III),
while in contrast Se(VI) has less affinity for adsorption on metal
oxides than Se(IV) (Plant et al., 2003). This means that in oxic envi-
ronments Se is more mobile than As.
All these considerations are only valid during thermodynamic
equilibrium, while in nature kinetics must also be considered. Fur-
thermore, volcanic settings are extreme environments, while the
Pourbaix diagrams are valid for standard conditions (T = 25 °C,
1 bar). The extended use of these graphs could produce a misun-
derstanding of the geochemical processes occurring at high
temperature and pressure (Brantley et al., 2008). Although extrap-
olation of equilibrium constants at elevated temperatures occurs, it
has only been performed for relatively simple systems. Therefore,
these databases lack thermodynamic data for potential species,
including metal selenides (D’yachkova and Khodakovskiy, 1968;
Xiong, 2003; Akinfiev and Tagirov, 2006).
Selenium compounds have vaporization temperatures between
41 and 680 °C (Table 1), which is generally low enough to be vol-
atilized during volcanic activity and other high temperature pro-
cesses, such as coal burning (e.g. Zeng et al., 2001; Yan et al.,
2001, 2004; Monahan-Pendergast et al., 2008). Important differ-
ences exist between the vaporization temperatures of S- and Se-
compounds (Table 1). The biggest dissimilarity is observed be-
tween SO2 and SeO2. While SO2 is a widespread volcanic gas, being
in the gas form even at ambient temperatures given its vaporiza-
tion temperature of 10 °C, SeO2 has a vaporization temperature
S
1.0
HSO 4-
0.5 SO 42-
Eh(V)
S
0.0 H2S
HS -
-0.5
14 0 2 4 6 8 10 12 14
pH
HSeO 4-
1.0 Se
H 2SeO 3
SeO 42-
0.5 HSeO 3-
AsO43 -
Se
SeO 32-
H2Se
AsO33-
-0.5 HSe -
 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531
Table 1
Vaporization temperature of some S, Se ad As compounds.
Sulfur Selenium Arsenic
Compound VT in °C Compound VT in °C Compound
H2S 60 H2Se 41 AsH3
S(0) 445 Se(0) 680 As(0)
SO2 10 SeO2 315 (subl) As2O3
H2SO4 290 H2SeO4 260 H2AsO4
of 315 °C. This means that during cooling processes within a volca-
nic plume, SeO2 is very unstable in the atmosphere and can usually
readily transform to particulate phases (Wen and Carignan, 2007).
3. Selenium in volcanic soils
3.1. Role of soils in selenium cycle
The behavior of Se in soils is the basis of the Se cycle in a geo-
ecosystem. Soils play a key role in trace element cycling, because
they are an important environmental interface between the litho-
sphere, atmosphere, hydrosphere and the biosphere. They deter-
mine the Se level in food and water and thereby human intake
(Brady and Weil, 2001). In this perspective, volcanic soils are par-
ticularly significant due to their high potential for agricultural pro-
duction. Although they globally make up less 0.8% of the Earth’s
surface, they are important and productive soils that host 9% of
the world population (Small and Naumann, 2001). In Indonesia
there is a strong relationship between the population density and
the input of volcanic ash with 3–4 times higher population density
around Merapi volcano compared to areas without young volcanic
ash (Mohr, 1938). Soils formed in volcanic areas have many dis-
tinctive properties that are rarely found in soils derived from other
parent materials (Shoji et al., 1993). These properties strongly con-
trol the trace element behavior.
The Se content of most soils is very low at 0.01–2 mg/kg with a
world mean of 0.4 mg/kg. However, Se concentrations vary widely
and amounts up to 1200 mg/kg have been reported in Ireland
(Fordyce, 2005). It was recognized early on that volcanic soils from
Hawaii have relatively high Se content (1–20 mg/kg) compared to
other USA soils, but that its mobility is low (Byers, 1935, 1936;
Byers et al., 1936, 1938). An overview of the processes impacting
Se content and mobility in volcanic soils is given in Fig. 4. The
volcanic activity influences the characteristics of the parental
materials, the atmospheric deposition and indirectly the sorption
processes by pH and redox conditions, Se speciation and input of
other anions potentially competitive for adsorption sites. Further-
more, human activity can result in an important input of compet-
itive anions by the addition of fertilizers. The mineralogy of the
parent material changes during weathering, impacting the sorp-
tion characteristics of the materials. In this section the parental
materials, atmospheric deposition and sorption processes will be
discussed in more detail.
3.2. Parent materials
3.2.1. Types of parental materials
In soil classifications it is not common to group soils based on
the parent material, as is the case for volcanic soils. Nevertheless,
soils with volcanic parent material have a unique combination of
soil properties, resulting from weathering of, above all, volcanic
glass (Shoji et al., 1993). Volcanic products, both ash and rocks,
contain a proportion of volcanic glass. The distinctive properties
and fertility of volcanic soils are often related to the addition of
volcanic ash (Shoji et al., 1993). However, soils can also form
521
VT in °C
55
614
100
Fig. 4. Overview of the processes impacting Se content and mobility in volcanic
soils.
directly on igneous volcanic rock. The parental materials form an
essential control on Se concentrations in soils (Fordyce, 2005).
Therefore, in this section the Se contents of igneous volcanic rock
and volcanic ash are discussed.
3.2.2. Volcanic rock
Selenium escapes as high-temperature gas during volcanic
eruptions due to its volatility (Section 2.2). Consequently, Se con-
centrations left behind in volcanic rocks are commonly assumed
to be low (Table 2, Fordyce, 2005) with estimated average concen-
trations between 0.01 and 0.14 mg/kg (Malisa, 2001, and refer-
ences therein). However, as observed in Table 2, some reported
values are one to two orders of magnitude higher. It is hard to
judge the quality of the data, because a number of papers lack ade-
quate descriptions of the analytical procedures. Moreover, since
several studies do not focus on Se behavior, some of the chosen
methodologies lack adequate limits of detections (LODs) for Se. Re-
ported Se/S values are in the order of 10 4 and 10 5 (Jenner et al.,
2008). Given the fact that Se concentration data in volcanic rocks
are relatively scarce and the impact of a range of magmatic pro-
cesses is unknown, it is impossible to predict Se contents based
on rock characteristics.
3.2.3. Volcanic ash
Davidson and Powers (1959) recognized that tuffs (consisting of
consolidated volcanic ash) can be several orders of magnitude
more enriched in Se compared to volcanic rocks. Enrichments of
volatile elements in volcanic ash are believed to originate from
adsorption processes on the ash surface during interactions within
the eruption plume (Rose, 1977; Oskarsson, 1980; Delmelle et al.,
2007). The soluble compounds might be readily mobilized from
fresh volcanic ash upon exposure to water (Witham et al., 2005,
and references therein). This can cause both contamination prob-
lems and release of essential nutrients (Cook et al., 1981; Cronin
et al., 1997, 1998; Stewart et al., 2006; Jones and Gislason, 2008;
Martin et al., 2009; Duggen et al., 2010). Weathered ash has often
been mentioned as being an important Se source in selenosis areas
such as Ziyang Country in China and the Keterson reservoir in the
USA (Presser, 1994; Kulp and Pratt, 2004; Kunli et al., 2004). Stew-
art et al. (2006) modelled the impact of volcanic ash from the 1995
eruption of the Ruapehu volcano (New Zealand) and predicted that
ash fall has a strong influence on the Se concentration in water.
Moreover, Se concentrations in pasture increased markedly after
this eruption with higher Se concentrations with thicker tephra
deposits (Cronin et al., 1997). Reported total Se content in volcanic
ash vary between 0.1 and 7 mg/kg (Table 3). The average value is
1.7 mg/kg, four times above the average concentrations in soils.
522 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531

Table 2
Examples of Se contents in volcanic rocks.

Location Se content in mg/kg (methodology) References

USA Various locations <1, except for tuffs Davidson and Powers (1959)
Keneewan peninsula <LOD (INAA) Nicholson (1992)
Canada Superior province Median 0.34, range 0–5.5 (RNAA, XRF) Crocket et al. (2005), Stone et al.
(1993, 1996), Walker and Stone (2001)
Appalachians Only one rock above LOD (RNAA, LOD 1–2) Bédard and Stevenson (1999)
Central Atlantic mp Median 1.4, range 0–3.2 (INAA) Pepezik et al. (1988)
Tasmania Great Lake Median 0.11, range 0.05–2.29 (HG-AAS) Greenland and Campbell (1977)
Brasil Serra Geral Median 0.08, range 0.01–0.24 (INAA) Hughes et al. (1986)
Japan Several locations Median 0.01, range 0.001–0.123 (fluometry) Tamari et al. (1990)
Iceland Eldfell volcano (1973) Median 2.77, range 2.17–3.69 (INAA) Higgins and Roberge (2007)
Various locations Median 0.04, most <0.25 (colometrically) Koljonen (1973)
USSR Various locations Median 0.14, range 0.1–0.37 Sindeeva (1964)
Finland Various locations Range <0.5–7.1 (XRF), 75% below LOD Papunen et al. (2009)
Germany Hessian Depression Most samples <0.2 Wedepohl (1983)
Italy Campanian vp <1 (max LOD, methodology unclear) Paone et al. (2001), Paone (2008),
Ayuso et al. (1998)
Turkey Afyon vc <3 (LOD, ICP-MS) Akal (2003)
Tenerife Bandas der Sur formation Median 0.42, range 0.01–1.57 (XRF) Kröchert and Buchner (2009)
Oceanic MORB Atlantic Median 0.23, range 0.16–0.36 (LA-ICP-MS)
Volcanic MORB Pacific Median 0.23, range 0.16–0.35 (LA-ICP-MS)
rock Pual Ridge, SW Pacific Median 0.15, range 0.05–0.29 (LA-ICP-MS) Jenner et al. (2010)
Reference basalts <0.1 (isotope dilution HG-ICP-MS) Marin et al. (2001), Forrest et al. (2009),
(BHVO-2, BIR-1, BE-N) Savard et al. (2009)

Mp magmatic province.
Vp volcanic province.
Vc volcanic complex.

To understand the environmental impact of ash fall, the geo-
chemical mobility of the deposited Se is more important than the
total concentrations. For example for the 1995 Ruapehu eruption,
the total Se deposition rate for a 1 mm tephra thickness greatly ex-
ceeded the recommended amount of Se fertilization for agricultural
soils. Nevertheless, only up to 5% of the Se in the tephra was leach-
able. Therefore, the mobile Se was just 11–22% of the normally ap-
plied Se from fertilizer (Cronin et al., 1997). To study the mobility of
the elements adsorbed on the ash, ash leachate experiments are of-
ten performed. Only some of the ash leachate studies include Se
data (Table 3). The concentrations in ash leachates strongly de-
pends on the characteristics of the volcanic eruption (i.e. magma
type, mode of eruption, concentration of the plume, ratio of parti-
cles to gas, particle size-fractions, temperature within the plume,
environmental conditions including wind and humidity). More-
over, it is strongly influenced by the experimental approach (e.g.
leaching solution used, ash/leach-solution ratio, reaction time,
ash grain-size fraction used: Witham et al., 2005). Therefore, the
number of variables is much higher than the number of data for
Se concentrations in ash leachates, making systematic interpreta-
tions impossible with the current data. The limited available data
show that between 0.001 and 0.64 mg/kg is mobile Se. High mobil-
ity seems only be present in samples from Fuego Volcano, Guate-
mala, although total concentrations are not reported for these
samples (Rose et al., 1978). This low mobility for most ash samples
seems in contradiction with the observation that weathered ash
and/or tuff has a high content of mobile Se (Davidson and Power,
1959; Presser, 1994). The Se/S ratios in the ash and in the leachate
solutions (Table 3) are in the same order of magnitude as volcanic
emissions (Table 4, Section 3.3). Given the importance of volcanic
ash as parental material, more studies focussing on Se behavior
in both fresh and weathered volcanic ash are required.
3.3. Atmospheric deposition
3.3.1. Volcanoes as a source of selenium
Atmospheric deposition can cause a Se flux towards soils. During
degassing processes Se is transferred from the magmatic system to-
wards the atmosphere. Due to this mechanism, volcanoes emit Se in
substantial concentrations (Table 4). Jenner et al. (2008, 2010)
showed that S concentrations in SW Pacific back-arc basin and
Hawaiian glasses are considerably lower than in MORB glasses,
while Se contents are comparable. Moreover, Se follows the
behavior of other chalcophile elements such as Au, Ag and Cu. This
indicates that Se is not as volatile as S. This is supported by the
observation that reference materials prepared from basaltic rocks
at atmospheric pressure and high temperatures lost almost all their
S, but retained Se (Jochum et al., 2006). The lower volatility for Se
than for S is also sustained by data from fumaroles where lower
Se and Se/S are observed for lower temperatures (Suzuoki, 1964;
Murata and Richter, 1966). The different behavior of Se and S within
the magmatic chamber can explain the high range of Se/S observed
in volcanic emissions, even within one volcanic system (Table 4).
Moreover, these observations are in line with the higher
vaporization temperatures for Se than for S compounds (Table 1,
Section 2.2). The implication of this lower volatility is that higher
Se/S ratio and the highest Se release is expected during high-
temperature events.
The total volcanic Se flux is poorly constrained and estimates on
the importance of volcanic emissions for atmospheric Se budget
vary significantly (between 1% and 12% of total Se emissions
assuming total emissions of 15.6 Gt/a (Wen and Carignan, 2007)).
It is extremely difficult to estimate accurately the volcanic Se flux.
The estimation is based on the Se/S ratio and the total S emissions
of volcanoes. This raises a number of challenges. Firstly, it is diffi-
cult to obtain quantitative data for Se in volcanic gases (Finnegan
et al., 1989; Toutain et al., 2003). Secondly, the Se/S ratio is based
on a relatively small number of accessible volcanoes and volcanic
vents at a given point in time. As mentioned above, the Se/S varies
significantly from volcano to volcano but also temporally and spa-
tially within one volcanic system (Table 4), making it difficult to
upscale to a time-average global degassing flux. Thirdly, there is
significant uncertainty on the amount of S emitted by volcanoes
(Mather et al., 2003).
For S it has been estimated that 2=3 of volcanic emissions occur
during passive degassing (Bluth et al., 1993). Unfortunately, with
current knowledge the relative contribution of explosive eruptions
to the total volcanic Se flux cannot be estimated.
 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531 523

Table 3
Total and leachable Se concentrations in volcanic ash in mg/kg. For comparison, the WHO guideline for drinking is 10 lg/L which corresponds to 0.01 mg/kg.

Volcano Distance Date Se conc (mg/kg) Se/S  104 Comments on methodology References
crater (km)
Se total concentration (in mg/kg)
15 1995 (11 October) 3.7 1.2
155 1995 (11 October) 3 0.98
18 1995 (14 October) 3 3.9
Raupehu 48 1995 (11 October) 2.5 7.2 Cronin et al. (1997)
New Zealand 36 1996 (17 June) 2 2.8 Cronin et al. (1998)
38 1996 (17 June) 2.4 0.74
80 1996 (17 June) 2.2 0.78
141 1996 (17 June) 2.4 1.7
Mount St 100 1980 0.5 Taylor and Lichte (1980)
Helens 400 2
USA 790 <0.2
Augustine Alaska 1976 0.34 2.0 Lepel et al. (1978)
El Chicón Mexico 1982 7 Kotra et al. (1983)
6.5 2006 (November) 0.9 Encountered interaction Calabrese (2009)
with rainwater
5.5 2006 (November) 0.8 16
7.3 2006 (December) 0.7 14
5.5 2007 (March) 0.9 90
Mount Etna 5.5 2007 (April) 0.7
Sicily 9.5 2007 (April) 0.3
Italy 5.5 2007 (May) 1.1
Europe 1.2 2007 (May) 0.8 2.2
1.2 2007 (September) 0.9 45
1.2 2007 (October) 0.7
Se leaching concentration (mg/kg expressed per weight ash)
Popocatépetl 13.4 1997 (12 May) 0.09 Ratio 1:25 2 h agitated Armienta et al. (2002)
ICP-MS
Mexico 15.9 0.04
21.5 0.03
25.5 0
1974 (14 October) 0.36 (0.22–0.48) 6.3 Methodologies not specified Rose et al. (1978)
Fuego 1974 (17 October) 0.27 (0.16–0.40) 4.3
Guatemala 1974 (19 October) 0.55 (0.32–0.64) 9.7
1974 (23 October) 0.20 (0.06–0.48) 7.4
Ruapehu Several 1995 and 1996 0.1 or <0.1 X Ratio 1:25, 24 h agitated Cronin et al. (1997)
distances Close to DL
New Zealand 5 different 1980 <0.025 Ratio 1:2.5, 1 h agitated Cronin et al. (1998)
locations
Mount St 110 0.001 10 Ratio 1:0.6 4 h in column Nehring and Johnston (1981)
Helens 115 0.003 0.12
USA 250 0.003 0.17 Taylor and Lichte (1980)
400 0.002 0.11

Despite the uncertainty, at a global (Mosher and Duce, 1987;
Nriagu, 1989; Wen and Carignan, 2007) or subglobal (Ross, 1985)
scale anthropogenic emissions are dominant over volcanic. Never-
theless, this may be different at a regional scale. This is for example
the case for the Etna volcano. It has been shown that the Etna vol-
cano emits an order of magnitude more Se than all anthropogenic
sources on the island, even during passive degassing. Therefore,
Etna volcano is the main point source of Se in the Mediterranean
area (Calabrese, 2009).
3.3.2. Atmospheric processes
The effects of the Se release on the local environments strongly
depend on atmospheric processes. Not many data are available for
Se speciation in volcanic plumes. Thermodynamic calculations on
volcanic gas compositions from Mt St Helens show that Se is trans-
ported as H2Se (Symonds and Reed, 1993). This is different for S,
which is only transported as H2S at low temperatures, but as SO2
at high temperatures. For two Japanese volcanoes, elemental Se
was the thermodynamic stable species (Suzuoki, 1964). The appro-
priateness of thermodynamic modelling depends on whether vol-
canic gases approach chemical equilibrium (i.e. if kinetically
retarded reactions are present), the quality of the input gas compo-
sition and the quality and quantity of the thermodynamic data (i.e.
missing species). Therefore, it is important to check the results
with field data. Measurements of the fumarolic gas at Vulcano Is-
land, Italy, indicate the occurrence of elemental Se, as Se is trapped
on the filter rather than present in the condensate as would be ex-
pected for SeO2 or H2Se (Bichler et al., 1995). No measurements are
available at other locations. However, volcanic emissions and coal
combustion share both elevated temperatures and the excess of
SO2 which may act as a reducing agent. Therefore, coal combustion
can be used as an analog to predict the behavior of Se in volcanic
emissions. In coal combustion gases H2Se, SeO, SeO2, SeCl2 and ele-
mental Se were all found to be possible thermodynamically stable
species (Monahan-Pendergast et al., 2008 and references therein).
Moreover, experiments on coal combustion confirmed the pres-
ence of elemental Se and its oxides (Yan et al., 2001, 2004; Senior
et al., 2000).
The convergence of high temperature and reduced volcanic
gases with the atmosphere triggers a series of cooling and redox
reactions (Fig. 5). Hydrogen selenide will be oxidized to SeO2. Sele-
nium dioxide can be transformed to elemental Se by reactions with
SO2 or with SO2 and water (Andren and Klein, 1975; Wen and
Carignan, 2007). However, whether thermodynamic equilibrium
occurs during this process is untested and kinetic investigations
need to be carried out on the thermodynamically favored path-
524 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531

Table 4
Se fluxes and Se/S for some volcanoes.

Location Period Se Se/ Comments References

4
(Gg/ S  10
year)
Worldwide 0.4–1.2 Estimates vary between 1 Mosher and Duce (1987)
emissions of and 12 of total Se emissions
subaerial
volcanism
0.3–0.5 Mather et al. (2003)
0.1–1.8 0.007–0.35 Nriagu (1989)
Antarctica Mount Erebus 1986–1991 0.002 0.2–30 Zreda-Gostynska et al.
(1997)
1997–2000 0.0001 0.1 Wardell et al. (2008)
New Zealand White Island 2000–2001 0.0005 0.06–0.009
Indonesia Merapi 1984 (January– 3–60 Symonds et al. (1987)
February)
Russia Kurile Island 1990–1993 0.1 Taran et al. (1995)
USA Kilauea 1983 (November) 0.6 Max value. System not Finnegan et al. (1989)
quantitative for Se
1983–1984 6–30 Olmez et al. (1986)
1984–1996 0.023 0.64 Hinkley et al. (1999)
St Helens 1980 (May) 1.3 Collected with aircraft: just Vossler et al. (1981)
after major eruptions
1980 (September) 0.037 3.55 Collected with aircraft: Phelan et al. (1982)
stable plume emission
Augustine 1976 5–10 Collected with aircraft Lepel et al. (1978)
Mexico El Chicón 1982 0.0014 Collected with aircraft: Kotra et al. (1983)
particulate only
Caribbean Montserrat 1996 0.4–4 Allen et al. (2000)
Italy Stromboli 1993–1997 0.055 0.3–46 Allard et al. (2000)
La Fossa, Vulcano 1994 0.0008 Bichler et al. (1995)
Etna Total 1976 0.23 15 Eruption Faivre-Pierret and Le
Guern (1983)
Main plume 1976 (June) 6.77 Moderately pyroclastic Buat-Menard and
activity Arnold (1978)
Lava vents 32.1
Bocca Nuova 1987 (July) 0.016 1.16 Relatively quiet activity Andres et al. (1993)
SE Crater 0.002 0.24
Total 0.018 0.86
Bocca Nuova 2001 (3 May) 18.2 Before eruption Aiuppa et al. (2003)
2001 (18 May) 8.39
2001 (5 June) 9.27
2001 (29 June) 50.8
2001 (12 July) 5.84
Lava flow 2001 (19 July) 15.0 Eruption
Monti Carcazzi 1.12
Vent
2001 (25 July) 20.0
2001 (1 August) 14.3
Crater rims Min 2004–2007 0.0003 0.001 Passive degassing Calabrese (2009)
Max 0.216 0.25
Mean 0.019 4.15

ways. Due to the relatively high vaporization temperatures, both
elemental Se and SeO2 can be condensed and rapidly form partic-
ulate Se under normal atmospheric conditions (Zhang et al.,
2002). Selenium dioxide is soluble in water and can dissolve in
rainwater to form H2SeO3 (Zhang et al., 2002). The reaction
between elemental Se and sulfoxy radicals transforms insoluble
elemental Se to soluble Se(IV) and Se(VI) with unstable polyselen-
odithionates as intermediate products (Bronikowski et al., 2000).
Therefore, independent of the species present in the plume, sele-
nate and selenite are the expected species in rainwater. Data from
Floor et al. (2011a) indicate the likeliness of the dominance of sel-
enate in Etnean rainwater, although more detailed studies are re-
quired. The Etna volcano is the only location where Se deposition
has been investigated (Calabrese, 2009; Calabrese et al., 2011).
The Se content of rainwater in this area rapidly decreases with dis-
tance from the volcano, confirming the prevailing volcanic contri-
bution to rainwater composition (Fig. 6). The concentrations in the
rain water close to the crater depend strongly on the volcanic
activity, but are up to 13 lg/L and, thereby, significantly higher
than most worldwide reported values (generally <1 lg/L; Conde
and Sanz-Alaejos, 1997, and references therein). Also in anthropo-
genic acid rain water samples from Canada much lower Se con-
tents were detected (Milley and Chatt, 1987). Selenium/S ratios
in the rainwater vary significantly between 10 3 and 10 5
(Calabrese et al., 2011). However, no systematic changes in Se/S
are observed with location (Fig. 6) or with volcanic activity (i.e.
no clear correlation with F , which is a good tracer of plume emis-
sions (Aiuppa et al., 2004)). Moreover, rainwater Se/S ratios are in
the same range as the ratios in the plume (Table 4). This would
indicate that deposition processes produce no evident S–Se frac-
tionation around the Etna volcano (Calabrese, 2009).
Even though the measured concentrations in Etna rainwater
correspond to significant deposition of Se (up to 15 lg/m2 per
day), only 0.8–2.2% of the total Se emissions is deposited locally.
The low percentages of local deposition have been related to the
high altitude of the volcano, wherefore the volcanic output is
 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531 525

Fig. 5. Atmospheric transformations of selenium.

6
average Se concentration
5 2
power R = 0.98
Se ( µ g/L)

4
3
2
1
0
1.0
average Se/S ratio
0.8
Se/S x 10 -4

0.6
0.4
0.2
0.0
0 1 2 3 4 5 6 7 8 9 10
Distance from craters (km)

Fig. 6. Average Se and Se/S in Etna rainwater and its changes with distance from the volcano. For comparison the average Se/S ratio within the plume (Table 4) for the same
period is indicated with a dashed line. Data from Calabrese (2009).

directly injected above the boundary layer (Calabrese, 2009; Cala-
brese et al., 2011). Since this has only been measured at Mt Etna
during quiescent degassing activity, there is a need to investigate
Se around other volcanoes and during eruptions to identify the
general trends of local deposition. For example, at Masaya volcano
in Nicaragua the surface is at the same altitude as the plume vent,
so direct plume fumigation often occurs (Delmelle et al., 2001). In
contrast, Mt Etna has a conical form with the plume vents at the
top. This geometry does not allow frequent direct fumigation of
its flanks significantly reducing the deposition of acidic
compounds.
Even with the significant Se deposition in the Mt Etna area,
there is no evidence that this atmospheric deposition impacts the
Se content of the soils, given the lack of spatial distribution in
the total Se concentrations (Floor et al., 2011b). Again, this should
be investigated around other volcanoes. However, for F it was
found that topsoils from the eastern, downwind sector of Mt Etna
volcano are typically richer in F compared to soils on the western
upwind flank (Bellomo et al., 2007). This indicates the importance
of sorption processes for the behavior of Se within soils.
3.4. Soil sorption processes
Selenium mobility is determined by sorption processes, affected
by bio-physiochemical parameters such as pH and redox conditions,
Se speciation, soil texture, mineralogy, organic matter content and
competitive ions (Fordyce, 2005). Strong sorption on soil com-
pounds causes a soil enriched in Se, but with low Se mobility. Studies
on volcanic soils from New Zealand (John et al., 1975) point out the
importance of poorly crystalline Fe oxides (e.g. ferrihydrite) for Se
adsorption properties. Nakamaru et al. (2005, 2006) and Nakamaru
and Sekine (2008) demonstrated with the combination of adsorption
experiments and sequential extractions that there was high correla-
tion between Se adsorption and the presence of aluminosilicates
(e.g. allophane and imogolite) for Japanese volcanic soils. These
poorly crystalline Fe and Al phases are typical weathering products
from volcanic glass, usually the first component to undergo weath-
ering. They are an intermediate step in the formation of more or-
dered clay minerals, like halloysite, kaolinite, gibbsite and
montmorillonite. The high content of short-range-ordered com-
pounds (SROCs) also causes many other specific characteristics of
526 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531
volcanic soils, such as a high content of amorphous and poorly crys-
tallized silicate minerals, fast accumulation of organic matter, high
water retention and high pH dependent charge (Shoji et al., 1993).
Previous work in non-volcanic areas attributes a key role for soil or-
ganic matter in the behavior of Se within soils (Gustafsson and
Johnsson, 1992). Firstly, organic matter acts as a sorbent itself (Ka-
mei-Ishikawa et al., 2007). Secondly, dissolved organic carbon can
compete for adsorption sites (Dynes and Huang, 1997; Wijnja and
Schulthess, 2000b). Thirdly, the soil organic matter impacts on the
stability of the Al phases present (Shoji et al., 1993). Lastly, both soil
organic matter and Fe oxides can induce redox changes (Myeni and
Tokunaga, 1997; Bruggeman et al., 2007; Scheinost et al., 2008). Sel-
enite can be easily reduced to elemental Se in the presence of DOC
(Bruggeman et al., 2007). In contrast, selenate has been shown to
be a meta-stable species which can be present in non-favorable ther-
modynamic conditions (Bruggeman et al., 2007; Floor et al., 2011a).
Given the fact that volcanic soils can have high soil organic matter
(Shoji et al., 1993), this is expected to play a key role in Se behavior
in such soils.
The study of Se sorption processes in natural soils is extremely
challenging due to the high heterogeneity of its compounds. For
this reason, sorption mechanisms and the effect of a range of
parameters (Se speciation, pH and time) are mainly studied with
pure phases under controlled conditions (Balistrieri and Chao,
1990; Wijnja and Schulthess, 2000a; Peak and Sparks, 2002; Wu
et al., 2000). These works have been summarized for different min-
eral phases in the review of Fernández-Martínez and Charlet
(2009). Under most circumstances adsorption of selenite is much
greater than selenate. In general, more adsorption occurs at lower
pH due to the more positive surface charge of minerals (Yu, 1997;
Neal et al., 1987; Barrow and Whelan, 1989). However, in extreme
pH variations this can be counteracted by the higher protonization
of the Se species (Fig. 3). Few studies exist on the kinetics of Se
adsorption processes, but most show fast kinetics (<2 h). However,
Se adsorption has not yet been studied for all compounds relevant
to volcanic soils. For example, the Se adsorption capacity of volca-
nic glass remains unknown, while this has been shown to be an
important adsorption site for As (Sigfusson et al., 2008).
The competition of other anions, such as SO24 and PO34 , also
strongly influences Se sorption. Fertilizers containing significant
amounts of phosphate might reduce selenite adsorption (He
et al., 1994; Dhillon and Dhillon, 2000; Goh and Lim, 2004; Naka-
maru et al., 2006; Nakamaru and Sekine, 2008). Sulfate is widely
abundant in volcanic environments. Its competitive effect strongly
depends on the Se speciation. Selenate is similar to SO24 and,
therefore, similar surface complexes form with both oxyanions
(Wijnja and Schulthess, 2000a). During acid rain events (Sec-
tion 3.3.2) and direct plume fumigation (Delmelle et al., 2003;
Delfosse et al., 2005, 2006) SO24 might be transferred from the
atmosphere towards soils. For example, rainwater around Mt. Etna
contains up to 450 mg/L SO24 (Calabrese, 2009). It has been shown
that the presence of SO24 causes greater selenate mobilization (20–
30 times more) during interaction between rain and poorly devel-
oped soils (Floor et al., 2011a,b). This mechanism did not release
As, resulting in differences in Se and As behavior. More systematic
studies are required to study the role of sorption processes in Se
(im)mobilization in soils during natural processes.
4. Selenium in volcanic waters
4.1. Processes influencing Se contents in groundwater
Groundwater is often used as drinking water, which is one of
the main sources of trace elements for human and animals
(Hartikainen, 2005). In contrast to the extensive database of As
concentrations in water, Se is often not included in the list of ana-
lyzed elements. As a consequence, Se concentration data are
scarce. In general, Se contents of groundwater are often below
1 lg/L and rarely exceed the WHO guideline of 10 lg/L. However,
Se can be enriched in volcanic waters (Table 5). The trace element
content in volcanic aquifers varies due to different mechanisms: (i)
hydrothermal activity, (ii) host rock interactions (weathering,
sorption processes) and (iii) input from rainwater and leaching
from soils and volcanic ash (Fig. 7). The latter was discussed in
the previous section, the other two processes will be discussed
here.
4.2. Hydrothermal activity
Geothermally active areas occur where an above average geo-
thermal gradient allows hot water or steam to emerge at the
Earth’s surface. High temperature geothermal systems occur
throughout the world, generally at tectonic plate boundaries or
along hotspots. Selenium belongs to the typical ´geothermal suite
of contaminants, which additionally includes As, V, B, F, TI, Li, Hg,
Sb and H2S (Webster and Nordstrom, 2003). Selenium is often
not included in measurements of geothermal trace elements, prob-
ably due to the difficulties regarding sampling and measurements.
The published data for thermal waters are included in Table 5. It
shows that the thermal groundwaters at Vulcano and Ischia Islands
(Southern Italy) are strongly enriched in Se with values above the
WHO guideline of 10 lg/L (Aiuppa et al., 2000b; Daniele, 2004, Ta-
ble 5). Around Etna volcano the highest Se concentrations (66 lg/L)
are observed where thermal saline brines from the sedimentary
basement enter the aquifer (Aiuppa et al., 2000a, Table 5). This
demonstrates that magmatic gas or hydrothermal water inputs
can enrich aquifers in Se. However, a number of hydrothermal
waters have relatively low Se concentrations with values below
the 10 lg/L WHO guideline for drinking water (Table 5). When
the geothermal fluids rise through the crust, the fluids separate
into steam and water as a response to pressure changes. Accord-
ingly, two end-members of geothermal fluids can be distinguished.
The direct discharge of the hot water phase causes springs with a
near-neutral pH and rich in Cl and silica. The steam can interact
with shallow aquifer water and cause acidic, SO24 -rich springs
(Webster and Nordstrom, 2003). In thermal groundwaters at Vul-
cano Island in Sicily Se is enriched in oxidized Cl-rich water and de-
pleted in Fe–S rich waters (Table 5, Aiuppa et al., 2000b). These
differences might be related to the presence of volatile Se com-
pounds under reducing conditions, which are lost during sampling
procedure (Conde and Sanz-Alaejos, 1997) or due to the immobil-
ity of reduced forms (Aiuppa et al., 2000b; Plant et al., 2003). In
contrast, Se(VI) is more mobile. This is different to As, as strong
As enrichments have been observed for reducing waters (Plant
et al., 2003).
4.3. Substrate interactions
Magmatic gas input (especially CO2) can enhance leaching from
the host rock into water (Giammanco et al., 1998; Brusca et al.,
2001). This has often been mentioned to be a controlling factor
in the trace element composition of volcanic aquifers (Giammanco
et al., 1998: Aiuppa et al., 2000a,b; Flaathen et al., 2009). Neverthe-
less, it is doubtful if this mechanism plays an important role in Se
distribution. As discussed in Section 3.2.2, total Se concentrations
in volcanic rocks are generally low. Tamari et al. (1990) showed
that for basalts and gabbros less than 10% of the total Se was mobi-
lized in contact with CO2-bubbling water. Flaathen et al. (2009)
confirm that very low amounts of Se are mobilized during CO2-rich
fluid–basalt interaction in groundwaters around Hekla volcano
(Table 5). Therefore, it seems that water–rock interaction is not
 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531 527

Table 5
Selenium concentrations in volcanic waters. For comparison: the WHO guideline for drinking water is 10 lg/L.

Location Water type Se concentration range (lg/L) References

USA Arizona, USA Thermal waters <2–256 Callender et al. (1977)
New Mexico, USA <2–16
Up to 300 Summers (1970)
10 Schulze-Makuch and Kennedy (2000)
Yellowstone, USA <1–9 Ball et al. (2008)
Latin America El Chicón, Mexico Thermal waters and crater lake 0.1–54 Taran et al. (2008)
Póas volcano, Costa Rica Crater spring nd–15 Martínez (2008)
Crater lake 1–500
Estado Mèrida, Venezuela Thermal waters 10.7 ± 0.1 Burguera et al. (1996)
Guadeloupe, Lesser Antilles nd–3 Floor, unpublished data
Africa Limpopo, South Africa nd–1.66 Olivier et al. (2008)
Europe Germany <2 Grosser and Heumann (1988)
Hungary <2 Bozsai and Karpati (1989)
Catalonia, Spain Most <1, one 620 De la Fuente and Alonso (1994)
Tenerife, Spain Groundwater nd–2.17 Rodríguez-Rodríguez et al. (2003)
Gran Canaria, Spain nd–1.35
Italy Thermal waters <0.002–0.15 Dall’Aglio et al. (1978)
Vulcano Island, Oxidized Thermal groundwater 1.5–237 Aiuppa et al. (2000b)
Sicily Italy Reduced 0.8–16
Ischia, Southern Italy 0.6–150.8 Daniele (2004)
Etna, Sicily Italy Groundwater 0.6–66.8 Aiuppa et al. (2000a)
Vesuvius, Italy nd–24.1 Aiuppa et al. (2005)
Reykjanes, Iceland Thermal water 0.46–0.83 Ólafsson and Riley (1978)
Hekla, Iceland Groundwater nd Flaathen et al. (2009)
Asia Patuha volcano, Indonesia Flank springs nd–1.87 Sriwana et al. (2000)
Crater lake 4.2–23
Asia unspecified Thermal waters 6 Robberecht and Van Grieken (1982)
Henan Province, China <0.1–1.2 Haiyan (2003)
China unspecified 1.33–1.38 Shaopu et al. (1990)
Oceania North Island, New Zealand <6 Hirner et al. (1998)
<1 Vega (2007)
Ocean East Pacific Rise <0.02 Von Damm et al. (1985)

nd – not detected.

Fig. 7. Overview of the processes controlling the Se content in groundwater.

an important process regarding Se enrichment in volcanic aquifers.
In contrast, Aiuppa et al. (2005) showed that Se is among the most
mobile elements during rock weathering at Vesuvius Volcano,
Italy.
On the other hand, the aquifer substrate can contain adsorption
sites on which dissolved Se is adsorbed (Kent et al., 1995: Basu
et al., 2007). Since selenite is more prone to adsorption than sele-
nate, this mechanism is expected, in particular, to immobilize
Se(IV). As far as the authors are aware, this process has not been
studied for Se in volcanic aquifers.
5. Conclusions and perspectives
In the present paper, the behavior of Se within volcanic systems
has been discussed. Although Se and S chemistry are often com-
pared, the existing data show the different behavior of Se com-
pared to S in volcanic environments. Also the comparison
between the chemical fate of As and Se seems to be invalid. More-
over, kinetics appears to be important. Therefore, more measure-
ments of Se concentration and speciation are required.
With the current data, a preliminary model can be constructed
for the Se cycle around volcanoes. However, there are several pro-
cesses which require more investigation in the near future. A more
precise model of Se cycling around volcanoes is not only important
for geochemists, but also needed to evaluate how the health of
populations is affected by volcanically-derived Se. Normally water
and food are assumed to be the most important sources for trace
elements. Therefore, the focus was on the processes causing poten-
tial Se enrichment in volcanic waters and affecting Se mobility in
soils.
528 G.H. Floor, G. Román-Ross / Applied Geochemistry 27 (2012) 517–531
Volcanic soils can be relatively enriched in Se, but with low
mobility. Although volcanic ash has been identified as an impor-
tant Se source, there is a lack of Se studies in fresh volcanic ash.
As they form the parent material for fertile volcanic soils exten-
sively used for agricultural activities, a better understanding of
Se in volcanic ash will be a key in constructing a model of the Se
cycle around volcanoes. Atmospheric deposition of Se present in
volcanic gases can be a Se flux to soils. The Se contents of gases
are correlated with the temperature, suggesting more volatiliza-
tion at higher temperatures. However, in the future a more precise
estimate of the volcanic Se flux is required, distinguishing different
geological settings. Moreover, investigations are needed to esti-
mate the relative importance of local deposition of Se and long-
range transport, for example towards oceans. At Mt. Etna it has
been shown that only a small percentage of Se is deposited locally.
More studies are needed to see if similar behavior is observed
around other volcanoes. Sorption is a key process for Se content
and mobility and is expected to be affected by processes such as di-
rect plume fumigation, acid rain interaction and weathering, but
this has barely been studied in natural conditions.
Although As in groundwater has received significant attention,
there is a lack of Se data within volcanic aquifers. Nevertheless,
there is evidence that Se can be strongly enriched in such waters.
Dissolution of the host rock does not seem to be a key factor.
Rather the input of geothermal waters seems to have a central role.
However, not all geothermal waters are enriched in Se. The mech-
anism for these differences in Se content should be investigated.
Acknowledgements
The lead author had many fruitful discussions with people
which contributed to this paper and I suppose most of them are
even not aware of that. To mention some of them, thanks to: Paul
Mason and Manfred van Bergen, because the idea for this paper
started in their offices; Sergio Calabrese and Walter D’Alessandro,
for providing me with their data and knowledge to help me to form
my ideas about Se behavior around Mt Etna, David Polya for his
support and Romain Millot, Paul Mason and Walter D’Alessandro
for critical reading of the manuscript. This is a contribution of
the AquaTRAIN Marie Curie Research Training Network (Contract
No. MRTN-CT-2006-035420) funded under the European Commis-
sion Sixth Framework Programme (2002–2006) Marie Curie Ac-
tions, Human Resources & Mobility Activity Area – Research
Training Networks. It reflects the views of the authors but not nec-
essarily those of the European Community, which is not liable for
any use that may be made of the information contained therein.
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