Arsenic Pollution Sources

Hemda Garelick(*), Huw Jones, Agnieszka Dybowska,

and Eugenia Valsami-Jones

I Introduction ................................................................................................................ 17
II Arsenic Speciation ..................................................................................................... 19
III Natural Sources .......................................................................................................... 20
A Arsenic Minerals in the Environment ................................................................. 20
B Arsenic Occurrence and Concentrations in Rock-Forming Minerals ................. 21
C Arsenic Occurrence and Concentrations in Rocks ............................................. 24
D Groundwater Contamination ............................................................................... 25
IV Anthropogenic Sources .............................................................................................. 41
A Modern and Historical Uses of Arsenic ............................................................. 41
B Mining as a Source of Arsenic in the Environment ........................................... 42
C Arsenic Emissions from Coal Burning ............................................................... 44
D Agricultural Use of Arsenic Compounds ........................................................... 46
E Wood Preserving Industry ................................................................................... 47
Summary ............................................................................................................................. 48
References .......................................................................................................................... 51

H. Garelick
Department of Natural Sciences, School of Health and Social Sciences, Middlesex University,
The Burroughs, London NW4 4BT, UK, e-mail: h.garelick@mdx.ac.uk

H. Jones
Institute of Social and Health Research, School of Health and Social Sciences, Middlesex
University, The Burroughs, London NW4 4BT, UK, e‐mail: h.jones@mdx.ac.uk
A. Dybowska
Department of Mineralogy, The Natural History Museum, Cromwell Road, London
SW7 5BD, UK

E. Valsami-Jones
Department of Mineralogy, The Natural History Museum, Cromwell Road, London
SW7 5BD, UK
I Introduction

Arsenic is a group V element, together with nitrogen, phosphorus, antimony and

bismuth. Its electronic configuration is [Ar]3d104s24p3; it has an atomic weight of
75 and commonly occurs naturally in two oxidation states, þ5, þ3, and, more
rarely, in the 0 or –3 state. Arsenic is classified as a metalloid in that it has a
chemical nature intermediate between that of metals and nonmetals.
The environmental presence of arsenic derives from both natural and anthropo-
genic sources. Many natural processes contribute to environmental background
concentrations of arsenic, including pedogenesis, dust storms, volcanic eruptions,
geothermal/hydrothermal activity, and forest fires.
Arsenic is widely distributed and is present in the Earth’s crust at an average
abundance of about 5 mg/kg. It occurs naturally in more than 200 mineral forms, of
which approximately 60% are arsenates, 20% sulfides and sulfosalts, with the remain-
ing 20% comprising arsenides, arsenites, oxides, silicates, and elemental arsenic
(Onishi 1969). The main mineral hosts of arsenic are arsenopyrite, orpiment, and
realgar; these are As(III) compounds that were formed under reducing, subsurface
conditions. When exposed to surface conditions of the Earth, such compounds are
oxidized to form pentavalent forms such as iron arsenate and, in calcareous soils, as
calcareous arsenolite. Arsenic, in its most recoverable form, occurs as a trace constit-
uent in iron pyrite, galena, and chalcopyrite (Goldschmidt 1954).
Arsenic contamination in the environment is causing a significant global human
health problem. It has been estimated that 60–100 million people, in India and
Bangladesh, are currently at risk of arsenic-related disease as a result of drinking
arsenic-contaminated waters (Ahmad 2001; Chakraborti et al. 2002). Arsenicosis is
also prevalent in certain areas of China including Shanxi, Xinjiang and Inner
Mongolia (Wang et al. 2000; Guo et al. 2001) and in Taiwan (Chen et al. 1999),
Vietnam (Berg et al. 2001) and Nepal (Neku and Tandukar 2003). In these areas of
endemic contamination, the major arsenic exposure pathway is believed to be from
drinking groundwater contaminated with natural (geological) sources of arsenic.
Similarly, geologically based arsenic contamination occurs in areas where geother-
mal fluids rich in arsenic enter surface waters, e.g., geothermally active regions of
Yellowstone National Park in the United States (US) and the Taupo Volcanic Zone
in New Zealand (Webster and Nordstrom 2003).
Significant amounts of arsenic are also introduced into the environment from
anthropogenic sources, among which metal mining and smelting are the most
important. Arsenic pollution of soils, sediments, surface waters, and groundwater
is reported from mining districts worldwide. Mining-related arsenic pollution has
been reported in the US (Moore and Woessner 2003), Australia (Smith et al. 2003),
Brazil (Borba et al. 2003), Northern Chile (Oyarzun et al. 2004), Czech Republic
(Filippi et al. 2004), Northern Peru (Bech et al. 1997), Taiwan (Shih and Lin 2003),
Hetao area of China (Zhang et al. 2002), Portugal (Patinha et al. 2004), Iran
(Modabberi and Moore 2004) and Mexico (Carillo-Chávez et al. 2000).
In some parts of the world, coal mining and burning of arsenic-rich coals have been
reported as an important source of arsenic contamination. Elevated concentrations of
arsenic from coal burning were reported in Guizhou Province (Dai et al. 2005) and
other areas of China (Sun 2004). The major exposure pathway for the population in
these areas of China has been linked to ingesting food contaminated by
arsenic deposited during burning of coal for cooking, crop drying and heating
(Liu et al. 2002).
Arsenic has also been introduced into the environment through extensive use of
arsenical compounds in agriculture. Until the 1970s, approximately 80% of arsenic
production was for the manufacture of pesticides in the form of simple inorganic salts.
Today, approximately 50% of arsenic production is dedicated to making pesticides,
with organic arsenic compounds comprising the more important forms (Matschullat
2000). Wood preservatives account for another 30% of the world arsenic market.
Arsenic has long been an important constituent of wood preservative formulations,
among which the most commonly used was chromated copper arsenate (CCA), which
contains 22% pure arsenic. Many sites used by the timber industry to treat lumber,
dispose of treated lumber, or use treated timber in construction (including children’s
playgrounds) have been contaminated with arsenic.

II Arsenic Speciation

Similar to other metalloids, arsenic exists in a number of forms or species. Both

bioavailability and toxicity are influenced by the type of arsenic species present.
The predominant form of arsenic, in solution, is controlled by both redox potential
(Eh) and pH. The stability of different arsenic aqueous species is shown as a
function of pH for As(III) (Fig. 1a) and As(V) (Fig. 1b).
The stability of arsenic is shown in a combined Eh–pH diagram (Fig. 2), which
allows predictions of the most stable form of arsenic. The system modeled also
includes oxygen, water, and sulfur. Soluble species and solids with solubilities
sufficiently low to occur in the system are illustrated. Regions of solubility less than
10–5.3 mol/L are shaded. From Fig. 2 it can be seen that arsenates are stable
(H3AsO4, H2AsO4–, HAsO42–, and AsO43–) at the high Eh values of oxygenated
(surface) waters. The following arsenite species occur at mildly reducing conditions
(i.e., low Eh values): H3AsO3, H2AsO3–, and HAsO32–. Arsenic oxides are too
soluble to appear on the diagram.
Under conditions in which S2– is stable in its reduced form, the minerals realgar
(AsS) and orpiment (As2S3) may be formed at pH values below rv5.5 and when Eh
values are near 0. HAsS2(aq) is stable at low pH in the presence of sulfide and
arsenic concentrations of up to 10–6.5 mol/L. At low Eh values As0, i.e., pure arsenic
in its metallic form, is stable and, at very low Eh values, arsine (AsH3) may be
formed.
Arsenic concentrations lower than 10–5.3 mol/L (Fig. 2) will diminish the pre-
dominance of solid species. Sulfide concentrations influence the boundary between
arsenic sulfides and arsenic metal. Organic species are not shown in Fig. 2 because
they are stable only at extremely low Eh values (Gupta and Chen 1978).
 Fig. 1 Arsenic (III and V) predominance diagrams. (Modified from Gupta and Chen 1978.)

Eh–pH diagrams provide no information on kinetics. The oxidation of arsenite to

arsenate in the presence of oxygen is reported to be very slow at neutral pH but
proceeds faster in strongly alkaline or acid solutions.

III Natural Sources

A Arsenic Minerals in the Environment

Arsenic occurs as a major constituent in more than 200 minerals including elemen-
tal arsenic, arsenides, sulfides, oxides, arsenates, and arsenites. The most commonly
found arsenic minerals are listed in Table 1.
Fig. 2 Redox (Eh)-pH diagram for arsenic at 25o C and 1 atm with total As =10–5.3 mol/L and total
S = 10–3 mol/L. Solid species depicted in parenthes-es in grey (shaded) area. (Adapted from
Ferguson and Gavis 1972.)

The greatest concentrations of these minerals occur in mineralized areas asso-

ciated with the presence of cadmium, lead, silver, gold, antimony, phosphorus,
tungsten and molybdenum. The most abundant arsenic ore mineral is arsenopyrite,
FeAsS, which contains 46% arsenic by mass.

B Arsenic Occurrence and

Concentrations in Rock-Forming
Minerals

Sulfide Minerals

Arsenic is present in varying concentrations in many common rock-forming miner-

als. The typical ranges of recorded concentrations are presented in Table 2. Because
the chemistry of arsenic has some similarities to that of sulfur, the greatest con-
centrations of the element tend to occur in sulfide minerals, of which pyrite is the
most abundant. Concentrations in pyrite, chalcopyrite, galena and marcasite can be
quite variable, even within a given grain, but in some cases exceed 10% by mass
(Smedley and Kinniburgh 2002).
Pyrite can be formed in low-temperature sedimentary environments under re-
ducing conditions. It is present in the sediments of many rivers, lakes, and oceans
and also occurs in many aquifers. Pyrite commonly forms preferentially in zones of
intense reduction such as around buried plant roots or other nuclei of decomposing
organic matter. Pyrite is not stable in aerobic systems and oxidizes to Fe oxides,
with the release of large amounts of sulfate ions, acidity and associated trace
constituents, including arsenic. The presence of pyrite as a minor constituent in
Table 1 Arsenic minerals occurring in nature
Mineral Composition Occurrence
Native arsenic As Hydrothermal veins and deposits that contain
other arsenic minerals
Niccolite NiAs A minor component of Ni-Cu ores in high-
temperature hydrothermal veins
Safflorite (Co,Fe)As2 Hydrothermal veins
Realgar AsS Vein deposits often associated with orpiment,
clays, and limestones, deposits from hot
springs
Orpiment As2S3 Hydrothermal veins, hot springs, volcanic
sublimation products
Cobaltite CoAsS Medium-temperature hydrothermal deposits,
metamorphic rocks
Arsenopyrite FeAsS The most abundant arsenic mineral,
dominantly in veins of hydrothermal
origin, found in pegmatites, high-
temperature gold, quartz and tin veins, in
contact metamorphic sulfide deposits, also
in gneisses, schists and other metamorphic
rocks
Arsenian pyrite Fe(As,S)2 Hydrothermal veins, accessory mineral in
igneous rocks, pegmatites and contact
metamorphic deposits
Lollingite FeAs2 Mesothermal deposits associated with other
sulfides and calcite gaunge
Tennantite (Cu, Fe)12As4S13 Hydrothermal veins and contact metamorphic
deposits
Enargite Cu3AsS4 Hydrothermal vein deposits formed at
medium temperatures
Arsenolite As2O3 Secondary mineral formed by oxidation of
FeAsS, native arsenic and other arsenic
minerals
Scorodite FeAsO4·2H2O Secondary mineral formed by oxidation of
arsenic-bearing sulfides
Annabergite (Ni,Co)3(AsO4)2·8H2O Secondary mineral formed by the alteration of
Co-Ni-bearing arsenides and sulfides, in
the oxidized zone of hydrothermal mineral
deposits
Hoernesite Mg3(AsO4)2·H2O Secondary mineral, in limestone blocks and
volcanic tuff
Symplesite Fe2+3(AsO4)2·8H2O Secondary mineral in the oxidized zone of
some arsenic-rich hydrothermal mineral
deposits
Conichalcite CaCu(AsO4)OH Secondary mineral in the oxidized zone of Cu
deposits, an alteration product of enargite
Pharmacosiderite KFe4(AsO4)3(OH)4·6‐7H2O Secondary mineral formed by oxidation of
FeAsS and other arsenic-bearing sulfides
Source: Modified from Goldschmidt (1954); Anthony et al. (1990); Azcue and Nriagu (1994);
Anthony et al. (2000); Smedley and Kinniburgh (2002).
Table 2 Typical arsenic concentrations in rock-forming minerals
Mineral Arsenic concentration (mg/kg)
Sulfide minerals
Arsenopyrite 46% by mass
Pyrite 100–77,000
Pyrrhotite 5–100
Marcasite 20–126,000
Galena 5–10,000
Sphalerite 5–17,000
Chalcopyrite 10–5,000
Oxide minerals
Haematite Up to 160
Fe oxide (undifferentiated) Up to 2,000
Fe III oxyhydroxide Up to 76,000
Magnetite 2.7–41
Ilmenite <1
Silicate minerals
Quartz 0.4–1.3
Feldspar <0.1–2.1
Pyroxene 0.08–1.17
Carbonates
Calcite 1–8
Dolomite <3
Siderite <3
Other minerals
Apatite <1–1,000
Fluorite <2
Source: From Smedley and Kinniburgh (2002).

sulfide-rich coals is ultimately responsible for arsenic pollution in the vicinity of

coal mines and in areas of intensive coal burning.

Oxide Minerals

High arsenic concentrations are also found in many oxide minerals and hydrous metal
oxides, either as part of the mineral structure or as sorbed species. Concentrations in
iron oxides can attain weight percent values, particularly where they form as oxidation
products of primary iron sulfide minerals, which have abundant arsenic. Adsorption of
arsenate to hydrous iron oxides is particularly strong (Goldberg 1986; Manning and
Goldberg 1996; Hiemstra and van Riemsdijk 1996). Adsorption to hydrous aluminum
and manganese oxides may also be important, if these oxides are present in quantity
(Peterson and Carpenter 1983; Brannon and Patrick 1987). Arsenic may also sorb to the
edges of clays and on the surface of calcite (Goldberg and Glaubig 1988), a common
mineral in many sediments. However, all these loadings are much smaller on a weight
basis compared to arsenic loadings on iron oxides.
Phosphate and Other Minerals

Arsenic concentrations in phosphate minerals are variable but can reach high values,
up to 1000 mg/kg in apatite (Smedley and Kinniburgh 2002). However, phosphate
minerals are much less abundant than oxide minerals and thus make a correspond-
ingly smaller contribution to the arsenic loading of most sediments. Arsenic can also
substitute for Si4þ, Al3þ, Fe3þ, and Ti4þ ions in many mineral structures and is
therefore present in many other rock-forming minerals, although at much lower
concentrations. Most common silicate minerals contain approximately 1 mg/kg or
less arsenic, and carbonate minerals usually contain less than 10 mg/kg of arsenic.
Comprehensive data on arsenic concentrations in common rock forming minerals
are presented by Smedley and Kinniburgh (2002).

C Arsenic Occurrence and Concentrations in Rocks

Igneous Rocks

Arsenic concentrations in igneous rocks are usually low, and there is relatively little
difference between concentrations in different igneous rock types. Among igneous
rocks, volcanic rocks (especially ashes) are often implicated in the generation of
high aqueous arsenic concentrations. Arsenic concentrations in most metamorphic
rocks are similar to the average crust concentrations of 5 mg/kg or less. Higher
arsenic concentrations are typically associated with pelitic rocks (slates, phyllites)
with average values of arsenic of rv18 mg/kg (Goldschmidt 1954).

Sedimentary Rocks

The concentration of arsenic in sedimentary rocks is typically in the range 5–10 mg/kg
(Webster 1999), and average sediment concentrations are enriched in arsenic
relative to igneous rocks. Sands and sandstones tend to have the lowest concen-
trations, reflecting the low arsenic concentrations of their dominant mineral
components, i.e., quartz and feldspars. The average sandstone arsenic concentra-
tion is approximately 4 mg/kg. Argillaceous deposits have a broader range and
higher average arsenic concentration than do sandstones, with a typical value of
approximately 13 mg/kg (Ure and Berrow 1982). The higher values reflect the
larger proportion of sulfide minerals, oxides, organic matter and clays. Black
shales have relatively high arsenic concentrations, mainly because of their en-
hanced pyrite content. Arsenic concentrations in coals and bituminous deposits
are variable but often high. Some coal samples have been found with extremely
high arsenic concentrations, up to 35,000 mg/kg (Belkin et al. 2000), although
generally low concentrations (2.5–17 mg/kg) were reported by Palmer and Klizas
(1997). Carbonate rocks typically have low concentrations, reflecting arsenic con-
centrations of their constituent minerals (3 mg/kg). Some of the highest observed
arsenic concentrations are found in ironstones and Fe-rich rocks; concentrations up
to 2900 mg/kg were reported by Boyle and Jonasson (1973). Phosphorites are also
relatively enriched in arsenic, with reported values of up to 400 mg/kg (Smedley
and Kinniburgh 2002).

D Groundwater Contamination

Occurrence and Sources

The occurrence, origin and mobility of arsenic in groundwater are primarily

influenced by local geology, hydrogeology, and geochemistry of the aquifer sedi-
ments. Elevated arsenic concentrations may arise from natural weathering and
leaching of arsenic from geological materials containing arsenic (e.g., arsenopyrite,
base metal sulfides, realgar, orpiment), and drainage from thermal springs and
geysers, as well as atmospheric deposition.
Arsenic sulfides, arsenic-rich pyrite, and arsenic-rich iron oxyhydroxides are the
most commonly found natural sources of arsenic contamination in groundwater
worldwide. Various studies have suggested that the primary source of arsenic in
groundwater derives from dissolution of arsenic-bearing sulfide minerals, or de-
sorption from, or reductive dissolution of, arsenic-rich Fe oxides.
Arsenic contamination of groundwater from natural sources worldwide has been
attributed to several geochemical processes. These pathways include oxidation of
arsenic-bearing sulfides, desorption of arsenic from oxides and hydroxides, reductive
dissolution of arsenic from oxides/hydroxides, release of arsenic from geothermal
waters and evaporative concentration (Welch et al. 2000), and leaching of arsenic from
sulfides by carbonate (Kim et al. 2000). Because these processes are complex, idengi-
fication of the mechanism responsible for contamination in a particular case is often
difficult. At times, despite the natural origins of contamination (e.g., the presence of
arsenic-rich minerals) natural processes of arsenic leaching from the host minerals
have been significantly enhanced by anthropogenic activities such as mining.
In Bangladesh and West Bengal, the alluvial Ganges aquifers used for public
water supplies are polluted with naturally occurring arsenic. Several researchers
attribute arsenic contamination in this region directly to oxidation of arsenic-rich
pyrite in the aquifer sediments as atmospheric oxygen invades the aquifer in
response to lowering of the water level by abstraction (Das et al.1996; Saha and
Chakrabarti 1995; Chowdhury et al. 1999; Mandal et al. 1996).
Other researchers suggest that arsenic contamination comes from the reductive
dissolution of arsenic-rich iron oxyhydroxides, which are derived from weathering
of base metal sulfides (Nickson et al. 1998, 2000; Chowdhury et al. 1999; Bhatta-
charya et al. 1997; McArthur et al. 2001).
Further pathways for release of arsenic into drinking water have been described
by Islam et al. (2004). These workers have shown microbial mediation to be a
possible mechanism for reductive dissolution of arsenic-bearing hydrated ferric
oxides. Other important factors that potentially influence the occurrence of arsenic
in water include the presence of organic carbon species that correlate with the
arsenic levels found in sand and gravel glacial aquifers in central Illinois (Kelly
et al. 2005).
Further mechanisms of arsenic release include requires indenting the oxidation
of the arsenic-bearing sulfides pyrite and marcasite. This mechanism was the source
of arsenic contamination in groundwater from a sandstone aquifer in the Fox River
Valley in eastern Wisconsin, USA (Schreiber et al. 2003).
Pyrite, with arsenic-rich domains [up to 8.5 arsenic weight percent (wt.%)], was
identified in the Mississippian Marshall Sandstone, the principal bedrock aquifer
in the region. Arsenic-rich Fe oxyhydroxides (up to 0.7 wt.% arsenic) were
also identified in samples of tills derived from the Marshall Sandstone. Depending
on redox conditions, Fe oxyhydroxides provide a potential source of arsenic in
groundwater. Kolker et al. (2003) concluded that three different mechanisms were
responsible for widespread arsenic mobilization in eastern and southeastern Michi-
gan groundwaters: weathering of pyrite in tills derived from the Marshall Sand-
stone, reductive dissolution of Fe oxyhydroxides in tills, and potential pyrite
oxidation in bedrock aquifers.
Other data reported in the literature on arsenic contamination of groundwater
derived from natural sources are summarized in Table 3.
Therefore, the major hypothesized arsenic release mechanisms include sulfide
oxidation and reductive dissolution of As-bearing phases (Fe-Mn oxides), as well as
microbially enhanced reductive dissolution. In addition, on a local scale, factors
such as anion competition (PO43– leaching from fertilizers) enhance mobilization.
Many high-concentration arsenic-bearing groundwaters exist in areas where only
moderate levels of arsenic occur in the host formation (and often within normal range).
Stuben et al. (2003) suggest that the mechanism of solubilization is more important
than source type in accounting for such behavior. The mechanism for solubilizing
arsenic from relatively low content host formations to create high arsenic levels in
groundwater is often related to redox conditions and pH of the water, as previously
described. The presence of peat deposits in sediments may contribute to arsenic
release, because peat degradation creates acidic and reducing conditions, and, in
addition, soluble organics may compete with arsenic for sorption sites.

Arsenic Enrichment in Areas of Geothermal Activity

Arsenic is a ubiquitous component of active and fossil geothermal systems. A sum-

mary of arsenic concentrations in selected geothermal systems is provided in
Table 3 Geographic locations, levels, and sources of naturally enriched arsenic contamination in groundwater

Arsenic Pollution Sources

Location Arsenic concentrations N Identified source Arsenic Mobilization mechanism Reference
range/mean (mg/L) concentration
(source material)
(mg/kg)

USA, <0.0003–180 992 Arsenopyrite (FeAsS), Dissolution of Peters and Blum

New Hampshire westerveldite (FeAs) nanocrystalline As- 1999;
bearing phases Utsunomiya
As-enriched pegmatite Pegmatites: Rock–water interaction: et al. 2003
dikes in the bedrock up to 60 dissolution from
pegmatites
USA, From 5 to >50 88 Meta-sedimentary Meta-sedimentary ND Ayotte et al. 2003
New England Highest detected bedrock Highest bedrock: 3–40
in metamorphosed arsenic in groundwater
marine sediments. (GW) from
29% wells >10, metamorphosed
14% >20 and 4% marine sediments
>50 g/L variable calcareous,
with As present in
sulfide minerals
(pyrite, pyrrhotite)
1–380 1,572 NA 0.2–554 ND Robinson and
Ayotte 2006
USA, 10–210 41 Supai and Verde NA ND Foust et al. 2004
(Verde Valley) formations, organic As
Central Arizona complexes common:
arsenobetaine,
dimethylarsinic acid,
As-glutathione
complex
(continued)

27
 28
Table 3 (continued)
Location Arsenic concentrations N Identified source Arsenic Mobilization mechanism Reference
range/mean (mg/L) concentration
(source material)
(mg/kg)

USA, 0.5–278 73 Marshall Formation and NA Reductive dissolution of Kim et al. 2002
Michigan Coldwater shale, both arsenic-rich iron
of Mississipian age: hydroxide/
arsenic-rich pyrite, oxyhydroxide
arsenopyrite and Dissolution of arsenic
glacial deposits sulfide minerals
(arsenic adsorbed on
Fe oxyhydroxides)
As-rich pyrite: up Carbonation of arsenic Kolker et al. 2003
to 8.5 wt% sulfides, reduction of
As sorbed in the
aquifer
FeOOH: up to 0.7 Weathering of arsenic
wt% As pyrite
1–1310 Most common 262 Arsenopyrite and As-rich NA Carbonation of sulfide Slotnick et al. 2003
levels: 5–50 pyrite present in minerals
Marshall sandstone Arsenopyrite
oxidation primary
mechanism for As
release in the vadose

H. Garelick et al.
zone but not the
primary factor
controlling As in
groundwater
 Arsenic Pollution Sources
USA, 0.3–166 (Schreiber 5 Sulfide-bearing horizon in NA Sulfide oxidation Schreiber et al.
Wisconsin et al. 2000) sandstone aquifer; As (atmospheric oxygen 2000
occurs in pyrite, introduced through
marcasite, but not well boreholes,
arsenopyrite, also extensive
As-rich FeOOH groundwater
withdrawal exposes
sulfide-bearing
horizon to oxygen)
Taiwan, 470–897; mean, 54 Likely to be pyritic NA Oxidation of Chen et al. 1994
South-West 671 ± 149 material or black shale pyrigiferous material
0–1000 NA NA NA Reductive dissolution of Wang et al. 2007
As-rich Fe
oxyhydroxides
20–1200; mean, 395 22 NA NA Pyrite oxidation and Lin et al. 2006
siderite dissolution
Taiwan, 10–1800 (mean = 500) 126 NA NA ND Kuo 1968
North-East Mean = 135 377 NA NA ND Hsu et al. 1997
<0.15–3590 3,900 NA NA ND Yang et al. 2003
(median As, from
0.15 to 140)
India, 50–100 in 20% <1,000 As associated with Fe NA ND Das et al. 1994
West Bengal samples, 100–500 pyrites
in 60% samples,
500–1000 in 15%
samples, and
>1000 in 5%
samples
(continued)

29
 30
Location Arsenic concentrations N Identified source Arsenic Mobilization mechanism Reference
range/mean (mg/L) concentration
(source material)
(mg/kg)
50–1250 1,420 Iron pyrites in arsenic-rich Aquifer sediments: Oxidation of As-rich Das et al. 1996
layers in the alluvium 1–31 mg/kg As, pyrite, arsenopyrite
alongside River Ganga max. 125 and (lowering of
196 mg/kg water )
0.74–470 21 As-rich base metal As sorbed to Microbially mediated Stuben et al. 2003
deposits, As-bearing FeOOH: reductive
pyrite 300–500 dissolution of Fe-
Mnoxyhydroxides
(changing redox
conditions, presence
of organic material)
Not clear what drives
creation of reducing
conditions (flooding,
biodegradation of
buried peat deposits,
human-related
activities, pumping,
land use, sewage
pollution, or intensive
GW exploitation that
promotes movement
of reducing GW in the

H. Garelick et al.
aquifer
 Arsenic Pollution Sources
50–3700 4,800 NA NA ND Chowdhury et al.
(mean, 290) 1997
Mean, 200; maximum, 20,000 As in pyrite 11–78 (As in bore- Oxidation of As- Mandal et al. 1996
3700 hole sediments) enriched pyrite
caused by high GW
withdrawal
10–590 NA As in the silty clay and Bhattacharya et al.
sandy layers of the 1997
aquifer sediments –
occurs as coatings on
mineral grains,
occasionally also as
arsenopyrite
37.5–450 NA As sorbed on amorphous Total As in Anion exchange of Charlet et al. 2007
Fe oxides, carbonates sediment sorbed arsenate and
and micas sample: 3.0 aqueous HCO3– (and
(34%) to a smaller extent
associated with PO4 3–) Arsenic
amorphous release from the
FeIII oxides and dissolution of As-
19% with enriched carbonates
carbonates/acid
volatile
sulfides)
(continued)

31
 32
Location Arsenic concentrations N Identified source Arsenic Mobilization mechanism Reference
range/mean (mg/L) concentration
(source material)
(mg/kg)
Bangladesh <0.5–2500 3,534 Holocene/alluvial deltaic Sediments: 1–30 Microbial dissolution of BGS/DPHE 2001
sediments - micaceous max. 196 mg/kg FeOOH (reducing McArthur et al.
quartzo-feldspathic As (where conditions created 2001
sands Arsenic rich pyrite locally mainly by microbial Nickson et al.
FeOOH occurred and degradation of buried 1998
scavenged peat deposits and Chowdhury
arsenic) organic waste) et al. 1999
Distribution of As
pollution controlled
by buried peat
deposits rather than
distribution of As in
aquifer sediments
Contamination
related to well depths
(hand-dug wells
mostly unpolluted,
30–45 m the highest
pollution level)
0.7–640 112 Friesbie et al. 2002
<10–332 45 As in sediments: Reductive dissolution of Nickson et al. 2000
9–28 FeOOH driven by
microbial

H. Garelick et al.
degradation of
sedimentary organic
matter
 Arsenic Pollution Sources
Mexico, Mean, 404 Geological; not specified NA ND Del Razo et al. 1994
Lagunera region
Mexico, Maximum, 53.5 53 Lacustrine sediments NA ND Planer-Friedrich
Rioverde basin Majority of (chalk and gypsum) et al. 2001
samples, 5–10
Chile, <100 to >800 23 Volcanic sediments, NA ND Caceres et al. 1992
Northern region minerals and soil
Argentina, 100–316; maximum, NA Loess and loess-like Loess sediments: ND Astolfi et al. 1981
South-east 3810 sediments (mostly 5.5–37.3
Pampa Province pyroclastic material),
of Cordoba and rhyolitic volcanic
glass
Volcanic glass: Nicolli et al. 1989
6.8–10.4
Argentina, 470–770 NA Tertiary-Quaternary NA ND De Sastre et al.
North-west volcanic deposits, 1992
Salta and Jujay post-volcanic geysers
provinces and thermal springs
Levels in thermal
springs: 50-9900 mg/L
Argentina, 10–593 Mean, 108 66 Loess and loess like NA Not specified Farias et al. 2003
Pampean Plain sediments
Argentina, Up to 5300 NA Quaternary loess aquifer Loess sediments: Desorption from Fe Smedley et al. 2005
Central As associated with Fe 3–18 (mean = 8) oxides caused by
La Pampa oxides and Mn oxides high pH and
province competition
3–
with
PO4 and HCO3–
(continued)

33
 34
Table 3 (continued)
Location Arsenic concentrations N Identified source Arsenic Mobilization mechanism Reference
range/mean (mg/L) concentration
(source material)
(mg/kg)
Vietnam, 1–3050 Mean, 159 196 Quaternary formation Sediments: 0.6–33 Reductive dissolution Berg et al. 2001
Red River Basin with sediments beds of
Pleistocene and
Holocene age (with
peat deposits) As
present in iron Oxides
phases, not abundant
in sulphide phases
Japan, 1–293 67 No detailed source NA Elution of arsenite/ Kondo et al. 1999
southern region identified arsenate by anion
of Fukuoka exchange with OH–
Prefecture and reductive
dissolution of As-
bearing phases
Japan, Chicugo Plain, 11–370 11,673 Quaternary sediments Sediments: Dissolved from the host Shimada 1996
Kumamoto, (mud, sand, gravel and Chicugo plain, formation, desorption
Fukui, Takatsuki clay-silt layers, 0.8–33 from Fe oxides by
Kumamoto Plain, 46 volcanic ash) Arsenic Kumamoto Plain, reductive dissolution
5–66 sorbed on Fe-oxides <0.5–20.6 and competing ions
and clay minerals Fukui Plain, <0.5– effect (PO4 3–)

H. Garelick et al.
Fukui and Takatsuki
Plains, 11–60 14 Takatsuki Stagnant
Plain, 2–386 groundwater with
reducing and alkaline
conditions
accelerated As
release
 Arsenic Pollution Sources
China, <1 to 1480 73 Quaternary lacustrine and As sorbed on Reductive dissolution of Smedley et al. 2003
Inner Mongolia, fluvial sediments FeOOH: 3–29 oxides, competing
northern China Arsenic associated ions 3–effect (mainly
(Huhhot basin) with Fe-oxides PO4 ), diagenetic
evolution of Fe
oxides
(transformation from
amorphous to
crystalline forms
Cambodia 10–500 100 Quaternary alluvial NA Microbially mediated Smedley 2003
(Mekong Valley) sediments (most likely dissolution of As-
As sorbed to FeOOH) bearing FeOOH
Mean of 210 ± 310 >1,000 Holocene and Quaternary NA Microbially mediated Polya et al. 2004,
and a maximum of sediments (As in Fe reductive dissolution 2005; Charlet
1700 bearing phases, of As-rich hydrous Fe and Polya 2006
carbonates, sulfides, oxides (source of
and in organic matter) organic carbon
driving these
microbial processes
disputed, e.g., peat
layers within the
sediments, surface-
derived organic
matter)
1–1610 Mean, 217 200 Holocene sediments Reductive dissolution of As- Berg et al. 2007
bearing Fe phases in
aquifer sediments
(continued)

35
Table 3 (continued)

36
Location Arsenic concentrations N Identified source Arsenic Mobilization mechanism Reference
range/mean (mg/L) concentration
(source material)
(mg/kg)
Australia, Up to 7000 68 Pyritic sediments As-rich pyrite, Oxidation of pyritic Appleyard et al.
Western Australia 0.5%–0.7% sediments exposed as 2006
Pyritic a result of reduced
sediments, 300 rainfall, increased
groundwater
abstraction, and
dewatering carried
out during urban
construction
Hungary, 0–300 (mean, 51) (but NA Pleistocene sediments Pleistocene Microbially mediated Versanyi and
Pannonian Basin samples found with with arsenic sorbed on sediments: reductive dissolution Kovacs 2006
up to 2250) amorphous Fe oxides 0.09–10.8 of Fe oxyhydroxides,
(extracted with mobilization with
hydroxylamine organic ligands from
hydrochloride) the sediment organic
matter
Spain, 0.42–614 (mean, 41) 514 Organic-rich sediments of Below detection Desorption from Fe, Mn Gomez et al. 2006
Duero Cenozoic the Middle Miocene limit: 337 oxides and organic
Basin clayey Zaratan facies (mean, 23) matter under
(As present in Fe and oxidizing and
Mn oxides, authigenic alkaline conditions;
pyrite,Ti-Fe oxides, oxidation and
phyllosilicates and dissolution of pyrite

H. Garelick et al.
organomineral
compounds)
N, number of measurements; where several concentration ranges were reported for an area, the appropriate reference is provided for each reported range.
NA, not available; ND, not discussed.
Table 4. Such systems occur throughout the world in one of three general tectonic
settings (Webster and Nordstrom 2003):
lNear tectonic plate boundaries [e.g., edge of the Pacific Plate: geothermal fields in
New Zealand, Papua (New Guinea), Philippines, Indonesia, Japan, Kamchatka,
Alaska, Western USA, Mexico, Central America, and Chile].
l Intraplate hot spots: Hawaii, Yellowstone (USA), and the Azores.

l Rift zones, where the tectonic plates diverge: Gregory Rift Valley in Ethiopia,

Kenya, and Tanzania, the Rio Grande Rift Valley in Colorado and New Mexico
(USA), and the rift system in Iceland.
Many geothermal systems have been, or will be, developed to generate energy
from steam and hot water reservoirs beneath the earth’s surface. Therefore, the
potential exists for further mobilization and exposure to arsenic from such
development.
Arsenic is an important trace constituent in geothermal fluids, where concentra-
tions range from less than 0.1 to nearly 50 mg/kg (Ballantyne and Moore 1988).
These wide variations can be attributed to local water physico-chemistry (in particu-
lar, low- or high-sulfide fluids), salinity, temperature, and host rock composition.
Laboratory experiments have demonstrated that arsenic in geothermal fluids may
originate from rock leaching (Criaud and Fouillac 1989). It has also been postulated
that some of the arsenic may be of magmatic origin (Ballantyne and Moore 1988).
Arsenic occurs predominantly in pyrite, or is associated with Fe oxides in geother-
mally altered rocks; up to 3.8 wt.% arsenic was reported in pyrite originating from hot
springs (Ballantyne and Moore 1988). Arsenic minerals are uncommon in geothermal
reservoir rocks. However, a variety of these occur in hot spring deposits including
orpiment, realgar, As-rich marcasite, and As-rich stibnite (Ballantyne and Moore
1988). Arsenic (III) predominates in geothermal water directly discharged from an
underground reservoir, although it is gradually oxidized to As (V) on the surface. In
acid sulfate- and bicarbonate-type springs, As (V) is a predominant species (Ballan-
tyne and Moore 1988). Arsenic (III) can be oxidized to arsenic (V) when a rising
geothermal fluid is exposed to atmospheric oxygen or is mixed with another oxidizing
fluid such as shallow groundwater. In geothermal waters containing sulfide or tiosul-
fate, arsenic (III) is preserved until the reduced sulfur is oxidized or volatilized
(Webster and Nordstrom 2003). The source of arsenic in geothermal fluids, arsenic
speciation, and the fate of arsenic from geothermal fluids are discussed further by
Ballantyne and Moore (1988) and Webster and Nordstrom (2003).
Geothermal fluids commonly contain elevated arsenic concentrations. A list of
these, grouped by geographic location, is presented in Table 4. Part of the arsenic in
this matrix is volatilized and released into the atmosphere. Although arsenic speciation
in geothermal fluids has been extensively studied, there is a paucity of information on
volatile arsenic in geothermal fields. However, Planer-Friedrich et al. (2006) have
attempted the quangification of total volatile arsenic and have described its specia-
tion in one of the world’s best known geothermal fields, namely Yellowstone
National Park (USA). They measured concentrations of 0.5–200 mg/L at the surface
of the hot springs and identified chloro- and thioarsine species, which have not been
Table 4 Arsenic concentration ranges in hot springs of various regions.
Country Geothermal field Arsenic concentration Reference
(mg/L)
United States Yellowstone National 160–3600 (hot springs) Stauffer and
(USA) Park Thomson 1984
Lassen Peak, California 2200–24300 (thermal
waters)

Geyser Bight, Umnak up to 3800 White et al. 1963

Island, Alaska

Valles Caldera, New 21–2400 (spring water) Criaud and Fouillac

Mexico 1989

Honey Lake Basin, up to 2600 Welch et al. 1988

California
Coso Hot Springs, up to 7500
California
Imperial Valley, up to 15,000
California
Long Valley, California up to 2500
Steamboat Springs, up to 2700
Nevada

New Zealand Taupo Volcanic Zone, 0.71–6.5 mg/kg Webster 1990

Waiotapu and 0.64–1.34 mg/kg
Rotokawa (hot spring waters)
geothermal fields

Kawerau geothermal 20–30 (river Tarawera Mroczek 2005

field receiving input of
geothermal fluids)

Wairakei, Broadlands, 3800 (groundwater Robinson et al. 1995

Orakei Korako and from Waikarei) up
Atiamuri geothermal to 121 (river and
fields lake waters with
inputs from
geothermal fields)

Bulgaria Southwestern Bulgaria 3–9.8 Criaud and Fouillac

1989
France Chassolle group, 240–509
Cezallier

Dominica Wooten Waven Valley 0.3–775

of Desolation <0.3–650

Mexico Los Azufres, Mexico 5–30,000 (drainage Birkle and Merkel

water from different 2000
evaporation basins)
8-8200 (springs and
surface runoffs in
and outside
geothermal field)
 19,000 (geothermal Birkle and Merkel
brine) 160 mg/kg 2002
(max in pond
sediments) 24,000
(pond water)

Philippines Mt Apo Philippines 31–6200 Webster 1999

(hot spring water)

Japan Kyushu geothermal 700–4600 (geothermal Yokoyama

fields water) et al. 1993

Russia Kamchatka 2.0–3.6 mg/kg Karpov and Naboko

1990

100–5900 (thermal White et al. 1963

waters)

Italy Ischia island 0.5–1558 (shallow Lima et al. 2003

thermal wells and
thermal spring
waters)

Phlegrean Fields, 0.1–6940 Aiuppa et al. 2003

Volcano island, Mt (groundwaters)
Etna, Mt Vesuvius

Iceland Nafmafjall, Krafa high- 0.001–0.048 mg/kg Arnorrson and

temperature fields Linvall 2001

50–120 (thermal White et al. 1963

waters)

Chile El Tatio system 45,000–50,000 Ellis and Mahon

(Antofagasta region) 1977

Germany Wiesbaden spa (thermal 37–110 (public thermal Schwenzer

springs) water taps) et al. 2001

Turkey Geothermal fields in 130–280 (geothermal Baba and

Turkey: Alibeykoy water) Armannsson
(Canakkale), 2006
Kızılkoy (Balıkesir),
Kukurtlu (Bursa),
Cumali-Seferihisar
(Izmir), Doganbey-
Seferihisar (Izmir),
and Balcova (Izmir)

previously documented in the natural environment. The toxicity, mobility, and

degradation products of these arsenic species are not known, nor are the processes
that lead to their formation, although microbial transformation is implicated.
 Volcanic degassing also represents an important natural source of arsenic release
to shallow aqueous systems. Groundwaters circulating in active volcanic areas may
contain appreciable amounts of arsenic as a result of their interaction with deep-
rising fluids or leaching of ore deposits (Welch et al. 1988; Yokoyama et al. 1993;
Aiuppa et al. 2003).
Volcanic aquifers often constitute an important water resource for people living
near them. For example, the Etnean aquifer represents the main water supply for
drinking and agricultural purposes for about 1 million people living in eastern
Sicily, Italy (Aiuppa et al. 2003). The potential therefore exists for exposure of
these communities to elevated arsenic concentrations under conditions favorable to
its release to potable water supplies.
In general, surface waters are more susceptible to arsenic contamination than
corresponding groundwaters in areas of geothermal systems. Mixing of geothermal
waters with groundwater and surface waters is known to increase the arsenic con-
centrations in the latter (Webster 1999; Robinson et al. 1995). Some soil contamina-
tion also occurs in such areas, but tends to be local; in contrast, water flowing through
the surface and subsurface catchments of the geothermally active areas may transport
arsenic beyond the boundary of the geothermal field. Geothermal waters also affect
the arsenic content of plants in the vicinity of hot springs (Loppi and Bonini 2000).
Arsenic levels and geothermal activity are so closely related that arsenic anomalies in
soils and waters have been used as geochemical indicators for geothermal areas
(Bingqiu et al. 1986; Shiikawa 1983). Elevated arsenic concentrations in surface
waters, which may be locally used for drinking and irrigation, and accumulation of
arsenic in edible aquatic plants in river systems receiving geothermal fluids, consti-
tute the main exposure pathways for local populations in geothermally active areas.
The solubility of arsenic entering surface waters from geothermal fluids is affect-
ed by the extent of arsenic adsorption onto particle surfaces. Under the higher rock:
water ratios present in aquifers, arsenic concentrations may be reduced through
adsorption onto clays and other silicate surfaces, particularly in the presence of
Fe-Mn oxides. Appropriate pH conditions, as determined by the pH of the zero
point of charge (ZPC) of the available sorbing surfaces (Manning and Goldberg
1997), facilitate this process. In addition, the solubility of geothermally derived
arsenic may be limited by the precipitation of orpiment if high sulfide concentrations
accompany arsenic in geothermal fluids (Ballantyne and Moore 1988).
Little can be done to control arsenic inputs from geothermal springs; indeed,
future geothermal power developments may increase amounts of arsenic entering the
aquatic biosphere. Hazards may increase as geothermal fields are more often tapped
for power generation because of the corresponding increases in rates and volumes of
geothermal fluids reaching the surface. Disposal of wastewaters from operations of
such plants will exacerbate the problem because of arsenic enrichment of the
wastewater. In developed geothermal fields, wastewater is reinjected into the field
to avoid environmental pollution. Reinjection is expensive and reduces productivity
of the field. Therefore, where not required by law, wastewaters are discharged into
the local environment, resulting in contamination of soils and waterways. Examples
of such problems are provided in Mroczek (2005) and Baba and Ármannsson (2006).
IV Anthropogenic Sources

Anthropogenic arsenic sources include the following:

l Metal acquisition and processing: Ore production and processing, ore melting
and roasting in nonferrous smelters, metal melting in iron works; metal treat-
ment admixture in bronze, lead, and copper alloy production; galvanizing
processes; ammunition factories; battery plate production.
l Energy: High-temperature oil and coal burning; and operation of power plants.

l Agriculture and livestock: Use of arsenical insecticides, algaecides, and defoli-

ants; debarking trees, soil sterilants, feed additives, cattle and ship dips, intense
husbandry disinfectants; compost and dung surplus (arsenic from animal feeding).
l Wood preservatives.

l Medicine: Pharmaceutical substances: antisyphilitic drugs; treatment of trypano-

somiasis, amebiasis, and sleeping sickness.

l Waste material: Waste incineration; household waste disposal.

l Other industrial uses/sources: Glassware and ceramics production; use in deco-

loring agents; electronics industries; solar cells, optoelectronic devices, semi-

conductor applications, light-emitting diodes (digital watches); dyes and colors;
pyrotechnics; drying agents for cotton; oil and solvent recycling; cement works;
angifouling agents; catalysts.

A Modern and Historical Uses of Arsenic

Although there is no agreement as to the first intentional use of arsenic in antiquity,

arsenic poisoning was among the first occupational diseases to be recognized by
mankind (Azcue and Nriagu 1994). The first documented historical uses of arsenic
were pharmaceutical and medicinal. Arsenic was also commonly used in pigments,
poisons, and in the manufacturing of glass.
A major modern use for arsenic was as pesticides in agriculture: monosodium
methylarsenate (MSMA), disodium methylarsenate (DSMA), dimethylarsinic acid
(cacodylic acid), and arsenic acid (Azcue and Nriagu 1994). Arsenic acid is also used
in the manufacture of wood preservative salts. Arsenillic acid is used as an additive in
poultry, swine, and veterinary feeds. Until the 1970s, approximately 80% of the
arsenic produced was used to manufacture simple inorganic salts for use as pesticides.
Today, pesticides account for approximately 50% of the arsenic consumed, with
organic arsenic compounds now dominating pesticide production. Another 30% of
the world arsenic market is accounted for by wood preservatives. The remaining
arsenic is used to manufacture glass, alloys, electronics, catalysts, fodder additives,
and veterinary chemicals (Matschullat 2000). Currently, the main arsenic producers
are located in China, Chile, Peru, Mexico, Russia, Kazakhstan, and France. These
countries account for more than 90% of world arsenic production (USGS 2006).
B Mining as a Source of Arsenic in the Environment

Mining, smelting, and ore beneficiation processes are major sources of arsenic
contamination worldwide. Arsenic is a natural component of lead-, zinc-, copper-,
and gold-bearing ores and consequently may contaminate soils, sediments, and
groundwater during mining and smelting operations. The most common source of
arsenic in such environments is from weathering of arsenic sulfides such as arseno-
pyrite and other arsenic-bearing metal sulfides exposed to atmospheric conditions
(for example, by placement on a heap or waste rock dump).
Arsenic can be leached from sulfide ores by mine water and may be further
concentrated during the metal sulfide beneficiation process, in which an arsenic-
hosting ore is chemically treated before smelting. The concentration of arsenic
liberated by sulfide oxidation and smelting is dependent on several factors:
l The arsenic concentration available in the ore or deposit (related to geology of
the original hydrothermal deposit)
l The Eh–pH regime of the environment from which the arsenic was liberated
l The chemistry of natural waters that promote release or attenuation of arsenic
Arsenic is a common constituent of many sulfide minerals, and thus no specific
arsenic-enriched mineral such as arsenopyrite need be present. However, all sulfide
mining and smelting sites are potential locations of future arsenic contamination
(Madhavan and Subramanian 2000). The contamination of soils, waters, and sedi-
ments by arsenic originating from mining and smelting activities has been widely
reported in the literature, and several examples are discussed next.
Because arsenic is associated with gold deposits, gold mining can contribute to
arsenic contamination. In fact, gold mining activities have been recognized as the
main source of arsenic pollution in many locales. Gold is an important commodity
that has been mined extensively within Australia, particularly in the state of Victoria,
where elevated arsenic concentrations are associated with gold mining residues
(Hinwood et al.1998; Lamb et al. 1996). Concentrations of arsenic reported from
gold mining areas varied among regions. In addition, the concentrations at specific
sites were found to be dependent on the type of ore body being mined, the type of
ore processing used, and the means of waste disposal (Ellice et al. 2001). High
concentrations of arsenic have been reported in mullock heaps and mining waste
disposal areas in Victoria, where concentrations ranged from 280 to 15,000 mg/kg
in areas of former mine waste disposal (Hinwood et al. 1998; Ellice et al. 2001).
Arsenic contamination related to gold production has also been reported in Brazil
(Borba et al. 2003). These authors estimated that 390,000 t arsenic was discharged to
the environment during three centuries of gold mining in the Iron Quadrangle mining
district. Arsenic concentrations up to 4,800 mg/kg were found in gold deposits in this
area. The highest arsenic concentrations in water and stream sediments were reported
in the vicinity of mining areas. Up to 300 mg/L was found in surface water, whereas
the arsenic content in stream sediments was in the range of 20–4,000 mg/kg. Although
no arsenic poisoning cases were reported from the area, there are arsenic hazards from
dispersion of old tailings by flooding, construction of settlements on arsenic-con-
taminated soils, and occasional consumption of contaminated groundwater.
Contamination arising from gold mining activities in the Takab area of Iran
resulted in severe pollution of a local river system (Modabberi and Moore 2004).
Arsenic-gold is the main ore deposit in the area, and its mining history dates back
hundreds of years. Sediments from a stream (Zashuran) contained arsenic residues
ranging from 125 to 125,000 mg/kg; levels in sediments from a river (Sarouq)
ranged from 27 to 148 mg/kg. The range of arsenic concentrations detected in
waters associated with these sediments was 28–40,000 mg/L in the Zashuran stream
and 25–280 mg/L in the Sarouq River.
Arsenic enrichment in sediments from the Elqui watershed river system in
Northern Chile was reported to result from gold mining activities (in the El-Timbro
District) as well as geological processes (Oyarzun et al. 2004). Arsenic levels were
very high in both stream (55–485 mg/kg) and the Early Holocene sequence
lacustrine sediments (119–2344 mg/kg), suggesting that contamination, in this
region of Chile, derives both from industrial (mining operations) and major geo-
logical processes (long-term erosion from arsenic-rich epithermal ores and alter-
ation zones).
Historical mining activity has led to significant anthropogenic contamination of
soils and estuaries in Cornwall and Devon, SW England. Arsenic-rich polymetallic
ores were processed in these areas by heat treatment to remove arsenic, leaving
residues of metalloids and metals. At some sites, arsenic ore (arsenopyrite) was
processed (smelted and refined) and As2O3 was produced (Barton 1971). Very high
arsenic concentrations were reported from several mining sites in the area: Poldice,
432–37,600 mg/kg (Thornton and Farago 1997), Roseworthy, 815–67,300 mg/kg
with extreme values of 10% and 16% by mass (Frizzeli 1993), and Devon Great
Consols Mine, 173–52,600 mg/kg (Kavanagh 1998).
Poisoning from arsenic release to the environment from mining activities is well
documented in Thailand. Approximately 1,000 people in Southern Thailand have
been diagnosed with arsenic-related skin disorders. People living in and near Ron
Phibun town were particularly affected (Williams 1997; Choprapawon and Rodcline
1997). The affected area lies within the South-East Asian Tin Belt. Arsenic was found
at concentrations up to 5,000 mg/L in shallow groundwaters from Quaternary alluvial
sediment that had been extensively dredged during tin mining operations. Deeper
groundwaters from older limestone aquifers were less contaminated (Williams et al.
1996), although high arsenic concentrations were found in a few cases, presumably
from mining activities. The mobilization of arsenic is believed to be caused by
oxidation of arsenopyrite and is exacerbated by former tin mining activities.
Ghana, an important gold-mining country, has been active in mining since the late
19th century. The most important mining area in Ghana is the Ashanti Region. The
gold found there is associated with sulfide minerals, particularly arsenopyrite. Arse-
nic is mobilized from arsenopyrite by oxidation, which is either induced or exacer-
bated by mining activity. High regional arsenic concentrations have been found in
soils near the mines and the associated treatment works (Bowell 1992, 1993). In some
cases, high concentrations of arsenic were found in river waters from nearby mining
activity (Smedley et al. 1996). However, for mechanistic and physico-chemical
reasons peculiar to a region, high arsenic levels in soils and bedrocks near mines do
not necessarily contaminate local groundwater. For example, Smedley et al. (1996)
found that many groundwaters of the Ghanaian mining areas had low arsenic
concentrations, with a median concentration in tube well waters of just 2 mg/L.
Arsenic contamination from mining activities has been identified in numerous
areas of the US, many of which have been summarized by Welch et al. (1988,
1999). Groundwater from some areas has been reported to have very high arsenic
concentrations locally (up to 48,000 mg/L). Well-documented cases of arsenic
contamination include the Fairbanks gold mining district of Alaska (Wilson and
Hawkins 1978; Welch et al. 1988), the Coeur d’Alene Pb-Zn-Ag mining area of
Idaho (Mok and Wai 1990), Leviathan Mine in California (Webster et al. 1994),
Kelly Creek Valley, Nevada (Grimes et al. 1995), Clark Fork River, Montana
(Welch et al. 2000) and Lake Oahe in South Dakota (Ficklin and Callender 1989).
Many other areas of the world have high concentrations of arsenic in soils,
sediments, and waters as a result of mining activity. Documented cases include the
Lavrion region of Greece, associated with lead and silver mining activity (Kom-
nitsas et al.1995) and the Zimapán Valley of Mexico, South Africa, Zimbabwe and
Bowen Island, British Columbia (Boyle et al. 1998). Madhavan and Subramanian
(2000) investigated arsenic enrichment in the mining and smelting areas of the
Khetri (copper) and Zawar (lead-zinc) deposits in Rajasthan, India. The concentra-
tion of arsenic in Zawar zinc and Khetri copper tailings was found to be 1,519 and
1,179 mg/kg, respectively. Tailings at a local metal sulfide smelter contained
10,727 mg/kg (zinc), 61 mg/kg (lead), and 12 mg/kg (copper). The mean value of
arsenic in the mine water inlet of the Zawar region was 3 mg/L; in the mine water
outlet, 130 mg/L was reported. The mean value found for arsenic in groundwater
samples from this region (5.8 mg/L) was below the current MAC (maximum
allowable concentration) for arsenic. Generally, arsenic concentrations found in
inlet and outlet mine waters and in groundwaters from the Khetri region were low
(all values below 10 mg/L).
Although severe contamination of the environment has been documented in
many mining districts, it is surprising that, with the exception of Thailand, little
or no impact on the health of the local populations was reported.

C Arsenic Emissions from Coal Burning

Elements such as arsenic, selenium, fluorine, and mercury are commonly enriched
in coal deposits (Finkelman 2004). Coal, when combusted, volatilizes these ele-
ments and makes them available for inhalation, contamination of food and crops,
uptake by livestock, and bioaccumulation in birds and fish. Volatile elements such
as arsenic can also condense after coming in contact with ambient air to form
minerals (arsenolite, orpiment, realgar), which then fall to the ground. These
mineral contaminants may then be leached by rainwater and transported into
waterways. During coal combustion at power plants, most arsenic in coal volati-
lizes, with only a minor portion remaining in bottom ash. Most of the escaping
arsenic is captured by fly ash. Because 97%–99% of the fly ash is collected by
electrostatic precipitators, the atmospheric emission of arsenic (solid phase and
gaseous) is usually assumed to be minor (10%–30% of initial arsenic levels in coal).
However, arsenic can be leached from waste fly ash to create environmental pro-
blems. In the natural environment, arsenic is readily leached from acid (SiO2-rich)
bituminous coal ashes, but little is leached from alkali (CaO-rich) lignite ashes
(Yudovic and Ketris 2005).
Estimates put the proportion of arsenic derived from fuel combustion to total
anthropogenic arsenic emissions at 2–6% (Nriagu and Pacyna 1988), or up to 17%
(Kizilstein 1997, as cited in Yudovic and Ketris 2005). The amount of arsenic released
into the atmosphere depends on the particular combustion regime and pollution
control systems employed. Yudovic and Ketris (2005) estimate that 2%–47% of the
arsenic content in coal is released into the atmosphere from power plants.
The extent of arsenic volatility from coal is affected by modes of arsenic
occurrence in the coal (i.e., different forms of As such as those associated with
sulfide minerals or present as sorbed arsenate ions), with the dominant arsenic
forms being pyritic, that fraction of arsenic associated with the organic fraction of
coal and inorganic arsenate (Yudovic and Ketris 2005). The presence of chlorine in
coal can favor formation of gaseous arsenic compounds; the presence of illite or
CaCO3 favors immobilization of arsenic by the formation of refractory arsenates
such as KH2AsO4 and Ca3(AsO4)2, with high melting temperatures, above 1,000o C
(Yudovic and Ketris 2005).
The average arsenic content for bituminous coals and lignites in the world is 9.0
(±0.8) mg/kg and 7.4 (±1.4) mg/kg, respectively; on an ash basis this equates to 50
(±5) and 49 (±8) mg/kg, respectively (Yudovic and Ketris 2005). Arsenic may be
found in individual coal beds at levels as high as 3,845 mg/kg (Miocene bituminous
feed coal from Western Turkey) (Karayigit et al. 2000) and 35,000 mg/kg (Guizhou
Province in China) (Ding et al. 2001). Yudovic and Ketris (2005) suggest that a
relationship exists between the arsenic content in coal and its mode of occurrence in
coals. Typically, in coals with high arsenic content, arsenic-enriched sulfides domi-
nate (pyrite and other rare sulfides), whereas, in those with low arsenic content,
arsenic is associated with organic matter. There are four generic types of arsenic
accumulation in coal (Yudovic and Ketris 2005):
l Chinese type: hydrothermal arsenic enrichment
l Dakota type: hypergene enrichment from groundwaters draining arsenic-bearing
tufa host rocks
l Bulgarian type: arsenic enrichment resulting from arsenic-bearing waters enter-

ing coal-forming peat bogs from sulfide deposit aureoles

l Turkish type: volcanic input of arsenic in coal-forming peat bog as exhalations,

brines, and volcanic ash.

An increased exposure to arsenic from combustion of arsenic-rich coal has been
reported in Slovakia (Keegan et al. 2002; Pesch et al. 2002) and the Guizhou
Province of China (An et al. 1997; Liu et al. 2002; Ng et al. 2003; Finkelman et al.
1999; Dai et al. 2005). In the Guizhou Province of China, an estimated 3,000 people
were found to be suffering from severe arsenic poisoning and approximately
200,000 people were believed to be at risk of arsenic overexposure (Liu et al.
2002). The primary source of arsenic exposure in the Guizhou Province was
consumption of chili peppers and other food dried over fires fueled with high-
arsenic coal. Coal, when burned inside the home in open pits for daily cooking and
crop drying, produces a high concentration of arsenic in indoor air. High arsenic
residues from the air then permeate food during its preparation. Liu et al. (2002)
reported arsenic concentrations from the affected region of China to be 70 mg/kg in
smoked chili peppers (compared with 0.04 mg/kg in uncontaminated peppers) and
3.40 mg/kg in smoked corn.

D Agricultural Use of Arsenic Compounds

Arsenic has been widely used in insecticides and other pesticides. Arsenical
pesticides were used extensively in the orchards of many countries from the late
1800s until the introduction of DDT in the early 1960s. The extensive past use of
the horticultural pesticides lead arsenate (Pb3(AsO4)2), calcium arsenate
(Ca3AsO4)2, magnesium arsenate (Mg3(AsO4)2), zinc arsenate (Zn3(AsO4)2), zinc
arsenite (Zn3(AsO3)2), and Paris green [Cu(CH3COO)2·3Cu(AsO2)2] in orchards
has contributed to soil arsenic contamination (Folkes et al. 2001; Embrick et al.
2005; Brouwere et al. 2004; Wang and Mulligan 2006). Such pesticide use led to
extensive contamination of surface and subsurface soils in most Australian states
(Smith et al. 2003). Although a majority of this contamination is of a diffuse nature,
there are incidences of point-source contamination, largely at existing or former
pesticide storage sites. Arsenic concentrations up to 30 times background levels and
ranging from <0.5 to 115 mg/kg were reported at contaminated sites in Australia.
Similarly, there are reports that arsenic leached through soil profiles at some
Australian orchard sites (Smith et al. 2003). Other inorganic arsenicals, primarily
sodium arsenite, were widely used in agriculture, since about 1890, as weed killers
or nonselective soil sterilants (Reigart and Roberts 1999). Arsenic acid was also used
extensively as a cotton desiccant. Moreover, arsenic compounds such as H3AsO4, 3-
nitro-4-hydroxy phenylarsonic acid, and 4-nitrophenylarsonic acid were used as
animal feed additives (US Department of Agriculture 1970; Thompson 1973).
The use of sodium arsenite (NaAsO2) to control aquatic weeds has contributed to
the arsenic burden in New Zealand lakes (Tanner and Clayton 1990). Instances of
soil arsenic contamination have also been attributed to the extensive use of arseni-
cal insecticides in sheep and cattle dips to control ticks, fleas, and lice (McBride
et al. 1998; McLaren et al. 1998). Arsenic residues in surface soil (0–10 cm) of
historical sheep dip sites range between 37 and 3542 mg/kg. Arsenic at such sites
can penetrate deeply into soil; values up to 2282 mg/kg have been reported at
the 20–40 cm depth (McLaren et al. 1998). Smith et al. (2003) report the presence
in Australia of more than 1,000 arsenic-contaminated sites previously used as
cattle dips.
Arsenical pesticides, principally lead, calcium, and sodium arsenate, were wide-
ly applied on apple, blueberry, and potato crops in New England during the first half
of the 20th century. Extensive use of these compounds in an area correlate posi-
tively with levels of arsenic contamination in adjoining stream sediments; arsenic
residue values ranging from 0.3 to 93 mg/kg were reported in 1,600 screened stream
sediment samples (Robinson and Ayuso 2004).
Murphy and Aucott (1998) estimated amounts of arsenical pesticides historically
applied to cropland, turf, and golf courses in New Jersey (USA) to identify areas
with high arsenical pesticide residues that would require soil monitoring and
possible remediation.
Arsenical pesticides were extensively used in the US beginning with the second
half of the 19th century. Paris green, a copper and arsenic compound, was first used
in the US in 1865 for control of the Colorado potato beetle; by 1868 its use had been
well established. Another arsenical insecticide, calcium arsenate, was extensively
used for boll weevil control in US cotton production between 1920 and 1950.
Calcium arsenate was also used as a broad-spectrum insecticide on a variety of
vegetable crops and on white potatoes throughout the US (Murphy and Aucott
1998). Lead arsenates were also used, primarily in sprays and dusts, for protection
against insects attacking fruits and vegetables. Lead arsenate was recommended for
the routine spraying of apples throughout the growing season and its use continued
until 1964, when it was superseded by synthetic organic insecticides (primarily
DDT). Furthermore, Murphy and Aucott (1998) estimated that between 1900 and
1980, 25 million kg lead arsenate and 9 million kg calcium arsenate were applied to
soils in the state of New Jersey. The consequence is that residential developments
built in the area on former apple orchards are contaminated with arsenic and lead.
Beginning in the late 1980s, the US EPA (US Environmental Protection Agency)
banned the use of many inorganic arsenic-based pesticides (US EPA 1992a).
However, organoarsenical compounds such as monomethylarsenic acid (MMA)
and dimethylarsenic acid (DMA) are allowed to be used, because they are generally
considered to be noncarcinogenic. However, the lack of sufficient data in the
literature to define the stability of these compounds in the soil environment is
of concern (Datta et al. 2006); due to the potential for future release of arsenic
from these compounds following their breakdown or transformations in soil.

E Wood Preserving Industry

Arsenic has been commonly used in the wood preserving industry as a component
of preservatives (US EPA 2006). Timbers not naturally durable are treated with
preservatives to prevent decay by wood-boring Crustacea, mollusks, and fungi. The
most widely used wood preservative for timbers exposed to aquatic or moist
environments was CCA. The metal elements in CCA are present in the form of
oxides including CuO, Cr2O3 and As2O5. Three CCA formulations were developed
(Hingston et al.2001):
l Type A: CuO (18%), Cr2O3 (65%), and As2O5 (16%)
l Type B: CuO (20%), Cr2O3 (35%), and As2O5 (46%)
l Type C: CuO (19%), Cr2O3 (48%), and As2O5 (34%)
CCA-treated wood has been extensively used for more than 60 yr in Europe and
North America (Hingston et al. 2001). Since the late 1980s, US production of CCA-
treated lumber has averaged approximately 5 x 108 ft3 yr–1 (Solo Gabriele and
Townsend 1999). Because of the toxicity of arsenic and chromium used in CCA
treatment, regulatory and public attention has recently focused on the potential risks
from this exposure source, in particular, risks to children exposed to CCA-treated
wood decks and play sets (Kwon et al. 2004; Ursitti et al. 2004; Shalat et al. 2006;
Zartarian et al. 2006). Many sites used by the timber industry to treat wood, or to
dispose of waste, or sites where treated timber was used are contaminated with
arsenic (Rice et al. 2002; Hopp et al. 2006). In addition, timber treatment effluent
has been identified as an important source of arsenic contamination in aquatic and
terrestrial environments (Breslin and Adler-Ivenbrook 1998; Bolan and Thiyagar-
ajan 2001; Hingston et al. 2001; Rice et al. 2002).
The well-documented human and environmental toxicity of arsenic-based wood
preservatives led the European Commission to restrict use of these products (Euro-
pean Commission 2003). Since 2004, CCA-treated wood cannot be used for residen-
tial purposes or in marine water installations, and professional and industrial uses are
only permitted under strict conditions (Hopp et al. 2006). The US EPA also banned
the use of CCA-treated wood for residential purposes after 2003 (USEPA 2006).
Despite the reduction in CCA-treated wood production, the disposal of waste
CCA-treated wood in landfill raises concerns because of the potential for leaching
of arsenic. Townsend et al. (2005) investigated arsenic leaching from weathered
CCA-treated wood collected from demolition sites and disposal facilities. The
authors found the average leachable arsenic concentration (using the standard
Toxicity Characteristic Leaching Procedure, or TCLP) (US EPA 1992b) to be
3.2–13 mg/L. In 60 of 100 samples tested, the TCLP arsenic concentrations
exceeded the regulatory value of 5 mg/L, thus confirming the need to dispose of
weathered CCA-treated wood as a hazardous waste in the US Mandal and Suzuki
(2002) and Mukherjee et al. (2006) reviewed the literature and summarized data
(Table 5) on incidents of arsenic contamination from various industrial and mining
sources around the world.

Summary

Arsenic is a widely dispersed element in the Earth’s crust and exists at an average
concentration of approximately 5 mg/kg. There are many possible routes of human
exposure to arsenic from both natural and anthropogenic sources.
Table 5 Arsenic pollution from anthropogenic sources worldwide
Country Arsenic source Arsenic concentrations Reference
Mindanao Island, Geothermal power plant Matingao and Marebl Webster 1999
Philippines suspected source rivers
contaminated, 0.1
mg/L
Nakajo, Japan Waste water from a 0.025–4.00 mg/L in Terado et al.
factory producing local well water 1960a
arsenic sulfide
Toroku and Matsuo Arsenious acid and Not available Hotta 1989a,
villages, Japan white arsenic Tsuda et al.
produced from 1990a
FeAsS
Behalla area, South Industrial effluent 0.05–58 mg/L in well Guha Mujumder
Calcutta, India discharge from a water et al. 1988
factory
manufacturing
copper acetoarsenite
(Paris-Green)
Czech Republic Burning of arsenic Not available Bencko and
contaminated coal Symon 1977a
Toronto, Ontario Secondary lead smelters Vegetation and soils Temple
Canada contaminated et al. 1977a
Guizhou Province, Burning of arsenic rich Not available Dai et al. 2005
China coal
Srednogorie, Copper smelter Air pollution and soil Nilsson
Bulgaria processing high contamination, et al. 1993
arsenic sulfide ores local river:
0.75–1.5 mg/L
Anaconda, Montana Copper smelters As2O3 emitted Hwang
to the air, et al. 1997
contamination of
local vegetation and
soils, arsenic in
soils: 212–236
mg/kg
Ghana Gold mining, arsenic 0.90–8.25 mg/L arsenic Bennerman
rich mine tailings in water samples; et al. 2003,
942–10,200 mg/kg Serfor-Armah
arsenic in sediments et al. 2006
Lavrion, Greece Lead mining and Soils contamination. Stavrakis
smelting arsenic in garden et al. 1994a
soils and house
dusts: up to 14,800
and 3800 mg/kg
respectively
Mae-Moh Valley, Lignite mining and Arsenic-rich sediments Bashkin and
Northern power generation in streams, 1.2–325 Wongyai
Thailand g/L arsenic in 2002
surface waters,
groundwater from
deep tube wells
in Mae Moh mine
area – average 364
g/L As.
(continued)
Table 5 (continued)
Country Arsenic source Arsenic concentrations Reference
Nitra Valley in Coal burning power 8.8–139.0 mg/kg Keegan
central Slovakia station arsenic in garden et al. 2002
soils and 2.1–170
mg/kg in house
dusts
Australia Manufacture of: Soil contamination Smith et al. 2003
fertilizers, paint,
electronics; gas
works; mining
(mainly gold
deposits); power
stations; transport;
and wood
preservatives
Japan Wastewater from a Not available Mukherjee
factory producing et al. 2006
arsenic sulfide,
production of
arsenious acid,
manufacture of
insecticides
SW England Mining and smelting Over 700 km2 of Abrahams and
activities agricultural and Thornton
urban land 1987
estimated as
contaminated with
arsenic.
Soil contamination Farago
with concentrations et al. 1997,
up to 10% by mass Kavanagh
reported at some 1998
mining sites
Elevated arsenic Rawlins et al.
concentrations in 2003
stream waters
around former
mining sites
(5–30 g/L total As)
Patancheru, Andha- Production of veterinary Arsenic in Chandra Sekhar
Pradesh state, chemicals and groundwater: et al. 2003
India pharmaceuticals, 0.14–7.35 mg/L;
pesticide industries arsenic in surface
water: 0.30–8.95
mg/L
a
Cited in Mandal Suzuki (2002).

Arsenic occurs as a constituent in more than 200 minerals, although it primarily

exists as arsenopyrite and as a constituent in several other sulfide minerals. The
introduction of arsenic into drinking water can occur as a result of its natural
geological presence in local bedrock. Arsenic-containing bedrock formations of
this sort are known in Bangladesh, West Bengal (India), and regions of China, and
many cases of endemic contamination by arsenic with serious consequences to
human health are known from these areas. Significant natural contamination of
surface waters and soil can arise when arsenic-rich geothermal fluids come into
contact with surface waters. When humans are implicated in causing or exacerbat-
ing arsenic pollution, the cause can almost always be traced to mining or mining-
related activities.
Arsenic exists in many oxidation states, with arsenic (III) and (V) being the most
common forms. Similar to many metalloids, the prevalence of particular species of
arsenic depends greatly on the pH and redox conditions of the matrix in which it
exists. Speciation is also important in determining the toxicity of arsenic. Arsenic
minerals exist in the environment principally as sulfides, oxides, and phosphates. In
igneous rocks, only those of volcanic origin are implicated in high aqueous arsenic
concentrations. Sedimentary rocks tend not to bear high arsenic loads, and common
matrices such as sands and sandstones contain lower concentrations owing to the
dominance of quartz and feldspars.
Groundwater contamination by arsenic arises from sources of arsenopyrite,
base metal sulfides, realgar and orpiment, arsenic-rich pyrite, and iron oxyhydrox-
ide. Mechanisms by which arsenic is released from minerals are varied and
are accounted for by many (bio)geochemical processes: oxidation of arsenic-bearing
sulfides, desorption from oxides and hydroxides, reductive dissolution, evaporative
concentration, leaching from sulfides by carbonate, and microbial mobilization.
Arsenic enrichment also takes place in geothermally active areas; surface waters
are more susceptible than groundwater to contamination in the vicinity of such
geothermal systems, and evidence suggests that increased use of geothermal power
may elevate risks of arsenic exposure in affected areas.
Past and current mining activities continue to provide sources of environmental
contamination by arsenic. Because gold- and arsenic-bearing minerals coexist,
there is a hazard of mobilizing arsenic during gold mining activities. The Ashanti
region of central Ghana currently faces this as a real risk. Historical arsenic
contamination exists in Cornwall, UK; an example of a recent arsenic pollution
event is that of Ron Phibun town in southern Thailand, where arsenic-related
human health effects have been reported. Other important sources of arsenic
exposure include coal burning in Slovakia, Turkey, and the Guizhou Province of
China; use of arsenic as pesticides in Australia, New Zealand, and the US; and
consumption of contaminated foodstuffs (China) and exposure to wood preserving
arsenicals (Europe and North America).

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