The geochemistry 1

of arsenic
I. Thornton and M. Farago

1.1 INTRODUCTION

Understanding the natural occurrence and the chemical and mineral forms
of arsenic in the surface environment is of paramount importance in assess-
ing the sources and pathways contributing to human exposure. Arsenic is a
metalloid element, within Group Vb of the Periodic Table, but is often
incorrectly referred to as a metal. Arsenic is ubiquitous in the environment,
usually being present in small amounts in all rock, soil, dust, water, air and
biological tissues.
This chapter presents (a) a review of the geochemistry, hydrogeo-
chemistry, and biogeochemistry of arsenic, including present day knowl-
edge of the chemistry of arsenic in the soil, (b) applies this knowledge to the
understanding of arsenic sources and pathways in several site-specific stud-
ies where elevated concentrations of arsenic have led to excessive human
exposure and/or health effects, and (c) draws attention to research priori-
ties within the framework source-pathways-human exposure.

1.2 GEOCHEMISTRY, HYDROGEOCHEMISTRY

AND SOIL CHEMISTRY

The geochemistry of arsenic has recently been reviewed by Thornton

(1996). It is the main constituent of more than 200 mineral species, of which
approximately 60% are arsenates, 20% sulfides and sulfosalts and the re-
maining 20% include arsenides, arsenites, oxides, silicates and elemental As
(Onishi, 1970). Some common arsenic minerals are listed in Table 1.1.

C. O. Abernathy et al. (eds.), Arsenic

© Chapman & Hall 1997
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Table 1.1 Some common arsenic minerals

Sulfides Realgar AsS

Orpiment AS2S3
Arsenopyrite FeAsS
Sulfosalts Tennantite (Cu,Fe) 12AS4S13
Enargite Cu3AsS4
Arsenates Scorodite FeAs0 4,2H2O
Mimetite Pbs (As04) 3CI
Arsenites Trippkeite CUAS20 4

Arsenic is present in many mineral deposits and in particular those contain-

ing sulfide minerals. It is common in iron pyrite, galena, chalcopyrite, and
less common in sphalerite (Goldschmidt, 1954). The most common arsenic
mineral is arsenopyrite, FeAsS. Arsenic is used as an indicator or pathfinder
for gold mineralization in geochemical surveys.
The average concentration of As in igneous and sedimentary rocks
is 2mgkg-t, and in most rocks it ranges from 0.5 to 2.5mgkg-1 (Kabata-
Pendias and Pendias, 1984), though higher concentrations are found in
finer-grained argillaceous sediments and phosphorites. Arsenic is con-
centrated in some reducing marine sediments which may contain up to
3000mgkg-l . Arsenic may be coprecipitated with iron hydroxides and
sulfides in sedimentary rocks. Iron deposits, sedimentary iron ores, and
manganese nodules are rich in arsenic. The hydrogeochemistry of arsenic
has been discussed by Fordyce et ai., (1995) and Smedley et ai. (1996).
The concentration of As in unpolluted fresh waters typically ranges from
1-10/lgrl , rising to 100-5000/lgr1 in areas of sulfide mineralization and
mining (Fordyce et ai., 1995). At moderate or high redox potentials As
can be stabilized as a series of pentavalent (arsenate) oxyanions, H 3As0 4,
H2As04, HAsO~- and AsO;. However, under most reducing (acid and
mildly alkaline) conditions, the trivalent arsenite species (H3As0 3) pre-
dominates. The retention of As in solution is linked by coprecipitation with
elements such as Fe, Ba, Co, Ni, Pb, and Zn (Fordyce et ai., 1995). In the
Obuasi gold-mining area of Ghana, the highest concentrations of arsenic
were found in a deeper part of the aquifer. It was thought that the element
had built up as a result of longer residence times of groundwater (Smedley
et ai., 1996).
Complex organic arsenic compounds such as tetramethylarsonium salts,
arsenocholine, arsenobetaine, dimethyl (ribosyl) arsine oxides, and arsenic-
containing lipids have been identified in the marine environment (Irgolic et
ai., 1995). Only a very minor fraction of the total arsenic in the oceans
remains in solution in sea water, as the majority is sorbed on to suspended
particulate material.
_______T_H_E_G_E_O_C_H_E_M_I_ST_R_y_O_F_A_R'----SE_N_I_C ----'I 1__3
---J

The main sources of arsenic in soils are the parent materials from
which they are derived. These may be the underlying bedrock or materials
transported by wind and water. When rocks weather, arsenic may be mobi-
lized as salts of arsenous acid and arsenic acid (Irgolic et al., 1995). Arsenic
is present in soils in higher concentrations than those in rocks (Peterson,
et al., 1981). Uncontaminated soils usually contain 1-40mgkg-1 As, with
lowest concentrations in sandy soils and those derived from granites.
Larger concentrations are found in alluvial soils and in organic soils
(Kabata-Pendias and Pendias, 1984). Soils in the proximity of sulfide
ore deposits may contain up to 8000mgkg-1 As (Levander, 1977). High
concentrations are also found in soils and groundwaters affected by
geothermal activity (Reay, 1972). The roasting of arsenic-containing
(sulfide) ores and burning of arsenic-rich coal releases arsenic trioxide,
which may react in air with basic oxides, such as alkaline earth oxides, to
form arsenates, which can then be deposited on to soils (Irgolic et al., 1995).
For example, in mineralized areas of Cornwall, concentrations of arsenic in
surface soils range up to 2500mgkg-1, and in the vicinity of old roasting
ovens and smelter stacks may range from 0.1 to 1.0% or more (Thornton,
1995).
Under oxidizing conditions, in aerobic environments, arsenates (con-
taining pentavalent arsenic) are the stable species. Arsenic is precipitated
as ferric arsenate in soil horizons rich in iron. Elevated concentrations of
arsenic (8-40 mg kg-I) in acid sulphate soils in Canada and New Zealand are
associated with the presence of pyrite (Dudas, 1987), which typically holds
up to 0.5% As through lattice substitution for sulfur (Goldschmidt, 1954).
Leaching of arsenic derived from the weathering of pyritic slates in Alberta,
Canada, has led to the accumulation of up to several hundred mgkg-I in the
subsoil by adsorption on to secondary iron oxides (Dudas, 1984). Iron-rich
bauxites have also been recorded (>500 mg kg-I As20 3). Under reducing
conditions arsenites (containing trivalent arsenic) are the predotninant ar-
senic compounds. However, the reduction of arsenate to arsenite is slow,
and soil systems may not be at equilibrium. Inorganic arsenic compounds
can be methylated by micro-organisms, producing, under oxidizing condi-
tions, methylarsonic acid, dimethylarsinic acid and trimethylarsine oxide
(Irgolic et al., 1995). Under anaerobic conditions these can be reduced to
volatile and easily oxidized methylarsines.
The behaviour of arsenic in soil has been reviewed by O'Neill (1990).
Under the ranges of Eh and pH in soils, arsenic my be present as either
As(V) or As(III), with microbial activity causing methylation, demethy-
lation and/or change in oxidation state. Arsenates of Fe and Al are the
dominant phases in acid soils and are less soluble than calcium arsenate
which is the main chemical form in many calcareous soils (Woolson et al.,
1973; Fordyce et al., 1995). Arsenic sulfide minerals may form if sulfur
species are present and if the redox potential is low enough. Clay minerals,
4 II A_R_S_E_N_I_C_:E_XP_O_S_U_R_E_AN_D_H_E_A_L_TH_E_F_F_E_Cf_S _

Fe, Mn and Al oxides and organic matter can influence the sorption, solu-
bility and rate of oxidation of As species.

1.3 BIOGEOCHEMISTRY AND GEOBOTANY

Arsenic is a constituent of most plants. The metalloid can be phytotoxic and

the toxicity of arsenite is greater than that of arsenate (Peterson et aI.,
1981). It is suggested that As uptake is passive (Streit and Stumm, 1993),
and that it is translocated to most parts of the plant, most being found in
roots and old leaves. Natural As levels in plants seldom exceed 1f.tglg.
Markert (1992) has constructed a table showing the elemental concentra-
tions of a 'Reference Plant' using his own and other published data from the
literature. No concentration data from accumulators or rejector plants were
included. The hypothetical reference plant was assigned the arsenic concen-
tration of 0.1 flglg.
The uptake of As into crop plants is of concern, since this provides an
entry of the toxic element into the food chain. Xu and Thornton (1985)
surveyed 32 gardens in the Hayle-Camborne area in Cornwall, where soil
As concentrations were in the range 1~92f.tglg. They determined As in
lettuce, onion, beetroot, carrot, pea and bean; the As content of vegetables
increased with As content of the soil but only lettuce exceeded 1flglg (dry
weight). The relationships between As contents of beetroot, lettuce, onion
and pea and both total and extractable As in soil were significant showing
As levels in the edible tissue to increase with increasing soil content. As in
carrots and beans was not significantly related to soil content. Similar
concentrations of As were found in lettuce and strawberries in the Tamar
Valley area where the maximum reported values were 1.4f.tglg and 0.7f.tglg
(dry weight) respectively, with As content increasing with As in the soil
(Thoresby and Thornton, 1979).
Rice grown in polluted soil was shown to have a mean concentration of
0.19flglg (dry weight) but the roots contained a range of 936-1182flg/g
(Kitagishi and Yamane, 1981). Yields of rice, barley and alfalfa in cotton
fields previously treated with As may be reduced (Peterson et aI., 1981).
These authors have also suggested that low levels of phosphates displace As
from soil particles which increases its uptake and phytotoxicity, whereas,
larger amounts of phosphates compete with As at root surfaces to decrease
uptake and phytotoxicity.
Arsenic concentrations in plants may also reveal contamination. Arsenic
concentrations in leaves may be higher if arsenic pesticides have been used.
Arsenic accumulates in Pseudotsuga mensiesii; up to 2000-5000 flglg have
been reported in the plant ash (Hewitt and Smith, 1975). High concen-
trations of up to 16flg/g (dry weight) in dandelion (Taraxacum officinaIe)
growing around smelters in Bulgaria have been recorded by Djingova and
 THE GEOCHEMISTRY OF ARSENIC
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I 5

Kuleff (1993). This plant has also been used to compare urban pollution in
three European cities (Djingova and Kuleff, 1993). Samples were analysed
from Rotterdam Sofia (Bulgaria), Thessaloniki (Greece) and Rotterdam
(the Netherlands), where As values of <0.1,4.87 and 1.51lg/g (dry weight)
were recorded respectively. Higher As in Thessaloniki was associated with
traffic pollution. Otte et ai. (1988) studied the uptake of As by grasses, rush,
reed and nettle from the Rhine estuary and from waters near mines. Some
grasses showed higher As concentrations in dead leaves than in roots.
Growth of reed was more inhibited than growth of nettle. Iron plays a key
factor in determining the mobility of As in salt-marsh soils and in the
translocation processes in the plants (Otte et ai., 1988).
In south-west England metal enrichment in the soils is dominated by
Sn-Cu-As mineralization with additional contamination from mining and
smelting activities, many of which were very inefficient. Armeria maritima
(Mill) Willdenow (Farago et aI., 1980) which has long been recognized as an
indicator of mineralization and grew on all four sites was investigated
for its uptake of arsenic at three historic sites, the Botallack workings, the
Levant mine and the Poldice mine, with a site on the north coast of Corn-
wall at Portreath as a control. In addition, a number of plants colonizing the
highly contaminated land at Poldice were investigated for arsenic uptake.
Soil and plant arsenic concentrations at the four sites are shown in Table
1.2 and arsenic concentrations in some plants colonizing the Poldice site are
shown in Table 1.3. Arsenic levels are highest at the Poldice site, reflecting

Table 1.2 Ranges and means of concentrations of arsenic (Ilglg) in soils and
Armeria maritima (Am.), dry matter, from sites in sites in Cornwall, south-west
England

Botallack
workings Levant Mine Po/dice Mine Portreath

Site type Contaminated Contaminated Contaminated Coastal

uncontaminated
Soil
range 82.3-617 178-4540 1060-74900 27.3-41.5
mean 274 1106 6713 33
n 10 8 33 3
Am. Leaves
range 1.13-3.4 0.7-32.3 4.1-63.9 0.1
mean 2.2 3.0 18.3
Leaf/soil ratio 0.008 0.0027 0.0027
Am. Roots
range 7.1-26.4 6.6-171 11.1-454 2.3-3.4
mean 10.5 18.3 73.4 2.8
Root/soil ratio 0.038 0.017 0.011 0.085
Leaf/root ratio 0.21 0.16 0.25
6 I I A_R_S_E_N_I_C_:E_X_P_O_S_U_R_E_AN_D_H_E_A_L_TH_E_FF_E_CI'_S _

Table 1.3 Arsenic concentrations (Ilg!g, dry matter) in some plants colonizing con-
taminated land at the Poldice site (G. Sawbridge, unpublished data)

PLANT Plant part n Range Mean

Calluna vulgaris (heather) tops 25 5.95-370 32

Calluna vulgaris (heather) roots 25 36.4-153 92.5
Rubus ulmifulmus (bramble) tops 10 1.35-15.8 4.2
Ulex europaeus (gorse) tops 10 1.45-15.4 4.2
Cymbalaria muralis (ivy) tops 5 1.97-10.2 4.5

the fact that Poldice was primarily a copper and arsenic mining and smelting
site, whereas Botallack and Levant were mainly tin and copper mining sites.
The arsenic content of many of these plants was higher than that considered
to be toxic (Kabata-Pendias and Pendias, 1984; Fergusson, 1990) and yet
the plants displayed few symptoms of toxicity. Armeria maritima plants at
Poldice were in some cases very small and at some seasons the leaves had a
reddish coloration, which has been described as symptomatic of arsenic
toxicity (Fergusson, 1990). Using the mean concentrations in soils, leaves
and roots at each site, mean leaf/soil and root/soil concentration ratios are
also shown in Table 1.2. These are similar to concentration factors (CF)
calculated by Chamberlain (1983). The ratios for Armeria maritima growing
in a copper-impregnated bog have been discussed by Farago and Mehra
(1992); they considered that when the plant/soil ratios for any particu-
lar element are 0.1, then the plant can be considered as excluding the ele-
ment from its tissues. Thus although the soil concentrations may be high
and some arsenic is taken up into the roots, only a proportion of this is
translocated to the leaves, giving a leaf/root concentration ratio of about
0.2. This type of uptake is also shown by Calluna vulgaris at Poldice where
this ratio is 0.34.
This work has demonstrated that sites highly qmtaminated with arsenic
and other elements can be colonized by known indicator plants and also by
other wild plants. The plants can take up considerable concentrations of
arsenic into their aerial parts, but in particular into their roots.

1.4 GEOCHEMICAL MAPPING

Geochemical maps based on the analysis of stream sediments, soils and

waters are useful sources of baseline data showing arsenic distribution on a
regional or national scale. In certain cases, these maps have focussed atten-
tion on areas where arsenic enhancement is due to the presence of sulfide
minerals or contamination of soils with arsenic-rich mineral wastes or flue
dusts.
_ _ _ _ _ _ _T_H_E_G_E_O_C_H_E_M_I_ST_R_y_O_F_A_R_SE_N_I_C I 1 7

Geochemical surveys undertaken by the British Geological Survey have

indicated anomalous levels of As in the south-west Highlands and the
Grampian Highlands of Scotland, the English Lake District and North
Wales, associated with specific geological units (Plant et aI., 1989, 1991;
Simpson et al., 1993). These identify all the known gold mineralization, and
are also associated with Cu dominated multi-element mineralization
and complex Ph-As mineralization, together with environments in which
As has been complexed and absorbed in stream sediments by organic
matter and hydrous oxides in areas of impeded drainage. The Wolfson
Geochemical Atlas of England and Wales (Webb et aI., 1978) clearly shows
extensive contamination of soils in south-west England, with in excess of
700km2 affected (Webb et al., 1978; Abrahams and Thornton, 1987).
In Finland geochemical maps show arsenic anomalies in the south of the
country relating to sulfide mineralization and other geological features
(Koljonen et al., 1992).

1.5 NATURAL SOURCES OF ARSENIC LEADING TO

HUMAN EXPOSURE: LOCATION SPECIFIC STUDIES

There is increasing concern as to the possible adverse health effects from

exposure to elevated concentrations of arsenic in the natural geochemical
environment. As indicated above, sources of arsenic into drinking/irrigation
waters and into soils, dusts and the food chain may be derived from (a)
naturally occurring arsenic-rich minerals and rocks, such as pyrite, (b) from
sulfide mineralization and waste materials resulting from mining and smelt-
ing activities, and (c) from the burning of arsenic-rich coal. Examples are
listed in Table 1.4 and some are outlined below.

1.5.1 Arsenic-rich minerals and rocks

(a) South-west Taiwan

An epidemiological study undertaken in south-west Taiwan in the 1960s
showed a relationship between high concentrations of arsenic in drinking
water taken from artesian wells and skin cancer, keratosis and blackfoot
disease (a type of gangrene) (Tseng et al., 1968; Tseng, 1977). Further in-
vestigations in Taiwan have established relationships between high arsenic
exposure and cancers of the bladder and other internal organs (Chen et al.,
1992). The source material of the arsenic is not as yet known, but is likely to
be pyritic material or black shale occurring in underlying geological strata.
On exposure to air, oxidation of the pyritiferous material will lead to the
release of sulfuric acid and the solubilization of arsenic. The water from
these wells was used for both drinking and irrigation purposes. Few meas-
 8 ------JI
__ I A_R_S_E_N_IC_:_E_X_P_O_S_U_R_E_AN_D_H_E_A_L_T_H_E_FF_E_C_T_S _

Table 1.4 Natural sources of arsenic in the environment giving rise to human
exposure

1. Natural As-rich geological strata

South-West Taiwan Black shale? pyrite?
North-East Taiwan as above?
West Bengal Pyrite FeS 2
Mexico
Chile Volcanic sediments
South-East Argentine Loess with pyroclastic material
North-West Argentine Tertiary-Quaternary volcanic deposits/geothermal
Inner Mongolia
Finland Greenstone and volcanic-sedimentary rocks
Hungary
USA - Nevada Hydrothermal, pyrite

2. Mining/smelting residues
UK Arsenopyrite in Sn-Cu-As
Arsenic oxide - smelting
Scorodite - FeAs04 ·2H20
Thailand Arsenopyrite in SnoW-As
Fe oxides in alluvial soils
Ghana Arsenopyrite in Au ores
Chile Smelting copper ores
China Arsenopyrite
USA - Washington State Smelter wastes
USA - Anaconda Historic smelting emissions
USA - California Mine tailings

3. Coal burning
China - Yunnan, Guizhou
Slovakia
India.

urements have been made of arsenic in irrigated crops and fish. Dermal
exposure has not been evaluated.

(b) India
Arsenical skin lesions in over 175000 people living within an area of
34000km2 in six districts of West Bengal have been attributed to high
concentrations of arsenic in drinking water abstracted from tube-wells (Das
et ai., 1994, 1996). It is recognized that the source of the arsenic is geological
and associated with iron pyrites in arsenic-rich layers occurring in the
alluvium alongside the river Ganga. The release of arsenic is attributed to
excessive use of irrigation water for multiple rice cropping (the green revo-
lution). Dropping water-levels have resulted in the exposure of these ar-
_ _ _ _ _ _ _T_H_E_G_E_O_C_H_E_M_I_ST_R_y_O_F_A_R_SE_N_I_C II 9

senic rich beds to air, oxidation of the pyrite and solubilization of arsenic.
Concentrations of arsenic in waters from 51 tube-wells supplying drinking
water to schools ranged from 64 to 844Jlgr1• A survey of arsenic in waters
from 1420 wells ranged from 50 to 1250Jlgr1 As, present in equal propor-
tions as arsenite and arsenate (Das et al., 1996).

(c) Mexico
In parts of the Lagunera region in the central part of northern Mexico
chronic arsenic poisoning is endemic, leading to changes in skin pigmenta-
tion, keratosis, skin cancer, blackfoot disease and gastro-intestinal prob-
lems (Cebrian et al., 1983). A site-specific study in the town of Santa Ana
showed a mean concentration of arsenic in drinking water of 404Jlgr 1
compared with a control group in another town where arsenic averaged
19J1gr1 (Del Razo et al., 1994). The source of arsenic in the former area is
assumed to be geological.

(d) Northern Chile

Chronic arsenic poisoning has been reported in a population exposed to
elevated concentrations of arsenic in surface waters (rivers and creeks) used
for drinking water and irrigation. The sources of the arsenic have been
reported as volcanic sediments, minerals and soil (Caceres et al., 1992).
Samples taken from 23 locations at Aracamenan settlements near Calama
ranged from less than 100 to over 800Jlgr1 As. Most of the arsenic was
present as arsenate, but some arsenite was also determined.
Five soils irrigated with high arsenic waters ranged from 86 to
448mgkg-1 As compared to 64mgkg-1 in one control sample. Food crops
including cabbage, radish, beet, potato, broad bean and onions, ranged up
to 0.9Jlg/g As fresh weight.

(e) South-east Argentine

Chronic endemic regional hydroarsenicism resulting in a type of skin cancer
has been recognized in an area of the Pampa Province of Cordoba for many
years and has been associated with drinking water contaminated with ar-
senic (Astolfi et al., 1981). A strong natural contamination of groundwater
with arsenic and selenium has been recorded in the affected area, which
comprises a relatively depressed flat region known as Pampa hundida. The
arsenic content of nearly 50% of the water samples from this area ranged
from 100 to 316Jlgr1 As, with a maximum value of 3810JlgI-1 (Nicolli et al.,
1989). These groundwaters are alkaline and the highest arsenic contents are
found in waters with high levels of sodium and potassium. Groundwater
contamination is thought to be derived from loess, with arsenic concentra-
10 II A_R_S_E_N_IC_:_E_X_P_O_S_U_R_E_A_N_D_H_E_A_L_T_H_E_F_F_E_C_T_S _

tions ranging from 5.5 to 37.3mgkg-I, and rhyolitic volcanic glass ranging
from 6.8 to 1O.4mgkg-1 As. These anomalous loess-like sediments mostly
comprise pyroclastic material and differ in composition to loess from
Europe, Asia and North America (Nicolli et al., 1989).

(f) North-west Argentine

Elevated concentrations of arsenic in surface waters, shallow wells and
thermal springs have been reported from the Salta and Jujay provinces in
north-west Argentina (De Sastre et al., 1992). This natural contamination
has been related to Tertiary-Quaternary volcanic deposits, together with
post-volcanic geysers and thermal springs. Waters abstracted for drinking
supplies for the population of 5000 in the town of San Antonio de los
Cobres ranged from 470 to 770J.lgr1 As. Thermal springs ranged from 50-
9900J.lgr1 As.

(g) USA
The sources of arsenic in well waters in Nevada, Arizona and California are
geological, though the natures of the arsenic enriched deposits are as yet
unknown. It is probable that these are sulfur- and/or iron-rich deposits of
sedimentary origin or fine-grained argillaceous marine deposits in which
arsenic from biogenic sources has been concentrated. There is also a possi-
bility that arsenic has been derived as a result of geothermal activity. In
Nevada, elevated concentrations of arsenic occur in several groundwater
basins, and 5 community water systems exceed the current 50 J.lg r 1 standard
for the USA (Fontaine, 1994). The City of Fallon, with a population of 6000,
is served by a water supply with 100J.lgr1 As. As yet no adverse health
effects have been established.

1.5.2 Mining and smelting residues

(a) United Kingdom

The presence of arsenic in sulfide mineral deposits has been noted above,
and associated mining and smelting activities have led to high concentra-
tions ranging up to 1000mgkg-1 or more of this element in both agricultural
and garden soils and house dusts in old mining areas of Devon and Corn-
wall (Colbourne et al., 1975; Abrahams and Thornton, 1987). A study of
arsenic in surface waters in Cornwall has shown soluble arsenic in spe-
cific catchments to range from 10 to 50J.lgr1 (Aston et al., 1975). However,
abstraction of surface waters for processing and distribution avoids waters
contaminated by past mining activities, and water processing using alu-
minium hydroxide removes the majority of soluble arsenic. As a result
 THE GEOCHEMISTRY OF ARSENIC
-----------------------------' II 11

arsenic in drinking water in Cornwall rarely exceeds 10 flg r l (MAFF, 1982).

There are however some 20-30000 private wells in south-west England
for which little data are available and on which further study would be
advisable.
Current research concerns ingestion of arsenic-rich indoor dusts and
garden soils by young children, living on and near extensive areas of mine
waste, in which arsenic is present at concentrations up to and exceeding 1 %.
Early indications are that a proportion of the arsenic mined as arsenopyrite
and emitted from smelters as arsenious oxide has, with time, weathered to
scorodite, a relatively insoluble ferric arsenate (J. Watt, personal communi-
cation). The implications of the mineral forms of arsenic to bioavailability
and biological exposure are being assessed.

(b) Greece
Systematic sampling of soils and dusts in and around the ancient lead
mining and smelting site at Lavrion, Greece, has indicated extensive con-
tamination with arsenic as well as lead, and has instigated studies into
possible health implications to the local community (Stavrakis et al., 1994).
Concentrations of arsenic in garden soils and house dusts ranged up to
14800 and 3800 mg kg-I respectively. Current studies aim to characterize the
chemical and mineral phases of arsenic and their bioavailability.

(c) Thailand
Collaborative geochemical and hydrogeochemical studies into mmmg-
related arsenic contamination have been undertaken in the Ron Phibun
District of Thailand by the British Geological Survey and the Government
of Thailand Department of Mineral Resources (Fordyce et ai., 1995). Here
the sources of arsenic are high-grade arsenopyrite waste piles and alluvial
mineral deposits. Alluvial soils contained up to 5000mg/g As. It was found
that the waste materials contained only a small component of the primary
arsenopyrite, with most of the arsenic present as secondary arsenate miner-
als, in particular the relatively insoluble scorodite (FeAs0 4 ·2H20). Con-
centrations of arsenic ranged up to in excess of 5000 flg r l in shallow wells
used for drinking water, while water from deeper boreholes was much less
contaminated.

(d) Ghana
Arsenic in drinking water from streams, shallow wells and boreholes in
the Obuasi gold-mining area of Ghana range from <2 to 175 flg r l (Smedley
et al., 1996). The main sources are pollution from the mining activities and
oxidation of naturally occurring sulfide minerals, predominantly arsenopy-
12 II A_R_S_E_N_I_C_:E_X_P_O_S_U_R_E_AN_D_H_E_A_L_T_H_E_FF_E_CT_S _

rite (FeAsS). Some of the waters have a high arsenite content, which the
authors suggest is due to methylation and reduction reactions mediated by
bacteria and algae. Soils are leached kaolinite-muscovite laterites overlying
saprolite (Bowell, 1993). It is reported that in the saprolite, arsenopyrite
appears to have been replaced by secondary As- and Fe-bearing minerals,
including scorodite (FeAs0 4·2H20), arsenolite and arsenates (Bowell,
1992).

1.5.3 Coal burning

Environmental contamination with arsenic emitted from coal burning
power stations has been reported from several countries, including
Slovakia, China and India. The implications of these arsenic emissions to
human health have still to be fully assessed.
Burning local coal containing 900 to 1500mgkg-1 led to the mass extinc-
tion of honey bees within 30 km of a powerplant in Slovakia. Human epide-
miological studies in this area are reported by Bencko, in Chapter 8.
Endemic arsenosis has been reported in Guizhou Province, China, caused
by burning As-rich coal. The use of arsenic-rich coals in a power plant in
India has resulted in contamination of the atmosphere, soil and water.

1.6 RESEARCH PRIORITIES

1. While many research workers are now able to quantify soluble arsenic
species, such as trivalent arsenite and pentavalent arsenate, in water
supplies, there is still an urgent need to identify and quantify the known
mineral and chemical forms of arsenic in the rocks, soils and sediments
that constitute the natural sources of arsenic entering water and the food
chain. These different forms or species will have a marked influence on
the solubility and bioavailability of the arsenic.
2. There is also a need to further investigate the changes in different arsenic
species in the surface environment over time, as these changes may lead
to either increases or decreases in arsenic solubility and bioavailability.
3. It is accepted that the geochemistry and hydrogeochemistry of arsenic
will have a significant influence on total arsenic intake through the
consumption of food and water, the accidental ingestion of soil and dust,
the inhalation of arsenic-rich particulate material in the atmosphere, and
skin absorption of arsenic. This total intake which comprises both inor-
ganic and organic arsenic species present in the above media, requires
study in each of the areas where natural sources of arsenic constitute a
hazard to human health.
4. In order to understand the importance of total arsenic intake in risk
assessment procedures, it is imperative to determine the proportion of
'--- T_H_E_G_E_O_C_H_E_M_I_S_T_R_y_O_F_A_R_SE_N_IC I I 13

total intake resulting in biological exposure, i.e. the proportion absorbed

from the gastro-intestinal tract and the lung. In the absence of experi-
mental data, risk assessment will be made using assumptions that may be
faulted.

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