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Arsenic C.K. Jain
Arsenic C.K. Jain
4304±4312, 2000
7 2000 Elsevier Science Ltd. All rights reserved
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AbstractÐThe occurrence of arsenic in natural water has received signi®cant attention during recent
years. Arsenic exists in the environment in a number of valency states. The valency state of arsenic
plays an important role for its behavior and toxicity in the aqueous system. The toxicity and
bioavailability of arsenic can only be determined if all its forms can be identi®ed and quanti®ed.
Therefore, the aim of this article is to provide a general description of the occurrence of arsenic in the
environment, its toxicity, health hazards, and measurement techniques for speciation analysis. Dierent
techniques used for speciation of arsenic, viz., spectrometric, chromatographic, electrochemical, etc.
have been discussed. 7 2000 Elsevier Science Ltd. All rights reserved
(Penrose, 1974; Lewis and Tatken, 1978; Stugeron (1989) studied the distribution and mobilization of
et al., 1989). The concentration of arsenic in natural arsenic species in creek waters around the Blackbird
waters depends on the geological composition and mining district, Idaho, and reported that the release
the degree of pollution of the environment. The of arsenic was pH dependent and was related to the
concentration of As(III) to As(V) varies widely total iron and free iron oxides in the sediments.
depending on the redox conditions in the geological Leaching under a nitrogen atmosphere resulted in
environment (Braman and Foreback, 1973; an increased release of arsenic, which may be due
Andreae, 1977; Shaikh and Tallman, 1978). to the reduction of ferric-arsenate compounds to
the more soluble ferrous-arsenate forms.
OCCURRENCE
The knowledge of the geographic distribution of
dierent arsenic species in natural water systems is
Arsenic rarely occurs in free state, it is largely important for environmental consideration of the
found in combination with sulphur, oxygen and geochemical and biological cycling of the element.
iron (Brewstar, 1994; Chatterjee, 1994). Arsenic Furthermore, this will also provide insight into the
occurs in the environment as a result of several geochemical process responsible for elevated arsenic
inputs that contain this element as organic and concentrations in dierent hydrogeological environ-
inorganic forms (Rubio et al., 1992). The presence ments.
of arsenic in natural water is related to the process
of leaching from the arsenic containing source TOXICITY
rocks and sediments (Robertson, 1989; Hering and
Elimelech, 1995). In¯ux of arsenic from various The toxicology of arsenic is a complex phenom-
anthropogenically-induced sources may also con- enon as arsenic is considered to be an essential el-
taminate both soils and ground water especially ement also. Two types of toxicity, viz., acute and
under anoxic conditions (Bhattacharya et al., 1996, sub-acute are known from long time. The acute
1997). arsenic poisoning requiring prompt medical atten-
The presence of arsenic in natural water is gener- tion usually occurs through ingestion of contami-
ally associated with the geochemical environments nated food or drink. The major early manifestation
such as basin-®ll deposits of alluvial-lacustrine ori- due to acute arsenic poisoning include burning and
gin, volcanic deposits, inputs from geothermal dryness of the mouth and throat, dysphasia, colicky
sources, mining wastes and land®lls (Welch et al., abnormal pain, projectile vomiting, profuse diar-
1988; Korte and Fernando, 1991). Occurrence of rhea, and hematuria. The muscular cramps, facial
arsenic in natural water depends on the local ge- edema and cardiac abnormalities, shock can
ology, hydrology and geochemical characteristics of develop rapidly as a result of dehydration (Done
the aquifer materials (Bhattacharya et al., 1997). and Peart, 1971).
Furthermore, the geochemical characteristics of the Sub-acute arsenic toxicity mainly involves the res-
aquifer material and their interactions with the aqu- piratory, gastro-intestinal, cardio-vascular, nervous
eous media also play an important role in control- and haematopoietic systems. It may cause loss of
ling retention and/or mobility of arsenic within the appetite, nausea and some vomiting, dry throat,
subsurface environment (Bhattacharya et al., shooting pains, diarrhea, nervous weakness, tingling
1995a). Uncontrolled anthropogenic activities such of the hands and feet, jaundice and erythema.
as smelting of metal ores, use of arsenical pesticides Longer exposure resulted in dry, falling hair, brittle
and wood preservatives agents may also release loose nails, eczema, darken skin exfoliation and a
arsenic directly to the environment (Bhattacharya et hormy condition of the palms and soles (Holmquist,
al., 1995b). 1951; Pinto and Mcgill, 1953). The toxicities of var-
The redox conditions in the subsurface environ- ious arsenic compounds to man and animals have
ment also play an important role in determining the been studied by various workers (Sullivan, 1969;
mobility of arsenic (Robertson, 1986). The oxi- USEPA (United States Environmental Protection
dation of dierent mineral species causes arsenic to Agency), 1971; Fairchild et al., 1977). Chatterjee
become soluble and enter into the surrounding en- (1994) has discussed the toxicity of arsenic to dier-
vironment through drainage water. Any phenomena ent organs.
which aect the redox conditions such as pumping Biologically, As(III) is considered more toxic
rate and the land use pattern is of interest in ascer- than As(V) (NAS (National Academy of Sciences),
taining the primary mechanisms responsible for the 1977). Data on the dierences in toxicity between
excess arsenic content in ground water. Robertson As(III) and As(V) on human beings are very lim-
(1989) has further reported that occurrence and ori- ited. Trivalent arsenic is about 60 times more toxic
gin of arsenic in ground water depends on several than oxidized pentavalent state (Ferguson and
factors such as adsorption-desorption, precipitation- Gavis, 1972). Inorganic arsenic compounds are
dissolution, oxidation-reduction, ion-exchange, about 100 times more toxic than organic arsenic
grain size, organic contents, biological activity and compounds (DMMA and MMAA) (Nagy and
aquifer characteristics. For example, Mok and Wai Korom, 1983). Methylation of inorganic arsenic in
4306 C. K. Jain and I. Ali
the body is a detoxi®cation process, which reduces posure to arsenic contaminated water may lead to
the anity of the compound for tissue (Vahter and various diseases such as conjunctivitis, hyperkerato-
Marafante, 1988). sis, hyperpigmentation, cardiovascular diseases, dis-
The assessment of arsenic pollution in soils and turbance in the peripheral vascular and nervous
plants is also important from the toxicity point of systems, skin cancer, gangrene, leucomelonisis, non
view. Several studies have been conducted concern- pitting swelling, hepatomegaly and splenomegaly
ing arsenic and associated metals in stream sedi- (Kiping, 1977; WHO (World Health Organisation),
ments, soils, and crop plants. The Wolfson 1981; Pershagen, 1983). The eects on the lungs,
Geochemical Atlas of England and Wales clearly uterus, genitourinary tract and other parts of the
delineates the major arsenic province in Devon and body have been detected in the advance stages of
Cornwall (Webb et al., 1978). Subsequent studies arsenic toxicity. Besides, high concentrations of
comparing the distribution patters of arsenic in arsenic in drinking water also result in an increase
stream sediments and soils have con®rmed extensive in stillbirths and spontaneous abortions (Csanady
soil contamination throughout southwest England and Straub, 1995).
(Colbourne et al., 1975; Abrahams and Thornton, Arsenic contamination in ground water of Tai-
1987). The majority of this area is under agricul- wan is well known (Lu, 1990a,b) and has resulted
tural use for arable and vegetable crop production in arsenism and black-foot disease in people drink-
and for livestock farming. Thoresby and Thornton ing contaminated ground water. Some cases of can-
(1979) have reported uptake of arsenic by pasture cer are also prevalent in the endemic areas (Chem
herbage grown on a soil contaminated with arsenic. et al., 1988). In Antofagasta, over 12% of the popu-
The same ®ndings were also reported by Abrahams lation exhibiting dermatological manifestations re-
(1983). However there is little evidence of signi®cant lated to arsenic due to consumption of high arsenic
arsenic uptake into locally grown farm, horticul- containing drinking water (Borgono and Greiber,
tural and home garden crops. It can be concluded 1972). Chronic arsenic poisoning was also reported
that arsenic in these soils is present in forms that in some parts of North Mexico (Cebrian et al.,
are relatively insoluble and thus of low bioavailabil- 1983). The exposed population of the region
ity (Thornton, 1995). showed one of the cutaneous signs of chronic
Esser (1996) has studied the concentration of arsenic poisoning. A similar incident involving
arsenic in dierent soils and plant samples in agri- arsenic was also reported from Cardoba Province,
cultural regions of Norway and reported that soil north of Argentina (Astol® et al., 1981). Regular
cultivation in¯uences the relative concentration of intake of arsenic contaminated water resulted in
arsenic in the topsoil. Distribution of arsenic in skin cancer. The problem of arsenic contamination
soils formed in the Indiana dunes has also been stu- in ground water of West Bengal, India has been
died with respect to particle size, mineralogy, soil claimed as the biggest calamity in the world (Chat-
depth, soil age (Esser et al., 1991a) and eect of terjee, 1994; Das et al., 1994, 1995; Chatterjee et al.,
aerosol inputs with respect to distance from the pol- 1995; Mandal et al., 1996). Other incidents invol-
lution source, topography, vegetation and organic ving smaller population groups have been reported
matter (Esser et al., 1991b). There is obviously a in Poland, Minnesota, USA, Chile, North Mexico,
need for a multi-disciplinary study concerning en- Argentina, Canada, Hungary, Japan, New Zealand,
vironmental pathways, food chain transfer of and Spain and have been compiled by Chatterjee
arsenic and possible health eects due to consump- (1994). The important ®nding in most of these cases
tion of contaminated foods. was the close relationship between the prevalence of
cutaneous lesions and the exposure to drinking
HEALTH HAZARDS
water containing high levels of arsenic.
According to Lung (1990), speciation analysis of As(III) and As(V) species using silver diethyl-
involves the use of analytical methods that can pro- dithiocarbamate. Spectroscopic methods based on
vide information about the physico-chemical forms the formation of molybdenum blue have also been
of the elements. Schroeder (1989) distinguishes reported for arsenic speciation (Bogdanova, 1984;
physical speciation, which involves dierentiation of Matsubara et al., 1987; Nasu and Kan, 1988;
the physical size or the physical properties of the Tamari et al., 1989; Palanivelu et al., 1992). Aggett
metal, and chemical speciation, which entails the and Aspell (1976) has developed a method in which
dierentiation among the various chemical forms. control of pH of sodium tetraborate(III) reduction
The elements occur in the environment in dier- solution was used to dierentiate between As(III)
ent oxidation states and form various species. and total arsenic, prior to analysis by atomic
Dierent species of the same element may have absorption spectrometry.
dierent chemical and toxicological properties. Hydride generation atomic absorption spec-
Therefore, determination of the total concentration trometry is one of the most widely used methods
of an element may not provide information about for arsenic speciation due to its high sensitivity, low
the actual physico-chemical forms of the element, detection limit and high selectivity (Andreae, 1977;
required for understanding its toxicity, biotrans- Howard and Arbab-Zavar, 1981; Aggett and Haya-
formation, etc. Thus, in order to obtain information shi, 1987; Aggett and Boyes, 1989; Howard and
on toxicity and biotransformation of elements in Comber, 1992). Flow injection hydride generation
aquatic systems, quanti®cation of individual species atomic absorption spectrometry has also been used
of an element is needed. for arsenic speciation in water and urine, and in
The fundamental requirement in element specia- digested hair, nail and skin-scale samples (Chatter-
tion is the need to quantitatively determine each of jee et al., 1995; Das et al., 1995). Reports are also
the forms of a given element independently and available for arsenic speciation using graphite fur-
without interference from the other forms. In this nace (Shaikh and Tallman, 1978; Chakraborti et al.,
regard, an ideal element speciation method is one 1980, 1986, 1987; Chung et al., 1984). Howard and
that can provide the desired information without Arbab-Zavar (1981) described a microprocessor
altering the original sample. In the absence of such based ¯ow injection analysis system (FIAS) hydride
a method, elemental speciation has relied on a com- generator for accurate, fast and easy experimen-
bination of analytical techniques and method- tation. Arsenic speciation by ion-exchange separ-
ologies, including spectroscopic, chromatographic, ation followed by AAS determination has been
and electrochemical procedures. In many instances, reported (Grabinsk, 1981; Aggett and Kadwani,
physico-chemical approaches have been employed, 1983).
whereby all forms of the element of interest are Non-dispersive atomic absorption spectrometry
converted into one species and quanti®ed. for hydride-forming elements has also been devel-
The quanti®cation of dierent metal species is a oped. Compared to conventional dispersive AAS
rather dicult job as the concentration of heavy systems, this non-dispersive systems allow operation
metals in the environment are generally very low of the electrodeless discharge lamp (EDL) for
relative to the detection limits of the available ana- arsenic with high sensitivity and lower detection
lytical techniques. However, during recent years a limit (Haraguchi et al., 1981). Recently, a method
number of approaches have been employed to over- has been developed for the determination of trace
come this problem. In the following pages a amounts of As(III) and total arsenic with L-cysteine
detailed discussion is presented on the various tech- as prereductant using ¯ow injection hydride gener-
niques available for arsenic speciation, viz., spectro- ation coupled with a non-dispersive AAS device
scopic, chromatographic and electrochemical (Yin et al., 1996). Determination of arsenic by
methods, etc. inductively coupled plasma atomic emission spec-
A number of techniques are available for specia- trometry (ICP-AES) has also been developed with a
tion of arsenic compounds (Irgolic et al., 1983; detection limit below 0.1 mg/l (Pahlavanpour et al.,
Ebdon et al., 1988). Spectrometric methods for the 1980).
determination of arsenic involve the use of various Chromatographic techniques oer excellent possi-
spectrometric techniques such as UV, visible, bilities for separation of all arsenic species. Typical
atomic absorption, atomic emission, hydride gener- gas chromatographic methods involve conversion of
ation, graphite furnace, etc. The most widely inorganic and methylated arsenic compounds into
accepted procedures for the analysis of total arsenic their diethyldithiocarbamate complexes or tri-
exploit the reduction of arsenic compounds to gas- methylsilyl derivatives (Butts and Rainey, 1971;
eous arsine. This gas then either undergoes a calori- Henry and Thorpe, 1978). The approach of Berman
metric reaction (Kellen and Jaselskis, 1976) or is and co-workers (Braman and Foreback, 1973),
thermally decomposed to give elemental arsenic for however, involves the trapping of arsines formed by
atomic absorption spectrometry (Chu et al., 1972). reduction with sodium tetrahydroborate, and their
Howard and Arbab-Zavar (1980) has developed a subsequent sequential volatilization into an electric
spectrometric method for dierential determination discharge emission detector.
4308 C. K. Jain and I. Ali
Gas chromatography with ¯ame ionization detec- graphic approach that seems to overcome the limi-
tor has been used for the speciation of arsenic tations of HPLC is ion chromatography (IC). The
species (Beckermann, 1982; Ballin et al. 1994) with fundamental separation scheme involved here is ion
a detection limit of 0.1 ng. Methods have also been exchange. Ion chromatography with conductivity
developed based on headspace gas chromatography detection has been used for the determination of
following a chemical reaction and using ¯ame ioniz- arsenate in the presence of other ions (Hoover and
ation detector. Arsenic species have also been deter- Yager, 1984; Hemmings and Jones, 1991). Li et al.
mined by capillary gas chromatography using (1995) has speciated arsenite and arsenate using ion
microwave induced plasma atomic emission spec- chromatography with electrochemical detection.
trometer as the detector (Lobiniski and Adams, The columns generally used with ion chromatog-
1993). raphy include ion exchange, ion exclusion, etc.
With the development of high performance liquid (BDH, 1988; Korksich, 1989). Various detection
chromatography (HPLC) and other chromato- systems employed in ion chromatography include
graphic techniques, a variety of separation modes potentiometric, atomic spectrometry (AAS or AES)
have been employed to distinguish among dierent and photometric measurements after postcolumn
species, followed by calorimetric, spectroscopic, or derivatization of the separated species (Haddad and
electrochemical detection of the separated species Alexander, 1985; Kondratyunok and Schwedt,
(Van Loon, 1979; Eckho et al., 1982; Nisamanee- 1988). Ion chromatographic methods can be used to
pong et al., 1984; Haswell et al., 1985; Rauret et al., separate organic and inorganic ions, complex as
1991; Robards et al., 1991; Hakala and Pyy, 1992; well as simple ions, and neutral species. The tech-
Morita and Edmonds, 1992; Lopez et al. 1993; Le nique is particularly suitable for metal speciation in
et al., 1994; Hagege et al., 1995). Where metal aqueous solutions.
species are involved, chromatographic separation Polarography and voltametry techniques have
can take place either by direct separation of metal also been used for the speciation of arsenic (Flor-
ions using ion exchange columns or by adsorption ence, 1986). Anodic pulse voltameter, with a detec-
(reversed- or normal-phase) liquid chromatography tion limit of 0.2 ppb, has been used to dierentiate
if the metal species are complexed with organic between arsenite and arsenate (Pretty et al., 1990,
ligands. Irgolic et al. (1983) has described high per- 1992). Total arsenic concentration is determined by
formance liquid chromatography (HPLC) in combi- anodic voltametry by reducing As(V) into As(III)
nation with inductively coupled plasma atomic using SO2 (Pretty et al., 1993). Recently capillary
emission spectrometry (ICP-AES). High sensitivity electrophoresis has been used for the speciation of
has been achieved using ICP-MS (mass spec- inorganic and organic species (Gareil, 1990a,b;
trometry) in combination with HPLC (Beauchemin Lopez et al., 1993). It has also been coupled with
et al., 1989; Heitkemper et al., 1989; Hansen et al., mass spectrometry (Lopez-Sanchez et al., 1994).
1992). The coupling of mass spectroscopy with ICP
(Batley and Low, 1989; Rauret et al., 1991; Hakala
and Pyy, 1992; Hansen et al., 1992; Morita and CONCLUSIONS
Edmonds, 1992; Branch et al., 1994) is the most
eective detector in HPLC speciation studies. Arsenic contamination in natural water is a
Arsenite, arsenate, DMA and MMA have been spe- world wide problem and has become a challenge
ciated by HPLC using the coupling of mass spec- for the world scientists. The toxic eects of arsenic
trometry with ICP (Beauchemin et al., 1989; are related to its oxidation state, resulting in
Harrison and Rapsomanikis, 1989; Krull, 1991; increasing interests in the quantitative determi-
Rauret et al., 1991; Sheppared et al., 1992; Shum et nation of individual species. Speciation of trace el-
al., 1992; Weber, 1993; Demesmay et al., 1994; Le ements has become an important issue during the
et al., 1994). While numerous methodologies have past decade because of its impact on environmental
been developed employing HPLC where complexed chemistry, eco- and clinical toxicology and food
metals in clinical, environmental, and agricultural and energy related industries. Various approaches
samples are separated, the main drawback of this have been developed for speciation studies of
approach stems from the incompatibility of com- arsenic with its own advantages and limitations.
monly used mobile phase system with the ¯ame and However, research eorts are still needed to develop
plasma sources commonly used in atomic spec- inexpensive, rapid, sensitive and reproducible meth-
trometry. odologies for arsenic species capable of working in
The hyphenated techniques, HPLC±HGAAS the range of drinking water limits. It is obvious to
(Tye et al., 1985; Hakala and Pyy, 1992) and conclude that geographical distribution of arsenic,
HPLC±HGAES (Rauret et al., 1991) are now being quanti®cation of dierent species, their solubility
widely used for arsenic speciation. Super critical and bioavailability, and understanding of geochem-
liquid chromatography is another development in ical processes responsible for elevated arsenic con-
the ®eld of arsenic speciation (Laintz et al., 1992). centration in the environment is very much needed
A relatively new and fast growing chromato- for eective management of water resources.
Arsenic: occurrence, toxicity and speciation techniques 4309
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