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Arsenic: Occurrence, Toxicity and Speciation Techniques
Arsenic: Occurrence, Toxicity and Speciation Techniques
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INTRODUCTION
The elements occur in the environment in dierent oxidation states and form various species, e.g.,
As as As(V), As(III), As(0) and As (-III); Sb as
Sb(V), Sb(III), Sb(0), and Sb(-III); and Se as
Se(VI), Se(IV), Se(0) and Se(-II). In oxidized environment As, Sb and Se appear mostly as oxyanions (Cutter, 1992). The valency state of an
element plays an important role for the behavior of
the element in the aqueous system. For example,
toxicity of As(III) and Sb(III) is higher than that of
their pentavalent species (Berman, 1980; Gesamp,
1986). Similarly Cr(III) is an essential element while
Cr(VI) is highly toxic. The valency state of an element also determines the sorption behavior and
consequently the mobility in the aquatic environment.
Many metals occur in natural waters in dierent
physico-chemical forms. Among them simple
hydrated metal ions are considered to be the most
toxic, while strong complexes and species associated
with colloidal particles are usually assumed to be
less toxic (Russeva, 1995). Organometallic compounds of tin, mercury and lead (particularly simple
methylated species) are more toxic than the corresponding inorganic species. Organoarsenic compounds represent an exception in this series (Prange
and Jantzen, 1995). Current interest in the determination of dierent species of arsenic in natural
waters is caused due the fact that physiological and
toxic eects of arsenic are connected with its chemical forms. The toxicity of dierent arsenic species
varies in the order: arsenite > arsenate > monomethylarsonate (MMA) > dimethylarsinate (DMA)
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The toxicology of arsenic is a complex phenomenon as arsenic is considered to be an essential element also. Two types of toxicity, viz., acute and
sub-acute are known from long time. The acute
arsenic poisoning requiring prompt medical attention usually occurs through ingestion of contaminated food or drink. The major early manifestation
due to acute arsenic poisoning include burning and
dryness of the mouth and throat, dysphasia, colicky
abnormal pain, projectile vomiting, profuse diarrhea, and hematuria. The muscular cramps, facial
edema and cardiac abnormalities, shock can
develop rapidly as a result of dehydration (Done
and Peart, 1971).
Sub-acute arsenic toxicity mainly involves the respiratory, gastro-intestinal, cardio-vascular, nervous
and haematopoietic systems. It may cause loss of
appetite, nausea and some vomiting, dry throat,
shooting pains, diarrhea, nervous weakness, tingling
of the hands and feet, jaundice and erythema.
Longer exposure resulted in dry, falling hair, brittle
loose nails, eczema, darken skin exfoliation and a
hormy condition of the palms and soles (Holmquist,
1951; Pinto and Mcgill, 1953). The toxicities of various arsenic compounds to man and animals have
been studied by various workers (Sullivan, 1969;
USEPA (United States Environmental Protection
Agency), 1971; Fairchild et al., 1977). Chatterjee
(1994) has discussed the toxicity of arsenic to dierent organs.
Biologically, As(III) is considered more toxic
than As(V) (NAS (National Academy of Sciences),
1977). Data on the dierences in toxicity between
As(III) and As(V) on human beings are very limited. Trivalent arsenic is about 60 times more toxic
than oxidized pentavalent state (Ferguson and
Gavis, 1972). Inorganic arsenic compounds are
about 100 times more toxic than organic arsenic
compounds (DMMA and MMAA) (Nagy and
Korom, 1983). Methylation of inorganic arsenic in
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The results of clinical ndings for arsenic poisoning from drinking arsenic contaminated water show
the presence of almost all the stages of arsenic clinical manifestation (Hotta, 1989). After the intake of
arsenic into the human body, approximately 50%
of the arsenic is excreted in the urine (Das, 1995;
Das et al., 1995), with small portions through the
faeces, skin, hair, nails and lungs. Arsenic in urine,
faeces, skin, hair, nails and lungs has been used as
an indicator of the arsenic hazard to the population
(Borgono and Greiber, 1971; Goldsmith et al.,
1972; Yamamura and Yamauchi, 1980).
People drinking arsenic contaminated water generally show arsenical skin lesions, which are a late
manifestation of arsenic toxicity. Long term ex-
4307
of As(III) and As(V) species using silver diethyldithiocarbamate. Spectroscopic methods based on
the formation of molybdenum blue have also been
reported for arsenic speciation (Bogdanova, 1984;
Matsubara et al., 1987; Nasu and Kan, 1988;
Tamari et al., 1989; Palanivelu et al., 1992). Aggett
and Aspell (1976) has developed a method in which
control of pH of sodium tetraborate(III) reduction
solution was used to dierentiate between As(III)
and total arsenic, prior to analysis by atomic
absorption spectrometry.
Hydride generation atomic absorption spectrometry is one of the most widely used methods
for arsenic speciation due to its high sensitivity, low
detection limit and high selectivity (Andreae, 1977;
Howard and Arbab-Zavar, 1981; Aggett and Hayashi, 1987; Aggett and Boyes, 1989; Howard and
Comber, 1992). Flow injection hydride generation
atomic absorption spectrometry has also been used
for arsenic speciation in water and urine, and in
digested hair, nail and skin-scale samples (Chatterjee et al., 1995; Das et al., 1995). Reports are also
available for arsenic speciation using graphite furnace (Shaikh and Tallman, 1978; Chakraborti et al.,
1980, 1986, 1987; Chung et al., 1984). Howard and
Arbab-Zavar (1981) described a microprocessor
based ow injection analysis system (FIAS) hydride
generator for accurate, fast and easy experimentation. Arsenic speciation by ion-exchange separation followed by AAS determination has been
reported (Grabinsk, 1981; Aggett and Kadwani,
1983).
Non-dispersive atomic absorption spectrometry
for hydride-forming elements has also been developed. Compared to conventional dispersive AAS
systems, this non-dispersive systems allow operation
of the electrodeless discharge lamp (EDL) for
arsenic with high sensitivity and lower detection
limit (Haraguchi et al., 1981). Recently, a method
has been developed for the determination of trace
amounts of As(III) and total arsenic with L-cysteine
as prereductant using ow injection hydride generation coupled with a non-dispersive AAS device
(Yin et al., 1996). Determination of arsenic by
inductively coupled plasma atomic emission spectrometry (ICP-AES) has also been developed with a
detection limit below 0.1 mg/l (Pahlavanpour et al.,
1980).
Chromatographic techniques oer excellent possibilities for separation of all arsenic species. Typical
gas chromatographic methods involve conversion of
inorganic and methylated arsenic compounds into
their diethyldithiocarbamate complexes or trimethylsilyl derivatives (Butts and Rainey, 1971;
Henry and Thorpe, 1978). The approach of Berman
and co-workers (Braman and Foreback, 1973),
however, involves the trapping of arsines formed by
reduction with sodium tetrahydroborate, and their
subsequent sequential volatilization into an electric
discharge emission detector.
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Gas chromatography with ame ionization detector has been used for the speciation of arsenic
species (Beckermann, 1982; Ballin et al. 1994) with
a detection limit of 0.1 ng. Methods have also been
developed based on headspace gas chromatography
following a chemical reaction and using ame ionization detector. Arsenic species have also been determined by capillary gas chromatography using
microwave induced plasma atomic emission spectrometer as the detector (Lobiniski and Adams,
1993).
With the development of high performance liquid
chromatography (HPLC) and other chromatographic techniques, a variety of separation modes
have been employed to distinguish among dierent
species, followed by calorimetric, spectroscopic, or
electrochemical detection of the separated species
(Van Loon, 1979; Eckho et al., 1982; Nisamaneepong et al., 1984; Haswell et al., 1985; Rauret et al.,
1991; Robards et al., 1991; Hakala and Pyy, 1992;
Morita and Edmonds, 1992; Lopez et al. 1993; Le
et al., 1994; Hagege et al., 1995). Where metal
species are involved, chromatographic separation
can take place either by direct separation of metal
ions using ion exchange columns or by adsorption
(reversed- or normal-phase) liquid chromatography
if the metal species are complexed with organic
ligands. Irgolic et al. (1983) has described high performance liquid chromatography (HPLC) in combination with inductively coupled plasma atomic
emission spectrometry (ICP-AES). High sensitivity
has been achieved using ICP-MS (mass spectrometry) in combination with HPLC (Beauchemin
et al., 1989; Heitkemper et al., 1989; Hansen et al.,
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
Edmonds, 1992; Branch et al., 1994) is the most
eective detector in HPLC speciation studies.
Arsenite, arsenate, DMA and MMA have been speciated by HPLC using the coupling of mass spectrometry with ICP (Beauchemin et al., 1989;
Harrison and Rapsomanikis, 1989; Krull, 1991;
Rauret et al., 1991; Sheppared et al., 1992; Shum et
al., 1992; Weber, 1993; Demesmay et al., 1994; Le
et al., 1994). While numerous methodologies have
been developed employing HPLC where complexed
metals in clinical, environmental, and agricultural
samples are separated, the main drawback of this
approach stems from the incompatibility of commonly used mobile phase system with the ame and
plasma sources commonly used in atomic spectrometry.
The hyphenated techniques, HPLCHGAAS
(Tye et al., 1985; Hakala and Pyy, 1992) and
HPLCHGAES (Rauret et al., 1991) are now being
widely used for arsenic speciation. Super critical
liquid chromatography is another development in
the eld of arsenic speciation (Laintz et al., 1992).
A relatively new and fast growing chromato-
graphic approach that seems to overcome the limitations of HPLC is ion chromatography (IC). The
fundamental separation scheme involved here is ion
exchange. Ion chromatography with conductivity
detection has been used for the determination of
arsenate in the presence of other ions (Hoover and
Yager, 1984; Hemmings and Jones, 1991). Li et al.
(1995) has speciated arsenite and arsenate using ion
chromatography with electrochemical detection.
The columns generally used with ion chromatography include ion exchange, ion exclusion, etc.
(BDH, 1988; Korksich, 1989). Various detection
systems employed in ion chromatography include
potentiometric, atomic spectrometry (AAS or AES)
and photometric measurements after postcolumn
derivatization of the separated species (Haddad and
Alexander, 1985; Kondratyunok and Schwedt,
1988). Ion chromatographic methods can be used to
separate organic and inorganic ions, complex as
well as simple ions, and neutral species. The technique is particularly suitable for metal speciation in
aqueous solutions.
Polarography and voltametry techniques have
also been used for the speciation of arsenic (Florence, 1986). Anodic pulse voltameter, with a detection limit of 0.2 ppb, has been used to dierentiate
between arsenite and arsenate (Pretty et al., 1990,
1992). Total arsenic concentration is determined by
anodic voltametry by reducing As(V) into As(III)
using SO2 (Pretty et al., 1993). Recently capillary
electrophoresis has been used for the speciation of
inorganic and organic species (Gareil, 1990a,b;
Lopez et al., 1993). It has also been coupled with
mass spectrometry (Lopez-Sanchez et al., 1994).
CONCLUSIONS
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