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ARSENIC: OCCURRENCE, TOXICITY AND SPECIATION

TECHNIQUES
C. K. JAIN* and I. ALI
National Institute of Hydrology, Jal Vigyan Bhawan, Roorkee 247 667, India
(First received 1 January 1998; accepted in revised form 17 February 2000)
AbstractThe occurrence of arsenic in natural water has received signicant 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 identied and quantied.
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
Key wordsarsenic, toxicity, occurrence, speciation techniques, spectrometric, chromatographic, elec-
trochemical
INTRODUCTION
Arsenic contamination in natural water is a world
wide problem and has become a challenge for the
world scientists. It has been reported in recent years
from several parts of the world, like USA, China,
Chile, Bangladesh, Taiwan, Mexico, Argentina,
Poland, Canada, Hungary, Japan, and India
(Robertson, 1986, 1989; Moncure et al., 1992;
Schlottmann and Breit, 1992; Frost et al., 1993;
Das et al., 1994, 1995; Chatterjee et al., 1995). Her-
ing and Elimelech (1995) have reviewed the inter-
national perspective and treatment strategies on the
problem of arsenic contamination in ground water.
There is a growing awareness that the toxicity of
heavy metals is strongly dependent on their chemi-
cal form, resulting in increasing interests in the
quantitative determination of individual species
(Craig, 1986). Speciation of arsenic in environmen-
tal samples is gaining increasing importance, as the
toxic eects of arsenic are related to its oxidation
state. Many metallic ions are found in the environ-
ment in a variety of forms, that are dierentiated
not only by their physical and chemical forms, but
also by their diverse toxic activities with respect to
living organisms (Craig, 1986). Changes in the
degree of oxidation of an element also have an im-
portant eect on the degree of bioavailability and
toxicity (Stoeppler, 1992).
The elements occur in the environment in dier-
ent 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 en-
vironment As, Sb and Se appear mostly as oxya-
nions (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 el-
ement also determines the sorption behavior and
consequently the mobility in the aquatic environ-
ment.
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 com-
pounds of tin, mercury and lead (particularly simple
methylated species) are more toxic than the corre-
sponding inorganic species. Organoarsenic com-
pounds represent an exception in this series (Prange
and Jantzen, 1995). Current interest in the determi-
nation of dierent species of arsenic in natural
waters is caused due the fact that physiological and
toxic eects of arsenic are connected with its chemi-
cal forms. The toxicity of dierent arsenic species
varies in the order: arsenite > arsenate > mono-
methylarsonate (MMA) > dimethylarsinate (DMA)
Wat. Res. Vol. 34, No. 17, pp. 43044312, 2000
7 2000 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
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4304
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*Author to whom all correspondence should be addressed.
Tel.: +91-1332-72906, Ext. 249; fax: +91-1332-72123;
e-mail: ckj@nih.ernet.in
(Penrose, 1974; Lewis and Tatken, 1978; Stugeron
et al., 1989). The concentration of arsenic in natural
waters depends on the geological composition and
the degree of pollution of the environment. The
concentration of As(III) to As(V) varies widely
depending on the redox conditions in the geological
environment (Braman and Foreback, 1973;
Andreae, 1977; Shaikh and Tallman, 1978).
OCCURRENCE
Arsenic rarely occurs in free state, it is largely
found in combination with sulphur, oxygen and
iron (Brewstar, 1994; Chatterjee, 1994). Arsenic
occurs in the environment as a result of several
inputs that contain this element as organic and
inorganic forms (Rubio et al., 1992). The presence
of arsenic in natural water is related to the process
of leaching from the arsenic containing source
rocks and sediments (Robertson, 1989; Hering and
Elimelech, 1995). Inux of arsenic from various
anthropogenically-induced sources may also con-
taminate both soils and ground water especially
under anoxic conditions (Bhattacharya et al., 1996,
1997).
The presence of arsenic in natural water is gener-
ally associated with the geochemical environments
such as basin-ll deposits of alluvial-lacustrine ori-
gin, volcanic deposits, inputs from geothermal
sources, mining wastes and landlls (Welch et al.,
1988; Korte and Fernando, 1991). Occurrence of
arsenic in natural water depends on the local ge-
ology, hydrology and geochemical characteristics of
the aquifer materials (Bhattacharya et al., 1997).
Furthermore, the geochemical characteristics of the
aquifer material and their interactions with the aqu-
eous media also play an important role in control-
ling retention and/or mobility of arsenic within the
subsurface environment (Bhattacharya et al.,
1995a). Uncontrolled anthropogenic activities such
as smelting of metal ores, use of arsenical pesticides
and wood preservatives agents may also release
arsenic directly to the environment (Bhattacharya et
al., 1995b).
The redox conditions in the subsurface environ-
ment also play an important role in determining the
mobility of arsenic (Robertson, 1986). The oxi-
dation of dierent mineral species causes arsenic to
become soluble and enter into the surrounding en-
vironment through drainage water. Any phenomena
which aect the redox conditions such as pumping
rate and the land use pattern is of interest in ascer-
taining the primary mechanisms responsible for the
excess arsenic content in ground water. Robertson
(1989) has further reported that occurrence and ori-
gin of arsenic in ground water depends on several
factors such as adsorption-desorption, precipitation-
dissolution, oxidation-reduction, ion-exchange,
grain size, organic contents, biological activity and
aquifer characteristics. For example, Mok and Wai
(1989) studied the distribution and mobilization of
arsenic species in creek waters around the Blackbird
mining district, Idaho, and reported that the release
of arsenic was pH dependent and was related to the
total iron and free iron oxides in the sediments.
Leaching under a nitrogen atmosphere resulted in
an increased release of arsenic, which may be due
to the reduction of ferric-arsenate compounds to
the more soluble ferrous-arsenate forms.
The knowledge of the geographic distribution of
dierent arsenic species in natural water systems is
important for environmental consideration of the
geochemical and biological cycling of the element.
Furthermore, this will also provide insight into the
geochemical process responsible for elevated arsenic
concentrations in dierent hydrogeological environ-
ments.
TOXICITY
The toxicology of arsenic is a complex phenom-
enon as arsenic is considered to be an essential el-
ement also. Two types of toxicity, viz., acute and
sub-acute are known from long time. The acute
arsenic poisoning requiring prompt medical atten-
tion usually occurs through ingestion of contami-
nated 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 diar-
rhea, 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 res-
piratory, 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 var-
ious 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 dier-
ent 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 lim-
ited. 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
Arsenic: occurrence, toxicity and speciation techniques 4305
the body is a detoxication process, which reduces
the anity of the compound for tissue (Vahter and
Marafante, 1988).
The assessment of arsenic pollution in soils and
plants is also important from the toxicity point of
view. Several studies have been conducted concern-
ing arsenic and associated metals in stream sedi-
ments, soils, and crop plants. The Wolfson
Geochemical Atlas of England and Wales clearly
delineates the major arsenic province in Devon and
Cornwall (Webb et al., 1978). Subsequent studies
comparing the distribution patters of arsenic in
stream sediments and soils have conrmed extensive
soil contamination throughout southwest England
(Colbourne et al., 1975; Abrahams and Thornton,
1987). The majority of this area is under agricul-
tural use for arable and vegetable crop production
and for livestock farming. Thoresby and Thornton
(1979) have reported uptake of arsenic by pasture
herbage grown on a soil contaminated with arsenic.
The same ndings were also reported by Abrahams
(1983). However there is little evidence of signicant
arsenic uptake into locally grown farm, horticul-
tural and home garden crops. It can be concluded
that arsenic in these soils is present in forms that
are relatively insoluble and thus of low bioavailabil-
ity (Thornton, 1995).
Esser (1996) has studied the concentration of
arsenic in dierent soils and plant samples in agri-
cultural regions of Norway and reported that soil
cultivation inuences the relative concentration of
arsenic in the topsoil. Distribution of arsenic in
soils formed in the Indiana dunes has also been stu-
died with respect to particle size, mineralogy, soil
depth, soil age (Esser et al., 1991a) and eect of
aerosol inputs with respect to distance from the pol-
lution source, topography, vegetation and organic
matter (Esser et al., 1991b). There is obviously a
need for a multi-disciplinary study concerning en-
vironmental pathways, food chain transfer of
arsenic and possible health eects due to consump-
tion of contaminated foods.
HEALTH HAZARDS
The results of clinical ndings for arsenic poison-
ing from drinking arsenic contaminated water show
the presence of almost all the stages of arsenic clini-
cal 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 gen-
erally show arsenical skin lesions, which are a late
manifestation of arsenic toxicity. Long term ex-
posure to arsenic contaminated water may lead to
various diseases such as conjunctivitis, hyperkerato-
sis, hyperpigmentation, cardiovascular diseases, dis-
turbance in the peripheral vascular and nervous
systems, skin cancer, gangrene, leucomelonisis, non
pitting swelling, hepatomegaly and splenomegaly
(Kiping, 1977; WHO (World Health Organisation),
1981; Pershagen, 1983). The eects on the lungs,
uterus, genitourinary tract and other parts of the
body have been detected in the advance stages of
arsenic toxicity. Besides, high concentrations of
arsenic in drinking water also result in an increase
in stillbirths and spontaneous abortions (Csanady
and Straub, 1995).
Arsenic contamination in ground water of Tai-
wan is well known (Lu, 1990a,b) and has resulted
in arsenism and black-foot disease in people drink-
ing contaminated ground water. Some cases of can-
cer are also prevalent in the endemic areas (Chem
et al., 1988). In Antofagasta, over 12% of the popu-
lation exhibiting dermatological manifestations re-
lated to arsenic due to consumption of high arsenic
containing drinking water (Borgono and Greiber,
1972). Chronic arsenic poisoning was also reported
in some parts of North Mexico (Cebrian et al.,
1983). The exposed population of the region
showed one of the cutaneous signs of chronic
arsenic poisoning. A similar incident involving
arsenic was also reported from Cardoba Province,
north of Argentina (Astol et al., 1981). Regular
intake of arsenic contaminated water resulted in
skin cancer. The problem of arsenic contamination
in ground water of West Bengal, India has been
claimed as the biggest calamity in the world (Chat-
terjee, 1994; Das et al., 1994, 1995; Chatterjee et al.,
1995; Mandal et al., 1996). Other incidents invol-
ving smaller population groups have been reported
in Poland, Minnesota, USA, Chile, North Mexico,
Argentina, Canada, Hungary, Japan, New Zealand,
and Spain and have been compiled by Chatterjee
(1994). The important nding in most of these cases
was the close relationship between the prevalence of
cutaneous lesions and the exposure to drinking
water containing high levels of arsenic.
SPECIATION TECHNIQUES
The concept of speciation dates back to 1954
when Goldberg (1954) introduced the concept of
speciation to improve the understanding of the bio-
geochemical cycling of trace elements in seawater.
Kinetic and thermodynamic information together
with analytical data made it possible to dierentiate
between oxidized vs reduced, complexed or chelated
vs free metal ions in solution and dissolved between
particulate species.
Florence (1982) has dened the term speciation
analysis as the determination of the individual phy-
sico-chemical forms of the element, which together
make up its total concentration in a sample.
C. K. Jain and I. Ali 4306
According to Lung (1990), speciation analysis
involves the use of analytical methods that can pro-
vide information about the physico-chemical forms
of the elements. Schroeder (1989) distinguishes
physical speciation, which involves dierentiation of
the physical size or the physical properties of the
metal, and chemical speciation, which entails the
dierentiation among the various chemical forms.
The elements occur in the environment in dier-
ent oxidation states and form various species.
Dierent species of the same element may have
dierent chemical and toxicological properties.
Therefore, determination of the total concentration
of an element may not provide information about
the actual physico-chemical forms of the element,
required for understanding its toxicity, biotrans-
formation, etc. Thus, in order to obtain information
on toxicity and biotransformation of elements in
aquatic systems, quantication of individual species
of an element is needed.
The fundamental requirement in element specia-
tion is the need to quantitatively determine each of
the forms of a given element independently and
without interference from the other forms. In this
regard, an ideal element speciation method is one
that can provide the desired information without
altering the original sample. In the absence of such
a method, elemental speciation has relied on a com-
bination of analytical techniques and method-
ologies, including spectroscopic, chromatographic,
and electrochemical procedures. In many instances,
physico-chemical approaches have been employed,
whereby all forms of the element of interest are
converted into one species and quantied.
The quantication of dierent metal species is a
rather dicult job as the concentration of heavy
metals in the environment are generally very low
relative to the detection limits of the available ana-
lytical techniques. However, during recent years a
number of approaches have been employed to over-
come this problem. In the following pages a
detailed discussion is presented on the various tech-
niques available for arsenic speciation, viz., spectro-
scopic, chromatographic and electrochemical
methods, etc.
A number of techniques are available for specia-
tion of arsenic compounds (Irgolic et al., 1983;
Ebdon et al., 1988). Spectrometric methods for the
determination of arsenic involve the use of various
spectrometric techniques such as UV, visible,
atomic absorption, atomic emission, hydride gener-
ation, graphite furnace, etc. The most widely
accepted procedures for the analysis of total arsenic
exploit the reduction of arsenic compounds to gas-
eous arsine. This gas then either undergoes a calori-
metric reaction (Kellen and Jaselskis, 1976) or is
thermally decomposed to give elemental arsenic for
atomic absorption spectrometry (Chu et al., 1972).
Howard and Arbab-Zavar (1980) has developed a
spectrometric method for dierential determination
of As(III) and As(V) species using silver diethyl-
dithiocarbamate. 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 spec-
trometry 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 Haya-
shi, 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 (Chatter-
jee et al., 1995; Das et al., 1995). Reports are also
available for arsenic speciation using graphite fur-
nace (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 experimen-
tation. Arsenic speciation by ion-exchange separ-
ation 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 devel-
oped. 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 gener-
ation coupled with a non-dispersive AAS device
(Yin et al., 1996). Determination of arsenic by
inductively coupled plasma atomic emission spec-
trometry (ICP-AES) has also been developed with a
detection limit below 0.1 mg/l (Pahlavanpour et al.,
1980).
Chromatographic techniques oer excellent possi-
bilities for separation of all arsenic species. Typical
gas chromatographic methods involve conversion of
inorganic and methylated arsenic compounds into
their diethyldithiocarbamate complexes or tri-
methylsilyl 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.
Arsenic: occurrence, toxicity and speciation techniques 4307
Gas chromatography with ame ionization detec-
tor 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 ioniz-
ation detector. Arsenic species have also been deter-
mined by capillary gas chromatography using
microwave induced plasma atomic emission spec-
trometer as the detector (Lobiniski and Adams,
1993).
With the development of high performance liquid
chromatography (HPLC) and other chromato-
graphic 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; Nisamanee-
pong 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 per-
formance liquid chromatography (HPLC) in combi-
nation with inductively coupled plasma atomic
emission spectrometry (ICP-AES). High sensitivity
has been achieved using ICP-MS (mass spec-
trometry) 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 spe-
ciated by HPLC using the coupling of mass spec-
trometry 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 com-
monly used mobile phase system with the ame and
plasma sources commonly used in atomic spec-
trometry.
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 limi-
tations 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 chromatog-
raphy 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 tech-
nique is particularly suitable for metal speciation in
aqueous solutions.
Polarography and voltametry techniques have
also been used for the speciation of arsenic (Flor-
ence, 1986). Anodic pulse voltameter, with a detec-
tion 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 SO
2
(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
Arsenic contamination in natural water is a
world wide problem and has become a challenge
for the world scientists. The toxic eects of arsenic
are related to its oxidation state, resulting in
increasing interests in the quantitative determi-
nation of individual species. Speciation of trace el-
ements has become an important issue during the
past decade because of its impact on environmental
chemistry, eco- and clinical toxicology and food
and energy related industries. Various approaches
have been developed for speciation studies of
arsenic with its own advantages and limitations.
However, research eorts are still needed to develop
inexpensive, rapid, sensitive and reproducible meth-
odologies for arsenic species capable of working in
the range of drinking water limits. It is obvious to
conclude that geographical distribution of arsenic,
quantication of dierent species, their solubility
and bioavailability, and understanding of geochem-
ical processes responsible for elevated arsenic con-
centration in the environment is very much needed
for eective management of water resources.
C. K. Jain and I. Ali 4308
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