A Review On Sources, Toxicity and Remediation Technologies For Removing Arsenic From Drinking Water

Res Chem Intermed (2014) 40:447485
DOI 10.1007/s11164-012-1000-4
A review on sources, toxicity and remediation

technologies for removing arsenic from drinking water
Ankita Basu Debabrata Saha Rumpa Saha
Tuhin Ghosh Bidyut Saha
Received: 7 August 2012 / Accepted: 23 December 2012 / Published online: 9 January 2013
Springer Science+Business Media Dordrecht 2013
Abstract Arsenic is a natural element found in the environment in organic and

inorganic forms. The inorganic form is much more toxic and is found in ground water,
surface water and many foods. This form is responsible for many adverse health
effects like cancer (skin, lung, liver, kidney and bladder mainly), and cardiovascular
and neurological effects. The estimated number of people in Bangladesh in 1998
exposed to arsenic concentrations above 0.05 mg/l is 2835 million, and the number
of those exposed to more than 0.01 mg/l is 4657 million. The estimated number of
people in West Bengal, India (the border province to Bangladesh), in 1997 actually
using arsenic-rich water is more than 1 million for concentrations above 0.05 mg/l
and is 1.3 million for concentrations above 0.01 mg/l. The United States Environmental Protection Agency (USEPA) has estimated that 13 million of the US population are exposed to arsenic in drinking water at 0.01 mg/l. The situation has
prevailed for more than 10 years and is more severe now. The USEPA lowered the
maximum contaminant level (MCL) for drinking water arsenic from 50 to 10 lg/l in
2001 based on international data analysis and research. This recommendation is now
on hold. The level of 10 ppb become standard in the European Union (EU) in 2001.
Arsenic may be found in water flowing through arsenic-rich rocks. The source is
diverse. These include the earths crust, introduced into water through the dissociation
of minerals and ores, industrial effluents to water, combustion of fossil fuels and
seafoods. Arsenic-removal methods are coagulation (ferric sulfate, ferrous sulfate,
A. Basu R. Saha B. Saha (&)
Department of Chemistry, The University of Burdwan, Golapbag, Burdwan 713104,
West Bengal, India
e-mail: b_saha31@rediffmail.com
D. Saha
Department of Chemistry, Suri Vidyasagar College, Suri, Birbhum 731101, West Bengal, India
T. Ghosh
Department of Chemistry, A.B.N. Seal College, Cooch Behar 736101, West Bengal, India
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A. Basu et al.
ferric chloride, aluminum sulfate, copper sulfate, and calcium hydroxide as coagulants), adsorption (activated carbon, activated alumina, activated bauxite) ion
exchange, bio-sorption, etc.
Keywords
Arsenic Toxicity Source Removal techniques
Introduction
Sources of drinking water are of three different types. These sources are surface
water (river water, lake water and pond water), rain water and ground water. Surface
water needs processing while rain water needs proper storage, which may not be
sufficient. On the other hand, ground water does not require processing and storage.
In addition, agriculture is the main source of income for highly populated Asian
countries. During the dry season, surface water is not sufficient for irrigation.
Ground water is the only solution. Dangerous arsenic levels in natural waters are
now a universal problem and often referred to as a twentiethtwenty-first century
calamity. Arsenic contamination of ground water is now regarded as one of the
worst public health crises [13]. Arsenic also enters into the human body system via
the food chain. The presence of arsenic in ground water has been reported from
many parts of the world, such as Argentina [49], Australia [10, 11] Bangladesh
[1222], Cambodia [2327], Canada [28, 29], Chile [30, 31], China [3237], Ghana
[3840], Germany [4143], Hungary [44, 45], India [4669], Japan [7074], Laos
[75], Mexico [7682], Nepal [8386], Pakistan [8790], Poland [91, 92], Romania
[93], Taiwan [94100], Thailand [101], UK [102], USA [103, 104], and Vietnam
[105111].
With increasing population and with the change in climate, ground water
represents one of the most important and stable sources of drinking water. There is
an immediate, critical need to supply arsenic-free drinking water to society, and this
need will continue to grow. The magnitude of the problem of poisoning was so great
that the World Health Organization, having recognized the enormous health
implications, lowered the provisional guideline value for arsenic in drinking water
from 50 to 10 lg/l. One of the main uses of arsenic in the past was as pesticides in
agriculture, e.g. MSMA (monosodium methylarsonate, NaMeHAsO3), DSMA
(disodium salt, Na2MeAsO3) [112], and wood preservation with CCA (chromated
copper arsenate) [113]. Arsenic had its uses in medicine, too, against syphilis and
African trypanosomiasis, though in recent years these uses have become obsolete
[113]. Arsenic from the natural environment and anthropogenic sources can enter
the human body through food, water, soil, and air. Inhalation of airborne arsenic or
arsenic-contaminated dust is a common health problem in many ore mines. As the
particular species in the environment is not normally determined in routine
procedures, so the level and nature of arsenic exposure may not be known. Here,
Table 1 summarizes the documented cases of naturally occurring arsenic poisoning
throughout ground water in the whole world [78].
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A review on sources, toxicity and remediation technologies
449
Table 1 Naturally occurring poisoning throughout ground water in the whole world
Sl.
no.
Country/
religion
Potential
exposed
population
Concentration
(lg/l)
Environmental conditions
Reference
Bangladesh
30,000,000
\12,500
Natural; alluvial/deltaic sediments

with high phosphate, organics
[78]
West
Bengal
6,000,000
\103,200
Similar to Bangladesh
Vietnam
[1,000,000
13,050
Natural; alluvial sediments
Thailand
15,000
1[5,000
Anthropogenic; mining and

dredged alluvium
Taiwan
100,000200,000
101,820
Natural; coastal zones, black

shales
Inner
Mongolia
100,000600,000 \12,400
Natural; alluvial and lake

sediments; high alkalinity
Xinjiang,
Shanxi
[500
40750
Argentina
2,000,000
\19,900
Natural; loess and volcanic rocks,

thermal springs; high alkalinity
Chile
400,000
1001,000
Natural and anthropogenic;

volcanogenic sediments; closed
basin lakes, thermal springs,
mining
10
Bolivia
50,000
Natural; similar to Chile and parts

of Argentina
11
Brazil
0.4350
Gold mining
12
Mexico
400,000
8620

volcanic sediments, mining
13
Germany
\10150
Natural: mineralized sandstone
14
Hungary,
Romania
400,000
\2176
Natural; alluvial sediments;

organics
15
Spain
[50,000
\1100
16
Greece
150,000

thermal springs and mining
17
United
Kingdom
\180
Mining; southwest England
18
Ghana
\100,000
\1175
Anthropogenic and natural; gold

mining
19
USA,
Canada
\1[100,000

mining, pesticides, As2O3
stockpiles, thermal springs,
alluvial, closed basin lakes,
various rocks
Arsenic chemistry
The element arsenic (valence configuration 3d10 4s2 4p3) is known to exist in four
major oxidation states, ?5, ?3, 0, and -3. It is found as a commonly distributed
element in the atmosphere, rocks, minerals, soil, water, and in the biosphere. In
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A. Basu et al.
natural water, arsenic is mostly found in inorganic form as oxyanions of trivalent

and pentavalent arsenic [79]. Redox potential (Eo) and pH are the most important
factors controlling arsenic speciation. The toxicity of varies with the chemical form
in which it is found. The toxicity can range from essentially nontoxic to excessively
toxic, depending upon (1) oxidation state and (2) the groups bound to the arsenic.
AsH3 (arsine, the hydride) is considered to be the most toxic species whereas
arsenosugars and arsenobetaine are thought to be non-toxic [114]. Trivalent
inorganic arsenic compounds are considered to be more toxic than pentavalent
inorganic compounds, and organo-compounds in the pentavalent state are less toxic
than inorganic arsenic. Recent studies have shown that methylated trivalent arsenic
species may be more toxic than inorganic species [115]. They are certainly more
toxic than pentavalent organo arsenic [116]. Trivalent arsenic being soft prefers the
SH groups of different enzymes to inhibit the enzymatic process [116]. The
chemistry of arsenic is comparable with that of phosphorus. Arsenate is structurally
similar to phosphate, thus it can replace a phosphate group in ATP forming an easily
hydrolyzed arsenate ester of ADP. This leads to uncoupling of phosphorylation and
the breakdown of essential metabolic processes [114, 117]. 3-Arsenopyruvate [HO
As(O)(OH)CH2COCOOH] can competitively inhibit phosphoenolpyruvate
mutase (PEP mutase) which is required for the bio-synthesis of CP bonds in the
living bodies. So, arsenic toxicity may arise due to SH group blocking of the
different enzymes. Uncoupling of phosphorylation and the breakdown of essential
metabolic processes like glucose metabolism leads to denaturation of different
proteins.
The detection and quantification of individual forms of an element is called
chemical speciation. Arsenic may remain in four oxidation states (-3, 0, ?3, and
?5), but the -3 and 0 species prevail only in strongly reducing condition. Scheme 1
represents speciation in the environment [116].
There are a number of modern techniques for the speciation and separation for
trivalent and pentavalent . Carbon nanofibers (CNFs) are good sorbents for their
speciation and separation by column chromatography. A micro-column packed with
CNFs in the pH range 1.03.0 in the presence of ammonium pyrroinedithiocarbamate adsorbs trivalent arsenic whereas pentavalent arsenic gets released. The
detection limits for trivalent and pentavalent arsenic are 0.0045 and 0.24 mg/ml,
respectively [118].
Sources of arsenic
Minerals
Major arsenic minerals
Arsenic metal very rarely occurs in nature in its pure form. It occurs as a major
constituent in more than 200 minerals, including elemental , arsenides, sulfides,
oxides, arsenates, and arsenites. A list of some of the most common arsenic minerals
is given in Table 2; most are ore minerals or their alteration products. However,
123

Oxidation
Me2AsVO(OH)
Me2AsH
Reduction
Oxidation
Me 3 As
451
Bacterial
Reduction
V Biomethylation
Me3 As O
V
Me2As O(OH)
Biomethylation
V
As O2(OH)
Reduction
(Bacteria)
III
As O(OH)
Biomethylation
Reduction
Reduction
FeAsO4
V
MeAs O(OH)2
AsH3
(Sediment)
As 2S3
MeAsH2
(Sediment)
Scheme 1 Species distribution of in the environment
these minerals are relatively rare in the natural environment. Several other, less
common minerals contain arsenic, including orpiment, realgar, and enargite, which
are arsenic sulfides. Arsenic commonly accompanies deposits of copper, silver,
gold, zinc, cadmium, mercury, uranium, tin, lead, phosphorus, antimony, bismuth,
sulfur, selenium, tellurium, molybdenum, tungsten, iron, nickel, cobalt, and
platinum, particularly those containing sulfides and sulfosalts. The commonly
identified arsenic-bearing minerals are realgar (AsS), orpiment (As2O3), arsenopyrite (FeAsS), claudetite (As2O3), arsenolite (As2O3), pentoxide (As2O5), and
scorodite (FeAsO42H2O). Within this group of minerals, arsenopyrite is probably
the most common and abundant mineral [119121]. In the weathering of sulfides,
arsenic can be oxidized to arsenite and arsenate. Arsenic oxide is also formed as a
by-product of copper, lead, and nickel smelting. In fact, environmental laws require
that arsenic be removed from ores, so that it does not enter the environment in
effluent gases, fluids, or solids. The greatest concentrations of these minerals occur
in mineralized areas. It is generally accepted that arsenopyrite, together with the
other dominant As-sulfide minerals, realgar and orpiment, are only formed under
high temperature conditions in the earths crust. However, authigenic arsenopyrite
has also been reported in sediments [122]. Although often present in ore deposits,
arsenopyrite is much less abundant than arsenian (-rich) pyrite (Fe(S, As) 2), which
is probably the most important source of arsenic.
123
Low-temperature hydrothermal vein mineral associated

with other and antimony minerals,clays and
limestones; also occurs as volcanic sublimation,
deposits from hot springs. Vein deposits,often
associated with orpiment, clays andlimestones,also
deposits from hot springs
Hydrothermal viens, hot springs and occurs as
sublimation product in volcanic fumaroles
NiAs
AsS/As4S4
As2S3
CoAsS
FeAsS
Cu12As4S13
Cu3AsS4
(Cu2AsO4OH)
Niccolite/Nickeline
123
Realgar
Orpiment
Cobaltite
Arsenopyrite
Tennantite
Enargite
Olivenite
Ag3AsS3
As2O3
Proustite
Arsenolite
Secondary mineral formed by oxidation of arsenopyrite,

native and other As minerals
Late-forming mineral in hydrothermal deposits; in the

oxidized and enriched zone, associated with other
silver minerals and sulfides
Secondary mineral in lead ores

Secondary mineral in cobalt-bearing deposits
Pb5(AsO4)3Cl
Co3(AsO4)28H2O
Mimetite
Erythrite
Hydrated copper arsenate mineral, found in copper

deposits
Secondary mineral in the oxide zone of CoNiAsbearing mineral deposits
Hydrothermal veins and contact metamorphic deposits

in association with other CuPbZnAg sulfides and
sulfosalts
High temperature hydrothermal veins, in pegmatites,

and in areas of contact metamorphism or
metasomatism
High-temperature deposits, metamorphic rocks
Vein deposits and norites
Hydrothermal veins
As
Native
Occurrence
Composition
Mineral
Table 2 Major arsenic minerals occurring in nature
[122124]
Reference
452
A. Basu et al.
Secondary mineral formed by oxidation of realgar,

arsenopyrite and other As minerals
Hydrothermal deposits and as a secondary mineral in
gossans worldwide
Secondary mineral
Secondary mineral, smelter wastes
Weathering product, secondary mineral
Secondary mineral
Oxidation product of arsenopyrite and other As
minerals
Hydrothermal AsS veins, in the condensation zone of a
hydrothermal HgSbAs system, area of basaltic
shield volcano with lacustrine sediments,
hydrothermal fluids from hot springs
Uranium deposit, as a secondary fracture-filling mineral
As2O3
FeAsO42H2O
Ni3(AsO4)28H2O
Mg3(AsO4)28H2O
(Mn,Mg)4Al(AsO4)(OH)8
CaCu(AsO4)(OH)
KFe4(AsO4)3(OH)46-7H2O
Cu6Hg3As4S12
As8S9
Claudetite
Scorodite
Annabergite
Hoernesite
Haematolite
Conichalcite
Pharmacosiderite
Aktashite
Alacranite
As an encrustation on furnace walls in which ores are

roasted
A rare mineral in hausmannite ore from a
metamorphosed FeMn ore body; in a
metamorphosed stratiform zinc ore body
CaMgAsO4OH
Ni9(AsO4)2AsO8
(Mn,Mg)5(AsO4)2(OH)44H2O
(La/Ce)Cu6[(OH)6(AsO4)3]3H2O
Adamite
Adelite
Aerugite
Akrochordite
Agardite
Baritefluorite veins including copper, silver and lead

minerals, hosted by gneisses and triassic sandstones
A rare mineral in a metamorphosed FeMn ore body; on

willemitefranklinite ore from a metamorphosed
stratiform zinc ore body
Occurs as a secondary mineral in the oxidized zone of

zinc and -bearing hydrothermal mineral deposits
K2(UO2)2(AsO4)26H2O
Zn2AsO4OH
Abernathyite
Hydrothermal veins, Aktashskoye SbHg deposits
Occurrence
Composition
Mineral
Table 2 continued
Reference

453
123
123
Metamorphosed sulfosalt/sulfide deposit in sugary
dolomite
_
Pb3As4S9
Baumhauerite
In hydrothermal deposits
A post-mining superficial weathering product of FeAs

sulfides
_
_
_
Secondary copper arsenate mineral occurring in the
oxidized zones of some -bearing copper
Mg(AsO3OH)4(H2O)
Fe2(AsO4)(SO4)(OH)7(H2O)
(Ce,Nd,La)(Fe?3,Fe?2,Ti,Al)3O2 (Si2O7)(As?3O3)(OH))
(Ca(Mg,Al,Fe3?)2[AsO4]220(H2O,OH)
Ca2[AsO4][B(OH)4]
Cu2Al(AsO4)(OH)44(H2O)
Cu3AsO4(OH)3
Cu5(AsO4)2(OH)4
PbCuAsO4(OH)
Beudantite
Brassite
Bukovskyite
Cervandonite
Cabalzarite
Cahnite
Chalcophyllite
Clinoclase
Cornubite
Duftite
Uncommon mineral, occurs in the oxidized zone of

some sulfide deposits
Rare secondary copper arsenate mineral
Secondary copper mineral and forms acicular crystals in

the fractured weathered zone above copper sulfide
deposits
Rich vein-type AgCoNiBiU deposit
Secondary mineral occurring in the oxidized zones of

polymetallic deposits
PbCrO4, AsO4, SiO2
PbFe3(OH)6SO4AsO4
Bellite
A rare mineral in the oxidized zone of secondary

minerals of copper, -bearing base metal deposits
Cu6As
CaZnAsO4(OH)
Algodonite
An uncommon oxidation zone mineral in NiCoAs

deposits
Austinite
Low-temperature secondary parageneses
Ni3(AsO4)28H2O
Annabergite
Metamorphosed MnFe ore bodies
Mn7(AsO4)2(OH)8
KCdCu5[H2AsO4(AsO4)4]2H2O
Allactite
Occurrence
Composition
Andyrobertsite
Mineral
Table 2 continued
Reference
454
A. Basu et al.
Found in vein and replacement deposits formed at

moderate temperatures
_
Occurs in silver mines, hydrothermal deposits
Hydrothermal copper deposits

Occurs as a secondary mineral in the oxidized zone of
manganese
Cu3As
NiAs2
FeAs2
PbCuAsS3
CoAs2
Cu2AsO4OH3H2O
(Ag,Cu,Fe)12(Sb,As)4S13
Pb2Cu(CrO4)(AsO4)(OH)
(Cs,Tl)(Hg,Cu,Zn)6(As,Sb)4S12
Pb14(Sb, As)6S23
NiAsS
(Co,Fe)AsS
Pb9As4S15
Mn5(AsO3OH)2(AsO4)210H2O
(Tl,Pb)2As5S9
Ca(AsO3OH)H2O
Domeykite
Rammelsbergite
Lollingite
Seligmannite
Smaltite
Euchroite
Freibergite
Fornacite
Galkhaite
Geocronite
Gersdorffite
Glaucodot
Gratonite
Geigerite
Hutchinsonite
Haidingerite
Secondary Fearsenate minerals

Occurs as phase alpha-AsS, trimorph of realgar and
pararealgar
Fe(H2AsO4)35H2O
FeAsO435H2O
Kaatialaite
Kankite
Occurs as a dehydration product of pharmacolite in the

Getchell Mine
Rare hydrothermal mineral
Occurs in high temperature hydrothermal deposits with

pyrrhotite and chalcopyrite
Occurs as a hydrothermal vein mineral along with other

nickel sulfides
Found in hydrothermal veins usually associated with

other similar minerals, particularly the sulfides of iron
and copper
Occurs in Carlin-type hydrothermal deposits
Occurs in the hydrothermal veins
Found in mesothermal vein deposits
Commonly in mesothermal vein deposits
Occurrence
Composition
Mineral
Table 2 continued
Reference

455
123
Uncommon secondary mineral in the oxidized zone of

zinc-bearing deposits and occurs rarely in granite
pegmatite
Found as a secondary minerals in the oxidized zone of
primary copper ores
TlAsS2
NaCaCu5(AsO4)4Cl5H2O
Zn2(AsO4)(OH)(H2O)
Cu2AlAsO4(OH)44H2O
Lorandite
123
Lavendulan
Legrandite
Liroconite
Secondary minerals, associated with hydrothermal

nickel minerals in a metamorphosed ultramafic,
within serpentinite-hosted chromite deposits
Found in nature as a secondary mineral and can also be
formed by exposing realgar to light at wavelengths
between approximately 500 and 670 nm
Found worldwide and is an ore of silver. The name
comes from the number of base metals in the mineral
Formed as an oxidation product of -bearing sulfides in
reaction with surrounding calcium-bearing rocks
Ni11As8
Ni2FeAs2
b-AsS/As4S4
(AgCu)16(SbAs)2S11
Ca4Mg(AsO3OH)2(AsO4)211H2O
Maucherite
Oregonite
Pararealgar
Polybasite
Picropharmacolite
Occurs in hydrothermal veins alongside other nickel

arsenide and sulfide minerals
In a hydrothermal deposit with other sulfides

Occurs as a secondary mineral in the oxidized zones of
copper deposits, as radiating acicular prisms and
massive encrustations
AgHgAsS3
BiCu6(AsO4)3(OH)63(H2O)
Laffittite
Mixite
Uncommon copper arsenate mineral, associated with

erythrite, cuprite, malachite and cobaltian wad
Occurs in low-temperature hydrothermal associations

and in gold and mercury ore deposits
Occurs in the Geshiber vein, Svornost shaft intergrowth

with nickel skutterudite and sometimes with
tennantite
NiAs2
Krutovite
Occurrence
Composition
Mineral
Table 2 continued
Reference
456
A. Basu et al.
Extremely rare in a deep oxidation zone in a dolostonehosted hydrothermal polymetallic ore deposit
Occurs in the layered igneous complex, in the

Oktyabrskoye coppernickel deposit and in the
nickel ore deposit of Sudbury Basin
_
Secondary mineral formed by the weathering of
associated copper and minerals
Hydrothermally kaolinized zone in an F-enriched
granitic pegmatite intruded in Precambrian staurolite
schists
Occurs as a secondary mineral in the oxidized
weathering zone of hydrothermal uranium ore
deposits which contain
Zn3(AsO3)2
Tl(Cu,Ag)(Hg,Zn)2(As,Sb)2S6
(Co,Ni,Fe)As3
PtAs2
Ca4MgAs2B12O22(OH)1212(H2O)
CaCu5(AsO4)2CO3(OH)46H2O
(Na,K)2PbAs4(Nb,Ta,Ti)4O18
Cu(UO2)2(AsO4)210-16(H2O)
Reinerite
Routhierite
Skutterudite
Sperrylite
Teruggite
Tyrolite
Zimbabweite
Zeunerite
Hydrothermal ore mineral found in moderate to high

temperature veins with other NiCo minerals
In hydrothermal deposits in dolostone
Occurrence
Composition
Mineral
Table 2 continued
Reference

457
123
458
A. Basu et al.
In the case of the presence of arsenopyrite in sulfide ores having association with
sediment-hosted gold deposits, it is likely to be the earliest-formed minerals which are
obtained from hydrothermal solutions and formed around 100 C. It is responsible for
the native arsenic first and then arsenian pyrite, and even later, these are converted into
realgar and orpiment. This paragenetic sequence is often reflected by zonation within
sulfide minerals, with arsenopyrite cores zoning out to arsenian pyrite and realgar
orpiment rims. Oxides and sulfates are formed at the latest stages of ore mineralization
[123, 124].
Rock-forming minerals
Arsenic is often present in varying concentrations in other common rock-forming
minerals, not as a major component. As far as the crustal abundance of arsenic is
concerned, it is 1.5 mg/kg. The element is strongly chalocophile. Almost 60 % of
natural minerals are arsenates, 20 % sulfides and sulfosalts, and the remaining 20 %
are arsenides, arsenites, oxides, alloys, and polymorphs of elemental arsenic. As the
chemistry of arsenic closely follows that of sulfur, the greatest concentrations of the
element tend to occur in sulfide minerals, of which pyrite is the most abundant.
Arsenic concentrations of more than 105 mg/kg have been reported in sulfide minerals
and up to 7.6 9 104 mg/kg in iron oxides [125, 126]. However, concentrations are
typically much lower. Incorporation of arsenic into primary rock-forming minerals is
restricted in extent, for example by the substitution of As3? for Fe3? or Al3?.
Therefore, arsenic concentrations in silicate minerals are typically *1 mg/kg or less
[79]. Many igneous and metamorphic rocks have average arsenic concentrations of
110 mg/kg. Innumerable carbonate minerals and carbonate rocks contain similar
concentrations [127]. Concentrations in pyrite, chalcopyrite, and galena may change,
even within a given grain, but in some cases reach up to 10 % by weight (Table 3).
Arsenic may be found in the crystal structure of many sulfide minerals as a substitute
for sulfur. Apart from being a significant constituent of ore bodies, pyrite is also
formed in low-temperature sedimentary environments under reducing conditions
(authigenic pyrite). Authigenic pyrite plays a very important role in present-day
geochemical cycles. As for the natural formation of arsenic, the rich sources include
the sediments of a number of rivers, lakes and the oceans, as well as many aquifers.
Pyrite commonly forms preferentially in zones of intense reduction, such as around
buried plant roots or other nuclei of decomposing organic matter. It is sometimes
present in a characteristic form as framboidal pyrite. As and when this pyrite gets
formed, some of the soluble arsenic is liable to be imbibed. Pyrite is not stable in
aerobic systems and oxidizes to iron oxides with the release of large amounts of
sulfate, acidity, and associated trace constituents including arsenic. The presence of
pyrite as a minor constituent in sulfide-rich coals is ultimately responsible for the
production of acid rain and acid mine drainage (AMD), and for the presence of
problems around coal mines and areas of intensive coal burning. 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 Fe oxides can
also reach percent by weight values (Table 3), particularly where they form as the
oxidation products of primary iron sulfide minerals which have an abundant supply of
123
459
arsenic . Adsorption of arsenate to hydrous iron oxides is particularly strong, and

sorbed loadings can be appreciable even at very low arsenic concentrations in solution
[128130]. Adsorption by hydrous aluminium and manganese oxides may also be
important if these oxides are present in quantity [131133]. Arsenic may also be
sorbed to the edges of clays and on the surface of calcite, a common mineral in many
types of sediment [134, 135]. However, these loadings are much smaller on a weight
basis than for the iron oxides. It is adsorption reactions that are at the basis of the
relatively low (and non-toxic) concentrations of arsenic found in most natural waters.
Although arsenic concentrations in phosphate minerals indubitably vary, they can also
reach high values, for example up to 1,000 mg/kg in apatite (Table 3). However,
phosphate minerals are much less abundant than oxide minerals and so make a
correspondingly small contribution to the load of most sediments. Arsenic can also
substitute for Si4?, Al3?, Fe3?, and Ti4? in many mineral structures, and is therefore
present in many other rock-forming minerals, albeit at much lower concentrations.
Most common silicate minerals contain around 1 mg/kg or less. Carbonate minerals
usually contain less than 10 mg/kg (Table 3).
Rocks, sediments and soils

Earths crust
A little discussion is required pertaining to the concentration of arsenic in the earths
crust. Thus, the concentration is generally taken to be low. Onishi and Sandell gave
the average concentration of the lithosphere as about 2 mg/kg. A major source of
aqueous arsenic is derived mainly from concentration in all three types of rocks
igneous, sedimentary and metamorphicas has been stated in Table 4. An obvious
difference in arsenic concentration does not exist among the various types of
igneous rocks. Arsenic does, however, concentrate in some minerals. For instance,
arsenic readily substitutes for silicon, ferric iron, and aluminium in crystal lattices of
silicate minerals [136, 137]. As a result, concentrations tend to be relatively high in
volcanic glass, aluminosilicate minerals, and igneous rocks containing iron oxide.
Because the content of metamorphic rocks is dependent primarily on source-rock
composition, arsenic concentrations are highly variable in this rock type.
Sedimentary rocks generally contain higher arsenic concentrations than igneous
and metamorphic rocks. It was found that, in general, arsenic in non-marine shales/
clays has been adsorbed by clay minerals, whereas the arsenic associated with
marine shales/clays is present in pyrite and organic matter [138, 139].
Igneous rocks
Similarity may be found between concentrations of arsenic in igneous rocks and
those occurring in the crust. Ure and Berrow in 1982 [140] quoted an average value
of 1.5 mg/kg for all rock types (undistinguished). Averages for different types
distinguished by silica content (Table 4) are slightly higher than this value but
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460
Table 3 Typical concentrations
in common rock-forming
minerals
A. Basu et al.
Mineral
As concentration
range (mg/kg)
Sulfide minerals
References
[7682]
Pyrite
10077,000
Pyrrhotite
5100
Marcasite
20126,000
Galena
510,000
Sphalerite
517,000
Chalcopyrite
105,000
Oxide minerals
Haematite
Up to 160
Fe-oxide(undifferentiated)
Up to 2,000
Fe(III) oxyhydroxide
Up to 76,000
Magnetite
2.741
Ilmenite
\1
Silicate minerals
Quartz
0.41.3
Feldspar
\0.12.1
Biotite
1.4
Amphibole
1.12.3
Olivine
0.080.17
Pyroxene
0.050.8
Carbonate minerals
Calcite
18
Dolomite
\3
Siderite
\3
Sulfate minerals
Gypsum/anhydrite
\16
Barite
\112
Jarosite
341,000
Other minerals
Apatite
\11,000
Halite
\330
Fluorite
\2
generally less than 5 mg/kg. Volcanic glasses are only slightly higher with an
average of around 5.9 mg/kg (Table 4). Overall, there is relatively little difference
between the different igneous rock types. Despite not having exceptional
concentrations of arsenic, volcanic rocks, especially ashes, are often implicated in
the generation of high-arsenic waters. This may relate to the reactive nature of
recent acidic volcanic material, especially fine-grained ash and its tendency to give
rise to sodium-rich high-pH groundwaters [140].
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Table 4 Typical arsenic concentrations in rocks, sediments, soils and other surficial deposits
Rock/sediment type
As concentration
average and/or
range(mg/kg)
No. of
analyses
Igneous rocks
Ultrabasic rocks (peridotite, dunite
kimberlite, etc.)
References
[140143]
1.5 (0.0315.8)
40
Basic rocks (basalt)
2.3 (0.18113)
78
Basic rocks (gabbro, dolerite)
1.5 (0.0628)
112
Intermediate (andesite, trachyte, latite)
2.7 (0.55.8)
30
Intermediate(diorite, granodiorite, syenite)
1.0 (0.0913.4)
39
Acidic rocks (rhyolite)
4.3 (3.25.4)
Acidic rocks (granite, aplite)
1.3 (0.215)
116
Acidic rocks (pitchstone)
1.7 (0.53.3)
Volcanic glasses
5.9 (2.212.2)
12
5.5 (2.27.6)
Metamorphic rocks
Quartzite
Hornfels
5.5 (0.711)
Phyllite/slate
18 (0.5143)
75
Schist/gneiss
1.1 (\0.118.5)
16
6.3 (0.445)
45
Amphibolite and greenstone

Sedimentary rocks
Marine shale/mudstone
315 (up to 490)
Shale (Mid-Atlantic Ridge)
174 (48361)
Non-marine shale/mudstone
3.012
Sandstone
4.1 (0.6120)
15
Limestone/dolomite
2.6 (0.120.1)
40
Phosphorite
21 (0.4188)
205
Iron formations and and Fe-rich sediment
1-2,900
Evaporites (gypsum/anhydrite)
3.5 (0.110)
Coals
0.335,000
Bituminous shale (Kupferschiefer, Germany)
100900
45
5
Unconsolidated sediments
Various
3 (0.650)
Alluvial sand (Bangladesh)
2.9 (1.06.2)
13
Alluvial mud/clay (Bangladesh)
6.5 (2.714.7)
23
River bed sediments (Bangladesh)
1.25.9
Lake sediments, Lake Superior
2.0 (0.58.0)
Lake sediments, British Colombia
5.5 (0.944)
Glacial till, British Colombia
9.2 (1.9170)
World average river sediments
Stream and lake silt (Canada)
6 (\172)
119
310
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462
A. Basu et al.
Table 4 continued
Rock/sediment type
As concentration
average and/or
range(mg/kg)
Loess silts, Argentina
5.418
Continental margin sediments (argillaceous, some anoxic)
2.38.2
No. of
analyses
References
Soils
Various
7.2 (0.155)
Peaty and bog soils
13 (236)
327
14
Acid sulfate soils (Vietnam)
641
25
Acid sulfate soils (Canada)
1.545
Soils near sulfide deposits
126 (28,000)
18
193
Contaminated surficial deposits

Mining-contaminated lake sediment, British Colombia
342 (801,104)
Mining-contaminated reservoir sediment, Montana
100800
Mine tailings, British Colombia
903 (3962,000)
Soils and tailings-contaminated soil, UK
12052,600
Tailings-contaminated soil, Montana
Up to 1,100
Industrially polluted inter-tidal sediments, USA
0.381,260
Soils below chemicals factory, USA
1.34,770
Sewage sludge
86
9.8 (2.439.6)
Metamorphic rocks
Arsenic concentrations in the other two counterparts also have a direct bearing on
that in metamorphic rocks. Most contain around 5 mg/kg or less. Pelitic rocks
(slates, phyllites) typically have the highest concentrations, with on average ca.
18 mg/kg (Table 4).
Sedimentary rocks
The concentration of arsenic in sedimentary rocks is typically in the range 510 mg/
kg, i.e. slightly above average terrestrial abundance [141, 142]. Sedimentary rocks are
equally enriched in arsenic if a comparison is drawn with igneous rocks. Whereas
minerals such as quartz and feldspars predominantly abound in arsenic , sands and
sandstone are its relatively inferior containers. Average sandstone arsenic concentrations are around 4 mg/kg (Table 4), although Ure and Berrow gave a lower average
figure of 1 mg/kg. Argillaceous deposits have a broader range and higher average
arsenic concentrations than sandstones, typically an average of around 13 mg/kg
[140]. The higher values reflect the larger proportion of sulfide minerals, oxides,
organic matter, and clays. Arsenic concentration occurs in black shales mostly at the
high end of the range primarily owing to their enhanced pyrite content. Data given in
Table 4 suggest that marine argillaceous deposits have higher concentrations than
non-marine deposits. This may also be a reflection of the grain-size distributions, with
potential for a higher proportion of fine material in offshore pelagic sediments as well
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463
as systematic differences in sulfur and pyrite contents. Marine shales tend to contain
higher sulfur concentrations. Sediment provenance is also a likely important factor.
Particularly high arsenic concentrations have been determined for shales from midocean settings (mid-Atlantic ridge, average 174 mg/kg; Table 4). Atlantic Ridge
gases may in this case be a high-arsenic source. Concentrations in coals and
bituminous deposits are variable but often high. Samples of organic-rich shale
(Kupferschiefer) from Germany have arsenic concentrations of 100900 mg/kg
(Table 4). Some coal samples have been found with extremely high concentrations of
up to 35,000 mg/kg [143]. Carbonate rocks typically have low concentrations,
reflecting the low concentrations of the constituent minerals (ca. 3 mg/kg; Table 4).
Ironstones and Fe-rich rocks are the sources having the highest observed arsenic
concentrations, mostly several thousand mg/kg. Phosphorites are also relatively
enriched in arsenic (values up to ca. 400 mg/kg having been measured).
Unconsolidated sediments
Arsenic is the case with indurated equivalents such as muds and clays which have
usually higher concentration than sands and carbonates; in unconsolidated sediments,
concentrations are also of note. Values are typically 310 mg/kg, depending on
texture and mineralogy (Table 4). When concentrations are higher, they are likely to
reflect the amounts of pyrite or Fe oxides present. Higher values are also typically
found in mineralized areas. Placer deposits in streams can have very high
concentrations as a result of the abundance of sulfide minerals. Average arsenic
concentrations for stream sediments in England and Wales are in the range 58 mg/kg
[144]. Similar concentrations have also been found in river sediments where ground
water arsenic concentrations are high [145, 146]. It has been found that concentrations
in sediments from the River Ganges average 2.0 mg/kg (range 1.22.6 mg/kg), from
the Brahmaputra River they average 2.8 mg/kg (range 1.45.9 mg/kg), and from the
Meghna River they average 3.5 mg/kg (range 1.35.6 mg/kg). Cook et al. found that
the concentrations in lake sediments ranged between 0.9 and 44 mg/kg (median
5.5 mg/kg), but noted that the highest concentrations were present up to a few
kilometers down-slope of mineralized areas. The upper baseline concentration for
these sediments is likely to be around 13 mg/kg (90th percentile). They also found
concentrations in glacial till of 1.9170 mg/kg (median 9.2 mg/kg; Table 4) and
noted the highest concentrations down-ice of mineralized areas (upper baseline, 90th
percentile, 22 mg/kg) [147, 148]. Relative arsenic enrichments have been observed in
reducing sediments in both nearshore and continental shelf deposits. It is noted that
concentrations increase with depth (up to 30 cm) in continental shelf sediments as a
consequence of the generation of increasingly reducing conditions. Arsenic
concentrations can differ in quantity with the change of sites, but it was also found
to increase with depth in the range 2.38.2 mg/kg [149151].
Soils
Commonly, the order of 510 mg/kg characterizes the baseline concentrations of
arsenic in soils are general. Boyle and Jonasson quoted an average baseline
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A. Basu et al.
concentration in world soils of 7.2 mg/kg (Table 4) [119121] and Shacklette et al.
quoted an average of 7.4 mg/kg (901 samples) for American soils [152154]. Ure
and Berrow mentioned an even higher average value of 11.3 mg/kg. They also
quoted concentrations in the range 366732 mg/kg in orchard soils as a result of the
historical application of arsenic pesticides to fruit crops [141, 142]. Peats and bog
soils can have higher concentrations (average 13 mg/kg; Table 4), solely on account
of the elevated predominance of sulfide mineral phases under the reduced
conditions. Acid sulfate soils which are generated by the oxidation of pyrite in
sulfide-rich terrains, such as pyrite-rich shales, mineral veins, and dewatered
mangrove swamps, can also be relatively enriched in arsenic . Dudas found arsenic
concentrations up to 45 mg/kg in the B horizons of acid sulfate soils derived from
the weathering of pyrite-rich shales in Canada. Concentrations in the overlying
leached (eluvial, E) horizons were low (1.58.0 mg/kg) as a result of volatilization
or leaching of arsenic to lower levels [155, 156]. Gustafsson and Tin found similarly
elevated concentrations (up to 41 mg/kg) in acid sulfate soils from the Mekong delta
of Vietnam. In spite of the dominant sources of arsenic in soils being geological, and
thereby dependent to some extent on the concentration in the parent rock material,
extra inputs are likely to be obtained locally from industrial sources such as
smelting and fossil fuel combustion products, and agricultural sources such as
pesticides and phosphate fertilizers [110, 157].
Contaminated surficial deposits
Those sediments and soils which are contaminated by the products of mining
activity, including mine tailings and effluent, doubtlessly contain arsenic at much
higher than baseline values. Concentrations in tailings piles and tailings-contaminated soils can reach up to several thousand mg/kg (Table 4). Apart from reflecting
increased abundance of primary arsenic-rich sulfide minerals, the high concentrations reflect secondary iron arsenates and iron oxides formed as reaction products of
the original ore minerals. The primary sulfide minerals are susceptible to oxidation
in the tailings piles, and the secondary minerals have varying solubility in oxidizing
conditions in ground and surface waters. Scorodite (FeAsO42H2O) is a common
sulfide oxidation product, and its solubility is considered to control arsenic
concentrations in such oxidizing sulfide environments. Scorodite is metastable
under most ground water conditions and tends to dissolve incongruently, forming
iron oxides and releasing arsenic into solution [158]. However, in practice, a wide
range of Fe-As solubility relationships are found which in part pertain to the mineral
type [159, 160]. There is some confusion in the analysis of these solubility
relationships between congruent dissolution, incongruent dissolution, and sorption/
desorption reactions. Secondary arsenolite (As2O3) is also relatively soluble. Iron
oxide-bound arsenic is relatively immobile, particularly under oxidizing conditions.
The atmosphere
Although the above discussion has made it clear that arsenic concentrations in the
atmosphere are low, they are often increased by inputs from smelting and other
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industrial operations, fossil fuel combustion, and volcanic activity. Concentrations

amounting to around 10-510-3 g/m3 have been recorded in unpolluted areas,
increasing to 0.0030.18 g/m3 in urban areas, and greater than 1 g/m3 close to
industrial plants [300]. Much of the atmospheric arsenic is particulate. Total arsenic
deposition rates have been calculated in the range\11,000 `g/m2/years1 depending
on the relative proportions of wet and dry deposition and proximity to contamination sources [161]. An estimate of values for the mid-Atlantic coast ranged
38266 `g/m2/years1 (2955 % as dry deposition) [162, 163]. Aquatic arsenic is in
fact air-borne in nature whether the deposition be wet or dry and this may therefore
increase the aqueous concentration slightly. Yet it cannot be concluded that
atmospheric arsenic poses a real health threat for drinking-water sources.
Atmospheric arsenic issuing from coal burning has been invoked as a major cause
of lung cancer in parts of China (Guizhou Province), but the threat is from direct
inhalation of domestic coal-fire smoke and especially from consumption of foods
dried over coal fires, rather than from drinking water affected by atmospheric inputs
[164].
Anthropogenic sources
Arsenic has been used for a wide variety of purposes in different countries.
Anthropogenic sources of arsenic , such as smelters, mining operations and processing
wastes, poultry and swine feed additives, pesticides, herbicides, wood treatments,
electronic manufacturing, cattle dips, vitamin supplements, pharmaceuticals, nutraceuticals, coal combustion, FGD plants, cigarettes, paints, dyes, cosmetics, and highly
soluble trioxide stockpiles are also not uncommon. As the record runs, 70 % of the
world arsenic production is used in timber treatment as copper chrome arsenate (CCA), 22 % in agricultural chemicals, and the remainder in glass, pharmaceuticals, and non-ferrous alloys. Mining, smelting of non-ferrous metals, and burning
of fossil fuels are the major industrial processes that contribute to anthropogenic
arsenic contamination of air, water, and soil. History shows evidence as to how large
tracts of arable land have been contaminated as a result of excessive pesticides
containing arsenic. The use of arsenic in the preservation of timber has also led to
contamination of the environment. Agricultural applications, wood preservation, and
glass production have been the dominant uses in United States. With the development
of new analytical methods, much greater insight into the occurrence of the various
inorganic and organic forms of arsenic is being obtained. However, there are
estimates of the extent to which methylated arsenic compounds contribute to ambient
atmospheric arsenic levels and estimates of low temperature volatilization. Being
ubiquitous, in environmental occurrence, its sources may be both natural and
anthropogenic arsenic , the atmosphere being the major transport pathway for this
element. Total arsenic emissions into the atmosphere from anthropogenic sources are
of the order of 30,000 ton/years. Copper smelting and coal combustion alone
contribute to about 60 % of the arsenic contamination. Uncertainties regarding these
estimates depend mostly on the adopted value for emission factors. Since emission
factors have been taken from developed countries, estimated global source strengths
could be underestimated. For the refinement of the present global estimates, data from
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A. Basu et al.
countries outside Europe, the USA, and Canada are required. Also, there are still gaps
in the details of anthropogenic sources of arsenic such as herbicide use, agricultural
and forest burning, gold mining and smelting (especially from the USSR and South
Africa), and wood and cow dung burning (Africa and India being the major sources).
Chilvers and Peterson have calculated herbicide use of arsenic at 3,440 tons As/year,
coal combustion at 6,240 tons As/year and combined smelter and steel production at
14,350 tons As/year. While global emissions to the atmosphere from anthropogenic
sources, especially copper smelters, contribute indirectly to contamination of the land
and terrestrial waters, considerable amounts of arsenic are added to the land directly
as landfill from the dumping of slag and sludges, and in wastewater from smelting and
refinery activities. Such direct anthropogenic emissions to land and water are of
comparable magnitude to the atmospheric emissions, although their initial impact is
more likely to be of local concern, rather than of regional or global significance.
However, where these local imports involve high human population densities or large
populations per se, then their significance should not be minimized.
It is important that studies addressing the problems noted above take full
advantage of recent analytical developments allowing identification of both organic
and inorganic forms of arsenic in aquatic systems [165, 166]. The development of
analogous techniques for arsenic speciation in the atmosphere, soils, and biological
matrices is strongly recommended, together with the development of appropriate
reference materials relevant to local and regional issues. Arsenic occurs naturally in
sediments all over Asia, and is a particular problem in areas dominated by Holocene
and organic-rich sediments [167]. This issue shows that human alteration of
landscape, specifically the construction of artificial ponds, is making matters worse,
as these ponds contain significant quantities of easily degradable organic carbona
known factor in arsenic mobilization. Ground water pumping draws pond water to
depths, causing arsenic to be released from sediments into the ground water, and
thus into the human food chain.
Arsenic toxicity
Arsenic is classified as a hazardous material suspected to be a carcinogen mostly
affecting the lungs and skin. Arsenic is a promoter of cancer development [168].
Exposure to inorganic arsenic is associated with various internal cancersliver,
bladders, kidney, lung, and skin along with diabetes [169]. It is also a teratogen; i.e.,
it can cross the placental membrane into the metabolic system of the unborn child. It
is also known as a cumulative substance passing out of the body through urine, hair,
finger, toe-nails, and skin [170]. Arsenic also causes ischemic heart disease [171,
172]. Blackfoot disease is an endemic peripheral vascular disease leading to
gangrenous change of the feet and the lower extremities, which for approximately a
century was found to be confined to the southwestern coast of Taiwan [173175].
Cardio-vascular disease is also caused by arsenic [176]. In a few reports, it has been
found that the mental health of the inhabitants in Inner Mongolia, China, was
disturbed due to an arsenic-affected area [177]. This is not a common problem with
arsenic and needs further attention. Chronic kidney disease (CKD) in a Taiwanese
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population was also reported as an problem in which inorganic arsenic has been
linked to decreased kidney function through oxidative damage [178]. Arsenic
induces endothelial dysfunction and accelerates atherosclerosis in apolipoprotein E
(ApoE) [179]. Along with blackfoot disease, there is another arsenic-related skin
disease, Bowens disease (raindrop pigmentation on the left thigh of the victim),
which has been observed in some cases [180, 181]. Anthropogenic arsenic is
responsible for Alzheimers disease which is an increasing problem in European
countries [180, 182]. Actually, arsenic is one of those toxic metals which are able to
mimic the functions of useful bio-metals and, as a consequence, it substitutes
those metals in various cellular processes, thus causing serious malfunctions of
different vital cellular activities. It affects normal operation of the cellular cycle by
splitting the mitotic spindle in physiological human diploid fibroblasts [183186].
Arsenic causes complicated toxic cell damage mainly due to oxidative stress [187],
and chronic expose to arsenic results in chromosomal damage of the peripheral
lymphocytes [188190].
Technologies for removing

Arsenic has found widespread use in agriculture and industry to control a variety of
insect and fungicidal pests. Most of these uses have been stopped, but residues from
such activities, together with the on-going generation of arsenic from the smelting
of various ores, have left a legacy of a large number of arsenic-contaminated sites.
The removal of arsenic is hindered by the fact that arsenic has a variety of valence
states. Arsenic is most effectively removed or stabilized when it is present in the
pentavalent arsenate form. Different techniques are being found nowadays for the
removal of arsenic. There are several treatment methods capable of this level of
performancemembranes, coagulation, anion exchange, disposable iron media,
softening, etc. Treatment cost, operational complexity of the technology, skills
required to operate the technology and disposal of arsenic-bearing treatment
residues are factors that should be considered before selection of the treatment
method. We will discuss a few of them now.
Remediation by adsorption
Adsorption is a good technique for the removal of heavy metal from its aqueous
solutions. There are many known adsorbents which effectively remove arsenic from
ground water. They are represented below.
Commercial and synthetic activated carbons
The increased processing of complex sulfide ores (e.g., the bacterial oxidation of goldbearing arsenopyrite) has led to higher levels of impurities such as arsenic in process
streams. The removal of such impurities could become a new field of application for
activated carbon. Activated carbons, either synthetically or commercially activated,
are very useful adsorbents for removal. Different processes are used to increase the
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efficiency of activated carbon. The effect of pH and surface volume are important for
this work. The effect of activated carbon as an arsenic-removing agent are briefly
discussed here.
It has been found that As(V) is more effectively removed from solution by using
activated carbon with a high arsenic content. Pentavalent arsenic is adsorbed in granular
activated carbon [191]. Pretreatment of the carbon with Cu(II) solutions improves its
arsenic-removal capacity. The optimum pH for arsenic adsorption by pretreated carbon
is approximately 6. It applies two methods for arsenic removal [192]. Arsenic has also
been adsorbed onto activated carbon impregnated with metallic copper and silver [193].
The As(III) isosteric heat of adsorption varied from 4 to 0.75 kcal/mol and that of
As(V) is 42 kcal/mol, with increasing surface loading. This magnitude suggest that
physisorption occurred due to weak Van der Waals forces and due to this, it was found
that activated charcoal adsorbed 2.5 wt % As(V) and 1.2 wt % As(III) (based on weight
of carbon) [194]. Iron-impregnated activated carbons have been found to be very
effective in arsenic removal. Oxyanionic arsenate and arsenite adsorb at the iron oxyhydroxide surface by forming complexes with the surface sites. Increasing iron
impregnation, by precipitation or iron salt evaporation, increases the bed volumes (up to
25,00034,000) which enhances the adsorbent power [195]. Iron content is also
increased in activated carbon by the ferric chloride forced hydrolysis method. This
activated carbon removes 94 % of the arsenic present in ground water in the State of
Chihuahua in Mexico, where commercially activated carbon removes only 14 %. [196].
There is another case, in which iron-doped phenolic resin based on activated micro-/
nanoparticles of carbon act as an efficient adsorbent for As(III) and As(V) removal at
low concentration levels (\20 mg/l) [197]. The capacity of removal of activated carbon
fiber (ACF) is also increased by impregnation of nano-sized magnetite to the surface of
ACF with chitosan as the coating support; the As(V) adsorption capacity increased by 8
times even at As(V) concentrations lower than 10 lg/l without forming poisonous
As(III); and this modified activated carbon fiber works in a wide pH range from 2 to 8
for As(V) uptake [198]. Iron oxide/activated carbon (FeO/AC) composite can be used
as the adsorbent to remove arsenic from drinking water, obeying the Langmuir isotherm
adsorption equation. The main phases present in this composite are magnetite (Fe3O4),
maghemite (c-Fe2O3), hematite (a-Fe2O3), and goethite [a-FeO(OH)], and this
composite adsorbent showed that arsenic can be removed to below 0.01 mg/l. [199].
Granular activated carbon-based, iron-containing adsorbents (As-GAC) are also
becoming arsenic-removing adsorbents in some cases. The removal of arsenate
occurred in a wide range of pH examined from 4.4 to 11, but efficiency was decreased
when pH was higher than 9.0. The presence of phosphate and silicate could significantly
decrease arsenate removal at pH [ 8.5, while the effects of sulfate, chloride, and
fluoride were minimal [200]. There are also some low-cost activated carbons which
behave as good adsorbents. One of them is prepared from bean pods waste, and a water
vapor activation process was used to synthesize the activated carbon which is employed
for the removal of As(III). The maximum loading capacity for arsenic is 1.01 mg/g
[201]. Another recent example of activated carbon loaded with Fe3O4 prepared from
waste biomass is cited here. Fe3O4 particles were uniformly deposited on the surface of
the biomass and it showed a maximum adsorption capacity of 204.2 mg/g at pH 8.0
[202]. Arsenic adsorption capacity on the carbon obtained from agricultural waste was
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found to be similar to the more expensive commercial carbons showing high adsorption
capability. There is a report in which activated carbon along with a biosorbent,
Ralstonia eutropha MTCC 2487, removed arsenic from contaminated water in a batch
reactor. The adsorption obeyed the Temkin isotherm for As(V), but for As(III) it obeys
the Langmuir isotherm. The maximum removal of arsenic is 86 % in this case [203].
Copper-impregnated activated carbon derived from coconut husk is another adsorbent
of arsenic at pH 12. As(III) can be successfully removed from synthetic and industrial
wastewater using this adsorbent [204].
Low-cost adsorbents
The removal of arsenic from drinking and irrigation water is a recurring challenge,
especially in developing countries. Cost considerations can make it expedient to use
local materials, produced in agricultural or industrial operations, as arsenic adsorbents
for these toxins. The performance of these materials may not always be optimal, but
their immediate availability often makes them attractive choices. In a number of
cases, it has been found that low-cost adsorbents have demonstrated outstanding
removal capabilities for As(III) and As(V) compared to activated carbon.
Agricultural products and by-products The demand for effective and inexpensive
adsorbents is in response to the widespread recognition of the toxic health effects of
exposure through drinking water. And in this regard, agricultural products and byproducts are nowadays gaining in importance. One of the examples is chemically
modified maize cobs waste. When it is modified with phosphoric acid/ammonia, the
arsenite removal is 98 % from a 550-lg As/l solution for an adsorbent dose of
50 mg/ml, and when modified by phosphoric acid/urea, it removes 0.4 lg/g arsenate
from a 300-lg As/l solution [205]. Rice husks have been used in arsenic removal in
acidic medium (0.01 mol/l of HNO3, HCl, H2SO4 or HClO4) obeying the
Freundlich isotherm. The absorbance increases with increasing temperature [206].
Untreated rice husk can also remove arsenic from water. The given conditions
remove As(III) and As(V) completely: initial concentration, 100 lg/l; rice husk
amount, 6 g; pH, 6.06.5, respectively [207]. Rice polish, another agricultural
residue, was utilized successfully for the removal of As(III) and As(V) from
aqueous solution. The maximum sorption capacity was 138.88 lg/g for As(III) at
20 C and pH 7.0, and 147.05 lg/g at 20 C and pH 4.0 for As(V), which means
that As(III) can be easily separated by this sorbent in neutral pH [208]. Quaternized
rice husk (QRH) has the potential to remove As(V) from aqueous solution. The
adsorption process is pH- and temperature-dependent. The utility of the process is
that the adsorption process is done at almost neutral pH and room temperature.
Thus, the process is very economic [209]. Sawdust, a relatively abundant and
inexpensive material found almost everywhere, can remove arsenic from contaminated water [210].
Industrial by-products Arsenic concentrations above acceptable standards for
drinking water have been detected in many countries, and thus this is a global issue.
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The presence of arsenic in subsurface aquifers and drinking water systems is a

potentially serious human health hazard. Industrial solid wastes can be recycled
with arsenic non-conventional adsorbents, if they are nontoxic, to reduce the cost of
wastewater treatments. There are a number of industrial by-products which can
remove arsenic from contaminated water. One example is waste Fe(III)/Cr(III)
hydroxide, generated electrolytically in the treatment of Cr(VI)-containing wastewater in a fertilizer industry. It can remove As(V) from wastewater in a wide range
of pH. The spent adsorbent can be easily recycled by using NaOH solutions [211].
Fly ash, a by-product of coal power stations and many different industries, can
effectively remove As(V) from aqueous solutions, solid wastes, or the soil. A report
on lignite-based fly ash shows that the removal is pH-dependent. The experiments
show that the process is irreversible and so a good method for removal [212]. Blast
furnace slag (BFS), a steel industry by-product, has been used for the removal of
As(III) from ground water. The results suggest that 99.9 % As(III) at 1 mg/l can be
removed by 10 g/l BFS, which shows that this is a good sorbent for As(III) removal
[213]. Lignite, peat chars and bone char are nowadays drawing attention as biochars, produced from different industries, and they may be good substitutes for
activated carbon as they are comparatively plentiful, inexpensive, and locally
available [214218]. Fast wood/bark pyrolysis produces some bio-chars which are
being investigated as adsorbents for removal of As(III) from water. Wood and bark
of oak and pine trees are taken for pyrolysis at 400450 C. Maximum adsorption
occurs over a pH range of 34 for . As(III) removal follows this order: pine wood
char (1.20 lg/g) \ oak wood char(5.85 lg/g) \ oak bark char (12.1 lg/g) \ oak
bark char (12.15 lg/g) [219]. Another example is red mud, which is a waste product
from bauxite processing and has been explored as an arsenic-removing agent.
Alkaline aqueous medium (pH 9.5) favored the removal of As(III), whereas acid
medium (pH from 1.1 to 3.2) was effective for As(V) removal. It was found that the
adsorption of As(III) was exothermic, whereas As(V) adsorption was endothermic.
It would be advantageous to use this residue as an adsorbent for arsenic removal.
Heat and acid treatments on red mud increase its adsorptive capacities [220]. Seawater neutralized red mud, Bauxsol (either activated or not), can be used as an
arsenic-removing agent. The sorption increases with decreasing pH, higher
adsorbent dosage, and lower initial concentration of arsenic. Each work using this
sorbent shows that, after the treatment with Bauxsol, no arsenic was present in the
eluted water. A TCLP leaching test shows that the adsorbent is non-toxic. Acid as
well as heat treatment increases the removal efficiency and the combination of these
two is the best [221, 222].
Soil and constituent Arsenic can be removed from wastewater using different soil
materials; such as clay, mud, sand, rock, etc. A number of studies has been done by
groups of researchers. Laterite soil is an example. Under optimized conditions, the
laterite soil can remove up to 98 % of total arsenic . Aqueous NaOH (1 M) can
regenerate the adsorbent, and the regenerated adsorbent showed higher efficiency
[223]. A low-cost ferruginous manganese ore, formed by pyrolusite and goethite
minerals, can adsorb both As(III) and As(V), though the attachment is greater with
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As(III). Both As(III) and As(V) are adsorbed by the FMO in the pH range of 28.
The presence of bivalent cations, namely, Ni2?, Co2?, and Mg2?, enhances the
adsorption capability, and arsenic removal is almost 100 % with this ore [224].
Soyatal Formation, an ubiquitous clay-rich limestone, is superior to other rocks
which remove arsenic from ground water (found in the Zimapan region, Mexico).
Experiments shows that a rock:water weight ratio of 1:10 can reduce the aqueous
arsenic concentration from 0.5 to \0.030 mg/l. The calcareous shale of the Soyatal
Formation contains kaolinite and illite (both minerals known to adsorb ), and so it
can be used as a low-cost adsorbent for arsenic removal [225]. Adsorption of As(III)
and As(V) on kaolinite, montmorillonite, and illite have also been investigated as a
function of pH and competing anions. It has been found that, for these three
different materials, the maximum As(V) adsorption [0.150.22 mmol As(V)/kg]
takes place at three different pH: for kaolinite, pH 5.0; for montmorillonite, pH 6.0;
for illite, pH 6.5; in the presence of Mo and PO42-, the adsorption decreases [226
228]. The removal and fixation of As(III) and As(V) by a soilbentonite mixture is
another example which has been developed as reliable clay liners for waste landfill
sites. The main body of the liner was made up of Masatsuchi soil (weathered
granite) or Murram soil (pumice). The former removes more arsenic [229].
As(V) adsorption by Olivier loam, Sharkey clay, and Windsor sand has also been
reported [230]. A variety of treated and untreated sands are employed for arsenic
remediation [231235]. Iron-impregnated sand (IIS), a known granular medium,
removes As(III) and is more effective than iron oxide-coated sand (IOCS) [236].
Recently, iron oxide-coated sponge (IOCSp) has also been synthesized for As(III
and V) removal, which is more effective than the former [234]. Dimethyl arsenate
from tap water can be removed by using manganese greensand (MGS), iron oxidecoated sand (IOCS-1 and IOCS-2), and ion-exchange resin (Fe(III) form).
Manganese greensand is effective for removing to \25 lg/l [237, 238]. Sulfatemodified iron oxide-coated sand (SMIOCS) is another example of arsenic-removing
material [239, 240].
Oxides Natural zeolites, volcanic stones which contain a large amount of metal
oxide, remove As(III), As(V), dimethylarsinic acid (DMA), and phenylarsonic acid
(PHA) from aqueous solutions [241]. Another novel adsorbent, aluminum-loaded
Shiru-zeolite P1 (Al-SZP1), was employed for the adsorption and removal of
As(V) ion from an aqueous system over a pH range from 3 to 10. The addition of
arsenite, chloride, nitrate, sulfate, chromate, and acetate ions hardly affected the
As(V) adsorption. This adsorbent is well suited for As(V) removal in a low
concentration range [242]. Iron oxide (Fe2O3), due to its low cost and easy
availability, can act as a good adsorbent for As(V) for its relatively small surface
area. At acidic pH, it works well and removes 95 % of As(V) within a time period of
2060 min. Thus, Fe2O3 is a useful and effective adsorbent for small-scale
commercial or individual home water treatment systems. This is the same for Al2O3,
but Fe2O3 is a better sorbent than Al2O3 because the rate of adsorption is higher in
the case of the former [243]. A polymeric/inorganic hybrid sorbent prepared by Feoxide is very selective towards As(III) and As(V) removal from contaminated
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ground water. Each hybrid sorbent particle is essentially a spherical macroporous

cation exchanger bead within which agglomerates of nano-scale hydrated Fe oxide
(HFO) particles have been uniformly and irreversibly dispersed, using a simple
chemicalthermal treatment. This new sorbent is referred to as a hybrid ion
exchanger (HIX). The regeneration of HIX is also a very easy process [244].
Ce(IV)-doped iron oxide adsorbent is another As(V)-removing oxide that can be
given as an example. A maximum adsorption capacity of 8.3 mg/g was obtained
over a narrow pH range around 5.5 [245]. In another work, iron oxide-coated
cement is used as an adsorbent for As(III) and As(V) removal. As(III) and
As(V) exhibit the exothermic and endothermic nature of adsorption, respectively
[246]. Hydrated iron oxide along with a hybrid inorganic/organic polymer is another
adsorbent used in arsenic oxyanions removal from contaminated drinking water.
This novel hybrid material is very selective towards arsenic oxyanions even though
the presence of silica and phosphate reduces the adsorption capacity [247]. Instead
of a single metal oxide, binary metal oxides such as FeMn binary oxide can
remove As(III) from anaerobic ground water (collected from a suburb of Beijing).
The report shows that, after 4 months of treatment, As(III) concentration reduced
from 3545 lg/l to below 10 lg/l in the sample [248].
Hydrotalcites Hydrotalcites, also known as LDHs, have the structural formula

x? nII
III
[MII1-xMIII
denote divalent metals like Mg,
x (OH)2] Ax/n mH2O, where M and M
Ni, and Zn, and trivalent metals like Al, Fe, and Cr [249]. An- represents interlayer
anions, such as NO3-, SO42-, and CO32-, and x typically ranges from 0.17 to 0.33.
These materials consist of positively charged octahedral layers and a negatively
charged interlayer region containing anions and water molecules. The presence of
large interlayer spaces and a significant number of exchangeable anions cause
hydrotalcites to be good ion-exchangers and adsorbents [250]. Adsorption of arsenic
from dilute aqueous solutions by calcined and uncalcined LDH layered double
hydroxide was investigated, and it was found that these materials show a good
tendency to remove As(V) from the solution [251]. There is also an example of
layered double hydroxide MgAl hydrotalcite for arsenic removal. The removal
efficiency is further improved by pre-treatment with dilute H2O2 solution to oxidize
As(III) to As(V) and then exchange with hydrotalcites. This solid can also be
regenerated by saturated NaCl [252]. The use of this synthetically prepared clay
material, hydrotalcite (HT), for the removal of arsenite and arsenate from drinking
water has also been described in other cases. Percolation through HT of water
containing 5001,000 lg/l (levels often found in arsenic-contaminated well water)
reduces arsenic levels below 10 lg/l. The spent HT is easily converted into
valuable phosphate fertilizer that would have an insignificant effect on soil arsenic
levels, thereby reducing the overall cost of manufacture and distribution [253].
Another group used three types of HT (HTAL-Cl, HTAL-CO3, and HT-500) for
arsenic removal and found that HTAL-Cl showed a high adsorption capacity
(105 mg/g) in the neutral pH region [254].
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Phosphates Phosphate ions (which are interfering ions in arsenate separation) may
be used as adsorbent for separation in some cases. Fe(III) phosphate (amorphous or
crystalline) can remove As(III) and As(V). Oxidation of As(III) by Fe(III) and
phosphate substitution by As(V) occur during arsenic adsorption. Fe(III) phosphate
can remove As(III) more easily than As(V) [255].
Metal-based methods There are different methods where metallic compounds are
used as arsenic-removing adsorbents. Iron oxide in nanoparticle and microparticle
form is used as adsorbent in combination with multilayer ceramic membranes. The
results show that 2 g/l of nanoparticle adsorbent lowers the arsenate concentration
from an initial concentration of 1 mg/l down to10 lg/l [256]. The biopolymer
chitosan combined with iron can remove As(III) and As(V) at neutral pH. The
adsorption capacity of iron chitosan flakes (ICF) (22.47 0.56 mg/g for As(V) and
16.15 0.32 mg/g for As(III) was found to be considerably higher than that
obtained for iron chitosan granules (ICB) [2.24 0.04 mg/g for As(V);
2.32 0.05 mg/g for As(III)]. So, the adsorbent has been successfully applied
for the removal of total inorganic arsenic down to \10 lg/l from real-life arseniccontaminated ground water samples [257]. Zero-valent iron shows ability in
removing As(III) and As(V) from water. As(V) exhibited greater removal rates than
As(III). The process is temperature-dependent and phosphate and nitrate ions retard
the process [258]. Zero-valent iron (steel wool) (1.3 g/l) with one drop (ca. 0.04 ml)
of lemon juice (citrate concentration) in the presence of solar radiation can remove
99.5 % arsenic from natural water (in Camarones River, Atacama Desert in northern
Chile) and reduce arsenic concentrations below 10 lg/l. This highly effective
arsenic removal method is easy to use and inexpensive to implement [259]. Alumimpregnated activated alumina (AIAA) is another metal-based adsorbent which
selectively remove As(V) from ground water and is suitable for treatment of
drinking water. In the pH range of 2.811.5, arsenate predominantly exists as
H2O4- and HO42- species, and these are two major species being adsorbed on the
surface of AIAA. Thus, AIAA can also be used as an adsorbent [260]. Nanoactive
alumina can also remove As(V), and the adsorption maximum was observed at pH
3.24.6 [261]. Removal of As(III) in the KMnO4Fe(II) process is another method
which has been carried out in the pH range of 49 with permanganate and ferrous
sulfate and found to be a good one. But sulfate, phosphate, silicate, and humic acid
(HA) greatly reduce the rate of removal. As(III) removal decreased in the following
order: phosphate [ humic acid [ silicate [ sulfate [262].
Biosorbents Biosorption has been demonstrated to be a useful alternative to
conventional treatment systems for the removal of toxic metals from dilute aqueous
solution. Biosorbents are low-cost and eco-friendly adsorbents which remove
arsenic from ground water and day-by-day their use increases in this field. Iron
oxide-coated fungal biomass (Aspergillus niger) was found to be efficient in
removing arsenic from an aqueous solution. Iron oxide-coated biomass (IOCB)
effectively removed 75 % As(III) and 95 % As(V) at a pH 6 in approximately 7 h.
This process is temperature-dependent: at low temparature, As(V) is predominantly
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removed, and at relatively high temperature, As(III) is removed [263265]. Tea

fungal biomass, a waste produced during black tea fermentation, when pretreated
with FeCl3, becomes an active arsenic-removing agent. It can remove 100 % of
As(III) after 30 min contact time and 77 % of As(V) after 90 min contact time, and
the optimum adsorbent dosage was 1.0 g/50 ml of the water sample [266]. Lessonia
nigrescens, an algal biomass, removes As(V) at pH 2.5, 4.5, and 6.5. Maximum
adsorption capacities were estimated to be 45.2 mg/g (pH 2.5), 33.3 mg/g (pH 4.5),
and 28.2 mg/g (pH 6.5) indicating better adsorption at the lower pH [267].
P. chrysogenum biomass is another example of an arsenic-removing biosorbent.
The pretreatment of biomass with common surfactants like hexadecyl-trimethylammonium bromide and dodecylamine and a cationic polyelectrolyte was found to
improve the biosorption efficiency [268]. There has been some work on arsenic
absorbance by chitosan, a biopolymer extracted from the wastes of the seafood
industries. The sorption mechanism is shown to be by an electrostatic attraction,
with thermodynamic parameters indicating an exothermic and spontaneous reaction.
The main factors are temperature, pH, and the presence of other ions [269].
XPS analysis and desorption studies show that molybdate-impregnated chitosan
gel beads are very efficient biosorbents for the removal of As(III) and As(V). The
mechanism of As(V) uptake is due to the complex formation between molybdate ion
and As(V) in acid solution (optimum pH 23), but no such complexation occurs
between molybdate ion and As(III). So, this sorbent is much more efficient for
As(V) (230 mg/g Mo) than As(III) (70 mg/g Mo), and this can be used for industrial
effluent treatment [270]. Another example is chitosan-coated biosorbent impregnated with ceramic alumina used in As(III) and As(V) removal at pH 4. The
monolayer adsorption capacity of the sorbent, obtained from the Langmuir
isotherm, is 56.50 and 96.46 mg/g of chitosan for As(III) and As(V), respectively.
The difference in adsorption capacity for As(III) and As(V) was explained on the
basis of speciation of arsenic at pH 4.0 [271]. Oak bark, pine bark, oak wood, and
pine wood chars are also used as biosorbent for arsenic removal, in some cases at
pH range 34. Amongst them, oak bark out-performed the other chars and also
removed 70 % arsenic, so by-product chars from bio-oil production might be used
as plentiful and inexpensive adsorbents for water treatment at a value above their
pure fuel value [272]. Fe(III)-loaded ligand exchange cotton cellulose adsorbent
[Fe(III) LECCA], a novel macroporous bead adsorbent, can specifically remove
As(V) from contaminated water with 83 % efficiency at any pH [273]. An example
of biosorbent, Momordica charantia, shows its ability towards As(III) removal at
optimum pH 9, i.e., at alkaline pH. The uptake capacity is 0.88 mg As(III)/gm of
biomass. It appears that this biomass should be used as a palliative food item.
Furthermore, it also appears that the dietary habits may play a role in the toxic
effects of ingested arsenic [274]. Farmed shrimp shells can remove arsenic from
solutions. The shells of two species of farmed shrimp, black tiger shrimp (Penaeus
monodon) and white shrimp (Litopenaeus vannamei), have also been detected to be
arsenic biosorbents and the adsorption capacity of these two species are estimated to
be 8.1 9 10-35.0 9 10-1 and 7.8 9 10-32.4 9 10-1 mg/g, respectively. The
adsorption capacity increases with the initial arsenic concentration and retention
time in water. So, the shrimp shell, as a waste material, can be utilized potentially
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for the removal of arsenic from an aqueous medium [275]. Another example of the
same kind uses acid-washed crab shells, which can also remove As(V) from
aqueous solution at a low pH range due to arsenate binding on the amide groups
present in the shells. This shell has a dense structure and low extent of swelling in
aqueous solutions, so it can be used as low cost biosorbent for As(V) removal [276].
An industrial effluent treatment plant, Vapi, India, contains arsenic-hyper-tolerant
bacterial cells, Bacillus sp. strain DJ-1, which accumulate by arsenite binding
protein coming out of agricultural and industrial wastes and can easily be used as a
low cost biosorbent [277]. The stem of another plant, Acacia nilotica, can remove
arsenic from different water sources, such as lakes, canals, rivers, etc. The biomass
of A. nilotica was found to be effective for the removal of arsenic with 95 %
sorption efficiency at a concentration of \200 lg/l of arsenic solution, and thus
uptake capacity is 50.8 mg As/g of biomass [278]. The fresh and immobilized
biomass of Garcinia cambogia, an indigenous plant found in many parts of India,
has the ability to remove As(III) from solution at pH range 68, but the presence of
Fe(III) ions at 100 mg/l causes a noticeable drop in the extent of As(III) removal.
The biomass can be regenerated with NaOH solution in five cycles of loading and
elution; so this can be used as a cost-effective adsorbent for As(III) removal [279].
The non-living, dried roots of the water hyacinth plant [Eichhornia crassipes
(Mart.) Solms] can rapidly remove arsenic from water. It removes almost 93 % of
arsenite [As(III)] and 95 % of arsenate [As(V)] from a solution containing 200 lg/l
within 60 min of exposure to a powder produced from the dried roots. The amount
of arsenic remaining in solution was found to be less than 10 lg/l. Both As(III) and
As(V) are separated at the same rate [280]. Lamarck seed powder, from shelled
Moringa oleifera, which contains proteins in considerable amounts, can remove
60.21 % As(III) and 85.60 % As(V) from contaminated water at pH 7.5 and 2.5,
respectively. According to the author, the removal is due to amino acidarsenic
interactions [281]. Another example of biosorbent is a mixed culture of sulfatereducing bacteria, which remove both As(V) and As(III) from ground water. It was
found that about 77 and 55 % of As(V) and As(III), respectively, under the
following conditions: pH 6.9; biomass (2 g/l); 24 h contact time; initial concentration 1 mg/l of either species [282].
Coagulationprecipitation process
Coagulation of arsenic using different coagulating agents or precipitating it from its
aqueous solution may be good tools for arsenic separation. For the removal of
arsenic from wastewater, coagulation, normally using iron, is the preferred option.
In one study, arsenic precipitation in an Fe(II)NH3(NH4)2SO4O2 system is
carried out. The rate of precipitation increases with an increase in temperature,
increase in pressure of O2, and also increase in precipitation time. It is found that an
increase in pressure of O2 from 70 to 140 kPa results in an increase of arsenic
precipitation from 82 to 93 % at 15 min precipitation time, and at 45 min almost
98 % arsenic was precipitated [283]. Aluminum sulfate is another example in which
arsenic is removed by the precipitationco precipitation method. The optimum pH
range for maximum arsenate removal was 68. It is found that, in low initial
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A. Basu et al.
arsenate concentrations, the highest arsenate removal efficiency was obtained at

high aluminum sulfate doses, while in high initial arsenate concentrations, the
highest arsenate removal efficiency was provided at low coagulant doses. The use of
all types of coagulant aids increased the removal efficiency of the treatment method
but application of cationic polyelectrolyte was more effective than anionic and nonionic ones [284]. As(III and V) removal by ferric chloride coagulant has some effect
of organic matter and it has been found that organic matter enhances the coagulation
only of As(V) [285]. Ferric ion itself is a good coagulant for arsenic removal, but
micro-filtration (membrane as filter medium) was needed to remove the coagulates
from water. In the presence of coarse calcite, small arsenic-borne coagulates coated
on coarse calcite surfaces, increases the settling rate of the coagulates to a
considerable extent. This enhanced coagulation followed by conventional filtration
achieves a very high arsenic removal (over 99 %) from high-arsenic water (5 mg/l
concentration), producing a cleaned water with the residual arsenic concentration of
13 lg/l; thus, this enhanced coagulation process is a better option for arsenic
removal [286]. The presence of phosphate and silicate reduces the rate of
precipitation by ferric hydroxides. So, water which contains a large amount of
phosphate and silicate along with arsenate (e.g., well water in Bangladesh) needs a
special treatment. The Fe/As ratio should be greater than 40 (mg/mg) to reduce
arsenic to less than 50 lg/l (which is much greater than the toxicity limit !!!) in
Bangladesh. In this work, the researchers made a simpler method for household
filtration process: it included co-precipitation of arsenic by adding a packet
(approximately 2 g) of ferric and hypochlorite salts to 20 l of well water, and
subsequent filtration of the water through a bucket sand filter, and this water can be
easily used for cooking and drinking [18]. Removal of arsenate anions from aqueous
solution by co-precipitation with ferri-hydrite is employed as another arsenicremoval technique. An Fe/As ratio of 12 was chosen, and supersaturation was
controlled by varying the iron concentration or the pH. Higher supersaturation
removes arsenic at a higher rate [287]. Electrocoagulation (EC) is a very promising
electrochemical treatment technique that does not require the addition of chemicals
or regeneration. It has been treated as a treatment technology for arsenite [As(III)]
and arsenate [As(V)] removal from water. Three electrode materials, namely, iron,
aluminum, and titanium, are used to assess their efficiency, and iron has been found
to be the most efficient. EC was able to bring down aqueous phase arsenic
concentration to less than 10 lg/l with iron electrodes, and it was observed that
higher current density achieved rapid arsenic removal. EC has better removal
efficiency for As(III) in comparison with chemical coagulation (with ferric chloride)
[288].
Membrane process
The maximum contaminate level (MCL) for arsenic in drinking waste is to be lowered
in the United States. Membrane treatment is a viable method to meet the reduced MCL.
There are different types of membrane processes which are used for arsenic separation
from ground water. One of them is ultra filtration. Micellar-enhanced ultra filtration
(MEUF) is a low cost and easy method. In this work, four different cationic surfactants
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are used and the order of their efficiency is: cetyl pyridinium chloride (CPC) (96 %
removal) [ hexadecyltrimethylammonium bromide (CTAB) (94 % arsenic
removal) [ octadecylamine acetate(ODA) (80 % arsenic removal) [ benzalkonium
chloride (BC) (57 % arsenic removal). This removal is effective at a higher pH range
[289]. Cationic surfactant micelles along with ultrafiltration membrane separated
As(V) from a contaminated ground water sample. It was found that polyethersulfone
(PES) membranes without the surfactant micelles were found to be ineffective for
arsenic removal, but with the addition of cationic surfactant cetylpyridinium chloride
(CPC), the removal efficiency increases quickly [290]. In another study, the binding of
arsenic ions to cationic cetylpyridinium chloride (CPC) micelles has been investigated
using the semi-equilibrium dialysis (SED) technique. It has been shown that CPC
micelles are very effective at binding arsenic ions. At the studied pH (pH 8), the
unbound and bound arsenic exists primarily as divalent anions (HasO42-), while CPC
molecules exist as monovalent cations. Therefore, arsenic ions are bound electrostatically to the cationic micelle. The resultant colloid is large enough not to pass through
the dialysis membrane, producing a rejection greater than 99.59 % [291]. The
influences of membrane-operating conditions and water quality on the rejection of
arsenic by a negatively charged ultrafiltration (UF) membrane were investigated by a
group of workers. It is found that the presence of co-occurring divalent ions had a
detrimental influence on anionic As(V) rejection and As(V) can be easily removed by
this system [292].
Physical separation
There are different techniques other than the above by which arsenic can be separated
from its solutions. Solvent extraction is one of the tools. As(III) in the presence of
another metal and also As(V) can easily be separated from contaminated water by
bis(2,4,4-trimethylpentyl)dithiophsophinic acid (Cyanex 301) [293]. Arsenic in the
presence of another metal (e.g., Sb) can be separated from contaminated industrial
wastewater by a simple solvent extraction method. A recent work shows that the
organic heptane ? butanol mixture can be used for extraction of As(III) from a water
sample, and the process is eco-friendly, low-cost, and non-hazardous [294]. Arsenic
removal has been achieved by combining the processes of magnetic seeding
flocculation and open or high gradient superconducting magnetic separation.
Magnetite (Fe3O4) was used as magnetic seeding material and polymeric ferric
sulfate was added for combining the arsenic with the magnetite [295]. A novel
absorbent was prepared by dimercaptosuccinic acid chemically modifying mesoporous titanium dioxide which was employed as the micro-column packing material for
simultaneous separation of inorganic species. Both As(III) and As(V) species were
adsorbed quantitatively in the column within a pH range of 47, while at a pH range of
1011, only As(III) was retained in the column but As(V) species passed away. So,
this adsorbent could be a good material for species separation [296]. Liquidliquid
extraction processes can also separate As(V) from natural water sources using Aliquat
336, a supported liquid membrane which can transport As(V) at ppb level [297]. There
are some methods employed which use anion exchange chromatography to separate
the species and inductively coupled plasma-mass spectrometry as an arsenic-specific
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A. Basu et al.
detector. Anion-exchange chromatography (Hamilton, PRP 9100) with inductively

coupled plasma-mass spectrometry (ICP-MS) is commonly used for the speciation
and separation of arsenic in environmental and biological samples. The best result was
obtained with a mobile phase containing 30 mM NH4H2PO4 at pH 5.6, where the
separation of species, including arsenite [As(III)], arsenate [As(V)], dimethylarsinic
acid (DMA), and monomethylarsonic acid (MMA)], was achieved in a short period of
time [298]. A method has been proposed for separation from wastewater based on
progressive reduction of its solubility by a series of precipitation and solidification
agents. The most successful way is by embedding calcium and ferric arsenates/
arsenites in the cement matrix. The researchers have shown that it is possible to reduce
original arsenic solubility of 0,6430 mg/l from untreated waste to 0.823 mg/l from the
final solidificate by this technique [299].
Conclusion:
High levels of arsenic in groundwater commonly found in Bangladesh and West
Bengal, India, and other parts of the globe not only pose a risk via drinking water
consumption but also a risk in agricultural sustainability and food safety. The most
commonly used technologies are adsorption onto activated alumina, and precipitation
or adsorption by metal oxides, predominantly Fe(III) and membranes to remove
arsenic from wastewater. These technologies for arsenic removal from wastewater are
most appropriate for dealing with relatively low concentrations of arsenic, i.e. the low
lg/l level. However, the technique of precipitation, normally using Fe(III) or lime
softening, is matched at higher concentrations, normally at the low mg/l levels.
Adsorption is an important technique used in arsenic removal. Membrane technology,
especially nanofiltration, shows potential as a very good method in arsenic removal,
and is also widely being considered as the method that can be used to meet regulations
for lowered arsenic concentrations in drinking water. Future requirements on arsenic
elimination technology should take into consideration the lowering of the treatment
cost, the simplifying of the operational complexity of the technology, and the disposal
of arsenic-bearing treatment residues.
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A Review On Sources, Toxicity and Remediation Technologies For Removing Arsenic From Drinking Water

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Res Chem Intermed (2014) 40:447485

A review on sources, toxicity and remediation

Abstract Arsenic is a natural element found in the environment in organic and

Arsenic Toxicity Source Removal techniques

A review on sources, toxicity and remediation technologies

Natural; alluvial/deltaic sediments

Natural; alluvial sediments

Anthropogenic; mining and

Natural; coastal zones, black

Natural; alluvial and lake

Natural; alluvial sediments

Natural; loess and volcanic rocks,

Natural and anthropogenic;

Natural; similar to Chile and parts

Natural and anthropogenic;

Natural: mineralized sandstone

Natural; alluvial sediments;

Natural; alluvial sediments

Natural and anthropogenic;

Mining; southwest England

Anthropogenic and natural; gold

Natural and anthropogenic;

natural water, arsenic is mostly found in inorganic form as oxyanions of trivalent

A review on sources, toxicity and remediation technologies

Scheme 1 Species distribution of in the environment

Low-temperature hydrothermal vein mineral associated

Secondary mineral formed by oxidation of arsenopyrite,

Late-forming mineral in hydrothermal deposits; in the

Secondary mineral in lead ores

Hydrated copper arsenate mineral, found in copper

Secondary mineral in the oxide zone of CoNiAsbearing mineral deposits

Hydrothermal veins and contact metamorphic deposits

High temperature hydrothermal veins, in pegmatites,

High-temperature deposits, metamorphic rocks

Vein deposits and norites

Table 2 Major arsenic minerals occurring in nature

Secondary mineral formed by oxidation of realgar,

As an encrustation on furnace walls in which ores are

Baritefluorite veins including copper, silver and lead

A rare mineral in a metamorphosed FeMn ore body; on

Occurs as a secondary mineral in the oxidized zone of

Hydrothermal veins, Aktashskoye SbHg deposits

A review on sources, toxicity and remediation technologies

A post-mining superficial weathering product of FeAs

Uncommon mineral, occurs in the oxidized zone of

Rare secondary copper arsenate mineral

Secondary copper mineral and forms acicular crystals in

Rich vein-type AgCoNiBiU deposit

Secondary mineral occurring in the oxidized zones of

PbCrO4, AsO4, SiO2

A rare mineral in the oxidized zone of secondary

An uncommon oxidation zone mineral in NiCoAs

Low-temperature secondary parageneses

Metamorphosed MnFe ore bodies

Found in vein and replacement deposits formed at

Hydrothermal copper deposits

Secondary Fearsenate minerals

Occurs as a dehydration product of pharmacolite in the

Rare hydrothermal mineral

Occurs in high temperature hydrothermal deposits with

Occurs as a hydrothermal vein mineral along with other

Found in hydrothermal veins usually associated with

Occurs in Carlin-type hydrothermal deposits