What are the properties of arsenic?

Arsenic is a metalloid widely distributed in the earths crust and present at an average
concentration of 2 mg/kg. Arsenic can exist in four valency states: 3, 0, +3 and +5.
Under reducing conditions, arsenite (As (III)) is the dominant form; arsenate (As (V)) is
generally the stable form in oxygenated environments. Elemental arsenic is not soluble in
water. Arsenic salts exhibit a wide range of solubilities depending on pH and the ionic
environment.
Arsenic and its compounds occur in crystalline, powder, amorphous or vitreous forms.
They usually occur in trace quantities in all rock, soil, water and air. However,
concentrations may be higher in certain areas as a result of weathering and
anthropogenic activities including metal mining and smelting, fossil fuel combustion and
pesticide use.
There are many arsenic compounds of environmental importance. Inorganic compounds
include the trivalent arsenic trioxide, arsenic trichloride, arsenic trisulphide and sodium
arsenite. Pentavalent ones include arsenic pentoxide, arsenic acid and sodium arsenate.
Representative organic compounds are monomethyl-, dimethyl- and trimethylarsine, and
arsenobetaine.
How are arsenic levels measured?
There is a variety of instrumental techniques for the determination of arsenic. These
include atomic absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS),
inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled
plasma mass spectrometry (ICP-MS) and voltammetry. Some of these (e.g. ICP-MS) can
serve as element-specific detectors when coupled to chromatographic separation
techniques (e.g. HPLC and GC). These so-called "hyphenated" methods are used for
determining individual arsenic species. Additional sensitivity for a limited range of
arsenic compounds can often be achieved by the use of hydride generation techniques. A
test kit based on the colour reaction of arsine with mercuric bromide is currently used for
groundwater testing in Bangladesh and has a detection limit of 50100 g/litre under
field conditions.
What are the natural sources of environmental arsenic?
Sources and occurrence of arsenic in the environment.
Arsenic is present in more than 200 mineral species, the most common of which is
arsenopyrite.
It has been estimated that about one-third of the atmospheric flux of arsenic is of natural
origin. Volcanic action is the most important natural source of arsenic, followed by lowtemperature volatilization.
Inorganic arsenic of geological origin is found in groundwater used as drinking-water in
several parts of the world, for example Bangladesh.
Organic arsenic compounds such as arsenobetaine, arsenocholine, tetramethylarsonium
salts, arsenosugars and arsenic-containing lipids are mainly found in marine organisms
although some of these compounds have also been found in terrestrial species.

What are the man-made sources of environmental arsenic?

Elemental arsenic is produced by reduction of arsenic trioxide (As 2O3) with charcoal.
As2O3 is produced as a by-product of metal smelting operations. It has been estimated
that 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.
Historically, use of arsenic-containing pesticides has left large tracts of agricultural land
contaminated. The use of arsenic in the preservation of timber has also led to
contamination of the environment.

How is arsenic transported and distributed in the environment?

Environmental transport and distribution
Arsenic is emitted into the atmosphere by high-temperature processes such as coal-fired power
generation plants, burning vegetation and volcanism. Natural low-temperaturebiomethylation and
reduction to arsines also releases arsenic into the atmosphere. Arsenic is released into the
atmosphere primarily as As2O3 and exists mainly adsorbed on particulate matter. These particles are
dispersed by the wind and are returned to the earth by wet or dry deposition.
Arsines released from microbial sources in soils or sediments undergo oxidation in the air,
reconverting the arsenic to non-volatile forms, which settle back to the ground. Dissolved forms of
arsenic in the water column include arsenate, arsenite, methylarsonic acid (MMA) and dimethylarsinic
acid (DMA). In well-oxygenated water and sediments, nearly all arsenic is present in the
thermodynamically more stable pentavalent state (arsenate). Some arsenite and arsenate species
can interchange oxidation state depending on redox potential (Eh), pH and biological processes.
Some arsenic species have an affinity for clay mineral surfaces and organic matter and this can affect
their environmental behaviour. There is potential for arsenic release when there is fluctuation in Eh,
pH, soluble arsenic concentration and sediment organic content. Weathered rock and soil may be
transported by wind or water erosion. Many arsenic compounds tend to adsorb to soils, and leaching
usually results in transportation over only short distances in soil.
Three major modes of arsenic biotransformation have been found to occur in the environment: redox
transformation between arsenite and arsenate, the reduction andmethylation of arsenic, and the
biosynthesis of organo arsenic compounds. There is biogeochemical cycling of compounds formed
from these processes.
How much arsenic is there in the environment?
Environmental levels and human exposure
Mean total arsenic concentrations in air from remote and rural areas range from 0.02 to 4 ng/m 3.
Mean total arsenic concentrations in urban areas range from 3 to about 200 ng/m 3; much higher
concentrations (> 1000 ng/m3) have been measured in the vicinity of industrial sources, although in
some areas this is decreasing because of pollution abatement measures. Concentrations of arsenic in
open ocean seawater are typically 12 g/litre. Arsenic is widely distributed in surface freshwaters,
and concentrations in rivers and lakes are generally below 10 g/litre, although individual samples
may range up to 5 mg/litre near anthropogenic sources. Arsenic levels in groundwater average about

1t 2 g/litre except in areas with volcanic rock and sulfide mineral deposits where arsenic levels can
range up to 3 mg/litre. Mean sediment arsenic concentrations range from 5 to 3000 mg/kg, with the
higher levels occurring in areas of contamination. Background concentrations in soil range from 1 to
40 mg/kg, with mean values often around 5 mg/kg. Naturally elevated levels of arsenic in soils may be
associated with geological substrata such as sulfide ores. Anthropogenically contaminated soils can
have concentrations of arsenic up to several grams per 100 ml

What happens to arsenic absorbed by the body?

Absorption of arsenic in inhaled airborne particles is highly dependent on the solubility and the size of
particles. Both pentavalent and trivalent soluble arsenic compounds are rapidly and
extensively absorbed from the gastrointestinal tract. In many species arsenicmetabolism is
characterized by two main types of reactions: (1) reduction reactions of pentavalent to trivalent
arsenic, and (2) oxidative methylation reactions in which trivalent forms of arsenic are sequentially
methylated to form mono-, di- and trimethylated products using S-adenosyl methionine (SAM) as
the methyl donor and glutathione (GSH) as an essential co-factor. Methylation of inorganic
arsenic facilitates the excretion of inorganic arsenic from the body, as the end-products MMA and
DMA are readily excreted in urine. There are major qualitative and quantitative interspecies
differences in methylation, to the extent that some species exhibit minimal or no arsenic methylation
(e.g. marmoset monkey, guinea-pig, chimpanzee). However, in humans and most common laboratory
animals, inorganic arsenic is extensively methylated and the metabolites are excreted primarily in the
urine. Factors such as dose, age, gender and smoking contribute only minimally to the large interindividual variation in arsenic methylation observed in humans. However, lower methylation efficiency
in children has been observed in only one study out of three. Studies in humans suggest the
existence of a wide difference in the activity of methyltransferases, and the existence of polymorphism
has been hypothesized. Animal and human studies suggest that arsenic methylation may be inhibited
at high acute exposures. The metabolism and disposition of inorganic arsenic may be influenced by
its valence state, particularly at high dose levels. Studies in laboratory animals indicate that
administration of trivalent inorganic arsenic such as As 2O3 and arsenite initially results in higher levels
in most tissues than does the administration of pentavalent arsenic. However, the trivalent form is
more extensively methylated, leading to similar long-term excretion.Ingested organoarsenicals such
as MMA, DMA and arsenobetaine are much less extensively metabolized and more rapidly eliminated
in urine than inorganic arsenic in both laboratory animals and humans

What are the indicators of arsenic exposure?

The source document for this Digest states:
Levels of arsenic or its metabolites in blood, hair, nails and urine are used as biomarkers of
arsenic exposure. Blood arsenic is a useful biomarker only in the case of acute arsenic poisoning or
stable chronic high-level exposure. Arsenic is rapidly cleared from blood, and speciation of its
chemical forms in blood is difficult. Arsenic in hair and nails can be indicators of past arsenic
exposure, provided care is taken to prevent external arsenic contamination of the samples. Arsenic in
hair may also be used to estimate relative length of time since an acute exposure. Speciated

metabolites in urine expressed either asinorganic arsenic or as the sum of metabolites (inorganic
arsenic + MMA + DMA) provide the best quantitative estimate of recently absorbed dose of arsenic.
However, consumption of certain seafood, mainly seaweed and some bivalves, may confound
estimation of inorganic arsenic exposure because of metabolism of arsenosugars to DMA in the body
or the presence of DMA in the seafood. Such food should be avoided for 23 days before urine
sampling for monitoring of exposure to inorganic arsenic.

Can arsenic cause cancer and skin changes?

Effects on human health
() Long-term exposure to arsenic in drinking-water is causally related to increased risks of cancer in
the skin, lungs, bladder and kidney, as well as other skin changes such as hyperkeratosis
and pigmentation changes. These effects have been demonstrated in many studies using different
study designs. Exposureresponse relationships and high risks have been observed for each of these
end-points. The effects have been most thoroughly studied in Taiwan but there is considerable
evidence from studies on populations in other countries as well. Increased risks of lung and
bladder cancer and of arsenic-associated skin lesions have been reported to be associated
with ingestion of drinking-water at concentrations 50g arsenic/litre.
Occupational exposure to arsenic, primarily by inhalation, is causally associated with lungcancer.
Exposureresponse relationships and high risks have been observed. Increased risks have been
observed at cumulative exposure levels 0.75 (mg/m 3) year (e.g. 15 years of exposure to a
workroom air concentration of 50 g/m3). Tobacco smoking has been investigated in two of the three
main smelter cohorts and was not found to be the cause of the increased lung cancer risk attributed to
arsenic; however, it was found to be interactive with arsenic in increasing the lung cancer risk.
Even with some negative findings, the overall weight of evidence indicates that arsenic can cause
clastogenic damage in different cell types with different end-points in exposedindividuals and
in cancer patients. For point mutations, the results are largely negative.

What other health problems can arsenic cause?

Soluble inorganic arsenic is acutely toxic, and ingestion of large doses leads to gastrointestinal
symptoms, disturbances of cardiovascular and nervous system functions, and eventually death. In
survivors, bone marrow depression, haemolysis, hepatomegaly, melanosis, polyneuropathy and
encephalopathy may be observed. ()
Chronic arsenic exposure in Taiwan has been shown to cause blackfoot disease (BFD), a severe form
of peripheral vascular disease (PVD) which leads to gangrenous changes. This disease has not been
documented in other parts of the world, and the findings in Taiwan may depend upon other
contributing factors. However, there is good evidence from studies in several countries that arsenic
exposure causes other forms of PVD.

Conclusions on the causality of the relationship between arsenic exposure and other health effects
are less clear-cut. The evidence is strongest for hypertension and cardiovasculardisease, suggestive
for diabetes and reproductive effects and weak for cerebrovascular disease, long-term neurological
effects, and cancer at sites other than lung, bladder, kidney and skin

What has happened in areas where drinking water is heavily contaminated?

In nature, arsenic-bearing minerals undergo oxidation and release arsenic to water. This could be one
explanation for the problems of arsenic in the groundwater of West Bengal and Bangladesh. In these
areas the groundwater usage is very high. It has been estimated that there are about 410 million
tube wells in Bangladesh alone. [It was thought that] the excessive withdrawal and lowering of the
water table for rice irrigation and other requirements lead to the exposure and subsequent oxidation of
arsenic-containing pyrite in the sediment. As the water table recharges after rainfall, arsenic leaches
out of the sediment into the aquifer.
However, recent studies seem to favour the reduction of Fe/As oxyhydroxides as the source for
arsenic contamination in groundwater. Arsenic forms co-precipitates with ferric oxyhydroxide. Burial of
the sediment, rich in ferric oxyhydroxide and organic matter, has led to the strongly reducing
groundwater conditions. The process has been aided by the high water table and fine-grained surface
layers which impede the penetration of air to the aquifer. Microbial oxidation of organic carbon has
depleted the dissolved oxygen in the groundwater. The highly reducing nature of the groundwater
explains the presence ofarsenite (< 50%) in the water. The "pyrite oxidation" hypothesis is therefore
unlikely to be a major process, and the "oxyhydroxide reduction" hypothesis is probably the main
cause of arsenic contamination in groundwater. Although the oxyhydroxide reduction hypothesis
requires further validation, there is no doubt that the source of arsenic in West Bengal and
Bangladesh is geological, as none of the explanations for anthropogenic contamination can account
for the regional extent of groundwater contamination.
Although arsenic levels in natural waters are usually low (a few g/litre), there are several areas in the
world where humans consume drinking-water containing > 100 g As/litre resulting from natural
geochemical activity. In the West Bengal region of India it was estimated that over 1 000 000 people
consume drinking-water containing > 50 g/litre (up to 3.7 mg/litre) arising from normal geochemical
processes. In the areas of West Bengal and Bangladesh, 38% of groundwaters sampled in 27 districts
were > 50 g/litre. Natural geochemistry resulted in the pre-1970 exposure of about 100 000 people in
the south-western coastal region of Taiwan to variable but high (101800 g/litre, mean 500
g/litre)concentrations of arsenic in drinking-water. A similar problem was reported in Chile where 100
000 people consumed drinking-water containing 800 g As/litre between 1959 and 1970, when
the concentration was lowered to about 50 g/litre. About 200 000 people in north central Mexico
were reported to be exposed to >50 g/litre arsenic in drinking-water (410 g/litre in at least one
village).
Chronic skin effects of arsenic, including pigmentation changes, hyperkeratosis and skincancer, from
medicinal use but also from drinking-water, were reported as early as the 19th century. A large
number of case series on arsenical skin cancer after exposure via drinking-water were published from
Argentina, Chile, Mexico and Taiwan in the early 1900s.

An endemic peripheral vascular disease, known as wu chiao ping or blackfoot disease, leading to
progressive gangrene of the legs, has been known in Taiwan since the 1920s. It has increased in
prevalence since the 1950s, and has been the subject of intense investigation since the late 1950s.
Applications
Medical use
During the 18th, 19th, and 20th centuries, a number of arsenic compounds were used as medicines,
including arsphenamine (by Paul Ehrlich) and arsenic trioxide (by Thomas Fowler).[54] Arsphenamine,
as well as neosalvarsan, was indicated for syphilis and trypanosomiasis, but has been superseded by
modern antibiotics.
Arsenic trioxide has been used in a variety of ways over the past 500 years, most commonly in the
treatment of cancer, but in medications as diverse as Fowler's solution inpsoriasis.[55] The US Food
and Drug Administration in the year 2000 approved this compound for the treatment of patients
with acute promyelocytic leukemia that is resistant to all-trans retinoic acid.[56]
Recently, new research has been done in locating tumors using arsenic-74 (a positron emitter). The
advantages of using this isotope instead of the previously used iodine-124 is that the signal in
the PET scan is clearer as the body tends to transport iodine to the thyroid gland producing signal
noise.[57]
In subtoxic doses, soluble arsenic compounds act as stimulants, and were once popular in small
doses as medicine by people in the mid-18th to 19th centuries. [9]
Alloys
The main use of metallic arsenic is in alloying with lead. Lead components in car batteries are
strengthened by the presence of a very small percentage of arsenic. [6][58]Dezincification can be
strongly reduced by adding arsenic to brass, a copper-zinc alloy. [59] "Phosphorus Deoxidized Arsenical
Copper" with an arsenic content of 0.3% has an increased corrosion stability in certain environments.
[60]

Gallium arsenide is an important semiconductor material, used in integrated circuits. Circuits made

from GaAs are much faster (but also much more expensive) than those made in silicon. Unlike silicon,
it

has

a direct

bandgap,

convert electricity intolight.

so

can

be

used

in laser

diodes and LEDs to

directly

[6]

Military
After World War I, the United States built up a stockpile of 20,000 tonnes of lewisite (ClCH=CHAsCl2),
a chemical weapon that is a vesicant (blister agent) and lung irritant. The stockpile was neutralized
with bleach and dumped into the Gulf of Mexico after the 1950s.[61] During the Vietnam War, the
United States used Agent Blue, a mixture of sodium cacodylate and its acid form, as one of
the rainbow herbicides to deprive North Vietnamese soldiers of foliage cover and rice. [62][63]

Other uses

Copper acetoarsenite was used as a green pigment known under many names,
including Paris Green and Emerald Green. It caused numerous arsenic poisonings. Scheele's
Green, a copper arsenate, was used in the 19th century as a coloring agent in sweets.[64]

In bronzing[65] and pyrotechnics

Up to 2% of arsenic is used in lead alloys for lead shot and bullets.[66]

Arsenic is added in small quantities to alpha-brass to make it dezincification-resistant. This

grade of brass is used to make plumbing fittings or other items that are in constant contact with
water.[67]

Arsenic is also used for taxonomic sample preservation.

Until recently, arsenic was used in optical glass. Modern glass manufacturers, under pressure
from environmentalists, have removed it, along with lead.[68]

Biological role
Bacteria[edit]

Arsenobetaine
Some species of bacteria obtain their energy by oxidizing various fuels while reducing arsenate to
arsenite. Under oxidative environmental conditions some bacteria use arsenite, which is oxidized to
arsenate

as

fuel

for

their

metabolism. [69] The enzymes involved

are

known

asarsenate

reductases (Arr).[70]
In 2008, bacteria were discovered that employ a version of photosynthesis in the absence of oxygen
with arsenites as electron donors, producing arsenates (just as ordinary photosynthesis uses water as
electron donor, producing molecular oxygen). Researchers conjecture that, over the course of history,
these photosynthesizing organisms produced the arsenates that allowed the arsenate-reducing
bacteria

to

thrive.

One strain PHS-1

has

been

isolated

and

is

related

to

the gammaproteobacterium Ectothiorhodospira shaposhnikovii. The mechanism is unknown, but an

encoded Arr enzyme may function in reverse to its known homologues.[71]
Although the arsenate and phosphate anions are similar structurally, no evidence exists for the
replacement of phosphate in ATP or nucleic acids by arsenic.[

Bioremediation[edit]
Physical, chemical, and biological methods have been used to decrease the concentration of arsenic
in contaminated water.[124] Among these methods, bioremediation has been suggested to be cost
effective and environmentally friendly[125] Bioremediation of ground water contaminated with arsenic
aims to convert arsenite, the toxic form of arsenic to humans, to arsenate. Arsenate (+5 oxidation
state) is the dominant form of arsenic in surface water, while arsenite (+3 oxidation state) is the
dominant form in hypoxic to anoxic environments. Arsenite is more soluble and mobile than arsenate.
Many species of bacteria can transform arsenite to arsenate in anoxic conditions by using arsenite as
an electron donor.[126] This is a useful method in ground water remediation. Another bioremediation
strategy is to use plants that accumulate arsenic in their tissues viaphytoremediation but the disposal
of contaminated plant material needs to be considered. In order to choose a suitable bioremediation
approach for a site, its environmental conditions needs to be evaluated. Some sites may require the
addition of an electron acceptor while others require added microbes (bioaugmentation). Regardless
of the method used, constant monitoring is required to prevent future contamination.
Bioremediation is a natural process which relies on bacteria, fungi, and plants to alter contaminants as
these organisms carry out their normal life functions. Metabolic processes of these organisms are
capable of using chemical contaminants as an energy source, rendering the contaminants harmless
or less toxic products in most cases. Thus, bioremediation provides an alternative tool to destroy or
render the harmful contaminants through biological activity and this method is also cost effective
Bioremediation of Arsenic from Contaminated Water
Presently, over 100 million people worldwide are exposed to arsenic contaminated groundwater
making it one of the largest environmental catastrophes. Arsenic originates from the earths crust
which finds its way into groundwater as a result of various geological, biological and even
anthropological processes. Toxicity effects of arsenic have been reported in plants, animals and most
vividly in humans. WHO has recently brought down the permissible limit of arsenic in drinking water to
10 g/L. Various physicochemical and biological arsenic remediation methods have been reported
and applied to render groundwater potable for human use. Microbial remediation of arsenic from
aquatic environments presents an interesting option because of its high efficiency, low cost and most
importantly its ecofriendly nature. Microbial bioremediation of arsenic occurs through various
processes. Microbially mediated arsenic redox reactions are one of the most important phenomena
for arsenic remediation. We have reported Microbacterium lacticum, a unique bacterium that can
tolerate up to 3,000 mg/L arsenite and oxidizes it rapidly to arsenate almost totally and applied this
organism for arsenic bioremediation in field level operations in the arsenic affected areas. Besides
microbial oxidation, biosorption and methylation are other options that have been tried with limited
success. Thus many options are available for microbial bioremediation of arsenic from aqueous
environments; these can be effectively used with or without other physicochemical methods. Our
article will take an in-depth review of the fundamental processes involved as well as various
laboratory scale, pilot scale and field scale technologies developed.

Bioremediation of Heavy Metals

Bioremediation is the naturally occurring process in which microorganisms or plants either immobilize
or transform environmental contaminants to innocuous state end products [11]. During bioremediation,
microbes utilize chemical contaminants in the soil as an energy source and through redox-potential
they can metabolize the target contaminant into usable energy for microbes. Although multitudes of
reactions are adopted by microbes to degrade and transform pollutants but all the energy yielding
reactions are oxidation-reduction reactions and the typical electron acceptors are oxygen, nitrates,
sulfate and carbon dioxide.
For bioremediation, it is important that effective, microorganisms and plants may degrade the
pollutants in to harmless products by various enzymatic actions [7]. The microbes cant degrade
heavy metals directly but they can change the valence states of metals which may convert them into
immobile or less toxic forms. Collins and Stotzky [12] stated that several metals are essential for
biological systems and present in a range of certain concentration. The metals always have been
associated with metalloproteins and enzymes as co-factors. Its low concentrations lead to decrease in
metabolic activity while high concentrations could act in a deleterious way by blocking essential
functional groups, displacing other metal ions, or modifying the active conformation of biological
molecules. Besides, they are toxic for both higher organisms and microorganisms.
The progressive accumulation of metals may inhibit the degradation of organic pollutants or humic
substances in the environment. This problem can be solved by an increase of the heavy metal
resistance of the bioremediating system. Heavy metals are present in soils and aqueous streams as
both natural components or as a result of human activity (i.e., metal-rich mine tailings, metal smelting,
electroplating, gas exhaust, energy and fuel production, downwash from power lines, intensive
agriculture, sludge dumping [13]. 2.1. Bioremediation of Heavy Metals by Plants
Phytoremediation is the use of green plants to clean-up hazardous waste from the contaminated sites
[14]. Phytoremediation can be used either as an in-situ or ex-situ application. The in-situ applications
are frequently considered because it can minimize the disturbance of the soil and surrounding
environment and also reduce the spread of contamination via air and water borne wastes. Thus, it is
also known as green technology and proper implementation make it eco-friendly and aesthetically
pleasing to the public [15]. Phytoremediation does not require expensive equipment or highlyspecialized personnel, thus, it is relatively easy to implement. It is capable of permanently treating a
wide range of contaminants in a wide range of environments. There are various types of
phytoremediation processes, which may cover a large numbers of organic and inorganic compounds
discussed below.
2.2. Mechanisms of Bioremediation by Plants
2.2.1. Phytoextraction
Phytoextraction is primarily used for the treatment of contaminated soils. In this method plants absorb
the concentrated metals and after precipitated from contaminated soils these metals accumulate were
into the above ground parts of plants. There are few plants species known for higher accumulator and
show their potential towards the removal of metals from contaminated soils. Brennan and Shelley [16]

found that plants have the capability to extract large concentrations of heavy metals into their roots,
translocate them into the surface and produce a large quantity of plant biomass. Beside this there are
several limiting factors for phytoextraction. Metal bioavailability within the rhizosphere Rate of metal
uptake by roots Proportion of metal fixed within the roots Rate of xylem loading/translocation to
shoots Cellular tolerance to toxic metals.
2.2.2. Phytostabilization
Phytostabilization is the method used for the remediation of soil, sediment, and sludges. In this
method the use of plant roots may limit the contaminant in the soil through mobility and bioavailability
process. The plants decrease the amount of water percolating through the soil matrix, which may act
as a barrier and prevent direct contact with the contaminated soil. It may also prevent soil erosion and
distribution of the toxic metal to other areas [14]. Phytostabilization can occur through the sorption,
precipitation, complexation, or metal valence reduction. It is helpful in the treatment of contaminated
land areas affected by mining activities and Superfund sites [14]. Phytostabilization is commonly used
to treat the metals (arsenic, cadmium, chromium, copper and zinc) contaminants [17] . It has also
several disadvantages. Contaminant remaining in soil Application of extensive fertilization or soil
amendments
Bioremediation of Heavy Metals by Microbes
Soil, sediment and water sources were contaminated by hazardous heavy metals through industrial
activities, such as mining, refining, and electroplating. Mercury, arsenic, lead, and chromium are often
prevalent at contaminated sites. White et al. [20] reported that bacterial remediation is the process of
using metal reducing bacteria to break down the contaminants. The metal-reducing bacteria are able
to reduce very toxic soluble forms into less toxic forms. Macaskie et al. [21] found that sulfatereducing bacteria successfully treat the metal leachates generated by sulfuric-acid producing
Thiobacillus sp. However, Meysami and Baheri [22] reported that white rot fungi have the ability to
transform the pollutants from the contaminants in soil through ligninolytic enzymes. Moreover, Lang et
al. [23] have successfully used the production and activity of ligninolytic enzymes in the
bioremediation of contaminated from under field conditions. In natural soil a wide range of saprophytic
microorganisms are pre-exist but the introduction of white rot fungi requires effective growth and
competition with these native populations. Additionally, the fungi used for the bioremediation proposes
should also secrete the degrading enzymes into the soil matrix to enhance degradation of pesticide
that they are not able to incorporate across cell walls.
Bioremediation Arsenic by Microorganisms
The microbial activity could reduce the arsenic through sorption, biomethylation, complexation, and
oxidation-reduction processes. Microorganisms have evolved the biochemical mechanisms to exploit
arsenic either as an electron acceptor for anaerobic respiration, or as an electron donor to support
chemoautotrophic fixation of CO2 into cell carbon [37]. The key microbes involved are categorized as
dissimilatory arsenate-reducing prokaryotes from both bacterial and archaeal domains. It uses

arsenate as an electron acceptor and reducing it to arsenite. Chemoautotrophic arsenite oxidizers,

microorganisms use CO2 as a carbon source and use arsenite as an electron source, oxidizing it to
arsenate for energy. However, heterotrophic arsenite oxidizers use oxygen as an electron acceptor
and oxidize arsenite to arsenate. Arsenate-resistant microbes reduce arsenate into arsenite, which
allows the transport of toxic form from the cell
Case Study: Mobilization of Arsenite by Dissimilatory Reduction of Absorbed Arsenate
(Zobrist, 2000)
This study experiments with cell suspensions of Sulfurospirillum barnessii, a bacterium that reduces
arsenate to arsenite.
Introduction
Biological processes aid with the facilitation and mobilization of arsenic. This experiment
demonstrates that ferric oxide or oxyhydroxide phases are buried in sediments, and reductive
dissolution of ferric oxides can release arsenic and other trace metals into the soil. (Zobrist, 2000).
Solubilization of As (V) occurred when Fe (III)-respiring bacterium was incubated with contaminated
lake sediments.
Research is discovering anaerobic bacteria species that can achieve respiratory reduction of As (V) to
As (III) (Zobrist, 2000). Respiratory reduction of As (V) to As (III) is called dissimilatory reduction and
involves two bacteria strains, Sulfurospirillum arsenophilum and Sulfurospirillum barnesii (Zobrist,
2000). This experiment studies Fe (III) respiring Shewanella alga, an organism that does not respire
As (V), but can release As (V) and Fe (II) into solution (Zobrist, 2000).
Materials and Methods
The preparation of ferric and aluminum hydroxides involves the use of a 2-line ferrihydrite that was
synthesized in a polyethylene vessel under a nitrogen (N2) atmosphere (Zobris t, 2000). All chemicals
in this experiment were made with a reagent grade. The water in this study was double-deionized and
passed through a Milli-Q-System (Zobrist, 2000). Furthermore, gas from all the solutions was
removed, except for analytical reagents (Zobrist, 2000).
Bacteria
S. barnessii strain was grown in a batch culture with nitrate. Nitrate acts as the electron acceptor; this
situation allows the culture cells to reduce As (V) (Zobrist, 2000). Nitrate was chosen as the electron
acceptor in the presence of As (V) or Fe (III) (Zobrist, 2000). The cells were harvested by
centrifugation and washed twice with a solution consisting of a HEPES buffer at a pH of 7.3 and
neutral salts (Zobrist, 2000).
Conclusion
The cell suspensions of S. Barnessi were able to reduce arsenate to arsenite. The reduction of Fe (III)
in ferrihydrite to soluble Fe (II) occurred with the cultured cells (Zobrist, 2000). The rate of arsenate
reduction was affected by the method that involved arsenate becoming associated with the mineral
phases and the binding with the arsenate (Zobrist, 2000). The extent of the release of arsenite was

regulated by the absorption of arsenite into the ferrihydrite or aluminia phases (Zobrist, 2000). These
results help with understanding the mobilization of arsenic in large aquifers.
Case Study: A New Chemolithoautotrophic Arsenite-Oxidizing Bacterium Isolated from a Gold
Mine: Phylogenetic, Physiological, and Preliminary Biochemical Studies (Santini, Sly, Schnagl,
and Macy, 2000).
Introduction
Arsenic is a compound that is very toxic to many life forms. However, when arsenic is in its insoluble
form, it is not a harmful compound. Arsenic in its insoluble form is found in minerals, such as
arsenopyrite (FeAsS) (Santini, Sly, Schnagl, and Macy, 2000). The oxidation of the insoluble form of
arsenic results in its transformation. Chemical and microbial processes often facilitate this oxidation.
For instance, microbial processes can convert insoluble arsenic to arsenite (As III) (H3AsO3), now a
soluble form of arsenic (Santini, Sly, Schnagl, and Macy, 2000). Acid mines often possess high
concentrations of arsenite. The transformation of arsenite could be further oxidized by other microbial
and chemical reactions. The oxidation of arsenite results in the formation of arsenate (As V (H2 As04+ H+). Arsenite and arsenate are both very toxic forms of arsenic. Arsenite is more toxic than arsenate
(Santini, Sly, Schnagl, and Macy, 2000). This information is valuable to the advancement and
improvement of bioremediation techniques. History shows that arsenite-oxidizing bacteria was first
identified in 1918 (Santini, Sly, Schnagl, and Macy, 2000). Research also shows that more of these
organisms have been identified since 1918. Arsenite-oxidizing bacteria are heterotrophic, meaning an
organism requires organic matter for growth. Alcaligenes faecalis is the most common arseniteoxidizing bacteria. However, arsenite oxidizing bacterias heterotrophic condition is considered a
detoxification mechanism rather than a mechanism that supports growth. Pseudomonas
arsenitoxidans is the only organism known to gain energy in the presence of arsenite. This organism
holds its ability to grow chemolithoautotrophically with arsenite, oxygen,and carbon dioxide. This
experiment reports a new bacterium that was isolated from a gold mine in the northern territory of
Australia that can also grow chemolithoautotrophically with arsenite. In addition, this organism can
serve as an electron donor, with oxygen being an electron acceptor, and carbon dioxide (CO2) or
bicarbonate (HCO3-) as the carbon source (Santini, Sly, Schnagl, and Macy, 2000). This discovery is
important because it can help those interested in the bioremediation of arsenic understand the factors
that affect remedia ting arsenic. Studies show that microorganisms can contribute to the toxification of
arsenic. A site filled with arsenite-oxidizing bacteria will create more toxic forms of arsenic and
increase the ineffectiveness of bioremediating arsenic (Santini, Sly, Schnagl, and Macy, 2000). Until
the discovery of an organism or procedure that can counteract arsenic transformation, bioremediation
of arsenic will remain ineffective and costly.
TECHNOLOGIES FOR ARSENIC REMOVAL
In some areas, arsenic-contaminated water will be abundant and arsenic-free sources scarce or
polluted with other compounds. In these areas it may be most efficient to remove arsenic from the
contaminated water, at least as a short term measure. Many technologies have been developed for
the removal of arsenic. Most of the documented experience has been with large municipal treatment
plants, but some of the same technologies can be applied at community or household levels.

All of the technologies for arsenic removal rely on a few basic chemical processes, which are
summarized below:
Oxidation/reduction: reactions that reduce (add electrons to) or oxidize (remove electrons from)
chemicals, altering their chemical form. These reactions do not remove arsenic from solution, but are
often used to optimize other processes.
Precipitation: Causing dissolved arsenic to form a low-solubility solid mineral, such as calcium
arsenate. This solid can then be removed through sedimentation and filtration. When coagulants are
added and form flocs, other dissolved compounds such as arsenic can become insoluble and form
solids, this is known as coprecipitation. The solids formed may remain suspended, and require
removal through solid/liquid separation processes, typically coagulation and filtration.
Adsorption and ion exchange: various solid materials, including iron and aluminum hydroxide
flocs, have a strong affinity for dissolved arsenic. Arsenic is strongly attracted to sorption sites on the
surfaces of these solids, and is effectively removed from solution. Ion exchange can be considered as
a special form of adsorption, though it is often considered separately. Ion exchange involves the
reversible displacement of an ion adsorbed onto a solid surface by a dissolved ion. Other forms of
adsorption involve stronger bonds, and are less easily reversed.
Solid/liquid separation: precipitation, co-precipitation, adsorption, and ion exchange all transfer the
contaminant from the dissolved to a solid phase. In some cases the solid is large and fixed (e.g.
grains of ion exchange resin), and no solid/liquid separation is required. If the solids are formed in situ
(through precipitation or coagulation) they must be separated from the water. Gravity settling (also
called sedimentation) can accomplish some of this, but filtration is more effective. Most commonly,
sand filters are used for this purpose.
Physical exclusion: some synthetic membranes are permeable to certain dissolved compounds but
exclude others. These membranes can act as a molecular filter to remove dissolved arsenic, along
with many other dissolved and particulate compounds.
Biological removal processes: bacteria can play an important role in catalyzing many of the above
processes. Relatively little is known about the potential for biological removal of arsenic from water.
Boiling does not remove arsenic from water.
Most of the established technologies for arsenic removal make use of several of these processes,
either at the same time or in sequence. All of the removal technologies have the added benefit of
removing other undesirable compounds along with arsenic depending on the technology, bacteria,
turbidity, color, odor, hardness, phosphate, fluoride, nitrate, iron, manganese, and other metals can be
removed.
Historically, the most common technologies for arsenic removal have been coagulation with metal
salts, lime softening, and iron/manganese removal. Since the WHO Guideline Value for arsenic in
drinking water was lowered from 50 to10 g/L in 1993, several countries have lowered their drinking
water standards, in some cases to 10 g/L. In January 2001, the USEPA lowered the U.S. drinking
water standard from 50 to 10 g/L(only to postpone/reconsider this decision a few months later).

Coagulation processes are sometimes unable to efficiently remove arsenic to these low levels. As a
result, various alternate technologies have been developed or adapted that are capable of removing
arsenic to trace levels. These advanced treatment options include ion exchange, activated alumina,
and membrane methods such as reverse osmosis and nanofiltration. While these technologies have
all been shown to be effective in lab or pilot studies, there is still relatively little experience with fullscale treatment. In addition, a number of novel removal technologies are under development, some of
which show great promise. The main arsenic removal technologies are presented below, along with a
brief description of how removal efficiency is affected by arsenic concentration and speciation, pH,
and the presence of other dissolved constituents.
Emerging Technologies
In recent years, a tremendous amount of research has been conducted to identify novel
technologies for arsenic removal, particularly low-cost, low-tech systems that can be
applied in rural areas. Most of these technologies rely on oxidation of arsenite, followed
by filtration through some sort of porous material, where arsenic is removed through
adsorption and coprecipitation. Many of these systems make use of iron compounds,
which have a very strong affinity for arsenic. A brief review of some of the most
documented technologies is given below.
Fe-Mn Oxidation
Conventional iron and manganese removal can result in significant arsenic removal,
through coprecipitation and sorption onto ferric or manganic hydroxides. The
mechanisms involved are the same as in coagulation and filtration. Most low-cost
technologies for arsenic and manganese removal rely on aeration and filtration through
porous media such as sand and gravel. Any technology that effectively removes iron and
manganese could be evaluated to see if arsenic is also removed effectively. In this
respect arsenic removal is more convenient than that of fluoride, which does not
undergo oxidation, and is not removed by coprecipitation with iron.
In Bangladesh and West Bengal, elevated arsenic concentrations are often associated
with high iron and manganese levels. One survey in Bangladesh found that over 80% of
arsenic-affected tube wells (>50 g/L) also contained iron levels of 2 mg/L or more.
However, iron alone is not a good indicator of arsenic: 30% of the wells with safe levels
of arsenic also had 2 mg/L iron or more (DPHE/BGS/MML, 1999). Because of the link
between arsenic and iron levels, and the affinity of arsenic for iron hydroxides, there
have been calls for a simple solution to arsenic contamination: simple storage of pumped
water to allow iron to settle out, scavenging arsenic in the process. While this is an
appealing idea, successful application of this type of passive Fe-Mn oxidation is not
simple, for several reasons:

iron removal is not always easily accomplished. Some waters contain iron in a
form that is slow to oxidize, or may be complexed with organic material that
impedes oxidation and filtration. Precipitation may not occur if alkalinity is low;
without a filtration step, much of the iron can remain suspended as colloidal
matter, even after oxidation;
arsenite is not as strongly bound to iron as arsenate, if the waters contain mostly
arsenite arsenic removal will be less efficient; and
when water is stored in household containers, there is a high risk of bacterial
contamination.

When considering passive Fe-Mn oxidation, particularly at the household level, careful
pilot studies should be made using the local waters and local storage conditions, in order
to assess the effectiveness of this technique, and the possibility of pathogenic
contamination. It should be noted that chlorine addition would improve oxidation of both
iron and arsenic, and would provide protection against bacterial growth. However, as
discussed above, chlorination at the household level involves difficulties in ensuring the
correct dose, and the potency of the chlorine agent.
With support from the Dutch Government, the Department of Public Health Engineering
of Bangladesh has constructed three arsenic removal plants in small municipalities.
These plants are basically iron removal plants, and add no chemicals, but pump
groundwater over a series of cascades to aerate the water. Filtration then removes the
resulting iron and arsenic precipitate, and the water is chlorinated and stored in an
elevated tank for distribution. Water stored in the tank is periodically used to backwash
the filters. The waste water is stored in sludge ponds, and sludge is removed once or
twice annually. Arsenic removal efficiency varies considerably, and seems to improve
with higher iron levels.
Ion exchange and adsorption
Ion exchange resins developed for removal of anions such as sulfate and nitrate have
proven to be reasonably effective at removing arsenic, as discussed above. As materials
engineering becomes more advanced, researchers are increasingly able to design novel
ion-exchange materials with surficial properties that areparticularly specific to arsenate.
In particular, several researchers have found that copper-doped materials have a strong,
specific affinity for arsenate (e.g. Rajakovic and Mitrovicm, 1992; Ramana and Sengupta,
1992; Lorenzen et al., 1995). Fryxell and others have developed a novel mesoporous
silica sorbent which makes use of Cu(II)-based functional groups. This material has a
higher ion exchange capacity (75 mg As/g) than conventional resins, and shows a
stronger affinity for arsenate and chromate than for sulfate or nitrate. Therefore, unlike
the conventional resins, these materials will not release chromatographic peaks of
arsenic when exposed to high levels of sulfate (Fryxell et al., 1999).
While conventional synthetic ion exchange resins are the most commonly used media in
ion exchange, costs are relatively high ($USD 2-5 per liter of wet resin). A variety of
naturally occurring materials also have high ion exchange capacities, sometimes after
chemical pre treatment. Many of these materials are not pure ion exchangers: some
arsenic removal is through less reversible chemisorption. Especially in developing
countries, researchers have been evaluating the potential of these materials for use as
low-cost arsenic removal systems.
Zeolites are naturally occurring minerals with a crystalline structure characterized by
large internal pore spaces. Accordingly, they have very large surface areas, and ion
exchange capacities: zeolites were used extensively for water softening, before the
development of synthetic resins with faster exchange rates, higher capacity, and longer
life. A few arsenic removal studies have been conducted with zeolites.
Natural zeolite minerals such as clinoptilolite and chabazite have a strong affinity for
both arsenite and arsenate. A chabazite filter was able to remove 1000 g/L arsenate
from over 235 bed volumes before arsenic was detected in the effluent (Bonnin, 1997).
Adsorption of arsenate onto natural zeolites can be improved by organically modifying
the zeolite structure (Misaelides et al., 1998).

Chitosan and chitin are natural polyaminosaccharides occurring in crustacean shells, that
have good ion exchange properties. Shellfish wastes containing chitosan have been used
to remove arsenic from water contaminated by mining wastes (Luong and Brown, 1984).
Elson and others investigated a mixture of chitosan and chitin, and found a relatively low
arsenic removal capacity of about 0.01 mg As/g (Elson et al., 1980).
Adhesion of atoms, ions, bimolecules or molecules of gas, liquid or dissolved solids to a
surface is called adsorption. This process creates a film of the adsorbate the molecules
or atoms being accumulated, on the surface of the adsorbent.

Examples:

Activated charcoal adsorbs gases like CO2 , SO2, Cl2 etc.

Pt or Ni metal kept in contact with a gas adsorbs the gas - Hydrogenation of oils.
Animal charcoal, when added to acetic acid solution and shaken vigorously,
adsorbs acetic acid.
Molasses is decolourised by activated charcoal.

The molecules of gases or liquids or the solutes in solutions adher to the surface of the
solids. In adsorption process, two substances are involved. One is the solid or the liquid
on which adsorption occurs and it is called adsorbent. The second is the adsorbate,
which is the gas or liquid or the solute from a solution which gets adsorbed on the
surface.
Adsorbent: The substance on whose surface the adsorption occurs is known as
adsorbent.
Adsorbate: The substance whose molecules get adsorbed on the surface of the
adsorbent ( i.e. solid or liquid ) is known as adsorbate.
Adsorption is different from absorption. In absorption, the molecules of a substance are
uniformly distributed in the bulk of the other, whereas in adsorption molecules of one
substance are present in higher concentration on the surface of the other substance.

Types of adsorption:
Depending upon the nature of forces existing between adsorbate molecules and
adsorbent, the adsorption can be classified into two types:

1. Physical adsorption (physisorption): If the force of attraction existing between

adsorbate and adsorbent are Vander Waals forces, the adsorption is called physical
adsorption. It is also known as Vander Waals adsorption. In physical adsorption the force
of attraction between the adsorbate and adsorbent are very weak, therefore this type of
adsorption can be easily reversed by heating or by decreasing the pressure.
2. Chemical adsorption (chemisorption): If the force of attraction existing between
adsorbate and adsorbent are almost same strength as chemical bonds, the adsorption is
called chemical adsorption. It is also known as Langmuir adsorption. In chemisorption
the force of attraction is very strong, therefore adsorption cannot be easily reversed.
Comparison between Physisorption and Chemisorption

Physisorption

Chemisorption

1.

High heat of adsorption in the

Low heat of adsorption usually
range of 40-400 kJ mol-1
in the range of 20-40 kJ mol-1

2.

Forces of attraction are chemical

Force of attraction are Van der
bond forces
Waal's forces

3.

4.
5.

It usually takes place at low

It takes place at high temperature
temperature and decreases with
increasing temperature
It is irreversible

It is reversible

The extent of adsorption

It is related to the ease of generally
not
related
liquefaction of the gas
liquefaction of the gas
It is highly specific

6.

It is not very specific

7.

It forms multi-molecular layers

8.

It does not
activation energy

require

It forms monomolecular layers

any It requires activation energy

Factors affecting adsorption:

The extent of adsorption depends upon the following factors:
1.
2.
3.
4.

Nature of adsorbate and adsorbent.

The surface area of adsorbent.
Activation of adsorbent.
Experimental conditions. E.g., temperature, pressure, etc.

is
to

Adsorption Isotherm:

Adsorption process is usually studied through graphs known as adsorption isotherm.

That is the amount of adsorbate on the adsorbent as a function if its pressure or
concentration at constant temperature .The quantity adsorbed is nearly always
normalized by the mass of the adsorbent to allow comparison of different materials.

Basic Adsorption Isotherm:

From the above we can predict that after saturation pressure P s, adsorption does not
occur anymore, that is there are limited numbers of vacancies on the surface of the
adsorbent. At high pressure a stage is reached when all the sites are occupied and
further increase in pressure does not cause any difference in adsorption process. At high
pressure, Adsorption is independent of pressure.

Type of Adsorption Isotherm:

Five different types of adsorption isotherm and their characteristics are explained below.

Type I Adsorption Isotherm:

Type

Adsorption

Isotherm

The above graph depicts Monolayer adsorption.

This graph can be easily explained using Langmuir Adsorption Isotherm.
If BET equation, when P/P0<<1 and c>>1, then it leads to monolayer formation
and Type I Adsorption Isotherm is obtained.
Examples of Type-I adsorption are Adsorption of Nitrogen (N 2) or Hydrogen (H)
on charcoal at temperature near to -1800C.

Type II Adsorption Isotherm:

Type

II

Adsorption

Isotherm

Type II Adsorption Isotherm shows large deviation from Langmuir model of

adsorption.
The intermediate flat region in the isotherm corresponds to monolayer formation.
In BET equation, value of C has to be very large in comparison to 1.
Examples of Type-II adsorption are Nitrogen (N 2 (g)) adsorbed at -1950C on
Iron (Fe) catalyst and Nitrogen (N2 (g)) adsorbed at -1950C on silica gel.

Type III Adsorption Isotherm:

Type III Adsorption Isotherm

Type III Adsorption Isotherm also shows large deviation from Langmuir model.
In BET equation value if C <<< 1 Type III Adsorption Isotherm obtained.
This isotherm explains the formation of multilayer.
There is no flattish portion in the curve which indicates that monolayer formation
is missing.
Examples of Type III Adsorption Isotherm are Bromine (Br 2) at 790C on silica gel
or Iodine (I2) at 790C on silica gel.

Type IV Adsorption Isotherm:

Type IV Adsorption Isotherm

At lower pressure region of graph is quite similar to Type II. This explains
formation of monolayer followed by multilayer.
The intermediate flat region in the isotherm corresponds to monolayer formation.
The saturation level reaches at a pressure below the saturation vapor pressure.
This can be explained on the basis of a possibility of gases getting condensed in the tiny
capillary pores of adsorbent at pressure below the saturation pressure (PS) of the gas.
Examples of Type IV Adsorption Isotherm are of adsorption of Benzene on Iron
Oxide (Fe2O3) at 500C and adsorption of Benzene on silica gel at 500C.

Type

Adsorption

Isotherm:

Type V Adsorption Isotherm

Explanation of Type V graph is similar to Type IV.

Example of Type V Adsorption Isotherm is adsorption of Water (vapors) at 1000C
on charcoal.
Type IV and V shows phenomenon of capillary condensation of gas.

Freundlich Adsorption Isotherm:

In 1909, Freundlich expressed an empirical equation for representing the isothermal
variation of adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent with
pressure. This equation is known as Freundlich Adsorption Isotherm or Freundlich
Adsorption equation or simply Freundlich Isotherm.

Where,

x/m = adsorption per gram of adsorbent which is obtained be dividing the amount of
adsorbate (x) by the weight of the adsorbent (m).
P is Pressure, k and n are constants whose values depend upon adsorbent and gas at
particular temperature .
Though Freundlich Isotherm correctly established the relationship of adsorption with
pressure at lower values, it failed to predict value of adsorption at higher pressure. This
relation is called as the freundlich adsorption isotherm. As see the following diagram.
The value of x/m is increasing with increase in p but as n>1 it does not increase
suddenly. This curve is also called the freundlich isotherm curve.

Taking the logarithms of a first equation.

Hence, if a graph of log x/m is plotted against log p, it will be a straight line in the
following diagram.

From this the value of slope equal to 1/n and the value of intercept equal to log k can be
obtained. Over and above, it the graph of log x/m against log p comes out to be a
straight line, it can be assured that the freundlich adsorption isotherm is satisfied for this
system.

Langmuir Adsorption Isotherm:

In 1916, Irving Langmuir published a new model isotherm for gases adsorbed to solids,
which retained his name. It is a semi-empirical isotherm derived from a proposed kinetic
mechanism. This isotherm was based on different assumptions one of which is that
dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous
molecules.
It is based on four assumptions:
1.

The surface of the adsorbent is uniform, that is, all the adsorption sites are
equivalent.
2.
Adsorbed molecules do not interact.
3.
All adsorption occurs through the same mechanism.
4.
At the maximum adsorption, only a monolayer is formed: molecules of adsorbate
do not deposit on other, already adsorbed, molecules of adsorbate, only on the free
surface of the adsorbent.

Langmuir suggested that adsorption takes place through this mechanism:

Where ,
A(g) = unadsorbed gaseous molecule
B(s) = unoccupied metal surface
AB = Adsorbed gaseous molecule.
The direct and inverse rate constants are k and k-1
Based on his theory, Langmuir derived an equation which explained the relationship
between the number of active sites of the surface undergoing adsorption and pressure.
This equation is called Langmuir Equation.

Where,
= the number of sites of the surface which are covered with gaseous molecule,
P= pressure
K =is the equilibrium constant for distribution of adsorbate between the surface and the
gas phase .

The basic limitation of Langmuir adsorption equation is that it is valid at low pressure
only.
At lower pressure, KP is so small, that factor (1+KP) in denominator can almost be
ignored. So Langmuir equation reduces to

At high pressure KP is so large, that factor (1+KP) in denominator is nearly equal to KP.
So Langmuir equation reduces to

Adsorbents:

The material upon whose surface the adsorption takes place is called an adsorbent
.Activated carbon is used as an adsorbent

Adsorbents are used usually in the form of spherical pellets, rods, moldings, or
monoliths with hydrodynamic diameters between 0.5 and 10 mm.
They must have high abrasion resistance, high thermal stability and small pore
diameters, which results in higher exposed surface area and hence high surface capacity
for adsorption.
The adsorbents must also have a distinct pore structure which enables fast
transport of the gaseous vapors.

Most industrial adsorbents fall into one of three classes:

Oxygen-containing compounds - Are typically hydrophilic and polar, including

materials such as silica gel and zeolites.
Carbon-based compounds - Are typically hydrophobic and non-polar, including
materials such as activated carbon and graphite.
Polymer-based compounds - Are polar or non-polar functional groups in a porous
polymer matrix.
Activated carbon is used for adsorption of organic substances and non-polar adsorbates
and it is also usually used for waste gas (and waste water) treatment. It is the most
widely used adsorbent since most of its chemical (eg. surface groups) and physical
properties (eg. pore size distribution and surface area) can be tuned according to what is
needed. Its usefulness also derives from its large micropore (and sometimes mesopore)
volume
and
the
resulting
high
surface
area.

Mechanism of Adsorption Using Adsorbent:

Applications of adsorption:

The

1.
2.
3.
4.
5.
6.

principle

of

adsorption

is

in heterogeneous catalysis.
in gas masks where activated charcoal adsorbs poisonous gases.
in the refining of petroleum and decolouring cane juice.
in creating vacuum by adsorbing gases on activated charcoal.
in chromatography to separate the constituents' of a mixture.
to control humidity by the adsorption of moisture on silica gel.

employed,

7.

in certain titrations to determinate the end point using an adsorbent as indicator

(Example: Flouroscein).
What is Adsorption Isotherm?
The process of Adsorption is usually studied through graphs know as adsorption
isotherm. It is the graph between the amounts of adsorbate (x) adsorbed on the surface
of adsorbent (m) and pressure at constant temperature. Different adsorption isotherms
have been Freundlich, Langmuir and BET theory.
Basic Adsorption Isotherm
In the process of adsorption, adsorbate gets adsorbed on adsorbent.

According to Le-Chatelier principle, the direction of equilibrium would shift in that

direction where the stress can be relieved. In case of application of excess of pressure to
the equilibrium system, the equilibrium will shift in the direction where the number of
molecules decreases. Since number of molecules decreases in forward direction, with the
increases in pressure, forward direction of equilibrium will be favored.

Basic Adsorption Isotherm

From the graph, we can predict that after saturation pressure Ps, adsorption does not
occur anymore. This can be explained by the fact that there are limited numbers of
vacancies on the surface of the adsorbent. At high pressure a stage is reached when all
the sites are occupied and further increase in pressure does not cause any difference in
adsorption process. At high pressure, Adsorption is independent of pressure.
Freundlich Adsorption Isotherm
In 1909, Freundlich gave an empirical expression representing the isothermal variation
of adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent with

pressure. This equation is known as Freundlich Adsorption Isotherm or Freundlich

Adsorption equation or simply Freundlich Isotherm.

Where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure p and
k, n are constants whose values depend upon adsorbent and gas at particular
temperature. Though Freundlich Isotherm correctly established the relationship of
adsorption with pressure at lower values, it failed to predict value of adsorption at higher
pressure.
Langmuir Adsorption Isotherm
In 1916 Langmuir proposed another Adsorption Isotherm known as Langmuir Adsorption
isotherm. This isotherm was based on different assumptions one of which is that
dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous
molecules.

Where A(g) is unadsorbed gaseous molecule, B(s) is unoccupied metal surface and AB is
Adsorbed gaseous molecule.
Based on his theory, he derived Langmuir Equation which depicted a relationship
between the number of active sites of the surface undergoing adsorption and pressure.

Where the number of sites of the surface which are covered with gaseous molecule, P
represents pressure and K is the equilibrium constant for distribution of adsorbate
between the surface and the gas phase .The basic limitation of Langmuir adsorption
equation is that it is valid at low pressure only.
At lower pressure, KP is so small, that factor (1+KP) in denominator can almost be
ignored. So Langmuir equation reduces to
= KP
At high pressure KP is so large, that factor (1+KP) in denominator is nearly equal to KP.
So Langmuir equation reduces to

BET adsorption Isotherm

BET Theory put forward by Brunauer, Emmett and Teller explained that multilayer
formation is the true picture of physical Adsorption.
One of the basic assumptions of Langmuir Adsorption Isotherm was that adsorption is
monolayer in nature. Langmuir adsorption equation is applicable under the conditions of
low pressure. Under these conditions, gaseous molecules would possess high thermal
energy and high escape velocity. As a result of this less number of gaseous molecules
would be available near the surface of adsorbent.
Under the condition of high pressure and low temperature, thermal energy of gaseous
molecules decreases and more and more gaseous molecules would be available per unit
surface area. Due to this multilayer adsorption would occur. The multilayer formation was
explained by BET Theory. The BET equation is given as