SEMINAR REPORT

ON

Arsenic reduction from waste water

Submitted By

Akshay Wajge
310014

Department of Petrochemical Engineering

MAEERS, MAHARASHTRA INSTITUTE OF TECHNOLOGY
PAUD ROAD, KOTHRUD, PUNE 411038, (MS), INDIA

2015 - 2016

SEMINAR REPORT
ON

Arsenic reduction from waste water

Submitted By

Akshay Wajge
310014
Third Year (Petroleum Engineering)

Guided by

Mr. Vinayak S. Wadgaonkar

Assistant Professor

Department of Petrochemical Engineering

MAEERS, MAHARASHTRA INSTITUTE OF TECHNOLOGY
PAUD ROAD, KOTHRUD, PUNE 411038, (MS), INDIA

2015 2016

MAEERS, MAHARASHTRA INSTITUTE OF TECHNOLOGY

PAUD ROAD, KOTHRUD, PUNE 411038, (MS), INDIA

DEPARTMENT OF PETROCHEMICAL ENGINEERING

CERTIFICATE

This is to certify that, seminar report entitled Arsenic reduction from waste water submitted
by Mr Akshay wajge, Exam Seat number: T120027102, Third Year Petrochemical
Engineering, is a record of bonafide work carried out by him under my supervision, in partial
fulfilment for Third Year Course requirement of University of Pune, Pune, during the
academic year 2015-2016. To the best of my knowledge and belief this work has not been
submitted elsewhere for the award of any other degree.

Mr. Vinayak S. Wadgaonkar

Datta B. Dandge

Guide

Head of the Department

Date:

Place:

ACKNOWLEDGEMENT

I would like to express my special thanks of gratitude to my teacher Mr Mr Vinayak S.

Wadgaonkar as well as our Head of department Mr Datta B. Dandge who gave me the
goldern opportunity to do this wonderful project on the topic of Arsenic reduction from
waste water which also helped me in doing a lot of research and I came to know about so
many new things.I am really thankful to them.
Secondly I would also like to thank my parents and friends who helped me a lot in finalizing
this project within the limited frame time.

Akshay wajge
T120027102
Third Year (Petrochemical
Engineering)
Department of Petroleum
Engineering,
MAEERs Maharashtra Institute of
Technology,
124, Paud Road, Pune -411038

PAGE INDEX

Srno

Topic

Page no

Abstract

1
2

Introduction
2.1
2.2
2.3

3
4
5
5.1
5.2

Removal processes
Coagulationprecipitation
Adsorption
Membrane filtration
Comparison of arsenic removal processes
Developments in the area of arsenic removal techniques
Arsenic reduction by adsorption
Commercial Activated carbons
Low-cost adsorbents
Conclusion

Abstract

1
2
4
4
5
6
8
10
13
13
16
21

The use of arsenic in agriculture, industry, and domestic endeavours since the last century has
increased the concentration of arsenic in the environment. Since most of the arsenic
compounds are water soluble, in industries the compounds can be found in the waste water.
There are various methods for treating and removing arsenic from waste water.
Several methods of treating water/ waste water for arsenic reduction techniques with special
emphasis given on adsorption techniques are being discussed in this report. Despite having
some advantage over other methods removal of arsenic by adsorption method is not widely
used. A large number of adsorbents are chemically and physically tested for arsenic
remediation with a lots of research work still going on in the industry. Arsenic sorption by
commercially available carbons and other low-cost adsorbents with their sorption efficiencies
have been discussed in this report.
The purpose of this seminar report is to present a brief overview of presently used arsenic
removal processes, adsorption techniques and some of the adsorbents which experimentally
proven to be a better alternative to conventional processes and which could be used in near
future for arsenic remediation.

Chapter 1: Introduction

Arsenic is a heavy metal. It is a silver-grey brittle crystalline solid with atomic weight 74.9;
specific gravity 5.73, melting point 817 C (at 28 atm), boiling point 613 C and vapour
pressure 1 mm Hg at 372 C. The elements occur in environment in different oxidation states
and form various species, e.g., As as As(V), As(III), As(0) and As (-III). In oxidized
environment As appears mostly as oxyanions [1]. Arsenic cannot be easily destroyed and can
only be converted into different forms or transformed into insoluble compounds in
combination with other elements, such as iron. Many impurities such as lead, iron and
selenium may be mixed up together with arsenic wastes and make it uneconomical to
remove.
Inorganic arsenic generally exists in two predominant oxidation states, arsenite (NaAsO2)
and arsenate (Na 2HAsO4), both of which are toxic to the environment. Arsenic commonly
present in water are pH dependant species of the arsenic (H3AsO4) and arsenous (H3AsO3)
acid systems respectively. These anions have acidic characteristics, and the stability and
dominance of a specific species depend on the pH of the solution. Arsenates are stable under
aerobic or oxidizing conditions, while arsenites are stable under anaerobic or mildly reducing
conditions.
The sub surface mobilization of arsenic is caused by the combination of
chemical, physical and microbial factors. Many theories have been
proposed to explain this mobilization.
(i) Oxidation of As containing pyrites.
(ii) Release of As(V) from reduction of iron oxides by autochthonous
organic matter (e.g., peat).
(iii) Reduction of iron oxides by allochthonous organic matter (from
dissolved organics in recharging waters).
(iv) Exchange of adsorbed As(V) with fertilizer phosphates.
(v) Reduction of oxy hydroxides by microbial oxidation of sedimentary
carbon.
No matter from where arsenic comes in our environment it still effects many species. Arsenic
compounds cause short-term and long-term effects in individual plants and animals and in
populations and communities of organisms. These effects are evident, for example, in aquatic
species at concentrations ranging from a few micrograms to milligrams per litre. The nature
of the effects depends on the species and time of exposure. The effects include death,

inhibition of growth, photosynthesis and reproduction, and behavioral effects. Environments

contaminated with arsenic contain only a few species and fewer numbers within species. If
levels of arsenate are high enough, only resistant organisms, such as certain microbes, may be
present. The reason why arsenite is toxic is thought to be because it binds to particular
chemical groups - sulfhydryl groups - found on proteins. Arsenate, on the other hand, affects
the key energy producing process that take place in all cells.
Therefore it is necessary to employ techniques for proper treatment of arsenic in waste water.
Arsenic can be removed from contaminated water by physico-chemical as
well as biological techniques. These techniques are classified as below:
(I) Physico-chemical techniques
(a) Adsorption
(b) Ion exchange
(c) Precipitationcoagulation
(d) Membrane filtration
(e) Permeable reactive methods
(II) Biological techniques
(a) Phytoremediation
(b) Biological treatment with living microbes/bio-filtration

Chapter 2: Removal processes

Arsenic removal in the conventional techniques are performed by oxidation of soluble As(III)
to less soluble As(V) followed by separation of As(V) by exploiting any of the
physicochemical properties like coagulationprecipitation, adsorption, ion exchange, reverse
osmosis, electro dialysis, etc. The conversion of As(III) to As(V) is done by using some
oxidizing chemical agents like chlorine, potassium permanganate, etc. Addition of chemicals
in the oxidation step increases the cost of these techniques. There are a number of arsenic
removal processes.
These physico-chemical techniques can be classified as below.

2.1 Coagulationprecipitation:
In this process chemicals transform dissolved arsenic into an insoluble solid which is
precipitated. Dissolved arsenic may also be adsorbed on the surface and be co precipitated
with other precipitating species. Suspended/colloidal arsenic may also be separated by
coagulation and flocculation. The pH of the process highly influences the efficiency of
removal. Commonly used chemicals in this technique are ferric salts, alum, manganese
sulphate, ammonium sulphate, copper sulphate, etc. Some of the types of coagulation
processes are discussed below.

2.1.1 Lime softening:

It is a type of precipitation method where limes (lime stone, calcium hydroxide) are used for
the removal. The arsenic removal efficiencies of the lime softening process are significantly
affected by the pH and the presence (or absence) of chlorine. With lime softening, several
chemicals would be needed to achieve good arsenic removal rates. Chlorine, to oxidize the
arsenic, is required. Lime is, of course, needed and acid would probably be necessary to
lower the pH of the treated water to acceptable drinking water levels. The arsenic removed
from the water comes out in the clarifier with the lime sludge produced by the process.

2.1.2 Alum precipitation

It is the property of alum that it can remove solids and dissolved metals from liquids solution.

For the removal of arsenic, alum is most effective if an oxidizing agent, such as chlorine, is
added ahead of the flocculator and clarifier and the pH is reduced to 7 or less.

2.1.3 Iron precipitation

It has also been shown that arsenic can be precipitated using iron. In this process, an iron
compound, such as ferric sulphate [Fe2(SO4)3I, for example, is added to the untreated water.
The arsenic combines with the iron to form a precipitate that settles out in the clarifier.
Following the clarifier, a filter is employed which removes iron/arsenic particles not taken
out in the clarifier.

2.2 Adsorption:
In this technique arsenic species is attached on the surface of the adsorbent by physical as
well as chemical forces. The active surface area of adsorbent, its surface energy and the pH of
the solution highly influence the removal efficiency. Conventionally used adsorbents are
activated alumina, activated carbon, greensand (KMnO4 coated gluconite), granular ferric
hydroxide, iron oxide coated sand, copper-zinc granules, etc.

1.2.1 Activated alumina

Activated alumina has been known to remove arsenic in a number of instances. While it has
not been fully characterised, it isbelieved the arsenic absorbs into the surface of the activated
alumina. Eventually, the alumina surface becomes sufficiently saturated with arsenic that
adequate removal is no longer accomplished. It then becomes necessary to regenerate the
alumina. This is done by subjecting the alumina to a caustic bath, which appears to remove
the surface layer of alumina, and the arsenic absorbed into that layers. The alumina is then
neutralized with a sulfuric acid rinse, and placed back into service. Regeneration of alumina
is not complete: the alumina loses about 30-40% of its capacity with each regeneration so that
it must be replaced after only three or four regenerations. However, its low cost and relatively
high capacity lot. costs at an acceptable level.

2.2.2 Ion exchange:

Ion exchange has been used for many years to soften water, demineralize water, remove
nitrate, and for other water treatment applications. For arsenic removal an ion exchange resin,

usually loaded with chloride ions at the "exchange sites", is placed in vessels. The arsenic
containing water is passed through the vessels and the arsenic "exchanges" for the chloride
ions. The water exiting the vessel is lower in arsenic but higher in chloride than the water
entering the vessel.
In this technique arsenic ions held electro statically on the surface of a strong base anion
exchange resins are exchanged for ions of similar charge in the solution from the resin.

2.3 Membrane filtration:

In this technique arsenic is separated from water by passing it through a semi permeable
barrier or membrane. Pressure difference is the driving force for the separation. The removal
efficiency depends on the pore size in the membrane and the particle size of arsenic species.
Pre oxidation step improves the removal efficiency. However, certain drawbacks make these
processes inefficient in some cases, especially when Fe and Mn are available in water. Small
pores of these membranes are more prone to fouling. Fe and Mn promote fouling of
membrane due to co-precipitation that might be ir-reversible. It needs pretreatment of water,
monitoring of operational pressure and skilled operator, which makes the process costly.

2.3.1 Reverse osmosis

There are two types of reverse osmosis that can remove arsenic from water; Nano filtration
and hyper filtration. Nano filtration is a relatively low pressure reverse osmosis process that
removes primarily the larger dissolved solids as compared to hyperfiltration. Nanofiltration is
also known as membrane softening for its ability to remove the divalent ions in water that
cause hardness; i.e., calcium and magnesium. Nanofiltration (membrane softening) also
removes sulphate as well as lesser quantities of the monovalent dissolved solids such as
chloride and sodium. Conversely, hyperfiltration operates at higher pressures with greater
rejection (removal) of all dissolved solids. Examples of hyperfiltration include brackish water
and sea water desalting.
The wastewater (concentrate) from the reverse osmosis is reportedly something more than
10% of the feed water. The arsenic removed was concentrated in the wastewater; there is no
solid waste (sludge) produced by a reverse osmosis process itself.

2.3.2 Electro dialysis.

It is similar to reverse osmosis except the driving force; an electric field applied across a semi
permeable membrane in the contaminated water generates the driving force for separation.

These conventional techniques have some limitations i.e. use of chemicals, its handling and
impact on water quality; production of large volume of high arsenic contaminated sludge;
need of secondary treatment in some cases interference of sulfates and other ions on removal
efficiency and High installation and operation cost and lower efficiency in many cases.
The success of a particular removal technology depends upon the following factors.
(i) MCL target, 10 g/l
(ii) Influent arsenic concentration,
(iii) Population,
(iv) Region where the system is located,
(v) Source water,
(vi) Whether a system has existing treatment in place,
(vii) Co-occurrence of solutes and
(viii) Waste disposal issues.
A general comparison based on above factors are discussed in the following section.

Chapter 3: Comparison of arsenic removal processes

The parameters used for comparing removal processes are

1. Chemical intensity
4. Area required

Intensity
Chemicals
Power
labour
Area required
Waste
Solid
Liquid
Removal efficiency

2. Power intensity
5. Waste production (solid and liquid)

3. Labour intensity,
6. Removal efficiency

Precipitation

Membrane

Adsorption

High
Med
High
High

Low
High
Low
Low

Med
Low
Low
Low

Yes
No
Low

No
Yes
High

No
Yes
High

1. "Chemical intensity" is a measure of the quantities and numbers of the chemicals used
by a particular process.
The precipitation processes are rated "hi" in the table because, for example, the alum
process requires chlorine, acid, alum, and caustic.
The membrane and ion exchange processes are rated "low" because none of these
processes require significant amounts of chemicals except possibly for post-treatment
of the membrane process product water in the event the product water quality is "too
good".
2. "Power intensity" is a measure of the relative power consumption of the processes.
The membrane processes are rated "high" because of the need to pressurize the feed
water for reverse osmosis and the need to power the electrodes for electtodialysis.
The precipitation processes are rated "reed" because of the need to pump backwash
water and sludge, etc,
The power consumption of the adsorption processes is rated "low" because
substantially all of the power required is that needed to move the water through the
resin bed with a pressure less in the 5-10 psi range typically.
3. "Labor intensity" for the precipitation processes was rated "hi" because of the need for
more operator attention than for the "low" rated membrane and adsorption processes.
4. "Area required" refers to the land area required for a plant.
Precipitation processes require more area than membrane or adsorption processes.
5. The comparison with respect to "waste" is based on whether or not solid and/or liquid
wastes are produced by the processes.
the precipitation processes produce a liquid waste.
The membrane and adsorption processes do not produce a solid waste.

6. "Removal efficiency" is an indication of how much of the arsenic in a feed water

isremoved by a process.

Conclusion:
By a comparison among these processes it is evident that coagulationfiltration and lime
softening techniques are cheaper but the removal efficiency of these techniques are low
(<90%). Hence, the adsorptive process with activated alumina seems to be the most
inexpensive among the techniques with higher efficiency (95) The precipitation processes
can be used for larger water treatment plants.

Chapter 4: Developments in the area of

arsenic removal techniques
To meet the challenge of reducing arsenic concentration to the MCL value
of 10 g/l and its treatment cost, apart from the conventional removal
processes, search for new developed technique has been initiated in the
last decade of the 20th century. Although adsorption by alumina is a low
cost efficient treatment option for arsenic removal from contaminated
water, this technique is still cannot be used in the industries due to its
demerits. Hence, search for more efficient and cost effective alternate
adsorbents are in progress. Some of such alternatives are the surface
coated adsorbents.
Recently some adsorbents like coconut husk carbon, iron oxide coated
polymeric materials, low cost ferruginous manganese ore, iron oxide
coated sand, Mn greensand, etc., have been reported for effective
adsorption. The high ash containing charred carbon (ash content around
29%), obtained from fly ash has been reported to have 90% removal
efficiency. Similarly, coconut husk carbon has been reported to have more
than 95% removal efficiency with optimum adsorption at pH 12.0.
Adsorbent dose, contact time and initial concentration
of arsenic have been found to affect removal efficiency.
A low cost ferruginous manganese ore (FMO), US$ 5056 per tonne, has
been used as effective adsorbent to remove arsenic,this material is able
to treat water without pretreatment and at optimum conditions it is able
to remove arsenic by 98.599.8%. The presence of Ni+2, Co+2, Mg+2
enhances the adsorption capability of FMO. Manganese greensand (MGS)
and differently prepared iron oxide coated sands have been reported as
adsorbents for the removal of organic arsenic from water.
Recently, some techniques have been reported where conventional
chemical oxidizing agents are not used for oxidation of As(III) to As(V). UV
ray, living plants and microbes are responsible for oxidation of arsenic in

these cases. In 2002, oxidation of arsenic by UV ray and sunlight in

presence of iron and oxidation of arsenic by UV ray in presence of sulfite
has been reported. The reported conversion in both the cases was more
than 95%. In the first case residues passed the USEPA leach test with or
without solidification. In the second case no residue was obtained.
Upcoming waves of biotechnology also attracted the researchers to
investigate for alternative cost effective and eco-friendly removal
processes by the help of biochemical engineering. Phyto remediation and
bio-filtration using living microbes have recently been identified as two
main biological treatment techniques for removing arsenic from
contaminated water in an eco-friendly way.
In phyto remediation technique plant/fungal biomass is used as adsorbent.
The removal mechanism is similar to that of adsorption techniques. The
fungal/plant biomass is susceptible to chemical and engineering
improvements and regeneration of their capabilities. It has recently been
observed that the capability of fungal biomass for treating metal
contaminated effluents is better than activated carbon (F-400).
The pre-treatment of biomass of P. chrysogenum with common surfactants
(as hexadecyl-tri-methyl ammonium bromide and do-decyl amine) and a
cationic-polyelectrolyte was found to
improve the bio-sorption efficiency. The reported improvement in biosorption efficiency was 37.85, 33.31% and 56.07%, for hexadecyltrimethyl ammonium bromide, dodecyl amine and polyelectrolyte,
respectively. Moreover, this biosorptive process reduces capital cost by
20%, operational; cost by 36% and total treatment cost by 28% when
compared with conventional processes.
The tea fungus, a waste produced during black tea fermentation has been
examined for its capacity to sequester the metal ions from ground water
samples. Autoclaved tea fungal mat and autoclaving followed by FeCl3
pretreated tea fungal mat were exploited for removal of As(III), As(V) and
Fe(II) from ground water sample collected from Kolkata, West Bengal,
India. The biosorption rate tends to increase with the increase in contact
time and adsorbent dosage. FeCl3 pretreated and autoclaved fungal mats

removed 100% of As(III) and Fe(II) after 30 min contact time and 77% of
As(V) after 90 min contact time. The optimum adsorbent dosage was 1.0
g/50 ml of water sample. The results revealed that the FeCl3 pretreated
fungal mat could be used as an effective biosorbent for As(III) and As(V);
autoclaved fungal mat for Fe(II) removal from ground water sample. Living
plants like Brake fern (Pteris vittata) may also be used to take up arsenic
from contaminated water, which is accumulated into the plant body.
The mechanism of arsenic removal by using living microbes differs from
that of phyto remediation technique. Like other heavy metals, in this case
the conversion of As(III) to As(V) may be performed by an extra cellular
enzyme and the oxidized species may be adsorbed or precipitated/co
precipitated onto the bio layer formed on the solid support medium. Or, by
a trans membrane protein the arsenic may be entered into the microbial
cell where methylation or oxidationreduction of arsenic species may take
place. It has been reported that in most of the cases the removal
efficiency of this technique is controlled by plasmid gene. Hence, there is
a high possibility for improving the efficiency by genetic modification of
the microbes. However, the evaluation of the removal efficiency and the
reliability of these processes are yet to be found out.
In 2002, the biological oxidation of As(III) to As(V) by iron and Mn oxidizing
bacteria has also been reported. It has also been confirmed that trivalent
arsenic cannbe efficiently treated without any additional use of chemicals
in this bioprocess, the optimum conditions have also been reported.
Similarly in 2003, microbial sulfate reduction and subsequent precipitation
of Cu, Zn, Ni, Ce and As has been reported. The experiment has been
done with a mixed population of sulphate reducing bacteria (SRB) in an
up-flow anaerobic packed bed reactor (UPAB) containing silica sand.
In 2003, Casiot et al. by their study on the mobilization of arsenic in acid
mine drainage from Carnules creek in France, have suggested that the
immobilization of indigenous bacteria in the precipitates which cover the
bottom of the creek, is responsible for oxidation of arsenic. More than 75%
Arsenic removal in presence of bacteria as living cell and 22% arsenic
removal in absence of bacteria have been observed. Out of six indigenous

bacteria in the creek two have been found mainly responsible for As(III)
oxidation, and one for iron oxidation. An arsenic oxidizing bacteria has
been reported as Thiomonas Ynys1. The role of other bacteria is not
known. The experiment was carried out at pH 2.733.37 and through out
the year, creek temperature was varied from 13.2 to 16.5 C. No influence
of UV and photo oxidation on the arsenic removal has been reported in
this study.

Chapter 5: Arsenic reduction by adsorption

In recent years, efforts have been directed to improve the efficiency and
cost effectiveness of arsenic removal techniques either by modification of
the conventional techniques mainly adsorption or by inducing new
technology where chemical oxidation of As(III) to As(V) is avoided.
Adsorption is evolving as a front line of defence. Selective adsorption
utilizing biological materials, mineral oxides, activated carbons, or
polymer resins, has generated increasing excitement.
In this report Adsorbents are broadly divided into two classes:
(1) Commercial and synthetic activated carbons and
(2) low-cost adsorbents.

5.1 Commercial and synthetic activated carbons

5.1.1 Commercial Activated carbons
Active carbons can be prepared from wood, coal, lignite, coconut shell and
peat. However there are various material which can also be used to
produce activated carbons.
The adsorption of As(III) and As(V) on activated charcoal is dependent on
pH and temperature. The adsorption of As(III) on carbon is constant at pH
0.163.5. However
As(V) exhibited a maximum adsorption at pH 2.35 over the pH range of
0.866.33.
The As(III) isosteric heat of adsorption ion varies from 4 to 0.75 kcal/mol
and that for As(V), from 4 to 2 kcal/mol with increasing surface loading.
These magnitudes suggest that physisorption occurred due to weak Van
der Waals forces.
Activated charcoal can adsorb upto 2.5 wt.% As(V) and 1.2 wt.% As(III)
(based on the weight of carbon) at an equilibrium concentration of 2.2
102 M of both As(III) and As(V)
Activation refines the pore structure. Mesopores and micropores are
formed yielding surface areas up to 2000 m2/g. Acidic and basic activation
carbon exists according to the Steenbergs classification. The acidic
groups on activated carbons adsorb metal ions
Adsorption by activated carbon capacity depends on activated carbon
properties, adsorbate chemical properties, temperature, pH, ionic
strength, etc.
Examples

Activated carbons impregnated with metallic silver and copper are

also used for

arsenic remediation. A huge arsenic sorption capacity (2860 mg/g)

can be seen on this coal-derived commercial carbon.

Activated carbon with 5-6% ash content can also be used as an
adsorbent. Experimentally more As(V) is removed from water using

carbon with a high ash content.

Carbon pretreatment with Cu(II) improves arsenic removal capacity.
The optimum pH for arsenic adsorption by Cu-pretreated carbon is
near around 6. Mechanism of this process is Arsenic formes
insoluble metal arsenates with the impregnated copper and also
simultaneously adsorbs carbon independently. Arsenic was desorbed

using strongly acidic or alkaline solutions.

A combination of granular activated carbon and carbon steel wool
removed arsenic
from water.It is a common practice for removing impurities from
water. The adsorption ability of the steel wool was due to iron
arsenic electrochemical reactions.

Many activated carbons are available commercially but few are selective
for heavy metals. They are also expensive. Despite carbons prolific use
to treat wastewater, it remains expensive, requiring vast quantities of
activated carbon. Improved and tailor-made materials are sought.
Substitutes should be easily available, cheap and, above all, be readily
regenerated, providing quantitative recovery.

5.1.2 Synthetic activated carbons

Activated carbons are produced by carbonization employing slow
substrate heating in the absence of air below 600 C. This removes
volatiles. Then chemical or physical activation follows. Treatment with
oxidizing agents (steam, carbon dioxide, or oxygen) at elevated
temperature or with chemical activants (ZnCl2, H2PO4, H2SO4, KOH, K2S,
KCNS, etc.) completes the activation. Chemical activants may promote

crosslinking forming a rigid, less volatile matrix with a smaller volume

contraction going to high temperature.
An advantage of chemical activation is the lower temperature required
Chemical activation
gives higher global yields since char burn-off is not required.

Several types of activated carbons are synthesized and used for the
removal of arsenic from water/wastewater.

Iron-containing granular activated carbon adsorbents (As-GAC)

Iron-containing granular activated carbon adsorbents (As-GAC) is

one of the synthetically produced activated carbons which can be
used for arsenic removal from drinking water. The manufacturing of
As-GAC includes impregnation of ferric ions using aqueous ferrous

chloride (FeCl2) followed by NaClO chemical oxidation.

Arsenic is most efficiently removed when the iron content is 6%.
The removal of arsenate occurs in a wide pH range (4.411),but
arsenate adsorption decreased at pH > 9.0.

Activated carbon pre-treated with iron-salt solutions, shows improvement

in arsenic adsorption capacity. The salt type and concentration, pH, and
treatment time are examined to improve removal capacity. A 10-fold
capacity increase was finally achieved versus the untreated activated
carbon. Ferrous ions are adsorbed and As removal was enhanced by
arsenate complex formation.
Some materials like Modified sawdust carbon coconut husk carbon (CHC)
shows excellent arsenic adsorption capabilities. Coconut husk carbon can
be prepared by treating one part of coconut husk with 1.8 parts by weight
of sulphuric acid (18 M) at 150 C for 24 h. The carbonized material (CHC)
is then water washed to remove acid and dried at 105 C. The CHC (10 g)
is mixed with 100 mL of 100 mmol/L copper solution (initial pH 8.5). The

mixture was shaken for 24 h at 30 C and filtered. The filtrates pH was

6.5. The resulting copper-impregnated coconut husk carbon (CuCHC) is
water washed until the filtrate was copper free. Optimum As(III)
adsorption conditions on this copper-impregnated activated carbon were
established. Maximum adsorption capacity occurred at pH 12.0. Capacity
increased going from 30 to 60 C.

Zirconium-loaded activated carbon

zirconium-loaded activated carbon can successfully remove heavy metals
like arsenic, selenium, and mercury from water. Zirconium reacts with
heavy metal ion thus providing a better adsorption property than
activated carbon.

5.2 Low-cost adsorbents.

5.2.1 Agricultural products and by-products
Agricultural wastes are by-products, currently unused or underused for
animal feed. Agricultural waste/by-products such as rice husks can be
used for arsenic removal from water.
When untreated rice husk was utilized for aqueous arsenic remediation
complete removal (using rice husk columns) of both As(III) and As(V) was
achieved under the following conditions:
Initial As concentration
rice husk amount
flow rate,
pH

100 g/L
6g
6.7 and 1.7 mL/min
6.5 and 6.0

Desorption (7196%) was also achieved with 1 M of KOH.

5.2.2 Industrial by-products/wastes

5.2.2.1 Chars, and coals.
Lignite, peat chars bonechar use in wastewater treatment has received
increasing attention. They may be good substitutes for activated carbons.
They are plentiful, inexpensive and locally available.
Arsenic (V) removal from aqueous solution by mixture of synthetic
hydroxylapatite and barite or bone char was carried out in the
concentration range of 4100 mg/L. Although the hydroxylapatite and
baryte mixture had a small influence on arsenic concentrations, bone-char
was found to be a very effective sorbing agent for As(V) in the pH range of
25..

5.2.2.2. Red mud.

Red mud is a waste material formed during the production of alumina
when bauxite ore is subjected to caustic leaching. A typical large process
plant generates a 12 tonnes of red mud per ton of alumina produced.
In arsenic removing process by red mud an alkaline aqueous medium (pH
9.5) favoured As(III) removal, whereas the acidic pH range (1.13.2) was
effective for As(V) removal . Heat and acid treatments on red mud
increases its adsorptive capacity. The As(III) adsorption is exothermic,
whereas As(V) adsorption is endothermic process.
It is also suggested that it is advantageous to use a waste material of red
mud liquid phase in the treatment of arsenical wastewater possibly
conjunction with red mud solids as adsorbent.

5.2.2.3 Blast furnace slag.

Steel plants generate a large volume of granular blast furnace slag. It is

being used as filler or
in the production of slag cement. it can be converted into an effective and
economical scavenger and utilized for the remediation of aqueous arsenic.
Elemental iron, iron oxides, CaFe oxides and calcium hydroxides from
typical steel manufacturing processes were tested as adsorbents for
treating mine-tailing leachate with high As concentrations. These byproducts were placed in situ as permeable reactive barriers to control
arsenic release. Evaporation cooler dust (ECD), oxygen gas sludge (OGS),
basic oxygen furnace slag (BOFS) and, to a lesser degree, electrostatic
precipitator dust (EPD) effectively removed both As(V) and As(III).
Experimentally it is been proved that the maximum As(III) adsorption
capacity of BFS is
1.40 mg As(III)/g of BFS at 1 mg/L As(III) initial concentration. Oxidation of
As(III) to As(V) and its adsorption/precipitation onto BFS was the
dominating mechanism

5.2.2.4 Fly ash.

Coal combustion produces a huge amount of by-product fly ash, whose
disposal requires large quantities of land and water. Currently, its
applications are limited to civil engineering uses including cement and
brick production and roadbeds.
Bottom ash can also serve as an adsorbent. Resource recovery from coal
fly ash is one of the most important issues in waste management
worldwide. Since the major chemical compounds contained in fly ash are
aluminosilicate, intensive efforts have been recently made to utilize this
material as an adsorbent.
Fly ash obtained from coal power stations is examined for As(V) removal
from water and to restrict As(V) migration in the solid wastes or the soil.
For this lignite based fly ash is experimented to evaluate its As(V) removal
efficiency.

At low pH(4) results were better than at high pH(& or 10). The static tests
removed 80% arsenic while the arsenic concentration was reduced from
500 to <5 ppb in dynamic column experiments.

5.2.2.5 Ferruginous manganese ore (FMO)

A low-cost ferruginous manganese ore (FMO) is used to remove both
As(III) and As(V) from groundwater without any pretreatment in the pH
range of 28.
The major mineral phases present in the FMO were pyrolusite ( -MnO2)
and goethite [ -FeO(OH)]. The FeO(OH) can directly adsorb arsenite and
arsenate anions. Pyrolusite ( -MnO2), the major mineral phase of the FMO
behaved in a manner similar to hydrous manganese oxide, MnO(OH),
because of the presence of chemically bound moisture. As(III) adsorbed
more strongly than As(V). One of its demerit is once it adsorbs arsenic it
cannot be regenerated. Bivalent cations, Ni2+, Co2+, Mg2+, enhanced
the adsorption capability of the FMO. The cost of the FMO was 5056
US$ per metric ton. This is much cheaper than the commercially available
carbons.

5.2.3 Soils and constituents

5.2.3.1 Soils.

It is been experimentally seen that Arsenate [As(V)] adsorption

desorption capacity of Olivier loam, Sharkey clay, and Windsor sand
are similar to the most of the adsorbents which are available in the

market .
The soil with the highest Fe levels and clay has the highest affinity
for both As(III) and As(V). This soil displayed adsorption behaviour
similar to pure ferric oxide. As(V) adsorbed more strongly than As(III)

under most conditions.

The adsorption characteristics of arsenic on laterite soil, a low-cost natural adsorbent,
were studied in the laboratory scale using real-life sample. The studies were

conducted by both batch and continuous mode. Laterite soil was found to be an
efficient adsorbent for arsenic removal from the groundwater collected from arsenic
affected area. Under optimized conditions the laterite soil could remove up to 98% of

total arsenic.
The removal and fixation of As(III) and As(V) from water by
soil/bentonite mixtures is also examined to develop reliable clay
liners for waste landfill sites. Either Masatsuchi soil
(weathered granite) or Murram soil (pumice) is used as the liners
main body. Wyoming bentonite clays were mixed with each of these
soils because of its superior impermeability. More arsenic is removed
by Masatsuchi soil without any pH buffer.
Both soils exhibited highest As(V) and As(III) adsorption in the pH
ranges of 36.5 and 79.5. Due to the different source and iron
loadings, no consistency was obtained in the sorption capacities.

5.2.3.2 Sand.
A variety of treated and coated sands can be employed for arsenic
remediation for example sand coated with iron oxide, manganese
greensand (MGS) and iron oxide-coated sand (IOCS) show higher
adsorption capacity than the untreated sand.
The addition of iron coating on sand effects drastically on arsenic
adsorption capacity for example the iron coating on the sand shows five
times higher arsenic adsorption capacity (28.57 g/g) than the uncoated
sand (5.63 g/g) at pH 7.5 in 2 h.
As(V) sorption on such materials decreases slightly with increase in pH
from 5 to 9 but As(III) sorption remains stable
Manganese greensand
Manganese greensand is a specially processed medium for iron, manganese, and hydrogen
sulphide removal. Manganese greensand can effectively for remove arsenic to
a limit <25 g/L.

Other materials like sulphate modified iron oxide coated sand (SMIOCS)
and synthesized iron coated sponge (IOCSp) are also tested in laboratories
for removing As(III) and As(V) effectively in the pH range of 7-9.

Conclusion
Based on the above discussions the following conclusions are made:
1. By a comparison among the conventional processes it is evident that coagulationfiltration
and lime softening techniques are cheaper but the removal efficiency of these techniques are
low (<90%). Hence, the adsorptive process with activated alumina seems to be the most
inexpensive among the techniques with higher efficiency (95%). For ground water systems
without pre treatment in-place, the most suitable treatment technologies are ion exchange and
activated alumina.

2. In near future surface coated adsorbents might play a role in decreasing treatment cost of
arsenic contaminated water.
3. Out of the advances reported in cost effective arsenic removal techniques, the microbial
oxidation of arsenic draws maximum attention because it requires no chemicals and the
microbes are indigenous to the contaminated water. The percentage oxidation has already
been reported as 80%. In spite of the low oxidation efficiency it can be applicable to reduce
arsenic concentration in the lower contaminant level successfully.
4. Moreover, genetic modification of microbes by microbial cloning technique might improve
the efficiency of this technique in near future.

BIBLIOGRAPHY

1. Dinesh Mohan, Charles U. Pittman Jr. Arsenic removal from water/wastewater using
adsorbentsA critical review Journal of Hazardous Materials 142 (2007) 153
2. P. Mondal, C.B. Majumder, B. Mohanty. Laboratory based approaches for arsenic
remediation from contaminated water: Recent developments Journal of Hazardous
Materials B137 (2006) 464479
3. Ernest O. Kartinen, Jr. and Christopher J. Martin. An overview of arsenic removal
processes Desalination 103 (1995) 79-88

4. Thomas S.Y. Choonga, T.G. Chuaha*, Y. Robiaha, F.L. Gregory Koaya, I. Aznib
Arsenic toxicity, health hazards and removal techniques from water: an overview
Desalination 217 (2007) 139166

Internet resources:
http://www.greenfacts.org/en/arsenic/l-2/arsenic-6.html, Visited on 17/03/2016
https://en.wikipedia.org/wiki/Arsenic, visited on 01/02/2009