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Contents

Abstract ............................................................................................................................................... 1
1. Introduction ................................................................................................................................ 1
2. Electrocoagulation process ......................................................................................................... 2
3. Removal of arsenic by Electrocoagulation .................................................................................. 3
4. Comparison of Electrocoagulation and Chemical coagulation ................................................... 4
5. Conclusion ................................................................................................................................... 5
6. References .................................................................................................................................. 6
Abstract
Arsenic is suspected to be carcinogenic. Drinking arsenic contaminated water can
cause skin and lung cancer. Arsenic in ground water is a recognized problem in India.
There are various methods to being down the concentration of arsenic below
permissible limit, for example, lime precipitation, coagulation followed by filtration,
adsorption, ion exchange etc. Electrocoagulation process (EC) is an encouraging
technology for the effective removal of arsenic from aqueous solution. In this paper
removal of arsenic by electrocoagulation method has been discussed and result has
been compared with chemical coagulation. EC process was found to have higher
removal efficiency but, it had the problem of passivation of electrodes.

1. Introduction
Arsenic pollution is a result of geological processes. Arsenic dissolves from solid state
in soil grains to liquid state in water. Arsenic comes into soil by weathering of rocks
and minerals. It reaches into groundwater and surface water by leaching and runoff.
Further, the problem may have been modified by use of certain fertilizers. Arsenic
concentration in water is controlled by many factors such as redox potential (Eh),
adsorption/ desorption, precipitation/ dissolution, pH, presence of other ions etc.
In deeper levels (below 20 meters) arsenic is naturally present in water. This water is
extracted by tubewells and used for drinking. Water present in upper layers is
relatively less contaminated as it has spent less time in ground and absorbed less
amount of arsenic.
Bihar, Jharkhand, Uttar Pradesh in flood plain of river Ganga; Assam and Manipur in
flood plain of river Brahmaputra; and Imphal and Rajnandan village in Chattisgarh have
been reported to be exposed to arsenic contamination. In this region water extracted
from tubewells have been found to contain arsenic concentration above the
permissible limit of 50g/L.
Arsenic has many uses in agriculture, medicine and industry. Some of them are listed
below
(i) Production of semiconductor, glass, transistors, paper
(ii) Processing of dyes, pigments, paper, wood, glass
(iii) Pesticide, insecticide, wood preservatives and herbicides
(iv) Cotton desiccant, hide tanning process, pharmaceuticals
Following effect on human health have been noted in Arsenic polluted areas
(i) Itching skin, burning and watering of eyes, weight loss, appetite loss,
weakness

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(ii) Chronic respiratory complaints were also common. Chronic cough was
evident in more than 50%
(iii) Gastrointestinal symptoms of anorexia, nausea, dyspepsia, altered taste,
pain in abdomen, enlarged liver and spleen, and ascites (collection of fluid
in abdomen)
(iv) Moderate to severe anemia was evident in some cases

2. Electrocoagulation process
Electrocoagulation (EC) involves many physical and chemical processes. Metals
(aluminium, iron, zinc) are used as a sacrificial electrodes to generate coagulant. When
a potential is applied between two electrodes; oxidation of electrode occurs at anode;
releasing metal cations and electrons in same proportion. This reaction is given as
+
+

22 4 + + 2 + 4

Number of molecules dissolved from electrodes depends on the current density


applied. These metallic ions move to negatively charged materials and coagulation
occurs. At cathode, water molecules dissociate to give hydrogen gas and hydroxide
ions. Reactions is given as
22 + 2 + 2

Hydroxides are good adsorbent for pollutants. Generation of metal hydroxides


depends on the pH of the solution. Metal hydroxides like Mn (OH)n have large surface
area and they attach with pollutants by various mechanisms and create flocks. These
hydroxides grow in size and attain settling velocity. There are some flocks which are
not large enough to settle down on their own. These flocks are removed by hydrogen
gas generated at cathode. Hydrogen gas carries these flocks to the surface where they
are skimmed off. Thus hydrogen gas plays very important role in removal of pollutants.
Oxygen generated at anode is important as it helps in oxidizing some metals.
Electrocoagulation has been found to be effective in removing turbidity, hardness,
phosphate fluoride, mercury, lead, cobalt etc.

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Figure 1 Pollutant removal mechanism

3. Removal of arsenic by Electrocoagulation


Iron and aluminum are widely used metal for electrodes. These metals are preferred
because of low cast, availability and higher efficiency. Arsenic in water is found in the
form of arsenide (As3-), metallic arsenic (As0), arsenite (As3+) and arsenate (As5+).
Arsenic can be removed with higher efficiency in arsenate from than arsenite. To
increase the efficiency of removal arsenite in converted to arsenate. In
electrocoagulation process arsenic can be easily oxidized to arsenate. Some author
have added oxidizing agent (hypochlorite) in water prior to electrolysis. This resulted
in oxidation of all arsenic to arsenite and increased removal efficiency.
In initial stage of electrolysis, authors have observed an increase in concentration of
arsenate. This increase in concentration is supposed to be due to oxidation of other
arsenic forms to arsenate. Accumulation of arsenic occurs as more and more flocks are
formed and is removed rapidly. Same result can be obtained by anodic oxidation too.
Zong at el. (2014) coupled EC process with anodic oxidation. Anodic oxidation is
advanced process in which anodes are able to generate hydroxyl radicals. These
radicals oxidize the arsenic.

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Anions present in water also affect the removal of arsenic. Fluoride ion reduced the
efficiency of the process significantly (Vasudevan et al., 2010b), but the presence of
sulfate ions in the water medium did not affect the arsenic removal efficiency of EC
process (Wan et al., 2011; You and Han,2016).
The main floc, Fe(OH)2, Fe(OH)3 and Al(OH)3 formations also depends on the pH
conditions. Ferrous hydroxide starts to precipitates at pH of 5. Increase in pH,
increases the concentration of ferrous hydroxide concentration. The concentration of
insoluble ferrous hydroxide is maximum at pH 12 and decreases with increases in
solution pH. Similarly, the minimum pH required for the precipitation of ferric
hydroxide and aluminium hydroxides are 1 and 4, respectively.
The major pollutant removal mechanisms in an EC system are sweep floc coagulation;
and adsorption and charge neutralization. arsenite (As3+) is more toxic than arsenate
(As5+). That is why oxidation is recommended as first step in arsenic removal. Initially,
concentration of arsenat (As5) increases due to conversion of arsenite (As3+) to arsenat
(As5). After sometime concentration of both the arsenate and arsenite decreases due
to adsorption on hydroxide flocks.

4. Comparison of Electrocoagulation and Chemical coagulation


Arsenic removal efficiency of EC process is higher than that of conventional chemical
coagulation process. EC in the presence of aluminium and iron anodes is able to
remove 99.99% of arsenate from the water medium. Complete arsenite removal by EC
process carried out in the presence of aluminium anode was observed by Ihos et al.
(2005), while only 70% arsenate and 40% arsenite removal by aluminium salts are
reported (Ihos et al., 2005; Lacasa et al., 2013). Kumar et al observed that chemical
coagulation is also efficient to remove both arsenate and arenite from water medium.
But the amount of coagulant required is very high compared to that required in EC
process. The higher arsenite removal efficiency of EC compared to chemical
coagulation is mainly due to the ability of EC to oxidize arsenite to arsenate.
Authors have observed that arsenate removal efficiency is dependent on pH of water
for both EC and chemical coagulation. Efficiency is inversely relation with the pH.
Arsenite removal efficiency of EC process slightly depends on the solution pH, while
the efficiency of chemical coagulation is entirely independent of the variation in
solution pH.
Lacasa et al. (2013) explained the higher arsenic removal efficiency of EC process
compared to chemical coagulation process. The addition of chemical coagulants
decreases pH of solution. This condition is not favourable for the generation of
aluminium hydroxide precipitate. But, these concentrations are favourable for the
generation of aluminium arsenate and are the predominant insoluble species
responsible for the removal of arsenic from water via chemical coagulation in the
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presence of aluminium salts. Similarly, the arsenic removal in the presence of iron salts
is prevailed by the generation of ferric arsenate.
On the other hand, solution pH increases with electrolysis time in EC process. This
increase in pH is favourable for the removal of arsenic, especially arsenate from water
medium. Because, most of the arsenate species are insoluble at higher pH conditions.
Even though, the concentrations of arsenic and aluminium are favourable for the
generation of aluminium hydroxide and aluminium arsenate precipitates, aluminium
hydroxide plays a major role in the removal of arsenic from water medium by EC
process. Arsenic removal by EC in the presence of iron anode is complex, due to the
generation of ferrous ions in the electrolytic solution. Ferrous ions are more soluble
than ferric ions. Thus, the arsenic removal is retarded by the presence of ferrous ions
at the initial stages of electrolysis. But, the generation of ferric ion by the oxidation of
ferrous ion results in the generation of insoluble ferric hydroxide and is responsible for
the removal of arsenate.

5. Conclusion
In India, seven states namely, West-Bengal, Jharkhand, Bihar, Uttar Pradesh in the
flood plain of Ganga River; Assam and Manipur in the flood plain of Brahamaputra and
Imphal rivers and Rajnandgaon village in Chhattisgarh state have so far been reported
affected by arsenic contamination in groundwater above the permissible limit of 50
g/L.
EC process is very efficient process for arsenic removal. Highest efficiency of removal
was with iron and aluminium electrodes and efficiency depends upon pH of solution.
Efficiency of Chemical coagulation was much less than that of EC process, although
removal mechanism was same. Even though EC process is very effective for the
elimination of arsenic and its compounds from water medium, the passivation of
electrodes is a major drawback. The recent study by van Genuchten et al. (2016) gave
an excellent explanation for the electrode passivation during the arsenic removal by
EC process. The authors checked the electrodes used for arsenic removal in laboratory
experiments and in real field; and observed significant differences on the surface layer
size and texture of laboratory and field electrodes. The laboratory electrodes had a
light orange surface coating and were able to clean the surface with very less mass
reduction. On the other hand, the surface of the field electrodes was coated densely
and was able to remove the coating by chipping it. This produced black coloured flakes
with area 10 cm2 and several mm thicknesses. The surface of the field electrodes was
also in black colour, even after the chipping process. This indicates that the electrodes
were more corroded in field conditions than in laboratory conditions.
Another problem with real field water treatment is the absence of dissolved oxygen in
water medium. The conversion of ferrous to ferric ions accelerates in the presence of

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dissolved oxygen. Also, the aeration of EC system increases the efficiency of the
process, even in the case of real field water (Parga et al., 2005). Therefore, aeration of
EC system is an important step for enhancing the process efficiency. The aeration also
helps to increase the collision between the contaminant and floc, which shoot up the
subsequent removal of contaminant.

6. References
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You, H.J., Han, I.S., 2016. Effects of dissolved ions and natural organic matter on
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