Enivro. Treatment

National Conference on Environmental Conservation (NCEC-2006)
Birla Institute of Technology and Science (BITS) - Pilani
Removal of Toxic Metalloid from Water: Future Perspectives

Y Ravi Chandraa1 and Arvind Kumar Sharmaa*
a
Chemical Engineering Group, Birla Institute of Technology and Science (BITS), Pilani (Rajasthan), India.
1
Email: h2004407@bits-pilani.ac.in
b
*Tel.: 01596-245073 x 215 (O), Fax: 01596-244183 (O), Email: arvinds@bits-pilani.ac.in
ABSTRACT
In recent years, arsenic contamination has emerged as a fresh blow to the country. The increasing
concern over human exposure to arsenic in India has necessitated the development of rapid methods
for determination of trace levels of arsenic in water. The objective of this work is to critically review
the various aspects of the removal of arsenic from water and set forth the future directions. This
review will critically analyze different methods, like oxidation, co-precipitation, adsorption, ion
exchange, membrane separation, etc and project the future possibilities to reduce the arsenic from
water.
Keywords: Water Purification; Arsenic Removal.
1. INTRODUCTION
Arsenic in water is due to the dissolution of minerals from subterranean strata or from an
anthropogenic origin such as the leaching of manmade arsenic compounds from smelting of
metal ores, agricultural pesticides, desiccants and wood preservatives (Siddesh and Robert,
2004). Arsenic is widely distributed in nature in air, water and soil as a metalloid and as
chemical compounds both inorganic and organic (Robert, 2002). Arsenic occurs in the
environment mainly as the arsenite (+III) and arsenate (+V).
The presence of arsenic in groundwater has been a major public health concern in many
countries, such as Bangladesh, India, Taiwan, Thailand, Argentina, China, Canada, USA,
Mexico, Nepal and Vietnam (Viraraghavan and Pokhrel, 2006). Arsenic ingestion by
drinking water and food washed with the contaminated water may cause internal malignancies
cancers, vascular disease, and non-malignant skin alterations, arsenical dermatitis, skin
cancer, neurological effects, enlargement of liver, heart disease and internal cancers.
Therefore, there is a tremendous demand for developing efficient methods for arsenic removal
from drinking water. A short review of these technologies is intended to update the
technological development in arsenic removal, understand the problems, prospects and
limitations of different treatment processes and delineate the areas of further improvement for
successful implementation and adaptation of technologies to rural conditions.
2. TECHNOLOGIES FOR ARSENIC REMOVAL
2.1 Oxidation
Arsenic is present in the groundwater in As (III) and As (V) forms in different proportions.
Many of the arsenic removal technologies are most effective at removing the pentavalent form
of arsenic (arsenate), since the trivalent form (arsenite) is predominantly non-charged below
Proceedings of National Conference on Environmental Conservation (NCEC-2006), September 1-3, 2006, pp 301-308
Editors: B V Babu and V Ramakrishna
Session Title: Environmental Engineering - 3 (Technical Session-4)
301
Y Ravi Chandra and Arvind Kumar Sharma
the pH of 9.2. Therefore, many treatment systems include an oxidation step to convert
arsenite to arsenate (Richard, 2001).
Air Oxidation: Atmospheric oxygen is a readily available oxidizing agent. Clifford et al.
(1983) observed that 25% of As (III) was oxidized within 5 days when purging a solution
initially containing 200 µg/L As (III) with air. Böckelen & Niessner (1992) found that 19%
of As (III) was oxidized within 15 min in the presence of pure oxygen in a water initially
containing 69 µg/L As (III).
Chemical Oxidation: Arsenic can be oxidized from arsenite to arsenate under wide range of
conditions using the chemicals like ozone, chlorine, potassium permanganate, H2O2 and
Fenton’s reagent as well as photochemically and microbiologically.
An ozone dose of 2000 µg/L, contacted with the water containing arsenic of initial
concentration of 69 µg/L for 1 min prior to filtration, was shown to be effective in oxidizing
iron and manganese, at the same time removing arsenic and other metals to below detection
limits (Kim and Nriagu, 1999).
Viraraghavan and Pokhrel (2006) treated a raw water initially containing 200 µg/L As (III)
with KMnO4 coated sand and found that the As (III) concentration was reduced to 25 µg/L
and the formed As (V) was suggested to be removed in an Fe (II)/O2-process. Experiments on
the use of Fe (III) for the oxidation of As (III) were also conducted. The oxidation rate of As
(III) in the presence of Fe (OH)3 was much lower than the oxidation rate measured in the
presence of MnO2 (Monique and Fritz, 2003).
The oxidation rate of As (III) in the presence of oxygen could be increased by UV irradiation
of the water. Yang et al. (1999) investigated the oxidation of As (III) in the presence of
oxygen when using a UV/H2O2 treatment process. At an initial As (III) concentration of
40,000 µg/L and a molar ratio of As to H2O2 of 1 to 1, As (III) was oxidized within 10 min.
The oxidation rate of As (III) could be increased by more than four orders of magnitude in the
presence of Fe (III) and irradiating the water with near-UV radiation.
Bacteria could oxidize As (III) in the presence of at least 1000 µg/L of O2. As (III) could be
oxidized and removed without additional treatment step due to the presence of bacteria. The
biotic oxidation of iron by the microorganisms Gallionella ferruginea and Lepotothrix
ochracea was effectively used for the removal of arsenic from ground waters (Zouboulis and
Ioannis, 2004). Under the optimized experimental conditions, trivalent arsenic would be
oxidized by these microorganisms, contributing to increase in overall arsenic removal (up to
95 %) even when initial arsenic concentration was 200 µg/L. In addition, the pentavalent
arsenic, under the same experimental conditions was removed effectively, leading to residual
concentrations below the newly enforced limit of 10 µg/L.
302
2.2 Co-Precipitation
Arsenic removal by chemical precipitation is the best-known and most frequently applied
technique. At present many countries are successfully using the conventional method of
arsenic removal. The treatment process consists of coagulation followed by flocculation,
sedimentation and filtration.
Removal by Iron compounds: Jiang (2001) reported that the optimal pH for the removal of
arsenic by FeCl3 was 7. The extent of As (III) removal was lower than the extent of As (V)
removal. The removal of As (III) by FeCl3 was more strongly influenced by the composition
of the groundwater than the removal of As (V). Many of his studies showed that the removal
of arsenic decreased drastically at pH higher than 8. Borho and Merkl (1993) observed that
more than 95% of As (V) was removed with 0.09 mmol/L Fe (III) in waters initially
containing 300 µg/L As (V). At the same initial Fe (III) concentration, only 50 to 60% of As
(III) was removed. The effectiveness of arsenic removal did not only depend on the pH and
the iron content of the water but also on the presence of other water constituents such as
orthophosphate or the turbidity of the water.
Removal by Aluminum compounds: Arsenic adsorbed on aluminum hydroxide flocs as Al-As

complex is removed by sedimentation. Filtration may be required to ensure complete removal
of all flocs. In alum coagulation, the removal is most effective in the pH range 7.2 - 7.5.
Hering et al. (1997) observed that 80% of arsenic was removed from a water containing 20
µg/L arsenic by 4.9 mg/L FeCl3 compared to 40 mg/L Al2 (SO4)3· 90% of arsenic was
removed at pH 6 with 20 mg/L alum when treating a water initially containing 20 µg/L
arsenic. It was found that the removal of arsenic decreased rapidly at higher pH.
2.3 Adsorption
In the process of adsorption, the adsorbent should meet four important criteria: high removal
efficiency, safety, simple operation and minimum residual mass. The adsorption of arsenic on
the adsorbent mainly depends on the pH of the raw water and the experimental conditions.
The adsorbents mentioned below will give fairly a good idea regarding the adsorption of the
arsenic on various adsorbents.
Activated Alumina: Wang et al. (2002) investigated the removal of arsenic by activated
alumina in full-scale systems. The initial arsenic concentration was varied between 34 and 87
µg/L consisting primarily of As (V). An average removal of arsenic of 87 to 98% was
achieved. Selectivity sequence of activated alumina in the pH range of 5.5 to 8.5 was
reported by Clifford et al. (1983) as:
OH- > H2AsO4 - > Si(OH)3O- > HSeO3 - > F- > SO4 2- > CrO4 2- >> HCO3 - > Cl- > NO3 - > Br -
> I-
Removal efficiency of around 95% for both arsenite and arsenate was observed, but arsenic
capacity varied significantly, and was controlled primarily by pH and influent arsenic
concentration and speciation.
Alumina Manganese Oxide: Synthetic well water with characteristics similar to that of
groundwater as found in West Bengal, was treated with alumina manganese oxide (Kepner et
al., 1998). It removed up to 94% of As with the groundwater at initial arsenic concentrations
303
of 50, 000 µg/L. Alumina manganese oxide was most effective when its manganese
composition was greater than 10% in solutions of pH 7. Increasing manganese content
beyond 10% had no effect on the removal capacity. This adsorbent was also effective in
removing other toxic metals such as iron, cadmium, antimony, lead and uranium from the
well water.
Granular Ferric Hydroxide (GFH): Batch kinetic studies were conducted as a function of pH
to study the removal of both As (III) and As (V), spiked to required concentrations in tap
water. The mass of GFH used was kept at 0.2 g in the kinetic studies. The initial
concentration of both As (III) and As (V) in the tap water was 100 µg/l. The effect of solution
pH on adsorption of arsenic species onto GFH was studied at the pH levels of 5, 6, 7.6, and
8.5. GFH was effective in reducing both As (III) and As (V) to a level less than 5 µg/l in
drinking water and arsenic removal greater than 95% was observed (Vu. et al., 2003).
Kimberlite Tailings: An adsorbent dose of 20 g/L was used for the arsenic removal from
groundwater collected from various parts of West Bengal. Average flow rate of 10.13
cm3/min and arsenic concentrations in the influent of 1000 µg/L were maintained throughout
(Dikshit et al., 2000). Column studies were conducted to investigate the performance of fixed-
bed Kimberlite. This sorbent could remove 90-94% of arsenic in 12 h of contact time from
groundwater spiked with arsenic.
Gravel Bed Containing Iron-Coated Sand: Jiang (2001) reported the removal of arsenic by
iron oxide coated sand and found that up to 96% of arsenic was removed from waters initially
containing 21 to 1100 µg/L arsenic.
Hydrotalcite (Mg-Al-CO32-): Synthetic hydrotalcites (HT) were prepared by calcining Mg-

Al-CO3 2- at 500oC for 10 h (Lazaridis, 2002). The hydrotalcite was then added to a spiked
As (V) solution (initial arsenic concentration of 20,000 µg/L) in a dispersed-air flotation
environment with the usage of various nonthioionisable surfactants in the flotation process.
The efficiencies of both As (V) removal and downstream flotation recovery were well over
90% at natural pH. Arsenic removal was most effective at high ionic strength.
Iron Filings: Ramaswami et al. (2001) investigated Feo for arsenic removal using a batch-
mixed iron treatment with zerovalent iron against high-arsenic-content water [As (III) of 2000
µg/L]. Removal efficiency of 93% was achieved for a short contact time of 0.5-3.0 h and pH
of 5. Arsenic was found to adsorb strongly onto the iron filings and the treated water could
easily be decanted. Residual dissolved iron was at low concentrations that were safe for
drinking water.
2.4 Ion-Exchange
Korngold et al. (2001) used strong base anion-exchange resins for the removal of As (V).
They observed competing reactions between SO42–, NO3 –, Cl–, and arsenic anions so that the
efficiency of arsenic adsorption decreased in the presence of these anions. More than 99% of
arsenic was removed by the resins at an initial arsenic concentration of 600 µg/L.
304
Removal of arsenic with an ion-exchange resin in full-scale system was studied by Wang et
al. (2002). The initial arsenic concentration was varied between 34 and 87 µg/L consisting
primarily of As (V). Arsenic was removed to levels lower than 5 µg/L. The regeneration
wastewater contained 6.4 to 9.5 mg/L of As.
2.5 Membrane Techniques

Arsenic removal from water can be done by membrane filtration with Reverse Osmosis (RO),
Nanofiltration (NF) and Micro Filtration (MF) [Ming-Cheng, 2005]. Membranes normally
require relatively high pressures in the range of 5 psi to 1,000 psi to drive the liquid through
the pores to remove the contaminants present inside the water.
Nanofiltration Membranes: Membrane filtration using nanofiltration (NF) membranes has

also been identified as a promising technology for the small water treatment systems. A
survey was conducted at a 65,000 m3/day water treatment plant. The source water for the
water treatment plant was taken from the river, which contained naturally occurring arsenic.
Total arsenic and trivalent arsenic concentrations of raw water were about 5000–50,000 µg/L
and about 1000–10,000 µg/L, respectively.
Three types of NF membranes (ES-10, NTR-7250 and NTR-729HF, Nitto Electric Industrial
Co., Japan) were used in this study (Yuko et al., 2002). Removal efficiency for both arsenic
species [As (III) and As (V)] under low-pressure range between 0.2-0.6 MPa was investigated
by using ES-10 and was around 99% for arsenate and 55% for arsenite and it increased
slightly with the increase in applied pressure (Ming-Cheng, 2005).
Reverse Osmosis: Tests with a reverse osmosis system showed for an average initial arsenic
concentration of 60 µg/L, that the membranes lowered the arsenic concentration in the water
to 0.9 µg/L giving a total rejection of 99% (Membrane Technology Newsletter, 2001). In a
small town in Canada, a low-energy cross flow reverse osmosis system with permeate flush
was added to a water treatment system in order to remove arsenic from raw water. The
arsenic concentration was lowered from 48 µg/L to 1 to 2 µg/L. The three-step treatment
system operated with an oxidation step by addition of KMnO4 and O3. After oxidation, the
water was filtered through gravity filters where 20% of arsenic was removed. Then the water
was split into two streams, one stream passed through the reverse osmosis and one was stored
in a reservoir. The permeate of the reverse osmosis was blended with the gravity filtered
water so that the mineral profile of the water could be tailored (Public Works Magazine,
2002).
3. FUTURE PERSPECTIVES
Reliable, easy-to-handle and cost-effective removal technologies are necessary for the
treatment of arsenic contaminated water especially for application in developing countries.
Even though 90-95% removal is obtained from water containing high concentrations of
arsenic, still arsenic concentrations are exceeding the permissible limit. So, an alternative
should be considered for the removal of arsenic from water. As the As (V) can be removed
from waters containing arsenic but As (III) is the major contaminant, which cannot be
completely removed by using the above processes, an alternative is to be found so as to
305
remove the arsenic. Oxidation process, which can oxidize the As (III) to As (V), can improve
the efficiency of arsenic removal by the combination with some of the above processes.
Using low-cost adsorbents, coagulants, membranes combined with photochemical or
microbiological oxidation processes can increase the removal efficiencies to 100% and
decrease the cost of the process to reliably produce waters below the permissible limit.
Ming-Cheng (2005), for instance, investigated the combined Coagulation and Micro filtration
process (CMF) which could reliably produce treated water containing less than 2 µg
arsenic/L, with the feed water containing 40 µg arsenic/L. The removal efficiency for arsenite
was poorer than that for arsenate since arsenite existed as a neutral species and the hydroxide
coagulation process relied upon ionic interactions. For effective removal of arsenic from
water a complete oxidation of arsenite to arsenate was required to CMF process (Ming-
Cheng, 2005). Even though the micro filtration process was not effective in removing the
arsenic when added to coagulation process but when applied to the adsorbents, membranes
mentioned above could effectively remove the arsenite from the water.
In future, there is an opportunity for the Magnetic particle technology, which may provide a
viable, low-cost option for the arsenic removal from water. Magnetic particles for arsenic
removal would have to be composed of magnetic material (magnetite) of very small size (<10
µm). The magnetic particles are directly added to a drinking water storage vessel or small
pitcher and gently stirred after adding the contents with a spoon for a short period and the
magnetic particles would be removed with a simple bar magnet. The reaction rates may be
greater because the reactions occur at the high specific surface areas. More thorough
evaluation is needed to determine the efficacy of magnetic particles in removing arsenic (Vu.
et al., 2003).
4. CONCLUSION
Our review of arsenic removal technologies indicates that arsenic can be removed quite
efficiently by the methods mentioned above. There is, however, need to look for newer and
better methods or their effective, safe and economical combinations for the complete removal
of arsenic from water/wastewater. They also have to be encouraged for wider implementation
in the acute arsenic problem areas to avoid ingestion of excessive arsenic through water.
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National Conference on Environmental Conservation (NCEC-2006)

Birla Institute of Technology and Science (BITS) - Pilani

Removal of Toxic Metalloid from Water: Future Perspectives

2. TECHNOLOGIES FOR ARSENIC REMOVAL

Removal by Aluminum compounds: Arsenic adsorbed on aluminum hydroxide flocs as Al-As

Hydrotalcite (Mg-Al-CO32-): Synthetic hydrotalcites (HT) were prepared by calcining Mg-

2.5 Membrane Techniques

Nanofiltration Membranes: Membrane filtration using nanofiltration (NF) membranes has

Dikshit, A. K., Pallamreddy, K., Praveenreddy, L. V and Saha, J. C. (2000). “Arsenic in

Viraraghavan, T. and Pokhrel, D. (2006). “Arsenic Removal from an Aqueous Solution by a

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