Journal of Environmental Management 166 (2016) 387e406

Contents lists available at ScienceDirect

Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Review

Removal of arsenic from water using nano adsorbents and challenges:

A review
Sneh Lata, S.R. Samadder*
Department of Environmental Science & Engineering, Indian School of Mines, Dhanbad 826004, India

a r t i c l e i n f o a b s t r a c t

Article history: Many researchers have used nanoparticles as adsorbents to remove water pollutants including arsenic
Received 19 July 2015 after modifying the properties of nanoparticles by improving reactivity, biocompatibility, stability, charge
Received in revised form density, multi-functionalities, and dispersibility. For arsenic removal, nano adsorbents emerged as the
19 October 2015
potential alternatives to existing conventional technologies. The present study critically reviewed the
Accepted 24 October 2015
Available online 5 November 2015
past and current available information on the potential of nano adsorbents for arsenic removal from
contaminated water and the challenges involved in that. The study discussed the separation and
regeneration techniques of nano adsorbents and the performance thereof. The study evaluated the
Keywords:
Arsenic
adsorption efficiency of the various nanoparticles based on size of nanoparticles, types of nano adsor-
Adsorption bents, method of synthesis, separation and regeneration of the nano adsorbents. The study found that
Nano adsorbents more studies are required on suitable holding materials for the nano adsorbents to improve the
Regeneration permeability and to make the technology applicable at the field condition. The study will help the
Review readers to choose suitable nanomaterials and to take up further research required for arsenic removal
Separation using nano adsorbents.
Supporting material © 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
2. Applicability of various nano adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
2.1. Different nano adsorbents for arsenic removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
2.1.1. Iron oxides/hydroxides nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
2.1.2. Alumina nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
2.1.3. Copper oxide nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
2.1.4. Titanium dioxide nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
2.1.5. Zinc oxide nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
2.1.6. Mixed metal oxide (MMO's) nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
2.1.7. Carbon nano tubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
2.1.8. Others . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
3. Adsorption process of nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
4. Challenges in handling nano adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
4.1. Use of supporting materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
4.2. Separation of nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
4.3. Regeneration of nano adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
5. Comparison of arsenic removal using different nano adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
6. Critical discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
6.1. Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
6.2. Effect of synthesis method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403

* Corresponding author.
E-mail address: sukh_samadder@yahoo.co.in (S.R. Samadder).

http://dx.doi.org/10.1016/j.jenvman.2015.10.039
0301-4797/© 2015 Elsevier Ltd. All rights reserved.
388 S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406

6.3. Effect of initial concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403

6.4. Effect of particle size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
6.5. Effect of competing ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
6.6. Effect of contact medium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404

1. Introduction undesirable by-products and the used adsorbents can be regener-

ated for reuse upto reasonably good number of cycles. However,
Water contamination due to increased population and industrial adsorption has certain limitations also, such as it could not achieve
activities is one of the most challenging issues to the researchers, a good status at commercial levels due to the lack of suitable ad-
because it is continuously increasing threats to both human health sorbents of high adsorption capacity and unavailability of com-
and the environment. The main threats to human health from mercial scale columns (Grassi et al., 2012). Moreover, same
heavy metals contamination of water are associated with the adsorbent is not effective for different types of water pollutants. For
exposure to different heavy metals and metalloids such as lead, adsorption, various materials were used as adsorbents such as
cadmium, chromium, mercury and arsenic. The presence of these surfactants, synthetic activated carbon, industrial byproducts and
heavy metals and their effects on human health are studied and wastes, ferrous material, iron based soil amendment, and mineral
regularly reviewed by international bodies such as the WHO (J€ arup, products (Hashim et al., 2011). To fulfil the objective of the devel-
2003). Out of these heavy metals, arsenic is found to pose opment of an effective adsorbent that is active and rapid for arsenic
maximum adverse effects on human health through arsenic removal, nano size adsorbents were developed by researchers.
contaminated drinking water. Mining wastes, petroleum refining, Macromolecules have intra-particle diffusion that decreases the
sewage sludge, agricultural chemicals, ceramic manufacturing in- adsorption rate and available capacity of the adsorbent, while
dustries, and coal fly ash are some of the anthropogenic activities nanoparticles have small diffusion resistance that increased the
that increase arsenic concentrations in surface water as well as significance of the application of nanoparticles as adsorbent (Attia
groundwater (Viraraghavan et al., 1999). Natural sources such as et al., 2012). Nanoparticles also have some distinctive properties
weathering, erosion of rocks/soils and volcanic emissions also such as small size, catalytic potential, large surface area, high
contribute arsenic in aqueous system. Naturally, arsenic occurs reactivity, easy separation, and large number of active sites that
more than 200 different mineral forms. Of these, approximately facilitate better arsenic removal efficiency compared to other
60% are arsenates, 20% are sulphides and sulphosalts, and the available adsorbents. Ngomsik et al. (2005) compared efficiency of
remaining 20% are arsenide, arsenite, oxides, silicates and nano and micro sized particles and concluded nano adsorbents as
elemental arsenic (Onishi, 1969). The main arsenic containing comparatively better than micro adsorbents, though micro parti-
mineral arsenopyrite is formed by hydrothermal activity associated cles have been studied extensively for metal extraction and have
with the intrusion of granitic magma and orogenesis (Duarte et al., the advantage of easy separation. In the process of developing nano
2009). The occurrence of arsenic in drinking water can occur as a adsorbents, various transition metal based compounds have been
result of its natural geological presence in local bedrock (Garelick explored as arsenic removing adsorbents such as Cu, Fe, and Ti.
et al., 2008). In drinking water, it predominantly occurs as inor- Other materials like alumina and polymers like vinylpyridine have
ganic (arsenite, arsenate) and organic forms (methyl and dimethyl also been modified for the preparation of nano adsorbents. Though
arsenic compounds) mainly in surface water (Smedley and nano adsorbents give better results compared to other adsorbents
Kinniburg, 2002). High-arsenic bearing waters are not expected for arsenic removal, but there are two main challenges in using
where there is a high concentration of free sulphide, because in nanomaterials for water purification; one is the non-availability of
reducing condition it forms precipitate with arsenic (Moore et al., nanomaterials at economically affordable prices and the other is
1988). A recent publication reported that arsenic is a unique the toxicity and the environmental fate of nanomaterials (Mostafa
carcinogen. It is the only known human carcinogen for which there and Hoinkis, 2012). The cost is mainly dependent on availability,
is adequate evidence of carcinogenic risk by both inhalation and types, preparation and applicability in actual field conditions.
ingestion (Centeno et al., 2006). In six administrative blocks of the Toxicity of nanomaterials increases with atomic number with the
district Murshidabad of West Bengal, India, about 1.25 million exceptions of Fe2O3 (lower toxicity than expected) and CoO (higher
people are exposed to groundwater arsenic concentrations above toxicity than expected) (Huang et al., 2010). There are many review
0.05 mg/L (Samadder, 2011). Considering its toxicity, WHO decided papers available on arsenic removal using nano adsorbents, but this
maximum permissible limit for arsenic as 0.01 mg/L in drinking paper critically reviewed the comparative study of applicability and
water. Increasing risk of arsenic carcinogenicity for developing the challenges of selecting nanomaterials as adsorbents for removal
countries drawn the attention of the researchers to do more of arsenic from drinking water.
research on arsenic contamination and treatment for its removal.
To treat the contaminated groundwater or surface water econom-
ically, methods such as oxidation (Pierce and Moore, 1982; Sorlini 2. Applicability of various nano adsorbents
and Gialdini, 2010), co-precipitation (Choong et al., 2007; Kumar
et al., 2004), adsorption (Zaspalis et al., 2007; Bhatnagar et al., Development of nano adsorbent is regarded as the major step
2010), ion-exchange (Anirudhan and Unnithan, 2007), and mem- towards achieving the nanoscaling effects and properties that have
brane technologies (Brandhuber and Amy, 2001) were used. been utilised by nature for millions of years. Nanoparticles are small
But the adsorption evolved as the most promising method atomic clusters with <100 nm size (Husein and Nassar, 2008) and are
among the available methods as this method does not add efficient to remove arsenic 5e10 times more effectively than their
micron size counterparts (Ponder et al., 2001; Sharma et al., 2009).
 S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406
Several nanocomposites and nanoparticles have been used for
removal of arsenic from drinking water. Nano adsorbents can
transform toxic substances into non-toxic and can adsorb toxic
substances by ion exchange, ion precipitation and adsorption.
Nanocomposites are prepared using materials such as, ceramic or
polymer matrices strengthened by nanoparticles (Nassar et al.,
2005). In a study conducted by Hristovski et al. (2007), it was re-
ported that some metal oxide nanoparticles may end up in effluent
simply by washing the packed beds, but others such as Nikel (Ni) may
be dissolved in water prior to its treatment. Therefore, selection of
nano adsorbents for removal of arsenic or other heavy metals should
be done carefully to achieve maximum removal efficiency and easy
separation. Various metal oxides of transition metals have been used
for preparing nano adsorbent. Macroscopic studies showed that
amorphous metal oxides have large adsorption capacities (per unit
mass basis) due to their extremely high surface areas (Trivedi and
Axe, 1999; Dixit and Hering, 2003). Different methods such as pre-
cipitation, solegel, hydrothermal, dry vapour deposition, surfactant
mediation, micro emulsion, electro-deposition and sonochemical
methods have been reported in literature to synthesize nanoparticles
(Husein and Nassar, 2008; Mohapatra and Anand, 2010).
2.1. Different nano adsorbents for arsenic removal
2.1.1. Iron oxides/hydroxides nanoparticles
Iron compounds such as hematite, goethite, iron oxide-coated
materials and granular ferric hydroxide (GFH) are the preferred
group of substances for arsenic adsorption because they lead to low
leaching of adsorbed arsenic from exhausted adsorbent
(Ghanizadeh et al., 2010). Nassar (2012) reported different types of
iron oxides viz. hematite (a-Fe2O3), maghemite (g-Fe2O3), magne-
tite (Fe3O4), and wustite (FeO); oxides/hydroxides of iron viz.
goethite (a-FeOOH), akagneite (b-FeOOH), lepidocrocite (d-FeOOH),
feroxyhyte (d0 FeOOH); and hydroxides of iron viz. ferrihydrite
(Fe5HO8$4H2O) and bernalite (Fe (OH)3). These iron nanoparticles
have magnetic properties which facilitate easy separation from
water using high gradient magnetic separation (HGMS) technique
after adsorption. In addition to iron oxide nanoparticles, nano-
particles of its zero-valent form have also been reported for
removal of metallic pollutants such as cadmium (Cd), zinc (Zn),
selenium (Se), arsenic (As), chromium (Cr), silver (Ag) and lead (Pb)
from drinking water and industrial effluents to prove its potential
for environmental applications. Preparation of nano iron oxide
particles is a challenging area of research as it requires careful se-
lection of pH, concentration of the reactants, temperature, method
of mixing, and rate of oxidation (Domingo et al., 1994). Mamindy-
Pajany et al. (2011) studied arsenate adsorption on goethite, he-
matite, magnetite and found arsenic adsorption is related to the
iron content of adsorbents, and adsorption rate increases in the
order of goethite < hematite < magnetite < ZVI. To enhance surface
chemistry, particle stability and subsurface mobility potential of the
nanoscale zero-valent iron (NZVI) and polyvinyl alcohol-co-vinyl
acetate-co-itaconic acid (PV3A), a nontoxic and biodegradable
surfactant has been used by Sun et al. (2007). Sylvester et al. (2007)
used ArsenXnp, a hybrid sorbent, consisting of nanoparticles of
hydrous iron oxide distributed throughout a porous polymeric
bead. Arsenate interactions with iron oxides are dominated by the
formation of strong inneresphere complexes and to a lesser extent
by weaker ion exchange reactions. Feng et al. (2012) coated Fe3O4
nanoparticles with ascorbic acid in aqueous suspensions that
improved the dispersibility of nanoparticles as well as effectively
inhibited the leaching of Fe into the solution.
2.1.2. Alumina nanoparticles
Alumina nanoparticles in chitosan-graft-polyacrylamide (CTS-
389
g-PA) was used as adsorbent for arsenic removal by Saha and Sarkar
(2012). There were several reasons for grafting new functional
groups: (a) to increase the density of the sorption sites, (b) to
change the pH range for metal sorption, and (c) to change the
sorption sites and/or the uptake mechanism in order to increase
sorption selectivity for the target metal (Guibal, 2004). Darban et al.
(2013) used inexpensive kaoline as raw material to produce
nanoporous g-alumina by precipitation method with high surface
area (201.53 m2/g) and small particle size (22e36 nm). This nano-
alumina powder has good adsorption capacity and recovery effi-
ciency. Jang et al. (2003) investigated the types of surface
complexation and the rate of adsorption of nanostructured silicate
media impregnated with metal oxides. For the removal of arsenate
from groundwater they used mesoporous silica (SBA-15) as sup-
porting media impregnated with metal oxides such as iron,
aluminium and zinc. But aluminum-impregnated SBA-15 was
found attributed to the fast adsorption capacity. The hexagonal
open-pore structures of the MCM-41 (two-dimensional hexagonal
mesopore structure) and more number of monodentate hydroxyl
densities enhanced the accessibility and transport of arsenate
species on adsorbent surface (Jang et al., 2003).
2.1.3. Copper oxide nanoparticles
Cupric oxide (CuO) was found as an effective arsenic removal
nano adsorbent, because it did not require pH adjustments or
oxidation of As (III) into As (V) and it performed well in the pres-
ence of competing anions (Reddy, 2007; Reddy and Attili, 2005).
These nanoparticles are easy to regenerate and can be reused to
remove arsenic from water. In a study, cupric oxide nanoparticles
was used in polypropylene centrifuge tubes for batch study while
sand was used as supporting material of nanoparticles for column
study (Reddy et al., 2013).
2.1.4. Titanium dioxide nanoparticles
Various properties of TiO2 such as chemical stability, low cost,
nontoxicity and the resistance to corrosion (Hung et al., 2006),
strong oxidizing power of the holes, redox selectivity, easy prepa-
ration, high affinity to arsenic and its inherent photo-oxidizing
capability of As (III) into As (V) remove the need of pre-oxidation
(Bang et al., 2005; Pena et al., 2006). Various authors used tita-
nium as nanoporous titania and titatinum dioxide (Lee and Choi,
2002; Dutta et al., 2004; Pena et al., 2006) for arsenic removal.
Han et al. (2010) studied surface complexation model (SCM) to
explain the surface properties of nanoporous titania adsorbents
(NTAs). After SCM study, they identified the type of surface species
that contribute the apparent arsenic removal at specified pH. For
adsorption of As (III) onto Ti(25)eSBA-15 monodentate surface
complexes were found more efficient over wide range of pH, while
bidentate surface complexes were found efficient for As (V)
adsorption at pH 8 (Han et al., 2010).
2.1.5. Zinc oxide nanoparticles
ZnO is a nontoxic and very stable material. Zinc oxide effectively
works in the pH range of 5.8e6.8 that made it user friendly (Singh
et al., 2012).
2.1.6. Mixed metal oxide (MMO's) nanoparticles
Use of metal composite containing two or more metals inherits
the advantages of parent oxides and shows synergistic effect of
higher adsorption capacity rather than individual metal oxide.
Various metal oxide composites such as FeeCe (Zhang et al., 2005),
FeeMn (Kong et al., 2014), FeeTi (Gupta and Ghosh, 2009), CeeTi
(Li et al., 2010), FeeZr (Ren et al., 2011; Gupta et al., 2009), FeeCu
(Zhang et al., 2012), MneCo (Zhang et al., 2010), FeeCr (Basu and
Ghosh, 2011) and magnetite-graphene oxide (Chandra et al.,
390 S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406
2010) have been used for arsenic removal. Parsons et al. (2009)
selected Fe3O4, Mn3O4, and MnFe2O4 nanophases for their studies
and reported that bimetal oxide showed comparatively higher
adsorption capacity. Zhang et al. (2010) used MnFe2O4 and CoFe2O4
magnetic nanoparticles that were prepared by the chemical co-
precipitation method. Paramagnetic nature of these magnetic
nanomaterials made its separation easy from solution with mag-
netic field after adsorption or desorption. Chandra et al. (2010) used
magnetite reduced graphene oxide (M-RGO) composites as adsor-
bent and reported that arsenic (V) ion removal on the M-RGO
surface was due to the electrostatic attraction while As (III) ion
removal was due to the surface complexation. In the case of As (V)
at pH < pHzpc (pHzpc: zero potential charge) signifying more
availability of positively charged M-RGO surface that favoured the
increased adsorption rates. While in the case of As (III) at
pH > pHzpc signifying more availability of negatively charged
arsenic species rather than positively charged M-RGO surface that
reduced adsorption rates.
2.1.7. Carbon nano tubes
Carbon nanotubes (CNTs) provide sufficient adsorption sites as
well act as a good supporting material for other adsorbents (Ma
et al., 2013). Very few studies on the use of CNTs have been re-
ported for arsenic removal. CNTs are highly porous and have hollow
structure. Large specific surface area, light mass density, purity and
strong interaction between CNTs and pollutant molecules made the
CNTs extensively studied adsorbent. Inspite of these favourable
properties of CNTs, the adsorption capacities of metal ions using
raw CNTs are very low, but it can be significantly increased after
oxidizing the CNTs using HNO3, NaClO and KMnO4 solutions (Fu
and Wang, 2011). CNTs in different forms (single walled or multi-
walled, closed or open-ended CNTs) have been used for removal
of various contaminants. For better adsorption, CNTs modification
technique must be selected according to the contaminant of in-
terest. Metal oxides-decorated materials combine the adsorption
characteristics of metal oxides and the extraordinary properties of
CNTs, such as large surface area, uniformly distributed pores and
presence of functional groups on the surface (Chen et al., 2013).
Inspite of these spectacular properties, the use of CNTs as adsorbent
may also have serious concerns about the health and environ-
mental risks of iron oxide/CNTs once they are released into the
environment. These issues may ultimately hinder the scope of
practical applications of the iron oxide/CNT composites if the risk
assessment would not be considered before selecting it as
adsorbent.
Fig. 1. Pathways of adsorption process.
2.1.8. Others
2.1.8.1. Iron doped phenolic-resin based activated carbon.
Sharma et al. (2010) synthesized Fe-incorporated spherical beads
(PBFe) of particle size 0.2e1 mm and carbonized that followed by
activation. After that they crushed it with ball mill to a particle size
of approximately 100 nm. Crushing of beads provides more and
rough surface area that accelerates the adsorption of arsenic.
2.1.8.2. Iron cross-linked alginate nanoparticles. Singh et al. (2014)
used alginic acid that originates from brown seaweeds and has
high affinity towards divalent cations. Each divalent metal ion binds
two carboxyl groups of adjacent alginate molecules (Nestle and
Kimmich, 1996). Pre-treatment or doping of alginic acid with cat-
ions like Ba2þ, Fe2þ and Ca2þ allows interaction of anionic species of
arsenic with the alginate moiety.
2.1.8.3. Dendrimers. No systematic investigations on hydrolytic,
oxidative, photochemical and biological stability of dendrimers
nanomaterials have been reported so far. Sun et al. (2006) reported
application of dendritic polymers that showed good adsorption
capacities for silver, mercury and copper, but for arsenic removal its
application is not well known. But as dendritic polymers can effi-
ciently be recovered and the adsorbed ions/contaminants can be
recycled easily, so it may a potential adsorbent for the arsenic
removal from drinking water. Overall studies suggest that non-
toxic and biodegradable dendrimers can be synthesized through
a judicious selection of the dendrimer building blocks (e.g. core and
terminal group) (Savage and Diallo, 2005).
3. Adsorption process of nanoparticles
According to Gulipalli et al. (2011), the process of adsorption
occurs either in single step or in combination of the steps such as
film or external diffusion, pore diffusion, surface diffusion and
adsorption on the pore surface. It was also reported that adsorption
of arsenite and arsenate on the adsorbent surface proceeds in three
steps: (1) migration to the surface, (2) dissociation (or deprotona-
tion) of complexed aqueous arsenate or arsenite, and (3) surface
complexation (Zhu et al., 2009; Kong et al., 2014). Fig. 1 illustrates
the common pathways of adsorption process. Adsorbate (arsenate/
arsenite) is diffused on external surface of the adsorbent (nano
adsorbents) due to diffusion potential characterized by the con-
centrations of adsorbate and available external surface area on the
adsorbent (Fig. 1). After diffusion on the external surface of the
adsorbent, adsorbate is diffused on the available pores of the
 S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406 391

adsorbent. All the available exposed active sites, are occupied
during the adsorption process governed by either physisorption or
chemisorption. Saha and Sarkar (2012) reported that electrostatic
adsorption and complexation govern the adsorption behaviour of
arsenic on alumina loaded polymer beads. Badruzzaman et al.
(2004) supported Fick's second law of diffusion (i.e. adsorption
rates are inversely proportional to the square of the particle radius);
according to that adsorption kinetics is faster for smaller particles.
Malana et al. (2011) used nano aluminium doped manganese
copper ferrite polymer as adsorbent and reported that adsorption
followed the Fick's second law. However, according to Vignola et al.
(2005, 2008) it is not applicable to all types of adsorbent. For
example, though the small zeolite particles have high surface area,
but adsorbate diffuses onto adsorption sites more quickly on larger
crystals (Intra-crystalline) rather than smaller one and gives better
and quicker diffusion followed by adsorption. Pena et al. (2006) and
Kong et al. (2014) reported formation of inner sphere surface
complex during adsorption of both the arsenic species.
4. Challenges in handling nano adsorbents
4.1. Use of supporting materials
Most of the nanomaterials are usually synthesized as suspen-
sions in aqueous solution and are available only in fine powder
forms. Therefore, it is not suitable to use these fine powders in
column applications, because of their low hydraulic conductivity
(Zeng, 2003; Theis et al., 1992). Because of smaller particle size,
nano adsorbents cannot be applied in fixed-bed columns unless
they are granular in shape or supported on relatively larger size
porous materials such as polymers, sand, parent materials of used
nano adsorbents, activated carbon etc. But selection of suitable
supporting materials for nanoparticles is also problematic. For
example, for metal oxides it is difficult to obtain spherical beads of
suitable size for practical applications, so it is required to think of
other supporting options instead of preparing beads as supporting
materials (Balaji and Matsunaga, 2002). Many researchers studied
supporting materials and some of them found good results.
Different holding materials reported in the available literature so
far have been compiled and presented in Table 1. In general, re-
searchers used packaging materials such as glass wool or glass
beads to reduce the fast flow of nanoparticles through column, but
it is not sufficient to check or reduce the flow of nanoparticles along
with water in the effluent for sufficient period of time. The non-
uniformity in flow of treated water cause channelling and fouling
of the bed. Another study on holding material (composite gels) for
nanoparticles reported that composite gels have unique structure
of interconnected large pores, mechanical stability and low flow
resistance. In that study nanocomposite devices showed excellent
capability for the removal of trace concentrations of As (III) from
solution with a total capacity up to 3 mg As/g of nanoparticles
(Savina et al., 2011). Montmorillonite as a support material was
found useful on tailoring the dispersion and the aggregation
behaviour of magnetite nanoparticles, and thus facilitates pelleti-
zation, storage, and some related applications. Polyacrylamide has
been found as a suitable backbone to use even in mixed ion con-
taining waste water for treatment applications in various studies
€
(Lozinsky et al., 2003; Kirsebom et al., 2009; Onnby et al., 2012).
Some authors in their studies found that holding material itself
assisted in adsorption that enhanced the adsorption capacity of the
adsorbent. For example, chitosan-graft-polyacrylamide (CTS-g-PA)
was used as supporting material by Saha and Sarkar (2012) and
observed that the supporting material participated in adsorption
along with alumina nanoparticles. Zeolites (hydrated aluminosili-
cate solids with a cage-like structure) also offered large internal and
external surface area for ion exchange. Attia et al. (2012) performed

Table 1
Different supporting materials used for nano adsorbents.

S. No. Adsorbent Supporting material References Contact media

1 2 3 4 5

1 Nanoscale aluminium oxides Mesoporous silica media (SBA-15) Jang et al. (2003) Batch
2 Iron hydroxide Activated Al2O3 Hlavay and Polya k (2005) Column
3 Nanoscale zero-valent iron Polypropylene copolymer centrifuge tubes Kanel et al. (2005) Batch
4 Ceria nanoparticles Carbon nanotubes Peng et al. (2005) Batch
5 Nanocrystalline titanium Poly-ethylene terephthalate (PETE) Pena et al. (2006) Batch
6 Nanocrystalline titanium Immobilization on Sand Deedar et al. (2009) Batch
7 Nano-iron (hydr) oxide impregnated Lignite-based GAC Hristovski et al. (2009) Batch
granulated activated carbon
8 Cupric oxide nanoparticles Polypropylene centrifuge tubes Martinson and Reddy (2009) Batch
9 Nanoscale zero-valent iron Activated carbon Zhu et al. (2009) Batch
10 Fe3O4 nanoparticles Ascorbic acid coating Feng et al. (2012) Batch
11 Iron doped phenolic resin based Glass beads Sharma et al. (2010) Packed bed column
activated carbon nanoparticle
12 Bimetal oxide magnetic nanomaterials Polypropylene bottles Zhang et al. (2010) Batch
13 Aluminium Substituted Manganese Polymer Malana et al. (2011) Batch
Copper Ferrite
14 Nano P(4-Vinylpyridine)-based hydrogels P(4-VP) (nanocomposites) Sahiner et al. (2011) Batch
15 Iron nanoparticle-embedded macroporous Macroporous polymer gel Savina et al. (2011) Column
polymer composites
16 Magnetic nanoparticles coated zeolite Zeolite Attia et al. (2012) Batch
17 Aluminium nanoparticles (Alu-NPs), Polymer €
Onnby et al. (2012) Column
molecular imprinted polymers (MIP-cryo)
18 Alumina nanoparticle in Chitosan grafted polymeric beads Saha and Sarkar (2012) e
chitosan-graft-polyacrylamide (CTS-G-PA)
19 Cupric oxide nanoparticles Polypropylene centrifuge tubes (batch), Reddy et al. (2013) Column
sand layer (column)
20 Nanoscale FeeMn binary Oxides loaded Zeolite Kong et al. (2014) Batch
on zeolite
21 Iron cross-linked alginate nano adsorbent Glass wool Singh et al. (2014) Fixed-bed column
22 Fe-hydrotalcite supported magnetite Fe-hydrotalcite Türk and Alp (2014) Column
nanoparticle
392 S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406
the adsorption of arsenic onto magnetic nanoparticles coated on
zeolite (MNCZ) and observed rapid adsorption due to electrostatic
attraction of iron oxides. The high surface area of zeolite mineral
and protonated iron-oxide at low pH both participated in
enhancing adsorption of negatively charged oxyanionic arsenic
(AsO2
4 ) species. Cumbal et al. (2003) studied polymers as sup-
porting material for inorganic nanoparticles. In their study they
reported two classes of polymer-supported nanoscale particles: (i)
Magnetically Active Polymeric Particles (MAPPs), and (ii) Hydrated
Fe (III) Oxide (HFO) dispersed polymeric ion exchanger. Although
these are not economically viable, but are reusable and can be
reprocessed over many cycles of operation. In a separate study it
was mentioned that if an adsorbent has low solubility product then
it may be considered as a better filtration medium (Basu and Ghosh,
2011). Ghasemzadeh et al. (2014) emphasized the use of natural
nanomaterials such as allophane nano clay, surface-modified
smectite that are available at geological and pedological origins
and may reduce the environmental risk of nanoparticles. Separa-
tion and recovery of nano adsorbents remained a challenge after
their use.
4.2. Separation of nanomaterials
In the available literature, there are several reported methods
for separation of nanoparticles after establishment of the equilib-
rium during adsorption process such as magnetic separation,
filtration and centrifugation method. Separation of nanoparticles
from aqueous solution depends on their nature. The separation
methods adopted by different researchers are shown in Table 2.
Magnetic separation technique has been used to separate magne-
tite nanoparticles using magnetic field column separator consisting
of a stainless steel column (Chandra et al., 2010; Khodabakhshi
et al., 2011). Generally, magnetic nanoparticles contain magnetic
elements such as iron, nickel, and cobalt. These types of nano-
particles can be separated from water easily by high gradient
magnetic separation (HGMS) technique (Ali, 2012). In HGMS
method, the separation of nanoparticles depends on magnetic field
gradients, magnetic properties, and size of the nanoparticles
(Moeser et al., 2004). Mostly iron nanoparticles can be separated by
magnetic separation since they have very good magnetic property
(Nassar, 2012). Considering size and type of membranes, the pro-
cess of filtration has been selected by many researchers for sepa-
ration of akaganeite, carbon nanotubes supported ceria
nanoparticles, Fe3O4, nanocrystalline hybrid surfactanteakaganeite
and FeO nanoparticles (Deliyanni et al., 2003; Deliyanni and Matis,
2005; Deliyanni et al., 2006; Di et al., 2006; Niu et al., 2005). The
centrifugation separation of nanoparticles have been found more
effective method for non-magnetic nanoparticles due to its high
efficiency, capability of scalable production, free of nanoparticles
aggregation and the high density (Chen et al., 2010; Bai et al., 2010).
Generally, a centrifuge with a speed of 20,000e50,000 rpm is
capable of removing nanoparticles from water. External magnetic
field and membrane filtration methods have been used frequently
for the separation of nanoparticles from aqueous solution (Ali,
2012). Separation by filtration has been done by various re-
searchers using membrane filter of 0.45 mm (Table 2).
4.3. Regeneration of nano adsorbents
For practical use of an adsorbent, the regeneration of the
adsorbent material is very important to reduce the cost. After
adsorption of arsenic, the adsorbent gets exhausted. For reuse of
the adsorbent and to recover the adsorbate (arsenic) for safe
disposal of the pollutant, regeneration is required. The primary
objective of regeneration is to restore the adsorption capacity of the
exhausted adsorbent while the secondary objective is to recover
valuable components present in the adsorbed phase. Regeneration
of adsorbents makes the adsorption process economically viable.
Ali (2012) observed the crucial role of pH in regeneration of ad-
sorbents. From the pH study, it has been found that the adsorption
of cations is negligible in the acidic solution and vice-versa for
anions. Therefore, desorption could be easily performed by
adjusting the solution pH. After regeneration, nano adsorbents can
be reused for removal of metallic pollutants, because in many of the
cases they are able to retain their adsorption capacity (Sharma et al.,
2010). Nano sized iron-oxide-coated quartz (IOCQ) was regenerated
using HCl (Mostafa and Hoinkis, 2012). While alkalis are found to be
more efficient desorbing agents for regeneration of chemical ad-
sorbents or chemically modified adsorbents (Lata et al., 2015). In
most of the available literature, NaOH was found as an effective
regenerating agent for regeneration of nano adsorbents. In another
desorption study, 25e30% loss was found in adsorption capacity
after each desorption cycle for As (V) from akaganeite nanocrystals
(Deliyanni et al., 2003). Only 75% of the adsorbed metal could be
recovered during a desorption study of arsenic from zerovalent iron
onto activated carbon and activated carbon impregnated with nano
zerovalent iron adsorbents using 0.1 M NaOH solution (Zhu et al.,
2009). Zhang et al. (2012) regenerated synthetic FeeCu binary ox-
ide after 4 cycles and found that after regeneration, the reduction in
adsorption capacity for As (V) was only 6.2% and that for As (III) was
only 10.6%. That study found NaOH as an efficient regenerating
agent for FeeCu binary oxide. Another regeneration study using
NaOH (0.05 M) gave even better results with only 6% reduction in
adsorption capacity during the regeneration of CTS-g-PA (Saha and
Sarkar, 2012).
5. Comparison of arsenic removal using different nano
adsorbents
Use of nano adsorbents for arsenic removal from contaminated
groundwater emerged as a very promising method in recent years.
Nano adsorbents of various elements like iron, titanium oxide, and
iron oxides are found to be comparatively more effective than
macro sized adsorbents (Waychunas et al., 2005; Ferguson et al.,
2005; Auffan et al., 2008). To help the scientific community, a
detailed comparative study for selecting suitable nano adsorbent
for arsenic removal has been presented in Table 2. In the year 2003,
Deliyanni et al. worked on nano adsorbents and compared various
nano adsorbents (such as hydrous iron oxide, ferrihydrite, goethite,
hydrous ferric oxide, fly ash etc.) and found that at pH 7.5, arsenic
removal (100e120 mg As (V)/g) using akaganeite was compara-
tively better than other nanoparticles. Kanel et al. (2005) used nano
zero valent iron (NZVI) and found removal efficiency of 3.5 mg/g for
1 mg/L (As III) of initial concentration. But for As (V), they found
100% adsorption capacity using the adsorbent dose of only 0.1 g/L
(Kanel et al., 2006). They also found that NZVI resulted best per-
formance in acidic and neutral pH. They compared the performance
of micron ZVI and NZVI and found that though the removal kinetics
of both were similar, but NZVI removed at faster rate and adsorbed
As (V) over a wide pH range through the co-precipitation of various
iron oxide corrosion products. Again Zhu et al. (2009) used nano
zero valent iron (NZVI) along with activated carbon as a holding
media (the majority of the NZVI particles used are less than 100 nm
in diameter) to remove arsenic from aqueous solution. Study of
adsorption capacity resulted 18.2 mg/g of adsorbent for arsenite
and 12.0 mg/g for arsenate at pH 6.5. NZVI with activated carbon
was recommended as an effective adsorbent compared to other
available adsorbents, but interferences due to the presence of ions
like phosphate, silicate decreased the adsorption capacity that
limits its use. Another study of arsenate adsorption was carried out
Table 2
Comparative study of nano adsorbents using various parameters.

S.N. Adsorbents Dia. (nm) Preparation Initial conc. Adsorption Parameters Separation Authors Remarks
method capacity technique

1 2 3 4 5 6 7 8 9 10

Iron oxy/hydroxide nanoparticles

1 Akaganeite (b-FeO 2.6 Precipitation 5e20 mg/L As (V) 100e120 mg As Temperature 298 K, 0.45 mm membrane Deliyanni et al. Akaganeite can be
(OH)) nanoparticle (V)/g pH-7.5, AD0.5 g/L filter (2003) regenerated upto 3
or 4 cycles after
that it loses 25e30%
of its adsorption
capacity.
2 Nano zero-valent 1e120 FeCl3$6H2O 1 mg/L (As III) 3.5 mg/g BET surface area 0.45 mm membrane Kanel et al. (2005) Greater conc.
iron (NZVI) reduction by NaBH4 37.2 m2/g, AD 1 g/L, filter (>100 mM) of
pH 6.5, Temp. 25  C, competing ions

S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406

CT 12 h. such as NO 2
3 , SO4 ,
and HCO 3 did not
have significant
impact on As (III)
adsorption, but
H4 SiO04 and H2 PO24
reduced adsorption
capacity to zero.
The study also
considered
desorption. Results
of the study
revealed the nano
adsorbent can be
used for in situ
remediation.
3 Nano zero valent 30 FeCl3$6H2O 1 mg/L As (V) 100% As (V) AD 0.1 g/L, pH 7, e Kanel et al. (2006) The competing ions
iron Reduction by Temp. 25  C such as HCO3 , SO2 4
NaBH4 and NO 3 did not
interfere
significantly, but
H4 SiO04 and H2 PO24
reduced the
adsorption capacity
of As (V).
4 Nano zero valent <100 Chemical reduction 2 mg/L 18.2 mg/g (As III) pH 6.5, AD 1 g/L, 0.2 mm membrane Zhu et al. (2009) Arsenate,
iron supported on and 12.0 (As V) Temp. 25  C, CT filter phosphate, and
activated carbon mg/g 72 h. silicate competed
for similar binding
sites. Hence
interference of
these ions
decreased the
adsorption of
arsenic. Adsorbent
showed better
efficiency for hard
water. NZVI/AC can
be effectively
regenerated by
(continued on next page)

393
Table 2 (continued )

394
S.N. Adsorbents Dia. (nm) Preparation Initial conc. Adsorption Parameters Separation Authors Remarks
method capacity technique

1 2 3 4 5 6 7 8 9 10

elution with 0.1 M

NaOH.
5 Maghemite Fe2O3 3.8 (MM), 12.1 Mechano-chemical 1e11 mg/L 50.0 mg/g (MM), AD 0.06(MM), 0.1 mm membrane €rvi et al.
Tuutija It is economic and
(SM), 18.4 (CM) and solegel 25.0 mg/g (SM), 0.1(SM), 0.25(CM) filter (2010) efficient for
method 16.7 mg/g (CM) g/l, pH-3, 200 rpm, arsenate removal
50 h. due to its easy
separation after
adsorption.
6 Magnetite 20e40 Commercial-ly 1.5 mg/L for both 3.69 mg/g for As pH 2, AD 0.4 g/L 0.2 mm Nalgene Chowdhury and Electrostatic
maghemite available arsenic species (III) and 3.71 mg/g Surfactant Free Yanful (2010) attraction between
nanoparticles for As (V) Cellulose Acetate arsenic and

S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406

(SFCA) syringe adsorbent caused
filters. the removal of
arsenic. The
adsorbent was
found effective at
pH 6.5e8.5 of
groundwater.
Higher adsorbent
dose of magnetite-
maghemite
mixture
nanoparticles
reduced the
competing effect of
phosphate for
adsorption site.
7 Iron-doped 100e500 Suspension <20 mg/L ~15 and 5 mg/g for pH 5.5e6.5 As (V) 0.45 mm filter paper Sharma et al. (2010) Iron doping during
activated micro/ polymerization As (III) and As (V) and pH 6.5e7.5 As the preparation of
nano carbon (III), AD 5 g/L activated carbon
particles was found more
effective than
adding it into an
already prepared
activated carbon. It
is comparatively
better adsorbent as
it can remove As in
the pH range of 6.5
e8.5 or drinking
water.
8 NZVI 10e100 Reduction of ferric 1e30 mg/L (As III) 99.9% AD 1 g/L, CT 10 min 0.45 mm membrane Rahmani et al. Nanoparticles of
chloride by sodium and pH-7 filter (2011) zero valent iron has
borohydride better removal
efficiency than
micro zero valent
iron.
9 Nanocomposite 30e20 Cryo 2 mg/L (As III) ~9 mg As(III) per g pH 3e9 Centrifuge Savina et al. (2011) Though holding
gels containing a- Polymerisation of Fe particles (for material reduced
Fe2O3 and Fe3O4 free nanoparticles). the adsorption
nanoparticles ~3 mg As(III) per g capacity, yet it was
of Fe particles (for found to be
nanoparticles excellent
 embedded in supporting
macroporous gel) material. The effect
of competing ions
such as SO24 and
PO3
4 was
negligible. Small
decrease in As (III)
adsorption was
observed at
pH > 10.
10 Magnetic 10e20 Ultra sonication 20 mg/L, 95.6% within pH 2.5, AD 0.5 g/L. 50 nm filter film Attia et al. (2012) Adsorption using
nanoparticles 15 min. this adsorbent is
coated zeolite highly pH
dependent.
Adsorbent can be
reused upto 5
cycles without

S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406

losing its initial
adsorption capacity
after regeneration
with NaOH.
11 Ascorbic acid <10 Hydrothermal 0.10 mg/L 16.56 mg/g As (V) BET surface area External magnetic Feng et al. (2012) It has excellent
coated Fe3O4 and 46.06 mg/g As 179 m2/g, AD field arsenic removal
nanoparticles (III). 0.06 g/L, pH-7, CT potential. Ascorbic
0.5 h acid coated Fe3O4
nanoparticles
prevented the
leaching of iron into
the aqueous
solution.
12 Activated carbons 3e36 Hydrolysis of FeCl3 0.025e1.5 mg/L 0.37e1.25 mg/g pH 6e8, AD 0.75 g/ e Vitela-Rodriguez F400-M was found
modified with iron (for F400-M- L, BET surface area (2013) as the most
hydro (oxide) 0.85 mg/g) (As V) 1045 m2/g (for effective with
nanoparticles. F400-M). compared to other
adsorbents. But
anions (present in
groundwater) such

as SO2
4 and Cl
decreased the
adsorption
capacity.
Regeneration of
nano adsorbent
was not considered.
13 Fe-hydrotalcite 50 Co-precipitation 0.1e2.0 mg/L. As (V) and As (III) AD 5 g/L, pH 9 Magnetic separator Türk and Alp (2014) Fe-hydrotalcite
supported method. on M-FeHT 1.28 supported
magnetite and 0.12 mg/g magnetite showed
nanoparticle respectively. better adsorption
efficiency as well as
easy separation.
Aluminium oxide nanoparticles
14 Mesoporous silica 5.9 Incipient wetness 9.96e99.64 mg/L. 94% of arsenate pH 6e8, AD 2 g/L, 0.45-mm Uniflo Jang et al. (2003) Al10SBA-15 showed
media (SBAe15) impregnateon adsorption Temp.25  C ± 0.5  C filter unit almost 10.5 times
in12 min. higher adsorption
capacity than
activated alumina.
(continued on next page)

395
Table 2 (continued )

396
S.N. Adsorbents Dia. (nm) Preparation Initial conc. Adsorption Parameters Separation Authors Remarks
method capacity technique

1 2 3 4 5 6 7 8 9 10

Impregnation
techniques should
be attempted to
avoid the
heterogeneity of
pore structures and
to enhance the
surface hydroxyl
density. Only
arsenate was
considered for

S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406

removal.
15 Al2O3/Fe(OH)3 4.7e11.1 Precipitation 7.5 and 29.9 mg/L 3.89 mg/g (As III), AD 2.5 g/L, pH 6.6 0.45 mm pore size Hlavay and Poly
ak The adsorbent is
for As (III) and As 36.63 mg/g (As V) e6.7 (As III), pH filter paper (2005) mechanically and
(V) 7.15e7.2 (As V), chemically stable,
BET surface area efficient, and
95.7 m2/g, helped in selective
adsorption of
arsenate and
arsenite ions. The
adsorbent can be
directly filled in
columns. Low
waste technology
can be developed
after regenerating
the Fe(OH)3 active
layers.
16 Aluminium <50 (Alu-NPs), <38 Polymerization 5e100 mg/L (For 20.3 ± 0.8 mg/g pH 2e8, BET e €
Onnby et al. (2012) In comparison to
nanoparticles (Alu- (MIP-cryo) followed by colum–n study 5 (Alu-cryo) and surface area Alu-NIPs, MIP-cryo
NPs), molecular coupling and 10 mg/L) 7.9 ± 0.7 mg/g, 269.55 m2/g (NIPs) provided good
imprinted (MIP-cryo), for As mechanical
polymers (MIP- (V) respectively. strength, but
cryo) adsorption capacity
was low. It did not
have significant
effects at lower
concentration
range (Ce < 10 mg/
L). Alu cryo gave
comparatively
better results but
still it needs some
improvements.
17 Alumina 200e600 Reverse micro 25e80 mg/L 6.56 mg/g As (V) Optimum pH 7.2, e Saha and Sarkar 0.05 M NaOH was
nanoparticle in emulsion method Temp. 30  C (2012) found to be the
chitosan-graft- most suitable
polyacrylamide desorption agent
(CTS-G-PA) since it could
recover almost
100% without
deforming the
beads.
18 Nano-alumina 22e36 Precipitation 10 and 20 mg/L 40 mg/g (As III) pH-7.5, AD 1 g/L, CT Centrifuge Darban et al. (2013) Instead of using
powder method 30 min. BET surface expensive activated
area 201.53 m2/g. alumina they
prepared nano
meso alumina
particles from raw
inexpensive kaolin
clay that showed
better adsorption
capacity for arsenic.
Copper oxide nanoparticles
19 CuO nanoparticles 12e18 Microwave 0.1e100 mg/L. 26.9 mg/g As(III), pH 6e10, CT Centrifuge Martison and The presence of
irradiation 22.6 mg/g As (V) 30 min, AD 2 g/L, Reddy (2009) sulphate and
Temp. 21e25  C. silicate in water did
not inhibit
adsorption of As
(V), but slightly

S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406

inhibited
adsorption of As
(III). High
concentrations of
phosphate
(>0.2 mM) reduced
the adsorption of
arsenic onto CuO
nanoparticles.
20 Copper oxides 40,50e150 Thermal refluxing 0.1e1 mg/L 1.08 mg/g BET surface area e Goswami et al. This adsorbent was
nanoparticles technique 52.11 m2/g, pH > 8, (2012) found highly pH
AD 1 g/L, Temp. dependent. After
25 ± 2  C regeneration good
adsorption
efficiency was
found.
Titanium oxides nanoparticles
21 Nanocrystalline 6 Hydrolysis 1.0 mg/L As (V) or >98% As (V) pH 4e9.5 As (V), pH Centrifugat-ion at Pena et al. (2006) Study suggested
titanium dioxide As (III) 95% As (III) 9.5 As (III), BET 13,000 rpm for TiO2 as an effective
surface area 35 min. adsorbent for As
329 m2/g, AD removal due to its
0.2 g/L high surface area
and the presence of
high affinity surface
hydroxyl groups.
22 Titanium dioxide 108e65 Solegel method 5e90 mg/L 70%, 85% and 95% pH 1e2, AD 0.1 2-mm syringe filter Deedar et al. (2009) Iron doping with
(TiO2) with GPR, pure and e4 g/L titanium oxide
nanoparticles iron-doped TiO2 increased the
respectively. adsorption
potential of metal
oxide. It can also be
tried for other
inexpensive and
easily available
metal oxides.
Adsorption of As
(V) was more than
that of As (III).
Zinc oxide nanoparticles
23 6e60 Solegel method 2 mg/L 99.9% Singh et al. (2012)
(continued on next page)

397
Table 2 (continued )

398
S.N. Adsorbents Dia. (nm) Preparation Initial conc. Adsorption Parameters Separation Authors Remarks
method capacity technique

1 2 3 4 5 6 7 8 9 10

Acetate pH 5.8e6.8, AD Whatman filter Adsorbent was

functionalized zinc 2 g/L paper no. 42 or by found efficient in
oxide nano Buckner funnel. drinking water pH
materials range, so need not
to maintain pH in
field condition.
Mixed metal oxides nanoparticles
24 MnFe2O4 nano- 12 Microwave assisted 0.1 mg/L As (III) or 0.72 mg/g for As AD 2.5 g/L, Centrifuge-d at Parsons et al. The binding of As
adsorbents hydrotherma-l As (V) (III) and 2.13 mg/g independent of 3000 rpm for 5 min (2009) (III) or As (V) with
Method for As(V) (with studied pH (pH 2 the surface of the
MnFe2O4) e6) MnFe2O3 nano

S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406

adsorbent resulted
in higher binding
capacities because
of the possible
different electron
transfers from
either Mn or Fe
ions, which in turn
resulted in less
dissolution of the
mineral phase.
25 Nanostructure 16e21 e 5e10 mg/L 9.36 ± 0.31 mg/g pH 7, AD 2 g/L 0.45 mm membrane Gupta et al. (2009) The toxicity
Iron(III)- filters leaching
Zirconium(IV) characteristic
Bimetal Mixed procedure test
Oxide showed As (III)-
NHIZO as non-
hazardous waste.
26 Magnetite reduced 10 Chemical reduction 0.001e5 mg/L Over 99.9% arsenic at low External magnetic Chandra et al. High binding
graphene oxide removal within temperatures field. (2010) capacity was
(MRGO) 1 ppb (<100  C) observed for both
composites As (III) and As (V).
Adsorption
capacity increased
due to more
adsorption sites in
presence of the
reduced graphene
oxide. Super
paramagnetic
nature of the
adsorbent helped in
easy separation
after adsorption.
27 Bimetal oxide 30e50 (MnFe2O4), Chemical-co- 10 mg/L 94 mg/g (As III) and pH 3.0 As (V), pH Magnetic Zhang et al. (2010) Assisted in removal
magnetic 10e30 (CoFe2O4) precipitation 90 mg/g (As V) for 7.0 As (III), AD 0.2 g/ separation of wide range of
nanomaterials: and 10e20 (Fe3O4) MnFe2O4 and 100 L, temp. 25  C initial arsenic
MnFe2O4 and and 74 mg/g (As III) concentrations (0.5
CoFe2O4 and (As V) with e50 mg/L).
CoFe2O4 Desorption study
showed that over
80% of the As (III)
 and 90% of the As
(V) could be
desorbed from
MnFe2O4 with
0.1 M NaOH
solution. Phosphate
and silicate were
found to be
powerful
competitors with
arsenic for
adsorptive sites of
the adsorbent.
28 Synthetic 20e30 Chemical 7.5 and 9.7 mg/L 5.20 mg/g (in Removal capacity of e Basu and Ghosh Solubility products
nanostructured precipitation presence of HCO
3) As (III) enhanced (2011) (Ksp) of Fe and Cr
hydrous Fe (III) with increasing pH metal oxides were
eCr(III) (NHICO) from 3.0 to 7.0, AD low and hence

S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406

mixed oxide 1 g/L, CT 2 h. were found suitable
as safe filtration
medium.
Bicarbonate ion
showed positive
effect on As (III)
adsorption by this
adsorbent.
29 Nano aluminium 13 Chemical co- 0.02e0.2 mg/L 0.05 mg/g pH 6.0, AD 3.3 g/L, e Malana et al. (2011) Preparation of
doped manganese precipitation Temp. 313 K adsorbent is
copper ferrite Rotation 120 economical.
polymer strokes/min90 min.
(MA, VA, AA)
Composite
30 Synthesized nano- 50 Co-precipitation ~10 mg/L 82.7 mg/g (As V), pH-7, AD 0.2 g/L, 0.45 mm membrane Zhang et al. (2012) Effective for
structured FeeCu method 122.3 mg/g (As III) BET surface area filter adsorption of both
binary oxides 282 m2/g. As (III) and As (V).
The adsorbent gave
better adsorption
capacity at drinking
water pH range and
competing ions did
not hinder the
adsorption.
Regeneration was
easy using NaOH.
31 Nanoscale FeeMn 10e20 e 2 mg/L 296.23 and BET surface area 0.45 mm membrane Kong et al. (2014) The adsorption of
Binary Oxides 201.10 mg/g for 126 m2/g, AD 5 g/L, filter both As (III) and As
Loaded on Zeolite As(III) and As(V) Temp. 25  C, and (V) decreased with
pH 7.0 increased pH. The
anions of SiO2
3 ,
H2 PO4 , and HCO3


significantly
competed with
arsenic for the
adsorption sites.
Carbon nanotubes
32 Magnetic iron ~11 One-pot method e ~9.74 mg/g of As(V) BET surface area magnetic Ma et al. (2013) Though column
oxide/CNT and ~8.13 mg/g of ~662.1 m2/g, pH study was not done,
composites As(III) 4(As V) 7.5 (As III) but the authors
recommended its
(continued on next page)

399
Table 2 (continued )

400
S.N. Adsorbents Dia. (nm) Preparation Initial conc. Adsorption Parameters Separation Authors Remarks
method capacity technique

1 2 3 4 5 6 7 8 9 10

possible use in
large scale
application.
33 CeeFe mixed oxide 20e30 Catalytic chemical 5 mg/L 30.96 mg/g (As V), BET surface 0.45 mm membrane Chen et al. (2013) Though adsorbent
decorated vapor deposition 28.74 mg/g (As III) 216.3 m2/g, AD has significant
multiwalled carbon 0.2 g/L potential for
nanotubes arsenic removal but
practical
applicability is yet
to be explored.
34 Multiwall carbon 20e40 e 0.1 mg/L 2 mg/g (As III), pH 6, CT 6 h, BET 0.45 mm membrane Natim and Mitra No effect of

S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406

nanotubes zirconia 5 mg/g (As V) surface 152 m2/g syringe filter (2012) competing ions on
nano hybrid arsenate was
observed, but
arsenite removal
efficiency
decreased due to
the presence of
sulphate and
nitrate ions.
Adsorption
capacity was
independent of pH
for the initial
concentrations
taken for the study.

Dia.: diameter; Conc.: concentration; nm: nanometer; mM: milli mole, AD: adsorbent dose, CT: contact time, Temp.: temperature.
 S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406
using three different g-Fe2O3 nanoparticles: (a) homemade with
mechano-chemical method (MM 60 mg/L), (b) homemade with
solegel process (SM 100 mg/L), and (c) a commercially available
one (CM 250 mg/L). Adsorption capacities from different methods
were found to be 50 mg/g, 25 mg/g and 16.7 mg/g respectively for
MM, SM and CM. Characterization studies of adsorbent such as
Fourier transform infrared, X-Ray Photoelectron Spectroscopy, X-
Ray Diffraction, Transmission Electron Microscopy and Zeta Po-
tential also supported the investigation of adsorption capacity.
FTIR-spectra analysis revealed that bidentate binuclear complex
[(FeO)2AsO2] was formed at all studied pH values in case of MM and
only at pH 3 for SM and CM. While at pH 5, 7, and 9 with SM and
CM, arsenate formed mono-dentate complex [ðFeOÞAsO 3]
(Tuutija€rvi et al., 2010). Chowdhury and Yanful (2010) synthesized
magnetite maghemite nanoparticles that can readily adsorb arsenic
and chromium in an acidic pH range. The maximum arsenic
adsorption occurred at pH 2 with values of 3.69 mg/g for arsenic
(III) and 3.71 mg/g for arsenic (V) when the initial concentration
was kept at 1.5 mg/L for both the arsenic species using adsorbent
dose of 0.4 g/L. In the same year, Sharma et al. (2010) prepared
polymeric beads incorporated with nanoparticles by suspension
polymerization, and then micro and nano activated carbon particles
impregnated with iron were produced. They found better adsorp-
tion in the pH range of 6.5e7.5. Polymeric beads with nano size
showed good adsorption capacity of 15 mg/g for As (III) and 5 mg/g
for As (V). The interesting result was that no pre and post treat-
ments were required for the adsorbent used in that study. In a
comparative study, Rahmani et al. (2011) found nano zero valent
iron (nZVI) as the better adsorbent than micro zero valent iron
(mZVI). Nano zero valent iron showed removal efficiency of 99.9%
using adsorbent dose of 1 g/L at contact time of 10 min at pH 7 for
initial concentrations of As (III) ranging from 1 to 30 mg/L. Mac-
roporous polymer gel containing nanoparticles of a-Fe2O3 and
Fe3O4 were also found effective for As (III) removal with efficiency
of 3 mg/g at wide range of pH of 3e9 and interference of other ions
were also negligible (Savina et al., 2011). But the holding material
reduced the adsorption capacity. Attia et al. (2012) used magnetic
nanoparticles coated zeolite that resulted 95.6% arsenic removal
within 15 min of contact time at pH 2.5. But effectiveness of
adsorbent at lower pH restricts its use for drinking water. While
Feng et al. (2012) tried with Fe3O4 nanoparticles (diameter of less
than 10 nm) coated with ascorbic acid prepared under hydrother-
mal condition for arsenic removal from waste water in an envi-
ronmental friendly way. They reported that ascorbic acid improved
the dispersibility of Fe3O4 nanoparticles as well as inhibited the
leaching of iron into the solution. The maximum adsorption ca-
pacity was 16.56 mg/g for arsenic (V), and 46.06 mg/g for arsenic
(III). The arsenic removal by this adsorbent was quite impressive
with 97.5% removal efficiency using adsorbent dose of 0.06 g/L. pH
did not have significant effect on removal efficiency except at pH
more than 7 where removal efficiency of the adsorbent decreased
to less than 15%. Activated carbon modified with different modi-
fying agents has also been tried and gave good results. In a study,
different modified activated carbons (bituminous Filtrasorb-400
(F400-M) obtained from Calgon) were used as adsorbents. These
were modified with iron hydroxide/oxide nanoparticles. These iron
modified activated carbons were found as efficient adsorbents for
removal of initial arsenic concentrations ranging from 0.025 mg/L
to 1.5 mg/L. F400-M was found to be the most effective one with
adsorption capacity of 0.847 mg/g. But the presence of anions in

groundwater such as SO2 4 and Cl compete for active sites that
results in decrease in the adsorption capacity. Regeneration of nano
adsorbent was not considered in that study (Vitela-Rodriguez and
Rangel-Mendez 2013). In succeeding year, Türk and Alp (2014)
used magnetic iron hydrotalcite (M-FeHT) nanoparticles that
401
were effective in wide range of initial concentrations for removal of
both arsenite and arsenate. At pH 9, the adsorption capacities were
found to be 1.28 mg/g for As (V) and 0.12 mg/g for As (III).
Aluminium oxides also play an important role in arsenic
removal due to its various nano-structured properties and its low
cost. In the year 2003, it was reported that mesoporous silica media
impregnated with 10% of aluminium by weight (designated as
Al10SBA-15) had almost 10.5 times higher adsorption capacity than
activated alumina. The initial adsorption rate of Al10SBA-15 was 15
times greater than that of activated alumina. As aluminium-
impregnated SBA-15 provides higher adsorption capacity and
rate, it appears to have good potential for arsenate removal. But
impregnation techniques need more improvement to reduce the
heterogeneity of pore structures and to enhance the surface hy-
droxyl density so that it may participate in surface complexation
and ultimately facilitate better arsenic removal (Jang et al., 2003). In
a further study by Hlavay and Polya k (2005), iron hydroxide-coated
alumina was used as nano adsorbent [Al2O3/Fe(OH)3] and Al2O3 as a
support material that removed 3.89 mg/g (As III) and 36.63 mg/g
(As V) considering the parameters such as adsorbent dose of 2.5 g/L
at pH 6.6e6.7 (for As III), at pH 7.15e7.2 (for As V) and BET surface
area (95.7 m2/g). The adsorbent (iron hydroxide-coated alumina)
can be directly filled in columns to make the adsorbent low cost for
arsenic removal because there is no need of supporting material.
€
Onnby et al. (2012) evaluated the adsorption capacity of three ad-
sorbents namely SH-groups coupled with a polymer backbone
containing amine groups (SH-cryo), aluminium oxide nanoparticles
(Alu-NPs) incorporated into cryogels (Alu-NPs cryo), and molecu-
larly imprinted polymers (MIPs) incorporated into cryogels. Design
of NPs or MIPs using composite materials is a promising way to
incorporate small particles which otherwise is difficult to control.
Moreover, composites are easy to handle in large scale treatment
systems due to their compact design. Among the three adsorbents,
Alu-NPs cryo has better adsorption capacity and faster kinetics. The
most studied nano size adsorbent is iron based adsorbents such as
nano zero valent iron and Fe3O4 nanoparticles. Batch study was
performed for wide range of initial arsenic concentrations ranging
from 5 to 100 mg/L, but column study was done taking 7 mg/L of
initial concentration. In column study, Alu-NPs cryo gave compar-
atively better results but still it needs some improvements. The
study indicated that selective adsorbents can be useful when
multiple pollutants are present in raw water for evaluating the
adsorption performance of the pollutant of interest. Saha and
Sarkar (2012) synthesized an adsorbent by dispersing alumina
nanoparticles in chitosan-graft-polyacrylamide (CTS-g-PA). Apart
from studying arsenic removal efficiency, they also studied the
various influencing factors such as contact time, pH, effects due to
the presence of co-ions and regeneration. Polymeric adsorbents
were more efficient in arsenic removal than the nano-alumina and
CTS-g-PA. The adsorption was explained as a result of both chem-
ical and physical interaction. They recommended this as a noble
adsorbent due to three main reasons: (1) lenient operating condi-
tions such as temperature (250  C) and pH 7.2, (2) its high
adsorption capacity, and (3) recyclability. Nano-alumina powder is
also an efficient nano adsorbent as it can remove arsenite without
pre-oxidation of it into arsenate (AseV) from aqueous solution and
it was investigated for an initial concentration of 20 mg/L over a pH
range of 3.5e8.5 as the synthesized nano g-Al2O3 is insoluble and
stable within this range of pH. High adsorption was observed in the
pH range of 5.5e7.5. Maximum removal of arsenite was achieved
within the first 15 min of contact time and equilibrium reached in
30 min. About 97.65% of arsenite removal was achieved within
30 min from the samples containing initial arsenite concentration
up to 10 mg/L at pH 7.5. Adsorption isotherms were observed to be
well fitted with the Langmuir and D-R models and the maximum
402 S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406
adsorption capacity was 40 mg/g (Darban et al., 2013).
Copper oxide has also been used by various researchers for
arsenic removal. In a study, Martison and Reddy (2009) prepared
CuO nanoparticles (surface area of 85 m2/g and diameter of
12e18 nm) and successfully reduced the arsenic level to less than
3 mg/L (0.003 mg/L) in groundwater samples. They found that the
adsorption study using CuO nanoparticles best fitted with the
Langmuir isotherm, resulted in a maximum adsorption capacity of
26.9 mg/g for As (III) and 22.6 mg/g for As (V). At pH 9.3, the highest
percentage of As (III) was removed while As (V) found to be inde-
pendent of pH at the tested pH range. A reaction time of 30 min was
suitable for arsenic adsorption. Sulphate and silicate inhibited
slightly while high concentration of phosphate (greater than
0.2 mM) reduced the adsorption capacity of arsenic onto CuO. In
another study using the same adsorbent, the adsorption capacity of
1.08 mg/g was found. The efficiency of arsenic removal was 100% up
to 0.2 mg/L of initial arsenic concentrations using 1 g/L of adsorbent
dose with a contact time of 300 min, but high pH dependency made
it unsuitable for drinking water treatment. The regeneration of
adsorbent was done using NaOH solution and very low desorption
was observed, indicating strong attraction force between adsorbent
and arsenic. Competing ions such as phosphate and sulphate even
at high concentrations can be removed by copper (II) oxide nano-
particles (Goswami et al., 2012).
Titanium dioxide has also been extensively used for arsenic
removal (Jing et al., 2005; Bang et al., 2005; Lee and Choi, 2002;
Dutta et al., 2004; Pena et al., 2006). In a study for evaluating the
efficiency of nanocrystalline titanium dioxide for arsenic removal
from solution of 1 mg As/L, an experiment was conducted that
resulted adsorption efficiency of greater than 98% for As (V) and
95% for As (III). Titanium dioxide (TiO2) nanoparticles were further
used as adsorbents in various studies to evaluate adsorption po-
tential for removing arsenic from drinking water (Pena et al., 2006).
In a further study, pure and iron-doped TiO2 nanoparticles were
synthesized using solegel method and a comparison was done
using three types of TiO2 nanoparticles. The first one was general
purpose reagent (GPR) TiO2; second one was pure TiO2 and third
one was iron-doped TiO2 in air light (AL) and air dark (AD) and
nitrogen dark (ND) condition at different pH. The synthesized TiO2
nanoparticles were then immobilized on ordinary sand for
adsorption studies. Iron doping enhanced the adsorption capacity
of TiO2 nanoparticles by arresting the grain growth and making it
visible light responsive resulting in a higher affinity for arsenic. TiO2
possesses a high potential for environmental applications due to its
physical and chemical stability, low cost, non-toxicity and the
resistance to corrosion. Immobilized TiO2 nanoparticles on a
naturally available adsorbent like sand coupled with iron-doping
were found as cost effective arsenic treatment technologies. Iron
coated titanium oxide gave better adsorption capacity of 20.8 mg/g
for As (III) and 19.9 mg/g for As (V) in AL system when initial arsenic
concentration was 90 mg/L (Deedar et al., 2009). In another study,
using titanium oxide as adsorbent, a comparison between nano-
particles coated/embedded macroporous composite adsorbents for
As (V) removal was done. That study evaluated that nano sized TiO2
coated perlite (TOCP) has comparatively high adsorption capacity
of 0.41 mg/g in batch experiment (Mostafa et al., 2010).
Acetate functionalized zinc oxide nanomaterials of particle size
6e60 nm found to remove the arsenic upto 99% of initial concen-
tration 2 mg/L (Singh et al., 2012).
Some synthetic nano adsorbents (Fe3O4, Mn3O4, and MnFe2O4)
prepared by microwave assisted hydrothermal methods have also
been investigated for arsenic removal. The binding capacity was
0.03, 0.01, and 0.72 mg/g for As (III) and 1.58, 0.21 and 2.13 mg/g for
As (V) respectively for these adsorbents. But MMO's of MnFe2O4
revealed comparatively higher binding capacity for both the arsenic
species at pH 4, reaction time of 15 min and adsorbent dose of 2.5 g/
L (Parsons et al., 2009) (Table 2). Magnetite reduced graphene oxide
(MRGO) composites removed more than 99.9% arsenic to less than
1 ppb at low temperature (Chandra et al., 2010). Zhang et al. (2010)
used bimetal oxide magnetic nanomaterials (MnFe2O4 and
CoFe2O4) and found adsorption capacity of 94 mg/g for As (III) and
90 mg/g for As (V) with MnFe2O4; and 100 mg/g for As (III) and
74 mg/g for As (V) with CoFe2O4. In this case, pH 3 for As (V) and pH
7 for As (III) with adsorbent dose of 0.2 g/L at temperature 25  C
were found favourable for arsenic removal. Adsorption study
resulted arsenic removal for a wide range of initial concentrations
(0.5e50 mg/L). Desorption study showed that over 80% of As (III)
and 90% of As (V) could be desorbed from MnFe2O4 with 0.1 M
NaOH solution. Phosphate and silicate were found to be powerful
competitors with arsenic for adsorptive sites on the adsorbent.
Basu and Ghosh (2011) prepared synthetic nanostructured hydrous
Fe (III)eCr (III) (NHICO) mixed oxide for removal of arsenic from
aqueous solution. They investigated the effects of incinerating
temperature on NHICO, solution pH, and kinetics of As (III)
adsorption reaction with NHICO(incinerated at 350  C). Incinera-
tion of NHICO at 350  C resulted highest capacity of As (III) removal
at pH 7.0 (±0.2) from aqueous phase. Solubility product (Ksp)
values were found as 5  1038 [for Fe(OH)3] and 1030 [for
Cr(OH)3] at 25  C. Thus, the present material (NHICO) can be used
safely as a filtration medium due to low solubility in water. Malana
et al. (2011) used nano aluminium doped manganese copper ferrite
polymer composite as an adsorbent for removal of arsenic from
aqueous solution. The nano-composite was prepared by addition of
these nano ferrites during co-polymerization of methylacrylate
(MA), vinyl acetate (VA) and acrylic acid (AA) monomers using
ethylene glycol dimethyl acrylate (EGDMA) and benzoyl peroxide
(BPO) as cross linking agent and initiator respectively. The
maximum adsorption capacity on the nanocomposite was found to
be 0.053 mg/g. Freundlich model was found a better fit indicating
heterogeneous surface of the adsorbent. Adsorption of arsenic on
the nanocomposite followed pseudo-second order kinetics. For
evaluation of arsenic removal capacity of nano-structured FeeCu
binary oxides, a study was conducted that showed adsorption ca-
pacities of 82.7 mg/g for As (V) and 122.3 mg/g for As (III) at pH 7.
But researches are still in the process of granulating the nano-
structured FeeCu binary oxide particles, which could be readily
used in fixed beds. There were no significant effects of co-existing
ions such as sulphate and bicarbonate, but the higher concentra-
tion of phosphate reduced the arsenic removal (Zhang et al., 2012).
Another study compared macro and nano gels for arsenic removal
efficiency. These macro gels and nano gels were prepared using 4-
vinylpyridine (p-4VP) with redox and micro emulsion techniques.
Various parameters such as size of the absorbent, nature of the
quaternization agent/modifying agent [(double charge forming
agent, 2-bromoethylamine (2-BEA)], treated particles and macro
gels, the initial concentration of arsenic, pH and temperature
affected the adsorption capacity of As (V). Effect of coexisting ions
such as chloride and sulphate ions [(upto 15 mg/L chloride and
sulphate did not have any significant effect on As (V) removal)] have
also been studied. It was found that with nano sized quaternized
(p-4VP)-BE (bromoethane), about 97.1% removal was obtained in
just 15 min. These materials can be used upto 5 cycles with very
high desorption rate (~80% for macro and ~90% for nanomaterials).
Best results were obtained for As (V) removal using nano sized
quaternized (p-4VP)-BE (Sahiner et al., 2011).
Ma et al. (2013) used magnetic iron oxide/CNT composites as
adsorbent and found the adsorption efficiency efficiency of
~9.74 mg/g for As (V) at pH 4 and ~8.13 mg/g for As(III) at pH 7.5.
Chen et al. (2013) used CeeFe mixed oxide decorated multiwalled
carbon nanotubes and reported adsorption efficiency of 30.96 mg/g
 S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406
for As (V) and 28.74 mg/g for As (III) using adsorbent dose of 0.2 g/L.
Natim and Mitra (2012) used multiwalled carbon nanotubes zir-
conia nano hybrid that showed adsorption capacity of 2 mg/g for As
(III) and 5 mg/g for As (V) at pH 6 and contact time of 300 min.
6. Critical discussion
6.1. Effect of pH
Various nano adsorbents such as nano zero valent iron sup-
ported on activated carbon, akeganeite, iron doped activated nano
carbon particles, nano zero valent iron, ascorbic acid coated Fe3O4,
mesoporous silica media, Al2O3/Fe (OH)3, alumina nanoparticles in
chitosan graft polyacrylamide, and nano alumina powder have
been reported to remove arsenic from water at the drinking water
pH range 6.5e8.5. While some nano adsorbents such as maghe-
mites, titanium dioxide (Deedar et al., 2009), and magnetic nano-
particle coated zeolite (Attia et al., 2012) were found to have better
arsenic adsorption capacity at low pH, which are more suitable for
arsenic removal from waste water rather than drinking water. Most
of MMO's nanoparticles have great adsorption capacity for removal
of both the arsenic species and As (III) was found to be removed
more effectively at drinking water pH range.
6.2. Effect of synthesis method
Synthesis of NZVI was done mostly by reduction method (Kanel
et al., 2005, 2006; Zhu et al., 2009; Rahmani et al., 2011; Chandra
et al., 2010). Other adsorbents were synthesized by various
methods such as chemical precipitation (Basu and Ghose, 2011;
Zhang et al., 2012; Zhang et al., 2010; Darban et al., 2013; Hlavay
and Polya k, 2005; Türk and Alp, 2014; Delyanni et al., 2003); hy-
drolysis (Pena et al., 2006; Vitela-Rodriguez and Rangel-Mendez
2013); hydrothermal method (Parsons et al., 2009; Feng et al.,
€rvi et al., 2010);
2012); sol gel method (Deedar et al., 2009; Tuutija
polymerization (Sharma et al., 2010; Savina et al., 2011; Onnby€
et al., 2012) and sonication method (Attia et al., 2012).
Aluminium oxide was prepared by reverse micro-emulsion (Saha
and Sarkar, 2012) or incipient wet impregnation method (Jang
et al., 2003); whereas microwave irradiation method (Martinson
and Reddy, 2009) and thermal refluxing technique (Goswami
et al., 2012) were used for synthesis of copper oxide. Sharma
et al. (2010) prepared iron doped phenolic resin based activated
carbon nanoparticles by polymerisation method. For the
improvement of accessibility of iron to arsenic ions, they incorpo-
rated the iron during polymerization process. Researchers should
innovate other methods too, to improve the accessibility of nano
adsorbents to arsenic ions in an eco-friendly way.
6.3. Effect of initial concentration
Many of the studies have been carried out using batch studies to
understand the maximum uptake of arsenic on nano adsorbents
with high initial concentrations of arsenic to provide maximum
arsenic available for the nano adsorbents. In actual field condition,
groundwater arsenic concentrations may vary from very low con-
centration to very high concentration. In Table 2, various studies on
removal of arsenic concentrations along with their adsorption ca-
pacities are presented. A few authors observed excellent adsorption
capacity for both the arsenic species, in fact more satisfactory re-
sults were observed for As (III) at the drinking water pH range. For
example, adsorption capacities of 296.23 mg/g (for As III) and
201.10 mg/g (for As V) for initial concentration of 2 mg/L at pH 7
(Kong et al., 2014), and adsorption capacities of 122.3 mg/g (for As
III) and 82.7 mg/g (for As V) for initial concentration of 10 mg/L at
403
pH 7 (Zhang et al., 2012) were observed. While Deliyanni et al.
(2003) found adsorption capacity of 100e200 mg/g only for As
(V) at pH 7, but the adsorbent was found efficient to remove arsenic
with initial concentrations varying from 5 to 20 mg/L. From Table 2,
it is clear that aluminium oxides nanoparticles are comparatively
more efficient for the removal of high concentrations of arsenic that
may help in effective removal of arsenic from waste water with
high arsenic content.
6.4. Effect of particle size
Generally adsorption capacity increases with decrease in parti-
cle size, but it is not true for all the adsorbents. For example, zeolite
particles are reported to have high surface area, but adsorption
capacity of larger crystals was found to be more rather than smaller
particles (Vignola et al., 2005, 2008) due to the intra-crystalline
pore structure of zeolite (Rouquerol et al., 2014).
6.5. Effect of competing ions
To study the influence of interfering agents on the arsenic
removal using NZVI, Tanboonchuy et al. (2012) used six species
 2þ 
including SO2 3
4 , PO4 , HCO3 , Ca , Cl , and humic acid (HA) in a
study and concluded that HA, SO4 and PO3
2
4 have inhibitory ef-
fects, but Ca2þ has enhancing effect. Presence of HCO 3 has inhibi-
tory effect on the removal of both the arsenic species. Increased
Ca2þ concentrations and decreased PO3 4 and HA concentrations
create the condition for best removal of both As (III) and As (V). In
arsenic removal, silicate and phosphate were found to have
comparatively more interference (that reduced the adsorption of
arsenic) than NO 2 
3 , SO4 , and HCO3 (Kanel et al., 2005, 2006; Zhu
et al., 2009). While Savina et al. (2011) found negligible effects of
these interfering agents (Table 2). Martison and Reddy (2009), Kong
et al. (2014) and Zhang et al. (2010) also reported the interference of
sulphate, phosphate and silicate in arsenic removal. But for As (V),
their effect was found negligible (Martinson and Reddy, 2009;
Natim and Mitra, 2012).
6.6. Effect of contact medium
Different contact medium such as packed beds, packed bed with
nanoparticles coated media, fluidized beds, etc. have been reported
in literature to explain the way of application of nano adsorbents
for arsenic removal from water (Table 1). For arsenic removal, there
are very few column studies reported in available literature and
most of them found to be supported packed bed column studies.
While for column studies both packed bed and fluidized bed can be
used depending on type of adsorbents. For example, adsorbent of
acceptable hydraulic conductivity is suitable for fixed bed, while
adsorbent of low hydraulic conductivity found to be less suitable
for packed bed column. Coating of nano adsorbents on the material
of high hydraulic conductivity can solve this problem. In packed
bed column study, continuous operation becomes difficult because
of channelling and fouling due to non-uniformity of flow accom-
panied by loss of smaller size (nano) particles. Nano adsorbents
with or without supporting material should also be of sufficient
compressive strength, so that it can resist the hydraulic shock that
may lead to the fracturing of the adsorbent in a packed bed (Chen
et al., 2011). Fluidized bed can also be used for nanoparticles if
the adsorbent is coated with such materials that restrict the
agglomeration of nanoparticles in fluidized state. Less coating re-
sults the low adsorption capacity while more number of layers can
be easily shedded off, which leaves the coated sand with little
adsorption capacity and causes secondary pollution in drinking
water (Chen et al., 2009) that nececiated the researchers to use
404 S. Lata, S.R. Samadder / Journal of Environmental Management 166 (2016) 387e406
acrylic-styrene copolymer latex as binding agent. Other polymers,
such as polyacrylamide (PAM) and polyvinyl alcohol (PVA) were
also found as promising binders. A low cost “green” starch was used
as a stabilizer to prevent the agglomeration of magnetite nano-
particles and as a bridging agent for allowing the nanoparticles to
flocculate and precipitate with maintaining high arsenic adsorption
capacity (An et al., 2011).
Application of nano adsorbents are found to be more effective in
removal of both arsenite and arsenate from contaminated water. It
has been found that even waste water pollutants with high arsenic
concentrations can be effectively removed using different nano
adsorbents with a relatively small amount of adsorbent and short
time. The nanoparticles should have good adsorption capacity at
the pH range 6.5e8.5 with low adsorbent dose for initial concen-
tration upto 10 mg/L for selection of nanoparticles as the adsorbent
for arsenic removal from drinking water. The metal used as nano
adsorbent should not leach into treated water beyond its permis-
sible limit, otherwise a suitable coating with appropriate material
should be provided to stop leaching. MMO's nanoparticles found to
have comparatively better adsorption capacity at drinking water pH
range, competing ions do not hinder the adsorption capacity and
easily regenerable by NaOH. If the suitable supporting material is
explored for MMO's nanoparticles, it may prove to be an effective
feasible solution for the removal of arsenic at field condition.
7. Conclusions
This paper thoroughly reviewed the application and challenges
in the selection of nano adsorbents for arsenic removal. This study
also critically analyzed the desorption and separation studies
available for various nano adsorbents. The practical applicability of
nano adsorbents in field conditions (such as applicability of
adsorbent on a wide range of arsenic concentrations with better
adsorption efficiency and regeneration of nano adsorbents) re-
quires more attention. Considering the various studies reported so
far, it is concluded that aluminium oxides for waste water and
MMO's nanoparticles for drinking water may be the better option
for arsenic removal. Adsorption potential, high surface area, phys-
ical and chemical stability, solubility product of adsorbent, holding
materials (should be such that it participates in adsorption to
enhance adsorption capacity of the adsorbent), hydraulic conduc-
tivity of adsorbent, leachability of metallic nanoparticles into the
treated water, separation process of nano adsorbents from aqueous
solution, cost effectiveness, field applicability, environmental
impact and risk assessment should be considered before selection
of nano adsorbents for arsenic removal. The study will help the
readers to choose appropriate nanomaterials, to select suitable
holding materials for nano adsorbents for field application and to
understand the further research required for arsenic removal using
nano adsorbents.
Acknowledgements
The authors gratefully acknowledge the support provided by the
Department of Environmental Science & Engineering, Indian
School of Mines, Dhanbad for carrying out the present research
work.
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