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Journal of Environmental Management 162 (2015) 306e325

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Journal of Environmental Management


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Review

Arsenic and uoride contaminated groundwaters: A review of current


technologies for contaminants removal
Sachin V. Jadhav a, Eugenio Bringas b, Ganapati D. Yadav a, *, Virendra K. Rathod a,
Inmaculada Ortiz b, Kumudini V. Marathe a
a
Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga, Mumbai, 400019, India
b
Department of Chemical and Biomolecular Engineering, Universidad de Cantabria, Avda, Los Castros s/n. 39005, Santander, Spain

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

Article history: Chronic contamination of groundwaters by both arsenic (As) and uoride (F) is frequently observed
Received 23 November 2014 around the world, which has severely affected millions of people. Fluoride and As are introduced into
Received in revised form groundwaters by several sources such as watererock interactions, anthropogenic activities, and
26 June 2015
groundwater recharge. Coexistence of these pollutants can have adverse effects due to synergistic and/or
Accepted 7 July 2015
antagonistic mechanisms leading to uncertain and complicated health effects, including cancer. Many
Available online 8 August 2015
developing countries are beset with the problem of F and As laden waters, with no affordable tech-
nologies to provide clean water supply. The technologies available for the simultaneous removal are akin
Keywords:
Fluoride
to chemical treatment, adsorption and membrane processes. However, the presence of competing ions
Arsenic such as phosphate, silicate, nitrate, chloride, carbonate, and sulfate affect the removal efciency. Highly
Membrane efcient, low-cost and sustainable technology which could be used by rural populations is of utmost
Adsorption importance for simultaneous removal of both pollutants. This can be realized by using readily available
Electrocoagulation low cost materials coupled with proper disposal units. Synthesis of inexpensive and highly selective
Ion exchange, Contaminant removal nanoadsorbents or nanofunctionalized membranes is required along with encapsulation units to isolate
the toxicant loaded materials to avoid their re-entry in aquifers. A vast number of reviews have been
published periodically on removal of As or F alone. However, there is a dearth of literature on the
simultaneous removal of both. This review critically analyzes this important issue and considers stra-
tegies for their removal and safe disposal.
2015 Elsevier Ltd. All rights reserved.

1. Introduction potable purposes by over 50% of the global population. Thus,


groundwater is sometimes described as the hidden sea. This is
Water is not only an essential component for life but also a basic indeed true to a greater extent in countries like India where local
building block to maintain quality of life. Water scarcity has already supply to ~80% rural and ~50% urban dwellings is provided by
revealed adverse effects on all populations in every continent. More groundwater sources alone (Ayoob et al., 2008).
recently, UNICEF and WHO reports have conrmed that 748 million Presence of several naturally occurring, anthropogenic and in-
people do not have adequate and safe water resource and over 2.5 dustry generated ions such as uoride, arsenic, nitrate, sulfate, iron,
billion people have access to meagre water supply. The WHO also manganese, chloride, selenium, heavy metals, and radioactive
estimates that 1.8 billion people use faecally contaminated source materials may greatly compromise water quality, leading to health
of drinking water (UNICEF/WHO, 2014). Groundwater is used for problems. The most signicant inorganic pollutants in groundwater
affecting human health at the global scale, according to the WHO,
are arsenic and uoride (Thompson et al., 2007). In this context,
Abbreviations: WHO, World Health Organization; USEPA, United States Envi-
uoride pollution of drinking water receives much less consider-
ronmental Protection Act; CPC, chemical precipitation/coagulation; EC, electro-
coagulation; EF, electrocoagulation/otation; AD, adsorption; IE, ion exchange; MT,
ation than arsenic.
membrane technology; RO, reverse osmosis; FO, forward osmosis; NF, nano-
ltration; ED, electrodialysis.
* Corresponding author.
1.1. Health effects of single and combined As and F
E-mail addresses: gdyadav@yahoo.com, gd.yadav@ictmumbai.edu.in
(G.D. Yadav). Fluoride is the only chemical in potable water that can cause

http://dx.doi.org/10.1016/j.jenvman.2015.07.020
0301-4797/ 2015 Elsevier Ltd. All rights reserved.
S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325 307

different health effects depending upon its concentration in dis- ingested, they may function independently or synergistically or
solved form. A very small amount of uoride is benecial for bone antagonistically to one another (Chouhan and Flora, 2010). While
and teeth development and dental health. However, concentrations the harmful effects of As and F individually have been widely
higher than 1.5 mg/L are damaging to human health, causing dental studied, the exposure to both together has received little atten-
or skeletal uorosis (Miretzky and Cirelli, 2011). Children below 12 tion. Rao and Tiwari (2006) reported that As and F in combina-
years are likely to be most exposed to uorosis as their body tissues tion affect integrity of cells genetic material more than the
continue to grow during the formative age. Moreover, uorosis is individual exposure. In animal studies for rats, co-exposure of As
non-reversible and the disorder has no medical treatment. The and F even at low concentrations resulted in decreased comet tail
WHO permits a uoride concentration of 0.5e1 mg/L in drinking and detrimental effect on liver and kidney (Flora et al., 2009;
water (WHO, 2011). Efuent limit of 4 mg/L for F from the waste- Mittal and Flora, 2006). Wang et al. (2007) reported that chil-
water treatment facilities has been set by USEPA (Shen et al., 2003). dren's growth and intelligence were severely inuenced by high
Fig. 1 depicts the statistics on population exposed to F contamina- concentrations of As or F. Hence, it is important to remove these
tion. Clearly, China and India are the most affected countries where toxicants from potable water. Despite the extreme seriousness of
nearly 35 and 26 million, respectively, people are at uoride risk. the issue, very less data exist on the populations facing simul-
As for arsenic, As(V) (arsenate) and As(III) (arsenite) are the taneous toxicity of As and F.
most predominant valence states, which are found in aerobic sur- This article analyzes the genesis of the combined presence of
face waters and anaerobic groundwaters, respectively. Between pH geogenic uoride and arsenic in groundwater and drinking water as
4 and 10, major As(III) compound is charge neutral, whereas As(V) well as the treatment methods for their removal. Also, it reviews
species exists as charge negative. The occurrence of As in ground- the effectiveness of several treatment methods when these two
water poses even a greater danger than F hazards due to its extreme contaminants are present together.
toxicity at low concentration which goes undetected especially in
As(III) form (Camacho et al., 2011). Arsenic is well known for its
2. Occurrence of F and As in groundwaters
carcinogenicity in kidney, lung, liver, skin, and bladder. At high
concentrations, As causes gastrointestinal problems and arsen-
There is an evidence of the presence of uoride in different
icosis, which arise mainly via consumption of water containing As
latitudes such as south-east of Africa, United States, the Middle East
and its subsequent accumulation in the body (Sharma and Sohn,
of Asia, South America, and Asian countries. However, China and
2009; Villaescusa and Bollinger, 2008). Therefore, the WHO rec-
India are the worst affected countries (Fig. S-1, supplementary
ommends As concentration of 10 mg/L as the upper permissible
information).
limit in water (WHO, 2011). This limit is applicable in India, Japan
For past few decades, the areas with arid and semi-arid climates
Taiwan, USA and Vietnam (Hug et al., 2008; Reddy and Roth, 2013)
are suffering from the scarcity of water due to the fact that the
while other countries like China, Bangladesh, and most of South
uptake of groundwater is in far excess than water recharge as well
American nations have permitted a higher concentration of 50 mg/L
as excessive evaporation leading to decreased availability of water
(Camacho et al., 2011; Chakraborti et al., 2010). A report prepared
(Jakariya et al., 2003, 2007). Since uoride primarily originates from
by UNICEF consultant Ravenscroft (2007) estimates that natural As
uoride rich rocks, concentrations of uoride are directly propor-
pollution of groundwater and surface water affects more than 140
tional to the extent of leaching/dissolution of crystalline minerals
million people in at least 70 countries worldwide. A large popula-
through watererock interactions. The sources of uoride in
tion of South Asia is exposed to As toxicity (Fig. 2).
groundwater through uoride-rich rocks are (i) urospar (CaF2)
When two different types of harmful contaminants are
from lime stones, sand stone, sedimentary rocks; (ii) cryolite

Fig. 1. Estimated population exposed to F contamination in selected countries (103) (CDC, 1993; Diaz-Barriga et al., 1997; Fewtrell et al., 2006). * no recent data available.
308 S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325

Fig. 2. Estimated population exposed to As contamination in selected countries (103) (Ravenscroft, 2007).

(Na3AlF6) from igneous rocks, granite; (iii) uorapatite (Ca5(PO4)3F) As (10e5300 mg/L) and F (51e7340 mg/L) are reported in shallow
from igneous rocks, metamorphic rocks, and (iv) sellaite (MgF2) groundwaters, indicating potential risk of arsenicosis and uorosis
from bituminous dolomiteeanhydrite rock. in Chaco-Pampean plain of Argentina where As and F borne dis-
Arsenic occurs in the environment in several oxidation states as eases affect ~2e8 million people (Nicolli et al., 2012). The concur-
stated earlier. Parsa and Shahidi (2010) stated that unusual large rent presence of As and F in groundwater is connected to volcanic
proportions of As are present in potentially soluble forms. Studies eruptions, geothermal currents and mining activities (Alarcon-
have shown that over exploitation of shallow (or main) aquifer has Herrera et al., 2013).
been the source of many arsenic problems (Jakariya and Selected data on As and F levels in waters from around the world
Bhattacharya, 2007). Fig. S-2 (supplementary information) shows are presented in Table 1. Excessive rates of evaporation in arid and
the identied regions of world having arsenic contamination of semi-arid regions lead to generation of saline groundwaters and
groundwaters. Very high concentrations of As can be seen pre- alkaline pH, which are related to high concentrations of As and F in
dominant in Mexico, USA, China, Bangladesh, Vietnam and groundwater (Nicolli et al., 2008a, 2008b). Presence of Na and
Pakistan. Recently, groundwaters in Japan and Korea were also HCO 3 are also correlated with simultaneous presence of high
found to be contaminated with As (Ahn, 2012; Yoshizuka et al., concentrations of As and F. On the other hand, studies in Yuncheng
2010). The major mechanism responsible for the As contamina- Basin, northern China, have found a moderately positive correlation
tion in groundwater is desorption from iron oxides or hydroxides between pH and As and F concentrations indicating that high pH
from natural rocks and their reductive dissolution (Kim et al., 2012; may favor desorption of F and As, while HCO 3 may act as a sorption
Li et al., 2012). competitor (Currell et al., 2011). These authors also have found a
Fig. S-3 (supplementary information) shows the co-occurrence strong correlation between As and F, suggesting that the enrich-
of uoride and arsenic worldwide. Arsenic and F are found to co- ment of As and F is governed by a common mechanism and/or due
exist in groundwaters in China, Argentina, Mexico, and Pakistan to a set of aquifer conditions.
among other countries where As concentrations up to 5300 mg/L The sediment geochemical data of 2046 samples from northern
and F up to 29 mg/L are noticed in the same groundwaters (Jing Mexico were generated by Alarcon-Herrera et al. (2013). The region
et al., 2012). Recently, Australia, Japan, Korea, and Chile have also is surrounded by large basins lled with alluvium, and dominated
been shown with elevated levels of As and F co-occurrence (Fig. S-3, by a large number of wells. A strong correlation between As and F
supplementary information) (Ahn, 2012; Chakraborti et al., 2011; was observed in these localities where As has been reported in high
Fernandez-Turiel et al., 2005; Richards et al., 2009; Yoshizuka amounts indicating co-occurrences of As and F. Nicolli et al. (2008b)
et al., 2010). Table S-1 (supplementary information) presents have found a strong link between F and As concentration in deep
detailed information on As and F co-contamination in groundwa- wells in Cordoba province, Argentina.
ters with respect to geographical location and lists key ndings of
various publications. 3. Methodologies for toxicant removal from groundwaters
Arsenic is found to be frequently associated with uoride in
shallow aquifers around the world. A high concentration of As is 3.1. Fluoride removal
also found in semi-arid regions that contain oxidized groundwater
(Currell et al., 2011). The correlations between these two toxicants Basically, deuoridation of water can be introduced at two
are dissimilar as per redox potential (Kim et al., 2012). The Fe- organizational levels; as household deuoridation, carried out by
hydroxides adsorption capacity of F and As decreases with in- individual households for their own water consumption, and as
crease in pH, releasing both components into groundwater indi- community deuoridation, carried out at village, town, sub-urban
cating that the Fe-(hydr)oxides play an important role for hosting area levels. As it has been previously reported in the reviews of
the co-contamination (Streat et al., 2008). High concentrations of Ayoob et al. (2008) and Mohapatra et al. (2009), many technologies
S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325 309

Table 1
Data on groundwaters containing As and F.

Parameter Geographical location

Zhijiliang, Inner Meoqui City, Kalalanwala and Un-known site, Kyushu, Japan Chihuahua, Geumsan Santiago del Estero
Mongolia, China Chihuahua, Kot Asadullah, India 16 sites Mexico County, Province, Argentina
Mexico Pakistan Korea
2 sites 2 depths Min. and
Max.

pH 7.57 7.2 7.4 8 7.55 7.2 2.8-8.5 7.17 5.78 8.68 6.4-9.3
Temperature,  C 13 e e 25 2 25 2 20.5 e 25 12 23 e
Arsenic, mg/L 1.10 0.134 0.075 0.235 0.06 0.13 0.01e3.23 0.435 e 113 0.01-15
Fluoride, mg/L 1.59 5.9 4.8 11 1.47 5 0.04e3.76 11.8 e 7.54 0.7-22
Sodium, mg/L 119 e e 630 273 e 1.1e1501 250 1.64 66.8 e
Carbonate, mg/L 10 121 126 857 410 e e e 8.64 239 e
Turbidity, NTU 311 1.4 1.1 e e 320 e 1 e e e
Hardness, mg/L 51.5 24.5 58.3 e e e e e e e e

Reference Zhang et al. Pinon- Farooqui et al. Devi et al. Yoshizuka et al. Nevarez et al. Ahn Bhattacharya et al.
Miramontes
et al.

Year 2003 2003 2007 2008 2010 2011 2012 2006

have been employed and are currently being used to carry out the F been trying to develop a sustainable cost effective technology to
removal from potable water such as ion exchange (Chubar, 2011), reduce F concentrations in water. CSIR-NEERI in Nagpur, India,
adsorption (Bhatnagar et al., 2011; Gong et al., 2012a), coagulation developed the Nalgonda process for the deuoridation of drinking
and electrocoagulation (Behbahani et al., 2011; Gong et al., 2012b), water. The technique has been operated in a number of villages in
and membrane processes (Richards et al., 2010). Each of these India as ll and draw type and hand-pump attached plants
technologies has its own merits and demerits. Fig. 3 presents a (Meenakshi and Maheshwari, 2006).
typical initial concentration range treatable by a particular tech- Chemical precipitation technique involves addition of
nology and its corresponding removal efciency. It can be seen that aluminum salts along with lime to the F rich water followed by
chemical treatment is capable of treating very high concentrations occulation and sedimentation or ltration. In the rst step, lime
of F; since it cannot bring F concentration within WHO permissible reacts with F impurities such as NaF, HF, etc. to form insoluble
limit, it can be coupled with other technologies as a primary calcium uoride.
treatment method (Islam and Patel, 2007). This approach offers
advantage of better life expectancy of secondary or tertiary treat- Ca(OH)2 2F/CaF2 2OH (1)
ment due to reduced load.
Ca(OH)2 (aq) 2NaF (aq) / CaF2 (s) 2NaOH (aq) (2)
3.1.1. Chemical precipitation/coagulation (CPC)
The roots of the deuoridation processes can be traced to the Essentially, in the second step, aluminum sulfate or aluminum
early 1930's since when researchers from all around the world have chloride or both together, is added. Aluminum salt acts as a

Fig. 3. Fluoride removal performance of various technologies. Where, CPC-11 Reardon and Wang (2000); CPC AD-12 Islam and Patel (2007); EC EF-13 Zuo et al. (2008);
EC/EF-14 Bennajah et al. (2009); EC-15 Khatibikamal et al. (2010); AD-16 Cengeloglu et al. (2002); AD-17 Tripathy et al. (2006); AD-18 Tripathy and Raichur (2008); AD-
19 Thakre et al. (2010); AD-110 Ganvir and Das (2011); IE-111 Solangi et al. (2009); IE-112 Viswanathan and Meenakshi (2009); RO-113, NF-113 Kettunen and Keskitalo
(2000); RO-114, NF-114 Dolar et al. (2011); ED-115 Zeni et al. (2005); ED-116 Ergun et al. (2008).
310 S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325

coagulant and is often being used for viable and effective F removal deuoridation of the source waters. Developments during the
from water. The basicity present in water with alum yields an past decade have demonstrated that EC is an effective technique
aluminum salt, [Al(OH)3], which is insoluble. for F removal in drinking waters and industrial wastewaters
It has been reported that the pH of the contaminated water (Abuzaid et al., 2002; Essadki et al., 2009; Han and Kwon, 2002;
increases up to 12; however, the best F removal is achieved be- Holt et al., 2002; Khatibikamal et al., 2010; Mameri et al., 2001).
tween the pH range of 6e7 (Aoudj et al., 2012). The dose of alum is It has been reported that by using EC, uoride concentrations
typically around 20 fold the lime required. The uoride from could be reduced to values lower than 1.5 mg/L from initial con-
groundwater can be removed upto 96% from the initial concen- centrations ranging from 10 to 20 mg/L (Bennajah et al., 2009).
tration of 109 mg/L using lime (Reardon and Wang, 2000). Similar Another advantage is that EC processes are characterized by lower
ndings on F removal by calcium salts have been conrmed by amount of sludge and absence of chemical handling. However,
Jadhav et al. (2014). electricity is required to operate the plant which increases its
The Nalgonda technique has the advantages of low initial cost operating cost.
and effectiveness. However, Nalgonda technique is not recom-
mended owing to high maintenance cost, unpleasant water taste, 3.1.2. Adsorption (AD)
requirement of large area for sludge drying, and a very high residual Amongst other methods, adsorption (AD) is a conventional
aluminum (Liu et al., 2013). The residual aluminum in waters technique which is widely used for deuoridation of water because
ranges from 2.01 to 6.86 mg/L under different operating conditions. it is economical, robust, environmentally benign and efcient. New
Any amount over 0.2 mg/L of aluminum in drinking water can cause advanced materials have been developed recently for effective and
serious health problems, including dementia (Shrivastava and Vani, cheap uoride removal from potable water. Many low cost adsor-
2009). bents have also been employed for uoride removal like alumina,
red mud, clays, soils, activated carbon, calcite, brick powder, acti-
3.1.1.1. Electrocoagulation (EC) and electrocoagulation/otation (EF) vated coconut-shell, activated kaolinites, oxides ores, modied
Passage of an electric current into an aqueous medium helps to chitosan, bone char, and some other low cost materials (Mohapatra
destabilize suspended, dissolved and emulsied impurities, and the et al., 2009).
process is known as electrocoagulation (EC). During the past A common mechanism by which the adsorption of F ions
decade, the use of electrocoagulation (EC) as well as electro- occurs onto solid particles can be given by the following three
coagulation/otation (EF) process is on the rise. It can be effectively steps: (i) mass transfer of F ions to the external surface of
employed to treat oily wastewaters, dye and textile industry ef- the adsorbent, (ii) F ion adsorption onto external particle surface,
uents and removal of organic matter, heavy metals and uoride and (iii) intra-particle diffusion of F ions from the exterior surface
(Hu et al., 2003, 2005). EC is advantageous since no impurities are and possible exchange with elements on the pore surface
introduced and useful contents existing in raw water can be inside particles (Fan et al., 2003). Activated alumina happens to
retained during deuoridation. be one of the most popular and widely used solid adsorbents
Electrochemical cell (also known as electrolytic cell) is the for the deuoridation of potable water and many reports are
basis of electrocoagulation and electrootation techniques. An available on large-scale installations (Chauhan et al., 2007).
electrocoagulation reactor typically consists of an electrolytic cell Alumina is popular amongst other adsorbents because it main-
with an anode and a cathode. Passage of the electric current leads tains its structural stability without shrinkage, swelling or
to the deterioration of the anode and cathode which may be made disintegration in water (Serbezov et al., 2011). Granules of acti-
of the same or different materials and which act as sacricial vated alumina having a very high surface area of ~200e300 m2/g
electrodes (Mollah et al., 2001). It is reported that the following possess a substantial number of active sites to facilitate adsorp-
three routes are adapted for the electrocoagulation/otation tech- tion. At rst, the acidication of alumina is carried out with HCl
niques, namely, (i) electrode oxidation, (ii) generation of gas bub- as follows:
ble, (iii) otation and sedimentation of ocs (Emamjomeh and
Sivakumar, 2009). Alumina H2O HCl / Alumina HCl H2O (7)
Electrocoagulation deals with electrochemical production of
destabilization agents that lead to neutralization of electric charge ( represents activated state)
to remove pollutants. Charged particles coagulate together to make The acidic alumina on contact with F ions displaces the Cl ions
a mass. Effective removal of pollutants by otation and sedimen- and gets bonded to alumina.
tation is augmented by metal based coagulants having a similar
effect as the metal cations produced by anode. The key reactions are AluminaHCl NaF / AluminaHF NaCl (8)
as follows (Zuo et al., 2008):
Further, regeneration is carried out by rst treating the adsor-
Al / Al3 3e at the anode (3) bent with alkaline solution followed by acid wash. A few reports
mention that F removal is due to ion-exchange as well as adsorp-
Al3 3H2O / Al(OH)3 3H (4) tion following both Freundlich and Langmuir isotherms (Bansiwal
et al., 2010; Ghorai and Pant, 2005).
Al(OH)3 xF / Al(OH)3xFx xOH (5) Meenakshi and Maheshwari (2006) have reported the devel-
opment of domestic and hand-pump units with activated alumina
2H2O 2e / H2 2OH at the cathode (6) for deuoridation. The unit consists of ~20 L capacity bucket, tted
with a micro-lter at the bottom containing 5 kg of activated
Evolution of hydrogen bubbles at the cathode improves the F alumina. Activated alumina coated with manganese dioxide was
ion mass transfer rates and also leads to oating of the aluminum found to reduce F concentration to 0.2 mg/L from 10 mg/L at pH 5.5
complex (Al(OH)3xFx) ocs at the top of the electrocoagulation (Tripathy and Raichur, 2008). Magnesia-modied activated
system. Effective F removal can be achieved by isolating the alumina granules were also used successfully to reduce F from
aluminum complex from the aqueous phase periodically. There- drinking water with a maximum adsorption capacity of 10.12 mg/g
fore, formation of aluminum complex [Al(OH)3xFx] results in the at F concentration of about 150 mg/L (Maliyekkal et al., 2008).
S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325 311

Biswas et al. (2009) characterized the synthetic hydrated iron (III)e it generates a large volume of F loaded waste which again is a
tin(IV) mixed oxide (HITMO) for F removal. It was found that the F problem.
adsorption capacity decreased with increasing initial pH from 3.0 to
5.0, and it remained constant up to pH of 7.5. Also, the high bicar- 3.1.4. Membrane technology (MT)
bonate content showed adverse effects on F removal by HITMO. It In recent years, membrane-based techniques have got a lot of
was the pseudo-second order kinetics with multiple-stage which attention due to their performance and reliability in operation for
dened rate-limiting step. The equilibrium data was best portrayed the removal of F from groundwater. At present, nanoltration (NF),
by Langmuir isotherm model with adsorption capacity 10.50 mg/g reverse osmosis (RO), and electro-dialysis (ED) are the most pop-
and adsorption energy ~9 kJ/mol. The uoride-rich material was ular membrane processes for F removal.
successfully regenerated up to 75% in desorption studies.
All in all, the choice of the adsorbent seems to be reliant on 3.1.4.1. Reverse osmosis (RO) and nanoltration (NF)
factors such as the ability to adsorb from dilute solutions, pH, In membrane ltration, the water containing high concentration
removal duration, adsorbent stability, regeneration, and adsorption of pollutants is passed through a semipermeable membrane. The
capacity in the presence of competing ions, and the economics membrane discards atoms on the criteria of size and electric charge.
(Mohapatra et al., 2009). The main disadvantage of the adsorption The pollutants are removed from the water and collected at
process is that the adsorbent gets exhausted soon and considerable retentate side; whereas, clean water is recovered through
time is required for regeneration. Moreover, regeneration steps permeate. In RO, pressure greater than the natural osmotic pressure
leads to secondary pollution because F containing aqueous solution is applied to the concentrated side of the membrane. Kettunen and
is discarded as a waste. Keskitalo (2000) evaluated the performance of a low energy RO
membrane with a NF membrane. A membrane ltration plant of
3.1.3. Ion exchange (IE) 16e25 m3/h capacity was constructed in Laitila, Finland, to control
Many reports have highlighted the efcacy of ion exchange with F and Al concentration in drinking water. The comparative removal
other techniques (Onyango et al., 2005, 2006). Usually, ion ex- was above 95 and 76% for F and Al, respectively and RO needed
change technique removes F by adsorption rather than exchanging ~1.6 bar excess feed pressure than that used in NF. Sehn (2008)
ions. The fundamental reason is that the uoride concentration is studied a large scale RO plant in southern Finland for three years.
comparably lower than other ions present in water. Cation ex- The system was operated at a pressure of 6e11 atm and tempera-
change resins are more selective for F removal than anion exchange ture range of 5e11  C, which was until recently possible only with
resins (Meenakshi and Viswanathan, 2007). However, the NF membrane. This resulted in low power requirements and the
deuoridation capacity and selectivity for F is dependent on the plant was operated at 80% recovery without using a scaling inhib-
type of resin. The loading of metal ions inuences the uoride itor. Richards et al. (2011) used four commercial NF/RO membranes
removal drastically, owing to variations in their properties (Luo and in Australian groundwaters. Their investigations showed the in-
Inoue, 2004). Thus, it is difcult to maximize the deuoridation uence of solar irradiance levels on retention of F, Mg, NO3, K and
capacity (DC) of ion exchange resins while simultaneously Na where convection/diffusion predominated the retention. About
enhancing the F selectivity. 85% of all solutes were retained during solar irradiance conditions.
Viswanathan and Meenakshi (2008) used a widely available ion Nanoltration (NF) is a relatively new process in contrast to RO,
exchanger Indion FR 10 that has considerable F removal capabil- ultraltration (UF) and microltration (MF), and it is emerging as a
ities. It was chemically altered with Ce3, Fe3, La3, and Zr4 practically functional technology in treating industrial wastewa-
species to understand their selectivity for deuoridation. The ters. Nanoltration is characterized by attributes between reverse
maximum deuoridation capacity of all the modied resins was osmosis (RO) and ultraltration (UF). Regardless of the similarity in
measured around 0.5 mg/g. The authors pointed out that the operation with RO, NF is operated at a comparatively lower pres-
deuoridation was due to electrostatic adsorption and complexa- sure yielding identical permeate ux even at lesser pressure. NF
tion. Recently, they have modied Indion FR 10 into Na and Al3 removes less than 60% of the monovalent ions as opposed to 90% by
types by loading the metal ions in H type of resin (Viswanathan RO membranes. RO can completely demineralize water with very
and Meenakshi, 2009). low or practically no selectivity for monovalent ions but it suffers
Chubar et al. (2005) obtained a new ion exchanger from double from high operating pressure, low permeate ux and high energy
hydrous oxide (Fe2O3$Al2O3$xH2O) by the solegel method from requirements (Alarcon-Herrera et al., 2013). In particular, fractional
easily available raw materials, which was used for adsorption of F, deuoridation can be attained by altering the operating variables of
Cl, Br, and BrO3 simultaneously. It was found that the pH effect of the NF process; while simultaneously keeping the required F con-
F and Br was dependent on ion speciation. Sufcient capacity for tent in the water.
sorption of all these anions was in the pH range of 3e10. The F Two of the popular NF membranes, NF90 and NF400, were used
adsorption of 88 mg/g was the highest among all species. Solangi to practically remove F from groundwaters (Tahaikt et al., 2007).
et al. (2009) modied anionic resin Amberlite XAD-4, in which The quality of water achieved by the NF400 membrane was found
the amino group is introduced to the aromatic ring of the resin and to be satisfactory especially for lower F content. For higher F con-
utilized effectively for F extraction. They found that the modied tent, a double pass was required to reduce it to an acceptable level.
resin was efcient particularly at pH 9 and was also effective in the Further, these authors calculated the economics of a 100 m3/h NF
presence of other anions such as Br, NO   2
2 , NO3 , HCO3 and SO4 . plant corresponding to a recovery rate of 84%, F removal of 97.8%
Subsequently, the authors modied Amberlite XAD-4 resin by and pressure of 10 bar (Elazhar et al., 2009). The capital cost was
adding thio-urea binding sites into the aromatic rings (Solangi estimated to be 748,000 V with operating cost of 0.212 V per m3.
et al., 2010). The modied resin had high efciency for F removal Hu and Dickson (2006) investigated performance of negatively-
from aqueous solution at a wide range of pH from 4 to 10. The resin charged commercial thin-lm composite (TFC) nanoltration
could be regenerated several times and used as an ion exchange membranes. They conrmed that higher pressures exhibit sub-
material in lters for F removal from potable water. stantial positive effect on F removal along with increase in the ux.
Ion exchange treatment has a great F removal potential (up to Malaisamy et al. (2011) modied a commercially available NF
95%). However, the resins are costly , thereby making the entire ion membrane by layer-by-layer assembly of alternating poly-
exchange method expensive. Regenerating the resins is simple but electrolyte thin lms in order to promote removal and selectivity
312 S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325

towards monovalent ions, particularly F and Cl. Polystyrene sulfo- 3.2.1. Chemical precipitation/coagulation (CPC)
nate (PSS) was the anionic polyelectrolyte and polydiallyldimethyl Arsenic can be removed most commonly by precipitation as
ammonium chloride (PDADMAC) was the cationic polyelectrolyte. ferric arsenate, calcium arsenate or arsenic sulde. The ideal
Thin (0.5e8.5 mm) PDADMAC/PSS bilayers were deposited on the operating pH for calcium generated precipitation is 10.5. Though
substrate membrane. The F ion removal increased from 40% (un- the reported attainable As concentration is 10 mg/L, usually the
modied) to 70% (8-bilayer modied). These authors found that the concentrations below 1 mg/L are challenging to accomplish
selectivity for Cl over F was 2.7 times for an 8-bilayer modied (Robins, 2006). Additionally, As(III) removal during coagulation is
membrane compared to 1 for unmodied membrane. considerably less effective than As(V) under otherwise similar
conditions and pre-oxidation is required by using an oxidizing
3.1.4.2. Electrodialysis (ED) agent such as Cl2, NaOCl, or H2O2 to convert As(III) to As(V). It is also
Electrodialysis is another emerging technique for removing evident that As precipitation with ferric salts is more efcient than
ionic compounds from aqueous media using ion exchange mem- alum (Mohan and Pittman, 2007). Ferric salts are added to As
branes in which the applied electric eld acts as a driving force and contaminated water to form ferric arsenate (Holl, 2010):
is responsible for separation of contaminants. The application of
electric current between two electrodes results in passage of cat-
Fe3 AsO4
3 /FeAsO4 s (9)
ions to the cathode and anions to the anode through the negatively
charged cation exchange membrane and positively charged anion The efcacy of aluminum-based coagulation was examined with
exchange membrane, respectively. The end result is the increased reference to variable forms and As concentrations in three potable
and decreased concentration of cations and anions in alternate water treatment plants in New Zealand (Gregor, 2001). Soluble
partitions. The global trend is shifting towards electrodialysis as an As(V), in general, was transformed to particulate As(V) by adsorp-
alternate technique for deuoridation primarily because of its tion during fast mixing, and eventually was removed by clarica-
simplicity and ability to overcome the shortcomings of the chem- tion along with natural As. The soluble As(III) was oxidized during
ical processes. nal chlorination, to soluble As(V). Baskan and Pala (2010)
Zeni et al. (2005) examined two ion-exchange membranes, conclusively stated that aluminum sulfate is a very efcient coag-
namely, selenium AMP anionic membrane and photo-polymeric ulant at optimum pH of 6e8. The As removal efciency was found
anionic membrane (MZA) for electrodialysis. The AMP mem- to be higher than 85%. Song et al. (2006) studied coagulation with
brane removed 69% and 97% F when the applied current density Fe3 and coarse calcite, followed by normal ltration to achieve
was 0.1 and 0.7 A/dm2, respectively whereas the MZA membrane over 99% removal of As from a high-As water in mine drainage
removed 40% F without pretreatments. Ergun et al. (2008) reported (5 mg/L As). However, ltration was essential after precipitation. In
that electrodialysis is the best method for F removal wherein anion the absence of ltration, the As reduction was only ~30%, but with
exchange membrane SB-6407 was used and found that increasing 0.1 or 1.0 mm lter, the reduction exceeded 96% (Litter et al., 2010).
current density and feed concentration at pH 6 was the most The Stevens Institute of Technology introduced a two buckets
effective. The presence of Cl and SO4 ions in the feed decreased the technology. The setup consists of a mixing bucket (of iron sulfate
F removal efciency. The F ion concentration could be brought and calcium hypochloride) and a ocs separation bucket to achieve
down by 96% (0.8 mg/L), which is below the prescribed limit by sedimentation and ltration. The institute claimed to reduce As
WHO. Sahli et al. (2007) also suggested that electrodialysis gives content to less than 0.05 mg/L in 80e95% cases (Akter and Ali,
better performance for the removal of Cl and F from brackish water. 2011). The Bangladesh Council of Scientic and Industrial
The combination of adsorption and electrodialysis appears to be a Research (BCSIR) has introduced As removal technology by using
cost-effective and better method to remove F ions from brackish coagulation process followed by sand ltration involving ll and
groundwater. draw type units. The Bucket Treatment Unit (BTU) also uses two
The most predominant advantages offered by membrane pro- buckets of 20 L capacity and is based on the methods of coagulation,
cesses are: very high removal capacity (up to 98%), one step puri- co-precipitation and adsorption processes (Ahmed, 2001). It can
cation and disinfection, and no chemical usage. However, it is not remove As in nearly 2e3 h by this method. This technology is
entirely appropriate as it removes all ions from the water. A remi- simple with low installation cost and only common chemicals are
neralization process is required after the treatment as some min- used such as aluminum sulfate and potassium permanganate.
erals are essential and must be present in potable water. Moreover, Moreover, it is possible to easily apply this technology to huge
it is costly due to high initial membrane cost and operating cost. water volumes to serve large communities.
Also, disposal of concentrated F sludge which is produced at On the other hand, like F, As can also be separated by electro-
retentate side can be a major problem. coagulation method. The mechanism of electrocoagulation is was
already presented in section 3.1.1.1. Here the process can oxidize
3.2. Arsenic removal more harmful and not so easily removable As(III) to less harmful
and easy to remove As(V) by virtue of electric current. Wan et al.
The most commonly used As removal methods are also essen- (2011) carried out batch experiments using iron electrode to eval-
tially the same as those for F removal, namely, chemical treatment, uate the effect of various parameters on As removal. Faster removal
adsorption onto sorptive media, co-precipitation and adsorption of As(V) was achieved as compared to As(III) with over 99.9% overall
onto coagulated ocs, ion exchange resin and membrane processes. As removal efciency. The authors also pointed out that the As
Rahman et al. (2014) discuss a different approach from the con- removal was inuenced by the presence of phosphate, while sulfate
ventional methods and advocate utilizing exclusively bio- and silica did not show any signicant effect. Studies by Kobya et al.
organisms for As reduction. An assessment of the removal ef- (2011) have shown the effectiveness of electrocoagulation by
ciency of each of these can be seen in Fig. 4 along with the initial As lowering the As level to less than 10 mg/L. Arsenic removal was
concentration. Fig. 4 suggests that the overall treatable As con- observed to be slightly better in case of Al electrode (95.7%) as
centration ranges from 50 to 1000 mg/L. However, some researchers compared to Fe electrode (93.5%). The calculated operational cost
have successfully treated very high initial concentrations of As for Fe and Al electrodes was 0.020 V per m3 and 0.017 V per m3,
(5000e3,00,000 mg/L) (An et al., 2011; Robins et al., 2005; Song respectively. Similar results for the As removal have been reported
et al., 2006). elsewhere (Balasubramanian et al., 2009; Kumar and Goel, 2010).
S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325 313

Fig. 4. Arsenic removal performance of various technologies. Where, CPC-21 Baskan and Pala (2010); CPC-22 Oehmen et al. (2011); EC-23 Wan et al. (2011); EC-24 Kobya
et al. (2011) AD-25 Tubic et al. (2010); AD-26 Chatterjee (2007); AD-27 Maji et al. (2008); AD-28 Amin et al. (2006); AD-29 Rahman et al. (2004); AD-210 Kundu et al.
(2004); IE-211 Anirudhan et al. (2007); IE-212 Barakat and Shah (2013); IE-213 Urbano et al. (2012); IE RO-214 Oehmen et al. (2011); RO-215 Teychene et al. (2013); FO-
216 Mondal et al. (2014); NF-217 Floch and Hideg (2004); NF-218 Saitua et al. (2005); NF-219 Harisha et al. (2010). Note: Some treatment methods with greater removal are
not shown in the gure due to their very high initial concentration range between 5000 and 300000 mg As/L (An et al., 2011; Robins et al., 2005; Song et al., 2006).

Coagulation can remove up to 99% of the As (Choong et al., whereas As(III) adsorption is independent of pH (Ranjan et al.,
2007). Working at pH 3e4 reduces sludge generation. However, 2003). Adsorption of As(III) and As(V) onto activated alumina
the quantity of iron required for equivalent As removal also in- revealed that the best As(III) and As(V) removal can be carried out
creases (Camacho et al., 2011). By using this technique, a relatively at pH 6.1 and 5.2, respectively (Lin and Wu, 2001). Robins et al.
large volume of As laden sludge is formed, which is normally (2005) investigated the characteristics of Fe(III) and Al(III) hy-
disposed of to landlls, which is a probable source of further droxides in removing As(III) and As(V) from solution. Fe(OH)3 was
contamination (Litter et al., 2010). better than Al(OH)3 in adsorbing As(V). When Fe(OH)3 was used to
remove As(III) and As(V), with 10-fold ratio of Fe(III) to As, the re-
sidual concentration of As dropped from 10 mg/L to 0.2 mg/L at pH
3.2.2. Adsorption (AD) between 6 and 7.5. A comparative study was preformed over the
As per USEPA classication, activated alumina, and in turn performance of polyaluminum chloride, aluminum sulfate and
adsorption, is amongst the best available technologies for As ferric chloride for the removal of As from groundwater (60.5 mg As/
removal in potable water (Dambies, 2005). Activated carbon has L) (Tubic et al., 2010). Chlorine was utilized as the oxidizing agent
also been extensively studied for the removal of As and F in water. leading to the formation of insoluble hydroxides at pH 7. Despite
Arsenic adsorption by activated carbon is explored in detail by a the fact that excess ferric chloride was required, the freshly
number of researchers (Chuang et al., 2005; Gu et al., 2005). Ac- precipitated hydroxides were able to reduce the As levels to less
cording to the review published by Giles et al. (2011) the main than 10 mg/L. Reddy (2007, 2011) reported development of a novel
adsorbents of choice for As removal are Al2O3, Al(OH)3, carbon, FeO, adsorbent cupric oxide (CuO) which was free from limitations of pH
Fe2O3, modied iron oxides, SiO2, layered double hydroxides (LDH), or redox potential modication for As removal and its performance
and organic polymers either as adsorbents per se or as supports. A was excellent in the company of competing anions. Additionally,
broad overview of adsorbents for As removal from drinking water CuO can be regenerated, by leaching with NaOH solution for reuse.
has also been published by Yadanaparthi et al. (2009). The effectiveness of CuO particles was established over a range of
Hydrous metal oxide particles are useful for adsorption and pH from 7.11 to 8.95 wherein competing anions such as sulfate
form the hydroxyl groups in aqueous solutions leading to proteo- (1.3e735 mg/L), phosphate (0.05e3.06 mg/L) and silica
lytic reactions. The surface of such particles is at pH values below (1e54.5 mg/L) were present (Reddy and Roth, 2013).
the zero charge point and the surface gets protonated and thus On the other hand, several lowecost natural adsorbents are
adsorbs anions. This can be expressed as (Holl, 2010), found to be equally effective as the aforementioned adsorbents.
The As(V) removal efciency by using chitosan showed values
> Me  OH H / > Me  OH
2 (10) varied from 40 to 96.8%, depending upon: (i) tested temperature;
(ii) polymer characteristics, and (iii) water composition (Pontoni

> Me  OH
2 An / > Me  OH2 An (11) and Fabbricino, 2012). Another low cost material, laterite soil
reduced ~98% of As from initial 0.33 mg/L from groundwaters
where, Me trivalent metal atom on surface and Ane anions. within 30 min (Maji et al., 2008). Amin et al. (2006) also have
A nano-sized Fe(OH)3 (~5 nm) offers a relatively large surface reported complete removal of both As(III) and As(V) by using rice
area (200e500 m2/g), which is particularly useful for adsorbing a husk columns. The conditions were: 100 mg As/L, 6 g rice husk,
variety of anions and cations from waters (Gilbert et al., 2009; 6.7 and 1.7 ml/min ow rate at pH of 6.5 and 6.0, respectively. A
Pinney et al., 2009; Yavuz et al., 2006). As(V) adsorption is review presented by Malik et al. (2009) exclusively lists a number
strongly dependent on hydrous Fe(III) oxide concentration and pH, of low cost materials for As removal which could be benecial for
314 S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325

developing countries. by employing a new starchebridged magnetite nanoparticles. A


The presence of natural organic matter in water has also been recent work carried out on the As removal from Camarones River
reported to delay the adsorption equilibrium and limits the degree water, North Chile demonstrated very good results (Urbano et al.,
of As(III) and As(V) adsorption (Grafe et al., 2001; Redman et al., 2012). The river water contained sulfate (154 mg/L), chloride
2002). Also, in many cases, the aggressive potential of the toxi- (541 mg/L), boron (15.68 mg/L), chromium (<0.05 mg/L), and total
cants reduces after binding to humic substances (Perminova et al., dissolved solids (1650 mg/L) most of which are known to interfere
2006). Redman et al. (2002) studied the effect of natural organic with As exchange. Water insoluble polymereclay nanocomposite
matter on the adsorption of As onto hematite. Four organic sub- resin (using N-methyl-d-glucamine ligand groups) displayed
stances were seen to form aqueous complexes with As(V) and retention higher than 98% in laboratory studies but decreased to
As(III). The extent of complexation varied with the organic matter 75% in real water samples. Thirunavukkarasu et al. (2002) reported
origin and increased as the cationic metal (mainly Fe) content the removal capacities of the three As sorption media in the
increased. In addition, organic matter showed active redox following order: Amberlite IR-120 (max) > iron oxide-coated
behavior towards As species. This indicates that the presence of sand > manganese greensand.
organic matter may greatly inuence redox as well as complexation Resin Tech's strongly basic hybrid anion-exchange resin called
speciation of As. Similar reports about humic substances have been as TECH RESINTECH ASM-10-HP is a specically prepared sorbent
published elsewhere (Blinova et al., 2007; Perminova et al., 2007; to remove As amid competing ions (Mohan and Pittman, 2007).
Zhilin et al., 2004). The presence of amine groups in organic mat- Several commercial organizations have introduced new tailored
ter play signicant role due to their protonation at denite pH anionic exchangers to achieve As content below 10 mg/L which
values (Saada et al., 2003; Sorkina et al., 2014). As(V) sorption onto include resins of Dow Chem, Rohm and Haas, Purolite, Bayer.
different forms of kaolinite and two kaolinites coated with humic As(V) removal is achieved effectively by ion exchange method,
acids was carried out by Saada et al. (2003). The humic acid coat- with less than 1 mg/L of As in the efuent, while As(III), being un-
ings inuenced As sorption, signifying that adsorption rst charged, is not eliminated, and a prior oxidation step is required
occurred on the humic acid sites fully followed by the remaining on (Litter et al., 2010; Ravenscroft et al., 2009).
kaolinite sites. Studies on zero-valent iron by Mak et al. (2009)
suggested that, although the formation of Fe-humate complex in 3.2.4. Membrane technology (MT)
water delays the As(V) adsorption, As removal effectiveness re- Membrane technologies, especially RO, have proven reliable for
mains practically unaffected in calcium and bicarbonate environ- As removal. RO is probably the best practiced technology which can
ment once enough CaCO3 particles are formed. completely purify water and meet the strict water legislations. Both
Sono Arsenic lter and Kanchan Arsenic lter are currently in lab and pilot-scale experiments have shown more than 95% As(V)
use in Bangladesh and Nepal (Giles et al., 2011). The Sono lter is and 74% As(III) removal efciencies achieved by RO (Holl, 2010;
regarded as the best of 15 technologies to remove As (Chatterjee, Katsoyiannis and Zouboulis, 2006). Membrane processes get rid
2007; Khan et al., 2000; Hussam and Munir, 2007). It can reduce of As through ltration, electric repulsion, and adsorption of As
As concentration from 1100 mg/L to below the WHO permissible containing compounds. The mechanism of membrane ltration
limit. was mentioned earlier in Section 3.1.4.
The distinction between the removal of As(III) and As(V) was
explored by Seidel et al. (2001) with the help of polysulfone thin-
3.2.3. Ion exchange (IE)
lm NF membrane (BQ01). It was observed that elimination of
The application of synthetic ion exchange resins can remove As
As(V) was much higher than that of As(III). Only less than 30% of
species very effectively from drinking water described as by USEPA
As(III) was removed in contrast to 60e90% of As(V) removal. Floch
(An et al., 2011). The extensive reviews summarize the performance
and Hideg (2004) used pilot scale ZW-1000 (Zenon) membrane
of anion exchange resins, macro reticular resins and cation ex-
module, with 0.02 mm pore size, for As removal from waters and the
change resins such as Cu(II), Ce(IV), Fe(III), Y(III), La(III), Zr(IV)
pilot plant could remove As below 10 mg/L from an initial As con-
(Dambies, 2005; Mohan and Pittman, 2007). The order of exchange
centrations up to 300 mg/L. Another study on the NF operating
capacity for the most strongebase resins is given below:
conditions found that the transmembrane pressure, temperature
HCrO 4
   and crossow velocity had no effect on As removal (Saitua et al.,
(maximum) > CrO2 2 2
4 > ClO4 > SeO4 > SO4 > NO3 > Br > (HPO4 ,
2
2 2 2    4 4 2005). These results were supported further by Shih (2005). The
HAsO4 , SeO3 , CO3 ) > CN > NO2 > Cl > (H2PO , H2AsO ,
studies by Harisha et al. (2010) also conrm the aforesaid NF
HCO3) > OH > CH3COO > F
ndings on high As removal (99.80%).
For As removal, strongly basic ion exchange resins, particularly
Recently, a different approach was applied by Oehmen et al.
in the chloride form, have been recommended by EPA (Holl, 2010):
(2011) for As elimination from drinking water where a hybrid rig
    based on ion exchange membraneecoagulation was used. The nal
R  NCH3 3 Cl H2 AsO
4 /R  NCH3 3 H2 AsO
4
As concentration was reduced to 0.3 mg/L from an initial concen-
Cl tration of 53.4 mg/L with 99.43% removal efciency. The hybrid
(12) membrane-coagulation system also proved to be better than con-
ventional coagulation/ltration process where nal As concentra-
where, R matrix phase. tion was reduced to at 3 mg/L from an initial concentration of 57 mg/
Choong et al. (2007) proposed a mechanism of As elimination. L. Electrodialysis has similar efciency as RO which is used pri-
The ion exchange resins are normally loaded with chloride ions in a marily in treating water with high TDS. Electrodialysis with rever-
vessel/bed called as exchange sites and the As-laden water is own sion of polarity of the electrodes (EDR) is an improvement of ED
downward through the vessel where ion exchange takes place. The with minimum scaling (Litter et al., 2010; Ravenscroft et al., 2009).
exhausted resin is regenerated by using aqueous NaCl. However,
 
competing ions such as SO2 4 , NO3 , and F affect the ion exchange 4. Simultaneous removal of As and F
capacity (Baciocchi et al., 2005; Litter et al., 2010; Sharma and Sohn,
2009). The technologies that allow the simultaneous removal of As and
An et al. (2011) showed nearly complete As removal within 1 h, F are essentially similar to the individual removal using adsorption
S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325 315

(Jing et al., 2012; Li et al., 2011), membrane ltration (Padilla and and small community schemes. Extensive research has been car-
Saitua, 2010; Nevarez et al., 2011) and coagulation (Pinon- ried out using various adsorbents for individual as well as simul-
Miramontes et al., 2003; Ingallinella et al., 2011) and adsorption taneous removal of As an F. Adsorbents used for the simultaneous
on various low cost materials (Devi et al., 2008). However, each of removal of F and As are activated alumina (Li et al., 2011), activated
them presents several benets and shortcomings. Table 2 presents carbon (Jing et al., 2012), layered double hydroxides (Dadwhal et al.,
the consolidated information of the recent research work carried 2011; Delorme et al., 2007), ferric hydroxides (Streat et al., 2008),
out by various researchers on the above mentioned technologies goethite (Tang et al., 2010), FeeCe oxides (Zhang et al., 2010),
for simultaneous removal of As and F with their merits and de- inorganic ion exchange adsorbents (Chubar, 2011), volcanic ash
merits. Fig. 5 compares the simultaneous As and F removal (Chen et al., 2011), FeeAl doped polymers (Kumar et al., 2011),
performance. modied cellulose (Tian et al., 2011), and low cost materials such as
goethite coated sand, hematite coated sand and bone and cow char
4.1. Chemical precipitation/coagulation (CPC) (Brunson and Sabatini, 2009; Mlilo et al., 2010).
Activated alumina has proved to be one of the best adsorbents
As discussed earlier, chemical precipitation involves addition of for the As and F removal. Mechanism of adsorption has been dis-
cake alum and/or ferric chloride in the water body. Pinon- cussed earlier in sections 3.1.2 and 3.2.2. However, the use of this
Miramontes et al. (2003) evaluated the combined use of cake sorbent is limited by its strong dependence on solution pH and
alum and a polymeric anionic occulent (PAF) for the removal of As coexisting ions (Liu et al., 2013). To encounter these shortcomings,
and F from drinking water from two wells at Meoqui City, Mexico. mesoporous alumina and calcium-doped alumina were synthe-
As and F concentrations were reduced up to 99 and 77%, respec- sized (Li et al., 2011). Excellent F and As removal capacities were
tively at US$ 0.38 per m3 of treated water at the optimal pH 7.1. The obtained by using these materials reducing As(V) concentration
authors found that the efcacy of F removal was dependent on the from 100 mg/L to 1 mg/L (99% removal). The highest F removal ob-
cake alum quantity used and pH adjustment was needed, whereas tained was 450 mg/g while 1 g of mesoporous alumina was effec-
As removal had no effect of pH. Further studies have found that tive to treat 200 L of As water at pH 7.0. Comparatively, activated
efcient removal of F and As can be achieved using pre- alumina has removal capacity of ~9.0 mg As/g and 7.6 mg F/g (Ku
chlorination, aluminum sulfate and a cationic polyelectrolyte as and Chiou, 2002; Lin and Wu, 2001). Jing et al. (2012) developed
coagulant in precipitation (Ingallinella et al., 2011). a composite adsorbent with titania and lanthania supported on
ArCISeUNR process was developed and applied to groundwater granular activated carbon (TLAC) to effectively remove As(V) and F.
in Argentina, where the As and F concentrations vary between 100 Arsenic and F removal was found to be more than 80 and 35%,
and 150 mg/L and 1.7e2.5 mg/L, respectively (Ingallinella, 2008). respectively. On the other hand, Al- and Fe-doped, activated micro
The system consisted of a coagulationeadsorption process, using (~0.8 mm) and nano (~100 nm) sized porous adsorbents showed
polyaluminum chloride (PAC) as a coagulant with an initial pH signicant removal of F (~100 mg/g) and As(V) (~40 mg/g) ions
adjustment and two ltration stages. Further, the process was (Kumar et al., 2011). Delorme et al. (2007) evaluated mixed oxides
modied with F and As concentrations ranging from 2.4 to 3.2 mg/L synthesized from the mild thermal treatment of quintinite
and 60e90 mg/L, respectively (Ingallinella et al., 2011). The As and F (Mg4Al2(OH)12CO3$H2O) for the removal of F, As(V) from water.
removal efciency was up to 85 and 55%, respectively. 100% As and 80% F removal efciency was obtained from initial
It has been shown that electrochemical processes are an concentrations of 16 mg/L and 10 mg/L for As and F, respectively.
attractive alternative to the conventional methods. A primary However, CO3 addition led to 90 and 20% of the entrapped F and As
mechanism of coagulation and electrocoagulation was explained in being released in the solution conrming that the presence of CO3
sections 3.1.1 and 3.2.1. Vasudevan et al. (2011) studied the effect of ions can signicantly affect the removal efciency of mixed oxides.
various coexisting ions on the removal F using electrocoagulation. This is in agreement with numerous reports that analyzed the
The solutions with F concentration of 5e20 mg/L were treated with presence of competing ions such as phosphate, silicate, nitrate,
As(V) (0e5.0 mg/L) as a competing ion. Electrocoagulation removed chlorides, carbonates, and sulfates. Detailed information on several
F to the extent of 93, 85.3, 77, 69 and 35% in the presence of As(V) other adsorbent studies are summarized in Table 2. The presence of
concentrations of 0, 0.5, 1, 3 and 5 mg/L, respectively. The authors humic acid also affects As and F adsorption on various adsorbents
attributed the reduction in F removal to the preferential adsorption (Dadwhal et al., 2011; Guan et al., 2012; Jimenez-Nunez et al., 2012;
of As(V) ions over F ions with increase in the As(V) concentration. Wei et al., 2011). In fact, the coexistence of As and F too affects the
The presence of carbonate, phosphate and silicate also reduced the individual removal (Chen et al., 2010, 2011; Zhang et al., 2010).
F removal efciency. In order to develop simple and cost effective processes to serve
Zhao et al. (2011) designed an integrated electro-oxidation and on the community level, several low cost materials have been
electrocoagulation system to simultaneously remove As(III) and F evaluated and found to be equally effective in F and/or As removal
ions from water. By utilizing one Fe plate piece and three parts of Al (Brunson and Sabatini, 2009; Mlilo et al., 2010). Fish bone char and
plate electrodes, which reduced As(III) to less than 10 mg/L cow bone char were used for treating water with high concentra-
compared to its initial level of 1 mg/L and F 1 mg/L when its initial tions of As and F (Brunson and Sabatini, 2009). Fish bone char was
concentration was 4.5 mg/L. Rise in the pH of the solution led to better in removal of F and As simultaneously with minimal
increase in the As(III) removal efciency with best removal at 6e7 competition; F was removed more efciently than As. Further, the
pH. When Fe plate was employed as anode in the electro- use of sh bone char is a practical solution for F removal in poor
coagulation process, As(V) was effectively removed from water countries where rural populations cannot meet the expense of
because of the co-operation between Fe and As ions (Ratna Kumar membranes and electricity. Mlilo et al. (2010) have reported that F,
et al., 2006). Arsenic and F co-removal by coagulation/precipitation As(III) and As(V) adsorption capacity was higher in bone char than
is summarized in Table 2. in goethite coated sand and hematite coated sand.

4.2. Adsorption (AD) 4.3. Membrane technology (MT)

Adsorption technique is more popular due its simplicity, better Membranes have well-proven their use in various processes
efciency at high levels of total solids and suitability for household especially in desalination, membrane distillation and membrane
Table 2

316
Potential treatment methods for the simultaneous removal of As and F.

Technology Investigators and level of Type of water, raw materials/ Maximum removal capacity, Reference Merits Demerits Cost
development composition, geographical origin optimal/affecting parameters

Coagulation  Combination of cake alum and  Groundwater  F removal 99% Pinon-Miramontes et al.  Low cost  As/F laden sludge Lowa
polymeric anionic occulent  Composition: Well 1:  As removal 77% (2003)  Simple to use generation
(PAF) F 5.9 mg/L; As 0.139 mg/L ;  Optimal pH 7  Well proven  Unpleasant water
 Pilot plant lab scale research Well 2: F 4.8 mg/L;  Readily available taste
As 0.075 mg/L chemicals  Residual aluminum
 Meoqui City, Chihuahua,
Mexico
 ArCIS-UNR process  Groundwater  F removal 50e55% Ingallinella et al. (2011)
optimization  Composition: F 2.4e3.2 mg/L  As removal 75e85%
 Polyaluminum chloride As 60e90 mg/L
 Pilot plant
 Direct current  Synthetic water  F removal 91.5e93% Vasudevan et al. (2011)
electrocoagulation processes  Composition:  F removal (For As(V)

S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325


 Aluminum alloy as electrodes F 5e20 mg/L concentrations of 0, 0.5, 1, 3
 Lab scale research As(V) 0e5 mg/L and 5 mg/L) 93, 85.3, 77, 69
and 35%, respectively.
 integrated electro-oxidation  Synthetic water  F removal 81% Zhao et al. (2011)
and electrocoagulation (hybrid  Composition: F 4.5 mg/L  As(V) removal 98%
DSA-Fe-Al electrode) As 1 mg/L  Optimal pH 5e7
 Current density mA/cm2
 Duration 40 min
Adsorption  Adsorbent prepared through  Synthetic water  As(V) adsorption 97.9% at pH Ruixia et al. (2002)  Low to medium cost  pH sensitive Low to medium
the cross-linking reaction of  Composition: F 10 mg/L, 3.5 to 7  Simple to use  Considerable
PANF by hydrazine hydrate PO3 30 mg/L As(V) 38 mg/L  F adsorption 90.4% at pH 3  Efcient adsorbent
and functionalized reaction of (Separately treated) Mixed  PO3 adsorption > 99% at pH 3  Commercially available regeneration time
hydrazine-modied ber in ions, F 5 mg/L, PO3 50 mg/ to 5.5 sorbents  Needs standby process
mixture of sulfur powder and L, and As(V) 34.23 mg/L  In mixed ions F, As(V) and PO3  Can handle high levels of during regeneration
ethylenediamine treated in another run adsorption was ~50, 85 and solids  Exhausted adsorbent
 Lab scale research  Flow rate 2.5e3.5 ml/min 90% respectively disposal problem
 Equilibrium was reached  Competing ions reduce
within 5 min for all the efciency
experiments
 CeeFe adsorbent  Groundwater  Phosphate seriously affected Zhang et al. (2003)
 Lab scale research  Composition: As(V) 1.1 mg/L removal of As(V) while F did
F 1.59 mg/L not compete with As(V) even
 Zhijiliang Village, Inner at F/As molar ratio as high as
Mongolia, China 30, suggesting that adsorption
sites for As(V) and F were
different
 Mean As(V) adsorption
capacity 16 mg/g at pH 3-7
 Max As(V) adsorption
capacity 8.3 mg/g at pH 5.5
 Granular activated carbon-  Synthetic water  As removal > 98% Gu et al. (2005)
based iron-containing adsor-  Composition: As 105 mg/L  Max As adsorption (prepared
bents (As-GAC) and 1031 mg/L 90.0 mg solid by NaCl oxidation) 6572 mg/g
 Lab scale research per 30.0 ml solution  Presence of P and SiO
 pH 4.7 signicantly decreased As(V)
 Duration 24hr removal at pH > 8.5
 Effects of Cl, and F were
minimal
 Synthetic water  F removal 80% Delorme et al. (2007)
 Mixed oxides obtained from  Composition:  As(V) removal 100%
the moderate thermal F 10 mg/L As(V) 16 mg/L  NO3 removal 15%
treatment of quintinite NO3 100 mg/L  CO3 addition resulted
 Lab scale research in trapped ion leaching (90% F
and 20% As released)
 Three types of granular ferric  Synthetic water  F adsorption Streat et al. (2008)
hydroxide materials  Composition: capacity 1.8 mmol/g
 Lab scale research As(V) 0.0133 mmol/L  As(V) adsorption
F 0.0133 mmol/L capacity 0.9e1 mmol/g
P 0.0133 mmol/L  Phosphate adsorption
 pH 4e8 capacity 0.65e0.75 mmol/g
 Being not a triprotic acid, F did
not compete for same sites
with As
 Cow and sh bone char  Synthetic water  As(V) showed no Brunson and Sabatini
 Lab scale research  Composition: F 10 mg/L signicant competition for F (2009)
As(V) 0.250 mg/L  F adsorption
capacity 3.94 0.15 mg/g

S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325


 As(V) adsorption
capacity 4.41 0.23 mg/g
 Bone char showed greater
capacity to remove F than As
 Magnetite-type adsorbent  Groundwater  Reduction of As concentration Yoshizuka et al. (2010)
 Lab scale research/Field  Composition: to less than 0.01 mg/L was
sample testing As 0.01e3.23 mg/L F 0.04 obtained up to bed
e3.76 mg/L B 0.1e33.9 mg/L volume 200
 16 sites, Kyushu, Japan  Remarks:
 The focus was only on As; no
mention on F removal
 Ceramic adsorbent prepared  Synthetic water As(V) 10  As(V) adsorption Chen et al. (2010)
with a mixture of akadama and 20 mg/L (kinetic studies) capacity (Langmuir
mud, wheat starch, and Fe2O3 As(V) 5, 10, 20, 50, 65, 80, isotherm) 4.19 mg/g
 Lab scale research and 100 mg/L, respectively  Complex multilayer As(V)
(isotherm studies) adsorption was observed on
ceramic material
 Presence of P and F affected
As(V) adsorption
 Bone char, goethite coated  Synthetic water  F and As(III) and As(V) Mlilo et al. (2010)
sand (G-IOCS) and hematite  Composition: F 1e200 mg/L adsorption capacity was
coated sand (H-IOCS) with or without As (0.25 mg/ higher in bone char than in
 Lab scale research L) As 0.1e2.5 mg/L with or G-IOCS and H-IOCS
without F (10 mg/L)  F removal was not affected by
the presence of
environmentally signicant
As(III) and As(V)
concentrations
 F competes with As(V) for
adsorption onto bone char
 Goethite  Synthetic water  F adsorption Tang et al. (2010)
 Lab scale research  Composition: capacity 0.191e0.518 mg/g
F 5.1e25.1 mg/L  As(V) adsorption
As(V) 2.51e10.12 mg/L capacity 0.247e0.941 mg/g
 F and As adsorption was seen
strongly dependent on
contact time, pH, and surface
loading
(continued on next page)

317
Table 2 (continued )

318
Technology Investigators and level of Type of water, raw materials/ Maximum removal capacity, Reference Merits Demerits Cost
development composition, geographical origin optimal/affecting parameters

 F and As(V) adsorption onto


goethite obeyed pseudo
second-order rate law
 As(V) showed much stronger
afnity for goethite than F
 FeeCe oxide  Synthetic water  P strongly inhibited adsorption Zhang et al. (2010)
 Lab scale research  Composition: of As(V) at the low-binding-
As(V) 13.3 mmol/L Series of energy sites
molar ratios of As to P (1:0.1,  Coexistence of F, only
1:1, and 1:10) and As to F (1:1, inuenced total adsorption
1:10, and 1:100) capacity of As(V) at high
 pH 5.0 0.2 simultaneous F concentrations
 As(V) and P were mainly
adsorbed through the

S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325


substitution of Fe surface
active sites
 F was mainly adsorbed
through substitution of Ce
surface active sites on FeeCe
surface
 Adsorption on layered double  Power plant efuent data from  Effect on As adsorption Dadwhal et al. (2011)
hydroxides greater Los Angeles, USA used F < NO3 < Cl < CO3 < SO4 < P
 Lab scale research to simulate water  Presence of F greatly affected
 Composition: As 0.02 mg/L adsorption equilibrium
F 1 mg/L NO3 5 mg/L constant in As adsorption
Cl 100 mg/L CO3 5 mg/L  As adsorption
SO4 100 mg/L HPO4 1 mg/L capacity 3.6 mg/g
 pH 8  F adsorption
capacity 34.9 mg/g
 Inorganic ion exchangers  Synthetic water  Very fast kinetics of arsenate Chubar (2011)
developed based on double adsorption was observed
hydrous oxides of Mg and Al  As(V) adsorption
 Lab scale research capacity 220 mg/g
 As(III) adsorption
capacity 30e35 mg/g
 Fluoride, bromate, bromide,
selenate, borate, etc. compete
for adsorption sites
 Adsorption on  Synthetic water and surface  As(V) adsorption Chen et al. (2011)
ferric-impregnated water capacity (Langmuir
volcanic ash  Composition: As z 1 mg/L isotherm) 6.13 mg/g
 Lab scale research F 0.2e0.5 mg/L  Existence of multivalence
 Lake Kasumigaura, Japan metallic cations improved
As(V) adsorption
 Competing anions (F and P)
affected As(V) adsorption
 Fe and Al doped micro and  Synthetic water  F adsorption Kumar et al. (2011)
nano-polymeric beads  Composition: capacity 100 mg/g
 Lab scale research F 10e100 mg/L As 1  As adsorption
e50 mg/L (Separately treated) capacity 40 mg/g
 Mesoporous alumina and  Synthetic water  F adsorption Li et al. (2011)
calcium-doped alumina  Composition: F 2e1000 mg/ capacity 450 mg/g
 Lab scale research L As 100e200 mg/L  As(V) adsorption
(Separately treated) capacity 19.8 mg/g
 As(III) adsorption
capacity 5 mg/g
 N-methylglucamine  Synthetic water  Adsorption was highly pH Wei et al. (2011)
immobilized onto cross-linked  Composition: As(V) 0 dependent
chitosan beads e150 mg/L F 0e1 mM  As(V) adsorption
 Lab scale research capacity 69.28 mg/g at pH 5
 Effects of competitive anions:
SO4 >> P >> F
 Cellulose-g-PDMAEMA  Synthetic water  F adsorption capacity 1.5 Tian et al. (2011)
adsorbent prepared by  Composition: e7.5 mg/g
modifying surface of native F 1.8e12.8 mg/L  As(III) adsorption
cellulose bers with poly (N,N- As 0.05e8.9 mg/L capacity 0.06e7.8 mg/g
dimethyl aminoethyl  As(V) adsorption
methacrylate) capacity 0.05e8.7 mg/g
 Adsorption capacities
calculated from Langmuir and
Freundlich equations were

S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325


both in the order of
As(V) >> As(III) > F
 Composite adsorbent with  Synthetic water and  As removal > 80% Jing et al. (2012)
titanium and lanthanum groundwater  F removal > 35%
oxides impregnated on  Groundwater Composition:
granular activated carbon As(III) 0.73 mg/L
 Lab scale research As(V) 0.69 mg/L F 2.01 mg/
L TOC 7.5 mg/L
 pH 8.0
 TLAC 1 g/L
 Shanxi Province, China
 Nickel and magnesium  Synthetic water  The interference of other Jimenez-Nunez et al. (2012)
hydrotalcite-like compounds  Composition: F 5 mg/L 5 ml anions in the sorption kinetic
(NiAlHT, MgAlHT) of one of the following of F ions by NiAlHT and
 Lab scale research solutions: Cl 20 mg/L, MgAlHT was: SO4 > As(V) > Cl
SO4 35 mg/L or
As(V) 2 mg/L to 50 mg of
each hydrotalcite-like
compound
 Speed 200 rpm
Membrane  Combination of solar energy  Groundwater  F rejection  88% Richards et al. (2009)  Highly efcient  High initial cost High
ltration and NF/RO (PV-membrane)  Composition:  As rejection 78%  No chemicals required  High operating cost
 Pilot plant F z 10 mg/L As z 5e6 mg/L  Mg rejection 99%  Does not inuence water  High water rejection
Mg z 150 mg/L  Pine Hill taste and color  Brine disposal
Station and Ti Tree Farm,  Ability to completely problem
Australia purify water  Need of after
 Nanoltration  Synthetic water  As(V) rejection 93% Padilla and Saitua (2010) treatment re-
 Pilot plant  Composition As(V) 180 mg/L  F rejection 89% mineralization
F 5 mg/L HCO3 84 mg/L  HCO3 rejection 85%
 pH 8
 Pressure 7 bar
 Solar (photovoltaic) powered  Groundwater  More than 85% overall Richards et al. (2011)
UFeNF/RO system  Composition: F 1.1 and rejection
 Lab scale research 0.464 mg/L As 0.005 and  As rejection ~64e79% on
0.003 mg/L TDS 5700 and BW30, TFC-S, ESPA4, and
1080 mg/L NF90 membranes
 Pine Hill and Ti Tree, Australia  F rejection ~98.5% on BW30
membrane
 Rejection of arsenic was
independent of pH from
3 to 11
(continued on next page)

319
320 S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325

reactors. As described earlier, although there are several reports


on F as well as As removal from synthetic aqueous solutions by
employing RO and NF processes with high removal efciencies,

Very high
only a few reports have dealt with natural groundwater (Nevarez
Cost

Low
et al., 2011). A widely known separation mechanism has already
been described in section 3.1.4.
A series of experiments were performed in Central Australia to
evaluate elemental retention with four different membrane
modules (BW30, ESPA4, NF90, and TFC-S) at different pH values
ranging from 3 to 11 (Richards et al., 2009). A pilot plant using
solar energy and a two-staged membrane process consisting of UF
Demerits

followed by NF/RO was developed for water purication. The


average removal of F and As was found to be nearly 88 and 78%,
respectively, on NF90 membrane. Moreover, F and As removal was
observed to be independent of pH. Average retention of As was 79,
65, and 75% for the BW30, TFC-S, and ESPA4 membranes,
respectively. It has been suggested that variations in retention
based on membrane type were likely due to membrane charac-
teristics. Further, the same membranes were used in another study
for photovoltaic powered UFeNF/RO system in real water treat-
Merits

ment to conrm the results (Richards et al., 2011). A recent study


on forward osmosis (FO) has demonstrated promising results
(~95%) for As(V) removal in presence of F (Mondal et al., 2014). A
Yarlagadda et al. (2011)

pre-oxidation of As(III) was necessary for efcient As removal at


 As rejection 17.80e25.40% Nevarez et al. (2011)

pH 7. Also, a two pass FO-RO system was proven to be more


Devi et al. (2008)

sustainable than a two pass RO system.


A pilot scale NF plant was operated to evaluate performance on
Reference

simultaneous removal of As, F and HCO3 from a synthetic water


solution laden with 180 mg As(V)/L, 5 mg F/L and 84 mg HCO3/L
(Padilla and Saitua, 2010). At 7e8 bar, the removal of As and F was
e10,000 mg/L As and U 10  As, F and U reduction ~96.5
matter present in groundwater
(solar irradiance between 0.2

affected by ionic and organic


and 1.0 kW/m2) inuenced F

93 and 89%, respectively. However, reducing the pressure to 2 bar


membranes was found to be
 F rejection 14.29e27.14%

20 ppm (>99% rejection of


composition, geographical origin optimal/affecting parameters
Maximum removal capacity,

reduced the removal efciency to 91.6 and 73.3% for As and F,


concentrations less than

respectively. These ndings are in consonance with the so-called


 As removal 93.07%
F 11.8 mg/L As 0.435 mg/L  As and F removal by

 F removal 85.60%

dilution effect; at higher pressures, the permeate water ux


 Energy variations

Synthetic water and brackish  Dissolved solids

increases more than the salt ux (Seidel et al., 2001). Therefore,


(0.009 mg/L)

the salt concentration in permeate is reduced due to increased


(0.72 mg/L)
rejection

removal. Further, by reducing the pressure, the convection is low


e99.9%
salts)

and consequently, the diffusive contribution becomes signicant.


Similar ndings have been reported by other workers as listed in
Table 2.
Brackish water composition:

An interesting investigation carried out on nanocomposite


F 5 mg/L As 0.13 mg/L
Unknown source, Probably
Type of water, raw materials/

e400 mg/L F 1e30 mg/L

membranes suggested that As and F removal can be inuenced by


Dissolved solids 1000

ionic and organic matter content in groundwater (Nevarez et al.,


The cited literature does not give actual costs and hence this is relative.
Chihuahua, Mexico

2011). Nanocomposite membranes synthesized from propio-


Drinking water

nated lignin (such as Kraft, Organosolv and Hydrolytic) and cel-


Composition:

Composition:
Groundwater

lulose triacetate (CTA), removed 17.80e25.40% As and


pH 7.17

14.29e27.14% F. Membrane effectiveness was also inuenced by


water
India

The bold text represents the country of groundwater source.

suspended solids (Meenakshi et al., 2004).


There are several RO plants operating in Argentina and Mexico









for F and As removal. Regardless of their high separation efciency,


 Filtration on home-made lter
tion method from propionated
lignin and cellulose triacetate
vapor-induced phase separa-

RO systems suffer from considerable water loss (35e65%) due to


 Direct contact membrane
distillation (DCMD) using

the discharge of concentrated retentate stream which should be


membranes prepared by
 Nanocomposite (NF/RO)

polytetrauoroethylene
Investigators and level of

treated before being discharged. However, there are no means to


ltration/Distillation

 Lab scale pilot plant


polypropylene and

treat or safely dispose the rejected brine. Moreover, poor com-


 Lab scale research

munities cannot afford the high running cost (Ingallinella et al.,


membranes

2011).
 Membrane
 Pilot plant
development

 Filtration

media

4.4. Other technologies


Table 2 (continued )

In a quest to develop appropriate technology for the concurrent


elimination of As and F, a limited number of researchers have
Technology

made out of the box efforts to see the opportunities. Devi et al.
(2008) carried out removal of F and As by modied home-made
Others

lter media for potable water. The system consisted of two


a

metal tanks, each with 30 cm diameter and 100 cm height, tted


S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325 321

with 1.25 cm outlet pipe, a drain valve and an outlet tap. One tank selectivity of activated alumina towards As(V) resulting in regen-
was lled with 10 cm stone at bottom (pebbles); 8 cm lter gravel eration problems.
consisting of two layers of different sizes of 4 cm deep each (particle Pre-oxidation step is required to convert As(III) to As(V) for
size ranges 0.8e1.5 mm) and a layer at the top of 40 cm deep lter practical removal of As(III). Strong dependency on pH limits the
sand (size of 0.2e0.8 mm). The second tank was also lled similarly applicability of adsorption. Moreover, regeneration steps result in
except that a 10 cm crushed brick (particle size ranging from 0.25 to secondary pollution which is also applicable to ion exchange;
0.5 mm) was added to operate the experiments in batches for 2, 4, although in the case of ion exchange resins, high cost of resins is
6, 8, 10 and 12 h. The initial concentrations of F and As were kept at always associated with high removal (~95%) performance for As
5 mg/L and 0.13 mg/L, respectively during the experiment. This and F (Mohan and Pittman, 2007; Solangi et al., 2009). Fluoride,
simple set-up was effective to remove F and As nearly by 86 and sulfate, nitrate, selenium and phosphate are competitive species
93%, respectively. with arsenic affecting the duration of adsorption. Improved
Yarlagadda et al. (2011) used a different approach of direct removal along with the reduction in regeneration cycle can be
contact membrane distillation process for the recovery of potable achieved by passing of water through a series of columns. Ion ex-
water from As, U and F contaminated groundwaters. Polypropylene change beds are susceptible to clogging due to the presence of
and polytetrauoroethylene membranes were evaluated with suspended solids and pretreatment is recommended which
synthetic brackish water composition: As and U: 10e400 mg/L; F: otherwise escalates the equipment and operating cost (Shah,
1e30 mg/L; and salts: 1000e10,000 mg/L. The results showed more 2008).
than 99% removal of salts along with As, F and U removal in the More than 95% As and F removal is achieved by RO along with
range of 96.5e99.9%. complete purication and disinfection when the operating pressure
is ideal (Dolar et al., 2011; Oehmen et al., 2011). For instance, Fig. 5
5. Disposal of trapped/separated As and F demonstrates that RO and NF are the most useful technologies in As
and F removal. Literature reports illustrate that electrodialysis
Although a lot of work has taken place to remove As and F in reversal can eliminate 80% of the pollutants (Litter et al., 2010;
isolation or together from a mosaic of ions, the real worry is two- Ravenscroft et al., 2009). However, the release of brine is also of
fold: how to dispose of the concentrate or retentate and how to great concern. Moreover, these membranes suffer from 35 to 65%
stop its recycle back into the groundwaters. Communities using any water loss at retentate side which should be treated before being
of the low-cost technologies to make their local potable water discharged. Although membrane distillation has shown promising
supply free of As and F, also need to be provided with low-cost and co-removal potential, it turns out to be the most expensive tech-
effective means of dealing with the loaded and exhausted adsor- nique for As and F removal (Fig. 5). Fig. 5 also shows that co-
bents or concentrated brines. There is no worthwhile technology presence of As and F results in nearly 15e20% reduction in
available except the disposal of concentrated streams in sea. removal efciency of any treatment method. Therefore, consider-
The foregoing discussion illustrated that successful treatment of ation must also be given to this issue while synthesizing and/or
water containing high dissolved solids (TDS) can be carried out by selecting the treatment route. On the other hand, although cost
using activated alumina (AA). Conversely, the presence of effective, the precipitation scheme for F removal leaves toxic re-
competing ions (sulfates, nitrates, selenium, chlorides, etc.) may sidual aluminum complex in drinking water.
seriously affect the adsorption rates. Nearly 5e10% loss of absorp- The synthesis of nanosized adsorbents and encapsulation
tive sites for every run should be considered as a benchmark while technologies to isolate loaded adsorbents and dispose them as
separating As(V) with activated alumina. This is due to high landll or for burial will be highly useful. Synthesis of highly

Fig. 5. Simultaneous uoride and arsenic removal performance of various technologies. Where, CPC-31 Pinon-Miramontes et al. (2003); CPC-32 Ingallinella et al. (2011); EC-
33 Zhao et al. (2011); AD-34 Ruixia et al. (2002); AD-35 Jing et al. (2012); AD-36 Brunson and Sabatini (2009); RO/NF-37 Richards et al. (2009); RO/NF-38 Richards et al.
(2011); RO/NF-39 Padilla and Saitua (2010); RO/NF-310 Nevarez et al. (2011); Other-311 Devi et al. (2008); Other-312 Yarlagadda et al. (2011). Note: A special note of
Delorme et al. (2007) should be taken as this is not shown in gure due to drawing constraints. The authors obtained 100% As and 80% F removal from initial concentrations 16 mg
As/L and 10 mg F/L.
322 S.V. Jadhav et al. / Journal of Environmental Management 162 (2015) 306e325

selective nanomaterials for membranes could be used for both As Appendix A. Supplementary data
and F removal. Activated alumina treatment is pH dependent and
hence treatment of water with mineral acids will be required. This, Supplementary data related to this article can be found at http://
however, needs further research, particularly sustainable means of dx.doi.org/10.1016/j.jenvman.2015.07.020.
contaminants laden sorbents. Rice husk, bone char, red mud, coal,
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