S. Iftekhar et al.
/ Chemosphere 204 (2018) 413e430
3.3. Commercially available adsorbents
Commercially available adsorbents including MWCNTs
(Koochaki-Mohammadpour et al., 2014), graphene oxide (Ashour
et al., 2017a), activated carbon (Marwani et al., 2013) and tailored
activated carbon-silica composite have demonstrated great po-
tential for La recovery. Although commercially available adsorbents
offer high surface area, the major drawback of using commercially
available adsorbents is their high cost as compared to locally
available biosorbents or other low cost hybrid materials.
4. Factors of operating conditions on La adsorption by
various materials
A wide range of materials including naturally occurring, syn-
thetic and hybrid adsorbents has been investigated for La separa-
tion under different operating conditions such as pH, adsorbent
dose and contact time (Table 1). However, efforts are required to
systematically analyze the wealth of studies to estimate operating
conditions to achieve efficient La adsorption. In this section, the
influence of operating conditions on La adsorption process by
different materials is elucidated based on the data presented in
Table 1.
4.1. Effect of pH
pH is one of the most important process variables that can
directly affect the uptake of La by adsorbents because it can affect
the extent of La ionization as well as the surface characteristics of
an adsorbent. In order to understand La behavior in solution, the
chemical equilibrium for the estimation of La speciation over a pH
range of 1e12 was carried out by Visual MINTEQ (ver. 3.0). Up to pH
6, La is the dominant species in solution, while it converts to
LaOH3þ by increasing the pH of the solution beyond 6 (Fig. 2).
A number of biosorbents have been studied for La adsorption.
These biosorbents include Sargassum polycystum (Diniz and
Volesky, 2005b), Sargassum fluitans (Palmieri et al., 2002),
Sargassum biomass (Diniz and Volesky, 2005a), Grobacterium sp.
(Shuxia et al., 2011), marine algae (Vijayaraghavan et al., 2011), crab
shell (Vijayaraghavan et al., 2009), fish scale (Das et al., 2014), peels
(Torab-Mostaedi, 2013; Torab-Mostaedi et al., 2015) and leave
powders (Sert et al., 2008; Kütahyali et al., 2010), modified and
unmodified biochar (Wang et al., 2016b). These biosorbents have
been reported to show pH-dependent La adsorption. For example,
Palmieri et al. (2002) observed ten-fold increase in La uptake by
S. fluitans when pH of the process was changed from 2 to 5. In
another study by Diniz and Volesky (2005a), a rapid increase in La
adsorption on Sargassum biomass was observed following an in-
crease in pH. Similarly, by increasing the pH to 6.8, La adsorption
rate on Agrobacterium sp. was also improved (Shuxia et al., 2011).
Based on the comprehensive literature survey in this study, it
seems that the mechanism of La removal by adsorbents can change
from adsorption to precipitation, depending on the pH of the re-
action media. For example, Vijayaraghavan et al. (2009) studied the
efficacy of pre-treated crab shells (PCSP) for La adsorption. They
observed that PCSP can act as a nonspecific chelator and forms
weak hydrogen bonds with La due to the presence of chitin in PCSP.
In addition, an increase in the pH of the reaction media from 5 to
9.6 was also observed during La adsorption by PCSP, which can be
attributed to dissolution of carbonate groups available on PSCP
surface (Vijayaraghavan et al., 2009). Notably, due to change in the
pH of the reaction media, the dominant mechanism of La removal
was changed from adsorption to precipitation in the form of LaCOþ 3 3 < pH < 6, thus La adsorption may increase in this range
and La(CO3)-2 (Vijayaraghavan et al., 2009). Although pH is reported
as the most important performance governing factor, Wang et al.
417
(2016b) observed that La adsorption by ammonium-citrate-
modified biochar was not affected by solution pH. Although the
author did not elucidate the reason, it can be seen from proposed
structure of adsorbent shown in Scheme 3 that adsorbent surface
contains various functional groups including carboxyl, hydroxyl
and, providing an opportunity for the optimization of adsorbent
dose. Another possible explanation might be that after modification
of biochar with ammonium citrate, the zero point charge of surface
lies around pH 3.5e4. Thus, the adsorbent is efficient enough to
adsorb La at pH 4 (slight acidic) due to presence of different func-
tional groups and in acidic region (i.e. pH 3) due to electrostatic
repulsion between surface functional groups and Hþ ions.
In addition to different biosorbents, a variety of other adsorbent
materials have been employed for La removal. These adsorbents
include organic-inorganic hybrid nanocomposites, while some are
modified silica-based materials (Table 1). Among these organic-
inorganic hybrid materials (Table 1), the application of magnetic
nanoparticles in the organic matrix is widely used. Due to the
presence of organic matrix, La adsorption occurs by complexation
of surface functional groups with La at a certain pH (Wu et al.,
2010). A similar observation was made when Cysteine functional-
ized chitosan magnetic nanocomposite (Cys@CHI-magnetic) were
assessed for La adsorption at pH 5 (Galhoum et al., 2015). Notably,
the formation of La-organic complexes did not change the solution
pH, and this was attributed to the buffering capacity of Cys@CHI-
magnetic nanocomposite (Galhoum et al., 2015). Other adsor-
bents exhibiting buffering capacity against pH change include
Layered double hydroxides (LDH) based materials (Kameda et al.,
2011; Granados-Correa et al., 2012; Iftekhar et al., 2017d). Howev-
er, it is important to note that not all adsorbents can act as a buffer.
For example, Ashour et al. (2016) reported that Cys@Fe3O4 nano-
particles did not seem to have the buffering capacity, despite hav-
ing amine and carboxylic functional groups.
Some organic grafted materials achieved promising results for
La adsorption. These materials include CTS-g-PAA/APT (Zhu et al.,
2015a), HPC-g-PAA/APT (Zhu et al., 2015b) and DGA-g-PAA (Zhou
et al., 2016). The optimum pH for these materials ranged from 5
to 7 (Table 1). A large number of silica-based adsorbents reported in
the literature were proved to be quite effective for La adsorption. In
a study by Tadjarodi et al. (2015), HESI-SBA-15 achieved effective La
adsorption (96%) at pH 7. In recent studies, various modified silica
gels such as amine-functionalized silica (Ramasamy et al., 2017c),
hybridized silica-chitosan (Ramasamy et al., 2017d) and silica-
carbon composites (Ramasamy et al., 2018b) were subjected to
the investigation of REEs uptake including La. These adsorbents
when grafted with silanes and ligands, exuded an enormous po-
tential for the recovery of La in the acidic pH regime. The interesting
observation made during one of these studies was that when the
ligands, 1- (2-pyridylazo)-2-naphthol (PAN) and acetylacetone
(Acac), were chemically immobilized onto the silica surface by
means of a coupling agent, such as 3-aminopropyltriethoxy silane
(APTES) and 3-aminopropyltrimethoxy silane (APTMS), resulted in
a supreme La adsorption from a lower pH regime of 4 and 5. On the
other hand, the same ligands, when grafted via physical loading
process without any coupling agent resulted in shifting the opti-
mum adsorption pH to 7 (Ramasamy et al., 2017a). Similarly, when
the chitosan units containing pH-responsive functional groups
were hybridized with amine-functionalized silica, caused the
adsorption of La to occur from the acidic pH range of 2e3
(Ramasamy et al., 2017d, 2018a).
Commercially available MWCNTs and GO have also been used
for La adsorption. MWCNTs becomes negatively charged at
(Koochaki-Mohammadpour et al., 2014). GO sheets seem to be
highly negatively charged due to the presence of oxygen functional