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Recent innovative research on chromium (VI) adsorption mechanism

Md. Aminul Islam, Michael J. Angove, David W. Morton

PII: S2215-1532(19)30168-0
DOI: https://doi.org/10.1016/j.enmm.2019.100267
Reference: ENMM 100267

To appear in: Environmental Nanotechnology, Monitoring & Management

Received Date: 6 July 2019

Revised Date: 22 August 2019
Accepted Date: 12 October 2019

Please cite this article as: Islam MA, Angove MJ, Morton DW, Recent innovative research on
chromium (VI) adsorption mechanism, Environmental Nanotechnology, Monitoring and amp;
Management (2019), doi: https://doi.org/10.1016/j.enmm.2019.100267

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Recent innovative research on chromium (VI) adsorption mechanism

Md. Aminul Islam a, b, *, Michael J. Angove a and David W. Morton a

a
Colloid and Environmental Chemistry (CEC) Research Laboratory, Department of

Pharmacy and Biomedical Sciences, La Trobe Institute for Molecular Science (LIMS), La

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Trobe University, Bendigo, VIC-3550, Australia

b
Department of Arts and Sciences, Faculty of Engineering, Ahsanullah University of Science

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and Technology (AUST), Dhaka-1208, Bangladesh

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*
Corresponding authors E-mail: aminul.chem.as@aust.edu (Md. A. Islam
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Graphical abstract
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Number of papers revomed Cr(VI) using

various substrates
Period: 1985-2019;
Sources: Google Scholar, Web of Science,
Number of papers

PubMed and Scopus

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50 22 18 29 23 14 31 14
0
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Substrate

Highlights

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  Cr(VI) adsorption has been studied using a wide range of materials;

 Low-cost or composite materials exhibited excellent Cr(VI) adsorption;

 The nature of Cr(VI) adsorption onto substrates was primarily chemisorption;

 Cr(VI) adsorbed by forming both outer and inner-sphere Cr(VI) complexes;

 There is a need to study spectroscopic, surface complexation model SCM) and density

functional theory (DFT).

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Abstract
Chromium (VI) is an important heavy metal commonly found in tannery wastewater.

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In order to manage this type of environmental pollution, there needs to be a better

understanding of Cr(VI) adsorption mechanisms. This article reviews the recent usage of
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various adsorbents to adsorb Cr(VI) from wastewater. The paper provides an overview of the
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removal capacity of numerous adsorbents in terms of Cr(VI) speciation, empirical modeling,

surface complexation model (SCM) and spectroscopic measurements carried out by a wide
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number of researchers. Special emphasis was given to summarise various proposed Cr(VI)

adsorption mechanism. It has been noted that Cr(VI) adsorption has been studied using a
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wide range of adsorbent materials with adsorption capacity from low to higher depending

several factors including the nature and type of adsorbent, surface property of adsorbent,
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surface modification, pre-treatment of substrate, coexisting substrate and experimental

conditions (equilibration time, solution pH, initial Cr(VI) concentration, ionic strength).
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Cr(VI) adsorption was highly dependent on solution pH and Cr(VI) adsorbed strongly in

acidic pH while it exhibited weak or no adsorption in alkaline pH condition. Cr(VI)

adsorption data has been studied using proton stoichiometry, kinetic, Langmuir, Freundlich,

and surface complexation model (SCM). Adsorption data commonly fitted with a pseudo-

second-order (PS2) kinetic model and Langmuir equation. Cr(VI) adsorbed typically by

2
inner-sphere Cr(VI) complex at pH below 6.0 and by outer-sphere Cr(VI) complex above pH

6.0. Proton stoichiometry indicated that more than one reaction was involved in Cr(VI)

adsorption. This review can be a centrepiece of researchers who wish to work on Cr(VI)

adsorption. This study will shed new light on the understanding Cr(VI) adsorption onto the

substrate at the water-solid interface and develop high-performance substrate to remove

pollutants efficiently from wastewater.

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Keywords: Wastewater, Chromium (VI), Adsorption, Adsorbent, Langmuir, Surface
complexation model.

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1. Introduction
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Chromium (VI) is an important naturally occurring metal widely used in a variety of areas,
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including mining, wood preservation, leather tanning, paint pigments, textile printing and

dyeing, refractories (chrome and chrome-magnetite), aerospace, and electroplating (Dehghani

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et al., 2015; Dupont and Guillon, 2003; Fendorf, 1995; Nriagu and Nieboer, 1988). The

release of a considerable amount of chromium in the environment is the result of leakage,

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poor storage, and improper disposal practices associated with industrial processes (Barakat,

2011; Jacobs and Testa, 2005; Palmer and Wittbrodt, 1991). At the same time, various
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chromium bearing minerals, including chromite are available in the soil and bedrock also

releases natural chromium into the environment. Chromium is available in six different
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oxidation states (0 to VI) on the Earth’s surface (Chebeir et al., 2016). Among them, Cr(VI)

is a priority contaminant in soils and aquifers in industrial areas and is ranked the top sixteen

toxic pollutants that have very harmful consequences on human health and aquatic life.

Cr(VI) contamination of soil and aquatic systems is a significant problem worldwide. Acute

exposure to Cr(VI) can cause diarrhea, nausea, kidney failure, liver diseases, lung cancer,

3
ulcer formation and respiratory troubles (Ghashghaee and Farzaneh, 2016; Owalude and

Tella, 2016b; Saha et al., 2011; Zhitkovich, 2011). Since Cr(VI) causes a great threat to

humans as well as animals, removal of the contaminant to an acceptable threshold before its

discharge from various industrial sources into the soil and water is of the utmost importance

(Dupont and Guillon, 2003; Owalude and Tella, 2016b). The maximum allowable

concentration limit for Cr(VI) in drinking waters suggested by the Environmental Protection

Agency (EPA) is 0.05 mg/L (Parlayici and Pehlivan, 2019).

Chromium is an important metal contaminant commonly found in tannery waste.

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However, chromium (III) is an important trace metal for plants and animals (Katz and Salem,

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1994). Often it becomes a problem in environments rich in manganese oxides because of

oxidation from Cr(III) to Cr(VI) (Fandeur et al., 2009; Nriagu and Nieboer, 1988). Cr(III)
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tends to be associated with solids, whereas Cr(VI) is quite soluble, mobile, and is a toxic

contaminant in natural waters (Buerge and Hug, 1999). Those processes that increase the
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environmental concentration of Cr(IV) are, therefore, important to understand, due to the
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mobility and persistence of this toxic species (Sun et al., 2018). The oxidation of Cr(III) by

oxide minerals is thought to involve an initial adsorption step, and the tendency for Cr species

to remain at the mineral surface is likely to be a function of the affinity the species has for the
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surface. The enrichment of Cr(VI) in the soil is an important environmental concern because

of its mobility and acute toxicity. The mobility of Cr(VI) is largely governed by adsorption
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and desorption processes on substrates.

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In order to remove Cr(VI) from the aquatic environment, a wide number of technologies

have been adopted with the success of these procedures depending on Cr(VI) concentration

and nature of Cr(VI) sources. Commonly used removal procedures are adsorption (Ma et al.,

2016), membrane separation (Modrzejewska and Kaminski, 1999), reverse osmosis (Rad et

al., 2009), coagulation-flocculation (Akbal and Camcı, 2011), chemical precipitation

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(Kongsricharoern and Polprasert, 1996), photocatalytic degradation (Singh and Sarma, 2016),

and ion-exchange (Rengaraj et al., 2001). Each of the procedures has its own advantages and

disadvantages depending on the application and concentration of pollutants. However, these

methods are insufficient or costly when Cr(VI) is present at trace levels. Among them,

adsorption has been proved to be a very efficient method for Cr(VI) removal from aquifers.

There are several reviews related to Cr(VI) published in recent years. These include the

chemistry, occurrence and treatment of Cr(VI) (McNeill et al., 2012), sources and distribution

of Cr(VI) (Ertani et al., 2017; Hausladen et al., 2018), health impact, and regulations analysis

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of Cr(VI) (McLean et al., 2012), aqueous geochemistry of chromium (Richard and Bourg,

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1991), application of Cr(VI) in cement preparation (Hills and Johansen, 2007), treatment

technologies for Cr(VI) (Hawley et al., 2004), methods for Cr(VI) reduction (Barrera-Díaz et
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al., 2012) and bio reduction (Pradhan et al., 2017), genotoxicity of Cr(VI) (De Flora et al.,

1990), (eco)-toxicology of Cr(VI) (Katz and Salem, 1993; Proctor et al., 2002; Shahid et al.,
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2017; Velma et al., 2009; Zhitkovich, 2005), carcinogenicity of Cr(VI) (Costa, 1997; Dayan
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and Paine, 2001; Sedman et al., 2006), Cr(VI) removal (James, 1996; Owlad et al., 2009;

Thatoi et al., 2014) by bioadsorption and biotransformation (Jobby et al., 2018), Cr(III/VI)

removal by (raw and modified) lignocellulosic materials (Miretzky and Cirelli, 2010),
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agricultural waste biomass (Garg et al., 2007), polyaniline-based adsorbents (Jiang et al.,

2018), Cr(VI) detoxification by microorganism and bioremediation application mechanism

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(Cheung and Gu, 2007), toxic and mutagenic impacts of Cr(VI) (Cieślak-Golonka, 1996),
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chemical and microbial remediation of Cr(VI) (Dhal et al., 2013), Cr(III/VI) removal by

activated carbon and low cost adsorbents (Mohan and Pittman Jr, 2006), inorganic materials

(Rosales-Landeros et al., 2013) and carbon nanotubes (Anastopoulos et al., 2017). In

addition, individual removal of Co(II) (Islam et al., 2018b), Ni(II) (Islam and 2019; Raval et

al., 2016), Mn (Patil et al., 2016), phosphate (Huang et al., 2017), fluoride and arsenic (John

5
et al., 2018) and As(III/V) (Asere et al., 2019) are available in literature. (Rosales-Landeros

et al., 2013) explicitly reviewed Cr(VI) adsorption using various pure and modified inorganic

substrates such as clays, zeolites, and silica from aqueous solution. They noted that some of

the low-cost substrates showed good Cr(VI) adsorption performance and modification of

these surfaces by impregnation or coating dramatically improved Cr(VI) adsorption capacity.

(Dimos et al., 2012) systematically reviewed recent advances of Cr(VI) adsorption onto raw

and modified natural minerals. The authors summarized the theoretical approaches of Cr(VI)

removal using adsorption and ion-exchange process and present a detailed view of

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experimental parameters in terms of equilibrium isotherm and thermodynamic calculation. In

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addition, they described the potential of low-cost natural and modified minerals in Cr(VI)

adsorption from aqueous solution. However, there is no such systematic review in literature
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which summarises the recent development of Cr(VI) adsorption onto a wide number of

surfaces together with comparative, competitive and mechanisms of C(VI) adsorption.

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The objective of this review is to summarise recent application of various adsorbents to
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adsorb Cr(VI) from wastewater and provide up to date information in this area. Special

emphasis was given to the Cr(VI) adsorption mechanism in terms of empirical, spectroscopic
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and surface complexation modelling (SCM). The review also focuses on comparative and

competitive adsorption of Cr(VI) in the presence of other cations, anions, HA, and their
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impact on Cr(VI) adsorption. The various pathways of Cr(VI)-surface interaction, the impact

of solution chemistry, environmental conditions and substrates characterization are also

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described. This study advances knowledge on Cr(VI) adsorption behavior on diverse surfaces

and may provide new insights to assist in the development of environmentally friendly and

low-cost substrates for the purification of Cr(VI) contaminated water.

6
1.1. Adsorption

Adsorption is a complex surface phenomenon for retaining metal ions and organic

ligands in the soil environment. It is the accumulation of a solute from a solution onto a solid

surface (Toth, 2002). The process is generally considered as an equilibrium between

adsorbate and the surface to form a complex via adsorption or precipitation:

≡S (surface) + M (adsorbate) ↔ ≡SM (complex)

Competitive adsorption is the accumulation of a species in the presence of another sorbing

species. This is highly relevant because in nature various sorbate species exists together (Hu

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et al., 2018; Violante et al., 2010). Often their individual adsorption properties change

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significantly due to the presence of another species (Hu et al., 2018; Violante et al., 2010).

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Multiple species in the system must compete for a finite number of surface sites. As

the cumulative adsorption of all species will exceed that of any individual element,
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competitive adsorption will generally act to reduce the adsorption of a given species (Griffin

and Au, 1977; Zhao et al., 2016). Generally, the system will reach equilibrium if sufficient
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contact time is available. However, total adsorption/total concentration relationships may be

nonuniquely defined (Murali and Aylmore, 1983). Furthermore, some sites may only be
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available to one type of competing ion (Hu et al., 2018; Murali and Aylmore, 1983).

Competitive adsorption of metal ions and contaminants onto soil minerals is important
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because of their fate and transport properties in the natural environment. Competitive surface

adsorption has been demonstrated in several previous studies for metal ions (Hu et al., 2018;
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Rout et al., 2013; Srivastava et al., 2009) and anions (Wang et al., 2013; Wu et al., 2000; Wu

et al., 2001). In this study, the competitive adsorption of Cr(VI) in the presence of another

metal ions, anions, and HA has been reviewed using several substrates.

7
2. Chromium adsorption onto mineral surfaces

There are numerous classes of adsorbents that have been applied to adsorb Cr(VI)

from the aquatic environment. Examples include activated carbon or carbonaceous materials

(Chaudhuri and Azizan, 2012; Enniya et al., 2018; Huang et al., 2015), agriculturally based

low-cost substrates (Fan et al., 2017; Gorzin and Bahri Rasht Abadi, 2018), metal oxides

(Gheju et al., 2016; Granados-Correa and Jiménez-Becerril, 2009), clay materials (Liu et al.,

2016; Zhou and Chen, 2000), zeolites (Adam et al., 2018; Yusof and Malek, 2009),

biopolymers (Dupont and Guillon, 2003; Sessarego et al., 2019), and miscellaneous

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substrates (Alemu et al., 2018; Burillo et al., 2013). Activated carbon and some agriculturally

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based substrates show promising Cr(VI) adsorption from the aquatic environment. Some of

these adsorbents have their own drawbacks related to the difficulty of their separation after
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the adsorption process and high cost. However, there is still an increasing demand for the

development of high-efficiency and economic substrates for Cr(VI) adsorption. In the

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following section, the detailed Cr(VI) adsorption study performed by various researchers is
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described.
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2.1. Activated carbon/carbonaceous surface

Commonly, activated carbon or carbonaceous materials are capable of adsorbing a

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wide pollutant species including metal ions, anions, organic dyes, and humic substances

(Huang et al., 2015; Islam, 2018). However, the high cost of these substrates limits their
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application in many cases. There is a recent demand to prepare these materials from locally

abundant waste substrates. Previously, several papers have dealt with Cr(VI) adsorption using

carbonaceous surfaces (Chaudhuri and Azizan, 2012; Enniya et al., 2018; Huang et al., 2015).

Recently, Huang et al. (Huang et al., 2015) investigated the potential of magnetic multi-

walled carbon nanotubes (MWCNTs) in Cr(VI) adsorption from simulated wastewater. They

8
noted that Cr(VI) adsorption was highly pH dependent and adsorption was tended to decrease

with increasing pH of solution due to the surface chemistry of the nanotubes. Langmuir

equation better reflected Cr(VI) adsorption than the Freundlich equation while PS2 described

adsorption kinetic data satisfactorily. Maximum surface coverage was 13.2 mg/g at 30 °C. A

spontaneous and endothermic process occurred in Cr(VI) adsorption. Cr(VI) adsorption onto

the surface was primarily driven by physical adsorption. (Yusuff, 2019) launched Leucaena

leucocephala seed pod activated carbon (SSA 90 m2/g; pHPZC 5.2) to adsorb Cr(VI) from

aqueous solution. pH was highly sensitive to Cr(VI) adsorption with maximum adsorption

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occurring across the pH range of 5.0 to 7.2. It was found that the Langmuir equation

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described equilibrium data well while PS2 followed kinetic data reasonably with a maximum

surface coverage of 27 mg/g at pH 6.0 and 40 °C. Thermodynamic behavior of Cr(VI)

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adsorption was spontaneous and endothermic. Application of NaOH showed satisfactory

regeneration capacity of the substrate. (Parlayici et al., 2015) prepared AC functionalized

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MWCNTs and CNTs and used these surfaces to adsorb Cr(VI) from aqueous solution (Fig.
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1). The maximum Cr(VI) adsorption (%) was achieved at pH 2.0. The Langmuir equation

described the Cr(VI) adsorption data very nicely. AC supported with f-MWCNTs in tubular

morphology provided higher Cr(VI) adsorption performance compared to other forms and the
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maximum adsorption was found to be 113.3 mg/g at pH 2.2 and 25 °C. In addition, 0.1 M

HCl and 0.1 M NaOH treatment of these substrates after Cr(VI) adsorption showed excellent
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regeneration capabilities.
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(Valentín-Reyes et al., 2019) investigated Cr(VI) adsorption onto activated carbon

(AC) and noted that the functional groups present on the AC played a vital role in Cr(VI)

adsorption. They proposed four mechanisms for Cr(VI) adsorption based on their

experimental findings and the complex nature of AC (Fig. 2). Mechanism I involves anion

exchange by basic sites; Mechanism II involves the reduction of Cr(VI) to Cr(III) by AC

9
under acidic conditions; Mechanism III involves three steps Cr(VI) - surface interaction: (i)

Cr(VI) adsorption on the basic sites by anionic adsorption, (ii) direct reduction mechanism

where Cr(VI) may be reduced to Cr(III) by an adjacent electron donor group on the substrate,

and (iii) Cr(III) is released to the solution by electrostatic repulsion between positively

charged Cr(III) and positively charged surface functional groups (Fig. 2). Mechanism IV

involves a coupled reduction-adsorption mechanism for Cr(III) adsorption by cation-

exchange on acidic sites. Moreover, Cr(III) species may precipitate as Cr(OH)3 of the cation

species which are not adsorbed onto the acidic functional groups of the substrate when pH is

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higher than 5.0.

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A list of publications that investigated Cr(VI) adsorption using a wide range of carbon

materials together with maximum surface coverage under given experimental situations is
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shown in Table 1. It can be noted from Table 1 that a diverse range of AC from various
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sources together with modified forms have been commonly used for Cr(VI) adsorption. In

most cases, the PS2 and Langmuir model described Cr(VI) adsorption perfectly. There are
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only a few studies that used spectroscopic and SCM for Cr(VI) adsorption. Therefore, this

could be an important future research area.

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2.2. Agriculturally based low-cost adsorbents

Recently, agricultural and natural substances have been very popular as low-cost
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adsorbents (Gao et al., 2008). Often, they are locally available, cost-effective, and in most

cases readily usable as adsorbents (Islam et al., 2018b). Historically, straws, leaves, barks,
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peels, marine algae, tea-waste, pulp and paper-waste, medical waste, and sand are used in

their original form or in a pre-treated form (Liu et al., 2019). Sometimes they are impregnated

or coated with metal oxides or other materials to improve their adsorption performance. Their

adsorption performance primarily depends on the nature, treatment, and mode of activation.

Being comparatively cheaper and locally available, agricultural-based materials are superior

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to activated carbon because of modern waste disposal technologies. These materials require

acid or alkali treatment to improve their adsorption capacity.

Many research groups have investigated the possibility of various agro-based

substrate for Cr(VI) adsorption from the aquatic environment (Fan et al., 2017). (Gorzin and

Bahri Rasht Abadi, 2018) explored the use of paper mill sludge (SSA 133 m2/g) in Cr(VI)

adsorption from aqueous solution. The Langmuir equation showed a better agreement with

equilibrium isotherm data producing maximum adsorption of 23.2 mg/g at pH 4.0 and 45 °C.

PS2 followed kinetic data well while the thermodynamic calculation revealed that Cr(VI)

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adsorption was feasible, spontaneous and endothermic in nature. The high enthalpy change

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(62.72 kJmol-1) indicated that chemisorption was responsible for Cr(VI) adsorption while the

positive value of entropy revealed the increase in irregularity or randomness at the water-
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solid interface during adsorption onto this substrate. Moreover, the substrate showed a
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permissible regeneration capability. (Fan et al., 2017) used tea-waste/Fe3O4 composite to

adsorb Cr(VI) from simulated water and the surface, exhibited an adsorption maximum of
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75.76 mg/g based on the Langmuir equation with the PS2 model fitting kinetic data nicely.

The substrate displayed good reusability with adsorption more than 70% after five
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consecutive cycles. They proposed that Cr(VI) adsorption involved three steps (Fig. 3).

Firstly, Cr(VI) adsorbed onto the substrate because of electrostatic attraction or an ion
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exchange or surface complexation; Secondly, some of Cr(VI) can be converted to Cr(III)

species and finally, some Cr(III) can adsorb onto the substrate by ion-exchange or surface
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complexation with some Cr(III) released into the solution because of electrostatic repulsion

(Fig. 3).

Chromium (VI) adsorption performance onto low-cost materials under given

experimental conditions is displayed in Table 2. The study revealed that agriculturally based

low-cost substrates have been encouraging adsorbents for Cr(VI) adsorption from

11
wastewater. They were highly dependent on solution pH with a maximum adsorption found

in the pH range 2.0-3.0. From Table 2, it is evident that most of the work reported in the

literature demonstrates that Cr(VI) adsorption behaviour is highly dependent on the surface

nature of these substrates. In most cases, PS2 and the Langmuir equation describes Cr(VI)

adsorption data satisfactorily.

2.3. Nanosized metal oxides

Metal oxides are abundant in soil, sediment and the aquatic environment as discrete

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particles, colloid, nodules, and coatings (Islam, 2010; Islam, 2015; Islam and 2018; Islam et

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al., 2018a; Islam and Rahman, 2013a, b, 2014, 2015). Nanosized metal (oxy-hydro) oxides

such as Fe, Al, Mn, Ti, Zn-oxides have proved to be outstanding adsorbents for Cr(VI)
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adsorption owing to their large specific surface area (SSA), porous structure and variable

surface charge (Islam, 2010; Islam, 2015, 2018; Islam et al., 2018a; Islam et al., 2018b; Islam
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and Rahman, 2013c). Chromium (VI) adsorption to mineral surfaces has been typically found
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to decrease with increasing pH (Gheju et al., 2016), which is thought to be due to changes in

the electrostatic interaction between the negatively charged adsorbing ions and mineral
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surface. (Gheju et al., 2016) investigated Cr(VI) adsorption onto pyrolusite (β-MnO2) and

found that Cr(VI) adsorption was fast in the first 3-5 min, reaching equilibrium after 1 h.
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They noted that uptake of Cr(VI) reduced with increasing solution pH, initial Cr(VI)

concentration, and temperature, while adsorption increased with increasing the ionic strength.
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(Granados-Correa and Jiménez-Becerril, 2009) explored Cr(VI) adsorption onto boehmite

and noted that the Cr(VI) uptake was fast and the system reached a complete equilibrium

within 1 h. They also found that the amount of Cr(VI) sorbed reduced with increasing pH and

a significant amount of Cr(VI) sorbed at above pH 10 (60%). Recently, (Deng et al., 2015)

investigated Cr(VI) adsorption onto CoFe2O4/MgAl-LDH in aqueous solution. Cr(VI)

12
adsorption data could describe both the PS2 and Langmuir equation nicely while maximum

adsorption was found to be 72.4 mg/g at 10 °C with an equilibration time of 5h. Cr(VI)

adsorption onto the composite was spontaneous and exothermic. The mechanism of

adsorption was likely to occur as both chemi- and physisorption (Fig. 4). Firstly, Cr(VI)

adsorbs and enters into the pores of the surface via physical adsorption. Secondly, Cr(VI)

adsorbs via electrostatic interaction between the positively charged surface and Cr(VI) anion

forming an outer-sphere complex. In addition, nitrate (NO3-) anions present in the interlayer

of the surface could exchange with Cr(VI) through anion exchange (Fig. 4).

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(Gheju et al., 2016) demonstrated Cr(VI) adsorption onto MnO2 and noted that the

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amount of Cr(VI) adsorbed increased with increasing pH, temperature, initial metal

concentration, and ionic strength. The presence of sulphate, phosphate, bicarbonate, citrate,
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and oxalate caused a decrease of Cr(VI) adsorption whilst the existence of nitrate, acetate,
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and chloride did not exert any notable influence. Cr(VI) adsorption data nicely fitted the PS2

model. The maximum adsorption capacity was 0.84 mg/g at pH 5.9 and 20 °C. Intra-particle
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and film diffusion processes were the rate-limiting steps of Cr(VI) adsorption. They

speculated that Cr(VI) adsorption onto the surface might involve physical/nonspecific
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adsorption by electrostatic interaction (outer-sphere complexation) and chemical/specific

adsorption by chemical interaction (inner-sphere complexation). The thermodynamic

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calculation showed that Cr(VI) adsorption was spontaneous. (Li et al., 2014) developed a new

composite of titanium oxide-graphene oxide (Fe3O4@mTiO2@GO) composite whose SSA

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was 405.2 m2/g. They used this novel substrate to adsorb Cr(VI) from simulated wastewater.

The Freundlich and PS2 model could describe Cr(VI) adsorption data nicely implying

heterogenous surface nature. The maximum surface coverage was 117.94 mg/g at pH 2.0.

They proposed that Cr(VI) adsorbed onto the surface by two steps: firstly, with the help of ℼ

electrons on the carbocyclic six-membered rings of substrate, Cr(VI) is reduced to Cr(III),

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followed by release of Cr(III) species by electrostatic repulsion between protonated hydroxyl

groups and cationic Cr(III) or binding of Cr(III) species on the surface by the electrostatic

attraction between Cr(III) and negatively charged -COOH groups of substrate. Secondly,

Cr(VI) can bind with the substrate by the electrostatic interaction between Cr(VI) and the

protonated hydroxyl groups of the composite. Recently, (Islam, 2018) explored Cr(VI)

adsorption onto six different substrates such as birnessite, pyrolusite, hausmannite,

manganite, boehmite and Mn-Al binary oxide in 1 mM NaNO3 solution. As can be seen from

the correlation coefficients, the adsorption data were better modeled with the Langmuir

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equation with boehmite having the highest sorption capacity, and birnessite the least. Cr(VI)

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adsorption was found to depend highly on solution pH and because of the anionic nature of

the chromium species, sorption decreased with increasing solution pH and maximum sorption
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was approached (~100%) at pH 2.0 for birnessite, while for other surfaces maximum sorption

was across the pH range of 5.8-8.2.

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General Cr(VI) adsorption capacity by metal oxides have been presented in Table 3.
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It is noticed that composite materials obtained from metal oxides have been common for

Cr(VI) adsorption. Similar to the previous trend, PS2 and Langmuir equation typically
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describe Cr(VI) adsorption data nicely.

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2.4. Clay materials

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As one of the most important groups of natural and abundant minerals, clay minerals

have been used to adsorb Cr(VI) from aqueous solution (Liu et al., 2016; Zhou and Chen,

2000). Applicability of kaolin was tested by (Liu et al., 2016) for Cr(VI) and Cr(III)

adsorption in single and binary solute with Cu(II) in the pH range of 2.0-7.0. It was noted that

Cr(III) could change zeta potential (ZP) from negative to positive and Cr(III) adsorbed onto

14
the surface via electrostatic attraction below pH 4.0. Langmuir could describe Cr(III) and

Cr(VI) adsorption in single and binary solute systems implying monolayer adsorption.

Primarily, the adsorption mechanism involved physico-chemical in nature. Cr(III) adsorbed

specifically in the interior of the kaolin while electrostatic attraction and protonation were the

prime Cr(VI) adsorption mechanisms. (Zhou and Chen, 2000) reported Cr(VI) adsorption

onto six different clay substrates, namely kaolinite, montmorillonite, indicotic black (IB),

yellow-brown, red soil, and laterite. It was found that Cr(VI) adsorption was fast and reached

equilibrium in two hours at moderate temperature. Adsorption was enhanced within the pH

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range of 2-7 and then decreased at higher pH. Adsorption isotherm fitted Freundlich equation

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quite well. The maximum adsorption at 12 °C follows the order: kaolinite > Laterite ~ Red

soil > Yellow brown > indicotic black > montmorillonite. Adsorption was found to be
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exothermic and the amount adsorbed decreased with increasing temperature of the

system. (Bhattacharyya and Sen Gupta, 2006) investigated the interaction of Cr(VI) with
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kaolinite and its modified forms acid activated kaolinite, poly(oxozirconium) kaolinite, and
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tetrabutylammonium kaolinite in aqueous medium. Cr(VI) adsorption was found to be highly

dependent on pH, with uptake increasing from pH 2.0 to 9.0, and then decreasing. The results

have shown that the process attained equilibrium in 4 h. Both the Langmuir and Freundlich
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equation could describe Cr(VI) adsorption quite well while the maximum adsorption at 30 °C

follows the order: acid activated kaolinite > kaolinite > poly(oxozirconium) kaolinite at pH
ur

6.0. The adsorption process was endothermically followed by an increase in entropy and a
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decrease in Gibbs free energy. They speculated that Cr(VI) adsorbed onto these clay by the

formation of Cr(VI)-surface complexes.

A list of past papers that have dealt with Cr(VI) adsorption using clay materials is

displayed in Table 4. Our survey shows that a diverse range of clay in pure or modified

15
composite form has been used for Cr(VI) adsorption from aqueous solutions. There is no

SCM study reported for Cr(VI) adsorption onto clay materials.

2.5. Zeolites

Natural zeolites are typical inorganic cation exchangers that show high ion exchange

capacity, selectivity, and compatibility with natural surroundings (Algamal, 2018). Zeolites

are a hydrated aluminosilicate substrate and are abundant in nature. They are typically

comprised of symmetrically stacked alumina (Al3+) and silica (Si4+) tetrahedra and readily

of
form an open and stable three-dimensional structure with a negative charge ion. The most

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common and cheapest zeolite is the clinoptilolite. In recent years, several research groups

have studied Cr(VI) adsorption using zeolite materials (Adam et al., 2018; Nadeem, 2014;
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Yusof and Malek, 2009). The potential of natrolite as an adsorbent was tested in Cr(VI)

adsorption (Nadeem, 2014). The result showed that Cr(VI) adsorption was pH dependent
re
with maximum adsorption occurring at pH 2.0. The Langmuir equation could potentially
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describe isotherm data, yielding a maximum adsorption of 7 mg/g at 30 °C. Thermodynamic

calculations demonstrated that Cr(VI) adsorption was exothermic. (Adam et al., 2018)
na

demonstrated Cr(VI) removal using a zeolite based hollow fibre ceramic membrane and

found the substrate could remove 75.5% Cr(VI) at pH 4.0 with an initial concentration of 40
ur

mg/L. Based on their experimental findings, they proposed the mechanism as shown in Fig.5

(a-c) (description in the Figure caption).

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A list of papers that used various zeolites for Cr(VI) adsorption is shown in Table 5.

It is seen that various types of zeolite materials have been used for Cr(VI) adsorption. In most

instances, PS2 and Langmuir equation could potentially describe adsorption data.

16
2.6. Biopolymers

Biopolymeric materials have been gradually investigated for separation and

enrichment of Cr(VI) as an ideal surface because of their large surface area (SSA), tuneable

pore size and highly ordered pores, mesoporous structure and high adsorption capacity

(Dupont and Guillon, 2003; Sessarego et al., 2019). They are widely abundant and

environmentally friendly. These materials include chitosan, alginate, cellulose, lignin,

proteins, chitin, carrageenan and chitin derivatives (Schmuhl et al., 2001). These materials

have different functional groups such as hydroxyl and amine groups to which pollutants can

of
readily adsorb (Schmuhl et al., 2001).

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A wide number of papers have used biopolymer-based materials for Cr(VI)

adsorption from aqueous solutions (Baran et al., 2007; Karthik and Meenakshi, 2015;
-p
Sessarego et al., 2019). Recently, the applicability of phosphonium enhanced chitosan (PCC)
re
was tested for Cr(VI) adsorption by (Sessarego et al., 2019). PCC showed better adsorption

performance than chitosan. Adsorption followed the PS2 model, while the Langmuir equation
lP

described the adsorption data nicely at pH 3.0, producing a maximum adsorption of 221

mg/g. The composite also exhibited reasonable regeneration capacity. Batch adsorption
na

experiments have been applied for Cr(VI) adsorption onto chitin, chitosan, purolite CT-275,

purolite MN-500, and Amber lite XAD-7 from water (Baran et al., 2007). Both Langmuir and
ur

Freundlich models could properly describe the isotherm data. Under optimal conditions the

order of maximum adsorption capacity (mg/g) was found to be at 25 °C, chitosan (154) >
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purolite MN-500 (127) > chitin (70.4) > purolite CT-275 (89.3) > amber lite XAD-7 (6).

These substrates also showed sufficient regeneration capability at 25 °C using EDTA.

(Karthik and Meenakshi, 2015) explored Cr(VI) adsorption onto sodium alginate- polyaniline

nanofibers. Cr(VI) adsorption was highly pH dependent. PS2 followed kinetic data well. The

Langmuir equation could correlate equilibrium isotherm data nicely producing a maximum

17
adsorption of 73.3 mg/g at 25 °C. Thermodynamic calculations indicate the feasibility and

spontaneous nature of the Cr(VI) adsorption process. Desorption experiments showed that the

substrate could be reused for more than three successive cycles. Macroscopic data and FTIR

indicated that Cr(VI) adsorption was primarily driven by an electrostatic adsorption coupled

reduction mechanism.

A summary of the applicability of various polymeric substrates have been used to

adsorb Cr(VI) from water is given in Table 6. It is readily understandable that a diverse range

of biopolymeric substrates has been used to adsorb Cr(VI) from aqueous solutions. In most

of
cases, Langmuir and PS2 have been found to fit Cr(VI) adsorption data reasonably well.

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2.7. Miscellaneous adsorbents -p
Apart from the aforementioned adsorbents, several research groups have also used
re
numerous novel miscellaneous substrates for Cr(VI) adsorption. Examples include diatomite
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(Du et al., 2015), radiation grafted N, N-dimethyl aminoethylmethacrylate-polypropylene

(Burillo et al., 2013), kaolin supported biofilm of E. Coli (Quiton et al., 2018), D-MoS2 (Sun

et al., 2018), hydrous stannic oxide (Goswami and Ghosh, 2005), non-living biomass of
na

Chlorella vulgaris, Clodophara crispata, Zooglcea ramigera, Rhizopus arrhizus and

Saccharomyces cerevisiae (Nourbakhsh et al., 1994) and CaCO3 (Correa et al., 2013). The
ur

applicability of vesicular basalt volcanic rock in Cr(VI) adsorption was tested by (Alemu et
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al., 2018). The Cr(VI) adsorption capacity was found to decrease with increasing solution pH,

with an optimum adsorption pH of 2.0 observed. The PS2 and Freundlich equation were

found to fit experimental Cr(VI) adsorption data nicely implying heterogeneous surface

chemistry. The maximum surface coverage was 79.2 mg/g at pH 2.0. (Mondal and Basu,

2019) studied the potentiality of human hair (layer-like structure, pHPZC 6.94) towards Cr(VI)

18
adsorption from aqueous solution in the batch method. Cr(VI) adsorption was highly pH

sensitive and maximum adsorption occurred at nearly pH 1.0. PS2 model could correlate

Cr(VI) adsorption data well while both Langmuir and Freundlich equations fitted data nicely

with a maximum adsorption of 10 mg/g. The thermodynamic calculations revealed that

Cr(VI) adsorption was endothermic and physisorption in nature. In addition, the substrate

showed a reasonable regeneration capability. (Mandal et al., 2017) studied the reduction of

Cr(VI) onto modified biochar and proposed a plausible adsorption mechanism (Fig. 8).

Results showed that modified biochar with improved surface characteristics (Fig. 8), in terms

of
of SSA and functional groups, enhanced Cr(VI) reduction in soils compared to pure biochar

ro
and manure. Substances used to modify biochar therefore had an important role on biochar

adsorption characteristics.
-p
A list of miscellaneous substrates that have been used for Cr(VI) adsorption is
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displayed in Table 7. It is apparent from Table 7 that a diverse range of surfaces have been

utilized as adsorbents to adsorb Cr(VI) from water, wastewater, and simulated wastewater.
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These substrates all exhibited moderate to high adsorption capacity. In most instances, both

PS2 and Langmuir equation have been correlated nicely for Cr(VI) adsorption data. However,
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there is no study involved the application of spectroscopic and surface complexation model

(SCM) which could be a future potential research area.

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3. Comparative Cr(VI) adsorption study

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To understand the performance of an individual adsorbent in Cr(VI) removal, several

authors conducted comparative studies using diverse groups of substrates (Dubey and Gopal,

2007; Hu et al., 2007; Nourbakhsh et al., 1994; Owalude and Tella, 2016a; Parlayici and

Pehlivan, 2019). (Dubey and Gopal, 2007) explored Cr(VI) adsorption onto ground husk

19
carbon (GHC) and silver impregnated ground husk carbon (SGHC) in spiked samples of

drinking water by a batch method. Cr(VI) adsorption data could correlate the Freundlich

model implying a heterogeneous surface. Cr(VI) adsorption was endothermic in nature. A

modified sample (11.4 mg/g) exhibited better adsorption performance than a pure one (7.0

mg/g). This could be ascribed to the modification of the surface property giving rise to

oxidation of Cr(VI). It can react with Cr(VI) to form insoluble silver chromate which could

be readily separated by filtration.

4Ag+ + Cr2O7- + H2O = 2AgCrO4 + 2H+

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(Owalude and Tella, 2016a) used modified and unmodified groundnut hull to adsorb Cr(VI)

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from aqueous solution. Langmuir and PS2 could describe Cr(VI) adsorption data nicely and

maximum surface coverage (mg/g) of these substrates observed at pH 2 and 28 °C.

-p
Adsorption capacity follows the order: 131 mg/g (modified GS) ≥ 90 mg/g (unmodified GS)
re
with Cr(VI) adsorption onto these substrates exothermic. In another study, (Parlayici and

Pehlivan, 2019) compared Cr(VI) adsorption performance of three different bio-wastes;

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cranberry kernel shell (CKS), rosehip seed shell (RSS), and banana peel (BP). Langmuir

equation described equilibrium isotherm data well producing the order of maximum
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adsorption (mg/g) 10.4 (BP) > 15.2 (RSS) > 6.8 (CKS) at pH 2.0. FT-IR analysis showed that

Cr(VI) formed a complex with these substrates through electrostatic interaction. (Hu et al.,
ur

2007) prepared six different magnetic nanoparticles by a co-precipitation method and applied

these substrates in Cr(VI) adsorption. Under their experimental conditions (mass 5 g/L, C(VI)
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concentration 100 mg/L, 25 °C), Cr(VI) adsorption capacity followed the order: MnFe2O4

(100%) > MgFe2O4 (85%) > ZnFe2O4 (65%) > CuFe2O4 (50%) > NiFe2O4 (32%) > CoFe2O4

(20%).

20
4. Competitive adsorption measuring chromium (VI)

Previously, most of the published work dealt only with Cr(VI) adsorption under

simple solution conditions. Multiple pollutants that co-exist in the aquatic environment may

interact with one another and exert combined effects that are different from their respective

individual effects. Therefore, to develop a better understanding of Cr(VI) adsorption under

more complicated geochemical conditions, the current study also summarises Cr(VI)

adsorption in presence of other pollutants in binary component systems onto surfaces.

Cr(VI) can influence the adsorption of metal ions and humic acid to substrates to a

of
significant extent. Cr(VI) adsorption in presence of a metal ion or a ligand depends on the

ro
extent of the interaction between the anion, metal ion, and substrate sites, and also the

concentration of the other species and the order of addition (Aksu, 2005; Aksu et al., 2002;
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Komárek et al., 2015; Wen et al., 2017; Wu et al., 2000; Wu et al., 2013a). Previous

investigations have been conducted studying the impact of Cr(VI) on metal ion or ligand
re
adsorption to mineral surfaces with these suggesting Cr(VI) adsorption may be enhanced,
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decreased or be essentially unaffected (Aksu, 2005; Aksu et al., 2002; Komárek et al., 2015;

Wen et al., 2017; Wu et al., 2013a; Wu et al., 2013b; Yang and Lee, 2006). In most cases,

Cr(VI) adsorption was reduced significantly in the existence of organic compounds compared
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with the amount of Cr(VI) adsorbed when in solution. However, a range of different results

has been reported on the interaction between Cr(VI) and HA. (Yang and Lee, 2006)
ur

investigated the competitive adsorption between Cr(VI) and HA onto TiO2 and found that the
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adsorption of Cr(VI) was greatly enhanced in the ternary system compared to Cr(VI) alone.

HA adsorption was also found to increase when the system contained both Cr(VI) and HA

compared to HA alone. (Li et al., 2010) explored Cr(VI) adsorption onto kaolin and found

that the amount of chromium(VI) sorbed was enhanced with increasing pH, reaching a

maximum observed in the range of pH 4.0-6.0. Then Cr(VI) adsorption reduced as pH

21
increased further. The existence of HA clearly increased chromium (VI) adsorption and this

was attributed to the formation of soluble complexes with HA in solution. (Aksu et al., 2002)

studied the simultaneous adsorption of Cr(VI) and Ni(II) onto dried activated sludge and

noticed that presence of Ni(II) caused a reduction in the equilibrium Cr(VI) adsorption where

the amount of Cr(VI) sorbed decreased with increasing concentration of Ni(II) at pH 4.5. It

was also noted that the inhibitory effect of Ni(II) on Cr(VI) was most pronounced at higher

initial Ni(II) concentrations at pH 1.0 and 4.5. (Wu et al., 2013b) investigated competitive

adsorption of Cr(VI) and Ni(II) onto coconut shell activated carbon and observed that in the

of
two-component system, Ni(II) inhibited Cr(VI) adsorption. They speculated that the presence

ro
of Ni(II) competed with chromium(VI) for adsorption sites on the substrate, resulting in

reduced chromium(VI) adsorption. These somewhat contradictory findings should stimulate

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further research to clarify the effect of competition between Cr(VI), metal ions and HA on

mineral surfaces.
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Previous reports on Cr(VI)-HA-mineral systems have noted a decrease in Cr(VI)
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adsorption in the presence of HA (Dries et al., 2005; Wu et al., 2000). The authors of these

studies suggested that the influence of HA on Cr(VI) adsorption was more significant at

lower pH as was noted in this study. Both the availability of substrate sites and electrostatic
na

effects have been proposed to play an important role in Cr(VI) adsorption in the presence of

HA (Jiang et al., 2013; Wu et al., 2000). A similar influence may account for the changes in
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Cr(VI) adsorption when HA is present with electrostatic repulsion between negatively

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charged HA and Cr(VI), where competition for surface sites acts to decrease Cr(VI)

adsorption.

(Zhang et al., 2015) studied the mechanism of Cr(VI) adsorption onto AC in the existence of

HA and proposed ta mechanism that occurred in four steps as shown in Fig. 6. Firstly, in the

pre-equilibrium process, protonation of the AC functional groups and binding of HA;

22
Secondly, Cr(VI) was adsorbed by the protonated substrate by forming Cr(VI)-HA

complexes. Thirdly, adsorbed Cr(VI) was reduced by the adjacent electron donor groups of

AC or HA and finally, the formation of chemical complexation, electrostatic attraction or

cation exchange took place between Cr(III) and AC surface and surface-bound HA. In

addition, Cr(III) can also interact with HA in solution to produce Cr(III)-HA complexes

which were further adsorbed by the substrate (Fig. 6).

5. Chromium(VI) adsorption mechanism

Cr(VI) adsorption mechanism involves mainly two general surface complexes and is

of
described by the configuration geometry of the sorbate-surface interfaces (Islam, 2018).

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These include inner-sphere and outer-sphere complexes which are defined by the presence or

absence of the hydration sphere of adsorbate upon interaction with mineral surfaces (Islam,

2018; Violante et al., 2010).

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Inner-sphere complexation

The surface complexation model (SCM) can identify the specific and nonspecific
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adsorption characteristics of adsorbing species onto the mineral surface as inner- and outer-

sphere complexes respectively (Islam and David W. Morton, 2019; Smith, 1999). When
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adsorbing ions bind directly to a specific site on the surface with no intervening water

molecules, an inner-sphere complex is formed. These are restricted to ions that have a strong
ur

affinity for the surface and specifically react with the surface by forming a covalent or ionic

bond. This process is slower than outer-sphere complexation and is not fully reversible.
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Based on the adsorbing species and the surface, inner-sphere can be monodentate, bidentate

(metal atom bonded to two surface oxygen species), mononuclear or binuclear (Islam, 2018).

Outer-sphere complexation

23
 When sorbing ions bind to the surface by the hydration shell of water molecules an

outer–sphere complex is formed (Islam, 2018; Violante et al., 2010). At least one water

molecule is involved, between the adsorbing ions and the surface functional group (Sposito,

1989). The adsorbing species are held by the surface functional group via electrostatic

columbic interactions, van der Waals interactions, and hydrogen bonding. The process is

usually rapid and reversible, and uptake takes place only on the surface that is of opposite

charge to the adsorbing species. The distinction between these two complexes has been made

using several spectroscopic techniques, shifting of the point of zero charge (pHPZC), and ionic

of
strength effects (Goldberg, 2014; Goldberg et al., 2007). Formation of inner-sphere

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complexes involves the shifting of pHPZC while pHPZC has no effect on the establishment of

the outer-sphere complexation (Goldberg, 2014; Goldberg et al., 2007). Outer sphere
-p
complexes have an important influence on ionic strength with high ionic strength tending to

decrease outer-sphere complexation (Hayes et al., 1988).

re
lP

5.1. Chromium adsorption data modeling

Modeling of adsorption data is useful for obtaining parameters that describe the
na

surface adsorption process. The modeling is important for the following reasons (Islam,

2018):

- It can deliver information on the pathways for the adsorption process;

ur

- It can predict adsorption beyond the range of the current interest of experimental conditions;
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- It allows predictions for adsorption systems similar to those being studied; and

- It can enable an estimate of the thermodynamic parameters for adsorption reactions.

The adsorption studies have been modeled using a number of empirical models such as

kinetic models (PS1, PS2, E, and IPD), equilibrium isotherm models (Langmuir, Freundlich,

Sips, Temkin, R-P and Dubinin-Radushkevich), and surface complexation models (SCMs)

24
which provide valuable information on the overall adsorption processes (Demirbaş and

Alkan, 2011; Dinh et al., 2018; Islam and David W. Morton, 2019; Kawashima et al., 1986;

Mustafa et al., 2006). The detailed description of these models is found in our previously

published article (Islam et al., 2018b).

5.2. Surface complexation modeling for Cr(VI) adsorption

Several mechanistic surface complexation models have been put forward as a tool for

predicting the adsorption process for Cr(VI)-mineral systems. These include constant

of
capacitance model (CCM) (Reich and Koretsky, 2011), extended constant capacitance model

ro
(ECCM) (Islam, 2018; Ruyter-Hooley et al., 2015), diffuse layer model (DLM) (Komárek et

al., 2015; Veselská et al., 2016), triple layer model (TLM) (Reich and Koretsky, 2011; Wu et
-p
al., 2000) and the charge distribution multi-site complexation (CD-MUSIC) model (Gu et al.,

2017; Xie et al., 2015). These models typically differ mainly in their adjustable parameters.
re
Compared with the literature for the adsorption of Cr(VI) using iron and aluminium oxides
lP

and clay mineral systems, studies of Cr(VI)-manganese oxide systems are rare despite its

prevalence in the soil environment (Veselská et al., 2016). Previously, for Cr(VI) adsorption,
na

only outer sphere chromate and bichromate complexes were assumed to develop on

ferrihydrite surfaces (Fig.7) (Zachara et al., 1989). A recent study shows that Cr(VI) forms
ur

monodentate and bi-dentate inner-sphere complexes with the ferrihydrite surface depending

on solution pH, surface loading and ionic strength (Fig.7) (Chrysochoou et al., 2013). (Islam,
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2018) explored the simulation of the Cr(VI) adsorption data onto six different substrates such

as birnessite, pyrolusite, hausmannite, manganite, boehmite and Mn-Al binary oxide in 1 mM

NaNO3 solution using ECCM. They considered one inner-sphere surface complex, [≡SOH2+-

CrO42-] and one outer-sphere complex, [≡SOH2+ …CrO42-] and it appears from Cr(VI) edges

data simulation that ECCM could be reasonably fitted to the data with a small

25
under/overestimation in some cases. ECCM results show that Cr(VI) adsorbs onto mineral

surfaces by inner-sphere complexes at pH below 6.0, while outer sphere complexes tend to

dominate at higher pH values.

On the other hand, although pH dependence Cr(VI) adsorption data onto mineral

surfaces fitted reasonably well, in most cases, the model overestimates at low pH values. This

might be because of the partial dissolution of minerals at low pH which might contribute

Cr(VI) adsorption. There is also the probability that the sorbed Cr(VI) might be released into

of
solution collected with the dissolved Mn and Al under acidic conditions, which could account

ro
for the model overprediction at low pH (Veselská et al., 2016). Previous reports have found

that dissolution of minerals can notably change their surface reactivity and make consequent
-p
changes in their adsorption properties (Komárek et al., 2015). It is difficult to solve this

problem in modeling because the quantification of intrinsic surface complexation constants

re
for Mn and Al is required.
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The speciation of Cr(VI) sorbed complexes proposed in this review indicated the

inner-sphere complex dominated at pH below 6.0 while the outer-sphere complex dominated

at higher pH values. The tendency to develop the inner-sphere complexes at low pH and
na

outer-sphere complexes at higher pH has also been found for Cr(VI) adsorption onto

birnessite, ferrihydrite, illite and kaolinite (Veselská et al., 2016), and for other anionic
ur

species such as the adsorption of inositol onto kaolinite (Ruyter-Hooley et al., 2017), gibbsite
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(Ruyter-Hooley et al., 2015), and for benzene carboxylates using goethite (Boily and Fein,

2000), and phenyl phosphate using alumina (Johnson et al., 2002).

26
5.3. Spectroscopic mechanism

Several spectroscopic techniques have been used to investigate the mechanism of

interaction of Cr(VI) with mineral surfaces (Dehghani et al., 2015; Huang et al., 2016;

Johnston and Chrysochoou, 2015; Komárek et al., 2015; Veselská et al., 2016; Weilong and

Xiaobo, 2013), including FTIR (Dupont and Guillon, 2003), XPS (Dupont and Guillon,

2003) and EXAFS (Dupont and Guillon, 2003). These investigations have suggested that the

mechanism of Cr(VI) adsorption onto mineral surfaces involves electrostatic interaction, ion-

exchange, Cr(VI) reduction to Cr(III), and surface complexation (Johnston and Chrysochoou,

of
2015; Komárek et al., 2015). Both outer and inner-sphere surface complexes have been

ro
proposed for Cr(VI) adsorption to mineral surfaces (Johnston and Chrysochoou, 2015;

Komárek et al., 2015). (Komárek et al., 2015) investigated the competitive adsorption of
-p
Cr(VI), Cd(II) and Pb(II) using nanomaghemite. Spectral analysis with XPS and XAS

indicated that Cr(VI) was adsorbed to the substrate mainly as outer sphere complexes
re
whereas Pb(II) was adsorbed primarily due to inner-sphere complexation, while Cd(II) was
lP

complexed by means of both outer and inner-sphere complexation. (Huang et al., 2016)

explored the adsorption of Cr(VI) onto hematite (α-Fe2O3) using in situ ATR-FT-IR

spectroscopy. The spectral analysis indicated that Cr(VI) was adsorbed onto the substrate via
na

the formation of both monodentate and bidentate inner-sphere surface complexes. In another

report, XPS and XANES spectral analysis of the data for the adsorption of Cr(VI) onto
ur

hematite showed that the accumulation of Cr(VI) onto the substrate was involved in an ion
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exchange between Cr(VI) and the hematite hydroxyl groups (Cao et al., 2012). (Veselská et

al., 2016) studied Cr(VI) adsorption onto ferrihydrite, birnessite, kaolinite, and illite using

spectroscopic techniques (FT-IR, EXAFS, and XPS) coupled with a diffuse layer surface

complexation modeling (DLM). For the birnessite surface, FTIR spectral analysis indicated

the formation of an outer-sphere hydrogen-chromate complex which was dominant at low

27
pH. In contrast, EXAFS studies indicated that approximately 75% of Cr(VI) was bound to

birnessite via a monodentate inner-sphere complex while 25% was sorbed by a bidentate

inner-sphere complex of chromate and hydrogen-chromate. The DLM indicated preferred

adsorption of the bidentate complex. Combining macroscopic Cr(VI) adsorption results with

XPS studies, it has been suggested that Cr(VI) adsorbed onto Fe-Mn mixed metal oxide by

means of both electrostatic attraction and an ion exchange process (Weilong and Xiaobo,

2013). In another study, the interaction of Cr(VI) with boehmite was found to involve

primarily an outer-sphere complex over a range of pH values and concentrations, while small

of
fractions of monodentate and bidentate inner-sphere complexes existing under acidic

ro
conditions were identified by in-situ ATR-FTIR and EXAFS measurements (Johnston and

Chrysochoou, 2015). Although several studies have combined a spectroscopic approach with
-p
surface complexation modeling, such investigations for Cr(VI) interaction with manganese

oxides remain scarce.

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5.4. Proton stoichiometry for Cr(VI) adsorption

Proton stoichiometry (χ), or proton exchange ratio, ([H+]released/[Cr(VI)]sorbed), refers to

the moles of protons released for every mol of Cr(VI) sorbed onto a particular mineral
na

surface (Islam, 2018). The number of protons released per Cr(VI) ion adsorbed is calculated

from the number of moles of standard NaOH (0.1 M) required to maintain the pH of selected
ur

mineral suspension during sorption isotherm experiments at pH 6.0 and 8.5, with the values
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of proton stoichiometry estimated from the Cr(VI) adsorption isotherm (Islam, 2018). The

proton stoichiometry values of a wide number of studies of Cr(VI) adsorption onto various

surfaces were in the range of 0.78 to 2.0 (Aide and Cummings, 1997; Islam, 2018; Wu et al.,

2000). It has been suggested that proton stoichiometry represents the effects of each surface

reaction involved in Cr(VI) adsorption and its value is influenced by pH, metal adsorption

28
density, the nature of the substrate, and the sorbate to surface site concentration ratio (Aide

and Cummings, 1997; Honeyman and Leckie, 1986). (Ainsworth et al., 1989) found that the

proton stoichiometry for Cr(VI) adsorption onto the three different substrates were 1.45 (L-Fe

goethite), 1.42 (M-Fe goethite) and 1.11 (M-Al goethite), respectively. (Wu et al., 2000) also

found that proton stoichiometry values of various anions onto γ-Al2O3 were 0.68 (MoO42-),

0.17 (CrO42-), 0.17 (SO42-), 0.22 (SeO42-), and 0.38 (SeO32-), respectively. Similarly, proton

stoichiometries for Cr(VI) adsorption have been found to be 0.384 onto boehmite (Aide and

Cummings, 1997) and 0.35 onto Al-oxide containing clays (Zachara et al., 1989). Therefore,

of
these results suggest that multiple protonated surface sites may be involved for each Cr(VI)

ro
species adsorption onto the substrates.

6. Thermodynamics of chromium(VI) adsorption

-p
A thermodynamic investigation of Cr(VI) adsorption is essential to identify whether
re
Cr(VI) adsorption is spontaneous or not and provide in-depth evidence about internal energy

changes that are related to adsorption (Ali et al., 2019). Where applicable, experimental
lP

Cr(VI) adsorption data at sufficient equilibrium at different temperatures is typically applied

to estimate Gibbs free energy change (∆G), enthalpy change (∆H) and entropy change (∆S)
na

for Cr(VI) adsorption using the equations as below (Deng et al., 2015).

∆G = -RT lnKc
ur

∆G = ∆H - T∆S

Where, Kc denotes the equilibrium constant. ∆H and ∆S can be estimated from the slope and
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intercept of van’t Hoff plot of lnKc versus 1/T. Assessment of these parameters indicates

whether the Cr(VI) adsorption is feasible, spontaneous or non-spontaneous. The values of

different thermodynamic parameters obtained for Cr(VI) adsorption onto various substrates at

different temperatures is displayed in Table 8. The negative values of Gibbs free energy

29
demonstrated the feasibility and spontaneous nature of the Cr(VI) adsorption process. It is

noted that the value of Gibbs free energy became more negative with the decrease in

temperature implying that lower temperature facilitated Cr(VI) adsorption onto mineral

surfaces. The negative value of ∆H indicates that Cr(VI) adsorption reaction was exothermic

and the uptake amount of Cr(VI) decreased with increasing temperature of the solution (Liu

et al., 2019). The negative value of entropy change of Cr(VI) adsorption using substrate is

linked to a decrease in randomness at the solid-water interface (Liu et al., 2019).

of
7. Regeneration of spent adsorbents

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In order to get insight into the actual application of various adsorbents in Cr(VI)

adsorption, the regeneration and reuse of substrates have been investigated using various
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eluents such as HCl, NaOH, H2SO4, Na2CO3, etc. (Deng et al., 2015; Liu et al., 2019;

Sessarego et al., 2019). (Deng et al., 2015) explored the regeneration and reuse of
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CoFe2O4/MgAl-LDH using Na2CO3 as eluent. They noted that the amount of Cr(VI)
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adsorbed onto this surface was notably high in the sixth regeneration cycle with 14.86 mg/g

of Cr(VI) adsorption which reduced by 9.5% compared with the first cycle, implying that the
na

substrate could be regenerated and reused effectively, therefore having the potential to

effectively treat water polluted with Cr(VI). (Wu et al., 2013a) explored the regeneration
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efficiency of AC which was prepared from coconut charcoal after Cr(VI) adsorption and it

was noticed that the maximum desorption was 73.2% using NaOH (0.5 M) solution. After six
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consecutive regeneration cycles, the surface could adsorb 64% Cr(VI), indicating reasonable

recyclability of the substrate. (Liu et al., 2019) studied the regeneration capability of

graphene oxide/polyamidoamine (GO/PAMAMs) composite after Cr(VI) adsorption. It was

noted that Cr(VI) adsorption efficiency decreased a little after five successive cycles and the

30
removal performance reduced from 72.8% to 65.2% at pH 2 using 0.02 M NaOH solution as

eluent, implying good regeneration capability of the substrate for Cr(VI) adsorption.

8. Conclusions and future perspective

This review shows that a diverse range of materials have been applied for Cr(VI)

adsorption from water and has attracted the attention of many researchers. It is evident from

our literature survey that Cr(VI) adsorption is strongly dependent on pH and because of the

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anionic nature of the chromium species, adsorption decreased with increasing solution pH. In

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most instances, the maximum Cr(VI) adsorption was approached (~ 100%) at pH 2.0, while

for some surfaces maximum adsorption was across the pH range of 5.8-8.2. The amount of
-p
Cr(VI) sorbed onto mineral surfaces enhanced with increasing initial Cr(VI) concentration.

Adsorption isotherm could be mostly fitted well with the Langmuir equation. Overall, the
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Langmuir constants were relatively small suggesting that Cr(VI) had a weak affinity for the
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surfaces compared to metal ions. Proton stoichiometry measurements indicated that Cr(VI)

adsorption is likely to involve multiple processes. Previous studies have proposed that the
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Cr(VI) adsorption mechanism involves primarily ion-exchange, electrostatic attraction,

Cr(VI) reduction to Cr(III), and complexation. Surface complexation model (SCM) results

show that Cr(VI) sorbed onto mineral surfaces by inner-sphere complexes at pH below 6.0,
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while outer sphere complexes tend to dominate at higher pH values.

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The results of this study show that competitive adsorption of Cr(VI) and metal ions,

anions, and humic acid (HA) in presence of each other was generally found to depend on the

pH of the solution, the nature of the substrates and type of sorbate used. The decrease of

Cr(VI) adsorption in the presence of metal ions and vice versa likely resulted from the

competition of both metal ions for a limited number of surface sites. The reduction of Cr(VI)

31
adsorption in the presence of anions or HA is most likely to a limitation in the available

surface sites and electrostatic repulsion between the negatively charged HA and Cr(VI)

species.

As a result of our survey the following recommendations for future adsorption studies in

removing Cr(VI) from wastewater are given below.

i. Macroscopic data are incapable of explaining the actual mechanism involved in

competitive adsorption data. More evidence of the solid-water interface is required to

distinguish between surface coprecipitation, precipitation, and adsorption mechanisms.

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Distinctly, the presence of HA modifies the adsorption mechanism of Cr(VI) at both

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low and high pH, as well as low and high surface coverage, notably in diverse ways. In

this regard, appropriate spectroscopic studies of these systems are warranted.

ii.
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Only limited information is available on competitive adsorption of Cr(VI) in the

presence of HA. Due to the complexity and lack of ternary complexation data,
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attempts to describe the surface complexation model (SCM) for these ternary systems
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have not been successful.

iii. Future research needs to focus on the impact of different coexisting anions in

adsorption behaviors of Cr(III) and Cr(VI).

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iv. Cr(VI) adsorption mechanisms need to be verified via quartz crystal microbalance

dissipation (QCM-D) measurements.

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v. Cr(VI) adsorption in single and binary component systems could be analyzed using
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ATR-FT-IR, extended X-ray absorption fine structure (EXAFS) and XPS

measurements. These investigations may provide detailed information on adsorption

mechanisms involved in single component systems and provide more insight into the

interactions taking place in binary component systems, together with and coordination

numbers and composition of neighboring atoms on the mineral surfaces. Because the

32
 ions in these systems are highly charged, it is likely that surface charge effects would

be very prominent.

vi. Generally, little is understood on the complete mechanism of Cr(VI) and HA removal

using manganese oxides and boehmite. Since most of the published works have dealt

with only birnessite, future research should focus on the use of manganese oxides as

sorbents for various metal ions and contaminants from large-scale environmental

samples.

vii. Most of the investigations reported in the literature to adsorb Cr(VI) have been carried

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out using conventional adsorbents, with very little information available on the use of

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various microorganisms (algae, bacteria, fungi, etc.) due to toxicity limitations.

viii. The batch method is commonly applied for Cr(VI) adsorption in the literature.
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However, effluents mainly originate from industries involved in production of large

amounts of waste, so treatment using a batch mode process is no longer feasible.

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Therefore, an appropriate strategy needs to be developed for continual removal of
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Cr(VI) from industrial effluents.

ix. Most of the studies that are reviewed in this work are limited only to an initial
evaluation of removal capacity, and there is a need to continue future studies at the
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pilot-plant scale.
x. So far, only one type of SCM has been applied to simulate Cr(VI) adsorption data.
However, a comparison of various SCM for the same data set is necessary to reduce
ur

inconsistency in data fitting.

xi. Previously all studies have involved batch or column processes, with no Cr(VI)
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adsorption studies using a continuous mode (in which the suspension remains in the

reaction vessel for the entire period of the experiment) (Islam, 2018) to estimate the

variation of environmental conditions in real time.

xii. In recent years, the application of density functional theory (DFT) (for adsorption

geometry and energy) (Johnston and Chrysochoou, 2014; Li et al., 2018; Yin and Ellis,

33
 2009) in adsorption study has been very popular. However, DFT has not been widely

used in Cr(VI) adsorption.

xiii. Nowadays, statistical hypothesis testing (to analyze the optimal combination of

independent variables leading to maximum Cr(VI) adsorption capacity) (Kaushal and

Singh, 2017; Uddin and Salah, 2018) is also used to study adsorption behavior.

However, this is not well known in Cr(VI) adsorption.

Despite limitations, this work is worthwhile because it enables us to better understand the

Cr(VI) adsorption process in single and binary solute systems. This review will advance

of
knowledge gaps in Cr(VI) adsorption and is a timely reference article for future researchers

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working in this area.

Conflict of interest
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There is no financial conflict for publishing this review.
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Acknowledgments
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The first author (M. A. Islam) is the recipient of both La Trobe University Post

Graduate Research Scholarship (LTUPRS) and La Trobe University Full Fee Research
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Scholarship (LTUFFRS) (17801371) to pursue his PhD research. The authors thank the editor

and anonymous reviewers for their constructive comments and suggestions which enabled
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them to improve the clarity and impact of the manuscript substantially.

Jo

34
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 of
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Fig. 1: Synthesis routes of activated carbon functionalized (AC/f-MWCNTs) (a) and AC

functionalized carbon nanotubes (AC/f-CNTs) (b) and Cr(VI) adsorption process onto these
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substrates (Figure taken from (Parlayici et al., 2015)).
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51
Fig. 2: Proposed Cr(VI) adsorption mechanism onto activated carbon (AC) (Figure taken
from (Valentín-Reyes et al., 2019)).

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Fig. 3: Proposed mechanism of Cr(VI) adsorption onto tea waste/Fe3O4 composite (Figure
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taken from (Fan et al., 2017)).

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Fig. 4: Proposed mechanism of Cr(VI) adsorption onto CoFe2O4/ MgAl-LDH composite.
(Figure taken from (Deng et al., 2015)).

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Fig. 5: Cr(VI) adsorption mechanism onto zeolite : (a) Si-O and Al-O bonds for tetrahedral

arrangement where replacement of Al(III) towards Si(IV) creating negative surface sites; (b)

neutralization of negative sites by Na+ from substrate create negative site on the surface; (c)

53
Cr(VI) attachment onto negatively charged surface (Figure taken from (Adam et al., 2018))

(colour online).

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Fig. 6: Probable mechanism of Cr(VI) adsorption onto activated carbon in the presence of

HA (Figure taken from (Zhang et al., 2015)). -p

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Fig.7: Formation of outer and inner-sphere Cr(VI) complexes (Figure adapted from

(Chrysochoou et al., 2013)).

54
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Fig. 8. A plausible proposed mechanism of modified biochar induced Cr(VI) reduction. BC

indicates Biochar, SOM denotes soil organic matter and DOC represents dissolved organic
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carbon. (Figure taken from (Mandal et al., 2017).

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55
Table 1 Chromium (VI) adsorption performance onto carbon materials under given

experimental conditions. PS1 denoted pseudo-first-order, PS2 represents pseudo-second-

order; IPD indicates intra-particle diffusion; E denoted Elovich and L, F, T, D-R are the

Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models respectively.

Adsorbent SBET Time pH T [Cr(VI)]0 [Dose] Adsorp Kinetic Isotherm References

(m2/g) (h) (°C) (mg/L) (g/L) tion model model
capacit
y
(mg/g)
Magnetic multi-walled / 1 3-9 30 2 0.1 13 PS1, L, F (Huang et al.,
carbon nanotubes PS2, 2015)

of
IPD
Activated carbon from apple / 4 2-7 10- 10-50 0.025- 36 PS1, L, F, T (Enniya et al.,
peels 40 0.15 PS2 2018)

ro
Coconut coir activated 826 4 1-6 22 20-60 0.1 39 PS1, L, F (Chaudhuri and
carbon PS2 Azizan, 2012)
Commercial activated carbon 626 4 1-6 22 20-60 0.1 28 PS1, L, F (Chaudhuri and
PS2 Azizan, 2012)
Hevea Brasilinesis sawdust
activated carbon
Coconut charcoal
/

800
5

6
2

1-10
20

30
50-200

25
-p 0.1

1
44

5
PS1,
PS2
PS1,
L, F

L, F, D-R
(Karthikeyan et
al., 2005)
(Wu et al.,
re
PS2, E 2013a)
Rice husk carbon / 2 2-6 22 20-80 1-10 48 PS1, L, F (Khan et al.,
PS2 2016)
lP

Activated carbon 735 168 6 25 10-500 0.5 49 / F (Valentín-Reyes

et al., 2019)
Activated carbon derived 1131 24 4 10- 100-400 0.3 125 PS1, L, F, T, (Malwade et al.,
from Leucaena leucocephala 50 PS2, E R-P 2016)
waste sawdust
na

Z. jujuba rubidium 608 24 1-6 20- 50-500 0.5-3 124 PS1, L, F, T, (Labied et al.,
carbonate-activated carbon 40 PS2, E D-R, S, 2018)
R-P
Biomass waste material- 608 24 2-8 22- 30 0.2-0.6 1123 PS1, L, F, T, (Duranoğlu and
ur

derived activated carbon 45 PS2, E D-R, S, Beker, 2015)

R-P
Activated carbon produced 448 1 1.5- / 4-50 0.25 26 PS1, L, F (Attia et al.,
Jo

from olive stones 10 PS2, 2010)

IPD
Commercial AC 663 1 1.5- / 4-50 0.25 71 PS1, L, F (Attia et al.,
10 PS2, 2010)
IPD
Chemically activated carbon / 2 1.5-8 23 100 0.25 125 PS1, L, F (Dula et al.,
prepared from waste of PS2, 2014)
bamboo (Oxytenanthera IPD
abyssinica)

56
Leucaena leucocephala seed 90 ~2 2-10 25- 50-250 0.2-1 27 PS1, L, F (Yusuff, 2019)
pod activated carbon 45 PS2,
IPD
Activated carbon-supported 875 24 2.2 25 52 0.01- 105 / L, F (Parlayici et al.,
functionalized carbon 0.1 2015)
nanotubes (AC/f-CNTs-3 %)
Commercial AC 496 24 2.2 25 52 0.01- 54 / L, F (Parlayici et al.,
0.1 2015)
AC/f-MWCNTs-1 % 566 24 2.2 25 52 0.01- 61 / L, F (Parlayici et al.,
0.1 2015)
AC/f-MWCNTs-3 % 982 24 2.2 25 52 0.01- 113 / L, F (Parlayici et al.,
0.1 2015)
AC/f-MWCNTs-5 % 374 24 2.2 25 52 0.01- 95 / L, F (Parlayici et al.,
0.1 2015)
Acid activated carbon / 24 4 25- 50-300 0.8 23 PS1, L, F, T, (Ali et al.,

of
prepared from Juniperus 40 PS2 D-R 2019)
procera Leaves
Graphene / 24 1.5-7 30 50 0.05 211 PS1, L (Liu et al.,
oxide/polyamidoamine
PS2 2019)

ro
dendrimers (GO/PAMAMs)
composites

-p
re
lP
na
ur
Jo

57
Table 2 Chromium (VI) adsorption performance onto low-cost materials under given

experimental conditions.

Adsorbent SBET Time pH T [Cr(VI) [Dose] Adsorpti Kinetic Isotherm References

2
(m /g) (h) (°C) ]0 (g/L) on model model
(mg/L) capacity
(mg/g)
Rice straw / 1.5 2-6 27 100 10 3.2 / L, F (Gao et al., 2008)
Paper mill sludge 133 2 2-6 25- 10-100 1.5-7 23.2 PS1, L, F (Gorzin and Bahri
45 PS2, Rasht Abadi, 2018)
IPD
Rice straw / 1.5 2-6 27 100 10 3.2 / L, F (Gao et al., 2008)
Peels of pea (Pisum / 5 2 25 30 10 4.3 / L, F, T (Sharma et al., 2016)
sativum) pod

of
Tea (Camellia / 5 2 25 30 10 7.3 / L, F, T (Sharma et al., 2016)
sinensis)
Ginger (Zingiber / 5 2 25 30 10 7.3 / L, F, T (Sharma et al., 2016)

ro
officinale)
Banana (Musa / 5 2 25 30 10 10 / L, F, T (Sharma et al., 2016)
lacatan) waste
Grainless stalk of / 3 4.6 20 147 0.5 7.1 PS1, L, F (Bellú et al., 2008)
corn
treated waste
newspaper
885 1 3 25 5-50 3
-p 60
PS2
PS1,
PS2
L, F, T (Dehghani et al., 2016)
re
Modified groundnut / 2 1-8 28 31.1 0.1-0.5 90 PS1, L, F (Owalude and Tella,
hull PS2 2016b)
Olive cake / 5 1-10 30 20- 2-24 33 PS2 L, F (Dakiky et al., 2002)
lP

1000
Wool / 5 1-10 30 20- 2-24 41 PS2 L, F (Dakiky et al., 2002)
1000
Sawdust / 5 1-10 30 20- 2-24 16 PS2 L, F (Dakiky et al., 2002)
1000
na

Pine needles / 5 1-10 30 20- 2-24 22 PS2 L, F (Dakiky et al., 2002)

1000
Almond shells / 5 1-10 30 20- 2-24 11 PS2 L, F (Dakiky et al., 2002)
1000
ur

Cactus leaves / 5 1-10 30 20- 2-24 7 PS2 L, F (Dakiky et al., 2002)

1000
Charcoal / 5 1-10 30 20- 2-24 7 PS2 L, F (Dakiky et al., 2002)
Jo

1000
Cassava (Manihot / 2 2-7 30 50-400 2 61.8 PS2 L, F (Horsfall Jr et al.,
sculenta) Cranz. 2006)
Waste moringa / 2 1-10 / 10 0.25- 119 PS1, L, P, S, (Shirani et al., 2018)
oleifera seed pods 1.5 PS2 D-R
Cranberry (Conus 1 1.5-6 25 50 0.1 6.8 PS1, L, F, D-R (Parlayici and
mas) Kernel shell PS2 Pehlivan, 2019)
(CKS)

58
Rosehip (Rosa 1 1.5-6 25 50 0.1 15.2 PS1, L, F, D-R (Parlayici and
canina) seed shell PS2 Pehlivan, 2019)
(RSS)
Banana (Musa 1 1.5-6 25 50 0.1 10.4 PS1, L, F, D-R (Parlayici and
cavendishii) peel PS2 Pehlivan, 2019)
(BP)

of
ro
-p
re
lP
na
ur
Jo

59
Table 3 Chromium (VI) adsorption performance onto metal oxides under given experimental

conditions.

Adsorbent SBET Time pH T [Cr(VI)]0 [Dose] Adsorpti Kinetic Isoth References

2
(m /g) (h) (°C) (mg/L) (g/L) on model erm
capacity mod
(mg/g) el
Flower-like 66.5 5 2 RT 10-250 0.04 61 / L, F (Du et al., 2015)
MnO2/diatomite
Wire-like 144.2 5 2 RT 10-250 0.04 101 / L, F (Du et al., 2015)
MnO2/diatomite
Sheet-like 49.5 5 2 RT 10-250 0.04 48 / L, F (Du et al., 2015)
MnO2/diatomite
Mn3O4 / 0.1 2-6 4-45 1000 0.1 4 PS2 L (Cantu et al., 2014)

of
Manganese oxide 94.1 1 2 25 40 0.15 15 PS1 L (Qusti, 2014)
nanofibers PS2
MnO2 / / 5.9 20 10.4 2 1 PS1 / (Gheju et al., 2016)

ro
PS2
IPD
Birnessite 34.9 24 3-10 25 5.20 20 100% / / (Veselská et al., 2016)
Ferrihydrite 323.4 24 3-10 25 5.20 2 100% / / (Veselská et al., 2016)
Boehmite 224 72 3-13 20-
50
5.20
-p
0.1 98 PS1
PS2
L, F,
D-R
(Granados-Correa and
Jiménez-Becerril,
2009)
re
Rose like-NiO / 12 3-11 25 25 0.2 2974 PS1 L, F (Ma et al., 2016)
PS2
Pinecone like-ZnO / 12 3-11 25 25 0.2 14256 PS1 L, F (Ma et al., 2016)
lP

PS2
Sponge like-CoO / 12 3-11 25 25 0.2 408 PS1 L, F (Ma et al., 2016)
PS2
Fe3O4@mTiO2@GO 405.2 / 2-10 30 40-140 0.1 118 PS1 L, F (Li et al., 2014)
PS2
na

γ-Al2O3 160 1.5 3-11 / 5-15 0.5-2 30 PS1 L, F (Golestanifar et al.,

PS2 2015)
Graphene coated 315 0.5 2-10 20- 25-175 0.01 121 PS1 L, F, (Khare et al., 2018)
iron oxide (GCIO) 50 PS2 T, D-
ur

nanoparticles IPD R
TiO2 50 24 4.5 / 5.20 0.5 143 / L, F (Doan et al., 2015)
Maghemite- 126 24 2.5- 50-500 0.025- 26 PS1, L, F, (Seraj et al., 2018)
Jo

polyrhodanine 11 0.25 PS2 T,

/
Birnessite 363 0.5 2.5- 22 ± 6 0.28 2.5 L, F (Islam, 2018)
12 2 μmolm-2
Pyrolusite 4.8 0.5 2.5- 22 ± 6 20.82 1.1 / L, F (Islam, 2018)
12 2
Hausmannite 56 0.5 2.5- 22 ± 6 1.81 1.8 / L, F (Islam, 2018)
12 2
Manganite 66 0.5 2.5- 22 ± 6 1.52 3.9 / L, F (Islam, 2018)
12 2

60
Boehmite 220 0.5 2.5- 22 ± 6 0.45 5.8 / L, F (Islam, 2018)
12 2
Mn-Al binary oxide / 0.5 2.5- 22 ± 6 0.73 5.9 / L, F (Islam, 2018)
12 2
MnFe2O4 180 24 2-9 22.5 100 5 100% (Hu et al., 2007)
MgFe2O4 70.3 24 2-9 22.5 100 5 85% (Hu et al., 2007)
ZnFe2O4 80 24 2-9 22.5 100 5 65% (Hu et al., 2007)
CuFe2O4 94 24 2-9 22.5 100 5 50% (Hu et al., 2007)
NiFe2O4 101.2 24 2-9 22.5 100 5 32% (Hu et al., 2007)
CoFe2O4 55.1 24 2-9 22.5 100 5 20% (Hu et al., 2007)

of
ro
-p
re
lP
na
ur
Jo

61
Table 4 Chromium (VI) adsorption performance onto clay materials under given

experimental conditions.

Adsorbent SBET Time pH T [Cr(VI)]0 [Dose] Adsorp Kinetic Isother References

(m2/g) (h) (°C) (mg/L) (g/L) tion model m
model
capacit
y
(mg/g)
Kaolinite 15.8 24 3-10 25 5.2 20 90% / / (Veselská et al.,
2016)
Illite 16.5 24 3-10 25 5.2 20 60% / / (Veselská et al.,
2016)
Mg−Al hydrotalcite / 8 7.5 25 5.8 8 16 PS1, L, F (Deng et al., 2014)
supported kaolin PS2

of
Kaolinite / 24 2.5- 12- 5 0.1 195 PS1, L, F (Zhou and Chen,
8.0 22 PS2 2000)
Montmorillonite / 24 2.5- 12- 5 0.1 6.2 PS1, L, F (Zhou and Chen,
8.0 22 PS2 2000)

ro
Indicotic black (IB) / 24 2.5- 12- 5 0.1 18 PS1, L, F (Zhou and Chen,
8.0 22 PS2 2000)
Yellow brown / 24 2.5- 12- 5 0.1 48 PS1, L, F (Zhou and Chen,
8.0 22 PS2 2000)
Red soil / 24 2.5- 12- 5 0.1 152 PS1, L, F (Zhou and Chen,

Laterite

Kaolin
/

/
24

24
8.0
2.5-
8.0
2-10
22
12-
22
10-
5

1-20
-p
0.1

0.2
166

10.4 /
PS2
PS1,
PS2
L, F

L, F
2000)
(Zhou and Chen,
2000)
(Li et al., 2010)
re
30
Kaolin / 2 2-7 25 200 10 256 PS1, L, F (Liu et al., 2016)
PS2,
IPD
lP

Fire clay / 4 2-10 / 2-10 0.5-4.5 0.11 PS1, L, F, (Rahmani et al.,

PS2 D-R 2016)
Kaolinite 3.8 6 1-10 30 10-50 4 12 PS1, L, F (Bhattacharyya and
PS2, Sen Gupta, 2006)
IPD
na

Acid activated 15.6 6 1-10 30 10-50 4 14 PS1, L, F (Bhattacharyya and

kaolinite PS2, Sen Gupta, 2006)
IPD
poly(oxozirconium) 13.5 6 1-10 30 10-50 4 11 PS1, L, F (Bhattacharyya and
ur

kaolinite PS2, Sen Gupta, 2006)

IPD
tetrabutylammonium 14 6 1-10 30 10-50 4 11 PS1, L, F (Bhattacharyya and
Jo

Kaolinite PS2, Sen Gupta, 2006)

IPD
Ca-BBT 36 24 1-13 25 10.4- 0.2 624 PS1, L, F, S, (Guerra et al., 2014)
(natural bentonite) 270.3 PS2, R-P,
E, D-R
Avrami
Ca-BBTAPS 605 24 1-13 25 10.4- 0.2 16 PS1, L, F, S, (Guerra et al., 2014)
(3- 270.3 PS2, R-P,
aminopropyltrietoxisil E, D-R
Avrami

62
ane modified
bentonite)
Ca-BBTAEAPS 624 24 1-13 25 10.4- 0.2 18 PS1, L, F, S, (Guerra et al., 2014)
(3(2-aminoethyl) 270.3 PS2, R-P,
aminopropyl] E, D-R
trimetoxisilane Avrami
modified bentonite)
Micelle-clay complex / 3 1-6 25 300 5 9.4 / L (Qurie et al., 2013)
Natural clay / 3 2 25 50 1 19 / L (Algamal, 2018)
Bentonite 34 2 2-6.5 30 42 0.5 33 / L, F, (Khan and Khan,
D-R 1995)
Brazilian smectite 51.2 24 1-8 25 6.5-130 0.2 60 / L, F, S (Guerra et al., 2010)

of
ro
-p
re
lP
na
ur
Jo

63
Table 5 Chromium (VI) adsorption performance onto zeolites under given experimental

conditions.

Adsorbent SBET Time pH T [Cr(VI)]0 [Dose] Adsorp Kinet Isother References

2
(m /g) (h) (°C) (mg/L) (g/L) tion ic m
capacit mode model
y l
(mg/g)
zeolite based 24 4 / 40 0.4 44% PS1, / (Adam et al., 2018)
hollow fibre PS2
ceramic
membrane
HDTMA- 507 48 3-10 / 10-70 0.5 21 / L (Yusof and Malek, 2009)
modified zeolite

of
Y (SMZY-50-
S)
SMZY-100-S / 48 3-10 / 10-70 0.5 38 / L (Yusof and Malek, 2009)

ro
SMZY-200-S / 48 3-10 / 10-70 0.5 31 / L (Yusof and Malek, 2009)
SMZY-50-C 485 48 3-10 / 10-70 0.5 26 / L (Yusof and Malek, 2009)
SMZY-100-C / 48 3-10 / 10-70 0.5 31 / L (Yusof and Malek, 2009)
SMZY-200-C / 48 3-10 / 10-70 0.5 27 / L (Yusof and Malek, 2009)
Mercaptosilane
functionalized
sepiolite
/ 24 2-4.5 25 10 2
-p 53 / L, F,
D-R
(Marjanović et al., 2011)
re
Amine- / 24 2-4.5 25 150 0.05 53 PS1, L, F, (Marjanović et al., 2013)
functionalized PS2, D-R
natural sepiolite IPD
lP

Amine- / 24 2-4.5 25 150 0.05 81 PS1, L, F, (Marjanović et al., 2013)

functionalized PS2, D-R
acid-activated IPD
sepiolite
Hexadecylpyrid 48 24 3-11 20 30-150 0.5 / PS1, L, F, (Zeng et al., 2010)
na

inium bromide PS2 D-R

(HDPB)
modified
natural zeolites
ur

Zeolite 6 24 2-8 25±2 20-200 1.0 70 PS1, L, F (Pang et al., 2015)

PS2
Synthetic 2 1-11 / 50-1000 0.25 55% / L, F (Barakat, 2008)
Jo

zeolite
Natrolite / 2 2-8 30 20 0.1-0.6 7 / L, F (Nadeem, 2014)

64
Table 6 Chromium (VI) adsorption performance onto biopolymers under given experimental

conditions.

Adsorbent SBET Time pH T [Cr(VI)]0 [Dose] Adsorp Kinetic Isother References

2
(m /g) (h) (°C) (mg/L) (g/L) tion model m
capacit model
y
(mg/g)
Lignocellulosic 24 2-8 RT 0.1 30 35 / L (Dupont and
substrate extracted Guillon, 2003)
from wheat bran
Amberlite IRA 458 / 2 2-7 25 5.20 0.2 52 PS1, L, F (Jachuła and
PS2, IPD Hubicki, 2013)
Amberlite IRA 958 / 2 2-7 25 5.20 0.2 52 PS1, L, F (Jachuła and

of
PS2, IPD Hubicki, 2013)
Amberlite IRA 402 / 2 2-7 25 5.20 0.2 51 PS1, L, F (Jachuła and
PS2, IPD Hubicki, 2013)
(Jachuła and

ro
Amberlite IRA 900 / 2 2-7 25 5.20 0.2 51 PS1, L, F
PS2, IPD Hubicki, 2013)
Composite chitosan 125 24 4 25 100 0.1-0.5 154 L (Boddu et al., 2003)
Cr(III)-IIP 589 6 25 5 0.02 39 PS1, L, F, (Liu et al., 2013)
supported by SBA
15
Zeolite/chitosan 9.3 24 2-8 25±2 20-200 1.0
-p 109
PS2,
E
PS1, PS2
D-R

L, F (Pang et al., 2015)

re
hybrid composite
Chitosan 92 24 2-8 25±2 20-200 1.0 92 PS1, PS2 L, F (Pang et al., 2015)
Natural clinoptilolite / 2 6 50 8 5.4 PS1, PS2 L, F, (Jorfi et al., 2017)
lP

zeolite D-R, T
Chitosan-starch / ~6 4-8 30 200 1-3 476 / L, F (Ramasubramaniam
blend et al., 2012)
Ternary biopolymer / 1 4-8 30 200 1-6 114 PS1, PS2 L, F (Rajeshwari et al.,
blend 2018)
na

Phosphonium- / 48 2-12 25 25-800 0.01 221 PS1, PS2 L, F (Sessarego et al.,

enhanced chitosan 2019)
Magnetic natural / 24 2-12 25- 300 0.15 345 PS1, L, F (Mthombeni et al.,
zeolite-polymer 45 PS2, IPD 2015)
ur

composite
Polyacrylonitrile- 2151 24 1-6 25 235.3 1 375 PS1, PS2 L (Feng et al., 2018)
based porous
Jo

carbon
Chitosan / 2.5 2-11 25 10-1000 3 78 / L, F (Schmuhl et al.,
2001)
Chitosan-coated fly / / 2-8 25 40-100 0.1 33.3 / L, F (Wen et al., 2011)
ash composite
Chitin / 72 3 25 25-250 1 / PS1, / (Sağ and Aktay,
PS2, E 2002)
Chitosan / 72 3 25 25-250 1 / PS1, / (Sağ and Aktay,
PS2, E 2002)

65
Rhizopus arrhizus / 72 3 25 25-250 1 / PS1, / (Sağ and Aktay,
PS2, E 2002)
Chitin / 1.5 1-9 25 100 0.1 70 / L (Baran et al., 2007)
Chitosan / 1.5 1-9 25 100 0.1 154 / L (Baran et al., 2007)
Purolite CT-275 / 1.5 1-9 25 100 0.1 89 / L (Baran et al., 2007)
Purolite MN-500 20 1.5 1-9 25 100 0.1 127 / L (Baran et al., 2007)
Amberlite XAD-7 450 1.5 1-9 25 100 0.1 6 / L (Baran et al., 2007)
Sodium alginate- / 2-10 30 100 0.1 73.3 PS1, L, F (Karthik and
polyaniline PS2, E Meenakshi, 2015)
nanofibers
Calcium alginate / 72 3-6 / 52 0.5-2 86.4 PS1, PS2 L (Fiol et al., 2004)
beads
Kraft lignin / 3 20 100 5 0.22 / L, F, T, (Brdar et al., 2012)
D-R, T,
S, R-P

of
Orthophosphoric / 3 2-8 / 25-103 0.1-0.5 / / / (Albadarin et al.,
acid-activated lignin
2012)
Modified lignin / 4 2-6 17 / / 9.3 / L (Demirbaş, 2005)

ro
-p
re
lP
na
ur
Jo

66
Table 7 Chromium (VI) adsorption performance onto miscellaneous materials under given

experimental conditions.

Adsorbent SBET Time pH T [Cr(VI)]0 [Dose] Adsorp Kinetic Isother References

2
(m /g) (h) (°C) (mg/L) (g/L) tion model m
capacit model
y
(mg/g)
Diatomite 25 5 2 RT 10-250 0.04 29.4 / L, F (Du et al., 2015)
Radiation grafted N, / 3 5.5 20 5.20 0.1 16 / L, F (Burillo et al., 2013)
N-
dimethylaminoethylme
thacrylate-
Polypropylene

of
Kaolin supported 5.4 36 2-6 25 10-200 0.5 91 PS1, L, F, (Quiton et al., 2018)
biofilm of E. Coli PS2, T, D-R
IPD

ro
Kaolin supported / 36 2-6 25 10-200 0.5 56 PS1, L, F, (Quiton et al., 2018)
biofilm of gram- PS2, T, D-R
positive IPD
staphylococcus
epidermidis
D-MoS2 34.4 / 6 25 10-350
-p
0.5 84 PS1,
PS2
L, F (Sun et al., 2018)
re
Hydrous stannic oxide / 1.5 1-10 25 5-25 0.2 1 PS1, L, F, T, (Goswami and
PS2 R-P Ghosh, 2005)
CaCO3 10 4 5.5 20 5.20 / 0.11 PS1, L, F, (Correa et al., 2013)
lP

PS2 D-R
Vesicular basalt / 9 2-11 25 5 50 78 PS1, L, F (Alemu et al., 2018)
volcanic rock PS2
Biogas residual slurry 160 5 2 30 10-40 4 6 PS1, L, F (Namasivayam and
PS2 Yamuna, 1995)
na

Waste human hair / 0.5 1-10 40 10-30 0.01-1 10 PS1, L, F, (Mondal and Basu,
PS2 D-R 2019)
Oak wood biochar 2.73 48 2-10 25- 20-80 10 3 PS1, L, F, (Mohan et al., 2011)
45 PS2 R-P, T,
ur

S
Oak bark biochar 1.88 48 2-10 25- 20-80 10 5 PS1, L, F, (Mohan et al., 2011)
45 PS2 R-P, T,
Jo

S
Modified biochar from / 120 2-10 25 100 1-16 88.2 PS1, L, F (Chen et al., 2018)
Enteromorpha
PS2. E
prolifera
Magnetic biochar from 5.2 48 3 25 5-150 0.5 25.3 PS1, L, F, T, (Zhang et al., 2018)
Melia azedarachwood
PS2, R-P
IPD

67
Table 8 Thermodynamic parameters for Cr(VI) adsorption onto various substrates at
different temperatures

Substrate Temperature (K) ∆G ∆H (kJ/mol) ∆S References

(kJ/mol) (J/mol/K)
CoFe2O4/MgAl-LDH 283 -1.14 -7.18 -21.36 (Deng et al., 2015)
303 -0.71
323 -0.28
Magnetic multi-walled carbon 293 -0.80 3.85 15.83 (Huang et al., 2015)
nanotubes 303 -0.96
323 -1.28
343 -1.59

Activated carbon from apple peels 283 -0.25 1.99 7.90 (Enniya et al., 2018)
293 -0.33

of
303 -0.41
323 -0.49
Paper mill sludge 298 -3.38 62.72 21.8 (Gorzin and Bahri Rasht

ro
308 -5.51 Abadi, 2018)
318 -7.75
Rice husk carbon 298 -0.64 33.56 115.23 (Khan et al., 2016)
308
318
333
-2.31
-3.20
-4.72
-p
re
Tea-waste/Fe3O4 298 -2.58 11.96 48.77 (Fan et al., 2017)
308 -3.02
318 -3.55
Treated waste newspaper 298 -5.57 19.89 8.50 (Dehghani et al., 2016)
lP

308 -6.47
318 -7.23
Activated carbon derived from 283 -16.08 3.95 0.07 (Malwade et al., 2016)
Leucaena leucocephala waste sawdust 293 -16.79
na

303 -17.50
313 -18.20
323 -18.91
Chemically activated carbon prepared 298.2 -8.28 -18.91 0.07 (Dula et al., 2014)
ur

from waste of bamboo 308.2 -9.52

(Oxytenanthera abyssinica) 318.2 -19.45
Jo

Leucaena leucocephala seed pod 298 -2.07 25.56 0.09 (Yusuff, 2019)
activated carbon 303 -2.63
308 -2.78
313 -3.67
318 -3.87
Bentonite 293 -0.24 5.69 0.02 (Khan and Khan, 1995)
303 -0.44
313 -0.64
Acid-activated carbon prepared from 298 -4.2 78.59 274.4 (Ali et al., 2019)
Juniperus procera Leaves 303 -5.5

68
 313 -8.3
323 -11.0
Graphene oxide/polyamidoamine 293.15 -1.98 50.86 180.25 (Liu et al., 2019)
dendrimers (GO/PAMAMs) 303.15 -3.78
composites 313.15 -5.58
Cranberry (Conus mas) Kernel shell 298.15 -8.63 -26.70 132.15 (Parlayici and Pehlivan,
(CKS) 308.15 -7.32 2019)
318.15 -59.97
328.15 -46.75
Rosehip (Rosa canina) seed shell 293.15 -10.07 -77.87 220.03 (Parlayici and Pehlivan,
(RSS) 303.15 -7.87 2019)
313.15 -5.67
Banana (Musa cavendishii) peel (BP) 293.15 -4.71 -48.0 -132.15 (Parlayici and Pehlivan,
303.15 -39.92 2019)
313.15 -32.79

of
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lP
na
ur
Jo

69