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Current advancement and future prospect of biosorbents for

bioremediation

Simranjeet Singh, Vijay Kumar, Shivika Datta, Daljeet Singh

Dhanjal, Kankan Sharma, Jastin Samuel, Joginder Singh

PII: S0048-9697(19)35890-5
DOI: https://doi.org/10.1016/j.scitotenv.2019.135895
Reference: STOTEN 135895

To appear in: Science of the Total Environment

Received date: 14 August 2019

Revised date: 2 November 2019
Accepted date: 1 December 2019

Please cite this article as: S. Singh, V. Kumar, S. Datta, et al., Current advancement
and future prospect of biosorbents for bioremediation, Science of the Total Environment
(2018), https://doi.org/10.1016/j.scitotenv.2019.135895

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© 2018 Published by Elsevier.

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Current advancement and future prospect of biosorbents for

bioremediation

Simranjeet Singh1,2,3#, Vijay Kumar4#, Shivika Datta5, Daljeet Singh Dhanjal1, Kankan

Sharma1, Jastin Samuel1 and Joginder Singh1*

1
Department of Biotechnology, Lovely Professional University, Phagwara - 144411, Punjab,

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INDIA

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2
Punjab Biotechnology Incubators, Mohali - 160059, Punjab, INDIA
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4
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Regional Advanced Water Testing Laboratory, Mohali - 160059, Punjab, INDIA

Regional Ayurveda Research Institute for Drug Development, Gwalior – 474009, MP,
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INDIA
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5
Department of Zoology, Doaba College Jalandhar, Punjab, INDIA
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*Corresponding author: joginder.15005@lpu.co.in

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# = Equal contribution
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Highlights

 Recent advances in biosorbents and their mechanism

 Strategies to enhance the efficiency of adsorbents

 Adsorbent limitation and dynamics shift

 Limitations in integrating bio-sorbent based technology with existing pilot plants

 Integrating nano-adsorbents with biosorbent carriers and various isotherms

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Current advancement and future prospect of biosorbents for

bioremediation

Abstract

The increasing use of heavy metals, synthetic dyes and pesticides is a major environmental

concern. Wastewaters containing heavy metals and dyes, extensively released from small and

large scale industries enter excessively into food chains resulting in mutagenesis,

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carcinogenicity and serious health impairments in living systems. The arrays of technologies

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are implemented to date to remediate both inorganic and organic contaminants from

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wastewaters. Among which, adsorption is the most attractive method as it employs eco-

friendly, sustainable and cost-effective biomaterials. Use of bioadsorbents is advantageous

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over the conventional adsorbents. Clay, chitin, peat, microbial biomass and agricultural
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wastes are commonly used bioadsorbants. These bioadsorbents are extensively used for

elimination of dyes, heavy metals, adsorption of toxic industrial effluents, removal of

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fertilizers/pesticides, atmospheric pollutants and nuclear waste from the environment. The
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current review presents state of the art knowledge on various types of biosorbents, their uses,
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and mechanism of action. Various strategies to enhance the efficiency of bioadsorbents and
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physicochemical conditions to remediate dyes and heavy metals from waste streams are also

incorporated in this review. Use of nano-bioadsorbents in industries to minimize the

hazardous effect of solid and liquid waste has also been discussed.

Keywords: Bioadsorbent; origin; recyclabale; mechanism; application; efficacy

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Graphical Abstract

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Novelty Statement
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By virtue of their higher efficiency and lower costs, biosorbents can be the suitable options
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for efficient environmental cleaning technologies. Environmental friendly biosorbents

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represent efficient, stable, and novel adsorbents for organic and inorganic pollutants removal

applications, due to (i) unique physicochemical properties, (ii) metal-ion binding functional

groups, and (iii) excellent sorption properties with synergetic effect of environmentally

friendly constituents. Moreover, due to the reusability of the biosorbent, the proposed

environmental technology is also economically acceptable and contributes to zero waste

concepts.

Although, it is very well known, that biosorbents are efficient and eco-friendly option,

transfer of the lab scale results to field scale applications remains distant dream due to several

limitations. This review article discusses the advancement in biosorbents to overcome the

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limitations and understanding their mechanisms and scale-up applications. This would give

the readers a thorough insight on several possible modifications of biosorbents and the reason

for.

Introduction

The primary sources of water contamination include discharge of wastewater from municipal

wastewater, industries and agricultural activities, global and environmental changes (Sharma

et al. 2018). The presence of heterogeneous contaminants such as pharmaceutical

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compounds, heavy metals, dyes, microorganisms etc. even in low concentrations is very

hazardous to the environment aquatic ecosystems and human health (Singh et al. 2018). Even
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a trace concentration of heavy metal ions, dyes and pharmaceutical compounds is a concern
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for human beings (Bharat and Manchanda, 2017). Wastewater restrains various pathogenic
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organisms like protozoan bacteria, helminths and viruses which are directly involved in

causing various diseases like Campylobacteriosis, Hepatitis A, and Leptospirosis etc.

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Treatment of such compounds which exists in small concentrations is a challenging and

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difficult task. Various technologies such as coagulation, electrochemistry, photo-

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electrochemistry, ion exchange, membrane filtration, reverse osmosis, precipitation,

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flocculation, incineration have been developed so far for the treatment of dyes, fertilizers,

organic acids, pesticides, phenolic compounds, halogenated compounds etc. with their

diverse ranges of remediation potential (Singh et al. 2018). Some major limitations of these

technologies include sewage sludge production, energy and non-cost efficiency, low removal

efficiency, generation of toxic metabolic or by-products, and sometimes the introduction of

more potent toxic chemicals into the ecosystem (Uddin et al. 2017).

Bioabsorbents, also called biosorbents, have attained considerable attention for their

application in cleaning the environment pollutants (Xu et al. 2016). The biosorption

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technology has emerged worldwide and extensively used as it is very economical in the

processing of biosorbents (Gupta et al. 2015). From the last few decades, adsorption

technology has been regarded as the most cost-effective & potent process. During recent

years, various data on the use of various adsorbents from various sources have been isolated

and carried out for the purpose for purification of wastewater.

Bioadsorbents are the materials derived from different biological sources like agricultural by-

products. The most common of them are microorganisms, i.e. fungi, algae, yeasts, bacteria

and (Mathew et al. 2016). They serve as an effective adsorbent to accumulate elemental and

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toxic wastes, including industrial wastes, heavy metals, fertilisers, pesticides, and

atmospheric pollutants from the environment (Srinivasan and Sadgir, 2018). Adsorption
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processes like physical, chemical and ionic are involved in sorption of different contaminants
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(Fomina and Gadd, 2014). These adsorption processes are effective due to involvement of
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different specific mechanisms like absorption, acid-base interactions, adsorption, cation- π

EDA interactions, chelation, complexation, complexes involving association (cooperative

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effect of the grid of the polymer network), diffusion, electrostatic attraction, electrostatic
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interactions, hole-filling, hydrophobic interactions, hydrogen bonding, ion-exchange, instance

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ion exchange, microprecipitation, nonspecific hydrophobic partition, p/π–π, pore-filling,

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physical shielding, surface sorption, surface complexation, van der Waals forces, van der

Waals interactions, Yoshida forces etc. Also, the presence of high pore volume, large surface

area, various functional groups and ligands groups in biosorbents make them suitable for the

absorption process. Ligands such as amine, phosphate sulphydryl, carboxyl etc. are involved

in chelation of different organic and inorganic contaminants (Arief et al. 2008). The

interaction of adsorbate molecules with the surface ligands of adsorbents expedites the

processes of adsorption by forming bonds with the surface molecules and holding them inside

the pores. The electrostatic attraction between metal ions and negatively charged reaction site

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on the sorbent paves the way for the formation of complex molecules. This forms to be the

general mechanism of biosorption. The presence of negative charge on the surface of the

biosorbent also facilitates the adsorption of the positively charged cationic dyes via a similar

mechanism. Presence of ligands and other functional groups on the surface also assist the

formation of complexes which lead to further adsorption (Ayangbenro and Babalola, 2017).

The all-inclusive purpose of this review paper is to make a comprehensive analysis of various

classes of biosorbents, their source of isolation, various factors configuring the biosorption

process along with their fundamental mechanism and kinetics. The analyses and findings are

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henceforth represented in this review under various sections, and sub-sections. Current

research works on the biosorption along with future directions are suggested.
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Types of adsorbents
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Based on their source of origin, biosorbent has been broadly classified as natural, biological

and those derived from waste. Different types of biosorbents have been discussed below in
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details under three headings. Also, their categories and examples presented in Table 1.
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Natural adsorbents
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Various naturally occurring materials are present in nature which were having characteristics

of an adsorbent and are easily available in the ecosystem. Although, there are various

naturally occurring adsorbents, clay, zeolite, and siliceous material have been successfully

utilised for the eradication of a number of contaminants like dyes, heavy metals,

pharmaceutical compounds, & other organic contaminants from wastewater or water.

Clay: Clay is the most abundant, naturally occurring biosorbent. Low cost, high adsorption

property, high porosity, large surface area, ease of chemical modification and suitability for

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remediation makes it an important adsorbent (Olu-Owolabi et al. 2016, Ahmaruzzaman,

2008). Clay is composed of a layered structure and on the basis of the differences in their

structures they are classified as (i) Kaolinite (such as serpentine, pyrophyllite, vermiculite,

sepiolite) (ii) Micas (such as illite) and (iii) smectites (such as montmorillonite, saponite)

(Shichi and Takagi, 2000). Out of all three types, montmorillonite has the smallest crystallite

size; hence, it possesses the largest surface area and has the highest cation exchange capacity

(Uddin, 2017). According to Babel and Kurniawan (2003), montmorillonite is 20 times

economical than activated carbon & possess highest cation exchange property and largest

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surface area. Clay possesses net negative charge on their surface which neutralises the by

adsorption mechanism. But many researchers have reported that the clay is capable of
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adsorbing anions also after surface modification. According to Krishna et al. 2001,
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unmodified clay minerals show no affinity for oxyanion of chromate; but after modification
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with a cationic surfactant (Hexadecyl trimethylammonium (HDTMA) bromide), a

considerable amount of chromate was found to adsorb on clay minerals like kaolinite,
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montmorillonite, and pillared montmorillonite.

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Siliceous material: Naturally occurring siliceous materials include dolomite, glasses, perlite
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silica beads and alunite (Siddique et al. 2017). The silica beads have silanol group which

attributes to the chemical reactivity of their hydrophilic surface and irreversible non-specific

adsorption (Ahmaruzzaman et al. 2008). High abundance, availability, low price, mechanical

stability, large surface area and porous structure make them good adsorbents (Crini et al.

2006). According to Ahmed and Ram, 1992, siliceous materials are limited to the usage in

media less than pH 8, as they have a tendency to resist alkaline solutions. Alunite is an

important siliceous adsorbent which is widely used for dye adsorption (Akar et al. 2016).

Alunite is a type of mineral extracted from jarosite group & consists of 50% SiO2. Alunite

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without layering does not have good adsorption properties. That’s why alunite-layered

compounds are taken up for the adsorption process. Other siliceous materials like dolomite,

glass and perlite are used for dye removal from water/wastewater (Gaur and Sharma, 2017).

The use of natural perlite for adsorption of Rhodamine-B (basic dye) from water has been

reported by Vijayakumar et al. (2012). Perlites, due to its low density have the ability to

spread the oil and float on the surface and thus also have the capability for oil sorption

(Bastani et al. 2006). Perlite forms to have different compositions with respective properties

that depend on its origin (expanded and unexpanded).

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Zeolites: These are crystalline hydrated aluminosilicates having a highly porous 3-D
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structure with a negatively charged lattice (Jha and Singh, 2016). The framework structure
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contains pores that are occupied by alkali, alkaline earth cations and water (Wang et al.
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2010). Exchangeable cations present in the interstices balance the negative charge. Large

surface areas with high ion exchange capacity & cost-effective make zeolite an attractive
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adsorbent (Hor et al. 2016). More than 40 natural species of zeolites are reported, out of
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which, clinoptilolite is most abundant (Barbosa et al. 2016). Chemical modification such as
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surface functionalization ion exchange and acid treatment elevates the adsorption capability
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of zeolites (Ennaert et al. 2016). Natural Chinese zeolite has the capability to remove

ammonium ions from liquid solution (Huang et al. 2010). Manganese oxide-coated zeolite

was also reported to remove Pb (II) and Cu (II) ions from the aqueous solution by adsorption

process (Lee et al. 2015).

Biological adsorbents

They are mostly originated from biological sources and microorganisms, i.e. fungi, algae,

yeasts, bacteria and even shells of higher animals. They have a strong affinity towards

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various contaminants present in the water and soil ecosystems. Different types of biological

biosorbents, along with their properties, have been discussed below in details under three

sections.

Chitin and Chitosan

Chitin is an important natural biopolymer, is the second most widely used polymer after

cellulose. It is a hard, white, inelastic nitrogenous polysaccharide, which forms supporting

material of crustaceans, insects, etc. (Elieh-Ali-Komi and Hamblin, 2016). Depending on the

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number N-acetyl-glucosamine units present in the biopolymer it can be termed as chitin and

chitosan with a number of units less than 50 % and higher than 50 %, respectively (Khor et
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al. 2003). Chitosan and chitin are chiefly isolated from crustaceans (crayfish, krill crab) (de
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Queiroz Antonino et al. 2017). Crustaceans exoskeleton are present in large number and are
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readily available as a metabolite of food processing (Assam, Silchar). Chitin is a copolymer

of N-glucosamine and N-acetyl-glucosamine units. Many studies demonstrated the use of

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chitosan and chitin-based biosorbents as efficient materials for adsorption. Nair and
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Madhavan (1984) reported the use of chitosan for the adsorption of mercury ions from
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aqueous solutions. In another study, Jha et al. (1988) confirmed the use of chitosan powder
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for the adsorption of Cd ions at a concentration range of 1–10 ppm using various particle

sizes. Chitosan was demonstrated for the complete adsorption of reactive dyes. Chitosan

cannot be used as an insoluble sorbent as it is soluble in acidic media. Chemical modification

of chitosan not only solve the solubility issue but also control diffusion properties, improves

the removal performance and decreases the sensitivity of sorption to environmental

conditions (Ahmaruzzaman et al. 2008).

Alginate compounds

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They are mostly found in brown seaweeds and composed of linear polysaccharides and are

highly soluble in water (Yu et al. 2017). Being water-soluble has restricted its application for

removing radionuclides and heavy metals. They are used after processing them ion exchange

reaction with multivalent metal ions. After processing, they can be used as an adsorbent or

entrapment of various contaminants. They are also converted into hydrogels using calcium

and have wide applications in the removal of various heavy metals (Gok and Aytas 2009).

They are reported to have a sorption capacity of 70% to 91%. The process in adsorption using

alginate compounds is usually endothermic (Pang et al. 2010)

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Peat
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It is abundant, relatively inexpensive and readily available biosorbent. Raw peat is composed
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of cellulose, lignin, fulvic and humic acid. It is a porous composite soil material having a
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large amount of organic matter (humic substances) at various stages of decomposition

(Sanghi and Verma, 2013). The lignin and humic acid have the ability to form chemical
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bonds; they also have polar functional groups, ketones, aldehydes, alcohols, carboxylic acids
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phenolic hydroxides and ether. On the basis of nature of the source material, peat is
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differentiated into four groups: moss peat, woody peat, sedimentary peat and herbaceous
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peat. The efficacy of peat for dye adsorption from the solution is well demonstrated by many

researchers (Crini, 2015; Chieng et al. 2015; Zehra et al. 2015; Fernandes et al. 2010;

Balasubramanian et al. 2009; Fernandes et al. 2007; Allen et al. 2004; Gündoğan et al. 2004;

Ringqvist et al. 2002; Ho et al. 2002; Chen et al. 2001; Ho et al. 1998). But there are many

limitations associated with raw peat, as it has poor chemical stability, high affinity for water,

tendency to shrink, low mechanical strength and swell and to leach humic substances fulvic

acid (Balasubramanian et al. 2009; Couillard et al. 1994). Chemical modifications of peat,

however, provide robust results by improving the adsorption capacities and selection.

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Biomass

Bioadsorbents such as living or dead biomass, including white-rot fungi & various microbial

cultures also form a potential source for the process of bioadsorption (Gupta et al. 2016; Abdi

and Kazemi. 2015; Kaushik et al. 2009). A large amount of by-product is generated when

microbial biomass is produced during fermentation processes for antibiotic and enzyme

synthesis. This can be used for bioadsorption of pollutants (Gazso et al. 2001). Different

microbial biomasses mainly used for the treatment of toxic heavy metal ions from different

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water systems along with their biosorption capacities have been presented in Table 2. A large

variety of fungal organisms have the capability of decolorizing various dyes. Different
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functional groups such as phosphate amino carboxyl, and thiol groups present in the cell wall
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of fungus facilitate the binding of dye with the fungi (Bayramoglu et al. 2006). Although
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biosorption of dyes onto the cell surface seems to be a swift process, it is evidenced that the

entire process still takes a couple of hours (Mou et al. 1991). The fungal biomass can be
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immobilized for dye adsorption even in restricted growth conditions, which is advantageous
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when the effluent is toxic and inhibits cellular growth. The inactive biomass can be reused
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without any additional nutrient supply (Prigione et al. 2008). Living cells have been reported
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to bioadsorb and also to biodegrade toxic compounds (Fu and Viraraghavan, 2001).

Photosynthetic organisms, such as cyanobacteria or algae, have a wide distribution and are

receiving much attention due to their biodegrading and biosorption capabilities (Alcántara et

al. 2015). Algal biomass is capable of chromophore adsorption. The usage of biomass is very

interesting when the effluent or the solution is very toxic and does not support the growth of

biosorbent (Das et al. 2008). In such a case, the utilization of dead biomass eliminates this

problem. The production of fungal biomass as bioadsorbent is easy and economically viable

by using an inexpensive growth media.

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Bioadsorbents from waste materials/by-products

Agricultural wastes, vegetable and fruits peels are the discarded waste materials and may

have wide significant application (Cho and Park, 2018). These materials could be utilized as

low-cost adsorbents after some processing. The main aim to use these agricultural by-

products is to minimize their accumulation and reuse them for productive purpose. This has

led to their application as biosorbents for removal of environmental pollutants.

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Activated carbon from solid waste: In 1900-1901, the existence of active carbon came into

being to substitute the bone-char for the process of sugar refining (Bansal et al. 1988). The
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commercial production of active carbon from wood was first reported in the early 19th
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century in Europe (Rangari and Chavan, 2017). Activated carbon possesses an amorphous or
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random structure and is a crude form of graphite. Activated carbon is extremely porous,

exhibits a broad range of pore sizes, from slits visible cracks and crevices of molecular
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dimensions (Xia and Shi, 2016; Yuen and Hameed, 2009; Hamerlinck et al. 1994). Any
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material rich in carbon can be a precursor for generating activated carbon. They can be
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derived from various sources such as wood char, coconut shells, peat, petroleum coke, carbon
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black, lignite, sugar, fish, bone char, and fertilizer waste (Ali, 2010; Mohan and Pittman,

2006). Amongst all the sorbent materials, activated carbon is the widely accepted adsorbent

for the adsorption of pollutants from wastewater (Babel and Kurniawan, 2003; Rao et al.

2008). There are many reports of using coal-based adsorbents (Hassani et al. 2014; Khan et

al. 2013; Mohan and Gandhimathi, 2009; Anwar et al. 2009; Dincer et al. 2007; Li et al.

1998).

Adsorption, with the help of activated carbon, is effective in treating wastewater effluents

rich in both organic and inorganic contaminants (Namasivayam and Kavitha, 2002). The US

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Environmental Protection Agency (USEPA) has mentioned activated carbon one of the best-

controlled remediation technologies worldwide (Derbyshire et al. 2001; Hamdaoui and

Naffrechoux, 2007). Mainly, coal is extensively used for producing activated carbon. But, it

is non-selective many times and sometimes ineffective; also greater is its quality, higher is

the cost.

Agricultural waste: Biosorbents derived from agricultural solid waste are cheap and readily

available. Common examples are coir pith coco (Namasivayam and Sureshkumar, 2008); rice

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husk biomass (Han et al. 2008); sugar peat pulp (Yao et al. 2011); orange and banana peels

(Annadurai et al. 2003); and corn cob (Nethaji et al. 2013). Another agricultural side product,
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tree fern is also used to adsorb pollutants (Ho et al. 2005). Tree fern is composed of lignin
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and cellulose. Bark, a polyphenol-rich compound, which is a by-product from timber
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industries, has also been found very effective in adsorption of dyes and various other

compounds from aqueous solutions. Tannin present in the bark basically imparts adsorption
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properties to the bark (Bacelo et al. 2016; Arasaretnam and Karunanayake, 2010; Morais et
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al. 1999). The only investment cost on such forest waste is the transportation charges for
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moving the waste from storage houses and different sites, where they will be valorized and
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used (Palma et al. 2003). Plant bioadsorbents showing capabilities for the adsorption of heavy

metals along with their adsorption capability has been presented in Table 3. Different types of

plant processed biomass into usable industrially important bio sorbent materials are

illustrated in figure 1.

Industrial waste: Industrial by-products such as sawdust derived from wood industry are

widely used as important adsorbents. Sawdust contains organic compounds with

polyphenolic groups (such as cellulose, lignin, and hemicellulose) which assist the binding of

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sawdust with dyes through different mechanisms (Inoue et al. 2017; De Gisi et al. 2016;

Gupta et al. 2015). Sawdust is either positively or negatively charged if the pH of the mixture

is beyond its characteristic neutral pH. One major problem associated with sawdust materials

is that pH values play an eminent role in sorption processes (Garg et al. 2004). Other

industrial wastes used as adsorbents include red mud, blast furnace slag, metal hydroxide

sludge and fly ash. The sludge derived from electroplating is a rich source of chromium,

nickel and other heavy metals (Ahmaruzzaman 2011). It also contains various salts, insoluble

metal hydroxides etc. which is formed during precipitation of metal ions with calcium

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hydroxide in wastewater (Zhou and Haynes, 2010).

Biosorption mechanisms
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The mechanism of biosorption has been proven to be of great significance due to their ability
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to adhere to metals to different biological material. Biosorption mechanism is diverse, as the

sorbents have unique biological sources. Understanding the mechanism helps, to control the
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pollutant removal, increase the sorbent’s efficiency and use the biosorbents for in situ bio-
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remediation process. The collaboration of different factors on unambiguous biosorbents

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makes it an unfeasible to imply a common mechanism. Even, many different metal binding
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mechanisms have been proposed, such as coordination/chelation, complexation, ion-

exchange, as well as physio-adsorption (Fosso-Kankeu and Mulaba-Bafubiandi, 2014). But

the true mechanism involved in metal biosorption is still incompletely comprehended (Wang

and Chen, 2006). Mechanism of biosorption or metal microbe interaction is provided in

figure 2.

Chemisorption mechanisms

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The chemisorption mechanisms chiefly comprise ionic exchange, electrostatic interaction,

chemical precipitation and complex of functional groups present on the outer surface of

bioadsorbent. Sorption could involve the electrostatic attraction, complexed carboxyl or free

inner-sphere complex, alcoholic hydroxyl, otherwise phenolic hydroxyl groups of biochar

(such as –ROMe, –COOMe, R–COOH, and –ROH, where Me is metal atoms) as well as

superficial or co-precipitation (Nartey and Zhao, 2014). Phenolic or alcoholic hydroxyl

groups (R–OH) and carboxyl (R–COOH) are usually acknowledged since these groups

contribute as well as coordinate among heavy metals and surface of the sorbent (Nartey and

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Zhao, 2014).

Ion-exchange, as the name states are the irreversible reaction in which, ions suspended in the
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solution gets replaced with similarly charged ion onto the absorbent (Han et al. 2006). The
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reaction mechanism involved can be illustrated by the Eq. 1:
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MX+ + X(AB) ⇌ XA+ + MBX (1)

Where, AB = amount of acid sites over the adsorbent surface, MX+ = Ions of metal, and MBX
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= amount of MX+ sorbed.

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On following the, Eq. (1) as illustrated above, the equilibrium constant of ion-exchange can
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be ascertained by Eq. (2):

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(2)

According to the reports, the ion-exchange mechanism is the leading bioadsorption processes.

During this process, the metal sequestration clings to a multifaceted mechanism which

comprises of complex formation among metal of cationic nature and ligands present on the

cell wall, ionic interactions, and also precipitation over the cell surface (Gavrilescu, 2004).

Another biosorption mechanism is Chelation, which can be termed as the process in which

metal ions attaches with organic ligand molecules to construct a ring-like structure. RCOO−,

OH−, SO2−, P(=O) (OR)3, and NH3+ are some of the functional groups which are involved

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biosorption of metals (Flora and Pachauri, 2010). Out of which NH3+ is found to be most

efficient in removing the heavy metals as both the chelation as well as electrostatic

interaction/hydrogen bonding takes place.

Physio-adsorption mechanisms

Physical adsorption involves the interaction between the surface of the adsorbate and

adsorbent by Vander Waals forces. In the context of thermodynamics, this adsorption

mechanism is exothermic (Value of DH8 is negative) and spontaneous (Gibbs energy is

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negative). It is stated that physical adsorption has no vital role in the biosorption mechanism.

But with few exemptions, physical adsorption between olive cake (Anber and Matouq et al.
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2008) and Cd(II) as well as rubber leaf powder and Cu(II) were found to be dominant (Ngah
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and Hanafiah 2008). Various biosorptions processes and mechanism are discussed in section
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4.
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Functional groups involved in adsorption process

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The various functional groups involved in the adsorption process are carboxylic groups,
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amino groups and a hydroxyl group (Rajapaksha et al. 2016). Figure 3 represents different
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mechanisms involved in biosorption phenomenon. The oxygen functional groups, in

particular, the phenolic and lactonic groups are capable of binding efficiently with the heavy

metal, and the oxygen level also increases due to oxidation reaction occurs at the biochar

surface (Harvey et al. 2011). These groups are intended to participate in the metal adsorption

process (Deliyanni et al. 2015). These groups are controlled by pyrolysis temperature, as the

biomass pyrolysis carbonization under high temperature its organic composition and the

carbon atoms cross-link, resulting in the formation of a porthole on the biochar surface. In

certain cases, the increase in the pH, porosity, surface area etc. does not affect the mechanism

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of functional groups although temperature and a high degree of carbonization have resulted in

the major declination of these groups (Chen et al. 2018; Li et al. 2017). The characterization

of these groups has been done by the use of FTIR (Fourier Transform Infrared Spectroscopy).

FTIR functions by producing a different range of spectra at different temperatures that show

dehydration of cellulosic as well as ligneous compounds in plant material. These are expected

to show peaks by 3500-3200 cm-1 if heated at 300°C.In the presence of lignin or cellulose

products, the peaks are meant to be observed by 1600-1700 cm-1 (Keiluweit et al. 2010). The

FTIR spectra of wood and grass feedstock biomass show no prominent change in their

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functional groups when heated below 100-200°C. The process where there is an increase in

the temperature during pyrolysis has deliberately shown results in the loss of functional group
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(Yuan et al. 2011). This loss of carboxyl functional groups has been detected using FTIR
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photoacoustic spectroscopy, where a decrease in the peak intensity of carboxylic (-COOH)
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and hydroxyl (-OH) group at temperature 300-700°C is noted (Cantrell et al. 2012). Along

with the use of FTIR, nuclear magnetic resonance (NMR) is used to illustrate the various
al

functional groups in rice straw produced at 100-800°C. The biochar of rice straw undergoes
n

dihydroxylation/dehydrogenation and aromatization process (Hossain et al. 2011; Chen et al.

ur

2014; Zhang et al. 2015). The conventional types of processes illustrate the formation of
Jo

anomeric O-C-O carbons and O-alkylated groups by increasing the temperature, resulting in

the production of biochar at a temperature below 300 ° C having dominant O-alkylated

carbons, which generally loose their identity in biochar which is produced at >300°C (Li et

al. 2013). Functional groups such as carboxyl, hroxyl, alcoholic etc. involved in adsorption

process undergo certain mechanisms which are influenced by the extrinsic parameters

resulting in the change of the complexity of these groups. The group considered to be work

efficiently at pH 3-4 is a carboxyl group (Pulido-Novicio et al. 2001). Increase in pH, the

carboxyl group of biosorbent forms a complex with the positively charged metals after

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deprotonation. Therefore, the straw will be negatively charged because of the functional

group deprotonation (Yuan et al. 2011). The adsorption behaviour of biochar employs a

certain mechanism which is therefore governed by biochar properties like, surface area,

mineral component, porous structure and surface functional groups (Mohan et al. 2014; Tan

et al. 2015; Ahmad et al. 2012). The removal of heavy metals in their best possible way

involves intrinsic effects of various interactions, namely, cation exchange, precipitation,

electrostatic interaction and chemical reduction, complexation. Surface functional groups like

hydroxyl (-OH) and carboxylate (-COOH) is present on the surface of biochar having strong

f
oo
interaction with heavy metals, for example surface complexation, electrostatic attraction and

ion-exchange. The functional group changes are noticeable after and before the adsorption of
pr
metals (Khare et al. 2013). In a theoretical study, it was reported that sugar beet in biochar
e-
tailing could remove Cr(VI) to Cr(VI) by electrostatic attraction latter which can be reduced
Pr

to trivalent Cr and trivalent Cr complexation. This process is understandable into three major

parts: Firstly, the negatively charged on the Cr(VI) species transported to positively surface
al

of biochar under low pH conditions. Secondly, hexavalent Cr is reduced to trivalent Cr by the

n

involvement of electron donors and hydrogen ions from biochar. Thirdly, the trivalent Cr
ur

reduced to hexavalent Cr released in aqueous solution, and the remaining Cr(III) parts made a
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complex with functional groups on biochar (Dong et al. 2013). The Pb(Lead) adsorption on a

sludge-based biochar have a huge participation of functional groups, which include metal

exchange with Na+ & K+ due to surface complexation, electrostatic outer-sphere

complexation, with free -COOH functional group and OH- functional group and inner-sphere

complexation with free OH- group (Lu et al. 2012). A similar mechanism is also observed in

the adsorption of Hg(II) on soybean stalked based biochar (Kong et al. 2011).

Adsorption thermodynamics & Kinetics

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Thermodynamic behaviour of heavy metals on different biosorbent is termed as endothermic

or exothermic sorption processes based on nature of adsorbent. In addition to that, free energy

insights the chemical or physical sorption (Sahmoune, 2018; Madala et al. 2017; Yao et al.

2010; Ramesh et al. 2005).

∆G = - RT ln Kad

ln Kad = ∆S/R-∆H/RT

Where ∆G (J/mol) = Gibb’s energy, T = temperature (Kelvin) (K), ∆S (J/mol K) = adsorption

entropy, ∆H (J/mol) = adsorption enthalpy, R = ideal gas constant (8.314 J/mol K) and Kad is

f
oo
the adsorption equilibrium constant.

The Kad is equilibrium adsorption constant for thermodynamics which can be taken from the

Langmuir equilibrium constant.

pr
e-
Kad = KL
Pr

Here, the Langmuir constant at equilibrium is used for the determination of ΔG0.

The Langmuir equation is given as following (Sahmoune, 2018):

al

qe = qmax CeKL/CeKL + 1
n

In which qe (mg/g) and qmax (mg/g) are the amount adsorbed at equilibrium and maximum
ur

adsorption capacity of adsorbent.

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KL = Langmuir equilibrium constant related to the energy of adsorption (lmg-1).

The Langmuir model suggests that uptake occurs on a homogeneous surface by monolayer

sorption without interaction between adsorbed molecules. In addition, the model assumes

uniform energies of adsorption onto the surface and no transmigration of the adsorbate

(Sahmoune et al. 2018).

The development of the most suitable adsorption equilibrium correlation is vital, in order to

retrieve an ideal adsorption system which is important for authentic prediction and

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quantitative comparison of adsorbent behaviour for various adsorbent systems and adsorption

parameters.

Pseudo-first order and Pseudo second-order:

Many workers have studied reaction kinetics-based models for the adsorption of organic and

inorganic pollutants from wastewater (Tan and Hameed, 2017; Malamis and Katsou, 2013;

Gupta and Bhattacharyya, 2011). The most studied model for adsorption is the pseudo-first

order rate equation of Lagergren which originally appear in literature in 1898 (Inglezakis et

f
oo
al. 2019; Ho, 2006):

dqt/dt = k (q∞ - qt)

Where, k is the reaction rate constant.

pr
e-
After integration: In (q∞/q∞ - qt) = k t
Pr

Tran et al. (2017) discussed pseudo-second-order rate equation while presenting adsorption of

contaminants from aqueous solutions, which was first presented by Blanchard et al. (1984):
al

dqt/dt = k (q∞ - qt)2

n

After integration: 1/q∞ - qt) = 1/q∞ + k t

ur

The first pseudo order and second pseudo order kinetics and equilibrium study is limited by
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chemisorption process and kinetic analysis can be done by using

Where qt & qe (mg/g) heavy metal adsorption at time t (h) and k1 (1/h) & k2 (g/(mg.h) are rate

constant for the pseudo & second-order adsorption kinetics, respectively (Aljeboree et al.

(2017).

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The adsorption capacity of each metal ion adsorbed by the carbon activated carbon or biochar

was determined (qe, mmol g-1) as the difference between their initial & final concentrations as

given by Karunanayake et al. (2018).

Where, Co = initial metal concentration (mM), W= amount of sorbent (g), Ce = metal

concentration at equilibrium (mM), and V = volume of metal solution (L).

In most of the studies, experimental data were found to be best fitted to the Langmuir

f
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isotherm and the pseudo-second-order kinetic model suggesting the predominance of

chemical forces in the biosorption of rare earth elements (REEs) from waste solutions (Gupta

et al. 2019). pr
e-
Pr

Application of bioadsorbents

Low cost, high adsorption capacities, presence of different functional groups and high
al

chances of metal recovery makes biosorbents as most suitable candidates for the eradication
n

of environmental toxins and pollutants. Biosorbents have widespread applications in the

ur

removal of dyes, heavy metals, adsorption of toxic industrial effluents, removal of

fertilizers/pesticides, atmospheric pollutants and nuclear waste.

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Removal of heavy metals ions

The use of bioadsorbents for removal of heavy metal has been a subject of special attention

due to the increasing demand for high-quality water (Zwain et al. 2014). The continuous

demand for high-quality water has incited great attention among researchers to work towards

the recovery and reuse of wastewater to generate consumable high-quality water

(Kanamarlapudi et al. 2018). Industrial wastewater mostly comprises of both organic and

inorganic pollutants, which deteriorate the quality of water. These pollutants enter the natural

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water bodies from various industries, household etc. and thus enter the food chain. These

pollutants are highly toxic to both biotic and abiotic sources (Goel 2006).

The persistence of these heavy metals is the primary concern for all. Different industrial

processes such as leather tanning, electroplating, foundry, chemical manufacturing, dye

manufacturing, jewellery works, mining, Cd-Ni phosphate fertilizer, batteries, pigments, etc.

are the major source of water pollution (Thairuddin et al. 2013). Continuous disposal of

industrial waste builds up the concentration of metal ions in natural water bodies (Turhanen

et al. 2015). Conventional methods for the treatment of wastewater include membrane

f
oo
filtration, chemical coagulation, electrodialysis, ion exchange, reverse osmosis, etc. (Das and

Osborne, 2018; Rao et al. 2003). High cost of operation, sludge disposal aspects face and
pr
high maintenance are certain factors which limit these methods. The use of low-cost
e-
bioadsorbents is the most viable method for the removal of heavy metal ions from polluted
Pr

water (Gunatilake, 2015). This area of bioadsorbents is less explored and holds lots of

opportunities for the researchers to find a better solution to the problem of heavy metals.
al

The use of teak leaves (Tectona grandis) has been reported by Ajmal et al. (2008) for the
n

removal of lead ions from aqueous solution. Teak leaves show with a maximum adsorption at
ur

pH 5.0 and the breakthrough capacity 30 mg/g of adsorbent (Mohammed et al. 2008).
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Benavente et al. (2008) have demonstrated the use of chitosan for adsorption of Cu(II),

Hg(II), Zn(II) and As(V) metals. Shivamani and Prince (2008) have reported the use of Crude

& acidified Pongamia Leaf Powder (CPLP)) as adsorbents for removal of Cr(VI). Plant

bioadsorbents showing capabilities for the adsorption of heavy metals along with their

adsorption capacity has been presented in Table 5.

Adsorption of toxic industrial wastes

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Disposal of toxic dyes into water bodies by textile, printing leather tanning and cosmetic

industries is another cause of water pollution and degradation of water resources (Rasalingam

et al. 2014). Bioadsorbents derived from agricultural by-products, industrial solid waste,

biomass-based activated carbon, clay minerals and other inorganic oxides, are used for

removal of the dyes from aqueous solution (Barakat, 2011). Adsorption capacities Q (mg/g)

of different waste materials derived from raw agricultural byproduct in the removal of dyes is

mentioned in Table 6. Researchers have demonstrated the use of modified barley straw for

the adsorption of RB4 dye. Biosorbent derived from barley straw shows 100 % adsorption

f
oo
efficiency for removal of RB4 at pH, which is then reduced by 50 % with an increase in pH

(Yagub et al. 2014). Here are few adsorbents with their maximum adsorption capacity which
pr
adsorb the different dyes. A mechanism for the reduction of azo dyes by whole bacterial cells
e-
is exhibited in figure 4.
Pr

Adsorptive removal of fertilizers/pesticides

al

The excessive use of fertilizers and pesticides in forestry, agriculture & domestic activities to
n

increase production and for controlling pests is another cause for water pollution (Khatri and
ur

Tyagi, 2015). These fertilizers and pesticides are washed away with rainwater into river
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streams. As a result of the concentration of chemical nutrient increase in the water bodies

causing eutrophication hence adversely affecting aquatic life (Bhateria and Jain, 2016). The

use of activated carbon in the form of an adsorbent is widely accepted technology used for

purification of polluted water contaminated by toxic chemicals and pesticides. However, the

use of activated carbon has economical restrictions due to the cost of activated carbon. This

has led to a search for new cheap and easily available adsorbent materials. Owing to it,

wastes from agricultural and industrial, synthetic and natural materials such as carbon cloth,

resin wood charcoal, bagasse fly ash, porous wheat-residue black carbon, lignin, polymeric

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adsorbents, waste tire rubber granules, etc. have been used for this purpose (Demirbas, 2008;

Sud et al. 2008; Abdel-Halim et al. 2003). The carbonaceous adsorbent can be a better

alternative for activated carbon for the removal of the fertilizers and pesticides from the water

bodies (Gupta et al. 2006).

Adsorption of atmospheric pollutants

Emissions from different chemical, petrochemical, and allied industries result in Volatile

Organic Compounds (VOCs) which are the common air pollutants. VOCs are one of the main

f
oo
sources of photochemical reaction in the atmosphere and lead to the generation of reactive

oxygen species (George et al. 2015; Khan and Ghoshal, 2000). The reactive oxygen species
pr
degrade ozone and pose a threat to the environment by creating an ozone hole. Volatile
e-
Organic Compounds (VOCs) are widely used in chemical industries as solvent thinners,
Pr

liquid fuels lubricants, degreasers and cleaners (Petrauskaite et al. 2017). Some common

examples of VOCs are ethane, methane, methyl chloride, tetrachloroethane, chloro-

al

hydrocarbons and perfluorocarbons (Khan and Ghoshal, 2000). VOC’s have an adverse effect
n

on climate, on the health of animals and human beings and the growth and decay of plants.
ur

This alarming situation calls for controlling the VOCs emission from the industry.
Jo

Carbon adsorption is a very common method of VOCs emission control. They are removed

by physical adsorption of the air which is passed through the inlet over the surface of the

carbon. VOC molecules are physically attracted and held to the surface of the carbon.

Activated carbon has a vast infrastructure of pores and micropores and acts as a good

adsorbent due to its large surface area (Khan et al. 2000). Carbon adsorption systems involve

low installation costs and flexible and inexpensive to operate.

Usually, pristine biosorbent produced from biomass feedstock has reduced sorption capacity

(Yang and Jiang 2014). The limited adsorption capacity of bioadsorbents can be enhanced by

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several chemical processes, like surface treatment, oxidization of surface, and

functionalization. Use of bioadsorbents is advantageous over the practice of conventional

adsorption methods. The bioadsorbents derived from biological waste are cost-effective,

highly efficient minimal of chemical and low biological sludge, do not require any additional

nutrient, have high chances of metal recovery and most important the regeneration of

bioadsorbents is facile and cheap.

Strategies to enhance the efficiency of Bioadsorbents

f
oo
Generally, biosorbent produced from biomass feedstock without treatments have reduced

sorption capacity (Yang and Jiang 2014). Different approaches are reported to elevate the
pr
adsorption capacity by increasing the number of functional groups as well as to increase
e-
sorption sites on biosorbents surface, which involve oxidization of surface, surface
Pr

amendment, functionalization, etc. (Wang et al. 2017; Sizmur et al. 2017; Rajapaksha et al.

2016; Ma et al. 2014; Loganathan et al. 2013). The description of strategies for enhancing the
al

sorption capacities of different adsorbents is summarized in figure 5.

n

Pyrolysis is an important pre-treatment strategy to enhance the efficacy of the bioadsorbents.

ur

In this process, the biomaterial is disintegration under limited oxygen condition to convert the
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biomaterial into the char. This process is very different from the gasification, in which the air

is supplied insufficient amount, as a result of which syngas is synthesized. Pyrolysis can be

differentiated on the basis of the temperature at which they are treated, heating rate. Till date,

the exact definition to describe the pyrolysis is not quoted. Different types of pyrolysis

methods are as follows. Slow pyrolysis is a method to disintegrate the biomaterial at the

temperature ranging from 350-800 °C with a heating rate of <10 °C per minute. The

biomaterial which has been converted into the biochar by this method are pine wood, wheat

straw, green waste, dried algae, hickory wood, olive pomace, orange waste and compost

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(Ding et al. 2016; Ronsse et al. 2013; Pellera et al. 2012). Torrefaction is a process in which,

the biomaterial is disintegrated at the temperature ranging from 200-300 °C with a heating

rate of <10 °C per minute. The biomaterial which has been converted into the biochar by this

method cotton/corn stalk, rice husk, sawdust, peanut husk, bagasse, and water hyacinth (Chen

et al. 2014; Pimchuai et al. 2010). Applying fast pyrolysis, biomaterial is disintegrated at the

temperature ranging from 400-600 °C with heating rate is very fast, i.e. 1000 °C per second.

The biomaterial which has been converted into the biochar by this method are pitch pine, oak

wood, oak bark, guayule bagasse, soybean straw and water hyacinth (Mohan et al. 2014; Kim

f
oo
et al. 2012; Lima et al. 2010). Using gasification, the biomaterial is disintegrated at the

temperature ranging from 700-1500 °C with heating rate is moderately fast. The biomaterial
pr
which has been converted into the biochar by this method are eucalyptus wood chunks, wheat
e-
straw, sewage sludge and wood pellets (Hansen et al. 2015Sattar et al. 2014; Deal et al.
Pr

2012).

Hydrothermal carbonization is a pretreatment by which, biomaterial is disintegrated at the

al

temperature ranging from 175-250 °C with heating rate is very slow. The biomaterial which
n

has been converted into the biochar by this method comprises bamboos, coconut fibres,
ur

eucalyptus leaves, pinewood, peanut shell, wheat straw, corn stock and sawdust (Sun et al.
Jo

2015; Huff et al. 2014; Liu and Balasubramanian, 2014; Schneider et al. 2011). The pre-

treatment of pristine bioadsorbent materials with acid and/or base is an important method of

preparation of sorbents. The acid-base treatment helps to functionalize the bioadsorbent and

enhance the efficacy by the increased interaction of adsorbate with adsorbent through newly

formed functionalities (Chen and Wu, 2004). In this process, the pyrolysed biomaterial is

treated with 72 % H2SO4 in the ratio of 1:10 for biomass and acid, respectively. After the

addition of acid, the biomaterial is heated at 50 °C followed by the filtration. After filtration,

the filter material is exposed to 95°C for 6 h for dehydration, polymerization and

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carbonization in order to obtain the solid final product. Repeated washing of solid product is

done to completely remove the sulphate ions. After the neutralization of the hydrochar, it is

heated at 120 °C for overnight (Wang et al. 2010). For the further modification, the hydrochar

is treated with 7M KOH, which increase the porosity as well as the surface area of the

biochar. It has even been reported that the yield of the KOH treated hydrochar was 48 % at

150 °C and 1.52 MPa pressure (Dehkhoda and Ellis, 2013; Dehkhoda et al. 2010). Biochar

after acid-base treatment forms a solid product hydrochar, which is hydrophobic and non-

toxic in nature which can be used as activated carbon, solid-fuel and adsorbent (Guo et al.

f
oo
2016). The enhanced performance of hydrochar over biochar is attributed to its low ash

content, high adsorption affinity for both polar/nonpolar functional groups (Kambo and Dutta

2015).
pr
e-
Hydrothermal modification of shaped zeolite 13X in alkali, NaOH was c-ompared with
Pr

unmodified adsorbent and it was found that modified adsorbent exhibited higher adsorption

capacity and uptake rate for carbon dioxide. This was expected due to the increase effective
al

adsorption surface and the decrease in diffusion resistance (Zhao et al. 2007). Zeolite
n

synthesized from coal flash has been affirmed for adsorption of humic acids from water (Li et
ur

al. 2011).
Jo

Nano-bioadsorbents

The alarming situation of increasing water and air pollution not just calls for a solution but

for advanced material with maximum efficiency. A vast amount of research is done and on-

going in the area of bioadsorbents. Efforts are being made to explore new materials and to

increase the efficiency of existing bioadsorbents. The scope for finding new materials is

limited due to certain factors. The use of hybrid technologies is an answer to the existing

problem. It’s high time to step up from single component system to multicomponent

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bioadsobent. This can be realized by forming nanohybrids. Playing with the chemistry helps

us to combine the bioadsorbents with nanoparticles to form nano bioadsorbents (Boubakri et

al. 2017). Both the parent materials (nanoparticles and bioadsorbent materials) combine to

results in a novel material with multifold enhancement in terms of performance Conversion

of large particles of bioadsorbents to ultrafine particles results in the increased surface area.

But ultra-fine powders may have a strong tendency to agglomerate into larger particles,

resulting in an adverse effect on both catalyst performance and effective surface area (Li et al.

2017). The nanoparticle present over the surface of bioadsorbent prevents their aggregation

f
oo
and in turn stabilise the porous structure of adsorbent (Gehrke et al. 2015). This helps in

maximizing the available site, attaining high adsorption capacity high surface area.
pr
Soleymanzadeh et al. 2015 reported the synthesis of Nanoscale zerovalent iron supported on
e-
sineguel as seed waste and its use for the removal of Cd(II) ions. The combination of
Pr

nanoparticles over the surface of the surface of sineguelas waste can help to overcome the

aadsorption of cadmium ions. Arshadi et al. (2017) have reported the preparation of nano
al

zero valent iron modified with an aquatic plant Azolla filiculoides for the removal of Pb(II)
n

and Hg(II) from the water. The use of nano-bio adsorbent also reduces the cost by reducing
ur

the dose amount of adsorbent required for adsorption. The loading of nanocarbons onto the
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surface of clay results in improved the organophilic property of palygorskite and high

adsorption ability for phenols which is also comparable to active carbon (Wu et al. 2015).

Thanh et al. (2011) have reported enhanced performance of nanocomposites of perlite with

iron and manganese nanomaterials for As (V) removal compared to pristine perlite. The

presence of nanoparticles helps enhance the probability of transport and in turn, reduce the

potential for toxicity. The use of nanobiocomposites is a new and effective approach for

removal toxic pollutant and heavy metals from aqueous solution.

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Isotherms for Biosorbent based Adsorption Systems

Adsorption isotherms usually describe the interaction of pollutants with the adsorbent

material and are critically important for expressing surface capacities, surface properties and

moreover effective designing of the adsorption systems. Adsorption isotherms are

indispensable curve stating the mechanism governing the retention or mobility of adsorbing

material from the aquatic environments at sustained pH and temperature (Limousin et al.

2007). The point of adsorption equilibrium is reached when an adsorbate comes in contact

with adsorbent with adequate time, keeping the concentration of adsorbate in a dynamic

f
oo
balance. Usually, the mathematical modeling constitutes a significant role towards the co-

relation analysis, applicable practices and operational designing of the adsorption systems
pr
and is illustrated by presenting graphically depicting concentration against solid phase
e-
(Lashgari et al. 2015). It provides an insight into surface properties, degree of affinity and
Pr

adsorption mechanisms (Koçer and Acemioğlu, 2016). Isotherms models employed as well as

the best fit for the study of adsorption processes of different materials on adsorbates are
al

shown in Table 4. Various adsorption isotherm models have been formulated based on three
n

basic approaches. First one simply refers to a state of dynamic equilibrium in which
ur

desorption and adsorption rates are almost equal. The second one provides an outline of
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deriving various adsorption isotherm models and third is simply helps in the generation of

curve fits. Based on these approaches, they are simply classified into two-parameter, three-

parameter and multilayer physisorption isotherms (Foo and Hameed, 2010).

The adsorption of major biosorbents tends to follow Langmuir isotherm, of which most of

them tend to fit the non-linear regression. Generally, the biosorbents tend to have

heterogeneous surface properties which affect the kinetics and adsorption equilibrium. This

suggests that more than one type of adsorption site can bind the target pollutant, and there is a

different heat of adsorption for each type of site in a biosorbent which follows the said

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isotherm. Interestingly, Langmuir isotherm, describes most of the heterogeneous surface

based adsorption systems, despite being developed for sorbents which possess characteristics

which is based on homogeneous surface sites. The adsorption of malachite green dye,

methylene blue, basic dyes, and basic red 9 by activated carbon tend to fit the Langmuir

isotherm adsorption. The adsorption of 2-picoline and brilliant green dye by bagasse fly ash,

strontium by bentonite, Hg(II) and Pb(II) by biochar, zinc (II) ions by Ca-alginate beads,

cadmium ions by eucalyptus bark, Pb sorption by montmorillonite, and kaolinite, safranin by

rice husk, brilliant green dye by rice husk ash, lead, cadmium, chromium, copper, and zinc by

f
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sesame straw biochar; Ni(II), Cd(II) and Cr(VI) by sunflower plant biomass-based carbons;

cadmium, lead, nickel, zinc and copper by sugarcane (Saccharum officinarum) bagasse;
pr
methylene blue dye by water hyacinth; cadmium ions by Wheat bran are few of several
e-
reports which affirm the biosorbent based adsorption systems to follow monolayer adsorption
Pr

model i.e. Landmuir isotherm (Altin 1998; Tsai and Juang 2000; Kumar 2006; Kumar et al.,

2006a; Kumar et al., 2006b; Nouri et al., 2007; Mane et al., 2007a; Mane et al., 2007b;
al

Kumar and Sivenasan 2007; Kumar et al., 2008a; Kumar et al., 2008b; Lataye et al., 2008;
n

Ghodbane et al., 2008; El-Khaiary et al., 2008; Homagai and Ghimire 2010; Park et al., 2016;
ur

Jain et al., 2016; Wang et al., 2018).

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In specific cases like adsorption of large sized molecules, like dyes, it is not easily in

agreement with the monolayer sorption theory upon which is the basis of Langmuir isotherm

model. This is due to the hindrances that are present between adsorbate and the pores so that

α remains < 1. In such cases the best fit of the adsorption system tends to follow Redlich

Peterson (R-P) isotherm. The adsorption of basic blue 9 dye by activated carbon is

corroborates the aforementioned argument (Jumasiah et al., 2005). Few reports suggest that

the sorption system like sorption of green dye, methylene blue, basic dyes, and basic red 9 by

activated carbon, 2-picoline and brilliant green dye by bagasse fly ash, direct solophenyl

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brown dye by fibrous biomass, safranin by rice husk, brilliant green dye by rice husk ash

despite its fit to Langmuir model follows the R-P isotherm too (Kumar 2006; Kumar et al.,

2006a; Kumar et al., 2006b; Mane et al., 2007a; Mane et al., 2007b; Kumar and Sivenasan

2007; Ncibi 2008; Kumar et al., 2008a; Lataye et al., 2008). This suggests that these systems

can be better understood by R-P isotherm (Wu et al., 2010) provided α value is not equal to

or more than 1 as well as it is more simple and accurate calculation method.

The biosorbents that have heterogeneous surface with exponentially distributed active sites

and their energies tend to fit Freundlich isotherm. Freundlich isotherm is an indicator of

f
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adsorption intensity (n value 1 to 10) and capacity. This model has best application for the

multilayer as well as non-ideal adsorption. The reports on adsorption of fluoride by Alumina

pr
cement granules, lead by chitosan, dyes by fly ash, Cr (III) by Landfill clay, Cd by
e-
montmorillonite, kaolinite, and Ochratoxin A by Yeast biomass having the best fit with
Pr

Freundlich isotherm explains that the parameters of the model can be further construed

shedding insights on surface properties adsorption mechanism, and ion exchange affinity
al

(Altin 1998; Mohan et al., 2002; Ng et al., 2003; Ringot et al., 2007; Ayoob and Gupta 2008).
n
ur

In some cases of multi ion sorption by biosorbent, the systems exhibited agreement with the
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Langmuir-Freundlich sorption isotherm. The qm values calculated for Cu2+, Zn2+, Pb2+, Cd2+,

Co2+ sorption onto carbon nanotube (CNT) sheets using the Langmuir isotherm as well as the

KLF and n value for the same suggest a favourable adsorption of metal ions on the oxidized

CNT sheets (Tofighy and Mohammadi 2011). The biosorption of Cu(II) and Cr(VI) onto

coffee waste also claims to fit the Langmuir-Freundlich isotherm (Kyzas et al., 2012). The

extracellular polymeric substances extracted from Klebsiella sp. J1 reportedly adsorbed Cu2+

and Zn2+ effectively with its higher correlation coefficients fitting to Langmuir–Freundlich

model (Yang et al., 2015). The results of Langmuir-Freundlich sorption isotherm explain that

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one binding site is available for each metal ion, and competitive adsorption between the metal

ions will occur in the binary and multi ion system.

Drawbacks of using of biosorbents at pilot/Industrial scale

Laboratory studies using bioadsorbents have limited applicability. Field and pilot studies are

crucial for understanding the role and impacts of different bioadsorbents in different

conditions. All the bioadsorbents are efficient in lab studies, but there are very few reported

studies and assessment for their feasibility at industrial scale. Laboratory to field technology

f
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transfer of industrial effluent treatment by bioadsorbents are expensive for the treatment of

wastewater with low concentration of heavy metals. Bioadsorbent technology commonly

pr
used in detoxifying heavy metals would face some challenges in this technique as various
e-
adsorption processes are highly competitive and expensive. USA and Canada have
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constructed some commercial scale units and few pilot installations that narrate the

applicability of biosorption as the bais for recovery process. It has also helped to ascertain the
al

limitations of the industrial application of biosorption. There is absence of a reliable supply

n

of waste microbial biomass suitable for biosorption application.

ur

Use of biofilters in adsorption process at industrial level is generally not feasible because
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wastewater from electroplating effluents contains variable concentrations of different toxic

metals with varying pH. Such conditions will not always induce growth and maintenance of

active biofilters. Adsorption process is very much affected by the agitation rate of the

solution. Increased agitation rate leads to increased adsorption capacity. This is because the

agitation process provides additional turbulence in the solution leading to enhanced process

of diffusion with the surface of metal ions. At industrial scale, the process is very rapid and

surface gets saturated within few minutes to hours. So, it not feasible to transfer lab studies

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directly to field studies. Most of the technology in the lab scale is yet to be commercialized,

established and scale up.

In lab studies, with increase in contact period, the amount of adsorbed metal ions also

increases due to abundant vacant active sites available for adsorption. With the increase in

time, availability of these vacant sites is progressively decreased till the saturation, hence less

likely to adsorb actively in the later time. In field experiments, the contact period is very less

(STP and WTP release effluents in millions of tonnes) resulting in the decrease of

contaminants adsorption.

f
oo
Some bioadsorbents has certain disadvantages as metals and other contaminants get

accumulated until saturation, after that they start leaching out the contaminants directly into
pr
the water. Use of biochar on calcareous soils will reduce the rate of nitrification, thereby,
e-
escalating the microbial nitrogen immobilization. Phosphorous availability to the plant is
Pr

further expected to decline due to the formation of complexes between the biochar particles

and essential metal ions.

al

The application of biosorbent systems is dependent upon the cost. The cost of
n

procuring/growing the biomass and the cost of immobilization process influence the overall
ur

economics of the process of biosorption. The cost of ion ion-exchange resins, activated
Jo

carbon and other agents should be considerably higher than the cost of commercialized

biosorbents. Bulk production costs of specifically cultured algae and fungi are in the order of

£2000–£10000/tonne (Wang and Chen, 2009). The immobilization of biomass is simple and

relatively inexpensive, therefore the source of raw biomass terms the final cost of a

biosorbent. The regeneration, kinetics, biosorption performance, etc are the factors that

account for the cost of a biosorption process. Fermentation industry was reluctant or unable

to secure a steady supply of waste microbial biomass as an inexpensive raw material.

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Furthermore, the immobilized biomass distribution, regeneration, recycling and re-use made

the above issues even more complex and more difficult (Tsezos, 2001).

The biosorbent regeneration represents the classic version of increasing the economic

efficiency of biosorption processes; the tendency in recent years is to use the exhausted

biosorbents to develop high-value ecological materials (Bădescu et al. 2018). Many studies

reported that the efficiency of regenerated biosorbents in the biosorption processes decreases

as the number of desorption/biosorption cycles increases, so that their utilization is no longer

economically viable after more than 5–6 repeated use (Cechinel et al. 2018; Tran and Chao,

f
oo
2018). As a result, biosorption processes are beginning to be seen as a method of designing

new ecological materials with well-developed practical application, starting from cheap raw
pr
materials that have already been used in the industrial wastewater treatment. To overcome the
e-
economic issue arising with reduction in sorbent efficiency due to regeneration, further
Pr

studies are required to develop a noble eluent that can be applicable for many biosorbents, to

study the ultimate fate of the pollutant loaded spent biosorbents to recover the pollutants like
al

metal ions and etc. that may be used as a resource (up cycle/down cycle) for manufacturing
n

industries to reduce the waste to zero. Only a few studies are available on the detailed
ur

mechanism of desorption. Therefore, further studies should focus on understanding the

Jo

desorption mechanism such as change of chemical conditions, thermal desorption, stripping,

reduction in pressure and etc. acting during desorption to aid the scientific fraternity in

finding the most competent and diverse desorbing agent (Lata et al. 2015).

Conclusion and future perspectives

Adsorption based remediation is a propitious technology owing to its high selectivity, low

operational costs, high level of efficiency, and a minimal degree of toxic sludge generation. It

is widely applied for the adsorption of toxic industrial effluents, removal of heavy metals,

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fertilizers/pesticides, atmospheric pollutants and nuclear waste. Despite a large number of

laboratory studies performed on the biosorption process, the commercialization has been a

distant horizon due to the redundant publication centred approach. The scientific community

can break the achilles’ heel of commercializing biosoption if it takes into consideration, the

national and international policies and the industry’s requirement while solving several

technical and scientific problems to scale-up the technology aiming at its commercialization.

In few cases like the commercial application of activated carbon makes the adsorption

process expensive, which is overcome by the use of low-cost adsorbents, such as agricultural

f
oo
wastes which helps to sustain the adsorbent based remediation market. Also, solid waste

materials such as rice husks, sugarcane bagasse, orange peels, sawdust, coffee residue, rice
pr
husks, and yeast biomass have been utilized for the eradication of heavy metals, toxic
e-
industrial effluents, fertilizers/pesticides, air pollutants and nuclear wastes. Low cost, high
Pr

adsorption capacity, the presence of various functional groups and a high chance of metal

recovery makes biosorbent a most suitable candidate among adsorbents for the remediation of
al

environmental pollutants. The cost-effective and simple process of making biosorbents has
n

resulted in the establishment of a mature and widespread adoption of biosorption technology.

ur

Biosorption employs a wide spectrum of mechanisms to regulate the concentrations of heavy

Jo

metals, toxic industrial dyes, fertilizers, pesticides, atmospheric pollutants and waste

management in the environment. Large surface area, high pore volume and presence of

ligands and functional groups in the biosorbent make them efficient for the remediation

process. The adsorption potential of bioadsorbents can be enhanced by surface treatment,

oxidization of surface, and functionalization. Efforts are being made to explore new

materials, increase the efficiency of existing bioadsorbents and design hybrid technologies

targeting multicomponent bioadsorption. The use of nanobiocomposites is a new and

effective approach for the removal of toxic pollutant and heavy metals from aqueous solution,

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which has a long way before reaching the on-site application. To conclude, bioadsorbents are

eco-friendly, biodegradable and low-cost adsorbent, which represents smart technology

concept constantly evolving with the rising needs. In future, bioadsorbents are poised to

witness extensive applications at domestic and industrial scale to minimize the menace of

environmental pollution.

Acknowledgments

Authors are profoundly grateful to Mr. Anil, School of Bioengineering and Biosciences,

f
oo
Lovely Professional University, for motivating us throughout this manuscript.

Conflict of interest
pr
e-
The authors declare that they have no conflict of interest.
Pr

Compliance with Ethical Requirements: This article does not contain any studies with
al

animals performed by any of the authors.

n
ur

Author contributions
Jo

SS and VK have contributed equally in exploring literature and writing. JS and SS

conceptualized, and acquired the entire concept and guided the authors for writing this

review. SD, DSD, KS and JS have made the contributions including drafting and data

verification under the leadership of Dr JS (Corresponding author). All authors read and

approved the final manuscript.

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Table 1. Classification, categories and important examples of bioadsorbents

Category of
Nature Examples References
bioadsorbants

Clay Serpentine, pylophyllite,

montmorillonite, saponite
vermiculite,
f
sepiolite,

o
illite, Shichi and Takagi, 2000; Krishna et

al. 2001; Ahmaruzzaman, 2008

Natural Siliceous Glasses, silica beads, alunite, dolomite and perlite

r o Ahmaruzzaman et al. 2008; Crini et

- p
materials

Zeolites r e
Clinoptilolite, natrolite, phillipsite, stilvite
al. 2006; Bastani et al. 2006

Wang et al. 2010, Huang et al. 2010

Chitin and
l P
3,4-dimethoxybenzaldehyde chitosan derivative (Chi/DMB), Arvand et al. 2013; Chen and Wang,

Chitosan
n a
xanthate-modified magnetic cross-linked chitosan (XMCS), 2012; Gandhi et al. 2012; Kyzas and

u r
chitosan beads Bikiaris, 2015; Anastopoulos et al.

Biological
Peat
Jo
Herbaceous peat, moss peat, woody peat and sedimentary peat
2017

Ho et al. 1998; Allen et al. 2004;

Ringqvist et al. 2002; Chen et al.

2001; Fernandes et al. 2010; Chieng

et al. 2015; Gündoğan et al. 2004;

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Ho et al. 2002; Fernandes et al. 2007

Biomass White rot fungi, cyanobacteria or algae Kaushik et al. 2009; Huang et al.

2010

Solid waste coir pith, Bagasse, neem sawdust, date piths, banana pith, Valix et al. 2004; Namasivayam and

(activated
o f
Coniferous pinus bark powder, sago waste, silk cotton hull, corn Kavitha, 2002; Khattri et al 2009;

carbon
r o
cob, sugar beet pulp, maize cob, Guava seed carbon, straw, rice Kadirvelu et al. 2003; Banat et al.

- p
husk, rice hulls, Orange peel activated carbon, fruit stones, 2003; Ahmad et al. 2009; Juang et al.

r e
pinewood, nutshells, sawdust, coconut tree sawdust, bamboo and 2002a; Elizalde-González et al.

P
cassava peel, Waste tyres, garbage, sewage sludge, newspaper 2009; Kannan and Sundaram, 2001;

l
Waste waste

n a Ahmedna et al. 2000; Khaled et al.

u r 2009; Aygün et al. 2003; Tseng et al.

Jo
2003; Malik et al. 2003; Wu et al.

1999; Rajeshwarisivaraj et al. 2001a;

Gupta et al. 2011; Nagano et al.

2000; Zhang et al. 2005; Tan et al.

2008; Okada et al. 2003; Guo et al.

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2003

Agricultural chitosan, bone charcoal, coconut shell, egg shell, rice husk, sea food Namasivayam and Sureshkumar,

waste waste, corn stack, sunflower seed shell, coir pith; rice husk; sugar 2008; Han et al. 2008; Yao et al.

peet pulp orange and banana peels; corn cob 2011; Annadurai et al. 2003; Nethaji

o f et al. 2013

Industrial waste
ro
Coal fly ash, Bagasse fly ash, red mud, metal hydroxide sludge, Wang et al. 2005a; Batabyal et al.

blast furnace slag, fly ash and red mud

-p 1995; Namasivayam and Arasi 1997;

P re Wang et al. 2005b

a l
r n
u
Jo

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Table 2. Comparison of biosorption capacities of microbial biomass for removal of toxic metal from wastewater

Removal percentage/ Adsorbent Dosage pH Temperature

Maximum removal

Biomass source Metal ions capacity References

Aspergillus sp. Cr(VI) 92% 100 mg/l

o f
5.0 35oC Congeevaram et al. 2007

Aspergillus sp. Ni(II) 90% 50 mg/l

ro 5.0 35oC Congeevaram et al. 2007

Aeromonas caviae Cd(II) 155.32 mg/g

-p
5 and 50 mg dm−3 7.0 20 oC Loukidou et al. 2004

Aspergillus niger Cu(II) 70%

P re10-100 mg/l 6.0 33oC

25oC
Mukhopadhyay et al. 2007

Bacillus thuringiensis

Bacillus thuringiensis
Cr(IV)

Ni(II)
24.1%

a
15.7% l 250 mg/l

250 mg/l
2.0

6.0 35oC
Sahin & Ozturk 2005

Ozturk 2007

Baker’s yeast Cd(II)

r n
11.63 mg/l 1.5 g/100ml 6.0 37 oC Yu et al. 2007

u
Jo
Baker’s yeast Pb (II) 45.87 mg/l 1.5 g/100ml 6.0 37 oC Yu et al. 2007

Chrococcus Cr(VI) 21.36 20 mg/l 3-4 26 oC Anjana et al. 2007

Corynebacterium glutamicum Pb(II) 2.74 mmol/l 5 g/L 5 20 oC Choi & Yun 2004

Cyanobacterium Zn(II) 71.42 mg/g 100mg/L 8 37 oC Gaur & Dhankhar 2009

Cystoseira baccata Hg(II) 90 mg/g 0.25 g/100ml 4.5 25 oC Herrero et al. 2005

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Enterobacter sp. Pb(II) 50.9mg/g 0.15–0.25g/100ml 5 25 oC Lu et al. 2006

Enterobacter sp. Cu(II) 32.5 mg/g 0.15–0.25g/100ml 5 25 oC Lu et al. 2006

Enterobacter sp. Cd(II) 46.2 mg/g 0.15–0.25g/100ml 6 25 oC Lu et al. 2006

Fucusceranoides Cd(II) 90mg/g 0.25 g/100ml 4.5 25 oC Herrero et al. 2005

Gelidium sesquipedale Cd(II) 87% 0.2g/100ml

o f
5.3 20 oC Vilar et al. 2006

Micrococcus sp. Cr(VI) 90% 100 mg/L

ro 7 35oC Congeevaram et al. 2007

Micrococcus sp. Ni(II) 55%

e -p
50 mg/L 7 35oC Congeevaram et al. 2007

Mucor hiemalis Cr(VI) 47.4-53.5 mg/g

P r 0.1 g/100ml 2 27 to 50 °C Tewari et al. 2005

N. calicola Cr(VI)

Pb(II)
a l
12.23 %

93.50 mg/g
20 mg/l

0.5 g/L
3-4

5
26 oC

25 oC
Anjana et al. 2007

Gupta & Rastogi 2008c

rn
Nostoc

25 oC
Nostoc Cr(VI)

o
Cd(II) u 22.92 mg/g

88.90 mg/g
1.0 g/L

1.0 g/L
3

5 25 oC
Gupta & Rastogi 2008a

Gupta & Rastogi 2008b

J
Oedogonium hatei

Oedogonium hatei Pb(II) 145.00 mg/g 0.5 g/L 5 25 oC Gupta & Rastogi 2008c

Oedogonium hatei (Raw 1.0 g/L 2 44 oC

treated) Cr(VI) 31 mg/g Gupta & Rastogi 2009

Oedogonium hatei (Acid Cr(VI) 35.2 mg/g 1.0 g/L 2 44 oC Gupta & Rastogi 2009

41
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treated)

S. wightii Ni(II) 71.2% 2 g/L 4 30 oC Vijayaraghavan et al. 2006

Penicillium chrysogenum Cu(II) 92 mg/g 0.1g/100ml 5.5 - Deng & Ting 2005

Penicillium chrysogenum Pb(II) 204 mg/g 0.1g/100ml 5.5 - Deng & Ting 2005

Penicillium chrysogenum Ni(II) 55 mg/g 0.1g/100ml

o f
5.5 - Deng & Ting 2005

1g/1000ml
r o 4.0– 30oC

Penicillium chrysogenum Ni(II) 13.2 mg/g

- p 5.0 Tan and Chen 2003

re 1g/1000ml 4.0– 30oC Tan and Chen 2003

Penicillium chrysogenum Cr(III)

l
18.6 mg/g
P 5.0

n a 1g/1000ml 4.0– 30oC Tan and Chen 2003

Penicillium chrysogenum Zn(II)

u r6.8 mg/g 5.0

Jo
Penicillium oxalicum Pb(II) 47.4 mg/g 300 mg/ L 5.0 20oC Svecova et al. 2006

Phomopsis sp. Cd(II) 26 mg/g 50mg/100ml 6.0 - Saiano et al. 2005

Phomopsis sp. Zn(II) 10.3 mg/g 50mg/100ml 6.0 - Saiano et al. 2005

Pseudomonas fluroscens Cd(II) 66.25 mg/g 5 g/L 5.0 28oC Yu et al. 2011

Pseudomonas putida Cu(II) 89.60 mg/g 25 mg/ 50 mg/L 6.5 25 oC Zheng et al. 2008

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Pseudomonas putida Pb(II) 270.4 mg dm−3 10 cm3/90 cm3 5.5 25 °C Uslu & Tanyol 2006

Pseudomonas putida Cu(II) 96.85 mg dm−3 10 cm3/90 cm3 5.5 30 °C Uslu & Tanyol 2006

Pseudomonas sp. Cd(II) 278.0 mg/g 1g/1000ml 7.0 - Ziagova et al. 2007

Pseudomonas sp. Cr(IV) 95.0 mg/g 1g/1000ml 7.0 - Ziagova et al. 2007

Saccharomyces cerevisiae Cd(II) 0.137 mmol/g 0.1g/50ml

o f - 30 °C Cheng & Wang 2007

Saccharomyces cerevisiae Pb(II) 0.413 mmol/g 0.1g/50ml

ro - 30 °C Cheng & Wang 2007

Saccharomyces cerevisiae Ni(II) 0.108 mmol/g

e -p
0.1g/50ml - 30 °C Cheng & Wang 2007

Saccharomyces cerevisiae Cr(III) 0.247 mmol/g

P r0.1g/50ml - 30 °C Cheng & Wang 2007

Oedogonium hatei (untreated) Ni(II)

Ni(II)
a l
40.9 mg/g

44.2 mg/g
0.7 g/L

0.7 g/L
5.0

5.0
25 °C

25°C
Gupta et al. 2010

Gupta et al. 2010

n
O. hatei (acid-treated)

Sargassum sp. (modified) Pb(II)

u r
1.46 mmol/g 1 g/L 5.0 25°C Chen & Yang 2005

Jo
Sargassum sp. Pb(II) 1.26 mmol/g 100 mg/25ml 5.0 25°C Martins et al. 2006

Sargassum sp. Ni(II) 181.2 mg/g 0.5g/100ml 5.0 30°C Kalyani et al. 2004

Sphigomonas p. Cu(II) 50.1 mg/g 0.5 g/l 5.0 20°C Wang et al. 2010

Spirodela polyrhiza (L.) 0.1/100ml 6.0 20°C

Schleiden biomass Cd(II) 36 mg/g Meitei & Prasad 2013

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Spirodela polyrhiza (L.) 0.1/100ml 4.0 20°C

Schleiden biomass Pb(II) 137 mg/g Meitei & Prasad 2013

Spirogyra Pb(II) 140.00 mg/g 0.05/100ml 5.0 25°C Gupta & Rastogi 2008

Spirogyra Cu(II) 133.30 mg/g 20g/L 5.0 22°C Gupta et al. 2006

Spirogyra Cr(VI) 14.7×103 mg/kg 5mg/l

o f2.0 18°C Gupta et al. 2001

Spirulina Cd(II) 98%

ro 7.5 20°C Solisio et al. 2008

Staphylococcus xylosus Cd(II) 250.0 mg/g

-p
1g/L 6.0 - Ziagova et al. 2007

Staphylococcus xylosus Cr(IV) 143.0 mg/g

P re 1g/L 6.0 - Ziagova et al. 2007

Streptomyces coelicolor Cu(II)

Ni(II)
21.8%

a
7.3%
l 1g/L

1g/L
5.0

8.0
25°C

25°C
Ozturk et al. 2004

Ozturk et al. 2004

n
Streptomyces coelicolor

Streptomyces rimosus Cd(II)

u r31.9 mg/g 3g/L 8.0 - Selatnia et al. 2004

Jo
Thiobacillus ferrodoxins Pb(II) 443.00 mg/g - 5.0 25°C Rodelo et al. 2002

Thiobacillus ferrooxidans Zn(II) 172.4 mg/g - 6.0 40°C Liu et al. 2004

Thiobacillus ferrooxidans Cu(II) 39.84 mg/g - 5.0 40°C Liu et al. 2004

Tolypocladium sp. Hg(II) 161.1 mg/g 300 mg/ L 5.0 20oC Svecova et al. 2006

U. lactuca (dried) Cr(VI) 10.61 mg/g 50mg/L 1.0 25oC El-Sikaily et al. 2007

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 Journal Pre-proof

U. lactuca (Activated carbon 50mg/L 1.0 25oC

developed) Cr(VI) 112.36 mg/g El-Sikaily et al. 2007

Ulva onoi (Non-treated) Cd(II) 61.9 mg/g 1g/L 8.0 - Suzuki et al. 2005

Ulva onoi (Alkali pretreated) Cd(II) 90.7 mg/g 1g/L 8.0 - Suzuki et al. 2005

Ulva onoi (alkali pretreated) Zn(II) 74.6 mg/g 1g/L

o f8.0 - Suzuki et al. 2005

r o
- p
re
l P
n a
u r
Jo

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Table 3. Maximum bioadsorption capacities of plant derived biomasses for removal of toxic metal ions from wastewater

Biomass Biomass Treatment Adsorption

source Metals capacity (mg/g) References

Rice Rice husk

Rice husk
Phosphate treated

Alkali treated
Cd(II)

Cd(II)
o f
2,000.00

125.94
Ajmal et al 2003

Akhtar et al. 2010

Rice husk -
r
Cd(II) o 73.96 Akhtar et al. 2010

- p
Rice husk H3PO4 treated

r e Cd(II) 102.00 Ye et al. 2010

Rice husk

Rice husk
NaOH treated

NaHCO3 treated
l P Cd(II)

Cd(II)
20.24

16.18
Kumar et al. 2006

Kumar et al. 2006

Rice husk
n a
Epichlorohydrin treated Cd(II) 11.12 Kumar et al. 2010

Rice husk
u r
Sulfuric acid treated Cd(II) 40.92 El-Shafey 2007

Rice husk ash

Rice husk
Jo-

Acid treated
Cd(II)

Cu(II)
39.87

29.00
Zulkali et al. 2006

Wong et al. 2003

Rice husk Sulphuric acid treated Se(IV) 41.15 El-Shafey 2007

Rice husk Sulphuric acid treated Hg(II) 384.62 El-Shafey 2010

Rice husk Acid treated Pb(II) 108.00 Wong et al. 2003

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Rice husk ash - Pb(II) 91.74 Naiya et al. 2009

Rice husk ash - Pb(II) 39.74 Quek et al. 1998

Wheat Wheat straw Urea treated Cd(II) 4.25 Farooq et al. 2011

Wheat bran Ultrasonic treatment Cd(II) 51.58 Nouri et al. 2007a

Wheat bran - Cd(II)

o f22.78 Nouri et al. 2007a

Wheat straw - Cd(II)

ro 39.22 Farooq et al. 2011

Wheat straw -

e -p
Cd(II) 21.00 Verma and Shukla 2000

Wheat bran -

P r Cd(II) 21.00 Nouri et al. 2007b

Wheat bran

Wheat straw
-

-
a l Cd(II)

Cd(II)
15.82

14.56
Nouri et al. 2007b

Dang et al. 2009

r n
Wheat straw -
u Cd(II) 11.60 Tan and Xiao 2009

Jo
Wheat straw Chemically modified Cr(VI) 322.58 Chen et al. 2010

Wheat bran Chemically modified Cr(VI) 93.00 Farajzadeh et al. 2004

Wheat bran - Cr(VI) 310.58 Singh et al. 2009

Wheat straw - Cr(VI) 21.34 Wang et al. 2010

Wheat bran Cu(II) 8.34 Basci et al. 2004

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Wheat bran - Cu(II) 6.85 Wang et al. 2009

Wheat straw - Cu(II) 11.43 Dang et al. 2009

Wheat bran - Cu(II) 12.70 Dupont et al. 2005

Wheat bran - Cu(II) 17.42 Aydin et al. 2008

Wheat bran Dehydrated Cu(II)

o f51.50 Ozer et al. 2004

Wheat bran - Pb(II)

ro 87.00 Naiya et al. 2009

Wheat bran Chemically modified

e-p
Pb(II) 62.00 Farajzadeh et al. 2004

Wheat bran -

P r Zn(II) 16.40 Dupont et al. 2005

Wheat bran

Puresorbe
Chemically modified

-
a l Hg(II)

Cd(II)
70.00

285.70
Farajzadeh et al. 2004

Pino et al. 2006

n
Coconut

Coir pith -
u r Cd(II) 93.40 Kadirvelu et al. 2003

Jo
Copra meal - Cd(II) 4.99 Ho and Ofomaja 2006

CSC chitosan+ HNO3 Cr(VI) 10.88 Babel & Kurniawan 2004

CSC chitosan+ H2SO4 Cr(VI) 4.05 Babel & Kurniawan 2004

CSCCC Chitosan Cr(VI) 3.65 Babel & Kurniawan 2004

Coir pith (PGCP-COOH) Hg(II) 13.73 Anirudhan et al. 2008

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Coir pith - Co(II) 12.82 Parab et al. 2006

Coir pith waste - Pb(II) 263.00 Kadirvelu & Namasivayam 2000

Coir pith - Ni(II) 15.95 Parab et al. 2006

Peels Orange peel Chemical modification Cd(II) 136.05 Sha et al. 2009

Mango peel - Pb(II)

o f99.05 Sha et al. 2009

Banana peel - Pb(II)

ro 2.18 Anwar et al. 2010

Orange peel -

e-p
Cd(II) 47.60 Sha et al. 2009

Mango peel -

P r Cd(II) 68.92 Iqbal et al. 2009

Banana peel

Banana peel
-

-
a l Cd(II)

Cd(II)
35.52

5.71
Memon et al. 2008

Anwar et al. 2010

r n
Pomelo peel -
u Cd(II) 21.83 Saikaew et al. 2009

Jo
Potato peel ZnCl2 treatment Cu(II) 74.00 Moreno-Piraján et al., 2011

Orange peel Chemical modification Cu(II) 70.67 Sha et al. 2009

Orange peel - Cu(II) 50.94 Sha et al. 2009

Mango peel - Cu(II) 46.09 Iqbal et al. 2009

Banana peel - Cr(VI) 131.56 Memon et al. 2009

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 Journal Pre-proof

Lemon peel - Co(II) 22.00 Bhatnagar et al. 2010

Mango peel - Zn(II) 28.21 Iqbal et al. 2009

Orange peel - Ni(II) 158.00 Ajmal et al. 2000

Pomegranate peel - Ni(II) 52.00 Bhatnagar et al. 2010

Mango peel - Ni(II)

o f39.75 Iqbal et al. 2009

Seeds Raw date pit - Cd(II)

ro 35.90 Kahraman et al. 2008

Sapotaceae seed Chitosan + Acid

e -p
Cr(VI) 84.31 Kahraman et al. 2008

Sapotaceae seed Chitosan coated

P r Cr(VI) 76.23 Kahraman et al. 2008

Sapotaceae seed

Cicerarientinum
Acid coated

-
a l Cr(VI)

Cu(II)
59.63

18.00
Kahraman et al. 2008

Mohammad et al. 2010

r n
Cicerarientinum -
u Zn(II) 20.00 Mohammad et al. 2010

Jo
Cicerarientinum - Pb(II) 20.00 Mohammad et al. 2010

Shell Chestnut shell Acid treated Pb(II) 8.50 Vázquez et al. 2009

Almond shell - Cr(VI) 3.40 Pehlivan and Altun 2008

Hazelnut shell - Cr(VI) 8.28 Pehlivan and Altun 2008

Walnut shell - Cr(VI) 8.01 Pehlivan and Altun 2008

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 Journal Pre-proof

Chestnut shell - Cu(II) 12.56 Yao et al. 2010

Chestnut shell Acid treated Cu(II) 5.48 Vázquez et al. 2009

Walnut shell ZnCl2 Hg(II) 151.50 Zabihi et al. 2009

Shell carbon H3PO4+chitosan Zn(II) 60.41 Amuda et al. 2003

Shell carbon chitosan mod Zn(II)

o f50.93 Amuda et al. 2003

Chestnut shell Acid treated Zn(II)

ro 2.41 Vázquez et al. 2009

Shell carbon -

e -p
Pb(II) 30.00 Sekhar et al. 2008

Hazelnut shell -

P r Pb(II) 28.18 Pehlivan et al. 2009

Almond shell

Pinus roxburghii bark

-

-
a l Pb(II)

Cd(II)
8.08

3.01
Pehlivan et al. 2009

Padmini & Sridhar 2007

n
Bark

Casuarina equisetifolia -
u r Cu(II) Mohan et al. 2008

Jo
bark 16.58

Rhizophoraapiculata - Cu(II) Oo et al. 2009

tannin 8.78

Pinus roxburghii bark - Cu(II) 3.81 Sarin & Pant 2006

Pinus roxburghii bark - Cr(VI) 4.15 Sarin & Pant 2006

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Moringa oleifera bark - Pb(II) 34.60 Reddy et al. 2010

Rhizophoraapiculata - Pb(II) Oo et al. 2009

tannin 31.32

Pinus roxburghii bark - Ni(II) 3.53 Sarin & Pant 2006

Acacia leucocephala - Ni(II)

o f Subbaiah et al. 2009

bark
ro 294.10

Tea Tea waste -

-p
Cd(II) 11.29 Cay et al. 2004

Tea waste -

P re Ni(II) 73.00 Ahluwalia & Goyal 2005

Tea waste

Tea waste
-

-
a l Cu(II)

Cu(II)
8.64

48.00
Cay et al. 2004

Amarasinghe & William 2007

Spent black tea -

rn Pb(II) 129.90 Zuorro & Lavecchia 2010

u
Jo
Spent green tea - Pb(II) 90.10 Zuorro & Lavecchia 2010

Tea waste - Pb(II) 65.00 Amarasinghe & William 2007

Tea waste - Zn(II) 8.90 Choi and Yun 2004

Hull Peanut hull - Cu(II) 21.25 Zhu et al. 2009

Peanut hull pellet - Cu(II) 12.00 Johnson et al. 2002

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Peanut hull - Cu(II) 9.00 Johnson et al. 2002

Husk Groundnut husk Ag coated Cr(VI) 11.40 Dubey & Gopal 2007

Groundnut husk - Cr(VI) 7.00 Dubey & Gopal 2007

Coffee - Cd(II) Azouaou et al. 2010

waste Raw coffee powder

o f15.65

Coffee Coffee ZnCl2 modified Pb(II)

ro 63.00 Reddy et al. 2010

Fruit Bael fruit -

-p
Cr(VI) 17.27 Anandkumar and Mandal 2009

Sago Sago husk ash -

P re Cu(II) 12.40 Quek et al. 1998

a l
r n
u
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Table 4. Isotherms models for adsorption of different materials on adsorbates

Adsorbent material Adsorbate Isotherms used Best fit Isotherm References

Malachite green Freundlich, Langmuir, Redlich–

Activated carbon Langmuir and Redlich–Peterson Kumar 2006

f
dye Peterson

Activated carbon Methylene blue

Redlich–Peterson, Freundlich,

o o
Langmuir and Redlich–Peterson Kumar et al., 2008a
Langmuir

p r
-
Redlich–Peterson Freundlich,

e
Activated carbon Malachite green
Langmuir

P r Langmuir and Redlich–Peterson Kumar et al., 2006a

Activated carbon Basic dyes l

Redlich–Peterson, Freundlich,

a Langmuir and Redlich–Peterson Kumar et al., 2006b

n
Langmuir

r
u Redlich–Peterson, Freundlich,

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Activated carbon Basic red 9 Langmuir Kumar et al., 2008b
Langmuir,

Dubnin–Radushkevich, Ayoob and Gupta

Alumina cement granules Fluoride
Freundlich, Langmuir Freundlich 2008

Redlich–Peterson, Freundlich, Redlich–Peterson

Activated carbon Basic blue 9 dye Jumasiah et al., 2005
Langmuir

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Langmuir, Freundlich, Redlich–

Bagasse fly ash 2-picoline Peterson, Temkin equilibrium Langmuir and Redlich–Peterson Lataye et al., 2008

equations

Dubnin–Radushkevich,
Bagasse fly ash
Brilliant green dye Freundlich, Langmuir, Redlich–
o f
Langmuir and Redlich–Peterson
Mane et al., 2007a

Peterson, Temkin
r o
Bentonite Strontium Freundlich, Langmuir
- p Langmuir Tsai and Juang 2000

r e
Langmuir, dual Langmuir-
Biochar Hg(II) and Pb(II)

l P
Langmuir and Freundlich
Langmuir Wang et al., 2018

Ca-alginate beads Zinc (II) ions

a
Langmuir- Freundlich

n
Langmuir-Freundlich Lai et al., 2008

Carbon nanotube (CNT) Cu2+, Zn2+, Pb2+,

u r
Langmuir-Freundlich Langmuir-Freundlich
Tofighy and

Jo
sheets Cd2+, Co2+ Mohammadi 2011

Freundlich, Langmuir and

Chitosan Lead Freundlich Ng et al., 2003
Redlich–Peterson

Langmuir, Freundlich and Kyzas et al., 2012

Coffee waste Cu(II) and Cr(VI) Langmuir-Freundlich
Langmuir-Freundlich

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Eucalyptus bark Cadmium ions Freundlich, Langmuir Langmuir Ghodbane et al., 2008

Direct Solophenyl Langmuir, Redlich–Peterson, Ncibi 2008

Fibrous biomass Redlich–Peterson
Brown dye Temkin

Fly ash Dyes Freundlich, Langmuir Freundlich Mohan et al., 2002

2+ 2+
Langmuir and Langmuir–
o f
o
Klebsiella sp. J1 Cu and Zn Langmuir-Freundlich Yang et al., 2015
Freundlich

p r
Landfill clay Cr (III) and Cd(II)
Langmuir and Freundlich

e - Freundlich – Cr (III) Ghorbel-Abid and

isotherms

P r Langmuir – Cd (II) Mailka 2015

Montmorillonite, l
Langmuir–Freundlich, Redlich–

a
Petersen, Toth, Dubinin– Langmuir –Pb

kaolinite
Heavy metals

u rn
Radushkevich and Modified Freundlich –Cd
Altin 1998

J o Dubnin–Radushkevich

Redlich–Peterson, Freundlich,

Rice husk Safranin Langmuir, Dubnin– Kumar and Sivenasan

Langmuir and Redlich–Peterson
Radushkevich, Elovich, Redlich– 2007

Peterson, Temkin

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Dubnin–Radushkevich, Redlich–
Rice husk ash Brilliant green dye
Peterson, Temkin Freundlich, Langmuir and Redlich–Peterson Mane et al., 2007b

Langmuir

Sesame straw biochar Pb, Cd, Cr, Cu ,Zn Freundlich and Langmuir Langmuir Park et al., 2016

Sunflower plant biomass- Ni(II), Cd(II) and

Langmuir, Freundlich
o f
Langmuir Jain et al., 2016
based carbons Cr(VI)
r o
Cadmium, lead,
- p
Sugarcane (Saccharum
nickel, zinc and Langmuir model
r e Langmuir
Homagai and Ghimire

officinarum) bagasse
copper
l P 2010

Wheat bran Cadmium ions

a
Freundlich, Langmuir

n
Langmuir Nouri et al., 2007

u rFreundlich, Langmuir, Brunauer–

Jo
Yeast biomass Ochratoxin A Emmett–Teller, Hill, Redlich– Freundlich Ringot et al., 2007

Peterson, Radke–Prausnitz, Toth

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Table 5. Performance of plant derived bioadsorbents for removal of heavy metals

Heavy Maximum adsorption Adsorbent Dosage pH Temperature

Materials metal capacity /Percentage References

f
ions Removal

Rice husk Cd (II) 125.94 mg/g 0.2g

o 6 30 oC Akhtar et al. 2010

Parthenium 0.5/50mL

p ro 3–4 30 oC

hysterophorous Cd(II) 99.7%

e - Ajmal et al. 2006

Mango peel Cd(II) 68.92 mg/g

P r 2.5g/L 5.0 25 oC Iqbal et al. 2009b

Mango peel Pb(II) 99.05 mg/g

a l 2.5g/L 5.0 25 oC Iqbal et al. 2009b

Bael fruit Cr (VI)

u
17.27 mg/g rn 1 g/100 mL 2.0 - Anandkumar et al.

Hazelnut shell Cr (VI)

J o
28.18 mg/g 0.5g/20mL 6.0 25 oC
2009

Pehlivan et al. 2009

Wheat bran (dehydrated) Cu (II) 51.50 mg/g 0.1/100mL 5.0 20 oC Ozer et al. 2004

Pinus roxburghii bark Cr (VI) 45 mg/g 5g/L 2.0 32oC Sarin et al. 2006

Walnut shell (ZnCl2 mod) Hg (II) 151.50 mg/g 0.05 g/50mL 2.0 29 oC Zabihi et al. 2009

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Almond shell Pb (II) 8.08 mg/g 0.5g/20mL 7.0 25 oC Pehlivan et al. 2009

0.5g/100mL 5.0 30 oC Ahluwalia & Goyal

Tea waste Ni (II) 58%
2005

Coconut husk As(III) 146.30mg/g 0.1g/50mL 12.0 30 oC Manju et al. 1998

Chitosan As(V) 58.00% 1g/L

o f
4.0 - Mcafee et al. 2001

Açaí endocarp Cd2+, 90% for Cd, 98%, for Pb &

ro
8, 20, 12 g of Cd(II),

p
6.0 Cd(II) 25oC Goncalves et al.

Pb2+ and 63% for Cr

-
Pb(II) and Cr(III)

e
5.0 Pb(II) 2018

Cr3+

P r per litre 4.0 Cr(III)

Sesame stalk

a l
Ni(II) and 30.61 ± 0.72 mg/g for Ni 10g/L 6 - Kırbıyık et al. 2012

Zn(II)
n
and 18.88 ± 0.54 mg/g for

r
Zn

o u
Alkaline treated carob

shells
Cd2+ and

Co2+
J
37.79 mg/g for Cd & 25.50

mg/g for Cobalt

1g/L 6 250C Farnane et al. 2017

Chest nut Cd2+ and 34.77 mg/g Cd(II); 2g/L 4 20–25 °C Kim et al. 2015

Pb2+ 74.35 mg/g Pb(II)

Moringa pods Cu, Ni, 90%, 68% and 91% 1g/L - 20–25 °C Matoug et al. 2015

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Cr

Green algae waste Pb, Cd 31.70% for Pb(II), 21.93% 0.2g/25mL 2.0 200C Bulgariu and

biomass and Co for Cd(II) and 11.39% for Bulgariu 2012

Co(II)

Spirogyra hyalina Cd, Hg, 18.181 mg/g for Cd, 35.714 250mg
o f - Room Kumar & Oommen

Pb, As mg/g for Hg, 31.250 mg/g

p ro temperature 2012

and Co for Pb, 4.808 mg/g for As

e -
and 12.821 mg/g for Co

P r
Hemicellulose–chitosan Pb2+,
l
2.90, 0.95, and 1.37 mg/g of

a
∼0.30 g/g 5.0 Room Ayoub et al. 2013

biosorbent Cu2+, and

r n
Pb2+, Cu2+, and Ni2+ ions temperature

Ni2+

o u
Prunus domestica and

Jacaranda mimosifolia
Pb2+
J
47.571 mg/g for Jacaranda

mimosifolia
5.0 30oC Treviño-Cordero et

al. 2013

Date palm fibres Cr(VI) 98.7% 5g 7.0 - Haleem et al. 2018

Tectona grandis biochar Ni2+ and 92.46% for Ni and 91.21% 3 g/L for Ni and 6.0 for Ni 30oC Vilvanathan, and

Co2+ for Co 2g/L for Co and 5.0 for Shanthakumar 2018

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Co

Rose biomass Cr, Hg Adsorption capacity (mg/g) 2g 2.0-7.0 Room Aman et al. 2018

and Zn 8.18 for chromium, 12.53 temperature

for mercury and

1.4 for zinc

o f
Burmese grape leaf Cd 44.73 mg/g 0.1g

p ro 4.0 25 oC Borah et al. 2018

extract

e -
Malva sylvestris biomass Cu (II) 172–202 mg/g (oven dried)

P r 10g/L 5.0 35 oC Ramavandi and

a l
118–133 mg/g for sun-dried Asgari 2018

Orange Peel Cr(VI) 86%

r n 0.5g 2.0 25°C Tejada-Tovar et al.

o u 2018

Tomato waste and apple

juice residue
Pb(II)
J
152 for tomato waste and

108 mg/g and apple juice

0.100 mg/25 mL 4.0 Room

temperature
Heraldy et al. 2018

Groundnut (Arachis Pb(II), - 2g 5.0 28oC Babarinde and

hypogaea) Cd(II) Onyiaocha 2016

and

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Zn(II)

o f
r o
- p
r e
l P
na
u r
J o

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Table 6. Adsorption capacities qm (mg/g) of waste materials derived from raw agricultural by-products in the removal of dyes

Adsorbent Maximum adsorption pH Optimum

Waste Materials Dye References
Dosage capacity qm (mg/g)

o f temperature

Pinewood Acid Blue 264 0.1g 1176 g/kg

r o8.53 - Tseng et al. 2003

Cane pith Basic red 22 0.1g 941.7 g/kg

- p 4.1 30oC Juang et al. 2001

Corncob Acid blue 25 0.1g 1060 g/kg

r e 5.9 30oC Juang et al. 2002

Bagasse Basic red 22 0.1g

l P
942 g/kg 4.1 30oC Juang et al. 2002

Pinewood Basic blue 69 0.1g

a 1119 g/kg 8.53 - Tseng et al. 2003

Rice husk Basic green 4

u
0.8g
rn - 6.59 25oC Guo et al. 2003

Bagasse

Coal
Acid blue 80

Basic blue 9 J o 10mg

-
391 mg/gm

250 mg/g
7.4

-
-

20oC
Valix et al. 2004

McKay et al. 1999

Waste carbon slurries Acid blue 113 0.01g 219 mg/g 7 25oC Jain et al. 2003

Sewage sludge Basic red 46 0.4g 188 mg/g 11 20oC Martin et al. 2003

Mahogany sawdust Acid yellow 36 - 183.8 mg/g - 30oC Malik et al. 2003

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Coal Basic red 2 - 120 mg/g 3 20oC McKay et al. 1999

Sewage sludge Basic blue 9 1g 114.94 mg/g - 25oC Otero et al. 2003

Charcoal Acid red 114 0.05g 101 mg/g - 20oC Choy et al. 1999

Rice husk Acid yellow 36 - 86.9 mg/g 3 30oC Malik et al. 2003

Rice husk Acid blue 10mg 50 mg/g 2

o f 25oC Mohamed et al. 2004

Sugarcane dust Basic green 4 0.25g 20.6mg/g

ro - - Ho et al. 2005

Palm Basic yellow - 327 mg/g

e -p - 25oC Nassar and Magdy, 1997

Treated sawdust Basic green 4 400mg

P r
74.5 6-9 26oC Garg et al. 2003

Metal hydroxide
Reactive red 141
0.100g

a l 98%
2 30oC
Netpradit et al. 2003
sludge

r n
Fly ash Alizarin Sulfonic

ou 1g 7.13mmol/kg 8 - Woolard et al. 2002

Neem sawdust

Phragmites australis
Basic violet 3
J 0.5g

2.0g
3.78 mg/g 7.2

6.0
30oC

30oC
Khattri and Singh, 2000

Basic blue 154.756 mg/g Akar et al. 2018

spongy tissue

Orange solimax 2.8g 1.5 40oC

Malt bagasse 23.2 mg g−1 Fontana et al. 2016
TGL

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Methylene blue 0.25 g 6.5 25 oC

Phragmites australis 22 mg/g Kankılıç et al. 2016
(MB)

Sphagnum peat Malachite green 0.6g 121.95 mg/g 6.5 30oC Hemmati et al. 2016

Acid Blue 113 0.2 to 8 g/L 6 30oC

Cucumis sativus peel
dye
8.21 to 73.60%

o f Lee et al. 2016

Methylene Blue 0.5g/L

189.83 mg/g for
p ro
2 25oC

(MB),

e -
Pear cactus (Opuntia Eriochrome

P r
Methylene Blue, 200.22

mg/g for Eriochrome Barka et al. 2013

ficus indica) Black T (EBT)

a l
Black T and 118.35 mg/g

rn
and Alizarin S
for Alizarin S
(AS)

o u
Porous cellulose-based
J
Blue 93 (AB93)

methylene blue
2.5g
93.7% (AB93) and
9 40oC

Liu et al. 2015

96.5% (MB)
(MB)

Modified sugarcane 0.4 g 6 26oC

Methyl red (MR) - Saad et al. 2010
bagasse

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Acid Orange 7 10 2.5 25oC

and Remazol
Canola stalks (CS) > 90% Hamzeh et al. 2012
Black 5 reactive

dye

methylene blue 0.2g 2-8

o f 20oC

Cupressus (MB) and 0.62 mmol/g for MB and

r o
sempervirens cones rhodamine B
-
0.24 mmol/g for RhB p Fernandez et al. 2010

(RhB)
r e
0.4 g/L for
l P 8 20oC
Basic Blue 41,
a
Basic Blue 41 67.6 mg/g,

rn
BB41, 2 g/L
Basic Red 46 Basic Red 46 49.0 mg/g,
Canola hull
and Basic Violet
o u
for BR46
Basic Violet 16 25.0
Mahmoodi et al. 2010

16 J and 1 g/L

for BV16)
mg/g

Methylene blue 0.5g 7.81 mg/g for methylene 3 to 10 Room temperature

de Oliveira Brito et al.
Brazil nut shells and indigo blue, and 1.09 mg/g for
2010
carmine indigo carmine

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Figure legends:

Figure 1. Processing of different types of biomass resources into industrially relevant biosorption

materials

Figure 2. Scheme of microbial interactions with metal ions present in various organic and

inorganic pollutants under natural and experimental conditions

Figure 3. Diagrammatic presentation of multiple mechanisms involved in adsorption

phenomenon

Figure 4. The proposed mechanism of reduction of azo dyes by bacteria. RMS (root mean

f
oo
square; line), exclusion sphere (range in A°), centroid (average position) drawn with

ChemDraw Ultra ver. 8.0.

pr
Figure 5. Strategies for enhancing the sorption capacities of different adsorbents
e-
Pr
n al
ur
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pr
e-
Pr
al

Figure 1. Processing of different types of biomass resources into industrially relevant

n
ur

biosorption materials
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f
oo
pr
e-
Pr

Figure 2. Scheme of microbial interactions with metal ions present in various organic and
al

inorganic pollutants under natural and experimental conditions

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f
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pr
e-
Pr
al

Figure 3. Diagrammatic presentation of multiple mechanisms involved in adsorption

n

phenomenon
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f
oo
pr
e-
Pr
al

Figure 4. The proposed mechanism of reduction of azo dyes by bacteria. RMS (root mean
n

square; line), exclusion sphere (range in A°), centroid (average position) drawn with
ur

ChemDraw Ultra ver. 8.0.

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Figure 5. Strategies for enhancing the sorption capacities of different adsorbents

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Highlights

 Recent advances in biosorbents and their mechanism

 Strategies to enhance the efficiency of adsorbents

 Adsorbent limitation and dynamics shift

 Limitations in integrating bio-sorbent based technology with existing pilot plants

 Integrating nano-adsorbents with biosorbent carriers and various isotherms

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