overview of modified and non- modified biomass to remove...

Overview of modified and non-

modified biomass to remove

toxic metals from polluted waters

Mehmet Yaman Firat University, Sciences Fac. Chem. Dep.

Elazig-Turkey

[email protected]

SWBDCWECWP 20-23 Feb. 2017 Sindh-Pakistan 1

Prof.

Yaman

Editor-in-Chief: Inter. J. Pure and

Appl. Chem

Member of consultative

committee of TÜBİTAK (the Scientific and Social

Research Council of Turkey).

Between 2010-2013.

Supervised: 11 PhD:

9 complet, 2 cont.

22 M.Sc. 20 complet,

2 cont.

Int. Book Chapter:

Air Pollution-

Monitoring,

Modelling, Health

and Control,2012

110 articles in SCI,

more than 1900 cita.

4

Collaboration partners (14 Universities)

• Univ. of Canakkale 18 Mart, Science Fac. (Prof. Yusuf Dilgin)

• University of Kirklareli, Science Fac. (Dr. Cemile Ozcan)

• University of Kilis, Science Fac. (Assoc. Prof. Halim Avci)

• University of Bozok, Science Fac. (Assoc. Prof. Ismail Akdeniz)

• Univ. of Firat, Medicine Fac. (Prof. Mehmet Simsek)

• Univ. of Firat, Health Science. Fac. Assoc Prof. Gokce Kaya)

• Univ. of Firat. Engineer. Fac. (Prof. Ahmet Sasmaz, Halil Hasar, and others)

• Univ. of Tunceli, Chem. Engineering Fac. (Dr. Nagihan Karaaslan,

Muharrem Ince and Olcay Kaplan)

• Univ. of Yildiz Technic, Science Fac. (Assoc. Prof. Sezgin Bakirdere)

• Univ. of Istanbul Technical, Science Fac. (Prof. Dr. Filiz Senkal)

• Univ. of Bingol, Agricultural Fac. Prof. Mehmet Aycicek

• Univ. Of Gaziantep, Medicine Fac. Assoc. Prof. Nese Kizilkan)

• Univ. of Mardin Dep. Chem. Assoc. Prof. Ersin Kilinc

• Univ. Of Karaman, Science Fac. Prof. Dr. Fevzi Kilicel

5

• Outline of the presentation In this lecture,

• An overview of analytical and environmental

applications of biosorbents will be presented, by

focusing on the mechanisms involved.

- Among types of biomaterial species, it will be

focused on modified and non-modified

agricultural wastes to be considered in removing

of toxic metals from waste waters.

- The major points to consider in this study are

removing of toxic metals such as lead, cadmium,

and nickel from waste water and metal recovery

interests.


Problem ? and solution -To solve the water pollution problem by toxic metal

resulting from anthropogenic and industrial activities

has for long time a most important popularity.

-Biosorption can be a part of the solution.

-Some types of biosorbents such as seaweeds, molds,

yeasts, bacteria or crab shells have been more studied

examples of biomass for metal biosorption with very

encouraging results.

-New biosorbents can be developed for better

efficiency (up to 50% of the biomass dry weight) and

multiple re-use to increase their economic

attractiveness.


Tendency • A large amount of researches on metal biosorption

have been published to elucidate the principles of

the effective metal-concentration phenomenon

during the past 30 years.

• Thousands of publications show that materials of

biological origin including biosorbents can be

considered as effective material to remove different

substances.

• Hovever, there have been few investigations on

determining the compatibility of the biosorbent for

real industrial effluents.

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(biosorption or biosorbent or

biosorbents) AND TOPIC: (removing or

remove or bioremediation or purification or

purifying or cleaning)

What is biosorption ? • Biosorption is the process of sorption of a dissolved

substance using a biomaterial/biomass.

• In other words, biosorption is a physical-chemical process,

simply defined as the removal of substances from solution by

biological material.

• Among biomaterials including microorganisms (such as

bacteria, fungi, yeast, algae) and plants, use of hyper-

accumulator plants opens a new branch of bioremediation for

polluted water as well as preconcentration in trace element

determinations.

This is an ecofriendly and scientific approach to remove, extract

and/or determine metal ions.

-This technique has also a strong potential for recovery of

precious metals as well as removal of toxic metals from

waters.

13

Why Biosorption? The use of biosorbents is one of the alternative

options, when traditional wastewater treatment

methods, such as biological treatment or chemical

precipitation, cannot be used because of:

-the high costs;

-low removal efficiency;

-large amount of chemicals used or sludge produced.

In other words, biosorption offers the advantages of

low cost and good efficiency and thus is a recently

raising and attractive technology.


Sources of biomass

• Biomass can come from

• (i) Agricultural and industrial wastes which should

be obtained free of charge;

• (ii) organisms easily available in large amounts in

nature; and

• (iii) organisms of quick growth, especially cultivated

or propagated for biosorption purposes.

15

SWBDCWECWP 20-23 Feb. 2017 Sindh-Pakistan

16

The main advantages and disadvantages of methods for

treatment of heavy metal in wastewater.

19

Why metal should be removed There are at least three major points to consider,

when choosing the metal for biosorption studies:

metal toxicity (Direct health threat)

metal costs (Recovery interests)

Scientific studies (how representative the metal may be in

terms of its behavior)

20

Factors influencing sorption performance

• The factors that influence the biosorption process

can be classified as:

• 1.Physical and chemical properties of metal ions

(e.g., molecular weight, ionic radius, oxidation state)

• 2.Properties of the biosorbent (e.g., the structure of

the biomass surface)

• 3.The experimental conditions (e.g., pH,

temperature, concentration of biosorbent, the

concentration of sorbate, contact time, etc.)

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- Basic of Biosorption

• Metals can be removed from solution only when

they are appropriately immobilized.

- In most of the applications, the element species

interact with functional groups including amine,

amide, carboxylate, hydroxyl, imidazol, phosphate,

thioethers, and thiols on the material surface.

- Based on the understanding of metal uptake

mechanism, engineered technologies including the

cell surface display technology, have been used to

improve the performance of biomass in metal

removal from aqueous solution.


Selectivity and maximum sorption capacity can be

achieved by suitable adjustment of the expr. conditions

such as pH, the contact time, ionic strength, particle

size, temperature, and concomitant species and

concentrations.

The functional groups present in biomass molecules

acetamido, carbonyl, phenolic, structural

polysaccharides, amido, amino, sulphydryl carboxyl

groups alcohols and esters.

25

26

These groups have the affinity for metal complexation

These groups have the affinity for metal

complexation. Some biosorbents are non-selective

and bind to a wide range of metals with no specific

priority, whereas others are specific for certain types

of metals depending upon their chemical

composition.

In order to understand how metals bind to the

biomass, it is essential to identify the functional

groups responsible for metal binding.

27

Some Ligands used for preconcentration of metals

29

Amino and amidoxime groups

• Amino (-NH2) groups have a lone pair of

electrons on the nitrogen and may form a

covalent bond with a metal.

• The amidoxime group is a bidentate

ligand and has both an acidic group which

loses a proton and a basic lone pair of

electrons on the nitrogen which can

coordinate with the metal ion (Liu et al., 2002; Lutfor

et al., 2000).

31

Imidazole group

• Imidazole has also been used as a

binding agent on a glycidyl methacrylate grafted

cellulose adsorbent (O’Connell et al. 2006a,b,c).

• The imidazole is a five-membered ring

molecule containing two nitrogen atoms. The

imidazole group has the ability to impart

rigidity to the ligand system, due to its

aromatic ring system.

32

• Agricult-materials are usually composed of lignin

and cellulose as major constituents and may also

include other polar functional groups of lignin, which

includes alcohols, aldehydes, ketones, carboxylic,

phenolic and ether groups [21].

• These groups have also the ability to bind some

metals by donation of an electron pair from those

groups to form complexes with the metal ions [11].

• In conclusion, metal biosorption is a rather

complex process affected by several factors.

33

Biosorption Mechanism

• Mechanisms involved in the biosorption process

include chemisorption, complexation, adsorption–

complexation on surface and pores, ion exchange,

microprecipitation, heavy metal hydroxide

condensation onto the biosurface, and surface

adsorption [155–157].

34

• Most of the functional groups involved in the binding

process are found in cell walls.

• Plant cell walls are generally considered as

structures built by cellulose molecules, organized in

microfibrils and surrounded by hemicellulosic

materials (xylans, mannans, glucomannans,

galactans, arabogalactans), lignin and pectin along

with small amounts of protein [68,158,159].

• The behavior of cellulose as a substrate is highly

dependent upon the crystallinity, specific surface

area, and degree of polymerization of the fibers

being studied [160]

Mechanisms controlling metal biosorption

37

There is a relatively strong interaction between neighbouring

cellulose molecules in dry fibres due to the presence of the

hydroxyl (–OH) groups, which stick out from the chain and form

intermolecular hydrogen bonds. Regenerated fibres from

cellulose contain 250–500 repeating units per chain. This

molecular structure gives cellulose hydrophilicity, chirality and

degradability. Chemical reactivity is largely a function of the high

donor reactivity of the OH groups (Klemm et al., 2005).

38

39

There are one primary hydroxyl group and two

secondary hydroxyl groups in the cellulose chain.

Functional groups may be attached to these hydroxyl

groups through a variety of chemistries.

The principle and main routes of direct cellulose

modification (with the introduction of chelating or metal

binding functionalities) in the preparation of adsorbent

materials are esterification, etherification, halogenation

and oxidation.

Alternative approaches have focused on grafting of

selected monomers to the cellulose backbone

either directly introducing metal binding capability or

with subsequent functionalisation of these grafted

polymer chains with known chelating moieties.

Untreated wastes

• Most of the adsorption studies have been focused on

untreated plant/agricultural wastes such as

• papaya wood (Saeed et al., 2005),

• maize leaf (Babarinde et al., 2006),

• teak leaf powder (King et al., 2006),

• lalang and rubber leaf powder (Hanafiah et al., 2007 and 2006b,c ),

• Coriander (Karunasagar et al., 2005),

• peanut hull pellets (Johnson et al., 2002),

• sago waste (Quek et al., 1998),

• saltbush leaves (Sawalha et al., 2007a,b),

• tree fern (Ho and Wang, 2004; Ho et al., 2004; Ho, 2003),

• rice husk ash and neem bark (Bhattacharya et al., 2006),

grape stalk wastes (Villaescusa et al., 2004), etc. 44

Solution or sample digest (about 100 mL)

Adjust pH

Addition of buffer and read just pH

Addition of biomass

Stirring

Filtration and drying

Elution (desorption)

Measurement

Typic scheme of adsorption by untreated wastes

Modification of biosorbents

• Biosorbents can be modified in order to reduce

several deficiencies, which are:

• -Low sorption capacity

• -Poor chemical stability

• -Low mechanical strength

• -Tendency of biosorbent particles to expand or shrink

• It should be noted that the modification reagents

or equipment used leads to additional costs.

However, it should be strongly emphasized that

the costs of modification are never mentioned in

research papers, as well as cost evaluation in

general. 47

Modification of biomass

• Particular functional groups on the biosorbent

surface can be substituted through different

chemical pretreatment methods.

• The introduction of new binding sites to the

biosorbent surface can enhance the sorption

capacity.

50

Esterification

• The citric acid (CA) modification on the wood involved an

esterification reaction process of the carboxyl groups in

citric acid and the hydroxyl groups on the wood surface.

• Chemical treatment with CA at high temperature

produced condensation product and CA anhydride.

• The reactive CA anhydride can react with cellulosic

hydroxyl groups to form an ester linkage and

introduce carboxyl groups to the cellulose (Marshall et al., 1999).

• The esterification process increases the carboxylic acid

content of the wood surface and leads to an increase in

the sorption of metal cations (101.16 mg Cd g1 by

treated, and 48.33 mg Cd g1 by untreated orange

waste). 52

Etherification

• In order to add cyano groups to the cellulose

structure, sawdust was modified chemically

with amidoxime groups by reacting

acrylonitrile with the sawdust, through an

etherification reaction (Saliba et al. (2005).

• These cyano groups were then amidoximated

by reaction with hydroxylamine.

• This amidoximated sawdust had a high

adsorption capacity of 246 mg g1 for Cu(II)

and of 188 mg g1 for Ni(II).

54

The biosorption commercialization

• Although some commercial biosorbents

(Vitrokele 573 for Hg, The biosorbent BIO-FIX

for Al3+>Cd2+>Zn2+>Mn2+,) were reported,

biosorption has not been commercially

successful and its traditional direction as a low-

cost and environmentally-friendly pollutant

treatment method should be re-considered.

• Attempts to improve biosorption (capacity,

selectivity, kinetics, re-use) by physicochemical

and biotic manipulations increase cost and may

raise environmental issues. 64

• Pretreatment of plant wastes can extract soluble

organic compounds and enhance chelating

efficiency (Gaballah et al., 1997).

• For this purpose, different kinds of modifying agents that

are commonly used;

• Base solutions (sodium hydroxide, calcium hydroxide,

sodium carbonate),

• Mineral and organic acid solutions (hydrochloric acid,

nitric acid, sulfuric acid, tartaric acid, citric acid,

thioglycollic acid), organic compounds (ethylenediamine,

formaldehyde, epichlorohydrin, methanol),

• Oxidizing agent (hydrogen peroxide), etc. for increasing

efficiency of metal adsorption have been performed (Dewayanto, 2010).

65

Biosorbent selection and assessment

• The selection of a proper sorbent for a given

separation is a complex problem.

• How to select the suitable biosorbent among a

large quantity of biomass tested?

• The predominant scientific basis for sorbent

selection is the equilibrium time.

• Diffusion rate is generally secondary in importance.

From the viewpoint of practical application, availability

and economy is a major factor to be taken into account

for selecting the biomass for clean-up purposes

66

OPAA was prepared from hydrolysis of the grafted copolymer, which was

synthesized by interacting methyl acrylate with crosslinking orange peel. 71

Removing Interfering Sorption Sites

The natural biomass of biosorbents has many surface

functional groups, some of which could interfere with

the sorption of target metal species.

For instance, -N-H groups have a role as sorption

sites for anionic metal removal by electrostatic

interaction, whereas negatively charged -COOH

groups could repel anionic metals.

Thus, elimination of interfering binding sites from the

biomass surface could result in more efficient

biosorbents (Vijayaraghavan and Yun, 2008).

72

The manipulation of interfering sites has been

reported previously as the

(1)methylation of –N-H groups,

(2) acetylation of –N-H and -OH groups,

(3) esterification of -COOH groups, and

(4) esterification of phosphonate groups.

Gong et al. (2005) removed -COOH groups from

peanut hulls by methylation of the –N-H group,

esterification of the -COOH group, and acetylation of

the –N-H and -OH groups. Therefore, the addition of

positively charged –N-H groups and elimination of

-COOH groups is a highly attractive strategy for

developing more effective biosorbents to recover

negatively charged Precious Ms and positively

charged heavy metals in water and wastewater. 73

Coating With Ionic Polymers Coating the biosorbents and biochars with ionic

polymers could be an efficient way to enhance the

recovery of PMs ions (Fig. 7.3C). For example, the

combination of an ethanolamine molecule with the

biomass can create amine sites on the material

surface.

In addition, the association of polyethyleneimine (PEI)

with the biosorbent and biochar biomass can result in

the generation of a large number of amine groups. PEI

is made of several primary and secondary –N-H

groups and can lead to a significant increase in

sorption capacity for negatively charged PM ions (Mao

et al., 2011). 74

In contrast to methylation pretreatment, in which

residual methanol needs to be removed after

biosorbent and biochar preparation, PEI-coated

biosorbents and biochars can provide a low-cost and

more environmentally friendly solution for metal

removal and recovery.

Yu et al. (2007) synthesized poly(amic acid)-grafted

baker’s yeaste derived biomass by reacting with

pyromellitic dianhydride and thiourea. The authors

reported 15- and 11-fold increases in Cd and Pb

removal, respectively.

75

The OP collected from a local plantation field was cut into

small pieces, washed several times with distilled water and

dried at 80 ◦C. The product was crushed and sieved to obtain

a particle size lower than 0.45 mm. 5.0 g of OP was mixed

together with 25 mL of saturated calcium hydroxide and 25

mL of 0.1 mol L−1 NaOH solutions for 20 h and occasionally

stirred. After filtered, the residue was rinsed several times with

distilled water and thereafter cross-linked with

epichlorohydrin. The obtained sample is abbreviated as COP.

Preparation OPAA

77

COP was added to 100 mL of HNO3 solution (2.5×10-2 mol L-

1) in a three-necked flask, then stirred and purged by passing

nitrogen for 30 min. Ceric ammonium nitrate (5.0×10−3 mol L-

1) was then added in the reaction mixture and allowed to

interact with substrate. After 30 min, 15 mL of methyl acrylate

was added to the reaction flask to start polymerization.

Polymerization was allowed to proceed for 60 min in N2

atmosphere and the reaction was stopped by the addition of 2

mL of 5% (w/v) quinone solution.

Preparation OPAA

78

The polymerization product was filtered, washed several times

with distilled water, and dried in an oven at 60 ◦C to constant

weight.

Finally, removal of the homopolymer from the grafted samples

was carried out with a Soxhlet extractor, using acetone as a

solvent, for 24 h.

The grafted product was then dried in an oven at 60 ◦C for 12

h, hereafter this obtained sample is abbreviated as OPMA.

The grafted copolymer (OPMA) together with 300 mL of 0.5

mol L−1 sodium hydroxide solution was put in a three-necked

flask and the mixture was stirred under reflux at 60 ◦C for 10 h.

Preparation OPAA

79

After cooling dawn to room temperature, the pH of the

reaction mixture was adjusted to ∼6.5 by adding

hydrochloric acid. The residue was filtered off and washed

with ethanol. It was then dried in vacuum, hereafter this

obtained sample is abbreviated as OPAA. The product was

crushed and sieved to obtain a particle size lower than 0.45

mm and used in this study.

Preparation OPAA

80

Effect of pH

• Variation in pH can affect the surface charge of

the adsorbent and the degree of ionisation and

speciation of the metal adsorbate. At very low

solution pH, the binding sites on the modified

cellulose materials are likely to be protonated

resulting in poor metal binding levels.

• An optimum pH range usually between pH 4.0

and pH 6.0 leaves the binding sites unprotonated

and metal binding is maximised.

• At pH’s above this optimum range, most metals

tend to precipitate out of solution in the hydroxide

form. 93

Solution or sample digest (about 100 mL)

Adjust pH

Addition of buffer and read just pH

Addition of biomass Stirring

Filtration and drying

Elution (desorption)

Measurement

122

123

Optimum conditions;

pH= 4,0±0.2,

Elution volume=2,5 mL,

Stirring time=30 min,

Recovery= 91%.

0

300

600

900

1200

1500

1800

2100

0 1 2 3 4 5 6 7

Pb

c

on

c. p

pb

pH

Willow-Pb-pH Biomass Pb conc.(ppb)

(filtrate Pb conc. (ppb)

124

In CONCLUSION The performance of biosorbents could be

enhanced through different surface

pretreatment methods, and among them,

coating with ionic polymers appears to be the

most effective pretreatment method.

However, there is a lack of understanding

about how chemical surface pretreatment

coupled with polymer coating can further

increase the metal sorption capacity for

maximum recovery. 129

Evaluation of Sorption performance

• The optimum pH should be about 7 when a

biomass will be used to remove toxic

elements from vast amount of municipial

waste water, because it is not practice the

use of chemicals for adjustment of pH of a

such large sample.

• Economic analyses are required to

obtain the overall cost of the sorbent and

biosorption process

131

Future directions

• One efficient way to introduce

functional groups on the biomass

surface is the grafting of long polymer

chains onto the biomass surface via

direct grafting, or the polymerization

of the monomer [20].

• Cooperation between scientists would

be advisable, as multidisciplinary

skills are needed

133

References 1- Khairia M. Al-Qahtani, Journal of Taibah University for Science 10

(2016) 700–708.

2- O’Connell et al. Biores Technol 99 (2008) 6709–6724

3-Sud D et al. Bioresource Technology 99 (2008) 6017–6027.

4- Abdel-Ghani N et al. Int J Latest Res Sci Technol, 3(1), 24-42, 2014.

5- Feng N. et al. J Hazardous Materials 185 (2011) 49–54.

6- Niazi NK et al. Environmental Materials and Waste.

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

7-Mahajan G, Sud D. Pol. J. Chem. Tech., Vol. 16(4), 6-13, 2014.

8- Memon JR et al. Colloids and Surfaces B: Biointerfaces 70 (2009)

232–237.

9- Ngah WSW et al., Bioresource Technology 99 (2008) 3935–3948.

10- Malik, DS et al Appl Water Sci Published online 04 april 2016


http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

http://dx.doi.org/10.1016/B978-0-12-803837-6.00007-X

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