introduction -...

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INTRODUCTION

In the process of human evolution, some of the key issues confronting today’s society are safe

guarding the natural environment and maintaining a good quality of life. However, a slight imbalance

in any equilibrium in the environment is bound to manifest itself in the form of pollution. Toxic

metals/metalloids are the important member of dirty dozen clubs of pollutants. The scale of the

problem is illustrated by the frequently used term “Mass Poisoning”.Despite strict environmental

rules and regulations for wastewater management, particularly in developing countries, industrial

effluents released into water streams contain heavy metals. Deterioration of water quality due to

presence of toxic heavy metals in environmental water resources introduced by industrial pollution is

a serious matter of concern today.

Long-term intake of drinking water with elevated arsenic concentrations can cause the expansion of

Arsenicosis, the collective term for diseases caused by chronic exposure to arsenic(Hamadani et al.

2010). Arsenic toxicity causes skin lesions, damage mucous membranes, nervous system,

cardiovascular, genotoxic, mutagenic and carcinogenic effects(Tofail et al. 2009, Bose et al. 2011).

The major arsenic species found in environmental samples are arsenite As (III), arsenate As (V),

arsenious acids (H3AsO3), arsenic acids (H3AsO4), dimethylarsinate, monomethylarsonate,

arsenobetaine and arsenocholine. Among the arsenic compounds, arsenite (III) is 10 times more toxic

than arsenate (V) and 70 times more toxic than methylated species(O’Day et al. 2005).

The commonly used procedures for removing toxic metal/metalloid from aqueous streams include

Oxidation, Ion exchange, Reverse osmosis,NanofiltrationandAdsorption.These currently

practiced technologies for removal of pollutants from industrial effluents appear to be inadequate,

creating often-secondary problems with metal bearing sludge, which are extremely difficult to dispose

off. These conservative methods used for abatement of toxic metal/metalloid are as well often limited

because of technical, economical and environmental constraints(Johnston et al. 2001, Malik et al.

2009).

To combine technology with environmental safety is one of the key challenges of the new

millennium(Hoque at al. 2006). Biosorption is one of the phenomenon’s, which is based on one of the

twelve principles of green chemistry using renewable resources from biomaterials under the domain

of Green Technologies andcan be defined as the ability of biological materials to accumulate heavy

metals from wastewater through metabolically mediated or physico-chemical pathways of uptake

(Ahalya et al. 2003).Bioremediation involves processes that reduce overall treatment cost through

the application of biomaterial which are particularly attractive as they lessen reliance on expensive

water treatment chemicals, negligible transportation requirements and offer genuine, local resources

as appropriate solutions to tackle local issues of water quality problems(Katsoyiannis et al. 2004).

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In recent years, it is realized that biomaterials have been found to be associated with less sorption

efficacy and stability, restricting their commercial use. Research interest has been focused on

increasingthe sorption capacity of the biomaterials through physical and chemical methods.

Consequently, the major challenge for the biosorption processes was to select the most promising

types of biomaterial from an extremely large pool of readily available and inexperience

biomaterials.

The development of nanotechnologies is nowadays on the “crest of the wave” and has valuable

contribution in science and technology which can make global dimensions for social and economic

benefit .Latest progress is in the development of Green nanotechnology for solving many of the

current problems involving water quality. Nanoparticles exhibit good adsorption efficiency especially

due to higher surface area and greater active sites for interaction with metallic species.

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PRESENT STATE OF KNOWLEDGE IN THE AREA OF RELEVANCE

A vigorous survey of the literature on the topic at International and National level has been

conducted and presented in a concise manner.

Biosorption; An emerging trend:Bioremediation becomes a promising process to remediate the

environmental pollutants(Vasudevan et al. 2001). It has many advantages like environmental

friendly, good performance, possible recyclingandlow cost for remediation of toxic

metals/metalloids. A range of plant biomaterials have been reported for efficient remediation of

arsenic from water bodies.

Plant Biomaterial used so far for remediation of Arsenic

Portulacaoleracea As (III) Vankar&Tiwari, 2002

Water lettuce As (V) Basu et al. 2003

Orange waste As (III) & As (V) Ghimre et al. 2003

Cupresus Female Cone As (III) Murugan&Subramaniam, 2004

Garcinia cambogia As (III) Kamala et al. 2005

Unmodified and modified sawdust As(V) & Hg(II) Igwe et al. 2005

Cellulose Loaded Iron Oxyhydroxide As (III) & As (V) Guo et al. 2005

Methylated yeast biomass Arsenic Seki et al. 2005

Sorghum biomass As (V) Haque et al. 2005

Chitosan As(III) Kartal& Imamura, 2005

Coconut fiber As (V) Igwe&Abia, 2006

Powdered chitosan Arsenic Chen & Chung, 2006

Rice husk As (III) & As (V) Amin et al. 2006

Bio-char Arsenic Mohan et al. 2006

Jute leaf, sugarcane powder As (V) Islam et al. 2007

Bone char As (V) Chen et al. 2008

Banana peel As (V) Memon et al. 2008

Piceaabies As (V) Urik et al. 2009

Withaniafrutescens As (III) Chiban et al. 2009

Pterisvittata As (III) & As (V) Wang et al. 2011

Seaweed As (III) & As (V) Llorente-Mirandes et al. 2011

Water hyacinth As (III) & As (V) Mahamadi, 2011

Tea Waste As (III) Shaikh et al. 2011

Carpobrotusedulis As (III) & As (V) Chiban et al. 2011

Farm Rice Total As Rezaitabar et al. 2012

Palm bark biomass As (III) Kamsonlian et al. 2012

Cellulose; An important cost effective biosorbent:As the most important skeletal

components(Park et al. 2010, Teixeira et al. 2010) in plants, the polysaccharide cellulose is an almost

inexhaustible polymeric raw material with fascinating structure and properties (Abdel-Halim et al.

2012, Coseria et al. 2012). It is formed by repeated connection of D-glucose building blocks (Ping and

You-Lo, 2010). It is highly functionalized(Kim et al. 2007, Lee et al. 2011, Pahimanolis et al.

2011),linear stiff- chain homo polymer is characterized by its hydrophilicity, chirality,

biodegradability, broad chemical modifying capacity

et al. 2011) of versatile semi crystalline fibers morphologies due to sensitivity toward the hydrolysis

and oxidation of the chain forming acetal gro

friendly and biocompatibility (Peng et al.

donor reactivity of the OH groups

cellulose from various origins can fall in the range 1000 to 30,000, which corres

lengths from 500 to 15000nm (Ioelovich, 2012).

Nano cellulose; Natural green resource:

especially cellulose and lignocelluloses, will undoubtedly play a large role in the nanotechnology

research effort(Dongping et al.

resource. A polymer composed of cellulose nanofibres (1

2012), whose functional properties are determined by the fibril structure is called Nanocellulose

(Zimmermann et al. 2010, Antczak et al. 2012)

may lead to the designing of novel biomaterial with enhanced sorption efficiency and stability

et al. 2010, Hashaikeh et al. 2011

The exhausted survey of the literature indicates:

� Special emphasis is required to

stability of biosorbentsmaking them viable for commercial use.

� Abatement of arsenic has been largely attempted using inorganic coagulants. Not

much attention has been paid on decontamination of arsenic using or

biomaterials.

� For the abatement of arsenic species advancements have been made on to

inorganic nano materials

raised recently.

� Organic nanoparticles can easily be functionalized with various

to increase their affinity towards target species. The complexity of organic

materials represents the achievement of structural order over many length

scaleswith the full structure developed from the nested levels of structural

hierarchy, in which self

chain homo polymer is characterized by its hydrophilicity, chirality,

biodegradability, broad chemical modifying capacity(Gilberto et al. 2010). Its formation

of versatile semi crystalline fibers morphologies due to sensitivity toward the hydrolysis

and oxidation of the chain forming acetal groups, determine its chemistry, handling, environmental

(Peng et al. 2011). Chemical reactivity is largely a function of the high

donor reactivity of the OH groups (Klemm et al. 2005). The Degree of polymerization of native

cellulose from various origins can fall in the range 1000 to 30,000, which corres

(Ioelovich, 2012).

atural green resource: Nanomaterials derived from renewable biomaterials,


2007, Donia et al. 2012). Nanocellulose is a kind of natural green

A polymer composed of cellulose nanofibres (1-100nm)(Lu et al. 2010, Korotkov et al.

, whose functional properties are determined by the fibril structure is called Nanocellulose

Antczak et al. 2012). Strengthening of functional groups in the biomaterial

may lead to the designing of novel biomaterial with enhanced sorption efficiency and stability

, Hashaikeh et al. 2011).

The exhausted survey of the literature indicates:

Special emphasis is required to enhance sorption efficiency and environmental

stability of biosorbentsmaking them viable for commercial use.

Abatement of arsenic has been largely attempted using inorganic coagulants. Not

much attention has been paid on decontamination of arsenic using or

For the abatement of arsenic species advancements have been made on to

inorganic nano materials. Toxicity issues of such compounds in health have been

Organic nanoparticles can easily be functionalized with various




n which self-assembled organic materials can form templates.

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chain homo polymer is characterized by its hydrophilicity, chirality,

. Its formation(Sadeghifar

of versatile semi crystalline fibers morphologies due to sensitivity toward the hydrolysis

handling, environmental

. Chemical reactivity is largely a function of the high

. The Degree of polymerization of native

cellulose from various origins can fall in the range 1000 to 30,000, which corresponds to chain

Nanomaterials derived from renewable biomaterials,


Nanocellulose is a kind of natural green

Lu et al. 2010, Korotkov et al.

, whose functional properties are determined by the fibril structure is called Nanocellulose

ional groups in the biomaterial

may lead to the designing of novel biomaterial with enhanced sorption efficiency and stability(Habibi

enhance sorption efficiency and environmental

Abatement of arsenic has been largely attempted using inorganic coagulants. Not

much attention has been paid on decontamination of arsenic using organic

For the abatement of arsenic species advancements have been made on to

oxicity issues of such compounds in health have been

Organic nanoparticles can easily be functionalized with various chemical groups




assembled organic materials can form templates.

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� Cellulose is most abundant and low cost renewable polymer resource for the

sorption of cationic species and need modifications for the sorption of anionic

species (Dieter et al. 2005).

� No attention has been paid on the physico-chemical interaction of arsenic and

cellulose which is strongly required for explaining the mechanistic aspects of

different species of arsenic sorption.

Functionalization on Cellulose/ Nanocellulose

Type of modification Modification agent/approach References

Grafting of PEG-NH2 of Nano cellulose Reaction of PEG-NH2 Araki et al. 2001

Grafting on Cellulose Acrylic Polymers Margutti et al. 2002

Silylation Titanium(IV) Oxide with Organosilicone Meng et al. 2002

Silylation of Nano cellulose Series of alkyldimethylchlorosilanes Gousse et al. 2002

Silylation Functionalised silanes Abdelmouleh et al. 2004

Acetylation of Nano cellulose Alkyenyl succinic anhydride (ASA) Yuan et al. 2006

TEMPO oxidation of Nano cellulose 2,2,6,6-tetramethylpiperidine-1-oxyl Habibi et al. 2006

Fluorescently labelled NCC Fluorescein-5_-isothiocyanate (FITC) Dong & Roman 2007

Cationisation of Nano cellulose Epoxypropyltrimethylammonium chloride Hasani et al. 2008

Grafting of Nano cellulose Polycaprolactone Habibi&Dufresne, 2008

Grafting of Nano cellulose Styrene Yi et al. 2008

Grafting of Nano cellulose Azobenzene polymers Xu et al. 2008

Grafting of Nano cellulose DMAEMA Morandi et al. 2009

Grafting Polymer Roy et al. 2009

Esterification of Nanocellulose Gas phase evaporation of palmitoyl chloride Berlioz et al. 2009

Surface acetylation of Nanocellulose Vinyl acetate Cetin et al. 2009

Esterification of Nanocellulose Fischer process Braun & Dorgan, 2009

Silylation of Nanocellulose Mercaptosilane Zhang et al. 2010

Graft Copolymerization Lignocellulosic fibres Sinha et al. 2010,

Graft Copolymerization Lignocellulosic fibres Siqueria et al. 2010.

Graft Copolymerization Lignocellulosic fibres Siro et al., 2010

Grafting of cellulose Poly(methacrylic acid) Anirudhan et al. 2011

Silane treatment of short cellulosic fibres Silylation Lopattananon et al. 2011

Acetylation Cellulose acetate membrane Tian et al. 2011

Grafting of Nanocellulose Poly(acrylic acid)-poly glycidylmethacrylate Anirudhan et al. 2012

Amination of Nanocellulose Quaternary ammonium salts Salajkova et al. 2012

Carboxymethylation Polyacrylic acid Mishra et al. 2012

Grafting onto cellulose microspheres Radiation-induced styrene Zhang et al. 2012

Grafting of Nanocellulose Acrylamide Yang et al. 2012

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OBJECTIVES

To convey the technology with the harmony of natural environment is the key

challenge of this millennium. The treatment of environmental troubles requires

discovery of newer, cost effective and eco-friendly methods based on biomaterials,

using renewable resources. Functionalization of biomaterials for the waste water

treatment is in great demand.

Keeping above views in mind, the present piece of work addresses the

functionalizationof cellulose/nanocellulose to enhance the sorption efficacy for

arsenic species from water bodies.

It is proposed to carry out the present work with the following specific aims:

�� Functionalization (Grafting through the combination of Periodate oxidation and

reductive-amination reaction, Silylationwith Aminosilane, Cationization using

Epoxy propyl trimethylammonium chloride, EPTMAC and Epoxypropyl N-

methylmorpholinium chloride, EPMMC and AminationbyEthylenediamine) in

laboratory batch conditions and standardization of the optimum conditions for the

evaluation of sorption efficiency of cellulose/nano cellulose for anionic arsenic

species, As(III) and As(V) from water bodies.

�� Designing of functionalized cellulose/nano cellulose Filter aid(Tea bags and non-

woven Poly Propylene bags)to be used in arsenic remediation from water bodies.

�� Application of functionalized cellulose/nano cellulose material as filler in small

bags for decontamination of arsenic in real waste water treatment.

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PLAN OF WORK

�� Preparation of cellulose powder from wood pulp using green methods of enzymatic

treatment and its functionalization, making it suitable for the sorption of anionic arsenic

species [Designing of biomaterial for arsenic sorption].

�� Preparation of nano cellulose from cellulose powder, its characterization for nano-scale

particle size, morphology and structure (SEM, TEM, FTIR, XRD and TGA) followed by

functionalization to enhance the sorption efficiency [Nanotech and Synthetic

Enhancement in arsenic sorption efficiency].

�� Standardization of the optimum conditions for the evaluation of sorption efficiency

offunctionalized cellulose/nanocellulose for anionic arsenic species (As III and As V) from

aqueous system as a function of biomass dose, concentration of arsenic species, initial

volume, contact time and pH [Process Optimization].

�� Characterization of functionalized cellulose/nanocellulose to highlight the mechanistic

aspects of sorption on the basis of the records of BET surface area, XRD, SEM, FTIR and

TGAetc. [Academic interest].

�� Regeneration of arsenic loaded tailored biomaterial by green eluting agents for its

reusability [Cost effectiveness].

�� Designing of functionalized cellulose/nanocellulose filter aidinsmall bags of non-woven

poly propylene material for the use in arsenic remediation from water

bodies[Decontamination of arsenic at Commercial scale].

METHODS AND METHODOLOGY Proposed plan of work is depicted schematically as follows.

A. Preparation of Cellulose Powder from Wood pulp

B. Preparation of Nanocellulose from Cellulose Powder

Soak wood pulp in water followed by digestion with Caustic solution under controlled conditions of Time and temperature

Neutral pulp is treated with Cellulase enzyme in controlled pH, concentration, time and temperature

After the digestion process, material is washed and bought to pH 7

At the end of the reaction, material is washed and cellulose powder

METHODS AND METHODOLOGY

Proposed plan of work is depicted schematically as follows.

Preparation of Cellulose Powder from Wood pulp(Mora’n et al., 2008

Preparation of Nanocellulose from Cellulose Powder (Ioelovich,

Soak wood pulp in water followed by digestion with Caustic under controlled conditions of Time and temperature

under high shear agitation

Neutral pulp is treated with Cellulase enzyme in controlled pH, concentration, time and temperature


At the end of the reaction, material is washed and cellulose powder is dried in fluid bed drier

10

Mora’n et al., 2008)

Ioelovich, 2012)

Soak wood pulp in water followed by digestion with Caustic under controlled conditions of Time and temperature

Neutral pulp is treated with Cellulase enzyme in controlled pH,


At the end of the reaction, material is washed and cellulose powder

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C. Functionalization of Cellulose/Nano cellulose using standard reactions

I. Grafting through Periodate oxidation and reductive-amination scheme

II. Silylation with Aminosilane

Cellulose/nano cellulose will be pretreated with NaOH for about half an hour prior to

its coupling with silane

Silane will be taken in 95% alcohol

Soak Cellulose/nano cellulose in a solution of 2%

silane for 5min

pH value will be adjusted 4.5–5.5 followed by 30 min air drying for hydrolyzing

the coupling agent

Cellulose/nano cellulose + sodium periodate (pH 4.0)

Solution warmed to 38 ºC

Stirred for 1 h under a nitrogen atmosphere in the

absence of light

Filtration or centrifugation

Agitated for about 15 min and filtered

2,3-dialdehyde products of cellulose/nano

cellulose

Amination through Schiff base reaction

Amine derivative of 2,3-dialdehyde products of cellulose/nano cellulose

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III. Amination with Ethylenediamine

IV. Amination

IV. Cationization using EPTMAC andEPMMC

Cellulose/nano cellulose dissolved in distilled water

Potassium peroxydisulphate will be added as an initiator and kept under stirring

After 10 min 1.0 g of acrylamide will be added and stirred for 90 min. at 50°c and

washed with deionised water dried at 50°c

Ethylenediamine will be added and refluxed for 8 h

After proper pH adjustment, the aminatedcellulose/nanocellulose

purified by washing with deionized water, and then dried in a vacuum

oven at 50°c

Cellulose/nano cellulose alkalinized with 5% NaOH with the ratio of 1M OH group equivalent to

1.5M NaOH for 15 min at room temperature with stirring

EPTMAC or EPMMC (1.5

equiv/cellulose hydroxyl group) will

be added into suspensions, which then

alkalinized by NaOH treatment and

the mixture will be stirred for 5 hours

at 50°C

Suspensions will be sonicated

and concentrated by reduced

pressure evaporation in the

room temperature

After 5 hours, the reaction will be

quenched by water and diluted to 5-fold

and dialyzed against distilled water for

5 days

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D. Experimental conditions for sorption

Sorption efficiency at laboratory scale using standard practices would be carried out in batch

experiments under various experimental conditions

E. Standardization and characterization of arsenate and arsenite,Cellulose/Nanocellulose interactions for the evaluation of sorption and regeneration efficiency

STOCK SOLUTION OF ARSENIC SPECIES SALTS

(NaAsO2, Na2HAsO4,) As (III) As (V)

FILTRATE

BIOSORBENT PREPARATION (Cellulose/nanocellulose) • Collection • Isolation • Purification

FILTRATION Whatman 42 filter paper

CHARACTERIZATION �� BET �� SEM �� FTIR �� XRD

RESIDUE (Metal loaded

biomass)

BIOSORPTION STUDIES Contact time pH adjustments Shaking Arsenic sp. conc. Biomass dose

Metalloid ESTIMATION (In terms of % sorption)

ICP-AES

DESORPTION STUDIES

• Stripping agent [Acid, Base and Distl. Water

• Contact with metal loaded biomass

• Shaking

BATCH EXPERIMENTS

TEST VOLUME (100, 200, 300 ml)

BIOMASS DOSAGES (1.0, 2.0, 4.0, 5.0 g)

pH RANGE [2.5, 3.5, 4.5, 6.5, 7.5, 8.5]

CONTACT TIME (10, 20, 30, 40, 50 min)

ARSENIC SPECIESCONCENTRATION (1, 5, 10, 25, 50, 100 mg/L)

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IMPORTANCE OF THE PROPOSED WORK IN THE PRESENT CONTEXT

The preparation of functionalized cellulose/nanocellulose may lead to the formation of need based

tailored biomaterial having enhanced sorption efficacy and environmental stability. Process

development based on the use of Nanocellulose is deemed to be a strong foundation for the

development of cost effective, ecofriendly, green nanotechnology for removal of Arsenic species from

waste water particularly for rural and remote areas as a pretreatment step of waste water

treatment. Functionalized cellulose/nanocellulose could be a potential challenge for inorganic

materials.

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REFERENCES

1. Abdel-Halim ES. Physiochemical properties of differently pretreated cellulosic fibers. Carbohydr.

Polym. 88, 1201– 1207, 2012.

2. Abdelmouleh M, Boufi S, Belgacem MN, Duarte AP, Salah A, Gandini A. Modification of cellulosic

fibres with functionalisedsilanes: development of surface properties. Int J AdhesAdhes. 24, 43–54,

2004.

3. Ahalya N, Ramachandra TV, Kahamadi RD, Biosorption of heavy metals. Journal of chemistry and

environment, 7(2), 71-79, 2003.

4. Amin MN, Kaneco S, Kitagawa T, Begum A, Katsumata H, Suzuki T. Ohta K. Removal of arsenic in

aqueous solutions by adsorption onto waste rice husk. Ind. Eng. Chem. Res.45, 8105-8110, 2006.

5. Anirudhan TS, Rejeena SR. Poly(acrylic acid)-modified poly(glycidylmethacrylate)-grafted

nanocellulose as matrices for adsorption of lysozyme from aqueous solutions. Chem. Eng. J. 187, 150–

159, 2012.

6. Anirudhan TS, Tharun AR, Rejeena SR. Investigation on poly (methacrylic acid)-grafted

cellulose/bentonite superabsorbent composite: synthesis, characterization, and adsorption

characteristics of bovine serum albumin. Ind. Eng.Chem. Res. 50, 1866–1874, 2011.

7. Araki J, Wada M, Kuga S. Steric Stabilisation of a Cellulose Microcrystal Suspension by Poly (ethylene

glycol) Grafting. Langmuir. 17, 21–27, 2001.

8. Basu A, Kumar S, Mukherjee S. Arsenic reduction from environment by water lettuce (Pistiastratiotes

L.). Ind. J. Environ. Health. 45, 143-150, 2003.

9. Berlioz S, Molina-Boisseau S, Nishiyama Y Heux L. Gas-Phase Surface Esterification of Cellulose

Microfibrils and Whiskers. Biomacromolecules. 10, 2144–2151, 2009.

10. Bose U, Rahman M, Alamgir M. Arsenic toxicity and speciation analysis in ground water samples: A

review of some techniques. Int. J. Chem. Tech. 3(1) 14-25, 2011.

11. Braun B, Dorgan JR. Single-Step Method for the Isolation and Surface Functionalisation of Cellulosic

Nanowhiskers. Biomacromolecules. 10, 334–341, 2009.

12. Cano-Aguilera I, Haque N, Morrison GM, Aguilera-Alvarado AF, Gutierrez M, Gardea-Torresdey GL,

De la Rosa G. Use of hydride generation-atomic absorption spectrometry to determine the effects of

hard ions, iron salts and humic substances on arsenic sorption to sorghum biomass. Microchem. J.

81(1) 57–60, 2005.

13. Cetin NS, Tingaut P, Ozmen P, Henry N, Harper D, Dadmun M, Sebe G. Acetylation of Cellulose

Nanowhiskers With Vinyl Acetate under Moderate Conditions. Macromol. Biosci. 9, 997–1003 2009.

14. Chen CC, Chung YC. Arsenic removal using a biopolymer chitosan sorbent. J. Environ. Sci. Health

Part A: Toxic/Hazard. Substances Environ. Eng. 41(4) 645–658, 2006.

15. Chen YN, Chai LY, Shu YD. Study of arsenic (V) adsorption on bone char from aqueous solution. J.

Hazard. Mater. 160, 168-172, 2008.

16. Chiban M, Lehutu G, Sinan F, Carja G. Arsenate removal by Withaniafrutescensplant from the south–

western Morocco. Environ. Eng. Manage. J. 8, 1377-1383, 2009.

17. Chiban M, Soudani A, Sinan F, Persin M. Single, binary and multi-component adsorption of some

anions and heavy metals on environmentally friendly Carpobrotusedulisplant. Colloids Surf. B:

Biointerfaces. 82, 267-276, 2011.

18. Coseria S, Biliuta G, Simionescua BC, Stana-Kleinschekc K, Ribitschd V, Harabagiua V. Oxidized

cellulose—Survey of the most recent achievements. Carbohydr. Polym. xxx xxx– xxx, 2012.

19. Dieter K, Brigitte H, Hans-Peter F, Andreas B. Cellulose: fascinating biopolymer and sustainable raw

material. J. polym. Sci. A polym. Chem. 44, 3358-3393, 2005.

20. Dong SP, Roman M. Fluorescently Labeled Cellulose Nanocrystals for Bioimaging Applications. J. Am.

Chem. Soc. 129, 13810–13811, 2007.

21. Dongping S, Lingli Z, Qinghang WU, Shulin Y. Preliminary research on structure and properties of

nanocellulose. J. Wuhan Univ. Technol. 22(4) 677-680, 2007.

22. Donia AM, Atia AA, Abouzayed FI. Preparation and characterization of nano-magnetic cellulose with

fast kinetic properties towards the adsorption of some metal ions. Chem. Eng. J. 191, 22– 3, 2012.

23. Ghimire KN, Inoue K, Yamaguchi H, Makino K, Miyajima T. Adsorptive separation of arsenate and

arsenite anions from aqueous medium by using orange waste. Water Res. 37, 4945-4953 2003.

16

24. Gilberto S, Julien B, Alain D. Cellulosic Bionanocomposites: A Review of Preparation, Properties and

Applications.Polymers, 2, 728-765, 2010.

25. Gousse CH, Chanzy G, Excoffier L, SoubeyrandFleury E. Stable Suspensions of Partially Silylated

Cellulose Whiskers Dispersed in Organic Solvents. Polym. J.43, 2645–2651, 2002.

26. Guo X, Chen F. Removal of arsenic by bead Cellulose loaded with iron Oxyhydroxide from

groundwater. 2005.

27. Habibi Y, Chanzy H, Vignon M. TEMPO-Mediated Surface Oxidation of Cellulose Whiskers. Cellulose.

13, 679–687, 2006.

28. Habibi Y, Dufresne A. Highly Filled Bionanocomposites from Functionalised Polysaccharide

Nanocrystals. Biomacromolecules. 9, 1974–1980, 2008.

29. Habibi Y, Lucia LA, Rojas OJ. Cellulose nanocrystals: chemistry, selfassembly, and applications.

Chem. Rev. 110(6) 3479–3500, 2010.

30. Hamadani JD, Mcgregor SMG, Tofail F, Nermell B, Fanstrom B. Pre and postnatal arsenic exposure

and child developments at 18 months of age: A cohort study in rural Bangladesh. Int. J. Epidemiol.

2010.

31. Hasani M, Westman G, Potthast A, Rosenau T. Cationization of cellulose by using N-oxiranylmethyl-

N-methylmorpholinium chloride and 2-oxiranylpyridine as etherification agents. J ApplPolym Sci.

114(3) 1449–1456, 2009.

32. Hashaikeh R, Abushammala H. Acid mediated networked cellulose: Preparation and characterization.

Carbohydr. Polym. 83, 1088–1094, 2011.

33. Hoque BA, Yamaura S, Sakai A, Khanam S, Karim M, Hoque Y, Hossain S, Islam S, Hossain O.

Arsenic mitigation for water supply in Bangladesh: appropriate technological and policy

perspectives. Water Qual. Res. J. Can. 41(2), 226–234, 2006.

34. Igwe JC, Abia AA. Sorption kinetics and intrapaticulate diffusivity of As (III) bioremediation from

aqueous solution, using modified and unmodified coconut fiber. Ecl. Quim. Sao Paulo. 31(3), 23-29,

2006.

35. Igwe JC, Nwokennaya EC, Abia AA. The role of pH in heavy metal detoxification by biosorption from

aqueous solutions containing chelating agents. Afri. Jourl. of Biotech. 4(10) 1109-1112 2005.

36. International Agency for Research on Cancer: Some drinking waterdisinfectants and contaminants,

including arsenic. IARC Monographs on the evaluation of carcinogenic risks to humans. 84, 2004.

37. Ioelovich M. Optimal Conditions for Isolation of Nanocrystalline Cellulose Particles.Nanoscience and

Nanotechnology. 2(2) 9-13, 2012.

38. Islam MJ, Hossain MR, Yousuf A, Subhan MA. Removal of arsenic from drinking water using bio-

adsorbents. Proc. Pakistan Acad. Sci. 44(3) 157-l64, 2007.

39. Johnston R, Heijnen H. Safe water technology for arsenic removal, in: M.F. Ahmed, et al. (Eds.),

Technologies for Arsenic Removal from Drinking Water, Bangladesh University of Engineering and

Technology, Dhaka, Bangladesh, 2001.

40. Kamala CT, Chub KH, Chary NS, Pandey PK, Ramesh SL, Sastry ARK, Chandrasekhar K. Removal of

arsenic (III) from aqueous solutions using fresh and immobilized plant biomass. Water Res. 39, 2815-

2826, 2005.

41. Kamsonlian S, Suresh S, Majumder CB, Chand S. Biosorption of As (III) from contaminated water

onto low cost palm bark biomass. Inte. Jour. of Curr. Eng. and Tech. 2(1) 153-158, 2012.

42. Kartal SN, Imamura Y. Removal of Cu (II), Cr (III) and As (III) from CCA-treated wood onto chitin

and chitosan. Bioresource Technol. 96, 389-392, 2005.

43. Katsoyiannis IA, Zouboulis AI. Application of biological processes for the removal of arsenic from

ground waters. Water Res. 38, 17–26, 2004.

44. Kim SY, Zille A, Murkovic M, Guebitz G, Cavaco-Paulo A. Enzymatic polymerization on the surface of

functionalized cellulose fibers. Enzyme Microb. Technol. 40, 1782–1787, 2007.

45. Klemm D, Schumann D, Kramer F, Hebler N, Koth D, Sultanova B. Nanocellulose Materials Different

Cellulose, Different Functionality. Macromolecule Symposium, 280, 60–71, 2009.

46. Korotkov AN, Voskoboinikov IV, Konstantinova SA, Gal’braikh LS, Mikhailov AI. Some observations

on obtaining cellulose nanocrystals. Fibre Chemistry, 43 (5) 2012.

47. Lee KY, Quero F, Blaker JJ, Hill CAS, Eichhorn SJ, Bismarck A. Surface only modification of

bacterial cellulose nanofibres with organic acids. Cellulose. 18, 595–605, 2011.

17

48. Llorente-Mirandes T, Ruiz-Chancho MJ, Barbero M, Rubio R, Lopez-Sanchez JF. Determination of

water-soluble arsenic compounds in commercial edible seaweed by LC-ICPMS. J. Agric. Food Chem.

59, 12963–12968, 2011.

49. Llorente-Mirandes T, Ruiz-Chancho MJ, Barbero M,Rubio R, Lopez-Sanchez JF. Measurement of

arsenic compounds in littoral zone algae from the Western Mediterranean Sea: Occurrence of

arsenobetaine. Chemosphere, 81, 867–875, 2010.

50. Lopattananon, Natinee, Jitakalong, Dolmalik, Seadam, Manus, Sakai, Tadamoto. Effect of silane

treatment on hybridized use of short cellulose fibres and silica particles for natural rubber

reinforcement. Seikei-kokou. 23(11) 2011.

51. Lu P, Hsieh YL. Preparation and properties of cellulose nanocrystals: Rods, spheres, and network.

Carbohydr. Polym, 82, 329–336, 2010.

52. Mahamadi C. Water hyacinth as a biosorbent: A review. Afr. J. Environ. Sci. Technol. 5(13) 1137-1145,

2011.

53. Malik AH, Khan ZM, Mahmood Q, Nasreen S, Bhatti ZA. Perspectives of low cost arsenic remediation

of drinking water in Pakistan and other countries. J. Hazard. Mater. 168,

1–12, 2009.

54. Meenakshi, Maheshwari RC. Arsenic removal from water: a review. Asian J. Water Environ. Pollut.

3(1) 133–139, 2006.

55. Meng L, Du C, Chen Y, He Y. Preparation, Characterization, and Behavior of Cellulose–Titanium (IV)

Oxide Modified with Organosilicone. J. Appl. Polym. Sci. 84, 61–66, 2002.

56. Mishra S, Rani GU, Sen G. Microwave initiated synthesis and application of polyacrylic acid grafted

carboxymethyl cellulose. Carbohydr. Polym. 87, 2255– 2262, 2012.

57. Memon SQ, Bhanger MI, Memon J. Evaluation of banana peel for treatment of arsenic contaminated

water. 1st Technical Meeting of Muslim Water Researchers Cooperation (MUWAREC), Malaysia,

2008.

58. Mohan D, Pittman CU, Steele PH. Pyrolysis of wood/biomass for bio-oil: a critical review, Energy

Fuels. 20(3) 848–889, 2006.

59. Mora´n JI, Alvarez VA, Cyras VP, Va´zquez A. Extraction of cellulose and preparation of

nanocellulose from sisal fibers. Cellulose, 15, 149–159, 2008.

60. Morandi G, Heath L, Thielemans W. Cellulose Nanocrystals Grafted With Polystyrene Chains Through

Surface-Initiated Atom Transfer Radical Polymerisation (SI-ATRP). Langmuir 25, 8280–8286, 2009.

61. O’Day PA, Vlassopoulos D, Meng X, Benning LG (Eds.) Advances in Arsenic Research, American

Chemical Society, Washington, DC, ACS Symposium Series 915, ISBN 0841239134, 2005.

62. Pahimanolis N, Hippi U, Johansson LS, Saarinen T, Houbenov N, Ruokolainen J, Seppala J. Surface

functionalization of nanofibrillated cellulose using click-chemistry approach in aqueous media.

Cellulose, 18, 1201–1212, 2011.

63. Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK. Cellulose crystallinity index: measurement

techniques and their impact on interpreting cellulase performance. Biotechnology for Biofuels, 3(10),

2010.

64. Peng BL, Dhar N, Liu HL, Tam KC. Chemistry and Applications of Nanocrystalline Cellulose and its

Derivatives: a Nanotechnology Perspective. The Canadian Journal of Chemical Engineering, 9999, 1-

16, 2011.

65. Rezaitabar S, Esmaili-Sari A, Bahramifar N. Potential health risk of total arsenic from consumption of

farm rice (Oryza sativa) from the Southern Caspian Sea Littoral and from imported rice in Iran.Bull.

Environ. Contam. Toxicol. 88(4), 614-616, 2012.

66. Roy D, Semsarilar M, Guthrie JT, Perrier S. Cellulose Modification by Polymer Grafting: A Review.

Chem. Soc.Rev. 38, 2046–2064, 2009.

67. Sadeghifar H, Filpponen I, Clarke SP, Brougham DF, Argyropoulos DS. Production of cellulose

nanocrystals using hydrobromic acid and click reactions on their surface. Journal of Material Science.

46, 7344–7355, 2011.

68. Salajkov M, Lars A, Berglund, Zho Q. Hydrophobic cellulose nanocrystals modified with quaternary

ammonium salts. J. Mater. Chem. 22, 2012.

69. Seki H, Suzuki A, Maruyama H. Biosorption of chromium (VI) and arsenic (V) onto methylated yeast

biomass. J. Colloid Interf. Sci. 281(2) 261–266, 2005.

70. Shaikh MS, Qureshi K, Bhatti I. Utilization of Tea Waste for the Removal of Arsenic (III) from Aqueous

Solution. Sindh Univ. Res. Jour. (Sci. Ser.) 43 (1) 97-104, 2011.

18

71. Sinha AS, Rana RK. Enhancement of hydrophobic character of lignocellulosicfibres through graft-

copolymerization. Advance Material Letter, 1(2), 156-163, 2010.

72. Siqueira G, Bras J, Dufresne A. Cellulosic Bionanocomposites: A Review of Preparation, Properties

and Applications. Polymers. 2, 728-765, 2010.

73. Siro I, Plackett D. Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose.

459–494, 2010.

74. Teixeira EM, Correa AC ,Manzoli A, Leite FL, Oliveira CR , Mattoso CLH. Cellulose nanofibers from

white and naturally colored cotton fibers. Cellulose. 17, 595–606, 2010.

75. Tian Y, Wu M, Liu R, Li Y, Wang D, Tan J, Wu R, Huang Y. Electrospun membrane of cellulose acetate

for heavy metal ion adsorption in water treatment. CarbohydrPolym, 83, 743–748, 2011.

76. Tofail F, Vather M, Hamadani JD, Nermell B, Huda SN. Effect of arsenic exposure during pregnancy

on infant development at 7 months in rural Matlab, Bangladesh. Environ. Health Perspec. 117, 288-

293, 2009.

77. Urik M, Littera P, Sevc J, Kolencik M, Cernansky S. Removal of arsenic (V) from aqueous solutions

using chemically modified sawdust of spruce (Piceaabies): Kinetics and isotherm studies. Int. J.

Environ. Sci. Technol. 6(3) 451-456, 2009.

78. USEPA. Treatment technologies for arsenic removal. National Risk Management Research

Laboratory, Cincinnati, 2005.

79. Vankar PS, Tiwari V. Phytofiltration of Toxic Metals Ions by Portulacaoleracea. Journal of Analytical

Chemistry, 36, 327-332, 2002.

80. Vasudevan P, Padnavathy V, Tewari N, Dhingra SC. Biosorption of heavy metal ions.

J. Sci. Ind. Res. 60, 112-120, 2001.

81. Wang X, Ma LQ, Rathinasabapathi B, Cai Y, Liu YG, Zeng GM. Mechanisms of efficient arsenite

uptake by arsenic hyperaccumulatorPterisvittata. Environ. Sci. Technol. 45, 9719–9725 2011.

82. Xu Q, Yi J, Zhang J, Zhang H. A Novel Amphotropic Polymer Based on Cellulose Nanocrystals Grafted

With Azo Polymers. Eur. Polym. J. 44, 2830–2837, 2008.

83. Yang J, Ye yong D. Liquid crystal of nanocellulose whiskers grafted with acrylamide. Chin. Chem.

Lett. 23, 367-370, 2012.

84. Yi J, Xu Q, Zhang X, Zhang H. Chiral-Nematic Self-Ordering of Rodlike Cellulose Nanocrystals

Grafted With Poly(styrene) in Both Thermotropic and Lyotropic States. Polym. J.49, 4406–4412,

2008.

85. Yuan H, Nishiyama Y, Wada M, Kuga S. Surface Acylation of Cellulose Whiskers by Drying Aqueous

Emulsion. Biomacromolecules. 7, 696–700, 2006.

86. Zhang X, Huang J. Functional surface modification of natural cellulose substances for colorimetric

detection and adsorption of Hg2+ in aqueous media. Chem. Commun. 46, 6042–6044, 2010.

87. Zhang Y, Xu L, Zhao L, Peng J, Li C, Li J, Zhaia M. Radiation synthesis and Cr (VI) removal of

cellulose microsphere adsorbent. Carbohydr. Polym. 88, 931– 938, 2012.

88. Zimmermann T, Bordeanu N, Strub E. Properties of nanofibrillated cellulose from different raw

materials and its reinforcement potential. Carbohydr. Polym. 79, 1086–1093, 2010.

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