ijirae::biodegradable surfactant from natural starch for the reduction of environmental pollution...

International Journal of Innovative Research in Advanced Engineering (IJIRAE) ISSN: 2349-2163 Volume 1 Issue 8 (September 2014) www.ijirae.com

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Biodegradable Surfactant from Natural Starch for the Reduction of Environmental Pollution and Safety for Water

Living Organism

Abstract: The chemical contamination of water from a wide range of toxic derivatives, in particular soap, surfactants, heavy metals, aromatic molecules and dyes, is a serious environmental problem owing to their potential human toxicity. Therefore, there is a need to develop natural polymeric surfactant from starch that can free from toxic pollutants found in wastewaters, ponds, drains, canals and rivers. Among all the treatments proposed, adsorption is one of the more popular methods for the removal of pollutants from the waste water and soap-detergent free water. On the other hand, water living organism can live smoothly without chemically substances (soap, surfactants) in the mentioned sources by using naturally polymeric surfactants (prepared from potato starch). Adsorption is a procedure of choice for treating industrial effluents, and a useful tool for protecting the environment. In particular, adsorption on natural polymers and their derivatives are known to remove pollutants from water. The increasing number of publications on adsorption of toxic compounds by modified polysaccharides shows that there is a recent increasing interest in the synthesis of new low-cost adsorbents used in wastewater treatment and using natural polymeric surfactants from natural sources for better washing in garments, textiles and household washing. The present review shows the recent developments in the synthesis of adsorbents containing polysaccharides, in particular modified biopolymers derived from chitin, chitosan, starch and cyclodextrin. New polysaccharide based-materials are described and their advantages for the removal of pollutants from the wastewater discussed. The main objective of this review is to provide recent information about the most important features of these polymeric materials and to show the advantages gained from the use of adsorbents containing modified biopolymers in waste water treatment where chemical substances (surfactant like CTAB, Tween-20, SDS) mixing when they are used as washing purposes in textile industries. From the experimental results of viscosity, surface tension and other physical properties it indicated that adding starch in detergent as soap filler these properties have changed which also indicated the more washing activity of polymeric starch (potato) were cheaply available indoor market in Bangladesh. Biodegradable starch interactions with ionic surfactants (CTAB, SDS) by the way of H-bond formation to ensure complexation and reduced the harmful criteria of living organism in water also to ensure maximum protection of water pollution. The formed complexes from starch-ionic surfactant-water were analyzed and characterized by XRD and SEM instruments. Some of the complexes exhibited excellent emulsifying efficiency and polymeric surfactants performance properties with this biodegradable natural starch polymer.

Keywords- biodegradable, CMC, Natural Starch, SEM, surfactants, water pollution and XRD.

I.INTRODUCTION

Water pollution due to toxic metals such as soluble soap-detergents in water in ponds, rivers, canals and organic compounds remains a serious environmental and public problem Moreover, faced with more and more stringent regulations, water pollution has also become a major source of concern and a priority for most industrial sectors such as textile Industry, soap Industry, detergent Industry. Heavy metal ions, aromatic compounds (including phenolic derivatives, and polycyclic aromatic compounds) and dyes are often found in the environment as a result of their wide industrial uses. They are common contaminants in wastewater and many of them are known to be toxic or carcinogenic. For example, chromium (VI) is found to be toxic to bacteria, plants, animals and people [1]. Mercury and cadmium are known as two of the most toxic metals that are very damaging to the environment [2]. In addition, heavy metals are not biodegradable and tend to accumulate in living organisms, causing various diseases and disorders. Therefore, their presence in the environment, in particular in water should be controlled. Chlorinated phenols are also considered as priority pollutants since they are harmful to organisms even at low concentrations. They have been classified as hazardous pollutants because of their harmful potential to human health [3,4]. 2,4,6-trinitrotoluene (TNT) is a nitro-aromatic molecule that has been widely used by the weapon industry for the production of bombs and grenades. This compound is recalcitrant, toxic and mutagenic to various organisms [5,6]. Many synthetic dyes, which are extensively used for textile dyeing, paper printing and as additives in petroleum products are recalcitrant organic molecules that strongly color waste water.Strict legislation on the discharge of these toxic products makes it

Md. Ibrahim H. Mondal Department of Applied Chemistry & Chemical

Engineering, (ACCE) University of Rajshahi, Rajshahi -6205,

Bangladesh

Md. MohsinHossain Department of Applied Chemistry & Chemical

Engineering, (ACCE) University of Rajshahi, Rajshahi -6205,

Bangladesh



then necessary to develop various efficient technologies for the removal of pollutants from waste water. Different technologies and processes are currently used. Biological treatments [7–9], membrane processes [10–13], advanced oxidation processes [14–17], chemical and electrochemical techniques [18–20], and adsorption procedures [21–49] are the most widely used for removing metals and organic compounds from industrial effluents. Amongst all the treatments proposed, adsorption using sorbents is one of the most popular methods since proper design of the adsorption process will produce high-quality treated effluents. Adsorption is a well-known equilibrium separation process. The adsorbents may be of mineral, organic or biological origin: activated carbons [21–26], zeolites [27,28], clays [29–33], silica beads [34,35], low-cost adsorbents (industrial by-products [36–41], agricultural wastes [42,43], biomass [44,45]) and polymeric materials (organic polymeric resins [46,47], macro porous hyper-cross linked polymers [48,49]) are significant examples. Table.1 shows a non-exhaustive list of some selected examples of adsorbents used in wastewater treatment. Recently, numerous approaches have been studied for the development of cheaper and more effective polymeric surfactant for better washing containing natural polymers. Among these, polysaccharides such as chitin [50–52] and starch [53–55], and their derivatives (chitosan [56,57], cyclodextrin [58–60]) deserve particular attention. These biopolymers represent an interesting and attractive alternative as cleansing substances because of their particular structure, physico-chemical characteristics, chemical stability, high reactivity and excellent selectivity towards aromatic compounds and metals, resulting from the presence of chemical reactive groups (hydroxyl, acetamido or amino functions) in polymer chains. Moreover, it is well known that polysaccharides which are abundant, renewable and biodegradable resources, have a capacity to associate by physical and chemical interactions with a wide variety of molecules [61,62] Hence adsorption on polysaccharide derivatives can be a low-cost procedure of choice in water decontamination for extraction and separation of compounds, and a useful tool for protecting the environment [63]. Besides, the increasing number of publications on adsorption of toxic compounds by these natural polymers shows that there is a recent interest in the synthesis of new adsorbent materials containing polysaccharides. Polysaccharides, stere oregular polymers of mono saccharides (sugars), are unique raw materials in that they are: very abundant natural polymers (they are referred to as biopolymers); inexpensive (low-cost polymers); widely available in many countries; renewable resources; stable and hydrophilic biopolymers; and modifiable polymers. They also have biological and chemical properties such as non-toxicity, biocompatibility, biodegradability, poly functionality, high chemical reactivity, chirality, chelation and adsorption capacities. The excellent adsorption behavior of polysaccharides is mainly attributed to: (1) high hydrophilicity of the polymer due to hydroxyl groups of glucose units; (2) presence of a large number of functional groups (acetamido, primary amino and/or hydroxyl groups); (3) high chemical reactivity of these groups; (4) flexible structure of the polymer chain. From the above mentioned features, it is proved that many researchers have paid their attention on this field. In spite of half century of great effort, many academic aspects such as, chemistry, chemical reactions, bond formation on starch-surfactants interaction are still open for discussion. The purpose of the present investigation is to explore the effect of starch interaction with various surfactants and the better understanding the mechanism between starch and surfactants complexes formed as polymeric surfactants studied by the ternary phase diagram, interfacial surface tension and viscosity measurement and characterized by the XRD and SEM analysis.

I I . EXPERIMENTAL 2.1Materials

Potato starch as powder formwaspurchased fromUNI-CHEM, China and its degreeof substitution (DS) was

0.80.Starch solution was prepared byheating thestarchin waterin anautoclave at1200C for30min. All solutions were

prepared at least24h before measurement was performed. The surfactants sodium dodecyl sulphate (SDS), N-cetyl-

N,N,N-trimethyl ammoniumbromide (CTAB) and Tween-20 were purchased as analyticalgrade and were used without

further purification.The water used was ion exchanged and distilled. Its conductivity, and reduced viscosity were 2.0

µs and 4.0 dm3/mol, respectively and its surface tension was 71.5×10-3±0.5N/mat300C. All other chemicals were

analytical grade and were used without further purification.

METHODS

2.2.1 Surfaceandinterfacialtensionmeasurement

Surface tension was measured with a drop weight method (Stalagmometer i nstruments).In the calculation of surface

tension ,the correction factors of Huh and Mason [65] were used. The reproducible result between measurements of

thesamesamplewas±0.5mN/m. The results of the surface tension measurement were presented as () values calculated



fromrf

mg

2

. Where, f is equal to 3

1v

, v i s the volume of the drop and r is its radius, mg is the weight of falling

drop and is its surface tension. A drop of the weight(mg) given by the above equation has been designated as the

ideal drop. Repeated measurements (2-4 times) were conducted on each sample from which equilibrium surface or

interfacial tension values were obtained by averaging the values at very long periods, where the surface and interfacial

tension values showed little or no change with time. Prior to running tests with the starch solutions, the instrument was

calibrated with water and then checked by measuring the interfacial tension between water and pure starch.

2.2.2Viscosity

Viscosities were determined with an Ostwald viscometer according to British standard (Fisher Scientific TM 200) with

a fluctuation of ±0.10C was used. The flow of time was recorded by a timer accurate up to ±0.01 second. At certain

surfactant/starch ratios the aggregates formed were very mobile flocks, which tended to form in the samples. This could

be partly avoided by draining the capillary fully between measurements. The results of the viscosity values calculated

fromct

tt

red0

0 )(

. where t is the measured efflux time of solutions and t0 is the efflux time of the pure solvent (water)

and C is the weight concentration of the surfactant, starch & surfactants mixed polymer.

2.2.3 Ternary Phase Diagram

2.2.3.1 Sample Preparation

For the development of ternary phase diagrams, the sample components were taken into the test tube by varying

composition in such a way that the total composition remains 100%. The components were added by varying

weight or volumes. The samples were prepared by varying 5% composition of two components simultaneously

keeping the third component constant, alternatively in a test tube. The open end of the test tube was then closed

with rubber cork in such a way that the vapour would come out and would enter into the test tube, here the cork

reacted with the sample. The samples were then shaken for well mixing of the components and placed into the

diagram are put according to the composition and mark. After completion of the 228 samples according to the

diagram on the wooden frame. The open end of the test tube was then closed tightly with cork, so that this would

remain no leakage or the lower part of the cork did not touch the sample solution and after that these samples were

then left to equilibrate in a thermostat box at 30°C for at least ten days and would be shaken from time to time. The

equilibrium was established within this period.

2.3 Characterization

2.3.1 SEM analysis

Scanning Electron Microscope (SEM, JEOL, JSM 6301F, Japan), Fine coaster (JFC 1200,JEOL, Japan), Aluminum

specimen stub, Double-sided adhesive tape.

2.3.1.1 Procedure for sample determination Scanning Electron Microscope (SEM) of potato starch, surfactant sample and starch-surfactant complexes samples were

less than 4% moisture content before examined. Dried sample and sprinkle were taken onto the double-sided adhesive

tape attached to the specimens tub. The excess sample was removed and the sample was placed in fine coater of gold



coating for150seconds. The coated sample was then placed in the sample chamber of the SEM .The sample was

examined at magnification of 2,500 and 6,000 with the accelerating voltage of 10 Kv.

Model and specification:

2.3.2 XRD analysis

2.3.2.1Preparation of sample for XRD

The preparation of starch sample ,the dried sample is saturated with water by stirring repeatedly with a glass rod; this

step is performed by 2g of st arch with 100 ml of hot water which is 100% distilled and stirred at room

temperature for 1h,centrifuging the suspensions and decanting the supernatant solutions. This process is repeatedly three times.

Then the starch solution is dried in oven at temperature 80oC.2h after proper drying the powder sample iskeptinasealedbottle.

The syntheses of cationic surfactants were undertaken by the following procedure: 2gofSodium dodecyl sulphate was first

dispersed in100 ml of deionized water then under mechanical stirring for about 1h. A pre-dissolved starch

solution of same amount was slowly added to that suspension near about at 80oC. The reaction mixtures were

stirred for 1h at 80oC using mechanical stirring after proper drying the powder sample is kept in a sealed bottle then dried

products were stored in vacuum desiccators.

Starch powders to be used for X-ray diffraction (XRD) measurements were equilibrated in desiccators containing

saturated solutions of K2CO3 at 20-22oC.Under these conditions, the relative humidity (RH) at 20°Cwas shown to be

44% and the final water content of pea, maize, potato, and wheat starches was 13–14,12,15,and 12%,respectively.

Wet starch powder (from potato) for XRD measurements was produced by first equilibrating the starch in excess water.

The starch suspension was then centrifuged (3000 g) and the supernatant removed. The starch precipitate appeared as a

hard wet powder that was slightly more moist at the top. This moisture was dried with tissue paper. The wet starch

powder had a water content of 49%. It was apparent that the proportion of water was slightly overestimated, because the

precipitated starch granules would have a small amount of free space between them, which would be filled with free

water. This over estimation, however, can be considered to be very small as the granules in the precipitate were closely

packed. Since the water content with in the crystallites is fixed, near about 24% the proportion of water in the amorphous

part of starch can be estimated at 55–60%. It was assumed that total crystalline of starch and complexes. Apparatus was

Wide-angle X-ray diffractometer (JEOL, JDX 3530, Japan), Silicon sample cell and Computer with program MDI Jade

6.5 (Japan)

From the polymer chemist’s point of view, the chemical substitution of chitin and starch offers enormous challenges.

These are provided by the presence of the numerous functional groups of starch molecules, which are available for

chemical reactions. However, their reactivity depends on experimental conditions. This makes, in general, selective

substitution relatively difficult and different mono, di or tri-derivatives can then be obtained, yielding modified

polysaccharides (starch). The modification of the existing polysaccharides is one possible method of obtaining more

polar sorbents. The possible chemical derivatization of starch and chitin is also an interesting property because it is well-

known that the grafting of ligands can improve their adsorption properties. By incorporating some functional

(hydrophobic) groups either into the backbone of the network structure or as pendant groups it is possible to prepare

materials with strong adsorption properties. The chemical modification of the starch also allows preparation of

derivatized polysaccharide called cyclodextrin.



III. RESULTS AND DISCUSSIONS Some of the prepared starch-surfactant mixture lowered the surface tension of water, namely at lower concentration of

the sample(Table1). The functional properties of some of the prepared surfactant and starch mixed surfactant solutions

were tested for emulsifying efficiency, washing power and anti redeposititative efficiency. The emulsifying efficiency

was characterized by the stability of the paraffinic Tween-20/water emulsions and other surfactant mixture at definite

ratio. The results of reduced viscosities in CTAB and SDSsummarizedin Table 2 and 3 which show that some of the

surfactant made emulsions of the oil/ water type stable even after 24h. Their efficiency was comparable to that of the

commercial emulsifier Tween-20. Some of the tested mixture showed excellent washing power exceeding that of the

anionic detergent, name SDS containing dodecyl chains. The anti-redepositive efficiency was higher than the starting

SDS, but moderate in comparison to starch used as a co-builder in detergents [64]. in case of ionic surfactant (SDS,

CTAB) the changing is remarkable due to maximum interactions occurred with starch polymer. Here, we mentioned that

temperature has a remarkable effect in the complexes of starch-ionic surfactant, here it is obtained according to Arrhenius

rule increasing temperature reduced viscosity and specific viscosity is reduced due to the freeness of solution which has

been seen in Table 2 and 3.

Table 1: The value of surface tension of surfactants (Cationic, Anionic and Non-ionic)) with added starch

Table2 at temperature range (25oC-85oC) solution viscosity of starch mixed CTAB

% Log Conc. of surfactant solution % Conc. of surfactant solution

Surface tension of SDS mixed with

starch soln.

Surface tension of CTAB mixed

with starch soln.

Surface tension of Tween-20 mixed with starch soln.

-2.00 0.01 48.11 48.19 52.11 -1.69 0.02 47.02 46.15 49.19 -1.52 0.03 44.35 44.67 48.75 -1.39 0.04 44.21 43.89 47.61 -1.30 0.05 42.13 43.15 45.63 -1.22 0.06 41.95 42.37 44.84 -1.15 0.07 41.73 41.69 44.45 -1.09 0.08 41.55 41.46 44.05 -1.04 0.09 41.52 41.45 43.05 -1.00 0.10 40.51 41.41 42.07

Temp oC

Reduced Viscosity (polymer) reduced Viscosity (polymer-surfactant mixture)

0.0625% 0.125% 0.250% 0.500% 1.000% 0.0625% 0.125% 0.250% 0.50% 1.00%

25 1644.528 813.616 411.320 213.134 116.297 1549.392 912.256 539.508 298.854 182.692

35 1385.072 823.416 481.496 288.598 170.153 1298.592 786.768 454.012 240.734 159.576

45 1229.392 718.792 426.532 247.572 151.884 1177.504 703.104 392.944 216.802 135.538

55 1065.072 645.592 374.624 218.512 133.615 1021.824 608.992 344.088 192.870 125.923

65 926.688 572.392 341.036 201.418 121.115 918.048 541.016 307.448 168.940 108.615

75 857.504 525.328 313.556 184.324 110.538 822.912 488.728 279.968 155.264 99.961

85 771.024 478.272 286.076 168.94 99.961 753.728 441.672 252.488 141.588 90.346



Table 3 at temperature range (25o-85oC) solution viscosity of starch mixed surfactant (SDS) compounds Temp

oC Reduced Viscosity (polymer) reduced Viscosity (polymer-surfactant mixture)

0.0625% 0.125% 0.250% 0.500% 1.000% 0.0625% 0.125% 0.250% 0.500% 1.000%

25 1644.528 813.616 411.320 213.134 116.297 1549.392 912.256 539.508 298.854 182.692

35 1385.072 823.416 481.496 288.598 170.153 1298.592 786.768 454.012 240.734 159.576

45 1229.392 718.792 426.532 247.572 151.884 1177.504 703.104 392.944 216.802 135.538

55 1065.072 645.592 374.624 218.512 133.615 1021.824 608.992 344.088 192.870 125.923

65 926.688 572.392 341.036 201.418 121.115 918.048 541.016 307.448 168.940 108.615

75 857.504 525.328 313.556 184.324 110.538 822.912 488.728 279.968 155.264 99.961

85 771.024 478.272 286.076 168.94 99.961 753.728 441.672 252.488 141.588 90.346

Scanning Electron Microscopy (SEM)

Figs. 1a, 1b and 1c show the individual surface image of starch, SDS and starch-SDS mixture, respectively studied by

SEM. It can be seen from Figs. 1a, 1b and 1c that the surface images of the starch and surfactant are quite different from

each other. The surfaces of the starch, SDS and mixture of these two looks like granules, pop-corn and needle like

respectively. It is clear that, at a certain temperature and concentration, the starch interacts with the surfactant through the

formation of H-bonds and changes its surface structure.

(a) starch (b) Surfactant (SDS) (C) starchwithSDS mixture

Fig. 1.SEM Image of (a) starch, (b) surfactant (SDS) and (c) starch with SDS mixture

H-bond formation with Surfactant

Fig.2: H-Bond formation starch with cationic surfactants. Fig.3: Only cationic surfactant molecule.



From fig. 2 and fig. 3, it can be seen that starch molecule have many hydroxyl groups and hydrogen atoms which bind with surfactant molecule through H-atom called H-bond formation. So bond break down is easily of hydrophilic and hydrophobic parts of surfactant molecule, finally cleansing activity increased although starch are biodegradable and eco-friendly. XRD Figures 4, 5 and 6 has been given below for better understanding starch, SDS, CTAB complexes as variation of concentration.

The interactions between starch and all type of surfactants and their mixtures were studied by using surface

tension, solution viscosity measurements and to do the ternary phase diagram, FT-IR analysis for H- bond detection

and identification , SEM analysis for characterization for smoothness of surfaces and XRD analysis for crystallization

of complexes structure. The composition and structure of the complexes of starch and surfactants mixture were

studied by using phase equilibrium determination, Scanning electron microgram (SEM) and X-ray diffraction (XRD)

measurements. Critical association concentrations (cac) are well below the critical micellisation concentrations (CMC)

of the surfactants. Associative phase separation occurs in extremely dilute systems when the charge ratio between the

surfactants and the polymer is close to one. The effect of mixing on micellization of the binary surfactant solution

can be described by taking into account the effects of the volume difference between the hydrocarbon chains.

V. CONCLUSION The investigations presented in this paper show that strong ionic interaction occurs between cationic and anionic

surfactants (CTAB, SDS) except nonionic surfactant (Tween-20) and starch polymer, leads to phase separation

and precipitation of the formed amorphous complexes. Complex formation on starch depends on the chain length

difference in exactly in the same way as for free mixed micelles .The separated complex phase is a hydrophobic,

highly viscous and gel like containing 40 to 60% water. The highly and low water content of the complex phase

indicates that the interactions between the starch and ionic surfactants are very strong and they are capable more

effective washing properties in textile industry, dishwash in household, garments and laundry shops than normal

chemical detergent available in our indoor market. The polymeric surfactants which are newly prepared from

potato starch is also biodegradable and eco-friendly for environment not only this thisnatural surfactant from

natural sources help our green chemistry to safety for water living organism due to washable surfactant from

polymeric potato starch where small amount of chemical detergents also present.

Fig.4StarchXRD Fig.5Starch-SDScomplexesXRD

Fig.6Starch-CTABcomplexesXRD Fig. 4StarchXRD Fig.5Starch-SDScomplexesXRD



VI. ACKNOWLEDGMENT

The author is acknowledged to ministry of Science communication and Information Technology, Bangladesh for funded financial fellowship assistance for doctoral research work to continuous three fiscal year . I also Thanks to my beloved spouse SP Farida Yasmin BPM who inspired me to perform my Ph.D research work and my Supervisor Prof. Dr. Md. Ibrahim H. Mondal who helped me to reach my goal.

REFERENCES

[1] CA. Kozlowski,W.Walkowiak,“Removal of chromium(VI) from aqueous solutions by polymer inclusion membranes”. WaterRes 2002;vol.36:pp.4870–4876.

[2] S. Rio,A. Delebarre, “Removal of mercury in aqueous solution byfluidizedbedplantflyash”.Fuel2003;vol.82pp.153–159.

[3] R .Vander Oost,J. Beyer,PE. Vermeulen,“Fish bioaccumulation and biomarkers in environmental risk assessment”: a review.EnvironToxicolPharm2003;vol.13:pp.57–149.

[4] H. Bagheri,M. Saraji,“New polymeric sorbent for the solid- phase extraction of chlorophenols from water samples followed by gas chromatography-electron-captured etection”. J .Chromatogr A2001;910:87–93.

[5] KB. Lee, MB. Gu,SH.Moon,“Degradation of 2,4,6- tri nitrotoluene by immobilized horseradish peroxidase and electro generated peroxide”.WaterRes2003;vol.37:pp.983–992.

[6] HM. Hwang,LF. Slaughter, SM. Cook, H. Cui, “Photo chemical andmicrobialdegradationof2,4,6-trinitrotoluene(TNT)ina fresh water environment”.BullEnvironContamToxicol2000;vol.65:pp228–235.

[7] CI. Pearce,JR. Lloyd,JT.Guthrie,“The removal of colour from textile waste water using whole bacterial cells”: a review. Dyes Pigments 2003;vol.58:pp.179–196.

[8] G. McMullan,C. Meehan,A. Conneely,N. Kirby,T. Robinson, P. Nigam, et al. “Microbial decolourisation and degradation of textile dyes”.Appl. Microbiol Biotechnol2001;vol.56: pp.81–87.

[9] Y. Fu, T.Viraraghavan, “Fungal decolorization of dye wastewaters”: a review. Bio resour Technol 2001; vol.79:pp.251–262.

[10] B. Vander Bruggen,C. Vandecasteele,“Removal of pollutants from surface water and groundwater by nanofiltration:overviewof possible applications in the drinking water industry”. EnvironPoll2003;vol.pp.122:435–445.

[11] CassanoA, Molinari R, Romano M,Drioli E.“Treatment of aqueous effluents of the leather industry by membrane processes”: areview.JMembrSci2001;vol.181:pp.111–126.

[12] VV. Goncharuk , DD.Kucheruk, VM. Kochkodan , VP. Badekha,“Removal of organic substances from aqueous solutions by reagent enhance dreverseosmosis”.Desalination2002;143:45–51.

[13] RY. Ning, Arsenic removal by reverseosmosis.Desalination2002;vol.143:pp.237–41. [14] JM.Lee,MS. Kim,B. Hwang,W. Bae,BW. Kim,“Photo- degradation of acidred114dissolved using a photo-Fenton

process with TiO2”.Dyes Pigments2003;vol.56:pp59–67. [15] T. Kurbus, YM.SlokarLe .MajcenA. Marechal,DB, Voncina,“The use of experimental design for the evaluation of the influence of variables on the H2O2 /UV treatment of model textile waste water” Dyes Pigments 2003; vol.58:pp.171–178. [16] F. Torrades,M. Perez,HD. Mansilla,J. Peral,“Experimental design of Fenton and photo-Fenton reactions for the treatment of cellulose bleaching effluents”. Chemosphere2003;vol.53:pp.1211–1220. [17] F. Al-Momani,E. Touraud,JR. Degorce-Dumas,J. Roussy, O. Thomas,“Biodegradability enhancement of textile

dyes and textile waste water by VUV photolysis”. J.PhotochemPhotobiolAChem.2002;vol.153:p p.191–197. [18] U. Von Gunten,“Ozonation of drinking water: Part -IOxidation kinetics and product formation”. Water Res.2003;vol.37:pp.1443–1467. [19] X. Chen ,G. Chen , PL. Yue. “Novel electrode system for electro flotation of waste water”. Environ Sci.Technol

2002;vol.36:pp.778–783. [20] CY. Hu,SL. Lo,WH. Kuan,“Effects of co-existing anions on fluoride removal in electrocoagulation(EC) process

using aluminum electrodes.WaterRes2003;37:4513–4523.



[21] Z, Hu,L, Lei,Y.Li,Y. Ni, Chromium adsorption on high-performance activated carbons from aqueous solution. Sep. Purif Technol2003;vol.31:pp.13–18. [22] JM. Chern,YW. Chien,“Competitiveadsorption ofbenzoic acidandp-nitrophenol ontoactivatedcarbon:isotherm and

breakthrughcurves”.WaterRes2003;vol.37:pp.2347–2356. [23] MFR, Pereira,SF.,Soares, JMJ. Orfao,JL. Figueiredo, Adsorption of dyes on activated carbons :influence of

surface chemical groups”.Carbon2003;vol.41:pp.811–821. [24] J. Rivera-Utrilla,I. Bautista-Toledo,MA.Ferro-Garcia,C. Morenoastilla,“Bio adsorption of Pb(II) Cd(II), and

Cr(VI) on activated carbon from aqueous solutions”.Carbon2003;vol.41:pp.323–330. [25] S. Nouri,F. Haghseresht,GQM. Lu, “Comparison of adsorption capacity of p-cresol, 1p-nitrophenol by activated

carbon in singleanddoublesolute”.Adsorption2002;vol.8:pp.215–223. [26] MW. Jung,KH. Ahn,Y .Lee,KP.Kim,JS. Rhee,JT. Park,etal,“Adsorption characteristics of phenol and chloro phenolson Granular activated carbons (CAC) ”.Microchem.J.2001;vol.70:pp.123–131.

[27] ST. Bosso,J. Enzweiler,Evaluation of heavy metal removal from aqueous solution on toscolecite. Water Res.2002;vol.36:pp.4795–4800.

[28] VJ, Inglezakis,MD. Loizidou,HP. Grigoropoulou, “Ion exchangeof Pb2C,Cu2C, andCr3Connatural clino- ptilolite: selectivity determination and influence of acidity on metal uptake”J.ColloidIntSci2003;vol.261:pp.49–54.

[29] O. Abollino,M. Aceto,M. Malandrino,C. Sarzanini, E. Mentasti,“Adsorption of heavy metals on Na-montmorillonite Effect of pH and organic substances”. WaterRes2003;vol.37:pp .1619–1627.

[30] S. Al-Asheh,FA. Banat,L.Abu-Aitah,“Adsorption of phenol using different types of activated bentonites”. Sep Purif Technol2003;vol.33:pp.1–10.

[31] YH. Shen, “Removal of phenol from water by adsorption- flocculation using organobentonite”. Water Res.2002; vol.36:pp.1107–1114.

[32]R. Celis,Carmen,M. Hermosin , J . Cornejo,“Heavy metal adsorption by functionalized clays”. Environ Sci.Technol2000;vol.34:pp.4593–4599.

[33] O .Yavuz,Y. Altunkaynak,F.Guzel, .“Removal of copper, nickel, cobalt and manganese from aqueous solution by kaolinite”. WaterRes2003;vol.37:pp.948–952.

[34] M. Ghoul,M. Bacquet,M. Morcellet,“Uptake of heavy metals from synthetic aqueous solutions using modified PEI-silica gels”.WaterRes2003;vol.37:pp.729–734.

[35] A. Krysztafkiewicz,S. Binkowski,T. Jesionowski,“Adsorption of dyesonasilica surface”. ApplSurf.Sci2002; vol.199:pp31–39.

[36] FA. Lopez , MI. Martin , C. Perez, A. Lopez-Delgado, FJ. Alguacil,“Removal of copper ions from aqueous solutions By a steel- making by-product”. WaterRes2003;vol.37:pp.3883–3890. [37] VK. Garg,R. Gupta,AB. Yadav,R. Kumar.“Dye removal from aqueous solution by adsorption on treated saw dust” Bioresour Technol2003;vol.89:pp121–124. [38] S. Netpradit,P. Thiravetyan,S. Towprayoon,“Application of waste metal hydroxide sludge for adsorption of azo

reactive dyes”. WaterRes2004;vol.38:pp.71–78. [39] VK. Gupta,CK. Jain,I .Ali,M. Sharma,VK.Saini,.“Removal of cadmium and nickel from waste water using

bagasse fly ash a sugar industry waste”.WaterRes2003;vol.37:pp.4038–4044. [40] Z. Reddad,C .Gerente,Y. Andres,JF.Thibault,P..LeCloirec, “Cadmium and lead adsorption by natural polysaccharide in MF membrane reactor: experimental analysis and modeling WaterRes2003;vol.37:pp.3983–3991. [41] N. Calace,E. Nardi,BM. Petronio,M. Pietroletti,.Adsorption of phenols by paper mill sludges. Environ Poll

2002;118:315–319. [42] T. Robinson,B. Chandran,P.Nigam,“Studies on desorption of individual textile dyes and a synthetic dye effluent

from dye- adsorbed agriculturalresiduesusingsolvents”.BioresourTechnol2002;vol.84:pp.299–301. [43] T. Robinson,B. Chandran,P. Niga,“Removal of dyes from a synthetic textile dye effluent by biosorption on

applepomace and wheatstraw”.WaterRes2002;vol.36:pp.2824–2830. [44] P.Vasudevan,V. Padmavathy , SC. Dhingra,“Kinetics of bio sorption of cadmium on Baker’syeast”.Bioresour

Technol 2003;89:281–7. [45] MX. Loukidou ,KA. Matis,AI. Zouboulis,M..Liakopoulou- Kyriakidou,“Removal of As(V) from waste waters by



chemically modified fungal biomas”s.WaterRes.2003;vol.37:pp.4544–4552. [46]A. Zhang , T. AsakuraG.Uchiyama,“The adsorption mechanism of uranium(VI) from sea water on a

macroporous fibrous polymeric adsorbent containing amidoxime chelating functional group”. React Funct Polym. 2003;vol.57:pp.67–76.

[47]A.Atia,AM. Donia,SA. Abou-El-Enein,AM. Yousif,“Studies on uptake behavior of copper(II) and lead(II)by amine chelating resins with different textural properties”. Sep Purif Technol2003;vol.33:pp.295–301.

[48]BC. Pan,Y. Xiong,Q. Su,AM. Li,JL. Chen,QX. Zhang, “Role of amination of a polymeric adsorbent on phenol adsorption from aqueous solution”.Chemosphere2003;vol.51:pp.953–962. [49]VV. A zanova,J. Hradil,“Sorption properties of macroporous and hyper cross linked co-polymers”. React Funct

Polym1999;vol.41:pp.163–175. [50]J. Synowiecki, NA. Al-Khateeb,“Production, properties, and some new applications of chitin and its derivatives”.

Critical RevFoodSciNutr2003;vol.43:pp.145–171. [51] MNV. Ravi Kumar. “A review of chitin and chitosan applications”.React.FunctPolym2000;46:1–27. [52] SE.BaileyTJ. Olin,RM. Bricka,DD. AdrianA review of potentially low-cost sorbents for heavy metals. Water Res.

1999; vol.33:pp.2469–2479. [53] VP,YuryevA Cesaro,WJ Bergthaller,editors. Starch and starch containing origins-structure, properties and new

technologies Starch”. NewYork: NovaSciencePublishers, Inc.;2002. [54] OB. Wurzburg.In:OB. Wurzburg,editor.Modified starches: properties anduses.BocaRaton:CRCPress;1986. [55] PA. Sandford,J.BairdIn:GO. Aspinall, editor.“Industrial utilization of polysaccharides”. New York: Academic

Press;1983.p.983. [56] S.Babel ,TA.Kurniawan.“Low-cost adsorbents for heavy metals uptake from contaminated water”: a review.

JHazardous Mat2003;B97:pp.219–243. [57] AJ.Varma,SV.Deshpande,JF.Kennedy, “Metal complexation by chitosan and its derivatives”: a review.

Carbohydr Polym2004; vol.55:pp.77–93. [58] M.Singh R.Sharma UC.Banerjee,“Bio technological applications of cyclo dextrins”Bio technol Adv 2002; vol. 20: pp.341–359. [59] G,.CriniM. Morcelle,“Synthesis andapplications of adsorbents containing cyclodextrins”. J Sep Sci2002;vol.25:pp.789–813. [60] EMM.DelValle,“Cyclodextrinsandtheiruses:areview”.ProcBiochem2004;vol.39:pp.1033–46.

[61] W. Ciesielski CY. Lii MT, P.YenTomasik, Interactions of starch with salts of metals from the transition groups” CarbohydrPolym2003; vol.51:pp.47–56. [62] E.PolaczekF.StarzykK.MalenkiP. Tomasik,“Inclusion complexes of starches with hydrocarbons”. Carbohydr Polym2000;vol.43:pp.291–297.

[63] BA. Bolto,“Soluble polymer sin water purification.ProgPolymSci1995; vol.20: pp.987–1041. [64] Y.H.Paik,and G.Swift, “Chemistry of Industrial”,1995,Vol.16, pp. 55-62. [65] C.Huh, andS.G. Mason, “Colloid Polymer Sciience” ,1995 Vol. 253, p.566.

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