Removal of Copper and Methylene

Blue Dye from Artificial Wastewater Using

Sargassum-Bentonite Admix

by

Ma. Elena B. Bithao

Ma. Lorelie A. Nuez
Arman O. Suetos

An Undergraduate Research Report Submitted

to the School of Chemical Engineering and Chemistry
in Partial Fulfillment of the Requirements for the Degree

Bachelor of Science in Chemical Engineering

Mapa Institute of Technology

December 2006
 APPROVAL SHEET

This is to certify that we have supervised the preparation of and read the undergraduate
research report, entitled Removal of Copper and Methylene Blue Dye from Artificial
Wastewater Using Sargassum-bentonite Admix, prepared by Ma. Elena B. Bithao, Ma.
Lorelie A. Nuez and Arman O. Suetos and that the said report has been submitted for
final examination by the Oral Examination Committee.

Manuel R. De Guzman Arvin Neile B. Arugay

Course Coordinator Research Adviser

As members of the Oral Examination Committee, we certify that we have examined this
report hereby recommend that it be accepted as a fulfillment of the requirements for the
Degree in Bachelor of Science in Chemical Engineering.

Alvin R. Caparanga Kevin B. Dagbay

Panel Member 1 Panel Member 2

Rhoda B. Leron
Panel member 3

This undergraduate research report is hereby approved and accepted by the School of
Chemical Engineering and Chemistry as a partial fulfillment of the requirements for the
Degree in Bachelor of Science in Chemical Engineering.

Alvin R. Caparanga Luz L. Lozano

Dean, School of Chemical
Chair, Chemical Engineering
Engineering and Chemistry

ii
 ACKNOWLEDGEMENT

Completing a research study is not an easy task. It needs much time and effort for it to be
completed. Also, this study will not be successful without the great support from the people
whom we humbly extend our gratitude and appreciation. They are as follows:

To our family and friends, for their love and support and for being our inspirations in
completing this report.

To our research adviser, Engr. Arvin Neile Arugay, for sharing his knowledge and ideas,
for giving us directions, for helping us understand theories behind the studies, for motivating
us to complete this report and for his continuous guidance up to last minute of completion.

To our course adviser, Engr. Manuel de Guzman, for equipping us the knowledge we need
in completing our study, for his insights and suggestions and for patiently checking our draft
paper.

To Engr. Rhoda Leron, Research Center Head and Engr. Ariziel Ruth Marquez,
Laboratory Head for trusting and allowing us to use the laboratory equipments, apparatus,
glasswares and other facilities.

To Dean Luz Lozano, for allowing us to use the school facilities.

To the ChE-Chm laboratory personnels, Ate Kathleen, Ate Karen, Ate AJ, Ate Annilyn,
Ate Claire, Ate Lolit, Kuya Rico, Kuya Benjie, for all the assistance they extended to us.

To Engr. Blessie Basilia, for providing us the bentonite we need.

Most of all, to our Almighty Father, for the gift of life, the strength, wisdom of unconditional
love, in accomplishing this fruit of our labor, we offer to You our good Lord, our deepest
thank you LORD for all the gifts You have given us and for directing our path to the
following persons who have been instrumental in the completion of our undergraduate
research report.

For this achievement, we give back all the glory and praises to the omnipotent Father
Almighty.

Ma. Elena B. Bithao

Ma. Lorelie A. Nuez
Arman O. Suetos

iii
 TABLE OF CONTENTS

TITLE PAGE i

APPROVAL SHEET ii

ACKNOWLEDGEMENT iii

TABLE OF CONTENTS iv

LIST OF TABLES vi

LIST OF FIGURES viii

ABSTRACT ix

Chapter 1 : INTRODUCTION 1

Chapter 2 : LITERATURE REVIEW 4

2.1 Adsorbents 4

2.2 Sorption Kinetics 6

2.3 Sorption Equilibria and Isotherm 8

2.4 Factors Affecting Adsorption of Dyes and Heavy Metals 10

2.4.1 Influence of Initial pH 10

2.4.2 Influence of Shaking Rate 12

2.4.3 Influence of Sorbate Concentration 13

2.5 Removal of Copper and Dye in Textile Wastewater 14

Chapter 3 : REMOVAL OF COPPER AND METHYLENE BLUE DYE FROM

ARTIFICIAL WASTEWATER USING SARGASSUM-BENTONITE ADMIX 16

Abstract 16

Introduction 16

Methodology 19

iv
 v

Preparation of Sargassum ilicifolium 19

Preparation of Biomass 19

Protonation of Biomass 19

Preparation of sodium bentonite 20

Preparation of Sargassum ilicifolium sodium bentonite admix 20

Preparation of artificial wastewater 21

Sorption of copper and dye by Sargassum-bentonite admix 22

Sorption Kinetics 22

Sorption Equilibrium Experiments 25

Influence of pH 27

Determination of methylene blue dye and copper concentation 28

Results and Discussion 28

Sorption kinetics 28

Sorption isotherms 32

Influence of pH on sorption of copper and methylene blue dye

adsorption 37

Conclusion 40

References 41

Chapter 4 : CONCLUSION 45

Chapter 5 : RECOMMENDATION 46

REFERENCES 47

APPENDIX A : Sorption Kinetics 51

APPENDIX B : Sorption Isotherm 59

APPENDIX C : Influence of pH 63
 LIST OF TABLES

Table 2.1 Effect of Initial Dye Concentration on the MB Removal by Raw and
Chemically Activated Baggasse ( Raghuvanshi et al., 2004) 13
Table 2.2 Equilibrium Uptakes and Fraction of Copper Removed by Sargassum sp. at
Different Temperatures and Initial Concentrations (Antunes et al., 2003) 13

Table 1 Composition of Admix 20

Table 2 Amounts of Copper Nitrate Trihydrate 21
Table 3 Kinetic Parameters Obtained from the First Order and Pseudo-Second
Order Equations for the Sorption of Methylene Blue Dye at Different
Sorbent Composition 31
Table 4 Kinetic Parameters Obtained from the First Order and Pseudo-Second Order
Equations for the Sorption of Copper at Different Sorbent Composition 32
Table 5 Color Uptake and % Adsorption of Methylene Blue Dye at Different
Sorbent Compositions 34
Table 6 Methylene Blue Dye Uptake at Different Sorbent Compositions 35
Table 7 Copper Uptake at Different Sorbent Compositions 36
Table 8 Langmuir and Freundlich Parameters for Methylene Blue Dye at Different
Sorbent Compositions 37
Table 9 Langmuir and Freundlich Parameters for Copper at Different
Sorbent Compositions 37

Table A.1 Flame Atomic Absorption Spectrometer Analyzer (FAAS) Data of Copper
for Sorption Kinetics (DF = 25) of Wastewater Containing Copper and
Methylene Blue Dye at Different Sorbent Compositions 51
Table A.2 UV-VIS Spectrometer Data of Methylene Blue Dye for Sorption
Kinetics of Wastewater Containing Copper and Methylene Blue Dye at
Different Sorbent Compositions 52
Table A.3 Flame Atomic Absorption Spectrometer Analyzer (FAAS) Data of Copper
for Sorption Kinetics (DF = 25) of Wastewater Containing Copper Only at
Different Sorbent Compositions 53
Table A.4 UV-VIS Spectrometer Data of Methylene Blue Dye for Sorption
Kinetics of Wastewater Containing Methylene Blue Dye Only at
Different Sorbent Compositions 54
Table A.5 Methylene Blue Dye Uptake at Different Sorbent Compositions 55
Table A.6 Copper Uptake at Different Sorbent Compositions 56

Table B.1 Flame Atomic Absorption Spectrometer Analyzer (FAAS) Data of

Copper for Sorption Isotherm (DF = 10) of Wastewater Containing
Copper and Methylene Blue Dye at Different Sorbent Compositions 59
Table B.2 UV-VIS Spectrometer Data of Methylene Blue Dye for Sorption
Isotherm of Wastewater Containing Copper and Methylene Blue Dye
at Different Sorbent Compositions 59

vi
 vii

Table B.3 Flame Atomic Absorption Spectrometer Analyzer (FAAS) Data of

Copper for Sorption Isotherm (DF = 10) of Wastewater Containing
Copper Only at Different Sorbent Compositions 59
Table B.4 UV-VIS Spectrometer Data of Methylene Blue Dye for Sorption
Isotherm of Wastewater Containing Copper and Methylene Blue Dye at
Different Sorbent Compositions 60
Table B.5 Methylene Blue Dye Uptake at Different Sorbent Compositions 60
Table B.6 Copper Uptake at Different Sorbent Compositions 60
Table B.7 %Copper Adsorbed at Different Sorbent Compositions 60
Table B.8 %Methylene Blue Dye Adsorbed at Different Sorbent Compositions 61

Table C.1 Influence of pH on Copper Adsorption 63

Table C.2 Influence of pH on Methylene Blue Dye Adsorption 63
 LIST OF FIGURES

Figure 2.1 Sargassum ilifolium 5

Figure 2.2 Effect of Contact Time on Metal Sorption (Jeffers et al., 1990) 8
Figure 2.3 Freundlich Isotherm Plots for Adsorption of Copper and Cadmium
(Kapoor and Viraraghavan, 1998) 10
Figure 2.4 Effect of the Initial pH on Equilibrium Copper Ions Uptake by
Sargassum sp., (Antunes et al., 2003) 11
Figure 2.5 Influence of Shaking Rate on Equilibrium Copper Ions Uptake by
Sargassum sp. (Antunes et al., 2003) 12

Figure 1 Sorption Kinetics of Copper and Methylene Blue Dye fromWastewater

Containing Copper and Methylene Blue Dye at Different Sorbent
Compositions 29
Figure 2 Sorption Kinetics of Copper from Wastewater Containing Copper Only
at Different Sorbent Compositions 30
Figure 3 Sorption Kinetics of Methylene Blue Dye from Wastewater Containing
Methylene Blue Dye at Different Sorbent Compositions 30
Figure 4 Adsorption Isotherm of Copper from Wastewater Containing Copper and
Methylene Blue Dye at Different Sorbent Compositions 33
Figure 5 Adsorption Isotherm of Copper from Wastewater Containing Copper only at
Different Sorbent Compositions 33
Figure 6 Adsorption Isotherm of Methylene Blue Dye from Wastewater Containing
Copper and Methylene Blue Dye at Different Sorbent Compositions 34
Figure 7 Influence of pH on Copper Adsorption 38
Figure 8 Influence of pH on Methylene Blue Dye Adsorption 39

Figure A.1 First Order Kinetics for Methylene Blue Dye at Different Sorbent
Compositions 57
Figure A.2 Pseudo-Second Order Kinetics for Methylene Blue Dye at Different
Sorbent Compositions 57
Figure A.3 First Order Kinetics for Copper at Different Sorbent Compositions 58
Figure A.4 Pseudo-Second Order Kinetics for Copper at Different
Sorbent Compositions 58

Figure B.1 Langmuir Isotherm for Methylene Blue Dye at Different

Sorbent Compositions 61
Figure B.2 Freundlich Isotherm for Methylene Blue Dye at Different
Sorbent Compositions 61
Figure B.3 Langmuir Isotherm for Copper at Different Sorbent Compositions 62

viii
 ABSTRACT

The ability of combined Sargassum ilicifolium and sodium bentonite on

simultaneous removal of copper and methylene blue dye was investigated by batch kinetic
and isotherm experiments using artificial wastewater and different composition of the
sorbents. The rate of removal of copper and methylene blue was very fast for the first 30
minutes of the experiment where most of the copper and methylene blue were adsorbed.
Sorption kinetics and isotherm experiments of copper and methylene blue have been best
described by pseudo-second order equation and Freundlich isotherm, respectively. The admix
containing 50%Sargassum;50%bentonite was the most effective in reducing copper with
maximum copper uptake of 85.163 mg/g sorbent. On the other hand, for methylene blue
adsorption, the admix having 25%Sargassum;75%bentonite was the most effective with
maximum methylene blue uptake of 4.985 mg/g sorbent. For the simultaneous removal of
copper and methylene blue, the most effective sorbent composition was
50%Sargassum;50%bentonite.The sorption capacity increases as the initial copper
concentration increases while sorption capacity on methylene blue decreases as the initial
copper concentration increases. No effects of pH were observed at pH 3-6; however, greatest
adsorption for copper and methylene blue was achieved at pH 5. The results obtained in this
study have shown that Sargassum-bentonite admix constitutes a promising sorbent which
could compete with the existing commercial sorbents because of its high adsorption capacity
on simultaneous removal of color and heavy metal from aqueous solutions.

Keywords: Sargassum ilicifolium, sodium bentonite, copper, methylene blue dye,

simultaneous removal

ix
 Chapter 1

INTRODUCTION

Recently, water consumption and waste generation have become considerable

concerns for textile manufacturers and finishers. Textile industry uses dyes to color their final

products and their discharge into natural waters causes severe problems because textile

industry wastewater is characterized primarily by measurements of total dissolved suspended

solids, BOD, COD, color and. heavy metals. The presence of color and heavy metals are

considered to be very important with respect to their effects in the environment.

Heavy metals released into the environment tend to persist indefinitely, circulating

and eventually accumulating throughout the food chain thus becoming a serious threat to the

environment. Of various pollutants contained in industrial wastewaters, color is considered to

be very important especially from the aesthetic nature of the environment (Raghuvanshi et

al., 2004). Aside from aesthetic problem, the greatest environmental concern with dyes is

their absorption and reflection of sunlight in water which interferes with the growth of

bacteria to levels insufficient to degrade impurities in water (Allen and Koumanova, 2005).

Therefore, it is necessary to alleviate heavy metal burden and color of wastewaters before

discharging them into waterways.

The effluents of textile industry are difficult to treat by conventional biological and

physical-chemical techniques due to the complex structure of dyes (Robinson et al., 2001).

Sorption has evolved into one of the most effective processes for decolorization and heavy

metals removal of wastewater (Voudrias et al., 2001; Vieira and Volesky, 2000). Bentonite

clay had been utilized and proven effective in decolorization process in some studies. One of

1
 2

these studies is the study done by Go and Sese (2002), wherein they found out that heat-

treated bentonite clay can reduce the color of wastewater. Biomaterials such as seaweeds,

specifically Sargassum biomass are very promising materials to be used as sorbents in

wastewater treatment because they represent cheap source of sorbent since they are readily

available in large quantities. A study conducted by Antunes et al. (2003) showed that

Sargassum biomass is an excellent biomaterial for accumulating and recovering copper from

industrial solutions since it has high metal binding capacity.

Since textile effluents are characterized by heavy metals and color, developing a

new process that can simultaneously remove it is very promising. The possibility for

simultaneous removal of color and heavy metals from wastewater can be done through the

combination of Sargassum ilicifolium and sodium bentonite. To the best of our knowledge,

studies on simultaneous sorption of dye and heavy metal are not available; therefore, to

explore this field of sorption is desirable.

The main objective of this study is to evaluate the capability of the Sargassum-

bentonite admix in removing heavy metals and color from wastewater simultaneously.

Specifically, this study investigated the batch adsorption of the Sargassum-bentonite admix

which includes determination of the influence of sorbent composition on adsorption kinetics

and isotherms, and the effect of initial copper concentration on adsorption isotherms. In

addition, the effect of pH on copper and methylene blue dye adsorption was also evaluated.

The percentage composition of Sargassum-bentonite admix was varied, since two

kinds of sorbent were used. Batch adsorption studies of the Sargassum-bentonite were done

using artificial wastewater.

 3

The amount of sorbents used for the batch adsorption studies was constant.

Temperature, methylene blue dye concentration and shaking rate were constant. Column

studies were not included in the experiment.

The success of the study would constitute a sorbent that could remove color and

heavy metals from wastewater simultaneously. This study will open a way for other

researches that will explore the application of admix to actual textile wastewater.
 Chapter 2

LITERATURE REVIEW

Textile wastewaters contain harmful contaminants making their disposal deleterious

to environment and to humans. The major problem in wastewater treatment is the removal of

color and heavy metals. Several techniques of treating wastewaters already exist; however,

these techniques are extremely expensive and sometimes ineffective. Studies show the

efficiency of Sargassum ilicifolium and sodium bentonite in metal sorption and color

removal, respectively in treating wastewater; however, the treatment is usually done

separately (Antunes et al., 2003; Go and Sese, 2002; Voudrias et al., 2001; Vieira and

Volesky, 2000). Based on these studies, it is possible to develop for an effective way of

simultaneous removal of color and heavy metals and this is through the combination of

Sargassum ilicifolium and sodium bentonite. To our knowledge, there have been no studies

conducted regarding the combination of Sargassum-bentonite.

This literature review is divided into five areas: (1) Adsorbents (2) Sorption Kinetics

(3) Sorption Equilibria and Isotherm (4) Factors Affecting Sorption Capacity of Adsorbents,

and (5) Removal of Copper and Dye.

2.1 Adsorbents

Sorption has evolved into one of the most effective processes for heavy metals

removal and decolorization of wastewaters (Voudrias et al., 2001; Vieira and Volesky,

2000). The most commonly used adsorbent for color removal is activated carbon because of

its capability for efficiently adsorbing a broad range of different types of adsorbates.

4
 5

However, its use is limited because of its high cost (Voudrias et al., 2001). Bentonite clay is

also effective in treating wastewater and it is usually used as an alternative sorbent primarily

because of its low cost. Biosorption is the capacity of certain kinds of biomass to bind and

concentrate metals. The most commonly used biosorbents are seaweeds, molds, bacteria and

yeasts.

Sargassum ilicifolium is the type of biomass frequently utilized in the biosorptive

process due to its high adsorption capability. Figure 2.1 shows the picture of Sargassum

ilicifolium, the berrylike gas-filled bladders keep the plants afloat, thus promoting

photosynthesis. Many plants have rough sticky textures, which together with robust but

flexible bodies, help to withstand strong currents.

Figure 2.1 Sargassum ilifolium

Sargassum biomass is especially suitable for biosorption because its polysaccharide

content is not as easily leached out as those of other brown seaweeds used commercially as a

source of alginate (Vieira and Volesky, 2000). Sargassum species can be found throughout

tropical areas of the world and is widely distributed in the coastal waters of the Philippines

(Hurtado and Ragaza, 1999).

 6

Researches on the effectiveness of Sargassum ilicifolium in biosorption agree that

when biomass concentration and initial metal concentration increase, the rate of biosorption

also increases (Bungabong, 2003; Dadural and de Dios, 2005; Bautista and Demition, 2005).

However, the presence of other substances lowers the adsorption performance of the biomass

as shown in the studies of Dadural and de Dios (2005) and Bautista and Demition (2005)

where anionic and cationic impurities and non-ionic surfactant were introduced respectively.

On the other hand, bentonite has been used mainly for dye removal from

wastewater. Bentonite is a fine powder clay that has adsorbent properties and an alkaline pH

due to the presence of sodium, potassium and calcium components. Bentonite possesses

permanent negative charges on its surface due to isomorphous substitution and also has pH-

dependent negative or positive charge at the edges.

Go and Sese (2002), Ozcan et al. (2004) and Voudrias et al. (2001) agree that

bentonite is efficient in treating colored wastewaters. Voudrias et al. (2001) and Ozcan et al.

(2004) found out that natural bentonite clay could be employed as an alternative for activated

carbon, while Go and Sese (2002) preferred heat-treated bentonite than natural one.

Bentonite is also known to adsorb heavy metals from aqueous solutions. The study

done by Viraraghavan and Kapoor (1994) demonstrated the ability of bentonite to adsorb

mercury. It was also known to adsorb cesium (Khan et al., 1994) and Mn2+, Zn2+, Cd2+ and

Hg2+ (Stuanes, 1976).

2.2 Sorption Kinetics

The time concentration profile for adsorption is shown in adsorption kinetics. It is

mainly the particle mass transfer, which controls the overall adsorption kinetics (sorbent
 7

particle size, porosity, sorbate size and mixing in the sorption system). Knowing the kinetic

experiment helps us see and understand factors that affect the biosorption system. Thus,

sorption kinetics constitutes a major criterion in the determination of interest of sorption

processes (Volesky, 1999).

The minimum contact time is determined through a series of kinetics tests in which

a known mass of media is exposed to a polluted waste stream of known concentration for

specific amounts of time. At the end of each time increment, the concentration of the

metals/dyes in the solution are measured and the ratio of the final concentration to the initial

concentration is plotted against time. The time at which the curve begins to flatten is the

minimum contact time required for the development of pseudo-equilibrium. Although

removal may continue past this minimum time, longer contact times in general are not

economically efficient because the size of the adsorber will need to be much greater for

minimal additional removal (Clark et al., 2000).

Almost all researches regarding sorption have kinetics studies; among these

researches are the studies done by Jeffers et al. (1990) and Hu et al. (2005). Hu et al. (2005)

focused on the removal of commercial dye, Basic Red 2 (BR2) by bentonite and Jeffers et al.

(1990) focused on the removal of metal contaminants by immobilized biomass. In both

studies, equilibrium time was found to be less than 30 minutes which indicated that sorption

was very fast. Figure 2.2 shows the effect of contact time on metal sorption by Jeffers et al.

(1990). It can be observed from the figure that almost 50 % of the metal contaminants were

absorbed within 5 minutes of contact.

 8

Figure 2.2 Effect of Contact Time on Metal Sorption (Jeffers et al., 1990)

2.3 Sorption Equilibria and Isotherm

The most appropriate method for assessing sorbent capacity is the derivation of a

whole sorption isotherm. Sorption isotherm is the equilibrium between the concentration in

the fluid phase and the concentration in the adsorbent particles at a given temperature. For

liquids, concentration is usually expressed in units of mass, such as parts per million or mg of

metal/dye per liter of solution. The concentration of sorbate on the solid is expressed as mass

sorbed per unit of mass of the original sorbent.

An isotherm is favorable if its fixation capacity grows rapidly with concentration, is

in equilibrium in the liquid phase, and is in convex form. The highly favorable isotherm is

irreversible adsorption, where the amount adsorbed does not depend on the decrease in
 9

concentration down to very low values; unlike unfavorable isotherms, which have low

adsorption capacity at low concentrations, are in equilibrium and are in concave form.

In order to obtain the different points of the adsorption isotherm, the method in a

closed reactor consists of putting different known masses of the sorbent in contact with a

given volume of the solution containing the solute at an initial known concentration. After

the sorbent comes in contact with the solute solution, the samples are agitated in a uniform

manner to reach equilibrium. The time necessary to reach equilibrium depends on the system

being studied, so it is necessary to have prior knowledge of it to be used in the concentration

being measured.

Once equilibrium has been reached, the concentration of each sample is measured,

as is the final pH of the solution. The sorption capacity (color/metal uptake) is expressed as

follows:

Q=
(Ce Co )V (2.1)
M

where C0 and Ce are the initial and equilibrium concentrations in the solution (mg/L),

respectively; V is the solution volume (L); and M is the mass of sorbent (g).

Several equations or concepts in both static and dynamic contact model the mass

transfer between the solution and the solid phase. Sorption isotherms show the distribution of

solute between the liquid and solid phases. This relation is used in several models of dynamic

studies for the prediction of breakthrough curves, assuming various hypotheses as regards

mechanism and performances.

A wide array of equilibrium based models has been used to describe sorption on

solid surfaces. These include the usual isotherm such as those described by Freundlich,

Langmuir, and Braunner, Emmet and Teller (BET).

 10

In the study done by Kapoor and Viraraghavan (1998), the Freundlich model best

fitted their data on adsorption isotherms as shown in figure 2.3. As observed in figure 2.3, the

adsorption capacity for copper was higher than for cadmium when the equilibrium

concentration was less than 2.5 mg/L and for equilibrium concentration greater than 2.5

mg/L, cadmium adsorption was higher than copper adsorption.

Figure 2.3 Freundlich Isotherm Plots for Adsorption of Copper and Cadmium (Kapoor and
Viraraghavan, 1998)

2.4 Factors Affecting Adsorption of Dyes and Heavy Metals

2.4.1 Influence of Initial pH

It is well known that the pH of the medium affects the solubility of metal ions and

the concentration of the counter ions on the functional groups of the biomass cell walls, so

pH is an important parameter on sorption from aqueous solutions (Antunes et al., 2003).

 11

Sargassum species presents high content of ionizable groups (carboxyl groups from

mannuronic and guluronic acids) on the cell wall polysaccharides, which makes it, at least in

theory, very liable to the influence of the pH. As shown in Figure 2.4, the uptake of free ionic

copper depends on pH, increasing with the increase in pH from 2.0 to 3.0 and then reaching a

plateau in the range 4.0 - 5.0 (Antunes et al., 2003).

5
4
q (mg/g)

3
2
1
0
2 3 4 5
pH

Figure 2.4 Effect of the Initial pH on Equilibrium Copper Ions Uptake by Sargassum sp.,
(Antunes et al., 2003)

Similar results were reported on literature for different Cu (II)-biomass systems (Sag

et al., 1998; Zhou et al., 1998; Matheickal and Yu, 1999). At pH values lower than 3.0,

copper (II) removal was inhibited, possibly as a result of the competition between hydrogen

and copper ions on the sorption sites, with an apparent preponderance of hydrogen ions,

which restricts the approach of metal cations as in consequence of the repulsive force. As the

pH increased, the ligands such as carboxylate groups in Sargassum sp. were exposed,

increasing the negative charge density on the biomass surface, increasing the attraction of

metallic ions with positive charge and allowing the biosorption onto the cell surface (Antunes

et al., 2003).
 12

For copper (II) biomass systems experiments, initial pH values lower than 6.0

should be used since insoluble copper hydroxide starts precipitating from the solutions at

higher pH values (Antunes et al., 2003). For bentonite systems, pH ranges from 4.0 to 6.0

(Kapoor and Viraraghavan, 1998).

2.4.2 Influence of Shaking Rate

Antunes et al. (2003) investigated the influence of shaking rate in their evaluation of

copper biosorption by Sargassum species. Results of their study indicated that for shaking

rates higher than 100 rpm no significant changes in copper accumulation were observed as

shown in Figure 2.5.

5
4
q (mg/g)

3
2
1
0
0 50 100 150 200 250 300
pH

Figure 2.5 Influence of Shaking Rate on Equilibrium Copper Ions Uptake by Sargassum sp.
(Antunes et al., 2003)

According to Antunes et al. (2003), shaking rate in the range of 100-250 rpm is

sufficient to assure that all the cell binding sites is made available for copper uptake; while

for bentonite adsorption systems 125 rpm was enough (Kapoor and Viraraghavan, 1998)
 13

2.4.3 Influence of Sorbate Concentration

In sorption processes, most studies agreed that increasing the initial sorbate

concentration will increase the initial adsorption capacity because mass transfer driving force

is increased. One of the studies that proved the above-stated phenomenon is the study done

by Sotayco and Tamayo (2005) where they observed that increase in initial concentration of

Cu2+, Ni2+ and Pb2+ increases the amount of adsorbed metals at fixed seaweed loading.

Raghuvanshi et al. (2004) and Antunes et al. (2003) have the same observations. The results

of their studies are presented in Table.2.1 and Table 2.2, respectively.

Table 2.1 Effect of Initial Dye Concentration on the MB Removal by Raw and Chemically
Activated Baggasse ( Raghuvanshi et al., 2004)
Conc 50 ppm 100 ppm 150 ppm 200 ppm 250 ppm 300 ppm
Time RB CAB RB CAB RB CAB RB CAB RB CAB RB CAB
(mins)
15 61 71.5 56 66.3 44.5 61.6 38.7 55.5 28.5 43 20.6 31.9
30 80 80.9 69 77.9 58.8 67.5 48 60.3 35.5 48.9 33.7 36.6
45 84 89.5 78 83 66.2 72.6 54.7 64.9 41.2 54.8 38 39.2
60 86 92.5 84 85.7 70.3 78.9 56.6 68 47.4 57.3 39.9 42.7
90 89 94.8 86 87 74.3 83 61.3 69.7 49.3 59.3 42.4 44.6
120 90 96.1 89 90.1 78.3 84.9 66.2 72 51.8 61.5 44.4 46.3

Table 2.2 Equilibrium Uptakes and Fraction of Copper Removed by Sargassum sp. at
Different Temperatures and Initial Concentrations (Antunes et al., 2003)
Co 298 K 313 K 328 K
(g/mL) qc (mg/g) Xa (%) qc (mg/g) Xa (%) qc (mg/g) Xa (%)
a
18.4 4.3 (0.1) 89.1 (1.6) 4.3 (0.1) 89.3 (1.5) 4.1 (0.1) 87.6 (1.5)
36.9 8.3 (0.2) 90.1 (1.8) 8.3 (0.2) 90.2 (1.7) 8.3 (0.2) 86.8 (1.9)
92.2 21.3 (0.5) 92.4 (1.7) 21.3 (0.6) 92.3 (1.9) 21.4 (0.4) 91.6 (1.8)
184 40.0 (0.8) 87.0 (1.9) 38.0 (0.9) 82.6 (1.7) 42.5 (1.0) 92.4 (1.8)
277 53.3 (1.3) 77.0 (1.5) 53.1 (1.2) 76.6 (1.8) 57.0 (1.3) 82.2 (1.9)
369 57.9 (1.7) 62.8 (1.6) 57.6 (1.5) 62.4 (1.4) 60.8(1.6) 65.9 (1.5)
585 70.1 (1.9) 47.9 (1.7) 75.6 (2.0) 51.7 (1.9) 80.1 (1.9) 54.8 (1.8)
780 76.2 (2.0) 39.1 (1.4) 86.0 (1.8) 44.1 (1.6) 86.6 (1.9) 44.4 (1.8)
878 77.4 (2.1) 35.3 (1.7) 86.2 (2.0) 36.6 (2.0) 87.1 (2.0) 39.7 (1.9)
 14

2.5 Removal of Copper and Dye in Textile Wastewater

Water consumption and waste generation have become considerable concerns for

textile manufacturers and finishers. The presence of heavy metals and color are considered to

be very important in terms of their effects to the environment and to human life.

Heavy metals and color are introduced into the wastewater of textile manufacturing

through the use of premetalized dyes and heavy metal afterwashes, which are used to

increase the light fastness of the finished product (Demmin and Uhrich, 1988). A typical

heavy metal present in the textile wastewater is copper, which is very hazardous to human

and aquatic life at relatively low concentrations (Demmin and Uhrich, 1988). Copper may be

found as a contaminant in food, especially shellfish, mushroom, nuts, and chocolate. The

presence of copper (II) ions causes serious toxicological concerns (Davis et al., 2000), so

several studies were done to find the best method of removing it from wastewater. One of

these methods is biosorption. Biosorption is the capacity of certain kinds of biomass to bind

and concentrate metals.

Different biomasses were studied for biosorption which including Ulva reticulata

(Vijayaraghavan et al., 2004) and Sargassum species (Antunes et al., 2003; Bungabong,

2003; Davis et al., 2004). The influence of different experimental parameters such as initial

pH, shaking rate, sorption time, equilibrium conditions and initial concentrations of copper

ions on copper uptake was evaluated. Researchers agree that for shaking rates higher than

100 rpm no significant changes in copper accumulation as well as for pH were observed;

Ulva reticulata has a maximum copper (II) uptake of 74.63 mg/g determined at a pH of 5.5

and its equilibrium data fitted both Langmuir and Freundlich isotherm models
 15

(Vijayaraghavan et al., 2004). Outstanding copper uptake was also observed in Sargassum

species which is 1.48mmol/g biomass (Antunes et al., 2003).

Aside from heavy metals, another major problem encountered in the textile industry

wastewater is color coming from dyes (Pala, 2001; Raghuvanshi et al., 2004). Dyes are

chemicals which on binding with a material will give color to the material. Dyes are ionic,

aromatic organic compounds with structures aryl rings which have delocalized electron

systems. One of the major dyes used in textile industry is methylene blue dye, a cationic dye

with an amine group attached to polycyclic carbon atoms which is widely used in cotton

fabrics. It is known for its strong adsorption onto solids and its recognized usefulness in

characterizing adsorptive material (Demmin and Urich, 1998).

The greatest environmental concern with dyes (specifically methylene blue dye) is

their absorption and reflection of sunlight in water which interferes with the growth of

bacteria to levels insufficient to degrade impurities in water (Allen and Koumanova, 2005).

Studies regarding the reduction of color in wastewater were conducted to alleviate the

previously stated problem. Sorption was found to be a very promising process. Among of the

sorbents strudied for methylene blue dye removal were bagasse (Raghuvanshi et al., 2004)

and bentonite (Al-Asheh et al., 2003; Go and Sese, 2002).

Bagasse and bentonite were proven effective in adsorbing color. Raghuvanshi et al.

(2004) proved that rate of methylene blue dye adsorption on baggase increases with rising

temperature. However, with regards to the use of bentonite, thermal or heat-treated bentonite

was more effective than natural bentonite as demonstrated in the studies of Go and Sese

(2002) and Al-Asheh et al. (2003). It was also observed by Al-Asheh et al. (2003) that

greater removal of methylene blue dye occurred at higher bentonite concentration.

 Chapter 3

REMOVAL OF COPPER AND METHYLENE BLUE DYE FROM ARTIFICIAL

WASTEWATER USING SARGASSUM-BENTONITE ADMIX

Abstract

The ability of combined Sargassum ilicifolium and sodium bentonite on

simultaneous removal of copper and methylene blue dye was investigated by batch kinetic
and isotherm experiments using artificial wastewater and different composition of the
sorbents. The rate of removal of copper and methylene blue was very fast for the first 30
minutes of the experiment where most of the copper and methylene blue were adsorbed.
Sorption kinetics and isotherm experiments of copper and methylene blue have been best
described by pseudo-second order equation and Freundlich isotherm, respectively. The admix
containing 50%Sargassum;50%bentonite was the most effective in reducing copper with
maximum copper uptake of 85.163 mg/g sorbent. On the other hand, for methylene blue
adsorption, the admix having 25%Sargassum;75%bentonite was the most effective with
maximum methylene blue uptake of 4.985 mg/g sorbent. For the simultaneous removal of
copper and methylene blue, the most effective sorbent composition was
50%Sargassum;50%bentonite.The sorption capacity increases as the initial copper
concentration increases while sorption capacity on methylene blue decreases as the initial
copper concentration increases. No effects of pH were observed at pH 3-6; however, greatest
adsorption for copper and methylene blue was achieved at pH 5. The results obtained in this
study have shown that Sargassum-bentonite admix constitutes a promising sorbent which
could compete with the existing commercial sorbents because of its high adsorption capacity
on simultaneous removal of color and heavy metal from aqueous solutions.

Keywords: Sargassum ilicifolium, sodium bentonite, copper, methylene blue dye,

simultaneous removal

Introduction

Recently, water consumption and waste generation have become considerable

concerns for textile manufacturers and finishers. Textile industry uses dyes to color their final

16
 17

products and their discharge into natural waters causes severe problems because textile

industry wastewater is characterized primarily by measurements of total dissolved suspended

solids, BOD, COD, color and. heavy metals. The presence of color and heavy metals are

considered to be very important with respect to their effects in the environment.

Heavy metals released into the environment tend to persist indefinitely, circulating

and eventually accumulating throughout the food chain thus becoming a serious threat to the

environment. Of various pollutants contained in industrial wastewaters, color is considered to

be very important especially from the aesthetic nature of the environment (Raghuvanshi et

al., 2004). Aside from aesthetic problem, the greatest environmental concern with dyes is

their absorption and reflection of sunlight in water which interferes with the growth of

bacteria to levels insufficient to degrade impurities in water (Allen and Koumanova, 2005).

Therefore, it is necessary to alleviate heavy metal burden and color of wastewaters before

discharging them into waterways.

The effluents of textile industry are difficult to treat by conventional biological and

physical-chemical techniques due to the complex structure of dyes (Robinson et al., 2001).

Sorption has evolved into one of the most effective processes for decolorization and heavy

metals removal of wastewater (Voudrias et al., 2001; Vieira and Volesky, 2000). Bentonite

clay had been utilized and proven effective in decolorization process in some studies. One of

these studies is the study done by Go and Sese (2002), wherein they found out that heat-

treated bentonite clay can reduce the color of wastewater. Biomaterials such as seaweeds,

specifically Sargassum biomass are very promising materials to be used as sorbents in

wastewater treatment because they represent cheap source of sorbent since they are readily

available in large quantities. A study conducted by Antunes et al. (2003) showed that
 18

Sargassum biomass is an excellent biomaterial for accumulating and recovering copper from

industrial solutions since it has high metal binding capacity.

Since textile effluents are characterized by heavy metals and color, developing a

new process that can simultaneously remove it is very promising. The possibility for

simultaneous removal of color and heavy metals from wastewater can be done through the

combination of Sargassum ilicifolium and sodium bentonite. To the best of our knowledge,

studies on simultaneous sorption of dye and heavy metal are not available; therefore, to

explore this field of sorption is desirable.

The main objective of this study is to evaluate the capability of the Sargassum-

bentonite admix in removing heavy metals and color from wastewater simultaneously.

Specifically, this study investigated the batch adsorption of the Sargassum-bentonite admix

which includes determination of the influence of sorbent composition on adsorption kinetics

and isotherms, and the effect of initial copper concentration on adsorption isotherms. In

addition, the effect of pH on copper and methylene blue dye adsorption was also evaluated.

The percentage composition of Sargassum-bentonite admix was varied, since two

kinds of sorbent were used. Batch adsorption studies of the Sargassum-bentonite were done

using artificial wastewater.

The amount of sorbents used for the batch adsorption studies was constant.

Temperature, methylene blue dye concentration and shaking rate were constant. Column

studies were not included in the experiment.

 19

The success of the study would constitute a sorbent that could remove color and

heavy metals from wastewater simultaneously. This study will open a way for other

researches that will explore the application of admix to actual textile wastewater.

Methodology

Preparation of Sargassum ilicifolium

Preparation of Biomass

The biomass used in this study was Sargassum ilicifolium, a brown seaweed collected

from Bolinao, Pangasinan. The seaweeds were washed with fresh water to remove shells,

stones, sand and other nutrients deposited on the seaweeds. The seaweeds were sun dried to

remove the moisture content. The seaweeds were then transferred to an oven maintained at

temperature of 60C and dried there to constant weight. The dried seaweeds were milled

using Wiley Mill to reduce the size and were screened using RO-tap Sieve Shaker with mesh

numbers 30, 50, 70 and 100. Particles mesh number -100 were used for protonation.

Protonation of Biomass

Protonation was done to enhance the active surface sites of the seaweed. The dried

seaweed or biomass was soaked in 0.1 M HCl for 24 hours. The solution was decanted and

the seaweed was washed thoroughly with distilled water. After the final washing, the

biomass was filtered to drain the water and then dried in the oven set at 60C. The seaweeds
 20

were left in the oven until they attained a constant weight to ensure that no more moisture

was present in the biomass.

Preparation of sodium bentonite

Sodium bentonite was dried and milled using Wiley Mill. The milled bentonite was

screened using RO-tap Sieve Shaker with mesh numbers 30, 50, 70 and 100. Particles mesh

number -100 were collected, placed in a plastic container and stored in a dessicator.

Preparation of Sargassum ilicifolium sodium bentonite admix

Different samples of S. ilicifolium and sodium bentonite admix were prepared. And

the percentage compositions of the two components were varied. Each sample was composed

of approximately twenty grams with varying amounts of S. ilicifolium and sodium bentonite.

Table 1 shows the composition of different admix samples used in the experiment.

Table 1 Composition of Admix

Sargassum ilicifolium Sodium Bentonite

SAMPLE
grams grams

A 20 0
B 15 5
C 10 10
D 5 15
E 0 20
 21

Preparation of artificial wastewater

Different samples of wastewater containing methylene blue dye and copper were

prepared. The methylene blue dye concentration was constant for varying copper

concentrations. A separate set of wastewater was also prepared which contained separately

the methylene blue dye and copper. These samples of wastewater were prepared to compare

the efficiency of the sorbents in removing color and heavy metals from wastewater.

The concentration of methylene blue dye was held constant at 50 ppm. This was

based on the studies conducted by Gupta et al. (2000) and Raghuvanshi et al. (2004) because

in their studies, maximum adsorption of methylene blue dye was achieved at an initial

concentration of 50 ppm.

Copper concentration was varied by adding different amounts of copper nitrate

trihydrate presented in table 2.

Table 2 Amounts of Copper Nitrate Trihydrate

Copper Concentration Copper Nitrate

Ppm Trihydrate, g

200 0.7601
400 1.5202
600 2.2803
800 3.0404
1000 3.8005

The artificial wastewater was prepared by dissolving 55.63 mg methylene blue dye

with 1000 mL of distilled water. The desired amount of copper nitrate trihydrate was then
 22

added to 100 mL of the methylene blue dye solution diluting it quantitatively to 1000 mL

using the rest of the dye solution.

Sorption of copper and dye by Sargassum-bentonite admix

To evaluate the efficiency of Sargassum-bentonite admix, the effect of contact time,

sorbent composition, initial copper concentration, and pH on heavy metal and color removal

were studied in a series of kinetic and equilibrium experiments.

In this study, two kinds of sorbents were used, Sargassum ilicifolium and sodium

bentonite. To evaluate its sorption behavior, different sorbent compositions were studied. The

sorbent compositions include (100% bentonite, 0% Sargassum), (75% bentonite, 25%

Sargassum), (50% bentonite, 50% Sargassum), (25% bentonite, 75% Sargassum), and (0%

bentonite, 100% Sargassum).

Sorption Kinetics

In each kinetic experiment, 4g of sorbent was contacted with 400 mL of artificial

wastewater in a 750 mL erlenmeyer flask and was shaken constantly using Gyrotory Bath

Shaker at room temperature for 3 hours. The initial concentrations of copper and methylene

blue dye are 200 ppm and 50 ppm, respectively. Aliquots (15 mL) were withdrawn after 1

minute of contact and then for every 5 minutes interval for 1 hour and for the second and

third hour, aliquots were taken every 30 minutes. The collected aliquots were then

centrifuged for 30 minutes. Two mL were collected from each aliquot for digestion to

determine the final concentration of copper. The remaining sample was used for the
 23

determination of the final concentration of methylene blue dye. Digestion was done by

diluting the sample to 50 mL, adding 5 mL of concentrated nitric acid and heating the

solution at very low temperature until its total volume was decreased by half. After heating,

the solution was diluted to 50 mL

The samples were analyzed for methylene blue dye and copper content using UV-

VIS Spectrophotometer and Flame Atomic Absorption Spectrophotometer analyzer (FAAS),

respectively.

The data from this experiment was used to determine the rate constants for the

sorption of methylene blue dye and copper. These experiments were used to establish the

equilibrium time between the sorbent and the wastewater. This equilibrium time was used as

contact time in the equilibrium and isotherm experiments.

The amount of adsorption at time t or the adsorbate uptake (Qt, mg/g) was calculated

by:

Qt =
(Co Ct )V (3.1)
m

where the C0 and Ct are the initial concentration and equilibrium concentration at time t in

the solution (mg/L), respectively; V is the solution volume (L); and m is the mass of sorbent

(g).

In order to elucidate the behavior of the adsorption process, several models were

tested. A simple kinetic analysis is the first order Lagergren equation as shown in equation

3.2 (Lagergren, 1898).

dQt
= k1 (Qe Qt ) (3.2)
dt
 24

Integrating equation 3.2 for the boundary conditions Qt = 0 at t = 0 and Qt = t at t =

t gives equation 3.3.

ln (Qe Qt ) = ln Qe k1Qt (3.3)

Equation 3.3 is the integrated rate law for a first order reaction. Where Qe and Qt are

the sorption capacity at equilibrium and at time t, respectively (mg/g) and k1 is the

equilibrium rate constant of first order sorption (min-1). Equation 3.3 can be expressed as

follows:

(
Qt = Qe 1 e k1t ) (3.4)

Pseudo-second order equation (Ho et al.,1996; Ho and Mckay, 1998; Ho and

Mckay, 2000) based on the adsorption equilibrium capacity, was tested:

dQ 2
= k 2 (Qe Qt ) (3.5)
dt

After integration, applying boundary conditions ns Qt = 0 at t = 0 and Qt = t at t = t

gives equation 3.6.

2
Qe k 2 t
Qt = (3.6)
1+ Qe k 2 t

Equation 3.6 is the integrated rate law for a pseudo-second order reaction. Where Qe

and Qt are the sorption capacity at equilibrium and at time t, respectively (mg/g) and k2 is the

equilibrium rate constant of pseudo-second order sorption (gmg-1min-1). Equation 3.6 can be

rearranged in linear form as shown in equation 3.7.

t 1 1
= 2
+ t (3.7)
Qt k 2 Qe Qe
 25

If pseudo-second order kinetics are applicable, the plot of t/Qt against t should give a

linear relationship, from which Qe and k2 can be determined from the slope and the intercept,

respectively.

Sorption Equilibrium Experiments

In each sorption experiment, 1 g of sorbent was contacted with100 mL of artificial

wastewater. The experiment was done at room temperature with constant shaking rate.

In this study, the effect of initial copper concentration on equilibrium isotherm was

investigated. The concentrations of copper solution prepared were 200, 400, 600, 800 and

1000ppm with constant methylene blue dye concentration of 50 ppm on a 250-ml

Erlenmeyer flask with a volume of 100ml. Different percentage compositions of sorbents

were used in each initial copper concentration. The resulting mixtures were placed in a

Gyrotory Bath Shaker at 125 rpm for 3 hours to allow the constituents to be in contact with

each other, so that equilibrium would be reached between the medium and the solution.

The pH of all concentration was maintained at pH 5 by adding 0.1 M NaOH and 0.1

M HCl every 15 minutes. At the end of the contact period, the media were allowed to settle

and the supernatant solutions were centrifuged for 30 minutes. Ten mL was collected from

each aliquot for digestion to determine the final concentration of copper. The remaining

sample was used for the determination of the final concentration of methylene blue dye using

UV-VIS Spectrophotometer. Digestion was done by diluting the sample to 50 mL, adding 5

mL of concentrated nitric acid and heating the solution at very low temperature until its total

volume was decreased by half. After heating, the solution was diluted to 50 mL and analyzed

for copper content using Flame Atomic Adsorption Spectrometer (FAAS).

 26

Two models were used to plot the sorption isotherm, which were used to predict the

media adsorption capacity. The Langmuir sorption model was chosen for the estimation of

maximum copper sorption by the biosorbent. The Langmuir isotherm can be expressed as,

Qmax bCe
Q= (3.8)
1 + bCe

where Q is the color/metal uptake, Qmax is the maximum color/metal uptake (mg/g), Ce is the

equilibrium concentration and b is the Langmuir equilibrium constant (L/mg). The

constant b is a direct measure for the intensity of the sorption process (L/mg). For fitting the

experimental data, the Langmuir model was linearized as shown in equation 3.9.

1 1 1
= + (3.9)
Q Qmax bQmax Ce

The Freundlich model is represented by the equation,

1
n
Q = KCe (3.10)

where Q is the color/metal uptake, Ce is the equilibrium concentration, K (L/g) and n are

constants. K represents the quantity of dye/metal sorbed in mg/g adsorbent for a unit

equilibrium concentration of the compound under test and 1/n is a measure for the sorption

intensity. For n=1 the partition between the two phases is independent of the concentration. A

value for 1/n below one indicates a normal Langmuir isotherm, while 1/n above one is

indicative for a cooperative sorption (Mohan and Karthikeyan, 1997; Atkins, 1970). For

fitting the experimental data, the Freundlich model was linearized as follows,

1
ln Q = ln K + ln Ce (3.11)
n
 27

The amount of color and metal adsorbed by the sorbent was calculated from the

differences between color and metal quantity added to the biomass and color and metal

content of the supernatant using equation 3.12.

Q=
(Ce Co )V (3.12)
M

where Q is the color/metal uptake (mg/g); C0 and Ce are the initial and equilibrium

concentrations in the solution (mg/L), respectively; V is the solution volume (L); and M is

the mass of sorbent (g).

Influence of pH

In the evaluation of the influence of pH on sorption capacity of the sorbent, sorbent

composition of 50% bentonite and 50% Sargassum was used. The experiment was carried

out by having constant initial methylene blue dye of 50 ppm and initial copper concentration

of 200 ppm with varying values of pH from 3-9. The pH was adjusted every 15 minutes

using 0.1 M NaOH and 0.1 M HCl. The resulting mixtures were placed in a Gyrotory Bath

Shaker at 125 rpm for 3 hours to allow the constituents to be in contact with each other, so

that equilibrium would be reached between the medium and the solution.

At the end of the contact period, the media were allowed to settle and the

supernatant solutions were centrifuged. Twenty-five mL was collected from each aliquot for

digestion to determine the final concentration of copper. The remaining sample was used for

the determination of the final concentration of methylene blue dye using UV-VIS

Spectrophotometer. Digestion was done by diluting the sample to 50 mL, adding 5 mL of

concentrated nitric acid and heating the solution at very low temperature until its total
 28

volume was decreased by half. After heating, the solution was diluted to 50 mL and analyzed

for copper content using Flame Atomic Adsorption Spectrometer (FAAS).

Determination of methylene blue dye and copper concentation

The concentrations of methylene blue dye and copper in the solutions before and

after the equilibrium were determined using UV-VIS Spectrophotometry and Flame Atomic

Absorption Spectrometry (FAAS), respectively. The equipment used for FAAS was Perkin-

Elmer Analyst 300 atomic absorption spectrometer equipped with deuterium arc background

corrector, an air-acetylene burner and controlled by IBM personal computer. The hollow

cathode lamp was operated at 15 mA and the analytical wavelength was set at 324.8 nm for

copper determination. For UV-VIS Spectrophotometry, the equipment used was Perkin

Elmer Lambda 40. The analytical wavelength used was 665 nm to determine methylene blue

dye concentration.

Results and Discussion

Sorption kinetics

Figure 1 shows the comparison of sorption kinetics at different sorbent compositions

whrerein shaded and unshaded points represent data for copper and methylene blue dye,

respectively. It can be observed that the rate of removal of copper and methylene blue was

very fast for the first 30 minutes where most of the copper and methylene blue dye was

adsorbed. Determination of equilibrium time was not necessary since the adsorption was very
 29

fast. Comparing figures 1, 2 and 3, it can be observed that more copper and/or dye were

removed when both contaminants were present in the wastewater.

60
200 Shaded points: for copper (primary axis)
Unshaded points: for methylene blue dye (secondary axis)
100%Sargassum;0%Bentonite 75%Sargassum;25%Bentonite
50
50%Sargassum;50%Bentonite 25%Sargassum;75%Bentonite
Cf,mg/L(for COPPER)

0%Sargassum;100%Bentonite 100%Sargassum;0%Bentonite

Cf, mg/L (for MBD)

150 75%Sargassum;25%Bentonite 50%Sargassum;50%Bentonite
40
25%Sargassum;75%Bentonite 0%Sargassum;100%Bentonite

100 30

20
50
10

0 0
0 10 20 30 40 50 60 70
Time, minute

Figure 1 Sorption Kinetics of Copper and Methylene Blue Dye from Wastewater Containing
Copper and Methylene Blue Dye at Different Sorbent Compositions
 30

200
100%Sargassum;0%Bentonite
75%Sargassum;25%Bentonite
150 50%Sargassum;50%Bentonite
Cf, mg/L 25%Sargassum;75%Bentonite
0%Sargassum;100%Bentonite
100

50

0
0 20 40 60 80 100 120 140 160 180
Time, minute

Figure 2 Sorption Kinetics of Copper from Wastewater Containing Copper Only at Different
Sorbent Compositions

60
100%Sargassum;0%Bentonite
50 75%Sargassum;25%Bentonite
50%Sargassum;50%Bentonite
40
Cf, mg/L

25%Sargassum;75%Bentonite
30 0%Sargassum;100%Bentonite

20

10

0
0 20 40 60 80 100 120 140 160 180
Time, minute
Figure 3 Sorption Kinetics of Methylene Blue Dye from Wastewater Containing Methylene
Blue Dye Only at Different Sorbent Compositions

The experimental data were fitted to first order and pseudo-second order equations

to determine rate constants and adsorption capacities at equilibrium. The kinetic parameters

for methylene blue dye and copper adsorption were calculated by fitting experimental data
 31

results to equation 3 and 7 for first order and pseudo-second order, respectively. It was found

that the adsorption for both copper and methylene blue dye on different sorbent compositions

show better compliance with the pseudo-second order equation which were based on the

correlation coefficients generated. The values obtained for kinetic parameters of methylene

blue dye and copper adsorption are shown in tables 3 and 4 together with their corresponding

correlation coefficients.

Highest equilibrium adsorption capacities for copper and methylene blue dye were

obtained at 100%Sargassum; 0%bentonite while lowest equilibrium adsorption capacities

were obtained at 75% Sargassum; 25% bentonite for copper and 50% Sargassum; 50%

bentonite for methylene blue dye. As for the rate constants, high values for copper and

methylene blue dye were obtained at 75% Sargassum; 25% bentonite and 50% Sargassum;

50% bentonite, respectively while lowest rate constants were obtained at 100%Sargassum;

0%bentonite for copper and methylene blue dye.

Table 3 Kinetic Parameters Obtained from the First Order and Pseudo-Second Order
Equations for the Sorption of Methylene Blue Dye at Different Sorbent Composition
First Order Pseudo-Second Order
Composition 2
Qe k1 R Qe k2 R2
100% S;0%B 1.0180 0.0003 0.6058 55.5556 0.0016 1.0000
75% S;25%B 1.0421 0.0010 0.6209 21.0970 0.0111 1.0000
50% S;50%B 1.1148 0.0017 0.9141 4.5413 0.2360 0.9986
25% S;75%B 1.0221 0.0004 0.8030 4.9875 0.2005 1.0000
0% S;100%B 1.0260 0.0004 0.8204 4.9751 0.2010 0.9999
 32

Table 4 Kinetic Parameters Obtained from the First Order and Pseudo-Second Order
Equations for the Sorption of Copper at Different Sorbent Composition
First Order Pseudo-Second Order
Composition 2
Qe k1 R Qe k2 R2
100% S;0%B 1.1216 0.0023 0.7212 13.2802 0.0687 0.9988
75% S;25%B 1.4486 0.0052 0.9143 4.8804 0.7080 0.9828
50% S;50%B 1.4487 0.0044 0.6439 7.0522 0.3222 0.9723
25% S;75%B 2.0892 0.0128 0.9247 1.3617 8.3104 0.8951
0% S;100%B 1.8080 0.0092 0.6875 2.3491 1.7325 0.9691

Sorption isotherms

The copper and methylene blue dye sorption isotherms are shown in figure 4 and

figure 5, respectively. Ce (mg/L) is the final equilibrium concentration remaining in the

solution and Q (mg/g) is the color and metal uptake.

Copper adsorption isotherm is non-linear indicating that the sorption occurred by

physical adsorption mechanism. Physical adsorption occurs when weak interparticle bonds

exist between the adsorbate and adsorbent. The isotherm generated for methylene blue dye

was linear (as shown in Figure 6) since constant initial concentration of methylene blue dye

was used. When both copper and methylene blue dye were present in the wastewater (based

on figures 4, 5, and 6 and table 5), it can be observed that higher uptake of copper and/or dye

was observed.
 33

90.000
80.000
Q (mg copper/ g sorbent)

70.000
60.000
50.000
40.000
30.000
20.000
100%Sargassum;0%Bentonite
10.000 75%Sargassum;25%Bentonite
50%Sargassum;50%Bentonite
25%Sargassum;75%Bentonite
0.000
0 50 100 150 200
Ce(mg/L)

Figure 4 Adsorption Isotherm of Copper from Wastewater Containing Copper and

Methylene Blue Dye at Different Sorbent Compositions

80
70
Q (mg copper/ g sorbent)

60
50
40
30
20
100%Sargassum;0%Bentonite 75%Sargassum;25%Bentonite
10 50%Sargassum;50%Bentonite 25%Sargassum;75%Bentonite
0%Sargassum;100%Bentonite
0
0 50 100 150 200 250 300 350 400 450 500
Ce(mg/L)

Figure 5 Adsorption Isotherm of Copper from Wastewater Containing Copper only at

Different Sorbent Compositions
 34

6.000

Q(mg MBD/g sorbent) 5.000

4.000

3.000

2.000 100% Sargassum;0%Bentonite 75%Sargassum;25%Bentonite

50%Sargassum;50%Bentonite 75%Sargassum;25%Bentonite
1.000 0%Sargassum;100%Bentonite

0.000
0 0.5 1 1.5 2 2.5 3 3.5
Ce(mg/L)

Figure 6 Adsorption Isotherm of Methylene Blue Dye from Wastewater Containing Copper
and Methylene Blue Dye at Different Sorbent Compositions

Table 5 Color Uptake and % Adsorption of Methylene Blue Dye at Different Sorbent
Compositions
Composition Color Uptake % Adsorption
100% S;0%B 4.840 96.790
75% S;25%B 4.504 90.072
50% S;50%B 3.727 74.540
25% S;75%B 3.146 62.928
0% S;100%B 3.479 69.572

Based on batch adsorption tests, figure 4 shows the effectiveness of Sargassum-

bentonite admix towards copper adsorption which was composition

50%Sargassum;50%bentonite>75%Sargassum;25%bentonite>100%Sargassum;0%bentonite

>25%Sargassum;75%bentonite>0%Sargassum;100%bentonite. As shown in figure 6, the

performance of sorbents in color reduction can be summarized as follows, composition 25%

Sargassum; 75% bentonite > 0% Sargassum ; 100% bentonite > 100% Sargassum; 0%

bentonite > 25% Sargassum; 75% bentonite > 50% Sargassum; 50% bentonite. These results

indicate that sorbent composition has an effect in the adsorption of copper and methylene
 35

blue dye. In sorbents containing more Sargassum, higher copper uptake was observed, while

in sorbents having higher amount of bentonite color higher uptake was also observed.

The results on methylene blue dye adsorption at different sorbent compositions are

close to each other and the highest copper removal was observed at sorbent composition

50%Sargassum;50%bentonite. Therefore, for the simultaneous removal of copper and

methylene blue dye, the most effective sorbent composition was

50%Sargassum;50%bentonite.

The adsorption of copper and methylene blue dye in both Sargassum and bentonite

can be explained by the compatibility of their respective properties. Methylene blue dye

carries positive charges similar to heavy metals. Bentonite possesses permanent negative

charges on its surface due to isomorphous substitution, while, the presence of carboxyl and

sulphate groups (metal-sequestering sites) in seaweeds generate a negatively charged surface.

Sorption of positively charged methylene blue dye and copper is governed by ion exchange

with interlayer cations and formation of surface complexes in bentonite, and electrostatic

interaction between negative and positive ions in Sargassum (Sabodina et al., 2004; Cossich

et al., 2002).

Table 6 Methylene Blue Dye Uptake at Different Sorbent Compositions

Q (metal uptake in mg metal/g sorbent)
Concentration
A B C D E
200 4.981 4.969 4.959 4.985 4.983
400 4.975 4.961 4.954 4.978 4.977
600 4.962 4.961 4.943 4.977 4.976
800 4.907 4.888 4.817 4.947 4.924
1000 4.840 4.810 4.707 4.922 4.895
 36

Table 7 Copper Uptake at Different Sorbent Compositions

Q (metal uptake in mg metal/g sorbent)
Concentration
A B C D E
200 18.925 19.378 19.533 18.319 16.686
400 37.740 39.087 39.187 32.422 27.064
600 55.214 57.450 58.715 49.047 45.013
800 67.996 72.715 76.082 63.687 62.605
1000 82.666 83.110 85.163 82.559 80.593

The results presented on table 6 and 7 show the effect of initial concentrations of

copper on copper and methylene blue dye uptake. The results illustrated that the copper

uptake increases when initial concentration of copper increases for each sorbent composition.

This phenomenon can be explained by the fact that at higher concentrations more sorbate are

available than binding sites which hinder adsorption. However, on methylene blue dye

adsorption shown on table 6, methylene blue dye uptake decreases as the initial copper

concentration increases. The reason for this is the low competitive behavior of methylene

blue dye compared to copper.

The equilibrium binding was described using two adsorption models, Langmuir and

Freundlich. These models were applied to the experimental data shown in Appendix B (Table

1B and Table 2B). The Langmuir model assumes that there is no interaction between the

sorbate molecules and that the sorption is localized in a monolayer. It is then assumed that

once a dye/metal molecule occupies a site, no further sorption can take place at that site.

Theoretically, when a saturation value is reached, no further sorption can take place. The

Freundlich model is an empirical relationship describing the sorption of solutes from a liquid

to a solid surface. The Freundlich model assumes that the sorption takes place on

heterogenous surfaces and adsorption capacity depends on the equilibrium concentration of

copper and methylene blue dye (Allen et al., 2003 and Mckay et al., 1982).
 37

In order to decide which type of isotherm fits better for copper and methylene blue

dye sorption, ln Q against ln Ce for Freundlich isotherm and 1/Q against 1/Ce for Langmuir

isotherm were plotted. The fit of the the R2 values (goodness of fit criterion) computed by

linear regression for the two types of isotherms are presented tables 8 and 9 for all sorbent

composition. Freundlich isotherm is most appropriate for sorption of both copper and

methylene blue dye at all sorbent compositions.

Table 8 Langmuir and Freundlich Parameters for Methylene Blue Dye at Different Sorbent
Compositions
Langmuir Parameters Freundlich Parameters
Composition
Qmax,(mg/g) b, (L/mg) R2 K, (L/g) N R2
100% S;0%B 4.8709 146.6429 0.8524 4.9013 75.7576 0.9623
75% S;25%B 4.8972 0.2042 0.9284 4.9116 97.0874 0.9824
50% S;50%B 4.9164 339.0000 0.8913 4.9180 119.0476 0.9714
25% S;75%B 4.9456 674.0000 0.9322 4.9357 178.5714 0.9830
0% S;100%B 4.9579 1008.5000 0.9844 4.9461 238.0952 0.9960

Table 9 Langmuir and Freundlich Parameters for Copper at Different Sorbent Compositions
Langmuir Parameters Freundlich Parameters
Composition b,
Qmax,(mg/g) (L/mg) R2 K, (L/g) N R2
100% S;0%B 15.8228 0.9107 0.5900 0.8895 0.3137 0.8915
75% S;25%B 29.9401 0.4550 0.6461 0.8855 0.2530 0.8905
50% S;50%B 47.8469 0.3501 0.6281 0.8994 0.2284 0.9007
25% S;75%B 57.8035 0.0625 0.9205 0.8401 0.1983 0.9805
0% S;100%B 69.9301 0.0371 0.9926 0.8212 0.1842 0.9981

Influence of pH on sorption of copper and methylene blue dye adsorption

The pH is one of the most important factors controlling the adsorption of dye and

metal onto adsorbent. It is well known that the pH of the medium affects the solubility of

metal ions and the concentration of the counter ions on the functional groups of the biomass
 38

cell walls, so pH is an important parameter on sorption of ions from aqueous solutions

(Antunes et al., 2003).

It was observed that most studies conducted on sorption of dye and copper observed

that there was little copper and dye uptake at low at pH usually pH lower than 3 while

working over pH 6.0 was avoided to prevent the possible precipitation of copper hydroxide.

Little copper uptake at low pH values is an indication of competition of excess of protons for

the same binding sites on the algal cell wall (Puranik and Paknikar, 1999).

In this study, the effect of pH on simultaneous removal of copper and methylene

blue dye was investigated, specifically, pH 3 - 9. The generated plots of copper and

methylene blue dye sorption are shown in figure 7 and figure 8, respectively, using

composition C (50%Sargassum;50%bentonite) at initial copper and methylene blue

concentration of 200 ppm and 50 ppm, respectively.

120
% Adsorption Cf (mg/L)
100

80

60

40

20

0
3 4 5 6
pH

Figure 7 Influence of pH on Copper Adsorption

 39

119
% Adsorption Cf (mg/L)
99

79

59

39

19

-1
3 4 5 6
pH

Figure 8 Influence of pH on Methylene Blue Dye Adsorption

During the experiment, precipitation of copper was evident at pH 7 to 9 as observed

by other researchers. Since the main concern of this study is the sorption mechanism, the data

obtained for pH 7-9 were not included in the discussion since precipitation is a different

mechanism from sorption.

Generally, increasing pH will increase metal uptake. This could be explained by the

increase in density of the negative charge on the cell surface, causing proton removal on the

cell bonding sites, thereby increasing its sorption capacity. However, based on the results of

this study, varying the pH of the solution, most likely, has no effect on the sorption capacity

of Sargassum-bentonite admix. The probable reason for this is that the initial concentrations

used in this study were not sufficient to fill up the active sites available for adsorption due to

the large amount of sorbent used. Maximum % adsorption was found as 97.2785% and

99.83105% for copper and dye, respectively, at pH 5. Above and under this point, adsorption

of methylene blue and copper on Sargassum-bentonite admix tends slightly to decrease.

 40

Conclusion

Sargassum-bentonite admix was able to effectively adsorb copper and methylene

blue dye simultaneously. The rate of removal of copper and methylene blue was very fast for

the first 30 minutes of the experiment where most of the copper and methylene blue dye was

adsorbed. Sorption kinetics of copper and methylene blue dye has been best described by

pseudo-second order equation.

The admix containing 50% Sargassum;50% bentonite was the most effective in

reducing copper from artificial wastewater with maximum copper uptake of 85.163 mg/g

sorbent. On the other hand, for methylene blue dye adsorption, the admix having 25%

Sargassum;75% bentonite was found to be the most effective with maximum methylene blue

dye uptake of 4.985 mg/g sorbent. For the simultaneous removal of copper and methylene

blue dye, the most effective sorbent composition was 50%Sargassum;50%bentonite.

The effect of initial concentrations of copper on copper is that the copper uptake

increases when initial concentration of copper increases for each sorbent composition.

However, methylene blue dye uptake decreases as the initial copper concentration increases.

Freundlich isotherm best describes the sorption of copper and methylene blue dye.

Variation of the pH of the solution, most likely, has no effect on the sorption

capacity of Sargassum-bentonite admix. Maximum % adsorption was found as 97.2785%

and 99.83105% for copper and dye, respectively, at pH 5.

 41

References

Allen, S.J. and B. Koumanova (2005). Decolorization of Water/Wastewater Using

Adsorption. Journal of the University of Chemical Technology and Metallurgy, Volume 40
(3), 175-192.

Allen, S.J., Q. Gan, R. Matthews, and P.A. Johnson (2003). Comparison of Optimized
Isotherm Models for Basic Dye Adsorption by Kudzu. Bioresource Technology, Volume 88,
143-152.

Al-Asheh S., F. Banat and L. Abu-Aitah (2003). The Removal of Methylene Blue Dye from
Aqueous Solutions Using Activated and Non-activated Bentonites. Adsorption Science and
Technology, Volume 21 (5), 451-462.

Antunes, W.M., A.S. Luna, C.A. Henriques, and A.A. Costa (2003). An Evaluation of
Copper Biosorption by a Brown Seaweed Under Optimized Conditions. Electronic Journal
of Biotechnology, Volume 6 (3), 174-184.

Atkins P. (1970), Color Removal from Dye Wastewater Using Vermiculite. Environmental
Technology, Volume 17, 1169-1180.

Bautista, D. and M.A. Demition (2005). Cadmium (Cd2+) and Nonionic Surfactant (Triton X-
100) Interference on Lead (II) Biosorption of Sargassum ilicifolium. Undergraduate Thesis,
Mapua Institute of Technology.

Bungabong, M. (2003). Kinetics and Equilibrium Studies on the Biosorption of Lead (II) on
Brown Seaweeds (Sargassumilicifolium). Undergraduate Thesis, Mapua Institute of
Technology.

Clark, S., P. Brown, and R. Pitt (2000). Wastewater Treatment Using Low-cost Adsorbents
and Waste Materials. Department of Civil and Environmental Engineering, University of
Alabama.

Cossich, E. (2002). Biosorption of Chromium (III) by Sargassum sp. Biomass. Electronic

Journal of Biotechnology, Volume 5 (2), 35-54.

Dadural, L.J. and M.A de Dios (2005). Effects of Secondary Alkyl Amine and Alkylbenzene
Sulfonic Acid on the Biosorption of Lead (II) Using Sargassum ilicifolium. Undergraduate
Thesis, Mapua Institute of Technology.

Davis, T.A., B. Volesky, and R.H.S.F. Vieira (2000). Sargassum Seaweed as Biosorbent for
Heavy Metals. Water Research, Volume 34 (17), 4270-4278.
 42

Demmin, T.R. and K.D. Uhrich (1998). A new Development for (Textile Mill) Wastewater
Treatment. Report Prepared for Publication in the American Dye Stuff, Andco
Environmental Processes, Inc.
Go, M. and R.D. Sese (2002). Use of Heat Treated Bentonite Clay for Reducing the Color of
Wastewater in the Textile Industry. Undergraduate Thesis, Mapua Institute of Technology.

Gupta, R., P. Ahuja, S. Khan, R.K. Saxena, and H. Mohapatra (2000). Microbial
Biosorbents: Meeting Chalenges of Heavy Metal Pollution in Aqueous Solutions. Journal of
Current Science, Volume 78 (8), 967-973.

Ho, Y.S., D.A.J. Wase, and C.F. Forster (1996). Kinetic Studies of Competitive Heavy Metal
Adsorption by Sphagnum Moss Peat. Enviromental Technology, Volume 17, 71-77.

Ho, Y.S. and G. Mckay (1998). A Comparison of Chemisorption kinetic Models Applied to
Pollutant Removal on Various Sorbents. Transactions of the Institution of Chemical
Engineers, Volume 76, 332-340.

Ho, Y.S. and G. Mackay (2000). The Kinetics of Sorption of Divalent Metal Ions onto
Sphagnum Moss Peat. Environmental Technology, Volume 34, 735-742.

Hu, Q.H., S.H. Qiao, F. Haghseresht, M.A. Wilson, and G.Q. Lu (2005). Adsorption Study
for Removal of Basic Red Dye Using Bentonite. American Chemical Society, Volume 45 (2),
733-738.

Hurtado, A.Q. and A.R. Ragaza (1999). Sargassum Studies in Currimao Ilocos Norte,
Northern Philippines I. Seasonal Variations in the Biomass of Sargassum carpophyllum J.
Agardh, Sargassum ilicifolium (Turner) C. Agardh and Sargassum siliquosum J. Agardh
(Chaeophyta, Sargassaceae). Botanica Marina, Volume 42, 321-325.

Jeffers, T.H., C.R. Ferguson, and P.G. Bennet (1990). Biosorption of Metal Contaminants
Using Immobilized Biomass A Laboratory Study. Report of Investigations, United States.
Bureau of Mines, 9340.

Kapoor, A. and T. Viraraghavan (1998). Use of Immobilized Bentonite in Removal of Heavy

Metals from Wastewater. Journal of Environmental Engineering, Volume 124 (10), 1020-
1024.

Khan, S.A., R. Rehman, and M.A. Khan (1994). Sorption of Cesium on Bentonite. Waste
Management, Volume 14 (7), 629.

Lagergren, S. (1898). About the Theory of So-called Adsorption of Solutble Substances.

Kungliga Svenska Vetenskapsakademiens Handlingar, Volume 24, 1-39.
 43

Matheickal, J.T. and Q. Yu (1999). Biosorption of Lead (II) and Copper(II) from Aqueous
Solution by Pre-treated Biomass of Australian Marine Algae. Bioresource Technology,
Volume 69 (3), 223-229.

Mckay, G., H.S. Blair, and J.R. Gardener (1982). Adsorption of Dyes on Chitin. I.
Equilibrium Studies. Journal of Appl Polym Sci, Volume 27, 3043-3057.

Mohan, S. and J. Karthikeyan (1997), Removal of Lignin and Tannin Color from Aqueous
Solution by Adsorption onto Activated Charcoal. Environmental Pollution, Volume 97, 183-
187.

Ozcan, A.S., B. Erdem, and A. Ozcan (2004). Adsorption of Acid Blue 193 from Aqueous
Solution onto Na-bentonite and DTMA-bentonite. Journal of Colloid Interface Science,
Volume 280 (1), 44-54.

Pala, A. (2001). Chemical Treatment of Textile Wastewaters: Statistical Characterization,

Color and Sulfide Removal. Indian Journal of Environment and Health, Volume 43 (3), 128-
134.

Puranik, P.R. and K.M. Paknikar (1999). Biosorption of Lead, Cadmium and Zinc by
Citrobacter Strain of MCM B-181: Characterization Studies. Biotechnology Progress,
Volume 15 (2), 228-237.

Raghuvanshi, S. P., R. Singh, and C.P. Kaushik (2004). Kinetics Study of Methylene Blue
Dye Bioadsorption on Baggase. Applied Ecology and Environmental Research, Volume 2
(2), 3543.

Robinson, T., G. McMullan, R. Marchant, and P. Nigam (2001). Remediation of Dyes in

Textile Effluent; a Critical Review on Current Treatment Technologies with a Proposed
Alternative. Bioresource Technology, Volume 77, 247-255.

Sabodina, M.N., S.N. Kalmykov, and Y.A. Sapozhnikov (2004). Sorption Properties of
Bentonite Clays Towards Several Radionuclides. Electronic Scientific Information Journal,
Volume 22 (1), 1-5.

Sag, Y., A. Kaya, and T. Kutsal (1998). The Simultaneous Biosorption of Cd(II) and Zn(II)
on Rhizopus arrhizus: Application of the Adsorption Models. Hydrometallurgy, Volume 50,
(3), 297-314.

Sotayco, R. and H. Tamayo (2005). Biosorption of Lead (Pb2+), Copper (Cu2+), and Nickel
(Ni2+) from Artificial Wastewater Using Sargassum cristafolium. Undergraduate Thesis,
Mapua Institute of Technology.

Stuanes, A. (1976). Adsorption of Mn2+, Zn2+, Cd2+, and Hg2+ from Binary Solutions by
Mineral Materials. Acta Agricultur Scandinavica, Volume 26, 243-250.
 44

Vieira, R.H.S.F. and B. Volesky (2000). Biosorption: A Solution to Pollution?. Journal of

International Microbiology, Volume 3, 17-24.

Vijayaraghavan, K., J.R. Jegan, K. Palanivelu, and M. Velan (2004). Copper Removal from
Aqueous Solution by Marine Green Alga Ulva reticulate. Electronic Journal of
Biotechnology, Volume 7 (1), 61-71.

Viraraghavan, T. and A. Kapoor (1994). Adsorption of Mercury from Wastewater by

Bentonite. Applied Clay Science, Volume 9, 31-49.

Volesky, Bohumil (1999). Biosorption of Metals. Encyclopedia of Biotehnology, Wiley &

Sons, New York, 433-453.

Voudrias, E., K. Fytianos, and E. Bozani (2001). Sorption Desorption Isotherms of Dyes
from Aqueous Solutions and Wastewaters with Different Sorbent Materials. Global Nest: the
International Journal, Volume 4 (1), 75-83.

Zhou, J.L.; P.L. Huang, and R.G. Lin (1998). Sorption and Desorption of Cu and Cd by
Macroalgae and Microalgae. Environmental Pollution, Volume 101 (1), 67-75.
 Chapter 4

CONCLUSION

Sargassum-bentonite admix was able to effectively adsorb copper and methylene

blue dye simultaneously. The rate of removal of copper and methylene blue was very fast for

the first 30 minutes of the experiment where most of the copper and methylene blue dye was

adsorbed. Sorption kinetics of copper and methylene blue dye has been best described by

pseudo-second order equation.

The admix containing 50% Sargassum;50% bentonite was the most effective in

reducing copper from artificial wastewater with maximum copper uptake of 85.163 mg/g

sorbent. On the other hand, for methylene blue dye adsorption, the admix having 25%

Sargassum;75% bentonite was found to be the most effective with maximum uptake of 4.985

mg/g sorbent. For the simultaneous removal of copper and methylene blue dye, the most

effective sorbent composition was 50%Sargassum;50%bentonite.

The effect of initial concentrations of copper on copper is that the copper uptake

increases when initial concentration of copper increases for each sorbent composition.

However, methylene blue dye uptake decreases as the initial copper concentration increases.

Freundlich isotherm best describes the sorption of copper and methylene blue dye.

Variation of the pH of the solution, most likely, has no effect on the sorption

capacity of Sargassum-bentonite admix. Maximum % adsorption was found as 97.2785%

and 99.83105% for copper and dye, respectively, at pH 5.

45
 Chapter 5

RECOMMENDATION

Experimental research on the sorption of effluents with competing ions (multimetal

systems) and mixture of different polarities of dye must be further studied to determine the

effect on sorption if ionic hindrances are present. In this manner, the experiment will be more

realistic since textile effluent may contain mixtures of heavy metals and various polarities of

dye.

The problem encountered when using bentonite as an adsorbent for the removal of

color from wastewater is that bentonite on contact with water swells and forms highly

colloidal suspension, making its separation from water following adsorption very difficult. In

case of Sargassum biomass, clogging of columns is the usual problem especially when fine

particles of the biomass were used. So, it is recommended that the sorbents be immobilized

in polymer matrix in the form of spherical beads to solve these problems to improve sorbent

performance.

It is also recommended that the sorption performance of the combined immobilized

Sargassum-bentonite be compared with the combined non-immobilized Sargassum-bentonite

since immobilization of the sorbents hinders or lessens the efficiency of sorption process.

46
 REFERENCES

Allen, S.J. and B. Koumanova (2005). Decolorization of Water/Wastewater Using

Adsorption. Journal of the University of Chemical Technology and Metallurgy, Volume 40
(3), 175-192.

Allen, S.J., Q. Gan, R. Matthews, and P.A. Johnson (2003). Comparison of Optimized
Isotherm Models for Basic Dye Adsorption by Kudzu. Bioresource Technology, Volume 88,
143-152.

Al-Asheh S., F. Banat and L. Abu-Aitah (2003). The Removal of Methylene Blue Dye from
Aqueous Solutions Using Activated and Non-activated Bentonites. Adsorption Science and
Technology, Volume 21 (5), 451-462.

Antunes, W.M., A.S. Luna, C.A. Henriques, and A.A. Costa (2003). An Evaluation of
Copper Biosorption by a Brown Seaweed Under Optimized Conditions. Electronic Journal
of Biotechnology, Volume 6 (3), 174-184.

Atkins P. (1970), Color Removal from Dye Wastewater Using Vermiculite. Environmental
Technology, Volume 17, 1169-1180.

Bautista, D. and M.A. Demition (2005). Cadmium (Cd2+) and Nonionic Surfactant (Triton X-
100) Interference on Lead (II) Biosorption of Sargassum ilicifolium. Undergraduate Thesis,
Mapua Institute of Technology.

Bungabong, M. (2003). Kinetics and Equilibrium Studies on the Biosorption of Lead (II) on
Brown Seaweeds (Sargassumilicifolium). Undergraduate Thesis, Mapua Institute of
Technology.

Clark, S., P. Brown, and R. Pitt (2000). Wastewater Treatment Using Low-cost Adsorbents
and Waste Materials. Department of Civil and Environmental Engineering, University of
Alabama.

Cossich, E. (2002). Biosorption of Chromium (III) by Sargassum sp. Biomass. Electronic

Journal of Biotechnology, Volume 5 (2), 35-54.

Dadural, L.J. and M.A de Dios (2005). Effects of Secondary Alkyl Amine and Alkylbenzene
Sulfonic Acid on the Biosorption of Lead (II) Using Sargassum ilicifolium. Undergraduate
Thesis, Mapua Institute of Technology.

Davis, T.A., B. Volesky, and R.H.S.F. Vieira (2000). Sargassum Seaweed as Biosorbent for
Heavy Metals. Water Research, Volume 34 (17), 4270-4278.

47
 48

Demmin, T.R. and K.D. Uhrich (1998). A new Development for (Textile Mill) Wastewater
Treatment. Report Prepared for Publication in the American Dye Stuff, Andco
Environmental Processes, Inc.
Go, M. and R.D. Sese (2002). Use of Heat Treated Bentonite Clay for Reducing the Color of
Wastewater in the Textile Industry. Undergraduate Thesis, Mapua Institute of Technology.

Gupta, R., P. Ahuja, S. Khan, R.K. Saxena, and H. Mohapatra (2000). Microbial
Biosorbents: Meeting Chalenges of Heavy Metal Pollution in Aqueous Solutions. Journal of
Current Science, Volume 78 (8), 967-973.

Ho, Y.S., D.A.J. Wase, and C.F. Forster (1996). Kinetic Studies of Competitive Heavy Metal
Adsorption by Sphagnum Moss Peat. Enviromental Technology, Volume 17, 71-77.

Ho, Y.S. and G. Mckay (1998). A Comparison of Chemisorption kinetic Models Applied to
Pollutant Removal on Various Sorbents. Transactions of the Institution of Chemical
Engineers, Volume 76, 332-340.

Ho, Y.S. and G. Mackay (2000). The Kinetics of Sorption of Divalent Metal Ions onto
Sphagnum Moss Peat. Environmental Technology, Volume 34, 735-742.

Hu, Q.H., S.H. Qiao, F. Haghseresht, M.A. Wilson, and G.Q. Lu (2005). Adsorption Study
for Removal of Basic Red Dye Using Bentonite. American Chemical Society, Volume 45 (2),
733-738.

Hurtado, A.Q. and A.R. Ragaza (1999). Sargassum Studies in Currimao Ilocos Norte,
Northern Philippines I. Seasonal Variations in the Biomass of Sargassum carpophyllum J.
Agardh, Sargassum ilicifolium (Turner) C. Agardh and Sargassum siliquosum J. Agardh
(Chaeophyta, Sargassaceae). Botanica Marina, Volume 42, 321-325.

Jeffers, T.H., C.R. Ferguson, and P.G. Bennet (1990). Biosorption of Metal Contaminants
Using Immobilized Biomass A Laboratory Study. Report of Investigations, United States.
Bureau of Mines, 9340.

Kapoor, A. and T. Viraraghavan (1998). Use of Immobilized Bentonite in Removal of Heavy

Metals from Wastewater. Journal of Environmental Engineering, Volume 124 (10), 1020-
1024.

Khan, S.A., R. Rehman, and M.A. Khan (1994). Sorption of Cesium on Bentonite. Waste
Management, Volume 14 (7), 629.

Lagergren, S. (1898). About the Theory of So-called Adsorption of Solutble Substances.

Kungliga Svenska Vetenskapsakademiens Handlingar, Volume 24, 1-39.
 49

Matheickal, J.T. and Q. Yu (1999). Biosorption of Lead (II) and Copper(II) from Aqueous
Solution by Pre-treated Biomass of Australian Marine Algae. Bioresource Technology,
Volume 69 (3), 223-229.

Mckay, G., H.S. Blair, and J.R. Gardener (1982). Adsorption of Dyes on Chitin. I.
Equilibrium Studies. Journal of Appl Polym Sci, Volume 27, 3043-3057.

Mohan, S. and J. Karthikeyan (1997), Removal of Lignin and Tannin Color from Aqueous
Solution by Adsorption onto Activated Charcoal. Environmental Pollution, Volume 97, 183-
187.

Ozcan, A.S., B. Erdem, and A. Ozcan (2004). Adsorption of Acid Blue 193 from Aqueous
Solution onto Na-bentonite and DTMA-bentonite. Journal of Colloid Interface Science,
Volume 280 (1), 44-54.

Pala, A. (2001). Chemical Treatment of Textile Wastewaters: Statistical Characterization,

Color and Sulfide Removal. Indian Journal of Environment and Health, Volume 43 (3), 128-
134.

Puranik, P.R. and K.M. Paknikar (1999). Biosorption of Lead, Cadmium and Zinc by
Citrobacter Strain of MCM B-181: Characterization Studies. Biotechnology Progress,
Volume 15 (2), 228-237.

Raghuvanshi, S. P., R. Singh, and C.P. Kaushik (2004). Kinetics Study of Methylene Blue
Dye Bioadsorption on Baggase. Applied Ecology and Environmental Research, Volume 2
(2), 3543.

Robinson, T., G. McMullan, R. Marchant, and P. Nigam (2001). Remediation of Dyes in

Textile Effluent; a Critical Review on Current Treatment Technologies with a Proposed
Alternative. Bioresource Technology, Volume 77, 247-255.

Sabodina, M.N., S.N. Kalmykov, and Y.A. Sapozhnikov (2004). Sorption Properties of
Bentonite Clays Towards Several Radionuclides. Electronic Scientific Information Journal,
Volume 22 (1), 1-5.

Sag, Y., A. Kaya, and T. Kutsal (1998). The Simultaneous Biosorption of Cd(II) and Zn(II)
on Rhizopus arrhizus: Application of the Adsorption Models. Hydrometallurgy, Volume 50,
(3), 297-314.

Sotayco, R. and H. Tamayo (2005). Biosorption of Lead (Pb2+), Copper (Cu2+), and Nickel
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Mapua Institute of Technology.

Stuanes, A. (1976). Adsorption of Mn2+, Zn2+, Cd2+, and Hg2+ from Binary Solutions by
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 50

Vieira, R.H.S.F. and B. Volesky (2000). Biosorption: A Solution to Pollution?. Journal of

International Microbiology, Volume 3, 17-24.

Vijayaraghavan, K., J.R. Jegan, K. Palanivelu, and M. Velan (2004). Copper Removal from
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 APPENDIX A

Sorption Kinetics

Table A.1 Flame Atomic Absorption Spectrometer Analyzer (FAAS) Data of Copper for
Sorption Kinetics (DF = 25) of Wastewater Containing Copper and Methylene Blue Dye at
Different Sorbent Compositions
Time Composition
A B C D E
minutes
Cf, ppm Cf, ppm Cf, ppm Cf, ppm Cf, ppm
0 200 200 200 200 200
1 99.775 79.625 81.975 129.575 153.325
5 88.500 77.850 83.825 123.975 145.875
10 91.000 64.025 58.325 120.175 133.625
15 86.950 65.025 64.450 122.525 118.825
20 85.225 62.600 54.250 115.750 126.450
25 87.200 60.650 53.700 113.550 121.400
30 84.650 55.175 51.225 109.625 114.025
35 84.150 59.175 55.350 102.225 108.575
40 80.075 50.400 57.525 83.725 120.800
45 80.225 47.750 57.425 62.700 122.950
50 79.650 49.000 52.275 62.925 115.575
55 78.275 33.875 49.950 60.700 106.600
60 82.450 25.575 22.950 65.675 100.375
90 82.375 24.650 18.825 58.950 107.300
120 79.700 20.175 19.325 54.000 89.025
150 78.450 22.625 17.725 55.375 90.650
180 78.575 21.425 18.950 53.575 90.050

51
 52

Table A.2 UV-VIS Spectrometer Data of Methylene Blue Dye for Sorption Kinetics of
Wastewater Containing Copper and Methylene Blue Dye at Different Sorbent Compositions
Time Composition
A B C D E
minutes
Cf, ppm Cf, ppm Cf, ppm Cf, ppm Cf, ppm
0 50 50 50 50 50
1 2.017 3.821 6.456 1.394 1.453
5 1.379 3.272 5.540 1.330 1.181
10 1.012 2.695 5.369 1.309 1.322
15 0.878 0.962 4.569 0.674 1.050
20 0.803 0.922 5.608 0.530 0.885
25 0.684 0.793 3.698 0.516 0.873
30 0.655 0.788 3.741 0.488 0.824
35 0.644 0.769 4.021 0.387 0.959
40 0.768 0.694 3.704 0.340 1.096
45 0.621 0.650 2.439 0.273 0.642
50 0.608 0.582 2.523 0.336 0.391
55 0.579 0.560 1.916 0.284 0.312
60 0.566 0.711 1.032 0.136 0.141
90 0.542 0.794 1.065 0.238 0.166
120 0.462 0.754 1.097 0.102 0.178
150 0.469 0.876 1.148 0.151 0.107
180 0.344 0.899 1.064 0.109 0.109
 53

Table A.3 Flame Atomic Absorption Spectrometer Analyzer (FAAS) Data of Copper for
Sorption Kinetics (DF = 25) of Wastewater Containing Copper Only at Different Sorbent
Compositions
Time Composition
A B C D E
minutes
Cf, ppm Cf, ppm Cf, ppm Cf, ppm Cf, ppm
0 200 200 200 200 200
1 90.725 89.625 94.025 67.550 106.425
5 88.825 84.650 76.375 62.375 95.700
10 84.100 80.700 73.675 61.775 80.700
15 79.650 73.000 67.875 58.050 76.025
20 78.750 69.675 62.600 53.825 57.225
25 77.125 66.275 58.850 54.525 52.600
30 75.750 66.500 60.375 54.975 47.600
35 73.225 63.525 57.050 52.900 44.675
40 73.525 64.025 58.350 51.400 42.650
45 74.200 63.875 58.075 50.700 44.125
50 72.850 63.850 60.375 50.850 39.625
55 72.825 67.100 55.650 46.850 38.400
60 71.850 62.625 55.350 44.850 35.100
90 65.325 61.825 51.525 40.300 37.950
120 70.575 60.125 53.800 43.375 37.425
150 65.975 59.575 51.650 43.800 33.925
180 70.675 55.825 54.675 39.925 32.175
 54

Table A.4 UV-VIS Spectrometer Data of Methylene Blue Dye for Sorption Kinetics of
Wastewater Containing Methylene Blue Dye Only at Different Sorbent Compositions
Time Composition
A B C D E
minutes
Cf, ppm Cf, ppm Cf, ppm Cf, ppm Cf, ppm
0 50 50 50 50 50
1 7.657 2.773 3.205 9.866 14.115
5 7.054 2.130 2.943 7.043 13.024
10 6.007 2.143 2.484 7.256 12.057
15 4.642 2.224 2.707 6.597 11.595
20 4.310 2.338 1.941 3.468 11.637
25 2.439 1.931 1.733 1.946 10.527
30 1.948 2.042 1.596 1.711 9.971
35 1.347 1.935 1.629 1.586 9.298
40 1.074 1.743 1.204 1.681 9.868
45 1.097 1.659 1.308 1.694 8.995
50 0.927 1.535 1.434 1.589 7.995
55 0.948 1.619 1.284 1.464 7.449
60 0.794 1.861 1.211 1.564 6.838
90 0.794 1.245 1.169 1.415 6.536
120 0.395 1.199 1.146 0.968 5.188
150 0.524 1.082 1.171 1.132 5.649
180 0.462 1.007 1.148 1.264 6.434
 55

Table A.5 Methylene Blue Dye Uptake at Different Sorbent Compositions

Time Q (mg MBD / g sorbent)
Composition
Minutes
A B C D E
0 0 0 0 0 0
1 4.798 4.618 4.354 4.861 4.855
5 4.862 4.673 4.446 4.867 4.882
10 4.899 4.731 4.463 4.869 4.868
15 4.912 4.904 4.543 4.933 4.895
20 4.920 4.908 4.439 4.947 4.911
25 4.932 4.921 4.630 4.948 4.913
30 4.935 4.921 4.626 4.951 4.918
35 4.936 4.923 4.598 4.961 4.904
40 4.923 4.931 4.630 4.966 4.890
45 4.938 4.935 4.756 4.973 4.936
50 4.939 4.942 4.748 4.966 4.961
55 4.942 4.944 4.808 4.972 4.969
60 4.943 4.929 4.897 4.986 4.986
90 4.946 4.921 4.893 4.976 4.983
120 4.954 4.925 4.890 4.990 4.982
150 4.953 4.912 4.885 4.985 4.989
180 4.966 4.910 4.894 4.989 4.989
 56

Table A.6 Copper Uptake at Different Sorbent Compositions

Time Q (mg copper / g sorbent)
Composition
minutes
A B C D E
0 0 0 0 0 0
1 10.023 12.038 11.803 7.043 4.668
5 11.150 12.215 11.618 7.603 5.413
10 10.900 13.598 14.168 7.983 6.638
15 11.305 13.498 13.555 7.748 8.118
20 11.478 13.740 14.575 8.425 7.355
25 11.280 13.935 14.630 8.645 7.860
30 11.535 14.483 14.878 9.038 8.598
35 11.585 14.083 14.465 9.778 9.143
40 11.993 14.960 14.248 11.628 7.920
45 11.978 15.225 14.258 13.730 7.705
50 12.035 15.100 14.773 13.708 8.443
55 12.173 16.613 15.005 13.930 9.340
60 11.755 17.443 17.705 13.433 9.963
90 11.763 17.535 18.118 14.105 9.270
120 12.030 17.983 18.068 14.600 11.098
150 12.155 17.738 18.228 14.463 10.935
180 12.143 17.858 18.105 14.643 10.995
 57

0.140
0.120 100%Sargassum;0%Bentonite
75%Sargassum;25%Bentonite
0.100
50%Sargassum;50%Bentonite
0.080
ln (Qe - Qt)

25%Sargassum;75%Bentonite
0.060 0%Sargassum;100%Bentonite
0.040
0.020
0.000
-0.020 0 10 20 30 40 50 60 70
-0.040
Time, minute

Figure A.1 First Order Kinetics for Methylene Blue Dye at Different Sorbent Compositions

14
100%Sargassum;0%Bentonite
12 75%Sargassum;25%Bentonite
50%Sargassum;50%Bentonite
10 25%Sargassum;75%Bentonite
0%Sargassum;100%Bentonite
8
t/Qt

6
4
2
0
0 10 20 30 40 50 60 70
Time, minute

Figure A.2 Pseudo-Second Order Kinetics for Methylene Blue Dye at Different Sorbent
Compositions
 58

1
100%Sargassum;0%Bentonite
0.8 75%Sargassum;25%Bentonite
50%Sargassum;50%Bentonite
ln (Qe - Qt)
0.6
25%Sargassum;75%Bentonite
0.4 0%Sargassum;100%Bentonite

0.2

0
0 10 20 30 40 50 60 70
-0.2
Time, minute

Figure A.3 First Order Kinetics for Copper at Different Sorbent Compositions

8
100%Sargassum;0%Bentonite
7 75%Sargassum;25%Bentonite
6 50%Sargassum;50%Bentonite
25%Sargassum;75%Bentonite
5 0%Sargassum;100%Bentonite
t/Qt

4
3
2
1
0
0 10 20 30 40 50 60 70
Time, minute

Figure A.4 Pseudo-Second Order Kinetics for Copper at Different Sorbent Compositions
 APPENDIX B

Sorption Isotherms

Table B.1 Flame Atomic Absorption Spectrometer Analyzer (FAAS) Data of Copper for
Sorption Isotherm (DF = 10) of Wastewater Containing Copper and Methylene Blue Dye at
Different Sorbent Compositions
Composition
Concentration A B C D E
Ce (ppm) Ce (ppm) Ce (ppm) Ce (ppm) Ce (ppm)
200 10.748 6.219 4.675 16.811 33.138
400 22.603 9.129 8.128 75.776 129.36
600 47.865 25.503 12.853 109.534 149.87
800 120.04 72.847 39.176 163.128 173.954
1000 173.345 168.901 148.373 174.412 194.066

Table B.2 UV-VIS Spectrometer Data of Methylene Blue Dye for Sorption Isotherm of
Wastewater Containing Copper and Methylene Blue Dye at Different Sorbent Compositions
Composition
Concentration A B C D E
Ce (ppm) Ce (ppm) Ce (ppm) Ce (ppm) Ce (ppm)
200 0.19 0.3134 0.4142 0.148 0.1715
400 0.2497 0.3872 0.4641 0.2167 0.2327
600 0.379 0.3937 0.5683 0.2303 0.2375
800 0.9346 1.1193 1.8294 0.5346 0.7573
1000 1.605 1.8961 2.926 0.7844 1.053

Table B.3 Flame Atomic Absorption Spectrometer Analyzer (FAAS) Data of Copper for
Sorption Isotherm (DF = 10) of Wastewater Containing Copper Only at Different Sorbent
Compositions
Composition
Composition A B C D E
Cf (ppm) Cf (ppm) Cf (ppm) Cf (ppm) Cf (ppm)
200 23.68 26.47 27.19 22.95 31.47
400 78.31 75.86 79.98 70.63 175.3
600 153.2 145.8 136.4 146.8 344.5
800 209.6 215.6 215.9 249.7 507.1
1000 278.4 264.7 286.7 321.4 522.4

59
 60

Table B.4 UV-VIS Spectrometer Data of Methylene Blue Dye for Sorption Isotherm of
Wastewater Containing Copper and Methylene Blue Dye at Different Sorbent Compositions
Composition Concentration
A 1.605
B 4.964
C 12.73
D 18.536
E 15.214

Table B.5 Methylene Blue Dye Uptake at Different Sorbent Compositions

Q (metal uptake in mg metal/g sorbent)
Concentration
A B C D E
200 4.981 4.969 4.959 4.985 4.983
400 4.975 4.961 4.954 4.978 4.977
600 4.962 4.961 4.943 4.977 4.976
800 4.907 4.888 4.817 4.947 4.924
1000 4.840 4.810 4.707 4.922 4.895

Table B.6 Copper Uptake at Different Sorbent Compositions

Q (metal uptake in mg metal/g sorbent)
Concentration
A B C D E
200 18.925 19.378 19.533 18.319 16.686
400 37.740 39.087 39.187 32.422 27.064
600 55.214 57.450 58.715 49.047 45.013
800 67.996 72.715 76.082 63.687 62.605
1000 82.666 83.110 85.163 82.559 80.593

Table B.7 %Copper Adsorbed at Different Sorbent Compositions

% Adsorption
Concentration
A B C D E
200 94.626 96.891 97.663 91.595 83.431
400 94.349 97.718 97.968 81.056 67.660
600 92.023 95.750 97.858 81.744 75.022
800 84.995 90.894 95.103 79.609 78.256
1000 82.666 83.110 85.163 82.559 80.593
 61

Table B.8 %Methylene Blue Dye Adsorbed at Different Sorbent Compositions

% Adsorption
Concentration
A B C D E
200 99.6200 99.3732 99.1716 99.7040 99.6570
400 99.5006 99.2256 99.0718 99.5666 99.5346
600 99.2420 99.2126 98.8634 99.5394 99.5250
800 98.1308 97.7614 96.3412 98.9308 98.4854
1000 96.7900 96.2078 94.1480 98.4312 97.8940

0.2500

0.2000

0.1500
1/Q

100%Sargassum;0%Bentonite
0.1000 75%Sargassum;25%Bentonite 50%Sargassum;50%Bentonite
25%Sargassum;75%Bentonite 0%Sargassum;100%Bentonite
0.0500

0.0000
0 2 4 6 8
1/Ce

Figure B.1 Langmuir Isotherm for Methylene Blue Dye at Different Sorbent
Compositions
1.8000
1.6000
1.4000
1.2000
100%Sargassum;0%Bentonite 1.0000
LN Q

75%Sargassum;25%Bentonite
0.8000
50%Sargassum;50%Bentonite
0.6000
25%Sargassum;75%Bentonite
0.4000
0%Sargassum;100%Bentonite
0.2000
0.0000
-3 -2 -2 -1 -1 0 1 1 2
LN Ce

Figure B.2 Freundlich Isotherm for Methylene Blue Dye at Different Sorbent
Compositions
 62

0.07

0.06

0.05

0.04
1/Q

100%Sargassum;0%Bentonite
0.03 75%Sargassum;25%Bentonite
0.02 50%Sargassum;50%Bentonite
25%Sargassum;75%Bentonite
0.01 0%Sargassum;100%Bentonite
0
0 0.05 0.1 0.15 0.2 0.25
1/Ce

Figure B.3 Langmuir Isotherm for Copper at Different Sorbent Compositions

5
4.5
4
3.5
3
LN Q

2.5
2 100%Sargassum;0%Bentonite 75%Sargassum;25%Bentonite
1.5 50%Sargassum;50%Bentonite 25%Sargassum;75%Bentonite
1 0%Sargassum;100%Bentonite
0.5
0
0 1 2 3 4 5 6
LN Ce
Figure B.4 Freundlich Isotherm for Copper at Different Sorbent Compositions
 APPENDIX C

Influence of pH

Table C.1 Influence of pH on Copper Adsorption

Ce, ppm
pH Ce, ppm % Adsorption
(w/ dilution factor)
3 0.8774 8.774 95.613
4 0.7408 7.408 96.296
5 0.5443 5.443 97.2785
6 0.5686 5.686 97.157
7 4.0904 40.904 79.548
8 1.0084 10.084 94.958
9 1.5735 15.735 92.1325

Table C.1 Influence of pH on Methylene Blue Dye Adsorption

pH Ce, ppm % Adsorption
3 0.9497 98.1006
4 0.9284 98.1432
5 0.3379 99.3242
6 0.6313 98.7374
7 3.9512 92.0976
8 2.1376 95.7248
9 2.1982 95.6036

63