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© University of Peradeniya 2013 Ceylon Journal of Science (Physical Sciences) 17 (2013) 19-29 Chemistry Breadfruit (Artocarpus altilis) Waste for Bioremediation of Cu (II) and Cd(II) Ions from Aqueous Medium Namal Priyantha 1,2* , Linda B.L. Lim 3 , D.T.B. Tennakoon 3 , Nur Hakimah Mohd Mansor 3 , MuhdKhairud Dahri 3 and HeiIng Chieng 3 1 Department of Chemistry, University of Peradeniya, Peradeniya, Sri Lanka. 2 Postgraduate Institute of Science, University of Peradeniya, Peradeniya, Sri Lanka 3 Department of Chemistry, Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, Gadong, BE 1410, Negara Brunei Darussalam. (*Corresponding author’s email: [email protected]) Received: 17 September2012 / Accepted after revision: 14 January 2013 ABSTRACT The skin and the core of breadfruit (Artocarpus altilis) show great affinity toward Cd(II) and Cu(II), showing high extent of removal. Consequently, the metal ion – bread- fruit waste system reaches adsorption equilibrium within a short period of time. It is found that both breadfruit skin and core are able to adsorb Cu(II) more easily than Cd(II), and further, the extent of sorption of each metal by both the skin and the core is approximately equal. Acidification of the solution phase decreases the extent of mass transfer of each metal ion from the solution phase to the solid biosorbent phase. Nev- ertheless, acidification of the solid phase (each adsorbent) shows no impact on Cd(II) removal, while the Cu(II) removal is improved by 20%. Further, it is determined that both Cu(II) and Cd(II) obey the Langmuir adsorption isotherm with a high regression coefficient. INTRODUCTION Expansion of industrialization and ur- banization has resulted in the generation of large quantities of toxic materials, including heavy metals and dyes, due to the extensive use of these materials in industry. For in- stance, cadmium and its compounds are widely used for batteries, ceramics, alloys, and in mining and metal plating industries, while copper metal and its compounds are used in industries, including pulp and paper, fertilizer, petroleum refinery and aircraft plating (Gupta et al., 2006; Bazrafshan et al., 2006). Cadmium is considered to be one of the more toxic heavy metals found in indus- trial effluents, while copper is not as toxic as cadmium (Rao and Khan, 2009). Free aqua forms of metal ions are biologically active as compared to other chemical forms, and hence toxic metal ions, such as heavy metal ions, cause health effects. Among them, cadmium is carcinogenic and causes lung fibrosis, kidney failure and bone softening, while copper causes gastrointestinal ca- tarrh, cramps in calves and hemochrometo- sis (Anirudhan and Radhakrishnan, 2008). Moreover, continuous drinking of beverages containing Cu (II) leads to harmful diseases, such as necrotic changes in the liver and kidney, lung cancer and capillary damage (Naughton et al., 2011). Contamination of water by these heavy metals thus causes harmful effects to living organisms and to the environment, which has already become a major global issue. It is therefore a re- sponsibility of the human to find ways to minimize pollution and to help improve the quality of human life. Methods successful in removing heavy metals from waste water include chemical precipitation, ion-exchange, osmosis, elec-

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Page 1: Breadfruit (Artocarpus altilis) Waste for Bioremediation ... 17_3.pdf · Breadfruit (Artocarpus altilis) Waste for Bioremediation of Cu (II) ... Jackfruit (Arto- ... the feasibility

© University of Peradeniya 2013

Ceylon Journal of Science (Physical Sciences) 17 (2013) 19-29 Chemistry

Breadfruit (Artocarpus altilis) Waste for Bioremediation of Cu (II) and Cd(II) Ions from Aqueous Medium

Namal Priyantha1,2*, Linda B.L. Lim3, D.T.B. Tennakoon3, Nur Hakimah Mohd Mansor3,

MuhdKhairud Dahri3 and HeiIng Chieng3

1Department of Chemistry, University of Peradeniya, Peradeniya, Sri Lanka. 2Postgraduate Institute of Science, University of Peradeniya, Peradeniya, Sri Lanka

3Department of Chemistry, Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, Gadong, BE 1410, Negara Brunei Darussalam. (*Corresponding author’s email: [email protected])

Received: 17 September2012 / Accepted after revision: 14 January 2013

ABSTRACT

The skin and the core of breadfruit (Artocarpus altilis) show great affinity toward

Cd(II) and Cu(II), showing high extent of removal. Consequently, the metal ion – bread-

fruit waste system reaches adsorption equilibrium within a short period of time. It is

found that both breadfruit skin and core are able to adsorb Cu(II) more easily than

Cd(II), and further, the extent of sorption of each metal by both the skin and the core is

approximately equal. Acidification of the solution phase decreases the extent of mass

transfer of each metal ion from the solution phase to the solid biosorbent phase. Nev-

ertheless, acidification of the solid phase (each adsorbent) shows no impact on Cd(II)

removal, while the Cu(II) removal is improved by 20%. Further, it is determined that

both Cu(II) and Cd(II) obey the Langmuir adsorption isotherm with a high regression

coefficient.

INTRODUCTION

Expansion of industrialization and ur-

banization has resulted in the generation of

large quantities of toxic materials, including

heavy metals and dyes, due to the extensive

use of these materials in industry. For in-

stance, cadmium and its compounds are

widely used for batteries, ceramics, alloys,

and in mining and metal plating industries,

while copper metal and its compounds are

used in industries, including pulp and paper,

fertilizer, petroleum refinery and aircraft

plating (Gupta et al., 2006; Bazrafshan et al.,

2006). Cadmium is considered to be one of

the more toxic heavy metals found in indus-

trial effluents, while copper is not as toxic as

cadmium (Rao and Khan, 2009). Free aqua

forms of metal ions are biologically active as

compared to other chemical forms, and

hence toxic metal ions, such as heavy metal

ions, cause health effects. Among them,

cadmium is carcinogenic and causes lung

fibrosis, kidney failure and bone softening,

while copper causes gastrointestinal ca-

tarrh, cramps in calves and hemochrometo-

sis (Anirudhan and Radhakrishnan, 2008).

Moreover, continuous drinking of beverages

containing Cu (II) leads to harmful diseases,

such as necrotic changes in the liver and

kidney, lung cancer and capillary damage

(Naughton et al., 2011). Contamination of

water by these heavy metals thus causes

harmful effects to living organisms and to

the environment, which has already become

a major global issue. It is therefore a re-

sponsibility of the human to find ways to

minimize pollution and to help improve the

quality of human life.

Methods successful in removing heavy

metals from waste water include chemical

precipitation, ion-exchange, osmosis, elec-

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Priyantha et al., /Ceylon Journal of Science-Physical Sciences 17 (2013) 19-29

20

trolytic processes and membrane separa-

tion (Srivastava et al., 2008; Vimala and Das,

2009; Rathinam et al., 2010; Xiao et al.,

2010; Ahmaruzzaman, 2011; Masoudzadeh

et al., 2011). These techniques produce

large volumes of sludge, and further they

are not economical. Therefore, adsorption

has become an attractive alternative in re-

moving heavy metals from waste water.

Although activated carbon is an effective

adsorbent (Ahmaruzzaman, 2011; Ma-

soudzadeh et al., 2011; Budinova et al.,

2009), its use has been limited due to eco-

nomic factors. In an attempt to search for

economical adsorbents, much research has

focused, in recent years, on the use of bio-

mass, such as bacteria, fungi, yeast, fruit and

plant materials, to remove heavy metals

(Ahluwalia and Goyal, 2007; Naughton et al.,

2011). Biosorption, in general, provides en-

vironmentally-friendly and low-cost ap-

proaches for the removal of pollutants from

waste water.

Artocarpus altilis (breadfruit) is an Arto-

carpus variety which is grown in many

Asian countries. Traditionally, the leaves of

breadfruit have been used in the treatment

of liver cirrhosis, hypertension and diabetes

(Amarasinghe et al., 2008). Although many

equilibrium and kinetics studies have been

reported on the biosorption of heavy met-

als, especially Cd (II) and Cu(II), by different

types of biomass (Gupta et al., 2006; Rao

and Khan, 2009; Panda et al., 2006; Solisio

et al., 2008; Cojocaru et al., 2009; Luo et al.,

2010; Areco and Afonso, 2010), studies of

Artocarpus fruit biomass are very limited.

Among them, biosorption ability of Tarap

(Artocarpus odaratissimus), Jackfruit (Arto-

carpus hetorophyllus) and Cempedak (Arto-

carpus champeden), all of which belong to

the Artocarpus family, have been investigat-

ed recently (Inbaraj and Sulochana, 2004;

Lezcano et al., 2010; Lim et al., 2011). Fur-

ther, the chemical characterization of bread-

fruit has recently been reported (Amara-

singhe et al., 2008; Nwokocha and Williams,

2011; Maxwell et al., 2011) although its be-

havior in removing heavy metals has not

been reported to the best of our knowledge.

Despite many advantages in using bio-

mass in removing heavy metals, some com-

plications arise at research level and in fu-

ture applications. The same type of fruit ob-

tained from different places would have dif-

ferent texture, leading to variations in the

chemical composition, the structure, and the

chemistry of the biomass (Lim et al., 2011).

Due to these factors, accuracy and the preci-

sion of the final outcome would be of doubt

unless necessary precautions are practiced.

Proper sampling techniques, parameter op-

timization, and pre-treatment and pro-

cessing of the biomass are some steps re-

quired to address the above issues and to

enhance the efficiency of biosorption.

The aim of this research is to investigate

the feasibility of using breadfruit biomass,

in particular, its peel and core, for the re-

moval of cadmium and copper species from

aqueous solution under equilibrium condi-

tions. Effect of shaking time, settling time,

acidification and medium pH, on the extent

of biosorption was monitored in order to

optimize experimental conditions for the

most efficient removal. Additionally, the va-

lidity of adsorption isotherm models was

tested in order to obtain more information

on the interaction of the two metal ions with

breadfruit waste.

MATERIALS AND METHODS

Stock solutions of Cd (II) and Cu (II) of

concentrations ranging from 5 ppm up to

500 ppm were prepared by dissolving the

analytical grade nitrate of the respective

metal in deionized water. Solutions used for

acidification of the biomass and solutions of

different pH were prepared using NaOH

(Univar) and HNO3 (AnalaR). Samples of

breadfruit skin and core were dried in an

oven at 80 °C for about one week. Dried

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Priyantha et al., /Ceylon Journal of Science-Physical Sciences 17 (2013) 19-29

21

samples were blended and sieved to obtain

particle sizes in the range of 355 - 850 µm.

Cadmium and copper ion concentra-

tions were determined using Atomic Ab-

sorption Spectrophotometer (NOVAA 300)

at the wavelengths of 228.8 nm and 324.8

nm, respectively. Thermo-Scientific pH me-

ter (Orion 2-Star Bench-top model) was

used in monitoring pH, and an electric shak-

er (Thermo-Scientific MaxQ) was used in

agitating the metal ion solutions at a speed

of 250 rpm. FTIR spectra were recorded on

Shimadzu spectrophotometer (IRPrestige-

21), which had the wavelength range be-

tween 750 cm-1 and 4000 cm-1, with a reso-

lution of 2 cm-1. X-ray fluorescence (XRF)

spectra were recorded using XRF

spectrophotometer (PANalytical Axios), and

morphological characteristics of the adsor-

bent surface were carried out using Scan-

ning Electron Microscope (SEM) (Tescan

Vega XMU).

Optimization of experimental parameters

A series of suspensions consisting of

0.100 g of each biosorbent and 50.0 mL of

10 ppm each metal ion solution was shaken

at a speed of 250 rpm. The filtrate of each

suspension at different shaking time peri-

ods up to 4 h was analyzed for the metal ion

content to determine the optimum shaking

time. Another series of suspensions of the

same composition was allowed to shake for

the optimum period and then each suspen-

sion was allowed to stand for different set-

tling time periods up to 4 h to determine the

optimum value. Many trials were conducted

for each experiment and the average was

reported.

Suspensions of the biosorbent of the

same composition (50.0 mL of 10 ppm met-

al ion solution with 0.100 g biosorbent)

were used for the investigation of the effect

of pH on the extent of removal. For this pur-

pose, the pH of the suspension was con-

trolled at the desired value with 12 M solu-

tions of NaOH and/or HNO3.

Determination of the acid content of the

adsorbent

A mixture of a sample of breadfruit skin

(0.500 g) and 25.0 mL of distilled water was

stirred well and the initial pH of the solution

was measured. The solution was then titrat-

ed with a standardised NaOH solution

(0.010 M), and the pH of the solution was

monitored until it reached up to about 10.

The titration was repeated two more times.

The same titration was performed for

breadfruit core as well.

Acidification of the biosorbent

In order to investigate the effect of acid-

ification of breadfruit waste on metal ion

removal, 0.100 g of each adsorbent was

treated with 50.0 mL of 70 % nitric acid and

shaken for one hour. The resulting suspen-

sion was then filtered and washed with dis-

tilled water. The residue was oven dried at

80 °C for one day and used to investigate the

metal ion removal ability from 10 ppm met-

al ion solutions under optimized conditions.

The extent of removal of each metal ion by

the acidified adsorbent was then compared

with the untreated adsorbent.

Adsorption isotherms

A series of suspensions consisting of

0.100 g of each biosorbent and 50.0 mL of

each metal ion solution of concentration

varying from 5 ppm to 500 ppm was al-

lowed to reach equilibrium under optimized

conditions. The filtrate of each solution was

analyzed for the respective metal content.

The amount of each metal adsorbed by each

biosorbent was calculated using Equation

(1).

Mm

VCCq

fi

e

1000

)( )g (mmol 1-

(1)

where qe is the amount of metal being ad-

sorbed by the adsorbent at equilibrium, Ci is

the initial concentration of the metal ion (in

ppm), Cf is the final concentration of the

metal ion in solution after being adsorbed

(ppm), V is the volume of the solution used

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Priyantha et al., /Ceylon Journal of Science-Physical Sciences 17 (2013) 19-29

22

(mL), m is the mass of adsorbent used (g)

and M is the molar mass of the metal (g mol-

1).

FTIR spectra

Dried samples of breadfruit skin and

core were separately crushed into a fine

powder, mixed with dried KBr solid in a ra-

tio of 1:100 and pellets were prepared for

recording FTIR spectra.

RESULTS AND DISCUSSION

Optimization of experimental parame-

ters

Contact time

Among many factors that govern the ex-

tent of biosorption of Cd (II) and Cu(II) on

breadfruit biomass, the contact time, which

includes both shaking time and settling

time, is an important parameter as it pro-

vides information on time scale to reach

equilibrium. Figure 1 shows the effect of

shaking time on the extent of each metal ion

removed, which can be used to determine

the time required to reach equilibrium. Re-

moval of Cu (II) by breadfruit skin and core

is greater as compared to that of Cd (II), and

further the skin samples show stronger af-

finity toward Cu (II). Nevertheless, Cu (II)

takes a longer time to reach equilibrium,

which is expected because a longer equili-

bration time period would be needed when

more adsorbate is transferred to the surface

of the solid adsorbent. By careful analysis of

the amount adsorbed – shaking time rela-

tionships, it is recommended that shaking

time periods of 180 - 210 min (skin – 180

min; core – 210 min) be needed to achieve

sorption equilibrium of Cu (II), while a

shorter time period of 120 min is sufficient

for Cd (II) on both skin and core.

Many natural adsorbents in raw or

modified forms, including Sri Lankan bread-

fruit, have shown stronger sorption toward

Cu (II) than Cd(II) (Chang and Huang, 2008;

Su et al., 2012; Mohapatra and Anand, 2010)

to support this observation. This can be

partly attributed to the smaller radius of

0.80 °A of the aqua complex of Cu(II) as

compared to that of Cd(II) (0.96 °A) (Per-

son, 2010).

It is observed that there is not much

change in the amount adsorbed of each

metal ion when the adsorbate–adsorbent

system is allowed to stand for up to 4 h,

demonstrating that the equilibrium has es-

tablished upon exposure to the shaking time

period selected (Figure 2). This behavior is

common for all four systems; Cd (II)-

breadfruit skin, Cd (II)-breadfruit core, Cu

(II)-breadfruit skin and Cu (II)-breadfruit

core. Although it is not necessary to opti-

mize settling time after optimization of

shaking time, it is recommended that a min-

imum settling time of one hour be used to

assure equilibrium characteristics of the

systems.

Figure 1: Effect of shaking time on the extent of adsorption of Cu(II) (■) and Cd(II) () on bread-fruit skin (top) and core (bottom) [50.0 mL of 10 ppm metal ion solution, 0.100 g of biosorbent].

Other Artocarpus species are also re-

ported to have comparable shaking and set-

tling times for biosorption of Cu (II) and Cd

(II) (Lim et al., 2011). However, Punicgran-

atum (pomegranate) required an equilibra-

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Priyantha et al., /Ceylon Journal of Science-Physical Sciences 17 (2013) 19-29

23

tion period of 10 h for biosorption of Ni (II)

(Bhatnagar and Minocha, 2010).

Figure 2: Settling time of Cu(II) (■) and Cd(II)

() on breadfruit skin (top) and core (bottom) [50.0 mL of 10 ppm metal ion solution, 0.100 g of biosorbent, shaking times are as given in the text].

Solution pH

The extent of removal of both metal

ions, Cd (II) and Cu (II), is much decreased

when the solution is acidified with HNO3,

probably due to the competition with H+

ions, as reported earlier (Priyantha and

Bandaranayaka, 2011). Increase in the pH of

the solution beyond 6.0 does not significant-

ly increase the extent of removal as com-

pared to that at ambient pH (Table 1). As

additional interference would result in due

to the presence of ionic constituents in

HNO3 and NaOH used for pH adjustments, it

is recommended that the biosorption of Cd

(II) and Cu(II) be carried out under ambient

conditions without any pH adjustment.

Determination of the acid content of

breadfruit skin and core

Determination of the acid content of the

sorbent is useful to gain information on the

mechanism of metal ion uptake by exploring

the type of interaction between each metal

ion and each biosorbent. The pH-titration

curve and its first order derivative plot the

titration of breadfruit skin which can be

used to quantify the acidic content are

shown in Figure 3. The total amount of acid-

ic protons present in breadfruit skin, based

on the equivalence point of the titration, is

estimated to be 2.4 10-4mol per gram of

adsorbent (Vend = 12.0 mL of NaOH). Fur-

ther, the presence of two types of acidic or-

ganic functional groups with ionizable hy-

drogen can be identified by observing two

maxima in the derivative plot shown in Fig-

ure 3. Subsequently, the pKa values of the

two types of acidic groups are determined

to be approximately 5.8 and 7.4 from the

pH-titration curve based on the fact that the

pH at the half-equivalence point during a

pH-titration is equal to the corresponding

pKa value. A similar pH-titration curve and a

derivative plot were observed for breadfruit

core as well. The smaller pKa value would

correspond to carboxylic acid groups while

the larger value corresponds to alcohol or

phenolic groups in comparison with the pKa

values of aliphatic and aromatic carboxylic

acids, and those of alcohols and phenols

(http://research.chem.psu.edu/brpgroup/p

Ka_compilation.pdf). The absence of well-

defined (sharp) peaks in the derivative plot

is due to the availability of many types of

carboxylic acid and phenolic groups in the

biosorbent, and the gradual change in pH in

the titration curve is due to the weak acidic

character of the constituents present.

Sorption of Cu (II) and Cd (II) on bread-

fruit skin and core

The presence of carboxylic acids and alco-

hols/phenolic compounds in breadfruit

waste is supported by FTIR spectra (Figure

4, Table 2). Changes in intensity observed in

the peaks between 1000 cm-1and 1750 cm-1

in the spectra recorded before and after

sorption of Cd(II) provide evidence for in-

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Priyantha et al., /Ceylon Journal of Science-Physical Sciences 17 (2013) 19-29

24

volvement of carbonyl groups in the bond

formation with Cd(II). Cu (II) also results in

Figure 3: The pH-titration curve (top) and the first order derivative plot (bottom) for the reac-tion of a suspension of breadfruit skin with a solution of 0.010 M NaOH.

similar changes in the FTIR spectrum. In-

corporation of the two metal ions to the-

breadfruit matrix is further evidenced by

observing a significant enhancement in the

intensity of the peak for each metal in the

XRF spectrum when metal ion solutions are

treated with each of breadfruit skin and

core. A sample XRF spectrum for Cu (II)-

treated breadfruit skin is shown in Figure 5.

SEM images obtained before and after sorp-

tion of 500 ppm Cu (II) solution provide ad-

ditional support for strong affinity of Cd (II)

on breadfruit skin (Figure 6). Similar chang-

es in SEM images were observed for Cu (II)

as well.

Stronger interaction of Cu (II) as com-

pared to Cd (II), and complexation being the

principal mode of mass transfer (bioreme

diation) are further evidenced from the

formation constants (Kf) of the two metals

with organic functionalities (Bunting and

Thong, 1970). For example, log (Kf) for the

Cu(II)-benzoic acid complex is 1.51, while

that for Cd(II)-benzoic acid is 1.15. These

values are 1.76 and 1.30, respectively, for

acetic acid.

Figure 4: FTIR spectrum of breadfruit core be-fore () and after sorption of Cd (II) (---).

Figure 5: XRF spectra of breadfruit skin before ( ) and after treatment with 100 ppm Cu (II) ( ) and 500 ppm of Cu (II) ( ).

Table 2: Assignment of FTIR peaks for bread-fruit core

Peak locations (cm-1)

Assignment

Untreated Treated with Cd(II)

1736 1736 C=O stretching

1635 1635 C=O stretching

1416 1416 C=C stretching

1153 1155 C-O stretching

Stronger interaction of Cu (II) as compared

to Cd (II), and complexation being the prin-

cipal mode of mass transfer (bioremedia-

tion) are further evidenced from the for-

mation constants (Kf) of the two metals with

organic functionalities (Bunting and Thong,

1970). For example, log (Kf) for the Cu (II)-

benzoic acid complex is 1.51, while for Cd

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Priyantha et al., /Ceylon Journal of Science-Physical Sciences 17 (2013) 19-29

25

(II) )-benzoic acid is 1.15. These values are

1.76 and 1.30, respectively, for acetic acid.

Table 1: Extent of removal of each metal at ambient pH (50.0 mL of 10 ppm metal ion solution, 0.100 g of biosorbent).

Biosorbent Adsorbate Ambient pH Extent of

removal (mmol g-1)

Before metal ion addition

After metal ion addition

Breadfruit skin Cu(II) 5.60 4.89 0.060 Breadfruit skin Cd(II) 5.60 4.81 0.040 Breadfruit core Cu(II) 5.18 4.84 0.058 Breadfruit core Cd(II) 5.18 4.77 0.040

Figure 6: SEM images (approximately 525x magnification) of breadfruit skin (i) before and (ii) after

treatment with 500 ppm Cd (II).

Acidification of the biosorbent

Analysis of the suspension of the acidi-

fied adsorbent and each metal ion solution

indicates that the extent of removal is better

with the acidified adsorbent as compared to

the untreated adsorbent. However, the per-

centage difference of the extent of removal

of Cd (II) is only 2-3 %, while that for Cu (II)

is greater than 20%. This is indicative of the

fact that protonation of the surface of the

biosorbent have no impact on the interac-

tion of Cd (II) and the biosorbent surface.

Hence, the principal mode of mass transfer

from the solution phase to the biosorbent

phase is not ion-exchange, which further

supports the complex formation between Cd

(II) and organic functional groups, as indi-

cated in earlier sections. Nevertheless, ion-

exchange of Cu (II) with H+ contributes to

about 20% of the overall mass transfer pro-

cess, and the remainder is mainly complex

formation. The stronger affinity of Cu (II)

over Cd (II) for ion-exchange with H+ has

already been reported in many instances in

support of the above findings (Chang and

Huang, 1998, Su et al., 2012).

Sorption isotherms

Biosorption of heavy metals on the sur-

face of biomass is mainly due to the chemi-

cal or physical binding between the adsorb-

ate and the biosorbent. The mechanism of

biosorption depends on the type of func-

tional groups present in the surface of the

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Priyantha et al., /Ceylon Journal of Science-Physical Sciences 17 (2013) 19-29

27

biosorbent although the complete mecha-

nism of removal would have many other

contributions.

Amount adsorbed – initial concentra-

tion relationships for a biosorption system

provide information on the type of the iso-

therm, the concentration range for mono-

layer coverage, and the concentration at

which the multilayer coverage begins. The

amount of each metal ion adsorbed on

breadfruit skin and core at different concen-

trations ranging from 5 ppm to 500 ppm

indicates that biosorption leads to a mono-

layer initially up to about 100 ppm of each

metal ion, and the sorption process then

slowly continues (Figure 7). This is a signifi-

cant finding because this demonstrates the

potential of breadfruit waste to be used in

bioremediation of waste water containing

high levels Cu (II) and Cd(II). Howeverinitial

concentrations beyond 500 ppm would not

provide reliable information due to possible

precipitation.

As Figure 7 indicates, the Langmuir iso-

therm, which assumes a monolayer uptake

of an adsorbate on a homogeneous surface,

was tested for both metal ions on each bio-

sorbent surface. The Langmuir model is

represented by Equation (2),

e

ee

CK

CKqq

1

max (2)

Where qe is the amount of the adsorbate be-

ing adsorbed, qmax is the maximum adsorp-

tion capacity, K is the Langmuir constant

and Ce is the concentration of the adsorbate

at sorption equilibrium. Equation (2) is lin-

earized to the form,

maxmax

1

qKq

C

q

C e

e

e

(3) Although this model is empirical, reasona-

bly reliable results can be obtained for the

extent of surface coverage under various

experimental conditions.

Figure 8 shows the linearized Langmuir

adsorption isotherm model for biosorption

of each meal on each biosorbent. Having the

R2 value close to 1.0 suggests that biosorp-

tion of Cu (II) and Cd (II) leads to monolayer

coverage initially (Table 3). Further, it is

evident from the results given in the table

that the Langmuir constant, which is a

measure of the strength of sorption, for

Cu(II) sorption is higher for both skin and

core, further supporting the fact that Cu(II)

is more strongly removed by each bio-

sorbent.

Table 3: Regression coefficients and isotherm constant for biosorption of Cu (II) and Cd(II) on breadfruit skin and core.

Adsorbent Adsorbate Langmuir model

R2 b Breadfruit skin

Cd(II) 0.9823 0.0489

Cu(II) 0.9847 0.0361

Breadfruit core

Cd(II) 0.9245 0.0264

Cu(II) 0.9254 0.0617

Figure 7: Amount of sorption of Cd (II) () and

Cu (II) (■) on breadfruit core.

Thorough mixing of metal ion adsorbed

breadfruit waste with deionized water is

not able to release them to the solution

phase, further demonstrating the strong af-

finity on the biosorbent. Treatment with

strong mineral acids would not be a good

option as certain compounds present in the

biosorbent would denature and mix with

metal ions released. Thus, electrochemical

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Priyantha et al., /Ceylon Journal of Science-Physical Sciences 17 (2013) 19-29

28

reduction under mild acidic conditions

would be a possible approach for the recov-

ery of adsorbed metal ions.

Figure 8: Langmuir adsorption isotherm for biosorption of Cu (II) (■) and Cd (II) () on breadfruit skin (top) and core (bottom).

CONCLUSION

Biosorption ability of both breadfruit

skin and core toward heavy metals ions, Cd

(II) and Cu (II), is so strong that sorption

equilibrium attains efficiently. The optimum

shaking and settling times for Cd (II) are

determined to be 120 min and 60 min for

both skin and core, while the optimum

shaking time for Cu (II) is 180 – 210 min,

with the same settling time period of 60

min. Complexation of Cd (II) and Cu (II)

with acidic functional groups present in

breadfruit waste would probably provide

the principal contribution to the mass trans-

fer of Cd (II) and Cu (II) from aqueous solu-

tion. The maximum removal under opti-

mized conditions from a 10 ppm solution is

0.040 mmol g-1 for Cd (II) by both skin and

core of breadfruit. The corresponding val-

ues for Cu (II) are 0.060 mmol g-1 and 0.058

mmol g-1, respectively. Stronger interaction

of Cu(II) and breadfruit waste is further ev-

idenced by greater Langmuir adsorption

constant (K) for Cu(II) as compared to that

of Cd(II) for both skin and core, and further,

K is greater on skin than core for both met-

als.

Acknowledgements

The authors would like to thank the Gov-

ernment of Negara Brunei Darussalam and

the Universiti Brunei Darussalam for their

financial support. The authors would also

like to thank the Energy Research Group

and Biology Department at the Universiti

Brunei Darussalam for allowing the use of

SEM and XRF instruments.

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