Adsorption Efficiency of Lead by Sargassum crassifolium in Different

Biomass Size and Dose

Lily Surayya Eka Putri

, Eka Syafiqa

and Eka Apriliyani

State Islamic University Syarif Hidayatullah Jakarta, Jl. Ir. H. Djuanda No. 95, Ciputat 15412, Indonesia

Keywords: Adsorption, biomass size and dose, lead, Sargassum crassifolium

Abstract: Lead is the dominant water pollutants emerged in high concentration in a watershed of Jakarta, Indonesia.

Biosorption using macroalgae is the efficient method used to eliminate heavy metals from liquid

waste.Sargassum crassifolium is the original species of macroalgae from Indonesia that was used to analyze

the ability of adsorption of lead (Pb) from industrial wastewater at different biomass size and dose.Samples

collected at Pari and Kotok Besar Island, Seribu Island, North Jakarta, Indonesia were used to adsorb Pb

from industrial wastewater with the biomass size of 10-50 µm and 25-500 µm and biomass dose of 0.1,

0.2,and 0.3 mg/L , using duplicate assessment. The adsorption of S. crassifolium on lead was higher in the

size of 10-50 µm than in 250-500 µm, within 60 minutes oscillation at a particular pH. There was not a

significant differentiation between biomass weight and adsorption capacity (p>0.05). Thus, S. Crassifolium

can be used as an alternative biosorbent which has high efficiency for wastewater treatment, even in less

biomass amount.

1 INTRODUCTION

Many industries whose materials are not widely

used from processes such as discharge as high-color

wastewater, biochemical oxygen demand (BOD),

chemical oxygen demand (COD), pH, temperature,

turbidity and toxic chemicals including heavy metals

(Davies et al , 2003). all of that will be responsible for

the release of heavy metals into the environment

through the production process. the process of direct

and indirect disposal of this waste water into water

bodies pollutes water and affects aquatic organisms.

Industrial wastes usually contain metals and a large

number of potentially harmful compounds. This can

cause environmental pollution and affect ecosystems

(Hussein et al., 2004).

The treatment systems of industrial waste are

many and most of them are physic and chemical

processes. Less biological methods are chosen by

industry to treat the wastewater. One of the

biological methods is through biosorption process

using macroalgae. Various macroalgae are found

throughout the world’s oceans including in

Indonesian water which consists of three basic

colors such as green, brown and red algae

(Muhammad and Nwaedozie, 2011).

The presence of heavy metals in the environment

is a major concern due to the toxicity effect to the

aquatic living organisms (Romera, 2007). Thus,

heavy metals recovery from industrial wastewater is

becoming increasingly important in terms of

neutralizing the hazards of heavy metals.

Many studies on heavy metal adsorption by

macroalgae have largely been restricted to various

species of brown macroalgae (Surjani, 2010; Al

Homaida et al, 2011; Huang and Lin, 2015; Sweetly

et al, 2014), microalgae (Putri et al, 2015),

mushroom (Vimala and Das, 2009), and agriculture

waste (Ashraf et al, 2011). In Indonesia, study of

macroalgae as biosorbent of heavy metal is also

developed which reported adsorption of Cu(II) on

Sargassum crassifolium (Ronaldo et al, 2013),

Cr(III) on Euchema spinosum (Sudiarta and

Diantariani, 2008), Pb in Eucheuma spinosum,

Padina minor and Sargassum crassifolium (Putri,

2016), and Pb(II) on Sargassum duplicatum (Buhani

et al, 2006). However, those studies were

experimented in aqueous solution, and less in

industrial wastewater. Therefore, this study was

done to evaluate the potential of brown algae

Sargassum carssifolium to remove heavy metals

from industrial wastewater. As biosorbent, S.

crassifolium are widely found in Indonesian water

and also has the important advantages including low

Eka Putri, L., Syaﬁqa, E. and Apriliyani, E.

Adsorption Efﬁciency of Lead by Sargassum crassifolium in Different Biomass Size and Dose.

DOI: 10.5220/0009935618091814

In Proceedings of the 1st International Conference on Recent Innovations (ICRI 2018), pages 1809-1814

ISBN: 978-989-758-458-9

1809

cost, the abundance distribution in water, size, high

ability to accumulate metals through its cell wall

(Ashraf et al, 2011).

However, the obstacle of the biosorption

method carried out in previous studies was the

availability of biosorbent raw materials in a

relatively limited in the nature. It is known that to

process 10 L of industrial wastewater it takes 100 g

of dried weight of macroalgae or equal to 1000 g of

wet weight of macroalgae. This means that it takes 1

kg of macroalgae to process 10 L of wastewater.

Meanwhile, the amount of wastewater processed by

an industry reaches thousands of liters, so a lot of

macroalgae is needed. Accommodating this

problem, the size and dose of biomass will be an

important aspect. This study focused on the size and

dose of S. crassifolium and analyzing the adsorption

capacity on lead form industrial wastewater. A small

amounts of biomass used will result in cutting costs

for proper industrial wastewater treatment. In

addition, it also conserves macroalgae in the nature

and provides an alternative increase for the economy

of coastal communities.

2 MATERIALS AND METHOD

In this research, it will be conducted at the integrated

laboratory center of the UIN faculty of science and

technology, which will be held in May until October

2018. The macroalgae samples used in this study are

Sargassum crassifolium which is transported from

water around Pari Island and Big Kotok, Seribu

Kepulauan, North Jakarta, Indonesia to the

laboratory. Industrial wastewater is provided from

hazardous waste processing companies located in

Cileungsi, Bogor.

2.1 Preparation of Biosorbent

Before being taken to the laboratory, all samples will

be put into a zip plastic bag, then washed with

seawater to clean from sediments or small organisms

trapped in the macroalgae. henceforth in the

laboratory, all samples were washed and rinsed

again using distilled water then dried in an oven at

50 C for 24 hours to get a stable weight. Dry

samples were grounded with mortars and filtered in

sizes 250-500 μm and biosorbents were ready for

use. Another 10-50 μm size was prepared at

BATAN (National Agency for Nuclear Energy in

Indonesia) using a milling device with 12 balls for 1

hour process.

2.2 Adsorption Test

The experimental design used was Completely

Randomized Design with two (2) replications. Three

variables were tested in this study, including pH,

size and weight of biomass. The variety of biomass

size was 250-500 µm (sa) and 10-50 µm (sb)

whether for biomass dose was 0.1, 0.2, and 0.3 ppm

were examined. All samples were tested in pH 7 and

9 and were oscillated for 60 minutes (Putri, 2016).

The correlation between size and weight of biomass

with adsorption efficiency was analyzed using one-

way ANOVA.

Firstly, for the size 250-500 µm, 0.1, 0.2 and 0.3

g of the dried S. crassifolium was put into 50 ml

wastewater respectively and stirred for 60 minutes

using a magnetic stirrer at 200 rpm. The solution pH

was adjusted to 7 and 9 with NaOH (0.1 M). Then,

the solution were filtered with Whatman paper BF/C

code and the filtrate was analyzed using ICP to

determine the metals concentration at 543 nm

wavelength. The experiment was repeated in the size

10-50 µm.

Metals uptake and removal were calculated as

the difference in the metal concentration(s) before

and after sorption (Ok et al, 2007), according to Eq.

(1).

q = ( ) x

(1)



x 100% (2)

Where q = metal adsorption (mg/g); M = dry

biomass (g); V = volume of the initial lead solution

(L); C

= initial concentration of lead in aquatic

solution (mg/L); C

= final concentration of lead in

the aquatic solution (mg/L) at given time (t; min); R

= removal percentage (%).

3 RESULTS AND DISCUSSION

3.1 Lead Adsorption

The original strain of Indonesian marine brown

algae Sargassum crassifolium was examined for lead

removal at different variation of size of biomass,

250-500 µm (sa) and 10-50 µm (sb), and also

different biomass dose, namely 0.1, 0.2, and 0.3 g.

Different pH was also tested which were pH 7 and 9.

Most of studies were examined adsorption of lead in

aqueous solution (Putri, 2016; Sweetly et al, 2014;

ICRI 2018 - International Conference Recent Innovation

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Vimala and Das, 2009) using macroalgae and also

mushrooms.

The concentration of hydrogen ions is one of the

important parameters in adsorption process which

affects the ionization degree of absorbate during the

reaction and replacement of positive ion in active

sites of cell wall (Sudiarta and Diantariani, 2008).

Figure 1 showed that S. crassifolium in aqueos

solution could remove 98.4% of lead at 60 minutes

oscillation. This rapid metal adsorption for

Sargassum was due to the active binding sites

owned by macroalgae such as –COOH, –OH and –

(Wang and Chen, 2009). This contact time was

further used for the study in wastewater solution.

98.5

Removal

97.5

96.5

95.5

10 20 30 45 60 90 120

time (minute)

Figure 1: Effect of contact time on the adsorption

of lead (Putri, 2016)

Similar findings for adsorption of heavy metals

such as chromium, nickel and lead by other

adsorbents have been reported by Das and Mondal,

2011; Singh and Singh, 2012 who have shown a

balance with achieving 60 minutes. The presence of

a fast adsorption rate is likely due to the increasing

number of empty sites available for adsorption and

is usually controlled by the diffusion process from

bulk to surface (Agarry and Ogunleye, 2014).

Adsorption after 60 minutes may be a process that is

controlled by attachments because the adsorption

site is less available in the macroalase cell wall

Figure 2 and 3 shows the observed removal

percentage for the assayed Pb ion in the wastewater

solution by S. crassifolium at various size and

weight of biomass and at pH 7 and pH 9. The

percentage removal or adsorption efficiency of Pb

from the wastewater by dried S. crassifolium

biomass was found to be 98.11-98.5% (sa) and

99.99% (sb) in various dose of biomass at pH 7, as

shown in Fig. 2. At pH 9, the removal percentage

almost the same as at pH 7 which was 98.34-98.76

(sa) and 97.71-99.99% (sb) in various biomass dose.

This was evidenced by statistical tests that there was

no difference in the ability of lead adsorption on

both biomass size (p>0.05) and also at various dose

of biomass (p>0.05).

100.5

100

99.5

98.5

97.5

0.1 0.2 0.3

weight of biomass (g)

Figure 2: Adsorption capacity on Pb at pH 7

100.5

100

99.5

98.5

97. 5

96.5

0.1 0.2 0.3

weight of biomass (g)

Figure 3: Adsorption capacity on Pb at pH 9

This result was different from the study

conducted by Lee and Park (2012) which reported

pH 4 was the maximum adsorption of lead in

aqueous solution. Similar result was also reported

by Vieira et al (2007), Nessim et al (2011), Sweetly

et al (2014) and Putri (2016) which was pH 4.5, pH

4-5.5 and pH 5 respectively, showed the optimum

lead removal.

Those studies were in aqueous solution which is

the heavy metals were adjusted in specific

concentration to be tested the capability of

adsorption. On contrary to wastewater solution

which is used directly without adjustment of the

concentration. The heavy metals contained in the

wastewater were the mixture of various types of

wastes from the various industries. Therefore, it can

be presumed that the pH condition was seemly

different in aqueous solution and wastewater. There

are a lot of types of heavy metals mixed together in a

very high concentration and this causes the pH

increases. The pH lower than 3.0, the removal of

lead was inhibited possibly as result of a competition

Adsorption Efﬁciency of Lead by Sargassum crassifolium in Different Biomass Size and Dose

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between lead and hydrogen ions and when the pH

increased, the negative charge density on the

macroalgae will also increased due to the

deprotonation of the metal binding sites, which

resulted in increasing the lead adsorption (Vieira et

al, 2007; Nessim et al, 2011).

The most important parameters of biosorption is

the pH (Dubey el, 2014) and regarding to Sargassum

sp. which contains many ionizable groups (carboxyl

groups), it is liable to be influenced by the pH of the

medium which will play a role in binding metallic

ions (Sweetly et al, 2014). The higher the pH value,

the higher the dissociation if the free sites for the

binding process can be produced, and this occurred

at pH values over 5.5 (Vieira et al, 2007). That is

supported by Ho (2005) which reported pH values in

the range of 4.0 to 7.0 were adequate for lead

binding. These values are similar to those obtained

in the present research, of which was pH 7 the

predominance of lead precipitation.

The biomass size, 250-500 µm and 10-50 µm

tested in the present study, showed no significant

differentiation in adsorption efficiency, nevertheless

achieved maximum removal of lead at size 10-50

µm which was higher than at size 250-500 µm. This

is supported by the study conducted by Cossich et al

(2002) which found the biosorbent size did not

influence the capacity and rate of lead removal.

However, this is very important for the industry

because it is related to the cost of processing waste.

Meanwhile, the biomass dose used in the

present study was 0.1, 0.2 and 0.3 g, was not also

showed significant different with removal efficiency

of lead in wastewater solution. This present study

showed that the removal efficiency of lead from

wastewater was not improved with the increasing

dose of assayed biomass. This result was contrary to

Dubey et al (2014) reported that the removal

efficiency was improved with the increasing dose of

biomass 0.25-1.5 g as more surface area in cell wall

of biomass was available for adsorption due to

enhance in the active sites. Leusch et al. (1995) also

found that larger biomass particles of Sargassum

fluitans and Ascophylum nodosum had higher metal

uptake than smaller particles in the case of cadmium,

copper, nickel, lead and zinc. However, these can be

explained by the study by Jia et al (2003) that was

the smaller particles provide a larger surface area for

the attachment of chemical reaction and a shorter

diffusional path for the substrates which supported

the findings of the present study. However, the

findings of this study were in accordance with

observation made by Sweetly et al (2014) in the

uptake of lead by S. myriocystum which decreased

gradually with increased concentration greater than

2g. Vieira et al (2007) was also found the same

results as our findings. Thus, the influence of

biosorbent size on metal adsorption apparently is a

function of both the type of biomass and the metal

ion.

The initial concentration on lead was 13.09

mg/L and after treated by S. crassifolium the final

concentration was ranged 0.001-9.52 mg/L. The

capability of S. crassifolium was definitely high.

Despite, the final concentration of lead at 0.1 and 0.2

dose and size 10-50 µm was below the permissive

level (0.03 mg/L) which is set in the Government

Regulation of Republic of Indonesia No. 82/2001 on

Water Quality Treatment and Water Pollution

Control. The high adsorption ability and achieving

safe concentration to be discharged into the waters

are the advantages of using macrolgae for industrial

wastewater treatment and also environmentally

friendly ways.

3.2 Future Trends

A natural environmentally friendly biopolymer

recently is definitely found its place among the most

important carbohydrates. It is now used effectively

in a wastewater treatment. One of them is guar gum

silica nano-composites were effectively used in the

removal of Cd (II) from aqueous solution at pH 8,

contact time 2 hours, temperature 30

C and

adsorbent dose 10 mg (Singh and Singh, 2015).

Other novel study was hydrogel based on guar gum

(Abdel-Halim and Al Deyab, 2011; Khan et al,

2017) economic and ecofriendly biocomposite for

removal of hexavalent chromium ion Cr (VI).

Utilization of nanocomposite based on

biopolymers is the future developed biosorbent with

the environmental and economic considerations on

replacing the synthetic polymers. Nanocomposite of

biomass is also developed well such as Zhao et al

(2011) for chitosan. Our future research targets are

to prepare nanocomposite from macroalgae and

developed hydrogel based on macroalgae for

wastewater treatment, particularly for heavy metals

uptake. Therefore, environmental quality could be

prevented earlier and the nanocomposite

biotechnology can help industries for waste

treatment process efficiently.

ICRI 2018 - International Conference Recent Innovation

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4 CONCLUSION

The biological method for wastewater treatment has

been used as the efficiency on cost and time to

adsorb heavy metals, which in addition showed high

adsorption capability on heavy metal. The original

species of Indonesian marine macroalgae Indonesia

Sargassum crassifolium exhibited high lead uptake

from industrial wastewater reached almost 99.99%

in smaller size and dose of biomass at pH 7 and 9 for

60 minutes oscillation. Size and dose of biomass was

mentioned and the different pH was analyzed. It was

established that smaller size and dose of biomass

could alleviate the adsorption capacity of heavy

metals in industrial wastewater. This indicated that

S. crassifolium belonging to Phaeophyta division

could be chosen as an alternative environmentally-

friendly method for wastewater which mostly using

chemical methods.

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