Optimisation of Heavy Metals Uptake from Leachate Using Red Seaweed Gracilaria changii

Journal of Environmental Treatment Techniques

2020, Volume 8, Issue 3, Pages: 1089-1092

J. Environ. Treat. Tech.

ISSN: 2309-1185

Journal web link: http://www.jett.dormaj.com

Optimisation of Heavy Metals Uptake from Leachate

Using Red Seaweed Gracilaria changii

Nithiya Arumugam , Shreeshivadasan Chelliapan , Sathiabama T. Thirugnana and Aida

Batrisyia Jasni²

Department of Engineering, Razak Faculty of Technology and Informatics, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra, 54100 Kuala Lumpur,

Malaysia

School of Civil Engineering, Faculty of Engineering, Universiti Teknologi Malaysia, Johor Bahru, Malaysia

Received: 28/03/2020

Accepted: 07/07/2020

Published: 20/09/2020

Abstract

Heavy metal is one of the pollutants in landfill leachate besides organic and inorganic pollutants. The presence of heavy metal is alarming

due to its harmful nature; makes it incompatible to be discharged into water bodies before treatments. There are many treatment techniques

to remove heavy metals from wastewater, where some of them even involve the coupling of one or more techniques to facilitate and improve

the removal efficiency. However, the adsorption using seaweed is one of the known techniques to eliminate heavy metals from wastewater

efficiently. Therefore, this study introduced a new adsorbent for heavy metal adsorption: red seaweed Gracilari changii. The effect of

operational parameters such as leachate pH (2-7), seaweed dosage (2-10 g), rpm (10-100), and contact time (10-60 min) on the optimum

adsorption of Gracilaria changii was studied. At optimum pH (pH=5), seaweed dosage (10g), rpm (rpm=50) and contact time (30min),

Gracilaria changii showed maximum metal ion removal of 45%, 35%, and 30% for Fe , Cr and Ni respectively. The adsorption was

rapid and reached equilibrium after t=30min in general. This optimisation result can be used as a reference to study the effect of different

dosages of the adsorbent towards the removal rate.

Keywords: Seaweed, Adsorption, Leachate, Heavy metals, Adsorbent

adopted for the treatment of leachate: biological, physical,

Introduction

chemical, and physico-chemical techniques. Nevertheless, the

preference of a technique or coupling of techniques is solely based

on the characteristics of leachate (13). Lately, the removal of

heavy metals by adsorption method using various types of

adsorbents received great interests, with seaweed being one of

them. Seaweeds are macroalges and consists of 10,000 naturally

existing species. These seaweeds can vary in size and typically

grow up to 30 meters in length. Although seaweed has plant-like

physical structure and components, they are not genuine vascular

plants, but are referred as marine algae. Marine algae belongs to

the Kingdom Protista group, which by default are neither plants

nor animals.

Leachate is the dark form of liquid generated via percolation

of rainwater through dumping of solid wastes into landfills.

Rainwater undergoes biochemical processes with wastes and also

with the water contents of the waste itself (1). Random studies

showed that 0.2m of leachate are generated from every one

metric ton of municipal solid waste (2). The qualities and

quantities of leachate vary from one site to another depending on

factors: moisture content, landfill age, climate, site hydrology,

and the degree of waste stabilisation (3).

Leachates are a mixture of colour components, heavy metals,

ammoniacal nitrogen, organic compounds, and inorganic

compounds (4,5). Among these, heavy metals are the most toxic

compounds and draw great attention due to their negative impact

towards both living organisms and the environment as a whole

There are three different groups of seaweeds and they are

identified based on the colour of their thallus namely brown,

green, and red algae. A number of studies show that different

types of seaweeds have been used for the adsorption of heavy

metals from wastewater. There are also vast studies on utilising

red seaweeds as an adsorbent for removal of heavy metals.

However, to date, there are no reported studies on Gracilaria

changii specifically as an adsorbent for the purpose of wastewater

treatment. Therefore, this study focused on determining the

(

6). The presence of heavy metals in leachate are sourced from

used batteries, electronic wastes, paint, construction materials,

mines, fertilisers, and others (7,8) . The most commonly found

heavy metals in leachate are Iron (Fe), Chromium (Cr), Arsenic

As), Nickel (Ni), Lead (Pb), Copper (Cu), Cadmium (Cd), and

Mercury (Hg); are threats to living organisms even in small

amounts (9–12).

(

optimal conditions for the removal of Fe Cr and Ni from

In practice, different modes of treatment methods have been

leachate using the biomass of Gracilaria changii.

Corresponding author: Nithiya Arumugam, Department of Engineering, Razak Faculty of Technology and Informatics, Universiti

Teknologi Malaysia, Jalan Sultan Yahya Petra, 54100 Kuala Lumpur, Malaysia. Email: nithiya85.a@gmail.com.

089

Journal of Environmental Treatment Techniques

2020, Volume 8, Issue 3, Pages: 1089-1092

initial metal ion concentration of 20mg/L. It was visible that the

removal percentage of all metal ions by Gracilaria changii

increased with the increment of pH from 2-5 and was

subsequently reduced as the pH increased further. This could be

explained based on the functional groups of seaweed and the

speciation of metal ions at varying pH levels. The cell wall of

seaweed is made of polysaccharides, carboxyl, and sulphonate

groups. These functional groups are negatively charged and at

Materials and Methods

.1 Leachate

The leachate sample collection was done at Worldwide

Landfill Sdn. Bhd., Jeram, Selangor. The raw leachate sample

was collected and immediately transferred to laboratory in a

sealed high-density polyethylene (HDPE) container and stored at

⁰C to reduce chemical and biological reactions (14).

lower pH,, these groups are protonated with H . Therefore,

.2 Metal Solution

seaweed is unable to hold the positively charged metal ions. At

The stock solutions of Fe (II), Cr(VI) and Ni (II) were prepared

increased pH level of upto 5, the concentration of H were

4 2

from Iron (II) sulphate heptahydrate (FeSO .7H O), Potassium

dichromate (K Cr ) and Nickel (II) nitrate hexahydrate

Ni(NO .6H O) being dissolved in distilled water. During the

course of the experiment, the preferred constant concentration of

0mg/L for each metal ion solution was achieved by diluting the

relatively lower and therefore, the metal ions were able to bind

with the negatively charged surface of the seaweed (15). The

removal percentage started to reduce at pH>5 and the metal

precipitation (formation of metal hydroxide complexes) could be

the reason behind this occurence (27). Therefore, the optimum pH

for heavy metals adsorption using Gracilari Changii in this study

was 5. A maximum of 10%, 5% and 5% of metal ions were

2 7

(

)

stock solution further with distilled water (15). The pH of the

solutions was altered to the required level using 0.1 M NaOH and

2 4

.1 M H SO .

removed for Fe , Cr , and Ni , respectively.

.3 Preparation of Adsorbent

The red seaweed was collected from a cultivation pond in

Kedah. The harvested seaweed was transferred to the laboratory

in a container filled with seawater. The red seaweed was cleaned

and dried. The seaweed was firstly washed with sea water,

followed with tap water and lastly with distilled water to eliminate

epiphytes, debris, sand and salts (16,17). The cleaned seaweed

was subsequently oven-dried at 40⁰C (18) for 24 hr in order to

preserve the phytochemical content of seaweed. The red seaweed

was not chopped into smaller sizes prior to oven-drying to prevent

significant loss of bioactive compounds (19). The dried seaweed

was crushed using a laboratory blender and sieved using a sieve

shaker to obtain sample sizes ranging from 150 to 300 µm (20–

2).

Figure 1: Effect of pH on removal percentage of metal ions

.4 Optimization Study

Batch adsorption experiments were conducted at room

.2 Effect of seaweed dosage

temperature using a jar test apparatus comprised of six rotor

paddles connected to a speed controller to adjust the rotational

speed of the rotor paddles. Glass beakers of 1 litre volume was

filled with 100ml leachate and desired amounts of seaweed was

added. The solution was stirred for different contact time. After

the reaction, the solution was allowed to settle and collected for

heavy metals analysis (23). The supernatant was filtered using a

glass microfibre filter to detach the solid and liquid phases. The

precipitant was analysed for residual heavy metals concentration

in the leachate (24) using atomic absorption spectrometry (25).

The similar method was used throughout the experiment to

investigate the effect of different parameters: pH level, seaweed

dosage, rpm, and contact time on the adsorption rate.

Seaweed dosage is one of the fundamental parameters in

determining the optimum uptake of heavy metals. Therefore, the

effect of seaweed dosage was studied by varying composition.

Figure 2 shows that metal ion removal is proportional to the

increasing seaweed dosage. As the mass increased from 2g to 10g,

the removal percentage increased as well (28–30). As per the

studied dosage range, 10g of seaweed is the optimum composition

for maximum metal ion uptake for all three metals (31). Higher

dosage offers higher surface area or greater active sites for

binding of a constant metal ion concentration. Therefore, more

metal ions bind on the surface of the seaweed and increased the

removal rate (32). A maximum of 60%, 25% and 20% of metal

ions were removed for Fe , Cr , and Ni , respectively.

Results and Discussions

.3 Effect of agitational speed

Figure 3 illustrates the effect of agitation speed of the rotor

.1 Effect of pH

One of the major parameters in deciding the maximum

towards the heavy metals uptake by Gracilari Changii. The effect

was studied within the range of 10-100 rpm. The results showed

that the maximum removal of heavy metal ions occurred at 50

rpm. At lower agitation speed, the seaweed aggregated and did

not spread within the liquid. Therefore, the active binding sites of

the bottom layer were covered and not available for metal

binding, while only the upper layer of the adsorbent was able to

adsorb the metal ions. Thus, sufficient agitation speed is

adsorption ability of an adsorbent is the pH of a leachate. It

influences the solubility of metals, the surface charge of the

adsorbent and the ionisation of the functional groups on the cell

walls. Hence, the effect of the pH value of the leachate varied over

a range of 2-7 on the removal of metal ions was conducted and

the results are as shown in Figure 1 (26). The sample was

collected at t=10min, with seaweed dosage of 2g and showed an

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Journal of Environmental Treatment Techniques

2020, Volume 8, Issue 3, Pages: 1089-1092

necessary to ensure that every active sites were readily accessible

and exposed for heavy metal bindings (33). However, the removal

percentage decreased above 50rpm. This can be explained by the

increase in desorption capacity of the adsorbent at higher agitation

speed (34). A maximum of 60%, 25% and 20% of metal ions were

of 20mg/L. The adsorption process was dependent on the pH of

the solution and pH 5 is the optimum pH value for metal ion

removal by Gracilaria changii. The adsorption process was rapid

for the first 30 minutes and equilibrium was achieved at t=30min

for all three metal ions studied.

removed for Fe , Cr , and Ni , respectively.

Figure 4: Effect of contact time on removal percentage of metal ions

Figure 2: Effect of seaweed dosage on removal percentage of metal ions

Due to seaweed aggregation at lower agitation while

desorption occured at higher speed, the optimum rotational speed

was identified at 50 rpm for maximum removal of metal ions.

Lastly, seaweed dosage of 10g was opted for maximum metal ion

uptake as more active sites were available for binding. Taking into

consideration of the results obtained from this optimisation study

for ion concentration of 20mg/L, it can be concluded that these

parameters can be used to investigate the effect of varying metal

ions concentrations on the adsorption performance of Gracilaria

changii. These optimum conditions show that Gracilaria changii

can adsorb heavy metals and the performance can be improved in

further investigations.

Acknowledgment

The authors would like to thank and extend their greatest

appreciation to the Ministry of Education, Malaysia for funding

this study under the Research University Grant (RUG) Vote

Number: R. Q.K130000.2656.15J80. This work was extensively

supported by Universiti Teknologi Malaysia, Kuala Lumpur by

providing the laboratory facilities.

Figure 3: Effect of rotor’s rotation on removal percentage of metal ions

.4 Efffect of contact time

Figure 4 shows the efficiency of the seaweed adsorbent in

adsorbing metal ions from the leachate with different contact

time. In general, the adsorption increases with increased contact

time for the first 10 to 30 min, and then the rate becomes constant

at t=40-60 min. The decrease in adsorption indicates that the

seaweed surface has reached a saturation level where all the active

sites are not available for further bindings of metal ions (20). The

different metal ions did not significantly affect the performance

of the adsorbent, as the the removal of all of the metal ions

Ethical issue

Authors are aware of, and comply with, best practice in

publication ethics specifically with regard to authorship

(avoidance of guest authorship), dual submission, manipulation

of figures, competing interests and compliance with policies on

research ethics. Authors adhere to publication requirements that

the submitted work is original and has not been published

elsewhere in any language.

increased with increased time. The maximum removal of Fe ,

Cr and Ni was achieved at t=30min. No significant effect in

removal was observed with further increase in contact time

(

35,36). A maximum of 62.5%, 29.3% and 30% of metal ions

Competing interests

2+ 6+ 2+

were removed for Fe , Cr , and Ni , respectively.

The authors declare that there is no conflict of interest that

would prejudice the impartiality of this scientific work.

Conclusions

This paper studied the optimum conditions for Gracilaria

Authors’ contribution

All authors of this study have a complete contribution for data

collection, data analysis and manuscript writing.

changii as a potential adsorbent in removing metal ions (Fe ,

Cr and Ni ) from landfill leachate. The optimisation of four

different factors (pH, seaweed dosage, rpm and contact time) on

adsorption rate was conducted at constant metal ion concentration

091

Journal of Environmental Treatment Techniques

2020, Volume 8, Issue 3, Pages: 1089-1092

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