Exoskeleton of Two Decapod Species as Biosorbents for Heavy Metal Removal

in Selected Water Samples

Cruz, Daniela Ann S.
Ganalon, Ronin Ric L.
Lazaro, Sofia Kayle R.
Quiñones, Christine Ann M.
Sandajan, Emili Ann J.
Manila Science High School, Manila, Philippines

ABSTRACT. Heavy metals are being discharged in large amounts as contaminants in waste waters which
has posed several health risks to living things. Meanwhile, several studies have presented crustaceans
exoskeletons are able to possess biopolymers which are good in removing these heavy metal ions and the
Philippines being an archipelagic country focuses majorly in aquaculture products namely shrimp and
crabs. With this in mind, this study focuses in the utilization of crab and shrimp shells as efficient and
low-cost biosorbent for the removal of heavy metal contaminants in water. These shell samples were
collected from a public market in Sta.Ana, Manila as wastes which were then washed, sun-dried and
pulverized separately. Two Lead and Cadmium contaminated water samples were prepared and then used
to test for the biosorptive capability of the crab and shrimp shell samples.The results were analyzed using
the Atomic Absorption Spectroscopy (AAS) and interpreted using T-test analysis in SPSS statistics. The
research revealed that there is no significant difference in the biosorptive capability of the crab and shrimp
shells. That being said the outcome of this research could be used to propose methods for improved waste
water treatment.

Keywords: Exoskeleton, Decapods, Biosorptive Capability, Heavy Metals

1. INTRODUCTION
Rapid industrialization, urbanization and anthropogenic activities, whether direct or indirect
human activities, are great sources in the occurrence and accumulation of heavy metals in the environment,
specifically on waters. Heavy metals are naturally occurring elements that have a high atomic weight and a
density at least five times greater than that of water. Their multiple industrial, domestic, agricultural,
medical and technological applications have led to their wide distribution in the environment; raising
concerns over their potential effects on human health and the environment (Tchounwou et al., 2014).

Heavy metals such as Cadmium (Cd), Chromium (Cr), Copper (Cu), Nickel (Ni), Arsenic (As),
Lead (Pb), and Zinc (Zn) are discharged in large amounts as metal-contaminated waste water in industries,
which then are considered as the most hazardous among chemical-intensive industries. In addition, their
high solubility in aquatic environment, they could be absorbed by living organisms. Once they enter the
food chain, it could pose a serious problem in the human body, even at low concentrations (Barakat et.al.,
2012). Generally humans are exposed to these heavy metals via water consumption, dermal contact of
contaminated water, and inhalation of dust. Multiple studies have been conducted in the recent years to
assess the health risks due heavy metals various exposure pathways (Liu et al., 2012). According to Malik
and Khan (2017), presence of these heavy metals in drinking water is a threat to human health, and people
exposed to heavy metals through direct ingestion of water are vulnerable to cancer and other risk. Therefore
it is obligatory to treat metal contaminated water prior to its discharging into the environment. (Arbabi,
Hemati, and Amiri, 2015).

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 Numerous adsorbents like activated carbons, plant or lignocellulosic wastes, clays and biopolymers
are commonly used to eradicate different types of dyes and heavy metal ions from waste water especially
those that are harmful to mankind. Biopolymers possess a number of functional groups, such as hydroxyls
and amines, whichincrease the efficiency of metal ion uptake and the maximum chemical loading
possibility (Rahim, Rakim, and Haris, 2015).

In recent years, few researches have said that exoskeletons of crustaceans, such as crabs, shrimps
and lobsters, and many other organisms, including insects and cell walls of fungi, are able to possess
adsorbents like biopolymers which is good in removing kinds of anionic and cationic dyes as well as heavy
metal ions (Arbia et al., 2012). The effectiveness of these crustacean shells are attributed to their excellent
binding capability to metal ions, their rigid structure, mechanical strength, and ability to survive extreme
conditions employed during regeneration process. In addition to this is that they can be obtained at low or
no cost from seafood industries (Aris, et al., 2015).

The Philippines being an archipelagic country, it has miles and miles of coastlines surrounding
seven thousand plus islands which harbors the highest marine biodiversity in the world (Pimentel, 2016).
Marine aquaculture products are abundant and are naturally a strong point of the country. Majority of the
aquaculture products of the Philippines include shrimps, prawns, and many more (dela Cruz, 2012).

Local markets and businesses of the country serve shrimps and crabs as one of the main ingredient
in Filipino cuisines. And in the processing of these marine food products for human consumption, only
between 50 and 60 % of the total mass are partaken. About 40 % of the waste are the shells and containing
meat and a small amount of lipid residues (Arbia et al., 2012). A small portion of this unprofitable waste is
dried and used as poultry feeds in farms, while the remaining are dumped to the sea, which is one of the
main cause of coastal pollution in regions.

This research paper aspired to determine whether shells of Crustaceans - shrimps and crabs, that are
often just considered unprofitable wastes and coastal pollutants could be utilized as an economical
biosorbent that could assist in removing heavy metals in waste waters.

1.1 Statement of the Problem

The following questions are sought by the researcher along the course of this study:

1. What is the biosorptive capability of the shells of crab after contact to Lead and Cadmium
contaminated water?
2. What is the biosorptive capability of the shells of shrimp after contact to Lead and Cadmium
contaminated water?
3. What significant difference is present between the biosorptive capability of the shrimp and crab
shells?

1.2 Hypothesis

This study was designed to assess the hypothesis that the exoskeletons from decapods, specifically
of shrimps and crabs, are capable biosorbents for the removal of heavy metals in waste water.

Ho : There is no significant difference between the biosorptive capability of shrimp and crab shells.

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1.3 Significance of the Study

This research would determine the biosorptive potential of the Decapods shrimp and crab in the
removal of the heavy metal contaminants present in wastewater.
The results of this study would raise awareness in the people under Local Government Units
about the wide distribution of heavy metal in the environment particularly in water. Better waste disposal
would be formulated to ensure that the heavy metals shall be handled properly and will be thrown in the
right places.
This research would also be significant to future researchers in serving as way in for a new
research that will be beneficial for the further advancement and improvement of water treatment methods.
Findings about this investigation would be utilized by industrial companies particularly those that
work with industrial wastes. The samples utilized, shells of crabs and shrimps, can be used as an
economical alternative in treating water that have been contaminated by impurities caused by commercial
activities and other pollutants.
Lastly, the researchers themselves would also benefit in this study from the experiences and
knowledge they will gain upon the venture.

1.4 Scope and Delimitation

The research was conducted by using the shells of Decapod species and heavy metal - Lead (Pb)
and Cadmium (Cd), diluted in the water sample.

The study was limited to two selected species of the order Decapoda which consists of: (1)
Shrimps; and (2) Crabs.

The experiment was performed within the whole month of July and August, and the researchers did
the experiment in a laboratory supervised by an expert.

1.5 Definition of Terms

The study utilized the following terms that are operationally defined to serve as an aid in understanding
the research:
Biosorption. A property of certain biomass to bind and concentrate heavy metals from even very dilute
aqueous solutions. In this study, it is the capability being tested.
Decapods. Crustaceans with five pairs of thoracic appendages one or more of which are modified into
pincers, with stalked eyes, and with the head and thorax fused into a cephalothorax and covered by a
carapace. In this study, they are the variables used for biosorption.
Exoskeleton.The external skeleton that supports and protects an animal's body, in contrast to the internal
skeleton (endoskeleton). In this study, it is the variable specifically used to adsorbed heavy metals.
Heavy Metal. Used in industrial processes, they are carried by air and water when discharged in the
environment. Cadmium, chromium, lead are some of the metals which persist in nature and can cause
damage or death in animals, humans, and plants even at very low concentrations. In this study it is the
variable to be adsorbed.

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Wastewater. A large expanse of water which is contaminated with pollution agents such as heavy metals
and is commonly found unfit for aquatic wildlife. In this study, it is the variable where heavy metals are to
be adsorbed.

2. METHODOLOGY

This research was approached with three methods namely (1) Sample Collection and Preparation, (2)
Dilution of Heavy Metal, and (3) Adsorption.

2.1 Sample Collection and Preparation

The researchers began by collecting the needed samples for the study. The raw crab shell and shrimp
shell waste were taken from a public market in Sta. Ana, Manila. The shells were then separated from their
meat by steaming, washed and then dried under the sun for 5 hours without any special treatment. The shells
were then separately pulverized to a geometric mean particle size of 0.5mm and placed into two different
containers each containing 40g. The samples were then stored in a closed container prior to use.

2.2 Dilution of Heavy Metal

Due to high level of exposure may result in toxic biochemical effects, the researchers asked help from
Adamson University in the AUTRDC Department in diluting heavy metal into water. Lead (Pb) and
Cadmium (Cd) with an initial concentration of 0.08 mol/L were diluted in a 50 ml distilled water. The
researchers prepared two samples for each crustacean (shrimp and crab).

2.3 Adsorption
The researchers brought the shrimp and crab shells to AUTRDC in Adamson University to determine
their biosorptive capability. The samples were then separately placed in the prepared two water samples
containing Lead and Cadmium, The adsorption experiment were conducted under room temperature with
150 rpm shaking condition to study the effects of mass adsorbent (40g) and time of exposure at 48 hours.
The Lead (Pb) and Cadmium (Cd) concentrations in the supernatant were analyzed through Flame Atomic
Absorption Spectroscopy (Flame AAS) - a technique used for the determination of single elements in
compounds.

Exoskeleton of Two Decapod

Species as Biosorbents for
Heavy Metal Removal in
Selected Water Samples

Collection of
Crab Shrimp
Exoskeletons
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 Dilution of Lead and Cadmium with
distlled water to create synthetic
water.

Testing of treated exoskeleton

in removal of heavy metal in
synthetic water using Flame
AAS

T-test

Proposal for Improved

Wastewater Treatment

Figure 1. Methodological Framework

Figure 1 shows the process of the study wherein the researchers collected samples of the Crab and
Shrimp exoskeletons from a public market in Sta.Ana, Manila. After the shells samples were set, with the
help of the Adamson University Technology Research and Development Center, the synthetic water sample
was created by dilution of the Lead(Pb) and Cadmium(Cd). Then the shells were submerged in the water
sample and tested for their biosorption capability. Afterwards, the results were interpreted using the T-test
to ascertain if there is a significant difference in the biosorptive capability of each shell sample. The
outcome of this research could be used to propose methods for improved waste water treatment.

3. RESULTS AND DISCUSSION

The results were given by Adamson University (AUTRDC) showing the Lead and Cadmium content with
an initial concentration of 0.8 mol/L absorbed by two different decapod species in three trials.

Table 1. Trials for the biosorption of the decapod specie in heavy metal - Lead (Pb) and Cadmium (Cd),
contaminated water sample.

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 Decapod Species Trial Result Unit

1 0.019

Crab Shells 2 0.017

3 0.022
mol/g
1 0.020

Shrimp Shells 2 0.018

3 0.022

The table shows the Lead and Cadmium content absorbed by the thetwo decapod species, the crab
shells imbibed 0.019 mol/g, 0.017 mol/g and 0.022 mol/g. The shrimp shells imbibed 0.020 mol/g, 0.018
mol/g and 0.022 mol/g.

Table 2. T-test Result of the two variables using SPSS.

Tabular Computed
Group Mean Decision Interpretation
Value Value

Crab Shell 0.01933

2.776 0.359 Accept null Not Significant

Shrimp Shell 0.02000

Through T-test the researchers found out that there is no significant difference between the
biosorptive capability of the the shrimp and crab shells. The Null Hypothesis is accepted since the tabular
value 2.776 is greater than the computed value 0.359 the level of significance is 0.05.

4. CONCLUSION AND RECOMMENDATION

With the statistical treatment of the recorded results from the trials of the two exoskeleton variables, it
shows that the null hypothesis is accepted which suggests that there is no significant difference in the
biosorptive capability of the crab and shrimp shells.

In light with the findings of this research, the researchers made the following recommendations; (1)
Widen the scope of the study by adding more selected species to be used as variables for the study. (2)
Widen the scope of the study by utilizing other heavy metal contaminants for the study. (3) Conduct a
campaign regarding the wide distribution of the heavy metals among waters to raise awareness on the health
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risks it poses to living organisms. (4) Contribute on ways with how to treat metal contaminated water prior
to its discharging into the environment. (5) Further study the specific component in the Decapods’ body that
enables it to absorb heavy metals.

ACKNOWLEDGMENT

The researchers would like to express their deepest gratitude and appreciation to Mr. Jonas Feliciano
C. Domingo, the researchers’ teacher in Practical Research 2, for the completion of this paper would not
have been possible without his venerated guidance and support. To Adamson University Technology
Research and Development Center, for giving the researchers’ their time, effort and sharing their
knowledge in helping the researchers in the construction of this endeavour. Furthermore, the researchers
extend their gratitude to Mr. Lanze Andrew V. Molina a chemist from Adamson University for his
in-depth analysis, consultations and insights on this research endeavor.

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