Journal of Chemical

GhusoonTechnology and Metallurgy,

Jawad Shabaa1, 59, 1,Zabibah
Rahman Sahib 2024, 97-104

TREATMENT OF OYSTER SHELLS AND PREPARING THEM

AS AN ADSORBENT SURFACE TO TOLUIDINE BLUE DYE

Ghusoon Jawad Shabaa1, Rahman Sahib Zabibah2

1
College of Medicine, Jabir Ibn Hayyan Medical University
Najaf, Iraq
2
Medical Laboratory Technology Department
College of Medical Technology, The Islamic University
Najaf, Iraq
Email: [email protected]
Received 14 June 2023
Accepted 04 September 2023 DOI: 10.59957/jctm.v59.i1.2024.11

ABSTRACT

The presence of dyes in drainage water is one of the important problems that many seek to solve. This study
included the preparation of the adsorbent surface using the oyster shells as a basis for the preparation of chitosan,
which is a series of carbohydrates and saccharides, by treating them with some simple chemical reactions that grab
the acetyl group (de-acetylation), which is a part of the structure of chitin. Then the basic formula of Chitosan is
ready to carry positive charges, which act as magnet to attract molecules of any substance beside it. A series of assays
were undertaken to assess the efficiency of the adsorption process, such as the weight of oyster shells, equilibrium
time, effect of pH, initial concentration of toluidine blue dye, and particle size of the adsorbent. These experiments
have shown that the equilibrium time was 120 min, the optimum weight of oyster shells was 0.1 g in 100 mL of dye
solution, and the particle size was 150 µm. They also showed there is an effect of the pH on the adsorption of the
dye. The adsorption isotherm was well fitted to both the Freundlich and Langmuir models.
Keywords: adsorption, Langmuir model, Freundlich model, toluidine blue, chitosan, oyster shells.

INTRODUCTION that covers it by secreting calcareous material around

them so as not to affect it and turn into pearls [1 - 4].
Oyster is a marine animal that belongs to the division Chitin, a polyacetylglucosamine with huge functional
of echinoderms and lives in coastal regions and oceans groups including acetyl amino, primary amino, and
characterized by warm or temperate climates where the hydroxyl group that have significantly higher
its shells are glued to the solid bodies found in the adsorption capacities, is the principal main constituent
sea and ocean bottoms and the sea rocks. The oyster’s of oyster shells. Moreover, several linear amino sites
body is surrounded by a bivalve shell and feeds on on every glucose circle of chitin make it simple for the
organic granules and primitives, and it is known that doublet electron pair to join metal ions [3]. A chitin
the vast majority of its kinds live in shallow coastal derivative known as chitosan [beta-(1,4)-2-amino-2-
waters. It is an useful seafood for humans, as it contains deoxy-D-glucose] has been created for a variety of uses,
mineral salts such as zinc, calcium, phosphorus, iron, including as an absorbent. Chitosan-based material,
manganese, sodium, and potassium, which is why it is which serves as a process to remove numerous oyster
an expensive food. And it should be noted that oysters shell piles that not only take up land but also induce a
are a source of pearls, which are formed when an multitude of environmental and cleanliness issues, such
interloper, such as a grain of sand, glides in between one as mosquito larvae, a strong smell, and poor drainage is
of the two shells of the oyster and the protective layer more appealing for use as a sorbent compared to other
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existing biopolymers [5 - 8]. effectiveness of oyster shell as an adsorbent for TB

Due to their ability to prevent light from penetrating, dye was examined. TB adsorption as a function of
dyes discharged by industry into natural water bodies pH, temperature, the starting amount of TB dye, and
seriously harm the environment by interfering with adsorbent particle size has been also studied.
biological processes. Moreover, there are numerous
poisonous dyes for some organisms that cause the EXPERIMENTAL
extinction of water groups. The numerous methods
include biological processing, coagulation, flotation, Apparatus
adsorption, and oxidation to eliminate colors from Shimadzu UV-Vis spectrophotometer (1650 PC)
industrial wastewaters. Adsorption tends to have the was used in spectral studies. Also, pH-meter (WTW3),
most potential for removing it from industrial wastes Electric shaker (Barnstead International), Sensitive
among the alternative treatments [9 - 13]. Toluidine blue analytical balance with four decimal places (Denver
(TB) is regarded as a natural dye, which is described as Instrument), and Heater (Ardeas 51) were used.
a coloring compound produced from naturally occurring
resources of either plants or animals. While charcoal Preparation of the adsorbent (Oyster shells)
and petroleum are the two primary materials used in The process of preparing the surface of the adsorbent
industrial production [14]. Toluidine blue, also known begins by taking samples of oyster shells from the bank
as 7-amino-8-methylphenothiazin-3-ylidene)-dimethyl of the Euphrates River overlooking the Al-Hashemite
ammonium chloride, is a cationic thiazine pigment of area in the city of Hilla. The samples were cleaned up,
the phenothiazine class used in the lab to kill certain the oyster’s body inside was removed, and they were
microorganisms by activating lighting. The structural washed with warm water for half an hour to get rid of
formula is shown in Fig. 1, and it is used as an electron mud and other plankton, then washed with distilled
receptor assay for pneumonia coating in healthy lungs [15]. water and dried by exposure to the sun for 6 hours, and
Adsorption is a separation method, especially for then they were crushed with a special rock grinder. After
the ones that can’t be done with classic methods such the grinding process, the powder of the oyster shells is
as distillation and absorption, in which a substance treated with the following chemicals and several steps:
dissolved in a liquid is deposited on the surface of • Deproteinization: This step involves boiling the
another solid substance named an adsorbent. The powder in a solution prepared from 3 % NaOH for
removal of impurities from wastewater, particularly 60 min. It takes 1 g of the powder to make 10 mL of
utilized in industrial applications, is one of the most the prepared sodium hydroxide solution (1:10, w/v)
significant applications of the adsorption technology and then washing the model with distilled water.
[16, 17]. There are various models that can be used to • Demineralization: The powder is placed in a solution
explain the adsorption mechanism [18]. of acid (1 N HCl) for 30 minutes at room temperature
This is the first study to evaluate the viability of in 1g to 15 mL of prepared acid solution (1:15, w/v),
using oyster shell as a technique to remove TB dye and then the form is washed with distilled water.
through thermodynamic and kinetic experiments. The • Deacetylation is the process of converting chitin
to chitosan by removing the acetyl group. This is
achieved by adding a NaOH solution (40 - 50 %)
usually at 100oC or higher for 30 min to remove the
acetyl groups from the polymer, which is 1 g of the
powder to 10 mL of the prepared NaOH solution
(1:10, w/v). Then it is washed with distilled water
and dried. In the last step, the adsorbent is separated
into different grain sizes using special sieves.
Fig. 2 illustrates the synthetic form of chitin and
Fig.1. (7-amino-8-methylphenothiazin-3-ylidene)-dimethyl chitosan, which was prepared after removing the
ammonium chloride) TB dye. acetyl groups.

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Fig. 2. The structural formula of chitin and chitosan.

Preparation of the adsorbate Table 1. Physical and chemical characteristics of the

The parameters of the dye are shown in Table 1 TB dye.
after 1 g of TB dye has been dissolved in 1000 mL of Parameter Value
distilled water to create the stock solution of 1000 mg
Molecular formula C15H16ClN3S
L-1. Hydrochloric acid (0.1 M) or sodium hydroxide (0.1
M) solutions are used to adjust pH. Molecular mass 305.82 g mol-1
C.I. Name 52040
Batch equilibrium and thermodynamic studies Absorption maxima 590 nm
The equation 1 was used to determine the quantity of
Nature Salt-free dye
TB dye adsorbed onto the oyster shell powder (mg g-1):

qe = (C˳- Ct) × m /V (1)

where qe corresponds to the quantity of dye absorbed

on the adsorbent mass (mg g-1); Co and Ct (mg L-1) are A dimensionless constant called the equipoise factor,
the initial and equilibrium TB dye concentrations in the denoted by the letters RL [19, 20], is discernible through
aqueous medium, respectively; V (L) is the solution’s Eq. 4.
volume; m (g) is the adsorbent mass.
The well-known Freundlich and Langmuir models (4)
are used to describe the distribution of the compound
studied between the liquid and the adsorbent, which is where b is Langmuir constant; Co is initial concentration.
a measurement of the adsorption equilibrium, (Eq. 2). The value of RL indicates whether the line’s outline
is unavailing (RL >1), linear (RL = 1), positive (0<
(2) RL<1), or irreversible (RL = 0).
The sorption of TB through oyster shells was also
where qe is the amount adsorbed in milligrams per gram functionally accomplished by the Freundlich model
of absorbent at equilibria; qm is adsorption capacity [21], (Eq. 5).
maximum (mg g-1); Ce is the dye concentration at
equilibrium; Ka is the equilibrium adsorption coefficient. (5)
The sorption of black tea is monitored via the
Langmuir isotherm model, as shown by the plot of Ce/ Freundlich factors, also known as Kf and n, offer an
qe against Ce as shown in Eq 3. idea of the vantage and Kf [mg g-1(L mg-1)1 n-1]. In the
linearized form (Eq. 5) n is found from the slope of the
(3) line and Kf - from the intercept from the y-axis.

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RESULTS AND DISCUSSION Impact of the contact time

Eight conical flasks were used to study the impact
Calibration Curve of contact time. Each flask contained 0.1 g of the
The varied quantities of TB dye solutions in the adsorbent (oyster shells) and 100 mL of TB dye with a
range of 0.5 - 35 mg L-1 were created after measuring concentration of 100 mg L-1. Fig. 5 depicts the impact
at λmax= 590 nm. The calibration graph of the TB dye of contact time on the adsorption process after samples
and correlation coefficients (R2 = 0.9985) were provided were placed in the shaker instrument for times ranging
while measuring the absorbance values of the various from 20 to 180 min. It was discovered that 120 minutes
concentrations at the maximum value λmax, Fig. 3. is the optimal contact time during which equilibrium is
established. It is caused by the saturation of the active
Determining the optimum conditions sites [22].
Impact of the oyster shells’ mass
A collection of masses in the range of 0.1 - 1.5 g in Impact of sorbents’ size of particles
100 mL of dye at a quantity of 100 mg L-1 of dye were Using a variety of particle sizes (75 – 850 µm),
used to study the impact of the oyster shell’s mass on the the impact of particle size on the TB adsorption was
adsorption of TB dye. After 3 hours of contact time, it was
discovered that 0.1 g is the best mass to obtain the highest
removal ratio at the lowest price. The removal percentage
increased incrementally with weight gain, from 66.03 to
95.75 %, indicating high adsorption as well as a large
number of effective sites, as shown in Fig. 4(a) and
4(b) [20]. Equation 6 is used to get the dye’s adsorption
percentage for each mass of the components (Eq. 6).

(6)

where R is the removal extent, %; C0 is the initial

concentration of TB; Ce is the equilibrium concentration
of TB. Fig. 3. The calibration curve of TB dye.

Fig. 4. Effect of adsorbent amount in the removal of TB dye via oyster’s shells (a)Adsorption percentage. (b) Amount
of dye adsorbed (mg g-1).
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Fig. 5. The impact of contact time on the removal of Fig. 6. The impact of particle size on the removal of TB.
TB dye.

Fig. 7. Adsorption of TB dye by oyster shells at different pH.

examined. Six conical flasks are filled with 0.1 g of each dye at 100 mg L-1 concentration; the pH was controlled
of these six types after being weighed with 100 ml of at (2 - 11) using dissolved HCl or NaOH, each adding
TB dye solution with a concentration of 100 mg L-1 and 0.1 g of oyster shells at 150 µm particle size, and then
shaken for 120 min. It was established that the smaller shaking for 120 minutes. Fig. 7 shows the impact of pH
the oyster shell’s particle size, with regard to a specific on the adsorption mechanism, with an optimum value
quantity of them, the increased is the surface area that of pH = 2.
exists, and as a result, the better the total of obligatory
findings accessible [20 - 23], and the particle size was Impact of the initial TB dye concentration
maintained at 150 µm. This is illustrated in Fig. 6. Various dye concentrations (50 - 250 mg L-1) were
introduced to six conical flasks containing 0.1 g of
Impact of pH oysters with 150 µm particle sizes in order to study
The adsorption capacity was affected by the pH of the impact of the initial concentration of TB dye on
the medium. The dye adsorption was analyzed at various the effectiveness of the adsorption. The flasks were
pH values using six conical flasks, each with 100 mL of then shaken for 120 min. Fig. 8 shows that as the dye
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concentration is increased, more TB is collected onto Table 2. Isotherms data for the removal of the dye.
the adsorbent. This is as a result of the concentration Langmuir Freundlich
gradient’s driving power being stronger with increasing KF(mg-1g)(1mg-1)1/n =
qm(mg g ) = 166.666
-1
initial dye concentrations [24 - 27]. The values for the 32.673
adsorption capacity ranged from 24.75 to 119.9617 mg g-1. Ka(L mg-1) = 0. 208 1/n = 0.5423
R2 = 0.9206 R2 = 0.9750
Isothermal analysis 0.877 – 0.0189)) RL
The Freundlich and the Langmuir models were
employed to explain the connection between the dye and
the surface of the adsorbent. The two equations (3, 5) can
be used to describe these concepts, and Table 1 shows
that both the Langmuir and Freundlich isotherms are
satisfied by the adsorption of TB dye using oyster shells.
Fig. 9 (a, b), illustrates the applicability of both models
to the adsorption of TB dye on the surface of oyster.
Fig. 10 shows the relationship between the separation
factor (RL) and the initial TB concentration. The oyster
shells’ RL value was found to be in the range of 0 to 1,
indicating that the adsorption method was successful. Fig. 8. The influence of the initial TB dye concentration on
Fig. 11 illustrates how the models fit the experimental the adsorption capacity.

Fig. 9. Linearized TB dye isotherms on oyster shells (a) The Langmuir model; (b) The Freundlich model.

Fig. 10. Initial TB concentration onto oyster shells against Fig. 11. Langmuir and Freundlich line information for the
separation factor. TB-oyster shell adsorption.

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data. It seems that the two isotherms could effectively epoxidized palm oil/fatty nitrogen compounds
describe the TB dye adsorption on the oyster shells. modified clay nanocomposites by melt blending,
This discovery relates to the character of oyster shell Polym. Sci. - Series A, 53, 2, 2011, 149-157.
surfaces, which suggests that each TB molecule has 8. E. Guibal, E. Touraud, And J. Roussy: Chitosan
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