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Test The Effectiveness and Characterization of Quartz Sand/Coconut

Shell Charcoal Composite as Adsorbent of Manganese Heavy Metal
To cite this article: Pranoto et al 2020 IOP Conf. Ser.: Mater. Sci. Eng. 858 012041

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ICAMBF 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 858 (2020) 012041 doi:10.1088/1757-899X/858/1/012041

Test The Effectiveness and Characterization of Quartz

Sand/Coconut Shell Charcoal Composite as Adsorbent of
Manganese Heavy Metal
Pranoto1*, Tri Martini1, Fitri Astuti1, Winda Maharditya1
1
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sebelas
Maret University, Jl. Ir. Sutami 36A Surakarta, 57126 Indonesia

*E-mail: pakpranotomipa@staff.uns.ac.id

Abstract. The research on the effectiveness and characterization of quartz sand/coconut

shell charcoal composite as adsorbent of Manganese (Mn) heavy metal has carried out.
Quartz sand was previously activated by using Na2CO3 while the coconut shell charcoal
was activated by using HCl 4 M. The adsorbent characterization was carried out by
Fourier Transform Infrared Analyzer (FTIR), X-RayDiffraction(XRD), Scanning Electron
Microscopy-mapping Energy Dispersive X-Ray (SEM-EDX), and Surface Area Analyzer
(SAA). The adsorption experiment of the Mn metal was carried out by varying the
composition of quartz sand/ coconut shell charcoal. The variations were in the number of
100:0, 0:100, 25:75, 50:50, 75:25 (b/b) at the degree of pH 1- 6 and contact time 10, 15,
20, 30, 45, 60, 75, and 90 minutes by using batch method. The measurement of final
concentration at the equilibrium phase was carried out by using AAS. The optimum
adsorption condition of the Mn metal occurred in the comparison of quartz sand/coconut
shell charcoal 50:50 (b/b), the best condition at the degree of pH 5, contact time during 30
minutes with adsorption capacity of 0.56 mg/gram. The type of adsorption isotherm of
composite quartz sand/coconut shell charcoal adsorbent towards the metal of Mn followed
the Freundlich isotherm theory.

1. Introduction
Water is generally sourced from ground water and naturally contains inorganic elements, such as
ferrous metal (Fe), manganese (Mn), zinc (Zn), lead (Pb) and so on. Mn is an essential heavy metal, where
its presence in certain levels is needed by the human body, but in excessive levels can cause toxic effects.
In drinking water, the allowable manganese level is 0.4 mg/L [1]. According to Purwonugroho research
(2013) [2] the Mn content in ground water reaches 0.8 mg/L. Mn in water can cause turbidity, corrosion
and hardness. Mn also causes a yellowish tint on the laundry. Manganese can cause toxic effects in the
human body if the concentration is too high. The Mn effect mainly occurs in the respiratory tract and
brain. Symptoms of Mn poisoning are hallucinations, forgetfulness and nerve damage. Mn can also cause
Parkinson's disease, lung disease and bronchitis. Prolonged exposure to manganese can cause impotence
[3]. If Mn metal is absorbed by the body it will be difficult to excrete, as well as if contaminated in the
eating environment will be difficult to clean. Therefore, the presence of Mn metal needs to be minimized
or even eliminated.
Many methods have been developed to reduce levels of heavy metals from water bodies, one of which
is the adsorption method [4]. Adsorption is a relatively simple method, the preparation process is simple,
the cost is relatively cheap, efficient, can be done at low concentrations and can use natural adsorbents [5].
Adsorbents that are often used in adsorption include zeolites, natural allophane, chitin, chitosan,
biosorbents from algal species, fly ash, activated carbon and cellulose [6]. Coconut shell can be used as an

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IOP Conf. Series: Materials Science and Engineering 858 (2020) 012041 doi:10.1088/1757-899X/858/1/012041

adsorbent because of the availability of abundant coconut shell and is a good adsorbent for purification,
removing color, odor, dechlorination, detoxification, filtering, separation and can be used as a catalyst [7].
Coconut shell charcoal also has hydroxyl and carboxyl active groups which influence the adsorption
process [8]. Rahmawati and Dony (2016) [9] use activated coconut shell charcoal to adsorb Fe, Mn and Al
metals in water up to 20%. Quartz sand has active groups of silanol (Si-OH) and siloxan (Si-O-Si) so that
quartz sand can be used as manganese metal adsorbent (Mn). Quartz sand can be used as an adsorbent as
previously reported research which shows quite good efficiency. Lindasari et al (2017) [10] conducted a
study on the adsorption of chloride ions in water using quartz sand and had an adsorption capacity of
0.2711 mg/g. However, an adsorbent without pre-treatment if applied as an adsorbent gives less than
optimal results. Therefore, this research is conducted to increase the activity of adsorbent.
In this research, in addition to activation, physical merging of quartz sand and coconut shell charcoal is
also carried out so that quartz sand/coconut shell charcoal will be formed. The merger will add active
groups to the adsorbent and increase the surface area of the adsorbent so that it is expected to optimize the
performance of the composite of quartz sand/coconut shell charcoal in absorbing the metal of Mn.

2. Materials and Methods

2.1. Materials
Quartz sand, coconut shell, distilled water, Mn 1000 ppm mother solution, HCl p.a (Merck), concentrated
HNO3 p.a (Merck), Na2CO3 p.a (Merck), ammonia p.a (Merck).

2.2. Preparation of Adsorbent

Quartz sand is cleaned of impurities, sifted and finely ground. After smooth, proceed with sifting using
150 mesh sieve. Then wash with 0.1 M HNO3 while stirring with a magnetic stirrer for 1 hour. Washing is
done 3 times and dried by aerated [11]. Coconut shell is cut into small pieces, washed 3 times, dried in the
sun, purified with 400 oC for 1 hour, grinded and sieved using a 150 mesh size sieve [12]. The quartz sand
powder and coconut shell which has dried then are identified.

2.3. Adsorbent Activation

Chemical activation is carried out for quartz sand, 165 grams of quartz sand and 135 grams of sodium
bicarbonate are mixed and the mixing process is carried out evenly. Then put in a crucial and then heated
to a temperature of 1100 °C for 2 hours. Then the melt is cooled and crushed into powder [13]. Then for
the coconut shell, as much as 50 grams of coconut shell soaked with 100 mL of 4 M HCl solution for 24
hours, then filtered and washed with distilled water. The activated carbon produced is then dried in an
oven at 110 °C for 3 hours, then cooled in a desiccators [14]. The activated adsorbent is then characterized
by FTIR, XRD, SAA and a specific total acidity test.
The next step is to make variations in the composition of the adsorbent between quartz sand and
coconut shell, which are 25:75, 50:50, and 75:25 (w/w). Mixing each variation of the composition was
carried out using stirring for 1 hour. Then after being filtered the solid phase is washed with distilled
water. Furthermore, the resulting composition is heated at a temperature of 105 oC for 4 hours. The dry,
solid phase is then crushed with a mortar and sieved with another 150 mesh sieve.

2.4. Adsorbent Effectiveness Test

Optimization of the composition of the adsorbent is done by as much as 0.1 gram of composite quartz
sand / coconut shell charcoal with variations in the composition of 100: 0, 75:25, 50:50, 25:75 and 0: 100
(w/w) mixed with 10 mL of solution Mn 6 ppm with pH 5. The solution is stirred for 60 minutes at a
constant speed at room temperature. The composite was filtered with Whatman No. filter paper. 42.
Filtrate is measured by AAS. The pH optimization of the solution was carried out by as much as 0.1 gram

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ICAMBF 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 858 (2020) 012041 doi:10.1088/1757-899X/858/1/012041

of quartz sand/coconut shell charcoal composite at an optimal composition mixed with 10 mL of 6 ppm
Mn solution using a buffer variation of pH 1, 2, 3, 4, 5, and 6. The solution was stirred for 60 minutes at a
constant speed at room temperature. The composite was filtered with Whatman No. filter paper. 42.
Filtrate is measured by AAS. Then the optimization of the contact time of the solution is done by as much
as 0.1 gram of composite quartz sand/coconut shell charcoal at an optimal composition and pH mixed with
10 mL of 6 ppm Mn solution, stirring with contact time variations of 10, 15, 20, 30, 45, 60 , 75 and 90
minutes at constant speed at room temperature. The mixture was filtered with Whatman No. filter paper.
42. Filtrate is measured using AAS.
2.5. Determination of Adsorption Isotherms
There are 0.1 gram of composite quartz sand/coconut shell charcoal at optimum conditions was added
with a solution of Mn 2, 4, 6, 8, 10 and 12 ppm as much as 10 mL then stirring with the maximum contact
time at room temperature. The adsorption results were filtered with Whatman No. filter paper. 42 and
measured by AAS. The results obtained were then analyzed by the Langmuir and Freundlich isotherms.

3. Result and discussion

3.1. Identification of Adsorbent
3.1.1. FTIR Characterization
FTIR characterization is used to determine the functional groups found in raw materials. The results of
FTIR analysis of coconut shell charcoal showed the presence of hydroxyl and carboxyl active groups
while the results of quartz sand analysis showed the presence of silanol and siloxan active groups. These
active groups can be used as adsorbents. FTIR spectra of coconut shell charcoal and quartz sand are
shown in Figure 1. Data on functional group analysis is shown in Table 1.

(a)
914
C-O
1707
C=O
Transmittance (a.u)

1576 1037
C=C C-O
3421
O-H
(b)
758
1635 Si-O-Si
H-O-H

3436 449
1437 1022
O-H O-Si-O
H-O-H Si-O-Si
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavelength (cm )

Figure 1. FTIR spectra of coconut shell charcoal (a) and quartz sand (b)

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ICAMBF 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 858 (2020) 012041 doi:10.1088/1757-899X/858/1/012041

Table 1. Data from the analysis of the functional group coconut shell charcoal and quartz sand

No Functional Group Wavelength (cm-1)

Reference Coconut shell charcoal Quartz sand
[15]
1 O-H 3550-2000 3421 3436
2 H-O-H 1641[16] - 1635; 1437
3 C=O 1705[8] 1705 -
4 C=C 1589[8] 1576 -
5 C-O 1300-800[8] 914; 1037 -
6 Si-O-Si asymmetric strech 1076[17] - 1022
7 Si-O-Si symmetric strech 771[17] - 758
8 O-Si-O 461[18] - 446

3.1.2. XRD Characterization

XRD characterization was used to determine the mineral content of coconut shell charcoal and quartz
sand. The results of XRD analysis showed that coconut shell charcoal contains cristobalite (C), fayalite (F)
and manganoan (M) minerals while quartz sand contains quartz minerals (Q). XRD diffractogram is
shown in Figure 2.

C
F M

(a)
Intensity (a.u)

Q Q

Q Q

Q
Q

(b)

20 40
o
2theta ( )

Figure 2. XRD diffractograms of coconut shell charcoal (a) and quartz sand (b)

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ICAMBF 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 858 (2020) 012041 doi:10.1088/1757-899X/858/1/012041

3.1.3. Surface Area and Acidity Analysis

The surface area will provide an area on the surface of the adsorbent so that the Mn metal can be
adsorbed. The specific total acidity analysis aims to show the presence of active sites on the surface of the
adsorbent and determine the effect of acidity on the adsorption capacity. More acidic sites indicate that the
adsorbent has more active sites so that it will make it easier for the adsorbent to interact with the Mn metal
in the adsorption process. The more active sites on the adsorbent, the more likely the adsorption capability
will be. The results of surface area and acidity analysis of coconut shell charcoal and quartz sand are
shown in Table 2.

Table 2. Surface area and acidity of coconut shell charcoal and quartz sand
Sample Surface area (m2/g) Acidity (mmol/g)
charcoal 51,420 7,647
quartz 17,458 9,882

3.2. Adsorbent Effectiveness Test

3.2.1. Optimization of Adsorbent Composition
Optimization of the adsorbent composition was carried out on a comparison of the composition of quartz
sand composites: coconut shell charcoal 100: 0, 0: 100, 25:75, 50:50 and 75:25 (w/w). The optimum
composition of quartz sand/coconut shell charcoal adsorbent composites is at a ratio of 50:50 (w/w) with
an adsorption capacity of 0.573 mg/g and an absorption percentage of 97.02%. These results indicate that
the composite of quartz/coconut shell charcoal with a ratio of 50:50 (w/w) supports each other to form
more active sites and increase the surface area so that they are able to absorb Mn metals maximally.

3.2.2. Optimization of pH Conditions

Optimization of pH conditions aims to determine the optimum pH conditions in Mn metal adsorption. In
this study the optimum pH of Mn solution was obtained at pH 5 with an adsorption capacity of 0.556 mg/g
and an adsorption percentage of 94.59%. At pH 5 the H+ ions contained in the solution are relatively small
so that the active group of adsorbent binds more easily to the metal Mn.

3.2.3. Contact Time Optimization

The optimum contact time of Mn metal adsorption occurred at 30 minutes contact time with adsorption
capacity of 0.56 mg/g and the percentage of adsorption of 94.22%. The longer the contact time of the
solution with the adsorbent, the greater the adsorption capacity. However, if the contact time is sufficient,
the adsorption capacity will be stable.

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ICAMBF 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 858 (2020) 012041 doi:10.1088/1757-899X/858/1/012041

3.3. Characterization of Adsorbent Composites Before and After Adsorption

3.3.1. FTIR Characterization
FTIR spectra of adsorbents before and after adsorption are shown in Figure 3.

(a)
. 790
Si-O-Si
443
O-Si-O
Transmittance (a.u.)

1575
C=C 1033
Si-O-Si; C-O
3443 779
(b)
O-H Si-O-Si

1564
469
C=C O-Si-O
3421
O-H
1070
Si-O-Si: C-O

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavelength (cm )

Figure 3. FTIR spectra of composite before and after adsorption

FTIR analysis aims to determine the possibility of interaction between the active group on the
adsorbent with Mn metal after the adsorption process. The possibility of this interaction can be seen by the
shift of the wave numbers in the FTIR spectra. Active groups such as Si-OH /-COOH will interact with
Mn metals to form Si-O-Mn /-COO-Mn. A lower wave number shift indicates that the bond strength
decreases while a higher wave number shift indicates an increase in bond strength.

3.3.2. SEM-EDX characterization

The SEM test results are shown in Figure 4 while the EDX test results are shown in Table 3. The
appearance of the adsorbent surface before adsorption tends to have many open pores that allow Mn metal
to fill the empty space on the surface of the adsorbent. After the adsorption process, the pores on the
surface of the adsorbent are more closed which is possible because it is covered by Mn metal. The EDX
test results of adsorbent composites after adsorption contained more Mn content than before adsorption
that is equal to 1.2% which proves that the adsorbent composites are capable of absorbing Mn.

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ICAMBF 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 858 (2020) 012041 doi:10.1088/1757-899X/858/1/012041

(a) (b)

Figure 4. Composite morphology adsorbent quartz sand/ coconut shell charcoal 50:50 (w/w) before
adsorption (a) and after adsorption (b)
Table 3. Content of elements in composite adsorbent

Element content (%)

No Adsorbent
Si C O Mn
Quartz sand/ coconut shell charcoal
1 composite before adsorption 9,3 38,7 46,9 0,1
Quartz sand/ coconut shell charcoal
2 composite after adsorption 12,6 31,6 31,6 1,2

3.4. Determination of Adsorption Isotherms

The adsorption isotherm curve is shown in Figure 5. Based on the isotherm curve, shows that the R 2 value
for the Langmuir isotherm is 0.935 with an adsorption capacity of 0.304 mg/g while the R2 value on the
Freundlich isotherm is 0.994 with an adsorption capacity of 0.661 mg/g. The process of adsorption
between Mn metal with quartz sand/coconut shell charcoal composites follows Langmuir and Freundlich
isotherm models because the R2 values are equally close to 1. However the Mn metal adsorption capacity
is greater in the Freundlich isotherm, so it can be concluded that the adsorption of Mn metal by composite
quartz sand/coconut shell charcoal is more dominant in the Freundlich isotherm. The Freundlich isotherm
shows that the adsorption process between adsorbents and adsorbates occurs physically through the van
der Waals force. Mn metal which has a positive charge will interact with O atoms in the negatively
charged Si-OH group so that the distance between Mn ions and O atoms is closer due to dipoles. The
interaction between adsorbent and adsorbate occurs by the way Mn metal attaches to the pores of the
adsorbent with weak binding energy through van der Waals forces. The existence of a weak pulling force
causes the adsorbate to move from one part of the surface to another part of the surface of the adsorbent so
that it can form a multilayer.

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ICAMBF 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 858 (2020) 012041 doi:10.1088/1757-899X/858/1/012041

(a) (b)

Figure 5. Isotherms curve of Langmuir (a) and Freundlich (b)

4. Conclusion
The results of adsorbent characterization showed the presence of active groups which indicated that the
adsorbent was able to absorb Mn metal. The quartz sand/coconut shell charcoal adsorbent composite can
adsorb Mn metal with the composition of quartz sand/coconut shell charcoal 50:50 (w/w), the best
conditions at pH 5, contact time for 30 minutes with adsorption capacity of 0.56 mg/g and the adsorption
percentage of 94.22%. Type of adsorption isotherm composite of quartz sand/coconut shell charcoal
adsorbent on Mn metal is more dominant in Freundlich isotherm with adsorption capacity of 0.661 mg/g.

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