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Investigation of Oyster Shell Powder and Zero-valent Iron as
bioinfiltration media to remove heavy metals from Stormwater
Trung Nguyen Thanh1, Po-Hsun Lin2
1
Department of Safety, Health and Environmental Engineering, Ming Chi University of Technology
2
Department of Materials Engineering, Ming-Chi University of Technology
*Corresponding author. E-mail address: phlin@mail.mcut.edu.tw

Abstract
In Taiwan, the huge amounts of abandoned oyster shells have caused problems including their noxious odor and illegal dumping into the sea. It is an urgent requirement,
therefore, to find environmentally safe and profitable uses for waste oyster shell. This paper presents a column study conducted to investigate the potential use of Oyster
Shell Powder (OSP) and Zero-Valent Iron (ZVI) and manganese oxide coated oyster-shell powder (MOCOSP) as filter medium for treatment of heavy metal in stormwater.
Three PVC laboratory-scale columns (4 cm diameter, 40 cm deep) were carried out under dynamic flow conditions and packed with 25cm depth MOCOSP (0.84 – 1 mm),
the mixture of sieved ZVI (1 mm) and sieved OSP (0.84 – 1 mm) in the ratio of 1 to 10 (by weight) and sieved OSP (0.84 – 1 mm) and, respectively. Synthetic stormwater
including Cu, Ni, Pb, Zn was used to introduce to the columns at a flow velocity at 1.67 cm/min. All three columns demonstrated good ability to remove heavy metals
followed the order of (MOCOSP)>(OSP+ZVI)>(OSP), especially Cu and Pb , followed by Zn and Ni. In addition, the removal efficiencies were in the steady decline over
time. The results suggested that OSP is no longer waste, so we fully utilize it as an absorbent for treating heavy metals in water.

Material and methods Results

1. Oyster-shell powder The detailed removal efficiency of Cu(II), Ni(II), Pb(II) and Zn(II) of each
Oyster-shell wastes were washed and at 105oC for 3 hours and dried shells were media (column) are shown on Figure 4, 5, 6, and 7, respectively.
then crushed by hammer and crusher prior to sieving through two sieves of
1.190 and 0.840 mm (figure 1c). 100 100

90

2. Manganese oxide coated oyster-shell powder (MOCOSP)

Removal of Ni by MOCOSP
90
80 Removal of Ni by OSP+ZVI
Removal of Ni by OSP

Removal efficiency (%)

Removal efficiency (%)

70

OSP was base activated to improve the specific surface area. Washed OSP was 80
60

suspended in NaOH solution for 24 hours, then washed with DI water and dried 70 50

in an oven at 105 oC for 5 hours. The prepared base-activated OSP was 60

40

suspended in KMnO4 solution for 24 hours, then calcinated in a muffle furnace

30

Removal of Cu by MOCOSP 20
50
at 250 oC for 4 hours. The KMnO4 was decomposed (Reaction Equation (1)). Removal of Cu by OSP+ZVI
Removal of Cu by OSP 10

40 0

2KMnO 4  K 2 MnO 4  MnO 2  O 2 (Equation 1) 0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180 200

Time (hours) Time (hours)

Figure 4: Removal efficiency of Cu Figure 5: Removal efficiency of Ni

OSP
DI water
100 100
Washed OSP 90

Dried 105 C 5 hours

80
o 90
Figure 1a: Washed OSP
Removal efficiency (%)

Removal efficiency (%)

70

Dried OSP 80
60

50

NaOH (9%) 24 hours 40

30
70

105 oC 5 hours Removal of Pb by MOCOSP

Removal of Pb by OSP+ZVI
20
Removal of Zn by MOCOSP
Removal of Zn by OSP+ZVI
Removal of Pb by OSP 10
Removal of Zn by OSP

Figure 1b: Crushed OSP

60 0

KMnO4 (7%) 24 hours 0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180 200

Time (hours) Time (hours)

Figure 6: Removal efficiency of Pb Figure 7: Removal efficiency of Zn

Calcination 250 oC 4 hours

MOCOSP

Figure 1c: OSP Figure 2: Process of making MOCOSP

Conclusions
In this study, the adsorption potential of OSP was investigated for the removal
3. Column experiments of Cu(II), Ni(II), Pb(II) and Zn(II) from aqueous systems. The kinetic of Cu(II),
Ni(II), Pb(II) and Zn(II) onto media are study with three columns. The
Three PVC columns (4 cm diameter, 40 cm deep) were carried out and packed following results are obtained:
with 25 cm depth MOCOSP, the mixture of sieved ZVI (1 mm) and OSP in the
1. All three columns show the ability to remove heavy metals well but
ratio of 1 to 10 (by weight) and OSP, respectively. Flow velocity was 1.67
tend to decrease over time.
cm/min. Experimental diagram is designed as figure 3.
2. MOCOSP and the mixture of OSP and ZVI exhibited significantly
The heavy metal solution was prepared using the following salts: PbCl2, ZnCl2,
better heavy metal removal efficiency then OSP, especially Pb(II) and
NiCl2, Cu(NO3)2 with few drops concentrated HNO3 in order to prevent the
Cu(II).
precipitation by hydrolysis. The concentration of Pb(II), Zn(II), Ni(II) and
Cu(II) are 1 ppm, 2 ppm, 1 ppm and 1 ppm, respectively. 3. MOCOSP demonstrated the most outstanding and most durable metal
removal capacity. It is worth noting that MOCOSP is a potential media
used to removal Nickel from water.
4. OSP is no longer waste, so we fully utilize it as an absorbent for
treating heavy metals in water.

Acknowledgements
The authors express their sincere gratitude to Ming Chi University of Technology
(MCUT) in Taiwan for the financial support and Wen-Hui Kuan’s lab (MCUT) for
Figure 3: Column experiment helping with the heavy metal analysis.

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