AbstractThis study investigates the removal ability of Fe and

Mn by limestone, starfish, black shale, sand, and concrete from

wastewater impacted by acid mine drainage. Natural materials or
waste products with a high capacity for heavy metals can be obtained
and employed of with little cost. For investigating the neutralization
capacity, the change in pH, Eh, and EC as a function of time was
quantified. Of the adsorbing agents, concrete showed that the high
neutralization efficiency for AMD and maintained the pH value above
11. The experimental results of desorption revealed that when the
adsorption or precipitation occurs, there was no significant releasing
from all adsorbing agents.

KeywordsAcid mine drainage, Fe, Mn, adsorption, precipitation,
desorption.
I. INTRODUCTION
EAVY metals discharged by abandoned acid mine
drainage (AMD) are one of the major causes of
contaminated subsurface environment (Akcil et al., 2006). The
removal of metal species can be vulnerable by the absence of
reliable adsorbents and solution chemistry adequate to
understanding metal adsorption. The dynamic equilibrium
between metal in water and that adsorbed on the solid phase of
the soil depends on many factors including pH and ionic
strength, aqueous-phase speciation of metal, the chemical
nature and surface area of mineral and organic adsorbents, and
the presence of competing ions.
Residual waste crushed rock from mining activities
represents a major source for metal rich AMD water. AMD
formation involves (Kalin et al., 2006) iron sulphide oxidation
(1), ferrous iron oxidation (2), ferric iron hydrolysis (3), and the
enhanced oxidation of ferric sulphide ions (4). Quite a number
of studies in many countries have been performed to study the
release of metals from coal mine spoils, but only a few in South
Korea. They focused on only how the metals are leached out.
However, the mechanisms leading to the possible migration of
heavy metals further away downstream from the mining site is
still not clear. In this paper the sorption relationship between
wastewater containing Fe and Mn and six adsorbing agents
based on same solution composition and aging conditions was
investigated. The choice to investigate Fe and Mn is based on
the reasoning that these metals are some of the most commonly
occurring base metals in mine discharge.
II. PROCEDURE
A. Study Area
In the Yeongdong Mining District of eastern Gangneung
Province, Fe and Mn is the contaminant of concern with respect
to aquatic life, human health, and wild life. In 1970, the the
Yeongdong mine and mill was identified as the largest remaing
metal loader in Gunsun river. Gunsun river is developed
following the Eest Taeback Mts., which ultimately flows into
East sea in South Korea. On the basis of data collected by the
Mine Reclamation Corporation in 2005, the Yeongdong mining
site contributed approximately 209.6 mg/L Fe and 11.4 mg/L
Mn load to this drainage at summer and winter seasons,
respectively. The primary source of the metals loading was
originated from Sadong Formation including coal mine strata,
Upper Jurassic, Pyungan Superformation. The Sadong
Formation consists of grey sandstones, dark grey shales, coal,
and conglomerates, with a total thickness of 2500 m..

B. Material and Method
AMD water samples from a coal mine disposal area in
Gangneung Province, South Korea (Yeongdong coal mine)
were collected from five sites of a pond during summer season
(August). All water samples were quantified by Inductively
Coupled Plasma Emission Spectroscopy (Varian Co., ICP-OES
730). Chemical compositions for all adsorbing agents were
analysis by X-ray Fluorescence Spectrometry (XRF, RIGAKU
2SX100E) and illustrated on Table I. Miscible displacement
(flow) experiments were conducted at room temperature (295.5
0.5 K) and constant ionic strength (0.01 M). Adsorbing
agents filings were then uniformly mixed with Jumunjin sand
(79.55 % SiO
2
; surface area, 0.05 m
2
/g; 0.5-0.7 mm in
diameter) and packed into polyvinylchloride (PVC) columns
(30 cm long, 10 cm in diameter). Each sand-adsorbent mixture
was first homogenized and then dry packed under the same
pressure for each sample. The ratio of each adsorbing agents
filings to Jumunjin sand illustrated on Table II. Total one
hundred liter (3800 pore volumes) of Yeongong AMD waste
water (initial conc. 209.6 mg/L Fe and 11.4 mg/L Mn) solutions
was passed through each column for 90 days. The columns
were slowly flushed from the bottom and mixed heavy metal
solution was introduced to each columns at a specific discharge
of 4.3 ml/h. Effluent samples were collected with small vial
once a day for 10 min at same time for measuring pH, redox
potential (Eh), electric conductivity (EC), and metal
concentrations.
.
III. RESULTS AND DISCUSSION
MINEQL+ (Version 4.5, Schecher and McAvoy, 1998) was
used to determine the upper concentration limit to avoid the
Comparison of Fe and Mn Removal Using
Treatment Agents for Acid Mine Drainage
Jaeyoung Choi, Ju Young Lee, and Jung-Seek Yang
H
World Academy of Science, Engineering and Technology
International Journal of Environmental, Earth Science and Engineering Vol:1 No:4, 2007
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supersaturation of the metals in this study (Fig. 1). Since the
chemical speciation of Fe and Mn have a different selective
affinity to adsorbent and toxicity (Beveridge and Doyle, 1989).
Ferrous iron exists as Fe
2+
in acid environment. As pH
increases in an open system, composite hydrolyzed ionic
species predominate, and the degree of Fe complexation with
carbonate increases as well. The Mn commonly occurs as oxide
minerals birnesite and vernadite. The manganese oxides vary in
their solubility and easy of reduction. The Mn
2+
ion is a very
soluble species in water, forming hydroxide and carbonate
precipitates only at high pH (>7). However, as the pH increased
above 6, Mn
2+
ion, despite being the most weakly complexing
transition metal, bond with organic matter, oxides, and silicates
and its solubility decreases (Sposito, 1989).

Mn
2+
pH
0 2 4 6 8 10 12 14
%

o
f

s
p
e
c
i
e
s
0
20
40
60
80
100
Mn
2+
MnOH
+
Mn(OH)
3
-
Mn(OH)
4
2-
MnNO
3
+
Pyrochroi

Fe
2+
pH
0 2 4 6 8 10 12 14
%

o
f

s
p
e
c
i
e
s
0
20
40
60
80
100
Fe2+
Fe(OH)
3
-
FeOH
+
Wustite

Fig. 1 Speciation of 10 mg/L Fe and Mn as a function of pH:
Calculation made with MINEQL (ref) using the standard
thermodynamic database. Calculations made for an open system with
log pCO
2
= 10
-0.3
in 0.01 M KNO
3


The six adsorbing agents investigated in this study, white
limestone, gray limestone, concrete, starfish, black shale, and
Jumunjin sand were compared on neutralization efficiency and
ability of metal uptake after treatment (Fig. 2).

Time (day)
0 20 40 60 80 100
C
o
n
d
u
c
t
i
v
i
t
y

(

S
/
c
m
)
0
500
1000
1500
2000
2500
p
H
0
2
4
6
8
10
12
14
R
e
d
o
x

p
o
t
e
n
t
i
a
l

(
m
V
)
-200
0
200
400
600
(A)
Time (day)
0 20 40 60 80 100
C
o
n
d
u
c
t
i
v
i
t
y

(

S
/
c
m
)
1200
1300
1400
1500
1600
1700
1800
1900
2000
p
H
0
2
4
6
8
10
12
14
R
e
d
o
x

p
o
t
e
n
t
i
a
l

(
m
V
)
-200
0
200
400
600
(B)
Time (day)
0 20 40 60 80 100
C
o
n
d
u
c
t
i
v
i
t
y

(

S
/
c
m
)
1000
1100
1200
1300
1400
1500
1600
p
H
0
2
4
6
8
10
12
14
R
e
d
o
x

p
o
t
e
n
t
i
a
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(
m
V
)
-400
-200
0
200
400
600
(C)
Time (day)
0 20 40 60 80 100
C
o
n
d
u
c
t
i
v
i
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y

(

S
/
c
m
)
0
2000
4000
6000
8000
10000
12000
p
H
0
2
4
6
8
10
12
14
R
e
d
o
x

p
o
t
e
n
t
i
a
l

(
m
V
)
-400
-200
0
200
400
600
(D)
Time (day)
0 20 40 60 80 100
C
o
n
d
u
c
t
i
v
i
t
y

(

S
/
c
m
)
0
500
1000
1500
2000
2500
p
H
0
2
4
6
8
10
12
14
R
e
d
o
x

p
o
t
e
n
t
i
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(
m
V
)
-400
-200
0
200
400
600
(E)
World Academy of Science, Engineering and Technology
International Journal of Environmental, Earth Science and Engineering Vol:1 No:4, 2007
18
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Time (day)
0 20 40 60 80 100
C
o
n
d
u
c
t
i
v
i
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y

(

S
/
c
m
)
0
2000
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6000
8000
p
H
0
2
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14
R
e
d
o
x
p
o
t
e
n
t
i
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(
m
V
)
-400
-200
0
200
400
600
(F)
Time (day)
0 20 40 60 80 100
C
o
n
d
u
c
t
i
v
i
t
y

(

S
/
c
m
)
400
600
800
1000
1200
1400
1600
1800
2000
p
H
0
2
4
6
8
10
12
14
R
e
d
o
x

p
o
t
e
n
t
i
a
l

(
m
V
)
-400
-200
0
200
400
600
(G)

Fig. 2 Conductivity, pH, and Redox potential at adsorption step in (A)
control, (B) EX1, (C) EX2, (D) EX3, (E) EX4, (F) EX5, and (G) EX6

For investigating the neutralization capacity, the change in
pH, Eh, and EC as a function of time was tested. A summary of
the results illustrating the dependence of chemical properties of
adsorbing agent on the rate of neutralization is represented in
Fig. 2.
The results obtained for limestone and white limestone are
consistent with those reported by Maree et al. (1999). They
mentioned that neutralization and partial sulfate removal were
highly dependent on the surface area exposed to the liquid and
the OH

, oxygen, CaCO
3
, suspended solids and iron(II)
concentrations, and less dependent on specific surface area and
pressure. They mentioned that two stage processes on the
neutralization were occurred. The first stage is associated with
the neutralization of pure sulfuric acid. The slower second
stage can be attributed to the increasingly thick layer of ferric
hydroxide precipitate forming on the limestone particles,
masking them from further dissolution. The pH for both
limestones was maintained at the neutral range and Eh showed
that the system fulfilled with limestone keeps at the reduced
environment (< 0 mV) after 90 days. The chief difference
between limestone and white limestone is the percentage of
calcite. Similar trends are also present in the starfish for pH, Eh,
and EC.
Especially, Jumunjin sand and black shale lost the
neutralization capacity easily (pH<5), other agents can keep the
pH as above 7.0. In the case of black shale, the pH was reached
at 3.5 after 90 days and Eh was increased to acidic environment
( +200). Otherwise, initial EC is smaller than other agents, and
was decreased from 1500 S/cm to 1100 S/cm since its
property is consisted of hydrophobic material, clay mineral and
organic matter, and then less soluble in the system.
As a result, for each of the 6 agents, only concrete reached
sufficiently low values of Eh, alkaline pH value, low Fe and Mn
concetrations after treatment. However, adsorption ability of
agents for Fe and Mn is very different due to the dissimilar
element character. In addition, the order of adsorption ability of
Fe and Mn onto the various components is inconsistent, which
might indicate that different sorption mechanisms occurred
simultaneously rather than only one sorption mechanism works
in the sorption process of heavy metals onto components. In
this study the effect that various particle sizes of the treated
agents have on the neutralization rate is not investigated. In
general an increased surface area resulted in an increased
neutralization rate, as can be expected. To verify these
conclusions further studies are needed, which are based on
comparisons with different flow rate, redox chemistry with
coexisted ions, and which are competed with other inorganic
cations and anions, and organic materials coexisting in AMD.

ACKNOWLEDGMENT
The project was financially supported by the
KIST-Gangneung Institute (Grant. 2Z03040).

REFERENCES
[1] Akcil, and S. Koldas, Acid Mine Drainage (AMD): causes, treatment and
case studies, J. Clean. Prod. Vol 14, 2006, pp.1139-1145.
[2] T. J. Beveridge, and R.J. Doyle, Metal Ions and Bacteria (Book style),
New York, John Wiley & Sons Inc, 1989.
[3] J. P. Maree, W.F. Strydom, M. de Beer, Integrated iron(II) oxidation and
limestone neutralisation of acid mine water, Water Sci. Technol. Vol 39,
1996, pp. 231-238.
[4] W. D. Schecher, D.C. McAvoy. MINEQL+, A chemical equilibrium
modeling system. Version 4.0 for window, Environmental Research
Software, ME, USA, Hallowell, 1998.






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