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DOI 10.1007/s10653-010-9353-3
ORIGIN PAPER
Received: 20 March 2010 / Accepted: 3 August 2010 / Published online: 3 November 2010
Springer Science+Business Media B.V. 2010
Abstract A pilot-scale plant consisting of an oxidation basin (OB), a neutralization basin (NB), a
reaction basin (RB), and a settling basin (SB) was
designed and built to conduct pilot-scale experiments.
With this system, the effects of aeration and pH on
ferrous oxidation and on precipitation of the oxidized
products were studied systemically. The results of
pilot-scale tests showed that aeration at 300 L/min
was optimum for oxidation of Fe(II) in the OB, and
the efficiency of oxidation of Fe(II) increased linearly
with increasing retention time. However, Fe(II) was
still present in the subsequent basinsNB, RB, and
SB. Results from pilot-scale tests in which neutralization was excluded were used to obtain rate
constants for heterogeneous and homogeneous oxidation. Oxidation of Fe(II) reached almost 100%
when the pH of the mine drainage was increased to
more than 7.5, and there was a linear relationship
between total rate constant, log (Ktotal), and pH.
Absorbance changes for samples from the NB under
different pH conditions were measured to determine
the precipitation properties of suspended solids in the
SB. Because ferrous remained in the inflow to the SB,
oxidation of Fe(II) was dominant initially, resulting
Introduction
In South Korea, there are approximately 2,500 mines,
including 906 metal mines, 379 coal mines, and 1,173
non-metal mines. Among these mines, approximately
150 abandoned surface and underground coal mines
are responsible for acid drainage discharges into
water streams, and are continuously contaminating
surface and groundwater. An estimated 100,000 tons
per day of mine drainage is being discharged from
these mines into water streams (CIPB 1995; Jung
2003). Acid mine drainage (AMD) from abandoned
metal mines not only pollutes the natural environment, for example surrounding soil, and surface and
ground water, but also has toxic effects on crops and
humans as a result of concentration of the contamination (Jung 1994).
In general, drainage from coal mines is not only of
low pH but also contains high levels of SO42- and
heavy metals, including Fe, Al, and Mn (Sengupta
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92
123
concepts with advantages and disadvantages, a complementary new approach should be developed to
minimize maintenance and chemical input and
enhance treatment efficiency.
The objective of this study was to investigate the
applicability of aeration and pH adjustment for
treatment of mine drainage with net alkalinity on a
large scale by conducting pilot-scale tests. A pilotscale (30 m3/day) plant was designed and built to
conduct experiments on the large-scale treatment of
the mine drainage (about 6,000 m3/day). The main
themes were to determine the effects of aeration,
retention time, and pH change on the oxidation of
ferrous, and the effect of ferrous oxidation on
precipitation of the oxidized products. The results
of pilot-scale tests could be expected to contribute to
the design of a full-scale plant on the actual site by
constructing the optimized process on the uneven
ground of the site.
93
123
94
pH
ORP (RmV)
TDS (mg/L)
EC (ls/cm)
Alkalinity (mg/L)
DO (mg/L)
11.8
6.6
237.1
245
500
11.15
93
7.78
Table 2 Concentrations of total recoverable metals and anions in mine drainage (unit: mg/L)
Al
As
Ca
Cd
Co
Cr
Cu
Fe
Sb
0.023
0.003
60.9
ND
0.007
0.005
ND
25.28
1.66
0.005
Li
Mg
Mn
Mo
Na
Ni
Pb
Si
0.04
16.28
1.39
ND
0.91
0.01
0.022
ND
69.39
3.55
Sn
Sr
Ti
Zn
F-
Cl-
NO2-
NO3-
0.96
1.03
0.001
0.047
0.001
0.01
0.501
0.919
0.167
ND
123
95
Type of test
Fixed conditions
II
III
IV
7.2
100
pH
7.0
6.8
40
B
30
SB
80
OB
NB
RB 300 L/min
400 L/min
450 L/min
60
200 L/min
40
20
control
Time (hr)
20
C
12
10
20
40
60
80
100
Time (min)
Fig. 2 Effect of aeration in the oxidation basin on a dissolved
oxygen, b pH, and c Fe(II) oxidation efficiency (aeration rate:
200 L/min, retention time: 1.2 h)
123
96
100
SB
OB
RB
NB
80
SB
OB
NB
60
RT 0.8hr at OB
RT 1.2hr at OB
RT 2.0 hr at OB
OB
SB
40
NB RB
20
0.0
1.5
3.0
4.5
6.0
Time (hr)
Fig. 4 Fe(II) oxidation efficiency in each basin with different
retention times
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1
1
Fe(II) O2 H2 O Fe(III) OH
4
2
dt
fH g2
4
dt
fH g
dFeII
dt
6
Fe2 O2
Since ktotal
k2 Fe3 H k1
dFedtII
Fe2
-1
0.0003
0.0001
0.0000
10
15
20
25
30
ktotal H 2
k2 Fe3 H k1
O2
By plotting [Fe3 H against
y = 1E-05x - 2E-05
R2 = 0.3066
0.0002
9
ktotal H 2
O2
the slope
Ktotal[H+]2/[O2]
ktotal
97
y = 7E-14x + 2E-20
R2 = 0.134
2e-19
1e-19
1e-6
1e-6
2e-6
+
[Fe (III)][H ]
Fig. 5 Relationships between Fe(III) concentration and Ktotal
(a) and between Ktotal[H?]2/[O2] and [Fe(III)][H?] (b)
Figure 6 shows relationships between pH, alkalinity, and dissolved oxygen measured throughout pilot
tests in which neutralization was excluded. As shown
in Fig. 6, pH and alkalinity were in the range 6.76.8
and 92105 mg/L, respectively (average. 93 mg/L as
CaCO3) for non-aeration. However, when the OB was
aerated, pH increased to 6.857.2 and alkalinity
decreased to 7085 mg/L (avg. 75 mg/L as CaCO3).
Based on stoichiometric consideration of Eqs. 1 and
2, 1.8 mg/L alkalinity as CaCO3 could be removed by
1 mg/L Fe(II) oxidation and precipitation of the
oxidation products. Considering the oxidation of
approximately 90% of total Fe(II) which corresponds
to approximately 10 mg L-1 Fe(II), alkalinity should
be reduced by 18 mg/L. Thus, this result is a good
match with the stoichiometric concept.
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7.4
DO vs pH
DO vs alkalinity
pH
90
7.0
80
6.8
Alkalinity (mg/L)
100
7.2
70
aeration
6.6
10
12
60
98
100
NB
60
RB
SB
40
20
pH not adjusted
pH 7.5
pH 8.0
pH 8.5
OB
80
Time (hr)
Fig. 7 Fe(II) oxidation efficiency in each basin for different
pH in the neutralization basin
0
-
K = 0.0551x1014[OH ]2
123
-1
14
2
K = 0.061x10 [OH ]
log(Ktotal, s-1)
-2
-3
log(Ktotal) = 2.1701 pH - 19.208
-4
-5
6.5
7.0
7.5
8.0
8.5
9.0
pH
Fig. 8 Correlation between pH in the NB and log (Ktotal)
(R2 = 0.8395)
99
10
11
Absorbance at 560 nm
0.5
without pH adjustment
pH 7.5
pH 8.0
pH 8.5
0.4
0.3
0.2
0.1
0.0
0
12
Time (hr)
Fig. 9 Kinetics of absorbance at 560 nm of effluents under
different pH conditions in the neutralization basin
Conclusions
The efficiency of Fe(II) oxidation, and precipitation
of the oxidized products, as a result of aeration of
the OB and pH variation in the NB was investigated
in this study. When aeration rates in the OB were
varied (0450 L/min) and the RT was fixed (1.2 h),
pilot-scale tests on the oxidation of Fe(II) showed
that aeration at 300 L/min resulted in the optimum efficiencyapproximately 50% oxidation. With
higher aeration rates, oxidation efficiency did not
increase. With increasing RT in the OB, the efficiency
of oxidation of Fe(II) increased linearly and efficiency
was approximately 72% when the RT was 2 h.
However, Fe(II) still remained in subsequent basins
(neutralization, reaction, and settling basins). Because
of the limited volume of the oxidation basin and the
limited geological configuration of the site, it was not
possible to increase the volume of aeration unit or its
retention time in order to achieve 100% Fe(II)
oxidation. Results from pilot-scale tests in which
neutralization was excluded were used to obtain the
rate constants of heterogeneous and homogeneous
oxidation. The results showed the rate constants were
lower than literature values. Because a very low
determination coefficient resulted from the modeling,
however, the analysis was not suitable for obtaining
reliable values of the rate constants. Enhancement of
the oxidation of Fe(II) by changing the pH in the NB
was also investigated. Oxidation of Fe(II) reached
almost 100% when the pH of the mine drainage was
increased to more than 7.5, and there was a linear
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100
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