Environ Earth Sci (2011) 64:311–318
DOI 10.1007/s12665-010-0848-0
ORIGINAL ARTICLE
Experimental study on prevention of acid mine drainage by silica
coating of pyrite waste rocks with amorphous silica solution
Masahiko Bessho • Takaaki Wajima •
Takuro Ida • Takashi Nishiyama
Received: 17 November 2009 / Accepted: 30 October 2010 / Published online: 18 November 2010
Ó Springer-Verlag 2010
Abstract Acid mine drainage (AMD) is a widespread
environmental problem associated with working and aban-
doned mining operations. It results from the microbial oxi-
dation of pyrite in the presence of water and air, affording an
acidic solution that contains toxic metal ions. Pyrite micro-
encapsulation, utilizing silica coating, is a novel approach for
controlling AMD that has been shown to be very effective in
controlling pyrite oxidation. The roles of the solution pH and
silica concentration in the formation mechanism for the
AMD-preventing coating were investigated. A silica coating
can be formed from silica solution at pH 7, at which the
amount of Fe eluted from pyrite into the solution is small. No
coating was formed at other pH values, and the amounts of
eluted Fe were larger than at pH 7, especially at pH 11. The
silica coating forms from 2,500 to 5,000 mg/L silica solu-
tions, but not from 0 or 1,000 mg/L silica solutions. The
coating formation rate was slower in the 2,500 mg/L silica
solution than in the 5,000 mg/L silica solution. The forma-
tion of silica coating on pyrite surfaces depends on three
main steps: formation of Fe(OH)3 on the surface of pyrite,
reaction between Fe(OH)3 and silicate in the solution on the
M. Bessho  T. Ida
Department of Energy Science and Technology,
Faculty of Energy Science,
Graduate School of Kyoto University,
Yoshida-Honmachi, Sakyo-ku, Kyoto 606-8501, Japan
T. Wajima (&)
Department of Materials-Process Engineering and Applied
Chemistry for Environments, Faculty of Engineering and
Resource Science, Akita University, 1-1 Tegata,
Gakuen-machi, Akita 010-8502, Japan
e-mail: wajima@gipc.akita-u.ac.jp
T. Nishiyama
Emeritus professor of Kyoto University, Kyoto, Japan
pyrite surface, and growth of the silica layer on the first layer
of silica. The best pH condition to enable these steps was
around 7, and the silica coating formation rate can be con-
trolled by the concentration of silica.
Keywords Acid mine drainage  Pyrite  Silica 
Precipitation  pH
Introduction
Acid mine drainage (AMD) is a serious environmental
pollution issue in the mining industry. AMD is caused by
the oxidation of sulfides such as pyrite, chalcopyrite,
galena or sphalerite by surface or ground water (MSD
1956; Gissinger et al. 1998; Zhang and Evangelou 1998;
Sasowsky et al. 2000). It has an extremely acidic pH value
(as low as 2), and contains a large amount of heavy metals
(Fe, Cu, Pb, Zn, etc.). Thus the effluents, released into lakes
and rivers around mines, pose an immediate threat to the
ecological balance. This threat posed by AMD continues
after mining ceases, since AMD can also be formed when
rain water passes through tailings or mine wastes in
repository sites. In Japan, there are numerous closed mines,
such as the former Matsuo mine. To prevent degradation of
the surrounding environment, the neutralizing agent
CaCO3 has been added to AMD for pH adjustment and
removal of metal ions as hydroxides. However, this neu-
tralizing method must be applied almost permanently
because it cannot suppress the generation of AMD. In the
long term, the cost of this treatment is high (Gazea et al.
1996).
Pyrite in mine waste is initially oxidized by atmospheric
O2, releasing H?, SO42- and Fe2? and is the main source
of acid mine drainage:
123
312 Environ Earth Sci (2011) 64:311–318

FeS2 þ 7=2O2 þ H2 O ¼ Fe2þ þ 2SO42 þ 2Hþ
The Fe2? produced can be oxidized by O2 into Fe3?, and
at pH around 3 (due to acid production), Fe2? is rapidly
oxidized by Thiobacillus ferrooxidans to Fe3? which
oxidizes pyrite at a much faster rate than O2 (Singer and
Stumm 1970). As the activity of Fe3? in solution increases,
oxidation of pyrite by Fe3? becomes the main mechanism
for acid production. The role of Fe3? in the oxidation of
pyrite is demonstrated below:
FeS2 þ 14Fe3þ þ 8H2 O ¼ 15Fe2þ þ SO2 þ the formation mechanism before the coating technique can
4 þ 16H
Commonly, limestone is mixed with waste rock to
prevent pyrite oxidation. This approach, however, has a
short span of effectiveness because after treatment, the
surfaces of pyrite particles remain exposed to atmospheric
O2 and oxidation continues.
A new approach to inhibit pyrite oxidation is through
formation of a coating on the surface of the pyrite which
would prevent both O2 and Fe3? from further oxidizing the
pyrite. Once a coating is established on the surface of
pyrite, oxidation of pyrite and production of AMD would
be prevented. There are reports on the application of sili-
cate (Zhang and Evangelou 1998), phosphate (Vandiviere
and Evangelou 1998; Evangelou 2001) and 1, 3-benzene-
diamidoethanethiol (Matlock et al. 2003) as coating
materials. Among these coating approaches, silica coating
seems to be superior to other methods, because silica
coatings are relatively water-stable solids at circumneutral
pH, are more resistant to acidic surroundings, and sustain
the inhibition of AMD production for several years (Zhang
and Evangelou 1998).
Silica (silicon dioxide) is the most abundant mineral in
the Earth’s crust, so silica coating is friendlier to the
environment than other coating methods. Silica exists in
various forms such as quartz, cristobalite and opal, and is
most commonly found in nature as sand, as well as in the
cell walls of diatoms. Amorphous silica is characterized by
considerable alkaline dissolution, which is different from
crystalline silica. The solubility of amorphous silica is
substantial at pH values well above 7, and decreases
solution, prepared from diatomaceous earth with biogenic
amorphous silica, was used as a coating material, and silica
coating of mine wastes taken from the ex-Matsuo mine,
Iwate, Japan, was attempted (Nishiyama et al. 2003). Our
silica coatings were successful in preventing AMD from
mine waste, and our results further confirmed that the
coating properties of amorphous silica solutions are sig-
nificantly influenced by the pH and silica concentration.
There is little information, however, on the details of the
formation of the silica coating. It is imperative to elucidate
be applied in practice.
This study investigated silica coatings on pyrite sur-
faces. The coatings were prepared from amorphous silica
solutions (from sodium silicate), at various pH values and
silica concentrations. The elution behavior of Fe from
pyrite during silica coating was also examined. The basic
chemistry involved in the formation of a silica coating on
pyrite is reported.
Experimental
Samples
In this study, pyrite samples from the Yanahara mine,
Okayama, Japan, were supplied by Nichika Inc., Kyoto,
Japan. The Yanahara Mine was operated from 1916 to
1991, and pyrite was mined there. Figure 1 shows the
X-ray diffraction pattern of the sample, together with that
of pure pyrite from Joint Committee for Powder Diffrac-
tion Standard (JCPDS) card. It was confirmed that the
sample was almost identical to pure pyrite. For the
Intensity, cps

drastically with decreasing pH (Faure 1991). The solubility

of silica is also affected by temperature and co-existing
elements (Alexander et al. 1954; Iler 1979; Alexander Pyrite
1957; Marshall 1980). Thus, silica can be polymerized
easily in aqueous solutions by decreasing the pH of an
alkaline silica solution, and the polymerization of silica can
be controlled by increasing concentration of silica in the
solution, decreasing temperature, or adding other cations,
such as Fe3?, Al3? and so on (Iler 1979). Therefore, the
10 20 30 40 50 60 70 80 90
silica, which is precipitated from concentrated silica solu-
2
tions by pH adjustment, can be applied as an infill to
prevent AMD. In our previous study, amorphous silica Fig. 1 XRD pattern of the pyrite sample

123
Environ Earth Sci (2011) 64:311–318 313

experiments, specimens were ground and sieved to under

50 lm.

Silica coating on pyrite samples in amorphous silica

solutions

Sodium silicate was purchased from Nacalai Tesque, Inc.,

Kyoto, Japan. The amorphous silica solutions with various
concentrations (0–5,000 mg/L) of silica were prepared by
dissolving sodium silicate in distilled water, and solutions
were adjusted to various pH values by HCl and NaOH
solutions (Nacalai Tesque). It is noted that all silica solu-
tions remained clear (no precipitation occurred).
The silica solution (50 mL) was poured into a poly-
propylene beaker. 0.5 g of pyrite sample was added into the
solution, which was stirred with a magnetic stirrer. After a
predetermined stirring time, each suspended solution was
filtered through a 1 lm pore size filter, and the residues
were dried at 80 °C. The pH of each filtrate was determined
by a pH meter (F-22, Horiba, Ltd., Kyoto, Japan). A con-
trol experiment which used solutions without silica (initial
pH 3, 5, 7, 9 and 11) was also carried out.

Quantitative analysis of Fe and silica

After silica coating, eluted Fe and dissolved silica in
solutions were examined. Fe and Si concentrations in the
filtrates were measured by atomic adsorption spectrometry
(AAS, AA-8500, Thermo Electron Corporation). The silica
concentration was calculated using conversion factors of
28.09 (g/mol Si) and 60.09 (g/mol SiO2).
Observation of pyrite samples after silica coating
Scanning electron microscopic images were recorded using
a scanning electron microscope (SEM, S-3500H, Hitachi)
operated at 15 kV. Carbon was coated on the surface of the
samples under vacuum. Their chemical compositions were
characterized by energy dispersive X-ray spectroscopy
(EDX, Deltaplus, Kevex).
Results
Effect of pH on silica precipitation for coating
on pyrites
Figure 2 shows an SEM image of an untreated pyrite
sample, together with its EDX spectrum. Angulated grains
of approximately 50 lm in size can be seen. It was con-
firmed that the EDX spectrum had peaks comparable to S
and Fe. This is consistent with the X-ray diffraction pattern
(Fig. 1).
Fig. 2 SEM image and EDX spectrum of the pyrite sample. Scale
bar represents 100 lm
Silica coating on pyrite grains was carried out using
5,000 mg/L silica solutions at initial pH values of 3, 5, 7, 9
and 11. Figure 3 shows SEM images of samples treated in
silica solutions at initial pH values of 3, 7 and 11, together
with the EDX spectra of the samples. The features
observed under SEM reflect the changes observed in the
EDX spectra of samples after 6 h of stirring. A plate-like
coating on the pyrite grains was observed in the sample
from the solution with an initial pH of 7 (Fig. 3b), while
angular grains were confirmed in the samples from solu-
tions with initial pH values of 3 and 11 (Fig. 3a, c), as well
as the untreated pyrite sample (Fig. 2). An appropriate
silica coating appears to have formed when an initial pH of
7 was used. As shown in Fig. 3b, the major peak corre-
sponding to Si could be detected in this sample, and the
peak heights for S and Fe decreased drastically, in com-
parison with the untreated sample. In contrast, the samples
treated at initial pH values of 3 and 11 showed only the
major peaks for S and Fe, as did the untreated pyrite
sample.
The pH values of the filtrates after sufficient stirring for
silica coating were examined. Table 1 shows equilibrium
pH values (after stirring for 6 h) of silica solutions and
distilled water as a function of initial pH. It was confirmed
that the pH reached equilibrium after 6 h of stirring. When

123
314
Fig. 3 SEM images and EDX spectra of samples stirred for 6 h with a silica solution (5,000 mg/L) at initial pH values of 3 (a), 7 (b) and 11 (c).
Scale bars represent 100 lm
Table 1 Equilibrium pH values of silica solution (5,000 mg/L) and
distilled water as a function of initial pH after stirring for 6 h
Initial pH Equilibrium pH
Silica solution Distilled water
3 3.2 3.2
5 4.1 3.9
7 7.0 3.9
9 9.1 3.9
11 10.9 7.4
the pyrite sample was added to solutions without silica at
various initial pH values, the pH values of the filtrates
decreased below 4 after 6 h of stirring, except for the fil-
trate with an initial pH of 11, which decreased to 7.4. This
implies that oxidation of pyrites occurs in the solutions
without silica. However, when the coating method was
carried out with the silica solution, the equilibrium pH of
the filtrates was almost the same as the initial pH,
regardless of the initial pH value.
Figure 4 shows the time course of the Fe concentration
in solutions (a) with and (b) without silica during stirring at
various pH values. For the solutions without silica (the
control experiment), no soluble Fe was detected at an ini-
tial pH of 11. The concentration of Fe increased to
approximately 26 mg/L as the pH decreased (Fig. 4b). In
the solution with silica, the Fe concentration at pH 11
increased to 50 mg/L after 6 hours. However, the eluted Fe
concentrations did not exceed 8 mg/L for initial pH values
of 3, 5, 7 and 9 (Fig. 4a). In particular, no soluble Fe was
detected in the filtrate at pH 7.
123
Environ Earth Sci (2011) 64:311–318
Figure 5 shows the time course of the silica concentra-
tion in solutions with silica during stirring at various pH
values. Silica in the filtrate at pH 7 decreased to a con-
centration close to the solubility of amorphous silica,
implying that at this pH the silica was precipitated. For the
other pH values, the silica concentrations of the filtrates
barely changed. These results concur with the results of the
EDX spectra (Fig. 3). Therefore, pH 7 was found to be
optimal for silica coating on pyrites.
Effect of silica concentration on precipitation
for coating on pyrites
To determine the effect of the silica concentration on the
coating formed on pyrites, the silica coating process was
carried out with 1,000, 2,500 and 5,000 mg/L silica solu-
tions at an initial pH of 7. Figure 6 shows SEM images of
the samples treated with 1,000, 2,500 and 5,000 mg/L
silica solutions, together with EDX spectra of the respec-
tive samples. There was no difference in appearance
between the untreated sample and the sample treated with
the 1,000 mg/L silica solution. The major peaks of S and
Fe corresponding to pyrites were detected. As shown in
Fig. 6b and 6c, silica solutions of 2,500 mg/L and over
produced a plate-like coating on the pyrite samples. The
peak heights of S and Fe decreased, while that of Si
increased drastically. The peaks from Na and Cl occurred
because NaCl was produced by the neutralization with
HCl. These results suggest that silica coatings can be
formed at silica concentrations of 2,500 mg/L or greater.
Table 2 shows the pH values of the solutions with var-
ious silica concentrations after 6 h of stirring. It was also
Environ Earth Sci (2011) 64:311–318
Fig. 4 Time courses of Fe
concentrations in silica
solutions (a) and distilled water
(b) with pyrite powder at
various initial pH values. The
Fe concentration (mg/L)
initial concentration of silica
solution was 5,000 mg/L
6000
Silica concentration (mg/L)
5000
4000
3000
2000
pH 3
pH 5
1000
0
0 1 2 3
Duration time (h)
Fig. 5 Time courses of silica concentrations at various initial pH
values. The initial concentration of all silica solutions was 5,000 mg/L
confirmed that the pH achieved equilibrium after 6 h of
stirring. The pH values of the solutions with initial silica
concentrations of 0 and 1,000 mg/L decreased to about 3.9
and 4.6, respectively, while those of the solutions with
initial silica concentrations of 2,500 and 5,000 mg/L barely
changed from the initial pH. The time courses of the silica
concentrations in the solutions with silica are plotted in
Fig. 7. In the solution with an initial silica concentration of
1,000 mg/L, the silica concentration did not change.
However, the silica concentration in the solution with an
initial silica concentration of 2,500 mg/L began to decrease
after 180 min of stirring. The silica concentration in the
solution with an initial silica concentration of 5,000 mg/L
decreased drastically after a few minutes, to a value close
to the solubility of amorphous silica.
Figure 8 shows the Fe concentration eluted from pyrite
into the solutions with various silica concentrations during
315
50
(a) (b)
pH 3
pH 5
40 pH 7
pH 9
pH 11
30
20
10
0
0 1 2 3 4 5 0 1 2 3 4 5 6
Duration time (h)
the experiment. The dissolved Fe concentrations in the
solutions decreased with increasing initial silica concen-
trations. The amounts of eluted Fe in the solutions with 0
and 1,000 mg/L of silica increased in the early stages, and
then became almost constant. However, the Fe concentra-
tions in the solutions with 2,500 and 5,000 mg/L of silica
were always lower than 2 mg/L, and decreased further after
2 h and 5 min, respectively.
pH 7 pH 11
pH 9
Discussion
4 5 6 When pyrite samples are immersed in water, Fe is eluted
from them. This reaction leads to a decrease in pH,
which promotes further elution of Fe, as shown in Fig. 4.
However, most silica solutions eluted less Fe than the
water solutions. The equilibrium pHs of the solutions
using distilled water were acidic (pH 3.2–3.9) for all
initial pH values (apart from the solution with initial pH
11). In contrast, the equilibrium pH values of the solu-
tions containing silica were almost same as the initial
pH. Fe3? in aqueous solution is mostly present as Fe3?
at pH lower than 2.2, Fe(OH)2? at pH 2.2–4.3,
Fe(OH)3(s) at pH 4.3–8.7, and Fe(OH)4- at pH higher
than 8.7; the solubility of Fe decreases from low pH to
around pH 4.3 and increases as pH increases from
around pH 8.7 (Faure 1991). It was also reported that
when pyrite is oxidized by H2O2 in the presence of
sodium acetate and at pH of 4–6, an amorphous ferric
hydroxide (Fe(OH)3) coating was formed (Evangelou
1995). Therefore, little Fe was eluted from the pyrite in
sufficiently concentrated silica solution, especially when
the initial pH was 7 (Fig. 4a, Fig. 8). In the case of an
initial pH of 11, the amount of Fe eluted into the silica
solution increased over time (Fig. 4a), while Fe was not
eluted into distilled water (Fig. 4b), because the
123
316 Environ Earth Sci (2011) 64:311–318

Fig. 6 SEM images and EDX spectra of samples treated with silica solutions of 1,000 (a), 2,500 (b) and 5,000 mg/L (c) (initial concentrations).
Scale bars represent 100 lm

Table 2 Solution pH after 25

Silica Equilibrium
stirring for 6 hours as a function
concentration pH 0 mg/L
of initial silica concentration
(mg/L) 1000 mg/L
20 2500 mg/L
Fe concentration (mg/L)

0 3.9 5000 mg/L

1,000 4.6
15
2,500 7.1
5,000 7.0
10

6000 5

1000 mg/L
Silica concentration (mg/L)

5000 2500 mg/L 0

5000 mg/L 0 1 2 3 4 5 6
4000 Duration time (h)

3000 Fig. 8 Time courses of Fe concentrations in silica solutions of 0,

1,000, 2,500 and 5,000 mg/L after addition of pyrite powder
2000
As shown in Figs. 3 and 5, silica coating at an initial pH
1000 of 7 was confirmed, while silica precipitation was not
observed at initial pH values of 3, 5, 9 or 11. As mentioned
0 above, Fe(OH)3 was formed on the surface of pyrite at pH
0 1 2 3 4 5 6
Duration time (h) 7. It was also reported that rapid gelation of soluble silica
occurs at around pH 7 (Iler 1979). Our experimental results
Fig. 7 Time courses of silica concentrations after addition of pyrite reflect that Fe(OH)3 on the surface of pyrite reacts with
powder. The initial silica solution concentrations were 0, 1,000, 2,500
soluble silica (Si(OH)4) to create a ferric hydroxide silica
and 5,000 mg/L
coating.
The silica concentration also has an influence on the
equilibrium pHs of the silica solution and distilled water precipitation. Pyrites in the silica solutions with initial
were alkaline (pH 10.9) to dissolve as Fe(OH)- 4 and concentrations 2,500 and 5,000 mg/L were coated with
natural (pH 7.4) to form as Fe(OH)3(s) (Table 1). silica (Fig 6). Iler (1979) has reported that the gelation time

123
Environ Earth Sci (2011) 64:311–318 317

Fig. 9 Proposed formation (a) (b)

mechanism of silica coating on
pyrite surface S Fe O Si(OH)
Fe
S Fe S Fe OH
pH 7
Fe S in silica solution
Fe O
S Fe S Fe OH Si(OH)

Fe S Fe O
S Fe S Fe OH
Fe S Fe O Si(OH)

Ferric hydroxide layer

(c) (d)
H
Fe H Fe O O
O O
O

S S Fe O Si O Si OH
Fe O Si OH 3 (HO)SiOSi(OH) 3
OH Fe OH
Fe O O O
OH OH
S S Fe O Si O Si OH
Fe O Si OH

Fe O Fe O O
OH
O OH
Si(OH)
S Fe Si OH S Fe O Si O Si OH
O
Fe O Fe O OH O
O
H
Silica layer

for silicate solutions decreased with an increase in the silica
concentration. This trend corresponds approximately to the
time course of silica concentrations in Fig. 7. On the other
hand, silica solutions with 0 and 1,000 mg/L did not pro-
vide a silica coating (Fig. 6), because the equilibrium pHs
of the solutions were 3.9 and 4.6, respectively.
The coating behavior may be explained in terms of the
reaction between the oxidized surface of pyrite and silicate
ions in aqueous solution, as shown in Fig. 9. The dotted
line indicates the interfacial physical contact between
pyrite surface and iron oxide. The hypothetical mechanism
involved in this scheme was that the pyrite surface was
already oxidized in air, and ferric ion (Fe3?), a pyrite
oxidation product, was dissolved into the solution
(Fig. 9a). At equilibrium pH 7, where the formation of
Fe(OH)3 was favored, Fe3? was hydrolyzed to form iron-
oxyhydroxide precipitate on the surface of pyrite, but at
other equilibrium pHs, iron-oxyhydroxide was not formed
(Fig.9b). A high concentration of silica solution can
maintain the pH of the solution even after pyrite has been
added, while adding pyrite to solutions with low
concentrations of silica leads to a decrease in pH (as also
observed for distilled water) (Tables 1, 2). In the solutions
with higher silica content, the soluble silicates (monomeric
and oligomeric species based on Si(OH)4) in the coating
solution then react with OH groups to form a silica polymer
on the iron-oxyhydroxide surface (Fig. 9c). Once the sur-
face is covered with silica polymer, further condensation of
silica produces a surface silica film (Fig. 9d). Higher
concentration of silica leads to faster production of the
silica film (Fig. 7). The combination of an outer layer of
silica and interior iron-oxyhydroxide layer constitutes an
iron-oxyhydroxide/silica coating.
This mechanism can explain both the optimal pH region
for the silica coating and the relationship between Fe elu-
tion and silica coating.
Conclusions
A silica coating was formed on pyrite grains in silica
solutions under various conditions. The roles of the pH and

123
318
the silica concentration were investigated. A silica coating
can be formed by silica solution at pH 7, and correspond-
ingly, the amount of Fe eluted from pyrite into solution is
lowest at pH 7. The silica coating was formed by the fol-
lowing steps: (1) the surface of pyrites was oxidized by
water or air, and Fe(OH)3 was formed on the surface of
pyrite at pH 7; (2) silicate in the solution reacted with
Fe(OH)3 to form the first layer of silica; (3) assembly of
silicate on the silica layer on the surface of the pyrite
enables growth of the silica layer. Therefore, the optimal
pH to form silica coating on surface of pyrite was 7. The
silica coating was formed in 2,500 and 5,000 mg/L silica
solutions but not in 0 and 1,000 mg/L silica solutions. The
formation rate of the silica coating in the 2,500 mg/L silica
solution was slower than that in the 5,000 mg/L solution.
The formation rate of the silica coating can be controlled
by the concentration of silica, because of the promotion of
silica assembly.
References
Alexander GB (1957) The effect of particle size on the solubility of
amorphous silica in water. J Phys Chem 61:1563–1564
Alexander GB, Heston WM, Iler RK (1954) The solubility of
amorphous silica in water. J Phys Chem 58:453–455
Evangelou VP (1995) Potential microencapsulation of pyrite by
artificial inducement of ferric phosphate coatings. J. Environ.
Quality 24:535–542
123
Environ Earth Sci (2011) 64:311–318
Evangelou VP (2001) Pyrite microencapsulation technologies: prin-
ciples and potential field application. Ecol Eng 17:165–178
Faure G (1991) Principles and applications of inorganic geochemis-
try. Macmillan, New York
Gazea B, Adam K, Kontopoulos A (1996) A review of passive
systems for the treatment of acid mine drainage. Miner Eng
9:23–42
Gissinger PB, Alnot M, Ehrhardt JJ, Behra P (1998) Surface oxidation
of pyrite as a function of pH. Environ SciTechnol 32:2839–2845
Iler RK (1979) Chemistry of silica. Wiley-Interscience, New York
Marshall WL (1980) Amorphous silica solubilities—I. Behavior in
aqueous sodium nitrate solution; 25–300 °C, 0–6 molal.
Geochim Cosmochim Acta 44:907–913
Matlock MM, Howerton BS, Atwood DA (2003) Covalent coating of
coal refuse to inhibit leaching. Adv Environ Res 7:495–501
Mine Safety Department (MSD), Ministry of International Trade,
Industry, Japan (1956) Koen oyobi kouhaisui. Japan Mining
Industry Association, Tokyo
Nishiyama T, Hodo T, Yamada M, Bessho M (2003) Preventing the
escape of harmful elements using silica coating. J Jpn Soc Eng
Geol 43:390–395
Sasowsky ID, Foos A, Miller CM (2000) Lithic controls on the
removal of iron and remediation of acidic mine drainage. Water
Res 34:2742–2746
Singer PC, Stumm W (1970) Acidic mine drainage: the rate-
determining step. Sci 167:1121–1123
Vandiviere MM, Evangelou VP (1998) Comparative testing between
conventional and microencapsulation approaches in controlling
pyrite oxidation. J Geochem Explor 64:161–176
Zhang YL, Evangelou VP (1998) Formation of ferric hydroxide–
silica coatings on pyrite and its oxidation behavior. Soil Sci
163:53–62