minerals

Article
Acid Mine Drainage Sources and Impact on Groundwater at the
Osarizawa Mine, Japan
Naoto Nishimoto 1, *, Yosuke Yamamoto 1 , Saburo Yamagata 2 , Toshifumi Igarashi 3 and Shingo Tomiyama 3

1 Division of Sustainable Resources Engineering, Graduate School of Engineering, Hokkaido University,

Sapporo 060-8628, Japan; culuclunosuke@eis.hokudai.ac.jp
2 Mitsubishi Materials Corporation, 3-2-3, Marunouchi, Chiyoda-ku, Tokyo 100-8117, Japan;
s-yamaga@mmc.co.jp
3 Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan; tosifumi@eng.hokudai.ac.jp (T.I.);
tomiyama@mmc.co.jp (S.T.)
* Correspondence: nishimoto.naoto.p9@elms.hokudai.ac.jp; Tel.: +81-11-706-8191

Abstract: Understanding the origin of acid mine drainage (AMD) in a closed mine and groundwater
flow system around the mine aids in developing strategies for environmental protection and manage-
ment. AMD has been continuously collected and neutralized at Osarizawa Mine, Akita Prefecture,
Japan, since the mine was closed in the 1970s, to protect surrounding river water and groundwater
quality. Thus, water samples were taken at the mine and surrounding groundwaters and rivers to
characterize the chemical properties and environmental isotopes (δ2 H and δ18 O). The results showed
that the quality and stable isotope ratios of AMD differed from those of groundwater/river water,
indicating that the recharge areas of AMD. The recharge area of AMD was evaluated as the mountain





 slope at an elevation of 400–500 m while that of the surrounding groundwater was evaluated at an
elevation of 350–450 m, by considering the stable isotopes ratios. This indicates that the groundwater
Citation: Nishimoto, N.; Yamamoto,
affected by AMD is limited to the vicinity of the mine and distributed around nearby rivers.
Y.; Yamagata, S.; Igarashi, T.;
Tomiyama, S. Acid Mine Drainage
Sources and Impact on Groundwater
Keywords: abandoned and closed mine; acid mine drainage (AMD); water quality; stable isotope
at the Osarizawa Mine, Japan. ratio; groundwater
Minerals 2021, 11, 998. https://
doi.org/10.3390/min11090998

Academic Editors: Benoît Plante, 1. Introduction

Thomas Pabst and David Wilson Acid mine drainage (AMD) is generally characterized by low pH and high concentra-
tions of sulfate, heavy metals, and metalloids, and is a serious environmental problem at
Received: 31 July 2021
many active, closed, and abandoned mines worldwide [1–4]. Japan has a long history of
Accepted: 10 September 2021
metal mining, and was a global metal producer in the 17th to 19th centuries, with some
Published: 13 September 2021
5000 mines extracting mineral resources. Sulfide minerals such as pyrite, chalcopyrite,
sphalerite, and galena were mined, and the remaining minerals in excavated areas react
Publisher’s Note: MDPI stays neutral
with groundwater and the atmosphere to generate AMD, even today after mines were
with regard to jurisdictional claims in
closed or abandoned [5].
published maps and institutional affil-
From the beginning of the 20th century to the 1960s, acidification of river water caused
iations.
by the inflow of untreated AMD became a social problem in many parts of Japan, with
contamination of agricultural land downstream of mines by copper (Cu) and cadmium
(Cd) being problematic and, in some cases, leading to human health problems. In response,
mining concession holders and local governments have implemented mine pollution
Copyright: © 2021 by the authors.
prevention projects, and the local governments as well as the Ministry of Economy, Trade
Licensee MDPI, Basel, Switzerland.
and Industry of Japan provided support for the reliable and sustainable treatment of
This article is an open access article
mine drainage under the mine pollution prevention fund program [6]. Therefore, no
distributed under the terms and
serious contamination has occurred in recent decades. On the other hand, tunnels and
conditions of the Creative Commons
Attribution (CC BY) license (https://
excavated areas created during mining are suitable for investigations of properties of rock
creativecommons.org/licenses/by/
and groundwater deep underground, with depths from the ground surface exceeding
4.0/).
several hundred meters. As many mines in Japan were still in operation up to the 2000s,

Minerals 2021, 11, 998. https://doi.org/10.3390/min11090998 https://www.mdpi.com/journal/minerals

Minerals 2021, 11, 998 2 of 15

it was possible to undertake studies in mine tunnels, including on the permeability of

rock fractures [7] and the quality and quantity of AMD seepage from tunnel walls [8–10].
In the period since most of the mines were closed after the 2000s, further studies have
been undertaken to reduce the burden of AMD treatment, which is expected to continue
semi-permanently, such as studies of the formation and reaction of AMD with minerals [11],
future forecast for the quality of AMD [12–15], adsorption and sedimentation of heavy
metals from wastewater [16–19], mechanisms of AMD generation [20,21], and the effects of
backfilling of excavated areas on the quantity and quality of AMD [22,23]. The findings of
these studies have been incorporated into mine pollution control projects undertaken by
the government, mine operators, and researchers with some success. At the same time, in-
depth studies of the impact of mining on the groundwater environment have recently been
conducted worldwide. Based on this historical background, we focused on the relationship
between AMD and groundwater around mines. Over the last decade, studies of the impact
of mining on the surrounding groundwater environment have been vigorously pursued
worldwide, with examples being the impact of AMD generated in coal mines on karst
groundwater [24,25], estimation of natural and mining impacted contributions to instream
metals [26,27], and the evaluation of AMD attenuation using stable-isotope ratios of metals
as tracers [28]. Case studies have also been reported, including on the calculation of mixing
ratios of AMD and surface water based on stable-isotope ratios [29], chemical transfer
processes in waste-rock piles [30,31], and conceptualization of underground flooded mine
reservoirs and groundwater flow modeling [32]. On the other hand, metal mines in Japan
were mainly underground mines, and some mines still have drainage tunnels accessible
to the public. Geochemical studies have examined the origin of AMD and groundwater
flowing from old mine workings, but more detailed information is required to address all
relevant issues [33,34].
An understanding of the origin and flow of groundwater in closed and abandoned
mines can provide information useful in developing reasonable countermeasures such
as back filling of excavated areas and revegetation of surfaces. However, there is little
hydrological information for abandoned mines, and the way in which groundwater is
impacted by AMD from abandoned mines has received scarce attention. Few studies
have identified the recharge areas of AMD and groundwater around abandoned mines
or evaluated the relationship between them. The Osarizawa Mine area, northern Honshu
Island, Japan, was selected for this study because this is a closed non-ferrous sulfide mine
that had produced chalcopyrite, galena, and sphalerite, and these sulfide minerals still
exist in the mine. In addition, there are many springs nearby the Osarizawa Mine, which
are used for sake brewing as valuable groundwater resources in the local industry. To
prevent AMD from affecting these groundwater resources, a project to drain AMD from
the drainage tunnels and lower the groundwater table is underway. However, lowering the
groundwater table may stimulate AMD, so it is important to clarify whether AMD affects
the groundwater and, if so, to what extent. The objectives of the study were to evaluate the
geochemistry of AMD, and to assess its impact on the surrounding groundwater and river
for restricting the influenced areas by the AMD. Characteristics of AMD, groundwater, and
river water were evaluated based on major anion, cation, and heavy-metal concentrations,
and stable isotope ratios by considering topography, and geology around the mine.

2. Materials and Methods

2.1. Geology and History of the Osarizawa Mine
The Osozawa Mine is located in northern Akita Prefecture, Japan (Figure 1). The ore
deposit is classified as a vein type deposit formed through Tertiary igneous activity, and
the host rocks are Neogene green tuff, lava, and siliceous shale. There are about 470 veins
distributed over an area of 2 km E–W and 3 km N–S (Figure 2). Ore minerals are mainly
chalcopyrite and pyrite, with sphalerite at the periphery of the deposit. Galena and gold
(Au) occur in the upper parts of the veins. Quartz and chlorite occur universally as vein
minerals, with barite at the periphery of the deposit [35].
Minerals 2021, 11, 998 3 of 15

Figure 1. Topographic map of the study area showing the locations of water sampling points. The
inset shows the location of the mine area in Japan.

The mine has a long history of operation since it opened in the 8th century, according
to oral tradition. Detailed records of mining are available since the 16th century, and the
mine flourished as a leading Cu mine in Japan. By 1963, the annual crude ore output was
807,000 tons with average Cu, lead (Pb), and zinc (Zn) grades of 1.07%, 0.19%, and 0.13%,
respectively. Decreasing metal prices and appreciating Japanese Yen eventually made the
operation unprofitable, and it was closed in 1978 [36,37]. The mine is located in the green
tuff region where Neogene formations, Quaternary volcanic rocks, and pyroclastic flow
deposits are widely distributed on pre-Tertiary basement rocks. The area around the mine
is mountainous, and there are two peaks of the Quaternary volcanoes Mt. Hachimantai
(1613 m above sea level, a.s.l.) and Mt. Yakeyama (1366 m a.s.l.) located 25 km to the
south of the mine, with decreasing elevation northward. The mine lies on a mountain at
an elevation of 500–600 m a.s.l., and the ruins of an old concentrator and other facilities
Minerals 2021, 11, 998 4 of 15

still exist. Some old mine workings, such as tunnels and excavated areas, are open to
the public for tourism and are maintained as drainage tunnels. To the east of the mine,
the Yoneshirogawa River flows northward from its source on Mt. Hachimantai. Terrace
deposits are distributed along this river, with groundwater springs at the foot of terraces
being used by local residents for drinking and a raw material for sake.

Figure 2. Geological map and locations of water sampling sites, with corresponding water sample
properties indicated by Stiff diagrams.

All operations involved underground mining, with two excavation methods used
depending on the strength of host rocks: cutting and filling with sand slime, sludge, and
tailings, or the shrinkage stoping method [30]. Following mine closure, old workings
deeper than the drainage level (−5.5 L level; 140 m a.s.l.) were submerged, and AMD
from shallower mining areas was drained through the drainage tunnel. Since then, AMD
neutralization has been continued by the operator to protect surrounding groundwater
and rivers. Four treatment plants are operating for treatment of AMD from former mining
areas including dumping sites, the concentrator, and buried adit mouths.
Minerals 2021, 11, 998 5 of 15

2.2. Water Sample Collection and Analysis

Samples of river water, groundwater, and mine drainage were collected during 4–
6 September and 9–11 December 2020, from sites shown in Figures 1 and 2. In the drainage
tunnel, the seepage sample was collected from the tunnel wall (sample M-1) and AMD
samples were collected from cross cuts to the drainage tunnel (samples M-2 and M-3).
Groundwater samples were collected at springs on five locations around the mine (sam-
ples S-1 to S-5). River water samples were also collected from at the tributaries of the
Yoneshirogawa River (samples R-1 to R-26). To elucidate the effect of elevation on H–O
stable-isotope ratios, river water sampling locations ranged from lowlands to highlands
around the mine. All samples were divided into three 0.25 L polypropylene bottles; one
was filtered through a 0.45 µm membrane filter, and the other two were unfiltered. One of
the unfiltered samples was kept aside in case reanalysis was necessary. In the laboratory,
samples were acidified with 1% (v/v) nitric acid (HNO3 ). Temperature, pH, electrical
conductivity (EC), and oxidation–reduction potential (ORP) were measured in situ us-
ing a pH meter (HM-30P, DKK-TOA, Tokyo, Japan), an EC meter (CM-31P, DKK-TOA,
Japan), and an ORP meter (RM-30P, DKK-TOA, Japan), respectively. The ORP meter was
equipped with an Ag–AgCl electrode, and measured values were converted to standard
redox potentials (Eh) by applying a temperature-dependent constant appropriate for the
electrode solution.
Collected water samples were analyzed as follows. Alkalinity was determined by
the drop-test method, by titration with 0.02 M sulfuric acid (H2 SO4 ) to pH 4.8, using
50 mL of unfiltered samples. Major anion (Cl− , SO4 2− and NO3 − ) concentrations of
filtered samples were determined by ion chromatography with a Dionex Integrion RFIC
System (Thermo Fisher Scientific K.K., Tokyo, Japan). Major cation (Na+ , K+ , Ca2+ , and
Mg2+ ), Si, total Fe, Cu, and Zn concentrations of filtered samples were determined using
a multitype inductively coupled plasma emission spectrometer (ICPE-9000; Shimadzu
Corporation, Kyoto, Japan). For heavy metals, the major components targeted by the
AMD neutralization process were selected. Three repeat analyses by ion chromatography
and spectrometry were performed for each sample. The standard deviation (S.D.) of the
repeated measurements was within 1% of the concentration value for all samples collected
in both September and December 2020.
H–O isotopic ratios were determined by laser absorption spectroscopy using a liquid-
water isotope analyzer (DLT-100; Los Gatos Research, San Jose, CA, USA). The δD
(1000((2 H/1 H)sample /(2 H/1 H)VSMOW ) − 1), ‰) and δ18 O (1000((18 O/16 O)sample /
(18 O/16 O)VSMOW ) − 1), ‰) values were calculated relative to Vienna Standard Mean
Ocean Water (VSMOW) with analytical precisions of 1.0‰ and 0.1‰, respectively.

2.3. Principal Component Analysis

Multivariate principal component analysis (PCA) was undertaken to examine major
trends and interrelationships in the analysis results for each sample. The approach has
been applied in many studies comparing the qualities of AMD, groundwater, and river
water in mine areas [38–40]. Here, PCA was performed using the multivariate analysis
software IBM SPSS Statistics 25 (IBM Japan, Ltd., Tokyo, Japan), and it was applied to four
variables measured in situ (temperature, pH, EC, and Eh), the concentrations of seven
major ions (Na+ , K+ , Ca2+ , Mg2+ , Cl− , HCO3 − , SO4 2− , and NO3 − ), Si, three heavy metals
(total Fe, Cu, Zn), and the isotopic ratios of δD and δ18 O.

3. Results and Discussion

3.1. Geochemistry of Water Samples
The geochemical and isotopic properties of water samples collected from the Os-
arizawa mine area and the surrounding areas are summarized in Tables 1 and 2. Stiff
diagrams are shown in Figure 2, and the Piper diagrams are shown in Figure 3.
Minerals 2021, 11, 998 6 of 15

Table 1. Physicochemical properties of water samples collected during 4–6 September 2020.

Stable-Isotope
EC Eh Temp. Concentration (mg L−1 )
Sample 1 pH Ratios (‰)
(mS m−1 ) (mV) (◦ C)
Na+ K+ Ca2+ Mg2+ Cl− HCO3 − SO4 2− NO3 − Si T-Fe Cu Zn δD δ18 O
R-1 6.3 9.88 423 18.5 4.3 1.2 4.5 3.5 6.1 15.4 23.4 0.6 7.1 0.17 <0.01 <0.01 −66.9 −10.4
R-2 6.5 10.1 465 18.9 4.4 1.1 4.6 2.6 6.9 10.7 17.2 0.6 6.6 <0.01 <0.01 <0.01 −65.1 −10.3
R-3 6.8 10.4 402 19.1 4.7 0.9 7.1 2.6 6.2 32.2 8.5 1.4 5.3 <0.01 <0.01 <0.01 −66.0 −10.4
R-4 6.8 8.43 431 18.8 4.8 0.8 4.3 1.3 7.6 18.6 5.3 1.2 5.8 <0.01 <0.01 <0.01 −64.1 −10.1
R-5 7.1 5.51 445 20.6 3.6 0.8 2.1 1.1 6.1 11.7 4.3 0.4 4.5 0.18 <0.01 <0.01 −63.0 −10.1
R-6 6.9 8.79 500 18.8 4.1 2.4 3.6 2.2 7.6 13.2 9.5 0.5 7.0 <0.01 <0.01 <0.01 −64.2 −10.1
R-7 6.3 16.5 426 23.8 3.2 1.3 18.1 2.5 6.0 5.1 52.2 0.9 6.1 0.66 0.43 0.51 −65.0 −10.1
R-8 3.5 29.9 608 17.9 7.1 6.3 3.6 3.6 8.3 <0.01 61.5 2.8 9.0 <0.01 1.2 <0.01 −63.9 −10.0
R-9 6.8 18.4 504 22.1 6.4 1.7 13.7 5.4 10.4 22.2 43 1.6 9.5 <0.01 0.11 0.15 −63.4 −9.8
R-10 6.7 8.19 410 20.4 5.4 1.2 4.5 1.4 8.1 20.7 6.3 1.5 10.8 <0.01 <0.01 <0.01 −61.9 −9.4
R-11 6.8 9.00 427 22.8 5.7 1.3 4.9 1.5 9.2 29.5 11.4 1.5 13.1 <0.01 <0.01 <0.01 −61.8 −9.4
R-12 6.5 12.1 428 22.2 7.6 1.9 7.9 2.0 9.9 35.9 10.5 0.6 15.5 0.15 <0.01 <0.01 −60.9 −9.3
R-13 7.0 10.0 426 19.8 4.3 1.9 5.2 3.5 7.7 20.5 15.2 0.8 6.1 <0.01 <0.01 <0.01 −63.3 −10.3
R-14 7.5 8.63 441 23.0 3.8 1.1 6.2 1.6 6.0 34.9 5.2 0.9 6.1 <0.01 <0.01 <0.01 −65.7 −10.3
R-15 7.3 8.96 440 20.3 3.4 0.9 7.9 1.8 4.7 17.3 17.0 0.3 6.3 <0.01 <0.01 <0.01 −66.3 −10.6
R-16 7.1 7.61 451 19.5 4.1 0.8 6.3 1.2 5.2 36.9 6.9 0.5 6.7 <0.01 <0.01 <0.01 −65.9 −10.6
R-17 7.0 8.16 441 22.4 3.4 1.0 6.7 1.6 3.7 15.6 16.0 0.4 11.0 <0.01 <0.01 <0.01 −71.5 −11.4
R-18 7.3 7.52 445 17.7 4.6 0.9 6.0 1.0 5.1 27.8 5.0 0.6 10.4 <0.01 <0.01 <0.01 −68.5 −10.9
M-1 7.2 60.5 262 13.8 12.6 9.6 60.0 32.6 9.7 59.2 237 2.4 9.0 <0.01 <0.01 <0.01 −63.3 −10.1
M-2 4.1 183 591 13.7 10.3 8.4 107 147 10.2 <0.01 1040 2.7 14.3 35.7 1.4 47.2 −61.2 −10.0
M-3 3.2 387 603 14.5 17.1 11.6 177 217 1.7 <0.01 3237 <0.01 16.5 522 3.8 55.5 −62.9 −10.2
1 R-1 to R-18, river water; M-1 to M-3, mine drainage.

Table 2. Physicochemical properties of water samples collected during 9–11 December 2020.

Stable-Isotope
EC Eh Temp. Concentration (mg L−1 )
Sample 1 pH Ratios (‰)
(mS m−1 ) (mV) (◦ C)
Na+ K+ Ca2+ Mg2+ Cl− HCO3 − SO4 2− NO3 − Si T-Fe Cu Zn δD δ18 O
S-1 6.3 18.4 446 13.0 13.6 3.7 18.6 4.3 10.0 44.2 25.5 7.6 11.2 0.17 <0.01 <0.01 −63.2 −9.6
S-2 6.3 17.1 429 10.3 14.4 2.5 15.3 3.6 10.0 30.0 16.5 19.9 28.3 <0.01 <0.01 <0.01 −61.9 −9.9
S-3 6.4 17.1 412 10.1 15.5 2.4 15.2 3.6 9.9 32.7 16.5 19.9 28.7 <0.01 <0.01 <0.01 −63.1 −10.0
Minerals 2021, 11, 998 7 of 15

Table 2. Cont.

Stable-Isotope
EC Eh Temp. Concentration (mg L−1 )
Sample 1 pH Ratios (‰)
(mS m−1 ) (mV) (◦ C)
Na+ K+ Ca2+ Mg2+ Cl− HCO3 − SO4 2− NO3 − Si T-Fe Cu Zn δD δ18 O
S-4 6.5 15.7 424 9.5 11.8 0.4 17.3 4.0 10.4 44.2 12.0 9.8 15.8 <0.01 <0.01 <0.01 −61.2 −9.8
S-5 6.7 25.6 411 8.3 14.1 0.4 27.2 10.9 15.1 78.1 22.6 15.7 15.6 <0.01 <0.01 <0.01 −62.0 −9.9
R-7 6.4 13.3 657 4.8 4.8 0.9 15.3 2.1 6.3 6.8 36.1 2.1 4.4 0.01 0.26 0.36 −61.7 −9.9
R-9 7.1 18.8 449 5.1 10.5 1.6 17.3 5.4 12.4 24.2 44.4 2.1 8.4 <0.01 0.26 0.17 −60.3 −9.6
R-19 7.4 8.8 342 5.5 6.8 0.3 9.4 2.4 6.6 22.5 10.2 1.1 6.2 <0.01 <0.01 <0.01 −64.8 −10.4
R-20 7.3 13.5 339 6.8 11.9 0.6 13.3 3.2 15.6 32.5 9.8 2.2 9.0 0.01 <0.01 <0.01 −63.4 −10.1
R-21 7.5 9.31 415 3.9 7.5 0.3 10.9 2.1 9.5 29.3 5.3 0.94 7.8 <0.01 0.11 0.15 −64.6 −10.2
R-22 7.5 10.3 402 5.0 7.5 0.2 13.4 2.0 8.7 29.8 9.2 1.2 6.8 <0.01 <0.01 <0.01 −64.3 −10.5
R-23 5.6 7.1 390 3.1 7.5 0.7 4.2 1.5 5.4 23.9 11.6 0.82 9.2 <0.01 <0.01 <0.01 −66.9 −10.6
R-24 6.4 8.4 381 4.3 6.2 0.7 10.7 2.1 3.7 29.3 9.1 0.92 9.2 0.15 <0.01 <0.01 −69.2 −11.1
R-25 4.3 9.2 657 4.6 5.3 0.5 1.2 1.3 6.9 <0.01 15.0 1.4 4.0 <0.01 <0.01 <0.01 −62.7 −10.0
R-26 5.0 6.9 610 5.3 0.5 0.3 1.4 1.7 7.7 0.5 13.2 0.48 4.6 <0.01 <0.01 <0.01 −61.3 −19.8
M-1 7.2 61.8 252 12.2 17.1 4.7 67.6 37.8 9.9 62.7 249 4.6 8.9 <0.01 <0.01 <0.01 −62.2 −10.0
M-2 3.8 183 609 13.4 10.6 5.5 89.2 151 10.1 <0.01 1128 4.4 14.9 31.2 0.61 45.7 −61.3 −9.9
M-3 3.4 347 605 14.4 23.1 10.4 165 238 8.6 <0.01 2981 4.7 17.3 462 8.4 63.5 −62.6 −10.2
1 S-1 to S-5, groundwater; R-1 to R-18, river water; M-1 to M-3, mine drainage.
Minerals 2021, 11, 998 8 of 15

Figure 3. Piper diagram showing the hydrochemical facies of river water, groundwater, and mine
drainage.

The pH, EC, Eh, and temperature of river water samples were in the ranges of 3.5–7.5,
5.5–29.9 mS m−1 , +339 to +657 mV, and 5.5 ◦ C–29.9 ◦ C, respectively (Tables 1 and 2). The
HCO3 type, which is rich in Ca2+ and HCO3 − , was relatively common, but there were other
types in which Na+ and Mg2+ were the predominant cations and SO4 2− the predominant
anion. HCO3 − was the dominant anion in the Yoneshirogawa River tributaries (Na, Ca,
Mg−HCO3 type water) while SO4 2− was the dominant anion when the pH was low
(3.5–6.4) of the samples collected at the former mining area (Ca, Mg−SO4 type water;
samples R-7, R-8, R-9, R-25, and R-26). In the Piper diagram (Figure 3), some river water
samples collected at the former mining area had chemical compositions similar to those of
AMD. This implies that river samples collected at the former mining area may be affected
by AMD, although no AMD inflow or outflow was observed. Tailings remain in the former
mining area, and these may cause acidification of rainwater due to the oxidation of sulfide
minerals. River water samples in the area of terrace sediments were of the Ca−HCO3 type,
similar to groundwater samples (R-19 to R-22). Concentrations of heavy metals (total Fe,
Cu, Zn) were <1 mg L−1 in the former mining area, and concentrations of other elements
were below the detection limit.
The pH, EC, Eh, and temperature of groundwater samples were in the ranges of 6.3–
6.7, 15.7–55.6 mS m−1, +411 to +446 mV, and 8.3 ◦ C–13.0 ◦ C, respectively (Tables 1 and 2).
All samples (S-1 to S-5) were Ca–HCO3 type, with higher concentrations of dissolved ions
than river water. The groundwater samples were characterized by NO3 − rich
(7.6–19.9 mg L−1 ) relative to river water samples (0.3–2.8 mg L−1 ) and mine drainage
samples (2.4–4.7 mg L−1 ). Thus, the groundwater quality is considered to be controlled
by reactions between dissolved CO2 and minerals in sediments such as feldspar and is
affected by fertilizer [41,42].
The pH, EC, Eh, and temperature of mine drainage samples (M-1, M-2, and M-3)
were in the ranges of 3.2–7.2, 60.5–387 mS m−1 , +252 to +609 mV, and 12.2 ◦ C–14.5 ◦ C,
respectively (Tables 1 and 2). Sample M-1 (seepage from tunnel wall) was a Ca–SO4 type
although samples M-2 and M-3 were Mg–SO4 type (Figure 2). AMD samples M-2 and
M-3 from the mining cross cuts had lower pH and higher EC values than seepage sample
M-1, indicating the influence of oxidation of ore minerals that remain in the excavated
areas. The pH of seepage sample M-1 was 7.2 in both sampling periods, and was similar to
that of groundwater samples. The EC value of seepage sample M-1 was 60.5–61.8 mS m−1 ,
slightly higher than that of groundwater. A similar trend was observed for concentrations
Minerals 2021, 11, 998 9 of 15

of total Fe, Cu, and Zn in three mine drainage samples. Total Fe, Cu, and Zn concentrations
in samples M-2 and M-3 were >31, 0.6, and 45 mg L−1 , respectively, while those in sample
M-1 were below the detection limit. The difference in water quality between AMD samples
and seepage sample was also evident in Eh values, with the former ranging from 591 to
601 mV and the latter from 252 to 262 mV, indicating that seepage sample was reductive in
nature (Tables 1 and 2).

3.2. H–O Isotopic Ratios

The δD and δ18 O values of river water samples were in the ranges of −71.5‰ to
−60.9‰ and −11.4‰ to −9.3‰ for samples collected in September 2020, and −69.2‰
to −60.3‰ and −11.1‰ to −9.6‰ for samples collected in December 2020, respectively,
as illustrated in Figure 4. The meteoric water line in the area of the Japan Sea around
northern Japan [43] is depicted in this figure. From these figures, there was no significant
difference in values between the two periods, but there was a slight difference between
the obtained date and the local meteoric water line (LMWL; Figure 4), likely due to the
different sampling sites. The ranges of δ18 O and δD values of groundwater and mine
drainage samples approximate those of river water samples, and are plotted near LMWL.
Therefore, it is considered that groundwater and mine drainage were originated from
rainwater on the area, the same as river water. River water samples from higher elevations
(samples R-23 and R-24) have lower δ18 O and δD values, with the relationship between
elevation and isotopic ratios likely being due to isotopic fractionation during precipitation
(Figure 4b) [44,45]. Samples R-17 and R-18 also have low isotopic ratios, reflecting values
of the catchment area, as the upper reaches of the rivers at these two sites are at high
elevations (Figure 4a).

Figure 4. Relationship between δD and δ18 O values of water samples, relative to the local meteoric
water line (LMWL). (a) September 2020; (b) December 2020.

There is a clear negative correlation between the average catchment elevation of river
which was calculated with that of the water sampling site and most upstream site, and
isotopic ratios, for both δ18 O and δD values (Figure 5). The origin of groundwater and
mine drainage can be inferred by comparing these values with those of river water. As the
spring is located at the foot of a terrace, it was assumed that groundwater originated from
rainwater on the terrace, but the isotopic ratios do not match river water on the terrace. The
Minerals 2021, 11, 998 10 of 15

recharge area assumed from the isotopic ratios is at 350–450 m a.s.l., which corresponds to
the elevation of the boundary between terrace and mountain (Figure 5c,d). The difference
in isotopic ratios between groundwater and river water suggests that the river water on the
terrace is upstream of the high-elevation Neogene mountains, and that the groundwater
originates from rainwater infiltrating the terrace surface. The mine drainage generally
originates at 400–500 m a.s.l., which corresponds to the elevation of the mountain body
where the ore veins are distributed (Figure 2), in both sampling periods.

Figure 5. Relationship between the elevation of river catchment areas and stable-isotope ratios,
including regression lines. (a) September 2020, δD; (b) September 2020, δ18 O; (c) December 2020, δD;
(d) December 2020, δ18 O. The elevation of the river catchment area was calculated by averaging the
elevations of the water sampling site and the most upstream site.

3.3. Principal Component Analysis

PCA results are shown in Table 3. Three principal components (PC1, PC2, and PC3)
were selected, which together account for 80% of the total variability of the dataset, with
water quality thus being dominated by these factors. PC1 had high loadings for EC, pH, K+ ,
Ca2+ , Mg2+ , SO4 2− , total Fe, Cu, and Zn with an absolute value of >0.79. The low pH and
SO4 2− loadings may be explained by oxidation of pyrite (FeS2 ), a common sulfide mineral
Minerals 2021, 11, 998 11 of 15

in metal deposits and altered rocks. Pyrite oxidation is facilitated by Fe3+ formed through
the oxidation of Fe2+ by dissolved O2 , and promotes dissolution of Cu and Zn [45,46]. The
high Ca2+ loading is related to reactions of AMD and calcite (CaCO3 ), which is a vein
mineral, and possibly to interactions of river water in the mining area with concrete used
in drainage roads. The significant Mg2+ loading is related to reactions of AMD with the
mineral chlorite ((Mg,Fe,Al)6 (Al,Si)4 O10 (OH)8 ) associated with veins.

Table 3. Factor loadings and contributions of principal components.

Variable PC1 PC2 PC3

Temperature −0.03 −0.32 −0.05
EC 0.98 −0.06 0.10
pH −0.79 −0.14 0.34
Eh 0.56 −0.32 −0.60
Na+ 0.67 0.63 0.33
K+ 0.90 0.04 0.07
Ca2+ 0.95 0.05 0.17
Mg2+ 0.97 −0.06 0.06
Cl− −0.04 0.83 –0.23
Chemical composition SO4 2 − 0.97 −0.12 0.12
HCO3 − −0.39 0.63 0.50
NO3 − 0.09 0.79 0.16
Si 0.42 0.61 0.21
Total Fe 0.90 0.15 0.18
Cu 0.88 −0.11 0.10
Zn 0.95 −0.10 –0.01
δD 0.32 0.64 –0.61
Stable-isotope ratio
δ18 O 0.13 0.60 –0.66
Rate of contribution (%) 49.5 19.7 10.5

For PC2, there were high loadings for Na+ and Si with values of >0.61, and it is
considered to be the groundwater and river water quality were controlled by reactions
between dis-solved CO2 and silicate minerals such as feldspar. The relatively high load of
HCO3 was 0.63, supporting this consideration. In addition, for PC2, there was high loading
for NO3 − with values of 0.79, reflecting the high concentrations of NO3 − in groundwater.
Orchards on the terrace were assumed to be a recharge area for groundwater, with NO3 −
originating from artificial fertilizer.
For PC3, there were high loadings for H–O isotopic ratios with absolute values of
>0.61, reflecting the effect of isotopic fractionation (Figure 5).
The sum of the contributions of PC1, PC2, and PC3 is 69% (Table 3), indicating
that the geochemistry of river water, groundwater, and mine drainage were satisfactorily
explained by the three PCs. A scatterplot of PC1 vs. PC2 and PC1 vs. PC3 are shown in
Figure 6, indicating three different data groups: (a) river water, (b) groundwater, and (c)
mine drainage and river water in the mining area. The figure shows that seepage water
(sample M-1) from mine drainage was similar to groundwater in terms of water quality
and isotopic ratios.
Minerals 2021, 11, 998 12 of 15

Figure 6. Principal component scores of (a) PC1 vs. PC2 and (b) PC1 vs. PC3.

3.4. Groundwater Flow and Discharge

A conceptual model of infiltration and groundwater flow was devised on the basis
of results described in Sections 3.1–3.3, as shown in Figure 7. Groundwater infiltrating
from the terrace and mountain surface (350–450 m a.s.l.) on the true right bank of the
Yoneshirogawa River reacts with felspars in terrace deposits, releasing Ca2+ , Na+ , and
HCO3 − before discharge as spring water. Some groundwater also enters the river, affecting
the composition of the river water. The orchard terrace surface releases fertilizer NO3 −
to groundwater. Infiltration and groundwater enter rivers on the surrounding moun-
tain surface, with the water quality being altered by reaction with feldspars in Neogene
volcanic rocks.

Figure 7. Conceptual model of discharge and groundwater flow from the Osarizawa Mine area.
Minerals 2021, 11, 998 13 of 15

The Osarizawa Mine is on the left bank of the Yoneshirogawa River, and groundwater
that has infiltrated to the excavated areas from the directly overlying mountain surface
(400–500 m a.s.l.) reacts with sulfide minerals to generate AMD, which flows from the
drainage tunnel to the treatment facility. The water table is maintained at a constant level
by drainage. Mine drainage seepage from the walls of the drainage tunnel has a neutral pH,
a low content of heavy metals, and is not significantly affected by the AMD. River water
in the former mining area is affected by tailings remaining on the ground surface, and is
relatively acidic. The area affected by AMD is limited to near the mining area, with no
effect on surrounding groundwater, mainly because the flooded surface of the Osarizawa
Mine is maintained at a constant level.

4. Conclusions
The findings of this geological, hydrological, geochemical, and isotopic study of
groundwater at the Osarizawa Mine area are as follows:
(1) AMD is formed through interactions between groundwater and sulfide minerals in
excavated areas.
(2) The groundwater recharge area for AMD formation is located on the mountain slope
at 400–500 m a.s.l.
(3) Groundwater infiltrating from the terrace and mountain surface at 350–450 m a.s.l.
reacts with felspars in terrace deposits and is discharged as spring water.
(4) Based on a conceptual model of discharge and groundwater flow at the mine area, the
area affected by AMD is limited to near the mine area, with no effect on surrounding
groundwater.

Author Contributions: Conceptualization, N.N. and S.T.; software, N.N.; validation, T.I. and S.Y.;
investigation, N.N., S.T. and Y.Y.; writing—original draft preparation, N.N. and S.T.; writing—review
and editing, T.I.; visualization, S.T.; supervision, S.T. All authors have read and agreed to the
published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Data for this study are presented in the paper.
Acknowledgments: The authors thank the editor and anonymous reviewers for their constructive
comments that improved this manuscript. We also thank the staff of Mitsubishi Materials Corporation,
Eco-Management Corporation, and Mitsubishi Materials Techno Corporation for their help, advice,
and cooperation during this study.
Conflicts of Interest: The authors declare no conflict of interest.

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