368

Journal of Mineralogical and

Petrological
Sciences,
Volume 99, page 368 374, 2004
H. Miura,
K. Wada
and Y. Katsui

Tephrochronology and diagenesis of the manganese wad deposit

at the Akan Yunotaki hotspring, Hokkaido, Japan
Hiroyuki MIURA*, Keiji WADA** and Yoshio KATSUI*
*

Division of Earth and Planetary Sciences, Graduate School of Science, Hokkaido University,
N10 W8 Sapporo 060 0810, Japan
**
Hokkaido University of Education at Asahikawa, Asahikawa 070 8620, Japan

An outcrop of manganese oxide about one meter thick, inter bedded with several volcanic ash layers, is found
at the Yunotaki hotspring, Hokkaido, Japan. The manganese wad is precipitated from hydrothermal water. On
the basis of the previously known age of the inter bedded volcanic ash layers, linked to well known eruptions, it
has been possible to determine the chronology of the manganese oxide precipitation. The ash layers were identified by the chemical composition of the separated volcanic glasses. Since the lowermost manganese oxide
layer of this outcrop occurs immediately above the mud flow of Mt. Ponmachineshiri (one volcano of Mt.
Meakan) without the presence of any intermediate soil layer between them, its age of formation could be near
the age of the mud flow, i.e. 4500 5000 years BP. The manganese oxide layers in the top 50 cm of the outcrop
are comparatively softer than those occurring below 50 cm and commonly have the texture of the aggregate of a
filament structure. Manganese oxide occurring below 50 cm is hard and has a diagenetically altered texture
reflecting change in the filament structure to a grain aggregate structure. These oxides have lost their structural
water and the mineralogy has begun to change from todorokite (10 phase) to birnessite (7 phase) during the
diagenetic process.

Introduction
Present day manganese deposits formed by hotsprings on
land have been reported in the U.S.A. (Hewett and
Fleischer, 1960) and in Japan (Yoshimura, 1952; Hariya
and Harada, 1957; Konoya et al., 1968; Miura and Hariya,
1997). These deposits are important for understanding
the process of deposition of older manganese deposits
because the precipitation process can be observed directly.
Recent studies have shown that most of these deposits are
formed as a result of microbial activity (Hariya and
Kikuchi, 1964; Mita et al., 1994; Usui and Mita, 1995;
Mita and Miura, 2003). However, data on the depositional processes and deposition rates of these manganese
oxides are very limited. At present, a deposition rate has
only been estimated for the Yunotaki manganese deposit
(Hariya et al., 1992). To determine the deposition rate
precisely, a key marker in the deposit is necessary. So far,
one has not been available. However, in the course of the
field survey of the Yunotaki manganese deposit by Ashoro
Town Board of Education, we found an outcrop of manganese deposit inter bedded with several volcanic ash layH. Miura, hiro@ep.sci.hokudai.ac.jp Corresponding author
K. Wada, wada@asa.hokkyodai.ac.jp

ers. We have identified the source and date of eruption of

each ash layer and established the chronology of manganese deposit. On the basis of the chronology, we have
studied the diagenesis of the manganese wad over the last
4500 5000 years. This is the first report of the chronology of a present day manganese deposit.
Yunotaki manganese deposit
The Yunotaki manganese deposit is located southwest of
Meakan volcano, Ashoro town, Hokkaido, Japan. Figure
1 shows the location of Yunotaki and of selected active
volcanoes with the distribution of widespread tephra. The
dimensions of the manganese deposits are approximately
150 m 70 m with a maximum thickness of about 2 m.
During 1951 1954, approximately 3500 tons of manganese ore was mined from this area. (Umemoto et al.,
1956). The deposit is precipitated from hotspring water
which emerges from the mountain slope and forms two
waterfalls (Fig. 2). The depositional rate of manganese
oxide has been estimated to be about 1100 kg/year (Hariya
et al., 1992). The Yunotaki deposit is an example of manganese biomineralization (Mita et al., 1994) and is the
largest recent manganese deposit in the world where biologically activated precipitation is taking place.

Tephrochronology and diagenesis of the manganese wad deposit

369

from top to bottom is as follows: A, weathered soil; B,

manganese oxide deposit, 3 cm thick (samples 1 and 2); C,
volcanic ash layer (ash 1); D, soil layer containing manganese oxide (sample 3); E, volcanic ash layer (ash 2); F,
volcanic ash layer (ash 3); G, altered volcanic ash volcanic sand layer; H, black manganese oxides, 8 cm thick
(sample 4); I, volcanic ash layer (ash 4); J, manganese
oxide deposit, 20 cm thick (samples 5 and 6); K, mud
flow deposit at the bottom of the outcrop. A manganese
oxide sample was also collected from the present hotspring for comparison (sample 0). Volcanic ash samples
collected from layers of C, E, F, and I were used for identification of their source.
Figure 1. Schematic map showing the location of Yunotaki and the
widespread distribution of tephra from Ko c1, Ta a, Ko c2, and
Ma b. Yu, Yunotaki manganese deposit and hotspring; Me,
Mt. Meakan; Ko, Mt. Komagatake; Ta, Mt. Tarumai; Ma, Mt.
Mashu. The distribution of tephra is taken from Machida and
Arai (1992) and Nakamura and Hirakawa (2003).

Sample collection
The outcrop of the manganese oxide deposit indicates
sequences of the deposition of volcanic ash layers are
found at the terrace, at opposite side of the Yunotaki falls
(Fig. 2). Figure 3 shows an outcrop of about 1 m in
thickness. Several volcanic ash layers, a mud flow
deposit, and layers of manganese oxide were observed
within the deposit. The observed stratigraphic sequence

Experiments and results

Identification of ash layers
Four ash layers were identified by the chemical compositions of volcanic glass as well as the stratigraphy of widespread ashes in eastern Hokkaido. The chemical composition of the volcanic glass was determined by electron
probe micro analyzer (JEOL 8600) at the Hokkaido
University of Education at Asahikawa. The beam current
and beam scanning area were 0.8 108A and 4 to 10
m2 , respectively. The results are shown in Table 1.
Na2O content showed a slight decrease because of the
counting loss by beam irradiation in the case of a small
beam scanning area (<10 m2).
The compositions of the analyzed volcanic glass in

Figure 2. Geologic sketch map of Yunotaki hotspring (after Katsui et al., 1999).

370

H. Miura, K. Wada and Y. Katsui

Figure 3. The outcrop of manganese oxide interbedded with several ash layers.
A: weathered soil, B: manganese oxide deposit, C: ash layer (ash
1), D: soil layer containing manganese oxides, E: ash layer (ash
2), F: ash layer (ash 3), G: altered black ash layer, H: manganese
oxide deposit, I: ash layer (ash 4), J: manganese oxide deposit, K:
mud flow deposit. Numbers 1 6 show the sample positions of
the manganese oxides.

the 4 ash layers were compared with standard glass compositions of pumice from four historical eruptions (Fig. 4).
Ash 1 of the uppermost ash layer (Fig. 3) was identified

as the Ko c1 ash from the 1856 AD eruption of

Komagatake volcano. Although the standard values of
Ko c1 and Ko c2 volcanic glasses are chemically similar
(Fig. 4A), the Ko c1 volcanic glass is distinguished from
the Ko c2 volcanic glass by lower Al2O3 and CaO content
(Fig. 4B). The volcanic glass from ash 2 is identified as
the widespread ash from the 1739 AD eruption of Tarumai
volcano (Ta a) which is characterized by lower TiO2 and
higher K2O content (Fig. 4A). The volcanic glasses from
ash 3 are identified as the Ko c2 ash from the 1694 AD
eruption of Komagatake volcano. The volcanic glasses in
the lowermost ash layer (ash 4) are characterized by low
K2O content and are identified as Ma b ash erupted about
1000 years ago from Mashu volcano. The high MnO content of the volcanic glasses in this layer (Table 1) could be
due to the effect of chemical leaching of Mn from the
overlying and underlying manganese layers. Since there
are 14 ash layers (Po12 25) from Ponmachineshiri
between Ma b and Ko c2, the G layer should be identical
to some of these ash layers. However, we could not identify the G layer in this study. The age of the mud flow
deposit at Yunotaki, 4500 to 5000 years ago (K in Fig. 3),
was based on the same stratigraphic succession of the
mud flow deposit which originated from Me akan volcano near the Nonaka Onsen spa about 3 km north of
Yunotaki. The age was taken from the unpublished data
of 14C ages of wood in the mudflow deposits at Nonaka
Onsen spa (Wada et al., 1997). The geographical distribution of Ma b, Ko c2, Ta a, and Ko c1 ash layers (Fig. 1)
which occur in the Yunotaki manganese deposit is compatible with the identification of each of the ash layers.
The presence of the volcanic ash layers from Mt.
Komagatake, Mt. Tarumai, and Mt. Kamuinupuri are used
as key markers to determine the relative age of each manganese layer. Since these ashes originated from volcanoes
located far afield (Fig. 1), they did not have any thermal

Table 1. Chemical compositions of the volcanic glasses within the layers of ash

Tephrochronology and diagenesis of the manganese wad deposit

371

Figure 4. Chemical compositions of volcanic glasses in the four ash layers are compared with the standard glass compositions of pumice from
four historical eruptions.
Table 2. The position of the collected samples within the deposit

influence on the adjacent manganese oxide layers. The

mineralogical differences of the manganese deposits
observed here are believed to have been caused by the
differences in their age and variable post depositional
changes. Table 2 summarizes the relative chronology of
the samples collected during this study and Figure 5
shows the schematic presentation of the columnar section
of the total outcrop.
Chemical composition and morphology of manganese
oxides

Figure 5. A columnar section showing the distribution of the manganese oxide deposits and volcanic ash layers within the outcrop.
(1) (6) indicate the sample position of the manganese oxides.

Bulk chemical compositions, analyzed by Inductively

Couple Plasma Mass Spectroscopy in ACTLABS,
Canada, are listed in Table 3. Total Fe and Mn values are
shown in Fe2O3 and MnO, respectively. Samples 1 4
show high SiO2 content derived from soil contamination.
Samples 1 to 4 are muddy and very soft but samples
5 and 6 are hard. Particularly the oldest sample (sample 6)
has solidified and is very hard to dig by shovel. In the
scanning electron microscope (SEM) image, sample 0
(Fig. 6A), the most recently deposited manganese shows

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H. Miura, K. Wada and Y. Katsui

Table 3. Bulk compositions of manganese oxides (wt%)

Figure 6. SEM image of manganese minerals from the Yunotaki manganese deposit. A: Sample 0, Recent manganese sample. B: Sample 2,
Sample younger than 145 years old. The original texture is well preserved. C: Sample 4, Sample between about 1000 and 400 years old. D:
Sample 6, Sample about 4500 5000 years old. Samples 4 and 6 are diagenetically affected to coarse grained spherules. The original filament
structure of the manganese wad in samples 0 and 1 had disappeared in the diagenetic process of 4500 5000 years. The grain size in sample 6
is larger than in sample 4. All samples contained diatoms which showed that the depositional environment was very similar during the entire
depositional history.

aggregates of an elongated filament structure of algal origin (Usui and Mita, 1995; Miura and Hariya, 1997).
Sample 2 (Fig. 6B), which is less than 145 years old,
shows the same type of filament structure. However, the
image of each filament is not clear compared to the recent

manganese sample. The original filamental structure of

sample 4 which is younger than 1000 years (Fig. 6C) has
been diagenetically altered and has changed to a tabular
structure or lamination of a tabular structure. Sample 6,
which is 4500 5000 years old (Fig. 6D) is also diageneti-

Tephrochronology and diagenesis of the manganese wad deposit

373

X ray diffraction study

XRD profiles from 5 90 2 in 0.05 2 steps were
obtained using Cu K radiation (35kV, 30mA) with a
graphite monochromator. Samples were attached on silicon plates in a wet condition. The results are shown in
Figure 7, together with sample 0. The diffraction data
display peaks of impurities such as quartz and feldspar.
However, it is possible to identify the diffraction peak of
manganese at 10 which correspond to todorokite.
Sample 6 shows both 10 and 7 peaks which are
derived from todorokite and birnessite, respectively.
Samples 1, 2, 3, and 4 show increased background
between 20 and 40 2 (background halo). However,
samples 5 and 6, which precipitated about 1000 to 5000
years ago, display a flat background. Sample 6 has two
basal diffraction peaks of 10 and 7, whereas the
younger manganese samples occurring above 50 cm in
the outcrop display only the 10 peak.
Discussion

Figure 7. X ray diffraction profiles. The increased background of

samples 0 to 3 between 20 and 40 indicates the presence of
structural water. By contrast, samples 5 and 6 precipitated from
about 1000 to 5000 years before show a flat background. The
structural water of these two samples has been released and the
structure starts to change from the 10 phase to 7 phase. The
width of basal diffraction peaks (=10) decreases with age
which reflects the increase of crystallinity with time after precipitation. T, todorokite; B, birnessite; Q, quartz; F, feldspar.

cally altered. These samples consist of manganese oxide

grains of about 50 60 m in diameter. Sample 6, the oldest sample, has the largest grain size. The original filamental structure of the manganese wad disappeared in the
diagenetic process of 4500 5000 years ago. All samples
contained diatoms which show that the depositional environment was very similar during the entire depositional
history.

The widespread tephra layers identified in the manganese

deposits remarks the depositional history of the last 4500
5000 years at Yunotaki hotspring. Since sample 6 was
deposited directly on the mud flow of Ponmachineshiri
and with no old soil layer existing between them, it can be
assumed that the age of the sample 6 could is very close
to the age of the mud flow, i.e. 4500 5000 years BP. The
established chronology of the Yunotaki manganese
deposit then represented calibration of the rate of deposition of the three manganese layers (Table 4). They range
from 50000 200000 mm/106 years. The apparently slow
deposition rate of the bottom layer may be caused by
compression from the upper layers. Deposition rates of
manganese nodules and crusts in freshwater lakes summarized range from 3000 to 150000 mm/106 years (Roy,
1981). The depositional rate in the hotspring deposit is
very close to that of freshwater deposits.
The manganese oxide of sample 6 became very hard
and the manganese oxide grains became larger (Fig. 7D)
during the subsequent 4500 5000 years. The background
halo in the XRD data of the wet samples (at top 50 cm of
the outcrop) disappeared when they were dried at 40C in
air for 24 hours. This fact demonstrates that the back-

Table 4. The calculated depositional rates of manganese oxides for layers B, H and J

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H. Miura, K. Wada and Y. Katsui

ground halo is caused by the presence of water in the mineral structure. Samples 1, 2, and 3 which are younger
than 260 years, show larger background haloes than samples 5, and 6. These data indicate that the structural water
is retained in the manganese wad during wetter conditions
and is gradually released with time during the recrystalization process, which lasts thousands of years. Sample 4,
which occurs just under the ash layer from Ponmchineshiri, shows a background halo. This indicates that the
ash layer did not have any thermal influence on the manganese deposit, and the change in manganese oxide in
samples 1 and 2 are derived from the effects of ageing.
The decrease in the basal diffraction peak (10 peak)
width with age also suggests that the manganese crystals
increase their crystallinity with age. Sample 6, which displays both 10 and 7 peaks, shows a decrease in interlayer distance from 10 to 7 and this could be due to
release of interlayer structural water.
Conclusion
Manganese precipitation started at Yunotaki more than
4500 5000 years ago. Over this long period, the precipitated manganese oxide lost its structural water, thereby
increasing its crystallinity. The mineralogy also changed
from todorokite (10 phase) to birnessite (7 phase).
The Yunotaki manganese deposit is important not only as
an example of recent manganese precipitation but also
because it enables us to establish diagenetic processes
within the last 4500 5000 years.
Acknowledgments
The authors thank the board of education of Ashoro town
and Ashoro Museum of Paleontology for help in the field
survey, Dr. R. Banerjee of the National Institute of
Oceanography, Goa, India and Dr. G.P. Glasby of
University of Tokyo for critical reading of the manuscript.
References
Hariya,Y. and Harada, Z. (1957) On manganese wads from some
localities in Hokkaido, Studies on manganese oxide minerals
(Report No.1). Journal of the Mineralogical Society of

Japan, 3, 300 313 (in Japanese).

Hariya, Y. and Kikuchi, T. (1964) Precipitation of manganese by
bacteria in mineral springs. Nature, 202, 416 417.
Hariya,Y. Miura, H. and Mita, N. (1992) Manganese and manganiferous iron deposits of northeastern Hokkaido. 29th IGC
Field Trip Guide Book, 6, 1 15.
Hewett, D.F. and Fleischer, M. (1960) Deposits of the manganese
oxides. Economic Geology, 55, 1 55.
Katsui, Y., Kitagawa, Y. and Higashihara, T. (1999) Recommendation on the preservation and exploitation of Yunotaki fall.
Research Report on the Manganese Production at Onneto
Yunotaki, Ashoro Town Board of Education, 38 44 (in
Japanese).
Konoya, N., Kobayashi, T., Kim, C.W. and Kawachi, S. (1968)
Explanatory text of the geological map of Japan, Asahidake.
Geological Survey of Hokkaido (in Japanese).
Machida, H. and Arai, F. (1992) Atlas of tephra in and around
Japan. University of Tokyo Press, Tokyo (in Japanese).
Miura H. and Hariya Y. (1997) The recent manganese deposit in
Hokkaido, Japan. In Manganese Mineralization: Geochemistry and Mineralogy of Terrestrial and Marine Deposits
(Nicholson, K., Hein, J.R., Buhn, B. and Dasgupta, S. Eds.).
Geological Society Special Publication No.119, 281 299.
Mita, N., Maruyama, A., Usui, A., Higashihara, T. and Hariya, Y.
(1994) A growing deposit of hydrous manganese oxide produced by microbial mediation at a hot spring, Japan. Geochemical Journal, 28, 71 80.
Mita, N. and Miura, H. (2003) Evidence of microbial formation
of manganese wads at the Asahidake hot spring in Hokkaido,
Japan. Resource Geology, 53, 233 238.
Nakamura, Y. and Hirakawa, K. (2003) Identification of Holocene
tephras in the eastern part of Hokkaido, Japan. Proceedings
of the General Meeting of the Association of Japanese
Geographers, 63, 241(in Japanese).
Roy, S. (1981) Manganese deposits, pp. 458 Academic Press,
London.
Umemoto, S., Matsumura, A., Yamaya, M. and Ishibashi, Y. (1956)
Sulphur, iron and manganese deposits around the Mt.
Meakan dake.
Bulletin of the Geological Survey of
Hokkaido, 24, 21 35 (in Japanese).
Usui, A. and Mita, N. (1995) Geochemistry and mineralogy of a
modern buserite deposit from a hot spring in Hokkaido,
Japan. Clay and Clay Minerals, 43, 116 127.
Wada, K., Inaba, C. and Nemoto, Y. (1997) Eruption history of
Me akan Volcano, eastern Hokkaido, during the last 12000
years. Fall session of the Volcanological Society of Japan,
100 (in Japanese).
Yoshimura, T. (1952) Manganese deposits of Japan. Kyushu
University, Fukuoka (in Japanese).
(Manuscript received; 10 September, 2003)
(Manuscript accepted; 8 September 2004)