Clay Science 5, 9-18 (1976) 9

MINERALOGY AND CHEMISTRY OF THE KAOLIN

DEPOSITS OF THE SETA MINE, HOKKAIDO

T. KOMURA AND T. SUDO

Geological and Mineralogical Institute , Faculty of Science, T
okyo University of Education, Otsuka , Bunkyo-ku, Tokyo.
(Received February 13, 1975)

ABSTRACT

The kaolin deposits of the Seta mine , Hokkaido were formed by

hydrothermal kaolinization of tuffaceous rocks . The kaolin of the Taisei-
1 deposit replacing fine-grained rhyolitic tuff is of the highest quality
,
composed of about 60 percent kaolinite , 30-40 percent quartz and about
5 percent pyrite. Kaolinite may be classified into two types , A and B,
by slight differences in crystallinity ; A is a well crystallized type with
a triclinic cell, while B is a more disordered type , probably a "b-axis
disordered kaolinite". Kaolinite in the peripheral and basal parts of
the deposit is of type A usualy accompanied by a minor amount of
alunite, whereas kaolinite in the central part is mainly of type B.
Micas are absent in this deposit , except for a small amount of a mixed-
layer mineral of mica-montmorillonite . Mineral assemblages, represent-
ed by quartz-kaolinite-alunite in the fine-grained tuff and kaolinite -quartz-
montmorillonite in propylite , show that the alteration took place at high
activity of H+ relative to activities of metal cations .

INTRODUCTION

Occurrence, geology and mineralogy of kaolin deposits in Japan were

reviewed by Nagasawa et al . (1969) . Though mineralogical and chemical
studies of kaolin deposits have been carried out recently along with geologi -
cal and mining surveys, further details are still required for developing
most of the deposits. Mining of the Seta kaolin deposits was started in
1948. In spite of the long period of mining , the kaolin deposits have not b
een described, except a brief decription by Yamada (1953) and Tanemura
(1954) . In the present paper, the mineralogy, clay mineralogy and chemis-
try of the Seta Kaolin deposits are given and their mode of formation is
discussed.

Geological Setting

The Seta kaolin deposits are situated on the southern slope of Mt . Nyofu
of the Shikaribetsu volcanic zone in Tokachi Province , Hokkaido. The area
around the deposits consists of Miocene sedimentary rocks such as fine-
grained tuff, sandy tuff, tuff breccia, hard siliceous sandstone and shale.
10 T. Komura and T. Sudo

Brecciated rock fragments in the tuffaceous rocks are largely of black-

colored hard andesite, 5-20 cm in size. Thin pumice beds are intercalated
in the fine-grained tuff in places. Mercury mining was conducted in several
areas where hard sandstone and shale are distributed.
The kaolin deposits are of hydrothermal origin related genetically to
mercury deposition. There are three workable kaolin deposits; Taisei-1,
Taisei-2, and Tobu.
Taisei deposits occur in the boundary zone between fine-grained tuff and
tuff breccia. Taisei-1 deposit is found as a replacement deposit in the fine-
grained tuff, and Taisei-2 deposit in the tuff breccia.
Major mineral components of Taisei-1 deposit and its altered wall rocks
are quartz and kaolinite. The altered wall rocks are divided into several
zones in terms of mineral assemblages. Although some of the zones are
gradational, these zones are discriminated also by microscopic textures and
macroscopic properties. In the profile along the NE-SW direction through

FIG. 1. A section of the Taisei-1 de-

posit showing alteration zones. FIG. 2. A section of the Taisei-1
1: quartz zone. 2: quartz- deposit showing mineral
kaolinite-alunite zone. 3 and distribution. F-F : fault
4: kaolinite-quartz-pyrite zone zone.
(workable kaolin body ; 3: red
kaolin. 4 : blue kaolin). 5:
kaolinite - quartz - montmorillo-
nite zone. 6 : kaolinite-quartz-
montmorillonite rock retaining
the texture of propylite distrib-
uted locally. F-F: fault zone.
Ml: metre-level.
 Kaolin Deposits 11

the kaolin deposit, the following zones are discernible: quartz zone — quartz-
kaolinite-alunite zone — kaolinite-quartz-pyrite zone (workabe kaolin body) —
(f ault zone) -- kaolinite-quartz-montmorillonite zone (Fig. 1) .
The workable kaoln is brecciated in places near the fault zone .
Progressing toward Taisei-2 kaolin body, tuff breccia has suffered progres-
sive alteration as indicated by the aspect of andesite breccias changing in
the following order, unaltered — altered along peripheral layers — altered
entirely.
Tobu deposit is found as a replacement deposit in thin layers of tuff
intercalated in hard sandstone and shale. Its general strike and dip are in
accord with those of the country rocks.
Taisei-1 kaolin in fine-grained tuff is of the highest quality in the mine
area. It forms a lenticular body, its workable portion being about 100
metres along its trend, 100 metres in depth and 10-15 metres in width .
The following description is concerned mostly with the Taisei-1 kaolin
deposit.

Analytical Procedures

Specimens of kaolin and its wall rocks were studied by means of chemical
analysis, X-ray diffractometry and electron microscopy. Values of pH of
water-suspended powdered specimens were measured . Identification and
quantitative analysis of the constituent minerals of each sample were made
by X-ray analysis.
Calibration curves for the quantitative analysis were drawn using ZnO as
an internal standard in the following ways. (a) Quartz and kaolinite :
Quartz from a pegmatite and kaolinite from the Seta mine were mixed in
various proportions. A fixed amount of ZnO (100 mg) was mixed with each
of the various mixtures (500 mg) . Calibration curves were based on the
relationship of the ratio IQ : IZ versus weight percent of quartz , or of the
ratio IK : Iz versus weight percent of kaolinite ; 4, IK, IZ are intensities of
3.36 A-peak of quartz, 3.59 A-peak of kaolinite, and 2.81 A-peak of ZnO, res-
pectively. (b) K-feldspar : Mixtures of quartz and K-feldspar from a peg-
matite were prepared in various proportions. Calibration curves were based
on the ratio IF : IZ versus weight percent of K-feldspar, where IF means the
intensity of 3.24 A-peak of K-feldspar. (c) Alunite: This mineral is usually
associated with quartz and kaolinite in the alteration zone. In a preliminary
experiment the proportions of quartz and kaolinite associated with alunite
were estimated to be in a range of 3 : 1-1 : 1. Then, a mixture of quartz
and kaolinite in the ratio 3 : 2 was used as a diluent of alunite from the
Ugusu, Izu. The 2.96 A-peak of alunite was used. (d) Pyrite: The mineral
is usually found in association with kaolinite and quartz. Proportions of
kaolinite and quartz accompanied by pyrite were estimated to be nearly 3 : 2
by a preliminary experiment. Then, a mixture of kaolinite and quartz in
the ratio of 3 : 2 was used as a diluent of pyrite from the Shakanai mine,
Akita. The 2.71 A-peak of pyrite was used. (e) Montmorillonite : Mont-
12 T. Komura and T. Sudo

morillonite and kaolinite from the Seta mine were mixed in various propor-
tions. Calibration curves were based on the relationship of the ratio IN: IK
versus weight percent of montmorillonite, where IM means the intensity of
15A-peak of montmorillonite.
Minor amounts down to 2-3 percent could be detected with reproducible
results in the cases of such minerals as quartz, K-feldspar, alunite and
pyrite, because weak peaks were confirmed on account of their sharpness.
Reliablity and reproducibility are likely to decline in obtaining the contents
less than 10 percent of clay minerals such as kaolinite and montmorillonite;
probably the contents may be in error by a few percent. The total amounts
of the constituent minerals in the rocks including alunite often fell short
of 100 percent. This may be due to the presence of opaline silica which is
usually found in association with alunite.
Rock fragments were pulverized. 10 g of fine powder which passed through
a 100-mesh screen was suspended in 50 ml of distilled water. The pH-values
of the suspension were measured with a pH-meter. Factors controlling pH-
values of water suspension of mineral powder are diverse, but the follow-
ing three may be most important.(a) Surface acidity or alkalinity of
mineral grains, particularly of clay mineral particles.(b) Hydrogen ions
dissociated in water by the hydrolysis reaction of mineral grains suspended
in water.(c) The pH-values of pore solutions in interspaces of mineral
grains in superficial rocks, originated from rain water, surface water and
underground water and also from a mineral acid owing to oxidation of
sulfide minerals. The pH-values controlled by factor (b) may correspond
to "abrasion-pH" proposed by Stevens and Carron (1948), usable in mineral
identification because the hydrolysis reaction is characteristic of many
minerals. Though the pH-values of water-suspended mineral powders are
diverse, different values are obtained for different alteration zones.

Mineralogical and Chemical Properties of the Alteration Zones

of Taisei-1 Kaolin Deposit

On the profile of the Taisei-1 kaolin and its wall rock along the NE-SW
direction, distributions of mineral kinds, mineral contents, and pH-values
are shown in Figs. 2, 3 and 4, respectively.
Quartz zone (pH: 5) is a fine-grained rock composed of 80-90 percent
quartz and 5-15 percent K-feldspar without clay minerals and alunite.
Quartz grains show a fine mosaic texture as a whole. K-feldspar grains
have euhedral shapes in mosaic of quartz but they are usually replaced by
quartz sporadically within each crystal particle. Quartz and K-feldspar are
also found in the wall rock, which is loose and porous and free from alter-
ation related to the kaolin deposition. However, the amount of quartz in
the wall rock is less than that in the quartz zone. It may be interpreted
that the quartz zone is a part of the wall rock suffered from intense si-
licification, and the K-feldspar is not an alteration product related to the
kaolin mineralization.
 Kaolin Deposits 13

FIG. 3. Mineral contents of Taisei-1 kaolin deposit and its altered

wall rocks. Left: 0-Ml to minus 31-M1. Right:+37-M1,
Ml: metre-level. Black spots in each level means stations
for collecting samples. 1: quartz zone. 2: quartz-kaolinite-
alunite zone. 3: kaolinite-quartz-montmorillonite rock re-
taining the texture of propylite distributed locally. 4:
workable kaolin (kaoinite-quartz-pyrite zone). 5: kaolinite-
quartz-montmorilonite zone. F-F: fault zone.

Quartz-kaolinite-alunite zone (pH: 4-5) is a transitional zone between the

quartz zone and the kaolin body. It is porous and is largely composed of
quartz veinlets which are traversed by kaolin veinlets in places. The
alunite content is less than 5 percent. The proportion of quartz to kaolinite
in this zone is in the range 3: 1-1: 1.
Kaolinite-quartz-pyrite zone (pH: 2.5-3.5)(workable kaolin) is composed
of uniform, earthy and massive aggregates of kaolinite (about .60 percent),
quartz (30-40 percent) and pyrite (about 5 percent). Minor amounts of
alunite and opaline silica tend to occur in deeper parts of the zone. The
quality of kaolin is likely to decline when associated with alunite and o-
paline silica. In the basal part of the zone, the kaolin is grayish blue in
color (blue kaolin) owing to contamination by fine-grained pyrite. Along
the periphery of the upper part, the kaolin is reddish brown in color (red
14 T. Komura and T. Sudo

FIG. 4. A section of the Taisei-1 FIG. 5. A section of the Taisei-1

deposit showing the pH- deposit showing the dis-
values. 1: lower than tribution of two types of
pH 3. 2: pH 3-4. 3: pH kaolinite. 1: type B (a
4-5. 4: higher than pH 5. slightly disordered type).
F-F: fault zone. 2: either type A or B.
3: type A (a well-crystal-
lized type).

kaolin) owing to contamination by limonite derived from oxidized pyrite.

Red kaolin has been decolorized to pure white kaolin along small fissures in
the superficial parts as a result of bleaching by surface water and circulat-

ing ground water.

Kaolinite may be divided into two types, A and B, by slight differences

in the X-ray powder diffraction pattern. Type A is a well-crystallized

kaolinite having, in most cases, a triclinic cell. Type B is slightly lower

in crystallinity than A; the reflections with k indexes not a multiple of 3

(k•‚3n) tend to be weak and the resolution of neighbouring X-ray peaks is

not so good as in A. However, the differences between the two types are

hardly discernible on differential thermal analysis curves, or in particle

size and crystal shape observed under the electron microscope; both types

are platy crystals with hexagonal shapes, 0.35-0.5 micron in diameter.

Therefore, these two types may be discriminated only by X-ray analysis.

Type B is slightly disordered, probably a" b-axis disordered kaolinite".

Harvey and Vitaliano (1962) reported that the degree of crystallinity of

kaolinite increases as the alunite-quartz-zone is approached. Robertson et al.

 Kaolin Deposits 15

(1954) reported the crystallographical and mineralogical properties of a

completely b-axis disordered kaolinite comparing with those of a well-crys-
tallized one; the former occurs as fine-grained euhedral crystals , whereas
the latter occurs as coarse-grained crystals being less perfect in crystal
shape. The relation between the crystallinity and the environmental con-
dition of the formation of kaolinite has not been made clear.
In the present kaolinite samples, the difference in crystallinity between
A- and B-types is slight; the difference in their particle size is hardly
discerned. Thus it is still more difficult to discuss the environmental condi-
tion of their formation without considering differences in their modes of
occurrence.
Type B tends to be widely distributed in the central part of the kaolin
body associated with pyrite and without alunite. It is noticed that the
range of distribution of pyrite shown in Fig . 2 nearly coincides with that
of type B shown in Fig. 5.
Type A seems to become dominant along the periphery associated with
alunite. Probably it may be said that kaolinite crystals may favorably
develop into ordered crystals in an oxidizing condition yielding H2SO4 from
either H2S or metal sulfides, and an increase of the dissociation of H2SO4.
Kaolinite-quartz-montmorillonite zone (pH: 3) is mainly distributed on the
north side of the fault zone and is composed of kaolinite, quartz and mont-
morillonite. The wall rock of this alteration zone is propylite which is
seen sporadically in this zone grading into the clayey part. Low pH-values
may be due to mineral acids in circulating ground water along the fault
one and to the surface acidity of montmorillonite.
Chemically, Al2O3, Fe2O3 and H2O are likely to increase and SiO2 and K2O
decrease toward the kaolin body. Variation of TiO2 may not be discernible
(Table 1).

Mode of Formation of the Taisei-1 Kaolin Deposit

Hemley and Jones (1964) and Hemley et al. (1966) carried out experimen-
tal and theoretical studies on hydrothermal alteration dealing with the
stability relations among K- and Na-feldspars, micas , kaolinite and alunite
in terms of physicochemical conditions such as temperature, pressure and
metal cation/H+ ratio, and showed three stages of hydrolytic alteration;
incipient, intermediate, and advanced. The incipient alteration is represented
by propylitic alteration, and the advanced alteration is represented by
alunite-kaolinite-quartz bearing assemblage. Progressive increase of the
activity of H+ relative to the activities of metal cations such as K+ or Na+
would push on the following change in the mineral kinds from left to
right: K-feldspar-K-mica-kaolinite-quartz. Possible reactions may be
expressed as follows:

3KA1Si3O8+2H+=KAl3Si3O10 (OH) 2+6SiO2+2K+ (1)

K-feldspar K-mica
16 T. Komura and T. Sudo

KAl3Si3O10(OH) 2+H++1.5H2O=1.5Al2Si2O5 (OH) 4+K+ (2)

K-mica Kaolinite
1.5Al2Si2O5(OH) 4+9H+=3SiO2+7.5H2O+3Al3+ (3)
Kaolinite
The following facts present problems in considering the mode of formation
of Taisei-1 kaolin deposit and related wall rock alteration. (1) The deposi-
tion occurred along the channels in porous wall rocks such as fine-grained
tuff and tuff breccia. (2) Propylite is found as a wall rock along with the
tuffaceous rocks in the altered area. Usually, it is altered partially to
montmorillonite and occurs in contact with the kaolin or with the fault
zone which was formed after the kaolin deposition. (3) Intense silicification
is seen in quartz rock. (4) Micas can not be detected in the representative
samples, except for a small amount of a mixed-layer mineral of mica-mont-
morillonite. (5) Mineral assemblages are represented by kaolinite-quartz-
alunite in fine-grained tuff and kaolinite-quartz-montmorillonite in propylite.
In every respect the alteration of the Seta mine shows the advanced

TABLE 1. Chemical composition of representative specimens from Taisei-1

and Taisei-2 kaolin deposits and from the altered wall rocks

1-3: Taisei-1 kaolin deposit and the altered wall rock.

1: Fine-grained tuff nearly free from hydrothermal alteration related to
the kaolin deposition.
2: Kaolin (Type B, less-than-2 microns fraction).
3: Propylite free from hydrothermal alteration related to the kaolin
deposition.
4-7: Andesite fragments in tuff breccia which is wall rock of Taisei-2
kaolin deposit.
4: Unaltered breccia. Glassy matrix is free from the hydrothermal effect.
5: Unaltered breccia. Glassy matrix has been slightly altered by the
hydrothermal alteration.
6: Altered peripheral part of a fragment. Its central part is still free
from alteration.
7: Entirely altered fragment. Its outline is still retained in the clayey
matrix.
 Kaolin Deposits 17

stage of hydrolytic alteration of Hemley and Jones (1964).

Probably potassium ions were partly taken part in a chemical reaction to
form alunite. Generally speaking, the principal alteration is shown by kao-
linite-alunite assemblage with quartz suggesting such environmental condi-
tions leading to superficial oxidation, marked base leaching , increase of the
dissociation of H2SO4, and high activities of HP and silica (aqueous) be-
fore crystallization of quartz. The main wall rock of the present kaolin de-
posit is rhyolitic glassy tuff. It is considered that potassium in alunite and
aqueous silica with a high activity are originated from rhyolitic volcanic
glass in the tuff.

Taisei-2 Kaolin Deposit

Tuff breccia distributed in the area about 50 metres away from the kaolin
body contains andesite fragments of 5 cm in mean size . Its superficial part
has suffered slight alteration and contains kaolinite, montmotrillonite , quartz
and a minor amount of gypsum. Montmorillonite and plagioclase are the
only detectable crystalline minerals in deeper parts. Kaolinite and quartz
may be of the supergene origin.
Tuff breccia distributed within 50 metres from the kaolin deposit has
relatively large andesite fragments, about 20 cm in size, and has suffered
progressive alteration toward the deposit. Hard andesite fragments are
usually more resistant to the alteration than the cementing glassy material .
Mineral assemblages found in fragments that suffered progressive alteration
are as follows. Unaltered fragments: F+C+T, fragments altered along its
peripheral layer: F+C+T+M+Q, and fragments entirely altered (its outline
remains in clayey material): F+C+T+K, where F: plagioclase , C: cristo-
balite, T: tridymite, M: montmorillonite and Q: quartz. Further toward the
deposit, the outlines of clayey fragments fade out , and the tuff breccia
grades into a body with a uniform clayey appearance. It is composed of
kaolinite and quartz as two major components with cristobalite , tridymite,
alunite and pyrite as accessories. Plagioclase, cristobalite and tridymite
are widely found in Taisei-2 kaolin and its altered wall rocks , but they are
not detected in Taisei-1 kaolin. Progressive alterations of andesite frag-
ments demonstrate decrease of FeO, CaO, MgO and K2O and no appreciable
change of SiO2, Al2O3 and TiO2 (Table 1).

ACKNOWLEDGEMENTS
The authors gratefully acknowledge the help of A. Sanjo, Manager of the Chuo
Kaolin Co. Ltd. and T. Esaki, Manager of the Seta Mine, who gave support for the
field investigations. Thanks are due to the officials of the Ministry of Education for
their kindness in granting fund for this study.
18 T. Komura and T. Sudo

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HEMLEY, J. J. and JONES, W. R. 1964. Chemical aspect of hydrothermal alteration
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HEMLEY, J. J., HOSTETLER, P. B., GUDE, A. J. and MOUNTJOY, W. T. 1969. Some sta-
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kaolin clays from Pugu, Tanganyika : Amer. Miner., v.39, p.118-138.
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Japan, v.5, No.9, p.27-32.