doi: 10.1111/j.1751-3928.2010.00114.x Resource Geology Vol. 60, No.

1: 52–70

Original Article rge_114 52..70

Application of Chlorite Geothermometry to Hydrothermal

Alteration in Toyoha Geothermal System, Southwestern
Hokkaido, Japan

Atsuyuki Inoue,1 Kyohei Kurokawa2* and Tamao Hatta3

1
Department of Earth Sciences, Chiba University, Chiba, Japan, 2Graduate School of Natural Science, Chiba University, Chiba,
Japan and 3Japan International Research Center for Agricultural Science, Tsukuba, Japan

Abstract
In this study, we applied chemical geothermometers to the estimation of formation temperatures of chlorites
from various types of hydrothermally altered rocks in the Toyoha geothermal field, using core samples from six
drill holes (TH-2 to TH-7) together with wasted ore samples from Toyoha vein-type ore deposit. Based on the
preliminary examination of mineral assemblages by X-ray powder diffraction and optical microscopy, hydro-
thermal alteration observed through the drill holes was classified into four types of alteration zones: propylitic,
mixed-layer minerals, kaolin minerals, and ore mineralized zones. The mineral assemblage of the ore miner-
alized zone observed through TH-2, TH-4, and TH-6 is similar to those of Toyoha ore veins reported previ-
ously. The Fe3+/SFe ratios of chlorites were determined by X-ray photoelectron spectroscopy (XPS), in addition
to the usual microprobe analyses. The ratios ranged from 0.20–0.26 for chlorites from the propylitic alteration
zone and from 0.13 to 0.17 for those from the ore mineralized zone associated with sulfide minerals. After
correcting the Fe3+ contents in the octahedral sites of chlorite structures, we obtained acceptable temperatures
of the chlorite formation by application of geothermometers, for instance, a similar range of 150–300°C for
chlorites from either the propylitic zone or the ore mineralized zone developed through TH-2, TH-4, and TH-6.
Chlorites from the ore mineralized zone proximal to the Toyoha deposit are characterized by high Fe and Mn
contents compared to the propylitic chlorites, which is similar to the Toyoha vein-filling chlorites; the forma-
tion temperatures were close to both the homogenization temperatures of fluid inclusions and the present
subsurface temperatures measured through drill holes. Chlorites from the Toyoha ore veins, however, gave
slightly higher formation temperatures (180–350°C) than those of chlorites from the ore mineralized zone in
the drill cores. This suggests that several types of hydrothermal alteration occurred at different stages in the
Toyoha geothermal field and the composition of product chlorite was controlled not only by the temperature
but also the composition of fluid related to the formation. Reliable estimation of temperature for the chlorite
formation provides basic information on evaluating correctly other physicochemical conditions prevalent at the
formation.
Keywords: chlorite geothermometer, ferric iron content, hydrothermal alteration, Toyoha epithermal vein-type
deposit, XPS.

Received 5 January 2009. Accepted for publication 13 March 2009.

Corresponding author: A. INOUE, Department of Earth Sciences, Graduate School of Science, Chiba University, Yayoi-cho 1-33,
Inage-ku, Chiba 263-8522, Japan. Email: atsuyuki_inoue@faculty.chiba-u.jp
*Present address: Kamioka Mining & Smelting Co. LTD., Gifu, Japan.

© 2010 The Authors

52 Journal compilation © 2010 The Society of Resource Geology

1. Introduction
Chlorite is a common rock-forming mineral that
constitutes diagenetically altered and low- to high-
grade metamorphosed rocks. It is also ubiquitous in
hydrothermally altered rocks developed in active and
fossil geothermal fields involving epithermal vein-
type ore deposits, as well as massive sulfide deposits.
Chlorite displays a wide range of non-stoichiometric
compositional variations depending on bulk rock com-
position and physicochemical conditions prevalent at
the formation. The variation of chemical composition
in chlorite therefore is useful to obtain information
on the physicochemical conditions of the formation;
the use of chlorite composition for estimating the
formation temperature is called chemical chlorite
geothermometry.
Several approaches of chlorite geothermometry have
been proposed, for instance (i) empirical calibrations
based on the tetrahedral Al occupancy and/or the octa-
hedral vacancy as a function of measured temperatures
in active geothermal systems and homogenization
temperatures of fluid inclusions in fossil geothermal
systems (e.g. Cathelineau & Nieva, 1985; Cathelineau,
1988; Hillier & Velde, 1991) and (ii) thermodynamic
calculation of equilibrium conditions for chlorites
whose composition is expressed as the activities of
end-member components of known thermodynamic
properties (e.g. Walshe & Solomon, 1981; Walshe, 1986;
Vidal et al. 2001). The first geothermometry has been
applied to diagenetic to low-grade metamorphic chlo-
rites because of its simplicity. However, many previous
studies indicated that chlorite compositions are not
only sensitive to prevailing physicochemical condi-
tions but also to bulk rock composition (e.g. Kranidi-
otis & MacLean, 1987; Jowett, 1991; De caritat et al.,
1993; Zang & Fyfe, 1995; Frimmel, 1997; Xie et al. 1997;
Zane et al. 1998). Although various equations based on
different rock compositions have been proposed, none
of them has given reliable results over a wide range of
physicochemical conditions of formation (De caritat
et al., 1993; Vidal et al. 2001).
Compared to the first empirical geothermo-
metry, there are many advantages in the second
thermodynamics-based geothermometry. In addition
to the estimation of formation temperature and
pressure, it accounts for the variations of the rock min-
eralogy including elemental partitioning between
coexisting minerals (e.g. Vidal et al. 2001) and the
potential influence of additional physicochemical
parameters like fluid composition and redox condi-
© 2010 The Authors
Journal compilation © 2010 The Society of Resource Geology
Application of chlorite geothermometry
tions (e.g. Walshe & Solomon, 1981; Walshe, 1986;
Kavalieris et al., 1990; Lonker et al., 1990). Nevertheless,
no single chlorite geothermometer has performed sat-
isfactorily over the whole range of natural conditions,
as pointed out by De caritat et al. (1993). This ineffi-
ciency probably resulted from the uncertainties of the
thermodynamic properties of chlorites used, the
unsuitable mixing model for chlorite solid solution
used, and more importantly neglecting the effect of
ferric iron contents in estimating the formation tem-
perature in many previous studies. After the review of
De caritat et al. (1993), thermodynamic properties of
end-member chlorite have been continued to accumu-
late and the mixing properties of the solid solution
have been revised (e.g. Saccocia & Seyfried, 1994; Baker
& Holland, 1996; Holland et al., 1998; Vidal et al., 1992,
1999, 2001, 2005; Parra et al. 2005 and many others). As
for the effect of ferric iron contents, Vidal et al. (2006)
and Inoue et al. (2009) demonstrated that the estimation
of the formation temperature of chlorite was more
improved taking into consideration the effect of ferric
iron contents for chlorites from diagenetic to low-grade
metamorphic rocks.
In this contribution, the validity of the chlorite geo-
thermometer will be tested by applying it to hydrother-
mally altered rocks in the Toyoha geothermal system.
The geothermal system contains the Toyoha epithermal
vein-type ore deposit that is polymetallic with mainly
Pb, Zn, and Mn ores, together with Ag, Cu, Bi, In, Sn,
Au, W, etc. (e.g. Shikazono, 2003). It is also noted that
Fe and Mn-rich chlorites occur as gangue minerals
associated with the ore mineralization. Many works on
the ore mineralization at Toyoha have been published,
but few on the hydrothermal alteration of the country
rocks including those of the peripheral area (e.g. Sawai,
1984, 1986, 1999, 2006). In the present study we exam-
ined chlorites using core samples from the periphery of
Toyoha deposit, in addition to those in wasted ore
samples from the deposit, because the Toyoha mine has
been ceased on 2006 and we cannot collect directly
samples from the pits. We will address to the relation-
ship between the temperatures of chlorite formation
and the chemical compositions so as to discriminate
different types of hydrothermal alteration developed
in the Toyoha geothermal system.
2. Geologic settings and ore deposit
The Toyoha geothermal system, located at about
30 km west of Sapporo city, south-western Hokkaido,
Japan, is situated in a volcano-depression structure
53
A. Inoue et al.
Fig. 1 Simplified geologic map of the Toyoha geothermal field showing the ring structure, faults, and drilling sites, together
with the distribution of veins at Toyoha deposit (after NEDO, 1988; Yajima et al. 1993). Lines W-E and S-N indicate
locations of cross sections in Figures 2 and 3.
surrounded by several volcanic summits like Mts
Muine and Nagao (Fig. 1). The geology of the Toyoha
area has been studied in detail by Akome and Hara-
guchi (1963), Kuwahara et al. (1983), NEDO (1988),
et al. According to NEDO (1988), thick piles of
Miocene sedimentary and volcanic rocks bury the
depression structure (Fig. 2). The basement is rock of
the pre-Tertiary Usubetsu Formation that consists of
sandstone and mudstone. The basement heaves and
submerges in the south-eastern and north-western
parts of Toyoha area, respectively, inferred from the
encounter depth through Holes TH-2 and TH-7. The
Miocene formations that unconformably overly the
basement rocks are divided into three groups in
the Toyoha area: in the ascending order from the
basement, Lower Miocene Jozankei Group, Middle
Miocene Toyoha Group, and Upper Miocene Asari
Group. Each Group is further subdivided into the
Shiramizugawa and Koyanagisawa Formations of the
Jozankei Group, the Motoyama, Nagato, Takinosawa,
and Otarunaigawa Formations of the Toyoha Group,
and the Tokiwa and Oheyama Formations of the
Asari Group (NEDO, 1988). Among the formations,
we encounter the Shiramizugawa, Koyanagisawa,
54
Motoyama, and Nagato Formations through the drill
holes examined. The Shiramizugawa Formation con-
sists of dacitic to andesitic lavas and their pyroclastics
locally intercalated with the alternation of silts to fine-
grained sandstones and tuffs characteristically in
Holes TH-3 and TH-5. Andesites from the Shirami-
zugawa Formation yielded K–Ar ages of 18.3–21.4 Ma
(Watanabe, 1997; MITI, 1998). The Koyanagisawa
Formation is composed mainly of andesitic to basaltic
and rhyolitic lavas and their pyroclastics. The
Motoyama Formation of the Toyoha Group, which
unconformably overlies the Koyanagisawa Formation,
is conglomeratic rock with fine-grained sandstones,
siltstones, and mudstones in the upper part. Plant
fossils, correlated to the Daijima-type flora of Middle
Miocene (16–18 Ma), occur commonly in the
Motoyama Formation. The Nagato Formation consists
of andesitic lavas and their pyroclastics. All the rocks
described above are propylitized pervasively with
various degrees of alteration. The country rocks of
Toyoha deposit are the Koyanagisawa, Motoyama, and
Nagato Formations. Andesitic volcanic activities at
Mts Muine and Nagao have continued since 3 Ma
(NEDO, 1988). Besides them, many types of intrusive
© 2010 The Authors
Journal compilation © 2010 The Society of Resource Geology
 Application of chlorite geothermometry

Takinosawa Fault
Yunosawa Fault
Kurumisawa Drill hole
Kurumisawa Fault
MAJT-12, 13

Yunosawa Fault
MAJT-9

R. Ogawa

R. Shiramizu
MAJT-14
1000

MAJT-10
N

TH-5
R. Shirai

TH-7
TH-2
TH-6
S
500
Elevation (m)

-500

0 1 2 km

-1000
Kurumisawa Drill hole
Kurumisawa Fault
MAJT-16, 19

Yunosawa Fault
Oenosawa

MAJT-17, 18
Kurumisawa

1000 W
R. Shirai

R. Shirai
TH-6
TH-4

TH-1

TH-3
500 Jozankei

E
Elevation (m)

-500

0 1 2 km

-1000
Legend
Q u a t e r n a ry Vo l c a n i c s Jozankei Group (Miocene) P r e -Te r t i a r y
Mt. Nagao Andesite Koyanagisawa Formatio n Usubetsu Formatio n

To yo h a G r o u p ( M i o c e n e ) I n t r u s i ve R o c k s
Takinosawa, Shiramizugawa Formatio n
Quartz Diorite
Nagato Formations

Motoyama Formatio n

Fig. 2 Geologic cross sections along lines N-S and W-E of Figure 1 (simplified from NEDO, 1988).

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Journal compilation © 2010 The Society of Resource Geology 55
A. Inoue et al.
rocks from basaltic to granitic compositions are
encountered through the drill holes examined in the
present study. The K–Ar ages of granitic intrusions
occurred in the bottom of several holes are reported to
be 14.0 ⫾ 0.7 and 18.2 ⫾ 0.7 Ma of TH-4, 12.1 ⫾ 0.6 Ma
of TH-5, and 9.1 ⫾ 0.8 Ma of TH-7 (NEDO, 1988). The
ages of TH-4 and TH-5 granitic intrusions are corre-
lated to that of the Migimatagawa quartz diorite (13.9
⫾ 0.7 Ma reported by NEDO, 1988) that crops out in
the northern part of Toyoha area; that of TH-7 may be
correlated to the lower lithologic facies of Jozankei
quartz porphyry (9.5 ⫾ 0.7 Ma) exposed in the eastern
part of Toyoha. The K–Ar age of TH-7 granodiorite
also is close to those of illite (9.8–11.5 Ma reported by
Aoki et al., 1999) that occurs as veinlets with an E-W
strike associating with galena and dolomite along the
River Ogawa.
As shown in Figures 1 and 2, faults having NW-SE
and E-W trends predominate in the Toyoha area, as
well as minor those of NE-SW and N-S trends. Two
stages of mineralization are generally distinguished in
the Toyoha deposit based on the cross cutting relation-
ship of veins and the paragenesis of ore minerals (e.g.
Yajima & Ohta, 1979; Narui et al., 1988; Yajima et al.
1993). The early veins, mainly consisted of galena, low
FeS-bearing sphalerite, and pyrite, tend to be emplaced
along the E-W fractures; the later veins with galena and
relatively high FeS-bearing sphalerite in addition to In,
Bi, Ag, and Sn minerals are emplaced mainly along the
NW-SE fractures. K–Ar ages of illite from 3.0 to 0.5 Ma
are reported for the mineralization ages of the Toyoha
deposit (e.g. Marumo & Sawai, 1986; Sawai et al., 1989;
Aoki et al., 1999). The K–Ar ages tend to decrease
toward the veins extended to the southeastern area of
the deposit. It is also known that the formation tem-
peratures of veins tend to increase from the early to the
later stages of mineralization, inferred from the homog-
enization temperatures of fluid inclusions (Yajima &
Ohta, 1979; Kanbara et al., 1989; Sanga et al., 1992;
Masuta et al., 1996). The K–Ar ages of illitic minerals
collected from exposures along the River Yunosawa
outcrops near TH-4 and TH-6 are reported to be 0.8–
2.4 Ma (Sawai et al., 1989; Aoki et al., 1999). The ages
overlap with those of the ore mineralization (<3.0 Ma)
at Toyoha deposit.
The distribution of subsurface temperature in the
Toyoha geothermal system is illustrated in Figure 3,
cited from NEDO (1988). Maximum bore hole tem-
perature attains more than 300°C at the bottom of
TH-2 and TH-4. The broad interval of isothermal con-
tours observed at the intermediate depth ranges of
56
TH-6 and the Kurumisawa drillhole indicates that
convective circulation of fluids occurs there. In
contrast, the reversal distribution in temperature at
TH-5 suggests incursion of colder waters from the
surface.
3. Samples and methods
Samples used in the present study were those collected
from 6 drill holes (TH-2, TH-3, TH-4, TH-5, TH-6, and
TH-7) and from several outcrops along the Rivers
Shirai, Yunosawa, and Ogawa, in addition to the wasted
ore samples of the Toyoha mine (Fig. 1). The whole
rock mineralogy of about 700 samples in total was
determined by X-ray powder diffraction (Rigaku
RAD I-B, Tokyo, Japan 40 kV, 25 mA, graphite-
monochromatized Cu Ka radiation) and optical
microscopy using about 300 thin sections. Clay frac-
tions (<2 mm) that were separated from rocks by ultra-
sonic vibration and centrifugation were X-rayed to
examine the nature of interlayering, the polytypic
structure, and the d060 values. Percentages of expand-
able layer of interstratified minerals were determined
by comparing the observed XRD patterns with
computer-simulated patterns using a NEWMOD
program (developed by R. C. Reynolds, Jr.). Identifica-
tion of the polytype structures for chlorite, illite, and
kaolin minerals was assigned to following the database
of Bailey (1980).
Chemical analysis of secondary minerals in polished
thin section was carried out with an energy-dispersive
microanalyser (JEOL JSM-5600 equipped with an
Oxford Link ISIS-300, Tokyo, Japan). Analyses were
determined using the conditions: an accelerating
voltage of 15 kV, a beam current of 0.8 nA, a beam
diameter of about 10 mm, and a counting time of 100 s.
EDS data were reduced by a ZAF correction scheme.
The standard included quartz (Si), corundum (Al),
periclase (Mg), synthetic fayalite (Fe), rhodonite (Mn),
anatase (Ti), wollastonite (Ca), albite (Na), and adularia
(K). Chlorite of interest in the present study is often
interlayered with smectite in shallower depths or
makes intimate aggregates with illite and/or carbon-
ates in the matrix of altered rocks. Thus, chlorite analy-
ses were selected using an arbitrary upper limit of
0.5 wt% for total CaO + Na2O + K2O, following Hillier
and Velde (1991).
We used X-ray photoelectron spectroscopy (XPS) to
determine the Fe3+/SFe ratio in chlorite in the present
study. The Scienta ESCA-300 (Uppsala, Sweden) used
for XPS measurements employs an intensity of 1 kW of
© 2010 The Authors
Journal compilation © 2010 The Society of Resource Geology
 Application of chlorite geothermometry

Fig. 3 N-S and W-E cross sections showing the distribution of hydrothermal alteration zones and measured subsurface
temperature (after NEDO, 1988). Dashed lines denote the first appearance depth of epidote (Ep) and actinolite (Act).

© 2010 The Authors

Journal compilation © 2010 The Society of Resource Geology 57
A. Inoue et al.

monochromatized Al Ka radiation under vacuum con-

ditions of 10-9 torr. Charge broadening and shift of
peaks were partially compensated for by flooding the
sample with low energy electrons. Peak shift was cali-
brated with the peak position of C 1s (284 eV). We used
the Fe 3p peak for determining the Fe3+/SFe ratio. The
spectral analytical methods followed the previous ones
adopted by Raeburn et al. (1997a, b) who applied the
methods to the quantification of Fe3+/SFe ratio in
biotite. A Shirley background (Shirley, 1972) was sub-
tracted from the summed spectra using an iterative
approach and the peaks were modeled by a Gaussian-
Lorentzian product function with an added tail func-
tion on the high binding energy side. In preliminary
measurements of hematite and hedenbergite, the
Fe3+ peak of hematite was fitted by a single Gaussian
curve without tail function, whereas the Fe2+ peak of
hedenbergite was composite of Gaussian and Lorentz-
ian functions having asymmetry component on the
high binding energy side. Assuming the existence of
asymmetry only for Fe2+ peak, we could obtain reason-
able goodness values through least squares fitting of
chlorite Fe 3p spectra. The Fe3+/SFe ratio was calculated
from the relative areas of Fe2+ and Fe3+ peaks. The
FeO and Fe2O3 wt% were recalculated from the FeO*
(total iron as FeO) determined by microprobe analyses
using the Fe3+/SFe ratios obtained by XPS peak analy-
sis. The ferric iron was recast into the chlorite structure
formula based on O = 14, in which we assumed that
Fe3+ substitutes only for the octahedral Al in chlorite
structure.

4. Results and discussion

4.1 Alteration zoning
Hydrothermal alteration observed through the drill
cores examined is classified into four zones: ore
mineralized zone, mixed-layer minerals zone, kaolin
minerals zone, and propylitic zone (Fig. 3). The ore
mineralized zone is characterized by the occurrence of
sulfide minerals (pyrite, sphalerite, galena, and locally
chalcopyrite) and/or rhodochrosite, which are similar
to the vein mineral assemblage of Toyoha deposit. The
distribution of this zone is restricted to the lower parts
of Holes TH-2, TH-4, and TH-6. Relatively high Fe Fig. 4 Plots of Al(Total)-Fe*-Mg- Mn atomic ratios for
three types of chlorites in the Toyoha geothermal
(Fe*/Fe* + Mg + Mn = 0.4–0.95) and Mn (Mn/Fe* + Mg system (a) chlorites from the propylitic zone (b) chlo-
+ Mn > 0.05) contents are diagnostic of chlorites in the rites from the ore mineralized zone in drill cores, and
ore mineralized zone as shown in Figure 4, where Fe* (c) chlorites from the ore mineralized zone of Toyoha
is Fe2+ calculated as total iron from microprobe analy- deposit. Fe* denotes Fe2+ calculated from the micro-
ses. The associated illite has usually 2M1 polytype probe analyses.
structure. Sphalerite is generally fine-grained and

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58 Journal compilation © 2010 The Society of Resource Geology

shows yellow to red in color, reflecting the low con-
tents of FeS molecules (<5%).
The mixed-layer minerals zone is composed of inter-
stratified illite-smectite (maily rectorite), chlorite-
smectite, quartz, pyrite, calcite, and small amounts of
trioctahedral chlorite. Sudoite was found locally in the
zone. Plagioclase is partially replaced by the interstrati-
fied minerals. This zone develops in the upper parts of
the ore mineralized zone of TH-2, TH-4, and TH-6
(Fig. 3). No systematic variation in the percentage of
expandable layers in interstratified minerals was recog-
nized as a function of depth within the zone.
The kaolin minerals zone, also distributed in the
upper parts of the ore mineralized zone of TH-2,
TH-4, and TH-6, is defined by the occurrence of well-
crystallized kaolinite, dickite, nacrite, and/or pyro-
phyllite associated with quartz, anhydrite, and locally
alunite and fluorite. Dickite and nacrite occur usually
as monomineralic veinlets. Calcite and pyrite are
also common in the kaolin minerals zone. Primary
plagioclase completely altered to clay minerals in
this zone.
The propylitic zone is distributed pervasively in the
periphery of the central ore mineralized, mixed-layer
minerals, and kaolin minerals zones. The propylitic
zone is well recognized in Holes TH-3, TH-5, and
TH-7. This zone is actually subdivided into several
subzones: from the shallow to the deep, mixed-layer
minerals subzone consisting of interstratified chlorite-
smectite and corrensite with laumontite, chlorite-illite
subzone, chlorite-epidote subzone, and chlorite-
epidote-actinolite subzone. Biotite was identified from
rocks near the bottom of TH-3, though it may be a
contact metamorphic product due to later intrusion
of granitic dike rock. The first appearance depths of
epidote and actinolite are nearly parallel to the present
elevation, but subparallel to the formation boundaries
(Fig. 3). From the distribution of alteration zones, the
propylitic alteration is an earlier product compared
to the other alteration zones, probably at >11 Ma.
However, the propylitic alteration defined as a massive
group above, in more detail, consists of two types
of alteration: early propylitic alteration and later
K-alteration, in terms of the characteristic mineral
assemblage and chemical composition of chlorite
(Inoue et al. in preparation). The K-alteration that is
characterized by the mineral assemblage such as abun-
dant K-feldspar, well-crystallized 2M1 illite, relatively
Fe-rich chlorite, garnet, and locally tourmaline over-
laps on the early-formed propylitic alteration. The
K-alteration probably occurred in relation to the intru-
© 2010 The Authors
Journal compilation © 2010 The Society of Resource Geology
Application of chlorite geothermometry
sion (about 9 Ma) of quartz porphyry encountered at
the bottom of TH-7. Despite the complicated superpo-
sition of alteration, the two types of propylitic alter-
ation are classified as a group for simplicity in the
present study. Chlorite from the propylitic zone has
relatively lower Fe and Mn contents compared to that
from the ore mineralized zone (Fig. 4).
4.2 Ferric iron contents of chlorites
Ferric iron contents were determined by XPS using
seven chlorite samples separated from rocks by
repeated decantation and centrifugation. The examined
samples are six core samples (TH-2-509, TH-2-894,
TH-2-964, TH-2-1272, TH-5-696, TH-6-833) and one
outcrop sample (092701), where the numerical values
after the core number denote the depth. Samples TH-2-
509, TH-2-894, and TH-6-833 are chlorites from the ore
mineralized zone; samples TH-2-964, TH-2-1272, TH-5-
696, and 092701 are those from the propylitic zone. The
XRD patterns of some samples are given in Figures 5
and 6. All the samples examined contain impurities
like illite, quartz, plagioclase, and calcite in various
proportions, but Fe-rich minerals like pyrite were com-
pletely removed by the present sample preparation,
confirmed by the XRD and XPS measurements. The
effect of iron in illite was not taken into consideration in
the present XPS measurements. Fe, Mg-chlorites from
the propylitic zone generally have a IIb polytype struc-
ture, while Fe-chlorites from the ore mineralized zone
may be Ib (b = 97° or 90°) polytype (Fig. 6). Mn-rich,
Fe-poor chlorite like sample TH-2-894 seems to be IIb,
despite serious interference with illite.
Summed XPS spectra and fitted Fe2+ and Fe3+ peaks
are shown for seven samples in Figures 7 and 8. The
relative areas of each peak gave that the Fe3+/SFe ratios
ranged from 0.13–0.17 for chlorites from the ore min-
eralized zone and 0.2–0.26 for those from the propylitic
zone (Table 1). The mean values of Fe3+/SFe ratios of
chlorites from the propylitic zone and the ore mineral-
ized zone associated with sulfide minerals were
approximately 0.23 and 0.15, respectively. The mean
values were used in the geothermometric calculation
of chlorites from the propylitic and ore mineralized
zones, respectively, throughout the present study.
4.3 Formation temperature estimated by
chlorite geothermometry
In the present study, the temperatures of chlorite for-
mation were estimated using three geothermometers
59
A. Inoue et al.

1626
T (° C ) = − 273
1 (2)
6.542 + log K(1)
3

where K(1) is the equilibrium constant of Equation 1

assuming that aquartz = awater = 1. The activities of chlorite
solid solution components in log K(1) were represented
by the ideal ones (Table 2), assuming the random
mixing of cations and vacancies in the six identical
octahedral sites of chlorite structure as well as the par-
tially ordered mixing of Si and Al in the four tetrahe-
dral sites. It should be kept in mind, however, that
Walshe (1986) added another assumption in his actual
calculations of geothermometer as apyrophyllite-gibbsite =
Xpyrophyllite-gibbsite, where X is the mole fraction of a fictive
pyrophyllite-gibbsite component having a kaolinite
composition. Following Walshe (1986), Mn was
regarded as equivalent to Mg through the present
study.
Vidal et al. (2001) proposed a thermodynamic model
for Fe-Mg partitioning of aluminous trioctahedral
chlorites (Si < 3 p.f.u.) applicable to a wide range of T
(100–600°C) and P (1–25 kbs) conditions by calibrating
data from phase equilibrium experiments and natural
mineral assemblages. Using the calibrated thermody-
namic properties, they estimated the formation tem-
peratures of the chlorite + quartz assemblage that is
expressed by the reaction (Eqn 3):

2Mg 5 AlSi 3 AlO10 ( OH )8 + 3Mg 2 Al 3 Si 3 AlO10 ( OH )8

= 4Mg 4 Al 2Si 2 Al 2 O10 ( OH )8 + 7SiO 2 + 4H 2 O ( l )
(3)

In the Vidal’s model, the ideal activities of the end-

member components in chlorite solid solution are
based on the ordered site occupation (Table 2). From
the regression analysis of the estimated temperatures
of low-temperature (T) chlorite (<480°C) listed up in
Fig. 5 X-ray powder diffraction patterns of some chlorite Vidal et al. (2001), neglecting the contribution of non-
samples examined by X-ray photoelectron spectros-
ideal part in the equilibrium constant K(3), Inoue et al.
copy, except for sample TH5-696. The data of sample
TH5-696 were recorded using the material prior to (2009) gave an approximate equation for the Vidal’s
purification. chl: chlorite, ill: illite, qtz: quartz, pl: pla- geothermometer as follows:
gioclase, cal: calcite.
1
T (° C ) = − 273
0.00184 − 1.113 × 10 −4 x + 3.407 × 10 −6 x 2
developed by Walshe (1986), Vidal et al. (2001), (4)
and Inoue et al. (2009). Walshe (1986) proposed a geo- where
thermometer (Eqn 2) for the reaction (Eqn 1) as
follows: x = log K(′3) = 4 log acrdp
ideal
− 2 log aideal
clin
− 3 log aideal
sud (5)

6Mg 5 AlSi 3 AlO10 ( OH )8 + 14SiO 2 + 8H 2 O ( l ) K’(3) is the ideal part of equilibrium constant for
= 5Mg 6Si 4 O10 ( OH )8 + 3Al 4 2 Si 4 O10 ( OH )8
(1)
Equation 3, assuming that aquartz = awater = 1. The

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60 Journal compilation © 2010 The Society of Resource Geology

Fig. 6 X-ray powder diffraction pat-
terns of chlorites showed the
polytype structure. The data of
sample TH5-696 were recorded
using the material prior to purifi-
cation. The numerical values indi-
cate the hkl index and the dhkl
value. qz: quartz, ill: illite, py:
pyrite or marcasite.
abbreviations of Equation 5, crdp, clin, and sud denote
corundophilite with an amesite composition, cli-
nochlore, and sudoite components, respectively. On
the other hand, it is known that low-T chlorites have
higher Si contents and octahedral vacancies and lower
Fe + Mg contents even in rocks of similar Al2O3 content
compared to higher-grade metamorphic chlorites
(e.g. Hillier & Velde, 1991). Thus, Inoue et al. (2009)
replaced the end-member component of chlorite solid
solution from clinochlore adopted by Vidal et al. (2001)
to Al-free chlorite (Afch) with a serpentine composition
so that the chosen end-member components of solid
solution are more suitable for describing the wide
range of elemental substitutions in low-T chlorites.
Finally, Inoue et al. (2009) proposed the following new
geothermometer;
1 temperatures of chlorites in Toyoha geothermal system
T (° C ) =
0.00293 − 5.13 × 10 −4 x + 3.904 × 10 −5 x 2
rdp − 3log asud − log aAfch
x = log K(7 ) = 3 log acideal ideal ideal
for the reaction:
3Mg 2 Al 3 Si 3 AlO10 ( OH )8 + Mg 6 Si 4 O10 ( OH )8
= 3Mg 4 Al 2Si 2 Al 2 O10 ( OH )8 + 7SiO 2 + 4H 2 O ( l )
Here the random mixing of cations and vacancies in
the six octahedral sites of chlorite solid solution is
© 2010 The Authors
Journal compilation © 2010 The Society of Resource Geology
Application of chlorite geothermometry
assumed, which is similar to Walshe (1986), as given in
Table 2. It is also assumed aquartz = awater = 1.
Inoue et al. (2009) demonstrated that neglecting the
presence of ferric iron in chlorite causes a serious error
for the estimation of the formation temperatures of
chlorites from rocks of diagenetic-hydrothermal series.
This was the same case for the Toyoha chlorites what-
ever the geothermometer used, and thus we used the
structure formulas of chlorites recalculated on the
basis of the Fe3+ contents by XPS determination. As the
result, the estimated temperatures of chlorite forma-
tion are summarized in Figure 9 on the basis of classi-
fication of the propylitic zone, the ore mineralized
zone from drill cores, and the mineralized zone from
the Toyoha deposit, using three geothermometers of
Equations 2, 4, and 6. It is seen from the figure that we
obtain apparently reasonable values for the formation
− 273
whatever the geothermometer used, if the structure
formulas corrected in regard to the ferric iron contents
(6) were used in the temperature estimation. Neverthe-
less, closer comparison of the figure indicates that the
Walshe’s geothermometer provides the lowest esti-
mates of formation temperatures, the Vidal’s is the
(7)
highest ones, and the temperature estimation by our
geothermometer is an intermediate. We use the data
estimated by our geothermometer in the subsequent
discussion.
61
A. Inoue et al.

Fig. 7 Results of constrained least squares fitting of the Fe 3p spectra of X-ray photoelectron spectroscopy for Toyoha
chlorites from the propylitic zone. Crosses: measured data for total Fe (SFe), thin solid curves: curves fitted for the SFe and
Shirley base lines, thick solid curves: curves fitted for Fe2+ (lower binding energy side) and Fe3+ (higher binding energy
side), respectively.

4.4 Relationship between the formation
temperature and composition of chlorite
Figure 10 shows the distribution of formation tempera-
ture estimated by Equation 6 for chlorites from the pro-
pylite zone, the ore mineralized zone in drill cores, and
the mineralized zone in Toyoha deposit. The data are
grouped for convenience into three types on the basis
of different ranks in the Fe + Mn contents. Chlorites in
the propylitic zone have relatively low Fe + Mn con-
tents (Fig. 4) and the formation temperatures concen-
trate in the range from 150 to 300°C (Fig. 10). The range
of formation temperatures coincides with those
reported previously from active geothermal fields (e.g.
Browne, 1978; Henley & Ellis, 1983; Inoue, 1995). Com-
positional variation in epidote coexisting with chlorite
from the propylitic zone in Toyoha is plotted in
Figure 11. Similar to Shikazono (1984), the Fe3+ con-
tents in epidote seem to vary with the bulk rock com-
position of original rocks: high in Fe3+ for basic rocks
with basaltic to andesitic compositions and low in Fe3+
for silicic rocks involving sandstones, tuffs, and quartz
diorite. In contrast, the Mg/(Mg + Fe2+) ratios in chlo-
rites are controlled rather by temperature (Fig. 12). The

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62 Journal compilation © 2010 The Society of Resource Geology
 Application of chlorite geothermometry

Fig. 8 Results of constrained least squares fitting of the

Fe 3p spectra of X-ray photoelectron spectroscopy
for Toyoha chlorites from the ore mineralized zone.
Crosses: measured data for total Fe (SFe), thin solid
curves: curves fitted for the SFe and Shirley base lines,
thick solid curves: curves fitted for Fe2+ (lower binding
energy side) and Fe3+ (higher binding energy side),
respectively.

ratios of chlorites without epidote and actinolite vary

broadly, probably reflecting varied compositions of
original rocks, but those of chlorites with epidote
and/or actinolite tend to concentrate within a
restricted composition regardless of different bulk rock
compositions.
Chlorites from the ore mineralized zone of drill
cores (TH-2, TH-4, and TH-6) have higher Fe + Mn
contents compared to those from the propylitic zone
(Fig. 4). But the modal value of the formation tem-
perature is similar, around 230°C, between chlorites
from the two zones (Fig. 10), although there is a ten-
dency that chlorites from the ore mineralized zone of
drill cores exhibit slightly broad distribution of the
formation temperatures compared to those of propy-
litic zone. It suggests that the high Fe + Mn contents
in chlorites from the ore mineralized zone of drill
cores were originated from the differences in fluid
composition prevailed at the formation rather than
the factor of temperature, because both Fe and Mn are
partitioned preferentially into chlorite relative to Mg
with decreasing temperature (Sverjensky, 1985). On
the other hand, the estimated temperatures of chlorite
formation in the ore veins of Toyoha deposit show a
clear tendency to shift toward higher temperature
side; they range from 180°C to 350°C and the mode is
around 300°C (Fig. 10). The data used in the calcula-
tions contain those of chlorites from Tajima, Soya, and
Izumo veins, together with Hole no. 70 (drilled near
the River Kurumisawa), of which compositions were
cited from Sawai (2006). Assuming that Fe3+/SFe =
0.15 for the chlorites analysed by Sawai (2006), the
estimated formation temperatures resulted in 338°C
for the Tajima vein, 280°C for the Soya vein, 278°C for
the Izumo vein, and 356°C for no. 70 on average. It
has been reported that the homogenization tempera-
tures of fluid inclusions in quartz and sphalerite from
the Toyoha deposit range from 150–250°C for the
early veins (which include the Tajima vein) and from
200–300°C for the later veins (which include the Soya
and Izumo veins) (e.g. Enjoji, 1972; Yajima & Ohta,
1979; Kanbara et al., 1989; Sanga et al., 1992; Masuta

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Journal compilation © 2010 The Society of Resource Geology 63
64
A. Inoue et al.

Table 1 Chlorite compositions determined by EDS and XPS and the formation temperatures

Samples Propylitic zone Ore mineralized zone

TH-2-964 TH-2-1272 TH-5-696 902701 TH-2-509 TH-2-894 TH-6-833
SiO2 29.98 28.08 27.34 28.98 24.26 27.17 22.86
Al2O3 15.56 18.34 18.58 19.05 17.64 18.77 17.55
TiO2 0.00 0.07 0.03 0.04 0.01 0.05 0.03
FeO 16.45 13.82 16.42 11.26 33.82 19.37 30.55
Fe2O3 6.36 3.80 4.51 3.91 5.56 3.76 6.40
MgO 16.68 19.08 17.75 20.30 1.37 13.71 1.92
MnO 0.40 1.12 0.35 0.60 3.34 3.21 2.15
CaO 0.17 0.16 0.04 0.13 0.08 0.06 0.07
Na2O 0.00 0.13 0.16 0.04 0.00 0.08 0.01
K2O 0.16 0.02 0.07 0.12 0.03 0.10 0.05
Total 85.75 84.60 85.24 84.45 86.09 86.29 81.59
Fe3+/SFe by XPS 0.26 0.20 0.20 0.24 0.13 0.17 0.16
Structure formula on the basis of O = 14
Si 3.15 2.92 2.86 2.96 2.85 2.89 2.80
Al 0.85 1.08 1.14 1.04 1.15 1.11 1.20
STetrahedral cations 4.00 4.00 4.00 4.00 4.00 4.00 4.00
Al 1.08 1.17 1.16 1.26 1.28 1.24 1.33
Fe3+ 0.50 0.30 0.36 0.30 0.49 0.30 0.59
Fe2+ 1.44 1.20 1.43 0.96 3.31 1.72 3.11
Mg 2.61 2.96 2.77 3.09 0.24 2.17 0.35
Mn 0.04 0.10 0.03 0.05 0.33 0.29 0.22
SOctahedral cations 5.67 5.73 5.75 5.66 5.65 5.72 5.60
Numbers of vacant 0.33 0.27 0.25 0.34 0.35 0.28 0.40
Temperature (oC) by Equation 6 159 236 264 196 221 240 220
Original rock Andesite Sandstone Sandstone Sandstone Tuff Basalt Tuff
Associated minerals Qtz, Pl, Cal, Qtz, Pl, Ep, Qtz, Pl, Ep, Qtz, Ill, Qtz, Sphal, Qtz, Ill, Cal, Qtz, Py,
Sphene Ill, Cal Ill, Cal Smt, Py Py Sphal, Chalco Sphal, Ill

Cal, calcite; Chalco, chalcopyrite, Ep, epidote; Ill, illite; Pl, plagioclase; Py, pyrite; Qtz, quartz; Smt, smectite; Sphal, sphalerite.

© 2010 The Authors

Journal compilation © 2010 The Society of Resource Geology
 Application of chlorite geothermometry

Table 2 Three models for ideal activities of chlorite solid solution components used in the calculations of geothermometry
Walshe (1986) model
Component (abbreviation)
C1: Al-free chlorite (Afch)
C2: Clinochlore (Clin)
C3: Chamosite (Chm)
C4: Pyrophyllite-gibbsite (Pyp)
Vidal et al. (2001) model
Component
C1: Clinochore (Clin)
C2: Chamosite (Chm)
C3: Sudoite (Sud)
C4: Corundophilite (Crdp)
Inoue et al., (2009) model
Component
C1: Al-free chlorite (Afch)
C2: Corundophilite (Crdp)
C3: Chamosite (Chm)
C4: Sudoite (Sud)
Chemical formula (half formula unit)
[Mg6][Si4]O10(OH)8
[Mg5Al][Si3Al]O10(OH)8
[Fe2+5Al][Si3Al]O10(OH)8
[Al4䊐2][Si4]O10(OH)8
Chemical formula (half formula unit)
[Mg5Al][Si3Al]O10(OH)8
[Fe2+5Al][Si3Al]O10(OH)8
[Mg2Al3䊐][Si3Al]O10(OH)8
[Mg4Al2][Si2Al2]O10(OH)8
Chemical formula (half formula unit)
[Mg6][Si4]O10(OH)8
[Mg4Al2][Si2Al2]O10(OH)8
[Fe2+5Al][Si3Al]O10(OH)8
[Mg2Al3䊐][Si3Al]O10(OH)8
Ideal activity
a1 = k1(XMg, oct)6(XSi, tet)2
a2 = k2(XMg, oct)5(XAl, oct)(XSi, tet)(XAl, tet)
a3 = k3(XFe, oct)5(XAl, oct)(XSi, tet)(XAl, tet)
a4 = X4
where k1 = 1; k2 = 59.720 = k3; X4 is the mole
fraction of C4.
Ideal activity
a1 = k1(XMg, M1)(XMg, M2+M3)4(XSi, T2)(XAl,T2)
a2 = k2(XFe, M1)(XFe, M2+M3)4(XSi, T2)(XAl, T2)
a3 = k3(X䊐, M1)(XAl, M2+M3)2(XMg, M2+M3)2(XSi, T2)(XAl, T2)
a4 = k4(XAl, M1)(XMg, M2+M3)4(XAl, T2)2
where k1 = 4 = k2; k3 = 64; k4 = 1
Ideal activity
same as a1 of Walshe (1986) model
a2 = k2(XMg, oct)4(XAl, oct)2(XAl, tet)2
same as a3 of Walshe (1986) model
a4 = k4(XMg, oct)2(XAl, oct)3(X䊐, oct)(XSi, tet)(XAl, tet)
where k2 = 45.563; k4 = 1728

Note: Xj, s is the mole fraction of the j cation on the s site and ki is a normalization factor.

Fig. 9 Comparison of temperatures of chlorite formation estimated by three geothermometers, Equations 2, 4, and 6. (a)
Chlorites from the propylitic zone, assumed Fe3+/SFe = 0.23 (b) Chlorites from the ore mineralized zone and Toyoha veins,
assumed Fe3+/SFe = 0.15.

et al., 1996). The formation temperatures estimated
by chlorite geothermometry seem to be a little bit
high compared to the homogenization temperatures
of fluid inclusions, though there is the uncertainty
of Fe3+/SFe ratio assumed in the present study.
Despite the differences between chlorite formation
temperatures and homogenization temperatures of
fluid inclusions, it is likely from Figure 10 that gangue
chlorites associated with sulfide minerals in the
Toyoha deposit formed at higher temperatures than
those in the marginal ore mineralized zone observed
through drill cores.

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Journal compilation © 2010 The Society of Resource Geology 65
A. Inoue et al.
Fig. 10 Comparison of the formation temperatures of
chlorites from three zones, calculated using the geo-
thermometer of Equation 6 in the text. The data were
ranked following the Fe + Mn contents in chlorites.
4.5 Relation between formation temperature
and bore hole temperature
Figure 13 is a diagram showing the relationship
between the formation temperatures of chlorites and
the present subsurface temperatures observed through
four drill holes, together with the homogenization tem-
66
Fig. 11 Distribution of Fe3+/(Fe3+ + Al) in epidote coex-
isting with chlorite in different original rocks.
Fig. 12 Epidote projection of chlorite and actinolite com-
positions from the propylitic zone of Toyoha geother-
mal field. AF* is (Al2O3 + Fe2O3 - Na2O - 0.75CaO) for
the common assemblage of chlorite, albite, and quartz,
with or without epidote and actinolite. The Mg/(Mg +
Fe) ratios for chlorite and actinolite were calculated
assuming that Fe3+/SFe = 0.23 as determined by the
present XPS measurements.
peratures of fluid inclusions in quartz, calcite, anhy-
drite, sphalerite, and fluorite, reported by NEDO
(1988). TH-2 and TH-4 contain the ore mineralized
zone, and TH-3 and TH-7 consist mainly of the propy-
litic zone (Fig. 3). In the three holes of TH-2, TH-4, and
TH-7, the estimated temperatures of chlorite formation
© 2010 The Authors
Journal compilation © 2010 The Society of Resource Geology
 Temperature ( ) Temperature ( ) Temperature ( )
Temperature ( )

© 2010 The Authors

100 200 300 400 100 200 300 400 100 200 300 400 100 200 300 400
0 0 0 0
Motoyama F.
Motoyama F. Shiramizugawa F.
TH-4 TH-3
Koyanagisawa F.

Epidote in

500 500 500 500

Usubetsu F.

Koyanagisawa F.
Epidote in

Koyanagisawa F.
Epidote in
Actinolite in

Depth (m)
Depth (m)

Depth (m)
Depth (m)

Journal compilation © 2010 The Society of Resource Geology

Actinolite in
Shiramizugawa F.

1000 1000 Actinolite in 1000

Shiramizugawa F.
1000

Qtz Diorite

Shiramizugawa F.
Usubetsu F.
TH-7

Usubetsu F.
Qtz Diorite
1500 1500 Legend
TH-2
Quartz Fluorite

Anhydrite Sphalerite

Calcite Rhodochrosite

Fig. 13 Comparison of the estimated formation temperatures of chlorites, the present bore hole temperatures (solid curves) and homogenization temperatures
of fluid inclusions measured by NEDO (1988). Dashed curves stand for the boiling point curves of pure water. Solid and open circles indicate the mean values
for chlorites from the ore mineralized zone and the propylitic zone, respectively. Bars denote the range of estimated temperatures.

67
Application of chlorite geothermometry
A. Inoue et al.
are close to the homogenization temperatures of fluid
inclusions, though there are some exceptions. The dis-
crepancy of the two data seems to be conspicuous near
the location at which the boiling of fluid occurred, for
instance, around 300 m depth of TH-2. Additionally,
the homogenization temperatures of fluid inclusions
are consistent with the present subsurface tempera-
tures observed in TH-2 and TH-4. It is assured that
chlorites observed in the two drill holes formed under
physicochemical conditions close to the present ones.
In TH-7, the formation temperatures of chlorites are
consistent with the homogenization temperatures of
fluid inclusions but both are inconsistent with the
present subsurface temperatures. It implies that the
fluid inclusions were trapped in minerals at the same
stage as that of chlorite formation, i.e. the propylitic
alteration stage. In contrast, the three temperatures
plotted in Figure 13 are inconsistent with one another
in TH-3, indicating that chlorite formed at earliest stage
of propylitization, then hydrothermal fluids with
lower temperatures circulated through the propyli-
tized rocks, and TH-3 has been cooled down at present
by incursion of cold waters. If this is the case, chemical
composition of chlorite early formed at relatively
higher temperatures was not modified so strongly by
superposition of later low-T hydrothermal activities.
5. Concluding remarks
In this study, chemical geothermometry was applied to
the estimation of temperatures for chlorite formation
which occurred in the Toyoha geothermal system,
where a polymetallic epithermal vein-type ore deposit
is contained. As well as in our previous study (Inoue
et al., 2009), it was found that the independent determi-
nation of ferric iron contents is indispensable to esti-
mate correctly the temperatures of chlorite formation.
The Fe3+/SFe ratios determined by XPS ranged from
0.20 to 0.26 and 0.23 on average for chlorites from the
propylitic alteration zone and from 0.13 to 0.17 and 0.15
on average for chlorites from the ore mineralized zones
associated with sulfide minerals. These ratios are inter-
estingly similar to those of diagenetic Fe-rich chlorites
(0.22–0.34) of Niger, propylitic chlorites (0.16–0.32) of
Saint Martin, and chlorites associated with pyrite
(0.14–0.24) of Rouez, Massif Armorican that were
determined by Mössbauer spectroscopy (Inoue et al.,
2009).
Assuming the average value of Fe3+/SFe for chlorites
from the propylitic and ore mineralized zones at
Toyoha, the formation temperatures of chlorites were
68
estimated to be within the range of 150–300°C for the
two zones. In the propylitic alteration, the composition
of chlorite varied with different bulk rock compositions
of original rocks if the chlorites did not coexist with
other Fe-bearing minerals. However, the composition
of chlorite coexisting with epidote and/or actinolite
was restricted within a narrow range of Mg/Fe2++Mg
ratio whatever the bulk rock composition. Chlorites
from both the ore mineralized zones of Toyoha deposit
and the contiguous drill cores are characterized by the
high Fe and Mn contents, associated with abundant
sulfide minerals and rhodochrosite. Despite the similar
compositional characteristics, the formation tempera-
tures estimated were slightly higher (180–350°C) for
chlorites from the ore deposit than those (150–300°C)
from the contiguous drill cores. In addition, compari-
son between the temperatures of chlorite formation,
the observed subsurface temperatures, and the mea-
sured homogenization temperatures of fluid inclusions
through the drill holes examined provided insight into
understanding the complicated history of hydrother-
mal activities for the latest 10 My that contains the
activities of polymetallic ore mineralization in the
Toyoha deposit.
Acknowledgments
We thank Minoru Utada for providing the core samples
used in the present study. Kiyoko Nemoto kindly
helped us with X-ray photoelectron spectroscopy.
Reviews by Olivier Vidal and Osao Sawai led to sub-
stantial improvements in this paper.
This work was partly supported by the Science Grant
of the Ministry of Education, Science, and Culture.
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