Bull. Natl. Mus. Nat. Sci., Ser. C, 35, pp.

11–18, December 22, 2009

Chloritized granitic rock in the Nagato Tectonic Zone, southwest Japan:

an example of a static metasomatic rock in the serpentinite mélange zone

Kazumi Yokoyama1, Atsushi Goto2 and Yukiyasu Tsutsumi1

1
Department of Geology, National Museum of Nature and Science,
3–23–1, Hyakunin, Shinjuku, Tokyo, 169–0073, Japan
E-mail: [email protected] and [email protected]
2
Petrology Course, School of Science, University of Hyogo (Branch of Himeji Institute of Technology),
2167, Shosha Himeji, Hyogo 671–2201, Japan
E-mail: [email protected]

Abstrast Chloritized granitic rock occurs in the serpentinite mélange of the Nagato Tectonic
Zone, southwest Japan. The rock occurs as a small block of ca. 1m in diameter in the sheared ser-
pentinite matrix and is difficult to distinguish from massive serpentinite. It consists mostly of chlo-
rite with basal spacing of 14ÅEand FeO content <0.3 wt. %. It is homogeneous under a micro-
scope with plane-polarized light. Twinnings with Carlsbad and polysynthetic textures are remark-
able under crossed polars, suggesting that pseudomorphs were parentally K-feldspar and plagio-
clase, respectively. Rare relict minerals are apatite and biotite. Grain sizes of pseudomorphs after
feldspars and quartz are similar to those in normal granitic rock. The relict minerals and grain
sizes suggest that they were replaced almost totally by FeO-free chlorite from a granitic rock.
Although quartz and feldspar were well preserved in a large granitic and gneissose blocks from
the serpentinite mélange, replacement by FeO-free chlorite is observed along the twin plane of pla-
gioclase in the rocks. Preservation of twinning texture in the chloritized granite implies that the
metasomatism took place under static conditions without deformation.
Key words : Nagato Tectonic Zone, serpentinite mélange, Chloritization, Granite, Pseudomorph

metasomatic process occurs when a single miner-

Introduction
al is replaced as in carbonatization (Nakamura
The chemical composition of a rock often and Kato, 2004) and sericitization of volcanic
changes radically during low-grade metamor- rock and serpentinization of peridotite. Chloriti-
phism or hydrothermal alternation. Rocks having zations of volcanic rocks are also reported from
undergone such changes are known as metaso- altered igneous rocks (Greenough, 1985). In the
matic rocks. A metasomatic rock usually has no serpentinization of peridotite, chemical composi-
source rock corresponding in chemistry. Howev- tion is not so severely altered, but it also belongs
er, we can sometimes identify their original rocks to one of the metasomatic rocks.
by macroscopic to microscopic textures. For ex- In the metasomatic rocks, the outer shapes of
ample, a silicified wood and pyritized fossil can phenocrysts or porphyroblasts are occasionally
change their chemical compositions completely observed as pseudomorphs. As far as we know,
while still retaining wood and fossil structures however, the preservation of a clear twin texture
(e.g. Akahane et al., 1999; Briggs et al., 1996). has not been reported in the metasomatic rocks.
In such cases, the original rock will not be identi- In this paper, we present chloritization of excep-
fied by chemical analyses but by macroscopic tionally preserved twinning texture including
and microscopic observations. In many cases, the outer shapes, clearly showing that the rock was
metasomatic processes take place under static derived from a granitic rock.
conditions, namely, deformation-free. Another
12 Kazumi Yokoyama, Atsushi Goto and Yukiyasu Tsutsumi

massif has been described as a blackwall (e.g.

Nagato Tectonic Zone
Frost, 1975; Leach and Rodgers, 1978). Since
The Nagato Tectonic Zone crops out intermit- minerals in large blocks in the serpentinite
tently as a narrow belt with an extension of about mélange are well preserved, their ages were ob-
35 km with a maximum width of 2 km, trending tained by various methods. Kawano et al. (1966)
from NNE to SSW in western end of the reported the K-Ar age, 424 Ma, of muscovite in a
Chugoku district, southwest Japan (Fig. 1). The gneiss enclosed in the sheared serpentinite at the
zone is in fault contact with the post-Triassic for- Dai district. Hornblende age in amphibolite in
mations and the Mine Formation of Triassic age the same area was obtained as 373 Ma by K-Ar
and upper Paleozoic formations. It is uncon- method (Shibata and Murakami, 1975). Mus-
formably overlain partly by the Toyoura Forma- covite in a granitic rock from the Nishiichi dis-
tion of Jurassic age and the Kanmon Group of trict was 371 Ma (Murakami et al., 1977). Shiba-
Cretaceous age. From south to north, the main ta and Nishimura (1989) reported a Rb-Sr mus-
localities of the zone are the Toyogatake district, covite-whole rock age of 303 Ma for the Sangun
the Nishiichi district, the Dai district and the pelitic schist in the Toyogatake district.
Misumi district (Murakami and Nishimura,
1979).
Petrography of the Chloritized Rock
The main rock types of the Nagato Tectonic
Zone are the Sangun metamorphic rocks, upper The chlorite rock was found as a block in a
Paleozoic formations (unidentified age to Permi- small serpentinite quarry of about 30 meters
an), serpentinite and amphibolite (Murakami and across in the Dai district (Fig. 1). The block is
Nishimura, 1979). The serpentinite is highly about 1 meter in diameter and has been left on
sheared and includes various types of blocks the sheared serpentinite. The rock is faintly dark
such as orthogneiss, gabbro, granodiorite, trond- green and more transparent than the surrounding
hjemite and diabase. The blocks are mostly more serpentinite. The block is composed almost
than several meters in diameter and preserve the wholly of colorless chlorite and is traversed by
original minerals and texture. Chlorite rocks de- veins consisting of serpentine and/or chlorite.
velop at the boundaries between serpentinite and Under a microscope with plane-polarized
blocks. Such a chlorite rock from the serpentinite light, the rock is homogeneous locally with dusty

Fig. 1. Geological sketch map of the Nagato Tectonic Zone. (after Murakami and Nishimura, 1979) a and b:
outcrops of the Nagato Tectonic Zone, c: sample locality of the chlorite rock in the Dai District.
 Chloritized granitic rock in the Nagato Tectonic Zone, southwest Japan 13

Fig. 2. Microphotographs of chloritized rock in thin section. A and B; chlorite showing twinning textures under
plane-polarized light and crossed polar, respectively. C and D: ibid. E; chlorite rock with twinning texture
under crossed polar. F: concentration map of Ca in the same area as photo E. Abbreviations, p-qz: pseudo-
morph after quartz, p-pl: pseudomorph after plagioclase with polysynthetic twin, p-Kf: pseudomorph after
K-feldspar with Carsbad twin, an:ankerite or dolomite, ser:serpentine.
14 Kazumi Yokoyama, Atsushi Goto and Yukiyasu Tsutsumi

parts (Fig. 2 A and C). Under the microscope gate without any twinning texture (Fig. 2) should
with crossed polars, the granitic texture appears correspond to quartz. As rare minerals, apatite,
(Fig. 2 B, D and E). Textures of polysynthetic biotite, pyrophanite, ankerite and zircon were
and Carlsbad twins are remarkably well pre- also found. Biotite with size around 0.1 mm is
served in the rock. In normal granitic rocks, found in the chlorite matrix (Fig. 3A). It is sur-
polysynthetic twinning is common and represen- rounded by chlorite with a greenish color. Green-
tative in plagioclase, whereas Carlsbad twinning ish chlorite without a biotite core sometimes oc-
is prevalent in monoclinic K-feldspar (ortho- curs in the colorless chlorite matrix. The grain
clase). Hence, it is reasonable to assume simply size of greenish chlorite is around 1 mm in
at first that the pseudomorph with polysynthetic length. Apatite is found as anhedral grains of 0.2
twinning corresponds to that of plagioclase, mm diameter. Pyrophanite, MnTiO3, occurs as an
whereas the pseudomorph with Carlsbad twin- aggregate and apparently forms a pseudomorph
ning to that of K-feldspar. Grain sizes of the probably of ilmenite (Fig. 3C). Carbonate miner-
pseudomorphs are 0.5–2 mm, similar to those in als, dolomite and ankerite, are fine-grained and
granitic rocks. If the parental rock for the chlorite form an aggregate. They appear like opaque min-
rock was a granitic rock, cryptocrystalline aggre- erals under plane-polarized light. Zircons usually

Fig. 3. Back-scattered electron image of minerals in Fe-free chlorite matrix. A: relict biotite (bio) surrounded
by Fe-rich greenish chlorite. B: relict apatite. C: aggregate of pyrophanite showing pseudomorph after il-
menite. D; various types of zircon grains concentrated in a part.
 Chloritized granitic rock in the Nagato Tectonic Zone, southwest Japan 15

Fig. 4. Partly chloritized plagioclase in a large granitic block occurring in a sheared serpentinite. A: micropho-
tograph of plagioclase with polysynthetic twin (crossed polars). B: concentration of Mg showing crystalliza-
tion of chlorite (white) along twin planes and fractures.

occur as fine-grained crystallites up to ca. and Science. The analytical conditions were
100 m m in length (Fig. 3D). They vary in shape; 15 kV and a current of 20 nA with a beam diame-
acicular, euhedral and fragmented, and are con- ter of about 2 mm. The following synthetic and
centrated in a part (Fig. 4). Zoning and heteroge- natural materials were used as standards: wollas-
neous patterns are not observed in the BSE tonite for Si and Ca, anatase for Ti, corundum for
image of zircon. Monazite rarely occurs forming Al, Mg2SiO4 for Mg, Fe2SiO4 for Fe, rhodonite
an aggregate. for Mn, albite for Na and adularia for K. Chemi-
The microscopical features and minerals clear- cal compositions of chlorite and other representa-
ly show that the protolith of the chlorite rock was tive minerals are listed in Table 1.
evidently a granitic rock and was transformed Chlorite is confirmed to have a basal spacing
into a monomineralic rock by a metasomatic of 14 Å by X-ray diffractometry. It is almost Fe-
process. The chlorite rock seems to have been free with less than 0.3 wt% as FeO content. The
protected from any deformation after chlorite Al2O3 content is mostly around 10 wt%, very low
crystallization, suggesting that the original as a chlorite composition reported (Deer et al.,
granitic rock was metasomatized statically. As 1962). Although the CaO content in normal chlo-
shown in the map in Fig. 1, there are many tec- rite should be usually negligible, it is recogniz-
tonic blocks larger than several meters across. able at around 0.15 wt% in a quartz pseudo-
Chlorite formation occurs at the boundary be- morph, whereas around 0.1 wt% in plagioclase
tween the block and serpentinite, but the original and K-feldspar pseudomorphs are present (Table
minerals are more or less preserved in these large 1). Mapping of the rock by Ca shows that the
blocks. At a marginal part of a granitic block, re- plagioclase pseudomorph is clearly poorer in
placement of plagioclase by chlorite was ob- CaO content than that of the quartz pseudomorph
served (Fig. 4). The replacement occurs along the (Fig. 2 F). Al2O3 content is slightly higher in the
twin plane and fractures. It is probable that quartz pseudomorph than that in feldspar (Fig.
preservation of twin textures in the chlorite rock 4). Chlorite around biotite differs in chemical
was due to the replacement by chlorite progress- composition from the Fe-free chlorite mentioned
ing in each twin plane. above. It is usually Fe-rich and varies in FeO con-
tent up to 19 wt%. The Al2O3 content is also up
to 19 wt%. Biotite is a less resistant mineral
Chemical Comppositions of Minerals
against alteration of granite (e.g. Wilamowski,
The chemical compositions of minerals were 2002). The chlorite around biotite is negligible in
analyzed by electron microprobe analyzer, JEOL CaO content (0.03 wt%), similar in composi-
8800, located in the National Museum of Nature tion to those around altered biotite in a granitic
16 Kazumi Yokoyama, Atsushi Goto and Yukiyasu Tsutsumi

Table 1. Chemical composition of various chlorites and other representative minerals. P-mineral: pseudomorph
after the mineral.

Mineral chlorite chlorite chlorite chlorite biotite chlorite pyrophanite

Texture pseudomorph pseudomorph pseudomorph vein relict pseudomorph pseudomorph
(Pseudomorph) (quartz) (plagioclase) (K-feldspar) - - (biotite) (ilmenite)

wt% 1s wt% 1s wt% 1s wt% 1s– wt% 1s wt% 1s wt% 1s

SiO2 37.65 0.64 38.27 1.02 38.09 1.17 37.21 0.88 39.53 0.42 33.47 2.77
Al2O3 10.80 0.43 9.86 1.46 9.86 1.10 11.12 0.71 12.53 0.25 11.96 4.30
TiO2 1.51 0.20 0.41 0.24 54.53 0.66
FeO 0.11 0.03 0.25 0.11 0.20 0.04 0.15 0.04 14.72 0.86 10.59 4.66 0.10
MnO 0.08 0.02 0.09 0.02 0.07 0.02 0.10 0.03 0.18 0.08 0.25 0.07 45.60 0.47
MgO 38.86 0.32 39.28 0.68 39.31 0.63 38.93 0.50 17.36 0.79 31.32 5.48
CaO 0.15 0.04 0.10 0.02 0.09 0.03 0.14 0.03
K2O 9.90 0.35 0.03 0.02 9.90 0.35
Total 87.66 0.67 87.88 0.76 87.68 0.84 87.68 0.81 95.73 0.83 88.03 0.76 100.13 0.71

ence of relict minerals indicate that the rock in

the serpentinite mélange was originally a granitic
rock. Chloritization of feldspar was described
from altered sandstones through SEM observa-
tion. Pervasive replacement of detrital feldspar
by chlorite was confirmed in variously replaced
feldspar (Marad and Aldaham, 1987). The au-
thors concluded that the replacement is due to
Fig. 5. Diagram showing compositional variation dissolution of feldspar.
of CaO and Al2O3 contents of chlorites in The microscopic observation of chloritization
pseudomorphs after quartz and feldspar and in
vein.
of feldspar reported here is unusual in that al-
most complete preservation of the twinning tex-
ture of igneous feldspar in the chloritized rock
rock. Pyrophanite is almost pure with FeO con- occurs. Most of the original minerals were re-
tent less than 0.1%. This mineral has not been placed by Fe-free and Mg-rich chlorite. Green
found as an igneous stage mineral in granitic Fe-rich chlorite, which was present prior to the
rock. The outer shape of the aggregate suggests Mg-rich chloritization, has not been replaced.
that it was replaced from ilmenite. Furthermore, biotite, partly replaced by greenish
chlorite, also survived at the time of Mg-rich
chloritization. Apatite will be preserved as a min-
Discussion
eral of the igneous stage. There is a transfer of
Replacement of a rock by a single species of elements from the original rock to the outer side:
mineral is not uncommon, well-known examples removal of Na, Si, K and Fe to the outside,
are: silicification, pyritization, carbonatization, whereas addition of Mg from the outer side. As
sericitization, serpentinization and chloritization. the rock is enclosed in the serpentinite, there is
In most of the cases, metasomatic replacement abundant Mg to supply to the original granitic
has been explained as interaction between rock rocks as discussed in a chlorite rock, blackwall,
and seawater and/or hot water, but the mecha- occurring at the boundary between serpentinite
nism remained incompletely understood. In the and enclosed block (e.g. Frost, 1975; Leach and
chloritized rock studied here, the petrographical Rodgers, 1978). In spite of the difficulty to find
texture of pseudomorphs with twinning and pres- where the Na and K elements were moved, it is
 Chloritized granitic rock in the Nagato Tectonic Zone, southwest Japan 17

reasonable that transfers of the elements were in- shearing stage. Age analyses of fine-grained zir-
duced by fluids migrating through the serpenti- con and monazite may reveal the timing of the
nite. Although it is also hard to explain the mech- chloritization.
anism, it is clear that the replacement occurred
under static conditions without deformation.
Acknowledgements
Preservations of twinning and partly replaced
plagioclase by chlorite (Fig. 2 and 4) show that The authors are very grateful to Ms. M. Shi-
the replacement started from the twin plane in geoka for her help with chemical analyses
spite of the differences of crystal structure. Chlo- throughout this study.
rite and serpentine veins developed in the chlori-
tized blocks. Although timing of vein is clearly
References
later than the chloritization of granitic rock, it is
hard to discuss the timing of serpenitization Akahane, H., Furuno, T., Miyajima, H., Goto, M., Ota, T.
and/or shearing of the serpentinite blocks. and Yamamoto, S. (1999) Experimental study on wood
silicification in the stream of hot spring water. Estima-
The most unusual observation is the presence tion of rapidity and mechanism of silicification. Jour-
of relict biotite. Biotite is the first mineral re- nal of the Geological Society of Japan, 105, 108–115.
placed by chlorite in an altered granite. As the bi- (in Japanese with English abstract)
otite is surrounded by normal Fe-rich greenish Briggs, G., Raiswell, R., Botrell, S. H., Hatfield, D. and
chlorite, preservation of biotite may imply that Bartels, C. (1996) Controls on the pyritization of ex-
ceptionally preserved fossils: An analysis of the Lower
the biotite was protected by the Fe-rich chlorite
Devonian Hunsruck slate of Germany. American Jour-
during the crystallization of Fe-free chlorite. nal of Science, 296, 633–663
Dubińska et al. (2004) reported zircon crystals Deer, W. A., Howie, R. A. and Zussman, J. (1962) Rock-
in a chlorite rock occurring at the boundary be- forming minerals, vol. 3 Sheet Silicates. Longmans,
tween serpentinite and rodingite. They concluded Green and Co LTD, London.
that the zircons were formed by a metasomatic Dubińska, E., Bylina, P., Kozlowski, A., Dörr, W., Ne-
jbert, K., Schastok, J. and Kulicki, C. (2004) U-Pb dat-
process at around 300ºC during serpentinization. ing of serpentinization: hydrothermal zircon from a
In the chlorite rock studied here, fine-grained zir- metasomatic rocdingite shell (Sudetic ophiolite, SW
cons with acicular, euhedral or fragmented tex- Poland). Chemical Geology, 203, 183–203.
tures are concentrated in a part (Fig. 3D). It sug- Frost, B.R. (1975) Contact metamorphism of serpentinite,
gests that an original zircon grain was fragment- chloritic blackwall at Paddy-Go-Easy pass, central Cas-
cades, Washington. Journal of Petrology, 16, 272–313.
ed and dissolved. The presence of some euhedral
Leach, T.M. and Rodgers, K.A. (1978) Metasomatism in
zircon may show that they were newly formed at the Wairere serpentinite, King Country, New Zealand.
the time of chloritization. Elementary Zr is gen- Mineralogical Magazine, 42, 45–62.
erally considered to be an immobile element. Greenough J. D. and Papezik, V.S. (1985) Chloritization
Dissolved Zr may recrystallize in situ as zircon. and carbonatization of Cambrian volcanic rocks in east-
Ilmenite and monazite are commonly observed in ern Newfoundland and southern New Brunswick,
Canada. Chemical geology, 53, 53–70
granitic rocks. In the chlorite rock, ilmenite Kawano Y., Ueda, Y. and Murakami, N. (1966) K-Ar dat-
(FeTiO3) was replaced by pyrophanite (MnTiO3), ing on the granitic rock from Miner City, Yamaguchi
whereas monazite was recrystallized into a newly Prefecture. The Journal of the Japanese Association of
formed aggregate. A newly formed Ti-phase, py- Mineralogists, Petrologists and Economic Geologists,
rophanite, is in agreement with the observation 56, 183–186. (in Japanese with English abstract)
Morad, S. and Aldahan, A.A. (1987) Diagenetic chloriti-
that the mobility of Ti is very low during serpen-
zation of feldspars in sandstones. Sedimentary
tinization (e.g. Schandl et al., 1989). REEs may Geology, 51, 155–164.
be also immobile elements. So far it is hard to Murakami, N. and Nishimura, Y. (1979) Nagato Tectonic
discuss the age of chloritization; whether it oc- zone. In “The basement of the Japanese Islands” Pro-
curred at the serpentinization stage or before fessor Hiroshi Kano memorial volume. Toko Printting
18 Kazumi Yokoyama, Atsushi Goto and Yukiyasu Tsutsumi

Co. Ltd. Sendai, 153–181 (in Japanese with English ab- Abitibi greenstone belt, Ontario. Canadian Mineralogy,
stract) 57, 579– 591.
Murakami, N., Ueda, Y. and Mikami T. (1977) K-Ar ages Shibata, K. and Murakami, N. (1975) K-Ar age of amphi-
of the granites from Nagato Tectonic Zone and granitic bolite from the Dai area, Nagato Tectonic zone, South-
pebbles in the Traissic Mine Group, and their geologic west Japan. Bulletin of the Geological Survey of Japan,
significance. The Journal of the Japanese Association 26, 421–423. (in Japanese with English abstract)
of Mineralogists, Petrologists and Economic Shibata, K. and Nishimura, Y. (1989) Isotopic ages of the
Geologists, 72, 277–287. (in Japanese with English ab- Sangun crystalline schists, Southwest Japan. The Mem-
stract) oirs of the Geological Society of Japan, 33, 317–341.
Nakamura, K. and Kato, Y. (2004) Carbonatization of (in Japanese with English abstract)
oceanic crust by the seafloor hydrothermal activity and Wilamowski, A. (2002) Chloritization and polytypism of
its significance as a CO2 sink in the Early Archean. biotite in the Lomnica granite, Karkonosze Massif,
Geochimica et Cosmochimica Acta, 68, 4595–4618 Sudetes, Poland: stable isotope evidence. Chemical Ge-
Schandl, E. S., O’Hanley, D. S. and Wicks, F. J. (1989) ology, 182, 529–547
Rodingites in serpentinized ultramafic rocks of the