THE AMERICAN
MINERALOGIST,
VOL. 52, NO\IEMBER-DECEMBER,
1967
ERIONITE, PHILLIPSITE AND GONNARDITE IN THE
AMYGDALES OF ALTERED BASALT FROM MAZE,
NIIGATA PREFECTURE,JAPAN
Kazuo HAnAnA,ChichibuMusewmoJNatural,History,
I{ agator
o, I{ ogami-machi,Chichibugun, Sa'itamaPreJecture,
J apon
AND
Snrcerr lweuoto, KuNrarr Kruana, Geologicaland.Mineralogical Institute, Faculty oJ Science,Tokyo Uniaersity of Educat'ion, Otsuha,Bunkyo-ku, Tokyo, Jopan.
Aesrnacr
Erionite, phillipsite and gonnardite have been found in the amygdales of altered basalt'
Maz6, Niigata Prefecture, Japan. Chemical, physical, optical and X-ray data are provided.
Erionite is hexagonal, P6z/mmc.
IurnooucrtoN
Ofiretite, describedby Gonnard in 1890 (seeDana's System,6th Ed.,
p. 1043),was examinedby Hey and Fejer (1962) who stated that it was
identical to erionite. Bennett and Gard (1967, personal comm.) and the
present writers found at the same time but independently that erionite
and offretite were both valid species.This paper deals with erionite in
some detail together with phillipsite, gonnardite, natrolite and analcime.
There are many descriptions of zeolites and associatedminerals in the
amygdales of thoroughly weathered and altered olivine basalt and in the
andesite exposed along the seashoreof Maz6, in the Iwamure district,
Niigata Prefecture. They include apophyllite (Jimbo, 1907), chabazite
(Shimazu and Kawakau;ri, 1967), analcime (Shimizu, 1915), natrolite,
thomsonite (Mumeikai Group, 1948), heulandite (Harada, Tomita and
Sudo, 1966), iron-rich saponite (Miyamoto, 1957). It is the first discovery of erionite in Japan. One other occurrence of erionite in altered
basalt was describedby Kamb and Oke (1960) with type paulingite.
Zaortrn Assnunr-acBs
The above-mentioned zeolites and associatedminerals in the amygdales of olivine basalt resemble those of the amygdales of the Antrim
basalts reported by Walker (1951, 1959, l96la and l96Ib), although
levyne, gmelinite and scoleciteare absent at Maz6,.
The following zeolitesare often recognizedin zonal zeolite assemblages
in amygdales (1-10 cm. in diameter) in sequencesfrom the outer wall to
central parts, which probably correspond to earlier and later stages of
crystallization:
1785
1786KAZUO IIARADA, SHIGEKI IWAMOTOAND KUNIAKI KIHARA
o ) T h o m s o n i t e( a : 1 . 5 0 7 , B : 1 . 5 2 0 , 7 : 1 . 5 3 1 , ' y - a : 0 . 0 2 4 a n d ( + ) 2 V
:68') and/or gonnardite (a:1.500, 'y:1.504, c:0.004, cAX: Oo)
f o l l o w e db y n a t r o l i t e( o F t . 4 76 , P : 1 . 4 8 6 , t : 1 . 4 8 7 , t - a : 0 . 0 1 3 a n d ( * )
2V:60") followed by analcime (n:1.a87). This sequencemight be
explained by decreasing Cat+ and increasing Na+ in the host solution
during crystallization.
X-ray powder data for gonnardite, which has been misidentified as
natrolite due to the similarity of its X-ray powder pattern, is identical to
that of Meixner, et al. (1956). Chemical compositions and features of
this zeolite assemblagesare shown in Figure 1 and Table 1.
Fro. 1. Zonal arrangements of zeolites in an almond-sharped amygdale of basalt'
Note: L, analcime; N, natrolite and G, gonnardite.
-D)
Heulandite followed by phillipsite followed by natrolite. c) Heulandite
followed by chabazite followed by erionite (Fig. 2). This sequencemay
be explained by the similarity of the crystal structures (Struntz, 1960)
of this type
and chemicalcompositons(Hay, 1964).Mineral assemblages
were describedalso by Hey (1959).rl) Heulandite followed by analcime.
Yellow calcite is abundant throughout the zeolite assemblages,and
qrartz is always absent in the amygdales, as well as in the basalt host
rocks. These zeolite assemblagesare silica-poor species,which may be
indicate that silica activity was notably low (Hay, 1964) during crystalIization.
. fn andesitic rocks, ordinary silica-rich zeolite assemblages,as clinoptilolite-heulandite-mordenite-analcime'assemblages
were observed,sometimes with quartz. Stilbite and laumentite have not been found at Maz6.
1787
ERION ITE, P H I LLI PSI TE A N D GONN A RDITE
Tesln 1. Cnrurcer, An,lrvsps or GoNNAR.DrrE,
NArnoutn, Axelcrur,
EnroNrrl:,lrqD PErLLrpsnB
SiOz
TiOz
AlzOr
FeO*Fe:Oa
MnO
Mgo
42.71
none
46.82
none
27.43
0.14
31.02
0 .1 6
none
none
5.28
none
11.12
none
0.64
0. 55
none
CaO
KzO
NagO
HtOHrO(+)
)
)1 1 3 . e 1
Total
100.69
15.00
0.46
< at
100.39
5 5. 8 6
none
22.29
0 .1 6
none
0 .1 5
o.47
0.07
122l
0.39
8.06
)
lr9.12
99.66
99.07
46.O3
none
21.43
0.99
none
none
54.72
none
15.24
1.04
none
l.l7
4.32
2.46
1.00
J. /J
5.59
3 .1 3
I
.22
)lr7
I00.L2
1. Gonnardite, this correspondsto structural formula:
(Cao zrNa: s7)(Fe6slAla36Sibffi)Or0.6.17HrO (K. Nagashima and K. Nakao analysis, 1967).
2. Natrolite, this corresponds to structural formula:
Nar zeMgoorCaoo+Siz35A12
22016'140 HzO (K. Kihara analysis, 1967),
3. Analcime, this corresponds to structural formula:
'1.03 HrO (K. Harada analysis, 1967)'
Nao ezCaoroMgoorAlomSizosOe
4. Erionite, this corresponds to structural formula:
Ko zsNaoroMgorcCaoasAlrrssiassOrz'5.20HzO (K. Nagashima and K. Nakao analysis, 1967).
5. Phillipsite, this corresponds to structural formula:
Ko zsNao6sCas63FesosAlzerSir rzor6'6.39 H2O (K. Nagashima and K' Nakao analysis, 1967).
* (Nos. 1-3 correspond to the specimen shown in Fig. 1).
Puvsrcer, AND OPTTcALPRoPERTTES
The erionite specimensdescribed in this paper are those of Shimazu
and Kawakami (1967). Some reference specimens including offretite
from another locality came from Dr. Sakurai of the National Science
Museum, Tokyo.
The erionite-bearing materials occur in intensely deuterically altered
and weathered basalt soil. They contain woolly white radial aggregates
of fibrous erionite and anhedral chabazite, as shown in Figure 2. Erionite
fibers 2 X 0.05 mm terminate with a needle-like appearanceor with a
rectangular profi.le suggesting the possible development of weak basal
cleavage.
Under the petrographic microscope, this mineral is colorless, with
1788 KAZUO HARADA, SHIGEKI IWAMOTO AND KUNIAKI
RIHARA
Frc. 2. Erionite. (A) Fibrous erionite closely associated with chabazite. Note; c,
chabazite and e, erionite. (B) Erionite in thoroughly weathered basalt soil. (C) Photomicrographof erionite; the fibrous figures terminate with needle-like appearance or rectangular
profile, and possible development of weak basal cleavage was suggested (Polars not closed).
parallel extinction and positive elongation. It is uniaxial positive and the
refractive indices measured by the immersion method using Na light at
0.003. Thesevalues
1 8 o Ca r e e : I . 4 7 7 - f 0 . 0 0 2 , u : 1 . 4 8 0 + 0 . 0 0 2 a n d < . r -: e
are somewhat higher than those hitherto reported for this mineral
(Defieyes, 1959, Staples and Gard,1959, Kamb and Oke, 1960 and
Sheppard, et al., 1965). The specific gravity measured by pycnometer is
ERION I TE, PH I LLI PSI TE A N D GONN A RDITE
1789
2.08 as the average of three measurements. Calculated specific gravity
but with (Si+AD adjustedto 36.0,basedon chemicalanalyses(Table 1),
gave 2.13.
Eakle's analysis (Eakle, 1898) leads to a calculated specific gravity of
2.07 (observed specific gravity 2.02) but with (Si*Al) adjusted to 3.60.
The higher density of Maz6, erionite is due to the higher water content.
Phillipsite, deposited at Geological and Mineralogical Institute,
Tokyo University of Education, was collected by Mr. N. Miyamoto in
1956.This mineral occursas interpenetrating twin or single crystals (rare)
up to 3 X4 mm, closely associatedwith heulandite. It is optically biaxial,
z o n e d ,w i t h ( f ) 2 7 : 6 3 " , c I v Z: 2 3 o , a : 1 . 4 8 3 + 0 . 0 0 2 ,B : 1 . 4 8 5 + 0 . 0 0 2 ,
WAVELENGTH4
7
1800 1700 1600 rs00 t100 1300 1200
cm.
WAVENUMBER
Frc. 3. Inlrared absorption spectra for erionite (upper) and phillipsite (lower). ffole.' Dotted
line indicates elimination of the peaks due to Nujol.
7-a:0.004 in Na light, and specificgravity (mean)
t:1.487*0.002,
:2.t9.
Under the petrographic microscope, single crystals of phillipsites are
always zoned. Refractive indices increase progressively away from the
central parts of the crystals. A phillipsite gives 'y:1.488*0'002 in
the rim.
INrnannt AnsonptroN Spncrne
Infrared absorption spectra for erionite and phillipsite were obtained
using a Nippon Bunkd D5-401-G grating-type spectrophotometer and
the Nujol paste method (Fig. 3). The spectra are similar and have absorption bands at 1040 cm,-1 1640 cm-l and 3400 cm-l. The bands at
I7W KAZUO HARADA, SHIGEKI IWAMOTO AND KI]NIAKI KIHARA
1040 cm. I are attributed to Si-O stretching vibrations (Milkey, 1960).
When closely examined, absorption bands at 3400 cm-1 in the waterstretching region are broad and spread toward higher frequencies.This
phenomenon has also been described in gonnardite, phillipsite and
stilbite by Eva and Vela (1965) and Harada and Tomita (1967).It may
be explained if part of water in these zeolitesis structurally bound.
X-nav Dare
Approximate unit-cell dimensions were determined for erionite from
rotation and zero-layer, normal beam, Weissenbergphotographs. A
,.,:;'r .'"':.
:l
.'.1t.,
,t
Frc. 4. Rotation photograph
for erionite, with crystal rotated about the c-axis. CuKa
radiation with Ni-filter. Camera diameter 57.3 mm.
clear transparent crystal, 0.1X0.3 mm, was rotated parallel to the
longer axis- The rotation photograph (Fig. a) gave a lattice spacing as
15.2+0.2 A based on accuratemeasurementsof high-level spols, which
were obtained with Ni-filtered CuKa radiation, camera diameter 57.3
mm, exposure up to 8 hours. The even-layer lines have considerably
greater intensity than odd-layer lines and have a symmetry of C27,,which
agreeswell with X-ray data by Deffeyes (1959). The 15.2 A spacingis
assumedto be c.
The rotation photograph establishesan important point. The weak,
odd-layer lines result from the AABAACAABAAC stacking in erionite,
where A, B, C are the stacking positions of a 6-membered ring of (Si,
AI)Oa tetrahedra. Recently, J. A. Gard (personal communication, 1967)
DRIONITE, PHILLIPSITE AND GONNARDITD
I79I
has shown that the unit-cell of offretite from Montbrison, France is
h e x a g o n a lw
, ith a:13.31, c:7.59 A, i.e., with c half that of erionite.
X-ray powder patten for offretite disagree with erionite in detail.
Offretite has a stacking of AABAABAABAAB. Mixtures of the two
stackings lead to streaks in the c* direction on the rotation photograph
( B e n n e t ta n d G a r d , 1 9 6 7 ) .
The same crystal was used in the zero- and first-layer Weissenberg
photograph with the crystal oscillating about c. Exposures up to 48
Frc. .5. Zero-layer, normal beam Weissenberg photograph of erionite, with crystal oscillated
about the c-axis. CuKa radiation, Ni-fiiter. Camera diameter 57.3 mm.
hours were required in Ni-filtered CuKa radiation with camera diameter
57.3 mm (Fig.5). The positions and intensity of the spots on the film
gave both zero- and first-level symmetry which corresponds to Dan
( B u e r g e r ,t 9 4 2 , p . 4 7 4 a n dp . a 8 3 ) .A n o b s e r v e do s p a c i n gg a v e 1 3 . 1 f 0 . 2
A f.om zero-levelspots.
There are no systematically absent spots on the zero-level Weissenberg photograph and the only systematic absences on the 1st-level
Weissenbergphotograph are h.h.2h.l when I is odd. No pyroelectric
effect was detected when crystals were placed on an aluminium foil and
soaked in liquid air. The mineral is probably centrosymmetric with
space group confirmed as P6sf mmc-Dnun,
Tl.lln 2. PRrrr,rpsrrn:X-R,ry Powom PerronN
pseudorhombic:
a:9.96, b:14.23 and c:74.23 A
d (meas.)
d (calc.)
8.r7
8 .1 9
7. 1 9
6.41
5.37
5. 0 6
4.98
4.69
4.31
4.13
4.07
3.96
5.(X
4.98
4.70
4.29
4.tl
4.08
3.95
J- /t,
.t.o/
3.54
3.47
3.26
3.19
3.54
/.IJ
o..J/
J.J/
5.40
3.26
3 . 1 9 , 31 8
.t.14
J.IJ
2.930
2.893
2.857
2.754
2.698
2 667
2. 5 7 7
2.946
2 .898
2 .850
2.740
2.691
2.674
2.578
2.543
2.295
n
<n1
2.389
2.309
2.259
2.160
2.136
2.053
2.00r
1.981
1.964
1. 9 1 0
I .834
I .810
1.787
I.
/JJ
|.721
1.680
r.652
1.6M
1.600
1.548
* Unidentified.
hhl
101
020,oo2
ol2
r21
022
200
210
IUJ
131,113
202,220
032
123
222
0r4
t4l
024,O42,123
311
32r
240,204
034
143,105
151,115
331,313
r25
323
t_nt
I
100
12
10
25
3
10
40
13
6
J
6
6
30
85
34
T4
6
4
2l
34
9
o
8
8
z
2.253
2.163
2.139
2. 0 5 3
2.007
1.976
1 .963
1. 9 1 5
1. 8 3 7
1. 8 1 4
1.782
1.736
7.723,1.779
1 . 6 8 0 , 1, 6 7 7
1.645
1 .599
1.548
062,026
343,305
315,351
262,226
3M
064,046,
155,117
, 171
424,M2
361
264,246
452
080,008
s07
355,371,317,460,406
066,208,290
*
183
365
464,46
A
4
3
o
3
8
7
3
7
3
4
7
A
a
A
4
4
ERIONITE, PH ILLIPSITE
AN D GONN ARDITE
1793
With the obtained space group and cell dimensions, X-ray powder
diffraction peaks are indexed; they conform well to previous data
(Staplesand Gard, 1959,and Deffeyes,1959).Then, using this indexing,
accurate values of hexagonal lattice dimensions were obtained using
q u a r t z a s a n i n t e r n a l s t a n d a r d :a : 1 3 . 2 4 a n d c : 1 5 . 1 2 , b o t h + 0 . 0 2 A ,
which are very closeto the data of Staplesand Gard (1959).
Diffractometer peaks of phillipsite were indexed using cell dimensions
and space group proposed by Steinfink (1962) (Table 2) and pseudorhombic lattice dimensionswere obtained from powder data: a:9.96,
b:14.23 and c: 14.23,all being *0.02 A. These values agreewell with
the data by Steinfink (1962).
Cnpivrrcar Dare
About 2 g of pure samplesfor erionite and phillipsite were separatedby
hand picking and were carefully analysed chemically by normal wet
methods (Table 1). Recast in terms of structural formulae, they correspond to:
( K o . z o N a o . r( o
M)g o r a C a or r )( A l r . n r S i o . 1O61)25' . 2 0H r O f o r e r i o n i t e;
and
K o . z g N a o e C a eoa F e o . o r A l : . a r S i r . r : O 1 6 'H
62
. 3O9f o r p h i l l i p s i t e
These formulae conform well with previous analyses.The Ca, Mg are
higher, and Na, K lower than for Eakle's (1S9S)and Hoagland's (Staples
and Gard, 1959) analysesof erionite from the type locality. An erionite
from Central Nevada (J. A. Gard, personalcomm.) had (Ca, MS):0.27,
(K, Na):7.57 and O:72. Wide variations are expectedin the cations,
as discussedby Hay (1964, p. I379).
AcrNowt,roGwNts
The writers wish to express their heartfelt thanks to Prof. T. Sudo of Tokyo Univ. of
Education, Dr. J. A. Gard of Univ. of Aberdeen, Scotland, Prof . D. S. Coombs of Univ. of
Otago, Prof. Y. Seki of Saitama Univ., Dr. A. Kato of National Science Museum, Tokyo,
Prof. R. L. Hay of Univ. of California Berkeley, Dr. A. Iijima of Univ. of Tokyo for helpful
comments and discussions.
Thanks are also due to Prof. K. Nagashima and Mr. K. Nakao for chemical analyses
and to Dr. K. Sakurai and Prof. M. Shimazu for generous zeolite specimens.
Rnrpnr,Nces
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Delrnves, K. S. (1959) Erionite from Cenozoic tufiaceous sediments, Central Nevada.
Atner. M ineraL, 44, 501-509.
1794 KAZUO
IIARADA,
SHIGEKI
IWAMOTO
AND
KUNIAKI
KIHARA
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experimental studies concerning the conversion oI stilbite to wairakite at low water
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loundin Japan.
Onthezeolite
Jnrno,K. (1907)
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-
of gmelinite. Minual. Mag ,32,202-217 .
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M anuscript receioed,A pri'l 17, 1967; anepted Jor publicat'ion Julry 18, 1967'