Chemical Geology, 67 (1988) 261-273 261

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

[5]

CHEMISTRY AND ORIGIN OF ZEOLITES IN SANDSTONES AT

DSDP SITES 445 AND 446, DAITO RIDGE AND BASIN
PROVINCE, NORTHWEST PACIFIC

YONG IL LEE

Department of Geological Sciences, Seoul National University, Seou1151 (South Korea)

(Received March 15, 1987; revised and accepted September 17, 1987)

Abstract

Lee, Y.I., 1988. Chemistry and origin of zeolites in sandstones at DSDP Sites 445 and 446, Daito Ridge and Basin
Province, northwest Pacific. Chem. Geol., 67: 261-273.

Andesitic volcaniclastic sandstones of Middle Eocene age recovered from DSDP Sites 445 and 446, a back-arc basin,
contain clinoptilolite, heulandite and analcite as a pore-filling cement. Clinoptilolite and heulandite at Sites 445 and
446 contain different chemical composition from other deep-sea clinoptilolites and heulandites. The dominant cation
of both clinoptilolite and heulandite is Na , indicating that Na + ion activity in pore water was greater at the time of
their formation. Volcanic glass has acted as a precursor for both clinoptilolite and heulandite at Sites 445 and 446.
Biogenic silica is also suggested as a precursor.
High Na + ion activity in pore water also helped to transform clinoptilolite and heulandite to analcite downhole.
The necessary Na + ions for this clinoptilolite, heulandite and analcite at Sites 445 and 446 might have been provided
by hydrothermal circulation of seawater through more permeable sandstones deposited during early stages of back-
arc basin rifting.

1. I n t r o d u c t i o n atively older sediments. Several chemical anal-

Many studies on volcanogenic sediments in
various sedimentary environments or hydrol-
ogic systems report the occurrence of zeolites
as a diagenetic product. Many authigenic zeo-
lite occurrences show characteristic patterns of
zeolite zoning (Hay, 1978). In deep-seasedi-
ments, zeolites occur both in volcanogenic sed-
iments and pelagic sediments (Stonecipher,
1976, 1978; Boles and Wise, 1978; Kastner and
Stonecipher, 1978; Boles, 1981 ). Phillipsite and
clinoptilolite are the two most abundant zeo-
lites in deep-sea sediments. Minor amounts of
analcite may be present also, especially in rel-
yses of deep-sea clinoptilolites and heulandites
exist, whereas the chemistry of analcites in
deep-sea sediments has not been reported ex-
cept for two samples (Houghton et al., 1979).
The origin of these zeolites in deep-sea sedi-
ments is poorly known and most reports only
describe the occurrence and distribution
(Kastner and Stonecipher, 1978 and references
therein).
Sandstones of Middle Eocene age at DSDP
Sites 445 and 446 in the Daito Ridge and Basin
Province, a back-arc basin, northwest Philip-
pine Sea (Fig. 1 ) contain clinoptilolite, heulan-
dite and analcite pore-fill cements in amounts

0009-2541/88/$03.50 1988 Elsevier Science Publishers B.V.

 bO
O~
SITE 445 SITE 446 to

o :~::~ puo , ......

125 130 ~35 140 ~+~++4-2'_++~+++C 0 12:

1 Korea Honshu t~ ~ ~-~++:~-+++~-+"+" 0 ~ " - - - - ~

a

2oo-1 ~ , :i:

~ ~ _~ ,,,A
W 3
i"I' 300 I oz --1
=i ~ - ~ 300
Shikoku
~ ....
i ~0 - =~
~,t
__ ,,B ~ , , .~
- 1 ,,,B -_----i---i- if!
~:___=~:~f.::~
f ~Am~m Basin , ~ <m' ~ L 3 : _~4.~.~

u #C ~ ~ .'3 L>__'-~

.~ I O d ~ >~ Iv "=----'-
b, 500- D
25 liD
46 Daito ! u~ ~ ....... r
" -v-~-~->-

Parece IV .....
Philippine { _ --
Ve,a I ~ RADIOLARITE ~ SILT
o Sea / Basin 700- zm i L"~ NANNO-FORAMI SAND
- [r.T~,3:LlJ FORAM-NANNO OOZE
O J ~ NANNOFOSSlL CHALK ~ CONGLOMERATE
J i~--~" 5---:i![~ ~ LIMESTONE VOLCANIC ASH
J ~
125 130 135 140 800- VB i[T~.+ ::: ~.~, ~ CLAY ~ BASALT
~ [~-~ PELAGIC CLAY ql SAMPLE
CLAYEY SILT
900 J

Fig. 1. Location and stratigraphy of D S D P Sites 445 and 446.


up to 17%. Sandstone deposition at these sites
occurred on submarine fans during early stages
of basin rifting ( Klein et al., 1980). Generally,
back-arc basins are characterized by a large heat
flow (Watanabe et al., 1977). In parallel with
mid-ocean-ridge spreading zones, it is expected
that some thermal influence exists from newly
formed basement during deposition of sedi-
ment coeval with active rifting (Sclater et al.,
1980). Elevated temperatures due to thermal
influence may enhance the reaction rate be-
tween sediments and pore solution and thus lead
to thermal diagenesis, which is defined here as
thermal alteration of sediments in excess of
normal burial conditions (Lee, 1987).
The purpose of this study is to provide the
chemical composition of deep-sea clinoptilol-
ite, heulandite and analcite in back-arc basin
sandstones and to interpret the origin of these
zeolites in the context of geodynamics in an ac-
tive tectonic domain,
2. Geologic s e t t i n g
The stratigraphy at Sites 445 and 446 is
nearly identical (Fig. 1 ). The basal part of the
section consists of interbedded volcaniclastic
mudstone, siltstone, graded turbidite sand-
stone, and debris-flow conglomerate (Klein et
al., 1980; White et al., 1980). These are overlain
by re-sedimented pelagic foraminifera, nanno-
plankton ooze, chalk and limestone at Site 445,
and pelagic clay at Site 446. The volcaniclastic
sediments at Site 446 are intruded by at least
26 basalt sills. These sills were derived probably
from the remnant arcs of the Daito Ridge and
the Oki-Daito Ridge.
Sediments at Site 445 range in age from Mid-
die Eocene to Pleistocene and those at Site 446
from Early Eocene to Pleistocene (Klein et al.,
1980). Based on paleontological evidence at Site
445, an 8-Ma hiatus encompasses the Early and
Middle Oligocene. This hiatus occurs at ~ 550
m subbottom depth (Fig. 1). At Site 446, a large
number of hiatuses was observed downhole from
a subbottom depth of 170 m. Such hiatuses are
263
known to favor advection of water within the
sediments (Abbott et al., 1981 ).
3. A n a l y t i c a l m e t h o d s
Samples were obtained from most sandstone
intervals in cores of DSDP Sites 445 and 446.
Thin-sections were made of vertical slices of
each sample. Scanning electron microscopy
(SEM) analysis was carried out on a Cam-
bridge Stereoscan Mark II instrument. Min-
erals were examined also with energy-dispersive
X-ray fluorescence spectrometry (EDAX). The
identification of minerals was also corrobo-
rated by an X-ray diffractometer and a mi-
croanalyzer. Quantitative analyses for chemical
composition of zeolites were carried out using
polished thin-sections on an automated
JEOL -50A electron probe microanalyzer with
an energy-dispersive spectrometer. The oper-
ating conditions were: excitation voltage 20 kV;
sample current, 300 pA; beam diameter, ~ 2 zm;
count time, 120s. Point analyses were made in
each single crystal. Si, A1, Na, K, Ca, Mg and
Fe were the seven elements that were mea-
sured. Precision of analysis is around + 2%. The
matrix correction was made using the Z A F
program.
4. S u m m a r y of p e t r o l o g y a n d d i a g e n e s i s
The detailed petrology and diagenesis of
sandstones at Sites 445 and 446 are described
in Lee (1984) and Lee and Klein (1986). Here
reported is a brief summary which is relevant
to the present paper. Sandstones at Sites 445
and 446 are classified as volcanic arenites. The
most abundant components are volcanic rock
fragments of which andesitic rock fragments
predominate, indicating a volcanic arc source.
These comprise in amounts up to 83 % and 65 %
at Sites 445 and 446, respectively. Matrix, where
present, is partially altered volcanic glass.
Downhole diagenetic changes consist of
smectite and chlorite rim cement, microsparry
and sparry calcite cement, clinoptilolite and
264

IvoLc^.,c QL^SSI TABLE I

~/?? Chemical analyses and unit cell contents of five representative cli-
noptilolites and heulandites at Sites 445 and 446

~ @ ~ ' ' " ~ /// I Clinoptilolite heulandite

c~'*av.r /~ ,( _ ~. + ~ Core(cm) (70-72} (24-26) (81-86) (0-4) (24-26)

Smec
i
te/ll e ~ ~ ~ SiO2 66.33 68.58 65.71 64.41 65.71
A[20:~ 13.15 13.31 12.93 15.31 14.99

, +~ -- K20 2.82 3.34 1.65 1.40 2.80

r~ ~ ~,,~
e ~| CaO 1.12 1.48 2.03 1.66 2.40
['LB,er' Ca~c,eI MgO 0.51 0.50 0.14 0.74 0.72

~ +~ Fe203*'
H20 .2
Total
12.27
100
10.02
100
0.04
13.27
100
0.18
11.66
100
0.10
10.48
100
Fig. 2. Authigenic mineral paragenesis derived from a vol-
canic glass precursor at DSDP Sites 445 and 446. Number of cations on the basis of 72 oxygens:
Si 29.23 29.43 29.24 28.13 28.47
Al 6.83 6.73 6.77 7.88 7.65
heulandite pore-fill cement, analcite pore-fill Na 3.25 2.30 3.64 4.35 2.36
cement and later sparry calcite cement. Detri- K 1.59 1.83 0.94 0.79 1,54
Ca 0.53 0.68 0.97 0.78 1.11
tal grain replacement by calcite, microcrystal- Mg 0.34 0.32 0.09 0.48 0.47
line quartz and zeolite is also frequently Fe 0.01 0.06 0.04
observed. In addition, authigenic feldspars were Si/A1 4.28 4.37 4.32 3.57 3.72
observed in the lower part of the sandstone col- Si+Al 36.06 36.16 36.01 36.01 36.12
umn at Site 445 and in relatively shallow depths *~Fe203is total iron.
above 260 m at Site 446. Albite and K-feldspar *~Bydifference.
are present both as overgrowths on the detrital
feldspar grains and as euhedral crystals with- 5.1. C h e m i s t r y o f clinoptilolite, h e u l a n d i t e a n d
out nucleation. Most authigenic minerals are analcite
observed within interstices. Reactive volcanic
glass matrix appears to be the primary source Both clinoptilolite and heulandite belong to
of these authigenic minerals (Lee, 1984). The the heulandite group minerals. The composi-
paragenesis of authigenic minerals derived from tional distinction between clinoptilolite and
a volcanic glass precursor is shown in Fig. 2. heulandite is somewhat arbitrary. The present
The crystal length of clinoptilolite ranges author adopts Boles' (1972) nomenclature,
from 0.09 to 0.32 mm with an average of 0.17 separating these two minerals by a Si/A1 ratio
mm and that of heulandite is in the range of 4.0. Clinoptilolite contains a Si/A1 ratio
0.017-0.05 mm. The average diameter of anal- ranging from 4.0 to 5.1 and dominant cations
cite is ~ 0.16 mm. are K + and Na +, whereas heulandite contains
a Si/A1 ratio ranging from 2.9 to 4.0 with Ca 2+
5. R e s u l t s a n d d i s c u s s i o n and Na + as dominant cations.
Chemical analyses for some representative
clinoptilolites and heulandites are presented in
The number of analyses on clinoptilolite to- Table I. Both clinoptilolite and heulandite show
tals 45 ( Site 4 4 6 - - 31; Site 4 4 6 ~ 14), on heu- a very narrow compositional range in Si/A1 ra-
landite 52 (Site 4 4 5 ) , and 84 on analcite (Site tios (Fig. 3a). Fig. 4 shows a N a - ( Ca + M g ) - K
445 - - 62; Site 4 4 6 ~ 22 ). plot of deep-sea clinoptilolites and heulandites.
 265

310 " 360" ~ \

Clinoptilolite ~ Analcite
o Site 4 4 5 ~ o Site 4 4 5
Site 4 4 6 \ - Site 4 4 6
Heulandite 358 \
300 o A Site 4 4 5
o o \
o
\
290 o A (~ 340 ~\ o
\

28.0 330 :o

A %"

270 \~,\ 320

\ \
81o ~io 8'0 ~'0 ,28 ,30 ,,)o ,;0 ,~o
AI/72 Ox A I / 9 6 O

(a) (b)

Fig. 3. Variation of Si vs. AI for clinoptilolite and heulandite (a) and for analcite (b) at DSDP Site 445 and 446, Daito
Ridge and Basin Province.

Ca+Mg 439 (off Sanriku, Japan) to be Na although

Na ' ,, ~ ,, ~ ~
Fig. 4. Ternary ( C a + M g ) - N a - K diagram in atomic per-
cent of deep-seaclinoptilolitesand heulandites.Numbers
in parentheses represent the number of analysis,
The analyses of other deep-sea clinoptilolites
by Boles and Wise (1978), Stonecipher (1978)
and Iijima et al. (1980) are also shown in Fig.
4 for comparison. At Sites 445 and 446, clinop-
tilolites are predominantly sodic, in agreement
with Sheppard's (1971) finding that Na is the
dominant cation in most sedimentary clinop-
tilolites. Those of Boles and Wise (1978) and
Stonecipher (1978) contain K as a dominant
cation. Iijima et al. (1980) also suggested the
dominant cation in clinoptilolites at DSDP Site
Clinopt*lo,ite
o Site 4 4 5 [ 3 1 )
their results of 15 analyses are plotted as more
Site 4 4 6 ( 1 4 )
u Stoneci13her(1978}[25)
K than Na because they adjusted their data for
Boles & Wis6[1978)(6)
lijima et al.(1980)(15)
a machine factor. Heulandite in the present
Heulandite samples also contains more Na than Ca-Mg and
K. The dominance of Ca and K is interchange-
able compared to most sedimentary heulan-
dites (Boles, 1972 ). However, as shown in Fig.
4 heulandite contains more Ca-Mg than
clinoptilolite.
The main difference seems to lie in the pore-
water chemistry of the system. If the sediments
are relatively impermeable, the system be-
~ ~ , ,, ' K
comes isochemical and preserves K derived from
the dissolution of volcanic material, resulting
in an increasing K / H ratio with negligible al-
teration of the Na/H ratio ( Kastner and Siever,
1979). In a relatively open pore-water system
or in the presence of brines, the relative pro-
portion of K decreases with increasing other
cations. Most host sediments of clinoptilolites
reported by Boles and Wise (1978) and Sto-
necipher (1978) are dominantly clays and muds
and rare siliceous oozes. The dominance of K
in clinoptilolite composition may be due to the
presence of clay, whereas a relatively open sys-
tem provides Na to the pore waters by advec-
tion (Abbott et al., 1983) and thus may account
for the Na dominance over K in the clinoptil-
266

olite composition in sandstones at Sites 445 and TABLEII

446. Chemical analyses and unit cell contents of three repre-
Heulandite was reported in deep-sea sedi- sentative analcites at Sites 445 and 446
ments by Boles and Wise (1978) from organic-
rich sediments in the Indian Ocean and possi- No. 445-90-2 445-90-2 446-29-1
bly by Stonecipher (1978; see Gottardi and Core ( c m ) (11-14) (22-26) (13-15)
Galli, 1985, p. 280). Sheppard (1971) reported si02 56.47 55.32 52.22
that heulandite is characterized by a A1203 21.40 20.67 19.89
(Na+K)/(Na+K+Ca+Mg) ratio<0.5. At Na20 12.70 12.22 11.80
K20 0.04 0.04
Sites 445 and 446, however, most heulandites CaO 0.01
show this ratio to be > 0.5. MgO 0.04
This consideration suggests that at the time Fe~O.~.1 0.15 0.01
of heulandite formation, the activity ratio of al- H20"2 9.43 11.60 15.97
Total 100 100 100
kali to alkaline-earth ions seemed to be rela-
tively large, as in clinoptilolite formation, Number of cations on the basis o[96 oxygens:
although the Si activity was reduced in the pore- Si 33.30 33.36 33.18
water chemistry. AI 14.79 14.69 14.87
The average chemical composition of clinop- Na 14.43 14.28 14.51
tilolite at Sites 445 and 446 is: K O.O4 0.O3
Ca
Na3., K,.5 Cao.sMgo.3A16.s8i29.2072" 21 H2 0 Mg 0.04
Fe 0.06 0.02
and of heulandite is:
Si/Al 2.25 2.27 2.23
Na3., K,.2 Ca,.3 Mgo.5A17.9Si2s., 072" 23H20 Si + AI 48.09 48.05 48.05
Chemical analyses of three representative *'Fe203 is total iron.
*2By difference.
analcites are presented in Table II. The com-
positional range of most analcites shows the
Si/A1 ratio to be 2.08-2.32 and two analcites observed rarely. In this study, analcite shows
show a larger ratio up to 2.8. Analcite also shows about the same compositional range regardless
of association with authigenic feldspar.
a very narrow compositional range (Fig. 3b).
However, at Site 446 analcites contain less Si The only data of analcite composition in
than those at Site 445. Analcite composition deep-sea sediments were reported by Houghton
does not show any relationship with burial et al. (1979). Two analcites from DSDP Site
386 (Central Bermuda Rise) in the western
depth. In a study of nonmarine analcites, Iijima
and Hay (1968) reported two groups of analcite North Atlantic show a composition comparable
with Si/A1 ratios of 2.0-2.30 and 2.60-2.80, to Sites 445 and 446 and their Si/A1 ratio is 2.16.
which is inversely proportional to the amount The average chemical composition of analcite
of authigenic alkali feldspar. They suggested at Sites 445 and 446 is:
that low-silica analcite is formed generally as Na,~AllsSi33096"16H20
an intermediate stage in the reaction of sili-
ceous analcite to form alkali feldspar. Although
the compositional range of Si/A1 ratios of an- 5.2. Origin of deep-sea zeolite
alcite at Sites 445 and 446 is comparable to the
low-silica analcite of their study, no confirma- 5.2.1. Clinoptilolite and heulandite. Zeolitic al-
tion could be established of such an intermedi- teration of volcanic glass is typically a solu-
ate stage because high-silica analcites are tion-precipitation phenomenon and not a

process of devitrification or hydration in the
solid stage (Deffeyes, 1959). The origin of cli-
noptilolite and heulandite in deep-sea sedi-
ments is not well known although in other
geologic settings, these minerals were reported
as a diagenetic alteration product of rhyolitic
glass (Hay, 1966; Sheppard and Gude, 1968,
1969; Iijima and Utada, 1971). However, differ-
ence in pH and precursor materials may result
in different diagenetic mineralogy. For exam-
ple, phillipsite forms from rhyolitic glass in sa-
line lakes; and in a deep-sea environment from
basaltic glass. In oceanic environments, Cook
and Zemmels (1972) reported an occurrence of
clinoptilolite associated with rhyolitic glass at
DSDP Site 84. However,the precursor could not
be determined because of the presence of unal-
tered rhyolitic glass. Therefore, based on the
association of clinoptilolite with both volcanic
and nonvolcanic sediments, several possible
precursors are known including rhyolite to an-
desitic glass, basaltic glass + silica ( mainly bio-
genic), smectite + phillipsite + biogenic silica
(Kastner and Stonecipher, 1978). The follow-
ing are several possible diagenetic reactions for
clinoptilolite formation in deep-sea sediments
( Kastner, 1981, table 1 ).
andesitic and rhyolitic glass + H4 Si04 ~
clinoptilolite (1)
phillipsite + Ht SiOt -, clinoptilolite (2)
opal-A + A1 ( OH ) 4 + K + -~
opal-CT + clinoptilolite (3 )
opal-A+Al(OH)~- + K + -~
clinoptilolite (4)
phillipsite + smectite + H4 SiO4-,
clinoptilolite + palygorskite (5 )
Clinoptilolite and heulandite are treated to-
gether in considering their origin because these
two minerals show similar physical and chem-
267
ical properties as discussed on p. 266. Only less
silica and somewhat higher Ca 2+ and Mg 2+ ac-
tivities in the pore water are suggested for the
formation of heulandite.
Reactions (2) and (5) are not suggested for
clinoptilolite formation at Sites 445 and 446 be-
cause these reactions require the presence of a
phillipsite precursor. No zeolite minerals, in-
cluding phillipsite, were observed in the sedi-
ments younger than the sandstones at Sites 445
and 446 ( Chamley, 1980; Nagel et al., 1981 ).
Clinoptilolite and heulandite occur only in the
sandstone intervals in which no evidence of
phillipsite exists.
Although reaction (1) was suggested before
for the formation of clinoptilolite, no evidence
existed for it ( Gottardi and Galli, 1985, p. 281 ).
However, in the sandstones at Sites 445 and 446,
the association of clinoptilolite and heulandite
with an altered glass matrix, and the replace-
ment of volcanic glass matrix by clinoptilol-
ite-heulandite are observed frequently (Fig. 5),
thus showing that volcanic glass is a direct pre-
cursor of these zeolite minerals. Microprobe
analysis shows that volcanic glass matrix at
both sites contains an andesitic compositional
range, although it is altered indicating reaction
(1) to be the most probable. Further, analyses
of tiny clinoptilolite/heulandite crystals re-
placing volcanic glass matrix (Fig. 6) at Site
446 contain unusually low in Si/A1 ratios, sug-
gesting they are metastable crystals although
they are visible under the petrographic
microscope.
Therefore, reaction (1) is the most probable
one in the formation of clinoptilolite and heu-
landite in sandstone diagenesis at Sites 445 and
446. However, reactions (3) and (4) cannot be
excluded. These reactions are also probable but
less certain than reaction (1). For clinoptilolite
and heulandite at Sites 445 and 446 these re-
actions need Na + ion instead of K + ion. Both
reactions (3) and (4) need the presence ofbio-
genic silica as a precursor. Siliceous microfos-
sils are reported to be rich in the upper part of
sandstone intervals at Site 445 and the entire
268

Fig. 5. Replacementof volcanic glass by clinoptiloliteand heulandite.

A. Photomicrographshowingthat small tiny heulandite (H) euhedral crystals replace volcanic glass matrix. Such crystal
forms suggest precipitation from solution. Cristobalite (Cr) layer on volcaniclastic grain is shown in upper right-hand
corner. Plane light; sample 445-74-1 (93-97), subbottomdepth 693.47 m.
B. SEM photomicrograph.Developmentof clinoptilolite (Cl) euhedralcrystalsfromvolcanicglass. Sample445-71-1 (90-91 ),
subbottom depth 664.9 m.

sandstone interval at Site 446. Deep-sea clinop-
tilolite occurrence may be closely associated
with cristobalite (variety opal-CT), an associ-
ation reported by several researchers (Moiola,
1970; Iijima, 1978; K a s t n e r and Stonecipher,
1978; Moncure et al., 1981). The presence of
cristobalite indicates t h a t at the time of its for-
mation, the pore water was supersaturated with
respect to silica.
The formation of clinoptilolite and heulan-
dite is favored by the presence of dissolved sil-
ica to promote reaction (1). Silica may be

Fig. 6. Photomicrographshowingthat clinoptilolite-heulandite(CH) euhedralcrystals replacevolcanicglassmatrix. Plane
light; sample446-20-1 (84-88), subbottomdepth 137.34m.
contributed from several sources. The most im-
portant sources are volcanic glass and volcanic
rock fragments. Surdam and Boles (1979)
pointed out that t h e andesitic glass to zeolite
reaction does not require large amounts of mass
transfer. This finding would explain the clinop-
tilolite-heulandite replacement of volcanic glass
without additional ions except addition of water,
Silica may be provided also by the dissolution
of siliceous microfossils (radiolaria) and sponge
spicules which will increase the silica activity
and raise the Si/A1 ratio of the immediate en-
vironment. Altered siliceous microfossils are
reported to be rich within the sandstone inter-
val at Sites 445 and 446 where zeolite minerals
are observed ( Klein et al., 1980 ). This biogenic
silica source also leads to the above-mentioned
reactions ( 3 ) and (4). Some silica may be added
from the alteration of the basement basalt by
possible upwelling hydrothermal waters. The
alteration of basalt glass to smectite (palagon-
ite) caused the release of about one half of the
original Si and A1, two-thirds of the original Mg
and Na, and >90% of the original Ca (Ailin-
Pyzik and Sommers, 1981). Some of these re-
leased ions may be reprecipitated within the
269
0.1 m m
basalt as zeolites, clay minerals or calcite. The
resulting pore fluid seems to contain more silica
and Ca than seawater and a slight depletion in
Mg (Abbott et al., 1983). Similar results were
obtained by the calculations of "high-temper-
ature" alteration of basalts based on laboratory
experiments (Bischoff and Dickinson, 1975)
and on Gal~ipagos hot springs (Edmond et al.,
1979). Additional silica is suggested to come
from the conversion of montmorillonite to illite
in marine sediments to provide some of silica
necssary for clinoptilolite formation ( Stoneci-
pher, 1976). It is possible that at Sites 445 and
446 authigenic pure smectite released some sil-
ica and reached the present composition of 20%
of illitic layers.
5.2.2. A nalcite. Analcite may have been derived
form an alkali zeolite precursor such as clinop-
tilolite or heulandite. Hay (1966) and Shep-
pard and Gude (1969) also concluded from a
study of tufts in saline lake deposits that anal-
cite formed commonly from alkalic silicic zeo-
lite precursors. Analcite also has been
synthesized from natural clinoptilolite and
heulandite by Boles (1971).
270

0.1 mm

Fig. 7. A. Photomicrograph.Analcitepore-fillcement (A) pseudomorphafter heulandite (H) which replacedvolcanicglass

matrix. Small relict crystals of heulandite are shown in analcite crystal. Cristobalite (Cr) layer developedalongthe volca-
niclastic grain in the upper left-hand corner. Plane light; sample 445-85-1 (18-20), subbottomdepth 797.18 m.
B. SEM micrograph.Analcite (A) crystaloccupiesthe center ofthe pore. Dissolutionfeaturesofclinoptiloliteand heulandite
suggest the developmentof analcite at the expense of clinoptilolite (Cl) and heulandite (H). Sample 445-88-2 (24-26);
subbottom depth 827.24 m.

Analcite occurs as both precipitation and re-
placement products at Sites 445 and 446. In
thin-section, analcite replaces heulandite which
already replaced volcanic glass (Fig. 7A). Un-
der the SEM, dissolution features of clinoptil-
olite and heulandite suggest t h a t they are
metastable and are in favor of the development
of analcite at the expense of clinoptilolite or
heulandite (Fig. 7B ).
The reaction of clinoptilolite and heulandite
to analcite would be, respectively:

clinoptilolite-.analcite
or
Na3.1 K1.5Cao.sMgo.3A16.8Si29.2072" 21H20
+3.65Na+-,0.45Na1~All~Si33096
16H20+14"35SiO2+l'5K+ +0"8Ca2+
+0.3Mg 2+ +13.9H20 (6)
heulandite-~analcite
or
Na3.~ KL2 Cal.3Mgo.sA17.9Si2s.1072"23H2 0
+ 4.85Na + -. 0.55Na15 All5 Si33 096"
16H20+9.85Si02 +1.2K + 1.3Ca 2+
+ 0.5Mg 2 + 14.4H2 0 (7)
The equations show that the activities of the
cations, silica and water control the reactions.
The major changes are a gain of Na + and losses
of K +, Ca 2+, and Si02 and H20, assuming con-
servation of alumina,
The physicochemical conditions for analcite
formation can be considered in the following
ways:
(1) The increase in temperature in the sys-
tem enhances the transformation from clinop-
tilolite and heulandite to analcite. Temperature
is a significant factor in controlling zeolite sta-
bility largely because of the hydrated state of
zeolites in marine environments, although al-
kaline saline conditions may control the kinet-
ics in nonmarine environments. Thus, from a
thermodynamic point of view, clinoptilolite and
heulandite are less stable than analcite at the
elevated temperatures. In a field occurrence of
thick marine deposits, the clinoptilolite zone
was succeeded by an analcite zone with increas-
ing depth, implying increasing temperature
(Iijima, 1978). Differences in the formation
temperatures of these minerals can be seen in
the oxygen isotope composition, which shows a
tendency to decrease downhole in parallel with
these mineralogical changes (Lee, 1987 ).
271
( 2 ) As shown in the above reactions, analcite
formation is favored by the relatively large ac-
tivity of Na + and small silica activities. Inter-
stitial water chemistry of analcite-bearing
sediments shows such water to contain molar
Na/K ratios of ~160 (Gieskes, 1976) com-
pared to that of seawater ~ 40. Molar Na/K ra-
tios of interstitial waters in clinoptilolite-
bearing sediments average ~ 6 0 (Boles, 1981).
A continuous supply of Na + from the intersti-
tial water is required to form analcite. Contin-
uous addition of fresh seawater, the largest
reservoir of Na, is suggested to provide neces-
sary Na to the system, thus implying hydro-
thermal circulation of seawater by advection.
Independent evidence for hydrothermal advec-
tion at Sites 445 and 446 is suggested also by
oxygen isotope measurements of zeolites (Lee,
1987) and by a large number of hiatuses attrib-
utable to water advection (Abbott et al., 1981 ).
This phenomenon can explain also that both
clinoptilolite and heulandite are dominated by
Na + over K +, which is not in agreement with
other deep-sea clinoptilolites and heulandites
(Boles and Wise, 1978; Stonecipher, 1978).
This hydrothermal circulation would account
also for an additional Na source and thermal
conditions to favor the reaction of clinoptilol-
ite-heulandite to analcite. However, at a later
stage, probably because of reduction in heat
fl0w, the hydrothermal circulation would be less,
or episodic and this is suggested by the presence
of authigenic potassium feldspar and some dis-
crete illite cements because their presence sug-
gests large activity of K + over Na + in the pore-
water composition. K is also derived from the
reaction of clinoptilolite-heulandite to analcite.
6. C o n c l u s i o n s
The deep-sea clinoptilolite as well as heulan-
dite does not show uniform chemical composi-
tion even though their occurrence is restricted
in deep-sea sediments. The dominant cation of
both clinoptilolite and heulandite at Sites 445
and 446 is Na +, which differs from other deep-
272
sea clinoptilolites and heulandites, whose dom-
inant cations are K + for clinoptilolite and Ca e+
for heulandite. This difference indicates a
greater activity of Na + ions in pore water from
which clinoptilolite and heulandite w e r e p r e -
cipitated. A continuous supply of Na to the pore
w a t e r by hdyrothermal circulation of seawater
through the sediments would provide the nec-
essary amounts of Na to form clinoptilolite and
heulandite at Sites 445 and 446, considering that
sandstones containing these zeolites were de-
posited during early stages of rifting in a back-
a r c basin. Reaction of volcanic glass and pos-
sibly some volcanic rock fragments with pore
water rich in silica resulted in the formation of
clinoptilolite and heulandite. Biogenic silica
might have acted as a precursor also, but less
certain,
Increasing burial depth and consequently el-
evated temperature caused later mineral trans-
formation of clinoptilolite and heulandite to
analcite. To derive these mineralogical changes
additional Na may have been provided by the
above-mentioned fluid circulation.
Acknowledgements
This paper is extracted from a Ph.D. disser-
tation submitted to the University of Illinois at
Urbana-Champaign.
I wish to thank Dr. G. deV. Klein, disserta-
tion supervisor, for his invaluable help and e n -
couragement throughout this research. This
work was supported by the Graduate College of
the University of Illinois at Urbana-Cham-
paign, the American Association of Petroleum
Geologist, and National Science Foundation
Grant OCE 81-09447 to G. deV. Klein. I also
thank Drs. R.L. Hay, A.T. Hsui, S. Marshak
and P.A. Sandberg for their comments on ear-
lier versions of this manuscript. Mr. Cameron
Begg is thanked also for his assistance with mi-
croprobe work. Dr. J.R. Boles and a n a n o n y -
mous referee are acknowledged also for their
constructive c o m m e n t s o n this paper.
References
Abbott, D.H., Menke, W., Hobart, M. and Anderson, R.,
1981. Evidence for excess pore pressures in southwest
Indian Ocean sediments. J. Geophys. Res., 82:
1813-1827.
Abbott, D.H., Menke, W. and Morin, R., 1983. Constraints
upon water advection in sediments of the Mariana
Trough. J. Geophys. Res., 88: 1075-1093.
Ailin-Pyzik, I.B. and Sommers, S.E, 1981. Microscale
chemicaleffectsof low temeraturealteration of DSDP
basaltic glasses. J. Geophys. Res., 86: 9503-9510.
Bischoff, J.L. and Dickinson, F.W., 1975. Seawater-basalt
interaction at 200 C and 500 bars: implications for or-
igin of sea-floor heavy metal deposits and regulation of
seawater chemistry. Earth Planet. Sci. Lett., 25: 385-397.
Boles, J.R., 1971. Synthesis of analcime from natural heu-
landite and clinoptilolite. Am. Mineral, 56: 1724-1734.
Boles, J.R., 1972. Composition, optical properties, cell di-
mensions, and thermal stability of some heulandite group
zeolites. Am. Mineral., 57: 1463-1493.
Boles, J.R., 1981. Zeolites in deep-sea sediments. In: F.A.
Mumpton (Editor), Mineralogy and Geology of Natu-
ral Zeolites. Mineral. Soc. Am., Rev. Mineral., 4: 137-163.
Boles, J.R. and Wise, W.S., 1978. Nature and origin of deep-
sea clinoptilolite. In: L.B. Sand and F.A. Mumpton
(Editors),NaturalZeolites: Occurrence, Properties, Use.
Pergamon, New York, N.Y., pp. 235-243.
Chamley, H., 1980. Clay sedimentation and paleoenviron-
ment in the area of the Daito Ridge since the Early
Eocene. In: G. deV. Klein, K. Kobayashi et al. (Edi-
tors), Initial Reports of the Deep Sea Drilling Project,
Vol. 58. U.S. Gov. Print. Off., Washington, D.C., pp.
683-694.
Cook, H.E. and Zemmels, I., 1972. X-ray mineralogy stud-
ies - - Leg 9. In: J.D. Hays, H.E. Cook et al. (Editors),
Initial Reports of the Deep Sea Drilling Project, Vol. 9.
U,S. Gov. Print. Off., Washington, D.C., pp. 707-778.
Deffeyes, K.S., 1959. Zeolites in sedimentary rocks. J. Sed-
iment. Petrol., 29: 602-609.
Edmond,J.C. Measures, C., McDuff, R.E., Chan, L.H.,
Collier, R. and Grant, B., 1979. Ridge crest hydrother-
mal activity and the balances of the major and minor
elements in the ocean: the Galapagos data. Earth Planet.
Sci. Lett.,46: 1-18.
Gieskes,J.M., 1976. Interstitial water studies, Leg 33. In:
S.O. Schlanger, E.D. Jackson et al. (Editors), Initial
Reports of the Deep Sea Drilling Project, Vol. 33. U.S.
Gov. Print. Off., Washington, D.C., pp. 563-570.
Gottardi, G. and Galli, E., 1985. Natural Zeolites. Springer,
Heidelberg, 409 pp.
Hay, R.L., 1966. Zeolites and zeolitic reactions in sedimen-
tary rocks. Geol. Soc. Am., Spec. Pap. No. 85, 135 pp.
Hay, R.L., 1978. Geologic occurrences of zeolites. In: L.B.
Sand and F.A. Mumpton (Editors), Natural Zeolites:

Occurrence, Properties, Use. Pergamon, New York, N.Y.,
pp. 135-143.
Houghton, R.L., Rothe, P. and Galehouse, J.S., 1979. Dis-
tribution and chemistry ofphillipsite, clinoptilolite and
associated zeolites at DSDP Sites 382, 385, and 386 in
thewestern North Atlantic. In: B.E.Tucholke, P.R. Vogt
et al. (Editors), Initial Reports of the Deep Sea Drilling
Project, Vol. 43. U.S. Gov. Print. Off., Washington, D.C.,
pp. 463-483.
Iijima, A., 1978. Geologic occurrences of zeolite in marine
environments. In: L.B. Sand and F.A. Mumpton (Edi-
tors), Natural Zeolites: Occurrence, Properties, Use.
Pergamon, New York, N.Y., pp. 175-198.
Iijima, A. and Hay, R.L., 1968. Analcime composition in
tuffs of the Green River Formation of Wyoming. Am.
Mineral., 53: 184-200.
Iijima, A. and Utada, M., 1971. Present-day zeolitic diagen-
esis of the Neogene geosynclinal deposits in the Niigata
oil field, Japan. In: R.F. Gould (Editor), Molecular Sieve
Zeolites, I. Am. Chem. Soc., Adv. Chem. Set., 101:
327-357.
Iijima, A., Matsumoto, R. and Tada, R., 1980. Zeolite and
silica diagenesis and sandstone petrography at Sites 438
and 439 off Sanriku, northwest Pacific, Leg 57, Deep
Sea Drilling Project. In: R. Von Huene, N. Nasu, M.
Langseth, H. Okada et al. (Editors), Initial Reports of
the Deep Sea Drilling Project, Vols. 56 and 57, Part II.
U.S. Gov. Print. Off., Washington, D.C., pp. 1143-1158.
Kastner, M., 1981. Authigenic silicates in deep-sea sedi-
ments: formation and diagenesis. In: C. Emiliani (Edi-
tor), The Oceanic Lithosphere, The Sea, Vol. 7. Wiley,
New York, N.Y., pp. 915-980.
Kastner, M. and Siever, R., 1979. Low temperature feld-
spar in sedimentary rocks. Am. J. Sci., 279: 435-479.
Kastner, M. and Stonecipher, S.A., 1978. Zeolites in pe-
lagic sediments of the Atlantic, Pacific, and Indian
Oceans In: L.B. Sand and F.A. Mumpton (Editors),
Natural Zeolites: Occurrence, Properties, Use. Perga-
mon, New York, N.Y., pp. 199-220.
Klein, G. deV. and Lee, Y.I., 1984. A preliminary assess-
ment of geodynamic controls on depositional systems
and sandstone diagnesis in back-arc basins, western Pa-
cific Ocean. Tectonophysics., 102: 119-152.
Klein, G. deV., Kobayashi, K. et al., 1980. Initial Reports
of the Deep Sea Drilling Project, Vol. 58. U.S. Gov. Print.
Off., Washington, D.C., 1017 pp.
Lee, Y.I., 1984. Petrology and diagenesis of the medium-
grained clastic sediments in the back-arc basins of the
western Pacific Ocean. Ph.D. Dissertation, University
of Illinois at Urbana-Champaign, Urbana, Ill., 208 pp.
Lee, Y.I., 1987. Isotope aspects of thermal and burial dia-
genesis of sandstones at DSDP Site 445, Daito Ridge,
northwest Pacific Ocean. Chem. Geol. (hot. Geosci.
Sect.), 65" 95-102.
Lee, Y.I. and Klein, G. deV., 1986. Diagenesis of sandstones
273
in the back-arc basins of the western Pacific Ocean. Se-
dimentology, 33: 651-675.
Moiola, R.J., 1970. Authigenic zeolites and K-feldspar in
the Esmeralds Formation, Nevada. Am. Mineral., 55:
1681-1691.
Moncure, G.K., Surdam, R.C. and McKague, H.L., 1981.
Zeolite diagenesis below Pahute Mesa, Nevada Test Site.
Clays Clay Miner., 29: 385-396.
Nagel, U., Muller, G. and Schumann, D., 1981. Mineralogy
and sediments cored during Deep Sea Drilling Project
Legs 58-60 in the north and south Philippine Sea: re-
suits of X-ray diffraction analyses. In: D.M. Hussong,
S. Uyeda et al. (Editors), Initial Reports of the Deep
Sea Drilling Project, Vol. 60. U.S. Gov. Print. Off.,
Washington, D.C., pp. 415-436.-
Sclater, J.G., Jaupart, C. and Galson, D., 1980. The heat
flow through oceanic and continental crust and the heat
loss of the earth. Rev. Geophys. Space Phys., 18: 269-311.
Sheppard, R.A., 1971. Zeolites in sedimentary deposits of
the United States - - review. In: R.F. Gould (Editor),
Molecular Sieve Zeolites, I. Am. Chem. Soc., Adv. Chem.
Set., 101: 273-310.
Sheppard, R.A. and Gude III, A.J., 1968. Distribution and
genesis of authigenic silicate minerals in tuffs of Pleis-
tocene Lake Tecopa, Inyo County, California. U.S. Geol.
Surv., Prof. Pap. No. 597, 38 pp.
Sheppard, R.A. and Gude III, A.J., 1969. Diagenesis of tuffs
in the Bastow Formation, Mud Hills, San Bernardino
County, California, U.S. Geol. Surv., Prof. Pap. No. 634,
35 pp.
Stonecipher, S.A., 1976. Origin, distribution and diagene-
sis of phillipsite and clinoptilolite in deep-sea sedi-
ments. Chem. Geol., 17: 307-318.
Stonecipher, S.A., 1978. Chemistry of deep-sea phillipsite,
clinoptilolite, and host sediment. In: L.B. Sand and F.A.
Mumpton (Editors), Natural Zeolites: Occurrence,
Properties, Use. Pergamon, New York, N.Y., pp.
221-234.
Surdam, R.C. and Boles, J.R., 1979. Diagenesis of volcanic
sandstones. In: P.A. Scholle and P.R. Schluger (Edi-
to .rs), Aspects of Diagenesis. Soc. Econ. Paleontol.
Mineral., Spec. Publ., 26: 227-242.
Watanabe, T., Langseth, M.G. and Anderson, R.N., 1977.
Heat flow in back-arc basins of the western Pacific. In:
M. Talwani and W.C. Pittman III {Editors), Island
Arcs, Deep Sea Trenches and Back-Arc Basins. Am.
Geophys. Union, Washington, D.C., Maurice Ewing Set.,
1: 137-161.
White, S.M., Chamley, H., Curtis, D.M., Klein G. deV. and
Mizuno, A., 1980. Sediment synthesis: Deep Sea Drill-
ing Project Leg 58, Philippine Sea. In: G. deV. Klein, K.
Kobayashi et al. (Editors), Initial Reports of the Deep
Sea Drilling Project, Vol. 58. U.S. Gov. Print. Off.,
Washington, D.C., pp. 964-1014.