FACIES

10

2 Tab.

19 Abb.

257-290

ERLANGEN 1984

On the Origin of Cherts

Zur Genese von Cherts
Christoph Laschet, Aachen

KEYWORDS:

SEDIMENTARY
GENETIC

SCHLUSSEI,WORTER:

PETROGRAPHY

MODEL

- SILICEOUS

- NOMENCLATURE

- GENETISCHES

- KIESELIGE

MODELL

SEDIMENTE

concerns

- NOMENKLATUR

the s i l i c a

the f o r m a t i o n
classification

detrital

siliceous

and p r o b l e m s

are d i s c u s s e d ,
presented.

and

and q u a r t z - s i l i c a

The d i a g e n e t i o

silica

from opaline

in

180-isotopes

retention

of

160-isotopes,

step

precursors.

transformation
conversions

primary

silica

take p l a c e
silica.

solution
are pH,

caused

processes

by the

during

for w h i c h

re-

no

is n e c e s s a r y .

Address:

which

control

and p r e c i p i t a t i o n
temperature,

and w a t e r

Christoph

a sufficient
to e x p l a i n

as no r e l a t i o n

necessary

be c o n s i d e r e d
as c h e r t

volcanic

subordinate

supply

for

silica
silica

amount

cherts.

as the

formation

can

of b i o g e n i c

sources
sources

as w e l l
cannot

of d i s s o l v e d

extensive

of v o l c a n i s m

chert

formations

to m a n y

occurrences

is r e a d i l y

apparent

in r e s p e c t

to s e c o n d a r y

cherts

Dissolved
tal c h e m i c a l

chert

particurlarly
in carbonates.

tributing

phases

of CO 2

Institut

2, D - 5 1 0 0

silica

source

The rate

controlled

by e x t e n s i v e

zones w i t h

ferralitic

of A 1
trated
and

f~r A l l ~ e m e i n e

Aachen

silica, r e s u l t i n g from
weathering,

formation.

silicates

The main question

Laschet,

WHllnerstraBe

the

of s i l i c a

the p r e s e n c e

turbulence.

and s e c o n d a r y

the p r e s e n c e

silica

by the p r e f e r r e d

and the p r e f e r r e d

of s i l i c a u n i t s

factors

cannot
source

without

Also

as o t h e r

sources

of p r i m a r y

silica

conditions
The m a i n

- CHERT

~ 180 in the v a r i o u s

of

solution

of the q u a r t z

as a s o l i d / s o l i d

expulsion

crystallization

is

opal-

is d i s c u s s e d ,

are e x p l a i n e d

reorganization

of cherts

between

that m o s t

differences

phases

Biogenic

facts

a new g e n e t i c m o d e l

opal/quartz

is i n t e r p r e t a t e d
isotopic

the o r i g i n

phases

originated

for non-

is proposed,

The r e l a t i o n s h i p

and it is s u g g e s t e d
cherts

scheme

rocks

concerning

- DIAGENESIS

- PAL~OGEOGRAPHIE

S U M M A R Y

A new

- CHERT

- PALEOGEOGRAPHY

SEDIMENTPETROGRAPHIE

DIAGENESE

ROCKS

initiating

of s i l i c a
global

the s o l u b i l i t y

is low,

and A 1

in r e s i d u a l

laterite.

Geologie

is,

chert

Under

deposits

th e s e

and

the s o l u b i l i t y

therefore,

The d i s s o l v e d

is

palaeoclimatic

of s i l i c a

while

con-

supply

weathering.

is increased,

continen-

is the m a i n

concen-

such as b a u x i t e
silica

und P a l ~ o n t o l o g i e ,

is

RWTH Aachen,

25B

ZU S AMM E N F A S S

supplied to ocean waters where it gives

UNG

rise to increased Si/AI ratios in the

chemical composition of the water. This
increase is mainly influenced by low fluvial
input of disordered
silicates)

clay-minerals

(A1-

which under normal conditions

This is evidenced

by the fact that siliceous

deposits are

very often associated with Al-poor,

ne wird vorgeschlagen. Fakten und Probleme

der Chert-Genese werden d i s k u t i e r t und ein
neues Modell fur die Chert-Genese wird vorg e s t e l l t . Im einzelnen wird die genetische

influence or control the silica concentration of seawater.

Ein neues Klassifizierungsschema fur

n i c h t - d e t r i t i s c h e kieselige Sedimentgestei-

Si-rich

Beziehung von Opal- und Quarz-Phasen aufgez e i g t , wobei ein Ursprung der meisten Cherts

possible under conditions with low concen-

aus opalinen Vorl~ufern angenommen wird,die diagenetische Umwandlung von Opal zu

Quarz als eine f e s t / f e s t Umformung i n t e r p r e t i e r t , und die Unterschiedein den ~180-

tration of Al-silicates,

Isotopenverh~Itnissen in den einzelnen

clay-minerals

and zeoliths,

such as paly-

gorskite, sepiolite and clinoptilolite.

A primary precipitation of silica is therby

pressure-,

and low temperature-,

water turbulence-

and pH-valvues

or high CO2-values.
The increased Si/Al-ration also influences the productivity of silica secreting organisms.

At the same time as oceanic

water becomes enriched in dissolved silica w

continental groundwater

(meteoric water)

also becomes enriched in dissolved silica;

this leads to secondary silification proces-

$i02-Phasen durch die bevorzugte Freisetzung

von 180-1sotopen und die bevorzugte Einbindung von 160-1sotopen, bei der Neuanordnung von Si02-Einheiten bei R e k r i s t a l l i s i e rungsprozessen, wozu kein L~sungsschritt
notwendig i s t , e r k l ~ r t . Die Hauptfaktoren,
die die L~sung und Ausf~llung von SiO2Phasen k o n t r o l l i e r e n , sind der pH-Wert,
die Temperatur, die Anwesenheit von CO2
und die Wasserturbulenz.

ses in perraeable sediments of coastal reThis process is caused by the formation of

Die wichtigste Frage i s t die nach der

Herkunft des gel~sten Si02, das zur Bildung

mixing

von prim~ren und senkund~ren Cherts fUhrt.

gions on contact with marine phreatic water.

zones of marine-phreatic

and silica-

rich meteoric-phreatic waters in which the

precipitation of silica is initiated by
lowering of pH, increase in C02-generation
and eventually also by salinity changes.
This explains the maximum of secondary chert
formation in sedimentary rock sequences of
near shore positions.

Extensive mixing zones

can arise by transgression,

regression and

tectonic uplifting and downfaulting.

These considerations

ohne die Anwesenheit von biogenem SiO 2

stattfinden kann. Auch eine SiO2-Freisetzung
durch Vulkanismus kann neben anderen untergeordneten Si02-Quellen nicht genUgend gel~stes SiO 2 b e r e i t s t e l l e n um eine ausgedehnte Chert-Bildung zu erkl~ren, zumal bei
den meisten Chert-Vorkommen kein Bezug zu
Vulkanismus zu erkennen oder zu finden i s t ,
besonders in Hinsicht auf sekund~re Chert-

help to explain

the almost time-equivalent occurrences

Biogenes SiO 2 kann nicht als die prim~re

SiO2-Quelle gelten, da Chertbildung auch

of

Bildungen in Karbonaten.

primary and secondary cherts in distinct

periods of the earth history,

in addition

to the increase in the productivity

silica secreting organisms.

of

The supposed

Gel~ste SiO 2 aus kontinentalen, chemischen Verwitterungsprozessen i s t die wicht i g s t e Quelle, und der Ausl~ser fur eine

restrictions of secondary chert formation

ausgedehnte Chert-Bildung. Oas Angebot

to near-shore positions could prove to be

an SiO 2 wird so durch ausgedehnte globale,

pal~oklimatische Zonen mit f e r r a l i t i s c h e r

a very important tool in palaeogeographic

sequences now found in deeper water environ-

Verwitterung k o n t r o l l i e r t . Unter chemischen

Verwitterungsbedingungen (z.B.warmfeuchtem

ments,

Klima) s t e i g t die L~slichkeit von SiO 2

reconstructions

especially

for sedimentary

und Silikaten an, w~hrend die L~slichkeit

259

yon Al gering i s t und Al daher in residua-

sen in permeablen Sedimenten von KUstenre-

fen Ablagerungen wie Bauxit und L a t e r i t

gionen kommt bei Kontakt mit marinem phreati-

konzentriert wird. Das gel~ste SiO 2 wird

dem Meerwasser zugefUhrt und verursacht

schem Porenwasser. Dieser Proze~ wird durch

dort ein ansteigendes Si/Al Verh~Itnis in

phreatischem und Si02-reichem meteorisch-

der chemischen Zusammensetzung des Wassers.

Dieser Anstieg wird weiter durch eine geringe Zufuhr von Tonmineralien ( A l - S i l i k a -

Wert Senkung, C02-Entwicklung und eventuell

auch durch Salinit~ts~nderung hervorgerufen.

ten) verst~rkt, die unter normalen Bedingungen die Si02-Konzentration im Meerwasser beeinflussen oder k o n t r o l l i e r e n . Geringe
Mengen von Tonmineralien im Meerwasser k~nnen daher zu einem Anstieg der Si02-Konzent r a t i o n im Meerwasser fUhren. Dies wird
durch die Tatsache belegt, dab kieselige
Ablagerungen oft mit Al-armen, Si-reichen
Tonmineralien und Zeolithen wiePalygorskitt
Sepiolith und C l i n o p t i l o l i t h assoziiert
sind. Eine prim~re Ausf~llung von SiO2 i s t
daher unter Bedingungen mit niedrigen Konzentrationen von Al-Silikatenm und niedrigen
Temperatur-, Druckp Wasserturbulenz-, pH-

die Bildung von Mischungszonen aus marinphreatischem Porenwasser, bei einer pH-

Ausgedehnte Mischungszonen entstehen durch

Transgressionen, Regressionen und durch
tektonische Hebung und Senkung. Dies erk l ~ r t , warum ein Maximum der Verbreitung
von sekund~ren Chert in sediment~ren Sequenzen eines kUstennahen Bereiches zu beobachten i s t . Diese Betrachtungen machen es
sowohl m~glich, das fast g l e i c h z e i t i g e Auftreten yon prim~ren und sekund~ren Cherts
in bestimmten Perioden der Erdgeschichte
wie auch die BIUtezeiten von Organismen mit
kieseligem Skelett zu erkl~ren.
Eine Beschr~nkung der sekund~ren Chert-

Werten oder erh~hten C02-Werten m~glich.

Ein zunehmendes Si/Al-Verh~Itnis beeinfluBt
ferner auch die Produktivit~t von Kiesel-

Bildung auf kUstennahe Bereiche k~nnte sich

als ein wichtiges H i l f s m i t t e l bei pal~ogeographischen Rekonstruktionen herausstellen,

organismen. Zur gleichen Zeit, in der Meerwasser mit gel~stem SiO 2 angereichert wird,
wird auch kontinentales Grundwasser (meteo-

speziell im Hinblick auf Sedimentfolgen mit

sedund~ren Cherts, die j e t z t in gr~Beren
Wassertiefen angetroffen werden.

risches Wasser) mit gel~stem SiO 2 angereichert, wodurch es zu S i l i f i z i e r u n g s p r o z e s -

INTRODUCTION

D e a l i n g w i t h chert genesis m e a n s d i s c u s s ing

several

problems,

troversial subjects

w h i c h h a v e b e e n con-

for c e n t u r i e s of geo-

logical r e s e a r c h work;

as a r e s u l t v a r i o u s

cesses

leading to the p r e s e r v a t i o n of

s i l i c e o u s d e p o s i t s or concretions,

the

r e s t r i c t i o n of e x t e n s i v e chert f o r m a t i o n
to d i s t i n c t g e o l o g i c a l p e r i o d s

and the

t h e o r i e s on the o r i g i n of cherts h a v e b e e n

d i a g e n e t i c e v o l u t i o n of s i l i c a p h a s e s and

suggested,

deposits,

The m a i n p r o b l e m is the q u e s t i o n

F i r s t of all an i n t r o d u c t i o n to

of the sources of silica leading to any kind

the silica p r o b l e m is given,

of chert formation,

Other problems which

the c o n f u s i o n w h i c h exists in the nomen-

have b e e n d i s c u s s e d

c o n c e r n the p r i m a r y and/

clature of n o n d e t r i t a l

depicting

sediments

and rocks

or s e c o n d a r y o r i g i n of chert - a l t h o u g h it

(for w h i c h a new c l a s s i f i c a t i o n m o d e l is

should be w e l l a c c e p t e d by now that there

proposed),

are s i l i c e o u s rocks of p r i m a r y as w e l l as

posing non-detrital

of s e c o n d a r y o r i g i n - the time of s e c o n d a r y

the d i f f e r e n t silica sources and their in-

chert formationj

the e n v i r o n m e n t in w h i c h

c h e r t f o r m a t i o n takes place,
silica replacement,
i n o r g a n i c origin,

the c a u s e of

the o r g a n i c and/or

the c o n d i t i o n s

and pro-

fluences,

the d i f f e r e n t S i 0 2 - p h a s e s
siliceous

the p h y s i c o c h e m i c a l

controlling

the solutions~

and p r e s e r v a t i o n

com-

formations,

parameters

precipitation

of s i l i c a phases,

facies d e p e n d e n c e of p r i m a r y

the

and s e c o n d a r y

260

chert formation,

Aachen).

and last but not least

the diagenetic evolution of SiO2-phases.

This thesis and further

concerning

studies

the behavior of silica resulted

in a model demonstrating mechanisms which

This paper tries to give a critical review of about 700 papers,

studied in con-

nection with the silica problem.

The litera-

ture study was the main part of the author's

thesis at the Geological

Institute

might explain the genesis of all kinds of

siliceaous

sediments

and concretions of

non-detrital primary or secondary origin

inititated by one single process.

(RWTH

PROBLEMSAND FACTS CONCERNING THE ORIGIN OF SILICEOUS ROCKS

2.1

THE CLASSIFICATION (NOMENCLATURE) PROBLEM place-name bound (novaculite: Arkansas,

opoka: Poland); idiomatic expression:
OF SILICEOUS SEDIMENTS AND ROCKS OF NON(Feuerstein, flint, silex); etc.

USA;

DETRITAL ORIGIN

Early in the history of mankind siliceous

rocks were used by our ancestors t and names
such as flint,
focaria

flynte,

frystan and petra

(the cook's stone)

(HILL, 1911)

indicate the use of siliceous

stones as

tools.

Siliceous

tires)

are primary non-detrital

deposits

sediments and rocks

(silici-

siliceous

and secondary silicifications

inorganic or organic origin.

silicification

of

Two types of

can be observed:

I. Silica impregnation of a sediment or

rock by silica-cement
KALKOWSKY

(= Einkieselung:

(1902)~ e.g.: Tertiary quartzites)

2. Replacement of a sediment or rock by

silica

The following terms in arbitrary succession are used for siliceous rocks or sediments (silicitites):
chert, Hornstein (hornstone), silexite,
phthanite, Kieselschiefer, Lydit, Lydianstone, novaculite, jaspis, jaspilite,
jasperoid, jasperite, Jasper, radiolarite,
diatomite, spicularite, spongio!ithe,
spongit, spongilite, spiculite, Feuerstein,
flint, silex, porcelanite, opoka, chaille,
chaize, tripel, tripoli, tripoli,e, sillcrete, Kieselsinter, geyserite, microquartzite, Kieselgur, InEusorienerde, rottenstone, buhrstone, adinole, Kieselkalk,
Chalcedonilite, Polierschiefer, Klebschiefer, basanite, touchstone, limnoquartzite,
opalite, opaline claysteone, whetstone,
h~lleflinta, Lechatelierite, Diatdmeenerde,
petrosilex, Hottenstein and perhaps even
more (LASCHET, 1982).

(chert-nodules

in carbonates)

Some of the above terms are ambiguous,

as for example adinole
1918); basanite,

Over forty names have been given to

siliceous rocks and sediments
ture of earth-sciences,

in the litera-

all describing more

or less the same or slightly different

siliceous formation,
of non-detrital
siliceous

(The deposition of

skeletons is not considered here

as detrital).
confusing,

which consist mainly

silica.

This variety of names is

particularly

if they are used

under different points of view and with

varying definitions.

(albite rock: DAVIS

siliexite and spiculite

(magmatic rocks),

shouldn't be used at all.

Some terms are even wrong,

"Kieselschiefer"

as for instance

(siliceous shale)

a sili-

ceous rock which is often not cleaved at

all. Buhrstone,

rottenstone,

Hottenstein,

Fuller's earth and tripoli are terms for

weathering products of siliceous rocks.
until now a useful nomenclature
ceous sediments and rocks

So

for sili-

(silicitites)

has

been missing.

The following aspects

have led to different names for siliceous

sediments and rocks:

In Table 2 I have tried to develop a

classification scheme which takes into
consideration the diagenetic degree,

crystallinity (opalite); stratigraphic

reference (Flint; -Upper Cretaceous silifications); application (flintstone, wetstone, touchstone); origin (radiolarite) ;

the content of the impurities

and

and of the

biogenic silica in silicitites.

This scheme

can be used for silicitites of primary and

261

of more impure and porous siliceous rocks

Def.: Opalite (redefinedLASCHET

HILL 1911)

(but does not have the true vitreous

Opalite is a poorly consolidated, solid,

siliceous rock which consists more than
50 % of inorganic and organic opaline
s i l i c a phases (opal-A) and porosity of
more than 40 %. Opalites are porcelanite
and chert precursors.

appearance

of chert),

and opalite to

describe rather pure siliceous

porcelanite precursors

chert or

(Table I).

Rather pure immature silicitites

Def.: Porcelanite (partly after BRAMLETTE 1946,

IIJIMA & TADA 1981)
Porcelanite is a consolidated siliceous
rock which consists mainly of organic and/
or inorganic, non-detrital opal- and
quartz-silica phases (50-90 %). Compared
to cherts i t has an higher content of
other components (10-50 %) and a higher
porosity (15-40 %). The higher porosity,
and the higher content of other components gives siliceous rock the appearance
of unglazed porcelain, through i t s dull
luster. Porcelanite is normally less
hard, dense and vitreous than chert.
A true porcelanite shows a high porosity and a high opal-CT content and should
be termed c r i s t o b a l i t i c porcelanite. A
siliceous rock wlth less porosity and
consisting mainly of non-detrital quartz
s i l i c a phases (50-75 %) and 25 to 50 %
of other components should be termed
(quartz)-porcelanite because of i t s dull
luster.
A use of the term porcelanite in a
mineralogical sense is not advisable
because i t is a descriptive term which
conforms to the dull luster of a s i l i ceous rock. The dull luster (of unglazed
porcelain) is more or less due to the
higher degree of impurities. A siliceous
rock consisting to 75-90 % of nondetrital quartz-silica phases should
be called porcelanitic chert (impure
chert).

sisting mainly of opal-CT

be called "cristobalitic
field 3). The adjective

for differentiating
and immature

5) should

chert"

(Table 2,

"cristobalitic"

takes into consideration

stage of silicitites

con-

(Fig.

the diagenetic

and is, thus, useful

between mature

(cristobalitic

chert)

(chert)
silici-

tites. Mature silicitites with more than

10 % and up to 25 % of impurities
be termed porcelanitic

should

chert, because of

their duller appearance

(Table I). Field

12 (Table 2) is problematic.

Although the

term porcelanite has been mainly used to

describe highly siliceous
silicitites

(but impure)

consisting mainly of opal-CT,

impure silicitites

(25-50 % impurities)

consisting only of non-detrital quartzsilica phases should be likewise called

porcelanite because of their unglazed
porcelain appearance.
chert"

The term "porcelanitic

for a siliceous rock with 25-50 %

of impurities would be wrong.

porcelanite

Therefore,

consisting mainly of opal-CT

should be called "cristobalitic porcelanite"

Def.." Chert

(partly after llJl~

& TADA 1981)

Chert is a dense, compact, hard, though

and nearly vitreous rock with l i t t l e
porosity (0-15 %). I t consists mainly of
non-detrital q u a r t z - s i l i c i a phases of
organic and/or inorganic o r i g i n and shows
only a small amount of impurities
(0-10 %). Cherts with opal-CT and Quartzphases should be called c r i s t o b a l i t i c
chert. A chert with more than 10 % and
up to 25 % of other components (impurit i e s ) than non d e t r i t a l q u a r t z - s i l i c a
phases should be called porcelantic
chert.
Table I. Definitions
and chert,

of opalite,

porcelanite

to distinguish it from porcelanite consisting

of quartz-phases
"cherty"

only. Terms as the adjective

shouldn't be used,

sandstone"

(HUMPHRIES,

i.e.,

"cherty

1956).

The outer appearance of silicitites

be described by adjectives
lenticular,

bedded,

etc.

porcelanitic radiolarian

can

such as nodular,

(e,g., bedded
chert - Table 2,

field 8).
Siliceous rocks containing more than
25 % of skeletons of siliceous organisms
should be called radiolarian chert

secondary origin. Basic terms used are

opalite
laneous,
"chert"

(opaline),

porcelanite

porcelanitic)

(porce-

and chert. The term

is applied because it is the most

popular name for a rather pure, dense and

hard siliceous rock; porcelanite
because it best describes

is used

the appearance

(Table

2c, field 4), or clayey radiolarian opalite

(clayey radiolarite)

(Table 2c, field 10).

For silicitites with less than 25 % of

siliceous

skeletons,

radiolarian-rich
bearing

a description such as

(10-25 %) and radiolarian-

(0-10 %) should be used.

262

Non-detrital siliceous componentsincluding biogenic siliceous skeletons in %

go - 100

,o

,02,

251o

O-

Othercomponents
(includingdetritalsilica-phases)in %
k
0 - I0

10 - 25

ms

0s

25 - 50

[7590

10

9000

13
17
21
.... bearing
...... rich
.............
si I iceous
opal-rich
opal-bearing
siliceous ooze, earth or mud
]
[
.......................... ou,
]
T
10.............
7 .... bearing ~ ...... rich
,, opaline I'8 opal-rich
122opal-bearing
opalite
]
[
[
...........................
]
=
3 .... bearing
7 ......rich ] II............. 15 porcelanitic T19
-&
(cristobal I tic)]
opal<T-rich 123opal=CT_bearing
[
cristoballtlc
cristobalitic
porcel
anite
[
...........................
]
chert
]
I

4 .... bearing

12... ..... . ....

...... rich
porcelanitic
chert

I porcelanite
(quartz)

T24

16 porcelaneous 20 miqoquartz-,
microquartz-,
or cnalceoony- [or chalcedonyrich
oearlng
..oo.

....

. .....

oo,.

....

o..o

Table 2 a. Classification scheme of non-detrital siliceous sediments and rocks (including

biogenic silica

clay-bearlng j 5
stl

clay-rich
ceous

I9 clayey
mud

clay-bearing 16

day-rich
opalite

I I0 clayey

clay-rich

1 clayey.

3 clay-bearing 7
cristobalitlc
chert

13 siliceous [17 opal-rich ]21 opal-bearing

I
argillaceous
mud
j

14 opaline
I

15 porcelaneceous[19
123
(cristobalitic)
opa1-CT-rich opa1-CT-bearing
]
[
claystone
]

cristobalitic porcelanite

cl ay-bearing 8
(quartz )
porcel
chertanitic I

[18 opal-rlch 122 opal-bearing

clay
]

6 porcelaneceous IrmCOqartz
crja.lceoony- 12
or ocoqartz
I:naK,eoonyrlcn
oearlng

porcelanite

sbale

Table 2 b. Example for the classification of siliceous sediments and rocks with variable
clay content.,

I clay-bearing [5 clay-rich I9 clayey

[
radiolarian ooze
or
earth

13 si.li~eous
F radio1i~rian- F radiolarianraaloJarlan
rlcn
bearina
[
argillaceous
mud
J

clay-bearing ~-_~ clay-rich [10 clayey

radiolarian
opali te
0

ad i o l

opaline
radiolarian

radiolarianrich

a rite

radiolarianbearing

clay

clay-bearing 7

Icristobalitic
radiolarian I
chert
4 clay-bearing 8

I radiolarian
chert

clay-rich

[11 clayey

cristobalttic
radio]orlon porcelanite
clay-rich
raalchert
ol an an

112 clayey
porcelanlte

15 porcelaneceous1lg radiolarian 123 radiolarian

(cristobal i tic)
(opal-CT)(opal-CT)radiolarian
rich
bearing
[
claystone
l
16 porcelaneceous]20radiolarian 124 radiolarian
Lmicroquartz/chalc~ (m,iq'oqqa~tT.orl .(mjcrqqu.artz.or
radiolarian ] cnaicea.)-ncnI cnaJceojoeanng
[
shale
1

Table 2 c. Example for the classification of siliceous sediments and rocks with variable
radiolarian and clay content.

263

Impure s i l i c e o u s rpcks b e c o m e m o r e and

m o r e p u r i f i e d d u r i n g d i a g e n e s i s by the
e x p u l s i o n of pigments.
porcelanite

into a true chert

neous

A cristobalitic

/opal

-A ,~ opaI-AG
I. opal- AN
opal- CT (p00rly ordered)

(field 7) could t h e r e f o r e e v o l v e
(field 4) and a p o r c e l a -

(cristobalitic)

limestone

could b e c o m e a (quartz)

(field 15)

porcelanite

in

an i n c r e a s i n g t r a n s p a r e n c y in the s i l i c e o u s
rocks. A very h i g h t r a n s p a r e n c y
considered

::,.~7 opal- C

(field

12). This p u r i f i c a t i o n p r o c e s s results

--.

~7opal-CT

ordered)
(:well

should be

as a c r i t e r i o n for the d e s c r i p -

tion of true q u a r t z - c h e r t s

such as f l i n t s

(field 4), w h i l e impure m a t u r e

siliceous

microquartz

rocks should be called p o r c e l a n i t i c chert

(75-90 % quartz)

or quartz p o r c e l a n i t e

megaquartz

(50-75 % quartz).

A l t o g e t h e r there should be not p r o b l e m

in p l a c i n g

siliceous,

s i l i c a - r i c h and

s i l i c a - b e a r i n g rocks of v a r i o u s

composition

in one of the fields of this c l a s s i f i c a t i o n

scheme.

E x a m p l e I: A c o n s o l i d a t e d n o d u l a r h i g h l y
s i l i c e o u s rock w i t h m a i n l y q u a r t z - s i l i c a
phases and less than 10 % clayey m a t e r i a l
should be d e s c r i b e d as: c l a y - b e a r i n g n o d u l a r
chert (short form: nodular-chert)
E x a m p l e 2| A c o n s o l i d a t e d b e d d e d s i l i c e o u s
rock w i t h m o r e than 50 % n o n - d e t r i t a l
s i l i c a - p h a s e s (opal-CT) w i t h m o r e than
25 % of the s i l i c a being r a d i o l a r i a n
skeletons, and w i t h a c a r b o n a t e c o n t e n t
50 % should be d e s c r i b e d a s : c a l c a r e o u s
b e d d e d (cristobalitic) r a d i o l a r i a n porcelanite (short form: b e d d e d porcelanite)

Fig. I". S o l u b i l i t y of s i l i c a phases:

i m m a t u r e (metastable) silica phases,
m a t u r e (stable) silica phases

L ~ s l i c h k e i t von Si0~-Phasen; + m e t a s t a b i l e
Si02-Phasen , ++ s t a b i l e Si02-Phasen
A = a m o r p h o u s (amorph) t G = g e l - l i k e (Gel~hnlich), N = n e t - l i k e (Netz-~hnlich) ,
C = c r i s t o b a l i t e (Cristobalit), T =
t r i d y m i t e (Tridymite), LF = length-fast,
LS = l e n g t h - s l o w

M e t a s t a b l e silica p h a s e s can only be

found in s i l i c i t i t e s no older than the
Early Cretaceous

(v. RAD & ROSCH,

1979),

w h i l e stable s i l i c a - p h a s e s occur m a i n l y

in

s e d i m e n t s and rocks older than the O l i g o c e n e

and only in m i n o r amounts
younger

than the E o c e n e

in s i l i c i t i t e s

(Riech & RAD,

1979),

w h i c h may be the r e s u l t of u n u s u a l d i a g e n e t i c
Detailed classification

e x a m p l e s for

conditions.

With increasing geological

age

s i l i c i t i t e s w i t h d i f f e r e n t clay or radio-

the q u a r t z / o p a l ratio becomes higher,

larian content are given in T a b l e s

does the c r i s t a l l i n i t y due to the d i a g e n e t i c

2b, 2c.

evolution

NON-DETRITALSILICA-PHASES

2.2

Siliceous

s e d i m e n t s and rocks

(Fig. 5 and S e c t i o n 2.5).

The d i f f e r e n t s i l i c a - p h a s e s
products
(siliciti-

of

can be

true p r e c i p i t a t i o n ,

zation or r e p l a c e m e n t

recrystalli-

(indirect p r e c i p i t a t i o n ) .

tes) of p r i m a r y and s e c o n d a r y o r i g i n can

T r u e c h e m i c a l or b i o g e n i c p r e c i p i t a t e s

c o n t a i n or C o n s i s t of v a r i o u s

opal-A

(metastable)
phases)

and m a t u r e

immature

(stable silica-

of n o n - d e t r i t a l origin. The f o l l o w i n g

silica p h a s e s can be d i s t i n g u i s h e d .
Metastable silica-phases:
opal,

opal-A,

opal-CT,

Stable silica phases:

quartz,

LF-chalcedony,

dony,

lutecite,

(Fig.

I).

(Fig.

pseudo-cubic quartz

b i o g e n i c opal-A,
and cavities).

as o p a l - C T
I).

microquartz,megaLS-chalce-

are

(opal-AG and o p a l - A N as cements),

and m e g a q u a r t z

(in v o i d s

O p a l - C T can be either a

p r i m a r y a u t h i g e n i c p r e c i p i t a t i o n p r o d u c t such

biogenic

opal-C

as

ties,

lephispheres

in v o i d s and cavi-

or a s e c o n d a r y d i a g e n e t i c r e c r y s t a l l i -

zation p r o d u c t of b i o g e n i c or i n o r g a n i c
opal-A.

The m o s t i m p o r t a n t r e c r y s t a l l i -

zation p r o d u c t is m i c r o q u a r t z w h i c h seems
to d e v e l o p either d i r e c t l y from b i o g e n i c

264

and inorganic opal-At

or indirectly with an

intermediate step of metastable

formation

opal-CT

1.440 ~ O.O2

(BRAMLETTE,

1946), Opal of

inorganic origin in the porcelanite layers

(It can't be excluded that all

of the Monterey Formation shows an average

silica phases can be formed by precipita-

water content of 3 % and a refractive index

tion).

of approcimately

1.46

(BRAMLETTE,

1946)

which should therefore be opal-CT

(Fig. 2).

It is still disputed whether or not opal-

H2 0 %

CT forms from opal-A through a solution

step where as it seems to be quite clear
that microquartz
microstructural
1979; Sec.

forms through solid-solid

conversion

(RIECH & v. RAD,

2).

3,55
-5,3
6,17
m

Silioa-x
1975)

(HEYDEMANN,

1964; FLORKE e t a l . ,

and kenyaite are intermediate experi-

mental transformation products from opal-A

to opal-CT.

EUGSTER

(1969) has shown that

kenyaite also occurs in natural environments.

The position of the chalcedony

6,27
8,36
"=9
9,16
:" 9
--

refractive
index
1,478
1,4592
1,455
1~4525
1,4478
1,448
lt4499
114425
1,4420
1,4410
1~4380
1~435

occurrences point to an origin of primary

in voids and cavities prior

to the precipitation of megaquartz,

But

(1975) has said: the

"morphology of much chalcedony

in the optical microscope)

I-- ~=

.~., u,_ ~,

-D

,',, 40~
27~

--0

,,- 2oA
-,~12a

~-~
~

.g

-,=, --'~-

"-' 30

yet. Observations of natural chalcedony

as FLORKE et al.

opal-phases

N
-4J

='

silica-phases

in respect to their genesis is not certain

precipitation

size of
crystallites

1,406

Fig. 2. Water content, refractive index,

size of crystallites and scope of opal
phases (modified after data from KOKTA,
1931; MURATA & NAKATA, 1974 and HEIN e t a l . ,
1979).

H~O-Gehalt, Brechungsindex, GreBe der K r i s ~ a l l i t e und Reichweite von Opalphasen.

(as seen

is very simular

to that of much opal-CT and may possibly

be considered

as paramorphic".

So perhaps

the paramorphic crystal habit means that

some chalcedony originated from recrystallization of opal-CT.

Opal precipitation

The highest recognizable

opal-concentrations

are found in the vast

amounts of biogenic opaline silica in deepsea Cenozoic

2.2.1

AMORPHOUS OPALINE SILICA-PHASES

OPAL-A

sedimentary rocks. Biogenic

silica forms from solutions with monomeric

silica

(LEVIN,

1961) which are undersaturated

in silica. According
Opal

(SiO 2 x n H20)

is an amorphous,

hydrated and the least mature and stable

non-detrital

silica phase

(Fig.

I). The

solubility of opal depends on its water

content

(3-30 %). Decreasing water content

of opal results in a decreased

solution

rate of opal and a higher refractive index

(Fig,

2). With t h e loss of water larger

opal particles grow at the expense of

smaller particles which results in a reduced
surface and surface energy of opal particles
accompanied by a decreased solubility
(YARIV & CROSS,

can be an organic or

inorganic process.

1979). Opal of organic

origin is rather uniform in this composition

in the various types of siliceous organisms
indicated by an average water content of
9 % and a refractive index of about

to HEIN et al.

(1978)

biogenic opal-A can be distinguished

inorganically precipitated opal
size of crystallites

from

(opal-A';

20-27 ~; see Fig.

2)

and is thought to be an intermediate

diagenetic product in the transformation
process of biogenic opal-A cement. But
inorganic opal-A does not orSginate

just

from the dissolution of biogenic opal-A

and subsequent reprecipitation;
v. d. BORCH

PETERSON &

(1965) give one of the few

observed examples of inorganically precipitated, unconsolidated,

opaline silica-gel

without participation of biogenic silica.

This amorphous

silica-gel consists of

spherical units with a diameter

range of O.1 - 1.2 ~ m

in the

(10OO-83OO ~, POLLARD

265

& WEAVER,

1973), which are made up of eve~

of LF-chalcedony by the better organization

smaller spherical subunits of 200 ~

of a gel-like opal into LF-chalcedony

(200-500 ~ ~, DARRAGH et al.,

fibers, whose c-axes are orientated

1976) with

a regular spatial arrangement.

These rounded

subunits of silica have the dimensions of

the colloidal system

'SIGH] HOH
content temperature
opaI-AG high high

low

low

opal-CT low

silica
concentration

rate of
precipitation

supersaturated
true solution

rapid

highly diluted
true solution

rapid
Fig. 4. (A) ~ettling of polymeric silica
chains from - neutral solution with tangential orientation to the growing surface
(c-axis perpendicular to the fiber); (B)
Settling of ionized silica tetrahedra from
alkaline solution with perpendicular orientation to the growing surface (c-axis
parallel to the fiber; a f t e r F O L K & PITTMAN

SiOH-.HOH-Gehalte und Bedingungen der

Opal-Phasen-Bildung

such as evaporation,

etc. t

which cause the saturation of dissolved

silica in aqueous solution lead to the
precipitation of inorganic opal by the
slow settling of polymeric
LANGER & FLORKE
a

network structure)

silica units.

(three dimensional

and a gel-like,

amorphous

Their opal-AN is formed from

(with a low value of for "n" in

and its ions

(VARIV & CROSS,

(H3SiO~, H5Si20~,

1979),

etc.), and

opal-AG is formed from supersaturated

LF-chalcedony

true

solutions or sols by rapid precipitation

and the intermediate opal CT(FLORKE,

1955; MALLARD,

1890), whose c-axis is also perpendicular

to the fibers

a high concentration of hydrous silica

SinOn_ I (OH) 2n_1;

Hence opal-AG could be the precursor of

phase Lussatit

supercritical SiO2-HOH fluid phases with

species

1971),
(A) Ablagerung von polymerem SiOp-Ketten
aus * neutraler L~sung mit tangefftialer
Orientierung zur Wachstumsoberfl~che (cAchse senkrecht zur Faser); (B) Ablagerung
von i o n i s i e r t e n Si02-Tetraedern aus a l k a l i ner L~sung mit senkrechter Orientierung
zur Wachstumsoberfl~che (c-Achse p a r a l l e l
zur Faser).

(1974) distinguish between

glass-like opal-AN

opal-AG.

(Fig. 4).

slow

Fig. 3. SiOH-, HOH-content and conditions of formation of coal chases

(after YARIV & CROSS 1979,
3-13% HOH, KEENE 1976; * * 3-6% HOH,
FLORKE 1972)

Processes

tial to the growing surface and perpendicular to the fibers

(10-1OO0 ~).

high-temperature
hot-.- cold supercritical
quenching ~SiO2- H2Q-fluids

opal-AN

tangen-

(Sections 2.2.2,

2.2.6).

If

opal-AG is the precursor of LF-chalcedony,

opal-AN could possibly be the precursor of
LS-chalcedony

and Lussatin

(LAVES,

1939)

whose c-axes are parallel with the fibers

(correct quartz orientation,

Fig.

5).

of more polymeric hydrous silica-species

(with higher values for "n", such as
HI2Si7018).

Opal-AN has the highest SiGH-

content but the lowest HOH-content because

of its dense Si02-network , while opal-AG
has a high SiGH and HOH-content

(Fig. 3).

As illustrated by FOLK & PITTMAN

LS-chalcedony

or in a sulphate rich environment,

The opal-AG type silica quickly precisolution at

a ~ neutral or low pH and low temperature

where

silica is more highly ionized into single

tetrahedra,

which attach one by one to the

growing surface, with the resulting

pitates from supersaturated

(1971)

seems to form in a high pH

(LS-

chalcedony

fibers having the correct quartz

orientation

(c-axis parallel to the fiber,

Fig.

4)).

in the form of silica-tetrahedra which are

polymerized into spiral chains,
by FOLK & PITTMAN

(1971)

as proposed

for the formation

In the high-temperature
Si02-HOH

superciritical

fluid described by FLORKE

(1972)

266

LS-chalcedony

l biogenic opal

] I

inorganic opal

and p e r h a p s opal-AN

is

further i n d i c a t e d by the fact that all

three s i l i c a - p h a s e s v e r y r a r e l y o c c u r as
precipitates

o..-,,
c:

I - -

- - - -

~
.-

--F
~

---'1
sihca-X * 1
or

~e

=
~

"

~-

~,l
~l
"L

,-.

,,!

":'

"

--

.'_

and L F - c h a l c e d o n y m a k e

formed as p r e c i p i t a t e s

in cavities
2.2.6).

(Sections

2.2.2,

such as k e n y a i t e

x 3H20) , m a g a d i i t e

poorly ordered

well ordered
I

""

well
"

ordered

d (Io~)~4.04

Silthydrite
1972)

S H E P P A R D et al.,
inorganic,
deposits

true
precipitate

dony

chalcedony
+ lutecite

1970)

are c o m p o n e n t s of

in Lake Magadi,

w h i c h show s i m i l a r i t i e s
nH20) , and,

according

quartz

silica phases

(Africa),

to opal

(SiO 2 x

to E U G S T E R

of cherts.

O p a l - C T is an i n t e r m e d i a t e ,

metastable

s i l i c a - p h a s e w h i c h can be either a re-

1978;

(MEYERS & JAMES,

S W I N E F O R D & FRANKS n 1959)

(RIECH & v. RAD,

ranging
KELTS,

of any

or a true p r e c i p i t a t e in the form

of o p a l - C T - l e p i s p h e r e s

Diagenetische Entwicklung von opalinen

Si02-Phasen und ihre m~gliche genetische
Beziehung zu stabilen Quarz-Phasen
~FLURKE et a l . , 1975;**auch natUrlich
auftretend; EUGSTER, 1969).

(1969),

OPAL-CT

opal-A,
Fig. 5. D i a g e n e t i o e v o l u t i o n of o p a l i n e
silica phases and their p o s s i b l e g e n e t i c
r e l a t i o n s h i p s to m a t u r e quartz silicap h a s e s (*FLORKE et al., 1 9 7 5 ; * * a l s o natural occurring; EUGSTER, 1969).

to Recent

Kenya

crystallization product

GUDE & SHEPPARD,

(NaSi203(OH) 3 x H20),

siliceous Quaternary

are p r e c u r s o r s

(NaSi11020,5(OH)4

(NaSi7OI3(OH) 3 x 3H20),

(3SiO 2 x H20),

and m a k a t i t e

2.2.2

~-"1 ,
~' ~:

and

massive
fibrous
?
length- slow
9

(Sections

Lussatite

voids

Minerals

fibrous
length-fast

z'~

~1 ~.

g,a

---

and voids

w h i l e opal-AG,

up the m a j o r i t y of s i l i c a - p h a s e s w h i c h are

kenyaite*~
--1-

in c a v i t i e s

2.2.7),

(common o p a l - C T

I
I
I
I

2.2.2,

1979),

in c a v i t i e s or voids
the l e p i s p h e r e s

in size from 4 to 30 ~ m

(WISE &

1972}. T h e r e is still d i s a g r e e m e n t

over the t e r m i n o l o g y of opal-CT,

it consits of d i s o r d e r e d ,

wether

interlayered

~-cristcbalite

and e - t r i d y m i t e

SEGNIT,

or only of d i s o r d e r e d

1971),

tridymite

(OEHLER,

1974). O p a l - C T

(JONES &
low-

1973; W I L S O N et al.,

is the c h a r a c t e r i s t i c

and

s i l i c a should also be m o r e h i g h l y ionized

m o s t common

into single tetrahedra,

as i n d i c a t e d by

where

of hydrous

in the form of a c e m e n t and/or as a m a t r i x

the high c o n c e n t r a t i o n s

silica

s i l i c a - p h a s e in p o r c e l a n i t e s ,

it o c c u r s m a i n l y

species w i t h a low value of "n"

(YARiV &

replacement

CROSS,

fluid.

of f o r m a t i o n opal-CT

shows a bulk r e f r a c t i v e

index of abo,it ].448

(poorly o r d e r e d opal-

1979)

in a s u p e r c r i t i c a l

in a d d i t i o n to high t e m p e r a t u r e
S i 0 2 - H O H fluids,

high p r e s s u r e

So

supercritical
supercritical

S i 0 2 - f l u i d s , and S i O 2 - H O H - F l u i d s w i t h high

CT, Fig.

(KEENE,

as m a s s i v e o p a l - C T

1976).

In an early stage

2). This p r o g r e s s i v e o r d e r i n g of

the d i s o r d e r e d

atomic s t r u c t u r e of o p a l - C T

pH should also result in the f o r m a t i o n of

is also seen in the i n c r e a s i n g

an o p a l - A N - t y p e

x-ray r e f l e c t i o n s

silica-phase

pressure-release

(by quenching,

or l o w e r i n g of pH, etc.)

as a r e s u l t of rapid p r e c i p i t a t i o n
supersaturated
silica.

from a

s o l u t i o n w i t h r e s p e c t to

The r e l a t i o n s h i p of L u s s a t i n and

d(101)-spacing

s h a F p n e s s of

(Fig. 6) and the d e c r e a s i n g

of opal-CT

samples.

~)r- -.

with more than 25 ppm dissolved

silica

under conditions where crystal growth is

slow. Because of its large inner surface
and usually irregular microstructure
contains

the greatest amount of HOH

3 and 4)

(LANGER & FLORKE,

solubility

of opal-CT

R~ntgenbeugungsdiagramm yon opalinen

SiO2-Phasen (nach v. RAD & R~SCH, 1978)
Der kleine Peak auf 4er linken Seite wi~d
durch ~-Tridymit hervorgerufen.

REX,

(FOURNIER,

(GARRISON et al.,

1970; CALVERT,
1972), opoka

diatomites
GRUNER,
earth,

(WEAVER &

(FLORKE et al.,

and bentonites

1940); Fullers's

(FLORKE,

1975),
1955;

earth, diatom-

tripoli and volcanic ashes

1940). Various

1975;

1971; WILSON et al.,

1974) but also from flint-clays

WISE,

1973).

is mainly reported from porcelanite

samples of DSDP
Fig. 6. X-ray diagram of opaline silica
phases (after v. RAD & ROSCH, 1978). The
little peak on the left side is caused
by ~ -%ridymite.

1974). The

lles somewhere near

40 to 70 ppm at 25 ~
Opal-CT

opal-CT
(Figs.

(GRUNER,

terms in the literature

are

more or less identical with opal-CT:

The total variation of d(IO1)

for opal-CT

from the Monterey shale ranges from

4.115 ~ for poorly ordered opal-CT to
about 4.04 ~ for well ordered opal-CT
(MURATA & NAKATA,

Lussatin (LAVES, 1939), Lussatit (MALLARD,

1890), low-temperature cristobalite (FLORKE,
1962), e -cristobalite (REX & MURRAY, 1970);
opal-cristobalite (BRAITSCH, 1957).

1974). The maturity

process of opal-CT is related to temperature

and pressure increases.

The d(I01)

of opal-

Lussatin

(Section 2.2.1)

is a fibrous

e - c r i s t o b a l i t e with its c-axis parallel to

CT seems to be smaller in porcelanite

the fibers,

(impure silicitite;

e-cristobalite with its c-axis perpendicular

coexisting

Table

cristobalitic

silicitite;).

I) than in
cherts

(pure

This points to a petrographic

and Lussatite

to the fiber. Both are varieties

and LF-chalcedony

formation,

LS-chalcedony,

that in purer sili-

of opal-CT

and could be the precursors of LS-chlcedony

dependence in the beginning of opal-CT

suggesting

is a fibrous

(Fig.

5). Lussatin

like

is more bladed than fibrous

ceous rocks opal-CT formation starts earlier

(BRAITSCH,

at lower temperatures

dony has very fine fibers in comparison with

and pressures during

1957). Lussatit like LF-chalce-

the diagenetic evolution than in more impure

LS-chalcedony with more bladed fibers

silicous rocks

(Sections 2.2.2;

(porcelanites),

where opal-

2.2.7).

CT formation starts later in the diagenetic

evolution at higher temperatures
sures

(The difference

results

in d(IO1)

and pres-

2.2.30PAL-C

spacing

from a different time of formationl).

The degree of disorder in the opal-CT lattice

is higher, and the grain-size of opal-CT

Opal-C is a naturally occurring silicaphase associated with volcanic rocks

especially with lava. It is a well-ordered

is lower in clay-rich siliceous sediments

~-cristobalite with minor traces of tridy-

than in carbonate-rich

mite according

to the classification of

JONES & SEGNIT

(1971). The stability of

same age

sediments of the

(The difference

in d(IO1)

is related to petrographic
Mg 2+ - and OH--ions

spacing

conditions[).

in the ration Mg/OH

1:2 enhance the transformation of opal-A

to opal-CT

(KASTNER et al,,

low SiOH-content

opal-C should be higher than poorly ordered

opal-CT and lower than well ordered opal-CT
(Fig. I and 7).

1977). The

(Fig. 3) of opal-CT

supports the assumption that opal-CT

2.2.4

MICROQUARTZ

is

formed very slowly from a highly diluted

Microquartz

(Fig.

8) consists of more or

true solution at relatively low temperatures

less even-grained,

(REYNOLDS,

quartz grains varying between

1970; LANGER & FL~RKE,

1974)

polyhedral,

uniform
I ~/a to max.

268

by relict textures of evaporites

opaI-A

in megaquartz

(CHOWNS & ELKINS,

G e n e r a l l y megaquartz

4.13,~

and dolomite
1974).

can be considered as

a silica-cement precipitating mainly in

opal-CT

cavities.
the

4,03~

2&l

opal-C

There in these cavities

slow precipitation

from

highly diluted solutions with

high pH, high

(ARBEY,1980)
ions,

sulphate

and mobilized

free, limpid crystals.

40 ~

30 ~

to LS-chalcedony

20 ~

content
silica-

leads to well-terminated

crystallographically
50 ~

of silica

inclusion-

Megaquartz

is

and optically related

and lutecite

(SIEDLECKA

1976), which are also formed from solutiQns

with higher pH

(OH-ions)

and higher con-

Fig. 7. X-ray diffraction patterns of opal

and quartz, CuK-radiation (after KASTNER,
1980) 0

centrations

RSntgenbeugungsmuster yon Opal und Quarz

(nach KASTNER, 1980).

evident from transition forms such as

of Mg 2+ and

(Sections 2.2.7;

flamboyant megaquartz
lutecite

sulphate-ions

2.2.8). This is also

and flamboyant

(megaquartz and lutecite with

flamboyant extinction under transmitted

30 ~ m #
MEYERS

(ARBEY,
& JAMES,

1980; FOLK & WEAVER,

1978; THURSTONf

1952;

1972),

It

light)
other

passing

imperceptibly

(CHOWNS & ELKINS,

is the most abundant silica-phase in cherts

PITTMAN,

and shouldn't be considered

from LS-chalcedony

as a cement,

but rather as a recrystallization

product

of metastable opaline silica-phases

ERS & JAMES,

(MEY-

1978). Also microspheres

lephispheres,

1974; FOLK &

1976). Transitions

to petaloid megaquartz

have been observed too

(ARBEY,

In cavities megaquartz

is often found in

1980).

contact zones between LS-chalcedony and

(25-40 ~ m ~) which could formerly have

been opal-CT

1971; TUCKER,

into each

lutecite

are possilby

(SIEDLECKA,

1976) growing in

solutions w i t h a relatively high pH and

evidence of the transformation of opal to

decreased

microquartz

of a higher silica-concentration

(WISE, BUIE & WEAVER,

1972),

silica-concentration,

precipitation of opal
Cryptocrystalline
1 ~m

quartz smaller than

~ is isotropic and shows a brown color

(under the microscope

in transmitted

light),

at the time
the

(opal-AN ?) and LS-

chalcedony could have taken place. Megaquartz shows the slowest rate and is therefore less soluble than microquartz

and

which should result from submicroscopic

pores,

as found in chalcedony.

stalline quartz therefore

Cryptocry-

is, treated as a

variety of chalcedony by LANCELOT

2.2.5

(1973),

quartz

MEGAQUARTZ

n= 1.544 -

The size of quartz grains in megaquartz

varies between 30-250 ~ m
1978). Megaquartz

(MEYER & JAMES S

is macrocrystalline

usually forms mosaics of uniform,

quartz grains. Megaquartz

and

[ fibrou!quartz]

L granularquartz ]

SMITH

1.567

l't

chalcedony
1.539

r)=1,534-

'960 }

mcgaquartzI I micr~

{ ORME

LS-

LF-

4 Lchalcedony~,chalcedony

anhedral

in cavities

shows a tendency to elongate,

[,Jl

197':1 }

idiomorphic

-quartz/

I '"'""' J

grains specially in association with former

evaporites which have been replaced by
silica

(GRIMM,

SIEDLECKA,

1964; RICHTER,

1972),

1971;

sometimes illustrated

Fig. 8. Quartz-phases
relationship.

and their genetic

Quarz-Phasen und ihre 9enetische VerknUpfung.

269

chalcedony
PITTMAN,

(Fig. I). Megaquartz

1971)

(FOLK &

is a final precipitate

in

chalcedony

or its precursors must have

formed generally in solutions with low

solutions with low silica concentrations

Mg 2+ and/or sulphate concentrations

and should be uncommon

(KASTNER et al.,

in cherts of deeper

1977).

water origin.
2.2.7
2.2.6

LS-CHALCEDONY

LF-CHALCEDONY
LS-chalcedony

LF-chalcedony

is the most common

chalcedony-species,

(MUNIER-CHALMAS,

1890)

quartzine is rarer than LF-chalcedony;

with an anomalous

fibers are cruder,

orientation of the x-axis perpendicular

(SIEDLECKA,

1976)

thicker, more bladed

and may show different

to the fiber. LF-chalcedony has an optical

length grading outward until they mimic

orientation of I =

quartz terminations

(-). It is nearly almost

always found as a cavity-filling.

of LF-chalcedony
up to 5 mm long

The fibers

1971; CHOWNS

or
its

(FOLK & PITTMAN,

& ELKINS,

1974).

are about 20 ~ m thick and

(SIEDLECKA,

1976). LF-

LS-chalcedony,

in fact, is rich in fluid

chalcedony forms very neat regular spheru-

inclusions

lites of delicate fibers,

interstitial water:

arranged in a

(high water contentL ; saline

SMITH,

1960) but general-

precise radial pattern with all the fibers

ly shows fewer impurities

having the same length

dony. Opal-AN which might be a precursor

(FOLGK & PITTMAN,

1971). The c-axis is orientated

to the growth surface
MAN,

1971; WILSON,

tangentially

(Fig. 4), FOLK & PITT-

1966). It forms at

relatively high silica-concentration

low pH from polymeric

(MILLOT,

captured

1970)

(SWINEFORD & FRANKS,

a recrystallization

1959)

inclusions

oriented parallel to the fibers

1976).

According
from

(opal-AG) . Evidence

chalcedony

to FOLK & PITTMA/~

alkaline solutions with a high initial pH

or in a sulphatic environment with freefloating

fact, that LF-chalcedony

SiO2-concentration.

shows no pseudo-

crossings,

no texture

no relict carbonate inclusions,

and that impurities

as Fe-ions are incor-

porated into the precipitation,

which is

shown by Fe-rich growing rings in cavityfilling

LF-chalcedony

(SIEDLECKA,

1976).

ionized SiO2-units

at a high

Observations

of KEENE

(1976) who described the association of

LS-chalcedony with barytes
or Mg-calcite,

and/or dolomite

and of KASTNER

(1980) who

showed the importance of Mg- and sulphateions for the formations

of LS-chalcedony,

verify the above conclusions.

Such Fe-rich layers are not found in LS-

FOLK & PITTMAN

chalcedony.

evaporitic

This suggests that LF-chalce-

(1971) LS-

forms in an environment with

for this conclusion is supported by the

morphs after other minerals,

flamboyant

extinction into megaquartz with numerous

(TUCKER,

suggests

of LF-chalcedony

opal-CT or, even opal-A

has the highest SiOH

! Sometimes LS-chalcedony passes

and the

similarity with cavity-filling banded

opal-CT

content

imperceptibly with undulous

and

silica chains. The

anomalous crystal structure,

water inclusions

of LS-chalcedony

than LF-chalce-

(1971)

But after

postulated

an

influence for the LS-chalcedony,

dony isn't a primary precipitation product

KASTNER

but rather a recrystallization

with high pH and Mg- and/or sulphate-ion

product of

opal-AG perhaps with an intermediate

(1980) pointed out that conditions

concentration

are sufficient to explain

transition step through opal-CT

(lussatite)

the environment of LS-chalcedony-formation.

which is shown by LF-chalcedony

sponge

LS-chalcedony

(or its precursors opal-AN ?

spicules which were originally opal-A

and lussatin)

can mainly be found replacing

(opal-AG)

evaporites

(CHOWNS & ELKINS,

1974).

fossils
Devonian filamentous algae microfossils
in LF-chalcedony

(FAIRCHILD et al.,

1973)

also support the theory of a gel-like

opaline precursor for LF-chalcedony.

MAN,

(anhydrites,

gypsum),

(CHOWNS & ELKINS,

1971; SIEDLECKA,

In Sabkha-like

as well as

1974; FOLK & PITT-

1976; TUCKER,

1976).

environments or sediments

with alkaline or sulphate-rich pore fluids

LF-

(containing Mg-, Ba-, St-, SO4 and Na-ions)

270

ideal c o n d i t i o n s are a v a i l a b l e for the

f o r m a t i o n of L S - c h a l c e d o n y

SILICA-SOURCES

2.3

(McBRIDE & FOLK0

1977)o

T h e m o s t i m p o r t a n t factor in r e s p e c t to
the o r i g i n of cherts are the silica sources

2.2.8

LUTECITE

leading to the f o r m a t i o n of p r i m a r y and

s e c o n d a r y cherts.

Lutecite

(MUNIER-CHALMAS,

1890)

is the

But w h a t kind of s i l i c a

source can p r o c i d e the v a s t amounts of

third c h a l c e d o n y s i l i c a - p h a s e w i t h a f i b r o u s

silica is also v e r y decisive.

habit;

silica s o u r c e w h i c h is active over long

its c-axis is o r i e n t e d a p p r o x i m a t e l y

30 ~ to the fibers. A c c o r d i n g
ELKINS

(1974)

to C H O W N S

&

l u t e c i t e is p s e u d o - f i b r o u s

Only a

p e r i o d s of time and w h o s e i n f l u e n c e s extend into larger r e g i o n s b e y o n d local

and a t r a n s i t i o n form b e t w e e n L S - c h a l c e d o n y

boundaries

and m e g a q u a r t z

p r e t a t i o n of p r i m a r y s i l i c e o u s d e p o s i t s

(flamboyant lutecite).

It

is i m p o r t a n t for a g e n e t i c inter-

occurs c h i e f l y as a r e p l a c e m e n t in the same

and s e c o n d a r y

environment wheme LS-chalcedony

one thing is c e r t a i n - p r i m a r y and s e c o n d a r y

Its m o s t c o ~ o n

o c c u r r e n c e is a s y m m e t r i -

cally-extinguishing

c h e v r o n - l i k e grid of

c o a r s e fiber c r o s s i n g
grading

2.2.9

is found.

into q u a r t z

at about 60 ~ and

(FOLK & PITTMAN,

P S E U D O C U B I C QUARTZ

1971).

(MELANOPHLOGITE)

C u b i c - or f o r t i f i c a t i o n - z o n e d quartz is
a low t e m p e r a t u r e S i O 2 - m o d i f i c a t i o n
BRIDE & FOLK,
1963),

and,

(Mc

1977; S K I N N E R & A P P L E M A N I

like L S - c h a l c e d o n y and lutecite,

occurs as an a u t h i g e n i c m i n e r a l
phatic environment
B a S O 4 and CaSO4;

in a sul-

(paragenesis w i t h SrSO4,

TROGER,

1967).

Sabkha-

like c o n d i t i o n s w e r e also d e s c r i b e d by
WITTENBORG

(1933)

for the f o r m a t i o n of

p s e u d o c u b i c quartz

in the D e v o n i a n jaspis

of the R h e n i s h - S c h i e f e r g e b i r g e .
o r i e n t a t i o n of the c-axis,

The

is per-

p e n d i c u l a r to the g r o w i n g

surface.

o p i n i o n of M c B R I D E

(1977)

& FOLK

In the

two

morphoses

I. Quartz p s e u d o -

after cubic m i n e r a l s

because

cherts h a v e a v e r y close g e n e t i c r e l a t i o n s h i p .
T h e fact t h a t p r i m a r y
occur t o g e t h e r

and s e c o n d a r y cherts

in d i s t i n c t p e r i o d s of the

earth's h i s t o r y

s u p p o r t s the theory of a

contemperaneous

f o r m a t i o n of p r i m a r y cherts

and s e c o n d a r y cherts.

One e x a m p l e may stand for m a n y others

here:

Secondary

chert nodules in the car-

b o n a t e s of the Lower C a r b o n i f e r o u s
Belgium,

England

contemporaneous

of

and Ireland are a l m o s t

(secondary s i l i c i f i c a t i o n

takes p l a c e in s e d i m e n t s w h i c h are just

s o m e w h a t older than c o n t e m p o r a n e o u s p r i m a r y
siliceous

sediments

I) to the d e p o s i t i o n a l

s i l i c e o u s rocks of the C u l m
schiefer)

(Kulm-Kiesel-

in the " R h e n i s h - S c h i e f e r g e b i r g e " .

t r a t i o n s of p r i m a r y s i l i c e o u s
biogenic)

deposits

(mainly

in d e e p sea s e d i m e n t s of

the Upper C r e t a c e o u s

and E a r l y T e r t i a r y

(described in m a n y DSDP-reports)

p o s s i b i l i t i e s e x i s t for the f o r m a t i o n of
p s e u d o c u b i c quartz:

formations,

A l s o p r o c e s s e s w h i c h lead to high concen-

like the c-axes

of l u s s a t i n and L S - c h a l c e d o n y ,

siliceous

should be

seen in c o n n e c t i o n w i t h the c o n t e m p o r a n e o u s
f o r m a t i o n of s e c o n d a r y chert n o d u l e s

(e.g. halite)

(flints)

in the U p p e r C r e t a c e o u s . M a n y m o r e e x a m p l e s

or 2. D i r e c t p r e c i p i t a t i o n of s i l i c a in a

can be found in other d i s t i n c t p e r i o d s of

pseudocubic

the e a r t h ' s history.

form.

GRIMM

(1962) d e s c r i b e s

halite cubes e n c r u s t e d by a quartz skin,

The h i g h number of i n c l u s i o n s

in layers

T h e s e time e q u i v a l e n c e s

s u g g e s t t h a t p r i m a r y as w e l l as s e c o n d a r y
cherts of d i s t i n c t p e r i o d s in the earth's

of p s e u d o c u b i c q u a r t z also s u g g e s t s an

h i s t o r y must,

o r i g i n from a p r e c u r s o r

e x p l a i n e d by one and only one m a j o r initia-

as o p a l - A

silica-phase

such

(opal-AN ?). The layered s t r u c t u r e

of p s e u d o c u b i c q u a r t z

is p r o n o u n c e d or

ting p r o c e s s

or at least should be,

leading to a h i g h e r supply of

d i s s o l v e d s i l i c a in any w a t e r

pherhaps

caused by fibers of fluid in-

cluding the p o r e - w a t e r

clusions

(O.2 ~im). It shows one to s e v e r a l

rather u n l i k e l y

sharply defined straight-lined

segmented

system

system).

that one s i l i c a source leads

to the f o r m a t i o n of p r i m a r y s i l i c e o u s de-

zones, w h i c h have a b r o w n color in trans-

posits,

mitted

s i l i c a s o u r c e leads to a s e c o n d a r y

light, due to fluid inclusions.

(in-

It is

and another a l m o s t c o m t e m p o r a n e o u s

271

s i l i c i f i c a t i o n p r o c e s s in s e d i m e n t a r y

be found in the Lower C a r b o n i f e r o u s

rocks w h i c h have a l r e a d y b e e n deposited.

b o n a t e s of Belgium.

If this r e a s o n i n g is correct,

be very hard to e x p l a i n or to prove,

example,

The a r g u m e n t

it w i l l

originated

for

cherts

from the d i s s o l u t i o n of s i l i c e o u s

microfossils

that the " K u l m - K i e s e l s c h i e f e r "

that s e c o n d a r y

car-

and the r e s u l t i n g i n o r g a n i c

(primary cherts or p o r c e l a n i t i c cherts;

r e p r e c i p i t a t i o n of s i l i c a in the form of

S e c t i o n 2.1)

n o d u l e s by r e p l a c i n g c a r b o n a t e s

of the Lower C a r b o n i f e r o u s

(Tournaisian and Vis~an)

secondary chert-nodules

be q u i t e p l a u s i b l e at first sight;

as w e l l as the

(Tournaisian and Vis~an)

s i l i c a release.

n o d u l e s in L a t e P r e c a m b r i a n

the Harz M o u n t a i n s

release,

w h i c h o r i g i n a t e d under d i f f e r e n t g e o l o g i c a l
conditions

W h i l e the K u l m - K i e s e l s c h i e -

silica-source.

the L o w e r C a r b o n i f e r o u s

necessary

in

primary,

in B e l g i u m , w h i c h

productivity

for the f o r m a t i o n of chert

biogenic,

siliceous

in

sediments

and

rocks c a n ' t be e x p l a i n e d by the d i s s o l u t i o n

(cements)

and r e p r e c i p i t a t i o n of b i o g e n i c s i l i c a as

and p a r t i a l c a r b o n a t e - r e p l a c e m e n t by silica,
to the same process.

at least not

nodules. A l s o the s i l i c e o u s m a t r i x

c a r b o n a t e s of

r e s u l t e d f r o m silica i m p r e g n a t i o n

To our k n o w l e d g e no s i l i c e o u s

in the d i m e n s i o n s w h i c h w o u l d h a v e been

it is d i f f i c u l t to r e l a t e the

the n e a r l y c o n t e m p o r a n e o u s

times,

for an i n o r g a n i c

o r g a n i s m s e x i s t e d at that time,

silica-

f o r m a t i o n of s e c o n d a r y chert nodules

compared w i t h P h a n e r o z o i c

but w h i c h call n e v e r t h e l e s s

and

could still be ex-

p l a i n e d by an i n c r e a s e d v o l c a n i c

carbonates

(period w i t h a m a x i m u m in chert-formation)

are both due to

or h y d r o t h e r m a l -

fer of the " R h e n i s h - S c h i e f e r g e b i r g e "

but

it can't e x p l a i n the f o r m a t i o n of chert

in the p l a t f o r m

c a r b o n a t e s of the L o w e r C a r b o n i f e r o u s

an i n c r e a s e d v o l c a n i c -

seems to

the s i l i c e o u s s k e l e t o n s often show no sign

A l s o an i n c r e a s e d

of d i s s o l u t i o n

of s i l i c e o u s m i c r o o r g a n i s m s ,

(ROBERTSON,

1977)

and

w h o s e s k e l e t o n s could have b e e n another

t h e r e f o r e c a n ' t have t h e m s e l v e s b e e n the

e f f e c t i v e silica source,

s i l i c a source.

contemporanity,

can't e x p l a i n the

If we c o n s i d e r

the v i e w

m o r e c l o s e l y that the g e n e s i s of cherts

as h a r d l y any i n d i c a t i o n s

of an e a r l i e r h i g h c o n t e n t of s i l i c e o u s

m i g h t be r e l a t e d to b i o g e n i c a l l y

microorganisms

silica,

(e.g., r a d i o l a r i a n s )

can

secondaryi

I Si0 -SOURCESi

primary ]k

fixed

it m u s t b e c o m e obious that b i o g e n i c

dissolved silica

J
rrestrial: fluvial
: eolian

fluvial
: glacial
- meteoric-phr.
- vadose
~J__~i.n e- phreatic
,'

~ - 2

]~

_: volcanic
N ~"
Fine: biogenic
_g nic (authigen3
(aut]
9 mineral-hooformationJ---I

hydrnthermal

ion

J precipitation
1. direct: inorganic physico-chemical
2. indirect: by siliceous organisms
3. indirect: by mineral-neoformation

so,d si,,c,

Fig. 9. C i r c u l a t i o n of d i s s o l v e d and solid silica p h a s e s

L A S C H E T 1982).

accumulation and concentration J

of silica phases in,or as sediments

in the w a t e r systems

(from

Kreislauf von gel~sten und festen SiO2-Phasen in Wassersystemen (aus LASCHET, 1982).

272
A.

Input of dissolved silica into ocean water:

Total of silica sources:

silica

8,5
5

HEATH (1974)
BURTON & LISS (1973)

source

I)eMASTER (1981)

by silica

6,1
6

12
12

1,8

4,3

CALVERT (1968)
in detail:

fluviatil dissolved silica:

3,2
4,2 ~
4,27
4,3
6
4,25

0,8

GOLDBERG (1963)
DeMASTER (1981)
HEATH (1974)
CALVERT (1968)
HOLLAND (1978)
LIVINGSTON (1963)

(Fig,

can't
9),

be

It only

of

fixed

the

organisms

related
silica

as E L D E R F I E L D
have

shown,

to t h e

dissolved silica of esturarine mixinq

processes:

and

tions?

dissolved silica of artic weathering

processes:
0,02

HURD (1977)

to t h e

(1972)

balance

authors

(Figs.

101

1,9
+
0,001 0,3
0,054
0,0003

play

a subordinate

EDMOND et al. (1979)

CALVERT (1968)
WOLERY & SLEEP (1976)
HEATH (1974)
WOLLAST (1974)

0,03
0,81

CALVERT (1968)
BERGER (1968)

Extraction of dissolved silica from ocean

water:

neither

the

organisms
and

the

terrains

lakes,

cherts,

and

continental

only

and
sediments

silicifica-

silica

sources

and can

explain

of a l l p r i m a r y

those

the

released

transported

the

silica-

of s i l i c e o u s

But

that

surface

is o f

leads

demonstrate

formation

silica

(1974)

of v a r i o u s

also

role

clearly

dissolved

secondary

proliferation

secondary

show quite

of

or hydrothermal

nor

of

siliceous

11)

is

processes,

source

calculations

volcanic

1,0
0,01
0,9

release

the deposition

of

that

source,

siliceous

silica

of primary

formation

Mass

of

productivity

organisms,

by

Neither

and GARRISON

But which

hydrothermal and volcanic dissolved silica:

dissolved silica of submarine weathering

processes:

B.

the

silica

by volcanogenic

increased

secreting

originated

organisms,

productivity

dissolved

source

a potential

which

of a n o t h e r

secreting

increased

silica

represents

silica

the utilizaition

preservation

BIEN et al. (1958)

a primary

calculations

amount

form

of

terrestrial

by ravers

run off

highest

and by

to o c e a n s

and

order.

biogenic extraction:

I*

250
77

170 - 320
8 0 0 - 1600
3,2

0,3

0,1

3,6

WOLLAST (1974)
HARRIS (1966)
HEATH (1974)
LISITZIN (1967)

4,4 (total)
2,8 deep sea (antarctic)
DeMASTER
0,4 remaining deep sea
1981
1,2 shelf region
0,8 estuarine region
(total)
3,0 antarctic
CALVERT
2,0 pelagic regions
BURTON & LISS (1973) 1968
6,0 mainly in the
antarctic

esturarine extraction:
I

BURTON & LISS (1973)

extraction by mineral-neoformation and

trans forn~tion :
0,43

HEATH (1974) ;
WOLLAST (1974)
Fig. 10. M a s s b a l a n c e c a l c u l a t i o n s in r e s p e c t to d i s s o l v e d s i l i c a in t h e o c e a n w a t e r
system.

An

increased

silicates

on

initiated

under

Massenbilanz

von gelSstem S i 0 2 i m

Meerwasser.

high

supply

silica

conditions

rate

silica

of

organisms,
silica

But

the

lakes

increased

formation

amounts

processes

in unconsolidated

as w e l l

(pore-fluids)

3),

can

silica,

water

lead

can

1973),

But

water,

depressions

such

also

in

upon

contact

in c o a s t a l
decreased

surface
ground

formation

silica-rich
running

water

enriched

silica-rich

as o c e a n s

the

siliceous

sedimentary

also become

to t h e

also

silicification

Continental

Thus

line ground

result

the

as c o n t i n e n t a l

dissolved

to

of

can

of p r i m a r y

as w e l l

(Section

as

lead

to other

silica

deposits,

rocks

can

dissolved

in silica secreting

dissolved

waters

Thus,

in comparison

sources

terrestrially
explain

and

productivity

and

chemical

of t e r r e s t r i a l l y

to oceans

increased

nes

A l l e Werte x 1014 g / J ' a h r ; 1014 = 100 Mio t ;

~die
hohen Werte ergeben s i c h aus dem
R e c y c l i n g von biogenem SiO 2.

of

is e s p e c i a l l y

weathering(allitic-ferralitic),

(SHALE,
A l l v a l u e s x 10 TM g / y e a r ; 10 TM = 100 M i o t;
the high values are due to recirculation
processes of biogenic silica.

solubility

continents

of s i l c r e t e s
meteoric

and

formation

pH-values

(KNAUTH,
and

alka-

subsurfacially
lakes,

1979)

increased

zowaters

where
C O 2-

to

can

of m i x i n g

with marine-phreatic

regions

in

ground

273

Fig. 11. Sources, d i s t r i b u t i o n and c i r c u l a t i o n of d i s s o l v e d silica in the o c e a n (data from

WOLLAST, 1974)
The f o l l o w i n g v a l u e s x are all x 10 TM g/year; 10 TM = 1OO Mio t
(O) d i s s o l v e d s i l i c a from c o n t i n e n t a l w e a t h e r i n g (no value); (?) diss. silica in m e t e o r i c p h r e a t i c p o r e f l u i d s (no value); (I) river input 4.3; (2) b i o g e n i c f i x a t i o n in the p h o t i c
zone 250 ; (3) d i s s o l u t i o n of b i o g e n i c silica 245
(= 97 %): 120 by w a t e r t u r b u l e n c e
(4), and 125 by w a t e r c u r r e n t s (5); (6) f i x a t i o n in m a r i n e s e d i m e n t s 7,5z p r e s e r v a t i o n
0,8 (7), and d i s s o l u t i o n 6.7 (8) in m a r i n e sediments: (9) f i x a t i o n of 3.5 by n e o f o r m a t i o n
of m i n e r a l s (9), and 3.2 d i f f u s i o n into the o c e a n w a t e r (IO).

Quellen, Verteilung und Kreislauf von ge1~stem Si0~ im Meerwasser (z.T. nach WOLLAST 1974);
Die folgenden Wert x sind alle x 1014 g/Jahr; 1014~= 100 Mio t
(0) gel~stes Si02 aus kontin~ntaler Verwitterung (keine Angabe); (?) gelbstes SiO2 in
meteorisch-phreatischen Porenw~ssern (keine Angabe); ( i ) FluBzufuhr 4,3; (2) biogene
Fixierung in der photischen Zone 250 ; (3) LSsung von biogenem Si02 245 i~ 97 %);
120 durch Wasserturbulenz (4), und 125 durch Wasserstr~mungen (5); (6) Fi 'erung in
marinen Sedimenten 7,5: s
0,8 (7) und Aufl~sung 6,7 (8) davon: Fixierung von
3,5 durch Mineralneubildung und Diffusion von 3,2 ins Meerwasser (10)

p r e s e n c e r e s u l t in an i n o r g a n i c p r e c i p i t a t i o n of silica

(Fig.

11; S e c t i o n 3).

efficient

silica source,

i n d i c a t e d by the

fact that b i o g e n o u s s i l i c e o u s s e d i m e n t s
are not always formed t but show m a x i m a in

A further silica source for the f o r m a t i o n

of s e c o n d a r y cherts is seen by ILLIES

d i s t i n c t p e r i o d s of the earth's history.

(1949)

in the f o r m a t i o n of s i l i c a - r i c h c o m p a c t i o n
water;

resulting ascending solutions

to the p r e c i p i t a t i o n of silica.

lead

2.4

Diagenetic

FACTORS CONTROLLING THE SOLUTION,

s i l i c a r e l e a s e is also d i s c u s s e d by other

PRECIPITATION AND PRESERVATION OF

authors

SILICA-PHASES

(BRAMLETTE,

1946; DAPPLES,

1979;

GA/~RISON et al. t 1975; KEENE & KASTNER,

1974; TOWE,

1962). The i n f l u e n c e of

diagenetically

released

p l a c e at the b o t t o m of the o c e a n
PILSON,

1973; HEATH,

As shown in S e c t i o n 2.2 the e q u i l i b r i u m

s i l i c a takes

s o l u b i l i t y of silica p h a s e s d e c r e a s e s w i t h

(FLANNING &

1974; S C H I N K et al.,

1975), but this is not of s i g n i f i c a n t

importance.

H e n c e it seems o b v i o u s

increasing

stability, w h i c h is m a i n l y due

to a h i g h e r d e g r e e of c r y s t a l l i n i t y .

in a d d i t i o n to c r y s t a l l i n i t y the e q u i l i b r i u m

that

t e r r e s t r i a l d i s s o l v e d s i l i c a is m o s t p r o b a b l y

solubility
perature,

is a f f e c t e d by p r e s s u r e ,
pH-value,

the d e c i s i v e s i l i c a source in r e s p e c t to

parameters

c h e r t genesis,

d e t a i l in this p a p e r

last not least b e c a u s e of the

f o r m a t i o n of s i l i c a - r i c h p o r e water.

But

All

other silica sources should have only a

tem-

etc. The d i f f e r e n t

can't be d i s c u s s e d in m o r e
(see LASCHET,

1982),

but are s h o w n in a c o n s o l i d a t e d form in

Fig.

12.

local i n f l u e n c e on the f o r m a t i o n of cherts.

A d i r e c t b i o g e n i c s i l i c a source s h o u l d n ' t

In g e n e r a l

it can be said that i n c r e a s i n g

be c o n s i d e r e d as b i o g e n i c b o u n d s i l i c a can

temperature,

only be r e g a r d e d

w a t e r t u r b u l e n c e , w a t e r - c o n t e n t of silica

as the p r o d u c t of another

pressure,

pH-value

( >

8,5),

274

tendencey in the solubility of opaline silica in respect

to the increase and decrease in"

pressure
pH (-71

.~

..-

water turbulence

at
at
at

O~
25~
2~

at

2~

at
at

25~
25~

calm

60 - 80 p p m
loo - 1 4 o p p m
+
I atm: 56 p p m
+ 1ooo atm:
70 p p m
+ pH
+ pH

water

stirred

erystzllinity
Q
__ ~

5,25
13,7

C02-- presence
-

presence

~-

% H~O
% H~O

JONES

& PYTKOWICZ

1973

ca. 6 p p m
80-375 ppm

water

1956

KRAUSKOPF

7,7: Ioo p p m
lo,6:112o ppm

opal-CT,d(lol)4,11~,[5o
opal-CT,d(lol)4,o4A,29o

water content

OM

authors

examples

ppm
ppm

A L E X A N D E R et
1954

al.

MOREY

1962

et

al.

FOURNIER

8 ppm
12o p p m

YARIV

1973

& CROSS
1979

LOVERING &
P L A T T E N 1962

due

to p H - c h a n g e s

due

to C O 2 - d e v e l o p m e n t

m~

'~

adsorption of impurities

.Q

size of surface area

"~

high adsorp_tion
to a d e c r e a s e in

HURD
YARIV

reducing conditions

lowering

AI 3" - presence

-~

rate leads
solubility

in the

& CROSS
1979

of p h - v a l u e

pH-range

5 - Io,5

WEY

MO / Ca

)~-

1973

& SIFFERT
1961

LOWERING &
P L A T T E N 1962
AMIT

_ _

1969

ID

NaCI-presence

Mg 2" presence

'1~

WEY

& SIFFERT
1961

in the

pH-range

Io - 12,5

WEY

& SIFFERT
1961

Fig. 12. T h e i n f l u e n c e of d i f f e r e n t f a c t o r s o n t h e s o l u b i l i t y of o p a l i n e s i l i c a p h a s e s
i n o p e n or c l o s e d w a t e r s y s t e m s , ~ T h e s e
f a c t o r s l e a d to a d e c r e a s e o f d i s s o l v e d s i l i c a i n
t h e w a t e r s y s t e m s , r e s u l t i n g i n an u n d e r s a t u r a t i o n
i n r e s p e c t to o p a l i n e s i l i c a , a n d
t h e r e f o r e n in an h i g h e r d i s s o l u t i o n r a t e
of o p a l i n e s i l i c a ( h i g h e r s o l u b i l i t y ) . T h e b l a c k
w e d g e s i n d i c a t e h i g h and l o w v a l u e s of t h e d i f f e r e n t f a c t o r s .

Einflu~ der verschiedenen Faktoren auf die LUslichkeit yon opalinen SiOg-Phasen in offenen
und geschlossenen Wassersystemen.:W-Diese Faktoren fUhren zu einer Abnah~e des geIUsten
SiOp in den Wassersystemen, welches eine Unters~tttigung bezUglich opalinem SiOp zur Folge
hat'und sich in einer h~heren L~sungsrate von opalinem SiO 2 ~uBert.
Die schwar2en Keile
zeigen hohe und niederige Werte der verschiedenen Faktoren an.

phases,

surface

salinity,

area

and

on silca-phases
silica.

of

(Fig.

silca

seen

e t al,,

shown

12).

resulting

The

minerals

(1962)

the

solubility

The

decreased

with

decreasing

presence

of

tion

impurities
solubility

have

that high water

in a reducing

in c o n n e c t i o n

(pH 5-10;

C02-content ,

adsorption

increases

phases

phases,

r e s u l t in a h i g h e r

MOREY

experimentally
bulence

silica

and decreasing

crystallinity

of

of

of

tursilica-

solubility

environment

can be

CO2-development

and

pH-values.

of A 1 3 +

(Al-silicates)

and disordered
in s e a w a t e r

leads

systems

to

a higher

solution

(Fig.

12).

of

1005-12.5

the
The

1967);
of

results

of opaline

in

silica

equilibrium
same

mainly

where

of d i s s o l v e d

silica

etal,,

i n turn,

rate

for M g - c o n c e n t r a t i o n s
range

from

in a fixa-

concentration

which

by establishing

solubility

results

(McKENZIE

a lower

silica

phases

13)

silica

seawater

dissolved

uptake

clay

12;

of d i s s o l v e d

enriched
this

Figs.

is t r u e

in the pH-

an i n c r e a s e d

silica

takes

place,

For

the

inorganic

precipitation

silica

the

following

conditions

of

should

be

275

on the c o n t i n e n t s

are found in e n v i r o n m e n t s

of c h e m i c a l w e a t h e r i n g

in an w a r m or hot

humid to s e m i - h u m i d climate,
which ferralitic welthering

a c l i m a t e under
takes p l a c e

leading to the f o r m a t i o n of bauxite,

l a t e , i r e and similar AI, F e - r i c h r e s i d u a l
deposits

(Fig.

14). Therefore,

climate seems to control

the palaeo-

the p r e c o n d i t i o n s

u n d e r w h i c h chert f o r m a t i o n is possible.

Under c o n s t a n t c o n d i t i o n s

the above

cited p r e m i s e s C and D should also lead to

the p r e s e r v a t i o n of p r e c i p i t a t e d
phases.

If d i s s o l v e d

silica

silica c o n c e n t r a t i o n

is too high w i t h r e s p e c t to a d i s t i n c t
solid s i l i c a phase,
Fig. 13. S u p e r i m p o s e d curves of the
s o l u b i l i t y of silicap A13+, Mg 2+ and tendencies in the s o l u b i l i t y of s i l i c a
i n f l u e n c e d by the p r e s e n c e of A13+, Mg 2+
and N a C I (after KRAUSKOPF, 1956; WEY &
SIFFERT, 1961).

Da~tellung der h~slichkeitskurven von Al 3+,

Mg
und Tendenzen der SiOp-LSslichkeit bei
Beeinflu~sung durch die AnWesenheit von
Al3+, Mg~+ und NaCl (nach KRAUSKOPF, 1956;
WEY & SIFFERT, 1961).
maintained:

A. W e a t h e r i n g

the less stable silica

phase will precipitate;

this m e a n s

the higher the c o n c e n t r a t i o n ,

unstable

is the p r e c i p i t a t e d

As under n a t u r a l conditions,
of stable s i l i c a p h a s e s
process,

that

the m o r e
silica phase.
the p r e c i p i t a t i o n

is a very slow

the p r e c i p i t a t i o n of m o r e u n s t a b l e

silica p h a s e s is m o r e p r o b a b l e in the

conditions with

high s o l u t i o n rates of silica and s i l i c a t e s

(higher t e m p e r a t u r e I pH, etc., Fig.

12)

leading to h i g h e r c o n c e n t r a t i o n s of d i s s o l v e d
silica in w a t e r

systems.

This gives rise to

B. s i l i c a sources w h i c h are able to supply

sufficent dissolved
w i t h C. c o n d i t i o n s

silica into e n v i r o n m e n t s
leading to s a t u r a t i o n or

s u p e r s a t u r a t i o n of s o l u t i o n s w i t h r e s p e c t
to d i s s o l v e d silica,
w a t e r turbulence,
pressures,
etc..
D.

such as little

low c o n c e n t r a t i o n s

of AI-, M g - i Q n s ,

Some of these c o n d i t i o n s

are found in

zones w i t h r e d u c i n g e n v i r o n m e n t s

in d e p r e s s i o n s

such as

at the b o t t o m of the sea or

in p o r e w a t e r systems,
layered w a t e r

or no

low t e m p e r a t u r e and

etc.,

c a u s e d by

systems and/or m o r e or less

closed w a t e r systems w h e r e d e c a y i n g o r g a n i c
m a t t e r or m i x i n g of m e t e o r i c p h r e a t i c w i t h
marine phreatic water
for example,
of CO 2.

takes place,

to p H - c h a n g e s

leading.

and the g e n e r a t i o n

(Many d i f f e r e n t r e l a t i o n s h i p s of

conditions

leading to i n o r g a n i c silica

p r e c i p i t a t i o n can be c o n s t r u c t e d ~ . )

The ideal c h e m i c o - p h y s i c a l p r e r e q u i s i t e s
leading to the i n c r e a s e d s o l u t i o n of silica

Fig. 14. S o l u b i l i t y of SiO~, A I g o ~ and

F e ~ O 3 in the zones of the ~ a n t l ~ 5f w a s t e
w i ~ h the l a r g e s t d i f f e r e n c e b e t w e e n SiO^
and A l ~ O q in the p H - r a n g e of 8 to 9 (after
SMIRNOW,'1976).

h~slichkeit von Si02, AI~OR und Fe~OR in

der Verwitterungszone mit ~em h~ch~t~n
LSslichkeitsunterschied im pH-Bereich von
8 his 9 (nach 5MIRNOW, 1976).
i n i t i a t i o n of any c h e r t formation.
the p r o c e s s of s i l i f i c a t i o n is a

That
rather

276

fast process is seen in the well preserved

fication processes

organic material

ses which take place under alkaline condi-

found in cherts, where

there wasn't enough time left for the

organic matter to decay

tions, A higher pH can therefore result in

(FAIRSCHILD et al,,

1973),

the dolomitlzation of Ca-carbonates by Mgrich solutions;

following the lowering of

the pH selective
Thus,

to dolomitization proces-

as opal-A is the first and

leaching of calcite and

precipitation of silica may take place,

easiest silica phase to form, conditions

if silica-rich solutions are present,

for the formation of chert precursors

dence of this process is found in dolomite-

are

Evi-

necessary where silica concentrations

rhombs which are very often preserved in

reach more than 60 ppm

silicificated

up to 140 ppm
temperatures

(O~

(25 ~ , pH 9)

pH 7,7) and
At low

the difference in the solubi-

lity of silica phases is more pronounced

(O ~

carbonates,

2.5

DIAGs

opal/quartz quartz = 60 ppm/6 ppm =

EVOLUTION OF SILICEOUS

SEDIMENTARY ROCKS AND SILICIFICATIONS,

10 : I) than at higher temperatures, where

AND THE DIAGENETIC RELATIONSHIP

the ratio decreases

BETWEEN THEIR SILICA-PHASES

to values of less than

2 : I, The great differences

in the solubiThe transformation of silica phases

lity of silica phases at medium temperatures

indicate also the formation of opal-CT as

during diagenetic processes is strongly

an intermediate silica phase of the trans-

affected by temperature

and pressure

(in-

formation from opal-A to quartz. Factors

fluence of burial depth, or tectonic down-

which initiate the precipitation of silica

faulting and uplifting or folding) s pH-

phases are shown below. Direct and indirect

values

precipitating

purity of silica phase, nucleation rate

factors can be distinguished.

(akalinity),

length of time,

etc.
A. Direct precipitation

factors:

I. evaporation of silica-rich solutions

2. quenching of warm silica-rich solutions
3. neutralization of alkaline silica-rich
solutions
4. stabilizing of stirred silica-rich
solutions
5. production, addition or presence of CO 2
(at pH > ~ 7 )
6, pressure release of high pressure silicarich solutions
7. mixing of solutions with different pH,
salinity and silica concentration sometimes through the production of CO2, etc.

genesis the following changes take place;

B. Indirect precipitation

true precipitates

factors:

I. adsorption and uptake of dissolved silica

by other mineral phases or organic matter
2. utilization of dissolved silica by silica
secreting organisms etc.
Increased temperature,
value, Mg/Ca-ratio,

salinity,

reducing

decreasing CO2-content

pH-

conditions

and

are typical facies

indicators of regression periods

(RAMSBOTTOM,

Incirect factors such as the petrology

of the host rock, porosity and permeability, composition of the pore fluids etc, t
also play an important role, During dia-

Increase of density,

orystallinity,

purity

(expulsion of impurities)- and decrease

of porosity
and

and permeability,

~ 180 values,

chalcedony

H20-content

Silica phases occur as

(opal 0 opal-CT and

(?)) either in a closed system

(cavities and voids),

or in an open system

(as cement from fluid systems in an open

pore spacer

or at the bottom of oceans

and lakes),

as replacement products of

carbonate and evaporitic minerals,

recrystallization
metastable

or as

products of other

silica phases,

1973; Section 3) leading eventually to

higher inorganic concentrations
silica,

by evaporation,

& v.d. BORCH,

of dissolved

for example

(PETERSON

;965).

Recrystallization

products can arise

from true metastable precipitates

opal, or from replacement products

such as
(trans-

foramtion of opalized carbonate fossil

The initial alkaline character of silica-

shells to quartz),

Recrystallization

rich pore fluids which may cause replacement

processes

take place under true diagenetio

is shown by the close relationship of silici-

conditions as well as under subaerial

277

conditions.

Recrystallization processes

can only be o b s e r v e d in s e d i m e n t s

related to the spatial p o s i t i o n of a die-

and

genetic

zone. T e c t o n i c p r o c e s s e s

such as

rocks no older than the E a r l y C r e t a c e o u s

f a u l t i n g and folding as w e l l as an in-

in w h i c h m e t a s t a b l e

creased rate of burial

still be present.

s i l i c a phases m i g h t

Three diagenetic

zones

can be d i s t i n g u i s h e d :
I. opal-zone:

f o r m a t i o n zone in

which opaline silica phases

AG,

opal-AN

precipitate

into p o s i t i o n s w i t h higher g e o t h e r m a l
gradients.

Primary

such as opal-

and b i o g e n i c o p a l - A can
and a c c u m u l a t e

zones

1975).

(including p o s t

s e d i m e n t a r y rocks).

T h e s e silica p h a s e s

can be c o n s i d e r e d

In a stable p o s t s e d i m e n t a r y
(constant temperature,

as

chert p r e c u r s o r s .

environment

pressure,

etc.)

d i a g e n e t i c e v o l u t i o n of silica phases

the
is

d e p e n d e n t only on time and should be

2. o p a l - C T - z o n e :

o p a l - A species b e c o m e

m o r e and m o r e u n s t a b l e and r e c r y s t a l l i z e

c o m p l e t e d at least after
years

120 Mio.

~ 10 Mio.

(Section 2,2).

or r e p r e c i p i t a t e d as

In this zone o p a l - C T m a t u r e s

p o o r l y o r d e r e d opal-CT

(d(IO1)

to well o r d e r e d opal-CT
(Fig.

it is p o s s i b l e that

located in d i f f e r e n t d i a g e n e t i c

s e d i m e n t a r y i n t r o d u c t i o n of o p a l i n e s i l i c a

opal-CT.

Therefore,

p a r t s of one s t r a t i g r a p h i c h o r i z o n can be

(MURATA & RANDALL,

into u n c o n s o l i d a t e d

to form opal-CT,

can bring such zone

from

-- 4.115 ~)

(d(I01)

= 4,04 ~)

5).

The m a i n q u e s t i o n in the d i a g e n e t i c
e v o l u t i o n of silica phases

solid reaction,

3. q u a r t z - z o n e :

Final diagenetic

zone

is, w h e t h e r

t r a n s f o r m a t i o n of silica phases
or w h e t h e r

the

is a solid-

it is linked

w i t h a s o l u t i o n step.

w h e r e even opal-CT b e c o m e s u n s t a b l e and

recrystallizes

to stable q u a r t z v a r i e t i e s

(microquartz),

or r e p r e c i p i t a t e s

stable quartz v a r i e t i e s

as

The m o s t i m p o r t a n t tool for a n s w e r i n g

this q u e s t i o n is the d e t e r m i n a t i o n of the

(megaquartz).

180 v a l u e s of s i l i c a - p h a s e s

rock, The d i f f e r e n t
D i r e c t m e g a q u a r t z p r e c i p i t a t i o n seems
to be p o s s i b l e in all d i a g e n e t i c

zones if

a local a l k a l i n e e n v i r o n m e n t exists
et al.,

(MURATA

1977; S e c t i o n 2.2.5). T e m p e r a t u r e

in v a r i o u s

in s i l i c e o u s

180/160-ratios

silica p h a s e s are i n t e r p r e t e d

v e r y often as e v i d e n c e for a s o l i d - l i q u i d
t r a n s f o r m a t i o n of silica phases,
for the t r a n s i t i o n

especially

from o p a l - A to opal-CT,

and p r e s s u r e are the m a i n factors i n i t i a t i n g

but also for the t r a n s i t i o n of o p a l - C T

the t r a n s f o r m a t i o n of o p a l i n e s i l i c a p h a s e s

quartz.

(CARR & FYFE,

c o n v e r s i o n of opal-CT to quartz was sug-

1958). The h i g h e r

the tempera-

to

A quasi solid-solid microstructural

ture the q u i c k e r is the t r a n s f o r m a t i o n of

g e s t e d by RIECH & v. RAD

silica p h a s e s

ference to the w e l l - p r e s e r v e d quartz re-

(MIZUTANI,

higher t e m p e r a t u r e s

1977). B e s i d e s

and p r e s s u r e s h i g h e r

pH and i o n i c - s t r e n g t h

Therefore,

spherules

and s k e l e t o n s of

also seems to e n h a n c e

the t r a n s f o r m a t i o n rate of o p a l - p h a s e s
quartz.

placed opal-CT

(1979), in re-

to

the t r a n s f o r m a t i o n

should p r o c e e d m o r e slowly in a cold freshwater

environment

(~ n e u t r a l m e t e o r i c

p h r e a t i c p o r e fluids),
marine

conditions,

than under cold

e s p e c i a l l y w h e r e asso-

ciated w i t h c a r b o n a t e s (KASTNER, 1981) in

+
a - a l k a l i n e m a r i n e p h r e a t i c environment.
Nevertheless,

the t e m p e r a t u r e e f f e c t seems

to be stronger,

because subaerial exposed

cherts r e a c h their m a t u r i t y m o r e q u i c k l y
than cherts in deeper w a t e r e n v i r o n m e n t
at t e m p e r a t u r e s of only 5 ~

Temperature

(pressure)

or less.

i n c r e a s e is

Fig. 15, a. crystal s t r u c t u r e of e - c r i s t o b a l i t e (opal-CT); b. c r y s t a l s t r u c t u r e of

e - q u a r t z (from HEATH & M O B E R L E Y 1971). The
d i f f e r e n t s t r u c t u r e s d e m o n s t r a t e the bond
r e o r g a n i z a t i o n w h i c h m u s t a c c o m p a n y an
i n v e r s i o n of o p a l - C T to quartz.

a. K r i s t a l l s t r u k t u r yon ~ - C r i s t o b a l i t
(Opal-CT); b. K r i s t a l l s t r u k t u r von a-Qua?z
(von HEATH & MOBERLs 1971). Die verschiedenen Strukturen demonstriert eine Bindungs-Reorganisierung, die einer Inversion
yon Opal-CT zu Quarz begleiten muB.

278

siliceous

fossils. They also concede the

CT lattice show bonds to other silica

possibility that opal-CT forms in situ from

tetrahedra as is shown by the presence of

opal-A because of opaline skeletons which

SiOH groups

(Fig. 3). The rearrangement of

have been transformed into opal-CT.

the opal-CT

lattice to a quartz

lattice

is connected with the loss of all OH--poa

Ib

["1- Si

A 'A4

sitions

necessarily
be either

Si(OHh

in a loss of O--ions which may

180 or 160. A preferred expulsion

the quartz

SilOHh --~$i~O(OH)s"OH'+H"

15). This process results

of 180 and a preferred retention of 160 in

'

(Fig.

lattice

temperatures

(mainly due to higher

at the time of quartz-formation)

leads to lower 180/160 ratios,

usually found in

(quartz-)

as they are

cherts,

comparison to cristobalitic

cherts

with higher 180/160-ratios.

Thus,

differences

in
(opal-CT)
the

in isotopic composition are

also explainable through a solid-solid

conversion,

9 =Si

an no solution step is necessary

to account for the differences

o-0

Fig. 16. Rearrangement_of H +-, OH- or 02-ions. The amount of OH -ions decreases from
a to b and from c to e (c = opal; e =
quartz).
U m s t r u k t u r i e r u n g yon S i O p - E i n h e i t e n u n t e r
V e r l u s t yon H
O H ' - I o n ~ n . Der A n t e i l von
OH--Ionen nimmt von a nach b und von c
nach e ab (c = o p a l ; e = q u a r z ) .

The isotopic composition of mineral

phases is dependent on the temperature
the time of formation.

At higher tempera-

expelled during the formation of the crystal-lattice of stable silica phases or

to stable silica phases.
cherts normally

step in the transformation of silica

megaquartz,

and

which are found in cavities or

void-spaces.

They could have formed in a

to the preferred
demonstrated

cherts

(opal-CT)

due

(1977), where it is shown that in the

mobility of silica ions

Monterey Formation opal-A

1970) .

a solution step is not

necessary to explain the differences

(quartz)

in a paper by MURATA et al.,

three diagenetic

But generally

Therefore,

fixation of 160. This is

low temperature environment with a low

(REYNOLDSe

of metastable

show a lower 180/160 ratio

than cristobalitic

phases is given by opal-CT lepispheres

at

tures 180 isotopes become more and more

during the recrystallization

The only true evidence for a solution

in ~180.

zones

~ 1 8 0 values of 37.4%0
in

(see above)

of the

(I st zone) has

(~15

opal-CT

(2nd zone) has a value of 29,4 ~ 1.5 ~.

the 180/160-ratio of silica phases. Thus,

(48 ~ 8 ~

HEATH & MOBERLEY

value of 23.8 ~ 0~

(1971) describe a sawtooth

and microquartz
%o

(3rd zone)

(79 ~ 2 ~

contact between crystobalite and chalcedonic quartz as a classic solid-solid

The fact that cristobalitic porcelanite

inversion front.

(mainly opal-CT)

has a greater amount of

180 than coexisting cherts

During the rearrangement of SiO2-units
(and/or)

SiOH4)

quartz)

to more stable crystal

time of higher diagenetic temperature

(Fig. 15). The

different crystal structures demonstrate

(KOLODNY & EPSTEIN,

the

bond reorganization which must accompany an

inversion of opal-CT quartz

(Fig.

16).

In contrast to quartz-silica phases not

in an opal-

1976). The diagenetic

delay in the evolution of porcelanites

can be explained by a greater amount of
clay-minerals

in porcelanites,

diagenetic reaction,

all silica tetrahedra positions

the

diagenetic evolution takes place later at

lattice, more and more H +-, OH-- and 02-ions become superfluous

(mainly micro-

proves that in porcelanites

6180

which buffer

The almost constant

values for opal-CT are not only an

evidence that the maturing process of

279

poorly ordered opal-CT

to well o r d e r e d o p a l - C T
is a s o l i d - s o l i d
LARSON,

(d(IO1)

= 4.115 R)

(d(IO1)

conversion

= 4.O4 ~)

1975), but they also show that

r e a r r a n g e m e n t of the o p a l - C T

lattice

(Fig.

15), w h e r e only a small n u m b e r of new

O - b o n d s b e t w e e n the s i l i c a - t e t r a h e d r a
constructed

are

and so only a small loss of

is involved.

Thus only the

~180 v a l u e s of true p r e c i p i t a t e s ,

such as

m a s s i v e o p a l - A or opal-A,

lepi-

spheres and m e g a q u a r t z

opal-CT

s t r u c t e d w i t h some k n o w l e d g e of the en-

as o p a l - A phases,

as no
takes place.

only some of the o x y g e n - i s o t o p e s

or r e t a i n e d

(180)

(160) during r e c r y s t a l l i z a t i o n

phases w h i c h r e s u l t e d from r e c r y s t a l l i z a t i o n

First,

such

lephispheres

and

But in this case one

also has to be aware of the p r o b l e m that

smchsilica-phases precipitate
or closed fluid systems.

while opal-CT
The i s o t o p i c c o m p o s i t i o n of s t a b l e silica-

opal-CT

and drusy m e g a q u a r t z .

precipitate mainly

processes.

processes

pore

fluids from true silica p r e c i p i t a t e d

d i c a t o r s of the c o n d i t i o n s at the time

i n v o l v e d are p r e f e r e n t i a l l y e x p e l l e d

formation,

such as m e t e o r i c - p h r e a t i c - m a r i n e

zation can not be true t e m p e r a t u r e in-

Therefore,

of silica

v i r o n m e n t of the s i l i c a - p h a s e

w h i c h m i g h t have formed by r e c r y s t a l l i -

c o m p l e t e s o l u t i o n of the phases

p h a s e s can thus only be d e d u c e d and recon-

All the other s i l i c a - p h a s e s

of f o r a m t i o n of theses phases,

Example: Opal w i t h a p r i m a r y high ~180

v a l u e and its r e c r y s t a l l i z a t i o n at a high
m p e r a t u r e (which should lead t~ v e r y low
~O v a l u e s ) m a y cause an average
ISO value
in the final silica phase,%~hile opalT,rith a
low p r i m a r y ~ 1 8 0 value and its r e c r v s t a l lization at a high t e m p e r a t u r e could result
in an e x t r e m e l y low ~ 1 8 0 value .So the isotopic c o m p o s i t i o n of a stable silica recryst a l l i z a t i o n ~ r o d u c t can sho~ n e i t h e r the true
r e c r y s t a l l i z a t i o n t e m p e r a t u r e nor the isotopic c o m p o s i t i o n of its precursor.
The f o r m a t i o n t e m p e r a t u r e

in c a v i t i e s and

voids can be taken as a real t e m p e r a t u r e

indicators.

above two influences:

(MURATA &

the opal-CT m a t u r i n g p r o c e s s r e s u l t s in a

OH--groups

cherts can thus be e x p l a i n e d solely by the

systems

from an open fluid system,

(lephispheres)

should precipitate

from open

O p a l - A phases

an m e g a q u a r t z

from m o r e closed fluid

(cavities and voids).

is i n f l u e n c e d by two m a i n factors:
It is s u g g e s t e d here that the m a i n for-

the ~ 1 8 0 v a l u e s of final stable

silica-recrystallization phases

m a t i o n p r o c e s s of stable silica p h a s e s is

are in-

f l u e n c e d by the p r i m a r y i s o t o p i c c o m p o s i tion of an u n s t a b l e o p a l - A - t y p e p r e c u r s o r

v o l v e s no other

and this p a r t i a l l y r e c o r d s the i s o t o p i c

c o m p o s i t i o n of the p r e c u r s o r .

Secondly,

a recrystallization process

the

w h i c h in-

true s o l u t i o n step but the

e x p u l s i o n of o x y g e n and h y d r o g e n ions.
(Fig,

~ 1 8 0 v a l u e s of the final stable silica

(especially

w i t h r e s p e c t to a silica matrix)

15).

recrystallization phases partially record

the t e m p e r a t u r e

at w h i c h r e c r y s t a l l i z a t i o n

took place. No third i n f l u e n c e such as the

i s o t o p i c c o m p o s i t i o n of a late d i a g e n e t i c
pore fluid stage is n e e d e d to e x p l a i n differing i s o t o p i c v a l u e s of stable silicaphases,

b e c a u s e no c o m p l e t e s o l u t i o n of

the s i l i c a - p h a s e s

is n e c e s s a r y d u r i n g

the

t r a n s f o r m a t i o n to stable s i l i c a phases.
Therefore,
fluids,

the i s o t o p i c c o m p o s i t i o n of p o r e

from w h i c h s i l i c a

is p r e c i p i t a t e d ,

The above c o n s i d e r a t i o n s m i g h t

c l a r i f y the p r o b l e m w h i c h c o n c e r n s

the

i n t e r p r e t a t i o n of some of the ~ 1 8 0 v a l u e s
of s i l i c a - p h a s e s

(D/H) values

can

m e n t a l r e c o n s t r u c t i o n by k e e p i n g in m i n d
the r e s t r i c t i o n s m e n t i o n e d

above. A m o r e

v a l u a b l e tool for the p a l a e o e n v i r o n m e n t a l

and d i a g e n e t i c r e c o n s t r u c t i o n

could be

found in the ~ 1 3 C v a l u e s b e c a u s e they are

not i n v o l v e d in the c r y s t a l g r o w t h of silica
phases.

(chert precursors)

is v e r y i m p o r t a n t in

r e s p e c t to the final i s o t o p i c c o m p o s i t i o n
in cherts.

L i k e the ~ 1 8 0 value, ~ D

be s i m i l a r l y u s e d for the p a l a e o e n v i r o n -

o b s e r v e d by other authors.

The d i f f e r e n t i s o t o p i c v a l u e s for quartz

I n t e r p r e t a t i o n of i s o t o p i c v a l u e s of
silica-phases

should be m o r e v a l u a b l e

c o m p a r i s o n w i t h i s o t o p i c values

in

from

other m i n e r a l phases w h i c h have a g e n e t i c

relationship
et al.

to c h e r t - f o r m a t i o n .

(1977)

Monterey Shale

MURATA

showed that d o l o m i t e from the

is always i s o t o p i c a l l y h e a v i e r

280

than a s s o c i a t e d cherts S w h i c h could m e a n

and c h e r t p r e c u r s o r s w e r e formed one after

that d o l o m i t e p r e c i p i t a t e d b e f o r e the

the other in close g e n e t i c r e l a t i o n s h i p ,

silica-phase

but that the q u a r t z has lost the i s o t o p i c

(microquartz)

w h i c h formed

last, or the i s o t o p i c c o m p o s i t i o n of the

c o m p o s i t i o n of its p r e c u r s o r s

d o l o m i t e m o r e ore less i n d i c a t e s

r e c r y s t a l l i z a t i o n processes.

the true

through

c o m p o s i t i o n of the fluid in w h i c h d o l o m i t e

A GENETIC MODEL

The

p r o c e s s of p r i m a r y and s e c o n d a r y

chert g e n e s i s has not been w e l l u n d e r s t o o d

s o l u b i l i t y of s i l i c a p h a s e s and silicates.
At times of c h e m i c a l w e a t h e r i n g ,

or c o m p l e t e l y e x p l a i n e d u n t i l now b e c a u s e

chemical sediments

different processes

open w a t e r systems,

and i n f l u e n c e s

cate the g e n e r a l picture.

compli-

F o l l o w i n g our

r e a s o n i n g in S e c t i o n 2.3 we see that the

terrestrial

s i l i c a source is the s i l i c a

preferably

(carbonates and salt)

and laterite,

and red soils as w e l l as k a r s t f e a t u r e s in

continental deposits preferentially
formed. Thus,

are

u n d e r c o n d i t i o n s of c h e m i c a l

s o u r c e w i t h the m a i n i n f l u e n c e on c h e r t

weathering

formation;

are d e p o s i t e d in the w a t e r systems w h i l e

the c o n d i t i o n s w h i c h r e s u l t e d An

rather Al-poor

chemical sediments

an i n c r e a s e d d i s s o l u t i o n of s i l i c a on the

at the same time A l - r i c h m i n e r a l s

c o n t i n e n t s w e r e d i s s c u s s e d in S e c t i o n

c o n c e n t r a t e d in c o n t i n e n t a l deposits.

2,4.

are

The m a i n factor w h i c h causes the d i f f e r e n t

D u r i n g times of m o r e p h y s i c a l w e a t h e r i n g

k i n d of w e a t h e r i n g

conditions,

palaeoclimatic

and s e d i m e n t s

is a

factor, The facies of sedi-

m e n t a r y d e p o s i t i o n is further

influenced

by r e g r e s s i o n and t r a n s g r e s s i o n p e r i o d s
(Fig.

19), w h i c h are p a r t l y c o n t r o l l e d by

palaeoclimate

(glaciation periods)

t e c t o n i c events.
topography,

Other

vegetation,

i n f l u e n c e s s u c h as
w a t e r sheds

(direction of w a t e r - r u n of),
materia%

and

kind of p a r e n t

(petrology), p o r o s i t y and p e r m e a b i -

mainly Al-rich sediments

(shales)

are d e p o s i t e d and s i l i c a is fixed w i t h i n

silicates.

McKENZIE

by e x p e r i m e n t s

et al.

(1967) have shown

that u n d e r normal m a r i n e

c o n d i t i o n s m o s t of the d i s s o l v e d
taken up by d i s o r d e r e d
silicates),

silica is

clay-minerals

(A1-

if the c o n c e n t r a t i o n of

d i s s o l v e d s i l i c a b e c o m e s h i g h e r than 6 ppm.
This i n d i c a t e s that c l a y - m i n e r a l s

in some

way control the s i l i c a c o n c e n t r a t i o n in

lity have to be c o n s i d e r e d as a f f e c t i n g

sea water,

But considering

the fact that

the rate of c h e m i c a l w e a t h e r i n g S the n a t u r e

u n d e r the w e a t h e r i n g

of the w e a t h e r i n g p r o d u c t s and the rate

above o n l y small amounts of d i s o r d e r e d

of d i s s o l v e d s i l i c a transport.

rich)

c o n d i t i o n s cited

is that the

(AL-

c l a y - m i n e r a l s or d i s s o l v e d A 1 3 + are

b r o u g h t into the w a t e r systems

The b a s i c idea of the m o d e l

in

bauxite

clay-minerals

(Fig.

11),

can take up only a m i n o r

f o r m a t i o n of s i l i c e o u s r o c k s in one w a y or

a m o u n t of d i s s o l v e d silica, T h e i n c r e a s e

another is c o n n e c t e d w i t h h i g h S i / A l - r a t i o s

of d i s s o l v e d s i l i c a s h o u l d t h e r e f o r e r e s u l t

in aqueous

solutions

in the cycle of

w e a t h e r i n g and s e d i m e n t a t i o n
p o r e cements).

(including

H i g h S i / A l - r a t i o s under

c o n d i t i o n s of c h e m i c a l w e a t h e r i n g

lead to

in a h i g h e r

s i l i c a c o n c e n t r a t i o n in the

w a t e r system.

S i l i c a c o n c e n t r a t i o n should

be even m o r e e n h a n c e d by the i n c r e a s e d
d i s s o l u t i o n of s i l i c a on continents,

which

i n c r e a s e d f i x a t i o n of A1 in r e s i d u a l

is t r a n s p o r t e d

w e a t h e r i n g p r o d u c t s on the c o n t i n e n t s

at the same time e s p e c i a l l y A l - m i n e r a l s

and to higher

are held b a c k in r e s i d u a l d e p o s i t s on the

c o n c e n t r a t i o n s of s i l i c a in

to lakes and oceans,

while

any w a t e r s y s t e m s u b j e c t to the influx of

continents.

c h e m i c a l w e a t h e r i n g products.

d i s s o l v e d s i l i c a m i g h t r e s u l t in the in-

conditions

where chemical weathering

process,

Climatic

can g i v e rise to g l o b a l belts,

is the p r e v a i l i n g

r e s u l t i n g also in an i n c r e a s e s

So the i n c r e a s e d input of

o r g a n i c p r e c i p i t a t i o n of silica in open
water-systems

under b a s i n a l

sheltered

c o n d i t i o n s w i t h little or no w a t e r turbu-

281

fence,

etc.

(see S e c t i o n 2.4). P r o o f of

the d e c r e a s i n g

such as lakes and o c e a n s by fluvial or sur-

a v a i l i a b i l i t y of A1 in the

o c e a n w a t e r at times of s i l i c e o u s d e p o s i t s

face w a t e r run-offt

the p o r e - w a t e r

system

should also b e c o m e e n r i c h e d w i t h d i s s o l v e d

f o r m a t i o n is g i v e n by the fact that

s i l i c a and d e p l e t e d

Mesozoic

p o r e w a t e r has an a l k a l i n e c h a r a c t e r

and C e n o z o i c s i l i c e o u s d e p o s i t s

(DSDP-sites)

are v e r y o f t e n a s s o c i a t e d

with minerals

such as p a l y g o r s k i t e ,

sepiolite,K-feldspar
(Fig.

pH range of 8-9

(sepiolite)

1980; LANCELOT,

BORCH

(palygorski-

or are A l - p o o r

( c l i n o p t i l o l i t e and K-feldspar)
1973; TIMOFEEV,

(Fig.

if
in the

14), or even as

high as 10.5 as shown by P E T E R S O N

and c l i n o p t i l o l i t e

117), w h i c h can be A l - p o o r

te), A l - f r e e

in AI, e s p e c i a l l y

& v. d.

(1965)o But also in a n e u t r a l s o l u t i o n

dissolved

s i l i c a can get e n r i c h e d up to

10OO p p m w i t h o u t

the p r e c i p i t a t i o n of s i l i c a

(KASTNER,

as L O V E R I N G

1978);

Such s i l i c a - r i c h c o n t i n e n t a l pore- or ground

this

& PLATTEN

(1962)

have shown.

is also shown by h i g h ratios of p a l y g o r s k i t e /

w a t e r s can lead to the formation

montmorillonite,

( S M A L E , 1 9 7 3 ) , b u t in coastal regions silica-

clinoptilolite/phillipsite

and K - f e l d s p a r / p l a g i o k l a s
siliceous

in samples of

layers from D S D P - s i t e s .

The same

a s s o c i a t i o n of s i l i c a - r i c h m i n e r a l s
sepiolite,

palygorsklte,

rich d e p o s i t s

such as

etc. w i t h s i l i c a -

is r e p o r t e d f r o m on land ex-

posed siliceous deposits

v. RAD & ROSCH,

(LANCELOT,

1972; REX,

1973;

of s i l c r e t e s

rich g r o u n d - w a t e r can i n t r u d e o o r o u s and perm e a b l e m a r i n e s e d i m e n t s filled w i t h

marine

s e d i m e n t s f i l l e d w i t h m a r i n e or m a r i n e - i n f l u e n c e d pore-water. The i n t r o d u c t i o n of
meteoric-phreatic

terrestrial

silica-rich

g r o u n d w a t e r into s e d i m e n t s w i t h m a r i n e or brackish p h r e a t i c pore w a t e r leads to the f o r m a t i o n

1972).

of m i x i n g zones (Figs. 11;19). M i x i n g p r o c e s s e s

of w a t e r s of d i f f e r e n t c o m p o s i t i o n can r e s u l t

Minerals
-Al-poor:
Palygorskite
Clinoptilolite
Sepiolite
A I - rich:

Si : At
3,5:1
3,5 : 1
4 : 0
1
1

Kaolinite
Illite

in a p H c h a n g e ( l o w e r i n g ) , s a l i n i t y change (in-

(also 1 :

1)

c r e a s e ) , a n d an i n c r e a s e of C O 2 - c o n c e n t r a t i o n .
T h e s e c h a n g e s can lead to the p r e c i p i t a t i o n
of silica w h i c h is d e m o n s t r a t e d

: 1
: 1

sufficiently high
Fig.

in Figs.

12

and 19, if the silica c o n c e n t r a t i o n is

(KNAUTH,

1979).

17. S i / A l - r a t i o s of some m i n e r a l s .

Si/Al-Verh~Itnisse einiger Minerale.

LANCELOT

(1973)

suggests

Favorable conditions

that h i g h e r

p r o p o r t i o n s of p a l y g o r s k i t e

for the f o r m a t i o n

of m i x i n g

zones are e s t a b l i s h e d

sediments

(mainly shallow)

if m a r i n e

are slowly

r a i s e d by t e c t o n i c u p l i f t i n g or by sea

and s e p i o l i t e

level c h a n g e s

above or near sea level and

are i n d i c a t o r s of a m o r e s i l i c i c o c e a n i c
e n v i r o n m e n t than today.

The i n c r e a s e d input of d i s s o l v e d
into the w a t e r

s y s t e m also e x p l a i n s

silica
the

i n c r e a s e d p r o d u c t i v i t y of s i l i c e o u s organisms
at d i s t i n c t times and in d i s t i n c t regions.
Thus,

the first p a r t of the m o d e l d e m o n s t r a -

tes the p o s s i b i l i t y of an i n o r g a n i c formation

of p r i m a r y s i l i c e o u s deposits,

as w e l l as

an i n c r e a s e d p r o d u c t i v i t y of s i l i c e o u s
organisms.

H o w e v e r the f o r m a t i o n of secon-

dary s i l i c e o u s rocks can also be e x p l a i n e d

by d i s s o l v e d

silica from c o n t i n e n t a l

weathering.

B e s i d e s higher c o n c e n t r a t i o n s

of d i s s o l v e d

silica w h i c h are b r o u g h t into d e p r e s s i o n s

Fig. 18. C h e r t o c c u r r e n c e s along the A p t i a n

s h o r e - l i n e in the L o w e r C r e t a c e o u s of
s o u t h - E n g l a n d (after M I D D L E M I S S , 1978).

Chert-Vorkommen entlang der KUstenlinie des

Aptian in der Unterkreide von SUdengland
(nach MIDDLEMISS, 1978).

282

are t h e r e b y exposed to i n c r e a s e d i n f l u e n c e s

sediments

of m e t e o r i c p h r e a t i c p o r e - f l u i d s

b o n a t e s are u n d e r l a i n by porous

in Fig,

19

as d e p i c t e d

(A, B, C), U s u a l l y at times of

regressions

are g i v e n if t h e s e m a r i n e car-

such as s a n d s t o n e s

(Fig,

sediments

19 B).

large a m o u n t of p r i m a r y m a r i n e

deposits will become subaerially exposed

or at least raised to near sea level w i t h
their pore w a t e r coming under

the i n f l u e n c e

N o d u l a r or other forms of s e c o n d a r y
cherts of any age are n o r m a l l y found in
p l a t f o r m c a r b o n a t e s m a i n l y of s h a l l o w

of m e t e o r i c w a t e r systems of coastal re-

m a r i n e origin. The same is true for s i l i c i f i e d

gions;

(cemented) sandstones. It is p r o p o s e d here that

this gives rise to m i x i n g

m e t e o r i c and m a r i n e p o r e w a t e r

zones of

(Fig.

19 B) ,

if a certain p o r o s i t y and p e r m e a b i l i t y
given,

is

The i n f l u e n c e of m e t e o r i c w a t e r s

all,or at least m o s t , s e c o n d a r y cherts are formed in c o a s t a l regions or r e l a t i v e l y u p l i f t e d

areas under the i n f l u e n c e of m e t e o r i c water. The

on the f o r m a t i o n of cherts in m a r i n e

formation

sediments

ably be in s e d i m e n t s w i t h m i g r a t i n g pore fluids,

is i n d i c a t e d by o x y g e n i s o t o p i c

ratios in the s i l i c a p h a s e s of cherts

(Section 2,5) w i t h h i g h e r v a l u e s

for

of any kind of nodules s h o u l d p r e f e r -

w h e r e a s in s t a g n a n t pore w a t e r systems, such as

160.

in deep sea sediments, the f o r m a t i o n of nodules

The b e s t c o n d i t i o n s for the i n t r o d u c t i o n of

is harder to explain. C a r b o n a t e nodules s e e m to

s i l i c a - r i c h t e r r e s t r i a l s o l u t i o n s into m a r i n e

have formed in n e a r - s h o r e areas under the in-

Fig. 19. I n f l u e n c e s of (A) t r a n s g r e s s i o n , (B) r e g r e s s i o n ,

and d o w n f a u l t i n g on the d e v e l o p m e n t of p o r e w a t e r systems

and (C) t e c t o n i c u p l i f t i n g
(not to scale),

Der Einf]u~ yon (A) Transgression, (B) Regression und (C) tektonischer Hebung und $enkung
auf die s
von Porenwassersystemen (nicht maBst~blich).

285

f l u e n c e of m e t e o r i c w a t e r a as s u g g e s t e d for

it is still m e n t i o n e d here,

c a r b o n a t e n o d u l e s of the C a m b r i a n L i o n

v e s t i g a t i o n might,

M o u n t a i n S a n d s t o n e in C e t r a l T e x a s

a d d i t i o n a l proof can be found.

1979), M a n y e x a m p l e s

(CHAFETZ,

in the l i t e r a t u r e

coasts)

away from coastal r e g i o n s

(Fig.

18; M I D D L E M I S S ,

in fact show if new and

(palaeo-

1978).

have b r o u g h t such s i l i c i f i e d s e d i m e n t s from

a s h a l l o w w a t e r e n v i r o n m e n t to the deeper
w a t e r d e p t h s w h e r e they are found today.
If the above c o n s i d e r a t i o n

GRIPP
higher

(1954)

states in his p a p e r

Faulting

caused by p l a t e t e c t o n i c s m i g h t p o s s i b l y

i n d i c a t e that s e c o n d a r y c h e r t c o n c e n t r a t i o n
decreases

and further in-

"the

and n e a r e r to an old surface,

is true,

secon-

d a r y chert m i g h t become an i m p o r t a n t

the m o r e

in p a l a e o g e o g r a p h i c

tool

reconstructions.

intense is the o c c u r r e n c e of flint in the

Upper C r e t a c e o u s of Denmark, N W - G e r m a n y

and

Silica-rich

s o l u t i o n from c h e m i c a l

the Paris B a s i n e s p e c i a l l y in its b o r d e r

weathering

region",

f o r m a t i o n of p r i m a r y s i l i c e o u s d e p o s i t s

but a t t r i b u t e s

this to a v e r t i c a l

r e g i o n can,

thus, e x p l a i n the
in

i n f l u e n c e of s i l i c a - r i c h t e r r e s t r i a l p o r e -

b a s i n s or d e p r e s s i o n s w i t h m o r e sheltered,

fluids. A p r o b l e m arises in r e g a r d to all

quiet, m a i n l y a n a e r o b i c c o n d i t i o n s

nodular

w i t h o u t the i n f l u e n c e of b i o g e n i c silica;

cherts found in d e e p sea deposits,

sometimes

at w a t e r d e p t h s of m o r e than

such as P r e c a m b r i a n

cherts),

(also

and the for-

3000 m. But in these cases it is also sup-

m a t i o n of s e c o n d a r y cherts in m a r i n e sedi-

posed,

m e n t s t w h i c h have been or come under the

that the f o r m a t i o n of those n o d u l a r

cherts o c c u r r e d in p o s i t i o n s w i t h m e t e o r i c
water

influences,

for there are i n d i c a t i o n s

that such s e d i m e n t s

(now found at w a t e r

i n f l u e n c e of m e t e o r i c
fluids,

silica-rich pore

as w e l l as an i n c r e a s e d p r o d u c t i v i t y

of s i l i c e o u s organisms.

This m o d e l can

d e p t h of m o r e than 3000 m) w e r e at one time

further explain,

in a m o r e s h a l l o w m a r i n e

c o n n e c t i o n can be seen b e t w e e n them, why

(coastal)

position.

a l t h o u g h in m o s t cases no

This

is p e r f e c t l y shown in the p a p e r by

p r i m a r y and s e c o n d a r y cherts occur at the

LAND

(1979). He d e s c r i b e s

same time i n t e r v a l s

a Miocene chalk

f o r m a t i o n w i t h c h e r t n o d u l e s w h i c h had been

the earth history,

divided

cation processes

(during the L a t e M i o c e n e to the

M i d d l e Pliocene;
uplifted part

WRIGHT,

1974)

into an

part.

the s e c o n d a r y silifi-

lead n e c e s s a r i l y

to the

s i l i c i f i c a t i o n of sediments, w h i c ~ are at

(partially s u b a e r i a l l y exposed)

and in an up to 4200 m d o w n f a u l t e d

in d i s t i n c t p e r i o d s of

lower

The n o w s u b a e r i a l l y e x p o s e d chert

n o d u l e s c o n s i s t only of q u a r t z - p h a s e s ,

least s o m e w h a t older than c o n t e m p o r a n e o u s

p r i m a r y s i l i c e o u s deposits.

Thus the Si/A1-

r a t i o or b e t t e r the r a t i o of d i s s o l v e d
while

s i l i c a to d i s s o l v e d A1 plus d i s o r d e r e d A1-

the cherts in the d o w n f a u l t e d p a r t c o n s i s t

silicates

of o p a l - C T

s e d i m e n t a t i o n seems to be a v e r y i m p o r t a n t

(porcelanite nodules;

LAND,

1979).

The i s o t o p i c c o m p o s i t i o n of b o t h chertand p o r c e l a n i t e - n o d u l e s

r e f l e c t the ~ o n d i t i o n s
ACKNOWLEDGEMENTS

precursors

took p l a c e

suggesting

that b o t h kind of n o d u l e s w e r e

formed u n d e r

factor w i t h r e s p e c t to chert genesis.

if the

under w h i c h the f o r m a t i o n of the chert

faulting.

and

are n e a r l y the same;

this s h o u l d n ' t be too surprising,

isotopic compositions

in the cycles of w e a t h e r i n g

(Section 2.5),

similar c o n d i t i o n s prior

More examples

to

can be found in

the l i t e r a t u r e g i v i n g e v i d e n c e or an

I am p a r t i c u l a r l y g r a t e f u l
Dr. W. K a s i g

(Aachen)

to w r i t e this paper s for n u m e r o u s discussions,

as w e l l as for his support in

i n d i c a t i o n that s e d i m e n t s w i t h chert

every respect,

n o d u l e s or s i l i c i f i e d s e d i m e n t s o r i g i n a t e d

E c h l e and Prof.

in a s h a l l o w m a r i n e e n v i r o n m e n t p o s s i b l y

for s u g g e s t i n g

under the i n f l u e n c e of m e t e o r i c waters.

the m a n u s c r i p t .

A l t h o u g h these c o n s i d e r a t i o n s

seem to

be s o m e w h a t i n c r e d i b l e and even u n b e l i e v a b l e

to Prof.

for his e n c o u r a g e m e n t

Further
Mrs.

M.-L.

and also to Prof.

Dr. H. F H c h t b a u e r
valuable

Dr. W.
(Bochum)

improvements

I w o u l d like to thank Dipl.

F r e y for w r i t i n g

to

Geol.

the m a n u s c r i p t ,

284

my wife Marie-Theres,
rich, Mrs. Wette,
and colleagues

welcomed

Dipl. Geol. V. Diede-

E. Brazil

and my friends

version of an aspired

for their assistance.

As the research
for any omissions

has been written

is only at a beginning

stage I would like to apologize

for. This paper is a very early

to PH.D.

on the genesis

of chert. As only some of

the references

from the thesis

1982) have been cited,

in advance

interested

or misinterpretations

ferences

(about 700)

comments

for a copy.

(LASCHET t

those who are

in the complete

which may have crept in. Any critical

to this paper are sought and

thesis and

to provoke new discussions

list of re-

are invited

to ask

R E F E R E N C E S
ALEXANDER,

G.B., HESTON,

W.M.

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O.

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(Israel).ARBEY,

F.

I Pl.,
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Geol., ~,

121-129,

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4 Figs.,

72 Figs.,

Bull. Cent.

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silica in

in the water of the Dead Sea

4 Tabs., Amsterdam

Les formes de la silioe et l'indification

silifi~es.-

W.H.

(1954): The solubility

Easton

Silica content and silica-clay

Chem.

(1980):

formation

& ILER, R.K.

58, 453-455,

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Prod.

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309-365,

Pau

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BRAITSCH,

O.

D.E. & THOMAS,

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J.D.

& LISS, P.S.

CALVERT, S.E.
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5 Figs.,

H.S.

CHOWNS,

T.M,

DAPPLES,

& ELKINS,

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25/A,

DARRAGH, P.J.,
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DAVIS,

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Bull.,
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J.E.

GASKIN, A.J.

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J.M., MEASURES,

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Nature,

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219,

919-920,

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49/1,

(1974): The origin of geodes

nodules.-

of amorphous

I Tab,, Washington
215-222,

tidal inlet

7 Figs.,

and cauliflower

Tulsa

cherts through

J. Sed. Petrol., 4_~4/3, 885-903,

Developments

9 Figs.,

in Sedimentology,

& SANDERS,

J.B.

(1976):

Opals.-

Sci. Am.,

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Acta,

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