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L. Paul Knauth*
A model for the origin of chert Department of Geology
Louisiana State University
in limestone Baton Rouge, Louisiana 70803

ABSTRACT
It is proposed that many nodular cherts in limestone have formed in
the ground water of mixed meteoric-marine coastal systems where dissolu-
tion of biogenic opal and mixing of marine and fresh waters can produce
waters highly supersaturated with respect to quartz and undersaturated
with respect to calcite and aragonite. Aspects of cherts readily explained
by this model include the observed isotopic ratios in cherts, typical field
relationships, the relative resistance of d o l o m i t e to silicification, the
source-of-silica problem, the preservation of siliceous fossils in cherts,
and aspects of chert morphology and mineralogy.

INTRODUCTION waters highly supersaturated with respect aragonite shell debris accumulated during
to quartz and undersaturated with respect large tides and storms, as observed in
In order to explain chert replacement to calcite and aragonite. modern carbonate environments. In typical
of limestone it is necessary to identify geo- pre-Cenozoic carbonate environments
logic conditions where diagenetic waters silica-secreting sponges were abundant,
are simultaneously supersaturated with CALCITE-SILICA SOLUBILITY and it is reasonable to assume that these
respect to crystalline silica and under- RELATIONSHIPS IN A MIXING ZONE older subaerial sediments contained an
saturated with respect to calcite. Correns A generalized geologic situation where abundance of biogenic silica debris pro-
(1969) suggested that a solution with a pH meteoric water mixes with marine water portional to the amount of offshore silica
that decreases with time from values above in a coastal setting is shown in Figure 1. production. For the purposes of the model
9 should cause calcite dissolution and silica In this figure the subaerial sediment is to be developed here, however, it is not
precipitation. However, such waters are composed predominantly of calcite and critical that the silica be sponge spicules.
not common in sediments; therefore, this
model fails to adequately explain typical
chert occurrences.
A surprising result of the hydrogen-
and oxygen-isotope analyses of Phanero-
zoic nodular cherts (Knauth and Epstein,
1976) is the observation that most of the
samples analyzed, although collected pre-
dominantly from marine carbonate se-
quences, appear to have formed in waters ///.'//
that were meteoric or at least contained //////
a major meteoric-water component. This
observation, together with the solubility
relationships of silica and the thermo- OCEAN
dynamic properties of mixed carbonate
waters, suggests a simple model for the
origin of nodular cherts in limestone.
Following the ground-water dolomitiza-
tion models of Hanshaw and others (1971),
Land (1973), and Badiozamani (1973),
I propose that much of the chert replace-
ment of limestone has occurred in mixed
meteoric-marine coastal systems, where
dissolution of biogenic opal and mixing of
marine and fresh waters have produced

*Present address: Department of Geology,

Arizona State University, Tempe, Arizona Figure I. Generalized hydrologie situation along a coast. All sediments are carbonate contain-
85281. ing significant amounts of sponge spicules or other forms of opal-A.

274 GEOLOGY, v. 7, p. 274-277, JUNE 1979

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Radiolarian silica or any silica with a solu- oric and marine waters has produced a at 25 °C of ~ 6 ppm (Morey and others,
bility comparable to that of biogenic silica zone of waters undersaturated with respect 1962). Opal-CT (Jones and Segnit, 1971)
will yield similar results. to calcite. The shape of the solubility has a higher solubility, probably between
If two solutions saturated with respect curve depends on many variables and can 40 and 70 ppm (inferred from data of
to calcite are mixed, the resultant solution be strongly asymmetric with respect to the R. O. Fournier figured in Kastner and
can be undersaturated if the original waters degree of mixing (Wigley and Plummer, others, 1977). Both surface sea water and
have either different C 0 2 partial pressures 1976). meteoric waters are undersaturated with
or different temperatures (Bogli, 1964; Opal-A (Jones and Segnit, 1971) with respect to these phases. Using the solu-
Thrailkill, 1968). Wigley and Plummer an equilibrium solubility at 25 °C of bility curve for opal-A across the mixing
(1976) and Hanor (1978) have shown that ~ 100 to 140 ppm, is precipitated bio- zone, the solubility relationships for quartz
ground water in carbonate sediments can genically from surface sea water contain- and opal-CT in the mixing zone are readily
show this effect if the system is effectively ing ~0.1 to 4 ppm silica (Krauskopf, constructed and are shown in Figure 2.
closed with respect to C0 2 . 1959). It is suggested here that as meteoric The shaded area of Figure 2 represents
Possible solubility relationships for cal- water moves through carbonate sediment a zone where ground water in the mixing
cite and silica for the situation depicted containing biogenic particles of opal-A, zone can be simultaneously supersaturated
in Figure 1 are illustrated in Figure 2. the silica concentration can rise and ap- with respect to quartz and opal-CT and
Meteoric water moving down and through proach equilibrium saturation values as undersaturated with respect to calcite.
the carbonate sequence become saturated shown in Figure 2. The silica concentra- It is here that the thermodynamic condi-
rapidly with respect to calcite by dissolu- tion will approach saturation as the mixing tions for silica replacement of limestone
tion of aragonite and magnesian calcite. zone is encountered and will then decrease are met.
Modern surface sea water is supersaturated as mixing with undersaturated sea water It should be noted that kinetic questions
with respect to calcite, and it seems reason- progresses. The low silica content of concerning nucleation and the rate of pre-
able to assume that in shallow carbonate modern surface sea water is attributed to cipitation of crystalline silica from super-
environments throughout Phanerozoic the large amount of biogenic silica re- saturated solutions are not addressed in
time, the ocean was likewise either satu- moval by diatoms. In pre-Cenozoic time this model. It is suggested only that the
rated or supersaturated with respect to it is likely that other pelagic organisms, mixing zone is a geochemical environment
calcite. The idealized calcite saturation such as radiolarians, kept the soluble where silica can replace carbonate under
curve in Figure 2 shows the degree of silica content of marine waters low. As equilibrium conditions.
saturation relative to calcite as a function long as the oceans are not saturated with Chertification in a mixing zone is com-
of the degree of mixing of saturated mete- respect to opal-A, the maximum silica patible with available isotope data. These
oric water with supersaturated marine concentration for the situation shown in data indicate that the waters involved in
water in a system closed with respect to Figure 1 would be in the mixing zone. typical nodular chert formation were
C0 2 . In this example, mixing of the mete- Quartz has an equilibrium solubility marine with a variable meteoric-water
component. Cherts forming nearer the
marine side of the mixing zone would
have isotopic ratios more nearly reflecting
precipitation from sea water. Others would
show varying degrees of meteoric-water
influence.

VERTICAL EXTENT OF THE ZONE

OF SILICIFICATION
Chert nodules in limestones are usually
not evenly distributed, but are often con-
centrated along certain horizons parallel
to bedding. This can be understood in
terms of the geometry of the mixing zone.
The mixing zone is often a near-horizontal
zone which can extend inland many kilo-
metres; the size depends on the land area,
the topographic relief, and the freshwater
flux. For example, on the Yucatan Penin-
% SEA WATER sula of Mexico the mixing zone is en-
countered at a depth of about 70 m across
Figure 2. Solubility relationships of calcite and silica in mixed meteoric-marine ground waters an area of many thousands of square kilo-
closed with respect to CO2. The saturation state is expressed in terms of log £2, where £2 = the
ratio of the ion activity product to the mineral equilibrium constant. A solution is saturated with metres (Back and Hanshaw, 1970).
respect to the mineral phases when log £ 7 = 0 . Positive values of log £2 indicate supersaturation, Another situation is depicted in Figure 3
and negative values indicate undersaturation. In the hypothetical case depicted, mixing of meteoric where shoreline sediments prograde over
and marine waters has produced ground water simultaneously undersaturated with respect to calcite
and supersaturated with respect to crystalline silica. The shaded zone defines conditions in which lagoonal and other offshore deposits.
it is thermodynamically possible for silica to replace carbonate. The spacing of abscissa increments Here the mixing zone can be less than a
is arbitrary. few metres thick and restricted to the sub-

GEOLOGY 275
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interpreted as indicating that dolomite is

not readily replaced by silica and that
silicification occurred during dolomitiza-
i:ion of calcite and aragonite. The mixing
zone is a proposed zone of dolomitization
PROGRADING SHORELINE SEQUENCE (Badiozamani, 1973). According to the
model presented above, chertification oc-
curring during mixing-zone dolomitization
would produce some cherts that enclose
dolomite rhombs. Subsequent burial might
ZONE OF bring about later dolomitization and dia-
CHERTIFICATION
genesis of the surrounding carbonate, but
the dolomite rhombs in the chert would
SEA WATER
be preserved. This possibility could be
explored by examining the isotopic ratios
OFFSHORE MARINE SEDIMENT
of dolomite rhombs in cherts. The in-
W I T H L O W POROSITY, LOW PERMEABILITY cluded dolomite should show isotopic
evidence of having precipitated from
meteoric waters low in O 18 content. In
Figure 3. Effect of porosity-permeability on the thickness of the zone of chertification. Rela-
tively porous and permeable shoreline sediments prograde over offshore sediments of low porosity addition, this model explains why dolomite
and low permeability. The mixing zone is effectively confined to a narrow interval above the con- was not silicified while the calcite was—
tact of these contrasting sediments to produce a relatively thin horizon of silicification. waters of the mixing zone are supersatu-
rated with respect to dolomite (Hanshaw
and others, 1971; Land, 1973; Badio-
surface zone above the offshore deposits. The variability of the distribution of
zamani, 1973).
As progradation occurs, a sheet of sedi- replacement chert in ancient carbonates
ment is progressively exposed to the mixing that contain abundant opal-A is readily
zone, as shown in Figure 3. The vertical understood in terms of variable 2. Thin
extent of this sheet is a function of the chert horizons should overlie carbonate SILICA SOURCE FOR THICK
relative permeabilities of the different sediments that had low initial permeabili- CHERT HORIZONS
sediment layers. A horizon of silicifica- ties as in the case where porous shoreline It has often been questioned whether
tion can be produced with a thickness sediments prograde over lagoonal sedi- silica-producing organisms could have
proportional to the vertical extent of the ments of low porosity-permeability. In this existed in enough abundance to produce
mixing zone. Similar geometries involving case the flow of ground water through the the large amount of chert observed along
transgressive-regressive episodes in a sub- mixing zone is greatest immediately above some horizons in ancient limestones (for
siding basin or other changes in the posi- the contact of coastal and offshore example, Tarr, 1926; Dapples, 1959).
tion of the beach can easily be constructed. sediment. Although possible, it is difficult to argue
If the system is open with respect to that the majority of mineral-producing
C0 2 , the mixing-zone waters would not organisms in carbonate depositional en-
DISCUSSION necessarily be undersaturated with respect vironments could have been silica sponges.
In this model three critical variables are to calcite. However, the silica solubility However, this would be required if the
(1) the amount of opal-A incorporated in curve in Figure 2 would not change. In silica that formed many chert-rich horizons
supratidal carbonate sediment, (2) the rela- this case, silica might be expected to pre- was derived in situ from the opaline debris
tive permeability of subaerial versus off- cipitate as a cement in open voids rather of sponges or other shallow-water silica-
shore sediment, and (3) the question of than replace carbonate. During burial, producing organisms. According to the
whether the system is open or closed with the carbonate would undergo diagenesis, model developed here, the silica is derived
respect to C0 2 . and the final product would be a limestone from the entire sediment pile through
The absence of chert nodules in modern with finely disseminated chert grains rather which the meteoric water travels before
carbonate deposits is readily explained in than nodules. Such limestones are numer- reaching the mixing zone. The silica is
terms of variable 1. None of the studies ous in the geologic column (Folk, 1968). concentrated in the mixing zone. If the
of modern carbonate environments refer In one case, Moore and others (1972) sug- mixing zone is narrow and the flush of
to any but trace amounts of biogenic silica gested that wholesale silica cementation silica-saturated water large, almost com-
in the subaerial sediments. This is the re- of upper foreshore carbonates by reflux plete replacement of the limestone in the
sult of absence of abundant silica sponges waters from prograding supratidal sedi- mixing zone can occur. Biogenic silica
and other silica-producing organisms in ments had occurred. need not make up the majority, or even
modern carbonate environments. If a a major part, of the sediment pile to pro-
modern carbonate environment containing duce a local concentration of chert.
abundant silica sponges or other forms of RELATIONSHIP TO MIXING-ZONE
soluble silica can be found, this model DOLOMITE
would predict that shallow drill cores Unreplaced dolomite rhombs are often PRESERVATION OF SILICEOUS
into the mixing zone would reveal silicifi- observed in nodular cherts. The surround- FOSSILS IN CHERT
cation, providing the system is closed ing carbonate may be extensively or totally In this model sediment exposed to the
with respect to C0 2 . dolomitized. This relationship is usually mixing zone has interstitial waters which

276 JUNE 1979

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are postulated to have approached satura- ing zone, the ground water is super- m i t i z a t i o n by g r o u n d w a t e r : E c o n o m i c
tion with respect to opal-A. Biogenic G e o l o g y , v. 6 6 , p. 7 1 0 - 7 2 4 .
saturated only with respect to quartz.
H a n o r , J. S., 1 9 7 8 , P r e c i p i t a t i o n of b e a c h r o c k
silica in this sediment has little or no In such cases, carbonate would be re- c e m e n t s : Mixing of m a r i n e a n d m e t e o r i c
tendency to dissolve and is more likely placed directly by quartz. If the amount w a t e r s vs. CO2 degassing: J o u r n a l of Sedi-
m e n t a r y P e t r o l o g y , v. 4 8 , p. 4 8 9 - 5 0 1 .
to remain in place and subsequently invert of opal-A initially in the sediment pile is
J o n e s , J. B., a n d Segnit, E. R., 1 9 7 1 , T h e n a t u r e
to quartz. The good morphologic preserva- very small, saturation of the ground water of o p a l : I. N o m e n c l a t u r e a n d c o n s t i t u e n t
tion of silica-sponge spicules commonly with respect to opal-A is improbable. phases: Geological S o c i e t y of Australia
J o u r n a l , v. 18, p. 5 7 - 6 8 .
observed in cherts is thus explained by However, the concentration of dissolved K a s t n e r , M., K e e n e , J. B., and Gieskes, J. M.,
this model. Such preservation is otherwise silica will still reach a maximum in the 1 9 7 7 , Diagenesis of siliceous o o z e s . I.
difficult to understand if the biogenic mixing zone, and as long as it exceeds C h e m i c a l c o n t r o l s o n t h e r a t e of opal-A
t o o p a l - C T t r a n s f o r m a t i o n — A n experi-
material were an in situ source of silica 6 ppm, carbonate can be replaced by m e n t a l s t u d y : G e o c h i m i c a et C o s m o c h i m i c a
for cherts and had to be mobilized to quartz. Acta, v. 4 1 , p. 1 0 4 1 - 1 0 5 9 .
form chert nodules. K n a u t h , L. P., a n d E p s t e i n , S., 1 9 7 6 , H y d r o g e n
a n d o x y g e n i s o t o p e r a t i o s in n o d u l a r and
b e d d e d c h e r t s : G e o c h i m i c a et C o s m o c h i m i c a
SUMMARY A c t a , v. 4 0 , p. 1 0 9 5 - 1 108.
CHERT MORPHOLOGY AND K r a u s k o p f , K. B., 1 9 5 9 , T h e g e o c h e m i s t r y of
The simple model presented above is silica in s e d i m e n t a r y e n v i r o n m e n t s , in
MINERALOGY
an attempt to represent general deposi- Ireland, H. A., ed., Silica in s e d i m e n t s :
S o c i e t y of E c o n o m i c P a l e o n t o l o g i s t s and
Chert that has replaced limestone occurs tional and diagenetic conditions conducive Mineralogists Special P u b l i c a t i o n no. 7,
as nodules, thin beds, and irregular ac- to the replacement of carbonate by chert. p. 4 - 1 9 .
cumulations. The form of the replace- There are certainly other conditions that Land, L. S., 1 9 7 3 , C o n t e m p o r a n e o u s d o l o m i -
t i z a t i o n of m i d d l e P l e i s t o c e n e reefs by
ment is probably controlled by the poros- can allow replacement chert to form, m e t e o r i c w a t e r , N o r t h J a m a i c a : Bulletin of
ity-permeability distribution of the carbon- especially those encountered in high-pH Marine Science, v. 2 3 1 , p. 6 4 - 9 1 .
ate, the hydrologic flow, and various evaporite horizons and during deep-burial M o o r e , C. H., S m i t h e r m a n , J. M., a n d Allen,
S. H., 1 9 7 2 , Pore s y s t e m e v o l u t i o n in a
factors affecting nucleation. For example, diagenesis. The model is used only to sug- C r e t a c e o u s c a r b o n a t e beach s e q u e n c e :
nodules might grow outward from a nucle- gest a way in which many cherts in lime- I n t e r n a t i o n a l Geological Congress, 2 4 t h ,
ation site where the mixing zone occurs stones could have formed. It readily ex- M o n t r e a l , S e c t i o n 6, p. 1 2 4 - 1 3 6 .
M o r e y , G. W., F o u r n i e r , R. O., a n d R o w ,
in sediment that is fairly homogeneous plains many features of cherts common J. J., 1 9 6 2 , T h e s o l u b i l i t y of q u a r t z in
with respect to mineralogy, grain size, in typical Phanerozoic carbonates. Future w a t e r in t h e t e m p e r a t u r e interval f r o m
porosity, and permeability. Thin beds testing and experiment will indicate how 2 5 ° t o 3 0 0 ° C : G e o c h i m i c a et C o s m o c h i m i c a
A c t a , v. 2 6 , p. 1 0 2 9 - 1 0 4 3 .
might occur along the boundaries of a well it can be applied to a solution of Tarr, W. A., 1 9 2 6 , T h e origin of c h e r t a n d f l i n t :
narrow zone of relatively permeable sedi- the chert problem. University of Missouri S t u d i e s , v. 1, no. 2.
ment. CO z introduced into the waters by Thrailkill, J., 1 9 6 8 , C h e m i c a l a n d h y d r o l o g i c
f a c t o r s in t h e e x c a v a t i o n of l i m e s t o n e caves:
biologic activity or by the decay of organ- Geological S o c i e t y of A m e r i c a Bulletin,
isms might locally affect the calcite solu- REFERENCES CITED v. 7 9 , p. 1 9 - 4 6 .
Wigley, T.M.L., a n d P l u m m e r , L. N., 1 9 7 6 ,
bility and further affect the chert- Back, W., a n d H a n s h a w , B. B., 1 9 7 0 , C o m p a r i s o n Mixing of c a r b o n a t e w a t e r s : G e o c h i m i c a
replacement distribution. of c h e m i c a l h y d r o g e o l o g y of t h e c a r b o n a t e et C o s m o c h i m i c a A c t a , v. 4 0 , p. 9 8 9 - 9 9 5 .
p e n i n s u l a s of Florida a n d Y u c a t a n : J o u r n a l
In siliceous oozes, opal-CT is the first of H y d r o l o g y , v. 10, p. 3 3 0 - 3 6 8 .
silica phase to form during diagenesis. B a d i o z a m a n i , K., 1 9 7 3 , The D o r a g d o l o m i t i z a -
t i o n m o d e l — A p p l i c a t i o n t o t h e Middle ACKNOWLEDGMENTS
The opal-CT is subsequently transformed O r d o v i c i a n of W i s c o n s i n : J o u r n a l of Sedi-
to quartz. At the present time there is no m e n t a r y P e t r o l o g y , v. 4 3 , p. 9 6 5 - 9 8 4 . Reviewed by C. H. Moore, H. Blatt, F. T.
compelling evidence to indicate that opal- Bogli, A., 1 9 6 4 , M i s c h u n g s k o r r o s i o n : Ein MacKenzie, and R. Siever. The geochemistry
Bertrag Z u m V e r k a s t u n g s p r o b l e m : E r k u n d e , o f m i x e d meteoric-marine waters was greatly
CT initially replaces carbonate except in v. 18, p. 8 3 - 9 2 . clarified b y discussions with J. S. Hanor, w h o
deep-sea cherts. In terms of the equilib- C o r r e n s , C. W., 1 9 6 9 , I n t r o d u c t i o n to min- also read an early version o f the manuscript.
rium relationships shown in Figure 2, both eralogy: N e w Y o r k , Springer-Verlag, 4 8 4 p.
The e f f e c t s o f porosity and permeability on
Dapples, E. C., 1 9 5 9 , T h e behavior of silica in
opal-CT and quartz could replace carbon- diagensis, in Ireland, H. A., ed., Silica in mixing-zone g e o m e t r y were explained to me
ate in the mixing zone. Opal-CT would s e d i m e n t s : S o c i e t y of E c o n o m i c Paleon- by C. H. Moore. Supported by the Louisiana
subsequently be transformed to quartz. tologists a n d Mineralogists Special Publica- State University Applied Carbonate Research
t i o n n o . 7, p. 3 6 - 5 4 . Program and National Science F o u n d a t i o n
However, the solubility of opal-CT is F o l k , R. L., 1 9 6 8 , P e t r o l o g y of s e d i m e n t a r y Grant E A R 7 8 - 0 2 6 2 2 .
poorly known and may be significantly rocks: Austin, Texas, Hemphill's Bookstore,
higher than indicated by Figure 2. It is 170 p. M A N U S C R I P T R E C E I V E D DEC. 2 6 , 1 9 7 8
H a n s h a w , B. B., Back, W., and Deike, R. G.,
conceivable that across much of the mix- 1 9 7 1 , A g e o c h e m i c a l h y p o t h e s i s f o r dolo- M A N U S C R I P T A C C E P T E D MARCH 2 3 , 1 9 7 9

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Geology

A model for the origin of chert in limestone

L. Paul Knauth

Geology 1979;7;274-277
doi: 10.1130/0091-7613(1979)7<274:AMFTOO>2.0.CO;2

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