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(-
Diagenesis
(Geoscience Canada reprint series; 4) c
Includes bibliographical references.
ISBN 0-919216-40-4
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1. Diagenesis. 2. Rocks, Sedimentary.
c
I. Mcllreath , Ian A. II. Morrow, D.W. c
III. Geological Associat ion of Canada. IV. Series. c
QE571.D43 1990 552'.03 C90-090377-5 c
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Cover Explanation: Realms of burial dia-
genesis (mesogenesis) are colour-coded in
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shades of yellow. Early diagenesis (eogene- c
sis) is shown in purple and post-uplift dia-
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(

r:

CONTENTS
(
r
Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v

Introduction .
I.A. Mcllreath and D. W Morrow
r:
Limestones - Introduction .
N.P James and P W Choquette

( Limestones - The Sea Floor Diagenetic Environment


N.P James and PW Choquette
(
Limestones - The Meteoric Diagenetic Environment @§)
N.P James and P W Choquette

Limestones - The Burial Diagenetic Environment @


P W Choquette and N.P James

Dolomite - Part 1: The Chemistry of Dolomitization and 113


c Dolomite Precipitation
D.W Morrow

Dolomite - Part 2: Dolomitization Models and Ancient Dolostones . . 125


D.W Morrow

~~1P~~~~~e;~~d ·I i<.·L~~~~~t~i~' 8
Aspects of the Diagenesis of Coarse-Grained Siliciclastic Rocks .. @
r
I.E. Hutcheon

r: Catagenesis of Argillaceous Sedimentary Rocks 177


A. E. Foscolos .
r
Chemistry and Diagenesis of Organic Matter in Sediments 189
and Fossil Fuels
M.A. Barnes, WC. Barnes and R.M. Bustin

Determining Levels of Organic Diagenesis in Sediments 205


and Fossil Fuels
R.M. Bustin, M.A. Barnes and we. Barnes

Origin of Chert: Diagenesis of Biogenic Siliceous Sediments 227


R. Hesse

Silica Diagenesis: Origin of Inorganic and Replacement Cherts .. .. 253


R. Hesse

Early Diagenetic Pore Water/Sediment Interaction: 277


Modern Offshore Basins
R. Hesse

Fluid Geothermometry in Sedimentary Systems 317


I.E. Hutcheon, H.L. Abercrombie and D. Gardner

Index 325
/

c v

Co PREFACE
r:
The articles that formed the Diagenesis series in Other new contributions to the original series have
G Geoscience Canada were initiated by the senior editor, Ian A. been provided by R. Hesse, and I.E. Hutcheon, H.J. Aber-
Mcllreath, in the March 1982 issue of Geoscience Canada. crombie and D. Gardner concerning Inorganic Chert and
C The underlying philosophy of the Diagenesis series was Fluid Geothermometry, respectively. We are grateful for
o similar to that of the Facies Models series edited by Roger G.
Walker. Like the Facies Models series, the Diagenesis series
these additional contributions. The emphasis of the latter
paper is not on the origin of a particular rock type, but rather
( has been directed toward the non-specialist, the "general on an important aspect of the subsurface diagenetic
( , purpose geologist" alluded to by Professor Walker in the environment. This paper was included to remind even the
preface to the Facies Models series, and toward research casual reader that diagenesis involves the study of pro-
r:
scientists interested in aspects of diagenesis outside their cesses that affect the physico-chemical characteristics of
normal fields of specialization. The enormous success of the the diagenetic environment and to encourage the reader to
G first review series indicated that other aspects of the geo- look beyond the geologist's natural emphasis on the " end
o sciences, such as diagenesis , would benefit from this type of
simplified approach. As with the Facies Models series,
products " of diagenesis to the conditions and processes that
formed these "end products". The paper by Hutcheon,
o authors were asked to prepare reviews dealing with aspects
of diagenesis that entailed a minimum of jargon ,but yet
Abercrombie and Gardner fulfils this need by showing how
dissolution and precipitation of minerals in the subsurface is
c covered a signif icant part of the subject. Diagenesis itself is a closely related to temperature and solution composition.
natural associate of the subject of sedimentology, the main Ian Mcllreath originated this series and invited one
focus of the Facies Models series. An appreciation of both of the authors , David W. Morrow, to later join him as co-editor
o sedimentology and diagenesis are, of course, necessary for in order to facilitate the handling of what proved to be a

o an overall comprehension of the origin of sedimentary rocks.


In this sense, the Diagenesis review series is a natural
review series of unusual length. The length of this series has
also led to the decision not to include papers dealing pri-
o
r:
complement to the Facies Models series.
Twelve of the fifteen contributions within this vol-
marily with techniques for the study of diagenesis. This has
led to the exclusion of some papers that were part of the
ume originally were published in Geoscience Canada and original Geoscience Canada series from the final Diagenesis

o have since been revised for publicat ion here. Three papers
are new to this series and have been included to broaden the
volume and to the inclusion of some addit ional papers that
were submitted after publication of the Geoscience Canada
volume coverage on the subject of diagenesis . In this regard series. This is an unfortunate, but necessary, consequence
we extend our special thanks to Dr. R.J. Spencer of the of the decision to give priority to a more cohesive series and
University of Calgary for providing us, at relatively short we extend our apprec iation to the authors of papers that

c notice , with a review paper dealing with the diagenesis of


evaporites.
have been excluded for their understanding with regard to
this decision. Revised versions of some of these techniques
This series emphasizes the role that diagenesis papers have recently been included in other compilations
plays in the origin of common sedimentary rock types or, in (see Hutcheon , 1989).
o other words, how diagenesis transforms unconsolidated Monica Easton, as Managing Editor for Geoscience
o sediments into Iithified sedimentary rocks. Most of the
papers in this volume deal with specific sedimentary rock
Canada, has been more than helpful in editing and in hand-
ling the manuscripts for the printer. We thank a succession of
o types and their diagenesis and_are segregated into groups
according to general rock type so that carbonates and
chairpersons (Glen Caldwell, John Kramers , Godfrey
Nowlan and Bob Baragar) of the Geological Association of
evaporites are grouped separately from siliciclastics. Dia- Canada publications committee for their help. Peter Russell
genesis of organic material also is discussed separately and designed the sketches that head each article. Also, thanks
not as part of other rock types because of its widespread are due to Bob McNutt and Andrew Miall, the editors-in-chief
o occurrence as a constituent in all rock types and because of
its paramount economic importance both as coals and as
of Geoscience Canada during the progress of this series.
Finally, we extend our thanks to all authors and contributors
o fluid hydrocarbons. of illustrations and photographs for their willingness to fulfil
o our requests and for their monumental patience in waiting for
final publication. We hope their patience has been rewarded.

Ian A. Mcllreath and David W. Morrow


Petro-Canada and the Institute of Sedimentary and
Petroleum Geology, 1990
General Introduction

L ! ",,, ~
11 01
cesses such as compaction, cemen- is possible to assert, in a general way,
( tat io n, solut Lo~lJ.:Ill.adlated minera) that the realm of diagenesis is charac-
recrystallization and r.eRlacement, sub- ter ized by pressures of 0.1 MPa to
surface_solutiQo:IeJiching,.coaliflcatic;>..D.. 10MPa(1.0 bar to 1kb) and by tempera-
aiidttle degradation of organic material tures ranging from 0° to 300°C (see
( and generation of h drocarbon5.""Some Bates and Jackson , 1987). This corr
au ors, part icularly Russian workers sponds to a maximum burial depth of
(e.g., Strakhov, 1956), differentiate about 10 to 15 kilometres. In other
( between the period of initial lithification words, diagenesis occurs under the
of unconsolidated sediment and later pressure-temperature conditions char-
( changes that affect already lith ified acteristic of the earth 's outer crust and
Diagenesis
( rock. Strakhov (1953, 1956) restr icted the earth's surface.
General Introduction the use of the term " diagenesis" to One natural thermodynamically de-
apply only to the initial lithification fined interface that might be consid-
stage and applied the term " cata- ered to place an absolute operational
David W. Morrow
genesis" or "metagenesis" to any and upper limit on the realm of diagenesis
Institute of Sedimentary and
all subsequent changes that affect coincides with the critical points of
Petroleum Geology
sedimentary rocks. However, in Norti ' aqueous solutions involved in diagene-
( 3303 - 33rd Street N. W
America and Europe, the term " d i ag e ~­ sis. This is the curvilinear plane in pres-
Calgary, Alberta T2L 2A 7
esis" is taken to embrace all Chang~ sure - temperature - composition
Ian A. Mcllreath that occur in sediments and sedimen space across which liquid solutions
Petro-Canada tary rocks up to the time when they and their associated vapour phases
enter the realm of metamorphism merge to become single fluid phases.
c P. O. Box 2844
Calgary, Alberta T2P 3E3 (Larsen and Chilingar, 1979; see also
Foscolos, this volume, p. 177-187).
Little is known about the effects of
supercritical fluids on sedimentary
INTRODUCTION .;;!.. The transition between diagenesis rocks except to say that recrystalliza-
In this general introduction to a review ~nd metamorphism has not been as tion is likely to be much more rapid and
of diagenesis, we want to give the rigorously defined as the transition complete under the ir influence than
reader a broad overview of the papers between sediment deposition and that experienced by rocks containing
that are gathered together in this vol- subsequent diagenesis. As discussed subcritical solutions. One problem with
ume. Also, we aim to provide insight by Larsen and Chilingar (1979), it is im- this type of demarcat ion of the diagen-
( into what constitutes the scope of dia- possible to determine a unique combi- esislmetamorphism boundary is that
genesis and comment on some practi- nation of pressure and temperature even for pure water the critical tempera-
cal if not economic reasons why we that could be taken to characterize the ture of 374°C is considerably greater
should study diagenesis. Lastly, we transition between diagenesis and than that generally assumed to coincide
hope to give the interested reader some metamorphism because of the greatly with the upper temperature limit of the
indication as to what are the directions contrasting degrees of mineralogic diagenetic realm. This natural thermo-
of modern research toward the study of stabilities that characterize different dynamic demarcation is even less realis-
diagenesis. rock types. For example, evaporites tic for the much higher critical tempera-
recrystallize at temperatures and pres- tures and pressures that apply to the
DIAGENESIS - DEFINITION AND sures that have little affect on quartz saline aqueous soutions (Crawford,
SCOPE sandstones. Most workers would pro- 1981, fig. 4.12) that predominate in the
The term "diagenesis", like the term bably concur with Fyfe at al. (1958)that subsurface (Dickey, 1969). Conse-
"facies " (e.g., Walker, 1979), has diagenesis involves minor changes in quently, the pressure-temperature
undergone continual redefinition and the rock matrix and "crystallization of boundary separating diagenetic from
discussion since its introduction to the cement minerals in the hitherto open metamorphic conditions in the subsur-
geological literature by Von Guembel pores" whereas metamorphism occurs face occurs at considerably lower tem-
(1868). Larsen and Chilingar (1979), in where "the coarse crystal grains are peratures and pressures than those
their comprehensive review of diagene- also extensively involved in reaction so which characterize the critical points of
sis in all its aspects, provide an excel- that the rock becomes substantially subsurface fluids. In other words, dia-
lent historical summary of the term recrystallized". In essence, therefore, genesis of rocks proceeds only under
"diagenesis" as it applies to the origin of the classification of a particular rock as the influence of subcritical fluids; liquids
sedimentary rocks. Broadly speaking, metamorphic indicates that the original and their associated vapour phases.
as Larsen and Chilingar (1979) have sedimentary components are no longer Important consequences of the sub-
stated, "diagenesis can be defined as discernible as might be inferred from critical chemical behaviour of diage-
the changes whi ur in the charac- the etymology of the word "metamor- netic fluids include the fractionation of
ter and com osition of sed iments~ phosis". gases, such as carbon dioxide, hydro-
ginning from the moment of de osi' Although it is not possible to assign gen SUlphide, methane and other light
and lasting until the resultin materials unique ranges to the pressure and tem- hydrocarbons between the gaseous
roc s ~eJI1QY..e.d.J.ntQ the...r.e.al!J:L..Dl perature conditions characteristic of and liquid phases (i. e., dissolved
~9J: ~_ " alJd includes ro- subsurface diagenetic environments, it gases). For example, the existence of a
c
2 Diagenesis Geoscience Canada Reprint Series 4 c
(

large subcritical H20-C02 unmixing cipitation. Exceptions to this rule occur sents a quantitative, or at least semi- c
solvus (Todheide and Franck, 1963)
controls the composition of the CO2 -
where secondary porosity is developed
with the opportunity for further signifi-
quantitative, approximation of objec-
tively measureable parameters such as
c
bearing diagenetic solutions that are
most important for the creation and
cant porosity occlusion by diagenetic
minerals precipitated during later burial
mineralogic composition and texture.
In contrast, the classification of Cho-
c
destruction of subsurface porosity episodes . The effects of telogenesis quette and Pray (1970) and other simi-
through their participation in equilibria
involving carbonate minerals (see
can, of course, be repeated many times
and are particularly important in the
lar schemes primarily are inferential
and are based on the inferred origin or
c
Hutcheon , this volume, p. 165-176). diagenesis of soluble carbonates and genesis of diagenetic features observed
In recognition of the fundamentally
different processes that affect sedimen-
evaporites. Telogenesis can totally
erase the effects of earlier diagenetic
in sedimentary rocks. It is precisely
these features and phenomena about
c
tary rocks in a variety of diagenetically events in these soluble rock types. which our knowledge is very in - c
distinctive near-surface and deeper
subsurface environments many modern
Conversely, telogenesis may have only
a minor effect on insoluble siliciclastic
complete. Rocks which have very dif-
ferent diagenetic histories can be quite c
workers have adopted classification
schemes that subdivide these settings
rocks and on organic material. similar in mineralogy and texture. Dolo-
mites (or dolostones) are perhaps the
c
into two or three diagenetic realms. THE DIAGENETIC CYCLE - prime example of a rock type for which c
Recently, the tripartite classification of
Choquette and Pray (1970) has gained
PROCESSES, CONTROLS AND
PRODUCTS
classifications such as that of Choquette
and Pray (1970) can not be used with c
in popular usage (e.g., Schmidt and
Macdonald, 1979). In this classification
Classifications, such as that of Cho-
quette and Pray (1970), are useful in
confidence even though dolostones
themselves are considered by most
c
of diagenetic realms, eogenesis is that they communicate to the reader workers to be, almost invariably, com- c
(b defined as those diagenetic changes important information in a cursory pletely diagenetic in origin (Larsen and
c
that occur at or near the sediment@.olJ manner and the reader is forced to Chilingar, 1979). Consequently, the
SUrface where the interstitial solutiollS_
are still in communication with the over-
understand the rationale that underlies
these classificat ions. However, all clas-
objective of the reviews gathered
together in this series of articles lies in
c
lying water mass. After burial has effec- sifications have a drawback in that they demonstrating the diversity of pro- c
tively sealed the pore-filling solutions
from the overlying water mass , the
are generalizations. If a classification
scheme deals with purely descriptive
cesses through which sediments are
diagenetically altered and Iithified rather
c
enclosing sediments are considered to
r ~h ave passed into the mesogenetic dia-
attributes, such as classifications of
sedimentary rock types, then it pre-
than to categorize them rigorously
within classification schemes.
c
~genetic realm of the dge~ubsurface. c
THE DIAGENETIC CYCLE
Most sediments remain in the meso-
genetic regime throughout most of their
c
c
.
diagenetic history. Diagenesis that
occurs under the direct influeMfLQf.
r?i\eteoric solutions following uplift and SEDIMENTS c
\.:::::./eroslon IS conl:1!gne.cLto..tbe..telogeaetic
diagenetic .J..Ei9.i.m_e.... Other, similar
\ c
schemes that separate early diagenesis DIAGENETIC PROCESSES
~
c
from later diagenesis during burial and
from diagenesis after uplift and erosion INCREASING
ROCK/FLUID INTERACTION
DECREAS.... c
have been proposed (Fairbridge, 1967).
Organic geochemists tend to use the
THERMODYNAMIC
GRADIENTS
THERIIIOGYNAMIC
8RADIENTS c
term catagenesis in place of "meso- ,r------,~
DIAGENETIC PRODUCTS c
genesis" to indicate the diagenetic
changes that affect organic material
ROCK AND PORE SPACE
WITH CONTAIMED FLlHDS c
during burial (see Bustin and Barnes, c
this volume, p. 000-000).
Diagenesis for most ancient sedimen- +
ROCK C
tary sequences involved the repeated
exposure of these sequences to diage-
NON-POROUS
HtGHL Y-CEMENTED
E
netic realms as these sequences under-
Figure 1 A schematic representation of burial diagenesIs. The commonly observed correla-
\.
went cycles of subsidence and uplift.
Generally, however, the imprint of the tion of porosity reduction with burial depth is accompanied by repeated departures of the rock/
water system from thermodynamic equilibrium. These departures result in mineral precip itation
C
original eogenetic and mesogenetic his-
tory is preserved because of the large
or dissolution until the pore solution becomes saturated with respect to potential mineral C
precipitates. The natural evolution of pore fluids in the direction of increasing concentration or
porosity reduction and lithification that salinity with increas ing depth of burial favours mineral precipitation and porosity reduction C
occurs during the initial episodeof burial during burial diagenesis . However, many processes can interrupt or reverse this trend and
diagenesis. This severely limits the cause the retention or secondary development of porosity in the subsurface that is necessary C
extent of subsequent mineral pre- for the emplacement of hydrocarbon accumulations and many mineral deposits.
l
'--
<.
(,
( General Introduction 3
(

c Commonly, sediments undergo mul- formities. The immense Fateh Field of crystallization from clay minerals during
o tiple stages of diagenesis in the subsur-
face reflecting a succession of epi-
the United Arab Emirates, with over on
billion barrels of ultimate recoverable oil
burial-induced clay diagenesis also has
the potential to cause mineral under-
( sodes of cementation, dissolution and reserves, is an outstanding example of saturation in pore solutions and may

c recrystallization. In a very generalized


manner, these episodes may be viewed
reservoir enhancement by secondary
porosity development during the circula-
play a significant role in the develop-
ment of subsurface "overpressured"
( as part of an overall diagenetic cycle tion of low salinity meteoric ground zones (see Foscolos, this volume,
(Figure 1) involving cyclical departures water beneath an unconformable s - p. 177-187).
( of the rock/fluid system from thermo- face (Jordan et aI., 1985).

o dynamic equilibrium. These depar-


tures from equilibrium are followed by
It can readily be appreciated then that
the occurrence of hydrocarbon accu-
SEDIMENTARY ROCKS AND FLUIDS
- DIAGENETIC END PRODUCTS
o rock/fluid interaction that may be man-
ifested as the precipitation of mineral
mulations of economic size is linked to
the preservation of original or primary
The primary focus of the articles pre-
sented in this volume is on the end pro-
o cements, as pore space creation and porosity, or to the creation of secondary ducts of diagenesis - the rocks them-

o enlargement by dissolution or by fluid-


mediated mineral replacement reac-
porosity throughout the burial range
favourable for the maturation of hydro-
selves and the processes that led to the
development of individual rock types.
o tions. These processes all reflect the carbons (see Barnes et a/., this volume,
p. 189-204). This is true also for the
The sequence of articles here is dif-
ferent from their original order of
o return to thermodynamic equilibrium of
the rock/fluid system. occurrence of many economic metal appearance in the Geoscience Canada
This type of generalization empha- deposits which, in addition, depend series. Here, there is an overall subdivi-
C- sizes the great variety of subsurface upon the generation of subsurface solu- sion between sedimentary rocks that
O chemical processes that cause dissolu- tion salinities compatible with the for- originated as chemical sediments and

o tion and precipitation in response to


departures from thermodynamic equi-
librium. However, diagenesis itself is
mation of soluble chloride metal com-
plexes favourable for the transport of
metals in solution to precipitation sites in
those that are siliceous or siliciclastic.
Papers concerned with organic material
are included in the latter part of the
often represented in terms of unidirec- porous rock (Hanor, 1979). In other volume because of their emphasis on
o tional trends of porosity reduction words, under normal conditions, burial- the maturation of organic material in sili-

o through physical compaction, pressure


solution and mineral precipitation that
dependent processes of hydrocarbon
generation and metal concentration in
ciclastic sediments.
The first four papers by James and
commonly reflect the initial cycle of bur- subsurface fluids are countered by the Choquette deal with the diagenesis of
ial of a sediment which may have en- progressive disappearance of porosity limestones from their initial deposition
dured multiple episodes of burial and and hence a reduced opportunity for the through deep burial diagenesis and

o uplift. Diagenesis during burial is


almost universally accompanied by a
entrapment of hydrocarbons or forma-
tion of ore deposits. Atypical events are
subsequent exposure to meteoric
waters. They point out that diagene-
o trend of increasing pore water salinity
that commonly, though not invariably,
necessary for the generation of en-
hanced subsurface porosity although
sis in limestones is profoundly influ-
enced by the initial sediment miner-
o is linked to a progressive approach to there is now some evidence to suggest alogy, whether it is dominantly magne-

o saturation with respect to dissolved


minerals (Hanor, 1979). Consequently,
that organic maturation itself is respon-
sible, in some cases, for the develop-
sian calcite or aragonite. They outline
the intriguing research that has increas-
o there is an overall tendency for pre-
cipitation of mineral cements to con-
ment of "aecondary porosity t1:1"Ol 19b tb~
generation of organic acids during early
ingly indicated that shallow marine car-
bonate sedimentation and associated
tinue throughout the burial history of a bur ial diagenesis (e.g., Surdam and synsedimentary cementation has not
o sedimentary rock resulting in a rock
that is highly cemented and containing
Crossey, 1985). Commonly, however,
undersaturation with respect to diage-
always been dominated by aragonite.
Early Paleozoic seas may have been t.-
o little porosity (Figure 1). netic minerals in subsurface fluids and dominated by calcite, rather than arag-LV 'f

o Reversals to the general trend of


porosity reduction occur if major mineral
consequent porosity enhancement
through mineral dissolution is accom-
onite precipitation.
The role of climate as a major control
c components of the rock become under-
saturated during diagenesis. The gener-
plished by mixing with less saline mete-
oric solutions. This can occur where
on meteoric diagenesis (i.e., telogene-
sis) and the discussion of pressure-solu-
( ation of secondary porosity in carbon- deeply buried sediments are uplifted to tion effects during burial diagenesisare
ates by subsurface carbonate mineral shallower depths so that the sedimen- emphasized. Pressure-solution, both
l dissolution during burial (Schmidt and tary pile can be infiltrated by fresh or intergranular and along stylolites, is
r MacDonald, 1979) is an excellent exam- brackish ground water. An excellent identified as the most active process in
ple of this type of reversal in which example of meteoric ground water inva- porosity reduction and as a major con-
"~ cementation is followed by dissolution sion that accompanied post-burial uplift tributor of cement during deep burial
and porosity enhancement leading to is afforded by the Mesozoic and Tertiary diagenesis. An abundance of textural,
the development of subsurface hydro- foreland basin sediments of western chemical and isotopic evidence is uti-
carbon reservoirs. Many examples of Canada that were uplifted and subaeri- lized to compare modern with ancient
hydrocarbon reservoir facies and ore ally exposed during the Tertiary Lara- examples of carbonate diagenesis or to
deposit host facies exist because of mide Orogeny (Hitchon, 1984). The re- simply infer diagenetic processes or
porosity enhancement beneath uncon- lease of interlayer water and water of conditions. Among these criteria, oath-
c
4 Diagenesis Geoscience Canada Reprint Series 4 c
c
odoluminescence of cement fabrics, is addressed through the development teins, carbohydrates, lipids and lignin c
although commonly used to infer pre-
cipitational conditions during the
of criteria for the identification of cemen-
tation and recrystallization textures. The
into hydrocarbons. Early diagenesis
ends with the synthesis of " kerogen",
c
cementation of ancient limestones,
appears to us to lack documentation in
presence of certain " high temperature
salts" in evaporites may be useful as
the ubiquitous source material for
hydrocarbons . Unlike many other dia-
c
modern examples of diagenesis. Some minimum temperature geothermom- genetic processes, maturation of hy-
key research, in our estimation, could eters and, along with fluid inclusions, drocarbons is irreversible and strictly c
be done through the systematic inves-
tigation and documentation of the cath-
provide evidence as to temperatures
and pressures that affected these evap-
temperature dependent. Plots of the
hydrogen 'to carbon ratio versus the c
odoluminescent character of modern or
near-modern calcite cements from a
orites during diagenesis.
The second half of the volume, deal-
oxygen to carbon ratio of kerogen (or
bitumen) and coals on "van Krevelen"
c
variety of diagenetic environments. This
would place inferences concerning the
ing with siliciclastic and siliceous rocks
and the diagenesis of organic material,
diagrams delineates the progressive
thermal maturation of these residual
c
significance of cathodoluminescent ce- begins with Hutcheon's paper on the organic solids during burial and gener- c
ment stratigraphy in ancient limestones
on a firmer footing. The role of organic
diagenesis of coarse-grained siliciclas-
tics. Burial diagenetic reactions, such as
ation of hydrocarbons of progressively
shorter carbon chain lengths. Their
c
maturation toward the generation of feldspar albitization and reactions second paper outlines the tremendous c
secondary porosity and late stage ce-
mentation is described in the paper
between clay minerals and carbonates
occur in many siliciclastic sequences
advances that have been made in the
quantification of stages in the thermal c
dealing with deep burial diagenesis. It is
evident that research into the interaction
and are shown to have a profound effect
on the chemistry of pore solutions and
maturation of kerogens and coal. They
discuss vitrin ite reflectance and the
c
of organic material with carbonates dur- on the potential for porosity reduction othe r, less well documented optical c
ing diagenesis has barely begun.
Two papers by Morrow discuss dolo-
through reaction-related cementation.
Some of these reactions generate CO2
methods , such as conodont colour
alteration indices (CAl), palynomorph c
mitization, one of the more elusive dia-
genetic gremlins . The first paper deals
in addition to CO2 generated by organic
maturation. This CO2 can contribute to
thermal alteration indices (TAl), and lip-
tinite fluorescence that are commonly
c
with what is known concerning the the development of secondary porosity compared to an equivalent rank of c
chemistry of dolomitization and dolo-
mite precipitation. The influence of a
or to additional carbonate cementation
and porosity reduction depending on
vitrinite reflectance . Chemical meth-
ods for evaluating source rock potential c
variety of kinetic inhibiting factors
affecting dolomite precipitation at low
whether carbonate equilibria or non-car-
bonate equilibria control the hydrogen
and for characterizing maturation rank
also are discussed. These include tech-
c
temperature is discussed and the re- ion activity (pH) of diagenetic pore solu- niques for isolating biological markers c
cent perception that the presence of
sulphate in solution strongly inhibits
tions. Hydrocarbon recovery efficien-
cies are related to the presence of pore-
or " geochemical fossils", such ho-
panes and steranes, from extractable
c
the precipitation of dolomite, even at filling diagenetic clay and carbonate organic matter (i.e., organic matter sol- c
the high temperatures typical of deep
burial, is assessed. The following paper
minerals.
Diagenes is of fine-grained argilla-
uble in standard organic solvents).
These markers provide information c
deals with the origin of ancient dolo-
stones and a wide variety of models for
ceous sediments is outlined by Fos-
colos. Here, the emphasis is on the
concerning the source rocks for par- •
ticular hydrocarbon accumulations .
c
dolomitization in synsedimentary to effects of the temperature controlled, Rock-EvaliP analysis is presented as a c
deep burial settings are described.
Emphasis is given to mass balance
dominantly isochemical clay reactions
by wh ich swelling clays (smectites)
means for the routine estimation of
both the organic source rock potential c
considerations in assessing the poten-
tial relevance of particular models for
evolve to the non-swelling iIIitic clays
that characterize most ancient basinal
and the maturation rank of most sedi-
mentary rocks in a manner that is most
c
dolomitization. Recent research con- shales. These changes are accom- accessible to petroleum exploration ists c
cerning the origins of dolomite crystal
textures and their potential application
panied by the sporadic release of water
from clay minerals to the pore solution
unfamiliar with organic geochemistry.
Modelling of thermal maturity in basins c
as diagenetic geothermometers are
discussed along with the recent
and may contribute to the development
of overpressured zones in shale se-
is also discussed using calculated time-
temperature indices (TTl) based on
c
application of fluid inclusion studies to quences and, possibly, to hydrocarbon subsidence histories. c
the problem of the origin of dolomite.
Spencer's contribution concerning
migration. The dissolution of feldspars
generates amorphous hydrous gels of
The origin of chert and siliceous sedi-
ments is discussed in two following e
the diagenesis of evaporites rounds out silica, aluminum and iron that can par- papers by Hesse. In the first paper, he
the first half of the volume series. Tex- ticipate in later stages of clay diagene- describes the origin and distribution of
tural studies and criteria for the recogni- sis, such as the growth of diagenetic siliceous sed iments in the world's <--
tion of successive episodes of evaporite chlorite in pore spaces. oceans emphasizing the important role
diagenesis are emphasized. The long Diagenesis of organic material is of water depth in relation to the calcite
C
neglected importance of diagenetic reviewed in the follOWing two papers by compensation depth. Low temperature C
cementation, inferred from the degree Barnes , Bustin and Barnes. In their first maturation of siliceous radiolarians and
of porosity reduction observed in buried paper, they outline the transformation diatoms results in their transformation C
evaporites and ancient evaporites, of initial biologic materials, such as pro- from opal-A to the opal-CT of porcel-
C
C
C
C
r:
c., General Introduction 5

C
r lanites and finally to chert composed example, externally imposed changes search toward understanding diagene-
o dominantly of quartz. The shift in the
d(101) peak position of opal-CT has
in fluid chemistry commonly exert a
strong effect on the diagenesis of car-
sis. Such summaries become dated
very quickly with respect to such a
o some potential as a maturation indicator bonate, clays and aluminosilicates and rapidly evolving subject in which re-

c in sediments less than 100 million years


old. The second paper emphasizes the
silica but has little effect on the dia-
genesis of organic material or evapo-
search efforts are proceeding in many
different directions. With this caveat in
c various modes of siliceous replace-
ments that sediments and rocks
rites. Organic material is commonly not
affected because its diagenesis is dom-
mind, certain aspects of diagenesis can
be identified as undergoing particularly
c undergo. Commonly, such replace- inated by thermal organic maturation intensive research at the present time.

c ments occur under high pH conditions


that favour silica precipitation.
whose reactions proceed relatively
rapidly to form liquid hydrocarbons that
The final paper of this volume by
Hutcheon, Abercrombie and Gardner
( The final two papers of the series, by tend to exclude other fluids from the highlights one important and very active
Hesse and Hutcheon, Abercrombie and pore space. Evaporites are little modern research direction. This is the
( Gardner depart from the main series affected by compositional changes in application of computer-based models

o theme emphasizing the "end products"


of diagenesis in that they deal instead
pore solutions because dissolution of
soluble evaporite minerals effectively
of mineral and aqueous chemistry to
simulate the thermodynamic state of
o with diagenetic conditions and pro- buffers the solution composition diagenetic systems. Figure 2 is an

o cesses. Hesse shows how the inter-


pretation of concentration profiles of
against externally imposed solution
composition changes. Temperature is,
example of a stability diagram gener-
ated by the PC-based program (PTA) of
o pore water chemistry in modern marine
basins can be used to infer rates of
of course, an important external control
on all diagenetic changes involving
Brown et al. (1988). This diagram was
used to infer the compositional changes
o sedimentation and pore water advection
with respect to ongoing sediment reac-
chemical reactions. Silica cementation
has been singled out as an exception to
of waters that participated in diagenesis
of the Clearwater Formation at Cold
tions. The role of organic material in this rule because of the greatly domi- Lake, Alberta, based on the petro-
o controlling early sediment diagenesis
because of the generation of carbon,
nant role that the pH of the solution plays
in silica diagenesis, particularly during
graphically determined sequenceof dia-
genetic minerals (Abercrombie, 1989).
nitrogen, sulphur and hydrogen as bac- early diagenesis, or eogenesis. The rate Programs such as PTA of Brown et al.

o terial metabolites is emphasized.


Hutcheon, Abercrombie and Gardner
of fluid flow has a strong effect in most
diagenetic situations, but generally not
(1988)generate phase diagrams in pres-
sure - temperature - activity space for
show how concentrations of ions, such on the diagenesis of organic material. thermodynamic systems with user-
as sodium, potassium and silica, in solu- Similar reasoning may be applied to the defined components. Other programs,
C tion can be used as geothermometers in other cited diagenetic controls in such as SOLMNEQ (Kharaka and
the presence of equilibrium mineral assessing their relative significance. Barnes, 1973) bridge the gap between
l asemblages. This table is presented merely to give the thermodynamic activities of com-
( Table 1 is meant to provide a gener- the reader an overview of the gener- ponents and their concentrations in
alized assessment of the relative degree alized diagenetic controls that apply to aqueous systems to permit the calcula-
C of importance of individual diagenetic the diagenetic end product rock types tion of mineral saturations from con-
o controls on the development of the dia-
genetic rock types that are described
discussed in this volume. centration data. Other programs, such
as PHREEQE (Parkhurst et al., 1980),
in this series. These controls are DIRECTIONS OF MODERN have been developed which permit the
envisaged as primarily being external in RESEARCH modelling of reaction pathways, which
nature and are imposed upon the rock- It is difficult to summarize in a concise may be plotted on phase diagrams, and
or sediment-pore fluid system. For manner the directions of modern re- can even give estimates of the extent of

Table 1 Dependence of diagenesis on major diagenetic controls.

Diagenetic Controls
Diagenetic Products Biologic Time Temperature Pressure Fluid Flow Fluid
Activity Chemistry
l Carbonate Cementation and Strong Weak Strong Strong Strong Strong
r
Recrystallization
Evaporite Cementation and Weak Weak Strong Strong Strong Weak
Recrystallization
Clay and Alumino-Silicate Weak Strong Strong Weak Strong Strong
Diagenesis
Organic Material Strong Strong Strong Weak Weak Weak
Silica Cementation and Strong Weak Weak Weak Strong Strong
Recrvstallization

"
'---
c
6 Diagenesis Geoscience Canada Reprint Series 4 c
c
mass transfer of chemical components c
between the solid phases and the solu-
tion during fluid-mediated chemical
c
reactions . Ultimately, this approach will
yield important quantitative estimates COMPUTER-GENERATED
c
(
of the amount of porosity loss or gain
MINERAL PHASE DIAGRAM
during successive stages of diagenesis
12
c
for a wide range of rock types .
A closely related intensive research
effort has recently been devoted toward
c
an improved understanding of the inter-
action between organic matter and min-
eraI diagenesis. The production of
organic acids and carbon dioxide as 10 Analcime c
reaction products during the diagenesis
of organic matter has been shown to
c
exert a strong influence on the satura- c
tion state of carbonate minerals and the
acidity of subsurface environments c
(Surdam and Crossey, 1985). Again the
accuracy of the assessment of values
C
for these solution parameters is depend- C
ent upon the development of accurate
models of aqueous chemistry. One Potassium
C
important aspect with regard to the
Feldspar C
improvement of these models concerns
the acquisition of more accurate ther- C
modynamic data for organic acids, such
as acetic acid, which are abundant in
C
subsurface environments. Recent ad- C
vances in the understanding of early
diagenesis of organic material have C
been made concerning the correlation
of early diagenetic mineral reactions,
C
such as the generation of pyrite by sul- C
phidic diagenesis, with the degree of
preservation and availability of organic C
material for diagenesis during later bur-
ial (Gautier, 1985).
C
The diagenetic aspects of models for C
basin development have undergone
definite changes under the impact of o C
new ideas concerning the role of
organic acids. For example, Surdam et
o 2 10 12 C
aJ. (1989) have shown that variations in C
the amounts and types of organic
material results in profound differences C
in the style of mineral diagenesis and in
the evolution of porosity during burial
C
diagenesis of many hydrocarbon-bear-
Figure 2 A computer-generated phase diagram that has been used to infer the evolution of
C
ing siliciclastic sequences .
Rapid recent advances have also fluid compositions during diagenesis of the Clearwater Formation in the Cold Lake heavy oil C
area, Alberta (Abercrombie, 1989). The succession of diagenetic minerals observed in this unit
occurred with respect to techniques that
indicate initial deposition in brackish waters of mixed marine/river composition (stage I).
provideestimates of the relative and abso-
luteagesof subsurfacediageneticevents.
Enrichment of sodium and potassium is reflected by the progression from mixed layer clays (lIa)
to the maximum diagenetic assemblage, stage lib, comprising quartz-Kspar-analcime-iIIite(?). c
Absolute ages for the precipitation of This was followed by precipitation of Kaolinite and isotopically distinct calcite reflecting Tertiary (
authigenic clay minerals and feldspars in uplift of the Clearwater, an influx of low salinity meteoric fluids, and biodegradation of oil. This
siliciclastic sediments may be obtained caused pore fluids to change composition along the path labelled 1/1. C
from the K/Ar, 4OArJ39Ar, and K/Ca iso-
topic dating techniques and from fission C
track dating with greatly improved (
C
C
/'

(
General Introduction 7
r

accuracy in recent years. Such ad- Chilingar, G.V. and Wolf, K.H., 1988, eds., Lundegarde, P.D., 1989, Temporal recon-
C vances greatly improve our ability to Diagenesis , I: Elsevier, Amsterdam , struction of sandstone diagenetic histo-
unravel the geochronological history of Developments in Sedimentology, v. 41, ries, in Hutcheon, I.E., ed., Burial Dia-
G diagenetic cements and consequently 591 p. genesis : Mineralogical Association of
( our ability to understand the history of Choquette, P.w. and Pray, L.C., 1970, Geo- Canada, Short Course Handbook, v. 15,
logic nomenclature and classification of p. 161-194.
diagenesis and its application to basin
( analysis (Lundegarde, 1989). Fission
porosity in sedimentary carbonates: Naeser, N.D., 1986, Neogene thermal his-
American Association of Petroleum Geo- tory of the northern Green River Basin,
( track dating of heavy minerals, such as logists Bulletin, v. 54, p. 207-250. Wyoming-Evidence from fission track
apatite and zircon, also gives important Crawford, M.L., 1981, Phase equilibria in dating, in Gautier, D.L., ed., Roles of
( paleotemperature infor mat ion that aqueous fluid inclusions, in Hollister, Organic Matter in Sediment Diagenesis:
spans the temperature range for oil L.S. and Crawford , M.L. , eds., Short Society of Economic Paleontologists and
( Course in Fluid Inclusions: Applications
generation (Naeser, 1986). Mineralogists, Special Publication No.
c Modern studies of diagenesis have
also moved in the direction of semi-
To Petrology: Mineralogical Association
of Canada, Short Course Handbook Vol-
38, p. 65-72.
Parkhurst, D.L., Thorstenson, D.C. and
o quantitative to quantitative modelling ume 6, p. 75·100.
Dickey, P.A., 1969, Increasing concentration
Plummer, N.L., 1980, PHREEQE - a
Computer Program for Geochemical
o of diagenetic processes from the scale
of diagenetic micro-environments to a
of subsurface brines with depth: Chemi- Calculations: United States Geological

c global scale. Chilingar and Wolf (1988)


provide a broad overview of research
cal Geology, v. 4, p. 361-370.
Fairbridge, R.W., 1967, Phases of diagenesis
and authigenesis , in Larsen, G. and
Survey, Water-Resources Investigations
80-96 (revised and reprinted in 1987),
193 p.
concerning models for diagenesis, Chilingar, G.V., eds., Diagenesis in Sedi- Schmidt, V. and McDonald, DA , 1979, The
particularly as they apply to the ori- ments: Elsevier, Amsterdam . role of secondary porosity in the course
gin of ore deposits and hydrocarbon Fyfe, W.S., Turner, F.J. and Verhoogen, J., of sandstone diagenesis, in Scholle, P.A.
o reservoirs. 1958, Metamorphic reactions and meta-
morphic facies: Geological Society of
and Schluger, P.R., eds., Aspects of
Diagenesis: Society of Economic Pale-
o It is evident that the study of diagene-
sis has expanded far beyond a purely America, Memoir 73, 259 p.
Gautier, D.L., 1985, Interpretations of early
ontologists and Mineralogists, Special
Publication No. 26, p. 209·226.
descriptive stage involving merely the
diagenesis in ancient marine sediments, Strakhov, N.M., 1953, Diagenesis of sedi-
identification of minerals or rocks of in Gautier, D.L., Kharaka, Y.F. and Sur- ments and its significance for sedimen-
diagenetic origin. This series has dam, R.C., eds., Relationship of Organic tary iron formation: Izvestia Akademia
emphasized the contribut ion of diage- Material and Mineral Diagenesis: Nauk SSSR, Series of Geology, v. 5,
netic processes to the origin of specific Society of Economic Paleontologists and p. 12-49.
o rock types. The reader will appreciate,
however, that diagenesis itself involves
Mineralog ists, Short Course No. 17,
p.6·72.
Strakhov, N.M., 1956,Towards knowledgeof
diagenesis, in Questions of Mineralogy
o the interaction of many different pro-
cesses in the lithosphere , biosphere
Hanor, J.S., 1979, The sedimentary genesis
of hydrothermal fluids, in Barnes, H.L.,
of Sedimentary Formations: L'vov Gos.
Univ., L'vov.
and hydrosphere. The complexity of ed., Hydrothermal Ore Deposits: John Surdam , R.C. and Cressey, L.J., 1985,
Wiley and Sons, New York, p. 137·169. Mechanisms of organic/inorganic inter-
some of these processes may be
Hitchon, B., 1984, Geothermal gradients, actions in sandstone/shale sequences,
glimpsed in the papers of this series. It
o is our hope that this information may be
hydrodynamics, and hydrocarbon occur-
rences: American Association of Petro-
in Gautier, D.L., Kharaka, Y.F. and Sur-
dam, RC. , eds., Relationship of Organic
o of assistance to the reader in pursuing
his or her research interests or as an aid
leum Geologists , Bulletin, v.68,
p.713·743.
Matter and Mineral Diagenesis: Society
of Economic Paleontologists and Miner-
to exploration ists involved in the search Hutcheon, I.E., 1989,ed., Burial Diagenesis: alogists, Short Course No. 17, p. 177-232.
for hydrocarbon and mineral resources. Mineralogical Association of Canada , Surdam , RC., Dunn, T.L., Heasler,H.P. and
Short Course Handbook, v. 15, 409 p. MacGowan, D.B., 1989, Porosity evolu-

o REFERENCES CITED Jordan, C.F., Jr., Connally, T.C., Jr. and Vest,
H.A., 1982, Middle Cretaceous carbon-
tion in sandstone/shale systems , in
Hutcheon, I.E., ed., Burial Diagenesis,

o Abercrombie, H.J., 1989, Water-rock inter-


action during diagenesis and thermal
ates of the Mishrif Formation, Fateh
Field, offshore Dubai, UAE., in Roehl,
Mineralogical Association of Canada,
Short Course Handbook, v. 15, p. 61-127.
( recovery, Cold Lake, Alberta, Ph.D . P.A. and Choquette , P.W. eds., Carbon- Todheide, K. and Franck, E.U., 1963, Das
thesis, Department of Geology and Geo- ate Petroleum Reservoirs: Springer-Ver- Zwe iphasengebeit und die kritische
r:
physics, The Unversity of Calgary, Cal- lag, New York, p. 425-442. Kurve im system Kohlendioxid-Wasser
gary, Alberta , 183 p. Kharaka, Y.K. and Barnes, I. , 1973, bis zu Drucken von 3500 bar: Zeitschrift
Bates, RL. and Jackson, J.A., 1987, Glos- SOLMNEQ: Solution-mineral equilib- fur Physiks und Chernie, N.F., v.37,
sary of Geology, Third Edition: American rium computations : Un ited States p.388-40t
Geological Institute, 788 p. Department of Commerce, NTIS Report Von Guernbel, C.w., 1868, Geognostische
Brown, T.H., Berman, R.G. and Perkins, PB 215-899, Springfield, Virginia, 81 p. Beschreibung des ostbayerischen
E.H., 1988, GEO-CALC: Software pack- Larsen, G. and Chilingar, G.v., 1979, eds., Grenzgebirges, I-III, 700 p.
age for calculation and display of pres- Diagenesis in Sediments and Sedimen- Walker, R.G., 1979, ed., Facies Models:
sure-temperature-composition phase tary Rocks: Elsev ier, Amsterdam, Geoscience Canada Reprint Series 1.
diagrams using an IBM or compatible Developments in Sedimentology, v.25A, 211 p.
personal computer: Computers and 579 p.
Geosciences, v. 14, p. 279-289.
c
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SEM photomicrograph of sandstone in the Cretaceous Viking Formation ofthe Caroline Oil Field. Intergrown clusters of authigenic c
microquartz and chlorite (OC) are interspersed with authigenic pyrite (P) in the deeply buried, chert-rich Caroline sandstones.
Chlorite is commonly associated with late-stage burial diagenesis of siliciclastic sediments. Photograph courtesy G.E. Rein!lon
and A.E. Foscolos (Geological Survey of Canada).
c
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Limestones: Introduction 9

tion is surface and subsurface fluid tation, although not ubiquitous, is the
composition. Waters most commonly in most important diagenetic process on
contact with carbonate rocks and sedi- the modern sea floor. It is manifest in the
ments are marine, meteoric or deeE f ormation of grains (i.e., ooids), the hard-
subsurface in origin ~With time, as car- ening of soft grains by intragranular pre-
bonates are deposited, precipitated, cipitat ion (i.e., peloids), and the lithifica-
buried, eroded, exposed and reburied, tion of loose carbonate sediments to
they interact with these fluids, each of form sea floor limestone. In contrast, the
which affects the sediments or rocks in main biological process is boring, by a
a special way and leaves a unique dia- variety of macro and microendoliths,
Limestones: genetic signature. Each region charac- who may destroy much depositional
terized by waters of different composi- fabric .
Introduction tion (Figure 1) can be thought of as a -1k Both of these processes, precipitation
separate diagenetic environment (Pur- and boring, take place on the shallow
dy, 1968). In this synthesis we recog- tropical sea floor. With increasing water
Noel P. James nize three major diagenetic environ- depth, accompanying increases in pres-
Department of Geological Sciences ments : (1) the sea floor and underlying sure and decreases in temperature
r: Queen's University shallow marine phreatic, characterized combine to result in some cases in ~ neo-
Kingston, Ontario K7L 3N6 by marine waters, together with the morphism ..and ultimately in complete
strandline bathed in mixed marine and dissolution. _
Philip W. Choquette fresh waters; (2) the meteoric distin- The Meteoric. If carbonate sedi-
Department of Geological Sciences guished by the freshwater vadose and ments are, through uplift, fluctuations in
University of Colorado plireatic zones and the shallow phre- sea level or simply rapid accretion,
Boulder, Colorado 80309-250 atic region of mixed fresh and marine exposed subaerially to percolating
waters ; and (3) the deep burial, where meteroic waters, dramatic changes take
INTRODUCTION pores are filled with waters that may place. Diagenesis is driven by two reac- 0'1
Limestones are among the most once have been marine but have been tions, one between the carbonates , LV
capricious of rocks. Mostly born from moderately to drastically modified by regardless of composition, and meteonc
the sea and generally biologic in origin, burial diagenesis. Changes that take waters of differing temperature andlor ~~
they possess an extremely sensitive place in each of these settings is the Peo• called water-controlled meteoric V
record of past life and conditions on topic of a separate article in the follow- diagenesis and another between miner-
earth, yet because they are lime and so ing series, but to place the whole spec- als of differing solubilities and meteoric
easily susceptible to chem ical change , trum in context we first summarize the water calledminerakontrolled meteoric
this record is commonly blurred or ren- main attributes of all the realms and diagenesis. Water-controlled alteration is
dered unreadable by diagenesis. Para- outline the diagenetic changes that reflected by the formation of caves and
doxically, this same diagenesis is eco- occur in each. Other karst features, local precipitation of
nomically beneficial because the holes The Sea Floor. Carbonate precipi- spelean carbonates ao.d_calccete-d~I-
and voids created during alteration
may be later filled by base metal pre- /VCr X,'lA..j 2.-0"~ (f,f)lAJ.. .0~ I-/t)
cipitatesor hydrocarbons. So, to under-
stand limestones for any purpose it is
'hV/Iet c-s« * c)
imperative to decipher the often com-
plex series of processes that have mod-
ified their texture and composition
through geologic time.

o
r
The following articles are an overview
and not an in-depth treatment of the
topic ; they are intended as a guide to
r current understanding and a synthesis
®
, ' h:j..
of concepts useful when interpreting the
diagenetic history of limestones. Since DEEP BURIAL
most limestones are marine, the articles
r
. ;...

...... t-- 1. / Y concentrate on these rocks. The papers


,.- '<
were originally written between 1982 (;'j~ I,
} and 1986 and have been revised and .. J7;;';;::;t? .r~"
~j -; Y-;,' \,\t. updated for this volume. l\)nD~ uO#'/ (~"
~ ./ ~ Figure 1 A sketch outlining the main diagenetic environments through which carbonate
,,,)1 \; ~v DIAGENETIC ENVIRONMENTS sediments and rocks pass in geologic history. Depending upon hydrodynamics, configuration
LV' ~\" Since rock-water jnteractionJs the pri- of the aquifer and permeability, the freshwater phreatic waters may underlie only the exposed
1\'" \ i , mary force driving carbonate diagene- area as illustrated here or may extend seaward beneath the shelf and underlie a thin shallow
l'\f'~1 Y sis, a key tactonln the diagenetic equa- ,~t IV marine phreatic zone.
'-'" v· ~ \ ' \..~( ~\ (btl I( I J.t 1 / _ tiC " 0'1 V'!f
r , i"\J~ Q M~'" ~(' '6' ~<,((}v c /)l/f()..rf~1J.0 U.lI\lvV~ l
{f.Jl.l/tl I l l , , , -( .,
~ I). j I' \1lI' >\l ~
/ \) II 1.:-......... lJY~i...,I "!~.-.:!.!!./7'oJ~ -!.-_--
~ ~ <:l \ \I\I"~V 'j \
C~ ~ ~ ~ U1u ~16'''r;j /</1(/
' I) J
,J'....f --.-/ . II i I-(JI/Y YI"'V 'I
D' o U (1'1 "'., 0 'I . I
c
10 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
~
o opment. Mineral-cQntrolled alteration
results in the transformation Qf arag-
burial environment for extended
periods. NQt all carbonates , however,
TECHNIQUES AND LITERATURE
The indispensable source of information c
onite and magnesium-calcite (high
magnesium calcite) to calcite witfi neg-
are flushed by meteor lc waters . Nev-
ertheless, it is common to see some
on the topic of carbonate diagenesis is
the text by Bathurst (1975) and the fol- c
Iigible magnesium CQntent (low magne-
sium calcite). Many components have
evidence of meteoric diagenesis, gen-
erally because in shallow-marine set-
lowup article in 1980 . For a more general
treatment of the subject the reader is
c
their microstructure altered dramat- tings they accumulate rapidly to sea referred to the books by Friedman and c
ically during this process ot mineral
transformation, while others are dis-
level. Combined with subtle fluctua-
tions in sea level, this commonly leads
Sanders (1979), Blatt et al. (1980) and
Flugel (1982). Good sourcesfor the iden- c
solved completely leading tQ new pat- to subaerial exposure and thus mete- tification of components are the vol- c
terns of porosity and permeability.
These changes are accompanied by
oric diagenesis, even if short lived.
In actual experience different dia-
umes by Scholle (1978) and Horowitz
and Potter (1971). For a parallel treat- c
widespread lithfficatlon through ce-
ment precipitation.
genetic processes vary markedly in
importance Irorn environment to en-
ment of diagenesis with a somewhat
different approaches the articles by
c
The processes and products of mete- vlronrnent (Table 1). Most sediments on Longman (1980) and Harris et al. (1985) c
oric diagenesis cannot be applied
equally tQ carbonates ot all ages
the modern sea floor are affected to
some degree by bloerosion, but ce-
are recommended. Papers treating spe-
cific aspects of cementation and neo- c
because ot changes in the biosphere
(varying skeletal mineralogy and ter-
mentat ion is facies specific and most
deposits are unlithified. Once exposed
morphism, petrography and geochem-
istry, can be found in compilations by
c
restrial vegetation) and the atmosphere to percolatinq non-marine fluids, all Schneidermann and Harris (1985) , c
(varying PC0 2) through geQIQgic time.
The rates at which mineral transforma-
sediments suffer some dissolution
toqether with variable cementation and
Schroeder and Purser (1986) and James
and Choquette (1988). c
.t ion, dissoiution, early cementation and neomorphism. The effect of organisms Since the changes that take place are
largely chemical, the study of carbonate
c
the formation of karst features occur
[ are strongly influenced by local surface
is localized to the soil zone with the
formation of calcrete and phytokarst. In <!@geoesjs requires both petrograpbk; c
temperature and rainfall.
The Deep Burial. As carbonate
the deep subsurface compaction and
cementation affect all rocks and sedi-
~Emligal an~sis . The basic
relationships are seen fr.om-stamea c
sediments undergo proqresslve burial ments and are commonly accompanied slabs and thin seJ;.tlons.or,acetate -peels
a~y' be ~lJgmented QY scanning
c
and are subjected tQ increasing temper-
ature and pressure during and after lithi-
by neomorphism. Dissolution, how-
ever, appears to be restricted to spe- electron microscopy. Especially useful c
fication, they go through a variety of
liiO'dftications. The important changes
cific situations.
The degree to which carbonate is
are the trace-element concentrations of
strontium, magnesium, iron and manga- c
which occur include mechanical and altered in any of these settings de- nese and the concentration ratios of car-
bon (13C/12C), oxygen (180/ 160) and, in
c
chemical compaction - during which
porosities may be shar ply reduced;
pends upon (1) the cornposltlon and
flux of the waters through the sediment special cases, sulphur and strontium c
cementation by carbonate, ~hate ,
~ilic.a .silicate mmerals; conversion
or rock, and. ~2) the I~ngth of tim~ t~e
rock or stabilized sediment rernams m
isotopes. Cathodoluminesence, in-
duced in carbonate minerals mainly by
c
of metastable forms of CaC03 to low-Mg
A&-
the environment. excitation of reduced manganese
(Mn2+) and allowing differentiation of
c
calcite (often accompanied by other Because cements are progressively
changes such as clay and gypsum dehy- '-added to the rock as it passes from one various zones within carbonate crystals, c
dration); decomposition, as well as bio-
chemical and thermochemical trans-
diagenetic environment to another, the
sequence of alteration can often by
has become widely used in recent years.
Finally, the nature of past fluids them-
c
formation of original organic matter. .I!!fl worked out best by examining the selves may sometimes be ascertained c
dominan tre 'n burial dia enesi::i ~
long-term rec!..Ud.ioo..af..p.Q.r..Q.s.i.tY-tbJ:gJJgh
"Cement Stratigraphy" in detail. from study of fluid inclusions.
c
tllousands of metres of burial. Under
Table 1 Relative importance of diagenetic processes in carbonates.
c
some conditions, however, porosity ap-
pears to be created anew during bur-
fz,) al di enesis through dissolution of
Diagenetic
Process Shallow Tropical
Diagenetic Environment
Deep
c
Sea Floor
Meteoric
Subsurface C
~
arbon ate grains ana-eemenrs. he de-
~ tails 0 t e 1580 litlon process are still Biogenic
Alteration
extensive localized -- E
unclear, but apparently involve the pro-
duction of CO2 by organic compounds Cementation localized extensive ubiquitous C
undergoing thermobiochemical reac-
tions in the presence of other pore
Dissolution -- ubiquitous localized C
fluids. Neomorphism -- extensive extensive (
Diagenetic Pathways. Most car-
bonates, because they sit on the sea
Compaction -- -- ubiquitous (
floor or in reef cavities for a while before
being buried, suffer some degree of syn-
• Neomorphism as used in these articles refers to the alteration of carbonate minerals in a wet
diagenetic environment through processes of polymorphic transformation (e.g., " inver-
C
sedimentary diagenesis. Similarly, most sion" of aragonite to calcite) or recrystallization (e.g., finely crystalline calcite to coarsely C
ancient limestones have been in the crystalline calcite), but not simple pore-space filling .
C
C
c./
( Limestones Introduction 11

C
f
SELECTED REFERENCES Friedman, G.M. and Ali, SA, 1981, Diagene- Milliman, J.D., 1974, Marine carbonates:
c The literature on carbonate diagenesis
is vast - the following texts and papers
sis of Carbonate Rocks: Cement-
porosity relationships: Society of Eco-
New York, Springer-Verlag, 375 p.
Good review sections on techniques and
o together, give the reader a working nomic Paleontologists and Mineralo-
gists, Reprint Series No. 10.
diagenesis of modern carbonates.
Purdy, E.G., 1968, Carbonate Diagenesis:
r overview and introduction to the topic.
A collection of 12 papers on carbonate An environment survey: Geologica

c Amieux, P., 1982, La cathodolominescence:


methode d'etude sedimentologie des
diagenesis which have appeared in the
Journal of Sedimentology Petrology.
Fuchtbauer, H., 1969, ed., Lithification of
romana, v. 7, p. 183-228.
A beautifully presented, wide-ranging
paper on diagenetic environments.
C Carbonates: Bulletins des Centres carbonate sediments, parts 1 and 2: Roeder, R.J., 1983, Carbonates: miner-
Ressources Exploration Prod. Elf Aqui- Sedimentology, v.12, p.7-159, and alogy and chemistry: Reviews in Miner-
taine, v. 6, p. 457-483. p. 163-222. alogy, v. 11, 394 p.
o An excellent overview of cathodolumi- These 2 volumes contain a suite of excel- A number of excellent short papers, with

o nescence - as applied to carbonates,


with good photographs.
lent papers on carbonate cementation.
Harris, P.M., Kendall, C.G. St.C. and Lerche,
superb, pertinent reviews on crystal
chemistry (R.J. Roeder and J.A. Speer),

o Bathurst, R.G.C., 1975, Carbonate Sedi-


ments and Their Diagenesis: Elsevier,
I., 1985, Carbonate cementation-a brief
review, in Schneidermann, N. and
Magnesian calcites (F.T. Mackenzie et
al.), Aragonite-calcite transition (W.O.

c New York, 658 p.


The authoritative text on the subject of
Harris, P.M., eds., Carbonate Cements:
Society of Economic Paleontologists and
Carlson), dissolution and precipitation
(J. W. Morse) and trace elements and
c carbonate diagenesis - very readable
with exhaustive scholarship. Any worker
Mineralogists, Special Publication No.
36, p. 79-96.
isotopes (J. Viezer).
Roehl, P.O. and Choquette, P.W, 1985,
o in the field should have this book.
Bathurst, R.G.C., 1980, Lithification of car-
A succinct overview of carbonate
cements in different settings.
Carbonate Petroleum Reservoirs:
Springer-Verlag, New York, 622 p.
( bonate sediments: Science Progress Horowitz, A.S. and Potter, P.E., 1971, Intro- A series of 35 papers on the geology of
Oxford, v. 66, p. 451-471. ductory Petrography of Fossils: carbonate reservoirs, many of which
An update on research in limestone dia- Springer-Verlag, New York, 302 p. deal extensively with diagenesis.
genesis since 1975. Good photomicrographs of wide variety Schneidermann, N. and Harris, P.M., 1985,
Blatt, H., 1982, Sedimentary Petrology: of limestones. Carbonate Cements: Society of Eco-
WH. Freeman, San Francisco, 564 p. Hudson, J.D., 1977, Stable Isotopes and nomic Paleontologists and Mineral-
A good chapter reviewing carbonate Limestone Lithification: Journal of the ogists, Special Publication No. 36,
diagenesis. Geological Society, v. 133, p. 637-660. 379 p.
Blatt, H., Middleton, G. and Murray, R., An excellent overview and good place to A collection of 21 papers on the petro-
1980,Origin of Sedimentary Rocks: Pre- start when consid~ring the application of graphic and geochemical attributes of
ntice-Hail, Englewood Cliffs, NJ, 782 p. stable isotope analysis to carbonates. cements in all diagenetic environments.
One overview chapter on carbonate James, N.P. and Choquette, P.W, 1988, Scholle, P.A., 1978, A Color Illustrated
diagenesis. Paleokarst: Springer-Verlag, New York, Guide to Carbonate Rock Constituents,
Bricker, O.P., 1971, Carbonate Cements: 421 p. Textures, Cements and Porosities:
Johns Hopkins Press, Baltimore, MD, A variety of different papers on all aspects American Association of Petroleum
376 p. of karst and paleokarst, ranging in age Geologists, Memoir 27, 241 p.
Numerous short articles which together from Precambrian to modern. An excellent reference while doing car-
illustrate the spectrum of cements in car- Longman, M.W., 1980, Carbonate diage- bonate petrography with a good
, bonate rocks, modern and fossil. netic textures from nearshore diagenetic bibliography on techniques and class-
Flugel, E., 1982, Microfacies Analysis of environments: American Association of ification.
Limestones: Springer-Verlag, New York, Petroleum Geologist, Bulletin, v. 64, Schroeder, J.H. and Purser, B.H., 1986,
633 p. p.461-487. Reef Diagenesis: Springer- Verlag, New
Although this is a general text there are A good review of the processes and pro- York, 455 p.
good reviews on diagenesis - and an ducts from nearsurface diagenetic The biological and chemical aspects of
excellent source of information on Meso- realms. diagenesis in modern and fossil reefs
zoic-Cenozoic carbonates. Machel, H., 1985, Cathodoluminescence in are treated in 21 papers.
Folk, R.L., 1965, Some aspects of recrystall- calcite and dolomite and its chemical
ization in ancient limestones, in Pray, interpretation: Geoscience Canada,
L.C. and Murray, R.C., eds., Dolomitiza- v. 12, p. 139-147.
( tion and Limestone Diagenesis, a sym- An excellent overview of the chemical
posium: Society of Economic Paleon- considerations that should be taken into
l tologists and Mineralogists, Special account when using cathodolumines-
Publication, No. 13, p. 14-48. cence.
6 A good introduction to a complex topic. Meyers, W.J., 1974, Carbonate cement Originally published in
Folk, R.L., 1973, Carbonate petrography in stratigraphy of the Lake Valley Forma- Geoscience Canada v. 10 Number 4
the post-sorbyan age, in Ginsburg, R.N., tion (Mississippian) Sacramento Moun- (December 1983)
ed., Evolving Concepts in Sedimen- tains, New Mexico: Journal of Sedimen- Revised 1988
tology, Johns Hopkins Press, Baltimore, tary Petrology, v. 44, p. 837-861.
MD, p. 118-159. A landmark paper introducing the con-
A thoughtful and readable essay on the cept of cement stratigraphy and illustrat-
petrography of carbonate diagenesis. ing the use of cathodoluminescence in
Friedman, G.M. and Sanders, J.E., 1978, carbonates.
Principles of Sedimentology: John Wiley,
New York, 792 p.
A short section on diagenesis.
c
12 Diagenesis Geoscience Canada Reprint Series 4 c
(
c
c
c
c
c
(
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
e
(

Cements fabrics in ooid peloidal grainstone, Stubbs Cay, Turks and Caicos Islands, British c
Bahamas . Sample is from a Pleistocene exposed surface immediately below a Holocene,
eolian, ooid sand dune. Early meniscus cement between grains is blocky, anhedral low
magnesium calcite. Later cement, filling cavity, is randomly oriented rhomb ic . needle and
bladed low magnesium calcite. Enlargement illustrates the complex arrangement of rhomb
c
units within the later cement fabric. Thesub-structure of the bladed crystals is similar to that of c
"Iublinite ' ~ Subaerial-vadose environment. Photograph courtesy of A. Oldershaw (University
of Calgary) . c
c
c
~;;-'2tA.-:.;:.;" ~.
c LJ-'VZO £:(/./ {n <./
1'1 ~ b~aA'1~
LlF" -,.{

( Limestones - The Sea-Floor Diagenetic Environment _ J0J


jVVt l->.. J'l - ~ II:s ) fc:) d r cr« /Q":;' ( 13
_ (.AI,",~o-- _ C~{o~o. k\ c.~ Itr.'J..J' 'VI). ~~
(
s:- e.g. (r l/VIJ M t Q. ). • J

c knowledge would be a powerful tool


fJ flu ~::... n () k{!-t>"w et~
10 cm/1000 years) from the fallout of
o when attempt ing to predict trends of
reservoir lithologies in subsurface
calcareous plankton in the ocean
worldwide. Sediments on the slopes of
o carbonates .
Carbonates lying on the sea floor are
shelves and platforms are mixtures of
shallow-waterand pelagic components.
( affected by a variety of chemical and Whereas shallow-water deposits accu-
o biological processes. Precip itation of mulate quickly and form impressively

o CaC0 3 predominates in shallow tropi-


cal marine environments, whereas dis-
solution is im ortant at nig latitudes
thick carbonate bodies, comparatively
thin pelagic carbonates , because of
their enormous extent covering more
Limestones - The and in deeB..'lolat~. The most important than a quarter of the Earth's surface,
( bIOlogical process is infestation of car- account for over two-thirds of the car-
Sea-Floor Diagenetic
o Environment
bonate hosts by a s~%ctr~ of large ang
small boring organisms Because geolo-
bonate currently being extracted from
seawater (Scholle et al., 1983). Current
o gists are so preoccupied with lithifica-
tion, any pore-lining or pore-filling car-
estimates indicate that between 75 and
95 percent of pelagic carbonate is sub-
c Noel P. James bonate precipitate is commonly called sequently dissolved (Broecker, 1974) at

o Department of Geological Sciences


Queen's University
"cement", whether it acts as a binding
agent or fills a pore inside a grain. Since
the sediment-water interface in the deep
sea (Adelseck and Berger, 1975).
o Kingston, Ontario K7L 3N6 both carbonate genesis and diagenesis
occur within the environment of depo-
In the perspective of geologictime it is
important to recall that carbonate sedi-
c Philip W. Choquette sition, often under identical conditions, ments made up of pelagic organisms

o Department of Geological Sciences


University of Colorado
the line between the two is often blurred.
In this essay we arbitrarily consider all
are largely a Mesozoic and Cenozoic
phenomenon and are insignificant in
Boulder, Colorado 80309-250 processes outside direct biomineraliza- Paleozoic and Precambrian strata.
tion as being diagenetic, even though Vertical Zonation. The general pat-
INTRODUCTION some processes involve actual particle terns of carbonate accumulation have
Diagenesis commonly begins as soon formation. been known for over a century (Murray
as carbonate sediments are formed: Sedimentary particles and cements and Renard, 1891; Murray and Hjort ,
o tests of foraminifers settling onto the are either calcite or aragonite. The cal- 1912). The primary controls on carbon-

o deep sea floor gradually dissolve; living


bivalves are infested w ith boring
cite may be enriched in magnesium up
to about 18 mole% . Calcites are com-
ate precipitation and dissolut ion are
Pea?and wa~r~m peratu re and pres- ~ lJi:
o sponges; cement precipitates in coral
pores just below the living surface.
monly referred to as calcite or low-
magnesium calcite or LMC_(less.tba0.2
sure. Although water pressure in-
~ses in a linear fashion with depth,
o These early changes are in many cases mole% MgC0 3 ) and Mg-calcite or high- water temperature does not. Seawater

o the most critical in the history of a lime-


stone because they both modify depo-
magnesium calcite or HMC (12-18
mole% MgC03 ) . While this has proven
at low latitudes is temperature stratified
and comprises three layers (Figure 1):
o sitional facies and direct the pathways
of future diagenesis. For example - if
a useful separation in the past because
most shallow water components are
a warm, homogeneous, near-surface
mixed layer;!!J.e thermocline, a zone at
crusts of lithified sediment sporadically one or the other, discovery of precipi- rapid temperature decreasEU:l/ith deptb
develop on the surface of a carbonate tates in deeper waters with interme- to around 5°C; and a deep-water zone
sand shoal through precipitation of diate amounts of magnesium (2-12 where temperature is more or less con-
intergranular cement, a new hard sub- mole% MgC03 ) has made the differen- stant to abyssal depths.
strate suitable for colonization by skele- tiation somewhat artificial. Precise determination of the solubility
tal invertebrates is created where none In the following pages, we first sum- of calcite and aragonite in seawater
existed before. This new community of marize our current understanding of has proved to be one of the more elusive
organisms may in turn build reefs - the diagenesis of carbonate sediments quests of low-temperaturegeochemists,
and so, in a very short time , a sand on the modern sea floor, and then and as Morse and Berner (1979, p. 531)
( shoal facies has been replaced by a assess the applicability of these obser- point out, "after 100 years of study
reef facies with no change in the vations to the rock record. the major problem of determination of
environment except partial lithification the saturation state of the deep ocean
of the sediment. The effect of this local ZONES OF SEA-FLOOR remains largely unresolved ". At pre-
cementation will continue as these car- DIAGENESIS sent our understanding rests on the
bonate sands pass through subse- There are two realms of carbonate often conflicting results of laboratory
quent diagenetic environments - the deposition in the modern ocean :' exper imentation, mapping of bottom
unlithified and porous parts will be the, ( 1 ) shallow water, characterized ....Qy sediments, and field observations of
first flushed by new diagenetic fluids;~\l ra idl accumulatin sediments ca. particles hung in open containers at
the cemented, non-porous parts will be t 100 cm/1000 years) ~.hich form mainly various depths in the ocean. These
,. affected more slowly. Thus, if the rela in warm tro u.o.a a d ~J,! bt ro ical envi- data have most recently been synthe-
tive intensity of sea-floor diagenesis ronments; and (2 dee -w !!~ sized by Broecker and Takahashi (1978)
could be tied to depositional facies, this by slowly accumulating sedir:R9Ats-(ca. and Morse and Berner (1979). For a
r
c
14 Diagenesis Geoscience Canada Reprint Series 4 c
c
summary of carbonate dissolution and lysocline", that zone determined byfield lysocline and compensation depth are
c
precipitation kinetics the reader is experiments in the water column, and poorly known. A good practical mea- c
referred to the excellent review by
Morse (1983).
the "sedimentary lysocline", marking
an increase in the amount of dissolution
sure for aragonite saturation is the dis-
solution behaviour of pteropods, small c
In general, near-surface tropical and
subtro pical seawater appears to be
on the sea floor (Berger, 1975). In fertile
regions, near the continental margins in
pelagic gastropods with an aragonite
shell (Berger, 1978). In marginal seas
c
supersaturated with re~m.e.Q.L1P-b.Q!b. particular, the sedimentary lysocline with anti-estuarine circulation, such as c
aragonite and calcite to depths of about
500 metres in the Pacific and 2,000
may rise toward the surface and
become diffuse.
the Mediterranean Sea, Red Sea and
Persian Gulf, pteropods are common in c
metres in the Atlantic (Takahashi, 1975).
Below this supersaturated water, sedi-
But what of sediments on the sea floor
in the several thousand metres between
sediments at all depths, indicating arag-
onite saturation of these waters. At low
c
ments on the sea floor are exposed to the shallow saturated waters and the latitudes in the open ocean pteropods c
more and more undersaturated water
with increasing depth because of
lysocline? Why, if water pressure is
the main control , is there not a gradual
disappear below about 1,500 m with
depth valuesshoaling toward the higher c
increasing pressure and, to a lesser
~temperature. Thus,
but steady increase in dissolution latitudes. On average, the aragonite
com ensfltion..depthTACDTIl:igUl:eJ n~
c
sediments are subjeCtetl to Ilrster and
with depth, and why do the particles
that lie on the sea floor show only shallower by3 kilometres than the CCO, c
faster dissolution rates until finall y a
depth is reached where the rate of . -
scant evidence of corrosion? The
answer appears to be a complex inter-
llYt this maY~rY. As with the CCO, tile
ACD is deeper in the Atlantic than ii1tlie
c
so u Ion IS equal to the rate of sediment play between rates of carbonate accu- Pacif ic because Atlantic waters are c
supglv from above. !3elow this depth,
c alled the carbonate cO,JJJP.ensation-
mulation, kinds and sizes of sedimentry
particles and, perhaps most important,
closer to being saturated for calcite and
aragon ite due to different overall pat- c
oop th or ~(Figure 1), !ill-QaLcite..is-
dissolved. In regions where carbonate
the kinetics of dissolution (Morse and
Berner, 1979; Morse, 1983). In addition,
tern S-.oLdeep_water_c~. In the
northeast Pacific and eastern tropical
c
productivity and resulting sedimenta- orthophosphate, present as strongly Pacific aragonite dissolution begins c
tion rates are high, such as those near
the equator, the CCD is depressed.
adsorbed coatings on grain surfaces, is
an inhibitor of calcite and Mg-calcite (but
right below the mixed layer (500 m)
within an oxygen minimum layer. c
Oceanic Q.CD.for.calcite is now at about not aragonite) dissolution (Berner and Zonation with Latitude. There is a c
~n the Pacific ~~d 5,500 m in
the Atlantic. _and is sfiallowesCiii1he
ri9.Ltb..ea~ifjc.ancld~.e.p-estJRi~ii
"*
Morse, 1974).
T~D is the deRth at whiJ:<ILG.alcite
much poorer understanding of latitude
variations in shallow-water carbonate c
~nt1c. Variations of the CCD in the
dissolution balances deposition; the
other two common seaimenta~ry-car­
solubility. Obvious changes in carbon-
ate sediments are complicated or c
world oceans are discussed in detail by
Kennett (1982). Hills that rise from
bonate minerals, Mg-calcite and arag-
onite, likewise have compensation
masked by the effects of surface cur-
rents, terrigenous sedimentation and
c
abyssal depths up through the CCD can depths. Because there are no signifi· climate, as well as by the fact that out- c
be pictured as "the snow-capped moun-
tains of the deep sea" (Berger, 1975),
cant Mg-calcite plankton the Mg-calcite side the tropics many of the carbonates
c
their lower slopes below the CCD cov- TEMPERATURE °c "10 CARBONATE c
ered by red clays and siliceous ooze,
and their tops above the CCD mantled 0
OF SEAWATER
,0 20 30 0
IN SEDIMENT
50 100 c
with white carbonate sediment.
0 0
c
7
I ZONE OF
Evidence for dissolution can be seen PRECIPITATION
at depths considerably shallower than ",0
-t....'i..'if.
c\,\~'i..
c
the CCD. This gives rise to the concept
of tb!!JYAo.cUoe (Berger, 1968), or depth ZONE OF
c
where evide[lC_e~of.conside.r.able.(selec­
tive) dissolution is first .e n c9M.r.tt~ d .
:l:
~2
:n: DISSOLUTION
AND
c
The lysocline is in general 1,000 m shal- x
.....
PRECIPITATION
c
lower than the CCD and most dissolu-
tion takes place within this 1,000 m
Q.
ILl
Cl 3
DEEP
WATER 3 c
interval. Broecker and Takahashi (1978)
have demonstrated that to within
ll:
ILl m:
ZONE OF
ACTIVE
e
± 200 m the depth of the calcite lyso-
cline can be explained in terms of car-
.....
c(
~ 4 4
DISSOLUTION
c
ZONE OF (
bonate ion concentration in deep :nL NO
waters: the lysocline lies at greatest
5 5
CARBONATE
c
depth where waters with high carbon-
ate ion concentrations extend to the c
bottom.
It should be noted that there is often a
Figure 1 Generalized diagrams illustrating the relative positions of calcite and aragonite
solubilityprofiles in the modern tropical ocean and the variation in temperature with depth. The
c
difference between the "hydrographic major zones of diagenesis are plotted to the right. c
c
c
(

C' Limestones - The Sea-Floor Diagenetic Environment 15


(

C. are relict (Emery, 1968; Ginsburg and skeletons from latitudes above 40° . near the surface in polar seas, are dis-
o James, 1975).
In general, rapid fixation of biogenic
Although the actual removal of carbon-
ate is thought to be mostly by physical
tinguished by wholly biogenic calcite
accumulation showing abundant evi-
o and inorganic carbonate in shallow abrasion aided by maceration, dissolu- dence of corrosion.

o water appears to be limited tothetropics


and subtropics and rarely extends north
tion "opens up" the grains and aids in
these processes. There is no clear evi-
IV. Zone of No Carbonate. Wholly
deep-sea settings, below the CCD
o or south of 30° latitude .Although acorn-
plete spectrum of carbonate skeletons
dence of dissolution on a large scale.
Thus, in shallow-water environments
where no carbonate is accumulating.
It should be stressed that this is a
o is produced in these environments,they
are distinguished by abundant produc-
north andsouth of the tropics conditions
seem to be similar to those below the
generalized zonation and appl ies
chiefly to the open ocean and to associ-
tion of corals and green algae, both of zone of saturation and above the ated shelf-slope and platform-slope
o which are aragonite . Lees and Buller lysocline in the deep tropical ocean. systems. The major part of the following

o (1972)have, as a result, designated this


the Chlorozoan assemblage to differen-
On balance we can roughly differenti-
ate four zones in the modern ocean in
discussion on sea-floor diagenesis is
focussed on Zones 1 and II.
o tiate it from the Foramol assemblage of
temperate and polar seas.The principal
which the conditions for carbonate dia-
genesis are the same (Figures 1 and 2). ZONE I: WARM SHALLOW WATER
o contributors to the cooler water carbon- I. Zone of Precipitation. These are PLATFORM CARBONATES

o ate assemblages are molluscs, foramin-


ifers and bryozoans with echinoids, bar-
shallow tropical to subtropical settings
in which a complete spectrum of skele-
Mineralogy of Precipitates.
Sedimentary particles on \he modern
o nacles and coralline algae often
present. The bulk of these higher latl -
tal and non-skeletal particles of arag-
onite, Mg-ealcite andlor calcite occur,
shallow sea floor in tropical regionscon-
sist of aragonite or calcite or magne-
o tude carbonates are Mg-ealcite or cal- as well as aragonite and Mg-calcite sium-enriched calcite (Mg-calcite).

o
*
cite with rare aragonite, and in mixed- cements. The lower limit of this zone Although some organisms precipitate
layer mineralogies there are lower where seawater becomes undersatu- skeletons of calcite , only Mg-calciteand
amounts of aragonite in colder climates rated with respect to aragonite is about aragonite appear to precipitate directly
(Milliman, 1974). Non-skeletal grains 1,000 m (varying between 500 m and
o (ooids, peloids and lumps) and marine
cements do not generally occur in these
2,000 m depending on the ocean) in the
tropics and shoals to the surface around
from seawater here.
It is still not clear what control
the mineralogy and crystal habit of
cooler waters and are restricted to the 30 0N and 30 0S latitude . these minerals or why both Mg-calcite
tropical zone, although Alexandersson II. Zone of Dissolution/Precipita- and aragonite are so common (see
(1974) has found aragonite and Mg- tion. Shallowtemperatewatershelfset- Bathurst, 1980,for summary). The com-
o calcite cements inside coralline algae tings north and south of about 30° lati- plexities involved as well as the dif-

o nodules in the North Sea where waters


are undersaturated, suggesting strong
tude to the polar regions, which are
characterized by wholly biogenic car-
ferences between experimental results
and natural observations are discussed
o biological influence.
Even though rates of carbonate pro-
bonate accumulat ion (mainly Mg-
calcite and calcite), no intergranular
and debated by Given and Wilkinson
(1985a,b) and Morse (1985). From a
() duction are much lower in cooler latl- cementation, and minor dissolution. thermodynamic standpoint, calcite with
o tudes than in the tropics, carbonates
may locally constitute up to 50% of the
Deep-water tropical slope and basin
settings from the base of Zone I to the
from 2 to 7 mole% MgC03 is the pre-
ferred stable phase in seawater(Berner,
o sediment. Observing the high produc- calcite lysocline are likewise cnarac- 1975). It has been suggested that the

o tivity and lack of terrigenous mater ial in


such areas, however, the amount of car-
terized by local dissolution of alloch-
thonous aragonite and ?Mg-calcite
presence of strongly hydrated Mg2+
ions absorbed onto the crystal surface
o bonate is somewhat lower than might be
predicted - suggesting removal of
components, neomorphism and preci-
pitation of calcite (LMC) cements.
(the Mg/Ca ratio in seawater is ca. 511)
inhibits the growth of calcite, and that
o some portion (Milliman, 1974; p. 105). It III. Zone of Active Dissolution. Deep- the Gibbs free energy needed to dehy-

o is common to observe the effects of


dissolut ion in both calcite and aragonite
sea settings between the calc ite
lysocline and the CCD which may rise to
drate the ions and form aragonite is
lower (Bathurst, 1968). On the other
o ~
hand, it is also known that calcite crys-
tals may precipitate and absorb large
o . : \...

~'\'\~ 70 60
NORTH

50 40 30 20
LATITUDE

10 0 10 20 30
SOUTH

40 50 60 70 quantities of Mg2+ as they grow


(Berner, 1966). The Mg-calcites so
6
\~ :\'~ mnTTfm~W~w'm7TI77J
[7'
formed are in non-exchange kinetic
C lCJ-
equilibrium with seawater.
The main conclusion of much experi-
mental work and observat ion of natural
:x:
l- systems appears to be, as summarized
n. 4 -
w
o by Mackenzie et al. (1983) and echoed
5 - by Given and Wilkinson (1985a,b), that
ZONE n
6 - ' - - - - - - -- - - - - - - - - - - - - -- - - ' the MgC0 3 contents of magnesium cal-
cite precipitated from seawater, includ-
Figure 2 Variations in the different zones of sea-floor diagenesis in the modern ocean. ing organism skeletons and cements,
c
16 Diagenesis Geoscience Canada Reprint Series 4 c
c
are related to temperature and CO~' Petrography of Precipitates. entirely filled. Thus, the addition of Mg-
c
concentration of the water. The amount Magnesium calcite (Figure 3). calcite micrite cement may, in the pro- c
of MgC0 3 in the calcites increases with:
(1) increasing temperature (Burton and
Magnesium-enriched calcite precipi-
tates generally contain a range of
cess of lithification, change the texture
of a grainy sediment from a grainstone c
Walter, 1987), (2) increasing carbonate between 12 and 19 mole% MgC03. The to packstone . (
ion concentration (Given and Wilkin- crystals (trigonal CaC0 3) precipitate Of interest here is the ubiquitous
son, 1985) and (3) increasing Mg/Ca
ratio of the fluid (Mucci and Morse,
either as tiny rhombs less than 4 micro-
metres across (micrite-size) or as fibres
association of micro-peloids, ranging in
sizefrom 20 to 100 mlcrornetres on aver-
c
(
1983). It is also clear that the rates of a few tens of micrometres long. Al- age, with micrite cement. This is the
fluid flow are important. Mg/Ca ratios do
not seem to be sufficently variable in the
though iron can be accomodated in the
calcite crystal lattice, microprobe analy-
structure grumuleuse of Cayeux (1935),
a fabric of numerous clots or vague
c
modern ocean to account for observed sis of these cements reveals no detect- small peloids (aggregates of Mg-calcite c
trends in mineralogy. Since tempera-
ture and carbonate ion concentration
able Fe2 + . Probably th is is because
there is very little iron in seawater and
rhombs), surrounded by micr ite and
microspar. While these may well be
c
are covarient in the ocean it is difficult to
determine which is the most critical
most precipitation takes place under
oxidizing conditions where any iron pre-
sedimentary particles of uncertain ori-
gin, the persistent association has led
c
factor. The importance of temperature sent is the Fe3 + state, and the partition Macintyre (1983) and Marshall (1985) to c
has been stressed by Burton and Walter
(1987) who confirm that the growth rates
coefficient is close to one (Richter and
Fuchtbauer, 1978). Because strontium
suggest that the peloids are the resutrof
sp-ontaneous nucleation and preciRita-
c
of aragonite versus calcite increase with its relatively large ionic radius fits ·tion-ofMg-calcite in the water column C
with increasing temperature. Aragonite
has about the same solubility as Mg-
uneasily into the calcite lattice, Mg-
calcite rarely contains contains more
Which- men settle out of suspension.
Ttiis precipitation may be eIther i:lirector r
calcite with ca . 12 mole% MgC03 (WaI-
ter and Morse, 1984; Walter, 1985).
than a thousand ppm Sr2 + (Kinsman,
1969).
organically induced. Chafetz (1986) has
found that the finely crystalline nucleus
C
Seawater has been described as Micrite-size crystals. This is the most contains rods of bacteria , suggesting C
"a dilute electrolytic organ ic soup" so common type of Mg-calcite cement that the crystallites originated as a pre-
that prediction of any reactions that occurring in awide variety of sediments . cipitatewithin and around active clumps C
lead to precipitation must also take into
account the large amount of organic
It ranges from thin rinds only tens of
micrometres thick around particles and
of bacteria and that the vital activity of
the bacteria influenced precipitation of
C
material. That organics affect precipita- algal filaments to complete fillings of the calcite . C
tion is clear, but their role is ambiguous pore spaces. Although micrite is easily Fibrous crystals. This cement (Figure
(Mitterer and Cunningham, 1983). Inthe seen as cement when encircling parti- 3) is generally found as isopachous C
first place, all particles are coated with
layers of organic molecules which
cles or lining ooids, it is difficult to dif-
ferentiate from lime mud if the pores are
encrustations up to several hundred
micrometres thick.The elongatecrystals
C
inhibit nucleation, allowing seawater to C
maintain supersaturation (Suess, 1970, SHALLOW MARINE CEMENTS
1973). At the same time, organic matter
C
extracted from ooids is similar in com- C
position to that found in skeletons (Mit- MAGNESIUM CALCITE ARAGONITE
terer, 1971). These proteins and humic C
substances contain carboxyl groups
with similar geometry and charge as the
C
carbonate anion. Thus, there may be C
substitution by the anion for the organic
group, and so crystals may be nucle-
MICRITE
C
ated and grow by epitaxy. The presence
of more 13C in marine cements than
expected if they were completely
Ye.,{o·, ~ ~
Ctl l-WV"·
11 \~ (<t(ll ~
OOp/)
IlIl MESH OF
NEEDLES
C
C
inorganic precipitates (Milliman and
Muller, 1977) also points to some sort of 000" c
involvement by organics.
~ Although in general Mg-calcite
e
r'\
appears to be the most widespread
marine cement (James and Ginsburg,
c
1979), aragonite is common in waters of
slightly elevated temperature and salin-
ity. Finally, in ooids it appears that the FIBROUS TO BLADED
BOTRYOIDAL c
degree of seawater agitation mayfavour RINDS 10 -.r~( erA (D ""8 ~
the precipitation of one mineral over .£'7 1-(e.' <. C--l/ '~ r:-r~.(A Ci..- 1_n
another (Davies et sl., 1978). Figure 3
/)/c<-, /-
Different types of modern sea-troor carbonate cements. I 1t:lV\.L
L
t.( V'
1'oW)
/'<-.0 II, ~ II-./'
C
J
rd.r
o
J~)
U,-"tn.f
/h-CJUl tJ,"""
,
I
C
'7 f' ·o /11,R .I ~/

c
l
( Limestones - The Sea-Floor Diagenetic Environment 17

c are either nucleated picket-fence style increasin g organics favouring nanno-


flO C
tures" in the form of 0180/160 and
( on the substrate or located at intervals, J1,rains. The cements are reviewed and ~otoPic ratios as well as minor
cation (e.g., Sr2+, Mg2+, Na +) con-
o and grow as small spherulites which
quickly interfere with one another as
illustrated in a recent article by Sand-
berg (1983). Strontium isthe majortrace!J centrations (Viezer, 1983). Many ana-
o they develop. The spherulites are often
arranged in tiers in the cement rind.
element in a'ragonite whose orthorhom-
bic structure accomodates it easily and
lyses have been done on carbonate
sediments and on many of their more
c Blocky or equant crystals. These cement crystals usually carry about common constituents, such as ooids,

o small crystals, ranging in size from 20 to


50 micrometres, are not common as
shallow marine precipitates, but do
8,000 to 9,000 ppm, as do most arag-
onite skeletons (Kinsman, 1969; Bath-
urst, 1975). The major exceptions are
calcareous green and red algae, corals,
brachiopods, molluscs, lime mud, etc.
(Figure 4). Milliman (1974), Bathurst
occur locally in both reefs and hard- aragonite molluscs which contain (1975) and Morrison and Brand (1986)
o grounds. between 4,000 and 1,000 ppm Sr2+ , have summarized many of these iso-

o Epitaxial crystals. Although particles


of echinoderm skeletons, composed
The needles occur in a variety of dif-
ferent habits (Figure 3): (1) Isopachous
topic data on Recent marine carbonate
sediments including the pioneering
o generally of a single crystal of Mg-
calcite, are common elements in many
rinds, particularly common in ooid and
skeletal sands and as epitaxial growths
work of Gross (1964).
Though much of the spectrum of
o modern carbonate sediments, the on aragonite substrates such as corals, marine cements and cementation pro-

o development of marine epitaxial Mg-


calcite cement on these grains has not
green algae and gastropods. (2) An
intergranularmesh of crystals nucleated
cesses is poorly understood, enough
isotopic data has been gathered to sug-
o yet been reported. The closest occur-
rence is the presence of epitaxial crys-
randomly on grain surfaces and grow-
ing in a variety of directions into a void
gest some general relationships. ~
know most about cements being pre-
o tallites developed on cores of echino- until the void is completely filled by an cipitated in modern sediments and reefs

o derms in ooid cortices (Marshall and


Davies, 1975).
irregular growth of crystals or crystal-
lites. (3) Botryoids, which range in diam-
at low latitudes, in warm shallow-shelf
and platform setti nqs. These cements
o Aragonite (Figure 3). Aragonite eter from tens of micrometres to cen- have relatively heavy, 180-enriched

c (orthorhombic CaCOa ) precipitates are


either microcr ystalline or needles a few
timetres, sometimes developed in
coarse carbonate sands but most spec-
oxygen-isotopic compositions of 0 to
+ 3%0 (Gross, 1964; Shinn, 1969; Milli-
o micrometres or tens of~icrometres
long. Loreau (1982) separates these
tacular in reef cavities.
Isotopic Composition of Precipitates.
man, 1974; James and Ginsburg, 1979),
and their 13CS are heavier (ca. + 2 to
nannocrystals, from largest to smallest, When CaCOa is precipitated from sea- + 5%0) than would be expected had they
into needles (generally cements), water - whether in calcareous skel- been precipitated in isotopic equilib-
baguettes (generally in the ooid cortex) etons, as non-skeletal grains such as rium with seawater ( + 2.0 to + 2.5%0 at
o and nannograins, with increasing tur-
bulence favouring needle formation and
ooids, or as marine cements - it ac-
quires characteristic chemical "signa-
25°C; Lloyd, 1971). Specifically (Fig-
ure 5), relative to calcite equilibrium
o compositions, aragonite cements are

o enriched by 1.0to 1.4%0 013C and 1.5to


2,0%0 018 0 while magnesium calcites
o +6
,------,---,----,---,-----, ..
o ARAGONITE

o +4

o o
-e
o
o
o ~ +2
z
Seds.

oCD
0' a:
cl
u OI--------------i----------i~.-:.:--1-~~-_t
MAGNESIUM
...---!
SEDIMENTS 8
// /
CALCITE
r:
SKELETONS, Recent,
Shallow Warm Water
II '
\ / .,
8 \
,' ....... _,,'"
-2 ,,///
/

-2 -, ., '2 +3
OXYGEN i "0 ('M)

Figure 5 Isotopic composition of aragonite


Figure 4 Cross-plot of carbon versus oxygen isotopic compositions for recent sediments and and Mg-calcite cements in modern reefs from
component particles, and for buried chalks. PDB-1is the isotopic standard in this diagram. Data Bermuda, Enewetak, Bikini and Belize.(Modi-
are from Gross (1964), Anderson and Schneidermann (1973), Milliman and Muller (1977), ~ fi d from Gonzalez and Lohmann, 1985).
Schlager and James (1978) and Rao and Green (1982). V fa..e n /L, (. 'df~ C O\.~·
--
X/pV:"'J
( ~ fit. ( I~
(<(
~.~ Ill"~5yfl--f ..
C) It~ ~'/i Q M' .... ~6.J::O;......,.-.-r-rN~"""r,--.-
I of, eQ

('PIJ-,~0 {h( y":;r'l 1 ,$'1 LI ~ t I


t..~tI.,!VV!J.:
c
18 Diagenesis Geoscience Canada Reprint Series 4 c
c
(average 16 mole% MgC0 3) are en- Loreau, 1982), although Mg-calcite cipitates lining chambers and other
c
riched by 0 .3 to 0.4%0 <5 13C and 1.8 to ooids (Marshall and Davies, 1975) and pores inside skeletal elements (Alex· c
1.9%0 <5 180 (Gonzalez and Lohmann,
1985). Because of the consistent frac-
even bimineralic ooids (Land et al.,
1979) do form locally.
andersson, 1978; James et al., 1976)
and as precipitates in micro- and macro- c
tionation relative to predicted composi-
tions it is clear that the cements do not
Although there is compelling evi-
dence that the lime mud found in many
borings. Thus, it is not unusual in the
fossil record to find grains exhibiting
c
represent equilibrium precipitates. shallow marine settings IS mostly bio- good evidence of internal ssa -noor c
Since the aragonitic thalli of calcareous
green algae and the Mg-calcite of mic-
genic in origin (Stockman et aI., 1967;
Weumann and Land, 1975), some may
CaC03 precipitation, yet showing little
or no indication that they were actually c
rite rims produced by endolithic algae
also have heavy <5 13Cs, dominantly of
be due to direct precip itati on. The cemented together in the sea-floor c
+ 2 to + 6%0, several workers have pro-
clouds of aragonite crystallites or "whit-
ings" seen in many shallow tropical
environment.
Between Particles. This type of c
posed that these groups of algae are
" involved" if not directly responsible for
EWvironments are commonly thou ght to
be mud derived from benthic sources
precipitation is the least common in the
sea-floor environment but the most
c
the origin of marine CaC0 3 cements stirred up by feeding fiSh - yet in some important geologically because it is c
(Lloyd, 1971; Schroeder, 1972; Moore,
1973; Milliman and Muller, 1974). Bio-
cases they may be products of sponta-
neous precipitation. In the Persian Gulf,
"rock-making" cement.Thuslimestones
may be formed soon (tens to thousands c
logically mediated precipitation should
result in isotopically depleted carbon-
for example, there are few aragonitic
~Igae~ yet numerous whitin gs and mu ~
ofyears)after deposition ifconditionsare
right in the environmentof accumulation
c
ates due to incorporation of metabolic mud , and many fish . While Loreau (Figure 6). The habitats of these inter- c
CO2(Viser, 1983), yet cements depleted
in 13C and 180 are not known from shal-
(1982) suggests, on the basis of Sr2+
and Mg2+ contents, that both Persian
granular cements are varied.
(1) Platforms. The most desirable c
low marine environments.
I/t...- In any event, marine cements in mod-
Gulf and Bahamian aragonite needle"
muds are likely inorganic precipitates ,
conditions for interparticle cementation
appear to be water turbulence and sta·
c
~ern warm/shallow environments can be Ellis and Milliman (1985) found thattlTe- bilized sediment. Both conditions are c-
clearly differentiated isotopically from
Late Cenozoic meteoric vadose to
suspended sediments in the Persian
Gulf and..Bed-Sea...ar:.ELbl..ogenic and
met on the insides of reefs, especially at
or near the platform margin (Ginsburg c
shallow-phreatic cements, and the evi- detrital. and Schroeder, 1973; James et al., 1976; c
dence is accumulating that these dif-
ferences survive, though often much
While most readers will agree that we
are stretching the concept of sea-floor
Macintyre , 1977 ; Aissaoui et al., 1986)
or on the windward sides of platform c
reduced, in the face of complex diage-
netic histories spanning tens to hun-
diagenesis by including these sedi-
ments, we have done so to place the
reefs (Marshall, 1986). Likewise, sand
shoals near the platform edge are
c
dreds of millions of years. whole topic in context. likely locales, but here most lithification c
Precipitated Particles.
Perhaps the most important precipi-
Style of Cementation.
Inside grains and skeletons. This
takes place when the sediments are
at rest inside the sand shoals or bound c
tates in terms of the amount of CaC0 3
removed from shallow seawater are
type of precipitate, found inside parti-
cles and/or skeletons, is the most wide-
by micro-organisms in sheets (Dravis,
1979) or stromatolites (Dill et al., 1986).
c
ooids. They may have a cortex of tan- spread CaC0 3 "cement", occurring In contrast, muddy lagoonal sediments c
gentially or radially oriented crystallites.
In the modern ocean the overwhelming
even in grains still rolling around on the
sea floor. The cements occur between
are rarely Iithified, probably because of
sluggish water movement, continuous c
majority are aragonite (Simone, 1980; silt-size particles inside peloids, as pre- bioturbation and general reducing
c
c
ZONE I • : : • • • • ~ . .. . '0 .'1. ';,.
..... . ..:,.....
~ ,,', -.-.. '. c
100'S
to ' :_ .0. ; : : :. ;: .;:.•..: v-
c
1000'S
of meters
DEEP BASIN SHALLDW IPLATFORM or LAGOON I c
MARGIN
c
ZONE ]I
.' ~. , 0, . ," , ', : . , :', ' : •• • ••
L-::.'-='-'-' sANDSHQAls
extenSive
hardoroundS
or
hardQrounds

REEFS
SAND SHEETS - sporadic lithification or
extensive hardgrounds
REEFS- sporadIC lithIfIcatIon
SANDYBEACH
beachrock e
Carbonate ....... ..;.' pi '" of sand extenS ive MUDDYTIDAL
Sediment '" : "" " and limestone cemen tat ion MUDDY LAGOON - no cementation FLAT
Lysocl ine- blocks
hardgrounds In upper
ZONE ill port crusts, dolomIte
- - CCD
ZONE IS[
-- no
DEEP SEA Carbonate ~
;-' REEF MOUNDS
eJlU!ns iwe c
I~~~~:::='ii=-~)~ c
cementation
neomorphism

Figure 6 The locations of sea-floorprecipitation and neomorphism on a shallow carbonate platform and in adjacentdeep-water settings. In a/l .
of these habitats, most sediments are unlithified. l
('.
Limestones - The Sea-Floor Diagenet ic Environment 19

c. conditions . Strandline sands also are


( commonly cemented but this may notbe
entirely due to reaction with seawater.
G Even though the majority of sediments
o on shallow carbonate platforms are not

o cemented, when viewed in total there


appears to be a facies preference for
precipitation.
(
While this generalization may hold
c true for muddy shelves and platforms,

c cemented crusts or hardgrounds (Fig-


ure 7) are common in extensive sand
sheets on parts of the Bahama Banks
(Taft et a/., 1968), wide gently dipping
shelves such as off the Trucial Coast in

c the Persian Gulf (Shinn, 1969),and par-


tially enclosed embayments such as
Shark Bay, Australia (Read, 1974). Lithi-
fication is most intense at the surface
and decreases in intensity downward,
generally ceasing within tens of cen-
timetres below the sediment-water
interface. As Wilkinson et al. (1982)
point out in a discussion of fossil hard-
grounds , the processes of lithification
may be quite different between plat-
form-margin reefs which have large
Figure 7 An irregular submarine hardground (between 129 and 128 em on the tape) cavities and are subject to strong cur-
developed in Lower Cambrian ooid limestones of the Forteau Fromation, western Newfound- rents or waves moving large volumes of
land . The photomicrograph illustrates the truncated ooids and cements at the hardground
normal seawater, and non-reefal sands
surface (arrow indicates location; scale bar 0.5 mm).
where current velocities are reduced,
pore volumes small and communication
with surrounding waters limited.
(2) Shallow enclosed basin. In rela-
tively shallow basins such as the east-
ern Mediterranean and the Red Sea,
where there is anti-estuarine circulation
and warm waters extend to the seafloor,
basin-floor sediments are locally
cemented by Mg-calcite and occa-
sionally aragonite to form crusts
(Gevirtz and Friedman, 1969; Milliman
and Muller, 1977).
(3) Slope and deep basin. The ocean-
facing slopes of shelves and platforms
r:
illustrate a range of Iithified sediments.
The top of the slope, which generally
comprises deep portions of the mar-
ginal reef and forereef, locally exhibits
extensive cementation (James and
~ G i n s b u rg , 1979;Land and Moore, 1980).
gementation seems to die opt with
increasing water depth so that below,
300 m OI-SO ha.J:dgrQullds-give way
first to nodules alliLt b~ILto unlithified
~e dime ot (James and Schlager, pers.
Figure 8 A debr is flow from the Ordovician part of the Cow Head Group , a carbonate slope
deposit in western Newfoundland, illustrating the effects of multi-generation sea-floor cemen-
observ. , 1979; Mullins et al., 1980).
tation. The tabular clasts are fragmented thin-bedded lime mudstones that were lithitied.on the These partly to completely lithified
slope before being eroded and incorporated into the flow. The boulders of tabular clast breccia slope sediments are commonly subject
to the left of the hammer and at upper right were debris flow deposits lithified on the sea floor to failure and become clasts in gravity
before being incorporated into yet another flow. Photograph, M. Coniglio. flow deposits (Figure 8).
(
20 Diagenesis Geoscience Canada Reprint Series 4 (
(

Hardgrounds are common off the have been redeposited as sediment equant, bladed and radiaxial fibrous cal-
C
western Bahama Banks where the sea gravity flows. Cementation in shallow- cite, both clear and inclusion rich. In Cre- r
floor is swept by the Gulf Stream. In water temperate carbonates appears to taceous limestones the cements are
depths of 600 00 or so, Iithified mounds be limited to prec ipitation within lntrapar- medium to coarsely crystalline (100-300 C
(lithoherms) formed by numerous
superimposed crusts and populated by
ticle pores (Rao, 1981) and there are to
date no reports of sea-floor neomor-
micrometres) equant spar.
These calcites contain low to inter-
C
deep-sea ahermatypic corals and cri- phism.ln contrast, in deep-water tropical mediate amounts of magnesium , in C
noids rise 50 m or more above the bot- settings where the sea floor lies within accordance with the experimental re- (
tom (Neuman net al., 1977). The cement the thermocline or just below it, waters sults of Fuchtbauer and Hard ie (1976)
in these structures is Mg-calcite.
Below these depths (Figure 6) is the
are close to or below aragon ite satu ration
but supersaturated with respect to cal-
and BurtonandWalter(1986)which indi-
~e that calcites precipitated from
C
transition zone where water tempera- cite. Thus, a situation is created similar waters of decreasing tem r on- C
tures decrease rapidly in the thermo- to that in meteoric environments (see tarnpro essrve y less magnesium. The
cline and waters at the sea floor pass James and Choquette, this volume) in l inely crys talffiie calcite cements in C
from Zone I (precipitation) to Zone II
(dissolution and precipitation).
which the metastable carbonates have a
high "diagenetic potential" to alter to
Bahamian peri platform ooze contain
3-5 mole% MgC03 while the radiaxia
C
Neomorphism. calcite through dissolution and precl- calcite cements from Enewetak contain C
On the shallow tropical sea floor, when pitation . There are relatively few docu- 5.0-11.6 mole% MgC03.
aragonite and Mg-calcite are precipi- mented cases of this diagenesis, be- Neomorphism. C
tated they appear to remain I r.ge.ly cause of the great difficulty in studying While some aragonite pteropods are I C
unchange untl a fected by waters of a such sediments in waters 100s to 1000s dissolved, others are partially miCj
radicallyaTferen character. Neverthe- of metres deep. ritized. There is also selective alteration C
less, there are some reports of re- (1) Holocene fore-reef limestones off of Mg-calcite allochems, e.g., some for-
crystallization: Mg-calcite foraminifers Jamaica appear to be undergoing local aminifera illustrate crystal enlarge-
C
and coralline algae altering to aragonite neomorphism (Land and Moore, 1980). ment. C
(Murray, 1966; Kendall and Skipwith. (2) Pleistocene periplatform ooze in Isotopic Compositions.
1969; Purdy, 1968); aragonite cements the Bahamas is lithified by dissolution While the 0'3C values for lithified Baha- C
partially replacing aragonitic mollusc
shells (Shinn, 1969); parts of aragonitic
and reprecipitation when exposed for
long periods as vertical erosional valley
mian peri-platform ooze in the Tongue of
the Ocean are roughly similar to the
C
cements and skeletons changing to Mg- walls in isolated troughs (Schlager and values from shallow water precipitates, C
calcite (Alexandersson, 1972; Scherer, James, 1978) or buried in the shallow the heavier oleo values clearly ind icate
1974). These occurrences seem to be subsurface (less than 30 00) on ocean precipitation from cold ocean waters C
rare but do point out again the subtletie-S.
governing prec iRit at ion of different
facing slopes (Mullins et et., 1985) .
Metastable components in carbonate
(Figure 4). The isotopic record of the
radiaxial and equant calcites is, how-
C
cac 0 3 phases and tell us that the pos- turbidites are also altered in a similar ever, unclear. These are clearly marine C
Sibi lities fo r ne-o.mar.pfiiSii'CCti5-ex.lSf; fashion (Gomberg and Bonatti, 1970). precipitates but their isotopic composi-
although they ma~ not be co m!J.lQD.J.o. (3) Relict sediments on seamounts tions do not confirm precipitation from C
today's sbaIlQW.S.e.as._ are altered when exposed and win-
nowed for IQngperiods (Milliman, 1966).
cold waters. i
The importance of this deeper water
C
ZONE II: TEMPERATE WATER (4) Cretaceous to Miocene shallow neomorphism in the modern ocean is C
SHELVES, TROPICAL CARBONATE water limestones which have subsided difficult to ~~ at present. It is
SLOPES into deep water by vertical platform localized to areas hich receive meta- C
Perhaps the single most intriguing accretion suffer dlssolutlon and calcite stable sediments from platforms. In C
advance in our understanding of sea-
floor diagenesis since this article was
first written (James and Choquette.
1983) has been the confirmation that
fabric-selective dissolution, calcite
precipitation (Saller, 1985; Freeman-
Lynts et aJ. , 1986).
Di~owtron.
Aragonite appears to be the only mi -
j
eral undergoing dlssolutton, resulting i
most of the deep ocean, where sedi-
ments are composed of calcite plank-
tonic organisms, there is little "diage-
netic potential". In the Paleozoic when
there were virtually no planktonics and
C
C
(
cement precipitation and calcitization of
metastable carbonates do take place in
partial to complete fossil molds.
Precipitation.
all deep-water carbonate sediments
including lime mud came episodically c
some cool Qcean water 89tliR§s. Cool-
water environments occur in two
All of the precipitates are calcite. In deep
water Bahamian muds the crystals are
from nearby platforms or shelves, the
times between sedimentation events
e
locales; (1) in shallow temperate en- blocky calcite, 2-4 micrometres in size, as equid have been periods of recrystalliz-
vironments where carbonate sediments cement QvergrQwing coccoliths, as druse ation and cementation by calcite on the
are dominated by the foramol assem- in foraminifera chambers, calcispheres, sea floor. "-
blage (Mg-calcite and calcite); (2) and the molds of pteropod shells. Calcite (
in deepwater, along the margins ottropi- also precipitates as epitaxial overgrowths ZONES III AND IV: DEEP BASINAL
cal carbonate platforms and on the on echinoid particles. In MiQcenereef car- ENVIRONMENTS
tloors of intervening basins where shal-
low water sediments of the chlorozoan
bonates intergranular pores, sponqe bor-
ings and aragQnitefossil molds are IQcally
For deep-water environments, numer-
ous studies confirm that very little dis- c
assemblage (araqonite and Mg-calcite) lined with crusts, 0.05 to 2.0 moo thick, of solution occurs as particles settle c
(
c
c
(
Limestones - The Sea-Floor Diagenetic Environment 21

o
C' through the water column; most carbon- death, filling of their holes by fine sedi- (Zankl and Schroeder, 1972;James and
o ate is dissolved at the sediment-water ment and/or cement. Ginsburg, 1979; Land and Moore, 1980).

o interface.
If the sea floor is overlain by well-
Particle Alteration.
On a microscale this process involves
The end result, however, is the same: a
skeletal-rich rock is transformed by sev-

o oxygenated water, as is the case in most boring by endolithic algae or fungi into
sand-sized particles. Algae, mostly
eral generations of alteration into a
muddy limestone and much of the ori9.!:..

--
modern oceans, then burrowing allows
( mixing of interstitial and overlying blue-green and green, appear to be JiaL texture is lost.
waters, and thus dissolution may take most effective in the upper part of the
( place some centimetres below the sedi- photic zone to depths of about 70 m STRANDLINE DIAGENESIS
c ment surface.
::::J.t- If euxini c ~nditions prevail and the
(Budd and Perkins, 1980). Fungi extend
to depths of 500 m and more, whereas
Diagenetic processes that characterize
the sbaU~GfiiiOllQor iiIso pre-
( ' \ ~verlying waters are CO2 rich, corrosion heterotrophic algae and bacteria occur dominate in the intertidal and supratidal
may take place on the sediment surface. to abyssal depths (Friedman et a/., zones.gHere the environment IS more
Dissolution ceases once the carbonate is 1971). Infestation appears to be most complex: (1) instead of a simple rock-
buried just below the surface, because active (Kobluk and Risk, 1977) when water system the setting is three-phase,
an increase in alkalinity within the sedi- grains are at rest in lagoonal or other on- rock-water-air; (2) freshwater flow from
ment is brought about by bacterial sul- shelf settings. land extends seaward out underneath

c phate reduction (Berner, 1971). Carbon-


ates may not suffer dissolution in euxinic
In shallow tropical environments
where precipitation is dominant (Zone I)
the shore, with the water table at or just
below the strandline sediment surface;
basins or on slopes where the oxygen- the vacated holes of endoliths are filled and (3) the waters themselves are com-
minimum zone impinges on the sea floor. by Mg-calcite and/or aragonite cement monly mixtures of marine and meteorip
Although corrosion surfaces have been (Margolis and Rex, 1971; Alexanders- fluids. __ £r() /),/.1- , W/VJ t::j"w47
reported in limestones of basins inter- son, 1978).If the numerous generations Beaches. ~ 10. (er.R.cll1~{
preted as rather restricted (e.g., Lind- of boring endoliths are restricted to the The most com ffl6~ifestation of
strom, 1979), signs of dissolution grain margin, a rind of microcrystalline strandline precipitation is beachrock-
beneath such surfaces appear to be Mg-calcite or aragonite called a "micrite layers of cemented beach calcarenite
extremely rare. In fact, under the right envelope" (Bathurst, 1966) develops. (Figure 9) that dip seaward at the same
conditions carbonate precipitation will The formation of these envelopes is attitude as beach sediments and are
occur, the chemistry of which is dis- often critical to grain preservation in composed of the same grains as the
cussed by Hesse (this volume). later diagenetic environments. beach sand, which can be anything from
Summary. If infestation is intense and prolonged carbonate to quartz to volcanic litho-
In summary, there is a clear zonation in the entire grain may be transformed to clasts; good reviews are to be found in
,. diagenesis along the margins of tropical microcrystalline Mg-calcite or arag- Stoddart and Cann (1965)and Milliman
carbonate platforms facing deep water onite, with little trace left of the original (1974). Some tropical. intertidal zones
(Figure 6); parts of shallow water reefs structure (Kendall and Skipwith, 1969). are all beachrock, others have only scat-
and sand shoals are commonly lithified This pervasive micritization is par- tered layers, and many are without it.
early by aragonite and Mg-calcite, as ticularly common in grapestone lumps Strata generally are localized to the
are the adjacent fore-reef sediments (Bathurst, 1975) and in stromatolites intertidal zone extending up into the
(Zone I); .lithification decreases down (Logan, 1974). These "diagenetic pel- zone of wave splash and disappearing
.§lQp.e, as the waters become cooler, oids" are in some instances difficult if seaward, landward, and with depth into
grading from pavements to nodules to not impossible to distinguish from fecal unconsolidated sediment. The beach-
little cementation; in cold wate..!§., which pellets or Mg-calcite cement aggre- rock may be present as scattered nod-
,..
are undersaturated with resRectto arag- gates. As a result, it should be stressed ules, isolated slab-like layers, or whole
onite, dissolution of the metastable that the term "peloid" applies to grains thicknesses of beach sediment, gener-
sediments and precipitation of calcite, that may have had very different origins ally developing a few centimetres below
resulting in cementation, may occur but look the same. the sediment surface.
(Zone II); in very cold deep waters most Outside the tropics and in deeper water The surface of the beachrock is com-
(Zone III) or all (Zone IV)ofthe carbonate (Zone II)infestation is often just as intense monly pitted and bored and exhibits dis-
is dissolved. but the holes are not filled because of the solution basins or potholes. In cross-
lack of precipitation and so the grains are section beachrock is well laminated and

or: BIOLOGICAL ALTERATION


Even though neomorphism sensu
gradually broken down into smaller parti-
cles (Alexandersson, 1979).
the base of each layer is sharp. The rock
is characteristically jointed into blocks
strictu is not a common process in shal- Limestone Alteration. and textured by cracks and channels.
low-water carbonates, sedimentary Voring also occurs on a macroscale with Erosion of rock slabs and reworking dur-
particles and rocks do undergo drastic ~ 'sponges, bivalves and polychaete ing intense storms leads to conglomer-
alteration to micrite or mudstone worms being the excavating organisms. ates or ramparts of beachrock clasts.
through a combination of biological and Particularly common in reefs and on The grain-size of the sediment ranges
chemical processes. The mechanism hardground surfaces, the cavities cre- from sand to boulders.
involves infestation of the carbonate ated by these larger excavating inverte- Induration varies from loosely ce-
host by one of a variety of boring or Qrates may be filled with fine sand- to mented sand that can be disaggre-
endolithic organisms and, after their
-silt-sized sedirrumt,and/or .ceme.riC:. gated by rubbing to well-lithified rock
c
22 Diagenesis Geoscience Canada Reprint Series 4 c
c
that can be broken only with a hammer. beaches predominate, but the rate and cite. In the more seaward channel belt,
c
Commonly the surface is hard and the intensity of peritidal diagenesis appear crusts are peloidal sediment without c
inside soft. Cements are aragonite or
Mg-calcite with the same spectrum of
to be functions of climate . On humid
tidal flats, as typified by the Bahamas,
filaments cemented by Mg-calcite mic-
rite (and often containing dolomite) in c
fabrics as on the sea floor, but micro-
crystalline aragonite cement is par-
cemented crusts are relatively rare.
Only a few centimetres thick (Figure
which cracks and fenestrae are filled
with acicular to bladed aragonite
c
ticularly common (see numerous arti-
cles in Bricker, 1971). In some localities
10), they are found just above the
normal high-tide mark. In the inland
(Hardie, 1977).
On arid tidal flats, such as those
c
these cements have a pendulous or marshes crusts are composed of algal along the Trucial Coast of the Persian
mini-stalactite orientation, signifying
vadose precipitation in an air-filled
filament molds encrusted with Mg-cal- Gulf (Taylorand lIIing, 1969)and around c
void. c
Beachrock forms at surprisingly
rapid rates on the order of years to c
tens of years, so that today coins, bot- c
tles, skeletons and other artifacts are
commonly found in beachrock. Most c
workers now seem to agree that pre-
cipitation of beachrock cement is from
c
seawater by evaporation and CO 2 (
degassing in the intertidal zone during
low tide (Bricker, 1971; Meyers, 1986), c
although the composition of the water
may be modified greatly by meteoric
c
mixing (Moore, 1983). Other alterna- c:
tives are by degassing of CO 2-rich
carbonate-saturated groundwaters c
which have migrated into shore areas
(Hanor, 1978), or by biologically in-
c
duced precipitation. c
Beachrock is particularly susceptible
to alteration by biological alteration c
(James and Choquette, 1984).
Figure 9 A group of geologists walking on the black, algal-infested surface of beachrock
composed of ooid and grapestone particles cemented by aragonite on the shore of Cock- c
Aragonite crusts. Aragonite crusts
up to 20 mm thick and called "conia-
roach Cay, Berry Islands, Bahamas. The white sand near the trees (right) and the sediments
beneath the water (left) are unlithified. c
tites" (Purser and Loreau, 1973) often
coat beachrock, carbonate grains and c
exposed bedrock in the splash zone. c
These coatings, which look like grey to
cream-coloured enamel paint, range c
from smooth encrustations to porous
surfaces that resemble tufa or traver-
c
tine. Beneath overhangs or in beach- c
rock they have dripstone morpho-
logies. These crusts appear to develop c
only when the substrate is imperme-
able. In the fossil record such crusts
c
could easily be mistaken for ~ea-f1oor
precipitates. ~ \Vv 1J'I'N~ V"'oj \ ~
c
Tidal Flats. \ c
Diagenesis of carbonate sediments on -
wide, muddy tidal flats is discussed in
e
part in other articles in Geoscience (
Canada (James, 1984; Kendall, 1984;
Morrow, this volume). The diagenetic c
processes are complex and involve not c
only CaC0 3 precipitation but also the
formation of dolomite and evaporite c
minerals.
In terms of limestone formation in
Figure 10 Brecciated crusts composed of peloids and algal tubules, cemented by Mg-
calcite and containing minor dolomite in the supratidal zone of the muddy tidal flats along the
c
particular, the same processes seen on western side of Andros Island, Bahamas (handle of the dive knife is 10 em long). c
c
c
Limestones - The Sea-Floor Diagenetic Environment 23

Shark Bay, (Logan, 1974), cementation from the Phanerozoic, with little informa- once they undergo neomorphism to cal-
is more extensive and crusts extend tion on Precambrian limestones. cite in another diagenetic environment,

c over the whole tidal range . Crypto-


crystalline aragonite is the most com-
Biological Alteration.
Microborings. Endol ithic algae are
and (2) were aragonite and Mg-calcite
always the normal precipitates on shal-
mon cement, quickly lithifying intertidal known in carbonates as old as Precam- low carbonate platforms in the past?

o stromatolites and algal-bound sed i-


ment.ln Shark Bay,this grades seaward
brian (Campbell, 1982) and micritized
grains are an integral part of most shal-
In our experience , marine cementa-
tion is not a common or widespread
r into acicular aragonite cementing hard-
grounds offshore. In some instances,
low-water limestone suites.
Macroborings. Macroboring ichno-
feature in ancient limestones. It is usu-
ally documented from fossil reefs (Fig-
Q the aragonite cement forms pendant fossils are known in limestones as old as ure 11), especially from reef-mounds
growths from the ceilings of farge voids Lower Cambrian (James et a/., 1977) (James, 1983, 1984) and reef blocks in
( and fenestrae. but only one, Trypanites (a probable fore-reef deposits (Figure 12), where
( Perhaps most useful as signatures of siphonculid worm trace), is found until marine cement may make up 50% or
shoreline precipitation are the large- the Middle Ordovician when reefs con - more of the rock volume . It is commonly
( scale structures produced. Rapid inter- taining large skeletons developed and inferred to be present from field evi-
granular precipitation at or near the there was a rapid diversification of endo- dence of hardgrounds yet rarely is dem-
sediment surface produces expansion liothictaxa(Kobluketal., 1978). Thebor- onstrated there on the petrographic
fractures and arcuate to polygonal ings of various small bivalves, sponges level, possibly because micrite-size
ridges and tepees. These broken crusts and echinoids are found in reefs , reef- cements are the norm and cannot be
may in turn be reworked by storms to mounds and hardgrounds of later resolved microscopically. Fibrous ce-

o produce pavements of tabular clasts.


Micritization of skeletal and oo id
Paleozoic and particularly Mesozoic
and Cenozoic age (Warme, 1975).
ments are rarely seen in marine-shelf
gra instones but have been described
o grains in many of these crusts is so
intensive that peloidal sediment is in
Cementation.
Confident recognition of sea-floor
from fossil beachrocks (Purser, 1969;
Choquette and Steinen, 1980).
part depositional and in part diagenetic. cementation and its spectrum of pro- Recognition of Sea-floor Lithification.
ducts is a critical part of any study in Prior to any analysis of sea-floor cement
THE FOSSIL RECORD carbonate petrogenesis, yet two pro- fabrics the following criteria are useful
C The products of sea-floor diagenesis can blems bedevil this seemingly simple in establishing early lithification on the
be recognized in carbonates of all ages. task: (1) what precisely are the fabr ics of sea floor (Figure 13):
O Almost all information, however, comes the aragonite and Mg-calcite cements (1) If in bedded sediments, are the litho-
o I).
1,J!./
qt. o "~J-
I\
logic contacts knife-sharp, and if grains
or cements are present are they trun-
O~ ~D c " cated (e.g., Figure 7)?
,...", ..' (2 Is the surface sta ined by iron or man-
ganese salts or phosphate minerals?
(3) Are there cobbles or pebbles of lime-
stone or sand-grade lithoclasts similar in
composition to the matrix, and if so are
they encrusted with organisms?
(4) Is the surface encrusted by orga-
nisms that require a solid substrate?
(5) Is the rock surface bored and, in thin
section , if cements are present, are they
bored as well?
(6) If in reefs, is the first-stage cement
localized to the reefs?
r (7) If in reefs or hardgrounds, is the first-
stage cement interlayered with marine
sediment in cavities (Figure 14)?
(8) If in reefs, are there n ep.tu ~n ("J-IJ
dykes? s:r...-rAIJI~ r.~('" 'tfI'(.pt 'I r
~ . H'.~ r.e.all)~
(9) In reef talus, are there clasts with
first-stage cement or clasts of the
cement (Figure 12)?
(10) If in bedded sed iments, are expan-
sion ridges and polygons present?
While these features point to early lith-
Figure 11 Photomicrograph of reef mound limestone composed of the ? phyllo id alga ification, many alone may be the result
Palaeoaplysina (P)surroundedby several generations offibrous calcite submarine cement (C) of a short-lived period of subaerial
(interpreted to have been Mg-calcite originally) and internal sediment (5); Lower Permian exposure.
Nansen Formation, Ellesmere Island, NWT. (scale 0.5 em). Photograph, G. Davies.
c
24 Diagenesis Geoscience Canada Reprint Series 4 c
c
(

c
c
c
c
Figure 12 Fore-reef debris from an Upper
Devonian reef, Canning Basin, WesternAus-
c
tralia. Theclast at centre is composed of reef c
limestone (R) (mostly the alga Renalcis and
small stromatoporoids) and fibrous calcite c
(C). Thiscement is abundant in contempora -
neous reef deposits. Such clasts are often c
good evidence that the reef itself was subject
to sea-floor cementation. c
c
c
c
c
c
(;
c
Sediment
overlying
cement
c
Clasts of
cemented l imestone c
Figure 13 Criteria for the recognition of
Encrusting
fossils c
see-tloor cementation.
Fe/Mn/P c
impregnated
surface c
dork colour
increase in c
c
amount of
sea floor cement
r
c
c
c
c
c
Figure 14 Photomicrograph of i nter-
layered marine sediment and radiaxial c
fibrous calc ite cement in laminar cavities
from a Middle Ordovician reef mound at c
Meiklejohn Peak, Nevada. (scale 1 mm).
e
(

c
c

c
(
(
(

Limestones - The Sea-Floor Diagenetic Environment 25


r
r

..
il!.,_""""_~ ,,.r m lc robOnngs
roun ded groins
f ibrous or
rnrcrocr ystcltine
cement

Figure 15 Criteria for the recogn ition of


fossil beachrock,
pilled and
( corroded
surfaces

Figure 16 Photomicrograph of a bioclas-


tic grainstone from the Ste. Genevieve For-
mation (Mississippian) Bridgeport Field ,
Illinois Basin , in which the first cement is a
fringe of fibrous calc ite that is thickest on the
undersides of grains (arrows) resembling
c small stalactites. Thisearly cementprobably
developed while the sediment was beach-
rock . (scale 2 mm).

r:

--
8 '
~
I _ _ FASCICULAR
) OPTIC
C) I I' CALCITE

curved
FIBROUS
0
.- CALCITE
cleo~Dges

~
RAOIAXIAL
FIBROUS
CALCITE
'--' Figure 17 Fabrics and morphologies of
coarse marine cements . Fibrous calcite is
generally interpreted as derived from calcite
,- or Mg-calcite and spherulitic calcite from
" reloC~
botryoidal aragonite.
PARAMORPHIC
raYs~
'- REPLACEMENT
SPHERULITI C
square
CALCITE
-~
SPAR-FILLED
'- MOLDS

spherulitic cetcue
cement
c
26 Diagenesis Geoscience Canada Reprint Series 4 c
c
In the fossil record, beachrock can be is almost unknown from modern set- 1985). On balance, the wide variety of c
differentiated from sea-floor hard- tings, and so has long been an enigma- fabrics shown by these cements in the
fossil record (James and Klappa, 1983),
c
grounds only with difficulty, butthis may
be facilitated by the observation of fea-
tic cement fabric. These two types are
not mutually exclusive and may grade even when dolomitized (Tucker, 1983), c
tures such as (1) associated edgewise
conglomerates, (2) intertidal erosion
laterally into one another along the
same cementfringe.lt seems clear that
and the wide range of magnesium con-
tents in Miocene radiaxial fibrous cal-
c
features, (3) jointing, (4) keystonevugs, these cements were originally precipi- cites, suggest that these fibrous ce- c
(5) meniscus or pendulous cements,
and (6) associated facies (Read and
tated as calcite (Sandberg, 1985). The
problem is whether this calcite was
ments may have had a rangeof magnes-
ium contents originally, depending c
Grover, 1977; Donaldson and Ricketts,
1979; Figures 15 and 16).
low-magnesium calcite, and sois moreor
less original, or whether it was high-
upon the chemisty of the precipitating
waters. Thus, those that were LMC have
c
Cement Petrography. magnesium calcite which subsequently remained unaltered while those that c
A helpful guide is the petrographic
nature of the cements themselves.
altered to its present form . This is com-
plicated because diagenesis appears
were HMC have neomorphosed.
These fibrous calcites are generally c
Accumulated evidence from the fossil
record suggests that most "fibrous"
to favour selective alteration of com-
positionally uniform Mg-calcite (re-
preferentially enriched in Mg2+ and
have c5 13 C values consistent with pre-
c
cements as well as many "spherulitic" flecting differences in the original crys- cipitation from seawater (e.g., Davies, c
or mammillary cements were marine
originally, although they are also pre-
tal structure) leading to calcite with
highly variable magnesium contents
1977; Walls et al., 1979; Given and
Lohmann, 1985; Kerans et al., 1986). c
sent in speleothems. Although micro-
crystalline calcite, or Mg-calcite and
(Videtich, 1985). On the one hand, cal-
cite skeletons, known to have been
Stromatactis. An important struc-
ture in fossil carbonates, especially mud
c
possibly aragonite, were precipitated HMC originally, now contain tiny mounds, is stromatactis, loosely de- c
from seawater in the past as they are
today,the small size of the crystals, their
rhombs of dolomite, 1-10 micrometres in
size (Macqueen and Ghent, 1970).
fined as irregular masses of fibrous cal-
cite spar often displaying a flat base.
c
similarity to carbonate mud and their Since many, but not all, fibrous calcites These features originally were thought c
susceptibility to rapid recrystallization
all make their identification difficult
also contain these dolomite inclusions
they are likewise interpreted to have
to be the recrystallized remains of a
mound-forming organism, but since the c
(Mountjoy and Riding, 1981).
Fibrous calcites. These cements
been HMC originally (Lohmann and
Meyers, 1977). On the other hand, on
work of Bathurst (1959) are now known
to be sediment-floored cavities filled
c
(Figure 17) fall into two general groups: the basis of petrography and geochem- with fibrous , radiaxial calcite cement. c
(1) fascicular-optic (Figure 18) cones of
fibrous calcite with divergent optic
istryof Paleozoic and very young Ceno-
zoic radiaxial fibrous calcites it seems
Furthermore, Bathurst (1982) thinks
that the whole structure is marine in c
axes (Kendall, 1977), and (2) radiaxial-
fibrous crystals (Figure 19) with conser-
that these cements precipitated as LMC
and HMC (Kendall, 1985 ; Saller, 1986).
origin and forms by a complex history of
multigeneration sea-floor cementation
c
tal boundaries and convergent optic The peculiar fabric of radiaxial fibrous and cavity formation . c
axes (Bathurst, 1959; Kendall and
Tucker. 1973). While common in fossil
calcite is thought to form by a process of
asymmetric growth within calcite crys-
Epitaxial cement. In contrast to the
modern sea floor, there seems to be c
reefs and reef mounds. radiaxial calcite tals undergoing split-growth (Kendall. abundant evidencefromthe fossil record c
c
~
c
c
c
c
c
e
c
c
c
Figure 18 Photomicrograph in partially polarized light of fascicular
optic calcite cement from Lower Cambrian reef mounds in the Forteau
Figure 19 Photomicrograph in partiaffy polarized light of radiaxial
fibrous calcite cements in the Middle Ordovician reef mound at c
Formation, southern Labrador. The numerous nested cones have the
same irregular crystal boundaries as radiaxial fibrous calcite but lack
Meikeljohn Peak, Nevada. The crystals characteristicaffy have con-
certal boundaries, curved twins, convergent optic axes and contain c
the curved twins and have divergent optic axes. (scale 0.5 mm). diverging subcrystals. (scale 0.5 mm).
c
c
c
C'
C Limestones - The Sea-Floor Diagenetic Environment 27

C
C that syntaxial overgrowths of Mg-cal- and Riding, 1983). Lasemi and Sand- than near-surface meteoric or burial-
o cite cement on echinoderm particles
were common phenomena in the shal-
berg (1982) have discovered that those
micrites and microspars with appar-
diagenetic cements. Compared with
co-existing skeletal debris believed to
(
low marine environment (Meyers, 1974; ently aragonite-dominated lime mud have been low-Mg calcite originally and
r Lohmann and Meyers, 1977) . In some
localit ies, marine epitaxial cements are
precursors have neomorphic calcite
crystals which show pitted surfaces
thus relatively stable (e.g., brachio-
pods, bryozoans, trilob ites), marine ce-
( also common on brachiopods, corals, and/or relic aragonite inclusions in pol- ments have roughly the same e5 13 C but
stromatoporoids, calcispheres and ished and etched sections . In contrast, e5 18 0 which may be lighter or heavier. It
C ooids (Kerans et al., 1986). micrite with apparent calcite-dominated now seems clear that these cements,
o Scalenohedral cement. Clear col-
umnar crystals which contain few inclu-
precursors are characterized by finely
crystalline < 4 micrometre textures,
along with all other CaC0 3 components
of limestones, undergo varying degrees
( sions and display unit extinction are lack any inclus ions and have unpitted of geochemical alteration from slight to
c locally common and interpreted as
marine cements (Kerans et a/., 1986).
crystal surfaces .
Isotopic Signature of Fossil Marine
extensive (Brand and Veizer, 1980, 1981;
Given and Lohmann , 1985) depending
o Spherulitic calcite. There are
numerous instances of spherulitic cal-
Cements.
From a number of careful studies involv-
in part upon whether the majority of
their diagenesis took place in closed,
cite (Figure 20) which mimic the geome- ing selectively sampled cements and partly closed or open systems with
o try of Holocene aragonite sea-floor
cements, especially in reefs. Like for-
other components of limestones (e.g.,
Choquette, 1968; Hudson, 1977; Dick-
respect to pore wate r. Given and
Lohmann (1985) have argued , using
o mer aragonite skeletons, the fabric in son and Coleman , 1980; Brand and both cathodoluminescence petrogra-

o these botryoids is preserved either as a


mosaic of tiny crystals or as a para-
Veizer, 1981; Given and Lohmann, 1985;
Lohmann, in press), it is clear that
phy and a large body of isotopic ana-
lyses, that closed-system diagenesis
o morphic replacement (Assereto and
Folk, 1980; Mazzullo, 1980) or even as
marine and other CaC0 3 cements in the
fossil record have by and large pre-
operates on a microscale to preserve
the isotopic signatures of many marine
chert (Grotzinger and Read, 1983). For a served enough of their original signa- cements.

o detailed discussion on styles of altera-


tion see Sandberg (1985) and the follow-
ture to be distinguishable from one
another (Figure 21). In general , the
There is growing evidence that iso-
topic compositions of botryoidal (former
o ing chapter on meteoric diagenesis.
Actual aragonite cement crystallites
marine cements (isopachous, radiaxial
fibrous, micritic and botryo idal) contain
aragonite) and fibrous calcite cements
show systematic yariations through the
preserved in calcite have been dis- isotopically heavier carbon and oxygen Phanerozoic which seem to transcend

o covered in rocks as old as Pennsylva-


nian (Sandberg and Popp, 1981). These
replaced aragon ite spherulites are +6

o sometimes still enriched in Sr and again


have a e5 13 C consistent with marine
o precipitation .
+4

..
Microcrystalline calcite. Finely
o crystalline calcite is extremely difficult
~

o to interpret as a fossil cement (Mountjoy


o
~ +2
z
o

o lD
II:
e:t
ol-------------_.,....",...,.,=-.:-----t--------I
o o

o
o -2

(
- ~1L,.2-....L..-+-.l.---,1,----l--!---l--+-.l.----!1,----l-~-....L..-+--.l----'·
l -6 -4 -2
OXYGEN, 8 180 ("10.)
+4

C.
( Figure 21 Cross-plot of carbon versus oxygen isotopic compositions of Holocene and
ancient fibrous and spherulitic (botryo idal) carbonate cements. The values shown are the
" heaviest" compos itions from covar iate populations of data, believed to approximate most
Figure 20 Photomicrograph of coa- closely the original marine-isotopic compositions of the cements (method of Given and
lesced, strontium-rich calcite botryoids Lohmann, 1985). The data are from James and Ginsburg (1979), Moldavanyi and Lohmann
(interpreted to have been aragonite origi- (1982), Marshall and Ashton (1980), Given and Lohmann (1983), Davies and Krause (1975),
/" nally) from a reef mound in the Nansen For- Lohmann (1983) , MeyersandLohmann(1983), Walls etal.(1979), MattesandMountjoy(1980),
mation (Lower Permian) Ellesmere Island, Cercone and Lohmann (1983), Sears and Lucia (1980), Ross et al. (1975), and James and
NWT. (scale 2 mm). Photograph, G. Davies. Klappa (1983), listed in order of increasing age of the stratigraphic units involved.
; . ? '" • !.'''-''''''v- ';;~ L~C'r-v--
J 11C) -. I (in\' )lQ!J..;a.--
c
28 Diagenesis Geoscience Canada Reprint Series 4 c
c
regional differences in diagenetic his- An original model of linear change patterns in the lithosphere. Sea level c
tory (Figures 21 and 22). These varia- from calcite seas in the early and middle is high and shallow seas vast because (
tions are consistent overall with the vari- Paleozoic to later aragonite seas has of extension in the length and width of
ability of isotopic compositions through now been replaced by a non-linear the mid-ocean ridge system; the "sub- c
Phanerozoic time for whole-rock lime-
stones (e.g., Veizer and Hoefs, 1976)
model tied to changes in atmospheric
PC0 2 (Mackenzie and Pigott, 1981;
mergent mode" of Wilkinson et al.
(1985). c
and for brachiopods (Pigott, 1981). Iso- Pigott, 1981; Sandberg and Popp, 1981; Aragonite Seas. Theatmosphereisin c
topic variations ofthis magnitude can be
explained in a number of ways, includ-
Sandberg, 1983). This most recent
model has more universal appeal as it is
the "icehouse" mode with lower Pco,
because of the reduced volcanism due c
ing differences in degree of diagenetic
alteration and re-equilibration (e.g.,
also related to world-wide sea-level fluc-
tuations (e.g., Vail et ei., 1977) and
to sluggish plate movement and aggre-
gated continents. Sea level is low and
c
Dickson and Coleman, 1980). There is a global tectonics. Fischer (1981) usesthe shallow seas reduced to narrow strips c
grOWing basis for believing that the oxy-
gen isotopic composition of seawater
term "greenhouse mode" to label times
when the atmosphere contained more
along continental margins because the
mid-ocean ridge system has dropped;
c
itself has varied since Precambrian
time (Brand and Veizer, 1981; Popp et al.,
CO 2 than it does today and so the sur-
face of the earth was warmer, and the
the "emergent mode" of Wilkinson et al. c
1981; Lohmann, 1988). Differences of
up to 5.5%0 in 0180 between present-day
term "icehouse" to characterize times
(1985).
The systematic variations in isotopic c
and past seawater have been postu-
like the present, with lower CO 2 , cooler
temperatures and continental glacia-
composition of brachiopods (Veizer et
et., 1986; Poppetal., 1986), fossil marine
c
lated by Brand and Veizer (1981), and
differences in 013C may have been
tion. Integrating these concepts, it is
postulated that in the past shallow-
cements (Figures 20 and 21) and car-
bonates in general (Veizer and Hoefs,
c
nearly as great (Figure 22). water carbonate deposition took place (
1976) tend to support this hypothesis

THE PRESENT IS NOT ALWAYS THE


under one of the following conditions
(Figure 22):
since "aragonite seas" and "calcite
seas" should be characterized by heav-
c
KEY TO THE PAST Calcite Seas. The atmosphere is in ier and lighter 013C, respectively. Since c
One of the guiding tenets of carbonate
petrology is uniformitarianism . espe-
the "greenhouse" mode with high PC0 2
because of increased volcanism result-
marine carbonates show a linear rela-
e
tionship between 013 and 0180 (Milli- c
cially the concept that, as in present
times, aragonite and Mg-calcite were the
ing from rapid and complex convective man and Muller, 1974), we would expect c
most common carbonates forming on EUSTATIC c
shallow sea floors ofthe past. This axiom
has recently been challenged, and it now
MARINE
bleo s
CEMENTS
~p C.
RISING - SEA LEVEL--FALLING c
c
0/00
seems quite likely that an alternative is 8 0 +8 W
o o
possible, i.e., thatthere were times when
calcite was the normal sea-floor precipi- W T c
tate (see Sandberg, 1983 and an excel-
lent review by Wilkinson, 1982).
(f)
:::l
0 c
I
K
Twenty-five years ago, Lowenstam
(1963) pointed out that the composition
Z
W
w
100
c
of marine skeletons apparently had
0:
(9
II II
J C
200
changed during the Phanerozoic:
Paleozoic seas were dominated by cal-
w
(f)
ARAGONITE
SEAS
R E
~
:::l
cite-secreting invertebrates, Cenozoic 0
I C
and modern seas were characterized by W

organisms which secreted aragonite ~ C 300 C


and Mg-calcite skeletons, and Meso-
zoic seas contained roughly equal num-
w
(f)
:::l 0 C
bers of each. In the last few years, on the
0
I
S
400 C
c
Z
basis of new data from fossil skeletons W
W
(Wilkinson, 1979; Pigott, 1981), ooids 0:
0
(Sandberg, 1975; Pigott and Mack-
enzie, 1979; Wilkinson et al., 1984),
(9
500 e
c.
i
cements (Folk, 1974; Wilkinson, 1982; £
Sandberg, 1983), and carbonate muds
(Folk, 1974; Sandberg, 1975), it appears pe; 600 c
that much carbonate in the fossil record
was deposited or precipitated as cal-
c
cite. Milliken and Pigott (1977) coined Figure 22 (Right) The possible distribution of "calcite" and "aragonite" seas in geologic
(
the term "calcite seas" to differentiate
these periods from times similar to the
history. Modified from Fischer (1981) and Wilkinson (1982).
(Left) Variations in oxygen and carbon isotopic compositions of marine cements through
c
"aragonite seas" of today. Phanerozoic time. The data are from the sources acknowledged in Figure 21 (caption).
(
c' Limestones - The Sea-Floor Diagenetic Environment 29

c:
c that radiaxial fibrous , botryoidal and of these features . There is a clear zona- read by R.G.C. Bathurst, N. Chow, M.
(, other marine CaC0 3 cements also tion present on reef-rimmed platforms Coniglio, P. Sandberg and R.K. Ste-
should have had original isotopic signa- with cementat ion decreasing into the vens, to all of whom we owe special
o tures which were heavier during times of
"aragonite seas" and lighter during
lagoon, onto the platform and down-
slope into deep water. If the lower parts
thanks. N.P. James acknowledges the
Natural Sciences and Engineering
C times of "calcite seas", This is exactly of the slope are in waters undersatu- Research Council of Canada for on-
o the relationship we appear to be seeing
in Figure 22, where, from groups of ana-
rated with respect to aragonite, then
lithification may take place in deep cold
going financial support

( lyses the heaviest (most nearly original) waters by dissolution and reprecipita- REFERENCES
o isotopic values have been plotted
versus geologic time, The departure of
tion. Such azonation is less apparent on
open platforms and ramps, where ex- General References and Reviews
( the curves for 0'80 and 0'3C in late tensive lithification of sand sheets to
Bathurst , R.G.C., 1975, Carbonate Sedi-
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( implies a diagenetic and/or original sea- The major prerequisites for early sea- North Holland, 658 p.
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eral relationship suggests some con-
floor cementation appear to be an oxi-
dizing environment, a stable substrate
Chapter 9 and the updated appendix are
a good introduction to this topic.
( sistent non-linear trends in seawater and good water exchange. Recognition Bathurst, R.G.C., 1980, Lithification of car-

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An excellent update to the material cov-
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o The question of whether seawater sence is easily inferred but proven with
Bathurst , R.G.C., 1986, Carbonate diagen-
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o isotopic composition has, indeed, var-
ied significantly and systematically
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The present is but a general guide to
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through time is critically important in sea-floor dia enesis in the ast. Th~ Environments; Part5: Diagenesis 1, Col-
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o rocks using geochemical compositions,


If this is the case then the discussion of
main precipitate and periods when, Iik
today, aragonite and Mg-calcite we
An essay focussed on porosity highlight-
ing the importance of early diagenesis.

o carbonate precipitation on the modern


sea floor outlined in this essay applies
dominant Geochemical interpretations
of fossil precipitates are further compli-
Br icker, O .P., 1971, ed . , Carbonate
Cements: The Johns Hopkins University

o mainly to specific times in the past :


(1) late Precambrian and Cambrian,
cated by the fact that the isotopic com-
position of seawater seems to have var-
Press, Baltimore, MD, p. 201-236.
Theearly work on sea-floor diagenesis is
G (2) Pennsylvanian to Triassic, possibly ied with time.
well documented in 7 important papers.
Hudson, J.D., 1977, Stable isotopes and
o Jurassic and (3) Cenozoic - the " emer-
gent" modes. During the early and
The implications of sea-floor cemen-
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limestone lithification: Journal of the

o middle Paleozoic and much of the new environments, maintenance of


Geological Society, v. 133, p. 637-660.
An excellent overview of stable isotopes,

o Mesozoic abiotic carbonate precipita-


tion in shallow seas would have been
large carbonate structures and the pre-
servation of depositional textures and
carbonates and seawater.
James, N.P.and Ginsburg, R.N., 1979, The

o mostly calcite.
Another impliction is that clear, rhom-
fabrics. ~xtensive intergranular pre-
cipitation, however, reduces dramat-
seaward margin of Belize barrier and
atoll reefs: International Association of
( bic calcite cement, generally thought to ica y the depositiona porosl yan per-
Sedimentologists, Special Publication
3,199 p.
o be characteristic of precipitation from
fresh water (see the next article in this
meabilit of s ecific aCles ren erm
them unsuitable as reservoirs for hydro-
A detailed, well-illustrated documenta-

o series) is not diagnostic alone as evi- carbons a e metals.


tion of early diagenesis along a modern
platform margin setting.

o dence of exposure to meteoric fluids


(Given and Wilkinson , 1985), and may
be a sea-floor precipitate (Wilkinson et
ACKNOWLEDGEMENTS
This series of articles is an outgrowth of
Milliman, J.D. and Muller, J., 1977, Charac-
teristics and genesis of shallow-water
and deep-water limestone , in Anderson,
al., 1982). a graduate-level course in carbonate N.R. and Malahoff, A., eds., The Fate of
petrogenesis given at Memorial Univer- Fossil Fuel CO2 in the Oceans: Plenum
Press, New York, p. 655-673.
SUMMARY sity and a carbonate training seminar
A summary of the attributes of marine
Taken as a whole, marine sea-floor presented to Marathon Oil Company.
c diagenesis is not common in either mod-
ern or ancient carbonate sediments.
We thank all those willing and unwilling
participants who helped shape our
cements.
Schneidermann, N. and Harris, P.M., 1985,
eds., Carbonate Cements: Society of
Cementation, however, is of major ideas . K.C. Lohmann generously Econom ic Mineralogists and Paleon-
importance in certain facies, namely allowed us to use some of his unpub- tologists, Special Publication No. 36,
along platform and reef margins, on lished data on the isotopic composition 379 p.
sand shoals and in the strandline. Early, of fossil cements, thus enabling us to A collection of papers on modern and
shallow water lithification of platform present a much more coherent picture ancient carbonate cements, a good
and reef margins is probably one of the than would otherwise have been possi- source of current information on the
topic.
main reasons for the structural integrity ble. This article was originally critically
c
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( Limestones - The Sea-Floor Diagenetic Environment 31

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C.H ., eds ., Carbonate Depositional
c:
mound of Meiklejohn Peak, Southern original isotopic conpos itions in some Environments: American Association of
Petroleum Geologists , Memoir 33 ,
c
Nevada: United States Geological Sur-
vey, Professional Paper 871, 48 p.
Paleozoic limestones : Geological
Society of America, Bulletin, v.97, p.345·440. c
Sears, S.D. and Lucia, EJ., 1980, Dolomiti-
zation of northern Michigan Niagara
p. 1262-1268.
Sandberg , P.A., 1975, New interpretations
James, N.P., 1984, Shallowing-upward
sequences in carbonates , in Walker, c
reefs by brine refluxion and freshwater/
seawater mixing , in Zenger, D.H., Dun-
of Great Salt Lake ooids and nonskeletal
carbonate mineralogy: Sedimentology,
°R.G., ed., Facies Models, Second Edi-
tion : Geological Association of Canada, c
ham, J.B. and Eth ington, R.L., eds .,
Concepts and Models of Dolomitization:
v. 22, p. 497-537.
Sandberg, P.A., 1983,An oscillating trend in
Geoscience Canada Reprint Series 1,
p.213-228 .
c
Society of Economic Paleontologists Phanerozoic non-skeletal carbonate James, N.P., 1984, Reefs, in Walker, R.G., c
and Mineralogists, Special Publication
No. 28, p. 215·237.
mineralogy: Nature, v. 305, p. 19-22.
Vail, P.R., Mitchum, J.R. and Thompson, S.,
ed., Facies Models, Second Edition :
Geological Association of Canada, Geo- c
Veizer, J. and Hoefs, J., 1976, The nature of
180 /180 and 13C/12C secular trends in
11I,1977, Seismic stratigraphy and global
changes in sea-level, part 4, in Peyton,
science Canada Reprint Ser ies 1,
p.229-244. c
sedimentary rocks : Geochimica et Cos-
mochimica Acta, v. 40, p. 1387-1395.
C.E., ed., Seismic Stratigraphy: Ameri-
can Assoc iation of Petroleum Geolo-
Kendall , A.C., 1978, Evaporites, in Walker,
R.G., ed., Facies Models, Second Edi- c
Walls, R.A., Mountjoy, E.W. and Fritz, P. ,
1979, Isotopic composition and diage-
gists , Memoir 26, p. 83-97.
Veizer,J., Fritz, p. and Jones, B., 1986,Geo-
tion : Geological Associat ion of Canada,
Geoscience Canada Reprint Series 1,
c
netic history of carbonate cements in chemistry of brachiopods: oxygen and p.259-296.
Devonian Golden Spike reef, Alberta,
Canada: Geological Society of America,
carbon isotopic records of Paleozoic
oceans : Geochimica et Cosmochimica
Murray, J.L. and Renard, A.F., 1891, Report
on deep sea deposits based on the c
Bulletin, v. 90, p. 963-982. Acta, v. 50, p. 1679-1696.
Wilkinson, B.H., 1979, Biomineralization,
specimens collected during the voy-
age of H.M.S. Challenger in the years c
Temporal Variations In the Mineralogy
and Isotopic Composition of Sea-floor
paleoceanography and the evolution of
calcareous marine organ isms: Geology,
1872-1876, 525 p. [Reprinted by
Johnson Reprint, London, 1965. J c
Precipitates v. 7, p. 524-527.
Wilkinson, B.H., 1982, Cyclic cratonic car-
Murray, J. and Hjort, J., 1912, The Depths of
the Oceans: Macmillan , London. 831 p.
c
Fischer, A.G., 1981, Climatic oscillations in
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bonates and phanerozo ic calcite seas:
Journal of Geological Education , v. 30,
e
Biotic Crises in Ecological and Evolu- p.189-203. (
tionary Time: Academic Press , New
York, p. 103-133.
Wilkinson, B.H., Bucynski, C. and Owen,
R.M., 1984, Implications from Upper c
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Originally published in
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p.932-947.
(December 1983)
Revised 1988
c
cago Press, Chicago, p. 137-195.
vV
c
\\1 (

sy --- \/)/ (
C
Limestones - The Meteoric Diagenetic Environment 35

r: ~The meteoric diagenetic env iron- large skeletons of the same mineralogy
/~ent is one with many apparent contra- change more slowly. Individual grains

o dictions. For example, the main process


is carbonate dissolution , yet here is
will also alter at diffe rent rates, depend-
ing upon the crystal size and relative
c where soft sediment is transformed into
hard limestone, the same waters that
amount of organic material. Finally,
porosity and permeability of the sedi-
precipitate CaC0 3 when mixed may dis- ment, which govern the rate at which

c solve CaC0 3 ; while spectacular caves


are being excavated, delicate fossils are
fluids flow through and the length of
time they are in contact with the sedi-
being preserved. ment or rock, affect the speed at which
Limestones - The The environment has been studied changes take place.
more intensively than any other diage- Perhaps the most "cruclal extrinsic
Meteoric Diagenetic netic realm, yet we are really only rea- factor is climate; in areas of extensive
Environment sonably confident about processes and rainfall and warm temperatures diagen-
o products that occur above the water
table.
esis proceeds quickly and with great
vigour, whereas in warm arid regions,
Noel P. James The wide variety of limestones that because of little water, sediments are
r Department of Geological Sciences
Queen's University
result from meteoric diagenesis -
often beginning with the same sedi-
often unchanged for long periods, or
are virtually unaffected by subaerial
Kingston, Ontario K7L 3N6 ment - are the end result of several exposure. As the dissolving power of
reactions, governed by intrinsic and fresh water is largely controlled by bio-
( Philip W. Choquette extrinsic factors (Figure 2) that may logically produced CO2 , the amount of
Department of Geological Sciences proceed at different rates for varying large vegetation is also important.
University of Colorado lengths of time. The most important Finally time is critical: the longer a sedi-
Boulder, Colorado 80309-250 intrinsic factor is original mineralogy: ment is exposed in the meteoric
sediments composed of several CaC0 3 environment, the more intensive the
minerals , dominated by aragonite and changes will be.
INTRODUCTION magnesium-rich calcite (Mg-calcite),
Carbonate sediments, born in the sea, which are metastable with respect to THE METEORIC SETTING
remain largely unaltered while bathed in fresh water, alter most; those sedi- As outlined in the introduction to this
c their embryonic fluids of high ionic
strength. With time, however, the com-
ments composed only of various calcite
minerals alter least. Grain size control
series on limestone diagenesis, the me-
teoric environment can be subdivided in
position ofthe pore waters will inevitably the rate at which these components most general terms into vadose and
change , and if exposed to circulating change; fine-grained sediments and phreatic settiogs.(Figure 3).
ground water, the sediments may finely crystalline particles, because of ~he water table marks the top of the
undergo profound and geologically their large ratio of surface area to parti- phreatic zone and represents the level
rapid diagenesis (Figure 1). cle size, change most rapidly, whereas at which hydrostatic pressure is equal
to atmospheric pressure. The most
common aquifers are unconfined, or
open to the atmosphere, and the hydro-
r static level is within the water-bearing
unit. There are two types of gravity.
induced flow in this situat ion (White,
1969). Under conditions of diffuse flow

METEORIC DIAGENESIS

CONTROLS SETTINGS -. C
INTRINSIC ;l"" fi ll
~ ~ : ~ : a / .' .
MINERALOGY
.~ • .,'-"<>.

ll";~I
GRAIN SIZE
POROSITY" PERMEABlUTY
ZONE

EXTRINSIC
.. ~ .

CUIoIATE WATER TABLE


. ~

VEGETATION
PHREATIC
TIME ZONE
I ~
'r ..XING ZONE

Figure 1 Theshore of Bimini, The Bahamas. The rock on the right is carbonate sediment that Figure 2 The principal controls on, and
has been cemented by exposure to meteoric waters over the last several thousand years. settings of, meteoric diagenesis.
c
36 Diagenesis Geoscience Canada Reprint Series 4 c
c
there is a well-defined water table and Unconfined aquifers characterized limestone via a network of tiny fractures
c
water movement obeys or nearly obeys
Darcy's law. The sediment or rock has
by diffuse flow are most usefully divided
into the vadose zone, above the water
or small pores. In contrast, vadose flow
(Thrailkill, 1968) is the relatively rapid
c
relatively homogeneous porosity and table; the active, shallow, freshwater movement of water downward via joints, c
permeability characteristics, karst phreatic zone or lenticularphreatic zone large fissures and sinkholes, ofte ~ 1.,":/ (
landforms are rare and subdued on a
generally low-relief surface , small cav-
(Jakucs, 1977), below the water table;
and the sublenticular mixing zone, also
directly to the water table. ~""~
The Wafer Table. Dl<;S1:>W . ~ ,,,IT'
e c
ities are somewhat randomly arranged referred to as the transition, mixing, As will be discussed later;-CUie water
and flow is relatively deep. In contrast, diffusion or dispersion zone. The gen- table is'a surface of great inportance in C
under free flow conditions water moves
through integrated conduits which func -
eral relationships of these settings are
shown in Figure 3.
carbonate diagenesis. In older, pre-
Pleistocene limestones its former pre-
c
tion like a series of three-dimensional The Vadose Zone. sence and position can often only be C
subterranean rivers. The water table is Rainwater, meltwater or runoff enters a recognized approximately if at all
discontinuous or difficult to recognize at carbonate sequence either directly on because of long and complex diage- C
all, but there is nevertheless a continu-
ous potentiometric surface. Diffuse
bare rock or through a calcrete or soil.
The zone of infiltration (Figure 3) is a
netic histories . Some criteria that can be
helpful in delineating paleowater tables
C
flow aquifers with a well-defined water realm of complex carbonate-water in- are presented later in this article. On C
table are typ ically developed in newly teraction. Although water may pass relatively small , present-day limestone
exposed young carbonate sediments, directly into the rock, in most situations islands the water table is usually very C
but with time and diagenesis aquifers
evolve into the free flow type charac-
there is a soil or protosoil on top of
bedrock. Biological activity in the soil
gently bowed upward toward the island
interior, as a rule rising less than a metre
C
terized by conduit flow and a discon- not only alters the composition of the per kilometre (Figures 3 and 4). Beneath C
tinuous water table. In this paper the fresh water but, in many cases, induces widespread carbonate platforms and
focus is on diffuse flow aquifers. carbonate precipitation. This zone is mainland carbonate plains underlain by
C
The other entirely different type of subject also to evaporation or evapo- flat-lying strata the water table appears C
flow is confined. The aquifers are transpiration, especially in the tropics, to have almost imperceptible relief (Fig-
bounded by aquitards (impermeable so that some of the downward percolat- ure 3). For example, two of the better C
layers), and are not connected vertically
to the atmosphere. Waterflow is by pres-
ing waters are drawn back up to the
surface, again leading to carbonate
known karst terrains of North America
- the northern Yucatan and the south-
C
sure and will rise above the level of the precipitation. ern peninsula of Florida (Back and C
aquifer inwells (artesian flow). Confined The underlying and more extensive Hanshaw, 1970; Back et et., 1976)
aquifers are particularly important as zone of gravity percolation is charac- regions of about 50,000 km2 - have C
conduits by which fresh water can flow terized by pores variably filled with watertable elevations which reach max-
deep into sedimentary basins and con- water andlor air or organically produced ima of only a few metres and mostly less
C
siderable distances out beneath the gas. Under conditions of vadose than 20 metres, respectively. C
continental shelf. seepage water trickles through the
C
C
THE METEORIC C
ENVIRONMENT ~
C
C
C
C
SHALLOW PHREATIC LENTICULAR ZONE
(FRESH WATER) .> -: >:MA~INE' ::
-: :"::::\::'2 :. '.'
c
~
~
~
r :
: . : ...'.: . .::- ·.: · · PHREATIC ~ e
MIXING ZONE (BRACKISH WATER)
? .. . . .
. ~ .. ..... :-:: ::.:.::::.-:: ::::.-:::.:..: .:.:.:-: . .. ZONE
.
<.".::'
-
c
::: ::::::::::::::::::::::::.:::::: ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: ::::.:.: ::::::::::.::::::.::::::::.:.::: ::::. :: :.:: (.S~~ ~.~~~ c
-:.:.:-:.:-:-:-:..:.::-:-:-:-:.:.: -:-:-:".::-:-:..::":-: DEEP PHREATIC ZONE .:-:-:.:":.:-:..:.::..:.::..::..:.:.::...: : : : : : . : : :." ...":-. :-:- :-:-:"....:
:::::::::::::::::::::::::::::::::: :::::::::::::::::::::::::: .(~~l:~~. ~~:r.~~). ::::::::::::::::.::::::: ::::::::::::::::::::': :::::" .::':::::::::::'.::::.: '::::::::.:: C
.... ... .. . .. .. . . . . . . . .. \.
. . . . . . . . . . ... .. .. .. . . ... . .. ... .. . . . . . . . . . . . . ... . .. . . . . . . . .. . .. . ... . . .. . . . .. . .. ..... . ... . .-. . . . . .. - . ,

C
Figure 3 A sketch outlining the main zones of the meteoric diagenetic environment.
C
C
C
~
( ~y~-'~~~'\tJt!'~ Q~J fhJ~ kJ«I-!?Vv~ ;nC-rr~ ..
~ :::;6171) L,.-. l r- ~ 0 - l .;;) ;:'V'v""'.- J. I'Yr.f t.. /Al 0 /~
C p.
(J" ,f'. -
~9' O l!.imestones "f The Meteoric Diagenetic Environment ... l,I C/V'-
-
....... ~ I

37

C tJ' ~~ fv'~t..fo"~-l~ (ODD~ clJ'~ CO~1l <;:kx-l<J..t, ri


C' (oJ"' > w~ en s: 6a ~~ ;.-v-- F"f7.s:k
f-
The r Jnticular Zane. less, the important point is that only relationship. In strongly dynamic sys-
(' This zone has as its lower boundary minorelevation above sea level can lead tems, "tongues" of fresh water may
either an aquiclude or a water mass of to deep penetration of meteoric water extend many tens of kilometres sea-
G- different composition (Figure 4). A and attendant diagenesis. ward beneath the continental shelf in
r common situation today is one in which
the freshwater lens "floats", iceberg
Inthiszonewater, which fills the avail-
able pore spaces, is actively moving.
confined aquifers (Manheim, 1967;
Johnson, 1983).
C style, balancing on a column of denser Except in regions of relatively high ele- The Transition or Mixing Zone.
marine water beneath it. Early ob- vation, water movement in the lenticular The brackish water zone at the base of
C servers (DuCommun, 1828; Ghyben, zone is largely horizontal or subhorizon- the freshwater lens is of great geologic
1888-89; Herzberg, 1901, cited by Fet- tal (Figures 3 and 4) and directed toward as well as practical interest. It has been
C ter, 1980) noted in unconfined coastal the local baselevel of erosion which may suspected since the early 1970s that
C aquifers that the depth to which the
lenticular zone extends below sea level
be a spring, river or other inland water
body, or the ocean.
this zone may be a site where earlY
dolomitization take.s.place (see Morrow,
(
is about forty times the height of the If the aquifer is very permeable and this volume). Processes that occur in
o water table above sea level. This rela-
tionship is commonly called the Ghyben-
there is dynamic water movement in the
lenticular zone, the interface may be
the transition zone are still poorly un-
derstood, but its hydrologic and chemi-
C- Herzberg principle (e.g., Todd, 1980). deeper and displaced seaward toward cal characteristics are becoming better
The precise configuration of the lens is the coast compared to what would be known through studies such as those
O dependent also upon, amongst other predicted by the Ghyben-Herzberg rela- on which this brief discussion is largely
o things, the permeability of the rock and
rate of ground-water recharge (Bud-
tionship, because the marine water
beneath the lens is actively moving
based: Bear and Todd(1960); Back and
Hanshaw (1970); Back et al. (1976);
o demeir and Oberdorfer, 1986). Regard- rather than static, as assumed for the Vacher (1974); Plummer et al. (1976);

o SMALL SAND CAY OR OCEANIC ATOLL


Wigley and Plummer (1976); and Back
et al. (1979, 1984, 1986).
o In general, the transition zone is a

o product of physical and diffusive mix-


ing. It is thickest in more permeable
o strata where these mixing processes

~ mm;:-~2 ~~@»
are more effective, and also it isthickest
toward the coast because of both the

c '~; ~ .......
... :: :;:..;: :.:: : : : : : : : : :: : :: : " . _. . __ ._-- - - _.. -- ... - .. . ...... .
higher velocities of ground-water flow
near coastal discharge points and the
o .. .. ..
'

,
, • • I • ,
influx of seawater drawn shoreward and
upward in the shallow subsurface to
a LARGE CARBONATE PLATFORM replace the discharge.

o Salinity profiles in the transition zone


- as well as profiles of water velocity,
o concentrations of single and multiple
ion species and such water-dependent
o mass properties as electrical conduc-

o tivity - have the form of an s-shaped


curve (Figure 5). Because flow velocity
o and salinity are inversely related, pro-
files of the two essentially mirror one
o another; therefore, flow will be faster

o and waters more dilute in the upper part


of the transition zone. The importance
o TECTONICALLY UPLIFTED TERRANE of these relationships here is that both
conditions should have a bearing on
c whether carbonate will dissolve or
~~~ t precipitate.
It is important to be aware that,
c ~ although the transition zone is often
portrayed as being quite thin compared
to the freshwater zone above it, the
zone can be quite thick in permeable
carbonates of oceanic islands. Figure 5
illustrates the variations in transition
zone thickness that Vacher(1974) found
in the main freshwater lens on Ber-
Figure 4 A sketch showing different scales and configurations of freshwater lenses . muda, where the transition zone is
......
,'" ,
c
38 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
c
c
E c
W
c
~
WATER
-l
CD Page l Fm
et
I-
0:
\ (low permeab il i ty) c
Figure 5 A hydrological case study : map
of the water table and profiles of the transi-
UJ
I-
-c
~
\
\
c
tion (mixed-water brackish) zone in the main ~ 15
\
-,
!.-- <,'00% _ _
/ 1 ......
./ C
(Devonshire) lens on the main island of Ber- o -,

muda . (Mod ified from Vacher, 1974).


-l
UJ
CD 20L-
./ / 1 Belmont Fm .
---l.--....::........: --=-_--'
'(h igh permeab il ity)
C
:x:
l-
m
HYDROGEOLOGIC CROSS SECT ION C
ll. WITH RELATIVE SALINITY CONTOURS THRU
UJ
o TRANSITION ZONE C
TRANSITION ZONE
PROFILES IN 5 WELLS
C......
o 50 100
C
REL. SALINITY, %

C
C
IK m
C
V1lJ Pagel Fm C
March 1974 ' . , C
AVG . ELEVATION OF WATER TABLE C
C
C
C
C
C
C
® C~~~:'~N <. \~'t~~\
SIMPLE
,~,\~~~\~\
~,~~\\ ~ \;\~ \\:~\ \\\
;---7" PRECIPITATION
e-;
C
(j) CORROSION ~ ;X ~~ \ \ \~ \ \\
(C02 LOSS)
C
C
WATER TABLE ~~ ~ L..----'~
~ ~ DEGASSING
C
C
FRESH WATER
.s> E
.> MARINE
l_
WATER C
C
MIXED WATER C
Figure 6 A sketch illustrating the areas of dissolu tion (corrosion) and prec ipitat ion of carbonate dur ing the exposure of calc ite limestone to
C
percolating meteoric waters ; surface features are sketched in Figures 12 and 14, detail of square in Figure 21. (.

<---
(
t:
( Limestones - The Meteoric Diagenetic Environment 39

c
c often as thick as or thicker than the processes which are happening at rosion is the dissolution brought about
r freshwater lens itself (as defined by the
1% relative salinity contour) . To a close
once is much like learning to juggle:
having finally mastered the art of keep-
by rainfall on bare rock surfaces
(Figure 6).
o approximation the Ghyben-Herzberg ing three objects in the air, you are Biogenic corrosion. Air in the soil

c relationship, which assumes no mixing


of waters, would apply in effect to the
handed several more and told to put on a
good show!
zone has a significantly higher Pco 2
than the atmosphere because of plant
o part of the lens bounded by the 50% The reaction between carbonate
minerals and meteoric waters in general
respiration and decay of organic matter.

o relative salinity surface and the water


table (Vacher, 1978). is most simply expressed by the
As rainwater percolates through the
soil, addition of biogenic CO2 increases
o Deep Phreatic.
Water in the deeper phreat ic zone may
equation
CaC03 + H20 + CO2 = Ca2 + + 2HCO; .
the CO2 content , typ ically to an equiv-
alent PC0 2 of about 10 - 1.0 atm. Values
C~ be slowly moving or almost stagnant
The exact mechanisms of the CaC0 3 of 1-2% are common, but in some poorly
ground water, or in the case of young
ventilated tropical soils may be as high
\ exposed carbonate platforms or
- CO2 - H20 chemical system are com-
plex, involving a series of reversible and as 20-25% (PC0 2 = 1O- 0 .7 atm). Conse-
o islands, it may be seawater.
An important result of the dominance
mutually interdependent reactions, all quently, waters emerging from below
o of vertical, gravity-controlled seepage
proceeding at different rates and each
regulated by different equilibrium con-
the soil are very "aggressive " chemi-
cally and can rapidly dissolve orders of
o and flow in the vadose zone, compared
with horizontal water movement in the
straints. Recent reviews can be found in
Bathurst (1975), Plummer et al. (1979),
magnitude more.carbonate than could

o phreatic zone, is that large solution cav-


ities formed in the two zones have dif-
Bogli (1980), and Drever (1982).
ordinary rainwater.
Mixing corrosion. Runnels (1969)
o ferent elongation , commonly vertical in
Under natural conditions this equilib-
rium reaction is represented by (1) dis-
has emphasized that mixing of two solu-
tions which are both saturated with
c the vadose zone, but mostly horizontal
along and for a short distance below the
solution of carbonate, (2) oversatu- respect to a given mineral may lead to a

o water table. Caves that clearly have


formed in brackish-water transition
rat ion and (3) precipitation of new
carbonate. Diagenetic processes would
mixture which is either supersaturated
or undersaturated depending upon the
o zones have been documented along
be relatively simple if this reaction were
all that was involved, but dissolution and
character of the original solutions and
on the minerals in question . These non-
o the eastern Yucatan coast (Back et el.,
1979), a setting where one would expect
precipitation rates are often slowed linear relations can result in extensive

o them to be elongate parallel to the main


flow direction, as suggested in Figure 3.
down or halted altogether by kinetic fac-
tors. Kinetics are particularly important
subsurface limestone alteration .
Mixing of waters in the subsurface
o Where dissolution in the phreatic zone
in slowing down precipitation and thus
maintaining supersaturation.
can be expected to bea common pheno-
menon in all carbonate terranes. In the
o is strongly influenced by flow rates,
transition-zone caves may tend to be
Dissolution (Corrosion). simplest cases this may involve (1) mix-
o larger and more numerous toward the
coast where flow rates are particularly
Dissolution and precipitation of CaC0 3
are controlled in most natural situations
ing of different meteoric waters, (2) mix-
ing of meteoric and deeper subsurface
o high.
by the flux of CO2 in and out ofthe water.
Addition of CO2 by any means will drive
br ines, and (3) mix ing of meteoric

o Changes in base level due to tectonic


disturbances or world-wide sea level
the reaction to the right, resulting in
waters and seawater.
When carbonate ground waters are

o changes must inevitably shift the posi-


dissolution. The simplest way is to
increase pressure or decrease temper-
mixed, the resulting saturation state
depends upon (1) the PC0 2, (2) the tem-
o tions and spatial relationships between
the major hydrologic zones of the mete-
ature. Kinetic effects do not seem to be
significant. In the meteoric environ-
perature, (3) the ionic strength (salin-
o oric environment.
ment, dissolution (corrosion) is brought
ity), (4) the degree of calcite saturation,
and (5) the pH of the end member solu-
o DISSOLUTION AND PRECIPITATION
It is well kn that limestone d' -
about in several ways (Figure 6), some
of which are quite unexpected. The
tions prior to mixing.
Chemically, the simplest type of mix-
reader is referred to excellent treat-
...§pl\l en ex osed to fres ing occurs when two bodies of meteoric
ments of th is topic by Thrailkill (1968)
( Although the processes are easily water, isolated from contact with the
and Bogli (1980).
observed and the general theory is well atmosphere and each at equilibrium but
Simple corrosion. The amount of
G understood, some of the principles gov-
CO2 dissolved in water open to the air
with different CO 2 contents , come
erning the dissolution and precipitation together (Figure 6). The resulting mix-
depends upon the part ial pressure of
of carbonate are still poorly known. This ture will lie somewhere along the
c is because we must deal with a multi-
component system simultaneously
CO2 (PC0 2 ) in the air at the air/water
interface. Calcite is soluble to the extent
straight dashed line joining A and B in
Figure 7, depending upon the propor-
c involving all three natural phases -
gas, liquid and solid. An additional com-
of about 12 to 15 ppm in pure water
(depending upon the temperature).
tions of each.The composition will move
up and to the left until the saturation
plicating factor is that in perhaps the Rainwater, however, is in equilibrium line is reached, with dissolution occur-
with atmospheric CO2 , which averages
" more important case, the transforma-
tion of sediment into limestone, we must about 0.03% by volume (PC0 2 about
ring in the process. This has been called
"mixing corrosion " by many authors,
also deal with a suite of several different 10- 3 .5 atm) and so is in reality an but Wigley and Plummer (1976) prefer

I
minerals. Trying to understand all the extremely weak acid. Thus simple cor- to call it the PC0 2 effect, because

,-.
c
40 Diagenesis Geoscience Canada Reprint Series 4 c
c
there are other types of mixing corro- ventilated caves this is more than bal- tions . As might be expected, mixing of c
sion as outlined below. This process is
most effective when each of the waters
anced by precipitation from waters
supersaturated with respect to calcite.
waters with varying pH may also lead to
corrosionwith the degreeof undersatura-
c
mixed is saturated with respect to the When otherwise similarly saturated tion increasing with decreasing pH. c
calcite. If one of the waters is supersatu-
rated, then the effect is diminished or
solutions with differing ionic strengths
are mixed, appreciable undersaturation
Undersaturationcan also resultfrom a
decrease in Ca2 + concentration in sur-
c
negligible, as can be seen in Figure 7 by
joining waters of compositions A and C.
may result. In natural systems, because
waters of differing salinity generally
face streams during times of high flow,
which then descend to the water table by
c
In natural systems this mixing can be have unlike PC0 2 and pH values and are vadose flow and mix with ground water. c
envisaged as the mixing of high Pco 2 at different saturation states when Hydrostatic corrosion. As the (
vadose water with low Pco 2 phreatic mixed, the results may bequite variable; hydrostatic head increases in the phre-
water. The effect is much reduced, how- a spectrum of expected situations has atic zone, so pressure increases, and c
ever, if the vadose water is in equilib-
rium with a low PC0 2 (e.g., vadose
been synthesized by Plummer (1975).
Although the precise curves for any
thus fluids are able to dissolve more
carbonate . This process was thought by c
flow), the phreatic water is in equilib- given pair of variables are different, the many European karst workers to be at
least as important as mixing corrosion in
c
rium with a high PC0 2 (because of slow results follow the same general trend
(Figure 8), showing that as seawater the subsurface (Jakucs, 1977). c
degassing), or if the vadose seepage or
ground water is supersaturated with
mixes with carbonate-bearing ground
water the mixtures initially become
Oversaturation and Precipitation.
Under this topic we must consider two c
respect to calcite.
A similar corrosion effect may be
increasingly undersaturated with reactions: (1) a first-order reaction in
which precipitation occurs because of
c
achieved by mixing waters of different
temperature. This can occur when
respect to calcite. With continuing addi-
tion of seawater undersaturation Pco 2 variations in the meteoric water, c
vadose seepage is cooled at the water
decreases, so that mixtures containing
large amou nts of seawater are oversatu-
here called water-controlled precipita-
tion, andlor (2) a second-order reaction
c
table. If the system is closed to PC0 2,
then the effect is minimal; but if it is open
rated. Once in the field of oversatura- in which precipitation is brought about c
to Pco 2 , changes as small as 1°C can be
tlon, precipitation should result but is
generally inhibited kinetically by high
by differences in CaC0 3 mineral solu-
bility, here called mineral-controlled c
significant. In reality, however, in well- Mg2+, PO~- and SO~- concentra- precipitation. .
J'/ Q'v'" <v- c
)J 1 {I\","
.;,\\ J,/.fr[. v[v.
c
OVERSATURATION
I
/'VI I' /1''1 t-v(.I
w· c
20 c
>< 1.0 c
III
Q
z
0.8 Undiluted
Seawater~ c
z 0.6 OVERSATURATION c
oj: 0.4 c
e(
~ 0.2 /
Calcite-Saturated
Fresh Groundwater c
~
l-
e(
c
tn
w -0.2
c
I-
(j -0.4 · .
c
..J
-e
~.-.""'--'--'

-0.6 ::· :: :: :: ::: : :: :: :: :: : UNDERSATURATION ::.


c
(J
.· . . . . . . . . . . . . . . . . . . . . . . . . . .. c
-0.8
o 20 40 60 80 100 e
5 10 15 20 25 30 % SEA WATER IN MIXTURE L
4
EQUILBRIUM ~02(atm)X 1 0 C
Figure 7 A diagram illustrating the non-linear relationship
Figure 8 A generalized diagram based on families of curves from C
Yucatan, Bermuda and Florida illustrating the effect on calcite sat-
between equilibrium PC0 2 and dissolved CaC03- The mixing uration in groundwater by mixing waters of different ionic strength, in C
this case seawater and meteoric groundwater. The curve is a spec-
of waters such as A andB in any proportion will result in undersatura-
tion. The mixing of waters such as A and C will lead mostly to trum ofblends representing the mixing of seawater with a groundwa- C
oversaturation. (After Thrailkill, 1968). ter that is exactly saturated with respect to calcite.
C
C
C
(
( Limestones - The Meteoric Diagenetic Environment 41

c.
c Water-controlled precipitation.
Precipitation of calcite (low magnesium
dynamic drive is reached that is suffi-
cient to overcome the kinetic problem.
in relative terms, magnesium-calcite
components with more than 12 mole%
(
calc ite, i.e., calci te with less .~ As rates are commonly the main pro- MgC0 3 should be the most soluble and
o mole% MgC03 ) can occur only under blem given sufficient time precipitation so alter the most rapidly, followed by

c conditions of oversaturation. From the


earlier equatl ori it can be seen that one
will occur.
At our present level of understanding ,
aragonite and magnesium calcites with
about 12 mole% MgCOa and then mag-
( way in which this may be achieved is by it seems that the phreatic lens and tran- nesium calcites with less magnesium,
removing some CO2 from the system, sition zones in calcite-only systems are the least soluble phase of all being cal-
o most simply by heating the water,
decreasing the pressure, or evapora-
zones of dissolution, and if, cementa-
tion does take place there, the process
cite with virtually no magnesium . In
( addition, many of these components,
tion. Nearthe top ofthevadose zonethis by which it does so is poorly understood. because they are either biogenic or are
c. occurs by either evaporation or loss of
CO2, Assimilating plants also can take
An exception might occur near the
shoreline where CO2 evasion, induced
precipitated from seawater and have
variable microstructures, relatively high
( their CO2 from the water, causing pre- by tidal pumping, is important (Hanor, trace cation contents as well as organic

o cipitation. Vadose waters that are at


equilibrium with a high PC0 2 degas and
1978).
Mineral-controlled precipitation.
and fluid inclusions, are slightly more
soluble than pure minerals. In certain
o precipitate carbonate when emerging Aragonite, magnesium-calcite (HMC) situations grain-microstructural com-

o into a cave or the atmosphere with a


lower PC0 2'
and calcite (LMC) are the CaC0 3 miner-
als that make up most shallow-water
plex ity can override thermodynamic
restraints (Walter and Morse, 1985). In
o If the CO 2 content of the water carbonate sediments. The processes of
dissolution described above are equally
the Pleistocene Miami Oolite for, exam-
ple, aragonite ooids have dissolved but
o remains constant as in the phreatic
zone, for example, where it is isolated
from contact with the atmosphere, then
applicable to these minerals, but pre-
cipitation is another matter. Because we
magnesium-calcite foraminifera are
unchanged (Evansand Ginsburg, 1987).
theoretically the subsurface waters are now dealing with a group of minerals All of the CaC0 3 mineral transforma-
should be saturated with respect to cal- with differing solubilities, the main pro- tions take place by dissolution of one
cess is not one of calcite dissolution, but
o cite. But they should not be oversatu-
rated, because there are calcite nuclei instead (1) dissolution of the more sol-
uble phases (aragonite and magne-
mineral and precipitation of calcite.
What is important in this process is
that, unlike the simple calc ite-water
O· everywhere in the surrounding lime-
stone available for precipitation. In addi- sium-calcite), (2) resultant oversatura- interactions described previously, large
o tion, from the previous discussion of
dissolution it is clear that if two waters
tion with respect to calcite, and
(3) precipitation of new calcite.
amounts of water are not necessary.
Consider, for example, the aragonite-
saturated with respect to calcite are calcite reaction, which can be en-
o mixed, dissolution and not precipitat ion
will occur, and the same situation seems CaCO a ~
calcite
Ca 2 + + CO~-
visaged as occurring in a beaker of
fresh water (Figure 9-1) in which two
o to be true for seawater-freshwater aragonite carbonate minerals, a piece of arag-

o mixing .
Under natural conditions, however,
Mg-calcite onite and a piece of calcite, are immer-
sed. Immediately after immersion (Fig-
o ground waters are commonly super-
saturated. Once the waters are satu-
The important point here is that,
in this process, calcite is never dis-
ure 9-2) both the calcite and the
aragonite begin to dissolve until the
o rated, calcite will precipitate if it can, but solved because oversaturation is water is saturated. As noted in the ear-

o is often prevented from doing so by


various inhibiting factors. This aspect is
achieved and maintained by dissolution
of aragonite, and to a lesser degree by
lier section , this reaction is almost in-
stantaneous. However, since calcite
o poorly understood and several things,
such as kinetics of crystal growth, flux of
magnesium-calcite. In addition, this
process leads to a wholesale change in
is less soluble than aragonite, the water
becomes saturated with respect to cal-
o CO2 and inhibition by other ions, serve mineralogy, from metastable carbon- cite first, but is still undersaturated with
c to illustrate the problems . It is well
known, for example, that more energy is
ates to calcite.
Aragonite and magnesium-calcite
respect to aragonite, so the aragonite
continues to dissolve. But now (Figure
r. needed to grow a crystal than to dissolve are stable when bathed in warm sea- 9-3) the water is oversaturated with

c it, and so the rate of crystal growth is


slow relative to dissolution . Also, the
rate at which CO2 gas dissolves in water
waterbecause it was from this seawater,
with its high ionic strength , that they
respect to calcite, and as there is a
calcite crystal present, CaC0 3 will pre-
cipitate as calcite crystal cement. With
were precipitated. All three minerals,
is very fast, but the rate at which a solu- however, are soluble in fresh water, but this precipitation the solution is now
tion evolves CO2 to the atmosphere is to differing degrees. Specifically, the undersaturated with respect to arag-
very slow, and the rate of calcite growth solubility of magnesium-calcite pro- onite again, and so more aragonite dis-
is slower still. Finally, ions such as gress ively increases with increasing solves. Thus the process continues,
Mg2+, SO~ - and PO~ - are known to magnesium content, as the calcite lat- with aragonite continuing to dissolve
inhibit both dissolution and/or precipita- tice becomes more and more distorted . but never contributing enough CaC03
tion . If precipitation is prevented, then Aragonite is also more soluble than cal- to reach saturation because of continu-
the saturation state will continue to rise, cite and has the same solubility as mag- ing calcite precipitation. Eventually
with the solution becoming progres- nesium-calcite with about 12 mole% (Figure 9-4) all the aragonite is gone
sively oversaturated, until a thermo- MgC03(Walterand Morse, 1984).Thus, and the process stops, the final product
c
42 Diagenesis Geoscience Canada Reprint Series 4 c
(

being an original calcite crystal or grain throughoutthesystem isgone, and now, within grains, orcan be precipitated on a c
surrounded by newly precipitated cal- in a monomineralic all-calcite system, microscale inside a particle, replacing c
cite. This process, in which dissolution
is followed by precipitation of a second-
precipitation is localized and largely
water-controlled.
the original aragonite or magnesium
calcite. c
ary carbonate phase, is referred to by
some as incongruent dissolution (Turner
Kinetics also are important in this
system. Under natural conditions, if the
Styles of Diagenesis.
From the foregoing, it is clear that mete-
c
et al., 1986). freshwater diagenetic alteration of oric diagenesis is driven by two rock- c
Quite clearly the same reactions
could begin all over again if a new arag-
aragonite and magnesiumcalcite to cal-
cite were governed solely by equilib-
water reactions, one involving con-
gruent dissolution and generally water- c
onite crystal were introduced. The-
oretically, the same beaker of water
rium processes, then ground waters
would never be very oversaturated with
controlled alteration, and the other
incongruent dissolution which is min-
c
could be used to alter large amounts of respect to calcite, whereas in reality erai-controlled. Congruent dissolution c
aragonite and magnesium-calcite to
calcite. In reality, what would happen is
they are. Also, if the kinetics of the pro-
cesses were rapid relative to the age of
means that the entire solid dissolves
and generally no solid phase is precipi- c
that the ions from the aragonite and
magnesium-calcite that do not fit into
the ground waters, all water should be
in equilibrium with calcite, but it is not.
tated atthe site of dissolution.lncongru-
ent dissolution means that part of the
c
the new precipitated calcite, especially In most instances, the waters are over- solid dissolves to leave behind a solid c
Mg2+ and Sr2+, would become so con-
centrated in the water as to inhibit the
saturated with respect to calcite and
just undersaturated with respect to
phase different in composition from the
original, and the reaction is usually c
precipitation of calcite. In the intermedi- aragonite (Plummer et al., 1976). Thus accompanied by precipitation of a new c
ate stages, though, because of the ris-
ing trace-element concentration in the
non-equilibrium processes such as dis-
solution, precipitation and crystal
phase (Drever, 1982; Turner etaI., 1986).
The new phase maydiffer in crystal form c
water and selective absorption on the
calcite, these elements would be parti-
growth as well as the flux of CO2 in and
out of the ground water are again
from the original but havegenerally sim-
ilar composition, like dLMC compared c
tioned into the new calcite in small but important. For example, it has been with dissolved aragonite, or maydiffer in c;
ever-increasing amounts. An analo-
gous situation exists in nature. Waters
estimated that the rate of aragonite dis-
solution in "fresh" meteoric water is
composition but essentially not in crys-
tal form, like dLMC compared with pre- c
at the recharge end of a freshwater aqui-
fer have low trace element concentra-
100 times faster than the rate of calcite
precipitation (Schmalz, 1967). Thus it is
cursor HMC, or may have both new
crystal form and new composition,
c
tions, but by the time they reach the important to remember that waters in like dolomite compared with HMC or c
distal, discharge point, because they
have taken part in so many reactions
the meteoric environment, as long as
they are still in contact with metastable
aragonite.
c
along their path, they have relatively
high trace element concentrations. Cal-
carbonates, may be several times over-
saturated with respect to calcite, not
c
cites precipitated in the distal parts of because the nuclei are not there to pre- c
the aquifer will therefore have higher
trace element concentrations com-
cipitate on, but because the processes
are slow in the time frame of water c
pared to those precipitated in the proxi-
mal part (Kinsman, 1969).
movement.
In summary, the mineral-controlled
c
An important point that must be processes involve dissolution of arag- c
remembered in all of this is that once
the aragonite and magnesium-calcite
onite and magnesium-calcite and pre-
cipitation of calcite. This new calcite, c
have all dissolved to produce new cal-
cite, the process stops. The intrinsic
called diagenetic calcite (dLMC) by
some workers, can be precipitated in
c
driving force for calcite precipitation open voids ascement between grains or c
- DISSOLUTION & PRECIPITATION ~
c
c
c
~~ ~ r ~ r: ~ ~ r: (
Ca++
ca::, ca H
,
c
DH 0
2
fS r ++@
tIl Sr++ c
i8£HC0 3 O~HCO=
3 HCO= Figure 10 Modern hard laminated caliche C
3
(e) developed on the upper part of Pleisto-
(1) (2) (3) (4) cene reef limestone, Barbados. (Scale in
em). c
Figure 9 A sketch illustrating the simultaneous dissolution of aragonite and precipitation of
calcite in a beaker of distilled water.
C
l
C
(
(
Limestones - The Meteoric Diagenetic Environment 43
C
r:
In a suite of metastable minerals, the sediments are still aragonite and permeab ility, or the presence or
( either water-controlled alteration (con- high-magnesium calcite, provided that absence of fissures and cracks . Most
o gruent dissolution) or mineraI-control-
led alteration (incongruent dissolut ion
the flow of meteoric water is slow
enough that solubility differences can
changes will not be governed by the
fabric of the limestones and so will be
c and dLMC precipitation) may be opera- make the precipitation operative. The cross-cutting or "non-fabric selective",

o tive, depending mainly on the amount


and flow rate of meteor ic water through
alteration is mineral-controlled and
might in fact be viewed as incongruent
In the following sections , we first out-
line the processes of water-controlled
() the system . The difference between diagenesis. Diagenesis of this kind may (congruent) diagenesis because they
these processes is well illustrated in often be dominant in zones of relatively are applicable to virtually all carbonates
( the vadose zone. Water coming into slow diffuse flow. in relatively high-flow systems. Next,we
contact with metastable aragon ite Because the flux of water through the describe processes that occur during
( and high-magnesium calcite directly system is such a dominant control, it mineral-controlled (incongruent) dia-
c beneath the soil profile will dissolve all
species until it is saturated, but as this
seems quite possible that both mineral-
and water-controlled alteration (incon-
genesis because they appear to be
widespread in limestones containing
() solut ion percolates downward, altera- gruent and congruent diagenesis) take metastable suites of CaCOs minerals
o tion will occur because of differing min-
erai solubilities, not changes in Peo z'
place simultaneously and side by side
in some sequences. For example, in a
where there is relatively slow, diffuse
flow of meteoric water.
But if these waters should subsequently newly exposed sequence of little-ce-

c emerge into a cave open to the atmo-


sphere, then precipitation due to
mented aragonitic and high-magne-
sium calcite sediments , relatively slow-
moving diffuse flow may occur in most
PART 1 - WATER-CONTROLLED
METEORIC DIAGENESIS
The Rock-Air Interface.
degassing and not different solubilities
will take place. In contrast, if sediments places, fostering incongruent dissolu- The limestone surface in the meteoric
in the vadose zone are entirely calcite, tion and mineral-controlled alteration , environment , whether open to the air or

o then dissolution beneath the soil and


precipitation in the cave will still occur,
but higher volume channel flow may
develop locally along incipient joints or
beneath a soil cover, is the first carbon-
ate to come in contact with acidic
o but no mineralogical changes will take
place in the bulk of the vadose zone.
root molds, such that the dissolution
there is congruent and the diagenesis
waters. Limestone surfaces forming the
upper part of the zone of infiltration are
Congruent dissolution takes place in is water-controlled. usually altered intensively and develop
both situations, in response to flow- In mineral-controlled, incongruent features that are easily discerned in
through of water in large enough vol- diagenesis, because each kind of grain outcrops, cores and thin section and so
umes to prevent oversaturation for cal- is different mineralogically, dissolution are valuable indicators of subaerial
cite at the sites of dissolution. Water- and other forms of alteration will tend to exposure. Esteban and Klappa (1983)
controlled alteration under conditions of be " fabric selective" (Choquette and havesynthesized what was previously a

o this sort might be thought of as con-


gruent diagenesis .
Pray, 1970). In water-controlled, con-
gruent diagenesis, reactions and reac-
very diverse and widespread literature
concerning these structures, and much
o Still using the vadose zone as exam-
ple, incongruent dissolution and pre-
tion rates are governed by differences in
crystal size, grain size, amount of
of the following section is condensed
from their article. They concluded that
cipitation of dLMC will take place where adsorbed organic matter, porosity and there are really two end-member diage-

o netic facies here: (1) the caliche facies


and (2) the surface karst facies . These
c diagenetic facies are not mutually
exclusive: karst and caliche may co-
exist at anyone time and overlap in any
one area. Whereas karst can develop
under all climatic conditions, caliche is
attribu table to a generally semi-arid cli-

c matic reg imen . Before outlining the


attributes of these two facies, it should
be stressed that many subaerial
(
exposure surfaces may not contain any
l' diagenetic features, so the absence of
such features in the rock record does
not necessarily mean that the limestone
was never subaerially exposed.

CALICHE
Caliche (or calcrete or duricrust) is that
carbonate-Iithified port ion of the soil
I' ,
profile developed commonly, but not
exclusively, on carbonate sediments
Figure 11 Ancient caliche (C - between arrows) illustrating good alveolar texture , and rocks (Figures 10 and 11). Because
developed in the Carboniferous Newman Limestone, Kentucky. (Scale in em). caliches are accretionary and thus
c
44 Diagenesis Geoscience Canada Reprint Series 4 c
c
commonly preserved in the rock record, soil cover, there is a series of thin, com- replacement of roots by calcite in the
c
they have been intensively studied over monlyfriable,horizontaltosub-horizon- form of root molds, casts of tubules , c
the last twenty years.
Caliche zones range from centi-
tal plates or sheets which are separated
from one another but join and bifurcate
concretions or actual petrification -
are a diagnostic fabric of the caliche c
metres to metres in thickness and may
be complex in the extreme, with part of
laterally. This zone, which generally
grades down into nodular calcrete, may
profile. Roots both contribute to the for-
mation of platy calcrete and leadto brec-
c
the profile resulting from alteration of be several metres in thickness. ciation . This brecciation, which also c
the underlying limestone, part from
precipitation of new calcite and much
Caliche nodules (glaebules of soil ter-
minology) range from silt to pebble size
may be due to expansive crystallization ,
results in teepee and pseudo-anticline c
from a combination of both sets of pro-
cesses. Characterized by such features
and from spherical to irregular or cylin-
drical in shape, and may be isolated or
structures.
Included in many calcrete profiles are
c
as irregular, often laminated crusts, coalesced in arrangement. Thesestruc- black pebbles. The blackening may be c
rh izoconcretions, diagenetic peloids,
ooids and pisoids, breccias, clotted
tures, which are commonly concentric-
ally laminated, have been called caliche
due either to trapped organics within
crystals (Ward et al., 1970), metallic c
micritic and chalky carbonate, leached
and vuggy porosity and microborings
ooids, pseudo-ooids, oollths, peloids,
pellets, pelletoids, pisolites , coated par-
oxides precipitated on fungal hyphae
(Esteban and Klappa, 1983) or fires
c
and iron oxide, these horizons com- ticles, and, more recently, have been (Shinn and Lidz, 1988). c
monly stand out in a sedimentary se-
quence. Because their features are
included by Peryt (1983) under the term
vadoids.
Petrography. The petrographic
appearance of caliche is best described
c
similar to some formed in the marine Chalkycaliche is often well developed as messy. The wide variety of precipi- c
environment, however, they are often
overlooked (James, 1972; Read, 1976).
and may be up to one metre in thick-
ness, but is generally absent in areas
tates are reviewed by Chafetz et al.
(1985). Predominant fabric is a clotted c
Lithologies. As with other soils,
modern caliche is vertically zoned and
where the rocks have high initial poros-
ity. The white- to cream-coloured unce-
peloidal micrite with microspar-filled
channels and cracks. Grains and frag-
c
upward is composed of four rock types:
(1) massive chalky carbonate, (2) nodu-
mented carbonate is composed of silt-
sized calcite grains, commonly micro-
ments of limestone are separated from
thesurroundingmatrixbycircumgranu-
c
lar and crumbly carbonate, (3) irregular spar, with scattered nodules . lar cracks due to shrinkage and expan- (
plates and sheets, and (4) a compact
crust or hardpan. The position and
The transition zone down into the host
carbonate is characterized by strong evi-
sion . Fragments of original limestone ,
or individual grains if a relatively young
c
development of these lithologies in a dence of in-place alteration and replace- carbonate sediment, may be coated c
vertical sequence is highly variable
(Figure 12),but the massive chalky car-
ment of the original carbonate. Fossils,
for example, are often preserved but
with micrite laminations, which in turn
may be connected by thin laminations c
bonate most commonly is found at the
base, grading downward into underly-
embedded in calcified host material, or
coated with calcite laminations. If
bridging grains. A complete spectrum of
partly replaced (micrit ized) particles to
c
ing rocks or sediment. developed on bedded carbonate , altera- completely altered grains may be vis- c
The caliche hardpan, usually cream
to brown in colour, may range from 1 mm
tion takes place preferentially along bed-
ding and joint planes. This basal zone
ible. Replacement of some grains and
not others commonly results in a "float- c
to over a metre in thickness, is com-
posed of microcrystalline to crypto-
may be absent or metres in thickness.
Because roots may penetrate any of
ing texture" of particles in a micrite
matrix.
c
crystalline calcite, and ranges from the zones, rhizoconcretions - features Voids in the caliche profile often dis- C
structureless to horizontally laminated. formed by the precipitation around or play an alveolar texture (Figure 11),or a
E
Thicker hardpan generally is brecciated .. ~ o~
C
~?~Y
and exhibits dissolution and precipita- VARIATIONS
tion features, pisoids and rhizoconcre-
CALICHE C
tions. The upper surface ofthe hardpan
PROFILE l(}\tJ'
in semi-arid climates commonly is colo-
nized by lichens which may cause tex-
C
tural and fabric changes as deep as C
2 cm below the surface, producing
spongy, microscopic or micritic layers HARDPAN c
composed of organic-rich and organic-
poor mm laminations. Thus, the fabric
PLATES &
CRUSTS - - -
i e
of the hardpan may resemble that of a
~~~~~~~.
0

nm c
stromatolite and, in fact, Klappa (1979)
has called these structures "lichen stro-
LIMESTONE - - - ~ ! c
matolites". Criteria that can be used to OR - (
differentiate calcrete crusts from SEDIMENT
marine stromatolites have been out-
lined by Read (1976).
c
Beneath the hardpan or, if the hard-
(
Figure 12 Sketch of a caliche (calcrete) profile showing all the elements (left) and some of the
pan is not developed, directly beneath observed variations from various modern examples (right). c
c
c
r:
Limestones - The Meteoric Diagenetic Environment 45
r:

r:
network of anastomosing micrite walls zone and just above because there the cess beneath tropical soils, dissolution
100-150 JLm across inside cylindrical to sea spray supplies carbonate to the duetoother acids, such asfulvic,crenic,
irregular holes. Some open voids may crust , enabling precipitation to continue sulphuric and nitr ic, is also significant,
be floored with geopetal crystal silt at a more rapid rate; as would be but unlike the reactions associated with
(Dunham, 1969) which filters into cav- expected , the calcite there has a higher carbonic acid, many of these reactions
ities from the chalky zone . In other MgCOs content (James, 1972). In some are irreversible. The style of develop-
instances, the rock has a more vermicu- areas, such as the shoreline along the ment also depends a great deal on the
lar texture, or dense networks of micrite southern Persian Gulf where virtually porosity and permeability of the lime-
tubules and rods in a micr ite matrix the only source of water is sea spray, stone itself, with surface features
yielding a spaghetti-like texture. caliche crusts and pisolites develop but developed best on well-lithified lime-
In addition to micrite, needle fibres of are composed of Mg-calcite and arag- stones.
calcite a few microns to tens of microns onite (Scholle and Kinsman, 1974). Regardless, it is clear that climate is a
long are common . They may be a ran- In summary, the caliche zone is a major controlling factor in the develop-
domly oriented mesh (the " Iublinite" of diagenetic soil profile which involves ment of karst. Surface alteration at high

o
r:
soil science) and occur in voids within
the hardpan; they may form platy hori-
alteration of original limestone or sedi-
ment and precipitation of new carbon-
latitudes or altitudes is restricted to
slowly developed karst. In temperate or
zons or nodules; or they may be tangen- ate, both of which are modified or partly Mediterranean-type climates, karst and
tial with the needle-shaped crystals controlled by plants of various types. calcrete are common, but their develop-
o arranged in a band. This assemblage, which changes char- ment is seasonal. In general, deserts
Another distinctive caliche precipi- acter with time , is probably the most display poor karst and in semi-arid
tate is Microcodium or elongated to obscure and confusing of all diagenetic regions caliche is common. But, in re-
o petal-shaped calcite prisms or ellip-
soids or bell-shaped clusters which
zones.
Calcrete may be locally transitional
gions of high rainfall, karst forms a fan-
tastic array of towers, jagged ridges,
o Klappa (1978) proved to be calcified into terra fossa and similar soils (Gold- hogbacks, canyons and sinkholes
o mycorrhizae (soil fungi and cortical
cells of higher plant roots).
hammer and Elmore, 1984; Wright and
Wilson, 1987). Detailed geolog ical
which, together with extensive vegeta-
tion, make such regions pract ically
Variations. Depending upon the study ofthese featu res isjust beginning . impenetrable to surface travel and
length of exposure and climate, the cali- Ancient caliche. There are few well- poorly known.
che profile will change with time. Follow- documented examples of caliche in the Even though surface karst is most
o ing the development of weathered
detritus and a protosoil by the coloniza-
rock record (Estebanand Klappa, 1983),
and none from the Early Paleozoic.
intense in the humid tropics in areas of
substantial relief, in the past most car-
o tion by lower plants (lichen, fungi, algae, bonate platforms were exposed as vast

o bacteria), the caliche profile becomes


differentiated into two separate hori-
SURFACE KARST
Surface karst or exokarst, because it is a
flat plains. just above sea level with little
relief. Such a platform today in the Nul-
zons; water percolation and plant roots dissolution and not an accretionary larbor Plain in southern Australia (oneof

o generate the upper transition zone; pre-


cipitation of calcite forms the chalk
phenomenon , is difficult to recognize in
the rock record. In vertical section, it is
the world's largest karsts, ca. 100,000
km 2 ) which, because of the semi-arid
o zone. As accumulation of CaCOs con-
tinues, a point is reached where soil-
represented only by irregular bedding
contacts, and so only on well-exposed
climate, is heavily mantled with cal-
crete, exhibits minimal solution sculp-
or:
forming organisms can no longer main-
tain viability so that soil-forming pro-
bedding planes can the style be deter-
mined with any confidence. Paleokarst
ture and contains less than a score of
caves that reach to the water table and
....... cesses decrease and cementation and has only recently been recognized by relatively few shallow caves (Jennings,
r hardpan formation increase, fossilizing sedimentologists (James and Cho- 1971). Other level karst plateaus, such
the profile. Finally, the profile is so quette , 1988),although there is awealth as the Yucatan Peninsula (Stringfield
"'o"" Iithified that it is just another limestone of information about modern karst in the and LeGrand, 1974) or Bahama Banks,

o and the process begins again, a proto-


soil forms and plant roots penetrate the
geomorphological literature (Jennings,
1971; Sweeting , 1972; Jakucs, 1977;
because they are in a rainy climate,look
like Swiss cheese from the air,with innu-
o hardpan, leading to brecciation and
rhyzoconcretions.
Ritter, 1978).Karst occurs in all modern
climates, is the result of normal and
merable dolines or sinkholes (Figure
13). On the ground, the limestone is
...... Seminiuk and Searle (1985)differen- biogenic corrosion, and is slow under fluted or pitted by solution sculpture and
r tiate between vadose or rhizoconcre- arctic conditions but extremely rapid in dotted with small, solution basins (Bour-
tionary calcrete and ground-water cal- the tropics. The process of dissolution rouilh, 1974).
crete (massive, mottled, laminar) in the takes place both on bare rock and Surface karst features , from a practi-
zone of capillary rise just above the beneath soil, but generates somewhat cal standpoint, can be subdivided into
water table. different features under the two condi- small-scale solution sculpture or fea-
As with the other features described tions . Corrosion is especially active tures smaller than a metre in size which
in this article, there is a gradation from beneath soil and intensive in the humid can be seen in outcrop-size exposures,
the wholly meteoric formation of caliche tropics because of high temperature and large-scale features tens of metres
inland to a transition zone along the and increased vegetal litter and soil. to kilometres in size which, although
shoreline. It is common to find the hard- Although biogenic corrosion by car- sometimes seen in outcrop, are better
est crusts developed in the supratidal bonic acid is the most important pro- thought of as karst landforms.
(
46 Diagenesis Geoscience Canada Reprint Series 4 C
C
Solution Sculpture. These dis- Solution basins (kamenitza or faces (Figure 17). They can develop as
C
solution or corrosion features, devel- kamenica) are small, flat-bottomed rainwater collects in small depressions, (
oped either beneath a soil or on bare pans or basins often exhibiting over- beneath humus patches or in the inter-
rock, are generally called "karren" in hanging edges which characteristically tidal zone through the combined action
(
the English and German literature, or develop on horizontal limestone sur- of mixing corrosion and bioerosion. (
"Iapies" in the French and eastern
European literature. These features (
have a wide variety of shapes, and as
B6gli (1980, p. 53) succinctly states, C
" the multiplicity of possible karren
forms makes a morphological system
C
endless". Nevertheless, there are a C
number of common, recurring shapes
(
which are outlined below and dia-
grammed in Figure 14.As ageneral rule, (
the sculptures tend to be sharp and
jagged on exposed rock, but rounded if C
below a soil cover.
(a) Small karren: In temperate cli-
C
mates bare limestone surfaces are gen- (
erally smooth (although the larger-scale
sculptures may be sharp edged), but, in C
tropical climates or where there is rain-
splash and mist, the rock surface is
C
textured by tiny, slightly elongate , cup- C
like pits generally less than 3 cm in
diameter called "cockling", which inter- C
sect at knife-sharp edges and give the (
rock a crinkly or cindery appearance
(Figure 15). In tropical regions, a similar Figure 13 Areal photograph of large sinkholes, several hundred metres in diameter, (
texture of black-coated , jagged pinna- developed in Pleistocene limestone, Andros Island, TheBahamas, and now filled with water or
cles, marked by delicate, lacy dissec-
vegetation. (
tion, has been called "phytokarst" (Folk
SURFACE SOLUTION SCULPTURE (KARREN) (
et al., 1973) because of the intensive
activity of endolithic microflora in its (
formation. These smallest of features FLUTES GROOVES HEEL-PRINTS
can form very quickly, in as little as four C
years. They are especially characteris-
tic of limestones with good intergranular
C
porosity and are well developed in the C
intertidal and supratidal zones. (
(b) Medium-sized karren : These
slightly larger features on bare rock (
develop in the form of solution runnels
and solution pans. Two of the most dis- C
tinctive forms are solution flutes (
(rillenkarren) or razor-sharp finely chis- BASINS OR PANS CLiNTS & GRIKES ROOTS
elled runnels (Figure 16) and solution- (
grooves (rin nenkarren) or slightly larger
runnels with rounded furrows, both of
(
which develop on slopes of well-
cemented hard limestones. All of these -~- E
forms develop quickly and may reach C
lengths of metres in the tropics . These
may be straight on steep surfaces or
(
meandering on flattish surfaces. On (
more horizontal surfaces,hee/-printkar-
ren (frittenkarren), in the form of cres- C
centic steps, are more common. Figure 14 Sketches of different types of surface solution sculpture .
(
C
(
C
(
r:
Limestones - The Meteoric Diagenetic Environment 47
r

o
r-
/

(
( Figure 15 Syngenetic phytokarst charac-
terized by sharp irregular cockling and
o numerous irregular pores in Pleistocene

r. limestone, Andros Island, The Bahamas.


(Arrow points to hammer for scale).

o
o
c
o
o
o
o
o
o
o Figure 16 Ancient rillenkarst (Late Devo-
nian - Early Mississippian) developed on
o Ordovician limestone, western Newfound-
land (scale in em). The sculpted runnels are
o partially to completely filled with light grey

o Mississippian limestone.

o
o
o
o
o
o
o
o
r
,.

Figure 17 Modern solution pans (kame-


nitza), developed on Pleistocene lime-
stones, Bermuda and partially filled with
modern carbonate sand. (Scale bar in 2 cm
divisions).
c
48 Diagenesis Geoscience Canada Reprint Series 4 c
(

(c) Large karren: Once covered by soil cover or subsurface dissolution and lution or precipitation takes place. Con-
c
soil, increased corrosion tends to either gradual subsidence or collapse. sequently, this zone is relatively "inac- c
smooth all edges and points, remove
small karren forms and widen and
Breccias that fill collapse dolines are
characterized by mixed soils and
tive". Reaction does take place, how-
ever, if the limestone grains are extrem- c
deepen pre-existing features (Figure
18). The general term rundkarren is
speleothems together with the v-shape
of fallen overlying beds.
ely small and so reactive, or if mixing of
vadose seepage and vadose flow
c
applied to these features, which range The other large-scale features, such occurs, or if large cavities open to the c
from wavekarren or wavy surfaces like
corrugated tin in temperate climates to
as cenotes, cockpits, mogotes, uvalas,
karst valleys and poljes, are more in the
atmosphere are encountered, or if there
are changes in temperature. c
cavernous karren in the tropics. realm ~f geomorphology, and excellent Conversely (Figure 19), if the sedi- c
Forms that seem to develop best
under these conditions are clints and
summaries of these landscapes can be
found in general texts 'o n karst (e.g.,
ments are composed of a mixture of
aragonite, magnesium-calcite and cal- c
grikes (f1achkarren) or flat-topped
blocks (clints) bounded on all sides by
Jennings, 1971; Sweeting, 1972;
Jakucs, 1977; Bogli, 1980).
cite, each with a different solubility, then
this is a zone of intensive activity (see c
solution-widened joints (grikes) which part 2 of this discussion). c
are rectangular to diamond-shape in
plan. While most workers (e.g., Sweet-
SUBSURFACE KARST
Many characteristics of dissoiutional
Under conditions of vadose flow, the
system is effectively open to CO2 and c
ing, 1972; Bogli, 1980) think that these
develop beneath soil, Purdy (1974) sug-
cave systems in carbonate rocks are
discussed in detail by Ford (1988).
the aggressiveness of the waters after
initial dissolution is governed by the
c
gests that they may also develop on The Vadose Zone. diffusion rate of CO2 across the water- c
bare rock surfaces. At joint intersec-
tions, cylindrical pits several metres
The zone of inflitration is dominated by
processes of intensive physicochemi-
air interface. If the channels are large,
rapidly flowing water may be aggressive c
deep may be produced, which may
evolve into solution pipes or potholes.
cal and biological corrosion related to
intensive organic activity (Esteban and
to depths of 100 metres or so (Thrailkill,
-1968). Dissolution also occurs, when
c
As the grikes widen with time, the sur- Klappa, 1983)::Vertical.caves- are ' pro- - vadose seepage and vadose flow meet, c
face passes through a phase referred to
as kluftkarren to a stage of solution pin-
nounced .here. iand collapse breccias
may be common. Precipitates are usu-
by mixing corrosion.
Many caves found in the vadose c
nacles (spitzkarren) or assemblies of ally fine grained (moonmilk) and/or zone are due to dissolution at perched c
upward-pointing pyramidal or projec-
tile-shaped bodies of rock separated by
globulites (popcorn).
As the CO 2-rich acidic waters emerge
water tables or are relic water-table
caves abandoned when the water c
interconnected clefts or basins. While
these pinnacles may develop beneath
from below the soil they dissolve car-
bonate quickly, become saturated, and
level dropped. It is clear that some
caves, however, particularly those c
soil-cover inland, they also form on bare lose their aggressiven!3ss within a few strongly elongated vertically, form in the c
rock and on coastal carbonate rocks in
the intertidal zone and higher.
decimetres of. the soil -zone. Once the
waters -are saturated -in -an -all-calclte
vadose zone itself, either to survive
- unchanqed orto be modified by phreatic c
In addition to the soil, the roots of
plants and trees in the tropics etch tor-
carbonate host rock, no further disso- processes.
c
tuous single and branching chan nels in
the rock (hohlkarren) that may reach
c
depths of 25 metres. Locally, the chan- C
nels may criss-cross the limestone so
densely as to turn it into something
E
resembling a sponge, in places with C
more than 75% pore space. In four to
ten years, for example, a hairline crack C
can be turned into a rock channel of arm
or thigh thickness (Jennings, 1972). In
C
Pleistocene carbonates, the complex C
interrelationship between karst and
caliche is well demonstrated by com- c
mon pipes which owe their origin to root
corrosion but are lined by calcrete and
e
filled with rhyzoconcretions, formed by c
organically-induced precipitation.
Karst Landforms. The most wide- c
spread of these larger features are do- c
lines or sinkholes which may be funnel-
to bowl- to flat, dish-shaped structures, c
metres to kilometres in diameter and up
to 100 metres deep (Figure 13). They
Figure 18 Ancient ;undkarst developed on Ordovician limestone: the depressions are filled
by light grey Mississippian limestone (arrows), western Newfoundland. (Scale bar in 2 em
c
owe their origin to dissolution beneath a divisions). c
c
c
r:

Limestones - The Meteoric Diagenetic Environment 49

The Water Table. Dissolution. Most dissolution corrosion. It is here that many caves are
o
o
This realm, including the base of the
vadose zone, the water-table surface
occurs at or below the water table, in the
phreatic part of this realm .
formed. Phreatic water movement is
generally horizontal and the origin of the
and the upper part of the phreatic zone , (a) Processes: If the system is en- waters may be allochthonous, from out-
is one of intense chemical activity, per- tirely subterranean, closed to outside side the local area . Since the level of the

o haps more intense than anywhere else


in the shallow subsurface.
air, then this region where vadose and
phreatic waters mix is a level of intense
water table varies seasonally, the water
table may rise into the vadose zone

o METEORIC DIAGENESIS
during times of flood, resulting in a
whole zone of caves at this level.
o EFFECT OF (b) Features: There area wide variety
of dissolution features, such as pas-
ORIGINAL CARBONATE MINERALOGY

o
o
---I
CALCITE
Mg-CALCITE
ARAGONITE
CALCITE
sages, chan nels and shafts (Figure 20),
which can be related to both the type of
water flow and lithology (Bagli, 1980;
Ford, 1988). Smaller cave karren are
I
o w
NO EXTENSIVE
superimposed on the larger cavities.
The walls and ceilings may be smooth or
o
(I)
g
c
ALTERATION ALTERATION
wcN
pockmarked with corrosion pockets,
dimples and pits, or textured by rills and
>
grooves similar to surface karst and

t
DISSOLUTION & PRECIPITATION

o WCA WCA~
~~:r-<~~!(.::..-(-W-C-A-)-1WATER TABLE f---:(::-M-C--A"'-)--='!.4~.Yl~~
especially common where vadose
waters emerge. Pendants of relic lime-
o MINOR
DISSOLUTION
EXTENSIVE
DISS. & PRECIP.---r--,·
stone in the form of cones of rock may
hang down from the ceiling or protrude
o (
NON-FABRIC )
"SELECTIVE
( FABRIC & )
~~~cM~~C
up from the floor.
Scallops or crescentic, shell-shaped
: : ",::':".". dissolution features can form on the
"/=!-- DISSOLUTION DISSOLUTION
surface where a stream flows over lime-
(W C A) (W C A)
stone, but are particularly common in
o NO NO caves. The crests in these features lie

o ALTERATION ALTERATION transverse to flow and the steeper


slopes face downstream.
o Figure 19 A sketch illustrating the different diagenetic processes that affect a carbonate
Precipitation. Most precipitation,
but not all, takes place in the meteoric
composed 0.' calcite (sediment or limestone). versus one composed of a mixture of magne- part of this realm, in the upper parts of
sium-calcite. aragonite and calcite. Water-controlled diagenesis (WCA) is driven by evasion caves and cavities above the water table.
and Invasion of CO2 while mineral-controlled diagenesis (MCA) is driven by differences In (a) Processes: Regardless of the
o CaC03 mineral solubility. mineralogy of the sediment or rock, if
the system is ventilated with atmo-
o spheric air, the reverse occurs. High
Peo, vadose waters emerging at the top
of water-table caves equilibrate with
low-Peo, atmospheric air, degas and
o precipitate carbonate. Exactly the same
phenomenon occurs as springs emer-
o ging from a hillside precipitate traver-

o tine (Julia, 1983; Chafetz and Folk,


1984). Flowing waters in the cave are
also at equilibrium with atmospheric air,
and so precipitation only occurs be-
e cause of vanattons in temperature and
o turbulence.
It is a paradox that once caves are
open and can be visited by geOlogists,
the processes which formed them
largely have ceased, and they are in the
process of being decorated by various
precipitates (Thrailkill, 1976; Moore and
Sullivan, 1978).
Figure 20 Large dissolution cavities (ca . 1.5 m in diameter) excavated into Permian carbon-
ates, Carlsbad Caverns. New Mexico - note the lack of decoration.
c
50 Diagenesis Geoscience Canada Reprint Series 4 c
c
(b) Features: Subterranean precipi- growing surface. This two-stage process thought to form at the water surface c
tates can be subdivided into two types:
(1)calcareous tufa - soft porous rock to
leadstofrettedcrystal boundariesand not
to straight ones, as might be expected
because of CO2 diffusion into the air.
These may sink or may aggregate into
c
which plants contribute significantly,and from competitivegrowth of large crystals. small rafts. Cave pearls (concentrically c
(2) calcareous sinter (speleothems) -
nonporous, crystalline, hard limestone.
Those crystals in speleothems with para-
axialboundariesareinterpretedto bedue
laminated pisoids) form in pools of mov-
ing water or splash pools. c
The most common tufa is moonmilk, to precipitation during episodes of cave Plant life in caves has important geo- c
which is composed of microscopic car-
bonate crystallites or lublinite (random
flooding. The variety of fabrics are
reviewed and illustrated by Chafetz et a/.
logical implications. As caves lack light,
heterotrophic bacteria (including ac- c
needle crystals); although plastic and
containing from 35% to 75% water
(1985) and Gonzalez and Lohmann
(1988).
tinomycetes or mold-like filamentous
bacteria), algae and fungi as well as
c
when precipitated, upon drying it turns In addition to these deposits in the chemo-autotrophic bacteria are the c
into a powder. Plants playa significant
role in the precipitation by removing
vadose part of the cave, bars of sinter
called rimstone form on the cave floor,
most common forms . In addition to their
contribution to the formation of moon- c
CO2 from the water, and the resulting
crystallites are enmeshed in a net of
where water from a pool flows over an
obstruction as a thin film. When it flows
milk, these organisms result in the pre-
cipitation of other minerals. The black,
c
filaments from bacteria, actinomycetes over this rim, there is an increase in the sooty coating on cavewalls and pebbles c
and algae.
Sinter is precipitated either from thin
loss of CO2 and calcite is precipitated.
Most precipitation in pools or beneath
is a variety of manganese minerals
whose precipitation is aided by spe- c
films of water flowing over the rock or in
pools of water. Precipitation from water
the water table in the phreatic part ofthe
zone, however, is different. Because
cialized bacteria. On the other hand,
chemo-autotrophic iron bacteria, which
c
films results in crystals that grow out- there is no bounding surface, crystals obtain N2 from the air and carbon from c
ward from the rock surface for only a
short distance, with growth terminated
grow out into the water equally in all
directions as true crystals with scaleno-
iron carbonates, liberate ferrous iron,
which is oxidized to give a red colour to c
at the air-water interface (Figure 21). As hedral terminations (Figure 21). The cave sediments. ~
a result, the outer surface of the calcite largest crystals grow in the quietest The Lenticular Zone.
is smooth, with scalenohedral termina- water; the more the water flows, the Carbonate-water interaction in this c
tions never developing. This style of
precipitation is typical of the vadose
more numerous the calcite nuclei are
and the closer the calcite crystals stand,
shallow phreatic setting is poorly under-
stood because it is inaccessible, and
c
part of the cave, and forms flowstone and in rapidly moving water, rounded conclusions must be drawn from the- c
and dripstone (Figure 22).
Dripstone ranges from draperies to
surfaces like cauliflower, composed of
innumerable tiny crystals, can form.
oretical calculations and laboratory
experimentation (Plummer, 1975) and c
"soda-straws" to stalagmites and sta-
lactites to helectites. Deposition starts
The seed crystals for precipitation are data from wells (Back et a/., 1979).
c
from a drop of water on the ceiling, with c
precipitation beginning at the area of
attachment. Since CO2 is given off from c
the surface of the drop, precipitation
starts there, causing a ring of calcite.
c
Ring is added to ring to form a tubular
structure - the "soda straw". Water
flowing as a film over the exterior sur-
) c
c
SC~LLOPS
face of the soda straw deposits a second
. / c
type of calcite which constructs the
familiar conical or candle-shaped form . ) DRI~STONE c
This outer coating is most commonly
composed of elongate calcite crystals
HELECTITES 6 b c
which, in sections cut normal to the sta-
lactite long axis, have their long and
FLOWSTONE
----~..,;;;:~ / -.:.. 0 c
optic axes radially disposed. Some of
~

c
the growth surfaces are discernible by
bands which contain abundant impuri- CAVE e
ties. In an effort to reconcile the growth PEARLS (
of large crystals with a complex internal
fabric from a thin film of water, Kendall SCALLOPS c
and Broughton (1978)suggest that pre-
cipitation takes place initially from thin
COLLAPSE
BRECCIA c
water films in the form of tiny crystallites c
which grow syntaxially. The columnar
crystals form by a process of syntaxial Figure 21 A sketch illustrating the styles of precipitates (sinter) formed above and below the c
coalescence immediately behind the water table in a cave open to the atmosphere.
c
c
c
G
C Limestones - The Meteoric Diagenetic Environment 51
-,

r: Dissolution. There is a brackish SYNGENETIC KARST stone and is a distinctive trait of these
zone of mixing at the base of the fresh- The rock-air interface in metastable car- early caves. Once welliithified into cal-
r water lens. Theoretical calculations bonates is particularly susceptible to cite limestone, the full specturm of karst
and observations, especially near the alteration because of the generally features may develop.
r shoreline, from Yucatan (Back et al., porous nature of the sediments. The

c 1979, 1986; Hanshaw and Back, 1980)


and Bermuda (Palmer, 1984) indicate
that this mixing zone between fresh and
sediment surface hardens almost in-
stantaneously as a thin, millimetre-
thick crust of altered grains cemented
PALEOKARST
Numerous examples of ancient karst,
ranging in age from Precambrianto Cre-
(
marine waters is dominantly one of cor- by calcite. This grey crust also contains taceous, are documented in the compi-
c rosion and porosity formation. It is sig-
nificant to note that corrosion becomes
algae and fungi and develops within
months to years in quarries and new
lation by James and Choquette (1988).
Choquette and James (1988), recog-
C' more intensive when fresh and hyper- road cuts. The porous natureofthesedi- nize3typesof paleokarst: (1) depositional
,.' saline waters mix (Plummer, 1975). ments also aids in the rapid and deep paleokarst, formed at the top of metre-
Since the saturation state is dependent development of caliche, particularly in scale shallowing-upward sequences,
o upon so many factors, however, in some
areas of the Florida aquifer mixing does
semi-arid climates.
In spite of the often poorly consoli-
(2) local paleokarst, generatedwhenpart
of a carbonate shelf or platform is
not result in undersaturation. dated nature of metastable sediments exposed by local tectonism or small
In areas far removed from the effect of during early phases of meteoric diagen- drops in sea level, and (3) interregional
seawater, Jakucs (1977)has noted that esis, karst processes are ongoing. The paleokarst, related to major eustatic-
caves are common at the base of the products have been called syngenetic tectonic events and commonly defining

r lenticular zone (see Vernon, 1969, for


examples in the Florida aquifer) and has
karst (Jenn ings , 1971) because they
develop during lithification. Not all karst
sequence boundaries.
Since karst is a dissolution pheno-
ascribed their formation to hydrostatic features develop, however. Solution menon, a major problem is recognizing
corrosion, but some of this may be due sculpture is minor, except where cal- when dissolution occurred (Wright,
to mixing of fresh waters from the upper crete is exposed directly to rainwater. 1982), i.e. , whether the features ob-
phreat ic and more stagnant and saline Solution pipes are common, espec ially served were formed soon after deposi-
waters from the lower phreatic. those associated with roots, but the tion, or are the result of present pro-
Precipitation. There is consider- familiar solution features along joint cesses, or were formed at some un-
able confusion about calcite precipita- intersections are missing . Caves are known time. Particularly troublesome
tion in the lenticular zone. From the well developed, generally due to lateral is intrastratal or subjacent corrosion,
above, it appears that corrosion is the dissolution at the water table and minor which forms in the subsurface along
dominant process in calcite limestones . vertical dissolution. Because excava- lithologic boundaries and creates fea-
Hanor (1978) has proposed several pro- tion accompanies lithification and the tures that resemble surface karst and
cesses to promote degassing and so surrounding poorly lithified sediments could be mistaken for such. The surest
precipitation near the area of outflow, are inherently weak, roof collapse way of confirming that the feature is
but there does not seem to be much dominates more of their history than is fossil is to find skeletons or calcretes
suggestion of widespread prec ipitation . characteristic in consolidated lime- cemented onto, or borings penetrating
into, the paleosurface. Other criteria
that might be useful in certain casesare
suggested by Read and Grover (1977)
and Wright (1982). On a smaller scale,
there is a problem in the differentiation
of paleokarst surfaces and stylolites

o (Walkden, 1974).

o PART 2 - MINERAL-CONTROLLED
METEORIC DIAGENESIS
o This diagenesis can be seen going on
today or, at least, inferred to havetaken
place recently in Holocene and Pleis-
tocene carbonates in numerous warm,
r sunny places, and so is exceptionally
well documented. The reader is referred
to excellent recent reviews by Bathurst
(1980), Longman (1980) and Fliigel
(1982) for additional information .
The Process.
The commonstagesbywhich metastable
carbonatecomponentsalterto calciteare
Figure 22 Dripstone curtains about 1 m in length decorated by cave popcorn, Carlsbad now well known (Friedman, 1964; Land,
Caverns, New Mexico - arrows point to water droplets. 1967; Purdy, 1968; Matthews, 1974). Soon
c
52 Diagenesis Geoscience Canada Reprint Series 4 c
c
after meteoric waters begin percolating dence of a limestone in different parts of with either water or air or both,with water c
through a sediment , small elongate or the meteoric diagenetic environment. just wetting the grain surfaces. This, and c
equidimensional calcite crystals pre-
cipitate as cement on grain surfaces.
Many examples of these cements are
illustrated in Bricker (1971), Halley and
the fact thatvadosepercolationof wateris
not uniform, results in cements that typ- c
They grow equally on magnesium-cal-
cite or aragonite particles and earlier
Harris (1979), and Jones et a/. (1984);
their main attributes are outlined below.
ically show quite irregular distribution .
Inoutcrops or subsurface cores of Pleis-
c
submarine cements, giving the sedi- Vadose cements. These precipi- tocene limestones it is common to see c
ment some coherence . The next step,
which occurs as more cement is being
tates grow from void walls into poresthat
mayat different times be completelyfilled
relatively well cemented areas only
millimetres away from areas that are c
precipitated , is the start of alteration of
magnesium-calcite components to cal- SHALLOW DEEPER SHALLOW MIXED-WATER c
cite bydissolution of Mg-calcite and rep- VADOSE PHREATIC TRANSITION
I I
c
recipitation of calcite on a microscale I I c
(Turner et al. , 1986).By now, most parti- I I

cles are coated with a rind of calcite


cement which may constitute up to one-
CALCITE CEMENT IN MACROPORES
I I c
quarter of the rock volume. It is at this I
I
c
stage that aragonite alteration usually
begins, either dissolving to form molds c
or altering to calcite across an alteration
front with much textural preservation.
c
Dissolution of aragonite produces cop- en
zt-
c
ious quantities of CaCOa to be precipi-
tated locally as cement both inside and
c~
a:: CJ ARAGONITE I ."':".~.::f::L''....L.LCL.!.J.W-'~~. I c
between particles and in new holes cre-
CJ W (GRAINS & MARINE . .. .
~! :: CE~~~~)
CALCITE CEMENT IN MOLDS
»:'<'::'::- ':'.:.'.:'.:.':':..:.''.'-:. '::: c
ated by aragonite dissolution. By the
time all aragonite has gone , the sedi- a .'. .
_
~ I .. '
. , .:"
'. ' LOW-Mg CALCrtE (NEOMORPHIC) ' ' . '
Mg-CALCIT~ . . . I • • • • • . •
:"1'" .: : .-
: c
c
' . . . . . . . ." • • : • • • . • . '" .' .
ment has generally been transformed
into hard calc ite limestone (Figure 23).
~ CIll ~~I~~. ~ ~r'~.I~~ . ~!-~.'. :'.'.... '.: '.'.'.'.' .:.,:'.'.:..:'. :.'.1: . -:: . ' '. '. '.':
In this system, it seems that almost all - - - BURIAL-DIAGENETIC STAGE ----~ c
the cement needed for lithification can
be derived locally from aragonite dis- Figure 23 Idealized diagenetic evolution of an aragonite and magnesium-calcite sediment c
solution. So, in spite of wholesale fabric
rearrangement, there may be only
as it passes through meteoric diagenetic zones , in a terra in of low to moderate rainfall . Inferred
changes in the trans ition at the base of the lenticular zone are based on calcite saturation c
minor net loss of carbonate and just a relationships suggested in Figure Z
c
change in the style of porosity, from (", d\. -o o--.I-0v c
intergranular to moldic.
METEORIC CEMENTS ~~IQ.A,Jb"
Cementation.
By the term "cement" we mean here the
c
growth of precipitated calcite into origi-
VADOSE ZONE PHREATIC ZONE
c
c
~
nal pore space, either between grains
or inside grains, or into holes newly cre-
ated by the dissolution of aragonite.
Techniques for differentiating cement
c
from neomorphic or altered pre-existing c
precipitates are outlined by Bathurst
(1975, p. 416-439) and Dickson (1983).
MENISCUS ,
./)
VADOSE
ISOPACHOUS c
Among the more useful criteria, al- ~~ SILT c
~~
' ). r
though neither is foolproof, are (1)
increase in crystal size away from the
substrate and (2) development of sea-
lenohedral terminations directed away
EPITAXIAL
e
from the nucleation surface or sub- STALAGTITIC t .:'- . \ l
strate. Even these criteria are best
(
checked in fossil limestones by staining MICRITE
and cathodoluminescence for the pos-
sibility that the crystals are neomorphic
.. / ENVELOPE C
(e.g., Bathurst, 1983).
Vadose and phreatic cements gener- Figure 24 The different types of cement prec ipitated in the vadose (left) andphreatic (right)
ally have differing morphologies and so
(
parts of the meteoric diagenetic environment. Epitaxial cements on echinoderm particles may
can provide a useful guide to the resi- be precipitated in either zone.
C
C
C
(
(
Limestones - The Meteoric Diagenetic Environment 53
r

uncemented. Although some cements partly filled pores and so have men- if cementation is prolonged and pores
may be in layers of equal thickness iscus or pendant shapes (Figure 24). are filled, these characteristic shapes
around pore walls (precipitated when Crystals in these settings rarely have are usually lost. In our experience, epi-
the pores are filled with water), more good terminations (Figure 25). Men- taxial overgrowth cements also develop
commonly cements reflect growth out- iscus and pendant cements are excel- here, particularly on echinoderm grains
ward to capillary water-air interfaces of lent criteria for vadose precipitation, but and some benthic foraminifer tests. It
also seems that some early cements in
this zone become detached from pore
ceilings and fall to the bottom of the
pores forming geopetallayers of vadose
crystal silt (Dunham , 1969).
Phreatic cements. Pores in the
phreatic zone, unlike those in the
vadose, are always filled with water,and
so crystals can grow unimpeded except
by intercrystalline competition. Thus
cement rinds formed here, at least inthe
shallow lenticular phreatic, are either
well developed isopachouslayers of cal-
cite crystals around pore walls (Figure
24) or blocky calcite (Figure 26). As a
general rule, crystals are somewhat
larger than in the vadose zone and epi-
taxial growth on echinoderm particles is
more rapid. These cement morphol-
ogies are, unfortunately, not restricted
to this zone and form in deeper burial
and cold water marine settings. So
shape alone is not a reliable criterion.
Staining. A useful technique for dif-
ferentiating separate stages of cement
precipitation and determining cement
Figure 25 Pore-rounding cements, probably of vadose origin, in ooid grainstone. The morphologies is staining with an acid
arrows show location of meniscus-style cement borderingpartly filled interparticle pores. 5te .
solution of potassium ferricyanide,
Genevieve Formation, Bridgeport field, southeastern Illinois. (Width of photograph is 0.5 mm).
which imparts a blue stain to iron-rich
( calcites (Dickson, 1966; Lindholm and
Finkleman, 1972). Since the vadose
zone is an air-water system, conditions
there are generally oxidizing, so that
any iron is in the ferric state (Fe3 +) and
can not be incorporated into calcite. As a
result, vadose calcite cements are iron-
poor. On the other hand,phreatic waters
are often reducing, and so iron is in the
ferrous state (Fe2 +) and can be incorpo-
rated easily into the calcite lattice , with
the result that phreatic cements are
commonly slightly iron-rich. There are,
however, some caveats to this concept:
first, a source of iron must be present;
--. second, perched water tables are com-
mon in the vadose zone; third, not all
phreatic waters are reducing; and
fourth, many ferroan calcite (and dolo-
mite) cements form in the deep subsur-
face, below the lenticular zone. Conse-
quently, the interpretation of the stain
should be used with caution, remember-
Figure 26 Partially to completely dissolved ooids with some aragonite remaining which are ing that the lack of an iron-rich calcite
surrounded by medium crystalline phreatic calcite cement. (Photomicrograph, partially cement does not preclude the pos-
polarized light, is 2.5 mm across). sibility that it is phreatic in origin.
c
54 Diagenesis Geoscience Canada Reprint Series 4 c
c
Cement stratigraphy. Identifi- appears that even before the skeleton seawater contains negligible iron,
c
cation of stages of cement precipita- loses much MgC03 , calcite cement is grains with excellent fabric preserva- c
tion can be a powerful tool in ascertain-
ing the sequence of diagenetic environ-
precipitated into these small intragranu-
lar pores.
tion but composed of iron-rich calcites
must, at some stage, have altered in c
ments through which a limestone has
passed (Figure 27). In some areas,
A potentially useful technique for dif-
ferentiating between original magne-
contact with phreatic or deep subsur-
face waters. As calcite is stable and
c
such stages have been found to be sium-calcite and calcite components in should not alter, these iron-rich calcite c
systematically arranged and correla-
table over tens of kilometres through
the fossil record, since both display
excellent microstructure, has been sug-
grains must have been magnesium-eal-
cite originally.The converse, however,is c
tens of metres of limestones (Meyers,
1978; Meyers and Lohmann, 1984).
gested by Richter and FOchtbauer
(1978). Since calcite precipitated from
not true, as magnesium-calcite grains
altered in the vadose zone would also
c
This "cement stratigraphy" (Meyers, c
1974), also discussed in Choquette and
James, this volume, can be best
CEMENT STRATIGRAPHY c
unravelled by using a combination of
staining and cathodoluminescence.
c
Alteration of Magnesium-Calcite c
Components.
On the modern sea floor, particles and
c
cements are composed of micritic and c
fibrous magnesium-calcite crystallites
(Folk and Land, 1975). As outlined c
above, magnesium-calcite, because of
its generally greater solubility in dilute
c
waters, begins to alter to calcite before c
aragonite, very soon after percolating
waters have entered the sediment. c
Because the change does not involve
a modification of the original crystal ha-
c
bit, textural changes that accompany al-
1.
2.
MARINE
VADOSE
1. BEACHROCK
2. VADOSE
c
teration to calcite are invisible with the
light microscope (Figure 28). There is, 3. DEEP PHREATIC 3. DEEP BURIAL c
however, dissolution-reprecipitation,
and under the SEM it is clear that micro- Figure 27 A sketch illustrating t wo different examples of cement stratigraphy.
c
metre-size crystallites undergo slight c
enlargement (Towe and Hemleben,
1975; Oti and Muller, 1984). Regardless, c
the precise crystal orientation of crys-
tals is preserved, which is especially
c
evident in echinoderm tests . c
Skeletal magnesium-calcite is het-
erogeneous, divided into domains
c
having different levels of MgC0 3 c
(Moberly, 1970; Blake and Peacor, 1981;
Turner et et., 1986). Although the c
replacement process is not precisely
known, magnesium calcites do dissolve
c
incongruently, probably reflecting the (
greater solubility of the MgC03 phases
(Schroeder, 1969). Thus, it is probable c
that the MgC03-rich domains dissolve
first and calcite is simultaneously pre-
e
cipitated. Under the SEM the new cal- c
cite can be seen to have grown epi-
taxi ally on adjacent calcite surfaces, c
preserving the original crystallographic (
orientation (Benson and Matthews,
1971). Consequently, the resultant cal- Figure 28 Pleistocene limestone (Bermuda) in which the Mg-calc ite grains (Foramin ifera- C
cite component is partly original and left, lower right, centre) are now calcite while the mollusc (centre) is still aragonite: the
partly diagenetic. Most particles, how- isopachous cement rind is probably phreatic. (Photomicrograph, partially polarized light, is
l.
ever, are somewhat porous, and it 2.0 mm across). C
C
C
c
c Limestones - The Meteoric Diagenetic Environment 55
('
(
be iron-free calcite. In add ition, some and finally d issolves the crystals however,suggest that underdeep burial
o aragonites calcitize with considerable
iron incorporation (Sandberg and Hud-
altogether (James, 1974). This dissolu-
tion may begin at one point and expand
cond itions an d/or later fltiSfilng by
waters in ne~s.ur.fac.e-emlimen1s....-. -
C) son, 1983), but the replacement tex- outward or it may proceed from nu- some original low-magnesium calcite~
( tures are coarsely crystalline. merous starting points. may dissolve selectively, leaving molds
Alteration of Aragonite Components. From a geological viewpoint, it is the (Donath et al., 1980 ; James and Klappa,
( Aragonite is volumetrically more abun- way in which the subsequent calcite 1983; Sandberg, 1983). This may be due

c dant than magnesium-calcite in most


modern shallow-water, low-latitude car-
precipitation takes place that is impor-
tant (Sandberg, 1965), and two styles
to subtle differences in crystal size, con-
tained organicmatter ordomainsof unre-
( bonate sediments (e.g., most ooids, are common (Figure 29): placed calciteof low,but notlowest, mag-
gastropods, codiacean algae , dasyclad (1) Macroscale: In some cases the nesium content (e.g., 4-10 mole%).
( algae and corals are aragon ite). Particle whole component - grain, fossil or (2) Microscale: In other examples,
and cement habits range from micro- cement - dissolves away, leaving a dissolution of aragonite takes place
crystalline to platy to acicular to fibrous, hole that mayor may not be filled with simultaneously with precipitation of cal-
o though most modern marine cement
maybe acicular. Unlike magnesium-cal-
calcite cement (Figure 26). This is pro-
bablythe single most important process
cite on the opposite side of a water film
nannometres to micrometres in thick-
c cite, the change from aragonite to cal- creating small-scale porosity in the ness (Wardlaw et al., 1978), and the
o cite involves a wholesale crystallo-
graphic change from orthorhombic to
meteoric environment. The mold may
be filled quickly by cement in the mete-
basic structure of the original compo-
nent is partially retained (Figure 30) -
o hexagonal and the resultant process is oric zone or may remain open during that is, the resulting "calcitized " arag-

o one of complete dissolution of aragonite


and precipitation of calcite.
burial to be filled much later by deep
subsurface cements, brines or even
onite is generally a mosaic of calcite
crystals which cross-cut original fabric,
o Aragon ite dissolution is controlled
by the microfabric of the particle, skele-
hydrocarbons .
A note of caution! In our experience,
with the former structure outlined by
relics of organic matter and other insol-
ton or cement. It begins in areas with the magnesium-calcite grains in the mete- uble material (James, 1974; Pingitore,

o highest organic content or smallest


crystal size, then proceeds to etch
oric environment do not generally dis-
solve to form molds (but see Schroeder,
1976). This process generally is called
neomorphism. In some instances, re-
o along intercrystalline boundaries com-
monly yielding a "chalky" aragonite,
1979, for such an example). Recent
studies of pre-Pleistocene limestones,
placement is incomplete and tiny crys-
tallites of aragonite remain as relics
o entombed in the new calcite (Sandberg
et al., 1973; Sandberg and Hudson,
1983). Also, because of the fine scale
o and the microenvironment in which
alteration takes place, the concentra-
o tion ofSr2+ mayquickly rise inthis water

o film and so be partitioned back into the


new calcite in relatively large amounts
o /Jtr,~
JffY' 6' t vi"
(rarely, up to almost 1%; Davies, 1977).

o DISSOLVED
_0
""""~/p.um.e-
Because fine-scale replacement re-
suits in calcitized components that
o CALCITIZED clearly resemble their aragonitic pre-

~ ~
cursors, interpretation of original arag-
o onite mineralogy in ancient limestones

o STAYS OPEN FILLED PHREATIC VADOSE


is often difficult. Sandberg (1983) sug-
gests a range of criteria that may be
o i- -!- -!- -!-
used with increasing levels of confi-
dence to confirm original aragonite min-
o MOLD CEMENT-RLLED
MOLD
POOR
PRESERVATION
GOOD
PRESERVATION eralogy (Table 1).
It appears possible that this process
G may operate in slightly different ways in
8 the vadose and phreatic zones (Pingi-
tore , 1976). Aragonitic components
r
altered in the vadose zone tend to have
fabric-selective mosaics with relatively
MACROSCALE MlCROSCALE small crystal sizes, show excellent
ALTERATION ALTERATION replacement, and contain some organic
residue. The resulting calcites have a
Figure 29 A sketch illustrating the different ways in which an original aragonite skeleton may relatively low Mg2 + and high Sr2+ con-
be changed during meteoric diagenesis. If dissolved, a moldis formed which may later be filled tent. Aragonite components that have
by cement. If calcitized, some relics of shell structure (often including aragonite relics) remain changed in the phreatic zone reportedly
in the replacement calcite. The best preservation generally occurs in the vadose zone. show poor preservation in coarse,
c
56 Diagenesis Geoscience Canada Reprint Series 4 c
c
C
C
C
C
('

C
C
(

C
C
C
C
C
C
C
C
C
C
C
C
C
Figure 30 A Pleistocene gastropod in cross-section (Strombus gigas) wh ich is partially aragon ite andpartially altered to calcite (C); the lower C
part of the photograph is enlargedatthe leftillustrating excellentreplacement of aragonite (A) bycalcite (C) with the or iginal fabric now entombed
in new calcite as relic organ ic material and inclusions. C
C
C
C
Table 1 Aragonite Replacement Criteria C
1. PRESERVATION OF ARAGONITE
a. with aragonite relics
C
2. COARSE" CALCITE MOSAIC ,
b. no aragonite relics but ~ <-
IRREGULAR CROSS-CUTIING ::::i
STRUCTURE (AS SHOWN BY ORGANIC
high Sr ' iii
<: C
RELICS OR FLUID INCLUSIONS) { c. no aragonite relics, and
low Sr '
::::i
w
II: c
3. CEMENT-FILLED MOLDS
" relative to original aragonite
o
Z
u;
e
-c (
n.b. 2b, 2c and 3 are strengthened for cements if external morphology shows large ~
square-ended crystals. ~ \.
Criteria, in order of increasing reliability, for determining original aragonitic nature of C
calcitized components (after Sandberg, 1983). Although useful alone, they are best utilized
in conjunction with observations on the whole spectrum of preservation styles within a C
single limestone.

(
C
(
c
( Limestones - The Meteoric Diagenetic Environment 57

c
c cross-cutting mosaics and have rela- Importance of Grain Size. The importance of grain size or crys-
o tively high Mg2+ contents and low Sr2+ Most of the processes and products out- tal size is well illustrated in the common

o values. These differences are thought


to result from alteration across a film of
lined above have been worked out from
Pleistocene and Holocene calcarenites
phenomenon of micrite envelopes
(Bathurst, 1966;Alexandersson, 1972).

o water micrometres thick in the vadose


zone but across a chalky zone in the
because of their convenient grain size
and pore diameters. Likewise, grainy
On the sea floor, the outsides of carbon-
ate particles, such as bivalve shells,
phreatic zone. In the phreatic, because rocks should be looked at first in ancient commonly are bored byendolithic algae
the skeleton is surrounded by water, limestones to establish the general dia- whose vacated microborings are filled
( calcite continues to grow into a void, genetic sequence. When considering by microcrystalline aragonite or magne-
( whereas in the vadose zone the voids the full spectrum of carbonate sedi- sium-calcite cement, forming an "envel-
may be filled with air. These changes ments, however, it is clear that grain size ope" of finely crystalline carbonate.
o imply that alteration in the vadose zone
can be viewed as somewhat closed,
plays an important role. Mudstones, for
example, because of their small grain
When these grains come in contact with
meteoric waters the small crystals inthe
whereas phreatic calcitization takes size, alter much more rapidly than do envelope, because of their tiny size,
o place in a more open system.
This process is also viewed as oc-
contemporaneous calcarenites. Even
in calcarenites, the finer grained layers
alter quickly to calcite (more quickly if
magnesium-calcite than if aragonite),
curring in a "two-water system" are commonly cemented first, probably before the aragonite of the bivalve
(Pingitore, 1982), with (1) a small because the finer grained layers hold begins to dissolve. So for a time the
amount of slow-moving water at the dis- water longer by capillary action (Evans bivalve is still aragonite while the envel-
c solution- reprecipitation interface
which exchanges with (2) a large vol-
and Ginsburg, 1987).Such preferential
cementation of calcarenites is impor-
ope is calcite. Eventually the shell may
be leached away and only a thin micro-
ume of faster-moving water percolating tant because subsequent water move- crystalline rind is left outlining the
or flowing through the rock or sedi- ment is preferential through channels bivalve mold.This mold isthen filled with
ment. Water at the interface can be and voids around the cemented layers, calcite cement (Figure 24). If it were not
o considered an almost closed system leading to rapid porosity enhancement for the difference in grain size, miner-

o which is, in turn, connected by diffusion


to a large open reservoir.
The alteration of aragonite skeletons
and beginnings of karstification.
The alteration of polymineralic muds
in the meteoric environment is difficult
alogy, or relative resistance to dissolu-
tion (if both aragonite), and thus dif-
ferent alteration rates, all would have
to calcite also results in changed to study because oftheirsmall grain size been dissolved together and there
o petrophysical characteristics. In corals, and propensity for rapid alteration. would be no record of the presence of

c for example, calcitization leads to an


overall decrease in porosity, mainly
Recent studies utilizing SEM (Steinen,
1978,1982;Lasemi and Sandberg, 1984)
bivalve shells.
At the other end of the spectrum,
o because of precipitation of calcite
cement into pores, but an increase in
indicate that the same processes occur
as in calcarenites. Plio-Pleistocene
large whole aragonitic fossils (gastro-
pods, bivalves, corals) alter more slowly
C permeability because of changes in mudstones formed from aragonite-rich than sand-size aragonite particles, and
pore-aperture size (Pittman, 1974). muds are composed of both micrite and it is not uncommon to see partly altered
G Alteration of Calcite Components. microspar (sensu Folk, 1965) and corals surrounded by well-cemented,
o Biogenic components composed of cal-
cite, such as brachiopods, some
appear to be the end result of concur-
rent aragonite calcitization and pore-
but porous, calcite limestone containing
molds of smaller aragonite grains.
o bryozoans, planktonic foramininfers
and layers in some molluscs, appear to
filling cementation. The neomorphic
calcite exhibits aragonite pits and relics
Diagenesis in Vadose versus
Phreatic Settings.
remain unaltered under most meteoric on polished and etched surfaces and The style of and relative rates of sedi-.
o conditions. It should be remembered,
however, that these particles are not
the rocks have been called ADP (arag-
onite-dominated precursor) mudstones
ment alteration in the vadose and phre-
atic zones have been studied on rela-
o pure crystalline calcite, but are com- by Lasemi and Sandberg (1984). The tively large oceanic islands mantled

o posed of calcite, organic templates,


usually small crystallites, and numer-
cement regions are commonly com-
posed of several crystals in which each
by Pleistocene carbonates (Bermuda:
Land, 1970; Plummer et al., 1975;
c. ous micropores. Thus, they are more
soluble than the new diagenetic calcite.
continues into adjacent relic-rich neo-
morphic calcite as minute examples of
Jamaica: Land, 1973b; Barbados:
Steinen and Matthews, 1973). These
C. 0
So, once all aragonite and Mg-calcite "cross-cutting mosaics" observed by results can be used in a general way to
components have altered to calcite, the Pingitore (1976)in calcitized corals. This approximate conditions on larger car-
( limestone is composed of original cal- process transforms carbonate mud with bonate platforms. Studies on small
l cite particles and less soluble diage-
netic calcite components. A second
50% to 70%. porosity into mudstone
with commonly less than 5% porosity.
Holocene sand cays (e.g., Joulters
Cay: Halley and Harris, 1979) probably
(
stage of alteration, affecting only these These mudstones contrast with better reflect conditions of ephemeral
original calcite elements may then take COP (calcite-dominated precursor) exposure of small portions of plat-
place in deeper parts of the meteoric mudstones, which are mostly micrite forms. Two examples of vadose versus
environment (AI-Aasam and Veizer, composed of crystals with no relics or phreatic alteration are outlined in Fig-
1986a, b) or in the burial setting (Cho- pits, and are from more ancient ures 31 and 32.
quette and James, this volume). limestones.
c
58 Diagenesis Geoscience Canada Reprint Series 4 c
c
Suspicion that sediments continu- different, then mixing is likely to result little vadose flow, only seepage. Al-
c
ously in contact with meteoric waters in in dissolution, as in a wholly calcite though sediments are only in the ini- c
the phreatic zone alter more quickly
than those in the vadose zone, where
system.
Meteoric diagenesis on small islands
tial stages of alteration, several trends
are nonetheless evident. The main c
water flow is ephemeral, is borne out by
studies on the larger islands. Waters in
or sand cays with only local aquifers
appears somewhat different. Diagene-
point is that on small islands the rates of
diagenesis above and below the water
c
these large phreatic lenses not only per- sis throughout is very rapid in the best table do not appear to be much different . (
colate down from the vadose zone, but
also arrive at the water table directly
studied example, Joulters Cay (Halley
and Harris, 1979), but this may be due
In both cementation is patchy, but oolite
is more friable below the water table c
from lakes, swamps, rivers, and via
vadose flow through fissures. Because
partly to the high aragonite content of
the sediments (almost all ooids). An
than above because precipitated calcite
is a true "cement" in the vadose zone,
c
the phreatic waters are from different
sources, their chemistries and mineral
important difference from large islands
is that all the waters pass downward
forming an "onion skin" on the grains
and concentrating as a meniscus at
c
(
saturations show considerable tem- through the vadose zone before they grain contacts . In contrast, calcite in
poral variation. In some areas, it is reach the water table and there is the phreatic zone is precipitated as c
estimated that the bulk of the water in
the phreatic lens is not from vadose PETROGRAPHY GEOCHEMISTRY c
seepage but from vadose flow or lakes,
rivers and bogs. Thus, the phreatic
CAUCHE MARINE c
waters should be of different composi- 0/00
LEVELS
o + c
tion than the overlying vadose waters
and, because of mixing, the water table c
should be a level of considerable chemi-
cal activity.
c
Mg++-I I c
I:
Sediments composed of metastable
carbonates seem to alter rapidly in the
phreatic zone. Those areas studied to VADOSE c
date display both cementation and dis-
solution that result in extensive lithifica-
Sr+++--
I I
c
tion and in abundant aragonitic fossil
I I c
molds as well as calcitized skeletons.
There is no clear information about
I c
where in the phreatic zone grains alter
most quickly or in what manner, or I I c
whether all parts are affected equally. I I c
However, Longman (1980) has outlined a
hypothetical sequence of alteration for I I c
this zone, which remains to be tested.
PHREATIC
I I c
In any case , because of these dif-
ferences a common situation in Pleis- I I c
tocene carbonates is for sediments in
the vadose zone to be poorly lithified
I I c
and still mainly metastable, while the
same sediments in the phreatic zone
c
are calcite limestone, with a striking
MARINE
c
mineralogical discontinuity developed
at or near the water table.
c
It is not clear whether dissolution or c
precipitation will prevail in the phreatic
zone during these early stages of dia-
Figure 31 A sketch illustrating a hypothetical core through an ooid grainstone shoal
exposed to meteoric diagenesis under semi-arid conditions, resulting in a caliche profile.
c
genesis because the processes depend
upon so many factors. If, for example,
Sediments below the mixing zone are saturated with marine pore waters and essentially
uncemented. The geochemical curves are based on results one might obtain from "bulk"
e
vadose waters several times oversatu- analyses. The limestone was originally composed of aragonite ooids, hence the high initial
Sr2+ and low Mg2+ concentrations. Stabilization is essentially complete in the freshwater
c
rated with respect to calcite because of
abundant dissolution of aragonite are phreatic zone.
(
A Pa/eoexposure Surface - caliche crust, partial conversion of ooids to calcite micrite,
mixed with phreatic waters that are just
saturated with respect to calcite, and needle and other calcite cements, gravity effects, vadoids. C
PC0 2 levels in the waters are not too
B Vadose zone - conversion of ooids to calcite with mostly good preservation, meniscus and
gravity calcite cements.
l
different, then cementation can occur at
least adjacent to the water table . If, on
C Freshwater Phreatic Zone - extensive dissolution (fabric selective). calcitization, iso-
pachous calcite cement.
l
the other hand, PC0 2 levels are very o Mixing Zone - preservation of aragonite ooids, poor induration, some rhombs of low to C
high magensium-calcite.
C
C
c
c Limestones - The Meteoric Diagenetic Environment 59
c
c
o scattered rhombs all over the grain sur-
faces and not necessarily at grain con-
tacts . The most intensively cemented
sand cay, whereas stabilization will pro-
bably take some 100,000 to 1,000 ,000
years on Bermuda and along the coast-
Cementat ion of limestones by CaC03
in mixing zones may not be extensive. In
very young Holocene sediments (ca.
(J zone is right at the water table . Cemen- line of South Australia (Reeckmann and 1,000 years old) beneath south Joulters
( tation decreases with depth in the phre- Gill, 1981). Cay on Northeastern Great Bahama
atic zone as the proportion of seawater The Freshwater-Seawater Mixing Zone. Bank, for example, there is virtually no
( increases. The possibil ity that dolomite may form cementation at all below the freshwater
( Interestingly,calculations suggest that in miXing zones has provoked consider- phreatic lens. Minor amounts of low-Mg
at the currentrate all the sediment will be able interest in the hydrology, chemistry calcite cement have been found in
( stabilized 16 calcite within 10,000 to and mineralogy of such zones (see Mor- paleo-mixing zones on Barbados (Ben-
20,000 ye~rs on this small carbonate row, th is volume) . son, 1973; Steinen, 1974), northern
( Jamaica (Land, 1973a, b), and a coastal
( area of Grand Cayman Island (Moore,
PETROGRAPHY GEOCHEMISTRY 1973). Coastal mixing zones are, in a
o sense, involved in the formation of

o MARINE
LEVELS
beachrock (discussion in James and
Choquette , this volume), but CO 2
o o + degassing in these zones, rather than

o ® /
/
/
mixing effects , may be mainly respon-
sible for CaC0 3 cements there (Hanor,
o S
/
I 1978).
There is considerable evidence that
o Mg++ ,
~I
I dissolution is important in mixing zones.
Non-fabric selective dissolution occurs
0_ VADOSE /: I along some 150kilometres of the north-
o "" I I
eastern Yucatan coast, apparently in a
coastal mixing zone (Back at al., 1978,
o l{}.1J I ~ h?-f ~ I
I/v e:r Id--v I /
1979, 1984), producing a striking scal-
loped morphology and related collapse
(
(-1- features (Figure 33). Mixing corrosion

: I
I I
PHREATIC I I

o : I
I I

MARINE

o
Figure 32 A sketch illustrating a hypothetical core through a reef limestone exposed to
meteoric diagenesis in a warm , moderately humid climate . Subaerial exposure produced a
corroded fractured surface karst. Sediments below the mixing zone are saturated with marine
l pore waters. The geochemical curves are based on results one might obtain from "bulk "
analyses . The limestone was originally composed of coralline algae (A, magnesium-calcite),
l bivalves and corals (8 and C, aragonite). Stabilization is mostly complete in the freshwater
phreatic and the offset of the 5' 3C profile at the water table is due mostly to precipitation of
diagenetic calcite cement. Figure 33 An oblique areal photograph of
A Pa/eoexposure Surface - dissolution and fracturing, geopetal vadose sediments, good the coastline at Caleta XelHa, Quintana Roo,
skeletal preservation. Yucatan Peninsula Mexico. The irregular
B Vadose Zone - mostly good preservation though skeletal aragonite is calc itized, minor coastline is the result of dissolution of Pleis-
development of molds and matrix vugs. tocene limestone along joints by brackish
C Freshwater Phreatic Zone - extensive dissolution , prolonged flushing, non-fabr ic selec- groundwaters which are undersaturated
tive voids, some calc itization and calc ite cement precipitation (black = porosity) . because of mixing fresh water and seawater.
D Mixing Zone - not exposed to meteoric waters, aragonitic fossils may be calcitized, The waters come to the surface in this
magnesium content of coralline algae high in lower part, dissolution likely in upper part (dilute locality at the irregular area about 200 m
pore waters). across marked by the arrow.
(

60 Diagenesis Geoscience Canada Reprint Series 4 C


C
on a large scale has probably occurred and geographic extent have been docu- 17). ThislossinSr2+ and Mg2+ is appar-
C
along the base of the vast freshwater mented in some widespread conti- ently reversed with passagethrough the C
lens in parts of the south Florida aquifer nental-coastal aquifers (e.g., the South mixing zone (Wagner, 1983) , which
(Vernon , 1969), and distributions of Florida aquifer: Back and Hanshaw, appear to be particularly well defined by C
caves in limestones beneath large downward increases in Mg2+ content.
oceanic islands, such as Bermuda, sug-
1970).
The curve in Figure 8, illustrating the Below the water table, beyond the
C
gest that brackish waters may have had effect of mixing fresh and seawater, is reach of oxygenated water, metals that C
a part in their origin (Palmer, 1984) . plotted for calcite only. Other minerals can exist in lower oxidation states such
Where CO 2 is not a major factor show the same effect, but have different asMn 2+ andF&+ become available for C
and fresh water and seawater mix saturation indices. Thus, there is a por- incorporation into diagenetic calcite (
according to the error function relation- tion of the curve (or percentage of sea- (C02+ and Ni2+ also may playa role
ship described earlier, it seems likely water in the mix) where waters are satu- here) , result ing in an overall net C
that dissolution is favoured in the rated or oversaturated with respect to increase in these elements with pro-
upper, more dilute reaches of the mix- calcite, yet undersaturated with respect gressive burial Meyers and Lohmann C
ing zone (see Figure 3), as might be
expected from Figure 8, and that
to aragonite - a situation which would
lead to aragonite alteration. Along parts
(1984).
The level of cathodoluminescence
C
CaCOa precipitation (and dolomite for- of the Yucatan coast, for example, the (Cl) varies sharply among growth C
mation?), if significant, should take critical mixture appears to be between zones in crystals of carbonate cement
place in the lower reaches of this zone. 50% and 60% seawater (Back et aI., (see Machel, 1985, for detailed discus-
C
Where calcite is the cement precipi- 1986). sion). As illustrated in Figure 34 , vadose C
tated, in metastable limestones it might It is likely that the rock record will be cements show little or no Cl because
be expected to become more Mg-rich found to contain more examples of dia- vadose waters normally are well oxyge- C
downward in the mixing zone. This Mg- genesis and cement stratigraphies nated, so that neither Fe2+ or Mn2+
rich fingerprint should not be preserved imprinted by local and regional mixing exist. Below the water table oxygena-
C
long or deeply into the sublenticular zones. tion and Eh decrease rapidly, so in the C
phreatic realm, however, unless by such shallow lenticular phreatic zone Cl is
features as microdolomite inclusions GEOCHEMICAL ASPECTS OF both present and highly variable, but is C
(Meyers and Lohmann, 1978). It is
attractive to interpret as products of mix-
METEORIC DIAGENESIS
Minor Elements. Dissolution of arag-
essentially nil (dark) in the deeper phre-
atic zone. Variability can best be
C
ing-zone precipitation those calcite onite (at whatever scale from micro to attributed to fluctuations in supply of C
cements which have these inclusions, macro) releases strontium (Sr2+) and activator ions (mainly Mn2+) and sup-
are clearly not synsedimentary marine other less abundant trace cations to the pressor ions (mainly F& +) and to varia- C
in origin , and are spatially associated
with identifiable phreatic cements.
surrounding pore waters ; incongruent
disssolution of Mg-calcite releases
tions in water flux in response to either
seasonal or longer cycles; these fluctu-
C
Meyers and Lohmann (1984) argue per- Mg2+ . The result in the carbonates is a ations are greatest in near-surface C
suasively for precipitation of these in- net decrease in both Sr2+ and Mg2+ hydrologic regimes, particularly, the
clusion-rich cements from regionally either with accompanying passage vadose. Phreatic-zone Cl, first identi- C
extensive transition zones, and it is true
that modern brackish mixed-water
through the vadose and freshwater
phreaticzones, or during continued res-
fied by Meyers (1974) in a landmark
study, has since been described in
C
zones with comparable distributions idence in either zone (Figures 16 and many parts of the Phanerozoic (e.g.,
E
l
C
C
C
c
e
(
(
C
Figure 34 (Left) two stages of cementation in an Early Cambrian grainstone: V, vadose pendulous cement; P, phreatic blocky calcite (plane
(
polarized light).
(Right) cathodoluminescence, vadose cement has irregular trace element content, phreatic cement is two-staged; p,.dark and bright \-
luminescent zones, probably shallow phreatic; P 2 , dull luminescence, probably deep phreatic. (Photo width is 5 mm).
C
C
C
c
c Limestones - The Meteoric Diagenetic Environment 61

C'
c. Grover and Read, 1983; James and Although the tempo of research on and oxygen isotopes within the near-
o Klappa, 1983 ; Meyers and Lohmann,
1984). Cathodoluminescence is a
minor elements in carbonate diagene-
sis is increasing (see discussions by
surface meteoric. At present, our knowl-
edge of carbonate-ion isotopic com-
o powerful tool for deciphering of ten-
complex cementation histories, par-
Brand and Veizer, 1980 ; and Lohmann,
1983, 1988), our understanding of the
positions diminishes with increasing
depth below subaerial exposure sur-
( ticularly where CL zones can be cali- behav iour of these elements even in the faces, even in Holocene and Pleisto-
c brated with minor-cation compositional
data . Mussman et al. (1988), for exam-
near-surface meteoric environment is
still fragmentary and evolving . In gen-
cene carbonates. The profiles in Fig-
ures 31 and 32 typify fairly well the kinds
( ple, have utilized these techniques to eral terms, however, the profiles in Fig- of stratigraphic distributions of carbon-

c interpret the depth to which meteroic


fluids were important diagenetic agents
ures 31 and 32 appear to be reasonable.
Stable Isotopes.
ate 51 3C and 51 80 in young Pleistocene
sequences. In these profiles, the pat-
c below the Middle Ordovician, post- Considerably more is understood about terns are emphasized rather than abso-

c Knox interregional unconformity in the


Appalachians.
the distribution and diagenetic "behav-
iour" in carbonates of stable carbon
lute values, and it is clear that with varia-
tions in absolute composition these
patterns are valid for many, if not most,
+6 limestones SUbjected to near-surface
c AVG 0 0 OF I
18 meteoric diagenesis at least as far back

o CALC ITE PPT'D


IN OPEN METEORIC' ®
in geologic time as Late Paleozoic. The
profiles are based on a series of recent
o +4 PORE-WATER SYST I INCREASING
METEORIC EFFECTS
studies (e.g., Magaritz, 1975, 1983;
Allan and Matthews, 1977, 1982;
o Q If MARINE Salomons et ei. , 1978; Videtich and Mat-
+2
AVG"O I3C - t;~-,I4ilIjj_~~, SEDIMENTS thews, 1980; Wagner, 1983). The gen-
eral subject of 51 3C and 5180 isotopic
MARINE SEDS
o ~w
z~
compositions and isotope geochemis-
try has been ably summarized by others
o o w~
::Eo::
(e.g., Bathurst, 1975; Hudson, 1977;
Veizer, 1983) and a lucid view of princi-
OW ~~
w~
-2 <
~~
~I
ss s
~-~
~~CJ
~ ,14J ples is provided by Lohmann (1983,
1988).
With sound petrographic work, it
(J)~ s s» is possible to interpret isotopic signa-

©
~g <---~
-4 C
c>z
0::
~
,..g/B
,..
tures of meteoric diagenesis with a
high degree of accuracy, provided
z- '<C otJ l4J
-W iil4J~ that one can get an estimate of the origi-
(J)u ~o nal marine 513 C and 5180 of a limestone
<z §iil4J
-6 Ww o'<CC) or limestone sequence prior to altera-
0:::;) o~~
u....J ~'<C tion. This can be done, as numerous
~u. OCJ~ studies (e.g., Lohmann , 1984; Given
Z , .........1.1'1
-8 and Lohmann, 1985) have convincingly
demonstrated, by taking the "heaviest"
PLEISTOCENE composit ions in a linear, covariant
COMPOSITIONS CALCITE PRECIPITATED series of values determ ined for those
-10 @ BARBADOS IN CALCITE & SOIL marine components that show the least
evidence of alteration. Such compo-
@ BERMUDA PROFILES
nents might be well-preserved brachi-
-12 opods (calcite originally) or marine radi-
-10 -8 o +4 axial cement, or originally aragonitic
rudists in which critera from Table 1 in-
l dicate good preservation following
Sandberg (1983). The covariant trend
Figure 35 A diagram showing isotopic compositions and trends in metastable carbonates approach, illustrated in Figure 35, has
where mineraJ-controlled alteration takes place in a meteoric system capped by a caliche-soil been used by Lohmann (1983) and
profile. The covariant trend (A) has as end member marine sediments (seawater) and 13C_ others to estimate orig inal marine
enrichedpore waters; diagenetic calcites precipitatedin a marine-meteoric mixing zone might
CaC0 3 compositions with apparent
have compositions along such a trend. If no caliche-soil profile existed, alteration of marine
accuracy. These graphs were presented
sediments might follow the trend shown by the top arrow gently down to the left (B). The long
vertical trend (C) would apply to rock-water interaction beneath a caliche-soil profile in the in the first of this servies of re views (see
shallow vadose, where 613C becomes heavier downward as "rock" CO~- overpowers soil James and Choquette, this volume).The
COz while 6180remains the same, as shown in Figures 31 and 32. The data fields are from Gross need for a " marine baseline" is critical
(1964) andAllan and Matthews (1977, 1982). The trends are in part based on interpretations by in older Paleozoic limestones - and
Hudson (1977), Lohmann (1982, 1983), and Magaritz (1983). possibly Cretaceous limestones -
c
62 Diagenesis Geoscience Canada Reprint Series 4 c
c
where original 01ac and 01eO of marine ence of isotopically "light" (1aC-poor) positions through the meteoric are
c
sediments and cements appear to have carbon. Calcites precipitated in caliche much less variable than carbon-isotope
values. The 01eO values of carbonates
c
been several per mille "lighter" than in
the present-day ocean (James and Cho-
and soil profiles - in hardpans, nodules
and associated vadoids - are typically in caliche and soil profiles are much like c
quette, 1983,Figs. 20 and 21). Contrary -7%0 to -13%0 in Recent and Pleistocene those of carbonates in the rest of the
to earlier ideas that this isotopic "light- profiles, changing downward within a vadose zone and the lenticular phreatic
ness" was the result of more prolonged few centimetres to metres at most to (except for the evaporation effect men- c
diagenetic alteration in older Pleisto-
cene limestones, it now appears that
values of -2%0 to -4%0, which are typical
for the rest of the vadose. The "light"
tioned earlier), generally -2%0 to -6%0 in
young Cenozoic carbonates. c:
real, non-linear variations in the com-
position of seawater through Phaner-
compositions reflect contributions of
CO2 from decaying organic matter to
Covariant trends of 01ac and 01eO
should also be displayed by CaCOa
c
ozoic time are represented. vadose pore waters seeping down- cements precipitated from mixtures of c
The range, and more significantly the
pattern, of carbon and oxygen isotope
ward or being drawn upward to evapora-
tion throughout the caliche-soil profiles
marine and fresh meteoric waters, as in
a mixing zone. The "end members" can c
compositions found in many Cenozoic (for discussion of these effects see be identified most clearly if they are c
limestones in shallow meteoric settings
- where limits of present-day or former
Rightmire and Hanshaw, 1973;Hudson,
1977; Allan and Matthews, 1982;
original marine CaCOa and carbonate
precipitated in a caliche or soil profile c
vadosezones, phreatic lenses and even
mixing zones can be determined with
Lohmann, 1983, 1988). Deeper in the
vadose, dissolved CO2 in pore water
(Figure 35). In progressively more
altered carbonates below profiles of this
c
increasing confidence - also occur in
many Phanerozoic limestones. Ranges
rapidly equilibrates isotopically with the
marine carbonate sediment through
kind (Figures 31 and 32), one often sees
an inverted "J" or "L" shaped trend, as
c
in fossil limestones are usually smaller which it is percolating. pointed out by Lohmann (1982, 1983),
(
because of the damping effects of later
burial cements or other forms of altera-
Speleothems, however, do not have
the same isotopic signature as vadose
Magaritz (1983) and AI-Aasam and
Veizer(1986).This kind oftrend on cross
c
tion, but patterns are similar. cements, generally because of kinetic plots is a result of the extremely "light", c
The general tendency in stratigraphic
profiles through young metastable car-
isotopic fractionation during rapid
degassing. Both 01ac and 01eO are
1aC-impoverished CO 2 supplied to
near-surface pore waters by decaying c
bonate sequences in near-surface
meteoric environments is for carbon-
enriched (Hendy, 1971; Lohmann, 1988;
Gonzalez and Lohmann, 1988).
organic matter, as noted earlier, and
the differences in rates at which pore
c
isotope compositions to vary consider- Oxygen in the CaCOa-H 20-C02 sys- waters equilibrate isotopically with the c
ably down through the vadose, par-
ticularly within short distances (metres
tem can come from the minerals, the
water and lor the gas, but in reality con-
host CaCO a sediments and rocks
through which they pass. Where organic c
or less)of subaerial exposure surfaces;
then to stabilize and remain relatively
tributions from dissolved CO2 are min-
iscule compared to contributions from
matter did not exist or was very sparse at
the surface, so that a caliche or soil pro-
c
constant through the shallow phreatic; the water and from host sediment or file did not develop, a "J"-shaped trend c
and finally to change through the mixing
zone toward marine or nearly marine
limestone. Thus oxygen-isotope com- will not be expected to develop.
c
values. Oxygen-isotope compositions c
show little variation through the vadose
and shallow phreatic except in the mix- c
ing zone where they become heavier,
enriched in 1eO because of preferential
c
loss of 160 by surface evaporation. c
Lohmann (1988) has called this invar-
iant 01eO value, when preserved in car- c
bonate precipitates, the meteoric cal-
cite line, which is likely to be unique for
c
each sequence and locality studied. c
These general relationships are shown
in Figures 31 and 32. Although the rela- c
tionships were recognized first in Pleis-
tocene sequences, they are commonly
e
preserved in Phanerozoic limestones
(Allan and Matthews, 1982)where they
c
may have value for signalling the pre-
(
sence of ancient subaerial surfaces. c
In the CaCOa-H 20-C02 system car-
bon comes almost wholly from the origi- Figure 36 Hard Pleistocene reef limestones overlying softOligocene chalks, Barbados. The c
nal carbonate and CO2 gas. Carbon-
isotope variability in near-surface
Pleistocene limestone hardened quickly in the meteoric environment because it was com-
posed of metastable minerals. The chalk remained soft because it was originally, and still is,
c
vadose zones is due mainly to the influ- composed of calcite. c
c
c
c
c Limestones - The Meteoric Diagenetic Environment 63

c
c- DIAGENESIS OF STABLE tionally well preserved. There is some by James and Choquette, this volume).
o CARBONATE (CALCITE)
SEDIMENTS
calcite cement, precipitated mostly as
epitaxial overgrowths on coccoliths and
If meteoric diagenesis, or more prop-
erly, the lack of meteoric diagenesis of
( It is clear that the extensive alteration echinoids. This minor cement is likely chalk, is any guide, then the subaerial

c and cementation of metastable carbon-


ate sed iments is driven by the co-ex is-
derived from the very smallest, super-
soluble particles . Compared with the
exposure of sediments in the lower and
middle Paleozoic, for example, should
c tence of different minerals with different
solubilities. But what about carbonate
metastable suites just described, these
sediments are virtually unaltered! The
leave little discernible evidence in the
form of diagnostic cement, signs of fab-
( sediments that are mostly calcite? We contrast is probably nowhere better dis- ric-selective dissolution, or geochem-
cannot, unfortunately, make a direct played than on the island of Barbados ical signatures. Since there were likely
comparison because shallow-water where soft Oligocene chalks directly some aragonitic components in these
C' Neogene carbonate sediments are usu- underlie hard, Pleistocene reef lime- calcite sediments, there was probably
a little cementation , but very little.
ally a mixture of minerals, but we can stones and, even though the permeabil-
( lookat deep-water chalks (Cretaceous- ity of the chalk is much less than that of Instead, the signature would be more in
o Recent) to gain some insights. These
sediments are , or were , composed
the reef limestone, both have been
exposed to percolating fresh waters for
the form of surficial karst, etc. These
conclusions have yet to be tested
almost entirely of calcite skeletal ele- nearly the same length of time, about against the rock record.
ments originally, with relatively few 500 ,000 years (Figure 36). It is impor-
( aragonite bioclasts. Exposures of Cre- tant , however, to note that in spite of the CRITERIA FOR THE RECOGNITION
o taceous chalk are widespread in north-
west Europe. Where these sediments
fact that the chalks are soft, they com-
monly exhibit deep surficial weathering
OF THE PRODUCTS OF METEORIC
DIAGENESIS
( have not been affected by deep burial or and solution cavities, to an extent remi- In summary, it is often possible to recon-

o percolation of hot waters they are


extremely soft, with over 40% porosity,
niscent of calcite limestones.
This striking difference becomes
struct whether a given stratigraphic unit
has resided in a vadose or phreatic zone
o and have altered relatively little despite
70 to 90 m.y. of shallow burial and pro-
extremely important if the composition
of carbonate 'sediments in the past was
(or both) , either from field relationships,
from petrographic features seen at
o longed exposure. The chief alteration is at times different from those of today, scales ranging from hand specimen to

o the loss of organic matter, aragonite and


opaline silica. Calcite fossils are excep-
and dominated by calcite constituents
(see discussion of sea-floor diagenesis
the light and scanning-electron micro-
scopes or, in some cases from geo-
c. chemical information. Careful petro-
graphic observation, aided by analysis
( Table 2 Some features helpful in identifying former vadose and of cathodoluminescent zonation and
phreatic diagenetic zones. cement chemistry, can make possible
detailed reconstructions of residence
VADOSE OR in a succession of diagenetic environ-
PHREATIC RELIABILITY ments. Many of the petrographiccriteria
MEGASCOPIC have been distinguished in very young
( Holocene and Pleistocene carbonates,
Calcrete, soil-zone features, root casts, often- V
complex travertine-filled fractures but are commonly preserved in the older
stratigraphic record. Large-scale fea-
Speleothems V tures of karst terrains are being applied
Stratified/laminated sediment in larger cavities P 2 with increasing success to the fossil .
(vadose sediment often inclined) record (James and Choquette, 1988)
Trains of horizontally elongate large solution P 2 and a great deal is now known about
cavities (may cross-cut structural dip) the kinds, if not always the origins, of
features formed in the vadose zone. The
Doninantly vertical solution cavities P 2
criteria outlined in Table 2 are often
MICROSCOPIC helpful in both distinguishing and identi-
fying the interface or transition zone
Preserved needle-fibres, flower spar, fungal V between vadose and phreatic zones in
sheath & related near-surface cements the fossil record . Many of these criteria
Meniscus cement V are quite reliable. Others are less so,
Gravity cements (micro-stalactite, -stalagmite) V either because they may be produced
in both zones near the water table, or
Isopachous cements" P 2 because they may originate in other
depositional-diagenetic settings , such
• 1 is more reliable than 2. as beachrock where gravity cements
•• May be difficultor impossible to distinguish from isopachous cements of submarine,
are well known.
sea-floororigin (see James and Choquette, 1983).
The complexities of overprinting in
this realm are well illustrated in nu-
merous studies (Heckel, 1983; Roehl
c
64 Diagenesis Geoscience Canada Reprint Series 4 c
c
over precipitation , and both fabric- Geochemical profiles in metastable
c
and Choquette, 1985).Atthesame time,
we now understand the main processes selective and non fabric-select ive fab- limestone beneath a karsted surface, c
and products well enough so that for-
ward modelling of meteoric diagenesis
rics should occur. Caves and solution-
enlarged fractures should be very
outlined in part in Figure 32, ideally may
resemble those in the right portion of c
in specific settings is being proposed extensive (Figure 37), stabilization to Figure 38. Because of high-volume flow
(Matthews and Frohlich, 1987). calcite limestone rapid, and vadose flow
dominant over seepage. Congruent
in the phreatic zone, substantial effects
can be seen in compositional profiles. c
THE EFFECTS OF CLIMATE
Since water and temperature are the
meteoric diagenesis is dominant. For the 0'3C and 0'80 profiles in the
c
two most important extrinsic factors in CLiMATE & METEORIC DIAGENESIS c
the processes of meteoric diagenesis,
climate - particularly the availability of ARID SEMI-ARID c
meteoric water - influences both the
intensity and rate of carbonate altera-
c
tion (Figure 37). The effects are strong- c
est in the vadose zone.
Under hot , arid desert conditions c
both karst and calcrete may develop, c
butslowly and intheformofthin profiles ;
likewise, alteration in the vadose zone
VADOSE
c
is slow. Thus, carbonates exposed for
extended periods under these condi- WATER c
tions mayshow little or no effect of mete-
oric diagenesis. In the phreatic zone,
TABLE b-=- :P~/-~~ 7'-l
c
alteration may be more extensive. PHREATIC CALCITE c
Water flow in the phreatic is likely to be
slow because of limited recharge .
CALCITE
c
Cementation may be limited and poros- c
ity and permeability high. There are few
case studies, however, and so clear Figure 37 A diagram illustrating the effects of different climates on a series of metastable c
information is lacking .
If the climate is warm and semi-arid,
carbonates of the same age and composition. The geochemical profiles in Figure 38 apply
largely to semi-arid and wet (high rainfall) situatio?s.t\l,J ,J\.v{·
c
caliche should be both thick and exten- .Y\ EJ"')
y9 .J'\~~ /:<t
P ~l' c
sive, with surface karst also present
locally. Alteration in the vadose zone
SEMI ARID
depletion ~(--~) enrichme
Of \y _\ \,.3\
I .oJ..,..r<-~
HUMID
depletion ~(--~) enrichment
c
is relatively rapid and is dominantly in-
congruent, if the mineralogies are ~===:::::::=====::::=~~r=:~~~::::t~UBAERIA;:;r-;-~
-...!:6~18;0~;1~3:===:;~=~;~~~u~~:=1 c
metastable. Alteration is most gener-
EXPOSURE
SURFACE c
ally fabric-selective, and replacement of
original aragonite textures is good. Min-
VADOSE c
eralogical changes have been dis-
cussed earlier and diagrammed in Fig- 1
r - --,l---,l--~l----j
WATER
TABLE - 1 1 \ c
c
1 1
I I I I I I
ure 23. Geochemical changes, also r 11<) PHREATIC I I I
discussed earlier and outlined in part in
Figures 31 and 32, seem to follow the
I
I 1
I I I

,I-- ,.L---!-,--+---'t----l
1 I
TOP OF c
general direction shown , with slight
abrupt offsets at the water table if the
\ \ 1:3/
\
\
'\
MIXING
ZONE
\
\
-,
\ c
phreatic and vadose zones behave as
\ \
)<
/
'\
\
c
somewhat separate systems (Wagner,
1983). Changes are rapid in the vadose
Figure 38 Stratigraphic patterns of geochemical profiles in a sequence of initially aragonite
and magnesium-calcite limestones beneath a subaerial exposure surface, under arid or semi-
c
and very subdued or essentially nil in
the phreatic. Caves are rare and small ,
arid conditions (left) and humid conditions (right). Open arrows show dominant directions of
groundwater movement. Offsets in isotopic composition, cation concentrations and cath-
e
and movement of ground water in the odolum inescence (Lum, mainly reflecting Mn z + if FeZ+ is not excessive) occur at the water (
vadose is mostly by vadose seepage.
Under warm and rainy conditions
table because the vadose and phreatic zones behave as more or less separate hydrologic
systems , particularly in the humid setting where water is greater in the phreatic and water c
(subtropical to tropical), although mod-
chemistry is affected by other recharge sources as well. In the ertd-semi-eria setting there is
upward enrichment in Sr z + , MgZ + , and 18 0 in the shallow vadose due in part to upward c
ern diagenetic changes are difficult to
determine because of extensivevegeta-
movement of vadose pore waters in response to high surface evaporation " wicking effect':
Profiles for the phreatic and mixing zone are similar in both situations. The profiles are
c
tion and rugged karst topography, sur-
face and subsurface karst should be
somewhat modified from Wagner(1983). They were developed from data from boreholes in the c
extensive, dissolution would prevail
Pleistocene of Barbados (see text) and from profiles of various ancient stratigraphic
sequences beneath subaerial exposure surfaces (Allan and Matthews, 1982; Wagner, 1983). c
c
c
c
C' Limestones - The Meteoric Diagenetic Environment 65

C
C phreatic there may be an offset toward PC02 levels were higher than those that were available to be altered. As
pointed out by Lowenstam (1963) and
C heavier compositions if cementation by
calcite has been slight , or offset toward
today, and an "icehouse" mode when
they were more like the modern atmo- Wilkinson (1979), the mineralogical
C. lighter values if meteoric calc ite cemen- sphere (Fischer, 1981). During the composition of shallow-water skeletons
tation has been extensive . Dissolution greenhouse mode, meteoric waters , has varied through geologic t ime.
C of aragonite and magnesium alteration with increased PC02, would have been Although the trends are not yet firmly
of Mg-calcite may be so extensive in the established, first-order variations seem
C vadose zone that greatly enriched pore
more aggressive than they are today.
clear (Figure 39). In general, sediments
How this would be reflected in the rock
C waters lead to enrichment of Sr2+ and record is difficult to assess. In areas of on modern and Cenozoic shallow plat-
Mg2+ in diagenetic calcite. forms are or were mostly aragonite and
C In summary, in warm climates the
thin soil cover, or at times when soils
were poorly developed, increased sim- magnesium-calcite, whereas those in
( supply of meteoric water is important in ple corrosion would lead to more exten- similar Mesozoic settings were about
determining the rate, intensity and even sive surface karst. Intuitively, one feels equally aragonite and calcite (either
( direction of diagenetic alteration. Varia- high-magnesium and low-magnesium).
that there should be more extensive
o tions in rainfall may be substantial
across the larger oceanic islands that
karst development during these times, In contrast, sediments in the middle and
early Paleozoic were mostly calcite
o rise some hundreds of metres above
yet most extens ive dissolution occurs
beneath a soil and not on bare rock. So (except perhaps for the earliest Cam-

o sea levelbecause of rain shadow effects


and are generally even greater across
the effect should be most noticeable in
areas where there is little soil develop-
brian). The history of the mineralogy of
non-skeletal particles seems more
( large land masses. ment, or at times when soils were poorly complex (Sandberg, 1983), and varied
in an oscillating fashion. Because the
o LARGE-SCALE VARIATIONS
developed.
Changes in the Biosphere. style of diagenesis is partly dependent

o THROUGH GEOLOGIC TIME


It is common practice to extrapolate the
Terrestrial: Weathering effects and
the generation of CO2-charged waters
upon sedimentary mineralogy, those
sediments with abundant aragonite will
o processes and products of meteoric
diagenesis observed today to the fossil
are heavily dependent upon the pre-
sence and evolution of higher plants.
have undergone the most extensive
alteration and have been cemented
record. As emphasized by James and Although land plant fossils are known most in the meteoric environment. Con-
r: Choquette (this volume) , however, from the early Paleozoic, theywere not a versely, those predominantly calcite
there have been changes in the nature significant part of the terrestrial land- and Mg-calcite sediments will be little
of the atmosphere and biosphere scape until Devonian time, but were affected and illustrate features because
through geologic time which may have widespread by the early Mississippian . of water-controlled alteration. These dif-
C profoundly influenced the style of Thus, even though soils may have ferences are well demonstrated byany-
meteoric diagenesis (Figure 39). one who has marvelled at the superb
l Changes in the Atmosphere.
existed in the early and middle Paleo-
preservation of early Paleozoic fossils,
o It now seems probably that there have
been variations in atmospheric PC02
zoic, they would have been close to the
protosoils of today, dominated by algae
and lichens , and unlike the complex
yet struggled to discern the nature ofthe
numerous recrystallized and partially
C through the Phanerozoic. The atmo- biogenic profiles in true soils. dissolved skeletons in Cenozoic lime-
stones (Figure 40). It often seems that
(' sphere seems to have oscillated Marine: Of equal importance is the
the older the limestone, the better the
between a "greenhouse" mode when mineralogy of carbonate sediments
(I preservation!
SEDIMENTARY MINERALOGY
Synthesis: By integrating these vari-
LANO CUMATIC METEORIC ables in a general way,wecan speculate
o
r
0
T
PLANTS

ANGIOSPERMS
EPISODES

ICE HOUSE
OIAGB4ESIS
1 T
on potential variations in diagenesis.
The Phanerozoic could be subdivided
into five periods when the effects of
100 K GREEN K
( meteoric diagenesis were probably dif-
J GYMNOSPERMS HOUSE 2 J
ferent (Figure 39).
200 'Ii 'Ii
(, I LOWER ICEHOUSE
~
1. OLIGOCENE - PRESENT. Since
300 3 conditions were similar to those today
C VASCULAR C
PLANTS and in the recent past, the present mete-
D 0 oric environment is a good guide to
6 400 S GREEN
HOUSE 4
S
rocks of this age.
0 ALGAE 0
2 . LATE TRIASSIC - EOCENE. A
500 • period when sediments had less arag-
r
C ,, LICHENS
ICE HOUSE 5
C
800 P-C , PC onite, atmospheric CO2 was higher and
there were no terrestrial grasses,
Figure 39 A plot of variations in non-skeletal mineralogy (James and Choquette, 1983; although plant cover in general was
Sandberg, 1983), skeletal mineralogy (approximated from Lowenstam, 1963; Wilkinson, 1979), extensive. The spectrum of textures and
terrestrial vegetation and atmospheric PC02 (Fischer, 1981) throughout Phanerozoic time. fabrics describedin this article shouldbe
Numbers at right indicate approximate intervals when the combined effects of these variables expected for rocks of this age, with per-
probably resulted in different styles of meteoric, particularly vadose, diagenesis. haps more obvious surface karst.
,-
c
66 Diagenesis Geoscience Canada Reprint Series 4 c
c
3. LATE DEVONIAN/EARLY It must be remembered that this Although many reactions take place c
CARBONIFEROUS - MID TRIASSIC.
During these times, the atmospheric
scheme is a generalization, a back-
ground against which to consider
in this setting, in terms, of carbonate
diagenesis two are critical: (1) a first-
c
PC0 2 was similar to that of today, plant meteoric diagenesis, realizing that local order reaction, water-controlled (con- c
cover was potentially extensive, and
sedimentary mineralogy was roughly
conditions may completely overprint
the general trends. Conversely, where
gruent) meteoric diagenesis, controlling
dissolution and precipitation in general c
the same as in younger rocks (less skel- lack of alteration or absence of mete- by invasion and evasion of CO2 from
oric diagenetic features has in the past meteoric waters; all CaC0 3 minerals
etal aragonite). Both surface karst and
calcretes probably developed com- been interpreted as lack of exposure, it including calcite are dissolved, but only c
monly at this time, with somewhat less
cementation and dissolution and so less
is also clear that exposure may have
taken place without any significant
calcite is precipitated; (2) a second-
order reaction, mineral-controlled c
fabric-selective diagenesis than in signature. (incongruent) meteroric diagenesis, c
younger rocks.
4.MID CAMBRIAN-MID DEVONIAN. SUMMARY
which affects minerals of differing sol-
ubilities; aragonite and Mg-calcite, but c
A time quite different from the recent Carbonate sediments commonly are
exposed to percolating meteoric waters
not calcite, are dissolved and new dia-
genetic calcite is precipitated. Both
c
past: atmospheric PC0 2 was relatively
high. There were no true land plants, so
at various times during their history. reactions occur concurrently when c
soils were poorly developed. Carbonate
Since they are mostly deposited in shal-
low waters, small changes in sea level,
metastable carbonates are flushed by
meteoric waters, but once the minerals c
sediments were composed mostly of
calcite. The effects of meteoricdiagene-
whatever the cause, will result in sub-
aerial exposure early in their history,
haveall changed to calcite, only the first-
order reaction continues and much of
c
sis at this time were probably minimal
and confined to surface and subsurface
either immediately after deposition or the meteoric environment becomesdia- c
karst, non-fabric-selective alteration,
little cementation, little or no caliche
after shallow burial. Once they are
exposed, a predictable hydrologic regi-
genetically inactive.
Regardless of which reaction is pre- c
and much fabric retention.
men is established, with only minor sur- valent and what carbonate minerals are (
ficial exposure resulting in relatively present, there is a net loss of carbonate
5. LATE PRECAMBRIAN? - EARLY
CAMBRIAN. Scant evidence suggests
deep percolation of fresh water and from the system. This is best reflected c
that the atmosphere was like that of
accompanying diagenesis. Although
the occurrence of meteoric diagenesis
in a variety of karst-related features.
Atthe sametime, soil-related processes c
today in terms of Pco 2 and sedimentary
mineralogy was like that in the middle
can be established from textural and
fabric criteria, pinpointing specific
form a variety of very distinctive caliche
carbonates which, because they are
c
Paleozoic, but that there were poor zones of alteration is difficult because, accretionary, are preserved and are c
soils. Again much karst, and little or no
caliche were developed, but some fab-
with time and fluctuating sea level, the
zones migrate through the rock. Stages
extremely useful as criteria of subaerial
exposure. If the exposed sediments are c
ric-selective alteration. Cementation of alteration are thereby superimposed composed of metastable carbonates, a c
would have been the most significant
results of meteoric diagenesis.
or early stages of diagenesis are oblite-
rated by later ones.
specific, predictable series of changes
takes place, and lithification is achieved c
c
c
c
c
c
c
c
c
e
c
(
C
l
Figure 40 (Left) Ordovician limestone with all the fossils, trilobites (T), brachiopods (B), and bryozoans (C), preserved because they were
originally calcite. C
(Right) Pleistocene limestone illustrating porosity developed by dissolving stick-corals (C) and gastropods (G).
C.
(

C
(
( Limestones - The Meteoric Diagenetic Environment 67

c
C' by precipitation of cements with distinc- REFERENCES Esteban, M. and Klappa , C.F., 1983, Sub-

o tive structures which are preserved in


ancient limestones . Concomitantly, General References
aerial exposure, in Scholle, P.A.,
Bebout , D.G. and Moore , C.H., eds.,
CJ because the process of alteration These articles and books address various
aspects of meteroic diagenesis and
Carbonate Depositional Environments:
American Associat ion of Petroleum
involves dissolution and precipitat ion,
together cover most of the topics discussed Geolog ists, Memoir No. 33 , p. 1-54.
there is important cation and isotopic
in this paper . A beautifully illustrated, up to date refer-
exchange with meteoricwaters,leading
C' generally to lower Mg2+ and Sr2+ con-
ence synthesizing much of our under-
Allan, J.A. and Matthews, A.K., 1982, Iso- standing of surficial diagenesis .
( tents and higherFe2+ , Ca2 + and Mn2 + , tope signatures associated with early Folk, A.L., 1973, Carbonate petrography in
as well as depletion in both 513C and meteoric diagenesis : Sedimentology, the post -Sorbyian age, in Ginsburg,
/) 1 8 0 , compared with the original v. 29, p. 797-817. A.N., ed., Evolving Concepts in Sedi-
c sediments.
The intensity of meteoric diagenesis
A good discussion of the theory behind
and examples of isotop ic variations dur-
mentology : Johns Hopkins University,
Studies in Geology, v. 21, p. 118-158.
( is dependent not only upon where in the ing meteoric diagenes is. A succinct essay presenting, amongst
Bathurst, A.G.C ., 1975, Carbonate Sedi- other things, an outline of the processes
environment changes have take place,
( ments and their Diagenesis: Elsevier and products during subaerial diagene-
but also upon the residence time in any
Scientific Publishing Co., Amsterdam , sis of metastable carbonates.
particular zone . Climate is also an 658 p. Halley, A.B. and Harr is, P.M., 1979, Fresh-
important factor in vadose alteration . Bathurst, R.G.C., 1980, Lith ification of car- water cementation of a 1,000 year old
The processes and products of mete- bonate sediments: Science Prog ress oolite: Journal of Sedimentary Petrol-
o oric diagenesis described in this article
cannot be applied equally to carbonates
Oxford, v. 66, p. 451-471.
These two references are the best syn-
ogy, v. 49, p. 969-988 .
One of the few studies to integrate
o of all ages. Changes in the biosphere theses of information concerning the petrographic, geochemical and hydro-

o (vary ing skeletal mineralogy and


changes in terrestrial vegetation) and
alteration of metastable carbonates in
the meteoric environment.
graphic data in the study of the early
diagenesis of metastable carbonates.

o the atmosphere (varying Peo.) through


Bathurst, A.G.C., 1986, Carbonate diagen-
esis and reservoir development: con-
James , N.P. and Choquette , P.W., 1988,
eds., Paleokarst: Springer-Verlag, New

o geologic time will have had a profound ,


but as yet uncertain, effect on the style
servation , destruction and creation of
pores : Colorado School of Mines Quar-
York, 421 p.
A series of 18 papers covering all major

o and intensity of freshwater diagenesis .


Finally, when examining any lime-
terly, v. 81, No.4, p. 1-24.
A succinct review of meteoric and other
aspects of karst and paleokarst, exam-
ples range in age from Precambrian to
c stone outcrop it should be remembered
that this rock is now in the meteoric
diagenesis , focussed on the evolution of
porosity.
modern.
Longman, M.W., 1980, Carbonate diage-
Bagl i, J., 1980, Karst Hydrology and Physi- netic textures from near-surface diage-
environment and many of the fabrics
o and textures present may be the result
of very recent processes!
cal Speleo logy: Springer-Verlag, Berlin,
285 p.
netic environments: American Associa-
tion of Petroleum Geologists, Bulletin,

o ACKNOWLEDGEMENTS
A text devoted to the processes of karst
formation: a good single source outlining
basic concepts of rock-water inter-
v. 63, p. 461-487.
A useful summary of the processes and
products of meteoric diagenesis of meta-
We thank many colleagues who offered actions. stable carbonates, a good place to begin.
o suggestions and guidance during the
preparation of this manuscript: W. Back,
Bricker, O.P. , 1970, ed ., Carbonate
Cements: The Johns Hopkins Press,
Matthews, A.K., 1974, A process approach
to the diagenesis of reefs and reef-asso-
R.G.C. Bathurst , N. Chow, M. Coniglio, Baltimore, MD, 376 p. ciated limestones , in Laporte, L.F., ed.,
This book conta ins a suite of papers on
o D.H. Craig, A. Desrochers , J.A.D .
Dickson, D. Haywick, J. Kennard, K.C. meteoric diagenesis with excellent
Aeefs in Time and Space: Society of
Economic Paleontolog ists and Mineral-

o Lohmann, R. Reeder, P. Sandberg, L.


Vacher, P. Wagner and B.H. Wilkinson .
illustrations of different types of meteoric
cements.
ogists, Special Publication No. 18,
p.234-256.

o N.P. James acknowledges the Natural


Sciences and Engineering Rese