Eur. J. Mineral.

2005, 17, 7-20

Clay minerals and sedimentary basin history

RICHARD J. MERRIMAN*

British Geological Survey, Keyworth, Nottingham NG12 5GG, U.K.

Abstract: Clay minerals in the mud and soil that coat the Earth’s surface are part of a clay cycle that breaks down and creates rock
in the crust. Clays generated by surface weathering and shallow diagenetic processes are transformed into mature clay mineral
assemblages in the mudrocks found in sedimentary basins. During metamorphism, the release of alkali elements and boron from
clay minerals generates magmas that are subsequently weathered and recycled, representing the magma-to-mud pathway of the
clay cycle. Volcanogenic clay represents an important but hitherto underestimated proportion of recycled clay. Within sedimentary
basins, immature clays are transformed to mature and supermature clay assemblages by a series of reactions that generally obey
the Ostwald Step Rule. Bedding-parallel microfabric generated by these reactions produce significant changes in the physical
properties of deeply buried mudrocks. Clay minerals react to form equilibrium assemblages in 1 x 104 years in some hydrothermal
systems, but immature clays may survive for up to 2 x 109 years in mid-continental rift basins. Clay mineral assemblages and the
b cell dimension of K-white mica can be used to infer the geotectonic settings of sedimentary basins.

Key-words: clay minerals, sedimentary basins, clay cycle, clay maturity.

1. Introduction mature chemically, mineralogically and texturally. Basins

Clay minerals are the key constituents of the mud and
soil that coat the Earth’s surface, forming a thin buffer zone
between the atmosphere, hydrosphere and biosphere and
the underlying crust of crystalline rock. This coating of
clay, formed by chemical reactions between water and
rock, is the most important product of the process of weath-
ering since it provides the essential constituents for the soil
and deep-sea mud supporting biogenic activity that first
appeared on this planet around 3800 Ma. Without such
reactions rock dust would cover the Earth’s surface as it
does on the Moon and other planets in the solar system. But
while clay minerals may be vital to Earth’s life support
system, they are also an essential group of minerals in a
clay cycle that regenerates the crust and creates new crust
from the underlying mantle (Merriman, 2002a).
Sedimentary basins are an important stage in the clay
cycle, where the predominantly juvenile clays formed by
surface weathering are collected into large deposits and
mature before they progress to the next stage of the cycle.
In the broad sense, sedimentary basins are those areas of
the Earth’s crust where sediments accumulate to some
considerable thickness (> 0.5 km?) over geological time
periods. Although they are highly variable in size, they tend
to be at least 100 km long and tens of km wide (Einsele,
2000). The tectonic setting of sedimentary basins strongly
influences deposition and the rate at which sediments
generated at active margins, i.e. where plate boundaries are
in collision, commonly experience rapid sediment loading
and the contents are likely to mature by rapid burial,
followed by deformation and metamorphism. Where basins
have formed within stable cratons (e.g. intracontinental sag
basins) or on some passive margins of long-lived rifts (e.g.
the Atlantic margins), they experience slow subsidence
rates and may preserve non-metamorphosed sedimentary
sequences that span a considerable part of the Phanerozoic
time scale, with some surviving from Proterozoic times.
This review is written from a personal perspective that has
evolved from some 40 years of applying clay mineral
studies to geological research. It explores how clay
minerals behave in different basinal settings in response to
the variable rates and types of maturation processes, and
how clay maturation can be used to characterize the
thermal and tectonic history of sedimentary basins.
2. The clay cycle
Weathering can be regarded as the starting point of the
clay cycle since it produces new clay minerals from rock-
forming minerals and also liberates existing clay minerals
(Fig. 1). Almost all of the common rock-forming minerals
are capable of forming clay minerals during weathering,
with the notable exception of quartz. Minerals that initially

*E-mail: rjme@bgs.ac.uk

0935-1221/05/0017-0007 $ 6.30
DOI: 10.1127/0935-1221/2005/0017-0007 © 2005 E. Schweizerbart’sche Verlagsbuchhandlung. D-70176 Stuttgart
8 R. J. Merriman
crystallized at the highest temperatures, for example those
in a basalt, are least stable when they cool to surface condi-
tions and most susceptible to clay mineral formation. Early
models of the clay cycle (e.g. Eslinger & Pevear, 1988)
tended to ignore the contribution from volcanic activity.
Glass is the most voluminous product of volcanic erup-
tions, on the land and beneath the oceans, and readily alters
to clay minerals. A conservative estimate of the volume of
volcanic ash erupted annually is around 0.15 km3, half the
minimum annual global production of magma in volcanic
arc settings; this is equivalent to at least a 2 mm-thick layer
of ash over the entire Earth’s surface every 1000 years
(Sparks, 1999). If most of the annual production of ash is
converted to clay minerals, then this suggests that at least
2 % of the present day global sediment yield from rivers,
estimated at 7.5 km3/year (Einsele, 2000) is probably
volcanogenic clay. Contributions from other sources,
particularly submarine volcanism, are more difficult to esti-
mate, but are likely to double the above figure of 2 %.
Clay minerals produced by subaerial weathering are
mostly transported into sedimentary basins where they are
collected and matured as they move to the next phase of the
cycle. When clay minerals are buried in sedimentary basins
they undergo a series of transformations in response to the
geothermal conditions within the basin, and the geotec-
tonic evolution of the basin. In some passive margin basins,
and also some intercontinental sag and rift basins, burial
without pervasive tectonism results in diagenetic transfor-
mations in response to temperatures that barely reach
200ºC. At active plate margins, diagenetic burial is usually
succeeded by low-grade metamorphism, due to higher
geothermal gradients or tectonism, or a combination of
both. As a result, clay minerals are further transformed to
equilibrium assemblages dominated by white mica and
Fig. 1. The clay cycle showing
different pathways for recycling clay
minerals in the Earth’s crust. After
weathering and pedogenesis,
neoformed and inherited clays are
deposited in a sedimentary basin.
Burial and tectonism transforms
clays to low-grade metamorphic
mudrocks composed mainly of
white mica and chlorite. Basin
inversion and uplift returns low-
grade mudrocks to surface weath-
ering, completing the clay cycle.
Deep burial and high-grade meta-
morphism leads to breakdown of
micas and magma generation.
Surface volcanism and weathering
begins a new clay cycle.
chlorite, marking the onset of greenschist facies metamor-
phism and temperatures above 300ºC.
Further temperature increases and fabric-forming
deformation of mudrocks produces coarsely crystalline
metamorphic rocks, such as muscovite-chlorite schists and
biotite gneisses. Where these rocks are assembled into a
mountain belt, crustal thickening causes further tempera-
ture and pressure increases in the most deeply buried meta-
morphic rocks, which begin to melt. Rocks containing
micas and other hydrous minerals are usually the first to
melt and generate migmatites, a mixture of melted and
non-melted rock. Magmas that escape from this zone of
partial melting move upwards to form granitic intrusions in
the crust, where they weather to begin another cycle of clay
mineral production. Where water circulates through a
system of shrinkage cracks and joints in consolidated
granitic intrusions, clays may also form by hydrothermal
alteration (Fig. 1).
The mud-to-magma pathway of the cycle can be by-
passed by the uplift of sedimentary basins or metamorphic
terrains, returning mudrocks and metapelites to surface
weathering (Fig. 1). The rate at which the different path-
ways complete the clay cycle vary considerably. In some
accretionary complexes clays can be recycled in less than 1
Ma, as in the case of the Pliocene-Pleistocene Coast Range
of eastern Taiwan (Dorsey et al., 1988). In contrast, the
pathway that results in orogenic magma genesis may take
well over 100 Ma to complete the cycle.
Clay minerals generated by submarine weathering are
also recycled. Sea floor basalts, making up nearly 60 % of
the Earth’s crust, readily react with seawater at low temper-
atures to produce clay minerals which tend to be Fe- and
Mg-rich, such as saponite and celadonite (Alt, 1999).
Similar Fe, Mg-rich clays also form around submarine
 Clay minerals and sedimentary basin history 9

Fig. 2. The origin of clay minerals in

different geotectonic settings. (a) Basin
formed in active margin setting.
Extensional back-arc basins contain
inherited clays from volcanic arc and
hinterland terranes, and also neoformed
volcanogenic and hydrothermal clays
formed in situ. Fore-arc and foreland
basins mainly contain inherited clays
from eroded mountain belts. Inherited
clays in accretionary prisms are trans-
formed to low-grade metamorphic clays
during underplating; transformed clays
also predominate in fold-and-thrust
belts. (b) Basins formed at passive
margins or within plate settings may
retain a higher proportion of neoformed
clays. Inherited clays are predominant in
typical passive margin basins, but
shallow shelf basins on passive margins
may contain a high proportion of
neoformed Fe-rich clays. Neoformed
clays also form around mid-oceanic
ridge systems and in basalt-floored
oceanic basins. Continental rift basins
have significant amounts of neoformed
clays. Inherited clays predominate in
continental sag basins formed on shields
with varied topographic relief.

hydrothermal mounds. These clays and other minerals
generated by basalt-seawater reactions are closely associ-
ated with marine organic debris, distal clays discharged
from continental river systems and wind-blown dust.
Together they give rise to the pelagic mud that covers wide
areas of typical oceanic basins. Recycling of oceanic crust
takes place at active plate margins where approximately
half of the subducted sediment is accreted or underplated to
generate new crust (Einsele, 2000). The remainder,
together with argilized basaltic rock, is conveyed into the
mantle on a slab of oceanic crust. The breakdown of clay
minerals which are carried on and within the subducted
slab has been linked with the generation of magmas, partic-
ularly by the release of the fluids containing alkali
elements and boron that promote partial melting of the
mantle wedge beneath volcanic arcs (e.g. Mezler &
Wunder, 2000; Patino et al., 2000). The rate at which
basalt-derived clays and pelagic mud complete the clay
cycle depends on the geotectonic setting of the basin.
Oceanic basins with active margins, such as the eastern
Pacific, promote the fastest cycles, in some cases taking
less than 150 Ma to recycle basalt from mid-oceanic fissure
volcanoes, perhaps with a thin drape of pelagic mud, to the
eruption of new lava above a subduction zone. In contrast,
clay recycling is much slower where certain types of
passive margin form the borders of major oceanic basins.
Much of the Atlantic Ocean is fringed by passive margin
basins containing mud-dominated sediments that have
accumulated for up to 200 Ma. Active recycling of these
sediments is restricted to subduction zones in the southern
Atlantic and the Caribbean. Tens of millions of years may
pass before such activity becomes widespread and more of
the vast accumulation of muddy sediment around the
Atlantic is recycled into magma.
3. Modes of origin
Up to 60 % of strata in sedimentary basins are mudrock
lithologies such as mudstone, shale and slate (Potter et al.,
1980), with clay as the dominant mineral component. Clay
minerals can form by a variety of processes that reflect
their sensitivity to physical and chemical changes at the
Earth’s surface and in the shallow crust. Within sedimen-
tary basins clay minerals have three modes of origin
(Millot, 1970; Eberl, 1984). Neoformed clay minerals are
formed in sedimentary basins by direct precipitation from
solution or via the crystallization of amorphous materials,
such as glassy volcanic ash. Inherited clay minerals are
transported into sedimentary basins with little modifica-
tion, having been formed elsewhere. Transformed clay
minerals develop as sedimentary basin mature, when both
inherited and neoformed clays react in response to diage-
netic and low-grade metamorphic conditions. Hence a
transformed origin indicates that the clay mineral devel-
oped from a pre-existing mineral, either by dissolution-
precipitation or solid-state replacement, including resulting
overgrowths. Some well characterized transformations
proceed by a sequence of reactions via a series of
metastable intermediate products, as in the case of the
smectite-to-illite transformation (e.g. Altaner & Ylagan,
1997; Stixrude & Peacor, 2002). Prograde transformations
10 R. J. Merriman
are generally characterized by progressive increases in
crystal thickness (“crystallinity”), and decreases in crystal
defect densities, lattice strain and compositional variability
(Peacor, 1992). These changes, together with the develop-
ment of new microfabrics in clay minerals, convert soft
muds to lithified mudstone and shale, and subsequently
slate (Merriman & Peacor, 1999). Retrogressive transfor-
mations essentially reduce the crystal thickness of clay
minerals by introducing stacking defects, and also increase
defect densities, lattice strain and compositional variability.
Retrogression is the dominant mechanism of clay mineral
weathering and soil formation (Millot, 1970; Środoń,
1999), and biogenic degradation (e.g. McIlroy et al., 2003).
Regional retrogressive events in metamorphic terrains are
associated with fluid movement (e.g. Nieto et al., 1994;
Zhao et al., 1999; Abad et al., 2003).
The different thermal histories and geotectonic settings
of basins are reflected in the origins of their clay mineral
assemblages (e.g. Velde & Vasseur, 1992). Basins formed
at active plate tectonic margins tend to have a greater diver-
sity of clay origins than passive margin or within-plate
basins (Fig. 2). An extensional back-arc basin typically
contains inherited clays derived from volcanic arc and
hinterland terranes, and also neoformed volcanogenic and
hydrothermal clays formed within the basin. Basins that
develop by rapid subsidence, such as fore-arc and foreland
basins, tend to contain predominantly inherited clays
derived from eroded mountain belts. In accretionary prisms
inherited clays are soon transformed to low-grade meta-
morphic clay assemblages, especially during tectonic
underplating (e.g. Sample & Moore, 1987; Merriman &
Roberts, 2001). Transformed clays also predominate in
fold-and-thrust belts, which may develop when back-arc or
foreland basins are contracted and deformed. Basins
formed at passive margins or within plates may retain a
higher proportion of neoformed clays. Inherited clays in
passive margin basins may reflect the weathering condi-
tions and the maturity of the hinterland. For example, juve-
nile clays such as kaolinite or smectite may be the
dominant inherited minerals derived by tropical weathering
whereas illite and chlorite are more likely to be derived
from temperate weathering of a mature hinterland. In
contrast, shallow shelf basins on passive margins may
Fig. 3. Schematic diagram showing the series of clay
mineral reactions that characterize transformations in
mudrock lithologies found in sedimentary basins.
Reaction progress is from top to bottom, indicated by
heavy arrows. Diagonal arrows indicate products
contributed from one reaction series to another. The
products of two or more reaction series constitute a
clay mineral assemblage in a typical mudrock.
contain a high proportion of neoformed Fe-rich clays such
as glaucony or verdine ‘facies’ minerals. Neoformed clays
also predominate around mid-oceanic ridge systems and in
basalt-floored oceanic basins. Continental rift basins or
some perimarine basins tend to contain significant amounts
of neoformed clays, commonly formed in saline or hyper-
saline conditions (e.g. Jones & Galan, 1988). These condi-
tions may also influence the type of clays that occur in
continental ‘sag’ basins, but inherited clays normally
predominate on shields with varied topographic relief.
These within-plate basins preserve some of the oldest non-
metamorphic clay assemblages.
4. Clay mineral transformations
Prograde clay mineral transformations in a sedimentary
basin are primarily a response to burial and varying degrees
of tectonic fabric development at temperatures below
300°C. Some transformations produce predictable patterns
of change in mineral assemblages that can be used to char-
acterize the conditions of diagenesis and low-grade meta-
morphism in basins. Such patterns were first recognized by
Hower et al. (1976) from their study of the smectite-to-
illite transformation in the Tertiary shales of the Gulf
Coast, U.S.A. During the past two decades, a series of
studies stimulated by these observations have shown that,
as sedimentary basins mature, this transformation is part of
a more extended series of reactions in 2:1 dioctahedral clay
minerals that ultimately transform smectite to muscovite
via a sequence of metastable intermediate products (e.g.
Moore & Reynolds, 1997; Merriman & Peacor, 1999). The
series of reactions: smectite → mixed-layer illite/smectite
(I/S) → illite → muscovite (Fig. 3) is characterized by a
progressive increase in crystal thickness (illite “crys-
tallinity”), and decreases in crystal defect densities, lattice
strain and compositional variability as illite-muscovite
becomes better ordered (Peacor, 1992). In marine sedimen-
tary basins this is the most widely reported and best char-
acterized clay mineral reaction series, despite ongoing
controversy on the precise nature of reactants and products
(e.g. Peacor, 1998; Stixrude & Peacor, 2002). Although
rarely very abundant, a sub-series of reactions involving
 Clay minerals and sedimentary basin history
Na-rich 2:1 dioctahedral minerals has been reported in
some mudrock sequences (Fig. 3). Products first appear in
late diagenetic mudrocks as nanometer-scale intermediate
Na/K-mica coexisting with K-micas, and these evolve to
form 2M1 paragonite and muscovite in higher grade slates
(Merriman & Roberts, 1985; Jiang & Peacor, 1993; Li
et al., 1994; Livi et al., 1997).
A similar sequence of transformations in 2:1 trioctahe-
dral Mg,Fe-rich clay minerals is analogous to the smectite-
I/S-illite-muscovite reaction series. Although trioctahedral
saponite (Mg-dominant in octahedral sites) is much less
plentiful than dioctahedral smectite in sedimentary basins,
it is the most common neoformed clay mineral replacing
mafic volcanic glass, microcrystalline mafic lava debris,
and Mg,Fe-silicates including olivine, pyroxene, amphi-
bole and biotite. During prograde transformation saponite
is replaced by corrensite, ordered 1:1 mixed-layered chlo-
rite/smectite (C/S), or vermiculite/chlorite; corrensite is in
turn replaced by trioctahedral chlorite in the late diagenetic
zone or low anchizone (Fig. 3). This series of reactions in
trioctahedral clays has been observed in a wide variety of
environments, including the prograde regional metamor-
phism of mudrocks from diagenesis through to the epizone,
in hydrothermal systems and in hydrothermally metamor-
phosed oceanic crust (Alt, 1999; Merriman & Peacor,
1999, and references therein). However, in the majority of
immature mudrocks, trioctahedral smectite is a scarce
component whereas chlorite is a common end-product of
this reaction series in mature mudrocks. This suggests that
the Fe and Mg necessary for chlorite formation is
contributed from other reactions, most likely from diocta-
hedral smectite where Fe + Mg is usually higher than in
reaction product illite (Hower et al., 1976; Drief & Nieto,
2000).
Although products of the kaolin 1:1 group of minerals
are reported as minor constituents of clay assemblages in
many mudrock sequences, it is not clear whether the trans-
formations shown in Fig. 3: kaolinite → dickite/nacrite
(+SiO2) → pyrophyllite form a reaction series. Examples
of kaolinite transforming to the 2-layer polytype dickite are
well known in sandstone lithologies (e.g. Ehrenberg et al.,
1993; Ruiz Cruz & Andreo, 1996). However, the kaolinite
→ dickite/nacrite transformation has not been widely
recorded in mudrocks, possibly because of problems with
the XRD identification of polytypic reflections from these
minerals in the presence of other clay minerals. Using TEM
techniques, Buatier et al. (1997) showed that kaolinite
transforms to dickite within black marls in a thrust-fault
zone. In aluminous, Fe-poor mudrocks, kaolinite will react
in the presence of quartz to form pyrophyllite, and this has
been mapped as a reaction isograde in very low-grade
metamorphic terrains (Frey, 1987).
The formation of intermediate metastable mixed-layer
minerals in dioctahedral and trioctahedral 2:1 clay minerals
suggests that this type of reaction progress obeys the
Ostwald step rule (Morse & Casey, 1988; Essene & Peacor,
1995). The rule recognizes that each phase transition
and/or crystal-structural modification in the reaction series
reduces the Gibbs free energy of the system, and with each
step the system approaches chemical (thermodynamic)
11
Fig. 4. Schematic diagram illustrating the Ostwald Step Rule as
applied to reactants and products in the smectite-I/S-illite-
muscovite reaction series. Direct transformation from smectite to
muscovite requires a large activation energy ∆Ga, and is unlikely in
a normal sedimentary basin setting. Transformation via a series of
intermediate products requires smaller activation energies, and is
kinetically more likely in sedimentary basins (modified from
Putnis, 1992; fig. 11.53).
equilibrium (Fig. 4). In the low temperature environment of
sedimentary basins, clay mineral transformations with low
total energy requirements are likely to be favoured in terms
of reaction progress (Stixrude & Peacor, 2002). Activation
energies are minimized in minerals related by similar
chemical compositions and/or crystal structure allowing a
sequence of reactants and products (reaction series) to form
in 2:1 dioctahedral and trioctahedral clay minerals
(Merriman & Peacor, 1999). Because of the metastable
nature of clay assemblages, the reactants and products of a
series may coexist and be closely intergrown. While it is
likely to be kinetically more favourable for clay minerals to
be produced by reactions within a given series, it does not
preclude reactions in one series contributing products to
another series, as indicated by the diagonal arrows in
Fig. 3. The example of dioctahedral smectite contributing
to chlorite-forming reactions has been mentioned above.
Further examples include that of kaolinite-bearing
mudstones and shales where illite or chlorite can form by
the breakdown products of kaolinite reacting with available
Fe and Mg (e.g. Boles & Franks, 1979), and dickite
replacement by illite in sandstones (e.g. Patrier et al.,
2003).
Mineral fabrics associated with prograde metamorphic
reactions have been widely recognized and recorded by
metamorphic petrologists. Although such fabrics are easily
observed in most meta-sedimentary rocks with a petrolog-
ical microscope, the submicroscopic fabrics found in
diagenetic and very low-grade mudrocks require more
powerful microscopes. During the past two decades, elec-
tron microscopic techniques have revealed two types of
diagenetic microfabric produced by the bedding-parallel
orientation of the a-b crystallographic plane of clay
12
Fig. 5. Transmission electron micrograph showing bedding-parallel
microfabric in illite. Note the absence of compaction or deflection
microtextures in straight illite crystals enclosing the rigid quartz silt
grain. Gulf Coast Shale, 4745m depth (TEM by Hailiang Dong).
minerals. Bedding-parallel microfabric in illite appears to
develop when the smectite-to-illite reaction has progressed
beyond 60 % illite in I/S (Fig. 5). The characteristics of this
microfabric include: a) straight, defect-free illite crystal-
lites replacing smectite crystallites with a high density of
defects (e.g. Dong et al., 1997); b) penetration of prograde
illite crystallites into pore space, such as compaction
shadows around rigid, non-clay detrital grains; c) termina-
tion of illite crystallites against rigid detrital grains at high
angles to the a-b crystallographic plane (e.g. Warr & Nieto,
1998; Merriman & Peacor, 1999). The development of
bedding-parallel microfabric replaces the random or
Fig. 6. Back-scattered scanning electron micrograph showing
bedding-parallel microfabric in chlorite-mica stacks. The stacks are
composed of chlorite (bright grey) and thin laminae of white mica
(mid to dark grey) sharing the same crystallographic a-b stacking
planes. Primary bedding lamination is orientated ENE-WSW; a
weak spaced cleavage cuts the lamination and is orientated WNW-
ESE. Despite the variation in size and shape of the stacks, the
stacking planes maintain the same overall bedding-parallel orienta-
tion. Silurian mudstone, central Wales (see Li et al., 1994).
R. J. Merriman
isotropic microfabric of diagenetic mudrocks and also
reduces porosity (Worden et al., 2003). These changes
represent the beginning of burial metamorphism.
A second type of bedding-parallel fabric is found in
chlorite-mica stacks that originated as detrital components
of some mud-turbidites (Fig. 6). The stacks are predomi-
nantly the products of the trioctahedral 2:1 reaction series,
and probably represent a variety of ferromagnesian mineral
grains, including biotite, and also mafic volcanic detritus.
Replacement of ferromagnesian and mafic detritus by
trioctahedral smectite occurred either during initial weath-
ering and transport or in the early stages of diagenesis. The
development of thin white mica laminae as intergrowths
with approximately the same orientation of the a-b crystal-
lographic plane as the host trioctahedral phase appears to
have occurred during late diagenesis or very low-grade
metamorphism (Dimberline, 1986; Milodowski &
Zalasiewicz, 1991). Some of the white mica laminae may
represent a by-product of the corrensite to chlorite reaction
(Fig. 3), whereas others formed by migration of K and Na
into the stacks (Li et al., 1994). Despite the varied shape of
the stacks, the stacking planes maintain an overall bedding-
parallel orientation in mudrocks that lack well-developed
tectonic fabrics. Both types of microfabric, in illite and
chlorite-mica stacks, are probably related to the approxi-
mately ground-parallel isocryst surfaces and mineral zones
found in burial metamorphic sequences (Roberts et al.,
1996; Neuhoff et al., 1997).
5. Basin maturity
Several factors contribute interactively to clay mineral
reactions rates in sedimentary basins, including heat flow,
fluid movement and composition, sedimentary overburden
and tectonic deformation. Although the products of clay
reactions cannot be used directly as geothermometers
(Essene & Peacor, 1995), correlation of reaction progress
with organic thermal maturity indicators (Merriman &
Kemp, 1996; Merriman & Frey, 1999) suggests that three
stages of basin maturity can be recognized in terms of clay
mineral evolution (Fig. 7). Immature basins contain sedi-
mentary sequences that have not passed through the oil
window and are dominated by neoformed and inherited
clays of the shallow diagenetic zone. Clays in this type of
basin may have experienced initially rapid reaction rates
during neoformation, for example palygorskite formation
in saline lakes and perimarine basins, but have not been
buried deeply enough to transform to more evolved clay
mineral assemblages. However, some rapidly subsided,
deep basins can remain immature because of low heat flow
and the reaction-inhibiting effects of overpressure on both
clays and organic materials (e.g. Carr, 1998). Clay mineral
assemblages in immature basins can provide useful infor-
mation on sediment provenance and mechanisms of
neoformation (e.g. Hillier, in press), and also provide
evidence of the distribution and sources of volcanogenic
clays (Jeans et al., 2000). Most commercial clay deposits
are found in immature basins, including bentonite, ball
clay, flint clay and brick clay.
 Clay minerals and sedimentary basin history
Fig. 7. Basin maturity chart correlating clay maturity zones and Kübler index of illite “crystallinity” with organic maturity indices and
hydrocarbon maturation zones. Modified from Merriman & Kemp (1996).
Mature basins contain sedimentary rocks that are
within the oil and gas windows. In terms of clay minerals
they are characterized by the partial transformation of
neoformed and inherited clays in response to deep diagen-
esis. Reaction rates are largely controlled by basin heat
flow. Hence high-heat flow basins, such as back-arc or
marginal basins, mature relatively rapidly under a thin
overburden, whereas low heat-flow basins such as fore-arc
basins and some passive margin basins are slow to mature
even under a thick overburden. The transformation of
smectite to illite is largely completed at this stage of basin
evolution, and has the effect of converting soft clays and
mudstone into well-lithified, brittle mudstones and shales.
Although a bedding-parallel microfabric may be generated
by illite crystal growth in the mudstone or shale, tectonic
fabrics are usually absent or very weakly developed.
Reaction progress can be measured using % illite in I/S, or
clay “crystallinity” (see below), and used to characterize
hydrocarbon zones (e.g. Pollastro, 1993), and estimate
maximum palaeotemperatures (Środoń & Clauer, 2001).
Dating of illite using the K-Ar technique can be used to
model the burial history of mature basins (Środoń, 2002).
Supermature basins generally lack any hydrocarbon
potential and represent the early stages of regional meta-
morphism. In basins of this type deformation plays a
crucial part in completing the transformation of metastable
diagenetic and inherited clays to equilibrium assemblages
of white mica (including muscovite, phengite, paragonite)
and chlorite. Deformation also returns overpressured
basins to hydrostatic pressures, so that any retardation of
13
reaction progress in clays is restored (e.g. Colten-Bradley,
1987). Tectonic fabric formation may be initiated in the
low anchizone by mechanical kinking and rotation of
detrital grains, and crenulation of bedding parallel micro-
fabric in clays (van der Pluijm et al., 1998). As tempera-
tures increase through the high anchizone and epizone
(Fig. 7), chemical processes such as dissolution/precipita-
tion, and mechanical processes including intracrystalline
deformation and dislocation creep, contribute interactively
to the crystal growth of metamorphic phyllosilicates
(Merriman et al., 1995; Árkai et al., 2002). White micas
that develop in tectonic fabrics can be used to date
cleavage-forming events in supermature basins using
40Ar-39Ar laser microprobe techniques (Sherlock et al.,
2003).
Three types of observation and measurement, detailed
in Merriman & Peacor (1999), can be made to assess reac-
tion progress in transformed clay mineral as an indication
of sedimentary basin maturity:
The clay mineral assemblage
Quantification of mixed-layer minerals
Clay mineral “crystallinity” – Kübler and/or Árkai index
Clay mineral assemblages. In a typical mudrock, the
clay mineral assemblage comprises the products of two or
more reaction series and can be used to indicate the state of
reaction progress in terms of metapelitic grade (Merriman
& Peacor, 1999, fig. 2.1) or the clay mineral maturity zones
shown in Fig. 7. Because of the metastable nature of clay
assemblages, the reactants and products of a series may
coexist and be closely intergrown. As a consequence it is
14 R. J. Merriman

Fig. 8. Schematic plot illustrating the time taken for some clay minerals to progress from mature to supermature (very low-grade meta-
morphic) assemblages in different sedimentary basin settings. The x-axis shows typical geothermal gradients for a range of basin settings.
The y-axis is a log-scale estimate of the geological time interval between basin formation and the transformation to a supermature clay
mineral assemblage.

not possible to limit the stability of a particular clay
mineral to a single zone. As general rule however, the pres-
ence of neoformed clays such as smectite and kaolinite in
assemblages is a good indication of an immature stage of
basin evolution (shallow diagenetic zone), whereas an
assemblage of mature illite-muscovite and chlorite indi-
cates a supermature basin (Fig. 7). Most mixed-layer
minerals are formed when immature clays are transformed
to mature mudrocks, i.e. the shallow-to-deep diagenetic
zone transition (Fig. 7), and become scarce or absent in
supermature basins.
Quantification of mixed-layer minerals. Early reaction
progress in 2:1 layer silicates (Fig. 3) generates mixed-
layer clays with varying proportions of reactant and
product. Measurement of the proportions and degree of
ordering in the smectite-I/S-illite reaction series is the most
widely used indicator of reaction progress for the immature
to mature stage of basin evolution (Środoń, 1999, and
references therein). NEWMOD computer modelling of the
mixed-layer components has become the standard tech-
nique of quantification (Moore & Reynolds, 1997).
Clay mineral “crystallinity”. This type of XRD
measurement has been widely used as an indicator of reac-
tion progress in mudrock lithologies found in mature and
supermature basins. The Kübler index of illite “crys-
tallinity” (KI) can be used to indicate reaction progress
when the smectite-to-illite reaction has progressed to
> 80 % illite. The KI technique measures changes in the
width of the first basal reflection of dioctahedral illite-
muscovite at an XRD spacing of approximately 10 Å. The
width of the 10-Å peak is inversely related to the thickness
of illite-muscovite crystallites, as shown by TEM crystal-
lite thickness measurements and predicted by the Scherrer
equation (Warr & Nieto; 1998; Merriman & Peacor, 1999).
Progress in the trioctahedral 2:1 reaction series can be also
be monitored using the Árkai Index of chlorite “crys-
tallinity” (Árkai, 1991; Guggenheim et al., 2002). This
measurement also provides a useful link with mineral
facies indicators of grade in meta-igneous rocks (Árkai &
Ghabrial, 1997).
6. Clay mineral maturity rates
As discussed in Section 2, the history of clays in sedi-
mentary basins largely depends on geotectonic setting. Clays
in some basins are uplifted and recycled in less than 1 million
years whereas those in other basinal sequences survive for
orders of magnitude longer. Since differences in heat flow
are the main distinguishing characteristic of the various
geotectonic settings where basins develop, to what extent
does thermal history influence clay mineral maturity rates?
Heating rates in sedimentary basins, which are in the
range 1-10°C/million years, are derived from the product
of the geothermal gradient (°C/km) and sedimentation rates
(metres/million years). Where sedimentation rates are
unknown, as is often the case, basin thermal history is
commonly described in terms of geothermal gradients,
which are typically in the range 15-60°C/km. In Fig. 8,
typical geothermal gradients for basins developed in
different geotectonic settings have been used schematically
to illustrate how long clays appear to survive as immature
or mature clays before transforming to equilibrium assem-
blages typical of supermature basins. It must be empha-
 Clay minerals and sedimentary basin history
sized that the information used to construct Fig. 8 was diffi-
cult to come by, and in some cases depended on experi-
enced guesswork, largely because clay mineralogists in the
past paid scant attention to basin type or thermal history
when sampling clays for analysis. Given these shortcom-
ings, Fig. 8 indicates that the oldest immature clay minerals
are likely to be found in mid-continental ‘sag’ basins or
failed rifts, and may survive for up to 2000 Ma. In basins
of this type a combination of low or medium geothermal
gradients and non-pervasive tectonic events, such as
faulting but not fabric-forming events, generally results in
low maturity rates. For example, in the Middle Proterozoic
Lake Superior Basin, a mid-continental rift, the Nonesuch
Formation contains immature 1Md illite-rich I/S and a one-
layer chlorite, indicating that matrix clays are still at the
deep diagenetic stage of basin evolution 1100 Ma after
deposition (Li et al., 1995). An older example is provided
by the Middle Proterozoic Kombolgie Supergroup, 1800
Ma, deposited in the mid-cratonic McArther Basin,
Northern Territories, Australia. Diagenetic dickite in sand-
stone pores is preserved but locally replaced by deep diage-
netic illite when the sequence was buried to depths of 5 km
or more (Patrier et al., 2003).
At the higher geothermal gradients shown in Fig. 8, in
basins such as the Pannonian Basin system, clay mineral
maturity rates are relatively rapid, reaching the mature
basin stage by simple burial in 8-10 Ma (Hillier et al.,
1995). In very high heat-flow geothermal systems, such as
the Salton Sea geothermal field, clays reach the super-
mature stage during a heating event that lasted 10,000 years
(Yau et al., 1988; Velde & Lanson, 1993), i.e. up to three
orders of magnitude quicker than relatively high heat-flow
sedimentary basins. However, at the other end of the range
of typical geothermal gradients, clays in accretionary
complexes assembled under very low heat flow conditions
may also mature rapidly, particularly where they have been
tectonised. In the Barbados accretionary complex, for
example, the smectite-to-illite transformation is initiated at
temperatures of only 30°C below a major décollement zone
(Buatier et al., 1992). Moreover, when clay-rich rocks are
subducted and underplated, lattice strain resulting from
accretionary tectonism plays a significant role in
progressing clay reactions through the mature → superma-
ture transformation (Merriman et al., 1995).
The general conclusion to be drawn from Fig. 8 is that
the rate at which clay mineral reactions progress from
mature to supermature assemblages can range from 1 x 104
to 2 x 109 years (or more), and both heat and tectonism
contribute to the more rapid rates of maturation.
Although clay mineral maturity and organic maturation,
particularly vitrinite reflectance (R0 %), can be correlated
in simplified diagrams, such as Fig. 7, it is widely recog-
nized that these two types of shallow crustal materials
mature at different rates. Both Robert (1985) and Kisch
(1987) suggested that clay mineral reactions tended to be
slower to respond to temperature increases than vitrinite
reflectance. This is perhaps to be expected given the
different nature of reaction progress in these two materials.
Vitrinite maturation progresses by loss of water, carbon
dioxide, methane and higher hydrocarbons, and as these
15
are eliminated the initially amorphous kerogen solids are
progressively aromatised to incipient graphite crystals.
Clay minerals on the other hand are usually crystalline
throughout the reactions that typically occur during basin
diagenesis, and the greatest loss is water that may mobilize
variable amounts of cations such as Ca, Na, K and Si.
Differences in the reaction kinetics of clay and organic
materials were demonstrated in a study of the Pannonian
Basin System by Hillier et al. (1995). They found that
correlation between R0 % and progress in the smectite-to-
illite reaction varied systematically from one sub-basin to
another. In sub-basins characterized by lower heating rates
the smectite-to-illite reaction is advanced in relation to
R0 %, whereas smectite-to-illite reactions are retarded rela-
tive to R0 % at higher heating rates.
Similar differences at more advanced stages of basin
maturity are shown in Fig. 9, where two trends are
displayed. A plot of Kübler indices and R0 % values derived
from a wide range of basin types and covering a broad
spectrum of geothermal gradients, from 15-45°C/km, is
labeled a ‘normal’ correlation curve. A similar trend was
identified by Underwood et al. (1993). A second curve was
derived from coal-bearing Carboniferous strata in the
South Wales Coalfield (White, 1992), and the Clare
Coalfield in southern Ireland (Wagner, 2003). The South
Wales Coalfield appears to have experienced high heat
flow (50-75°C/km) that matured coals to anthracite rank
(Alderton & Bevins, 1996), and the Clare Coalfield is
suspected to have a similar history. The two curves suggest
that at high heating rates vitrinite matures more rapidly
than illite but maturation of vitrinite is slower where the
normal geothermal gradients of burial diagenesis and very
low-grade metamorphism apply.
A significant difference between the mudrocks repre-
sented by the two curves in Fig. 9 is the development of
slaty cleavage fabrics. In the case of the ‘normal’ heat-flow
data, the mudrocks with KI values less than 0.30∆˚2θ have
a well-developed penetrative slaty cleavage (e.g. Merriman
& Peacor, 1999, fig. 2.1). In contrast, the mudrocks from
which data for the high heat-flow curve were derived lack
any cleavage fabric, even those with R0 > 5 % (Wagner,
2003). Again, this emphasizes the importance of tectonism
in progressing clay reactions through the mature → super-
mature transformation, and underlines the conclusions of
Essene & Peacor (1995) that clay mineral reactions are not
accurate geothermometers.
7. Geotectonic setting and clay minerals
The range of tectonothermal conditions under which
sedimentary basins evolve (Fig. 8) suggests that the clay
mineral assemblages developed should be indicative of
different geotectonic settings. But can differences that may
developed at the immature or mature stages of basin evolu-
tion be preserved in supermature clay mineral assemblages
that result from low-grade metamorphism?
Very few studies have made detailed regional compar-
isons between clay minerals generated in different geotec-
tonic settings. Recently, Merriman (2002b) reviewed
16 R. J. Merriman

Fig. 9. Plot of vitrinite reflectance R0 % against the Kübler index of illite “crystallinity”. The curve labeled ‘normal’ heat flow represents
a wide variety of basin types, and is based on unpublished and published data (Dalla Torre et al., 1996). The curve labeled high heat flow
is based on data from Carboniferous strata in the South Wales Coalfield (White, 1992), and the Clare Coalfield in southern Ireland
(Wagner, 2003).

regional differences in clay mineralogy found in British
Lower Palaeozoic slate belts formed during Caledonian
terrane amalgamation, completed approximately 400 Ma
ago. The different clay assemblages and clay microfabrics
found in extensional basins were contrasted with those
found in convergent basin settings (Fig. 10). Mature and
supermature stages of clay mineral evolution (Fig. 7) are
preserved in both settings. The extensional back-arc basins,
characterized by high heat flow (> 35ºC/km) and
volcanism with localized hydrothermal activity, contain a

Fig. 10. Schematic diagram illustrating differences in clay mineralogy typical of convergent and extensional basin settings in British
Caledonian terranes (Merriman, 2002b).
 Clay minerals and sedimentary basin history
greater diversity of clay minerals, including K-, K/Na- and
Na-micas and pyrophyllite, as well as chlorite/mica stacks.
K-white micas in these assemblages are typically alumi-
nous with b cell dimensions < 9.01 Å. Convergent basins,
characterized by low heat-flow (< 25ºC/km) tend to have
simple clay mineral assemblages of K-white mica and
chlorite, and the K-micas are phengitic with b cell dimen-
sions > 9.02 Å (Stone & Merriman, 2004).
The Na-micas and diversity of clay mineral assem-
blages found in the extensional basins may have been
generated by interaction between hydrothermal systems
and seawater, producing fluids with high Na/K ratios
(Merriman, 2002b). Paragonitic alteration appears to be a
feature of modern mid-oceanic hydrothermal systems
(Honnorez et al., 1998). The Trans-Atlantic Geotraverse
(TAG) found that extensively chloritized basalts subse-
quently reacted with alkali-enriched fluids with high Na/K
ratios generated by mixing hydrothermal fluids with
seawater. These reactions, at temperatures of 250-360°C,
produced the quartz + paragonite + pyrite assemblages that
characterize the main TAG stockwork (Alt & Teagle, 1998).
Paragonite and mixed Na-K-white micas have also been
recorded from extensional settings in Crete (Christidis et
al., 2003), and in the Eastern Taurides, Turkey, from very
low-grade Palaeozoic mudrocks (Bozkaya et al., 2002).
Bedding-parallel microfabric in illite, and bedding-
parallel stacking planes in chlorite-mica stacks are an addi-
tional characteristic of mudrocks found in the Caledonian
extensional basins, but not found in the convergent basins
(Merriman, 2002b). These microfabrics appear to develop
in response to high heat flow causing clay reactions during
‘static’ (non-tectonic) burial metamorphism in the exten-
sional basins. The absence of bedding-parallel clay micro-
fabrics in Caledonian convergent basins, particularly the
accretionary complex of the Scottish Southern Uplands,
may be due to the timing of tectonic events in relation to
trench deposition in such settings. Deposition, deformation
and burial metamorphism by thrust stacking are almost
synchronous events in the accretionary Southern Uplands
terrane (Stone & Merriman, 2004), and probably prevented
or disrupted the growth of ‘static’ microfabrics. In their
place, tectonic microfabrics have developed and are
commonly parallel or subparallel with bedding because of
the effects of bedding plane slip during imbrication of the
accreted tectonostratigraphy (Merriman et al., 1995).
In addition to clay mineral assemblages and clay micro-
fabrics, variation in the b unit cell dimension of illite-phen-
gite-muscovite (K-white mica) have provided reliable
indicators of geotectonic setting in British Caledonian
terranes. Using data from a range of British Lower
Palaeozoic mudrocks, Stone & Merriman (2004) showed
that the largest b dimensions are found in convergent basin
setting, representing the intermediate to high pressure
facies series with low geothermal gradients (Table 1).
Independent assessments of the heat flow characteristics in
these basins suggest geothermal gradients of 15-25°C/km.
Smaller b dimensions were found in extensional basins,
corresponding to the low-pressure facies series with the
highest geothermal gradients. Once again the gradients
inferred from Table 1 are in agreement with independent
17
Table 1. K-white mica b dimensions and pressure facies series
(Guidotti & Sassi, 1986).
Facies series bÅ Inferred geothermal gradient
low pressure <9.000 >35°C km-1
intermediate 9.000-9.040 25-35°C km-1
high pressure >9.040 <25°C km-1
estimates, particularly for the Welsh Basin (e.g. Bevins &
Merriman, 1988; Roberts et al., 1996).
The b dimension data presented by Stone & Merriman
(2004) suggests that the phengite content of K-white micas
generated in mature and supermature sedimentary basins is
a useful indicator of geothermal conditions rather than
geobarometric conditions.
8. Summary
Clay minerals in sedimentary basins are part of a cycle
of tectonothermal events that degrade and regenerate rock
in the Earth’s crust (Fig. 1). Neoformed clay minerals,
generated by surface weathering and shallow diagenetic
processes, are transformed into mature clay mineral assem-
blages as sedimentary basins are filled, deformed and
metamorphosed. Because of their crystal-chemical proper-
ties, neoformed clay minerals are hosts for a suite of alkali
elements and boron that are released during metamor-
phism. At active plate margins the release of these mobile
elements promotes magma generation, and when the prod-
ucts of these magmas are weathered they are recycled
largely as clay minerals, representing the magma-to-mud
pathway of the clay cycle.
The transformation of neoformed and inherited clays
within sedimentary basins can be characterized by a series
of reactions in 2:1 dioctahedral and trioctahedral minerals
(Fig. 3). These reactions generally obey the Ostwald Step
Rule, i.e. they represent an approach to chemical equilib-
rium through a series of crystal-chemical changes that
sequentially reduce the free energy of the system (Fig. 4).
Bedding-parallel microfabrics in clays generated by these
reactions provide submicroscopic evidence of the early
stages of burial metamorphism in mudrocks (Fig. 5, 6).
Several techniques can be used to indicate reaction
progress in clays as they mature in sedimentary basins. By
correlating clay reactions with organic thermal maturity
indicators three stages of basin maturity can be recognized
(Fig. 7). Immature basins are characterized by neoformed
and inherited clays of the shallow diagenetic zone that have
not been buried deeply enough to transform to more
evolved clay mineral assemblages. Most commercial clay
deposits are found in immature basins. Mature basins are
within the oil and gas windows, and are characterized by
the partial transformation of neoformed and inherited clays
in response to deep diagenesis. The transformation of
smectite to illite is largely completed at this stage of basin
evolution. Supermature basins have reached the early
stages of regional metamorphism where metastable diage-
18 R. J. Merriman
netic and inherited clays have been largely transformed to
equilibrium assemblages of white mica and chlorite.
The rate at which clay minerals react to form equilib-
rium assemblages ranges from 1 x 104 years in some
hydrothermal systems, to more than 2 x 109 years in some
mid-continental rift basins. The most rapid rates are found
along active plate margins, where both heat flow and
tectonism contribute to clay maturation (Fig. 8). In
contrast, immature or mature clay minerals are able to
survive for 2000 Ma or more in mid-continental rift basins
through a combination of low or medium geothermal gradi-
ents and non-pervasive tectonic events.
Clay mineral assemblages and the b cell dimension of
K-white mica can be used to infer the geotectonic settings
of sedimentary basins (Fig. 10). Mudrocks that evolved in
high heat-flow extensional basins may contain a diverse
assemblage of clay minerals, including K-, K/Na- and Na-
micas and pyrophyllite, as well as chlorite/mica stacks. K-
white micas in these assemblages are typically aluminous
with b cell dimensions < 9.01 Å. In contrast, mudrocks that
evolved in some convergent basins appear to have simple
clay mineral assemblages of K-white mica and chlorite, and
the K-micas are phengitic with b cell dimensions > 9.02 Å.
Acknowledgments: Earlier drafts of the article have bene-
fited from reviews by Simon Kemp, Alain Meunier and Jan
Środoń. Publication is by permission of the Executive
Director, British Geological Survey (N.E.R.C.).
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Received 2 April 2004
Modified version received 21 June 2004
Accepted 13 September 2004