1 Geology of Clays

B. VELDE

The chapters which follow deal with the occurrence of clays in nature. This
concerns the geology of clays: the geological processes which lead to the
creation of clays, the transformation of clays and the destruction of clays in
different geological environments. Clays, as is the case for most objects on the
Earth, are ephemeral. They have a life span which is governed by their geo-
logic history. Clays occur under a limited range of conditions in geological
space [time and temperature (essentially depth)]. They are found mainly at the
surface of the Earth: their origin is for the most part initiated in the weathering
(rock-atmosphere interface) environment. Some clays form at the water-
sediment interface (deep sea or lake bottom). A smaller number of clays form
as a result of the interaction of aqueous solutions and rocks, either at some
depth in the sedimentary pile or in the late stages of magmatic cooling
(hydrothermal alteration). Although, this last occurrence is not of great extent
it is very important to geologists as they have been called upon to aid human
activity. Hydrothermal alteration often leads to the accumulation of useful
heavy metals, such as gold, tungsten, and uranium. Therefore, when geologists
encounter rocks which have altered to clay, and they determine that this
occurred at depth (i.e. not weathering or superficial phenomena), they often
take a sample in order to assess the heavy metal content. In addition to the
accumulations of interesting metals, the extensive alteration of rocks due to
hydrothermal alteration can produce pure clay deposits which are also of
economic interest, e.g. clays for ceramics, and silica for industrial uses. Thus, as
is often the case, the rare occurrence is of greater interest to humans than the
more common, overall changes of geologic materials. However, in problems of
environmental importance, the general, common occurrence is of greatest im-
portance and the rare case is more of an anecdote. Environment is concerned
with the everyday, while industry is concerned with the exceptions.

1.1 Why Clays Form

Most clays are the result of the interaction of aqueous solutions with rocks.
The dissolution and recrystallization which occurs at this encounter is the
process by which clay minerals are formed and transformed. Clays are not
2 B. Velde

stable in anhydrous environments. The proportion of water, compared to that

of the solids (rock), which interacts determines the rate and type of chemical
reaction and ultimately the type of clay mineral formed. When large amounts
of water are present, the solids in the rock tend to be very unstable and they
dissolve for the most part. Dissolution is the first step of most water-rock
interactions. The greater the renewal of the water input (rain or fluid circula-
tion) the more dissolution will occur. As the ratio of water to rock approaches
one, the reactions are more and more dominated by incongruent dissolution,
in which certain elements go into solution and others remain in the solid state
in the skeleton of the altered rock. The new solids are generally clay minerals.
They are hydrated, having interacted with water, and they have a special
physical structure which is very different from that of the pre-existing minerals
which originally reacted with the aqueous solution. Because of their hydration,
the newly formed minerals have a greater volume than the original minerals.
Because the initial stages of alteration, and those that follow, include signifi-
cant dissolution of rock material, the formation of clays results in an aggregate
of lower density than the initial rock. During water-rock interaction voids are
usually produced in the alteration or clay-forming process. The proportion of
voids produced is a function of the relative amounts of water and rock which
interact.
In Fig. 1.1 the relationship of the relative amount of water available
compared to the interacting rock are indicated in such a manner that the
different types of geological phenomena which give rise to clay minerals are
outlined. Each of the geological environments indicated is the subject of a
chapter in this book. The geological environments are weathering, deposition
or sedimentation, burial which creates diagenesis and hydrothermal alteration.
In geology, when one thinks of environmental problems one is in fact thinking
of the interaction between man-made chemicals, or those chemicals that have
been concentrated by the industrial activities of humans. This initial thought is,
in fact, that of the soil-atmosphere interface. This is where agricultural chemi-
cals are used, where they are dispersed and, often, where they are eventually

water- rock

I H2O
I Sat ISolids

dissolution incongruent dissolution ppt solid-solid

reaction:
no clays clays + solution clays clay-clay
reactions
WEATHERING
DEPOSITION
Fig. 1.1. Interaction
DIAGENESIS levels and chemical
processes responsible
< HYDROTHERMAL ALTERATION ~ for clay minerals
 Geology of Clays 3

destroyed by bacterial action. The pathways by which surface waters reach

groundwater resources may bring the water into contact with compounds from
the use of agrochemicals. Industrial wastes, either released by intent or acci-
dent, can be considered in the same framework. In this context attempts to
centralize and neutralize man-made chemicals in waste disposal sites come
into prominence. The structure and clay mineralogy of soils and surface sys-
tems is very important to an understanding of the problems of agro-chemicals
and industrial pollution.
However, the environments of sedimentation and the burial of sediments
are also very important for the eventual cycling of toxic materials. Environ-
mental problems do not stop at the water table. For example, water-borne
contaminants will follow the paths of water flow into rivers and streams,
affecting the plant and animal life there. The sedimentation of suspended
matter (clays) into sedimentary reservoirs will capture or reject these contami-
nant materials, either isolating them from the biosphere or concentrating them
at certain levels. The sedimentary processes are important for environmental
problems. Burial will eventually isolate sediments and pollutants from the
biosphere. One must find out how this system works to be able to master its
potential.

1.2 Where Clays Form

The different clay mineral environments are, of course, related in space, at or

close to the surface of the Earth. The clay environment is limited to a certain
range of temperatures and it is also limited in time. For most clays stability is
in fact only attained at the very surface of the Earth, in say the upper several
hundreds of meters of the Earth's crust. When temperatures exceed 50 to
80°C the clays are unstable and they begin to change into other minerals,
either other clay minerals or different mineral structures such as micas,
feldspars, etc. The range of origin and evolution of clay, and its stability in time
and temperature coordinates is given in Fig. 1.2. The different geological

TIME

diagenesis

Fig. 1.2. Stability range of clays in T-t space un-

der weathering, sedimentation, burial diagenesis
and hydrothermal alteration conditions
4 B. Ve1de

environments such as weathering, sedimentation, burial diagenesis and

hydrothermal alteration form the subjects of major chapters in this book. Long
periods of time can cause changes in clay mineralogy. If temperatures are less
long lived, i.e. for periods of days or years, the temperatures needed for clay
formation can reach several hundreds of degrees centigrade.
The rate of change of clays is dependent upon temperature. This is the
common law for chemical reaction; the higher the temperature, the faster the
change. However, the rate of change in the temperature acting on the clays is
also variable. In geological situations one can have rapid heating, such as the
situation in which a magma intrudes a rock or a lava spills out onto the Earth's
surface. The rapid increase in temperature (many hundreds of degrees centi-
grade) can be effected in the space of days or years, this would be a short lived
geologic event. Tectonic events can produce fractures and thereby introduce
hot hydrothermal fluids (i.e. high temperature, undersaturated aqueous solu-
tions) Possibly associated with magmatic action. These fluids heat the rocks
locally at approximately the same rates as the intrusion of magma, but to lower
temperatures. Such events are rapid, and they create unstable mineral assem-
blages due to the high rate of thermal, and induced chemical, change. There-
fore, such assemblages are highly localized in the Earth's crust.
By contrast, the normal sequence of sedimentation and burial, formation
of sedimentary rocks from clay-rich sediments, is one that can take several
millions, or hundreds of millions, of years. One finds that clays are highly
transformed in some old, shallow basins (200 million years, 2km deep, low
temperatures of 80 DC) while they are much less affected in young deep basins
(2 million years, 5 km deep, temperatures of 180 DC). Thus, the dimension of
time can be as important as that of temperature in many instances of clay
stability and transformation.

soil

10

'l~ij~§~~s:e:dimentation
100

hydrothermal fluids

10~0!~
T -I- +.r-="I compaction
magma + and
hydrothermal
diagenesis
alteration
Fig. L3. The clay cycle in geological terms. Origin at surface leads to transport and deposition.
More deposition leads to burial and transformation, gradually into rocks which in turn can be
moved upward to be eroded and altered at the Earth's surface. Vertical scale is log of depth to
emphasize the scale of the events. The transformation of clays and their origin is at the surface
 Geology of Clays 5

In Fig. 1.3 one can see the spatial relations of depth and geological envi-
ronment where one finds clays. The vertical scale in the figure is logarithmic,
which de-exaggerates the importance of depth for the shallower phenomena.
In fact, most clays originate at the very surface of the Earth and begin their
migration shortly after their formation, by river transport, eventually reaching
large bodies of water such as littoral ocean environments. Hydrothermal al-
teration is revealed at or near the surface of the Earth by the action of erosion,
which brings deep-seated materials to the surface. As mountains are eroded
their roots are exposed to the eye and the use of mankind.
The contact of rocks and water produces clays, either at or near the surface
of the earth.

1.3 Clay Formation: The Chemical Necessity

The origin of clays is found in the interaction of rocks (silicate minerals) and
water. This indicates not only that clays are hydrous but also that clays are
more hydrous than the minerals in most rocks. The overall reaction of
rock + water ~ clay (1)
is a reasonable starting point. However, things are more complex than that.
The mechanism by which water "hydrates" silicate minerals that of hydrogen
exchange. Most clay minerals in fact contain (OH) molecules which have a
specific role in the mineral structure. The only difference between, say, a
potassium ion (K+) and a hydrogen ion (H+), contained in water, is that the
hydrogen ion can be expelled from the mineral structure at lower tempera-
tures than the potassium ion. In fact the potassium ion will be incorporated
into another mineral instead of leaving the solid phase, whereas the hydrogen
ion tends to form a gas (combining with oxygen to form water) leaving the
system when a high enough temperature is reached (usually between 400 and
600°C in clay minerals). In a very simple-minded way one can write the
stability of clays as
clay + heat ~ rock + water, (2)
which is roughly the reverse process of clay formation.
The chemistry of the hydration mechanism is one of exchange of cations
for hydrogen ions such as:
feldspar + hydrogen ions ~ clay (kaolinite) + cations, solids, water (3)
3KAISi30 g + 6H+ = AI2Si20s(OH)4 + 2K+ + 4Si02 + H 20.
In most clay-forming reactions, several phases are produced from an initial
mineral species and water. The reaction produces clays and other minerals.
Silica is a common by-product of hydration reactions; it can go into aqueous
6 B. Velde

solution or it can form a solid phase such as quartz or amorphous silica.

Production of clays is an incongruent process, one where solids and give rise to
solids and material in solution.
The chemistry of the reverse, dehydration mechanism can be written as
clay (kaolinite) = aluminosilicate + quartz + water, (4)
or,
AlzSizOs(OH)4 = AlzSiOs + SiOz + HzO.
The dehydration process creates water but no soluble ions in solution.
Thus the reactions are not "mirror images"; some materials is always displaced
from solids into solution in clay forming reactions. Reaction (3) is not equiva-
lent to reaction (4). Therefore, the origin of clays is in water and their destruc-
tion creates water; however part of the material of the initial anhydrous
mineral from which the clay forms is lost to the altering solution.
The altering aqueous solution finds its way, most often, into the ocean
where there is a large pool of dissolved ions derived from the alteration of
silicate minerals into clay minerals. The ions of greatest abundance are Na, K
and Ca. This transfer of material from one geologic environment, crystalline
rocks, to another, soils or clay deposits and aqueous solution, is a fundamental
process which is very important to an understanding of geological processes at
or near the Earth's surface. In this surface environment (aqueous and low
temperature) strong chemical segregations occur which effect redistribution of
material from one place to several others. Sediments and sedimentary rocks,
which are the solids resulting from alteration, tend to have compositions with
few elements present. For example, carbonate rocks have high Ca concentra-
tions, whereas sandstones are often over 90% Si02 , and highly evolved soils
tend to concentrate Al and Si.
Although the chemical necessity of exchange of hydrogen for mobile
mono- and di-valent ions is the motor of clay formation at the Earth's surface,
the process operates at different rates under different climatic conditions, and
is very often not fully achieved before erosion strips off the partially reacted
material. Sediments are most often a mixture of different phases in different
states of chemical equilibrium with each other. The amount of chemical
change is governed by the two determinant factors in reaction rate: time and
temperature. The higher the temperature, the faster the reaction proceeds and
the lower the temperature, the slower the reaction. Transformation of clays
and other metastable materials such as amorphous silica on the ocean bottom
(4°C) is very slow.
The range of temperatures in which clays form is from 4°C (ocean
bottom) to approximately 400°C (under short thermal pulses during
hydrothermal alteration). The time spans can range from hours (laboratory
experiments and intrusions) to hundreds of millions of years (burial
diagenesis). Since time is a factor, the reaction rate is critical and the relative
stability, or instability (distance from thermodynamic equilibrium), are the
 Geology of Clays 7

factors which determine the limits of the clay environmental conditons. Stabil-
ity, and the rate of reaction or the time necessary for it to be achieved, is
important for problems regarding burial containment, e.g. nuclear waste de-
positories. If clays are used in containment structures, they must maintain
their physical and chemical characteristics (remain stable) during periods of
time of up to a million years, in order to protect the future of humanity and to
a certain extent that of other species present. In regard to soil formation, clays
can form from rock fragments in hundreds of years and can form, or be
destroyed, in clay-rich samples in a similar time span. Thus the regeneration of
clays at the Earth's surface is a process which can take place on the time scale
of human life.
The process of hydration of solids, clay formation, occurs at the earth's
surface, but it is slow. This slowness means that some material is left in an
"unfinished" state, and is not in equilibrium with its fellow particles. This gives
the potential for transformation of altered products that is of the greatest
importance when dealing with clays. In a soil, one finds clay minerals formed
in place, one finds old but partially altered minerals from the parent rock and
one finds some original minerals in an un altered state. This aggregate material
has a high capacity for change, and it will continue to react if given enough
time. Thus sediments have a high reaction potential, both in their initial sites
of deposition and as they are buried and their ambient temperature increases.
If one changes the chemistry of the ambient soil or surface materials, for
example by introducing an alkaline or basic solution into their milieu, there
will be a high potential for mineral change. All the more so if the initial
materials are only partially reacted. Thus in pollution problems involving
chemical material there will be a high potential for change in the clay miner-
alogy of the surface material. Chemical spills in soils will certainly cause
change to the minerals present and hence their physical behavior. This change
can be hastened by changing the temperature of the system. Thus the stability
and reaction rate of clay mineral formation is of the greatest importance in
environmental problems.
The geologic causes of clay mineral formation are temperature change in
chemical change. The different environments of clay mineral origin will be
considered in much greater detail in the chapters that follow. However, one
should first have a working idea of the mineralogy (chemical composition,
crystal structure, and physical nature) of clay minerals, and this is found in the
chapter which follows.