SHALE

Devanarayanan EM
I.Msc Applied Geology
MINERAL COMPOSITION
Shales, also known as mud rock or clay rock, are very fine-grained
sedimentary rocks with a particle size less than 0.06 mm. This rock deposits
in terrestrial as well as marine environments.Shale is composed of quartz
and feldspar and major minerals with many accessory minerals. The major
minerals in shale are kaolinite, illite, and semectite. Other minor
constituents are organic carbon, carbonate minerals, iron oxide minerals,
sulfide minerals, and heavy minerals.Shale is distinguished from other
mudstones because it is fissile and laminated.
Shales may be classified as quartzose, feldspathic or micaceous shale
depending on the predominance of the minerals quartz, feldspar or mica,
respectively, in the rock after appropriate XRD analysis

Texture
Shales characteristically contain fine-grained silt and clay particles (<
0.063mm). They are therefore classified as silty shale or clay shale,
depending on whether silts or clays dominate in the constituents of the
rock. Silty shale and clay shale may collectively be called argillaceous shales.
Occasionally, shales may also contain appreciable amounts of sands, in
which case they may be called sandy shale or arenaceous shale.
Elemental Distribution
Silicon, aluminum, titanium, zirconium, and gallium generally are the
principal elements in the detrital mineral fraction of these rocks.
Locally, boron, beryllium, scandium, and vanadium are also in the
detrital fraction. Calcium, magnesium, and manganese are associated
chiefly with the carbonate-mineral fraction, where present. Different
groups of elements are associated with the organic-matter fraction of
these rocks in the different sets of samples.
Physical properties
Presence of shale in a reservoir:

● decreases the reservoir quality (porosity, permeability);

● creates an additional electrical conductivity component—any formal

application of Archie's equation results in an overestimate of water saturation.

The electrical properties of clay minerals surrounded by an electrolyte (water)

act as a second conductivity component in addition to the electrolytic
conductivity of the formation water in the connected pore space.
This conductivity contribution of shale/clay depends on:

● shale type (clay mineral);

● shale content (volume fraction );

● distribution of shale in the formation (laminar shale, dispersed shale,

structural shale).

A parallel conductor system of the two conductivity components is the

philosophy of most shaly-sand models.
The mineral and petrographic composition of shale rocks is investigated by
means of petrographic analysis.

Petrographic analysis is used to determine the following characteristics of the

tested rocks:

●mineral composition,

●origin of particular constituents,

●texture (layout and distribution of grains, the degree in which they fill the
rock spaces),

●structure (grain size and shape),pore space characteristics (size, type and
interconnections of empty voids and micr-fractures).
Shale rocks are frequently very heterogenous at a small scale.

Standard examinations of shale rocks include the determination of the

mineral composition using:

● XRD (X-ray diffraction),

● petrographic thin section studies (using both transmitted light and

cathodoluminescence – CL), and

● SEM (scanning electron microscope) analyses.

XRD analyses of mineral composition are intended to establish the

presence of specific minerals (qualitative analysis) or their percentage
share (quantitative analysis). In some of the samples detailed quantitative
XRD studies of clay minerals are made
Depositional Environments
 Shales are typically deposited in very slow moving water and are often
found in lakes and lagoonal deposits, in river deltas, on floodplains and
offshore from beach sands. They can also be deposited in sedimentary
basins and on the continental shelf, in relatively deep, quiet water.
Clay Minerals (Shale minerals)
There are three main groups of clay minerals:

Kaolinite - also includes dickite and nacrite; formed by the decomposition of

orthoclase feldspar (e.g. in granite)

Illite - also includes glauconite (a green clay sand) and are the commonest clay
minerals; formed by the decomposition of some micas and feldspars;
predominant in marine clays and shales

Smectites or montmorillonites - also includes bentonite and vermiculite;

formed by the alteration of mafic igneous rocks rich in Ca and Mg; weak
linkage by cations (e.g. Na+, Ca++).
Clay Minerals are Phyllosilicates:

The kaolinite clays are 1:1 phyllosilicates

The montmorillonite and illite clays are 2:1 phyllosilicates

Kaolinite Al2Si2O5(OH)2
Kaolinite clays have long been used in the ceramic
industry, especially in fine porcelains, because they can be
easily molded, have a fine texture, and are white when
fired.

Kaolinite is the purest of clays, meaning that it varies little

in composition. It also does not absorb water and does
not expand when it comes in contact with water.
Thus,kaolinite is the preferred type of clay for the ceramic
industry.
This layer is coupled to a gibbsite-like layer consisting of octahedral aluminium
bonded to four OH units and two oxygen atoms. These layers are joined as
sheets to other layers and may form a large set of clay layers known as a kaolinite
book.Kaolinites may be classified according to their order. A highly ordered
kaolinite is a kaolinite with very few defect structures and the stacking is perfect.

In X-ray crystallography various techniques have been employed to provide

some measure of this order. One such technique known as the Hinckley index is
based upon the ratio of intensity of peaks in the XRD pattern. Kaolinites with
many defects in the stacking are known as disordered kaolinites.

The inner hydroxyl points towards the ditrigonal cavity of the siloxane layer. The
inner surface hydroxyls point away from the surface and hydrogen bond to the
next adjacent siloxane surface.
Illite

Illite has a layer charge of about 0.8 per half-

cell formula unit, intermediate between
smectite and mica. Grim et al. (1937) developed
the term illite to describe clay-size mica that
was found in argillaceous rocks. Other terms
that have been used in lieu of illite are
hydromica, hydromuscovite, hydrous illite,
hydrous mica, K-mica, micaceous clay, and
sericite. Illite has more Si4+, Mg2+, and H2O
but less tetrahedral Al3+ and K+ and water
than muscovite. While K+ is the predominant
interlayer ion along with divalent ions such as
Ca2+ and Mg2+, NH4+ can also occur in illite.
This reaction involves an increase in layer charge to accommodate the K+
in place of the more weakly bonded exchangeable cations in the
smectite. This is achieved through substitution of Al3+ for Si4+ in
tetrahedral sites and a reduction in octahedral iron. In fact, many
sandstones have pore fluid in thermodynamic equilibrium with illite, but
little precipitation occurs due to an extremely low kinetic precipitation
rate at temperatures of less than 120°C.
Smectite
Montmorillonite or smectite is family of
expansible 2:1 phyllosilicate clays having
permanent layer charge because of the
isomorphous substitution in either the
octahedral sheet (typically from the
substitution of low charge species such as
Mg2+, Fe2+, or Mn2+ for Al3+)The most
common smectite is Montmorillinite, with a
general chemical formula:

(1⁄2Ca,Na)(Al,Mg,Fe)4(Si,Al)8O20(OH)4.nH2O
Smectite group includes dioctahedral aluminum micas of montmorillonite–
beidellite and nontronite series or Fe–smectite belonging to clay minerals.

The structure is made up of three-layer package, one layer of Al octahedron

sandwiched between two layers of SiO4 tetrahedra. Water molecules are set
between three-layer ions of Al, Mg and Fe. The package can expand or narrow
due to these ions, and manifests itself by changing of the volume or strong
swelling.

Smectite crystallizes in monoclinic system in the form of small sheets (<1 μm)
and can be explored only by the electron microscope and X-ray powder
diffraction and chemical analysis with the help of electronic microsonde.
 Uses
 Shales are commercially important, having many applications in the ceramics
industry in particular. They are a valuable raw material for tile, brick, and pottery
and constitute a major source of alumina for Portland cement. In addition, advances
in recovery methods may one day make oil shale a practical source for liquid
petroleum.
 Montmorillonite clay is used in some natural pet foods for a very specific purpose.
Pet food manufacturers add anti-caking agents to their formulas, to adsorb excess
moisture and help keep the food from clumping.
 Kaolinite, also called china clay, soft white clay that is an essential ingredient in the
manufacture of china and porcelain and is widely used in the making of paper,
rubber, paint, and many other products. 
 The crystallinity of illite has been used as an indicator of metamorphic grade in
clay-bearing rocks metamorphosed under conditions between diagenesis and low-
grade metamorphism. With increasing temperature, illite is thought to undergo a
transformation into muscovite.
 Oil shales
 Oil shale is an organic-rich fine-
grained sedimentary rock containing
kerogen from which liquid
hydrocarbons can be produced,
called shale oil.
 Shale oil is similar to petroleum, and
can be refined into many different
substances, including diesel fuel,
gasoline, and liquid petroleum gas
(LPG). Companies can also refine shale
oil to produce other commercial
products, such as ammonia and sulfur.
References
● Helmenstine, Anne Marie, Ph.D. (2018, October 22). Shale Rock: Geology,
Composition, Uses. Retrieved from
https://www.thoughtco.com/shale-rock-4165848

● A.M. Dayal, in Shale Gas, 2017

● RAY L. FROST, JANOS KRISTOF, in Interface Science and Technology, 2004

● Donald L. Sparks, in Environmental Soil Chemistry (Second Edition), 2003

● S.K. Haldar, Josip Tišljar, in Introduction to Mineralogy and Petrology, 2014

● J.M. Huggett, in Encyclopedia of Geology, 2005