© TGS, 2006 - Tulsa Geological Society Digest, Volume 24, 1956

Tulsa Geological Society Digest 47

CLAY MINERALS FROM THE VIEWPOINT OF THE

PETROLEUM GEOLOGIST

by
W. D. KELLER1

Abstract

Clay minerals, of great importance in the manufacturing, agricultural and

building industries, are possibly equally and fundamentally as important to the
petroleum geologist. They are often dominant in the argillaceous rocks and
are therefore perhaps the most important constituent of source rocks of
petroleum and rocks which form the seals in oil and gas traps. Also, on the
industrial side, certain clay minerals are used in drilling muds, and as catalysts,
decolorizers, absorbents and purifiers in refining.
In spite of their importance and abundance clay minerals are not easy
to identify and classify. For purposes of discussion of this factor they will be
referred to a group of minerals sufficiently similar in composition and struc-
tural properties to be called a mineralogical group. In the field a geologist
usually presumes that a fine grained, earthy, more or less soft and plastic rock
is composed of one or more clay minerals. These criteria are usually correct,
but may be deceptive. For instance, bauxite, some laterites, and other finely
divided earthy rocks may not be accepted in a classification as clay minerals.
Plasticity may be misleading; fine-grained calcite and dolomite mud and mar]
may be highly plastic. At the opposite extreme the flint fire clays of Missouri,
although they contain crystallized kaolinite, are highly non-plastic.
The physical characteristics of clays therefore are not absolutely depend-
able for the recognition of clay minerals. This invites the use of chemical
composition of materials for the identification of these minerals. The following
table gives such composition for representative minerals.

SiO.. 45.44 51.14 55.86 43.51 34.46 36.84 51.22 48.66

ALOs 38.52 19.76 0.13 2.94 16.95 3.50 25.91 8.46
Fe-O* 0.80 0.86 0.03 28.62 6.21 17.85 4.59 18.80
FeO 0.99 1.70 3.98
CrsO* 18.85
ZnO 0.10 23.10
MgO 0.08 3.22 25.03 0.05 1.10 2.84 3.56
CaO 0.08 1.62 Trace 2.22 1.39 0.16 0.62
K=O 0.14 0.11 0.10 0.49 6.09 8.31
Na=O 0.66 0.14 2.68 0.17
LiO= 1.05
TiO2 0.24
F 5.96
H=O 0.60 14.81 9.90 14.05 6.72
-105°
HsO 13.60 7.99 2.24 6.62 10.67 22.46 7.49 6.56
+ 105O
Total 100.08 99.75 102.98 100.02 99.95 100.89 100.17 99.08
100.47 0-F
1. University of Missouri, A. A. P. G. Distinguished Lecturer.
48 Tulsa Geological Society Digest

1. Kaolinite, Roseland, Va. Hydrous aluminum silicate. 9 Ross, C. S., and

Paul, 1930. The Kaolin minerals, U. S. Geol. Survey Prof. Paper 165E.
2. Montmorillonite, Montmorillon, France. Contains more silica and less
aluminum than kaolinite, plus some magnesium. Ross, C. S., and Hen-
dricks, S. B., 1945 Minerals of the Montmorillonite group, 17. S. Geol.
Survey Prof. Paper 205B.
3. Hectorite, Hector, Cal. Hydrous magnesium silicate with fluorine, lithium
and sodium. (Ross and Hendricks, 1945.)
4. Nontronite, Woody, Cal. Hydrous ferric silicate, with minor aluminum.
(Ross and Hendricks, 1945).
5. Sauconite, Friedensville, Pa. Hydrous zinc silicate. Ross, C. S., 1946. Sau-
conite—a clay mineral of the Montmorillonite group, Amer. Mineral., 31,
411-425.
6. Volkonskoite, Okhansk, Siberia. Hydrous chromium and iron silicate.
(Ross and Hendricks, 1945).
(All of the clays from 2 to 6, inclusive, are members of the montmorillon-
ite group.)
7. Illite, Fithian, Vermillion County, 111. Hydrous potassium aluminum sili-
cate (or hydrous mica). Grim, R. E., Bray, R. H., and Bradley, W. F.,
1937. The mica in argillaceous sediments, Amer. Mineral., 22, 813-829.
8. Glauconite, St. Joseph Lead Mines, Missouri. Hydrous potassium iron
(ferric) aluminum silicate. Hendricks, S. B. and Ross, C. S., 1941. Chemi-
cal composition and genesis of glauconite and celadonite, Amer. Mineral.,
26, 683-709.
° The references listed give the actual chemical formulas.
It is apparent from the table that clay minerals contain many metallic ele-
ments other than aluminum. Indeed, the only elements common to all the clay
minerals are oxygen, silicon and hydrogen, which in general are not definitive.
Hence it may be concluded that chemical composition is not a closely restric-
tive criterion. It is then necessary to look into their crystal or lattice structure.
X-ray crystallography shows clay minerals to be built of ions arranged
into geometrical patterns of sheet-like structures. In Figure 1 (which is the
only illustration presented with this abstract) the structure of kaolinite is
shown diagrammatically in cross section.
From bottom upward in the diagram the open circles are oxygen ions; the
solid black circles are silicon ions, which are so arranged that each silicon ion
has four nearest oxygen ions in tetrahedral distribution about it. Above the
silicon sheet is another sheet of oxygen and hydroxyl (double circle) ions,
then aluminum (cross-hatched) ions, hydroxyl ions, and so on. Looking upon
the oxygen and hydroxyl layers as being three slices of bread and the silicon
and aluminum layers as two layers of fillings, the arrangement may be called
a "two decker sandwich." This kaolinite crystal sandwich is 7.1 Angstrom
 Tulsa Geological Society Digest 49

/H04.5

Koolinite
FIGURE 1
Diagrammatic cross section through crystals of kaolinite. From Brindley, et al.

units thick (1 A is lO-'mm).

Proceeding with this sandwich idea, montmorillonite may be called a
"three layer sandwich" with 4 sheets of oxygen and hydroxyl ions and three
fillings; two of these fillings are of silicon and one of aluminum, the latter
being filling. Each of the silicon ions has the tetrahedral arrangement with
oxygen or hydroxyl ions which is characteristic of kaolinite, but in the central
filling each aluminum ion has six nearest oxygen or hydroxyl ions in octahedral
arrangement with it. The ion content of the central filling in the montmoril-
lonite group, rather than kaolinite, may be ferric iron, when the mineral is
nontronite; if magnesium, hectorite, if zinc and chromium, saucanite and vol-
konskoite, respectvely.
In the bentonite clays of the montmorillonite group trivalent positive alum-
inum ions in the central sheet may have divalent positive magnesium as a
substitute, in which case the crystal lattice becomes deficient by one positive
charge with each substitution. The electrical deficits may then be satisfied by
sodium of one positive charge, divalent positive calcium, or hydrogen of one
positive charge, etc. The bentonite of Wyoming usually carries ths positive
sodium ion, which is commonly hydrated with an accompanying molecular
film of water which brings about the familiar slippery swollen phase of ben-
tonite, these characteristics varying with the amount of hydration.
This possibility of exchange of ions gives rise to base exchange in the
montmorillonite group. If calcium is the replacement ion the permeability of a
sandstone in which it occurs may be satisfactory, since a large amount of
swelling does not occur. However, encroachment of salt water into the sand-
stone may bring about the replacement of calcium by sodium with resulting,
swelling and filling of pore spaces.
50 Tulsa Geological Society Digest

The illite or hydrous mica group also has a three layer sandwich structure,
but in this lattice the substitution of ions takes place significantly in the silicon
sheets rather than in the central sheet. Part of the quadravalent positive silicon
ions are replaceable by trivalent aluminum ions. Usually the deficit of one
positive electric charge for each such substitution is compensated by a
potassium ion. The potassium ion has characteristics which cause it to fit
snugly in the lattice framework, with the result that a non-swelling clay
mineral is formed. This is a factor in the differentiation of illite and the kao-
linite and montmorillonite groups.

In the chlorite type of clay minerals the lattice structure is essentially

an alternation of 3 layer and single layer sandwiches (the latter being brucite,
Mg (OH*). This type is common in shales, and there is evidence that they form
in place under sedimentary conditions as well as by deposition as clastic
material.

There are many other minerals which are classified as clay minerals.
Some are accepted by all investigators but some are excluded by others.
Defined, a typical clay mineral is a hydrous silicate of aluminum, magnesium
or iron, or, less commonly, zinc, chromium and vanadium, whose crystals are
sheet-like in structure, usually micaceous, fibrous or tubular in shape, colloidal
in size in one dimension at least, and which commonly develop plasticity when
sufficiently pulverized and wetted.

The processes of origin of clay minerals are tabulated in the following:

1. Crystallization of clay minerals from solution.

2. Weathering of minerals and rocks, including volcanic glass, by

(a) Cold "fresh" water, regularly renewed, usually more less carbonated.
(b) Supplemental action of macro- and micro-flora.
( c) Ocean water (briny).
(d) Lake water (various ionic concentrations).
3. Dialysis of clay minerals (Donnan effect) by
(a) Fresh water.
(b) Aided by supplemental action of plants.

4. Reconstitution of degraded clay minerals (inheritance of lattice energy)

by
(a) Restoration of M ions in vacated positions.
(b) Exchange or replacement of critical ions.
5. Hydrothermal alteration of solid rocks.
6. Laboratory synthesis at elevated temperatures and pressures.
Although clay minerals are sparingly soluble in pure water there is good
evidence that dickite and kaolinite have been deposited from solution in cav-
 Tulsa Geological Society Digest 51

ities within chert nodules and geodes. The formation of clay minerals by the
weathering of silicates, including those in volcanic materials, is foremost in
geologists' minds when considering the process. The chemical reactions by
which the silicate feldspar, for example, becomes clay minerals include hydro-
lysis, surface reactions, diffusion and ion exchange diffusion. Acceleration of
alteration takes place by a concentration of positive hydrogen ions derived
from carbonic, organic and other acids. Such a concentration promotes the
formation of kaolin minerals while a lack of these ions during hydration
brings about the formation of montmorillonite. The presence of calcium,
magnesium, sodium and potassium in the chemical system brings about the
different filling in the sandwiches previously described. In other words, the
sandwich formed during a geologic process is a reflection of both the parent
rock and the participating solutions. The word "climate" in reference to
geologic processes applies to the chemical environment of the alteration, or
to the conditions at the specific spot of the alterations. Such environments or
climates are classified as atmospheric; subsurface, either in or below the
upper soil; and subaqueous, either below the ground water table, in open
fresh water or open briny sea water. Temperature variations are important
since they affect chemical reactions and biological activity.

The rootlets of plants carry positive hydrogen ions which may be trans-
ferred to partially weathered minerals. Clay minerals themselves may coat
unweathered rocks and hasten their weathering. Bacteria in weathering and
the formation of clay minerals may not be fully appreciated, just as apprecia-
tion of their role in other geologic processes has been neglected.
Dialysis of clay minerals, by the Donnan effect, is illustrated by the re-
moval of potassium from illite through the movement of ions across a clay
surface permeable to ions. This is believed to have been an important factor
in the origin of Missouri fire clays, which are thought to have been formed by
accumulation of illite in marshes and low basins with potassium and other
metals passing from the clay particles by dialysis. The ions diffused upward into
water kept fresh by rains and the clay was thereby "purified" into fire clay.
If certain clay minerals are leached, dialysed or affected by the weather-
ing action of plant roots the crystal lattice of the clay mineral is partially de-
graded at first and completely destroyed as the degrading reactions become
more intense. However, in the early stages of this process the major struc-
tural units remain essentially intact because of the strong chemical bonds be-
tween oxygen, silicon and aluminum. If such a partially degraded clay moves
into an environment in which there are ions which can refill vacated sites in
the lattice structure a reconstitution of the clay mineral will occur. Such a
process may take place during the deposition and diagenesis of clay bearing
sediments. The type of clay mineral formed will depend upon the suitable
available minerals.
At temperatures above those of ordinary surface rocks, or those with the
so-called hydrothermal range, aqueous solutions may react with rocks and
minerals. Different clay minerals have been developed by such hydrothermal
alteration. They may form deposits in themselves or accompany ore bodies.
The minerals are simply the products of a chemical reaction as in other pro-
cesses of their formation.
52 Tulsa Geological Society Digest

There have been successful syntheses of clay minerals in different labor-

atories, including even the substitution of aluminum and silicon by ions of
minerals foreign to natural clay minerals. This work has served to strengthen
the conclusions which have been made concerning the geologic environment
of formation of the various clay minerals.

NORTH GARBER

by
VERNON R. BAKER1

EDITOR'S NOTE: We have not received an abstract of Mr. Baker's talk,

which dealt with the geologic and production history of the North Garber
Field, and with the prospects of the surrounding area. Apparently Mr. Baker
has spent much time in and around the field as consultant and participant in
the operations. Unfortunately, the date of his talk, December 19, was so close
to Christmas that many members were unable to attend the meeting and the
group that heard him was very small. So far as this editor is qualified to do so
he apologizes for a situation that might have been foreseen by himself as
secretary when he sent out the notices for the meeting.

'Phillips University, Enid. Oklahoma.