Introductory Concepts Final Draft, Revised 1/18/00 Page 1

IX. REFERENCES ................................................................................... 14

An Introduction to Soil Mineralogy X. LIST OF FIGURES............................................................................. 14
XI. LIST OF TABLES .............................................................................. 15
Darrell G. Schulze, Purdue University, West Lafayette

Table of Contents
I. CHEMICAL AND STRUCTURAL CLASSIFICATION OF
MINERALS ................................................................................................... 2
A. Composition of the Earth’s Crust ..................................................... 2
B. Definition of a Mineral ..................................................................... 2
C. Mineral Classification....................................................................... 2
1. Halide, Sulfate, and Carbonate Minerals ..................................... 3
2. Sulfides......................................................................................... 3
3. Oxides, Hydroxides and Oxyhydroxides...................................... 3
4. Silicates ........................................................................................ 4
II. PHYLLOSILICATE MINERALS IN SOILS ....................................... 4
A. Basic Structural Concepts................................................................. 4
1. Closest Packing of Spheres .......................................................... 4
2. Tetrahedra and Octahedra ............................................................ 4
3. Representing Tetrahedra and Octahedra ...................................... 5
4. Ionic Radii and Radius Ratios...................................................... 5
5. Tetrahedral and Octahedral Sheets............................................... 6
B. Phyllosilicate Minerals Common in Soils......................................... 7
1. The 1:1 Type Minerals ................................................................. 7
2. The 2:1 Type Minerals ................................................................. 7
C. Structural Details of Phyllosilicates.................................................. 9
III. OTHER ALUMINOSILICATE MINERALS COMMON IN SOILS 10
A. Zeolites ........................................................................................... 10
B. Allophane and Imogolite ................................................................ 10
IV. SOME CRYSTALLOGRAPHIC CONCEPTS .................................. 11
A. Periodicity in Crystals..................................................................... 11
B. The Unit Cell .................................................................................. 11
C. Miller Indices.................................................................................. 12
D. X-ray Diffraction ............................................................................ 12
1. Bragg's Law................................................................................ 12
2. The Scherrer Equation................................................................ 13
V. SUMMARY ........................................................................................ 13
VI. SUGGESTED READING .................................................................. 13
VII. QUESTIONS AND EXERCISES ...................................................... 13
VIII. ACKNOWLEDGMENTS................................................................... 14
Introductory Concepts Final Draft, Revised 1/18/00
An Introduction to Soil Mineralogy
Darrell G. Schulze, Purdue University, West Lafayette, Indiana
Minerals make up about one-half of the volume of most soils. They
provide physical support for plants and create the water- and air-filled pores
that make plant growth possible. Mineral weathering releases plant nutrients
that are retained by other minerals through adsorption, cation exchange, and
precipitation. Minerals are indicators of the amount of weathering that has
taken place and the presence or absence of particular minerals gives clues to
how soils formed. The physical and chemical characteristics of soil minerals
are important considerations in planning, constructing, and maintaining
buildings, roads, and airports. Soil minerals can adsorb many organic and
inorganic environmental pollutants, promoting their degradation to nontoxic
forms, attenuating their movement through the soil, or preventing their
uptake by plants and their introduction into the food chain. Some minerals
are themselves pollutants and can cause serious environmental problems
when they are exposed to weathering at the soil surface by man’s activities.
An understanding of soil mineralogy is central to understanding virtually all
facets of man’s use and misuse of soils and is often the key to solving
specific environmental problems.
This chapter develops a core of concepts and terminology needed for
understanding soil minerals. The chemical composition of the earth's crust is
discussed first to show that the most abundant elements in the crust are, not
surprisingly, the ones most likely to be encountered in soil minerals. Then
the chemical and structural classification of minerals is discussed and the
major minerals represented in soils are mentioned. The phyllosilicate
minerals are covered separately because of their major role in soils. Basic
structural concepts common to all minerals are covered at this point to
provide the background for the discussion of the phyllosilicate structures.
The overall structural theme of the phyllosilicates is then presented along
with a very brief summary of their most important properties. The chapter
concludes with a treatment of some crystallographic and x-ray diffraction
concepts used throughout the book.
I. CHEMICAL AND STRUCTURAL CLASSIFICATION OF
MINERALS
A. Composition of the Earth’s Crust
Most of the weight and volume of the earth's crust is made up by only a
few elements (Table 1-1). Oxygen and Si make up most of the weight, while
oxygen alone accounts for more than 90% of the volume. In general, the
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larger O atoms are in an approximately close-packed arrangement held
together by smaller metal atoms in the interstitial space. Most of the
elements in the crust and in soils occur in minerals. Thus, the elements listed
in Table 1-1 are major constituents of the minerals discussed in this book.
B. Definition of a Mineral
Klein and Hurlbut (1993) define a mineral as follows: "A mineral is a
naturally occurring homogeneous solid with a definite (but not generally
fixed) chemical composition and a highly ordered atomic arrangement. It is
usually formed by inorganic processes." Both chemical composition and
crystal structure (ordered atomic arrangement) are important parts of this
definition. Neither alone is sufficient to explain the properties of minerals.
Minerals with similar chemical composition but different crystal structures
— or, conversely, minerals with similar crystal structures but different
chemical compositions — can be quite different from one another despite
their chemical or structural similarities.
C. Mineral Classification
Although different classification schemes could be used, mineralogists
have determined that first separating minerals into groups based on their
chemical composition gives classes with the greatest similarities in many
other properties. Thus, minerals are first divided into classes depending upon
the dominant anion or anionic group. The classes include: (1) native
elements, (2) sulfides, (3) sulfosalts, (4) oxides and hydroxides, (5) halides,
(6) carbonates, (7) nitrates, (8) borates, (9) phosphates, (10) sulfates,
(11) tungstates, and (12) silicates (Klein and Hurlbut, 1993). These classes
are then subdivided based on chemical and structural similarities. This same
general classification is followed in this book, but with some exceptions.
Mineral classes such as the native elements, sulfosalts, nitrates, borates, and
tungstates that occur only rarely in soils, are covered only briefly or not at
all. Commonly occurring mineral classes, particularly the silicates, are
covered in detail.
Soil minerals are also referred to as either primary or secondary
minerals. Primary minerals form at elevated temperatures. They are usually
derived from igneous or metamorphic rocks, but they can be inherited from
sedimentary rocks as well. Secondary minerals are formed by low-
temperature reactions and are either inherited from sedimentary rocks or
formed in soils by weathering (Jackson, 1964). The separation of minerals
into primary and secondary mineral classes is not mutually exclusive and
some minerals can occur in both. The concept is useful however, and
appears widely in the soil science literature. The major mineral classes
represented in soils are discussed below.
Introductory Concepts Final Draft, Revised 1/18/00
1. Halide, Sulfate, and Carbonate Minerals
The major soil minerals of this group are halite (NaCl), gypsum
(CaSO4•2H2O), calcite (CaCO3), and dolomite [CaMg(CO3)2] (Table 1-2).
This group is characterized by minerals with relatively simple structures.
The halite structure is one of the simplest of all minerals. It consists of
alternating Na+ and Cl- ions arranged in cubic closest packing (Fig. 1-1). The
other minerals in this group have similar structures with cations such as
Ca2+, Mg2+, or Fe2+ alternating with anions such as S22-, SO42-, or CO32-. The
bonds between the cations and anions are predominantly ionic. These
minerals are among the most soluble and the softest of all soil minerals and
they are easily broken down by physical and chemical weathering processes.
They occur mainly in soils of arid regions or in youthful soils in more humid
regions, where weathering has been minimal.
Halite is the most soluble of this group and accumulates in only the most
arid environments. It is one of the minerals present in the salic horizon of
Aridisols. Gypsum is about 100 times less soluble than halite, but it too is
abundant only in arid regions. Gypsum is a major mineral in the gypsic
horizon of Aridisols. Halite and gypsum could also occur in soils that have
been contaminated by salt water, or by soluble salts leaching from industrial
stock piles or waste piles.
Calcite and dolomite are common carbonate minerals that occur in a
variety of soils. These minerals precipitate in the soil profile in arid and
semiarid climates (aridic and some ustic soil moisture regimes). Calcic and
petrocalcic horizons form if the accumulation is great enough. Carbonate
minerals in many soils are inherited from limestone or other calcareous
parent materials. Carbonates are usually stable and can be found throughout
the soil profile under aridic and ustic soil moisture regimes (arid to
subhumid climates), but are leached from the soil profile and are generally
present only in the C horizons under the udic soil moisture regime (humid
climates). Calcite and dolomite can be introduced into soils originally free of
these minerals via the limestone aggregate used for road construction in
some areas.
2. Sulfides
Pyrite, FeS2, the most common mineral in this group, does not occur
extensively in soils, but when it is present it causes some unique problems.
Pyrite precipitates in soils on wet tidal flats and river deltas of some coastal
areas and also occurs in some geologic formations originally deposited in
similar environments. Thus, pyrite often occurs in close association with
coal. Pyrite is unstable under oxidizing conditions and weathers quickly
when pyritic soils are drained or when mining leaves pyritic material on the
surface. The weathering products include the minerals jarosite,
KFe3(SO4)2(OH)6, and gypsum and sulfuric acid, H2SO4. The large amount
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of acidity causes problems in utilizing pyrite-containing soils and in
revegetating mined areas and is a serious and costly environmental problem.
3. Oxides, Hydroxides and Oxyhydroxides
Primary minerals break down during weathering and release cations and
anions that recombine to form other more stable minerals. Several elements,
in particular Al, Fe, and Mn, form oxide, hydroxide, or oxyhydroxide
minerals that are stable in the soil weathering environment. Representative
mineral species are given in Table 1-2.
a. Aluminum
Gibbsite, [Al(OH)3] is the most common Al hydroxide mineral in soils.
It is generally associated with the latter stages of weathering when leaching
of silica has progressed to the point that phyllosilicate minerals no longer
form. Gibbsite is common in highly weathered Oxisols of tropical regions. It
has a very low cation exchange capacity and contributes to the low native
fertility of most Oxisols. Gibbsite is also commonly found at the weathering
interface between igneous rock and saprolite and in Andisols formed from
volcanic ash. Despite the high solution silica content in these environments,
gibbsite precipitates as a metastable phase that eventually dissolves and
gives way to more silica-rich minerals (Sposito, 1989, p. 101).
b. Iron
Iron oxide minerals form from Fe released from primary minerals. Iron
oxides are strong pigments and small amounts of these minerals account for
most of the brown and red colors of soils. Goethite (FeOOH) is the most
common mineral of this group. It accounts for the brownish to yellowish
color of many soils, although it may be present in only small quantities.
Hematite (Fe2O3) is only slightly less common than goethite and usually
occurs in association with it. Hematite is usually bright red and is
responsible for the red color of many soils. Goethite and hematite are stable
minerals in an oxidizing environment. Large amounts of these two minerals
in well-aerated soils, usually in association with gibbsite and kaolinite,
usually indicate an advanced stage of weathering. In soils that are saturated
with water for at least some time during the year, the very insoluble Fe3+ in
goethite, hematite, and other iron oxides can be reduced to very soluble Fe2+.
The Fe2+ can easily move with the soil water to other parts of the soil profile,
or even to other associated soils in the landscape, where it can then reoxidize
to Fe3+ and reprecipitate as goethite, lepidocrocite, or ferrihydrite when
oxidizing conditions return. Repeated cycles of oxidation and reduction give
rise to mottles and nodules that reflect an inhomogeneous distribution of
iron oxide minerals within a soil. Soil scientists use these inhomogeneous or
mottled color patterns to estimate the depth to a soil water table and the
length of time the soil is saturated during the year. Thus, when delineating
wetlands, determining the best location for a septic system leach field, or
Introductory Concepts Final Draft, Revised 1/18/00
mapping soils, soil scientists rely on predictable soil color patterns that result
from iron oxide mineralogy and distribution.
c. Manganese
Manganese oxides and hydroxides (Table 1-2) are commonly found in
soils as brown or black nodules or as thin coatings on the faces of soil
structural units. They are often associated with Fe oxides. Manganese occurs
frequently as birnessite or lithiophorite in soils. Manganese can be oxidized
and reduced in the soil environment similar to iron. Thus, the
inhomogeneous distribution of Mn into nodules is an indicator of reduction
and oxidation as a result of periodic water saturation.
d. Titanium
Rutile and ilmenite (Table 1-2) occur in soils mainly as primary
minerals inherited from igneous rocks. Anatase is less common and is
generally considered a secondary mineral. Although frequently found in
soils, these minerals do not occur in sufficient quantity to impact soil
physical or chemical properties.
4. Silicates
The silicate mineral class is an extremely large and important group of
minerals. Nearly 40% of the common minerals are silicates, as are most
minerals in igneous rocks. Silicates constitute well over 90% of the earth's
crust (Klein and Hurlbut, 1993) and comprise the bulk of most soils as well.
Silicates occur as both primary minerals inherited from igneous or
metamorphic rocks and as secondary minerals formed from the weathering
products of primary minerals.
As explained in more detail below, the fundamental unit of all silicate
structures is the SiO4 tetrahedron. It consists of four O2- ions at the apices of
a regular tetrahedron coordinated to one Si4+ at the center. The individual
tetrahedra are linked together by sharing O2- ions to form more complex
structures. Several different arrangements of the SiO4 tetrahedra occur,
partly accounting for the large number of silicate minerals and providing the
basis for their classification. The tetrahedra may be present as single
tetrahedra (nesosilicates), double tetrahedra (sorosilicates), rings
(cyclosilicates), single or double chains (inosilicates), sheets (phyllosilicates)
or three-dimensional frameworks (tectosilicates) (Table 1-3). In most of
these arrangements adjacent SiO4 tetrahedra share corners, that is, they share
a common O2-. The more common minerals from each silicate class likely to
be found in soils are given in Table 1-3.
The most common minerals in igneous rocks are the olivines,
pyroxenes, amphiboles, micas, feldspars, and quartz. These primary minerals
predominate in the sand and silt size fractions of soils. The clay (<2 µm)
fraction of most soils is dominated by phyllosilicate minerals. Because of
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their importance in soils and sediments, phyllosilicates are discussed in
detail below and in other chapters of this book.
II. PHYLLOSILICATE MINERALS IN SOILS
Phyllosilicate minerals strongly influence both the chemical and
physical properties of soils because of their generally small particle sizes,
high surface areas, and unique cation exchange properties. A clear
understanding of the phyllosilicate minerals is central to understanding soil
clay mineralogy and many environmental processes.
The discovery in the early 1920's that clays are crystalline was the key to
understanding many of the properties of soils and clays. The crystal
structures of the phyllosilicates define the different mineral species and
account for many of their unique properties. The structural schemes of these
minerals are discussed in sections II and III. The purpose is to give an
overview of the most commonly occurring structures and on the major
properties of each major mineral group. Subsequent chapters will add
details, if necessary. Emphasis will be placed on developing an
understanding of the various structural representations encountered in the
literature.
A. Basic Structural Concepts
The following discussion will treat atoms as rigid spheres. This is an
oversimplified but convenient model for developing the key concepts of
mineral structures.
1. Closest Packing of Spheres
The most efficient way of packing spheres in one plane is called
hexagonal closest packing (Fig. 1-2). Each sphere touches six of its
neighbors and a hexagon results if the centers of these six neighbors are
connected. There are two types of voids between the spheres: "A" voids
where the triangular outline points downward in the figure, and "B" voids
where the triangular outline points upward. If a second plane of spheres is
placed on top of the first (Fig. 1-3), and if the first sphere of the second
plane is placed in the dimple formed by the three spheres surrounding an A
void, then all the remaining spheres of the second plane must be placed over
A voids as well. The spheres illustrated in Fig. 1-3 represent O2-, OH-, or F-
in the phyllosilicate structures, while positively charged cations occupy the
space between these negatively charged anions.
2. Tetrahedra and Octahedra
Another examination of Fig. 1-3 shows that there are two different types
of sites into which cations can be placed. The "A" sites, formed over the "A"
Introductory Concepts Final Draft, Revised 1/18/00
voids of the lower plane of spheres, are called tetrahedral sites because the
four O2- ions surrounding this site form the apices of a regular tetrahedron.
The "B" sites, formed over the "B" voids of the lower plane of spheres, are
called octahedral sites because the six O2- ions surrounding each of these
sites form the apices of a regular octrahedron (Fig. 1-3). This illustrates that
both octahedral and tetrahedral sites are a consequence of the closest
packing of two planes of spheres.
A cation in a tetrahedral site is in 4-fold (or tetrahedral) coordination
because it is bonded to four O2- ions whose centers define the apices
(corners) of a tetrahedron. Likewise, a cation in an octahedral site is in
6-fold (or octahedral) coordination because it is bonded to six O2- ions
whose centers define the apices of an octahedron. Tetrahedrally and
octahedrally coordinated cations—tetrahedra and octahedra for short—are
common structural elements in many mineral structures. The approach of
describing mineral structures as assemblages of polyhedra is used widely
and, once mastered, provides an efficient way to understand even complex
mineral structures.
3. Representing Tetrahedra and Octahedra
Octahedra and tetrahedra are commonly represented using three
different types of models. Each model portrays the same concept, but
different representations are necessary to show various structural features.
Fig. 1-3 shows two views of a tetrahedron and of an octahedron drawn in
these three different ways.
The sphere-packing model gives an impression of the space occupied by
the atoms in a structure. The sphere-packing model is particularly useful for
visualizing the shape of the external surface of a mineral, but it does not
allow one to easily see the interior of the structure. The ball-and-stick model
shows the bonds within the crystal since the bonds are represented as
"sticks" connecting the balls. The tetrahedra and octahedra are more difficult
to visualize, but the interior of the structure is easier to see because the
atoms are drawn much smaller than in the close-packed model. The
polyhedral models give the best impression of tetrahedra and octahedra since
the atoms are represented only as points in space or as small spheres. The
centers of the O2- ions are connected by lines to form the edges of tetrahedra
and octahedra. Thus, each apex represents the position of an O2- ion, while a
cation resides in the center of the tetrahedron or octahedron. In general, only
those tetrahedra or octahedra actually occupied by cations are represented by
a solid polyhedron, sites that are not occupied by cations are not represented
by solid polyhedra. One should use care in interpreting polyhedral models,
since it is easy to get the impression that a structure contains a large amount
of open space or pores. The same structure drawn as a close-packed model
will show that much of the space is actually occupied by the large oxygen
atoms. Other ways of representing mineral structures are encountered as
well. Sometimes, polyhedral models are drawn without spheres to represent
Page 5
the oxygens and hydroxyls at the corners of the polyhedra (see, for example,
Fig. 1-9 later in this chapter), while other models show only sticks to
represent bonds, but no spheres to represent the atoms.
There is some ambiguity associated with each type of representation,
and it is important to understand the correspondence between, and
limitations of, each of the different structural representations. Thus, it is
important to utilize as many different learning aids as possible. Computer
graphics programs that allow the viewer to rotate and manipulate structural
models on the computer screen offer significant advantages over static
drawings. Physical models should be studied as well, if they are available.
Far from being child’s play, building your own models is one of the best
ways to learn about mineral structures. Models can be built with inexpensive
balls and some glue or with paper polyhdera [see Moore and Reynolds
(1997) for templates].
4. Ionic Radii and Radius Ratios
Whether or not a given atom can occupy a tetrahedral or an octahedral
site depends both on the atom’s charge and size. The size of atoms and ions
varies depending on their atomic number, ionization state, and coordination
number (Table 1-4).
The central void within a tetrahedron is smaller than the one within an
octahedron. In other words, the largest sphere that can be placed in a
tetrahedral site without pushing the O2- ions apart is smaller than the sphere
that can be placed in an octahedral site without pushing. Simple calculations
(see, for example, Klein and Hurlbut, 1993) illustrate that the maximum
radius of a sphere that will just fit in the tetrahedral site is 0.225 times the
radii of the 4 surrounding O2- ions. For an octahedral site, the maximum
radius is 0.414 times the radii of the 6 surrounding O2- ions. The next larger
type of site (not illustrated) is a cubic site consisting of 8 O2- ions arranged at
the corners of a cube. For a cubic site, the maximum radius is 0.732 times
the radii of the 8 surrounding O2- ions. Assuming a radius of 0.140 nm for
the O2- ions, the limiting radius for a tetrahedral site is 0.032 nm (0.140 nm
× 0.225 = 0.032 nm), for an octahedral site it is 0.058 nm, and for a cubic
site it is 0.102 nm. The Si4+ ion has a radius <0.032 nm (Table 1-4). Thus,
Si4+ always occurs in tetrahedral rather than octahedral sites. The Mg2+ ion
has a radius that is >>0.032 so Mg2+ is unlikely to occur in tetrahedral
coordination, but since its radius is between 0.058 and 0.102 nm, it fits
easily in an octahedral site. The Al3+ ion, with a radius near to the limiting
radius of 0.032 nm, can fit in both tetrahedral and octahedral sites. Cations
with radii >~ 0.102 nm tend to occur in cubic, dodecahedral (12-fold) or
higher coordination sites rather than in octahedral or tetrahedral sites
(Table 1-4).
Introductory Concepts Final Draft, Revised 1/18/00
5. Tetrahedral and Octahedral Sheets
Tetrahedra arranged into sheets are common to the structures of all
phyllosilicates. Octahedra arranged into sheets are present in the structures
of phyllosilicates and in some hydroxide minerals as well. The structure of
tetrahedral and octahedral sheets will be discussed first, then it will be
shown how different combinations of tetrahedral and octahedral sheets give
rise to the different clay mineral structures. Most of the diagrams in this
chapter show ideal crystal structures based on the approximate closest
packing of spheres.
a. The Octahedral Sheet
Consider two planes of spheres representing hydroxyl (OH-) ions in
hexagonal closest packing. (The H+ takes up very little space and the OH-
can be considered a sphere of roughly the same size as an O2- ion). There are
two ways of filling the octahedral sites depending on the valence of the
cation. A divalent cation, such as Mg2+, can be placed into each octahedral
site to obtain the network of octahedra illustrated in Fig. 1-4a. This
arrangement is called trioctahedral because 3 of every 3 octahedral sites are
occupied by a cation. This gives a formula of Mg3(OH)6 or Mg(OH)2 for the
whole sheet; each Mg2+ is surrounded by 6 OH-'s, but since each OH- is
shared equally among 3 different Mg2+ atoms, each OH- contributes only 1/3
of its negative charge to each Mg2+, giving the formula Mg(OH)2. The sheet
is electrically neutral because the charge is balanced within the sheet.
The other possibility is to place a trivalent cation, such as Al3+, into the
octahedral sites. To preserve charge neutrality, only 2 trivalent cations are
needed compared to 3 divalent cations, giving the formula Al2(OH)6 or
Al(OH)3. Thus, only 2 of every 3 possible octahedral sites are filled. This
arrangement is called dioctahedral and is illustrated in Fig. 1-4b. The unit
formula for the dioctahedral sheet can be deduced by following the same
reasoning used above. Each Al3+ is surrounded by six OH-'s, but since each
OH- is shared equally between 2 different Al3+ ions (not 3 as for Mg2+), each
OH- contributes 1/2 of its negative charge to each Al3+, giving the formula
Al(OH)3. Again the charge is balanced and the sheet is electrically neutral.
Note how the trioctahedral and dioctahedral sheets appear in the
different types of representations. The sphere-packing model shows that
both the trioctahedral and dioctahedral sheets contain the same dense
packing of OH-'s. The pattern of unoccupied octahedral sites is more evident
in the polyhedral model, where unoccupied octahedra appear as open spaces,
and in the ball-and-stick model.
Octahedral sheets, stacked one on top of the other and held together by
weak residual bonds, make up the structures of gibbsite (Fig. 1-7) and
brucite [Mg(OH)2]. Gibbsite and brucite differ in that gibbsite contains Al in
the octahedral sites and is dioctahedral, while brucite contains Mg in the
octahedral sites and is trioctahedral. The structures of gibbsite and brucite
are the simplest in a series of structures containing octahedral sheets.
Page 6
The discussion above followed a sphere-packing approach in which we
showed that the structure of the octahedral sheets could be derived assuming
that the large oxygen atoms were hard spheres of identical size closely
packed in three dimensions. Thus, we assumed that the oxygen atoms were
our basic structural units and that the cations merely served to balance the
negative charge of the oxygens. This approach works for some of the oxide
and hydroxide minerals, but in many mineral structures the oxygen atoms
are not as closely packed as strict geometric packing would dictate. A more
general way of describing mineral structures is called the polyhedral
approach. In the polyhedral approach, the coordination polyhedra, primarily
octahedra and tetrahedra in the phyllosilicates, are considered the basic
structural building blocks. Thus, we can consider the octahedral sheets
illustrated in Fig. 1-4 as an assemblage of octahedra in which adjacent
octahedra share two oxygens with one another. In other words, the octahedra
share edges with one another. In general, coordination polyhedra can share
corners (one shared oxygen), edges (two shared oxygens), or faces (three or
more shared oxygens) with adjacent polyhedra. The octahedral sheet could
be described using either the sphere packing or polyhedral approaches. The
tetrahedral sheet described below can only be describe using the polyhedral
approach because the oxygens in the tetrahedral sheet are not close-packed
as they are in the octahedral sheet.
b. The Tetrahedral Sheet
The tetrahedral sheet consists of SiO4 tetrahedra arranged such that
three O2- ions of each tetrahedron are shared with the three nearest neighbor
tetrahedra (Fig. 1-5). These shared O2- ions are all in the same plane and are
referred to as basal oxygens. Note that two adjacent tetrahedra share only
one O2- between them. (The tetrahedra share apices or corners.) The fourth
O2- ion of each tetrahedron is not shared with another SiO4 tetrahedron and
is free to bond to other polyhedral elements. These unshared O2- ions are
referred to as apical oxygens. Since each basal oxygen contributes a formal
charge of -1 to each Si4+ ion, the addition of H+ ions to the apical oxygens to
form hydroxyls should result in an electrically neutral tetrahedral sheet. Such
individual tetrahedral sheets, although sometimes postulated to occur as
transient weathering products in aqueous solution, do not stack to form
stable mineral structures on their own. Thus, tetrahedral sheets only occur in
combination with octahedral sheets as described below.
The upper half of Fig. 1-5 shows all of the apical oxygens pointing in
the same direction, namely, out of the plane of the paper towards the reader.
Structures in which the apical oxygens of a single sheet all point in the same
direction are the most common, but structures also occur in which the apical
oxygens point alternately in opposite directions. Minerals containing this
Introductory Concepts Final Draft, Revised 1/18/00
sheet-like arrangement of SiO4 tetrahedra are called "phyllosilicates1" or
"sheet silicates.”
B. Phyllosilicate Minerals Common in Soils
Phyllosilicates are divided into two groups, 1:1 and 2:1-type minerals,
based on the number of tetrahedral and octahedral sheets in the layer
structure.
1. The 1:1 Type Minerals
a. The 1:1 Layer Structure.
The 1:1 layer structure consists of a unit made up of one octahedral and
one tetrahedral sheet, with the apical O2- ions of the tetrahedral sheets being
shared with (and part of) the octahedral sheet (Fig. 1-6a and 1-6b). There are
three planes of anions (Fig. 1-6b). One plane consists of the basal O2- ions of
the tetrahedral sheet, the second consists of O2- ions common to both the
tetrahedral and octahedral sheets plus OH- belonging to the octahedral sheet,
and the third consists only of OH- belonging to the octahedral sheet.2
The edge view of the 1:1 layer in Fig. 1-6b is one of two possible
depictions often encountered in the literature. The other view is obtained by
rotating the structure around an axis normal to the sheet and viewing the
structure along a different crystallographic axis (Fig. 1-6c).
b. Kaolinite.
The structure of kaolinite consists of 1:1 layers stacked one above the
other. Kaolinite is dioctahedral and contains Al3+ in the octahedral sites and
Si4+ in the tetrahedral sites (Fig. 1-7). The 1:1 layer is electrically neutral and
adjacent layers are held together by hydrogen bonding between the basal
oxygens of the tetrahedral sheet and the hydroxyls of the surface plane of the
adjacent octahedral sheet.
1
The prefix phyllo-, derived from the Greek word phyllon, meaning leaf, should not be
confused with the prefix phylo-, derived from the Greek word phylon, meaning tribe.
Phyllo- is pronounced fil’o, while phylo- is pronounced fi’ lo. Thus, the proper
pronunciation for phyllosilicate is fil’o sil’ i kat.
2 belonging to the octahedral sheet.
The usage of the terms plane, sheet, and layer follows the recommendations of the
AIPEA Nomenclature Committee. They refer to increasingly thicker arrangements such
as a single plane of atoms, a tetrahedral or octahedral sheet and a 1:1 or 2:1 layer. A
sheet is a combination of planes, and a layer is a combination of sheets. Layers can be
separated by various interlayer materials, such as cations, hydrated cations, organic
molecules, and hydroxide octahedral groups and sheets. The total assembly of a layer
plus interlayer material is called a unit structure (AIPEA Nomenclature Committee,
1980).
Page 7
Kaolinite is a common mineral in soils and is the most common member
of this subgroup. It tends to be particularly abundant in more weathered soils
such as Ultisols and Oxisols. Kaolinites have very little isomorphous
substitution in either the tetrahedral or octahedral sheets and most kaolinites
are close to the ideal formula Al2Si2O5(OH)4. The 1:1 layer has little or no
permanent charge because of the low amount of substitution. Consequently,
cation exchange capacities and surface areas are typically low. Soils high in
kaolinite are generally less fertile than soils in which 2:1 clay minerals
dominate.
Kaolinite can form in soils from Al and Si released by the weathering of
primary and other secondary minerals. For example, feldspars often weather
to kaolinite in soils formed from igneous rocks. Kaolinite can also be
inherited from the soil parent material — i.e. clayey sediments. Kaolinite is
used widely in a variety of industrial applications such as fillers for plastics,
in ceramics, and as a filler and coating for paper.
c. Halloysite.
Halloysite has a 1:1 layer structure similar to kaolinite except that the
1:1 layers are separated by a layer of H2O molecules when fully hydrated
(Fig. 1-7). Most clay silicates occur as thin plates, but halloysite often occurs
as tubular or spherical particles.
Halloysite is usually found in soils formed from volcanic deposits,
particularly volcanic ash and glass. It is a common clay mineral in the
Andisol soil order. Halloysite forms early in the weathering process but it is
generally less stable than kaolinite and gives way to kaolinite with time.
2. The 2:1 Type Minerals
In contrast to the 1:1 minerals, which are mostly represented in soils by
only 2 major minerals, the 2:1 minerals are structurally more diverse and are
represented by several mineral species.
a. The 2:1 Layer Structure.
The 2:1 layer structure consists of 2 tetrahedral sheets with one bound to
each side of an octahedral sheet (Fig. 1-6b). There are four planes of anions.
The outer two consist of the basal oxygens (O’s) of the two tetrahedral
sheets, while the two inner planes consist of oxygens common to the
octahedral sheet and one of the tetrahedral sheets, plus the hydroxyls (OH’s)
b. Talc and Pyrophyllite.
The simple structures of talc and pyrophyllite are good starting points
for discussing 2:1 structures. Both minerals consist of 2:1 layers stacked one
above the other. Talc has Mg2+ in the octahedral sites and is trioctahedral,
while pyrophyllite (Fig. 1-7) has Al3+ in the octahedral sites and is
dioctahedral. The tetrahedral sheets of both minerals contain only Si4+,
Introductory Concepts Final Draft, Revised 1/18/00
giving ideal formulas of Mg3Si4O10(OH)2 for talc and Al2Si4O10(OH)2 for
pyrophyllite. In each case the charge is balanced within the 2:1 layer,
making it electrically neutral. Adjacent 2:1 layers are held together only by
weak van der Waals forces.
Talc and pyrophyllite occur only rarely in soils, usually only when they
are inherited from low-grade metamorphic rocks. Talc and pyrophyllite are
used industrially as ingredients in paints, ceramics, plastics, paper, and
cosmetics. The occurrence of talc in river and estuarial sediments when there
is no geological source is a reflection of industrial activity in the watershed.
c. Micas.
Mica minerals have the 2:1 layer structure described for talc and
pyrophyllite but with two important differences. First, instead of having only
Si4+ in the tetrahedral sites, one-fourth of the tetrahedral sites are occupied
by Al3+. Because of this substitution, there is an excess of one negative
charge per formula unit in the 2:1 layer. Second, this excess negative charge
is balanced by monovalent cations, commonly K+, that occupy interlayer
sites between two 2:1 layers. This gives an ideal formula of
KAl2(AlSi3)O10(OH)2 for a mica mineral with Al in the octahedral sites.
Just as in talc and pyrophyllite, the octahedral sheet can be either
dioctahedral (Fig. 1-7) or trioctahedral. There are several different mica
species because Fe2+ and Fe3+ can substitute for Mg2+ and Al3+ in the
octahedral sheet and Na+ and Ca2+ can substitute for K+ in the interlayer.
Mica in soils is usually inherited from the parent rock and is likely to
occur in soils derived from various igneous and metamorphic rocks, as well
as from sediments derived from them. Muscovite, biotite, and phlogopite are
the three most common mica group minerals in rocks, and consequently in
soils. All three contain K in the interlayer (Table 1-3), but they differ in the
composition of the octahedral sheet and whether they are di- or trioctahedral.
Mica in the clay fraction of soils and sediments differs somewhat from
the macroscopic muscovite mica it most closely resembles. This clay-size
mica is often referred to as illite. Glauconite is another mica mineral that is
similar to illite, but it contains more Fe and less Al in its octahedral sheet
than illite.
Micas weather to other minerals, particularly to vermiculites and
smectites and the K+ released during weathering is an important source of K
for plants. As a rule, the dioctahedral micas, such as muscovite, are more
resistant to weathering than trioctahedral micas. Thus, muscovite tends to be
the most common mica mineral found in soils. Micas are used commercially
in paints and cosmetics.
d. Vermiculites.
Vermiculite has a 2:1 layer structure as described for mica, but instead
of having a layer charge of ~1 per formula unit and K+ in interlayer
positions, vermiculite has a layer charge of 0.9 to 0.6 and contains
Page 8
exchangeable cations, primarily Ca and Mg, in the interlayer (Fig. 1-7). The
high charge per formula unit gives vermiculites a high CEC and causes them
to have a high affinity for weakly hydrated cations such as K+, NH4+ and
Cs+. Fixation of K+ by vermiculites can be significant in soils high in
vermiculite.
Vermiculites in soils are believed to form almost exclusively from the
weathering of micas and chlorites. The weathering of micas to vermiculite
(or smectite) is believed to occur by replacement of K+ in the interlayer sites
with hydrated exchangeable cations. The integrity of the 2:1 layer is
preserved but there is a reduction in the layer charge. Vermiculite does not
swell as extensively as smectite and this is illustrated in Fig. 1-7 by the
presence of only two planes of water molecules surrounding the hydrated
cations in the interlayer space. Some commercial uses of vermiculites
include horticultural potting media and thermal insulating materials.
e. Smectites.
The smectite group consists of minerals with the 2:1 structure already
discussed for mica and vermiculite, but with a still lower charge per formula
weight, namely 0.6 to 0.25. As in vermiculite, the interlayer contains
exchangeable cations (Fig. 1-7).
As for the micas and vermiculites, dioctahedral smectites are more
common in soils than trioctahedral smectites. The most common smectite
minerals range in composition between the three end-members:
montmorillonite, beidellite, and nontronite. All are dioctahedral, but they
differ in the composition of the tetrahedral and octahedral sheets. Smectites
do not fix K+ as readily as do vermiculites because smectites have a lower
layer charge, but smectites swell more extensively than vermiculite. This is
illustrated in Fig. 1-7 by the larger spacing between the 2:1 layers.
Smectites are important minerals in temperate region soils because of
their high surface area and their adsorptive properties. Smectites shrink upon
drying and swell upon wetting. This shrink-swell behavior is most
pronounced in the Vertisol order and in vertic subgroups of other soil orders.
The shrink-swell properties lead to cracking and shifting problems when
houses, roads, and other structures are built on smectitic soils. Smectites are
used widely in industry as catalysts, adsorbents for spills, as sealants for
ponds and abandoned wells, in drilling fluids for oil wells, and in liners for
landfills.
f. Chlorites.
Like mica, chlorite minerals have a 2:1 layer structure with an excess of
negative charge. In contrast to mica, however, the excess charge is balanced
by a positively charged interlayer hydroxide sheet (Fig. 1-7), rather than K+.
The interlayer hydroxide sheet is an octahedral sheet as illustrated in Fig. 1-4
and can be either di- or trioctahedral. Instead of being electrically neutral as
in brucite or gibbsite, the hydroxide sheet has a positive charge cause by
Introductory Concepts Final Draft, Revised 1/18/00
substitution of higher valence cations for lower valence ones, for example,
Mg2Al(OH)6+. Either octahedral sheet — the one that is part of the 2:1 layer
or the interlayer hydroxide sheet — can be di- or trioctahedral, and can
contain Mg2+, Fe2+, Mn2+, Ni2+, Al3+, Fe3+, and Cr3+, giving a large number
of different mineral species.
Chlorite minerals in soils may be primary minerals inherited from either
metamorphic or igneous rocks. They may also be inherited from sedimentary
rocks such as shales, or from hydrothermally altered sediments. Chlorites are
rather infrequent minerals in soils and when they do occur they generally
make up only a small amount of the soil. Chlorite weathers to form
vermiculite and smectite and the ease with which they break down makes
them sensitive indicators of weathering.
g. Hydroxy-interlayered vermiculite and smectite.
Hydroxy-interlayered vermiculite and smectite can be considered a solid
solution with vermiculite or smectite as one end member and chlorite as the
other. Hydroxy-interlayered minerals form as Al3+ released during
weathering hydrolyzes and polymerizes to form large polycations with a
postulated formula of Al6(OH)153+ (or similar) in the interlayers of
vermiculite and smectite. These polycations balance some of the charge of
the 2:1 layer. The combination of a 2:1 layer with hydroxy Al in the
interlayer gives a structure similar to that of chlorite (Fig. 1-7). Thus, these
minerals are also called secondary chlorites. The degree of filling of the
interlayer with hydroxy Al can vary from none to almost complete, with
properties of the clay varying accordingly. The interlayer hydroxy Al is not
exchangeable, therefore it lowers the CEC of smectite or vermiculite almost
linearly as a function of the amount of Al adsorbed in the interlayer.
Interlayer hydroxy Al prevents smectite from shrinking and swelling as
it normally would. In vermiculite, it reduces K+ fixation by lowering the
exchange capacity and by preventing the interlayer from collapsing around
the K+. The positively charged hydroxy interlayers also provide potential
sites for anion adsorption.
Hydroxy-interlayered vermiculite and smectite are most common in
Alfisols and Ultisols. Within a given profile they tend to be most abundant
near the soil surface. Hydroxy-interlayered smectites produced industrially
are used as catalysts in the chemical industry.
h. Interstratification in Phyllosilicates.
Phyllosilicates in soils do not always occur as discrete particles of mica,
vermiculite, smectite, chlorite, or kaolinite. For example, instead of being
made up of a stack of identical 2:1 vermiculite layers, one physically discrete
particle may consist of a mixture of both mica and vermiculite layers instead.
Such minerals are referred to as mixed-layer or interstratified minerals.
Different types of interstratified minerals have been identified. Two-
component systems include: mica-vermiculite, mica-smectite, mica-chlorite,
Page 9
chlorite-vermiculite, chlorite-smectite, chlorite-swelling chlorite, and
kaolinite-smectite. Three-component mixed layer systems can also occur.
The sequence of layers can be either regular or random. A regularly
interstratified mineral consisting of two types of layers denoted by A and B
could have a sequence like ABABAB…, or ABBABBABB…, or any other
repeating sequence. In a randomly interstratified mineral the sequence of
layers is random — for example, ABBABAABBAAA…. Random
interstratification of layer-silicates is more common in soils than regular
interstratification, though regular interstratification, especially in weathering
micas, is not rare.
Partial removal of interlayer K from micas or of interlayer hydroxide
from chlorite is one way that interstratified minerals can form in soils. Other
possibilities include (i) fixation of adsorbed K+ by some vermiculite layers
to give mica-like layers, and (ii) the formation of hydroxide interlayers to
produce chlorite-like layers.
i. Palygorskite and sepiolite.
Palygorskite and sepiolite are considered phyllosilicates, but are distinct
structurally from the typical 1:1 and 2:1 layer structures. Both minerals have
continuous tetrahedral sheets, but adjacent bands of tetrahedra within one
tetrahedral sheet point in two opposite directions rather than in one direction
as in the 1:1 and 2:1 structures. The result is a structure that can be described
as ribbons of 2:1 layers joined at their edges as illustrated in Fig. 1-8. Water
molecules occur in the spaces between the ribbons. The 2:1 ribbons are
wider in sepiolite than in palygorskite.
Palygorskite and sepiolite are often found in soils of arid and semiarid
environments. Both minerals have a fibrous morphology in contrast to the
platy morphology of most 1:1 and 2:1 minerals. Because of their fibrous
morphology, suspensions of these clays can form thick gels even at low solid
concentrations. Thus, palygorskite and sepiolite are used industrially as
gelling agents to keep other solids in suspension.
C. Structural Details of Phyllosilicates
Figures 1-1 through 1-8 illustrate “ideal” mineral structures based on the
regular close packing of spheres. As a consequence, all of the octahedra in
Fig. 1-4 are exactly the same size and all are regular (undistorted) solids.
Likewise, in Fig. 1-5, all of the tetrahedra are regular solids, the 6-member
tetrahedral rings form a regular hexagon, and the basal oxygens all lie in
exactly the same plane. Crystallographic structure refinements of real
phyllosilicate minerals show distortions from the ideal structures illustrated
up until now in this chapter. These distortions are similar for all of the
phyllosilicate minerals, although they vary somewhat in magnitude.
There are two reasons why real minerals deviate from these ideal
structures. First, atoms are not hard spheres whose closest approach is
determined solely by the sum of their radii. Second, if one does try to join
Introductory Concepts Final Draft, Revised 1/18/00
octahedral and tetrahedral sheets built of hard spheres like those illustrated
in Fig. 1-4 and 1-5, geometry alone dictates that they will not fit together if
the spheres representing the oxygen atoms touch each other in both the
octahedral and tetrahedral sheets. The reason becomes apparent by
examining the sphere-packing model of the tetrahedral sheet in Fig. 5. Since
the apical oxygens are common to both the tetrahedral and octahedral sheets,
two adjacent apical oxygens in the tetrahedral sheet also define the edge of
an octahedron in the octahedral sheet (Fig. 1-6a). Note that, although basal
oxygens touch neighboring basal oxygens, apical oxygens do not touch
neighboring apical oxygens (Fig. 5). Thus, the octahedral sheets illustrated
in Fig. 1-4 cannot share apical oxygens with the tetrahedral sheet illustrated
in Fig. 1-5 because the tetrahedral sheet is larger than the octahedral sheet.
This problem was overcome in Fig. 1-6 to 1-8 by increasing the oxygen-
oxygen distance in the octahedral sheet to match the oxygen-oxygen
distance of the apical oxygens of the tetrahedral sheet. Thus, the octahedra
remain undistorted but they are larger than they would be if the spheres
representing oxygen touched.
In the real phyllosilicate structures, this mismatch between the
octahedral and tetrahedral sheets is compensated, not by an expansion of the
octahedral sheet, but primarily by distortions in the tetrahedral sheet. The net
effect is that, the tetrahedra are rotated from the ideal arrangement shown in
Fig. 1-5 such that the hexagonal shapes outlined by the 6-membered
tetrahedral rings in Fig. 1-5 become the ditrigonal shapes illustrated in Fig.
1-9. In addition, the tetrahedra are tilted such that the basal oxygens no
longer lie in the same plane, resulting in a corrugated basal plane in which
some rows of atoms lie slightly below and some lie slightly above the
average plane of the basal oxygens. These corrugations are best seen in the
lowermost edge view in Fig. 1-9 where spheres representing the oxygen
atoms have not been drawn. The implications of these distortions are that
molecules interacting with phyllosilicate surfaces “see”, not the ideal surface
illustrated in Fig. 1-6a, but the more distorted surface illustrated in Fig. 1-9.
The octahedral sheet is distorted from the ideal structure as well. First,
because of the attraction of each central octahedral cation to its 6
surrounding oxygens, octahedra occupied by cations are smaller than
octahedra in which the central sites are unoccupied (Fig. 1-9). In addition,
when two octahedra share two adjacent oxygens (the octahedra share edges),
the oxygen-oxygen distance along this shared edge is shorter than the
oxygen-oxygen distance along an edge that is not shared with an adjacent
occupied octahedron (Fig. 1-9). Thus, the octahedra are distorted from the
ideal Euclidean solids in very predictable ways. In general, trioctahedral
phyllosilicates show less structural distortion and more closely resemble the
“ideal” structures than do the dioctahedral phyllosilicates.
The structural distortions just discussed probably account for relatively
minor differences in the properties of the phyllosilicates, with the major
differences determined mainly by whether the mineral has a 1:1 or 2:1 layer
structure and by the layer charge. On the other hand, since dioctahedral
Page 10
phyllosilicates are more common in soils than trioctahedral phyllosilicates,
water, ions and molecules interact predominately with surfaces like those
illustrated in Fig. 1-9, rather than surfaces with the more regular
arrangement illustrated in Fig. 1-4 and 1-6a.
III. OTHER ALUMINOSILICATE MINERALS COMMON IN
SOILS
A. Zeolites
Zeolites are of a large group of minerals that consist structurally of SiO4
tetrahedra arranged in ways that result in large amounts of pore space within
the crystals (Fig. 1-8). Aluminum substitutes for Si in the tetrahedral sites
and, as a result, the (Si,Al)O4 framework has a net negative charge. The
charge is balanced by cations that reside in the channels and pores, along
with water molecules. Because the cations are exchangeable, zeolites have
cation exchange properties similar to the phyllosilicates, but because the
tetrahedral framework of the zeolites is rigid and the size of the pores is
fixed, small cations can move into and out of the pores freely, while larger
cations are excluded. Thus, zeolites are often referred to as “molecular
sieves” because of their very selective cation exchange properties.
Zeolites are relatively rare in soils because they weather easily in humid
regions, but they do occur in some soils in arid regions. Zeolites are widely
used in industry and agriculture, for example, as catalysts and adsorbents in
the chemical industry, as additives in animal feeds, and as ingredients in
laundry detergents. Thus, zeolites may be introduced into soils and
sediments in unexpected ways.
B. Allophane and Imogolite
The aluminosilicate minerals discussed above have three-dimensional
crystal structures with atoms packed together in a more or less regular
manner over relatively long distances (10's of nm's). They exhibit long range
order. Two other aluminosilicates, allophane and imogolite, exhibit short-
range (or local) order. Structures with short-range order exhibit order over
several nm’s, but on a larger scale the structure is disordered.
Allophane is a material consisting chemically of variable amounts of
O2-, OH-, Al3+, and Si4+, and characterized by short-range order and a
predominance of Si-O-Al bonds. It consists of small (3.5-5.0 nm) spheres,
the structure of which has not been determined. The spheres clump together
to form irregular aggregates.
Imogolite consists of tubes several µm long with an outer diameter of
2.3 to 2.7 nm and an inner diameter of ~l.0 nm. The tubes consist of a single
dioctahedral sheet with the inner surface OH replaced by SiO3OH groups
(Fig. 1-8; Farmer, et al., 1983). Several individual tubes are arranged in
Introductory Concepts Final Draft, Revised 1/18/00
bundles 10-30 nm across to give thread-like particles several micrometers
long.
Allophane and imogolite usually occur as weathering products of
volcanic ash and are important minerals in the Andisol soil order. Imogolite
has also been identified in the Bs horizons of Spodosols. Allophane and
imogolite can specifically adsorb many inorganic and organic compounds.
Andisols, for example, usually fix large amounts of phosphate, making it
unavailable to plants, and the large amounts of organic matter common in
Andisols may be due, in part, to adsorption of organic molecules by
allophane and imogolite. Soils containing large amounts of allophane and
imogolite usually have unique physical properties such as a low bulk
density, high water holding capacity, high liquid and plasticity limits, and a
thixotropic consistence.
IV. SOME CRYSTALLOGRAPHIC CONCEPTS
In 1912 Max von Laue conducted an experiment to see if the "x-rays"
discovered 17 years earlier by Wilhelm Conrad Röntgen could be diffracted
by a crystal. This one experiment had two very important results: (1) it
proved that x-rays behaved as waves, and (2) it showed that crystals were
made up of a regular array of atoms in space, and could therefore serve as a
grating to diffract the x-rays. Within a few years of von Laue's discovery,
much of the mathematical theory describing the diffraction of x-rays by
crystals had been developed and the atomic structures of some simple
crystals had been determined (Azároff, 1968; Klug and Alexander, 1974).
As early as 1923 and 1924 several clays were shown to be crystalline by x-
ray diffraction, but it was not until 1930 that some of the first structure
determinations of clay minerals were made. About the same time, two
independent papers, one by S. B. Hendricks and W. H. Fry in 1930 and the
other by W. P. Kelly, W. H. Dore, and S. M. Brown in 1931, gave the first
x-ray diffraction evidence that soil materials, even those in the finest
fractions, were crystalline (Marshall, 1949; Grim, 1968).
X-ray diffraction remains the most important method for identifying soil
minerals. A working knowledge of certain concepts of crystallography and
x-ray diffraction is necessary for understanding clay mineralogy. A brief
introduction to some of these concepts follows.
A. Periodicity in Crystals
In a crystal, a particular pattern or arrangement of atoms is repeated over
and over in three dimensions. Repeating patterns occur not only in crystals
but also in many familiar places such as wallpaper, tile floors, and brick
walls. Concepts that apply to crystals can be developed by starting with
these familiar examples.
Fig. 1-10a illustrates a pattern made up of leaves much like the pattern
on a piece of wallpaper. The periodicity of this pattern can be characterized
Page 11
with three parameters. Along the X axis the pattern is repeated at intervals of
a. We also say that the pattern is translated (moved) along X at increments of
a. The translation interval along the Y axis is designated b and the angle
between the X and Y axes is designated by the angle γ. The array of leaves in
Fig. 1-10a consists of real objects, namely, leaves. We can represent the
periodic nature of this pattern by an array of points in space, each point
having identical surroundings (Fig. 1-10b.). Such an array is called a lattice.
A lattice of points is imaginary since each point is an imaginary infinitesimal
spot in space. The concept of a lattice is useful because it allows us to
represent the periodic nature of a pattern regardless of the actual object or
configuration of objects at each lattice point. The lattice depicted in Fig. 1-
10b is called a plane lattice because it has only two dimensions. The concept
can be extended to three dimensions to give a space lattice. A space lattice is
a regular and unlimited distribution of points in space (Fig. 1-11). The
concept of a space lattice is used in describing crystal structures because
crystals are three dimensional objects3. The directions of the crystallographic
axes in three dimensions are designated by X, Y and Z, and a, b, and c are
used for the repeat distances along these axes (AIPEA Nomenclature
Committee, 1980). The angles between the axes are designated α between Y
and Z, β between X and Z and γ between X and Y.
B. The Unit Cell
Joining the points of a space lattice produces a series of parallel-sided
unit cells (Fig. 1-11). Each unit cell contains a complete unit of the crystal
pattern because the complete pattern is reproduced at each lattice point. Note
that there are alternative ways of outlining the unit cell. The choice of the
"best" unit cell for a mineral is made when the structure is determined. A
unit cell is chosen for convenience in visualizing the symmetry and in
making mathematical calculations. Different researchers will occasionally
choose different unit cells to describe the same mineral structure.
There are 14 unique ways of arranging points in three-dimensional
space. These are known as the 14 Bravais lattices. They form the
geometrical basis for all possible unit cells. Each Bravais lattice belongs to 1
of 6 crystal systems depending on the symmetry of the lattice (Table 1-5).
The cubic system is most symmetric. All axial translations are equal (a = b
= c) as are all axial angles (α = β = γ). The triclinic system is most general
3
The terms lattice and structure are often misused by authors and speakers. The two
terms are not synonymous. Lattice is the mathematical concept of an infinite uniform
distribution of points in space (e.g., the 14 Bravais lattices). Structure refers to the actual
physical assemblage of atoms (e.g., the 2:1 structure) (AIPEA Nomenclature Committee,
1980). The concept of a lattice is used to describe the periodicity in crystal structures.
Introductory Concepts Final Draft, Revised 1/18/00
(and least symmetric). All axial translations and axial angles are different.
The unit cell dimensions and the axial angles are important parameters in
describing the crystal structure of a mineral.
C. Miller Indices
A consistent and concise notation is used when planes of atoms in a
crystal are discussed. Different planes are generally referred to by their
Miller indices, designated as (hkl). For example, we may speak of (001)
planes, (110) planes and (431) planes. The concept of Miller indices follows
from the lattice concept just discussed. Consider the lattice of points in Fig.
1-12a and a plane that is parallel to c and passes through any two lattice
points (represented in an edge view by the heavy line). An identical plane
must pass through each and every lattice point (light lines) because the
lattice is periodic and each point is the same as any other. This family of
parallel planes cuts the a dimension of the unit cell into 2 parts and the b
dimension into 3 parts. The c dimension is not cut at all (zero parts) because
the planes are parallel to Z. The Miller indices are thus (230). In terms of
(hkl), the planes cut the a dimension of the unit cell into h parts, the
b dimension into k parts, and the c dimension into l parts. Additional
examples of Miller indices are given in Fig. 1-12b.
D. X-ray Diffraction
X-ray diffraction (XRD) is the main analytical technique used both to
identify unknown mineral phases and to determine crystal structures. Soil
minerals are usually studied using the powder diffraction method. A
powdered sample, with particles typically <50 µm in diameter, is placed in a
diffractometer and irradiated with x-rays. A plot of diffracted x-ray intensity
versus the diffraction angle — i.e. 2θ — is obtained. A simple mathematical
relationship called Bragg's Law is then used to relate the peaks on the x-ray
chart with the distances between the diffracting planes of atoms within the
crystals.
1. Bragg's Law
X-rays are electromagnetic waves with wavelengths on the order of the
spacings between the planes of atoms in crystals. Thus, crystals diffract x-
rays. Understanding the additive relationships of waves that are in phase or
out of phase is important to understanding x-ray diffraction. Fig. 1-13a
illustrates three different sine waves, all of which begin at the same point in
their cycles. The waves are in phase because the maxima of each wave
coincide. The sum of all three waves is a much larger wave with the same
period (distance between successive maxima) as the original waves but with
three times the intensity. The three waves on the right are identical to those
on the left, except that they are out of phase. Each wave begins at a different
Page 12
point in its cycle relative to the others. The maxima of the three waves no
longer coincide and thus the sum, which takes into account the positive and
negative aspects of the three individual waves, approaches zero.
In x-ray diffraction, constructive interference occurs when many waves
are in phase. The energy from the large summation wave is detected by the
diffractometer. Destructive interference occurs when the waves are out of
phase. In this case no appreciable energy is detected. The peaks of an x-ray
diffraction pattern correspond to areas where constructive interference
occurs. Bragg's Law relates the position of these peaks to the distances
between planes of atoms in the crystal. This information, along with the
intensities of the peaks is then used for identifying mineral phases and
determining crystal structures. The following derivation of Bragg's law will
show how it works.
Consider the parallel planes of atoms with indices (hkl) separated by a
distance d depicted in Fig. 1-13b. A parallel (or collimated) beam of x-rays
of wavelength λ impinges on the (hkl) planes at an angle θ. The incident x-
rays are in phase with one another. Two waves, one traveling along OA and
being reflected off the upper plane of atoms and traveling along AP, and a
second wave traveling along O'C and being reflected off the second plane of
atoms and then traveling along CP' may, under specific conditions, be in
phase when they reach points P and P', respectively. If the waves are in
phase at line AB, when will they be in phase at line AD and thus at PP'? A
wave along CP' is in phase with a wave along AP only if the distance BC +
CD is an integral number of wavelengths. Thus
BC + CD = nλ, where n = 1,2,3,.... [1]
Since BC = CD, substituting into [1] gives
2BC = nλ. [2]
From Fig. 1-13b,
sin θ = BC/d, [3]
which can be rewritten as
BC = d sin θ. [4]
Multiplying both sides by 2 gives
2BC = 2d sin θ. [5]
Substituting [2] into [5],
nλ = 2d sin θ. [6]
This expression is Bragg's Law. Rewritten as
d/n = λ/(2 sin θ), [7]
Bragg's Law relates the perpendicular distance between diffracting planes, d,
to the diffraction angle θ. Since the order of diffraction, n, is not always
known, n is usually set to 1 and the quantity d/n is referred to as the
"d-value" of a diffraction line.
Note that the quantity needed in eq. [7] is in units of θ, while the data
from x-ray diffractometers is in units of 2θ. This is a consequence of the
physical construction of the diffractometer and division by 2 is necessary to
obtain θ from 2θ data before using eq. [7] to calculate d-values. The d-
values can be easily calculated with a pocket calculator or a computer
Introductory Concepts Final Draft, Revised 1/18/00
program. Tables for determining d-values from 2θ data are also given in
Brindley and Brown (1980) for several common x-ray wavelengths.
The distances between the diffracting planes in the crystal, d in eq. [7],
are fixed by the structure of the crystal. However, x-ray wavelengths (λ's)
used for diffraction experiments are not always the same. If λ in eq. [7]
changes, θ must change because d/n is a constant fixed by the crystal
structure of the sample. X-ray line positions expressed in 2θ can only be
compared when the x-ray wavelength is the same. Calculating the d-values
for the diffraction lines allows comparison of d-values regardless of the
wavelength.
The d-values are directly related to the unit cell dimensions and the
Miller indices. The d-value of a line with Miller indices (hkl), dhkl, in the
orthorhombic system is given by the relationship:
dhkl = [(h2/a2) + (k2/b2) + (l2/c2)]-1/2, [8]
where a, b, and c are the unit cell dimensions. Relationships for the other
crystal systems are given elsewhere (for example, Klug and Alexander,
1974).
The d/n values obtained from Bragg's Law can, in most cases, be related
to actual distances between planes of atoms in the crystals. Thus, the d-
values between successive phyllosilicate layers listed in Fig. 1-7 show up in
x-ray diffraction patterns of soil clays and are used to identify the specific
clay minerals present in unknown samples. In some cases however, in
particular for randomly interstratified minerals or cases where diffraction
lines are very broad due to the small size of the crystals, d/n values from
Bragg's Law are not directly related to the distances between planes of atoms
in the crystal. To explain these effects more inclusive diffraction theory
utilizing the concepts of the reciprocal lattice, structure factor, atomic
scattering factors, etc. must be applied.
2. The Scherrer Equation
Once a mineral phase has been identified based on its diffraction peaks,
additional information can often be obtained from diffraction line widths.
Well-crystallized minerals of sand and silt size give sharp diffraction lines
whose widths are determined only by broadening caused by the x-ray
diffractometer itself. Clay size particles show broader lines caused by
diffraction effects from the small particles. The smaller the particles are, the
broader the diffraction lines. X-ray line width and particle size are related by
the Scherrer equation:
Lhkl = (Kλ)/(β cos θ), [9]
where Lhkl is the mean crystallite dimension perpendicular to the diffracting
planes with Miller indices (hkl), K is a constant equal to 0.9 if the particles
are cubes, λ is the x-ray wavelength, β is the width (in radians) at one half
peak height corrected for instrumental broadening, and θ is the diffraction
line position. The application of the Scherrer equation involves a
considerable number of assumptions (Klug and Alexander, 1974; p. 634-
Page 13
642, 687-704) and an understanding of these assumptions is essential. In
addition, Lhkl measures the size of the coherently diffracting domains within
the crystals. If the crystals consist of several coherently diffracting domains,
then Lhkl will be smaller than the actual physical size of the crystals observed
by electron microscopy (Schulze and Schwertmann, 1984).
V. SUMMARY
This chapter has developed some of the terminology used later in this
book. It has shown how the abundance of aluminosilicate minerals is a
consequence of the abundance of Si, Al, and O in the earth's crust. It has
introduced the chemical and structural classification of minerals, mentioned
the major minerals that will be encountered in soils, and mentioned some of
the environmental implications of some of the mineral. It has developed the
major structural themes of the phyllosilicate minerals, and it has explained
some of the crystallographic and x-ray diffraction terminology used in later
chapters.
The chapters that follow will discuss in more detail the many facets of
soil mineralogy, particularly as it relates to current environmental concerns.
VI. SUGGESTED READING
For a more information on general mineralogy, see introductory texts
such as Klein and Hurlburt (1993) or Nesse (1999). Azároff (1968) and
Moore and Reynolds (1997) provide good, readable introductions to
crystallography and x-ray diffraction theory.
VII. QUESTIONS AND EXERCISES
1. Draw sketches from memory of an octahedron and a tetrahedron using
the sphere-packing, ball-and-stick, and polyhedral representations.
2. Draw sketches from memory of sphere-packing models of a tetrahedral
sheet, a dioctahedral sheet, and a trioctahedral sheet. (A coin makes a
good template for a circle.)
3. Draw three sketches of a unit cell and label the cell dimensions a, b, and
c as shown in Fig. 1-12b. On the first cell sketch in the planes with
Miller indices (002), on the second cell sketch planes with indices (111),
and on the third cell sketch planes with indices (021).
4. a. Calculate the d-values of x-ray diffraction lines that occur at 8.84,
12.36, and 26.68° 2θ for a sample x-rayed using CuKα radiation (λ =
0.15418 nm). b. Calculate the 2θ positions for these same three lines
when the sample is x-rayed using CoKα radiation (λ = 0.179026 nm).
Answers: a. 1.000, 0.716, and 0.334 nm, respectively. b. 10.27, 14.36,
and 31.09° 2θ, respectively.
5. A goethite sample was x-rayed with CoKα radiation. The 111
diffraction line was centered at 24.70° 2θ and its width at half-height
Introductory Concepts Final Draft, Revised 1/18/00
(corrected for instrumental broadening) was found to be 0.35° 2θ. Use
the Scherrer equation to calculate the size of the crystals (more exactly,
the size of the coherently diffracting domains) perpendicular to the
(110) planes. Assume that K = 0.9. Answer: 27 nm.
VIII. ACKNOWLEDGMENTS
I thank the many students over the years that have provided feedback on
this chapter.
IX. REFERENCES
AIPEA Nomenclature committee. 1980. Summary of recommendations
of AIPEA nomenclature committee. Clays Clay Min. 28:73-78.
Allen, B. L. and D. S. Fanning. 1983. Composition and soil genesis.
p. 141-192. In L. P. Wilding, N. E. Smeck, and G. F. Hall (ed.) Pedogenesis
and soil taxonomy I. Concepts and interactions. Elsevier, New York.
Azároff, L. V. 1968. Elements of x-ray crystallography. McGraw-Hill
Book Co., New York. 610 p.
Brindley, G. W. and G. Brown (eds). 1980. Crystal structures of clay
minerals and their x-ray identification. Mineralogical Society, London.
495 p.
Farmer, V. C., M. J. Adams, A. R. Fraser, and F. Palmieri. 1983.
Synthetic imogolite: Properties, synthesis, and possible applications. Clay
Min. 18:459-472.
Grim, R. E. 1968. Clay mineralogy. 2nd Ed. McGraw-Hill Book Co.,
New York. 596 p.
Jackson, M. L. 1964. Chemical composition of soils. p. 71-141. In F. E.
Bear (ed.) Chemistry of the soil. Reinhold Publishing Co., New York.
Kämpf, N., A. C. Scheinost, and D. G. Schulze. 1999. Oxide minerals.
p. F125 – F168. In: M. E. Sumner (ed.), Handbook of Soil Science. CRC
Press, Boca Raton, FL.
Klein, C. and C. S. Hurlbut, Jr. 1993. Manual of mineralogy (after
James D. Dana). 21st Ed. John Wiley & Sons, New York. 681 p.
Klug, H. P. and L. E. Alexander. 1974. X-ray diffraction procedures for
polycrystalline and amorphous materials. 2nd Ed. John Wiley & Sons, New
York. 966 p.
Marshall, C. E. 1949. The colloid chemistry of the silicate minerals.
Academic Press Inc., New York. 195 p.
Moore, D. M. and R. C. Reynolds, Jr. 1997. X-ray diffraction and
identification and analysis of clay minerals. 2nd ed. Oxford University Press,
New York. 378 p.
Nesse, William D. 1999. Introduction to mineralogy. Oxford University
Press, New York. 464 p.
Rothbauer, R. 1971. Untersuchung eines 2M1-Muskovits mit
Neutronenstrahlen. N. Jahrbuch f. Mineralogie. Monatsheite 1971:143-154.
Page 14
Schulze, D. G. and U. Schwertmann. 1984. The influence of aluminium
on iron oxides: X. Properties of Al-substituted goethites. Clay Min. 19:521-
539.
Sposito, G. 1989. The chemistry of soils. Oxford University Press, New
York. 277 p.
X. LIST OF FIGURES
Fig. 1-1. The structure of halite (NaCl).
Fig. 1-2. Hexagonal closest packing of spheres in a plane.
Fig. 1-3. Octahedra and tetrahedra as a consequence of two planes of close-
packed spheres and three ways of representing octahedra and tetrahedra.
Fig. 1-4a. A trioctahedral sheet.
Fig. 1-4b. A dioctahedral sheet.
Fig. 1-5. The tetrahedral sheet.
Fig. 1-6. (a) Oblique view of the 1:1 layer structure illustrating the
relationship between the tetrahedral and octahedral sheets. Note that
adjacent apical oxygens of the tetrahedral sheet (arrows ‘a’) also define
edges of octahedra in the octahedral sheet. Arrows marked “b” point to OHs
that lie directly in the center of the hexagonal rings of tetrahedra, although
they appear off-center in this oblique view. (b) Edge view of the 1:1 and 2:1
layer structures illustrating phyllosilicate nomenclature. (c) An alternate
edge view that arises when the 2:1 structure above is rotated normal to the
plane of the layer.
Fig. 1-7. Structural scheme of soil minerals based on octahedral and
tetrahedral sheets.
Fig. 1-8. Structural models of representatives of three other aluminosilicate
mineral groups that occur frequently in soils. All three are drawn to the same
scale.
Fig. 1-9. Structural details of phyllosilicates as illustrated by the octahedral
and tetrahedral sheets of muscovite. Figures were prepared from the single-
crystal structural refinement data of Rothbauer (1971).
Fig. 1-10. (a) A lattice array of leaves and (b) a plane lattice of points.
Introductory Concepts Final Draft, Revised 1/18/00 Page 15

Fig. 1-11. A space lattice with several alternative unit cells outlined (after Ti 4.4 0.0019 0.061 (6) 0.03
Klug and Alexander, 1974). H 1.4 0.0289 ‡ ‡
P 1.0 0.0007 0.017 (4) 0.00
Fig. 1-12. (a) Planes with Miller indices 230 (c axis is out of the plane of the Mn 0.9 0.0003 0.083 (6) 0.01
figure) and (b) planes with different Miller indices on an orthogonal lattice.
† Numbers in parentheses refer to coordination number. Radii for Fe and Mn are
Fig. 1-13. (a) In phase and out of phase waves, and (b) geometry of the for the reduced (2+) form.
Bragg "reflection" analogy for diffraction of x-rays by crystals (after ‡ Ionic radius and volume of H+ are negligible compared to O2-.
Azároff, 1968).

XI. LIST OF TABLES

Table 1-1. The twelve most common chemical elements in the earth's crust
(Klein and Hurlbut, 1993).

Table 1-2. Classification of common non-silicate minerals in soils.

Table 1-3. Classification of primary silicate minerals.

Table 1-4. Ionic radius, radius ratio and coordination number of common
elements in silicate minerals (Klein and Hurlbut, 1993).

Table 1-5. Axial ratios and angles between crystal axes for the six crystal
symmetry systems.

Table 1-1. The twelve most common chemical elements in the earth's crust
(after Klein and Hurlbut, 1993).

Element Crustal Mole fraction Ionic radius† Volume

average
g kg-1 (nm) %
O 466.0 0.6057 0.136 (3) 92.88
Si 277.2 0.2052 0.026 (4) 0.22
Al 81.3 0.0626 0.039 (4) 0.23
Fe 50.0 0.0186 0.078 (6) 0.54
Ca 36.3 0.0188 0.100 (6) 1.15
Na 28.3 0.0256 0.102 (6) 1.66
K 25.9 0.0138 0.151 (8) 2.89
Mg 20.9 0.0179 0.072 (6) 0.41
Introductory Concepts Final Draft, Revised 1/18/00 Page 16

Table 1-2. Common non-silicate minerals in soils. Table 1-3. Classification of silicate minerals.

Mineral class Mineral Chemical formula† Silicate class,

Halides Halite NaCl unit composition,
Arrangement of
Sulfates Gypsum CaSO4•2H2O
SiO4 tetrahedra† Mineral Ideal Formula‡
Jarosite KFe3(SO4)2(OH)6
Sulfides Pyrite FeS2 Nesosilicates (SiO4)4- Olivine (Mg,Fe)2SiO4
Carbonates Calcite CaCO3 Forsterite Mg2SiO4
Dolomite CaMg(CO3)2 Fayalite Fe2SiO4
Nahcolite NaHCO3 Zircon ZrSiO4
Trona Na2CO3•NaHCO3•2H2O Sphene CaTiO(SiO4)
Topaz Al2SiO4(F,OH)2
Soda Na2CO3•10H2O
Garnets X3Y2(SiO4)3,
Oxides and Hydroxides X=Ca,Mg,Fe2+,Mn2+,
Aluminum Gibbsite Al(OH)3 Y=Al,Fe3+,Cr3+
Iron Hematite Fe2O3 Andalusite Al2SiO5
Goethite FeOOH Sillimanite Al2SiO5
Lepidocrocite FeOOH Kyanite Al2SiO5
Staurolite Fe2Al9O6(SiO4)4(O,OH)2
Maghemite Fe2O3
Ferrihydrite Fe5O7(OH)•4H2O Sorosilicates (Si2O7)6- Epidote Ca2(Al,Fe)Al2O(SiO4)
Magnetite Fe3O4 (Si2O7)(OH)
Manganese Birnessite (Na,Ca,Mn2+) Mn7O4·2.8
H2O Cyclosilicates (Si6O18)12- Beryl Be3Al2(Si6O18)
Lithiophorite LiAl2Mn24+Mn3+ O6(OH)6 Tourmaline (Na,Ca)(Li,Mg,Al)(Al,Fe,
Hollandite Ba(Mn4+,Mn3+)8O16 Mn)6 (BO3)3(Si6O18)(OH)4
Todorokite (Na,Ca,K)0.3-0.5(Mn4+,Mn3+)6
Inosilicates Pyroxenes
O12·3.5H2O
(single chains) (SiO3)2- Augite (Ca,Na)(Mg,Fe,Al)(Si,Al)2O6
Titanium Rutile TiO2 Enstatite MgSiO3
Anatase TiO2 Hypersthene (Mg,Fe)SiO3
Ilmenite Fe2+TiO3 Diopside CaMgSi2O6
† after Klein and Hurlburt (1993), Kämpf et al. (1999) Hedenbergite CaFeSi2O6
Pyroxenoids
Wollastonite CaSiO3
Rhodonite MnSiO3

Inosilicates Amphiboles
(double chains) (Si4O11)6- Hornblende (Ca,Na)2-3(Mg,Fe,Al)5Si6
(Si,Al)2O22(OH)2

Tremolite Ca2Mg5Si8O22(OH)2
Actinolite Ca2(Mg,Fe)5Si8O22(OH)2
Introductory Concepts Final Draft, Revised 1/18/00 Page 17

Cummingtonite (Mg,Fe)7Si8O22(OH)2 Table 1-4. Ionic radii and coordination of common elements in phyllosilicate
Grunerite Fe7Si8O22(OH)2 minerals.

Phyllosilicates (Si2O5)2- Micas

Muscovite KAl2(AlSi3O10)(OH)2 Ion Ionic radius†
Biotite K(Mg,Fe)3(AlSi3O10)(OH)2
Phlogopite KMg3(AlSi3O10)(OH)2 (nm)
Chlorites (Mg,Fe)3(Si,Al)4O10(OH)2 ..........
O2- 0.140(6)
Clay minerals
(selected) F- 0.133(6)
Talc Mg3Si4O10(OH)2
Pyrophyllite Al2Si4O10(OH)2 Cl- 0.181(6)
Kaolinite Al2Si2O5(OH)4
Smectite M+0.3Al2(Al0.3Si3.7)O10(OH)2 Si4+ 0.026(4) tetrahedral sites
M+= Ca2+, Mg2+, K+, etc.
Vermiculite M+0.7Al2(Al0.7Si3.3)O10(OH)2 Al3+ 0.054(6)
M+= Ca2+, Mg2+, K+, etc.
Serpentines Fe3+ 0.065(6)
Antigorite Mg3Si2O5(OH)4
Chrysotile Mg3Si2O5(OH)4 Mg2+ 0.072(6)
octahedral sites
0 Ti4+ 0.061(6)
Tectosilicates (SiO2) Feldspars
Orthoclase KAlSi3O8
Fe2+ 0.078(6)
Albite NaAlSi3O8
Anorthite CaAl2Si2O8
Mn2+ 0.083(6)
SiO2 Group
Quartz SiO2
Na+ 0.118(8)
Tridymite SiO2
Cristobalite SiO2
Ca2+ 0.112(8)
Zeolites
Analcime NaAlSi2O6•H2O cubic and
K+ 0.151(8)
Feldspathoids dodecahedral sites
Nephelene (Na,K)AlSiO4
Ba2+ 0.142(8)
† after Allen and Fanning (1983).
‡ Klein and Hurlbut (1993).
Rb+ 0.161(8)

† Ionic radii vary with coordination number. Radii are for ions with the
coordination numbers listed in parentheses (from Klein and Hurlbut, 1993, p.
188).
Introductory Concepts Final Draft, Revised 1/18/00 Page 18

Table 1-5. Axial ratios and angles between crystal axes for the six crystal
symmetry systems (after Klug and Alexander, 1974).

System Axial ratios Angles between crystal axes

Cubic (isometric) a=b=c α = β = γ = 90°
Hexagonal a=b„c α = β = 90°, γ = 120°
Tetragonal a=b„c α = β = γ = 90°
Orthorhombic a„b„c α = β = γ = 90°
Monoclinic a„b„c α = γ = 90°, β > 90°
Triclinic a„b„c α „ β „ γ = 90°
 Inserts for Table 3

Nesosilicates
Cyclosilicates

Sorosilicates

Phyllosilicates

Inosilicates
(double chains)

Tectosilicates
Inosilicates
(single chains)
 Na Cl

Fig. 1-1. The structure of halite (NaCl).

 "A" voids "B" voids

Fig. 1-2. Hexagonal closest packing of spheres in a plane.

 Face Edge

"A" site "B" site

Sphere-Packing
Model

Ball-and-Stick
Model

Polyhedral
Model

Tetrahedron Octahedron Tetrahedron Octahedron

Fig. 1-3. Octahedra and tetrahedra as a consequence of two planes of close-packed spheres and three ways of representing octahedra and tetrahedra.
 The Octahedral Sheet (trioctahedral)

Mg2+

OH-

Figure 1-4a. A trioctahedral sheet. The upper three rows of hydroxyls in the face view of the sphere-packing model have been omitted for clarity.
 The Octahedral Sheet (dioctahedral)

Al3+

OH-

Figure 1-4b. A dioctahedral sheet. The upper three rows of hydroxyls in the face view of the sphere-packing model have been omitted for clarity.
The Tetrahedral Sheet

apical oxygens
Si4+

basal oxygens

Figure 1-5. The tetrahedral sheet.

a
b
b
a

b
PLANES OF IONS SHEETS, LAYERS
basal O's
tetrahedral cations tetrahedral
sheet 1:1
OH's & apical O's
octahedral cations octahedral layer
sheet
OH's

basal O's
tetrahedral cations tetrahedral
sheet
OH's & apical O's
octahedral cations octahedral 2:1
sheet layer
OH's & apical O's
tetrahedral cations tetrahedral
sheet
basal O's

c
Alternate
edge view

Fig. 1-6. (a) Oblique view of the 1:1 layer structure illustrating the relationship between
the tetrahedral and octahedral sheets. Note that adjacent apical oxygens of the
tetrahedral sheet (arrows ‘a’) also define edges of octahedra in the octahedral sheet.
Arrows marked “b” point to OHs that lie directly in the center of the hexagonal rings
of tetrahedra, although they appear off-center in this oblique view. (b) Edge view of the
1:1 and 2:1 layer structures illustrating phyllosilicate nomenclature. (c) An alternate edge
view that arises when the 2:1 structure above is rotated normal to the plane of the layer.
 Gibbsite
OH-
0.46 nm
(4.6 Å)
Al3+

Kaolinite
O2-

0.72 nm
(7.2 Å)
Si4+
Al3+

Halloysite (hydrated)

1.00 nm
H 2O
(10.0 Å)
Si4+
Al3+

Pyrophyllite
Si4+
Al3+
0.92 nm
(9.2 Å)

Mica (muscovite)
Si4+,Al3+
Al3+
1.00 nm
fixed K+
(10.0 Å)

Fig. 1-7. Structural scheme of soil minerals based on octahedral and tetrahedral sheets.
 Vermiculite
Si4+,Al3+
Al3+

1.4 nm hydr. Ca2+,

(14 Å) Mg2+, etc.

Smectite

H 2O
>1.8 nm exch. Ca2+,
(>18 Å) Mg2+, etc.

Hydroxy-interlayered
Vermiculite and Smectite

Al3+ poly.,
1.4 nm exch. Ca2+,
(14 Å) Mg2+, etc.

Chlorite

1.4 nm Mg2+, Al3+,

(14 Å) Fe3+, etc.

Fig. 1-7. Continued.

 Palygorskite
Si4+
Mg2+,Al3+
H 2O
H2 O
(not shown)

Clinoptilolite (a zeolite)
Si4+,Al3+

exch. cations
& H2O
(not shown)

Imogolite

Al3+
Si4+

H2O
(not shown)
1.0 nm
(10 Å)

Fig. 1-8. Sturctural models of representatives of three other aluminosilicate mineral

groups that occur frequently in soils. All three are drawn to the same scale as Fig. 1-9.
 Structural Details Common to Phyllosilicate Minerals
Tetrahedral Sheet Octahedral Sheet

ditrigonal
hole
occupied
octahedra
smaller than
unoccupied

shared edges
shorter than
unshared

corrugated
basal plane

Fig. 1-9. Structural details of phyllosilicates as illustrated by the octahedral and tetrahedral sheets of muscovite. Figures prepared from the single-
crystal structural refinement data of Rothbauer (1971).
 a b

g
b

a
Fig. 1-10. (a) A lattice array of leaves and (b) a plane lattice of points.
Fig. 1-11. A space lattice with several alternative unit cells outlined (after Klug and
Alexander, 1974).
Fig. 1-12. (a) Planes with Miller indices 230 (c axis is out of the plane of the figure) and
(b) planes with different Miller indices on an orthogonal lattice.

Fig. 1-13. (a) In phase and out of phase waves, and (b) geometry of the Bragg "reflection"
analogy for diffraction of x-rays by crystals (after Azároff, 1968).