Composition and Structure of

Soil Minerals
Soil solid phase
Soil minerals
z Primary minerals
z Secondary Minerals
Some characteristics of soil minerals
Identification of soil minerals

Soil Solid Phase

A typical
yp soil constitutes (volume
( basis))
z 50% solid component
z Inorganic mineral (90%)
z Organic matter (10%)
z 25% gases
z 25% liquid phase (water)

Pores ↕ Solid
 z Elements found in soils, earth’s crust and
sediments:

‹ M j elements
Major l t found
f d in
i soils,
il earth’s
th’ crustt and
d
sediments are similar

‹ Major elements in soil (median value): O (49%),, Si (31%),

Al (7%), Fe (4%), C (2%), Ca (1.5%), K (1.4%), Na (0.5),
and Mg (0.5%)

‹ Most abundant element in earth’s crust: Oxygen

• ~ 47% by weight
• > 90% by volume

z Inorganic mineral component accounts for 90% of

soil solid

‹ Mineral--- natural inorganic compounds that have definite

physical, chemical and crystalline properties

• Primary mineral --- Not chemically altered since deposition

and crystallization from molten lava.

– Examples: Quartz, feldspars

– In sand fraction (0.05-2 mm) and silt fraction (0.002 – 0.05 mm)

• Secondary mineral --- Altered chemically due to weathering of

primary mineral (through structural change or reprecipitation
of the products of dissolved primary minerals

– Examples: Kaolinite (aluminosilicates), Gibbsite

(oxide/shydroxides)
– Primarily in clay (<0.002 mm) but some in silt (0.002 – 0.05 mm)

‹ Common primary and secondary minerals (Table 2.2

Textbook)
 How Mineral Structure is Arranged ?

¾Pauling’s 5 Rules in Predicting

Mineral Structure
Linus Pauling

1954 Chem

z Rule 1. Coordination number principle 1962 Peace

‹ In a mineral in which coordinated polyhedron of

anions is formed about each cation, the cation-
anion distance is determined by y radius sum ((sum
of cation and anion radii) and coordination
number of the cation by radius ratio

‹ Coordination number--- # of nearest anions

surrounding the cation in a mineral

Pauling’s 5 Rules

z Rule
R l 11. C
Coordination
di ti
number principle

Ca2+/O2- = 0.703
CN=8, cube
• Relationship of
radius ratio,
Coordination
and
geometrical
arrangement

Tetrahedron and octahedron: single and sheet

(Fundamental structural unit)
 Octahedral sheet

T t h d l sheet
Tetrahedral h t

z Rule 2. Electrostatic Valency Principle.

‹ In a stable coordination structure, the total strength of
the valency bonds which reach a centrally coordinated
anion from all neighboring cations is equal to the
charge of the anion

• This principle also applies to situation of centrally coordinated

cation (reaching a centrally coordinated cation from all
neighboring anions is equal to the charge of cation)

‹ S = Z/CN e.g. Tetrahedron : Si-O , S=4/4=1;

Octahedron: Al-O, s=3/6=0.5

‹ Bonding character:
• Si-O 50% ionic & 50% covalent
Al-O, 60% ionic and 40% covalent
z Rule 3. On sharing polyhedra 1:
‹ The existence of edges, and
particularly of faces common to the
anion polyhedron in a coordinated
structure decreases its stability; this
effect is large for cations with high
valency and small coordination
number and is especially large when
the radius ratio approaches the
lower limit of stability of the
polyhedron.

z 3 ways
y for tetrahedral and
octahedral polyhedra to bond

‹ Point to point : stable

‹ Edge to edge: somewhat not stable
‹ Face to face: least stable
a

z Rule 4. On sharing polyhedra 2:

‹ In minerals containing different cations, those of
high valency and small coordination number tend
not to share polyhedra with each other.
other

z Rule 5. Principle of parsimony

‹ In a crystal, the number of essentially different
kinds of constituents (cations , anions groups)
tends to be small-----although elements can
substitute
b tit t for
f each h other
th during
d i mineral
i l formation
f ti
 Structure of Some Primary Minerals
z Neso-silicates (isolated tetrahedron)

z Soro-silicates ((isolated double

tetrahedrons)

z Ino-silicates (single and double

tetrahedral chains)

z Phyllo-silicates (tetrahedral sheets)

‹ Clay minerals (secondary) in this group

z Tecto-silicates (tetrahedral
Framework)

z Neso-silicates (isolated tetrahedron)

‹ Si:O ratio = 1:4

‹ Oxygen ions of each tetrahedron not
Top view
shared
‹ Bound by ionic forces from interstitial
cations (Mg, Ca, Fe)
‹ Example:

• Olivine: M2SiO4
– Forsterite, Mg2SiO4
z Soro-silicates (isolated double
tetrahedrons)

‹ Two tetrahedrons share a single apical

oxygen
‹ Si:O ratio = 2:7

‹ Bound by Interstitial cations (e.g. Ca2+)

‹ Example:
p
• Epidote: Ca2Al2 (FeO) (SiO4)(Si2O7)(OH)
– Mixture of “soro-” and ‘neso-”

z Cyclo-silicates (linked rings of

tetrahedrons)

‹ Each tetrahedron share two oxygens

‹ Si:O ratio = 1:3

Example:
• Beryl
y : Be3Al2((Si6O18)
 z Ino-silicates (tetrahedron chains)

‹ Single Chain
• Si:O ratio = 1:3
• Example: Pyroxenes
– Enstatite: MgSiO3
– Rhodonite: MnSiO3

‹ Double Chain
• Si:O ratio = 4:11
• Example: Amphiboles
– Tremolite: Ca2Mg5Si8O22(OH)2

z Phyllo-silicates (tetrahedral
sheets)

‹ One of most important

p
mineral groups (clay minerals)

‹ Structures: tetrahedral and

octahedral sheets

• Tetrahedral
T t h d l Sheets
Sh t
– 3 out of 4 oxygens in tetrahedron
shared with neighboring
tetrahedrons

– Si:O ratio = 2:5

z Phyllo-silicates (tetrahedral sheets)

‹ Octahedral sheet
a

• Dioctahedral: Cations are trivalent and each O2-

or OH- is shared by 2 cations.
– e.g. Gibbsite, Al(OH)3

• Trioctahedral: Cations are divalent and each O2-

or OH- is surrounded by 3 cations.
– e.g. Brucite, Mg(OH)2

z Phyllo-silicates (tetrahedral
sheets)
Octahedral sheet

• Trioctahedral: 3/3 cation

positions filled
– e.g. Brucite, Mg(OH)2

• Di
Dioctahedral:
t h d l 2/3 cation
ti
positions filled
– e.g. Gibbsite, Al(OH)3
z Phyllo-silicates (tetrahedral sheets)

‹ Combination of tetrahedral and Octahedral sheets

(e.g. 2 sheets of tetrahedra and 1 sheet of
octahedra)

• 2:1 combination (mica): Dioctahedral mineral

– Muscovite, KAl2(Si3Al)O10(OH)2.

• 2:1 combination (mica): Trioctahedral mineral

– Biotite, K(MgFe)3(Si3Al)O10(OH)2.

• Dioctahedral (muscovite) more resistant to weathering than

trioctahedral (biotite)

z Tecto-silicates (3-dimensional
tetrahedral framework)

‹ All oxygens (4 out of 4) in each

tetrahedron are shared

‹ Si:O ratio = 1:2

• Quartz, SiO2

• Feldspars
– Orthoclase, KAlSi3O8 (Al and Si tetrahedra)
Structure of Clay minerals
z Phyllo-silicates
‹ Layer minerals: Combination of tetrahedral and octahedral sheets

Unit cell

Phyllosilicate nomenclature

Structure of Clay minerals

z Phyllo-silicates
‹ Layer minerals: Combination of tetrahedral and octahedral sheets

Phyllosilicate nomenclature
 Structure of Clay minerals

z Isomorphous substitution:
‹ Substitution of one atom by another of similar size in the crystal
lattice without disrupting the crystal structure of the mineral

Al3+ for Si4+ a

Mg2+ for Al3+
a

a
a
Isomorphous
a w
aa
a

substitution

Structure of Clay minerals

z Dioctahedral vs trioctahedral
minerals

‹ Dioctahedral---2/3 cation positions

occupied (e.g. Gibbsite, Al(OH)3 )

‹ Trioctahedral---3/3 (all) cation

positions occupied (e.g. Brucite,
Mg(OH)2 )

‹ Trioctahedral minerals in drier

climate (e.g. W. of Mississippi
River) Vs. dioctahedral minerals in
wet climate (E. of Mississippi River)
 Structure of Clay minerals
¾1:1 Clays (Kaolin-Serpentine Group)

Dioctahedral : Kaolins--- Kaolinite, Halloysite

Trioctahedral : Serpentites--- Antigorite (not

common)
z Kaolinite structure
‹ Strong H bonding
(between adjacent basal
O and OH planes).
NO Interlayer space

‹ NO isomorpous
substitution,
b tit ti hence
h no
layer charge

‹ Ideal 1:1 formula (full

cell): Si4IVAl4VIO10(OH)8

z Halloysite same as Kaolinite

but with H2O in interlayer

Structure of Clay minerals

z 2:1 Clays

‹ Pyrophyllite-Talc Group (not common)

‹ Clay mica (Illite or hydrous mica)

‹ Smectite-Saponite Group

‹ Vermiculite Group
Structure of 2:1 Clay minerals

► Pyrophyllite
Pyrophyllite--Talc Group

ƒ Dioctahedral: Pyrophyllite, Si8IVAl4VIO20(OH)4

ƒ Trioctahedral: Talc, Si8IVMg6VIO20(OH)4

ƒ NO apparent isomorphous substitution

ƒ No layer charge and interlayer space
ƒ Adjacent 2:1 layers weakly held together

ƒ Found in soils of Southern America but generally NOT

common in soils

Structure of 2:1 Clay minerals

¾Clay mica (Illite, hydrous mica, hydromuscovite)

Dioctahedral: Half Cell:
K0.74(Si3.4Al0.6)IV(Al1.53Fe3+0.22Fe2+0.03Mg0.28)VIO10(OH)2
‹ Isomorphous substitutions
( in both tetrahedral and
octahedral sheets)

‹ Layer charge: 0.6— 0.9/half

cell (balanced by interlayer K+)
• Adjacent 2:1 layers
strongly held by K (in
hexagonal hole) , Mg

• K nott exchangeable
h bl

‹ Clay mica has more water, Si4+

and Mg2+ but less K+ and Al3+
than parent Mica (muscovite)
 Structure of 2:1 Clay minerals
• Vermiculite (layer charge: 0.6-0.9/half cell)
Higher interlayer charge than smectitite (0.2-0.6/half cell)

‹ Occur in both types of octahedra

• Dioctahedral more common

, Ca

‹ Weathering of mica but with reduced

layer charge a
spacing
1-14 Å
• Interlayer K+ replaced by
hydrated cations, e.g. Ca2+,
Mg2+

‹ Isomorphous sub. in both tetra- and a

octa-hedral sheets
a
‹ Interlayer cations exchangeable
Half cell for dioctahedral vermiculite:
‹ Interlayer semi-expansible
M0.74, H20 (Si3.56Al0.44)IV(Al1.4 Fe3+,Mg2+)0.3)VIO10(OH)2

Structure of 2:1 Clay minerals

z Smectite-Saponite group (layer charge: 0.2-0.6/half cell)

‹ Saponite– Trioctahedral, not common in soils
‹ Smectite– Dioctahedral, common and important in soils of
temperate regions (e
(e.g.
g Midwest US)
Montmorillonite, Beidellite, Nontronite

‹ Montmorillonite --- Isomorphous substitution of Al3+ by

Fe2+ and Mg2+ in octahedral sheet

‹ Beidellite--- Si4+ by Al3+ in tetrahedral sheet

‹ Nontronite--- Si4+ by Al3+ in tetrahedral sheet. Fe3+

dominate in octahedral sheet
Structure of 2:1 Clay minerals
Montmorillonite: Isomorphous sub. in octahedral

„ Charge balanced by interlayer cations e.g. Ca2+, Mg2+ , Na+

„ Presence of interlayer
y water: swell-
swell-shrink characteristics

„ Half cell: M0.33, H20 (Si4)IV(Al1.67 Fe2+, Mg2+)0.33)VIO10(OH)2

„ Interlayer cations exchangeable

, Ca

Clay mica
Comparison: 0.6-0.9/half cell
Tetra- and octa-

Three main
2:1 minerals

Vermiculite
0.6-0.9/half cell
Tetra- and octa-

Montmorillonite
0.2-0.6/half cell
Octa- only
 Structure of 2:1:1 Clay minerals
z Chlorite

‹ 2:1 layer plus a hydroxide interlayer e.g. gibbsite-like, Al(OH)x or

brucite-like, Mg(OH)x where x <3 or 2

‹ Hydroxide interlayer positively charged and continuos

‹ Isomorphous substitution and layer charge variable

‹ Hydroxide interlayer strongly bond to tetrahedral sheets of 2:1

layer by H-bonding, therefore no shrink-swell

ƒ Interlayer cations are not readily

g
exchangeable
ƒ Tri, trioctahedral chlorite vs. Di,
dioctahedral chlorite
ƒ Half cell for Tri, trioctahedral chlorite
(clinchlore):
(Mg2AlOH6)(Si3Al)IV(Mg)3)VIO10(OH)2

Intergrade 2:1 Clay minerals

z Hydroxy-interlayered smectite or vermiculite

‹ Hydroxy interlayer islands (gibbsite-like or brucite-like) but not continuous

‹ Hydroxy-interlayered vermiculite (HIV) with hydroxy-Al common in acid

soils but in alkaline soils, hydroxy interlayer with hydroxy-Mg common

‹ Effect of hydroxy interlayer on cation exchange properties (e.g. K)

Text, Table 2.4

summary on
phyllosilicate clay
minerals
 Interstratified Clay minerals

z Different layers can stack together to form

mixed clay minerals.
‹ e.g. 1:1 chlorite to smectite

z Weak bond between layers cause

formation of mixed clay minerals

Allophane and Imogolite

z Formed from volcanic ash materials

z Allophane
‹ amorphous, weak x-ray diffraction pattern
‹ molar Si/Al ratio = 1:1~1:2
‹ Al in both tetrahedral and octahedral coordination

z Imogolite
‹ molar Si/Al ratio =1:2 constant
‹ Al in octahedral coordination only
 Other Secondary minerals
z Oxides/hydroxides/oxyhydroxides

‹ Generally as oxides

‹ Small quantity in soils but extremely important

‹ High specific surface area and reactivity

‹ Exist as discrete crystals, coatings, gels

Other Secondary minerals

z Major oxides in soils

‹ Aluminum oxides
Gibbsite γ-Al(OH)3
• Gibbsite,
– Octahedral coordination
– Common in highly
weathered soils (tropical
areas)

a a

• Boehmite, γ-AlOOH

• pH-dependent charge (edge)

-Al-OH1/2- + H+ → -Al-OH21/2+
 Other Secondary minerals
z Major oxides in soils

‹ Iron oxides
• Goethite, α-FeOOH, most common
• Hematite, α-Fe2O3, second most common
• Maghemite, γ-Fe2O3

‹ Octahedral coordination

‹ Isomorpous substitution (e.g. Al, Ni, Mn, Cu)

‹ Found in highly weathered soils

‹ α phases (O or OH ions hexagonally close

packed) stable than γ phases (cubic closed
packed)

Other Secondary minerals

z Major oxides in soils

‹ Manganese oxides

• Most Mn oxides are

amorphous (weak x-ray
diffraction)

• Common as coating on soil

particles
Gray Birnessite

• Birnessite, MnO2, most

prevalent in soils
 Carbonate and Sulfate Minerals
z Both commonly found in arid and semiarid
regions
z Much more soluble than silicate minerals
z Carbonates
‹ Calcite, CaCO3 can be both primary or secondary
‹ Mg-Calcite, MgxCa1-x (CO3)2 soil
‹ Dolomite, CaMg(CO3)2
‹ Important on P fixatiobn

Sulfate

‹ Gypsum, CaSO4.2H2O

Si, Al, Fe, and Ti

Alteration pathways to secondary minerals Mason, 1966

Main chemical
mechanisms on
weathering:
Hydration-hydrolysis

Exchange reaction
H+ from water or carbonic
acid to replace base cations

Oxidation reaction
Fe2+ in certain minerals
oxidized
Weathering of mica

Arizona: 2-5’’ (5-12 cm)

North Louisiana : 48-52” (122-132 cm)
Type of minerals as indicators for relative degree of soil development
‹ In young soils,
Relative degree of Prominent minerals in soil clay fractions more primary
minerals
soil development
‹ Tectosilicates and
1 Gypsum, other soluble salts phyllosicates (high
Si/O ratio) more
2 Calcite, dolomite and apatite resistant than
3 Olivine minerals neosilicate and
inosilicate minerals
4 Biotite, chlorite (low Si/O) ratio.
5 Feldspars
6 Quartz ‹ Kaolinite more in
relatively
7 Muscovite-illite developed soils
8 Interstratified 2:1 layer silicates and vermiculite (e.g. Southeastern
US) than
9 Montmorillonites montmorillonite
10 Kaolinite and halloysite (more in temperate
regions)
11 Gibbsite and allophane
12 Hematite-goethite ‹ In highly
g y weathered
13 Anatase (TiO2) soils, more metal
oxide minerals
(Gibbsite, Goethite)
(Jackson&Sherman, 1953)

Relationship between relative degree of soil

development and mineral types

Characteristics of Soil Minerals

z Specific surface of soil minerals
• External surface---Surface of clay particles
– Area measured by non-polar N2 absorption following BET Equation
(B
(Brunauer, E
Emmert,
t and
dTTeller,
ll 1938)

P = pressure of gas e.g. nitrogen gas (in Pa)

P0 = pressure required for saturation at the temperature of experiment (in Pa)
V = volume of gas adsorbed at pressure (in m3)
Vm = volume of gas for monolayer coverage over the solid surface (in m3)
E1 =heat of adsorption for first layer of gas molecule
EL =heat of liquefaction of gas
N = Avogadrao’s number (6.02X10-6 molecules/mole)
o
S =cross sectional area of gas (in m2)
Vo = molar volume of gas (m3) a = weight of solid
 Characteristics of Soil Minerals
z Specific surface of soil minerals
• Internal surface---Surface of mineral interlayer space (e.g.
(e g
montmorillonite)
– Non-polar N2 unable to penetrate interlayer space so not able to
measure
– As high as 80-90% of total surface area can come from internal
surface in certain minerals

• Total Surface area usually determined by monolayer absorption

of polar ethylene glycol (EG) or ethylene glycol monoethyl ether
(EGME).
EGME

• Difference used to calculate internal surface area

Characteristics of Soil Minerals

M in e ra l S p e c ific s u ra fc e
2
(m /g )

Specific K a o lin ite 7 -3

30
H a llo ys ite 1 0 -4 5
surface P yro p h yllite 6 5 -8 0
T a lc 6 5 -8 0
M o n tm o rillo n ite 6 0 0 -8 0 0
D io c ta h e d ra l V e rm ic u lite 5 0 -8 0 0
T rio c ta h e d ra l V e rm ic u lite 6 0 0 -8 0 0
M u s c o v ite 6 0 -1 0 0
B io tite 4 0 -1
100
C h lo rite 2 5 -1 5 0
A llo p h a n e 1 0 0 -8 0 0
A lu m in u m o x id e s 1 0 0 -2 2 0
Iro n o x id e s 7 0 -2 5 0
M a n g a n e s e o x id e s 5 -3 6 0

(S p a rk s , 2 0 0 3 )
 Characteristics of Soil Minerals
z Surface Charge of Soil minerals

• Type
T off charge
h
– Permanent (or constant charge)

– Variable (or pH-dependent charge)

• Due to protonation and deprotonation of functional groups (edge
sites)
• Cation(anion) exchange capacity (CEC/AEC): sum of exchangeable
cations (anions) that a soil or soil constituent can absorb at a
specific pH

• Contribution of function groups to CEC/AEC (Depending on pKa)

– Example

Characteristics of Soil Minerals

Mineral CEC
z Kaolinite - no isomorphous sub.,
(cmol/kg) edge site

Kaolinite 2- 15 z Talc - no layer charge

Halloysite 10- 40
z Montmorillonite –
Talc <1
Montmorillonite 80- 150
z Dioctahedral Vermiculite -
Dioctahedral Vermiculite 10- 150 tetrahedral sub, K+
Trioctahedral Vermiculite 100- 200
Muscovite 10- 40 z Chlorite -- interlayer blocking
Bi tit
Biotite 10 40
10- cation exchange
Chlorite 10- 40
Allophane 5- 350 z Allophane - Si4+ by Al3+, and
edge site

(Sparks, 2003)
Calculation of CEC from Unit Cell
formula
 Identification of Soil Minerals
z X-ray Diffraction Analysis: (crystal vs. amorphous)

CB + BD must be = nλ

n, order of reflection (integer) Bragg’s Equation: nλ = 2dsinθ

d-spacing is interlayer or diffraction
spacing
z Organoclays
Clays (Montmorillonite) have large
surface areas but not effective in
retaining natural nonionic organic
compounds (e.g. PAHs)

Ethylbenzene sorption (Boyd, 1991)

Organoclays: Clays modified to become

organic
i surface
f (organophilic)
( hili ) by
b
reacting with positively charged
surfactants, e.g. hexadecyltrimethyl
ammonium

Used as liner materials in landfills, and

in spill control situation