Lecture 4

z
Soil Mineralogy
x y
and
Chemistry
Phyllosilicate
Minerals
 4.31
Phyllosilicates, NO layer charge

T:O trioctahedral dioctahedral

(class)

octahedra oct oct

brucite gibbsite

tet tet
1:1
oct oct
serpentine kaolinite

tet tet
2:1 oct oct
tet tet
talc pyrophyllite
Building of Tetrahedral Sheets

* Linked SiO4 tetrahedra

 SiO4 Tetrahedron

z z

x y
x y
SiO4 Tetrahedron

Polyhedral View
 z

y
x
Si6O18
Linking Rings to Form
Tetrahedral Sheets
 Tetrahedral Sheet

y Si:O
z 2:5
Building of Octahedral Sheets
Al(OH)6 or Mg (OH)6 Octahedra

OH
Al(OH)6 or Mg (OH)6 Octahedra
 4.18

Octahedral Sheet

OH
z

y
x
 4.19
(tri)Octahedral Sheet

y Mg (OH)6 Octahedra
x
A Georgian
Ultisol
Octahedral-Tetrahedral
Linkage
Sharing of Apical Oxygens in Tetrahdral Sheet with
Hydroxyls of Octahedral Sheet
Serpentine (1:1 trioctahedral mineral)

tet

oct

x y
 Sharing of Apical Oxygens in Tetrahdral Sheet with
Hydroxyls of Two Octahedral Sheets

Talc (2:1 trioctahedral mineral)

tet

oct

tet

x y
Short-hand Symbols

tet

oct

Short hand,
Block notation
Phyllosilicates, NO layer charge

T:O trioctahedral dioctahedral

(class)

octahedra oct oct

brucite gibbsite

tet tet
1:1
oct oct
serpentine kaolinite

tet tet
2:1 oct oct
tet tet
pyrophyllite talc
Charge Development

Isomorphic Substitution
Î permanent (layer) charge
 4.28
Isomorphic Substitution

tet
Al3+
Si4+

oct Al3+,
Mg2+ Fe3+

x y
 NET
Charge
- - - - - - -
++ ++ ++ ++ ++ ++ ++ 0
- - - - - - -

Isomorphic substitution

- - - - - - -
++ + ++ ++ ++ + ++ -2
- - - - - - -
Charge Development

Terminal Bonds
ÎpH-dependent charge
(ionizable functional groups)
 Terminal Bonds

terminal
bonds

x y
Terminal Bonds: Ionizable Functional Groups

O
Al

Al-OH2+ ÅÆ Al-OHo + H+ ÅÆ Al-O- + H+

Low pH High pH

-pH-dependent charge
- edges of phyllosilicates; all surface on Fe- and Al-oxides
Phyllosilicates: 2:1 with layer charge

micas 2:1 clay minerals

tet tet
oct oct
tet tet
K+ K+ K+ 2+ H2O H O K+
H2O Ca 2
tet tet
oct oct
tet tet
1 unit of (-) layer charge < 1 unit of (-) layer charge
per formula unit per formula unit
General Classes (layer build-up) of Phyllosilicate Minerals:
Layer Type Charge† Trioctahedral Dioctahedral

1 octahedra 0 brucite, Mg(OH)2 gibbsite, Al(OH)3

1 tet. : 1 oct. 0 serpentine, Mg3Si2O5(OH)4 kaolinite, Al2Si2O5(OH)4

2 tet. : 1 oct. 0 talc, Mg3Si4O10(OH)2 pyrophyllite, Al2Si4O10(OH)2

2 tet: 1 oct. 1 phlogopite muscovite

KMg3(AlSi3O10)(OH)2 KAl2(AlSi3O10)(OH)2

1 biotite
KFe3(AlSi3O10)(OH)2

0.6-0.8 illite (hydrous mica)

K(Na,Ca) Al1.3Fe0.4Mn0.2Si3.4Al0.6O10(OH)2

0.6-0.9 vermiculite

0.25-0.6 smectite
† The layer charge per formula unit
Swelling Potential?
Interlayer Status: d-spacing
Structure d-spacing

K+

(and mica)
 4.35
Properties of Clay Minerals

Surface Area (m2/g) Interlayer Cation

CEC
Size (µm) External Internal Spacing (nm) cmol/Kg
Sorption
Kaolinite 0.1-5.0 10-50 - 0.7 5-15
Smectite <1.0 70-150 500-700 1.0-2.0 85-110
Vermiculite 0.1- 5.0 50-100 450-600 1.0-1.4 100-120
Illite 0.1-2.0 50-100 5-100 1.0 15-40
Humus coatings - - - 100-300
Accessory
Minerals

Kaolin and Oxide

Rich Soil

Western GA
Ultisol
 Smectite Soil Iron and Al-oxide Rich

NE Montana Vertisol
Hawaiian Oxisol
Clay mineralogy reflects weathering processes

Micas Æ Vermiculite Æ Smectite Æ Kaolinite Æ Al,Fe-Oxides

Young, weakly weathered soils

= fine-grained mica, chlorite, vermiculite
(Entisol, Inceptisol)

Intermediate weathering
= vermiculite, smectite, kaolinite
(Mollisol, Alfisol, Ultisol)

Strong weathering
= kaolinite, hydrous oxides
(Ultisol--> Oxisol)
 Mol
E/I E/I
Alf

Ult
Organic Matter

- reactive functional groups: carboxyl, hydroxyl, phenolic

* Humus, Humic Acid, Fulvic Acid