Applied Mineralogy (GG50005)

Autumn 2022

Lecture-1: Introduction
011.01.2024
Sujoy Ghosh
Department of Geology & Geophysics
Indian Institute of Technology Kharagpur
sujoy.ghosh@gg.iitkgp.ac.in
 Most abundant elements in Earth’s crust and mantle (by weight %)

Most abundant elements in Earth’s

crust (by vol. %)

Oxygen – 86 vol.%
Other elements – 14 vol.%

[Hint: Volume – Mass/Density]

Density of oxygen gas at 1 atm

pressure is 0.01429 g/cc.

Density of silicon at 1 atm pressure

is 2.33 g/cc.

Three most abundant elements = 82 wt.% Three most abundant elements = 95 wt.%
(Oxygen, Silicon and Aluminum) (Oxygen, Magnesium and Silicon)
https://opengeology.org/Mineralogy/
Most abundant elements in Earth and universe (by weight %)
 Structure of the Earth
Crust:
Oceanic crust
Thin: 10 km – Basaltic
Continental Crust
Thicker: 20-90 km
Average ~ granodiorite

Mantle: (35 – 2900 km)

Peridotite (ultramafic) Richard Dixon Oldham
Upper mantle  SiIV

Lower mantle  SiVI

Core: (2900 – 6370 km)

Fe-Ni metallic alloy
Increasing volume
Outer Core is liquid
IC<OC<UM<LM
No S-waves
Inner Core is solid Inge Lehmann
 How far down have we gone?

Tau Tona Gold mine, Johnnesburg (3.9 km)

Mantle xenolith
(150-200 km)

Kola Superdeep Borehole Diamond (150-700 km)

(12.3 km)
 The Preliminary Reference Earth Model (PREM)

Prof. Don Anderson

Cal Tech

Prof. Adam Dziewonski

Harvard University

Crafoord Prize (1998)

Swedish Academy/$ 500000 [Dziewonski and Anderson, 1981]
• Dunite named after Dun
Mountain in New Zealand).

• Lherzolite after É tang de

Lherz in the French Pyrenees.

• Harzburgite after the

town of Harzburg in the
Harz Mountains of
Germany.

• Wehrlite named after a

19th century petrologist
by the name of Alois Wehrle,
who produced the
first analysis of such rock.

• Websterite after Webster

County, North Carolina

Cambridge University Press 2010

 Model composition for Earth's upper mantle
(Pearson et al., 2014, Nature)

Prof. Alfred E Ringwood

(1930 – 1993)
Australian National University Super deep diamond from Juina with a
ringwoodite inclusion containing
~1 wt.% water
(3-4 oceans of water in transition
zone)

Wadsleyite was first identified by Prof. Ringwood and was

named for mineralogist Arthur David Wadsley (1918–1969)

A. E. Ringwood Medal
 Pyrolite model
The upper mantle is mineralogically dominated by pyroxenes and olivine (hence pyr-ol-ite).

Basic assumptions in this model are

1) basaltic volcanism at mid-ocean ridges is the most fundamental volcanism that

is due to the partial melting of rocks in the deep upper mantle,

2) Mg- and Fe-rich rocks (peridotite) occasionally found as xenoliths are the
residue of partial melting.

Ringwood called this hypothetical rock in the source region pyrolite which is a
mixture of mid-ocean ridge basalt and (depleted, i.e., differentiated) peridotite
such as harzburgite.

Chemical composition of some peridotite xenoliths is close to the pyrolite (e.g.,

xenolith from Kilbourne Hole (KLB1) in New Mexico in USA.

The pyrolite model for mantle composition assumes that the mantle has a nearly
homogeneous (with depth) composition.
 Pyrolite model

1 Primitive mantle based on the pyrolite model based on peridotites, komatiites and basalts.
2 Primitive mantle based on the pyrolite model based on MORB and harzburgite.
3 The model composition based on the CI chondrite.
4 Mid-ocean ridge basalt.
5 Depleted peridotite made mostly of olivine and orthopyroxene.
 Most common minerals in the Earth’s crust (vol.%)

minerals in the Earth’s crust

 Naica crystal cave (Chihuahua, Mexico)

Selenite – variety of
gypsum

Hydrous calcium sulfate

(CaSO4.2H2O)
Most common minerals in the Earth’s mantle (vol.%)

Upper SiIV
mantle
SiIV

Transition
zone
SiIV and SiVI

Lower
mantle
SiVI
(Frost, 2005, Elements)
2900 km
Depth variations of the Bullen parameter

where dρ/dz is the density gradient (z is the

depth) in a real Earth model.

(dρ /dz)ad is the adiabatic density gradient

calculated from seismic wave velocities and
gravity.
Most common minerals in the Earth’s mantle (vol.%)

Upper SiIV
mantle
SiIV

Transition
zone
SiIV and SiVI

Lower
mantle
SiVI
(Frost, 2005, Elements)
2900 km
Deep seismic tomography
 Water storage capacity of mantle silicates
Nominally Anhydrous Mineral
(NAM)

When there is on (OH)1- in the

mineral formula.
(Pearson et al., 2014, Nature)

Ringwoodite

Super deep diamond from Juina, Brazil with a

ringwoodite inclusion containing ~1 wt.% water modified from
(3-4 oceans of water in transition zone) Litasov and Ohtani, 2007
10th September 2008
Most common minerals in the Earth’s mantle (vol.%)
Most common minerals in the eclogitic mantle (vol.%)

CF - Calcium ferrite Ca(Fe,Al)2O4

NAL - New hexagonal alumina phase
 Abundant element in Earth’s crust and upper mantle

Common
Chemical
Name Charge coordination Ionic radius (Å)
symbol
number with oxygen
oxygen O 2- - 1.40

silicon Si 4+ 4 0.26

aluminum Al 3+ 4-6 0.39-0.54

3+ 4-6 0.49-0.65
iron Fe
2+ 6 0.78
magnesium Mg 2+ 6 0.72

calcium Ca 2+ 6-8 1.00-1.12

sodium Na 1+ 6-8 1.02-1.18

potassium K 1+ 8-12 1.51-1.64

Cuboctahedron
 Three views of a silicon tetrahedron
• Tetra means four in Greek and Hedra means face/side.
[SiO4]4-
• Net charge on a silicon tetrahedron = (4+)X1 + (2-)X4
= (4+) + (8-)
= (4-)
• Bridging and non-bridging oxygen

• Si-O bond length – 1.60 Å & Si-O-Si bond angle - 140°

• Aluminum tetrahedron - [Al3+O4]5-

• In silicate structure, Al3+ is substitute for Si4+ in

tetrahedron, such substitution must be accompanied
by some compensating replacement in the cation
content to maintain electrical neutrality.

http://www.chem.ox.ac.uk/vrchemistry/chapter6/Page21.htm
 Pauling’s Third Rule - Sharing of polyhedral elements I

• Sharing of edges or faces by two anion polyhedral decreases the stability of a crystal.

Klein and Dutrow (2007)

 Mineral formula
Basic rules
VI IV
1) Charge balance must be maintained. Forsterite (Mg2+) 2 Si4+ O4

2) The atom must fit into the structure.

3) Elements with subscripts to indicate the relative numbers of atoms present.

4) Cations (positively charged ions) before anions (negatively charged ions) and
molecular anionic species, with the largest cations coming first.
VI IV
Olivine - (Mg2+,Fe2+) 2 Si O4
XII VI IV
Muscovite – K Al2 (AlSi3O10) (OH)2

olivine from Hawaii muscovite from Brazil

 Silicates
Depolymerized Nesosilicates Si:O = 1:4
Example: olivine, garnet
Sorosilicates Si:O = 2:7
Example: epidote
Inosilicates Si:O = 1:3 (single chain)
Example: pyroxene
Inosilicates Si:O = 4:11 (double chain)
Example: amphibole
Ringsilicates Si:O = 6:18
Example: beryl
Phyllosilicates Si:O = 2:5
Example: mica
Tectosilicates Si:O = 1:2
Polymerized Example: quartz, feldspar
 Discovery of Hiroseite (a new mineral)

The Suizhou meteorite fell in 1986

in Hubei province, China

With Prof. Kei Hirose

(University of Tokyo, Japan)
The Commission on New Minerals, Nomenclature and Classification (CNMNC) of
the International Mineralogical Association (IMA)
A small hiroseite crystal
(Fe-rich analog of bridgmanite) Bindi et al., 2020, Science Advance
 Crystal structure of olivine (α phase)

General formula: (Mg,Fe)VI2SiIVO4

Density of olivine – 3.22 g/cm3.

Structure:

Structure of olivine projected

perpendicular to the a-axis

M2 octrahedra corner sharing O

with SiO4 tetrahedra

M2 and M1 octrahedra edge sharing

Fe, Mg randomly occupying M1 and

M2 sites (equal prob.)
http://www.alexstrekeisen.it/english/vulc/olivine.php
 Crystal structure of garnet

General formula - XVIII3YVI2SiIV3O12

X – 8 fold coordination
Y – 6 fold coordination
Si – 4 fold coordination
 Crystal structure of pyroxenes

General formula - XVI2SiIV2O6

X – 6 fold coordination
Si – 4 fold coordination

M1 and M2 sites
 Majoritic garnet

Dodecahedral Octahedral Tetrahedral

Normal
garnet
(Mg,Fe,Ca,Mn)3 Al2 (SiO4)3
Occurs on solution of
clinopyroxene and garnet at Si, Mg Al
pressures ~ 13-19 GPa (400 –
550 km)

Dod Oct Tetr

Classical majorite Mg3(MgSi)(SiO4)3

Named after Alan Major, who assisted A.E. Ringwood in the high-pressure synthesis of majorite. The term
“majorite” was first proposed by Smith & Mason (1970) who obtained its composition in the shock
meteorites.
 Crystal structure of majorite
Classic majorite - MgXII3(MgSi)VI(SiO4)3

• Occurs on solution of clinopyroxene and

garnet at pressures ~ 8-27 GPa (250–700
km).
• Majorite was first found in nature in the
Coorara meteorite (L6 chondrite meteorite)
from Western Australia.
• Orange spheres represent Mg2+ which
occupy 12-fold sites (the interstitial site
between tetrahedral and octahedral sites).

• Blue octahedra are occupied by Si4+ and

orange octahedra are occupied by Mg2+.

• Blue tetrahedrons are occupied by Si4+.

Lou et al., 2020, PEPI
 Crystal structure of wadsleyite (β phase)
• Wadsleyite, a high-pressure phase of olivine, is
an orthorhombic mineral with the formula β-
(Mg,Fe)2SiO4. Density of wadsleyite – 3.47 g/cm3.

• Wadsleyite was first found in nature in the Peace

River meteorite (L6 chondrite meteorite) from
Alberta, Canada.

• Wadsleyite was named for mineralogist Arthur

David Wadsley (1918–1969).

• SiO4 tetrahedra (blue) are shown with

MO6 octahedra (brown),
• Mg-Fe atoms (orange) and O atoms (red).

Anhydrous wadsleyite – modified spinel

Water-rich wadsleyite - monoclinic

https://home.hiroshima-u.ac.jp/kawazoe/html/Kawazoe03-Crystal-EN.html
 Crystal structure of ringwoodite (γ phase)
• Ringwoodite, a high-pressure phase of olivine, is
an isometric mineral with the formula γ-(Mg,Fe)2SiO4.
Density of ringwoodite – 3.55 g/cm3.

• Ringwoodite was first found in nature in the Tenham

meteorite (L6 chondrite meteorite) near the Tenham
station, South Gregory, in western Queensland.

• Ringwoodite was named for mineralogist Ted

Ringwood (1930–1993).

Prof. Alfred E Ringwood

(1930 – 1993)
Spinel – 64 T sites (8 are occupied) and 32 O sites (16 are Australian National University
occupied)
https://home.hiroshima-u.ac.jp/kawazoe/html/Kawazoe03-Crystal-EN.html
 Crystal structure of Akimotoiite (ilmenite-structure)

Akimotoiite – MgSiO3
 Crystal structure of bridgmanite
• Bridgmanite mainly exist in the lower part of Earth's mantle, between
about 660 and 2,700 km, is an orthorhombic mineral with the formula
(Mg,Fe)SiO3. Density of bridgmanite – 4.10 g/cm3.

• Bridgmanite was first found in nature in the Tenham meteorite (L6

chondrite meteorite) near the Tenham station, South Gregory, in
General formula – XXIIYVIO3 western Queensland.

• Bridgmanite was named for Percy Williams Bridgman (1882–1962).

Percy W. Bridgman 1946 Nobel Price in Physics for

(1882–1962) his work on the physics of high
American experimental physicist pressures
https://www.danshimlab.info/resources/images
 Crystal structure of post-perovskite
General formula – XXIIYVIO3
• Post perovskite mainly exist in the base of Earth's lower
mantle, between about 2,700 and 2,900 km, is an
orthorhombic mineral with the formula (Mg,Fe)SiO3.

• Post perovskite structure is a stacked SiO6-octahedral sheet along

the b axis.

• SiO6-octahedra edges sharing along a-axis.

• SiO6-octahedra corners sharing along c-axis.

• SiO6-octahedra alternating with MgO8.

https://www.danshimlab.info/resources/images
High pressure phase relation in olivine
Depth variations of the Bullen parameter

where dρ/dz is the density gradient (z is the

depth) in a real Earth model.

(dρ /dz)ad is the adiabatic density gradient

calculated from seismic wave velocities and
gravity.
 Forces that holds things together

1. Gravitational Force F = G m1.m2 ;

r2

2. Electrostatic Force F= 1 q1.q2 ;

4πϵ0 r2

Calculate the gravitational force and electrostatic forces that holds 2Fe atoms together.
 Electronegativity
Electronegativity is a value that describes the ability of an atom to attract electrons
towards it in a bond.
Electronegativity increases

Highest electronegative
are towards upper right
of periodic table.

Metals are least

Electronegativity decreases electronegative of the
elements.
1. Ionization energy
(energy required to remove e-
present in the outer shell of an Francium – 0.7 ev
atom)
2. Electron affinity
(energy required to attract an
e- to an atom from infinity)
2 Where XA and XB are
% of ionic character = 1 − 𝑒 −1/4 𝑋𝐴−𝑋𝐵 electronegativity of atom A
and B
 Electronegativity
Cation/Anion Ionic radius (Å) Electronegativity (eV)
Si4+ 0.26 1.90
Ti4+ 0.68 1.54
Al3+ 0.39-0.54 1.61
Mg2+ 0.72 1.31
Linus Carl Pauling
Fe2+ 0.78 1.83 (1901-1994)

Mn2+ 0.80 1.55

Ca2+ 1.00-1.12 1.00
Na1+ 1.02-1.18 0.93
K1+ 1.51-1.64 0.82 1954 Nobel Price in Chemistry for his
work on the nature of the chemical bond.
O2- 1.40 3.44
1962 Nobel Peace Price for his opposition
to weapons of mass destruction.
 Ionic Bonds
Na (1s22s22p63s1) –> Na+(1s22s22p6) + e-
• When two atoms with extreme
Cl (1s22s22p63s23p5) + e- –> Cl- (1s22s22p63s23p6)
differences in electronegativity (>1.8
ev) come together, the result is
termed as ionic bond (70%). Most
common in non-opaque minerals.
• Ionic bond involves complete
transfer of electrons.

• Melting point NaCl – 801oC whereas

(Mg,Fe)O - 2800oC.
• Density NaCl – 2.17 g/cm3 whereas
(Mg,Fe)O – 3.58 g/cm3.

• Poor conductors, have high

symmetry and coordination.
 Covalent Bonds
• When atoms of identical and high electro Cl:1s2 2s2 2p6 3s2 3p5
negativities brought close together, bonding
occurs by sharing of outer shell electrons.

• strongest of all chemical bonds

• most covalent minerals are insoluble in water

• high melting points, “The sharing of an electron pair constitutes a single bond”

• hard, nonconductive

• have lower symmetry and coordination.

Example: Diamond
www.tf.uni-kiel.de
 Calculate percentage of ionic character in SiO2?
EN (XB) = 1.90 for Si atom, EN (XA) = 3.44 for O atom

ΔEN (ΔX) = (3.44-1.90) = 1.54

2
−1/4 1.54
% of ionic character = 1 − 𝑒

= 1 − 𝑒 −1/4(2.73)

= 1 − 𝑒 −0.5929

= 1 - 0.55 = 0.45

So Si-O bond is ~ 45% ionic and 55% covalent.

% of ionic character in diamond: C-C bond is ~ 0% ionic and 100% covalent.
Note that ΔEN is 0 for diamond.
 Calculate percentage of ionic character in NaCl?
EN (XB) = 3.16 for Cl atom, EN (XA) = 0.93 for Na atom

ΔEN (ΔX) = (3.16-0.93) = 2.23

2
−1/4 2.23
% of ionic character = 1 − 𝑒

= 1 − 𝑒 −1/4(4.97)

= 1 − 𝑒 −1.24

= 1 – 0.29 = 0.71

So Na-Cl bond is ~71% ionic and 29% covalent.

% of ionic character in Al2O3: Al-O bond is ~57% ionic and 43% covalent.
Note that ΔEN is 1.83 for Al2O3.
 Percentage of Ionic and Covalent character

Ionic
Δx for Si-O = 1.54

Δx for Mg-O = 2.13

Δx for K-O = 2.62

Forsterite – 68% ionic; 32% covalent

Covalent
 Metallic Bonds
• Metals are formed between atoms with low and similar
electronegativity.

• If closely pack them can get up to 12 nearest neighbors. This

causes a high density of valence e- around any given atom & also
a high density of neighbor atoms around the loose valence e-

• These become a sea of mobile electrons. Metals are excellent

conductors

• Typical of elements with low ionization potential. Valence

electrons easily stripped.

• Yields minerals with minerals that are soft, ductile/malleable,

highly conductive (due to easily mobile electrons).

• Non-directional bonding produces high symmetry

 Ionic, Covalent, and Metallic Crystals
van Arkel–Ketelaar triangles

Melting Temp (Tm)

Diamond (4027 oC)

Al2O3 (2074 oC)

𝑿𝑨 − 𝑿𝑩 SiO2 (1710 oC)

NaCl (801 oC)

𝑿𝑨 − 𝑿𝑩

𝑿𝑨 + 𝑿𝑩 /2

https://opengeology.org/Mineralogy/