P.T.

INCO

Revised: May 12, 2005

P.T. INCO TYPICAL WB LATERITE PROFILE

Red Laterite

Limonite zone

Saprolite zone

Bedrock pinnacle
P.T. INCO WHAT ARE NICKEL LATERITES?

• Nickel laterites are residual soils that have developed

over ultramafic rocks through processes of chemical
weathering and supergene enrichment

• Critical conditions for the formation of nickel laterites:

§ Appropriate accumulation of soil
§ Appropriate rock type
§ Appropriate weathering conditions
§ Appropriate conditions for supergene enrichment
P.T. INCO APPROACH TO LATERITE STUDY

• Study of Laterites requires a good knowledge of the

relevant principles of:

• Chemistry
• Mineralogy
• Petrology
• Geomorphology
• Soil formation
• Processing constraints & technology
P.T. INCO Module 1

Forms of matter
Metals and non-metals
Nature of elements
Atomic number
FUNDAMENTALS Atomic weight
Ion, Cation, Anion
OF CHEMISTRY
Ionic Radii
Valency
Multiple valencies
Natural abundance of elements
P.T. INCO FORMS OF MATTER

• Five forms of matter are generally recognised:

§ Solid
§ Liquid
§ Gaseous
§ Plasma
§ Liquid crystal
P.T. INCO METALS AND NON-METALS

Metals have the following characteristics:

§ Metallic lustre
§ Opaque
§ Conduct heat and electricity
§ Malleable (can be shaped by a hammer)
§ Ductile (can be drawn into a wire)

§ Play the role of a cation or basic element in simple compounds

P.T. INCO NATURE OF ELEMENTS

All elements are made up of:

§ Proton: 1.00728 units — Positively charged particle
§ Neutron: 1.00867 units — Neutral
§ Electron: 0.00055 units — Negatively charged particle
§ Sub-atomic particles: Neon Atom

• A proton or neutron
is 1830 times heavier
than an electron

• Practically all the weight 10 Protons

of an atom lies in its nucleus 10 Neutrons
10 electrons
(protons and neutrons) (2-2-6)
P.T. INCO ATOMIC NUMBER / ATOMIC WEIGHT

ATOMIC NUMBER
• The number of protons indicates the Atomic Number
§ Hydrogen: At. No. 1 (one proton)
§ Helium: At. No. 2 (two protons)
§ Lithium: At. No. 3 (three protons)
§ Beryllium: At. No. 4 (four protons)
§ Boron: At. No. 5 (five protons)
§ Carbon: At. No. 6 (six protons)
§ Nitrogen: At. No. 7 (seven protons)

ATOMIC WEIGHT
• The weight of an atom’s protons, neutrons and electrons
• The weight is determined in relative terms
P.T. INCO Computation of Atomic Weights

Analysis of 100g of water — H2O:

§ 11.1g Hydrogen
§ 88.9g Oxygen
§ Formula of water = H2O ( H=2; O=1)
§ 2(H) + 1(O) = 100
§ 2(5.55) + 1(88.9) = 100
§ Atomic weight of Oxygen = 88.9 / 5.55 = 16.0

Analysis of 100g of Silica — SiO2:

§ 46.7g Silicon
§ 53.3g Oxygen
§ Formula of Silica = SiO2
§ Atomic weight of Si = 46.7 / (53.3/2) = 1.7523 x 16 = 28.0
P.T. INCO ION, CATION AND ANION

ATOMS REACT ONLY UNDER THEIR IONIC STATES

ION: An atom that has acquired a net electrical charge by either

gaining or losing an electron from its outer-most shell

CATION: A positively charged ion (mostly metals).

The atoms has lost electrons from its outer-most shell.
[Al, Ca, Cr, Co, Cu, Fe, K, Pb, Mg, Mn, Na, Ni, Si, Ti]

ANION: A negatively charged ion (mostly non-metals).

The atom has gained electrons in its outer-most shell.
[Br, Cl, F, O, S]

• All inorganic compounds are based on a cation-anion bond

• The union of cation and anion cancels the charges
P.T. INCO PACKING OF ATOMS

Linear Packing Triangular Packing

H2O CO3

Tetrahedral Packing
Silicon Tetrahedra Cubic Packing
SiO4 Native metals
P.T. INCO IONIC RADII

• Ionic radius is the radius of an ion that is reported in

terms of angstrom units.
One angstrom is one ten millionth
of a millimetre (1°A = 10-7 mm) Co = 0.62

Fe3 = 0.64

Mg = 0.66

Ni = 0.69
Si
0.42 O
1.40 S Fe2 = 0.74
1.84
P.T. INCO VALENCY

• Valence (or valency) is the capability of an atom to

combine in particular proportion with another atom

Maximum allowable
• Requirements electrons in each shell 10
for a stable (inert) 6 3d
atom
2
6 3p
• Valence is
1s 2 3s
controlled by the 2
number of free 2p
2s
electrons in the
outer most shell
or shells of the atom
Stable Configuration of
inert gases
P.T. INCO Making Sodium Chloride — NaCl
11 Protons 17 Protons
11 Electrons 17 Electrons
Cl
Na (2-2-6-1) (2-2-6-2-5)
5
1
2
6 6
2 2 2
2

Sodium achieves stability by

losing 1 electron. Its ion
becomes positively charged
(valency of 1+). The last shell
now has stable 6 electrons.
Chlorine achieves stability by
gaining 1 electron. Its ion
becomes negatively charged
(valency of 1-). The last shell
now has stable 6 electrons.
P.T. INCO DIFFERENT VALENCIES

• NaCl Na Cl
• CaCl2 Ca Cl2
• AuCl3 Au Cl3
• SnCl4 Sn Cl4

• PCl5 P Cl5

Other
Valency atoms Examples

Monovalent 1 H, K, Li, Na, Ag, F, Cl, Br, I

Divalent 2 Be, Ca, Co, Mg, Sr, Ba, O, S,
Trivalent 3 B, Al,
Tetravalent 4 C, Si, Ti, Zr
Pentavalent 5 V, Nb, Ta
P.T. INCO DUAL ROLE OF SOME IONS

Some ions can act as both a Cation and an Anion:

§ SO2 Sulphur dioxide (S as a cation)

§ FeS2 Iron sulphide — Pyrite (S as an anion)

§ AsS Arsenic sulphide — Realger (As as a cation)

§ NiAs Nickel arsenide — Niccolite (As as an anion)

§ Sb2S3 Antimony sulphide — Stibnite (Sb as a cation)

§ NiSb Nickel antimonide — Breithauptite (Sb as an anion)

• Elements such as As, Sb, Bi, Te and Se play dual role in

chemical bonding and are called “semi-metals”
P.T. INCO MULTIPLE VALENCIES

• Fe and O:
§ FeO Fe++O-- Iron protoxide (Ferrous divalent iron)
§ Fe2O3 Fe+++O-- Iron sesquioxide (Ferric trivalent iron)
• N and O:
§ N2O N+O-- (Nitrogen is monovalent)
§ NO N++O-- (Nitrogen is divalent)
§ N2O3 N+++O-- (Nitrogen is trivalent)
§ NO2 N++++O-- (Nitrogen is tetravalent)
§ N2O5 N+++++O-- (Nitrogen is pentavalent)
• S and O
§ SO2 S++++O-- Sulphur dioxide (S is tetravalent)
§ S2O3 S+++O-- Sulphur trioxide (S is trivalent)
P.T. INCO MULTIPLE VALENCY ELEMENTS

Valency State
1 2 3 4 5 6
Cu +1 +2
Au +1 +3
Pb +2 +4
Co +2 +3
Ni +2 +3
Fe +2 +3
Mn +2 +3 +4
Cr +2 +3 +6
As +3 +5
Sb +3 +5
Bi +3 +5
P.T. INCO NATURAL ABUNDANCE OF ELEMENTS

% of Earth’s Crust % of total Earth

O 46.6 29.5
74.3%
Si 27.7 15.2
Al 8.1 1.1
Fe 5.0 34.6 92 %
Ca 3.6 1.1
Na 2.8 0.6
K 2.6 0.1
Mg 2.1 12.7
Total 98.5 94.9
P.T. INCO Module 2

Definition of mineral
Classification of minerals
Mineral formulas
Mineral compositions
Examples of ionic replacement
FUNDAMENTALS
Binary diagrams
OF MINERALOGY Ternary diagrams
Assay reporting conventions
Element to oxide conversion
Calculation of formula from assays
Chemical analysis of minerals
Identification of minerals
P.T. INCO WHAT IS A MINERAL

A mineral:
§ Occurs naturally
§ Is a solid
§ Is crystalline
§ Has a definite chemical composition
(not necessarily a fixed composition)

• “A mineral is a naturally occurring crystalline solid with

a definite chemical composition”

• Laboratory made minerals are called “synthetic

minerals”
• Non-crystalline and amorphous substances are not truly
minerals (asbolite, bauxite, limonite, opal, psilomelane)
P.T. INCO MINERAL CLASSIFICATION

Classification according to Dana

Native Elements Carbonates (R.CO3) Arsanates (R.AsO4)

Titanates (R.TiO3) Vanadates (R.VO4)
Sulphides (R.S)
Niobates (R.NbO3) Antimonates (R.SbO4)
Selenides (R.Se)
Tantalates (R.TaO3) Borates (R.BO4)
Tellurides (R.Te)
Arsenides (R.As) Nitrates (R.NO3) Sulphates (R.SO4)
Antimonides (R.Sb) Uranates (R.UO3) Chromates (R.CrO4)
Tellurates (R.TeO3) Tungstates (R.WO4)
Halides:
Molybdates (R.MoO4)
(R.Cl), (R.Br), (R.I)
(R.F) Oxides (R.O)

Hydroxides (R.OH)

Silicates (R.SiO4)
P.T. INCO MINERAL FORMULA

• Mineral Formula:
§ Cation is written first, followed by anion or anionic group
§ Total charge of cations and anions must balance
§ Cations that replace each other are grouped together

Mineral Diopside:

• Empirical Formula: CaMgSi2O6 Wo

• Molecular Formula: CaO.MgO.2SiO2
• Structural Formula: VIIICaVIMgIVSi
2O6
Diopside
• End-member Formula: Wo50En50Fs0

En Fs
P.T. INCO FIXED vs. VARIABLE COMPOSITION

• Most minerals have a very fixed chemical composition

and do not alter from this fixed formula:
§ NaCl (Sodium chloride, or common salt)
§ H2O (Ice)
§ SiO2 (Silica)

• Many minerals show wide variation in chemical

composition:
Composition Range

§ Sphalerites: (Zn,Fe)S ZnS FeS

§ Olivines: (Mg,Fe)2SiO4 Mg2SiO4 Fe2SiO4
§ Orthopyroxene: (Mg,Fe)2Si2O6 Mg2Si2O6 Fe2Si2O6
§ Plagioclases: (Na,Ca)AlSi3O8 NaAlSi3O8 CaAl2Si2O8
P.T. INCO Distinct oxides of Iron
31
Fe2O3 Hematite (Fe sesquioxide)
30
Only three
29 compositions
Fe3O4 along this
28 (FeO.Fe2O3) line are
%O 27 Magnetite
possible

26

25
24

23 FeO
(Fe protoxide)
22
69 70 71 72 73 74 75 76 77 78
%Fe
P.T. INCO ZnS – FeS Solid Solution
70 ZnS
(Sphalerite)
60

50 All
compositions
% Zn 40
between pure
sphalerite
and pure
30 troilite are
possible

20

10 FeS
(Troilite/Pyrrhotite)
0
0 10 20 30 40 50 60 70
% Fe
P.T. INCO Forsterite-Fayalite Solid Solution
70 Fe2SiO4
(Fayalite)
60

50 All
compositions
% FeO 40
between pure
Forsterite
and pure
30 Fayalite are
possible

20

10 Mg2SiO4
(Forsterite)
0
0 10 20 30 40 50 60 70
% MgO
P.T. INCO IONIC REPLACEMENT

Certain Cations can replace each

other to form isomorphous series.
Following are the conditions:

• Cations should have about

the same ionic radii

Same size cations

• The minerals formed should
have the same crystal structure

• The difference in charge is

no more than one valency

• Suitable contact is available

among the various cations
P.T. INCO IONIC REPLACEMENT — Example 1

• Fe replaces Mg in olivines
Mg2SiO4 Forsterite (magnesian olivine)
Fe2SiO4 Fayalite (iron olivine)
(Mg,Fe)2SiO4 Solid solution of Mg and Fe olivines

• Fe replaces Mg in pyroxenes
MgSiO3 Enstatite (magnesian pyroxene)
FeSiO3 Ferrosilite (iron pyroxene)
(Mg,Fe)SiO3 Solid solution of Mg and Fe pyroxenes

• Ni replaces Mg in olivines
§ Small quantities of Ni, usually up to 0.4% Ni, replace Mg
§ In terms of atoms, approximately every 275th Mg is replaced by Ni
 OLIVINE
P.T. INCO STRUCTURE
P.T. INCO IONIC REPLACEMENT — Example 2

Al replaces Si in plagioclases
§ Al+++ is trivalent while Si++++ is tetravalent

§ Replacement of Si by Al leaves one + charge short

§ To complete the charge, another cation comes in

§ Basic plagioclase structure is = Si4O8

§ In Albite, every fourth Si is replaced by Al and Na

[NaAlSi3O8]

§ In Anorthite, every second Si is replaced by Al and divalent Ca

[CaAl2Si2O8]
P.T. INCO MINERAL COMPOSITION DIAGRAMS

Pure Binary Diagram Pure

Forsterite Fayalite

0 10 20 30 40 50 60 70 80 90 100

Olivine of intermediate
composition Fo90Fa10
Wo

Ternary Diagram P yro xe ne

Wo = 50%
En = 42%
Fs = 8%
En Fs
P.T. INCO REPORTING CHEMICAL COMPOSITION

Two conventions are used for reporting chemical

compositions of minerals:

§ Composition in terms of elements

§ Composition in terms of oxide or other anionic groups

• Example: Forsterite (Mg2SiO4)

§ In terms of elements: Mg Mg Si OOOO

§ In terms of molecular groups: 2MgO SiO2

P.T. INCO Assay Reporting Conventions

Forsterite: Mg2SiO4
Mg = 34.6%

24.3 24.3 24.3 24.3

O = 45.5%

16 16 16 16 16 16 16 16

MgO = 57.3%
28 28
Si = 19.9%
SiO2 = 42.7%

Assays reported in terms of Assays reported in terms of

elements oxides
P.T. INCO Reporting of LOI

• Many minerals lose weight if heated at high temperatures

(ignited)

• The loss on ignition (LOI) is reported as weight

percentage

• LOI can consist of water of crystallisation or gasses

such as CO2

• If LOI is water of crystallisation, it is reported as weight

percentage of H2O+
P.T. INCO Oxides associated with laterites
+1 +2 +3 Spinels +4 +5 +6
Al2O3
CaO
Co Co2O3
Cr2O3 CrO3
(CrO4)
FeO Fe2O3 Fe3O4
K2O
MgO
MnO Mn2O3 Mn3O4 MnO2
Na2O
NiO
P2O5
SiO2
TiO2
P.T. INCO CONVERSIONS (element to oxide)

Relationship between Ni and NiO:

At. Wt. of Ni = 58.7
At. Wt of O = 16
At. Wt. of NiO = 58.7 + 16 = 74.7
Ratio of Ni to NiO = 74.7 / 58.7 = 1.273

• Ni to NiO = 74.6 / 58.6 = 1.273

• Co to CoO = 74.9 / 58.9 = 1.272
• Fe to FeO = 71.8 / 55.8 = 1.287
• Fe to Fe2O3 = 79.8 / 55.8 = 1.430

• In the bedrock, iron is in two forms: mostly as FeO in

olivines and pyroxenes; some as Fe2O3 in magnetite
• In Limonite layer, iron is as Fe2O3 in hematite, goethite
and limonite
P.T. INCO FORMULA FROM CHEMICAL ANALYSIS

Wt. % Molecular Moles Oxide Ratios

Sorowako Olivine Weight
SiO2 40.3 60.0

FeO 8.92 71.8

MgO 50.8 40.3

NiO 0.37 74.6

Al2O3 0.41 101.8

CaO 0.007 56.0

P.T. INCO FORMULA FROM CHEMICAL ANALYSIS

Wt. % Molecular Moles Oxide Ratios

Sorowako Olivine Weight
SiO2 40.3 60.0 0.672

FeO 8.92 71.8 0.124

MgO 50.8 40.3 1.261

NiO 0.37 74.6 0.005 1.395

Al2O3 0.41 101.8 0.004

CaO 0.007 56.0 0.001

P.T. INCO FORMULA FROM CHEMICAL ANALYSIS

Wt. % Molecular Moles Oxide Ratios

Sorowako Olivine Weight
SiO2 40.3 60.0 0.672 1.0

FeO 8.92 71.8 0.124

MgO 50.8 40.3 1.261

NiO 0.37 74.6 0.005 1.395 2.08

Al2O3 0.41 101.8 0.004

CaO 0.007 56.0 0.001

Cations : SiO2 ratio is 2:1

Formula: 2MgO.SiO2 or 2(Mg,Fe)O.SiO2 approximate formula
2(Mg,Fe,Ni,Al)O.SiO2 exact formula
P.T. INCO FORMULA FROM CHEMICAL ANALYSIS

Wt. % Molecular Moles Oxide Ratios

Sorowako pyroxene Weight
SiO2 55.1 60.0 0.918 1.0
FeO 5.79 71.8 0.081
MgO 33.5 40.3 0.831
NiO 0.076 74.6 0.001
Al2O3 3.23 101.8 0.032 0.984 1.07
CaO 1.87 56.0 0.033
Cr2O3 0.58 152.0 0.004
MnO 0.13 70.9 0.002

Cations : SiO2 ratio is 1:1

Formula: MgO.SiO2 or (Mg,Fe)O.SiO2 approximate formula
(Mg,Fe,Ca,Al)O.SiO2 exact formula
P.T. INCO FORMULA FROM CHEMICAL ANALYSIS
Wt. % Molecular Moles Oxide Ratios
Petea Serpentine Weight
SiO2 42.0 60.0 0.700 1.0
FeO 3.0 71.8 0.042
MgO 39.5 40.3 0.980
NiO 0.25 74.6 0.003
Al2O3 1.0 101.8 0.010 1.049 1.499
CaO 0.3 56.0 0.005
Cr2O3 0.5 152.0 0.003
MnO 0.4 70.9 0.006
H2O+ 13.0 18.0 0.722 1.03
Cations : SiO2 : H2O ratio is 1.5:1:1 (or 3:2:2)
Formula: 3MgO.2SiO2.2H2O approximate formula
3(Mg,Fe,Al)O.SiO2.H2O exact formula
P.T. INCO CHEMICAL ANALYSIS OF MINERALS
• Wet Chemical Methods
§ Gravimetric
§ Colorimetric
§ Titration

• Instrumental Procedures
§ Atomic Absorption Spectrometry (AAS)
§ Mass spectrometry
§ X-Ray Fluorescence
§ Electron probe analysis
§ Raman spectrometry
§ Nuclear Magnetic Resonance spectrometry
§ Neutron Activation Analysis
§ Optical Emission spectroscopy
§ Plasma Emission Spectroscopy
P.T. INCO IDENTIFICATION OF MINERALS

• Hand sample identification

• Thin section identification
• Grain mount identification
• X-Ray Diffraction method
• Use of mineral association and paragenesis
P.T. INCO
P.T. INCO
P.T. INCO Module 3

Overview
Silicon Tetrahedron
Olivine group
Pyroxene group
Serpentinisation of olivines

MINERALS Serpentine group minerals

Chlorite group
ASSOCIATED
Spinels
WITH LATERITES
Oxides
Hydroxides
Clays
Nickel hydrosilicates
Asbestiform minerals
Compositions of various minerals
 P.T. INCO MINERALS ASSOCIATED WITH LATERITES
Oxides & Nickel
Mafics Spinels Clays Hydroxides Silicates

Primary Olivine Magnetite

igneous Pyroxene Chromite
minerals

Hydro-
Serpentine Magnetite
thermal Talc
minerals Chlorite

Serpentine Kaolinite Silica Nepouite

Secondary Talc Smectite: Hematite Willemsite
Laterite Chlorite (Mont- Goethite Pimellite
weathering morillonite) Limonite Connarite
(Nontronite) Bauxite Falcondite
minerals
Illite Gibbsite Nimite
Mixed Layer Noumeite
P.T. INCO MAFIC MINERAL STRUCTURE
Silicon Olivine
Tetrahedron

Pyroxene

Amphiboles

Micas
Sheet silicates
P.T. INCO FIELDS OF MAFIC MINERALS

Numbers indicate SiO2

MgO or FeO
content in %

En PYROX
ENES
40
Serpentine
44 Ferrosilite
Fo 54.5
57
OLIVINES Fa
70.5

MgO FeO
P.T. INCO OLIVINE GROUP

• Orthorhombic structure (3 unequal axes)

• Individual silicon-oxygen tetrahedra
linked by magnesium atoms

Forsterite Chrysolite Fayalite

Olivine type Magnesian Ferro-mag. Ferrous

Formula Mg2SiO4 (Mg,Fe)2SiO4 Fe2SiO4
Density 3.22 4.39
Hardness 7.0 6.5
Melting point 1890°C 1205°C
Composition MgO=57.3% FeO=70.5%
SiO2=42.7% SiO2=29.5%
P.T. INCO Olivine Crystals
z
Forsterite z Fayalite
Mg2SiO4 Fe2SiO4

y
y
x
x
 OLIVINE
P.T. INCO STRUCTURE
P.T. INCO OLIVINES — Chemical compositions

• There is a complete solid solution between Mg and Fe olivines

• Chemical composition of olivines is generally indicated by FoxxFayy
• Pure Mg and Fe end members are rare in nature
• Composition of olivine from dunite of Dun Mountain is Fo92
• Mg-olivine crystallises first from the magma. Usually Fo88 to Fo82
• Average composition of peridotite olivine is Fo88
• Olivines of basic igneous rocks is generally Fo80 to Fo50
• Olivine in ferro-gabbros of Skaergaard intrusion is Fo39 to Fo2

Soroako Unserp. Poro Harz. Tiebaghi Harz.

SiO2 40.3 40.8 39.2
FeO 8.9 7.8 9.0
MgO 50.8 49.2 51.4
NiO 0.37 0.50 0.30
P.T. INCO Some Olivine Compositions
Sorowako Poro Tiebaghi Goro Goro
Unserp. Harzburg. Harzburg. Olvine Olivine
SiO2 40.3 40.8 39.2 39.9 40.9
TiO2 0.02 0.016 0.046
Al2O3 0.41 0.38 0.63
Cr2O3 0.02 0.21 0.08
Fe2O3 All iron reported as FeO
FeO 8.92 7.8 9.0 7.95 10.27
MnO 0.13 0.12 0.157
NiO 0.37 0.5 0.3 0.356 0.304
CoO 0.013 0.010 0.019
MgO 50.8 49.2 51.4 51.4 47.1
CaO 0.07 0.039 0.69
Totals 101.28 98.3 99.9 100.84 100.2
P.T. INCO OLIVINES — Formation

• Forsterite crystallises first (higher melting temperature)

• If the olivine is allowed to react with the liquid magma, it
will change its composition towards ferrous olivine
• As the larger ferrous cations replace the smaller Mg
cations, the melting temperature is progressively
reduced
• If the original magma has more silica than can be used
by the olivines (> 40%), then the more siliceous mafic
minerals such as pyroxenes will be formed
• Olivines can take up to 0.5% of NiO (0.4% Ni)
• Ni occurs as replacement of Mg atoms by Ni atoms
P.T. INCO OLIVINES — Formation

Forsterite forms first MAGMA

High melting temp.

Magma with < 40% SiO2

Only olivine forms. Successive
Crystals Crystals crystals richer in Fayalite.
settle on allowed to
the bottom react with
of magma magma
chamber.
Magma with > 40% SiO2
Original
Pyroxenes form, depending on
Forsterite silica availability.
composition
preserved
P.T. INCO ALTERATION OF OLIVINE
Alteration of Forsterite
+800°C: Fo to En Magmatic
625-800°C: Fo to En to Talc
500-625°C: Fo to Talc Hydro
200-500°C: Fo to Serpentine
thermal H2O

Serpentine

Talc

MgO Fo En SiO2
 P.T. INCO HEAT GRADIENT IN THE CRUST
Volcanic Areas: 1 ºC / 10m
Heat Gradients: Average Earth: 1 ºC / 30-35m
Thick Continental crust: 1 ºC / 100m
350
Volcanic Average
Temperature, Celcius

300
Areas Earth
250
200
150
Thick
100
Continent
50
0
0 2 4 6 8 10 12 14 16 18 20

DEPTH, kilometres
P.T. INCO PYROXENES

• General Formula: R2Si2O6 or RO.SiO2

• Orthopyroxenes:
Wo
§ Enstatite: MgSiO3
§ Ferrosilite: FeSiO3
Diopside
§ Hypersthene: (Mg,Fe)SiO3
Ferro-
• Clinopyroxenes: Augite augite

§ Diopside: (Ca,Mg)SiO3 Pigeonite

Orthopyroxenes
§ Augite: (Ca, Mg, Fe)SiO3 En Fs
P.T. INCO Some Pyroxene compositions
Soroako Soroako Poro Tiebaghi Goro Goro
Unserp Unserp. Harzburg. Harzburg.
Opx Cpx Opx Opx Opx Cpx
SiO2 55.1 53.2 60.1 61.8 55.9 50.5
TiO2 0.05 0.09 0.022 0.55
Al2O3 3.23 3.47 1.72 4.09
Cr2O3 0.58 0.86 0.57 0.916
FeO 5.79 2.52 5.8 5.4 5.3 3.96
MnO 0.13 0.08 0.13 0.105
NiO 0.076 0.05 0.1 0.06 0.073 0.074
CoO 0.006 <0.006 0.006 0.003
MgO 33.5 18.5 34.7 32.7 35.1 22.3
CaO 1.86 21.7 1.04 17.65
Totals 100.7 101.1 100.7 99.96 99.97 101.5
P.T. INCO SERPENTINISATION OF OLIVINES
• Serpentinisation occurs under hydrothermal alteration
• Serpentinisation of olivines requires:
§ Addition of water
§ Addition of silica (or removal of magnesia)
§ Release of Fe
§ Conversion of released Fe from ferrous to ferric state to form
magnetite. Thus, serpentinised rocks are more magnetic.
• Serpentinisation occurs at 200 - 500 °C

Fo Olivine Serpentine
Composition: 2MgO.SiO2 3MgO.2SiO2.2H2O
MgO: 57.3% 43.0%
SiO2: 42.7% 44.1%
H2O: 13.0%
Density: 3.2 2.2 – 2.4
P.T. INCO SERPENTINISATION – at Constant Weight

• Serpentinisation by adding water and silica

3Mg2SiO4 4H2O SiO2 2H4Mg3Si2O9

Forsterite + Water + Silica = Serpentine
76.2 g 13 g 10.8 g 100 g
23.6 cm3 39.8 cm3 (+ 68% increase)
In In

• Accompanied by significant increase in volume

• No field evidence is available for this change in volume
(serpentinised olivines still retain their original shape)
P.T. INCO SERPENTINISATION – at Constant Volume (1)

• Serpentinisation at constant volume - 1

(with release of magnesia and silica)

5Mg2SiO4 4H2O 2H4Mg3Si2O9 4MgO SiO2

Forsterite + water = Serpentine + Magnesia + Silica
126.8 g 13 g 100 g 29 g 10.9 g
39.8 cm3 39.8 cm3

In Out Out

• No geological evidence is available for large-scale

removal of silica and magnesia around serpentinised
rocks
P.T. INCO SERPENTINISATION – at constant Volume (2)

• Serpentinisation at constant volume - 2

(with the formation of brucite)

2Mg2SiO4 3H2O H4Mg3Si2O9 Mg(OH)2

Forsterite + water = Serpentine + Brucite
72.4 g 19.5 g 100 g 21.1 g
22.6 cm3 19.5 cm3 42.1 cm3 8.8 cm3

Out
In
• Brucite is a common mineral seen among serpentinised
peridotites
P.T. INCO SERPENTINE MINERALS

• Lizardite: (not the same as serpentinite)

§ Most common form
§ Massive
• Antigorite:
§ Micaceous, foliated, lamellar, columnar form
§ Lamellae are stiff and brittle
• Chrysotile:
§ Delicately fibrous
§ Fibres are flexible and easily separable
§ Occurs in veins or matted masses
§ Most common constituent of commercial “asbestos”
§ Hazardous to human health if fibres are inhaled
P.T. INCO LOI in Serpentine

• Magnesian Serpentine
3MgO.2SiO2.2H2O : H2O = 13.0%
• Iron Serpentine (Greenalite)
3FeO.2SiO2.2H2O : H2O = 9.7%

• Ferro-magnesian Serpentine
Mg-serpentine = 92%
Fe-serpentine = 8%
3(Mg,Fe)O.2SiO2.2H2O : H2O = 12.66%
• Magnesian Serpentine + Brucite mixture
Mg-serpentine = 92%
Brucite = 8%
Serpentine + Brucite : H2O = 15.75%
P.T. INCO Genesis of Serpentine

Genesis of Serpentine
• Pervasive hydrothermal metamorphism of oceanic crust
[producing large serpentinite bodies associated with
subduction melange and orogenic belts]
• Tectonism along faults and shear zones [limited
serpentinisation due to limited access of hydrothermal
fluids along shear zones]
• Secondary serpentine formed during lateritisation [non-
hydrothermal, serpentine-like and talc-like minerals]
P.T. INCO Other Serpentine group minerals

• Talc
§ H2Mg3Si4O12 (4.8% LOI)

• Sepiolite
§ H4Mg2Si3O10 (12.1% LOI)

• High-water Sepiolite
§ H10Mg4Si6O21 (14.7% LOI)

• Saponite
§ H32Mg9Al2Si10O48 (21.3% LOI)

• Iddingsite
§ H8MgFe2Si3O14 (15.9% LOI)
P.T. INCO CHLORITE MINERALS

Chlorite (clinochlore) falls in composition in between

serpentine and amesite:

• Serpentine H4Mg3Si2O9 (13.0% LOI)

• Clinochlore H8Mg5Al2Si3O18 (13.0% LOI)

• Amesite H4Mg2Al2SiO9 (12.9% LOI)

P.T. INCO SPINELS and OXIDES

SPINELS: RO.R2O3 [R=Fe, Mg, Mn, Ni, Zn]

[R2=Al, Fe, Cr, Mn]

• Magnetite: Fe3O4 FeO.Fe2O3 [Fe=72.3%]

• Chromite: FeCr2O4 FeO.Cr2O3
• Common spinel: MgAl2O4 MgO.Al2O3

OXIDES:
• Hematite: Fe2O3 [Fe=69.9%]
• Maghemite: Fe2.66 O4 [Fe=69.9%]
• Silica: SiO2
P.T. INCO Iron and Chrome Spinels

FeO

Magnetite Chromite

Fe2O3 Cr2O3
Magnesioferrite Magnesiochromite

MgO
P.T. INCO HEMATITE / MAGHEMITE

• Hematite – Fe2O3
§ Non-magnetic
§ Formed through reduction of Ferric Hydroxides
§ Gives the laterite its distinctive “red” colour (laterite rouge)

• Maghemite – Fe2O3 — Fe3O4

§ Magnetic variety of hematite
§ Partial reduction of hematite through forest fires?
§ Crystal structure closer to that of magnetite (Fe2.66 O4)
§ Iron deficiency in structure amounts to 11.33%
§ The spinel structure of maghemite inverts to the hematite
structure on heating
P.T. INCO HYDROXIDES

• Hydroxides of Iron: H2O+

§ Turgite Fe2O3.0.5H2O 5.3%
§ Goethite Fe2O3.H2O 10.1%
§ Hydrogoethite Fe2O3.1.33H2O 13.1%
§ Limonite Fe2O3.1.5H2O 14.5%
§ Xanthosiderite Fe2O3.2H2O 18.4%
§ Esmeraldaite Fe2O3.4H2O 31.1%

• Hydroxides of Aluminium:
§ Boehmite Al2O3.H2O 15.1%
§ Bauxite Al2O3.2H2O 26.1%
§ Gibbsite Al2O3.3H2O 34.7%

• Hydroxide of Magnesium
§ Brucite MgO.H2O 30.9
P.T. INCO GOETHITE — Fe2O3.H2O

• Ferrous iron is released from the weathering of primary

mafic minerals (olivines and pyroxenes)
• Ferrous iron gets oxidised to ferric iron and is
precipitated as hydroxide (goethite)
• Goethite appears amorphous and occurs as concretions
and clay-like earthy mass. Concretions have layers
indicating rhythmic precipitation
• Goethite is very stable under prevailing pH-Eh
conditions
• Significant quantities of Al and Cr replace Fe in Bonsora
goethite: Al2O3 = 10-12%
Cr2O3 = 3.1-3.4%
NiO = 0.1 – 0.4%
P.T. INCO Bonsora Goethite Compositions

3 – 6m 6 – 9m 9 – 12m
SiO2 1.61 1.33 2.71
TiO2 0.08 0.18 0.09
Al2O3 10.24 11.13 11.95
Cr2O3 3.25 3.37 3.15
Fe2O3 71.96 70.23 68.79
MnO2 0.08 0.04 0.08
NiO 0.41 0.36 0.13
CoO
MgO 0.48 0.46 0.47
CaO 0.02 0.01 0.01
LOI ? ? ?
Totals 88.26 87.13 87.41
P.T. INCO ASBOLITE

• Asbolane or manganese wad is black and amorphous

• It occurs as thin coatings on joints, fractures and
occasionally as nodules and beads
• The material is rich in manganese and contains
appreciable quantities of Fe2O3, Al2O3, CoO and NiO
• Significant amount of water of hydration may be present
(12% in a sample from New Caledonia)
Soroako Soroako Soroako Soroako New
Lim. 3-6m Lim. 6-9m Lim. 9-12m Saprolite Caledonia
Al2O3 9.0 15.0 7.0 3.5 19.2
Fe2O3 18.4 14.3 36.0 14.2 16.0
Mn2O3 31.0 33.6 33.0 32.0 39.3
NiO 1.7 3.4 2.3 16.2 n.a.
CoO 7.1 7.4 5.0 3.2 7.0
P.T. INCO OCCURRENCE OF IRON

• Primary iron in ultramafics is in the form of:

§ Magnetite (as FeO and Fe2O3)
§ Iron in iron-bearing olivines (as FeO)
§ Iron in iron-bearing pyroxenes (as FeO)

• Primary Magnetite
§ Eventually breaks down under chemical weathering
§ Initial product is hematite
§ hematite eventually gets hydrated to goethite and limonite

• Iron in olivines and pyroxenes

§ On serpentinisation, iron is released as magnetite
§ On lateritic weathering, olivines and pyroxenes release iron that
gets hydrated to goethite and limonite
P.T. INCO CLAY MINERAL GROUP

The word “clay” is used in two meanings:

§ Fine-grained particles of less than 0.002mm (any composition)
§ Group of sheet silicates of a certain chemical composition

Clay Group minerals have two types of sheets:

§ Octahedral sheets (called O sheets)
§ Tetrahedral sheets (called T sheets)

§ Clay group minerals are made up of alternating layers of above

two types of sheets. The unit thickness of a set of sheets
designates the basal spacing in angstrom units
P.T. INCO CLAY MINERAL STRUCTURES
Basal spacings are given in Angstrom units

Kaolinite Smectite Illite Chlorite

O T T T
7 T O O O
10 10
T T 14 T
O
T T T O
O O T
Weak T T O
electrostatic T
bonding Cation
Well bonded.
bonding.
Not easy for Weak
Water resides
water to get in electrostatic
between layers
bonding
P.T. INCO CLAY MINERAL COMPOSITIONS

• Kayolinite/Nacrite/Dickite Al2Si2O5(OH)4

• Smectite/Halloysite/endellite Al2Si2O5(OH)4.2H2O

• Montmorillonite/Pyrophyllite (Mg,Ca)Al2Si4O10(OH)2

• Nontronite Fe2Si4O10(OH)2

• Illite KAl3Si3O10(OH)2

• Chlorite group

• Mixed-Layer clay minerals

P.T. INCO HYDROSILICATES OF Mg AND Ni
Magnesian Hydrosilicates Nickel Hydrosilicates

(Serpentine & Talc Division)

Serpentine H4Mg3Si2O9 Pecroaite / H4Ni3Si2O9
(Chrys. / Lizard.) Nepouite
Talc H2Mg3Si4O12 Willemsite H2Ni3Si4O12

Kerolite H2Mg3Si4O12.nH2O Pimellite H2Ni3Si4O12.nH2O

(Hydrous Talc)
Sepiolite (Dana) H4Mg2Si3O10 Connarite H4Ni2Si3O10

Sepiolite (hi-H2O) H10Mg4Si6O21 Falcondite H10Ni4Si6O21

(Chlorite Division)
Clinochlore H8Mg5Al2Si3O18 Nimite H8Ni5Al2Si3O18
P.T. INCO GARNIERITE GROUP

SiO2

10°A basal
Mg3Si4O10(OH)2.nH2O spacing
Kerolite - Talc Ni3Si4O10(OH)2.H2O
Serpentine GARNIERITES Pimelite
Mg3Si2O5(OH)4
Nepouite
7°A basal Ni3Si2O5(OH)4
spacing

MgO NiO
P.T. INCO NICKEL HYDROSILICATES

• In nickel hydrosilicates, nickel replaces the Mg atoms

• Replacement occurs in serpentine, talc and chlorite
• Garnierite is a group name for nickel hydrosilicates
• Garnierites have the crystal structure of serpentine, talc,
or chlorite
• Garnierites are largely of supergene origin
• Garnierites occur as fillings in open spaces or as
coatings in joint and fracture surfaces
• Garnierites range in colour from green (light and dark),
to yellow-green, to light blue and turquoise blue. Dark
green varieties carry more nickel
P.T. INCO GARNIERITE COMPOSITIONS-1

KONDE, Test Pit - 717

SiO2 MgO FeO NiO
43.8 36.8 4.2 1.3
Wall
43.7 30.3 6.0 4.3
52.5 25.3 0.2 9.4
48.7 25.2 0.0 12.8
51.1 22.6 0.1 14.7
50.6 16.1 0.0 22.2
37.6 0.7 0.3 47.1
Centre
P.T. INCO GARNIERITE COMPOSITIONS-2

NEW CALEDONIA

SiO2 MgO FeO NiO

Sample-1 53.0 18.1 0.1 20.9

Sample-2 49.0 18.9 0.2 21.7

Sample-3 53.2 15.0 0.0 24.5

Sample-4 49.8 13.5 0.2 29.2

Sample-5 37.4 2.7 0.3 49.6

P.T. INCO GARNIERITE COMPOSITIONS-3

OTHER AREAS

SiO2 MgO FeO NiO

Morro do Cerisco, 43.7 30.4 5.5 5.5
Brazil
Morro do Niquel, 52.9 18.3 0.2 16.8
Brazil
Riddle, Oregon, 47.8 18.6 0.1 19.6
USA
Riddle, Oregon, 52.3 16.3 n.a. 20.8
USA
P.T. INCO ASBESTIFORM MINERALS

• Serpentine Minerals
§ Chrysotile

• Amphibole Minerals
§ Tremolite-Actinolite
§ Crocidolite
§ Cummingtonite
 P.T. INCO ASBESTIFORM MINERALS
Ca H Ca Si O
2 7 8 24

Tremolite Calcic amphiboles H2Ca2Fe5Si8O24

H2Ca2Mg5Si8O24
Actinolite Ferro
Actinolite

Cummingtonite Grunerite
H2Mg7Si8O24 Mg Fe H2Fe7Si8O24

Glaucophane Riebeckite (Crocidolite)

H2Na2Mg3Al2Si8O24 Sodic amphiboles
H2Na2Fe5Si8O24

H2Na14Si8O24
Na
P.T. INCO

Tigereye: Silica replacing crocidolite amphibole

P.T. INCO Module 4a

Classification of Rocks
Mafic and Felsic rocks
Basic and ultrabasic rocks
ULTRAMAFIC Ultramafic rocks
Classification of Ultramafics
PETROLOGY
Ni in Ultramafic Rocks
Magmatic Differentiation
Bowen’s Reaction Series
P.T. INCO CLASSIFICATION OF IGNEOUS ROCKS

Parameters used for classification:

§ Degree of silica saturation (Acid, Intermediate, Basic, Ultrabasic)

§ Colour Index (Leucocratic, Mesocratic, Melanocratic, Ultramafic)
§ Type of feldspar (Alkalic; Calc-alkalic)
§ Presence or absence of unsaturated minerals (feldspathoids)
§ Nature of mafic minerals (olivine, pyroxene, hornblende, etc.)
§ Texture (Porphyritic; Orbicular)
§ Mode of occurrence (Pyroclastic; Effusive; Hypabyssal; Plutonic)
§ Grain size (fine; medium; coarse; v. coarse)
(< 1mm) (1–5mm) (5–30mm) (>30mm)
P.T. INCO Alkalic and Calc-alkalic Feldspars

Anorthite
CaAl2Si2O8

An
By
Calc-Alkalic
La
Feldspars
No Solid
And Solution
Ol
Al Alkalic Feldspars

Albite K-feldspar
NaAlSi3O8 KAlSi3O8
 P.T. INCO CLASSIFICATION OF IGNEOUS ROCKS

Arrows indicate increasing change from Calc-alkalic to Alkalic Feldspar

Acid Intermed. Basic Ultra Basic
CI <40 CI >40 CI >70
65 – 75% SiO2 55 – 65% SiO2 45 – 55% SiO2 < 45% SiO2
+10% Free < An50 > An50
Silica Amphiboles Pyroxenes
Extrusive CA Dacite Andesite Basalt
or Rhyodacite Trach. And.
Volcanic Rhyolite Trachyte Neph. Bas.
A
Intermediate
CA Granodiorite Diorite Gabbro Peridotite
Plutonic Adamellite Monzonite Kimberlite
Granite Syenite Alkali Gabb.
A
 P.T. INCO CLASSIFICATION OF PLUTONIC ROCKS

Mafic Minerals < 90% P (Plagioclases)

Albite-
Anorthite
Anorthosite

Gabbro
Diorite
Leucite
Feldspa- Nepheline
Sodalite
Tonalite thoidal Analcine
Diorite &
Gran. Dio. Gabbro
Qtz. Rich
Q Granitoids
Foidolites F
Ademell.

(Feldspathoids)
Foids
Feldspa
Quartz

Syenite
thoidal
Granite
Syenite

Orthoclase
Microcline
Perthite
A (Alkali Feldspars)
P.T. INCO CLASSIFICATION OF PLUTONIC ROCKS

Mafic Minerals > 90%

PLAGIOCLASE

ANORTHOSITES
90 90

GABBROIDS

PYROXENITES &
HORNBLENDITES

10
PERIDOTITES

OLIVINE 40 PYROXENE &

HORNBLENDE
P.T. INCO CLASSIFICATION OF ULTRAMAFICS-1

Classification OLIVINE
In terms of Dunite
Oliv.-Pyrox.-Hnde 90% OL.

Peridotites
Harzburgite
Lherzolite
Wehrlite
40% OL.

Pyroxenites
Orthopyroxenite Hornblendites
Websterite
Clinopyroxenite

PYROXENE HORNBLENDE
P.T. INCO CLASSIFICATION OF ULTRAMAFICS-2

Classification OLIVINE
In terms of
Olivine-Opx-Cpx Dunite

Harzburgite Wehrlite

Lherzolite
OL+OPX+CP
40% OL
Olivine
Olivine
Olivine Clinopyroxenite
Orthopyroxenite
Websterites
Ortho- OL+OPX+CP Clino-
Pyroxenite Pyroxenite
Websterites
ORTHO- CLINO-
PYROXENE PYROXENE
P.T. INCO Peridotite samples from Petea

41 samples OLIVINE
Petrography by
J. Babineau
Dunite

Harzburgite Wehrlite
Lherzolite

OPX CPX
P.T. INCO FELSIC AND MAFIC ROCKS

• FELSIC
§ Feldspar, silica, feldspathoids, muscovite

• MAFIC
§ Ferro-magnesian minerals
[olivines, pyroxenes, amphiboles, biotite, tourmaline, chromite,
iron oxides]

§ Leucocratic 0 – 30% coloured minerals

§ Mesocratic 30 – 60% coloured minerals
§ Melanocratic 60 – 90% coloured minerals
§ Hypermelanic 90 – 100% coloured minerals
P.T. INCO BASIC AND ULTRABASIC ROCKS

• Term “Ultrabasic” means deficiency of silica (<45%)

• Term “Ultramafic” means predominance of mafic

minerals (>70%)

• Most ultrabasic rocks are also ultramafic. However, there

are exceptions:
§ Orthopyroxenite [UM=Yes UB=No (SiO2=60%)

§ Harzburgite (50/50) [UM=Yes UB=No (SiO2=51%)

§ Anorthosite [UM=No UB=Yes (SiO2=43%)

P.T. INCO CLASSIFICATION OF ULTRAMAFICS

DUNITE
• Monomineralic rock composed entirely of olivine. Originally seen at
Dun Mountain in New Zealand
PYROXENITE
• Monomineralic rock composed entirely of pyroxene
§ Orthopyroxenites: Bronzitites
§ Clinopyroxenites: Diopsidites; diallagites
HORNBLENDITES
• Monomineralic rocks composed entirely of hornblende
SERPENTINITE
• Monomineralic rock composed entirely of serpentine
PERIDOTITE
• Ultramafic rocks containing olivine and other mafic minerals
• Pyroxene peridotite / Hornblende peridotite / Mica peridotite
P.T. INCO ULTRAMAFIC ROCKS

TERMINOLOGY
• Rich in mafic (ferro-magnesian) minerals
• Generally contain less than 45% SiO2 (except pyroxenite)
• Colour indices of more than 70
• Generally lack any feldspar
• No exact counterpart among lavas (extrusive rocks)
• The density of ultramafic magma is too high to rise through the
sialic portion of the crust

FORMATION
• Crystal settling (by gravity) in a magma chamber (layered intrusions)
• Intrusion of hot, semi-solid, crystalline mass (dykes, lenses, stocks)
• Through obduction of oceanic crust upon continental landmass in
orogenic belts
P.T. INCO WORLD’S SERPENTINE BELTS
P.T. INCO CRUST OF THE EARTH

Ocean
Sial Continental Crust
M

Oceanic
Sima Crust

Mantle
 P.T. INCO STRUCTURE OF OCEANIC CRUST

Seismic Metamorphic
Layer Velocity Grade Thickness
Sea Level
1 2.0 km/sec Marine Sediments 0 – 4 km

Oceanic Crust
2 5.1 km/sec Zeolite Ocean basalts 1 – 2.5 km

5 – 8 km
Greenschist
3 6.7 km/sec Gabbros 5 km
Amphibolite
4 8.1 km/sec Layered Peridotite 0.5 km

Mohorovicic
8.1 km/sec Mantle Peridotites
Discontinuity
 P.T. INCO STRUCTURE OF OCEANIC CRUST

Seismic Metamorphic
Layer Velocity Grade Thickness
Sea Level
1 2.0 km/sec Marine Sediments 0 – 4 km

Oceanic Crust
2 5.1 km/sec Zeolite Ocean basalts 1 – 2.5 km

5 – 8 km
Greenschist
3 6.7 km/sec Gabbros 5 km
Amphibolite
4 8.1 km/sec 0.5 km

Mohorovicic
8.1 km/sec Mantle Peridotites
Discontinuity
 P.T. INCO SCHEMATICS OF ACCRETION

Deep Shallow
Earthquakes Volcanic Earthquakes
Front

Peridotitic blocks in
the oceanic crust
200

400
Km
P.T. INCO Ni IN ULTRAMAFIC ROCKS

• Ni in ultramafic rocks is primarily in mafic minerals

§ High in olivines (0.2 – 0.3% Ni)
§ Low in orthopyroxenes (0.05 – 0.1% Ni)
§ Very low in clinopyroxenes (< 0.05% Ni)
• Thus, decrease in the olivine content of the ultramafic
reduces the overall nickel content of the rock:
§ Highest Ni grades in dunites
§ Lower Ni grades in peridotites
§ Lowest Ni grades in pyroxenites
• Ni in mafic minerals is largely as a replacement of Mg
• Ni in mafic minerals falls with the order of crystallisation
• Some Ni may exist as replacement of the larger Fe atoms
• Primary chromite and magnetite may contain minor Ni
P.T. INCO MAGMATIC DIFFERENTIATION

• Through Magmatic Differentiation, a homogeneous

magma crystallises into rocks of different compositions

• Magmatic differentiation is achieved through Fractional

Crystallisation in which different crystals are formed at
different temperatures during the cooling of magma

• The early formed crystals achieve equilibrium with the

magma in two ways:
§ Through Continuous Reaction with Magma
• Crystal composition changes while crystal structure remains
the same
§ Through Discontinuous Reaction with Magma
• Crystal composition as well as crystal structure change
P.T. INCO BOWEN’S REACTION SERIES

Olivine Ca-Plagioclase

Mg-Pyroxene Ca-Na-Plagioclase
Mg-Ca-Pyroxene
Na-Ca-Plagioclase
Amphibole
Discontinuous Na-Plagioclase Continuous
Series Biotites Series

Muscovite
Quartz
Zeolites
Hydrothermal
solutions
P.T. INCO Module 4b

Purpose of Phase Diagrams

Ice-Water-Vapour system
PHASE
Two components: with solid solution
DIAGRAMS Two components: with no solid solution
Phase Chemistry in PTI furnaces
P.T. INCO PHASE DIAGRAMS

• Phase diagrams are used to describe equilibrium

conditions of different components and phases at
varying temperatures and pressures

• Components:
Chemically different components of a system

• Phases:
Physically different characteristics of the same chemical
component
P.T. INCO ICE-WATER-VAPOUR SYSTEM
Note:
All three phases
co-exist at point “P”

P
R
E
WATER
S (Liquid)
S ICE
U (Solid)
R
E
P
4.8mm
VAPOUR
(Gas)

0.008°C
TEMPERATURE
P.T. INCO ICE-WATER-VAPOUR SYSTEM

Notes on the phase diagram:

• One component system (H2O)

• Three phases involved (solid, liquid, gas)
• All three phases can co-exist at 0.008°C and a pressure
of 4.8mm
• At higher temperature, water can be turned directly into
vapour just by changing the pressure
• At lower pressure, water can be turned into ice by
changing the temperature
P.T. INCO TWO COMPONENT SYSTEMS

• Two components form a solid solution

§ All compositions between the components are possible
§ Examples:
q Forsterite – Fayalite
q Enstatite – Ferrosilite
q Albite – Anorthite

• Two components do not form solid solution

§ Intermediate compositions are not possible
§ Examples:
q Forsterite – Diopside
q Diopside – Anorthite
P.T. INCO TWO COMPONENTS / WITH SOLID SOLUTION

• Two components have complete solid solution

• All compositions between the two end members are
possible
• All compositional ranges have the same crystal structure
• End members could have different melting temperatures
• Both end members yield a completely miscible liquid on
melting
• Example:
• Forsterite – Fayalite
• Enstatite – Ferrosilite
 P.T. INCO FORSTERITE – FAYALITE SYSTEM
Starting
Composition
A
Liquidus LIQUID
1890°C
S1 L1
T1
S2
T2

Temperature
L2
Temperature

LIQUID + SOLID

S3 L3
T3
S4 L4
T4 SOLID
1205°C
Solidus

C1 C2 C3 C4
0 50 100
Mg2SiO4 Fe2SiO4
P.T. INCO FORSTERITE – FAYALITE SYSTEM

Notes on the Forsterite – Fayalite system:

• Consider a liquid made up of forsterite and fayalite of composition
“A” (equivalent to C3)
• As the liquid cools, no change occurs until the Liquidus curve is
reached at temperature T1
• At T1, crystals of composition C1 separate. C1 represents a solid
solution of forsterite and fayalite
• With further cooling, the composition of liquid moves towards
fayalite
• If crystals are allowed to react with the liquid, they will change
composition until all liquid is solidified with a uniform composition
of C3
• If crystals separate out through gravity, newer crystals will move in
composition towards fayalite and later crystals may be more fayalitic
than the starting composition of the liquid
P.T. INCO TWO COMPONENTS / WITH NO SOLID SOLUTION

• Two components cannot yield a solid solution

• Intermediate compositions between the two components
are not possible
• The two components may have different melting points
• The liquids of the two components are miscible
• Examples:
§ System Diopside – Anorthite is an example of above system with
a eutectic temperature of 1270°C and a composition of Di58An42

§ System Forsterite – Diopside is another example with a eutectic

temperature of 1400°C and a composition of Fo12Di88
P.T. INCO TWO COMPONENTS – NO SOLID SOLUTION

LIQUID 2
Liquidus T4
1 LIQUID T5
Liquidus + SOLID
T1
T2
Crystals of B
Crystals of A and liquid in
and liquid in equilibrium
equilibrium
T3 T3
E
SOLID Crystals of A and B in equilibrium

C1 C2
A B
P.T. INCO TWO COMPONENTS – NO SOLID SOLUTION

Notes on the two component non-solid-solution system:

• Consider liquid of composition 1
• As the liquid cools, crystals of A appear at temperature T2 (the
liquidus)
• Composition of liquid moves towards point E
• At temperature T3, crystals of A and B form simultaneously
(Eutectic temperature)
• Crystals of A and B are in proportion of A-C1 : C1-B
• Consider liquid of composition 2
• As the liquid cools, crystals of B appear at temperature T5 (the
liquidus)
• Composition of liquid moves towards point E
• At temperature T3, crystals of A and B form simultaneously
(Eutectic temperature)
• Crystals of A and B are in proportion of A-C2 : C2-B
P.T. INCO
P.T. INCO PTI Furnace

Copper “fingers”
(water cooled)

Slag

Slag Matte
Matte

18 m Refractory bricks on
Sidewalls & hearth
P.T. INCO PTI FURNACES – Initial plan

• 18-m diameter furnaces with power requirement of 45MW

• Initial plan to smelt high S/M ratio West Block ore alone
• Initial smelting showed that:
§ Liquidus temperature of the slag was low at 1430 – 1475°C
§ S/M of 2.4 allowed pyroxene to coexist with the slag. Pyroxene is
too acidic for the magnesia refractory
§ To dissolve the coarse, unaltered, olivine-bearing peridotite,
superheat was required
§ High superheat made it difficult to freeze the protective slag layer
on the refractory walls
§ Furnace rebuild was required every 8-20 months (instead of +60)
P.T. INCO PTI FURNACES – Corrective action

• East Block ores with low S/M ratio were blended with
West Block feed
• A S/M ratio of 1.9 was targeted during the 1980s
• A S/M ratio of maximum 2.1 was allowed during 1990s
• Ore blending had the following benefits:
§ The amount of coarse, unaltered peridotite was reduced
§ The blending reduced the S/M ratio or acidity of the ore
[olivine+pyroxene coexist with the slag]
§ The smelting temperature or liquidus climbed by 50°C which
avoided superheating the slag
§ Slag skimming temperature stabilised at 1550°C
§ Matte tapping temperature also climbed to 1360°C that saved fuel
consumption in the Converters
P.T. INCO PHASE DIAGRAM PTI FURNACES

Current 1979
T°C 20% 25% 30%
FeO FeO FeO
1700
LIQUID
1600

1500

1400
SOLID
1300
1 2 3 4 5 6
Silica / Magnesia Ratio
P.T. INCO PHASE CHEMISTRY AT PTI FURNACES

• Liquidus temperatures are controlled by S/M ratio and

amount of Fe
• Eutectic temperatures lie between 1425°C and 1475°C
corresponding to S/M ratio of 2.4 to 3.0 and Fe = 20-30%
• Below S/M of 2.1, the liquidus is controlled only by S/M
ratios; Fe content has little effect
• Above S/M of 2.2, both S/M ratio and Fe content control
the liquidus:
§ Melting temperature increases with increasing S/M ratio
§ Melting temperature falls with increasing Fe content
P.T. INCO Module 5a

Processes of change
Nature of Weathering
WEATHERING Chemical Weathering
Chemical mobility of elements
Factors Influencing Chemical Weathering
P.T. INCO WEATHERING

Four major processes under which rocks change their

physical or chemical properties:
§ Melting (at very high temperatures)
§ Metamorphism (high temperatures / pressure / addition)
§ Hydrothermal alteration (through high-temperature fluids)
§ Weathering (at ordinary temperatures and pressure)

Types of weathering:
§ Physical (mechanical breakdown of rocks)
• erosion, thermal expansion/contraction, action of plants
§ Chemical (breakdown of rocks through chemical processes)
• contact with water, oxygen, carbon dioxide, etc.
P.T. INCO CHEMICAL WEATHERING

“The process in which rocks react to atmospheric,

hydrospheric and biologic agencies to produce mineral
phases that are more stable”

1. Hydrolysis
Oxygen, carbon dioxide, ground water, dissolved acids attack the
minerals in the rock
2. Oxidation
Elements released by chemical weathering are oxidised
3. Hydration
Reaction with water adds the hydroxyl ion to newly formed minerals
4. Solution
The more soluble products of weathering are dissolved and removed

And the cycle continues .....

P.T. INCO
CONDITIONS FOR CHEMICAL WEATHERING

Acidic Acidic
RAIN AND THUNDER STORMS
Rain Rain Nitrous oxides, CO2

HUMOUS (Organic) LAYER

(Reducing conditions)

ZONE OF OXIDATION

WATER TABLE

(Reducing conditions)
P.T. INCO CHEMICAL WEATHERING – 1. Hydrolysis

• According to Pauling’s Rule, the sum of negative and

positive charges must be equal within a crystal
• However, exposed atoms and ions on crystal surfaces
possess unsaturated valencies and are thus charged
• Contact with water causes hydration of the surface
through attraction of water molecules to the charged
surfaces
• Attractive forces cause polarisation of water into H+ and
OH- ions
• Hydroxyl (OH)- ions then bond to exposed cations
• Hydrogen ions (H)+ bond to exposed oxygen and other
negative ions
P.T. INCO CHEMICAL WEATHERING – 2. Oxidation

• Common oxidising agent in the soil is oxygen dissolved in ground

water
• Much of ferrous ions in the weathering profile are converted to ferric
state under highly oxidising conditions.
• Oxidising conditions exist only above the water table
• Below the water table, conditions are generally reducing
• Organic matter at the very top may also create reducing conditions
• Hot, well-drained environment favours oxidation through the
destruction of organic matter and lowering of water table
• Cool, poorly-drained environment promotes accumulation of
organic matter and reducing conditions
P.T. INCO CHEMICAL WEATHERING – 3. Hydration

• In the presence of Hydroxyl ion (OH)-, many freshly created oxides

from the breakdown of minerals are converted to hydroxides
• The more common hydroxides found in lateritic soils include:
§ Hydrated iron oxides: Goethite / Limonite
§ Hydrated Aluminum oxides: Boehmite / Bauxite / Gibbsite
§ Hydrated manganese oxides: Pyrochroite / Manganite / Psilomelane
• Many new secondary mafic minerals are formed due to hydration:
§ Serpentine / Talc / Chlorite
• Hydration also results in the formation of clay minerals:
§ Kayolinite / Nacrite / dickite
§ Hallyosite
§ Illite
§ Smectite
§ Montomorillonite / Saponite / Pyrophyllite
§ Nontronite
P.T. INCO CHEMICAL WEATHERING – 4. Solution

• For chemical weathering to continue, broken down constituents

must be removed
• Solution of broken down constituents exposes new surfaces
• Dissolved constituents are removed by percolating ground waters
• Ground waters generally travel from top to bottom in a weathering
profile
• Dissolved constituents are eventually drained out to rivers, lakes
and the ocean
• The relative proportions of dissolved constituents in ground water
confirm the relative solubilities of various oxides in the laboratory
• Dissolved CO2 in ground water is a very strong leaching agent
P.T. INCO SOLUBILITIES OF MINERALS

• Solubilities of some minerals:

§ Halite (NaCl): 3005 g/litre
§ Gypsum (CaSO4.2H2O): 1.8 g/litre
§ Silica gel: 0.12 g/litre
§ Quartz (SiO2): 0.007 g/litre

• Relative solubilities of some minerals (Paul Golightly):

§ Forsterite Highly soluble
§ Enstatite
§ Serpentine
§ Talc
§ Amorphous silica
§ Nickel Talc (Kerolite)
§ Gibbsite
§ Goethite Highly insoluble
P.T. INCO RELATIVE MOBILITIES

• Polynov’s estimate of elemental mobilities:

Cl SO4 Ca++ Na+ Mg++ K+ SiO2 Fe2O3 Al2O3

100 57.0 3.0 2.4 1.3 1.25 0.2 0.04 0.02

• Hudson’s estimate of elemental mobilities

Cl > SO4 > Na > Ca > Mg > K > Si > Fe+++ > Al

• Berger’s estimate of hydroxide mobilities:

Soluble Supergene Residual
Mg Mn++ Co++ Ni++ Al+++ Cr+++ Fe+++
3.1 1.3 -1.7 -3.2 -15.3 -16.4 -18.1
P.T. INCO AFFECTIVE MOBILITIES

• Highly soluble and highly mobile

§ Easily leached out of the laterite profile
§ Taken to lakes, rivers and the sea
Ca, Na, Mg, K, Si

• Non soluble and residual

§ Insoluble in ground waters at ordinary pH / Eh conditions
§ Make up bulk of the residual soil
Al+++, Fe+++, Cr+++, Ti, Mn+++

• Limited solubility –— Supergene enrichment

§ Partly soluble in acidic ground water
§ Insoluble in the presence of more soluble elements (Si, Mg)
Ni++, Co++, Mn++
P.T. INCO Residual Concentrations at Petea

Original Limonite Concentration

Bedrock Zone Factor
Ni 0.28 1.00 3.6
Fe 6.0 50.0 8.3
Co < 0.007 0.131 18.7
SiO2 40.9 2.3 Leached out
MgO 35.3 1.5 Leached out
Al2O3 1.13 8.5 7.5
Cr2O3 0.45 3.44 7.6
MnO 0.13 1.25 9.6
TiO2 0.01 0.086 8.6
P.T. INCO FACTORS INFLUENCING CHEMICAL WEATHERING

The following factors influence the speed as well as the

character of chemical weathering:

1. Stability of Minerals (crystal structure, melting points)

2. Acidity / basicity (pH) conditions
3. Reduction / oxidation (redox potential) of the environment
4. Grain size and rock openings
5. Rate of removal of dissolved constituents
6. Climate (temperature, rainfall, fluctuation of water table)
7. Topography
8. Time
9. Rock conditions (Fracturing, Jointing, Grain size)
10. Role of water table
P.T. INCO 1. Stability of Minerals

Goldich (1938) determined the following sequence of decreasing

weathering susceptibilities for the common rock-forming minerals

Olivine Ca-Plagioclase

Augite

Hornblende Na-Plagioclase
Biotites

K-Feldspar

Muscovite

Quartz
P.T. INCO 1. Stability of Minerals (continued)

• In general, crystal structure of mafic silicates controls weathering:

§ Olivine, with its independent silicon tetrahedra is the most unstable
§ Pyroxenes, with polymerised chains, are more stable
§ Amphiboles, with their ring structures, are still more stable
§ Clays and micas with their sheet-like structure are the most stable
• Reiche (1943) devised a Weathering Potential Index:
§ Forsterite 66
§ Enstatite 55
§ Anthophyllite 40
§ Augite 39
§ Hornblende 36
§ Talc 29
§ Biotite 22
§ Orthoclase 12
§ Quartz 0
§ Muscovite - 11
§ Kayolinite - 67
§ Gibbsite -300
P.T. INCO 2. Acidity / basicity (pH) conditions

• pH of ground water controls solution of different minerals

• pH of normal waters lies between 4 and 9
• Most oxides show some solubilities in natural waters
• Oxides of Ca, Mg, Na and K are completely soluble
• Oxides of Ti, Al, and Ferric iron (Fe+++) are insoluble
• Solubilities of many oxides are pH dependent:
§ Ti, Ca, Fe++ iron
• Alumina is not soluble in the normal range of ground water pH
• Alumina is soluble at pH < 4 and at pH > 10
• Where abundant organic matter is available, pH may drop to < 4
• Plant roots carry low pH values, commonly 4 but down to 2
• Where abundant basic minerals are being weathered (olivine,
pyroxene, nepheline), pH conditions may climb to beyond 9
P.T. INCO 3. Role of Redox (Eh) Potential

• Redox Potential of a system is a measure of the ability to bring

about reduction or oxidation reactions
• Reduction: decrease in the positive valency of an element (Fe+++ to
Fe++) or an increase in the negative valency of an element
• Oxidation: increase in the positive valency of an element (Fe++ to
Fe+++) or the decrease in the negative valency of an element
• The neutral value of Redox Potential is zero
• At lower values (-), the R. Potential represents reducing conditions
• At higher values (+), the R. Potential represents oxidising conditions
• Two factors control the Redox Potential during weathering:
§ Availability of atmospheric oxygen (creates oxidising conditions)
§ Availability of organic matter (creates reducing conditions)
 P.T. INCO Influence of Eh and pH on iron

1.0
Fe+++
0.8
Fe++ O2
Oxidising

0.6
Natural H2O
0.4 Environments
0.2
Eh 0.0
H2O
- 0.2
Reducing

H2 Fe+++
- 0.4
Fe++
- 0.6
0 2 4 6 8 10 12 14
Acidic pH Alkaline
P.T. INCO 4. Rate of removal of dissolved material

REMOVAL
• For chemical reactions to proceed, the dissolved material must be
removed
• The rate of removal depends on:
§ The relative solubilities of oxides
§ The amount of water moving through the system
§ The presence of crystal fractures, cleavages, porosity

FIXATION
• While alkalis have high solubilities in ground water, potassium gets
“fixed” in clay minerals
• Igneous rocks contain almost equal amounts of sodium and
potassium (Na2O = 3.9% ; K2O = 3.1%)
• Concentration of K in seawater is only one tenth of Na
P.T. INCO 5. Role of Climate

Climatic factors have a great influence on chemical weathering:

• Rainfall: Provides moisture for chemical reactions and supplies
water for removal of dissolved material. Gentle and persistent
rainfall is more effective compared to sudden heavy rain
• Temperature: According to Van’t Hoff’s rule, each 10°C change in
temperature increases the speed of chemical reaction by 2 to 3
times. Chemical weathering and leaching in the tropics is 20 – 40
times higher than in temperate zones
• Vegetation: High accumulation of organic material leads to low pH in
ground waters
• Equatorial Humid Climate: Results in good and constant flushing of
magnesia and silica and does not allow the formation of
smectite/nontronite clays
• Tropical Wet-Dry Climate: Results in poor flushing of silica and
magnesia and allows the formation of smectite/nontronite clays
P.T. INCO 6. Role of Topography

• Run-off versus absorption of rainwater:

§ On steep slopes, much of the water runs off. Promotes physical
weathering and erosion
§ On gentle slopes, some water gets absorbed. Promotes chemical
weathering
• Rate of sub-surface drainage:
§ Higher areas afford better drainage and removal of dissolved material
§ Low-lying areas are poorly drained
• Rate of erosion:
§ Very steep areas keep losing the soil or laterite as it forms
Slopes of < 20% (preferable < 15%) are necessary to retain the laterite
• Ideal conditions for chemical weathering:
§ Rolling to gently sloping morphology
§ Elevated area
§ Surface runoff is not excessive
§ Sub-surface drainage is good
P.T. INCO Various topographic profiles

Steep Hill

Gentle Hill
Depression / basin

Plateau

River Terrace

Dissected Plateau
P.T. INCO 7. Role of Water Table

• The position of water table depends on:

§ Amount of rainfall
§ Ground porosity/permeability
§ Topographic characteristics

• Permanently High water table

§ Much of rock filled with water
§ Less oxygen being supplied

• Permanently Low water table

§ Likely less rainfall and little ground water to attack minerals
§ Slow removal of dissolved material

• Fluctuating water table

§ Varying zones of oxidation and reduction
§ Frequent flushing of system to remove dissolved material
P.T. INCO SOILS

• A soil is a naturally occurring body made up of layers

which differ from the parent material in their physical,
chemical, mineralogical, biological and textural
characteristics.

• Soils are formed through several processes that include:

§ Addition through transportation
§ Removal at the top of the profile through erosion
§ Removal from the soil profile through leaching
§ Migration of elements through the soil profile (through leaching)
P.T. INCO PROCESS OF SOIL FORMATION

Surface additions
(organic matter, transported material)
Surface erosion

Chemical and
Supergene
physical changes
transfers

Leaching and
removal of solubles
P.T. INCO SOILS & RELATIVE DEPTH OF WEATHERING

Tundra

Savannas
Savannas
Semi-desert
& Desert
Steppes
Taiga (Northern
Forests
Tropical
Rainfall, 0 – 3,000 mm
Temperature, 0 - 30ºC

K Fe/Al
I/M
K
Legend:
I/M
Fe/Al: Oxides/Hydroxides
Bedrock with incipient
K: Kaolinite clays chemical alteration
I/M: Illite/Montmorillonite
 GREAT SOIL GROUPS OF THE WORLD
P.T. INCO
Dry Wet
Cold TUNDRA Cold
TUNDRA
Degraded
Degraded
Chernozem
Chermozem PODZOL

Chemozem
Brown PODZOL

Chestnut
Gray Desert &
Sierozem

Gray
TEMPERATURE

Desert Chestnut Brown Podzolic

Brown
and Sierozem Brown Podzolic
Brunizem
Gray-Brown
Gray-Brown Podzolic

Podzolic
Brunizem
Redd
ish
Red-Yellow
Reddish Brown

Bro Red-Yellow Podzolic

wn
Podzolic
Chestnut
Reddish

Reddish
Chestnut Reddish
Red
Red Desert Prairie
Reddish Yellow-brown
Yellowish brown Latosolic
Desert Latsolic
Prairie
Reddish-brown
Reddish brown Latosolic
Latsolic
LATERITE
Hot LATERITE Hot
Dry Wet
HUMIDITY / RAINFALL
P.T. INCO

Weathering of Ultramafic rocks

Behaviour of MgO, SiO2, Fe, Al, Ni
WEATHERING OF Laterite Profile: Limonite zone
ULTRAMAFIC ROCKS
Laterite Profile: Intermediate zone
AND LATERITES
Laterite Profile: Saprolite zone
Rates of Laterisation
P.T. INCO LATERITES

• The term “Laterite” is derived from the Latin word “later” which
means brick
• Buchanan Hamilton first introduced the term in 1807 to the earthy
iron crusts that were being cut into bricks by the people of south-
central India
• Currently, the term Laterite is used for soils that are rich in
sesquioxides of iron and aluminium, formed under the influence of
chemical weathering with special ground water conditions
• Development of laterites require:
§ Availability of appropriate rocks that contain iron and aluminium
§ Relatively high temperatures (to aid chemical attack)
§ High rainfall (to aid chemical weathering)
§ Intense leaching (to remove mobile elements)
§ Strongly oxidising environment (to make sesquioxides)
§ Gentle topography (to preserve the laterite once it is formed)
P.T. INCO WEATHERING OF OLIVINE

Forsterite: 2MgO.SiO2 (MgO = 57.3%) Sorowako Olivine:

• FeO = 9.0%
Replacements • Al2O3 = 0.4%
• NiO = 0.37%
• Highly unstable in weathering • MnO = 0.12%
environment • Cr2O3 = 0.02%
• Individual SiO4 tetrahedra are • TiO2 = 0.02%
weakly bonded by cations
• Magnesia is highly soluble in ground water
• Release of magnesia breaks down the Olivine structure
• Breakdown of Olivines releases various cations:
§ MgO, FeO, NiO, MnO
P.T. INCO WEATHERING OF PYROXENE

Enstatite: MgO.SiO2 (MgO = 40.2%) Sorowako Pyroxene:

Opx Cpx
Replacements • FeO = 6.0 2.5
• Al2O3 = 3.2 3.5
• Relatively unstable in weathering
• CaO = 1.9 21.7
environment (but < Olivine)
• NiO = 0.08 0.05
• Individual SiO4 tetrahedra are
• MnO = 0.13 0.08
bonded by shared Oxygen
• Cr2O3 = 0.58 0.86
• Magnesia is highly soluble in • TiO2 = 0.05 0.09
ground water
• Release of magnesia breaks down the Pyroxene
• Breakdown of Pyroxenes releases various cations:
§ MgO, FeO, CaO.Al2O3.NiO, MnO
P.T. INCO Weathering of Serpentine

• Serpentine: 3MgO.2SiO2.2H2O
• Magnesia is leached out first, leaving behind a silica
enriched phase or montmorillonite and chlorite
• Ni and Fe can replace the magnesium being leached.
This results in the formation of:
§ Iron containing serpentine
§ Nickeliferous serpentine
• Through a similar process, nickel is also fixed in Talc,
Chlorite, and Smectite
• Eventually, montmorillonite and chlorite also break
down, releasing remaining magnesia and silica
P.T. INCO Behaviour of Magnesia (MgO)

• Magnesia is present in Olivine, Pyroxene and Serpentine

• Magnesia is released by the breakdown of olivines
• Magnesia has very high solubility in ground water
• It is the first major component to be leached out in large
quantities
• Some magnesia may stay in the laterite profile to form
clay minerals and nickel hydrosilicates
• Final product of lateritic weathering (Goethite/limonite)
does not contain any magnesia
P.T. INCO Behaviour of Silica (SiO2)

• Silica is present in Olivine, Pyroxene and Serpentine

• Silica is released by the breakdown of ferro-magnesian
silicates
• In humid environments, laterite is constantly flushed and
little silica gets fixed as smectite/nontronite clays
• In wet-dry environments, flushing of laterite profile is
poor and silica gets fixed as smectite/nontronite clays in
the Intermediate Zone
• In the alkaline environment (where MgO is being
released), silica can precipitate from solution as
amorphous silica (silica veins, boxwork, coatings)
P.T. INCO Behaviour of Iron (Fe)

• Iron is present as: Ferrous Ferric

§ In olivine (MgO.FeO.SiO2) : Fe++
§ In pyroxene (MgO.FeO.2SiO2) : Fe++
§ In chromite (FeO.Cr2O3) : Fe++
§ In ilmenite (FeO.TiO2) : Fe++
§ In magnetite (FeO.Fe2O3) : Fe++ Fe+++

• Breakdown of mafic minerals releases Ferrous ions

• Ferrous ion is quite soluble and mobile
• Ferrous ions get quickly oxidised to ferric ions, as:
§ Hematite / Maghemite, Goethite, Limonite

• Iron in primary magnetite and ilmenite oxidises to form:

§ Hematite / Maghemite, Goethite, Limonite

• Iron in the Ferric (Fe+++) state is very insoluble

P.T. INCO Behaviour of Alumina

• Alumina is present in:

§ Pyroxenes (as impurity and as solid solution)
§ Common Spinel (MgO.Al2O3)

• On the breakdown of pyroxenes, alumina is temporarily

fixed in the chlorites (Clinochlore: 5MgO.Al2O3.3SiO2.4H2O)
• After the breakdown of chlorites, alumina is fixed in
gibbsite (Al2O3.3H2O)
• Alumina is very insoluble in ground water in the pH
range commonly found (4 – 9)
• Al+++ and Fe+++ are truly residual elements in laterites
P.T. INCO Behaviour of Mn and Co

• Minor amounts of Mn and Co are present in the mafic

minerals (Olivine and Pyroxene)
• On the breakdown of mafic minerals, Mn and Co are
released
• Mn and Co are slightly soluble in acidic waters at the top
of the laterite profile
• Mn and Co are very insoluble in alkaline waters
• Mn and Co concentrate at the bottom of the Limonite
Zone
• Much of Cobalt is tied to the manganese wad
P.T. INCO Behaviour of Ni

• Minor Ni is present in Olivines (0.3%), Orthopyroxenes

(0.1%), and Clinopyroxenes (< 0.05%)
• Ni can replace the Mg being leached out of serpentines,
Talcs and Chlorite to form nickeliferous silicates
• Ni is soluble in acidic water but insoluble in alkaline
water
• Ni travels down the profile and gets precipitated as Ni
hydrosilicates in the Saprolite Zone (alkaline environment,
where solubility of Mg is higher than that of Ni)
• Some Ni gets permanently tied to the goethite structure
(as solid solution, from 0.5 to 1.5% Ni)
• Ni is also tied to Asbolite / Manganese wad at the base of
the Limonite Zone
P.T. INCO TYPICAL WB LATERITE PROFILE

Red Laterite

Limonite zone

Saprolite zone

Bedrock pinnacle
P.T. INCO LATERITE PROFILE

Laterite Zones Processes at work

“Red” Hematite • Acidic environment

• Collapsed profile
•“Soluble” ions leached (Ca, Mg, Si, Na, K)
“Yellow” Limonite • “Insoluble” ions concentrated (Cr, Al, Fe)
• Mn, Co show supergene enrichment
• Alkaline environment
• Un-collapsed profile
Saprolite zone • Leaching/residual concentration in progress
• Boulder formation
• Ni shows supergene enrichment

• Alkaline environment
• Joints / fractures exposed to U/G water
Bedrock zone • Chemical attack is just beginning
• Channelways provide removal of dissolveds
P.T. INCO LATERITE PROFILE – Limonite zone

• The uppermost zone is rich in hematite and goethite

• The limonite may be remobilised in near-surface acid
conditions and crystallised to hard ferricrete/iron cap
• Extremely insoluble minerals may persist in this zone
(spinel, magnetite, primary talc)
• The base of the limonite zone is enriched in manganese,
cobalt and nickel (manganese wad). This wad occurs as
coatings on joints and fracture planes
• Limonite zone represents laterite that has collapsed
• The dry bulk density in the limonite zone is higher than
in the Transition zone
• Due to collapse, the original texture and structure of rock
is completely obliterated
P.T. INCO LATERITE PROFILE – Intermediate zone

• Contains soft Smectite clays – usually nontronite (Fe2O3.2SiO2.2H2O)

– and hard crystalline quartz

• Leaching is advanced but collapse is not complete

(resulting in low bulk density)

• Some original texture/structure is still preserved

• The formation of distinct intermediate zone requires wet-dry climate

• If the Intermediate Zone is developed, the occurrence of manganese

wad is more prominent in the upper part of the Intermediate Zone

rather than in the lower part of the Limonite Zone

P.T. INCO LATERITE PROFILE – Saprolite zone

• The Zone consists of: bedrock fragments, saprolised rims of

boulders, precipitated quartz, and garnierite
• Chemical weathering is proceeding along joints & cracks
• Saprolisation along joints leads to the formation of “boulders”
• The boulders can have a significant saprolised crust
• Original rock texture and structure are well preserved
• Most parent rock minerals are preserved
• In Unserpentinised rock, saprolisation is limited to boulder surfaces
since the rock is very hard (boulders are free of replacement nickel)
• In serpentinised rock, saprolisation proceeds through much of the
rock mass since it is soft (boulders may contain significant
quantities of replacement nickel)
P.T. INCO

Development of weathering crust

on a West type peridotite boulder
P.T. INCO FORM OF NICKEL MINERAL

Nickel as hydroxide essentially in the

Limonite zone goethite-limonite (Fe2O3.nH2O) structure.
Some Ni adsorbed in Mn-O / Mn-OH.

Nickel as hydro-silicate essentially with

the talc-serpentine lattice structure:
Saprolite zone Nickel talc: (Mg,Ni)3Si4O10(OH)2
Nickel serpentine: (Mg,Ni)3Si2O5(OH)4

Nickel as silicate essentially in the olivine

lattice structure, as ionic replacement of
Bedrock Mg and Fe atoms:
Olivine: (Mg,Fe)2SiO4
Pyroxene: (Mg,Fe)2Si2O6
P.T. INCO SOROWAKO LATERITE PROFILE

WEST BLOCK EAST BLOCK

UNSERPENTINISED SERPENTINISED
DEPTH (m)
0 Iron cap

Limonite
5 Overburden

Limonite ore
10

Saprolite Ore
15

20 Bedrock
 P.T. INCO NICKEL LATERITE PROFILES
SILICATE CLAY OXIDE
(eg New Caledonia) (eg Murrin Murrin) (eg Moa Bay)
DEPTH (m)
Iron cap
0 Cuirasse Colluvium
Limonite
Red Ferruginous overburden
limonite zone

Yellow Limonite
limonite Smectite
zone

Earthy Saprolite
ore
20

Ore with
boulders Saprolite
(Serpentine,
chlorite, Bedrock
Rocky
smectite)
ore

Bedrock
40 Bedrock
P.T. INCO Silica / MgO as a function of Fe

45
40
% SiO2, % MgO

35
30
25 SiO2
20
15
10
MgO
5
0
5 10 15 20 25 30 35 40 45 50 55

% Fe
P.T. INCO Major Elements in Laterite Profile

50
Fe
45 SiO2
LIMONITE SAPROLITE
PERCENTAGES

40
35

Transition zone
30
MgO
25
20
15
AlO2O3
10
5
0
-6 -4 -2 0 2 4 6 8 10 12 14
DEPTH IN METRES
P.T. INCO Minor Elements in Laterite Profile
3.5
Cr2O3
3.0
PERCENTAGES

LIMONITE SAPROLITE
2.5 Supergene Ni
enrichment
2.0
MnO
1.5 Ni
Transition zone

1.0

0.5 Co
0.0
-6 -4 -2 0 2 4 6 8 10 12 14
DEPTH IN METRES
P.T. INCO Relative Concentration from Bedrock values

25
CONCENTRATION FACTOR
FROM BEDROCK VALUES

Transition zone
Fe
20 Co
Al2O3

Ni
15 SAPROLITE
Co

MnO
10
Ni Cr2O3

5
LIMONITE
0
-6 -4 -2 0 2 4 6 8 10 12 14
DEPTH IN METRES
P.T. INCO Dunite to Goethite — Mass Balance

1.0 m
Dunite 0.32 m
Goethite

Dunite Goethite
Mineral Olivine Goethite
Composition (Mg,Fe)2SiO4 Fe2O3.H2O
Block size, m. 1x1x1 1 x 1 x 0.32
Particle density 3.2 4.4
Dry Bulk Density 3.2 1.1
Fe content, % 5.5% 50%
Kg of Fe 176 176

Dunite: density x % Fe 17.6

Volume of Goethite = = = 0.32
Goethite: density x % Fe 55.0
P.T. INCO RATES OF LATERISATION
• Based on mineral solubilities in the laboratory:
§ 1mm / 100 years
§ 1m / 100,000 years
§ 10m / 1,000,000 years
§ 50m / 5,000,000 years

• According to Paul Golightly, water emerging from well-

drained ultramafics typically contains:
§ 25 ppm Mg
§ 10-20 ppm Silica
§ pH = 7 – 8
The above corresponds to maximum rock dissolution of:
§ 1.4mm / 100 years
§ 1.4m / 100,000 years
§ 14m / 1,000,000 years
§ 70m /5,000,000 years
 P.T. INCO RATES OF LATERISATION

100,000 100 metres

Based on water
m m o f L a te rite

10,000 10 metres compositions of

well-drained
Ultramafics
1,000 1 metre

100
Based on mineral
10 solubilities in the
Laboratory
1
1

10

1,

10

10

10
10

1,
00

00
0

,0

0,

,0
0

00

00

00
0,
00
0

,0
00
0
TIME IN YEARS
P.T. INCO Miscellaneous Aspects of Laterites

• Dry Bulk Densities in laterites

• Upgrading of laterites (rejection of rock, silica)
• Burial of laterites (by sediments, volcanic ash)
• Laterites as unconformities in stratigraphic sequences
• Laterites make poor soils for agriculture
• Laterites as source of metals:
§ Ni, Co, Cr (from basic/ultrabasic rocks)
§ Al (from aluminous rocks – Syenite, limestone)
§ Fe is not usually recovered due to better deposits
• Processing of laterites:
§ Pyrometallurgy: if MgO is high; Co is unimportant; cheap power
§ Hydrometallurgy: if MgO is low; Co is important
P.T. INCO Module B7

Use of nickel in the industry

World laterite deposits & resources
GLOBAL ASPECTS OF World nickel production
NICKEL LATERITES
Major laterite projects & companies
New laterite projects
Processing of nickel laterites
Sulphide vs. laterite processing
P.T. INCO USE OF Ni IN THE INDUSTRY

• Over 60% of the world’s nickel is used for making

stainless steel
• With the addition of nickel in steel, it is made resistant to
corrosion
• Nickel is also used in making superalloys that can
withstand high temperatures and pressures (also high
electrical conductivity)
• Nickel is also used for plating, making coins, Ni-Cd and
Ni-metalhydride batteries, and as a chemical catalyst
• Cobalt has properties similar to nickel but is more
expensive
• Primary nickel supply comes from newly mined ores
• Secondary nickel supply comes from recycling scrap
 World Nickel Laterite Deposits
P.T. INCO

Albania
Greece
Cuba Dominican India Burma
Republic Ivory Coast Philippines
Guatemala
Columbia VenezuelaBurundi Ethiopia Indonesia
Brazil Zimbabwe PNG
Madagascar New
Caledonia
Australia

Producing Countries
Non Producing Countries
P.T. INCO LATERITE vs. SULPHIDE DEPOSITS

CUBA
PHILIPPINES

INDONESIA

NEW CALEDONIA

AUSTRALIA

LATERITES SULPHIDES
 World Nickel Laterite Resources
P.T. INCO (Distribution by Contained Nickel)

Mt Resource % Ni Mt Ni %

Caribbean 2785 1.26 35.0 25

New Caledonia 1890 1.52 28.7 20
Indonesia 1401 1.63 22.8 16
Philippines 1162 1.30 15.1 11
Australia 1144 0.95 10.9 8
Africa 800 1.33 10.7 8
C. & S. America 661 1.60 10.6 8
Other 539 1.08 5.8 4

Total 10382 1.34 140 100

 World Nickel Laterite Resources
P.T. INCO
(Distribution by Contained Nickel)

C. & S.
America Other
4% Caribbean
Africa 8%
25%
8%
Australia
8%

Philippines
New
11%
Indonesia Caledonia
16% 20%
P.T. INCO WORLD’S LAND-BASED Ni RESOURCES
Excluding sea-based manganese nodules

Mt % Contained Relative
Ore Ni Nickel %

SULPHIDES 10,594 0.58 62 31%

LATERITES 10,382 1.32 140 69%

TOTAL 20,976 0.96 202 100%

P.T. INCO INCO RESERVES & RESOURCES

On the basis of contained nickel

Category Sulphide Laterite Total

Nickel Nickel Nickel
PN + PB 4.0 2.8 6.8
Reserves
M + IND 1.6 3.0 4.6
Resources
INF 0.8 7.7 8.5
Resources
Total Resource Base 6.3 13.5 19.8
(32%) (68%) (100%)
 P.T. INCO WORLD LATERITES – Grade/Tonnage Plot
LIM Producing (Yr 2000) LIM Likely to produce (by 2010) LIM Non-producing
SAP Producing (Yr 2000) SAP Likely to produce (by 2010) SAP Non-producing
2.8
SLN Hi grade
2.6
Taganito Koniambo
2.4 Hinatuan
Rio Tuba

2.2 Puma
Onca
Funguesso
2.0
% Ni Grade

R 1-5 C.Matoso
Soroako
C 1-5 Inco Pomalaa
1.8 Benguet Inco Coastal
Bahodopi
SOA
Exmibal 15 B lb Ni
B.Alto PTAT
1.6 Tocantins Falcondo
Loma Inv.
Gag 10 B lb Ni Goro Ni
Sipilou
B 1-5 N.Cal.
1.4 Codemin Cupey
Soroako Prony
Moa Inco Pomalaa Palawan Indep.
Apo Mindanao
1.2 M 1-5 P.Gorda Ambatovy
Nicaro Ramu R.
Murrin M. 6-20
1.0 2 B lb Ni Pinares
Bulong Marlboro 5 B lb Ni
Larco des Mayari
6-20
0.8 Raventhorpe Mt.Marg.
6-20
1 B lb Ni Cawse 6-20
0.6
0 50 100 150 200 250 300 350 400 450
Millions of tonnes of Resource/Reserve
P.T. INCO
WORLD Ni PRODUCTION & RESOURCES

PRIMARY Ni PRODUCTION WORLD Ni RESOURCES

60% 70%

SULPHIDE LATERITE

LATERITE SULPHIDE

40% 30%
P.T. INCO
INCO NICKEL PRODUCTION & RESOURCES

Ni PRODUCTION 1998 Ni RESOURCES

68% 68%

SULPHIDE LATERITE

LATERITE SULPHIDE

32% 32%
P.T. INCO MAJOR LATERITE PRODUCERS
For 2003
Country Producers Mt Ni % of
world
Indonesia PT Inco; ANTAM 79,100 16.9
Cuba Cuba Nickel 75,000 16.0
Australia QNI (BHP-B); Minara 67,383 14.4
Japan PAMCO; Hyuga; Nippon Yakin 63,000 13.5
New Caledonia Eramet/SLN 61,500 13.2
Columbia Cerro Matoso (BHP-B) 46,900 10.0
Brazil Anglo; others 30,000 6.4
Dominican Rep. Falcando (Falconbridge) 27,227 5.8
Venezuela Loma de Niquel (Anglo) 17,200 3.7
TOTAL 467,310 100%
 MAJOR LATERITE PROJECTS &
P.T. INCO
COMPANIES (2003)

World’s top three integrated laterite projects:

§ Sorowako Project (PT Inco): 70,200 t Ni
§ Doniambo Project (SLN): 61,500 t Ni
§ Cerro Matoso (BHP-B): 46,900 t Ni

World’s major laterite producing/processing companies:

(Government owned Cuba Nickel is excluded)
§ BHP-Billiton: 78,000 t Ni
§ PT Inco: 70,200 t Ni
P.T. INCO NEW LATERITE PROJECTS 2004-2007

New Projects:
§ Goro Nickel, New Caledonia 54 k
§ Coral Bay, Philippines 10 k
§ Ravensthorpe, Australia (QNI) 50 k
Under
Construction
Expansions:
§ Sorowako, Indonesia 22 k
§ Doniambo, New Caledonia 15 k
§ Pomalaa (ANTAM), Indonesia 15 k
§ Murrin-Murrin, Australia 10 k
P.T. INCO NEW LATERITE PROJECTS 2008-2012

New Projects:
§ Koniambo, New Caledonia 54 k
§ Vermellho, Brazil 45 k
§ Onca-Puma, Brazil 25 k
§ Ambatovy, Madagascar 40 k
§ Barro Alto, Brazil 20 k
§ Exmibal, Guatemala 20 k

Expansions:
§ Coral Bay, Philippines 15 k
§ Moa, Cuba 17 k
§ Loma de Niquel, Venezuela 17 k
P.T. INCO NEW LATERITE PROJECTS – Beyond 2012

New Projects:
§ Bahodopi, Indonesia
§ Gag Island, Indonesia
§ Weda Bay, Indonesia
§ Ramu River, Papua New Guinea
§ Sechol, Guatemala

Expansions:
§ Goro, New Caledonia
§ Sulawesi, Indonesia
§ Onca-Puma, Brazil
§ Cuba
 INDONESIA
P.T. INCO
Principal Nickel Laterite Deposits

SERAWAK

HALMAHERA
SULAWESI
GEBE
WEDA BAY WAIGEO IRIAN JAYA

SOROAKO OBI GAG PNG

BAHODOPI SENTANI
SUMATRA
KALIMANTAN POMALAA

JAVA
TIMOR

500km
 NEW CALEDONIA
P.T. INCO
Principal Nickel Laterite Deposits

Poum

Tiebaghi
Etoile du Nord
Tchingou
Koniambo
Moneo
Nepoui Poro
Louaoua
Me Maoya Nakety
Tene Bourail Thio
LEGEND

Residual Nickel Deposit

Sedimentary Nickel Deposit Tontouta Quinne
Ultramafic Yate
NOUMEA Goro
Pernod
Prony
 Range of Laterite Profiles
P.T. INCO
From dry to wet tropical climates

Dryer Climate Humid Climate Humid Climate

(Western Australia) (Goro Plateau) (Indonesia hills)

WA
Laterite
Profile
Ferricrete
Limonite
Nontronite
Saprolite
Altered Peridotite

%Ni %Co %Mg %Fe %Ni %Co %Mg %Fe %Ni %Co %Mg %Fe
Ferricrete .2 -.5 .02 .6 35+ .2 -.5 .02 .6 35+ .2 -.5 .02 .6 35+
Limonite .6-1.4 .1-.2 1-2 45 1.2-1.7 .1-.2 1-2 45 1.2-17 .1-.2 1 -4 45
Nontronite 1.2 .08 3.5 18
Saprolite .4 .02 12.0 9 1.5 -3 .05-.1 10-20 10-25 1.5-3 .05-.1 10-30 10-20
P.T. INCO PROCESSING OF Ni LATERITES

• Pyrometallurgical processing
(Ore is melted)
§ Production of Ferro-nickel
§ Production of Ni-S matte

• Hydrometallurgical processing
(Ore is leached with acid solutions)

• Combined pyro and hydro process (Caron)

(Ore is reduced at high temperature, then leached)
P.T. INCO Ferro-Nickel Projects in the world

Project Owner Country Remarks

Cerro Matoso BHP-B Columbia
Codemin Anglo Brazil
Doniambo SLN/Eramet New Caledonia
Exmibal Ex. Inco Guatemala Mothballed
Falcondo Falconbridge Dominican Rep.
Fenimark FENI (govt.) Macedonia Closed
Hyuga Sumitomo Japan Imported ore
Larymna Larco Greece
Loma de Hiero Anglo Venezuela
Morro do Niquel Anglo Brazil Closed
Oheyama Nippon Yakin Japan Imported ore
PAMCO Nippon Steel Japan Imported ore
Pomalaa ANTAM Indonesia Some imported ore
P.T. INCO Nickel-Matte Projects of the world

Project Owner Country Remarks

Sorowako PT Inco Indonesia
Doniambo SLN/Eramet New Caledonia
P.T. INCO HPAL Projects of the world

Project Owner Country Remarks

Bulong Australia
Cawse Australia
Murrin-Murrin Australia
Moa Bay Cuba First HPAL
Coral Bay Philippines Just completed
Goro New Caledonia Under construction
P.T. INCO CARON Projects of the world

Project Owner Country Remarks

Nicaro Union del Niq Cuba
Punta Gorda Union del Niq Cuba
Nonoc Philippines Closed
QNI BHP-Billiton Australia Imported ores
Tocantins Niquel Toc. Brazil
P.T. INCO PYROMETALLURGICAL PROCESSING

Ferro-Nickel Process Nickel-Matte Process

Upgrading in the mine Upgrading in the mine

Drying of ore Drying of ore

Upgrading after drying Upgrading after drying

Calcining Calcining

Electric Furnace Smelting Electric Furnace Smelting

Refining Furnace Converting

Ferro-Nickel Product Nickel-Matte Product

20 – 50% Ni 78% Ni
P.T. INCO PYROMETALLURGY

Important concerns:
• Slag should not attack refractory (S/M ratio)
• Melting temperature should be suitable (S/M; Fe)
• Olivine should not be introduced to the furnace
• Appropriate reduction of ore prior to smelting
• Ni/Fe ratio in the ore for ferro-nickel operation
P.T. INCO HYDROMETALLURGICAL PROCESSING

Ore Preparation: wetting, screening

Pre Heating through flash steam

Pressure Acid Leach in autoclave

Heat recovery from leached pulp

CCD thickening and washing

Neutralisation of pregnant solution

Precipitation of metals by adding H2S/alkali

Solid/liquid separation

Ni/Co products as mixed sulphides, oxides, hydroxides

P.T. INCO HYDROMETALLURGY

Important concerns:
• Amounts of soluble Mg and Al in ore (acid consumers)
• Acid to ore ratio required for process
• Minimum operating temperature required to leach
• What is the appropriate pressure during leaching
• Retention time in the autoclave
• Rheological behaviour during slurrying
• How to recover metals in the back end of processing
• What product to make
P.T. INCO CARON PROCESS

Ore Preparation: screening, upgrading

Drying, using oil or coal

Grinding

Reduction, using CO/H2

Ammonia leaching

CCD thickening and washing

Stripping, using steam

Calcining of Ni/Co precipitate

Sintering of calcine

Nickel oxide product

P.T. INCO NICKEL SULPHIDE vs. LATERITE PROCESSING

Nickel Sulphide Nickel Laterite

Mining Hard rock mining more Soft rock mining cheap.
expensive. Many sulphides U/G Only open cast mining
Deposit More uniform in chemistry and More varied in chemistry
uniformity mineralogy and mineralogy; stratified
Upgrading Highly upgradeable to sulphide Low upgradeability. Final
concentrate grade generally <2.0% Ni.
Ore/Con Relatively cheap (per lb Ni) due Relatively high (per lb Ni)
shipping to high upgradeability due to low upgradeability
Processing cost Modest due to high Ni content. High due to low Ni content.
Sulphur provides latent heat. High energy input required.
Ni recovery High due to consistency of ore Modest due to compromise
chemistry and mineralogy for prevalent chemistry
Capital cost Modest per lb of Ni High per lb of Ni
Project size/life Can be short to medium Long to pay for high capital