Lectures 1-3 COLOUR

20/07/2012
ESC2122
The Dynamic Earth II ‐ Global
processes
Dr Chris Folkes
Mon 23/7/2011
My contact details
• Email –
chris.folkes@monash.edu
• Office –
Office –
Room 104 (Bdg 28). Office hours – Mon 2‐4 pm & Wed
11am‐1pm
• Telephone –
(03)99053832. Just 53832 from internal Monash
telephones
Introduction and Housekeeping
Course goals?
We will be building on what you learned in first semester...(and
first year)
 In first semester (ESC2111) you studied processes that
( )y p
build and modify the Earth’s crust
 Specifically, how it deforms and how sedimentary
rocks and basins form in response to this
deformation
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 In first year (ESC1011 & 1022) you had an introduction to
most aspects of Earth Sciences
 In ESC2122 (this course!), we will be building on:
• The internal physical and chemical structure of the Earth
(and meteorites)
• Plate tectonics and related magmatism/volcanism
• Absolute dating of rocks (geochronology)
• Earth surface processes (e.g.,
hydrogeology/environmental science)
• The geochemical tools that we use to evaluate these
processes
 We will also be equipping you with new tools to be able to
identify rocks and minerals in hand specimen and thin
section (in practicals)
Read over your notes and study materials
from 1st year!!
• We
We will expect you all to already know the geologic processes
will expect you all to already know the geologic processes
and key terms that Marion taught in ESC1011 and ESC1022
• The practicals on mineral identification and igneous rocks you
did in 1st year will be particularly useful for the first half of
ESC2122 (especially the practicals!)
ESC 2122 Course Assessment
1. Practicals – 25% (most practicals will be assessed)
2. Practical exam – 15% (week 8 – during your usual

practical class  more information later)
practical class  more information later)
3. Two x 2 hour Closed book exams – 60% (End of
semester). Questions on all topics covered during
the entire ESC 2122 unit
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Important ‐ UCROO
• We will be trialing UCROO as a collaborative learning tool this semester (more
user‐friendly than Moodle for class discussions, forum posts etc…)
• It will be used alongside Moodle (not as a replacement)
• Before next week:
– Go to www.ucroo.com and sign up to UCROO
G d i UCROO
– Add your enrolled units for Semester 2 (including this one)
• You can direct questions and comments you have for me or fellow classmates
through this class’s feed on UCROO
• If you have any problems contact – team@ucroo.com
Lecture Series – Mon 4‐6pm here! (E2); Wed 1‐2pm (E2)
• 3 weeks of The Earth’s internal structure & composition – Dr Chris
Folkes
• 1 week of Physical Volcanology
1 week of Physical Volcanology – Prof. Ray Cas
Prof. Ray Cas
• 3 weeks of Magmatic Processes – Dr Chris Folkes
• 4 weeks of Hydrogeology, Groundwater & Environmental geoscience
– Prof. Ian Cartwright/Dr Sasha Wilson
• 1 week of Terrestrial planets and meteorites/geodynamics – Marion
Anderson
Lecture Series – Mon 4‐6pm here! (E2); Wed 1‐2pm (E2)
You can see that these are very diverse topics BUT there is a
common theme:
 We live on a differentiated (i.e. heterogeneous) planet
We live on a differentiated (i.e. heterogeneous) planet
 This course is designed to give you a broad‐based understanding
of the processes that lead to the Earth’s differentiated structure:
 That is how is stuff moved around within and on our planet??
 And how do we define the various geochemical reservoirs
that exist today
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• This subject will be a little different to others....
• Normally, the material in lectures serves as the theory to be applied in
the practicals
• However, at least in the first few weeks of this semester, the lectures and
However, at least in the first few weeks of this semester, the lectures and
practical classes will be somewhat detached
• This is because we need to introduce you to the basics and the theory of
petrology and optical microscopy whilst you have the microscopes in
front of you (in practical classes)
• The later lectures and practicals I will be giving should converge (as will
the other lectures/prac in this course)
Practical Series – Tues 9am‐12pm OR Thurs 2‐5pm:
• Starting in week 1 – That’s this week!
• 3 weeks of mineral/rock identification & introduction to
optical mineralogy – Chris Folkes
• No practical in week 4
• 3 weeks of continuation of mineral/rock identification &
optical mineralogy – Chris Folkes
• Practical exam (identification of rocks/minerals) – week 8
• 3 weeks of hydrogeology/environmental geoscience ‐ Ian
Cartwright/Sasha Wilson
• No practical in week 12
Practical Series – Tues 9am‐12pm OR Thurs 2‐5pm :
What else do you need to know about the pracs?
One prac session per week
Tuesday 9am‐12pm
OR Thursday 2‐5pm
Please go to your ALLOCATED prac session (swaps are
allowed but only if you find another student to swap
with and let me know)!!!!
Each prac session is designed to be 3 hours long
Located in G09 (down the corridor from G60 – 1st year lab),
building 28
If required, you will need to collect your allocated
microscope from the cupboards in G09
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Practical Series – Tues 9am‐12pm OR Thurs 2‐5pm :
What else do you need to know about the pracs?
 Late penalties: marks for practical work will be deducted 10% for
every 24 hours it is submitted after the deadline (unless
accompanied by a Special Consideration form and supporting
accompanied by a Special Consideration form and supporting
documents)
 Special consideration must be officially lodged within 48 hours of
the deadline for a particular piece of work
 You will need to supply a doctor’s certificate or other documents
supporting your request for an extension/special consideration to
the lecturer/unit coordinator. See the ‘Special Consideration’ link
on the Faculty of Science web pages (also on Moodle page)
Texts and recommended readings
 No single text will contain all of the information in this course
 Where appropriate, each section will have recommended
references, texts, websites, course notes. These resources
will be put on Moodle (‘Useful References’ document)
 I will occasionally refer to these but you will need to keep
track of these yourselves
The best way to learn in this course:
 PARTICIPATE!
 If in doubt ask questions
 If not in doubt ask questions
If not in doubt ask questions
 Think about your learning strengths:
What is your motivation for being here?
Come to lectures and practicals, relaxed and ready
Focus on understanding and learning, not the grade
Basic note taking (during lectures)
Use reference material where necessary
THINK and talk to you classmates!
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Lets get started!
Plan of attack for the Lectures
• Week 1 (this week): Introduction to key concepts and terminology
– Lectures 1 & 2: The physical structure of the Earth. The chemical
composition of the Earth. The major rock‐forming minerals
– Lecture 3: The major rock‐forming minerals (continued)
h j kf i i l ( i d)
• Week 2: Mantle mineralogy; The silicate Earth: The asthenospheric mantle,
Chemical reservoirs
• Week 3: Plate tectonics, terrestrial chemistry and magmatic processes, mantle
melting
• (Week 4: Physical Volcanology – Prof. Ray Cas)
• Week 5: Magmatism in the ocean basins, volcanic arcs, mantle plumes,
continental flood basalts
• Week 6: Geochronology; dating of igneous rocks and minerals and global
geochemical cycles, MORBs, OIBs, basaltic magmas
• Week 7: Granitoid magmas
Lets get started!
Plan of attack for the Lectures
• References and readings:
 Course notes ‐ Handouts detailing material delivered in the
lectures and practicals  put on Moodle (Resources
(
subheading – ‘Structure of the Earth’, ‘Optics Manual’)
 List of ‘Useful References’ also on Moodle
 Glossary to help get on top of the terminology
 Discussion forum on Moodle and UCROO
 Anything interesting that I can find in the primary
literature will be put on Moodle ‐ feel free to contribute!
 Check Moodle and UCROO regularly!!
Lecture 1:
The large scale structure of the Earth
The large scale structure of the Earth
Presented by Dr Chris Folkes
Room 104, Building 28
Email: chris.folkes@monash.edu
Ph: 03 990 53832
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Introduction to key concepts and
terminology
• The large scale physical structure of the
Earth:
– The metallic core
– The D” layer discontinuity
– The mantle
– Seismic velocities and tomography
terminology
The physical structure of the Earth
• On a broad scale earth can be divided
into three portions....
Lithosphere (never
greater than 100
km)
Outer silicate
Mantle (3000 km)
Metallic Core
(3400 km)
terminology
The physical structure of the Earth
• On a broad scale earth can be divided
into three portions.... • Contains numerous
chemical and physical
subdivisions which will be
the primary focus of this
the primary focus of this
course
Outer silicate
Mantle (Si and O)
Metallic Core
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terminology
The metallic Core
• Comprises 30% of the mass of the Earth, 15% of its volume
• It consists of a fluid outer core and a solid inner core
• ~3400 km thick and extends about half
way to the surface of the Earth
• Formed early in Earth history but when
it ceased to segregate is unclear
• Chemically and physically isolated from
the silicate mantle
• ~5.7% Ni, ~10% S with the rest being
metallic Fe
We know this from seismic tomography
and refraction and from metallic
meteorites
terminology
The metallic Core
• We also know/think that the core is
a sink for other metallic elements
• Eg. Re, Au, PGEs, W etc.
Poses a problem because if this is
true then the silicate portion of the
Earth should be depleted in these
extremely valuable elements
terminology
The metallic Core
However, when we estimate the
composition of the silicate Earth (mantle +
crust) we find that there is actually a
rather high abundance of other metallic
elements such as Au and Pt
Q/ Why is this so??
A/ Some believe that there was a late
heavy meteorite bombardment to the
Earth that delivered lots of metals to the
silicate Earth after the core had locked the
original budget away
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terminology
The D” layer
• A distinct seismic discontinuity present in the upper 200 km of
the core – or at approx. 2900 km depth in the Earth
• This layer is very heterogeneous and has a remarkable amount
o topog ap y
of topography
D” • How do we know it’s
there?
Picked up in seismology ‐
Seismic waves reflect and
refract during earthquakes
and atomic testing.
terminology
The D” layer
• There are two schools of thought
– D” is a chemical reaction front between silicates and metals,
OR
– It is an accumulation zone of subducted oceanic slabs
It is an accumulation zone of subducted oceanic slabs
D”  Is this the
‘graveyard’ for
subducted oceanic
crust?
terminology
The D” layer
• There are two schools of thought
– In either case, D” is a thermal boundary layer and hence is
anomalously hot.
 Potentially the origin of mantle plume magmatism!!!
Potentially the origin of mantle plume magmatism!!!
D” Whatever the case there is
a huge thermal gradient
between the outside of the
core and the bottom of the
silicate mantle
 Analogy to lava lamps –
D” is like the base of the
lava lamps (heat source)
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terminology
The Mantle (silicate Earth)
Comprises about 60% of the mass of the Earth & 84% of its
volume
The Mantle has three parts:
• Lower mantle (>650 km depth)
• Transition zone (410‐650 km depth)
• Upper Mantle:
• Asthenosphere = place where the
convecting solid, (peridotite
mantle) melts
• Lithosphere = upper mantle and
crust, does not convect but
deforms in a brittle manner
Introduction to key concepts and terminology
volume
Lithosphere = Upper mantle + Crust
• It is actually quite insignificant!!
‘Moho’ • Never thicker than 100 km
• Only 0.5% of the mass of the Earth
• But it is important because it is what
we can best see/measure
• Lithosphere = very heterogeneous,
which means there are a number of
definitions for lithospheres!!!!
volume
• We can discuss the lithosphere in the
‘Moho’ context of:
1) Rheology = of or pertaining to the
deformation or flow of matter
2) Heat or Thermal properties
3) Chemistry
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volume
‘Moho’
1)The RHEOLOGICAL lithosphere is the
boundary between the part of the
mantle that is able to convect and that
which is rigid
volume
‘Moho’ 2)The THERMAL lithosphere is
sometimes considered to be the
1290C isotherm, which is considered
the boundary between the ambient
mantle temperatures and the cooler
lithosphere.
volume
3)The CHEMICAL lithosphere is considered
‘Moho’ to be the boundary between the chemically
depleted upper mantle and the chemically
differentiated curst and peridotite.
•Does this makes things confusing??
Not really ‐ often there is virtually no
difference between these lithospheres… but
sometimes it is just more accurate to specify
which lithospheric properties you are
referring to
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Comprises about 60% of the mass of the Earth & 84% of its volume
• The thickness of the lithosphere varies dramatically and this is mainly because
The thickness of the lithosphere varies dramatically and this is mainly because
of the two types of crust:
1) Oceanic crust
2) Continental crust
oceanic crust continental crust

35-70 km
0-7 km
oceanic lithospheric
sub continental
mantle: <35 km asthenosphere lithospheric mantle
125-300 km
upper
lower mantle mantle
1) Oceanic crust is:
• Thin (approximately 6km)
• Nowhere is it older than ~200 Ma (subduction ‘destroys’ it)
• Beneath the oceanic crust is a correspondingly thin oceanic
lithospheric mantle (<35km)

35-70 km
0-7 km
oceanic lithospheric sub continental
125-300 km
upper
lower mantle mantle
2) Continental crust is:
• 35‐40 km thick on average
k hi k
• Relatively permanent (the oldest part of the lithosphere – 4.2 Ga
dated zircons from Jack Hills, WA ‐ Cratons)
• Beneath the continental crust is a correspondingly thick sub‐
continental lithospheric mantle (125‐300 km; SCLM)

35-70 km
0-7 km
oceanic lithospheric sub continental
125-300 km
upper
lower mantle mantle
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Precambrian (>540 Ma) cratons
 Old and stable part of the continental lithosphere (always remained as
continental crust)
Archean
>2.5 Ga
• Think of the lithospheric mantle as the
‘Moho’ keel of a ship (the main frame/structure
that sits below the water) that the
oceanic and/or continental crust floats on
• A thick keel is need to stabilise a thick
crust (hull of ship)
This is due to isostasy – zones of rigid
lithosphere “float” in plastically
deforming asthenosphere
The silicate earth is what we are
interested in for this course (major
rocks and minerals)
The lithosphere includes more than
just the crust
Wh i th
Why is the mantle important?!
tl i t t?!
The mantle comprises the
majority of the silicate earth and
the mantle is what controls plate
tectonics!!!
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We’ve just defined the major physical structures of
the Earth.
At this stage you might be wondering.....
How do we know all this?!
1. Seismology
2. Igneous geochemistry and samples from the mantle
3. Classes of Meteorites
4. Experimental Petrology
Seismology velocities and tomography
• Much of what we know comes from seismic studies:
• When an earthquake occurs, it sends
seismic waves through the earth that
can be detected around the globe
• The propagation of seismic (P and S)
waves through the interior of the Earth
are dramatically affected by variations
in mineral structure (i.e. Density!!)
• Denser materials allow seismic waves to
travel faster through them
• Seismic waves refract at boundaries
where major changes in density occur
• P and S waves
• The fastest wave, and therefore the first
to arrive at a given location, is called the
P (primary) wave.
• The P wave, or compressional wave,
alternately compresses and expands
material in the same direction it is
travelling.
• The S (secondary) wave is slower than

the P wave and arrives next, shaking the
ground up and down and back and forth
perpendicular to the direction it is
travelling.
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• P and S waves
Note the transition zone and the ~660
km discontinuity (more next week)
For example, this is how we distinguish between
the lower part of the lithospheric crust and the
upper lithospheric mantle...
• The boundary between the crust and the
mantle is defined by an abrupt change in
chemical composition
• This compositional change is accompanied
by a major change in seismic velocities
across the boundary
• This discontinuity is called the “Moho”
• Short for Mohorovicic (‘Moe‐hoe‐roe‐
vee‐cheech’) Discontinuity
• The Moho is commonly at 35‐40 km depth beneath the continents but it

can be as deep as 70 km (e.g. beneath the Himalayas) and it shallows as
continental crust thins towards the ocean basins where it is 5‐11 km deep
• It lies entirely within the lithosphere (except at mid‐ocean ridges – thin
crust, where it is the lithosphere‐asthenosphere
, p p boundary)
y)
Depth (km)
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In continents, the Moho is the transition from quartz rich rocks (i.e. granitic
continental crust) to ‘peridotite’ ‐ the main mantle material/rock type.
In oceanic crust, the Moho is a transition between basaltic oceanic crust and
p
peridotite.
Depth (km)
• Note also that there is a flattening
(slowing) in the rate of increase of
seismic velocities in the top of the
upper mantle
• This is due to the presence of small
volumes of partial melt. This portion of
the mantle is termed the asthenosphere
• S waves do not trave through
liquid/melts (e.g., the outer core)
• By far the biggest changes in density
occur at the core‐mantle boundary,
and at the outer core‐inner core
(li id lid) i
(liquid‐solid) interface
f
• Studies combining reflection and
refraction of seismic waves that
propagate through the Earth from
major earthquakes (or large
explosions) place constraints on the
broad scale structure of the Earth
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• Improvements in resolution due to
an increase in distribution of seismic
collectors, advances in number
crunching technology and more
sophisticated detectors have allowed
increasingly clearer tomographic
images of portions of the Earth
• Obviously, those areas closer to the
surface have better resolution
• For example, it is possible to image
the behaviour of subducting slabs
the behaviour of subducting slabs
down to depths of at least the
proposed 660 km discontinuity
• These images allow us to investigate
the fate of material which returns to
the mantle via subduction (more on
this in weeks 5 & 6)
• So too it is possible to use such
tomography to investigate sites of
active upwelling in the mantle, such
as beneath Hawaii and Iceland
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We’ve just defined the major physical structures of
the Earth.
At this stage you might be wondering.....
How do we know all this?!
1. Seismology 
2. Igneous geochemistry and samples from the mantle
3. Classes of Meteorites
4. Experimental Petrology
 We will examine points 2 and 3 in the rest of this course.
Point 4 is covered in ESC3421 – Volcanology & Igneous Petrology
A lot of effort has gone into understanding the physical and
chemical nature of the Earth’s mantle
A final question before we leave this topic......
Why is the mantle important???
Why is the mantle important???
1. The mantle is what controls plate tectonics
2. The mantle comprises the majority of the silicate Earth
(~90% of all known crustal minerals are silicates)
The mantle is what controls plate tectonics
1. The earth’s internal heat is responsible for tectonic processes
2. This internal heat decays over geologic time as it migrates to the surface
3.
3 Heat causes both the outer core and mantle to convect
Heat causes both the outer core and mantle to convect
4. The asthenospheric mantle below the lithosphere is hot enough and under
sufficient confining pressure that it flows
5. This convection drives tectonic processes, which mostly happens at plate
boundaries. For instance:
•Divergent plate boundaries – mid‐ocean ridges
• Convergent plate boundaries – subduction zones
• Convective upwelling in plate interiors – Mantle plumes
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Crust
Mantle
D’’
Core
• The red ‘upwelling’ portions are mantle ‘plumes’
• Note that the geometry (shape, size) of each plume is different
• This process may take millions of years (Myr’s) in the Earth’s mantle
• There is also the associated return flows of colder material (blue –
includes crust?)
• The D’’ region (lower mantle‐outer core boundary) is thought to be
responsible for the generation of major mantle plumes
The mantle comprises the majority of the silicate Earth
• The mantle is Ultramafic ‐ comparatively rich in
ferromagnesian (Fe & Mg) silicates (Si‐minerals)
 We can add to this the lithospheric crust as the other major
reservoir for the silicate minerals.
• Continental crust is Felsic – rich in alumino‐silicates (Al‐rich ‐
e.g., feldspars)
• Oceanic crust is Mafic – 50:50 mix of above
• The Mantle (and crust) comprises the majority of the silicate
Earth
– These differences in composition are accompanied by
h d ff db
differences in density
• Responsible for the layering of the Earth – the density
of each layer decreases outwards (towards the Earth’s
surface)
– The Continental crust is the least dense layer, which is part
of the reason why it sticks out above the ocean
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Continental Crust Oceanic Crust Mantle
 We will come back to this diagram. Also always keep in mind Bowen’s
reaction series....
Bowen’s reaction series
Low viscosity,
Mantle High‐T (up to
1300°C)
Oceanic
Oceanic
Crust
Continental Extremely
Crust viscous, low‐T
(700‐800°C)
 Generally, magmas/melts of different temperatures will crystallise different
minerals as they cool (as long as the magma has the right ingredients ‐ elements!!)
Topic 2:
The chemical composition of the
p
Earth I
Presented by Chris Folkes
Room 104, Building 28
Ph: 03 990 53832
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Chemical composition of the Earth
Outline
• The large scale chemical composition of the
Earth I
– Introduction to silicate mineralogy and
crystallography
• Elements: The building blocks
• The anatomy of the silicate tetrahedra
• The major silicate mineral groups
Introduction to mineralogy and crystal chemistry
• The Mantle and crust comprises the majority of the silicate
Earth
– The various parts of the silicate earth have different bulk
compositions that directly correlate with different bulk
mineralogy (i.e mineral assemblages)
– In other words mineralogy controls the physical structure
of the silicate Earth.
Earth
– In order to understand the nature of the differences in
mineralogical and chemical composition that resulted in
the layered structure of the Earth we need to talk about
mineralogy....
• Specifically, Crystal chemistry and the chemical
composition of minerals (and a bit of crystallography)
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Earth
– In first year you were introduced to the major mineral
groups (in hand specimens) so consider this the next step
in learning about silicates in the mantle and crust....
Earth
– Starting from the top: What is the definition of a mineral?
A mineral is defined as:

1. Naturally occurring
2. A homogeneous solid
3. Has a highly ordered atomic arrangement
(crystalline)
4. And has a definite (but not fixed) chemical
composition
Mineralogy and crystal chemistry of the major silicate
groups
Lets start with some facts about the basic building blocks of
minerals….Elements
• The abundance of Earth’s building materials (the whole Earth):
O and Fe – each close to 32%
Mg 15%
Mostly Si 14%
locked
Ni 1.8%
away in
Ca 1.7%
the
Earth’s Al 1.6%
core
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BUT, If we were to grind up only the whole of the silicate earth (crust +
mantle; Bulk Silicate Earth ‐ BSE) and analyse its chemical composition......
Graphical Representation of Elemental Abundance

In Bulk Silicate Earth (BSE)
Six elements make up 99.1% of BSE ->
From W . M . W hite, 2001
Mineralogy and crystal chemistry of the major silicate
groups
Lets start with some facts about the basic building blocks of
minerals Elements in the bulk silicate Earth (BSE)
minerals….Elements in the bulk silicate Earth (BSE)
Because of this the outer
O  44% portion of the Earth consists
Most principally of compounds
abundant Mg  23% known as SILICATES (Si & O):
Si  21%
• About 25% of all known minerals
Fe  8% are silicates
Ca  2.5% • Nearly 40% of the most common
minerals are silicates
Al  2.4% • All igneous rock‐forming
minerals (>90% of crust)
Mineralogy & crystal chemistry of the major silicate
groups
 Silicates are compounds based on the silica tetrahedron. This is
the main building block of all silicates
The silica tetrahedron
• Ions are atoms that have either gained or lost
electrons from their outer most valence shells
Anion = a negatively charged atom (O2‐)
Cation = a positively charged atom (Si4+)
• The tetrahedron structure is formed when one
Si4+ bonds with four O2‐
• These chemical bonds form by the sharing of
electrons between oppositely charged ions
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groups
Silicates are compounds based on the silica tetrahedron
How these electrons are shared determines the
How these electrons are shared determines the
nature of the chemical bond or BOND TYPE
Strongest
Covalent
Ionic All of these
bond types
Metallic
coexist in most
van der Waals silicate
minerals
Hydrogen bonding
Weakest
groups
• BOND TYPE is determined by the nature of the
electrical forces that exist between two
interacting atoms or ions or ion groups
• The type and strength of the bonds are
responsible for the physical and chemical
properties of the minerals:
Eg. Hardness and Cleavage
In general the stronger the bond the harder the
crystal, the higher the melting point, and the
smaller its coefficient of thermal expansion
groups
O2‐ = 1.40A
1 40A
• In addition to atomic number there are two
inter‐related characteristics that determine the
nature of the bonds that form between ions in a
crystal structure
Si4+ = 0.42A 1) Ionic charge & 2) Ionic Radii
Atom gains electron(s) = Anion (‐ve charge,
big)
Atom loses electron(s) = Cation (+ve charge, smaller)
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groups
O = 3.5 • IIn terms of bonding, these properties can be
f b di h i b
summarised by a concept developed by Linus
Pauling called ELECTRONEGATIVITY, which is the
tendency of an element to attract a shared
electron when bonded to another element.
Si = 1.8 • Values range from 0.7 (Cs) to 4.0 (F)
• The larger the difference in electronegativity the
more ionic the bond (>2 = ionic bond)
The more similar the values the more covalent
the bond
groups
O = 3.5
O‐Si = 1.7, therefore ~50% covalent and 50% ionic
Covalent Strongest
Ionic
Si = 1.8
Metallic
van der Waals
Hydrogen bonding
Weakest
groups
e‐
• Si4+cation shares an electron with each of
the four O2‐ anions
e‐ • But each O anion has two valence
electrons available for sharing so they can
form an additional bond
e‐ e‐
e‐ • This additional bond can be with another
e‐
e‐ metal cation OR it can be with a second Si
e‐
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groups
 When O bonds with a second Si this leads to linking
of the individual silica tetrahedra to form the following
structures:
Rings
Chains
Sheets
Frameworks
The O that forms the linking bond is referred to as the
bridging oxygen
groups
• The linking of tetrahedra is referred to as
polymerisation and this is the origin of the great
variety of silicate structures
• There are 6 primary structural types of silicates, all
based around our silica tetrehedra, each with a
characteristic Si:O ratio.
• Lets start with the least polymerised silicate….
groups
1) Orthosilicates or Nesosilicates (‘islands’) –

least polymerised
• Isolated Tetrahedra (Si:O = 1:4)
– E.g., Olivine: (Mg,Fe)2(SiO4)
1) Forsterite
Forsterite – Mg2SiO4
2) Fayalite – Fe2SiO4
26
20/07/2012
groups
2) Sorosilicates (minimal polymerisation, ‘double island’)
• 2 linked Tetrahedra (Si:O = 2:7)
– E.g., Epidote group of minerals
– Tanzanite: Ca
Tanzanite: Ca2Al3(SiO4)3
groups
3) Cyclosilicates (increased polymerisation, ring
structure)
• >2 linked Tetrahedra (Si:O = 1:3) Aquamarine
– Tourmaline:
(Na,Ca)X3Y6Si6O18(BO3)3(O,OH)3(OH,F)
– Beryl: Be3Al2Si6O18
Emerald
groups
4) Inosilicates (increased polymerisation,
single and double chain structure)
• Single linked Tetrahedra chain (Si:O = 1:3)
E.g., Pyroxenes:
Enstatite: Mg
Enstatite: Mg2Si2O6
Ferrosilite: Fe2Si2O6
27
20/07/2012
groups
5) Inosilicates (increased polymerisation, single
and double chain structure)
• Double linked tetrahedra chain (Si:O = 4:11)
E.g., Amphiboles ‐ AX2Z5(Si,Al,Ti)8O22(OH,F,Cl)2
Hornblende:
Ca2(Mg,Fe,Al)5Si8O22(OH)2
groups
6) Phyllosilicates (high polymerisation,
sharing 3 O’s between tetrahedra)
• Sheet structure (Si/Al:O = 2:5)
E.g., Micas:
Biotite: K2(Mg,Fe)6(Al2Si6O20)(OH)4
Muscovite: K2Al4(Al2Si6O20)(OH)4
groups
Tectosilicates (complete polymerisation, 3D network)
• Framework structure (Si:O = 1:2)
28
20/07/2012
groups
• Framework structure (Si:O = 1:2)
E.g., Quartz: SiO2
 Low temperature phase, found in highly evolved (High‐Si) igneous
rocks (Granites rhyolites)
rocks (Granites, rhyolites)
 Usually colourless/grey (glassy) but minor amounts of trace elements
(Li,Na,K,Al,Fe,Mn,Ti) can give rise to coloured quartz (e.g., Smoky, Rose,
Amethyst)
groups
• Framework structure (Si/Al:O = 1:2)
Feldspars: (K,Na,Ca)AlSi3O8
Most abundant constituents of igneous rocks. Two main types

Most abundant constituents of igneous rocks. Two main types
1) Alkali feldspars – (K,Na)[AlSi3O8]
E.g., Orthoclase, sanidine,
microcline
2) Plagioclase feldspars ‐
Na,Ca[Al1‐2Si2‐3O8]
groups
Okay, so that takes care of Si and O.
Hopefully at this stage you are wondering.......
1) What about those other elements that were mentioned a few slides back as
building blocks?
2) How do we know where and how many of these other elements go in the
crystal structure of a silicate mineral?
3) Part of the definition of a mineral was that it had a definite but not fixed
chemical composition – What does this mean?
29
20/07/2012
groups
To answer these questions we need to talk about
1. Electroneutralityy
2. Coordination number
3. Chemical substitutions
 We’ll examine these next lecture.....
groups
That’s it for now
• To reinforce these ideas, read section 1 of the ‘Structure of the Earth – Study
Guide’ on Moodle
• Next lecture we will look at chemical substitutions (solid solutions) in
minerals and continue exploring the silicate Earth
• For this week’s practical – revise 1st year notes on rock‐forming minerals
Reading for the next lecture (Wednesday 1pm):
• Read section 3 of the ‘Structure of the Earth ‐ study guide’ on Moodle
Lecture 3:
The chemical composition of the
Earth II
Wed 25/7/2012
Presented by Chris Folkes
Room 104, Building 28E
Ph: 03 990 53832
30
20/07/2012
groups
Last class we reviewed aspects of silicate mineralogy:
• The major silicate groups
Tanzanite • How atomic/ionic properties of the
elemental building blocks control the
structure of the crystal.
• Some of the more important principals of
crystal chemistry:
Emerald
‐ Bonding b/w Oxygens and cations
‐ Electronegativity
‐ General formula (of silicates)
‐ Coordination (today)
‐ Electroneutrality (today)
groups
Last class we reviewed aspects of silicate mineralogy:
Tanzanite • Today we will also continue the
discussion of mineralogy and
crystal chemistry in order to
crystal chemistry in order to
continue our introduction of key
concepts and terminology
regarding the chemical
Emerald
composition of the Earth
groups
Quick review:
• Silicon invariably occupies
the centre of tetrahedra in 4‐
fold coordination with O
• The total variety of silicate minerals is based around how
these tetrahedra are linked together:
1) Single tetrahedra (“orthosilicates”)
2) Linked tetrahedra (“sorosilicates”)
3) Chain (single and double) silicates (“inosilicates”)
4) Sheet silicates (“phyllosilicates”)
5) Closed ring silicates (“cyclosilicates”)
6) Framework silicates (“tectosilicates”)
31
20/07/2012
groups
To fully understand the differences in silicate groups and
their chemistry, we need to examine:
1. Electroneutrality
groups
1) Electroneutrality
• A
A final constraint on the stability of a mineral
final constraint on the stability of a mineral structure is that it
structure is that it
must be electrically neutral. That is that the total number of
positive charges must equal the total number of negative
charges.
• BUT…how many of which ions, in which silicate structures?
• Luckily the only anion we have to deal with is O, which we know
has a charge of ‐2
• And thankfully, we are fairly limited in terms of the number of
other readily available and/or abundant metal cations
groups
• For instance
For instance ‐ for every 100 atoms in the crust:
for every 100 atoms in the crust:
62.5 are O – (O2‐)
21.2 are Si – (Si4+)
6.5 are Al – (Al3+)
• Fe (2+ or 3+), Mg (2+), Ca (2+), Na (+) and K (+) each account for
about 2 atoms.
• There is also a bit of Ti (4+) and Mn (2+) plus a few others that
will be mentioned in the coming weeks.
32
20/07/2012
groups
• How many of which atoms?
How many of which atoms?
• Recall from the previous slides for the major silicate mineral
groups, each mineral had a formula that read…..
Something, something….,(SipOq)
where p:q ratio = major silicate group
• Well, for each group the silicate structure has a net excess of –ve
charges that can be determined by this ratio
• E.g., for our simple silicate tetraherdron (isolated/island):
(SiO4) = 1 x 4+ and 4 x 2‐ = 4‐  (SiO4)4‐
groups
• What about the double chain inosilicate
What about the double chain inosilicate structure
structure ‐ amphiboles?
• E.g., Hornblende: Ca2(Mg,Fe,Al)5Si8O22(OH)2
Where (SipOq) has a p:q ratio of 4:11 (same as 8:22)
• So the resulting charge (4 x 4+) ‐ (11 x 2‐)
= 16 – 22 = ‐6
(Si4O11)6‐
• In this case we have an excess of 6 –ve charges per 11 Oxygen
anions
groups
• We can balance this negative excess charge by either:
a) Adding 6 univalent (+1; e.g., Na,K) cations or
b) Adding 3 divalent (+2; e.g., Fe,Mg,Ca) cations ….
….into a space that closely neighbours the 4 oxygen anions (i.e.,
this cation becomes a coordinating cation for the neighbouring O
anions).
33
20/07/2012
groups
• The location of these cations must reside in the spaces (or sites)
between the individual chains of Si‐O tetrahedra such that they
simultaneously satisfy the requirement for electroneutrality of
all oxygens in the structure
• This means that ionic size matters and depending on the silicate
structure only certain cations will fit into certain sites (e.g.,
closest packed sites, tetrahedral interstitial sites, octahedral
interstitial sites)
• This is a good thing because it limits the range of chemical
compositions and structures found in silicates.
groups
1. Electroneutrality 
groups
2) Coordination Principal (using ionic radius ratios )
• Where are the cations
Where are the cations located and how are they arranged?
located and how are they arranged?
• Coordination describes how oppositely charged ions arrange
themselves when they unite to form a stable crystal structure
• The coordinated ions always cluster about the central
coordinating ion in such a way that their centres lie at the apices
of a polyhedron
4‐fold coordination • Thus in a stable crystal structure of a silicate mineral each Si
cation lies at the centre of a coordinated polyhedron of O anions
• The number of anions in the polyhedron is the coordination
number of the cation with respect to the given anion.
34
20/07/2012
groups
2) Coordination Principal using ionic radius ratios
In this figure we can see that the shape of the polyhedra
In this figure we can see that the shape of the polyhedra formed by a cation is defined by
formed by a cation is defined by
the relative size of the cations in grey (i.e. Si4+ plus other metals – e.g., Al3+, Mg2+) and the
bounding anions in white (O ) 2‐
groups
2) Coordination Principal using ionic
radius ratios
• The coordination number can be
determined by their relative sizes or
their ionic radii
• The ionic radius ratio (Rx:Rz) will predict
whether the coordinated O anions are
in 4‐fold, 6‐fold, 8‐fold or 12‐fold
coordination with the coordinating
cation
groups
2) Coordination Principal using ionic
radius ratios
• Atoms occupy specific sites in a crystal
structure (e.g., closest packed sites,
tetrahedral (4‐fold) interstitial sites,
octahedral (6‐fold), cubic (8‐fold)
icosahedral (12‐fold))
• Remember, the terms tetrahedral,
octahedral etc. refers to the number of
faces of the enclosing shape (i.e., an
octahedron), and not the number of
anions defining it
35
20/07/2012
groups
So now we can address the first two topics (electroneutrality and coordination number)
by remembering the general formula for the silicate mineral group.
XmYn(ZpOq)Wr
X = Large sized mono‐ (1+) or divalent (2+) cations that join in 8‐12‐fold coordination  (Na+, Ca+, K+)
Y = Medium sized 2+, 3+, 4+ cations that join in 6‐fold coordination  (Al3+, Fe3+, Mg2+, Fe2+, Mn2+)
Z = Small sized highly charged cations that can fit in the centre of the tetrahedra and thus forms 4‐fold

coordination  (Si4+ or Al3+)
O = oxygen (O2‐; always!!) But not all silicates will have all of
these....
W = other anions such as OH‐, F‐ and Cl‐
groups
Quick review: X, Y are cations (+ve ions) other than Si which act to

balance the excess –ve charges possessed by the O in the silicate
structure:
X = Large sized mono‐ XmYn (Z
( pOq)W
) r W = other anions such
or divalent cations that (OH‐, F‐ and Cl‐)
join in 8‐ or 12‐fold
coordination (Na+, Ca+, O = oxygen
K+) (always!!)
Z = Small, highly
charged cations,
Y = Medium sized 2+, 3+,
the tetrahedra
4+ cations that join in 6‐
centre, 4‐fold
fold coordination p:q = polymerisation
coordination
(Al3+, Fe3+, Mg2+, Fe2+,
(Si4+ or Al3+)
m, n, r = electroneutrality
Mn2+)
groups
We’ve replaced the something, something...., part of formula with something
more specific
XmYn (ZpOq) Wr
Just to reiterate, p:q ratio gives the degree of polymerisation – i.e. The major silicate

mineral group
BUT what do m , n and r do in this formula?
m and n ensures electroneutrality of the silicate structure by indicating the
number and types (ie. charge and radius) of cations positioned in specific
coordination sites in the mineral structure, that is m + n (+r) cancelling out
the excess negative charge
36
20/07/2012
groups
XmYn (ZpOq) Wr
This puts us in a good position to tackle the third topic.....
groups
1. Electroneutrality 
2. Coordination number 
Part of the definition of a mineral was that it had a definite but not
fixed chemical composition.
What does this mean?
groups
XmYn (ZpOq) Wr
The catch: Depending on the conditions of crystallisation (i.e.
temperature and melt composition) different cations will occupy
these sites “in turn” or more accurately in varying proportions,
resulting in a compositional spectrum for a single mineral type
The significance: That a mineral preferentially selects one
element over another at any given temperature and melt
composition and this is what drives magmatic differentiation
processes in the mantle
37
20/07/2012
groups
Chemical substitutions and solid solution
XmYn (ZpOq)Wr
• So, when we say that minerals have a definite but not fixed chemical
So when we say that minerals have a definite but not fixed chemical
composition....
• What we mean is most minerals do not exist as pure substances and this is
because nearly all minerals display extensive variation in chemical
composition
• Compositional variation is the result of substitution, in a given structure, of
an ion or ionic group for another ion or ionic group
 This type of relationship is referred to as ionic substitution or solid solution
groups
XmYn (ZpOq)Wr
When we talk about ionic substitution / solid solution in a mineral we are
(generally) talking about which part of the general formula?
XmYn (ZpOq)Wr
groups
XmYn (ZpOq)Wr
Several factors influence the extent to which substitution can take
place:
1. Ionic radius – two elements can readily substitute for each other only if
their ionic radii are similar or differ by less than 15%
2. Crystallisation temperature – the higher the temperature, the greater the
disorder, the less stringent the space requirements of the structure. This
means high temperature minerals generally have extensive ionic
substitutions compared to low temperature minerals
3. Electroneutrality is preserved
38
20/07/2012
groups
After O and Si, Al3+ is most important: XmYn (ZpOq)Wr
• Al3+ has a radius of 0.51, and a radius ratio Al:O =
0.364
Y = Medium sized
M di i d
• This corresponds to a 4‐fold coordination with O
2+, 3+, 4+ cations
Z = Small, highly
• However, this ratio is close enough to the upper that join in 6‐fold
charged cations,
limit for 4‐coordination that 6‐coordination is also coordination
the tetrahedra
possible for Al (Al3+, Fe3+, Mg2+,
centre, 4‐fold
Fe2+, Mn2+)
• This means Al3+ can substitute for ions in both the coordination
Y position and the Z position!! (Si4+ or Al3+)
• Al3+ is therefore important because of its
abundance (particularly in the crust) and its
flexibility to occupy more than one site in the
crystal structure
groups
 Other elements involved in substitutions: XmYn (ZpOq)Wr
Formula CN Ion Ionic Radius Ratio
Radius
• This table shows some
This table shows some of the more
of the more
Z 4 Si4+ 0.42 0.3 important elements involved in solid
4 Al3+ 0.51 0.364 solution substitutions in silicate
minerals
Y 6 Al3+ 0.51 0.364
6 Fe3+ 0.64 0.457 • Ionic substitution is common and
extensive between elements whose
6 Mg2+ 0.66 0.471 chemical symbols lie between a pair
6 Fe2+ 0.74 0.529 of horizontal lines (i.e. Where the CN
numbers are equal)
X 8 Na+ 0.97 0.693
8 Ca+ 0.99 0.707
groups
XmYn (ZpOq)Wr
There are three types of ionic or solid substitution
1. Substitutional solid solution

1. Simple
2. Coupled
2. Interstitial solid substitution (less common)
3. Omission solid substitution (less common)
39
20/07/2012
groups
Solid solution – 1) Simple Substitution
Orthosilicates or Nesosilicates (Isolated Tetrahedra, Si:O = 1:4)

– e.g., Olivine: (Mg,Fe)2(SiO4)
Yn (ZpOq)
Y = Mg2+ and Fe2+, where n = 2 ‐ (Mg, Fe)2 = (Mgx,Fe2‐x)
• Similar ionic radii therefore both have 6‐fold coordination with
Oxygen
• Their identical valency means that they can substitute for one
another and the olivine structure will remain electrically neutral
• Thus olivine can have a range of compositions (isomorphs)
depending on the relative proportions of Mg2+ to Fe2+
occupying the available sites
groups
Orthosilicates or Nesosilicates (Isolated Tetrahedra, Si:O = 1:4)

– e.g., Olivine: (Mg,Fe)2(SiO4)
Yn (ZpOq)
• The general formula above thus describes the solid solution series
for olivine, which consists of two end‐members:
• Forsterite (all Y = Mg, Mg2SiO4) to Fayalite (all Y = Fe , Fe2SiO4)
• In reality neither of these pure end‐members exist rather most
olivines consists of between 98% ‐ 2% Mg
• An olivine containing 98% Mg would then be written:
Mg1.96Fe0.04SiO4  Fo98
groups
XmYn(ZpOq)
• It turns out that Mg and Fe substitute for one another in a large number of
naturally occurring silicates forming solid solution series in:
Pyroxenes (Inosilicates): X1‐nY1+n(Z2O6)
• Orthopyroxene, n1  Enstatite: Mg2Si2O6‐ Orthoferrosilite: Fe2Si2O6
• Clinopyroxene, n= 0 to 1  Diopside: CaMgSi2O6 – Hedenbergite:
CaFeSi2O6
Amphibole group (Inosilicates): X2Y5(Z8O22)(OH,F)2
• Tremolite: Ca2Mg5(Si8O22)(OH,F)2 – Ferroactinolite: (Ca2Fe5(Si8O22)(OH,F)2
Mica group (Phyllosilicates): X2Y4‐6(Z8O20)(OH,F)4
• Phlogopite: K2Mg6(Al2Si6O20)(OH,F)4‐ Annite: K2Fe6(Al2Z6O20)(OH,F)4
40
20/07/2012
groups
Solid solution – In the Mantle
XmYn(ZpOq)
Question:
How does understanding solid solution help us understand and
How does understanding solid solution help us understand and
interpret what is happening in the mantle?
In other words, what does this mean in a petrological sense?
 When a mineral crystallises from a melt the chemical
composition varies according to the solid solution series for that
mineral
groups
Solid solution – In the Mantle
XmYn(ZpOq)
• For olivine and other ferromagnesian minerals this means
that the Mg‐rich end‐members are the first to crystallise at
that the Mg rich end members are the first to crystallise at
higher magmatic temperatures
• As crystallisation continues the temperature of the melt
decreases, the reservoir of Mg2+ in the melt becomes
depleted and so progressively more Fe2+ will be
incorporated into the mineral’s structure
groups
Fe2SiO4 Mg2SiO4
‘Phase diagram’ for Olivine
41
20/07/2012
groups
Solid solution – 2) Coupled Substitution
• Tectosilicates (Framework structure, Si:O = 1:2)

• e.g. Plagioclase: (Ca, Na) (Al, Si) Al1Si3O8
Feldspar X Y (Z O )
Xm Yn (ZpOq)
• Ionic radii of Ca2+ and Na+ are similar so they will both go
into 8‐fold coordination with O, BUT their charges are
different
• The charge difference is compensated for by coupled
substitution such that Na+ + Si4+ substitute for Ca2+ + Al3+
(both pairs total 5+).
• Thus plagioclase also has a range of isomorphs depending
on the relative proportions of Ca2+ and Na+ occupying the
available sites
groups
Solid solution – 2) Coupled Substitution
• Tectosilicates (Framework structure, Si:O = 1:2)

• e.g. Plagioclase: (Ca, Na) (Al, Si) Al1Si3O8
Feldspar X Y (Z O )
Xm Yn (ZpOq)
• As with olivine, the general formula above describes the
solid solution series for plagioclase feldspar, which consists
of two end‐members:
• Albite (all X = Na+) to Anorthite (all X = Ca2+).........An50
 Within a magmatic system the first plagioclase feldspar
to crystallise is the Ca‐rich end‐member. As Ca becomes
depleted in the melt more Na will take its place in the
plagioclase structure.
groups
Solid solution – 2) Coupled Substitution with Al3+
Xm Yn (ZpOq) Wr
• The importance of Al3+ in silicates is evident from it’s abundance and ability
to substitute for Si in the tetrahedron structure
b i f Si i h h d
• However, because of the charge imbalance it can only substitute for Si4+ if it
is coupled with another substitution on a nearby crystallographic site that
preserves charge balance (and electronuetrality)
42
20/07/2012
groups
Xm Yn (ZpOq) Wr
The substitution of a tetrahedral Al (written Aliv) for Siiv
 (AlivSiiv‐1)n‐
Could be coupled with the substitution of octahedral Al for Fevi or Mgvi

 (AlviMgvi‐1)n+
The complete coupled substitution can then be written:
AlivAlvi Siiv‐1Mgvi‐1
groups
Xm Yn (ZpOq) Wr
This coupled substitution is so common in silicate minerals that it has it’s own
special name:
p
 Tschermak’s substitution
AlivAlvi Siiv‐1Mgvi‐1
This substitution is particularly important in pyroxenes, amphiboles and micas
(three of the most common rock forming mineral groups)
groups
Solid solution – Compositional space (or maps)
Xm Yn (ZpOq) Wr
For each of these minerals we can illustrate the compositional effect of performing a
Tschermak’s substitution on the standard composition of the mineral by drawing maps
or vectors:
or vectors:
A point is awarded in compositional space each time the AlivAlvi Siiv‐1Mgvi‐1
substitution is imposed on the mineral’s starting composition
two
Pyroxene substitutions
starting are possible
composition
43
20/07/2012
groups
Solid solution – Compositional space (or maps)
Xm Yn (ZpOq) Wr
• It
It is possible to map out both the
i ibl t t b th th
simple and coupled substitutions in
compositional space…
• Consider biotites (sheet silicates):
Simple 6‐fold substitution of Mg for
Fe in the y‐axis, and Tschermak
substitutions on the x‐axis maps out
the natural range of biotite
compositions
groups
Solid solution – Summary
Xm Yn (ZpOq) Wr
• Combinations of substitutions account for the chemical variation of common
silicate minerals
• Simple substitutions of cations with the same co‐ordination are straight
forward
• Coupled substitutions of Al3+ for Si4+ (both tetrahedral) require a
corresponding substitution in the surrounding cationic crystallographic sites
(octahedral or greater)
groups
Solid solution – Summary
Xm Yn (ZpOq) Wr
• Rather than memorising a host of substitutions and obscure mineral names,
what we want is to impart a familiarity with:
what we want is to impart a familiarity with:
• The general structure of the common rock forming mineral families 
• The general form of common substitutions (eg, simple and coupled
such as Tschermaks substitution) 
This will allow a first principle understanding of what minerals are stable
within the Earth
44
20/07/2012
groups
That’s it for now
• To reinforce these ideas, read section 3.2 and 3.3 of the ‘Structure of the
Earth – Study Guide’ on Moodle
• Next lecture we will continue exploring the silicate Earth – The nature and
composition of the mantle
f h l
• For the upcoming practicals – revise 1st year notes on rock‐forming

minerals and read ‘Optics Manual’ (pages 1‐6) on Moodle
Interested in reading ahead?
• For Next Week’s lectures find out what a lherzolite is and why it is important....
• Also read Section 2 of the ‘Structure of the Earth – Study Guide’ on Moodle
45

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20/07/2012

2. Practical exam – 15% (week 8 – during your usual

oceanic crust continental crust

oceanic crust continental crust

oceanic crust continental crust

• The S (secondary) wave is slower than

• The Moho is commonly at 35‐40 km depth beneath the continents but it

Continental Crust Oceanic Crust Mantle

A mineral is defined as:

Graphical Representation of Elemental Abundance

Six elements make up 99.1% of BSE ->

From W . M . W hite, 2001

Si4+ = 0.42A 1) Ionic charge & 2) Ionic Radii

1) Orthosilicates or Nesosilicates (‘islands’) –

Most abundant constituents of igneous rocks. Two main types

Y = Medium sized 2+, 3+, 4+ cations that join in 6‐fold coordination  (Al3+, Fe3+, Mg2+, Fe2+, Mn2+)

Z = Small sized highly charged cations that can fit in the centre of the tetrahedra and thus forms 4‐fold

Quick review: X, Y are cations (+ve ions) other than Si which act to

Just to reiterate, p:q ratio gives the degree of polymerisation – i.e. The major silicate

There are three types of ionic or solid substitution

1. Substitutional solid solution

Orthosilicates or Nesosilicates (Isolated Tetrahedra, Si:O = 1:4)

Orthosilicates or Nesosilicates (Isolated Tetrahedra, Si:O = 1:4)

• Forsterite (all Y = Mg, Mg2SiO4) to Fayalite (all Y = Fe , Fe2SiO4)

• Tectosilicates (Framework structure, Si:O = 1:2)

• Tectosilicates (Framework structure, Si:O = 1:2)

Could be coupled with the substitution of octahedral Al for Fevi or Mgvi

• For the upcoming practicals – revise 1st year notes on rock‐forming

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