Atomic Substitution, Phase

and Igneous Diagrams

 ATOMIC (IONIC) SUBSTITUTION
IMPORTANT TO REMEMBER:
Minerals are composed of atoms or ions
that occupy structural sites in a crystal
structure.
ATOMIC (IONIC) SUBSTITUTION
Different ions can occupy the same structural
site if they have similar size, have similar
charge and are available in the environment in
which the mineral is forming.

This process of one ion replacing another ion

is called ion substitution .
ATOMIC (IONIC) SUBSTITUTION
In mineral formulas, ions that commonly
substitute for one another are generally
placed within a single set of parentheses.
Most Common example:
In the olivine group, iron and
magnesium can freely substitute for one
another in the six fold, octahedral site. As a
result, the formula for olivine is commonly
written as (Mg,Fe)2 SiO4 .
 Types of Ionic Substitution
1. Simple complete substitution

2. Coupled (paired) ionic substitution

3. Limited ionic substitution

Simple complete substitution

exists when two or more ions of similar

radius and the same charge substitute for one
another in a coordination site in any
proportions.
(Mg,Fe)2SiO4 , Mg +2 (radius = 0 .66
angstroms) and Fe +2 (radius = 0.74
angstroms) can substitute for one another in
the octahedral site in any proportion. The two
end members are the pure magnesium silicate
component called forsterite [(Mg) 2 SiO 4 ]]
and the pure iron silicate component called
fayalite [(Fe) 2 SiO 4 ]. Since these two end
members can substitute for one another in
any proportion in olivine, a complete solid
solution series exists between them.
 complete solid solution series are easily
represented by a number line called a tie line
between the two end members.

For example, an olivine with equal amounts of the two end member
components can be represented by the formula [(Mg 0.5, Fe 0..5 ) 2 SiO 4 ],
by its position on the line (halfway between the ends) or by the proportions
of either end member (Fo 50 or Fa 50 ). Typically the forsterite component
is used (e.g., Fo 50 ).
 Three Ions Substitute Freely For One
Another In The Same Coordination Site
So there will be 3 end- members

For example, ferrous iron (Fe +2 ), magnesium

(Mg +2 ) and manganese (Mn +2 ) can all
substitute for one another in any proportions
in the cation site of rhombohedral carbonates.
The general formula for such carbonate minerals can be
written as (Fe,Mg,Mn)CO3 .The three end member
components are the “ pure ” minerals siderite (FeCO 3 ),
magnesite (MgCO 3 ) and rhodochrosite (MnCO 3 ).

“TERNARY
DIAGRAM”
Point A,lies on the side opposite the magnesite apex and so contains no magnesium.
Because it lies halfway between rhodochrosite and siderite, its composition may be
written as Rc 50 Sd 50 or as (Mn 0.5, Fe 0.5 )CO 3 . Any point that lies within the
triangle represents a solid solution that contains all three end member components.
The precise composition of any three- component solid solution can be determined by
the distance from the point to the three apices of the triangle.
Point B lies closest to the rhodochrosite apex and farthest from the
magnesite apex and so clearly contains more Mn than Fe and more Fe
than Mg. Its precise composition can be expressed as Sd 10 Ms 2 Rc
88 or as (Fe 0.10 ,Mg 0.02 ,Mn 0.88 )CO 3 . Many other examples of
three- component systems with complete solid solution exist. All may
be represented in a similar fashion by their position on a triangular
diagram.
Coupled ( Paired) Ionic Substitution
involves the simultaneous substitution of
ions of different charges in two different
structural sites that preserves the electrical
neutrality of the crystal lattice.
The substitution of ions of different
charge in one structural site changes the
electric charge and requires a second set of
substitutions of ions in a second structural
site to balance that change in charge.
Most common example: The Plagioclase
Feldspar
In the plagioclase feldspars, similar size ions of
sodium (Na +1 ) and calcium (Ca +2 ) can
substitute for one another in any proportion
in the large cation coordination site. However,
when calcium (Ca +2 ) substitutes for sodium
(Na +1 ), the positive charge of the crystal
lattice is increased, and when the reverse
occurs, the positive charge of the lattice is
decreased.
 To accommodate the change:
These changes in charge are balanced by a
second set of substitutions. This second set of
substitutions occurs in the small tetrahedral
cation coordination site where aluminum (Al +3 )
and silicon (Si +4 ) substitute for one another.
When a sodium (Na +1 ) ion is added to the large
cation coordination site, a silicon (Si +4 ) ion is
added to the small cation structural site. The two
sites together contain a total charge of +5 that is
balanced by the anions in the plagioclase
structure.
The two components are the “ pure ” sodium
plagioclase called albite (Ab) , whose formula
can be written as NaSiAlSi2O8 (or NaAlSi3O8 ),
and the “ pure ” calcium plagioclase called
anorthite (An) , whose formula can be written
as CaAlAlSi2O8 (or CaAl2Si2O8 ). Since a
complete solid solution series exists
An or Ab
 Limited Ionic Substitution

Substitution is limited by significant

differences in the ionic radii or charge of
substituting ions. Ions of substantially
different size limit the amount of substitution
so that only a limited solid solution can exist
between end member components.
This situation can be illustrated in the
rhombohedral carbonates by the limited solid
solution series that exists between calcite
(CaCO3 ), the major mineral in limestone and
the raw material from which cement is refi
ned, and magnesite (MgCO3 ).
However, because calcium cations (Ca +2 ) are
more than 30% larger than magnesium (Mg +2
) cations, the substitution between the two
end members is limited. Because the amount
of substitution is limited, many potential
compositions do not exist in nature. Such gaps
in a solid solution series are called miscibility
gaps by analogy with immiscible liquids that
do not mix in certain proportions. In this
series, a miscibility gap exists between
approximately Ms 25 = Ct 75 and Ms 40 =
Ct 60 .
MAGMA SERIES
 MAGMA SERIES
Despite compositional variations resulting
from diversification processes, rocks derived
from a given parent magma can display
distinct geochemical signatures indicating
common origin.

As an analogy, consider the role of DNA in

assessing lineage.
 Variations in magma and rock
compositions may be due to:
• Widely varying chemistry of the initial magma,
related to source rock composition, melting
history and degree of melting.
• Alterations to the chemical composition of the
magma through differentiation.
• Interactions between magmas such as magma
mingling and mixing.
• Assimilation reactions with the surrounding
country rock.
• Post - crystallization alteration processes
(metamorphism).
A magma series consists of
genetically related magmas that have
changed composition from a
common original parental magma
 Igneous rock series include:

Calc- alkaline- have moderate

to high Na 2 O, K 2 O and SiO
2 concentrations.

Sub Alkaline

Tholeiitic- have low

Igneus Rock Magma Series Na 2 O and K 2 O but high FeO
and CaO concentrations.
Alkaline- high Na 2 O and K 2
O concentrations compared
to SiO 2 and are generally
undersaturated with respect
to SiO 2

Major, minor and trace element concentrations provide

critical information to understanding the origin and
evolution of igneous rocks and rock series.
 Bimodal magma suites are characterized by
the voluminous occurrence of silicic and basic
(e.g., rhyolite– dacite and basalt) rocks with
few intermediate (e.g., andesite) rocks.
Bimodal volcanism is associated with
continental rifts. The basic component is
derived by partial melting of the mantle. The
silicic component is derived by partial
melting of the continental crust heated by
rising basic magmas.
Calc -a lkaline magmas occur almost
exclusively at convergent margins.
Tholeiitic magmas are generated primarily at
ocean spreading centers, but also occur in
continental rifts, backarc basins, ocean islands
and hotspots.
Alkaline magmas occur primarily at hotspots,
ocean islands and rift environments.
Bimodal volcanism occurs at continental rifts.
 Tracking magma series using
variation diagrams

Variation diagrams provide a means to

concisely and clearly display rock chemistry
variations between samples collected in an
area with an eye to establishing their origins
and relationships.
Bivariate diagrams consist of two variables
plotted as an x- y coordinate system.

Trivariate diagrams contain three variables

and are plotted in a triangular field.
Bivariate diagrams: Harker diagrams
Harker diagrams are bivariate diagrams in
which the vertical ordinate (y- axis)
represents weight percents of major or minor
oxide compounds such as FeO, MgO, CaO, Na
2 O, K 2 O or TiO 2 . The horizontal abscissa (x
-a xis) represents weight percent SiO 2
content.
Bivariate diagrams: Harker diagrams
(1) Al 2 O 3 increases with the
crystallization of ferromagnesian
minerals (olivine, pyroxene,
amphibole), and then decreases with
the removal of plagioclase and micas;
(2) MgO and Fe 2 O 3 decrease with
the crystallization of ferromagnesian
minerals; (3) CaO decreases with the
crystallization of calcium plagioclase;
(4) NaO initially increases due to the
removal of MgO, Fe 2 O 3 and CaO,
and then decreases as sodium
plagioclase crystallizes in andesitic and
more silicic rocks; (5) SiO 2 and K 2 O
increase as MgO, Fe 2 O 3 , CaO, Na 2 O
and Al 2 O 3 are progressively
removed by crystallization.
If Harker diagrams display smooth, curvilinear
trends for all rock data points, then the
following three inferences can be made:
1 The rocks are genetically related.
2 Major element variations refl ect a liquid
line of descent from a common source in
which diversifi cation caused major elements
to either increase or decrease progressively
with respect to variations in weight percent
SiO 2
3 The parent magma from which the rocks
are derived has a composition near that of the
sample with the least SiO2 , that is, of basaltic
composition.
Bivariate diagrams: Spider Diagrams
In spider diagrams, trace element
concentrations on the abscissa are plotted
relative to a standard reference for each
element on the ordinate. The standard
reference varies depending upon the rock
type analyzed and the tectonic relationship
that the researchers wish to demonstrate.
The standard reference may include chondrite
meteorites, primitive mantle, normal mid-
ocean ridge basalt (N- MORB), enriched mid-
ocean ridge basalt (E- MORB) or an ocean
island basalt (OIB).
Flat trends indicate a close chemical
relationship to the standard reference. Spider
diagrams are useful in demonstrating the
enrichment or depletion of compatible versus
incompatible elements, LREE versus HREE
variation, or other data that may indicate
diversification trends or magmatic source.
Ternary Variation Diagrams: AFM
Diagram
(A, alkali; F, iron; M, magnesium) diagram.
Tholeiitic suites display significant iron
enrichment with increased fractionation while
the calc- alkaline suite does not display
meaningful iron enrichment.
 IUGS Classification Of Mineral
Groups, QAPF
The IUGS classifi cation is based upon the
modal concentrations of fi ve essential mineral
groups abbreviated by the letters Q, A, P, F
and M, respectively:
• Q = quartz, tridymite, cristobalite.
• A = a lkali feldspar, including orthoclase,
microcline, sanidine, perthite, anorthoclase
and albite plagioclase with up to 5 mole %
anorthite (An0-An5)
• P = plagioclase (An 5 – An 100 ) and
scapolite (altered plagioclase).

• F = feldspathoids, also known as foids.

The term foid is derived from being feldspath
oid rich
• M = mafi c and related minerals,
including olivine, pyroxene, amphiboles,
micas, melilite, opaque minerals, garnet,
epidote, calcite, allanite, zircon, apatite,
sphene and titanite
The QAPF modal classification applies for
igneous rocks with > 10% felsic minerals and <
90% mafic mineral (M) content by volume. The
QAPF plot is a diamond -shaped diagram
The QAPF mineral constituents are normalized
so that the sum total of these four mineral
constituents equals 100% as follows: