How many molecules?

• Pyrite – FeS2

• Would there be any other elements in

there???
Goldschmidt’s rules of Substitution
1. The ions of one element can extensively
replace those of another in ionic crystals
if their radii differ by less than about 15%
2. Ions whose charges differ by one may
substitute readily if electrical neutrality is
maintained – if charge differs by more
than one, substitution is minimal
Goldschmidt’s rules of Substitution
3. When 2 ions can occupy a particular
position in a lattice, the ion with the
higher charge density forms a stronger
bond with the anions surrounding the site
4. Substitution may be limited when the
electronegativities of competing ions are
different, forming bonds of different ionic
character
 FeS2
• What ions would
substitute nicely
into pyrite??

• S- radius=219
pm
• Fe2+ radius=70
pm
 Problem:
• A melt or water solution that a mineral
precipitates from contains ALL natural
elements

• Question: Do any of these ‘other’ ions get

into a particular mineral?
 Chemical ‘fingerprints’ of minerals
• Major, minor, and trace constituents in a
mineral
• Stable isotopic signatures
• Radioactive isotope signatures
Major, minor, and trace constituents
in a mineral
• A handsample-size rock or mineral has around 5*1024
atoms in it – theoretically almost every known element is
somewhere in that rock, most in concentrations too small
to measure…
• Specific chemical composition of any mineral is a record
of the melt or solution it precipitated from. Exact chemical
composition of any mineral is a fingerprint, or a genetic
record, much like your own DNA
• This composition may be further affected by other
processes
• Can indicate provenance (origin), and from looking at
changes in chemistry across adjacant/similar units - rate
of precipitation/ crystallization, melt history, fluid history
 Stable Isotopes
• A number of elements have more than one naturally
occuring stable isotope.
– Why atomic mass numbers are not whole  they
represent the relative fractions of naturally occurring
stable isotopes
• Any reaction involving one of these isotopes can
have a fractionation – where one isotope is favored
over another
• Studying this fractionation yields information about
the interaction of water and a mineral/rock, the
origin of O in minerals, rates of weathering, climate
history, and details of magma evolution, among
other processes
 Radioactive Isotopes
• Many elements also have 1+ radioactive isotopes
• A radioactive isotope is inherently unstable and
through radiactive decay, turns into other isotopes
(a string of these reactions is a decay chain)
• The rates of each decay are variable – some are
extremely slow
• If a system is closed (no elements escape) then the
proportion of parent (original) and daughter
(product of a radioactive decay reaction) can yield
a date.
• Radioactive isotopes are also used to study
petrogenesis, weathering rates, water/rock
interaction, among other processes
 Chemical heterogeneity
• Matrix containing ions a mineral forms in
contains many different ions/elements –
sometimes they get into the mineral
• Ease with which they do this:
– Solid solution: ions which substitute easily form
a series of minerals with varying compositions
(olivine series  how easily Mg (forsterite) and
Fe (fayalite) swap…)
– Impurity defect: ions of lower quantity or that
have a harder time swapping get into the
structure
 Stoichiometry
• Some minerals contain varying amounts of
2+ elements which substitute for each
other
• Solid solution – elements substitute in the
mineral structure on a sliding scale,
defined in terms of the end members –
species which contain 100% of one of the
elements
 Chemical Formulas
• Subscripts represent relative numbers of
elements present
• (Parentheses) separate complexes or
substituted elements
– Fe(OH)3 – Fe bonded to 3 separate OH
groups
– (Mg, Fe)SiO4 – Olivine group – mineral
composed of 0-100 % of Mg, 100-Mg% Fe
• KMg3(AlSi3O10)(OH)2 - phlogopite
• K(Li,Al)2-3(AlSi3O10)(OH)2 – lepidolite
• KAl2(AlSi3O10)(OH)2 – muscovite

• Amphiboles:
• Ca2Mg5Si8O22(OH)2 – tremolite Actinolite series
minerals
• Ca2(Mg,Fe)5Si8O22(OH)2 –actinolite

• (K,Na)0-1(Ca,Na,Fe,Mg)2(Mg,Fe,Al)5(Si,Al)8O22(OH)2
- Hornblende
 Minor, trace elements
• Because a lot of different ions get into any
mineral’s structure as minor or trace
impurities, strictly speaking, a formula
could look like:
• Ca0.004Mg1.859Fe0.158Mn0.003Al0.006Zn0.002Cu0.001Pb0.000
01Si0.0985Se0.002O4

• One of the ions is a determined integer, the

other numbers are all reported relative to that
one.
 Normalization
• Analyses of a mineral or rock can be reported in
different ways:
– Element weight %- Analysis yields x grams element in
100 grams sample
– Oxide weight % because most analyses of minerals and
rocks do not include oxygen, and because oxygen is
usually the dominant anion - assume that charge
imbalance from all known cations is balanced by some %
of oxygen
– Number of atoms – need to establish in order to get to a
mineral’s chemical formula
• Technique of relating all ions to one (often Oxygen)
is called normalization
 Normalization
• Be able to convert between element weight
%, oxide weight %, and # of atoms
• What do you need to know in order convert
these?
– Element’s weight  atomic mass (Si=28.09
g/mol; O=15.99 g/mol; SiO2=60.08 g/mol)
– Original analysis
– Convention for relative oxides (SiO2, Al2O3, Fe2O3
etc)  based on charge neutrality of complex
with oxygen (using dominant redox species)
 Normalization example
• Start with data from quantitative analysis: weight
percent of oxide in the mineral
• Convert this to moles of oxide per 100 g of
sample by dividing oxide weight percent by the
oxide’s molecular weight
• ‘O factor’ from page 204: is process called
normalization – where we divide the number of
moles of one thing by the total moles  all
species/oxides then are presented relative to
one another
Feldspar analysis
(Ca, Na, K)1 (Fe, Al, Si)4 O8
Oxide wt %
2-
Atomic in the # of moles moles of moles of O Number of
weight mineral of oxide in mole % of cations contributed moles of
2-
of oxide # cations in # of O (determined the oxides in in by each ion in the
oxide (g/mol) oxide in oxide by analysis) mineral the mineral Cation sample cation mineral
4+
SiO2 60.08 1 2 65.90 1.09687 73.83 Si 73.83 147.66 2.95
3+
Al2 O3 101.96 2 3 19.45 0.19076 12.84 Al 25.68 38.52 1.03
Fe 2O3 159.68 2 3 1.03 0.00645 0.43 Fe3+ 0.87 1.30 0.03
CaO 56.08 1 1 0.61 0.01088 0.73 Ca2+ 0.73 0.73 0.03
Na2O 61.96 2 1 7.12 0.11491 7.73 Na+ 15.47 7.73 0.62
K2O 94.20 2 1 6.20 0.06582 4.43 K+ 8.86 4.43 0.35

SUM 1.48569 100 125.44 200.38

# of moles Oxygen choosen: 8

Ca0.73 Na15.47 K8.86 Fe 0.87Al25.68 Si73.83O200.38

Ca0.03 Na0.62K0.35 Fe 0.03 Al1.03Si2.95 O8
to get here from formula above, adjust by 8 / 200.38
 Compositional diagrams
FeO Fe3O4 Fe2O3
wustite magnetite hematite

A
Fe O

A1B1C1

x
A1B2C3

B C
 Si

fayalite forsterite

enstatite ferrosilite
Fe Mg
fayalite forsterite

Fe Mg

Pyroxene solid solution  MgSiO3 – FeSiO3

Olivine solid solution  Mg2SiO4 – Fe2SiO4