PRINCIPLES OF

GEOCHEMISTRY
LECTURES FOR
UNDERGRADUATE STUDENTS

INTRODUCTION
AND
HISTORICAL REVIEW

HISTORICAL REVIEW
The name geochemistry was first introduced by Schonbein since more than
150 years.
Clark, who was a chief chemist of the US. Geological Survey from 1884 to
1925, has contributed very much to the science "geochemistry". The modern
science of geochemistry can be dated back to Clark who published a very
large number of chemical analyses of the various rocks in the earth's crust . He
computed averages for each common rock type and studied the mutual
abundance and distribution of many major and minor elements.
Goldschmidt (1888 - 1947) contributed significantly to the roles of ionic size,
coordination and atomic substitution in crystal lattices. He gave a practical
definition for the science geochemistry, as it deals with:
1) the abundance of elements in rock, mineral or crystal,
2) the distribution of the elements, and
3) lows governing the abundance and distribution of elements in rock, mineral
or crystal.

The contributions of the USSR geochemists are remarkable,

especially after the improvement of the analytical
techniques at the early decades of the present century.
There are several trials to classify elements on geochemical basis.
Names such as siderophile, chalcophile, lithophile, hydrophile,
thalassophile, atmophile are commonly used to denote particular
geochemical affinity of elements.
Modern advances in geochemistry are enormous in different
academic and applied disciplines. The revolution in the analytical
techniques, especially the coupled inductively plasma-mass
spectrometry facilitated data with very high precision on all
components of the earth, such as water, soil, sediments, air, rock,
crystals and minerals.
Recently, huge data are accumulating on the geochemistry of the
REE, PGM and the inert gases.

Geochemical Affinity

In the classification scheme of Goldschmidt, elements are divided according to how they
partition between coexisting silicate liquid, sulfide liquid, metallic liquid, and gas
phasedefined by examining ore smelting slags and meteorites
Melting a chondrite gives 3 immiscible liquids plus vapor:
Gas Phase

Silicate Liquid

Sulfide Liquid

Metallic Liquid

Atmophile

H, He, N, Noble gases

Lithophile

Alkalis, Alkaline Earths,

Halogens, B, O, Al, Si, Sc, Ti,
V, Cr, Mn, Y, Zr, Nb,
Lanthanides, Hf, Ta, Th, U

Chalcophile

Cu, Zn, Ga, Ag, Cd, In, Hg,

Tl, As, S, Sb, Se, Pb, Bi, Te

Siderophile

Fe, Co, Ni, Ru, Rh, Pd, Os, Ir,

Pt, Mo, Re, Au, C, P, Ge, Sn

To first order, the distribution of elements between core and mantle resembles
equilibrium partitioning between metal liquid and silicatesconfirmed by iron
and achondrite meteorites (but at high P, no separate sulfide phase)

What makes an element siderophile or lithophile?

Notably, the Goldschmidt categories are well-grouped in
the periodic table of the elements:

Properties derived from outer

electrons
Ionization potential energy required to
remove the least tightly bound electron
Electron affinity energy given up as an
electron is added to an element
Electronegativity quantifies the tendency
of an element to attract a shared electron
when bonded to another element.

ORIGIN
OF
ELEMENTS

ORIGIN OF
ELEMENTS
At the beginning,,,
Matter + antimatter
Matter has the advantage
baryons quarks, leptons,
electrons, photons (no
protons or neutrons)
Hadrons protons,
neutrons
Hydrogen, helium (1:10 H:He)

Nuclear reactions the beginning

Proton-proton chain
1
1

Hydrogen fusion

H 11H 12H 0.422 MeV

1.02 MeV
2
1

H 11H 23He 5.493MeV

3
2

He 23He 24He11H 11H 12.859MeV

Triple-alpha fusion
4
2

He 24He 48Be

8
4

Be 24He126C

Particles:
- 42He
proton, positron (+)
or negatively charged
electron (-)
- high energy photon
neutrino

12
6

C 11H 137N

13
7

N 136C

C 11H 147N

13
6
14
7

N 11H 158O

15
8

O157N

15
7

N 11H 126C 24He

Neutron-capture
Reactions
Neutrino capture

62
28

Ni n Ni
1
0

63
28

Radioactive decay

63
28

Ni Cu
63
29

12
6

C He O

16
8

O He Ne

4
2

4
2

16
8

20
10

What about the rest

of the elements??

MAGMATIC
DIFFERENTIATION

Earths Chemical Differentiation

3 Major Zones, 2 Transitions
CRUST

MOHO - ~40km

WiechertGutenberg
discontinuity

CORE

Mantle Composition
Mantle versus crust
Mantle makes up >2/3 of earths
mass
Composition approximated by
pyrolite, an invention of Ringwoods
to explain the way these waves
move through the mantle.
SiO2
45%
MgO
30-40%
FeO
8-13%
Al2O3
3%
CaO
3%
High Mn, Cr, Ti

Oxides

Mantle

Crust

SiO2

45

60

MgO

37

FeO

Al2O3

15

CaO

Na2O

0.5

Cr2O3

0.4

0.01

MnO

0.2

0.1

TiO2

0.1

MAGMATIC DIFFERENTIATION
Why earths crust has widely varying chemistry?
Differentiation processes affect all major rock types. Wide variety of specific
reactions happen as igneous, metamorphic, and sedimentary rocks form,
change, transport ions, and decompose which result in geochemical
differentiation.
How does Magma composition change?
Hot material in different parts of the mantle?
Melts some rocks into it interacts with surrounding material (Partial
Melting)
Fractional crystallization crystals form and get separated form
source.

Liquid
Magma

Residual melt
Fractional crystallization

Crystallized rock

Plate Tectonics - Igneous Genesis

1. Mid-ocean Ridges
2. Intracontinental Rifts
3. Island Arcs
4. Active Continental
Margins
5. Back-arc Basins

6. Ocean Island Basalts

7. Miscellaneous IntraContinental Activity
kimberlites,
carbonatites,
anorthosites, etc.

GEOCHEMISTRY
OF THE
ROCK-FORMING
MINERALS

GEOCHEMISTRY OF IGNEOUS ROCKS

Characterization of different types (having different chemistries):
Ultramafic Mafic Intermediate Felsic
Composition commonly presented in weight % of the oxides (40-78%
SiO2 and 12-18% Al2O3)

Melt:
Liquid composed predominantly of silica and oxygen. Like water,
other ions impart greater conductivity to the solution. Si and O are
polymerized in the liquid to differing degrees (how rigid this
network).
Viscosity of the liquid increases with increasing silica content, i.e. it
has less resistance to flow with more SiO2 related to polymerization??
There is H2O in the magma (typically 2-6%). H2O decreases the
overall melting T of a magma, what does that mean for mineral
crystallization?

Processes of chemical differentiation

Partial Melting: Melting of a different solid material into a hotter liquid

Fractional Crystallization: Separation of initial precipitates which selectively
differentiate certain elements. Equilibrium is KEY? Hotter temperatures mean
faster kinetics
Melting: First bit to melt from a solid rock is generally more silica-rich. At
depth in the crust or mantle, melting/precipitation is a P-T process

Minerals which form

are thus a function of
melt composition and
how fast they cool (reequilibration?). This is
governed by the
stability of those
minerals and how
quickly they may or
may not react with the
hosting melt during
crystallization

Melt-crystal equilibrium 1
X
Magma at composition X
(30% Ca, 70% Na)
cools first crystal
bytownite (73% Ca,
27% Na)
This shifts the
composition of the
remaining melt such
that it is more Na-rich
(Y)
What would be the next
crystal to precipitate?
Finally, the last bit would
crystallize from Z

Y
Z

Precipitated crystals react with

cooling liquid, eventually
will re-equilibrate back.
UNLESS it cools so quickly
the crystal becomes zoned or
the early precipitates are
segregated and removed
from contact with the bulk of
the melt
Why arent all feldspars zoned?
IF there is sufficient time,
the crystals will reequilibrate with the magma
they are in. They reflect the
total Na-Ca content of the
magma. IF not, then
different minerals of
different composition will be
present in zoned plagioclase
or segregated from each
other physically.

Melt-crystal equilibrium 1b

Combining phase and composition

diagrams for mineral groups
Mica ternary
Muscovite
KAl2(AlSi3O10)(OH)2

No micas
Miscibility
Gap
Biotite series
Annite
KFe3(AlSi3O10)(OH)2

Phlogopite
KMg3(AlSi3O10)(OH)2

SOLID SOLUTION
AXO4 + B BXO4 + A
Occurs in a crystalline solid when one element substitutes for another. For
example, olivine is often expresses as: (Mg, Fe) 2SiO4. This means that
Fe and/or Mg occupy the same cation site. It is possible to have
fayalite Fe2SiO4 or forestrite Mg2SiO4 or mixture of any
proportions between these two end members, i.e., fayalite or
forestrite.
2Fe2 SiO4 + 2Mg 2(Mg, Fe)2SiO4 2Mg2SiO4 + 2Fe
Another example; garnet may have the composition:
(Mg1.7Fe0.9Mn0.2Ca0.2)Al2Si3O12. The garnet is a solid solution of the
following end member components:
(1) Pyrope Mg3Al2Si3O12; (2) Spessartine Mn3Al2Si3O12;
(3) Almandine Fe3Al2Si3O12 & (4) Grossular Ca3Al2Si3O12

GOLDSCHMIDTS RULES
AND RINGWOODS MODIFICATION
1. The ions of one element can extensively replace those of another in ionic
crystals if their radii differ by less than approximately 15%.
2. Ions whose charges differ by one unit substitute readily for one another
provided electrical neutrality of the crystal is maintained. If the charges
differ by more than one unit, substitution is generally slight.
3. When two different ions can occupy a particular position in a crystal
lattice, the ion with the higher ionic potential forms a stronger bond
with the anions surrounding the site.
Ringwood proposed the modifications:
4. Substitutions may be limited, even when the size and charge criteria are
satisfied, when the competing ions have different electronegativities
and form bonds of different ionic character.
This rule was proposed in 1955 to explain discrepancies with respect to the
first three Goldschmidt rules. For example, Na + and Cu+ have the same
radius and charge, but do not substitute for one another.

Coupled atomic substitutions

A3+ + X5 B4+ + Y4+
Can Th4+ substitute for Ce3+ in monazite (CePO4)?
Rule 1: When CN = 9, rTh4+ = 1.17 , rCe3+ = 1.23. OK
Rule 2: Only 1 charge unit difference. OK
Rule 3: Ionic potential (Th4+) = 4/1.17 = 3.42; ionic potential (Ce3+) = 3/1.23
= 2.44, so Th4+ is preferred!
Rule 4: Th = 1.3; Ce = 1.1. OK
But we must have a coupled substitution to maintain neutrality:
Th4+ + Si4+ Ce3+ + P5+
Plagioclase: NaAlSi3O8 - CaAl2Si2O8

Other examples

Na+ + Si4+ Ca2+ + Al3+

Gold and arsenic in pyrite (FeS2):
Au+ + As3+ 2Fe2+
REE and Na in apatite (Ca5(PO4)3F):
REE3+ + Na+ 2Ca2+

Incompatible vs. Compatible

trace elements
INCOMPATIBLE ELEMENTS: Elements that are too
large and/or too highly charged to fit easily into
common rock-forming minerals that crystallize from
melts. These elements become concentrated in melts.
Large-ion lithophile elements (LIL s): Incompatible owing
to large size, e.g., Rb+, Cs+, Sr2+, Ba2+, (K+).
High-field strength elements (HFSEs): Incompatible
owing to high charge, e.g., Zr4+, Hf 4+, Ta4+, Nb5+, Th4+,
U4+, Mo6+, W6+, etc.
COMPATIBLE ELEMENTS: Elements that fit easily
into rock-forming minerals, and may in fact be
preferred, e.g., Cr, V, Ni, Co, Ti, etc.

Three types of
trace-element substitution
1) CAMOUFLAGE, 2) CAPTURE and 3) ADMISSION
CAMOUFLAGE: Occurs when the minor element has the same charge
and similar ionic radius as the major element (same ionic potential; no
preference.
Zr4+ (0.80 ); Hf4+ (0.79 ). Hf usually does not form its own mineral; it
is camouflaged in zircon (ZrSiO4).
CAPTURE: Occurs when a minor element enters a crystal preferentially to
the major element because it has a higher ionic potential than the major
element.
For example, K-feldspar captures Ba2+ (1.44 ; Z/r = 1.39) or Sr2+ (1.21
; Z/r = 1.65) in place of K+ (1.46 , Z/r = 0.68). This requires
coupled substitution to balance charge: K+ + Si4+ Sr2+ (Ba2+) + Al3+
ADMISSION: Involves entry of a foreign ion with an ionic potential less
than that of the major ion.
Example Rb+ (1.57 ; Z/r = 0.637) for K+ (1.46 , Z/r = 0.68) in Kfeldspar. The major ion is preferred.

Lecture 3

Weathering

WEATHERING

There is a distinction
between weathering and
erosion
Most of the earths surface is
covered by exposure of
sediment or sedimentary rock,
by area. But the sediment layer
is thin in most places, with
respect to overall crustal
thickness, so sedimentary rock
is a minor volume fraction of
the crust (in part by definition:
once buried to the mid-crust,
sediments get cooked to
metasediments).

STABILITY OF MINERALS
AGAINST
WEATHERING

Chemical weathering is driven by

thermodynamic energy minimization, just like
chemical reactions at high temperature.

The system seeks the most stable

assemblage of phases.

The differences are that

(1) kinetics are slow and metastability is

common;

(2) the stable minerals under wet,

ambient conditions are different from
those at high T and P;

(3) solubility in water and its dependence

on water chemistry (notably pH) are
major determinants in the stability of
minerals in weathering.
A fresh rock made of olivine and pyroxenes
will end up as clays and iron oxides, with
other elements in solution
A fresh rock made of feldspars and quartz will
end up as clays, hydroxides, and quartz in
most waters.

TYPES OF WEATHERING REACTIONS

Some minerals are congruently soluble in acidic water, leaving no residue

The most abundant is calcite: CaCO3 + H2CO3 = Ca2+ + 2HCO3 (the Tums reaction)
Effects of dissolution (and precipitation) of calcite can be dramatic, to say the least.

Sinkhole

Speleothems

Karst terrain

Formation of Kaolinite
The most common alteration product of feldspars is kaolinite,
Al2Si2O5(OH)4, which serves as a model for the formation of clays by
weathering generally.

The reactions of feldspars to kaolinite illustrate some of the basic

trends:
K, Na, Ca are highly soluble and readily leached by
chemical weathering.
Excess Si can be removed as silicic acid although quartz is
relatively insoluble.
Al is extremely insoluble, and is essentially conserved as
clays.
Weathering is a hydration process, leaving H O bound in
2
the altered minerals.
2 KAlSi3O8 + 9 H2O + 2 H+ Al2Si2O5(OH)4 + 2 K+ + 4 H4SiO4
Note the H+ on the left-hand sideonly acidic water can
drive this reaction

Production of strong weathering agents

2FeS2 + 7 O2 + 2H2O 2Fe2+ + 4 SO42- + 4 H+

Fe oxidizers, S oxidizers
Fe2+ + O2 + H+ Fe3+OOH + 2 H+
H+ + SO42- HSO4Reduction by bacteria in swamps and marches
CH2O + FeOOH Fe2+ + CO2
CH2O + SO42- HS- + CO2

Many factors affect the

rate at which a rock will
weather.

Some of these variables are

local (e.g., source rock),
some are global. These
include temperature and
pCO2, leading to the CO2weathering feedback cycle.

Sorption:

Attraction between a particular mineral surface and an ion

or molecule due to: (1) Electrostatic interaction (unlike
charges attract), (2) Hydrophobic/hydrophilic interactions,
and (3) Specific bonding reactions at the surface

Definitions:
Sorption: Removal of solutes from solution onto mineral surfaces.
Sorbate: The species removed from solution.
Sorbent: The solid onto which solution species are sorbed.
There are three types of sorption:
1. Adsorption - solutes held at the mineral surface as a hydrated
species.
2. Absorption - solute incorporated into the mineral structure at the
surface.
3. Ion exchange - when an ion becomes sorbed to a surface by
changing places with a similarly charged ion previously residing
on the sorbent.

Sorption to S-OH sites

S-OH + M2+ S-OM+ + H+
S-OH + L2- S-L- + OH-

In addition, can also have bi-dendate sorption reactions:

S-OH
+ M2+
S-OH

S-O
M + 2 H+
S-O

Effect of pH on surface charge (C m-2) of selected minerals. The

curve for calcite is valid for a suspension in equilibrium with air.

Adsorption of metal
In a natural solution, many metal cations compete for the available
sorption sites. Experiments show some metals have greater adsorption
affinities than others.
What factors determine this selectivity?
(1) Ionic potential: defined as the charge over the radius (Z/r).
(2) Cations with low Z/r release their waters of hydration more easily and can
form inner-sphere surface complexes.
(3) In a natural solution, many metal cations compete for the available
sorption sites.
Many isovalent series cations exhibit decreasing sorption affinity with
decreasing ionic radius:
Cs+ > Rb+ > K+ > Na+ > Li+ > Ba2+ > Sr2+ > Ca2+ > Mg2+ > Hg2+ > Cd2+ > Zn2+
For transition metals, electron configuration becomes more important than
ionic radius:
Cu2+ > Ni2+ > Co2+ > Fe2+ > Mn2+

Ion exchange reactions:

Ions adsorbed by outer-sphere complexation and diffuse-ion
adsorption are readily exchangeable with similar ions in solution.

Cation exchange capacity: The concentration of ions, in

meq/100 g soil, that can be displaced from the soil by
ions in solution.
Exchange reactions involving common, major cations are
treated as equilibrium processes. The general form of a
cation exchange reaction is:
nAm+ + mBX mBn+ + nAX
The equilibrium constant for this reaction is given by:
m
B
n
A

a N
K
a N

n
A
m
B

CRYSTAL CHEMISTRY
OF CLAY MINERALS

Geochemistry of clay minerals

Clay minerals can be described as hydrated
aluminosilicates having grain size less than
4 microns. They are composed of two main
structural units namely tetrahedral (silica)
and octahedral (alumina)

The crystal chemistry of clays controls their physical properties such as

swelling, cationic exchange capacity and stability against burial diagenesis
TO clays such as kaolinite and TOT
clays differ with interlayer cations

Swelling

Schematic illustration of the two-layer

(TO) and three-layer clays (TOT)

Schematic illustration of some threelayer clays (note the interlayer cations)

Clays can have significant chemical

substitution, they undergo phase transitions
as diagenesis proceeds
Illite Smectite + Mg2++ Fe2++SiO2+H2O
Al2Si4O10(OH)2*nH2O + KAlSi3O8
KAl2(AlSi3)O10(OH2) + 4 SiO2(aq) + n H2O

CARBONATES
GEOCHEMISTRY

Carbonate Solubility
The commonest form of carbonate in nature is CaCO3 which, like
other carbonates, dissolves in acid medium:
CaCO3 Ca+2 + CO32
Saturation state can be expressed as follows:
= IAP / K
Where is the saturation index and IAP is the ion activity product
(= [Ca+2][CO32]) for the solution, and with the apparent solubility
product for a solution in equilibrium with solid CaCO3, and K is
constant. K depends on mineralogy where calcite < aragonite < Mgcalcite, as well as on the prevailing T and P where solubility is higher
in deeper and colder water.
At equilibrium:
= IAP / K = [Ca+2][CO32] = 1
When > 1, solution is super-saturated
When < 1, solution is under-saturated

Often, [Ca+2] is considered as a constant function of salinity of ocean.

Then, can be expressed in terms of carbonate ion saturation as
follows:

[Ca +2 ][CO3-2 ]in situ

[Ca +2 ][CO3-2 ]in situ

'
K sp
[Ca +2 ][CO3-2 ]saturation
If [Ca+2] constant

[CO3-2 ]in situ

[CO3-2 ]saturation

Therefore, it is possible to define CO32 as ([CO32] in situ - [CO32]sat)

Pressure, temperature, and respiration will affect the [CO32] in situ. The [CO 32]
will be lower in deeper, colder, and older water
Carbonate ion saturation of seawater as function of T and P for the two polymorphs;
calcite and aragonite
Temperature
(C)
24
2
2
2

Pressure
(atm.)
1
1
250
250

Saturation of carbonate ion 10-6 mole/kg

Calcite
Aragonite
46
66
48
69
71
101
106
152

Redox Fronts

Oxic
Anoxic

Boundary between
oxygen-rich (oxic)
and more reduced
(anoxic) waters
Oxygen input through
entrainment (wind,
wave action,
photosynthesis)
Oxygen consumption
from heterotrophic
consumption, reaction
with reduced forms of
Fe, Mn, S