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Lecture 6:

A. THE COMPOSITION OF THE CRUST

B. THE COMPOSITION OF THE EARTH AS A WHOLE

C. GEOCHEMICAL CLASSIFICATION OF ELEMENTS

A. THE COMPOSITION OF THE CRUST

• According to Ronov and Yaroshevsky (in Hart, 1969),

there are three types of crust – continental, oceanic
and subcontinental.
• Each of which comprises shells of sedimentary and
igneous rocks.
• Average thicknesses, masses, and mean compositions
are derived for each of these shells, which are then
combined to give averages for each of the three types of
crust, and ultimately for the total crust (which they define
as the material above the Mohorovičić discontinuity).

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Their averages for continental crust and the total crust,

calculated on a CO2 and H2O free basis, are as follows:

Table 3.5 The average amount of the elements in crustal rocks in grams per ton or parts
per million*

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• Eight elements - O, Si, Al, Fe, Ca, Na, K, Mg – make up

nearly 99% of the total.

• Of these oxygen is absolutely predominant (Table 3.6).

• The earth’s crust consists almost entirely of oxygen

compounds, especially silicates of aluminum,
calcium, magnesium, sodium, potassium, and iron.

• In terms of numbers of atoms oxygen exceeds 60%.

• If the volume of the different atoms, or rather ions, is

recalculated, oxygen makes up more than 90% of the total
volume occupied by the elements.

• As Goldschmidt remarked, the lithosphere may well be called

the oxy-shere.

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Relative abundances:
• of the >100 known elements, only 90 occur naturally on Earth
• only 14 elements make up > 99% of the naturally occurring
inorganic chemical compounds (minerals)
✓ H, C, O, Na, Mg, Al, Si, P, S, K, Ca, Ti, Mn, and Fe
✓ O, Mg, Si, Fe, Al, and Ca make up > 99% of the BSE

B. THE COMPOSITION OF THE EARTH AS A WHOLE

• About 90% of the earth is made up of four elements, Fe,

O, Si, and Mg.

• The only other elements that may be present in amounts

greater than 1% are Ni, Ca, Al, and S.

• Seven elements, Na, K, Cr, Co, P, Mn, and Ti may occur

in amount from 0.01 to 1%.

• Thus the earth is made up almost entirely of 15

elements, and the percentage of all the others is
negligible, probably 0.1% or less of the whole.

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• The main differences in composition between the crust and

the bulk composition of the earth are:

✓ the lesser abundance of iron and magnesium in the crust,

✓ the nonappearance of nickel and sulfur, and
✓ the increased significance of aluminum, potassium, and
sodium.

• This suggests that the differentiation of the earth has led to a

concentration of relatively light, easily fusible alkali-aluminum
silicates at the surface.

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C. GEOCHEMICAL CLASSIFICATION OF
ELEMENTS

An element may be classified according to its

geochemical affinity into one of four
groups:
➢ Siderophile
➢ Chalcophile
➢ Lithophile, and
➢ Atmophile

✓ lithophile elements (oxygen, oxides, silicate minerals,

Greek lithos - stone)
✓ chacophile (sulphides, Greek khalkos=copper)
✓ siderophile (metallic, Greek sideros=iron)

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The geochemical character of an element is largely governed by the electronic

configuration of its atoms and hence is closely related to its systematic position in
the periodic table.

Siderophile Elements
Siderophile (from sideron, "iron", and philia, "love")
elements are the high-density transition metals which
tend to sink into the core because they dissolve readily
in iron either as solid solutions or in the molten state.
The siderophile elements include: gold, cobalt, iron, iridium,
molybdenum, nickel, osmium, palladium, platinum,
rhenium, rhodium, ruthenium, germanium, silver and
tungsten. Manganese may also be included in the
siderophilic classification by some

• Occur as native elements.

• Tend to form metallic bonding.
• Do not readily form compound with oxygen and sulfur.
• They are those of Group VIII and some neighboring
elements, whose outermost shells of electrons are for
the most part incompletely filled.

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Chalcophile Elements
• Chalcophile elements are those that remain on or close
to the surface because they combine readily with sulfur
and/or some other chalcogen other than oxygen, forming
compounds which do not sink into the core.
• The chalcophile elements include: Ag, As, Bi, Cd, Cu,
Ga, Ge, Hg, In, Pb, S, Sb, Se, Sn, Te, Tl and Zn.

• They make sulfides. e.g.,

Zn + S → ZnS
Pb + S → PbS

• Ionize less readily thus tend to form covalent compounds

with sulfur (and selenium and tellurium, when present).
• The chalcophile elements are those of the B subgroups
whose ions have 18 electrons in the outer shells.

Lithophile Elements
Lithophile elements are those that remain on or close to the
surface because they combine readily with oxygen, forming
compounds that do not sink into the core.
The lithophile elements include: Al, B, Ba, Be, Br, Ca, Cl, Cr,
Cs, F, I, Hf, K, Li, Mg, Na, Nb, O, P, Rb, Sc, Si, Sr, Ta, Th,
Ti, U, V, Y, Zr, W and the lanthanides.

• Occur mainly as oxygen compounds. e.g.,

4Na + O2 → 2Na2O

• Oxidized readily form stable oxy-ions (CO32-, SO42-)

• Bonding is mainly ionic in character.
• Those readily form ions with an outermost 8-electron shell.

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Atmophile Elements
• The atmophile elements are: H, C, N and the
noble gases.
• Atmophile elements (also called "volatile
elements") are defined as those that remain
mostly on or above the surface because they
are, or occur in, liquids and/or gases at
temperatures and pressures found on the
surface.
• Mainly gaseous elements.
• Present in the atmosphere.
• Not readily forming compounds.
• Sometimes show van der waals bonding

• Some elements show affinity for more than one group.

• The distribution of any element is dependent to some extent on

temperature, pressure, and the chemical environment of the system
as a whole.

• For example, chromium is a strongly lithophile element in the earth’s

crust, but if oxygen is deficient, as in some meteorites, chromium is
decidedly chalcophile (sulfo-spinel daubréelite, FeCr2S4).

In general, the classification of an element as lithophile, chalcophile, or

siderophile refers to its behavior in liquid-liquid equilibria between melts.

When an element shows affinity for more than one group, it is given in
parenthesis under the group or groups of secondary affinity.

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SOME GEOCHEMICALLY IMPORTANT ELEMENTS

A typical rock analysis
Wt. % Oxides to Atom % Conversion
Oxide Wt. % Mol Wt. Atom prop Atom %
SiO 2 49.20 60.09 0.82 12.25
TiO2 1.84 95.90 0.02 0.29
Al 2O3 15.74 101.96 0.31 4.62
Fe2O3 3.79 159.70 0.05 0.71
FeO 7.13 71.85 0.10 1.48
MnO 0.20 70.94 0.00 0.04
MgO 6.73 40.31 0.17 2.50
CaO 9.47 56.08 0.17 2.53
Na2O 2.91 61.98 0.09 1.40
K 2O 1.10 94.20 0.02 0.35
+
H2O 0.95 18.02 0.11 1.58
(O) 4.83 72.26
Total 99.06 6.69 100.00

Table 8-3. Chemical analyses of some representative igneous rocks

Peridotite Basalt Andesite Rhyolite Phonolite

SiO2 42.26 49.20 57.94 72.82 56.19
TiO2 0.63 1.84 0.87 0.28 0.62
Al2O3 4.23 15.74 17.02 13.27 19.04
Fe2O3 3.61 3.79 3.27 1.48 2.79
FeO 6.58 7.13 4.04 1.11 2.03
MnO 0.41 0.20 0.14 0.06 0.17
MgO 31.24 6.73 3.33 0.39 1.07
CaO 5.05 9.47 6.79 1.14 2.72
Na2O 0.49 2.91 3.48 3.55 7.79
K2O 0.34 1.10 1.62 4.30 5.24
H2O+ 3.91 0.95 0.83 1.10 1.57

Total 98.75 99.06 99.3 99.50 99.23

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I. Major element : usually greater than 1%

SiO2 Al2O3 FeO MgO CaO Na2O K2O H2O
II. Minor element : usually 0.1 - 1%
TiO2 MnO P2O5 CO2
III. Trace elements : usually < 0.1%
everything else

Element Wt % Oxide Atom %

O 60.8
Si 59.3 21.2
Abundance of the elements
Al 15.3 6.4
in the Earth’s crust
Fe 7.5 2.2
Ca 6.9 2.6
Mg 4.5 2.4
Na 2.8 1.9

I. MAJOR ELEMENTS

• Have concentrations in most geological materials

in excess of 1%.

• They are essential constituent of rock-forming

minerals.

• They are Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K and P.

• Their concentrations are expressed as a weight

percent (wt%) of the oxide.

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Table 1.1 Whole rock geochemistry of komatiite flows from the

Belingwe greenstone belt, Zimbabwe (Nisbet et al., 1987).

Wt% Bengal Sylhet Trough NASC PASS Wedepohl UC

Basin(centra (northeastern
l, eastern Bengal Basin)
and southern (n=20)
most part) (Rahman and
(n=15) Faupl, 2003)
SiO2 60.93 60.01 64.80 62.80 58.9 66.00
TiO2 0.82 0.88 0.70 1.00 0.78 0.50
Al2O3 15.79 17.14 16.90 18.90 16.7 15.20
Fe2O3 6.78 7.09 5.65 7.22 6.91 5.00
MnO 0.09 0.09 0.06 0.11 0.09 0.08
MgO 2.60 2.79 2.86 2.20 2.6 2.20
CaO 1.37 1.19 3.63 1.30 2.2 4.20
Na2O 1.49 1.53 1.14 1.20 1.6 3.90
K 2O 3.05 3.24 3.97 3.70 3.6 3.40
P2O5 0.14 0.14 0.13 0.16 0.16 -
LOI 6.55 6.39 6.00 6.3

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II. MINOR ELEMENTS

• The term minor element is sometimes applied to the less

abundant major elements, such as manganese (Mn) and
phosphorus (P) with oxide concentrations below 0.1 to
1%.

• Minor element determinations are usually made only for

cations.

• And it is assumed that they are accompanied by an

appropriate amount of oxygen.

• Iron may be determined as FeO and Fe2O3 but is sometimes

expressed as ‘total Fe’ and given as either FeO(tot) or
Fe2O3(tot).

III. TRACE ELEMENTS

• Those elements which are present at less than the 0.1

% level.

• Concentrations are expressed in parts per million (ppm)

or more rarely in parts per billion (ppb; 1 billion =109) of
the element.

• Convention is not always followed however, and trace

element concentrations exceeding the 0.1 % (1000 ppm)
level are sometimes cited.

• They may occur as dissolved ‘impurities’ in rock-

forming minerals, or in separate accessory minerals.

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Table 1.1 Whole rock geochemistry of komatiite flows from the

Belingwe greenstone belt, Zimbabwe (Nisbet et al., 1987).

• Some elements behave as a major element in one group of

rocks and as a trace element in another group of rocks.

• An example is the element K, which is a major constituent of

rhyolites, making up more than 4 wt % of the rock (occurs in
orthoclase and biotite).

• In some basalts, however, K concentrations are very low and

there are no K-bearing phases. In this case K behaves as a
trace element.

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Trace Element Grouping in the Periodic Table

Several groups of elements in the periodic table are of particular

geochemical interest.

a) elements with atomic numbers 57 to 71, the lanthanides

or rare earth elements (REE),

b) the platinum group elements (PGE) (atomic numbers 44

to 46 and 76 to 79) also known as the noble metals if they
include Au, and

c) the transitional metals (atomic numbers 21 to 30).

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Goldschmidt’s classification is based on distribution in

meteorites and Earth’s major geochemical reservoirs, but
elements can still be further grouped based on their relative
behavior in the Earth’s silicate portion, mantle and crust

• The elements of these respective groups have similar

chemical properties and for this reason are expected to
show similar geochemical behavior.

• This is not always the case, however, because

geological processes can take advantage of subtle
chemical differences and fractionate elements of a group
one from the other.

• Thus one of the tasks of trace element geochemistry is

to discover which geological processes may have this
effect and to quantify the extent of a particular process.

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RARE EARTH ELEMENTS (REE)

• Following the element lanthanum (La), electrons begin to

occupy the seven 4f orbitals, forming the fourteen metals
known as the lanthanides or rare earth elements (REE).

• The distinction between individual rare earths lies in the

number of 4f-electrons.

• These are mostly not involve in bonding, and the chemical

properties of all 14 elements, together with lanthanum, are
therefore remarkably similar. All have stable trivalent states.

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• The REE comprise the series of metals with atomic numbers 57 to

71, i.e., La to Lu (Table).

• Due to the increase in nuclear charge, there is a steady decrease of

ionic radius from lanthanum La+ to lutetium Lu+.

• Typically the low atomic number members of the series are termed
the light rare earths (LREE, La – Sm). The light rare earths’ are
incompatible elements.

• The heavy rare earths (HREE, Gd – Lu) are those with the higher
atomic number.

• Owing to their smaller ionic radii, the heavy rare earths (HREE, Gd –
Lu) are more easily accommodated in the crystal structures of some
rock-forming minerals, particularly garnet.

• The trace element yttrium (Y) also forms a 3+ ion. The ionic radius of
Y3+ is the same as Ho3+, and in geological materials yttrium is always
closely associated with the HREE.

• The rare earth elements (REE) are the most useful of all trace
elements and REE studies have important applications in
igneous, sedimentary and metamorphic petrology.

• Rare earth abundances in igneous rocks provide a very useful

trace element fingerprint for distinguishing between various
magma types and their different origins.

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The platinum group

• The platinum group metals (PGMs) are six transitional

metal elements that are chemically, physically, and
anatomically similar. PGMs include
•
• Iridium (Ir)
• Osmium (Os)
• Palladium (Pd)
• Platinum (Pt)
• Rhodium (Rh)
• Ruthenium (Ru)

VOLATILES

• Volatiles such as H2O, CO2 and S are normally included

in the major element analysis.

• Water combined within the lattice of silicate minerals and

released above 110°C is described as H2O+.

• Water present simply as dampness in the rock powder

and driven off by heating below 110 °C is quoted as
H2O- and is not an important constituent of the rock.

• Sometimes the total volatile content of the rock is

determined by ignition at 1000 °C and is expressed as
‘loss on ignition’ (Lechier and Desilets, 1987).

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