The Geochemistry of Rocks and

Natural Waters

Course no. 210301

1st part: Introduction and

Fundamentals in Geochemistry

A. Koschinsky

 Geochemistry - an Introduction
What is Geochemistry?

The urge to make geology more quantitative has led to the widespread
inclusion of the so-called basic sciences such as physics and chemistry into
the study of geology. The term geochemistry was first used by the Swiss
chemist Schnbein in 1838. V.M. Goldschmidt, who is regarded as the
founder of modern geochemistry, characterized geochemistry in 1933 with
the following words:

The major task of geochemistry is to investigate the composition of the Earth

as a whole and of its various components and to uncover the laws that
control the distribution of the various elements. To solve these problems, the
geochemist needs a comprehensive collection of analytical data of terrestrial
material, i.e. rocks, waters and atmosphere. Furthermore, he uses analyses
of meteorites, astrophysical data about the composition of other cosmic
bodies and geophysical data about the nature of the Earths inside. Much
useful information also came from the synthesis of minerals in the lab and
from the observation of their mode of formation and stability conditions.

 Definition and Sub-disciplines
Geochemistry uses the tools of chemistry to understand processes on
Earth.

The wide field of Geochemistry includes:

Trace element geochemistry

Isotope geochemistry
Petrochemistry
Soil geochemistry
Sediment geochemistry
Marine geochemistry
Atmospheric geochemistry
Planetary geochemistry and Cosmochemistry
Geochemical thermodynamics and kinetics
Aquatic chemistry
Inorganic geochemistry
Organic geochemistry
Biogeochemistry
Environmental geochemistry

 The Periodic Table of Elements

 The Periodic Table of Elements
Symbols and numbers Isotopes

The atoms of an element can differ in

mass from each other because they
have differing numbers of neutrons.
Those with more neutrons will weigh
more and be more massive. The
atomic mass (often referred to as
atomic weight) of an element is
calculated by adding together the
number of protons and the number of
neutrons.

Examples for isotopic couples:

Stable isotopes:
H-1, H-2 (D), H-3 (T) (or 1H, 2H, 3H)
C-12, C-13, C-14 (or 12C, 13C, 14C)
O-16, O-18
Radiogenic isotopes:
Fe-54, Fe-56
U-235, U-238

 The Electronic Structure of Atoms
Electrons and Orbits

The electronic structure of

an atom largely determines
the chemical properties of
the element.
Elements within the same
group of the Periodic Table
have the similar outer
electronic configuration and
behave chemically similar.

Each electron shell

corresponds to a period or
row in the Periodic Table.
The periodic nature of
chemical properties reflects
the filling of successive
shells with additional
electrons.

 The Electronic Structure of Atoms

Lshell
Kshell N
L M
K

Electron shell representation of

carbon atom: The copper atom has one lone
The inner-most (first) shell is full as it electron in its outer shell, which can
can hold only two electrons. The second easily be pulled away from the atom.
shell can hold eight but has only four.

Protons, neutrons, electrons

 The Electronic Configuration of the Elements

 Chemical Properties of the Elements
Ionization potential

The First Ionization

Potential is the energy
required to remove the
least tightly bound
electron from the atom.

Example: H --> H+ + e-

The second, third,

ionization potentials are
defined
correspondingly.

Valence is the number

of electrons given up or
accepted. Transition
metals often have more
than one valence.
Example: Fe(II) and
Fe(III)
 Chemical Properties of the Elements
Electron Affinity
Electron Affinity is a measure of the desire or ability of an atom to gain electrons. It is an
energy concept. The formal definition states that Electron Affinity is the amount of energy
released when an electron as added to an atom. Most atoms tend to lose energy when they
gain electrons. Some atoms do not. The elements located in the upper right corner of the
Periodic Chart have the high E.A. values (usually found as anions ) while those in the lower
left corner have the low E.A. value (usually found as cations ). A generic equation of the EA
process would be as follows.

X + e- --> X-1 + EA. Often this is measured in electronvolts.

Electronegativity
The concept of Electronegativity refers to the ability of a bonded atom to pull electrons
towards itself.
It is defined as the relative ability of an atom in a molecule to attract electrons towards itself.
As atoms bond, electrons are shared or transferred. The atom with the higher
electronegativity will dominate the electrons.

In order to be able to determine electronegativity values it is important to observe the

behavior of atoms in a bonded situation. Consequently, the Noble Gases do not usually
appear with listed electronegativity values.

 Chemical Properties of the Elements
Pauling Scale
The Pauling Scale is the most commonly used scale of electronegativity values. The
calculations used to arrive at the numbers in the scale are complex. It is most common to
simply know the results of those calculations. The scale is based on Fluorine having the
largest electronegativity with a value of 4.0. The Francium atom is assigned the lowest
electronegativity value at 0.7. All other values are located between these extremes.
Examples: Li--1.0 Be--1.5 B--2.0 C--2.5 N--3.0 O--3.5 F--4.0.

(Paulingscale)

 Chemical Properties of the Elements

 Chemical Properties of the Elements

R.S. Mulliken (1934) proposed an electronegativity scale in which the electronegativity, M is

related to the electron affinity EAv (a measure of the tendency of an atom to form a negative
species) and the ionization potential IEv (a measure of the tendency of an atom to form a
positive species) by the equation:

M = (IEv + EAv)/2

The subscript v denotes a specific valence state.

The Mulliken electronegativities are expressed directly in energy units, usually electron volts.

 Chemical Properties of the Elements
Ionic radius
Cations have smaller radii than anions. Ionic radius decreases with increasing charge.
Ionic radius is important for geochemical reactions such as substitution in crystal lattices,
solubility, and diffusion rates.

Comparisonofsomeatomicandrespectiveionic
radii(innanometers)

 Chemical Bonding
Ionic Bond: total transfer of electrons from one atom to another

Covalent Bond: the outer electrons of

the bound atoms are in hybrid orbits that
encompass both atoms.
Due to different electronegativity, covalent
bonds are often polar --> dipole
interactions (Van der Waals interactions)

 Chemical Bonding

Metallic Bond: valence electrons are not

associated with any single atom, but are
mobile (electron sea).

This bond type is less important in

geochemistry than the other bonds.

Chemical Properties of the Elements - Summary
Hydrogen Hydrogen is unique as it is the simplest possible atom consisting of
just one proton and one electron
Alkali Metals These are very reactive metals that do not occur freely in nature.
These metals have only one electron in their outer shell, therefore
they are ready to lose that one electron in ionic bonding with other
elements. The alkali metals are softer than most other metals.
Cesium and francium are the most reactive elements in this group.
Alkaline Earth The alkaline earth elements are metallic. All alkaline earth elements
Metals have an oxidation number of +2, making them very reactive.
Because of their reactivity, the alkaline metals are not found free in
nature.
Transition The transition elements are both ductile and malleable, and conduct
Metals electricity and heat. The interesting thing about transition metals is
that their valence electrons, or the electrons they use to combine
with other elements, are present in more than one shell. This is the
reason why they often exhibit several common oxidation states.
Other Metals The 7 elements classified as other metals, unlike the transition
elements, do not exhibit variable oxidation states, and their valence
electrons are only present in their outer shell. All of these elements
are solid. They have oxidation numbers of +3, +4, -4, and -3.

Chemical Properties of the Elements - Summary
Metalloids Metalloids are the elements found along the stair-step line that
distinguishes metals from non-metals. This line is drawn from
between Boron and Aluminum to the border between Polonium and
Astatine. Metalloids have properties of both metals and non-metals.
Some of the metalloids, such as silicon and germanium, are semi-
conductors.
Non-Metals Non-metals are not able to conduct electricity or heat very well. As
opposed to metals, non-metallic elements are very brittle. The non-
metals exist in two of the three states of matter at room temperature:
gases (such as oxygen) and solids (such as carbon). They have
oxidation numbers of +4, -4, -3, and -2.
Rare Earth The thirty rare earth elements are composed of the lanthanide and
Metals actinide series. They are transition metals. One element of the
lanthanide series and most of the elements in the actinide series are
called trans-uranic, and are synthetic or man-made
Halogens The term halogen means salt-former and compounds containing
halogens are called salts. All halogens have 7 electrons in their
outer shell, giving them an oxidation number of -1. The halogens are
non-metallic and exist, at room temperature, in all three states of
matter
Noble Gases All noble gases have the maximum number of electrons possible in
their outer shell (2 for Helium, 8 for all others), making them stable
and preventing them from forming compounds readily.

 What is the Solar System made of?

What is the relative abundances of the various elements throughout the Universe?
This turns out to be a difficult task for one obvious reason. Spectroscopic measurements
of elements from the distant stars are strongly biased towards only those elements in
excited states at or near the stellar surface. Those elements principally in the interior do
not contribute to surface radiation in the same proportions as actually exist in a star.
The situation is better for the Sun. When element distributions are stated as Cosmic
Abundances, they actually are rough estimates made from Solar Abundances .

What is the Solar
System made of?

From the figure, we see four

patterns:

An overwhelming abundance
of light elements
A strong preference for even-
numbered elements
A peak in abundance at iron,
followed by a steady decrease.
Elements 3-5, Lithium,
Beryllium and Boron, are very
low in abundance.

These patterns have to do with

nucleosynthesis (element
formation) in the stars.

 What is the Solar System made of?

If the Sun and Solar

System formed from the
same material, we would
expect the raw material of
the planets to match the
composition of the Sun,
minus those elements that
would remain as gases.
We find such a
composition in a class of
meteorites called
chondrites, which are
thought to be the most
primitive remaining solar
system material.
Chondrites are considered
the raw material of the
inner Solar System and
probably reflect the bulk
composition of the Earth.

 What is the
Earth made of?

Relative abundance by weight

of elements in the whole
Earth and in the Earths crust.
Differentiation has created a
light crust depleted in iron
and enriched in oxygen,
silicon, aluminum, calcium,
potassium, and sodium.

 What is the Earth made of?
Crustal Element Distribution

The abundance of elements in the Earth's crust is much different from the abundance of
elements that are to be found on the other planets and our Sun. The continental crust of
the Earth also differs radically from the overall composition of the Earth.
Our Earth as a whole and its crust, in particular, have extraordinary concentrations of
elements, all associated with silicate minerals like olivine, pyroxene, amphibole,
plagioclase, the micas, and quartz. Although there are a vast number of silicate minerals,
most silicate minerals are made from just eight elements.
The two most common elements in the Earth's crust, oxygen and silicon, combine to form
the "backbone" of the silicate minerals, along with, occasionally, aluminum and iron.
These four elements alone account for about 87% of the Earth's crust. This silicate or
alumina-silicate "backbone" carries excess negative charge, however. Positive charge in
the form of cations has to be brought in to balance this negative charge. The four most
important elements that fit in the mineralogical structures of the silicates are calcium,
sodium, potassium and magnesium. Taken all together, constituting nearly 99% of crustal
elements, leaves little room for all of the other elements.

As a consequence, all other elements are either nearly absent from the Earth's crust or
are found primarily in non-silicate rocks.

 What is the Earth made of?

The silica tetrahedron and the structure of silicate minerals

a. The silica tetrahedron

consists of a central
silicon atom bound to 4 b. In orthosilicates such as olivine, the tetrahedra are
oxygens. separate and each oxygen is also bound to other
metal ions that occupy interstitial sites between the
tetrahedra.
 What is the Earth made of?

d. In sheet silicates,
such as talc, mica, and
clays, the tetrahedra
each share 3 oxygens
and are bound together
into sheets.

c. In pyroxenes, the tetrahedral each

share two oxygen and are bound
together into chains. Metal ions are
between the chains.
located