University of Duhok / College of Spatial Planning and Applied Science / Department of Applied

Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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COURSE INFORMATION
Course Title: Geochemistry
Lecturer’s Name: Ameer Hayder Khalid
Day and time of lectures: Sunday (9:00 – 11:00 am)

SUPPORTING LITERATURES:
1. Goldschmidt, V. M. (1954): Geochemistry. Oxford University Press, London.
2. Henderson, P. (1982): Inorganic Geochemistry. Pergamon Press, 353 p.
3. Mason, B. (1958, 1966): Principles of Geochemistry. 2nd and 3rd Editions. John Wiley
and Sons. 310 p, 329 p.
4. Brown, G. C. and Mussett, A. E. (1981): The inaccessible Earth. George, Allen and
Unwin, London, 235 p.
5. Clarke, F. W. (1924): The Data of Geochemistry. US Geol. Surv. Bull. 770 p.
6. Krauskopf, K. B. (1979): Introduction to Geochemistry. 2nd Edition. McGraw Hill, 617
p.
7. Fergusson, J. E. (1982): Inorganic Chemistry and the Earth. Pergamon Press, 400 p.
8. Brownlow, A. H. (1979): Geochemistry. Prentice Hall Inc., Englewood Cliffs, 385 p.
9. Albarède, F. (2003): Geochemistry. An Introduction. Cambridge University Press, 248
p.
10. Misra, K. C. (200): Introduction to Geochemistry: Principles and Applications. 1st
Edition. Kindle Edition, 1315 p.

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 University of Duhok / College of Spatial Planning and Applied Science / Department of Applied
Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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Lecture One
Geochemistry: Definition and Overview
Geochemistry is the science that uses the tools and principles of chemistry to explain the
mechanisms behind major geological systems such as the Earth's crust and its oceans. In
another word, geochemistry is involved in understanding the different ways in which
elements move whether in the core, mantle, crust, oceans, sediments, air, space, or other
planets. It deals with all earth's material including rocks of different origins, soil, water,
gases, organisms etc.
The realm of geochemistry extends beyond the Earth, encompassing the entire Solar
System and made important contributions to the understanding of a number of processes
including mantle convection, the formation of planets and the origins of granite and basalt.
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-German chemist Christian Friedrich
Schönbein in 1838. However, for the rest of the century the more common term was
"chemical geology", and there was a little contact between geologists and chemists.
Victor Moritz Goldschmidt, a Swiss-born Norwegian mineralogist and petrologist
formulated a set of rules for how elements are grouped. Goldschmidt, who later became
known as the father of modern geochemistry, published this work in the series (Geochemical
Laws of the Distribution of Elements). He defined the study of geochemistry as: “the laws
governing the distribution of chemical elements and their isotopes throughout the earth’’. He
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 Earth’s inside. Much useful information also came from the

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 University of Duhok / College of Spatial Planning and Applied Science / Department of Applied
Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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synthesis of minerals in the lab and from the observation of their mode of formation and
stability conditions.”
Important subfields of geochemistry are: Isotope geochemistry, Planetary geochemistry and
cosmogeochemistry, Petroleum geochemistry, Biogeochemistry, Organic geochemistry,
Marine geochemistry, Geochronology, Aqueous geochemistry, Regional geochemistry,
Photogeochemistry, Industrial minerals and rocks, Medical geology, Soil geochemistry,
Sediment geochemistry, Trace elements geochemistry, Inorganic geochemistry, Atmospheric
geochemistry, Environmental geochemistry etc.

The relationship between geochemistry and other sciences

Geochemical Classification of Elements:

Chemical elements distribute in patterns based on the nature of materials in the different
parts of the Earth. Goldschmidt (1937) laid out the basic conceptions of the geochemical
classification of elements derived from their distribution in the mineral phases composing
the meteorites as well as observing their distribution during melting of some ores like

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 University of Duhok / College of Spatial Planning and Applied Science / Department of Applied
Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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Cu-bearing slate rocks. Accordingly, elements are classified by their geochemical affinity
into the following groups:
1. Siderophile Group: (from sideron, "iron", and philia, "love"), literally “iron-loving”,
represents the transition elements with the affinity to be present with metallic iron phase or
native mineral phase. Elements of this group tend to concentrate in the core because they
dissolve readily in iron either as solid solutions or in the molten state, although some
sources include elements which are not transition metals in their list of siderophiles, such
as germanium (Ge).
2. Chalcophile Group: derives from Greek khalkós (χαλκός), meaning "ore" (it also meant
"bronze" or "copper", but in this case "ore" is the relevant meaning), and is taken to mean
"chalcogen-loving" by various sources. Chalcophile “sulphur- loving” or “copper-loving”
includes metals and heavier non-metals that remain on or close to the surface because they
combine readily with sulfur (S) other than oxygen to form highly insoluble sulphide phases
and compounds which do not sink into the core. These elements tend to concentrate in the
mantle and the crust.
Although no chalcophile element is of high abundance in the Earth's crust, chalcophile
elements constitute the bulk of commercially important metals.
3. Lithophile Group: “oxygen-loving” or “stone-loving”, contains elements that remain on
or close to the surface because they have the ability to combine readily with oxygen in
phases of oxides, silicates, carbonate etc. (i.e., excluding sulphides and metallic phases).
Elements of this group tend to concentrate in the crust and the mantle.
Because of their strong affinity for oxygen, most lithophile elements are enriched in the
Earth's crust relative to their abundance in the solar system.
4. Atmophile Group: (also called "volatile elements") are 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.
Elements of this group concentrate in the atmosphere. Carbon is also classed as an atmophile
because it forms very strong multiple bonds with oxygen in CO (slowly oxidized in the
atmosphere) and CO2. The latter is the fourth-largest constituent of the Earth's atmosphere,

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 University of Duhok / College of Spatial Planning and Applied Science / Department of Applied
Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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while CO occurs naturally in volcanoes and has a residence time in the atmosphere of a few
months.
Hydrogen, which occurs in the compound water, is also classed as an atmophile. Water is
classified as a volatile because most of it is liquid or gas, even though it does exist as a solid
compound on the surface.
Because all atmophile elements are either gases or form volatile hydrides, atmophile
elements are strongly depleted on earth as a whole relative to their solar abundances owing
to losses from the atmosphere during the formation of the Earth. The heavier noble gases
(krypton and xenon) are the rarest stable elements on Earth.

Geochemical classification of elements depending on their distribution in meteorites

Siderophile Chalcophile Lithophile Atmophile

Fe* Co* Ni* (Cu) Ag Li Na K Rb Ce (H) N (O)
Ru Rh Pd Zn Cd Hg Be Mg Ca Sr (I) He Ne Ar
Os Ir Pl Ga In Tl Ba B Al Sc Y La - Lu Kr Xe
Au Ret Mo+ (Ge) (Sn) Pb Si Ti Zr Hf Th
Ge* Sn* W‡ As (Sb) Bi P V Nb Ta
C‡ {U* Ga* S Se Te O Cr U
Ge* As‡ Sb+ (Fe) Mo (Os) H F Cl Br I
(Ru) (Rh) (Pd) (Fe) Mn (Zn) (Ga)
* Chalcophile and
lithophile in the
earth’s crust
+ Chalcophile in the
earth’s crust
‡ Lithophile in the
earth’s crust

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 University of Duhok / College of Spatial Planning and Applied Science / Department of Applied
Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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Oxygen (O) is present as atmophile in atmosphere, and also as lithophile in the minerals such
as (silicates, oxides, carbonates etc.).
Iron (Fe) is present in metallic phase as siderophile, and in troilite FeS as chalcophile, and in
olivine (a silicate mineral) as lithophile.
The classification of an element depends on its environmental conditions. For example;
chromium (Cr) is lithophile in oxidation environment such as chromite (FeCr2O4), while in
reduction environment it is chalcophile such as daubréelite (FeCr2S6).
Thallium (Tl) is classified as chalcophile, while it is abundant in the earth’s crust as
lithophile.

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

of its atoms and hence is closely related to its position in the Periodic Table. In general,
lithophile elements (contains 8 electrons in their outer orbitals) are to the left of the center,
siderophile elements are concentrated at the center and chalcophile elements (contains 18

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 University of Duhok / College of Spatial Planning and Applied Science / Department of Applied
Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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electrons in their outer orbitals) to the right of the Periodic Table, and atmophile elements to
the extreme right as shown in the following figure:

In the relation of atomic volume – atomic number of elements, siderophile elements are
found at the minima of this relation, whereas chalcophile elements are found at the lift up
side of the relation (where atomic volume increases with atomic number). Lithophile and
atmophile elements are at the maxima and turn down of the relation.
Element groups can be recognized by heat of formation of their oxides. Lithophile elements
oxides have a higher heat of formation than ferrous oxide. Otherwise, elements belong to
either chalcophile or siderophile groups.

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 University of Duhok / College of Spatial Planning and Applied Science / Department of Applied
Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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* + +
Siderophile + +
Chalcophile
+ +
+ +
Lithophile + +
Atmophile +
Atomic volume

*** ***

Atomic number

The relationship between the atomic volume, the atomic number of elements, and the locations of
their geochemical classification groups

It can also be correlated with their electrode potentials. Siderophile elements are mostly
noble metals with low electrode potentials; Lithophile elements have high electrode
potential (1 - 3 volt), and chalcophile elements have intermediate values.
Geochemical properties of an element vary by the type of bond (metallic, covalent and ionic)
with which it is bonded in the mineral phase. Many studies discussed the relation between
the type of bond and the chemical and physical properties of the element that can be
measured quantitatively, such as the melting point, heat of formation of element compounds,
light refraction factor in minerals, ionization potential and electronegativity of ions.
Despite criticism of the said relations, electronegativity remains an important property to
determine the type of bond between atoms of element. Pauling in 1945 defined
electronegativity as “the ability of the atom of an element in a molecule to attract electron”.
Electronegativity ranges from (1 – 4). Elements in minerals are combined in different
amounts of a certain type of bond or of several types of bonds. The amount of each bond
depends on the difference in electronegativity between bonded elements.

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 University of Duhok / College of Spatial Planning and Applied Science / Department of Applied
Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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Elements are classified by electronegativity as follows:
1. Elements with electronegativity of (1.6) and less and capable of forming ionic bonds with
oxygen are lithophile.
2. Elements with electronegativity of (1.7 - 2.0) with the affinity of making covalent bonds
with sulfur are chalcophile.
3. Elements with electronegativity of (2.0 - 3.0) and combined by metallic bonds are
siderophile.
It is clear from the above that the increase in the difference in electronegativity of two
bonded atoms will results in an increase in the amount of ionic character of their bond, and
vice versa.

The degree of ionic character of a single chemical bond between an element (A) and oxygen (B) as a
function of the electronegativity difference |xA − xB|. An electronegativity difference of about 1.7
corresponds to a bond that is 50% ionic; bonds with larger electronegativity difference are primarily
ionic, those with a smaller difference are primarily covalent, but there are exceptions.

There is another way of subdividing the elements for geochemical purposes:

1. Major elements: usually considered to be above (1%). These include Si, (Ti), Al, Fe,
Mn, Mg, Ca, Na, K, and (P)… and H. These are typically given in weight percent oxide
(%wt.). Major elements above should total to about 100%. This is a general guide to
reliability.

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 University of Duhok / College of Spatial Planning and Applied Science / Department of Applied
Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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2. Minor elements: between 0.1% and 1%.
3. Trace elements: generally present in less than 0.1% of a rock (including rare earth
elements REE) and usually measured and expressed as parts per million (ppm) or billion
(ppb).
10,000 ppm = 1% 1,000,000 ppm = 100%
These include (but are not limited to):
- The transition elements = Sc, Ti*, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn.
- The Platinum group elements PGEs = Ru, Rh, Pd, Os, Ir, Pt, and Au.
- The Rare Earth Elements (REEs) = Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,
Lu.
- Other important ones.
Some elements behave as a major element on one group of rocks and as a trace element in
another group of rocks.
4. Volatiles (Gases): e.g. F, Cl, water (as both H2O and OH), CO2, SO2, etc. More
appropriately, they are the elements that easily enter the gaseous state at relatively low
temperature.
The case of water:
– Water released above 110 OC is described as H2O+. This is combined within the lattices of
(silicate) minerals.
– Water present in dampness in the rock powder and driven off by heating below 110 OC is
quoted as H2O-. This is simply loosely-held and not bonded and is not an important
constituent of the rock itself.
Sometimes the total volatile content of the rock is determined by ignition at 1000 OC and is
expressed as Loss on ignition (LOI) (i.e. heat rock to above 1000 OC).
Isotopes are subdivided into radiogenic and stable isotopes. Radiogenic isotopes include:
1) those isotopes which decay spontaneously due to their natural radioactivity and 2) those
which are the final daughter products of such a decay scheme. They include the parent-
daughter element pairs Rb-Sr, Sm-Nd, U-Pb, Th-Pb and K-Ar.

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 University of Duhok / College of Spatial Planning and Applied Science / Department of Applied
Geosciences / Geochemistry/ Third Stage / First Semester 2020-2021 / Ameer Hayder Khalid

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Stable isotopes studies in geology concentrate in the naturally occurring isotopes of light
elements such as H, O, Ca and S which may be fractionated on the basis of mass differences
between the isotopes of the element. Stable isotopes contribute significantly to an
understanding of fluid and volatile species in geology.
Abundances of the Elements in the Solar System:
• Hydrogen (H) is the most abundant element in the Universe; Helium (He) is second.
• Abundance of first 50 elements decreases exponentially.
• Abundance of elements with atomic number Z > 50 is very low and not predictable
variable abundance with increased Z.
• Even Z elements are more abundant than immediate neighbour odd Z.
• Li, Be and B anomalously low compared to other low Z elements because they are poorly
synthesized in the Big Bang and also in stars.
• Abundance of Fe is notably higher than other elements of similar Z because it represents
the minimum energy nuclide that can be made by fusion of helium in supernovae.
• Elements with Z > 83 have no stable isotopes but are found naturally because they are
long-lived daughters of U and Th. Elements such as Technetium (Tc) and Promethium
(Pm) not found in solar system because all their isotopes are unstable and decay rapidly.

Abundances of the chemical elements in the solar system in terms of atoms per 10 6 atoms of Si. The
data were derived primarily by analysis of carbonaceous chondrite meteorites and by optical
spectroscopy of light from the sun and nearby stars (Anders and Ebihara, 1982).

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