INTRODUCTION

 Definition of Geochemistry as a science. Object of study.

The study of a new science or discipline always implies the need to analyze its foundations,
conceptual system, branches, links with other sciences and methods used, together with an
adequate analysis of its emergence and historical development.
Geochemistry as a science is not immune to these requirements and, therefore, it is advisable
to initially refer to each of the topics that define it as such, which must be a starting point to
delve into the knowledge that came from its evolution. .
What is the object of study of Geochemistry?
The different aspects to be discussed in this book will be derived from the answer to this
question, this being an unavoidable principle in order to understand the essence of its
cognitive wealth and the possibilities of application for the benefit of society.
In first approximation, Geochemistry could be defined as the science that studies the chemical
processes that occur on Earth. Some consider it to be an intermediary between Geology and
Chemistry, giving it a hybrid meaning, proposing that Geochemistry takes those fundamental
facts of both sciences and applies them to the more exact determination of the chemical
phenomena that take place in nature.
These definitions could be considered valid in a first approximation, but if we delve deeper it
must be appreciated that Geochemistry goes beyond the mere application of Chemistry to
Geology.
The historical development of this science allowed it to be assigned a role at all times that
was expressed through various definitions, which show the points of view of numerous
scientists involved in its emergence and subsequent evolution.
F. W. Clarke (1924) in his classic book “The Data of Geochemistry” defines the object of
study of Geochemistry as follows:
“From various points of view, each rock can be considered as a chemical system where
different agents carry out chemical changes. Each of these changes implies a disturbance of
equilibrium and causes the formation of a new system, which, under the new conditions,
becomes stable. The study of such changes is the object of study of Geochemistry. The
mission of the geochemist is to determine what changes are possible, how and when they will
occur, observe the phenomena that accompany them, and record the final result... From the
geological point of view, the Earth's crust is its main object of study and the reactions that
occur in it can be classified into three large groups: 1) reactions between the essential
constituents of the Earth itself; 2) reactions due to its aqueous envelope; and 3) reactions
produced by atmospheric agents.”
In this definition the inclusion of everything that is chemistry in geology is palpable, leaving
its specific functions undefined. In this way, the very breadth of the object of study stated for
Geochemistry restricts its true role and excludes the participation of the biosphere.
For his part, the Russian geochemist A. AND. Fersman (1922) had incorporated significant
aspects that more clearly synthesized the object of study of this science, expressed in the
following terms:
“The purpose of Geochemistry is the study of the element-atom in the conditions existing in
the Earth's crust. Geochemistry studies: a) the quantitative distribution of elements in the
Earth's crust and their dispersion and local concentration; b) the combinations of elements in
the different parts of the Earth's crust and their distribution in space and time under the action
of different chemical processes; c) the migration of elements and the laws that govern such
migration determined by the thermodynamic conditions of the environment; d) the behavior
of chemical elements, both inside the Earth's crust and in the form of compounds and
particularly crystals. Expressed in the simplest way, it can be said that Geochemistry studies
the history of the elements in the Earth's crust and their behavior under various natural
thermodynamic and physicochemical conditions.

1
 Fersman considered that chemical processes in nature have an external thermodynamic
component and that elements have the capacity to migrate in time and space in different
ways, the inclusion of these concepts to characterize geochemical systems constituting a
novelty. Although he does not refer to the role played by living organisms in this definition, it
is no less true that he already gave great significance to the participation of the biosphere in
geochemical processes guided by the ideas developed by his teacher VI Vernadsky.
Vernadsky also, in a very summary manner, offers his opinion about the main characteristics
of this science:
“Geochemistry studies the chemical elements, that is, the atoms in the Earth's crust and, to the
extent possible, throughout the Earth. “She studies history, the genetic relationships with our
planet and the distribution in space and time of chemical elements.”
From this definition it is deduced that Geochemistry studies not only the historical
distribution of chemical elements but also their migration or displacement.
Lastly, V.M. Goldschmidt (1935) in his book “Geochemistry” describes Geochemistry in the
following terms:
“The fundamental objective of Geochemistry is to quantitatively determine the composition
of the Earth and its component parts, as well as to discover the laws that govern the
distribution of chemical elements. To solve these problems, the geochemist needs a broad
collection of analytical data on Earth materials such as rocks, water, air; It also uses analysis
of meteorites, astrophysical data on the composition of other cosmic bodies, and geophysical
data on the nature of the Earth's interior. The most valuable information comes from the
synthesis of minerals carried out in the laboratory and the investigation of their modes of
formation and their stability conditions.”
In Goldschmidt's definition it can be seen that for the geochemist, geological observations are
aimed at establishing the abundance and distribution of chemical elements on Earth,
establishing links with the chemical composition of extraterrestrial matter.
As a summary, it can be established that Geochemistry studies:
1- The determination of the absolute and relative abundance of chemical elements and their
nuclides on Earth.
2- The study of the distribution of chemical elements and their nuclides in the different
component parts of the Earth.
3- The determination of the forms of existence of chemical elements in nature.
4- The analysis of the factors that contribute to the migration of chemical elements in
different natural conditions.

GEOCHEMIST
RY

CHEMICAL ELEMENTS LAND

(NUCLIDIOS) (EARTH CRUST)

Abundance Distribution Ways to Migration Endogeno Exogenous

existence us systems systems

 Branches of Geochemistry.

2
As an immediate result of its own historical development as an integral part of the scientific-
technical revolution in which the sciences are immersed in the 20th century, Geochemistry as
a science acquired an extraordinary boom that led to its ramification. In this way, the great
wealth of knowledge accumulated since its emergence has led to its subdivision, keeping the
roots of this science unchanged and enabling a more rational distribution of its themes. This
can be seen briefly in the following synoptic table:

 Relationship of Geochemistry with other sciences and disciplines.

Geochemistry, as a result of the development of science and technology itself, has established
unilateral and/or bilateral links with other sciences and disciplines. In this way, it has
managed to draw on methods that favor the creation of its own system of concepts, laws,
definitions, rules, etc., typical of the natural sciences. These links have also meant that much
scientific knowledge achieved in the light of geochemical ideas has immediate impact and
can be applied in other sciences.
Below is a schematic representation of a model of the relationships established by
Geochemistry with other sciences. The arrows constitute a symbolic index of the reciprocity
or not that exists in the established links: the double arrow will indicate, therefore, that the
dependence and benefit in the links is bilateral, while a single arrow means the direction of
the science that is benefited from that link.
The mutual relationships between Geochemistry and its original sciences (Geology and
Chemistry) are very complex, so a detailed analysis of these links would be too extensive.
Chemistry provided very valuable basic information that contributed to creating the basis of
the system of concepts and laws of Geochemistry, considering that chemical elements (and
their nuclides) represent an important part of its object of study; It also provided analytical
methods for determining the relative and absolute abundances of chemical elements (and their
nuclides) in the different component parts of the Earth (rocks, minerals, soils, waters, air,
plants, etc.). Geochemistry, for its part, provided Chemistry with a broader field of action in
which the laws of nature could be verified, based on the establishment of rules and
generalizations that have expanded the spectrum of application of the properties of chemical
elements to geochemical processes and using the stability of the atomic nucleus to
demonstrate the unequal abundance of chemical elements in nature.

OPTICA NUCLEAR SISMICA RADIOMETRIA

COSMOQUIMICA
FISICA GEOFISICA

QUIMICA GEOLOGIA
FISICA ESTRUCTURAL

QUÍMICA GEOQUIMICA GEOLOGIA

ANÁLISIS GEOLOGÍA
QUÍMICO HISTÓRICA
MINERALOGÍA

MATEMÁTICA PETROGRAFÍA

 Brief overview of the emergence and development of geochemistry.

3
1- Emergence of Geochemistry as a science.
Christian Friedrich Schonbeing (1799-1868); Swedish chemist. He used the term
"geochemistry" for the first time in 1838.
J. Berzelius (1779-1884). He actively participates in the development of mineral chemistry
as an immediate preamble to the emergence of geochemistry.

2- Events related to the initial stage of development of Geochemistry.

Discovery of most chemical elements at the end of the 19th century, linking this fact mainly
with rocks and minerals.
Discovery of the Periodic Law of chemical elements by D. YO. Mendeleev (1867).
Discovery of radioactivity by the Curie couple.
Discovery and description of the crystalline structure of minerals using X-rays.
Discovery of the atomic structure.

3- Main scientists and events linked to the development and consolidation of

geochemistry.
Frank W. Clarke (1847-1931); American mineralogist chemist. He publishes the article "The
relative abundance of chemical elements" (1889) and the book "The Data of Geochemistry"
( ).
V. M. Goldschmidt (1888-1947); Norwegian mineralogist. He exposes his hypothesis about
the structure and internal composition of the Earth (1922), proposing a geochemical
classification of the elements that is still valid. He publishes the book "Geochemistry" ( ),
which is one of the classic books of this science.
Vernadsky (1863-1945); Russian mineralogist and geochemist. Actively participates in the
completion of the system of concepts, laws, rules, etc. that theoretically base this science. It
contributes to the incorporation of the biosphere into the field of action of Geochemistry,
giving rise to the emergence of Biogeochemistry.
TO. Fersman (1883-1945); Russian geochemical mineralogist. Actively participates in the
behavior of the system of concepts, laws, rules, etc. From Geochemistry, together with Clarke
and relating it to their location in Mendeleev's Periodic system. His ideas are successfully
applied in the development of mineral deposits on the Kola Peninsula, thus contributing to the
emergence and application of geochemical prospecting methods.
TO. Q. Vinogradov ( ); Russian geochemist, develops and consolidates biogeochemical and
geobotanical methods applied to the prospecting of mineral deposits, as a faithful follower of
Vernadski's ideas.
In recent years, multiple novel applications of geochemistry have been reported, highlighting:
the study of geotectonic environments of rock formation and mineral deposits; isotopic
studies aimed at clarifying the origin of rocks, ore-forming fluids and mineral deposits;
environmental studies, etc.

4
 CHAPTER I

ABUNDANCE AND DISTRIBUTION OF CHEMICAL ELEMENTS (AND THEIR

NUCLIDIES) ON EARTH

1.1- Geochemistry and Cosmochemistry.

Cosmochemistry is the science that studies the chemical composition of cosmic bodies (stars,
planets, satellites, comets, meteorites, interstellar matter, etc.), the abundance and distribution
of chemical elements in the Universe, as well as the nuclear processes that occur in stars that
give rise to the formation of chemical elements (Fig. 1.1).
The study of cosmic phenomena from the point of view of Cosmochemistry contributes to the
achievement of superior knowledge about the processes that occur in the Universe, to the
definition of hypotheses about the formation of the Solar System and to consolidate ideas
about the structure and internal composition of the Earth.

COSMOCHEMIST
RY

CHEMICAL ELEMENTS
UNIVERSE
(NUCLIDIOS)

Abundance Distribution Ways to Migration

existence

Fig. 1.1- Object of study of Cosmochemistry

1.1.1- Universal abundance of chemical elements.

To estimate the universal abundance of chemical elements, researchers have resorted to
processing numerous data referring to the chemical composition of meteorites, solar and
stellar matter, comets and the rocks that make up the Earth's crust.
The first table with reliable information on the universal abundance of elements was proposed
by Goldschmidt (1937), based on the information available up to that year. Later, Suess and
Urey (1956), through careful compilation, review and processing of new data, published their
results which reflected some differences in details with respect to the previous ones but,
essentially, kept its main features unchanged (Table 1.1 ).

5
Table 1.1
Cosmic abundance of the elements.

Cosmic Cosmic Cosmic

abundance abundance abundance
Element Z (atoms per Element Z (atoms per Element Z (atoms per
10,000 Si 10,000 Si 10,000 Si
atoms) atoms) atoms)
h 1 4·108 Ge 32 0.51 eu 63 0.002
I have 2 3.1·107 Ace 33 0.04 gd 64 0.007
Lee 3 1 HE 34 0.68 tb 65 0.001
Be 4 0.2 Br 35 0.13 Dy 66 0.006
b 5 0.24 Kr 36 0.51 Ho 67 0.001
c 6 35000 Rb 37 0.07 Er 68 0.003
N 7 66000 Mr 38 0.19 Tm 69 0.0003
EITHER 8 215000 AND 39 0.09 Yb 70 0.002
F 9 16 Zr 40 0.55 Lu 71 0.0005
ne 10 86000 Nb 41 0.01 Hf 72 0.004
na 11 440 mo 42 0.02 ta 73 0.0007
Mg 12 9100 tc 43 - W 74 0.005
To the 13 950 Ru 44 0.015 Re 75 0.001
Yeah 14 10000 Rh 45 0.002 You 76 0.01
Q 15 100 P.S 46 0.007 Go 77 0.008
Yes 16 3750 Ag 47 0.003 Pt 78 0.016
CL 17 90 CD 48 0.009 Au 79 0.001
Ar 18 1500 in 49 0.001 Hg 80 0.003
K 19 32 Yes 50 0.013 Tl 81 0.001
AC 20 490 Sb 51 0.002 Pb 82 0.005
Sc 21 0.28 Tea 52 0.047 Bi 83 0.001
You 22 24 Yo 53 0.008 po 84 -
V 23 2.2 Xe 54 0.04 At 85 -
Cr 24 78 cs 55 0.005 Rn 86 -
mn 25 69 Ba 56 0.037 Fr 87 -
Faith 26 6000 The 57 0.02 Ra 88 -
Co 27 18 EC 58 0.023 Ac 89 -
Neither 28 270 Pr 59 0.004 Th 90 0.0004
Cu 29 2.1 nd 60 0.014 Da 91 -
Zn 30 4.9 P.m 61 - OR 92 0.0001
Ga 31 0.11 YE 62 0.007

It is necessary to clarify that the tabulated information does not represent the chemical
composition of a cosmic object or of particular geochemical systems, but rather is an
approximate expression of the chemical composition of the Universe as a whole. It should be
noted that such data are useful to substantiate the physical, chemical and physicochemical
processes involved in cosmochemical (chemical differentiation of the Universe) and
geochemistry (chemical differentiation of the Earth) evolution.
A fuller appreciation of the regularities about the universal abundance of elements can be
achieved by graphically representing their variations as a function of atomic number (Fig.
1.2).

6
 9
H
8 H e

6 E le m e n to d e n ú m e ro a tó m ic o im p a r
L o g a ritm o d e la a b u n d a n cia có sm ica

O
N e E le m e n to d e n ú m e ro a tó m ic o p a r
5 C
N
M g Si
4 S
Fe

Ar
3 Al
C a
N i
Na
C r
2 P Cl Ti Mn
K
1 F Co Zn

0 Li
V Cu G e Se Kr Zr
Be Sr
Sc
-1 B
Ga Br Te Xe Ba
Rb Y M o R u C e
As Sn N d Pt
O s
Pd C d
-2 Nb
La Sm G d D y
Er H f W H g
Pb
I Yb Ir
Cs Pr
Ag
-3 Rh
In
Sb Eu
Tb Ho Re Au Tl Bi Th
Ta
Lu
Tm U
-4

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95
N ú m ero atóm ico

Fig. 1.2- Relationship between the universal abundance of the elements and the atomic
number.

The analysis of this graph allows us to reach the following conclusions:

1- The universal abundance of elements tends to decrease with increasing atomic number.
For elements with low atomic numbers (Z<30), a sharp exponential decrease in their
logarithmized universal abundances is observed, while in the rest this trend is smoother.
2- The universal abundances of elements with atomic numbers higher than nickel (Z=28)
vary less than those of those with lower atomic numbers.
3- Only ten elements (H, He, C, N, O, Ne, Mg, Si, S and Fe), all of them with an atomic
number less than 27, show appreciable universal abundances; Among them, hydrogen and
helium predominate notably.
4- Elements with even atomic numbers are more abundant in the Universe than those with
odd atomic numbers (except hydrogen). This regularity had been predicted by Harkins
and Wilson (1915) when presenting their theory on the structure and stability of atomic
nuclei. Harkins (1917) demonstrated this idea by finding that the seven most abundant
elements in meteorites (O, Fe, Ni, Si, Mg, S and Ca) constitute 98.6% by mass of
meteoritic matter; He was also able to verify the validity of this rule in the Earth's crust,
determining that six of the most abundant elements are of even atomic number (O, Si, Fe,
Ca, Mg and Ti) and represent 85.74% by mass of it, while three other elements of odd but
small atomic number (Al, Na and K) constitute only 12.77%.
5- Elements of even atomic number are almost always more abundant than the two adjacent
elements of odd atomic number. This regularity was predicted by Oddo (1914) and
Harkins (1917), and is currently recognized as the Oddo-Harkins rule. According to
Harkins (1931), in those particular cases in which this rule does not hold, the abundance

7
 of the element with even atomic number is greater than the arithmetic mean of the
abundances corresponding to the two adjacent elements.
6- Some elements with significant atomic numbers (Z=43, Z=61 and Z>92) are extremely
deficient, because they show notable natural radioactivity.

According to what has been discussed, it is possible to infer that the abundance of the
elements depends largely on the atomic number and not on their position in the Periodic
System. This suggests that nuclear properties (related to the structure and stability of the
atomic nucleus) govern the abundance of elements, rather than chemical properties (linked to
the electronic structure of the atom). From here it is necessary to demonstrate the relationship
between the structure of the atomic nucleus and the abundance of nuclides.

1.1.2.- Position of the Earth in the Universe.

The Universe is made up of billions of nebulae, galaxies and many cosmic bodies of
relatively small dimensions.
The Earth, represented as a significant point in the Universe, is the third planet of the Solar
System, which, in turn, is an integral part of a galaxy called the Milky Way.
Due to its shape, our galaxy resembles a biconvex lens, surely of similar dimensions and
shapes to those of other galaxies, the diameter of the Milky Way being 100,000 light-years. A
considerable part of the stars of the Milky Way (including our Sun) rotate around its center of
gravity in orbits, whose shape is close to circular, close to the plane of symmetry of the
galaxy; Another part, in its movement, moves considerably away from the plane of symmetry
of the Milky Way, and the shapes of its orbits differ greatly from the circular one.
Together with other stars, the Sun rotates around the center of mass of the Milky Way with a
rotation period of 100-250 million years. The distance from the Sun to its center is around
30,000 light-years.
In addition to the Sun, the Solar System is made up of nine planets (Mercury, Venus, Earth,
Mars, Jupiter, Saturn, Uranus, Neptune and Pluto), several natural satellites, an asteroid belt
(located between Mars and Jupiter), comets and other cosmic bodies of small dimensions
(Fig. 1.3).

Fig. 1.3- Structure of the Solar System.

The Earth moves around the Sun at an average speed of 30 km/s and makes one complete
revolution every 365.25 days, following a weakly elongated elliptical orbit that approximates
a circle with a radius of 149.5 million kilometers. At the same time, the Earth rotates on itself
(according to a slightly inclined axis) at such a speed that it completes one revolution after 23
hours and 65 minutes.
Its only natural satellite revolves around the Earth: the Moon, which describes a rather
eccentric and complex orbit, moving with an average speed of 1.2 km/s.

8
 Ideas regarding the origin of the Solar System.
All the information that man has been obtaining as a result of astronomical, astrophysics,
cosmochemical and other research has enormous significance in elucidating the much-
discussed problem of the formation of the Solar System. Thus, humanity approaches day by
day to the discovery of the truth about this secret that, without a doubt, has scientific
implications, including philosophical conceptions.
Currently, it is proposed that the validity of any scientific theory or hypothesis about the
origin of the Solar System is determined by its correspondence with the different
astrophysical observations and the values of the most important physical parameters (table
1.2) of the Sun and the planets that surround it. they surround

Table 1.2
Main physical parameters of the Sun and planets.

Average
Radio Density
distance to Mass
Solar system Half (g/cm 3 )
the Sun
Compared to Earth
Sun - 109,1 333 400 1,41
Mercury 0,39 0,38 0,055 5,44
Venus 0,72 0,97 0,815 5,25
Land 1,00 1,00 1,00 5,42
Mars 1,52 0,53 0,107 3,94
Jupiter 5,20 10,95 318,05 1,33
Saturn 9,54 9,02 95,147 0,69
Uranus 19,19 4,00 14,58 1,26
Neptune 30,70 3,92 17,23 1,67
Pluto 39,52 0,46 0,1 4,90

From the analysis of this table and other known astronomical and astrophysical data, some
interesting regularities can be seen that can serve as a basis for critically evaluating the
fundamental hypotheses stated about the origin of the Solar System. Among these
regularities, the most important are:
1. The Sun contains more than 99.8% of the mass of the Solar System as a whole.
2. All its planets revolve around the Sun in the same direction in almost circular orbits,
practically in the same plane. The greatest deviations from this are observed in the extreme
planets (Mercury and Pluto), which also have more elongated elliptical orbits.
3. The rotation of the planets around their axes coincides in direction with that of the Sun,
with the exception of Venus and Uranus; most satellites rotate in the same direction. The
axes of rotation of most planets form a nearly right angle to the plane of their orbits.
4. Most of the kinetic momentum of the Solar System is concentrated in the planets (98%),
even though the mass concentration is in the Sun.
5. The planets show a somewhat regular distribution, forming two contrasting groups: 1)
Mercury, Venus, Earth and Mars (terrestrial or inner group planets); 2) Jupiter, Saturn,
Uranus and Neptune (giant or outer planets).
The planets of the terrestrial group are characterized by: small dimensions, high density,
small mass and insignificant speed when rotating around their axes. They have few
satellites: Earth (1) and Mars (2), whose densities are close to those of the corresponding
planets.

9
 Giant planets are characterized by having: immense dimensions, low density, considerable
mass and high rotation speeds that cause strong contraction at the poles; They have
numerous satellites: Jupiter (12), Saturn (10), Uranus (5) and Neptune (2). Due to their
physical characteristics, these satellites resemble the planets of this group, and the density
of some Saturn satellites drops to 0.1 g/cm 3.
According to the hypothesis formulated by the English theorist R. TO. Litleton, Pluto may
have been a former satellite of Neptune which moved away from the latter as a result of its
approach (collision) with Triton. For some years now, this hypothesis has been highly
discussed, especially after Pluto's satellite was discovered, and there is no reliable
explanation for the origin of the strange double system of Pluto and its satellite on the
periphery of the Solar System.
6. The movement of asteroids and planets is quite similar. Most asteroids move in circular
orbits in the same direction as all planets. The plane of their orbits is close to the total
plane of the system's orbits. It means that the asteroids are large pieces of a tenth planet in
the Solar System (called Phaethon) that was destroyed due to a cosmic catastrophe and has
even been destroyed. propose that Phobos (one of the satellites of Mars) represents one of
these fragments attracted by the gravitational field of Mars.

In accordance with everything explained up to this point, it is now possible to delve into the
critical analysis of the most important hypotheses stated about the origin of the Solar System.
To do this, it must initially be stated that there have been two fundamental trends in this
sense: hot or nebular origin, cold or meteoric origin.

 Kant-Laplace hypothesis.
Among the numerous hypotheses formulated about the origin of the Solar System, the one
independently presented by the German philosopher I. Kant (1755) was absolutely valid for
more than a century. According to this hypothesis, the Solar System was formed from an
enormous incandescent nebula that rotated around a central axis. The initial dimensions of
this nebula were much larger than the current dimensions of the Solar System. As time went
by, the nebula cooled and, therefore, its dimensions decreased, with a consequent increase in
its rotation speed and centrifugal force. Gradually, the nebula became more and more
flattened, widening around the equator, thus acquiring a disk shape, rings of water began to
separate. The cooling of the rings led to their disintegration and the grouping of the substance
forming the primitive planets, while the Sun was formed in the core of the nebula. Rings
could also separate from these planets, which, finally, fragmented and agglomerated, forming
satellites (fig. 1.4).

10
 Fig. 1.4- Scheme of the formation of the Solar System (according to Kant and Laplace).

According to this hypothesis, the formation of the planets and their satellites began before the
sun had been completely structured. The physical-mechanical argument for this hypothesis
was stated by Laplace based on different astronomical observations made on nebulae that
have different degrees of compression, and assuming that these were similar to the one that
gave rise to our Solar System.
The further progress of astronomy has shown that the visible nebulae of the Universe are not
gaseous clouds gradually concentrating into stars and planets, but gigantic galaxies separated
from us by enormous distances.
This hypothesis managed to explain many structural peculiarities of the Solar System, such
as: the unique direction of rotation of the Sun and the planets, the shapes of the planetary
orbits close to circular, etc.
However, as new data about the structure of the Solar System became available, many
contradictions arose that made it inconsistent. From here a series of criticisms were derived,
among which the following stand out:
1- It does not explain the causes of the opposite rotation of some planets (Venus and Uranus)
and several of their satellites (Mars, Jupiter).
2- It is incompetent to argue the observed differences in density, dimensions and mass
between the planets of the terrestrial group and the giant planets.
3- It does not provide a solution to the problem of the anomalous distribution of kinetic
moments between the Sun and the planets.

 Schmidt's hypothesis.
The hypothesis proposed by the Soviet academic O. AND. Schmidt (1944) included a
fundamentally new idea that considered the “cold” origin of the Solar System.
He assumes that the Sun and the planets originated from different sources. In one of the
phases of its development, the sun (whose origin is not examined) attracted a cold nebula of
gas and dust into the galaxy, which had its own considerable kinetic momentum. The rotation
in the strong gravitational field of the sun led to a complicated redistribution of meteoric
particles (according to mass, density, dimensions). Originally these particles moved around
the sun in elliptical orbits with the most variable eccentricities and directions. The emergence
of collisions between these particles caused their orbits to become less eccentric until most of
them were approaching a central plane. The result of this was that the nebula flattened and
condensed, with collisions (collisions) becoming more frequent, accumulating the particles in

11
a disk of much greater density than the original nebula. Upon reaching a certain critical
density, the system of small particles became unstable, and under the influence of the gravity
of those of larger masses, the first condensations of mass (comparable to that of asteroids)
were formed, which constituted the embryos of the future planets. The incorporation of
dispersed dust particles led to an increase in the dimensions of all initial condensations; At the
same time, the gravitational fields of these embryos were intensifying, thus facilitating the
capture of all the particles that moved in their vicinity. Finally, from a small number of these
massive bodies the planets originated and continued to move around the Sun in a direction
equivalent to that of the original cloud (fig 1.5).

Fig. 1.4- Formation of the Solar System according to the hypothesis of

O. AND. Schmidt (1944). (Taken from the book General and Historical
Geology, Editorial Mir, 1981).

In a similar way, the satellites of each planet were formed, which were trapped by the
gravitational field that corresponds to them and, by virtue of this, kept rotating around them.
During the process of planet formation, a chemical differentiation of the original dust and gas
nebula occurred, as a result of the action of solar radiation on the particles that composed it.
This led to the fact that, in the regions close to the Sun, there were no volatile compounds
(NH 3 , CH 4 , H 2 O) since these volatilized and moved to the outermost regions of the
nebula, where temperatures were close to zero. absolute with which you favor the
solidification of these gases. Hence, in the innermost part of the nebula, only the compounds
with the highest fusion temperatures (silicates and some metals) remained. This is how
Shmidt explains the differences that can be seen between the physical parameters of the
planets of the terrestrial group and the planets. giants; The first would originate mainly from
the silicate compounds and metals that were abundant in the inner part of the nebula, while
the others were formed due to the accumulation of frozen volatile compounds that constituted
most of the mass of the original nebula.
According to Schmidt's hypothesis, the Earth's initial thermal state was cold. The heating of
the Earth's depths was linked to radioactive decay processes that caused an intense release of
heat and, as a result, the partial melting of the Earth's interior would occur.
Something similar is supposed to have happened in the initial stages of consolidation of the
remaining planets, thus explaining the gravitational differentiation of the substance inside
them and the formation of concentric layers as an immediate result of this.

12
EITHER. AND. Schmidt and later his disciples presented a serious physico-mathematical
argument for this model of formation of the planets of the Solar System, from which they
estimated at what distances they must have arisen from each other. Amazingly, these
theoretical calculations coincided almost exactly with the actual distances separating the
planets from the Sun.
In summary, this hypothesis convincingly explains the particularities of the movement of the
planets (shape of the orbits, rotation in various directions, etc.), their real distribution
according to their masses and densities, the relationship between the planetary kinetic
moments and the solar kinetic moment, etc.
The main flaw of Schmidt's hypothesis lies in the low probability that the Sun has attracted a
nebula of gas and dust from the galaxy, because for this to occur the gravitational support of
another nearby star is necessary, the coincidence of these two conditions is quite unlikely, so,
if it had occurred, it would represent an extraordinary event.

 Fesenkov hypothesis.
The academic V. g. Fesenkov (1960) related the origin of the Solar System to the general
laws of formation of matter in cosmic space. This hypothesis conceived that the Sun and the
planets had formed within the limits of a gigantic nebula (globule), made up of a rather
rarefied matter (with a density of 10 -22 g/cm 3 ) represented mainly by hydrogen, helium and
a small amount of heavier elements. At first, the Sun was formed in the core of this nebula,
which was a hotter and more massive star than today. As a result of certain energy emission
processes, the Sun began to compress rapidly and its rotation speed to increase. These
processes caused the increase in centrifugal force and, consequently, repeated eruptions of
solar matter into the protoplanetary cloud that surrounded the Sun.
In this way, the Sun lost part of its mass and transmitted a considerable part of its kinetic
momentum to the planets that were forming. The calculations show that by counting on non-
stationary eruptions of matter from the interior of the Sun, a practical relationship could be
formed between the kinetic moments of the Sun and the protoplanetary cloud equivalent to
that currently observed between the Sun and the planets. The mechanism of planet formation,
according to this hypothesis, is similar to that proposed by Schmidt although, in this case, the
primary material was made up of condensed drops (chondras) of solar matter. The evolution
of the planets formed was oriented towards radiogenic heating (due to the radioactive decay
processes of the isotopes 40 K, 238 U, 235 U, 232 Th) and towards the partial fusion of their
interior.
Although some points of view were correct, this hypothesis also raised a series of objections,
of which the most important are:
1. Even admitting that the planets could have formed from the irruptions of solar matter
towards the protoplanetary cloud, it remains unexplained where the force that later
separated the planets, originating in the vicinity of the Sun, arose at the enormous
distances that exist today. .
2. The differences in the chemical composition of the Sun and the Earth cannot be
explained. Hydrogen and helium represent around 90% of its mass in the Sun, while on
Earth their quantities are insignificant.

Many other ideas have been put forward by numerous scientists from different parts of the
world, but, among them, one of the most interesting is put forward by the British
astrophysicist and science writer J. Gribbin in his article "How the blue planet was formed",
published in the magazine "The UNESCO Courier" (July, 1986), states that the Sun was
formed, just a little more than 4,550 million years ago, from of a hydrogen cloud that
contained in abundance elements such as iron, carbon, oxygen and nitrogen, which were
"sedimenting" from the cloud to form the planets. In the specific case of the formation of the
Earth, it is assumed that a small cloud that was probably composed of silicon, iron oxides and

13
magnesium oxides with a small amount of the rest of the elements, was what caused this
process. The formation of the Earth was accompanied by an increase in temperature due, first
of all, to the conversion of gravitational force into heat as particles fell and collided with the
protoplanet. In addition, the radioactive sediments contributed their share of heat as their
isotopes decayed, becoming stable atomic species.
In the first tens or hundreds of millions of years of its existence, the young iron-rich planet
must have been in a state of fusion, so globules of molten iron penetrated to the Earth's core
through the less dense rocky matter. , which remained on top, and when the crust cooled, it
formed a solid envelope; This constituted the beginning of a process of separation by layers
that was more or less completed 3.9 billion years ago.

1.1.3- Study of meteorites.

For many years, meteorites represented the only extraterrestrial bodies within the reach of
man, becoming the most appreciated samples by scientists for the study of the composition
and properties of interplanetary and interstellar matter. Fersman would designate them as
"emissaries of the Universe," a name that constitutes a faithful reflection of the invaluable
information that they are capable of providing about the history of the universe and in
relation to the evolution of cosmic bodies.
There were many scientific discussions around the problem of the origin of meteorites.
However, it is currently a general opinion in scientific circles that these bodies come from the
asteroid belt (whose orbits are located between Mars and Jupiter), so they represent fragments
of asteroids or complete asteroids that deviated from their orbits and became oriented. to the
Sun falling on the planets of the terrestrial group and its satellites. This leads to the
assumption that the meteorites constitute parts of a planet in the Solar System (similar in its
general physicochemical properties to the Earth), called Phaethon, which was destroyed as a
result of a cosmic catastrophe during the initial stage of its existence. By assuming that these
must be representative of their different parts, their study makes it possible to indirectly
evaluate the chemical composition of our planet and that of the remaining inner planets.
Meteorites are made up of three phases: metallic, silicate and sulfurous; However, the first
two are the most distributed among the meteorites found.
Precisely, the modern classification of meteorites is based on the proportions observed
between the silicate phase and the metallic phase in the wide variety of samples collected.
Accordingly, these cosmic bodies are divided into: ferrous meteorites or siderites,
petroferrous meteorites or lithosiderites, and stone meteorites or lithites.

 Iron meteorites or siderites

These meteorites are composed entirely of iron-nickel alloys: kamacite (with an approximate
content of 60% Ni) and taenite (which contains approximately 30-40% Ni). Other minerals
that are frequently included in small proportions are: troilite (FeS), schreibersite (Fe, Ni, Co)
3 P), cohenite (Fe 3 C), daubreelite (FeCr 2 S 4 ), oldhamite (CaS), graphite ( C), lawrensite
(FeCl 2 ), etc. (fig.1.5).

14
 Fig. 1.5- Siderite showing corrosion
surface
The fall frequency of the siderites is 5.7% and the average density corresponding to them is
close to 8 g/cm 3 . Their structures represent proof that they have cooled very slowly, which is
not common for natural processes that occur on Earth.
According to the characteristics of their structure, siderites are divided into: hexahedrites,
octahedrites and ataxites. However, these groups cannot always be distinguished in a defined
way, since they usually transition from one to another in a more or less gradual way.
Hexahedrites contain essentially kamacite, without taenite or plessite (mixture of kamacite
and taenite). Therefore, its nickel content is approximately 5-6%. Kamacite is found in
hexahedrites in the form of rounded or irregular grains. When their polished surfaces are
subjected to corrosion, lines parallel to each other usually appear, which are called Neyman
lines.

Fig. 1.6 – Sección de un octaedrito mostrando

la estructura de Widmanstatten.

The octahedrites are made up of kamacite plates that are surrounded by a thin layer of
taenite, and the interstices filled with plessite; It generally contains 6-13% nickel. The

15
kamacite plates are discovered when the octahedrites are sectioned, polished and corroded
with alcoholic solution of nitric acid (HNO 3 ), thus showing a network of intersecting
crystals which is called the Widmanstatten structure (fig. 1.6). In this lattice the kamacite
plates are arranged following the planes of an octahedron. The Widmanstatten model results
from the decomposition of an original solid solution of taenite at high temperatures, the
kamacite precipitating with the slow cooling of this iron-nickel alloy. The presence of the
thick Widmanstatten structure suggests that the precipitation of kamacite occurred under
conditions of very slow cooling, which is controlled by diffusion.
In this type of meteorites it is common for there to be a general relationship between the
amount of nickel, the presence of the Widmanstatten structure and the thickness of the bands.
Generally, this pattern is fine in octahedrites with high nickel contents; but other factors, such
as phosphorus and cobalt impurities could play an important role in the formation of this
structure.
Ataxites are mainly composed of taenite, corresponding, accordingly, to nickel contents
greater than 13%. These meteorites do not show any defined structural arrangement when
examined under a microscope, when their polished surfaces are subjected to corrosion with
acids.

 Petroferrous meteorites or lithosiderites .

Lithosiderites are mainly made up of iron-nickel alloys and silicate minerals in approximately
equal quantities. The silicate is generally olivine, but sometimes it can be pyroxene and
plagioclase, appearing in the form of more or less rounded grains included in spongy
formations of iron-nickel alloys.

Fig. 1.7- Superficie pulida de un pallasito compuesto

por cristales de olivino redondeados; ellos aparecen
oscuros envueltos por una matriz clara de hierro-
níquel.

It is considered that these form a transitional group between siderites and lithites, representing
only 1.5% of the meteorites found. Their corresponding density ranges between 5-6 g/cm 3.
Based on the composition of the silicate phase, lithosiderites are divided into: pallasites and
mesosiderites.
The pallasites are formed by a continuous base of iron-nickel alloy that includes
disseminated olivine (up to 40%) in the form of more or less rounded crystalline grains (fig.
1.7).
Small inclusions of troilite (FeS) and schreibersite (Fe, Ni, Co) 3 P) frequently exist in the
iron-nickel alloy. The metallic phase usually shows the Widmanstatten figures. It is suggested
that their formation occurred through the intrusion of an iron melt (containing considerable

16
amounts of iron sulfide) into an accumulation of olivine crystals. Thus, the metallic phase of
the pallasites represents samples of the original melt from which the different types of
siderites were formed.
The mesosiderites present a discontinuous iron-nickel metallic phase, and the silicates are
mainly represented by plagioclase, feldspars and orthopyroxenes, with accessory olivine
sometimes appearing.

 Stone meteorites or litliths.

In the stone stones, a predominance of the silicate phase over the metallic phase (iron-nickel
alloys) is observed. This silicate phase is mainly represented by olivine, hypersthene,
plagioclase and diopside. They constitute 92.8% of the meteorites collected and have an
average density of almost 3.5 g/cm 3 .
Based on the particularities of their structure, stone stones are divided into: chondrites and
achondrites.

Fig. 1.8- Litito (condrito). Una corteza de fusión

delgada con surcos cubre su superficie (Miller,
Arkansas).
Chondrites are the most widespread type of meteorites, reaching 85.7% occurrence. They
owe their name to the presence in them of rounded grains (chondrules) that are composed of
olivine and rhombic pyroxene. These consist of olivine (40%), rhombic pyroxene (30%),
iron-nickel alloy (10-15%), plagioclase (10%) and troilite (5-6%) (fig. 1.8).

Achondrites lack chondrules and are much less common than chondrites, accounting for only
7.1% of meteorites found. They are structurally similar to terrestrial rocks, but frequently
contain small amounts of iron-nickel alloy. They are composed of olivine (12-13%), rhombic
pyroxenes (50%), plagioclase (25%), diopside (12%) and iron-nickel alloy (1%).
To finally summarize the study of meteorites, it is convenient to check the chemical
composition of the 3 main classes of these (table 1.3).

Table 1.3
Average chemical composition (% by mass) of
meteorites (according to E. L. Krinov).

Chemical Meteorite type

elements Sideritos Lithosiderites Lititos
Faith 89,7 49,4 25,15
Neither 9,1 5,0 1,10

17
 Co 0,62 0,25 0,14
Q 0,18 - 0,10
c 0,12 - 0,16
Yes 0,08 - 1,89
Cu 0,04 - 0,01
EITHER - 21,30 36,30
Mg - 14,20 14,30
Yeah - 9,75 13,00
na - - 0,30
To the - - 0,76
AC - - 1,30
K - - 0,07
mn - - 0,18

The studies carried out on the mineralogical, chemical and isotopic composition of meteorites
have provided results of great interest for geochemistry:
1- In meteorites there is not a single chemical element that is not known on Earth.
2- A complete identity of the isotopic composition was obtained for a set of chemical
elements from terrestrial and meteoritic materials.
3- The age of the meteorites (determined by radiometric methods) has been found to be
3800-3900 million years, which is very close to the age of the oldest rocks discovered on
Earth (3800 million years).
4- There are some minerals in meteorites that have not been found on Earth, which could be
related to the lack of knowledge of the mineralogical composition of the bowels of our
planet. Among these minerals the most typical are: taenite, kamacite, plessite,
schreibersite, troilite, oldhamite, daubreelite, lawrencite.
5- The differentiated chemical composition of siderites, lithosiderites and lithites has made it
possible to evaluate the physical characteristics of the hypothetical planet Phaethon.
Furthermore, this chemical differentiation constitutes evidence that a similar process
could have occurred on Earth, and serves as an argument in favor of a heterogeneous
structure and composition for the interior of our planet.
6- The analogies found between meteorites and the Earth allow us to consider that they had a
common origin in the Solar System.

In this way, the study of meteorites is completed by subsequently analyzing the data collected
in recent years on the characteristics of other bodies in the Solar System. Some of them have
been obtained directly from different analyzes carried out on rock and gas samples collected
during space expeditions to the Moon and Venus, while others resulted from the application
of indirect methods (mainly spectral analysis) to determine the composition. chemistry of the
surface of the planets and their atmospheres, in addition to that of comets.

1.1.4- Study of the planets, satellites and other bodies of the Solar System.
The Moon represents, after meteorites, the cosmic body most studied by man, which is
explained by its relative proximity to the Earth.
The study of rock samples brought from the Moon by the Soviet automatic interplanetary
station "Luna-16" and by the North American "Apollo" spacecraft has contributed to
clarifying the chemical composition of the lunar surface. According to these data, primitive
lunar rocks present a deficiency of Ni, Co and noble metals, with some differences existing
between maritime basalts and continental anorthosites in terms of physical properties,
chemical composition and mineralogical composition.

18
Maritime basalts cover approximately 17% of the Moon's surface, with a maximum thickness
of around 1 km, so continental anorthosites and gabbro-anorthosites constitute the main
components of the crust. Lunar basalts are similar in composition to terrestrial basalts,
although in some samples a high content of titanium, zirconium, etc. was obtained; Likewise,
lunar anorthosites are close to the composition of terrestrial ones. Maritime basalts have high
iron content (approximately 20% FeO), while the anthracites of the continents contain almost
no this element. The gabbro-anorthosites of the continents have an approximate content of 4-
5% FeO and, finally, in non-maritime basalts the FeO content is around 9-10%. Continental
rocks contain a significantly greater amount of Al 2 O 3 and less TiO 2 than maritime basalts.
Oxygen is the most abundant element in both terrestrial and lunar rocks. This determines that
the similarity in the isotopic composition of oxygen for terrestrial and lunar rocks is
considered an accurate index of the fact that the Earth and the Moon were formed in the same
area of the protoplanetary cloud. In a broader sense, it is as if the Moon was a by-product
during the formation of the Earth, taking material from the feeding zone of the growing
proto-Earth.
The age of the rocks that make up the continents has been determined with the help of
radiometric methods. From these studies it was possible to conclude that the ages of
continental rocks can be grouped around two values: 4460 million years (which is interpreted
as the time of formation of the lunar crust) and 3860 million years (which agrees with the age
of the rain sea and is interpreted as the age of the eruptions during the formation of the
circular seas by impact).
For the condensation time of the protoplanetary cloud, the value of 4570 million years is
adopted, from which it follows that the accretion of the moon with its total fusion (or a
considerable part of it) and its consequent crystallization, concluded fairly speed.
The age of maritime basalt samples is in the range of 3160-3900 million years, and in the
eastern part of the Storm Ocean the minimum age value of 2600 million years has been
obtained. Maritime basalts were formed in the processes of partial melting of the moon's
upper mantle, which had previously lost the garbo-anorthositic material of the crust. The
crystallization of the rocks of the upper mantle took place 4.4 billion years ago, that is,
hundreds of years before the eruptions.
The fact that on the Moon there is no and, apparently, there never was a dense atmosphere or
hydrosphere, has contributed to the traces of the early history of the Solar System being
recorded on its surface. In this connection, research on the Moon is of exceptional importance
for the problem of the origin and evolution of the Earth and the planets.
The planets of the terrestrial group have been incorporated in recent years into the field of
cosmic research through the use of automatic interplanetary stations equipped with the
technical devices necessary for the processing of the information obtained and the
transmission of the results to the flight centers. terrestrial.
The main components of these planets are silicates and iron; All of them have a deficit of
water, methane and ammonia, compounds with low boiling temperatures and quite
widespread in the cosmos.
Venus is the planet of the terrestrial group that most resembles Earth, due to its dimensions
and mass. In addition, it is the planet that is the closest distance from Earth, but, despite this,
it was little known (and still is in many aspects). Until about twenty years ago, the most
complete information about Venus has been provided by the Soviet automatic stations of the
“Venera” series (16 in total) and by some North American spacecraft of the “Mariner” series
(Mariner 2, Mariner 5, Mariner 10 ) and “Pioneer-Venus” (2 released in 1978). The Soviet
spacecraft “VEHA 1” and “VEHA 2” intended for studies of Comet “Halley” were also
conceived for the exploration of Venus in 1985.
In October 1975, panoramic images of the surface of Venus were transmitted to Earth for the
first time from the descent modules of the “Venera-9” and “Venera-10” spacecraft. These
devices worked for hours in the “hellish” conditions of Venus, providing scientists with

19
information about the properties of the soil, the particularities of the atmosphere and its cloud
cover, etc.
The “Venera-11” and “Venera-12” spacecraft, as well as the “Pioneer-Venus 1” and
“Pioneer-Venus 2” together transmitted for about 6 hours from the surface of Venus, and the
accumulation of data collected It was such that it required many years to analyze them.
From these studies it was possible to verify that the chemical composition of the atmosphere
of Venus is completely different from that of the Earth, characterized by its high corrosivity.
From the ground to 48 km high the air is relatively clear and pure; It is composed of carbon
dioxide (97%), nitrogen (1-3%), water vapor (0.1-0.4%) and traces of argon, neon, helium,
oxygen and sulfur dioxide were detected. The second layer, located between 48 and 51 km
high, is characterized by enormous clouds of sulfuric acid. At heights between 52 and 60 km
the clouds are four times denser, and in addition to sulfuric acid they contain solid particles.
Up to 70 km the density becomes even greater and its composition includes hydrochloric acid
and hydrofluoric acid, accompanying sulfuric acid.

1.2- Forms of expression of the abundance of chemical elements in geochemical

systems.
First of all, it is necessary to define what we call a geochemical system?
A geochemical system represents any natural terrestrial system that can be characterized
through its actual or estimated chemical composition. These could be: the Earth as a whole,
structural parts of the Earth (core, mantle, oceanic crust, continental crust, hydrosphere,
atmosphere, biosphere, etc.), rocks (igneous, sedimentary and metamorphic), soils,
weathering crusts , waters (sea, river, lake, underground, etc.), plants, animals, air, etc.
But what forms can be used to express the quantitative chemical composition of such
geochemical systems?
To answer this question, it is first necessary to distinguish the following terms: absolute
abundance and relative abundance.
The absolute abundance expresses the average content of an element in the geochemical
system considered, or what is the same as its normal clarke (mass %, atomic %, ppm, ppb,
g/t, etc.)
Relative abundance expresses the proportional content of an element in a geochemical system
with respect to what it would have in another related geochemical system, or its clarke
concentration (dimensionless).
In this way, the following problems could arise, linked to the absolute abundance of the
elements:
What differences exist between the abundances of Ca and K on Earth?
Can this question be answered by comparing the normal clarkes of these elements on Earth?
In what type of igneous rocks is Na most abundant?
To answer this question, it is enough to compare the normal clarkes of these elements in the
different types of igneous rocks (ultrabasic, basic, medium and acidic).
Some questions could also arise in relation to relative abundances, such as:
How much more is Mg concentrated in ultrabasic rocks compared to medium rocks?
To determine this it is necessary to calculate the corresponding clarke concentration.

Between Fe and Al, which is more concentrated in the crust?

20
In this case it would be convenient to calculate the clarke concentration of both elements
taking as a common denominator the normal clarkes that correspond to them on Earth.

The final two situations are linked to the unequal distribution of elements in igneous rocks
and on Earth, respectively. This allows us to conclude that by properly comparing the
concentration clarkes, the chemical differentiation that has occurred during a given
geochemical process can be evaluated.

1.3- Structure and internal composition of the Earth. Primary geochemical

differentiation.
To make an adequate estimate of the structure and internal composition of the Earth, it has
been necessary to combine all the available geophysical, geochemical, cosmochemical and
geophysical information. The most significant geophysical data that have been taken into
account for this evaluation are those related to the density and propagation speed of seismic
waves. The geochemical data collected only considers the abundances of chemical elements
in the geochemical systems that make up the upper part of the Earth's crust. Among the
cosmochemical data, those relating to the chemical composition of meteorites have been of
extraordinary value. In this way, the normal clarkes of the main chemical elements that make
up the Earth have been estimated (table 1.4).

Table 1.4
Normal clarkes on Earth (% by mass).

Items Z normal clarke Items Z normal clarke

Faith 26 34,63 To the 13 1,09
EITHER 8 29,53 na 11 0,57
Yeah 14 15,20 Cr 24 0,26
Mg 12 12,70 mn 25 0,22
Neither 28 2,39 Q 15 0,10
Yes 16 1,93 K 19 0,07
AC 20 1,29 You 22 0,05

By briefly analyzing this table it can be confirmed that there are some non-compliance with
the laws and regularities on the universal abundance of the elements when trying to apply
them to the Earth:
1- Hydrogen (the most abundant element in the Universe) is not represented in the table,
which indicates that its abundance on Earth is lower than those of the tabulated elements.
2- Sodium (Z=11) is more abundant than neon (Z=10), and phosphorus (Z=15) is more
abundant than nitrogen (Z=14). Both situations constitute violations of the Oddo-Harkins
rule.

These irregularities reaffirm the idea that the Earth was formed as a result of a chemical
differentiation process verified during the formation of the Solar System, concentrating in it
the characteristic elements of the solid component (silicates, oxides, metals) of the gas cloud
and original powder, while the gaseous component dissipated.

21
1.3.1- Seismic model of the internal structure of the Earth.
The impossibility of penetrating the Earth's depths using the drilling technology that exists
today has forced man to search for and apply indirect methods to evaluate, with a certain
degree of approximation, the internal structure of the Earth and the properties of the
substances that make it up. The study of the speed of propagation of longitudinal (p) and
transverse (s) seismic waves through the interior of our planet has made it possible to
elucidate some of the questions related to this geological problem.
The propagation speed of longitudinal waves can be determined based on the sliding modulus
(  ), the multilateral compression modulus (K) and the density (  ) of the body crossed by
them, according to the following expression:

The propagation speed of transverse waves depends only on the slip modulus (  ) and the
density, as expressed below:

Longitudinal and transverse waves are susceptible to being reflected and/or refracted when
passing from one medium (or phase) to another, manifesting themselves in the form of
sudden changes in their propagation speeds. But what factors determine the occurrence of
these phenomena?
Among them, the most important are: crystalline structure of solids, state of aggregation of
substances, density, pressure and temperature.
1- Crystalline structure of solids. The spatial arrangement of ions in the crystal lattices of
solids determines the establishment of a phase through which longitudinal and transverse
waves propagate with constant velocities. In general, the increase in the compactness of a
crystal lattice as a consequence of the increase in the coordination number of the ions
causes an increase in the propagation speed of seismic waves. This knowledge has made it
possible to indirectly assess the properties of the minerals that make up the Earth's interior
and to state hypotheses about the occurrence of mineralogical phase changes
(polymorphic transformations) at certain depths. These changes cause sudden and
irregular jumps in the speeds with which these waves propagate at the dividing limit
between both media.
2- State of aggregation of substances. The arrangement of the particles of any substance
promotes the existence of a sufficiently elastic medium for seismic waves to propagate.
Crystalline solid media corresponds to the greater ordering of its component particles,
which is the reason why seismic waves are able to travel through them with greater speed.
Liquid media have a lower ordering of their component particles, which determines that
longitudinal waves significantly reduce their propagation speed and transverse waves are
completely reflected. Gaseous media are made up of particles in complete disorder, which
prevents the propagation of seismic waves through them. This aspect is of great
importance to indirectly evaluate the state of aggregation of the substances that make up
the Earth's interior.
3- Density of substances. According to the expressions that relate the speed of propagation
of seismic waves to the density of substances, it can be seen that they are inversely
proportional.
4- Pressure and temperature. These factors influence the speed of propagation of seismic
waves in completely opposite ways. The pressure exerted on a medium favors the
translation of these waves; This is explained by the positive influence caused by increases
in pressure on the compactness and elasticity of the affected substances. On the contrary,
high temperatures are unfavorable for the propagation of these waves; The cause of this

22
 phenomenon is related to the disorder that is created in the internal structure of the
substances when the temperature increases. Changes in pressure and temperature are also
linked to the transitions of mineralogical phases, which can cause sudden effects on the
propagation of seismic waves.

The comprehensive analysis of seismological data has made it possible to verify that the
Earth has a fairly well-defined concentric structure, which can be characterized through

Fig. 1.9- Internal structure of the Earth

(according to the seismic model)

layers with relatively homogeneous physical properties and chemical composition. The abrupt
changes in the speed of propagation of seismic waves at certain depths allow the delimitation
of concentric boundary surfaces that have come to be called discontinuities . Thus, within
the Earth, two first-order seismic boundaries stand out: the Mohorovicic discontinuity and the
Wiechert-Gutenberg discontinuity, which allow it to be subdivided into three main layers or
geospheres: crust, mantle and core. Other second-order seismic boundaries have also been
detected that allow, in turn, to subdivide each of these main geospheres (fig. 1.9).

1.3.2- Geochemical hypotheses about the internal composition of the Earth.

Many hypotheses have been put forward to estimate how the original distribution of chemical
elements occurred during the formation of the Earth and, consequently, what implications this
had on the composition of each of its interior parts. Among these hypotheses, the following
should be highlighted:
1- Goldschmidt hypothesis (1922)
2- Washington Hypothesis (1925)
3- Buddington Hypothesis (1943)
4- Bullen hypothesis (1953)
Each of them, in its own way, offers an internal subdivision of the Earth, which is essentially
similar to that represented by the seismic model. However, what is transcendent in each of

23
them are the arguments that support the internal composition of the Earth; Of these,
Goldschmidt's hypothesis has had a greater impact, in which it is established that the
distribution of elements inside the Earth is determined by the chemical affinity for a certain
phase (metallic, sulfurous and silicate).
METAL PHASE (Fe, Ni, Pt, Au, Ag)
SULFUROSE PHASE (Cu, Pb, Zn, Ga, In, Cd, Hg, As, Sb)
SILICATE PHASE (Na, K, Ca, Mg, Al, Fe 2+ , Ti, Cr, Ba)

The integration of these data allows us to judge the internal composition of the Earth, which
could be summarized as follows:

 Chemical composition of the nucleus.

The core is made up of a material of very high density, which is favored by the high pressures
that prevail at these depths, which determines the contraction of the crystalline structures.
The core is made up almost entirely of Fe, Ni, Co and smaller amounts of Ge, Pt, Au and
platinoids.

 Chemical composition of the mantle.

The mantle is fundamentally made up of igneous rocks rich in Mg, Fe and lower amounts of
Ni, Co, Cr, V, etc.

 Chemical composition of the earth's crust.

The crust is the outer layer or geosphere of the Earth, delimited at its base by the
Mohorovicic discontinuity.
The contribution of the crust to the total mass of the Earth is only 0.7%. Its thickness varies
from 6 to 70 km between the oceanic and continental regions, respectively, although it is
represented with an effective average thickness of 33 km.
The rocks that constitute it have densities that range between 2.0 and 3.0 g/cm 3 , and their
values can rarely reach 3.3 g/cm 3 for some of its varieties, more common in the zone
bordering the mantle. .
The Earth's crust is essentially made up of igneous rocks (95%), sedimentary rocks (4%) and
metamorphic rocks (1%). From here it can be deduced that the chemical composition of the
Earth's crust is determined by the existence of igneous rocks, which arise as a result of
magmatic processes that are generated in its lower part and in the asthenosphere.
When a detailed study of the crust is carried out, it is necessary to consider the existing
irregularities in its thickness and the great heterogeneity that is manifested in its composition.
This leads to its division into three main types: oceanic crust, continental crust and crust of
the intermediate regions (fig. 1.10).

24
 Fig. 1.10- Types of the Earth's crust.

The continental crust has thicknesses that vary between 30 and 70 km, being divided in
depth into: sedimentary layer, upper crust and lower crust. The rocks that make up these
layers are clearly differentiated by their densities. Those that form the sedimentary layer have
the lowest values (  = 2.0-2.3 g/cm 3 ); The upper crust is made up of igneous and
metamorphic rocks with intermediate densities (  = 2.4-2.7 g/cm 3 ); and to the lower crust,
igneous and metamorphic rocks with higher densities are associated (  = 2.8-3.3 g/cm 3 ).
For its geotectonic study, it is customary to classify this type of crust into: stable continental
regions (Precambrian shields, platforms and paleogenic orogenic chains) and orogenic
continental regions (young orogenic chains and continental rifts).
The stable continental regions correspond to average crustal thicknesses close to 40 km; In
the Precambrian shields the sedimentary layer is practically non-existent, while the platforms
have sedimentary covers that can reach up to 5 km thick.
Variable crustal thicknesses exist in orogenic continental regions. While young orogenic
chains can provide crust thicknesses that can reach up to 70 km, continental rifts are
characterized by having a thinner crust. The folded chains have sedimentary layers whose
thickness is several thousand meters (more than 10 km in the Himalayas).
The oceanic crust is characterized by having thicknesses that range between 5 and 9 km
below the bottom of the seas and oceans. Currently it has been considered to be made up of
three layers: layer 1, layer 2 and layer 3. Layer 1 is made up of poorly consolidated sediments
and sedimentary rocks to which very low densities correspond (  = 2.0-2.4 g/cm 3 ); Layer 2
is made up of igneous rocks with somewhat higher densities (  = 2.7-2.8 g/cm 3 ), layer 3 is
made up of igneous rocks whose densities are extremely high (  = 3.0-3, 1 g/cm 3 ).
As in the continental crust, this type of crust shows geotectonic differences of interest, which
has led to its classification into: oceanic basins, central-oceanic mountain ranges, oceanic
trenches and marginal basins.
The crust of the intermediate regions is characterized by its association with subduction
zones. Its thickness varies between 9 and 25 km, which constitutes evidence of its transitional
character between the continental crust and the oceanic crust.
The regions with this type of crust frame: island arcs and internal marine basins, which have
notable geotectonic differences.
An estimate of the average chemical composition of the Earth's crust and the Earth can be
seen in table 1.6.

Elem. Z normal clarkes Clarkes of

conc.

25
 Land Cortex Crust/Earth
EITHE 8 29,50 47,00 1,59
R
Yeah 14 15,20 29,50 1,94
To the 13 1,09 8,0,5 7,38
Faith 26 34,63 4,65 0,13
AC 20 1,13 2,96 2,62
na 11 0,57 2,50 4,39
K 19 0,07 2,50 35,7
Mg 12 12,70 1,87 0,15
You 22 5·10-2 0,45 9,00
h 1 - 0,15 -
mn 25 0,22 0,10 0,45
Q 15 0,10 0,093 0,93
F 9 - 0,066 -
Ba 56 - 0,065 -
Yes 16 1,93 0,047 0,024
Cr 24 0,26 0,020 0,077
Neither 28 2,39 0,0058 0,002

Table 1.6- Normal clarkes (% by mass) and concentration

clarkes for the main elements in the Earth and crust.

From the information provided in this table, the following conclusions can be reached:
1- The elements that tend to concentrate mostly in the crust are: K, Ti, Al, Na, Ca, Si, O.
They will be associated mainly with the silicate phase of the crust, even more so as the
clarkes concentration is higher.
2- The elements with the least tendency to concentrate in the crust and, therefore, more
associated with the core and mantle, are: Ni, S, Fe, Mg, Mn, P. Its geochemical affinity
will be given by the possible association with the metallic phase of the core (Fe, Ni, Cr),
with the sulphurous phase of the mantle (S, Mn, Fe) and the silicate phase of the mantle
(Mg, Cr, Ni).
3- There are several breaches of the laws and regularities about the universal abundance of
elements when trying to be applied to the crust:
a) Hydrogen is not the most abundant element.
b) The most abundant metal is Al, although the greatest tendency to concentration in the
crust corresponds to K.
c) Various violations of the Oddo-Harkins rule.

Mn > Cr Al > Mg Na > Mg

(Z=25) (Z=24) (Z=13) (Z=12) (Z=11) (Z=12)

In this way it would be necessary to consider the occurrence of a primary geochemical

differentiation of the Earth, largely responsible for the zonal structure that is characteristic of
it. These two aspects, therefore, have been regulated by the electronic configuration of the
atoms and ions in the physical-chemical conditions that prevail in each of the interior
geospheres.

1.4- Geochemical classification of elements.

All of the above analysis serves as a basis for defining Goldschmidt's geochemical
classification of elements, which considers that the primary geochemical differentiation of the

26
Earth corresponds to the geochemical affinity of the elements with respect to the three
indicated phases: metallic, sulphurous and silicate. .
Based on the performance of some metallurgical experiments and taking into account the
content of various elements in meteorites, Goldschmidt considered that the elements can be
classified according to their geochemical affinity into the following groups: siderophiles,
chalcophiles, lithophiles and atmophiles. Some elements have a tendency to occur in more
than one group, since their distribution depends on the physicochemical conditions of the
medium (temperature, pressure, composition).
The geochemical character of an element is widely regulated by the electronic configuration
of its atoms and, consequently, can be assessed based on the position it occupies in the
Periodic System (Table 1.5).

Table 1.5- Geochemical classification of elements (according to Goldschmidt).

27
Geochemical Electronic Position of the Examples
character configuration of its periodic system
ions
Siderophiles +8 and -18 e VIII-B Fe Ni Co
Chalcophile 18 and (18+2) e IB II-B and groups Cu Zn Ag
that follow Pb Hg Ga
Lithophile 8e IA II-A III-A Na Ca Ti Si Cl Cr V
IV-A GO VI-A Mn Al O Mg Zr
VII-A III-B IV-B
VB VI-B VII-B

Atmophile VIII-A He Ne Ar Kr Xe Rn

1.5- Abundance and distribution of chemical elements in endogenous geochemical

systems.
Within the endogenous geochemical systems the following pairs must be considered: magma -
igneous rock (or magmatic reservoirs) and hydrothermal solutions - hydrothermal minerals (or
hydrothermal reservoirs).

SISTEMAS GEOQUÍMICOS
ENDÓGENOS

Magma Solución hidrotermal

Roca ígnea Yacimiento Minerales Yacimientos

magmático hidrotermales hidrotermales

The genetic relationship between the components of these pairs is given by endogenous
processes: magmatic and hydrothermal, and they condition endogenous differentiation.

DIFERENCIACIÓN
ENDÓGENA

Diferenciación Diferenciación
magmática neumatolito-hidrotermal

In a first approach to this problem, it must be highlighted that there is a close link between the
crystallochemical, thermodynamic and geochemical properties that govern the unequal
distribution of chemical elements during endogenous processes, all based on the electronic
envelope of atoms and ions. .

29
 Ionic charge Ionic radius Wrapping type
and atomic external electronics

PROPERTIES THERMODYNAMIC GEOCHEMICAL

CRYSTALLOCHEMIS PROPERTIES PROPERTIES
TRIES

Link Coordination crystallin

type number e network lattice energy Geochemical affinity

Derived from this, some phenomena appear that must be taken into account when assessing the
distribution of chemical elements in the crystalline structures of the constituent minerals of the
endogenous geochemical systems of the Earth's crust: crystallization of minerals, isomorphic
substitutions (minor elements) and exchange reactions.
The crystallization of minerals is determined by the combination of thermodynamic (pressure,
temperature, composition), crystallochemical (type of crystalline structure) and geochemical
(chemical affinity) factors. Consequently, the chemical elements that will tend to form minerals
will be those that are most concentrated in some of the stages of the process (majority elements)
and can establish the most stable combinations within the crystalline structure. In general terms,
when the physicochemical conditions of the environment are favorable for the formation of
different minerals, the one with the highest lattice energy will be formed first and so on.
Isomorphic substitutions in the crystalline structures of minerals are possible whenever there
are similarities between the ionic (or atomic) radii, polarizing action and type of external
electronic envelope, which would guarantee the stability of the crystalline structure. When ions
of equal charge intervene in this phenomenon, the substitution is said to be isovalent; On the
contrary, if the participating ions have different charges, the substitution is heterovalent. There
are many tools to elucidate the possible occurrence of isomorphic substitutions; Among them,
Fersman's law of diagonal series stands out as a guide to determine the possible occurrence of
heterovalent isomorphic substitutions. Other procedures that may be useful are based on the
position that the elements occupy in the Periodic System, and the effect that d compression
(transition elements) and lanthanide contraction (rare earth elements) can cause on the
similarities of the ionic radii. , which may be valid to demonstrate the possible occurrence of
some isovalent isomorphic substitutions. Through isomorphic substitutions it is possible to
explain the tendency of some minority elements to concentrate in certain types of igneous rocks
and magmatic and hydrothermal minerals.
Exchange reactions are caused by the interaction between magma (or hydrothermal solution)
and surrounding rocks, which gives rise to the formation of alteration minerals. This process
gives rise to a more or less radical change in the chemical composition of part of the surrounding
rock depending on the physicochemical conditions prevailing in the alteration process.

30
1.5.1- Magmatic differentiation. Chemical composition of magma and igneous rocks.
Magmatic differentiation occurs through a complex mechanism that is based on the possible
existence of a silicate phase and a sulphurous phase coexisting in the molten state under certain
physicochemical conditions. Different types of igneous rocks are formed from the silicate phase
(ultrabasic, basic, medium and acidic) and the sulphurous phase is responsible for the formation
of some magmatic deposits associated with ultrabasic and basic rocks. This could be
schematized as follows:

MAGMA

Silicate phase Sulphurous

phase

Igneous rocks Magmatic sulfides

Ultrabasic acidic

Basic Socks

 Chemical composition of the silicate phase of magma and igneous rocks.

The unequal chemical composition of the different types of igneous rocks allows us to confirm
that their formation has taken place as a result of a process of chemical differentiation in which
the material that makes up the upper mantle and that originating from the Earth's crust itself
have actively intervened. This appreciation is what allows us to affirm that the Earth's crust is a
differentiated product of the mantle that has continued to evolve under the new conditions.
To demonstrate the joint role of crystallochemical, thermodynamic and geochemical
factors in magmatic differentiation, the abundance and distribution of chemical elements
in igneous rocks must be verified using the corresponding normal Clarkes table.
Elem Cut. ultrab Basic middle acid Ele Cut. ultrab Basic Middle acid
Z Z
. terr. rocks rocks rocks rocks m. terr. rocks rocks rocks rocks
EIT 8 47 42.5 43.5 46 48.7 Sc 21 1·10-3 5·10-4 2,4·10 2,5·10-4 3·10-4
-3
HER
-3
Yeah 14 29.5 19 24 26 23.3 Pr 59 1·10 (n·10 4·10-4 (6,2·10- 1,2·10
-
5 4 -3
) )
-1 -4
To 13 8.05 4,5·10 8.76 8.85 7.7 YE 62 8·10 (n·10 5·10 (7,5·10 9·10-4
- -4 -
5 4
the ) )
-4
Faith 26 4.65 9.85 8.65 5.85 2.7 gd 64 8·10 (n·10 5·10 (7,5·10- 9·10-4
- -4
5 4
) )
AC 20 2.96 7·10-1 6.72 4.69 1.58 Dy 66 5·10-4 5·10-6 2·10-4 (5,2·10- 6,7·10
4 -4
)
na 11 2.5 5,7·10-1 1.94 3 2.77 tb 65 4,3·10-4 (n·10 - 8·10-5 (1,2·10- 2,5·10
5 4 -4
) )
K 19 2.5 3·10-2 8,3·10-1 2.3 3.34 Be 4 3,8·10-4 2·10-5 4·10-5 1,8·10-4 5,5·10
-4

31
Mg 12 1.87 25.9 4.5 2.18 55 3,7·10-4 1·10-5 1·10-4 (1,5·10-
0.56 cs 5·10-4
4
)
-2 -1
You 22 4,5·10 3·10 9·10 8·10 2,3·10 Er 68 3,3·10 (n·10 2·10 (2,8·10-
-1 -4 - -4
4·10-4
-1 -1 5 4
) )
- -
h 1 1,5·10 - (1,2·10 (1,1·10 - Yes 50 2,5·10 5·10 1,5·10 (1,6·10-
-4 -5
1,7·10
-1 1 1 -4 4 -4
) ) )
-1 -1 -1 -1 -2
mn 25 1·10 1,5·10 2·10 1,2·10 6·10 ta 73 2,5·10 1,8·10 4,8·10 7·10-5
-4 -6
3,5·10
-5 -4
-2 -1 -1 -2 -4 -7 -5 -4
Q 15 9,3·10 1,7·10 1,4·10 1,6·10 7·10 OR 92 2,5·10 3·10 5·10 1,8·10 3,5·10
-2 -4
-2 -2 -2 -2 -4 -5 -4 -4
F 9 6,6·10 1·10 3,7·10 5·10 8·10 Br 35 2,1·10 5·10 3·10 4,5·10 1,7·10
-2 -4
-4 -2 -2 -4 -5 -4 -4
Ba 56 6,5·10 1·10 3·10 7,5·10 8,3·10 Ace 33 1,7·10 5·10 2·10 2,4·10 1,5·10
-2 -2 -4
-2 -2 -2 -2 -4
Yes 16 4,7·10 1·10 3·10 2·10 4·10 Ho 67 1,7·10 (n·10 1·10 (1,5·10 2·10-4
- -4 -
-2 5 4
) )
Mr 38 3,4·10 1·10-3 4,4·10-2 8·10-2 3·10-2 Ge 32 1,4·10-4 1·10 1,5·10 1,5·10-4 1,4·10
-4
-2 -4 -4
-2 -2 -2 -2 -4 -6 -4 -
c 6 2,3·10 1·10 1·10 2·10 3·10 eu 63 1,3·10 1·10 1·10 (1,2·10 1,5·10
-2 4 -4
)
CL 17 1,7·10 5·10-3 5·10-3 1·10-2 2,4·10 W 74 1,3·10-4 1·10-5 1·10-4 -4
1·10 1,5·10
-2 -2 -4
-3 -2 -2 -4 -5 -5
Zr 40 1,7·10 3·10 1·10 0.026 2·10 mo 42 1,1·10 2·10 1,4·10 9·10 1·10-4
-2 -4
-4 -3 -2 -2 -4 -5
Rb 37 1,5·10 2·10 4,5·10 1·10 2·10 Hf 72 1,1·10 1·10 1·10-4 1·10-4 1·10-4
-2

V 23 9·10-3 4·10-3 2·10-2 1·10-2 4·10-3 Tl 81 1·10-4 1·10-6 2·10-5 5·10-5 1,5·10
-4

Zn 30 8,5·10 3·10-3 1,3·10-2 7,2·10-3 6·10-3 Lu 71 8·10-5 (n·10 - 6·10-5 (8·10-5) 1·10-4
-3 5
)
Cr 24 8,3·10 3·10-2 2·10-2 5·10-3 2,5·10 Sb 51 5·10-5 1·10-5 1·10-4 2·10-5 2,6·10
-3 -3 -5

EC 58 7·10-3 (n·10 - 4,5·10-4 (6,5·10- 1·10-2 Yo 53 4·10-5 1·10-6 5·10-5 3·10-5 4·10-5
5 3
) )
Neith 28 5,8·10 2·10-1 1,6·10-1 5,5·10-2 1·10-4 Yb 70 3,3·10-5 (n·10 - 2·10-4 (2,8·10- 4·10-4
-3 5 4
er ) )
Cu 29 4,7·10 2·10-3 1·10-2 3,5·10-3 2·10-3 Tm 69 2,7·10-5 (n·10 - 2·10-5 (0,2·10- 3·10-5
-3 6 4
) )
nd 60 3,7·10 (n·10 - 2·10-3 (2,7·10- 4,6·10 in 49 2,5·10-5 1,3·10-6 2,2·10 (2,2·10- 2,6·10
-3 5 3 -3 -5 5 -5
) ) )
Lee 3 3,2·10 5·10-5 1,5·10-3 2·10-3 4·10-3 CD 48 1,3·10-5 5·10-6 1,9·10 (1,8·10- 1·10-5
-3 -5 5
)
AND 39 2,9·10 (n·10 - 2·10-3 (2,9·10- 3,4·10 Hg 80 8,3·10-6 1·10-6 9·10 (2,1·10-
-6
8·10-6
-3 5 3 -3 6
) ) )
The 57 2,9·10 (n·10 2,7·10 (3·10-3)
- -3
6·10-3 Ag 47 7·10-6 5·10-6 1·10 7·10-6
-5
5·10-6
-3 5
)
Nb 41 2·10 1·10-4 2·10-3 2·10-3
-3
2·10-3 HE 34 5·10-6 5·10-6 5·10-6 5·10-6 5·10-6
N 7 1,9·10 6·10-4 1,8·10-3 2,2·10-3 2·10-3 P.S 46 1·10-6 1,2·10-5 1,9·10 (n·10 - 1·10-6
-3 -6 7
)
Ga 31 1,9·10 2·10-4 1,8·10-3 2·10-3 2·10 -3
Bi 83 9·10 -7
1·10 7·10 1·10-6 1·10-6
-7 -7
-3

Co 27 1,8·10 2·10-2 4,5·10-3 1·10-3 5·10-4 Pt 78 5·10-7 2·10-5 1·10-5 - -

32
 -3

Pb 82 1,6·10 1,5·10-5 8·10-4 1,5·10-3 2·10-3 Au 79 4,3·10-7 5·10-7 4·10-7 (2,8·10- 4,5·10
-3 7 -7
)
Th 90 1,3·10 5·10-5 3·10-4 7·10-4 1,8·10 Tea 52 1·10-7 1·10-7 1·10-7 1·10-7 1·10-7
-3 -4

b 5 1,2·10 1·10-4 5·10-4 1,5·10-3 1,5·10 Re 75 7·10-8 - 7,1·10 - 6,7·10

-3 -3 -8 -8

Table 1.7- Normal clarkes (% by mass) of chemical elements in igneous rocks, according to A.
Q. Vinogradov (1962).

The chemical elements according to their abundance in igneous rocks should be classified as:
1- Major elements (O, Si, Al, Ca, Na, Fe, Mg).
2- Secondary elements (Cr, Ti, V, F, P, Zr, U, Th).
3- Rare or dispersed elements (Cu, Pb, Zn, Sn, Li, Rb, Be, Ba, Sr, Ta, Nb, etc.).

The distribution of chemical elements in the different types of igneous rocks responds to:
1. The possibility of forming petrographic minerals (olivines, pyroxenes, amphiboles, micas,
feldspars, feldspathoids, quartz, etc.).
2. The ability to form accessory minerals (chromite, chalcopyrite, magnetite, rutile, zircon,
apatite, uraninite, thorianite, etc.).
3. Incorporation as an isomorphic impurity in the crystalline structures of petrographic
minerals and accessories.

The order of crystallization of petrographic minerals, therefore, influences the tendency of the
majority elements to concentrate in a certain type of igneous rock. This can be seen by resorting
to the analysis of the Bowen series (fig. 1.11).

33
 Fig. 1.11 – Bowen series.

How is the relationship between crystallochemical, thermodynamic and geochemical factors

expressed when assessing the distribution of the major elements in igneous rocks as a result of
magmatic differentiation?
From this assessment the following conclusions can be reached:
1- Mg and Fe tend to concentrate in ultrabasic rocks.
2- Ca and Al reach their upper normal clarke in basic rocks.
3- Na and Al are concentrated in the middle rocks.
4- K and Si have their maximum concentrations in acidic rocks.

ionic Ionic radius External electronic

Items
charge (nm) envelope type
Mg +2 0,066 8e
Faith +2 0,074 +8 and -18 e
AC +2 0,099 8e
na +2 0,097 8e
K +2 0,133 8e
To the +2 0,051 8e
Yeah +2 0, 8e

DISCONTINUED SERIES

34
 Coordination Lattice energy Affinity
Mineral Cation
number (kJ/mol) geochemistry
Forsterite Mg 2+ 6 Lithophile
Fayalita Faith 2+ 6 Lithophile
Enstatite Mg 2+ 6 Lithophile
Ferrosilite Faith 2+ 6 Lithophile
hornblende Ca2 + 8 Lithophile
Mg 2+ 6 Lithophile
Faith 2+ 6 Lithophile
At 3+ 6 Lithophile
At 3+ 4 Lithophile
Biotite K 1+ 10 Lithophile
Mg 2+ 6 Lithophile
Faith 2+ 6 Lithophile
At 3+ 4 Lithophile

To this it must be added that the crystalline structures become more complex in the following
order of substitution, which corresponds to the formation of minerals at a lower temperature:

CONTINUING SERIES

Coordination Lattice energy Affinity

Mineral Cation
number (kJ/mol) geochemistry
Anorthite Ca2 + 8 Lithophile
At 3+ 4 Lithophile
Bitownite Ca2 + 8 Lithophile
Na + 8 Lithophile
At 3+ 4 Lithophile
Labrador Ca2 + 8 Lithophile
Na + 8 Lithophile
At 3+ 4 Lithophile
Andesine Na + 8 Lithophile
Ca2 + 8 Lithophile
At 3+ 4 Lithophile
Oligoclase Na + 8 Lithophile
Ca2 + 8 Lithophile
At 3+ 4 Lithophile
Albite Na + 8 Lithophile
At 3+ 4 Lithophile

It is necessary to remember that crystalline structures do not experience significant changes in

their complexity when one mineral is replaced by another in the given order.
The order of crystallization of accessory minerals depends on the integration of
crystallochemical, thermodynamic and geochemical factors and the physical-chemical conditions
under which their formation from magma takes place. We cannot forget the role that the
concentrations of secondary elements play during magmatic differentiation so that the formation
of these accessory minerals can occur. Even though there is no series that indicates the
replacement of one accessory mineral by another during magmatic differentiation, we can
approach an analysis of this type using a procedure similar to that used for major elements.

35
1- Cr, Au, Pt and platinoids tend to concentrate in ultrabasic rocks.
2- Ti and Cu reach their upper normal clarke in basic rocks.
3- P is concentrated in the middle rocks.
4- U and Th present their maximum concentrations in acidic rocks.

Items Ionic charge Ionic radius Wrapping type

(nm) external electronics
Cr +3 +8 and –18 e
Au 0 +8 and –18 e
Pt 0 +8 and –18 e
You +3 +8 and –18 e
+4 8e
Cu +2 +8 and 18 e
Neither +2 +8 and –18 e
OR +4
You +4

Finally, the incorporation of isomorphic impurities in the crystalline structures of petrographic

and accessory minerals is linked to the crystallochemical factors stated at the beginning.

 Chemical composition of the sulphurous phase of magma and magmatic sulphides.

1.5.2- Pneumatolite-hydrothermal differentiation. Chemical composition of pneumatolite-

hydrothermal solutions and pneumatolytic and hydrothermal minerals.
When dealing with this aspect, the fact that there are qualitative differences between the
composition of pneumatolytic solutions and that corresponding to hydrothermal solutions must
be considered. Furthermore, these processes are governed by the solubility of the substances in
the pneumatolite-hydrothermal solutions and by the chemical reactions that occur between the
different components under given physicochemical conditions (many of which lead to the
establishment of an equilibrium state).
Pneumatolytic differentiation occurs from a solution enriched in volatile components, which
includes the following elements: F, Cl, B, Li, Be and P. This is why, associated with the metallic
minerals that usually form during this stage (cassiterite, wolframite, scheelite, molybdenite,
native gold, chalcopyrite, bismuthite), non-metallic minerals such as: spodumene, beryl, topaz,
fluorite, etc. usually appear.
The formation of minerals in the pneumatolytic stage is justified by the occurrence of chemical
reactions and the establishment of equilibria under certain physical-chemical conditions, all of
which promotes the rapid and intense separation of highly soluble substances. Processes of this
nature can be exemplified in the way represented below:

SnF 4 + 2H 2 O = SnO 2 + 4HF

SiF 4 + 2H 2 O = SiO 2 + 4HF

The interaction of HF with the host rocks could lead to the formation of fluorite and topaz,
depending on the reaction:

Ca Al 2 Si 2 O 8 + 2HF = CaF 2 + Al 2 SiO 4 (OH , F) 2

Anorthite Fluorite Topaz

Hydrothermal differentiation manifests itself from a solution enriched in certain components,

which include elements that occupy a precise place in the Periodic System (predominantly

36
chalcophiles). The atomic numbers of these elements are in the following ranges: 29-34, 47-52,
79-83. Among these the most frequent are: Cu, Zn, As, Au, Ag, Hg and Pb.

The distribution of elements in pneumatolitic and hydrothermal minerals responds to:

1- The possibility of forming metallic minerals (cassiterite, wolframite, scheelite, pyrrhotine,
chalcopyrite, arsenopyrite, pyrite, antimonite, cinnabar, realgar, orpiment, galena, sphalerite,
native gold, native silver, acanthite, etc.).
2- The ability to form non-metallic minerals (calcite, fluorite, sericite, quartz, topaz, chlorite,
etc.).
3- Incorporation as an isomorphic impurity in the crystalline structures of metallic and non-
metallic minerals.

Fersman proposed a scheme for distributing the elements by levels, starting with the
pneumatolytic stage (temperature of 600ºC) and concluding in the low-temperature
hydrothermal stage (50ºC):

I Li, K, Mo, Sn, W, Bi, SiO 4 4- , PO 4 3- , O 2- , S 2-

II W, As, Au, Fe, Zn, SiO 4 4- , CO 3 2-
III Cu, Zn, Pb, As, Sb, CO 3 2- , SO 4 2-
IV Pb, As, Au, Co, Ni, As2S 4 2- , Sb 2 S 4 2-
V Sb, As, Hg, F - , S 2-
The order of deposition of metallic minerals coincides in principle with the decrease in lattice
energy, which is generally expressed as follows:

Mineral Cation ionic radius lattice energy

Molybdenite
Pyrotin
cassiterite
Wolframite
Bismith
Bismuthite
Scheelite
Native Gold I
Arsenopyrite
Pyrite
Chalcopyrite
Stalferite
Galena
Antimony sulfosalts
Arsenic sulfosalts
Uraninite
Native Gold II
Antimonite
Realgar
Orpiment

37
1.6- Abundance and distribution of chemical elements in exogenous geochemical
systems. Exogenous differentiation.

EXOGENOUS
GEOCHEMICAL SYSTEMS

Sedimentary rocks
Hydrosphe Biosphere Atmospher
and sediments
re e

1.5.1- Chemical composition of sedimentary rocks and sediments.

Elem Earth clayey Sandsto Carbona Ele Earth clayey Sandsto Carbona
Z Z
. crust rocks nes te rocks m. crust rocks nes te rocks
-3
EIT 8 47,0 52,8 51,72 49,51 b 5 1,2·10 1·10-2 2·10 -3
3·10-4
HER
Yeah 14 29,5 23,80 36,75 2,22 Sc 21 1·10-3 1·10-3 7·10-5 -
To 13 8,05 10,45 2,53 0,43 Pr 59 9·10-4 5·10-4 - -
the
Faith 26 4,65 3,33 0,99 0,40 gd 64 8·10-4 6,5·10-5 - -
AC 20 2,96 2,53 3,95 30,45 YE 62 8·10-4 6,5·10-5 - -
na 11 2,5 0,66 0,33 4·10-2 Dy 66 5·10-4 4,5·10-5 - -
K 19 2,5 2,28 1,10 0,27 tb 65 4,3·10-5 9·10-5 - -
Mg 12 1,87 1,34 0,71 4,77 Be 4 3,8·10-4 3·10-4 - -
-2
You 22 0,45 0,45 0,10 4·10 cs 55 3,7·10-4 1,2·10-3 - -
h 1 0,15 - - - Er 68 3,3·10-4 2,5·10-4 - -
mn 25 0,10 6,7·10-2 - 4·10-2 ts 2,5·10-4 3,5·10-4 - -
Q 15 9,3·10-2 7,7·10-2 3·10-2 2·10-2 Yes 50 2,5·10-4 1·10-3 - -
F 9 6,6·10-2 5·10-2 - 2,5·10-2 Br 35 2,1·10-4 6·10-4 - -
Ba 56 6,5·10-2 8·10-2 1,7·10-2 1,2·10-2 Ace 33 1,7·10-4 6,6·10-4 - -
Yes 16 4,7·10-2 0,3 0,28 0,11 Ho 67 1,7·10-4 1·10-4 - -
Mr 38 3,4·10 4,5·10-2
-2
2,6·10-3 6·10-2 Ge 32 1,4·10-4 2·10-4 3·10-4 -
c 6 2,35·10 1,45 1,48 11,39 eu 63 1,3·10-4 1·10-4 - -
-2

CL 17 1,7·10-2 1,6·10-2 - 2·10-2 W 74 1,3·10-4 3·10-4 - -

Zr 40 1,7·10-2 2·10-2 - - mo 42 1,1·10-4 2·10-4 - -
Rb 37 1,5·10-2 2·10-2 2,7·10-2 - Tl 81 1·10-4 1·10-4 2·10-4 -
V 23 9·10-3 1,3·10-2 2·10-3 1·10-3 Hf 72 1·10-4 6·10-4 - -
Cr 24 8,3·10-3 1·10-2 1,5·10-2 9·10-4 Lu 71 8·10-5 7·10-5 - -
Zn 30 8,3·10-3 8·10-3 2·10-3 5·10-3 Sb 51 5·10-5 2·10-4 1·10-4 -
EC 7·10-3 5·10-3 - - Yo 53 4·10-5 1·10-4 - -
Neith 28 5,8·10 9,5·10-3
-3
5·10-4 - Yb 70 3,3·10-5 3·10-4 3·10-4 -
er
Cu 29 4,7·10-3 5,7·10-3 - 2·10-3 Tm 69 2,7·10-5 2,5·10-5 - -
nd 60 3,7·10-3 2,3·10-3 - - in 49 2,5·10-5 5·10-6 - -
Lee 3 3,2·10-3 6·10-3 1,7·10-3 2,6·10-3 CD 48 1,3·10-5 3·10-5 - -

38
AND 39 3,2·10-3 3·10-3 - - Hg 80 8,3·10-6 4·10-5 1·10-5 3·10-6
The 57 2,9·10-3 4·10-3 1,6·10-4 - Ag 47 7·10-6 1·10-5 4,4·10-5 2·10-5
Nb 41 2·10-3 2·10-3 - - HE 34 5·10-6 6·10-5 - 1·10-5
N 7 1,9·10-3 6·10-2 - - P.S 46 1,3·10-6 - - -
Ga 31 1,9·10-3 3·10-3 7.4·10-4 3.7·10 -4
Bi 83 9·10 -7
1·10-7 3·10-5 -
Co 27 1,8·10-3 3·10-3 - - Pt 78 5·10-7 - - -
Pb 82 1,6·10-3 2·10-3 2·10-3 7,5·10 -4
Au 79 4,3·10 2,8·10-6
-7
2,8·10-6 7·10-7
Th 90 1,3·10-3 1,1·10-4 - - Tea 52 1·10-7 1·10-6 - -
b 5 1,2·10-3 1·10-2 2·10-3 3·10 -4
Re 75 7·10 -8
- - -

Table 1. – Normal clarifiers of chemical elements in sedimentary rocks.

1.5.2- Chemical composition of the hydrosphere.

Clarke's Clarke's
Earth Hydrosph Earth Hydrosph
Elem. Z concentratio Elem. Z concentrati
crust ere crust ere
n on
EITH 8 47,0 85,89 Ag 47 7,7·10-6 3·10 -8

ER
h 1 0,15 10,8 Kr 3·10-8
-2 -7
CL 17 1,7·10 1,93534 Bi 83 8·10 2·10-8
na 11 2,50 1,03534 HE 34 5·10-6 1·10-8
Mg 12 1,87 0,1297 CD 48 1,3·10-5 1·10-8
-2 -2
Yes 16 4,7·10 8,9·10 ne 10 1·10-8
-2
AC 20 2,96 4,08·10 Ge 6·10-9
K 19 2,50 3,8·10-2 Zr 5·10-9
-4 -3
Br 35 2,1·10 6,6·10 Sc 21 1·10-3 4·10-9
-2 -3
c 6 2,3·10 2,8·10 Ga 31 1,9·10-3 3·10-9
-2 -4
Mr 38 3,4·10 8·10 Pb 82 1,3·10-4 3·10-9
b 5 1,2·10-3 4,6·10-4 Hg 80 8,3·10-6 3·10-9
Yeah 14 29,5 3·10-4 Cr 2·10-9
-2 -4
F 9 6,6·10 1,3·10 in 1·10-9
-5
Ar 18 6·10 Th 90 1,3·10-3 1·10-9
N 7 1,9·10-3 5·10-5 Nb 1·10-9
Rb 37 1,5·10-2 2·10-5 Tl 1·10-9
-3 -5
Lee 3 3,2·10 1,5·10 Au 79 4,3·10-7 6·10-10
-5
W 1·10 I have 5·10-10
Q 15 9,3·10-2 7·10-6 The 57 2,9·10-3 2,9·10-10
-5 -6
Yo 53 4·10 5·10 Lu 1,2·10-10
-2 -6
Ba 56 6,5·10 2·10 eu 1,1·10-10
-4 -6
Ace 33 1,7·10 1,4·10 EC 58 7·10-3 1,3·10-10
To the 13 8,05 1·10-6 Dy 7,3·10-11
-6
Faith 26 4,65 1·10 Be 6·10-11
-3 -6
Zn 30 8,3·10 1·10 Er 6·10-11
-4 -6
mo 42 1,1·10 1·10 gd 6·10-11
Yes 50 2,5·10-4 3·10-7 Pr 6·10-1
-4 -7
OR 92 2,5·10 3·10 Yb 5,2·10-11
-3 -7
Cu 29 4,7·10 3·10 YE 4,2·10-11
-3 -7
V 23 9·10 3·10 nd 2,3·10-11

39
 mn 25 0,10 2·10-7 Ho 2,2·10-11
Neithe 28 5,8·10-3 2·10-7 Tm 1·10-11
r
You 22 0,45 1·10-7 Ra 1·10-14
Sb 5·10-8 Da 5·10-15
Co 27 5·10-8 Rn 6·10-20
cs 55 3,7·10-4 3,7·10-8 Ac 2·10-20
AND 39 2,9·10-3 3·10-8

Table 1. Clarkes of the chemical elements in the hydrosphere (according to A. Q. Vinogradov,

1967).

1.5.3- Chemical composition of the biosphere.

Clarke's Clarke's
Earth Biospher Earth Biospher
Element Z concentrati Element Z concentrati
crust e crust e
on on
-4
EITHER 8 47,0 70,0 Zn 30 5·10
c 6 0.023 18,0 Rb 37 5·10-4
h 1 0,15 10,5 Cu 29 4,7·10-3 2·10-4
-1
AC 20 2.96 5·10 V 23 9·10-3 n·10 -4
-1
K 19 2.5 3·10 Cr 24 8,3·10-3 n·10 -4
-1
N 7 3·10 Br 1,5·10-4
Yeah 14 29.5 2·10-1 Ge 1·10-4
Q 15 7·10-2 Neither 28 5,8·10-3 5·10-5
-2
Mg 12 1.87 4·10 Pb 82 5·10-5
-2 -2
Yes 16 4,7·10 2·10 Yes 5·10-5
na 11 2.5 2·10-2 Ace 3·10-5
CL 17 0.017 2·10-2 Co 27 2·10-5
-2
Faith 26 4.65 1·10 Lee 3 3,2·10-3 1·10-5
-3
To the 13 8.05 5·10 mo 1·10-5
Ba 56 6,5·10-2 3·10-3 AND 1·10-5
Mr 2·10-3 cs 1·10-5
-3
mn 25 0.10 1·10 HE <10-6
-3
b 1·10 OR <10-6
TR n·10 -3 Hg n·10 -7
-4
You 22 0.45 8·10 Ra n·10 -12
-2 -4
F 9 6,6·10 5·10

terrestri terrestri
Earth Earth
Elem. Floors al Elem. Floors al
crust crust
plants plants
Lee 3,2·10-3 3·10-3 1,1·10-3 Zn 8,5·10-3 5·10-3 9·10-2
Be 3,8·10-4 6·10-4 2·10-4 Ace 1,7·10-4 5·10-4 3·10-5
b 1,2·10-4 1·10-3 4·10-2 HE 5·10-6 1·10-1 -
F 6,6·10-2 2·10-2 1·10-3 Br 2,1·10-4 5·10-4 1,5·10-2
na 2,50 0,63 2,0 Rb 1,5·10-2 6·10-3 3·10-2
Mg 1,87 0,63 7,0 Mr 3,4·10-2 3·10-2 3·10-2
To the 8,05 7,13 1,40 Zr 1,7·10-2 3·10-2 -
Yeah 29,5 33,0 15,0 mo 1,1·10-4 2·10-4 2·10-3

40
 Q 9,3·10-2 8·10-2 7,0 Ag 7·10-6 1·10-5 1·10-4
Yes 4,7·10-2 8,5·10-2 5,0 CD 1,3·10-5 5·10-5 1·10-6
CL 1,7·10-2 1·10-2 1·10-2 Yes 2,5·10-4 1·10-3 5·10-4
K 2,50 1,36 3,0 Yo 4·10-5 5·10-4 5·10-3
-4
AC 2,96 1,37 3,0 cs 3,7·10 5·10-4 n·10 -4
You 0,45 0,46 0,1 Ba 6,5·10-2 5·10-2 n·10 -2
V 9·10-3 1·10-2 6,1·10-3 Au 4,3·10-7 - 1·10-4
Cr 8,3·10-3 2·10-2 2,5·10-2 Hg 8,3·10 -6
1·10-6 1·10-7
mn 1·10-1 8,5·10-2 7,5·10-1 Pb 1,6·10 -3
1·10-3 1·10-3
Faith 4,65 3,8 1,0 Ra 8,3·10-11 8,3·10-11 2·10-11
Co 1,8·10-3 1·10-3 1,5·10-3 Th 1,3·10-3 6·10-4 -
Neither 5,8·10-3 4·10-3 5·10-3 OR 2,5·10-4 1·10-4 5·10-5
Cu 4,7·103 2·10-3 2·10-2

1.5.4- Chemical composition of the atmosphere.

1.5.5- Exogenous differentiation.

Exogenous differentiation occurs through complex processes involving rocks, water, living
organisms, air, etc.
To carry out an adequate analysis of exogenous differentiation, the following must be combined:
the pathways used by chemical elements to be incorporated into exogenous geochemical systems
and the interactions established between the components of the higher geospheres.

INCORPORATION
COMPONENTS THAT
PATHS
INTERACT

Weathering of Gaseous Liquids Solids Biogenic carbonate

minerals and emanations d
rocks from volcanic
activity

To complete this introductory table of exogenous differentiation, we only have to ask ourselves
the following questions: what must be the fate of the elements that originally made up these
geochemical systems? What role do physical (mechanical), physical-chemical, and chemical
processes play? and biochemicals in exogenous differentiation?
In a first approach to this problem, the elements that actively participate in the chemical
processes of exogenous differentiation must be differentiated from those that are inert to the
chemical agents during this process.

Chemically active elements Chemically inert elements

Mineral formers that are not very resistant to
chemical weathering.
Gas formers of inorganic and/or biological
origin (O 2 , HCl, etc.)
Resulting from the ionization of acids and
Mineral formers very resistant to chemical
weathering.
Inert gas formers (He, Ne, Ar, N 2 ).

41
bases and the hydrolysis of some salts (H 3 O + ,
OH - , ect).

Correspondingly, exogenous differentiation will occur following three main mechanisms:

For example, when the weathering of an ultrabasic rock mass or that corresponding to a pyrite-
chalcopyritic mineral body occurs, chemical differentiation would predominate because the
EXOGENOUS
DIFFERENTIATION

Differentiation Differentiation Differentiation

chemistry mechanics biochemistry
minerals that constitute both endogenous geochemical systems are unstable in the presence of
chemical weathering agents.
On the other hand, if what is exposed to weathering is a mass of acidic rocks, a granitic
pegmatite or a cassiterite-wolframite mineral body, mechanical differentiation would
predominate since the minerals that make up these endogenous geochemical systems are
resistant. to chemical weathering.
In both cases there will be possibilities of biogenic differentiation occurring from the selective
absorption of nutrients by parts of plants and animals.

 Chemical differentiation.
This process presupposes the participation of water as the main solvent in nature and,
consequently, the occurrence of inorganic and organic chemical processes (ion exchange,
oxidation-reduction, acid-base, etc.) and surface (colloidal adsorption) in aqueous solutions.
Such a situation is governed by the joint role of chemical and physicochemical properties, which
are derived from the electronic shell of the ions.

42
 Ionic charge Radius Ionic Shell Type
external
electronics

CHEMICAL
PROPERTIES

Acid-base properties Redox properties Chemical affinity

(ion potential) (electrode potential ) (Electronegativity)

Neutralization Oxidation Carbonate formation

Hydrolysis Reduction Oxide formation
Formation of hydroxides
Sulfate formation
Sulfide formation
Silicate formation

PHYSICOCHEMICAL PROPERTIES

Colloidal properties

Colloid Colloidal
coagulation adsorption
 The role played by the ionic potential, the redox potential and the type of external electronic
envelope in the manifestation of the chemical properties of the different elements (ions) must
be clarified. To do this, the teacher must use the 18-column periodic table, returning to the
basic knowledge that the student has in the General Chemistry course. On this basis, the
influence of these factors on the chemical differentiation of the elements must be assessed,
together with the effect caused by pH and Eh in this process.
 Reference should also be made to the role that colloidal absorption plays in the separation of
some ions from natural waters, corresponding to the colloidal state with geochemical
systems composed of very fine particles (e.g., clayey sediments).

Derived from this, some phenomena appear that must be taken into account when evaluating the
distribution of elements during chemical differentiation. These phenomena are: dissolution of
minerals in water, hydrolysis capacity of ions, chemical combination capacity of ions, colloidal
absorption capacity of ions, coagulation of colloids, which depend on the physicochemical
conditions of the medium (pH , Eh, dissolved substances, etc.). All of this determines the fate
and unequal distribution of chemical elements during chemical differentiation.
Returning to the situation posed at the beginning, we could ask ourselves what will be the fate of
Fe and Mg during the chemical weathering of the intrusive massif of ultrabasic rocks? These
elements are integrated into olivines and pyroxenes, which result from moderate resistance to

43
chemical weathering. This means that they could be initially incorporated into weathering
solutions (rich in CO 2 , O 2 and other dissolved substances).
- Fe 2+ under these physicochemical conditions would be oxidized to Fe 3+ and, finally, would
be completely hydrolyzed due to the intermediate ionic potential it possesses. This would
lead to the formation of goethite (FeO(OH)) and hydrogoethite (FeO(OH)  nH 2 0), which
would precipitate from these solutions and integrate certain types of sediments. In this case,
the hydrolysis capacity of iron increases due to its oxidation.
- Mg 2+ could dissolve in the form of Mg(HCO 3 ) 2 , thus incorporating into natural waters,
which is favored by the relatively low ionic potential and its external envelope of 8 electrons.
Both issues hinder the hydrolysis of Mg 2+ and, consequently, its precipitation in the form of
hydroxides.
On the other hand, what would become of the Fe, Cu and S that make up the pyrite-
chalcopyritic mineral body?
Pyrite and chalcopyrite are minerals that are not very resistant to chemical weathering, so the
same considerations set out above must be taken into account:
- Fe 2+ follows a path similar to that explained in the previous example.
- Cu 2+ could initially dissolve in water because its ionic potential is lower than that of Fe 3+
and this makes its hydrolysis difficult, but its envelope of >8 and <18 electrons contributes to
this process finally occurring. . This inevitably leads to the formation of malachite and
azurite (basic copper carbonates) through their precipitation from weathering solutions.
- S 2- would be transformed into SO 4 2-, incorporating most of the sulfur into natural waters,
due to the notable increase in the ionic potential of sulfur as a result of its oxidation. This
allows it to form soluble oxyanions with little capacity to hydrolyze.

 Mechanical differentiation.
This process occurs with the participation of physical (mechanical) agents that promote the
mobility of those elements integrated into minerals resistant to chemical weathering.
This means that physical factors are dominant in this type of exogenous differentiation, which
would be closely linked to the integration of properties of the atomic nucleus and properties
derived from the electronic envelope.

Mass Charge Ionic Radius Type of Ionic Atomic Shell and External
Electronic Atomic

PHYSICAL PROPERTIES

Specific Hardness Color

weight

Under the action of a mechanical agent (water, wind), these minerals are differentiated based on
their mass, which is directly proportional to their specific weight.
In the situation initially proposed, it should be expected, assuming that the mineral grains are of
equal size, that the cassiterite would be more affected by the mechanical agents given its
somewhat lower specific weight.
 Biochemical differentiation.

44
This process occurs as a result of the selective absorption of elements from natural waters by
parts of plants and animals, accompanied by different phenomena that lead to the synthesis of
organic and inorganic compounds during their metabolic activity.
The final result of exogenous differentiation must be assessed taking into account the unequal
distribution of chemical elements in the different exogenous geochemical systems. This can be
seen by interpreting the normal Clarke tables of sedimentary rocks (carbonate rocks, clayey
rocks and sandstones), hydrosphere and biosphere (Table 1. )
Earth clayey Sandstone carbonate Hydrosphe Biospher
Element Z
crust rocks s rocks re e
Yeah 14 29,5 23,80 36,75 2,22 3·10-4 2·10-1
To the 13 8,05 10,45 2,53 0,43 1·10-6 2,5·10-4
-6
Faith 26 4,65 3,33 0,99 0,40 1·10 1·10-2
AC 20 2,96 2,53 3,95 30,45 4,08·10-2 5·10-1
na 11 2,5 0,66 0,33 0,04 1,035 2·10-2
K 19 2,5 2,28 1,10 0,27 3,8·10-2 3·10-1
Mg 12 1,87 1,34 0,71 4,77 0,13 4·10-2
You 22 0,45 0,45 0,10 0,04 1·10-7 8·10-4
mn 25 0,10 0,067 - 0,04 2·10-7 1·10-3
Q 15 0,093 0.077 0.03 0.02 7·10-6 7·10-2
-4
F 9 0,066 0,05 - 0,025 1,3·10 5·10-4
Ba 56 0,065 0,08 0,017 0,012 2·10-6 3·10-3
Yes 16 0,047 0,3 0,28 0,11 8,9·10-2 5·10-2
Mr 38 0.034 0.045 2,6·10-3 0.06 8·10-4 2·10-3
-3
c 6 0,023 1,45 1,48 11,39 2,8·10 18,0
CL 17 0,017 0,016 - 0,02 1,935 2·10-2
Zr 40 0,017 0,02 - - 5·10-9 -
-3 -3 -3 -8
V 23 9·10 0,013 2·10 1·10 3·10 n·10 -4
-3 -4 -9
Cr 24 8,3·10 0,01 0,015 9·10 2·10 n·10 -4
Neither 28 5,8·10-3 9,5·10-4 5·10-4 - 3·10-8 5·10-5
Cu 29 4,7·10-3 5,7·10-4 - 2·10-3 4,5·10-6 2·10-4
Lee 3 3,2·10-3 6·10-3 1,7·10-3 2,6·10-3 1·10-5 1·10-5
-3 -3 -4 -4 -8
Ga 31 1,9·10 3·10 7,4·10 3,7·10 5·10 -
Ge 32 1,4·10-4 2·10-4 3·10-4 - 6·10-9 1·10-4
W 74 1,3·10-4 3·10-4 - - 1·10-5 -

Table 1. Normal clarkes of chemical elements in sedimentary rocks, hydrosphere and

biosphere (% by mass).

However, once the chemical, physicochemical, physical and biochemical properties of the
chemical elements are known, it is possible to predict what their geochemical behavior will be
during exogenous differentiation.

45
1.7- Abundance of nuclides and isotopic composition of geological objects.
1.7.1- Generalities.
When studying the universal abundance of chemical elements, it was concluded that there was
a dependence of this on the atomic number and, consequently, on the properties derived from
the atomic nucleus.
If we consider that chemical elements are made up of atomic species (nuclides), it is expected
that what determines the abundance of the chemical element is the abundance of the atomic
species that make it up.
Each nuclide is characterized by defined properties of its atomic nucleus (number of protons and
number of neutrons), the sum of which determines the mass of the atom.

A=Z+N

where:
TO Mass number
Z Number of protons
N Neutron number

In such a way, any nuclide can be represented symbolically as:

A
E
where:
AND Symbol of the element to which the nuclide corresponds with number of protons Z

Examples:
12C 87 32S
Rb

Nuclides can be classified according to the properties of their atomic nuclei into:
Isotopes Isobarians Isotones

Nuclids with equal Nuclidians with equal Nuclids with equal N

Z A

46
1.7.2- Rules on the stability and abundance of atomic nuclei.
Multiple data confirm that the abundance of nuclides depends on the structure of the atomic
nucleus, which allows it to be related to the stability of the atom. Such ideas will be addressed in
the course of this section, but initially we propose to make a thorough assessment of the
information available about the abundance of nuclides.
Currently around 1000 nuclides are known, of which only about 280 are non-radioactive. The
vast majority of radioactive nuclides have been obtained artificially, characterized by having a
relatively short half-life.
Table ________ shows the relative abundances of isotopes of various elements, according to
data provided by Fridlender, Kennedi and Miller (1967). Combining this information with the
universal abundances of the elements shown in table 1.3, it has been possible to obtain the
universal abundances of the most important nuclides.
A detailed analysis of Table 1.5 serves as a starting point to corroborate the validity of some
rules that try to explain the abundance of nuclides on the basis of the relative stability of atomic
nuclei.

47
48
a) Rule of symmetry.
The relative stability of the atomic nuclei and, consequently, the abundance of nuclides depend,
in the first instance, on the degree of symmetry existing in them with respect to the number of
protons (Z) and neutrons (N). In other words, the most stable atomic nuclei and the most
abundant nuclides must correspond to those nuclear structures represented by a number of
protons approximately equal to the number of neutrons, a condition that is met when the atomic
number is small (Figure 1.7).
150

140

130

120

110

100

90

80
N

70

60

50

40 N u clid io s estab les

N u clid io s rad iactiv o s
30

20

10

10 20 30 40 50 60 70 80 90 100 110 120 130 140 150

Z
Fig. 1. Relationship between the atomic number (Z) and the number of neutrons (N) for the
different nuclides.

Note that the nuclides close to the coordinate origin are located on both sides of the bisector of
the angle formed by the Z and N axes. The highest abundances correspond to these nuclides
according to the data shown in table 2.5.
With the increase in atomic number, a progressive deviation is observed towards the N axis,
which is explained by the incorporation of neutrons into the nucleus more easily than protons,
since the latter are exposed to Coulomb repulsions. Long-lived unstable (radioactive) nuclides
are preferentially grouped in the area furthest from the bisector, also corresponding to those with
the smallest abundances. These heavy nuclides tend to disintegrate, producing more stable
nuclides and releasing a large amount of energy.
This rule serves as the basis for the proven fact of the decrease in the universal abundance of
elements with the growth of the atomic number and the impossibility of existence in nature of
elements whose atomic numbers are greater than 92.

b) Rule of layers.
In order to properly understand the meaning of this rule, it is necessary to previously group the
nuclides based on the even (p) or odd (i) number of protons and neutrons present in their atomic
nuclei. From this classification, 4 possible types of nuclides result: (pp), (pi), (ip), (ii), which are
exemplified below:

49
 Guy Symbol Z N
16
(pp) O 8 8
9
(pi) Be 4 5
7Li
(ip) 3 4
10B
(ii) 5 5

According to this rule, protons and neutrons tend to form layers of two in the atomic nucleus
(closed layers), a condition that determines that type (pp) nuclides are the most frequent in
nature. In the case in which a proton or a neutron were added to an atomic nucleus that only has
closed shells, the union between this incorporated particle and the nucleus would be relatively
weak (open shells of protons or neutrons) and, as a result of this, the resulting core would
acquire lower stability compared to the original; This justifies that nuclides of types (pi) and (ip)
are less frequent than those of type (pp). Consequently, if an additional proton and neutron were
simultaneously incorporated into an atomic nucleus made up of closed shells, it would be
expected that the instability would be maximum, an aspect that determines the rare appearance
of type (ii) nuclides. Table 1.8 shows the distribution of nuclides of these classes in nature.

Guy Number of nuclides Relative frequency

(pp)
(pi)
(i.p.)
(ii)

Table 1.8. Frequency of appearance of nuclide types in nature.

What was expressed above serves as an argument to justify why elements with even atomic
numbers are more abundant than those with odd atomic numbers.

c) Rule of isobars.
This rule is completely empirical and serves to indicate the existence or absence of isobars. It is
contained in the following principles:
1st- The difference between the number of protons of two stable isobars is greater than 1
(Mattauch's rule). In other words, there are no pairs of stable isobars whose atomic number
differs by unity.
2nd- If the mass number of a nuclide is even, the number of protons and the number of neutrons
must also be even. Consequently, nuclides of type (ii) could not exist.
3rd- Each of the nuclides of the types (pi) and (ip), which have the odd mass number, is
represented by a single stable isobar. This isobar is the most energetically favorable, while the
rest are unstable (  -active). In other words, there are no odd mass number isobars.

Using this rule, it is possible to substantiate at the atomic level the prediction made by Oddo and
Harkins about the higher abundance of chemical elements of even atomic number with respect to
those of their neighbors in the Periodic System.

d) Rule of the multiplicity of mass numbers.

Fersman grouped nuclides based on the multiplicity of their mass numbers by 4, defining the
following types: (4q), (4q+1), (4q+2), (4q+3).

Guy Example
16
4q O
13C
4q+1

50
 30
4q+2 Yes
43
4q+3 Ca
In correspondence with this, he could see that nuclides of type (4q) represent the most abundant
isotopes of each element.

1.7.3- Isotopic composition of geological objects.

In addition to their chemical composition, geological objects can be characterized by their
isotopic composition.
The development achieved by mass spectrometry techniques has made it possible to carry out
very sensitive studies of the isotopic composition of different geological objects, which has laid
the foundations for applying isotopic research to the solution of certain geological problems,
which will be briefly addressed during the development of this section.

This implies that each chemical species can be made up of several isotopic species.
Example 1
Calcite (CaCO 3 ) is made up of Ca, C and O atoms. If each of these elements is represented by
several isotopes, then we will have as many isotopic species as the product of the isotopes of
each element.
Ca has 6 isotopes: 40 Ca, 42 Ca, 43 Ca, 44 Ca, 46 Ca, 48 Ca
C has 2 isotopes: 12 C, 13 C
O has 3 isotopes: 16 O, 17 O, 18 O

This results in 36 isotopic species of the same chemical species (calcium carbonate).
However, the isotopic composition of calcite (CaCO 3 ) could be expressed only in terms of C
and O isotopes, thus resulting in 6 isotopic species.

Ca 12 C 16 O 3 Ca 12 C 17 O 3 Ca 12 C 18 O 3 Ca 13 C 16 O 3 Ca 13 C 17 O 3 Ca 13 C 18 O 3

As the abundance of each nuclide is different from that of the others, the resulting isotopic
species will also have unequal abundances, which could be expressed in a simplified way for the
chemical species as:
- The content of 16 O, 17 O, 18 O in calcite (CaCO 3 ).
- The content of 12 C , 13 C in calcite (CaCO 3 ).

In general, the isotopic composition of geological objects is expressed in terms of proportions

involving two isotopes: heavy isotope ( m A) and light isotope ( nA ). The most common ways
used to express these are: isotopic correlations and  values .

1. Isotopic correlation.

2. Values  .

(‰)

This parameter serves to express in what proportion the sample is more enriched in the heavy
isotope with respect to the standard, which can be represented by the following scheme:

51
 - 0 +

Light isotope enrichment Heavy isotope enrichment

in the sample with respect to the in the sample with respect to the
pattern pattern

The pattern used in determining the  values varies from one isotopic pair to another, this being
determined by the constancy in the isotopic composition of the object taken for this purpose.

1.8- Isotopic fractionation. Applications to the study of geological processes.

Isotopic fractionation consists of the differentiated distribution of 2 or more isotopes between
several objects involved in common physical, chemical or biochemical processes. Consequently,
this phenomenon leads to a more or less pronounced change in the isotopic composition of the
objects involved.

Evaporation
Physical
processes Sublimation
Condensation

Chemical Redox reactions

processes Ion exchange reactions

Bacterial sulfate reduction

Biochemical Bacterial methane formation
processes Plant photosynthesis
Assimilation of carbonates by calcareous organisms

Together with these processes, isotopic exchange reactions occur that tend to a state of isotopic
equilibrium.
Each isotopic exchange reaction in its equilibrium state will be characterized by an equilibrium
m
AX + n
OH n
AX + may >1  1
constant (K) at a given temperature. This magnitude expresses the intensity of isotopic
fractionation once the state of isotopic equilibrium is reached, hence the equilibrium constant
(K) is equivalent to the degree of isotopic fractionation (  ).

Each of these concepts can be represented symbolically by means of the isotopic exchange
reaction:
where:
m
AX, n AX: Isotopic species of substance AX

52
m
AY, n AY: Isotopic species of substance AY
m: Mass number of heavy isotope
n: Light isotope mass number
: Degree of fractionation

By definition, the equation that represents the isotopic exchange reaction is stated in such a way
that in the direct sense it indicates isotopic fractionation.
In general, isotopic fractionation decreases in speed with increasing temperature. This factor,
therefore, is opposite to isotopic fractionation and causes it to practically not exist in a magma at
700-1000 ºC, beginning to be important during petrogenetic processes that occur at lower
temperatures.
It is necessary to add that isotopic fractionation develops more widely in systems that involve a
gas phase, hence elements such as H, C, O and S, which form gaseous compounds, are those that
show greater isotopic fractionation.
The intensity of isotopic fractionation is a function of the relative differences between the mass
numbers of each isotope involved in the process (mass differential).
For example, if the mass differentials between the stable isotopes of hydrogen ( 1 H and 2 H) and
chlorine ( 35 Cl and 37 Cl) are compared, based on the corresponding expressions,

This allows us to consider that the isotopic fractionation of hydrogen is much more feasible than
that of chlorine.
To date, the heaviest element for which isotopic fractionation has been clearly demonstrated is
sulfur, in which the mass differential between its isotopes ( 32 S and 34 S) is 0.059.
Several aspects that are related to the genesis of mineral deposits can be assessed through stable
isotope investigations. Among them, the most notable are:
a) Physical conditions of mineral formation (temperature, pre sion and depth).
b) Hydrological issues of mineral formation systems (origin and mass of mineral-forming fluids,
duration of hydrothermal activity).
c) Origins of mineral constituents (sulfur, carbon and metals).
d) Chemical composition of mineral formation fluids (redox state, sulfate/sulfide ratios, pH and
CO 2 / CH 4 ratios).
e) Mechanisms used in the transport of metals and sulfur and mineral deposition.
f) The origin and evolutionary process of magmas related to mineral formation.

These aspects linked to mineral formation processes should not be treated in isolation since they
may exist among them. have numerous interrelationships. For example, the metal and sulfur
chemistry of a mineral formation fluid may depend on the origin of the carbon and water, the
hydrologic history of the fluid, and the origin of the sulfur and metals. Depositional processes
could, instead, be influenced by the geochemistry of the fluids.
Through the isotope systems of hydrogen, oxygen, carbon and sulfur, some useful information is
obtained on these six questions of mineral formation processes. Sulfur isotopes are more useful than
others for delimiting the formation temperatures of sulphurous ores; The analysis of the
hydrological aspects of mineral formation rests more strongly on the isotopic data of hydrogen and
oxygen than on others because water is the solvent par excellence of all meniferous constituents in
all deposits except in the "orthomagmatic" and The H and O isotopic composition of ore-forming
53
fluids reflects the origin and history of the water-rock interaction of such fluids; Sulfur and carbon
isotopes are used in the study of some details about the chemical aspects of mineral formation, as
well as the participation of biological processes on some occasions.
The applications of stable isotopes in this sense are summarized in several scientific articles
published in recent years. Taylor (1974, 1979) and Sheppar (1977) have devoted their summaries to
the isotopes of hydrogen and oxygen; meanwhile, Rye and Ohmoto (1974, 1979) developed these
for sulfur and carbon isotopes.
Isotopic investigations may also be of interest in clarifying some topics, such as:
a) Paleotemperatures of seas and oceans.
b) Origin of organic substances (methane and hydrocarbons).
c) Origin of the waters (meteoric, magmatic, etc.).
d) Differentiation of the origin of minerals.

 Isotopic fractionation of oxygen and hydrogen. Applications.

To evaluate the isotopic composition of geological objects, with respect to the isotopes of
hydrogen ( 1 H and D) and oxygen ( 16 O and 18 º), the values  D and  18 º, respectively, are
preferably used. In these cases, seawater is adopted as a universal standard.

a) By physical processes.
The phase changes of water promote the occurrence of isotopic fractionation of oxygen and
hydrogen, with a tendency to reach the state of isotopic equilibrium at a given temperature.
Understand within these physical processes: evaporation (liquid-vapor), condensation (vapor-
liquid), solidification (liquid-solid) and liquefaction (solid-liquid).
In all cases there is a tendency to enrich the less dispersed phase in the heaviest isotope of each
element ( 18 O and 2 H, respectively).

H 2 16 O (l) + H 2 18 O (v) H 2 18 O (l) + H 2 16 O (v)

1
H 2 O (l) + 2 H 2 O (v) 2
H 2 O (l) + 1 H 2 O (v)
b) By chemical processes.
The measurement of paleotemperatures of seas and oceans can be carried out by studying the
following isotopic exchange reactions:

16 - 18 18 - 16
HC
1/3 CaC OO
3 (ac)++ C
16
3(s) H 2
18
OO(l)2(g) HC
1/3 CaCO 18
3 O (ac) ++C
3(s) H 2
OO2(g)
16
(l)

16
1/2 O 2 (g) + H 2 18 O (l) 18 16
1/2 O 2 (g) + H 2 O (l)
 Carbon isotopic fractionation. Applications.
In the case of  13 C, a calcareous fossil called belemnite is used as a pattern.

a) By chemical processes.

H 12 CO 3 - (ac) + 13 CO 2(g) H 13 CO 3 - (ac) + 12 CO 2(g)

13
CH 4(g) + 12 CO 2(g) 12
CH 4(g) + 13 CO 2(g)

54
 Sulfur isotopic fractionation. Applications
For  34 S the chosen pattern was a meteoritic mineral known as troilite (FeS).

a) By chemical processes.
32
SO 4 2- (ac) + H 2 34 S (g) 34
SO 4 2- (ac) + H 2 32 S (g)

b) By biochemical processes.

32
SO 4 2- (ac) + H 2 34 S (g) 34
SO 4 2- (ac) + H 2 32 S (g)

reducing bacteria
of sulfates

1.9- Radioactive decay. Applications in determining the absolute age of geological

objects.

1.9.1- Modes of radioactive decay.

The nucleosynthesis processes that occurred in the ancestral stars produced more than 2200
nuclids, most of which were unstable and decayed in a short time. Only those nuclides that are
stable or slowly decay have survived to the present. However, some short-lived radioactive
nuclides (radionuclides) exist naturally because:
1- They are short-lived daughters of U and Th, both resulting from long-lived radioactive
isotopes.
2- They are produced by nuclear reactions between cosmic rays and atoms in the atmosphere,
as well as in rocks exposed on the surface.
A third group of radionuclides now exists on Earth due to man-made nuclear reactions. The
reactions consist primarily of the induced fission of 235 U in nuclear reactors, but also include the
detonation of nuclear devices in the atmosphere and underground. The anthropogenic
radioactive contaminants produced by these activities include a very long list of radionuclides,
including: 3 H, 14 C, 90 Sr, 129 I, 137 Cs. The containment of these radioactive wastes has become a
serious problem in environmental geochemistry.
Unstable nuclides are characterized by having excess or deficient neutrons in their atomic nuclei.
This largely determines how they disintegrate.
The phenomenon known as radioactivity consists of the spontaneous nuclear transformation of a
radionuclide (M) to a stable nuclide (H). This could be represented in a general way as follows:

These transformations are accompanied by the emission of alpha particles (  ), beta particles ( 
) and gamma rays (  ) from the nuclei. Some isotopes of light elements decay into alpha
particles or emit protons or neutrons. Most radionuclides undergo beta decay, a small number
are subject to alpha decay, and a few of the heavier isotopes decay by spontaneous nuclear
fission.

a) Beta decay (   and   ).

Beta decay can occur in three different ways, depending on whether the radionuclide is neutron-
excessive or neutron-deficient. Radionuclides that have an excess of neutrons emit a negatively

M h
55
charged beta particle from the nucleus. This has the effect of reducing the number of neutrons
and increasing the number of protons.

This particle   is identical to an extranuclear electron and  is an antineutrino.

Radionuclides located on the left side of the stable nuclide band in Figure ____ are neutron
deficient and decay by the emission of a positron (   ) or by the capture of an electron. These
forms of beta decay increase the number of neutrons and decrease the number of protons.
In the decaying positron, a proton is converted into a neutron by the transformation

The same result is obtained when the nuclei capture an extranuclear electron.

A few radionuclides can be decayed by one of these three variants and yet give rise to two
different stable nuclides. An example of this is 40 K, which decays by positron decay and
electron capture to the stable nuclide 40 Ar and is also transformed by   decay to the stable
nuclide 40 Ca.

b) Alpha decay (  ).
Since the alpha particle is composed of two protons and two neutrons, it is identical to the 4 He
nuclei. The emission of an alpha particle decreases the number of protons and the number of
neutrons of the product nuclei by two

Alpha decay may be followed by the emission of gamma rays.

This type of decay is available for a large nucleus of radionuclides having atomic numbers
greater than 58 and for a few low atomic number nuclides, including 5 He, 5 Li, 6 Be, and others
shown in Figure _____. The natural radioactive isotopes of U ( 235 U, 238 U) and Th ( 232 Th)
decay to stable isotopes of Pb through series

1.9.2- Law of radioactivity.

The law of radioactivity was discovered by Rutherford and Soddy (1902) and is expressed by
the statement that the rate of decay of a radioactive nuclide is proportional to the number of
atoms of that nuclide remaining at any time. If N is the number of atoms that remained, then:

where  is a proportionality factor called the decay constant and the minus sign indicates that the
decay rate decreases with time.
Integrating we obtain:
ln N = -  t + C
When t = 0, C = ln N 0 , with N 0 being the number of radioactive atoms at t = 0. Therefore, the
integrated form of the equation is:

It is convenient to define that the half-life time (T 1/2 ) is the time required for half of the
radioactive atoms to decay. Therefore, if t =T 1/2 , then N = N 0 /2. Substituting ______ into the
equation we will obtain:

56
Each radionuclide has a decay constant that must be determined experimentally. This can be
done by measuring their decay rates at time intervals and plotting the resulting decay curve.
According to the ________ equation, the disintegration rate (A) is equal to  N. Therefore, we
can reiterate the law of radioactivity in terms of decay rates by multiplying both sides of the
equation _______ by  .

Considering that A =  N, then we obtain

Logarithmizing the previous expression

This last expression represents the equation of a straight line where -  is the slope and ln A 0 is
the intercept. Obviously, the decay constant of a radionuclide can be determined from the slope
of the straight line fitted by measurements of the decay rate at known time intervals. The decay
curve can also be plotted in terms of the number of radionuclides remaining (N) versus time
measured in multiples of the half-life. Both forms of decay curves are illustrated in Figure 1.

1.9.3- Radiometric dating methods.

 K-Ar method.

+
40K 40
Ar T 1/2 = 1.19·10 10 a  e = 0.581·10 -10 a -1

40Ca
T 1/2 = 1.40·10 9 a   = 4.962·10 -10
to -1
In this case, two radioactive decay processes of 40
K are manifested:  + decay ( 40
K 40
Ar)
and  - decay ( 40 K  40 Ca).

This determines that the general equation of radioactive decay  + must be corrected with a
coefficient  e /  that expresses the fraction of 40 K atoms that decay at 40 Ar:

(1) (2)

where:

=e+

57
Knowing that 40 Ar does not originally exist in the rock, then the equations would be reduced to:

(3) (4)

This method is widely used for dating potassium minerals that retain 40 Ar quantitatively, such as
muscovite, biotite and hornblende in igneous and metamorphic rocks. The ages calculated from
equation (4) represent the time since the mineral being dated cooled through its blocking
temperature , below which 40 Ar is quantitatively retained. Therefore, the K-Ar ages of slowly
cooled minerals are underestimated.
It has also been used to date authigenic glauconite and illite in sedimentary rocks and for
samples of glassy basalt rocks. However, such applications require careful sample selection and
are not typical.
An alternative is radioactive decay  - , which would be expressed by complementary equations:

However, the possible application of this method collides with the facts that 40Ca is the most
abundant isotope of Ca (96.94%) and its isotopic composition is difficult to measure by mass
spectrometry.

 Rb-Sr method.
This method is based on radioactive decay  - ( 87 Rb  87 Sr).

87
Rb 87
Mr. T 1  2  48.8·10 9 a   1.42·10 -11 to -1
Considering that there is always a certain amount of 87 Sr in the original rocks, it is used as the
ratio ( 87 Sr/ 86 Sr) 0 = 0.7040 in oceanic basalts as an initial reference to the isotopic composition
of strontium.
In this way, the equations would be represented as:

 U-Pb, Th-Pb method.

This method is based on the occurrence of 3 radioactive decay processes: ( 238
U  206 Pb), ( 235

U  207 Pb) and ( 232 Th  208 Pb).

238U 206
Pb + 8 4 He T 1  2  4.468·10 9 a  1  1.55125·10 -10 to -1
235U 207
Pb + 7 4 He T 1  2  0.7038·10 9 a  2  9.8485·10 -10 a -1
232Th 208
Pb + 6 4 He T 1  2  14.010·10 9 a  3  4.9475·10 -11 a -1
To rectify the effect caused by the presence of 206 Pb, 207 Pb and 208 Pb originally in the rock, the
relations ( 206 Pb/ 204 Pb) 0 = 12.97, ( 207 Pb/ 204 Pb) 0 = 14, are introduced. 17 and ( 208 Pb/ 204 Pb) 0
= 33.90. According to this, the equations would be like:

58
59
 CHAPTER II

STATES OF EXISTENCE OF CHEMICAL ELEMENTS (AND THEIR NUCLIDIES) IN

NATURE

The study of the forms of existence of chemical elements in nature is of great significance
because in the different upper geospheres and natural formations manifestations of all the
elements are seen in which the chemical properties of each element and its compounds are
implicit. , its abundance in nature and the physical and chemical conditions of the environment
in which the formation of its compounds occurred.
The correct interpretation of all the information derived from the study of the forms of existence
presents great value for the location of meniferous accumulations of different elements in the
most varied geological conditions. But, it also becomes possible to infer the physical-chemical
conditions that led to the formation of these deposits.

2.1- States of existence from qualitative and quantitative points of view.

From a qualitative point of view, chemical elements can exist in two different states: mineral and
amineral.
Furthermore, regardless of the previous states, from a quantitative point of view, chemical
elements are characterized by two distinguishable aspects: concentrated and dispersed.

2.1.1- Mineral state and amineral state.

A chemical element is in a mineral state when it is part of natural chemical combinations (they
can rarely appear as native elements) that respond to stoichiometric laws (of defined chemical
composition) and with an ordered atomic arrangement (fixed crystalline structure). This
determines that the mineral state for a chemical element is only possible when it is part of a
crystalline and homogeneous solid.
A chemical element is in an amineral state when it does not form independent minerals, but
rather tends to be incorporated in the form of indefinite mixtures in minerals, rocks and other
natural formations. This implies that the amineral state for a chemical element can be
represented by different aggregation states of its compounds or ions (solid, liquid, gaseous).
In many cases the chemical composition of a substance is not what determines whether a
chemical element that forms it is in a mineral or amineral state. In these cases, we usually resort
to establishing the existence or not of a crystalline structure in the substance considered.
Examples :
Substances Mineral state Amineral state
H 2 O ice liquid water and vapor
SiO 2 opal quartz (hydrated)

In the different upper geospheres, the mineral state and the amineral state of the chemical
elements are manifested with predominances that are distinguished in each of them.
In the Earth's crust, the mineral state predominates for chemical elements, expressed in the fact
that 98.6% of the entire mass of this geosphere is found in this state.
In the hydrosphere there is a clear predominance of the amineral state for the chemical elements
that compose it. However, hydrogen and oxygen can be found in a mineral state in ice shields,
glaciers, polar icebergs, etc.
In the biosphere and the atmosphere, the amineral state largely predominates due to the
particularities of these two geospheres.
The limit between the sizes of the particles that form the amineral state is to a certain degree
conditional, and the maximum resolving power of the human eye (0.01 mm) can be established

60
as a limit. Therefore, finer mineral grains, molecular aggregates, colloidal dispersions and
mechanical impurities are conventionally included in the amineral state.

61
2.1.2- Dispersed state and concentrated state.
A chemical element exists in the dispersed state when its content in a natural formation is close
to the value of its clarke normal for the geosphere to which it belongs.
A chemical element is in the concentrated state when its content is close to that corresponding to
the industrial categories for its useful minerals. This means that the concentrated state for a
chemical element must be measured by tens, hundreds, thousands, etc. of their normal clarkes in
the corresponding geosphere.
Between the dispersed state and the concentrated state transitions are possible and their border,
to a large extent, is defined not by geological, but by economic reasons.
It is known that the reserves of the elements concentrated in mineral deposits make up only
hundredths or tenths of the percentage of the general reserves that correspond to them in the
Earth's crust (table 2.1).

Metal Reserves in a 1 km thick Reserves in the deposits Part of the metal

layer of crust (Ry) (in tons) concentrated in the deposits
(Rc) (in tons) (Ry/RC)
Faith 2,0·1016 4,2·1012 2,1·10-3
Cu 2,0·1013 1,8·1010 9,0·10-4
Pb 6,7·1012 9,9·109 1,5·10-3
13
Zn 3,5·10 11,3·109 3,2·10-4
Neither 2,4·1013 6,0·108 2,5·10-5
12
Co 1,2·10 5,1·107 7,1·10-6
Yes 1,1·1012 5,1·108 4,6·10-4
W 5,5·1011 1,14·108 2,1·10-4
11
mo 4,4·10 1,2·108 2,7·10-4
Hg 3,5·1010 3,6·107 1·10-3
9
Au 1,8·10 3,1·106 1,7·10-3
OR 1,0·1012 1,44·107 1,4·10-5

Table 2.1- Correlation between the concentrated and dispersed state for a group of meniferous
elements.

From the analysis of this table some important conclusions can be drawn:
1- The dispersed state considerably predominates over the concentrated state. This implies that
the dispersed state of existence of the chemical elements is considered normal, while the
other is taken as anomalous.
2- Between the dispersed state and the concentrated state, a clear correlation dependence can be
seen. This constitutes evidence of the dialectical unity that exists between these opposites,
such that the existence of the dispersed state conditions the scope of the concentrated state
and vice versa.

This last aspect is confirmed in the following graph:

62
Fig. 2.1 Relationship between the dispersed state and the concentrated state for various
meniferous elements.

The qualitative point of view should never be confused with the quantitative point of view
followed to establish the state of existence of chemical elements in nature. This is justified by
the fact that some chemical elements can be found in the concentrated state without necessarily
having to form minerals.

2.2- Forms of existence of chemical elements in the upper geospheres.

2.2.1- Forms of existence of chemical elements in the Earth's crust.
In the earth's crust it is necessary to make a clear distinction between the products that constitute
it, which could be represented as:

Earth crust

Rocks Solid products

of weathering

 Forms of existence of chemical elements in rocks.

Characteristic of rocks is the state of mineral existence of chemical elements, represented by
more than 2000 known minerals.
According to the main types of chemical combinations, mineral species are distributed as
follows (in %).
1- Silicates and alumosilicates ...................... 25,8 %
2- Phosphates and analogous minerals .................18.0%
3 - Sulfides and analogous minerals ................13.3%
4 - Oxides and hydroxides ........................................... 12,7 %
5 - Sulfates ................................................ ..... 9,4 %
6 - Halides ................................................ 5,8 %
7 - Carbonates ............................................... .4.5%
8 - Native elements ...................................... 3 %
9 - Borates ................................................. ...... 2,9 %

63
 10 - Others................................................. ....... 3.3%

As you can see, most of the mineral species correspond to silicates, phosphates, oxides, sulfides
and sulfates, which account for approximately 80%. This shows the chalcophilic character that
corresponds to a more limited quantity. The siderophile character is barely manifested in the
elements that make up the Earth's crust.
Taking into account the masses of the different mineral species in relation to the mass of the
Earth's crust, these are distributed as follows (in % by mass):
1- Silicates and alumosilicates ................................. 75.0 %
Feldspars................................................. .....55.0%
2 - Oxides and hydroxides ........................................... 17.0 %
Quartz (with chalcedony and opal) ..................... 12.6%
Iron oxides and hydroxides ......................... 3,6 %
3 - Carbonates ................................................. ....... 0.7%
4 - Phosphates and analogous minerals ......................... 0,7 %
5 - Halides ................................................. ...... 0,5 %
6 - Sulfides and sulfates ........................................... 0,3-0,4 %
7 - Native elements ........................................... 0,1 %

These data show that silicates and quartz alone constitute approximately 87% by mass of the
Earth's crust, while phosphates, sulfides, sulfates and oxides, represented in natural conditions
by numerous mineral species, are an insignificant part of the mass of the earth's crust.
Silicates and quartz are the main rock-forming minerals of the Earth's crust. Phosphates,
sulfides, sulfates and oxides contain valuable metals, many of them being meniferous minerals
of enormous importance for the minor metallurgical, chemical, etc. industries.
On the other hand, when checking the abundance of chemical elements in the Earth's crust (such
as atomic clarke) with the quantities of mineral species they form, we will see that between these
aspects there is a certain direct dependence, with some small exceptions.

Number of
Element atomic clarke
minerals
EITHER 53,39 1221
h 17,55 798
Yeah 16,11 377
To the 4,80 268
na 1,82 100
Mg 1,72 105
AC 1,41 194
Faith 1,31 170
K 1,05
c 0,51 194
You 0,22 30
CL 0,18 67
F 0,17 50

Table 2.2- Relationship between the abundance of chemical elements (atomic clarke) and the
minerals they form.

The ability of chemical elements to form various mineral species also depends on their chemical
properties and the fact that the greatest variety of mineral species corresponds to elements with
small atomic numbers (Z<26) is striking.

64
The chemical elements can be grouped as follows according to the order of decrease in the
ability to form minerals:

Groups Constituent Ability to form minerals Examples

elements
1st Group O, Si, Al, Fe, They are found mostly in a diopside (CaMg(SiO 3 ) 2 )
(8 items) Ca, Na, K, Mg. mineral state (99% by anorthite (CaAl 2 Si 2 O 8 )
mass) in the Earth's crust, albite (NaAlSi 3 O 8 )
forming: silicates, microcline (KAlSi 3 O 8 )
alumosilicates, carbonates quartz (SiO 2 )
and oxides, mainly calcite CaCO 3
siderite FeCO 3
dolomite CaMg(CO 3 ) 2
magnetite Fe 3 O 4
hematite Fe 2 O 3
goethite Fe(OH) 3
2nd Group Ti, H, C, P, S, They predominate in the Zircon ZrSiO 4
(6 items) Zr. mineral state (90% by kaolinite Al 4 Si 4 O 10 (OH) 8
mass) in the Earth's crust biotite K(Mg, Fe) 3 Si 3 AlO 10 (OH,
forming: silicates, F) 2
alumosilicates, oxides, rutile TiO 2
phosphates, sulfides, ilmenite FeTiO 3
carbonates and native apatite Ca 5 (PO 4 ) 3 (F, CI)
elements. pyrite FeS 2
gypsum CASO 4  2H 2 O
barite BaSO 4
calcite CaCO 3
magnesite MgCO 3
3rd Group Cr, Y, Ce, La, There is no predominance chromite: FeCr 2 O 4
(12 items) F, Cl, Cu, Ni, of the mineral state over pyrolusite: MnO 2
Os, Ir, Pt, Mn. the amineral state (50% by cuprite Cu 2 O
mass) in the Earth's crust. xenotime: YPO 4
apatite: Ca 5 (PO 4 ) 3 (F, Cl)
fluorite: CaF 2
halite NaCl
silvite KCl
carnallite: MgCl 2 • KCl • 6H 2 O
chalcopyrite CuFeS 2
Calcosin: Cu 2 S
pentlandite: (Fe, Ni) 9 S 8
4th Group Li, Be, B, Nb, They are found mainly in datolite CaBSiO 4 (OH)
(24 items) Ta, Th, U, Mo, an amineral state (90% by spodumene LiAlSi 2 O 6
W, Sn, Zn, Pb, mass) in the Earth's crust. beryl Be 3 Al 2 Si 6 O 18
Co, Hg, Ag, galena PbS
Au, Ge, As, Bi, ZnS sphalerite
Se, Tl, Sr, Ba, cinnabar: HgS
V sphalerite: ZnS
galena: PbS
realgar: AsS
molybdenite: MoS 2
cassiterite SnO 2

65
 uraninite UO 2
thorianite ThO 2
vanadinite Pb 5 (VO 4 ) 3 Cl
strontianite SrCO 3
wulfenite PbMoO 4
powelite CaMoO 4
columbite (Fe, Mn)Nb 2 O 6
tantalite (Fe, Mn) Ta 2 O 6
5th Group Rb, Cs, Sc, Cd, They are almost always
(35 items) Ga, Hf, In, Re, found in the amineral state
Ru, Rh, Pd, Br, in the Earth's crust.
I, N, He, Ne,
Ar, Kr, Xe, Pr,
Nd, Sm, Eu,
Gd, Tb, Dy,
Ho, Er, Tm,
Yb, Lu, Ra, Pa,
Po, Te.

Table 2.3- Groups of elements according to their ability to form minerals.

Although in the Earth's crust there is a complete predominance of the mineral state over the
amineral state, some forms of existence of chemical elements can be manifested in the latter
state, the study of which is very valuable for the resolution of certain geological problems
related to mineral processes. logénisis, petrogénisis and formation of reservoirs. Among these
forms of amineral existence, the most important are:
e) Solid solutions.
e) Interstitial forms.
e) Mechanical inclusions.
e) Intercrystalline inclusions.
e) Solutions in pore waters.

Next, the main characteristics of each of these forms of amineral existence will be studied,
highlighting the conditions that favor their manifestation for some chemical element. In
addition, certain information will be given about the importance of the study of each one of
them.

a) Solid solutions.
Solid solutions represent the product of the isomorphic substitution of one ion for another in a
defined crystalline structure. Solid solutions may be formed through the occurrence of isovalent
or heterovalent isomorphism, which is fundamentally determined by the similarity between the
sizes of the ions that are substituted.
The formation of solid solutions is closely related to the thermodynamic conditions of the
environment in which the mineral was formed; These determine the intensity and extent of
isomorphism in many minerals. In general, at high temperatures the isomorphic situation can
occur between ions whose sizes differ by up to 20-30%, while at low temperatures isomorphism
is only possible if the size of the ions does not differ by more than 10-15%. Another important
condition of isomorphism is the similarity of the electronic structure of the ions, and the affinity
of their chemical properties.
For minor elements (and especially rare and disperse elements) isomorphism and the formation
of solid solutions constitute their fundamental geochemical characteristic. As these elements are
not very abundant in any geochemical system, it is expected that the isomorphism will be limited
66
(imperfect) even when all the requirements are met so that this process can occur with complete
replacement of one ion by another in the considered crystalline structure. According to this, rare
and dispersed elements are found as isomorphic impurities in other minerals without forming
their own minerals.
To explain the isomorphic substitutions by which some of these elements are included in the
crystalline structures of minerals, Goldschmidt introduced three fundamental concepts
(occultation, capture and admission) that faithfully characterize isomorphism structurally and
energetically. These three varieties of isomorphism regulate the form of amineral existence of
most of the rare and dispersed elements in the Earth's crust.

Concealment.
A solid solution is formed by occultation when a minority element isomorphically replaces
another element with the same charge and similar ionic radius, in the crystalline structure of a
mineral formed by the latter.
Examples:
 Ga 3+ (0.062 nm) can isomorphically replace Al 3+ (0.051 nm) in the crystalline structures of
alumosilicates, oxides and other minerals.
Muscovite (KAl 2 (Si 3 AlO 10 )(OH,F) 2
Lepidolite (Kli 1 , 5 Al 1,5 (Si 3 AlO 10 )(OH, F) 2
 Sr 2+ (0.112 nm) isomorphically replaces Ca 2+ (0.099 nm) in the crystalline structure of
aragonite (CaCO 3 ) existing in the calcareous remains of marine organisms.
 Ge 4+ (0.053 nm) isomorphically replaces Si 4+ (0.042 nm) in silicates and quartz (SiO 2 ).

67
 Capture.
A solid solution is formed by capture when a minor element isomorphically replaces another
element of lower valence and similar ionic radius, in the crystalline structures of a material
formed by the latter.

Examples:
 Pb 2+ (0.120 nm) isomorphically replaces K + (0.133 nm) in the crystalline structure of
potassium feldspar (KAlSi 3 O 8 ) of granitic pegmatites.
 Ba 2+ (0.34 nm) and Sr 2+ (0.112 nm) can isomorphically replace K + in the crystal structure
of potassium feldspar (KAlSi 3 O 8 )
 In 3+ (0.081 nm) isomorphically replaces Zn 2+ (0.083 nm) in the crystal structure of
sphalerite (ZnS).

Admission.
A solid solution is formed by admission when a minor element isomorphically replaces another
element of higher valence and similar ionic radius in the crystalline structure of a mineral
formed by the latter.
Examples:
 Li + (0.068 nm) isomorphically replaces Mg 2+ (0.066 nm) in the crystal structure of
muscovite (KAL 2 (Si 3 ALO 10 )(OH,F) 2 ).
 Sc 3+ (0.081) isomorphically replaces Zr 4+ (0.087 nm) in the crystal structure of zircon
(ZrSiO 4 ).

ISOMORPHIC SUBSTITUTION BY:

CONCEALMENT CAPTURE ADMISSION
2+ 2+ 2+ 2+ + 2+ 2+ 2+
Mg - Fe - Mn - Co - Ni K - Ba - Sr - Pb O - OH - - F -
2-
2+ 2+ 3+
Ca - Y Yes 4+ - At 3+
Al 3+ - Ga 3+ - Mn 3+ Mg 2+ -Sc 3+ Mg 2+ - Li +
4+ 4+ 4+ 2+ 3+
Si - Ge - Ti Fe -Sc
5+ 5+ 5+
P - V - Ace Yes 4+ - P 5+
+ + + +
K - Rb - Cs - Tl
Ca 2+ - Sr 2+ - Mn 2+

The analysis of this table leads us to verify the similarities between the ionic radii in each of
these series.
Why is it useful to study solid solutions as forms of amineral existence of chemical elements in
the Earth's crust?
There are many applications of the results of research carried out in the study of solid solutions.
Among them it is interesting to highlight that:
1- It is possible to justify the existence of anomalous contents of many rare and dispersed
elements in minerals and rocks, through isomorphic substitutions. This constitutes an
important result that makes it possible to predict in which minerals and rocks the most
exceptional contents of chemical elements such as: Re, Cd, In, Hg, Se, Cs, etc. appear.
Which allows you to direct your search for them in certain natural formations and rock
formations. An example of this application is the discovery of anomalous Cd and In contents
in the sphalerite (ZnS) of the Amistad polymetallic deposit (NW of Pinar del Río).
2- It has been tried to be applied to determine the formation temperatures of minerals although
the effectiveness of this procedure has not been convincingly demonstrated since the content
of rare and dispersed elements can be variable in a more or less wide range for the same
mineral depending on much of the concentration of these in the geochemical system where
the mineralogenesis processes are occurring.

68
b) Interstitial forms.
Between the atoms, ions or ionic groups that are forming a compact packing in a crystal, there
are always some interstices or structural voids, it is proposed that they are in interstitial form.
Examples:
 The sodium and aluminum atoms are capable of occupying the interstices existing in the
crystalline structure of tridymite (SiO 2 ).
 The ions K + , Rb + , Cs + , as well as H 2 O and He can accommodate interstitially in the
hexagonal channels of Beryl (Be 3 Al 2 Si 6 O 18 ).

What usefulness can the study of interstitial forms bring?

In reality, these constitute curiosities of the crystalline structures of minerals in whose interstices
large ions, atoms and molecules tend to move away. Many times they resort to justifying the
existence of elements foreign to a crystalline structure through interstitial forms.

c) Mechanical inclusions.
These constitute microdispersed mechanical mixtures (crystallosals and crystallogels) of some
substances in certain minerals. These substances are distributed homogeneously throughout the
mineral but their presence cannot be explained on the basis of the crystalline structure and
chemical composition of the mineral in question.
Examples:
 Green quartz (prasem) owes its color to the fact that it contains mechanical impurities of
actinolite (Ca(Mg,Fe) 5 (Si 4 O 11 ) 2 (OH) 2 ) and chlorite ((Mg,Fe) 5 Al(AlSi 3 O 10 )(OH) 8 ).
Rose quartz (aventurine) presents mechanical impurities of hematite (Fe 2 O 3 ).
 Red calcite contains hematite crystallosols (Fe 2 O 3 ).
 In pyrite there may be very fine particles of gold that are considered crystallogels.

To what degree can the study of mechanical inclusions be important?

It is necessary to initially state that the existence of mechanical inclusions in minerals can be
harmful in some cases and useful in other cases. It all depends on the use that will be given to
the mineral raw material and the degree of purity that it must have to be used for certain
purposes.

The harmfulness of mechanical impurities in minerals can be seen in the manufacture of glass
for optical equipment, where the existence of iron oxides included in quartz makes it difficult to
achieve adequate product quality.

Mechanical impurities are useful from several points of view. Firstly, certain colorations of
minerals caused by the inclusions of other substances can give them ornamental and precious or
semi-precious stone qualities. On the other hand, the existence of noble metals in microdisperse
form in some minerals can constitute another source of obtaining them during mineral benefit
and metallurgical processes.

d) Liquid and gaseous intercrystalline inclusions.

These represent bubbles of liquids and gases contained in the crystalline structure of some
pneumatolytic and hydrothermal minerals.
Liquid and gas inclusions can be primary (mechanically imprisoned by the crystal in the process
of its rapid growth) or secondary (coinciding with the "healed" indentations of the crystals).
Many meniferous elements have been discovered in liquid inclusions, such as: Pb, Zn, Cu, Ag,
Sn, Ba, etc., in concentrations that exceed their normal clarkes in the Earth's crust by several

69
times. They express the chemical composition of the hydrothermal or pneumatolytic solution
that originated the mineral that contains them.
As part of the gas inclusions of some minerals appear: CO 2 , H 2 S, H 2 , NH 3 , F 2 , Cl 2 , and
other volatile components of the pneumatolytic and hydrothermal solutions that led to the
formation of the mineral in which they are they find.

What applications do investigations of liquid and gas inclusions have?

In modern research aimed at elucidating mineral formation processes, the particularities of liquid
and gas inclusions are playing a determining role. Among other issues, problems such as:
1. Determination of the chemical composition and the forms of existence of chemical elements
in pneumatolytic and hydrothermal solutions.
2. Determination of the formation temperatures of pneumatolytic and hydrothermal minerals.
For this, two methods are usually applied: hemogenization and decrepitation.
3. By applying the homogenization method, the origin of the mineral can be confirmed
(pneumatolytic and hydrothermal).

e) Solutions in pore waters.

All rocks, even those that are dry from the outside, contain a certain amount of water (about
0.7%). This can be of two types:
- Molecular-film water that surrounds all interior intergranular surfaces with a thin layer the
thickness of one molecule.
- Banded water - film that fills cracks and pores in rocks.

These pore waters can only be extracted from rocks by heating them to very high temperatures
(several hundred degrees Celsius).
The appearance of appreciable concentrations of meniferous elements dissolved in pore waters
is common.
Example:
 In some granites, accumulations of Pb, Zn, U, associated with pore waters, have been found,
their concentrations being hundreds of times higher than their normal clarkes in the rocks.

What is the usefulness of solutions in pore water?

Quantitatively, these solutions are not capable of providing sufficient quantities of metals to be
exploited industrially. However, from the point of view of research on rock formation processes
it can provide some useful information regarding the composition of aqueous solutions that
diffuse into their pores in the form of microscopic emanations.

 Forms of existence of chemical elements in weathering crust, sediments and soils.

Different forms of existence of chemical elements are characteristic of weathering crusts, related
to the processes of mechanical disintegration, chemical decomposition and biological activity
that give rise to their formation.
The formation of colloidal systems and the occurrence of surface phenomena (adsorption)
faithfully characterize the forms of existence in weathering crusts.
Between these two aspects there is a link that should not be ignored when studying them, that is,
adsorption depends on the existence of colloidal systems.
According to this, two forms of amineral existence of chemical elements can be manifested in
the weathering crusts: colloidal forms and sorbed forms.
Next, we will go on to study the essential characteristics of these forms of existence, establishing
the links that exist between them. In addition, a brief overview of the importance of studying
them will be made.

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a) Colloidal forms.
What are the causes of the formation of natural colloids in weathering crusts?
To answer this question we must resort to the analysis of the processes that occur during the
formation of the weathering crust from minerals and primary rocks.
In the course of the physical, chemical and chemical-biological weathering of primary rocks and
minerals, an uninterrupted grinding (mechanical disintegration) and a chemical transformation
(chemical decomposition) occur as a result of the action of different exogenous agents. As a
result of the mechanical destruction of rocks and minerals, the size of the particles decreases and
can acquire colloidal dimensions (10 -3 -10 -6 nm) with a certain residual electrical charge. On the
other hand, chemical decomposition can lead to the formation of poorly soluble oxides and
hydroxides that constitute colloidal particles that acquire their electrical charge by adsorption of
ions in weathering solutions.
Most of these natural colloids have a negative electrical charge, except for some iron (III) and
aluminum hydroxides.
Silica, humus, peat, hydrated manganese dioxide, iron (III) hydroxide, clays, phosphorites
constitute colloidal systems with negatively charged particles. These colloidal systems are
initially in the form of hydrosols. As a result of the mutual coagulation of hydrosols of opposite
charges or under the action of dissolved electrolytes, coagulation or precipitation of these
hydrosols can occur, with the consequent formation of hydrogels.
Among the most characteristic hydrogels of the weathering crust are: opal (SiO 2 .nH 2 O) and
hydrogoethite (FeO(OH).nH 2 O). When dehydrated and crystallized, these (amorphous)
hydrogels become crystalline structure.
The joint coagulation of hydrosols of SiO 2 , Fe(OH) 3 and Al(OH) 3 is completed with the
formation of clay minerals, whose finer particles behave as colloids.

b) Sorted forms
Many of the ions are part of the true solutions that are generated in the weathering crust; they
can be separated from them by virtue of the great adsorption capacity possessed by the colloidal
particles that make up this medium.
Examples:
Clay colloids adsorb potassium, vanadium, rubidium, cesium, nickel, among other elements.
The silica colloid adsorbs uranium.
The colloid of iron (III) hydroxides adsorbs arsenic, vanadium and phosphorus.
Magnesium (IV) hydroxide colloid adsorbs cobalt, nickel, copper, zinc, barium, radium and
among other heavy metals.

All these elements that are adsorbed by the colloids are found in a sectioned form in the
weathering crust, concentrating selectively in the mineral groupings that exist.
From what has been expressed so far, you will be able to realize that the importance of studying
the forms of amineral existence in the weathering crust lies in the consequences that surface
phenomena (adsorption) have on the selective accumulation of elements by colloids, which
could end up having some practical use for the exploitation of some radioactive, dispersed and
rare elements.

2.2.2- Forms of existence of chemical elements in the hydrosphere.

As already stated on one occasion, the mineral state in the hydrosphere is represented almost
exclusively by ice (H 2 O), which is permanently associated with the polar regions.
Water and the rest of the components found temporarily or permanently in it include the
chemical elements in the amineral state in this upper geosphere.
The chemical elements that form an integral part of the temporary or permanent components of
natural waters could be found in three possible forms of amineral existence:

71
a) Mechanical suspension.
b) Organic and inorganic colloids.
c) True solutions.
Next, the main differences that exist between these forms of amineral existence of chemical
elements in the hydrosphere will be analyzed. The essential causes that influence the fact that
certain chemical elements prefer to be part of them with respect to others, and the importance
that this can have in sedimentary processes and on the accumulation of chemical elements in
different systems must be highlighted. geochemical (water, sea, continental and marine
sediments, terrestrial and marine organisms, etc.).

a) Mechanical suspensions.
Mechanical suspensions are characterized by having particles whose sizes in the dispersed phase
are greater than 1  m (10 - 6 m).
It has been estimated that 2/3 of the material transported by river waters is in this state, although
the proportion may vary depending on the size of the particles that result from the disintegration
of minerals and rocks during weathering. to the sea where, finally, the mechanical separation
and disposal of this material occurs depending on the size of the suspended particles. Thus, large
particles tend to settle along the coast in a short time, while smaller ones manage to remain
suspended in seawater for thousands of years.
It is evident that mechanical suspensions are temporary in nature, their existence being
conditioned by the size of the particles in the dispersed phase and the kinetic energy of the water
flows that contain it.
It is logical to assume that these particles are very poorly soluble in water, and can be
represented by a wide variety of disintegrated mineral compounds that meet this condition.
Among them we should highlight: clay particles, iron (III) hydroxides, aluminum hydroxide,
manganese hydroxide, etc. It is characteristic that the continental or marine sedimentation of
these particles contributes to the enrichment of the hydrolyzed, oxidized and unattached
(resistates) in certain elements.

b) Organic and inorganic colloids.

Organic and inorganic colloids are represented by molecular aggregates whose sizes range
between 0.1 m (10 - 7 m) and 1 nm (10 - 9 m). These particles have the essential characteristic of
electric charge, which can be positive or negative.
This electrical charge can originate in two ways:
1- By adsorption of ions from the liquid.
For this to happen, the existence of small concentrations of electrolytes in the solutions is
necessary, which when adsorbed will give their charge to the colloidal particle.
2- By direct ionization of the particle material.
This process is closely linked to the weak acidic or basic properties that colloidal particles
exhibit in an aqueous medium that contains almost no dissolved electrolytes.
For example, iron (III) hydroxide has a weak basic character so it tends to form positively
charged colloidal particles in natural waters as a result of its autoionization. Meanwhile, silica
and manganese (IV) hydroxide have a weak acid character which determines that they form
negatively charged colloidal particles in natural waters through autoionization.
Among the most significant colloids we should point out:

POSITIVE COLLOIDS NEGATIVE COLLOIDS

Aluminum hydroxides Silica
Iron (III) hydroxides Manganese (IV) hydroxide
Chromium (III) hydroxides Clay particles
Hydrated titanium dioxide iron (III) hydroxides
Hydrated thorium dioxides Humic colloids
72
Hydrated zirconium dioxides Vanadium pentoxides

Colloidal systems in the dispersion medium is water are divided into: hydrosols and hydrogels.
Hydrosols are colloidal systems that resemble liquids due to their fluidity. These can be divided
into: hydrophilic and hydrophobic.
Hydrophilic sols are characterized by the existence of a strong interaction between the particles
and water molecules, which allows the colloidal solution to be stabilized.
In hydrophobic sols there is no such attraction between the particles and water molecules, and
because of this they are much less stable than hydrophilic sols and precipitate more easily. There
is no sharp boundary between these two types of hydrosols, but the division is useful. Silica is an
example of a hydrophilic sol; aluminum forms a hydrophobic sol.
Hydrogels are colloidal systems that exhibit some rigidity. These systems may form due to
coagulation of hydrophilic sols under the effect of dissolved electrolytes or some other physical
change. In this case, the lyophilic sols imprison appreciable quantities of water molecules, which
determines the gelatinous appearance of this rigid mass.
The coagulation of lyophobic colloids does not entail the dragging of any amount of water
molecules, but rather they precipitate in the form of fine powder or lumps.
Organic (humic) colloids seem to play a very important role in the stabilization and protection of
inorganic colloids against coagulation. It is significant that the existence of such colloids slows
down the coagulation process due to the effect of the electrolytes dissolved in the solutions,
allowing the hydrosols to remain as such for a longer time. The destruction of organic colloids
under the action of bacteria is an essential cause for the coagulation of hydrosols existing in
natural waters.
Everything discussed up to this point allows us to appreciate that hydrosols are temporary in
nature, and can exist when there are no appreciable concentrations of dissolved electrolytes or in
the presence of protective colloids.
At the mouths of rivers and in the sea itself, coagulation of hydrosols is very common due to the
action of dissolved electrolytes, which leads to the sedimentation of colloidal particles.
When most inorganic colloids coagulate, they separate from the true solution some ions that
have been adsorbed by them and accumulate in the hydrolysates. The study of these processes is
very useful in being able to establish the existence of certain elements associated with clay
sediments, iron (III) oxides and hydroxodes, iron (III) oxides and hydroxides; Among these
elements we should mention: Li, K, U, Th, Ra, etc.

c) True solutions.
True solutions are made up of a dispersed phase of ions, groups of ions and molecules whose
sizes range between 1 and 0.1 nm.
It can be assured that the determining factor for the existence of elements in true solution is the
solubility of their natural compounds. The content of each element in the weathered rocks and
the leaching of soluble products by weathering solutions and river waters is also a factor to be
taken into account when establishing the presence of certain elements in true solutions.
Depending on the solubility of the different natural compounds and their concentration in water,
true solutions can be divided into: saturated and unsaturated.
Saturated solutions are those that contain the maximum possible amount of dissolved substances,
so the addition of new amounts of said substance will not be able to remain in the solution and
will precipitate. It is clear that saturated solutions will transport part of the carbonates and silica
(CaCO 3 , MgCO 3 and SiO 2 ).
Unsaturated solutions are those that contain a certain amount of dissolved substance without yet
reaching the saturation state, that is, they can dissolve a certain amount of a given substance
without changing the external conditions. It is evident that easily soluble salts (NaCl, KCl,
MgSO 4 , CuSO 4 , MgCl 2 , CaCl 2 ) are transferred to unsaturated solutions.

73
Sedimentation of these compounds from true solutions can occur due to exceeding their
solubility products or due to evaporation of water. However, certain amounts of the ions present
in true solution are separated from it by the effect of colloid adsorption and as a result of
biogenic absorption.
When sedimentation occurs as a result of the compounds reaching their solubility limit, they
become incorporated into the inorganic precipitates. If this occurs as a result of the evaporation
of water, the compounds that settle tend to enrich the evaporated ones. The existence of colloids
in contact with the true solutions determines that some ions become part of the hydrolyzed and
oxidized ones. Finally, the biogenic adsorption that marine and terrestrial organisms develop on
certain compounds in true solution can constitute the beginning of the accumulation of some
elements in their different parts and their subsequent organic precipitation.

 Graphically show the distribution of elements and compounds in mechanical suspensions,

colloidal solutions, true solutions (saturated and unsaturated), relating it to the position
occupied by the different elements in the periodic table, giving students active participation
in the sense of the links that exist. can establish precedents with knowledge.
 Guide the study of the differences between mechanical suspensions, colloidal solutions and
true solutions based on: factors related to their formation, particularities of each one, ways of
separating the elements and their compounds from them, tendency of certain elements to be
found forming part of these in relation to their chemical properties.

2.2.3- Forms of existence of chemical elements in the atmosphere.

As is well known, in the atmosphere there is a complete predominance of the amineral state of
existence of the chemical elements.
All the components that are temporarily or permanently in it tend to be in an amineral state.
The chemical elements included in these components of the atmosphere must be found in five
main forms of mineral existence:
a) Gases and vapors.
b) Terrestrial and meteoritic dust.
c) Saline suspensions
d) Suspensions of organic matter.
e) Aerosol sprays.

a) Gases and vapors.

Gases and vapors are made up of covalent molecules and atoms that can remain in this state due
to their great volatility.
The chemical elements that are usually found in this form are carbon, nitrogen, oxygen, noble
gases, sulfur, hydrogen, among others.
Many of the gases that exist in the atmosphere have a more or less permanent character in it;
However, the interaction of several of them with the hydrosphere, Earth's crust and biosphere
gives them a somewhat temporary existence, although they have remained essential components
of the atmosphere for a long period of the Earth's geological history. Among these gases we
must mention oxygen, carbon dioxide and others of less global significance.
Other gases have a local character, this being determined by human activity and/or by the
occurrence of natural phenomena, which generate large quantities of these. Thus, industrialized
and highly populated regions usually contain some excessive amounts of gases in the atmosphere
that surrounds them, most of which come from the processes that take place during industrial
activity; the most common gases in these regions with carbon dioxide, sulfur trioxide, nitrogen
dioxide and several more. For their part, the regions where there are still signs of volcanic
activity contain different gases in the surrounding atmosphere from the emanations of various
volatile substances: water vapor is the most important component of both of these emanations,
followed by carbon dioxide. , nitrogen dioxide, sulfur, hydrogen chloride, etc. The
74
decomposition of organic matter and formation can constitute important sources for gases such
as carbon dioxide and methane. Helium and argon are related to the natural radioactive decay
processes of uranium, thorium and potassium-40, and can be found associated with volcanic
gases and natural petroleum gas.
The water vapor existing in the atmosphere has its origin in the hydrosphere and in its
emanations until the formation of rainwater and the dissolution of some gases in them,
contributed to the separation of various elements from the gaseous medium.

b) Terrestrial and meteoritic dust.

Volcanic eruptions and explosions throw considerable quantities of finely divided materials into
the atmosphere, which can remain suspended in the atmosphere for a longer time due to the
small size of the particles and the action of the winds. Other materials disintegrated on the
Earth's surface follow a similar path, also remaining temporarily in the atmosphere.
On the other hand, the atmosphere is constantly crossed by meteorites of various sizes, which
release very fine particles during their friction with the air. This phenomenon determines the
formation of meteoritic dust that is finally deposited on continental surfaces or on the bottom of
the seas.

c) Saline suspensions.
These salt suspensions originate from seawater splashing in coastal areas and on the high seas. In
this way, the chlorides and sulfates of the alkaline-earth metals pass into the atmosphere in the
form of very fine particles since it is necessary to highlight the role that the atmosphere and its
essential components play in the geochemical processes that take place in the remaining
geospheres. superiors; But, above all, it highlights how extremely harmful the large amount of
gases, vapors and smoke that man dumps into the atmosphere in the form of uncontrollable
sediments are for the biosphere.
Although some steps have already been taken in the use of industrial waste through the use of
filters that prevent the passage of these harmful substances into the atmosphere, this idea is still
incipient, so an additional push is required in this regard in adaptation with the meaning that this
has for the maintenance of life on our planet.
On the other hand, the industrial exploitation of several essential components of the atmosphere,
such as oxygen, carbon dioxide, helium, hydrogen, etc., is now common.

d) Suspensions of organic matter.

The wind is capable of keeping plants, animals and their products temporarily suspended in the
atmosphere. Humus particles suspended in the air have also been found, as a result of the same
mechanism.

e) Aerosol sprays.
Aerosols are colloidal dispersions of solids or liquids in gases. In the atmosphere, these varieties
of colloidal systems manifest themselves in the form of smoke (colloidal dispersions of solids in
the air) and fogs (colloidal dispersion of liquids in the air). Smoke has its origins in man-made
and natural combustion processes. They are fundamentally made up of very small carbon
particles.
Arsenic is highly concentrated in coal ash, which is why smoke particles from cities and
industrial centers and their surroundings tend to be enriched in this element. The smoke is not
only desiccatable in itself, but its particles act as condensation nuclei to form water droplets, thus
favoring the formation of fog, mist and all of it due to opal.
These examples shown are demonstrative of the existence of some chemical elements in the
mineral state of the biosphere. According to this, the main elements that are part of these
mineralized structures are Ca, Si, C, P, although strontium and sulfur could be found in small
quantities.

75
 2.2.4- Forms of existence of chemical elements in the biosphere.
In the biosphere, the mineral state of existence of chemical elements is rare. However, signs of
mineralization are evident in the skeletons and shells of numerous living organisms. Numerous
marine microorganisms and higher animals have calcareous shells or skeletons (mainly formed
by aragonite or calcite (CaCO 3 ). An example of this is the nacreous layers of many shells and
pearls, which are made almost entirely of aragonite.
Other organisms build their skeletons or shells of silicon material, which contributes to the
exceptional hardness of these structures. Thus, the skeletons of several sponges are formed in the
evaporation of water from said splash. Most of these salts return to the sea quickly, while some
quantities are transported by winds over long distances, precipitate in continental regions and
end up returning to the sea dissolved in river waters.
The greatest distribution of chemical elements in the biosphere corresponds to the state of
amineral existence. This is mainly represented by:
a) Organic material
b) True solutions of inorganic compounds.

76
a) Organic material
Many of the metabolic processes of living organisms (plants and animals) occur with the
participation of aqueous colloidal systems. The dispersed phase of these is adequately
characterized by a varied range of organic compounds, among which albumins, proteins, liquids
and carbohydrates should be highlighted. The elements that make up these substances are mainly
carbon, hydrogen, oxygen, phosphorus, potassium, nitrogen, among several others that fulfill
very diverse physiological functions.
When plants and animals die they decompose under the action of microorganisms, generally
leaving residues that resist microbial decomposition in which various elements essential for life
accumulate, especially combined nitrogen, carbon and phosphorus. These residual substances are
called humus and are formed by a very complex mixture of amorphous organic substances that
consist of waste and animals, plants and microorganisms, as well as compounds formed during
the decomposition of these substances under the action of microorganisms.
Humus contributes significantly to the adsorption processes that take place in the soil,
constituting in itself an organic colloidal system that, although not as stable as clay systems, has
an adsorbent capacity and water retention much higher than those of clay systems. other soil
components. The adsorption and base exchange phenomena in which humus participates are
explained by the negative charge of these colloidal particles that allow them to adsorb cations
from the true soil solutions.
If on the one hand the release of carbon dioxide during microbial activity can cause a decrease in
soil pH and thus activate chemical weathering, on the other hand, humic complexes play an
important role in the disintegration of rocks due to this capacity that They have the ability to
adsorb and exchange cations.

b) True solutions of inorganic compounds.

The nutrition of plants and animals is governed by the incorporation of essential elements in the
form of true aqueous solutions of various soluble substances. The appropriation of the true of
various soluble substances. The appropriation of the main nutrients occurs in the form of cations
(K + , Ca 2+ , Mg 2+ , Fe 2+ ) or in the form of soluble oxyanions (NO - 3 , PO 3- 4 , SO 2+ 4 ) in
solutions watery.
The accumulation of these and other elements in plants is not only related to their availability in
the soil but also to the water solubility of their compounds. It is necessary to point out that some
of these elements become part of cellular fluids, while others tend to form poorly soluble
organic compounds.

77
 CHAPTER III

GEOCHEMICAL MIGRATION DURING NATURAL AND ANTHROPIC PROCESSES

3.1- Geochemical migration. Fundamental concepts.

What should be understood by geochemical migration?
To establish the meaning of this term, it must be appropriately derived by adopting its
etymological conception. This could be expressed in a schematic table like the one shown
below:

GEOCHEMICAL MIGRATION

Translatio Chemical elements

n

Higher geospheres
Motion

Consequently, geochemical migration consists of the translation of chemical elements in the

upper geospheres, leading to their redistribution and changes in their forms of existence,
associated with the occurrence of endogenous and exogenous processes. The translation must be
understood not in a mere physical sense, but taking into account the different energy sources that
enable the occurrence of each migratory process, which act differently on each type of migrating
particle.

3.1.1- Directions of migration.

To understand the principle of the migratory processes of chemical elements, it is necessary to
approach the problem based on the analysis of the directions of migration.
The directions of migration must be considered based on the changes experienced by the
concentrations of chemical elements during the migration process, which can lead to the more or
less stable establishment of a dispersed state or a concentrated state. For this reason, two
opposite but complementary directions are defined: dispersion and concentration.
Dispersion is an oriented geochemical process whose tendency is to achieve maximum
homogeneity in the distribution of particles in space. This process includes:
The leveling of the concentrations of the elements in the different geospheres.
The destruction of rock masses and mineral deposits (and their surrounding areas with
significant accumulations of meniferous and accompanying elements).
Concentration is a oriented geochemical process that leads, under favorable conditions, to the
formation of mineral deposits and sectors of accumulation of chemical elements. This process
causes:
The heterogeneity in the concentrations of elements in the different geospheres.
The formation of deposits and minerals and sectors of accumulation of chemical elements.
Why does the dispersed state predominate over the concentrated state in light of the directions of
migration?
It is evident that this happens due to the fact that dispersion as a migratory process is more
favorable than concentration. This has its corresponding additional thermodynamic explanation,
depending on the energy changes that accompany both. Its fundamental meaning is expressed in
the dominant character of dispersion, while concentration is a circumstantial direction that
requires the manifestation of favorable conditions that counteract the previous tendency.

78
The directions of migration must be analyzed as opposites due to the way they manifest
themselves, but not exclusive; That is to say, the germ of one is always implicit in the other.
In summary, any migration process can be characterized in stages, which result from taking into
account the directions of migration:
Stage I (dispersion). Resulting from the activation of the migratory process and linked to the
existence of a sufficiently high energy source.
Stage II (concentration). Tendency towards the completion of the migratory process,
corresponding with an appreciable decrease in the energy of the system.

3.1.2- Means, forms and mechanisms of migration.

In the system of fundamental concepts of geochemical migration, it is necessary to first define
those referring to the means, forms and mechanisms used by chemical elements in migratory
processes.

 Migration means.
The medium of migration is understood to be the phase in which the translation of chemical
elements takes place in the different geospheres, and can manifest itself as: liquid (rocky molten
or aqueous solution), solid, gaseous, biogenic and technogenic.

 Forms of migration.
The form of migration refers to how the chemical elements are found in the migratory process.
Among these, the most common are: atomic particles (simple and complex ions, atoms,
molecules), fragments of minerals and rocks, molecular aggregates (droplets, colloidal particles),
organic matter.

 Migration mechanisms.
The migration mechanism represents the vehicle that guarantees the transfer of chemical
elements and, consequently, is closely linked to the energy source that serves as the driving force
in the migration process. Energy sources can have a diverse origin, being expressed
fundamentally in: physical energy (kinetic, gravitational, thermal), chemical energy,
physicochemical energy (thermodynamic, surface), biochemical energy and technogenic energy.
Its real representation is manifested in: the solvent and dispersing power of water, the
immiscibility of two molten phases, the fusibility of certain minerals under conditions of high
temperatures, diffusion, infiltration of aqueous solutions, interactions between colloidal
particles, the occurrence or non-occurrence of chemical reactions, the synthesis and
decomposition of organic compounds, the artificial production of material goods by man, the
relative stability of colloidal solutions, the evolution of gases during magmatic and hydrothermal
activity, the mechanical action of currents river and marine, displacement under the direct action
of the force of gravity, the mechanical action of the wind, biogenic absorption, etc.

3.1.3- Migration factors.

The variation in the physical, chemical, physicochemical, biochemical or technogenic conditions
of the environment in which the geochemical migration of one or several elements occurs can
decisively influence the manifestation of variations in their migration capacities. In turn, the
differences between the properties of the elements or those that they confer to the substances
they form, determine their differentiated migration capacity. From this statement it follows that
when analyzing migration processes it is necessary to consider the relationship that exists
between internal factors and external factors.
Internal factors are referred to the properties inherent to the migrating particles (ionic charge,
ionic radius, ionic potential, stability of colloidal systems, mass, electrode potential, specific
weight of minerals, etc.)

79
External factors include the physical, chemical, physicochemical, biochemical and technogenic
conditions of the environment in which geochemical migration occurs (Eh, pH, temperature,
pressure, concentration of cations or anions, concentration of dissolved gases, density, force of
gravity, biological activity, energy from river or sea water, wind, etc.).

3.1.4- Migration capacity of chemical elements.

In all migratory processes, it is characteristic that there are differences in the migration
capacities of some chemical elements with respect to others, an expression that is linked to the
unequal manifestation of internal factors.
This trend can be seen from the study of the zoning that is manifested in the distribution of the
chemical elements participating in a given migratory process when it has concluded.

3.1.5- Geochemical barriers.

Finally, some issues related to the cessation of geochemical migration must be briefly addressed,
for which it is essential to introduce the concept of geochemical barrier.
The geochemical barrier represents a sector of the Earth's crust in which a notable decrease in
the migration capacity of one or more chemical elements takes place. For this reason, from the
geochemical point of view, geochemical barriers are directly responsible for the formation of
mineral deposits.
Many phenomena can be linked to the cessation of migratory processes and the establishment of
certain geochemical barriers. Among them, the most common should be noted:

PHYSICAL CHEMICA PHYSICOCHEMIC BIOCHEMICAL TECHNOGENIC

LS AL S
Evaporation of Reactions Colloid coagulation Compound Traps for the
waters. acid-base Biogenic absorption synthesis collection of toxic
Force of gravity. Reactions Magma crystallization organic waste
decrease of redox Colloidal adsorption
mechanical
energy.

In all these phenomena, the decrease in the energy that controls the migratory process is
common, which leads, in conjunction with internal factors, to the cessation of the migration of
the particles that participate in it.

3.2- Endogenous migration.

Endogenous migration can be classified based on the particular characteristics of the
environment that the chemical elements use in the corresponding migratory process. In this way
the following types are reached:

ENDOGENOUS MIGRATION

Magmatic Hydrotherma gas migration

Each of themmigration
has a special meaning withinl migration
the geochemical cycle since the mobilization of
chemical elements occurs according to different pathways or mechanisms. Furthermore, not all
chemical elements participate in the same way in the migration medium, which is closely related
to their abundance in the migration medium and its geochemical character.

80
 To have a more complete idea of what has been proposed, it is enough to initially remember that
magma is a rocky melt, hydrothermal solutions represent aqueous solutions at elevated
temperatures and that there is a gas phase associated with magma and hydrothermal solutions.
Next, the most general aspects that contemplate the activation and cessation of endogenous
migration will be addressed.

3.2.1- Magmatic migration.

This migratory process presents its very particular characteristics, if it is taken into account that
the participating chemical elements are included in rock melt and that the formation of rocks
and/or mineral deposits are closely linked to thermodynamic and gravitational factors.
The way magmatic migration manifests itself is very complex, since it is very complete: the
formation of minerals (or liquid molecular aggregates) and the gravitational separation of these.
What are the most common means, form and mechanisms for magmatic migration?

Half Shape Mechanism

Liquid ions, atoms magmatic (thermodynamic)
melt
Liquid molecular aggregates liquefaction (gravitational)
(droplets)
Solid crystalline particles segregation (gravitational)

LEYENDA To a large extent, these means, forms

A ureola
G abros gravitacional de C u and mechanisms are revealed together in
E squistos
A ureola
gravitacional de N i
some of the stages of the magmatic
C uerpo m ineral de process, and cannot be clearly
pentlandita-calcopirita
differentiated. However, the study of the
directions of magmatic migration allows
us to shed some light on this issue.
Under conditions of high temperatures
and relatively low pressures, the fusion
of rocks is favored, which determines
the formation of magma and the
subsequent activation of the migratory
process for the different constituent
Fig. 3.1 – Schematic geologist-geochemical section of a
pentlandite-chalcopyrite liquefaction deposit and its
chemical elements.
gravitational halo. When the temperature decreases,
various situations can be generated
depending on the chemical composition of the magma.
In the case of a magma with an ultrabasic composition, the existence of a silicate phase and a
sulfur phase is common, whose miscibility is limited to a temperature below approximately 1200
ºC; The mechanism by which both phases are separated is called liquefaction. This phenomenon
gives particularities to the continuity of the migratory process initiated with the fusion of the
rocks, since from this moment drops of sulfurous composition begin to be generated within the
melted mass, thus beginning to materialize the differentiation of the chalcophilic elements.
associates. Considering that the density of these drops is higher than that of the magma that
surrounds them, they tend to separate gravitationally with the consequent tendency for their
concentration towards the lower parts of the magma chamber with a significant enrichment of
Cu, Fe, Ni and Co, among other chemical elements. The subsequent solidification of this
sulphurous melt would lead to the formation of magmatic deposits of pentlandite-chalcopyrite
liquefaction, while those particles that were not completely separated from the magmatic melt
and that were trapped in the formed rock would give rise to their gravitational haloes. This is

81
clearly seen when studying the section of a magmatic sequence where these geochemical
systems are housed (Fig. 3.1).
A similar situation can be seen in relation to the formation of chromite, titanomagnetite,
ilmenite, etc., during the cooling of a magma of ultrabasic composition; This mechanism is
called segregation. This determines the gravitational separation of the minerals formed, given
that they have a density higher than that of the magma in which they are found, occupying the
lowest parts of the magmatic chamber. In relation to this process, magmatic deposits can form
from the segregation of chromite, titanomagnetite, etc.; However, smaller particles that remain
suspended for a longer time in the magma have less chance of concentrating and, when
solidification occurs, they become trapped in the rock formed, also causing gravitational halos
(Fig. 3.2).
In both cases, the joint action of thermodynamic and gravitational factors guarantees that the
migratory process extends sufficiently towards the progressive concentration of the
aforementioned chemical elements, all of this occurring at the expense of the manifestation of
thermodynamic and gravitational barriers.
Another example could be that which corresponds to the formation of different types of igneous
rocks (ultrabasic, basic and medium) from a basaltic magma, which would be closely linked to
the fractional crystallization of the minerals formed from these rocks under particular
thermodynamic conditions. , which implies a tendency towards unequal concentration of Fe,
Mg, Na, K, etc. in the rocks that originate when the migratory process ceases. In both cases,
there is an extreme responsibility for the cessation of migration for thermodynamic factors.

3.2.2- Hydrothermal migration.

This migratory process takes place with the participation of a set of elements dissolved in a
superheated aqueous solution (hydrothermal solution). Thus, the formation of hydrothermal
reservoirs and hydrothermal alterations results from the cessation of the migration of one or
more of these elements present in the hydrothermal solution, with thermodynamic and chemical
factors having a determining influence.
During hydrothermal migration, the formation of complex ions, their decomposition and the
precipitation of minerals take place, in accordance with the physicochemical conditions of the
medium. In general terms, what are the most common means, forms and mechanisms in
hydrothermal migration?

Half Shape Mechanism

Liquid complex ions diffusion
(physicochemical)
infiltration
(physicochemical)

When the hydrothermal migration of one or more chemical elements is activated, the diffusion
and infiltration mechanisms can be jointly revealed, making it advisable to establish the
differences between them.
Diffusion occurs as a result of differences in concentrations of elements between different parts
of the hydrothermal solution and between the hydrothermal solution and the surrounding rock.
That is, diffusion tends to level the concentrations of the elements throughout the system,
generally leading to the concentration of hydrothermal solutions.

82
 LEYENDA
In another sense, infiltration
L u titas Z o n a d e sto ck -w o rk co n
contemplates the circulation of
m in eralizació n p irito -calco p irítica hydrothermal solutions through a
L im o litas C u erp o estratifo rm e
d e esfalerita-g alen a system of fractures, which leads to the
A ren iscas C u erp o estratifo rm e
d e g alen a-esfalerita
fractional precipitation of the elements
C u erp o estratifo rm e as the conditions of the hydrothermal
d e b arita
solutions change.
For these cases, given the influence of
the physicochemical conditions of the
medium on hydrothermal migration, it
is considered that the cessation of
migration is conditioned by the
existence of thermodynamic barriers
and chemical barriers (reducing,
oxidizing, etc.).
Fig. 3.3- Schematic geologist-geochemical section of a
Cu-Pb-Zn-Ba deposit. 3.2.3- Gaseous migration.
This type of migration occurs as a
result of the release of volatile substances from magmatic melts and hydrothermal solutions.
This develops, therefore, in the final stages of these migratory processes above the magmatic
and hydrothermal bodies formed previously. Thermodynamic factors are of transcendental
importance in the occurrence of this type of migration.
What are the means, forms and mechanisms of gas migration?

Half Shape Mechanism

Gaseous molecules Diffusion
(physicochemical)
Infiltration
(physicochemical)
LEYENDA
A u reo la d e
G ran ito s F alla em an ació n d e I In this way, elements such as Hg, I, As and S
A u reo la d e
A ren iscas G rietas
em an ació n d e H g tend to participate in this migratory process,
L u titas C u erp o m in eral d e
g alen a-esfalerita
ceasing their migration only when the
temperature becomes low enough for these
gases to liquefy or under the effect of surface
phenomena. (colloidal adsorption). Because
of these, the geochemical barriers that prevail
in these migratory processes are
thermodynamic and sorption barriers.

Fig. 3.4 – Schematic geologist-geochemical section of a

galena-chalcopyrite hydrothermal reservoir and its
emanation halo.

83
3.3- Exogenous migration.
Exogenous migration can be classified based on the particular characteristics of the environment
that the chemical elements use in the corresponding migratory process. In this way the following
types are reached:

EXOGENOUS MIGRATION

Natural processes Artificial processes

Mechanical Biogenic Technogenic

migration migration migration

water gas migration

migration

All these migratory processes present as a common characteristic the influence of weathering
and erosive agents that cause the mobilization of chemical elements from the rocks and minerals
that contain them.
This idea would be more complete if we start from considering that the Earth's crust in its
superficial part is constantly being affected by exogenous agents, so all the rocks and minerals
that compose it experience physical and chemical changes that imply: the dissolution of some
elements in natural waters, the transformation of unstable primary minerals into stable secondary
minerals, the incorporation of some elements into the biosphere, the permanence of minerals
stable to weathering. To this must be added the influence of man's industrial activity on the
geological environment, which can give rise to significant changes in the processes that
determine the activation of the migration of certain chemical elements.
The most general aspects that contemplate the activation and cessation of exogenous migration
will be addressed below.

3.3.1- Mechanical migration.

This type of migration occurs in those cases in which there are minerals (primary or secondary)
that are stable against weathering agents.
What are the fundamental means, forms and mechanisms for mechanical migration?

Half Shape Mechanism

Solid fragments of minerals and wind activity
rocks River current activity
slopes of elevations

In this case, mechanical factors have a decisive influence, determined by the action of the force
of gravity on the migrating particles.
For example, when an acidic rock (granite) is affected by weathering, some of the minerals that
compose it remain unaffected chemically (SiO 2 , SnO 2 ). The physical destruction of the rock
enables the release of these minerals and the subsequent transport of these fragments from the
positive parts of the relief to the allochthonous deposition areas. This is possible with the
participation of erosive agents (water, wind, etc.) and thanks to the transformation of potential
energy into kinetic energy. The cessation of mechanical migration is given by the action of the
force of gravity on these solid particles, manifesting gravitational barriers.
* Make a schematic representation expressing the characteristics of a river basin and the
participation of the fragments of these minerals in mechanical migration.

84
85
3.3.2- Aqueous migration.
This migratory process is characterized by the fact that the participating chemical elements are
part of true solutions and colloidal solutions. For them, the chemical decomposition of minerals
during weathering and their dispersion in aqueous solutions is necessary, which contributes to
the activation of geochemical migration.
What are the most common means, forms and mechanisms for aqueous migration?

Half Shape Mechanism

Liquid Ions True solutions
Liquid Molecular Colloidal solutions
aggregates

For example, when the weathering of an ultrabasic rock (peridotite) occurs, all of the rock-
forming minerals (olivines, pyroxenes, etc.) are chemically decomposed, releasing a set of
lithophilic elements (Mg, Fe, Al, Ca , Yes) interact with weathering solutions. From this results
the incorporation of Fe 2+ , Mg 2+ and SiO 4 4- to aqueous solutions, although with a differentiated
tendency to remain in ionic form due to the existing distinctions in their chemical properties. For
Mg 2+ and Ca 2+, migration in ionic form within the true solution is more characteristic, which is
in correspondence with the relatively low ionic potentials that correspond to these two elements,
a factor that makes them hardly hydrolyzable. Fe 2+ is easily transformed into Fe 3+, which makes
its ionic potential intermediate and its hydrolysis is favored, thus forming iron oxides and
hydroxides (hematites and limonites); Fe 3+ in combination with AlO 3 3- and SiO 4 4- also has a
tendency to hydrolyze, forming clay minerals, which allows them to migrate in the form of
molecular aggregates (colloidal particles) within a colloidal solution, although a part
Considerable of these products precipitate from weathering solutions.
In this case, the joint action of chemical and physicochemical factors allows the migratory
process to extend sufficiently towards the dispersion of these elements. However, the opposite
influence of these factors themselves can lead to the cessation of migration.
For calcium and magnesium, the influence of pH on their precipitation in the form of carbonates
(calcite, magnesite) is characteristic, and a neutralization barrier must exist. In the case of Fe,
there is a decisive influence of the pH and Eh of the medium on its precipitation, which is why
oxidative barriers and neutralization barriers appear.
Both aluminum and silicon are influenced by pH for their precipitation in the form of
hydrosilicates, which is determined by the presence of neutralization barriers.

3.3.3- Gaseous migration.

This type of migration occurs as a result of the existence of gases in the atmosphere from
volcanic activity, photosynthesis processes, as a result of natural radioactive decay, etc.
Some of these gases are chemically active (H 2 S, SO 2 , SO 3 , CO 2, O 2 ) and interact with the
minerals that make up the Earth's crust in the presence of an aqueous medium. These gases
themselves are fundamental participants in biochemical processes (bacterial activity,
photosynthesis and respiration), thus integrating into the biosphere.
Other gases components of the atmosphere are chemically inert (Ar, He, N 2 ) so they tend to
maintain their migration for a very long time.
What are the means, forms and mechanisms of gas migration?

Half Shape Mechanism

Gaseous molecules diffusion
(physicochemical)
infiltration
(physicochemical)

86
In this way, elements such as O, C, S, N, He, Ar, tend to participate in this migratory process,
ceasing their migration only when the corresponding chemical interaction exists.
For example, CO 2 dissolved in natural waters is converted into H 2 CO 3 in an acidic medium by
chemically interacting with water, which is why there is a variation towards aqueous migration.
In another sense, CO 2 would be transformed into CO 3 2- in a basic medium, which would
guarantee its aqueous migration; However, in a medium where there are sufficient
concentrations of Ca 2+ and Mg 2+ this would tend to precipitate as a result of the existence of
neutralization barriers.

3.3.4- Biogenic migration.

The occurrence of this type of migration is determined by biological factors, for which the
incorporation of certain elements into living organisms and their participation in different
metabolic processes (nutrition, respiration, photosynthesis, etc.) is necessary.
What are the means, forms and mechanisms involved in biogenic migration?

Half Shape Mechanism

Biogenic molecules Biogenic absorption
Breathing
Photosynthesis

For example, a significant part of the potassium released during the weathering of an acidic rock
(granite) is absorbed by the root system of plants as it constitutes a macronutrient, being
incorporated in this way into cellular fluids, where it fulfills very important metabolic functions.
On the other hand, CO 2 is taken by plants to develop their photosynthesis process, converting it
into reduced organic compounds (chlorophyll).
In this way, plants would become a biogenic barrier for potassium that migrates in aqueous
solutions and for atmospheric carbon.
The death of the plant organism or the fall of the leaves (or other parts of the plant) conditions
the cessation of biogenic migration, creating the humus horizon in the soils; This layer of
decomposing organic matter has colloidal properties and is capable of retaining some elements,
thus becoming a sorption barrier.

3.3.5- Technogenic migration.

This type of migration takes place due to the incorporation of man's social and industrial activity
into the geological environment. To a large extent, this is harmful to the environment, which is
why it is essential to control it and minimize these side effects.
The means, forms and mechanisms of technogenic migration are very varied and are linked to
the characteristics of the industrial processes involved.
For example, the combustion of pyrite (FeS 2 ) for the production of H 2 SO 4 involves a large
amount of SO 2 and SO 3 , part of which is not used in this industrial process and passes into the
atmosphere. When these gases interact with rainwater, they cause a decrease in its pH, causing
the so-called acid rains.
To cause the cessation of technogenic migration, the use of technical control means is required
that prevent the expulsion of gases, heavy metals and other elements harmful to the
environment. In fact, these become technogenic barriers.

87