Geochemistry

▪ It is the study of the Earth’s chemistry employing chemical tools to comprehend

Earth’s processes.
▪ Its primary aim is to understand the principles that control the distribution and
redistribution of elements, ionic species, and isotopic ratios in the earth
materials.
▪ It helps in interpreting the formation of mineral assemblages, including the
conditions (such as pressure and temperature), processes (like magmatic
crystallization, weathering, chemical precipitations, and metamorphism), and
the ages of these formations.
▪ The term “Geochemistry” was first introduced by Christian Friedrich Schonbein
in 1838.

Chemical Tools
▪ Spectroscopy: Methods like X-ray fluorescence (XRF), Inductively Coupled
Plasma (ICP) Spectroscopy, Electron Microprobe Analysis (EMPA) and mass
spectrometry (MS) to determine the elemental composition.
▪ Chromatography: Techniques such as gas chromatography (GC) and liquid
chromatography (LC) to separate and identify chemical compounds.
▪ Microscopy: Tools like electron microscopes to study the mineral and chemical
structures at a microscopic level.
▪ Isotope Analysis: Measuring the ratios of isotopes to understand age, origin, and
processes involved in the formation of rocks and minerals.
▪ Chemical Reagents: Using specific chemicals to react with samples to identify
and quantify their components.
 Cosmic abundance of Elements
➢ Study of the cosmic abundance of elements involves understanding the distribution
and prevalence of chemical elements throughout the universe.
➢ This study provides insights into the processes of nucleosynthesis, stellar
evolution, and the overall chemical evolution of galaxies.
➢ Cosmic abundance refers to the relative quantities of elements found in the
universe. These abundances are typically expressed relative to hydrogen, the most
abundant element.
➢ The study of cosmic abundance is critical for understanding the origins of elements,
the processes occurring within stars, and the chemical evolution of the universe.

Methods of Measurement

The cosmic abundances of elements are determined using various observational and
theoretical methods:

• Spectroscopy: This is the primary observational technique used to measure the

abundances of elements in stars, nebulae, and galaxies.
• By analyzing the absorption and emission lines in the spectra of astronomical
objects, astronomers can infer the presence and abundance of different elements.
• Meteorites and Solar System Materials: The analysis of meteorites, particularly
chondrites, provides valuable information about the primordial solar system's
composition. The study of the Sun's spectrum also gives insights into the solar
system's elemental abundances.
• Cosmochemical Models: These models use theoretical frameworks and
nucleosynthesis calculations to predict the abundances of elements produced in
various astrophysical environments.
Spectroscopy

The position of these lines, which look like a cosmic barcode, tells us which
molecules and atoms are in the gas that absorbed parts of the light. This is how
astronomers determine the chemical composition of celestial objects, which can help
determine the habitability of a distant exoplanet or the age of some of the oldest
galaxies, whose light has greatly shifted into the infrared part of the spectrum.

Figure: The absorption lines we obtain from the spectrum of a star.

• At present only 118 elements are known, about 90 of these occur naturally, during
the Big Bang, only lightest of elements were formed such as H and He and some
trace amounts of Li and Be. The other 86 elements were formed in nuclear
reactions in the core of stars and in huge stellar explosions known as Supernovae.

Figure: Cosmological origin of each element

• The universe's 94 naturally occurring chemical elements are thought to have
been produced by at least four cosmic processes.
• Most of the hydrogen, helium and a very small quantity of lithium in the universe
was produced primordially in the first few minutes of the Big Bang.

Figure: The Big Bang

Figure: From Big bang to formation of Earth.

 .

Four Phases of nucleosynthesis.

Cosmological nucleosynthesis/ Big Bang Nucleosynthesis:
✓ This process occurred shortly after the Universe began and is responsible for
the cosmic inventory of H and He, and some of the Li (in Trace amounts).
✓ Helium is the main product of nucleosynthesis in the interiors of normal, or
"main sequence" stars.
Stellar Nucleosynthesis:
✓ The lighter elements, up to and including Si, but excluding Li and Be, and a
fraction of the heavier elements may be synthesized in the interiors of larger
stars during the final stages of their evolution (stellar nucleosynthesis).
Supernovae/ Explosive Nucleosynthesis:
✓ The synthesis of the remaining elements heavier than Iron, occurs as large stars
exhaust the nuclear fuel in their interiors and explode in nature's grandest
spectacle, the supernova.
Cosmic Ray Spallation:
✓ Finally, Li and Be are continually produced in interstellar space by interaction
of cosmic rays with matter (galactic nucleosynthesis/cosmic ray spallation/X
process).
 Figure: He burning in big stars.

Fig: Hertzsprurg-Russel Diagram of star classification.

Fate of Stars...
• White Dwarfs: Endpoints of low to intermediate-mass stars, stable if below the
Chandrasekhar limit (1.4 solar mass).
• Neutron Stars: Result from core-collapse supernovae of high- mass stars with
remnant core masses between ~1.4 and 3 solar masses.
• Black Holes: Form from the collapse of very massive stars or from merging
neutron stars, with remnant core masses exceeding -3 solar masses.
• Supernovae:
Type II Supernova: Result from the core collapse of high mass star.
Type Ia Supernova: Occur in binary systems when a white dwarf accretes
enough mass to exceed the Chandrasekhar limit.
 GEOCHEMICAL CLASSIFICATION OF ELEMENTS

• Elements may be classified in a number of ways that are useful in geochemical

investigations.
• The most significant of these classification schemes is that developed by V.M.
Goldschmidt.
• M. Goldschmidt is also called as the father of geochemistry.
• Based on the affinity of elements to form various types of compounds and is
relevant to how elements distribute themselves between the Earth's major
geochemical reservoirs: the core, the mantle and crust, and the hydrosphere and
atmosphere.
In Goldschmidt’s classification the chemical elements are divided into four groups-
➢ Lithophile,
➢ Chalcophile,
➢ Siderophile,
➢ Atmophile
Lithophile
• These elements (“rock loving”) are preferentially partitioned into silicate
minerals.
• These include cations that commonly form oxides, such as Ca, Mg, Mn, Ti, Na,
K, U, Th, Si, and Fe in its oxidized states.
• They are difficult to reduce to the elementary state and compounds with oxygen
are most characteristic of them.
• An overwhelming majority of these elements are components of silicates in
rocks.
• Lithophile elements also occur naturally as oxides, halides, phosphates, sulfates,
and carbonates and are concentrated in the silicate portion (i.e. crust and mantle)
of the earth.
Chalcophile
• These elements are those metals and heavier non-metals that have a low affinity
for oxygen and prefer to bond with sulphur to form sulphide type minerals or
highly insoluble sulphides.
• These include Cu, Pb, Zn, Cd, Mo, Hg, Sb, Sn, Tl, Te, As etc.
• Because these sulfides are much denser than the silicate minerals formed by
lithophile elements, chalcophile elements separated below the lithophiles at the
time of the crystallization and differentiation of the Earth's crust.
Siderophile

• These elements (“iron loving”) are those that are preferentially partitioned into
the metallic core, typically in the form of alloys with Fe.
• Thus, they are depleted in the silicate portion of the earth and presumably
concentrated in the core.
• Elements exhibiting metallic behavior include the noble metals (Pt, Pd, Ir, Ru,
Rh, and Os) as well as W, Ni, and Co.
• Some elements in their reduced states or at high enough pressures to impart
metallic behavior can alloy with Fe metal; these include Si, C, and some high
field strength elements like Nb.
• Sulfur may dissolve in the core as a sulfide complex and, under these conditions,
is also considered siderophile.
Atmophile

• These elements are those that readily form volatile (e (i.e., they form gases or
liquids at the surface of the Earth) compounds at relatively low temperatures
(<300 K) many of which are preferentially concentrated in planetary
atmosphere.
• Atmophile elements include C, O, H, N, S, and the noble gases.
Oddo-Harkins Effect

saw tooth or zig-zag abundance pattern

(Oddo-Harkins effect)
Explanation of the Oddo-Harkins Rule
• Atoms form when protons and neutrons bind together and form an atomic
nucleus. For most elements, this happens when the immense temperature,
pressure, and gravity within a star fuses protons and neutrons together. An
element’s atomic number is the number of protons in its atom.
• One explanation for the higher abundance of even-numbered elements is that
helium (atomic number 2) is a major building block for element formation. Fusion
of helium nuclei builds subsequent even atomic number elements.

(Then question arises…. How the odd atomic number elements are formed?
Ans - One of the most significant sources of an odd-numbered element is the CNO
cycle that operates to a minor extent in our Sun and more prominently in more
massive stars like Sirius. They all involve carbon, nitrogen and oxygen interchanging
through the absorption of protons and the emission of alpha and positron beta
particles.)
• Another explanation is that even atomic numbers mean protons are paired within
the nucleus. Parity makes the nucleons more stable, as the spin of one proton
offsets the spin of the other. Unpaired protons (odd number elements) more easily
capture another proton and form an even-numbered atom.
• The Oddo-Harkins rule is in action when massive stars die and explode. While
different stars uphold the rule, their element ratio differs according to the
metallicity of the star.

Exceptions to the Oddo-Harkins Rule

• Elements that serve as two exceptions to the Oddo-Harkins rule are hydrogen
(atomic number 1) and beryllium (atomic number 4). Hydrogen is the most
abundant element in the universe. It is more abundant than helium because of its
creation in the Big Bang. However, stars continuously fuse hydrogen into helium.
In the distant future, hydrogen will follow the even-odd rule.
• Beryllium is even more rare than lithium (atomic number 3) and boron (atomic
number 5), even though the primary source of the all three elements is cosmic ray
spallation. Scientists believe beryllium does not follow the rule because it only
has one stable isotope. Lithium and boron each have two stable isotopes.
(Be-7 quickly decays with half-life of 52 days).
 Geochemical Differentiation
The Earth as a Physico chemical system:
• Geochemically, the earth may be considered a closed system. Although some
materials- meteorites and meteoritic dust-is continually being received from outer
space, and that some hydrogen and helium is being lost by escape from the upper
atmosphere. These gains and losses are insignificant as compared with the system
as a whole.
• The chemical processes taking place on the surface and within the earth have
probably operated with a remarkable degree of uniformity for the last 4000
million years.
• Geochemist is mainly concerned with the surface of the earth, since it is the only
part accessible to direct examination.
• The general picture of a nickel-iron core, a mantle largely of magnesium-iron
silicate, and a crust in which O, Si, Al, Fe, Ca, Mg, Na and K are the major
constituents gives a consistent interpretation of information gleaned from many
independent sources like the study of meteorites, the physics and chemistry of the
earth, seismological data, and so on.
• The earth was not created in its present state. The geochemical evidence supports
the idea that its internal structure is probably the result of forces originating within
the earth itself. Earth, with considerable mass, exerts a gravitational force on its
own components.
• The resulting gravitational field has affected the distribution of material by
concentrating the heavier phases toward the center and the lighter towards the
surface. Goldschmidt termed this primary geochemical differentiation.
• The rate of such a gravitational differentiation clearly depends on the viscosity of
the system; it is more rapid in a gas than in a liquid. more rapid in a liquid than in
a solid.
• The idea of an earth at one time liquid is attractive, or it explains how such
gravitational differentiation could take place within a comparatively short time.
• Geophysical data sustain the theory that the earth has a layered structure due to
separation of its material into shells of different density. Goldschmidt termed this
the primary geochemical differentiation.
• It was a differentiation due to gravity acting on a system in which iron, oxygen,
magnesium, and silicon were the major components.
• Iron was the principal component, and the distribution of the elements between a
metallic core and a silicate mantle was controlled by their oxidation potential with
respect to that of iron. Elements more readily oxidized than iron concentrated in
the mantle; the others alloyed with iron to form the core.
• The fate of an element in this primary geochemical differentiation is in effect a
reflection of the number and arrangement of its orbital electrons. Those elements
forming ions with a noble gas structure went into the silicate phase; the transition
elements, on the other hand, concentrated in the metallic core or in a sulfide phase.

➢ The separation of crust, mantle, and core enables us to consider the outer part of
the earth as a distinct physicochemical system. Since the asthenosphere is
partially molten it may chemically, interact with layers above it, especially at
divergent or convergent plate margins.
➢ At divergent margins new material is added to the earth's surface. At convergent
margins subduction of surface materials into the mantle allows them to be melted
or mobilized and recycled to the earth's surface.
➢ The migration of material within the crust and upper mantle can then be discussed
as an independent phenomenon; it is partly mechanical, brought about by
orogenic movements or gravitational forces, and partly chemical. Mechanical
movements belong in the field of geology. Geochemistry is concerned with the
migration of the elements under the influence of physicochemical forces.
Figure: Schematic model of major long term geochemical processes at the earth’s
surface.

➢ This migration has been discussed in terms of the processes of magmatism,

sedimentation, and metamorphism.
➢ The fate of an element during magmatic crystallization is primarily a function of
its ionic size.
➢ A particular element appears in those minerals in the lattices-of which it fits most
readily and with the greatest decrease of free energy.
➢ The distribution of the elements by ionic size in this way was described by
Goldschmidt as the secondary geochemical differentiation.
 Conclusive statements of geochemical differentiation

Geochemical cycle
• Geochemical cycle refers to the chemical interactions that exist in crustal and sub
crustal reservoirs such as the deep earth and lithosphere.

Figure: The Geochemical cycle.

References:
• Books -