Geochemistry

-Science concerned with the chemistry of the earth as a whole and its component parts
-It involves application of principles of chemistry to the solutions of geological
problems.
-It deals with the distribution and migration of chemical elements within the earth in
space and time.

Elements in a rock after analysis

Major elements Minor elements Trace elements

(>1%) (1 to 0.1%) (<0.1%)
i.e. <1000ppm

Use of geochemical data

1. Use of major element data
 Use of major element data
- 10 elements have been given the status of major elements
- Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K and P
- In the form of oxides
- 3 ways to use the major element data
(i) In rock classification
(ii) In construction of variation diagrams
(iii) Petrogenetic interpretation
Processing of major element data

LOI: Loss on Ignition

Limestone : CaCO3 : 40+12+48 = 100

CaO + CO2 : 40+16 = 56 + LOI
Main tasks of a geochemist are:
1.To determine relative and absolute abundances of elements and isotopes in the earth
2.To study the distribution and migration of individual elements in the various parts of
the earth (atmosphere, hydrosphere, crust, mantle, core, minerals, rock types etc.)
with an objective of discovering principles governing these distribution and
migration.
Origin and abundance of chemical elements in the solar system, in the Earth and its
component parts :

- Big bang : about 10-15Ga ago

- Neocleosynthesis: Process leading to the formation of elements
- H : Most abundant element in the universe
- Origin of elements is related to the evolution of stars as elements form by different
types of nuclear reactions

-Cosmic abundance of elements :

Cosmic abundance of elements:
Solar (cosmic) abundances of the elements:
1. H and He are most abundant elements (primordial H, some He) in the solar system and atomic
H/He ratio is 12.5.

2. Abundance of the first 50 elements show exponentially decreasing abundances with increasing
atomic number.

3. Abundance of elements with atomic number > 50, are very low and do not vary appreciably
with increasing atomic number

4. Elements with even atomic number are more abundant than their immediate neighbours with
odd atomic numbers (Oddo-Harkins rule, a result of nuclear “magic numbers”)

5. Abundance Li, Be and B are anomalously low compared to other elements of low atomic
number. (Cause: nuclei are destroyed in stars or are weakly stable)

6. Abundance of Fe is of anomalously higher than those of other elements with similar atomic
numbers. (Cause: 56Fe is the most stable of all possible nuclear configurations)

7. Tc and Pm do not occur naturally in our solar system because all of their isotopes are unstable
and decay rapidly.
8. The element with atomic number > 83 (Bi) have no stable isotopes but occur naturally at low
abundances because they are daughters of long lived radio active isotopes of U and Th.
Origin of elements

Nucleosynthesis : Process of creation of different chemical elements

# Process of creating new atomic nuclei from pre-existing nucleons (protons + nutrons)

# Understanding of this is based on 3-sets of observation:

(i)Cosmic abundance
(ii) Experimental data on specific nuclear reactions occurring under specified conditions

Nucleosynthesis : Occurs in 4 phases

1.Big-bang nucleosynthesis (or cosmogenic) : Occurred immediately after Big Bang (BBN)
2. Stellar nucleosynthesis : In the interior of large stars during the process of stellar evolution.
3. Explosive nucleosynthesis ( in supernovae)
4. Galactic nucleosynthesis (cosmic ray spallation) in interstellar space

Proposed by four scientists Burdige, Buridge, Fowler, Hoyle (1957) : Hence also called
B2FH theory
Big-bang nucleosynthesis
-Initially the universe was very hot , temp of 1027K
- Process started when this temperature came down to 1013K within few seconds after
Big bang (10-15Ga back) , leading to formation of protons and nutrons
-Subsequently nuclear fusion processes started inside the starts leading to fusion of all
kinds of elements.
- These fusion processes are :

- 1. H- burning During Big bang nucleosythesis

- 2. He- burning
- 3. C- burning During stellar nucleosythesis
- 4. Ne- burning
- 5. O- burning
- 6. Si - burning
- 7. Nuclear statistical equilibrium
- 8. Neutron capture processes (S-process, r-process, rp-process, p-process)
1. H- burning:
- when the density reaches 6gm/cc
- T rises to 10106 to 20106 K
- Occurs in two ways (i) Direct proton-proton chain cycle
(ii) CNO cycle
 H- burning
ii) CNO cycle : In more massive
i) Direct proton-proton chain cycle: second generation stars in which the
central temperature exceeds
2  107 K and which contain 12C
synthesized by ancestral starts
He- burning :
-Begins in a star if it is massive enough for temperature to reach 108K and core density
104 gm/cc
-Critical reaction is 3- process in which 3 He- nuclei fuse to form nucleus of 12C
through 4Be
8
4Be : Very unstable. Decay quickly with a half life of
10-16secs : Explains low concentration of Be

4 1
2He + 1H  53 Li (half life of 10-21secs : Explains its low concentration)
4 1
 2He + 1H
5
3 Li

- This 3- process is the key to synthesise all the elements beyond He. Without this
stellar evolution will be shot circuited and universe would be composed of only H
and He.
- At this point of stellar evolution H is converted to He, which in turn is converted to
12C , followed by 16O and 14N. Other isotopes that can form in this process are 18O,
22Ne, 25Mg
C- burning

- It starts with an initial mass of stars of at least 8 solar masses when core generates a
heat of > 5108 K.
- At such a temperature it is possible to overcome the Coulomb repulsion between
the 12C nuclei and they fuse to form 24Mg* (unstable):
6C + 6C  12 Mg * ( excited nucleus of 12 Mg)
12 12 24 24

- This represents C-burning stage in the evolution of a star. 24 20

12 Mg* decays to Ne :

- Thus C-burning is a major producer of 20 10 Ne in the universe.

- During this phase and in subsequent process a number of less abundant nuclei are
also synthesized. They are Na, Al, P, S and K.
Ne-burning: Follows carbon burning and typically occurs at temperature 1.5 109 K,
but lasts for a very short duration. The reaction is :
O-burning : Follows Ne burning and typically occurs at temperature > 108 K.
28 31 32 32 32
The main products are 14 Si , 15 P and 16 S via 16 S* (an excited nucleus of 16 S)
The reaction is :

Si-burning: Commences when temperature and density inside the star exceed 3 109 K
and core 107gm/cc respectively. It lasts for a week or less depending on the mass of the
star. Its more complicated than previous stages.

Fe is stable and explains higher abundance of Fe in solar system.

 (Successive stages of stellar nucleosynthesis)
Evolutionary path of the core of a massive star of
25 solar masses (after Bethe and Brown, 1985).
The period spent in each step of the nuclear fusion
process depends on the mass of the star; more
massive stars would evolve more rapidly. For most
of the star’s lifetime the primary energy source is
the fusion of hydrogen nuclei to form helium. The
final stage of silicon fusion yields a core of iron,
from which no further energy can be extracted by
nuclear reactions. The iron core cannot resist
gravitational collapse, leading to a supernova
explosion.
Nuclear statistical equilibrium:
- 56
26Fe is the dead end of stellar fusion reactions.
- Up to this energy is released.
- Fusion reaction up to Fe release energy.
- Formation of elements with atomic number higher than Fe consumes energy. Hence small
amounts of elements heavier than Fe (eg. Au, Ag, U etc.) are formed in stars, hence low cosmic
abundance.
- When increasing temp at core of a star bring the chain of nuclear reactions to this dead end
disintegrative as well as constructive reactions begin to occur among the Fe group nuclei (such
51 52 55 56 59 59
as 23V, 24Cr, 25Mn, 26 Fe, 27Co, 28Ni leading to a nuclear statistical equilibrium, the relative
higher abundances of Fe group elements reflect this steady state.
Neutron capture processes:
- Heavier elements are synthesized by neutron capture process- called s- process or r- process :
in explosive environments such as supernovae or
- rp- process: involving rapid capture of protons
- p-process: involves photodisintegration of existing nuclei
s- process
62
- This starts with 28Ni which absorbs a neutron 10n and become unstable 28 63
Ni. This in turn
undergoes - decay to become stable 28 Cu
62
63
- 6228Ni + 0n  28 Ni (unstable)  28 Cu (stable) + 
1 62 -

- This process continues further.

- s-process takes place at low neutron density and intermediate temperature condition of stars.
 Radioactive
isotopes

Stable isotopes
Explosive nucleosynthesis
-Supernova : (Meaning an exploding star) begins with collapse of a stellar core from a radius of
several 1000s of Km to a radius of 100km or so in few tenth of a second.
-When a matter in the central region of the core is compressed beyond the density of nuclear
matter (31014 gm/cc) it rebounds sending massive shook wave outward.
-The resulting temp increase produces a breakdown of existing nuclei by photodisintegration eg.,

It produces large number of neutrons and protons which in turn leads to 3-additional
nucleosynthesis processes like:
(i) r- process (ii) rp- process (iii) p-process
- This initiates explosive He-burning, O-burning and Si-burning in stellar shales.
- These produces S, Cl, Ar, Ca, Ti, Cr and some Fe.
r-process (Nutron capture)
-r-process occurs during a large burst of neutrons leading to large neutron capture and
immediate transformation of nuclides by - decay .
-At the end of supernova explosion, nuclides form by successive - decays to more stable
nuclides.
Eg.

- The r-process is responsible for the production of large number of isotopes in the range of 70
 A  209 and also synthesis of U and Th.
-Many of these isotopes can also form by s-process but some isotopes such as 86Kr, 87Rb and
96Zr can form by r-process.
rp-process : 173
74 195
-A number of proton rich isotopes (eg.32Se, 78Pt, 70Yb) cannot be created by neutron capture on
any scale.
-There are two ways to increase the proton/neutron ratio in an atomic nuclei
-(i) add protons or (ii) subtract neutrons
-rp- process includes consecutive proton addition to seed nuclei.
-This needs H-rich environment i.e. large flux of protons as well as high Temp (>109 K) to
overcome the large coulomb barrier. The process is inhibited by -decay which puts an upper
limit of 105Te as the end point.
- p- process
- It’s a misnomer and misunderstood as it has nothing to do with proton capture.
- It operates through the mechanism of photodisintegration which occurs when -ray strip off
first neutrons and then protons and - particles from pre-existing r- and s-process isotopes.
- Hence the p-process is also referred to as r-process.
- Proton capture which must overcome Coulomb force of repulsion is less probable and less
effective.
- The p-process is only significant for those nuclei that cannot be produced by other
168 174 174
mechanism and the abundances of elements created by p-process only( 70 Yb, 72Hf , 73Ta) tend
to be low.
Cosmic spallation :
- Stellar and explosive nucleosynthesis do not produce lighter elements such as Li, Be and B.

- These are produced by cosmic ray spallation (CRS).

- CRS refers to fragmentation of O and N nuclei in interstellar medium by cosmic rays (i.e. fast
moving high energy particles such as - particles and protons which are abundant in the
interstellar gas.
-These reactions occur at high energies (higher than big bang and stellar interiors, but at low
2 6 9
temperature and responsible for all of some of the lightest isotopes such as 4He , 3 Li , 4 Be,
10 11 7 2
5 B , 5 B , 3 Li but not 1H.
Explaining Cosmic Abundances
1. H and He are most abundant
• Because they were formed in the Big Bang and these are the primary constituents of
primitive universe.
2. Exponential decrease in abundance off first 50 elements
•Reflects decreased productivity of He capture processes i.e. decreased nucleosynthesis in
the more advanced burning cycles.
3. Lower abundances off heavier elements
• Caused by sluggishness of neutron capture reactions in normal stars
4. Greater stability off nuclides with even-numbered numbers off protons and/or neutrons
• Nucleons with paired spins have stronger nuclear binding affinities. Elements with odd
atomic numbers have one unpaired proton and are more likely to capture another, thus
increasing their atomic number. In elements with even atomic number protons are paired,
thus enhancing the stability of atoms. Notable exception is 11H, the most abundant element in
the universe.
5. Low abundances of Li, Be, B
• Because production processes tend to bypass these elements, also they are destroyed by
nucleon bombardment inside the star and higher abundance of Fe-group relative to its
neighbour inside the stars.
• The high abundance of Fe makes it an inescapable candidate for being a major constituent
of planetary cores.