Geochemistry

Dewashish Upadhyay
Origin of elements

Some facts
Hydrogen makes up about 73% of the mass of the
visible universe
Helium makes up about 25% of the mass
Everything else represents only 2%
Abundance of heavy (A > 4) elements quite low

Important to remember that most matter on Earth is a
part of this small portion of the matter of the universe
Nuclide chart
Atomic number vs.
Neutron number

Horizontally-isotopes

Vertically-isotones
Valley of beta-stability-central dark region
Right of the valley-neutron rich nuclides-undergo -
decay
Left of the valley-proton rich nuclides-undergo
positron-decay or electron capture
Origin of elements

Three principal astrophysical settings for the
synthesis of elements

Cosmological Big Bang

Stars

Supernovae
Big Bang Theory
The Big Bang Theory is the cosmological model that best
explains the origin of the universe

According to the standard theory, our universe came into
existence 13.7 billion years ago as an infinitesimally small,
infinitely hot, infinitely dense discrete point - a singularity

The pressure is thought to be so intense that finite matter is
actually squished into infinite density

Where did it come from? We don't know. Why did it
appear? We don't know.
Big Bang Theory
Singularities defy our current understanding of physics.
They are thought to exist at the core of "black holes
(areas of intense gravitational pressure)

About 10
-35
seconds after its initial appearance, the
universe expanded exponentially (cosmic inflation)

After inflation stopped, the universe consisted of a
quark-gluon plasma

It continued to expand and cool from very, very small
and very, very hot, to its current size and temperature. It
continues to expand and cool to this day
Big Bang Theory

There was no giant explosion. Rather there was and
continues to be an expansion

Space didn't exist prior to Big Bang

Theory of Relativity says that time and space had a finite beginning
that corresponded to the origin of matter and energy. The
singularity didn't appear in space; rather, space began inside of the
singularity. Prior to the singularity, nothing existed, not space, time,
matter, or energy-nothing.

Where and in what did the singularity appear if not in space? We
don't know. We don't know where it came from, why it's here, or
even where it is. All we really know is that we are inside of it and at
one time it didn't exist and neither did we
Evidence supporting Big Bang Theory

1. Cosmological red shift

Doppler effect: When an observer is moving relative to the
source of waves, the wavelength of the wave changes,
becoming longer if the source is moving away from the
observer and vice-versa

The electromagnetic spectrum of stars is shifted to longer
(redder) or shorter (bluer) wavelengths, which has been
attributed to Doppler effect in light

Red shift- when star is moving away from Earth
Blue shift- when star is moving towards Earth
1. Cosmological red shift


Hubble's Law: linear relationship between distance and red-
shift

Galaxies are moving away from us at speeds proportional
to their distance. This supports uniform expansion of the
universe and implies that it was once compacted to a
point- source


2. Cosmic microwave background radiation

If the universe was initially very, very hot as the Big Bang
suggests, we should be able to find some remnant of this
heat
2. Cosmic microwave background


During the initial stages after the Big Bang, all particles
and photons in the universe were in thermal equilibrium.
Because electrons were unbound to nuclei, photons
were continuously scattered by the electrons, making
the early universe opaque to light


Temperature fell due to expansion, electrons and nuclei
combined to form atoms, scattering of photons ceased
and radiation became decoupled from matter, photons
could travel unimpeded and the universe became
transparent to light

2. Cosmic microwave background

Young universe filled with a uniform radiation (photon)
from its plasma

As it expanded, both plasma and radiation grew cooler

When the universe cooled enough that stable atoms
formed, these could no longer absorb the radiation

Photons existing at that time have been propagating ever
since, growing fainter and less energetic as they fill a
greater and greater universe. These photon form the
Cosmic Microwave Background radiation (CMB)

In 1965, Radio astronomers Arno Penzias and Robert Wilson
discovered a 2.73 K CMB which pervades the observable
universe
3. The relative abundance of H, He and Li in the universe


Hydrogen makes up about 73% of the mass of the visible
universe

Helium makes up about 25% of the mass

Abundance of the "light elements" H and He predicted
during Big bang nucleosynthesis matches that of the
observable universe


Big bang nucleosynthesis
Called primordial nucleosynthesis
Started 3 minutes after the beginning of space expansion and
lasted for just 17 minutes- after 20 minutes temperature and density
of the universe fell below that which is required for nuclear fusion

In the first few micro-seconds, because of the high energy density,
universe existed as a quark-gluon plasma in which particle-
antiparticle pairs of all kinds e.g., quark-anti quark, electron-
positron continuously created & destroyed in collisions

Quark: elementary particle and fundamental constituent of matter (combine to form
protons & neutrons)
Gluons: elementary expressions of quark interaction, are messenger particle of the strong
nuclear force, which binds quarks
Quarks interact by emitting and absorbing gluons, just as electrically charged particles
interact through the emission and absorption of photons
Big bang nucleosynthesis

By about 10
-4
seconds, the universe had cooled for the
primordial quark-gluon plasma to freeze out

An unknown process called baryogenesis produced
excess of particles (MATTER) (quarks, leptons) over
antiparticles (ANTI MATTER)

At 10
-6
seconds quarks and gluons combined to form
protons and neutrons (baryons)

Temperature no longer high enough to create new
proton-antiproton pairs, mass annihilation(total
destruction) occurred, leaving excess protons and neutrons
and none of their antiparticles
Big bang nucleosynthesis

By approx. 3 minutes, further expansion and cooling
allowed some neutrons and protons to fuse to D and He
nuclei. Most protons remained uncombined as hydrogen
nuclei

After about 379000 years, electrons and nuclei
combined into atoms, mostly H and the universe
became transparent to light

The 73% H and 25% He abundances that exists
throughout the universe today come from that
condensation period
Big bang nucleosynthesis
Fusion reactions during these initial stages formed
elements up to Li
No nuclides heavier than Be, Li was formed
No neutral atoms existed at this time
How did heavier elements form?
The evolution of the universe
Neutral atoms formed in the time scale of 379,000 years
once the universe was cool enough for free electrons
to be captured by nuclei
Stellar nucleosynthesis
Until stars formed, there was nothing except H and He

Stars
A star is a luminous ball of plasma held together by
gravity
Stars shine due to energy radiated from thermonuclear
fusion in their core
Almost all elements heavier than H and He are created
by fusion processes or neutron capture in stars and
supernovae
The evolution and eventual fate of a star is determined
by its mass
Stellar evolution
Formation of star
Stars form when a molecular cloud collapses
due to gravitational instability or supernova
shock wave

Molecular cloud is rotating cloud of:
Molecular H
2
gas, He, and molecules such as CO
About 1% by mass submicron-sized dust grains
Another 1% gaseous molecules and atoms of elements heavier
than He
T: 715 K and gas densities: 10
3
10
5
mol/cm
3
Mass: a solar mass to thousands of solar masses

Regions of active star formation are located within molecular
clouds
Collapse of molecular cloud
Dense rotating cloud cores supported against their own self-gravity by a
combination of turbulent motions, magnetic fields, thermal (gas) pressure,
and centrifugal force

Conglomerations of dense dust and gas formed Bok globules
Globules collapse, density increases, gravitational potential energy
converted into thermal energy temperature rises

Collapse can be of two types:
Self collapse - standard model of star formation
Magnetic support gradually lost through ambipolar diffusion (neutral
molecular gas slips past the small fraction of ionized gas and magnetic
field lines) allowing bulk of cloud to contract gradually & eventually
undergo a dynamic collapse phase

Collapse takes place on time scales of the order of 10 Myr

Presence of short-lived nuclides (e.g.,
26
Al,
60
Fe) with half-lives much less
than 10 Myr in early solar system indicates collapse was quicker

To explain the presence of these short-lived nuclides, a triggered collapse
model was proposed
Shock triggered collapse
Short-lived nuclei impose a time limit of at most about 1Myr
between their nucleosynthesis and their incorporation in the solar
nebula

Collapse of molecular cloud by a supernova shock wave
travelling at velocities between 20-40 km/sec

Supernova triggers the collapse of molecular cloud and injects
short-lived nuclides in to it on time scales of about 1 Myr

Most of the collapsing mass collects in the centre, forming a star,
while the rest may flatten into a protoplanetary disc (nebula) out
of which the planets, moons, asteroids, and other small bodies
form
Protostar and protoplanetary disk

As material within the nebula collapses, atoms within it collide with
increasing frequency converting kinetic/gravitational potential
energy into heat

Most of the mass collects in the centre which becomes
increasingly hotter than the surrounding disc

In about 100,000 years the interplay of gravity, gas pressure,
magnetic fields, and rotation leads to the flattening of the nebula
into a spinning protoplanetary disc

A hot, dense protostar (T-Tauri star) (has not begun fusing H) forms
at centre (shines by radiating gravitational potential energy)


Stars with discs of pre-planetary matter with masses of
0.0010.1 solar masses are called T Tauri stars


These discs extend to several hundred AUthe Hubble
Space Telescope has observed protoplanetary discs of
up to 1000 AU in diameter (200 AU for our solar system) in
star-forming regions such as the Orion Nebula

Within 50 Myr, T & P at core of star become so great (10
6

K) that its H begins to fuse, creating an internal energy
source which counters gravitational contraction until
hydrostatic equilibrium is achieved - Main sequence star
Classification of stars: HerzsprungRussell diagram
Main sequence90% of all stars
(>0.7 M
o
) at some stage in their life,
they are in H burning stage H He

GiantsMid sized stars (0.7 to a
few M
o
) after main sequence

White dwarfsfinal evolutionary
state of stars whose mass is not too
high (< 0.7 M
o
)

Supernovae- either massive stars or
white dwarfs in a binary star system
where one star gains mass from a
companion star
Star's absolute luminosity is plotted against its surface temperature (or
spectral type)
Main sequence stage

After formation, star creates energy in its core through
the nuclear fusion of H atoms into He
Hydrostatic equilibrium
outward radiation pressure
from the hot core is balanced
by the inward gravitational
pressure

Position on main sequence
depends on mass, chemical
composition
Giant
Period of stellar evolution undertaken by all low to
intermediate mass stars (0.6-10 solar masses) late in their
life (after main sequence)- Red giant
Main sequence star exhausts H by fusion in its
core- the core contracts, T increases
Outer layers of star expand and cool,
Thermal instability causes convection which
brings to the surface the product of H
burning- dredge up
Luminosity increases greatly red giant
Once temperature in the core reaches 3x10
8
K, He fusion starts
giving C, O
Asymptotic giant branch star
When He is exhausted in the core
the C, Ocore again contracts

The envelope becomes convective
again- second dredge up

Core contraction continues with H burning
in a shell with He in between the H shell and
the core

When T gets high enough, He ignites and burns in a runaway flash for
some time (thermal pulse). This process is repeated intermittently

The star is called a thermally pulsing Asymptotic giant branch star

Gradually the star has inert core of C and O, a shell where He is
undergoing fusion to form C (He burning), another shell where H is
undergoing fusion forming He (H burning) and a very large envelope of
material of composition similar to normal stars
Nuclear fusion in low mass stars
Hydrogen burning

Proton-proton (PP) chain
At T less than 5 million K (PPI)
1
p +
1
p
2
He
2
He
2
D +
+
+ neutrino
2
D + 1p 3He
3
He +
3
He
4
He + 2
1
p

At T of 15 million K (PPII)
3
He +
4
He
7
Be
7
Be +
-

7
Li + neutrino
7
Li +
1
p
8
Be
8
Be 2
4
He

At T above 25 million K (PPIII)
7
Be +
1
p
8
B + gamma ray
8
B
8
Be +
-
+ neutrino
8
Be 2
4
He
Nuclear fusion in massive stars
In massive or higher generation stars, H converted to He by
several reactions that use atoms of C, N, and O as catalyst
The cycle results in the fusion of four hydrogen nuclei
(
1
H, protons) into a single helium nucleus
Nuclear fusion in massive main sequence and
AGB stars
Two important fusion reactions in AGB stars
produce slow neutrons-nucleosynthesis of
heavy elements
13
C +
4
He
16
O + n
22
Ne +
4
He
25
Mg + n
Why does fusion stop with Fe-56 or Ni-56?
Supernovae

A supernova is an explosion of a star

Happens in massive stars or when a white dwarf gains
mass from a companion in a binary star system

Intense amount of energy and radiation released

Star expels most of its mass at high velocity-generates
shock wave into the interstellar medium
Supernovae
In later stages of a stars life, increasingly heavier
elements undergo nuclear fusion

Binding energy of the nuclei increases, fusion produces
progressively lower levels of energy

Once Ni-56 is produced, fusion becomes endothermic

Ni-56 decays to Fe-56
Ni-Fe core builds up, fusion
stops, and the outward
thermal pressure cannot
counterbalance gravitation
Supernovae
The core collapses in on itself with velocities reaching
70,000 km/s sending out a shock wave

Fe breaks down to electrons, protons, neutrons. Because
of the high P, electrons in core combine with protons
forming neutrons and neutrinos

Intense gamma radiation & high energy neutrons
produced

Nucleosynthesis of
neutron-rich and proton-rich
heavier nuclides take place
Iron core (a) collapses (b). The inner part of
core is compressed into neutrons (c), causing
infalling material to bounce (d) and form an
outward-propagating shock front (red).
The surrounding material is blasted away (f),
leaving a neutron star
Nucleosynthesis of heavier elements

S-process (slow neutron capture) in AGB stars

13
C +
4
He
16
O + n
22
Ne +
4
He
25
Mg + n

Fe-Ni seed nuclei undergo slow neutron capture
accompanied by beta decay
Forms nuclides along the
valley of beta stability
N
Z
S-process pathway
Termination of s-process
R-process (rapid neutron capture)-core
collapse supernovae

High neutron densities and fluences (10
22
neutrons per
cm per second)

Neutron captures occur much faster than beta minus
decays
Produces neutron rich
nuclides to the right of
the valley of stability
Need for a P-process
Some nuclides to the left of the valley of beta
stability shielded from s- and r-process pathways

P-process needed to explain their formation
P-process
Photodisintegration of nucleus during interaction with gamma
rays

Occurs in supernovae

Two types of photodisintegration:
neutron-photodisintegration (, n)

Alpha photodisintegration (, )

During core-collapse supernova explosion, T reaches up to 210
9

to 310
9
Kelvin

Intense gamma radiation is produced that can disintegrate seed
nuclei created by s-process & r-process

P-process operates for only a short time: p-nuclei less abundant