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

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) wavelengths, which has been attributed to Doppler effect in light Red shift- star is moving away from Earth

1. Cosmological red shift

Hubble's Law: linear relationship between distance and redshift

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, 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, 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 particleantiparticle pairs of all kinds e.g., quark-anti quark, electronpositron 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 10-6 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 10-4 seconds quarks and gluons combined to form protons and neutrons (baryons) Temperature no longer high enough to create new proton-antiproton pairs, mass annihilation 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
Stars

Until stars formed, there was nothing except H and He

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 H2 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: 103105 mol/cm3 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., 26Al, 60Fe) 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 its surrounding 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 (106 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

Star's absolute luminosity is plotted against its surface temperature (or spectral type)
Main sequence90% of all stars (>0.7 Mo) at some stage in their life, they are in H burning stage H He GiantsMid sized stars (0.7 to a few Mo) after main sequence SUN White dwarfsfinal evolutionary state of stars whose mass is not too high (< 0.7 Mo) Supernovae- either massive stars or white dwarfs in a binary star system where one star gains mass from a companion star

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 3x108 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) 1p + 1p 2He 2He 2D + + + neutrino 2D + 1p 3He 3He + 3He 4He + 21p

At T of 15 million K (PPII) 3He + 4He 7Be 7Be + - 7Li + neutrino 7Li + 1p 8Be 8Be 24He
At T above 25 million K (PPIII) 7Be + 1p 8B + gamma ray 8B 8Be + - + neutrino 8Be 24He

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 (1H, protons) into a single helium nucleus

Nuclear fusion in massive main sequence and AGB stars

Why does fusion stop with Fe-56 or Ni-56? Two important fusion reactions in AGB stars produce slow neutrons-nucleosynthesis of heavy elements 13C + 4He 16O + n 22Ne + 4He 25Mg + n

Supernovae
A supernova is an explosion of a star

Happens in massive stars (>9 solar masses) 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
13C

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

Fe-Ni seed nuclei undergo slow neutron capture accompanied by beta decay
Forms nuclides along the valley of beta stability

Z
N

S-process pathway

Termination of s-process

R-process (rapid neutron capture)-core collapse supernovae

High neutron densities and fluences (1022 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 2109 to 3109 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