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INTRODUCTION

TO GEOCHEMISTRY
Elements

• major elements: most abundant elements in a material


(often classified as more abundant than 1%)

• minor elements: less abundant elements between 0.1 and 1


%, but very loosely used

• trace elements: abundance is measured in ppm (parts per


million) or ppb (parts per billion)
Elements organized in periods (e-shells) and groups: the place in the system describes the physical parameters of the e-
configuration around the nucleus. These orbitals are described by quantum numbers like n (E, distance), l (shape), m
(orientation) and ms (spin) and are unique for each element. Elements with same number of p and different numbers of n
called isotopes. In chemical processes only the shells are important.

White P6 PERIODENSYSTEM
Here the e-configuration for the elements – in some periods special shells are filled before other sub-ordinated shells will
be completed. The K-shell contains a 1s configuration f.e. and He fills the places with two e. The L-shell contains two
Why
sub-shells (2s and 2p) and can hold 8 e. etc. The 4. Period: N-shell has several sub-shells, but instead of filling the 4p
shell, elements completing the 3d (energetic more convenient), then follows the 4p shell and these are then special
that
elements: the first transition metals. etc. -or elements like Rare earth elements including Lanthanides and Actinides.
diagram?
E of each e is individual and characteristic - it the e gets ‘exited’ (E adding) or
if it goes back on its place (E release)
BONDING

Ionic Bonds
• When an atom loses or Sodium atom (Na) Chlorine atom (Cl)
gains electrons, it
becomes electrically
charged
Complete
outer shells
• Ionic bonds are formed
between oppositely
charged ions

Sodium ion (Na+) Chloride ion (Cl−)

Sodium chloride (NaCl)


Properties of Ionic Bonds
•Results in minerals displaying moderate
degrees of hardness and specific density,
moderately high melting points, high degrees
of symmetry, and are poor conductors of
heat (due to ionic stability)

•Strength of ionic bonds are related:


1) the spacing between ions
2) the charge of the ions
Covalent Bond
Formed when atoms share electrons

•Hydrogen atoms form single bonds H―H


•Oxygen atoms form two bonds O=O
•Nitrogen atoms form three bonds N≡N
•Carbon atoms form four bonds O=C=O
Covalent Bonding
• formed by sharing of outer shell
electrons

• strongest of all chemical bonds


• produces minerals that are
insoluble, high melting points,
hard, nonconductive (due to
localization of electrons), have low
symmetry (due to directional
bonding).

• common among elements with high


numbers of vacancies in the outer shell
Diamond
(e.g. C, Si, Al, S)
Tendencies for Ionic vs. Covalent Pairing

Ionic Pairs
Covalent
Pairs
Metallic Bonding

• atomic nuclei and inner filled electron shells in a sea of electrons made
up of unbound valence electrons or not equally shared

• Yields minerals with minerals that are soft, ductile/malleable, highly


conductive (due to easily mobile electrons).

• Non-directional bonding produces high symmetry


van der Waals (Residual) Bonding

•created by weak bonding of oppositely di-


polarised electron clouds

•commonly occurs around covalently bonded


elements

•produces solids that are soft, very poor


conductors, have low melting points, low
symmetry crystals
Summary of Bonding Characteristics
Multiple Bonding in Minerals

• Graphite – covalently bonded sheets of C


loosely bound by van der Waals bonds.

• Mica – strongly bonded silica tetrahedra


sheets (mixed covalent and ionic) bound by
weak ionic and hydrogen bonds

• Cleavage planes (feldspar) commonly


correlate to planes of weak ionic bonding
in an otherwise tightly bound atomic
structure
1.Important parameter: Ionization
potential
This is the energy that is needed to remove the least tightly
bounded e from the element.
Low E on the left of the system, high E on the right –
The E that “changes” an element to an ion.

There is a second ionization E that measures the


amount of E is needed to take away
the second least bounded etc.

The higher the E the less is the possibility


to remove an element.
Or:
The lower the E the more mobile is an element.
Second important parameter: Electronegativity:
A value without unit and relative that quantifies the TENDENCY of an element to attract a shared electron when bounded with an other element in
ionic or covalent bonding. So, the e is physically closer to the element with the higher EN (stronger attracted!).
Again it is more complicated to release an element with a high EN from a molecule. Ionic bonding: Na & Cl “exchange” the e, means the Cl got
the e from the Na. This bounding exists only if delta EN >2 between the both elements as in NaCl.
Covalent bonding: e are shared as in H2O, the outer e is shared in a hybrid orbit by both atoms, very strong bonding - stable minerals.
Third parameter: Ionic radius
This described the bond length from 1 element to the other when bounded.
Cations are smaller than Anions because lacking an e!
If the ionic radius decreases, the charge increases: the loss of an e implies that orbits are shrinking
WHY? Because the same EM strength from the nucleus attracts less e (one less!)
A fact that is highly important for replacement of a major element.
Especially those major elements in group 1 (alkalis) and earth alkalis (group 2) forming ionic bonds which are weak, and are large (so
smaller ones can fit) so Na, K, Rb, Cs as major elements can be replaced easily, the same case for those of group 17 (Cl, Br, F, I) or replace
each other (Cs for K, f.ex.).
Elements of group 13-16 form covalent bonds and are more fixed or stable, so rarely involved in ionic bonding.
All other elements are variable. But the high charged elements are +/- not soluble in water, like Ti, Zr, Hf, Nb, Ta etc. with exceptions.

IONIC POTENTIAL= charge : radius and is a measure of solubility: the higher the IP, the lower S.
Different groups of elements can be distinguished:
Incompatibility and compatibility:
compatible: are mostly these elements which are retained in the residual solids during Partial
Melting and extracted in the crystallizing solids during Fractional Crystallisation;
incompatible vice versa

1. Volatile: H, N and noble gases


Extreme volatile and H on surface in water , in rocks as hydroxl-ion; the noble gases are chemically inert
and too large for rock forming processes; N is extreme volatile too and occurs only in gaseous
fraction of a silicate rock, strong N-N bond makes it not reactive
2. Semi-volatiles: C, S, Cl, F, Br, etc.
These elements partition readily into a fluid or gas phase or form volatile compounds(SO2, CO2); sulfide
is only slightly soluble in silicate melts, so high concentrations of sulfide in magmas will not
dissolve; CO2 solubility in silica is a function of p, so: high CO2 concentration can lead to form a
carbonate phase under high p (Carbonatites)
3. Alkali and Earth Alkaline Elements: Li, K, Rb, Cs, Sr, Ba, Pb etc.
Low EN and high ΔEN to molecule partners (mostly >2), big ionic radius, 1+/2+ valence,
so: ionic bonds which can be disrupted readily by water! because of its polarity; ionic potential (IP) is
low (charge/radius) makes them soluble and thus mobile
4. Rare earth Elements (REE) and Y: Trace elements
Incl. LANTHANIDES and ACTINIDES; only Th and U are stable enough to be recognizable in
geological processes and Y is like heavy REE; REE are distinguished in L (light), M (middle) and
H (heavy).
EN +/-, cations mainly, high IP so non soluble and incompatible mainly; 3+ but Eu can be 2+ (replace
Ca!) and Ce can be 4+ and is ultrastable under oxidizing conditions;
HREE can substitute Al in garnet; very similar habit of all of these REE.
5. High field strength elements: Zr, Hf, Ta, Nb, Th, U
Elements with a very high ionic charge and so a high IP and therefore mainly insoluble and immobile
during weathering etc. - less abundant in fluids
Ta and Nb is even strongly depleted in subduction related magma fluids probably because of the low
solubility and then the less chance to be transported in aqueous solutions generated by dehydration
away from the slab to the magma genesis zone

6. First series transition metals: Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn
More complex chemistry than other elements: 2-x+ valences; higher EN partly covalent bonds with S
f.e.; geometry of the d-orbital which favors a specific orientation of coordinating anions; solubility
depends on existing anions in the solution; behavior in magma is variable:
highly incompatible: Ti (upper mantle), Cu, Zn to very compatible: Sc, Cr, Ni, Co, Ti (in subduction
zones) as a function of composition

7. Noble metals: Rh, Ru, Pd, Os, Ir, Pt, Au


Firstly they are rare, secondly they are non reactive and stable in metallic form.
They are rare because only 1% of chondritic composition is found in rocks, so they are concentrated in
the core.
They are siderophile and chalcophile; two groups: Ir (Ir, Os, Ru): associated with chromites in ultra-
basics; Pd (Rh, Pd, Pt): associated with magmatic sulfides of Fe, Ni, Cu in gabbro.
Valence state governs the chemical reaction, high valence for Os leads to be highly volatile and forms
oxides; Pt, Au and Pd are more incompatible while Ru, Os and Ir are extremely compatible.
They dissolve in silica melts only in low valence state and are chalcophile, so S abundance is needed.
Residence time:
Is defined as the ratio of the mass of
an element in the ocean divided by
the flux to the ocean;
Assumption: ocean is a steady state:
flux-in equals flux-out !
Residence time means:
How long stays an element in the
medium (river, ocean) until it is
stored in the sediments (insolulable).
The longer the residence time
the less useful is the concentration of
an element to reflect the
concentration of its source!
Means an element with a long
residence time like Na (+/- 200 Ma)
will be well mixed in oceans and
cannot reflect local concentrations,
assuming that the oceans are mixed
every 1000 a.
BUT: it will reflect the average
ocean water concentration: Sr, C
for example.

WHY Na has a long τ and Sc a short


τ?
ELEMENT ABUNDANCES

Li, Be and B were


The decreasing abundance of
destroyed during
elements with heavier nuclei is
stellar processes
dependent on nuclear processes
which need high E to form stable
atoms.
Elements with even atomic
numbers are more abundant than
with odd numbers. WHY?
Abundance of elements in the silicate portion of the earth (crust and mantle)
Element Wt % Oxide Atom %
O 60.8
Si 59.3 21.2 Abundance of the elements
Al 15.3 6.4
in the Earth’s crust
Fe 7.5 2.2
Ca 6.9 2.6
Mg 4.5 2.4
Na 2.8 1.9

Major elements: usually greater than 1%

SiO2 Al2O3 FeO* MgO CaO Na2O K2O H2O

Minor elements: usually 0.1 - 1%

TiO2 MnO P2O5 CO2

Trace elements: usually < 0.1%

everything else
Ir 0.6-5 ppm
It is assumed that meteorites reflect the EARTH composition at 4.5-4.6 Ga.
Mineralogy and chemistry of chondrites and “primitive” mantle rocks.
Typical chemical compositions of the most important rock types

Granites or basalts from different tectonic settings vary in their


major elements slightly but strongly in their trace element
composition.
Ir (iridium) 0.002-0.02 ppm
Ir 0.6-5 ppm
It is assumed that meteorites reflect the EARTH composition at 4.5-4.6 Ga.
Why using major, minor but
favorably trace elements?

• Abundance
• fractionation