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LU1 INTRODUCTION TO GEOCHEMISTRY

◊INTRODUCTION

“The primary purpose of geochemistry is on the one hand to


determine the composition of the earth and its parts and on the
other to discover the laws which control the distribution of individual
elements”
– V. M. Goldschmidt, 1933.

Geochemistry deals with the

• Abundance and distribution of the elements and their isotopes.

• Distribution between core / mantle / crust / hydrosphere / atmosphere

• Geochemistry is the study of the sources and fates of chemical species


in natural environments and their evolution through Earth history.

• Geochemistry is a set of tools for helping to understand the Earth; these


tools are based upon chemical, instead of the physical observations.

• Viewing natural phenomena and natural materials at the chemical


level gives us insights into the underlying processes that can often not be
ascertained from other forms of observation.

• Understanding something about the chemistry of matter and the


parameters that affect it help us to explain how a natural environment
functions.

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The field of geochemistry involves study of the

• Chemical composition of the Earth and other planets,

• Chemical processes and reactions that govern the composition of


rocks and soils, and

• Cycles of matter and energy that transports the Earth's chemical


components in time and space.

The most important fields of geochemistry are:

1. Determination of the relative and absolute concentrations of the


elements and their isotopes in the earth and on earth´s surface.

2. Examination of the distribution and movements of elements in


different parts of the earth (crust, mantle, hydrosphere etc.) and in
minerals with the goal to determine the underlying legalities of
distribution and movement.

3. Analysis of the distribution of elements and their isotopes in the


cosmos (cosmochemistry).

4. A study of the role of processes and compounds that are derived from
living or once-living organisms (organic geochemistry)

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◊HISTORY OF GEOCHEMISTRY

• The term “geochemistry” was first used by the Swiss chemist Schönbein
in 1838.

• You might guess, merely from the etymology of the word, that the field of
geochemistry is somehow a marriage of the fields of geology and
chemistry. That would be a good guess.

• Geochemistry really couldn’t develop as a science until both chemistry


and geology had developed into mature sciences.

• But just how are chemistry and geology combined within geochemistry;
what is the relationship between them?
Perhaps the best explanation would be to state that in geochemistry, we
use the tools of chemistry to solve geological problems; that is, we use
chemistry to understand the Earth and how it works.

• The Earth is part of a family of heavenly bodies, our Solar System, that
formed simultaneously and are closely related. Hence, the realm of
geochemistry extends beyond the Earth to encompass the Solar System.

• Geochemistry is a very broad topic. So broad in fact that no one can


really master it all; geochemists invariably specialize in one or a few
aspects, such as atmospheric chemistry, geochemical thermodynamics,
isotope geochemistry, marine chemistry, trace element geochemistry etc.

• Much of the early development of geochemistry occurred in the then


USSR as an outgrowth of geochemical prospecting (Alexander
Fersman and V.I. Vernadsky).
• Geochemists then adopted theoretical and experimental approaches
(the latter best exemplified by Norman L. Bowen of the Geophysical
Laboratory of the Carnegie Institution of Washington, the Father of
Experimental Petrology).

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Geochemistry has both pure and applied components.

Pure Geochemistry: concerned with “How and Why did the Earth and
Solar System reach their current chemical state?” Current research topics
include:
• Chemical cycles:
Fluxes of elements between earth’s reservoirs, especially between crust
and mantle, and of greenhouse gases between atmosphere and
lithosphere
• Paleoclimates:
Application of stable isotope thermometry
• Astrobiology:
Despite the name, the search for life on other planets involves
geochemistry in a very significant way.

Applied Geochemistry: benefits humanity in many ways, including:


• Geochemical prospecting: search for natural resources (fossil fuels, ore
deposits)
• Environmental geochemistry: behavior of anthropogenic contaminants in
the environment (air and water pollution)

Note:

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◊ELEMENTS

• Generally, an element is a basic part that is the foundation of something.


• For a long time, elements (classical element) were believed (by the
pythagoreans and alchemists for example) to be the building blocks of all
matter in the universe.
• In chemistry, an element (chemical element) is a substances that cannot
be separated into simpler substances and that singly or in combination
constitute all matter.

The elements never created or destroyed. The Earth can be envisioned as a


recycling machine that redistributes these elements.

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Classification of the Elements

1. The Periodic Table.


This is the most universal classification.
Elemental Grouping: These elements may be bracketed together into
several chemical grouping. This grouping also serves as a useful guide to
the geochemical behavior of the elements

Widely Used Terms for Element Groupings


A. Alkali Metals,
B. Alkaline Earths,
C. Transition Metals/Heavy Metals,
D. PGE's, (Platinum Group Elements)
E. Halogens,
F. Noble (Inert) Gases,
G. REE's (Rare Earth Elements),
H. Actinides,
I. Metalloids,
J. Precious Metals

F
1 2
H He

A B C C C C E
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3 4 5 6 7 8 9
Ne
Li Be B C N O F

I
11 12 (Transition Metals/Heavy Metals in Bold) 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar

C C C C C C C C C C I I
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc T V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

D D D J I I
37 38 39 40 41 44 45 46 47 48 49 50 51 52 53 54
42
Rb Sr Y Zr Nb Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Mo
D D D J
55 56 57 72 73 74 75
76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re
Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88 89
Fr Ra Ac

G 58 59 60 62 53 64 65 66 67 68 69 70 71
REE Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
H 90 92
Actinides Th U

However, for some specific studies, we have other classifications to help


us understand how the elements behave.

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Important Ocean Elements

Important Atmospheric Elements

Important Biological Elements

Important Lithospheric Elements

2. Geochemical Classification

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(based on which part of Earth the element tends to reside in)
Goldschmidt (1922), the father of geochemistry, suggested a
classification based on where elements were usually found. Only
qualitative, but this classification works because of the similarities in
electronic configuration within the groups:

Lithophiles - found in rocks


Found as silicate minerals
(Form ionic bonds with oxygen,
Have valance electrons that are outside shell of 8 electrons)

Siderophiles - found in metals


Found as native elements
(Valence electrons are complete s subshell, not available for
combination)

Chalcophiles – found in sulfide deposits


Found as sulfides
(Form covalent bonds with sulfur,
Valence electrons are outside a shell of 18 electrons)

Atmophiles – found in the atmosphere


Found as gases (inert gases, halogens, C, N, O)
These are shown as below.

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The Geochemical Classification of the Elements

B E
A C D F
Large Ion Siderophil
Lithophile HFI Chalcophile Atmophile
Lithophil e
e
F F
1 2
H He
C E F A A
3 4 10
5 6 7 8 9
Li Be Ne
B C N O F
A A A A E D
17 18
11 12 13 14 15 16
Cl Ar
Na Mg Al Si P S
B A A A A A A E E E D D D E D D
35 36
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34
Br Kr
K Ca Sc T V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se
B B B C C E E E D D D E D D
53 54
37 38 39 40 41 42 44 45 46 47 48 49 50 51 52
I Xe
Rb Sr Y Zr Nb Mo Ru Rh Pd Ag Cd In Sn Sb Te
B B C C C E E E E E D D D D D
B 85 86
55 57 72 73 74 75 76 77 78 79 80 81 82 83 84
56 At Rn
Cs La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po
Ba
B B B
87 88 89
Fr Ra Ac
B B B B B B B B B B B B B
REE 58 59 60 62 53 64 65 66 67 68 69 70 71
Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
C C
Actinides 90 92
Th U

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Geochemical Affinity
• In the classification scheme of Goldschmidt, elements are divi ded according to
how they partition between coexisting silicate liquid, sulfide l iquid, metallic
liquid, and gas phase…defined by examining ore smelting slags and meteorites
• Melting a chondrite gives 3 immiscible liquids plus vapor:
Gas Phase Atmophile H, He, N, Noble gases

Alkalis, Alkaline Earths,


Silicate Liquid Lithophile Halogens, B, O, Al, Si, Sc, Ti,
V, Cr, Mn, Y, Zr, Nb,
Lanthanides, Hf, Ta, Th, U
Sulfide Liquid
Chalcophile Cu, Zn, Ga, Ag, Cd, In, Hg,
Tl, As, S, Sb, Se, Pb, Bi, Te
Metallic Liquid
Siderophile Fe, Co, Ni, Ru, Rh, Pd, Os, Ir,
Pt, Mo, Re, Au, C, P, Ge, Sn
• To first order, the distribution of elements between core and mantle resembles
equilibrium partitioning between metal liquid and silicates…conf irmed by iron
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and achondrite meteorites (but at high P, no separate sulfide phase)

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◊SOLAR SYSTEM COMPOSITE ABUNDANCE CURVE

Main features:

1. H and He are the most abundant elements.


2. Li, Be, and B have very low abundance because of low stability
3. Very high abundance of Fe
4. Abundance does not change much for heavier nuclides (Z>40)
5. Zig-zag pattern:
In terms of elements, elements with even Z are more abundant than
those with odd Z.
6. The general decline in abundance as Z increases is interrupted by a sizable
peak around Z=26, comprising elements in the neighbourhood of iron.

Relative Abundances in the Solar System and Universe

o abundances of the first 50 elements decrease exponentially with


atomic number
o abundances of the heavier elements independent of atomic number
o H and He are the most abundant elements.
In atomic terms, He has one-tenth of the abundance of H and together
they comprise 98% of the solar system.

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o progressing to higher atomic numbers leads to an overall decrease
in abundance, making the heaviest nuclei among the least abundant
o note anomalously low abundance of Li, Be, B as compared to other light
elements
o note anomalously high abundance of Fe
o zig-zag pattern:
Elements having even atomic numbers are on average about ten times
more abundant than elements with similar but odd atomic
numbers.

References:
Brownlow, A.H., 1979, Geochemistry, Prentice Hall.
Krauskopf, K.B. & Bird, D.K., 1995, Introduction to Geochemistry, WCB
McGraw Hill
Mason, B. and Moore, C.B., 1989, Prinsip-Prinsip Geokimia, DBP.

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