Modul B.Geo.

109 Vorlesung :






For skripts to part 1
see :
http://134.76.75.184


1. Hot Geochemistry: igneous processes and planetary differentiation

2. Low-temperature geochemistry: Surface processes, soils and weathering

3. Organic geochemistry : The geochemistry of life and its signals in rocks
4
6
8
10
12
14
2
16
70 60 50 40
Cox et al. (1979)
SiO
2
phonolites
trachytes
benmoreites
mugearites
hawaiites
basalts
andesites
dacites
rhyolites
Nomenclature based on major elements
4
6
8
10
12
14
2
16
70 60 50 40
SiO
2
basalts
The behaviour of trace elements in partial melting and weathering
2.0
1.5
1.0
0.5
0
1 2 3 4 5 6
Wertigkeit
Na
Li
Sr
Ca
Mn Fe
Co
Ni
Mg
La
Eu
Lu
Nd
Y
Th
U
Zr, Hf
Nb Mo
Sc
Cu
V
Cr
Ga
Al
Ti
Ge
Si
B
Se
Cs
Rb
Tl
K Sc
LILE
mobil in Wasser
HFSE
immobil in Wasser
2.0
1.5
1.0
0.5
0
1 2 3 4 5 6
Charge
Na
Li
Sr
Ca
Mn Fe
Co
Ni
Mg
La
Eu
Lu
Nd
Y
Th
U
Zr, Hf
Nb
Mo
Sc
Cu
V
Cr
Ga
Al
Ti
Ge
Si
B
Se
Cs
Rb
Tl
K Ba
LILE
mobile in water
HFSE
immobile in water
Mg
Si Ti
Al
Fe
Sm
Yb
Tm
Tb
Gd
Lu
Na
Sr
La
U
Th
Ba
Nd
Fe
Mn
Sc
Ca
Ce
Ca
0,001
0,01
0,1
1,0
10
K
1,01A
0,4 0,6 0,8 10 12
14
16
Ionic Radius, A
0,79 A
( Henderson 1984 )
In
Partition coefficients are controlled by
the size and charge of the atoms and
the available sites in the crystal lattice.
Partition coefficients are determined (1)
empirically by analyzing minerals in
matrix in natural rocks, (2) by
experimental crystal-melt equilibrium
and (3) by calculations based on the
crystal-lattice thermodynamic model of
Blundy and Wood (1994, 2003).

See GERM - Website for reference.

Blundy, J., Wood, B. 1994. Nature, 372,
452-454.
Blundy, J., Wood, B. 2003. Earth Planet Sci.
Lett. Frontiers, 210, 383-397.
1.3
1.2
1.1
1.0
0.9
57 60 65 70
The element
promethium
(Pm, Z=60) has no
stableisotope
Europium has two
stable valence states:
II and III, Eu
2+
is
Known to occur in
igneous melts under
low f
O2
conditions, and
substitutesfor Ca
2+
in
plagioclase.
Cerium is the only REE
to form a IV valence state
(in oxidizing sedimentary
environments)
La Ce
3+
Pr
Nd
Sm
Eu
3+
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Y
3+
LANTHANIDE
CONTRACTION
Ionic radii from
Whittaker and Muntus
A
t o
m
i c
n
u
m
b
e
r
Z
Eu
2+
Ce
4+
Gill (1996), p.231
400
100
50
10
1
0
Nd Ce SmEuGd DyEr Yb
Clinopyroxene
Zircon
Garnet
Apatite
Hornblende
Hypersthene
Biotite
Oivine
Partition coefficients for typical minerals in igneous petrogenesis
0,1
0,1
Nd Ce Sm Eu GdDyEr Yb
Anorthoclase
Plagioclase
K-Feldspar
0,05
0,01
1
4
0
0,1
0,005
0.5 1.0 0
BATCH PARTI AL MELTI NG
F
D = 10 D = 4 D = 2
FRACTI ONAL MELTI NG
C
l
/C
0
= F
(D-1)
0.5 0
F
0.01
100
0.01
0.1
1.0
D = 10
D = 4
D = 2
D = 1
D = 0. 75
D = 0.25
D = 0
1
C
l
/C
0
= 1/[D(1-F)+F]
0.1
10
D = 1
D = 0.75
D = 0
1
10
100
D = 0.25
Incompatible elements fractionate only during low degrees of partial melting (unless accessory minerals are involved).
Incompatible elemt concentration decreases with increasing degree of partial melting.
C
l
/C
o
=1/D*(1-F)
(1/D-1)
C
l
/C
o
=1/(F+D-F*D)
Batch partial melting Fractional crystallization
Cl/Co=1/(F+D-F*D) Cl/Co=F
(D-1)
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
F
0
2
4
6
8
10
12
14
16
18
20
Batch partial melting
Incompatible elements fractionate only during low degrees of partial melting (unless accessory minerals are involved).
Incompatible elemt concentration decreases with increasing degree of partial melting.
Incompatible elements fractionate only during low degrees of
partial melting (unless accessory minerals are involved).
Incompatible elemt concentration decreases with increasing
degree of partial melting.
Incompatible elements fractionate only during low degrees of
partial melting (unless accessory minerals are involved).
Incompatible elemt concentration decreases with increasing
degree of partial melting.
0 20 40 60 80 100
50%
0%
20%
10%
30%
40%
PARTI AL
MELTI NG
FRACTI ONAL
CRYSTALLI ZATI ON
0
20
40
60
80
100
R (D = 4) ppm
15%
30%
40%
10%
20%
Partial melting and crystallization are not reversible processes for trace elements ! The algorithms are different to
describe these processes and the melt/crystal mass rations are different.
C
l
/C
o
=F
(D-1)

Fractional Crystallisation:
Batch Partial Melting:


C
l
/C
o
=1/(F+D*F-D)
Batch
10
100
La Ce Nd SmEuGd Dy Er YbLu
Pri mi ti ve mantl e source
10%
5%
2%
1%
0.1%
Roll i nson (1993)
Chondr i te-nor mal i zed REE patter ns cal cul ated for
modal batch mel ti ng of a pri mi ti ve
mantl e source wi th ca. 2.15 condri ti c concentra-
ti on of REE and with the mi neral ogy -
oli vi ne 55%, orthopyroxene 25%, cl in opyroxen
11% and gar net 9%.
Incompatible elements fractionate during low degrees of partial melting. Thus, incompatible trace element ratios change
in magma series from the same source, but only at small degrees of melting. At large degrees of melting (>5 to 10%)
trace element rations will not change (much) during melting and can be used to distinguish different magma sources.
90%
70%
50%
30%
Komati i te-336
Chondri te-nor mal i zed REE pattern s cal cul ated for ol i vi ne fr action ati on
fr om a komatii te mel t (komatii te-336) at 30%, 50%, 70% and 90%
fr action al cr ystal l i zation .
Rol l i nson (1993)
10
100
La Ce Nd SmEuGd Dy Er YbLu
Incompatible elements do not fractionate during crystallization (unless accessory minerals are involved)
Thus, incompatible trace element ratios do not change in magma series and can be used to distinguish magma suites
from different degrees of melting or different sources.
Komatiite =ultra-mafic magma formed by high degrees (>30%) of partial mantle melting that was possible only during Archean and Proterozoic times
Ta (ppm)
0 1 2 3 4 5 6 7 8 9 10
10
8
6
4
2
0
Inkompatible Elemente
Titanit-Fraktionierung
Incompatible elements
Incompatible elements do not fractionate during crystallization (unless accessory minerals are involved)
Thus, incompatible trace element ratios do not change in magma series and can be used to distinguish magma suites
from different degrees of melting or different sources.
La/Sm
La (ppm)
0 5 10
2.0
0
1.0
Island
Reykjanes Rcken
fraktionierte Kristallisation

Chemical Geodynamics
The relation between crust and mantle geochemical reservoirs is
mostly based on our knowledge on the geochemical composition of
continental crust and mantle-derived basalts

... and thus
starts with a review of Basalt Classification and Petrogenesis and
geochemical discrimination diagrams
Basalt Classification
Basalt is the most common volcanic rock at the Earths
surface.
How do you safely recognize a basalt ?
How do you distinguish between a primitive and a primary
basalt ?
How do you distinguish basalt types (tholeiites, alkali
basalts, arc basalts, MORB, OIB, IAT CAB ?
How about exotic mantle-derived magmas : kimberlite,
boninite, komatiite,carbonatite, and other extreme
compositions
In late 1960s it was recognized that basalts formed in several
plate tectonic environments.

Basalts and Plate Tectonics
Alk MgO
FeO*
Calc-Alkaline
Tholeiitic
Myoshira suggests simple plots of certain
major element oxides could provide a better
basis for discrimination.
AFM diagram could provide a sensitive means
of differentiating island arc (calc-alkaline and
MORB (tholeiitic) basalts.
Alk = Na
2
O + K
2
O
MgO = MgO
FeO* = FeO + Fe
2
O
3
+ MnO
This works well for Japan, but has
shortcomings:
does not discriminate OIBs at all
does not allow for the effect of
continental crustal contamination


Myoshira AFM Diagram
Advantages:
Much more sensitive as concentrations vary over
orders of magnitude
A lot more of them and some are compatible with
basalts and some incompatible
Disadvantages
Require a much more sophisticated analytical
apparatus

First trace element basalt classifications are simple
and utilize few elements
Minor and Trace Elements as
Petrogenetic Indicators
MnO*10 P
2
O
5
*10
TiO
2
CAB
IAT
MORB
OIT
OIA
Mullen diagram plots the minor elements
TiO
2
, MnO and P
2
O
5
.
Discriminates a variety of plate tectonic
environments and basalt types:
OIT = ocean island tholeiite
MORB = mid-ocean ridge basalt
OIA = ocean island alkaline
IAT = island arc tholeiite
CAB = continental arc basalt
Mullen Diagram
Zr Y*3
Ti/100
C
D A
B
Island- arc A,B
Ocean-floor B
Calc-alkali B,C
Within-plate DD
One of many Pearce diagrams.
This one uses Ti, Zr and Y.
Does a good job of
discriminating basalts. Ocean
floor = MORB; calc alkali =
OIB
Pearce Diagram
Use and abuse of Ternary
Discrimination diagrams
The basic problem with such diagrams is that the basalts often
dont plot in fields that are consistent with geologic evidence
(i.e. a basalt that can be directly tied to a MORB origin ends up
plotting as a CAB).
Too many geologists have obtained geochemical data from
geochemist, plotted these in ternary cassification
diagramms ...., and failed badly with their interpretation !
GeoComics....
Solution 1) a better understanding of what tace element patterns
really mean (alteration, melting, fractional crystallization, source
differences).
Solution 2) use more and more sensitive elements, construct
spider diagrams (better trace element patterns)
Dont consider recent papers with ternary discrimination diagrams,
it may too simplistic for its geochemistry !
Along came the Spider ...
Spider diagrams have become the norm.
They display a spectrum of trace and minor
elements.
Elements are selected to cover a range
from incompatible to compatible.
They can be compared easily against any
standard.
Ocean island basalt
plotted on a mid-ocean
ridge basalt (MORB)
normalized spider
diagram of the type used
by Pearce (1983). Data
from Sun and
McDonough (1989).
Pearce-Spider Diagram : separate LIL and HFS elements, order in
increasing incompatibility towards the center of the diagram
Spider diagram for oceanic basalts
increasing incompatibility
Spider diagram for a typical alkaline ocean island basalt (OIB) and tholeiitic mid-ocean ridge
basalt (MORB). From Winter (2001) An Introduction to Igneous and Metamorphic Petrology.
Prentice Hall. Data from Sun and McDonough (1989).