Chapter 9: Trace Elements

Note
magnitude
of major
element
changes
Figure 8.2. Harker variation diagram for
310 analyzed volcanic rocks from Crater
Lake (Mt. Mazama), Oregon Cascades.
Data compiled by Rick Conrey (personal
communication). From Winter (2001) An
Introduction to Igneous and Metamorphic
Petrology. Prentice Hall.
Chapter 9: Trace Elements
Now note
magnitude
of trace
element
changes
Figure 9.1. Harker Diagram for Crater Lake. From data
compiled by Rick Conrey. From Winter (2001) An Introduction
to Igneous and Metamorphic Petrology. Prentice Hall.
Element Distribution
Goldschmidts rules (simplistic, but useful)
1. 2 ions with the same valence and radius should
exchange easily and enter a solid solution in
amounts equal to their overall proportions

How does Rb behave? Ni?
Goldschmidts rules
2. If 2 ions have a similar radius and the same valence:
the smaller ion is preferentially incorporated into the
solid over the liquid

Fig. 6.10. Isobaric T-X phase
diagram at atmospheric
pressure After Bowen and
Shairer (1932), Amer. J. Sci. 5th
Ser., 24, 177-213. From Winter
(2001) An Introduction to
Igneous and Metamorphic
Petrology. Prentice Hall.
3. If 2 ions have a similar radius, but different
valence: the ion with the higher charge is
preferentially incorporated into the solid over the
liquid


Chemical Fractionation
The uneven distribution of an ion between
two competing (equilibrium) phases
Exchange equilibrium of a component i between
two phases (solid and liquid)
i
(liquid)
= i
(solid)
eq. 9-2 K = =
K = equilibrium constant


a
solid

a
liquid

i

i

X
solid

X
liquid

i

i

i

i

Trace element concentrations are in the
Henrys Law region of concentration, so
their activity varies in direct relation to their
concentration in the system
Thus if X
Ni
in the system doubles the X
Ni
in
all phases will double
This does not mean that X
Ni
in all phases
is the same, since trace elements do
fractionate. Rather the X
Ni
within each
phase will vary in proportion to the
system concentration
incompatible elements are concentrated in the
melt

(K
D
or D) 1

compatible elements are concentrated in the
solid
K
D
or D 1
For dilute solutions can substitute D for K
D
:

D =

Where C
S
= the concentration of some element in
the solid phase
C
S

C
L

Incompatible elements
commonly two
subgroups
Smaller, highly charged
high field strength (HFS)
elements (REE, Th, U, Ce,
Pb
4+
, Zr, Hf, Ti, Nb, Ta)
Low field strength large ion
lithophile (LIL) elements
(K, Rb, Cs, Ba, Pb
2+
, Sr,
Eu
2+
) are more mobile,
particularly if a fluid phase
is involved
Table 9-1. Partition Coefficients (C
S
/C
L
) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine Opx Cpx Garnet Plag Amph Magnetite
Rb 0.010 0.022 0.031 0.042 0.071 0.29
Sr 0.014 0.040 0.060 0.012 1.830 0.46
Ba 0.010 0.013 0.026 0.023 0.23 0.42
Ni 14 5 7 0.955 0.01 6.8 29
Cr 0.70 10 34 1.345 0.01 2.00 7.4
La 0.007 0.03 0.056 0.001 0.148 0.544 2
Ce 0.006 0.02 0.092 0.007 0.082 0.843 2
Nd 0.006 0.03 0.230 0.026 0.055 1.340 2
Sm 0.007 0.05 0.445 0.102 0.039 1.804 1
Eu 0.007 0.05 0.474 0.243 0.1/1.5* 1.557 1
Dy 0.013 0.15 0.582 1.940 0.023 2.024 1
Er 0.026 0.23 0.583 4.700 0.020 1.740 1.5
Yb 0.049 0.34 0.542 6.167 0.023 1.642 1.4
Lu 0.045 0.42 0.506 6.950 0.019 1.563
Data from Rollinson (1993). * Eu
3+
/Eu
2+
Italics are estimated
R
a
r
e

E
a
r
t
h

E
l
e
m
e
n
t
s
Compatibility depends on minerals and melts involved.

Which are incompatible? Why?
For a rock, determine the bulk distribution
coefficient D for an element by calculating
the contribution for each mineral
eq. 9-4: D
i
= E W
A
D
i
W
A
= weight % of mineral A in the rock
D
i
= partition coefficient of element i in
mineral A

A
A
Example: hypothetical garnet lherzolite = 60% olivine, 25%
orthopyroxene, 10% clinopyroxene, and 5% garnet (all by weight),
using the data in Table 9-1, is:
D
Er
= (0.6 0.026) + (0.25 0.23) + (0.10 0.583) + (0.05 4.7) =
0.366
Table 9-1. Partition Coefficients (C
S
/C
L
) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine Opx Cpx Garnet Plag Amph Magnetite
Rb 0.010 0.022 0.031 0.042 0.071 0.29
Sr 0.014 0.040 0.060 0.012 1.830 0.46
Ba 0.010 0.013 0.026 0.023 0.23 0.42
Ni 14 5 7 0.955 0.01 6.8 29
Cr 0.70 10 34 1.345 0.01 2.00 7.4
La 0.007 0.03 0.056 0.001 0.148 0.544 2
Ce 0.006 0.02 0.092 0.007 0.082 0.843 2
Nd 0.006 0.03 0.230 0.026 0.055 1.340 2
Sm 0.007 0.05 0.445 0.102 0.039 1.804 1
Eu 0.007 0.05 0.474 0.243 0.1/1.5* 1.557 1
Dy 0.013 0.15 0.582 1.940 0.023 2.024 1
Er 0.026 0.23 0.583 4.700 0.020 1.740 1.5
Yb 0.049 0.34 0.542 6.167 0.023 1.642 1.4
Lu 0.045 0.42 0.506 6.950 0.019 1.563
Data from Rollinson (1993). * Eu
3+
/Eu
2+
Italics are estimated
R
a
r
e

E
a
r
t
h

E
l
e
m
e
n
t
s
Trace elements strongly partitioned into a single
mineral
Ni - olivine in Table 9-1 = 14
Figure 9.1a. Ni Harker Diagram for Crater Lake. From data compiled by Rick Conrey. From
Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Incompatible trace elements concentrate liquid
Reflect the proportion of liquid at a given state of
crystallization or melting
Figure 9.1b. Zr Harker Diagram for Crater Lake. From data compiled by Rick Conrey. From
Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Trace Element Behavior
The concentration of a major element in a
phase is usually buffered by the system, so
that it varies little in a phase as the system
composition changes
At a given T we could vary
X
bulk
from 35 70 %
Mg/Fe without changing the
composition of the melt or
the olivine
Trace element concentrations are in the
Henrys Law region of concentration, so
their activity varies in direct relation to their
concentration in the system

Trace element concentrations are in the
Henrys Law region of concentration, so
their activity varies in direct relation to their
concentration in the system
Thus if X
Ni
in the system doubles the X
Ni
in
all phases will double
Trace element concentrations are in the
Henrys Law region of concentration, so
their activity varies in direct relation to their
concentration in the system
Thus if X
Ni
in the system doubles the X
Ni
in
all phases will double
Because of this, the ratios of trace elements
are often superior to the concentration of a
single element in identifying the role of a
specific mineral
K/Rb often used the importance of amphibole in a source rock
K & Rb behave very similarly, so K/Rb should be ~ constant
If amphibole, almost all K and Rb reside in it
Amphibole has a D of about 1.0 for K and 0.3 for Rb
Table 9-1. Partition Coefficients (C
S
/C
L
) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine Opx Cpx Garnet Plag Amph Magnetite
Rb 0.010 0.022 0.031 0.042 0.071 0.29
Sr 0.014 0.040 0.060 0.012 1.830 0.46
Ba 0.010 0.013 0.026 0.023 0.23 0.42
Ni 14 5 7 0.955 0.01 6.8 29
Cr 0.70 10 34 1.345 0.01 2.00 7.4
La 0.007 0.03 0.056 0.001 0.148 0.544 2
Ce 0.006 0.02 0.092 0.007 0.082 0.843 2
Nd 0.006 0.03 0.230 0.026 0.055 1.340 2
Sm 0.007 0.05 0.445 0.102 0.039 1.804 1
Eu 0.007 0.05 0.474 0.243 0.1/1.5* 1.557 1
Dy 0.013 0.15 0.582 1.940 0.023 2.024 1
Er 0.026 0.23 0.583 4.700 0.020 1.740 1.5
Yb 0.049 0.34 0.542 6.167 0.023 1.642 1.4
Lu 0.045 0.42 0.506 6.950 0.019 1.563
Data from Rollinson (1993). * Eu
3+
/Eu
2+
Italics are estimated
R
a
r
e

E
a
r
t
h

E
l
e
m
e
n
t
s
Sr and Ba (also incompatible elements)
Sr is excluded from most common minerals
except plagioclase
Ba similarly excluded except in alkali feldspar
Table 9-1. Partition Coefficients (C
S
/C
L
) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine Opx Cpx Garnet Plag Amph Magnetite
Rb 0.010 0.022 0.031 0.042 0.071 0.29
Sr 0.014 0.040 0.060 0.012 1.830 0.46
Ba 0.010 0.013 0.026 0.023 0.23 0.42
Ni 14 5 7 0.955 0.01 6.8 29
Cr 0.70 10 34 1.345 0.01 2.00 7.4
La 0.007 0.03 0.056 0.001 0.148 0.544 2
Ce 0.006 0.02 0.092 0.007 0.082 0.843 2
Nd 0.006 0.03 0.230 0.026 0.055 1.340 2
Sm 0.007 0.05 0.445 0.102 0.039 1.804 1
Eu 0.007 0.05 0.474 0.243 0.1/1.5* 1.557 1
Dy 0.013 0.15 0.582 1.940 0.023 2.024 1
Er 0.026 0.23 0.583 4.700 0.020 1.740 1.5
Yb 0.049 0.34 0.542 6.167 0.023 1.642 1.4
Lu 0.045 0.42 0.506 6.950 0.019 1.563
Data from Rollinson (1993). * Eu
3+
/Eu
2+
Italics are estimated
R
a
r
e

E
a
r
t
h

E
l
e
m
e
n
t
s
Compatible example:
Ni strongly fractionated olivine > pyroxene
Cr and Sc pyroxenes olivine
Ni/Cr or Ni/Sc can distinguish the effects of olivine
and augite in a partial melt or a suite of rocks
produced by fractional crystallization
Table 9-1. Partition Coefficients (C
S
/C
L
) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine Opx Cpx Garnet Plag Amph Magnetite
Rb 0.010 0.022 0.031 0.042 0.071 0.29
Sr 0.014 0.040 0.060 0.012 1.830 0.46
Ba 0.010 0.013 0.026 0.023 0.23 0.42
Ni 14 5 7 0.955 0.01 6.8 29
Cr 0.70 10 34 1.345 0.01 2.00 7.4
La 0.007 0.03 0.056 0.001 0.148 0.544 2
Ce 0.006 0.02 0.092 0.007 0.082 0.843 2
Nd 0.006 0.03 0.230 0.026 0.055 1.340 2
Sm 0.007 0.05 0.445 0.102 0.039 1.804 1
Eu 0.007 0.05 0.474 0.243 0.1/1.5* 1.557 1
Dy 0.013 0.15 0.582 1.940 0.023 2.024 1
Er 0.026 0.23 0.583 4.700 0.020 1.740 1.5
Yb 0.049 0.34 0.542 6.167 0.023 1.642 1.4
Lu 0.045 0.42 0.506 6.950 0.019 1.563
Data from Rollinson (1993). * Eu
3+
/Eu
2+
Italics are estimated
R
a
r
e

E
a
r
t
h

E
l
e
m
e
n
t
s
Models of Magma Evolution
Batch Melting
The melt remains resident until at some point it is
released and moves upward
Equilibrium melting process with variable %
melting
Models of Magma Evolution
Batch Melting
eq. 9-5

C
L
= trace element concentration in the liquid
C
O
= trace element concentration in the original rock
before melting began
F = wt fraction of melt produced = melt/(melt + rock)
C
C
1
D
i
(1 F) F
L
O
=
+
Batch Melting
A plot of C
L
/C
O
vs. F for various
values of D
i
using eq. 9-5
D
i
= 1.0

Figure 9.2. Variation in the relative concentration of a
trace element in a liquid vs. source rock as a fiunction
of D and the fraction melted, using equation (9-5) for
equilibrium batch melting. From Winter (2001) An
Introduction to Igneous and Metamorphic Petrology.
Prentice Hall.
D
i
1.0 (compatible element)

Very low concentration in
melt

Especially for low %
melting (low F)

Figure 9.2. Variation in the relative concentration of a
trace element in a liquid vs. source rock as a fiunction
of D and the fraction melted, using equation (9-5) for
equilibrium batch melting. From Winter (2001) An
Introduction to Igneous and Metamorphic Petrology.
Prentice Hall.
Highly incompatible elements
Greatly concentrated in
the initial small fraction
of melt produced by
partial melting

Subsequently diluted as
F increases
Figure 9.2. Variation in the relative concentration of a
trace element in a liquid vs. source rock as a fiunction
of D and the fraction melted, using equation (9-5) for
equilibrium batch melting. From Winter (2001) An
Introduction to Igneous and Metamorphic Petrology.
Prentice Hall.
As F 1 the concentration of
every trace element in the
liquid = the source rock (C
L
/C
O

1)
As F 1
C
L
/C
O
1
C
C
1
D
i
(1 F) F
L
O
=
+
Figure 9.2. Variation in the relative concentration of a
trace element in a liquid vs. source rock as a fiunction
of D and the fraction melted, using equation (9-5) for
equilibrium batch melting. From Winter (2001) An
Introduction to Igneous and Metamorphic Petrology.
Prentice Hall.
As F 0 C
L
/C
O
1/D
i

If we know C
L
of a magma derived
by a small degree of batch melting,
and we know D
i
we can estimate
the concentration of that element in
the source region (C
O
)
C
C
1
D
i
(1 F) F
L
O
=
+
Figure 9.2. Variation in the relative concentration of a
trace element in a liquid vs. source rock as a fiunction
of D and the fraction melted, using equation (9-5) for
equilibrium batch melting. From Winter (2001) An
Introduction to Igneous and Metamorphic Petrology.
Prentice Hall.
For very incompatible elements as D
i
0
equation 9-5 reduces to:

eq. 9.7
C
C
1
F
L
O
=
C
C
1
D
i
(1 F) F
L
O
=
+
If we know the concentration of a very
incompatible element in both a magma and the
source rock, we can determine the fraction of
partial melt produced
Worked Example of Batch Melting: Rb and Sr
Basalt with the mode:






1. Convert to weight % minerals (W
ol
W
cpx
etc.)
Table 9-2 . Conversion from mode to
weight percent
Mineral Mode Density Wt prop Wt%
ol 15 3.6 54 0.18
cpx 33 3.4 112.2 0.37
plag 51 2.7 137.7 0.45
Sum 303.9 1.00
Worked Example of Batch Melting: Rb and Sr
Table 9-2 . Conversion from mode to
weight percent
Mineral Mode Density Wt prop Wt%
ol 15 3.6 54 0.18
cpx 33 3.4 112.2 0.37
plag 51 2.7 137.7 0.45
Sum 303.9 1.00
Basalt with the mode:






1. Convert to weight % minerals (W
ol
W
cpx
etc.)
2. Use equation eq. 9-4: D
i
= E W
A
D
i
and the table of D values for Rb and Sr in each mineral
to calculate the bulk distribution coefficients: D
Rb
=
0.045 and D
Sr
= 0.848
Table 9-3

. Batch Fractionation Model for

Rb and Sr

C

L

/C

O

= 1/(D(1-F)+F)

D

Rb

D

Sr

F

0.045

0.848

Rb/Sr

0.05

9.35

1.14

8.19

0.1

6.49

1.13

5.73

0.15

4.98

1.12

4.43

0.2

4.03

1.12

3.61

0.3

2.92

1.10

2.66

0.4

2.29

1.08

2.11

0.5

1.89

1.07

1.76

0.6

1.60

1.05

1.52

0.7

1.39

1.04

1.34

0.8

1.23

1.03

1.20

0.9

1.10

1.01

1.09

3. Use the batch melting equation
(9-5)

to calculate C
L
/C
O
for various values of F

From Winter (2010) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
C
C
1
D
i
(1 F) F
L
O
=
+
4. Plot C
L
/C
O
vs. F for each element
Figure 9.3. Change in the concentration
of Rb and Sr in the melt derived by
progressive batch melting of a basaltic
rock consisting of plagioclase, augite,
and olivine. From Winter (2001) An
Introduction to Igneous and
Metamorphic Petrology. Prentice Hall.
Incremental Batch Melting
Calculate batch melting for successive
batches (same equation)
Must recalculate D
i
as solids change as
minerals are selectively melted (computer)
Fractional Crystallization
1. Crystals remain in equilibrium with each
melt increment
Rayleigh fractionation
The other extreme: separation of each
crystal as it formed = perfectly continuous
fractional crystallization in a magma
chamber
Rayleigh fractionation
The other extreme: separation of each
crystal as it formed = perfectly continuous
fractional crystallization in a magma
chamber
Concentration of some element in the residual
liquid, C
L
is modeled by the Rayleigh equation:
eq. 9-8 C
L
/C
O
= F
(D -1)
Rayleigh Fractionation
Other models are used to analyze
Mixing of magmas
Wall-rock assimilation
Zone refining
Combinations of processes
The Rare Earth Elements (REE)
Contrasts and similarities in the D values:
All are incompatible
Also Note:
HREE are less
incompatible
Especially in
garnet
Eu can 2+
which conc.
in plagioclase

Table 9-1. Partition Coefficients (C
S
/C
L
) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine Opx Cpx Garnet Plag Amph Magnetite
Rb 0.01 0.022 0.031 0.042 0.071 0.29
Sr 0.014 0.04 0.06 0.012 1.83 0.46
Ba 0.01 0.013 0.026 0.023 0.23 0.42
Ni 14.0 5.0 7.0 0.955 0.01 6.8 29.
Cr 0.7 10.0 34.0 1.345 0.01 2.0 7.4
La 0.007 0.03 0.056 0.001 0.148 0.544 2.
Ce 0.006 0.02 0.092 0.007 0.082 0.843 2.
Nd 0.006 0.03 0.23 0.026 0.055 1.34 2.
Sm 0.007 0.05 0.445 0.102 0.039 1.804 1.
Eu 0.007 0.05 0.474 0.243 0.1/1.5* 1.557 1.
Dy 0.013 0.15 0.582 3.17 0.023 2.024 1.
Er 0.026 0.23 0.583 6.56 0.02 1.74 1.5
Yb 0.049 0.34 0.542 11.5 0.023 1.642 1.4
Lu 0.045 0.42 0.506 11.9 0.019 1.563
Data from Rollinson (1993). * Eu
3+
/Eu
2+
Italics are estimated
R
a
r
e

E
a
r
t
h

E
l
e
m
e
n
t
s
REE Diagrams
Plots of concentration as the ordinate (y-axis)
against increasing atomic number
Degree of compatibility increases from left to right
across the diagram (lanthanide contraction)
C
o
n
c
e
n
t
r
a
t
i
o
n

La Ce Nd Sm Eu Tb Er Dy Yb Lu
-3
-2
-1
0
1
2
3
4
5
6
7
8
9
10
11
0 10 20 30 40 50 60 70 80 90 100
Atomic Number (Z)
L
o
g

(
A
b
u
n
d
a
n
c
e

i
n

C
I

C
h
o
n
d
r
i
t
i
c

M
e
t
e
o
r
i
t
e
)
H
He
Li
Be
B
C
N
O
F
Sc
Fe
Ni
Ne
Mg
Si
S
Ca
Ar
Ti
Pb
Pt
Sn Ba
V
K
Na
Al
P
Cl
Th
U
Eliminate Oddo-Harkins effect and make y-scale
more functional by normalizing to a standard
estimates of primordial mantle REE
chondrite meteorite concentrations
What would an REE diagram look
like for an analysis of a chondrite
meteorite?
0.00
2.00
4.00
6.00
8.00
10.00
56 58 60 62 64 66 68 70 72
s
a
m
p
l
e
/
c
h
o
n
d
r
i
t
e

L

La Ce Nd Sm Eu Tb Er Yb Lu
?
Divide each element in analysis by the
concentration in a chondrite standard
0.00
2.00
4.00
6.00
8.00
10.00
56 58 60 62 64 66 68 70 72
s
a
m
p
l
e
/
c
h
o
n
d
r
i
t
e

L

La Ce Nd Sm Eu Tb Er Yb Lu
REE diagrams using batch melting model of
a garnet lherzolite for various values of F:
Figure 9.4. Rare Earth
concentrations (normalized to
chondrite) for melts produced at
various values of F via melting of a
hypothetical garnet lherzolite using
the batch melting model (equation
9-5). From Winter (2001) An
Introduction to Igneous and
Metamorphic Petrology. Prentice
Hall.
Europium anomaly when plagioclase is
a fractionating phenocryst
or
a residual solid in source
Figure 9.5. REE diagram for 10%
batch melting of a hypothetical
lherzolite with 20% plagioclase,
resulting in a pronounced negative
Europium anomaly. From Winter
(2001) An Introduction to Igneous
and Metamorphic Petrology.
Prentice Hall.
Normalized Multielement (Spider) Diagrams
An extension of the normalized REE
technique to a broader spectrum of elements
Fig. 9.6. Spider diagram for an alkaline basalt from Gough Island, southern Atlantic.
After Sun and MacDonough (1989). In A. D. Saunders and M. J. Norry (eds.),
Magmatism in the Ocean Basins. Geol. Soc. London Spec. Publ., 42. pp. 313-345.
Chondrite-normalized spider
diagrams are commonly
organized by (the authors
estimate) of increasing
incompatibility L R

Different estimates
different ordering (poor
standardization)
MORB-normalized Spider
Separates LIL and HFS
Figure 9.7. 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).
From Winter (2001) An
Introduction to Igneous and
Metamorphic Petrology.
Prentice Hall.
Application of Trace Elements to
Igneous Systems
1. Use like major elements on variation diagrams to
document FX, assimilation, etc. in a suite of rocks
More sensitive larger variations as process
continues
Figure 9.1a. Ni Harker Diagram for
Crater Lake. From data compiled by
Rick Conrey. From Winter (2001) An
Introduction to Igneous and
Metamorphic Petrology. Prentice Hall.
2. Identification of the source rock or a particular
mineral involved in either partial melting or
fractional crystallization processes


Table 9-1. Partition Coefficients (C
S
/C
L
) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine Opx Cpx Garnet Plag Amph Magnetite
Rb 0.01 0.022 0.031 0.042 0.071 0.29
Sr 0.014 0.04 0.06 0.012 1.83 0.46
Ba 0.01 0.013 0.026 0.023 0.23 0.42
Ni 14.0 5.0 7.0 0.955 0.01 6.8 29.
Cr 0.7 10.0 34.0 1.345 0.01 2.0 7.4
La 0.007 0.03 0.056 0.001 0.148 0.544 2.
Ce 0.006 0.02 0.092 0.007 0.082 0.843 2.
Nd 0.006 0.03 0.23 0.026 0.055 1.34 2.
Sm 0.007 0.05 0.445 0.102 0.039 1.804 1.
Eu 0.007 0.05 0.474 0.243 0.1/1.5* 1.557 1.
Dy 0.013 0.15 0.582 3.17 0.023 2.024 1.
Er 0.026 0.23 0.583 6.56 0.02 1.74 1.5
Yb 0.049 0.34 0.542 11.5 0.023 1.642 1.4
Lu 0.045 0.42 0.506 11.9 0.019 1.563
Data from Rollinson (1993). * Eu
3+
/Eu
2+
Italics are estimated
R
a
r
e

E
a
r
t
h

E
l
e
m
e
n
t
s
Garnet concentrates the HREE and fractionates among them
Thus if garnet is in equilibrium with the partial melt (a residual
phase in the source left behind) expect a steep (-) slope in REE and
HREE
Shallow (< 40
km) partial
melting of the
mantle will have
plagioclase in
the resuduum
and a Eu
anomaly will
result
0.00

2.00

4.00

6.00

8.00

10.00

56

58

60

62

64

66

68

70

72

s
a
m
p
l
e
/
c
h
o
n
d
r
i
t
e

La Ce Nd Sm Eu Tb Er Yb Lu

67% Ol 17% Opx 17% Cpx

0.00

2.00

4.00

6.00

8.00

10.00

56

58

60

62

64

66

68

70

72

s
a
m
p
l
e
/
c
h
o
n
d
r
i
t
e

La Ce Nd Sm Eu Tb Er Yb Lu

57% Ol 14% Opx 14% Cpx 14% Grt

Garnet and Plagioclase
effect on HREE
0.00

2.00

4.00

6.00

8.00

10.00

s
a
m
p
l
e
/
c
h
o
n
d
r
i
t
e

60% Ol 15% Opx 15% Cpx 10%Plag

La Ce Nd Sm Eu Tb Er Yb Lu

Figure 9.3. Change in the concentration
of Rb and Sr in the melt derived by
progressive batch melting of a basaltic
rock consisting of plagioclase, augite,
and olivine. From Winter (2001) An
Introduction to Igneous and
Metamorphic Petrology. Prentice Hall.

Element Use as a Petrogenetic Indicator
Ni, Co, Cr Highly compatible elements. Ni and Co are concentrated in olivine, and Cr in spinel and clinopyroxene. High concentrations
indicate a mantle source, limited fractionation, or crystal accumulation.
Zr, Hf Very incompatible elements that do not substitute into major silicate phases (although they may replace Ti in titanite or
rutile). High concentrations imply an enriched source or extensive liquid evolution.
Nb, Ta High field-strength elements that partition into Ti-rich phases (titanite, Ti-amphibole, Fe-Ti oxides. Typically low
concentrations in subduction-related melts.
Ru, Rh, Pd,
Re, Os, Ir,
Pd
Platinum group elements (PGEs) are siderophile and used mostly to study melting and crystallization in mafic-ultramafic
systems in which PGEs are typically hosted by sulfides. The Re/Os isotopic system is controlled by initial PGE
differentiation and is applied to mantle evolution and mafic melt processes.
Sc Concentrates in pyroxenes and may be used as an indicator of pyroxene fractionation.
Sr Substitutes for Ca in plagioclase (but not in pyroxene), and, to a lesser extent, for K in K-feldspar. Behaves as a compatible
element at low pressure where plagioclase forms early, but as an incompatible element at higher pressure where
plagioclase is no longer stable.
REE Myriad uses in modeling source characteristics and liquid evolution. Garnet accommodates the HREE more than the LREE,
and orthopyroxene and hornblende do so to a lesser degree. Titanite and plagioclase accommodates more LREE. Eu
2+
is
strongly partitioned into plagioclase.
Y Commonly incompatible. Strongly partitioned into garnet and amphibole. Titanite and apatite also concentrate Y, so the
presence of these as accessories could have a significant effect.
Table 9.6 A Brief Summary of Some Particularly Useful Trace Elements in Igneous Petrology
Trace elements as a tool to determine
paleotectonic environment
Useful for rocks in mobile belts that are no
longer recognizably in their original setting
Can trace elements be discriminators of
igneous environment?
Approach is empirical on modern occurrences
Concentrate on elements that are immobile
during low/medium grade metamorphism
Figure 9.8 Examples of discrimination diagrams used to infer tectonic setting of ancient (meta)volcanics. (a) after Pearce and Cann (1973), (b)
after Pearce (1982), Coish et al. (1986). Reprinted by permission of the American Journal of Science, (c) after Mullen (1983) Copyright with
permission from Elsevier Science, (d) and (e) after Vermeesch (2005) AGU with permission.
Isotopes
Same Z, different A (variable # of neutrons)
General notation for a nuclide:
6
14
C
Isotopes
Same Z, different A (variable # of neutrons)
General notation for a nuclide:
6
14
C
As n varies different isotopes of an element


12
C
13
C
14
C
Stable Isotopes
Stable: last ~ forever
Chemical fractionation is impossible
Mass fractionation is the only type possible
Example: Oxygen Isotopes
Concentrations expressed by reference to a standard
International standard for O isotopes = standard mean
ocean water (SMOW)
16
O 99.756% of natural oxygen
17
O 0.039%
18
O 0.205%
18
O and
16
O are the commonly used isotopes
and their ratio is expressed as o:

o (
18
O/
16
O) = eq 910



result expressed in per mille ()
( O/ O) ( O/ O)
( O/ O)
x 1000
18 16
sample
18 16
SMOW
18 16
SMOW

What is o of SMOW??
What is o for meteoric water?
What is o for meteoric water?
Evaporation seawater water vapor (clouds)
Light isotope enriched in vapor > liquid
Pretty efficient, since A mass = 1/8 total mass
What is o for meteoric water?
Evaporation seawater water vapor (clouds)
Light isotope enriched in vapor > liquid
Pretty efficient, since A mass = 1/8 total mass

o =


therefore <
thus o
clouds
is (-)
( O/ O) ( O/ O)
( O/ O)
x 1000
18 16
vapor
18 16
SMOW
18 16
SMOW

( O/ O)
18 16
Vapor
( O/ O)
18 16
SMOW
Figure 9.9. Relationship between d(
18
O/
16
O) and mean annual temperature
for meteoric precipitation, after Dansgaard (1964). Tellus, 16, 436-468.
O and H isotopes - juvenile vs. meteoric vs.
brine water
o
18
O for mantle rocks = surface-reworked
sediments: evaluate contamination of mantle-
derived magmas by crustal sediments
Stable isotopes useful in assessing relative
contribution of various reservoirs, each with
a distinctive isotopic signature
Radioactive Isotopes
Unstable isotopes decay to other nuclides
The rate of decay is constant, and not
affected by P, T, X
Parent nuclide = radioactive nuclide that
decays
Daughter nuclide(s) are the radiogenic
atomic products
Isotopic variations between rocks, etc. due to:
1. Mass fractionation (as for stable isotopes)
Only effective for light isotopes: H He C O S
Isotopic variations between rocks, etc. due to:
1. Mass fractionation (as for stable isotopes)
2. Daughters produced in varying proportions
resulting from previous event of chemical
fractionation
40
K
40
Ar by radioactive decay
Basalt rhyolite by FX (a chemical fractionation process)
Rhyolite has more K than basalt
40
K more
40
Ar over time in rhyolite than in basalt
40
Ar/
39
Ar ratio will be different in each
Isotopic variations between rocks, etc. due to:
1. Mass fractionation (as for stable isotopes)
2. Daughters produced in varying proportions
resulting from previous event of chemical
fractionation
3. Time
The longer
40
K
40
Ar decay takes place, the greater
the difference between the basalt and rhyolite will be

Radioactive Decay
The Law of Radioactive Decay
eq. 9.11


dN
dt
N or
dN
dt
= N

time
1






D = Ne
t
- N

= N(e
t
-1) eq 9.14

age of a sample (t) if we know:
D the amount of the daughter nuclide produced
N the amount of the original parent nuclide remaining
the decay constant for the system in question
The K-Ar System
40
K either
40
Ca or
40
Ar

40
Ca is common. Cannot distinguish radiogenic
40
Ca from non-radiogenic
40
Ca

40
Ar is an inert gas which can be trapped in
many solid phases as it forms in them
The appropriate decay equation is:
eq 9.16
40
Ar =
40
Ar
o
+
40
K(e
-t
-1)

Where
e
= 0.581 x 10
-10
a
-1
(proton capture)
and = 5.543 x 10
-10
a
-1
(whole process)


e
|
\

|
.
|
Blocking temperatures for various minerals
differ

40
Ar-
39
Ar technique grew from this discovery
Sr-Rb System
-
87
Rb
87
Sr + a beta particle ( = 1.42 x 10
-11
a
-1
)
- Rb behaves like K micas and alkali feldspar
- Sr behaves like Ca plagioclase and apatite (but not
clinopyroxene)
-
88
Sr :
87
Sr :
86
Sr :
84
Sr ave. sample = 10 : 0.7 : 1 : 0.07
-
86
Sr is a stable isotope, and not created by breakdown
of any other parent
Isochron Technique

Requires 3 or more cogenetic samples with a range
of Rb/Sr
Could be:
3 cogenetic rocks derived
from a single source by
partial melting, FX, etc.
Figure 9.3. Change in the concentration of Rb
and Sr in the melt derived by progressive batch
melting of a basaltic rock consisting of
plagioclase, augite, and olivine. From Winter
(2001) An Introduction to Igneous and
Metamorphic Petrology. Prentice Hall.
Isochron Technique

Requires 3 or more cogenetic samples with a range
of Rb/Sr
Could be:
3 cogenetic rocks derived
from a single source by
partial melting, FX, etc.
3 coexisting minerals with
different K/Ca ratios in a
single rock
For values of t less than 0.1: e
t
-1 ~ t
Thus eq. 9-15 for t < 70 Ga (!!) reduces to:
eq 9.18
87
Sr/
86
Sr = (
87
Sr/
86
Sr)
o
+ (
87
Rb/
86
Sr)t
y = b + x m
= equation for a line in
87
Sr/
86
Sr vs.
87
Rb/
86
Sr plot
Recast age equation by dividing through by stable
86
Sr

87
Sr/
86
Sr = (
87
Sr/
86
Sr)
o
+ (
87
Rb/
86
Sr)(e
t
-1) eq 9.17
= 1.4 x 10
-11
a
-1
a
b c
t
o

86
Sr
87
Sr
o
( )
86
Sr
87
Sr
86
Sr
87
Rb
Begin with 3 rocks plotting at a b c at time t
o

After some time increment (t
0
t
1
) each sample loses
some
87
Rb and gains an equivalent amount of
87
Sr
a
b c
a
1

b
1

c
1

t
1

t
o

86
Sr
87
Sr
86
Sr
87
Rb
86
Sr
87
Sr
o
( )
At time t
2
each rock system has evolved new line
Again still linear and steeper line
a
b c
a
1

b
1

c
1

a
2

b
2

c
2

t
1

t
o

t
2

86
Sr
87
Sr
86
Sr
87
Sr
o
( )
86
Sr
87
Rb
Isochron technique produces 2 valuable things:
1. The age of the rocks (from the slope = t)
2. (
87
Sr/
86
Sr)
o
= the initial value of
87
Sr/
86
Sr
Figure 9.12. Rb-Sr isochron for the Eagle Peak Pluton, central Sierra Nevada Batholith, California, USA. Filled circles are
whole-rock analyses, open circles are hornblende separates. The regression equation for the data is also given. After Hill et al.
(1988). Amer. J. Sci., 288-A, 213-241.
Figure 9.13. Estimated Rb and Sr isotopic evolution of the Earths upper mantle, assuming a large-scale melting
event producing granitic-type continental rocks at 3.0 Ga b.p After Wilson (1989). Igneous Petrogenesis. Unwin
Hyman/Kluwer.
The Sm-Nd System
Both Sm and Nd are LREE
Incompatible elements fractionate melts
Nd has lower Z larger liquids > does Sm
147
Sm
143
Nd by alpha decay
= 6.54 x 10
-13
a
-1
(half life 106 Ga)
Decay equation derived by reference to
the non-radiogenic
144
Nd

143
Nd/
144
Nd = (
143
Nd/
144
Nd)
o

+ (
147
Sm/
144
Nd)t
Evolution curve is opposite to Rb - Sr

Figure 9.15. Estimated Nd isotopic evolution of the Earths upper mantle, assuming a large-scale melting or
enrichment event at 3.0 Ga b.p. After Wilson (1989). Igneous Petrogenesis. Unwin Hyman/Kluwer.
The U-Pb-Th System
Very complex system.
3 radioactive isotopes of U:
234
U,
235
U,
238
U
3 radiogenic isotopes of Pb:
206
Pb,
207
Pb, and
208
Pb
Only
204
Pb is strictly non-radiogenic
U, Th, and Pb are incompatible elements, &
concentrate in early melts
Isotopic composition of Pb in rocks = function of

238
U
234
U
206
Pb ( = 1.5512 x 10
-10
a
-1
)

235
U
207
Pb ( = 9.8485 x 10
-10
a
-1
)

232
Th
208
Pb ( = 4.9475 x 10
-11
a
-1
)
The U-Pb-Th System
Concordia = Simultaneous co-
evolution of
206
Pb and
207
Pb via:

238
U
234
U
206
Pb
235
U
207
Pb
Figure 9-16a. Concordia diagram illustrating the Pb isotopic
development of a 3.5 Ga old rock with a single episode of Pb loss.
After Faure (1986). Principles of Isotope Geology. 2nd, ed. John
Wiley & Sons. New York.
The U-Pb-Th System
Discordia = loss of both
206
Pb and
207
Pb
Figure 9-16a. Concordia diagram illustrating the Pb isotopic
development of a 3.5 Ga old rock with a single episode of Pb loss.
After Faure (1986). Principles of Isotope Geology. 2nd, ed. John
Wiley & Sons. New York.
The U-Pb-Th System
Concordia diagram after 3.5 Ga total evolution
Figure 9.16b. Concordia diagram illustrating the Pb isotopic development of a 3.5 Ga old rock with a single episode of Pb loss. After
Faure (1986). Principles of Isotope Geology. 2nd, ed. John Wiley & Sons. New York.
The U-Pb-Th System
Figure 9.17. Concordia diagram for three discordant zircons separated from an Archean gneiss at Morton and Granite Falls, Minnesota. The
discordia intersects the concordia at 3.55 Ga, yielding the U-Pb age of the gneiss, and at 1.85 Ga, yielding the U-Pb age of the depletion event.
From Faure (1986). Copyright reprinted by permission of John Wiley & Sons, Inc.