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=

a solid
a i liquid
i

K = equilibrium constant

X solid
i
i
X liquid
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 XNi in the system doubles the XNi in
all phases will double
This does not mean that X in all phases
Ni
is the same, since trace elements do
fractionate. Rather the XNi within each
phase will vary in proportion to the
system concentration

incompatible elements are concentrated in the

melt
(KD or D) 1

compatible elements are concentrated in the

solid
KD or D 1

For dilute solutions can substitute D for K D:

CS
D = CL

Where CS = the concentration of some element in

the solid phase

Incompatible elements commonly two subgroups

Smaller, highly charged high field strength (HFS)

elements (REE, Th, U, Ce, Pb4+, Zr, Hf, Ti, Nb, Ta)
Low field strength large ion lithophile (LIL)
elements (K, Rb, Cs, Ba, Pb2+, Sr, Eu2+) are more
mobile, particularly if a fluid phase is involved

Compatibility depends on minerals and melts involved.

Which are incompatible? Why?

Rb
Sr
Ba
Ni
Cr
La
Ce
Nd
Sm
Eu
Dy
Er
Yb
Lu

Rare Earth Elements

Table 9-1. Partition Coefficients (CS/CL) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine
0.010
0.014
0.010
14
0.70
0.007
0.006
0.006
0.007
0.007
0.013
0.026
0.049
0.045

Opx
0.022
0.040
0.013
5
10
0.03
0.02
0.03
0.05
0.05
0.15
0.23
0.34
0.42

Data from Rollinson (1993).

Cpx
Garnet
0.031
0.042
0.060
0.012
0.026
0.023
7
0.955
34
1.345
0.056
0.001
0.092
0.007
0.230
0.026
0.445
0.102
0.474
0.243
0.582
1.940
0.583
4.700
0.542
6.167
0.506
6.950

Plag
Amph Magnetite
0.071
0.29
1.830
0.46
0.23
0.42
0.01
6.8
29
0.01
2.00
7.4
0.148
0.544
2
0.082
0.843
2
0.055
1.340
2
0.039
1.804
1
0.1/1.5*
1.557
1
0.023
2.024
1
0.020
1.740
1.5
0.023
1.642
1.4
0.019
1.563
* Eu3+/Eu2+

Italics are estimated

For a rock, determine the bulk distribution

coefficient D for an element by calculating
the contribution for each mineral
eq. 9-4:

Di = WA Di
A

WA = weight % of mineral A in the rock

DiA= partition coefficient of element i in
mineral A

Rb
Sr
Ba
Ni
Cr
La
Ce
Nd
Sm
Eu
Dy
Er
Yb
Lu

Rare Earth Elements

Table 9-1. Partition Coefficients (CS/CL) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine
0.010
0.014
0.010
14
0.70
0.007
0.006
0.006
0.007
0.007
0.013
0.026
0.049
0.045

Opx
0.022
0.040
0.013
5
10
0.03
0.02
0.03
0.05
0.05
0.15
0.23
0.34
0.42

Data from Rollinson (1993).

Cpx
Garnet
0.031
0.042
0.060
0.012
0.026
0.023
7
0.955
34
1.345
0.056
0.001
0.092
0.007
0.230
0.026
0.445
0.102
0.474
0.243
0.582
1.940
0.583
4.700
0.542
6.167
0.506
6.950

Plag
Amph Magnetite
0.071
0.29
1.830
0.46
0.23
0.42
0.01
6.8
29
0.01
2.00
7.4
0.148
0.544
2
0.082
0.843
2
0.055
1.340
2
0.039
1.804
1
0.1/1.5*
1.557
1
0.023
2.024
1
0.020
1.740
1.5
0.023
1.642
1.4
0.019
1.563
* Eu3+/Eu2+

Italics are estimated

Example: hypothetical garnet lherzolite = 60% olivine, 25%

orthopyroxene, 10% clinopyroxene, and 5% garnet (all by weight),
using the data in Table 9-1, is:
DEr = (0.6 0.026) + (0.25 0.23) + (0.10 0.583) + (0.05 4.7) = 0.366

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

Xmelt from 20 60 %
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 XNi in the system doubles the XNi 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 XNi in the system doubles the XNi 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 (CS/CL) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Rb
Sr
Ba
Ni
Cr
La
Ce
Nd
Sm
Eu
Dy
Er
Yb
Lu

Rare Earth Elements

Olivine
0.010
0.014
0.010
14
0.70
0.007
0.006
0.006
0.007
0.007
0.013
0.026
0.049
0.045

Opx
0.022
0.040
0.013
5
10
0.03
0.02
0.03
0.05
0.05
0.15
0.23
0.34
0.42

Data from Rollinson (1993).

Cpx
Garnet
0.031
0.042
0.060
0.012
0.026
0.023
7
0.955
34
1.345
0.056
0.001
0.092
0.007
0.230
0.026
0.445
0.102
0.474
0.243
0.582
1.940
0.583
4.700
0.542
6.167
0.506
6.950

Plag
Amph Magnetite
0.071
0.29
1.830
0.46
0.23
0.42
0.01
6.8
29
0.01
2.00
7.4
0.148
0.544
2
0.082
0.843
2
0.055
1.340
2
0.039
1.804
1
0.1/1.5*
1.557
1
0.023
2.024
1
0.020
1.740
1.5
0.023
1.642
1.4
0.019
1.563
* Eu3+/Eu2+

Italics are estimated

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 (CS/CL) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Rb
Sr
Ba
Ni
Cr
La
Ce
Nd
Sm
Eu
Dy
Er
Yb
Lu

Rare Earth Elements

Olivine
0.010
0.014
0.010
14
0.70
0.007
0.006
0.006
0.007
0.007
0.013
0.026
0.049
0.045

Opx
0.022
0.040
0.013
5
10
0.03
0.02
0.03
0.05
0.05
0.15
0.23
0.34
0.42

Data from Rollinson (1993).

Cpx
Garnet
0.031
0.042
0.060
0.012
0.026
0.023
7
0.955
34
1.345
0.056
0.001
0.092
0.007
0.230
0.026
0.445
0.102
0.474
0.243
0.582
1.940
0.583
4.700
0.542
6.167
0.506
6.950

Plag
Amph Magnetite
0.071
0.29
1.830
0.46
0.23
0.42
0.01
6.8
29
0.01
2.00
7.4
0.148
0.544
2
0.082
0.843
2
0.055
1.340
2
0.039
1.804
1
0.1/1.5*
1.557
1
0.023
2.024
1
0.020
1.740
1.5
0.023
1.642
1.4
0.019
1.563
* Eu3+/Eu2+

Italics are estimated

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

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
1
eq. 9-5 C L
C O Di (1 F) F
CL = trace element concentration in the liquid
CO = trace element concentration in the original rock
before melting began
F = wt fraction of melt produced = melt/(melt + rock)

Batch Melting
A plot of CL/CO vs. F for various
values of Di using eq. 9-5

Di = 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.

Di 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 (CL/CO
1)

1
CL
As F 1

C O Di (1 F) F CL/CO 1

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 CL/CO 1/Di

1
CL

C O Di (1 F) F

If we know CL of a magma derived

by a small degree of batch melting,
and we know Di we can estimate
the concentration of that element in
the source region (CO)

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 Di 0

equation 9-5

1
CL

C O Di (1 F) F

reduces to:

CL 1

eq. 9-7
CO F
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:
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

1. Convert to weight % minerals (Wol Wcpx etc.)

Worked Example of Batch Melting: Rb and Sr

Basalt with the mode:
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

1. Convert to weight % minerals (Wol Wcpx etc.)

2. Use equation eq. 9-4:

Di = WA Di

and the table of D values for Rb and Sr in each mineral

to calculate the bulk distribution coefficients: DRb =
0.045 and D = 0.848

3. Use the batch melting equation

(9-5)
to calculate CL/CO for various values of F
Table 9-3 . Batch Fractionation Model for
Rb and Sr

F
0.05
0.1
0.15
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9

C L/C O = 1/(D(1-F)+F)
D Rb
D Sr
0.045
0.848
9.35
1.14
6.49
1.13
4.98
1.12
4.03
1.12
2.92
1.10
2.29
1.08
1.89
1.07
1.60
1.05
1.39
1.04
1.23
1.03
1.10
1.01

Rb/Sr
8.19
5.73
4.43
3.61
2.66
2.11
1.76
1.52
1.34
1.20
1.09

From Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.

4. Plot CL/CO 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 Di 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, CL is modeled by the Rayleigh equation:

eq. 9-8 CL/CO = 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
Table 9-1. Partition Coefficients for some commonly used
trace elements in basaltic and andesitic rocks

HREE are less

incompatible
Especially in
garnet
Eu can 2+
which conc.
in plagioclase

Rb
Sr
Ba
Ni
Cr
La
Ce
Nd
Sm
Eu
Tb
Er
Yb
Lu

Rare Earth Elements

Also Note:

Olivine
0.006
0.01
0.006
14
2.1
0.007
0.009
0.009
0.009
0.008
0.01
0.013
0.014
0.016

Opx
0.02
0.01
0.12
5
10
0.02
0.02
0.05
0.05
0.05
0.05
0.31
0.34
0.11

data from Henderson (1982)

Cpx
0.04
0.14
0.07
2.6
8.4
0.08
0.34
0.6
0.9
0.9
1
1
0.2
0.82
* Eu3+/Eu2+

Garnet
0.001
0.001
0.002
0.4
0.17
0.05
0.05
0.07
0.06
0.9
5.6
18
30
35

Plag
0.1
1.8
0.23
0.01
10
0.14
0.14
0.08
0.08
0.1/1.5*
0.03
0.08
0.07
0.08

Amph
0.3
0.57
0.31
3
1.6
0.27
0.34
0.19
0.91
1.01
1.4
0.48
0.97
0.89

Italics are estimated

REE Diagrams

Concentration

Plots of concentration as the ordinate (y-axis)

against increasing atomic number
Degree of compatibility increases from left
to right across the diagram

La Ce Nd Sm Eu Tb Er Dy Yb Lu

Log (Abundance in CI Chondritic Meteorite)

11

H
He

10
9
8

7
6
5
4
3
2
1

Li

Ne MgSi
Fe
N
S Ar
Ca Ni
Na
Ti
AlP
K
F Cl
V
B
Sc

Sn

Ba

Pt Pb

Be

-1

Th

-2

-3
0

10

20

30

40

50

60

70

80

90

Atomic Number (Z)

Eliminate Oddo-Harkins effect and make y-scale more

functional by normalizing to a standard
estimates of primordial mantle REE
chondrite meteorite concentrations

100

What would an REE diagram look

like for an analysis of a chondrite
meteorite?
sample/chondrite

10.00
8.00
6.00

4.00
2.00
0.00
56 La58
Ce

60Nd 62Sm 64
Eu

66
Tb

68Er 70 Yb 72
Lu

Divide each element in analysis by the

concentration in a chondrite standard

sample/chondrite

10.00
8.00
6.00
4.00
2.00
0.00
56 La58
Ce

60Nd 62Sm 64
Eu

66
Tb

68Er 70 Yb 72
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.

Spider Diagrams
An extension of the normalized REE
technique to a broader spectrum of elements
Chondrite-normalized spider
diagrams are commonly
organized by (the authors
estimate) of increasing
incompatibility L R
Different estimates
different ordering (poor
standardization)
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.

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

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
Table 9-1. Partition Coefficients for some commonly used

Shallow (< 40
km) partial
melting of the
mantle will have
plagioclase in
the resuduum
and a Eu
anomaly will
result

Rb
Sr
Ba
Ni
Cr
La
Ce
Nd
Sm
Eu
Tb
Er
Yb
Lu

Rare Earth Elements

trace elements in basaltic and andesitic rocks

Olivine
0.006
0.01
0.006
14
2.1
0.007
0.009
0.009
0.009
0.008
0.01
0.013
0.014
0.016

Opx
0.02
0.01
0.12
5
10
0.02
0.02
0.05
0.05
0.05
0.05
0.31
0.34
0.11

data from Henderson (1982)

Cpx
0.04
0.14
0.07
2.6
8.4
0.08
0.34
0.6
0.9
0.9
1
1
0.2
0.82
* Eu3+/Eu2+

Garnet
0.001
0.001
0.002
0.4
0.17
0.05
0.05
0.07
0.06
0.9
5.6
18
30
35

Plag
0.1
1.8
0.23
0.01
10
0.14
0.14
0.08
0.08
0.1/1.5*
0.03
0.08
0.07
0.08

Amph
0.3
0.57
0.31
3
1.6
0.27
0.34
0.19
0.91
1.01
1.4
0.48
0.97
0.89

Italics are estimated

10.00

67% Ol

sample/chondrite

8.00

17% Opx

17% Cpx

Garnet and Plagioclase

effect on HREE

6.00

4.00

2.00

0.00
56

58 Ce 60 Nd 62Sm Eu
64
La

Tb66

68
Er

70 Lu 72
Yb

10.00

10.00

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

sample/chondrite

sample/chondrite

8.00

6.00

4.00

57% Ol

8.00

14% Opx

14% Cpx 14% Grt

6.00

4.00

2.00

2.00

0.00

0.00

La Ce Nd Sm Eu

Tb

Er

Yb Lu

56

58
La

64
Ce60 Nd 62Sm Eu

Tb66

68
Er

70 Lu
Yb

72

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.

Table 9-6 A brief summary of some particularly useful trace elements in igneous petrology
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.
V, Ti

Both show strong fractionation into Fe-Ti oxides (ilmenite or titanomagnetite). If they behave
differently, Ti probably fractionates into an accessory phase, such as sphene or rutile.

Zr, Hf

Very incompatible elements that do not substitute into major silicate phases (although they may
replace Ti in sphene or rutile).

Ba, Rb

Incompatible element that substitutes for K in K-feldspar, micas, or hornblende. Rb substitutes

less readily in hornblende than K-spar and micas, such that the K/Ba ratio may distinguish these
phases.

Sr

Substitutes for Ca in plagioclase (but not in pyroxene), and, to a lesser extent, for K in Kfeldspar. Behaves as a compatible element at low pressure where plagioclase forms early, but
as an incompatible at higher pressure where plagioclase is no longer stable.

REE

Garnet accommodates the HREE more than the LREE, and orthopyroxene and hornblende do
2+
so to a lesser degree. Sphene and plagioclase accommodates more LREE. Eu is strongly
partitioned into plagioclase.

Commonly incompatible (like HREE). Strongly partitioned into garnet and amphibole. Sphene
and apatite also concentrate Y, so the presence of these as accessories could have a
significant effect.
Table 9-6. After Green (1980). Tectonophys., 63,
63, 367385. From Winter (2001) An Introduction to Igneous
and Metamorphic Petrology. Prentice Hall.

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. (a) after Pearce and Cann (1973), Earth Planet, Sci. Lett., 19,
19, 290-300.
290-300. (b) after Pearce (1982) in
Thorpe (ed.), Andesites: Orogenic andesites and related rocks. Wiley. Chichester. pp. 525-548 , Coish et al. (1986),
Amer. J. Sci., 286,
286, 1-28.
1-28. (c) after Mullen (1983), Earth Planet. Sci. Lett., 62,
62, 53-62.

Isotopes
Same Z, different A (variable # of neutrons)
14
General notation for a nuclide:
6C

Isotopes
Same Z, different A (variable # of neutrons)
14
General notation for a nuclide: 6 C
As n varies different isotopes of an element

12

13

14

Stable Isotopes

Stable: last ~ forever

Chemical fractionation is impossible
Mass fractionation is the only type possible

Example: Oxygen Isotopes

O
17
O
18
O
16

99.756% of natural oxygen

0.039%

0.205%

Concentrations expressed by reference to a standard

International standard for O isotopes = standard mean
ocean water (SMOW)

O and 16O are the commonly used isotopes

and their ratio is expressed as :

18

18O/16O) =
eq

18
16

( O/ O) sample ( O/ O) SMOW
18

16

18

16

( O/ O) SMOW
result expressed in per mille ()

What is of SMOW??
What is for meteoric water?

x 1000

What is for meteoric water?

Evaporation seawater water vapor (clouds)

Light isotope enriched in vapor > liquid

Pretty efficient, since mass = 1/8 total mass

What is for meteoric water?

Evaporation seawater water vapor (clouds)

Light isotope enriched in vapor > liquid

Pretty efficient, since mass = 1/8 total mass
=

( 18 O/ 16 O) vapor ( 18 O/ 16 O) SMOW
18

16

( O/ O) SMOW

x 1000

( 18 O/ 16 O) Vapor < ( 18 O/ 16 O) SMOW

therefore
thus clouds is (-)

Figure 9-9. Relationship between d(18O/16O) and mean annual temperature

for meteoric precipitation, after Dansgaard (1964). Tellus, 16, 436-468.

Stable isotopes useful in assessing relative

contribution of various reservoirs, each with
a distinctive isotopic signature

O and H isotopes - juvenile vs. meteoric vs.

brine water
18O for mantle rocks surface-reworked
sediments: evaluate contamination of mantlederived magmas by crustal sediments

Radioactive Isotopes

Unstable isotopes decay to other nuclides

Radioactive Isotopes

Unstable isotopes decay to other nuclides

The rate of decay is constant, and not
affected by P, T, X

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

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

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
K 40Ar by radioactive decay

40

Basalt rhyolite by FX (a chemical fractionation process)

Rhyolite has more K than basalt
K more 40Ar over time in rhyolite than in basalt

40

Ar/39Ar ratio will be different in each

40

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 40K 40Ar 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
N
dt

or

dN
= N
dt

# parent atoms

time

D = Net - N = N(et -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

K either 40Ca or 40Ar

40

Ca is common. Cannot distinguish radiogenic

40Ca from non-radiogenic 40Ca
40Ar is an inert gas which can be trapped in
many solid phases as it forms in them

40

The appropriate decay equation is:

eq 9-16

40
Ar = 40Aro +

K(e-t -1)

40

Where e = 0.581 x 10-10 a-1 (proton capture)

and = 5.543 x 10-10 a-1 (whole process)

Blocking temperatures for various minerals

differ
40Ar-39Ar technique grew from this discovery

Sr-Rb System
Rb 87Sr + a beta particle

( = 1.42 x 10-11 a-1)

87

Rb behaves like K micas and alkali feldspar

Sr behaves like Ca plagioclase and apatite (but not

clinopyroxene)
Sr : 87Sr : 86Sr : 84Sr ave. sample = 10 : 0.7 : 1 : 0.07

88

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

Recast age equation by dividing through by stable 86Sr

Sr/86Sr = (87Sr/86Sr)o + (87Rb/86Sr)(et -1)
= 1.4 x 10-11 a-1

87

eq 9-17

For values of t less than 0.1: et-1 t

Thus eq. 9-15 for t < 70 Ga (!!) reduces to:
eq 9-18

Sr/86Sr = (87Sr/86Sr)o + (87Rb/86Sr)t

87

= equation for a line in 87Sr/86Sr vs. 87Rb/86Sr plot

Begin with 3 rocks plotting at a b c at time to

Sr
86
Sr
87

( )
Sr
86
Sr
87

b
Rb
86
Sr
87

to

After some time increment (t0 t1) each sample loses

some 87Rb and gains an equivalent amount of 87Sr

Sr
86
Sr
87

( )
Sr
86
Sr

c1

b1

a1

t1

87

b
Rb
86
Sr
87

to

At time t2 each rock system has evolved new line

Again still linear and steeper line
t2
Sr
86
Sr
87

c2
b2
a2

( )
Sr
Sr

c1

b1

a1

t1

87

86

to
Rb
86
Sr
87

Isochron technique produces 2 valuable things:

1. The age of the rocks (from the slope = t)
2. (87Sr/86Sr)o = the initial value of 87Sr/86Sr

Figure 9-9. 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

Sm 143Nd by alpha decay

147

= 6.54 x 10-13 a-1 (half life 106 Ga)

Sm 143Nd by alpha decay

147

= 6.54 x 10-13 a-1 (half life 106 Ga)

Decay equation derived by reference to

the non-radiogenic 144Nd
143Nd/144Nd = (143Nd/144Nd)
o
+ (147Sm/144Nd)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: 234U, 235U, 238U

The U-Pb-Th System

Very complex system.

3 radioactive isotopes of U: 234U, 235U, 238U

3 radiogenic isotopes of Pb: 206Pb, 207Pb, and 208Pb

The U-Pb-Th System

Very complex system.

3 radioactive isotopes of U: 234U, 235U, 238U

3 radiogenic isotopes of Pb: 206Pb, 207Pb, and 208Pb

U, Th, and Pb are incompatible elements, &

concentrate in early melts

The U-Pb-Th System

Very complex system.

3 radioactive isotopes of U: 234U, 235U, 238U

3 radiogenic isotopes of Pb: 206Pb, 207Pb, and 208Pb

Only 204Pb is strictly non-radiogenic

U, Th, and Pb are incompatible elements, &

concentrate in early melts
Isotopic composition of Pb in rocks = function of

U 234U 206Pb
235U 207Pb
232Th 208Pb
238

( = 1.5512 x 10-10 a-1)

( = 9.8485 x 10-10 a-1)
( = 4.9475 x 10-11 a-1)

The U-Pb-Th System

Concordia = Simultaneous coevolution of 206Pb and 207Pb via:
U 234U 206Pb
235U 207Pb
238

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
Pb and 207Pb

206

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 9-16a. 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.