Chapter 9: Trace Elements

Note
magnitud
e 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
magnitud
e 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
Goldschmidt’s 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?

Goldschmidt’s 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)
ai solid i Xi solid
eq. 9.2 K= ai liquid =  X liquid
i i

K = equilibrium constant

Trace element concentrations are in the
Henry’s 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?

Table 9-1. Partition Coefficients (CS/CL) 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.
Rare Earth Elements

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). * 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
 Table 9-1. Partition Coefficients (CS/CL) 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
Rare Earth Elements

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). * 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

Xbulk from 35  70 %
Mg/Fe without changing the
composition of the melt or
the olivine
Trace element concentrations are in the
Henry’s Law region of concentration, so
their activity varies in direct relation to their
concentration in the system
Trace element concentrations are in the
Henry’s 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
Henry’s 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

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
Rare Earth Elements

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). * 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

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
Rare Earth Elements

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). * 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
eq. 9.5 CL  1
CO 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)
CL 1 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.
 CL 1
As F  0 CL/CO  1/Di 
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
CL 1
equation 9.5  reduces to:
C O Di (1  F)  F

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 with the mode:
Basalt
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 with the mode:
Basalt
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
CL 1
(9.5) 
C O Di (1  F)  F
to calculate CL/CO for various values of F
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
From Winter (2010) 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 (CS/CL) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Also Note: Olivine Opx Cpx Garnet Plag Amph Magnetite
Rb 0.01 0.022 0.031 0.042 0.071 0.29
HREE are less 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
incompatible 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
Especially in La 0.007 0.03 0.056 0.001 0.148 0.544 2.
Rare Earth Elements

Ce 0.006 0.02 0.092 0.007 0.082 0.843 2.

garnet 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.
Eu can  2+ Dy 0.013 0.15 0.582 3.17 0.023 2.024 1.
which conc. Er
Yb
0.026
0.049
0.23
0.34
0.583 6.56
0.542 11.5
0.02
0.023
1.74
1.642
1.5
1.4
in plagioclase Lu 0.045 0.42 0.506 11.9 0.019 1.563
Data from Rollinson (1993). * Eu3+/Eu2+ Italics are estimated
 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”)
Concentration

La Ce Nd Sm Eu Tb Er Dy Yb Lu
 11
10
H
Log (Abundance in CI Chondritic Meteorite)
He
9
8
O
C
7 Ne MgSi
Fe
6 N S Ar
5 Ca Ni
4 Na
AlP Ti
3
K
2 F Cl V
Li Sn Ba
1 B Sc Pt Pb
0
-1 Be Th
-2 U
-3
0 10 20 30 40 50 60 70 80 90 100
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
What would an REE diagram look
like for an analysis of a chondrite
meteorite?
10.00

8.00
sample/chondrite

6.00

4.00
?
2.00

0.00
56 La58
Ce 60Nd 62Sm 64
Eu 66
Tb 68Er 70 Yb 72
Lu
L
Divide each element in analysis by the
concentration in a chondrite standard

10.00

8.00
sample/chondrite

6.00

4.00

2.00

0.00
56 La58
Ce 60Nd 62Sm 64
Eu 66
Tb 68Er 70 Yb 72
Lu
L
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
Chondrite-normalized spider
diagrams are commonly
organized by (the author’s
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 (CS/CL) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine Opx Cpx Garnet Plag Amph Magnetite
Shallow (< 40 Rb
Sr
0.01
0.014
0.022
0.04
0.031
0.06
0.042
0.012
0.071
1.83
0.29
0.46
km) partial 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.
melting of the 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.
mantle will have
Rare Earth Elements

Ce 0.006 0.02 0.092 0.007 0.082 0.843 2.

plagioclase in 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.
the resuduum 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.
and a Eu Er 0.026 0.23 0.583 6.56 0.02 1.74 1.5
anomaly will Yb
Lu
0.049
0.045
0.34
0.42
0.542 11.5
0.506 11.9
0.023
0.019
1.642
1.563
1.4

result Data from Rollinson (1993). * Eu3+/Eu2+ Italics are estimated

 10.00

8.00 67% Ol 17% Opx 17% Cpx

Garnet and Plagioclase

sample/chondrite

6.00

4.00 effect on HREE

2.00

0.00
56 58 Ce 60 Nd 62Sm Eu
La 64 Tb66 68
Er 70 Lu 72
Yb

10.00
10.00

60% Ol 15% Opx 15% Cpx 10%Plag 8.00 57% Ol 14% Opx 14% Cpx 14% Grt
8.00 sample/chondrite
sample/chondrite

6.00
6.00

4.00
4.00

2.00
2.00

0.00
0.00
56 58
La Ce60 Nd 62Sm Eu
64 Tb66 68
Er 70 Lu
Yb 72
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.
 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, 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, Platinum group elements (PGEs) are siderophile and used mostly to study melting and crystallization in mafic-ultramafic

Re, Os, Ir, systems in which PGEs are typically hosted by sulfides. The Re/Os isotopic system is controlled by initial PGE

Pd 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.

Eu2+ 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.

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

18O/16O) = eq

18 16
 18 16
( O/ O) sample ( O/ O) SMOW
18 16 x1000
( O/in per
result expressed O) SMOW
mille (‰)

What is  of SMOW??
What is  for meteoric water?
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
x 1000
 = 18 16
( O/ O) SMOW

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

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 mantle-
derived magmas by crustal sediments
 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
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
dN dN
eq. 9.11  N or  = N
dt dt
1
# parent atoms

time 
 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 40Ca or 40Ar
 40 Ca is common. Cannot distinguish radiogenic
40
Ca from non-radiogenic 40Ca
 40
Ar is an inert gas which can be trapped in
many solid phases as it forms in them
The appropriate decay equation is:
 e 
eq 9.16 40
Ar = 40Aro +    40K(e-t -1)

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
 40
Ar-39Ar technique grew from this discovery
 Sr-Rb System
 87
Rb  87Sr + 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 : 87Sr : 86Sr : 84Sr 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
Recast age equation by dividing through by stable 86Sr

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

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/86Sr = (87Sr/86Sr)o + (87Rb/86Sr)t

y = b + x m

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

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

87
Sr
86
Sr

( )
87

86
Sr
Sr o
to
a b c

87
Rb
86
Sr
After some time increment (t0 t1) each sample loses
some 87Rb and gains an equivalent amount of 87Sr

87
Sr
86
Sr t1
c1
b1
a1
()87

86
Sr
Sr o
to
a b c

87
Rb
86
Sr
At time t2 each rock system has evolved  new line
Again still linear and steeper line

t2
87
Sr c2
86
Sr t1
b2 c1
a2 b1
a1

()
87

86
Sr
Sr o a b c to
87
Rb
86
Sr
 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 9.12. 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 Earth’s 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  143Nd by alpha decay
 = 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 Earth’s 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
 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
 238
U  234U  206Pb ( = 1.5512 x 10-10 a-1)
 235
U  207Pb ( = 9.8485 x 10-10 a-1)
 232
Th  208Pb ( = 4.9475 x 10-11 a-1)
 The U-Pb-Th System
Concordia = Simultaneous co-
evolution of 206Pb and 207Pb via:

238
U  234U  206Pb
235
U  207Pb

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 207Pb

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.