Chapter 9: Trace Elements

Please bring to the Field

Trip on Saturday a color
copy of

http://www.kean.edu/~csmart/Petrol
ogy/Lectures/Field%20Trip%201%2
0Maps.pptx

Note small magnitude

of major element
changes. However
(next slide) …

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.
 Transition Elements

Transition elements often

vary by > 103 wrt SiO2.
Very useful since so
sensitive to distribution &
fractionation

Zr, a transition element

Incompatible HFSE
See slide 43

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.
 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? As K+,

concentrated in K-spars, micas, and evolved
melts
Ni++ behaves as Mg++, concentrates in Olivine
TAKE OUT YOUR COORDINATION NUMBERS AND IONIC RADII CHART
Rb+ [6] 1.57 Å follows K+ [6] 1.46 Å &
conc. in K-Spar, mica, & late melt.
Ni++ [6] 0.77 Å follows Mg++ [6] 0.8 Å
& conc in Mg-Olivine “Forsterite”
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 Bounces off the rim less
Smaller ion
preferentially -> solid
(Mg++ is smaller than
Fe++ so more Mg++ in
high temp Olivine than
in melt)

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.
 1 Ångström = 1.0 × 10-10 meters
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
Rutile TiO2
Example Ti+4[6] r=0.69 Angstrom versus
Other ions this size Fe +3 r=0.68 A Hematite Fe2O3
Mn +3 [6] r=.70 A
Ti+4 is always preferred in solids over liquids.
Example Cr+3 [6] r=0.76
Other ions this size Ni +2 [6] r=0.77 A
Fe +2 [6] r=.77
Cr+3 is always preferred in solids over liquids.
Anorthite higher T than Albite
Forsterite higher T than Fayalite

Chemical Fractionation
 The uneven distribution of an ion between
two competing (equilibrium) phases
 Example: the ratio of Ca++/Na+ is always
greater in plagioclase crystals than in the
coexisting melt. Ca++ higher valance than
Na+ , goes into Plag xtals. first.
If melting Plag, Na+ goes to melt first.
 Example: the ratio of Mg++/Fe++ is always
greater in Olivine than in the coexisting
melt.
 If the reaction between solid and liquid phases is a
phase change of some component i

i (liquid)  i (solid) Recall that we

used the lever
A distribution constant KD is principle to
estimate this
ratio from our
phase diagrams

Where Xi is the mole fraction of component i in some phase.

KD the ratio of solubility of component i in these two phases.
 Different units
As long as the concentrations of the components are
dilute, call KD the partition coefficient

Where C is the concentration of a trace element in

the phase indicated, solid and liquid, in ppm or wt%

Table 9.1 (three slides below this) gives partition coefficients for commonly used
trace elements in minerals precipitating from basaltic or andesitic melts.
 Trace element activity varies in direct relation
to their concentration in the system.
 Thus if for Nickel XNi in the system doubles
the XNi in all phases will double
– This does not mean that XNi in all phases is
the same, since trace elements do
fractionate. Rather the XNi within each
phase will vary in proportion to the system
concentration
For example: suppose C(Ni) = 20 ppm in a system
C(Ni) in olivine may be 100 ppm
C(Ni) in plagioclase may be 1 ppm
C(Ni) in liquid may be 10 ppm

Double C(Ni) in system to 40 ppm: Ol -> 200 ppm, Plag -> 2 ppm and
liquid -> 20 ppm
 Incompatible elements concentrate in the
melt

KD « 1 much less than 1

Lesson: incompatibles don’t stick on crystal faces unless the
Temps are low. Melt a xtal, incompatibles go to the melt.
 Compatible elements concentrate in the
solid
KD» 1 much more than 1
Compatibility depends on minerals and melts involved.
Which are incompatible? KD<< 1 , in liquid melt

I marked
some
extreme
examples
 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

Di = partition coefficient of element i in
A
mineral A
 Garnet Lherzolite

Mantle Xenolith (Garnet Lherzolite)

Kimberley, SOUTH AFRICA
Photographed by Tony Peterson
 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% Er = Erbium

orthopyroxene, 10% clinopyroxene, and 5% garnet (all by weight),
using the data in Table 9-1, the bulk distribution coefficient D for Er is:
http://earthref.org
DEr = (0.6 · 0.026) + (0.25 · 0.23) + (0.10 · 0.583) + (0.05 · 4.7) = 0.366 /KDD/e:68/
 We mentioned earlier
Transition elements often vary by > 103 wrt SiO2. Very useful
since so sensitive to distribution & fractionation
 Coef. D for Ni in Olivine in Tb 9-1 = 14>>1
The abrupt drop in Ni
below 55% SiO2
indicates fractionation
of Olivine there. At
SiO2 > 55% another
Ni
ppm mineral or process is
removing Ni

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 D<< 1 concentrate in the
liquid until the melt cools, which is when it has more
silica. So Trace Elements reflect the proportion of
liquid at a given state of crystallization or melting

Zr
ppm
Zr, a transition element
Incompatible HFSE
See slide 43

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 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
* "At a constant temperature, the amount of a given gas that dissolves in a given type
and volume of liquid is directly proportional to the partial pressure of that gas in
equilibrium with that liquid."
  K/Rb often used to measure the importance of amphibole
in a source rock
– K & Rb behave very similarly, so K/Rb should be ~
constant
– If amphibole important, 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 (Sanidine, Orthoclase, Microcline)
 ratio Ba/Sr increases w plagioclase,
decreases when orthoclase xtals present
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
re 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
 Sc Scandium element 21
Compatible example:
 Ni strongly fractionated (goes to solids) from olivines
to pyroxenes
 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 (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
 Models of Magma Evolution
 Batch Melting
 The melt remains in equilibrium with the solid until
at some point it floats upward, separating from the
solids
 Models of Magma Evolution
 Batch Melting (Shaw)
eq. 9-5 C L = 1
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)
Di = bulk distribution coefficient for element i
 low D =
incompatible

Batch Melting low F little

partial melting

A plot of CL/CO vs. F for

various values of Di using
eq. 9-5
For Di = 1.0 there is (by Unlikely
F values
definition) no fractionation,
concentration of element i
the same in solid and liquid
no fractionation
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.
The concentration of the trace element in the
liquid varies more as Di deviates from 1.

– Especially true for low % melting

(low F) and Di<< 1.0
(=incompatible element)

Example: D near 0.001, and

F near 0.02, CL/Co varies from 20
to 100
Figure 9-2. Variation in the relative concentration of a
trace element in a liquid vs. source rock as a function
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 Find a small early partial
elements melt, concentrated
incompatibles there
– Greatly concentrated
in the initial small
fraction of melt
produced by partial
melting Incompatibles go to liquid
– 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, everything is
Di the bulk distribution coefficient
melted, so 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.
Recall CL 1 then:
=
C O Di (1 - F) + F
As F  0 CL/CO  1/Di
Di the bulk distribution coefficient

If we know the concentration of

a trace element in a magma CL
, 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). This
tells us which area was the
source.
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 the bulk distribution coefficient

 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
Basalt with the “mode” = Volume% [cm3]:
Table 9-2 . Conversion from mode to

weight percent 15 cm3 x 3.6g/ cm3 = 54g

Mineral Mode Density Wt prop Wt%
54g/303.9g ~ 0.18
ol 15 3.6 54 0.18

cpx 33 3.4 112.2 0.37 so Wol ~ 0.18

plag 51 2.7 137.7 0.45

Sum 303.9 1.00

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

Done, see rightmost column above.
 Worked Example of Batch
A Basalt (ol, cpx, plag) with the mode: 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

1. Convert to weight % minerals (Wol Wcpx Wplag) (previous slide)

2. Use equation eq. 9-4: Di =  WA Di

and the table of D (Table 9.1) values for Rb and Sr in each
mineral to calculate the bulk distribution coefficients:
DRb = 0.01 x 0.18 + 0.031 x 0.37 + 0.071 x 0.45 = 0.045

DRb = 0.045 (Rb incompatible) and DSr = 0.848 (close to 1)

3. Use the batch melting equation

to calculate CL/CO for various values of F

For F =0.05 and for Rb: CL/Co = 1/ ((0.045(1-0.05)) +0.05) = 10.78

Similarly for F = 0.05 and Sr

CL/Co = 1.18

Then the ratio

Rb/Sr = 10.78/1.18 = 9.12

Continue with remaining F

From Winter (2010) 2nd edition An Introduction to Igneous and
Metamorphic Petrology. Prentice Hall.
 4. Plot CL/CO vs. F for each element

Rubidium incompatible
strongly partitions i.e. strongly
concentrated in the early small melt

Sr doesn’t change much, so Rb/Sr is

approximately the Rb value

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.
 Discussion
 Any ratio of Incompatible to Compatible
elements will be sensitive to the degree of
partial melting in initial stages

 Our experience with Ternary systems tells

us it is unrealistic to expect a ratio of the
minerals in the solid residues to remain
constant.
 What should we do?
 Incremental Batch Melting
 Calculate batch melting for successive
batches (same equation)
 Must recalculate Di as solids change and
minerals are selectively melted
 Figure 9-2 and 9-3 (earlier slides) show
that the model we just used is most
sensitive to Di at low values of F, so it is
most important to use small increments
in that area. Once F > 0.4, batch melts
vary less and are less likely anyway.
 Crystallization Extremes
Either: Crystals remain in equilibrium with
each melt increment
OR The other extreme: separation of each
crystal as it formed = perfectly continuous
fractional crystallization in a magma
chamber
 Rayleigh fractional crystallization
The second extreme: separation of
each crystal as it formed = perfectly
continuous fractional crystallization in a
magma chamber
Crystals accumulate on floor of magma
chamber, isolating formed crystals
– Concentration of some element in the
residual liquid, CL is modeled by the
Rayleigh equation:
eq. 9-8 CL/CO = F (Di -1)

Co conc. of element in original melt

F fraction of melt remaining after xtals removed
Other models are used to analyze
 Mixing of magmas

 Wall-rock assimilation

 Zone refining

 Combinations of processes

End of Part 1
The Rare Earth Elements (REE)
Begins Part 2
 REEs
 Group IIIA, +3 oxidation state, ionic radius
decreases with increasing atomic number (the
“Lanthanide contraction”) so right side smaller
ions, fit more readily, more compatible.

bigger smaller
 Density Groups of REEs
 LREE = light rare earth elements (Sc, La, Ce, Pr, Nd, Pm,
Sm, Eu, and Gd; also known as the cerium group)
 HREE = heavy rare earth elements (Y, Tb, Dy, Ho, Er,
Tm, Yb, and Lu; also known as the yttrium group)

 The densities of the LREEs (as pure elements) range

from 2.989 (scandium) to 7.9 g/cc (gadolinium), while
those of the HREEs are from 8.2 to 9.8, except for
yttrium (4.47) and ytterbium (between 6.9 and 7) The
latter are groups with the HREE due to similar geological
behavior.
 Oxygen Fugacity
 Fugacity is the partial pressure of a gas phase which takes into account
that the gas is able to chemically react with other components in the
system. A measure of departure from Ideal Gas behavior.
 Oxygen fugacity is the measure of the availability of oxygen (within a
given system) to partake in chemical reactions. It represents the
chemical potential of oxygen. It is also a way to quantify the redox state
of a given system.

This is very important in terms of determining the stable mineral present

in a given geological system.

More oxidizing conditions, in igneous or hydrothermal systems for

example, favor the crystallization (and stability) of the more oxidized
mineral phases.

More available oxygen in the system = more oxidizing

 System precipitates components with more oxygen (i.e.
Hematite Fe2O3 (ratio 3/2 = 1.5) would crystallize, rather than
Magnetite Fe3O4 (ratio 4/3 = 1.333).
 Incompatible elements
 An element unsuitable in size and/or charge to the cation sites of the rock forming
minerals. The partition coefficient for them between rock-forming minerals and melt
is much smaller than 1.
 During the partial melting of the Earth's mantle and crust, elements that have
difficulty in entering cation sites of the basaltic minerals (Olivine, Clinopyroxenes, Ca-
rich Plagioclases) are concentrated in the liquid phase of the magma. They are
destined for later minerals and glasses. For example, Potassium K enters the K-spars:
Sanidine, Orthoclase, Microcline very late in fractionation.

 Two groups of incompatible elements are known by acronyms. One group includes
elements having large ionic radius, (called LILE, or large-ion lithophile elements. This
LILE group includes potassium, rubidium, cesium, strontium, and barium.

 The other group includes elements of large ionic valences (or high charges), such as
zirconium Zr+4 , niobium, hafnium, rare earth elements (REE), thorium, uranium and
tantalum (called HFSE, or high field strength elements). These can occur in
pegmatites, for example the alkaline pegmatites we will see at Cranberry Lake.
 Europium
 Note: at low Oxygen fugacity, Europium can have a +2
valence, and Eu+2 can be more abundant than Eu+3

Eu+2 is a Large Ion Lithophile (LIL)

Eu+3 is a high field strength (HFS) element.

LILs include K, Rb, Cs, Ba, Pb+2 , Sr and Eu+2

LIL’s are low field strength, e.g. Potassium’s ion is K+, and are
generally more mobile if a fluid is adjacent.
 The term LILE is
restricted to
lithophile trace
elements having a
large ionic radius
to charge ratio;
that have ionic
radii greater than
those of Ca2+ and
Na1+, some of the
largest cations
common to rock
forming minerals.
By this definition,
LILEs are K, Rb,
Cs, Sr, Ba, Pb and
Eu+2
 11 Oddo-Harkins Rule: atoms with
even atomic numbers are more
H
Log (Abundance in CI Chondritic Meteorite)
10
He
stable, and thus more abundant,
9
8 O
7
C
Ne MgSi
Fe than their odd-numbered neighbors:
6 N S Ar
Ca Ni elements with odd atomic numbers have one unpaired
5 proton and are more likely to capture another
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
 Europium anomaly
 A negative dip is evidence liquid was in
equilibrium with now-absent plagioclase*,
which captured Eu+2

* It floated away

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.
 Application of Trace Elements to
Igneous Systems
1. Use like major elements on variation diagrams to
document fractionation, assimilation, etc. in a suite
of rocks
 TE 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.
 Application of Trace Elements to
Igneous Systems
2. Identification of the source rock or a particular
mineral involved in either partial melting or
fractional crystallization processes
Example: can use REE to distinguish between high
pressure and low pressure sources of a mantle-
derived magma
In the deep continental crust, and at depths over
about 100 km in the mantle, garnet and
clinopyroxene are important phases, which remain
as residual solids during the generation of up to
15-20% partial melting
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 concentration of Tb, Er,
Yb, and Lu in the Garnet
Table 9-1. Partition Coefficients for some commonly used
trace elements in basaltic and andesitic rocks
Shallow (< 40
km) partial Olivine Opx Cpx Garnet Plag Amph
Rb 0.006 0.02 0.04 0.001 0.1 0.3
melting of the Sr 0.01 0.01 0.14 0.001 1.8 0.57
mantle will have Ba 0.006 0.12 0.07 0.002 0.23 0.31
Ni 14 5 2.6 0.4 0.01 3
plagioclase in Cr 2.1 10 8.4 0.17 10 1.6
the residuum La 0.007 0.02 0.08 0.05 0.14 0.27
Rare Earth Elements

Ce 0.009 0.02 0.34 0.05 0.14 0.34

and a Eu Nd 0.009 0.05 0.6 0.07 0.08 0.19
anomaly will Sm 0.009 0.05 0.9 0.06 0.08 0.91
Eu 0.008 0.05 0.9 0.9 0.1/1.5* 1.01
result Tb 0.01 0.05 1 5.6 0.03 1.4
Er 0.013 0.31 1 18 0.08 0.48
Yb 0.014 0.34 0.2 30 0.07 0.97
Lu 0.016 0.11 0.82 35 0.08 0.89
data from Henderson (1982) * Eu3+/Eu2+ Italics are estimated
 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 K-
feldspar. 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
so to a lesser degree. Sphene and plagioclase accommodates more LREE. Eu 2+ is strongly
partitioned into plagioclase.

Y 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, 367-

385. From Winter (2001) An Introduction to Igneous
and Metamorphic Petrology. Prentice Hall.
Figure 9-8. (a) after Pearce and Cann (1973), Earth Planet, Sci. Lett., 19, 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, 1-28. (c) after Mullen (1983), Earth Planet. Sci. Lett., 62, 53-62.
Petrology Field Trip to Bemco Mining District, a side trip
 Ores from weathered Sulfide deposits
• Mineral deposits
containing sulfide
minerals, e.g. copper
sulfides that are
subjected to weathering,
can go into solution and
trickle down to the
reducing conditions
below the water table,
where native metals or
rich concentrations of
ores are precipitated.
Black Smokers, hydrothermal circulations
Gossan Intensely oxidized, weathered or decomposed rock, usually the upper and exposed part of an ore deposit or mineral
vein. In the classic gossan or iron cap all that remains is iron oxides and quartz often in the form of boxworks, quartz lined

cavities retaining the shape of the dissolved ore minerals .

 Solubility in water
The Solubility Rules
1. Salts containing Group I elements are soluble (Li+, Na+, K+, Cs+, Rb+). Exceptions to this rule are rare. Salts containing the ammonium ion (NH 4+) are also
soluble.
2. Salts containing nitrate ion (NO3-) are generally soluble.
3. Salts containing Cl -, Br -, I - are generally soluble. Important exceptions to this rule are halide salts of Ag+, Pb2+, and (Hg2)2+. Thus, AgCl, PbBr2, and
Hg2Cl2 are all insoluble.
4. Most silver salts are insoluble. AgNO3 and Ag(C2H3O2) are common soluble salts of silver; virtually anything else is insoluble.

5. Most sulfate salts are soluble, for example FeSO4 is

soluble. Important exceptions to this rule include BaSO , PbSO , Ag SO and SrSO . 4 4 2 4 4
6. Most hydroxide salts are only slightly soluble. Hydroxide salts of Group I elements are soluble. Hydroxide salts of Group II elements (Ca, Sr, and Ba)
are slightly soluble. Hydroxide salts of transition metals and Al3+ are insoluble. Thus, Fe(OH)3, Al(OH)3, Co(OH)2 are not soluble.
7. Most sulfides of transition metals are highly insoluble. Thus,
CuS, FeS, FeS2, ZnS, Ag2S are all insoluble. Arsenic, antimony,
bismuth, and lead sulfides are also insoluble.
8. Carbonates are frequently insoluble. Group II carbonates (Ca, Sr, and Ba) are insoluble. Some other insoluble carbonates include FeCO3 and PbCO3.
9. Chromates are frequently insoluble. Examples: PbCrO4, BaCrO4
10. Phosphates are frequently insoluble. Examples: Ca3(PO4)2, Ag3PO4
11. Fluorides are frequently insoluble. Examples: BaF2, MgF2 PbF2.
Putting insoluble sulfides into solution
• Oxidizing Zone above the water table
• Sulfide minerals, for example ferrous
and copper sulfides, are subject to
weathering.
• Sulfide minerals are oxidized near the
surface and produce sulfuric acid. For
example:
• FeS2 (s) + 7O + H2O →FeSO4 (aq) + H2SO4
 Reaction and Trickling Down
• Iron sulfate reacts with sulfides, they go into solution as
sulfates, acid rainwater then carries, for example copper,
as copper sulfate, down to the water table.
• CuS(s) + Fe2(SO4)3 (aq) →2FeSO4 (aq) + S(s) + CuSO4 (aq)
• The net result is that dissolved copper sulfide
trickles down from the oxidizing upper portion of
the deposit to that portion at and just below the
water table.
 Reducing Zone below the water table
• Below the water table, where additional sulfide
minerals remain solid and unoxidized (e.g. Pyrite
FeS2), any iron sulfide grains present will react
with the copper sulfate solution, putting iron into
solution and precipitating copper.

• FeS2 (s) + CuSO4 (aq) → FeSO4 (aq) + Cu(s) + 2S(s)

Hydrothermal Deposit, Bemco Mine