Trace Elements:

comparison with
major elements
The magnitude of
change of the major
elements during
magmatic processes is
frequently small. Trace
elements span a wider
range of geochemical
characteristics and so
can change
concentration more than
most major elements.
Diagrams for 310 volcanic rocks
from Crater Lake, Oregon Cascades.
Data compiled by Rick Conrey.

Red lines
show possible
trends

Trace elements:
magnitude of change
In this example set of lavas,
notice how these trace elements
change concentration over a wide
range:
250 ~0 ppm for Ni
~60 ~250 ppm for Zr
Also notice that the change is in opposite directions.

Harker Diagram for Crater Lake. From data compiled by

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

Trace elements: wide range of behavior

Partitioning of trace elements between phases

At equilibrium, a trace element in the different phases of a system
typically has different concentrations
The partitioning of a trace element i between two phases, in this
example a solid crystalline phase and magmatic liquid, is defined by the
equation:

Kdisolid/liquid = Cisolid/Ciliquid
Where:
Kdi

is the partition coefficient for element i between the solid phase

and the liquid phase

Cisolid is the concentration of element i in the solid phase

Ciliquid is the concentration of element i in the liquid phase

Partitioning of trace elements and Henrys Law

1. Trace element concentrations are low by definition, and so
are usually in the Henrys Law region of concentration.
2. This means that the concentration (more precisely activity)
of element i in the various phases varies directly (linearly)
with concentration in the system.
3. Thus, if XNi in the system doubles, the XNi in all phases will
double.
4. This does not mean that XNi in all phases is the same.
Rather the XNi in each phase will vary in proportion to the
system concentration.

Compatible and incompatible trace

elements
Compatible elements are concentrated in the solid
part of a system; that is, the elements are
comparatively compatible with the crystalline
structures of at least one of the solid phases present.
Kd > 1
Incompatible elements are concentrated in the
liquid part of a system; that is, the elements are
comparatively incompatible with the crystalline
structures of solid phases present.
Kd < 1

Example of typical incompatible elements: Kd < 1

High field strength (HFS) elements:
Smaller, high charge elements typically including REE3+, Th4+, U4+, Pb4+,
Zr4+, Hf4+, Ti4+, Nb5+, Ta5+. These elements are typically almost insoluble
in fluid phases and so are relatively immobile during alteration.
Large ion lithophile (LIL) elements:
Larger, low charge elements typically including K+, Rb+, Cs+, Ba2+, Pb2+,
Sr2+, Eu2+. These elements are typically quite soluble in fluid phases,
especially aqueous fluids, and so are mobile during alteration.

The term high field strength refers to the high surface charge gradient
on these ions, calculated as the ratio: (formal charge/ionic radius 2).
The term lithophile refers to the tendency of these elements to end up
in high concentrations in crustal rocks.

Incompatible element behavior

The expected behavior of incompatible elements is to increase in
concentration with crystallization.

This statement assumes

that the suite of rocks in
question is related to one
another largely by
crystallization, which is
not necessarily the case.

Example of typical compatible elements: Kd > 1

Medium-size first row transition metals (Cr3+, Co2+, Ni2+).
Chalcophile elements:
Elements that partition strongly into sulfide liquid or solid phases
(platinum group elements, gold, silver, copper, many semimetals).
The term chalcophile refers to the affinity these elements have for
sulfides.

Compatible element behavior

The expected behavior of compatible elements is to decrease in
concentration with crystallization.

This statement
also assumes
that the suite of
rocks in
question is
related to one
another largely
by
crystallization,
which is not
necessarily the
case.

Actual partitioning behavior varies

Crystal/liquid partition coefficients vary with:
Mineral of interest. The partitioning behavior of elements differs
between olivine, pyroxene, plagioclase, garnet, spinel, etc.
Liquid composition of interest. Typically, many elements become
more compatible with increasing silica content of the magma.
Mineral composition. The partitioning behavior of elements changes
with site size and shape which vary with mineral composition.
Temperature
Pressure

Crystal/liquid partitioning in basalt, several elements

Compatible elements
Incompatible elements

Crystal/liquid partitioning in basalt and dacite

Compatible elements
Incompatible elements

Bulk partition coefficients

Partition coefficients discussed so far are for single minerals in
equilibrium with a single liquid. If multiple minerals are involved,
partitioning behavior is modified depending on:
1. The minerals involved.
2. The proportions of the minerals involved.
3. The individual Kdicrystal/liquid values of each mineral involved.

i
n
j
Pj
Kdij/liquid

Element i for which the bulk Kd is being calculated.

The number of minerals j involved.
Mineral j, of which there may be several numbered 1 through n.
Proportion of mineral j in the solid portion of the system.
Kd for element i and mineral j.

Trace element ratios can identify equilibrium phases

The ratios of trace elements are often superior to the absolute element
concentration for identifying the role of a specific mineral.
Following are three examples:
1. K/Rb and amphibole.
2. Ba/Sr and K-feldspar.
3. Ni/Cr and olivine and pyroxene.
In these examples, the idea is to find a mineral with a unique pair of
elements for which it alone has a relatively high Kd for one element and
a relatively low Kd for the other. The ratio of these elements will be most
sensitive magmatic processes associated with that particular mineral.

K/Rb ratios and the involvement of amphibole

K/Rb ratios can help determine the importance of amphibole. Of common minerals in
mafic and ultramafic rocks, only amphibole has moderately high Kds for K and Rb.
K & Rb behave
similarly, so K/Rb
should be
~constant.
If there is much
amphibole, most
solid phase K and
Rb will reside in it.
Amphibole has a
Kd of about 1 for
K and 0.3 for Rb.
Presence of
amphibole will
cause lower K/Rb
ratio in the liquid.

Ba/Sr ratios and the involvement of K-feldspar

Sr and Ba are generally both incompatible elements, and can be
used to determine the presence of K-feldspar in a source rock.

Sr is excluded
from common
minerals except
plagioclase.
Ba excluded
from most
common
minerals except
K-feldspar.
Plagioclase
crystallization
tends to raise
Ba/Sr ratios.
K-feldspar
crystallization
tends to lower
Ba/Sr ratios.
Crystallization of
both may buffer
Ba/Sr ratios.

Ni/Cr ratios and the involvement of olivine or pyroxene

Ni and Cr are both generally compatible elements, though their
compatibility varies considerably with the mineral of interest.
Ni is partitioned
into olivine over
pyroxene.
Cr is partitioned
into pyroxene over
olivine.
Olivine
crystallization
tends to lower
Ni/Cr ratios.
Pyroxene
crystallization
tends to raise
Ni/Cr ratios.
Ni/Sc ratios
behave similarly
and can be used as
a check.

Fractional melting curves

Concentrations of an element in the liquid originally at a concentration of 1.

Equilibrium (batch) melting and trace elements

During equilibrium melting, the liquid remains resident with and in
equilibrium with the crystalline residue, until at some point it is released
and moves away. This equation describes the liquid composition for
element i at different proportions of melting:

Ciliquid Concentration of element i in the liquids produced.

Cioriginal Concentration of element i in the original solid rock.
F
Fraction (or proportion) of liquid produced.
Kdir/l

Bulk partition coefficient for element i between rock and liquid.

Equilibrium (batch) melting curves

Concentrations of an element in the liquid originally at a concentration of 1.

Fractional crystallization and trace elements

During fractional crystallization, the crystals formed are immediately
separated from the residual liquid, perhaps as layers on the magma
chamber floor or as phenocrysts that isolate their interiors from the liquid
by slow solid state diffusion. This equation describes the liquid
composition for element i at different proportions of crystallization:

Ciliquid Concentration of element i in the liquids that remain.

Cioriginal Concentration of element i in the original liquid.
F
Fraction (or proportion) of liquid remaining.
Kdir/l

Bulk partition coefficient for element i between rock and liquid.

Fractional crystallization curves

Concentrations of an element in the liquid originally at a concentration of 1.

Equilibrium crystallization and trace elements

During equilibrium crystallization, the crystals produced remain resident
and in equilibrium with the residual liquid. This equation describes the
liquid composition for element i at different proportions of melting:

Ciliquid Concentration of element i in the liquid remaining.

Cioriginal Concentration of element i in the original liquid.
F
Fraction (or proportion) of liquid remaining.
Kdir/l

Bulk partition coefficient for element i between rock and liquid.

Equilibrium crystallization curves

Concentrations of an element in the liquid originally at a concentration of 1.

Comparison of the model curves

Equilibrium curves are mirror images of each other, fractional curves are not.

Other end member processes for magma modeling

Some other models are commonly used to understand magma
geochemistry:
Mixing of magmas.
Wall-rock assimilation.
Zone refining.
Combinations of processes. Combined models are generally too
complicated to solve easily with a single equation, and so are usually
solved by small step iterations.

Mixing processes
Magma mixing and wall rock assimilation are basically mixing
processes, and use essentially the same equation as that used to calculate
the bulk partition coefficient.

i
j
n
Pj
Cij

The element for which the concentration is being calculated.

The components being mixed (e.g., basalt and granite magma).
The number of components being mixed together.
Proportion of component j in the mixture from j=1 to j=n.
The concentration of element i in each component j.

Cimixture The concentration of element i in the mixture.

The lanthanides and REE

Why the lanthanides are geochemically coherent

Steady decrease in lanthanide ionic radius with atomic number.

REE partition coefficients for minerals in basalts 1

This is a set of REE partition coefficients for six common minerals in
basaltic systems, slightly modified after Hollocher (1993). Notice that
these elements are mostly incompatible, but range from compatible (red)
to extremely incompatible.
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu

Amphibole
0.18
0.25
0.33
0.43
0.64
0.74
0.77
0.78
0.74
0.69
0.64
0.59
0.54
0.49

CPX
0.07
0.11
0.16
0.20
0.25
0.24
0.33
0.35
0.35
0.35
0.35
0.34
0.32
0.30

Garnet
0.01
0.02
0.05
0.09
0.24
0.30
0.60
0.90
1.40
2.00
2.80
4.00
6.00
9.30

Olivine
0.001
0.002
0.002
0.003
0.004
0.004
0.005
0.005
0.006
0.006
0.007
0.007
0.008
0.008

OPX Plagioclase
0.003
0.13
0.005
0.12
0.008
0.11
0.012
0.10
0.021
0.09
0.018
0.50
0.033
0.08
0.040
0.07
0.049
0.07
0.060
0.06
0.076
0.06
0.100
0.06
0.130
0.06
0.180
0.06

REE partition coefficients for minerals in basalts 2

This is a graph of the partition coefficients from the previous table.

Compatible
Incompatible

Plotting REE concentrations without normalization

Without normalizing, the result is a confusing Oddo-Harkins zig-zag pattern.

Plotting REE diagrams with chondrite normalization

With chondrite normalization, the result is relatively smooth REE patterns.

Model liquids from fractional melting of mantle 1

Model liquids from fractional melting of mantle 2

Summary of trace element uses

Summary of the value of elements of different compatibility for tracing
particular magmatic processes.

Sensitive to melting

Sensitive to crystallization

Small amounts
of melting:
<20%

Large amounts
of melting:
>20%

Small amounts
of
crystallization:
<20%

Large amounts
of
crystallization:
>20%

Compatible
elements

No

No

Yes

Yes (if any is

left)

Incompatible
elements

Yes

Marginal

Marginal

Yes

Elements with
Kdisolid/liquid ~1

No

No

No

No

Summary of some useful trace elements

Element

Common use as a petrogenetic indicator

Highly compatible elements. Ni and Co are concentrated in olivine, Cr in spinel
Ni, Co, Cr, Sc and clinopyroxene, Sc in clinopyroxene. High concentrations indicate a mantle
source and little fractional crystallization
V and Ti are strongly partitioned into the Fe-Ti oxides ilmenite, magnetite, and
titanomagnetite. If they behave differently, Ti is probably partitioning into an
V, Ti
accessory phase such as titanite or rutile.
Very incompatible elements that do not substitute into major silicate phases.
Zr, Hf, Nb, Ta They may replace Ti to a in titanite or rutile. Zr and Hf can be buffered by zircon
crystallization.
Incompatible elements that substitute for K in K-feldspar, micas, and
amphibole. Rb substitutes less readily in amphibole than in K-feldspars or
Ba, Rb
micas, so K/Ba ratios may indicate the involvement of amphibole.
Substitutes for Ca in plagioclase and to a lesser extent for K in K-feldspar, but
not for Ca in pyroxenes and amphiboles or K in micas. Sr bahaves as a
Sr
compatible element where plagioclase is involved (e.g., at low pressure), and
as an incompatible element under other circumstances.
Generally incompatible except for Eu2+ in plagioclase-bearing systems, and
HREE in garnet-bearing systems. Garnet, olivine, and OPX concentrate HREE,
REE, Y
CPX and amphibole concentrate MREE, and plagioclase and titanite
concentrate
LREE.
After Green (1980). Tectonophysics,
v. 63, p.
367-385; and Winter (2001) An Introduction to Igneous and Metamorphic Petrology, Prentice Hall.

Trace elements as a tool to determine paleotectonics

Trace elements in magmas are controlled by the source composition
and by post-melt generation processes.
Mantle compositions vary from one tectonic environment to another,
because of the different regions from which the mantle rock comes and
because of processes that modify the mantle composition.
Similarly, post-melt generation magmatic processes differ to some
extent from one tectonic environment to another.
Trace elements are useful for indicating the tectonic environment of
igneous rocks that are no longer recognizably in their original setting
(e.g., old rocks).
This approach is entirely empirical, based on modern occurrences.
This approach generally concentrates on elements that are relatively
immobile during hydrothermal alteration and low to medium grade
metamorphism (e.g., high field strength elements).

Example tectonic discriminant diagrams (basalts)

Pearce, 1982, in Thorpe (ed.),
Andesites: Orogenic andesites and
related rocks, Wiley, Chichester, p.
525-548.

Pearce and Cann,

1973, Earth and
Planetary Science
Letters, v. 19, p.
290-300.

WPB
IAT
CAB
(arcs)
MORB
OIT
OIA
basalt

Within-plate basalts
Island arc tholeiites
Calc-alkaline basalts
Mid-ocean ridge basalts
Ocean island tholeiite
Ocean island alkaline

Mullen, 1983, Earth

and Planetary Science
Letters, v. 62, p. 53-62.

Harker
diagrams

Harker variation diagrams of wt. % Na20 + K2O and wt % MgO

versus wt % SiO2 for a suite of cogenetic volcanic rocks related
by fractional crystallization of olivine, clinopyroxene and
magnetite. The highly magnesian basalts (MgO >12%) may have
accumulated olivine by crystal settling

Harker-type variation diagrams, with wt% MgO as abscissa,

for a cogenetic suite of volcanic rocks related by fractional
crystallization of olivine and clinopyroxene.