Using geochemical data in

igneous petrology
Trace elements: presenting and
interpreting them
4. Trace elements
1. Partition coefficients and bulk repartition
coefficient (Kd and D)
2. Representing trace element compositions:
the use of spidergrams
3. Main families of trace elements
4. The use of ratios
5. Some diagrams using trace elements
Selective affinities
Fe2+
Mg2+

Compatible
Ni2+
(right size & charge)

Au3+
Incompatible
(size/charge does
not match)
Ag3+

Fe2+ Mg2+
• Partition coefficient Kd = Cs/Cl
• Compatible, incompatible (relative to a
mineral)
• Bulk repartition coefficient D =  Kd X
i i
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 0.010 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
• Calculate DYb for…
– A lherzolite (80% Ol, 10% Opx, 10%Cpx)
– A Grt-bearing Lherzolite (70% Ol, 10% Opx-
Cpx-Gt)
• Calculate DSr for…
– A Cpx-Plag cumulate (50/50)
– A Cpx-Opx cumulate (50/50)
• How will the residual liquid evolve?
 4.2 Spidergrams
• Also (better) known as multi-elements
diagram
• Allow to represent the whole composition
of a sample on a single diagram
• Allow to compare the concentration in
elements in different ranges
• Allow to get rid of the effects of primordial
abundances
 Elements abundance patterns in
Earth are a product of
• Nucleosynthesis
– Lights > Heavies
– Even > Odd
– Abundance peak close to Fe (n=56)
• Differenciation
– Lithophile mantle (+ crust)
– Siderophile core
Solar system abundance
Concentration of REE in a sample
Chondrites
Contrasted REE patterns
Granites

Basalts
 Multi-elements diagrams

Normalized to the PRImitive Mantle (close to chondrites) (Wood version)

 Various normalizations:
To MORB (Mid-Oceanic Ridge Basalts – the most common type of basalt!)
Meaningful for basalts and co.

Look how the elements on the left-hand side behave in a different way as those
on the right-hand side!
 Various normalizations:
To the average continental crust.
Meaningful for granites, sediments, etc.
4.3 Families of elements
Commonly used trace elements
• LILE= Large Ion Lithophile Elements
– Cs, Rb, K, Ba, Sr, Pb
– Large atoms with a small charge
– Tend to be incompatible to very incompatible
– Some exceptions (Rb in Biotite, Sr in plag…)
– Typically fluid mobile (and therefore can be
subject to weathering)
– Interesting to use but some caution should be
exercised
• HFSE= High Field Strength Elements
– Sc, Y, Th, U, Pb, Zr, Hf, Ti, Nb, Ta
– Variable behaviours, generally incompatible
except in some specific phases (Y in Grt, Nb
in Hbl…)
– Normally fluid immobile, insensible to
weathering
– Regarded as good petrogenetic indicators
• HFSE: some interesting « pairs » with very
similar behaviours
– Nb and Ta (Nb/Ta chondritic ≈ 15-20, less for
crustal rocks)
– Zr and Hf (Zr/Hf chondritic ≈ 30-35)
– Values largely departing from this call for
explanation (phases able to fractionnate Nb
from Ta or Zr from Hf)
 OIB vs. Island-arcs: LIL and HFS
elements
Figure 14-3. Winter (2001) An Introduction to Igneous
and Metamorphic Petrology. Prentice Hall. Data from Sun
and McDonough (1989) In A. D. Saunders and M. J.
Norry (eds.), Magmatism in the Ocean Basins. Geol. Soc.
London Spec. Publ., 42. pp. 313-345.
Figure 16-11a. MORB-normalized spider diagrams for
selected island arc basalts. Using the normalization and
ordering scheme of Pearce (1983) with LIL on the left and
HFS on the right and compatibility increasing outward
from Ba-Th. Data from BVTP. Composite OIB from Fig
14-3 in yellow.
• REE= Rare Earth Elements
– La Ce Pr Nd (Pm) Sm Eu Gd Tb Dy Ho Er Tm
Yb Lu
– Technically they are HFS
– Rather incompatible, except in specific
phases
– For a given mineral phases, different REE
have different behaviours
– Nearly insensible to weathering
– Excellent petrogenetic indicators!
Kd’s for REE in basaltic liquids
 REE: the case of Eu
• REEs are normally 3+ (La3+, etc.)
• Eu can be Eu3+ or Eu2+
• Eu2+ strongly compatible
• Especially in reducing Reducing (Eu2+)
environments

Oxydizing (Eu3+)
• REE ratios
– Eu/Eu* is a measure of the size of the Eu anomaly
Eu Eu N
1
2 ( SmN  Gd N )
*
Eu
– La/Yb (or LaN/YbN, also written (La/Yb)N ) is an
indication of the slope of the REE pattern
• Transition elements
– Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn
– All compatible, no huge differences
– Low abundances in felsic or intermediate
rocks, useful for basic or ultrabasic systems,
or for some mineral deposits (chromite)
– Fluid immobile
• PGE= Platinum Group Elements
– Ru, Rh, Pd, Os, Ir, Pt, Au
– Not that well-known, large uncertainities on
Kd’s
– Low abudances, commonly below detection
limit (bdl) with usual mehods
– Economic importance, especially in
chromitites and sulphides
– Marginal petrologic use, could become more
significant in the future
 4.4 Trace elements ratios
Why?
• Couple of elements with similar behaviour,
normally not fractionnated and preserved
during most processes
– Nb and Ta
– Zr and Hf
• A measure of the importance of an
anomaly
– Eu/Eu*
– Eu/Sm or Eu/Gd (similar to previous)
– Nb/Th, Nb/Ce (Nb-Ta anomaly)
• A measure of the shape of a spidergram
– La/Yb, Ce/Yb, La/Lu…

• Elements with different behaviours in

different contexts
– LIL/HFS to differenciate subduction/OIB, e.g.
Ba/La
• Fingerprinting the role of a specific mineral
– Ni strongly fractionated  olivine > pyroxene
– Cr  pyroxenes » olivine
– Ni/Cr 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
La 0.007 0.03 0.056 0.001 0.148 0.544 2
Ce 0.006 0.02 0.092 0.007 0.082 0.843 2
 Trace elements ratios
How?
• Element-Element diagrams with linear
scale
 Trace elements ratios
How?
• Element-ratio diagrams with linear scale
 Trace elements ratios
How?
• Element-element diagrams with log scale 5
=20 a =1
50 /T
a /T 0
Ta
=
Nb Nb a =1
/ /T
Nb Nb
5
a=
/T
Nb

1
a=
/T
Nb
 Trace elements ratios
Be careful!
• Dividing by a common value yields
spurious correlations…
 4.5 Some trace element diagrams
• In general, far greater diversity than for
majors
• You can plot anything against anything
else, and then start again with ratios
• It’s easy to get confused…
 Some starting points/suggestions
• Diagrams using rare elements (Ni in a granite,
Rb in peridotites) will be highly sensitive to
analytical uncertainities, sampling conditions,
contamination, etc.

• Diagrams using elements from the same groups

are likely to give similar results (e.g. Sr and Ba,
Nb, Ta and Zr …) and are somehow redundant
to discuss magma evolution
• Use ratios of similar elements
(supposedely not fractionnated during
common petrogenetical processes) to
differenciate between different groups of
otherwise similar rocks

In this case: low Nb/Ta vs. High Nb/Ta

(and, well, variable Nb/Ta…)
• Look for correlations (« trends ») or
different populations (different sources or
petrogenetic history?)
• Check if trends or grouping are robust in
other diagrams with similar elements (e.g.,
replacing Rb by Th, Sr by Ba, etc.)
 Some starting points/suggestions
• Differenciation vs. different sources: check
using Harker type plots what is related to
differenciation!
• Two populations distinguished with Rb and
Sr (high Sr, and low Sr) ?
• A Harker-type diagram reveals that the Sr
contents –whatever the rock type– are more or
less correlated to differenciation. The two
« groups » simply reflect more or less
differenciated rocks from the same series!

On the other hand, the

low Rb, low Sr groups
seems to have an
independant existence…
• You will progressively learn, and get used
to certain elements – you’ll be familiar with
typical values, behaviours, etc.
• My personnal favorite subset (NB: I work on
granites!)
– LILE: Rb, Sr (used to trace plag, Bt, etc.)
• Th and Cs are too sensible to weathering and anyway more
difficult to analyse: not always possible to have data
– HFSE: Y (useful for Grt, amp); Nb
• Zr is too affected by zircon; Hf and Ta are not always
analyzed (good to look at Nb/Ta and Zr/Hf, though)
– REE: La (or Ce), Yb, Eu/Eu*
• This carries effectively most of the useful information
– No transition elements, no PGEs
• Too low to be meaningful
• Your own choice will be different (especially if
working on basalts…)
 Classical diagrams
• Spidergrams
• Harker type diagrams
• Check the litterature for your type of rocks –
there are some classical diagrams that people
are used to.
– e.g. TTG and Archaean rocks: Sr/Y vs. Y, La/Yb vs.
Yb (Martin 1987)
– Basalts (MORB): La/Sm, etc.
– Island arcs: HFS/LIL (Ba/La) etc.
• Geotectonic diagrams (to be discussed next
week)
 “Classification” based on trace elements

Pearce diagrams (for granites)

 “Classification” based on trace elements

Wood diagrams (for basalts)