Trace Elements - Definitions

Elements that are not stoichiometric constituents

in phases in the system of interest
For example, IG/MET systems would have
different trace elements than aqueous systems
Do not affect chemical or physical properties of
the system as a whole to any significant extent
Elements that obey Henrys Law (i.e. has ideal
solution behavior at very high dilution)

Graphical Representation of Elemental Abundance

In Bulk Silicate Earth (BSE)
Six elements make up 99.1% of BSE ->

The Big Six: O, Si, Al, Mg, Fe, and Ca

From W. M. White, 2001

Goldschmidts Geochemical Associations (1922)

Siderophile: elements with an affinity for a liquid
metallic phase (usually iron), e.g. Earths core
Chalcophile: elements with an affinity for a liquid
sulphide phase; depleted in BSE and are also likely
partitioned in the core
Lithophile: elements with an affinity for silicate phases,
concentrated in the Earths mantle and crust
Atmophile: elements that are extremely volatile and
concentrated in the Earths hydrosphere and atmosphere

Trace Element Associations

From W.M. White, 2001

Trace Element Geochemistry

Electronic structure of lithophile elements is such
that they can be modeled as approximately as hard
spheres; bonding is primarily ionic
Geochemical behavior of lithophile trace elements
is governed by how easily they substitute for other
ions in crystal lattices
This substitution depends primarily by two factors:
Ionic radius
Ionic charge

Effect of Ionic Radius and Charge

The greater the
difference in charge or
radius between the ion
normally in the site
and the ion being
substituted, the more
difficult the
substitution.
Lattice sites available
are principally those
of Mg, Fe, and Ca, all
of which have charge
of 2+.
Some rare earths can
substitute for Al3+.

Ionic Radii
Magnesium (Mg2+): 65 pm
Calcium (Ca2+): 99 pm
Strontium (Sr2+): 118 pm
Rubidium (Rb+): 152 pm
Values depend on Coordination Number
1 pm = 10-12 m
1 = 10-10 m
1 pm = 10-2

Classification of Based on Radii and Charge

Ionic Potential - charge/radius rough index for mobility
(solubility)in aqueous solutions:
<3 (low) & >12 (high) more
mobility
1) Low Field Strength (LFS)
Large Ion Lithophile (LIL)
2) High Field Strength (HFS)
REEs
3) Platinum Group Elements
NB 1 = 10-10 meters = 100 pm

More Definitions
Elements whose charge or size differs significantly
from that of available lattice sites in mantle
minerals will tend to partition (i.e. preferentially
enter) into the melt phase during melting.
Such elements are termed incompatible
Examples: K, Rb, Sr, Ba, rare earth elements (REE), Ta,
Hf, U, Pb

Elements readily accommodated in lattice sites of

mantle minerals remain in solid phases during
melting.
Such elements are termed compatible
Examples: Ni, Cr, Co, Os

Trace element substitutions

The (Lanthanide) Rare Earth Elements

H

He
Be

Ne

Na Mg

Al

Si

Cl

Ar

Zn Ga Ge

As

Se

Br Kr

Li

Ca

Sc Ti

Cr Mn

Fe Co

Ni

Rb

Sr

Nb Mo Tc

Ru Rh

Pd Ag

Cd

In

Sn

Sb

Te

Xe

Cs

Ba La Hf

Ta

Os

Pt Au

Hg

Tl

Pb

Bi

Po

At

Rn

Fr

Ra

Zr

Re

Ir

Cu

Ac

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Th

Pa

Np

Pu Am Cm Bk

Cf

Es

Fm Md No

Lr

Chondrite vs. Solar Chemistry

REE Characteristics

Rare Earth Element Behavior

The lanthanide rare earths all have similar outer
electron orbit configurations and an ionic charge
of +3 (except Ce and Eu under certain conditions,
which can be +4 and +2 respectively)
Ionic radius shrinks steadily from La (the lightest
rare earth) to Lu (the heaviest rare earth); filling forbitals; called the Lanthanide Contraction
As a consequence, geochemical behavior varies
smoothly from highly incompatible (La) to
slightly incompatible (Lu)

Rare Earth Element Ionic Radii

NB that 1 pm = 10-6 microns = 10-12 meters

Rare Earth Abundances in Chondrites

Sawtooth pattern of
cosmic abundance
reflects:
(1) the way the
elements were created
(greater abundances of
lighter elements)
(2) greater stability of
nuclei with even
atomic numbers

Partition Coefficients for REEs

crystal
Dmelt
=

(concentration in mineral)
(concentration in melt)

Partition Coefficients for REE in Melts

Amphibole-Melt

Dbulk = X1D1 + X2D2 + X3D3 + + XnDn

Trace Element Fractionation

Low Degree Partial Melts - REE Fractionation

Chondrite Normalized REE patterns

By normalizing (dividing by abundances in chondrites),

the sawtooth pattern can be removed.

Trace Element Fractionation

During Partial Melting

From: http://www.geo.cornell.edu/geology/classes/geo302

Differentiation of the Earth

Rb>Sr
Nd>Sm
La>Lu

Continental Crust
La

Lu

Rb>Sr
Nd>Sm
La>Lu

Mantle
(After partial
melt extraction)

Rb<Sr
Nd<Sm
La<Lu

La

Lu

Melts extracted from the mantle rise to the crust,

carrying with them their enrichment in incompatible
elements
Continental crust becomes incompatible element enriched
Mantle becomes incompatible element depleted
From: http://www.geo.cornell.edu/geology/classes/geo302

Uses of Isotopes in Geochemistry

Processes of magma generation and evolution source region fingerprinting
Temperature of crystallization
Thermal history
Absolute age determination - geochronology
Indicators of other geological processes, such as
advective migration of aqueous fluids around
magmatic intrusions

Isotopic Systems and Definitions

Isotopes of an element are atoms whose

nuclei contain the same number of protons
but different number of neutrons.
Two basic types:
Stable Isotopes: H/D, 18O /16O, C, S, N (light)
and Fe, Ag (heavy)
Radiogenic Isotopes: U/Pb, Rb/Sr, Lu/Hf, K/Ar

Radioactive decay and radiogenic Isotopes

Radiogenic isotope ratios are
functions of both time and
parent/daughter ratios. They can
help infer the chemical evolution
of the Earth.
Radioactive decay schemes

87Rb-87Sr

(half-life 48 Ga)
147Sm-143Nd (half-life 106 Ga)
238U-206Pb (half-life 4.5 Ga)
235U-207Pb (half-life 0.7 Ga)
232Th-208Pb (half-life 14 Ga)

Extinct radionuclides
Extinct radionuclides have
half-lives too short to survive
4.55 Ga, but were present in
the early solar system.

87Rb
87Sr

Half-life and exponential decay

Exponential decay:
Never get to zero!

Linear decay:
Eventually get to zero!

Rate Law for Radioactive Decay

Pt = Po exp - (to t)
1st order rate law
Where

Pt ! quantity of the parent isotope (i.e. 87Rb) at time t;

Po ! quantity of the parent isotope at some earlier time to, when the
isotopic system was closed to any additional isotopic exchange;
" ! is the characteristic decay constant for the system of interest, which
is related to the half-life, t1/2, by the equation below:
" = ln 2 / t1/2

t1/2 ! is defined as the half-life, which is the amount of time required for 1/2 of the
original parent to decay and is a constant.

Rb/Sr Age Dating Equation

Rbt = 87Rbo e -! (to t)
(Assume that t = 0, for the present)
87

87

Rbo + 87Sro = 87Rbt + 87Srt

(Conservation of Mass, with 87Sro as the initial

concentration and 87Srt as the concentration today)
87

87

87

Srt - Sro = Rbt (e

! to

1)

! 87Sr $ ! 87Sr $ ! 87 Rb$ 't

# 86 & = # 86 & + # 86 & (e ( 1)
" Sr % t " Sr % o " Sr % t

y = b + x)m

Rb/Sr Isochron Systematics

M1

M2

M3

Instruments and Techniques

Mass Spectrometry: measure different abundances of
specific nuclides based on atomic mass.
Basic technique requires ionization of the atomic species of
interest and acceleration through a strong magnetic field to
cause separation between closely similar masses
(e.g. 87Sr and 86Sr). Count individual particles using
electronic detectors.
TIMS: thermal ionization mass spectrometry
SIMS: secondary ionization mass spectrometry - bombard
target with heavy ions or use a laser
MC-ICP-MS: multicollector-inductively coupled plasma-ms

Sample Preparation: TIMS requires doing chemical

separation using chromatographic columns.

Clean Lab - Chemical Preparation

http://www.es.ucsc.edu/images/clean_lab_c.jpg

Thermal Ionization Mass Spectrometer

From: http://www.es.ucsc.edu/images/vgms_c.jpg

Schematic of Sector MS

Zircon Laser Ablation Pit

Mantle-Basalt Compatibility
Rb>

Sr
Th>
Pb
U> Pb

Parent->Daughter

Nd< Sm
Lu>Hf
Degree of compatibility

Radiogenic Isotope Ratios & Crust-Mantle Evolution

Continental Crust

Rb>Sr high 87Sr/86Sr

Nd>Sm low 143Nd/ 144Nd

Melt

Mantle
(After partial
melt extraction)

Rb<Sr

La

Lu

same 87Sr/86Sr and

143Nd/144Nd as mantle

low

87Sr/86Sr
La

Nd<Sm

Lu

high 143Nd/ 144Nd

Eventually, parent-daughter ratios are reflected in

radiogenic isotope ratios.
From: http://www.geo.cornell.edu/geology/classes/geo302

Sr Isotope Evolution on Earth

87Sr/86Sr)

Time before present (Ga)

87Sr/86Sr)

Time before present (Ga)

Sr and Nd Isotope Correlations:

The Mantle Array

147Sm->143Nd

(small->big)

87Rb->87Sr

(big->small)