22-07-2015

GS537
Geochemistry
Lectures, H. C. Sheth, Dept. of Earth Sciences, IIT Bombay

Mauritius coast, May 2008

GS 537 Geochemistry

Syllabus
Chemical composition of the Earth and its constituent reservoirs; meteorite
evidence; elementary statistics for geochemistry; major, minor and trace
elements including rare earth elements; element partitioning between
minerals and melts; oxide-element conversions; radioactivity and
geochronology; chemical and isotopic fractionation; application of Rb-Sr
and Sm-Nd isotope geochemistry to rock dating, petrogenesis, and crust-
mantle evolution; mixing phenomena in elements and isotopes; related
numericals.

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• Geochemistry is the science of the chemistry of the Earth

and its component parts (the crust and mantle, the
hydrosphere, the atmosphere, and the biosphere.
• It also studies chemical exchanges between these
reservoirs.
• It is both more restricted and more broad compared to
geology.
• The term “geochemistry” was introduced by Schönbein,
discoverer of ozone, in 1838.

Christian Schönbein (1799-1868)

Cosmochemistry
is a still broader
science, and
involves chemical
studies of stars,
planets, asteroids,
meteorites,
comets, etc.

The Eagle Nebula (20 light

years across) and the
associated star cluster
NGC 5611, located 6000
light years from Earth.

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Galaxies including the Milky Way

Evolution of the Solar System: Sun

and the planets condensed from a
rotating, hot Solar Nebula 4.5 billion
years ago

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Earth is a planet of the Solar System,

which consists of:
• the Sun
• Nine planets
• Over 60 moons of the planets (1 for the
Earth, 4 large and >60 small ones for
Jupiter)
• Vast numbers of asteroids
• Millions of comets
• Innumerable small fragments of rock
and dust called meteoroids

Physical and astronomical data for the Earth

The terrestrial and

Jovian planets

• Terrestrial planets: Mercury, Venus,

Earth, Mars
Closer to the Sun, small, rocky and
dense (≥3 gm/cm3)
• Jovian planets: Jupiter, Saturn, Uranus,
Neptune, Pluto
Much larger than the terrestrial planets
(except Pluto), largely made of very
light elements and volatile compounds
(H2, He, CO2, NH3); much less dense

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The Earth’s interior: major internal differentiation

Artist’s conception of the very early Earth

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Dmitri Mendeleev (1834-1907)

The Periodic Table

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The Periodic Table

Composition of the Earth: Clues from meteorites

• Meteorites are valuable as early Solar System samples.

• They are very diverse, but are classified broadly into:
Iron meteorites (Fe and Ni dominantly)
Stony meteorites (silicate minerals)
Stony irons (mixture of silicate and metallic phases).
• Meteorites are collected as “finds” and “falls”.
• The “finds” are usually iron meteorites. Stony
meteorites resemble terrestrial rocks and are difficult to
identify as such unless seen to fall.
• Common types of stony meteorites are chondrites and
achondrites.

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Formation of
different types of
meteorites due to
planetary
differentiation
followed by
explosions or
asteroid impacts

Chondrites are stony meteorites containing chondrules –

granular silicate minerals like olivine and pyroxene, which
probably represent molten or partially molten droplets in
space. Most meteorite falls are chondrites.

A specimen of the NWA 869 chondrite

A chondrite in thin section
(type L4-6), showing chondrules and
(enlarged ~12X)
metal flakes

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• Some chondrites also contain refractory inclusions of

minerals rich in Ca, Al and Ti, which are among the oldest
objects formed in the Solar System.
• Chondrites also contain grains rich in metallic Fe-Ni and
sulphides.
• Chondrites formed when various types of dust and small
grains that were present in the early Solar System accreted to
form primitive asteroids.
• Chondrites are thus primitive and undifferentiated
meteorites.
• There are over 27,000 chondrites in the world’s collections.
• The largest chondrite found weighs 1770 kg.

• Carbonaceous chondrites constitute <5% of all chondritic

meteorites.
• They are a type with at least 7 known groups and all
contain organic (C-H) compounds (like amino acids).
• They include some of the most primitive known
meteorites. Some famous ones are: Allende, Murchison,
Orgueil, Ivuna, Murray, and Tagish Lake.

• The type of carbonaceous chondrite

called CI chondrites (Carbonaceous
Ivuna) have a composition representing
the Solar System in its entirety, and
represent Bulk Earth composition. They
are the most primitive and
undifferentiated meteorites.

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• Achondrites resemble terrestrial basalts in mineral

composition and texture.
• They contain no chondrules and no metal.
• They are differentiated meteorites with compositions quite
different from the Solar Nebula.
• They may be fragments of already-differentiated planetary
crusts.

An achondrite in thin section (enlarged ~12X).

• The abundances of many refractory elements in the CI

chondrites correspond to those in the Solar photosphere. They
thus represent the Solar Nebula (and Bulk Earth) composition.
Achondrites have data quite off the 1:1 correlation line.

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• In the Solar System and chondrites, elements with even

atomic numbers are more abundant than elements with odd
atomic numbers on either side.
• This is called the Oddo-Harkins Rule/Effect, after Giuseppe
Oddo (1865-1954) and William Harkins (1873-1951).
11
10
H
Log (Abundance in CI Chondritic Meteorite)

He
9
8
O
C
7 Ne MgSi
6
Fe Note the saw-tooth or zig-zag abundance
N S Ar
5 Ca Ni pattern (Oddo-Harkins effect)
4 Na
AlP Ti
3
K
2 F Cl
Li V
1 B Sn Ba
Sc Pt Pb
0
-1 Be Th
-2 U
-3
0 10 20 30 40 50 60 70 80 90 100
Atomic Number (Z)

• Elements with even atomic numbers have electron spins

that are coupled and cancelling, resulting in stability.
• Also, elemental abundance generally smoothly decreases
with increasing atomic number (heavier elements are
progressively less abundant). (Fe is one of the exceptions).
11
10
H
Log (Abundance in CI Chondritic Meteorite)

He
9
8
O
C
7 Ne MgSi
6
Fe
N S Ar
5 Ca Ni
4 Na
AlP Ti
3
K
2 F Cl V
1
Li Sn Ba
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)

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• Early geochemists of the 19th century were

concerned with the composition of the Earth’s
crust, and various minerals and rocks including
the ore minerals.
Vladimir • They generated massive data sets after a lot of
Vernadsky
(1863-1945) slow and hard work, often during very difficult
times (e.g., Goldschmidt during WWII).

Frank W. Clarke
(1847-1931)

Victor Goldschmidt
(1888-1947), the father
of modern geochemistry

Seven elements that make up ~97% of the Earth by

mass, and which make up various minerals and
rocks

Granite

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The main elements that make up the Earth’s crust (by mass and by volume)

The crust is essentially a packing of oxygen atoms

(Goldschmidt).

Texts

• Mason, B. and Moore, C. B., 1982. Principles of Geochemistry, 4th Edn.

Wiley Eastern Ltd.
• Rollinson, H. R., 1994. Using Geochemical Data: Evaluation, Presentation,
Interpretation. Longman.
• Gill, R., 1996. Chemical Fundamentals of Geology, 2nd Edn. Chapman &
Hall.
• Faure, G., 1986. Principles of Isotope Geology, 2nd Edn. John Wiley.
• Best, M. G., 2003. Igneous and Metamorphic Petrology, 2nd Edn.,
Blackwell.
• Winter, J. D., 2010. Introduction to Igneous and Metamorphic Petrology,
2nd ed., Prentice-Hall.
• Ragland, P. C., 1989. Basic Analytical Petrology. Oxford Univ. Press.
•Albarede, F., 2003. Geochemistry: An Introduction. Cambridge Univ. Press.
• Richardson, S. M. and McSween, H. Y., 1989. Geochemistry: Pathways and
Processes. Prentice-Hall.

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Geochemical analyses of rocks

Geochemical data can be divided into:

• Major elements: > 1.0 wt.% of a rock
• Minor elements: 0.1 – 1.0 wt.% of a rock
• Trace elements: < 0.1 wt.% of a rock (i.e., < 1000 ppm)
• Isotopic ratios (e.g., 87Sr/86Sr).
• All major and minor elements together make up nearly
100% by weight.
• Any particular element can be a major element in one
rock (e.g., K in granite) and a minor element in another
rock (K in basalt).
• 1 wt.% = 10,000 ppm (because % is equivalent to pph).

Example: Geochemical analysis of a basalt lava flow SH88 from the Deccan Traps

Oxide Wt.% Trace elements (ppm)

SiO2 (silica) 51.10 Rb 24 La 16.7
TiO2 (titania) 2.33 Ba 199 Ce 35.9
Al2O3 (alumina) 15.45 Sr 304 Pr 5.15
Fe2O3 (ferric oxide) 2.07 Zr 162 Nd 22.2
FeO (ferrous oxide) 10.57 U 0.47 Sm 5.20
MnO (manganese oxide) 0.15 Th 2.2 Eu 1.68
MgO (magnesia) 4.11 Nb 12 Gd 5.92
CaO (lime) 9.73 Ta 0.75 Tb 0.93
Na2O (soda) 1.96 Cu - Dy 5.05
K2O (potash) 0.89 Zn - Ho 1.01
P2O5 0.24 V 300 Er 2.46
LOI (loss on ignition) 2.69 Co 39 Tm 0.35
Total 101.29 Ni 52 Yb 2.16
Cr - Lu 0.32

LOI includes the volatiles (H2O+, H2O–, and CO2), where H2O+ is structurally bound
water, and H2O– is simply the dampness in the rock powder.

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Weight-weight conversions of compositional data

2 gfw for EW for Conversion
1 Atom/oxide atom/ EW oxide in col. factor
Oxide for oxide 1
Note: Gram SiO2 Si 28.09 60.09 0.4675
formula wt. (gfw) TiO2 Ti 47.90 79.90 0.5995
of oxygen (O) is Al2O3 Al 26.98 50.98 0.5292
16; Molecular Fe2O3 Fe 55.85 79.85 0.6994
wt. of oxygen Fe2O3 FeO 71.85 79.85 0.8998
(O2) is 32.
FeO Fe 55.85 71.85 0.7773
For oxides (or
FeO Fe2O3 79.85 71.85 1.1113
other
MnO Mn 54.94 70.94 0.7745
compounds) with
just one cation, MgO Mg 24.31 40.31 0.6031
molecular weight CaO Ca 40.08 56.08 0.7147
and equivalent Na2O Na 22.99 30.99 0.7419
weight are the K2O K 39.10 47.10 0.8301
same. P2O5 P 30.97 70.97 0.4364
H2O+ H 1.01 9.01 0.1121
H2O+ OH– 17.01 18.01 0.9445
CO2 C 12.01 44.01 0.2729

Example:
Wt.% oxide Conversion Atom Wt.% atom
Oxide Factor
SiO2 48.70 0.4675 Si 22.80
TiO2 1.29 0.5995 Ti 0.77
Al2O3 16.60 0.5292 Al 8.78
Fe2O3 2.05 0.6994 Fe3+ 1.43
FeO 8.29 0.7773 Fe2+ 6.44
MnO 0.16 0.7745 Mn 0.12
MgO 6.63 0.6031 Mg 4.00
CaO 10.70 0.7147 Ca 7.65
Na2O 2.83 0.7419 Na 2.10
K2O 0.47 0.8301 K 0.39
P2O5 0.81 0.4364 P 0.76
H2O+ 0.20 0.9445 OH– 0.09
CO2 0.09 0.2729 C 0.02
Total 99.49 55.35
(O=44.1)

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Weight-weight conversions: Solved problems

Problem 1: A basalt has 10.23% CaO and 328 ppm of Sr.
Calculate its Ca/Sr ratio.
Solution: Ca must be calculated, and both Ca and Sr must be
in the same units.
Ca wt.% = (CaO wt.%) x (0.7147) = 10.23 x 0.7147 = 7.31%
And Ca ppm = Ca wt.% x 10000 = 73100 ppm
∴Ca/Sr = 73100/328 = 222.9. Work this out in wt.% units.
Problem 2: Calculate the Ba/Ti ratio of a volcanic rock
containing 300 ppm Ba and 3.50% TiO2. The gfw of Ti is
47.90 and the EW of TiO2 is 79.90.
Solution: The conversion factor for TiO2 into Ti is 47.90/79.90
= 0.5995
Ti ppm = (TiO2 wt.%) x (0.5995) x (10000) = 20982.5 ppm
∴ Ba/Ti = 300/20982.5 = 0.0143.

Iron in rocks: Ferrous, ferric, and total iron

• Iron in rocks has two oxidation states (Fe2+ as in FeO, Fe3+ as
in Fe2O3). (Pure Fe0 metal exists in meteorites.)
• Most modern analytical techniques measure total Fe in a
rock, not FeO% and Fe2O3% separately.
• Total Fe can be reported as FeO(T) or Fe2O3(T) – NOT the
same thing!
• FeO(T) or Fe2O3(T) CANNOT be obtained by simple
addition of FeO wt.% and Fe2O3 wt.%.
• FeO(T) is also written FeO* or ΣFeO, and Fe2O3(T) Fe2O3*
or ΣFe2O3.
• EW of Fe2O3 is 79.85, and EW of FeO is 71.85. Hence, to
convert Fe2O3 into FeO, multiply Fe2O3 by 0.8998.
• To convert FeO into equivalent Fe2O3, multiply FeO by
1.1113.

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Problem 1: Calculate FeO(T) and Fe2O3(T) for a rock having

8.29% FeO and 2.05% Fe2O3.
Solution:
To calculate FeO(T), keep the FeO wt.% as is, convert the
Fe2O3 wt.% into FeO wt.%, and then add the two.
i.e., FeO(T) = 8.29 + (2.05 x 0.8998) = 10.13 wt.%.

To calculate Fe2O3(T), keep the Fe2O3 wt.% as is, convert the

FeO wt.% into Fe2O3 wt.%, and then add the two.
i.e., Fe2O3(T) = 2.05 + (8.29 x 1.1113) = 11.26 wt.%.
Thus, FeO(T) and Fe2O3(T) for the same rock have different
values.
Also, both values are different from the simple sum of FeO%
and Fe2O3%, which is 10.34 wt.%.
Do not forget the units.

• How to obtain individual FeO% and Fe2O3% if FeO(T) or

Fe2O3(T) are reported?
• For this, assume a reasonable ratio between the two,
depending on the rock type.
• A 85:15 (or 90:10) ratio for FeO: Fe2O3 is good for unaltered
basic volcanic rocks.
• For altered and evolved rocks, will the Fe2O3:FeO ratio be
more or less?
• Problem 2: A fresh basalt has 12.00 wt.% FeO(T). Calculate
its FeO% and Fe2O3%.
Solution: Since total Fe is reported as FeO(T), calculate FeO
first. Assuming FeO/FeO(T) = 0.85, FeO% = 0.85 x 12.00 =
10.20. The remaining FeO must be multiplied by 1.1113 to
obtain Fe2O3.
i.e., Fe2O3% = (12.00 – 10.20) x 1.1113 = 2.00.

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Problem 3: A mafic rock contains 15.00 wt.% Fe2O3*.

Calculate its FeO% and Fe2O3%.
Solution: Here, since total Fe is reported as Fe2O3*, we will
calculate Fe2O3 first. Assuming Fe2O3/Fe2O3* = 0.15, Fe2O3 =
0.15 x 15.00 = 2.25.
The remaining Fe2O3 (15.00 – 2.25), after conversion, will be
the FeO. i.e., FeO% = 12.75 x 0.8998 = 11.47.
Problem 4: An igneous rock contains 2.50% TiO2, 1.50%
Fe2O3, and 8.00% FeO. Calculate its Fe/Ti ratio.
Solution: Fe wt.% (in Fe2O3) = Fe2O3 wt.% x 0.6994 = 1.50 x
0.6994 = 1.05%. Fe wt.% (in FeO) = FeO wt.% x 0.7773 =
8.00 x 0.7773 = 6.22%.
Total Fe wt.% = 1.05 + 6.22 = 7.27%
Ti wt.% = 2.50 x 0.5995 = 1.50%
∴ Fe/Ti = 7.27/1.50 = 4.85.

Geochemical data and petrogenetic models

• Geochemical data are essential for understanding the

petrogenesis of igneous rocks, and provide valuable
information about the following:
1. The nature of the source rocks.
2. The nature of the melting processes (fractional, batch...)
3. Processes of magmatic evolution (e.g., crystal
fractionation, contamination).
• Geochemical data are equally useful in studying
metamorphic rocks (e.g., ACF, AKF diagrams), and even
sedimentary rocks (e.g., provenance studies).

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The geochemical diversity of igneous rocks

Major element variation in the most common silicate magmas and rocks

Some typical rock analyses showing the diversity of igneous rock

compositions and their minerals

Peridotite Basalt Andesite Rhyolite Phonolite

SiO2 42.26 49.20 57.94 72.82 56.19
TiO2 0.63 1.84 0.87 0.28 0.62
Al2O3 4.23 15.74 17.02 13.27 19.04
Fe2O3 3.61 3.79 3.27 1.48 2.79
FeO 6.58 7.13 4.04 1.11 2.03
MnO 0.41 0.20 0.14 0.06 0.17
MgO 31.24 6.73 3.33 0.39 1.07
CaO 5.05 9.47 6.79 1.14 2.72
Na2O 0.49 2.91 3.48 3.55 7.79
K2O 0.34 1.10 1.62 4.30 5.24
H2O+ 3.91 0.95 0.83 1.10 1.57

Total 98.75 99.06 99.30 99.50 99.23

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Trace elements vary much

more than major elements,
and are very useful for
petrogenetic modelling,
forward or inverse.
• Forward modelling:
Assume starting
composition, calculate melts
• Inverse modelling: Take
melt compositions, work
back to sources

Right: Crater Lake (Oregon, U.S.A.)

volcanic rock data

The concentration of a
major element in a
phase is usually
buffered by the
system, so that it
varies little as the
system composition
changes. Here, at a
given T we could vary
Xbulk from 35 → 70 %
Mg/Fe without Trace elements behave as dilute
changing the solutions (Henry’s Law), and their
composition of the activity varies in direct relation to
melt or the olivine. their concentration in the system.
Thus if XNi in the system doubles
the XNi in all phases will double.

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A brief summary of some particularly useful trace elements in igneous geochemistry

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

Ir, 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.

• Incompatible elements are concentrated in the melt relative

to solid (during either melting or crystallization), e.g., Rb,
Na, K. They can be major or trace elements.
• Compatible elements are concentrated in the solid relative to
liquid (during melting or crystallization), e.g., Ni, Co.
• We define Nernst partition coefficient or distribution
coefficient, Kd, as
Kd = Cs/CL where Cs = concentration of an element in the
solid, and CL = its concentration in the liquid.
Walther Nernst
• For an incompatible element, Kd < 1 (1864-1941)

• For a compatible element, Kd > 1

• If Kd = 1, element is neither of the two.
• If Kd = 0, element is perfectly incompatible.

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• A Kd value is specific to an element and a mineral, and also

depends on temperature, melt composition, etc.
• Olivine has a very high Kd for Ni, pyroxene for Sc.
• Elements which are incompatible in most minerals are Rb,
Ba, Na, K, Ti, Zr, Hf, Nb, U, Th.
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

Some important elements and their preferred minerals:

• Ni, Cr: compatible in olivine.
• Sc: compatible in clinopyroxene.
• Sr, Eu: compatible in plagioclase.
• K: compatible in orthoclase, microcline, and certain
amphiboles.
• Rb: compatible in hornblende.
• Y, Yb, Lu (HREE): compatible in garnet.
• Ti: compatible in titanomagnetite and rutile.
• Zr: compatible in zircon.
• For a fractionation assemblage comprising olivine,
clinopyroxene, and plagioclase, the following elements are
highly incompatible: Cs, Rb, Ba, Nb, Ta, K, La, and Ce.

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• Kd values even for particular elements and minerals are

not fixed, but are affected by temperature, pressure, and
magma composition (felsic or mafic).
• What decides the partition coefficients: Goldschmidt’s
rules:
• If two ions have different radii and the same valency, the
smaller ion is preferentially incorporated into the solid over
the liquid.
• If two ions have similar radii, but different valencies, the
ion with the higher charge is preferentially incorporated
into the solid over the liquid.

Victor Goldschmidt (1888-1947), the father of modern geochemistry

• If a magma is fractionating not just one mineral, but

several minerals together, then the bulk distribution
coefficient (D) must be calculated.
• Likewise, for melting of a mantle source, D must be
calculated based on weight fractions of the minerals
contributing to the melt.
• Thus, for an element X, and a rock made up of minerals A,
B and C with mass proportions WA, WB and WC in the
rock, and individual partition coefficients for element X of
KdA, KdB and KdC, respectively,

DX = WAKdA + WBKdB + WCKdC

• Be sure to use mass fractions of minerals, not volume
fractions (mode). Convert mode to wt.%.

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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 above,
DEr = (0.6 x 0.026) + (0.25 x 0.23) + (0.10 x 0.583) + (0.05 x
4.7) = 0.366

Rayleigh fractional melting: trace element modelling

In Rayleigh fractional melting, each infinitesimally
small melt fraction produced is immediately
removed from the source. The melting equation is

CL = [CO (1 – F)(1/Do – 1)] / DO

Where
CL = concentration of an element in the liquid;
Lord Rayleigh
CO = concentration of the element in the original (John William
(unmelted) source rock Strutt), 1842-
1919
F = melt fraction (weight fraction of produced
melt);
DO = bulk distribution coefficient prior to the onset
of melting

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Rayleigh fractional melting (contd.)

• For the residuum (“restite”), CR = DO x CL

• For a perfectly incompatible element, CL /CO is infinity.
• When DO = 1, CL /CO = 1 (no change in concentration from
source to melt).
• For very low degrees of melting, highly incompatible
elements are very strongly enriched in the melts, while the
more compatible ones remain in the source (e.g., high La/Yb
ratios in melts with residual garnet in the source).

Q: A garnet lherzolite mantle source contains 10 ppm Sr and

2000 ppm Ni. The mineralogical composition of the source is
olivine (40%), clinopyroxene (30%), orthopyroxene (20%),
and garnet (10%). The Kd’s for Sr are: 0.005 (ol), 0.1 (cpx),
0.01 (opx), 0.001 (gt). The Kd’s for Ni are: 12 (ol), 2 (cpx), 4
(opx), and 0 (gt). What will be the Sr and Ni concentrations in
the basaltic melts and corresponding residues after 5% and
10% fractional melting?

A: DOSr = (0.4 x 0.005) + (0.3 x 0.1) + (0.2 x 0.01) + (0.1 x

0.001) = 0.034.
DONi = (0.4 x 12) + (0.3 x 2) + (0.2 x 4) + (0.1 x 0) = 6.2

25
 22-07-2015

Using CL = [CO (1 – F)(1/DO – 1)] / DO for 5% melting (F =

0.05),
CL (Sr) = 10 x [(1 – 0.05)(1/0.034 – 1)] / 0.034 = 68 ppm; CR
(Sr) = 0.034 x 68 = 2.31 ppm
CL (Ni) = 2000 x [(1 – 0.05)(1/6.2 – 1)] / 6.2 = 337 ppm; CR
(Ni) = 6.2 x 337 = 2089 ppm
Using the same relationship for 10% melting (F = 0.10),
CL (Sr) = 10 x [(1 – 0.10)(1/0.034 – 1)] / 0.034 = 14.7 ppm;
CR (Sr) = 0.034 x 14.7 = 0.50 ppm
CL (Ni) = 2000 x [(1 – 0.10)(1/0.034 – 1)] / 6.2 = 352 ppm; CR
(Ni) = 6.2 x 352 = 2182 ppm
Thus, for melts, greater degrees of melting mean dilution of
incompatible elements like Sr, and enrichment of compatible
elements like Ni. For residues, progressive melting means
depletion of incompatible elements like Sr, and enrichment of
compatible elements like Ni.

Equilibrium (batch) melting: trace element modelling

In equilibrium (batch) melting, melt continuously equilibrates

with rock and is removed as a single batch.

• The equations for modal batch melting are

CL = CO / [DO (1 – F) + F]
and C R = DO x C L

•For a perfectly incompatible element (DO = 0), CL /CO = 1/F

• For F = 1.0 (complete melting), CL = CO for all elements,
i.e., the melt has the same composition as the source
For DO = 1.0, CL = CO

26
 22-07-2015

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 the
equation for equilibrium
batch melting

Note how the

highly
incompatible
elements are
greatly enriched
in the initial low-
degree melt
fractions, and get
subsequently
diluted as melt
fraction increases.

27
 22-07-2015

As F → 1 the
concentration of
every trace element
in the liquid = the
source rock (CL/CO
→ 1)

Rayleigh fractionation
Rayleigh fractionation represents the idealized case of a
closed system (magma chamber), without magma recharge or
magma/wallrock mixing.
Q: Imagine a closed magma chamber with a cooling magma
body. No new magma is entering the chamber. Crystals of
three different minerals are forming from the magma, and
sinking to the base of the magma chamber. The starting
magma contained 100 ppm of a perfectly incompatible
element “X”. What will be the concentrations of X in the
residual liquids?
A: As the element X is perfectly incompatible in each of the
three fractionating minerals, Kd values for X for all three are
zero. Hence, D also equals zero. The concentrations of X will
be

28
 22-07-2015

% of Melt Fractional ppm of X

original fraction crystallization, in liquid
liquid (F) %
100% 1.0 0% 100 (Co)
50% 0.5 50% 200 (CL)
25% 0.25 75% 400 (CL)
12.5% 0.125 87.5% 800 (CL)
6.25% 0.0625 93.75% 1600 (CL)
The last Nearly Almost 100% Nearly
drop zero infinite CL

So, % fractionation = (1 – F) x 100 and CL = CO /F

Because CO is a constant, as F approaches zero, CL
approaches infinity.
• For a more realistic case where KD ≠ 0, the Rayleigh
fractionation equation is
• CL = COF D-1

Q: A magma, before the start of crystallization, contained

450 ppm Ni. Calculate how much Ni will be contained in
this magma after 40% fractional crystallization, the
fractional assemblage comprising ol:cpx:plag in the
proportion 40:25:35. The Kd values for Ni are 12.0 (ol), 2.00
(cpx), and 0.01 (plag), and the Rayleigh fractionation
equation is CL = COFD-1.
A: The weight fractions of ol, cpx, and plag are 0.40, 0.25,
and 0.35, respectively.
DNi = (0.4 x 12.0) + (0.25 x 2.00) + (0.35 x 0.01) = 4.80 +
0.50 + 0.0035 = 5.30.
CL = COFD-1
For 40% crystallization (F = 0.6), CL = 450 x 0.64.30 = 450
x 0.1112 = 50.0 ppm.

29
 22-07-2015

Q: A rhyolitic liquid, with

500 ppm Ba, is
undergoing fractional
crystallization with a bulk
distribution coefficient
DBa = 1. What will be the
Ba content of this liquid
after 25%, 50% and 75%
fractionation?
A: Using CL = COFD-1,
since D = 1, FD-1 = 1, and
hence CL = CO always
(i.e., no change in Ba
concentration during
fractionation).

LILE and HFSE

• Incompatible elements can

be divided into two groups
based on their field strength
(= ionic charge/size ratio),
equivalent to ionic potential
(= valency/ionic radius).
• High-field-strength
elements (HFSE) have high
ionic charge and small size,
and ionic potential > 2.0.
Examples are Nb, Ta, Zr,
Hf, REE, Th, U, Pb4+, Ti.

30
 22-07-2015

LILE and HFSE

• Large-ion-lithophile
elements (LILE) have large
ionic size and low ionic
charge, and ionic potential
< 2.0. They are also known
as low-field-strength
elements (LFSE).
Examples are Cs, Rb, K,
Ba, Pb2+. They are more
mobile, especially if fluids
are present.

Enriched and depleted geochemical reservoirs and

magma sources

• An enriched source is a source rich in incompatible elements

(Rb, Ba, K, Nb…). The cause of enrichment may be
metasomatism by aqueous fluids or silicate melts, or simple
partial melting. The continental crust is an example.
• A depleted source is a source poor in incompatible elements.
The cause is usually previous melt extraction which has
removed the incompatible elements.
• An “enriched” source (e.g., continental crust), with high Rb,
will develop high 87Sr/86Sr (>0.78..) with time, as the
radioactive decay of 87Rb produces 87Sr (86Sr is a stable
isotope). A “depleted” source like MORB mantle, with long-
term low Rb, generates low 87Sr/86Sr ratios (~0.7030) even
after a long time.

31
 22-07-2015

The Rare Earth Elements (REE)

At. REE name Sym Ionic ppm ppm C1 Normalized
No. -bol radius (Å) basalt chondrite conc. (CN)
57 Lanthanum La 1.160 Light 10.2 0.237 43.04
58 Cerium Ce 1.143 REE 25.2 0.612 41.18
59 Praseodymium Pr 1.126 3.44 0.095 36.21
60 Neodymium Nd 1.109 16.6 0.467 35.55
61 Promethium Pm Does not exist naturally
62 Samarium Sm 1.079 Middle 4.5 0.153 29.41
63 Europium Eu 1.066 REE 1.16 0.058 20.00
64 Gadolinium Gd 1.053 5.53 0.2055 26.91
65 Terbium Tb 1.040 0.83 0.0374 22.19
66 Dysprosium Dy 1.027 5.31 0.2540 20.90
67 Holmium Ho 1.015 0.98 0.0566 17.31
68 Erbium Er 1.004 Heavy 2.48 0.1655 14.98
69 Thulium Tm 0.994 REE 0.37 0.0255 14.51
70 Ytterbium Yb 0.985 2.48 0.170 14.59
71 Lutetium Lu 0.977 0.38 0.0254 14.96

32
 22-07-2015

• The REEs are petrogenetically

extremely important.
• Similar geochemical
properties; all are trivalent (Eu
both +3 and +2).
• From La (57) to Lu (71), ionic
radius systematically decreases
(lanthanide contraction) and the
compatibility in typical mantle
minerals increases.
• HREE are compatible in
garnet and MREE in
hornblende, sphene, and
clinopyroxene.

• As for other
elements, partition
coefficients for the
REE even in the same
mineral depend on
magma composition
(indirectly,
temperature).

33
 22-07-2015

• The Oddo-Harkins Rule is equally true of the REE.

• In the Solar System, chondrites, and igneous rocks, REE
with even atomic nos. are more abundant than REE with
odd atomic nos. on either side. The result is a zig-zag or
saw-toothed abundance pattern.
11
10
H
Log (Abundance in CI Chondritic Meteorite)

He
9
8
O
C
7 Ne MgSi
6
Fe
N S Ar
5 Ca Ni
4 Na
AlP Ti
3
K
2 F Cl V
1 Li Sn Ba
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)

34
22-07-2015

35
 22-07-2015

Chodrite-normalized REE diagrams

• Chondrite normalization (dividing REE concentration in an
igneous rock by that in chondrites) smooths out the saw-
toothed pattern. Note log scale to depict large range.
• Slope of the REE pattern (LaN/YbN or LaN/LuN) is of
petrogenetic interest. (N denotes normalized value.)

Note that we plot

actual concentrations
on log scale, not logs
of the concentrations.

REE diagram for a typical

alkaline ocean island basalt
(OIB) and tholeiitic mid-ocean
ridge basalt (MORB).

• Many alkali basalts have highly fractionated REE patterns

(steep slope). Possible explanations: → Residual garnet?
Fractionation? Mantle metasomatism? Contamination?…
• Most MORB have REE patterns tilted to the left, or flat
(Depleted mantle source).

• Granites of
the continental
crust also have
high
LREE/HREE
ratios.

36
 22-07-2015

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

Eu anomalies and Eu/Eu*

• Eu forms Eu+2 at low oxygen activity (reducing
conditions), which operate during crystallization of most
basaltic liquids. If so it can substitute for Ca+2 in plagioclase.
• If plagioclase fractionation occurs, the residual magma will
show a negative Eu (also Sr) anomaly.
• Eu/Eu* is a measure of the size of a Europium anomaly. Eu
is the observed normalized value, and Eu* is the normalized
value expected in the absence of a Eu anomaly.

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 22-07-2015

Eu anomalies and Eu/Eu*

• Eu forms Eu+2 at low oxygen activity (reducing
conditions), which operate during crystallization of most
basaltic liquids. If so it can substitute for Ca+2 in plagioclase.
• If plagioclase fractionation occurs, the residual magma will
show a negative Eu (also Sr) anomaly.
• Eu/Eu* is a measure of the size of a Europium anomaly. Eu
is the observed normalized value, and Eu* is the normalized
value expected in the absence of a Eu anomaly.
• Eu* is obtained by simply averaging the normalized Sm
and Gd values, since Sm and Gd are located on either side of
Eu, each 1 At. No. away.
• Eu anomalies can be positive or negative. Positive Eu
anomalies are characteristic of plagioclase accumulation
(e.g., lunar highland anorthosites).

38
 22-07-2015

Problem 1: A volcanic rock has chondrite-normalized values

of 31.7 (Eu), 46.4 (Sm), and 33.9 (Gd). Does it have a Eu
anomaly? If yes, is it positive or negative?
Solution: Eu* = (46.4 + 33.9) / 2 = 40.2.
The observed normalized value of Eu is 31.7.
Since Eu/Eu* = 31.7/40.2 = 0.79 < 1, the rock has a small
negative Eu anomaly.

Problem 2: Using the data in the table below, find out the REE abundances in an andesite magma after 40%
plagioclase fractionation, using the relationship CL = COFD-1. Will a rock formed by the solidification of this residual
magma have a Eu anomaly in its REE pattern?

Kd (plag) CO (ppm) CL (ppm) Chondrite CO(N) CL(N)

REE Rollinson, Ragland, S&M,’89
’93 ’89
La 0.1477 24.2 37.4 0.237 102 158
Ce 0.0815 53.7 85.8 0.612 87.7 140
Pr - 6.50 - 0.095 68.4 -
Nd 0.0551 28.5 46.2 0.467 61.0 98.9
Sm 0.0394 6.70 10.9 0.153 43.8 71.2
Eu 1.1255 1.95 1.83 0.058 33.6 31.5
Gd 0.0310 6.55 10.7 0.2055 31.9 52.1
Tb - 1.08 - 0.0374 28.9 -
Dy 0.0228 6.39 10.5 0.2540 25.2 41.3
Ho - 1.33 - 0.0566 23.5 -
Er 0.0202 3.70 6.10 0.1655 22.4 36.9
Tm - 0.51 - 0.0255 20.0 -
Yb 0.0232 3.48 5.73 0.170 20.5 33.7
Lu 0.0187 0.55 0.91 0.0254 21.6 35.8
Eu* 37.8 61.6
Eu/Eu* 0.89 0.51

39
 22-07-2015

Exercise: Interpret
the three patterns
given in the figure.

REE data for oceanic basalts

40
 22-07-2015

Question: Given the same source rock, (how) does the

LREE/HREE fractionation in the partial melt (i.e., slope of
the REE pattern) depend on the degree of partial melting?

REE concentrations
(normalized to
chondrite) for melts
produced at various
values of F via
melting of a
hypothetical garnet
lherzolite using the
batch melting
model.

41
 22-07-2015

Normalized multi-element diagrams

• An extension of the chondrite-normalized REE diagrams,
with more elements.
• Normalization with chondrite or primitive mantle (PM).
• PM is the (estimated) mantle composition before first crust
formation; Chondrite values are actually measured (so better?)
• Called “spiderdiagrams” or “spidergrams” (strangely); many
variations.
• Use logarithmic scale.
• Elements toward the right are increasingly more compatible
in mantle rocks.
• The sequence is Cs, Rb, Ba, Th, U, K, Nb, Ta, La, Ce, Pr, Pb,
Sr, Nd, P, Zr, Sm, Eu, Ti, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb, Lu.

• Overall slope of the pattern is of petrogenetic interest, as

are peaks and troughs (positive and negative anomalies).
• MORB normalization can be used for evolved basalts,
andesites, crustal rocks.

• Cs, Rb, K, U…
abundances are
affected by
weathering and
alteration.
• Th, Nb, Ta, Ti
etc. are little
affected by
weathering and
alteration.

42
 22-07-2015

Spiderdiagram for a typical alkaline ocean island basalt (OIB) and tholeiitic
mid-ocean ridge basalt (MORB). Data from Sun and McDonough (1989).

• Primitive mantle normalization (rather than chondrite

normalization) may be better – chondrites are not a standard
for elements like Cs and Rb.
100

Normal-MORB
Enriched-MORB
Ocean island basalt
Rock/Primitive Mantle

10

1
Rb Ba Th U K Nb Ta La Ce Pr Pb Sr Nd P Zr Sm Eu Ti Gd Tb Dy Y Ho Er Tm Yb Lu

43
 22-07-2015

Primitive mantle-normalized multielement patterns for

various types of continental crust (averages)
1000

Lower continental crust

Middle continental crust
Upper continental crust

100
Rock/Primitive Mantle

10

1
Rb Ba Th U K Nb Ta La Ce Pr Pb Sr Nd P Zr Sm Eu Ti Gd Tb Dy Y Ho Er Tm Yb Lu

Mixing processes: Simple (bulk) mixing

• In simple binary mixing, all mixtures are located between
the two components that are mixing (mixing end members).
• In simple ternary mixing, all mixtures are in a triangle
bounded by the three end members.

44
 22-07-2015

• For a simple binary mixture of a magma (M) and

country rock (R), the concentration C of an element z in
the mixture will be
CZ (mix) = (WM x CZM) + (WR x CZR)
where W is the weight fraction of each.
e.g., for a simple 60:40 mixture, CZ (mix) = (0.6 x CZM)
+ (0.4 x CZR)

Problem 1: Calculate the composition of a simple 70:30

mixture of basalt SH20 and upper continental crust
(UCC) using the data (in ppm) below. Plot the primitive-
mantle-normalized multielement patterns for the basalt,
crust, and the mixture.

SH20 UCC: Mixture (70:30) PM SH20N UCCN MixN

R&F,’95 S&M,’89

Cs - 5.6 - 0.079 - - -
Rb 22 112 49 0.635 34.64 176.38 77.16

Ba 278 550 360 6.989 39.78 78.69 51.51

Th 2.28 10.7 4.81 0.085 2.68 125.88 56.59

U 0.28 2.8 1.04 0.021 13.33 133.33 49.52

K 8096 28223 14134 250 32.38 112.89 56.54

Nb 9.1 11 9.67 0.713 12.76 15.43 13.56

Ta 0.56 0.92 0.67 0.041 13.66 22.44 16.34

La 17.8 30 21.5 0.687 25.91 43.67 31.29

Ce 37.6 64 45.5 1.775 21.18 36.06 25.63

Pr 5.01 7.1 5.64 0.276 18.15 25.72 20.43

Pb 5.6 20 9.9 0.071 78.87 281.69 139.44

Sr 299 350 314 21.1 14.17 16.59 14.88

Nd 23.4 26 24.2 1.354 17.28 19.20 17.87
P 1029 1745.6 1244 95 10.83 18.37 13.09

Zr 132 190 149 11.2 11.78 16.96 13.30

Sm 5.99 4.5 5.54 0.444 13.49 10.13 12.48

Eu 1.79 0.9 1.52 0.168 10.65 5.36 9.05

Ti 15200 2997 11539 1300 11.69 2.30 8.88

Gd 6.56 3.8 5.66 0.596 11.01 6.37 9.50

Tb 1.00 0.64 0.89 0.108 9.26 5.92 8.24

Dy 5.41 3.5 4.84 0.737 7.34 4.75 6.57

Y 29.7 22 27.4 4.55 6.53 4.83 6.02

Ho 1.13 0.80 1.03 0.164 6.89 4.88 6.28

Er 2.75 2.3 2.61 0.480 5.73 4.79 5.44

Tm 0.37 - - 0.074 5.00 - -

Yb 2.28 2.2 2.26 0.493 4.62 4.46 4.58

Lu 0.34 0.32 0.334 0.074 4.59 4.32 4.51

45
 22-07-2015

• Simple mixing with theoretical but possible mixing

components can sometimes explain observed compositions.
1000

Transitional-MORB
Upper continental crust
T-MORB:UCC mix (80:20)
Bushe (JEB185), Deccan

100
Rock/Primitive Mantle

10

1
Rb Ba Th U K Nb Ta La Ce Pr Pb Sr Nd P Zr Sm Eu Ti Gd Tb Dy Y Ho Er Tm Yb Lu

Effects of simple mixing on elements and element ratios

Magma 10% G 30% G 50% G 70% G 90% G Granite

Ba ppm 50 145 335 525 715 905 1000

Sr ppm 100 110 130 150 170 190 200
Ba/Sr 0.50 1.32 2.58 3.50 4.21 4.76 5.00
Rb (ppm) 10 19 37 55 73 91 100

Th (ppm) 2 6.8 16.4 26 35.6 45.2 50

Rb/Th 5 2.79 2.26 2.11 2.05 2.01 2.00
Rb/Sr 0.10 0.17 0.28 0.37 0.43 0.48 0.50

200

175
Sr (ppm)

150

125

100
0 100 200 300 400 500 600 700 800 900 1000 1100

Ba (ppm)

46
 22-07-2015

Observation: On binary plots of elements, simple mixing

always produces straight lines.
5.0

4.5

4.0
Rb/Th

3.5

3.0

2.5

2.0
0.00 1.00 2.00 3.00 4.00 5.00

Ba/Sr

Observation: On binary plots of element ratios, simple

mixing almost always produces hyperbolae.

Simple mixing: The case of straight lines on element ratio plots

Magma 10% G 30% G 50% G 70% G 90% G Granite

Ba ppm 50 145 335 525 715 905 1000

Sr ppm 100 110 130 150 170 190 200
Ba/Sr 0.50 1.32 2.58 3.50 4.21 4.76 5.00
Rb (ppm) 10 19 37 55 73 91 100

Th (ppm) 5 5.5 6.5 7.5 8.5 9.5 10

Rb/Th 2 3.45 5.69 7.33 8.59 9.58 10
Rb/Sr 0.10 0.17 0.28 0.37 0.43 0.48 0.50

10
9
8
Rb/Th

7
6
5
4
3
2
0.00 1.00 2.00 3.00 4.00 5.00

Ba/Sr

47
 22-07-2015

• In the plot above, of Rb/Th vs. Ba/Sr, a straight line is

obtained instead of a hyperbola.
• This is because, in this case, Srmagma/Srgranite =
Thmagma/Thgranite.
• Sr and Th are the denominators. For all values of this
ratio ≠ 1, hyperbolae are obtained.
• Plotting two ratios with the same denominator will
produce a straight line. (Plotting Rb/Sr vs. Ba/Sr is like
plotting Rb vs. Ba, as Sr is common.)
• Trends with petrological significance claimed on ratio
diagrams with common denominators are suspect, as the
same denominator element artifically enhances the
correlation without petrological reasons (the “common
denominator effect”).

• Substantial simple mixing is not a very realistic process in

Nature, because magmas would rapidly lose their heat.
Magmas usually do not contain superheat, and therefore
magmas must crystallize minerals to produce the heat
required for assimilating wall rocks.
• Combined assimilation-fractional crystallization (AFC) is
a more viable process, in which heat required for
assimilation comes from magma solidification releasing
latent heat of crystallization of minerals.

48
 22-07-2015

Isotope geochemistry

• An atom of an element contains

a very small, positively charged
nucleus which carries most of the
atom’s mass.
• The nucleus is surrounded by a
cloud of negatively charged
electrons that are in motion
around it.
• Atoms have diameters of ~ 10–8
cm (1 Å). The nucleus of an
atom, with a diameter of ~ 10–12
cm (10–4 Å), is 10,000 times
smaller.

• The nucleus contains positively charged

protons and electrically neutral neutrons.
• Protons and neutrons are together called
nucleons.
• An atom (syn. nuclide), is electrically
neutral because the number of protons equals John Dalton
(1766-1844)
the number of electrons.
• The number of protons in a nucleus is called atomic
number (Z) of that element.
• The number of neutrons in a nucleus is called its neutron
number (N).
• The sum of protons and neutrons in the nucleus is the
mass number (A).
A=Z+N

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 22-07-2015

• 6C14 is a nuclide of carbon containing 6 protons, 6 electrons,

and 14 nucleons, and therefore (14 – 6) = 8 neutrons.
• Similarly, 11Na23 is a sodium atom containing 11 protons
and 12 neutrons.
• Isotopes are atoms having the same atomic number (Z) but
different mass numbers (A), e.g., chlorine has two isotopes
(17Cl35, 17Cl37) and strontium has four (38Sr84, 38Sr86, 38Sr87,
88
38Sr ).
• Isotopes are thus atoms of the same element and occupy the
same place in the Periodic Table.
• They have very similar chemical properties and differ only
in their masses.
• Isotopes are of enormous value for petrogenesis, and
absolutely essential for dating rocks (geochronology).

• Isotones are atoms of different elements (different Z),

but have the same N (e.g., 6C16 and 7N17).
• Isobars are atoms of different elements (with different
Z and N both), but have the same masses (A) (e.g., 4Be12,
12 12
5B , 6C ).
• The isotopic abundance of an isotope of an element is
its relative proportion in percent.
• For example, the isotopic abundance of 37Rb85 is
72.15%, i.e., in a sample of Rb containing 10,000 atoms,
7215 atoms would be of Rb85.
• The atomic weight of an element is the sum of the
masses of its naturally occurring isotopes multiplied by
their respective abundances. For example,

50
 22-07-2015

Isotope Mass Abundance Product

35
17Cl 34.96885 amu 0.7577 26.4958
37
17Cl 36.96590 amu 0.2423 8.9568
Atomic wt. of Cl 35.45 amu

Amedeo Avogadro
(1776-1856)

• “Mole” or “gram atomic weight” of an element is the

atomic weight of an element in grams.
• One mole of an element or compound (e.g., 35.45 g of
chlorine), contains a fixed number of atoms or molecules.
This number is 6.02252 x 1023, and is called Avogadro’s
Number (N).
• amu = atomic mass unit; defined as 1/12th the mass of
an atom of 6C12, which is taken as exactly 12.000… amu
• 1 amu = 1/N g

Radioactivity: Half-life and decay constant

• Geological time is vast, measured in millions of years (Ma,

mega anna = 106 years) to billions of years (Ga, giga anna
= 109 years).
• Isotopes are classified into radiogenic isotopes and stable
isotopes. This nomenclature is not really correct, as the two
groups are not opposites.
• Radiogenic isotopes to be used for petrogenetic or
geochronological studies are often stable too.
• It is the radioactive isotopes which are unstable and
undergo decay, and are thus the opposite of stable isotopes.
• 87Rb, a radioactive isotope of Rb, decays to 87Sr. 87Rb is
called the parent isotope, and 87Sr the daughter isotope.

51
 22-07-2015

• The half-life (T1/2) for decay of

87Rb to 87Sr is 48.5 x 109 years. This

is the time it takes for half of the

original atoms of 87Rb to decay to
87Sr.

• If we start with 1000 atoms of

87Rb, then after years, 500 atoms of
87Rb will remain. After another

years, 250 will remain. After

another years, 125 will remain, and Marie Curie (1867-1934)
so on…
• The decay constant (λ) of any
radioactive isotope is equal to
0.693/T1/2. For the 87Rb-87Sr pair, λ
= 1.42 x 10-11 yr-1

Some radioisotopic decay schemes of fundamental

importance and wide use in geochronology
Technique Decay scheme Half-life (T1/2) (yr) Decay constant (λ)
(yr-1)
Rb-Sr 87Rb → 87Sr + β 48.8 x 109 1.42 x 10-11
Sm-Nd 147Sm → 143Nd +α 106 x 109 6.54 x 10-12
K-Ar 40K → 40Ar –β 1.250 x 109 0.581 x 10-10
Re-Os 187Re → 187Os + β 45.6 x 109 1.52 x 10-11
Lu-Hf 176Lu → 176Hf +β 35.7 x 109 1.94 x 10-11
U-Pb 238U → 206Pb 4.467 x 109 1.55125 x 10-10
U-Pb 235U → 207Pb 0.7037 x 109 9.8485 x 10—10
Th-Pb 232Th → 208Pb 14.010 x 109 4.9475 x 10-11

Question: How can year be a unit? A leap year has an

extra day (= 86,400 seconds).

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Decay of a radioactive parent to a stable daughter

The rate of decay (dN/dt) of an unstable parent nuclide is
proportional to the number of atoms (N) present at any time t.
Mathematically, – dN/dt α N (minus sign because the rate is
decreasing with time)
Therefore, – dN/dt = λN
where λ is a proportionality constant, and represents the
probability that an atom will decay within a given amount of
time. It is called decay constant.
The term λN means “rate of decay at any time t”.
Now, – dN / dt = λN, ∴ – dN / N = λdt
Integrating, – ∫ dN / N = λ ∫ dt
i.e., – ln N = λt + C (Eq. 1)
where ln N is the logarithm to the base e of N, e = 2.718…,
and C is the constant of integration.

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When t = 0, N = N0. Thus C = – ln N0 .

Substituting this value in Eq. (1),
we get – ln N = λt – ln N0
∴ ln N – ln N0 = – λt
∴ ln (N / N0) = – λt
∴ N / N0 = e–λt
∴ N = N0e–λt (Eq. 2)
Eq. (2) gives the number of radioactive parent atoms (N) that
remain after decay of an original N0 atoms for time t.
This is the basic radioactive decay equation.

The number of stable daughter atoms D* at time t = N0 – N

∴ D* = N0 – N0e–λt
or D* = N0 (1 – e–λt) (Eq. 3)
Eq. 3 is valid if no daughter atoms were added to or lost from
the system.

The half-life (T1/2) is the time required for one-half of a given

number of radioactive atoms to decay.
When t = T1/2, N = 1/2N0.
Substituting in Eq. (2) yields 1/2N0 = N0e–λT1/2
∴ ln (1/2) = – λT1/2
∴ ln 2 = λT1/2
∴ T1/2 = ln 2 / λ
∴ T1/2 = 0.693 / λ

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The basic age dating equation

If D* represents the number of radiogenic daughter atoms,
D* = N0 – N
Because N0 = Neλt (from Eq. 2), we get
D* = Neλt – N
D* = N (eλt – 1) (Eq. 5)
Generally, any rock has a number of daugher atoms (D0)
present originally (t = 0).
The total number of daughter atoms in such a system is
therefore D = D0 + D*
Since D* = N (eλt – 1) (Eq. 5),
D = D0 + N (eλt – 1) (Eq. 6)
This is the basic radiometric dating equation.
D and N are both measured in a sample, D0 can be calculated if
there are several cogenetic samples of the same age, λ is
known, and t is to be determined.

• The following conditions must be fulfilled for this equation

to be valid:
1. The rock or mineral to be dated must have been a closed
system (has neither lost or gained parent or daughter atoms),
and the ratio D*/N has increased with time only due to
radioactive decay.
2. D0 can be determined.
3. The value of the decay constant (λ) is known accurately.
4. The measurements of D and N must be accurate, and
representative of the rock or mineral to be dated.
Date vs. Age
Any solution of Eq. (6) above yields a “date” which may not
always be geologically meaningful or relevant. It represents
the age only when the four basic assumptions are satisfied,
and when associated with a significant geological event
(e.g., age of rock crystallization or metamorphism).

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Chemical and isotopic fractionation

• Fractionation or differentiation produces widely diverse
reservoirs from a homogeneous one (such as the Earth).
• Chemical fractionation during geological processes occurs
between different elements, due to their different chemical
properties.
• e.g., Rb/Sr ratio of a partial melt is greater than that of the
source (due to Rb being more incompatible than Sr).
• Isotopic fractionation occurs between isotopes of the same
element (with identical chemical properties), due to
difference in mass between them.
• e.g., during seawater evaporation, O16 enters the vapour
phase more than O17, which does so more than O18. Thus
clouds are enriched in O16 relative to seawater.

16O makes up 99.756% of natural oxygen

17O makes up 0.039% “
18O makes up 0.205% “
An international standard for O isotopes is SMOW
(Standard Mean Ocean Water). Any sample’s deviation
from SMOW is measured by the parameter δ18O. This is
calculated as follows and expressed in per mille (‰):

( 18 O/ 16 O) sample − ( 18 O/ 16 O) SMOW
18 16
x1000
( O/ O) SMOW
Thus, clouds have negative values of delta. Most
evaporation occurs over the Equator, clouds are formed,
and drift towards the poles.

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• Clouds cool as they drift poleward and produce rain. When

rain forms, reverse fractionation between 18O and 16O again
occurs, leaving the vapour with still lower delta values.
• The delta parameter is correlated with temperature and thus
O-isotopic studies of ancient marine limestones, corals,
seashells… tell about past temperatures and climates.

Relationship
between
d(18O/16O) and
mean annual
temperature for
meteoric
precipitation,
after Dansgaard
(1964).

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• Isotopic fractionation is pronounced when the relative

mass difference is large, and at low temperatures, e.g., 3He
and 4He are 25% different in mass; 16O and 18O have a
difference in mass of about 1 in 9, also considerable.
• Isotopic fractionation is much less or nonexistent when
relative mass difference is small, and temperatures are high.
• This is why, during partial melting or magma
crystallization, 87Sr and 86Sr are not fractionated from each
other. (Mass difference is only 1 in 87, so both isotopes are
mobilized to the same extent.)
• Therefore, co-existing melt and crystals during melting or
crystallization have the same 87Sr/86Sr ratio (note that
chemical fractionation does occur, e.g., quartz, biotite, K-
feldspar crystallizing from a granitic melt all have different
Rb/Sr ratios).

• Take a garden with many dogs and cats. They are different
animals (= elements). During a fight cats would climb a tree,
the dogs will stay on the ground below (stable equilibrium
positions). This is akin to chemical fractionation.

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• Yet, within cats, which are more or less the same weight (=
mass), but of different colours (white and black), the
white:black ratio of cats now in the tree will be the same as
what it was when they were below. This is akin to lack of
isotopic fractionation, a most useful property of many
geological processes.

• However, if some cats

were thin, and the others
were fat, there should be
more thin cats on the
tree relative to fat ones,
than on the ground. This
would correspond to
isotopic fractionation.

Geochronology: The Rb-Sr dating method

• Imagine a magma which came from the Earth’s mantle and

crystallized.
• When it formed, it inherited the 87Sr/86Sr ratio of its mantle
source, because heavy isotopes are not fractionated at high
(magmatic) temperatures.
• The magma also contained a certain amount of Rb, part of
which was 87Rb.
• As the magma solidified, 87Rb began decaying into 87Sr.
Thus, new 87Sr (= radiogenic growth) started to accumulate in
the rock, besides the 87Sr that originally existed (= initial).

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• If the rock remained a closed system for t years (i.e., no

subsequent loss of 87Sr or addition of new Rb), then
(87Sr)p = (87Sr)i + (87Rb)p (eλt – 1)
where
(87Sr)p = No. of atoms of 87Sr present today
(87Sr)i = No. of atoms of 87Sr initially present
(87Rb)p = No. of atoms of 87Rb present today
• It is difficult to measure the numbers of 87Sr and 87Rb
atoms individually, but mass spectrometers can measure
the relative abundances of various isotopes, i.e., isotopic
ratios, much more easily and precisely.

Alfred Nier (1911-1994), pioneer in the development of

mass spectrometry

• Hence, we introduce the stable isotope 86Sr as a common

denominator. The equation becomes
(87Sr/86Sr)p = (87Sr/86Sr)i + (87Rb/86Sr) (eλt – 1)

• This is the equation of a straight line, Y = C + Xm (m is

slope, C is intercept).
• (87Sr/86Sr)p and (87Rb/86Sr)p are actually measured with a
mass spectrometer.
• The Y-intercept C, here (87Sr/86Sr)i, is known as the initial
ratio and is of great petrogenetic importance.
• It is also written (87Sr/86Sr)t or (87Sr/86Sr)0.
• The slope m is proportional to the age. The slope is eλt –1.
• Solving this for t gives the age of the rock.
• Thus t = 1/λ ln (slope + 1).

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The Rb-Sr isochron diagram

• Plot (87Rb/86Sr)p on the X-axis and (87Sr/86Sr)p on the Y-

axis.
• Have as many rocks as possible with as much spread in the
Rb/Sr (i.e., 87Rb/86Sr) ratio as possible.
• All these rocks must be cogenetic, i.e., when they formed,
all had different Rb/Sr and 87Rb/86Sr ratios due to chemical
fractionation between the various minerals, but all the rocks
had the same (87Sr/86Sr)i due to lack of isotopic
fractionation at magmatic temperatures.
• This is a resonable assumption for different rocks
representing a single liquid line of descent.

Begin with three rocks plotting at a, b and c at time t0.

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

87Sr

86Sr
t1
c1
b1
a1
()87Sr
86Sr
to
a
o
b c

87Rb

86Sr

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At time t2 all rock sample points have again shifted and define
a new line. Thus at all times the rocks are on a straight line
which becomes steeper with time (i.e., slope is proportional
to age of the rocks.) The line’s Y-intercept is however fixed
(the initial ratio).
t2
87Sr
c2
86Sr
t1
b2 c1
a2 b1
a1
()87Sr
86Sr
o a b c to

87Rb/86Sr

• All samples must have been closed systems since

crystallization, i.e., none of the samples acquired 87Sr or lost
87Rb after formation.

• If a rock had minerals which contained no Rb, i.e., the rock

had 87Rb/86Sr = 0, it would simply retain its original 87Sr/86Sr
ratio at all future times.
• Straight lines are fit to the data points by the technique of
regression.
• Note that each data point has errors on both X and Y axes.
Simply put, the regression technique draws a “best-fit” line
through these data points such that the sum of the squares of
distances of the data points from the line is minimum.
• Squares of distances are taken because distances of points
from the line will be both positive and negative.

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• “Goodness of fit” of isochrons: Mean Squares of Weighted

Deviates (MSWD) is a measure of the fit of the line to the data
points within the limits of analytical error.
• Isochrons must have MSWD ≤ 2.5 (ideally < 1).
• Errorchrons have MSWD > 2.5; this means that the scatter is
not just analytical but also geological (= disturbance involving
gain and/or loss).
• Minimum three samples for an isochron; more is better.
• No two-point isochrons!

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• Rb-Sr mineral isochrons can also be derived, where one

plots (87Sr/86Sr)p vs. (87Rb/86Sr)p measured in various minerals
of a single rock sample.
• For example, K-feldspar, plagioclase, and biotite can be
separated from a granite, analyzed, and plotted. (Quartz would
not have either Rb or Sr.)

Disturbance and re-setting of an

isochron:
What does “resetting” of the
isotopic clock mean?

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• Mixing of two components can also produce linear arrays

in isotope diagrams. Even if such straight lines have MSWD
< 1, they are not isochrons.
• They are fictitious isochrons or mixing lines, and have no
age significance (i.e., the slope would yield a meaningless,
and misleading, age, if the mixing is not recognized).

Isotopic evolution diagrams

Plots of isotopic ratio vs. time for the Earth or its component
reservoirs (crust, mantle…)

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• From meteorite analyses,

the 87Sr/86Sr ratio in the
Earth at the time of its
formation is assumed to be
0.69899 (BABI, for Basaltic
Achondrite Best Initial).
• These basaltic achondrites
have no Rb, so their initial
ratio is still unchanged after
4.60 Ga.
• BABI is the lowest
87Sr/86Sr ratio known in the

Solar System; no terrestrial

rock can have a lower ratio
at any time.

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.

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Geochronology: The Sm-Nd Dating Method

• Sm (Z = 62) and Nd (Z = 60) are both lithophile REE.

• Nd has greater radius and smaller atomic number.
• Sm has several isotopes with A = 147, 148, 149, etc. Nd has
seven stable isotopes with A = 142, 143, 144, 145, 146, 147,
148.
• 147Sm decays to 143Nd with T1/2 of 106 Ga.
• So the ratios 147Sm/144Nd and 143Nd/144Nd are of interest.
• 144Nd is actually radioactive (decays to 140Ce), but T1/2 is so
long that it is considered stable. Over the entire 4.5 Ga history
of the Earth, the abundance of 144Nd has decreased due to
decay by only 0.00015%.
• The decay equation is 147Sm → 143Nd + 2He4 + decay energy.

The Sm-Nd System

Both Sm and Nd are LREE
Incompatible elements fractionate → melts
Nd has lower Z → larger → liquids > does Sm

Gerald Wasserburg
Donald J. DePaolo

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• The age dating equation, using 144Nd as the stable ratioing

isotope, is
(143Nd/144Nd)p = (143Nd/144Nd)i + (147Sm/144Nd)p (eλt – 1)
• On the Sm-Nd isochron diagram, plot (143Nd/144Nd)p on the
Y-axis and (147Sm/144Nd)p on the X-axis for the co-genetic
sample suite.
• If the data points for the sample suite do fall on a straight
line within the random errors of the analytical method, an
isochron has been obtained, provided the samples were
comagmatic – all started at the same time (age) with the same
(143Nd/144Nd)i.

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• The 147Sm-144Nd system is thus similar to (but opposite of)

the 87Rb-87Sr system.
• In the Sm-Nd system, it is the daughter element (Nd) which
is more incompatible than the parent element (Sm).
• In the Rb-Sr system, it is the parent element (Rb) which is
more incompatible than the daughter (Sr).
• Thus, during mantle melting, partial melts are “enriched” in
Rb relative to Sr, and in Nd relative to Sm.
• The residual mantle (“depleted” in the incompatible elements
Rb and Nd) acquires higher Sr and Sm.
• Over time, low Rb contents in such depleted sources impart
them low values of 87Sr/86Sr, but their high Sm contents
generate high values of 143Nd/144Nd.
• It is the opposite for enriched sources, such as continental
crust.

The CHUR model

• The isotopic evolution of Nd in the Earth can be represented
by a theoretical model which assumes that the Sm/Nd ratio
and 143Nd/144Nd ratio of the Bulk Earth is equal to that of
chondritic meteorites.
• From meteorite analyses, the present-day 143Nd/144Nd
isotopic ratio in the Bulk Earth is equal to 0.512638. The
present-day 147Sm/144Nd ratio in the Bulk Earth is 0.1967.
• This is the CHUR model, in which CHUR stands for
Chondritic Uniform Reservoir (DePaolo and Wasserburg,
1976).

Gerald Wasserburg Donald J. DePaolo

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The CHUR model

• The CHUR model assumes that terrestrial Nd has evolved in
a uniform reservoir with a Sm/Nd ratio equal to that of
chondritic meteorites.
• (143Nd/144Nd)p of CHUR is 0.512638, relative to
(146Nd/144Nd)p = 0.7219.
• (147Sm/144Nd)p of CHUR is 0.1967.
• Given these values, the (143Nd/144Nd)t ratio of CHUR can be
calculated for any time t , using the equation
(143Nd/144Nd)p = (143Nd/144Nd)t + (147Sm/144Nd)p (eλt – 1)

Partial melting of CHUR gives rise to magmas with lower Sm/Nd

ratios than CHUR. These rocks will therefore evolve lower
(143Nd/144Nd)p ratios than CHUR. The residual solids have
correspondingly higher Sm/Nd ratios than CHUR. These “depleted”
mantle regions will evolve higher (143Nd/144Nd)p ratios than CHUR.

Estimated Nd
isotopic evolution
of the Earth’s
upper mantle,
assuming a large-
scale melting or
enrichment event
at 3.0 Ga.

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Thousands of such partial melting events have occurred during

the long geological history of the Earth.

The Nd isotopic
evolution
curves are the
opposite of Sr
isotopic
evolution
curves.

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 22-07-2015

Nd-Sr isotopes in “depleted” and “enriched” sources

Isotope systematics of two-component mixtures

• For mixing of two end members A and B in varying

proportions, with f being the proportion of end member A in
the mixture, f = A/(A + B), where A and B are the weights of
the two components.
• If an element X has a concentration XA in end member A,
and XB in end member B, the concentration of element X in a
mixture of A and B will be
XM = XAf + XB (1 – f)
Or, XM = f (XA – XB) + XB
• Since XA and XB are constants, XM is a linear function of f.
• The value of f can be determined from the concentration of
any element X in a mixture, provided the concentrations of X
in the two mixing end members are known.

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Similarly, for two elements X and Y and two end members

A and B,
XM = XAf + XB (1 – f)
YM = YAf + YB (1 – f)
These two equations can be combined into one after
removing f.

(YA – YB) YBXA – YAXB

YM = XM ________ + ___________
(XA – XB) XA – XB

• This is the equation of a straight line in coordinates of

XM and YM. It is the locus of all points representing various
mixtures of components A and B.

• Binary mixing processes in geology produce linear

correlations between the concentrations of pairs of
elements, and hyperbolae for isotopic ratios.
• If A and B are components containing different
concentrations of element X, and RX is an isotope ratio of X,
then

RXA XA f + RXB XB (1 – f)
RXM = ____________________
XA f + XB (1 – f)

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Sr & Nd isotopes and binary mixing

• For end members A and B with Sr concentrations SrA and

SrB, and different 87Sr/86Sr ratios, the 87Sr/86Sr ratio in the
mixture would be

(87Sr/86Sr)A SrA f + (87Sr/86Sr)B SrB (1 – f)

(87Sr/86Sr)M = ________________________________
SrM
where SrM = SrA f + SrB (1 – f)
In most cases the binary mixing curve is a hyperbola.
• Also, the relationship between (87Sr/86Sr)M and SrM can be
represented by the equation of a hyperbola:
(87Sr/86Sr)M = a / SrM + b
where a and b are constants specified by the concentrations
and Sr isotope ratios in components A and B.

• This hyperbola can be transformed into a straight line by

plotting (87Sr/86Sr)M vs. 1/SrM.
• For Nd isotopes, the binary mixing equation is

(143Nd/144Nd)M

(143Nd/144Nd)A NdA f + (143Nd/144Nd)B NdB (1 – f)

= __________________________________________
NdM

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 22-07-2015

Problem 1: Given (87Sr/86Sr)A = 0.725, (87Sr/86Sr)B =

0.704, SrA = 200 ppm, and SrB = 450 ppm, plot a graph of
(87Sr/86Sr)M vs. SrM for various mixtures of A and B.

0.730

0.725

0.720
Sr/ Sr
86

0.715
87

0.710

0.705

0.700
150 200 250 300 350 400 450 500

Sr (ppm)

Observation: Isotopic ratio vs. concentration (same

element) = hyperbola

Problem 2: (87Sr/86Sr)A = 0.73691, (87Sr/86Sr)B = 0.70362, SrA

= 160 ppm, SrB = 318 ppm, (143Nd/144Nd)A = 0.51212,
(143Nd/144Nd)B = 0.51300, NdA = 31 ppm, NdB = 18 ppm. Plot
143Nd/144Nd vs. 87Sr/86Sr for various mixtures of A and B.

0.740
0.735
0.730
Sr/ Sr

0.725
86

0.720
87

0.715
0.710
0.705

0.700
0.512 0.5122 0.5124 0.5126 0.5128 0.513 0.5132
143 144
Nd/ Nd
Observation: Isotopic ratio vs. isotopic ratio (different
elements) = hyperbola usually

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Problem 3: Given (87Sr/86Sr)A = 0.72500, (87Sr/86Sr)B =

0.70500, SrA = 200 ppm, SrB = 350 ppm, (143Nd/144Nd)A =
0.51212, (143Nd/144Nd)B = 0.51300, NdA = 20 ppm, NdB = 35
ppm. Plot 143Nd/144Nd vs. 87Sr/86Sr for various mixtures of A
and B. 0.730

0.725

0.720
Sr/ Sr
86

0.715
87

0.710

0.705

0.700
0.512 0.5121 0.5122 0.5123 0.5124 0.5125 0.5126 0.5127 0.5128 0.5129 0.513 0.5131
143
Nd/144Nd

Observation: Two isotopic ratios – straight line –

how on Earth?

Answer:
• For simple binary mixing, the curvature of the mixing
hyperbola depends on (Sr/Nd)A / (Sr/Nd)B.
• The more (Sr/Nd)A is different from (Sr/Nd)B, the greater is
the curvature of the hyperbola.
• When (Sr/Nd)A = (Sr/Nd)B, the mixing curve is a straight
line. Check the values in the last example.

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Distinguishing mixing lines from isochrons

• An isochron, defined on a plot of (87Sr/86Sr)M vs.
(87Rb/86Sr)M always has a positive slope.
• A mixing line on the same diagram can have a positive or
negative slope depending on the mixing end member
compositions. If the latter, there is no ambiguity about it.
But a mixing line with a positive slope, which has no age
significance, must be distinguished from an isochron.
• If it is mixing, data points on a plot of (87Sr/86Sr)M vs. 1/Sr
will give a straight line (just like an isochron). This is why a
mixing line resembles an isochron, because 1/Sr or 1/86Sr
works like 87Rb/86Sr.
• However, for mixing, the sample points on a plot of
(87Sr/86Sr)M vs. Sr will define a hyperbola. (The property of
mixing.) For an isochron, points would be random.

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• For a mixing line, if the mixing event is old, the sample

points will define a straight line on a plot of (87Sr/86Sr)0 vs.
1/Sr, and a hyperbola on a plot of (87Sr/86Sr)0 vs. Sr.
• We should use initial ratios here because post-mixing
radiogenic growth in the individual samples would have
moved the points.

Age of the Earth

• If one wants to determine the age of the Earth, say with the
Sm-Nd method, one needs a reservoir in the Earth that has
not undergone any change in its Sm/Nd ratio since the
formation of the Earth.
• The continental crust, oceanic crust etc. have highly
variable Sm/Nd ratios today due to chemical fractionation of
Sm from Nd during previous and ongoing melting episodes.
• The existence of a primordial, undifferentiated reservoir is
theoretically improbable, and is not suggested by any
evidence.
• If such a reservoir does exist within the Earth, it is not
being sampled by any magmas and is therefore inaccessible
to us.

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• However, many stony meteorites have been thus dated with

the Sm-Nd isochron method at 4.5 to 4.6 Ga.
• By analogy and extrapolation, the age of the Earth is taken
as 4.5 Ga. We have seen chemical evidence that the Earth as
a whole is of chondritic composition.

The Mantle Array

• 143Nd/144Nd and
87Sr/86Sr ratios of young

oceanic volcanic rocks

worldwide vary widely.
• Early studies indicated
a tight anti-correlated
array of Nd-Sr isotopic
data in these rocks.
• No continental crust in
MORB and OIB;
isotopic variability must
reflect mantle source
compositions.
William Albrecht
White Hofmann

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 22-07-2015

• The Mantle
Array is believed
to be due to
mixing.
• However, with
many more
studies, two-
component
mixing cannot
explain the data,
many of which
are inclined to the
main array.
•“Mantle array” is an archaic concept
now, and many more components are
required in the oceanic mantle.

The Bulk Earth 87Sr/86Sr value and UR

• Unlike with Sm-Nd systematics, the Bulk Earth is not
chondritic in terms of Rb/Sr systematics. Rb is a volatile
element, and meteorites have widely varying Rb/Sr ratios
because variable and unknown amounts of Rb were lost to
space during planetary accretion.
• Rb/Sr or 87Sr/86Sr ratios of the Bulk Earth are therefore
impossible to know by comparison with meteorites.
• Bulk Earth (87Sr/86Sr)p can be estimated from the
intersection of the Mantle Array with the εNd = 0 line
(143Nd/144Nd = 0.512638 for Bulk Earth today).
• Thus Bulk Earth (87Sr/86Sr)p ~ 0.7045-0.7055 today. This is a
range, due to the horizontal width of the Mantle Array.
• The theoretical name for Bulk Earth in Sr isotopes is UR
(Uniform Reservoir). It is not chondritic.

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Question: What is the 87Rb/86Sr ratio of Bulk Earth?

Answer: The 87Sr/86Sr ratio in the Earth at the time of its

formation is assumed to be 0.69899 (BABI).
The Earth has 87Sr/86Sr today between 0.7045 and 0.7055.
So, if the age of the Earth is taken as 4.60 Ga,
(87Rb/86Sr)p required in the Earth to evolve from the BABI
value to the present-day value is 0.08165.

Additional slides (for M.Sc. lab class)

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 22-07-2015

Working with Numerical Data: Significant figures

• Question: 12.3 + 4.56 = ?

• 1250 and 569.5 both have four significant figures.

• 445 and 20.3 both have three significant figures.
• 569.55 and 569.50 both have five significant figures (if
the final zero were not significant, it would not be
reported).
• 0.253 and 0.0998 both have three significant figures (they
can also be written as 253 x 10-3 and 998 x 10-4
respectively).
• 34,200 m has anywhere from three to five significant
figures.

The rules are:

• Zeros in the middle of a number are like any other digit,

and always significant.
• Zeros at the beginning of a number are not significant
but act only to locate the decimal point, e.g., 0.029 can be
written 29 x 10-3.
• Zeros at the end of a number and after the decimal point
are always significant. 55.220 oC has five significant
figures. (If this was known to only four significant
figures, we would write 55.22 oC.)
• Zeros at the end of a number and before the decimal
point may or may not be significant, e.g., 34,200 m can be
written 0.34200 x 105 m.

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• During addition, subtraction, multiplication or division,

the result cannot have more significant figures than any of
the original values
i.e., 50.1 g + 0.397 g = 50.497 g; report this as 50.5 g
(three significant figures).
• Pocket calculators calculate results to too many
significant figures, e.g., 50.56 / 2.49 = 20.305221 (by
calculator); write this as 20.3 (three significant figures).
• Instruments that are more “precise” make measurements
to a greater number of significant figures.
• e.g., a simple weighing pan may measure the weight of a
test tube as 11.1 g. It simply cannot be sure about the
fourth figure (11.10 g? 11.13 g? 11.19 g?) A high-precision
electronic balance, however, could weigh it as 11.125 g.

Working with numerical data: Elementary Statistics

• Statistics are very important in geochemistry and
geochronology as these involve large analytical datasets.
• Geochemical data (e.g., SiO2 content of a rock) are
variables.

From “The Cartoon Guide to

Statistics” (Gonick & Smith)

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Histograms

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• Statistical parameters are used to describe two types

of properties of a given data set: central tendency and
dispersion.
• The central tendency is measured by parameters such
as the mean or the median (which are both different
types of averages), and dispersion by parameters such
as the variance or the standard deviation.

• The mean (arithmetic mean, x):

This is the average value of several values.
x = ∑Xi / n, where Xi is the sum of all values and n is
the number of values (measurements).
For eight values of a variable 3, 5, 4, 12, 9, 15, 5, 11,
x = (3 + 5 + 4 + 12 + 9 + 15 + 5 + 11) / 8 = 8

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• The median:
Given five variables 3,
12, 8, 11, 5, rearranging
from smallest to largest
gives 3, 5, 8, 11, 12:
value 8 is the median.
If the number of
variables is even, e.g., 3,
12, 8, 11, 5, 6,
Rearranging gives 3, 5,
6, 8, 11, 12; the median
is the average of the two
middle values, i.e., the
median is (6 + 8) / 2 = 7.

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• It is important to know
if the “average” being
reported is mean or
median. They can be
greatly different, and
can be used to mislead.

• The mean is highly

sensitive to outliers. The
median is not.

• Deviation (d) is a
measure of the difference
between an individual
value and the mean value,
i.e., d = Xi – x. It can be
measured as variance or
standard deviation.

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• Variance (σ2) is defined as σ2 = ∑(Xi – x)2 / (n – 1)

• Standard deviation (σ) is the square root of variance.
σ = √ ∑(Xi – x)2 / (n – 1)
Example: Calculate the mean, variance, and standard
deviation for the following set of measurements:
Xi (Xi – x) (Xi – x)2
1 -2 4
3 0 0
2 -1 1
5 2 4
4 1 1
1 -2 4
5 2 4
N = 7; x = 21 / 7 = 3 ∑(Xi – x)2 = 18
σ2 = 18 / (7 – 1) = 3 σ = 1.732

•Standard deviation has the same units as the arithmetic mean.

• The standard deviation σ is a measure of the dispersion

about the mean. Greater σ means wider curves.
• σ is also called error on the measurement. It does not mean
a mistake. It means the analytical uncertainty associated with
the measurement.
• For the same n (say, n = 25), a measurement 250 ± 10 (1σ)
is more “precise” than another measurement 450 ± 35 (1σ)
ppm.

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The Normal distribution

• Many data sets are “normally”

distributed around the mean. If a
frequency histogram of normally
distributed data is represented by
a smooth curve, the mean will be
at the centre and the mean will
divide the curve into two equal
halves. This is why the mean is
called a measure of central
tendency.
• Thus a normal (syn. Gaussian)
distribution has a symmetrical
bell shape.

• ~ 68% of the area under a normal distribution curve is

within ± 1σ of the mean, ~ 95% of the area under a normal
curve is within ± 2σ of the mean, and ~ 99% of the area
under a normal curve is within ± 3σ of the mean.

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•If σ = 20 ppm, 2σ = 40 ppm, 3σ = 60 ppm, and so on.

This is saying the same thing.
• If the mean Ba value for a normally distributed sample set
is 300 ppm and σ = 10 ppm, then ~68% of the area under
the normal curve will lie between 290 and 310 ppm, ~95%
of the area will lie between 280 and 320 ppm, and ~99% of
the area will lie between 270 and 330 ppm.
• This means that a 68% probability or confidence exists
that the “true” value is between 290 and 310 ppm (if we
were to measure the Ba value an infinite number of times,
then 68% of the times the obtained value would be between
290 and 310 ppm).
• Likewise, there is a 95% probability or confidence that
the true value lies between 280 and 320 ppm, and so on.

• Thus 1σ is called the 68% confidence level, 2σ is the 95%

confidence level, and 3σ is the 99% confidence level.
• Thus a value of 445 ± 15 ppm (1σ) is the same as saying
445 ± 30 ppm (2σ), or 445 ± 45 ppm (3σ). But while
reporting the error, the confidence level must be written.
• To be strictly correct, one should not calculate mean,
standard deviation, etc. unless a normal distribution can be at
least approximated for the variable involved.

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• The mode:
The mode is the value with the highest frequency in a
frequency histogram.
Given a dataset 3, 12, 8, 3, 11, 5, 3, 14, 25, 19, 3, 10
The mode is 3 (appears maximum – four – times).
• For a normal distribution, the mean, median and mode
are the same.

Accuracy and Precision

• These are both measures of quality of analytical data, but

mean quite different things.
• Accuracy indicates how close a measured value is to the
“true” or reference value.
• Precision indicates how reproducible is a measured value,
i.e., how close to each other the various individual
measurements are.
Example: The weight of 1 ml of water is 1.00 g (the “true”
value), so five measurements of
1.00, 1.01, 0.99, 1.01, 1.00 g: high accuracy and precision
1.10, 1.15, 0.90, 0.95, 0.99 g: good accuracy, poor precision
1.12, 1.11, 1.09, 1.10, 1.11g: good precision, poor accuracy
0.85, 1.01, 1.25, 1.07, 0.92 g: poor accuracy and precision

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In the figures
below,
a: Ten
measurements
that are both
accurate and
precise.
b: Ten
measurements
that are accurate
but not precise.
c: Ten
measurements
that are precise
but not accurate.
d: Ten
measurements
that are neither
precise nor
accurate.

Geochemical analyses of rocks

Geochemical data can be divided into:

• Major elements: > 1.0 wt.% of a rock
• Minor elements: 0.1 – 1.0 wt.% of a rock
• Trace elements: < 0.1 wt.% of a rock (i.e., < 1000 ppm)
• Isotopic ratios (e.g., 87Sr/86Sr).
• All major and minor elements together make up nearly
100% by weight.
• Any particular element can be a major element in one
rock (e.g., K in granite) and a minor element in another
rock (K in basalt).
• 1 wt.% = 10,000 ppm (because % is equivalent to pph).

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Making geochemical analyses

• Methods have greatly evolved over many decades.
• Rapid methods of rock analysis: many choices available
• Methods involving “inner” electrons: X-ray fluorescence, X-
ray diffraction, electron probe microanalysis
• Methods involving “outer” electrons: those involving
emission of electromagnetic energy (e.g., inductively coupled
plasma atomic emission spectrometry, ICPAES) and those
involving absorption of electromagnetic energy (e.g., atomic
absorption spectrophotometry)
• Methods involving natural and artificial radioactivity (e.g.,
neutron activation)
• Methods using mass differences (mass spectrometry)

Making geochemical analyses

• Rock crushing/powdering and dissolution in acid
• Avoiding contamination during rock crushing: contamination
from the air, other rock samples, grinding material…
• (Intentional) pre-contamination while grinding different
rocks in a series
• The importance of blanks (reagent blanks)
• Ensuring good precision and accuracy during analysis

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Rock standards/certified reference materials

• “True” values for elements in rock standards are known and
provide a means of estimating the accuracy of an analysis
• Commercially available from the USGS, GSJ and other
organizations
• How are the standards’ values known?
• Which rocks can be good rock standards?
A rock unit which is available in great quantity, fresh and
unaltered, homogeneous throughout…
• There are also standards for soils and other materials.

Calibration curves
• An analytical instrument gives a signal, never the value
directly. Rock standards are first used to make a calibration
curve (signal vs. known concentration). Unknown
concentrations of elements in samples to be analyzed are then
determined from the curve from the signals they produce.

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Regression
• Fitting a line to the
data points involves a
technique called
regression. Note that
all points have
associated errors on
both X and Y. The
line is fit such that
the sum of squares of
distances of points is
a minimum. This is
known as a best-fit
line.
Question: Why use squares of distances?

Calibration curves
• A calibration curve requires at least three standards. A blank
should plot at the origin.
• It is important to choose rock standards that are similar to the
unknown samples lithologically, and which bracket the
compositional range of the unknown samples. This means that
unknown samples should not be located outside the calibration
curve. Why so?

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• Is all of this enough to establish accuracy of the analysis? Is

a major oxide analysis totalling almost 100% necessarily good
(accurate)?
• How about running an additional standard as an unknown
sample? This is critical to demonstrate accuracy.

Correlations and correlation coefficients

Note: Correlation does not indicate causality.

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Spurious correlations and constant sum effect

• Geochemists are always looking for trends in data,
visually represented in various plots.
• A random scatter of data points in a plot does not help or
say much. A systematic linear or curved trend suggests a
systematic process, which needs to be identified, and can be
modelled to reproduce the obtained data.
• Apparent systematic trends, however, can be artificial and
unreal, and a consequence of the method of data treatment
before plotting.

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• AFM diagram: How can the • Moral: Don’t dump

“calc-alkaline” series be geochemical diagrams and
defined here? No calcium. plots, but be aware of their
• A serious problem of the pitfalls. Use them with
AFM diagram is closure. caution and sense!
• Not only do rock analyses add
up to 100% and are thus closed,
we use only four chemical
components out of ten, and
recalculate them to 100% for
the AFM diagram,
compounding the problem.
• Even the TAS diagram is
subject to closure!

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Additional slides (not for M.Sc. class)

The εNd parameter

DePaolo and Wasserburg (1976) defined a parameter
εNd
=
(143Nd/144Nd)sample – (143Nd/144Nd)CHUR
__________________________________ x 104
(143Nd/144Nd)CHUR
• This parameter is a measure of how different a given rock
(coming from a reservoir such as crust or mantle) is, compared
to CHUR (= Bulk Earth).
• For an igneous rock formed today or recently, use its
measured (143Nd/144Nd)p value with the present-day value of
CHUR in above equation.
• Positive values indicate “depleted” sources, and negative
values indicate “enriched” sources.

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• If a rock formed much earlier, say 500 million years ago,

then “age-correction” must be applied to obtain initial ratios.
• Thus (143Nd/144Nd)t at 500 Ma must be calculated for both
the rock and CHUR first, from their present-day 143Nd/144Nd
and 147Sm/144Nd ratios.
• Then, the initial 143Nd/144Nd ratios for both the rock and
CHUR should be used in the εNd equation.

Worked Example of εNd calculation:

Problem 1: An Archaean (3.54 Ga) sodic porphyry from South
Africa has present-day ratios of 143Nd/144Nd = 0.510487 and
147Sm/144Nd = 0.1030. Calculate its present-day and initial

εNd values. (143Nd/144Nd)p CHUR = 0.512638, (147Sm/144Nd)p

CHUR = 0.1967.

Solution: Given (143Nd/144Nd)prock = 0.510487 and (147Sm/144Nd)prock = 0.1030

(143Nd/144Nd)prock – (143Nd/144Nd)pCHUR
εNdprock = _________________________________ x 104
(143Nd/144Nd)pCHUR

(0.510487 – 0.512638)
εNdprock = ____________________ x 104 = – 41.96
0.512638

To determine the εNdtrock for 3.54 Ga, we must have the (143Nd/144Nd)t = 3.54 Ga ratio of
CHUR besides that of the rock.

For CHUR, (143Nd/144Nd)t = (143Nd/144Nd)p – (147Sm/144Nd)p (eλt – 1)

= 0.512638 – (0.1967) [e(6.54 x 10^-12) x (3.54 x 10^9) – 1]
= 0.512638 – 0.004607 = 0.508031

For the rock, (143Nd/144Nd)t = (143Nd/144Nd)p – (147Sm/144Nd)p (eλt – 1)

= 0.510487 – (0.1030) [e(6.54 x 10^-12) x (3.54 x 10^9) – 1]
= 0.510487 – 0.002412 = 0.508075

(0.508075 – 0.508031)
∴ εNdtrock = ____________________ x 104 = 0.87
0.508031

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The Meaning of εNd

• The continental crust is an enriched reservoir, with high
Rb and Nd, and therefore high time-integrated 87Sr/86Sr,
low 143Nd/144Nd, and negative εNd (about –15 or higher)
relative to CHUR.
• The MORB mantle is a depleted reservoir, with low Rb
and Nd (and higher Sr and Sm), and therefore low time-
integrated 87Sr/86Sr, high 143Nd/144Nd, and positive εNd
(about +12) relative to CHUR.
• By definition, CHUR has an εNd value of 0 for all times
– right now, in the past, and in the future.
• Igneous rocks with values ~ 0 need not have come from
CHUR. They can represent mixing of positive-εNd and
negative-εNd sources or their melts.

Nd model ages
• A model age is a
measure of the time a
rock sample has been
separated from its
(presumed) source
mantle (CHUR or DM,
Depleted Mantle).
• It is not a “real” or
direct age, but model-
dependent.

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• For any sample for which the (143Nd/144Nd)p ratio and

(147Sm/144Nd)p ratio are measured, the TCHUR model age
can be derived by constructing the sample’s 143Nd/144Nd
growth curve (with time).
• The intersection of the sample’s 143Nd/144Nd growth
curve with the CHUR 143Nd/144Nd evolution curve yields
the sample’s TCHUR.
• At all times before this, the sample was a part of and
evolving as CHUR.
• The DM 143Nd/144Nd growth curve is steeper than the
CHUR curve. Extending the sample’s 143Nd/144Nd growth
curve to the DM curve yields its TDM.
• As seen, TCHUR and TDM can differ for the same sample
by hundreds of millions of years, and there is no way to
“prove” origin in either.

Mantle components and reservoirs

Zindler and Hart (1986) defined various isotopic
components in oceanic basalts, which may
represent individual reservoirs.
Stan Hart

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• Depleted Mantle (DM): High 143Nd/144Nd, low 87Sr/86Sr

( 0.7030-0.7023), low 206Pb/204Pb. Dominant component
in MORBs.
• HIMU: High 206Pb/204Pb and 208Pb/204Pb, indicating
high long-term 238U/204Pb (this ratio is denoted μ).
Intermediate 143Nd/144Nd, and low 87Sr/86Sr (ca. 0.7030).
Interpreted to represent ancient, subducted,
hydrothermally altered oceanic crust, or Pb loss (relative
to U) from the mantle to the Core or due to
metasomatism.
• EM-I: Enriched Mantle 1, with low 87Sr/86Sr, low
143Nd/144Nd, and high 207Pb/204Pb and 208Pb/204Pb for a

given 206Pb/204Pb. EM-I has affinities with the lower

continental crust and may represent recycling of such
crust, or mantle metasomatism.

• EM-II: Similar, but with higher 87Sr/86Sr. EM-II has

affinities with upper continental crust, and may indicate
such recycled crust.
• Bulk Silicate Earth: Earth without the Core. No data
require the existence of such a reservoir today.
• PREMA: A large number of oceanic basalts have
143Nd/144Nd ~ 0.5130 and 87Sr/86Sr ~ 0.7033. They define

the PREMA (Prevalent Mantle) component. This has

206Pb/204Pb = 18.2-18.5.

• More components have been defined: FOZO (Focal

Zone), ‘C’ (Common), etc.

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FOZO (focal zone):

another
“convergence”
reservoir toward
which many trends
approach. Thus
perhaps a common
mixing end-member
in many ocean
island volcanoes.

Approximate isotopic ranges of various mantle

components and reservoirs
87
Reservoir Sr/86Sr 144
Nd/143Nd 206
Pb/204Pb 207
Pb/204Pb 3
He/4He 187
Os/186Os 18
O/16O
End-Member Mantle
DM 0.7015 - 0.7025 0.5133 - 0.5136 15.5 - 17.7 < 15.45 7 - 9 RA 0.123 - 0.126 low
HIMU 0.7025 - 0.7035 0.511 - 0.5121 21.2 - 21.7 15.8 - 15.9 2 - 6 RA? 0.15 low
EMI c 0.705 < 0.5112 17.6 - 17.7 15.46 - 15.49 2 - 6 RA? 0.152 low
EMII > 0.722 0.511 - 0.512 16.3 - 17.3 15.4 - 15.5 2 - 6 RA? 0.156? high
Other Mantle
BSE 0.7052 0.51264 18.4 15.58 40 - 80 RA? 0.129 low
PHEM 0.7042 - 0.7052 0.51265 - 0.51280 18.4 - 19.0 15.5 - 15.6 > 35 RA low low
PREMA 0.7033 < 0.5128 18.2 - 18.5 15.4 - 15.5
FOZO 0.7028 - 0.7034 0.51287 - 0.51301 19.5 - 20.5 15.55 - 15.71 8 - 32 RA low low
C 0.703 - 0.704 0.5128 - 0.5129 19.2 - 19.8 15.55 - 15.65 20 - 25+? low low
Continental Crust 0.72 - 0.74 0.507 - 0.513 up to 28 up to 20 ~ 0.1 RA high high
DM, HIMU, EMI, EMII, BSE from Rollinson (1993) p. 233-236, PHEM from Farley et al. (1992), FOZO from Hauri et al. (1994) and Stracke et al. (2005), C from
Hanan and Graham (1996), Os values from Shirey and Walker (1998) and van Keken et al. (2002), O estimates based on Eiler (2001).

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An (irritatingly) complex chemical geodynamics model for

oceanic magmatism
“Everything goes and nobody knows”

Credits for photos and images and diagrams:

H. C. Sheth, P. C. Ragland, F. Albarede, J. D. Winter, Wikipedia, and others

Please do not use or circulate without permission

This presentation last updated 14/07/15

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