Stable Isotopes

What is (stable) isotope?

The isotope of an atom is determined by the number of neutrons in the nucleus. Different
isotopes of the same element have very similar chemical properties because chemical
reactions depend almost entirely on the number of electrons that an atom has.

The number of protons and neutrons together determine the nuclide (type of nucleus). Protons
and neutrons have nearly equal masses, and their combined number, the mass number, is
approximately equal to the atomic mass of an atom. The combined mass of the electrons is
very small in comparison to the mass of the nucleus, since protons and neutrons weigh
roughly 2000 times more than electrons.

Stable isotopes are chemical isotopes that are not radioactive. Stable isotopes of the same
element have the same chemical characteristics and therefore behave almost identically. The
mass differences, due to a difference in the number of neutrons, result in partial separation of
the light from heavy isotopes during chemical reactions (isotope fractionation).

Radioactive decay is the set of various processes by which unstable atomic nuclei emit
subatomic particles (radiation). Decay is said to occur in the parent nucleus and produces a
daughter nucleus. This is a random process, i.e. it is impossible to predict the decay of
individual atoms. A lack of necessary neutrons makes a nucleus unstable. Protons in the
nucleus are positively charged, meaning they repel each other. The presence of neutrons is
necessary to separate these protons slightly, making the configuration stable. When the
configuration is unstable, nuclear decay can result, turning the atoms into showers of
radioactive particles.

The rate at which the isotope decays is given by its half-life, the interval after which half of
the material breaks down. Half-life varies between a fraction of a second and many times
longer than the age of the universe. Some isotopes, like Helium-3, are not radioactive.

Introduction

Most naturally occurring elements consist of more than one stable isotope. In elements with
an atomic mass of less than 40 (i.e. lighter than Ca) it is possible for the isotopes to be
fractionated through physical processes as a consequence of the mass difference between the
isotopes. The degree of mass fractionation is proportional to the mass difference. At atomic
masses higher than 40 the relative mass differences are too small to allow isotopes to become
physically separated.
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In geochemistry the study of stable isotopes is a powerful means of studying the light
elements H, C, N, O and S – a group of elements not easily studied in other ways. These
elements are often the main constituents of geologically important fluids, thus affording a
means of directly studying both the fluids and the effects of fluid-rock interaction. In addition,
stable isotopes are used as tracers to determine the source of an element, as
palaeothermometers and as a means of studying diffusion and reaction mechanisms in
geological processes. It is also used to illustrate its role in elucidation geochemical processes
in igneous, metamorphic and sedimentary rocks. More detailed treatments are given by Hoefs
(1987).

Conventionally stable isotopic are converted in to a gas (usually H2, CO2 or SO2)
analysis and the mass differences are measured in a mass spectrometer. With such commonly
occurring elements as O, H, C and S contamination during sample preparation and analysis is
a particular problem and great care must be taken to ensure clean sample handling.
Increasingly, however, the ion probe and laser microprobe are being used in stable isotope
analysis and a number of recent studies have illustrated how a much finer spatial resolution of
isotopic composition is possible using these techniques.

Notation

Stable isotope ratios are measured relative to a standard and are expressed in parts per
thousand, i. e. parts per mil (0/00). The isotope ratio is expressed as a δ value, or ‘del value’ as
it is sometimes called. Using oxygen isotopes as an example, the δ value is calculated as
follows:

⎡ 18 O/ 16 O (sample) −18 O/ 16 O (standard) ⎤

δ1800 / 00 = ⎢ 18 ⎥ X 1000
⎣ O/ 16 O (standard) ⎦

Thus a δ18O value of +10.0 means that the sample is enriched in 18O relative to the standard
by 10 parts in thousand and a value of -10.0 means that the sample is depleted in 18O relative
to the standard by 10 parts in a thousand.

Isotope fractionation

The chief purpose of studying stable isotopes is as a means of investigating the processes
which in nature separate isotopes on the basis of their mass rather than on the basis of their
chemistry. This is known as isotopic fractionation and takes place in nature in three different
ways:
(1) Isotopic exchange reactions: Isotope fractionation may take place in a conventional
exchange reaction in which, for example, oxygen is exchanged between quartz and magnetite

2Si 16O2 + Fe3 18O4 = 2Si 18O2 + Fe3 16O4

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The isotopic fractionation is controlled by bond-strength and follows the general rule that the
lighter isotope forms a weaker bond than the heavier isotope.

(2) Kinetic processes: Kinetically controlled stable isotope fractionation reflects the readiness
of a particular isotope to react. Kinetic effects are only observed when a reaction does not go
to completion.

(3) Physico-chemical processes such as evaporation and condensation, melting and

crystallization and diffusion.

The fractionation of an isotope between two substances A and B can be defined by the
fractionation factor α:

αA-B = ratio in A
ratio in B

For example, in the reaction in which 18O and 16O are exchanged between magnetite and
quartz, the fractionation of 18O/16O between quartz and magnetite is expressed as

(18 O/ 16 O in quartz
αquartz – magnetite =
(18 O/ 16 O) in manetite

Where ‘18O/16O in quartz’ and ‘18O and 16O in magnetite’ are the measured isotopic ratios in
coexisting quartz and magnetite.

Many physical and chemical factors such as temperature, pressure, kinetic effect, diffusion,
distillation, chemical composition of rocks, and crystal structures control the stable isotope
fractionation.

Oxygen Isotopes
There are three stable isotopes of oxygen which have the following abundances:
16
O = 99.763 %
17
O = 0.0375 %
18
O = 0.1995 %

The isotope ratio 18O/16O is the ratio which is normally determined in oxygen isotope studies
and δ values are calculated from Equation given above. There are currently two isotopic
standards in use for oxygen isotope measurements. Low-temperature geothermometry
measurements are made relative to PDB, a belemnite from the cretaceous Peedee formation of
South Carolina, a standard otherwise used for carbon isotope measurements whilst all other
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measurements are calculated relative to concentrations in Standard Mean Ocean Water

(SMOW). SMOW was originally a hypothetical water sample with oxygen and hydrogen
isotope ratios similar to those of standard ocean water. Currently a water standard distributed
by the Atomic Energy Agency in Vienna, known as Vienna- SMOW or V-SMOW is used.
This has an 18O/16O ratio identical to SMOW (Gonfiantini, 1978).V-SMOW and PDB δ18O
values are related by the expressions

δ 18OV-SMOW = 1.03091 δ18OPDB + 30.01

and
δ 18OPBD = 0.97002 δ18OV-SMOW – 29.98

Variations of δ18O in nature

δ 18O values vary in nature by about 100 0/00, about half of this range occurring in meteoric
eater (see Figure below). Chondritic meteorites have a very resticted range of δ18O values and
the mantle has a δ18O value of 5.7 ± 0.3 0/00 and this seems to have been constant through time
for the Earth and the Moon (Taylor, 1980). However, Kyser et al. (1982) found that the alkali
basalts in Hawaii are enriched in δ18O by values of 0.5 to 1.0 0/00 over tholeiites and suggested
on the basis of measured diffusion rates (Graham and Harmon, 1983) that the two had distinct
mantle sources. Thus there is some evidence for small isotope heterogeneities in the mantle.

Most granites, metamorphic rocks and sediments are enriched in δ18O relative to the mantle
value, whereas seawater and meteoric water are depleted, thus forming complementary δ18O
reservoirs.

(Figure shows natural oxygen isotope reservoirs)

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Oxygen isotope thermometry

One of the first applications of the study of oxygen isotopes to geological problems was to
geothermometry. Ure (1947) suggested that the enrichment of 18O in calcium carbonate
relative to seawater was temperature-dependent and could be used to determine the
temperature of ancient ocean waters. The idea was quickly adopted and palaeotemperatures
calculated for the Upper Cretaceous seas of the northern hemisphere. Subsequently, a
methodology was developed for application to higher-temperature systems based upon the
distribution of 18O between mineral-pairs. An excellent review of the methods and
applications of oxygen isotope thermometry is given by Clayton (1981).

There are both low-temperature and high-temperature application of oxygen isotope

thermometry.

Low-temperature thermometry: The earliest application of oxygen isotopes to geological

thermometry was in the determination of ocean palaeotemperatures. The method assumes
isotopic equilibrium between the carbonate shells of marine organisms and ocean water and
uses the equation of Epstein et at. (1953) which is still applicable despite some proposed
revision (Friedman and O’Neil, 1977)

T 0C = 16.5 – 4.3(δc – δw) + 0.14(δc – δw)2

Where δc and δw are respectively the δ18O of CO2 obtained from CaCO3 by reaction with
H3PO4 at 25oC and the δ18O of CO2 in equilibrium with the seawater at 25oC.

High-temperature thermometry: Stable isotope systems are frequently out of equilibrium in

rocks which formed at high temperatures as a result of equilibrium with a fluid phase
following crystallization. This fact can be used to make inferences about the nature of rock-
water interaction but it is not useful for peak-metamorphic temperatures in igneous and
metamorphic rocks.

Use of oxygen isotope, together with radiogenic isotope, in

correlation diagrams
Correlation between radiogenic and oxygen isotopes are particular importance because
variations in the two types of isotope come about through totally different mechanisms.

Recognizing crust and mantle reservoirs

Oxygen isotopes provide a very effective way of distinguishing between rock which formed
in equilibrium with the mantle and those which formed from the continental crust. In general
the continental crust is enriched in δ18O relative to the Earth’s mantle (see Figure below). This
has come about largely as a consequences of the long interaction between the continental
crust and the hydrosphere and the partitioning of 18O into crustal minerals during low-
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temperature geological processes. Oxygen isotope, therefore, are a valuable indicator of

surface processes and useful tracer of rocks which at some time have had contact with the
Earth’s surface.

(Figure shows approximate ranges of δ18O and 87

Sr/86Sr in common igneous and
sedimentary rocks)

Radiogenic isotope, on the other hand, show differences between crust and mantle reservoirs
which are a function of long-lived differences in parent/daughter element ratios and indicate
the isolation of the reservoirs from one another for long periods of Earth history. This give
rise to crustal reservoirs which generally are enriched in 87Sr/86Sr and in radiogenic lead
isotopes but depleted in 143Nd/144Nd relative to mantle.

Recognizing crustal contamination in igneous rocks

Crustal rocks are enriched in both strontium and oxygen isotopes relative to the mantle; thus a
bivariate Sr-O isotope correlation diagram is a powerful means of recognizing crustal
contamination in mantle-derived rocks. There are two contamination mechanism – the
contamination of the source region and contamination of a magma during its ascent through
the continental crust. These two types of contamination may be distinguished from one
another from the shape of mixing curve on a Sr-O isotope plot. In the case when the
contaminant in a source region is enriched in Sr relative to the mantle and form a relatively
small proportion of whole , then contamination on an 87Sr/86Sr vs δ18O mixing diagram is
characterized by the convex-downward curvature of the mixing line (see Figure below). This
arises because crustal materials are not only enriched in Sr relative to the mantle but also their
87
Sr/86Sr ratio is greater than that of the mantle and thus dominates any mixure of the two.
Oxygen concentrations, however, are broadly similar in all rocks so that there is no massive
increase in the oxygen isotope ratio of the derivative melt. The small increase in δ18O is a
simple linear function of the bulk proportion of crustal to mantle materials.
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Recognizing simple crystal fractionation in igneous rocks

An igneous system which has not suffered crustal contamination will exhibit the radiogenic
isotope characteristics of the source, for radiogenic isotope ratios are not altered by crystal-
liquid equilibria such as crystal fractionation. Oxygen isotopes, on the other hand, do show
small changes in isotope ratio with crystal fractionation, although extreme fractionation is
required to produce small changes in δ18O.