STABLE AND RADIOGENIC ISOTOPES

(in Ores and Host rocks)

Geochemistry involves a study of the chemical composition of Earth and other

planets. The Chemical processes and reactions that govern the composition of rocks
and soils, and the cycles of matter and energy that transport the Earth's chemical
components in time and space are revealed by geochemical studies. Isotope
geochemistry is the most important field of geochemistry which involves the
determination of the relative and absolute concentrations of the elements and their
isotopes in the earth and on its surface. Broadly, the field is divided into two
branches: stable and radiogenic isotope geochemistry.
Isotopes of an element are atoms that have the same numbers of protons and electrons
but different numbers of neutrons. This means that various isotopes of an element
have similar charges but different masses. The superscript number to the left of the
element designation indicates the number of protons plus neutrons in the isotope. For
example, among the hydrogen isotopes, deuterium (denoted as D or 2H) has one
neutron and one proton. This is approximately twice the mass of protium ( 1H) whereas
tritium (3H) has two neutrons and is approximately three times the mass of protium.
All isotopes of oxygen have 8 electrons and 8 protons; however, an oxygen atom with
a mass of 18 (denoted 18O) has 2 more neutrons than oxygen-16 (16O).
The original isotopic compositions of planetary systems are a function of nuclear
processes in stars. Over time, isotopic compositions in terrestrial environments change
by the processes of radioactive decay, cosmic ray interactions, and such anthropogenic
activities as processing of nuclear fuels, reactor accidents, and nuclear-weapons
testing.

Stable and Radiogenic Isotopes

Radioactive (unstable) isotopes are nuclei that spontaneously disintegrate over time to
form other isotopes. During the disintegration, radioactive isotopes emit alpha or beta
particles and sometimes also gamma rays. The so-called stable isotopes are nuclei that
do not appear to decay to other isotopes on geologic timescales, but may themselves
be produced by the decay of radioactive isotopes. For example, 14C, a radioisotope of
carbon, is produced in the atmosphere by the interaction cosmic-ray neutrons with
stable 14N. With a half-life of about 5730 years, 14C decays back to 14N by emission of
a beta particle; the stable 14N produced by radioactive decay is called "radiogenic"
nitrogen.
Terminology:

Stable isotope compositions of low-mass (light) elements such as oxygen, hydrogen,

carbon, nitrogen, and sulfur are normally reported as values. values are reported
in units of parts per thousand (denoted as or permil) relative to a standard of known
composition. values are calculated by:
(in ) = (Rx / Rs - 1) 1000

where R denotes the ratio of the heavy to light isotope (e.g., 34S/32S), and Rx and Rs are
the ratios in the sample and standard, respectively. For sulfur, carbon, nitrogen, and
oxygen, the average terrestrial abundance ratio of the heavy to the light isotope ranges
from 1:22 (sulfur) to 1:500 (oxygen); the ratio 2H:1H is much lower at 1:6410. A
positive value means that the isotopic ratio of the sample is higher than that of the
standard; a negative value means that the isotopic ratio of the sample is lower than
that of the standard.

Various isotope standards are used for reporting light stable-isotopic compositions.

Basic Principles
Because of their mass differences, different isotopes of an element have slightly
different chemical and physical properties. Isotopes of low atomic numbers have mass
differences that are large enough for many physical, chemical, and biological
processes or reactions to "fractionate" or bring about a change in the relative
proportions of various isotopes. As a result of fractionation, waters and solutes often
develop unique isotopic compositions (ratios of heavy to light isotopes) that may be
indicative of their source or of the processes that formed them. Two different types of
processes -- equilibrium and kinetic isotope effects -- cause isotope fractionation.
a) Equilibrium Isotopic Fractionation, and
b) Kinetic Isotopic Fractionation

Equilibrium Isotopic Fractionation: In equilibrium isotope-exchange reactions the

isotopes of an element are redistributed among various mineral species. At
equilibrium, the forward and backward reaction rates of any particular isotope are
identical. This does not mean that the isotopic compositions of two minerals in
equilibrium are identical, but that the ratios of different isotopes in each mineral are
constant. During equilibrium reactions, the heavier isotope generally becomes
enriched (preferentially accumulates) in the mineral or compound with the higher
energy state. For example, in coexisting sulfates and sulfides, 34S is enriched in the
sulfate relative to the sulfide; consequently, the sulfide is described as depleted in 34S
relative to sulfate. During phase changes, the isotopic ratios in molecules in the two
phases change. For example, as water vapor condenses (an equilibrium process), the
liquid phase becomes enriched in heavier isotopes ( 18O and 2H) while the vapour
phase become enriched in lighter isotopes (16O and 1H).
Kinetic Isotopic Fractionation: Kinetic isotope fractionations occur in systems out
of isotopic equilibrium where forward and backward reaction rates are not identical,
or the reaction is unidirectional. Some reactions may become unidirectional if the
reaction products become physically isolated from the reactants. Reaction rates
depend on ratios of the masses of isotopes and their vibration energies. As a general
rule, bonds between the lighter isotopes are weaker and hence broken more easily than
bonds between the heavy isotopes. Hence, the lighter isotopes react more readily and
become concentrated in the products, and the residual reactants become enriched in
the heavy isotopes.
In general, biological processes are unidirectional and are excellent examples of
"kinetic" isotope reactions. Organisms preferentially use the lighter isotopic species
because of the lower energy required for bonding. This results in significant
fractionations between the heavier (substrate) and the lighter (biologically mediated)
product. The magnitude of fractionation depends on the reaction pathway utilized and
the relative energies of the bonds being broken and formed during reactions. In
general, slower reactions show greater isotopic fractionation than faster reactions
because the organism has time to be more selective. Kinetic reactions can result in
fractionations much larger than equivalent equilibrium reaction.
Isotopic fractionation can take place either under purely equilibrium conditions or by
kinetic isotopic fractionation. It must be understood that whereas one or the other
may be the dominant process, in most cases there is always some contribution by the
other. For example, although evaporation can take place under purely equilibrium
conditions (i.e., at 100% humidity when the air is still), more typically the products
become partially isolated from the reactants (e.g., the resultant vapor is blown
downwind). Under these conditions, the isotopic compositions of the water and vapor
are affected by an additional kinetic isotope fractionation of variable magnitude.

Use of Various Isotopes Ores and Host Rocks

Sulfur Isotope Geochemistry: A substantial fraction of all economically valuable

metal ores are sulfides. These have formed in a great variety of environments and

under a great variety of conditions. Sulfur isotope studies have been very valuable in
sorting out the genesis of these deposits.
There are two major reservoirs of sulfur on the Earth that have uniform sulfur isotopic
compositions: the mantle, which has 34S of ~0 and in which sulfur is primarily
present in reduced form, and seawater, which has 34S of +20 and in which sulfur is
present as SO42-. Sulfur in sedimentary, metamorphic, and igneous rocks of the
continental crust may have 34S that is both greater and smaller than these values. All
of these can be sources of sulfide in ores, and further fractionation may occur during
transport and deposition of sulfides.

Oxygen Isotope Geochemistry: Oxygen isotope studies can be a valuable tool in

mineral exploration. Mineralization is very often (though not exclusively) associated
with the region of greatest water flux, such as areas of upward moving hot water
above intrusions. Such areas are likely to have the lowest values of 18O.

Lead-Lead Isotope Geochemistry: Lead has four stable isotopes

- Pb, Pb, Pb, Pb and one common radiogenic isotope 202Pb with a half-life of
204 206 207 208

~53,000 years. Lead is created in the Earth by the decay of transuranic elements,
primarily uranium and thorium.
Lead isotope geochemistry is useful for providing isotopic dates on a variety of
materials including ores and their host rocks. Because the lead isotopes are created by
decay of different transuranic elements, the ratios of the four lead isotopes to one
another can be very useful in tracking the source of melts in igneous rocks or the
source of sediments. It has been used to date ice cores from the Arctic shelf, and
provides information on the source of atmospheric lead pollution.

Samarium-Neodymium: Samarium-neodymium is an isotope system which can be

utilized to provide information on age as well as the source of ore material. 147Sm
decays to produce 143Nd with a half life of 1.06x1011 years. This initial ratio is
modelled relative to CHUR - the Chondritic Uniform Reservoir - which is an
approximation of the chondritic material which formed the solar system. CHUR was
determined by analysing chondrite and achondrite meteorites.
Differences in the ratios of the sample relative to CHUR can give information on
whether the ore material was supplied by a granitic source (depleted in radiogenic
Nd), the mantle, or an enriched source.

Rhenium-Osmium: Rhenium and osmium are chalcophile elements which are

present in very low concentrations in the crust. Rhenium undergoes radioactive decay
to produce osmium. The ratio of non-radiogenic osmium to radiogenic osmium varies
through geological time.
Rhenium enter sulfide minerals more readily than osmium. Hence, during melting of
the mantle, rhenium is stripped out, and prevents the osmium-osmium ratio from
changing appreciably. This locks in an initial osmium ratio of the sample at the time of
the melting event. Osmium-osmium initial ratios are used to determine the source
characteristic and age of mantle melting events.

3
He-4He: 3He was trapped in the earth at the time of its creation. It has been observed
that 3He is present in volcanic emissions and oceanic ridge samples. 3He associated
with the mantle and is used as a marker of material of deep origin. Due to similarities
in helium and carbon in magma chemistry, outgassing of helium requires the loss of
volatile components (water, carbon dioxide) from the mantle, which happens at depths
of less than 60 km. However, 3He is transported to the surface primarily trapped in
crystal lattice of minerals and in fluid inclusions.
4
He is produced by decay of uranium and thorium. The continental crust has become
enriched with these elements relative to the mantle and thus more 4He is produced in
the crust than in the mantle.
The ratio (R) of 3He to 4He is often used to represent 3He content. R is usually given as
a multiple of the present atmospheric ratio (Ra).
Common values of R/Ra for geological materials are:
Old continental crust: < 1
mid-ocean ridge basalt (MORB): 7 to 9
Spreading ridge rocks: 9.1 3.6
Hotspot rocks: 5 to 42
Ocean and terrestrial water: 1
Sedimentary formation water: < 1
Thermal spring water: 3 to 11
3
He/4He isotope chemistry is being used to date groundwater, estimate groundwater
flow rates, track water pollution, and provide insights into hydrothermal processes,
petrogenesis and ore genesis
Isotopic compositions are determined in specialized laboratories using isotope ratio
mass spectrometry. The analytical precisions are small relative to the ranges in
values that occur in natural earth systems. Typical one standard deviation analytical
precisions for oxygen, carbon, nitrogen, and sulfur isotopes are in the range of 0.05
to 0.2; typical precisions for hydrogen isotopes are poorer, from 0.2 to 2.0,
because of the lower 2H:1H ratio.

ORE DEPOSITS OF SUB AERIAL VOLCANIC ASSOCIATION

Volcanic ore deposits include metallic ores, non-metallic oresor industrial minerals
(clays, zeolites) and for that matter, water in its natural form (drinking, agricultural) or
as geothermal springs. Ore deposits associated with subaerial volcanism include Ni-
Cu PGE (platinum group elements) deposits associated with subaqueous ultramafic
flows, and Au-Ag and Zn-Cu-Pb (Au-Ag) deposits associated with subaerial
(epithermal deposits) and subaqueous (volcanic-associated massive sulfide) volcanic
centres respectively.

There is no doubt that metallic ores of Cu, Ni, Zn, Au, Ag and PGE hosted by
volcanic rocks are of great economic significance for many countries such as Canada,
Australia and Chile. Copper and gold has been mined from volcanic rocks in Rome,
Cyprus and Turkey around 2500 BC. Gold ores in volcanic rocks convinced investors
to support Columbus voyage to the Far East 1n 1492.

Two distinct types of Ni-Cu (PGE) ore deposits occur within komatiitic flow
sequences. The different types differ in their morphology, percent sulfide, grade and
location within different flow facies. Komatiite hosted Ni-Cu sulfide ores contain
approximately 25 % of the worlds known Ni resources.

Ore mineral assemblages occurring in volcanic rocks

a. Cu-Fe-Zn assemblages in volcanic rocks

b. Stratiforn Sulfide Deposits of marine and marine-volcanic affiliation. These

include chemical sedimentation and sulfide pyroclastic concentrations
interbedded with some lavas. All these are essentially sea floor volcanic
accumulations. A few of these are associated with basaltic and more mafic
lavas Eg Cyprus and Japan, whereas a vast majority are associated with
andesitic and dacitic rocks. Eg Base metals of Ontario, Mount Isa and
McArthur River (Precambrian); Bathurst, New Brunswick and E. Australia
(Paleozoic) and Japan (Tertiary).

c. Mineral deposits associated with flood basalts, for example the copper bearing
lavas of the Keweenaw Peninsula, Lake Superior; copper bearing lavas of the
Deccan traps around Bhawani Mandi, Rajasthan.