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Faculty of Engineering
Department of Geoscience and Environment

Principles of Geochemistry
Lecture 3: Chapter 3: Isotope Geochemistry
Lecturer: Dr. Abdullahi Osman Goyle
Oct 9th, 2024
 Introduction

❑ The chemical properties of an element are

defined by the number of protons in their
nucleus.
❑ Different isotopes of an element have
different numbers of neutrons,
❑ And therefore different atomic masses.
❑ Isotope geochemistry: study the behavior of
isotopes, in:
• Natural systems and earth processes
• And the causes of its relative abundance.
 Types of isotopes

Type Details
Stable isotopes Don’t decay (16O, ¹²C..)
Unstable isotopes Decay into another elements,
The more differences in number of p & n the
more the unstable atoms such as (U → Pb)

❑ Most elements have ≥ 2 stable isotopes

❑ Some have long-lived radioactive isotopes
❑ large group of short-lived radio isotopes does occurs in nature
❑ Isotopes of elements are found in nature with different abundances
 Introduction

❑ Radioactivity: Spontaneous decay (transform) of element to another and

doing so give off particles or radiation.
❑ Mass number (A): total number of protons (p⁺) + number of neutrons (n)
 The N-Z graph

❑A graph of the number of protons

(Z) against the number of neutrons (N) can
be used to predict which isotopes are stable
and which will emit alpha or beta radiation.
❑ Description:
o For proton numbers (Z) up to 20, N=Z is a
straight line.
o For all nuclei with Z >20 , unstable nuclei
have more neutrons than protons, the line
curves upwards.
o Unstable nuclei above the stability curve
are called neutron-rich.
History of Radiometric dating

❑ 1896 Henri Becquerel discovers that

uranium is radioactive
❑ 1898 Marie Curie discovers that thorium
is radioactive
❑ Then Marie Curie discovers that
Polonium and Radium are radioactive.
❑ Because of intensity of the rays that
Radium emits, She called Radioactivity
after this Element.
❑ Ernest Rutherford discovered Alpha
Beta, and Gama Rays.
❑ 1902 Rutherford & Frederick Soddy
discovered law of radioactivity decay
History of Radiometric dating

❑ The phenomenon of radioactive decay attracted

geologists.
❑ Arthur Holmes was leading work in this field.
❑ 1911 Arthur Holmes publishes chemical U-Pb
ages of rocks within 20% of modern values.
Estimates age of Earth at 3.3 Ga
❑ 1919 Francis Aston invents the mass
spectrometer
❑ 1938-1941 Alfred Nier lays foundations of
modern U-Pb isotopic geochronometry
❑ 1953 Clair Patterson measures the primeval Pb
in the Cañón Diablo meteorite and determines
the modern age of the solar system 4.55 Ga.
 Types of radioactivity

❑ Four types of radioactivity are known:

1) Alpha deay:
❑ Spontaneous emission of a nuclear particle comprising:
❑ 2 neutrons + 2 protons, i.e., a helium nucleus
A A - 4 D +4 He + Q
ZX Z-2 2

238
U 234
92 Th + 4 He + Q
90 2
 Types of radioactivity

2) Beta Decay: this can be happen in three ways:

❑ Neutron changes to proton and electron and the electron emitted from the
nucleus as beta negative β- .
o Atomic number increased by +1
o Radionuclides with excess neutrons undergo beta-minus decay
o No change in atomic weight
o It is assumed that the nucleus emits an antineutrino along with the electron.
o The decay equation is written:
Neutron Proton + 𝜷- + vҧ
 Types of radioactivity

❑ Beta-plus radioactivity:
o A proton disintegrates into a neutron.
o The nucleus emits a positron (anti-electron) at the same time as neutrino.
o Radionuclides with neutron deficiency undergo beta-plus decay
Proton Neutron + 𝜷+ + v + Q
40 K 𝟒𝟎
𝑨𝒓 + 𝜷++v+Q
19 18
 Types of radioactivity

❑Electron capture:
o One of orbital Electron is captured by the nucleus.
o Proton changes to neutron
o The Atomic number is decrease by 1 but the mass number remains constant
Proton + electron neutron + neutrino
AX + e- AY + v
𝒁 Z−1
o 40K + e- 40Ar + v + Q
𝟏𝟗 18
The N-Z graph
 Spontaneous fission

❑ Fission is a chain reaction caused by neutrons

when they have sufficient energy.
❑ The elementary reaction splits a uranium
nucleus into two unequal parts.
❑ For example a krypton nucleus and a xenon
nucleus, and many neutrons.
❑ These neutrons in turn strike other uranium
atoms and cause new fission reactions,
❑ And neutron reactions on the nuclei formed by
fission.
 Spontaneous fission

❑The nucleus that splits does not always produce the same nuclei but a
whole series of pairs.
❑ Notice that the last two types of radioactivity (and fission) breakup
the nucleus.
❑ They are called partition radioactivity.
 Radioactivity and heat

❑ Each form of radioactive decay is associated with the emission of particles

or 𝜸 electromagnetic radiation.
❑ Interaction of this radiation with the material surrounding the radioactive
isotope creates heat, as Pierre Curie and Albert Laborde realized in 1903.
❑ This heat is exploited in nuclear reactors to generate electricity.
 Radioactivity and heat

❑Inside the Earth, the radioactivity of (K-

40), 238
𝟗𝟐 U, 235U, and (Th-232) is one of
𝟗𝟐
the main sources of internal energy,
giving rise to plate tectonics and
volcanism and to the heat flow measured
at the surface.
❑ In the early stages of the Earth’s history,
this radioactive heat was greater than
today because the radioactive elements
above were more abundant
 Basic Principles

❑The Curie-Rutherford-Soddy (CRS) law says that the number of nuclei that
disintegrate per unit time is a constant fraction of the number of nuclei
present, regardless of the temperature, pressure, chemical form, or other
conditions of the environment.
❑It is written: dN/dt ∝ N
- dN/dt = λN
❑ Where N is the number of nuclei (parent atoms),
❑ and λ is a proportionality constant called the decay constant.
❑ It is the probability that any given nucleus will disintegrate in the interval of
time dt. It is expressed in yr-1 (reciprocal of time)
❑ The expression λN is called the activity and is the number of disintegrations
per unit time.
 Basic Principles

Integrating the previous equation gives:

dN
-‫׬‬ = λ‫ ׬‬d𝒕
N
-ln N = λt + C
Where C is the integral constant, which can be calculated when N = N0 and t = Zero,
Then: C = -ln N0
Substituting in the previous equation we get:
- ln N = λt – ln N0
N
Rearranging : ln N - ln N0 = - λt ⇒ ln - = - λt
N0
N
= e−λt ⇒ N = N0 e−λt
N0
Where N is the number of radioactive nuclei now remaining, N0 the initial number of
radioactive atoms, and t the interval of time measuring the length of the experiment.
 Half Life

❑ The half-life (t) (also written t1/2 ) of a radioactive element is defined by the time it
takes for half the radioactive isotope to disintegrate.
From the fundamental equation of radioactivity we have:
N
ln = - λt
N0
1
ln = - λ t1/2
2
From it t1/2 = ln 2/ λ = 0.69315/ λ
❑ The half-life is expressed in units of time, in thousands, millions, or billions of years.
❑ It can be used to evaluate, the speed at which any radioactive isotope decays.
❑ This observation immediately prompted Pierre Curie in 1902 and independently
Ernest Rutherford and Frank Soddy to think that geological time could be measured
using radioactivity.
 Example

87Rb decays to 87Sr with λ = 1.42× 10-11 y-1

t1/2 = ln 2/ 1.42× 10-11 y-1
t1/2 = 48.8 Ga
❑ λ is calculated experimentally as we can
see from the figure.
❑ A = -dN/dt = λN
A = A0e- λt
ln A = lnA0 - λt (straight line equation)
 The principles of radioactive dating

❑ It is safe to say that no modern discovery in geology could have been made
without radioactive dating.
❑ The ages involved in the earth sciences are very varied.
❑ They are measured in years (yr), thousands of years (Ka), millions of years
(Ma), and billions of years (Ga).
❑ Geological clocks must therefore be varied too, with mean lives ranging from
a year to a billion years.
Types of dating in Geology
Absolute Actual number to describe age (date in yr)
Relative Order of events relative to each other (older, younger, or same
age)
 Dating in Geology

❑ Absolute dating is done using the radioactive isotopes (which decay at a

constant rate)
❑ Rate of decays is constant because don’t depends on any conditions (T, P,
state…)
1) Dating by parent isotopes:
∗
o Imagine we have a radioactive isotope R and NR is the number of atoms of this
isotope.
o Suppose that geological circumstances (crystallization of a rock or mineral,
say) enclose an initial quantity of R,
o i.e., the number of atoms of R at time zero, written N*R(0), in a “box.”
o If the box has remained closed from when it first formed until today, the
number of atoms of R remaining is N*R(t) = N*R(0)e- λt
 Dating by parent isotopes:

❑ Where t is the time elapsed since the box was closed.

❑ If we know the quantity N*R(0) and the decay constant λ, by measuring N*R(t)
we can calculate the age t at which the box closed by using the radioactivity
formula:
1 N∗R(0)
t = ln ( ∗ )
λ N R(t)
2) Dating by parent-daughter isotopes:
o We can’t directly measure N0 (initial parent atom) so we must get expression
relative to daughter atoms and the remaining parent atoms
D* = N0 – N , we know N0 = N eλt
After substitution we get: D* = N - N eλt ⇒ N(1 - eλt )
1 D∗
D* = N(eλt - 1) ⇒ t = ln +1
λ N
 Dating by parent-daughter isotopes:

D = D0 + D* ⇒ D0 + N (eλT - 1)
o Assumptions for age equation
1. Nparant and Ndaughter atoms per
unit weight changed by decay of
parent to daughter
2. The isotopic composition of
parent element was not altered
by fractionation of isotopes at
time of formation of the mineral.
3. λparent is known accurately
4. The analytical data are accurate
 Radioactivity methods

Rubidium – Strontium dating:

❑ Rubidium is a constant companion of potassium during crystallization.
❑ It increases with the increase of K
❑ Rb increase in relative abundance in felsic rocks, and decreases sharply in
mafic and ultramafic rocks just like potassium.
❑ Rb has two isotopes: 85Rb, and 87Rb. The first is stable, and the second is
radioactive.
❑ The last one decays by beta emission to stable isotope 87Sr.
87Sr = 87Sr + 87Rb(eλT - 1)
0
Where 87Sr is the amount of 87Sr measured currently in the mineral or the
rock. And 87Sr0 is the amount of the same isotope in the rock when it was
crystalized. And 87Rb is the amount of Rb isotope that is present in the rock.
Rubidium – Strontium dating:

87Rb 87Sr + 𝜷 + v + E
37 38

D = D0 + N(eλt - 1)

87Sr = 87Sr + 87Rb(eλt - 1)

38 38 3𝟕
t 0
87Sr 87Sr 87Rb
38 = 38 + 37 (eλt - 1)
86Sr 86Sr 86Sr
38 38 38
 Example

Calculate Rb-Sr date and half-life for biotite in ingenious if

87Rb/86Sr = 107.1,
87Sr/86Sr = 3.093,
initial 87Sr/86Sr = 0.7030
and λ = 0.142× 10-10 yr-1
 Solution:

1.42× 10 −11t
3.093 = 0.703 + 107.1((e - 1)
3.093 − 0.703 −11 1.02232
t = ln ( + 1)/ 1.42 × 10 = ln × 1011 = 1.555 Ga
107.1 1.42
ln 2 ln 2
t1/2 = = 11 = 48.8 Ga
λ 1.42 × 10

87Sr
❑ 38
86Sr at 0 represents the initial ratio. i.e., when the rock crystalized. It can’t
38
be measured, but can be estimated using the isochron.
Isochron
End

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