LU 6 ISOTOPE GEOCHEMISTRY

◊ISOTOPES

DEFINITION

Two or more nuclides having the same atomic number, thus constituting the same element,
but differing in the mass number. Isotopes of a given element have the same number of
nuclear protons but differing numbers of neutrons.

Atoms: Atomic number – number of protons

Different atomic numbers – elements

Isotopes: Nuclide - protons and neutrons

Mass numbers - total number of protons and neutrons
Different number of neutrons in nuclei – create varieties of an element - isotopes
Different mass numbers due to different number of neutrons

Nuclide: Nucleus of an isotope is called a nuclide

Stable nuclides - maintain atomic configuration over long periods.
Unstable nuclides - spontaneously change into new atoms.

TYPES:
STABLE ISOTOPES
The atomic nuclei of these elements do not change to nuclei of other elements.

RADIOACTIVE ISOTOPES
The atomic nuclei of these elements give out radiation spontaneously and thereby change
to nuclei of other elements.

◊ RADIOACTIVE ISOTOPES

►NUCLIDE

Nucleus of an isotope is called a nuclide

Stable nuclides - maintain their atomic configuration over long periods of time.
Unstable nuclides - spontaneously change of an unstable nuclide into another nuclide.

►RADIOACTIVE DECAY

□Radioactive Isotopes

Unstable nuclides - spontaneously change of an unstable nuclide into another nuclide.

This phenomenon is called decay

The process is called radioactivity

The isotope is called a radioactive isotope with a radioactivity nuclide.

Parent nuclide (unstable) – before decay the atom containing the radioactive nuclide

Daughter nuclide (stable) – after decay to new configuration

□ Modes of Radioactive Decay

Radioactive decay occurs by one of three processes.

1. Alpha decay
Alpha emission results in releasing an alpha particle. An alpha particle has two protons and two
neutrons, so it has a positive charge. (Since it has two protons it is a helium nucleus.) It is written
in equations like this:

2. Beta decay
Beta emission is when a high speed electron (negative charge) leaves the nucleus. Beta
emission occurs in elements with more neutons than protons, so a neutron splits into a proton and
an electron. The proton stays in the nucleus and the electron is emitted. Negative electrons are
represented as follows:

3. Gamma Emission
Gamma Emission is when an excited nucleus gives off a ray in the gamma part of the
spectrum. A gamma ray has no mass and no charge. This often occurs in radioactive elements
because the other types of emission can result in an excited nucleus. Gamma rays are represented
with the following symbol.

The two types of artificial radiation are positron emission and electron capture.
Positron emission
Positron emission involves a particle that has the same mass as an electron but a positive charge.
The particle is released from the nucleus.
Electron capture
Electron capture is when an unstable nucleus grabs an electron from its inner shell to help
stabilize the nucleus. The electrons combine with a proton to form a neutron which stays in the
nucleus.

□Principle of Radioactive Decay

A key principle of radioactive decay is that there is a constant probability per unit of time (e.g.
1 year) of a decay event from parent atom to a new daughter atom.
This probability is expressed as the decay constant.
Here we explore the decay process graphically.
1. Imagine a batch of 36 parent atoms.
These spontaneously decay to daughter atoms (in green).
2. The probability of such a decay for each parent atom is 1/6 per unit of time.
So after 1 unit of time the most probable outcome is that 5/6 of the original batch of parents
remain (i.e. 30).
3. During the next interval of time 1/6 of the remaining parents will decay (leaving 5/6 of 30
=25 parents).
4. And so it continues.
Because the number of parents reduces for each new time interval, the number of events per
unit of time reduces (although the probability of each parent decaying is constant). This gives
the graph a characteristic shape - exponential decay.

The graph also shows the half-life concept. The half-life is the amount of time necessary to
reduce the number of parent atoms by 50% from the original number.
► The Basic Equation of Radioactive Decay

In any large number of atoms of a radioactive isotope, the decay follows a statistical rule:
During any fixed time interval, a definite proportion of the parent atoms change to the
daughter product.

The number of decays you will measure each second from a sample depends on the number of
atoms in the sample, N.
 2 kg 1 kg

Here are two blocks of exactly the same radioisotope. The chance of an atom decaying from one
is exactly the same as in the other but there are twice as many atoms in the 2 kg block so there
will be twice as many decays per second in the 2 kg block.

Thus the rate of decay, or the number of atoms of decay, is simply proportional to the total
number of parent atoms present:

where
λ = the constant of proportionality, called the Decay Constant.

The decay constant is the proportion of atoms that decay in an interval of time
The decay constant gives you an idea of how quickly or slowly a material will decay.

A large λ value means that the sample will decay more quickly.

Rate of decay of a radioactive nuclide is proportional to the number of atoms of that nuclide
remaining at any time.

If N is the number of atoms remaining, then

- dN/dt = λN (1)
where
λ is the proportionality constant known as the decay constant
N is the number of atoms remaining/present

and the minus sign indicates that the rate of decay decreases with time.

This is a first order differential equation

Solve for N as a function of time

Rearrangement
- dN/N = λdt (2)

Integrate both sides

N t
-∫ dN/N = λ ∫ dt (3)
No 0
By integrating and expressing as natural logarithm (logarithm to base e) we obtain

-In N = λt + C (4)

Where In is the logarithm to the base e

C is the constant of integration

The integration constant C may be expressed in terms of the original number of parent
atoms when t=0

When t=0,
No= number of nuclides at t=0
-In No = (0) + C
C = - In No

Therefore the integrated form of the equation is

In N = λt - In No (5)

Rearrangement
In N - In No = -λt (6)

Present Original
In (N/No) = -λt (7)

Switching to an exponential format (In y = x so y = ex)

N/No = e-λt (8)

The equation above is the basic relationship that describes all radioactive decay processes.

With it, we can calculate the number of parent atoms (N) that remain at any time t from the
original number of atoms (No) present at time t=0.

Rearrangement

Present Original
N = No e-λt (9)

N number of parent atoms currently present

No number of parent atoms originally present when mineral was formed
Λ Each radioactive isotope/ radionuclide has a characteristic decay constant that must be
determined experimentally.

This expression above is known as the Radioactive Decay Law.

It tells us that the number of radioactive nuclei will decrease in an exponential fashion with
time with the rate of decrease being controlled by the Decay Constant.

The Law is shown in graphical form in the figure below:

The graph plots the number of radioactive nuclei at any time, Nt, against time, t. We can see
that the number of radioactive nuclei decreases from N0 that is the number at t = 0 in a rapid
fashion initially and then more slowly in the classic exponential manner.

All three curves here are exponential in nature, only the Decay Constant is different.
• When the Decay Constant has a low value the curve decreases relatively slowly
• When the Decay Constant is large the curve decreases very quickly.

The equation can be rearranged

Original Present
No = N e λt (10)

N number of parent atoms currently present

No number of parent atoms originally present when mineral was formed
Λ Each radioactive isotope/ radionuclide has a characteristic decay constant that must be
determined experimentally.

Note:
 N = N0e-kt (exponential decay)

[ N = N0ekt (exponential growth) ]

where
• N0 is the initial quantity
• t is time
• N(t) is the quantity after time t
• k is the decay constant and
• ex is the exponential function (e is the base of the natural logarithm)

www.earth.northwestern.edu/people/seth/202/DECAY/decay.pennies.slow.html

Decay of parent produces daughter or radiogenic nuclides.

Number of daughters produced is simply the difference between initial number of parents
and number remaining after time t.

original present
D = No – N (11)

Substituting (10) into (11) we obtain (for No)

D = Neλt – N = N (eλt – 1) (12)

This tells us that the number of daughters produced is a function of the number of parents
present and the time.

Since in general there will be some atoms of the daughter nuclide around to begin with, i.e.
when t = 0, a more general expression is:

D = Do + N (e λt – 1) (13)

Where Do is the number of daughters originally present.

Rearrangement

T = 1/λ In (D/Do + 1) (14)

P

This is the time during which an amount of the daughter represented by D has accumulated,
leaving undecayed an amount of the parent represented by P.

Values of D and P are found by analyzing the rock or mineral in which the radioactive
isotope occurs.

If we can also find values for λ and Do the equation will give us the age of the rock or mineral in
years.

The decay constant λ is found by laboratory measurement of decay rate.

□Half-Life

A half-life is the time it takes for half of the parent radioactive element to decay to a daughter
product.
So if you have 10 grams of a radioactive element
After one half-life there will be 5 grams of the radioactive element left.
After another half-life, there will be 2.5 g of the original element left.
After another half-life, 1.25 g will be left.
Radioactive decay occurs at a constant exponential or geometric rate.
The rate of decay is proportional to the number of parent atoms present.

The proportion of parent to daughter tells us the number of half-lives

For example,
If there are equal amounts of parent and daughter, then one half-life has passed.
If there is three times as much daughter as parent, then two half-lives have passed.

We can use the number of half-lives to find the age in years.

o Age is usually the time of crystallization or formation

Approach
o Compare amount of daughter isotope to amount of parent originally there

Example:
Problem: The 235U: 207Pb ratio in a mineral is 1:7.
What is the age of the mineral?
Given: Half-life of 235U is 0.7 billion years (b. y.)

The half-life of an isotope equals the number of years it takes for an initial number of parent
atoms to be reduced to half that number by radioactive decay.

The half-life figure enables us to relatively quickly understand the useful age range of a
particular isotopic system.

For instance, the half life of the C-14 system is 5,730 years - you would never use C-14 to
determine the age of material older than 40 000 years which is the practical upper limit; all of the
radioactivity would be gone.
Each radioactive isotope has its own unique half-life.

Radioactive Parent Stable Daughter Half life

Potassium 40 Argon 40 1.25 billion yrs
Rubidium 87 Strontium 87 48.8 billion yrs
Thorium 232 Lead 208 14.0 billion years
Uranium 235 Lead 207 704 million years
Uranium 238 Lead 206 4.47 billion years
Carbon 14 Nitrogen 14 5730 years

XXXXXXXXXX
□Half-life Equations:

1) Suppose the amount of time for the number of parent atoms to decrease to half the original
number i.e. t when N/No =1/2 is required to be determined.

Take equation (4) below

In (N/No) = -λt (4)

and setting N/No to 1/2 rearrange it to get

In 1/2 = -λt1/2 or In 2= λt1/2 (5)

to finally get
t1/2 = In2/λ (6)

which gives the half-life.

2) Another equation for half-life calculations is as follows:

• AE is the amount of substance left

• A0 is the original amount of substance
• t is the elapsed time
• t1/2 is the half-life of the substance

3) Another variations of the half-life equation are as follows:

An example problem is if you originally had 157 grams of carbon-14 and the half-life of carbon-
14 is 5730 years, how much would there be after 2000 years?

There would be 123 grams left.

http://www.eas.asu.edu/~holbert/eee460/decay.html

http://www.earthsci.org/fossils/geotime/radate/radate.html

◊USE FOR RADIOMETRIC DATING: GEOCHRONOLOGY

Natural radioactive decay provides a variety of clocks that allow the determination of geological
time.

Many radioactive elements can be used as geologic clocks.

►PRINCIPLE OF RADIOMETRIC DATING

Naturally-occurring radioactive materials break down into other materials at known rates.

Each radioactive element decays at its own nearly constant rate.

Once this rate is known, the length of time over which decay has been occurring can be estimated
by measuring the amount of radioactive parent element and the amount of stable daughter
elements.

►RADIOACTIVE DECAY SYSTEMS OF GEOCHRONOLOGICAL INTEREST

The course examines K-Ar, U-Th-Pb, Rb-Sr decay systems and Carbon-14.

►RUBIDIUM-STRONTIUM

Rubidium decays to Strontium via a one step beta decay process with a half-life of 4.7 Ga.

(This method is good for minerals like

micas, k-spar, pyroxene, olivine and whole metamorphic rocks)
The Rb-Sr system exists because
87
Rb (Z=37) decays by beta (-) decay to 87Sr (Z=38)

The decay constant is

λ= 1.42x10-11 y-1.

□ Background

Rubidium: Strontium:
• Univalent • Divalent
• Not very common in the Earth's crust • Occurs as four stable isotopes
(88Sr, 87Sr, 86Sr and 84Sr).

The table below lists the naturally occurring isotopes of both Rb and Sr along with their isotopic
abundances (in atom %) and their nuclide weights in atomic mass units (a. m. u.).

Isotope Atom% abundance Nuclide mass (amu)

Rubidium Isotopes
87
Rb 27.8346 86.90918
85
Rb 72.1654 84.91171

Strontium Isotopes
88
Sr 82.53 87.9056
87
Sr 7.04 86.9089
86
Sr 9.87 85.9094
84
Sr 0.56 83.9134

□ Systematics of the Rb-Sr system

The isotopic composition of Sr in a sample that contains both Sr and Rb is given by:
 i) In this equation, t is the time since the system was formed
(Note that the system is assumed to have remained closed to the exchange of Rb and Sr
since its formation date)
The (87Sr/86Sr)o is the isotopic composition of Sr already in the system at the time of its
formation (the initial ratio) and 87Rb/86Sr is the ratio of Rb to Sr in the system.

ii) As in practice there are commonly daughter atoms already present in a material. So in this
case we must make a correction, estimating the original daughter concentration.
This is done by normalising against a stable reference isotope that is not itself radioactive
or produced by radioactive decay of another isotope. The reference isotope is 86Sr (86Sr)..

iii) The abundance of 87Sr (daughter) is measured relative to a reference isotope. Thus, the Sr
isotopic composition of a sample is reported as the ratio of 87Sr to 86Sr i.e. 87Sr/86Sr

iv) Of these terms, (87Sr/86Sr)t , which is the total 87Sr/86Sr, is measured in the laboratory;
87
Rb/86Sr is calculated from the measured Rb and Sr concentrations in the sample; and
(87Sr/86Sr)o and t are unknowns.

v) The initial ratio and age.

For an individual sample,
• the initial ratio can be calculated from the measured isotopic composition of the sample if
the age of the sample is known or
• the age of the sample can be calculated if the initial ratio is known.

However, if neither the initial ratio nor the age of the sample is known, then neither can
be computed using the equation above.

This limitation can be overcome by studying rocks with different Rb/Sr ratios

If the body of rock under study contains rocks with different Rb/Sr ratios and the rocks
are known, based on geological observations, to have formed at the same time from the
same source, then an equation like the one above can be written for each sample.

• If only two samples are available, the two equations may be solved simultaneously to give
both the initial ratio and the age of the samples.

• If more than two samples are available, then all of the equations are solved
simultaneously using least squares methods to give best fit values for the initial ratio
and the age of the samples. The latter approach is preferred and is called the Isochron
Method.
 □ Methods

Method #1: Direct comparison

• Analyze 87Rb - free sample to find non radiogenic 87Sr/86Sr ratio

(Since no 87Rb in this sample all 87Sr must have been present to start with-- it is not
radiogenic).

• Analyze 87Rb rich sample for 87Rb, 87Sr, and 86Sr

Method #2: The Isochron Method

In this method minerals with varying amounts of Rb are analyzed that are the same age.

• At time of crystallization 87Sr/86Sr ratio is the same for all minerals of the same rock.
• The amount of 87Sr that you measure is equal to the original amount PLUS what has been
generated by radioactive decay of rubidium.

• Samples with varying Rb fall on a straight line in a plot of 87Sr/86Sr vs 87Rb/86Sr as the
axes.

• Radioactive decay equation used as the equation for a line (y = mx + b), where the slope is
proportional to the age.

□ How does this work?

The diagram below
illustrates
the isochron
method.

Consider the four

samples shown as
black dots in the
diagram.
 • All four of these samples have the same initial 87Sr/86Sr ratio (shown by the black dashed
line) but different 87Rb content so different 87Rb/86Sr ratios.

• With time, some of the 87Rb in the samples decays to 87Sr. The red arrows show how the
locations of the samples move as a function of time (note that one Sr is produced by each Rb
that decays).

• The 87Rb decreases while the 87Sr increases. As Rb decays to form Sr and the samples
evolve, they remain colinear.

• You can think of the horizontal line originally defined by the initial ratio of the samples
rotating with its fixed point located at the initial 87Sr/86Sr ratio and an 87Rb/86Sr value of
zero.

Now consider the form of the Sr isotope evolution equation from above:

(λ = decay constant)
• For the variables in the diagram above, this equation is the equation of a straight line (y =
mx + b), where y = (87Sr/86Sr)t, x = (87Rb/86Sr), b = (87Sr/86Sr)o and the slope of the line (m)
is e λt -1.

• The Isochron Method thus consists of plotting measured 87Sr/86Sr values versus calculated
87
Rb/86Sr values for the samples.

• A straight line is then fit to the data using linear regression (most spread sheets and hand
calculators have linear regression functions).

• The slope of the straight line (m) is then equal to:

m = eλt - 1
Thus, the age of the sample suite is given by:
t = ln (m + 1)/ λ

• The intercept of the best fit line gives the initial ratio [(87Sr/86Sr)o] for the sample suite.

The use of this method is based on the validity of the following assumptions:

1. All of the samples are of the same age

2. All of the samples came from the same source and had the same initial ratio
3. The samples were closed to Rb and Sr exchange during their complete histories
 □ Recap

Recall the equation (9) above D = Do + N (eλt – 1) (9)

So! If we substitute in the appropriate

players in the Rb-Sr system:

Recall that there is some 87Sr in the rock

to start with, so what you measure is
equal to the original amount PLUS what
has been generated by radioactive decay
of rubidium.

What we actually measure is the ratio of

these elements relative to the stable
isoptope 86Sr. The equation becomes:

This looks remarkably like the standard

equation for a line
y = mx+b