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; 87Rb/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

87
Rb/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 87Rb/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
 ►POTASSIUM-ARGON (K–Ar) Dating

□ Principle

It is based on the fact that some of the radioactive isotope of

Potassium, Potassium-40 (K-40), decays to the gas Argon as Argon-
40 (Ar-40).

• Potassium (K) is one of the most abundant elements in the Earth's crust
(2.4% by mass).

• One out of every 100 Potassium atoms is radioactive Potassium-

40 (K-40).
40
• The nuclei of naturally occurring K are unstable so undergo
decay.
 The radioactivity of is unusual, in that two processes take place:
β -decay - 89% Electron capture: 11%

• For every 100 K-40 atoms that decay,

• 11 become Ar-40.
• The other 89% of the 40K atoms decay to 40Ca.

• This aspect of this system makes it special i.e. a branched decay:

• A 40K nucleus may decay to either a 40Ca by β- or to a 40Ar atom by

electron capture.

• It is impossible to predict how a given 40K atom will decay, just as it is

impossible to predict when it will decay. We can predict quite accurately what
proportion of a large number of 40K atoms will decay to each, however.

• The ratio of electron captures to beta decays, called the

branching ratio, is defined as:
R = λe / λβ

where the two lambda's are the decay constants (probability of

decay) for each mode.

• The branching ratio is 0.117, λe = 0.581 x 10-10 yr, λβ = 4.962 x 10-

10
yr.

• The total decay constant for 40K is:

λ = λe + λβ = 5.543 x 10–10 yr–1

□K and Ar Dating System

 40
• The decay scheme of the 11% of the K atoms to 40Ar is used. It is
this scheme that makes the K/Ar method work.

• For the K/Ar dating system, this decay scheme to calcium isotopes is
ignored.

• We need, however, to take account of the branched decay in

our equation, as while K decaying to Ca does not produce
radiogenic Ar, it is no longer K and not available for 40Ar
production.

• Thus our equation for radiogenic daughter production becomes:

40
Ar* = λe/λ 40K (eλt–1)

where the asterisk indicates radiogenic Ar.

40
• The buildup of radiogenic Ar (40Ar*) in a closed system can be
expressed by the equation:

• Once the 40Ar and potassium in a rock/mineral are accurately

measured, the amount of 40K (based on the relative abundance of
40
K to total potassium) and 40Ar* (radiogenic 40Ar) must be
calculated as 40Ar which also occurs in the atmosphere can
 adhere to the sample and contaminate it making the calculated
data inaccurate.

• To check for this it is necessary to analyze also for 36Ar which has
a known ratio to 40Ar in the atmosphere (40Ar/36Ar = 296).

• The formula for correcting for atmospheric argon is:

40
Ar (measured) – 296 (36Ar) = 40Ar* (radiogenic)
• The resulting 40Ar* and 40K can be plugged into the age
equation as follows:

□How is the Atomic Clock Set?

• When the rock crystallizes it becomes impermeable to gasses. Any
Ar-40 contained in the magma is already released into the
atmosphere.

• As the K-40 in the rock decays into Ar-40, the gas is trapped in the
rock.

□ Limitations of K-Ar Dating

• The rock should not have gone through a heating-recrystallization

process after its initial formation. No argon should have escaped or
leaked.

• No extra argon should have been added.

►URANIUM-THORIUM-LEAD

□ Nuclear Decay of Uranium

Uranium is a common element in the earth's crust and is widely
distributed in rocks such as granite and basalts.

The relevant radioactive isotopes are: 238U, 235U and 232Th.

The decay schemes are very complex as below

U-Th Decay Series

Since 238U is much more abundant than 235U, let’s look at the decay
sequence for 238U which is given below.
 (235U and 232Th have their unique decay sequences as well).

• Lead is formed by the radioactive decay of Uranium and Thorium.

• The final daughter products are: 206Pb, 207Pb and 208Pb.

 • One isotope of lead, 204Pb, is of non-radiogenic origin. The lead
isotope, 204Pb, is not produced by r. a. decay.

• A summary of the decay schemes and half-lives are:

Lead is formed by the radioactive decay of Uranium and Thorium, as

indicated below.
One isotope of lead, 204Pb, is of non-radiogenic origin.
Parent Daughter Half Life Relative Abundance of Parent
238 206
U Pb 4.468 Ga 99.27%
235 207
U Pb .7038 Ga 0.72%
232 208
U Pb 14.010 Ga ~100%

• The decay schemes above represent three separate

geochronometers

• The availability of three separate geochronometers is an

advantage.

• One problem is that some minerals which were dated contain

Pb at the outset and must be corrected for. This is called
common lead.

• Common lead is corrected for by measurement of 204Pb and

knowledge of the ratios of r. a. Pb relative to other Pb isotopes.

• As with the Rb-Sr system, we can use the stable isotope as a

standard to compare the abundance of the other isotopes

• With the stable isotope, 204Pb, as a standard to compare the

abundance of the other isotopes we have the three equations
below
 • Three sets of isochron diagrams are made based on these
equations above:

The ages should agree. If they do, they are called concordant; if not,
they are discordant.
• Discordant ages indicate that there has been some type of
disturbance which has reset the "time clock" at some time in the
past, such that the steady decrease in U has been interrupted
and reset (e.g., metamorphism).

Ideal closed system

In an ideal closed system, a plot may be made showing the locus of
pairs of the ratios of 206Pb/238U and 207Pb/235U that give the SAME age.

This plot is known as the CONCORDIA curve.

It illustrates the expected ratios in a closed system samples of

different ages.

A schematic one is shown below.

If the CONCORDIA curve is finely calibrated then the age may be

read off directly, otherwise the two isotope ratios for the intercept may
be read off and the age calculated from the equations at the top of
this page.

Loss of radiogenic lead

Few data sets lie on the CONCORDIA curve, however.

Loss of radiogenic lead from minerals usually causes data sets to lie
below CONCORDIA.

A good data set will usually produce a linear plot which may be
extrapolated back to intersect the CONCORDIA curve.

The intercept gives the 'age' of the discordant assemblage.

This is illustrated below:

Use
This dating method is used for zircon, uranite, pitchblende - any
uranium or thorium bearing mineral.

►CARBON-14

□How does Carbon-14 dating work?

a. (i) Cosmic rays (neutrons) from the sun strike Nitrogen-14
atoms in the atmosphere and cause them to turn (by losing a
proton) into radioactive Carbon-14,
(ii) Radioactive Carbon-14, which then combines with oxygen to
form radioactive carbon dioxide (CO2).

b. (i) Living things are in equilibrium with the atmosphere, and the
radioactive carbon dioxide is absorbed and used by plants.
(ii) The radioactive carbon dioxide gets into the food chain and the
carbon cycle.

c. All living things contain a constant ratio of Carbon-14 to Carbon-

12 (1 in a trillion).

d. At death, Carbon-14 exchange ceases and any Carbon-14 in

the tissues of the organism begins to decay to Nitrogen-14,
and is not replenished by new C-14.

The decay clock starts.

The change in the Carbon-14 to Carbon-12 ratio is the basis for

dating.
Assumes that the rate of Carbon-14 production (and hence the amount of cosmic
rays striking the Earth) has been constant (through the past 70,000 years).

As long as an organism is alive, it takes in carbon-14 and other carbon isotopes

in the same ratio as exists in the atmosphere.

Following death, however, no new carbon is consumed.

Progressively through time, the carbon-14 atoms decay and once again become
nitrogen-14.

As a result, there is a changing ratio of carbon-14 to the more atomically stable

carbon-12 in the dead tissue.
That rate of change is determined by the half-life of carbon-14, which is 5730 ±
40 years.

The half-life is so short (5730 years) that this method can only be practically used
on materials less than 40,000 years old.

Beyond 40-50,000 years, there usually is not enough carbon-14 left to measure
with conventional laboratory methods.

Half-Lives
Years Past C-14 Atoms C-12 Atoms

0 0 1N 1N
1 5,730 1/2 N 1N
2 11,460 1/4 N 1N
3 17,190 1/8 N 1N
4 22,920 1/16 N 1N
5 28,650 1/32 N 1N
6 34,380 1/64 N 1N
7 40,110 1/128 N 1N

N = some specific number of atoms

 >>>>>>>>

►AGE DATING ERRORS AND ASSUMPTIONS

1. Rate of decay is independent of external influences (heat, pressure,

etc.)
2. System is closed
3. No daughter present to start with
4. No laboratory error

o Age is given ± some value, which is the precision. Reflects ability to

measure.

Some other things to realize, think about, etc. about "absolute" age
determination:
• Even the best instruments carry an instrumental error of at least 0.2 -
2%, meaning that on a 100 Ma date: range is between 98-102 Ma.
• Records crystallization time (detrital zircon mineral in a sedimentary
rock records date of rock from which the zircon was eroded)
• Contamination problems abound (e.g., volcanic ash flow may pick up
older/detrital feldspar or biotite minerals on its excursion over a rock.
• Metamorphism may "reset" clock
• Loss of either parent or daughter rocks due to heat or weathering. Need
FRESH samples
• Have to have enough of an isotope to measure (low crustal abundance
of some elements, or low abundance in rocks being studied).
• Half-life has to be short enough to have produced enough daughter
isotopes for analysis (limits use of "long-term" isotopes such Rb-Sr, U-
Pb, Th-Pb to rocks over a 100Ma old).
• Half-life can't be so short such that the original parent is beyond
detection.
◊OTHER USES OF RADIOACTIVE ISOTOPES

► GEOCHEMICAL PROCESSES

RADIOGENIC ISOTOPES AS INDICATORS OF

DIFFERENTIATION

□Introduction

The Sr isotopic compositions are used as indicators of processes of

geochemical differentiation and of the isotopic compositions and histories
of the sources from which the present derivatives were derived.

□Uniform Reservoir (UR) model/Primitive Mantle Model (PMM).

Isotope geochemists have defined a model for the evolution of the Sr

isotopic composition from the undifferentiated (unfractionated) mantle. That
model is called the Uniform Reservoir (UR) model, although it is often
referred to as the Primitive Mantle Model (PMM).

• Any evolution model must have a starting point.

• The starting point for the UR model of the Sr isotopic composition of the
Earth is based on analyses of the Sr isotopic compositions (87Sr/86Sr) of
meteorites and is called the Basaltic Achondritic Best Initial ratio (BABI)
The value for BABI (0.69897±0.00003) was determined by the analysis of
a large number of basaltic composition achondritic stony meteorites,
which are thought to be representative of the material which accreted from
the solar nebula to form the Earth.
• The starting point in time for the UR model is the estimated age of the
Earth, based on dating of meteorites, which is 4.6 billion years (4.6 Ga
b.p.).
• The other parameter in the UR model is the 87Rb/86Sr ratio of the bulk
Earth, which has been estimated to be 0.0816.
• Thus the UR model for the evolution of the Sr isotopic composition of the
Earth is:
(87Sr/86Sr)t = 0.69897 + 0.0816(eλt-1)
(note: λ= 1.42x10-11 y-1)
 where the time (t) is the time since 4.6 Ga b.p. (i.e., the time since the
formation of the Earth).

• The diagram below is a plot of the Sr isotopic composition of the Earth as

a function of time from the formation of the Earth (left side of the diagram)
to the present (right side of the diagram).

• The UR model is indicated. For this model, the 87Sr/86Sr ratio of the Earth evolves from
0.69897 (BABI) 4.6 Ga ago to 0.7045 today.

□Generation of Crust
Now consider what happens when the Uniform Reservoir is partially melted to generate
melt, which becomes crust.
• During a partial melting event, the mantle that is partially melted, the
partial melt and the mantle that is left behind (residual mantle) all have
the same 87Sr/86Sr ratio (shown by the dot in the figure).
• However, partial melting does fractionate Rb from Sr in such a way that
the partial melt (= crust) has a higher Rb/Sr ratio than the original
mantle that was melted and the residual mantle has a lower Rb/Sr ratio
than the original mantle.
• Thus, the 87Sr/86Sr ratio of the partial melt (= crust) grows more quickly
than that of the original (UR) mantle (melt + crust line in the figure) and
 the 87Sr/86Sr ratio of the residual (depleted) mantle grows more slowly
than the UR mantle (residual mantle line in the figure).
• The result of this type of fractionation event is that crustal rocks, in
general, have higher 87Sr/86Sr ratios than the UR model and depleted
mantle rocks (from which partial melts were derived) have lower
87
Sr/86Sr ratios than the UR model.

□Melting of Crust
This type of modelling can be carried further by considering the isotopic
composition of a partial melt of the crust (i.e., a granite magma).
• During melting of the crust to form a granite magma, the magma will
again have a higher Rb/Sr ratio than the crust that is being melted and
the residual (unmelted) crust will have a lower Rb/Sr ratio than the
original crust.
• Thus, over time the (rock) granite's 87Sr/86Sr ratio will evolve to higher
values than the original crust that was melted and the 87Sr/86Sr of the
residual crust in the granite source region will evolve more slowly than
that of the original crust.
• Consequently, granites are expected to have quite high 87Sr/86Sr ratios (as
high as 0.715) compared to the UR model.

□Generation of Sea Floor Basalt

Similarly, consider a partial melting event in the residual mantle (blue line in
the diagram) that produces a sea floor basalt.
• While the basalt, which becomes part of the oceanic crust, will have a
87
Sr/86Sr ratio that grows more rapidly than the ratio of the residual
mantle from which it was derived, the resulting 87Sr/86Sr ratio will be
lower than that of a basalt derived from UR mantle at the same time by
the same extent of partial melting.

In both of these cases, the initial ratios of the basalt and the granite (the
87
Sr/86Sr composition of the melts at the time they were formed) will reflect
the isotopic compositions of the source regions of those melts. These initial
ratios are very useful to the isotope geochemistry.

►NATURAL TRACERS OF GEOCHEMICAL PROCESSES.

1ms = 10-6s, 1 ms = 10-3s,1 My = 106y, 1 Gy = 109y