Radiogenic Isotopes

Isotope Geology
Isotope Geology is concerned with the measurement and interpretation of the
variation/fractionation of the isotope composition of certain elements in natural
materials.

These variations or fractionation are the result of two quite different processes:
Closure temperature or blocking temperature:
 In radiometric dating, closure
temperature or blocking
temperature refers to the
temperature of a system, such
as a mineral, at the time given by
its radiometric date.

 The temperature below which the

diffusive exchange becomes
insignificant is called the closure
temperature (Tc) of the system.

 A knowledge of the cooling ages

and the corresponding closure
temperatures of two or more
minerals in a rock permits
calculation of the temperature drop
within a specific time interval, and
hence of an average cooling rate
within that interval.
The temperature below which the diffusive exchange becomes insignificant is called the
closure temperature (Tc) of the system.

A knowledge of the cooling ages and the corresponding closure temperatures of two or more
minerals in a rock permits calculation of the temperature drop within a specific time interval,
and hence of an average cooling rate within that interval.
Decay Scheme of Rb-Sr System:
Geochemistry of Rb and Sr:

1. Rb is an alkali metal belonging to Group IA which consists of Li, Na, K, Rb,

Cs.

2. Its ionic radius is 1.48 Å which is similar to that of K (1.33 Å).

3. This similarity allows Rb to substitute for K in K bearing minerals ( Mica:

Biotite, Muscovite, phlogopite, Lepidolite; K-feldspar: orthoclase and
microcline, certain clay minerals, evaporite ( sylvite and carnallite) etc.,

4. Rb has two naturally occuring isotopes 85Rb and 87Rb whose isotopic
abundances are 72.1654 and 27.8346 respectively.

5. Its atomic weight is 85.46776 amu.

6. 87
Rb is radiogenic and decays to 87Sr.
Decay Scheme of Rb-Sr System:
Geochemistry of Rb and Sr:

1. Sr is a member of alkaline earths of Group IIA which consists of Be, Mg, Ca, Sr, Ba

2. Ionic radius of Sr (1.13Å) is slightly larger than that of Ca (0.99Å).

3. Sr occurs in Ca-bearing minerals such as plagioclage, apatite, and Ca-carbonate.

4. The ability of Sr to replace Ca is somewhat restricted by the fact that Sr ions (Sr +2)
favor eightfold coordinated sites, whereas Ca ion (Ca+2) can be accommodated in
both six and eight fold coordinated lattice sites because of their smaller size.

5. Sr+2 can be also captured in place of K+1 ions by K-feldspar , but the replacement
must be coupled by the replacement of Si+4 by Al+3 in order to preserved electrical
neutrality.

6. Sr is the major cation in strontiatnite (SrCO3) and celestite (SrCO4).

Decay Scheme of Rb-Sr System:
Geochemistry of Rb and Sr:

Isotopes of Sr Abundances
88Sr 82.53
87Sr 7.04
86Sr 9.87
84Sr 0.56

Advantage and disadvantage of Rb-Sr system.

Decay scheme of K-Ar (Ar-Ar)
Decay Scheme of K-Ar System:
Geochemistry of K and Ar:

1. K is an alkali metal belonging to Group IA which consists of Li, Na, K, Rb,

Cs.

2. Its ionic radius is 1.51-1.64 Å

3. Lithophile (compatible in crust)

4. A major elements in metamorphic, igneous and sedimentary minerals

( mica: biotite, muscovite, phlogopite, lepidolite; K-feldspar: orthoclase and
microcline and certain clay minerals (smectite and Illite).
5. Ar is noble gas elements and do not form bonds with other atoms in a
crystal lattice.

Isotopic abundances of K Isotopic abundances of Ar

39
K 93.2581±0.0029
40
Ar 96.600
40
K 0.01167 ±0.00004
36
Ar 0.3364 ±0.0006
41
K 6.7302 ±0.0029
38
Ar 0.0632 ±0.0001
Decay Scheme of K-Ar System:
40
K-40Ca is not useful for dating. Why?
Because

1) 40Ca is the most abundant naturally occurring stable isotope

of Ca.

2) The formation of radiogenic 40Ca atoms in a rock or mineral

therefore increases its abundance only slightly.
Decay Scheme of K-Ar System:

40
Ar/36Ar)m = (40Ar/36Ar)o + (λe/ λ)40K/36Ar)(e λt-1))

(40Ar/36Ar)o = 295.5

Ar is an inert gas, which therefore has a low closure temperature.

In volcanic samples, initial Ar is effectively nil.
A single sample is enough to date
Decay Scheme of K-Ar System:

Limitation:
1. Two separate experiments are required.

 to determine no. of 40K atoms (concentration of K)

 to measure Ar concentration (by Gas source mass
spectrometry)

2. Ar being a noble gas is easily loss in open system

Ar-Ar Technique: Production of 39Ar from K

The number of 39Ar atoms formed during irradiation:

Irradiation refers specifically

39
Ar = K ΔT∫ ϕ(ε)σ(ε)d(ε)
39
to a process by which an
object is exposed to radiation

Where:

39
K is the number of atoms,

ΔT is the duration of the irradiation,

ϕ(ε) is the neutron flux density at energy ε, and

σ(ε) is the neutron capture cross section of 39K for neutrons of energy ε for
the neutron in/proton out.
Ar-Ar Technique: Estimation of irradiation parameters
The J value is determined by using
mineral standards of known age to
monitor the neutron flux.

The sample should be irradiated

along with a standard of a known age

Assuming that all the non-radiogenic argon is

atmospheric, the daughter/parent ratio
(40Ar*/39Ar) can be determined from the
equation:
Ar*/39Ar = [40Ar*/39Ar]m –
40

295.5[36Ar/39Ar]m

What about the other nuclear reactions i.e., 39K (n, p)39Ar take place in
the reactor?
Ar-Ar Technique: Nuclear reactions take place in the reactor
Ar-Ar Technique: Correction of interfering isotopes

a. Pure K salt (KCl or K2SO4) to estimate production of interfering isotopes

(40Ar) from K.

b. Pure Ca salt (CaF2) to estimate production of interfering isotopes (36A

and 40Ar) from Ca

c. A single experiments of Ar isotope ratios measurement, without

measuring K from different aliquot, provides the age !

d. No problem of sample heterogeneity.

Then, what about the Ar loss?

Ar loss is temperature dependant diffusion process

Where :
D is the diffusion coefficient (m2s-1),
D0 is the pre-exponential factor (the
theoretical diffusion constant at infinite temperature
or a measure of ‘conduction’ in the
mineral),
E is the activation energy (J),
R is the gas constant (J K-1 mol-1) and
T is temperature (K).

This logarithmic relationship between diffusion

rate and temperature means that at high
temperatures, argon can diffuse through a mineral
lattice and escape
Ar loss is temperature dependant diffusion process

Ar loss is higher

from the edge/rim
of the minerals
than that of the
interior/core.
Step heating experiment:

1. Heating the sample

with incrementally
increasing
temperature.
2. Calculating age at
each step heating.
3. Plotting apparent
age spectrum.
4. Helps to infer the
inner distribution of
radiogenic Ar.

A more representative age of initial cooling is given by the

"plateau age", where the edge effects give way to a
constant 40Ar/39Ar date.
U-Pb system
Geochemistry of U, Th:
1. U and Th are members of actinite series.
2. U (Z = 92) and Th (Z = 90) have similar chemical properties due to their
similar electron configuration (5f orbital filled with electron).
3. Both elements occur in nature as tetravalent state and their ions have
similar radii (U+4 =1.05Å; Th+4 = 1.10Å).
4. However, in oxidizing environment, U forms uranyl ion which is soluble in
water.

During partial melting and fractional crystallisation of magma, U and Th

are concentrated in the liquid phase and become incorporated into the more
silica-rich products. Therefore, igneous rocks of granitic composition are
more enriched in U and Th than basaltic or ultramafic rocks. Consequently,
the continental crust has more U and Th than the upper mantle.
U-Th-Pb decay system:
U-Th-Pb decay system: Half life time

238U = 4.510 billion years

235U = 0.7129 billion years
232Th = 13.890 billion years
U-Th-Pb decay system:
U-Th-Pb decay system:
U-Th-Pb decay system:
U-Th-Pb decay system:
U-Th-Pb decay system: Equation for dating
Discordant Ages:
In many instances dates calculated for
minerals containing U and Th are not
concordant (different ages depending on the
decay scheme used).

Pb, U or Th loss, Intermediate daughter

product loss

The effect of Pb loss on U-Pb dates can be

minimized by calculating a date based on
the 207Pb/206Pb ratio.

This ratio is insensitive to recent lead loss,

i.e., when the Pb that was lost had the same
isotope composition as the Pb that remained
in the mineral being analyzed.

The relationship between the 207Pb/206Pb

ratio and time results from the differences in
the half lives of their respective parents.
 Solid Earth Geochemistry:
To read the behaviors of trace elements and Isotopes in different magmatic systems

 Seeking to understand the origin of an ophiolite complex

 Thanks
To

The Geochemistry for providing different proxies to understand “Solid Earth Geological Processes”