Geochronology
III: Other Dating
Methods
Chapter 4
Cosmogenic Nuclides
Table 4.1. Data on Cosmogenic
Nuclides
Nuclide Half-life, yrs
λ, yr-1
14
C 5730
1.21 x 10-3
3
H 12.33
5.62 x 10-2
10
Be 1.50 × 106 4.64 x
10-7
26
Al 7.16 × 105
9.68 x 10-5
36
Cl 3.08 × 105
2.25 x 10-6
32
Si 276
2.51 x 10-2
Cosmic Rays
Cosmic rays are high-energy (several GeV up to 1019 eV) atomic nuclei,
mainly H &, but nuclei of all the elements have been recognized.
CERN’s Large Hadron Collider, mankind’s most powerful accelerator,
produces energies of ~1013 eV (10 GeV)
A significant fraction of cosmic rays originates in he Sun, although these
are mainly of energies too low to generate cosmogenic nuclides. The
origin of the remainder is unclear; most likely originate in supernovae or
similar high-energy environments in the cosmos.
The primary reaction that occurs when cosmic rays encounter the
Earth is spallation, in which a nucleus struck by a high energy particle
shatters into two or more pieces, including stable and unstable nuclei,
as well as protons and neutrons. Short-lived particles such as muons,
pions, etc. are also created. The interaction of a cosmic ray with a
nucleus sets of a chain reaction of sorts as the secondary particles and
nuclear fragments, which themselves have very high energies, then
strike other nuclei producing additional reactions of lower energy.
14
C
Carbon-14 is by far the most familiar and useful
of the cosmogenic dating schemes. Its
usefulness results from its relatively short half-
life, a relatively high production rate, and the
concentration of carbon in biological material.
14C produced primarily by reactions with
secondary particles, mainly by the 14N(n,p)14C
reaction involving relatively slow neutrons. The
high abundance of the target nuclide is part of
the reason for the high production rate.
Analytical Techniques
The traditional method of 14C determination is counting of the β-rays
produced in its decay.
Gas proportional counter. Carbon converted to CO2 and placed in a metal tube
with a negatively charged wire (the anode) running through it. The emitted
beta strips electrons from atoms which drift to the wire (the anode), producing
a measurable pulse of current.
In liquid scintillation counting, the carbon is converted into CO2 and then to
benzene (C6H6) and mixed with a liquid scintillator (an organic liquid). β
particle causes the scintillator to give off a photon, which is then detected with
a photomultiplier, and the resulting electrical pulse sent to a counter. This
technique is more sensitive and has largely replaced gas counters. Requires
~1g carbon.
Accelerator Mass Spectrometry. The low abundance of 14C compared to stable
C isotopes (14C/12C ~ 10–12) requires very high resolution to avoid interference
with those isotopes as well as others such as 14N. That requires the ions be
accelerated to high energies (MeV rather than keV of conventional mass
spectrometers). In the last few decades, dedicated instruments have been
built for this purpose. Requires only a few milligrams C.
C Dating
14
Reported in units of Beq/g C (counts per minute), known as
specific activity.
Equation of interest is:
where N0 is the atmospheric value of has 13.56 Beq/g.
By historical convention, radiocarbon ages are reported in
years before 1950 (the year the first 14C age determination;
the abbreviation BP thus means not before present, but
before 1950) and assuming a half-life of 5568 years (instead
of the currently accepted value of 5730 years).
Partly, this is a consequence of atmospheric nuclear weapons
tests in the ‘50’s, which contaminated the atmosphere with 14
C.
Cosmic Ray Flux
Cosmogenic nuclide production
affected by geomagnetic field,
which deflects cosmic rays.
Cosmogenic nuclide production
increases toward the poles (due to
magnetic field influence on cosmic
rays), but atmosphere is well mixed
for CO2.
Does affect other nuclides.
Field and production rate has varied
with time.
The solar wind modulates the solar
magnetosphere, which deflects
galactic cosmic rays at the outer
edge of the solar system (the
heliopause). Varies with the
sunspot cycle and perhaps on
longer time scales: so-called
deVries Effects.
Reservoir Effects
Specific activity also
varies because the
denominator
varies, .i.e., atmospheric
carbon levels.
Fossil fuel burning has
increased atmospheric
carbon by 30% since
Industrial Revolution
(this carbon is 14C-free)
Shifts of CO2 between
ocean and atmosphere
changes atmospheric
CO2 by 60% (oceanic
CO2 is ‘older’ and 14C
depleted).
Converting Radiocarbon
Years to Calendar Years
As a consequence of these effect,
the 14C time scale requires
calibration.
Initially based on ‘dendrochronology’
– tree rings.
Further back in time, 14C has been
calibrated against Th-U ages of
corals.
Because the effects are non-linear,
the conversion results in a
probability distribution of calendar
years.
Programs available such as Univ. of
Belfast
([Link] ) or
Columbia U.
([Link]
[Link]/ )
14
C Calibration based on
Th-U Dating of Corals.
Calibration based on corals from Barbados Barbados, Kiritimati Atoll in
the central equatorial Pacific, and from Araki Island in the southwest
Pacific (Faribanks et al., 2005).
10
Be, 26
Al, Cl
36
These nuclides have much longer half-lives than C and thus are be
14
applied to longer time-scale problems, such as Pleistocene chronology
and dating of groundwater.
Be is created by spallation reactions between cosmic rays and N and O
10
nuclei.
Al is produced by spallation of
26 40
Ar
Cl is produced by 40Ar(p,α)36Cl reactions (probably mainly with
36
secondary protons).
Production Rates
10
Be 10-2 – 10-3 atoms/cm2/sec
26
Al and 36
Cl 10-5–10-6 atoms/cm2/sec
Unlike 14C, all are quickly washed out of the atmosphere. There are
latitudinal variations in production and abundance.
Abundance of 10Be in marine sedimentation is, however, uniform due to
mixing in oceans.
10
Be Dating
Be mainly used for dating sediments (some tectonic/high-T
10
application as well - later).
Begin with the equation:
assuming a constant flux, ƒ, to the sediment:
where brackets denote concentration
Sedimentation rate, s, however, may vary, so:
sedimentation rate is related to time and depth as z = s ×t
10
Be Dating
Taking the log of the previous
equation,
log of 10Be is a linear function of z
if sedimentation rate is constant
(and no compaction).
If sedimentation rate is not
constant:
Better to think of 10Be as a
function of depth, not time (which
we do not know):
10
Be data in a sediment core
Sedimentation rate is
from the western tropical
Pacific.
10
Be Dating
substituting for s and integrating:
Solving for t(z):
The integral term is simply the sum of all 10Be above
depth z.
(Some similarity to constant flux model of 210
Pb)
This assumes a constant production rate (it is not
constant). If we know the production rate, we can
substitute ƒ(t) for ƒ in the above equation.
36
Cl Dating in Hydrology
C can be used for
14
groundwater dating, but C is
not conservative (respiration,
dissolution, precipitation of
carbonate).
Cl by contrast is nearly
36
conservative in groundwater.
Stable isotopes of Cl are 35Cl
and Cl.
37
36
Cl produced by cosmogenic
reactions on Ar in the
atmosphere, hence there is a
latitudinal dependence.
Quickly washed out by rain,
unlike C.
Activity usually ratioed to total
Cl.
Nucleogenic Production
Complicating matters, there is some production
of 36Cl in the Earth by 35
Cl capture of fission-
derived neutrons.
This nucleogenic 36Cl will build up over time:
where Φn is the neutron flux, ƒ is the capture cross
section and [35Cl] is the concentration of Cl.
35
So how will 36Cl vary with time according to this
equation?
36
Cl Dating
“Age” of groundwater can be determined from
But groundwater in a given location could have
multiple sources of multiple ages.
So we need to know the initial ratio and secular
equilibrium ratios as well.
Evaporation, mixing with formation brines,
dissolution of salt, etc. can all complicate age.
Great Artesian Aquifer of
Australia
Great Artesian Aquifer of
Australia
4
He dating of groundwater
4He produced by α-decay in rock
Assuming water flows by piston-flow,
accumulation of 4He will be:
where Rα is the production rate, and ϕ is
porosity.
Complication: high diffusivity of He
4
He in Great Artesian
Aquifer
4
He appears to be diffusing into the aquifer from
below
In Situ Produced
Cosmogenic Nuclides
Cosmic-ray spallation produces both stable and
unstable nuclides.
Of the stable ones, only those that are very rare
are of interest
In Situ Production
Some cosmic rays manage to
penetrate to the Earth’s the
surface. Flux then decreases
exponentially as:
where z is depth, ρ is density and l
is a constant that depends on the
nature of the particles, their
energy, and nature (composition)
of materials.
l is ~160g/cm2, most rock has
ρ~2.5g/cc, so flux would decrease
to 1/e or 0.36 at a depth of 64 cm.
Muons penetrate more effectively
(l~1000 g/cm2, but interact weakly
with matter).
3
He dating of surfaces and
erosion rates
Production of a stable nuclide at the surface will be
N = Pt
(Abundance increases linearly with time, assuming constant
production rate). 3He accumulation has been used to date lava
flow surfaces.
P is a function of both latitude and altitude.
The concentration as a function of time and depth will be
Of course if depth is constant, this integrates simply to:
Now suppose that depth varies as a result of erosion occurring at
rate ε. Depth is then a function of time:
3
He dating of surfaces and
erosion rates
Substituting for z:
Now substituting z0 = z + εt, at the surface (z=0) this reduces
to
Neither can be solved directly. However, if the age of the rock,
t, is known from some other method, one can measure a series
of values, C, as function of depth and make a series of guesses
of the erosion rate until a curve based on 4.28 fits the data.
Using this procedure, Kurz estimated an erosion rate of 10 m/Ma
for Haleakala (for higher erosion rates, it would be necessary to
take account of the muon-produced 3He).
Erosion Ages from Unstable
Cosmogenic Nuclides
For a nuclide such as 26Al or 36Cl, need to take account of
its decay. The concentration as a function of time and
depth will be:
After many half-lives the concentration at the surface of
eroding rock will be:
While the concentration is steady-state, it does depend on
the erosion rate, which we can easily solve for.
Exposure Ages with
Cosmogenic Nuclides
Concentration of unstable cosmogenic nuclide at
the surface will change with time as:
Integrating
What happens eventually?
36
Cl Dating of Moraine
Boulders in the Sierra Nevada
Comparison with Marine O
isotope chronology
Fission-Track Dating
Fission Track Dating
A small fraction of 238U decay through fission rather than α-decay.
λƒ = 8.46 x 10-17 yr-1.
Fission produces two unequal nuclear fragments (plus some neutrons).
Some of the decay energy converted to kinetic energy of the fragments,
which then fly through the crystal lattice, damaging it.
The lattice damage can be enhanced by acid leaching so it is visible
under the microscope.
Number fission tracks is a function of time:
where λƒ/λα = 5 x 10–7. Note that λƒ+λα ≈ λα
Tracks anneal at a temperature-dependent rate, with “closure T” being
fairly low, depending on mineral.
Analytical
Tracks must intersect
surface to be counted so the
track density, so density will
be:
U concentration is typically
determined by irradiating
the sample with neutrons
and inducing fission of 235U;
number of induced tracks is
where ϕ is thermal neutron
dose and σ is reaction cross
section.
Zeta Method
In practice, sample is etched, tracks
counted, then a “detector” placed
on sample and package is
irradiated. Induced tracks counted
in detector. Age is related to track
density as:
In practice, we irradiate a standard
of known age, and pile the various
constants into the zeta-factor, ζ:
where ρd is the track density in a U-
doped standard.
(similar to 40Ar/39Ar)
Rearranging and solving for t:
Assessing Results
Usually, fission track
ages on a number of
grains must be measured
for the results to be
significant. The results
are often presented as
histograms. Alternatively,
when the errors are also
considered, the results
may be presented as a
probability density
diagram, such as Figure
4.16.
Assessing Results
Yet another approach is to
plot the spontaneous track
density (ρs) vs the induced
track density (ρi), such as
Figure 4.17. From equation
4.39, we see that the slope
on such a diagram is
proportional to time. Thus
these kinds of plots are
exactly analogous to
conventional isochron
diagrams. There is a
difference, however. On a
plot of ρs vs. ρi the intercept
should be 0. Figure 4.17
Interpreting Ages
Closure Temperatures
Same dependence of
closure temperature on
cooling rate applies to
fission tracks (and U-Th-
He ages).
Figure shows comparison
of apparent closure
temperatures of fission
tracks, U-Th-He, and K-Ar
as a function of cooling
rate for a variety of
minerals. From Reiners &
Brandon (2006).
Uplift Rates
As mountains respond to erosion by uplift,
underlying rock cools as it approaches the
surface so that temperature at depth z will be:
where Ts is the surface temperature and TL is the
temperature of the base of a layer of thickness L,
HT is the radiogenic heating (˚C/Ma), κ is thermal
conductivity and ε is erosion rate.
If erosion rates are high, geothermal gradient can
be non-linear.
Erosion Rates, Geothermal Gradients,
and Closure Temperatures
Track Ages in the
Himalaya
Fission Track Lengths
Additional information may be
contained in the length of fission
tracks (resulting from partial
annealing).
When a grain is subjected to
elevated temperature, both the
track density and the mean track
length decrease. Because (1) tracks
tend to have a constant length
(controlled by the energy liberated
in the fission), (2) tracks become
progressively shorter during
annealing, and (3) each track is
actually a different age and has
experienced a different fraction of
the thermal history of the sample,
the length distribution records
information about the thermal
history of the sample.
Mass Spectrometry
Quick Overview
Magnetic Sector Mass
Spec
Consists of 3 parts
A ion source – to produce & accelerate ions
mass analyzer – deflects ions in proportion to mass
collector/detector – to detect or count ions
Ion Source
Ions can be produced by
thermal ionization
collisions with electrons produced by a hot
filament
plasma
secondary ionization
laser ionization
Mass Analyzer
A charged particle moving in a magnetic experiences a force
F = qv × B A.1
Since the force is always directed perpendicular to the direction of motion, the
particle begins to move in a circular path. The motion is thus much like swinging a
ball at the end of a string, and we can use equation for a centripetal force
Equating:
The velocity of the particle can be determined from its energy, which is the
accelerating potential, V, times the charge:
Substituting:
We select for mass by adjusting B
Typical value of r for a thermal ionization mass spec is 54 cm.
Energy Filtration
If ions are not mono-
energetic or to improve
abundance sensitivity,
some elements are fitted
with an electrostatic
analyzer, which selects
for ion energy.
Faraday Cup
Electron Multiplier
Ion beam strikes a
charged surface
producing a cascade of
electrons.
Can be used in either
analog or ion counting
modes.
Daly Detector
Quadrapole Mass Spec.
Quadrapole operates by
rapidly varying charge
between + and – on 4
cylinders at R.F..
Ion spirals through the
analyzer.
By tuning the rate of
variation, only one m/q
value will arrive at the
detector.
Most common kind of
mass spec, but less
accurate for isotope
ratios.
Can be combinedwith a
variety of ion sources
and detectors.
Accelerator Mass Spec.