The
influence of chlorine content on fission track annealing kinetics in
apatite
Natural apatites essentially
have the composition:
Ca5(PO4)3(F,OH,Cl)
with fluorine, hydroxyl and chlorine ions forming a substitution series.
Most common detrital and accessory apatites are predominantly fluor-apatites,
but some may contain appreciable amounts of chlorine.
Apatite
compositions: ternary plot - 4172 grains
*probe data;
OH by difference |
Typical
apatite Cl distributions |
The amount of chlorine in the apatite lattice exerts a subtle yet critical
compositional control on the degree of annealing, with apatites richer
in fluorine being more easily annealed than those richer in chlorine.
As a result, individual apatite grains within a single sample that has
been heated to the temperature range where the differential effect is
large will show a spread in the degree of annealing (i.e reduction in
fission track age and track length). This effect becomes most pronounced
in samples which have reached peak paleo-temperatures in the range 90
- 110°C. Below ~80°C, the difference in annealing sensitivity
is less marked, and compositional effects are less important.
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This
Figure shows single grain ages plotted against wt% Cl from a
sample of Early Cretaceous sandstone from a present-day temperature
of 100°C (~ 2585 m depth) in the Flaxmans-1 well in the
Otway Basin of SE Australia. Fission track ages in apatites
with low Cl contents are close to zero, while values in apatites
containing 2 wt% Cl are still close to the depositional age,
and have undergone very little age reduction. Redrawn from Green
et al. (1986).
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The influence of chlorine content is also readily observable in the
laboratory.
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This
Figure shows results from laboratory isothermal annealing experiments
involving four apatites with different chlorine contents. Mean
track length in each apatite is plotted against a combined function
of annealing temperature and time, to reduce the data to a common
scale. The systematic influence of Cl is clear. Pure fluorapatite
is totally annealed in conditions where the the mean track length
in apatite containing 0.8 wt% Cl is still around 12 microns.
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Since those early measurements, a consistent body of evidence has built
up to emphasise the importance of Cl content. Some typical examples
are shown below:
Taranaki Basin well Fresne-1 (from Crowhurst et al., 2002):
more details...
These plots
illustrate the relationship between fission track age and wt% Cl in
individual grains of apatite from eight samples downhole in the Fresne-1
well. With increasing depth and present-day temperature (shown for each
plot), the degree of annealing prior to cooling from the maximum post-depositional
paleotemperature increases, and apatites with progressively higher Cl
contents were totally annealed. The grey lines represent the predicted
trend from the best-fit history. Note that three grains, out of over
160 represented in these plots, do not fit the general pattern. These
probably represent second order influences on annealing, which are clearly
only of minor importance. Presentation of data in this way allows such
spurious data (e.g. contamination) to be easily identified and removed.
Another way of looking at these data is to plot the pooled age of each
compositional group against depth:
This illustrates the typical degree of differential annealing behaviour
introduced by chlorine. The difference in the depths at which apatites
containing 0.0-0.1 and those containing 0.5-0.6 wt% Cl are totally annealed
prior to the onset of cooling is almost 1 km, equivalent to a temperature
difference of about 25°C in this well.
Southern North Sea well 47/25-1:
In this well, fission track ages in individual apatite grains show distinct
trends of age vs wt% Cl. In the shallower sample (GC290-5), only apatites
containing less than 0.1 wt% Cl were totally annealed prior to cooling,
but in the deeper sample (GC290-6), the consistent ages over a range
of Cl contents from 0 to 0.5 wt% Cl show that all these apatites were
totally annealed prior to the onset of cooling. This trend helps to
define the time at which the sample cooled from the maximum paleotemperature,
around 60 Ma (note that the measured ages are less than this because
of further annealing after cooling began).
In samples which are now at their maximum post-depositional paleotemperatures,
the expected trends of AFTA parameters with Cl are fairly simple:
Patterns
of within-sample age variation:
Maximum temperatures at the present day
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Patterns
of within-sample length variation:
Maximum temperatures at the present day
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Here are
some data from a sample that corresponds to somewhere between the orange
and magenta trends in the above Figure:
Jurassic
sandstone, North Sea, 103°C |
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In samples which have been hotter in the past, the trends within the
age data are also quite simple, but trends within the length data are
much more complex, reflecting the relative contributions of short tracks
formed prior to the thermal maximum, and long tracks formed after the
onset of cooling:
Patterns
of within-sample age variation:
Hotter in the past |
Patterns
of within-sample length variation:
Hotter in the past |
Triassic
sandstone, Northern England, 100°C at ~60Ma |
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In samples that have been hotter in the past, it’s easier to look
at the track length distributions within each compositional division:
The red histograms represent the measured track length data, the blue
histograms represent the predictions of the best-fit thermal history,
and the overlap between the two is shown as magenta. Pure fluorapatites
(top left) were near-totally annealed prior to the onset of cooling,
and the track length distribution is unimodal, dominated by a peak of
long lengths around 14 microns. In contrast, the track length distribution
in apatites containing 0.3 to 0.4 wt% Cl (top right) is bimodal, with
a prominent peak of short tracks (formed up to the paleo-thermal maximum)
as well as a longer peak (tracks formed after the onset of cooling),
in roughly equal proportions. As the chlorine content increases, the
length of the shorter peak becomes increasingly longer, such that in
apatites containing 0.7 to 0.8 wt% Cl, the two components cannot be
resolved and the track length distribution is unimodal. This reflects
the decreasing degree of annealing of tracks formed up to the paleo-thermal
maximum as Cl content increases, as also reflected in the trend of age
reduction vs Cl shown in an earlier Figure.
The data from the Triassic sandstone sample shown above calls to mind
the AFTA data from the Lake District, published by Green (1986):
Samples show
a considerable spread in age within a relatively small area, mainly
reflecting variation in Early Tertiary paleotemperatures across the
region. The variation in age is due to different degrees of annealing
of tracks formed prior to the onset of Early Tertiary cooling, and correlates
with the variation in mean track length and the shape of the track length
distribution (below):
The right hand Figure illustrates the interpretation of the trend in
the measured parameters (left), showing how the shape of the track length
distribution changes systematically, reflecting the mixture two components,
a long population of tracks formed after the onset of Early Tertiary
cooling, and a shorter component representing tracks formed prior to
the onset of cooling, with the length of the shorter component decreasing
with the reduction in fission track age.
Compare these Figures, based on a suite of outcrop samples, to the variation
within the single sandstone sample shown earlier, introduced by the
influence of Cl content on annealing rates. The full spectrum of the
effects seen in the outcrop suite is present within a single
sample!
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