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term “kinetic fractionation” applies to
change of state processes
(evaporation/condensation), and that is
mostly what we are dealing with in the
application of oxygen isotopes to climate
studies.
Oxygen Isotope fractionation
“Kinetic fractionation” does also apply to
chemical reactions.
Oxygen has two main isotopes:
For our purposes, kinetic fractionation
16 O which accounts for 99.8% refers to the process whereby the
heavier isotope is concentrated in the
and liquid as compared to the gas on
18 O which accounts for most of
evaporation or condensation.
the remaining 0.2%
The lighter isotope ( 16 O) tends When water evaporates, the water
to move more quickly and react vapor becomes enriched in the lighter
at a faster rate than the heavier isotope and the water left behind
becomes “heavier”.
isotope ( 18 O) .
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When water vapor condenses the
water becomes enriched the heavier
isotope, and the water vapor becomes
“lighter”
The result is that equatorial waters
are relatively heavy
δ 18 O ~0
On earth most evaporation takes place
in the tropics, and the general trend is while temperate and nearpolar
for that evaporated water to move waters are lighter
towards the poles. δ 18 O 5 to 15
and polar ice is very light
δ 18 O 20 to 55
As the water vapour in the atmosphere Oxygen isotope fractionation is more
is gradually condensed into water on its pronounced at low temperatures, so
journey north or south, the rain the equatortopole isotope gradient is
produced is isotopically heavier than greater under cool conditions.
the vapour left behind, and this means
that the water vapour becomes lighter Oxygen isotope data from ice cores
and lighter as it moves towards the show low δ 18 O values for glacial
poles. periods.
This is known as Rayleigh fractionation.
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In foraminifer shells the
ratio of 16 O and 18 O in the
Under glacial conditions, a greater than carbonate records that
normal proportion of the earth’s water is ratio that is present in
locked up in glacial ice, which is mostly seawater,
situated near to the poles, and is isotopically Nutallides truempyi modified by the
very light. This means that the remaining temperature of the sea
sea water will be isotopically heavier than water (through
normal. fractionation of the 18 O
(i.e., δ 18 O values are higher than normal) and 16 O isotopes).
Both are benthic foraminifers.
Cibicidoides sp.
Biological processes fractionate oxygen isotopes during metabolism.
(organisms ‘like’ the light isotope better)
and the degree of fractionation is TEMPERATE DEPENDENT.
The temperature dependence of this biological fractionation is:
Oxygen isotope measurements of
marine sediments or of organisms 1 0 / 00 decrease in δ 18 O for each 4.2°C increase in
water temperature
in equilibrium with sea water are
more strongly affected by the or… 18 O becomes less abundant in the carbonate shells of forams when
volume of ice than the temperature. the temperature increases.
or… δ 18 O levels drop as temperature increases
This is the opposite to what we see in
Nevertheless, oxygen isotopes can be icecore records, where low δ18O
used as a measure of temperature. values are associated with cold periods.
Glacial ice has not always been In foram data from marine sediment
present, and where necessary the cores low δ18O values are associated
volume of ice can be corrected for. with high temperatures.
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