Two types of Fractionation: Kinetic and Equilibrium

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Two types of Fractionation Kinetic and
Equilibrium
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How it's done!
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EXAMPLE OF CO2
Mass Isotopomer 44 12C16O16O 45 13C16
O16O 12C17O16O 12C16O17O 46 13C17O16O
13C16O17O 12C17O17O 12C18O16O
12C16O18O
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The delta notation (not del)
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Alpha a
C18O H216O C16O H218O
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Example of calcite
CaCO3 phosphoric acid ? CO2 H2O
dissolved calcium phosphate
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THERMOMETRY
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Standards
Hydrogen V-SMOW standard mean ocean
water Carbon V-PDB Pee Dee belemnite Nitrogen A
ir air Oxygen V-SMOW, V-PDB Sulfur CDT
(V-CTD?) Cañon Diablo troilite
d18OSMOW 1.03091 d18OPDB 30.91
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Applications
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METEORIC WATER
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Altitude Effect
Seasonal Effect
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Hydrogen Isotope Contours of Meteoric Water
Sheppard et al., 1979
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Migration Studies Birds, for example
Insights into Wilson's Warbler migration from
analyses of hydrogen stable-isotope
ratios Jeffrey F. Kelly, , Viorel Atudorei,
Zachary D. Sharp and Deborah M. Finch
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White Crowned Sparrows
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Wilsons Warblers
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Positive correlation between migration and dD
value
The warblers from the north arrive first
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Winter breeding latitude vs dD value. Positive
correlation indicates that there is a leapfrog
migration
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Conclusions

• The dD values of Wilson Warblers can be used to
  determine the approximate latitude where they
  molt.
• Wilson Warblers from the North arrive in New
  Mexico before those from the South
• The warblers arriving from the north also fly the
  farthest south. They leapfrog their southern
  neighbors
• To obtain this information from tagging would
  have been extremely difficult. Using stable
  isotopes, every bird gives information

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Proportion of hydrogen incorporated from body
water
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Preliminary Conclusions

• Only a small fraction of hydrogen incorporated in
  proteins comes from water. The rest is from
  reorganized proteins.
• The dD value of protein in hair is close to that
  of the drinking water, suggesting that the
  fractionation is low, and/or the dD value of my
  food is different from the water so that the
  fractionation effect exactly cancels out.
• It takes about 10 days for body water to exchange
  its hydrogen isotopes
• Hair has a 8 day delay from body water

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Oxygen isotope study of fossil horse teeth,
paleoclimate info.
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Partial Conclusions

• The d18O values of biogenic phosphate can be used
  for paleoclimate work
• The tape recorder growth of horse teeth allows
  for them to be used for determining seasonal
  temperature variations in the distant past.
• In Texas, the climate was the same 8 million
  years ago as it is today

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Carbon Isotopes in Plants
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Evidence for a change in climate 8 million years
ago
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Lake Greifen, Switzerland, showing effect of
biological pump grey is winter profile
After McKenzie (1985)
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Kangaroo Rats do not change betweeen years
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• We can use carnivores and herbivores to assess
  relative humidity in the distant past
• We can estimate what was the diet of a poorly
  understood animal

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