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Site-Specific Isotopes in Small Organic Molecules


Piasecki, Alison Martha (2015) Site-Specific Isotopes in Small Organic Molecules. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z9833PZP.


Stable isotope geochemistry is a valuable toolkit for addressing a broad range of problems in the geosciences. Recent technical advances provide information that was previously unattainable or provide unprecedented precision and accuracy. Two such techniques are site-specific stable isotope mass spectrometry and clumped isotope thermometry. In this thesis, I use site-specific isotope and clumped isotope data to explore natural gas development and carbonate reaction kinetics. In the first chapter, I develop an equilibrium thermodynamics model to calculate equilibrium constants for isotope exchange reactions in small organic molecules. This equilibrium data provides a framework for interpreting the more complex data in the later chapters. In the second chapter, I demonstrate a method for measuring site-specific carbon isotopes in propane using high-resolution gas source mass spectrometry. This method relies on the characteristic fragments created during electron ionization, in which I measure the relative isotopic enrichment of separate parts of the molecule. My technique will be applied to a range of organic compounds in the future. For the third chapter, I use this technique to explore diffusion, mixing, and other natural processes in natural gas basins. As time progresses and the mixture matures, different components like kerogen and oil contribute to the propane in a natural gas sample. Each component imparts a distinct fingerprint on the site-specific isotope distribution within propane that I can observe to understand the source composition and maturation of the basin. Finally, in Chapter Four, I study the reaction kinetics of clumped isotopes in aragonite. Despite its frequent use as a clumped isotope thermometer, the aragonite blocking temperature is not known. Using laboratory heating experiments, I determine that the aragonite clumped isotope thermometer has a blocking temperature of 50-100°C. I compare this result to natural samples from the San Juan Islands that exhibit a maximum clumped isotope temperature that matches this blocking temperature. This thesis presents a framework for measuring site-specific carbon isotopes in organic molecules and new constraints on aragonite reaction kinetics. This study represents the foundation of a future generation of geochemical tools for the study of complex geologic systems.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:geochemistry; isotopes; organic molecules
Degree Grantor:California Institute of Technology
Division:Geological and Planetary Sciences
Major Option:Geology
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Eiler, John M.
Thesis Committee:
  • Sessions, Alex L. (chair)
  • Asimow, Paul David
  • Farley, Kenneth A.
  • Eiler, John M.
Defense Date:7 May 2015
Non-Caltech Author Email:alison.piasecki (AT)
Record Number:CaltechTHESIS:05292015-100107828
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8923
Deposited By: Alison Piasecki
Deposited On:29 May 2015 22:04
Last Modified:04 Oct 2019 00:08

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