TY - JOUR
T1 - Hydrothermal Experiments with Protonated Benzylamines Provide Predictions of Temperature-Dependent Deamination Rates for Geochemical Modeling
AU - Robinson, Kirtland J.
AU - Gould, Ian R.
AU - Hartnett, Hilairy E.
AU - Williams, Lynda B.
AU - Shock, Everett L.
N1 - Funding Information:
The authors thank Christa Bockisch for instruction in using the brass block heating apparatus and all past and present members of the Hydrothermal Organic Geochemistry (HOG) group at Arizona State University for critical feedback at weekly discussions. The authors thank Jeff Seewald for writing suggestions on early drafts. The authors specially thank Kristopher Fecteau for helpful feedback, especially regarding Arrhenius analysis. This work was supported by National Science Foundation grants OCE-0826588 and OCE-1357243, NASA Habitable World grants NNX16AO82G and 80NSSC20K1408, NASA grant 80NSSC19K1427, and a postdoctoral appointment to the NASA Postdoctoral Program at Woods Hole Oceanographic Institution, administered by Universities Space Research Association under contract with NASA.
Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/8/19
Y1 - 2021/8/19
N2 - In fluids of sufficient temperature and residence time, certain organic species are observed to equilibrate, and their abundances become diagnostic of reaction conditions, including temperature, redox state, and pH. Organic species released from remote geologic and planetary settings can therefore serve as geochemical tracers for environments that are difficult to observe directly. Here, we provide a framework for selecting organic compounds as geochemical tracers based on kinetic modeling. We characterized temperature-dependent rates of deamination substitution reactions for aqueous protonated benzylamines, i.e., benzylaminiums, to form benzyl alcohols and ammonium. Hydrothermal experiments were conducted at 200-300 °C at liquid-vapor water saturation pressures with ring-substituted benzylaminiums expected to have comparable deamination rates to environmentally abundant aminiums, e.g., amino acids. We compared rates extrapolated from experiments to idealized natural systems, taking into account fluid temperatures and residence times. Our results indicate that reversible deamination/hydration reactions may equilibrate over geologic time scales across diverse environments, including those approaching freezing temperatures for the most reactive benzylaminium. Therefore, similar reaction constituents may be useful targets for the exploration of potentially habitable subsurface environments, such as icy ocean worlds of the solar system. Our investigation supports previous findings that aqueous deamination of benzylaminiums operates via two simultaneous substitution mechanisms, SN1 and SN2. We find that for certain benzylaminiums, rates of each mechanism should be modeled individually to improve extrapolation across temperatures. Extrapolations of observed (i.e., bulk) deamination kinetics to near-ambient temperatures (∼50 °C) without mechanistic considerations can produce discrepancies in reaction half-lives on the order of a billion years.
AB - In fluids of sufficient temperature and residence time, certain organic species are observed to equilibrate, and their abundances become diagnostic of reaction conditions, including temperature, redox state, and pH. Organic species released from remote geologic and planetary settings can therefore serve as geochemical tracers for environments that are difficult to observe directly. Here, we provide a framework for selecting organic compounds as geochemical tracers based on kinetic modeling. We characterized temperature-dependent rates of deamination substitution reactions for aqueous protonated benzylamines, i.e., benzylaminiums, to form benzyl alcohols and ammonium. Hydrothermal experiments were conducted at 200-300 °C at liquid-vapor water saturation pressures with ring-substituted benzylaminiums expected to have comparable deamination rates to environmentally abundant aminiums, e.g., amino acids. We compared rates extrapolated from experiments to idealized natural systems, taking into account fluid temperatures and residence times. Our results indicate that reversible deamination/hydration reactions may equilibrate over geologic time scales across diverse environments, including those approaching freezing temperatures for the most reactive benzylaminium. Therefore, similar reaction constituents may be useful targets for the exploration of potentially habitable subsurface environments, such as icy ocean worlds of the solar system. Our investigation supports previous findings that aqueous deamination of benzylaminiums operates via two simultaneous substitution mechanisms, SN1 and SN2. We find that for certain benzylaminiums, rates of each mechanism should be modeled individually to improve extrapolation across temperatures. Extrapolations of observed (i.e., bulk) deamination kinetics to near-ambient temperatures (∼50 °C) without mechanistic considerations can produce discrepancies in reaction half-lives on the order of a billion years.
KW - Arrhenius
KW - Enceladus
KW - Eyring
KW - Hammett
KW - amino acids
KW - kinetics
KW - ocean worlds
KW - thermodynamics
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U2 - 10.1021/acsearthspacechem.1c00104
DO - 10.1021/acsearthspacechem.1c00104
M3 - Article
AN - SCOPUS:85114030633
SN - 2472-3452
VL - 5
SP - 1997
EP - 2012
JO - ACS Earth and Space Chemistry
JF - ACS Earth and Space Chemistry
IS - 8
ER -