Effect of temperature on the dissolution and thermal alteration of combined amino acids fixed in natural sediment under simulated hydrothermal conditions

Seafloor sediment containing biogenic amino acids was heated with NaCl solutions at 50–200 °C for 240 h to investigate the dissolution process of amino acids and evaluate their stabilities under hydrothermal conditions. Dissolved amino acids in the combined phase (dissolved combined amino acids, DCAAs) and free phase (dissolved free amino acids, DFAAs) were rapidly released into the solution during heating. The amount of DCAAs in the solutions was 4–9 times higher than the amount of DFAAs at each temperature. When heated at ? 100 °C, most of the total dissolved hydrolyzable amino acids (TDHAAs) were in the combined form (DCAAs/TDHAAs ratios > 0.9). The compositions of the DCAAs in solutions heated at ? 100 °C were similar to that of the total hydrolyzable amino acids (THAAs) of the initial sediment, indicating that the DCAAs, which are derived from organisms and biodebris in the sediment, are barely altered during the hydrothermal reaction at these temperatures. On the other hand, the DCAAs/TDHAAs ratios were 0.72 and 0.57 at 150 and 200 °C, respectively, and the compositions of the DCAAs at 150 and 200 °C were significantly different from that of the initial THAAs. In addition, non-protein amino acids (β-alanine and γ-aminobutyric acid), which are sensitive biochemical indicators of the diagenetic alteration of natural organic matter, drastically increased to 80.9% of the DCAAs after heating at 200 °C. These results suggests that DCAAs are thermally unstable in the hydrothermal solutions at ? 150 °C. These DCAA would be transformed into thermally stable geo-polymers such as humic-like substances and hydrolyzable kerogens.