Systematic chemotaxonomic profiling and novel paleotemperature indices based on alkenones and alkenoates: Potential for disentangling mixed species input

Abstract The unsaturation indices ( U 37 K , U 37 K' ) of long chain alkenones are powerful paleotemperature proxies and have been widely applied for sea surface temperature (SST) reconstructions in the past three decades. However, these indices encounter major difficulties in systems harboring different alkenone-producing haptophyte species, such as saline lakes and marginal ocean environments. All haptophytes produce C 37 alkenones, but different species often display large differences in temperature calibrations and may bloom in different seasons, hindering the use of U 37 K and U 37 K' indices for reliable paleotemperature reconstructions in mixed systems. To overcome these problems, we have recently reported a new analytical method that allows comprehensive separation of up to 32 alkenones, alkenoates and their double bond positional isomers in culture and sediment samples. Here we report a systematic analysis of alkenones and alkenoates from six haptophyte cultures growing at a wide range of temperatures (4–25 °C). Together with a compilation of 230 previously published culture data sets, we present here systematic calibrations of temperature-sensitive indices based on all alkenone and alkenoate homologues (including isomers). Using this dataset, we extract systematic chemotaxonomic criteria for differentiating individual haptophyte species and demonstrate such chemotaxonomic features can be encoded into a machine learning model for reliable species identifications. Specifically, we show that temperature calibrations based on C 38 methyl ketones and C 39 ethyl ketones are potentially useful for disentangling mixed inputs in estuarine systems where Group III ( E. huxleyi ) and Group II alkenones mix, and that C 36 ethyl alkenoate isomeric ratios display minimal species heterogeneity and are potentially more suited for reconstructing temperatures in mixed systems with different Group II haptophytes. Using the culture data as base profiles, we construct a mathematical model for estimating percentage inputs from alkenones of different Isochrysidales groups in mixed systems, with potential implications for inferring past salinity changes. Overall, the results from this study demonstrate important new applications of alkenone and alkenoate biomarkers in paleoclimate and paleoenvironmental research.