Lidia Romero-Viana, Ulrike Kienel, Heinz Wilkes, Dirk Sachse

• In this study, we evaluated the potential of the hydrogen isotopic composition of algal lipid biomarkers as a proxy for past hydroclimatic variability in hypersaline Isabel Lake, Mexico (Eastern Pacific). We compared rainfall variability recorded in the region over the last 65 years with changes in delta D values of the most abundant compounds preserved in the uppermost 16 cm of lake sediment. Changes in delta D values of the 1,15-C-32 diol (delta D-diol), a specific biomarker of algal populations, were related to rainfall variability; specifically, n-alkyl diols were more deuterium-enriched (depleted) during wetter (drier) periods. Strikingly, neither the magnitude of lipid biomarker isotopic changes over interannual timescales (of up to 70-80 parts per thousand) nor the direction of that variability can be explained by changes in delta D values of the water source or salinity fluctuations (approximately 30 on the practical salinity scale) controlled by seasonal rainfall. However, changes in sedimentary biomarker composition, higherIn this study, we evaluated the potential of the hydrogen isotopic composition of algal lipid biomarkers as a proxy for past hydroclimatic variability in hypersaline Isabel Lake, Mexico (Eastern Pacific). We compared rainfall variability recorded in the region over the last 65 years with changes in delta D values of the most abundant compounds preserved in the uppermost 16 cm of lake sediment. Changes in delta D values of the 1,15-C-32 diol (delta D-diol), a specific biomarker of algal populations, were related to rainfall variability; specifically, n-alkyl diols were more deuterium-enriched (depleted) during wetter (drier) periods. Strikingly, neither the magnitude of lipid biomarker isotopic changes over interannual timescales (of up to 70-80 parts per thousand) nor the direction of that variability can be explained by changes in delta D values of the water source or salinity fluctuations (approximately 30 on the practical salinity scale) controlled by seasonal rainfall. However, changes in sedimentary biomarker composition, higher total organic carbon content and less negative delta C-13 values of the 1,15-C-32 diol indicate enhanced algal growth during wetter periods. We find that these conditions result in less negative delta D values of n-alkyl diols. We hypothesize that due to higher lipid demand during enhanced algal growth, an increasing proportion of hydrogen for lipid synthesis is derived from the cytosol via oxidation of polysaccharides, which may cause a deuterium enrichment of the acetogenic compounds. This study has significant implications for paleohydrological reconstructions using algal lipid delta D values, particularly in highly seasonal environments such as Isabel Lake. In such environments, delta D values of specific algal lipid biomarkers may not record the full seasonal cycle in source water delta D but appear to be mainly controlled by the physiological state of algal populations. Our data provide the first evidence that changes in D/H fractionation due to algal growth conditions can be recorded in sediments. For paleoclimate reconstructions in such environments, algal growth conditions should be constrained with additional proxy data (delta C-13 values of the same biomarkers), as the net D/H fractionation between water and lipids may not have been constant over time.…