Description: Hydrogen isotope values (dD) of sedimentary terrestrial leaf wax such as n-alkanes or n-acids have been used to map and understand past changes in rainfall amount in the tropics because dD of precipitation is commonly assumed as the first order controlling factor of leaf wax dD. Plant functional types and their photosynthetic pathways can also affect leaf wax dD but these biological effects are rarely taken into account in paleo studies relying on this rainfall proxy. To investigate how biological effects may influence dD values we here present a 37,000-year old record of dD and stable carbon isotopes (d13C) measured on four n-alkanes (n-C27, n-C29, n-C31, n-C33) from a marine sediment core collected off the Zambezi River mouth. Our paleo d13C records suggest that each individual n-alkanes had different C3/C4 proportional contributions. n-C29 was mostly derived from a C3 dicots (trees, shrubs and forbs) dominant vegetation throughout the entire record. In contrast, the longer chain n-C33 and n-C31 were mostly contributed by C4 grasses during the Glacial period but shifted to a mixture of C4 grasses and C3 dicots during the Holocene. Strong correlations between dD and d13C values of n-C33 (correlation coefficient R2 = 0.75, n = 58) and n-C31 (R2 = 0.48, n = 58) suggest that their dD values were strongly influenced by changes in the relative contributions of C3/C4 plant types in contrast to n-C29 (R2 = 0.07, n = 58). Within regions with variable C3/C4 input, we conclude that dD values of n-C29 are the most reliable and unbiased indicator for past changes in rainfall, and that dD and d13C values of n-C31 and n-C33 are sensitive to C3/C4 vegetation changes. Our results demonstrate that a robust interpretation of palaeohydrological data using n-alkane dD requires additional knowledge of regional vegetation changes from which nalkanes are synthesized, and that the combination of dD and d13C values of multiple n-alkanes can help to differentiate biological effects from those related to the hydrological cycle.

Description: Different proxies for sea surface temperature (SST) often exhibit divergent trends for deglacial warming in tropical regions, hampering our understanding of the phase relationship between tropical SSTs and continental ice volume at glacial terminations. To reconcile divergent SST trends, we report reconstructions of two commonly used paleothermometers (the foraminifera G. ruber Mg/Ca and the alkenone unsaturation index) from a marine sediment core collected in the southwestern tropical Indian Ocean encompassing the last 37,000 years. Our results show that SSTs derived from the alkenone unsaturation index (UK'37) are consistently warmer than those derived from Mg/Ca by ~2-3°C except for the Heinrich Event 1. In addition, the initial timing for the deglacial warming of alkenone SST started at ~15.6 ka, which lags behind that of Mg/Ca temperatures by 2.5 kyr. We argue that the discrepancy between the two SST proxies reflects seasonal differences between summer and winter rather than post-depositional processes or sedimentary biases. The UK'37 SST record clearly mimics the deglacial SST trend recorded in the North Atlantic region for the earlier part of the termination, indicating the early deglacial warming trend attributed to local summer temperatures was likely mediated by changes in the Atlantic Meridional Overturning Circulation at the onset of the deglaciation, In contrast, the glacial to interglacial SST pattern recorded by G. ruber Mg/Ca probably reflects cold season SSTs. This indicates that the cold season SSTs was likely mediated by climate changes in the southern hemisphere, as it closely tracks the Antarctic timing of deglaciation. Therefore our study reveals that the tropical southwestern Indian Ocean seasonal SST was closely linked to climate changes occurring in both hemispheres. The austral summer and winter recorded by each proxy is further supported with seasonal SST trends modeled by AOGCMs for our core site. Our interpretation that the alkenone and Mg/Ca SSTs are seasonally biased may also explain similar proxy mismatches observed in other tropical regions at the onset of the last termination.

Description: We have analyzed the stable carbon isotopic composition of the diunsaturated C37 alkenone in 29 surface sediments from the equatorial and South Atlantic Ocean. Our study area covers different oceanographic settings, including sediments from the major upwelling regions off South Africa, the equatorial upwelling, and the oligotrophic western South Atlantic. In order to examine the environmental influences on the sedimentary record the alkenone-based carbon isotopic fractionation (Ep) values were correlated with the overlying surface water concentrations of aqueous CO2 ([CO2(aq)]), phosphate, and nitrate. We found Ep positively correlated with 1/[CO2(aq)] and negatively correlated with [PO43-] and [NO3-]. However, the relationship between Ep and 1/[CO2(aq)] is opposite of what is expected from a [CO2(aq)] controlled, diffusive uptake model. Instead, our findings support the theory of Bidigare et al. (1997, doi:10.1029/96GB03939) that the isotopic fractionation in haptophytes is related to nutrient-limited growth rates. The relatively high variability of the Ep-[PO4] relationship in regions with low surface water nutrient concentrations indicates that here other environmental factors also affect the isotopic signal. These factors might be variations in other growth-limiting resources such as light intensity or micronutrient concentrations.