Description: The hydrogen isotopic composition of plant leaf-wax n-alkanes (dDwax) is a novel proxy for estimating dD of past precipitation (dDp). However, vegetation life-form and relative humidity exert secondary effects on dDwax, preventing quantitative estimates of past dDp. Here, we present an approach for removing the effect of vegetation-type and relative humidity from dDwax and thus for directly estimating past dDp. We test this approach on modern day (late Holocene; 0-3 ka) sediments from a transect of 9 marine cores spanning 21°N-23°S off the western coast of Africa. We estimate vegetation type (C3 tree versus C4 grass) using d13C of leaf-wax n-alkanes and correct dDwax for vegetation-type with previously-derived apparent fractionation factors for each vegetation type. Late Holocene vegetation-corrected dDwax (dDvc) displays a good fit with modern-day dDp, suggesting that the effects of vegetation type and relative humidity have both been removed and thus that dDvc is a good estimate of dDp. We find that the magnitude of the effect of C3 tree - C4 grass changes on dDwax is small compared to dDp changes. We go on to estimate dDvc for the mid-Holocene (6-8 ka), the Last Glacial Maximum (LGM; 19-23 ka) and Heinrich Stadial 1 (HS1; 16-18.5 ka). In terms of past hydrological changes, our leaf-wax based estimates of dDp mostly reflect changes in wet season intensity, which is complementary to estimates of wet season length based on leaf-wax d13C.

Description: The past climate evolution of southwestern Africa is poorly understood and interpretations of past hydrological changes are sometimes contradictory. Here we present a record of leaf-wax dD and View the MathML source taken from a marine sediment core at 23°S off the coast of Namibia to reconstruct the hydrology and C3 versus C4 vegetation of southwestern Africa over the last 140 000 years (140 ka). We find lower leaf-wax dD and higher View the MathML source (more C4 grasses), which we interpret to indicate wetter Southern Hemisphere (SH) summer conditions and increased seasonality, during SH insolation maxima relative to minima and during the last glacial period relative to the Holocene and the last interglacial period. Nonetheless, the dominance of C4 grasses throughout the record indicates that the wet season remained brief and that this region has remained semi-arid. Our data suggest that past precipitation increases were derived from the tropics rather than from the winter westerlies. Comparison with a record from the Congo Basin indicates that hydroclimate in southwestern Africa has evolved in antiphase with that of central Africa over the last 140 ka.

Description: Diepkloof Rock Shelter (DRS) represents a site of major interest for reconstructing early human behaviours during the Middle Stone Age (MSA). Rock shelters such as DRS also potentially preserve information concerning the environmental context for such behaviours. In this respect the organic matter composition of rock shelter sediments has rarely been investigated in detail, particularly at the molecular level. Here, we used pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) to systematically assess the organic matter composition of bulk sediments within the MSA and Later Stone Age (LSA) sequence at DRS. From this we sought to gain insights into site usage, taphonomy and burning practices. Additionally, we analysed the chain length distribution of leaf-wax n-alkanes as well as their hydrogen and carbon isotopic compositions (dDwax and d13Cwax) to investigate their potential as hydroclimate and vegetation indicators. This constitutes the first leaf-wax isotopic data in a terrestrial context of this antiquity in South Africa. Py-GC/MS shows a dichotomy between stratigraphic units (SUs) of high organic matter content, producing a range of pyrolysis products, including homologous series of long chain n-alkene/n-alkane doublets and alkyl-nitriles, and SUs of low organic matter content, dominated by aromatic, heterocyclic N and polycyclic aromatic hydrocarbon (PAH) pyrolysis products; typical molecular burning products. Several SUs of the Intermediate Howiesons Poort interval exhibit the latter composition, consistent with micromorphological evidence. d13Cwax remains stable throughout the MSA, but leaf-wax n-alkane chain length and dDwax increase during the Late Howiesons Poort interval. Comparison with such patterns in modern plants in the region suggests this represents a shift towards the input of more arid-adapted vegetation into the shelter, driven either by aridification at the site locale or a change in selection practices. Our results suggest that these techniques have further potential in southern Africa and globally at sites where organic matter preservation is high.