Neodymium isotope constraints on provenance, dispersal, and climate-driven supply of Zambezi sediments along the Mozambique Margin during the past ∼45,000 years

Marine sediments deposited off the Zambezi River that drains a considerable part of the southeast African continent provide continuous records of the continental climatic and environmental conditions. Here we present time series of neodymium (Nd) isotope signatures of the detrital sediment fraction during the past ~45,000 years, to reconstruct climate-driven changes in the provenance of clays deposited along the Mozambique Margin. Coherent with the surface current regime, the Nd isotope distribution in surface sediments reveals mixing of the alongshore flowing Zambezi suspension load with sediments supplied by smaller rivers located further north. To reconstruct past changes in sediment provenances, Nd isotope signatures of clays that are not significantly fractionated during weathering processes have been obtained from core 64PE304-80, which was recovered just north of the Zambezi mouth at 1329 m water depth. Distinctly unradiogenic clay signatures (ENd values <214.2) are found during the Last Glacial Maximum, Heinrich Stadial 1, and Younger Dryas. In contrast, the Nd isotope record shows higher, more radiogenic isotope signatures during Marine Isotope Stage 3 and between ~15 and ~5 ka BP, the latter coinciding with the timing of the northern hemisphere African Humid Period. The clay-sized sediment fraction with the least radiogenic Nd isotope signatures was deposited during the Holocene, when the adjacent Mozambique Shelf became completely flooded. In general, the contribution of the distinctly unradiogenic Zambezi suspension load has followed the intensity of precession-forced monsoonal precipitation and enhanced during periods of increased southern hemisphere insolation and high-latitude northern hemispheric climate variability

Variation in hydrogen isotope composition among saltmarsh plant organic compounds highlights biochemical mechanisms controlling biosynthetic fractionation

Hydrogen isotopes of plant‐derived biomarkers can vary by >100‰ at a single location. Isotope fractionation associated with the movement of water in plant leaves cannot account for this variability alone. Biochemical processes therefore must play a fundamental role in controlling hydrogen isotope fractionation during secondary compound biosynthesis. Different biosynthetic pathways utilize discrete hydrogen pools, and occur within distinct cell compartments. We analysed hydrogen isotope compositions of C16 and C18 fatty acids and phytol from 7 saltmarsh plants, and compared these data with: (i) leaf water and n‐alkane δ2H; (ii) leaf carbon and nitrogen contents; and (iv) nitrogen isotopes of bulk tissue, to evaluate the relationship between biochemical processes, cellular compartmentalization, and hydrogen isotope fractionation. Interspecies variation in chloroplastic fatty acids and phytol δ2H exceeds leaf water δ2H, indicating that different commitments of metabolites among species at branching points in chloroplast metabolic processes may be important determinants of lipid δ2H values. Dominant osmoregulatory strategies, in particular, show strong correlation with leaf wax n‐alkane δ2H. Species that preferentially produce nitrogenous compounds (dicots/shrubs) as protective solutes have 2H‐enriched n‐alkanes relative to species that produce mainly carbohydrates (monocots). n‐Alkane δ2H values, in combination with δ15N data and elemental (C, N) composition, together provide information about biochemical environmental adaptations exhibited by different higher plant species in response to environmental stresses. Thus, while spatial and temporal integration of biomarkers may produce an isotopic record of ecosystem function, biomarkers from individual plant or microbial remains may hold additional details into biologic function and adaptation to ancient environments

Terrestrial temperature evolution of southern Africa during the late Pleistocene and Holocene:Evidence from the Mfabeni Peatland

The scarcity of suitable high-resolution archives, such as ancient natural lakes, that span beyond the Holocene, hinders long-term late Quaternary temperature reconstructions in southern Africa. Here we target two cores from Mfabeni Peatland, one of the few long continuous terrestrial archives in South Africa that reaches into the Pleistocene, to generate a composite temperature record spanning the last ∼43 kyr. The Mfabeni Peatland has previously been proven suitable for temperature and hydrological reconstructions based on pollen and geochemical proxies. Here we use branched glycerol dialkyl glycerol tetraethers (brGDGTs) preserved in the Mfabeni peatland to derive a new quantitative air temperature record for south-east Africa. Our temperature record generally follows global trends in temperature and atmospheric CO2 concentrations, but is decoupled at times. Annual air temperatures during Marine Isotope Stage (MIS) 3 were moderately high (c. 20.5 °C), but dropped by c. 5 °C during the Last Glacial Maximum, reaching a minimum at c.16–15 ka. Asynchronous with local insolation, this cooling may have resulted from reduced sea surface temperatures linked to a northward shift in the Southern Hemisphere westerly winds. Concurrent with the southward retreat of the westerlies, and increasing sea surface temperatures offshore, warming from minimum temperatures (c. 15.0 °C) to average Holocene temperatures (c. 20.0 °C) occurred across the deglaciation. This warming was briefly but prominently interrupted by a millennial-scale cooling event of c. 3 °C at c. 2.4 ka, concurrent with a sudden change in hydrological conditions. The average Holocene temperatures of c. 20.0 °C were similar to those reconstructed for MIS 3, but after the 2.4 ka cooling period, air temperatures in the Mfabeni peat recovered and steadily increased towards the present. In summary, our record demonstrates that land temperature in eastern South Africa is highly sensitive to global drivers as well as nearby sea surface temperatures

Paleohydrological dynamics in the Western Mediterranean during the last glacial cycle

The transitional regions between the low and high latitudes of the Northern Hemisphere are highly vulnerable to future climate change yet most of the current climate models usually diverge in their projections. To better understand the dynamics in these regions, the reconstruction of past hydrological fluctuations and precipitation patterns is of paramount importance to accurately constrain present and future climate scenarios. In this study, we investigated paleohydrological dynamics in the western Mediterranean region, a transitional zone between low-mid latitudes and Atlantic - Mediterranean realms. We reconstruct precipitation and moisture source changes during the last -35 ka in order to propose the potential mechanisms driving these oscillations. To do so, we use hydrogen isotopes from sedimentary leaf waxes, more specifically the C31 n-alkane homologue, and a precipitation proxy based on previously published pollen data from a sedimentary core (Padul-15-05) in southern Iberia (Padul wetland -37-N). With this combination we disentangle the coupled effect of precipitation amount and source on the hydrogen isotopic signature of the studied C31 n-alkane record. Our results show three main periods characterized by different precipitation patterns. Low precipitation, mainly linked to a significant contribution from an isotopically-enriched Mediterranean precipitation source, occurred from -30 to -15.5 ka BP and during the last -5 ka, whereas enhanced precipitation with a predominant isotopically-depleted Atlantic precipitation source prevailed from -15.5 to -5 ka BP. This latter stage is here defined as the Western Mediterranean Humid Period (WMHP). In addition, some occasional millennial-scale opposite precipitation patterns can be observed during these climatically distinct periods. These changes in the source of precipitation were likely coupled to a shift in the main rainy season from winter, when Atlantic precipitation prevailed, to late winter-early spring, when the contribution of Mediterranean moisture is higher. Comparison between the studied mid-latitude terrestrial Padul-15-05 core and a low-latitude marine record offshore of northwestern Africa shows clear long-term synchronous responses of both western Mediterranean precipitation and western African monsoon systems to northern Hemisphere atmospheric dynamics, ultimately controlled by orbital forcing and ice-sheets fluctuations.Peer reviewe

A comparison of biomarker records of northeast African vegetation from lacustrine and marine sediments (ca. 3.40 Ma)

Author Posting. © Elsevier B.V., 2007. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Organic Geochemistry 38 (2007): 1607-1624, doi:10.1016/j.orggeochem.2007.06.008.Integrated terrestrial and marine records of northeast African vegetation are needed to provide long, high resolution records of environmental variability with established links to specific terrestrial environments. In this study, we compare records of terrestrial vegetation preserved in marine sediments in the Gulf of Aden (DSDP Site 231) and an outcrop of lacustrine sediments in the Turkana Basin, Kenya, part of the East African Rift System. We analyzed higher plant biomarkers in sediments from both deposits of known equivalent age, corresponding to a ca. 50 – 100 ka humid interval prior to the β-Tulu Bor eruption ca. 3.40 Ma, when the Lokochot Lake occupied part of the Turkana Basin. Molecular abundance distributions indicate that long chain n-alkanoic acids in marine sediments are the most reliable proxy for terrestrial vegetation (Carbon Preference Index, CPI, = 4.5), with more cautious interpretation needed for n-alkanes and lacustrine archives. Marine sediments record carbon isotopic variability in terrestrial biomarkers of 2 – 3‰, roughly equivalent to 20% variability in the C3/C4 vegetation contribution. The proportion of C4 vegetation apparently increased at times of low terrigenous dust input. Terrestrial sediments reveal much larger (2 – 10‰) shifts in n-alkanoic acid δ13C values. However, molecular abundance and isotopic composition suggest that microbial sources may also contribute fatty acids, contaminating the lacustrine sedimentary record of terrestrial vegetation.Funding was provided by the U.S. National Science Foundation HOMINID Grant 0218511

Hydrogen isotope exchange between n-alkanes and water under hydrothermal conditions

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 77 (2012): 582–599, doi:10.1016/j.gca.2011.10.008.To investigate the extent of hydrogen isotope (2H and 1H) exchange between hydrocarbons and water under hydrothermal conditions, we performed experiments heating C1–C5 n-alkanes in aqueous solutions of varying initial 2H/1H ratios in the presence of a pyrite-pyrrhotite-magnetite redox buffer at 323ºC and 35–36MPa. Extensive and reversible incorporation of water-derived hydrogen into C2–C5 n-alkanes was observed on timescales of months. In contrast, comparatively minor exchange was observed for CH4. Isotopic exchange is facilitated by reversible equilibration of n-alkanes and their corresponding n-alkenes with H2 derived from the disproportionation of water. Rates of δ2H variation in C3+ n-alkanes decreased with time, a trend that is consistent with an asymptotic approach to steady-state isotopic compositions regulated by alkane-water isotopic equilibrium. Substantially slower δ2H variation was observed for ethane relative to C3–C5 n-alkanes, suggesting that the greater stability of C3+ alkenes and isomerization reactions may dramatically enhance rates of 2H/1H exchange in C3+ n-alkanes. Thus, in reducing aqueous environments, reversible reaction of alkenes and their corresponding alkanes facilitates rapid 2H/1H exchange between alkyl- and water-bound hydrogen on relatively short geological timescales at elevated temperatures and pressures. The proximity of some thermogenic and purported abiogenic alkane δ2H values to those predicted for equilibrium 2H/1H fractionation with ambient water suggests that this process may regulate the δ2H signatures of some naturally occurring hydrocarbons.This research received financial support from the Department of Energy (grant DE-FG02-97ER14746), the National Science Foundation (grant OCE-0549829) and the WHOI Deep Ocean Exploration Institute Graduate Fellowship (to E.P. Reeves)

Strengthening of North American dust sources during the late Pliocene (2.7Ma)

Here we present orbitally-resolved records of terrestrial higher plant leaf wax input to the North Atlantic over the last 3.5 Ma, based on the accumulation of long-chain n-alkanes and n-alkanl-1-ols at IODP Site U1313. These lipids are a major component of dust, even in remote ocean areas, and have a predominantly aeolian origin in distal marine sediments. Our results demonstrate that around 2.7 million years ago (Ma), coinciding with the intensification of the Northern Hemisphere glaciation (NHG), the aeolian input of terrestrial material to the North Atlantic increased drastically. Since then, during every glacial the aeolian input of higher plant material was up to 30 times higher than during interglacials. The close correspondence between aeolian input to the North Atlantic and other dust records indicates a globally uniform response of dust sources to Quaternary climate variability, although the amplitude of variation differs among areas. We argue that the increased aeolian input at Site U1313 during glacials is predominantly related to the episodic appearance of continental ice sheets in North America and the associated strengthening of glaciogenic dust sources. Evolutional spectral analyses of the n-alkane records were therefore used to determine the dominant astronomical forcing in North American ice sheet advances. These results demonstrate that during the early Pleistocene North American ice sheet dynamics responded predominantly to variations in obliquity (41 ka), which argues against previous suggestions of precession-related variations in Northern Hemisphere ice sheets during the early Pleistocene

Paleo-environmental effects of the mid-pleistocene transition in the tropical Atlantic and equatorial Africa

This thesis describes the environmental changes in the eastern tropical Atlantic and equatorial Africa during the Mid-Pleistocene Transition (MPT) as revealed by analyses of lipid biomarkers and their stable carbon isotope compositions. The MPT was the start of the Late Pleistocene ice ages, with an enlarged mean global ice volume varying in a predominant 100-kyr cyclicity. Before the MPT, global ice volume was, on average, smaller and had a prevalent 41-kyr cyclicity. The increase in mean global ice mass around 920 kyr BP significantly preceded the establishment of the 100-kyr cycle at 640 kyr 8P. A pronounced effect of the MPT was the temporary severe decrease of the Atlantic deepwater ventilation, caused by the strongest reductions of North Atlantic Deep-Water formation in the last 2.5 million years