Description: Benthic fluxes of dissolved silica (Si) from sediments into the water column are driven by the dissolution of biogenic silica (bSiO2) and terrigenous Si minerals and modulated by the precipitation of authigenic Si phases. Each of these processes has a specific effect on the isotopic composition of silica dissolved in sediment pore waters such that the determination of pore water δ30Si values can help to decipher the complex Si cycle in surface sediments. In this study, the δ30Si signatures of pore fluids and bSiO2 in the Guaymas Basin (Gulf of California) were analyzed, which is characterized by high bSiO2 accumulation and hydrothermal activity. The δ30Si signatures were investigated in the deep basin, in the vicinity of a hydrothermal vent field, and at an anoxic site located within the pronounced oxygen minimum zone (OMZ). The pore fluid δ30Sipf signatures differ significantly depending on the ambient conditions. Within the basin, δ30Sipf is essentially uniform averaging +1.2 ± 0.1 ‰ (1SD). Pore fluid δ30Sipf values from within the OMZ are significantly lower (0.0 ± 0.5 ‰, 1SD), while pore fluids close to the hydrothermal vent field are higher (+2.0 ± 0.2 ‰, 1SD). Reactive transport modelling results show that the δ30Sipf is mainly controlled by silica dissolution (bSiO2 and terrigenous phases) and Si precipitation (authigenic aluminosilicates). Precipitation processes cause a shift to high pore fluid δ30Sipf signatures, most pronounced at the hydrothermal site. Within the OMZ however, additional dissolution of isotopically depleted Si minerals (e.g. clays) facilitated by high mass accumulation rates of terrigenous material (MARterr) is required to promote the low δ30Sipf signatures while precipitation of authigenic aluminosilicates seems to be hampered by high water / rock ratios. Guaymas OMZ δ30Sipf values are markedly different from those of the Peruvian OMZ, the only other marine setting where Si isotopes have been investigated to constrain early diagenetic processes. These differences highlight the fact that δ30Sipf signals in OMZs worldwide are not alike and each setting can result in a range of δ30Sipf values as a function of the environmental conditions. We conclude that the benthic silica cycle is more complex than previously thought and that additional Si isotope studies are needed to decipher the controls on Si turnover in marine sediment and the role of sediments in the marine silica cycle.

Description: North African greening phases, during which large rivers ran through the Sahara Desert, occurred repeatedly during the Quaternary and are regarded as key periods for the development of past human populations. However, the timing and mechanisms responsible for the reactivation of the presently dormant fluvial systems remain highly uncertain. Here we present hydroclimate changes over the past 160,000 years, reconstructed from analyses of the provenance of terrestrial sediments in a marine sediment record from the Gulf of Sirte (offshore Libya). By combining high-resolution proxy data with transient Earth system model simulations, we are able to identify the various drivers that led to the observed shifts in hydroclimate and landscapes. We show that river runoff occurred during warm interglacial phases of Marine Isotope Stages 1 and 5 due to precession-forced enhancements in the summer and autumn rainfall over the entire watershed, which fed presently dry river systems and intermittent coastal streams. In contrast, shorter-lasting and less-intense humid events during glacial Marine Isotope Stages 3 and 4 were related to autumn and winter precipitation over the Libyan coastal regions driven by Mediterranean storms. Our results reveal large shifts in hydroclimate environments during the last glacial cycle, which probably exerted a strong evolutionary and structural control on past human populations, potentially pacing their dispersal across northern Africa.

Description: Ocean deoxygenation is a rising threat to marine ecosystems and food resources under present climate warming conditions. Organic-rich sapropel layers deposited in the Mediterranean Sea provide a natural laboratory to study the processes that have controlled changes in seawater oxygen levels in the recent geological past. Our study is based on three sediment cores spanning the last 10 000 years and located on a bathymetric transect offshore from the western distributaries of the Nile delta. These cores are partly to continuously laminated in the sections recording sapropel S1, which is indicative of bottom-water anoxia above the western Nile deep-sea fan. We used a combination of microfacies analyses and inorganic and organic geochemical measurements to reconstruct changes in oxygenation conditions at seasonal to millennial timescales. Millimetre-thick laminations are composed of detrital, biogenic and chemogenic sublayers reflecting seasonal successions of sedimentation. Dark layers reflect the deposition of summer floods and two types of light layers correspond to autumn plankton blooms and authigenic carbonates formed in the water column during spring–early summer, respectively. The isotopic signature of the authigenic carbonates suggests permanent anoxic to euxinic bottom waters resulting in high levels of anaerobic remineralization of organic matter and highlights their potential to reconstruct seawater chemistry at times when benthic fauna was absent. Ratios of major elements combined with biomarkers of terrestrial and marine organic matter and redox-sensitive compounds allow changes in terrigenous input, primary productivity and past deoxygenation dynamics on millennial timescales to be tracked. Rapid fluctuations of oxygenation conditions in the upper 700 m water depth occurred above the Nile deep-sea fan between 10 and 6.5 ka BP, while deeper cores recorded more stable anoxic conditions. Synchronous changes in terrigenous input, primary productivity and past oxygenation dynamics after 6.5 ka BP show that runoff-driven eutrophication played a central role in rapid oxygenation changes in the south-eastern Levantine Basin. These findings are further supported by other regional records and reveal time-transgressive changes in oxygenation state driven by rapid changes in primary productivity during a period of long-term deep-water stagnation.

Description: The Amazon River accounts for 20% of global freshwater runoff and supplies vital trace metals to the Atlantic Ocean. Suspended particles within its plume are thought to partially dissolve, constituting a large potential source of metals, which is, however, not well constrained. Here we used combined neodymium (Nd) and hafnium (Hf) isotopes to disprove the release of Nd and Hf from particles as the cause of the observed dissolved concentration increases and isotopic variability across the plume. Instead, the changes reflect admixture of nearby Pará River freshwater with exceptionally high dissolved Nd and Hf concentrations contributing 45–100% of the riverine fraction to the southern and outer estuary. This result led us to develop an empirical relationship between riverine Nd concentration and pH to revise the global dissolved riverine Nd flux, which accordingly is at least three times higher than commonly used estimates. Future work should focus on contributions of low-pH rivers to global metal fluxes.

Description: Black shale sediments from the Barremian to Aptian South Atlantic document intense and widespread burial of marine organic carbon during the initial stages of seafloor spreading between Africa and South America. The enhanced sequestration of atmospheric CO2 makes these young ocean basins potential drivers of the Early Cretaceous carbon cycle and climate perturbations. The opening of marine gateways between initially restricted basins and related circulation and ventilation changes are a commonly invoked explanation for the transient formation and disappearance of these regional carbon sinks. However, large uncertainties in paleogeographic reconstructions limit the interpretation of available paleoceanographic data and prevent any robust model-based quantifications of the proposed circulation and carbon burial changes. Here, we present a new approach to assess the principal controls on the Early Cretaceous South Atlantic and Southern Ocean circulation changes under full consideration of the uncertainties in available boundary conditions. Specifically, we use a large ensemble of 36 climate model experiments to simulate the Barremian to Albian progressive opening of the Falkland Plateau and Georgia Basin gateways with different configurations of the proto-Drake Passage, the Walvis Ridge, and atmospheric CO2 concentrations. The experiments are designed to complement available geochemical data across the regions and to test circulation scenarios derived from them. All simulations show increased evaporation and intermediate water formation at subtropical latitudes that drive a meridional overturning circulation whose vertical extent is determined by the sill depth of the Falkland Plateau. Densest water masses formed in the southern Angola Basin and potentially reached the deep Cape Basin as Walvis Ridge Overflow Water. Paleogeographic uncertainties are as important as the lack of precise knowledge of atmospheric CO2 levels for the simulated temperature and salinity spread in large parts of the South Atlantic. Overall temperature uncertainties are up to 15 °C and increase significantly with water depth. The ensemble approach reveals temporal changes in the relative importance of geographic and radiative forcings for the simulated oceanographic conditions and, importantly, nonlinear interactions between them. Progressive northward opening of the highly restricted Angola Basin increased the sensitivity of local overturning and upper ocean stratification to atmospheric CO2 concentrations due to large-scale changes in the hydrological cycle, while the chosen proto-Drake Passage depth is critical for the ocean dynamics and CO2 response in the southern South Atlantic. Finally, the simulated processes are integrated into a recent carbon burial framework to document the principal control of the regional gateway evolution on the progressive shift from the prevailing saline and oxygen-depleted subtropical water masses to the dominance of ventilated high-latitude deep waters.