Description: Boron isotope patterns preserved in cap carbonates deposited in the aftermath of the younger Cryogenian (Marinoan, ca. 635 Ma) glaciation confirm a temporary ocean acidification event on the continental margin of the southern Congo craton, Namibia. To test the significance of this acidification event and reconstruct Earth's global seawater pH states at the Cryogenian-Ediacaran transition, we present a new boron isotope data set recorded in cap carbonates deposited on the Yangtze Platform in south China and on the Karatau microcontinent in Kazakhstan. Our compiled d11B data reveal similar ocean pH patterns for all investigated cratons and confirm the presence of a global and synchronous ocean acidification event during the Marinoan deglacial period, compatible with elevated postglacial pCO2 concentrations. Differences in the details of the ocean acidification event point to regional distinctions in the buffering capacity of Ediacaran seawater.

Description: It has long been known that extreme changes in North African hydroclimate occurred during the late Pleistocene yet many discrepancies exist between sites regarding the timing, duration and abruptness of events such as Heinrich Stadial (HS) 1 and the African Humid Period (AHP). The hydroclimate history of the Nile River is of particular interest due to its lengthy human occupation history yet there are presently few continuous archives from the Nile River corridor, and pre-Holocene studies are rare. Here we present new organic and inorganic geochemical records of Nile Basin hydroclimate from an eastern Mediterranean (EM) Sea sediment core spanning the past 28 ka BP. Our multi-proxy records reflect the fluctuating inputs of Blue Nile versus White Nile material to the EM Sea in response to gradual changes in local insolation and also capture abrupt hydroclimate events driven by remote climate forcings, such as HS1. We find strong evidence for extreme aridity within the Nile Basin evolving in two distinct phases during HS1, from 17.5 to 16 ka BP and from 16 to 14.5 ka BP, whereas peak wet conditions during the AHP are observed from 9 to 7 ka BP. We find that zonal movements of the Congo Air Boundary (CAB), and associated shifts in the dominant moisture source (Atlantic versus Indian Ocean moisture) to the Nile Basin, likely contributed to abrupt hydroclimate variability in northern East Africa during HS1 and the AHP as well as to non-linear behavior of hydroclimate proxies. We note that different proxies show variable gradual and abrupt responses to individual hydroclimate events, and thus might have different inherent sensitivities, which may be a factor contributing to the controversy surrounding the abruptness of past events such as the AHP. During the Late Pleistocene the Nile Basin experienced extreme hydroclimate fluctuations, which presumably impacted Paleolithic cultures residing along the Nile corridor.

Description: The strontium (Sr), neodymium (Nd) and lead (Pb) isotope signatures of suspended particulate matter (SPM) in rivers reflect the radiogenic isotope signatures of the rivers' drainage basin. These signatures are not significantly affected by weathering, transport or depositional cycles, but document the sedimentary contributions of the respective sources. We report new Sr, Nd and Pb isotope ratios and element concentrations of modern SPM from the Brazilian Amazon River basin and document the past evolution of the basin by analyzing radiogenic isotopes of a marine sediment core from the slope off French Guiana archiving the last 40 kyr of Amazon River SPM, and the Holocene section of sediment cores raised between the Amazon River mouth and the slope off French Guiana. The composition of modern SPM confirms two main source areas, the Andes and the cratonic Shield. In the marine sediment core notable changes occurred during the second phase of Heinrich Stadial 1 (i.e. increased proportion of Shield rivers SPM) and during the last deglaciation (i.e. increased proportion of Madeira River SPM) together with elsewhere constant source contributions. Furthermore, we report a prominent offset in Sr and Nd isotopic composition between the average core value (εNd: −11.7 ± 0.9 (2SD), 87Sr/86Sr: 0.7229 ± 0.0016 (2SD)) and the average modern Amazon River SPM signal (εNd: −10.5 ± 0.5 (2SD), 87Sr/86Sr: 0.7213 ± 0.0036 (2SD)). We suggest that a permanent change in the Amazon River basin sediment supply during the late Holocene to a more Andean dominated SPM was responsible for the offset.

Description: Multiple batch experiments (100 °C, 200 °C; 40 MPa) were conducted, using Dickson-type reactors, to investigate Li and B partitioning and isotope fractionation between rock and water during serpentinization. We reacted fresh olivine (5 g; Fo90; [B] = 〈0.02 µg/g; d11BOlivine -14 per mil; [Li] = 1.7 µg/g; d7LiOlivine = +5.3 per mil) with seawater-like fluids (75 ml, 3.2 wt.% NaCl) adjusted with respect to their Li (0.2, 0.5 µg/ml; and d7LiFluid +55 per mil) and B (~10 µg/ml and d11BFluid -0.3 per mil) characteristics. At 200 °C a reaction turnover of about 70% and a serpentinization mineral assemblage matching equilibrium thermodynamic computational results (EQ3/6) developed after 224 days runtime. Characterization of concomitant fluid samples indicated a distinct B incorporation into solid phases ([B]final_200 °C = 55.61 µg/g; DS/FB200 °C = 13.42) and a preferential uptake of the lighter 10B isotope (Delta11BS-F = -3.46 per mil). Despite a low reaction turnover at 100 °C (〈12%), considerable amounts of B were again incorporated into solid phases ([B]final_100 °C = 25.33 µg/g; DS/FB100 °C = 24.2) with even a larger isotope fractionation factor (Delta11BS-F = -9.97? per mil. While magnitude of isotope fraction appears anti-correlated with temperature, we argue for an overall attenuation of the isotopic effect through changes in B speciation in saline solutions (NaB(OH)4(aq) and B(OH)3Cl-) as well as variable B fixation and fractionation for different serpentinization product minerals (brucite, chrysotile). Breakdown of the Li-rich olivine and limited Li incorporation into product mineral phases resulted in an overall lower Li content of the final solid phase assemblage at 200 °C ([Li]final_200 °C = 0.77 µg/g; DS/FLi200 °C = 1.58). First order changes in Li isotopic compositions were defined by mixing of two isotopically distinct sources i.e. the fresh olivine and the fluid rather than by equilibrium isotope fraction. At 200 °C primary olivine is dissolved, releasing its Li budget into the fluid which shifts towards a lower d7LiF of +38.62 per mil. Newly formed serpentine minerals (d7LiS = +30.58 per mil) incorporate fluid derived Li with a minor preference of the 6Li isotope. At 100 °C Li enrichment of secondary phases exceeded Li release by olivine breakdown ([Li]final_100 °C = 2.10 µg/g; DS/FLi100 °C = 11.3) and it was accompanied by preferential incorporation of heavier 7Li isotope that might be due to incorporation of a 7Li enriched fluid fraction into chrysotile nanotubes.