Description: The Central Andes of South America host the largest known lithium resources in a confined area, but the primary lithium sources of the salar deposits and the mobilisation process of lithium are still a matter of speculation. Chemical weathering at or near the surface and leaching in hydrothermal systems of the active magmatic arc are considered the two main mechanisms of Li extraction from the source rock. The lithium and strontium isotope composition of typical salar deposits offer insights into the processes on how Li brine deposits in Andean evaporites are formed. Data from the Salar de Pozuelos indicate near-surface chemical weathering in a cold and dry climate as the dominant mobilisation process of Li, with evaporation being responsible for the enrichment. The Cenozoic ignimbrites are the favoured source rock for the Li, with subordinate additions from the Palaeozoic basement. The identification of the source rocks is supported by radiogenic Nd and Pb and stable B isotope data from salar deposits. A comparison with other Li brine and salt deposits in the Altiplano-Puna Plateau and its western foothills places the Salar de Pozuelos as an endmember of Li solubilisation by chemical weathering with only minor hydrothermal mobilisation of Li.

Description: Universität Bremen (1013)

Description: Fluid-assisted mass transport reactions by dissolution-precipitation, where a precursor mineral reacts with a fluid, play an important role in metamorphism and metasomatism. We investigated titanite growth on rutile in time series experiments between one and 107 days at constant P-T conditions of 600 °C and 400 MPa in the system TiO2-CaO-SiO2-Na2O-HCl-H2O. A two-capsule assemblage allows for transport of Ca and Si from dissolving wollastonite to dissolving rutile, the Ti-source, in a NaCl-bearing aqueous fluid, according to the general reaction CaSiO3 + TiO2 = CaTiSiO5. Complete overgrowth of rutile by titanite occurred after just one day of experiment. Fine-grained lozenge-shaped titanite crystals of short-time runs (up to 14 days) reorganize to larger predominantly prismatic crystals after 〉14 days.After investigation by scanning electron microscopy, the titanite overgrowth was removed from the rutile by hydrofluoric acid, to provide a three-dimensional view of the dissolution-reaction front on the rutile surface. The morphology of the rutile surface is dominated by humps or ridges beneath the central region of a titanite crystal and valleys at the grain boundaries between adjacent titanite crystals. The dissolution pattern on the rutile surface mimics the titanite overgrowth and changes with changing grain size and shape of the titanite with longer run times. The preferred dissolution of rutile in the valleys is clearly linked to the position of the titanite grain boundaries, which served as pathways for fluid-assisted element transport. Rutile-titanite and titanite-titanite boundaries show a significant porosity in transmission electron microscopy images of foils prepared by focused ion beam milling. The large-scale dissolution pattern on the rutile surface is independent of the crystallographic orientation of the rutile and entirely dominated by the arrangement of titanite crystals in the overgrowth. Dissolution features on a scale smaller than ~1 μm are dominated by stepwise dissolution and etch-pits following the crystallographic orientation of the rutile. Similar observations were made in experiments with an additional Al-source, although these experiments result in a different overgrowth pattern; i.e., an exposed rutile surface is always present and solitary titanite crystals are accompanied by partial overgrowths. Quantitative characterization of the surface morphology by white-light interference microscopy demonstrates that, with increasing grain size of titanite, dissolution of rutile is strongly enhanced at the titanite grain boundaries.Natural examples of titanite overgrowths on rutile show the same relations between element pathways, arrangement of titanite crystals and 3D dissolution pattern on rutile as in the experimental systems. We conclude that the transport of Ti away from the rutile and of Ca + Si into the reaction rim occurred in a grain boundary fluid, the composition of which must have been strongly different from the composition of the bulk fluid in the experiment, as well as in the natural system. The reaction progress depends on the availability of a fluid, and relicts of rutile in titanite indicate restricted availability of fluid in the natural system (e.g., a fluid pulse that was consumed by the reactions). The reaction examined here can serve as a proxy for other reactions of the conversion of oxide minerals (e.g., spinel or corundum) into silicates.

Description: Few data exist that provide insight into pro- cesses affecting the long-term carbon cycle at shallow fore- arc depths. To better understand the mobilization of C in sediments and crust of the subducting slab, we investigated carbonate materials that originate from the subduction chan- nel at the Mariana forearc (〈 20 km) and were recovered during International Ocean Discovery Program Expedition 366. Calcium carbonates occur as vein precipitates within metavolcanic and metasedimentary clasts. The clasts repre- sent portions of the subducting lithosphere, including ocean island basalt, that were altered at lower blueschist facies conditions and were subsequently transported to the fore- arc seafloor by serpentinite mud volcanism. Euhedral arag- onite and calcite and the lack of deformation within the veins suggest carbonate formation in a stress-free environ- ment after peak metamorphism affected their hosts. Inter- growth with barite and marked negative Ce anomalies in car- bonate attest the precipitation within a generally oxic envi- ronment, that is an environment not controlled by serpen- tinization. Strontium and O isotopic compositions in car- bonate (87Sr/86Sr = 0.7052 to 0.7054, δ18OVSMOW = 20 to 24 ‰) imply precipitation from slab-derived fluids at tem- peratures between ∼ 130 and 300 ◦C. These temperature es- timates are consistent with the presence of blueschist facies phases such as lawsonite coexisting with the carbonates in some veins. Incorporated C is inorganic (δ13CVPDB = −1 ‰ to +4 ‰) and likely derived from the decarbonation of cal- careous sediment and/or oceanic crust. These findings pro- vide evidence for the mobilization of C in the downgoing slab at depths of 〈 20 km. Our study shows for the first time in detail that a portion of this C forms carbonate precipitates in the subduction channel of an active convergent margin. This process may be an important asset in understanding the deep carbon cycle since it highlights that some C is lost from the subducting lithosphere before reaching greater depths.

Description: research

Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Albers, E., Bach, W., Klein, F., Menzies, C. D., Lucassen, F., & Teagle, D. A. H. Fluid-rock interactions in the shallow Mariana forearc: Carbon cycling and redox conditions. Solid Earth, 10(3), (2019): 907-930, doi: 10.5194/se-10-907-2019.

Description: Few data exist that provide insight into processes affecting the long-term carbon cycle at shallow forearc depths. To better understand the mobilization of C in sediments and crust of the subducting slab, we investigated carbonate materials that originate from the subduction channel at the Mariana forearc (〈 20 km) and were recovered during International Ocean Discovery Program Expedition 366. Calcium carbonates occur as vein precipitates within metavolcanic and metasedimentary clasts. The clasts represent portions of the subducting lithosphere, including ocean island basalt, that were altered at lower blueschist facies conditions and were subsequently transported to the forearc seafloor by serpentinite mud volcanism. Euhedral aragonite and calcite and the lack of deformation within the veins suggest carbonate formation in a stress-free environment after peak metamorphism affected their hosts. Intergrowth with barite and marked negative Ce anomalies in carbonate attest the precipitation within a generally oxic environment, that is an environment not controlled by serpentinization. Strontium and O isotopic compositions in carbonate (87Sr∕86Sr = 0.7052 to 0.7054, δ18OVSMOW = 20 to 24 ‰) imply precipitation from slab-derived fluids at temperatures between ∼130 and 300 ∘C. These temperature estimates are consistent with the presence of blueschist facies phases such as lawsonite coexisting with the carbonates in some veins. Incorporated C is inorganic (δ13CVPDB = −1 ‰ to +4 ‰) and likely derived from the decarbonation of calcareous sediment and/or oceanic crust. These findings provide evidence for the mobilization of C in the downgoing slab at depths of 〈 20 km. Our study shows for the first time in detail that a portion of this C forms carbonate precipitates in the subduction channel of an active convergent margin. This process may be an important asset in understanding the deep carbon cycle since it highlights that some C is lost from the subducting lithosphere before reaching greater depths.

Description: Funding was provided by the Deutsche Forschungsgemeinschaft (grant no. BA1605/18-1) and the Natural Environment Research Council (grant no. NE/P020909/1). Elmar Albers received financial support from the BremenIDEA out-program and from GLOMAR – Bremen International Graduate School for Marine Sciences.

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: Sediments transported in rivers reflect the geology of the catchment area and its radiogenic isotopic composition. These isotopic signatures are not significantly altered by weathering, transport or deposition and hence can document variations in sediment supply. Here we present strontium (Sr), neodymium (Nd) and lead (Pb) isotope values from suspended and riverbed sediments of the Plata River drainage basin, the second largest on the South American continent, and from two marine sediment cores collected off the mouth of the Plata River in the western subtropical South Atlantic. Our modern riverine data suggest that the basin has three main sediment source areas, namely the upper Paraná River, the Uruguay River and the Andean draining rivers. Sediments from the Andean draining rivers (Salado and Bermejo Rivers) have the most radiogenic Pb (i.e. 〉18.5 for 206Pb/204Pb) and Sr (average of 0.726 ± 0.031; 2SD) isotopic signatures, and least radiogenic εNd values (average of -10.5 ± 3.1; 2SD). The upper Paraná and Uruguay Rivers have less radiogenic Pb (i.e. 〈18.5 for 206Pb/204Pb) and Sr (average of 0.715 ± 0.003; 2SD) isotopic signatures. While the upper Paraná River has average εNd values of -7.8 ± 1.1 (2SD), the Uruguay River has average εNd values of -5.9 ± 0.2 (2SD). The modern isotopic signature at the mouth of the Plata River is largely dominated by the Andean draining rivers. To reconstruct changes in sediment supply to the western subtropical South Atlantic, we used this new riverine dataset together with literature values from the Argentine continental margin to interpret the data from two marine sediment cores. The downcore records cover the last ~ 30 kyr and show two short-lived excursions (i.e. Heinrich Stadial 1 and the Younger Dryas) and two long-term trends (i.e. late Pleistocene (i.e. ~29 to 11 cal ka BP for Sr and ~29 to 25 cal ka BP for Nd), and early and mid-Holocene). We suggest that the short-lived excursions result from increased precipitation in the headlands of the Andean draining rivers during Heinrich Stadial 1 and the Younger Dryas. The late Pleistocene long-term change showed an increase in the contribution of material from the Plata River drainage basin in relation to material from the Argentine continental margin most probably due to low sea-level. The early and mid-Holocene long-term trend showed the opposite change in sediment input and was related to decreased precipitation over most of the Plata River drainage basin.