Precambrian to modern manganese mineralization: changes in ore type and depositional environment

Manganese mineralization is diverse in occurrence, origin, mineralogy and geochemistry. These variations reflect differences in the processes of formation and depositional environments, which in turn are a response to changes in the land-ocean-atmosphere system over geological time. As such, manganese deposits can act as markers of major events in the dynamic evolution of the Earth's surface. Modern manganese accumulations provide insights into key factors controlling manganese deposition that cannot readily be determined from examination of ancient ores. A knowledge of oceanic currents, ocean chemistry or small-scale variations in physicochemical patterns of recent basins, for example, may extend our understanding of depositional processes in the past. Equally, the study of Precambrian deposits not only elucidates ancient mechanisms of manganese metallogenesis, but also helps to unravel the impact of comprehensive environmental changes on metal deposition on a scale not realized in younger geological times

Seawater osmium isotope evidence for a middle Miocene flood basalt event in ferromanganese crust records

Three ferromanganese crusts from the northeast, northwest and central Atlantic were re-dated using osmium (Os) isotope stratigraphy and yield ages from middle Miocene to the present. The three Os isotope records do not show evidence for growth hiatuses. The reconstructed Os isotope-based growth rates for the sections older than 10 Ma are higher than those determined previously by the combined beryllium isotope (10Be/9Be) and cobalt (Co) constant-flux methods, which results in a decrease in the maximum age of each crust. This re-dating does not lead to significant changes to the interpretation of previously determined radiogenic isotope neodymium, lead (Nd, Pb) time series because the variability of these isotopes was very small in the records of the three crusts prior to 10 Ma. The Os isotope record of the central Atlantic crust shows a pronounced minimum during the middle Miocene between 15 and 12 Ma, similar to a minimum previously observed in two ferromanganese crusts from the central Pacific. For the other two Atlantic crusts, the Os isotope records and their calibration to the global seawater curve for the middle Miocene are either more uncertain or too short and thus do not allow for a reliable identification of an isotopic minimum. Similar to pronounced minima reported previously for the Cretaceous/Tertiary and Eocene/Oligocene boundaries, possible interpretations for the newly identified middle Miocene Os isotope minimum include changes in weathering intensity and/or a meteorite impact coinciding with the formation of the Nördlinger Ries Crater. It is suggested that the eruption and weathering of the Columbia River flood basalts provided a significant amount of the unradiogenic Os required to produce the middle Miocene minimum

Spectroscopic insights into ferromanganese crust formation and diagenesis

Author Posting. © American Geophysical Union, 2020. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 21(11), (2020): e2020GC009074, doi:10.1029/2020GC009074.Marine ferromanganese deposits, often called the scavengers of the sea, adsorb and coprecipitate with a wide range of metals of great interest for paleo‐environmental reconstructions and economic geology. The long (up to ∼75 Ma), near‐continuous record of seawater chemistry afforded by ferromanganese deposits offers much historical information about the global ocean and surface earth including crustal processes, mantle processes, ocean circulation, and biogeochemical cycles. The extent to which the ferromanganese deposits hosting these geochemical proxies undergo diagenesis on the seafloor, however, remains an important and challenging factor in assessing the fidelity of such records. In this study, we employ multiple X‐ray techniques including micro–X‐ray fluorescence, bulk and micro–X‐ray absorption spectroscopy, and X‐ray powder diffraction to probe the structural, compositional, redox, and mineral changes within a single ferromanganese crust. These techniques illuminate a complex two‐dimensional structure characterized by crust growth controlled by the availability of manganese (Mn), a dynamic range in Mn oxidation state from +3.4 to +4.0, changes in Mn mineralogy over time, and recrystallization in the lower phosphatized portions of the crust. Iron (Fe) similarly demonstrates spatial complexity with respect to concentration and mineralogy, but lacks the dynamic range of oxidation state seen for Mn. Micrometer‐scale measurements of metal abundances reveal complex element associations between trace elements and the two major oxide phases, which are not typically resolvable via bulk analytical methods. These findings provide evidence of post‐depositional processes altering chemistry and mineralogy, and provide important geochemical context for the interpretation of element and isotopic records in ferromanganese crusts.This research is supported by NASA Exobiology NNX15AM046 to Scott D. Wankel and Colleen M. Hansel, NASA NESSF NNX15AR62H to Kevin M. Sutherland, and WHOI Ocean Exploration Institute to Colleen M. Hansel. The Stanford Synchrotron Radiation Lightsource was utilized in this study. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE‐AC02‐76SF00515.2021-04-2

Fractionation profiling: a fast and versatile approach for mapping vesicle proteomes and protein-protein interactions.

We developed "fractionation profiling," a method for rapid proteomic analysis of membrane vesicles and protein particles. The approach combines quantitative proteomics with subcellular fractionation to generate signature protein abundance distribution profiles. Functionally associated groups of proteins are revealed through cluster analysis. To validate the method, we first profiled >3500 proteins from HeLa cells and identified known clathrin-coated vesicle proteins with >90% accuracy. We then profiled >2400 proteins from Drosophila S2 cells, and we report the first comprehensive insect clathrin-coated vesicle proteome. Of importance, the cluster analysis extends to all profiled proteins and thus identifies a diverse range of known and novel cytosolic and membrane-associated protein complexes. We show that it also allows the detailed compositional characterization of complexes, including the delineation of subcomplexes and subunit stoichiometry. Our predictions are presented in an interactive database. Fractionation profiling is a universal method for defining the clathrin-coated vesicle proteome and may be adapted for the analysis of other types of vesicles and particles. In addition, it provides a versatile tool for the rapid generation of large-scale protein interaction maps

Iterative in Situ Click Chemistry Assembles a Branched Capture Agent and Allosteric Inhibitor for Akt1

We describe the use of iterative in situ click chemistry to design an Akt-specific branched peptide triligand that is a drop-in replacement for monoclonal antibodies in multiple biochemical assays. Each peptide module in the branched structure makes unique contributions to affinity and/or specificity resulting in a 200 nM affinity ligand that efficiently immunoprecipitates Akt from cancer cell lysates and labels Akt in fixed cells. Our use of a small molecule to preinhibit Akt prior to screening resulted in low micromolar inhibitory potency and an allosteric mode of inhibition, which is evidenced through a series of competitive enzyme kinetic assays. To demonstrate the efficiency and selectivity of the protein-templated in situ click reaction, we developed a novel QPCR-based methodology that enabled a quantitative assessment of its yield. These results point to the potential for iterative in situ click chemistry to generate potent, synthetically accessible antibody replacements with novel inhibitory properties

Reconstructing the evolution of the submarine Monterey Canyon System from Os, Nd, and Pb isotopes in hydrogenetic Fe-Mn crusts

Author Posting. © American Geophysical Union, 2017. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 18 (2017): 3946–3963, doi:10.1002/2017GC007071.The sources of terrestrial material delivered to the California margin over the past 7 Myr were assessed using 187Os/188Os, Nd, and Pb isotopes in hydrogenetic ferromanganese crusts from three seamounts along the central and southern California margin. From 6.8 to 4.5 (±0.5) Ma, all three isotope systems show more radiogenic values at Davidson Seamount, located near the base of the Monterey Canyon System, than in Fe-Mn crusts from the more remote Taney and Hoss Seamounts. At the Taney Seamounts, approximately 225 km farther offshore from Davidson Seamount, 187Os/188Os values, but not Pb and Nd isotope ratios, also deviate from the Cenozoic seawater curve toward more radiogenic values from 6.8 to 4.5 (±0.5) Ma. However, none of the isotope systems in Fe-Mn crusts deviate from seawater at Hoss Seamount located approximately 450 km to the south. The regional gradients in isotope ratios indicate that substantial input of dissolved and particulate terrestrial material into the Monterey Canyon System is responsible for the local deviations in the seawater Nd, Pb, and Os isotope compositions from 6.8 to 4.5 (±0.5) Ma. The isotope ratios recorded in Fe-Mn crusts are consistent with a southern Sierra Nevada or western Basin and Range provenance of the terrestrial material which was delivered by rivers to the canyon. The exhumation of the modern Monterey Canyon must have begun between 10 and 6.8 ± 0.5 Ma, as indicated by our data, the age of incised strata, and paleo-location of the Monterey Canyon relative to the paleo-coastline.Funding was provided by the United States Geological Survey Pacific Coastal and Marine Science Center Marine Minerals Group, the University of California Santa Cruz Scholarship for Re-Entry Women in Science, and the UCSC Earth and Planetary Science Department Waters Award.2018-05-1