Thallium-isotopic compositions of euxinic sediments as a proxy for global manganese-oxide burial

© The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 213 (2017): 291-307, doi:10.1016/j.gca.2017.06.041.Thallium (Tl) isotopes are a new and potentially powerful paleoredox proxy that may track bottom water oxygen conditions based on the global burial flux of manganese oxides. Thallium has a residence time of ~20 thousand years, which is longer than the ocean mixing time, and it has been inferred that modern oxic seawater is conservative with respect to both concentration and isotopes. Marine sources of Tl have nearly identical isotopic values. Therefore, the Tl sinks, adsorption onto manganese oxides and low temperature oceanic crust alteration (the dominant seawater output), are the primary controls of the seawater isotopic composition. For relatively short-term, ~million years, redox events it is reasonable to assume that the dominant mechanism that alters the Tl isotopic composition of seawater is associated with manganese oxide burial because large variability in low temperature ocean crust alteration is controlled by long-term, multi-million years, average ocean crust production rates. This study presents new Tl isotope data for an open ocean transect in the South Atlantic, and depth transects for two euxinic basins (anoxic and free sulfide in the water column), the Cariaco Basin and Black Sea. The Tl isotopic signature of open ocean seawater in the South Atlantic was found to be homogeneous with ε205Tl = -6.0 ± 0.3 (± 2 SD, n = 41) while oxic waters from Cariaco and the Black Sea are -5.6 and -2.2, respectively. Combined with existing data from the Pacific and Arctic Oceans, our Atlantic data establish the conservatism of Tl isotopes in the global ocean. In contrast, partially- and predominantly-restricted basins reveal Tl isotope differences that vary between open-ocean (-6) and continental material (-2) ε205Tl, scaling with the degree of restriction. Regardless of the differences between basins, Tl is quantitatively removed from their euxinic waters below the chemocline. The burial of Tl in euxinic sediments is estimated to be an order of magnitude less than each of the modern ocean outputs and imparts no isotopic fractionation. Thallium removal into pyrite appears to be associated with a small negative fractionation between -1 and -3 ε205Tl, which renders Tl-depleted waters below the chemocline enriched in isotopically-heavy Tl. Due to the quantitative removal of Tl from euxinic seawater, Tl isotope analyses of the authigenic fraction of underlying euxinic sediments from both the Black Sea and Cariaco Basin capture the Tl isotope value of the oxic portion of their respective water column with no net isotope fractionation. Since the Tl isotope composition of seawater is largely dictated by the relative fraction of Mn-oxide burial versus oceanic crust alteration, we contend that the Tl isotope composition of authigenic Tl in black shales, deposited under euxinic conditions but well-connected to the open ocean, can be utilized to reconstruct the Tl isotope composition of seawater, and thus to reconstruct the global history of Mn-oxide burial.JDO and SGN would like to thank NSF and NASA for funding; JDO and TJH gratefully acknowledges support from the Agouron Institute Postdoctoral Fellowship Program

The James Webb Space Telescope Mission

Twenty-six years ago a small committee report, building on earlier studies, expounded a compelling and poetic vision for the future of astronomy, calling for an infrared-optimized space telescope with an aperture of at least $4m$. With the support of their governments in the US, Europe, and Canada, 20,000 people realized that vision as the $6.5m$ James Webb Space Telescope. A generation of astronomers will celebrate their accomplishments for the life of the mission, potentially as long as 20 years, and beyond. This report and the scientific discoveries that follow are extended thank-you notes to the 20,000 team members. The telescope is working perfectly, with much better image quality than expected. In this and accompanying papers, we give a brief history, describe the observatory, outline its objectives and current observing program, and discuss the inventions and people who made it possible. We cite detailed reports on the design and the measured performance on orbit.Comment: Accepted by PASP for the special issue on The James Webb Space Telescope Overview, 29 pages, 4 figure

Refining the roles of productivity, redox, and remineralization on the cadmium isotope composition of marine sediments

Cadmium (Cd) has a nutrient-like distribution in the ocean, similar to the macronutrient phosphate. Significant isotope fractionation induced by the biological cycling of Cd makes it a potential tracer for nutrients and productivity. However, the Cd flux and Cd isotope composition of marine sediments can also be influenced by local redox conditions and partial remineralization of organically hosted Cd. These confounding factors are under-constrained and render it challenging to use Cd as a reliable paleoproxy. To understand the relative importance of each of these processes, we examined the Cd isotope systematics of 69 modern sediments deposited across a wide range of environments. We complement these data with four profiles of particulate Cd isotope compositions from the Southern Ocean. We report three main results. First, we show that the sedimentary flux of Cd is tightly coupled to that of organic matter. Second, most Cd burial occurs in regions with some bottom-water oxygen, and the flux of CdS to anoxic regions is, globally, minor. Finally, we find that remineralization can substantially modify sedimentary Cd isotope compositions, though it is challenging to relate pelagic and sedimentary processes. For example, we find that the relationship between sedimentary Cd isotope compositions and surface seawater [Cd] is the reverse of that predicted by isotope reactor models. Likewise, sedimentary Cd isotope compositions are anti-correlated with bottom-water oxygen. While this pattern is consistent with preferential remineralization of isotopically heavy Cd, profiles of marine particulate matter reveal the reverse, whereby the Cd isotope composition of large particles, which are most likely to reach the seafloor, becomes increasingly ‘heavy’ with depth. These results highlight how productivity, redox, and remineralization all influence the flux and isotope composition of Cd to marine sediments. While our study suggests that there is no simple way to relate sedimentary Cd isotopes to surface nutrient utilization, our data point toward several potential controls that could form the basis of novel proxies for local redox conditions and remineralization