Reinhard
Christopher T.
Reinhard
Christopher T.
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PreprintTrace elements at the intersection of marine biological and geochemical evolution( 2016-10) Robbins, Leslie J. ; Lalonde, Stefan V. ; Planavsky, Noah J. ; Partin, Camille A. ; Reinhard, Christopher T. ; Kendall, Brian ; Scott, Clint ; Hardisty, Dalton S. ; Gill, Benjamin C. ; Alessi, Daniel S. ; Dupont, Christopher L. ; Saito, Mak A. ; Crowe, Sean A. ; Poulton, Simon W. ; Bekker, Andrey ; Lyons, Timothy W. ; Konhauser, Kurt O.Life requires a wide variety of bioessential trace elements to act as structural components and reactive centers in metalloenzymes. These requirements differ between organisms and have evolved over geological time, likely guided in some part by environmental conditions. Until recently, most of what was understood regarding trace element concentrations in the Precambrian oceans was inferred by extrapolation, geochemical modeling, and/or genomic studies. However, in the past decade, the increasing availability of trace element and isotopic data for sedimentary rocks of all ages have yielded new, and potentially more direct, insights into secular changes in seawater composition – and ultimately the evolution of the marine biosphere. Compiled records of many bioessential trace elements (including Ni, Mo, P, Zn, Co, Cr, Se, and I) provide new insight into how trace element abundance in Earth’s ancient oceans may have been linked to biological evolution. Several of these trace elements display redox-sensitive behavior, while others are redox-sensitive but not bioessential (e.g., Cr, U). Their temporal trends in sedimentary archives provide useful constraints on changes in atmosphere-ocean redox conditions that are linked to biological evolution, for example, the activity of oxygen-producing, photosynthetic cyanobacteria. In this review, we summarize available Precambrian trace element proxy data, and discuss how temporal trends in the seawater concentrations of specific trace elements may be linked to the evolution of both simple and complex life. We also examine several biologically relevant and/or redox-sensitive trace elements that have yet to be fully examined in the sedimentary rock record (e.g., Cu, Cd, W) and suggest several directions for future studies.
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PreprintAn evaluation of sedimentary molybdenum and iron as proxies for pore fluid paleoredox conditions( 2018-04) Hardisty, Dalton S. ; Lyons, Timothy W. ; Riedinger, Natascha ; Isson, Terry T. ; Owens, Jeremy D. ; Aller, Robert C. ; Rye, Danny ; Planavsky, Noah J. ; Reinhard, Christopher T. ; Gill, Benjamin C. ; Masterson, Andrew L. ; Asael, Dan ; Johnston, David T.Iron speciation and trace metal proxies are commonly applied together in efforts to identify anoxic settings marked by the presence of free sulfide (euxinia) or dissolved iron (ferruginous) in the water column. Here, we use a literature compilation from modern localities to provide a new empirical evaluation of coupled Fe speciation and Mo concentrations as a proxy for pore water sulfide accumulation at non-euxinic localities. We also present new Fe speciation, Mo concentration, and S isotope data from the Friends of Anoxic Mud (FOAM) site in Long Island Sound, which is marked by pore water sulfide accumulation of up to 3 mM beneath oxygen-containing bottom waters. For the operationally defined Fe speciation scheme, ‘highly reactive’ Fe (FeHR) is the sum of pyritized Fe (Fepy) and Fe dominantly present in oxide phases that is available to react with pore water sulfide to form pyrite. Observations from FOAM and elsewhere confirm that Fepy/FeHR from non-euxinic sites is a generally reliable indicator of pore fluid redox, particularly the presence of pore water sulfide. Molybdenum (Mo) concentration data for anoxic continental margin sediments underlying oxic waters but with sulfidic pore fluids typically show authigenic Mo enrichments (2-25 ppm) that are elevated relative to the upper crust (1-2 ppm). However, compilations of Mo concentrations comparing sediments with and without sulfidic pore fluids underlying oxic and low oxygen (non-euxinic) water columns expose non-unique ranges for each, exposing false positives and false negatives. False positives are most frequently found in sediments from low oxygen water columns (for example, Peru Margin), where Mo concentration ranges can also overlap with values commonly found in modern euxinic settings. FOAM represents an example of a false negative, where, despite elevated pore water sulfide concentrations and evidence for active Fe and Mn redox cycling in FOAM sediments, sedimentary Mo concentrations show a homogenous vertical profile across 50 cm depth at 1-2 ppm. A diagenetic model for Mo provides evidence that muted authigenic enrichments are derived from elevated sedimentation rates. Consideration of a range of additional parameters, most prominently pore water Mo concentration, can replicate the ranges of most sedimentary Mo concentrations observed in modern non-euxinic settings. Together, the modern Mo and Fe data compilations and diagenetic model provide a framework for identifying paleo-pore water sulfide accumulation in ancient settings and linked processes regulating seawater Mo and sulfate concentrations and delivery to sediments. Among other utilities, identifying ancient accumulation of sulfide in pore waters, particularly beneath oxic bottom waters, constrains the likelihood that those settings could have hosted organisms and ecosystems with thiotrophy at their foundations.
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PreprintChromium isotope fractionation during subduction-related metamorphism, black shale weathering, and hydrothermal alteration( 2016-01) Wang, Xiangli ; Planavsky, Noah J. ; Reinhard, Christopher T. ; Zou, Huijuan ; Ague, Jay J. ; Wu, Yuanbao ; Gill, Benjamin C. ; Schwarzenbach, Esther M. ; Peucker-Ehrenbrink, BernhardChromium (Cr) isotopes are an emerging proxy for redox processes at Earth’s surface. However, many geological reservoirs and isotope fractionation processes are still not well understood. The purpose of this contribution is to move forward our understanding of (1) Earth’s high temperature Cr isotope inventory and (2) Cr isotope fractionations during subduction-related metamorphism, black shale weathering and hydrothermal alteration. The examined basalts and their metamorphosed equivalents yielded δ53Cr values falling within a narrow range of -0.12±0.13‰ (2SD, n=30), consistent with the previously reported range for the bulk silicate Earth (BSE). Compilations of currently available data for fresh silicate rocks (43 samples), metamorphosed silicate rocks (50 samples), and mantle chromites (39 samples) give δ53Cr values of -0.13±0.13‰, -0.11±0.13‰, and -0.07±0.13‰, respectively. Although the number of high-temperature samples analyzed has tripled, the originally proposed BSE range appears robust. This suggests very limited Cr isotope fractionation under high temperature conditions. Additionally, in a highly altered metacarbonate transect that is representative of fluid-rich regional metamorphism, we did not find resolvable variations in δ53Cr, despite significant loss of Cr. This work suggests that primary Cr isotope signatures may be preserved even in instances of intense metamorphic alteration at relatively high fluid-rock ratios. Oxidative weathering of black shale at low pH creates isotopically heavy mobile Cr(VI). However, a significant proportion of the Cr(VI) is apparently immobilized near the weathering surface, leading to local enrichment of isotopically heavy Cr (δ53Cr values up to ~0.5‰). The observed large Cr isotope variation in the black shale weathering profile provides indirect evidence for active manganese oxide formation, which is primarily controlled by microbial activity. Lastly, we found widely variable δ53Cr (-0.2‰ to 0.6‰) values in highly serpentinized peridotites from ocean drilling program drill cores and outcropping ophiolite sequences. The isotopically heavy serpentinites are most easily explained through a multi-stage alteration processes: Cr loss from the host rock under oxidizing conditions, followed by Cr enrichment under sulfate reducing conditions. In contrast, Cr isotope variability is limited in mildly altered mafic oceanic crust.
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ArticleTechnical comment on "Reexamination of 2.5-Ga 'whiff' of oxygen interval points to anoxic ocean before GOE"(American Association for the Advancement of Science, 2023-03-03) Anbar, Ariel D. ; Buick, Roger ; Gordon, Gwyneth W. ; Johnson, Aleisha C. ; Kendall, Brian ; Lyons, Timothy W. ; Ostrander, Chadlin M. ; Planavsky, Noah J. ; Reinhard, Christopher T. ; Stüeken, Eva E.Many lines of inorganic geochemical evidence suggest transient "whiffs" of environmental oxygenation before the Great Oxidation Event (GOE). Slotznickassert that analyses of paleoredox proxies in the Mount McRae Shale, Western Australia, were misinterpreted and hence that environmental Olevels were persistently negligible before the GOE. We find these arguments logically flawed and factually incomplete.
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ArticleReconciling evidence of oxidative weathering and atmospheric anoxia on Archean Earth(American Association for the Advancement of Science, 2021-09-29) Johnson, Aleisha C. ; Ostrander, Chadlin M. ; Romaniello, Stephen J. ; Reinhard, Christopher T. ; Greaney, Allison T. ; Lyons, Timothy W. ; Anbar, Ariel D.Evidence continues to emerge for the production and low-level accumulation of molecular oxygen (O2) at Earth’s surface before the Great Oxidation Event. Quantifying this early O2 has proven difficult. Here, we use the distribution and isotopic composition of molybdenum in the ancient sedimentary record to quantify Archean Mo cycling, which allows us to calculate lower limits for atmospheric O2 partial pressures (PO2) and O2 production fluxes during the Archean. We consider two end-member scenarios. First, if O2 was evenly distributed throughout the atmosphere, then PO2 > 10–6.9 present atmospheric level was required for large periods of time during the Archean eon. Alternatively, if O2 accumulation was instead spatially restricted (e.g., occurring only near the sites of O2 production), then O2 production fluxes >0.01 Tmol O2/year were required. Archean O2 levels were vanishingly low according to our calculations but substantially above those predicted for an abiotic Earth system.