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  • 1
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    In:  Supplement to: Partin, C A; Bekker, A; Planavsky, Noah J; Lyons, Timothy W (2015): Euxinic conditions recorded in the ca. 1.93Ga Bravo Lake Formation, Nunavut (Canada): Implications for oceanic redox evolution. Chemical Geology, 417, 148-162, https://doi.org/10.1016/j.chemgeo.2015.09.004
    Publication Date: 2020-01-17
    Description: The composition of seawater changed dramatically during the initial rise of atmospheric oxygen in the earliest Paleoproterozoic, but the emerging view is that atmosphere-ocean system did not experience an irreversible transition to a well-oxygenated state. Instead, it has been suggested that the oxygen content of the atmosphere-ocean system decreased considerably after ca. 2.06 billion years ago (Ga), which resulted in a crash in marine sulfate concentrations. The end of the deposition of major granular iron formations at ca. 1.85 Ga has been linked either to the development of extensive euxinic conditions along continental shelves or a decrease in hydrothermal flux. The record of oceanic redox state is not well constrained for the period between ca. 2.06 Ga, the end of the Lomagundi positive carbon isotope excursion, and ca. 1.88 Ga when major granular iron formations appeared. We address this gap by presenting new iron-speciation, major and trace element data, as well as sulfur, organic carbon, and molybdenum isotopic data for greenschist facies organic matter-rich mudrocks (ORMs) of the ca. 1.93 Ga Bravo Lake Formation, Piling Group, Baffin Island. The iron speciation data suggest deposition of the Bravo Lake Formation under a euxinic (anoxic and sulfidic) water column. Trace metal enrichments and Mo isotope data suggest extensive marine euxinia ca. 90 million years before the disappearance of large-scale, economic granular iron formations. The addition of new Mo data in this time interval is important, as it contributes to filling in the sparse Proterozoic record. Lastly, this work provides further support for the idea that there was widespread anoxia shortly after the end of the Lomagundi Event.
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  • 2
    Publication Date: 2017-10-31
    Description: Author Posting. © The Author(s), 2012. This is the author's version of the work. It is posted here by permission of John Wiley & Sons for personal use, not for redistribution. The definitive version was published in Geobiology 11 (2013): 295-306, doi:10.1111/gbi.12036.
    Description: Here we explore enrichments in paleomarine Zn as recorded by authigenic iron oxides including Precambrian iron formations, ironstones and Phanerozoic hydrothermal exhalites. This compilation of new and literature-based iron formation analyses track dissolved Zn abundances and constrain the magnitude of the marine reservoir over geological time. Overall, the iron formation record is characterized by a fairly static range in Zn/Fe ratios throughout the Precambrian, consistent with the shale record (Scott et al., 2013, Nature Geoscience, 6, 125-128). When hypothetical partitioning scenarios are applied to this record, paleomarine Zn concentrations within about an order of magnitude of modern are indicated. We couple this examination with new chemical speciation models used to interpret the iron formation record. We present two scenarios: first, under all but the most sulfidic conditions and with Zn binding organic ligand concentrations similar to modern oceans, the amount of bioavailable Zn remained relatively unchanged through time. Late proliferation of Zn in eukaryotic metallomes has previously been linked to marine Zn biolimitation, but under this scenario, the expansion in eukaryotic Zn metallomes may be better linked to biologically intrinsic evolutionary factors. In this case zinc’s geochemical and biological evolution may be decoupled, and viewed as a function of increasing need for genome regulation and diversification of Zn-binding transcription factors. In the second scenario, we consider Archean organic ligand complexation in such excess that it may render Zn bioavailability low. However, this is dependent on Zn organic ligand complexes not being bioavailable, which remains unclear. In this case, although bioavailability may be low, sphalerite precipitation is prevented, thereby maintaining a constant Zn inventory throughout both ferruginous and euxinic conditions. These results provide new perspectives and constraints 50 on potential couplings between the trajectory of biological and marine geochemical coevolution.
    Description: This work was supported by a NSERC Discovery Grant to KOK, a NSERC PDF to SVL, a NSERC CGSM to LJR, and an NSF-EAR-PDF to NJP. MAS acknowledges support from the Gordon and Betty Moore Foundation Grant #2724. This work was also supported by grants from the Deutsche Forschungsgemeinschaft (DFG) to A.K. (KA 1736/4-1 and 12-1).
    Keywords: Paleomarine zinc ; Metallome evolution ; Metalloenzymes ; Eukaryotic evolution ; Iron formations
    Repository Name: Woods Hole Open Access Server
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  • 3
    Publication Date: 2018-01-10
    Description: © 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 Earth and Planetary Science Letters 463 (2017): 159-170, doi:10.1016/j.epsl.2017.01.032.
    Description: The Proterozoic Eon hosted the emergence and initial recorded diversification of eukaryotes. Oxygen levels in the shallow marine settings critical to these events were lower than today’s, although how much lower is debated. Here, we use concentrations of iodate (the oxidized iodine species) in shallow-marine limestones and dolostones to generate the first comprehensive record of Proterozoic near-surface marine redox conditions. The iodine proxy is sensitive to both local oxygen availability and the relative proximity to anoxic waters. To assess the validity of our approach, Neogene-Quaternary carbonates are used to demonstrate that diagenesis most often decreases and is unlikely to increase carbonate-iodine contents. Despite the potential for diagenetic loss, maximum Proterozoic carbonate iodine levels are elevated relative to those of the Archean, particularly during the Lomagundi and Shuram carbon isotope excursions of the Paleo- and Neoproterozoic, respectively. For the Shuram anomaly, comparisons to Neogene-Quaternary carbonates suggest that diagenesis is not responsible for the observed iodine trends. The baseline low iodine levels in Proterozoic carbonates, relative to the Phanerozoic, are linked to a shallow oxic-anoxic interface. Oxygen concentrations in surface waters would have at least intermittently been above the threshold required to support eukaryotes. However, the diagnostically low iodine data from mid-Proterozoic shallow-water carbonates, relative to those of the bracketing time intervals, are consistent with a dynamic chemocline and anoxic waters that would have episodically mixed upward and laterally into the shallow oceans. This redox instability may have challenged early eukaryotic diversification and expansion, creating an evolutionary landscape unfavorable for the emergence of animals.
    Description: TL, ZL, and DH thank NSF EAR-1349252. ZL further thanks OCE-1232620. DH, ZL, and TL acknowledge further funding from a NASA Early Career Collaboration Award. TL, AB, NP, DH, and AK thank the NASA Astrobiology Institute. TL and NP received support from the Earth-Life Transitions Program of the NSF. AB acknowledges support from NSF grant EAR-05-45484 and an NSERC Discovery and Accelerator Grants. CW acknowledges support from NSFC grant 40972021.
    Keywords: Proterozoic oxygen ; Shuram isotope anomaly ; Carbonate diagenesis ; Bahamas ; Iodine ; Metazoan evolution
    Repository Name: Woods Hole Open Access Server
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  • 4
    Publication Date: 2018-01-10
    Description: © 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 Earth-Science Reviews 172 (2017): 140-177, doi:10.1016/j.earscirev.2017.06.012.
    Description: Iron formations (IF) represent an iron-rich rock type that typifies many Archaean and Proterozoic supracrustal successions and are chemical archives of Precambrian seawater chemistry and postdepositional iron cycling. Given that IF accumulated on the seafloor for over two billion years of Earth’s early history, changes in their chemical, mineralogical, and isotopic compositions offer a unique glimpse into environmental changes that took place on the evolving Earth. Perhaps one of the most significant events was the transition from an anoxic planet to one where oxygen was persistently present within the marine water column and atmosphere. Linked to this progressive global oxygenation was the evolution of aerobic microbial metabolisms that fundamentally influenced continental weathering processes, the supply of nutrients to the oceans, and, ultimately, diversification of the biosphere and complex life forms. Many of the key recent innovations in understanding IF genesis are linked to geobiology, since biologically assisted Fe(II) oxidation, either directly through photoferrotrophy, or indirectly through oxygenic photosynthesis, provides a process for IF deposition from mineral precursors. The abundance and isotope composition of Fe(II)-bearing minerals in IF additionally suggests microbial Fe(III) reduction, a metabolism that is deeply rooted in the Archaea and Bacteria. Linkages among geobiology, hydrothermal systems, and deposition of IF have been traditionally overlooked, but now form a coherent model for this unique rock type. This paper reviews the defining features of IF and their distribution through the Neoarchaean and Palaeoproterozoic. This paper is an update of previous reviews by Bekker et al. (2010, 2014) that will improve the quantitative framework we use to interpret IF deposition. In this work, we also discuss how recent discoveries have provided new insights into the processes underpinning the global rise in atmospheric oxygen and the geochemical evolution of the oceans.
    Description: KOK, TJW, RH, CAP and AB would like to thank the Natural Sciences and Engineering Research Council of Canada (NSERC) for its financial support. LJR gratefully acknowledges the support of a Vanier Canada Graduate Scholarship. CMJ, DSH, NJP and TWL acknowledge support from the NASA Astrobiology Institute. SVL acknowledges support from the European Institute for Marine Studies (LabexMER, ANR-10-LABX-19). HT and PBHO thank ASSMANG Ltd for providing research funding.
    Repository Name: Woods Hole Open Access Server
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  • 5
    Publication Date: 2017-01-12
    Description: © The Author(s), 2016. This is the author's version of the work and is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Chemical Geology 423 (2016): 19-33, doi:10.1016/j.chemgeo.2016.01.003.
    Description: Chromium (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.
    Description: Funding for this research was provided by Agouron Institute to XLW, National Science Foundation (NSF) EAR-0105927 and EAR-1250269 to JJA, and NSF EAR-1324566 to ES. NJP and CTR acknowledge funding from the Alternative Earths NAI.
    Description: 2017-01-12
    Keywords: Chromium isotopes ; Redox proxies ; Metamorphism ; Subduction ; Hydrothermal alteration ; Black shale weathering
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  • 6
    Publication Date: 2018-01-10
    Description: © The Author(s), 2016. 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 Earth-Science Reviews 163 (2016): 323-348, doi:10.1016/j.earscirev.2016.10.013.
    Description: 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.
    Description: LJR gratefully acknowledges the support of a Vanier Canada Graduate Scholarship. Discovery Grants from the Natural Sciences and Engineering Research Council of Canada (NSERC) to CAP, BK, DSA, SAC, and KOK supported this work. This material is based upon work supported by the National Aeronautics and Space Administration through the NASA Astrobiology Institute under Cooperative Agreement No. NNA15BB03A issued through the Science Mission Directorate. NJP receives support from the Alternative Earths NASA Astrobiology Institute. Funding from the NASA Astrobiology Institute, and the NSF FESD and ELT programs to TWL, and the Region of Brittany and LabexMER funding to SVL are also gratefully acknowledged. AB thanks the Society of Independent Thinkers.
    Keywords: Iron formations ; Black shales ; Eukaryotes ; Prokaryotes ; Evolution ; Trace elements ; Biolimitation ; Precambrian
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  • 7
    Publication Date: 2018-08-29
    Description: Author Posting. © The Author(s), 2018. 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 American Journal of Science 318 (2018): 527-556, doi:10.2475/05.2018.04.
    Description: 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.
    Description: DSH, TWL, NJP, and CRT acknowledge support from the NASA Astrobiology Institute under Cooperative Agreement No. NNA15BB03A issued through the Science Mission Directorate. Financial support was provided to NR and TWL by NSF-OCE and an appointment to the NASA Postdoctoral Program, as well as to BCG via a postdoctoral fellowship from the Agouron Institute. DSH was supported by a WHOI postdoctoral fellowship.
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  • 8
    Publication Date: 2020-02-06
    Description: Over the last two decades, popular opinion about prevailing conditions in the mid-Proterozoic deep ocean has evolved from fully oxygenated to globally euxinic (sulfidic) to a more heterogeneous, stratified water column with localized pockets of euxinia existing in predominantly iron-rich (ferruginous) deep waters. The Animikie Basin in theL ake Superior region has been essential in shaping our view of marine redox evolution over this time period. In this study, we present a multi-proxy paleoredox investigation of previously unanalyzed strata of the late Paleoproterozoic AnimikieB asin using drill cores through the -1.85 Ga Stambaugh Formation (PaintR iver Group) in the Iron River-Crystal Falls district of the Upper Peninsula of Michigan, USA. Based on previous tectonic reconstructions and analysis of sedimentary regimes, theI ronR iver-Crystal Falls section captures strata from among the deepest-water facies of the AnimikieB asin.I n contrast to previous work on sedimentary rocks in this basin, we find evidence from iron speciation, trace metal, and Mo isotope data for episodes of at least local deep-water oxygenation within a basin otherwise dominated by ferruginous and euxinic conditions. While tracemetal enrichments and iron speciation data suggest predominantly anoxic conditions, the occurrence of Mn-rich intervals (up to 12.3 wt% MnO) containing abundant Mn-Fe carbonate, and a wide range of Mo isotope data with extremely negative values (8 98195 Mo = -1.0 to + 1.1 %0), record the shuttling of Mn-oxides from surface waters through oxic or suboxic waters to the sediment-water interface. We propose that such conditions are analogous to those of locally restricted modern and Holocene basins in the Baltic Sea, which receive episodic inflow of oxygenated water, producing similar geochemical signatures to those observed for the AnimikieB asin. We argue that the mid-Proterozoic was characterized by a lack of a strong redox buffer (low sulfide, ferrous iron, and oxygen contents), and thus was vulnerable to dramatic, and at least local, redox shifts-including briefly oxygenated bottom waters. A refined view of the mid-Proterozoic ocean is emerging: one that was still predominantly anoxic, but marked by regional heterogeneities and short-term redox variability that may, in part, reflect a transitional state between prevailingly anoxic Archean and predominantly oxic Phanerozoic oceans.
    Type: Article , PeerReviewed
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  • 9
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    PANGAEA
    In:  Supplement to: Wang, Xiangli; Reinhard, Christopher T; Planavsky, Noah J; Owens, Jeremy D; Lyons, Timothy W; Johnson, Thomas M (2016): Sedimentary chromium isotopic compositions across the Cretaceous OAE2 at Demerara Rise Site 1258. Chemical Geology, 429, 85-92, https://doi.org/10.1016/j.chemgeo.2016.03.006
    Publication Date: 2020-02-22
    Description: In order to advance our understanding of the emerging chromium (Cr) isotope system as a paleoredox proxy, we measured the 53Cr/52Cr of black shales deposited before, during, and after Cretaceous Oceanic Anoxic Event 2 (OAE2). We observed a 〉 1 per mil coherent negative 53Cr/52Cr excursion and significant drawdown in Cr enrichments during OAE2 coincident with a large positive carbon isotope excursion. Our observed negative 53Cr/52Cr excursion during OAE2 is most easily linked to an increase in the ratio of euxinic to reducing conditions. Additional work on other OAE sections is needed to determine the spatial significance of this Cr isotope trend.
    Type: Dataset
    Format: text/tab-separated-values, 261 data points
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  • 10
    Publication Date: 2016-06-01
    Print ISSN: 0012-821X
    Electronic ISSN: 1385-013X
    Topics: Geosciences , Physics
    Published by Elsevier
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