Description: Organic carbon-rich shales from localities in England, Italy, and Morocco, which formed during the Cenomanian-Turonian oceanic anoxic event (OAE), have been examined for their total organic carbon (TOC) values together with their carbon, nitrogen, and iron isotope ratios. Carbon isotope stratigraphy (d13Corg and d13Ccarb) allows accurate recognition of the strata that record the oceanic anoxic event, in some cases allowing characterization of isotopic species before, during, and after the OAE. Within the black shales formed during the OAE, relatively heavy nitrogen isotope ratios, which correlate positively with TOC, suggest nitrate reduction (leading ultimately to denitrification and/or anaerobic ammonium oxidation). Black shales deposited before the onset of the OAE in Italy have unusually low bulk d57Fe values, unlike those found in the black shale (Livello Bonarelli) deposited during the oceanic anoxic event itself: These latter conform to the Phanerozoic norm for organic-rich sediments. Pyrite formation in the pre-OAE black shales has apparently taken place via dissimilatory iron reduction (DIR), within the sediment, a suboxic process that causes an approximately -2 per mil fractionation between a lithogenic Fe(III)oxide source and Fe(II)aq. In contrast, bacterial sulfate reduction (BSR), at least partly in the water column, characterized the OAE itself and was accompanied by only minor iron isotope fractionation. This change in the manner of pyrite formation is reflected in a decrease in the average pyrite framboid diameter from ~10 to ~7 µm. The gradual, albeit irregular increase in Fe isotope values during the OAE, as recorded in the Italian section, is taken to demonstrate limited isotopic evolution of the dissolved iron pool, consequent upon ongoing water column precipitation of pyrite under euxinic conditions. Given that evidence exists for both nitrate and sulfate reduction during the OAE, it is evident that redox conditions in the water column were highly variable, in both time and space.

Description: An occurrence of the alkali-rich, Fe-Mn silicate sugilite [KNa2(Fe3+, Mn3+, Al)2Li3Si12O30] is reported from the Wolhaarkop manganese-rich chert breccia at the Bruce iron-ore mine, Northern Cape Province, South Africa. The upper portion of the breccia is dominated by braunite, albite, K-feldspar and aegirine, and locally hosts irregular-shaped void-fills (generally

Description: Iron formations (IFs) are important geochemical repositories that provide constraints on atmospheric and ocean chemistry, prior to and during the onset of the Great Oxidation Event. Trace metal abundances and their Mo-Cr- U isotopic ratios have been widely used for investigating ocean redox processes through the Archean and Paleoproterozoic. Mineralogically, IFs consist of three main Fe-bearing fractions: (1) Fe-Ca-Mg-Mn carbonates, (2) magnetite and/or hematite and (3) Fe-silicates. These fractions are typically fine-grained on a sub-μm scale and their co-occurrence in varying amounts means that bulk-rock or microanalytical geochemical and stable isotope data can be influenced by cryptic changes in mineralogy. Fraction specific geochemical analysis has the potential to resolve mineralogical controls and reveal diagenetic versus primary precipitative controls on IF mineralogy. Here we adapt an existing sequential extraction scheme for Fe-phases (Poulton and Canfield, 2005) to the high Fe-content in IF and the specific three-fraction mineralogy. We optimized the scheme for magnetite-dominated Archean IFs using samples from the hematite-poor Asbestos Hills Subgroup IF, Transvaal Supergroup, South Africa. Previously commonly-used hydroxylamine-HCl and dithionite leaches were omitted since ferric oxides are quantitatively insignificant in these IF samples. The acetate leach was tested at variable temperatures, reaction times and under different atmospheres in order to ensure that all micro-crystalline Fe-carbonates were effectively dissolved, resulting in an optimum extraction for 48 h at 50 °C under anoxic conditions. The dissolution of magnetite by NH4-oxalate was also tested, resulting in an optimum extraction for 24 h under an ambient atmosphere. Finally, a HF-HClO4-HNO3 leach was used to dissolve the residual silicate fraction which has to date not been considered in detail in IF. Accuracy of the extraction technique was generally excellent, as verified using 1) elemental recoveries, 2) comparison of major and trace element distributions against mineralogy and 3) comparison to results from microanalytical techniques. This study focuses on the distribution of three frequently used geochemical proxies in IF; U, Mo and Cr. Molybdenum abundances in the Kuruman and Griquatown IF are low and show an apparent correlation with mineralogical variability, as determined by the sequential extraction. This suggests that changes in bulk-rock mineralogy, rather than redox chemistry might significantly affect Mo stable isotopes. For Cr, a minor bulk-rock stratigraphic increase can be related to the oxide and silicate fraction. However, a positive relationship with Zr indicates that this was also controlled by detrital or volcanic ash input. Uranium is predominantly bound to the silicate fraction and shows clear correlations with Zr and Sc implying detrital reworking under anoxic conditions. The discrepant behaviour of these three proxies indicate that mineralogy should be taken into account when interpreting heterogeneous bulk-rock samples and that fraction specific techniques will provide new insights into the evolution of atmosphere and ocean chemistry.

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.