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The micronutrient iron plays a major role in setting the magnitude and distribution of primary production across the global ocean. As such, an understanding of the sources, sinks, and internal cycling processes that drive the oceanic distribution of iron is key to unlocking iron's role in the global carbon cycle and climate, both today and in the geologic past. Iron isotopic analyses of seawater have emerged as a transformative tool for diagnosing iron sources to the ocean and tracing biogeochemical processes. In this review, we summarize the end-member isotope signatures of different iron source fluxes and highlight the novel insights into iron provenance gained using this tracer. We also review ways in which iron isotope fractionation might be used to understand internal oceanic cycling of iron, including speciation changes, biological uptake, and particle scavenging. We conclude with an overview of future research needed to expand the utilization of this cutting-edge tracer.
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Reduced expression of iron transport and homeostasis genes in Pseudomonas fluorescens during iron uptake from nanoscale iron
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Permeable sediments, which represent more than 50% of the continental shelves, have been largely neglected as a potential source of Fe in current global estimates of benthic dissolved iron Fed fluxes. There are open questions regarding the effects of a range of factors on Fed fluxes from these deposits, including seasonal dynamics and the role of bioirrigation. To address these gaps, we performed laboratory-based sediment incubation experiments with muddy sands during summer (21 °C) and winter (7 °C). We used bioirrigation mimics to inject overlying water into the permeable sediment with patterns resembling the bioirrigation activity of the prolific bioturbating polychaete,Clymenella torquata. Newly developed in-line Fe accumulators were used to estimate Fe fluxes with a recirculating set-up. We found high Fed fluxes from sandy sediments, especially in benthic chambers with simulated bioirrigation. In the winter fluxes reached 200 µmol Fed m-2 d-1 at the onset of irrigation and then decreased over the course of a 13-day experiment while in the summer fluxes from irrigated sediments reached 100 µmol Fed m-2 d-1 and remained high throughout a 7-day experiment. Despite different geochemical expressions of Fe-S cycling and resulting porewater Fed concentrations in winter and summer, large Fed fluxes were sustained during both seasons. Solid-phase and porewater concentration profiles showed that maximum concentrations of key constituents, including total solid-phase reactive Fe, and porewater Fed and ammonium, were located closer to the sediment water interface (SWI) in irrigated cores than in non-irrigated cores due to the upward advective transport of dissolved porewater constituents. This upward transport also facilitated Fed fluxes out of the sediments, especially during times of active pumping. Our study demonstrates the potential for large Fed fluxes from sandy sediments in both summer and winter, despite relatively low standing stocks of labile organic matter and porewater Fed. The primary driver of these high fluxes was advective porewater transport, in our study induced by the activity of infaunal organisms. These results suggest that permeable sediments, which dominate shelf regions, must be explicitly considered in global estimates of benthic Fed fluxes, and cannot be simply extrapolated from estimates based on muddy sediments.more » « less
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Banded iron formations (BIF) are chemically precipitated sediments that can record Archean ocean geochemistry. BIFs are laminated silica- and iron-rich deposits that host a range of iron(II, III) minerals, including hematite, magnetite, siderite, greenalite, minnesotaite, and stilpnomelane. This diverse mineralogical assemblage reflects secondary mineralization reactions due to diagenesis and/or post-depositional alteration. While petrographic observations of BIFs sparingly contain the iron silicate greenalite, recent evidence of greenalite nanoparticles preserved in early-mineralizing BIF chert suggest this mineral was a primary phase in BIF progenitor sediments. Therefore, it is critical to investigate the formation and alteration of greenalite to constrain the Archean ocean environment and help unravel post-depositional processes. To examine how iron silicates precipitate and then crystallize and/or transform during diagenesis, we simulated these two processes under Archean ocean conditions. We first precipitated a poorly ordered Fe-rich serpentine with subsidiary ferrihydrite at neutral pH by performing in situ Fe(II) oxidation experiments at 25 °C in the presence of silica. Subjected to simulated diagenesis at 80 °C, the rudimentary Fe-phyllosilicate transformed into a crystalline phyllosilicate characterized as 30% cronstedtite and 70% greenalite accompanied by magnetite and persistent ferrihydrite. At temperatures ≤150 °C, we continued to observe ferrihydrite, increased magnetite formation, and elevated incorporation of Mg into the phyllosilicate as it further recrystallized into Mg-greenalite. Our findings demonstrate a possible formation mechanism of early silicates through partial Fe(II) oxidation and support petrographic observations that magnetite likely mineralizes during diagenesis. Additionally, we suggest that Mg contents in BIF iron phyllosilicates could serve as a tracer for diagenesis, with Mg signaling phyllosilicate-fluid interactions at elevated temperatures. Ultimately, our experiments help reveal how initial iron-silica coprecipitates are altered during diagenesis, providing novel insights into the interpretation of greenalite and magnetite in ancient BIF assemblages.more » « less
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A classical interatomic potential for iron/iron-fluoride systems is developed in the framework of the charge optimized many-body (COMB) potential. This interatomic potential takes into consideration the effects of charge transfer and many-body interactions depending on the chemical environment. The potential is fitted to a training set composed of both experimental and ab initio results of the cohesive energies of several Fe and FeF 2 crystal phases, the two fluorine molecules F 2 and the F 2 −1 dissociation energy curve, the Fe and FeF 2 lattice parameters of the ground state crystalline phase, and the elastic constants of the body centered cubic Fe structure. The potential is tested in an NVT ensemble for different initial structural configurations as the crystal ground state phases, F 2 molecules, iron clusters, and iron nanospheres. In particular, we model the FeF 2 /Fe bilayer and multilayer interfaces, as well as a system of square FeF 2 nanowires immersed in an iron solid. It has been shown that there exists a reordering of the atomic positions for F and Fe atoms at the interface zone; this rearrangement leads to an increase in the charge transfer among the atoms that make the interface and put forward a possible mechanism of the exchange bias origin based on asymmetric electric charge transfer in the different spin channels.more » « less
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Abstract N,N,N′,N′‐Tetramethylethylenediamine (TMEDA) has been one of the most prevalent and successful additives used in iron catalysis, finding application in reactions as diverse as cross‐coupling, C−H activation, and borylation. However, the role that TMEDA plays in these reactions remains largely undefined. Herein, studying the iron‐catalyzed hydromagnesiation of styrene derivatives using TMEDA has provided molecular‐level insight into the role of TMEDA in achieving effective catalysis. The key is the initial formation of TMEDA–iron(II)–alkyl species which undergo a controlled reduction to selectively form catalytically active styrene‐stabilized iron(0)–alkyl complexes. While TMEDA is not bound to the catalytically active species, these active iron(0) complexes cannot be accessed in the absence of TMEDA. This mode of action, allowing for controlled reduction and access to iron(0) species, represents a new paradigm for the role of this important reaction additive in iron catalysis.more » « less
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.impact.2018.08.009
