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1. Simulated diagenesis of the iron-silica precipitates in banded iron formations

   https://doi.org/10.2138/am-2022-8758  

   Hinz, Isaac L.; Rossi, Leanne; Ma, Chi; Johnson, Jena E. (September 2023, American Mineralogist)

   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. 

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2. A Continuum from Iron Oxide Copper-Gold to Iron Oxide-Apatite Deposits: Evidence from Fe and O Stable Isotopes and Trace Element Chemistry of Magnetite

   https://doi.org/10.5382/econgeo.4752  

   Rodriguez-Mustafa, Maria A.; Simon, Adam C.; del Real, Irene; Thompson, John F.H.; Bilenker, Laura D.; Barra, Fernando; Bindeman, Ilya; Cadwell, David (November 2020, Economic Geology)

   Abstract Iron oxide copper-gold (IOCG) and iron oxide-apatite (IOA) deposits are major sources of Fe, Cu, and Au. Magnetite is the modally dominant and commodity mineral in IOA deposits, whereas magnetite and hematite are predominant in IOCG deposits, with copper sulfides being the primary commodity minerals. It is generally accepted that IOCG deposits formed by hydrothermal processes, but there is a lack of consensus for the source of the ore fluid(s). There are multiple competing hypotheses for the formation of IOA deposits, with models that range from purely magmatic to purely hydrothermal. In the Chilean iron belt, the spatial and temporal association of IOCG and IOA deposits has led to the hypothesis that IOA and IOCG deposits are genetically connected, where S-Cu-Au–poor magnetite-dominated IOA deposits represent the stratigraphically deeper levels of S-Cu-Au–rich magnetite- and hematite-dominated IOCG deposits. Here we report minor element and Fe and O stable isotope abundances for magnetite and H stable isotope abundances for actinolite from the Candelaria IOCG deposit and Quince IOA prospect in the Chilean iron belt. Backscattered electron imaging reveals textures of igneous and magmatic-hydrothermal affinities and the exsolution of Mn-rich ilmenite from magnetite in Quince and deep levels of Candelaria (>500 m below the bottom of the open pit). Trace element concentrations in magnetite systematically increase with depth in both deposits and decrease from core to rim within magnetite grains in shallow samples from Candelaria. These results are consistent with a cooling trend for magnetite growth from deep to shallow levels in both systems. Iron isotope compositions of magnetite range from δ56Fe values of 0.11 ± 0.07 to 0.16 ± 0.05‰ for Quince and between 0.16 ± 0.03 and 0.42 ± 0.04‰ for Candelaria. Oxygen isotope compositions of magnetite range from δ18O values of 2.65 ± 0.07 to 3.33 ± 0.07‰ for Quince and between 1.16 ± 0.07 and 7.80 ± 0.07‰ for Candelaria. For cogenetic actinolite, δD values range from –41.7 ± 2.10 to –39.0 ± 2.10‰ for Quince and from –93.9 ± 2.10 to –54.0 ± 2.10‰ for Candelaria, and δ18O values range between 5.89 ± 0.23 and 6.02 ± 0.23‰ for Quince and between 7.50 ± 0.23 and 7.69 ± 0.23‰ for Candelaria. The paired Fe and O isotope compositions of magnetite and the H isotope signature of actinolite fingerprint a magmatic source reservoir for ore fluids at Candelaria and Quince. Temperature estimates from O isotope thermometry and Fe# of actinolite (Fe# = [molar Fe]/([molar Fe] + [molar Mg])) are consistent with high-temperature mineralization (600°–860°C). The reintegrated composition of primary Ti-rich magnetite is consistent with igneous magnetite and supports magmatic conditions for the formation of magnetite in the Quince prospect and the deep portion of the Candelaria deposit. The trace element variations and zonation in magnetite from shallower levels of Candelaria are consistent with magnetite growth from a cooling magmatic-hydrothermal fluid. The combined chemical and textural data are consistent with a combined igneous and magmatic-hydrothermal origin for Quince and Candelaria, where the deeper portion of Candelaria corresponds to a transitional phase between the shallower IOCG deposit and a deeper IOA system analogous to the Quince IOA prospect, providing evidence for a continuum between both deposit types. 

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3. Formation of iron oxide–apatite deposits

   https://doi.org/https://doi.org/10.1038/s43017-022-00335-3  

   Martin Reich, Adam C. (September 2022, Nature reviews)

   Renewed economic interest in iron oxide–apatite (IOA) deposits — containing tens to hundreds of millions of tonnes of Fe and substantial amounts of rare earth elements, P, Co and V — has emerged to supply the sustainable energy transition. However, the mechanisms that efficiently concentrate dense iron- rich minerals (for example, in ores up to ~90% magnetite) at the Earth’s near- surface are widely debated. In this Review, we discuss synergistic combinations of magmatic and hydrothermal iron- enrichment processes that can explain the available geochemical, petrological and geological IOA data. IOA deposits typically evolve from subductionrelated water- rich and chlorine- rich intermediate magmas under a wide temperature range, almost spanning the whole igneous–hydrothermal spectrum (from ~1,000 to 300 °C). Magmatic– hydrothermal fluids could efficiently scavenge Fe from magmas to form large IOA deposits (>100 million tonnes of Fe), whereas crystal fractionation and liquid immiscibility processes might account for more minor Fe mineralization occurrences. Igneous magnetite crystallization, volatile exsolution and highly focused transport of Fe- rich hydrothermal fluids through the crust under extensional tectonic conditions could be key factors enabling concentration of dense magnetite minerals in the less- dense upper crust. Future research should target both fertile and barren mafic–intermediate magmatic suites for distinctive signatures diagnostic of metallogenic fertility, to help unravel the genetic linkage between IOA and iron oxide–copper–gold systems. 

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4. Thermal evolution of Andean iron oxide–apatite (IOA) deposits as revealed by magnetite thermometry

   https://doi.org/10.1038/s41598-021-97883-3  

   Palma, Gisella; Reich, Martin; Barra, Fernando; Ovalle, J. Tomás; del Real, Irene; Simon, Adam C. (December 2021, Scientific Reports)

   Abstract Magnetite is the main constituent of iron oxide–apatite (IOA) deposits, which are a globally important source of Fe and other elements such as P and REE, critical for modern technologies. Geochemical studies of magnetite from IOA deposits have provided key insights into the ore-forming processes and source of mineralizing fluids. However, to date, only qualitative estimations have been obtained for one of the key controlling physico-chemical parameters, i.e., the temperature of magnetite formation. Here we reconstruct the thermal evolution of Andean IOA deposits by using magnetite thermometry. Our study comprised a > 3000 point geochemical dataset of magnetite from several IOA deposits within the Early Cretaceous Chilean Iron Belt, as well as from the Pliocene El Laco IOA deposit in the Chilean Altiplano. Thermometry data reveal that the deposits formed under a wide range of temperatures, from purely magmatic (~ 1000 to 800 °C), to late magmatic or magmatic-hydrothermal (~ 800 to 600 °C), to purely hydrothermal (< 600 °C) conditions. Magnetite cooling trends are consistent with genetic models invoking a combined igneous and magmatic-hydrothermal origin that involve Fe-rich fluids sourced from intermediate silicate magmas. The data demonstrate the potential of magnetite thermometry to better constrain the thermal evolution of IOA systems worldwide, and help refine the geological models used to find new resources. 

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5. Heavy iron in large gem diamonds traces deep subduction of serpentinized ocean floor

   https://doi.org/10.1126/sciadv.abe9773  

   Smith, Evan M.; Ni, Peng; Shirey, Steven B.; Richardson, Stephen H.; Wang, Wuyi; Shahar, Anat (March 2021, Science Advances)

   null (Ed.)

   Subducting tectonic plates carry water and other surficial components into Earth’s interior. Previous studies suggest that serpentinized peridotite is a key part of deep recycling, but this geochemical pathway has not been directly traced. Here, we report Fe-Ni–rich metallic inclusions in sublithospheric diamonds from a depth of 360 to 750 km with isotopically heavy iron (δ 56 Fe = 0.79 to 0.90‰) and unradiogenic osmium ( 187 Os/ 188 Os = 0.111). These iron values lie outside the range of known mantle compositions or expected reaction products at depth. This signature represents subducted iron from magnetite and/or Fe-Ni alloys precipitated during serpentinization of oceanic peridotite, a lithology known to carry unradiogenic osmium inherited from prior convection and melt depletion. These diamond-hosted inclusions trace serpentinite subduction into the mantle transition zone. We propose that iron-rich phases from serpentinite contribute a labile heavy iron component to the heterogeneous convecting mantle eventually sampled by oceanic basalts. 

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