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1. 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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2. The origin of sulfur in Canary Island magmas and its implications for Earth’s deep sulfur cycle

   https://doi.org/10.1073/pnas.2416070122  

   Taracsák, Zoltán; Hartley, Margaret E; Burgess, Ray; Edmonds, Marie; Longpré, Marc-Antoine; Monteleone, Brian D; Tartèse, Romain; Turchyn, Alexandra V (March 2025, Proceedings of the National Academy of Sciences)

   The global sulfur cycle plays a critical role in the redox evolution of Earth’s surface and upper mantle, yet the distribution and origin of sulfur in the mantle remains largely unconstrained. El Hierro is a volcanic island in the Canary archipelago that is fed by sulfur-rich magmas. To constrain the origin of sulfur in these melts, we combine in situ sulfur isotope analyses with regression modeling. We calculate that undegassed El Hierro melts have δ34S values of 0 ± 2‰. The average δ34S of undegassed El Hierro melts is 0.3‰ to 1‰ higher than magmas erupting at mid-ocean ridges. Mass balance calculations reveal that El Hierro’s mantle source contains 310 ± 120 μg/g sulfur and that on average 60% of sulfur in the source is of recycled origin. This recycled material should contain >1,800 μg/g sulfur to satisfy isotopic constraints on its mass fraction in the mantle source. The sulfur and oxygen isotopic signature in serpentinites and sediments deviate significantly from the upper mantle, making them unsuitable candidates for the recycled material. An oxidized partial melt of recycled oceanic crust that retained one third of its sulfur budget after subduction zone processing can explain excess sulfur in the Canary Island mantle. Recycled oceanic crust is expected to contain sulfur as sulfide, which is not capable of oxidizing the mantle. The presence of ferric iron in the recycled component is necessary to produce metasomatic melts that are oxidizing enough to carry sufficient sulfur into the mantle source of ocean island basalts. 

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3. Slab Transport of Fluids to Deep Focus Earthquake Depths—Thermal Modeling Constraints and Evidence From Diamonds

   https://doi.org/10.1029/2020AV000304  

   Shirey, Steven B.; Wagner, Lara S.; Walter, Michael J.; Pearson, D. Graham; van Keken, Peter E. (May 2021, AGU Advances)

   Abstract The nature and cause of deep earthquakes remain enduring unknowns in the field of seismology. We present new models of thermal structures of subducted slabs traced to mantle transition zone depths that permit a detailed comparison between slab pressure/temperature (P/T) paths and hydrated/carbonated mineral phase relations. We find a remarkable correlation between slabs capable of transporting water to transition zone depths in dense hydrous magnesium silicates with slabs that produce seismicity below ∼300‐km depth, primarily between 500 and 700 km. This depth range also coincides with theP/Tconditions at which oceanic crustal lithologies in cold slabs are predicted to intersect the carbonate‐bearing basalt solidus to produce carbonatitic melts. Both forms of fluid evolution are well represented by sublithospheric diamonds whose inclusions record the existence of melts, fluids, or supercritical liquids derived from hydrated or carbonate‐bearing slabs at depths (∼300–700 km) generally coincident with deep‐focus earthquakes. We propose that the hydrous and carbonated fluids released from subducted slabs at these depths lead to fluid‐triggered seismicity, fluid migration, diamond precipitation, and inclusion crystallization. Deep focus earthquake hypocenters could track the general region of deep fluid release, migration, and diamond formation in the mantle. The thermal modeling of slabs in the mantle and the correlation between sublithospheric diamonds, deep focus earthquakes, and slabs at depth demonstrate a deep subduction pathway to the mantle transition zone for carbon and volatiles that bypasses shallower decarbonation and dehydration processes. 

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4. Recycled calcium carbonate is an efficient oxidation agent under deep upper mantle conditions

   https://doi.org/10.1038/s43247-021-00116-8  

   Tao, Renbiao; Fei, Yingwei (February 2021, Communications Earth & Environment)

   Abstract Observations of high ferric iron content in diamond garnet inclusions and mantle plume melts suggest a highly heterogeneous distribution of ferric iron in the mantle. Recycling of oxidized materials such as carbonates from Earth’s surface by subduction could explain the observed variations. Here we present high-pressure high-temperature multi-anvil experiments to determine the redox reactions between calcium-, magnesium-, or iron-carbonate and ferrous iron-bearing silicate mineral (garnet or fayalite) at conditions representative of subduction zones with intermediate thermal structures. We show that both garnet and fayalite can be oxidized to ferric iron-rich garnets accompanied by reduction of calcium carbonate to form graphite. The ferric iron content in the synthetic garnets increases with increasing pressure, and is correlated with the Ca content in the garnets. We suggest that recycled sedimentary calcium carbonate could influence the evolution of the mantle oxidation state by efficiently increasing the ferric iron content in the deep upper mantle. 

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5. Mixed incorporation of carbon and hydrogen in silicate melts under varying pressure and redox conditions

   https://doi.org/10.1016/j.epsl.2020.116520  

   Karki, Bijaya B; Ghosh, Dipta B; Banjara, Dipendra (November 2020, Earth and planetary science letters)

   null (Ed.)

   Volatiles including carbon and hydrogen are generally considered to be more soluble in silicate melts than in mantle rocks. How these melts contribute to the storage and distribution of key volatiles in Earth's interior today and during its early evolution, however, remains largely unknown. It is essential to improve our knowledge about volatiles-bearing silicate magmas over the entire mantle pressure regime. Here we investigate molten Mg FexSiO3 ( , 0.25) containing both carbon and hydrogen using first-principles molecular dynamics simulations. Our results show that the dissolution mechanism of the binary volatiles in melts varies considerably under different conditions of pressure and redox. When incorporated as CO2 and H2O components (corresponding to oxidizing conditions) almost all carbon and hydrogen form bonds with oxygen. Their speciation at low pressure consists of predominantly isolated molecular CO2, carbonates, and hydroxyls. More oxygenated species, including tetrahedrally coordinated carbons, hydrogen (O-H-O) bridges, various oxygen-joined complexes appear as melt is further compressed. When two volatiles are incorporated as hydrocarbons CH4 and C2H6 (corresponding to reducing conditions), hydroxyls are prevalent with notable presence of molecular hydrogen. Carbon-oxygen bonding is almost completely suppressed. Instead carbon is directly correlated with itself, hydrogen, and silicon. Both volatiles also show strong affinity to iron. Reduced volatile speciation thus involves polymerized complexes comprising of carbon, hydrogen, silicon, and iron, which can be mostly represented by two forms: C1−4H1−5Si0−5O0−2 (iron-free) and C5−8H1−8Si0−6Fe5−8O0−2. The calculated partial molar volumes of binary volatiles in their oxidized and reduced incorporation decrease rapidly initially with pressure and then gradually at higher pressures, thereby systematically lowering silicate melt density. Our assessment of the calculated opposite effects of the volatile components and iron on melt density indicates that melt-crystal density crossovers are possible in the present-day mantle and also could have occurred in early magma ocean environments. Melts at upper mantle and transition zone conditions likely dissolve carbon and hydrogen in a wide variety of oxidized and non-oxygenated forms. Deep-seated partial melts and magma ocean remnants at lower mantle conditions may exsolve carbon as complex reduced species possibly to the core during core-mantle differentiation while retaining a majority of hydrogen as hydroxyls-associated species. 

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