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Xenolithic corundum aggregates in Cretaceous mafic pyroclastics from Mount Carmel contain pockets of silicate melts with mineral assemblages [SiC (moissanite), TiC, Ti2O3 (tistarite), Fe-Ti-Zr silicides/phosphides] indicative of magmatic temperatures and oxygen fugacity (fO2) at least 6 log units below the iron-wüstite buffer (ΔIW ≤ –6). Microstructural evidence indicates that immiscible, carbon-rich metallic (Fe-Ti-Zr-Si-P) melts separated during the crystallization of the silicate melts. The further evolution of these metallic melts was driven by the crystallization of two main ternary phases (FeTiSi and FeTiSi2) and several near-binary phases, as well as the separation of more evolved immiscible melts. Reconstructed melt compositions fall close to cotectic curves in the Fe-Ti-Si system, consistent with trapping as metallic liquids. Temperatures estimated from comparisons with experimental work range from ≥1500 °C to ca. 1150 °C; these probably are maximum values due to the solution of C, H, P, and Zr. With decreasing temperature (T), the Si, Fe, and P contents of the Fe-Ti-Si melts increased, while contents of Ti and C decreased. The increase in Si with declining T implies a corresponding decrease in fO2, probably to ca. ΔIW-9. The solubility of P in the metallic melts declined with T and fO2, leading to immiscibility between Fe-Ti-Si melts and (Ti,Zr)-(P,Si) melts. Decreasing T and fO2 also reduced the solubility of C in the liquid metal, driving the continuous crystallization of TiC and SiC during cooling. The lower-T metallic melts are richer in Cr, and to some extent V, as predicted by experimental studies showing that Cr and V become more siderophile with decreasing fO2. These observations emphasize the importance of melt-melt immiscibility for the evolution of magmas under reducing conditions. The low fO2 and the abundance of carbon in the Mt. Carmel system are consistent with a model in which differentiating melts were fluxed by fluids that were dominated by CH4+H2, probably derived from a metal-saturated sublithospheric mantle. A compilation of other occur-rences suggests that these phenomena may commonly accompany several types of explosive volcanism.

Xenocrysts and xenoliths in Upper Cretaceous pyroclastics on Mount Carmel (northern Israel) represent a series of similar magma-fluid systems at different stages of their evolution, recording a continuous decrease in oxygen fugacity (fO2) as crystallization proceeded. Corundum coexisting with Fe-Mg-Cr-Al spinels, other Fe-Mg-Al-Na oxides, and Fe-Ni alloys in apparent cumulates crystallized at fO2 values near the iron-wüstite (IW) buffer (fO2 = IW±1) and is zoned from high-Cr cores to lower-Cr rims, consistent with fractional crystallization trends. The reconstructed parental melts of the cumulates are Al-Cr-Fe-Mg oxides with ca. 2 wt% SiO2. Corundum in other possible cumulates that contain Cr-Fe (Fe 45 wt%) alloys has low-Cr cores and still lower-Cr rims. Corundum coexisting with Cr0 (fO2 = IW-5) in some possible cumulates has low-Cr cores, but high-Cr rims (to >30% Cr2O3). These changes in zoning patterns reflect the strong decrease in the melting point of Cr2O3, relative to Al2O3, with decreasing fO2. The electron energy loss spectroscopy (EELS) analyses show that all Cr in corundum that coexists with Cr0 is present as Cr3+. This suggests that late in the evolution of these reduced melts, Cr2+ has disproportionated via the reaction 3Cr2+(melt) → 2Cr3+(Crn) + Cr0. The most Cr-rich corundum crystallized together with β-alumina phases including NaAl11O17 (diaoyudaoite) and KAl11O17 (kahlenbergite) and β″-alumina phases; residual melts crystallized a range of (K,Mg)2(Al,Cr)10O17 phases with the kahlenbergite structure. The parental melts of these assemblages appear to have been Al-Cr-K-Na-Mg oxides, which may be related to the Al-Cr-Fe-Mg oxide melts mentioned above, through fractional crystallization or liquid immiscibility. These samples are less reduced (fO2 from IW to IW-5) than the assemblages of the trapped silicate melts in the more abundant xenoliths of corundum aggregates (fO2 = IW-6 to IW-10). They could be considered to represent an earlier stage in the fO2 evolution of an “ideal” Mt. Carmel magmatic system, in which mafic or syenitic magmas were fluxed by mantle-derived CH4+H2 fluids. This is a newly recognized step in the evolution of the Mt. Carmel assemblages and helps to understand element partitioning under highly reducing conditions.

Aggregates of corundum crystals with skeletal to hopper morphology occur in pyroclastic rocks erupted from Cretaceous basaltic volcanoes on Mt Carmel, N. Israel. The rapid growth of the crystals trapped volumes of the parental Al2O3-supersaturated melt; phenocrysts of tistarite (Ti2O3) in the trapped melts indicate crystallization at oxygen fugacities 6–7 log units below the Iron-Wüstite buffer (fO2 = ΔIW − 6 to − 7), induced by fluxes of mantle-derived CH4-H2 fluids. Cathodoluminescence images reveal growth zoning within the individual crystals of the aggregates, related to the substitution of Ti3+ in the corundum structure. Ti contents are 2 wt%. Numerical modelling indicates that the first skeletal crystals grew in an open system, from a moving magma. The subsequent linear increase in Ti reflects growth in a partially closed system, with decreasing porosity; the exponential increase in Ti close to melt pockets reflects closed-system growth, leading to dramatic increases in incompatible-element concentrations in the residual melts. We suggest that the corundum aggregates grew in melt/fluid conduits; diffusion modelling implies timescales of days to years before crystallization was terminated by explosive eruption. These processes probably operate in explosive volcanic systems in several tectonic settings.

Titanium diboride (TiB2) is a minor but common phase in melt pockets trapped in the corundum aggregates that occur as xenoliths in Cretaceous basaltic volcanoes on Mt. Carmel, north Israel. These melt pockets show extensive textural evidence of immiscibility between metallic (Fe-Ti-C-Si) melts, Ca-Al-Mg-Si-O melts, and Ti-(oxy)nitride melts. The metallic melts commonly form spherules in the coexisting oxide glass. Most of the observed TiB2 crystallized from the Fe-Ti-C silicide melts and a smaller proportion from the oxide melts. The parageneses in the melt pockets of the xenoliths require fO2 ≤ ΔIW-6, probably generated through interaction between evolved silicate melts and mantle-derived CH4+H2 fluids near the crust-mantle boundary. Under these highly reducing conditions boron, like carbon and nitrogen, behaved mainly as a siderophile element during the separation of immiscible metallic and oxide melts. These parageneses have implications for the residence of boron in the peridotitic mantle and for the occurrence of TiB2 in other less well-constrained environments such as ophiolitic chromitites.

The occurrence of moissanite (SiC), as xenocrysts in mantle-derived basaltic and kimberlitic rocks sheds light on the interplay between carbon, hydrogen and oxygen in the lithospheric and sublithospheric mantle. SiC is stable only at ƒO2

International audience; Coarse-grained xenoliths of hibonite + grossite + Mg-Al-V spinel from Cretaceous pyroclastic rocks on Mt. Carmel, N. Israel, and from Sierra de Comechingones, Argentina, include spherules, rods and dense branching structures of native vanadium and VAl alloys. Microstructures suggest that vanadium melts became immiscible with the host Ca-Al-Mg-Si-O melt, and nucleated as droplets on the surfaces of the oxide phases, principally hibonite. Many extended outward as rods or branching structures as the host oxide crystal grew. The stability of V0 implies oxygen fugacities ≥9 log units below the Iron-Wustite buffer, suggesting a hydrogen-dominated atmosphere. This is supported by wt%-levels of hydrogen in gasses released by crushing, by Raman spectroscopy, and by the presence of VH2 among the vanadium balls. The oxide assemblage formed at 1400–1200 °C; the solution of hydrogen in the metal could lower the melting point of vanadium to these temperatures. These assemblages probably resulted from reaction between differentiated mafic melts and mantle-derived CH4 + H2 fluids near the crust-mantle boundary, and they record the most reducing magmatic conditions yet documented on Earth.

Xenocrystic zircons from Cretaceous pyroclastic vents on Mt. Carmel, N. Israel, document two major periods of earlier mafic magmatism: Permo-Triassic (285–220 Ma) and Jurassic (200–160 Ma). Related alluvial deposits also contain these zircon populations. However, most alluvial zircons are Cretaceous (118–80 Ma) or younger, derived from Miocene to Pliocene volcanic episodes. The Permo-Triassic-Jurassic zircons are typically large and glassy; they have irregular shapes and a wide variety of internal zoning patterns. They appear to have grown in the interstitial spaces of coarse-grained rocks; many show evidence of recrystallization, including brecciation and rehealing by chemically similar zircon. Grains with relict igneous zoning have mantle-like δ18O (5.5 ± 1.0‰), but brecciation leads to lower values (mean 4.8‰, down to 3.1‰). Hf-isotope compositions lie midway between the Chondritic Uniform Reservoir (CHUR) and Depleted Mantle (DM) reservoirs; Hf model ages suggest that the source region separated from DM in Neoproterozoic time (1500–1000 Ma). Most Cretaceous zircons have 176Hf/177Hf similar to those of the older zircons, suggesting recrystallization and/or Pb loss from older zircons in the Cretaceous thermal event. The Permo-Jurassic zircons show trace-element characteristics similar to those crystallized from plume-related magmas (Iceland, Hawaii). Calculated melts in equilibrium with them are characterized by strong depletion in LREE and P, large positive Ce anomalies, variable Ti anomalies, and high and variable Nb, Ta, Th and U, consistent with the fractionation of monazite, zircon, apatite and Ti-bearing phases. We suggest that these coarse-grained zircons crystallized from late differentiates of mafic magmas, ponded near the crust-mantle boundary (ca 30 km depth), and were reworked repeatedly by successively younger igneous/metasomatic fluids. The zircon data support a published model that locates a fossil Neoproterozoic plume head beneath much of the Arabia-Levant region, which has been intermittently melted to generate the volcanic rocks of the region. The Cretaceous magmas carry mantle xenoliths derived from depths up to 90 km, providing a minimum depth for the possible plume head. Post-Cretaceous magmatism, as recorded in detrital zircons, shows distinct peaks at 30 Ma, 13 Ma, 11.4 ± 0.1 Ma (a major peak; n = 15), 9–10 Ma and 4 Ma, representing the Lower and Cover Basalts in the area. Some of these younger magmas tapped the same mantle source as the Permian-Jurassic magmatism, but many young zircons have Hf-isotope compositions extending up to DM values, suggesting derivation of magmas from deeper, more juvenile sources.

Oxygen fugacity (ƒO2) is a key parameter of Earth’s mantle, because it controls the speciation of the fluids migrating at depth; a major question is whether the sublithospheric mantle is metal-saturated, keeping ƒO2 near the Iron-Wustite (IW) buffer reaction. Cretaceous basaltic pyroclastic rocks on Mt. Carmel, Israel erupted in an intraplate environment with a thin, hot lithosphere. They contain abundant aggregates of hopper-shaped crystals of Ti-rich corundum, which have trapped melts with phenocryst assemblages (Ti2O3, SiC, TiC, silicides, native V) requiring extremely low ƒO2. These assemblages are interpreted to reflect interaction between basaltic melts and mantle-derived fluids dominated by CH4 + H2. Similar highly reduced assemblages are found associated with volcanism in a range of tectonic situations including subduction zones, major continental collisions, intraplate settings, craton margins and the cratons sampled by kimberlites. This distribution, and the worldwide similarity of δ13C in mantle-derived SiC and associated diamonds, suggest a widespread process, involving similar sources and independent of tectonic setting. We suggest that the common factor is the ascent of abiotic (CH4 + H2) fluids from the sublithospheric mantle; this would imply that much of the mantle is metal-saturated, consistent with observations of metallic inclusions in sublithospheric diamonds (e.g. Smith et al. 2016). Such fluids, perhaps carried in rapidly ascending deep-seated magmas, could penetrate high up into a depleted cratonic root, establishing the observed trend of decreasing ƒO2 with depth (e.g. Yaxley et al. in Lithos 140:142–151, 2012). However, repeated metasomatism (associated with the intrusion of silicate melts) will raise the FeO content near the base of the craton over time, developing a carapace of oxidizing material that would prevent the rise of CH4-rich fluids into higher levels of the subcontinental lithospheric mantle (SCLM). Oxidation of these fluids would release CO2 and H2O to drive metasomatism and low-degree melting both in the carapace and higher in the SCLM. This model can explain the genesis of cratonic diamonds from both reduced and oxidized fluids, the existence of SiC as inclusions in diamonds, and the abundance of SiC in some kimberlites. It should encourage further study of the fine fractions of heavy-mineral concentrates from all types of explosive volcanism.

Titanium oxynitrides (Ti(N,O,C)) are abundant in xenolithic corundum aggregates in pyroclastic ejecta of Cretaceous volcanoes on Mount Carmel, northern Israel. Petrographic observations indicate that most of these nitrides existed as melts, immiscible with coexisting silicate and Fe-Ti-C silicide melts, some nitrides may also have crystallized directly from the silicide melts. The TiN phase shows a wide range of solid solution, taking up 0–10 wt% carbon and 1.7–17 wt% oxygen, these have crystallized in the halite (fcc) structure common to synthetic and natural TiN. Nitrides coexisting with silicide melts have higher C/O than those coexisting with silicate melts. Analyses with no carbon fall along the TiN–TiO join in the Ti–N–O phase space, implying that their Ti is a mixture of Ti3+ and Ti2+, while those with 1–3 at.% C appear to be solid solutions between TiN and Ti0.75O. Analyses with &gt, 10 at% C have higher Ti2+/Ti3+, reflecting a decrease in fO2. Oxygen fugacity was 6 to 8 log units below the iron–wüstite buffer, at or below the Ti2O3–TiO buffer. These relationships and coexisting silicide phases indicate temperatures of 1400–1100 °C. Ti oxynitrides are probably locally abundant in the upper mantle, especially in the presence of CH4–H2 fluids derived from the deeper metal-saturated mantle.

Ultrahigh-pressure ( UHP ) materials ( e.g. , diamond, high-pressure polymorph of chromite) and super-reduced (SuR) phases ( e.g. , carbides, nitrides, silicides and native metals) have been identified in chromitites and peridotites of the Tibetan and Polar-Urals ophiolites. These unusual assemblages suggest previously unrecognized fluid- or melt-related processes in the Earth’s mantle. However, the origin of the SuR phases, and in particular their relationships with the UHP materials in the ophiolites, are still enigmatic. Studies of a recently recognized SuR mineral system from Cretaceous volcanics on Mt Carmel, Israel, suggest an alternative genesis for the ophiolitic SuR phases. The Mt Carmel SuR mineral system (associated with Ti-rich corundum xenocrysts) appears to reflect the local interaction of mantle-derived CH 4 ± H 2 fluids with basaltic magmas in the shallow lithosphere (depths of ∼30–100 km). These interactions produced desilication of the magma, supersaturation in Al 2 O 3 leading to rapid growth of corundum, and phase assemblages requiring local oxygen fugacity ( f O 2 ) gradually dropping to ∼11 log units below the iron–wustite (IW) buffer. The strong similarities between this system and the SuR phases and associated Ti-rich corundum in the Tibetan and Polar-Urals ophiolites suggest that the ophiolitic SuR suite probably formed by local influx of CH 4 ± H 2 fluids within previously subducted peridotites (and included chromitites) during their rapid exhumation from the deep upper mantle to lithospheric levels. In the final stages of their ascent, the recycled peridotites and chromitites were overprinted by a shallow magmatic system similar to that observed at Mt Carmel, producing most of the SuR phases and eventually preserving them within the Tibetan and Polar-Urals ophiolites.

The new mineral species carmeltazite, ideally ZrAl2Ti4O11, was discovered in pockets of trapped melt interstitial to, or included in, corundum xenocrysts from the Cretaceous Mt Carmel volcanics of northern Israel, associated with corundum, tistarite, anorthite, osbornite, an unnamed REE (Rare Earth Element) phase, in a Ca-Mg-Al-Si-O glass. In reflected light, carmeltazite is weakly to moderately bireflectant and weakly pleochroic from dark brown to dark green. Internal reflections are absent. Under crossed polars, the mineral is anisotropic, without characteristic rotation tints. Reflectance values for the four COM wavelengths (Rmin, Rmax (%) (&lambda, in nm)) are: 21.8, 22.9 (471.1), 21.0, 21.6 (548.3), 19.9, 20.7 (586.6), and 18.5, 19.8 (652.3). Electron microprobe analysis (average of eight spot analyses) gave, on the basis of 11 oxygen atoms per formula unit and assuming all Ti and Sc as trivalent, the chemical formula (Ti3+3.60Al1.89Zr1.04Mg0.24Si0.13Sc0.06Ca0.05Y0.02Hf0.01)&Sigma, =7.04O11. The simplified formula is ZrAl2Ti4O11, which requires ZrO2 24.03, Al2O3 19.88, and Ti2O3 56.09, totaling 100.00 wt %. The main diffraction lines, corresponding to multiple hkl indices, are (d in &Aring, (relative visual intensity)): 5.04 (65), 4.09 (60), 2.961 (100), 2.885 (40), and 2.047 (60). The crystal structure study revealed carmeltazite to be orthorhombic, space group Pnma, with unit-cell parameters a = 14.0951 (9), b = 5.8123 (4), c = 10.0848 (7) &Aring, V = 826.2 (1) &Aring, 3, and Z = 4. The crystal structure was refined to a final R1 = 0.0216 for 1165 observed reflections with Fo &gt, 4&sigma, (Fo). Carmeltazite exhibits a structural arrangement similar to that observed in a defective spinel structure. The name carmeltazite derives from Mt Carmel (&ldquo, CARMEL&rdquo, ) and from the dominant metals present in the mineral, i.e., Titanium, Aluminum and Zirconium (&ldquo, TAZ&rdquo, ). The mineral and its name have been approved by the IMA Commission on New Minerals, Nomenclature and Classification (2018-103).

The minimum oxygen fugacity ( f O2) of Earth’s upper mantle probably is controlled by metal saturation, as defined by the iron-wustite (IW) buffer reaction (FeO → Fe + O). However, the widespread occurrence of moissanite (SiC) in kimberlites, and a suite of super-reduced minerals (SiC, alloys, native elements) in peridotites in Tibet and the Polar Urals (Russia), suggest that more reducing conditions ( f O2 = 6–8 log units below IW) must occur locally in the mantle. We describe pockets of melt trapped in aggregates of corundum crystals ejected from Cretaceous volcanoes in northern Israel which contain high-temperature mineral assemblages requiring extremely low f O2 (IW < −10). One abundant phase is tistarite (Ti2O3), previously known as a single grain in the Allende carbonaceous chondrite (Mexico) and believed to have formed during the early evolution of the solar nebula. It is associated with other reduced phases usually found in meteorites. The development of super-reducing conditions in Earth’s upper mantle may reflect the introduction of CH4 + H2 fluids from the deep mantle, specifically related to deep-seated volcanic plumbing systems at plate boundaries.