Mantle Minerals Research Articles

In search for primary sources of placer diamonds of northeast Siberian craton: Evidence from the U–Pb ages and geochemistry of alluvial zircons

AbstractThe northeastern Siberian craton stores numerous placers of diamonds that differ in morphology and texture, and originate from different types of primary deposits, primarily kimberlites. Analyses of mantle zircons selected from samples of alluvial and coarse clastic sediments in the watersheds of the Olenek and Kyutyungde rivers in the Anabar‐Olenek subprovince of the Yakutian diamond province provide constraints on kimberlite magmatism events in the area. The new U–Pb ages and typical kimberlitic signatures of the Kyutyungde zircons trace‐element patterns reveal three main magmatic events that produced kimberlites: Middle Paleozoic (Late Devonian to Early Carboniferous), Jurassic and Triassic. The Jurassic zircons (177–149 Ma) are mainly related to kimberlites in the proximal Kuoika‐Molodo and Khorbusuon fields. Triassic zircons (240–221 Ma) were probably released during large‐scale erosion of the eastern Anabar shield, however, the presence of such zircons in the Kyutyungde area indicates that kimberlites of the respective magmatic stage may exist within the immediate vicinity of the area. The only Middle Paleozoic zircon sample (358.6 Ma, D3‐C1 boundary) may originate from a proximal kimberlite within the Kyutyungde area. The presence of Middle Paleozoic kimberlitic zircons, along with harzburgite–dunitic pyropes, indicates that the primary deposit of diamonds and related minerals may exist near or within the Kyutyungde area. Late Ediacaran–Early Cambrian (573–473 Ma) mantle zircons found in Early Cambrian conglomerates of the area, along with other mantle minerals including Cr spinel of a diamond assemblage, record another Precambrian event of potentially diamondiferous magmatism in the Kyutyungde basin.

A COMPARATIVE ANALYSIS OF DIAMONDS IN NON-KIMBERLITIC ROCKS OF THE WORLD AND NEOGENE SANDS OF UKRAINE

The diamond mineralogy from a number of different non-kimberlitic occurrences of the world was analyzed and a comparison to diamonds from Neogene placers of Ukraine was made. Diamonds from lamprophyres of the Canadian Shield, metakomatiites of the Guiana and West African Shields, and ultra-metamorphic rocks in Asian, European and African continental occurrences were considered. In general, Ukrainian Neogene placer diamonds have many similar mineralogical features to diamonds from lamprophyres and metakomatiites, which differ little from diamonds from kimberlites and lamproites. Ukrainian placer diamonds are characterized by their micron sizes (≤0.5 mm), many of them are colored and have a cubic habit and nitrogen-free compositions, relatively frequent spectral Ib and Iаb types, and orange photoluminescence behavior. In addition, many diamonds are characterized by a relatively high content of hydrocarbons (i.e., CH2, CH3 groups and bonds >C=CH2), OH groups, also C=O, N-H, CO3, NO3-groups. This is evidence for a volatile-rich environment during the diamond crystallization. The formation of diamonds from lamprophyres and metakomatiites, as well as from kimberlites and lamproites, occurred under mantle temperatures and pressures. The relatively recently discovered diamond-bearing lamprophyres and metakomatiites have a number of similarities. They are: i) both formed on the edges of Archean cratonic structures, ii) their old ages (2.7 billion years ago and 1.83 billion years ago for the lamprophyres and 2.2 billion years ago for the metakomatiites), iii) both are strongly metamorphosed, iv) both contain many fragments of rocks of various origins, v) both contain rare xenograins of mantle minerals having diamond-bearing peridotite and eclogite associations, and vi) the diamonds themselves are often microcrystals and many are colored and have a cubic habit. The main difference between diamonds from the lamprophyres and metakomatiites is in their carbon isotopic signatures and their thermal history in the mantle. This is expressed by their different nitrogen contents and the different degree of its aggregation. Diamond-bearing ultrametamorphic rocks are mainly Paleozoic-Mesozoic in age (i.e., 531-92 million years) and occupy a tectonic setting at convergent plate boundaries unlike diamond-bearing lamprophyres and metakomatiites. Diamonds from ultrametamorphic rocks differ from diamonds from lamprophyres and metakomatiites as well as from Ukrainian placer diamonds from Neogene sands in a number of ways.

Seismic signals induced by the Metasomatism of mantle wedge by siliceous melts: Insights from the elasticity of orthopyroxene at high pressure and temperature

Large amounts of silica held by slabs during subduction prefer to concentrate into the eclogite melts and further lead to the metasomatism of the overlying mantle wedge. However, the metasomatism process mediated by siliceous melts in the mantle wedge and the seismic signals associated remain poorly constrained. Peridotite in the mantle wedge is sufficiently silica undersaturated. Therefore, SiO2-rich melts would react with olivine in the peridotite to form orthopyroxene (opx). The local enrichment of opx has also been proposed to account for the observed low VP/VS ratio in the mantle wedges of a few subduction zones, revealing the metasomatism by silica saturated melts there. But the anomalously low VP/VS regions in a few subduction zones are inconsistent with the widespread metasomatism of the mantle wedge. In this study, we determined the elasticity of Fe-bearing opx (Mg0.875Fe0.125)SiO3 at high pressure and temperature (P-T) conditions. The VP/VS ratio of opx has a strong dependence on the pressure and temperature conditions, and only exhibits low VP/VS at low pressure and high temperature. Although the enrichment of opx may be widespread, it can only produce a discernible low VP/VS ratio at subduction zones with proper thermal conditions. Together with the elasticities of other major minerals in the upper mantle, we investigated the effect of opx enrichment on VP/VS ratio at mantle wedge conditions. The VP/VS ratio linearly decreases with the opx volume fraction (Ω), and the relationship can be described as VP/VS = 1.772 − 0.142Ω. Combining our high-quality mineral elasticity data with seismic tomography and thermal structure, we constrained the mineral proportions in the northern wedge of the Alaska subduction zone. The opx enriched area coincides well with the anomalously low VP/VS domain, indicating the strong metasomatism by siliceous melts in this mantle wedge.

Boron isotopes in blue diamond record seawater-derived fluids in the lower mantle

Boron is a quintessential crustal element but its conspicuous presence in diamond – a mantle mineral – raises questions about potential subduction pathways for boron and other volatiles. It has been a long-standing goal to characterize the isotopic composition of boron in blue, boron-bearing (Type IIb) diamonds to reveal its origin. Mineral inclusions indicate that Type IIb diamonds crystallize at transition zone to lower mantle depths, meaning that if the boron is subducted it would trace a pathway of volatile elements into the deep mantle. Here, using off-line laser ablation sampling, we present the first boron isotope compositions, along with trace element contents and carbon isotope compositions, of a suite of blue diamonds mainly sourced from the Cullinan diamond mine in South Africa. The ten analyzed blue diamonds have a wide range in δ11B, between −9.2 ± 2‰ and −0.5 ± 2‰, compared to the more restricted range for mid-ocean ridge basalts (−7.1 ± 0.9‰). Carbon isotope values for the blue diamonds range between −20.6 and −1.8‰, with a mode at −17‰, significantly more negative than the main mantle mode at −5‰. Combined, the boron and carbon isotope compositions require fluid input from subducted oceanic lithosphere down into deep mantle source regions of blue diamonds. This finding highlights a deep subduction pathway for volatiles to stoke the source regions of deeply-derived magmas.

Single‐Crystal Elasticity of Phase E at High Pressure and Temperature: Implications for the Low‐Velocity Layer Atop the 410‐km Depth

AbstractDense hydrous magnesium silicate (DHMS) phase E is a potential water carrier in subducting slabs that can transport water to the Earth's deep mantle between the bottom of the upper mantle and the uppermost transition zone. Therefore, knowledge on the high pressure‒temperature (P‒T) full elastic moduli of phase E at relevant mantle conditions is important in deciphering the existence of DHMS phases and their influences on seismic profiles in the region; however, the high P‒T elasticity data of phase E still remains lacking. In this work, we determined the combined effect of P‒T on the single‐crystal elasticity of phase E up to 24 GPa and 900 K by in situ X‐ray diffraction and Brillouin scattering measurements in externally‐heated diamond anvil cells. The aggregate elastic moduli and compressional‐wave (VP) and shear‐wave (VS) velocities of phase E are then derived by analyzing the single‐crystal elasticity and density data using the third‐order finite‐strain equations. We found that phase E exhibits much lower bulk and shear moduli and acoustic velocities than the most abundant constituent minerals in the upper mantle and transition zone, such as olivine, clinopyroxene, garnet, and wadsleyite. The modeled results using the obtained elasticity results show that the existence of phase E in a hydrated pyrolite model can result in relatively lower Vp and Vs profiles and negative velocity anomalies in seismic observations. The existence of phase E with relatively lower velocity profiles could be a possible origin of the low‐velocity layers atop the 410‐km discontinuity in some cold and highly‐hydrated regions.

Prediction of the melting curve and phase diagram for CaO using newly developed interatomic potentials

A comprehensive investigation of the melting curve and pressure–temperature (P–T) phase diagram for CaO, a candidate mineral in the Earth's lower mantle, is performed via atomistic simulations applying newly developed interatomic potentials. The efficiency and reliability of the new potentials under high temperature and pressure are verified with lattice dynamics, molecular dynamics, and first–principles approaches, where the fitting values of the potentials are extracted from the lattice parameters, elastic constants, and energy differences of rock–salt (B1) and cesium chloride (B2) phases in CaO. The melting temperatures of CaO with B1 structure at ambient pressure obtained from the single–phase method, void method, and two–phase method are 3080 K, 2775 K, and 2767 K, respectively. The structure and diffusion are evaluated by radial distribution functions, mean square displacements, and self–diffusion coefficients in the solid and liquid states for CaO. Simultaneously, the P–T phase diagram of CaO is calculated up to the core–mantle boundary pressure of 135 GPa, in which the Clausius–Clapeyron relation is introduced to determine the slope of the phase boundary between B1 and B2 phases. Other physical properties, including phase transition pressure, thermal expansion coefficient, isovolumic heat capacity, and entropy, are investigated. The limitations of the new potentials are discussed.

Development of Lattice‐Preferred Orientations of MgO Periclase From Strain Rate Controlled Shear Deformation Experiments Under Pressure up to 120 GPa

AbstractThe seismic anisotropy observed in Earth's lowermost mantle (D″ layer) is thought to originate from the lattice‐preferred orientation (LPO) of mantle materials induced by plastic deformation. Ferropericlase is the second most abundant mineral in the lower mantle, and its LPO induced by deformation may significantly contribute to the seismic anisotropy in the D″ layer. The slip system(s) of ferropericlase controlling the LPO in the D″ layer is still controversial, owing to technical difficulties in conducting high‐pressure deformation experiments. We conducted shear deformation experiments on MgO under pressures of up to 120 GPa and reported the LPO after the deformation experiments. Our results indicate that {100}<011> is the dominant slip system in the D″ layer. The LPO developed during shear deformation would result in shear wave splitting with VSH > VSV, consistent with seismic observations in the regions expected to accommodate large shear strain by subducted slabs in the D″ layer.

Adsorption behavior of molecular hydrogen in forsterite

Recent experimental studies have already discussed the existence of molecular hydrogen in mantle minerals. Here, we investigate the adsorption behavior of molecular hydrogen in forsterite with 0–15 Å intercrystalline pore at 0–519 MPa and 300–1800 K by using the Grand Canonical Monte Carlo (GCMC) method. Molecular hydrogen fills the interstitial positions of nonporous forsterite in an adsorbed state, whereas the filling of intercrystalline pore includes the adsorbed and free states. The adsorption of molecular hydrogen on the crystal surface of forsterite intercrystalline pore belongs to physisorption. The interaction between the adsorbate molecular hydrogen and the adsorbent forsterite framework weakens with pressure and strengthens with temperature, which is a crucial factor, and intercrystalline pore size. The adsorption capacity of molecular hydrogen in the intercrystalline pore of forsterite increases with pressure and intercrystalline pore size and decreases with temperature. By contrast, the adsorption capacity of molecular hydrogen in nonporous forsterite is controlled by pressure above 1200 K. Variations in intercrystalline pore size above 5 Å have a negligible effect on the capacity of adsorbed state molecular hydrogen at a given temperature and pressure. The adsorption of molecular hydrogen on different crystal faces of forsterite is anisotropic, with stronger adsorption on (001) and (100) than on (010) crystal faces. The adsorption capacity of molecular hydrogen in the intercrystalline pore decreases with the increase in oxygen fugacity at a given pressure, temperature, or intercrystalline pore sizes. The significant amount of molecular hydrogen stored in forsterite can provide a rich material basis for the short-term seismic precursor anomaly of hydrogen concentration and the formation of water through the reaction of silica with molecular hydrogen in the mantle.

Zinc isotope fractionation in mantle rocks and minerals, and a revised δ66Zn value for the Bulk Silicate Earth

The isotope composition of zinc (Zn) can be an important tracer of planetary formation and differentiation, but estimates of the Bulk Silicate Earth (BSE) and the extent and origin of Zn isotope variations in the mantle continue to be debated. We report 153 high-precision Zn isotope analyses of whole-rock samples and minerals of well-characterized, mantle-derived spinel and garnet peridotites from five sites in Siberia, Mongolia and China: 38 xenoliths in basaltic rocks (fertile to strongly melt-depleted as well as variably metasomatized or veined peridotites) and 3 orogenic peridotites. Data quality was rigorously tested by twenty-two duplicated analyses using several dissolution techniques. Spinel (Sp) contains 760–1460 μg/g Zn and hosts up to 58 % of whole-rock Zn budget in the peridotites followed by olivine (Ol, 30–66 % of whole-rock Zn budget), orthopyroxene (Opx), clinopyroxene (Cpx) and garnet, with abundance ratios of [Zn]Sp/[Zn]Ol = 15–47, [Zn]Ol/[Zn]Opx = ∼1.5, [Zn]Ol/[Zn]Cpx = ∼6. Spinel has higher δ66Zn values than coexisting silicates (∼0.12 ‰ higher than in Ol). Minerals in orogenic peridotites show disequilibrium Zn element and isotope partitioning due to slow inter-grain Zn diffusion at retrograde metamorphism.Fertile peridotites (≥3 wt% Al2O3) contain 52–60 μg/g Zn, usually higher than melt-depleted (<3 wt% Al2O3) rocks (40–53 μg/g). The δ66Zn values in the majority of spinel and garnet peridotites range from 0.11 to 0.26 ‰ and show no systematic co-variations with melt extraction indices (e.g., Al2O3, Mg#), suggesting, unlike some previous studies, that partial melting does not appreciably affect Zn isotope composition of residual mantle. Garnet lherzolites yield an average δ66Zn of 0.22 ± 0.09 ‰ (2SD), similar to that (0.18 ± 0.07 ‰, 2SD) for shallower spinel peridotites, indicating uniform Zn isotope composition with depth. Four fertile lherzolites from earlier work, duplicated in this study to assess inter-laboratory bias, fall in the same δ66Zn range, suggesting that previously reported higher δ66Zn for these samples could be due to analytical problems. We thus estimate the δ66Zn of the BSE at 0.19 ± 0.08 ‰ (2SD) based on suitable fertile peridotites from several localities in this study and the literature.The δ66Zn values (−0.10 to 0.04 ‰) are much lower in Fe-rich (9.3–13.1 wt% FeOT) and veined spinel peridotites as well as in spinel pyroxenite veins from Mongolia (−0.20 to 0.11 ‰). The Fe-rich peridotites and pyroxenites are rich in Zn (up to 113 μg/g) and were previously found to have anomalously low δ56Fe (−0.33 to − 0.27 ‰) and δ53Cr (−1.36 to − 0.05 ‰). We attribute these features to kinetic isotope fractionation during reaction with mafic melts migrating in conduits in the lithospheric mantle or intrusion of Fe-Zn-rich melts with light Fe-Zn isotope compositions. Kinetic Zn isotope fractionation, rather than equilibrium partial melting, may be a major cause of Zn isotope heterogeneity in the mantle.

XENOLITHS OF POLYMICTIC BRECCIAS FROM KIMBERLITES OF THE YAKUTIAN DIAMONDIFEROUS PROVINCE

The polymictic breccias, extremely rare mantle conglomerates being the fragments of rocks and large mantle minerals cemented with fine-grained mass have been long provoking interest of petrologists worldwide. This work provides a comparative analysis of two xenoliths of polymictic rocks from kimberlite pipes of different age and productivity occurring in the Siberian craton. The similarity of the chemical composition of some minerals of polymictic breccias from kimberlites within different parts of the Siberian craton assumes possible formation of these minerals caused by the same factors in the prekimberlite period of these parts of the lithospheric mantle. A wide range of compositions and chaotic zoning of minerals, the presence of exsolution textures in orthopyroxene, ilmenite, sulfide, and kelyphite rims on garnet suggest that the fragments of the studied xenoliths are unbalanced. Sample SH18/20 is the first polymictic breccia showing asthenospheric melt-fluids sampling shallow depths of the spinel facies.

Sound velocity anomalies of limestone at high pressure and implications for the mantle wedge

ABSTRACT Limestone mainly consisting of CaCO3 is one of the most abundant carbonates on Earth's surface. The sound velocities of limestone at high pressure were determined at room temperature using ultrasonic interferometry in a multi-anvil apparatus. Softening and discontinuities in compressional (P) and shear (S) wave velocities have been observed at around 1.45 GPa due to the phase transition of CaCO3-I to CaCO3-II, and the coexistence of CaCO3-IIIb and CaCO3-III stay up to ∼5 GPa. Limestone under CaCO3-I and CaCO3-III phase has much lower velocities and higher V P/V S ratio than most crustal and mantle minerals and the PREM model. Phase transitions from CaCO3-I to CaCO3-II cause the abrupt reduction of V P, V S, and V P/V S. The low velocities and high/low V P/V S ratio are well consistent with the seismology observed in the mantle wedge. The result suggests that the subduction of limestone into Earth's interior would cause low-velocity anomalies in mantle wedges.

Narrow, Fast, and “Cool” Mantle Plumes Caused by Strain‐Weakening Rheology in Earth's Lower Mantle

AbstractThe rheological properties of Earth's lower mantle are key for mantle dynamics and planetary evolution. The main rock‐forming minerals in the lower mantle are bridgmanite (Br) and smaller amounts of ferropericlase (Fp). Previous work has suggested that the large differences in viscosity between these minerals greatly affect the bulk rock rheology. The resulting effective rheology becomes highly strain‐dependent as weaker Fp minerals become elongated and eventually interconnected. This implies that strain localization may occur in Earth's lower mantle. So far, there have been no studies on global‐scale mantle convection in the presence of such strain‐weakening (SW) rheology. Here, we present 2D numerical models of thermo‐chemical convection in spherical annulus geometry including a new strain‐dependent rheology formulation for lower mantle materials, combining rheological weakening and healing terms. We find that SW rheology has several direct and indirect effects on mantle convection. The most notable direct effect is the changing dynamics of weakened plume channels as well as the formation of larger thermochemical piles at the base of the mantle. The weakened plume conduits act as lubrication channels in the mantle and exhibit a lower thermal anomaly. SW rheology also reduces the overall viscosity, notable in terms of increasing convective vigor and core‐mantle boundary heat flux. Finally, we put our results into context with existing hypotheses on the style of mantle convection and mixing. Most importantly, we suggest that the new kind of plume dynamics may explain the discrepancy between expected and observed thermal anomalies of deep‐seated mantle plumes on Earth.

First Experimental Synthesis of Mg Orthocarbonate by the MgCO3 + MgO = Mg2CO4 Reaction at Pressures of the Earth’s Lower Mantle

Mg-carbonate is one of the main carbonates subducting from the Earth’s surface into the mantle and possible reactions of this compound with the main mantle minerals determine the stability of carbonates into the Earth’s mantle. Recently, we have theoretically shown that at pressures and temperatures of the Earth’s lower mantle MgCO3 should react with MgO, producing Mg2CO4. Here, using diamond anvil cell technique, we have performed in situ investigation of the product of MgCO3 + MgO reaction at pressures around 50 GPa and temperatures above 2000 K. Investigation of Raman and X-ray diffraction patterns unambiguously indicates that reaction has been realized and as the reaction product we suggest the modification similar to M-g2CO4-P{{2}_{1}}{text{/}}c. Using the transmission electron microscopy technique, we show the presence of the new Mg-orthocarbonate/carbonate phase in the sample extracted from high-pressure environment.

First-row transition elements in pyroxenites and peridotites: A promising tool for constraining mantle source mineralogy

Mantle heterogeneity has a first-order control on the petrological and geochemical differences of erupted mafic lavas worldwide. Because of their contrasted distributions between mantle phases, First Row Transition Elements (FRTEs) have been considered potential lithological tracers. Using a combination of published data on natural and experimental samples and new high-precision analyses on a variety of pyroxenite samples, we investigate the parameters that control FRTE partition (Ds) and exchange (KDs) coefficients between common mantle minerals. We demonstrate that mineral-clinopyroxene exchange coefficients are independent of composition and temperature and that coefficients obtained from natural samples can be accurate as long a sufficiently high number of compositionally diverse samples are considered, making them reliable input parameters in mantle melting models. As a proof of concept, we use the exchange coefficients determined from natural mantle lithologies in this study, along with published experimental clinopyroxene/melt partitioning coefficients, to perform simple inverse modeling on two basalt suites from the Western Volcanic Zone in Iceland and Samoa, selected for their contrasted Mn/Fe and Zn/Fe ratios. Our results show that a given FRTE ratio in basalt can be explained by a large range of modal proportions in the source. However, when combined, FRTE ratios become a powerful tool to constrain the nature of the source.

H2O-induced sedimentary carbon migration from subducting slabs to the forearc mantle

Carbon in sedimentary carbonates dominates the global carbon input flux in subduction zones, the fate of which makes an impact on the global carbon cycle. At forearc depths, ∼32% of subducting water is released through slab dehydration and may greatly promote sedimentary carbon migration to the forearc mantle. However, it is controversial that considering the infiltration of external aqueous fluids, whether extremely limited or a significant portion of sedimentary carbon is liberated from subducting slabs in the forearc region. To explore to what extent hydrous fluids could facilitate carbon migration at forearc depths, hydrous carbonate-dominated sediment (1.14 wt.% H2O)-harzburgite reaction (layered) experiments have been performed at 1.5 GPa and 600–1000°C with various durations. For comparison, an anhydrous sediment-harzburgite reaction experiment was conducted to investigate the role of water on carbon migration. In hydrous experiments under subsolidus conditions (600–900°C), (1) a reaction zone comprised of clinopyroxene+dolomite forms at the sediment-harzburgite interface due to the metasomatic reaction; (2) the Ca# (100×Ca/[Ca+Mg+Fe], in molar) of calcite in the sediment layer drastically deceases when approaching the reaction zone; (3) newly formed dolomite and pargasite occur in the upper harzburgite layer. The above phenomena were not observed in the anhydrous experiment. Under a supersolidus condition (1000°C), a reaction zone composed of olivine+clinopyroxene+pargasite+CO2 formed as a result of hydrous carbonate melt-harzburgite interaction. The experiments demonstrate that aqueous fluids could significantly promote the chemical reaction and component exchange between sediments and mantle peridotite, and also induce subducting sedimentary carbon migration to the forearc mantle. It is estimated roughly that globally, ∼50% of subducting sedimentary carbon may be released at forearc depths. The carbon and water would be stabilized as carbonates (e.g., dolomite) and hydrous minerals (e.g., pargasite) in the forearc mantle, implying that the forearc mantle may be an important carbon reservoir. Our study explains the fate of a portion of carbon that is not returned to the atmosphere through arc volcanism.

Quench Products of K-Ca-Mg Carbonate Melt at 3 and 6 GPa: Implications for Carbonatite Inclusions in Mantle Minerals

Alkali-rich carbonate melts are found as inclusions in magmatic minerals, mantle xenoliths, and diamonds from kimberlites and lamproites worldwide. However, the depth of their origin and bulk melt composition remains unclear. Here, we studied quench products of K-Ca-Mg carbonate melt at 3 and 6 GPa. The following carbonates were detected at 3 GPa: K2CO3, K2Ca(CO3)2 bütschliite (R3¯2/m), o-K2Ca3(CO3)4 (P212121), K2Ca2(CO3)3 (R3), K2Mg(CO3)2 (R3¯m), Mg-bearing calcite, dolomite, and magnesite. At 6 GPa, the variety of quench carbonate phases includes K2CO3, K2Ca(CO3)2 bütschliite (R3¯2/m), d-K2Ca3(CO3)4 (Pnam), K2Mg(CO3)2 (R3¯m), aragonite, Mg-bearing calcite, dolomite, and magnesite. The data obtained indicate that alkali-bearing carbonate melts quench to the alkaline earth and double carbonates that are thermodynamically stable at quenching pressure and can be used as markers reflecting the pressure of their entrapment. Further, in this study, we established the fields of melt compositions corresponding to the distinct quench assemblages of carbonate minerals, which can be used for the reconstruction of the composition of carbonatitic melts entrapped by mantle minerals.

A relatively dry mantle transition zone revealed by geomagnetic diurnal variations.

The distribution of water within the mantle transition zone (MTZ) has important implications for the material circulation and partial melting of the mantle. Although solubility of hydrogen is very high, leading to speculations that the MTZ plays a key role in the deep-Earth water cycle, the actual water content remains an open question. Electrical conductivity of mantle minerals is very sensitive to water content, so reliable estimates of this physical parameter in the MTZ would provide valuable constraints. Here, we use recently developed joint inversion of geomagnetic diurnal variation for realistic source structure and one-dimensional mantle conductivity profile. Synthetic tests show that the resulting profile is a reasonable proxy for the electrical conductivity distribution of continental mantle over depths where model resolution is best (200 to 600 kilometer), even in the presence of lateral heterogeneity. The inferred water concentration in the MTZ is 0.03 weight %, one to two orders of magnitude below the solubility of wadsleyite and ringwoodite.

The solubility of N2 in silicate melts and nitrogen partitioning between upper mantle minerals and basalt

The solubility of N2 in basaltic (MORB) and haplogranitic melts was studied at oxidizing conditions (oxygen fugacity about two log units above the Ni–NiO buffer). Under these conditions, N2 is expected to be the only significant nitrogen species present in the melt. Experiments were carried out from 0.1 to 2 GPa and 1000–1450 ˚C using either an externally heated TZM pressure vessel, an internally heated gas pressure vessel or a piston cylinder apparatus. Nitrogen contents in run product glasses were quantified by SIMS (secondary ion mass spectrometry). To discriminate against atmospheric contamination, 15N-enriched AgN3 was used as the nitrogen source in the experiments. According to infrared and Raman spectra, run product glasses contain N2 as their only dissolved nitrogen species. Due to interactions with the matrix, the N2 molecule becomes slightly infrared active. Nitrogen solubility in the melts increases linearly with pressure over the entire range studied; the effect of temperature on solubility is small. The data may, therefore, be described by simple Henry constants Khaplogranite = (1461 ± 26) ppm N2/GPa and KMORB = (449 ± 21) ppm N2/GPa, recalculated to ppm by weight (μg/g) of isotopically normal samples. These equations describe the solubility of nitrogen during MORB generation and during melting in the crust, as we show by thermodynamic analysis that N2 is the only significant nitrogen species in these environments. Nitrogen solubility in the haplogranitic melt is about three times larger than for the MORB melt, as is expected from ionic porosity considerations. If expressed on a molar basis, nitrogen solubility is significantly lower than argon solubility, in accordance with the larger size of the N2 molecule. Notably, N2 solubility in felsic melts is also much lower than CO2 solubility, even on a molar basis. This implies that the exsolution of nitrogen may drive vapor oversaturation in felsic melts derived from nitrogen-rich sediments. We also measured the partitioning of nitrogen between olivine, pyroxenes, plagioclase, garnet, and basaltic melt by slowly cooling MORB melts to sub-liquidus temperatures to grow large crystals. The mineral/melt partition coefficients of nitrogen range from 0.001 to 0.002, and are similar to argon partition coefficients. These new data, therefore, support the assumption that there is little fractionation between nitrogen and argon during mantle melting and that the N2/Ar ratio in basalts and xenoliths is, therefore, representative of the N2/Ar ratio in the mantle source. This assumption is essential for assessing the size of the nitrogen reservoir in the mantle. Our data also show that for an upper mantle oxidation state that is similar to the one observed today, nitrogen outgassing by partial melting is extremely efficient and even low melt fractions in the range of a few percent may extract nearly all nitrogen from the mantle source.

Constraining Upper Mantle Viscosity Using Temperature and Water Content Inferred From Seismic and Magnetotelluric Data

AbstractMantle viscosity controls a variety of geodynamic processes such as glacial isostatic adjustment (GIA), but it is poorly constrained because it cannot be measured directly from geophysical measurements. Here we develop a method that calculates viscosity using empirical viscosity flow laws coupled with mantle parameters (temperature and water content) inferred from seismic and magnetotelluric (MT) observations. We find that combining geophysical constraints allows us to place significantly tighter bounds on viscosity estimates compared to using seismic or MT observations alone. In particular, electrical conductivity inferred from MT data can determine whether upper mantle minerals are hydrated, which is important for viscosity reduction. Additionally, we show that rock composition should be considered when estimating viscosity from geophysical data because composition directly affects seismic velocity and electrical conductivity. Therefore, unknown composition increases uncertainty in temperature and water content, and makes viscosity more uncertain. Furthermore, calculations that assume pure thermal control of seismic velocity may misinterpret compositional variations as temperature, producing erroneous interpretations of mantle temperature and viscosity. Stress and grain size also affect the viscosity and its associated uncertainty, particularly via their controls on deformation regime. Dislocation creep is associated with larger viscosity uncertainties than diffusion creep. Overall, mantle viscosity can be estimated best when both seismic and MT data are available and the mantle composition, grain size and stress can be estimated. Collecting additional MT data probably offers the greatest opportunity to improve geodynamic or GIA models that rely on viscosity estimates.

Spinel Harzburgite-Derived Silicate Melts Forming Sulfide-Bearing Orthopyroxenite in the Lithosphere. Part 1: Partition Coefficients and Volatile Evolution Accompanying Fluid- and Redox-Induced Sulfide Formation

We report abundances of major trace and volatile elements in an orthopyroxenite vein cutting a sub-arc, mantle-derived, spinel harzburgite xenolith from Kamchatka. The orthopyroxenite contains abundant sulfides and is characterized by the presence of glass (formerly melt) both interstitially and as inclusions in minerals, comparable with similar veins from the West Bismarck arc. The glass formed by quenching of residual melts following crystallization of abundant orthopyroxene, amphibole, and minor olivine and spinel. The interstitial glass has a low-Ti, high-Mg# andesite composition, with a wide range of H2O and S contents but more limited F and Cl variations. We calculate trace element partition coefficients using mineral and glass data, including those for halogens in amphibole, which agree with experimental results from the literature. Despite having a similar, high-Mg# andesite composition, the orthopyroxene-hosted glass inclusions usually contain much more H2O and S than the interstitial glass (4–7 wt% and ∼2,600 ppm, respectively). The initial vein-forming melts were oxidized, recording oxygen fugacity conditions up to ∼1.5 log units above the fayalite–magnetite–quartz oxygen buffer. They intruded the sub-arc mantle lithosphere at ≥1,300°C, where they partially crystallized to form high-Mg# andesitic derivative melts at ca. 1,050–1,100°C. Comparison with literature data on glass-free orthopyroxenite veins from Kamchatka and the glass-bearing ones from West Bismarck reveals fundamental similarities indicating common parental melts, which were originally produced by low-degree melting (≤5%) of spinel harzburgite at ≥1,360°C and ≤1.5 GPa. This harzburgite source likely contained ≤0.05 wt% H2O and a few ppm of halogens. Volatile evolution inferred from glass compositions shows that (i) redox exchange between S6+ in the original melt and Fe2+ in the host mantle minerals, together with (ii) the formation of an S-bearing, (H2O, Cl)-rich hydrothermal fluid from the original melt, provides the conditions for the formation of abundant sulfides in the orthopyroxenites during cooling. During this process, up to 85% of the original melt S content (∼2,600 ppm) is locally precipitated as magmatic and hydrothermal sulfides. As such, melts derived from spinel harzburgite sources can concentrate chalcophile and highly siderophile metals in orthopyroxenite dykes and sills in the lithosphere.