Hydrous Melts Research Articles

Trace elements and Li isotopes distinguish between liquid and solid phases contributing to mafic arc magmas

It is generally accepted that metasomatism of the mantle wedge peridotite by subducting slab-derived fluids plays a key role in dictating the composition of mafic arc magmas. However, this fluid metasomatism model has been challenged recently by the mélange diapirism model. In order to distinguish between liquid and solid phases that would exclusively contribute to mafic arc magmas, we have carried out an integrated study of whole-rock and mineral geochemistry for two types of contemporaneous mafic igneous rocks (gabbroic diorites and diorite dikes) from an accretionary orogen. The results indicate primary contributions from liquid phases composed of not only slab-derived aqueous solution but also seafloor sediment-derived hydrous melt. Although these mafic rocks all exhibit typical arc-like trace element distribution patterns, they show a series of differences in stable Li and radiogenic Sr–Nd–Hf isotope compositions as well as other geochemical variables. In general, the gabbroic diorites are characterized by enrichment in fluid-mobile elements (e.g., Rb, Ba, K, Pb, and Sr), high δ7Li and δ18O values, and depletion in Sr–Nd–Hf isotope compositions. By contrast, the diorite dikes exhibit enrichment in melt-mobile elements (e.g., LILE, LREE and Th), relatively low δ7Li values, and slight enrichment in Sr–Nd–Hf isotope compositions. There are also systematic differences and pertinent variations between Li isotope compositions and slab-derived fluid indicators such as whole-rock Rb/Nd, Sr/Nd, Nb/U, Th/La, Th/Nd and Th/Yb ratios for the two types of mafic igneous rocks. These indicate that the mantle sources of these mafic rocks would possess geochemical signatures that were acquired through chemical metasomatism by slab-derived fluids rather than physical mixing with mélange diapirs. Furthermore, the geochemical signatures allow for distinction between the oceanic slab-derived aqueous solution and the seafloor sediment-derived hydrous melt. This qualitative interpretation is quantitatively confirmed by model calculations of trace elements and Sr–Nd–Li isotopes in the two types of mafic igneous rocks. Therefore, the target mafic igneous rocks provide the geochemical evidence for the formation of their mantle sources through chemical metasomatism by incorporating the two types of metasomatic agent into the mantle wedge. This demonstrates a strong preference for the fluid metasomatism model over the mélange diapirism model for the origin of mafic arc magmas.

Sulfur isotope evidence from peridotite enclaves in southern West Greenland for recycling of surface material into Eoarchean depleted mantle domains

Eoarchean peridotite enclaves found in southern West Greenland's Itsaq Gneiss Complex (IGC) represent an important and valuable record of Earth's early geodynamic history. However, the origins of these rocks and the processes acting on them in the Eoarchean remain a subject of debate. Some researchers have proposed that these peridotites represent the oldest preserved pieces of Earth's mantle, while others have suggested that they represent ultramafic cumulates. Similarly, the geodynamic context in which they formed and were emplaced is subject to multiple interpretations. Some researchers argue that only vertical tectonic processes operated in the Eoarchean and others contend that these peridotites were embedded in the crust by horizontal tectonic processes. We present multiple sulfur isotope data from IGC peridotite enclaves, offering new insights into these rocks' origins and tectonic processes in the early Earth. Generally small but significant nonzero Δ33S values of 0.04 to 0.21‰ were detected in the studied peridotites. Peridotites with almost no petrographic signs of metasomatic alteration have on average slightly higher Δ33S values, whereas peridotites with clear petrographic and geochemical signatures of melt metasomatism were found to have slightly lower Δ33S values. These Δ33S values point to incorporation of surface-derived material of Archean age or older. Correlations between Δ33S values and previously published major and trace element data support the view that these peridotites were subject to hydrous melt depletion of incompatible elements, followed by variable melt re-enrichment. Notably, a distinct correlation also exists between previously published Hf isotope data and Δ33S values, indicating a depleted mantle source for melt percolating through the peridotites in the Eoarchean. The sulfur isotope data demonstrate that these processes included the introduction of surface-derived sulfur, pointing to an early onset of crustal recycling. These findings point to the existence of depleted mantle domains in the Hadean and suggest that crustal recycling processes operated during the Eoarchean or earlier.

The intrinsic effects of using rhenium gaskets in hydrothermal diamond anvil cell experiments on background fluorescence, contamination, and redox control

Because of the great stiffness and high melting point of rhenium (Re) metal, Re gaskets are widely used in hydrothermal diamond anvil cell (HDAC) experiments that involve aqueous fluids and even hydrous melts under high pressure–temperature (P–T) conditions. This metal was usually considered chemically inert in hydrothermal experiments, but some concerns have been raised about its reactivity with the fluids. Therefore, this communication addresses the intrinsic effects of using Re gaskets in HDAC experiments, including background fluorescence in Raman spectroscopy, contamination, and redox control. A series of hydrothermal experiments involving rhenium were performed in pure water, H2O-NaCl, and SiO2-COH systems using the HDAC up to 28.9 kbar and 850 °C and fused silica capillary capsule (FSCC) up to 87 bar and 300 °C, and Raman spectroscopy was employed for in situ analysis. The results indicate that (1) strong background fluorescence, often occurring between 200 and 700 °C, is caused by the dissolution of Re gaskets and the formation of aqueous species of Re with a low oxidation state, such as a Re2+cation and eventually, its hydroxide complexes; (2) in addition to the fluorescent Re species and unwanted carbon species produced from the diamond-water reaction catalyzed by Re, a considerable amount of ReO4−, which does not cause fluorescence and shows a dominant Raman peak at ∼970 cm−1, is detected in the fluids either in situ at high temperatures above 700 °C or under cooling conditions, and it can reduce the activity of H2O and the pH of the fluids and interfere with the assignments of Raman peaks of other species in the samples; and (3) the production of oxidizing aqueous species at high temperatures, including ReO4− and CO2, is attributed to the substantial loss of H2 and the corresponding increase in oxygen fugacity. Because of these intrinsic effects of using Re gaskets in HDAC experiments, implications for hydrothermal experiments are discussed with several previously reported examples such as the discrepancy in the solubility of rutile in water under elevated P–T conditions. Based on the results of the current and previous studies, four suggestions have also been made to minimize the unwanted effects of using Re gaskets, including the generation of a reduced experimental condition, a pre-heating treatment of Re gaskets, a gasket pre-indentation approach, and a gold-lined gasket method. Armed with the knowledge of these intrinsic effects as well as the advantages of using different HDAC metal gaskets, the researchers will be able to create appropriate experimental designs.

Reaction between volatile-bearing eclogite and harzburgite as a function of degree of interaction: Experimental constraints at 4 GPa

Abstract The mantle is known to be heterogeneous, mainly composed of peridotite and eclogite. Eclogite-derived hydrous melts may interact with harzburgite at the slab-mantle interface in subduction zones or in the sub-continental lithospheric mantle. In this study, such interactions were simulated by performing hybridization experiments in which a layer of eclogite was juxtaposed to a layer of harzburgite in the presence of H2O-CO2 at 4 GPa and 1200 °C, conditions where eclogite is super-solidus while harzburgite is sub-solidus. A diamond trap was placed in between the two layers to trap the fluid or melt phase, allowing direct determination of their composition. The multi-anvil was rotated at different frequencies to examine the effect of increasing degree of interaction on the melt composition as well as the mineral compositions. The interaction of eclogite-derived hydrous melt and harzburgite results in a reaction layer at the interface between the two lithologies, composed of Opx and garnet. The harzburgite above the reaction layer is metasomatized, containing various amounts of olivine, Opx, Cpx, and garnet. The eclogitic melt is modified during this interaction. With increasing interaction, a thicker reaction layer is formed. Both the eclogitic and the peridotitic garnet compositions approach each other and become intermediate between the composition of the garnet in the eclogite+H2O+CO2 system and the garnet in the harzburgite+H2O+CO2 system at these conditions. The Mg# of the peridotitic olivine and Opx decreases with increasing interaction. The initial basaltic melt in equilibrium with eclogite is metaluminous, turning to a peralkaline melt with increasing interaction with the harzburgite. The metasomatizing effect of the eclogite-derived hydrous melt on the harzburgite is observed by increasing the mode of the peridotitic Opx, Cpx, and garnet at the expense of peridotitic olivine and eclogitic garnet. A slight increase in melt fraction occurs as well. This interaction also results in a gradient in the log fO2. Relatively more oxidizing conditions occur near the reaction layer, becoming more reduced into the peridotite, suggesting that the reaction zones act as partial barriers for the melt to travel through the peridotite. Increased interaction leads to higher log fO2 values. These experiments demonstrate the influence of the degree of interaction on the range of melt compositions found in volcanic arcs as well as the degree of metasomatism in the mantle found in the sub continental lithospheric mantle.

Fingerprinting crustal anatexis with apatite trace element, halogen, and Sr isotope data

The geochemistry of apatite is a valuable tool for granite petrogenetic study. Here we explore the capability of apatite for fingerprinting anatectic reactions during crustal melting. We conducted a detailed petrographic, trace element, volatile, and Sr isotopic study of the apatites from four groups of leucosomes and leucogranites that formed by amphibole dehydration melting (group I), hydration melting (group II), muscovite dehydration melting (group III), and feldspar accumulation (Group IV) from the central Himalayan orogen. The coexistence of primary CO2-rich fluid and multiphase solid inclusions in apatite indicates fluid–melt immiscibility and suggests that C–O–H fluids were present during hydration melting. We observe marked differences in major and trace element, as well as halogen (F and Cl) contents in apatite from different groups, corresponding to different melting reactions. Apatite REE, Y, Mn, F, and F/Cl exhibit a decrease, whereas Sr/Y and Cl increase, from muscovite dehydration melting to hydration melting, and to amphibole dehydration melting. Amphibole dehydration melting results in similar CaO, Sr, and Eu/Eu* in apatite to hydration melting, but the latter leads to lower (La/Yb)N in apatite. These geochemical differences in apatite can be explained by different minerals participating in the melting reactions and varying melt polymerization resulting from the different melting reactions. The degree of melt polymerization decreases in the sequence from muscovite dehydration melting to hydration melting, and to amphibole dehydration melting. A higher degree of melt polymerization results in higher values for trace element partition coefficients between apatite and melt, and therefore the enhanced incorporation of REE, Y and Mn in apatite. Higher Sr and Eu/Eu* in apatite reflect the consumption of a larger amount of plagioclase in the melting reaction. The F and Cl contents in partial melts were calculated based on apatite composition, which exhibit an increasing trend from hydration melting to muscovite hydration melting, and to amphibole hydration melting. Such a trend can be explained by different proportions of hydrous minerals (muscovite and amphibole) participating in the melting reactions, with amphibole responsible for the high Cl content in melt and apatite. In addition, the apatite Sr isotopic compositions record the Sr isotopic disequilibrium during partial melting and exhibit distinct evolutional trends resulting from different anatectic reactions. Muscovite dehydration melting forms melt with higher 87Sr/86Sr than the restite due to radiogenic Sr released by muscovite. Apatite therefore records progressively decreasing 87Sr/86Sr during melt evolution before the isotopic homogenization between the partial melt and the restite. In contrast, apatites crystallized from the melt of hydration melting show an evolutional trend of increasing 87Sr/86Sr. In summary, the elemental and isotopic compositions of apatite can be related to different types of melting reactions, and can therefore be used as an indicator of the mechanisms of melt formation during crustal anatexis. We demonstrate such an application through the case study of group IV apatite from feldspar accumulation, and also explore its utility in granite petrogenetic studies.

Tonian-Cryogenian bimodal volcanism and related sulfide ores in the Arabian-Nubian Shield: An example from the Dendekan prospect in the Eastern Desert of Egypt

The Dendekan prospect is located in the southern segment of the Eastern Desert of Egypt, which constitutes the northwestern part of the Arabian-Nubian Shield. The volcanic rocks of the Dendekan prospect are considered to be the eastern part of the Shadli-Ranga bimodal volcanic belt. These volcanic rocks include massive basaltic flows that are intruded by porphyritic rhyolite. The porphyritic rhyolite yielded a SIMS U-Pb zircon age of 750 ± 10 Ma. Both basalt and rhyolite have a low-K tholeiitic affinity and their mantle-normalized trace element patterns show enrichment of large ion lithophile elements (LILE), U and Th over high field strength elements (HFSE) and pronounced negative Nb anomaly. These geochemical characteristics along with the bimodal nature of the volcanic rocks are consistent with incipient rifting in an intra-oceanic island arc tectonic setting. The onset of rifting promoted hydrous melting of depleted mantle as indicated by the low Nb/Yb ratio of the Dendekan basalt. Geochemistry of the Dendekan rhyolite and its high zircon εHf (T) values (9.5 average) suggest melting of mainly juvenile mafic lower crust. The Hydrothermal alteration in the prospect is represented by patchy and vein-like epidotization as well as silicification of basalt, while the porphyritic rhyolite exhibits extensive sericitization along the wall of old exploited trenches extending close to the contact between the rhyolite and the basalt. Pyrite occurs as disseminated crystals and aggregates in association with minor pyrrhotite and chalcopyrite. Pyrite is commonly altered to ferric oxyhydroxide, locally with native gold inclusions. Sulfides in the Dendekan prospect may represent a pyrite-rich deep part of a volcanic-associated massive sulfide system that was affected by weathering. Compared with the Tonian bimodal volcanic rocks of the Dendekan prospect, the volcanic assemblage from the western part of the Shadli-Ranga bimodal belt exhibits a younger Cryogenian age and a less pronounced subduction geochemical signature suggesting the evolution form Tonian incipient arc rifting to Cryogenian rifting in a back-arc setting.

Shallow subduction of Indian slab and tectono-magmatic control on post-collisional porphyry mineralization in southeastern Tibet

The 1500-km long Gangdese belt in southern Tibet shows uneven distribution of giant to large porphyry deposits over 45 Mt Cu mainly in the middle-east segment between longitude 87–92°E. However, the western (80–86°E) and eastern end (92–96°E) is generally barren. The recent discovery of Demingding, Cuibaizi and Tangbula porphyry deposits in the east of 92°E has attracted great attention on their origin. Recent high-resolution seismic imaging shows the torn Indian lithosphere subducts with diverse angle. In contrast to the middle-east segment with moderate angle Indian plate subduction, the southeastern Tibet is characterized with a shallow dip of subduction (eastern of Comei rift), where Demingding, Cuibaizi and Tangbula deposits are located. To reveal the formation mechanism of these deposits as well as the Indian slab motion pattern beneath them, we compiled reported whole rock major and trace elements, Sr and Nd isotope signature, zircon trace element, U-Pb ages and Hf isotope data of Miocene ore-related adakitic rocks from Demingding and Tangbula to the north, and Oligocene ore-barren adakitic rocks from Linchi to the south. There is a clear negative correlation between zircon U-Pb ages of rocks and their distance to Indus-Yarlung Zangbo suture: Linchi is around 20 km away from the suture, with an average U-Pb age of 27.1 Ma, while Demingding and Tangbula rocks are 50 and 90 km away from the suture, with ages of 20.3 and 19.7 Ma respectively. Granitoids from Linchi have less compatible element Ni and Cr contents of 4.07 and 5.84 ppm on average respectively, while those of Demingding (20.1 and 43.4 ppm) and Tangbula (5.52 and 7.90 ppm) are much higher. Ni and Cr as compatible elements are concentrated in mafic minerals, and are thus proper indicators for mantle imprint indicators. In addition, as shown by Sr-Nd isotopes, Linchi granitoids have features of ancient crust [(87Sr/86Sr)i = 0.7059 to 0.7085, εNd(t) = − 6.20 to −2.90], while Demingding and Tangbula granitoids show less radiogenic features [(87Sr/86Sr)i = 0.7059 to 0.7068, εNd(t) = − 3.27 to −1.70], which are more similar to coexisting juvenile arc. Demingding and Tangbula granitoids also show signature of high fO2 and hydrous melt condition, as indicated by calculated fO2 of ΔFMQ + 2, and amphibole fractionation indicated by decreasing Dy/Yb with SiO2, since amphibole favors MREE (Dy) rather than HREE (Yb). Combining above, our work shows that the Indian slab constantly subducted shallowly beneath these deposits, given no mantle-like signature of near-suture Oligocene adakitic rocks. We suggest the cause to the formation of Demingding, Tangbula and Cuibaizi deposits is the reactivation of pre-enriched arc root materials, triggered by constant northward migration of Indian slab. This is supported by similar isotope signature between Miocene Demingding and Tangbula ore-related porphyries and coexisting arc, and absence of coeval pre-collisional porphyry deposits. The essential components for these porphyry deposits, high fO2 and water content, were also likely contributed from the pre-enriched juvenile arc root.

Molybdenum isotopes record recycling of subducting sediment in active continental margin, Northeast China

Highly variable molybdenum (Mo) isotope compositions have been reported for mafic arc volcanics above oceanic subduction zones. The heavy Mo isotope signatures of mafic arc magmas are generally attributed to addition of high δ98Mo oceanic crust-derived fluids to the subarc mantle sources. However, subduction zone fluids at subarc depths may occur in the forms of aqueous solution and hydrous melts, and seafloor sediments would also be subducted to subarc depths to produce hydrous melts. If such sediment-derived melts were incorporated into the mantle wedge, it is intriguing what is their effect on the Mo isotope composition of mafic arc magmas. Here we report Mo isotope data for Early Jurassic mafic igneous rocks from Northeast China, which was an active continental margin during subduction of the Paleo-Pacific Plate in the Mesozoic. These rocks have δ98Mo values of −0.26‰ to 0.17‰, which are mostly higher than the normal mantle value of −0.20‰ ± 0.01‰. They also exhibit arc-like trace element compositions, moderate (87Sr/86Sr)i ratios of 0.7042 to 0.7047, and neutral εNd(t) values of −2.8 to 2.2. The high δ98Mo values are associated with low Mo/Ce ratios, enriched SrNd isotopes, and high melt-mobile element contents in the mafic igneous rocks. These geochemical features indicate that the heavy Mo isotope signatures in these rocks were mainly inherited from subducting sediment-derived melts. Subducting Paleo-Pacific oceanic crust-derived aqueous solutions and seafloor sediment-derived hydrous melts would metasomatize the overlying mantle wedge beneath the northeastern China continent, and the sediment-derived melts would have contributed the heavy Mo isotope signatures to the mantle sources of mafic arc magmas in the active continental margin. Therefore, the Mo isotope study of mafic igneous rocks is a powerful means to decipher the recycling of crustal components at convergent plate margins.

Arc signatures in abyssal peridotites and its implications

Investigating mass exchanges between the subduction zones and mid-ocean ridges provides essential clues to understanding recycling process and mantle convection in the Earth's mantle. In this study, we found evidence of recycled subduction signals in the abyssal peridotites from mid-ocean ridges through their extremely low bulk (Dy/Yb)N and bulk Al2O3, which could not be explained by normal decompression melting at mid-ocean ridges, but required a hydrous melting history. We show here that abyssal peridotites from the fast-spreading Pacific Oceanic Ridges (East-Pacific Rise and Pacific-Antarctic Ridge), to the ultraslow-spreading Southwest Indian Ridge and to the slow-spreading Mid-Atlantic Ridge, require increasing amount of slab-derived fluid in their mantle sources. Therefore, the subduction influence on abyssal peridotites is independent of the spreading rates of the overlying ridges. Locations, such as the Fifteen-Twenty Fracture Zone, the Rainbow Massif from the MAR and the Hess Deep from EPR, have abyssal peridotites overlap well with forearc peridotites, suggesting that the prominent characteristics of arc mantle wedge could be preserved in abyssal peridotites when the traveling distance or time is short for the recycled arc mantle migrating in the mantle convection flow. The well-preserved subduction-related signature in ridge areas that are relatively proximal to modern subduction zones imply that mass exchanges between the subduction zones and mid-ocean ridges may be more efficient than previously thought.

Triassic Appinite from the Qinling Orogen (Central China): Hydrous Melting of Depleted Mantle Wedge in Post-Collision Stage

Mantle wedge melting and the formation of hydrous mafic melts in collision orogenic belts have great significance for crustal melting and the related granitic magmatism, which can provide key messages about the crustal–mantle interaction in the convergent margin. This paper reported Late-Triassic appinite (212 ± 2 Ma), which is closely associated with Late-Triassic granites. The large euhedral hornblende crystals in the appinite indicate a water-rich feature. This appinite displays low SiO2 (46.55% to 50.44%) contents, high MgO (7.62 to 10.76%) and Cr and Ni contents, with high Mg# values of 61 to 75. It also displays insignificant Eu anomalies (Eu*/Eu = 0.91 to 0.93), high Sr (596 to 676 ppm) contents and moderate Sr/Y (34 to 40) ratios; these features are similar to those of Sanukite formed by the hydrous melting of the mantle wedge. Its depleted zircon Lu-Hf isotopic composition (εHf(t) = +0.97 to +18.21) indicates a depleted mantle source. Zircons in the appinite display extremely high Ti-in zircon temperatures (>1000 °C) and high oxygen fugacity, indicating a high-temperature hydrous condition. In combination with its typical arc-like trace element geochemistry (depletion in Nb, Ta and Ti), it is proposed that this appinite represents hydrous mafic melts that derived from the melting of the depleted sub-arc mantle wedge. The occurrence of this appinite has great significance for the further understanding of Triassic granitic magmatism and potential magmatic metal ore deposits in the Qinling orogenic belt.

Pervasive hydrous carbonatitic liquids mediate transfer of carbon from the slab to the subarc mantle

Carbonatitic liquids, as a medium for transferring carbon from the slab to the mantle at subarc depths, are thought to be restricted either to the hottest conditions or to be the hydrous melting of calcium-rich lithologies (i.e., carbonated gabbro and limestone rocks) in subduction zones. In this study, high-pressure experiments on carbonated hydrous pelites demonstrate that while silicate melts are produced at 2.5–4 GPa, hydrous carbonatitic liquids clearly dominate at 5–6 GPa. The stability of Ca-rich carbonate is strongly depressed by water at pressures exceeding ~4 GPa, promoting the formation of hydrous carbonatitic liquids at temperatures as low as ~850–900 °C; these temperatures correspond to intermediate thermal regimes at depths of 150–180 km. Hence, carbonatite production beneath arcs is more pervasive than previously thought, and the carbon cycle is most likely confined to depths of less than 200 km for many subduction zones.

High heat producing granites and prolonged extraction of tungsten and tin from melts

The granites associated with world–class W and Sn deposits generally have high concentrations of U, Th, and K and can be classified as high heat producing (HHP) granites (>5 μW m−3) because of high radiogenic heat production, but how long radiogenic heat can prolong the suprasolidus lifetime of magmas and whether radiogenic heat exerts an impact on W and Sn mineralization is poorly understood. To answer these questions, finite element numerical modeling was established to link magma cooling by heat conduction with diffusion of W, Sn, and H2O from silicate melts to coexisting aqueous fluids before the solidus is reached. The magma in the models is emplaced to a depth of 5 km and its size (vertical thickness of 4–5 km and horizontal length of 20 km) is constrained by the granites associated with world–class W and Sn deposits. Fluid convection was not considered in the models. The sensitivity analysis and comparison results suggest that the suprasolidus lifetimes of HHP magmas are positively correlated with the heat production and magma thickness and negatively correlated with the solidus temperatures and the thermal conductivity of host rocks. Average radiogenic heat of 5–10 μW m−3, together with decreased solidus temperatures due to magmatic differentiation and a moderate thermal conductivity of host rocks, can prolong the suprasolidus lifetime of HHP magmas by 49–427 ka (1 Ma = 1000 ka), corresponding to 11–85% of the suprasolidus lifetime of equally sized magmas with normal radiogenic heat (2 μW m−3). From the available gravity modeling data, over half of the granites associated with world–class W and Sn deposits are at least 1 km thicker than the values calculated from the empirical power–law equation, and the modeling results indicate that an increase of 500–1000 m in magma thickness prolongs the suprasolidus lifetimes of HHP magmas (5 μW m−3) by 50–74%. During magma cooling before solidus is reached, the diffusion of W and Sn is at least several orders of magnitude slower than that of H2O in hydrous melts; thus, the equilibrium partitioning of these two metals between silicate melts and coexisting aqueous fluids is not reached, and the metal diffusion from melts is a rate-limiting step. The prolongation of the suprasolidus lifetimes by radiogenic heat and decreased solidus temperatures can allow extraction of 17–95% more W and Sn from silicate melts before the solidus is reached and increase the possibility of producing W and Sn mineralization at later stages. Therefore, the coexistence of HHP granites and world–class W and Sn deposits is not accidental.

The petrogenetic relationship between migmatite and granite in the Himalayan orogen: Petrological and geochemical constraints

Partial melting of crustal rocks contributes to the formation of granites in collisional orogens. It is generally recognized that residual granulites are compositionally complementary to crustal-derived granites, yet the petrogenetic relationship between migmatites and granites remains obscure. To shed light on this issue, a comprehensive study of field geology, petrographic observations, whole-rock major and trace elements, mineral major elements, zircon and monazite U–Th–Pb isotopes and trace elements, and monazite SmNd isotopes was carried out for the Higher Himalayan leucosomes, leucocratic dikes, and leucogranites from the Cona area in eastern Himalaya. These rocks were formed by partial melting of the Higher Himalayan metasedimentary rocks and granitic gneisses in the Miocene, and are characterized by distinct petrological and geochemical features. Leucosomes and leucocratic dikes, which were derived from different source rocks (granitic gneisses and metasedimentary rocks, respectively), share many similarities. Both of them are rich in K-feldspar and have high K2O, Ba, and Sr contents and CaO/(CaO + Na2O) ratios, but low Rb/Sr and Sm/Nd ratios; LREE contents correlate positively with Th contents, but negatively with P2O5 contents; zircon and monazite have low MREE/HREE ratios. In contrast, leucogranites, which originated from mixed sources of metasedimentary rocks and granitic gneisses, are rich in plagioclase and have low K2O, Ba, and Sr contents and CaO/(CaO + Na2O) ratios, but high Rb/Sr and Sm/Nd ratios; LREE contents correlate positively with Th and P2O5 contents; zircon and monazite have high MREE/HREE ratios. The K2O-rich leucosomes and leucocratic dikes and the Na2O-rich leucogranites do not show geochemical signatures indicative of a link owing to melt evolution processes, suggesting that the two main groups are the products of distinct and independent anatectic processes in the source. The leucosomes and leucocratic dikes are associated with water-fluxed (hydration) melting at lower temperatures and pressures, whereas the leucogranites are related to water-absent (dehydration) melting at higher temperatures and pressures. In this regard, the leucosomes and leucocratic dikes in migmatites and the leucogranites likely represent two different types of anatectic products, which were respectively derived from partial meltig of the hydrated crustal rocks at the shallower level and the dehydrated crustal rocks at the deeper level. The hydrated-dehydrated crustal architecture is ascribed to the influx of water into the shallower crustal rocks caused by metamorphic dehydration at the deeper crustal level. The spatiotemporally coupled dehydration-hydration anatectic processes may be a common mechanism for the formation of coherent granite, migmatite, and granulite in collisional orogens.

Open system reaction between hydrous melt and gabbroic rock in the Finero Mafic Complex

Open system reaction between hydrous melt and gabbroic rock in the Finero Mafic Complex

Slab dehydration and magmatism in the Kurile arc as a function of depth: An investigation based on B-Sr-Nd-Hf isotopes

While chemical variability in volcanic arc lavas erupted perpendicular to the strike of subduction has been observed and studied for many years, how these variations may reflect slab dehydration or melting processes is still actively debated. Here we report new data for cross-arc geochemical variations in Quaternary volcanic rocks from the Kurile arc. Correlations among multiple isotopic tracers (B–Sr–Nd–Hf) and key elemental ratios (B/Nb, Ba/Nb, Th/Nb and Hf/Nd) show that these arc lavas reflect the influence of three discernible subduction components. Shallow slab-sourced low-temperature hydrous fluids (high B/Nb, Ba/Nb, and δ11B) and deeper high-temperature hydrous melts (moderate B/Nb, Ba/Nb and δ11B, and low Hf/Nd) show characteristics similar to those seen in Izu-Bonin-Mariana arc lavas and likely reflect similar slab-derived origins. In addition to these components, Kurile volcanic front samples document a component with high Th/Nb and depleted mantle-like Hf/Nd. This component may reflect Kurile forearc mantle that had been metasomatized by shallow slab-derived melts associated with the subduction of the Izanagi-Pacific ridge in the Eocene. We propose a new model to interpret the across-arc geochemical variations in the Kurile arc lavas. Kurile forearc mantle, with high Th/Nb due to Eocene ridge subduction, was added to the subduction channel via subduction erosion by the downgoing Pacific plate. This subduction interface reservoir was subsequently metasomatized by deep-sourced hydrous fluids and melts from the slab beneath the volcanic front. The gradual prograde metamorphic modification of these multiply-metasomatized, subducted materials provides the flux that triggered Kurile volcanic front magmatism.

Novel Amino Acid Derivatives for Efficient Methane Solidification Storage via Clathrate Hydrates without Foam Formation

Although anionic surfactants are considered the most efficient kinetic gas hydrate promoters for gas storage applications, gas recovery and reuse of surfactants are difficult due to high foam formation during hydrate melting. Additionally, most anionic surfactants are toxic, which has an intense environmental effect. In this study, novel amino acid derivatives (ACDs) were developed as the first class of superior promoters compared to surfactants without foaming during the formation and recovery of gas hydrates. The results of high-pressure autoclave experiments indicated that all ACDs significantly enhanced the kinetics of methane hydrate formation at 500 ppm. ACD5 derived from leucine showed the best promotion effect in distilled water by providing a total mole consumption of 436.1 mmol. ACD5 increased the degree of water-to-hydrate conversion from 39.6% in pure water to 94.3%, which was higher than in sodium dodecyl sulfate (SDS) solution (87.8%). Moreover, differential scanning calorimetry experiments demonstrated that ACDs could form methane hydrates at relatively lower temperatures than pure water. They increased the onset temperature of methane hydrate formation from −15 °C in pure water to −12 °C at 500 ppm. A higher promotion activity than SDS was also observed for ACDs in salt water, suggesting that seawater can be used to produce methane hydrate instead of pure water to reduce gas storage costs. Besides, visual observations revealed that no foam was formed during melting hydrates and releasing methane in the presence of ACDs. These findings show that a slight modification of amino acids makes them efficient candidates for improving gas hydrate formation for seawater desalination and gas storage applications.

Silicate mineral inclusions in chromite from the Eastern Bushveld complex: Implications for the origin and evolution of hydrous melt during chromite mineralization in the Critical Zone

Silicate mineral inclusions in chromite from the Eastern Bushveld complex: Implications for the origin and evolution of hydrous melt during chromite mineralization in the Critical Zone

Distinct contribution of aqueous solutions and hydrous melts to the mantle sources: Geochemical evidence from Late Paleozoic igneous rocks in Southwestern Tianshan, Western China

Distinct contribution of aqueous solutions and hydrous melts to the mantle sources: Geochemical evidence from Late Paleozoic igneous rocks in Southwestern Tianshan, Western China

Phase Equilibria and Thermodynamic Properties of Phases in the H2O–Gd(NO3)3 System

Solid–liquid equilibria in the system H2O–Gd(NO3)3 were measured from –20 to 70°C using the isothermal saturation method. The Pitzer–Simonson–Clegg thermodynamic model was implemented to obtain the temperature dependence of Gd(NO3)3⋅6H2O solubility constant, to calculate salt solubility and to construct a phase diagram of the system from eutectic point to hydrate melting. Thermochemical properties of gadolinium nitrate aqueous solutions, such as dilution enthalpies and heat capacities, were assessed also. The model has shown to be reliable for phase equilibria calculation from –35 to 90°C and from 0 up to ~15 mol % of salt as well as the thermodynamic properties of Gd(NO3)3 aqueous solutions at room temperature and around it.

Exotic REE behaviors of zircon in the Koktokay No. 3 granitic pegmatite, Xinjiang, northwest China

Rare earth elements (REEs) can be incorporated into zircon at significant concentrations that are controlled by the temperature, pressure, and composition of their growth environment. However, the distribution of REEs between zircon and melt does not always conform to the currently available partitioning data. This study presents evidence of exotic REE behaviors in zircon from the marginal zone of the Koktokay No. 3 granitic pegmatite in Xinjiang, northwest China. The behavior of the Koktokay REEs represents by large negative Ce anomalies, flat heavy REE patterns, and lanthanide tetrad effects. Two generations of zircon (Zrn-I and Zrn-II) are identified, which were formed by dissolution and re-precipitation processes. Zrn-I represents relic zircon domains with dissolution textures that formed from pegmatite melt during the late stage of the magmatic–hydrothermal transition. Zrn-II occurs as overgrowths and infilling fractures around or within Zrn-I, which formed by hydrothermal re-precipitation. From Zrn-I to Zrn-II, the zircon exhibits increasingly negative Ce anomalies and greater enrichment in light REEs and other non-stochiometric elements (e.g., Ca, Al, Fe, and Mg). Given the lack of Ce depletion in the host granite, the negative Ce anomalies in zircon can be attributed to Ce being sequestered into hydrothermal minerals (i.e., cerianite and/or Fe–Mn oxyhydroxides) as tetravalent Ce. In addition, the flat heavy REE patterns of both Zrn-I and Zrn-II likely resulted from the crystallization of heavy REE-enriched minerals, such as zircon and garnet, and were further enhanced by hydrothermal alteration. The two generations of zircon display identical M-type lanthanide tetrad effects in REE patterns, with similar TE3 values. This ubiquitous M-type tetrad effect of the REEs in garnet, zircon, and the host granite can be attributed to the exsolution and subsequent interaction with magmatically derived fluids containing F–aquo-complexes. Therefore, we conclude that such anomalous REE incorporation into zircon from a hydrous pegmatitic melt is controlled by the evolution of the hydrous melt and dissolution–re-precipitation processes. Our results suggest that the reliability of zircon REE partitioning data should be revaluated, and that further experimental studies are needed to fully understand the behavior of REEs in hydrothermal systems.