The subduction of oceanic slabs is widely accepted to be a main reason for chemical heterogeneities in the mantle. However, determining the contributions of slabs in areas that have experienced ...multiple subduction events is often difficult due to possible overlapping imprints. Understanding the temporal and spatial variations of source components for widespread intraplate small volume basalts in eastern China may be a basis for investigating the influence of the subducted Pacific slab, which has long been postulated but never confirmed. For this purpose, we investigated the Chaihe-aershan volcanic field (including more than 35 small-volume Quaternary basaltic volcanoes) in NE China and measured the oxygen isotopes and water content of clinopyroxene (cpx) phenocrysts using secondary ion mass spectrometry (SIMS) and Fourier transform infrared spectroscopy (FTIR), respectively. The water content of magma was then estimated based on the partition coefficient of H2O between cpx and the basaltic melt. The δ18O of cpx phenocrysts (4.28‰ to 8.57‰) and H2O content of magmas (0.19 wt.%–2.70 wt.%) show large variations, reflecting the compositional heterogeneity of the mantle source. The δ18O values and H2O content within individual samples also display considerable variation, suggesting the mixing of magmas and that the magma mixing occurred shortly before the eruption. The relation between the δ18O values of cpx phenocrysts and the H2O/Ce ratio, Ba/Th ratio and Eu anomaly of whole rocks demonstrates the contributions of three components to the mantle source (hydrothermally altered upper oceanic crust and marine sediments, altered lower gabbroic oceanic crust, and ambient mantle). The proportions of these three components have varied widely over time (∼1.37 Ma to ∼0.25 Ma). The Pacific slab is constantly subducted under eastern Asia and continuously transports recycled materials to the deep mantle. The temporal heterogeneity of the source components may be caused by ongoing Pacific slab subduction. Combined with other basalt localities in eastern China (Shuangliao basalts, Taihang basalts and Shangdong basalts), the contributions of recycled oceanic components in their mantle source are heterogeneous. This spatial heterogeneity of mantle sources may be induced by variable alterations and dehydration during the recycling process of the Pacific slab. Our results show that the source components of Cenozoic intraplate small-volume basalts in eastern China are temporally and spatially heterogeneous, which is likely induced by the ongoing subduction of the Pacific slab. This demonstrates that integrating the temporal variations in geochemical characteristics and tectonic history of a study region can identify the subducted oceanic plate that induced enriched components in the mantle source of intraplate basalts.
•Both upper and lower oceanic crust has been recognized in the mantle source of Chaihe-arershan basalts.•The recycled oceanic components in the mantle of whole eastern China varied widely, both spatially and temporally.•The ongoing Pacific slab subduction might trigger the heterogeneity of source components.•Recycled oceanic components for continental intraplate basalts could maintain more water than components of typical OIBs.
•Post-crystallization interactions between uraninites and fluids can result in strong chemical (major, minor, trace element) and isotopic (U-Pb-O) heterogeneities.•U-Th-Pb chemical and 207Pb/206Pb ...clustering ages should be used with caution as they may represent clusters of analyses of similar alteration intensity rather than distinct fluid flow events.•Elements that have been considered immobile, like REEs, may in fact be significantly affected by fluid-driven post-crystallization interactions.
This study presents systematic chemical (U, Pb, Ca, Si, Fe) mapping coupled with in situ analyses of major, minor and trace elements, U/Pb, 207Pb/206Pb, and O isotopic compositions of natural uraninites (UO2) from two samples of the high-grade uranium ore from the Cigar Lake unconformity-related uranium deposit (Athabasca Basin, Saskatchewan, Canada).
The studied uraninites are characterized by major chemical and isotopic heterogeneities expressed at small scale (µm to tens of µm), from almost pristine zones to strongly altered material. The 206Pb/238U and 207Pb/235U ratios of the different areas are widely spread and depict two similar and well-defined Discordia, providing an upper intercept age of crystallization at ca. 1300 Ma (1299 ± 4 and 1308 ± 14 Ma, respectively) and lower intercepts at 38 ± 13 and 72 ± 22 Ma, respectively.
The freshest areas are characterized by sub-concordant 206Pb/238U and 207Pb/235U ratios, identical chemical compositions and similar very low δ18O values (−39.3 to −31.4‰). These data indicate that the two uraninites both crystallized at ca. 1300 Ma, from the same fluid and under identical physico-chemical conditions.
Alteration is characterized by (i) the progressive incorporation of Ca, Si, and Fe, reaching several wt.%, which substitute to the radiogenic Pb and cause a progressive decrease in the Pb/U isotopic ratios. The radiogenic Pb is also substituted by water during the alteration, (ii) concomitant variations in trace element contents (As, Mn, V, LREEs, Sr, Th, B, Ba, Nb, for example) and (iii) heavier δ18O signatures (−22.5 to −8.91‰), typical of meteoric waters, in the altered zones. This combined approach demonstrates that fluid-driven post-crystallization exchanges affected each uraninite during recent fluid flow events (ca. 40 Ma and 70 Ma respectively). The relatively high dispersion of the Pb/U ratios in relation to the Discordia for both samples is considered as linked to a local (nm to µm-scale) differential mobility between lead and uranium within the uranium oxides.
The chemical changes affecting elements previously considered as immobile in uraninite, such as REEs, indicate that these elements are not preserved during the post-crystallization alteration process studied here. Alteration processes may therefore have a major impact on the classical geochemical tracers, such as REE patterns or LREE/HREE ratios, currently used in nuclear forensic studies. The isotopic and chemical tracers currently used to track back the origin, age and history of natural uraninites should therefore be considered with a high degree of caution to avoid misleading and erroneous conclusions.
Moreover, the comparison of calculated U-Th-Pb chemical, 207Pb/206Pb, and Pb/U isotopic ages shows that the use of age clustering for determining U-Th-Pb chemical ages and 206Pb/207Pb ages is not appropriate for constraining crystallization stage(s) of altered uraninites and for deciphering the different fluid events that potentially altered or recrystallized the uraninites over time. This study also indicates that estimation of the crystallization age of uraninite from substitution trends of Pb to Ca is not applicable to unconformity-related U deposits and results in overestimated ages because of an initial integration of calcium in the uraninite lattice at the time of crystallization.
Chondritic meteorites preserve extreme intra-sample 15N/14N variations, which exceed, in some cases, the range of nitrogen isotope ratios observed at the Solar System scale. These observations are ...based on in situ analyses of CN− molecular ions by secondary ionization mass spectrometry (SIMS) in carbon-rich phases. The distribution of nitrogen and its isotopes in silicate minerals and glasses has not been investigated to this date due to the lack of an appropriate analytical protocol, as well as of suitable N-bearing standards. In order to improve our knowledge of the nitrogen signature of both extraterrestrial and terrestrial silicate samples, we have developed a protocol for determining precise and accurate nitrogen abundances (and isotope ratios) in basaltic glasses using high mass resolution SIMS. Twelve (C-)N-bearing synthetic basaltic glasses, containing between <1 and 18,443 ± 966 ppm N, form the suite of reference materials for this study. By targeting the CN−, NO−, AlN−, and SiN− secondary molecular ions, nitrogen abundances can be detected down to the ppm level in both carbon-bearing and carbon-free glasses. The analytical precision and reproducibility of isotope ratios in the form of 15N16O−/14N16O− is on the order of 11‰ and 10 to 17‰ (2σ), respectively, for reference glasses containing ≥100 ppm N. Thus, nitrogen isotope ratios can be determined with an uncertainty that is small enough to resolve nitrogen isotope variations in extraterrestrial silicates. The study of four chondrules of the ordinary chondrite Semarkona (LL3.0) reveals that the nitrogen distribution in the mesostasis is highly heterogeneous, with concentrations ranging from 0 to 1099 ± 168 ppm. The δ15N values in mesostasis, olivine, and pyroxene vary between −36 ± 50‰ and +55 ± 72‰, indicating that silicate phases in chondrules do not host particularly 15N-poor nitrogen.
•(C-)N-bearing basaltic glasses with variable N contents were synthesized to serve as calibrants for SIMS analyses.•The CN−, NO−, AlN−, and SiN− secondary molecular ions are targeted for nitrogen abundance analyses by SIMS.•Nitrogen isotope ratios are determined in the form of 12C15N−/12C14N− and 15N16O−/14N16O−.•Mesostasis in Semarkona chondrules shows highly variable nitrogen concentrations at the micron-scale.
The occurrence of rhyolite melts in the mantle has been predicted by high pressure-high temperature experiments but never observed in nature. Here we report natural quartz-bearing rhyolitic melt ...inclusions and interstitial glass within peridotite xenoliths. The oxygen isotope composition of quartz crystals shows the unequivocal continental crustal derivation of these melts, which approximate the minimum composition in the quartz-albite-orthoclase system. Thermodynamic modelling suggests rhyolite was originated from partial melting of near-anhydrous garnet-bearing metapelites at temperatures ~1000 °C and interacted with peridotite at pressure ~1 GPa. Reaction of rhyolite with olivine converted lherzolite rocks into orthopyroxene-domains and orthopyroxene + plagioclase veins. The recognition of rhyolitic melts in the mantle provides direct evidence for element cycling through earth's reservoirs, accommodated by dehydration and melting of crustal material, brought into the mantle by subduction, chemically modifying the mantle source, and ultimately returning to surface by arc magmatism.
The Phalaborwa world-class phosphate deposit (South Africa) is hosted by a Paleoproterozoic alkaline complex mainly composed of phoscorite, carbonatite, pyroxenitic rocks, and subordinate fenite. In ...addition, syenite and trachyte occur in numerous satellite bodies. New petrological and in-situ geochemical data along with O and Sr isotope data obtained on apatite demonstrate that apatite is in the principal host rocks (pyroxenitic rocks, phoscorite and carbonatite) formed primarily by igneous processes from mantle-derived carbonatitic magmas. Early-formed magmatic apatite is particularly enriched in light rare earth elements (LREE), with a decrease in the REE content ascribed to magma differentiation and early apatite fractionation in isolated interstitial melt pockets. Rayleigh fractionation favored a slight increase in δ
18
O (below 1%) at a constant Sr isotopic composition. Intrusion of fresh carbonatitic magma into earlier-formed carbonatite bodies locally induced re-equilibration of early apatite with REE enrichment but at constant O and Sr isotopic compositions. In fenite, syenite and trachyte, apatite displays alteration textures and LREE depletion, reflecting interaction with fluids. A marked decrease in δ
18
O in apatite from syenite and trachyte indicates a contribution from δ
18
O-depleted meteoric fluids. This is consistent with the epizonal emplacement of the satellite bodies. The general increase of the Sr isotope ratios in apatite in these rocks reflects progressive interaction with the country rocks over time. This study made it possible to decipher, with unmatched precision, the succession of geological processes that led to one of the most important phosphate deposits worldwide.
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•Hydrothermal U deposits are hosted in Indosinian and Yanshanian granites.•U sources are Indosinian and Yanshanian peraluminous S, L-and A-type granites.•U mineralisation occurred ...over a long time span (>100 Ma) in two major events.•Early Yanshanian disseminated-to vein-type high-temperature U mineralisation.•Late Yanshanian vein-type low-temperature U mineralisation during crustal extension.
Granite-related hydrothermal U deposits from the Xiazhuang and Zhuguang ore fields are located within the Nanling Metallogenic Belt in South China. These deposits are hosted in Triassic and Jurassic granites that were emplaced during the Indosinian orogeny and the Yanshanian post-orogenic extension. Four main types of granitic host rocks were identified based on geochemical characteristics as the most favourable sources of U for the mineralisation in the district: (i-ii) Indosinian peraluminous S-type (Maofeng) and L-type leucogranite (Baishuizhai); (iii) Indosinian highly fractionated high-K calc-alkaline A2-type granite (Xiazhuang, Maofeng and Youdong) and (iv) early Yanshanian highly fractionated high-K, (Fe) calc-alkaline A2-type granite (Sundong, Siqian and Changjiang). They contain high U concentrations ranging from 15 to 28 ppm indicating the crystallisation of uraninite, which is a source of U easily leachable by oxidised fluids for the formation of hydrothermal mineralisation.
This study characterises the mineralogical, chemical and isotopic signatures of the U mineralisation from five representative deposits and occurrences in the Xiazhuang (Baishuizhai, Shituling, Xiwang and Xianshi) and Zhuguang (Mianhuakeng) ore fields. The 175 ± 16 Ma Baishuizhai occurrence and 162 ± 27 Ma Shituling deposit represent an early stage of U mineralisation (175–145 Ma) that occurred during the early Yanshanian. Disseminated Th-bearing uraninite at Baishuizhai and the association of U oxides with alteration minerals such as epidote and chlorite in both Baishuizhai and Shituling indicate temperatures >250 °C for the hydrothermal system. The early Yanshanian granites (190–150 Ma) provided the heat source and magmatic fluids to the hydrothermal system while U-rich Indosinian granites provided U for the Zr-Th-Ta-bearing U mineralisation. In contrast, the mineralisation from Xiwang, Mianhuakeng and Xianshi deposits (107 ± 16, 93 ± 15 and 79 ± 11 Ma, respectively) represent several pulses of the main mineralisation stage (110–50 Ma) that occurred during the late Yanshanian crustal extension. The mineralisation occurred at relatively low temperatures (<250 °C) as W-Y-Nb-Ti-rich pitchblende and uraninite veins associated with quartz, fluorite, calcite and pyrite. During Cretaceous-early Cenozoic crustal extension, oxidising meteoric and/or basinal waters percolated downward into the granitic basement through deep faults and mixed with CO2-rich magmatic fluids. These thermal solutions circulated along opening fractures and leached U from Indosinian and early Yanshanian U-rich granites and also possibly from early Yanshanian U mineralisation. After heating, the ore-forming fluids ascended along structures leading to the decrease of the hydrostatic fluid pressure, which promoted the deposition of U in veins. Therefore, granite-related hydrothermal U mineralisation in the province, formed over a long time span (>100 Ma) in two major stages related to different genetic conditions.
The intensive variables of dacitic-rhyodacitic magmas prior to four large Plinian eruptions of Santorini Volcano over the last 200 kyr (Minoan, Cape Riva, Lower Pumice 2 and Lower Pumice 1) were ...determined by combining crystallization experiments with study of the natural products, including the volatile contents of melt inclusions trapped in phenocrysts. Phase equilibria of the silicic magmas were determined at pressures of 1, 2 and 4 kbar, temperatures of 850-900 degree C, fluid (H sub(2)O + CO sub(2))-saturation, XH sub(2)O = molar H sub(2)O/(H sub(2)O + CO sub(2)) between 0.6 and 1 (melt H sub(2)O contents of 2-10 wt %), and redox conditions of FMQ (fayalite-magnetite-quartz buffer) or NNO + 1 (where NNO is Ni-NiO buffer). Experiments were generally successful in reproducing the phenocryst assemblage of the natural products. The phase relationships vary significantly among the investigated compositions, revealing a sensitivity to small variations in whole-rock compositions. Our results show that the pre-eruptive storage conditions of the four silicic magmas were all very similar. The magmas were stored at T = 850-900 degree C and P greater than or equal to 2 kbar, under moderately reduced conditions ( Delta NNO = -0.9 to -0.1), and were poor in fluorine (500-800 ppm) and sulphur ( less than or equal to 100 ppm), but rich in water and chlorine (5-6 wt % and 2500-3500 ppm, respectively). In all cases, the melts were slightly undersaturated with respect to H sub(2)O, but most probably saturated with respect to H sub(2)O + Cl plus or minus CO sub(2) and a brine. The Santorini magma plumbing system appears to be dominated by a large, long-lived ( greater than or equal to 200 kyr) predominantly silicic magma storage region situated at greater than or equal to 8 km depth, from which crystal-poor melt batches were extracted during the largest caldera-forming eruptions of the volcanic system.
The genesis of Cenozoic continental basalts in Eastern China is highly debated. Subducted oceanic crust (most probably the Pacific oceanic slab) has been increasingly suggested to be involved in ...their mantle source. The Taihang Mountains are located at a surface position corresponding to the western edge of a stagnant subducted Pacific slab revealed by geophysical investigations, and thus provide an opportunity to study the spatial extent of the effect of Pacific subduction on the mantle characteristics of Eastern China. In previous studies, alkali basalts from the Taihang Mountains were considered to be the products of interaction between asthenosphere-derived melts and the old, enriched lithospheric mantle; their magnesium isotope signature suggested the contribution of oceanic carbonate. To explore the possible contribution from recycled oceanic crust in the genesis of the Taihang basalts we estimated the water contents of the magmas by a phenocryst-based approach () and measured the oxygen isotope compositions of clinopyroxene phenocrysts by secondary ion mass spectrometry for the same sample suite as used in previous studies. The calculated water contents (H sub(2)O by weight) of the parental magmas range from 0.20 to 1.07wt %, and the corresponding H sub(2)O/Ce ratios correlate well with (Nb/La) sub(n) (where n represents primitive mantle normalization), (Ba/Th) sub(n) and epsilon Nd. The oxygen isotope ratios ( delta super(18)O sub(SMOW)) range from 5.8 to 7.4ppt, and the average value for each sample ranges from 6.6 to 7.0ppt. These new data indicate a large contribution from extremely dehydrated recycled oceanic crust together with entrained sediments. The minor element compositions (Ca, Mn and Ni contents) of olivine phenocrysts in the Taihang basalts suggest a pyroxenite source that was probably formed by the interaction between oceanic crust-derived melt and ambient mantle peridotite.
•First bromine partition experiments performed with natural silicate glasses.•First Br fluid/melt partition coefficients on mafic and intermediate compositions.•DBrf/m increases with SiO2 content of ...the melt, from basalt to rhyodacite compositions.•First Br data in melt inclusions from Etna, Stromboli, Merapi and Santorini volcanoes.•First model describing Br degassing behaviour in mafic volcanic systems.
Volcanogenic halogens, in particular bromine, potentially play an important role in the ozone depletion of the atmosphere. Understanding bromine behaviour in magmas is therefore crucial to properly evaluate the contribution of volcanic eruptions to atmospheric chemistry and their environmental impact. To date, bromine partitioning between silicate melts and the gas phase is very poorly constrained, with the only relevant experimental studies limited to investigation of synthetic melt with silicic compositions. In this study, fluid/melt partitioning experiments were performed using natural silicate glasses with mafic, intermediate and silicic compositions. For each composition, experiments were run with various Br contents in the initial fluid (H2O–NaBr), at T–P conditions representative of shallow magmatic reservoirs in volcanic arc contexts (100–200 MPa, 900–1200 °C). The resulting fluid/melt partition coefficients (DBrf/m) are: 5.0 ± 0.3 at 1200 °C–100 MPa for the basalt, 9.1 ± 0.6 at 1060 °C–200 MPa for the andesite and 20.2 ± 1.2 at 900 °C–200 MPa for the rhyodacite. Our experiments show that DBrf/m increases with increasing SiO2 content of the melt (as for chlorine) and suggest that it is also sensitive to melt temperature (increase of DBrf/m with decreasing temperature). We develop a simple model to predict the S–Cl–Br degassing behaviour in mafic systems, which accounts for the variability of S–Cl–Br compositions of volcanic gases from Etna and other mafic systems, and shows that coexisting magmatic gas and melt evolve from S-rich to Cl–Br enriched (relative to S) upon increasing degree of degassing. We also report first Br contents for melt inclusions from Etna, Stromboli, Merapi and Santorini eruptions and calculate the mass of bromine available in the magma reservoir prior to the eruptions under consideration. The discrepancy that we highlight between the mass of Br in the co-existing melt and fluid prior to the Merapi 2010 eruption (433 and 73 tons, respectively) and the lack of observed BrO (from space) hints at the need to investigate further Br speciation in ‘ash-rich’ volcanic plumes. Overall, our results suggest that the Br yield into the atmosphere of cold and silicic magmas will be much larger than that from hotter and more mafic magmas.
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