Large Isotopic Variations Research Articles

Paleoclimatic and paleoenvironmental significance of late Pleistocene pedogenic carbonates (‘Caliche Cordão’) from the coastal Pampa of southern Brazil

The pedogenic carbonates found in Pleistocene units of the coastal Brazilian Pampa, informally designated as ‘Caliche Cordão', include rhizocretions, soft masses and isolated or coalescent nodules, either isolated within the sediment or forming discrete horizons, the most developed horizons (Ca-01 and Ca-02) stretching for hundreds of meters along the banks of Chuy Creek. Petrographic analyses show micritic (Alpha-type) matrix in most samples, with few signs of recrystallization as circumgranular spar rims or cracked sand grains. Stable carbon (δ13C) and oxygen (δ18O) isotope values in samples from the lower horizon Ca-01 exhibit small variation and indicate C3-dominated plant assemblages and carbonate precipitation from relatively 18O-enriched water, whereas the δ13C and δ18O in samples from the upper horizon (Ca-02) exhibit wider variation, higher proportion of C4 plants and precipitation from 18O-depleted water in some samples. The δ18O variations can be explained by variable degrees of evaporative enrichment, or to relative contributions of 18O-depleted (tropical) or 18O-enriched (subtropical) rainfall, based on the similarity with estimates from fossils of mastodons. Nodules from other sites are similar, but larger isotopic variations indicate carbonate precipitation at distinct times and environmental conditions, and a few exhibit partial recrystallization as larger spar calcite crystals. Luminescence ages of ∼74.7 and ∼71.3 ka of quartz grains in two nodules from Ca-01 indicate precipitation during MIS 4, whereas ages of ∼52 ka from Ca-02, and ≥30 ka in nodules from the shores of Mirim Lagoon indicate carbonate formation between MIS 3 and MIS 2. The probable source of carbonate was calcium released from eolian-sourced silty dust produced by Andean glaciers and transported from loess deposits in Argentina during cold and dry intervals of the last glacial, when arid/semiarid environments expanded from Patagonia across the Pampas up to southern Brazil. The variations of δ13C in calcretes formed between MIS 4 and 2 point to changes in plant assemblages that could have contributed for the local extinction of the mammalian megafauna.

Calcium isotope compositions of subduction-related leucite-bearing rocks: Implications for the calcium isotope heterogeneity of the mantle and carbonate recycling in convergent margins

Large Ca isotope variations recorded in mantle xenoliths and mantle-derived igneous rocks have been widely used to decode the origin of mantle heterogeneity, especially to trace recycled sedimentary carbonates. However, it is still unclear whether and how the subduction of sedimentary carbonate causes significant Ca isotope fractionation in the mantle in correspondence of convergent margins. In this study, we present Ca isotope data for sixteen silica-undersaturated ultrapotassic leucite-bearing rocks and their clinopyroxene (Cpx) phenocrysts from the “Colli Albani” volcano (Italy), and for six carbonate-bearing sediments from nearby Apennine Chain. These subduction-related volcanic rocks have been widely accepted as deriving from a mantle source that involves recycled carbonated sediments indicated by their enriched incompatible trace elements and radiogenic isotopes, and olivine geochemistry. The δ44/40Ca values (normalized to NIST SRM 915a) of leucite-bearing rocks are uniform (from 0.64 to 0.79 ‰, with one exception of 0.86 ‰) with an average of 0.72 ± 0.03 ‰, 2SE, N = 16, which is 0.12 ± 0.03 ‰ (2SE) and 0.22 ± 0.03 ‰ (2SE) lower than MORBs (0.84 ± 0.02 ‰, 2SE, N = 25) and BSE (0.94 ± 0.01 ‰, 2SE, N = 14) respectively. In contrast, the carbonate-bearing sediments show variable and notably low δ44/40Ca values, ranging from 0.44 to 0.77 ‰. The δ44/40Ca of Cpx (0.70 to 0.76 ‰) is indistinguishable from their host rocks (0.73 to 0.76 ‰). In addition, the lack of correlations between δ44/40Ca and SiO2, CaO, Ni and P2O5, and the Ca isotopic simulation result indicate that Ca isotope fractionation caused by fractional crystallization is insignificant. Given that the Ca isotope fractionation is limited during the melting of spinel wehrlite-like mantle source (within ∼0.04 to 0.11 ‰), the slightly low δ44/40Ca values of the Italian leucite-bearing rocks require 10 % to 20 % addition of carbonated sediments in their mantle source. This indicates that recycled carbonated sediments can cause slight δ44/40Ca heterogeneity (∼0.1 to 0.2) of the mantle wedge in local/regional scales.

Lateral flow in bedrock dominates baseflow and flood flow in a catchment underlain with permeable sedimentary rock in the high‐relief Chichibu Mountains

AbstractDetermining the mechanisms of runoff generation is essential to land and water resource conservation, but lateral flow processes in high‐relief mountain areas remain unclear due to the difficulty to observe and measure these processes. This study demonstrates that lateral flow in bedrock dominates both high and low flows in a catchment underlain with permeable sedimentary bedrock in the high‐relief Chichibu Mountains. Through measurement of precipitation, discharge, soil, and stream temperatures and tracers (SiO2 and δ18O) in the first‐order stream Bakemonozawa (0.51 km2) and comparison of its water balance with the nested Kawamata catchment (93.58 km2) i, we showed that 831–1012 mm/year or 47%–53% of annual precipitation leaked from Bakemonozawa. The streamflow was discharged from an average depth of 2.3 m or deeper, which were deeper than the measured deepest soil near the gauge. Furthermore, stream temperature decreased significantly during a large summer storm, demonstrating that the relative contribution of the deep bedrock flowpath increased. Large isotopic variation in precipitation was dampened in the stream, suggesting that most baseflow and some higher flows arose from groundwater storage with a constant isotopic ratio due to dispersion and mixing. The discharge–SiO2 relationship suggested at least two groundwater sources, namely, shallow and deep bedrock groundwater, with different runoff responses. Discharge increased dramatically when the catchment became wet, coinciding with the deep bedrock groundwater contribution. Further research is needed to clarify the hydrological characteristics of bedrock.

A preliminary elemental and isotopic investigation to develop authentication tools for Chinese Ganoderma lucidum

Isotope ratio mass spectrometry (IRMS) combined with multivariate analysis was employed to develop a new quality control tool for Chinese Ganoderma lucidum. The effect of growth stage, substrate, cultivar type and geographical origin on the elemental and isotopic compositions was investigated. Stable isotopes (δ13C, δ15N, and δ18O) and elemental contents (%C, %N) showed significant variations at different growth stages. Growth substrate did not impart significant variations on δ13C or δ18O values; however, δ15N values of G. lucidum were strongly associated with the substrate. In addition, large isotopic variations were observed among different G. lucidum cultivars. A strong positive correlation was observed between major active compounds and elemental contents. Finally, classification models based on LDA and PLS-DA were constructed to discriminate the geographical origin of G. lucidum. Both models achieved very high classification rates in both the training and test set (up to 100% accuracy). In conclusion, elemental and isotopic fingerprints along with multivariate statistical analysis showed strong potential in characterizing G. lucidum according to variety, production region and cultivation method. These preliminary results will provide valuable insights in controlling the fraudulent labeling of Ganoderma lucidum and provide authentication tools for regulatory authorities to authenticate origin claims.

Nickel Isotope Fractionation During Magmatic Differentiation

AbstractThe behavior of nickel (Ni) isotopes during magmatic differentiation is not adequately explored. Here, we find that tholeiitic rocks in the Kīlauea Iki (KI) lava lake, Hawai'i, show progressively lighter Ni isotopic compositions with increasing magmatic differentiation, whereas calc‐alkaline rocks from the thick Kamchatka arc (30–45 km), located at the convergent boundary of the Eurasian and Pacific plates show increasing Ni isotope values as MgO and Ni decrease. Forty‐three global intermediate‐felsic continental igneous rocks analyzed in this study display large Ni isotopic variations, with the Eoarchean samples having light Ni isotopic compositions that fall in the trend defined by the KI lavas, and the post‐Eoarchean samples showing systematically heavier Ni isotopic compositions overlapping those of Kamchatka arc rocks. The isotopic dichotomy results from the crystallization of isotopically heavy magnetite during low‐pressure differentiation of KI lavas, whereas the participation of sulfide separation that removes isotopically light Ni during high‐pressure differentiation of magmas traversing thick continental crust. Combined with Rhyolite‐MELTS and sulfur concentration at sulfide saturation simulations, we demonstrate that the Ni isotope fractionation during magmatic differentiation is mainly controlled by the tempo of magnetite crystallization and sulfide formation, which is a function of pressure, oxygen fugacity, and water activity. High‐pressure calc‐alkaline differentiation usually suppresses magnetite crystallization while stabilizing sulfide, leading to heavy Ni isotopic compositions for the evolved magmas, significantly deviating from the low‐pressure fractionation trend seen in the KI lavas. Ni isotopes can be used in the future as a tracer of magmatic differentiation and processes of continent formation and differentiation.

A metamorphic devolatilization model for the granitoid-hosted Wulong lode gold deposit, Liaodong Peninsula, Eastern North China Craton: Evidence from geology, fluid inclusions, and O-Sr-Li isotopes

The genesis of the gold deposits in the eastern North China Craton (NCC) has long been disputed. Many would relate the gold mineralization to magmatism. The Wulong in the Liaodong Peninsula is a classic example in the eastern NCC and was considered to be of magmatic hydrothermal origin previously. Nevertheless, we propose a metamorphic devolatilization model to explain its genesis based on geological, fluid inclusion and O-Sr-Li isotopic study. The geological profiles, temperatures, salinities, and O isotopes of the ore-forming fluids at Wulong show no spatial variations over a 600 m vertical depth interval. These evidence convincingly prove its vertically extensive feature, which is similar to orogenic gold deposits, but different from magmatic hydrothermal systems. The initial Sr isotopes of the ore-forming fluids (0.71435 to 0.71578) fall into the range of metabasalts from the Liaohe Group (the Paleoproterozoic basement), indicating that metabasalts are the probable sources. Lithium and its isotopic modelling further suggest that metamorphic devolatilization of metabasalts (with chain silicates Ch, phyllosilicates Ph, and quartz Qtz as endmembers; Ch, Li ≈ 5 ppm, δ7Li ≈ 8‰; Ph, Li ≈ 63 ppm, δ7Li ≈ −1‰; Qtz, Li ≈ 10 ppm, δ7Li ≈ 30‰) could account for the Li concentrations (5–41 ppm) and δ7Li value of the fluid (21.4‰) of the Wulong gold deposit. Rayleigh fractionation in a closed system led to large Li isotopic variation of the ore-forming fluids (21.4 to 11.0‰). The metamorphic devolatilization model based on the vertically extensive feature, Sr isotopic constraint and Li isotopic modelling is in striking contrast with previous qualitative isotopic studies that support a magmatic hydrothermal origin for the Wulong and other granitoid-hosted gold deposits in the eastern NCC. Integrated with geological characteristics and radiogenic isotopes, this study here shows that Li isotopes can provide new constraints on the genesis of orogenic gold deposits.

Magnesium isotope fractionation in differentiation of mafic-alkaline-carbonatitic magma and Fe-P-REE-rich melt at Bayan Obo, China

The Bayan Obo area in the North China Craton (NCC) contains the largest rare earth element (REE) resources in the world. The key to this gigantic and efficient REE accumulation has been the focal point of century-long research efforts. Intense differentiation of mantle-derived alkaline magmas is envisaged as a highly viable process for REE enrichment based on the first discovery of mafic-alkaline-carbonatitic suite in the Bayan Obo region. Geochronological and Sr-Nd-Hf-O isotopic analyses revealed that these rocks derived from a common mantle source and evolved with magmatic differentiation at 1.31 Ga to 1.32 Ga. Elemental geochemistry and Mg isotopes in this magma series (alkaline diabase sill, syenite dyke and carbonatite) unambiguously support the differentiation model. The earliest ferrocarbonatite, with nearly undifferentiated REE concentrations, has mantle-like δ26Mg (−0.27 ± 0.03‰), and therefore can be considered as the original product of the mantle derived alkaline magma at Bayan Obo. The subsequent magnesiocarbonatites have a LREE enrichment feature, which is consistent with the alkaline diabase sills. The magnesiocarbonatites possess light Mg isotopic composition (from − 0.42‰ to − 0.50‰), whereas the alkaline diabase sills have heavy Mg isotopic composition (from − 0.03‰ to − 0.05‰). This rock assemblage should present two end members, which differentiated likely by immiscibility in the chamber from a common alkaline magma. The subsequent syenite dyke has no obvious Mg isotopic variation (from − 0.44‰ to − 0.39‰) during differentiation from the above alkaline magma. Notably, as the most important REE hosts, fine-grained ferrocarbonatites show large Mg isotopic variations (from − 0.85‰ to + 0.13‰) and present positive correlations with total MgO and CaO contents, but negative with total Fe2O3, P2O5 and REE contents. In fine-grained ferrocarbonatite, closely associated apatite, monazite, hematite and magnetite minerals occur as a special intergrowth texture. This unique paragenetic assemblage is likely the mineralization record of a Fe-P-REE-rich melt, which shows particular affinity of hydrothermal fluid and light Mg isotope in carbonatitic magma. By contrast, magnesian siderite phenocrysts as the early cumulates in carbonatitic magma are enriched in heavy Mg isotope (from − 0.07‰ to + 0.21‰). Immiscibility of Fe-P-REE-rich melt and fractional crystallization of carbonate minerals are responsible for large Mg isotope fractionation and giant REE enrichment in the Bayan Obo deposit.

A novel application of thallium isotopes in tracing metal(loid)s migration and related sources in contaminated paddy soils

Thallium (Tl) is a highly toxic heavy metal, which is harmful to plants and animals even in trace amounts. Migration behaviors of Tl in paddy soils system remain largely unknown. Herein, Tl isotopic compositions have been employed for the first time to explore Tl transfer and pathway in paddy soil system. The results showed considerably large Tl isotopic variations (ε205Tl = −0.99 ± 0.45 ~ 24.57 ± 0.27), which may result from interconversion between Tl(I) and Tl(III) under alternative redox conditions in the paddy system. Overall higher ε205Tl values of paddy soils in the deeper layers were probably attributed to abundant presence of Fe/Mn (hydr)oxides and occasionally extreme redox conditions during alternative dry-wet process which oxidized Tl(I) to Tl(III). A ternary mixing model using Tl isotopic compositions further disclosed that industrial waste contributed predominantly to Tl contamination in the studied soil, with an average contribution rate of 73.23%. All these findings indicate that Tl isotopes can be used as an efficient tracer for fingerprinting Tl pathway in complicated scenarios even under varied redox conditions, providing significant prospect in diverse environmental applications.

Rubidium and potassium isotopic variations in chondrites and Mars: Accretion signatures and planetary overprints

As moderately volatile elements, isotopes of Rb and K can trace volatilization processes in planetary bodies. Rubidium isotopic data are however very scarce, especially for non-carbonaceous meteorites. Here, we report combined Rb and K isotopic data (δ87/85Rb and δ41/39Κ) for 7 ordinary, 6 enstatite, and 4 Martian meteorite falls to understand the causes for the variations in volatile abundances and isotopic compositions. Bulk Rb and K isotopic compositions of planetary bodies are estimated to be (Table 1): Mars +0.10 ± 0.03 ‰ for Rb and −0.26 ± 0.05 ‰ for K, bulk OCs -0.12-0.24+0.15 ‰ for Rb and -0.72-0.41+0.28 ‰ for K, bulk ECs +0.02-0.26+0.29 ‰ for Rb and -0.33-0.23+0.37 ‰ for K. The bulk K isotopic compositions of subgroup OCs are estimated to be -0.72-0.55+0.26 ‰ for H chondrites, -0.71-0.39+0.23 ‰ for L chondrites, and -0.77-0.30+0.63 ‰ for LL chondrites. A broad correlation between the Rb and K isotopic compositions of planetary bodies is observed. The correlation follows a slope that is consistent with kinetic evaporation and condensation processes, suggesting volatility-controlled mass-dependent isotope fractionation (as opposed to nucleosynthetic anomalies).Individual ordinary and enstatite chondrites show large Rb and K isotopic variations (−1.02 to +0.29 ‰ for Rb and −0.91 to −0.15 ‰ for K). Samples of lower metamorphic grades display correlated elemental and isotopic fractionations between Rb and K, while samples of higher metamorphic grades show great scatter, suggesting that chondrite parent-body processes have decoupled the two elements and their isotopes at the sample scale. Several processes could have contributed to the observed isotopic variations of Rb and K, including (i) chondrule “nugget effect”, (ii) volatilization during parent-body thermal metamorphism (heat-induced vaporization and gas transport within parent bodies), (iii) thermal diffusion during parent-body metamorphism, and (iv) impact/shock heating. Quantitative modeling of the first two processes suggests that neither of them could produce isotopic variations large enough to explain the observed isotopic variations. Volatilization during parent-body thermal metamorphism [the scenario (ii)], which has been commonly invoked to explain the isotopic variations of volatile elements, is gas transport-limited and its effect on isotopic fractionations of moderately volatile elements should be negligible. Modeling of diffusion processes suggests that (iii) could produce K isotopic variation comparable to the observed variation. The large isotopic variations in non-carbonaceous meteorites are thus most likely due to diffusive redistribution of K and Rb during metamorphism and/or shock-induced heating and vaporization.

Extensive crystal fractionation of high-silica magmas revealed by K isotopes.

Fractional crystallization plays a critical role in generating the differentiated continental crust on Earth. However, whether efficient crystal-melt separation can occur in viscous felsic magmas remains a long-standing debate because of the difficulty in discriminating between differentiated melts and complementary cumulates. Here, we found large (~1 per mil) potassium isotopic variation in 54 strongly peraluminous high-silica (silicon dioxide >70 weight %) leucogranites from the Himalayan orogen, with potassium isotopes correlated with trace elemental proxies (e.g., strontium, rubidium/strontium, and europium anomaly) for plagioclase crystallization. Quantitative modeling requires up to ~60 to 90% fractional crystallization to account for the progressively light potassium isotopic composition of the fractionated leucogranites, while plagioclase accumulation results in enrichment of heavy potassium isotopes in cumulate leucogranites. Our findings strongly support fractional crystallization of high-silica magmas and highlight the great potential of potassium isotopes in studying felsic magma differentiation.

40Ar/39Ar geochronology of the Drakensberg continental flood basalts: Understanding large argon isotopic variations in mafic groundmass and plagioclase size fractions

The extrusive component of the Karoo Large Igneous Province, the Drakensberg Continental Flood basalts of South Africa and Lesotho, is mainly composed of altered tholeiitic basalts without uraniferous mineral phases that are suitable for high-precision dating (e.g. baddeleyite or zircon), and thus dating is restricted to 40Ar/39Ar groundmass and plagioclase. Previous 40Ar/39Ar dates of plagioclase span from 178.9 ± 4.2 Ma to 189.2 ± 3.3 Ma, while most dates range between 180 and 183 Ma (Jourdan et al., 2007b; Moulin et al., 2011; Moulin et al., 2017). Dating mafic rocks can be hindered by the presence of plagioclase xenocrysts (inherited 40Ar), and the ubiquitous presence of alteration phases. Separation protocols and acid leaching are used to minimize the effect of these issues, although previous 40Ar/39Ar studies of the Drakensburg lavas did not interpret their dates within a petrochronological context, and thus they are open to inaccuracy. We have used cathodoluminescence imaging, QEMSCAN analysis and optical petrology of thin sections to show that two distinct generations of plagioclase occur within the lavas, and at least two different phases of K-rich (adularia and K-rich clays) and Ca- alteration have occurred. 40Ar/39Ar dates have been obtained from some acid-leached and unleached aliquots of groundmass and both plagioclase generations. Our results show that i) large, cluster-forming plagioclase yield older 40Ar/39Ar dates and are interpreted to be xenocrystic, ii) apparently unaltered plagioclase in thin sections hosts secondary Ar reservoirs related to alteration, and iii) alteration and leaching can enhance the effects of 37,39Ar recoil in plagioclase. We conclude that the most accurate date for the Drakensburg lavas that applies to the entire thickness of the lava stacks is 184.4 ± 1.2 Ma, which was obtained from the matrix-forming plagioclase that contains the highest proportion of non-inherited radiogenic 40Ar, is least affected by secondary alteration and did not apparently suffer the effects of Ar isotope recoil.

Multi-mode chemical exchange in seafloor alteration revealed by lithium and potassium isotopes

Elemental exchange during seafloor alteration exerts substantial control on the chemical compositions of seawater and oceanic crust, as well as the global elemental cycling. However, detailed processes and mechanisms for element transport and isotopic exchange remain unclear. Here, we report Li and K isotopic compositions across an altered MORB-like pillow basalt from Mariana Trench. We find large and systematic isotopic variations on a centimeter scale, with δ7Li decreasing from +9.07‰ to +6.21‰ and δ41K increasing from −0.12‰ to +0.33‰ from the rim to the core. The heavier-than-mantle Li and K isotopic compositions in the core likely inherit from an enriched mantle source rather than post-magmatic alteration processes. The low K and high Li isotopic compositions at the outmost rims result from adsorption during seawater-rock interactions. The basin-shaped elemental and isotopic variations were subsequently formed by chemical diffusion and spontaneous seawater penetration from the weathered rind to the interior of pillow basalt sample. This study uses a small-scale sampling approach and provides the first evidence for multi-mode chemical exchange in oceanic basalts and improves our understanding of the seafloor alteration processes.

Calcium Isotope Ratios (δ44/40Ca) of Thirty‐Four Geological Chinese Reference Materials Measured by Thermal Ionisation Mass Spectrometry

High‐precision calcium isotopic ratios of thirty‐four Chinese geological reference materials, including igneous, metamorphic and sedimentary rocks, river/marine sediments and soils, are reported. Measurements were conducted by thermal ionisation mass spectrometry (Triton TIMS) using a 42Ca–43Ca double spike. These reference materials cover a wide range of chemical compositions with CaO ranging from 0.10 to 51.1% m/m. The δ44/40Ca variation of igneous rocks was up to 0.75‰, ranging from 0.61 ± 0.06‰ to 1.35 ± 0.04‰. Two metamorphic rocks yielded δ44/40Ca of 0.39 ± 0.02‰ and 0.86 ± 0.02‰, respectively. δ44/40Ca values of sedimentary rocks varied from −0.14 ± 0.09‰ to 0.98 ± 0.12‰, suggesting significant isotopic fractionation during low‐temperature processes. Like sedimentary rocks, river/marine sediments and soil displayed large Ca isotopic variations, with δ44/40Ca spanning from 0.12 ± 0.06‰ to 0.77 ± 0.03‰ and −0.09 ± 0.11‰ to 0.74 ± 0.08‰, respectively. The comprehensive data set reported in this study serves as a reference for quality assurance and inter‐laboratory comparison for high‐precision Ca isotopic studies.

Magma evolution of the South China Sea basin from continental-margin rifting to oceanic crustal spreading: Constraints from In-situ trace elements and Sr isotope of minerals

The South China Sea (SCS) has undergone a complete Wilson cycle. We studied the volcanic rocks from IODP Sites U1502, U1500, U1431, U1433, and U1434 that record the exact mantle dynamics of the SCS basin from continental rifting to oceanic crustal spreading. We present in-situ major and trace element data for minerals (olivine, clinopyroxene, and plagioclase) and melt inclusions; and in-situ Sr isotopic ratios for plagioclases from the volcanic samples. All SCS volcanic rocks belong to the tholeiite series. Most Site U1431 basalts are slightly depleted in light rare earth elements (LREEs) and large-ion lithophile elements (LILEs) and similar to that of normal mid-oceanic ridge basalts (N-MORB). All clinopyroxenes and olivines, and the calculated equilibrium melts of clinopyroxene cores display depletion of LREEs and enrichment of heavy rare earth elements (HREEs) similar to N-MORB-type primary magma. Thus, these volcanic rocks are likely formed by the extension decompression partial melting of shallow depleted magma. The Sites U1502, U1500, U1433, and U1434 bulk-rocks and melt inclusions show flat LREE and HREE patterns similar to that of enriched MORB (E-MORB), likely attributed to the partial melting of a depleted mantle source with different degrees of lower continental crustal contamination. The increase in 87Sr/86Sr ratios from core to rim in Site U1500 plagioclases further prove the crustal contamination during magmatism. Site U1431 clinopyroxene and Site U1500 plagioclase show normal zoning textures and slight enrichment of incompatible elements in their rims but depletion in their cores, likely indicating significant crystallization of late-stage differentiated melts. Although some clinopyroxene and plagioclase were likely crystallized in a relatively closed environment, the existence of melt inclusions and the large Sr isotopic variations between the plagioclase rim and groundmass suggest a dynamic and open magmatic system that likely experienced melt–rock interactions and magma mixing processes. Melt supply rate changes from low to high during the SCS evolution process from initial rifting (Site U1500) to later spreading (Sites U1431 and U1433) indicating that: (1) the number of high-An plagioclase-hosted melt inclusions has gradually decreased; and (2) the zoning textures of clinopyroxene and plagioclase have gradually changed from simple to complex. The influence of mantle plumes and the upwelling of fertile subduction-related asthenospheric magma were negligible during the continental-margin breakup and initial SCS spreading, but played an important role during the late SCS spreading period, as revealed by the variation in Sr isotopic compositions of high-An plagioclase cores, the different mantle potential temperatures and source lithologies.

Preferential dissolution of uranium-rich zircon can bias the hafnium isotope compositions of granites

Abstract Hafnium (Hf) isotopes in zircon are important tracers of granite petrogenesis and continental crust evolution. However, zircon in granites generally shows large Hf isotope variations, and the reasons for this are debated. We applied U-Pb geochronology, trace-element, and Hf isotope analyses of zircon from the Miocene Himalayan granites to address this issue. Autocrystic zircon had εHf values (at 20 Ma) of–12.0 to–4.3 (median =–9). Inherited zircon yielded εHf values (at 20 Ma) of–34.8 to +0.3 (median =–13); the majority of εHf values were lower than those of autocrystic zircon. The εHf values of inherited zircon with high U concentrations resembled those of autocrystic zircon. Geochemical data indicates that the granites were generated during relatively low-temperature (<800 °C) partial melting of metasedimentary rocks, which, coupled with kinetic hindrance, may have led to the preferential dissolution of high-U zircon that could dissolve more efficiently into anatectic melt due to higher amounts of radiation damage. Consequently, Hf values of autocrystic zircon can be biased toward the values of U-rich zircon in the source. By contrast, literature data indicate that granites generated at high temperatures (>820–850 °C) generally contain autocrystic and inherited zircons with comparable Hf isotope values. During higher-temperature melting, indiscriminate dissolution of source zircon until saturation is reached will result in near-complete inheritance of Hf isotope ratios from the source. Our results impose an extra layer of complexity to interpretation of the zircon Hf isotope archive that is not currently considered.

Constraints on triple oxygen isotope kinetics

Isotopic disequilibrium is not as well constrained as equilibrium, hindering interpretation of isotopic variations. Kinetic isotope effects, a subset of disequilibrium, are common in nature and have been assumed to be distinct from equilibrium and mass independent isotope effects based on underdeveloped criteria. Using basic physical principles, we provide needed mechanistic constraints on mass-dependent kinetic isotope effects for the triple oxygen isotope system. We find some kinetic isotope effects yield large isotopic variations, exceeding equilibrium, which could be mistaken for mass independent relationships. Meanwhile, other kinetic isotope effects are found to have triple oxygen isotope relationships that could be mistaken for equilibrium isotope effects. Comparison against prior case studies of thermal decomposition of calcite (CaCO3) and brucite (Mg(OH)2) further tests our results. Although oxygen is the focus here, our approach applies to any system with more than two isotopes.

Origins and implications of magnesium isotopic heterogeneity in Fe–Ti oxides in layered mafic intrusions

To constrain the mechanisms governing the extremely large variations of Mg and Fe isotopes in magmatic Fe–Ti oxides in layered mafic intrusions, we investigate Mg isotopic compositions of magnetite, coupled with its chemical data and whole-rock major element and Sr-Nd isotope compositions from the Baima layered mafic intrusion in the Emeishan large igneous province, SW China. The Baima intrusion is mainly composed of magnetite-wehrlite and magnetite-troctolite (i.e., oxide-rich rocks) in the Lower Zone, and troctolite and gabbro (i.e., oxide-barren rocks) in the Middle and Upper Zones. Magnetite separates display large Mg isotopic variation, with δ26Mg ranging from −0.17 ± 0.06 to +0.58 ± 0.04‰ in the oxide-rich rocks and from −0.18 ± 0.06 to +0.98 ± 0.04‰ in the oxide-barren ones. The lack of correlation of δ26Mg with trace elements in magnetite and whole-rock Sr-Nd isotopic compositions indicates that the large Mg isotopic variation in magnetite was not produced by fractional crystallization, magma mixing, crustal contamination, and/or trapped liquid shift. Instead, equilibrium isotope fractionation induced by Mg–Fe re-equilibration between magnetite and ilmenite at different subsolidus temperatures controlled the Mg isotopic variation in the oxide-rich rocks; and kinetic isotope fractionation driven by Mg–Fe inter-diffusion between magnetite and olivine and/or clinopyroxene dominated the oxide-barren rocks. Both processes were primarily controlled by the assemblage and modal abundance of coexisting minerals to which magnetite adjoins. Overall, fractional crystallization and subsequent subsolidus diffusion played crucial roles in the genesis of the Fe–Ti oxides in the Baima intrusion. Our results also reveal widespread isotope disequilibrium between coexisting minerals in mafic magma chambers and suggest that Mg isotope geochemistry has a great potential to characterize the formation of Fe–Ti oxides in layered mafic intrusions.

Spatial and temporal variations of hydrogen and oxygen isotopes and sources of water vapour indicated from satellite precipitation products along the transection of 38°north latitude in North China

The variations of hydrogen and oxygen isotopes in rainfall are critical for understanding the sources of rainfall and the influence of local evaporation. Satellite precipitation products with high time resolution (for instance 1 h) could be helpful for testifying the accuracy of water sources, as it can clearly illustrate the route of cloud movement. In this study, we analyzed the composition of hydrogen and oxygen isotopes in different rainfall events in three stations from 2015 to 2018 along the transection of 38° N latitude from Taihang Mountains to the coastal region in North China, Taihang Mountain Station (mountainous area), Luancheng Station (pre-mountain plain) and Nanpi Station (coastal low plain). By selecting typical rainfall events, water vapor sources and its influence rainfall on hydrogen and oxygen isotopes were analyzed with hourly available CMORPH satellite precipitation products. Results showed that the hydrogen and oxygen isotopes of precipitation were cha-racterized by enrichment in the rainy season and depletion in the dry season. The hydrogen and oxygen isotopes in the rainy season showed a tendency of depletion with the increases of precipitation. The slope and intercept of the fitted relationship of hydrogen and oxygen isotopes in the piedmont region of the mountains were the lowest, indicating that precipitation in the piedmont plain was significantly affected by secondary evaporation fractionation. The effect of evaporation resulted in the largest variations of isotope ratio in the dry year. In the mountainous station, due to the heavy rainfall, large isotopic variation was found in rich precipitation year. Based on the route analysis of sate-llite precipitation products, dominant water vapor in the region was inland and northwest-oriented water vapor, while water vapor in the rainy season was from southwest and from the Pacific Ocean. There was a significant difference in the hydrogen and oxygen isotopes of precipitation in the mountainous and plain stations in 2016, owing to water vapor sources and effects of rainfall for the mountainous and evaporation for plain. The results from HYSPLIT model showed that during the rainstorm on 19th July in 2016, water vapor at the mountainous station was mainly from the southwest, while that in the coastal plain was a mixture of southwest and southeast sources. Overall, our results showed that spatial and temporal variations of hydrogen and oxygen isotopes were controlled by both water sources and evaporation processes along the transection of 38° north latitude in North China.

Copper isotope evidence for a Cu-rich mantle source of the world-class Jinchuan magmatic Ni-Cu deposit

Abstract A Cu-rich mantle source may play a key role in generating giant magmatic Ni-Cu deposits worldwide, but evidence for the source’s Cu enrichment and its mechanism is still rare. Copper isotopes can provide novel and direct insights into this issue since metasomatism that causes Cu enrichment in the mantle is commonly associated with a huge Cu isotope fractionation. Here we present the first Cu isotopic study on the world-class Jinchuan magmatic Ni–Cu deposit in China, including disseminated, net-textured, and massive sulfides. The disseminated and net-textured sulfides have variable δ65Cu values (+0.36 ± 0.38‰, n = 42), which are higher than those of massive sulfides (−0.44 ± 0.28‰, n = 11). The country rocks have a narrow δ65Cu range of 0.21 to 0.23‰, which is unlikely to have caused the large δ65Cu variations. The absence of a relationship between δ65Cu and whole-rock Cu contents rules out the possibility of surface weathering and diffusion-driven processes. Furthermore, the lack of correlation between δ65Cu and whole-rock Cu/Ni and Pd/Ir ratios excludes large Cu isotopic variations as a result of the progressive evolution of parental magma or sulfide melt. Numerical modeling indicates that the initially segregated sulfide melt has a mean δ65Cu of 0.44 ± 0.22‰ (2SD). Sulfide-liquid fractionation could have contributed to the enrichment of 65Cu in the Cu-rich net-textured sulfides and depletion of 65Cu in massive sulfides, respectively. The fractionated sulfide melts were fragmented and assimilated by new magma pluses, and consequently, the new segregated sulfide melts acquired lighter and more variable δ65Cu values in comparison with the initially accumulated sulfide melts. The estimated Cu isotopic composition of parental magmas for the Jinchuan Ni-Cu deposit is 0.54 ± 0.22‰ (2SD), which is up to ~0.5‰ higher than the mantle value. Copper transportation from oxidized subducted slabs to mantle peridotites and/or dissolution of Cu-bearing sulfides in the mantle caused oxidative breakdown and reprecipitation of sulfides and shifted the hybridized mantle source toward heavy δ65Cu as previously observed in mantle xenoliths. Our study, therefore, suggests that the source’s pre-enrichment is a key step in the generation of giant magmatic Ni-Cu deposits.

First-principles calculations of equilibrium bromine isotope fractionations

Significant bromine (Br) isotope composition variations are found in natural salts and brines, which are often even larger than those of co-existing chlorine isotope compositions. The cause of such large Br isotope variations remains elusive. In this study, equilibrium Br isotope fractionations among Br-bearing gaseous molecules, aqueous species and crystalline minerals are provided via the density functional theory (DFT) based first-principles calculations. These fractionation factors form the base for future Br isotope geochemistry studies. Specifically, the first-principles molecular dynamics (FPMD) method is used to evaluate the tricky solvation effects, i.e., dozens of snapshots of FPMD trajectories are selected and re-optimized to their lowest energy atomic coordinates, then the reduced partition function ratios (i.e., β factors) of aqueous Br-bearing species are obtained by computing the average values of those snapshots. In this way, the configurational effects of aqueous Br-bearing species are included. For crystalline compounds, the static first-principles periodic DFT methods are used. We find that the β factors generally increase as the oxidation states of Br increase, indicating that heavy Br isotopes tend to be enriched in substances with higher Br oxidation states. The aqueous Br-bearing species in brines have detectable but small Br isotope fractionations with each other. However, the fractionations between gaseous molecules and NaBr(aq) are significantly larger, e.g., Δ81BrCH3Br(gas)-NaBr(aq) is 0.95 ± 0.041‰ at 20 °C. As for minerals, the fractionation between Br-halite(p) (pure NaBr crystal) and NaBr(aq) is close to zero, but for Br-halite(1/124) (Na125Cl124Br1) and NaBr(aq), the fractionation is 0.206 ± 0.041‰. Similar results are found for the fractionations between Br-sylvite, Br-bischofite and Br-bearing solutions, indicating that Br isotope compositions are closely related to Br/Cl ratios in minerals.By using the calculated isotope fractionation factors, we have modeled the Br isotope composition variations during salt precipitation processes. At 20 °C, the total variations of Br isotopes of salts and brines are found to be −0.45‰ to +0.21‰ and −0.39‰ to 0‰, respectively. They are much smaller than the observed Br isotope variations in natural samples. There must be other ways to fractionate Br isotopes to the extent that observed in nature. Based on the predicted equilibrium Br isotope fractionations among substances with different Br oxidation states, the large Br isotope variations in nature can be explained by the change of Br oxidation state. The sudden change of Br isotope compositions hence can be used as a new indicator for the change of redox conditions.