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The Moon's mare volcanism predominantly occurs within the Procellarum KREEP Terrane (PKT), which is widely thought to be associated with KREEP components within the lunar interior. The Chang'e-5 (CE-5) mission sampled a young (2 Ga) mare basalt Em4/P58 unit of northern Oceanus Procellarum. The geochemistry of the CE-5 mare basalt enables assessment of mantle source compositions which are essential to understand the thermo-chemical mechanism for prolonged volcanism during secular cooling of the Moon. Geochemical compositions of the CE-5 bulk soil, breccias, and basalt clasts from various depths within the drill core consistently display high concentrations of incompatible trace elements (ITE: ∼ 0.3 × high-K KREEP; ∼ 5 μg/g Th) with KREEP-like inter-element ratios, for example for La/Sm, Nb/Ta, and Zr/Y. Exotic impact ejecta, extensive magma differentiation (<70 % fractional crystallization) and significant assimilation of KREEP materials during magma transit and eruption cannot account for the ITE contents and ratios or radiogenic isotope compositions (e.g., εNd initial of + 8 to + 9 and εHf initial of + 40 to + 46) of the CE-5 basalts; instead, partial melting of their mantle source played a dominant role. The Chang'e-5 basalt is a chemically evolved low-Ti mare basalt (Mg# of ∼ 34) with enriched KREEP-like ITE compositions but high long-term time-integrated Sm/Nd and Lu/Hf ratios, which represent a hitherto unsampled type of mare basalt. It formed by melting of an augite-rich mantle source (late-stage magma ocean cumulates containing > 30–60 % augite, and little or no ilmenite), with a small amount of late-stage interstitial melt that resembles KREEP (∼1–1.5 modal %, equivalent to 0.2–0.3 μg/g Th in the mantle source). The voluminous mare basalts making up the Em4/P58 unit (>1500 km3) provide compelling evidence for large-scale, ITE enriched young mare magmatism within Oceanus Procellarum. In combination with remote sensing data and with the unique Th-rich Apollo 12 basalt fragment 12032,366–18 (impact ejecta likely from Oceanus Procellarum), this implies that significant portions of the FeO- and Th-rich mare regions of the western PKT may also have formed in a similar way. [ABSTRACT FROM AUTHOR]

The distribution and activity of polyphosphate-accumulating sulfide oxidizing bacteria within marine sediments control the spatial distribution of sedimentary phosphorite formation in the modern ocean. In modern phosphogenetic settings, the concerted effect of microbial sulfide oxidation and microbial sulfate reduction in sediment pore waters is preserved in the sulfur isotope composition of trace sulfate in authigenic and early-stage diagenetic carbonate cements and phosphatic cements, as well as that of authigenic pyrite. If such variations in microbial sulfur metabolism controlled the spatial distribution of early phosphate mineralization in the geologic past, then one would expect to find differences between the sulfur isotope composition of cement-forming minerals in phosphatic and non-phosphatic facies of ancient sedimentary phosphate deposits. Here, we present paired measurements of the sulfur isotope composition of structural sulfate and structural sulfide in pore cements from co-occurring phosphatic and non-phosphatic facies of the Ediacaran Salitre Formation (Northeastern Brazil). The difference between δ34S of trace structural sulfate in carbonate cements (CAS) or phosphate cements (PAS) and δ34S of structural sulfide in pyrite or chromium-reducible sulfur (CRS), defined as Δ34S, provides a constraint on sulfur cycling within the pore waters from which the cements precipitated. In carbonate-cemented textures of the Salitre Formation, Δ34S = 12 to 31 ‰. In phosphate-cemented textures, however, PAS and pyrite crystals had more similar sulfur isotope compositions: Δ34S = −5–12 ‰. These values support the hypothesis that microbial sulfide oxidation was more prevalent in pore waters where phosphate mineralization occurred compared to pore waters where carbonate mineralization occurred – suggesting that microbial sulfide oxidation may have enabled the formation of sedimentary phosphorite on an Ediacaran carbonate platform, just as in modern phosphogenetic sites. [ABSTRACT FROM AUTHOR]

The carbonatite-related Nb deposits of the Alto Paranaíba Igneous Province (APIP) in central Brazil, currently account for ∼92 % of the global Nb production. In the APIP, pyrochlore is abundant in magnetite–apatite–tetraferriphlogopite ± carbonate rocks or phoscorites, occurring as interbedded layers with carbonatites in the lower hypogene zone, feeding dike swarms of phoscorite and calcite carbonatite, and late-stage carbothermal veins in the upper hypogene zone. The origin of the phoscorite-carbonatite association can be explained by three hypotheses: (1) crystal segregation from fractional crystallization, (2) liquid immiscibility, and/or (3) phoscoritic magma formation after basement metasomatism (fenitization). However, it is not well understood whether pyrochlore formation is limited to a carbonatitic event, carbohydrothermal, or both, and this gap of knowledge is addressed in this work. To investigate the petrogenesis of pyrochlore-rich phoscorite, cathodoluminescence (CL) images, chemical maps, and LA-ICP-MS data were acquired of pyrochlore crystals from magmatic and carbothermal rocks from the Boa Vista Nb mine, Catalão II Complex. In the Boa Vista mine, oscillatory and patchy zoning were identified as primary pyrochlore textures commonly recorded at the lower hypogene zone, while secondary dissolution, skeletal and zonation-free textures are registered at shallower depths in the upper hypogene zone. Calciopyrochlore is the dominant Nb phase at the Boa Vista mine, with only two kenopyrochlore outliers. The pyrochlore CI chondrite-normalized REE distribution is consistent with geochemical results of the carbonatite and phoscorite rocks, indicating a magmatic origin for pyrochlore and the presence of pyrochlore antecrysts in carbothermal veins. The Sr/Y vs La and Na vs Ce diagrams in pyrochlore indicate a continuous fractionation pattern, with some mixtures of antecrysts and primary phases. An examination of intercumulus calcite using CL provide evidence of carbonatitic magma residues within tetraferriphlogopite phoscorite dikes and suggests that alkaline–carbonate-rich fluids played a role in transporting heavy minerals (i.e., magnetite, apatite, pyrochlore). Consequently, the textural and chemical evidence in the Boa Vista Nb mine indicates that the origin of pyrochlore-rich phoscorites is the result of physical segregation of heavy minerals from a carbonatite magma by fractional crystallization, leading to the emplacement of pyrochlore-rich carbonatite and phoscorite dikes. The implications at Catalão II may extend to other APIP alkaline-carbonatite complexes, as they share a genetic connection, and should motivate further studies focusing on pyrochlore geochemistry in other carbonatite-related Nb deposits, which will be crucial for advancing our knowledge of global Nb metallogenesis. [ABSTRACT FROM AUTHOR]

Hydrothermal Iron-oxide-Cu-Au (IOCG) deposits are important exploration targets for a number of metals of economic importance. Voluminous sodium metasomatism is ubiquitous in most IOCG provinces. The origin of the metasomatic fluid responsible for the formation of albite-rich rocks in such terranes is contentious; both evaporite-derived fluid and magmatic fluid have been advocated. The Singhbhum IOCG province in India is known for hosting several polymetallic deposits from which U, Cu, and apatite-magnetite are mined as principal commodities together with Ni, Au, Ag, Se, Te, Mo, and low-Ti magnetite as by-products. Voluminous albite-rich rocks occur at several sites along the mineralized belt. Metasomatic albite schist comprising predominantly albite and quartz at Pathargora contains tourmaline intricately associated with albite. Based on textures and mineralogical associations, tourmaline is classified as: tur 1 : coarse nodular tourmaline ± albite ± magnetite aggregate; tur 2 : disseminated fine-grained tourmaline in a schistose matrix; and tur 3 : tourmaline + biotite + magnetite + apatite clots. All tourmaline belongs to the alkali group and most to the dravite sub-group. Very low concentrations of Li (avg 3.8 ppm), Zn (avg 6 ppm) and Mn (avg 21 ppm) but high V (avg 2130 ppm) and Ni (avg 306.5 ppm) in tur 1 core (tur 1c) co-genetic with albite contrast with what is reported in magmatic/magmatic-hydrothermal tourmaline of granitic affinity. The δ11B values of tourmaline are mostly positive, ranging between –4.0 and 9.2 ‰ (avg 4.0 ± 3.0; n = 79); values of tur 1 cores are 4.9–9.2 ‰. Previous fluid inclusion studies described the presence of halite and barite daughter crystals in primary fluid inclusions and demonstrated the involvement of a high-temperature (≥450 °C) and high-salinity (≥50 wt% NaCl equivalent) brine in the formation of cores of tur 1. Calculated δ11B values of the hydrothermal fluid in equilibrium with tur 1c range from 7.3 to 11.5 ‰ (for a crystallization temperature of 450 °C). Based on the textural setting of the tur 1c -albite assemblage, geochemical and boron isotope composition of tur 1c , and evidence of a high saline brine, we propose that the albite schist is the product of Na-metasomatism by brines that derived major constituents from the dissolution of marine evaporite. The inferred paleo-latitude and geological environment of sedimentation related to the host lithologies are consistent with the evaporitic model. We further suggest that a similar mechanism might have played an important role in the formation of albite-rich rocks in other IOCG provinces where the involvement of evaporite-derived fluids in mineralization/alteration have been demonstrated. Similar major element, trace element and positive boron isotope (1.5–6.3 ‰) composition of tur 3 suggest similar source of fluid as that of tur 1c , and tur 3 formed either during the same alteration event or during a separate fluid pulse. On the other hand, the mode of occurrence, very low trace element concentration and weakly negative to positive δ11B (−4 to 2.3 ‰) value of tur 2 suggest their metamorphic origin. [ABSTRACT FROM AUTHOR]

Vanadium (V) is a redox-sensitive trace metal that typically exists in one of three oxidation states (+3, +4 and +5) in natural waters; a feature increasingly used in paleoredox studies of ancient marine sediments. However, our knowledge of V geochemistry in low-oxygen marine environments is still limited, especially regarding interactions of V with reduced iron minerals such as green rust. Carbonate green rusts (GR CO3) are mixed FeII/FeIII-phases found in some modern ferruginous settings, such as Lake Matano (Indonesia), and were likely abundant in ancient ferruginous marine systems where they may have played an essential role in authigenic V enrichments in sediments. Here, we present an abiotic pathway of V removal from seawater via reduction and adsorption onto amorphous GR CO3. Suspensions of the freshly precipitated GR CO3 (1 g L−1) were added to vanadate (1 mg VV L−1 initial concentration) in anoxic synthetic seawater solutions. Vanadium removal by GR CO3 was rapid and efficient, with 92 – 99% of V removed in under 20 seconds. Synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy showed that VV adsorbed by GR CO3 was partially reduced to a mixture of VV and VIV, with the average oxidation state of adsorbed V increasing (+4.3 to +4.7) with increasing solution pH (7.5 to 8.5). Upon subsequent exposure to aerated seawater, V-bearing GR CO3 oxidized to lepidocrocite [γ–FeO(OH)] within 24 h, with concomitant reduction of all solid-phase VV to VIV. During oxidation, V was not released back into solution; rather, extended X-ray absorption fine structure (EXAFS) modeling revealed that VIV was structurally incorporated into lepidocrocite as octahedral vanadyl (VO2+). Our work further constrains the aqueous geochemistry of V, which has implications for understanding V cycling and removal mechanisms in both modern and ancient marine systems. [ABSTRACT FROM AUTHOR]

In the Earth's crust, Ni is generally concentrated in mafic and ultramafic rocks and is coupled with Mg in Mg-olivine, Mg-pyroxene and spinel. Whether the Ni-rich, and in general, the mafic component of Australasian tektites and microtektites is terrestrial or meteoritic is still debated. To test the origin of the Ni-rich component, we studied the Ni versus Mg distribution in a large geochemical database of Australasian tektites (n = 208) and microtektites (n = 238) from the literature. Nickel contents of up to 428 µg/g in tektites and 678 µg/g in microtektites covary with Mg in tektites and in most (∼85%) of the microtektites defining a mixing trend between crustal and chondritic values, thereby documenting the chondritic origin of the Ni-rich component in Australasian tektites/microtektites. Mixing calculations indicate up to 4% and up to 6% by weight chondritic component in tektites and microtektites, respectively. A possible mafic component of terrestrial origin is observed in a minority of tektite and microtektite specimens. This finding is consistent with previous works suggesting a possible occurrence of a chondritic signature in high-Ni tektites, based on the study of highly siderophile elements and Os isotopes, and high-Ni microtektites, based on Ni, Co, and Cr ratios. The combined geochemical and isotopic analyses of high-Ni tektites and microtektites in collections worldwide may thus reveal the chondritic impactor type that generated one of the presumably largest impacts in the Cenozoic. [ABSTRACT FROM AUTHOR]

We have analyzed concentrations of Mo, Re and U in the suspended particles, water column, underlying carbonate-dominated sediments and pore waters of two contrasting marine lakes situated on the Adriatic Coast of Croatia. Our data are the first for Re in these lakes. Rogoznica Lake is mainly euxinic, but subject to occasional oxygenation events, whereas Mljet Island's Malo Jezero is currently oxic year around but historically was seasonally euxinic. These characteristics make the lakes useful testing grounds for redox proxies. We devote particular attention to Re/Mo ratios, which have great promise as redox proxies. In marine sediments, the range of log[Re auth /Mo auth ] exceeds 2, and typical analytical uncertainty is ±0.05, providing resolving power similar to δ98Mo. Authigenic [Re s /Mo s ] ratios in sediments depend on varying supplies of three components: FeMo,Re)S 4 coprecipitates, Fe(III) oxyhydroxides (plus Mn(III,IV) oxyhydroxides in some cases) and a still-uncharacterized Re-rich, Mo-poor component possibly of biological origin. Removal of the latter component explains a 50% depletion of Re aq without Mo aq from Rogoznica's oxic waters. Water column concentrations of Mo aq and Re aq , as well as [Re s /Mo s ] ratios in Rogoznica's suspended particles are predicted successfully by a model that attributes these elements' removal from sulfidic seawater solely to coprecipitation in Fe(Mo,Re)S 4 , assuming a partition coefficient of 0.6. However, to predict sediment compositions, additional authigenic Mo supplied by mainly Fe(III) oxyhydroxides during sporadic oxygenation events must be considered. In Malo Jezero, sulfide concentrations are too low even in pore waters for precipitation of Fe(Mo,Re)S 4. Consistent with earlier work, U aq profiles are best explained by eddy diffusive transport to the sediment rather than capture by a precipitate in the water column. In Rogoznica pore waters, Mo aq extracted through 0.45 μm pore size filters exceeds by 50-fold concentrations predicted by the model and measured previously with 0.15 μm filters. This observation implies presence of ferrothiomolybdate colloids, which could be important, overlooked participants in the sedimentary geochemistry of Mo. [ABSTRACT FROM AUTHOR]

A significant portion of the continental crust is composed of plutonic igneous rocks. However, little is known about the geochemical behaviour of N between the different minerals during magmatic differentiation. To provide new constraints for the behaviour of N during crust formation, we have characterised the geochemistry of nitrogen (N) in the compositionally zoned calc-alkaline pluton at Loch Doon, SW Scotland. We present N concentration and N isotope values for whole-rock data alongside biotite, plagioclase and K-feldspar mineral separates and assess the degree to which these data preserve equilibrium partitioning during magmatic differentiation. We show that whole rock likely inherited its N contents and δ15N signatures from the initial source composition and that this signature is homogenous at a pluton scale. Whilst the whole-rock data are best explained as crust-derived N in the source, the degree of homogenisation across a pluton scale is inconsistent with empirical N diffusivities, ruling out syn-emplacement crustal assimilation as the source of N. Instead, our data suggest a crustal signature inherited from depth associated with the Iapetus subduction zone. At a mineral scale, we find that N preferentially partitions into the feldspars over mica in this system in the order K-feldspar > plagioclase ≈ biotite > quartz, with average mineral–mineral distribution coefficients of D N plagioclase-biotite = 1.3 ± 0.6 and D N Kspar-biotite = 2.8 ± 0.6. Partitioning is accompanied by a large and near constant equilibrium isotope fractionation factor between biotite and both feldspars (averages are Δ15N Plag-Biotite = +7.8 ± 1.2‰ and Δ15N Kspar-Biotite = +7.9 ± 1.0‰). In contrast, Δ15N Kspar-Plagioclase closely approximates 0‰, where both minerals show δ15N values overlapping with the bulk rock δ15N values. These results show that mica crystallisation generates a 15N-depleted reservoir within plutonic rocks. Moreover, our dataset suggests that feldspars might be a more significant host of N in the igneous portion of Earth's continental and oceanic crust than previously thought. [ABSTRACT FROM AUTHOR]

Understanding siderophile element partitioning between metal and silicate melts under diverse conditions can be used to place important constraints on the materials and conditions of planetary accretion and core formation, as well as post core formation processes. However, the effects of Si on the partitioning and activity coefficients for these elements are not well known, despite Si likely being one of the dominant light elements in Earth's core. To address this gap in understanding, we have undertaken a systematic study of the highly siderophile elements Re, Pt, Os, and Ru, and the refractory lithophile elements Nb, Ta and Ti at 1600 °C and 1 GPa, to derive epsilon interaction parameters for these elements in FeSi metallic liquids. Positive epsilon interaction parameters were measured for Nb, Ta, Ti, Ru, Re, Pt, and Os, indicating that dissolved Si in Fe liquids causes a decrease in their metal/silicate partition coefficients (or 'silicophobic' behavior). Furthermore, ε Re , O s , o r R u Si > ε Re , O s , o r R u S which means Si causes a larger decrease in D(metal/silicate) than S, and the chalcophile behavior expected from some elements will be completely masked by the presence of Si in a metallic liquid. The new parameters are used to update an activity model that now includes 36 siderophile elements in Fe-Ni-Si-S-C liquids (27 trace elements considered here). Systematic assessment of these 27 elements shows which have the strongest affinity for Si, C, and S, and also how activity coefficients for these elements would vary during accretion and core formation in Earth, Mars, and Mercury of widely differing fO 2 and core compositional conditions. The activity model is combined with new partitioning expressions for Mo, W, Cr, Re Ru, Pt, and Os and applied to aspects of post core formation mantle geochemistry of Earth, Mars, and Mercury. Our updated expressions show that the BSE Mo/W ratio can easily be achieved with metal/silicate partitioning during growth of the Earth, whereas Re, Os and Ru become lower than and highly fractionated compared with BSE values during core formation and accretion, and thus nearly 99% of their BSE abundances are likely contributed by late accretion. Ru isotopes should be a very good indicator of the source material for the late accretion. The high Pt/Os and Re/Os developed in a deepening magma ocean during the growth of the Earth, indicates 186Os and 187Os isotopes could be coupled if this ancient material remained isolated and subsequently became entrained in mantle plumes and measured in surficial lavas. The extent to which this occurred will be limited by the low Os content of this ancient material, thus requiring mixing as a major component in plume sources. Martian mantle Hf/W ratio stays low during accretion and core formation modelling, suggesting that W isotope anomalies are more likely due to solid/liquid silicate fractionation than to core formation. Finally, Ti contents measured by MESSENGER at Mercury's surface can be explained by segregation of either a metallic core (IW-6 to -8) or metallic core + sulfide (IW-4 to -7.5) followed by mantle melting. [ABSTRACT FROM AUTHOR]

Clasts of feldspathic lithologies such as magnesian anorthosites, anorthositic troctolites, and granulites in lunar meteorites have greatly expanded knowledge of the lithologic diversity of the lunar crust. However, their origins and relationships to other major crustal lithologies such as the ferroan anorthosites, magnesian-suite, and alkali-suite are not fully understood. Here we present the results of phase equilibrium modeling using the MELTS and MAGFOX programs designed to investigate the origins of lunar crustal lithologies and petrologic connections between them. We show that the major and trace element compositions of the Mg- and alkali-suites are consistent with partial melting of hybridized sources and are inconsistent with decompression melting + assimilation models. Our results also show that the vertical trend in Mg# in mafic silicates vs. An# in plagioclase characteristic of feldspathic meteoritic lithologies and ferroan anorthosites can be produced by fractional crystallization of KREEP-free Mg-suite melts, but that these melts are not likely to contribute significantly to the composition of the global crust. Furthermore, we calculated potential parental melt compositions for these crustal lithologies using the abundances of REEs in plagioclase in FANs, the Mg- and alkali-suites, and clasts in feldspathic meteorites. Our results show that despite low bulk rock abundances of incompatible trace elements in many feldspathic lunar meteorites, parental melts with overall REE abundances similar to or in excess of KREEP are needed to reproduce the REE abundances in plagioclase in clasts from feldspathic lunar meteorites. However, the lack of a Na enrichment trend in their plagioclase compositions with decreasing Mg# requires very Na-depleted melts without a KREEP component. The available data regarding magnesian anorthosites, anorthositic troctolites, and granulites in lunar meteorites, and inferences made here regarding their parental melt compositions, lead to contradictory and ambiguous conclusions regarding their origins. [ABSTRACT FROM AUTHOR]

Ca isotope geochemistry has great potential for improving our understanding of magmatic systems and for tracing the deep Earth carbon cycle. There are still many open questions, however, regarding the proper application of this relatively novel proxy to the study of mantle-derived magmas, including (i) the possible effects of pressure on mineral-melt Ca isotope fractionation factors, and (ii) the potential for Ca isotopes to be used as tracers of recycled marine carbonates in mantle-derived magmas. Kimberlites are mantle-derived melts that are highly enriched in CO 2 and are the deepest-sourced magmas (>200 km depth) known to erupt at Earth's surface, providing an excellent opportunity to explore these questions. We present Ca isotope data combined with detailed petrographic observations, bulk-carbonate C-O isotope data, and bulk-rock major element analyses, for a suite of 23 well-characterized kimberlite samples from their type-locality (Kimberley, South Africa). These kimberlites have abundant previous evidence for recycled surface materials in their mantle source, including low S isotope and moderately radiogenic Sr isotope compositions, yet display only limited variations in their Ca isotope compositions (δ44Ca BSE of −0.08‰ to −0.27‰), with an average of −0.17 ± 0.02‰ (2SE, n = 21). This composition is indistinguishable from average carbonatites [−0.19 ± 0.03‰ (2SE, n = 106)] and OIB from recent studies [−0.16 ± 0.01‰ (2SE, n = 41)], and slightly lower than average MORB [−0.11 ± 0.02‰ (2SE, n = 31)]. Although our samples display a wide range of emplacement styles, alteration conditions, extents of magmatic differentiation, and degrees of mantle-cargo entrainment (i.e., xenocryst accumulation), we find no correlations between Ca isotopes and any of these factors. Instead, we find that low-degree partial melting of the likely kimberlite source lithology (i.e., carbon-bearing garnet lherzolite) yields modelled melt δ44Ca BSE values ranging between −0.12‰ and −0.16‰ (at 1400–1500 °C), in agreement with the measured Ca isotope compositions of the Kimberley kimberlites. This observation, and the lack of heavy carbon isotope signatures in the examined samples, indicates that kimberlites do not require subducted carbonates in their mantle sources, despite their very high CO 2 contents. Although several recent studies have suggested that equilibrium mineral-melt Ca isotope fractionation factors (e.g., 1000lnα grt-melt) could be significantly different at higher pressures (i.e., due to pressure-induced changes in Ca O bond lengths and coordinations), our models successfully reproduce the kimberlite data using pressure-independent predictions for mineral-melt fractionations. It remains possible, however, that differences in isotopic fractionation due to the peculiar composition of kimberlite melts (e.g., high CO 2 , low SiO 2) are effectively cancelled out by competing pressure effects, and future work independently targeting these factors will be especially important for our understanding of Ca isotope fractionation in mantle-derived melts and the Ca isotope systematics of Earth's mantle. [ABSTRACT FROM AUTHOR]

Understanding subduction processes is critical in assessing the long-term evolution of the upper mantle and continental crust. We present new geochemical data on glassy submarine lavas from the Bransfield Strait, the Phoenix and West Scotia ridges, and previously unpublished data of marine sediments from atop the Phoenix Plate. We combined new and published geochemical data from across the northern sector of the Antarctic Peninsula to unravel both large-scale mantle composition and flow across the region. The geochemistry of Phoenix and West Scotia Ridge basalts supports the hypothesis that both ridges are underlain by Pacific MORB mantle, brought into the region through the eastward expansion of the Scotia Plate. Comparisons among lavas from the Phoenix/West Scotia ridges, the South Shetland Islands volcanic arc, and the Bransfield Strait/Prince Gustav Rift back-arc region reveal that the Pacific upper mantle flowed into the mantle wedge and was subsequently modified by subduction processes. The compositions of Bransfield Strait lavas range from strongly subduction-influenced near the strait's center to akin to Phoenix Ridge MORB toward the strait's edges. This suggests that the Phoenix MORB mantle has flowed around the slab edges into the mantle wedge, diluting the subduction signal and focusing the subduction-modified mantle towards the center of the strait. Monte Carlo simulations indicate that mixing of Phoenix MORB mantle with 0 to 3 % subduction component having a fluid/sediment ratio of ∼1 can explain the compositional range in the Bransfield Strait. Furthermore, our modeling suggests the presence of a more depleted Phoenix MORB mantle beneath the South Shetland Islands modified by the addition of ∼3 % subduction component with a fluid/sediment ratio ranging from ∼0.18 to 4. The increase in fluid/sediment ratios in the South Shetland Island lavas corresponds to a spatiotemporal progression of volcanism from the southwest (40–140 Ma) to the northeast (30–60 Ma). Finally, we have identified a set of lavas with unique trace element and isotope compositions typical of alkaline volcanism found across other parts of the Antarctic Peninsula. Surprisingly, we find occurrences of these lavas on both sides of the South Shetland Trench, suggesting the presence of a distinct enriched source in the upper mantle throughout the region. [ABSTRACT FROM AUTHOR]

The direct determination of silicate melts iron and silicon isotopes signature remains a major challenge of high-temperature isotope geochemistry. For this reason, melts are often approximated by silicate glasses. Calculation of precise equilibrium Si and Fe isotopes fractionation factors between minerals and melt would indeed allow us to distinguish equilibrium fractionation from diffusion-driven kinetic fractionation involved in the iron and silicon isotopes signatures of Earth and other planets. In this study, we use for the first time, first-principles molecular dynamics based on density functional theory to determine iron and silicon isotope compositions of different silicate melts, namely: iron-rich basalt, iron-depleted basalt, basanite, trachyte and phonolite. The 57Fe/54Fe reduced partition function ratios (β-factors) of the different melts span over a 1.1 ‰ range at 1000 Kelvin (K) while 30Si/28Si β-factors are much less influenced by the melt composition with a 0.5 ‰ fractionation range at the same temperature. The main parameter controlling iron isotope fractionation in silicate melts having similar iron oxidation state is, after temperature, the average Fe-O bond length. The chemical environment around iron (e.g. Fe-Fe distances) is suggested to contribute to Fe isotope fractionation as well. Silicon isotopes fractionation seems also affected, but to a lesser extent, by its local chemical composition with decreasing Si-Fe distances leading to slightly higher Si β-factor in the melt. From these melts Fe and Si β-factors, a new set of equilibrium fractionation factors between a variety of minerals and melts has been calculated. These new Δ57Fe min-melt and Δ30Si min-melt sets allow us to discuss whether processes such as fractional crystallization, partial melting and diffusion could be responsible for the documented Fe and Si isotopes variations in igneous rocks. Our results suggest that: 1) fractional crystallization may explain at least part of the Fe and Si isotopic evolution during magmatic differentiation, for values up to δ57Fe = 0.65 ‰ and δ30Si = -0.1 ‰, respectively, 2) partial melting of the upper mantle can produce the Mid-Ocean Ridge Basalts (MORB) iron isotopes signature. Finally, we calculated that olivine at equilibrium with a basaltic melt could display an iron isotope composition down to −0.1 ‰ for δ57Fe. Hence, the lower isotopic compositions (δ57Fe < -0.1 ‰) observed in natural olivines are most likely due to diffusion-driven kinetic fractionation. [ABSTRACT FROM AUTHOR]

The super-chondritic Mo isotopic composition of the continental crust has been attributed to contributions from subducted oceanic slabs and/or sediments, which introduce isotopically light Mo to the mantle. It has been hypothesized that dehydrated oceanic slabs subduct into the deep mantle and contribute to the genesis of ocean island basalts (OIBs). However, OIBs have similar average δ98/95Mo values (−0.22‰± 0.04‰; 2SE; n = 87) to the depleted mantle. Subducted oceanic sediments may create a light-δ98/95Mo reservoir in the subcontinental lithospheric mantle, but this has not been investigated in detail. Understanding the Mo isotopic systematics of the continental crust and mantle requires an understanding of the Mo isotopic composition of lithospheric mantle-derived volcanic rocks. The lithosphere in the Tibetan region has experienced multiple stages of oceanic subduction and is thus ideal for studying magmas derived from sediment-modified lithospheric mantle. Mafic ultrapotassic volcanic rocks (UPVRs) from the Sailipu area on the southern Tibetan Plateau have high Mg# values (67.1–72.5) and enriched Sr–Nd isotopic compositions and are primitive magmas derived from the lithospheric mantle. These rocks have higher Ce/Mo ratios (225–422) and lighter δ98/95Mo values (−0.45‰ to −0.13‰) than the depleted mantle, mid-ocean ridge basalts (MORBs), and OIBs, as well as high ε Hf (t) values at given ε Nd (t) values compared with the terrestrial array (Δε Hf = 4.59–5.73). The involvement of Ca-poor pelagic sediments rather than the lower continental crust and hydrated oceanic slab best accounts for the high Ce/Mo ratios and light δ98/95Mo values of the studied rocks. The Sailipu UPVRs also have higher Nb/Ta (18.9–20.8) and Th/La (2.6–3.4) ratios than arc-related igneous rocks and MORBs, suggesting that their source was phlogopite-bearing lithospheric mantle with a metasomatic vein component (rutile + monazite ± lawsonite). We propose a two-stage geodynamic process to explain the formation of the Sailipu UPVRs: (1) a metasomatic vein component with high Th/La and Ce/Mo ratios formed in the lithospheric mantle during multiple stages of oceanic subduction; (2) high mantle temperatures related to convective thinning of the lithosphere resulted in melting of the vein component and the ambient mantle, which produced hybrid melts of various mantle domains during the post-orogenic stage. The Sailipu UPVRs have enriched Sr–Nd isotopic compositions and high Th/La and Ce/Mo ratios, similar to lamproites that are widespread in the Tethyan orogenic realm from the Mediterranean to the southern Tibetan Plateau. Given that UPVRs with light δ98/95Mo values have also been identified in the Western Alps, we propose that the isotopically light Mo component is widespread in Tethyan lithospheric mantle. This isotopically light Mo in the lithospheric mantle may be a complementary end-member to the isotopically heavier continental crust. The recycling of subducted oceanic sediments has a key role in the deep recycling of Mo. [ABSTRACT FROM AUTHOR]

The geochemistry of the carbonate sedimentary record is invaluable for understanding the ancient seawater evolution of carbon and redox-sensitive elements. However, the application of carbonate geochemical paleoredox proxies can be limited by our ability to recognize records impacted by syn- and post-depositional diagenesis with pore fluids that have geochemical compositions which are distinct from the overlying seawater—resulting from variable redox conditions, fluid sources, and sediment- vs seawater-buffered conditions. We extend a numerical framework, established for the application of Ca isotopes, for recognizing sediment- vs fluid-buffered alterations during aragonite-to-calcite recrystallization for widely applied carbonate paleoredox proxies: iodine ratios (I/Ca), cerium anomaly (Ce/Ce*), and carbonate-associated Cr, U, and S isotopes. We model endmember reducing and oxidizing fluid diagenetic scenarios, as opposed to incorporating biogeochemical evolution of pore fluids within the model. The results reveal that early, fluid-buffered diagenesis of relatively unevolved seawater ("seawater-buffered") represents the ideal scenario for preservation for all proxies, including C isotopes. Conversely, fluid-buffered alteration in pore fluids with redox conditions highly evolved from the overlying water column is likely to alter the primary carbonate geochemistry. Model calibration against records from the Bahamas Clino and Unda cores suggests each proxy is uniquely sensitive to a given style of diagenetic alteration, with Ce/Ce* the most robust and I/Ca ratios most sensitive to early diagenetic alteration. We recommend multiple strategies, including relationships with C, O, and Ca isotope data, that can be leveraged to identify the preservation of primary seawater geochemistry for a given proxy. Last, we compare the diagenetic model predictions with published records from the Permian/Triassic boundary to demonstrate how incorporating stratigraphic geochemical patterns alongside interpretation of diagenetic model results can support interpretation of secular seawater signals. To improve our understanding of the effects of diagenesis on carbonate paleoredox proxies, additional experimental constraints, field-based observations, and multi-proxy datasets are needed. [ABSTRACT FROM AUTHOR]

Lunar impact glasses can provide important information on the bulk compositions of their sources and the impact history of the Moon. Here, we report the chemical composition of fifty-four clean glass spherules containing neither relict clasts nor crystals from the Chang'e-5 (CE5) regolith. They can be subdivided into three compositional groups: (1) mid-Ti basaltic (TiO 2 = 4.1 ∼ 6.5 wt%), (2) low-Ti basaltic (TiO 2 = 1.3 ∼ 3.9 wt%), and (3) high-Al (Al 2 O 3 > 15 wt%). Fifty-one glasses (∼94 %) are mid-Ti basaltic, which form a loose compositional cluster for most major and trace elements. These glasses exhibit considerable variations in SiO 2 (35.3 ∼ 45.3 wt%). Their TiO 2 , Al 2 O 3 , MgO and CaO show negative correlations with SiO 2 , while the Na 2 O, K 2 O and P 2 O 5 positively correlate with SiO 2 , also yielding a positive correlation between the CIPW normative plagioclase and olivine. These variations likely result from differential vaporization of SiO 2 , strongly suggesting an impact origin of these glasses. Their major and trace element compositions are averagely similar to the bulk-rock, in turn indicating that they were formed from the local regolith. The remaining three glasses, including two low-Ti basaltic and one high-Al variety, exhibit distinct major and trace elements from the regolith, indicating an exotic source. In addition, the mid-Ti basaltic glasses provide another approach for estimating the average composition of the CE5 basalt other than directly measuring the small basalt fragments assuming that the exotic materials in the CE5 regolith were limited. This estimation reveals critical trace element characteristics of the CE5 basalt, e.g., it has higher La/Yb (3.71), Sm/Yb (1.76), Sr/Yb (31.6), and (Eu/Eu*) N (0.45) than KREEP, indicating that CE5 basalt must derive from a non-KREEP source. Chemical modeling indicates that the contribution of KREEP-rich materials in the mantle source should be less than 0.3 %. The trace element characteristics of the CE5 basalt can be reproduced by extensive (80 %) fractional crystallization after low-degree (2 %) melting. We propose that this fractional crystallization process might occur at depth, implying vast igneous underplating (7,250 ∼ 11,750 km3) beneath the CE5 landing area. This study also suggests that the high Th concentration (5.43 ppm) is an inherent property of the CE5 basalt resulting from extensive fractional crystallization. Thus, high Th detected by remote sensing may not be associated directly with a KREEP component but rather with highly fractionated basalts. [ABSTRACT FROM AUTHOR]

Eucrites exhibit a range of igneous and metamorphic textures and geochemistries that can be used to study the evolution of early planetary differentiation and crust formation in the solar system. We integrated petrologic/textural observations, in-situ geochemical analyses, and thermodynamic modeling to explore the petrogenesis of Elephant Moraine (EET) 90020, an unbrecciated meteorite. We identified microdomains that record relatively high metamorphic temperatures and concluded that diffusion processes likely modified EET 90020 during and/or after peak thermal conditions. There is little evidence that partial melting caused the distribution of minor and trace elements within or among the microdomains. Trace element linear transect measurements within the microdomains imply that phosphate minerals strongly controlled trace element distributions throughout the sample. The discrepancy between the observed metamorphic textures, major element chemistry, and the trace element distributions is a consequence of differing chemical mobility. Multiple processes are influencing geochemistry within a single sample which has implications for the development of petrogenetic models that seek to reconcile the differences observed between eucrite geochemical groups. [ABSTRACT FROM AUTHOR]

Although it has been suggested that the trace element patterns of sedimentary pyrite can be affected by early diagenesis, detailed studies on modern marine environments addressing this hypothesis are scarce. Organoclastic sulfate reduction (OSR) and sulfate-driven anaerobic oxidation of methane (SD-AOM) are the dominant sulfate reduction processes in organic-rich and methane-rich marine sediments, and commonly result in the formation of authigenic pyrite. To better understand how OSR and SD-AOM affect the trace element geochemistry of pyrite, we applied laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) to analyze trace element contents of pyrite from two methane-seep sites (DH-CL11 and HS148) of the South China Sea. The trace element data are complemented by the measurement of iron isotope compositions of authigenic pyrite. This new data set, supplemented by published sulfur isotope data, improves our understanding of the diagenetic processes during early diagenetic pyrite formation. High δ56Fe and δ34S values of pyrite reflect the dominance of SD-AOM within sulfate-methane transition zones (SMTZs) at both sites (i.e., from 705 to 767 cm below seafloor at site DH-CL11 and from 490 to 690 cm below seafloor at site HS148), whereas pyrite from shallow depth characterized by low δ56Fe values points to early OSR processes. Within the SMTZs, pyrite exhibits highly variable but overall high manganese (Mn) contents (12 to 732 mg/kg at site DH-CL11; 12 to 1145 mg/kg at site HS148), compared to OSR-derived pyrite from shallow depth. Similar to this pattern, pyrite formed at the SMTZ shows higher lead (Pb), zinc (Zn), copper (Cu), and vanadium (V) contents than pyrite formed at shallower depths above the SMTZ. Enrichments of these metals in pyrite forming at the SMTZ are best explained by enhanced reductive dissolution of iron and manganese (oxyhydr)oxides under sulfidic conditions induced by SD-AOM, and subsequent trace element incorporation into pyrite. Arsenic (As), molybdenum (Mo), and antimony (Sb) distributions in pyrite vary between the two study sites. Pyrite from shallow depth of site HS148 has high contents of all three elements, indicating effective immobilization of dissolved As, Mo, and Sb during pronounced OSR. In contrast, apparently less intense OSR at shallow depth of site DH-CL11 allowed for more dissolved As, Mo, and Sb to diffuse downward to greater depth, resulting in the enrichments of these elements in pyrite formed at or close to the SMTZ. Positive correlations between As and cobalt (Co), and between As and nickel (Ni) typify pyrite derived from both OSR and SD-AOM for both study sites, and As-rich pyrite from site DH-CL11 is characterized by a distinctly high Co/Ni ratio. Both patterns suggest that the presence of As affects the uptake of Co and Ni into pyrite. Our study documents that pyrite element contents in methane-rich environments are significantly influenced by different sulfate reduction processes during early diagenesis, allowing the differentiation of OSR-derived pyrite from SD-AOM-derived pyrite by means of trace element geochemistry. [ABSTRACT FROM AUTHOR]

The metamorphic reworking of mineralized pegmatites during orogenesis remains unclear, making the genesis and the tectonomagmatic significance of pegmatite mineralization obscure. This study demonstrates the multiple utilities of titanite geochemistry in establishing the Caledonian metamorphic evolution of the world's largest intra-plutonic Nb-Y-F pegmatites in the Paleoproterozoic host rocks in Tysfjord, Northern Norway. A combination of titanite-specific barometry, Zr-in-titanite thermobarometry, and titanite U-Pb geochronology yields peak metamorphism of ∼12 kbar and 730–750 °C at ∼410 Ma for the host rocks and the largest metamorphosed Paleoproterozoic pegmatite (meta -pegmatite) in the region. In relation to published U-Pb ages of 410–400 Ma for other regional meta -pegmatites, interpreted as Caledonian overprinting here, we argue that the Paleoproterozoic pegmatite protoliths have undergone metamorphism analogous to the host rocks, which was caused by allochthonous nappe stacking late in the Caledonian collisional orogeny (∼440–400 Ma). Published formation ages of ∼400–380 Ma for the regional undeformed pegmatites are 10–30 Ma younger than the peak metamorphism, supporting an anatectic link to the Caledonian post-collisional extension. The Caledonian orogeny led to strong shearing of preexisting pegmatite bodies and resetting of trace elements and U-Pb isotopic systems of the constituent minerals via mineral re-crystallization, inheritance of Pb isotopic components, and element diffusion. This cautions against the interpretation of meta -pegmatite-derived ages and geochemical information in tectonomagmatic terranes without detailed textural investigation. [ABSTRACT FROM AUTHOR]

Zircon oxygen isotope ratios have been used to trace the incorporation of sedimentary rocks into magmas. The dramatic increase in maximum zircon δ18O values in the Paleoproterozoic observed in global databases coincides with changes in surface environments (e.g., the rise of subaerial and oxidative weathering), implying a connection between elevated zircon δ18O and these changes. Zircon δ18O between 2.5 and 2.2 Ga, however, is relatively under-constrained owing to limited available data in this age range. To augment data from this critical time period and understand potential causes for the elevated zircon δ18O values, we report U-Pb zircon ages and δ18O values of zircon, as well as, whole-rock major and trace element geochemistry of Paleoproterozoic strongly peraluminous granites (SPGs) from the southwestern margin of the Yangtze Block (China). Our geochronological data demonstrate that these SPGs crystallized at ∼2.35 Ga and that inherited zircon with ages of 2428–2721 Ma are present in these granites, indicating the source rocks of these granites were deposited, subsequently metamorphosed, and partially melted between 2.43 and 2.35 Ga. Synmagmatic zircon from samples dated in this study have ε Hf (t) values of −6.4 to −0.9 and high δ18O values of 7.6–9.9‰, elevated above the maximum value observed in Archean zircon (∼7‰). These granites can be divided into two groups based on whole-rock geochemistry. Both Group 1 and Group 2 granites were derived from a similar high δ18O, metapelitic source, but were generated by dehydration melting and hydrous melting, respectively. Our results demonstrate that the fine-grained sedimentary rocks from which the SPGs were derived had relatively high δ18O (as compared to older sedimentary rocks) by 2.43–2.35 Ga. The depositional time interval of the high-δ18O sedimentary sources for SPGs studied here coincides with the emergence of continental crust above sea level and the Great Oxidation Event. Supporting the findings of previous studies, the contemporaneity of our dataset with these changes in Earth's surface environments suggests that subaerial and potentially oxidative weathering contributed (at least partially) to the elevation of δ18O of fine-grained sedimentary rocks. Recycling of these high-δ18O sedimentary rocks into magmas contributed to the dramatic change in δ18O of magmatic zircon in the earliest Paleoproterozoic. In addition, although this study is focused on a single locality, our results suggest that the abrupt shift observed in global zircon δ18O data sets likely occurred by 2.35 Ga. Last, a literature compilation of zircon δ18O data from SPGs suggested that zircon δ18O values may have also experienced a stepwise increase in the Neoproterozoic to Phanerozoic from 12 to 14‰. The coincidence of these increases in zircon δ18O values with global oxygenation events suggests that atmospheric oxygenation may have contributed to the increase in δ18O of sedimentary rocks. [ABSTRACT FROM AUTHOR]

To investigate the behavior of Li isotopes during magmatic differentiation and the petrogenesis of Cu-bearing ore deposits, a suite of post-collisional adakitic rocks from Qulong region, southern Tibet, was studied. Their lithologies range from diorite through granodiorite to granite porphyry with the latter containing giant Cu deposits. Detailed evidence of field observation and geochemical signature suggest that these three sets of rocks were most likely formed by various degrees of partial melting and fractional crystallization from the same source. The dioritic enclave, granodiorite and granite porphyry have δ7Li values ranging from 0.2 to 8.2‰, 3.1 to 6.8‰, and 3.9 to 7.4‰, respectively. Most of these samples are overlapping in Li isotope composition, comparable to other granitoids worldwide, indicating insignificant Li isotope fractionation during partial melting and magma differentiation in adakite-like rocks. By contrast, their Li concentrations are mainly controlled by fractional crystallization as suggested from different modal mineralogy. This process does not lead to further enrichment of Cu although they have initial high concentrations (an average of ∼ 104 ppm). In comparison, granite porphyry has extremely high Cu contents (up to 2000 ppm) and their δ7Li values are positively correlated with Cu content, suggesting the involvement of magmatic fluids that most likely exsolved from deep magma chamber. Such fluids not only modified the Li isotopic compositions of granite porphyries, but also extracted metal elements from the highly evolved magma, eventually resulting in the Cu mineralization. Our work here provides new insight into the formation and evolution of the porphyry Cu-bearing deposit. [ABSTRACT FROM AUTHOR]

Studies of heat and mass transport in hydrothermal systems are challenging owing to the complex feedback that exists between chemical and physical processes. Taking full advantage of the existing geochemical framework recently recognized for sublacustrine vent fluids in the Stevenson Island Deep Hole, Yellowstone Lake, here we apply a multiphase reactive transport model, coupling hydraulic and thermal effects, to simulate time series changes in mineralization associated with venting of vapor-dominated hydrothermal fluids. This distinctive region of the lake floor is characterized by a series of overlapping depressions hosting sites of active venting. Model results show that the addition of high enthalpy steam enriched in CO 2 and H 2 S, creates acidic and reducing conditions, while heating entrained lake water and coexisting sediment to temperatures in excess of 174 °C. The diatomaceous silica-rich substrate is predicted to dissolve, being replaced largely by pyrite, quartz, and kaolinite, in good agreement with the observed vent mineralization and fluid chemistry. Data suggest that vent-related mineral dissolution and transformation processes occur rapidly, on the order of 1 ka for the spatial scale of the modeled-up flow zone considered. The accuracy of time series changes predicted however, is explicitly linked to a number of physical and chemical factors imposed on the model, including source fluid, flow rate and gas enrichment, and sediment thermal conductivity, permeability, and reactive surface area, as well as mineral reaction rate data for primary and secondary alteration phases. When combined with robust field observations, as is the case here, reactive transport models can elucidate important, if not fundamental, controls on the temporal and spatial evolution of the geochemistry of modeled system, challenging chemical, and physical conditions notwithstanding. [ABSTRACT FROM AUTHOR]

The Plio-Pleistocene El Laco magnetite ore bodies in the Chilean Altiplano represent an unusual subvolcanic/aerial type of an iron oxide-apatite (IOA) deposit. The textures of these magnetite ore bodies have sustained a long-standing geological controversy on the origin of iron oxide deposits with models spanning the spectrum from purely igneous to magmatic-hydrothermal processes. In particular, the link between the geochemical processes taking place in the source magma and the subsequent evolution of the overlying magmatic-hydrothermal system are still not well understood. Here we address this problem by focusing on microtextural and geochemical features of iron ore and silicate gangue minerals retrieved from drill core samples from El Laco ore bodies, as well as from the andesite volcanic host rocks. We report a comprehensive geochemical dataset of magnetite assemblages at El Laco obtained using a combination of EPMA, LA-ICP-MS, and synchrotron radiation µ-XRF methods. Microtextural and geochemical data of magnetite reveal consistent variations with depth. Magnetite in the andesitic host rocks and from deep/intermediate levels of the ore bodies have a high concentration of trace elements including Ti, V, Ni, Mn, Zn, Cr, Al, Ga, Cu and Co in comparison with magnetite from the upper sections of the ore bodies. Clinopyroxene is present in the andesite host rocks as well as the ore bodies, showing chemical differences between both types, with Mn and Fe contents that are higher in the former, and Na and Ca concentrations enriched in the latter. We interpret the enriched-to-depleted compositional trends in magnetite and clinopyroxene as resulting from a transition from purely igneous conditions to a fluid-dominated, cooling magmatic-hydrothermal system. Detailed microtextural analysis of magnetite and clinopyroxene from the ore bodies support this notion, revealing multiple growth stages punctuated by dissolution-reprecipitation processes. Our data further supports a genetic model that explains the formation of the El Laco iron oxide deposit through the injection, upward migration and venting of magmatically-derived Fe-rich fluids. [ABSTRACT FROM AUTHOR]

Three sets of experiments were performed to test the stability and geologic importance of ferric (FeIII) chloride complexes in acidic, Cl-rich solutions at 150–300 °C, p = p sat. Experiment Set A used the change in solubility of AgCl(s) in the presence of FeCl 3 or FeCl 2 to determine the stoichiometry of Fe(III) and Fe(II) chloride complexes at ΣCl = 0.1–3.0 molal. Results show that FeCl 4 − and FeCl 2 (aq) are the dominant Fe(III) and Fe(II) species, respectively, at T > 200 °C and ΣCl ≥ 1 m. Set B experiments used the solubility of elemental gold as a redox sensor to determine the a O 2 of the FeCl 4 −/FeCl 2 (aq) boundary and log K values of +6.56 and +7.19 for the following reaction at 250 and 300 °C, respectively: FeCl 2 (aq) + ¼O 2 (g) + 2Cl− + H+ = FeCl 4 − + ½H 2 O(l). Ferric chloride complexes are stable under conditions of a Cl−, a O 2 , and pH where gold is soluble as AuCl 2 −. Set C experiments measured the solubility of hematite in NaCl-HCl solutions at 200–300 °C by preparing a series of silica tubes with identical matrix chemistry (0.9 m NaCl + 0.1 m HCl) and increasing concentration of FeCl 3. Hematite saturation was constrained by the tube with the lowest FeCl 3 concentration that precipitated hematite at high temperature. Set C results were used to compute log K values of +3.6, +5.2, and + 7.4 for the following reaction at 200, 250 and 300 °C, respectively: 0.5Fe 2 O 3 (s) + 4Cl− + 3H+ = FeCl 4 − + 1.5H 2 O. Hematite solubility as FeCl 4 − is independent of redox state, and increases quickly with an increase in temperature, increase in Cl− concentration (power of 4), and decrease in pH (power of 3). Concentrations in excess of 100 mg/L ΣFe are attainable under geologically realistic conditions. Once formed, FeCl 4 − is an extremely effective oxidizing agent, capable of destabilizing any sulfide mineral and dissolving Fe, Au, and other metals (e.g., Cu, Pt, Pd) as chloride complexes. In deep hydrothermal systems, FeCl 4 − is a more viable oxidant than dissolved O 2 gas, although its presence requires a source area with abundant hematite and a lack of reductants such as organic carbon, sulfides, or silicate minerals containing ferrous iron. Dissolved ferric chloride could be an important and previously overlooked reactant in the formation of certain types of hematite-rich hydrothermal mineral deposits, including iron oxide-copper–gold (IOCG) deposits. [ABSTRACT FROM AUTHOR]

The Marquesas islands are an age-progressive volcanic chain in French Polynesia formed by partial melting above a mantle plume. Previous studies have demonstrated the presence of an enriched mantle (EM2) endmember mixed with a high-3He/4He (up to 14.4 R A) component in Marquesas post-shield lavas. In contrast, Marquesas shield lavas sample a dilute high-μ (HIMU) type component with lower 3He/4He (∼8 R A). We report new incompatible trace element and highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances and osmium isotope data for bulk rocks from the islands of Fatu Hiva, Hiva Oa and Nuku Hiva, for which He, Sr, Nd and Pb isotope compositions have been reported previously (Castillo et al., 2007). As the HSE are chiefly hosted in sulfide phases in the mantle and all but Re are compatible during partial melting, they offer information on both sulfide-rich and melt-depleted mantle lithologies within the Marquesas plume. Primitive mantle-normalized HSE abundances show depletions in Ru and Pd, and fractionated (Ir/Os) N in fourteen of the seventeen analyzed samples. Ruthenium depletions and Ir-Os fractionations are likely caused by parental magma fractional crystallization. Palladium depletions are not easily explained by magmatic or secondary alteration processes and are instead likely to be a feature of the source mantle which was partially depleted in the more incompatible HSE by previous melting events within the Marquesas plume. Osmium isotopic systematics are mildly radiogenic relative to chondrites and are identical within uncertainties for shield-building Fatu Hiva (γOs = +2.9 ± 1.6; 2 SD; n = 7) and post-shield Hiva Oa (+2.7 ± 2.2; n = 9), showing no evidence for significant assimilation of radiogenic oceanic crust. The osmium budget of Marquesas lavas is controlled by a volumetrically dominant peridotite endmember that is incompatible element depleted while the Sr, Nd, and Pb budgets are strongly influenced by a volumetrically minor, incompatible element enriched EM2 component. The Nd-Sr-Os isotope systematics of the lavas can be explained by mixing of 0.3–0.7% of an EM2 type melt into the Marquesas source. Marquesas lavas offer further support that the high-3He/4He "focus zone" (FOZO) mantle has 187Os/188Os mildly more radiogenic than the depleted upper mantle, similar to estimates of the primitive mantle. Osmium isotope systematics offer a useful tool with which to characterize more depleted components within the ocean island basalt-source mantle that may be difficult to detect using lithophile isotope signatures. [ABSTRACT FROM AUTHOR]

Despite being volumetrically minor components, carbonate-rich ultramafic magmas like aillikites represent good candidates to investigate the compositional variations in plume and/or lithospheric mantle sources because they represent low-degree melts which preferentially sample highly fusible components including recycled crustal material. To gain new insights into the composition of the plume-related magmas and, more broadly, the petrogenesis of ultramafic lamprophyres, we have undertaken the first comprehensive study of bulk rock and mineral (olivine and Ti-magnetite) highly siderophile element (HSE) abundances and Re-Os isotopes combined with in situ major-, trace-element and Sr-Nd isotope analyses of apatite and perovskite from the Permian Wajilitag aillikites of the Tarim large igneous province, China. The Wajilitag aillikites have high PPGE (Pt and Pd) contents relative to IPGE (Os, Ir and Ru), which can be ascribed to low-degree partial melting and/or fractionation of olivine and laurite. Measured 187Os/188Os ratios are moderately to highly radiogenic (0.186–0.313) with age-corrected γOs values up to +113. In situ Sr and Nd isotope analyses of apatite phenocrysts (87Sr/86Sr (i) = 0.70349–0.70384; εNd (i) = +1.3 to +4.9) and fresh perovskite grains (87Sr/86Sr (i) = 0.70340–0.70390; εNd (i) = +1.3 to +3.8) exhibit limited variability both within and across samples from different aillikite dykes and the only volcanic pipe in the area. These Nd isotopic values resemble those from bulk-rock samples (εNd (i) = +1.9 to +5.2), whereas Sr in apatite and perovskite extends to marginally less radiogenic values than the bulk-rock compositions (87Sr/86Sr (i) = 0.70362–0.70432). The moderately depleted Sr-Nd isotope compositions of magmatic apatite and perovskite, and the previously reported mantle-like C isotope values of these samples suggest that the aillikites and their carbon probably derived from a sub-lithospheric (plume) source with minimal contribution of deeply subducted material. Conversely, the radiogenic Os isotope compositions of the Tarim aillikites and separated minerals require some contribution from recycled crustal material in the plume source. Mass balance calculations suggest that the radiogenic Os isotopes and moderately depleted Sr-Nd isotopes can be reproduced by less than one third of eclogite component addition to a moderately depleted mantle source. We conclude that the combination of complementary isotopic systems can enlighten contributions from different components to mantle-derived magmas and, in this case, clarifies the occurrence of carbon-free subducted oceanic crust in the Tarim plume. [ABSTRACT FROM AUTHOR]

The presence of tektite-like glasses from a geographically restricted area in Belize (Central America) has been known for several decades. We comprehensively studied 18 such Belize glasses by a variety of petrographic and geochemical methods, including major and trace element analysis, radiogenic isotopic composition (Rb-Sr, Sm-Nd, and Re-Os), water content, oxidation state, and cosmogenic radionuclides. The aims were to determine their compositional variation, their mode of formation and possible source rocks, and their relation to known tektites, and to search for evidence of an extraterrestrial component. In terms of petrography, the samples are similar to tektites from the four "classical" strewn fields, with the presence of lechatelierites, schlieren, and vesicles; these are also widely accepted indicators of an impact origin. No close similarities to volcanic glasses are evident. Water contents are very low, and iron oxidation states are mostly reduced, in both cases similar to observations for other tektites. The geochemical and isotopic data presented, such as Cr, Co and Ni elemental abundances and interelement ratios, as well as trace element patterns are typical for local and regional volcanics from the active Central American Arc. Particular similarities to material comparable to volcanic rocks from Honduras or Guatemala are noted. This is confirmed by Sr-Nd isotope signatures of the Belize glasses, showing close similarities to Central American volcanics in general, and Honduran and Guatemalan volcanic, in particular. Osmium concentrations and 187Os/188Os ratios are comparable to arc volcanics from world-wide locations, but - in a few of the samples - elevated Ir concentrations, near-chondritic Pt/Ir and 187Os/188Os ratios can also be interpreted with the admixture of a minor meteoritic component to some of the Belize samples. 10Be concentrations are consistent with values typical of both, young or deeply buried soils and with values for Central American volcanics, which carry subducted 10Be. Geochemical data clearly indicate a source different from that of the Australasian tektites. Both isotope data sets for the Belize glasses indicate a close relationship to local arc lavas, especially those from Guatemala and Honduras, suggesting that the glasses were not deposited very far from their source. The main evidence that the Belize glasses are of impact origin are their petrographic characteristics and low water content. The evidence from 10Be is consistent with, but does not require, a model of formation for the Belize glasses by an impact on loosely consolidated surface sediments exposed to rain. A probable meteoritic component is low and heterogeneously distributed. [ABSTRACT FROM AUTHOR]

Subduction of low-density continental crust to subarc depths is generally associated with preceding subduction of the oceanic slab. However, the original oceanic signature is often overprinted by subsequent fluid metasomatism from the subducting continental crust. As a result, it is generally difficult to trace the geochemical processes of previous oceanic subduction in collisional orogens. This issue can be potentially resolved by applying B isotopes to metamorphic rocks from continental subduction zones. Here a combined study of whole-rock geochemistry and in situ tourmaline B isotopes was carried out for coesite-bearing whiteschist and phengite schist, as well as country rock metagranitoids from the Dora-Maira Massif in the Western Alps. While all these metamorphic rocks have a similar protolith of Permian granites, whiteschist and phengite schist experienced Mg-rich fluid metasomatism during the continental subduction, evidenced by their much higher MgO contents than the metagranitoids. Tourmaline in the metagranitoid (Tur-G) is schorlitic (X Mg = 15–55) with low δ11B values from −13 to −6‰, and is consistent with a magmatic origin. In contrast, tourmaline in metasomatic rocks (Tur-S) is mainly dravitic with the highest X Mg worldwide (X Mg = 90–98) and high δ11B values of −5 to +1‰. Integrated with whole-rock geochemistry and previous studies, Tur-S is interpreted to grow during the infiltration of external fluids that were highly enriched in MgO and relatively enriched in 11B. According to the B isotope compositions of precursor tourmalines, it is estimated that the external fluids had significantly higher δ11B values than +2.4‰. Based on B isotope compositions of both Tur-S and metasomatic fluids, our quantitative modeling suggests that the metasomatic fluids most likely originated from the mantle wedge serpentinite that was formed during the preceding oceanic subduction stage. Therefore, tourmaline B isotopes in the ultrahigh pressure metamorphic continental crust can be used to trace preceding fluid metasomatism at the interface between oceanic slab and mantle wedge. The mantle wedge serpentinite plays an important role in modifying the geochemical composition of deeply subducted supracrustal rocks and probably also the mantle sources of arc magmas. [ABSTRACT FROM AUTHOR]

Although the heterogeneous nature of the chemical composition of Earth's mantle is now well established, the origin and longevity of the heterogeneities continue to be debated. In order to further study early-Earth heterogeneities, we present a set of Sm-Nd, Lu-Hf, Re-Os, and Hf-W isotope and lithophile and siderophile element abundance data for komatiites and basalts from the ∼3.53 Ga Coonterunah, ∼3.34 Ga Kelly, and ∼3.18 Ga Ruth Well and Regal systems of the Pilbara Craton in Western Australia. The Sm-Nd, Lu-Hf, and Re-Os isotope data yield isochrons consistent with the accepted emplacement ages of the respective komatiite-basalt lavas. The mantle sources evolved with long-term 147Sm/144Nd = 0.200 to 0.214 and 176Lu/177Hf = 0.0355 to 0.0395, spanning the entire range of the time-integrated Sm/Nd and Lu/Hf measured in the Archean and Proterozoic komatiite-basalt systems to-date. Unlike with the other early Archean komatiites and basalts, the coupled 143Nd-176Hf isotope systematics of the Pilbara lavas provide no evidence for the involvement of early magma ocean processes in the evolution of their mantle sources. Episodes of variable degrees of partial mantle melting and melt extraction can account for the observed large variations in the time-integrated Sm/Nd and Lu/Hf ratios in the early Archean mantle domains. In contrast to the highly variable Nd-Hf systematics, the initial γ187Os values vary within a narrow range from +0.9 to −0.4 indicating that the Pilbara mantle sources evolved with chondritic time-integrated Re/Os. The apparent discrepancy between the depletions in incompatible lithophile trace elements and near-chondritic Re/Os observed globally is reconciled via a model whereby early low-degree mantle melting events fractionated Sm from Nd and Lu from Hf, but had little effect on the Re/Os ratio. This in turn would imply early formation and long-term isolation of a basaltic crust highly enriched in incompatible lithophile trace elements. The calculated total HSE abundances in the komatiite mantle sources range from ∼30% in the Coonterunah to ∼70% in the Regal system, of those in the estimates for the modern BSE, indicative of a 2.4× increase in HSE abundances from 3.53 to 3.18 Ga. All four komatiite-basalt systems exhibit positive 182W anomalies ranging between +11.4 and +7.7 ppm. The 182W/184W compositions and calculated HSE abundances in the Pilbara komatiite-basalt sources are inversely correlated and are most consistent with grainy late accretion of large differentiated planetesimals. Regression of the combined 182W-HSE data for the komatiite systems allows an estimate of the W isotopic composition of the pre-late accretion BSE of +17 ± 7. This estimate is similar to that of the Moon of +25 ± 5 and lends further support to the notion regarding an initially common W isotopic composition in the Earth-Moon system. Regression of the available HSE abundance data for komatiite mantle sources worldwide provides an estimate for the time of complete homogenization of late accreted materials within the mantle by 2.5 ± 0.2 Ga. Calculations indicate an average survival time of late accreted planetesimals in the Earth's mantle of 1.9 ± 0.2 Ga, which constrains the average mantle stirring rates for the HSE in the Hadean and Archean. [ABSTRACT FROM AUTHOR]

The geochemistry of global mantle melts suggests that both mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) sample lithological and temperature heterogeneities originating in both the upper and lower mantle. Recently, non-traditional stable isotopes have been suggested as a new tool to complement existing tracers of mantle heterogeneity (e.g., major and trace elements, radiogenic isotopes), because mineral- and redox-specific equilibrium stable isotope fractionation effects can link the stable isotope ratios of melts to their source mineralogy and melting degree. Here, we investigate five stable isotope systems (Mg-Ca-Fe-V-Cr) that have shown promise in models or natural samples as tracers of mantle temperature and/or lithological heterogeneity. We use a quantitative model, combining thermodynamically self-consistent mantle melting and equilibrium isotope fractionation models, to explore the behaviour of the isotope ratios of these elements during melting of three mantle lithologies (peridotite, and silica-excess and silica-deficient pyroxenites), responding to changes in mantle mineralogy, oxygen fugacity, temperature and pressure. We find that, given current analytical precision, the stable isotope systems examined here are not predicted to be sensitive to mantle potential temperature variations through equilibrium isotope fractionation processes. By contrast, source lithological heterogeneity is predicted to be detectable in some cases in the stable isotope ratios of erupted basalts, although generally only at proportions of > 10% MORB-like pyroxenite in the mantle source, given current analytical precision. Magnesium and Ca stable isotopes show most sensitivity to a garnet-bearing source lithology, and Fe and Cr stable isotopes are potentially sensitive to the presence of MORB-like pyroxenite in the mantle source, although the behaviour of Cr isotopes is comparatively under-constrained and requires further work to be applied with confidence to mantle melts. When comparing the magnitude and direction of predicted equilibrium isotopic fractionation of peridotite and pyroxenite melts to natural MORB and OIB data, we find that aspects of the natural data (including the mean Mg-Ca-Fe-V isotopic composition of MORB, the range of Mg-Ca isotopic compositions seen in MORB data, the mean Mg-Ca-Cr isotopic composition of OIB, and the range of Mg-V-Cr isotopic compositions in OIB data) can be matched by equilibrium isotope fractionation during partial melting of peridotite and pyroxenite sources – with pyroxenite required even for some MORB data. However, even when considering analytical uncertainty on natural sample measurements, the range in stable isotope compositions seen across the global MORB and OIB datasets suggests that kinetic isotope fractionation, or processes modifying the isotopic composition of recycled crustal material such that it is distinct from MORB, may be required to explain all the natural data. We conclude that the five stable isotope systems considered here have potential to be powerful complementary tracers to other geochemical tracers of the source lithology of erupted basalts. However, continued improvements in analytical precision in conjunction with experimental and theoretical predictions of isotopic fractionation between mantle minerals and melts are required before these novel stable isotopes can be unambiguously used to understand source heterogeneity in erupted basalts. [ABSTRACT FROM AUTHOR]

The chemical composition of foraminiferal calcite reflects seawater variables and is therefore a popular paleoceanographic tool. The sedimentary record of foraminiferal shell chemistry is, however, mostly interpreted using empirical calibrations. Since geochemical patterns in foraminifera often deviate from inorganic analogues, there is an ongoing need for a more mechanistic understanding of foraminiferal biomineralization. One of the most elusive, but potentially important parameters characterizing foraminiferal biomineralization is the rate of calcite precipitation. Using a combination of labelling experiments and sub-micrometer imaging of the incorporated label with NanoSIMS, we show that the benthic foraminifer Ammonia beccarii precipitates its calcite at a rate of ∼24 ± 4 nmol/cm2/min. These values are close to maximum reported rates for inorganic calcite precipitation from Mg-depleted seawater, which is consistent with the strong fractionation against Mg during biomineralization. At the same time, the measured precipitation rate is in accordance with the similarity between the foraminiferal Sr/Ca values and ratios from calcite precipitated inorganically at these rates. Our results also show that the observed precipitation rate is surprisingly uniform among specimens and within chamber walls, indicating that the small-scale element banding is not reflecting variability in precipitation rate. Based on our results, we present a conceptual model where foraminiferal calcification is characterized by two major processes: first, active ion transport determines the composition of the calcifying fluid, whereas thermodynamics and process kinetics dictate fractionation and partitioning during the subsequent calcium carbonate precipitation. This model also accounts for a role of seawater transport, which may be important in the first steps of calcification to explain geochemical signatures of other foraminiferal taxa. [ABSTRACT FROM AUTHOR]

Rare Earth Elements, including the lanthanide series and Y (REYs), are important tracers and paleo-proxies of biogeochemical processes, water mass transport and oceanic mixing. At the interface between the continents and oceans, the geochemical behaviour of REYs in estuarine environments is generally described as being non-conservative, with large-scale removal by particle scavenging. This conventional interpretation stems from observations carried out in tropical or sub-tropical estuaries. However, major river systems in the mid- and high latitude regions are subjected to winter conditions when a frozen watershed and an ice cover may affect the continental input of particles and the REY geochemistry. Here, we investigate the geochemical behaviour of REYs in the Estuary and Gulf of St. Lawrence (EGSL) in spring 2003 as well as winter and summer 2020. In contrast to the ice-free seasons, REYs and Fe behave conservatively in the estuary during the winter. In addition, we observed a higher REY affinity toward particle surfaces and fractionation in REE patterns in the hypoxic deep waters of the estuary. The latter observation may reflect enhanced REY sorption to mineral-carrier surfaces exposed upon the remineralization of organic coatings on settling particles and to manganese oxides of benthic origin. Computed partition coefficient (K d) values and strong correlations between Y/Ho, Er/Nd and Ce anomalies with dissolved oxygen concentrations support this hypothesis. The estimated annual dissolved load of REYs from the EGSL to the ocean ranges from 0.4 to 75 tons per year, thus contributing significantly to the global marine budget. The global river loading of dissolved Nd to the ocean was also revised to 4000 tons per year based on data available for 21 river systems. [ABSTRACT FROM AUTHOR]

Direct studies of recent epeiric seawater chemistry and their geological significance are relatively few compared to the far more abundant studies from ancient epeiric marine carbonates. Acknowledging the limitations of analogue studies in the modern glaciated world, we propose that the recent Abu Dhabi offshore and lagoonal areas share important attributes with the shallow-marine coastal zones of a subtropical epeiric carbonate sea. The study area in Abu Dhabi is dwarfed by the vast epeiric seas of the geological past, but its seawater properties and related geochemistry have relevance for paleoenvironmental interpretations for similar ancient systems. This study documents the geochemical properties of seawater along the Abu Dhabi coast, and discusses their trends within a spatial context. Results show a positive correlation between salinity, temperature, elemental concentrations, and oxygen isotopic composition of seawater, indicating a significant influence of evaporation on seawater chemistry. A distal-to-proximal negative correlation between seawater Mg/Ca and Sr/Ca ratios may be related to a landward increase in abundance of high-Mg calcite foraminifera. After normalization to chloride, seawater elemental (Ca2+, Mg2+, Sr2+) concentrations and alkalinity show decreasing trends in a landward direction, consistent with seawater aging from the open marine to restricted lagoonal settings. Lower ΔAlk (alkalinity change) : ΔCa2+ (Ca2+ change) ratios in seawater compared with the theoretical value, and more negative δ13C DIC values relative to typical (sub)tropical oceans in the study area indicate an influence of factors apart from CaCO 3 precipitation on properties of aged seawater. An input of alkalinity and 12C-enriched carbon by organic carbon decomposition (via sulfate reduction) during early diagenesis is proposed to account for these deviations from typical values. The input of alkalinity and 12C-enriched carbon by organic carbon decomposition may be further related to reduced seawater p CO 2 and early-marine cementation. Findings discussed here suggest that organic carbon decomposition during early-marine diagenesis may influence the geochemical properties of the coastal areas of shallow epeiric seas, and thus assumedly produce significant differences in proxy data compared with those from carbonates deposited in open oceans. [ABSTRACT FROM AUTHOR]

Although forming one unified class, orogenic gold deposits may be associated with a range of ore mineral assemblages controlled by a variety of gold deposition processes that have a direct impact on gold grade. Whereas, a better understanding of the deposition process may be critical for effective targeting of highly-endowed gold deposits, it is challenging to establish a direct comparison between mineral systems formed under different conditions. Accordingly our ability to predict whether contrasted mineral associations may be more or less prospective for high grade mineralization remains poor. In this paper, we compare fluid-rock interaction processes that led to the coeval formation of two contrasting gold mineral assemblages within the world-class Callie orogenic gold deposit. Stratabound and vein-hosted lodes formed within the same structural framework but with contrasting grades (∼3 g/t Au and ∼8 g/t Au, respectively). The stratabound mineralization consists of bedding-parallel sulfides in which gold is preserved in arsenopyrite micro-fractures. The vein-hosted mineralization consists of locally very high-grade (up to 10,000 ppm Au) visible gold concentrated in quartz veins. Both mineralization styles are hosted within different metasedimentary stratigraphic horizons with contrasting compositions. The stratabound mineralization occurs in iron-oxide rich siltstones whereas the vein-hosted mineralization occurs in carbonaceous siltstones. We investigate the fluid-rock interaction mechanisms of the two styles of mineralization at the Callie deposit by combining petrographic observation with whole-rock geochemistry, quantitative chlorite and gold analyses and thermodynamic modeling. Our results show that the stratabound mineralization occurred in response to sulfidation of the host-rock whereas decarbonation alteration, associated with the vein-hosted mineralization, records oxidation of the host-rock. Our investigation shows that gold deposition induced by oxidation of the host-rock produces the valuable, locally very-high grade visible gold mineralization whereas the sulfidation process lead to the formation of lower grade gold mineralization disseminated within the sulphide ore assemblage. We conclude that the nature of the host-rock applies a first-order control on the gold deposition efficiency in metasedimentary-hosted gold deposits. [ABSTRACT FROM AUTHOR]

Relatively little is known about the deep water circulation and the role of deep weathering processes on the Critical Zone (CZ) evolution. In this study, major fractures from four deep boreholes and water collected from these fractures (20–60 m of depth) were studied to improve our understanding of the deep CZ in a granitic headwater watershed (Strengbach watershed, France). Geochemical analysis indicates that chemical composition of deep water (20–60 m) is clearly different than shallow subsurface waters (0–15 m), with higher mean concentrations and a stronger spatial variability across the watershed. Reactive-transport modeling performed with the 1D KIRMAT code (KInetic of Reaction and MAss Transport) highlights the role of minor mineral dissolution (i.e. dolomite) and of longer mean transit time (100–597 yr) along fractures for explaining these differences. The obtained results also shed light on the difference of hydrogeochemical functioning between shallow subsurface system (water sampled from springs and piezometers) and deep system (deep water from borehole fractures). The shallow subsurface system (0–15 m) is characterized by a spatially relatively homogeneous water flow, high mean pore velocities, and water–rock interactions in a porous regolith, while the deep water circulation (20–60 m) behaves much more as independent systems along fractures, with low mean pore velocities, and variable mineralogy and hydrodynamic conditions. A state of chemical equilibrium can also be reached along fractures in the deep CZ for some primary minerals (biotite and K-feldspar), a feature never observed so far in the simulations of shallow subsurface water chemical composition in the Strengbach watershed. Even if the deep water exhibits higher solute concentrations, significantly lower mean pore velocities inferred in the fractured zones imply that the deep water is responsible for a very small part of the total hydrologic and weathering fluxes in the watershed. The limited role of the deep weathering processes (20–60 m) compared to the shallow subsurface processes (0–15 m) suggests an up to bottom control of the CZ evolution at a millennial timescale. Our results also indicate that the majority of fresh water available for water supply at a human timescale originates from shallow subsurface waters, as the deep water circulation is too low for being critical at a timescale relevant for societal needs in this type of geological context. [ABSTRACT FROM AUTHOR]

Molybdenum (Mo) and tungsten (W) concentration patterns and isotope signatures are widely used to study changes in ocean redox conditions. This is in part due to the differential adsorption of Mo and W onto various types of minerals that are abundant under different redox regimes. The speciation of Mo and W, which also varies under different redox conditions, greatly controls their particle reactivities in the environment. Manganese (Mn) oxide minerals can not only provide surfaces for Mo and W adsorption, but also catalyze Mo and W speciation change. Thus, the Mn oxides that are often present at redox interfaces can play an important role in Mo and W speciation change. However, we lack knowledge of how rates for Mn oxide catalyzed Mo and W speciation transformation compare to rates for their adsorption and isotope fractionation processes, which creates uncertainty in our ability to interpret Mo and W concentration and isotope patterns in sediments and sedimentary rocks. Here, we present data that constrain rates, environmental controls, and mechanisms for tetrathiomolybdate (MoS 4 2–) and tetrathiotungstate (WS 4 2–) hydrolysis on Mn oxide surfaces, which transforms the thioanion species to oxyanion species. The experimental results show that hydrolysis rate constants for these Mo and W thioanions are first order with respect to Mn oxide surface areas. Hence, high abundance of Mn oxides in aquatic environments greatly catalyzes MoS 4 2– and WS 4 2– hydrolysis. In addition, experimental results indicate that crystal structure differences of Mn oxides contribute to differences in rates for Mo and W thioanion hydrolysis reactions. Solution pH and ionic strength have limited impacts on Mo and W thioanion hydrolysis rates catalyzed by Mn oxides, while sulfate has a moderate impact. Geochemical modeling results indicate that equilibrium times for MoS 4 2– and WS 4 2– hydrolysis reactions in the presence of Mn oxides at abundances found in the modern ocean are three orders of magnitude longer than those for adsorption and isotope fractionation of Mo and W on Mn oxide surfaces. This implies that Mn oxides play a larger role in affecting adsorption and isotope fractionation processes than Mo and W speciation transformation in the modern, well-oxygenated ocean. In contrast, the potentially high levels of dissolved Mn(II) in the Archean ocean would have shortened the equilibrium time for Mo or W speciation transformation such that this process could compete with their adsorption and isotope fractionation processes, and subsequently affect sedimentary Mo and W isotope records. The impact of dissolved Mn(II) catalyzed Mo and W speciation change should be considered in future studies of Archean Mo and W isotope records. [ABSTRACT FROM AUTHOR]

Silicate weathering is a critical process in Earth's carbon cycle, but the fundamental controls on weathering are poorly understood and its response to future climate change is uncertain. In particular, the potential for changes in seasonality or extreme weather events to control silicate weathering rates or mechanisms has been little studied. Here, we use lithium (Li) isotope measurements in bimonthly sampled drip-waters from two caves in the Yorkshire Dales (U.K.) to assess the response of silicate weathering processes to changes in temperature and hydrology over seasonal timescales. While the caves are contained in limestone bedrock, the drip-water Li isotope signal predominantly reflects silicate weathering of the overlying soils that are dominated by glacial till. Drip-water Li isotope compositions record spatial and temporal variability ranging from δ7Li values of +1 to +17‰, with a mean of +11‰. These values are significantly higher than local lithogenic inputs (δ7Li = −1 ± 1‰), consistent with isotope fractionation during secondary mineral formation. Comparison to temperature, precipitation, drip rates, and drip-water chemistry enables the controls on the Li isotope weathering signatures to be explored, revealing possible roles for both temperature and fluid residence time in setting the balance between primary rock dissolution and secondary mineral formation. Specifically, our Li isotope data are consistent with a scenario in which cooler temperatures and/or longer fluid residence times lead to enhanced secondary mineral formation relative to silicate dissolution. Overall, our results indicate the potential for Li isotope variability over short temporal and spatial scales, which is important to consider when interpreting past changes in weathering processes or fluxes from paleo-records. In addition, the seasonal changes in Li isotopes suggest that weathering processes may be sensitive to seasonality or to extreme weather events, rather than responding only to the mean climate state. With warmer temperatures and more intense rainfall events expected in future, both increased primary rock dissolution and enhanced weathering efficiency (due to reduced secondary mineral formation) could potentially contribute to increased carbon dioxide drawdown by silicate weathering. [ABSTRACT FROM AUTHOR]

• We report the first mantle degassing transect across a continental convergent margin. • Three levels of mantle He degassing are recognized based on 3He/4He distribution. • Causes for possible decoupled He-Sr isotopes of Quaternary basalts are explored. • Volatile origin and outgassing are controlled by continental convergence processes. Mantle degassing transect across different tectonic units within a plate convergent setting has been well documented for oceanic convergent margins by systematic changes in geochemistry (e.g., 3He/4He, δ13C, and CO 2 /3He) of hydrothermal gases. However, little is known about spatial variations in volatile geochemistry across a continental convergent margin. In this study, we identify a mantle degassing transect in the southeastern Tibetan Plateau using He-CO 2 systematics of hydrothermal gases, which extends from India-Asia continental convergent margin to intra-continent extensional region. δ13C-CO 2 (−11.8‰ to −3.1‰) and CO 2 /3He (1.7 × 108 to 7.1 × 1011) values of hydrothermal gases show large variations that are consistent with modification by secondary physico-chemical processes, such as multi-component mixing, hydrothermal degassing, and calcite precipitation. Three levels of He degassing can be recognized based on 3He/4He dataset (0.01–5.87 R A) of the hydrothermal gas samples and their distances to volcanic centers. A magmatic level He degassing (35–74% mantle He) is found near active and/or Quaternary volcanoes fed by mantle-derived magmas. With increasing distance to volcanic centers, the outgassed magmatic volatiles are gradually diluted by crustal components (e.g., radiogenic 4He), defining a transitional level He degassing (13–33% mantle He). The 3He/4He values (8.16–8.48 R A) of olivine phenocrysts indicate a MORB (mid-ocean ridge basalts)-type mantle source for the magmatic and transitional levels of He degassing that are localized in Quaternary volcanic fields. In contrast, a background level He degassing (<12% mantle He) dominates the entire study area, and can be attributed to (i) degassing of sub-continental lithospheric mantle, and/or (ii) higher degrees of crustal contamination than those of the transitional level He degassing near volcanic centers. Combined with olivine 3He/4He data reported in this study and whole-rock 87Sr/86Sr data of host basalts from literature, source components of the mantle-derived magmas are suggested to include the MORB-type convective mantle, subducted Indian slab materials, and less degassed mantle materials, which can account for the possible decoupling between He and Sr isotope systematics. These findings delineate the origin and outgassing of mantle volatiles controlled by the India-Asia continental convergence, and would contribute to a better understanding of the deeply-sourced volatile emissions in these tectonic settings. [ABSTRACT FROM AUTHOR]

Diversity, at every step along the scientific path, drives innovative research. Scientific societies, like the Geochemical Society (GS) and the European Association of Geochemistry (EAG), have a significant influence over which discoveries and innovators are celebrated. Such choices impact the future of research, and therefore influence the evolution of our discipline and its relationship to the global community. Our professional societies are well positioned to define and promote the success of all scientists, including those from under-represented groups, through proactive advocacy, inclusive mentorship, awards, and leadership. At present, only binary gender data are available to examine the distribution of under-represented groups among memberships, awardees, and leadership positions. To assess gender diversity in the geochemistry and cosmochemistry community, we have reviewed available records of GS and EAG membership through Goldschmidt Conference attendees, and compared these to awardees and leadership data. Awards have in the past been disproportionately given to white men, though this is changing. The GS and EAG have taken positive steps to increase both diversity of awardees (e.g., broadened definition of Fellows criteria) and inclusion (e.g., mentoring efforts aimed at early career and underrepresented minority scientists). This work identifies strategies to continue to improve professional societies' recognition of excellent science resulting in a more diverse representation of awardees. The strategies (e.g., revisions to award criteria and procedures to enlarge and diversify nomination pools) will require ongoing analysis and modifications. Future work is needed to address historically under-represented groups. We must work together to create a legacy of inclusion. [ABSTRACT FROM AUTHOR]

• Peatlands with similar geology, climate and Hg deposition differed in MeHg formation. • Vascular plant removal did not affect net MeHg formation or porewater geochemistry. • Electron donors, acceptors and bioavailable Hg correlated with net MeHg formation. • Short-term resource supply responses deviated from those caused by natural processes. A geographically constrained chronosequence of peatlands divided into three age classes (young, intermediate and old) was used to explore the role of biogeochemical influences, including electron donors and acceptors as well as chemical speciation of inorganic mercury (Hg(II)), on net formation of methylmercury (MeHg) as approximated by the fraction of MeHg to total mercury (THg) in the peat soil. We hypothesized that removing vascular plants would reduce availability of electron donors and thus net MeHg formation. However, we found no effect of the vascular plant removal. The sum of the potential electron donors (acetate, lactate, propionate and oxalate), the electron donation proxy organic C/Organic N, and the potential electron acceptors (Fe(III), Mn and sulfate) in porewater all showed significant correlations with the net MeHg formation proxies in peat soil (MeHg concentration and %MeHg of THg). Thus differences in both electron donor and acceptor availability may be contributing to the pattern of net MeHg formation along the chronosequence. In contrast, Hg(II) concentrations in peat porewater showed small differences along the gradient. A chemical speciation model successfully predicted the solubility of Hg and MeHg in the porewater. The modeling pointed to an enhanced concentration of Hg-polysulfide species in the younger peatlands as a potential factor behind increased Hg(II) solubility and methylation in the more nutrient-rich peatlands. This work contributes to the understanding of Hg and MeHg cycling in peatlands which can help guide mitigation measures to reduce aquatic MeHg biomagnification in peatland dominated landscapes. [ABSTRACT FROM AUTHOR]

The abundant occurrence of calcium carbonate minerals in marine sediments and their high fluorine content suggests that fluorine is a good candidate for reconstructing paleoceanographic parameters. However, the potential of fluorine as a paleoproxy had hardly been explored, and fundamental insights into the behaviour of fluorine in biogenic carbonates and marine sediments is required. A first-principles modelling approach is used here to analyse the incorporation mechanisms of fluorine into crystalline calcium carbonates. We compute F incorporation into the CaCO 3 lattice via a number of mechanisms, but concentrate on comparison of the energetics of the two easiest substitution mechanisms: replacing one oxygen atom within the carbonate group to form a (CO 2 F)− group as against a substitution involving replacement of the CO 3 group by two fluorine ions to form a CaF 2 defect. These incorporation mechanisms are fundamentally different from that of iodine into calcium carbonates, where a carbon atom is replaced. Our simulations suggest that the substitution of CO 3 2 - by F 2 2 - is the most favoured and that fluorine is preferentially incorporated into the three naturally-occurring polymorphs of calcium carbonate in the order vaterite ⪆ aragonite ≫ calcite. These results explain the previously-reported preponderance of fluorine in aragonite corals, and lend support to the use of F/Ca as a proxy for ocean p CO 2. [ABSTRACT FROM AUTHOR]

The South Pacific Superswell in Polynesia is associated with a large seismic mantle anomaly at depth, the Polynesian dome, and it is characterized by the volcanic activity of five different hotspots giving birth to the Marquesas, Society, Pitcairn-Gambier, Cook-Austral and Arago island chains. Here we present new isotopic and major and trace element data in basalts from two of these chains, the Society and Pitcairn-Gambier chains, in order to examine the similarities and differences of their mantle source regions. In the Society chain the entire geochemical diversity of the archipelago exists at the scale of individual islands with no systematic trend over time. In contrast, a clear geochemical dichotomy exists along the Pitcairn-Gambier chain between the old volcanoes (Muru basalts from Mururoa, Fangataufa, Gambier, >5 My) and their younger counterparts (Pitis basalts from Pitcairn Island and Seamounts, <1 My). The Muru group has high Nb N /Nb* and Ce/Pb, low 87Sr/86Sr and define a steep trend in Nd-Hf isotopic space, features that call for old eclogite in their mantle source. The unradiogenic Pb isotopic ratios of Muru basalts, well below the values observed in HIMU ("high µ", or high 238U/204Pb) localities, are not easily explained by varying the age and composition of the eclogite and may call for the involvement of Pacific lower mantle in the source region. In contrast, the Pitis basalts share with the Society basalts low Nb N /Nb* and radiogenic 87Sr/86Sr suggesting incorporation of continental material in their source region. While the Society source simply incorporates modern-like terrigenous sediments, the combination of low Ba/La, 143Nd/144Nd and 176Hf/177Hf and very high 208Pb*/206Pb* in Pitis basalts make the Pitis source unique and not sampled anywhere else on Earth. The Pitis source contains old, possibly Archean, material of unclear origin because it resembles neither modern lower continental crust nor modern pelagic sediments. Finally, the distribution of heterogeneities in the two mantle plumes is also very different: discrete filaments are randomly dispersed across the Society plume stem while eclogitic and continent-derived filaments are vertically separated under the Pitcairn-Gambier chain. By combining these results with those published for other Polynesian chains, we establish a snapshot of the composition, geometry and distribution of the crustal components present in the Polynesian dome. [ABSTRACT FROM AUTHOR]

• The Itasy volcanic field has experienced abundant Pleistocene monogenetic volcanism. • Itasy magmas have geochemical signatures similar to ocean island basalts. • Itasy magmas are produced by melting of upwelling polluted asthenospheric mantle. • The Itasy magmas may be sourced in part by mantle related to the African superplume. We present new major and trace element and Sr, Nd, Pb, Hf, and Os isotope data for Quaternary basaltic lavas and tephra from the Itasy volcanic field, in order to assess the origin and sources of recent volcanism in the central highlands of Madagascar. Our age determinations provide further evidence for Pleistocene volcanism on the island, with ages between ∼31 and 104 ka. Mafic magmas from Itasy exhibit significant geochemical heterogeneity, and they are chemically distinct from those of the neighboring Ankaratra volcanic complex. Trace element signatures of the Itasy volcanic field are very similar to those of ocean island basalts (OIB), with significant enrichment in high field strength elements (e.g. Nb and Ta) and depletion in large ion lithophile elements (e.g. Rb, Cs, and K), and relatively high Nb/U (>45) and Ce/Pb (>25) ratios. Significant intra-volcanic field isotopic heterogeneity is observed, with well-defined negative correlations of 87Sr/86Sr with 206Pb/204Pb and 143Nd/144Nd. These correlations, along with highly radiogenic Os isotopic signatures in many Itasy samples, could be attributed to assimilation of the Precambrian basement. However, with the exception of Os, the elemental and isotopic characteristics of the Itasy magmas are inconsistent with significant crustal assimilation, and instead are interpreted to represent features of their mantle sources. The Itasy Δε Hf and Δ7/4 values fall within the range of MORB and OIB, and indicate derivation primarily from an asthenospheric mantle source. The absence of significantly negative Δε Hf in the Itasy magmas argues against the involvement of ancient recycled oceanic crust or stranded lower crust in their sources, but the presence of a low µ (LOMU) component in some Itasy magmas can be attributed to pollution of the asthenosphere by delaminated subcontinental lithospheric mantle. A simple two-stage, three-component mixing model indicates that a mixture of mantle containing 90% depleted asthenosphere (DMM) and 10% foundered SCLM, which is further mixed with 30 to 50% of a plume-type mantle component, can reproduce the isotopic compositions of the Itasy magmas. Based on our model, it is possible that easily fusible superplume materials might be widely distributed in the upper mantle underneath the EARS, from the Indian Ocean to the Red Sea-Gulf of Aden, and mixed with shallow asthenosphere that has itself incorporated eroded SCLM. These components are heterogeneously distributed at a small spatial scale, similar to that observed recently in other mafic monogenetic volcanic fields in both intraplate and subduction settings. [ABSTRACT FROM AUTHOR]

Degradation of inshore water quality associated with catchment modification is threatening global coral reef ecosystems. Coral trace element proxies are widely applied to document the magnitude and timing of historical changes in river runoff and other disturbances. However, conflicting interpretations of commonly used coral proxies (Ba/Ca, Y/Ca and Mn/Ca) complicate their application for examining historical changes in coastal water quality. The exploration of other coral trace element proxies (such as rare earth elements, REE) is limited in space and time, and to few coral genera. This study examined the dynamics of dissolved REE and yttrium (REEY) in the Fitzroy and Burdekin river tributaries and estuaries, Queensland, Australia. In addition, monthly-resolution long-term temporal records of Ba/Ca, Mn/Ca, Y/Ca and REEY proxies were investigated in two Porites and one Cyphastrea coral colonies from the central and southern Great Barrier Reef in order to test the reliability of these proxies to record the variability of river runoff and local anthropogenic disturbances. The results showed large scale removal of REEY (55–86%) in the low salinity mixing zones of both estuaries with significant fractionation of Nd-Yb and Y-Ho, confirming the ability of coral REEY to act as a terrestrial runoff proxy. Coralline Ba/Ca, Y/Ca and Mn/Ca records generally lack coherence with proximal discharge. However, temporal fluctuations of REEY proxies, irrespective of geographic location and coral genus, showed consistent behaviour relative to regional discharge with progressive increase of total REE/Ca and shale normalized Nd/Yb and decrease of Y/Ho during high-flow summer periods. The shifting baselines of REEY proxies in Cyphastrea grown in the turbid water setting of Rat Island effectively captured the timing of Gladstone Port dredging activities. Our findings suggest that shale normalized coral REEY distributions outperformed other commonly used trace element proxies and are robust indicators of changing inshore water quality. Longer-term records of coral REEY, even covering the period before European settlement from the 1850s, may provide a means to identify shifting baselines and evaluate and quantify the impacts of catchment alteration on coastal water quality and specific coral reef communities. [ABSTRACT FROM AUTHOR]

Iron minerals are the most important arsenic host in As-contaminated deltaic sediments. Arsenic release from Fe minerals to groundwater exposes millions of people worldwide to a severe health threat. To understand the coupling of Fe mineralogy with As (im)mobilization dynamics, we analyzed the geochemistry and mineralogy of a 46 m long sediment core drilled into the redox transition zone where a high As Holocene aquifer is juxtaposed to a low As Pleistocene aquifer in the Red River delta, Vietnam. We specifically concentrated on mm- to cm-scale redox interfaces within the sandy aquifer. Various Fe phases, such as Fe- and Mn- bearing carbonates, pyrite, magnetite, hematite and Fe-hydroxides (goethite, lepidocrocite) with distinct As concentrations were identified by a combination of high-resolution microscopic, magnetic and spectroscopic methods. The concentration of As and its redox species in the different Fe-minerals were quantified by microprobe analysis and synchrotron X-ray absorption. We developed a conceptual model integrating Fe-mineral transformations and related As (im)mobilization across the redox interfaces. Accordingly, As is first mobilized via the methanogenic dissolution of Fe(III) (oxyhydr)oxide mineral coatings on sand grains when reducing groundwater from the Holocene aquifer intruded into the Pleistocene sands. This stage is followed by the formation of secondary Fe(II)-containing precipitates (mainly Fe- and Mn-bearing carbonates with relatively low As < 70 μg/g), and minor pyrite (with high As up to 5800 μg/g). Due to small-scale changing redox conditions these Fe(II) minerals dissolve again and the oxidative behavior of residual Fe(III)-phases in contact with the reducing water leads to the formation of abundant Fe(III)/Fe(II) (oxyhydr)oxides especially at the studied redox interfaces. Microcrystalline coatings and cementations of goethite, magnetite and hematite have intermediate to high As sorption capacity (As up to 270 μg/g) creating a key sorbent responsible for As (im)mobilization at interfingering redox fronts. Our observations suggest a dynamic system at the redox interfaces with coupled redox reactions of abiotic and biotic origin on a mm to cm-scale. In a final stage, further reduction creates magnetite with low As sorption capacity as important secondary Fe-mineral remaining in reduced gray Pleistocene aquifer sands while considerable Fe and As is released into the groundwater. The presented redox-dependent sequence of Fe phases at redox interfaces provides new insights of their role in As (im)mobilization in reducing aquifers of south and southeast Asia. [ABSTRACT FROM AUTHOR]

• Partition coefficients Kd for 58 elements are reported for volcanic gas – melt system. • Observed partition coefficients are almost indistinguishable from equilibrium ones. • Element properties, S and Cl contents and f O 2 of the gas are factors to determine Kd. By comparing high-quality volcanic gas and whole rock compositions, we calculated the apparent (observed) mass partition coefficients Kd * for 58 elements on six basaltic volcanoes located in arc and rift/hotspot settings. The inferred Kd * vary from ∼1100 for sulfur to 0.0001 for zirconium, i.e., within seven orders of magnitude. Only 14 elements have Kd * > 1, including highly volatile S, Se, Te and halogens, as well as Tl, Re, Os, Bi, Cd, Au, In and As. Alkali metals have Kd * in the range from 0.1 for Cs to 0.01 for Na. Partition coefficients of other rock-forming elements are <0.001. The partition coefficients for elements depend on element speciation and concentrations of ligand-forming elements in the gas such as sulfur and chlorine. Elements transported in the gas predominantly as halides have higher partition coefficients in HCl-rich arc gases, whereas elements preferably forming sulfides, hydrides and free atoms, have higher Kd * in sulfur-rich, HCl-poor and reduced rift/hotspot gases. Degassing directly from the free melt surface is negligible; deep gas passing through the erupting vent is quickly overwhelmed by the signal of low-pressure degassing. Equilibration of rising bubbles with the surrounding melt almost eliminates the difference between Kd * calculated for degassing lava flows (no connection with deep magma) and for lava lakes and open-vent volcanoes (convective mass exchange with deep magma takes place). Diffusion does not strongly affect the apparent partitioning of magmas degassing at surface. Gas bubbles growing in near-surface silicate melts at atmospheric pressure have a large density difference compared to the surrounding melt of 12–15 thousand times. This leads to the rapid expansion of such bubbles and a decrease in the thickness of the diffusion boundary layer in the melt due to its stretching around the growing bubble, which sharply decreases diffusion fractionation. As a result, the apparent partition coefficients (Kd *) for degassing basaltic volcanoes are close to the equilibrium ones (Kd) for most of the elements. The partition coefficients of volatile elements (S and Cl) calculated from the comparison of volcanic gas and rock compositions are in agreement with the values determined previously via experiments or theoretical modeling. [ABSTRACT FROM AUTHOR]

Redox-sensitive trace metal concentration patterns have been widely used to track redox conditions in aquatic environments. Among redox-sensitive trace metals, molybdenum (Mo) is of interest owing to its speciation behavior and associated changes in particle reactivity that cause significant changes in concentration patterns in oxic versus sulfidic conditions. However, current understanding of how to use Mo geochemistry of marine sediments as a paleoredox proxy is limited to determining presence or absence of, and in some cases the aerial extent of, sulfidic conditions in the past. Here, we present a combination work of field sampling analysis and experiments to link concentration patterns of another redox-sensitive trace metal, tungsten (W), to Mo in order to provide a framework for using these trace metals to track changes in sulfidic conditions in ancient aquatic environments. We analyzed W and Mo concentrations in the water column and sediment pore waters of the Chesapeake Bay. We found that dissolved Mo/W molar ratios varied under different redox conditions. Because concentrations of these trace metals are controlled by their speciation in solution, we defined three sulfidic zones based on W and Mo speciation and their impacts on particle reactivity: the weakly sulfidic zone (0.2 μM < [H 2 S] < ∼15 μM); the moderately sulfidic zone (∼15 μM < [H 2 S] < ∼600 μM); and the strongly sulfidic zone ([H 2 S] > ∼600 μM). In all sulfidic zones, dissolved W concentrations were positively correlated with dissolved Mn concentrations. In contrast, the dissolved Mo concentrations were negatively correlated with dissolved Mn concentrations. As a result, Mo/W molar ratios were negatively correlated with dissolved sulfide concentrations in the weakly, moderately, and strongly sulfidic zones. Our sorption experiment results indicate that the negative correlation between Mo/W molar ratios and dissolved oxygen concentrations in the oxic zone is likely due to the stronger adsorption of WO 4 2– onto Mn oxide surfaces compared with that of MoO 4 2–. In comparison, the negative correlation between Mo/W ratios and sulfide concentrations in sulfidic waters is attributed to the differences in thiolation processes of W and Mo, with Mo exhibiting a higher degree of thiolation than that of W. Because W and Mo speciation controls their particle reactivities, these results together indicate that both speciation of W and Mo and their particle reactivity with respect to solid phases control the behaviors of Mo/W molar ratios in various reducing environments. Our results also suggest that in both oxic and weakly sulfidic conditions, both WO 4 2– and MoO 4 2– dominate. In contrast, different thiolated anions of W and Mo are likely to be present in the sedimentary records deposited in sulfidic systems. Thus, the results suggest that the dissolved Mo/W molar ratio combined with their speciation information is a strong indicator of redox changes (including oxic and sulfidic changes). Solid phase Mo/W molar ratios increase as sulfide levels increase and thus can be used to track variations in redox conditions (as well as the severity of sulfidic conditions) in ancient oceans. [ABSTRACT FROM AUTHOR]

Jarosite [KFe 3 (SO 4) 2 (OH) 6 ] occurs both as a hydrothermal mineral and as the product of weathering and chemical sedimentation. It has been used in 40Ar/39Ar geochronology to date water–rock interaction and weathering processes on the surfaces of Earth and Mars, but the lack of information about Ar diffusivity parameters relevant to specific types of jarosites makes the interpretation of geochronological results tentative. We have filled this gap by investigating Ar diffusion parameters in representative supergene and hypogene jarosites. Detailed diffusion studies were carried out on a hypogene jarosite sample from Gilbert, Nevada, and two supergene jarosite samples from Baiyin, China. The diffusion studies were accompanied by in-situ heating investigations in a transmission electron microscope to directly determine the thermal stability and the phase transformations that jarosite undergoes under progressive heating under ultra-high vacuum. The TEM results suggest that jarosite is stable under vacuum up to ∼400 °C, when it undergoes phase transition to yavapaiite [KFe(SO 4) 2 ] and hematite (Fe 2 O 3). Incremental-heating experiments reveal average diffusion parameters of E a = 138.6 ± 4.2 kJ/mol and ln(D o /a2) = 9.9 ± 0.9 ln(s−1) for hypogene jarosite; E a = 110.3 ± 3.2 kJ/mol and ln(D o /a2) = 5.7 ± 0.7 ln(s−1) for one supergene jarosites; and E a = 141.2 ± 7.9 kJ/mol and ln(D o /a2) = 11.3 ± 1.7 ln(s−1) for the other supergene jarosite sample from the same weathering profile. Jarosite closure temperatures depend strongly on sieve size. For samples between 500–200 µm (grain size usually used for samples in Ar geochronology), at a cooling rate 100 °C·Ma−1, the closure temperatures are 143 ± 18 °C for the hypogene jarosite, and 105 ± 8 and 113 ± 14 °C, respectively, for the two supergene jarosites. Forward modelling of incremental-heating results predicts that coarse-grained hypogene jarosite is retentive of Ar below 50 °C for 100 Ma and below 25 °C for 4 Ga. Densely packed supergene jarosite grains larger than 200 µm are suitable for 40Ar/39Ar geochronology at the timescales suitable for investigating water–rock interaction at the surface of Earth and Mars. Fine-grained, porous jarosites require detailed diffusion analyses prior to geochronology due to possible high Ar losses over Ma timescales. The absence of jarosites older than ∼40 Ma on Earth suggests that jarosite may require continuous exposure to acid oxidizing conditions, and that it does not survive burial and exhumation. Therefore, the occurrence of jarosite on Earth and Mars may identify segments of the planets' surfaces continuously exposed to acid-oxidizing conditions since jarosite precipitation. [ABSTRACT FROM AUTHOR]

• Granitic rocks from the Yangkou region record crustal anatexis at HP to UHP conditions. • These rocks are derived from partial melting of the underlying granitic gneisses. • The pressure effect on melt composition reflects the key role of accessory minerals during anatexis. • The Nd-Hf isotope variation is due to dissolution of apatite and garnet into anatectic melt. The production of granitic melts by decompressional melting of deeply subducted crustal rocks under high-pressure (HP) to ultrahigh-pressure (UHP) conditions is important for the crust-mantle interaction at convergent plate boundaries. However, little is known on the geochemical composition of natural HP to UHP granitic melts from collisional orogens. This problem is partially resolved here through an integrated study of the Yangkou granitic veins in the Sulu orogen, which provide the excellent records of HP to UHP granitic melts from the deeply subducted continental crust. In trace element composition, these granitic veins show enrichment in LREE and LILE but depletion in HFSE with remarkable negative anomalies of Nb, Ta, P and Ti. They have low Sr/Y (5.92–26.3) and (La/Yb) N ratios (12.7–45.6), which are primarily controlled by the solubility of accessory minerals such as apatite and epidote/allanite in anatectic melts. Phengite in the granitic veins have high Si (3.29–3.42 p.f.u.) and Mg (0.16–0.35 p.f.u.) with Mg# of 37.7–68.1 and calculated pressures of 1.7–3.1 GPa, indicating their crystallization under HP to UHP conditions. Geochemical variables such as K 2 O/Na 2 O, A/CNK and LREE for whole-rock exhibit a positive correlation with pressure, indicating the significant pressure effect on the mineral stability that in turn controls the composition of anatectic melts. Furthermore, the granitic veins can be divided into two groups based on their formation pressures and geochemical compositions. Group I granitic veins formed at low pressures of 1.7–2.4 GPa and exhibit higher SiO 2 and Na 2 O contents, but lower contents of K 2 O, MgO, TiO 2 , P 2 O 5 and most trace elements (e.g., Rb, Ba, LREE) with lower K 2 O/Na 2 O ratios and A/CNK values compared to Group II granitic veins that formed at high pressure of 2.6–3.1 GPa. Zircon from the granitic veins give concordant U–Pb ages of 755 ± 10 to 769 ± 9 Ma with steep HREE patterns for relict magmatic cores and 216 ± 4 to 222 ± 4 Ma with steep to flattened HREE patterns for anatectic rims. In comparison to concordant U–Pb ages of 220 ± 3 to 227 ± 3 Ma for newly grown zircon in the host eclogites, it appears that these granitic veins were crystallized from anatectic melts produced by crustal anataxis during the exhumation of the deeply subducted continental crust. The anatectic rims are characterized by the absence of not only oscillatory zoning in CL images but also Eu anomalies and low U contents, indicating their growth from anatectic melts under HP to UHP conditions. The granitic veins show different Sr–Nd–O isotope compositions from the host UHP eclogites, indicating that the former did not originate from partial melting of the latter. This is also supported by the distinct δ18O and ε Hf (t) values for the Triassic zircon from the granitic veins and eclogites. Instead, there are comparable isotopic compositions between the granitic veins and regional UHP granitic gneisses, indicating that the granitic veins would be derived from partial melting of the underlying UHP granitic gneisses. Group II granitic veins have higher ε Nd (t) values than Group I ones and the granitic gneisses by 3–5 ε Nd unit, indicating that the anatectic melts forming Group II granitic veins are in Nd isotope disequilibrium with their source rocks. This can be caused by the behavior of accessory minerals like apatite and epidote/allanite during crustal anataxis at different pressures. The contributions of apatite together with garnet can also account for the increased Hf isotopes in the anatectic zircon. Therefore, the accessory minerals play a key role in constraining the geochemical features of incompatible-element enriched granitic melts during the crustal anatexis under HP to UHP conditions. [ABSTRACT FROM AUTHOR]

The concentrations and isotopic compositions of molybdenum (Mo), zinc (Zn) and cadmium (Cd) in organic-rich marine mudrocks may be used to characterize ocean chemistry in the geological past. These approaches rely on the rarely tested assumption that the geochemical signatures of these metals are not affected by the thermal maturation of the organic matter with which they are associated. We have conducted a series of artificial maturation experiments on two well-known immature organic-rich mudrocks, the Kimmeridge Blackstone Band (Late Jurassic age), and the Posidonia Shale (Early Jurassic age). These pyrolysis experiments allow us to trace changes in the composition of organic matter through varying stages of maturation, and the concentration and isotopic compositions of metals in rock residues and evolved organic fluids. Our results indicate that the thermal maturation of organic matter does not result in significant alteration of the isotopic compositions of Mo, Zn and Cd in the rock residues, which thus retain primary palaeodepositional information. Systematic increases in the concentrations of Mo, Zn and Cd in rock residues with progressively higher thermal maturity are attributed to the loss of substrate mass in the form of fluids released during pyrolysis-induced cracking of kerogen, and to the relatively low concentrations of Mo, Zn and Cd in these fluids. The Mo-isotope compositions of fluids produced during pyrolysis are isotopically similar to the bulk rock; in contrast the isotopic composition of Zn in organic fluids is ∼0.4–0.6‰ lighter than the bulk rock. The progressive loss of organic matter from rock residues during maturation coupled with the increases in metal concentrations leads to an increase of metal/TOC ratios, which may be up to double their original (syn-depositional) value in thermally mature rocks. This observation must be taken into account when using metal/TOC ratios as proxies for oceanic metal inventories throughout geological time. Finally, calculations using the mass of asphaltenes recovered during the pyrolysis experiments suggest that organically bound Mo, Zn and Cd account for several percent of the total rock metal inventory. [ABSTRACT FROM AUTHOR]