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The alteration of ocean crust through hydrothermal seawater circulation facilitates chemical exchange between Earth's surface and interior. Hydrothermal alteration leads to uranium (U) removal from seawater and net U uptake by the ocean crust, particularly during low temperature alteration that occurs on the vast ocean ridge flanks away from the spreading axes. Determining the timescales of U uptake and its associated 238U/235U signature has important implications for understanding U exchange processes during subduction and recycling into the mantle. Here we study the U systematics of ∼15 million year-old ocean crust drilled at Site 1256 on the eastern flank of the East Pacific Rise. Analysis of cores from the upper ∼1300 m of intact ocean crust at this site, reveal large variability in U concentrations and 238U/235U ratios. Many of the samples from the upper ∼600 m of extrusive lavas have elevated U concentrations and 238U/235U ratios lower than seawater, consistent with mechanisms of U uptake under relatively oxidised conditions. Samples from the underlying sheeted dikes and gabbros show evidence for hydrothermal U mobilisation, but negligible net U uptake. In contrast, in the transition zone between the extrusive lavas and the sheeted dikes, samples revealed large U enrichments and high 238U/235U ratios above seawater. This is consistent with uptake of the reduced U+4 species under relatively reducing conditions from seawater-derived hydrothermal fluids. In addition, large secular disequilibrium in 234U/238U ratios from samples in the lava-dike transition and upper sheeted dikes give evidence for U mobility within the last ∼1.5 million years, likely driven by deep channelled flow of seawater-derived hydrothermal fluids combined with preferential leaching of 234U from the rock matrix. Both the total estimated U uptake and mean 238U/235U at Site 1256 is lower than similar estimates from significantly older (>100 million years) altered ocean crusts at drill Sites 801 and 417/418. This shows the variable total U uptake and 238U/235U ratio in altered ocean crust over time, which needs to be taken into consideration when estimating global U budgets. [ABSTRACT FROM AUTHOR]

Fluids released from subducted slabs impart characteristic geochemical signatures on volcanic arc magmas and residual slabs transported into the deeper mantle. Yet, the sources and transport mechanisms of trace elements released from the slab are speculative. We investigate fluids released from subducted slabs from the perspective of 238U/235U and radiogenic Pb isotope ratios in lavas from the Izu volcanic arc in the Pacific ocean. Izu arc lavas are fluid-dominated end-member type magmas that allow a close characterisation of slab fluids. The Izu arc lavas have low 238U/235U ratios compared to the bulk Earth and mid-ocean ridge basalt (MORB). The low 238U/235U (δ 238 U = − 0.46 to −0.33‰, where δ 238 U = 238 U/235U sample /238U/235U CRM145 − 1) is associated with slab-derived fluids low in Th/U that are added to the magma sources. The radiogenic Pb isotope ratios of the lavas form an array between 'Indian' type MORB and subducting sediments that is inconsistent with fluids derived from the altered mafic oceanic crust (AMOC). We infer that 'fluid-mobile' elements, including U and Pb are mobilised from largely unaltered, deeper sections of the mafic crust by migrating fluids that are derived from the dehydration of underlying serpentinites. Uranium is only fluid-mobile as UVI and needs to be oxidised from predominant UIV in unaltered magmatic rocks in order to be mobilised by fluids. Uranium isotope fractionation of ∼0.2‰ in δ 238 U during this process is required to generate the low 238U/235U in the fluids. We propose that channelised fluid flow through the metamorphosed sheeted dyke and gabbroic sections of the mafic crust locally oxidises and mobilises U. We suggest that U isotope fractionation occurs within the fluid channels and is related to equilibrium isotope fractionation during the oxidation of U and the incorporation of UIV into secondary phases such as epidote, apatite and zircon that grow within the channels. These phases are predicted to carry isotopically heavy U into the deeper mantle beyond subduction zones. The δ 238 U is thus tracing the dehydration process of subducting slabs. Similar observations have been made for other, 'stable isotope' systems in different arcs and subduction-related metamorphic rocks, thus highlighting their potential for studying processes occurring within the slabs during subduction. This information is essential for understanding and the partitioning of elements between subducted slabs and the mantle wedge and constraining the role of subduction zones in global geochemical cycles. • Arc lavas have low 238U/235U ratios compared to MORB. • Uranium is mobilised from the mafic oceanic crust via channelised fluid flow. • Uranium isotope fractionation occurs during U mobilisation in the mafic crust. • Stable and near-stable isotope systems trace processes occurring during subduction. [ABSTRACT FROM AUTHOR]

Sedimentary molybdenum (Mo) and uranium (U) abundances, as well as their isotope systematics, are used to reconstruct the evolution of the oxygenation state of the surface Earth from the geological record. Their utility in this endeavour must be underpinned by a thorough understanding of their behaviour in modern settings. In this study, Mo-U concentrations and their isotope compositions were measured in the water column, sinking particles, sediments and pore waters of the marine euxinic Lake Rogoznica (Adriatic Sea, Croatia) over a two year period, with the aim of shedding light on the specific processes that control Mo-U accumulation and isotope fractionations in anoxic sediment. Lake Rogoznica is a 15 m deep stratified sea-lake that is anoxic and euxinic at depth. The deep euxinic part of the lake generally shows Mo depletions consistent with near-quantitative Mo removal and uptake into sediments, with Mo isotope compositions close to the oceanic composition. The data also, however, show evidence for periodic additions of isotopically light Mo to the lake waters, possibly released from authigenic precipitates formed in the upper oxic layer and subsequently processed through the euxinic layer. The data also show evidence for a small isotopic offset (∼0.3‰ on 98 Mo/ 95 Mo) between particulate and dissolved Mo, even at highest sulfide concentrations, suggesting minor Mo isotope fractionation during uptake into euxinic sediments. Uranium concentrations decrease towards the bottom of the lake, where it also becomes isotopically lighter. The U systematics in the lake show clear evidence for a dominant U removal mechanism via diffusion into, and precipitation in, euxinic sediments, though the diffusion profile is mixed away under conditions of increased density stratification between an upper oxic and lower anoxic layer. The U diffusion-driven precipitation is best described with an effective 238 U/ 235 U fractionation of +0.6‰, in line with other studied euxinic basins. Combining the Mo and U systematics in Lake Rogoznica and other euxinic basins, it is apparent that the two different uptake mechanisms of U and Mo can lead to spatially and temporally variable Mo/U and Mo-U isotope systematics that depend on the rate of water renewal versus removal to sediment, the sulfide concentration, and the geometry of the basin. This study further emphasises the potential of combining multiple observations, from Mo-U enrichment and isotope systematics, for disentangling the various processes via which redox conditions control the chemistry of modern and ancient sediments. [ABSTRACT FROM AUTHOR]

We have prepared a large volume of pure, concentrated and homogenous zinc standard solution. This new standard solution is intended to be used as a primary reference standard for the zinc isotope community, and to serve as a replacement for the nearly exhausted current reference standard, the so-called JMC-Lyon Zn. The isotopic composition of this new zinc standard (AA-ETH Zn) has been determined through an inter-laboratory calibration exercise, calibrated against the existing JMC-Lyon standard, as well as the certified Zn reference standard IRMM-3702. The data show that the new standard is isotopically indistinguishable from the IRMM-3702 zinc standard, with a weighted δ66/64Zn value of 0.28 ± 0.02‰ relative to JMC-Lyon. We suggest that this new standard be assigned a δ66/64Zn value of +0.28‰ for reporting of future Zn isotope data, with the rationale that all existing published Zn isotope data are presented relative to the JMC-Lyon standard. Therefore our proposed presentation allows for a direct comparison with all previously published data, and that are directly traceable to a certified reference standard, IRMM-3702 Zn. This standard will be made freely available to all interested labs through contact with the corresponding author. [ABSTRACT FROM AUTHOR]

A series of laboratory-controlled microbial experiments using gram-negative sulphate-reducing bacteria ( Desulfovibrio brasiliensis ) inoculated with natural uranium were performed to investigate 238 U/ 235 U fractionation during bacterially-mediated U reduction. Control experiments, without bacteria to drive U reduction, were conducted in parallel. Paired measurements of 238 U/ 235 U and U concentration for both the residual growth medium solution and the accumulated biologically-mediated precipitate were obtained using multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS). The control experiments show that only minor (<0.1‰), if any 238 U/ 235 U fractionation occurs during co-precipitation with calcite. This implies that carbonate sediments are capable of faithfully recording the signature of the global ocean during Earth’s major climatic events, including oxygenation and de-oxygenation transitions in the marine environment. The results for the microbial experiments demonstrate that the 238 U/ 235 U composition of the unreacted growth medium containing U(VI) is isotopically lighter than the composition of the U(IV)-bearing precipitate as U(VI) is consumed, in agreement with field-based observations of microbially-mediated U reduction. Uranium isotopic shifts of up to 0.8‰ were observed between the liquid and solid phases. These observations can be modelled using a Rayleigh distillation approach describing kinetic uptake in a closed system, which yields a fractionation factor α of 0.99923 ± 0.00004 ( ε = −0.77 ± 04‰) for U(VI)–U(IV) reduction mediated by the D. brasiliensis microbe. This fractionation behaviour is consistent with that observed in field-based redox environments, which give rise to similar α values. Competing processes such as U co-precipitation (e.g. adsorption) may act to lower the apparent value for α and possibly play a secondary role both in the microbial experiments of this study and in natural U reduction settings where variable α values are found. These results may suggest that microbes adept at inducing U(VI) reduction play a crucial role in facilitating significant 238 U/ 235 U isotope fractionation in nature. [ABSTRACT FROM AUTHOR]

Changing conditions on the Earth's surface can have a remarkable influence on the composition of its overwhelmingly more massive interior. The global distribution of uranium is a notable example. In early Earth history, the continental crust was enriched in uranium. Yet after the initial rise in atmospheric oxygen, about 2.4 billion years ago, the aqueous mobility of oxidized uranium resulted in its significant transport to the oceans and, ultimately, by means of subduction, back to the mantle. Here we explore the isotopic characteristics of this global uranium cycle. We show that the subducted flux of uranium is isotopically distinct, with high 238U/235U ratios, as a result of alteration processes at the bottom of an oxic ocean. We also find that mid-ocean-ridge basalts (MORBs) have 238U/235U ratios higher than does the bulk Earth, confirming the widespread pollution of the upper mantle with this recycled uranium. Although many ocean island basalts (OIBs) are argued to contain a recycled component, their uranium isotopic compositions do not differ from those of the bulk Earth. Because subducted uranium was probably isotopically unfractionated before full oceanic oxidation, about 600 million years ago, this observation reflects the greater antiquity of OIB sources. Elemental and isotope systematics of uranium in OIBs are strikingly consistent with previous OIB lead model ages, indicating that these mantle reservoirs formed between 2.4 and 1.8 billion years ago. In contrast, the uranium isotopic composition of MORB requires the convective stirring of recycled uranium throughout the upper mantle within the past 600 million years. [ABSTRACT FROM AUTHOR]

Abstract: The zinc (Zn) content and isotopic composition of marine biogenic opal have the potential to yield information about the nutrient availability, utilization and export of particulate organic matter from surface to deep waters. Here, we report the first measurements of the Zn isotopic composition of deep-sea marine sponge skeletal elements – spicules – collected in the Southern Ocean. Our results highlight different Zn uptake and isotopic fractionation behavior between the two major siliceous sponge clades (hexactinellids and demosponges), which is most likely linked to sponge feeding strategy. Hexactinellid spicule Zn isotopic compositions are not fractionated with respect to seawater, most likely due to Zn transport via the open internal structure of the sponges. In contrast, demosponge spicules exhibit a wide range of Zn isotopic compositions that are related to the opal Zn concentration, most likely reflecting variable Zn isotope compositions in the organic matter particles on which they feed, and internal fractionation processes. [Copyright &y& Elsevier]

Abstract: Historical 239Pu activity concentrations and 240Pu/239Pu atom ratios were determined in skeletons of dated modern corals collected from three locations (Chuuk Lagoon, Ishigaki Island and Iki Island) to identify spatial and temporal variations in Pu inputs to the Northwest Pacific Ocean. The main Pu source in the Northwest Pacific is fallout from atmospheric nuclear weapons testing which consists of global fallout and close-in fallout from the former US Pacific Proving Grounds (PPG) in the Marshall Islands. PPG close-in fallout dominated the Pu input in the 1950s, as was observed with higher 240Pu/239Pu atom ratios (>0.30) at the Ishigaki site. Specific fallout Pu contamination from the Nagasaki atomic bomb and the Ivy Mike thermonuclear detonation at the PPG were identified at Ishigaki Island from the 240Pu/239Pu atom ratios of 0.07 and 0.46, respectively. During the 1960s and 1970s, global fallout was the major Pu source to the Northwest Pacific with over 60% contribution to the total Pu. After the cessation of the atmospheric nuclear tests, the PPG again dominated the Pu input due to the continuous transport of remobilised Pu from the Marshall Islands along the North Equatorial Current and the subsequent Kuroshio Current. The Pu contributions from the PPG in recent coral bands (1984 onwards) varied over time with average estimated PPG contributions between 54% and 72% depending on location. [Copyright &y& Elsevier]

Abstract: We have developed cleaning methods for extracting diatomopal from bulk marine sediment samples, for measurement of both zinc (Zn) abundance and isotope composition. This cleaning technique was then applied to a set of Holocene core-top samples from the Southern Ocean. The measured δ66Zn (reported relative to the JMCLyon standard) and Zn/Si ratios from the Southern Ocean diatomopal samples range from 0.7 to 1.5‰, and from 14 to 0.9μmol/mol, respectively. The Zn abundance and isotope composition data show a clear correlation with opal burial rates and other oceanographic parameters. In common with previous work, we interpret the systematic changes in the Zn/Si ratio to be linked to the variability in the concentrations of bioavailable Zn in the ambient surface seawater where the diatom opal is formed. This variability is likely to be primarily controlled by the degree to which Zn is taken up into phytoplankton biomass. The observed systematic pattern in the δ66Zn compositions of the diatomopal core-top samples is, similarly, likely to reflect changes in the δ66Zn composition of the ambient Zn in the surface waters above the core-top sites, which is progressively driven towards isotopically heavier values by preferential incorporation of the lighter isotopes into phytoplankton organic material. Thus, the systematic relationship between Zn isotopes and abundance observed in the core-top diatomopal samples suggests a potential tool for investigating the biogeochemical cycling of Zn in the past surface ocean for down-core diatomopal material. In this respect, it may be possible to test hypotheses that attribute variations in atmospheric CO2 on glacial–interglacial timescales to the degree to which trace metals limited primary productivity in HNLC zones. [Copyright &y& Elsevier]

Abstract: Direct dating of fossil coral reefs using the U-series chronometer provides an important independent test of the Milankovitch orbital forcing theory of climate change. However, well-dated fossil corals pre-dating the last interglacial period (>130 thousand years ago; ka) are scarce due to, (1) a lack of sampling localities, (2) insufficient analytical precision in U-series dating methods, and (3) diagenesis which acts to violate the assumption of closed-system U-series isotopic decay in fossil corals. Here we present 50 new high-precision U-series age determinations for fossil corals from Henderson Island, an emergent coral atoll in the central South Pacific. U-series age determinations associated with the Marine Isotope Stage (MIS) 9 interglacial and MIS 7.5 interstadial periods are reported. The fossil corals show relatively little open-system U-series behaviour in comparison to other localities with fossil coral reefs formed prior to the last glacial cycle, however, open-system U-series behaviour is still evident in most of the dated corals. In particular, percent-level shifts in the [230Th/238U]act composition are observed, leading to conventional U-series ages that are significantly younger or older than the true sample age. This open-system U-series behaviour is not accounted for by any of the open-system U-series models, indicating that new models should be derived. The new U-series ages reported here support and extend earlier findings reported in , providing evidence of prolific coral reef development on Henderson Island at ∼320ka, most likely correlated with MIS 9.3, and subsequent reef development at ∼307ka during MIS 9.1, while relative sea-level was potentially ∼20m lower than during MIS 9.3. The U-series ages for additional well-preserved fossil corals are suggestive of minor reef development on Henderson Island during MIS 7.5 (245–230ka) at 240.3±0.8 and 234.7±1.3ka. All U-series observations are consistent with the Milankovitch theory of climate change, in terms of the timing of onset and termination of the dated interglacial and interstadial periods. The best preserved samples also suggest that the oceanic 234U/238U during MIS 9 and MIS 7.5 was within five permil of the modern open ocean composition. [Copyright &y& Elsevier]

Abstract: The daughter to parent (234U/238U) activity ratio in natural waters is often out of secular radioactive equilibrium. The major reason for this disequilibrium is related to the energetic α-decay of 238U and differential release of 234U relative to 238U. This disequilibrium originates from (1) preferential release of more loosely bound 234U from damaged mineral lattice sites or; (2) direct recoil of 234Th into surrounding media from near mineral surface boundaries, however, it is unclear which of the two mechanisms is most important in nature. To better quantify the effects of preferential release of 234U, two continuous laboratory granite leaching experiments conducted over 1100h were performed. The leachates were characterized by declining U concentrations with time and (234U/238U) initially greater than unity (up to 1.15), which changed to below unity during leaching (∼0.95). The early elevated (234U/238U) suggests that additional 234U is released into solution by preferential release of 234U from mineral phases. However, the excess 234U constitutes a finite pool of easy leachable 234U and the (234U/238U) values become lower than unity when this pool is used up. A model based on first-order kinetics, dissolution rates and preferential release of 234U from damaged lattice sites was developed and is able to quantitatively predict the observed pattern of (234U/238U) values and U concentrations for the two granite leaching experiments. Extending the modeling to longer time scales more comparable to natural systems shows that the production of waters with high (234U/238U) ratios can be achieved in two distinct regimes (1) slow weathering where the rate of directly recoiled 234U near mineral surfaces into waters is high; (2) fast weathering where the role of incipient chemical weathering and preferential release of loosely bound 234U are important. The model is able to explain apparent opposite correlations between physical erosion rates and (234U/238U) in waters and it provides a new framework that will be useful for examining weathering regimes, their timescales and their coupling with physical erosion. [Copyright &y& Elsevier]

Abstract: Absolutely dated records of past sea-level change are extremely important for understanding the advance and retreat of the large ice sheets. When combined with other complementary climate archives and climate models, such records offer the potential to gain an improved understanding of Earth''s natural climate cycles, providing a firmer basis for assessing the role of anthropogenic effects, such as greenhouse gas emissions, in modifying climate. The U-series dating of fossil coral reefs has been widely utilized to provide absolutely dated records of past sea-level change and numerous observations now exist for the past 130,000 years spanning the last glacial cycle. Despite this, controversies still exist regarding the exact timing and character of sea-level events within this time interval, and extending the sea-level history further back in time on the basis of robust and independent age constraints for older fossil reefs remains very elusive. This is primarily due to a progressive loss in the resolution of the U-series chronometer as one goes further back in time, coupled to a lack of well-preserved, dateable coral in older fossil reefs. To overcome these limitations, the primary challenges are three-fold. First, new analytical protocols are required to improve the resolution of the U-series chronometer. Enhanced analytical precision must be coupled to accuracy through continued refinement of the U-series decay constant determinations and via the implementation of rigorous inter-laboratory calibration exercises. Second, efforts should continue to be focussed on gaining an improved understanding of the mechanisms controlling open-system exchange of the U-series isotopes in fossil reef systems. This will allow the number of ‘reliable’ U-series observations to be extended. Third, alternative dateable archives of past sea-level change must continue to be emphasized to further complement the coral reef database. These limitations are discussed in the context of current developments that further advance the application of U-series chronology to older fossil reef systems formed prior to the last glacial cycle. [Copyright &y& Elsevier]

Abstract: Robust, independent age constraints on the absolute timing of climate events based on the U-series dating of fossil coral are sparse before the last glacial cycle. Using multiple-collector inductively coupled plasma mass spectrometry with multiple-Faraday protocols, we are able to date ∼600 ka samples with an uncertainty of better than ±15 ka (2σ), representing a three-fold improvement in precision compared with previous techniques. Using these methods, we report U-series measurements for a suite of >500 thousand year old (ka) corals from Henderson Island, an emergent atoll in the south-central Pacific Ocean. The fossil corals show extraordinarily little diagenetic alteration for their age and the best-preserved sample yields a U-series age of 600±15 ka (2σ), which overlaps with the timing of the warm Marine Isotope Stage (MIS) 15 interglacial. The open-system model of Villemant and Feuillet [Villemant B. and Feuillet N. (2003) Dating open systems by the 238U–234U–230Th method: application to Quaternary reef terraces. Earth and Planetary Science Letters 210(1–2), 105–118.] and the linear regression (or open-system isochron) is clearly limited for such old samples. However, the open-system model developed by Thompson et al. [Thompson W.G., Spiegelman M.W., Goldstein S.L., and Speed R.C. (2003) An open-system model for U-series age determinations of fossil corals. Earth and Planetary Science Letters 210(1–2), 365–381.] appears to reliably correct for open-system effects in roughly half of the corals, giving a MIS 15 origin for these. Thus the data provide evidence that the systematic addition of 230Th and 234U through α-recoil is a dominant open-system process occurring in the Henderson Island fossil reef system. Several coral samples yield significantly older Thompson et al. open-system ages between 650 and 750 ka. The uncertainty on these ages (typically±30 kyrs) is too great for precise assignment but most data overlap with the MIS 17 interglacial. The reliability of these ages is currently unclear. It is shown that separate aliquots of the same coral can yield different Thompson model ages. Therefore, there appear to be additional diagenetic mechanisms that create further anomalous excursions in the U-series systematics, limiting the reliability of the Thompson et al. open-system model. [Copyright &y& Elsevier]

Abstract: Uranium is the heaviest naturally occurring element and isotope fractionation between 235U and 238U is not normally considered significant given the small ∼1% difference in mass. It is therefore usual to assume that 238U/235U is constant in the terrestrial environment and equal to 137.88. We have developed experimental protocols for the precise measurement of 235U/238U by multiple-collector ICPMS (MC-ICPMS) and have analyzed a suite of samples formed in a range of low-temperature environments. Using a high-purity 233U–236U double spike to internally monitor the large (percent-level) but essentially constant instrumental mass bias effects that are inherent to plasma source mass spectrometry, we are able to resolve variations in 235U/238U at the 0.4 epsilon level (2σ; 1 epsilon=1 part in 10,000) on sample sizes comprising 50 ng of uranium. Here we demonstrate sizeable (13 epsilon units) natural variability in 235U/238U, exceeding the analytical reproducibility by more than an order of magnitude. Compositions that are both isotopically heavier and lighter than our terrestrial standard, by 4 and 9 epsilon units respectively, are observed. The largest excursions are found in speleothem samples. Furthermore, 235U/238U appears broadly correlated with 234U/238U in samples showing the most extreme isotopic compositions. The present study investigates the role of abiotic processes in fractionating 235U from 238U. Sequential leaching experiments of U-rich minerals indicate that mineral weathering is a possible mechanism by which 235U can be fractionated from 238U in groundwaters and incorporated into speleothems. The observed variability in 235U/238U indicates that uranium isotopes may offer the potential to monitor new reaction pathways, such as those activated during the redox transition between the U(IV) and U(VI) oxidation states. Experiments involving the redox transition of U(VI) to U(IV) in the presence of zero-valent zinc did not produce a resolvable shift in 235U/238U towards anomalous values, although fractionation need not occur if the reaction is governed by a fast kinetic process. Our observations have a direct impact on the U-series and U–Th–Pb chronometers, when applied to samples formed in low-temperature environments, as these chronometers currently assume an invariant 238U/235U equal to 137.88. [Copyright &y& Elsevier]

We apply the stable potassium isotope system (41K/39K) to well-studied Mariana arc lavas, in which inter-island geochemical variability has been interpreted to reflect near constant addition of an aqueous fluid flux, that dominantly samples the subducting mafic oceanic crust and variable amounts of sediment melt addition to the sub-arc mantle wedge. The nature of the sediment component in the Mariana arc lavas remains enigmatic, with a mixture of melts from all subducted sediment lithologies and the altered-mafic oceanic crust seeming likely, but some interpretations point towards a component from melting of the volcaniclastic sediment alone. We present K isotopic data on a set of well-characterised Mariana arc lavas and sediment samples (from Ocean Drilling Program site 801). Our data show that the majority of Mariana arc lavas are isotopically heavy (ẟ 41K), by up to ∼0.2 ‰, relative to mid-ocean ridge basalt (MORB), but most of the subducting sediment samples are slightly isotopically lighter than, or indistinguishable from MORB. The volumetrically important volcaniclastic sedimentary unit however is significantly isotopically lighter than MORB, by ∼0.8 ‰, which reflects marine diagenetic processes. Thus, volcaniclastic material significantly influences the bulk sediment K isotope composition. We show that ẟ 41K compositions of the Mariana arc lavas can be reproduced by the addition of an aqueous fluid with isotopically heavy K (relative to MORB) and an additional fraction of an incompatible-element-enriched isotopically light melt component. Modelling of K isotopes together with K/La and radiogenic Nd indicate that the melt component is best explained by a mix of melts from bulk sediment and altered-mafic oceanic crust. Our results show that distinctive K isotopic variations in subduction zone inputs and K isotopic fractionation during dehydration reactions makes K a useful tracer of subduction zone processes. [ABSTRACT FROM AUTHOR]

Marine animal diversity during the late Cambrian was reduced by a series of extinctions that have generally been attributed to oceanic anoxic events associated with positive carbon isotope excursions. Here we present carbon and uranium isotope ratios (δ13C and δ238U values) as proxies for global carbon cycle and oceanic redox conditions, respectively, from carbonate rocks of the Wa'ergang section, South China. The dataset spans an interval that includes the last major negative δ13C excursion (TOCE) of the Cambrian Period. The TOCE is a globally documented event, recovery from which corresponds to the terminal Cambrian extinction event. The δ13C and δ238U values covary through the section, shifting initially to lower values, with δ238U falling below the modern open-ocean seawater value from the start to the middle of the profile, followed by a shift to higher values towards the end of the Cambrian. Neither the co-occurrence of δ13C and δ238U negative excursions, nor the association of rising δ238U with extinction have been commonly reported. Here we argue that robust positive coupling of δ13C and δ238U relates to the existence of extensive intermediate reducing settings (from low-O 2 suboxia to intermittent anoxia) during the late Cambrian alongside low atmospheric p O 2 and a greenhouse climate. Similarly, a stepwise increase in the δ238U baseline in carbonates across the Ediacaran−Cambrian boundary is consistent with the growing importance of an intermediate reducing sink through that interval. We propose further that divergent trends in lower and upper ocean redox conditions could have driven the parallel isotope excursions. An expansion of intermediate reducing conditions, rather than persistent anoxic euxinia, is consistent with the recovery of δ13C and δ238U to higher values, as well as the presence of benthic fauna and shoreward extension of deeper-water fauna that may have had a greater tolerance against hypoxia. [ABSTRACT FROM AUTHOR]

Abstract: This work studied the buccal absorption of metoprolol in vitro, ex vivo and in vivo as a function of buffered pH at 7.4, 8.5, 9.0 and 9.5. Permeability studies showed a correlation (r 2 =0.92) between in vitro TR146 cell culture and ex vivo porcine buccal mucosa in a modified Ussing chamber. A higher apparent permeability was observed at higher pH values, i.e. the more compound that was unionised the higher the permeability. In vivo studies were conducted in anaesthetised Göttingen mini-pigs. A clear influence of pH on the absorption was seen and a significant higher absolute bioavailability was obtained after buccal dosing (58–107%) compared to oral (3%) administration, ranging 58–107% and 3%, respectively. Macroscopically, no local toxic effects were observed by visual inspection of mini-pig cheeks. A very clear level C in vitro in vivo correlation (r 2 =0.98) was obtained between the observed in vitro permeabilities and the bioavailability observed in vivo, suggesting that the two in vitro models have good predictive power for drug delivery, which could be a useful tool for future formulation developments intended for buccal delivery. [Copyright &y& Elsevier]

Abstract: This study investigates U-series, Sr isotopes, major and trace elements in a chalk aquifer system located in Eastern France. Soil and rock samples were collected along depth profiles down to 45 m in four localities as an attempt to investigate the weathering processes in the soil, the unsaturated zone and the saturated zone of the aquifer. Interstitial water was extracted from soils and rocks by a centrifugation technique. U-series offer a powerful tool to calculate weathering rates because the relative mobility of the U- and Th-isotopes can be precisely measured and it does not require the determination of a reference state as in other approaches. As expected, the data show very large mobile element depletion in the soil with large 230Th excess relative to 238U, while the rocks show more limited but not insignificant mobile element depletion. The U-series data have been used to constrain weathering rates based on a 1-D reactive transport model. Weathering rates in the near surface are about 10–100 times faster than at depth. However, when integrated over the depth of the cores, including the unsaturated and the saturated zones, this underground weathering represents more than 30% of the total weathering flux, assuming congruent dissolution of carbonates. The (234U/238U) ratios in interstitial water are consistent with solid samples showing 234U depletion near the surface and an excess 234U at depth. A leaching experiment performed on chalk shows that the excess 234U in natural waters percolating through carbonate rocks results both from preferential 234U leaching and direct recoil in the interstitial water. A new approach was used to derive the recoil ejection factor based on BET measurements and the fractal dimension of chalk surface. Consideration of preferential leaching and recoil allows a more accurate modeling of weathering rates. [Copyright &y& Elsevier]

Abstract: Uranium-series dating of carbonate materials requires precise determination of the spike sample thorium isotope ratio, 230Th/229Th. This ratio is commonly measured using ion counting techniques, however the precision of analyses using ion counting devices suffers from beam intensity limitations, drift in multiplier gain and non-linearities in electron multiplier response. Here, we describe the application of multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) to determine thorium isotope ratios at hitherto unattained precision. For the first time, thorium isotope analyses were performed using only Faraday collectors coupled to 1011 Ω feedback resistors in the amplifier system. Spiked thorium solutions were concentrated to produce 230Th and 229Th signal intensities of around 50mV and 100mV, respectively (across a 1011 Ω resistor) and are run at high intensity for a short period of time (∼1min). These analyses yield a 230Th/229Th external reproducibility of better than 0.3‰ for ∼25–30pg of consumed 230Th. This is a factor of two better than the best published thermal ionisation mass spectrometry (TIMS) and MC-ICPMS techniques for similar sample sizes, and represents up to an order of magnitude improvement over many other established protocols. Combined with new techniques for high precision Faraday measurement of uranium isotopic composition , this permits improvements in the uncertainty of U-series ages to better than 0.1 thousand years (ka) at 100ka and 1ka at 300ka. It should also be possible to resolve events to ∼14ka at 600ka. Using these techniques, the U-series dating limit can be extended from 500–600ka to 800ka enabling a more detailed study of the frequency of late Pleistocene climate events. [Copyright &y& Elsevier]

Novel metal isotope systematics are increasingly used to understand environmental change in geological history. On a global scale, the isotopic budgets of these metals respond to a range of environmental processes, allowing them to trace complex changes in the global climate system and carbon cycle. In particular, uranium (U) and molybdenum (Mo) isotopes are useful tools for quantifying the global extent of oceanic anoxia and euxinia respectively. The oceanic signature of these metals is recorded in contemporaneous marine sediments. Whilst, traditionally, organic-rich anoxic 'black shales' have provided a useful archive of these metals, carbonate sediments are increasingly being used as a passive recorder of ocean chemistry. The majority of published U and Mo isotope studies come from shallow water platform environments. By contrast, pelagic carbonate sediments are an under-explored archive for these metals, yet are widely available for important periods of Earth history. Despite their advantages, carbonates are a complex archive, containing multiple 'contaminant' components such as Mn-oxides, organic matter and detrital minerals. Each of these phases can have different metal concentrations and isotopic signatures, giving the potential to distort or bias the true oceanic signature recorded by the carbonate. Reductive cleaning procedures and selective leaching protocols can be used to avoid these contaminant phases, and are tested here on modern and ancient samples to judge their efficacy in isolating a 'carbonate-bound fraction'. To this end, leaching experiments were performed using different concentration acetic acid, HCl and HNO 3 , on reductively cleaned and uncleaned sample pairs. The data demonstrate that Mn-oxide coatings and exchangeable phases have a large impact on the Mo isotopic signature (δ98Mo) of carbonates, even when weak leaching techniques are used to preferentially dissolve them. Furthermore, detrital sources of Mo are also easy to liberate with different leaching protocols, and exert a significant control on leachate isotopic composition. The leaching studies identify that the pelagic carbonate end-member has a relatively high δ98Mo, but the precise relationship to seawater compositions remains unclear. For U, significant contributions from non‑carbonate phases can clearly be identified in higher concentration leaching acids using U/Ca ratios. However, U isotopes (δ238U) show no resolvable difference with different leaching procedures and are not affected by reductive cleaning. This result probably reflects (a) the low potential for leaching refractory residual detrital U phases (e.g., zircon) that contain the majority of U in the sample and (b) the low U inventories of Mn oxides versus those of Mo. Instead, leaching likely extracts U that is mineralogically bound in carbonates and authigenic clays, which share a common isotopic signature. These new data suggest that U incorporation into pelagic carbonates may be dominated by adsorption, and be offset from seawater by ~−0.15‰, in a similar manner to that seen for clays. [ABSTRACT FROM AUTHOR]

Constraining the timing of eukaryogenesis and the divergence of eukaryotic clades is a major challenge in evolutionary biology. Here, we present trace metal concentration and zinc isotope data for c. 2.1 billion-year-old Francevillian Group pyritized structures, previously described as putative remnants of the first colonial multicellular organisms, and their host black shales. Relative to the host rocks, pyritized structures are strongly enriched in zinc, cobalt and nickel, by at least one order of magnitude, with markedly lighter zinc isotope compositions. A metabolic demand for high concentrations of aqueous zinc, cobalt, and nickel combined with preferential uptake of lighter zinc isotopes may indicate metalloenzyme utilization by eukaryotes in marine habitats c. 2.1 billion years ago. Once confirmed, this would provide a critical calibration point for eukaryogenesis, suggesting that this major evolutionary innovation may have happened contemporaneously with elevated atmospheric oxygen levels during the latter part of the Great Oxidation Event, some 400 million years earlier than is currently widely accepted. • Biogenic origin of the c. 2.1-billion-year-old Francevillian Group biota. • Enrichment of light zinc isotopes in the Francevillian biota is consistent with eukaryotic metabolism. • Utilization of metalloenzymes by possible eukaryotes in the Paleoproterozoic oceans. • Possible eukaryotic biota preserved in the Paleoproterozoic Francevillian Group. • Inferred eukaryogenesis during the Great Oxidation Event. [ABSTRACT FROM AUTHOR]

Isotopic data collected to date as part of the GEOTRACES and other programmes show that the oceanic dissolved pool is isotopically heavy relative to the inputs for zinc (Zn) and nickel (Ni). All Zn sinks measured until recently, and the only output yet measured for Ni, are isotopically heavier than the dissolved pool. This would require either a non-steady-state ocean or other unidentified sinks. Recently, isotopically light Zn has been measured in organic carbon-rich sediments from productive upwelling margins, providing a potential resolution of this issue, at least for Zn. However, the origin of the isotopically light sedimentary Zn signal is uncertain. Cellular uptake of isotopically light Zn followed by transfer to sediment does not appear to be a quantitatively important process. Here, we present Zn and Ni isotope data for the water column and sediments of the Black Sea. These data demonstrate that isotopically light Zn and Ni are extracted from the water column, probably through an equilibrium fractionation between different dissolved species followed by sequestration of light Zn and Ni in sulfide species to particulates and the sediment. We suggest that a similar, non-quantitative, process, operating in porewaters, explains the Zn data from organic carbon-rich sediments. [ABSTRACT FROM AUTHOR]

Seawater 234U/238U provides global-scale information about continental weathering and is vital for marine uranium-series geochronology. Existing evidence supports an increase in 234U/238U since the last glacial period, but the timing and amplitude of its variability has been poorly constrained. Here we report two seawater 234U/238U records based on well-preserved deep-sea corals from the low-latitude Atlantic and Pacific Oceans. The Atlantic 234U/238U started to increase before major sea-level rise and overshot the modern value by 3 per mil during the early deglaciation. Deglacial 234U/238U in the Pacific converged with that in the Atlantic after the abrupt resumption of Atlantic meridional overturning. We suggest that ocean mixing and early deglacial release of excess 234U from enhanced subglacial melting of the Northern Hemisphere ice sheets have driven the observed 234U/238U evolution. [ABSTRACT FROM AUTHOR]

• Mo isotopes analysed in mid-ocean ridge basalts and sulphide–basalt experiments. • Significantly sub-chondritic Mo isotope composition in Earth's mantle. • Subducted ocean crust simultaneously lowers its 98Mo/95Mo and increases its Ce/Pb. • Addition of subducted ocean crust explains MORB source characteristics. Several studies have suggested that the Earth's upper mantle is slightly enriched in light molybdenum isotopes relative to bulk Earth, defined by chondrites, but there is no consensus on the presence of this subtle but potentially notable signature. To establish better whether or not the 98Mo/95Mo of Earth's upper mantle is indeed sub-chondritic, we have analysed hand-picked glasses of depleted (i.e. chondrite normalised La/Sm<1) mid-ocean ridge basalts (MORB) from the Pacific, Atlantic and Indian ocean basins. The mean Mo isotope composition of our depleted MORB relative to reference NIST SRM 3134 (δ 98 / 95 Mo NIST SRM 3134) is −0.22±0.03‰ (95% confidence interval, c.i.) compared to a value of −0.15±0.01‰ (95% c.i.) for bulk Earth. Our high precision analyses of the 234U/238U activity ratios of these samples are within uncertainty of unity, which rules out the effect of possible secondary, sea-floor processes as the dominant cause of their low δ 98 / 95 Mo NIST SRM 3134. We further report experimental data showing that sulphide liquid has δ 98 / 95 Mo NIST SRM 3134 0.25±0.01‰ lower than basaltic silicate liquid at 1400 °C. This fractionation is too small to significantly alter the Mo isotope composition of basalts relative to their sources during melting or differentiation. Our MORB data show that resolvably sub-chondritic Mo isotope compositions are common in the upper mantle. Moreover, an appropriately weighted average δ 98 / 95 Mo NIST SRM 3134 of depleted and enriched MORB, taken from this study and the literature, yields an estimated mantle value of −0.20±0.01‰, indicating that the upper mantle as a whole is sub-chondritic. Since prior work demonstrates that core formation will not create a residual silicate reservoir with a sub-chondritic δ 98 / 95 Mo NIST SRM 3134 , we propose that this feature is a result of recycling oceanic crust with low δ 98 / 95 Mo NIST SRM 3134 because of Mo isotope fractionation during subduction dehydration. Such an origin is in keeping with the sub-chondritic Th/U and low Ce/Pb of the depleted mantle, features which cannot be explained by simple melt extraction. We present mass balance models of the plate tectonic cycle that quantitatively illustrate that the δ 98 / 95 Mo NIST SRM 3134 of the Earth's mantle can be suitably lowered by such oceanic crustal recycling. Our Mo isotope study adds to the notion that the depleted mantle has been substantially modified by geodynamic cycling of subduction-processed oceanic crust. [ABSTRACT FROM AUTHOR]

The later stages of Earth's transition to a permanently oxygenated atmosphere during the Great Oxidation Event (GOE; ∼2.43–2.06 Ga) is commonly linked with the suggestion of an "oxygen overshoot" during the ∼2.22–2.06 Ga Lomagundi Event (LE), which represents Earth's most pronounced and longest-lived positive carbon isotope excursion. However, the magnitude and extent of atmosphere-ocean oxygenation and implications for the biosphere during this critical period in Earth's history remain poorly constrained. Here, we present nitrogen (N), selenium (Se), and carbon (C) isotope data, as well as bio-essential element concentrations, for Paleoproterozoic marine shales deposited during the LE. The data provide evidence for a highly productive and well-oxygenated photic zone, with both inner and outer-shelf marine environments characterized by nitrate- and Se oxyanion-replete conditions. However, the redoxcline subsequently encroached back onto the inner shelf during global-scale deoxygenation of the atmosphere-ocean system at the end of the LE, leading to locally enhanced water column denitrification and quantitative reduction of selenium oxyanions. We propose that nitrate-replete conditions associated with fully oxygenated continental shelf settings were a common feature during the LE, but nitrification was not sufficiently widespread for the aerobic nitrogen cycle to impact the isotopic composition of the global ocean N inventory. Placed in the context of Earth's broader oxygenation history, our findings indicate that O 2 levels in the atmosphere-ocean system were likely much lower than modern concentrations. Early Paleoproterozoic biogeochemical cycles were thus far less advanced than after Neoproterozoic oxygenation. • Enhanced oxygenic photosynthesis during the ∼2.22–2.06 Ga Lomagundi carbon isotope excursion. • Fully oxygenated continental shelf seawater column during the Paleoproterozoic Lomagundi Event. • Coevolution of deep redoxcline in the Paleoproterozoic oceans and atmospheric oxygen overshoot during the Lomagundi Event. • Modern biogeochemical cycles were not achieved in the Paleoproterozoic oceans during the Great Oxidation Event. [ABSTRACT FROM AUTHOR]

Abstract: A depth profile of 239Pu and 240Pu specific activities and isotope ratios was determined in an inter-tidal sediment core from the Esk Estuary in the northeastern Irish Sea. The study site has been impacted with plutonium through routine radionuclide discharges from the Sellafield nuclear reprocessing plant in Cumbria, NW England. A pronounced sub-surface maximum of ~10kBqkg-1 was observed for 239+240Pu, corresponding to the peak in Pu discharge from Sellafield in 1973, with a decreasing trend with depth down to ~0.04kBqkg-1 in the deeper layers. The depth profile of 239+240Pu specific activities together with results from gamma-ray spectrometry for 137Cs and 241Am was compared with reported releases from the Sellafield plant in order to estimate a reliable sediment chronology. The upper layers (1992 onwards) showed higher 239+240Pu specific activities than would be expected from the direct input of annual Sellafield discharges, indicating that the main input of Pu is from the time-integrated contaminated mud patch of the northeastern Irish Sea. The 240Pu/239Pu atom ratios ranged from ~0.03 in the deepest layers to >0.20 in the sub-surface layers with an activity-weighted average of 0.181. The decreasing 240Pu/239Pu atom ratio with depth reflects the changing nature of operations at the Sellafield plant from weapons-grade Pu production to reprocessing spent nuclear fuel with higher burn-up times in the late 1950s. In addition, recent annual 240Pu/239Pu atom ratios in winkles collected during 2003–2008 from three stations along the Cumbrian coastline showed no significant spatial or temporal differences with an overall average of 0.204, which supports the hypothesis of diluted Pu input from the contaminated mud patch. [Copyright &y& Elsevier]

The Ediacaran Period was characterised by major carbon isotope perturbations. The most extreme of these, the ∼570 Ma Shuram/DOUNCE (Doushantuo Negative Carbon isotope Excursion) anomaly, coincided with early radiations of benthic macrofauna linked to a temporary expansion in the extent of oxygenated seawater. Here we document an earlier negative excursion (the ∼610 Ma WANCE (Weng'An Negative Carbon isotope Excursion)) anomaly in the Yangtze Gorges area, South China, that reached equally extreme carbon isotope values and was associated with a similar degree of environmental perturbation. Specifically, new uranium isotope data evidence a significant, but transient, shift towards more oxygenated conditions in tandem with decreasing carbon isotope values, while strontium and sulfur isotope data support an increase in continental weathering through the excursion. We utilize a biogeochemical modelling approach to demonstrate that the influx of such a weathering pulse into an organically-laden, largely anoxic ocean, fully reproduces each of these distinct isotopic trends. Our study directly supports the hypothesis that a large dissolved marine organic pool effectively buffered against widespread oxygenation of the marine environment through the Proterozoic Eon, and in doing so, substantially delayed the radiation of complex aerobic life on Earth. • Extremely negative carbon isotope excursion identified in the early Ediacaran. • The excursion represents a short-lived but failed oxidation event. • Widespread oxygenation is prevented by a large dissolved marine organic pool. • The presence of a marine organic carbon pool delayed the rise of complex life on Earth. [ABSTRACT FROM AUTHOR]

Abstract: The short-lived nuclide 247Cm is produced by r-process nucleosynthesis. When the presolar nebula formed, 247Cm became isolated from r-process production and its abundance diminished as a result of radioactive decay. Given its short half-life of only ∼16 million years, 247Cm is presently extinct, but its former presence should be detectable as small variations in 235U/238U in primitive meteoritic material, provided Cm was chemically fractionated from U at the time these solid objects formed. The magnitude of U isotopic anomalies in meteorites can thus be used to elucidate the timing and character of the last r-process nucleosynthetic event for input into models describing the formation and evolution of the early solar system. Here we report coupled U isotopic determinations and Nd/U proxy measurements for Cm/U in a series of acid-etched leachates and mineral assemblages extracted from meteorites containing primitive phases expected to show strong Cm–U fractionations. Using multiple-collector ICPMS, we are able to determine 235U/238U with 2σ analytical uncertainties of ±1 epsilon (1 epsilon=1 part in 10,000) on sample sizes consisting of <3 ng of 238U and <20 pg of 235U. A double-spiking procedure using a mixed 236U–233U spike was employed to allow instrumental mass fractionation to be reliably corrected internally and at high precision. Uranium isotopic results for almost 40 different phases show no resolvable deviations in 235U/238U from the chondritic value, at the ∼1–2 epsilon level. These data supplement our previous observations for a suite of bulk meteorite samples [C.H. Stirling, A.N. Halliday, D. Porcelli, In search of live 247Cm in the early solar system, Geochim. Cosmochim. Acta 69 (2005) 1059–1071] and provide evidence for a solar system initial 247Cm/235U of <8×10−5. Such a low value is difficult to explain without a long time-scale of ∼2.3×108 years between the last actinide producing r-process event and the formation of the solar system. As such it is difficult to reconcile with a model of actinide production in the same r-process forming event as 182Hf with a half-life of 8.9 My [G.J. Wasserburg, M. Busso, R. Gallino, Abundances of actinides and short-lived nonactinides in the interstellar medium: Diverse supernova sources for the r-processes, Astrophys. J. 466 (1996) L109–L113]. The alternative models of 182Hf production via a neutron-rich fast s-process, occurring, for example, in the helium burning shell in a 25 solar mass star during explosive nucleosynthesis [G.J. Wasserburg, M. Busso, R. Gallino, Abundances of actinides and short-lived nonactinides in the interstellar medium: Diverse supernova sources for the r-processes, Astrophys. J. 466 (1996) L109–L113], or via a distinct r-process event that is separate from actinide production [G.J. Wasserburg, M. Busso, R. Gallino, K.M. Nollet, Short-lived nuclei in the early solar system: Possible AGB sources, Nucl. Phys. A (in press)], may provide a viable explanation. However, further studies are also required to assess the veracity of Cm–U systematics, which are critically dependent on the suitability of using Nd and the light rare earth elements (LREEs) as a chemical proxy for Cm. [Copyright &y& Elsevier]

Abstract: Past changes in the seasonal distribution of insolation across the Earth''s surface are thought to play a critical role in Quaternary climate cycles. In this study we use Sr/Ca and δ 18O as geochemical proxies in the skeleton of a fossil Porites coral to reconstruct the seasonal cycle of sea surface temperature (SST) at Henderson Island, southeast Pacific (24°S, 128°W) during the Marine Isotope Stage (MIS) 9 interglacial (∼ 339–303 ka). Previously-published closed-system U-series ages provide broad age constraints for the timing of reef growth for this unit on Henderson Island, ranging between 334 and 306 ka. We apply published δ 18O-SST slope relationships to the stacked δ 18O annual cycle in the fossil Porites, and find the amplitude of the seasonal cycle of SST recorded by the MIS 9 coral to be ∼ 4.1±0.57°C, which agrees within error with the modern seasonal cycle of SST (∼ 4.1°C). Sr/Ca-SST slope relationships applied to the fossil Porites stacked Sr/Ca annual cycle suggest the amplitude of the seasonal cycle of SST was ∼ 4.7±0.75°C, exceeding the modern cycle by ∼ 15%, but within error of the modern value. Taken together, these results suggest the seasonal cycle of SST at Henderson Island during MIS 9 equaled or exceeded the modern amplitude. Using modern latitudinal relationships between insolation seasonality and SST seasonality, we present a new application for SST amplitudes reconstructed from fossil corals that can be used in conjunction with U-series ages to provide additional geochronological constraints on the development of open-ocean, interglacial reefs. [Copyright &y& Elsevier]

[Display omitted] • Metamorphosed paleoproterozoic manganese mineralization from the Borborema Province. • Manganese ores consists mainly of manganese-oxyhydroxides, spessartine and rhodonite. • Carbonate inclusions and garnet composition suggests marly protoliths. • Anoxic sediments' deposition on the seafloor. • Medium-grade manganese ores development during exposure to surface water. The Paleoproterozoic Lagoa do Riacho manganese deposit in the Borborema Province is central to unravelling the genesis of Paleoproterozoic manganese deposits, Paleoproterozoic redox evolution and genetic relationship to the West African Craton. With manganese contents averaging 35 wt%, the Lagoa do Riacho manganese unit is lithologically subdivided into oxidized and silicate manganese ores and a garnetite (garnet-rich rocks) subgroup. The oxidized manganese ore consists mainly of pyrolusite, manganese-oxyhydroxide and spessartine. The silicate manganese ore has rhodonite, tephroite and spessartine. Garnetite contains spessartine and minor quartz and rhodonite. The main host rocks include garnet quartzite and graphite-bearing pelitic gneiss. The composition of carbonate inclusions in spessartine-rhodonite and Ca-Mn fractionation between garnet core and rim suggests all these manganese-rich rocks probably formed from protoliths of marl composition. Biogenic, syn-sedimentary graphite in the manganese-rich rocks and their host rocks indicates organic matter was deposited along with the marl protolith. Within this general context and through chemical-petrological relations, we outline an initial environment involving anoxic sediments' deposition (eg., organic matter-rich manganese marl and black shales, and wackes) on the seafloor. The presence of spessartine, rhodonite, and tephroite suggests peak metamorphic conditions reached amphibolite facies conditions (6–7 kbars and 550–700 °C). Amphiboles indicate later retrograde stages and carbonate veins suggest a possible hydrothermal stage after manganese deposition. The metamorphosed manganese-rich rocks were upgraded to medium-grade manganese ores during exposure to surface water. Our results indicated that the manganese-rich rocks and their host rocks were generated in a sedimentary context, possibly in a marine setting with carbonate and organic matter contribution. [ABSTRACT FROM AUTHOR]

Isotopic composition of uranium has previously been used to infer the depositional redox environment of uranium ore concentrates and also provide a potential signature to inform nuclear forensic investigations. This study evaluates the diagnostic power of the U isotope signature by investigating (1) the heterogeneity of U isotope compositions in samples collected from the same mine and/or vein, and (2) the influence of U ore processing on 238U/235U and 234U/238U ratios. These characteristics are explored via high precision mass spectrometric measurement of vein type uranium ore samples collected predominantly from mines located in central Portugal and Southwest England. Samples collected from the same vein and mine exhibit δ238U values from −0.16 to +0.03 (±0.04) ‰ and −1.6 to −64.7 (±0.4) ‰ for δ234U (±2SD). These variations can be attributed to redox-driven isotope fractionation processes and/or U redistribution during localised leaching and re-precipitation. Analyses of residues and leachates from small-scale batch experiments designed to simulate industrial U ore leaching procedures reveal significant positive and negative changes in isotope composition in the leachate relative to the bulk material (up to 0.21 ± 0.06‰ for δ238U and 62.0 ± 0.6‰ for δ234U). These findings highlight the possibility of significantly different δ238U and δ234U of uranium ore concentrate from the same mine even if manufacturing processes remain unchanged. • Localised U isotope heterogeneity is observed in vein type uranium ore deposits. • Changes in 234U/238U and 238U/235U are observed during acid leaching experiments. • These data suggest U isotope ratios change during conversion from ore to UOC. • Implications for the use of the uranium isotopic signature in nuclear forensics. [ABSTRACT FROM AUTHOR]

The molybdenum (Mo) and uranium (U) isotope compositions recorded in carbonate rich sediments are emerging as promising paleo-redox proxies. However, the effects of early diagenetic effects within the sediments on these isotope systems are not well constrained. We examined the Mo and U isotopic systematics in anoxic carbonate rich sediments in a semi enclosed karstic marine lake (Malo Jezero) of the Island of Mljet, Adriatic Sea. Measurements of water column redox behavior in the lake since the 1950s, have shown a transition from anoxic-sulfidic conditions in the deeper water column to more oxic conditions and anoxia refined to the sediment and pore-waters. A 50 cm long sediment core from the deepest part of the lake, show a transition from moderate to high authigenic Mo and U accumulation with depth, consistent with the changing lake redox environment in the past. In the deep euxinic part of the core, the authigenic Mo and U are isotopically lighter and heavier, respectively, than seawater, following similar systematics as observed in other modern euxinic basins, with high, but non-quantitative, Mo and U uptake into the sediments. Based on Bahamas bank carbonate sediments, it has been suggested that the 238U/235U ratio is ~+0.25‰ higher compared to seawater from the effects of early carbonate sediment diagenesis and this carbonate vs. seawater off-set is applicable to carbonate rich sediments across the geological past. The shallower part of lake sediment core was deposited under similar redox conditions as the Bahamas sediments, and these sediments show an average 238U/235U ratio +0.31 ± 0.01‰ (2SE) higher than seawater. Although the average 238U/235U ratios for these two carbonate rich settings are similar, caution is necessary when inferring seawater 238U/235U compositions from such sediments, as they contain U from different sources (e.g. diagenetic uptake and carbonate-bound). The Mo isotope compositions within the same Malo Jezero sediments are variable but approaches the seawater composition at low pore-water H 2 S concentrations. This show the potential of using the Mo isotope composition from carbonate rich sediments to infer the seawater composition, however, further work is required to establish the link between the Mo isotope composition and the chemistry of the pore water environment. • δ98Mo within carbonate rich sediments may be similar to seawater under certain conditions • diagenetic altered primary carbonates are enriched in heavy U isotopes • correlation of sedimentary organic matter with U and Mo was not observed • caution is necessary if applying off-sets values to infer seawater compositions • sedimentary δ98Mo likely is linked to the porewater [H 2 S] concentration • combined Mo and U isotope systematics is promising paleoredox tool [ABSTRACT FROM AUTHOR]