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Abstract: Investigations of ‘stable’ uranium isotope fractionation during low temperature, redox transformations may provide new insights into the usefulness of the 238U/235U isotope system as a tracer of palaeoredox processes. Sandstone-hosted uranium deposits accumulate at an oxidation/reduction interface within an aquifer from the low temperature reduction of soluble U(VI) complexes in groundwaters, forming insoluble U(IV) minerals. This setting provides an ideal environment in which to investigate the effects of redox transformations on 238U/235U fractionation. Here we present the first coupled measurements of 238U/235U isotopic compositions and U concentrations for groundwaters and mineralised sediment samples from the same redox system in the vicinity of the high-grade Pepegoona sandstone-hosted uranium deposit, Australia. The mineralised sediment samples display extremely variable 238U/235U ratios (herein expressed as , the per-mil deviation from the international NBL standard CRM145). The majority of mineralised sediment samples have values between and , spanning a ca. 2‰ range. However, one sample has an unusually light isotopic composition of , which suggests a total range of U isotopic variability of up to ca. 5‰, the largest variation found thus far in a single natural redox system. The 238U/235U isotopic signature of the mineralised sediments becomes progressively heavier (enriched in 238U) along the groundwater flow path. The groundwaters show a greater than 2‰ variation in their 238U/235U ratios, ranging from values of to . The majority of the groundwater data exhibit a clear systematic relationship between 238U/235U isotopic composition and U concentration; samples with the lowest U concentrations have the lowest 238U/235U ratios. The preferential incorporation of 238U during reduction of U(VI) to U(IV) and precipitation of uranium minerals leaves the groundwaters enriched in 235U, resulting in a progressive shift in 238U/235U towards lighter values in the aqueous phase as U is removed. These data can be modelled by a closed system Rayleigh fractionation model, with a fractionation factor (α, representing the 238U/235U composition of the groundwater relative to the solid uranium minerals) ranging from ∼0.9996 to 1.0000, with the majority of datapoints ranging from α values of 0.9998 to 0.9999. The sense and magnitude of the results of this study imply that 238U/235U fractionation is likely to be controlled by volume-dependent nuclear field shift effects during the reduction of U(VI) to U(IV) during mineralisation processes. These findings support the use of the 238U/235U isotopic system as a tracer to constrain the nature and timing of palaeoredox conditions. [Copyright &y& Elsevier]

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- Strontium (Sr) content of eggs collected from redds were used to determine the spawning contribution of resident and anadromous female brown trout in the Taieri River, New Zealand and were analysed on the catchment and tributary scale. At the catchment scale, analysis of Sr showed differences between eggs collected above and below the Taieri River Gorge. Samples collected above the gorge all had low-Sr concentrations similar to levels found in an entirely resident brown trout population. Samples collected below the gorge exhibited a broad range in Sr concentrations, ranging from levels comparable to the known anadromous samples to levels comparable to the known freshwater-resident samples. This suggests that the gorge prevents upstream migration by anadromous brown trout in the Taieri River. At the tributary scale, this pattern of anadromous brown trout spawning downstream of freshwater-resident fish was repeated in one of the two tributaries located downstream of the gorge. Energetic cost of migration is the most likely explanation for the observed patterns in catchment and tributary scale distribution of spawning by resident and anadromous brown trout. It is concluded that the use of Sr concentrations in eggs collected from redds is a cost-effective and reliable method to investigate the spawning contribution by anadromous brown trout. [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]

The composition of trench sediment at convergent margins exhibits strong compositional links to the corresponding arc magmas. To test for the existence of such links at the Hikurangi margin, we provide a first geochemical characterisation of the IODP sites U1518 and U1520 drilled at the upper and incoming plate respectively. The identification of a décollement in the trench sediments allows distinction of the accreting clastic sediment above the décollement and the subducting pelagic and volcaniclastic material below it. The accreted material and that located above the décollement show homogenous Pb, Sr and Nd isotope ratios with bulk compositions of 206Pb/204Pb: 18.8953, 207Pb/204Pb: 15.6552, 208Pb/204Pb: 38.8371, 87Sr/86Sr: 0.70935, 143Nd/144Nd: 0.51241. In contrast, the material located below the décollement shows more heterogeneous Pb-Sr-Nd isotope ratios and bulk compositions of 206Pb/204Pb: 20.4826, 207Pb/204Pb: 15.7355, 208Pb/204Pb: 39.9833, 87Sr/86Sr: 0.70752, and 143Nd/144Nd: 0.51286. Tectonic erosion in the Hikurangi margin implies that accreted material could subsequently be subducted from the underside of the upper plate. Therefore, this characterisation is of prime importance for future work to constrain the role that subducted materials play in the compositional variations of the arc magmatism associated with subduction along the Hikurangi margin. [ABSTRACT FROM AUTHOR]

Monogenetic volcanism in the Maniototo Basin in the Dunedin Volcanic Group was unusual because the eroded lavas, plugs and dikes comprise spatially and temporally restricted silica-saturated and silica-undersaturated magmas. 40Ar/39Ar dating coupled with existing data and field relationships indicate that volcanism was focused at ∼11 Ma. Major and trace element data show the volcanic rocks to have mafic compositions and little evidence for fractionation and/or crustal contamination, but to have been variably altered. The volcanic rocks comprise an alkaline group and an alkaline to subalkaline transitional group, with one intermediate unit. With the exception of one flow, the transitional group has more radiogenic 87Sr/86Sr and less radiogenic 143Nd/144Nd, 206Pb/204Pb and 208Pb/204Pb than the alkaline group, as well as smaller Ti and K primitive mantle-normalised anomalies. Overall, the different magma compositions cannot be related to varying degrees of melting of equivalent mantle sources. Trace element ratios indicate that residual Ti and K-bearing mantle phases (amphibole, phlogopite) probably played a major role in the source of alkaline group but a smaller role in the transitional group. Therefore, the varying compositions of the Maniototo volcanic rocks relates to melting of a heterogeneous lithospheric mantle, or/and varying degrees of interaction with mantle hydrous metasomes as the magmas ascended. [ABSTRACT FROM AUTHOR]

Mantle xenoliths in a nephelinite in the Little Lottery River provide insight into the Miocene mantle adjacent to the Australia-Pacific plate boundary in N Canterbury. The xenoliths comprise peridotite and pyroxenite extracted from depths of ∼ 40 to 60 km. The olivine Mg# < 89, a lack of spinel and occurrence of ilmenite, elevated bulk Cr and Al, light rare Earth element (REE)-enriched clinopyroxene, and 87Sr/86Sr15 Ma clinopyroxene populations (0.7029–0.7047) in most harzburgite and dunite samples, and in all lherzolite, wehrlite, olivine websterite and orthopyroxenites, indicate that most are the product of reaction of depleted peridotite with Fe, Ti, Al and light REE-bearing silicate melts of basaltic or similar composition. Available isotopic data indicate that the xenoliths could be derived from mantle lithosphere beneath the Hikurangi Plateau, in which case the reactive melts may have been associated with the Cretaceous plateau formation. Extensive recrystallisation of olivine indicates that portions of this lithosphere mantle were affected by the deformation close to the time of entrainment. Since the eruption occurred at ∼ 15 Ma, these textures require that the mantle lithosphere in this area was deforming before formation of today's expression of the proximal Hope Fault strand of the Australia-New Zealand plate boundary. [ABSTRACT FROM AUTHOR]

The 87Sr/86Sr isotopic properties of martian meteorites, measured by isolation and purification of Rb and Sr fractions, have long been used to partially characterise Mars' mantle. However, this method is time-consuming, destructive, and subject to incorporation of terrestrial contamination due to precipitation of phases in fractures and/or grain boundaries prior to meteorite collection. In this study, we test the effectiveness of in situ acquisition of 87Sr/86Sr by laser ablation in maskelynite - a typically low Rb/Sr (<0.1) feldspar-composition glass formed during high-P shock metamorphism – as a method of rapid characterisation of Mars' mantle Sr isotope ratios. Element concentration maps and the results of unwashed and gently surface-leached bulk rock analyses indicate that terrestrial Sr has infiltrated the studied meteorites and affected bulk rock trace element budgets. However, maskelynite trace element concentrations are largely unaffected and their martian igneous Rb/Sr is preserved. In situ 87Sr/86Sr analyses of maskelynite, checked against a newly developed Sr feldspar reference material (KAN, presented here and available on demand), accurately and precisely distinguish different shergottite mantle reservoirs. The measurements reproduce published data, have uncertainties on the 4th to 5th decimal place, and yield statistically indistinguishable results in analytical sessions separated by long periods of time. The data from 11 enriched shergottites reveal there to be subtle Sr isotope variation within the enriched shergottite mantle reservoir, or that there was crustal assimilation of radiogenic components into the shergottites, or that the shergottite liquids were extracted over a time period during which the mantle reservoir 87Sr/86Sr evolved. The limited published age range of the enriched shergottites, coupled with the absence of a correlation between in situ 87Sr/86Sr and REE, Sr or Pb concentration in maskelynite, suggests that the isotope range is best explained by small variations in the enriched mantle reservoir. Given the presence of maskelynite (or plagioclase) in many meteorites, the in situ method will be useful when there are only very small volumes of material available and/or where terrestrial contamination is suspected. [ABSTRACT FROM AUTHOR]

Although amphibole has long been predicted to be a major component in the mantle source of intraplate volcanic rocks in New Zealand, the physical evidence for this phase, despite inspection of hundreds of peridotite mantle xenoliths from across the country, is limited to a handful of samples in which it is mostly a sparse component. Here, we present a suite of ultra-refractory peridotite xenoliths in an ultramafic lamprophyre from the intraplate Alpine Dike Swarm, New Zealand, that contain abundant MARID-like veins of mica (phlogopite), amphibole (pargasite) and clinopyroxene, with minor to trace rutile, ilmenite, carbonate and apatite. A key feature of inspecting these formerly refractory peridotites (olivine Mg# commonly >92) is that the chemistry of the precipitated metasomatic agent is less diluted than in cases where an invading melt reacts with fertile lithosphere. The bulk compositions of the precipitated veins vary between sub-alkaline basalt and alkaline basanite, with the peridotite wallrock hosting the basanite veins commonly enriched in Fe ± K, Ti and Al. Amphibole in all veins has high Nb, and the 24 Ma age-corrected 87Sr/86Sr values for diopside and amphibole (0.7027 to 0.7031) are indicative of derivation from a depleted mantle free of crustal material, and thus not related to subduction and arc magmatism. The Sr isotope ratios also overlap with the composition of many primitive intraplate magmas across Zealandia. Melt modelling indicates that partial melting of the veins could generate magmas with geochemical aspects of the known intraplate rocks. These rare veined peridotite occurrences therefore confirm that the Zealandia mantle lithosphere contains fusible zones that, if melted, could have played an important role in the source of intraplate basaltic magma. • Amphibole has long been predicted in the mantle source of intraplate volcanic rocks in New Zealand. • A new set of ultra-refractory peridotite xenoliths contain abundant veins comprising phlogopite, amphibole and clinopyroxene. • Amphibole Nb and 87Sr/86Sr indicate fluid derivation from a depleted mantle unrelated to subduction. • Sr isotope ratios overlap with many primitive intraplate magmas across Zealandia. • Melt models indicates that vein partial melting could generate geochemical aspects of the intraplate magmas. [ABSTRACT FROM AUTHOR]

[Display omitted] • In-situ scheelite TE and 87Sr/86Sr distinguish two types of W mineralisation. • Scheelite compositions reflect the source of the fluids. • Proximal, non-economic scheelite occurrences have local controls on composition. • Distally-sourced W deposits form along crustal discontinuities • Distally-sourced W-bearing fluids homogenise with ascent through the crust. The Otago Schist in New Zealand hosts orogenic tungsten (W) mineralization in two types. Proximally-sourced ("proximal") mineralization in sub- to lower-greenschist facies Mesozoic metasedimentary rocks within the northern flank of the Otago Schist Belt comprise quartz-calcite veins with minor scheelite and few sulfides. Distally-sourced ("distal") deposits are hosted in major crustal discontinuities within Mesozoic sub-greenschist to upper-greenschist facies metasedimentary rocks and are associated with abundant sulfides ± Au. In-situ trace element (particularly REE, Sr, Mo, Na, As) and in-situ 87Sr/86Sr compositions of scheelite show the scheelite occurring in these different mineralization types to be geochemically distinct. Proximal occurrences are characterised by scheelite with both heterogenous trace element and Sr isotope compositions displaying variations that can be linked to different veins, host rock types and scheelite generations. In contrast, scheelite within distal scheelite deposits tends to have fairly homogenous trace element and Sr isotopic ratios at the deposit to grain scale. The heterogenous compositions of proximal occurrences represent local derivation of diverse components from the sub-millimetre to meter scales and small extents of fluid flow, which resulted in a high sensitivity to sources and local rock compositions and thus limited large-scale equilibration of elemental and isotopic systematics within the scheelite they contain. The larger distal deposits formed by regional leaching by metamorphic fluids, probably at the greenschist-amphibolite facies boundary, followed by homogenisation as they ascended through the crust and leading to deposition of scheelite with rather uniform chemical characteristics. Our data re-enforce the model that tungsten mobility in the Otago Schist involved local-scale mobilisation of W in the shallow crust by breakdown of detrital rutile and scheelite at low metamorphic grade. Burial of these veined scheelite-bearing rocks to temperatures of ∼500 °C enabled remobilisation of W by metamorphic fluids, concurrent with scavenging of Au, As and S, followed by return of the metal-bearing fluids towards mid to upper crustal levels, where they precipitated scheelite. [ABSTRACT FROM AUTHOR]

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]

The insular region of Wallacea has become a focal point for studying Pleistocene human ecological and cultural adaptations in island environments, however, little is understood about early burial traditions during the Pleistocene. Here we investigate maritime interactions and burial practices at Ratu Mali 2, an elevated coastal cave site on the small island of Kisar in the Lesser Sunda Islands of eastern Indonesia dated to 15,500-3700 cal. BP. This multidisciplinary study demonstrates extreme marine dietary adaptations, engagement with an extensive exchange network across open seas, and early mortuary practices. A flexed male and a female, interred in a single grave with abundant shellfish and obsidian at Ratu Mali 2 by 14.7 ka are the oldest known human burials in Wallacea with established funerary rites. These findings highlight the impressive flexibility of our species in marginal environments and provide insight into the earliest known ritualised treatment of the dead in Wallacea., (© 2024. The Author(s).)

The growth of phytoplankton in lakes is thought to be primarily controlled by macronutrient concentrations, but the availability of trace metal micronutrients, such as iron (Fe), are increasingly recognised as important regulators of lake primary production. This study evaluates the role of Fe in regulating phytoplankton growth in lakes of different nutrient status in New Zealand. The results of this unique year-long study, combining highly sensitive trace metal concentration analysis of waters and particulates with advanced trace metal bioavailability and speciation modelling, constrains thresholds for bioavailable Fe and colloidal Fe of 0.8 nmol·L -1 and 30 nmol·L -1 , respectively, below which phytoplankton growth-limitation occurs. These thresholds specifically control diatom bloom formation and termination in lakes, thereby exerting a strong influence on freshwater carbon sequestration, given the dominance of diatoms in lake bloom assemblages. Importantly, potentially toxic cyanobacteria thrived only after events of bottom water anoxia, when additional dissolved Fe in concentrations ≥4 nmol·L -1 was released into the water column. These new thresholds for bioavailable and colloidal Fe offer the potential to manage micronutrient levels in lakes for the purpose of regulating algal bloom formation and carbon sequestration, while at the same time, suppressing the formation of harmful cyanobacterial blooms., Competing Interests: Declaration of competing interest Piet Verburg, Claudine Stirling, Susie Wood, Niklas Lehto report financial support was provided by New Zealand Ministry of Business, Innovation and Employment., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Freshwater phytoplankton blooms are increasing in prevalence and there are conflicting views on whether trace metals limit growth of key species and thus bloom formation. The Taupō Volcanic Zone (TVZ), New Zealand, was formed by multiple eruptions of a super-volcano which emitted rhyolitic tephra leaving lakes depleted in trace metals. This provides an opportunity to test the potential of trace metal limitation on freshwater phytoplankton growth under nanomolar concentrations. Growth responses of two algal species isolated from Lake Taupō, Dolichospermum lemmermannii (cyanobacteria) and Fragilaria crotonensis (diatom), to six biologically important trace metals (manganese, iron, zinc, cobalt, copper and molybdenum) were examined in culture experiments. These were conducted at three trace metal concentrations: (1) ambient, (2) two-times ambient, and (3) ten-times ambient concentrations in Lake Taupō. Elevated concentrations of iron significantly increased growth rates and maximum cell densities in D. lemmermannii, whereas no significant concentration dependence was observed for other trace metals. Fragilaria crotonensis showed no significant growth response to elevated concentrations of trace metals. These results highlight the importance of iron as a growth limiting nutrient for cyanobacteria and indicate that even small (twofold) increases in Fe concentrations could enhance cyanobacteria growth rates in Lake Taupō, potentially causing cyanobacterial blooms., (© 2022. The Author(s).)