A growing literature is demonstrating that platinum (Pt) is transformed under surface conditions; yet (bio)geochemical processes at the nugget-soil-solution interface are incompletely understood. The reactivity of Pt exposed to Earth-surface weathering conditions, highlighted by this study, may improve our ability to track its movement in natural systems, e.g., focusing on nanoparticles as a strategy for searching for new, undiscovered sources of this precious metal. To study dissolution/re-precipitation processes of Pt and associated elements, grains of Pt-Fe alloy were collected from a soil placer deposit at the Fifield Pt-field, Australia. Optical- and electron-microscopy revealed morphologies indicative of physical transport as well as chemical weathering. Dissolution "pits," cavities, striations, colloidal nano-particles, and aggregates of secondary Pt platelets as well as acicular, iron (Fe) hydroxide coatings were observed. FIB-SEM-(EBSD) combined with S-μ-XRF of a sectioned grain showed a fine layer of up to 5 μm thick composed of refined, aggregates of 0.2 to 2 μm sized crystalline secondary Pt overlying more coarsely crystalline Pt-Fe-alloy of primary magmatic origin. These results confirm that Pt is affected by geochemical transformations in supergene environments; structural and chemical signatures of grains surfaces, rims, and cores are linked to the grains' primary and secondary (trans)formational histories; and Pt mobility can occur under Earth surface conditions. Intuitively, this nanophase-Pt can disperse much further from primary sources of ore than previously thought. This considerable mineral reactivity demonstrates that the formation and/or release of Pt nanoparticles needs to be measured and incorporated into exploration geochemistry programs.
Phosphorus is an essential element for all known life, and the global phosphorus cycle is widely believed to be a key factor limiting the extent of Earth's biosphere. The size and scope of any biosphere beyond our solar system is similarly likely to be limited by the planetary cycling of bioavailable phosphorus. Continental weathering has long been considered to be the only source of bioavailable phosphorus to the oceans, with submarine hydrothermal processes acting as a phosphorus sink. This opens up the possibility of severe phosphorus limitation on the early Earth prior to the widespread emergence of continental crust above sea level, and further implies that a common class of volatile-rich habitable exoplanet - so called 'waterworlds' - may be biological deserts. However, this framework is based on the behavior of phosphorus in modern hydrothermal systems interacting with pervasively oxygenated deep oceans. Here, we present new experimental results indicating that abiotic carbon dioxide sequestration during anoxic basalt alteration is an efficient source of bioavailable phosphorus. Placing these observations into the context of a simple model of planetary phosphorus-carbon-oxygen mass balance, we suggest that volatile-rich Earth-like planets lacking exposed continents may actually be more likely than Earth to develop robust biospheres that can lead to remotely detectable atmospheric biosignatures.
Phosphorus is an essential element for life, and the phosphorous cycle is widely believed to be a key factor limiting the extent of Earth's biosphere and its impact on remotely detectable features of Earth's atmospheric chemistry. Continental weathering is conventionally considered to be the only source of bioavailable phosphorus to the marine biosphere, with submarine hydrothermal processes acting as a phosphorus sink. Here, we use a novel 29Si tracer technique to demonstrate that alteration of submarine basalt under anoxic conditions leads to significant soluble phosphorus release, with an estimated ratio between phosphorus release and CO2 consumption (P/CO2) of 3.99+/-1.03 umol/mmol. This ratio is comparable to that of modern rivers, suggesting that submarine weathering under anoxic conditions is potentially a significant source of bioavailable phosphorus to planetary oceans and that volatile-rich Earth-like planets lacking exposed continents could develop robust biospheres capable of sustaining remotely detectable atmospheric biosignatures.
Abstract To address the limitations of current dating methods, it is crucial to not only enhance existing techniques like U–Pb zircon dating but also explore alternative tools. This study focuses on three common mineral phases—zircon, apatite, and titanite—in an I-type granite. The goal is to assess their reliability as dating tools and propose improved methods for dating granitic rocks. In the case study of the Mt Stirling pluton within the Mt Buller igneous suite in Southeastern Australia, significant variability in laser ablation U–Pb zircon ages (around 100 million years) was observed. To improve the reliability of zircon age data and reduce non-magmatic-related variabilities, a data filtering protocol is applied. This protocol involves several steps such as trimming zircons with excessive K and Ca, excluding zircons with unusual core–rim age relationships, removing zircons with excessive non-formula elements (Al, Fe, and Mn), identifying hydrothermally altered zircons, and applying a 10% discordance threshold. The filtered Concordia Age (406 ± 1 Ma; mean square weighted deviation (MSWD) = 0.7, n = 80) of the host rock exhibits improved precision and reduced error compared to the unfiltered data (399 ± 2 Ma; MSWD = 9.3, n = 240). The filtered individual dates show less scatter and a mean that is different (i.e. outside statistical uncertainty), noting that their total still spans a considerable time range of ~50 million years, exceeding the individual zircon analytical reproducibility of 2 standard errors (~15 million years of 2 SE). Caution is advised when using the proposed error for the pooled analyses as a definitive precision. Similarly, trace element filtering approaches were applied to apatite and titanite samples from Mt Stirling, two phases that arguably cannot be inherited. For apatite, monitoring Ca and P as well as Zr/Y and Th/U ratios, along with identifying age groupings based on Sr concentrations, was effective in eliminating outliers and enhancing dating precision. In the case of titanite, monitoring Ca and Ti, Sr/Zr and Sr/Th ratios, and Sr/Ca and Zr/Ti ratios successfully enhanced dating precision. Notably, apatite and titanite grains were grouped in distinct Sr concentrations (high-, mid-, and low-Sr), with these groups corresponding to different date groups: high-Sr apatite and high- and low-Sr titanite returned c. 403 Ma, while low-Sr apatite and mid-Sr titanite returned c. 420 and 393 Ma, respectively. The spuriously younger or older dates may indicate an open system and influences from various common-Pb sources. The 403 Ma date coincides with the filtered zircon data, placing further confidence in the coupled approach, and is interpreted here as the igneous intrusion age. Notable is that this age is 25 Myr older than previously reported K–Ar age data, thus far considered to be the age of the intrusion. This study underscores the potential for erroneous zircon dates due to cryptic chemical influences. To enhance the reliability of age interpretation using laser ablation analyses, employing a petrochronological approach using split-stream combined age and trace element data is recommended in addition to the combination of multiple geochronometers. In the case of Mt Buller, it has proven crucial to carefully verify chemical closure of all applied geochronometers by monitoring concomitant trace element concentrations. Applied to other intrusions, petrochronology can play a critical role in obtaining reliable age information, even for igneous rocks that appear pristine. With this, we emphasise the importance of a careful approach towards individual age data interpretation, which can be produced fast and in abundance with modern analytical approaches.
Understanding the speciation and thermodynamic properties of aqueous tungsten (W) complexes under various conditions is essential for predicting W transport in hydrothermal fluids relevant to ore formation and geothermal systems. Although previous experimental and geochemical modelling studies have provided insights into W solubility in hydrothermal systems, a comprehensive molecular-level understanding of W in hydrothermal fluids remains elusive. In this study, we employed ab initio molecular dynamics (MD) simulations to determine the speciation and coordination geometries of W(VI) complexes in NaCl, NaHS, and NaF-bearing brines at temperatures up to 600 °C and pressures up to 2 kbar. These theoretical calculations were complemented by synchrotron in-situ X-ray Absorption Spectroscopy measurements of W(VI) in chloride-, sulfide-, and fluoride-rich solutions under pressures of 600 bar and temperatures ranging from 25 to 429 °C. The speciation and geometrical properties obtained from ab initio MD simulations are in reasonably good agreement with the in-situ X-ray Absorption Spectroscopy data. Our study reveals that W-Cl complexes are not stable, and W is transported as tungstates (H2WO4(aq), HWO4− and WO42−)in NaCl-rich fluids. In sulfur-rich fluids under near-neutral pH and reduced conditions (sulfide predominant), S2− ions gradually replace O2− in tungstates to form thiotungstate complexes (WO4-xSx2−, where x = 1, 2, 3, 4). The MD results suggest that fluoride (F−) plays a significant role in W transport by forming WO3F− and WO3F22− complexes, or their hydrated ions. We employed thermodynamic integration to determine the formation constants of the WO3F− and WO3F22− complexes at temperatures up to 600 °C and 2 kbar, and extrapolated these properties across a broader range of temperatures and pressures. This study underscores the significance of W-F complexes in W transportation in fluoride-bearing, acidic to neutral (pH < 8) hydrothermal fluids. In contrast, W is most likely transported as thiotungstate complexes in sulfur-bearing hydrothermal fluids within a neutral to alkaline pH range (e.g., pH 5–8.5 at 300 °C) under reduced (sulfide-stable) conditions in the Earth's crust. Existing models for W transport in hydrothermal ore fluids need to consider the influence of W-F and thiotungstate species.
Replacement reactions ('pseudomorphism') commonly occur in Nature under a large range of conditions (T 25 to >600 °C; P 1 to >5 kbar). Whilst mineral replacement reactions are often assumed to proceed by solid-state diffusion of the metal ions through the mineral, many actually proceed via a coupled dissolution and reprecipitation (CDR) mechanism. In such cases, a starting mineral is dissolved into a fluid and this dissolution is coupled with the precipitation of a replacement phase across the reaction front. In cases where there are close relationships between the crystal structures of the parent and newly formed minerals, the replacement can be topotactic (interface-coupled dissolution and reprecipitation). The kinetics and chemistry of the CDR route are fundamentally different from solid-state diffusion and can be exploited i) for the synthesis of materials that are often difficult to synthesise via traditional methods and ii) to obtain materials with unique properties. This review highlights recent research into the use of CDR for such synthetic challenges. Emphasis has been given to i) the use of CDR to synthesise compounds with relatively low thermal stability such as the thiospinel mineral violarite ((Ni,Fe)3S4), ii) preliminary work into use of CDR for the production of roquesite (CuInS2), a potentially important photovoltaic component and, iii) examples where the textures resulting from CDR reactions are controlled by the nature and texture of the parent phase and the reaction conditions; these being the formation of micro-porous gold and three-dimensional ordered arrays of nanozeolite of uniform size and crystallographic orientation.
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