Bulk and Mapping Speciation Analyses Unveil the Pattern and Heterogeneity of Cu Species during Organic Waste Treatment.

Organic wastes (OWs) can be a common source of copper (Cu) contamination of agricultural soils. Here we conducted a comprehensive study of 22 raw and treated OWs sampled at 6 different full-scale OW treatment plants. Bulk XANES analysis findings indicated that the Cu oxidation state was subject to changes throughout the OW treatment process, mostly depending on the anaerobic/aerobic conditions prevailing in each treatment stage.

Environmental stability of a uranium-plutonium-carbide phase.

A plutonium-rich carbide, (U,Pu)(Al,Fe)C, was discovered in a hot particle from the Maralinga nuclear testing site in South Australia. The particle was produced between 1960 and 1963 and has been exposed to ambient conditions since then. The new phase belongs to a group of ternary carbides known as 'derivative-MAX phases'.

Microbial adaptations and biogeochemical cycling of uranium in polymetallic tailings.

Microorganisms inhabiting uranium (U)-rich environments have specific physiological and biochemical coping mechanisms to deal with U toxicity, and thereby play a crucial role in the U biogeochemical cycling as well as associated heavy metals. We investigated the diversity and functional capabilities of indigenous bacterial communities inhabiting historic U- and Rare-Earth-Elements-rich polymetallic tailings from the Mount Painter Inlier, Northern Flinders Ranges, South Australia. Bacterial diversity profiling identified Actinobacteria as the predominant phylum in all samples.

From biomolecules to biogeochemistry: Exploring the interaction of an indigenous bacterium with gold.

Specialised microbial communities colonise the surface of gold particles in soils/sediments, and catalyse gold dissolution and re-precipitation, thereby contributing to the environmental mobility and toxicity of this 'inert' precious metal. We assessed the proteomic and physiological response of Serratia proteamaculans, the first metabolically active bacterium enriched and isolated directly from natural gold particles, when exposed to toxic levels of soluble Au (10 μM). The results were compared to a metal-free blank, and to cultures exposed to similarly toxic levels of soluble Cu (0.

Nature and coordination geometry of geologically relevant aqueous Uranium(VI) complexes up to 400 ºC: A review and new data.

The structure of the uranyl aqua ion (UO) and a number of its inorganic complexes (specifically, UOCl, UOCl, UOSO, [Formula: see text] , [Formula: see text] and UOOH) have been characterised using X-Ray absorption spectroscopy/extended X-Ray absorption fine structure (XAS/EXAFS) at temperatures ranging from 25 to 326 ºC. Results of ab initio molecular dynamics (MD) calculations are also reported for uranyl in chloride and sulfate-bearing fluids from 25 to 400 ºC and 600 bar to 20 kilobar (kb). These results are reported alongside a comprehensive review of prior structural characterisation work with particular focus given to EXAFS works to provide a consistent and up-to-date view of the structure of these complexes under conditions relevant to U mobility in ore-forming systems and around high-grade nuclear waste repositories.

Silica-assisted pyro-hydrolysis of CaCl waste for the recovery of hydrochloric acid (HCl): Reaction pathways with the evolution of Ca(OH)Cl intermediate by experimental investigation and DFT modelling.

The chlorine evolution mechanism remains unclear during the thermal treatment of CaCl/Ca(OH)Cl-containing solid waste. In this paper, we have conducted both experimental investigation and density functional theory (DFT) calculation to elucidate the mechanism of pyro-hydrolysis of CaCl with and without SiO in the temperature ranges of 400-900 °C. It was determined that pyro-hydrolysis of CaCl alone generated a maximum of 12% HCl by decomposition into Ca(OH)Cl, which is a stable intermediate that can be reverted to CaCl at 800 °C.

Carbonate complexation enhances hydrothermal transport of rare earth elements in alkaline fluids.

Rare earth elements (REE), essential metals for the transition to a zero-emission economy, are mostly extracted from REE-fluorcarbonate minerals in deposits associated with carbonatitic and/or peralkaline magmatism. While the role of high-temperature fluids (100 < T < 500 °C) in the development of economic concentrations of REE is well-established, the mechanisms of element transport, ore precipitation, and light (L)REE/heavy (H)REE fractionation remain a matter of debate. Here, we provide direct evidence from in-situ X-ray Absorption Spectroscopy (XAS) that the formation of hydroxyl-carbonate complexes in alkaline fluids enhances hydrothermal mobilization of LREE at T ≥ 400 °C and HREE at T ≤ 200 °C, even in the presence of fluorine.

Kinetically driven successive sodic and potassic alteration of feldspar.

The dynamic evolutions of fluid-mineral systems driving large-scale geochemical transformations in the Earth's crust remain poorly understood. We observed experimentally that successive sodic and potassic alterations of feldspar can occur via a single self-evolved, originally Na-only, hydrothermal fluid. At 600 °C, 2 kbar, sanidine ((KNa)AlSiO) reacted rapidly with a NaCl fluid to form albite (NaAlSiO); over time, some of this albite was replaced by K-feldspar (KAlSiO), in contrast to predictions from equilibrium reaction modelling.

The nature of Pu-bearing particles from the Maralinga nuclear testing site, Australia.

The high-energy release of plutonium (Pu) and uranium (U) during the Maralinga nuclear trials (1955-1963) in Australia, designed to simulate high temperature, non-critical nuclear accidents, resulted in wide dispersion µm-sized, radioactive, Pu-U-bearing 'hot' particles that persist in soils. By combining non-destructive, multi-technique synchrotron-based micro-characterization with the first nano-scale imagining of the composition and textures of six Maralinga particles, we find that all particles display intricate physical and chemical make-ups consistent with formation via condensation and cooling of polymetallic melts (immiscible Fe-Al-Pu-U; and Pb ± Pu-U) within the detonation plumes. Plutonium and U are present predominantly in micro- to nano-particulate forms, and most hot particles contain low valence Pu-U-C compounds; these chemically reactive phases are protected by their inclusion in metallic alloys.

Trace element catalyses mineral replacement reactions and facilitates ore formation.

Reaction-induced porosity is a key factor enabling protracted fluid-rock interactions in the Earth's crust, promoting large-scale mineralogical changes during diagenesis, metamorphism, and ore formation. Here, we show experimentally that the presence of trace amounts of dissolved cerium increases the porosity of hematite (FeO) formed via fluid-induced, redox-independent replacement of magnetite (FeO), thereby increasing the efficiency of coupled magnetite replacement, fluid flow, and element mass transfer. Cerium acts as a catalyst affecting the nucleation and growth of hematite by modifying the Fe(aq)/Fe(aq) ratio at the reaction interface.

Selective radionuclide co-sorption onto natural minerals in environmental and anthropogenic conditions.

Anthropogenic activities can redistribute the constituents of naturally occurring radioactive materials (NORM), posing potential hazards to populations and ecosystems. In the present study, the co-sorption of several RN from the U decay chain- U, Th, Ra, Pb and Po, onto common minerals associated with mining activities (chalcopyrite, bornite, pyrite and barite) was investigated, in order to identify the various factors that control long-term NORM mobility and retentivity in environmental acid-mine drainage systems and hydrometallurgical processing. The results show selective RN co-sorption to the various natural minerals, suggesting that mineral-specific mechanisms govern the variability in NORM mobility and retentivity.

Understanding the mobility and retention of uranium and its daughter products.

Knowledge of the behavior of technologically enhanced naturally occurring radioactive materials derived through the decay of U and its daughter products, and their subsequent fractionation, mobilization and retention, is essential to develop effective mitigation strategies and long-term radiological risk prediction. In the present study, multiple state-of-the-art, spatially resolved micro-analytical characterization techniques were combined to systematically track the liberation and migration of radionuclides (RN) from U-bearing phases in an Olympic Dam Cu flotation concentrate following sulfuric-acid-leach processing. The results highlighted the progressive dissolution of U-bearing minerals (mainly uraninite) leading to the release, disequilibrium and ultimately upgrade of daughter RN from the parent U.

Synchrotron X-ray absorption spectroscopy study of the evolution of chlorine during the pyro-hydrolysis of calcium and magnesium chloride waste.

Effective liberation of chlorine (Cl) as a recoverable product such as hydrochloric acid is crucial for the clean disposal of massive Cl-bearing industrial solid waste. This study aims to clarify the evolution of Cl upon the pyrohydrolysis of CaCl waste. Particularly, the use of silica and MgCl to promote the breakage of Ca-Cl bonds to release HCl gas has been investigated, via synchrotron X-ray absorption spectroscopy (XAS).

Synthesis of in-situ Al-defected iron oxide nanoflakes from coal ash: A detailed study on the structure, evolution mechanism and application to water remediation.

The recovery of value-added materials from coal ash waste is of highly economic value and sustainable significance. However, researches on the synthesis of defect-engineering nanomaterials from coal ash are still blank. Herein, iron oxide (FeAlO simplified as FAO) nanoflakes were successfully synthesized from a brown coal fly ash (BCFA) waste.

Metal resistant bacteria on gold particles: Implications of how anthropogenic contaminants could affect natural gold biogeochemical cycling.

In Earth's near-surface environments, gold biogeochemical cycling involves gold dissolution and precipitation processes, which are partly attributed to bacteria. These biogeochemical processes as well as abrasion (via physical transport) are known to act upon gold particles, thereby resulting in particle transformation including the development of pure secondary gold and altered morphology, respectively. While previous studies have inferred gold biogeochemical cycling from gold particles obtained from natural environments, little is known about how metal contamination in an environment could impact this cycle.

The aqueous chemistry of polonium (Po) in environmental and anthropogenic processes.

The longest-lived naturally occurring isotope of polonium is polonium-210, one of the daughters of uranium-238 (138 days half-life). As a daughter radionuclide of radon-222, polonium-210 can become enriched in pore fluids in U-bearing rocks, leading to contents in excess of 100 Bq.g in some products from the mineral, coal, oil and gas industries (e.

Garnet peridotites reveal spatial and temporal changes in the oxidation potential of subduction.

Changes in the oxygen fugacity (fO) of the Earth's mantle have been proposed to control the spatial and temporal distribution of arc-related ore deposits, and possibly reflect the evolution of the atmosphere over billions of years. Thermodynamic calculations and natural evidence indicate that fluids released from subducting slabs can oxidise the mantle, but whether their oxidation potential varied in space and time remains controversial. Here, we use garnet peridotites from western Norway to show that there is a linear decrease in maximum fO with increasing depth in the mantle wedge.

Temporal Evolution of Copper Distribution and Speciation in Roots of Triticum aestivum Exposed to CuO, Cu(OH), and CuS Nanoparticles.

Utilization of nanoparticles (NP) in agriculture as fertilizers or pesticides requires an understanding of the NP properties influencing their interactions with plant roots. To evaluate the influence of the solubility of Cu-based NP on Cu uptake and NP association with plant roots, wheat seedlings were hydroponically exposed to 1 mg/L of Cu NPs with different solubilities [CuO, CuS, and Cu(OH)] for 1 h then transferred to a Cu-free medium for 48 h. Fresh, hydrated roots were analyzed using micro X-ray fluorescence (μ-XRF) and imaging fluorescence X-ray absorption near edge spectroscopy (XANES imaging) to provide laterally resolved distribution and speciation of Cu in roots.

Recrystallization of Manganite (γ-MnOOH) and Implications for Trace Element Cycling.

The recrystallization of Mn(III,IV) oxides is catalyzed by aqueous Mn(II) (Mn(II)) during (bio)geochemical Mn redox cycling. It is poorly understood how trace metals associated with Mn oxides (e.g.

Characterization of uranium redox state in organic-rich Eocene sediments.

The presence of organic matter (OM) has a profound impact on uranium (U) redox cycling, either limiting or promoting the mobility of U via binding, reduction, or complexation. To understand the interactions between OM and U, we characterised U oxidation state and speciation in nine OM-rich sediment cores (18 samples), plus a lignite sample from the Mulga Rock polymetallic deposit in Western Australia. Uranium was unevenly dispersed within the analysed samples with 84% of the total U occurring in samples containing >21 wt % OM.

Synergistic Toxicity of Copper and Gold Compounds in Cupriavidus metallidurans.

The bacterium can reduce toxic gold(I/III) complexes and biomineralize them into metallic gold (Au) nanoparticles, thereby mediating the (trans)formation of Au nuggets. In Au-rich soils, most transition metals do not interfere with the resistance of this bacterium to toxic mobile Au complexes and can be removed from the cell by plasmid-encoded metal efflux systems. Copper is a noticeable exception: the presence of Au complexes and Cu ions results in synergistic toxicity, which is accompanied by an increased cytoplasmic Cu content and formation of Au nanoparticles in the periplasm.

Thermodynamic modeling of poorly complexing metals in concentrated electrolyte solutions: an X-ray absorption and UV-Vis spectroscopic study of Ni(II) in the NiCl2-MgCl2-H2O system.

Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.

A novel route for the synthesis of mesoporous and low-thermal stability materials by coupled dissolution-reprecipitation reactions: mimicking hydrothermal mineral formation.

Replacement reactions ('pseudomorphism') commonly occur in Nature under a large range of conditions (T 25 to >600 degrees 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.

Mechanisms of gold biomineralization in the bacterium Cupriavidus metallidurans.

While the role of microorganisms as main drivers of metal mobility and mineral formation under Earth surface conditions is now widely accepted, the formation of secondary gold (Au) is commonly attributed to abiotic processes. Here we report that the biomineralization of Au nanoparticles in the metallophillic bacterium Cupriavidus metallidurans CH34 is the result of Au-regulated gene expression leading to the energy-dependent reductive precipitation of toxic Au(III)-complexes. C.