X-ray Absorption Near-edge Structure Spectroscopy Research Articles

Spectroscopy-guided discovery of three-dimensional structures of disordered materials with diffusion models

Abstract Spectroscopy techniques such as x-ray absorption near edge structure (XANES) provide valuable insights into the atomic structures of materials, yet the inverse prediction of precise structures from spectroscopic data remains a formidable challenge. In this study, we introduce a framework that combines generative artificial intelligence models with XANES spectroscopy to predict three-dimensional atomic structures of disordered systems, using amorphous carbon (a-C) as a model system. In this work, we introduce a new framework based on the diffusion model, a recent generative machine learning method, to predict 3D structures of disordered materials from a target property. For demonstration, we apply the model to identify the atomic structures of a-C as a representative material system from the target XANES spectra. We show that conditional generation guided by XANES spectra reproduces key features of the target structures. Furthermore, we show that our model can steer the generative process to tailor atomic arrangements for a specific XANES spectrum. Finally, our generative model exhibits a remarkable scale-agnostic property, thereby enabling generation of realistic, large-scale structures through learning from a small-scale dataset (i.e. with small unit cells). Our work represents a significant stride in bridging the gap between materials characterization and atomic structure determination; in addition, it can be leveraged for materials discovery in exploring various material properties as targeted.

Molecular mechanisms of iron nanominerals formation in fungal extracellular polymeric substances (EPS) layers during fungus-mineral interactions

Extracellular polymeric substances (EPS), which envelop on fungal hyphae surface, interact strongly with minerals and play a crucial role in the formation of nanoscale minerals during biomineralization in nature environments. However, it remains poorly understood about the molecular mechanisms of nanominerals (i.e., iron nanominerals) formation in fungal EPS halos during fungus-mineral interactions. This process is vital because fungi typically grow attached to various mineral surfaces in nature. According to the changes of thickness of the fungal cell and EPS layers during the Trichoderma guizhouense NJAU 4742 and hematite cultivation experiments, we found that fungal biomineralization could trigger the formation of EPS layers. Fe-dominated nanominerals, aromatic C (283-286.1 eV), alkyl C (287.6-288.3 eV), and carboxylic C (288.4-289.1 eV) were the dominant chemical groups on the EPS layers, as determined by nanoscale secondary ion mass spectrometry (NanoSIMS), high-resolution transmission electron microscope (HRTEM), and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Further, evidence from Fe K-edge X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopy (XPS) spectra indicated that oxygen vacancy (OV) was formed on the Fe-dominated nanomineral surface during fungus-mineral interactions, which played an important role in catalyzing H2O2 decomposition and HO∗ production. Taken together, the intrinsic peroxidase-like activity by reactive oxygen species (ROS) could modulate the Fe-dominated nanominerals formation in EPS layers to newly form a physical barrier between the cell and the external environments around hyphae, providing novel insights into the effects of ROS-mediated fungal-mineral interactions on fungal nutrient recycling, attenuation of contaminants, and biological control in nature environments.

Elucidating Phosphate and Cadmium Cosorption Mechanisms on Mineral Surfaces with Direct Spectroscopic and Modeling Evidence.

The simultaneous sorption of cations and anions at the mineral-water interface can substantially alter their individual sorption characteristics; however, this phenomenon lacks a mechanistic understanding. Our study provides direct spectroscopic and modeling evidence of the molecular cosorption mechanisms of the cadmium ion (Cd2+) and phosphate (P) on goethite and layered manganese (Mn) oxide of birnessite, through in situ attenuated total reflection Fourier-transform infrared (ATR-FTIR), P K-edge X-ray absorption near-edge structure (XANES) spectroscopy, and surface complexation modeling. Phosphate synergistically cosorbed with Cd on goethite predominantly through P-bridged ternary complexes (≡Fe-P-Cd) and electrostatic interactions at wide pH conditions. Likewise, P and Cd exhibited synergistic cosorption on birnessite by forming P-bridged ternary complexes (≡Mn-P-Cd) and weak competitive sorption at the layer edge sites. As pH and Cd loading increased, the surface P species transitioned from a binary complex to a ternary complex and/or Cd3(PO4)2 precipitate for both goethite and birnessite. Compared to that in solution at pH 8, the formation of Cd3(PO4)2 was inhibited by the presence of goethite and birnessite, ascribed to the specific adsorption of P and Cd, more pronounced in birnessite due to the stronger sorption of Cd at its vacant sites. The discovered cosorption mechanisms of P and Cd have important implications for understanding and predicting their mobility and availability in Cd-contaminated settings.

Ultrastructural Perspectives on the Biology and Taphonomy of Tonian Microfossils From the Draken Formation, Spitsbergen.

Silicified peritidal carbonates of the Tonian Draken Formation, Spitsbergen, contain highly diverse and well-preserved microfossil assemblages dominated by filamentous microbial mats, but also including diverse benthic and/or allochthonous (possibly planktonic) microorganisms. Here, we characterize eight morphospecies in focused ion beam (FIB) ultrathin sections using transmission electron microscopy (TEM) and X-ray absorption near-edge structure (XANES) spectromicroscopy. Raman and XANES spectroscopies show the highly aromatic molecular structure of preserved organic matter. Despite this apparently poor molecular preservation, nano-quartz crystallization allowed for the preservation of various ultrastructures distinguished in TEM. In some filamentous microfossils (Siphonophycus) as well as in all cyanobacterial coccoids, extracellular polysaccharide sheaths appear as bands of dispersed organic nanoparticles. Synodophycus microfossils, made up of pluricellular colonies of coccoids, contain organic walls similar to the F-layers of pleurocapsalean cyanobacteria. In some fossils, internal content occurs as particulate organic matter, forming dense networks throughout ghosts of the intracellular space (e.g., in Salome svalbardensis filaments), or scarce granules (in some Chroococcales). In some chroococcalean microfossils (Gloeodiniopsis mikros, and also possibly Polybessurus), we find layered internal contents that are more continuous than nanoparticulate bands defining the sheaths, and with a shape that can be contracted, folded, or invaginated. We interpret these internal layers as the remains of cell envelope substructures and/or photosynthetic membranes thickened by additional cellular material. Some Myxococccoides show a thick (up to ~ 0.9 μm) wall ultrastructure displaying organic pillars that is best reconciled with a eukaryotic affinity. Finally, a large spheroid with ruptured wall, of uncertain affinity, displays a bi-layered envelope. Altogether, our nanoscale investigations provide unprecedented insights into the taphonomy and taxonomy of this well-preserved assemblage, which can help to assess the nature of organic microstructures in older rocks.

Chromium Immobilization as Cr-Spinel by Regulation of Fe(II) and Fe(III) Concentrations

The complex environmental conditions at Cr-contaminated sites, characterized by uneven ion distribution, oxidants competition, and limited solid-phase mobility, lead to inadequate mixing of Fe-based reducing agents with Cr, posing significant challenges to the effectiveness of Cr remediation through Cr-spinel precipitation. This study investigates the distinct roles of Fe(II), Fe(III), and Cr(III) in Cr-spinel crystallization under ambient temperature and pressure. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray absorption near-edge structure spectroscopy, and Mössbauer spectroscopy were employed to elucidate the phase composition, microstructure, and ion coordination within the precipitates. Our findings indicate that Fe(II) acts as a catalyst in the formation of the spinel phase, occupying octahedral sites within the spinel structure. Under the catalytic influence of Fe(II), Fe(III) transitions into the spinel phase, occupying both the tetrahedral and the remaining octahedral sites. Meanwhile, Cr(III), due to its high octahedral site preference energy, preferentially occupies the octahedral sites. When Fe(II) or Fe(III) is present but does not meet the ideal stoichiometric ratio, a deficiency in Fe(II) leads to low yield and poor crystallinity of Cr-spinel, whereas a deficiency in Fe(III) can completely inhibit its formation. Conversely, when either Fe(II) or Fe(III) is in excess, the formation of Cr-spinel remains feasible. Furthermore, metastable Cr phases can be transformed into stable Cr-spinel by adjusting the Fe(II)/Fe(III)/Cr(III) ratio. These results highlight the broad range of conditions under which Cr-spinel mineralization can occur in environmental settings, enhancing our understanding of the mechanisms driving Cr-spinel formation in Cr-contaminated sites treated with Fe-based reducing agents. This research provides critical insights for optimizing Cr remediation strategies.

Mineral-associated organic carbon promoted phosphorus accumulation in long-term fertilized black soil

Soil phosphorus (P) pool is intimately connected to organic carbon (OC), especially mineral-associated OC (MAOC). However, the relationship and mechanism between MAOC fractions and P fractions and their response to fertilization remain unclear. According to a long-term field trial in black soil, topsoils from no-fertilizer control, chemical fertilizer (36 kg P ha-1), and straw addition (42 kg P ha-1) for 21 and 29 years were collected, and organo-mineral complexes (< 20 µm) were separated and analyzed. Compared to no-fertilizer control, chemical fertilizer resulted in soil acidification (soil pH 6.15–6.27), increasing the contents of the MAOC fraction bound to minerals by weak linkages in complexes. Straw addition maintained soil pH at 7.53–7.84, and the contents of some MAOC fractions (which were remaining water-soluble, bound by cations, encapsulated by resistant carbonate, and insoluble humin) were significantly higher than that of chemical fertilizer. Fertilization applications increased total P contents in organo-mineral complexes, with similar levels of total P observed between chemical fertilizer and straw addition. Chemical fertilizer mainly increased highly labile inorganic P (Pi) extracted from resin, NaHCO3 and NaOH, as well as organic P (Po) extracted by NaHCO3, and straw addition mainly increased moderately labile Pi extracted from dilute HCl. Correlation analysis showed that the increased and dominant MAOC fractions had positive relationships with the increased P fractions. X-ray absorption near-edge structure (XANES) spectroscopy further identified that chemical fertilizer increased the proportion of AlPO4, suggesting that MAOC promotes the retention of labile P via association with Al under weakly acidic conditions. Straw addition increased the proportion of Ca3(PO4)2 and Ca5(PO4)3OH; moreover, it also increased the maximum P sorption capacity of complexes, suggesting that MAOC enhances P sorption via association with Ca under weakly alkaline conditions and that adsorbed P will transform into more stable Ca-associated P. Our findings demonstrate that MAOC promotes P accumulation via association with different P fractions, and these processes are mineral and pH-dependent.

Synchrotron-based P K-edge XANES spectroscopy reveals the transition of phosphorus cycling in the early Cambrian ocean

Phosphorus, as a long-term limiting nutrient, is essential for the rapid animal diversification in the early Cambrian ocean. However, the widespread occurrence of phosphorites during this period indicates anomalous phosphorus cycling mechanisms that remain inadequately explored. To investigate the interplay between marine redox conditions and phosphorus cycling, we used geochemical proxies and synchrotron-based P K-edge X-ray Absorption Near Edge Structure (XANES) spectroscopy to analyze the Cambrian Terreneuvian Yurtus Formation (Fortunian to Stage 2) from the Tarim Block. Redox-sensitive elements, iron speciation and nitrogen isotopes reveal an expansion of the surface oxygenated waters, despite persistent ferruginous bottom waters. Moreover, a shift of phosphorus speciation was observed in bedded cherts via P K-edge XANES, suggesting a transition of phosphorus cycling. Specifically, the samples exhibit low total phosphorus contents with a high rate of carbonate-fluorapatite authigenesis in the lower Yurtus Formation. This is followed by an increase in the proportion of terrestrial-derived fluorapatite and iron-bound phosphorus, corresponding to the expansion of surface oxygenated waters. Our findings reveal a significant shift in dominant phosphorus speciation in the early Cambrian marine sediments, which is intricately linked to the coupled phosphorus‑iron‑carbon‑oxygen cycles in the Cambrian ocean.

Molecular understanding of speciation transformation of phosphorus and sulfur in food waste digestate during hydrothermal treatment

Recovering phosphorus (P) and sulfur (S) from biowaste is a key strategy to address the current P resources shortage and soil S deficiency. Food waste digestate (FWD) contains high contents of P and S, while its direct application is severely limited by available nutrient leaching loss and pollutant exposure. Hydrothermal treatment (HT) is an effective technique for biowaste disposal, enabling detoxification and resource recovery. The study systematically investigated the speciation transformation of P and S in FWD during HT, using chemical extraction and in-situ X-ray absorption near-edge structure (XANES) spectroscopy. The results revealed that up to 98% of P in FWD was enriched in the solid product (hydrochar) after HT, with organic P and labile P being converted into stable Ca-bound forms, predominantly hydroxyapatite. This transformation reduced the risk of P leakage loss compared to untreated FWD. Interestingly, the S speciation evolution exhibited more complexity. The highest S proportion in hydrochar of 73.6% was observed at 140 °C under HT. As the temperature increased from 140 °C to 180 °C, S in the hydrochar gradually dissolved into the liquid phase, attributed to unstable aliphatic compounds (mercaptan) and the sulfides oxidizing to sulfates. Above 180 °C, intermediate oxidation states and sulfates were reduced and formed metal sulfides. These findings have important implications for understanding the viability of HT for FWD disposal and the value-added utilization of FWD.

XANES spectroscopy proofs pH‐dependent P sorption partitioning to Fe oxyhydroxides versus montmorillonite in acidic soils

AbstractBackgroundFe and Al oxyhydroxides are well‐known phosphorus (P)‐retaining minerals in soils. Little information is available regarding the relevance of clay minerals for the sorption of P in mixed oxyhydroxide–clay mineral systems and pH effects on P sorption partitioning.Aims and MethodsWe wanted to investigate pH effects on P sorption partitioning between Fe oxyhydroxides and high‐activity clay minerals in mixed‐mineral systems. We quantified the relative contribution of ferrihydrite or goethite versus Al‐saturated montmorillonite (Al‐MT) to the retention of orthophosphate (oPO4) and inositol hexakisphosphate (IHP) at different pH values (3–6). We combined the analysis of P solution concentration changes with the quantification of P bound to Fe(III) versus Al in the Fe oxyhydroxide/Al‐MT mixtures by X‐ray absorption near‐edge structure (XANES) spectroscopy.ResultsOrthophosphate was preferentially retained by ferrihydrite, compared to Al‐MT at pH 3–6. The opposite was observed for goethite at low P solution concentrations. The contribution of Al‐MT versus Fe oxyhydroxides to oPO4 retention increased with pH. This is attributed to a speciation change of clay‐adsorbed Al from monomeric Al3+ to polynuclear Al hydroxy species. IHP was predominantly retained by Al‐MT rather than ferrihydrite at pH 3–6, probably by the formation of adsorbed and surface‐precipitated Al phytate complexes.ConclusionsSynchrotron‐based XANES spectroscopy allows for quantifying P adsorbed to co‐existing pedogenic Fe(III) oxyhydroxides versus Al‐MT in mixed‐mineral systems. Soil P retention partitioning to these minerals depends on (1) dominating P form (oPO4, IHP), (2) relative abundance of high‐activity clay minerals, short‐range ordered and crystalline Fe oxyhydroxides, and (3) solution pH.

Iron distribution and speciation in a 3D-printed hybrid food using synchrotron X-ray fluorescence and X-ray absorption spectroscopies

The bioavailability of iron from a food depends on its concentration and chemical form but also on dietary factors and nutrient interactions, which are affected by storage conditions and time. Here we investigated the time-course profile of iron in a hybrid 3D-printed food composed of alternating layers of liver and lentils after 0, 5, 7, 14 and 21 days of storage at 4 °C under oxygen or nitrogen packaging. Synchrotron X-ray fluorescence highlighted major variations in iron distribution in both the animal and plant parts of the food as a function of storage conditions. FeP and FeS positive spatial correlations pointed to iron-associated compounds. X-ray absorption near-edge structure spectroscopy showed spectral signatures specific to the animal and plant mixtures, and then highlighted interactions between animal and plant parts during food storage, with a change in iron forms in the plant part.

Evolution of fluid redox in a fault zone of the Pic de Port Vieux thrust in the Pyrenees Axial Zone (Spain)

Abstract. In mountain ranges, crustal-scale faults localize multiple episodes of deformation. It is therefore common to observe current or past geothermal systems along these structures. Understanding the fluid circulation channelized in fault zones is essential to characterize the thermochemical evolution of associated hydrothermal systems. We present a study of a palaeo-system of the Pic de Port Vieux thrust fault. This fault is a second-order thrust associated with the Gavarnie thrust in the Axial Zone of the Pyrenees. The study focused on phyllosilicates which permit the constraint of the evolution of temperature and redox of fluids at the scale of the fault system. Combined X-ray absorption near-edge structure (XANES) spectroscopy and electron probe microanalysis (EPMA) on synkinematic chlorite, closely linked to microstructural observations, were performed in both the core and damage zones of the fault zone. Regardless of the microstructural position, chlorite from the damage zone contains iron and magnesium (Fetotal / (Fetotal + Mg) about 0.4), with Fe3+ accounting for about 30 % of the total iron. Chlorite in the core zone is enriched in total iron, but individual Fe3+/Fetotal ratios range from 15 % to 40 %, depending on the microstructural position of the grain. Homogeneous temperature conditions about 280–290 °C have been obtained by chlorite thermometry. A scenario is proposed for the evolution of fluid–rock interaction conditions at the scale of the fault zone. It involves the circulation of a single hydrothermal fluid with homogeneous temperature but several redox properties. A highly reducing fluid evolves due to redox reactions involving progressive dissolution of hematite, accompanied by crystallization of Fe2+-rich and Fe3+-rich chlorite in the core zone. This study shows the importance of determining the redox state of iron in chlorite to calculate their temperature of formations and to consider the fluid evolution at the scale of a fault.

In-Depth XANES and EXAFS Characterization of the Ag+ Ion Coordination in Dimethyl Sulfoxide Solution.

X-ray absorption near-edge structure (XANES) spectroscopy has been used, in conjunction with extended X-ray absorption fine structure (EXAFS), to determine the coordination structure of the Ag+ ion in a dimethyl sulfoxide (DMSO) solution. From the EXAFS data analysis, the Ag-O first shell distance in DMSO was found to be 2.31(3) Å, with 4.1(5) oxygen atoms surrounding the Ag+ ion, in fair agreement with previous results. This technique did not allow us to determine the geometry of the 4-fold coordination complex and a quantitative analysis of the XANES region was carried out to shed light on this issue. The XANES data analysis confirmed the presence of a four-coordinated complex, unambiguously showing that a regular tetrahedral [Ag(DMSO)4]+ complex is formed when silver triflate is dissolved in DMSO solution.

Investigating the photocatalytic reduction of U(VI) over a single-atom Fe complex catalyst

Fabrication of effective photocatalyst for the U(VI) reduction is a promising approach to disposing the great challenges posed by rising the rapid development of nuclear energy. Herein, it rationally designed a single-atom Fe anchored g-C3N4 support (Fe-g-C3N4, Fe-N4 moiety), showing the ultrahigh photocatalytic performance towards over wide pH range of 3.0–8.0, outer-performing pristine g-C3N4 by 82 times. Combination with X-ray photoelectron spectroscopy and X-ray absorption near-edge structure spectroscopy, the highly photoreduction of U(VI) could be attributed to the highly activity of g-C3N4 and Fe2+. According to quenching experiments and EPR spectra, it is demonstrated that the superoxide (·O2–) radicals played an important role in the photoreduction of U(VI) on Fe-g-C3N4 rather than ·OH and 1O2 species. These findings are crucial for the actual application of single-atom photocatalyst in environmental remediation.

Distinguishing contributions of diverse sediment components to vanadium transport, immobilization and transformation in aquifer

Vanadium (V) occurs in environment naturally and anthropogenically, but little has been understood about its environmental behavior in groundwater aquifer with sediments. This study investigated the pentavalent V [V(V)] transport and transformation under the influence of different sediment components (minerals, organic matter, and microorganisms) through column experiments. All these components played pivotal roles in V immobilization. The synergistic effects of sediment components enhanced V retention compared to individual component. Mineral components, particularly those containing carbonates and metal oxides, predominantly influenced V(V) transport as indicated by XRD analysis. Organic matter, especially under low pH conditions, induced particle aggregation, thereby inhibiting the transport of V(V). The V K-edge X-ray absorption near-edge structure spectroscopy revealed the formation of tetravalent V[V(IV)] in treatments involving organic matter and microorganisms. Notably, organic matter exhibited the capability to directly reduce V(V). The introduction of microorganisms restricted V(V) transfer. V(V) reducing genera (e.g., Brevundimonas, Arenimonas, Xanthobacter) were detected, achieving V(V) reduction to insoluble V(IV). V(V) bioreduction was improved by minerals that promote microbial metabolism with enhanced electron transfer, or by organic matter that increases levels of intracellular nicotinamide adenine dinucleotide and extracellular polymeric substances. This study specifies the contributions of different sediment components to the transportation and transformation of V, deepening our understanding of V biogeochemistry in groundwater aquifer.

Unveiling the Mechanical and Electrochemical Evolution of Nanosilicon Composite Anodes in Sulfide-Based All-Solid-State Batteries

The utilization of silicon (Si) anodes in all-solid-state lithium batteries (ASLBs) provides the potential for high energy density. However, the compatibility of sulfide solid-state electrolytes (SEs) with Si and carbon is often questioned due to potential decomposition. To investigate this, operando X-ray absorption near-edge structure (XANES) spectroscopy, ex-situ scanning electron microscopy (SEM) and ex-situ X-ray nano-tomography (XnT) were utilized to study the chemistry and structure evolution of nano Si composite anodes. Results from XANES demonstrated a partial decomposition of SEs during the first lithiation stage, which was further accelerated by the presence of carbon. But the performance of first three cycles in Si-SE-C was stable, which proved the generated media is ionically conductive. XnT and SEM results showed that the addition of SEs and carbon improved the structural stability of the anode with fewer pores and voids. A chemo-elasto-plastic model revealed that SEs and carbon buffered the volume expansion of Si, thus enhancing mechanical stability. The balance between the pros and cons of SEs and carbon in enhancing reaction kinetics and structural stability enabled the Si composite anode to demonstrate the highest Si utilization with higher specific capacities and better rate than pure Si and Si composite anodes with only SEs.

Porous Bi Nanosheets Derived from β-Bi2O3 for Efficient Electrocatalytic CO2 Reduction to Formate.

The electrochemical CO2 reduction reaction (ECO2RR) is a promising strategy for converting CO2 into high-value chemical products. However, the synthesis of effective and stable electrocatalysts capable of transforming CO2 into a specified product remains a huge challenge. Herein, we report a template-regulated strategy for the preparation of a Bi2O3-derived nanosheet catalyst with abundant porosity to achieve the expectantly efficient CO2-to-formate conversion. The resultant porous bismuth nanosheet (p-Bi) not only exhibited marked Faradaic efficiency of formate (FEformate), beyond 91% in a broad potential range from -0.75 to -1.1 V in the H-type cell, but also demonstrated an appreciable FEformate of 94% at a high current density of 262 mA cm-2 in the commercially important gas diffusion cell. State-of-the-art X-ray absorption near edge structure spectroscopy (XANES) and theoretical calculation unraveled the distinct formate production performance of the p-Bi catalyst, which was cocontributed by its smaller size, plentiful porous structure, and stronger Bi-O bond, thus accelerating the absorption of CO2 and promoting the subsequent formation of intermediates. This work provides an avenue to fabricate bismuth-based catalysts with high planar and porous morphologies for a broad portfolio of applications.

Uranium oxidation states in zircon and other accessory phases

Zircon and other U-bearing accessory phases are important time-capsules for studying the evolution of Earth and other planetary bodies as these minerals can record both temporal and compositional information regarding their host rocks. In silicate melts, uranium can occur in either the UIV, UV, or UVI valence state and its redox sensitive nature could, in principle, allow for information on magma oxygen fugacity (ƒO2) to be gleaned from U-bearing phases provided they can incorporate multivalent U during crystallization. Currently, however, little is known regarding the details of how U is speciated in these minerals.In this study, we conducted conventional X-ray absorption near-edge structure (XANES) spectroscopy at the U M4-edge on a set of natural zircon (n = 140), titanite (n = 9), apatite (n = 7), baddeleyite (n = 7), and garnet (n = 2) samples to determine the oxidation state of U in these crystals. We also collected U L3-edge spectra for select zircon samples to investigate the bonding environment of U using extended X-ray absorption fine structure (EXAFS) analysis. The effects of crystallographic orientation and radiation damage on zircon U M4-edge spectra are found to be minimal compared to the magnitude of the peak shifts associated with U oxidation state. We find that titanite and garnet contain only tetravalent U, while zircon, apatite, and baddeleyite can contain U of variable valence. Of these phases, zircon shows the greatest variability, with white-line energy, Ewl (i.e., peak absorbance) covering a range of >2.0 eV between grains: i.e., the entire energy range expected between pure UIV and pure UVI species. Moreover, a correlation is observed between the Ewl of zircon U M4-edge spectra (i.e., relative proportions of UIV, UV, UVI) and the ƒO2 of their host rocks. Our results thus establish U oxidation states in zircon as a powerful new tracer of magma redox. Since XANES is non-destructive and can be performed in situ, this technique can be utilized alongside other microanalytical methods (e.g., LA-ICPMS, SIMS) to further expand the breadth of information that can be extracted from single mineral grains.

Volcanic Eruption in the Nanoworld: Efficient Oxygen Exchange at the Si/SnO2 Interface.

Here, a phenomenon of efficient oxygen exchange between a silicon surface and a thin layer of tin dioxide during chemical vapor deposition is presented, which leads to a unique Sn:SiO2 layer. Under thermodynamic conditions in the temperature range of 725-735°C, the formation of nanostructures with volcano-like shapes in "active" and "dormant" states are observed. Extensive characterization techniques, such as electron microscopy, X-ray diffraction, synchrotron radiation-based X-ray photoelectron, and X-ray absorption near-edge structure spectroscopy, are applied to study the formation. The mechanism is related to the oxygen retraction between tin(IV) oxide and silicon surface, leading to the thermodynamically unstable tin(II)oxide, which is immediately disproportionate to metallic Sn and SnO2 localized in the SiO2 matrix. The diffusion of metallic tin in the amorphous silicon oxide matrix leads to larger agglomerates of nanoparticles, which is similar to the formation of a magma chamber during the natural volcanic processes followed by magma eruption, which here is associated with the formation of depressions on the surface filled with metallic tin particles. This new effect contributes a new approach to the formation of functional composites but also inspires the development of unique Sn:SiO2 nanostructures for diverse application scenarios, such as thermal energy storage.

Fertilization efficiency of thirty marketed and experimental recycled phosphorus fertilizers

Recycling phosphorus (P) from waste streams like sewage sludge, animal manures or food industry by-products is required to sustain soil fertility without depleting non-renewable P resources. Several technologies are available for P recovery, leading to fertilizers differing in P solubility and bioavailability. In this study, thirty fertilizers obtained through different technologies were tested to assess if their fertilization efficiency was equivalent to mineral soluble fertilizer applied as triple superphosphate (TSP). The main selection criteria were (1) ensuring a wide chemical diversity, and (2) choosing products already on the market or at a late stage of development, to encompass a representative selection of current and future recycled fertilizers. The products were classified according to their organic carbon content and neutral ammonium citrate (NAC), and the main P species of each fertilizer was determined through K-edge and L2,3-edge X-ray absorption near edge structure spectroscopy (XANES). Three pot experiments with wheat, barley and ryegrass were conducted in three growing substrates with contrasting properties, all within a pH range of 5.8–6.9. Fertilizers containing ammonium magnesium phosphate, monoammonium phosphate, monocalcium phosphate, and dicalcium phosphate type species as dominant P species showed a similar fertilization efficiency to TSP, while fertilizers with hydroxyapatite, tricalcium phosphate, phytic acid or iron phosphates as their main P species had lower fertilization efficiencies. We conclude that while the trend towards high-efficiency, refined inorganic recycled P fertilizers is positive, lower-performing, mostly unrefined fertilizers must be assessed in light of their long-term P supply potential and additional benefits to soil health owing to their content of organic matter and other nutrients.

Enhancing Phosphorus Release from Sewage Sludge in Anaerobic Digestion via Thermal Hydrolysis Pretreatment: Insights from Phosphorus Speciation and Molecular Biological Pathways.

This study explores the mechanisms enhancing phosphorus (P) release from sludge in anaerobic digestion (AD) with thermal hydrolysis pretreatment (THP) using sequential chemical extraction, X-ray absorption near-edge structure spectroscopy (XANES), 31P NMR, and multiomics. THP-treated sludge notably increased liquid-phase P by 53.8% over 3 days compared to sewage sludge (SS), identifying solid-phase Fe-P as the primary P source. The THP+AD also provided a higher abundance of bacteria that contributed to P release through multiple pathways (MPRPB), whereas SS+AD enriched some microbial species with single P release pathway. Moreover, species co-occurrence network analysis underlined the pivotal role of P-releasing bacteria in THP+AD, with 8 out of 16 keystones being P-releasers. Among the 63 screened genes that were related to P transformations and release, the poly beta-hydroxybutyrate (PHB) synthesis genes associated with polyphosphate bacteria-mediated P release were more abundant in THP+AD than in SS+AD. Furthermore, the upregulation of genes involved in methyl phosphonate metabolism in the THP-treated sludge enhanced the methane production potential of the AD process. These findings suggested that MPRPB were indeed the main contributors to P release, and enrichment in the THP+AD process enhanced their capability for P liberation.