End-member Research Articles

Structure and microwave dielectric characteristics of (Ba,Sr,Ca)HfO3 ceramics

In the present work, the structure and microwave dielectric properties of (Ba,Sr,Ca)HfO3 ceramics were systematically investigated to understand the general mechanism of tuning the temperature coefficient of resonant frequency, τf in perovskite ceramics. Ba1–xSrxHfO3 and Sr1–yCayHfO3 could form continuous solid solutions while the solid solubility of Ca in Ba1–yCayHfO3 was about 20% (in mole). τf changed nonlinearly with increasing tolerance factor as the result of competition between the increase in the restoring force on the ions and the increase in polarizability. Under the guidance of three microscopic mechanisms affecting τf, a preliminary attempt was made to explore the suitable parameters to predict the variation trend of τf. Normalized ionic radii and the τf values of the end members were selected as independent variables, and τf was calculated by using multiple linear regression method. For Ba1–xSrxHfO3 and Sr1–yCayHfO3 with orthorhombic structures, the root mean square error between the calculated and measured τf was only 6.8×10–6 °C–1. The good agreement between the calculated τf values and the measured ones in Ba1–x–ySrxCayHfO3 ceramics confirmed its validity where three elements jointly occupy A-site, but it only works when there is no structural phase transition. Progresses in this research field would not only deepen our understanding of mechanism of regulating properties in multi-ion solid solutions, but also boost the developments of closely related fields such as machine learning-assisted design and high-entropy ceramics. Finally, a good combination of microwave dielectric properties was achieved in Sr0.15Ca0.85Hf0.96Ti0.040O3: εr = 27.8, Qf = 36,470 GHz, τf = +5×10–6 °C–1.

Chromophoric dissolved organic matter traces seasonally changing coastal processes in a river-influenced region of the western Bay of Bengal.

The optical characteristics of colored dissolved organic matter (CDOM) serve as a convenient tool for evaluating coastal processes, e.g., river runoff, anthropogenic inputs, primary production, and bacterial/photochemical processes. We conducted a study on the seasonal and spatial variability of absorbance and fluorescence characteristics of CDOM and nutrients in the coastal waters near the Gauthami estuary of River Godavari, the largest peninsular river of India, for a year. The surface aCDOM(350) showed a significant inverse relation with salinity in the coastal region, indicating a conservative mixing of marine and terrestrial end members. The aCDOM(350) was not conservative in the offshore (100m isobath) waters due to enrichment by secondary sources. Seasonal variability in optical properties indicated diverse sources for CDOM, as revealed by principal component analysis. The excitation-emission matrix (EEM) spectra followed by parallel factor analysis (EEM-PARAFAC) revealed four distinct fluorophores. The tyrosine (B) fluorophore showed a predominant increase in the post-monsoon season (October to January), while tryptophan (T) was relatively more enriched, coincident with nutrient enrichment and transparency increase during the early monsoon phase (July). The biological index (BIX), which reflects recent photosynthetic activity, also displayed relatively higher values during the early monsoon. The humic fluorophores A and M, and humification index (HIX) were relatively enriched during the later phase of monsoon (July-October). HIX was > 4 in a few samples of the offshore region (100-m isobath) and indicated a probable contamination from drill-mud (bentonite) used in hydrocarbon exploration. During the monsoon, the relationship between T and B with CDOM was not evident due to the masking of B fluorescence in intact protein. However, during the post-monsoon (POM) and pre-monsoon (PRM) periods, this masking effect was not observed, likely due to protein degradation via bacterial and photochemical processes, respectively. Temporal variability in nutrients indicated that high ammonium levels were produced during POM (OM bacterial degradation), and high nitrite levels were observed during PRM (due to primary production). This study provides foundational insights into the use of CDOM for understanding the impact of diverse environmental, river discharge, and anthropogenic factors on coastal ecosystems.

Iron redox states in closed-basin lakes on early Mars: Its sensitivity to water chemistry, hydrology, and atmospheric composition

Mars has experienced drastic environmental evolution in terms of pH, redox, and desiccation. NASA’s Curiosity rover discovered that the sediments of the Pahrump Hills member of the Murray formation in Gale Crater contained different redox states of Fe oxides. To interpret the observations, understanding the factors that control iron redox states within early Gale lakes on Mars is needed. Here, we present the results of a one-dimensional geochemical model of a closed-basin lake that considers the Fe(II) photo-oxidation reaction. Depending on the source of Fe(II) (groundwater vs. river flow), lake pH, advection rate, and atmospheric composition, we defined four types of chemical profiles in the lake; namely, Fe(II) dominated, Fe(III) dominated, carbonate precipitating, and redox-stratified profiles. The Fe(III) dominated profile corresponds to the end member case in which photo-oxidation effectively oxidizes the supplied Fe(II). The redox-stratified profile, interpreted as an intermediate condition between Fe(III) dominated profile and Fe(II) dominated profile, appears in broad parameter set when Fe(II) is supplied from the groundwater, typically with a low to moderate Fe(II) input flux at acidic to alkaline pH (pH 5–9) conditions; however, the low water flux due to the nature of the groundwater may be unable to explain the measured abundance of Fe oxides in the sediments. Another endmember case, the Fe(II) dominated profile, which would also be expected to generate mixed valence Fe oxides, occurs when the pH is acidic (pH 4–5); nevertheless, the acidic pH is inconsistent with the mineral assemblages of the sediments. Carbonate precipitating profiles were limited to the case in which Fe(II) is supplied by groundwater with high Fe input flux and alkaline pH of 8–9. These results may imply either the Fe(II) input flux was high enough for the redox-stratified case or Fe(II) photo-oxidation was suppressed by turbidity or by dusty/cloudy atmosphere, or possibly that Fe(II) oxides found in the Pahrump Hills member are, at least partly, of detrital origin. Although numerous other factors (ex., effect of lake depth, variable pH throughout the lake water, detailed chemical speciation) remain unconsidered, the diverse profiles in Fe redox resulting from Fe(II) photo-oxidation reaction sheds light on interpreting the variety and the evolution of redox condition on early Mars.

Phase transition in Eu2Zr2–xO7–2x (x = 0–1) solid solutions: A combined structural and spectroscopic study

AbstractZirconate pyrochlores have been extensively studied as candidate waste forms for the immobilization of actinide wastes due to their flexible crystal chemistry, excellent structural stability, and exceptional radiation tolerance. Herein, we report the synthesis of a series of compounds Eu2Zr2–xO7–2x (x = 0–1, step = 0.125) using a co‐precipitation route to form solid solutions between the two end members, Eu2Zr2O7 pyrochlore and Eu2ZrO5 defect fluorite. It is important to understand the pyrochlore to defect fluorite transformation as a function of Zr/Ln molar ratio. The structural investigation by x‐ray diffraction has shown the increasing cation disorder and corresponding structural transitions from the ordered pyrochlore to disordered pyrochlore, then to defect fluorite. While diffuse reflectance spectroscopy provides similar optical absorption features reflecting the presence of Eu(III) ion, Raman spectroscopy has revealed more details on the phase transition and short‐range structures. This work highlights the structural flexibility in zirconate materials as potential nuclear waste forms for the immobilization of actinide‐rich waste streams, especially suitable for the separated minor actinides.

A highly stable insertion type V1-xTixP solid solution as an anode material for high-rate lithium-ion batteries

As electric vehicles (EVs) grow in popularity, the demand for lithium-ion batteries (LIBs) simultaneously grows, and the fast-charging capability is becoming increasingly important. However, it is generally believed that graphite anode still suffers from a poor rate capability for fast-charging applications, and other insertion-type oxide anodes with a high rate capability exhibit too high Li+-ion insertion/extraction potential, which cannot meet a requirement for high energy density anodes. In this work, the hexagonal structure of V1-xTixP (x = 0.0, 0.25, and 1.0) phases were introduced as insertion-type anode materials for LIBs with a low reaction potential of Li+-ion insertion/extraction. The crystal structure and the corresponding electrochemical reaction mechanism of insertion-type anodes of TiP, VP, and MoP were compared. A facile strategy forming a substitutional solid solution is suggested to improve the electrochemical properties of anode materials by combining the end members among insertion-type VP, TiP, and MoP as forming V1-xTixP and V1-xMoxP compounds. V1-xTixP (x = 0.25) electrode, substituting V atoms with Ti atoms in VP structure, shows excellent long-term cycle stability at 1 A/g with a cycle retention of 87.7 % during 2500 cycles, delivering a two times higher capacity of 211.1 mAh g−1 compared to that of the commercial graphite electrode.

Boron-Doped Dinickel Phosphide to Enhance Polysulfide Conversion and Suppress Shuttling in Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are promising for next-generation high-energy energy storage systems. However, the slow reaction kinetics render mobile polysulfides hardly controlled, yielding shuttling effects and eventually damaging Li metal anodes. To improve the cyclability of Li-S batteries, high-efficiency catalysts are desired to accelerate polysulfide conversion and suppress the shuttling effect. Herein, we studied a doping system with Ni2P and Ni2B as the end members and found a B-doped Ni2P catalyst that demonstrates high activity for Li-S batteries. As anionic dopants, B demonstrates an interesting reverse electron transfer to P and tunes the electronic structure of Ni2P dramatically. The resultant B-doped Ni2P exhibits short Ni-B bonds and strong Ni-S interaction, and the electron donation of B to P further enhances the adsorption of polysulfide on catalysts. The S-S bonds of polysulfides were activated appropriately, therefore decreasing a low energy barrier for conversion reactions.

Magnetic properties of the solid solutions CePt1−x Au x Al (x = 0.1–0.9)

Abstract Members of the solid solutions CePt1–x Au x Al have been synthesized from the elements and pure samples could be obtained for the whole range of x from 0.1–0.9. Powder X-ray diffraction patterns indicated the TiNiSi-type structure (orthorhombic, space group Pnma) for the whole series, consistent with the end members CePtAl and CeAuAl. The lattice parameters and therefore also the unit cell volumes evolve in a linear fashion when going from CePtAl to CeAuAl. Magnetic susceptibility and magnetization investigations were performed for the compounds with x = 0.1, 0.2, 0.3, 0.5, 0.7 and 0.9. The results show that the ferromagnetic ground state of CePtAl gets destabilized for small degrees of substitution (x = 0.1) resulting in a lower Curie temperature. For larger values of x, changes towards an antiferromagnetic ground state are observed, in line with pure CeAuAl.

Evaluation and thermodynamic optimization of phase diagram of lithium niobate tantalate solid solutions

The lithium niobate–lithium tantalate solid solution’s phase diagram was investigated using experimental data from differential thermal analysis (DTA) and crystal growth. We used XRF analysis to determine the elemental composition of the crystals. The Neumann–Kopp rule provided essential data for the end members lithium niobate (LN) and lithium tantalate (LT). The heats of fusion of the end members, given by DTA measurements, are 103 kJ/mol at 1531 K for LN and 289 kJ/mol at 1913 K for LT. These values were used as input parameters to generate the data. This data served as the basis for calculating a phase diagram for LN-LT solid solutions. Finally, based on the experimental data and a thermodynamic solution model, the Calphad Factsage module optimized the phase diagram. We also generated thermodynamic parameters for Gibbs’ excess energy of the solid solution. A plot of the segregation coefficient as a function of Ta concentration was derived from the phase diagram.

Stream chemical response is mediated by hydrologic connectivity and fire severity in a Pacific Northwest forest

AbstractLarge‐scale wildfires are becoming increasingly common in the wet forests of the Pacific Northwest (USA), with predicted increases in fire prevalence under future climate scenarios. Wildfires can alter streamflow response to precipitation and mobilize water quality constituents, which pose a risk to aquatic ecosystems and downstream drinking water treatment. Research often focuses on the impacts of high‐severity wildfires, with stream biogeochemical responses to low‐ and mixed‐severity fires often understudied, particularly during seasonal shifts in hydrologic connectivity between hillslopes and streams. We studied the impacts of the 2020 Holiday Farm Fire at the HJ Andrews Experimental Forest where rare pre‐fire stream discharge and chemistry data allowed us to evaluate the influence of mixed‐severity fire on stream water quantity and quality. Our research design focused on two well‐studied watersheds with low and low‐moderate burn severity where we examined long‐term data (pre‐ and post‐fire), and instantaneous grab samples collected during four rain events occurring immediately following wildfire and a prolonged dry summer. We analysed the impact of these rain events, which represent the transition from low‐to‐high hydrologic connectivity of the subsurface to the stream, on stream discharge and chemistry behaviour. Long‐term data revealed total annual flows and mean flows remained fairly consistent post‐fire, while small increases in baseflow were observed in the low‐moderately burned watershed. Stream water concentrations of nitrate, phosphate and sulfate significantly increased following fire, with variance in concentration increasing with fire severity. Our end member mixing models suggested that during rain events, the watershed with low‐moderate severity fire had greater streamflow inputs from soil water and groundwater during times of low connectivity compared to the watershed with low severity fire. Finally, differences in fire severity impacts on concentration‐discharge relationships of biogenic solutes were most expressed under low catchment connectivity conditions. Our study provides insights into post‐wildfire impacts to stream water quality, with the goal of informing future research on stream chemistry responses to low, moderate and mixed severity wildfire.

Mineral chemistry and garnet U-Pb dating in the Bizmişen iron skarn deposit, Erzincan, East-Central Türkiye

In Bizmişen area, Middle Eocene (46.3–42.0 Ma) plutonic rocks (quartz diorite) were intruded into Triassic-Cretaceous limestones and Upper Cretaceous ophiolites and caused to skarn zones containing prograde (garnet, clinopyroxene) and retrograde (amphibole, epidote, calcite, magnetite, phlogopite, serpentinite and chlorite) minerals. Due to contact relationships of quartz diorites with both serpentinized ultramafic rocks and limestone blocks, the mineralogical associations represent calcic (grossular/andradite, amphibole, chlorite and epidote) as well as magnesian (diopside, serpentine, phlogopite, talc) skarns. During the skarnization process, garnet, diopside, epidote, scapolite and amphibole minerals developed in the endoskarn zone within quartz-diorite, and diopside, tremolite, serpentine, phlogopite, talc, Mg-chlorite and calcite minerals developed in the exoskarn zones in ophiolites (serpantinite and listwaenite) and limestones. Skarn and magmatic clinopyroxenes in serpentinized ultramafic hosted exoskarn zone have a compositional range of Wo45-53En35-53Fs0–15 and Wo24-51En38-76Fs0–11, and classified as diopside and augite, respectively. The end members of garnets are Adr46–54Grs43–50Prp1–2Sps1.1–5 in amphibole-epidote-calcite-garnet skarn in endoskarn zone, whereas Adr40–93Grs4–57Prp0.2–2.3Sps0.9–2 in epidote-calcite-garnet skarn in exoskarn zone, and classified as andradite-rich grandite garnets. FeO, MnO and partially MgO contents gradually increase from the edges to the center in zoned garnet grains. Amphibole compositions represent to calcic (Ca >1 atoms per formula unit) group (pargasite) and indicate the high oxygen fugacity conditions which caused the increase in the rate of magnetite crystallization. Al2O3 and FeO contents of epidotes range 23.68–27.63 and 9.10–14.45 wt%, respectively, correspond to composition of epidote and clinozoisite. The iron oxide contents (FeO, wt%) of magnetites change from 91.72 to 98.36 correspond to structural Fe3+1.88–1.97 and Fe2+0.91–1.0 values. The contents of Ti, divalent and trivalent metal cations correspond to ulvospinel-magnetite compositional line at the magnetite end-member. The mineral chemistry of skarn minerals shows similarities to those of most iron skarn deposits. Garnet U-Pb ages (46.95–45.63 Ma) are consistent with the cooling ages of the Bizmişen pluton. The prograde stage of skarn should be occurred syn-intrusion, whereas retrograde stage should be developed later than youngest garnet age (45.6 Ma) and before the oldest late stage argillic alteration (37.5 Ma).

Optical Probe of Magnetic Ordering Structure and Spin‐Entangled Excitons in Mn‐Substituted NiPS3

AbstractIn van der Waals magnets, the interplay between magneto‐excitonic coupling and optical phenomena opens avenues for directly probing magnetic ordering structures, manipulating excitonic properties through magnetic fields, and exploring quantum entanglement between electronic and magnetic states. Notably, NiPS3 stands out for its capacity to host spin‐entangled excitons, where the excitonic states are intricately tied with the material's spin configuration. Herein, it is experimentally showcased that the spin‐entangled excitons can be utilized for detecting the magnetic easy axis in Ni1‐xMnxPS3 (x = 0–0.1). The end members of this series exhibit distinct magnetic ordering patterns and easy axes: zigzag ordering with magnetic moments aligned along the a‐axis for NiPS3 versus Néel ordering with the out‐of‐plane easy axis for MnPS3. By combining angle‐resolved exciton photoluminescence with magnetic susceptibility measurements, it is observed that the magnetic easy axis rotates away from the local spin chain direction with increasing Mn content. Moreover, through a comprehensive thermal and substitution study, it is demonstrated that the energy and lifetime of spin‐entangled excitons are governed by two spin‐flip processes and are drastically influenced by disparate electronic states. These findings not only provide optical means to map out magnetic ordering structures but also offer insights into decoherence processes in spin‐exciton entangled states.

Evaluation of garnet phenocrysts in volcanic rocks (Görece/İzmir – Western Türkiye) for their usability as a semi-precious gemstone by multi-analytical methods

Garnets are observed as phenocrysts in blocky rhyolites of Cumaovası Volcanites and are reddish-blackish in color, show vitreous luster, and have dodecahedron forms varying between 0.5 and 2.0 cm in size. In optical microscope investigations, they exhibit fractured structures and contain quartz, hematite, chlorite, and acicular rutile inclusions. Garnet phenocrysts are highly consistent with spessartine-type garnet end members in the Raman spectrum. This result is supported by the mineral chemistry results determined as spessartine (Sps)0.50–0.52 almandine (Alm)0.47–0.48 grossular (Grs)0.01–0.02. In the chondrite, primitive mantle, and Mid-Oceanic Ridge Basalt normalized multi element variation diagrams, garnet phenocrysts show enrichment in all elements (except Sr, K, P, and Ti). In contrast, in the upper continental crust normalized multi element variation diagram, garnet phenocrysts show depletion in large ion lithophile elements (Rb, Ba, K, and Sr) relative to high field strength elements. They exhibit slight enrichment in light rare earth elements ((La/Sm)N = 0.11–1.07) relative to heavy rare earth elements ((Sm/Yb)N=0.78–0.97). Furthermore, garnet phenocrysts have significant negative europium (Eu) ((Eu/Eu*)N = 0.01–0.02) and mildly positive cerium ((Ce/Ce*)N = 2.43–13.77) anomalies indicating hot and reduced magma conditions. The Y/Ho ratios have ranged from 18.9 to 20.3 and are close to the chondrite value. The zircon saturation temperatures (TZr) of the garnet’s host rock was determined to be 756 °C. As a result of mineralogical, geochemical and gemological studies, it was concluded that Görece garnet phenocrysts have glassy luster and semi-transparent dodecahedral crystal shapes, so they can be classified as semi-precious gemstones. In addition, the rare earth element content of the garnet phenocrysts is similar to that of industrial garnet sands and it is thought that they may have potential.

Hydrogeochemical evolution and isotopic characteristics of groundwater-surface water interaction processes within the Kawere catchment and its hydrogeotechnical implication on pit slope stability at the Nsuta mine, Ghana

In geo-hazard prone heterogenous mining terrain with multiple geological structures, surface water may interact with its underlying groundwater system conveying large quantities of water to deeper aquifers, which could undoubtedly lead to pit-inflows and slope stability challenges for any close-by mining operation. A total of forty-three (43) water samples were collected from the atmosphere, surface, subsurface and the pit-water during dry and wet seasons, respectively to identify pit-inflow origin using hydrogeochemical evolution paths and end member mixing analysis of the major ions at the only manganese mine in Nsuta, Ghana. The major ions order was Na2+>Ca2+>Mg2+>K+ for cations and anions' order was HCO3− > SO42− > Cl−. The identified hydrogeochemical facies and proportions are Ca–HCO3- (68.75%), Ca–Cl2 (18.75%) and mixed Ca–Mg–Cl (12.5%) in the dry season and mixed Ca–Na–HCO3 (54%) followed by Ca–HCO3 (46%) in the wet season. Na+ is the preeminent cation whilst HCO3− is the preeminent anion. Saturation Index (SI) of carbonate and evaporate minerals, particularly calcite, identified groundwater-surface water (GW-SW) exchange flux pathways in the study area, and thus establishing geochemical modeling as a robust tool for identifying GW-SW exchange flux pathways in riverine and aquifer systems. The isotopic composition of the various water samples is depleted having strong mixing relationship of R2 = 0.96%, suggesting the waters have same origin with low d-excess indicating rainfall under lower humidity. End member mixing analysis suggested GW-SW interaction with the surface water contributing an average of 87% to groundwater in the mine pit during the dry season. The generally low hydrogeochemical and isotopic evidence of the various water sources indicate homogeneity pointing to the existence of GW-SW interaction. The fast-movement of the exchange flux has widened flow path leading to pit slope stability issues and huge pit-inflows. Therefore, the mine managers, stakeholders, and decision makers are strongly advised to promptly integrate hydrogeotechnical assessments into their operations as a sustainable remedial measure. This will enable them to continuously reduce the potentiometric head of the groundwater system and ensure cost-efficient mining activities. It is essential to take these actions due to the mine's location within two river stream catchments.

Penternary Wurtzitic Nitrides Li1-xZnxGe2-xGaxN3: Powder Synthesis, Crystal Structure, and Potentiality as a Solar-Active Photocatalyst.

We developed a new penternary wurtzitic nitride system Li1-xZnxGe2-xGaxN3 (0 ≤ x ≤ 1) by hybridizing LiGe2N3 and ZnGeGaN3. Fairly stoichiometric fine powder samples were synthesized by the reduction-nitridation process at 900 °C. While the end member LiGe2N3 possessed a relatively large band gap of 4.16 eV, the band gap of the developed penternary system varied in a broad range of 3.81 to 3.10 eV, showing promising responsivity to the solar spectrum. The crystal structure of LiGe2N3 was precisely determined by time-of-flight neutron powder diffraction for the first time, revealing the complete ordering of Li and Ge in the Cmc21 structure. The structural evolution from completely ordered LiGe2N3 to fully disordered ZnGeGaN3 was quantitatively analyzed by Rietveld refinement based on a partially disordered Cmc21 model, and the obtained results were also supported by 71Ga solid-state NMR spectroscopy. The synthesized Li1-xZnxGe2-xGaxN3 powder samples exhibited photocatalytic activities for the water reduction and oxidation reactions under solar light irradiation, with the H2 evolution rate of 0.3-59.0 μmol/h and the O2 evolution rate of 3.1-296.2 μmol/h, depending on the composition. Stable solar hydrogen generation of up to 48 h was demonstrated by the x = 0.80 sample, with the total amount of H2 evolved over 1.6 mmol and an external quantum efficiency of 2.1%.

Protracted magmatism and crust–mantle interaction during continental collision: insights from the Variscan granitoids of the external western Alps

Variscan granitoids and associated mafic rocks exposed in the External Crystalline Massifs (ECM) of the Western Alps document the Variscan stages from the early Carboniferous collision to the early Permian post-collisional setting. Our study focuses on the Central part of the ECM, synthesizing newly acquired and existing geochronological, whole-rock geochemical and isotopic data. We identified two distinctive magmatic series: (i) high-K calc-alkaline granitoids, which range from magnesian (MgG) to ferro-magnesian (FeMgG) rocks; (ii) ultra-high-K metaluminous (UHKM) rocks (“durbachites”). These series were emplaced roughly simultaneously between ca. 350 and 300 Ma, with two main episodes during the Visean (ca. 348–335 Ma) and the late Carboniferous (305–299 Ma), with a more limited activity in between. A younger Permian event at ca. 280–275 Ma has also been identified in one granitoid pluton. Contemporaneous emplacement of these two series reflects concomitant crustal anatexis and melting of LILE–LREE-rich metasomatized lithospheric mantle. Trace elements and Nd–Sr isotopes reveal significant hybridization between these two magmatic end members, by magma mixing, or assimilation of crystallized mafic ultrapotassic enclaves in the high-K calc-alkaline granitoids. Granitoid composition evolves over time, especially SiO2, Mg#, Sr/Y, La/Yb and Nb/Ta, possibly explained by increasing differentiation of magmas over time, changes in the crust versus mantle sources mass-balance, and decrease in melting pressure due to the orogenic collapse. The εNdi values of both high-K calc-alkaline granitoids and durbachites decreases from [− 3.8; − 2.9] to [− 6.4; − 5.2] between 345 and 320 Ma, possibly indicating an increasing influence of subducted/relaminated crustal material contaminating the lithospheric mantle source. εNdi values then rise to [− 3.7; − 0.5] during the late Carboniferous, possibly due to progressive exhaustion of the enriched mantle source, or advection of the asthenosphere during the post-collisional stage.Graphic abstractPossible geodynamic scenario along the central-eastern segment of the Variscan Belt, which may account for the temporal evolution of Variscan magmatism in the External Western Alps.

A typical point bar with atypical strata in the McMurray Formation, Alberta, Canada: Floods, tides and high suspended sediment concentrations

AbstractStratigraphic positions and the nature of some breccias and mudstones observed in the Lower Cretaceous McMurray Formation type section (Alberta, Canada) challenge the existing fluvial point bar facies models. The currently applied large‐scale, tidally influenced, sandy bedload facies model suggests that point bars fine upward, where breccias and cross‐strata occur at the base of the succession and mud content increases upward. Instead, this study documents that: (i) mudstone clast breccias are not exclusively associated with basal channel‐lag deposits and can occur throughout the point bar; and (ii) stratified mudstones are not limited to the top of the fining‐upward succession and can occur at or near the channel base. This outcrop data, including lithology, sedimentary structures, trace fossils, bed thickness and boundaries, and the nature of stratal packages, further suggests dynamic interplay between fluvial and tidal processes. This article discusses the potential role of high‐magnitude river floods in temporarily elevated suspended sediment concentrations and highlights that fluid mud processes played a crucial role in mud deposition in both tide‐influenced and fluvial parts of the system. Fluid mud processes allowed mud deposition along the channel base and across the point bar accretion surfaces. The breccias predominantly consist of broken pieces of inclined heterolithic strata and mostly occur on accretion sets of point bars, suggesting erosion and collapse of the point bar rather than of the cutbank. This work introduces a novel perspective to the existing models of point bar sedimentation, offering a new end member and concepts for the interpretation of subsurface data. The authors hope that this research encourages further investigations into similar phenomena elsewhere in the world.

Machine-learning structural reconstructions for accelerated point defect calculations

Defects dictate the properties of many functional materials. To understand the behaviour of defects and their impact on physical properties, it is necessary to identify the most stable defect geometries. However, global structure searching is computationally challenging for high-throughput defect studies or materials with complex defect landscapes, like alloys or disordered solids. Here, we tackle this limitation by harnessing a machine-learning surrogate model to qualitatively explore the structural landscape of neutral point defects. By learning defect motifs in a family of related metal chalcogenide and mixed anion crystals, the model successfully predicts favourable reconstructions for unseen defects in unseen compositions for 90% of cases, thereby reducing the number of first-principles calculations by 73%. Using CdSexTe1−x alloys as an exemplar, we train a model on the end member compositions and apply it to find the stable geometries of all inequivalent vacancies for a range of mixing concentrations, thus enabling more accurate and faster defect studies for configurationally complex systems.

Ruddlesden-Popper Oxyfluorides La2Ni1-xCuxO3F2 (0 ≤ x ≤ 1): Impact of the Ni/Cu Ratio on the Thermal Stability and Magnetic Properties.

Ruddlesden-Popper oxyfluorides of the substitution series La2Ni1-xCuxO3F2 (0 ≤ x ≤ 1) were obtained by topochemical fluorination with polyvinylidene fluoride (PVDF) of oxide precursors La2Ni1-xCuxO4. The thermal stability and the temperature-dependent unit cell evolution of the oxyfluorides were investigated by high-temperature XRD measurements. The oxyfluoride with x = 0.6 shows the highest decomposition temperature of θdec ∼ 520 °C, which is significantly higher than the ones found for the end members La2NiO3F2 (x = 0) θdec ∼ 460 °C and La2CuO3F2 (x = 1) θdec ∼ 430 °C. The magnetic properties of all La2Ni1-xCuxO3F2 oxyfluorides were characterized by field- and temperature-dependent measurements as well as DFT calculations of the magnetic ground state. An antiferromagnetic ordering was derived for all substitution levels. For the Néel temperature (TN), a nonlinear dependence on the copper content was found, and comparably high values of TN in the region of 200-250 K were observed in the broad composition range of 0.3 ≤ x ≤ 0.8.

Resolving the Interpretation of Magnetic Coercivity Components From Backfield Isothermal Remanence Curves Using Unmixing of Non‐Linear Preisach Maps: Application to Loess‐Paleosol Sequences

AbstractUnmixing of remanent magnetization curves, either isothermal remanent magnetization (IRM) or backfield IRM, is widely used in rock magnetic and environmental magnetic studies to discriminate between magnetic coercivity components of different origins. However, the wide range of physical properties of natural magnetic particles gives rise to an ambiguous interpretation of these components. To reduce this ambiguity and provide a straightforward interpretation of coercivity components in terms of domain state, interactions, and constituent magnetic phases, we combined backfield IRM unmixing with unmixing of nonlinear Preisach maps for two typical mid‐latitude northern hemisphere loess‐paleosol sequences. Both backfield IRM and nonlinear Preisach maps unmixing are based on the same non‐parametric algorithm, and provide similar endmembers (EMs) in the two sections studied. The first EM (EM1) has a low median coercivity (∼21 mT) and is a non‐interacting single domain (SD) magnetite/maghemite of pedogenic origin. The second EM (EM2) has a moderate median coercivity (∼60 mT) and is a mixture of pseudo‐single domain/multidomain, SD magnetite/maghemite and non‐interacting SD hematite, all of eolian origin. The same EM1 found in both sections suggests that this component's grain size and coercivity are independent of pedogenesis intensity. The same EM2 indicates that a similar magnetic population is being transported and deposited, irrespective of the dust source area and loess granulometry. The approach outlined here provides strong evidence that non‐parametric backfield IRM unmixing isolates physically realistic EMs. Unmixing nonlinear Preisach maps elucidates these EMs in terms of domain states and their constituent magnetic phases.

A new method to quantify the source contribution of mixed biodegraded oil based on pareto-optimized nonnegative matrix factorization and chord diagram visualization

The biogenic information of different components in crude oils with varying degrees of biodegradation is partially obscured, making traditional molecular indicators ineffective in determining the contributions of mixed sources. Previous studies have mainly focused on calculating mixed source proportion for normal oils, with few investigations involving biodegraded mixed oils. Developing a quantitative method for the mixed source contribution of biodegraded oils using machine learning (ML) algorithms is a significant attempt both to the exploration practice and theoretical progress. Taking the biomarker parameters resistant to biodegradation of 150 oil samples as input datasets, a new method called Pareto-Optimized NMF (PONMF) was proposed in this study, which combines multi-objective optimization (Pareto optimization) with non-negative matrix factorization (NMF) to analyze the relationship between biodegraded oils in the absence of source rock samples or original end-member (EM) oils while satisfying non-negativity constraints and additional constraint conditions. This method decomposes the matrix of crude oil samples into multiple end-members, each representing a possible input from a hydrocarbon source rock. Analysis of the end-member characteristics facilitates the deduction of potential hydrocarbon source layers and the traits of their depositional environments. This examination is supported by data derived from 15 prospective hydrocarbon source rock samples, which were employed to ascertain the actual geological significance of the end-members. The chord diagram depicts the visualization results of the overall relative contribution of source rock end members to crude oil in each area after the PONMF calculation results. The relative contribution of source rocks in different areas to the investigated crude oil samples is proportionate, and the arc length can reflect the contribution of the three sets of source rocks to a certain area. The findings indicate that the oils extracted from the stratified reservoirs in Eastern Chepaizi are primarily derived from the Permian source strata within the Shawan Depression, with a significant contribution ranging from 30% to 90% (EM2), and a lesser extent from the Carboniferous sources, contributing between 5% and 30% (EM1). Conversely, the provenance of oil in Western Chepaizi is overwhelmingly attributed to the Jurassic source interval located in the Sikeshu Depression, where EM3 accounts for over 85% of the source. Meanwhile, the oils in the Central Zone exhibit a composite origin, intermingling contributions from both EM1 and EM3. The advantage of this method is that it does not require direct access to hydrocarbon source rock samples or end-member oils but infers potential hydrocarbon source layers through the existing mixed-source oil samples. The PONMF method provides an effective tool for identifying the sources of biodegraded oils and can be used to study potential hydrocarbon source rock analysis for oils that have undergone biodegradation after hydrocarbon accumulation.