Edge Structure Spectroscopy Research Articles

Mercury Speciation and Stable Isotopes in Emperor Penguins: First Evidence for Biochemical Demethylation of Methylmercury to Mercury-Dithiolate and Mercury-Tetraselenolate Complexes

Apex marine predators, such as toothed whales and large petrels and albatrosses, ingest mercury (Hg) primarily in the form of methylmercury (MeHg) via prey consumption, which they detoxify as tiemannite (HgSe). However, it remains unclear how lower trophic level marine predators, termed mesopredators, with elevated Hg concentrations detoxify MeHg and what chemical species are formed. To address this need, we used high energy-resolution X-ray absorption near edge structure spectroscopy paired with nitrogen (N) and Hg stable isotopes to identify the chemical forms of Hg, Hg sources, and species-specific δ202Hg isotopic values in emperor penguin, a mesopredator feeding primarily on Antarctic silverfish. The penguin liver contains variable proportions of MeHg and two main inorganic Hg complexes (IHg), Hg-dithiolate (Hg(SR)2) and Hg-tetraselenolate (Hg(Sec)4), each characterized by specific isotopic values (δ202MeHg = 0.3 ± 0.2‰, δ202Hg(SR)2 = −1.6 ± 0.2‰, δ202Hg(Sec)4 = −2.0 ± 0.1‰). Using δ15N as a tracer of food source, we show that Hg(SR)2 is likely not obtained through dietary intake, but rather is present as a biochemical demethylation product. Furthermore, on average, female penguins transferred Hg to the egg strictly as MeHg in the egg albumen but as mixtures of MeHg and IHg in the membrane (89% and 11%, respectively) and yolk (32% MeHg and 68% Hg(Sec)4). Despite IHg species in eggs, MeHg is still the main species quantitatively transferred by the mother to the chick because of the disproportionate mass of the MeHg-rich albumen compared to the yolk. This work highlights the transformation of MeHg to Hg(SR)2 during demethylation for the first time in multicellular organisms, but further work is needed to understand the formation of Hg(SR)2 in the presence of relatively abundant Se biomolecules in lower trophic level predator species.

Structural and Biological Studies of Bioactive Silver(I) Complexes with Coumarin Acid Derivatives.

Two new Ag(I) complexes with coumaric carboxylic acid derivatives have been synthesized. Structural studies of these noncrystalline complexes have been performed using a methodology that combines laboratory and synchrotron techniques, supported by density functional theory calculations. The arrangement of ligands around the Ag(I) cation has been refined using infrared, extended X-ray absorption fine structure, and X-ray absorption near edge structure spectroscopies. Different coordination modes of carboxylate ligands are observed for the studied compounds. Carboxylate bridges are characteristic for the Ag(I) complex with 4-oxo-4H-1-benzopyran-2-carboxylic acid (1), while a bidentate chelating motif was found for the complex with 2-oxo-2H-1-benzopyran-3-carboxylic acid (2). Additionally, the carbonyl oxygen atom of the coumarin ring coordinates to the silver cation in complex 2, while it is inactive in complex 1. Antimicrobial evaluation has been performed for both compounds. The complexes show activity against selected bacteria as well as Candida yeast. This activity is slightly lower for bacteria and the same or higher for Candida in relation to the reference substances: ciprofloxacin or fluconazole.

Influence of the painting medium on the alteration process of smalt in oil paintings studied using combined K and Co K-edge XANES

This study investigates the alteration processes affecting the smalt pigment in historical artworks through a combination of analytical techniques including X-ray Absorption Near Edge Structure (XANES) spectroscopy at the potassium (K) and cobalt (Co) K-edges, coupled with scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) and micro X-ray fluorescence elemental mapping (µ-XRF). Laboratory mock-up samples prepared with different oil binding media were artificially aged, revealing varying rates of smalt degradation. µ-XANES analyses at the K K-edge provided grain-scale insights into smalt alteration, highlighting the influence of binding media composition on degradation kinetics. Crossed clustering data analysis over K µ-XANES acquired on both model samples and historical cross-sections corroborated findings and identified distinct spectral signatures associated with different stages of smalt degradation. Furthermore, identification of potential transformation products such as potassium alum in historical samples emphasized the dynamic nature of pigment alteration processes.

Multimodal, microspectroscopic speciation of legacy phosphorus in two US mid‐Atlantic agricultural soils

AbstractTo understand phosphorus (P) mobility in agricultural soils and its potential environmental risk, it is essential to directly measure solid phase P speciation. Often, bulk P K‐edge X‐ray absorption near edge structure (XANES) spectroscopy followed by linear combination fitting (LCF) is utilized to determine the solid P phases in soil. However, this method may limit results to only a few major phases. Additionally, XANES spectra for different P species may have very similar features, leading to an over‐ or underestimate of their contribution to LCF. Here, an improved P speciation by pairing multimodal microbeam‐X‐ray fluorescence (µ‐XRF) mapping coupled with µ‐XANES (microbeam‐X‐ray absorption near edge structure) analysis to directly speciate major and minor P phases on the micron scale is provided. We combined maps of both tender (P, sulfur, aluminum, and silicon) and hard energy (calcium, iron [Fe], and manganese) elements to evaluate the elemental co‐locations with P. To better account for uncertainty assigning XANES peaks to individual compounds, a more quantitative fingerprinting by “spectral feature analysis” was completed. With this analysis, an R‐factor is reported for the fit. These results were compared to traditional LCF. Pre‐edge fitting results revealed the presence of a two‐component pre‐edge feature for phosphate adsorbed to ferrihydrite. Additionally, phytate co‐precipitated with ferrihydrite (Phytate‐Fe‐Cop) had a pre‐edge feature, indicating direct association with Fe. Lastly, a unique P species associated with manganese oxide was identified in the soil via multimodal mapping and µ‐XANES. These results allow for better prediction of P dissolution and mobility.

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.

SYNCHROTRON BASED X-RAY ABSORPTION SPECTROSCOPY FOR STRUCTURAL ANALYSIS OF BASALT FIBERS

X-ray Absorption Near Edge Structure (XANES) spectroscopy at the Synchrotron Light Research Institute (Thailand) was used to investigate temperature related structural changes in basalt fibers. As a first step, XANES spectra of fiber samples cut from a basalt roving heated for 1 hour at 800 °C were recorded at the K absorption edges of three chemical elements and compared with the spectra of the untreated fibers. Silicon and calcium K-edge XANES spectra of the fibers were not affected by heating, whereas iron K-edge XANES spectra were significantly influenced by heating at 800 °C. The high iron content in basalt fibers has been attributed to their higher thermal stability compared to common natural or synthetic fibers. As a next step, iron K-edge XANES spectra of two types of fibers (basalt roving and uncoated chopped fibers) were recorded after heating at temperatures between 600 °C and 900 °C. In both cases, with increasing temperature the absorption edge shifts to higher energies, indicating progressing oxidation of the iron atoms in the fibers. These experiments demonstrate the potential of X-ray absorption spectroscopy as a powerful analytical tool to investigate structural changes in basalt fibers upon heating and to correlate them with changes in their mechanical properties.

Tuning the Bifunctional Properties of Cell Reversal-Tolerant Ir-Pt Electrocatalysts for HOR and Oer

Hydrogen starvation is still a big problem in PEM fuel cells [1]. In order to provide protons and electrons to the cathode during H2 starvation, the carbon oxidation reaction (COR) takes place at the anode [2]. To solve this issue, there are three main strategies: (i) utilization of corrosion resistant support materials, (ii) integration of extensive and complex system mitigation strategies and finally (iii) the addition of co-catalyst to promote the oxygen evolution reaction(OER) instead of COR. [3, 4]In this work, platinum-iridium (PtIr) nanoparticles (NPs) have been designed as a novel bifunctional electrocatalysts to accelerate either the hydrogen oxidation reaction (HOR) or the OER depending on the reaction conditions. Our catalyst concept is the combination of both functionality (HOR and OER) in single Pt-Ir alloy nanoparticles (NPs) deposited on the same support material. The Pt-Ir NPs with Pt:Ir ratios of 1:1 and 3:1 were prepared by two different (colloidal and wet-impregnation) routes. Very interestingly, the oxidation states of platinum and iridium as well as the particle size strongly vary depending on the synthesis route. More precisely, the wet-impregnation enables preparing Pt-Ir NPs of 3 – 4 nm size and mainly in the metallic state, while strongly oxidized NPs with ~2 nm size are produced by colloidal route. Despite the different oxidation states and particle sizes, the Pt-Ir NPs show considerable activity for HOR and OER compared to pure commercial Pt/C and IrOx catalysts. Very interestingly, the bifunctionality of these Pt-Ir is highly reversible and is robust during accelerated stress tests. Operando Quick-X-ray Absorption Near Edge Structure (XANES) spectroscopy were performed to provide fundamental insights into the reversibility and catalytically active states of these bifunctional catalysts under the working conditions by jumping with the potential between HER and OER within few seconds. The combination of operando XANES, RDE and MEA data show that the bifunctional approach is a promising way to improve the cell reversal-tolerant properties of anode catalyst materials compared to the state-of-the-art Pt-IrOx catalyst materials.

(Invited) Evolution of Single Atom Catalysts during CO2 Electrocatalytic Reduction

The re-utilization of CO2 via its electrocatalytic reduction (CO2RR) into value-added chemicals and fuels is a promising avenue to minimize the impact of existing technologies on the climate change. This requires the development of low cost, efficient, selective and durable electrocatalysts based of their rational understanding. Moreover, it should be considered that even morphologically and chemically well-defined pre-catalysts can be susceptible to drastic modifications under operation, especially when the reaction conditions themselves change dynamically.This talk will address the transformations that Metal-N-C catalysts (M=Cu, Ni, Co, Fe, Sn, Zn) experience during static and pulsed CO2RR using operando quick X-ray absorption spectroscopy (XAS) and Raman spectroscopy. In particular, I will illustrate the astonishing behaviordisplayed by Cu-N-C catalystsduring CO2RR, featuring reversible transformations from single atom sites towards Cu nanoparticles. The switchable nature of these species that can be achieved by applying different potential pulses holds the key for the on-demand control of the distribution of the CO2RR products and thus, a wide-spread adoption of this process.Moreover, I will elucidate the nature of the ligands forming under CO2RR at singly dispersed Ni sites in Ni-N-C catalysts, which are currently drawing great attention for their high performances in the CO formation. This will be achieved by a synergistic combination of conventional XAS, high energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) spectroscopy, and X-ray emission spectroscopy (XES) coupled with unsupervised and supervised machine learning methodologies and density functional theory.Overall, my lecture will feature the importance of operando characterization of electrocatalysts in order to unveil structure/composition-reactivity correlations during CO2RR.

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.

Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction

Chloroaluminate ionic liquids selectively transform (waste) polyolefins into gasoline-range alkanes through tandem cracking-alkylation at temperatures below 100 °C. Further improvement of this process necessitates a deep understanding of the nature of the catalytically active species and the correlated performance in the catalyzing critical reactions for the tandem polyolefin deconstruction with isoalkanes at low temperatures. Here, we address this requirement by determining the nuclearity of the chloroaluminate ions and their interactions with reaction intermediates, combining in situ 27Al magic-angle spinning nuclear magnetic resonance spectroscopy, in situ Raman spectroscopy, Al K-edge X-ray absorption near edge structure spectroscopy, and catalytic activity measurement. Cracking and alkylation are facilitated by carbenium ions initiated by AlCl3-tert-butyl chloride (TBC) adducts, which are formed by the dissociation of Al2Cl7− in the presence of TBC. The carbenium ions activate the alkane polymer strands and advance the alkylation cycle through multiple hydride transfer reactions. In situ 1H NMR and operando infrared spectroscopy demonstrate that the cracking and alkylation processes occur synchronously; alkenes formed during cracking are rapidly incorporated into the carbenium ion-mediated alkylation cycle. The conclusions are further supported by ab initio molecular dynamics simulations coupled with an enhanced sampling method, and model experiments using n-hexadecane as a feed.

Influence of the 4f5d-1S0 energy gap on the decay times of Pr3+-doped fluoride scintillating glasses

A comparative analysis of praseodymium (Pr3+)-doped fluoride glasses, APLF [20Al(PO3)3–80LiF–PrF3], BCAYF (19BaF2–33.25CaF2–42.75AlF3–5YF3–PrF3), and BCAPLF (19BaF2–33.25CaF2–42.75AlF3–15P2O5–20LiF–PrF3), reveals the effect of the host matrix on the optical properties, particularly the luminescence behavior of Pr3+ ions. X-ray absorption near edge structure (XANES) spectroscopy verifies the presence of Pr ions in the glasses with a +3 oxidation state. Absorption spectra results suggest that the lowest energy level of the Pr3+ 4f5d configuration is influenced by the oxide/fluoride ratio of the glasses. As both interconfigurational 4f5d and intraconfigurational 4f2 transitions are observed, the energy gap between the lowest level of the 4f5d configuration and the overlapping 1S0 level of the 4f2 configuration is found to influence the predominance of UV emissions from the 4f5d and 1S0 levels as well as their decay times. Consequently, a larger 4f5d-1S0 energy gap of ∼5000 cm−1 leads to a more intense UV emission from the 4f5d level with a faster decay time. These results underscore the significance of minimizing the energy of the 4f5d level and increasing the gap between 4f5d-1S0 levels to be able to obtain fast UV emissions from Pr3+-doped fluoride glasses.

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.

Uranium mineralization in the Thrace Basin, NW Türkiye: Evidence from radiation-induced defects in detrital quartz and synchrotron XRF/XANES analysis

The Paleogene-Neogene Thrace Basin in northwestern Türkiye has long been known to host economic gas and oil resources and has recently been reported to potentially host sandstone-type uranium deposits in the Oligocene Süloğlu Formation. The latter discovery raises questions about the source and deposition mechanism of uranium mineralization in the basin. This contribution reports on the results of a detailed electron paramagnetic resonance (EPR) spectroscopic study of detrital quartz from four sandstone and one mudstone samples in the Süloğlu Formation and documents the distribution and speciation of uranium using combined microbeam synchrotron X-ray fluorescence maps (μsXRF) and microbeam X-ray near edge structure spectroscopy (μsXANES). The EPR spectra of quartz separates are characterized by the presence of diagnostic radiation-induced defects (i.e., silicon-vacancy hole centers H′3, H′4, and H′7 with gmax = 2.049, 2.034, and 2.018, respectively, and the oxygen-vacancy electron center E′1), formed by the bombardment of alpha particles emitted from uranium, thorium, and their unstable progenies. Moreover, notable decreases in the intensity of silicon-vacancy hole centers in the EPR spectra of quartz separates after partial dissolution with hydrofluoric acid, provide compelling evidence for the circulation of uranium-bearing fluids in the Thrace Basin. The μsXRF and μsXANES data reveal the occurrences of mixed U6+ and U4+ species in hematite partially replacing pyrite aggregates but dominantly U4+ in disseminated pyrite and illite in sandstones of the Süloğlu Formation. These results provide new insights into uranium transport, reduction, and deposition mechanisms, with important implications for better understanding sandstone-type uranium deposits in general and further exploration in the Thrace Basin.

Fabrication of monolayer h-BN/LaB6 heterostructure thin film with low work function and high chemical stability

To expand the applications of low work function materials, high chemical stability is necessary to prevent the surface from unfavorable reactions. We developed a 20-nm-thick lanthanum hexaboride (LaB6) thin film covered by a monolayer hexagonal boron nitride (h-BN), which exhibits not only low work function but also high chemical stability. Results demonstrated that the h-BN/LaB6 heterostructure can be formed by vacuum annealing a nitrogen-doped LaB6 thin film. The formation process was investigated using Auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (HREELS), and X-ray absorption near edge structure (XANES) spectroscopy. We have elucidated that the doped nitrogen atoms and boron atoms in the film thermally diffuse into the surface during annealing, thereby forming the monolayer h-BN on the surface. Work function was measured using scanning tunneling microscopy (STM). From a practical perspective, chemical stability was evaluated with a heating temperature necessary for restoring the low work function state after air exposure. The work function was comparable to that of the clean LaB6(100) surface. Moreover, it recovered at a much lower temperature than the cleaning temperature of the LaB6(100) surface. We anticipate that this material development will facilitate implementation of the low work function material.

Effects of small-scale topography on organic sulfur mineralization of subtropical soils

Organic sulfur (S) mineralization is an important source of sulfate in soils, compared to atmospheric and weathering inputs. Previous studies on the effects of topography on the decomposition of organic matter have focused exclusively on mountainous regions with steep slopes, without considering low hilly regions with gentle slopes. It therefore remains unclear whether and how hilly regions create distinct environmental conditions that could affect organic S mineralization. We determined S sources, speciation and decomposition index in soil profiles and corresponding plant samples along a catena in a subtropical monsoon climate using a combination of S isotope ratios and S K-edge X-ray absorption near edge structure (XANES) spectroscopy. Sulfur in surface soils is mainly derived from decomposing litter. The decomposition of organic S is the primary process influencing the proportions of water-soluble and adsorbed SO42− in soil profiles. Pedogenic Fe and Al minerals contribute significantly to S stabilization in soils. The most oxidized S species are abundant in plants (10–56%) and may have the potential to stimulate biochemical mineralization through the hydrolysis of ester-S, thereby enhancing S-supplying capacity of soils. Water availability, influenced by small-scale topography, plays a key role in the S biological mineralization. The slower S decomposition rates at the lower elevation can be attributed to the high water content that inhibits microbial activities. Our results suggest that incorporating local-scale topography into the modeling frameworks may improve predictions of ecosystem S status and its responses to climate change.

Machine learning for efficient grazing-exit x-ray absorption near edge structure spectroscopy analysis: Bayesian optimization approach

In materials science, traditional techniques for analyzing layered structures are essential for obtaining information about local structure, electronic properties and chemical states. While valuable, these methods often require high vacuum environments and have limited depth profiling capabilities. The grazing exit x-ray absorption near-edge structure (GE-XANES) technique addresses these limitations by providing depth-resolved insight at ambient conditions, facilitating in situ material analysis without special sample preparation. However, GE-XANES is limited by long data acquisition times, which hinders its practicality for various applications. To overcome this, we have incorporated Bayesian optimization (BO) into the GE-XANES data acquisition process. This innovative approach potentially reduces measurement time by a factor of 50. We have used a standard GE-XANES experiment, which serve as reference, to validate the effectiveness and accuracy of the BO-informed experimental setup. Our results show that this optimized approach maintains data quality while significantly improving efficiency, making GE-XANES more accessible to a wider range of materials science applications.

Deep understanding of LiCoO2 electrode degradation for optimized recycling strategies

Empowered by a synergistic combination approach of Scanning Transmission X-ray Microscopy (STXM) imaging and X-ray Absorption Near Edge Structure (XANES) spectroscopy, a quantitative analysis on the composition and spatial distribution of the cathode in a failed 18650 LiCoO2 (LCO) battery was conducted. Distinct compositional differences between the central and peripheral cathode regions in the failed LCO battery were discerned by utilizing bulk XANES in Total Electron Yield (TEY) and Fluorescence Yield (FY) modes. The central region shows more severe degradation in terms of LCO reduction and excess cathode-electrolyte interface (CEI) buildup. Meanwhile, the STXM technique precisely imaged a specific region of interest in the center of the cathode, covering C, O, and F K-edges, and Co L2,3-edge, to deeply investigate the degradation. Quantitative chemical mapping with spatially resolved XANES spectroscopy, facilitate an in-depth understating of the interfacial reactions on battery electrodes and battery failure fundamentals.

Iron coupled with hydroxylamine turns on the “switch” for free radical degradation of organic pollutants under high pH conditions

Reducing iron by hydroxylamine (HA) can promote the generation of reactive oxygen species (ROS) in the Fenton reaction and play a crucial role in the degradation of organic pollutants. However, the performance of this system at wider environmental thresholds is still not sufficiently understood, especially in the highly alkaline environments resulting from human activities. Here, we assessed the impact of solution pH on organic pollutant degradation by goethite with the addition of HA and H2O2. The solid phase variation and ROS generation were analyzed using Mössbauer spectroscopy, X-ray absorption near edge structure spectroscopy, and electron paramagnetic resonance analysis. This study found that under alkaline conditions, the system can continuously scavenge organic pollutants through oxygen-mediated generation of free radicals. At lower pH levels, organic pollutant decomposition, exemplified by the breakdown of bisphenol A (BPA), is primarily driven by the Fenton reaction facilitated by iron. As pH increases, hydroxyl radical (•OH) production decreases, accompanied by decreased BPA removal efficiency. However, the removal efficiency of BPA increased significantly at pH > 9. At pH 12, the removal of BPA exceeded that of the acidic condition after one hour, which is consistent with observations in soil system studies. Unlike the Fenton reaction, which is not sensitive to oxygen content, the removal of BPA under alkaline conditions occurs only under aerobic conditions. H2O2 is hardly involved in the reaction, and the depletion of HA becomes a critical factor in the decomposition of BPA. Importantly, in contrast to acidic conditions, where the dramatic decomposition of BPA occurs mainly in the first 10 min, the decomposition of BPA under alkaline conditions continued to occur over the 2 h of observation until complete removal. For natural systems, the remediation of pollutants depends more on the active time of ROS than on their reactivity. Therefore, this idea can reference pollution remediation strategies in anthropogenically disturbed environments.

Non-Destructive and Non-Invasive Approaches for the Identification of Hydroxy Lead-Calcium Phosphate Solid Solutions ((PbxCa1-x)5(PO4)3OH) in Cultural Heritage Materials.

Lead-calcium phosphates are unusual compounds sometimes found in different kinds of cultural heritage objects. Structural and physicochemical properties of this family of materials, which fall into the hydroxypyromorphite-hydroxyapatite solid solution, or (PbxCa1-x)5(PO4)3OH, have received considerable attention during the last few decades for promising applications in different fields of environmental and material sciences, but their diagnostic implications in the cultural heritage context have been poorly explored. This paper aims to provide a clearer understanding of the relationship between compositional and structural properties of the peculiar series of (PbxCa1-x)5(PO4)3OH solid solutions and to determine key markers for their proper non-destructive and non-invasive identification in cultural heritage samples and objects. For this purpose, a systematic study of powders and paint mock-ups made up of commercial and in-house synthesized (PbxCa1-x)5(PO4)3OH compounds with a different Pb2+/Ca2+ ratio was carried out via a multi-technique approach based on scanning electron microscopy, synchrotron radiation-based X-ray techniques, i.e., X-ray powder diffraction and X-ray absorption near edge structure spectroscopy at the Ca K- and P K-edges, and vibrational spectroscopy methods, i.e., micro-Raman and Fourier transform infrared spectroscopy. The spectral modifications observed in the hydroxypyromorphite-hydroxyapatite solid solution series are discussed, by assessing the advantages and disadvantages of the proposed techniques and by providing reference data and optimized approaches for future non-destructive and non-invasive applications to study cultural heritage objects and samples.

Speciation and Possible Origins of Organosulfur Compounds in Rice Paddy Soils Affected by Acid Mine Drainage.

Although sulfur cycling in acid mine drainage (AMD)-contaminated rice paddy soils is critical to understanding and mitigating the environmental consequences of AMD, potential sources and transformations of organosulfur compounds in such soils are poorly understood. We used sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy to quantify organosulfur compounds in paddy soils from five AMD-contaminated sites and one AMD-uncontaminated reference site near the Dabaoshan sulfide mining area in South China. We also determined the sulfur stable isotope compositions of water-soluble sulfate (δ34SWS), adsorbed sulfate (δ34SAS), fulvic acid sulfur (δ34SFAS), and humic acid sulfur (δ34SHAS) in these samples. Organosulfate was the dominant functional group in humic acid sulfur (HAS) in both AMD-contaminated (46%) and AMD-uncontaminated paddy soils (42%). Thiol/organic monosulfide contributed a significantly lower proportion of HAS in AMD-contaminated paddy soils (8%) compared to that in AMD-uncontaminated paddy soils (21%). Within contaminated soils, the concentration of thiol/organic monosulfide was positively correlated with cation exchange capacity (CEC), moisture content (MC), and total Fe (TFe). δ34SFAS ranged from -6.3 to 2.7‰, similar to δ34SWS (-6.9 to 8.9‰), indicating that fulvic acid sulfur (FAS) was mainly derived from biogenic S-bearing organic compounds produced by assimilatory sulfate reduction. δ34SHAS (-11.0 to -1.6‰) were more negative compared to δ34SWS, indicating that dissimilatory sulfate reduction and abiotic sulfurization of organic matter were the main processes in the formation of HAS.