X-ray Absorption Near-edge Structure Analysis Research Articles

Correlation between biomedical and structural properties of Zn/Sr modified calcium phosphates.

This study investigates the correlation between the biomedical and structural properties of Zn/Sr-modified Calcium Phosphates (ZnSr-CaPs) synthesized via the sol-gel combustion method. X-ray diffraction (XRD) analysis revealed the presence of Ca10(PO4)6(OH)2 (HAp), CaCO3, and Ca(OH)2 phases in the undoped sample, while the additional phase, Ca3(PO4)2 (β-TCP) was formed in modified samples. X-ray absorption near-edge structure (XANES) analysis demonstrated the incorporation of Sr into the lattice, with a preference for occupying the Ca1 sites in the HAp matrix. The introduction of Zn, furthermore, led to the formation of ZnO and CaZnO2 species. The ZnSr-CaPs exhibited significant antibacterial activity attributed to the generation of reactive oxygen species by ZnO, the oxidation reaction of CaZnO2, and the presence of Sr ions. Cytotoxicity tests revealed a correlation between the variation in ZnO content and cellular viability, with lower ZnO concentrations corresponding to higher cell viability. Additionally, the cooperative effects of Zn and Sr ions were found to enhance the bioactivity of CaPs, despite ZnO hindering the apatite formation process. These findings contribute to the deep understanding of the diverse role in modulating the antibacterial, cytotoxic, and bioactive properties of ZnSr-CaPs, offering potential applications in the field of biomaterials.

Synthesis of eco-friendly borosilicate glass with Eu3+ dopants: harnessing recovered silica gel waste for reddish-orange emission materials

In this study, recovered silica gel waste (RSGW) is used as a key raw material to create borosilicate glass doped with Eu3+ ions in a new and environmentally friendly way. The glass compositions were fabricated using the melt quenching method, with different amounts of RSGW and a constant 1.0 mol% Eu3+ doping concentration. The study shows that increasing the doping concentration of RSGW improves the glass density and rigidity while reducing the molar volume, indicating enhanced glass stability. Photoluminescence and X-ray luminescence analyses confirm that the optimal composition with 50 mol% RSGW exhibits the strongest emission. Based on the phonon sideband analysis, the host glasses have a phonon energy of 966.53 cm− 1. An X-ray absorption near-edge structure (XANES) analysis showed that most of the europium ions were in the 3+ oxidation state. The CIE 1931 chromaticity investigation shows the x,y color coordinates at (0.645, 0.351) in the reddish-orange region. To optimize the doping concentration of Eu2O3, it was determined that a fixed concentration of 50 mol% RSGW created the most suitable mixture. Both luminescence emission spectra exhibit strong luminescence, with a peak emission wavelength of 615 nm (⁵D0→⁷F2), confirming concentration quenching in both photoluminescence and x-ray luminescence at a concentration of 1.0 mol%. The study explores potential applications of this novel material in photonics and suggests that this eco-friendly synthesis approach holds great promise for sustainable and efficient production of reddish-orange emission materials.

Synthesis and characterization of hexagonal ceria-BTC microrods for methanol decomposition

BackgroundNovel three-dimensional (3D) hydrated ceria-BTC (CeO2–1,3,5-Benzenetricarboxylic-acid) is the important material due to its unique chemical and physical properties compared to the other materials. A novel 3D ceria nanostructure has been examined as a promising and feasible technique for methanol decomposition. MethodsNovel 3D hydrated ceria-BTC microstructures were successfully synthesized via a hydrothermal route in an aqueous solution. Field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD) patterns show that a ceria-BTC framework diameter and length are approximately 1.45–2.4 and 5.5–6.5 µm, respectively, at 130 °C and with pH 2 for 72 h. The hexagonal ceria-BTC microrod comprises organic linkers, which are transformed into hierarchical ceria microrod in the presences of air at 400 °C was confirmed by Fourier transform infrared spectroscopy (FTIR). Significant FindingsThe Ce-O bonding of the hierarchical ceria microrod species has a bond distance and coordination number of 2.44 and 6.89, respectively, which attenuates the Extended X-ray absorption fine structure (EXAFS) spectra. Compared to the ceria powder, the hierarchical ceria microrods produced more oxygen vacancies and Ce3+as shown by the X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) analyses. The ceria microstructure exhibits excellent methanol decomposition activity.

First synthesis of RuSn solid-solution alloy nanoparticles and their enhanced hydrogen evolution reaction activity.

Solid-solution alloys based on platinum group metals and p-block metals have attracted much attention due to their promising potential as materials with a continuously fine-tunable electronic structure. Here, we report on the first synthesis of novel solid-solution RuSn alloy nanoparticles (NPs) by electrochemical cyclic voltammetry sweeping of RuSn@SnOx NPs. High-angle annular dark-field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy maps confirmed the random and homogeneous distribution of Ru and Sn elements in the alloy NPs. Compared with monometallic Ru NPs, the RuSn alloy NPs showed improved hydrogen evolution reaction (HER) performance. The overpotentials of Ru0.94Sn0.06 NPs/C and Ru0.87Sn0.13 NPs/C to achieve a current density of 10 mA cm-2 were 43.41 and 33.19 mV, respectively, which are lower than those of monometallic Ru NPs/C (53.53 mV) and commercial Pt NPs/C (55.77 mV). The valence-band structures of the NPs investigated by hard X-ray photoelectron spectroscopy demonstrated that the d-band centre of RuSn NPs shifted downward compared with that of Ru NPs. X-ray photoelectron spectroscopy and X-ray absorption near-edge structure analyses indicated that in the RuSn alloy NPs, charge transfer occurs from Sn to Ru, which was considered to result in a downward shift of the d-band centre in RuSn NPs and to regulate the adsorption energy of intermediate Hads effectively, and thus enable the RuSn solid-solution alloy NPs to exhibit excellent HER catalytic properties.

Structural and luminescence properties of transparent borate glass co-doped with Gd3+/Pr3+ for photonics application

A new glass system of lithium borate doped with Gd2O3 and Pr2O3 has been fabricated using a conventional melt quenching technique. The physical parameters, such as density, molar volume, and refractive index, were measured and found to increase as the concentrations of lanthanide oxide (Gd2O3 and Pr2O3) in the glass increased, revealing the underlying structural changes. According to the results of XRD and FTIR, the synthesized glasses exhibited an amorphous structure, and borate complexes served as the triangular BO3, tetrahedral BO4, and OH group amounts in oxide glass. The photoluminescence (PL) spectra show characteristic emission bands resulting from f-f transitions of Pr3+ ions. The strongest emission occurred at 603 nm, corresponding to the transition from the 1D2 state to the 3H4 state. The optimal concentration of Gd2O3 for maximizing emission intensity was found to be 5.0 mol%, and this concentration will be used in the next experiment with varying Pr2O3 concentrations. In the subsequent experiment, emission spectra were recorded by exciting the glass with light at wavelengths of 445 nm, 469 nm, and 483 nm. The resulting emission spectra displayed the characteristic pattern associated with the emission of Pr3+. This emission peak at 603 nm represented the strongest intensity in the spectra, which is a common characteristic of Pr3+ emission. The emission intensity of the glasses initially increases with increasing concentrations of Pr2O3 up to 0.3 mol%, but beyond this concentration, the emission intensity starts to decrease. This behavior indicates the occurrence of a quenching effect at the 0.3 mol% concentration of Pr2O3. X-ray absorption near-edge structure (XANES) analysis confirmed that praseodymium ions were predominantly in the 3 + oxidation state. The chemical composition of the created glass was confirmed to be suitable for photonics applications.

Effect of Re Addition on the Water–Gas Shift Activity of Ni Catalyst Supported by Mixed Oxide Materials for H2 Production

Water–gas shift (WGS) reaction was performed over 5% Ni/CeO2, 5% Ni/Ce-5% Sm-O, 5% Ni/Ce-5% Gd-O, 1% Re 4% Ni/Ce-5% Sm-O and 1% Re 4% Ni/Ce-5% Gd-O catalysts to reduce CO concentration and produce extra hydrogen. CeO2 and M-doped ceria (M = Sm and Gd) were prepared using a combustion method, and then nickel and rhenium were added onto the mixed oxide supports using an impregnation method. The influence of rhenium, samarium and gadolinium on the structural and redox properties of materials that have an effect on their water–gas shift activities was investigated. It was found that the addition of samarium and gadolinium into Ni/CeO2 enhances the surface area, reduces the crystallite size of CeO2, increases oxygen vacancy concentration and improves Ni dispersion on the CeO2 surface. Moreover, the addition of rhenium leads to an increase in the WGS activity of Ni/CeMO (M = Sm and Gd) catalysts. The results indicate that 1% Re 4% Ni/Ce-5% Sm-O presents the greatest WGS activity, with the maximum of 97% carbon monoxide conversion at 350 °C. An increase in the dispersion and surface area of metallic nickel in this catalyst results in the facilitation of the reactant CO adsorption. The result of X-ray absorption near-edge structure (XANES) analysis suggests that Sm and Re in 1% Re 4% Ni/Ce-5% Sm-O catalyst donate some electrons to CeO2, resulting in a decrease in the oxidation state of cerium. The occurrence of more Ce3+ at the CeO2 surface leads to higher oxygen vacancy, which alerts the redox process at the surface, thereby increasing the efficiency of the WGS reaction.

Investigating Metal–Tributyl Phosphate Complexes during Supercritical Fluid Extraction of the NdFeB Magnet Using Density Functional Theory and X-ray Absorption Spectroscopy

Supercritical fluid extraction (SCFE) is gaining significant interest as a green technology for the recycling of end-of-life waste electrical and electronic equipment (WEEE). Neodymium iron boron (NdFeB) magnets, which contain large quantities of critical rare-earth elements such as neodymium, praseodymium, and dysprosium, are widely used in wind turbines and electric/hybrid vehicles. Hence, they are considered a promising secondary resource for these elements when they reach their end-of-life. Previously, the SCFE process was developed for recycling WEEE, including NdFeB; however, the process mechanism remains unexplored. Here, density functional theory, followed by extended X-ray absorption fine structure and X-ray absorption near-edge structure analyses, are utilized to determine the structural coordination and interatomic interactions of complexes formed during the SCFE of the NdFeB magnet. The results indicate that Fe(II), Fe(III), and Nd(III) form Fe(NO3)2(TBP)2, Fe(NO3)3(TBP)2, and Nd(NO3)3(TBP)3 complexes, respectively. This theory-guided investigation elucidates the complexation chemistry and mechanism during the SCFE process by rigorously determining the structural models.

Tissue-variation of iron stable isotopes in marine fish coupled with speciation analysis using X-ray absorption fine structure

The Fe stable isotope ratio (δ56Fe) in tissues is a potential parameter for examining the Fe metabolism in marine fish. Although the effect of ferritin storage has been proposed as a possible cause of heavy isotope (56Fe) enrichment in the liver, no speciation and stable isotope ratio coupling data are available. Here, we report the δ56Fe values measured by multicollector ICP-MS and the result of Fe K-edge X-ray absorption near-edge structure (XANES) analysis of multiple tissues obtained from a skipjack tuna (Katsuwonus pelamis) and a chub mackerel (Scomber japonicus). Apparent isotopic fractionation between the liver and the muscle samples (Δ56FeL–M = δ56Feliver − δ56Femuscle) from these species was observed (0.85 ‰ and 0.57 ‰, respectively). The dominant Fe species in the muscle was heme Fe (the sum of methemoglobin, oxyhemoglobin, and deoxyhemoglobin), while ferritin was not detected according to the linear combination fitting of the XANES spectra. In the liver, ferritin contribution was ca. 28 %–54 % of the total Fe content. The apparent difference in δ56Fe between heme Fe and ferritin was estimated to range from 1.41 ‰ to 1.52 ‰ based on the tissue-specific δ56Fe values and the XANES results. These results indicate that the Fe storage as ferritin does not induce the lowering of δ56Fe in the muscle, considering the low contribution of the liver Fe to the total Fe content in the body.

Halide Layer Cathodes for Compatible and Fast-Charged Halides-Based All-Solid-State Li Metal Batteries.

Insertion-type compounds based on oxides and sulfides have been widely identified and well-studied as cathode materials in lithium-ion batteries. However, halides have rarely been used due to their high solubility in organic liquid electrolytes. Here, we reveal the insertion electrochemistry of VX3 (X=Cl, Br, I) by introducing a compatible halide solid-state electrolyte with a wide electrochemical stability window. X-ray absorption near-edge structure analyses reveal a two-step lithiation process and the structural transition of typical VCl3 . Fast Li+ insertion/extraction in the layered VX3 active materials and favorable interface guaranteed by the compatible electrode-electrolyte design enables high rate capability and stable operation of all-solid-state Li-VX3 batteries. The findings from this study will contribute to developing intercalation insertion electrochemistry of halide materials and exploring novel electrode materials in viable energy storage systems.

Visible Light Accelerates Cr(III) Release and Oxidation in Cr-Fe Chromite Residues: An Overlooked Risk of Cr(VI) Reoccurrence.

The reduced chromite ore processing residue (rCOPR) deposited in environments is susceptible to surrounding factors and causes reoccurrence of Cr(VI). However, the impact of natural sunlight on the stability of rCOPR is still unexplored. Herein, we investigated the dissolution and transformation behaviors of Cr(III)-Fe(III) hydroxide, a typical Cr(III)-containing component in rCOPR, under visible light. At acidic conditions, the release rate of Cr(III) under illumination markedly increased, up to 7 times higher than that in the dark, yet no Cr(VI) was produced. While at basic conditions, only Cr(VI) was obtained by photo-oxidation, with an oxidation rate of ∼7 times higher than that by δ-MnO2 under dark conditions at pH 10, but no reactive oxygen species was generated. X-ray absorption near-edge structure and density functional theory analyses reveal that coexisting Fe in the solid plays a critical role in the pH-dependent release and transformation of Cr(III), where photogenerated Fe(II) accelerates Cr(III) produced at acidic conditions. Meanwhile, at basic conditions, the production of intermediate Cr(III)-Fe(III) clusters by light leads to the oxidation of Cr(III) into Cr(VI) through the nonradical "metal-to-metal charge transfer" mechanism. Our study provides a new insight into Cr(VI) reoccurrence in rCOPR and helps in predicting its environmental risk in nature.

Preparation of iron/calcium-modified biochar for phosphate removal from industrial wastewater

Phosphorous pollution is one of the main factors causing water eutrophication. For the treatment of wastewater, metal-modified biochar has emerged as a promising adsorbent with enhanced affinity for anions such as phosphate. Biochar modified with Fe or Ca are suitable for the treatment of low-concentration phosphorous wastewater (<100mg/L). However, the use of modified biochar to remove high concentrations of phosphate from industrial wastewater is challenging. In this study, biochar from poplar wood, wheat bran, bagasse, and bamboo were prepared and loaded with Fe and Ca, and its adsorption performance and degradation mechanism in the presence of high phosphate concentrations were investigated. The phosphate adsorption capacity of the Fe/Ca-modified biochar was 12–70 times higher than that before the modification. The best type of biochar for phosphate removal was iron/calcium oxide-modified bamboo biochar (ZFCO-BC) through batch experiments. X-ray diffraction (XRD) and X-ray absorption near-edge structure (XANES) analyses showed that ZFCO-BC reacted with wastewater to produce stable vivianite (Fe3(PO4)2·(H2O)8), which did not cause secondary release. ZFCO-BC exhibited a synergistic effect on the removal of 21 metals, including Cr, Cu, Co, Cd, As, Pb, and Y, from complex polluted water. Meanwhile, after 48 h of reaction, the concentration of phosphate decreased from 1660 to 0.061 mg/L, and the final value in the wastewater was lower than the phosphate discharge index indicated by the GB T31962-2015 Sewage Discharge into Urban sewer Water Quality Standard. This study shows that a single remediation system based on ZFCO-BC can remove phosphate and multiple heavy metals from contaminated water, providing a cost-effective treatment solution for complex polluted water bodies, such as industrial wastewater and groundwater.

One-step natural pyrite-assisted mechanochemical detoxification of Cr(VI) in soda ash Chromite Ore Processing Residue: Effectiveness, mechanisms, and life cycle analysis

Traditional wet and dry Chromite Ore Processing Residue (COPR) detoxification methods consume acid for pH adjustment and produce greenhouse gasses (CO2), yielding potential secondary pollution. It is imperative to develop an environmentally-friendly, efficient, and effective method for COPR treatment. This study reported the one-step natural pyrite-assisted mechanochemical detoxification of Cr(VI) in COPR. Under optimal conditions (i.e., the pyrite/COPR mass ratio of 5% and mechanochemical treatment at 600 rev./min for 2.5 h), Cr(VI) in COPR was efficiently reduced and immobilized, and the leaching concentration of total Cr met the regulatory limit of 5 mg/L. The X-ray absorption near-edge structure (XANES) analysis further verified that the Cr(VI) in treated COPR was 100% reduced to Cr(III). Potential mechanism could be that the enclosed non-exchangeable Cr(VI) in the chromite matrix was exposed to the COPR particle surface under the mechanical action; then, the redox reaction between pyrite and Cr(VI) were induced and enhanced through accumulated crystal defects and generated new surfaces with dangling bonds under mechanical forces. Life cycle assessment (LCA) results highlight that the high energy input is the major contributor eliciting environmental impacts for this current technology. More efficient and cleaner energy supplies should be sought alternatively to overcome the overall sustainability.

Operando Laboratory‐Based Multi‐Edge X‐Ray Absorption Near‐Edge Spectroscopy of Solid Catalysts

AbstractLaboratory‐based X‐ray absorption spectroscopy (XAS) and especially X‐ray absorption near‐edge structure (XANES) offers new opportunities in catalyst characterization and presents not only an alternative, but also a complementary approach to precious beamtime at synchrotron facilities. We successfully designed a laboratory‐based setup for performing operando, quasi‐simultaneous XANES analysis at multiple K‐edges, more specifically, operando XANES of mono‐, bi‐, and trimetallic CO2 hydrogenation catalysts containing Ni, Fe, and Cu. Detailed operando XANES studies of the multielement solid catalysts revealed metal‐dependent differences in the reducibility and re‐oxidation behavior and their influence on the catalytic performance in CO2 hydrogenation. The applicability of operando laboratory‐based XANES at multiple K‐edges paves the way for advanced multielement catalyst characterization complementing detailed studies at synchrotron facilities.

Integrated Experimental and Computational K-Edge X-ray Absorption Near-Edge Structure Analysis of Vanadium Catalysts

Integrated Experimental and Computational K-Edge X-ray Absorption Near-Edge Structure Analysis of Vanadium Catalysts

Active Site Formation in Oxygen Deficient Cobalt Antimonate for Oxygen Evolution Reaction in Alkaline Media

Electrochemical water splitting is the one of the promising ways to obtain hydrogen from aqueous media. Oxygen evolution reaction (OER) at the anode is the rate-determining step due to the sluggish kinetics, which leads to reducing energy efficiency. Recently, anion exchange membrane water splitting has been considered as an alternative way because of its capability of producing hydrogen of high purity and the availability of iron-triad element-based catalysts because of their thermodynamically stability in alkaline media. Besides, cobalt oxides such as spinel, layered double hydroxide are being investigated as active OER electrocatalyst. Among them, the spinel-type Co3O4, which contains one Co2+ in the tetrahedral site and two Co3+ ions in the octahedral site, exhibits outstanding OER performance in alkaline media and has been actively investigated.In this study, we investigated oxygen-deficient cobalt antimonate oxide (CoSb2O6) as OER catalyst in alkaline media, which has unique crystal structure and contains abundant octahedral Co2+ compared to spinel-type cobalt oxide. Through in situ X-ray absorption near-edge structure analysis, we observed most of octahedral Co2+ ions were oxidized to Co4+ at OER potential, which leaded to increase the OER activity by extending the active site. We also carried out anion exchange membrane water splitting to confirm the availability as the anode catalyst to produce H2 gas.

Quantitative analysis on the redox conversion mechanism of Cr(VI) and As(III) by iron carbide based biochar composites

Fe-based materials have been widely used for removing Cr(VI) and As(III) in wastewater, however, the quantitative understanding of their removal mechanism and functions of Fe is lacking. In this study, three types of iron carbide based biochar composites (Fe3C@BC-A, Fe3C@BC-B, and Fe3C@BC-C) with different Fe dosages of 19.7%, 24.0%, and 26.5%, respectively, were prepared for Cr(VI) and As(III) removal. The removal of Cr(VI) and As(III) was found to increase as the Fe dosage increased. Fe3C@BC-C with the highest Fe content showed the greatest reduction and oxidation capacities for Cr(VI) and As(III). X-ray absorption near-edge structure analysis indicated that the reduction of Cr(VI) afforded FeCr2O4, (CrxFe1-x)(OH)3, Cr3+, Cr(OH)3, and Cr2O3, whereas AsO43- was the oxidation product of As(III). Results of a pickling experiment revealed that Fe accounted for 18.9%–47.4% and 98.1%–99.4% of the removed Cr(VI) and As(III), respectively. The adsorption mechanism revealed by Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy (XPS) suggested that Cr(VI) was adsorbed by the OH groups of biochar, whereas As(III) was bonded to γ-FeOOH of the reacted Fe3C particles. The quenching experiment, electron spin resonance analysis, and XPS suggested that Fe0, Fe2+, atomic H, and O-containing groups contributed to the reduction of Cr(VI), while •OH, •O2−, 1O2, and Fe(OH)3 were responsible for the oxidation of As(III). The quantitative mechanisms contributed to an improved understanding for the removal of Cr(VI) and As(III) by Fe/C composites, and the results may guide further preparation and application of Fe/C composites for redox-active contaminants removal.

Arsenic and uranium contamination of Orog Lake in the Valley of Gobi Lakes, Mongolia: Field evidence of conservative accumulation of U in an alkaline, closed-basin lake during evaporation

The shrinkage of inland, alkaline, and saline lakes has caused the elevation of arsenic and uranium concentrations in lake water. However, the chemical reactions associated with these enrichments remain unclear. We conducted a five-year study of the water chemistry of Orog Lake (Mongolia) and the chemical and spectroscopic characteristics of the sediment to determine the geochemical behavior of arsenic and uranium during evaporation. The arsenic and uranium concentrations increased as evaporation caused the lake to shrink. The maximum concentrations of arsenic and uranium exceeded 200 µg/L and 600 µg/L, respectively, when the lake area was the smallest. Comparisons of the monitoring results with predictions of geochemical modeling suggested that some arsenic was removed from the lake water under highly desiccated conditions. Sequential extraction and X-ray absorption near-edge structure analyses showed that ferrihydrite can take up As(V). The accumulation of uranium could be reproduced by considering only evaporation. The conservative behavior of uranium can be explained by the low affinity of U(VI) for carbonate and ferrihydrite at pH > 9 and high dissolved inorganic carbon concentrations. The ubiquitous formation of extremely soluble U-bearing salts after the complete desiccation of inland lakes may thus become a serious threat to limnetic ecosystems.

Investigation of Cerium Reduction Efficiency by Grinding with Microwave Irradiation in Mechanochemical Processing

This study evaluated the efficiency of cerium reduction by grinding with microwave irradiation in mechanochemical processing. Grinding experiments with microwave irradiation were conducted using an agitating mixer. Since the structure of the ground samples was amorphous and the cerium concentration was much lower than those of other elements, the valence change and structural change of cerium after grinding with microwave irradiation were investigated using X-ray absorption fine structure (XAFS) analysis in the cerium K-edge. The X-ray absorption near-edge structure (XANES) analysis revealed that a portion of tetravalent cerium was reduced to trivalent cerium by grinding with microwave irradiation. In addition, it was confirmed by extended X-ray absorption fine structure (EXAFS) analysis that oxygen vacancies were produced as a result of the cerium reduction reaction. To evaluate the efficiency of cerium reduction efficiency, the percentage reduction by grinding with microwave irradiation was compared to that by planetary ball milling and microwave irradiation. As a result, it was revealed that the efficiency of cerium reduction via grinding with microwave irradiation was higher than that via microwave irradiation and the same as that via planetary ball milling. Moreover, a larger amount of tetravalent cerium could be reduced to trivalent cerium by grinding with microwave irradiation than when using planetary ball milling and microwave irradiation.

Kinetic Modeling and Mechanisms of Manganese Removal from Alkaline Mine Water Using a Pilot Scale Column Reactor

Manganese (Mn) is a major element in various aqueous and soil environments that is sometimes highly concentrated in mine water and other mineral processing wastewater. In this study, we investigated Mn removal from alkaline mine water (pH &gt; 9) with an Mn-coated silica sand packed into a pilot-scale column reactor and examined the specific reaction mechanism using X-ray absorption near-edge structure (XANES) analysis and geochemical kinetic modeling. The kinetic effect of dissolved Mn(II) removal by birnessite (δ-Mn(IV)O2) at pH 6 and 8 was evaluated at different Mn(II)/Mn(IV) molar ratios of 0.1–10. Our results confirmed the positive effect of the presence of δ-MnO2 on the short-term removal (60 min) of dissolved Mn. XANES analysis results revealed that δ-MnO2 was more abundant than Mn(III)OOH in the reactor, which may have accumulated during a long-term reaction (4 months) after the reactor was turned on. A gradual decrease in dissolved Mn(II) concentration with depth was observed in the reactor, and comparison with the kinetic modeling result confirmed that δ-MnO2 interaction was the dominant Mn removal mechanism. Our results show that δ-MnO2 contents could play a significant role in controlling Mn removability from mine water in the reactor.

Metal (hydr)oxide surface precipitates and their effects on potassium sorption.

Surface precipitation has been shown to occur on rapid time scales in clay and metal oxide mineral systems. The formation of surface precipitates is hypothesized to present new potential sorption sites for potassium (K), where K can become incorporated into newly formed interlayer spaces (e.g., between tetrahedral-octahedral-tetrahedral stacked sheets). The objective of this study is to determine the effects of newly formed mineral surface precipitates on K sorption. Potassium adsorption experiments were conducted by utilizing Al2O3 and SiO2 sorbents in the presence of various cations (magnesium, zinc, and nickel) that helped to catalyze the formation of surface precipitates. Dissolved concentrations of elements were monitored via inductively coupled plasma optical emission spectrometry (ICP-OES). Solids were characterized via X-ray diffraction (XRD), and K surface complexation was analyzed via X-ray absorption near edge structure (XANES) spectroscopy. X-ray diffraction analysis indicated bayerite, layered double hydroxides (LDH), and silicated LDH were formed as reaction products, thus creating new surface sites for potential K adsorption. The presence of Si increased K adsorption perhaps due to its role in the formation of LDH surface precipitates. When the differences between observed and theoretical surface area normalized K sorption densities were averaged, a 31% increase in K adsorption was observed in the presence of Si. XANES analysis indicated that the binding mechanism of K to Si is different than that of K to Al, perhaps due to the presence of inner-sphere complexation of K to Al-oxide. Samples reacted for one month versus one week yielded more intense XANES post-edge peaks which indicated that the K sorption complex changes over time. Overall, our findings provide novel insights into the mechanisms of K fixation in soil and has high implication in providing improved K fertilizer recommendation to growers.