Inner-sphere Complexes Research Articles

Metal heteroatoms significantly enhance efficacy of TiO2 nanomaterials in promoting hydrolysis of organophosphates: Implications for mitigating pollution of plastic additives.

Organophosphate esters (OPEs) are prevalent pollutants in the aquatic environment. OPEs are released from many sources, particularly, from the breakdown and weathering of plastic wastes, as OPEs are commonly used plastic additives. Metal oxide mineral nanoparticles play critical roles in the hydrolytic transformation of OPEs. While natural minerals often contain metal impurities, it is unclear how metal heteroatoms affect the efficiency of mineral nanoparticles in mediating hydrolysis reactions. Herein, we show that transition metal-doped anatase titanium dioxide (TiO2) nanomaterials are more effective in catalyzing the hydrolysis of 4-nitrophenyl phosphate (pNPP), a model OPE compound, with the relative effects of the heteroatoms following the order of Fe > Cr > Mn ≈ Ni > Co > Cu. With multiple lines of evidence based on spectroscopic analysis, kinetics modeling, and theoretical calculations, we show that metal doping increases the Lewis acidity of the TiO2 nanomaterials by increasing the oxidation state of surface Ti atoms, inducing oxygen vacancies, and creating additional Lewis acid sites with stronger acidities. Moreover, the increased amounts of surface hydroxyl groups due to metal-doping enhance inner-sphere complexation of pNPP through ligand exchange. The interesting observation that Fe-doped TiO2 exhibited the highest catalytic efficiency may have important implications for reducing the risks of organophosphate plastic additives, as iron is the most common heteroatom of naturally occurring TiO2 (nano)materials.

Experimental and advanced equilibrium studies on the enhanced adsorption of phosphate, cadmium, and safranin dye pollutants using methoxy exfoliated glauconite

Natural glauconite, as a mixed-layered clay mineral, was subjected to exfoliation processes, producing silicate monolayers or individual sheets that were further modified with methanol into methoxy exfoliated glauconite (Mth/EXG). The structure was assessed as an enhanced adsorbent for three types of common water contaminants, including phosphate (PO43-), safranin-O dye (SFR), and cadmium metal ions (Cd2+). The Mth/EXG structure achieved promising adsorption capacities at the saturation points equal to 269.9 mg/g for PO43-, 312 mg/g for SFR, and 234.5 mg/g for Cd2+ which are significantly better than the reported values for several studied adsorbents of higher costs and complex production procedures. The adsorption processes and the predicted regulated mechanisms in terms of the adsorbate/adsorbent interface were illustrated based on the steric and energetic findings that correspond to the applied monolayer equilibrium model of one energy site. The structure displays active site densities of 82.5 mg/g (PO43-), 136.3 mg/g (SFR), and 83.4 mg/g (Cd2+), which illustrate the high uptake performance of SFR. Also, the steric parameters reflected the suitability of each existing site to be filled with 4 ions of PO43-, SFR, and Cd2+. The adsorption energy (less than 40 kJ/mol) in conjunction with free adsorption energy from D-R model (8–16 kJ/mol) and steric parameters validate the dominant impact of the multi-ionic physical mechanisms (hydrogen bonding and van der Waals forces), in addition to the assistant impact of some weak chemical processes that might be assigned to the formed inner-sphere complex. Also, these reactions all occurred spontaneously with exothermic behaviors according to the thermodynamic functions. Additionally, the structure exhibit significant affinity for the studied pollutants even in the existing of completive chemical including anions, cations and organic molecules.

Complexation of Trivalent Lanthanides with Hexaalkyl Nitrilotriacetamides into Methylimidazolium-Based Ionic Liquids: Spectroscopic, Electrochemical, Calorimetric, and Theoretical Insights.

Exothermic, spontaneous inner-sphere complexation of trivalent lanthanides with N,N,N',N',N″,N″-hexaalkyl-substituted nitrilotriacetamides (HRNTAs) into 1-hexyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (C6mim NTf2) is reported with a predominant presence of ML and ML2 complexes having complexation constants, β1Eu 3.10 ± 0.02 ,β1Nd 2.67 ± 0.03 and β2Eu 5.22 ± 0.04, β2Nd 4.95 ± 0.02, respectively, for the n-butyl-substituted HRNTA (HBNTA); while those for the n-hexyl derivative (HHNTA) are β1Eu 4.27 ± 0.03, β1Nd 3.71 ± 0.03 and β2Eu 7.70 ± 0.03, β2Nd 7.18 ± 0.04, respectively. HHNTA shows better complexing ability; whereas the stronger complexation of the Nd3+ over Eu3+ is attributed to the lanthanide contraction. Furthermore, the nature of the ionic liquid also influences the extent of complexation with the trend: C4mim NTf2 > C6mim NTf2 > C8mim NTf2, which follows the order of their dielectric constants. Judd-Ofelt parameters were calculated from photoluminescence data to get an idea about the symmetry of the Eu3+ complexes. Electrochemical investigations give diffusion coefficient values of 1.17 × 10-7 and 8.26 × 10-8 cm2/s for the Eu3+ complexes of HBNTA and HHNTA, respectively. Changes in the spectral characteristics and peak positions are evidenced in the FTIR spectra on the complexation of Eu3+ with the HRNTA ligands in C6mim NTf2. Structure optimization for the complexes was performed by DFT computations.

Removal of phosphate from wastewater using zirconium/iron embedded chitosan/alginate hydrogel beads: An experimental and computational perspective

Adsorptive removal of phosphate plays a crucial role in mitigating eutrophication. Herein, the Zr/Fe embedded chitosan/alginate hydrogel bead (Zr/Fe/CS/Alg) is reported as an effective phosphate adsorbent. This polymer nanocomposite is synthesized by the in-situ reduction of the metals on the polymer matrix. The synthesized adsorbent was characterized by the FTIR, SEM-EDX, TGA, BET, and XPS. The adsorbent showed a maximum phosphate adsorption capacity of 221.72 mg/g at pH 3. The experimental data fit well with the Freundlich isotherm and pseudo-second-order kinetics model, indicating a heterogeneous multilayer surface formation and a chemisorption-dominated adsorption process. Density Functional Theory (DFT) and Monte Carlo (MC) calculations revealed high negative adsorption energy due to the chemisorption of phosphate on the adsorbent. Hence, the major interactions such as electrostatic attraction, hydrogen bonding, and inner-sphere complexation of phosphate adsorption and Zr/Fe/CS/Alg hydrogel beads were investigated from the experimental and computational analysis. The negative values of thermodynamic parameters indicated a spontaneous, exothermic, and less random adsorption process. The synthesized adsorbent exhibited excellent selectivity toward phosphate and maintained 73 % efficiency after six adsorption/desorption cycles. The Zr/Fe/CS/Alg hydrogel beads reduced the phosphate concentration in real wastewater samples from 19.02 mg/L to 0.985 mg/L, suggesting that these nanocomposite hydrogel beads could be a promising adsorbent for real-world applications.

Enhanced adsorption of aqueous perfluorooctanoic acid on iron-functionalized biochar: elucidating the roles of inner-sphere complexation

Perfluorooctanoic acid (PFOA) is ubiquitously detected in various water bodies, which raises the urgent need for developing effective and economic remediation methods in response to its health risks. The adsorptive removal of PFOA by biochar (BC) is regarded as a simple, effective, and economical technique. However, engineered BCs, including FeCl3-activated BC, for PFOA removal and adsorption mechanisms have been ill-studied. In this study, a FeCl3-activated dairy manure-derived biochar (Fe@MBC) was prepared via one-step pyrolysis/activation, and its properties and adsorption characteristics were compared with a pristine manure-derived biochar (P-MBC). The FeCl3 activation largely increased the surface area of Fe@MBC and the deposition of FexOy minerals on surface of Fe@MBC while significantly elevating the surface roughness of Fe@MBC. The maximum adsorption capacity of Fe@MBC for PFOA (233 mg·g−1) was five times higher than that of P-MBC (46 mg·g−1). PFOA adsorption was favorable at low solution pH and was independent on ionic strength, which supported the major contribution by inner-sphere complexation rather than out-sphere complexation. This mechanism was further confirmed by the disappearance of FeO peak on Fourier transform infrared spectrum and the blue-shift of Fe binding energies on X-ray photoelectron Fe 2p spectrum of Fe@MBC after PFOA adsorption. Fe@MBC maintained a near 100% adsorption capacity for PFOA after 4 cycles of chemical regeneration. Fe@MBC also exhibited efficient removal for PFOA and other PFAS compounds at trace levels in the lake water and wastewater treatment plant effluent. Thus, this study highlights a promising insight for selectively eliminating PFASs from water.

The Performance and Mechanism of Solvothermal Synthesis of a Ca-Fe-La Composite for Enhanced Removal of Phosphate from Aqueous Solutions

Since it is a limiting nutrient element in rivers and lakes, the effective removal of phosphorus is key to alleviating eutrophication. In this study, the one-pot solvothermal method was adopted to prepare an environmentally friendly Ca-Fe-La composite. This is an amorphous material with a large specific surface area of 278.41 m2 g−1. The effects of coexisting anions and pH on the phosphate removal performance were explored. Phosphate adsorption mechanisms were revealed by various characterization techniques. The phosphate adsorption obeyed the fractal-like pseudo-second-order (PSO) kinetic model, implying that the overall adsorption system was highly heterogeneous. In this work, the maximum adsorption capacity predicted by the Langmuir model was 93.0 mg g−1 (as PO43−-P). The phosphate-loaded Ca-Fe-La composite could be used as a slow-release fertilizer, achieving waste management and resource utilization. The presence of SO42−, CO32− and HCO3− anions inhibited the phosphate adsorption significantly. It was unfavorable for phosphate removal at a high pH value. Inner-sphere complexation and electrostatic attraction were mainly responsible for phosphate adsorption onto the Ca-Fe-La composite.

Converting large-scale waste paper fibers into lanthanum-modified cellulose carbon aerogel adsorbents for efficient phosphorus removal

This study presents the synthesis of a novel lanthanum-modified cellulose-based carbon aerogel (La-CCA) from waste printing paper, aimed at addressing the issue of phosphate pollution in aquatic environments. The objective was to develop an effective and sustainable adsorbent to mitigate eutrophication caused by excess phosphates in water bodies. La-CCA exhibited a remarkable phosphate adsorption capacity, peaking at 44.32 mg/g under optimal conditions, demonstrating its efficiency as an adsorbent. The novelty of this work lies in the use of waste paper as a raw material, coupled with lanthanum modification, which enhanced adsorption performance through multiple mechanisms, including electrostatic interactions, ligand exchange, and inner-sphere complexation. The study also discussed the retention of the microfibrous structure of cellulose, contributing to the material’s stability and functionality. Comprehensive analyses including zeta potential, FTIR, and XPS elucidate the underlying adsorption mechanisms. La-CCA was demonstrated to be easily separable from solutions with minimal lanthanum leaching, particularly under conditions above pH 3.0, underscoring its potential for practical applications in phosphate removal from nutrient-enriched waters.

Interpretation of vertical migration and enrichment processes of rare earth elements (REEs) in ion-adsorption-type mineralization in Japan based on REE speciation analyses

Typical vertical profiles of ion-adsorption-type rare earth element (REE) deposits discovered in southwest Japan were studied by conducting speciation analyses, including X-ray absorption fine structure and laser-induced fluorescence spectroscopy combined with transmission electron microscopy and adsorption/desorption experiments. The results revealed that REE speciation, migration, and enrichment in weathered granite is largely controlled by soil pH, which in turn controls the variable charges of kaolinite, the REE host phase. Both the distribution coefficient Kd and the soil pH increase with depth. As a result, (i) REE dissolution and migration occur in the near-surface acidic environment of the upper layers, where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a lesser degree, and (ii) REEs accumulate in the relatively high-pH environment below the surface, where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a larger degree, producing REE adsorption sites with variable charges. An increase of soil pH to greater than 6 in deeper layers promotes inner-sphere complexation of REEs. Although inner-sphere complexation inhibits the ion-exchange extraction of REEs, the inner-sphere complexes can be still extracted by lowering the pH of the extraction solution. This fact, which indicates that the adsorption of both inner- and outer-sphere complexes is reversible, is important in terms of both (i) understanding vertical REE profiles in which the pH varies and (ii) the efficient recovery of REEs from REE-enriched layers at all depths in weathered granite.

Sorption of trivalent europium Eu(III) by Na+-substituted bentonite: Mechanistic insight and stabilization effect

The sorption of Eu(III) by Na+-substituted bentonite (Na-bentonite) was investigated as a function of pH and NaNO3 concentration ([NaNO3]0). At pH < ∼7.5, Eu(III) sorption decreased with the increasing [NaNO3]0, whereas at pH > ∼7.5, it remained nearly complete, independent of [NaNO3]0. Our thermodynamic model indicated that the sorption at pH < ∼7.5 occurred via a combination of cation exchange and surface complexation, with the former diminishing as [NaNO3]0 increased. Meanwhile, the sorption at pH > ∼7.5 was primarily due to surface complexation. By X-ray diffraction, the incorporation of hydrated Eu(III) in the interlayers of montmorillonite increased its lattice spacing and crystallinity along the c-axis, where cation exchange was predominant. Also, Eu LIII-edge X-ray absorption spectroscopy revealed that the sample dominated by cation exchange had an absorption edge energy and coordination structure similar to aqueous Eu(III), indicating outersphere complex formation. In other cases, Eu(III) sorption was characterized by innersphere complexation, as indicated by increased covalency and the presence of more pronounced second coordination shells. Importantly, the analysis of dissolved Si and Al suggested that the increased stability of Na-bentonite was likely due to the surface complexation of Eu(III) with aluminol groups at the edges, especially at higher surface coverages. Given its high sorption capacity for Eu(III) and stabilization effect mediated by sorption, Na-bentonite could be serve as an effective backfill material and migration barrier for containing actinides in nuclear waste repositories.

Corn stover waste preparation cerium-modified biochar for phosphate removal from pig farm wastewater: Adsorption performance and mechanism

The high phosphorus content in livestock and poultry wastewater is a significant factor contributing to water eutrophication. It is imperative to seek an economically efficient method for phosphate recovery. This study employed cerium-modified biochar to recover phosphate from pig farm wastewater. An investigation was conducted to examine the adsorption performance and removal mechanism of phosphate. Among the different samples, 0.1CeB-500℃ was selected for subsequent experiments. It exhibited a phosphate adsorption capacity of 9.58 mg/g and a removal efficiency of 95.75 %. The results showed that the phosphate adsorption process followed not only the pseudo-second-order kinetic model, but also the Langmuir isotherm model. It suggested that the adsorption of phosphate onto the biochar occurred in a monolayer chemical manner, with a maximum adsorption capacity of 10.86 mg/g. Phosphate adsorption was minimally affected within the pH range of 2–9, with Cl- having negligible impact, NO3- slightly inhibiting, and HCO3- and CO32- significantly hindering phosphate adsorption. A series of characterization results indicated that phosphate removal occurred through surface precipitation forming CePO4, ligand exchange between carbonate and phosphate, inner-sphere complexation, and electrostatic attraction. The phosphate removal efficiency from pig farm wastewater was 43.25 %, demonstrating promising potential for practical application.

The impact of organic matter and iron/calcium coupling on phosphorus retention in the hyporheic zone of the Danjiangkou area tributary: Evidence from bonding recognition

The coupling between organic matter (OM) and minerals considerably influences the phosphorus (P) cycle within the hyporheic zone, but the role of different geological mineral-organic complexes (MOCs) on P burial during hyporheic exchange remains under-explored. This study investigates the effects of OM and iron (Fe)/calcium (Ca) coupling on P migration within the hyporheic zone of an agricultural tributary to the Danjiangkou Reservoir. These relationships were explored by measuring hyporheic flow (q), organic and inorganic P forms, and sediment PO4-P adsorption capacity [following treatment with fulvic acid (FA), Fe-OM, or Ca-OM]. Multivariate statistical analysis, X-Ray Diffraction, Fourier-transform Infrared Spectroscopy, and X-ray Photoelectron Spectroscopy were employed to elucidate the underlying mechanisms. Results indicate that upward hyporheic flow transports dissolved porewater P into surface water, contributing 11.27–12.13 % of the total P flux. MOCs associated with Fe(III)/Ca silicate minerals, along with FA and labile OM, were identified as key OM fractions influencing P migration, contributing 5–24 %, 10–11.7 %, and 6–14.9 % to the overall flux, respectively. FA and labile OM facilitate P release, whereas MOCs enhance P retention. Ca-OM is the most efficient PO4-P adsorption [adsorption capacity (AC): 0.8980–0.9524 mg/g], followed by Fe-OM (AC: 0.5120–0.7020 mg/g), original sediment (AC: 0.4368–0.5596 mg/g), and FA (AC: 0.2657–0.2769 mg/g). Cation bridges, primarily formed by -OH and -NH2 groups within Ca-OM (outer-sphere complexes), promote greater P adsorption than Fe-OM (inner-sphere complexes, mainly associated with -COOH). However, Fe-OM-P exhibits a more stable structure. In high P environments, P adsorption onto Ca-OM may induce the release of labile OM, temporarily retaining P through resorption onto labile OM. Hyporheic flow with higher pH and Eh values promotes MOC formation, underscoring their significant P retention capacity. Therefore, strategic MOC use within the hyporheic zone is crucial for mitigating surface water eutrophication.

Insights into the removal of sulfamethazine and sulfonamide-resistant bacteria from wastewater by Fe-Mn spinel oxide modified cow manure biochar activated peroxymonosulfate: A nonradical pathway regulated by enhanced adsorption and 3d orbital electron reconstruction

Effectively regulating nonradical pathways is crucial for adapting to complex water environments in sulfate radical-based advanced oxidation processes (SR-AOPs). This study prepared manganese ferrite-modified cow-manure biochar composites (BC-FM) as peroxymonosulfate activators to remove sulfamethazine (SMT) and sulfonamide-resistant bacteria (SA-ARB) from wastewater. The extensive conjugated graphitic structure in biochar induced Fe 3d orbital electron reconstruction, promoting empty orbitals formation and enhancing peroxymonosulfate inner-sphere complexation. This facilitated 100 % electron-transfer-dominated nonradical regulation. BC-FM exhibited remarkable catalytic performance, with apparent rate constant of 0.170 min−1 for SMT, inactivating ∼8.6 log of SA-ARB, and effectively blocking horizontal transfer of antibiotic resistance genes in both single and complex pollution systems (SMT/SA-ARB). Moreover, ion leaching experiments, cycling tests, real-water experiments, fluidized-bed and fixed-bed experiments demonstrated BC-FM’s potential for prolonged utilization and practical implementation. This study offers new insights into designing high-performance, environment-friendly bimetal catalysts and provides a basis for remediating organic contaminants with SR-AOPs in livestock wastewater.

Molecular insights into the binding mechanism of strontium and cesium on phyllosilicates with different expandability

The environmental fate of strontium (Sr) and cesium (Cs), as the critical radioactive fission products, have raised significant concerns regarding radioactive waste disposal and environmental protection. The current study investigated the distinction in the binding configurations of Sr2+ and Cs+ on various 2:1 phyllosilicate (illite, vermiculite, and montmorillonite) by combining batch adsorption, sequential extraction, and spectroscopic analyses. The results show that strontium adsorption is strongly influenced by pH as well as ionic strength, while there is no significant variability in strontium adsorption by different types of clay minerals. EXAFS analysis confirms the outer complexation of strontium on the planar sites of the clay minerals, i.e., Sr2+ is surrounded by ~8.0 O atoms, RSr-O ≈ 2.6 Å, and that process is mainly realized by ion exchange. In contrast, Cs+ adsorption was markedly influenced by the variety of clay minerals but less by pH and ionic strength, the presence of humic acid (HA) inhibited Cs+ adsorption. The inner-sphere complexation formed mainly at the frayed edge sites on illite, and interlayer sites on vermiculite and montmorillonite, was the dominant mechanism for Cs+ adsorption. In addition, the collapse of the interlayer space of vermiculite induced by Cs+ adsorption on the interlayer sites was responsible for the more stable and irreversible immobilization. The findings in present work highlighted the significance of prevailed mineral in governing environmental migration risk of radionuclides, the revealed adsorption mechanism and binding configuration of Sr2+ and Cs+ on typical phyllosilicates would be referable in constructing a reliable migration model of Sr2+ and Cs+ in natural media.

Insights into the relationship between Nitrilotri(methylphosphonic acid) (NTMP) adsorption and physicochemical properties of iron oxides

Non-reactive phosphorus (e.g., phosphonate) contributes to eutrophication, while little attention has been paid to its control. The iron-based materials are highly efficient in orthophosphate removal from water, while the correlation between their physicochemical properties and selective phosphonate (e.g. Nitrilotri(methylphosphonic acid) (NTMP)) adsorption is still unclear. In this study, Fe3O4 (magnetite), FeOOH (goethite) and Fe2O3 (hematite) with different crystal structures, particle sizes and surface area were synthesized for NTMP adsorption. The physicochemical properties of the three kinds of iron oxides were characterized. The batch experiments were applied to explore the NTMP adsorption and desorption performance. The maximum adsorption capacity of NTMP on Fe3O4, FeOOH and Fe2O3 were 4.14, 1.91 and 0.99 mg-P/g, respectively. Results implied the crystal structure and surface area of iron oxides determined the maximum NTMP adsorption capacity. The NTMP adsorption on the three iron oxides was spontaneous, endothermic and randomness increase. The iron oxides showed high selectivity towards NTMP adsorption in water containing anions, while the co-existing Ca2+ and Mg2+ remarkably increased the adsorption capacity. The successive adsorption-desorption cycles suggested a favorable reusability of the above iron oxides and a high NTMP desorption efficiency. The specific NTMP adsorption capacity followed the sequence of FeOOH > Fe2O3 > Fe3O4, and was highly dependent on surface OH− proportion. The NTMP adsorption mechanism was mainly attributed to inner-sphere complexation. This study provides insights into the iron-based adsorbents design for selective phosphonate adsorption in the future.

Transferring red mud to efficient adsorbent for the adsorption and immobilization of Ni(Ⅱ) from aqueous solution

Red mud, a solid waste produced in large quantities, possesses a high specific surface area and is rich in metal oxides, making it a promising material for adsorbent preparation. However, its practical application is constrained by its relatively low adsorption capacity and the potential environmental risks it poses. This study focused on the preparation of modified red mud (MRM) with enhanced adsorption performance for Ni2+ using a hydrothermal method involving sodium hydroxide and colloidal silica. The maximum adsorption capacity of MRM for Ni2+ reached 8.22 mmol·g–1, a substantial improvement compared to raw red mud (0.28 mmol·g–1) and sulfuric acid-activated red mud (0.46 mmol·g–1). The pseudo-second-order kinetic and Langmuir isotherm models accurately described the monolayer chemical adsorption process of Ni2+ on MRM. Additionally, leaching tests with simulated rainwater demonstrated that Ni-loaded MRM exhibited high stability, suggesting its potential for safe stockpiling or repurposing, such as in construction materials. Sequential extraction, XRD, FT-IR, and XPS results revealed that cation exchange was the primary mechanism in the adsorption process, with Ni2+ being immobilized within the zeolite framework structure of MRM, contributing to its strong adsorption stability. Inner-sphere complex formation also played a role in Ni2+ adsorption. In conclusion, this method offers an effective approach to both red mud utilization and heavy metal removal from wastewater, presenting a practical solution for waste management through resource recovery and environmental remediation.

Crucial role of humic substance type in Cr(VI) reduction by humic substance-Fe(III) coprecipitates but not in adsorption

Wetlands exhibit a self-purification effect on Cr(VI) owing to the adsorption and reduction capabilities of their humic substance (HS)-Fe(III) coprecipitates. However, the similarities and differences in the adsorption and reduction of Cr(VI) by different types of HS-Fe(III) coprecipitates remains unknown. In this study, fulvic acid (FA)- and humic acid (HA)-Fe(III) coprecipitates were synthesized with initial C/Fe ratios ranging from 0.25 to 15, and a comparative analysis of their adsorption and reduction effects was conducted. The results showed that FA- and HA-Fe(III) coprecipitates exhibit similar abilities to adsorb Cr(VI) by forming inner-sphere complexes with ferrihydrite (Fh), as well as with FA/HA. The association between FA/HA and Fe(III) not only blocked certain FeOH adsorption sites, but also enhanced the electrostatic repulsion towards Cr(VI), resulting in a proportionate decrease in their adsorption ability. For reduction, inductive and intrinsic reduction were involved in both FA- and HA-Fe(III) coprecipitates. However, the synergism/antagonism differed with the inherent sites (e.g., phenolic hydroxyl, ArOH) and activated sites (e.g., alcoholic hydroxyl, AlOH). Based on the size differences between FA and HA, the AlOH contained in FA was more easily activated by Fe(III) than that in HA, owing to the shorter induction path required. Thus, consistent synergism was observed in FA-Fe(III) coprecipitates regardless of Fe(III) species. In contrast, synergism was only observed in HA-Fe(III) coprecipitates containing Fh, because the inductive ability of Fe(III) cations was too weak to activate AlOH through the longer path. Moreover, with irreversible consumption of AlOH, intrinsic reduction became the dominant pathway at concentrations >1 mM Cr(VI). The preferential elimination of ArOH subsequently led to a transition to antagonism. These outcomes deepen our scientifical understanding of the environmental effects of HS-Fe(III) coprecipitates and offer new perspectives for exploring their potential applications in the remediation of Cr-contaminated sites.

Enhancing Europium Adsorption Effect of Fe on Several Geological Materials by Applying XANES, EXAFS, and Wavelet Transform Techniques.

This study conducted adsorption experiments using Europium (Eu(III)) on geological materials collected from Taiwan. Batch tests on argillite, basalt, granite, and biotite showed that argillite and basalt exhibited strong adsorption reactions with Eu. X-ray diffraction (XRD) analysis also clearly indicated differences before and after adsorption. By combining X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and wavelet transform (WT) analyses, we observed that the Fe2O3 content significantly affects the Eu-Fe distance in the inner-sphere layer during the Eu adsorption process. The wavelet transform analysis for two-dimensional information helps differentiate two distances of Eu-O, which are difficult to analyze, with hydrated outer-sphere Eu-O distances ranging from 2.42 to 2.52 Å and inner-sphere Eu-O distances from 2.27 to 2.32 Å. The EXAFS results for Fe2O3 and SiO2 in argillite and basalt reveal different adsorption mechanisms. Fe2O3 exhibits inner-sphere surface complexation in the order of basalt, argillite, and granite, while SiO2 forms outer-sphere ion exchange with basalt and argillite. Wavelet transform analysis also highlights the differences among these materials.

Efficient phosphorus removal using the La-based perovskite oxides: Role of B-site metal for modulating the surface electronic structure

Highly efficient removal of phosphate from water bodies is of great importance to controlling eutrophication. Herein, the lanthanum-based perovskites (i.e., LaMnO3, LaFeO3) were synthesized and employed for phosphorus adsorption. Adsorption experiments showed that the phosphate removal by LaMnO3 was well fitted with the pseudo second-order kinetic model, with a multi-stage adsorption process. The LaMnO3 exhibited a maximum adsorption capacity of 51.3 mg/g for phosphate calculated using the Langmuir model, which was 2.1 times higher than that of LaFeO3 under neutral conditions. Characterization and DFT calculation results further revealed that the La element on the surface of perovskite was the main adsorption site via inner-sphere complex and/or electrostatic interactions, whereas the B-site metal (i.e. Mn element) could trigger the surface electronic structure modulation such as the reduction of surface bonding barrier, for further improving the phosphate adsorption. Additionally, the LaMnO3 adsorbent exhibited commendable performance in treating natural water with low phosphorus concentration and good regenerative capability. This work provides insight into the development of novel perovskite-type adsorbents for efficiently removing phosphorus in environmental remediation.

Enhanced phosphorus removal from anoxic water using oxygen-carrying iron-rich biochar: Combined roles of adsorption and keystone taxa

Anthropogenic enrichment of phosphorus (P) in water environment can cause eutrophication, harmful algal blooms, and water quality deterioration. Adsorbents are often used for the removal and recovery of P from water, however, P is highly susceptible to re-release in anoxic benthic environments. As a response, this study prepared oxygen-carrying iron-rich biochar (O-Fe-BC) as an effective oxygen micro-nanobubble carrier (Q = 8.7024 cm³/g STP at 1.5 MPa) and P adsorbent (qm = 16.7097 mg P/g, q0.1 = 3.1974 mg P/g). Over the 90-day experimental period with O-Fe-BC, dissolved oxygen (DO) levels in the overlying water could maintain at ∼4 mg/L (peaking at ∼9.5 mg/L), and total phosphorus (TP) and soluble reactive phosphorus (SRP) levels decreased by over 96 %. The higher inorganic phosphorus content in the surface sediment-biochar mixture, along with the lower labile P and Fe concentration in the sediment pore water in the O-Fe-BC group compared to other groups, suggested the enhanced P immobilization. Further mechanism exploration revealed the combined roles of adsorption and microbial response, in which O-Fe-BC achieved efficient phosphate adsorption primarily through inner-sphere complexation via ligand exchange and keystone taxa (particularly Candidatus Electronema) played a crucial role in driving water chemistry divergence. Specially, these cable bacteria could provide large pools of Fe oxides in the surface sediment, binding with P to prevent its release, as supported by significant correlations between Ca. Electronema abundance and oxidation–reduction potential (ORP), TP, SRP, and sediment Fe-P variations. Additionally, a pot experiment with mung bean seedlings showed that the recovered O-Fe-BC significantly promoted the seed germination and growth, indicating its potential as a novel material for removing and recovering P from eutrophic waters. Taken together, our work provided a promising strategy for sustainable anoxia and P pollution mitigation, and also highlighted the indispensable roles of inner-sphere adsorption in P recovery and microbial keystone taxa in P cycling regulation.

Mechanistic insights into selenite and selenate immobilization using brucite-rich magnesium precipitate derived from seawater electrochlorination facility

This study explored the application of magnesium precipitate (MP) obtained from seawater electrochlorination storage tanks as an innovative and sustainable adsorbent for Se(IV) and Se(VI) in water. Initially, the collected pristine MP mainly consisted of the low crystalline Mg(OH)2 (brucite) phase. Subsequently, the MP underwent calcination (CMP), and analyses via scanning electron microscopy (SEM) and X-ray diffraction (XRD) confirmed an improved crystallinity, displaying a typical hexagonal plate structure in the aqueous phase. Notably, the CMP exhibited a significant adsorption capacity (qm: 85.0 mg/g) for Se(IV), while the adsorption capacity for Se(VI) was lower, determined as 3.0 mg/g using the Langmuir adsorption model. Se(IV) adsorption remained relatively consistent across a wide pH range and ionic strength in the presence of competing anions. In contrast, Se(VI) adsorption varied under the same conditions. This differing adsorption behavior of Se(IV) and Se(VI) on CMP could be ascribed to different mechanisms: inner-sphere predominant surface complexation for Se(IV) and outer-sphere complexation for Se(VI). These mechanisms were confirmed via X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), XRD, and SEM analyses, and surface complexation modeling (PHREEQC–PEST) of the batch experimental results. In conclusion, these findings underscored the potential utility of MP as an effective adsorbent for selenium, positioning it as an environmentally sustainable and significant novel material. Furthermore, the study offered mechanistic insights into the interaction between CMP, Se (IV), and Se(VI) in the aqueous phase.