Outer-sphere Complexes Research Articles

Role of Organic Fertilizer in the Transfer of Lead to Vegetables Produced in Tropical Mountain Agroecosystems.

Understanding the relationship between the aerobic transformation of organic matter (OM) and the bioavailability of lead to plants may allow the safe application of organic fertilizers (OF) in agriculture. The present study aimed to elucidate the relationship of different OM structures with Pb, revealing the action of OF (poultry litter) on Pb dynamics, presenting the effects of OM transformations on bioavailability and transfer to vegetables produced in tropical mountain agroecosystems (TMA). The association of Pb with hydrophilic structures (CAlk-O and CAlk-di-O) during the aerobic transformation of poultry litter (PL) contributes to the increase in the water-soluble form of this metal (3.17-15.30%). The structural changes promoted by the transformation of OM, in addition to reducing the adsorption capacity of Pb in PL (Kd reduction from 1135.50 to 87.49), favor the formation of outer-sphere complexes. PL that have a more labile structure, i.e., those that are less humified, have greater affinity for Pb. The greater affinity of Pb for labile structures that are preserved in PL during OM transformations contributed to its increase and transport to edible plant parts. Considering the edible parts of vegetables grown in TMA and fertilized with fresh PL, 100% of broccoli, 91.78% of cabbage, 80.00% of tomato, 65.96% of parsley, 49.19% of lettuce, and 32.88% of cauliflower showed Pb contamination that exceeded the permitted level. Therefore, OF contributes to lead contamination of food produced in TMA, representing a risk to human health. Studies are needed to propose additional treatments for this residue before its use.

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.

Mechanistic insight into the simultaneous removal of Cr(VI) and phosphate by a novel versatile bimetallic material

Industrial wastewater containing hexavalent chromium Cr(VI) and phosphate poses a great threat to human health and the aquatic ecological environment. In this study, a novel La(OH)3- and CaO2-fabricated CNT (La-Ca-CNT) material was developed for the simultaneous and highly effective removal of aqueous Cr(VI) and phosphate. Characterization results showed that synergistic effects existed between the CNT support and La and Ca species. La-Ca-CNT showed high phosphate and Cr(VI) removal rates in acidic conditions with high stability. Kinetic study suggested that the fast adsorption of phosphate on La-Ca-CNT was controlled by intraparticle diffusion. The removal of Cr(VI) and phosphate interacted with each other, and the removal of Cr(VI) went through a slow-fast-slow reaction, reaching a Cr(VI) removal rate of over 97% within 180min. La-Ca-CNT had a high phosphate adsorption capacity (174.3mg/g), and over 70% of the adsorbed phosphate could be recovered. The presence of co-existing anions showed negative effects on phosphate adsorption but negligible effects on Cr(VI) reduction, while organic carbon in natural water showed no effect on phosphate and Cr(VI) removal. A mechanistic study revealed that phosphate was removed by physical-chemical adsorption (outer-sphere complexation and ligand exchange) over La-Ca-CNT, while Cr(VI) was reduced by H2O2 generated from CaO2 or directly by surface CaO2.

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.

Gel-type resin loaded with nano-hydrated ferric oxide for the removal of anions from papermaking wastewater

The main anions in papermaking wastewater are sulfate and chloride. In this paper, a strongly basic gel-type anion exchange resin (201×7) loaded with 20 ~ 200nm hydrated ferric oxide was prepared by dispersion impregnation with ethanol. The modified resin enhances the ability to remove sulfate by complexation of ligands to cause sulfate to form outer and inner sphere complexes on hydrated ferric oxide. The modified resin was dependent on acidic conditions, and the maximum exchange capacity for sulfate was enhanced by 14.2% under the optimal pH, exchange time, and ion concentration conditions. Competitive exchange experiments showed that the removal effect of the modified resin on chloride was almost unchanged under different chloride, sulfate ratios, and the degree of improvement of the removal effect on sulfate decreased from 9.5 ~ 5.5% with the increase of chloride ratio. The removal of sulfate by the modified resin was consistent with the proposed secondary kinetics and Langmuir adsorption model. In addition, the modified resin maintained 88% reuse after four desorption-adsorption cycles and achieved a regeneration rate of 93.1% after was eluted with HCl and reloaded with hydrated ferric oxide. The expected removal effect was well achieved when the resin was applied to the actual wastewater treatment. The above results indicate that the hydrated ferric oxide modification can improve the ability of the 201×7 resin to remove sulfate from water, and is a promising method for removing anions from papermaking wastewater.

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.

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.

Highly efficient removal of aqueous phosphate via iron-manganese fabricated biochar: Performance and mechanism

Biochar (BC) has emerged as a potential solution to phosphate removal from wastewater primarily resulting from global overuse of fertilizers. Further modification by embedment of iron (Fe)-manganese (Mn) oxides on BC can enhance phosphate removal; however, the modification method serves as a vital factor underlying distinctive removal performances and mechanisms, which have yet been systematically examined. Herein, two Fe–Mn modified BC, Fe/MnBC (comprised of Fe3O4 and MnO2) and Fe–MnBC (comprised of MnFe2O4), were comprehensively investigated for gaining insights into the unsolved perspectives. The results indicated that Fe–MnBC exhibited a markedly greater maximum phosphate adsorption capacity of 135.88 mg g−1 than that of Fe/MnBC with 17.93 mg g−1. The comparative results based on microstructure and spectroscopic analyses suggested that different Fe and Mn oxides were successfully loaded, which played a distinctive role in phosphate removal. Further characterizations unveiled that the key mechanisms for phosphate removal by Fe/MnBC are inner-sphere complexation and precipitation, while electrostatic interaction and outer-sphere complexation are the dominant mechanisms underlying the notable performance of Fe–MnBC. The delicately designed Fe–MnBC with special structure and property also enabled a superior regeneration capacity, which presented a promisingly high phosphate removal efficacy of over 81.34% after five cycles. These results enhance comprehension regarding the impact of biochar modification techniques on phosphate removal, offering positive indications for the remediation of excessive phosphate and other pollutant-containing water through feasible design and green chemicals.

Reclaiming selenium from water using aluminum-modified biochar: Adsorption behaviors, mechanisms, and effects on growth of wheat seedlings

Although selenium is an essential nutrient, its contamination in water poses serious risks to human health and ecosystems. In this study, aluminum-modified bamboo biochar (Al-BC) was developed to reclaim Se(VI) from water. Compared to pristine biochar (BC), Al-BC had a larger specific surface area (176 m2/g) and pore volume (0.180 cm³/g). The modification, achieved by loading AlOOH and Al2O3 particles onto the surface, enabled Al-BC to achieve a maximum adsorption capacity of 37.6 mg/g for Se(VI) within 2 h and remove 99.6% of Se(VI) across a pH range of 3–10. The main adsorption mechanism of Se(VI) involved electrostatic attraction, forming outer-sphere complexes between Se(VI) and AlOOH sites on the biochar. The bioavailability of Se sorbed on the spent biochar (Al-BC-Se) was thus evaluated. It was discovered that Al-BC-Se successfully released Se(VI), which impacted the growth of wheat seedlings. The Se content reached 134 μg/g dry weight (DW) in wheat shoots and 638 μg/g DW in roots, significantly exceeding normal selenium content (<40 μg/g DW). By successfully applying the modified biochar to capture selenium from water through adsorption and then reusing it as an essential nutrient in soil, this study suggests the promising feasibility of the "removal-collection-reuse" approach for the circular economy of selenium in wastewater.

Unveiling the Influence of Antimony Substitution on the Surface Properties and Adsorption Behavior of Ferrihydrite: From Molecular Mechanisms to Environmental Implications.

Antimony(V) substitution is common in secondary ferrihydrite, especially in mining areas and tailings. However, its impact on the adsorption behavior of ferrihydrite is still unclear. Therefore, this study investigated the influential mechanisms of Sb(V) substitution on the lattice structure and surface properties of Sb-substituted ferrihydrite (SbFh), and its adsorption of coexisting Sb(OH)6-. Antimony(V) is substituted at Fe1 sites and is primarily distributed on the surface. Substitution has opposing effects on the outer- and inner-sphere complexation of Sb(OH)6-. On one hand, substituted-Sb(V) transfers more positive charges to ≡FeOH, reducing the number of H bonds. Subsequently, the charge saturation of ≡FeOH decreases, surface charge increases, and outer-sphere complexation is promoted. On the other hand, the elevated bond valence of Sb-O increases charge saturation of ≡FeOH, reducing the charge capacity that ≡FeOH can accommodate from inner-sphere complexes. Thus, inner-sphere complexation is inhibited. Inner-sphere complexation plays a more important role, and Sb(OH)6- adsorption is inhibited. Additionally, the primary complexation modes of Sb(OH)6- transform from bidentate to monodentate complexation. This research has important implications for understanding the environmental behavior of ferrihydrite, as well as the fate and bioavailability of antimony in mining areas and tailings.

Supreme capture of Europium(ΙΙΙ) by silica-hyperbranched poly(ethylene imine) composites from aqueous solutions − A mechanistic study

Two bio-inspired variations of the sol–gel technique produced silica-hyperbranched poly (ethylene imine) (PEI) composite nanoparticles (NP) and xerogels (XG). Both methods are performed in ambient conditions and do not require toxic organic solvents or high temperatures. We have investigated the removal efficiency of trivalent europium by these two hybrid species in near-neutral aqueous solutions. The adsorption kinetics and isotherms, including data fitting with the pseudo-first and second order kinetic, and the Langmuir isotherm model are presented and discussed. Thermodynamic parameters indicate exothermic reaction (–180 kJ/mol for NP and –192 kJ/mol for XG, respectively) In addition, spectroscopic (Fourier Transform Infra-Red FTIR, Fluorescence Spectroscopy FS, X-ray Photoelectron Spectroscopy XPS) and microscopic techniques (Scanning Electron Microscopy SEM coupled with Energy Dispersive X-ray analysis EDX), as well as ζ-potential and Dynamic light scattering (DLS) measurements, have been employed to evaluate the interaction mechanism between the surface active moieties and Eu(III). The extremely high and homogeneous dispersion of the amino and silicate groups of the composites has led to the highest capacity value (22 mmol/g or 3343 mg/g and 14 mol/g or 2128 mg/g for the two distinct forms of the nanoparticles and the xerogels, respectively) reported up to today implying a potential application for lanthanide recovery. The adsorption data along with the spectroscopic and microscopic indicate that the adsorption is well described by the Langmuir isotherm model and is based on the formation of inner- and outer-sphere complexes between Eu(III) the amine and −Si-O− moieties.

Iron (hydr)oxides-induced activation of sulfite for contaminants degradation: The critical role of structural Fe(III)

Iron-based sulfite (S(IV)) activation has emerged as a novel strategy to generate sulfate radicals (SO4•-) for contaminants degradation. However, numerous studies focused on dissolved iron-induced homogeneous activation processes while the potential of structural Fe(III) remains unclear. In this study, five iron (hydr)oxide soil minerals (FeOx) including ferrihydrite, schwertmannite, lepidocrocite, goethite and hematite, were successfully employed as sources of structural Fe(III) for S(IV) activation. Results showed that the catalytical ability of structural Fe(III) primarily depended on the crystallinity of FeOx instead of their specific surface area and particle size, with ferrihydrite and schwertmannite being the most active. Furthermore, in-situ ATR-FTIR spectroscopy and 2D-COS analysis revealed that HSO3- was initially adsorbed on FeO6 octahedrons of FeOx via monodentate inner-sphere complexation, ultimately oxidized into SO42- which was then re-adsorbed via outer-sphere complexation. During this process, strong oxidizing SO4•- and •OH were formed for pollutants degradation, confirmed by radical quenching experiments and electron spin resonance. Moreover, FeOx/S(IV) system exhibited superior applicability with respect to recycling test, real waters and twenty-six pollutants degradation. Eventually, plausible degradation pathways of three typical pollutants were proposed. This study highlights the feasibility of structural Fe(III)-containing soil minerals for S(IV) activation in wastewater treatment.

Significant role of interlayer in strontium adsorption on weathered biotite

Weathering of micaceous minerals play a significant role in the adsorption and migration of radioactive strontium. Weathering changes the structure of minerals and the capacity of adsorption sites on their surfaces. The regulatory mechanism of environmental factors on radioactive strontium on weathered micaceous minerals remains to be sorted out and clarified. In this work, we studied the adsorption behavior of Sr2+ on weathered micaceous minerals with different weathering degrees via batch experiments and spectroscopic approaches. The batch experiment results indicated that the adsorption capacity of Sr2+ increased from 5.36 mg/g (Na-Bio) to 19.89 mg/g (SCa-Bio) as the weathering degree of biotite increased. The outer-sphere complexation and electrostatic attraction/ion exchange mainly governed the adsorption of Sr2+ on weathered biotite. The type of cation co-existing in solution and the weathering degree of biotite regulate Sr2+ adsorption into the interlayers. Owing to their similar ionic properties (e.g., hydration energy and hydrated radius), Sr2+ competed more fiercely with Ca2+ for adsorption sites. Hydrated Na+ and Sr2+ could enter and adsorb on the interlayer, but the difference is that the hydrated Na+ collapsed the interlayer of weathered biotite (from 15.0 Å to 11.8 Å), while the hydrated Sr2+ expanded the interlayers (from 12.0 Å to 14.8 Å). Nevertheless, the hydrated Sr2+ could occupy most interlayers when Na+ and Sr2+ co-existed in the solution. It was noted that dehydrated K+ present in the interlayer of weathered biotite could collapse the expanded interlayer of biotite. The d-spacing of weathered biotite (e.g., SCa-Bio) would decrease from 15.0 Å to 10.4 Å, significantly limiting the interlaminar adsorption of Sr2+. Furthermore, this inhibitory effect was based on the high weathering degree of micaceous minerals and the noticeable interlayer expansion. XPS results demonstrated that the co-existing cations hardly influence the adsorption form of Sr2+ on weathered micaceous minerals. The above findings provide intrinsic insights into the understanding of radioactive strontium transport and fate in the environment.

Competitive adsorption behavior of As(V) and Sb(V) on Hematite: Facet and pH dependent coordination affinity and role of outer-sphere complexes

The environmental mobility and fate of arsenic (As) and antimony (Sb) are influenced by ubiquitous iron minerals, but little is known about whether their co-adsorption behavior is affected by the exposed facets. Herein, we used cubic and rod-shaped hematite nanocrystals (HNC and HNR) to investigate the effect of exposed facets on competitive adsorption behaviors. TEM analysis indicated that the primary exposed facets of HNC and HNR were {110} and {012}, separately. Calculations supported the predictions of our model, revealing that the competition in acidic and alkaline environments was mainly influenced by the affinity and bond stability of facet-related adsorption configurations. However, the competition in neutral conditions was jointly influenced by facet-related coordination and adsorption behavior, due to the dependence of Sb(V) on protonation sites. On HNR (pH = 3), the adsorption of Sb(V) (50.6 %) was approximately twice that of As(V) (27.8 %) for its significant advantage in bidentate coordination on the {110} facet, whereas on HNC, As(V) (65.9 %) and Sb(V) (69.3 %) exhibited similar competitiveness. Notably, As(V) and Sb(V) tend to be adsorbed through outer-sphere coordination under alkaline conditions. On the {012} facet, As(V) and Sb(V) exhibited similar competitiveness for outer-sphere sites, whereas on the {110} facet, As(V) outer-sphere coordination showed stronger affinity, giving it an edge in competing on HNR. Overall, this study elucidated the critical role of varying exposed facets in the competitive adsorption process and proposed novel strategies for the selective removal of coexisting As(V) and Sb(V) through tailored fixed-facet iron oxides.

Lanthanum and cerium functionalised forestry waste biochar for phosphate removal: Mechanisms and real-world applications

Phosphorus as a diminishing finite resource, yet is an essential element for the growth of biota. However, elevated concentrations in water can imbalance ecosystems and cause eutrophication. To address both problems, two highly efficient biochars, namely La-OB and CeLa-OB were synthesised by lanthanum and cerium doping. The performance of La-OB and CeLa-OB were evaluated in both batch and dynamic regimes with synthetic phosphate (PO43--P) solutions and eutrophic lake water. PO43--P adsorption mechanisms were investigated in terms of pH, kinetics, isotherms, activation energy, thermodynamics and using in-depth characterisation (XPS, FTIR, XRD, BET, pHpzc and SEM-EDX). The feasibility of using such biochar in ‘real life’ situations was studied with column filtration of lake water with low and high PO43--P concentrations. Reusability/desorption and toxicity in the water environment was also considered. The mechanistic study showed that both biochars predominantly had inner-sphere complexes with La and Ce ligands (as a monolayer), while outer-sphere complexation was less common. The exothermic adsorption process followed the Elovich kinetic and Langmuir isotherm models, with a maximum adsorption capacity of 112 mg/g for La-OB and 40 mg/g for CeLa-OB. In column filtration trials the adsorption capacity reached 78 mg/g, while low metal leaching (0.08 mg/L) and low toxicity to Lepidium sativum germination were detected. The results indicated that these biochars, especially La-OB, could be used in circular economy-based water treatment.

Mechanistic study of highly effective phosphate removal from aqueous solutions over a new lanthanum carbonate fabricated carbon nanotube film

The effective purification of phosphate-containing wastewater is considered as increasingly important. In this study, a highly effective LC-CNT film was developed for efficient phosphate removal. Kinetic results showed that the adsorbent exhibited an improved mass transfer efficiency and a fast adsorption rate during adsorption (reaching 80% and 100% equilibrium adsorption capacity within 175 and 270 min, respectively). Kinetic model analysis suggested that the adsorption was a combined chemical physical process. Isotherm study revealed that the LC-CNT film showed a superior adsorption capacity (178.6 mg/g, estimated from the Langmuir model) with multiple adsorption mechanisms. pH study suggested that surface complexation and ligand exchange played important roles during adsorption, and the adsorbent worked well within the pH range of 3–7 with little La leakage. The ionic strength and competing anions showed little influence on the adsorbent effectiveness except for the carbonate and sulfate ions. The characterization and mechanism study revealed that the phosphate adsorption of the LC-CNT film was controlled by inner-sphere complexation, outer-sphere complexation and surface precipitation. The LC-CNT film also showed excellent regenerability and stability in cycling runs, further demonstrating its potential in industrial applications.

Insight into Adsorption Kinetics of Cs+, Rb+, Co2+, and Sr2+ on a Zeolites-Based Composite: Comprehensive Diffusional Explanation and Modelling

Kaolinite-rich soils were used to prepare zeolite-based composites via alkaline activation. The porous material was characterized by conducting XRD and microporosity measurements, as well as ESEM microscopy. The Weber and Morris (W-M) model was used for studying adsorption kinetics of radioactive cations on synthesized alkali-activated material. These investigations evidenced the effects of pore structure and the importance of the intrinsic characteristics of hydrated cations (ionic potential; hydrated radius; B-viscosity parameter; molar Gibbs energy of hydration of cation) on W-M kinetic rate constants. The application of diffusion-based models permitted us to assess the key diffusion parameters controlling successive diffusion regimes, and to reveal strong contributions of surface diffusion to adsorption kinetics during the course of the second and third kinetics stages of the W-M model. The magnitude of the surface diffusion coefficient was related to the capacity of hydrated cationic species to lose water molecules when penetrating brick pores. The HSDM model were tested for predicting radionuclide adsorption in a fixed-bed column. A breakthrough curve simulation indicated the predominance of the surface diffusion regime, which was in agreement with mathematical analysis of (batch) adsorption kinetics data. Ionic diffusion was linked to the characteristics of capillary porosity and connectivity of capillary pores in the composite, suggesting the generation of hydrated nuclides and their immobilization in the form of outer-sphere complexes.

Distinct photochemistry of adsorbed and coprecipitated dicarboxylates with ferrihydrite: Implications for iron reductive dissolution and carbon stabilization

Although ligand-promoted photodissolution of ferrihydrite (FH) has long been known for low molecular weight organic acids (LMWOAs), such as oxalate (Oxa) and malonate (Mal), photochemistry of coprecipitated FH with Oxa and Mal remains unknown, despite the importance of these mineral-organic associations in carbon retention has been acknowledged recently. In this study, ferrihydrite-LMWOAs associations (FLAs) were synthesized under circumneutral conditions. Photo-dissolution kinetics of FLAs were compared with those of adsorbed LMWOAs on FH surface and dissolved Fe-LMWOAs complexes through monitoring Fe(II) formation and organic carbon decay. For aqueous Fe(III)-LMWOAs complexes, Fe(II) yield was controlled by the initial concentration of LMWOAs and nature of photochemically generated carbon-centered radicals. Inner-sphere mononuclear bidentate (MB) configuration dominated while LMWOAs were adsorbed on the FH surface. MB complex of FH-Oxa was more photoreactive, leading to the rapid depletion of Oxa. Oxa can be readsorbed but in the form of binuclear bidentate and outer-sphere complexation, with much lower photoreactivity. While LMWOAs was coprecipitated with FH, the combination mode of LMWOAs with FH includes surface adsorption with a mononuclear bidentate structure and internal physical inclusion. Higher content of LMWOAs in the FLAs promoted the photo-production of Fe(II) as compared to pure FH, while it was not the case for FLAs containing moderate amounts of LMWOAs. The distinct photochemistry of adsorbed and coprecipitated Fe-LMWOAs complexes is attributed to ligand availability and configuration patterns of LMWOAs on the surface or entrapped in the interior structure. The present findings have significant implications for understanding the photochemical redox cycling of iron across the interface of Fe-organic mineral associates.

Surface properties of schwertmannite with different sulfate contents and its effect on Cr(VI) adsorption

Sulfate is a critical component of schwertmannite. However, the sulfate content of schwertmannite decreases with the increase in AMD-polluted river pH value, and its impact on the surface properties and Cr(VI) adsorption of schwertmannite remains unclear. To address this issue, different methods, including batch adsorption, N2 physisorption, scanning electron microscopy (SEM), potentiometric titration, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR) in combination with two-dimensional correlation spectroscopy (2D-COS) analysis, and surface complexation modeling (SCM) were employed. Our results showed that sulfate existed as both non-protonated bidentate-binuclear complexes and non-protonated outer-sphere complexes in schwertmannite. The surface morphology and particle size of schwertmannite were unaffected by the sulfate content. However, a decrease in sulfate content resulted in a drop in the negative charge on the surface of schwertmannite, which is conducive to particle aggregation. An increase in pH, on the other hand, raised the negative charge and encouraged the dispersion of the particles. And then, reducing the sulfate content of schwertmannite led to a decrease in acid-base buffer and Cr(VI) adsorption capacity of schwertmannite. The adsorption process of Cr(VI) by schwertmannite can be divided into two stages. In the first stage, Cr(VI) was adsorbed primarily through anion exchange reactions with the sulfate; however, the contribution of surface complexation gradually increased as the initial sulfate content decreased because of a reduced likelihood of anion exchange and an increase in the specific surface area of schwertmannite. Additionally, the behavior of sulfate and Cr(VI) in this stage could be predicted based on the initial sulfate content of schwertmannite. In the second stage, surface complexation with hydroxyl sites became the predominant mechanism of adsorption, which still exhibited great potential at higher Cr(VI) concentrations. Finally, the aforementioned hypothesis was used to establish a CD-MUSIC model, and the fitting results demonstrated that the density and Cr(VI) adsorption capacity of the sulfate site dropped as the sulfate content decreased, while the hydroxyl site was less impacted. The findings have provided insights into further understanding the properties of schwertmannite and its adsorption of Cr(VI).

Rare Earth Element Adsorption to Clay Minerals: Mechanistic Insights and Implications for Recovery from Secondary Sources.

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant.