Outer-sphere Surface Complexation Research Articles

Speciation studies at the Illite - solution interface: Part 2 – Co-sorption of uranyl and phosphate ions

Although it is well known that clays and phosphate ions (hereafter referred to as “P”) can contribute to the long term uptake of uranium (U) in a variety of geochemical systems, work is still needed to document the surface speciation of U(VI) and P sorbed on relevant clay minerals such as illite. Following on from previous work showing strong sorption of phosphate ligands on the surface of a homoionic Na-illite ([1]), we addressed the (competitive/synergistic) mechanisms of (co)sorption of trace levels of uranyl ions (1–10 µM) and phosphate ligands (100 µM) onto this clay, and the identity of the surface species formed, by in situ spectroscopy monitoring of the clay-solution interface along sorption. We also performed complementary batch sorption experiments and electrophoretic mobility (EM) measurements. Macroscopic data indicated a uranyl sorption dependent on pH, aqueous U concentration and clay-to-solution ratio, a signature of P on the U sorption, and a promotion of P sorption with U concentration. Macroscopic and EM data also suggested mostly reversible mechanisms of P and U co-sorption that confer negative charges on the mineral surface and involve several types of uranyl phosphate surface species and/or surface sites present on the clay edges. FTIR interface spectra confirmed that several types of inner sphere uranyl phosphate surface species formed at acidic pH at the illite-solution interface, as a function of U surface coverage and/or reaction time. An inner-sphere uranyl phosphate surface complex, likely with a U-bridging structure, was formed rapidly on high-affinity surface sites existing in limited quantities on the clay edges. Another U-P surface complex (with a possible P-bridging structure) was progressively formed in increasing amounts with U surface coverage and time on low affinity clay edge sites. Finally, a third U-P surface species having an autunite-like structure (probably a U-P polynuclear surface species) was formed on the illite surface at high U concentration (10 µM). The two later species competed with the existence on the illite surface of inner sphere surface complexes and outer-sphere surface complex of phosphate, which were identified in the absence of U. Information on uranyl surface speciation in the presence of phosphate ligands presented here is novel and provides for the first time in situ spectroscopic evidence of synergistic U-P sorption process leading in the formation of several types of uranyl phosphate sorption species on the surface of illite. These results provide a sound basis for better understanding / prediction of U sorption in the environment, including in clayey formations being considered as long term barriers to radionuclide migration in far field of high level radioactive waste repository.

Facile synthesis of flower shaped magnesium ferrite (MgFe2O4) impregnated mesoporous ordered silica foam and application for arsenic removal from water

Magnesium ferrite (MF0.33) impregnated flower-shaped mesoporous ordered silica foam (MOSF) was successfully synthesized in present study. MOSF was added with precursor solution of MF0.33 during MF0.33 synthesis which soaked the materials and further chemical changes occurred inside the pore. Therefore, no additional synthesis process was required for magnesium ferrite impregnated mesoporous ordered silica foam (MF0.33-MOSF) synthesis. MF0.33-MOSF showed higher morphological properties compared to other magnesium ferrite modified nanomaterials and adsorbed arsenic III [As(III)] and arsenic V [As(V)] 42.80 and 39.73 mg/g respectively. These were higher than those of other Fe-modified adsorbents at pH 7. As MOSF has no adsorption capacity, MF0.33 played key role to adsorb arsenic by MF0.33-MOSF. Data showed that MF0.33-MOSF contain about 2.5 times lower Fe and Mg than pure MF0.33 which was affected the arsenic adsorption capacity by MF0.33-MOSF. Adsorption results best fitted with Freundlich isotherm model. The possible mechanism of arsenic adsorption might be chemisorption by electrostatic attraction and inner or outer-sphere surface complex formation.

Speciation studies at the Illite - solution interface: Part 1 – Sorption of phosphate ions

Although phosphate ion (hereafter “P”) sorption is known to influence clay surface reactivity and trace metal behavior in the environment, there is still a lack of in situ spectroscopic evidence on the identity of phosphate sorption species formed at the interface between solution and clays with a 2:1 layered structure (2 silica tetrahedral: 1 octahedral layers), which are ubiquitous in soils and clay formations. We studied the surface speciation of phosphate ions by in situ spectroscopic monitoring along P sorption at the interface between a solution and a homoionic Na-illite, as a function of time or aqueous phosphate concentration (20–250 µM) leading to low/moderate P surface coverage. We also combined them with batch sorption experiments and electrophoretic mobility (EM) measurements. Macroscopic data indicated that the percentage of P sorption depends on pH, aqueous phosphate concentration, and the clay/solution ratio of the experiment, i.e., the coverage of the clay surface by P, with a maximal sorption capacity of the clay equal to ca. 6 µmol.g−1 at pH 4. Macroscopic and EM data further suggest that P sorption mechanisms onto illite confer negative charges on the surface and involve several sorption species and/or surface sites present on the clay edges. In situ FTIR spectra showed that, at acidic pH, three types of phosphate surface species exist at the illite-solution interface: an outer-sphere surface complex (OSSC) of phosphate (ΞSOH2+…H2PO4-, with S referring to a sorption site on the clay), an inner-sphere surface complex (ISSC) of phosphate, probably a monodentate binuclear surface complex ((ΞSO)2PO2) formed by surface ligand exchange with high-affinity aluminol sites and, to a lesser extent, low-affinity sites on the clay edges, and, in limited amounts, an Al-phosphate surface precipitate. Phosphate ion sorption occurs through the initial formation of the OSSC of phosphate, which dominates phosphate surface speciation at short reaction times and low P concentrations and transforms over time into the ISSC of phosphate. This study presents the first published in situ surface speciation of phosphate ions sorbed at the interface between a solution and an illite. The evidence of a strong sorption of phosphate ions at this clay surface provides new and sound knowledge to better understand the environmental fate of phosphate ions and trace metals, particularly in agricultural soil - groundwater continua or in clay host rocks considered for high-level radioactive waste disposal.

Distinct effects of Fe3+ on the adsorption of chromate and arsenate: A comparison of iron-bearing ferrihydrite and nano-TiO2 absorbents

Fe3+, a particularly prevalent ion in acid mine drainage (AMD), has a substantial impact on the crystallization of iron-bearing minerals and the immobilization of multiple co-existing oxyanions such as Cr(VI) and As(V). To investigate the varied effects of Fe3+ on Cr(VI) and As(V), ferrihydrite (Fh) and nano-TiO2 were selected due to their superior adsorption effectiveness and distinctive stability. As a result of the dissolution of Fe3+ in Fh and its subsequent promotion to As(V) adsorption, As(V) adsorption capacity on Fh (124.0 mg/g) was twice that of TiO2 (62.76 mg/g). The co-existence of Fe3+ in the As(V) adsorption system greatly enhanced As(V) sorption on TiO2 (18.9–56.5%) and Fh (1.03–15.7%), and an additional Fe-As complex was confirmed to contribute extra As(V) removal on both Fh and TiO2 by the FTIR and EXAFS spectra. On the other hand, TiO2 (18.15 mg/g) and Fh (19.50 mg/g) exhibited nearly identical Cr(VI) adsorption capabilities, and the co-presence of Fe3+ even slightly blocked Cr(VI) sorption on Fh. The spectroscopic and modeling results showed that the monodentate Cr(VI) adsorption complex was blocked by Fe3+, but the outer-sphere and bidentate inner-sphere Cr(VI) surface complexes were unaffected. Additionally, in the ternary As-Cr-Fe adsorbate systems, Cr(VI) had little effect on the development of As-Fe surface complexes or precipitates. With the interference mechanisms, actual AMD wastewater adsorption on Fh and TiO2 was well explained and predicted. The findings would offer fresh perspectives on the bioavailability and fate of hazardous metal compounds in the AMD-polluted locations.

Did Salts in Seawater Play an Important Role in the Adsorption of Molecules on Minerals in the Prebiotic Earth? The Case of the Adsorption of Thiocyanate onto Forsterite-91.

Thiocyanate may have played as important a role as cyanide in the synthesis of several molecules. However, its concentrationin the seas of the prebiotic Earth could have been very low. Thiocyanate was dissolved in two different seawaters: a) a composition that comes close to the seawater of the prebiotic Earth (seawater-B, Ca2+ and Cl-) and b) a seawater (seawater-A, Mg2+ and SO42-) that could be related to the seas of Mars and other moons in the solar system. In addition, forsterite-91 was a very common mineral on the prebiotic Earth and Mars. Two important results are reported in this work: 1) thiocyanate adsorbed onto forsterite-91 and 2) the amount of thiocyanate adsorbed, adsorption thermodynamic, and adsorption kinetic depend on the composition of the artificial seawater. For all experiments, the adsorption was thermodynamically favorable (ΔG < 0). The adsorption data fitted well in the Freundlich and Langmuir-Freundlich models. When dissolving thiocyanate in seawater 4.0-A-Gy and seawater 4.0-B-Gy, the adsorption of thiocyanate onto forsterite-91 was ruled by enthalpy and entropy, respectively. As shown by n values, the thiocyanate/foraterite-91 system is heterogeneous. For all kinetic data, the pseudo-first-order model presented the best fit. The constant rate for thiocyanate dissolved in seawater 4.0-A-Gy was twice that compared to thiocyanate dissolved in seawater 4.0-B-Gy or ultrapure-water. The interaction between thiocyanate and Fe2+ of forsterite-91 was with the nitrogen atom of thiocyanate. In the presence of thiocyanate, sulfate interacts with forsterite-91 as an inner-sphere surface complex, and without thiocyanate as an outer-sphere surface complex.

Investigating the influence of bentonite colloids on strontium sorption in granite under various hydrogeochemical conditions

The disposal of high-level radioactive waste in deep geological repositories is a critical environmental issue. The presence of bentonite colloids generated in the engineering barrier can significantly impact the transport of radionuclides, but their effect on radionuclide sorption in granite remains poorly understood. This study aimed to investigate the sorption characteristics of strontium (Sr) on granite as well as on the coexistence system of granite and colloids under various hydrogeochemical conditions, through batch experiments. Fourier transform infrared spectroscopy was employed to analyze the sorption forms of Sr on granite before and after sorption. Several hydrogeochemical factors were examined, including contact time, pH, ionic strength, coexisting ions, and bentonite and humic acid colloid concentration. Among these factors, the concentration of bentonite colloids exhibited a significant effect on Sr sorption. Within a specific range of colloid concentration, the sorption of Sr on the solid system increased linearly with the bentonite colloid concentration. pH and ionic strength were also found to play crucial roles in the sorption process. At low pH, Sr sorption primarily occurred through the outer sphere's surface complexation and Na+/H+ ion exchange. However, at high pH, inner sphere surface complexation dominated the process. As the ionic strength increased, electrostatic repulsion gradually increased, resulting in fewer binding sites for particle aggregation and Sr sorption on bentonite colloids. The results also indicate that with increasing pH, the predominant forms of Sr in the solution transitioned from SrHCO3+ and SrCl+ to SrCO3 and SrCl+. This was mainly due to the ion exchange of Ca2+/Mg2+ in plagioclase and biotite, forming SrCO3 precipitation. These findings provide valuable insights into the transport behavior of radionuclides in the subsurface environment of the repository and highlight the importance of considering bentonite colloids and other hydrogeochemical factors when assessing the environmental impact of high-level radioactive waste disposal.

In situ/operando XAFS investigation of the sorption/precipitation of Zn(II) on palygorskite surface at the molecular scale: Implications for Zn stable isotope fractionation

In aqueous geological environments, the fate and transport of Zn are controlled by geochemical reactions (e.g., sorption) occurring at the mineral/water interface. However, many of the underlying Zn fixation mechanisms, especially the kinetics of surface-induced precipitation, are still unclear. Additionally, Zn stable isotope fractionation during sorption has recently been shown to be an important process, but the relationship between Zn isotope fractionation and sorption mechanisms (e.g., surface complexation, precipitation) is also not well understood. To address these issues, we employed X-ray absorption fine structure (XAFS) spectroscopy, high-resolution transmission electron microscopy (HRTEM), and in situ/operando quick-scanning XAS (QXAS) spectroscopy to elucidate the sorption/precipitation mechanisms of Zn at palygorskite/solution interfaces. We also measured Zn isotope ratios during some sorption experiments to illustrate how Zn isotope fractionation behavior is affected by the evolution of coordination environments at different pH values, initial concentrations, and reaction times. Our results demonstrate that Zn sorption mechanisms vary as a function of pH, ionic strength, initial concentration, and reaction time. At low pH (pH < 7.0) and low ionic strength (I ≤ 0.01 M), Zn(II) predominantly forms an outer-sphere surface complex in octahedral coordination. At low pH (pH < 7.0) and high ionic strength (I = 0.1 M), Zn(II) is predominantly sorbed as an inner-sphere octahedral surface complex with insignificant isotopic fractionation (Δ66Znsorbed-aqueous = −0.02 ± 0.05‰). At high pH and high initial Zn concentration (pH 7.5, C0 ≥ 0.2 mM), the formation of octahedral Zn phyllosilicate precipitates is observed, yielding a small fractionation with an average Δ66Znsorbed-aqueous of 0.10 ± 0.07‰. In addition, in situ/operando QXAS of Zn sorption at pH 7.5 in a flow cell revealed that the predominant sorbed Zn species shifted from inner-sphere tetrahedral complexes during the initial stage (e.g., within minutes) to inner-sphere octahedral complexes during later stages (e.g., within hours), followed by the formation of Zn-phyllosilicate precipitates (e.g., within days). This molecular evidence coincides with the evolution of Zn isotope fractionation from a large Δ66Znsorbed-aqueous value (0.53 ± 0.05‰) to a small value of 0.05 ± 0.04‰ during the sorption process. The combination of QXAS and isotope fractionation results reveals a change in the Zn local environment from tetrahedral coordination to octahedral coordination. The findings in this study not only provide new insight into surface adsorption/precipitation mechanisms but also demonstrate that stable isotope fractionation is linked with the local molecular/bonding environments at mineral–water interfaces.

Fast Removal of Tetracycline from Aqueous Solution by Aluminosilicate Zeolite Nanoparticles with High Adsorption Capacity

Aluminosilicate zeolite nanoparticles were synthesized in a water-in-oil solvent and applied as an adsorbent for tetracycline (TC) removal from aqueous solutions. The large specific surface area at 495.8 m2 g–1 confirms that the zeolite nanoparticles have mesopores. The zeolite nanoparticles show an excellent removal efficiency for TC, achieving over 97% in the pH range of 4.70–7.17. A fast adsorption kinetics was observed, reaching equilibrium in only 20 min following a pseudo-second-order kinetic model. The adsorption isotherm was found to follow the Langmuir model, with a maximum adsorption capacity of TC of 454.55 mg g–1 at pH 6.7 with no salt added. After 6 cycles of reuse, the removal efficiency of TC remained high at 90.3%. It was understood that the adsorption process is spontaneous and exothermic, with an activation energy of 37.94 kJ mol–1. The high observed adsorption affinity is attributed to hydrogen bonding between TC and the hydroxyl groups on the zeolite nanoparticles and the formation of outer-sphere surface complexes. This study shows a new way to synthesize aluminosilicate zeolite nanoparticles that are an efficient and recyclable adsorbent for effective removal of TC from contaminated water.

Arsenic adsorption by carboxylate and amino modified polystyrene micro- and nanoplastics: kinetics and mechanisms.

We investigated adsorption characteristics of As(III) and As(V) onto two different functionalized polystyrene (PS) microplastics (MPs). Our results show that there is the potential for PS MPs to adsorb both As(III) and As(V). Using a particle size of 80-82 nm, maximum As(III) and As(V) adsorption capacities of 0.57 mg/g and 0.37 mg/g were obtained by PS-COOH MPs. These capacities were markedly higher than those for PS-NH2 MPs, which were 0.41 mg/g and 0.27 mg/g, respectively. The pseudo-second-order adsorption kinetic model was found to effectively describe the sorption kinetics of As(III)/As(V) on two different functionalized PS MPs. Langmuir isotherms better represented the equilibrium adsorption results. The kinetic models, XPS, and FTIR results indicate that hydrogen bonding, hydroxyl complexation, and outer-sphere surface complexation may have partly contributed to adsorption of As onto PS MPs. Adsorption capacity markedly decreases with increasing salinity or presence of humic acids (HA), suggesting an inhibiting effect of salinity and HA through outer-sphere complexation. These findings confirm that microplastics have great potential to adsorb As and hence are ultimately highly likely to affect the environmental behavior of As in an ecosystem.

Electrified nanohybrid filter for enhanced phosphorus removal from water.

Phosphorus (P) has been identified as a major cause of eutrophication. One feasible way to deal with P-containing wastewater is to employ advanced adsorbents with high P affinity. Towards this end, the loading of these sorbents onto a conductive scaffold would facilitate the introduction of an electric field into the reaction system thereby permitting a continuous-flow operation and improved P sorption kinetics. Here, the preparation and evaluation of an electroactive carbon nanotube (CNT) filter functionalized with cerium-based metal organic frameworks (Ce-MOF) is reported. Various advanced characterization techniques confirmed the successful fabrication of the Ce-MOF/CNT nanohybrid filter. The results suggested that the nanohybrid filter had a maximum P adsorption capacity of 22.41mgg-1, which compared favorably with other state-of-the-art P sorbents. Ce-MOF loading, applied voltage and flow rate each increased the rate constants for phosphate removal by factors of 1.6, 2.1 and 5.8 times relative to the absent states. The underlying P sorption mechanisms involved outer-sphere surface complexation (electrostatic attraction), inner-sphere surface complexation (Ce-O-P) and diffusion. The performance was tolerant of a wide operational pH range and different water matrices. The Ce-MOF/CNT electrochemical filter described in this study provides a viable strategy to address the challenging issues associated with aqueous P pollution.

Comprehensive evaluation of cobalt incorporated cryptomelane-type manganese oxide molecular sieve as an efficient adsorbent for enhanced removal of europium from wastewater systems

Extraction of radionuclide contaminants from wastewater systems has recently drawn widespread attention, and then developing a novel and green extracting technology has also become an enormous challenge. Herein, a facile hydrothermal method was employed to fabricate cobalt-incorporated cryptomelane-type manganese oxide molecular sieve (Co-OMS-2) for extraction Eu(III) from wastewater under diverse experimental conditions. All kinds of characterized techniques, such as SEM, TEM, XRD, FTIR, BET, EDS and XPS had verified the qualified synthesis process and splendid structural features of the Co-OMS-2. The maximum adsorption capacity of Co-OMS-2 was 7.62 × 10−4 mol/g for Eu(III) at 298 K, which was superior than primarily traditional materials reported previous literatures. The high adsorption capacity of Eu(III) onto Co-OMS-2 was primarily attributed to high specific surface area and abundant surface functional groups, and the interactions were mainly contributed to strong surface complexation and electrostatic attraction. Under the condition of low pH, the outer-sphere surface complexation and cation exchange were primary mechanisms to Eu(III) adsorption onto Co-OMS-2 composites, while inner-sphere surface complexation was mainly assigned to Eu(III) adsorption onto Co-OMS-2 under the high pH sections. The Co-OMS-2 composite achieved equilibrium in a relatively short time, and this excellent performance was conducive to the treatment of Eu(III) under the extreme emergency conditions. In view of the extraordinary adsorption capacity and recycled reusability, the Co-OMS-2 composites can be as prospective adsorbents adopted for the extraction of Eu(III) in real wastewater management.

Prediction and optimization of removal performance for europium onto phosphate decorated zirconium-based metal–organic framework nanocomposites: Structure-activity relationship and mechanism evaluation

• Oriented functionalization of UiO-66-PO 4 was successfully prepared. • The maximal adsorption capacity of Eu(III) by UiO-66-PO 4 was 3.86 × 10 -4 mol·g −1 . • UiO-66-PO 4 revealed excellent stability in the removal of radionuclides. • The surface complexation and electrostatic interaction were primary mechanisms. • Long-term evaluation of Eu(III) performances in aqueous medium were needed. Herein, phosphorylation modified zirconium-based metal–organic frameworks composites (UiO-66-PO 4 ) were synthesized by facile and green approach, which was employed to remove Eu(III) from water solution under various experimental conditions. The macroscopic experiments showed that the removal performance of Eu(III) onto the UiO-66-PO 4 composites was endothermic and spontaneous with the tremendous phosphate groups acting as critical binding sites. The SEM, XRD and FTIR provided beneficial evidence for propitious phosphate group grafted onto UiO-66 surfaces. The removal performance of Eu(III) onto UiO-66-PO 4 composites followed the pseudo-second-order model and the adsorption isotherms were well simulated by Langmuir model. The maximum adsorption capacity of UiO-66-PO 4 composites toward Eu(III) was calculated to 3.86 × 10 -4 mol·g −1 using Langmuir model. The UiO-66-PO 4 hybrids having excellently stable could be easily regenerated with no observed significant reduction in the elimination of Eu(III) even after five consecutive cycles. Furthermore, the XPS spectra results further revealed that those including zirconium, phosphate and oxygen functional groups played significantly role in the restricting of europium onto UiO-66-PO 4 surfaces. The experimental results further illustrated that the interactive mechanisms of Eu(III) onto UiO-66-PO 4 hybrids were primarily attributed to the outer-sphere surface complexation at low pH values and then inner sphere surface complexation at high pH values. Based on the discussed results, the UiO-66-PO 4 composites can be as promising candidates with favorably recycled reutilization for the elimination of europium from wastewater systems.

Understanding Cd2+ Adsorption Mechanism on Montmorillonite Surfaces by Combining DFT and MD

The adsorption mechanism of Cd2+ on different cleavage planes of montmorillonite was investigated using density functional theory (DFT) calculations and molecular dynamics (MD) simulations. The most stable adsorption energies of Cd2+ on the (001) and (010) surfaces were −88.74 kJ/mol and −283.55 kJ/mol, respectively. On the (001) surface, Cd2+ was adsorbed on the centre of the silicon–oxygen ring by electrostatic interactions, whereas on the (010) surface, Cd2+ was adsorbed between two ≡Al–OH groups and formed two covalent bonds with O, which was mainly due to the interaction between the Cd s and O p orbitals. Upon the partial substitution of Na+ by Cd2+, Cd2+ was adsorbed on the (001) surface as inner-sphere surface complexes, with a hydration number of 5.01 and a diffusion coefficient of 0 m2/s. Whereas, when Cd2+ completely replaced Na+, part of the Cd2+ moved from the inner-sphere surface complexes to the outer-sphere surface complexes owing to its competitive adsorption. In this case, its hydration number became 6.05, and the diffusion coefficient increased to 1.83 × 10−10 m2/s. This study provides the theoretical background necessary for the development of montmorillonite-based adsorbents.

Comparing the influence of humic/fulvic acid and tannic acid on Cr(VI) adsorption onto polystyrene microplastics: Evidence for the formation of Cr(OH)3 colloids

Microplastics (MPs) can act as vectors for various contaminants in the aquatic environment. Although some research has investigated the adsorption characteristics and influencing factors of metals/organic molecules on MPs, the effects of dissolved organic matter (DOM) (which are ubiquitous active species in ecosystems) on metal oxyanions such as Cr(VI) capture by MPs are largely unknown. This study explored the adsorption behaviors and mechanisms of Cr(VI) oxyanions onto polystyrene (PS) MPs using batch adsorption experiments and multiple spectroscopic methods. The effects of representative DOM components (i.e., humic acid (HA), fulvic acid (FA) and tannic acid (TA)) on Cr(VI) capture by PS were particularly studied. Results revealed a significantly enhanced adsorption of Cr(VI) on PS in the presence of TA. The Cr(VI) adsorption capacity was increased from 2876 μg g−1 to 4259 μg g−1 and 5135 μg g−1 when the TA concentrations raised from 0 to 10 and 20 mg L−1, respectively. Combined microscopic and spectroscopic investigations revealed that Cr(VI) was reduced to Cr(III) by TA and formed stable Cr(OH)3 colloids on PS surfaces. Contrarily, HA and FA inhibited Cr(VI) adsorption onto PS, especially at pH > 2.0 and higher DOM concentrations, due to site competition and electrostatic repulsion. Increase in pH was found to reduce zeta potentials of MPs, resulting in inhibited Cr(VI) adsorption. The adsorbed Cr(VI) declined with increasing ionic strength, implying that outer-sphere surface complexation affected the adsorption process in the presence of DOM. These new findings improved our fundamental understanding of the fate of Cr(VI) and MPs in DOM-rich environmental matrices.

Solution NMR investigation of phytic acid adsorption mechanisms at the calcite-water interface

As one of the most abundant organic phosphorus (P) species in soils, phytic acid could serve as a mineralizable P reservoir in soils and sediments. It has been widely acknowledged that the adsorption of phytic acid to soil minerals retards P mineralization in soils. However, the adsorption mechanisms of phytic acid in the minerals are not clearly understood. Using solution 31P NMR and 1H-31P 2D NMR, the adsorption mechanism of phytic acid was investigated at the calcite-water interface at pH 6 and 8. Maximum phytic acid adsorption reached 3.07 mmol/g, 2.60 mmol/g, 2.39 mmol/g at pH 6, 8, and 9.5, respectively. The presence of outer-sphere surface complex was evident by a lack of significant change in zeta-potential of phytic acid reacted calcite. Solution NMR analysis showed a fast exchange process between adsorbed and unreacted phytic acid at the mineral surface on an NMR time scale, also indicating the outer-sphere complexation mechanism at both pH values. Interestingly, a more active role of P5 and P4,6 in binding with calcite surface was observed at pH 6. Adsorbed phytic acid on the calcite surface should be labile and is not limiting P mineralization in the terrestrial environment.

Distinguished Ni(II) Capture with Rapid and Superior Capability Using Biochar: Behavior and Mechanism

Batch experiments were used to study the interaction mechanism of Ni(II) with biochar as a function of solution pH, contact time, initial concentrations, reaction temperature, and the addition of humic compounds. The results indicate that Ni(II) can be interacted with biochar by a compound mechanism under different environmental conditions. It is suggested that outer-sphere surface complexes at low pH are transformed into inner-sphere surface complexes and surface precipitates are formed at pH 8.89 or 10.18. The combined macroscopic and microscopic insights provide additional details regarding the mobility, fate, and risk of Ni(II) in a practical aquatic environment, as well as the natural purification of metals in ecological environments.

Zn stable isotope fractionation during adsorption onto todorokite: A molecular perspective from X-ray absorption spectroscopy and density functional theory

Mineral-solution interface reactions control the mobility and fate of trace metals (e.g., Zn) and may drive their associated isotopic fractionation in the natural environment, but understanding the coupling between interfacial reactions and isotopic behavior requires a molecular-level understanding of these processes. In this study, we investigate Zn stable isotope fractionation during adsorption to todorokite as a function of reaction time, pH and Zn concentrations. We show that Zn stable isotope fractionation reaches equilibrium at ∼12 h reaction time at pH 6 and Zn concentrations of 0.05 mM. For Zn concentrations of 0.05 and 0.2 mM, Zn isotopic fractionation between adsorbed and aqueous Zn (Δ66Znadsorbed-aqueous) is approximately −0.1 ± 0.04‰ at pH 3–5, and Δ66Znadsorbed-aqueous gradually increases from −0.1 ± 0.04‰ to 0.05 ± 0.05‰ at higher pH 6–8. Extended X-ray absorption fine structure (EXAFS) spectroscopy shows that Zn adsorbs to the todorokite surface as an outer-sphere octahedral complex with an average ZnO interatomic distance of 2.06 Å at pH 3. In contrast, Zn is predominantly present as a tetrahedral coordinated structure with a shorter average ZnO interatomic distance of ∼2.00–2.05 Å at pH 6 and 8, suggesting the presence of a mixture of octahedral outer-sphere and tetrahedral inner-sphere surface complexes. Density functional theory calculations suggest that outer-sphere surface complexes exist in the center of the structural tunnels of todorokite, yielding a theoretical Zn isotopic fractionation (Δ66Znadsorbed-aqueous) of −0.2‰ to −0.3‰, whereas the tetrahedral inner-sphere surface complex results in a large Δ66Znadsorbed-aqueous of +0.5‰ to +0.8‰. Combined laboratory experiments and theoretical calculations demonstrate that different magnitudes of Zn isotopic fractionation are controlled by structural changes (e.g., coordination and bond distance) in the Zn surface complexes formed on todorokite relative to its aqueous form (i.e., aqua Zn(H2O)62+). These results provide important new constraints for understanding Zn isotope signatures in natural Mn-rich sediments and lead to a more complete understanding of Zn isotopes in the ocean.

Adsorptive behavior of thallium using Fe3O4-kaolin composite synthesized by a room temperature ferrite process

Thallium (Tl) contaminants pose serious threats to the ecological environment and human health due to its acute/chronic poisoning on the health of most organisms even at low concentrations. To find a rapid and efficient technology in removing Tl from waters thus becomes a crucial issue. A magnetic Fe3O4-kaolin composite (denoted by FKC) with high specific surface area (133.7 m2/g) was successfully synthesized via a simple and low-cost technique for Tl(I) removing from various water media. The HRTEM images confirmed the existence of lattice fingers Fe3O4 and displayed that a large number of Fe3O4 nanoparticles dispersed on the surface of kaolin sheets. Compared with kaolin or Fe3O4 alone, FKC enhanced obviously the adsorption rate and capacity of Tl(I) over a wide pH range (4.5–9.0). The maximum adsorption capacity of FKC for Tl(I) was 19,347 mg/kg (calculated by Langmuir model), which was almost one hundred times and two times higher than those of kaolin and Fe3O4, respectively. Importantly, FKC was observed to have a great potential in removing Tl(I) from surface water, groundwater, and tap water in more alkaline conditions. By applying the external magnetic field, FKC could be recovered efficiently (99%) and rapidly (20 s). Moreover, Tl L3-edge XANES spectra revealed that Tl(I) was adsorbed on the FKC and would not be converted to more toxic Tl(III). The cations (CaCl2, NaCl, and KCl) and the ionic strength with concentrations of 0.001–1.0 mol/L showed a great influence on the adsorption of Tl(I) by FKC, implying that this adsorption was dominated by outer-sphere surface complexation at investigated pH values. The information provided is essential for designing a rapid and effective scavenger for removing Tl in various natural waters.

Facile synthesis of hydrochar-supported catalysts from glucose and its catalytic activity towards the production of functional amines

Since the utilization of abundant biomass to develop advanced materials has become an utmost priority in recent years, we developed two sustainable routes (i.e., the impregnation method and the one-pot synthesis) to prepare the hydrochar-supported catalysts and tested its catalytic performance on the reductive amination. Several techniques, such as TEM, XRD and XPS, were adopted to characterize the structural and catalytic features of samples. Results indicated that the impregnation method favors the formation of outer-sphere surface complexes with porous structure as well as well-distributed metallic nanoparticles, while the one-pot synthesis tends to form the inner-sphere surface complexes with relatively smooth appearance and amorphous metals. This difference explains the better activity of catalysts prepared by the impregnation method which can selectively convert benzaldehyde to benzylamine with an excellent yield of 93.7% under the optimal reaction conditions; in contrast, the catalyst prepared by the one-pot synthesis only exhibits a low selectivity near to zero. Furthermore, the gram-scale test catalyzed by the same catalysts exhibits a similar yield of benzylamine in comparison to its smaller scale, which is comparable to the previously reported heterogeneous noble-based catalysts. More surprisingly, the prepared catalysts can be expediently recycled by a magnetic bar and remain the satisfying catalytic activity after reusing up to five times. In conclusion, these developed catalysts enable the synthesis of functional amines with excellent selectivity and carbon balance, proving cost-effective and sustainable access to the wide application of reductive amination.

Efficient Sorption of Arsenic on Nanostructured Fe-Cu Binary Oxides: Influence of Structure and Crystallinity.

To study the structure-performance relationship, a series of nanostructured Fe-Cu binary oxides (FCBOs) were prepared by varying synthesis conditions. The obtained binary oxides were well characterized using X-ray diffraction (XRD), transmission electron microscope (TEM), Brunner-Emmet-Teller (BET), magnetic and Zeta potential measurement techniques. Both As(V) and As(III) sorption on the FCBOs were evaluated by batch tests. Results show that the surface structure and crystallinity of FCBOs are greatly dependent on preparation conditions. The crystallinity of FCBOs gradually increases as the synthesis pH value increasing from 9.0 to 13.0, from amorphous phase to well-crystalline one. Simultaneously, the morphology change of FCBOs from irregular agglomerate to relatively uniform polyhedron has been observed. The sorption of arsenic is greatly influenced by the crystallinity and structure of FCBOs, decreasing with increasing degree of crystallinity. The amorphous FCBO has higher surface hydroxyl density than well-crystalline one, which might be the reason of higher sorption performance. As(V) is sorbed by the FCBOs via formation of inner-sphere surface complexes and As(III) is sorbed through formation of both inner- and outer-sphere surface complexes. This investigation provides new insights into structure-performance relationship of the FCBO system, which are beneficial to develop new and efficient sorbents.