Xionghan Feng

Cation effects on the layer structure of biogenic Mn-oxides.

Biologically catalyzed Mn(II) oxidation produces biogenic Mn-oxides (BioMnO(x)) and may serve as one of the major formation pathways for layered Mn-oxides in soils and sediments. The structure of Mn octahedral layers in layered Mn-oxides controls its metal sequestration properties, photochemistry, oxidizing ability, and topotactic transformation to tunneled structures. This study investigates the impacts of cations (H(+), Ni(II), Na(+), and Ca(2+)) during biotic Mn(II) oxidation on the structure of Mn octahedral layers of BioMnO(x) using solution chemistry and synchrotron X-ray techniques. Results demonstrate that Mn octahedral layer symmetry and composition are sensitive to previous cations during BioMnO(x) formation. Specifically, H(+) and Ni(II) enhance vacant site formation, whereas Na(+) and Ca(2+) favor formation of Mn(III) and its ordered distribution in Mn octahedral layers. This study emphasizes the importance of the abiotic reaction between Mn(II) and BioMnO(x) and dependence of the crystal structure of BioMnO(x) on solution chemistry.

Effect of ferrihydrite crystallite size on phosphate adsorption reactivity.

The influence of crystallite size on the adsorption reactivity of phosphate on 2-line to 6-line ferrihydrites was investigated by combining adsorption experiments, structure and surface analysis, and spectroscopic analysis. X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that the ferrihydrite samples possessed a similar fundamental structure with a crystallite size varying from 1.6 to 4.4 nm. N2 adsorption on freeze-dried samples revealed that the specific surface area (SSABET) decreased from 427 to 234 m(2) g(-1) with increasing crystallite size and micropore volume (Vmicro) from 0.137 to 0.079 cm(3) g(-1). Proton adsorption (QH) at pH 4.5 and 0.01 M KCl ranged from 0.73 to 0.55 mmol g(-1). Phosphate adsorption capacity at pH 4.5 and 0.01 M KCl for the ferrihydrites decreased from 1690 to 980 μmol g(-1) as crystallite size increased, while the adsorption density normalized to SSABET was similar. Phosphate adsorption on the ferrihydrites exhibited similar behavior with respect to both kinetics and the adsorption mechanism. The kinetics could be divided into three successive first-order stages: relatively fast adsorption, slow adsorption, and a very slow stage. With decreasing crystallite size, ferrihydrites exhibited increasing rate constants per mass for all stages. Analysis of OH(-) release and attenuated total reflectance infrared spectroscopy (ATR-IR) and differential pair distribution function (d-PDF) results indicated that initially phosphate preferentially bound to two Fe-OH2(1/2+) groups to form a binuclear bidentate surface complex without OH(-) release, with smaller size ferrihydrites exchanging more Fe-OH2(1/2+) per mass. Subsequently, phosphate exchanged with both Fe-OH2(1/2+) and Fe-OH(1/2-) with a constant amount of OH(-) released per phosphate adsorbed. Also in this stage binuclear bidentate surface complexes were formed with a P-Fe atomic pair distance of ~3.25 Å.

DETERMINATION OF THE POINT-OF-ZERO CHARGE OF MANGANESE OXIDES WITH DIFFERENT METHODS INCLUDING AN IMPROVED SALT TITRATION METHOD

Manganese (Mn) oxides are important components in soils and sediments. Points-of-zero charge (PZC) of three synthetic Mn oxides (birnessite, cryptomelane, and todorokite) were determined by using three classical techniques (potentiometric titration or PT, rapid PT or RPT, and salt titration or ST) and a modified salt titration method with a prolonged equilibration time (ST method with a prolonged equilibration time [PST]). The same methods have been applied to goethite, which was used as a reference material. The PZC values of goethite obtained by PT and RPT methods were both 7.95, and those by the ST and PST method were 8.16 and 8.30, respectively, for birnessite cryptomelane, and todorokite. The PT method yielded PZC of 1.18, 1.98, and 3.98, and the RPT method yielded 1.60, 2.11, and 3.47, respectively, for birnessite, cryptomelane, and todorokite. In contrast to goethite, there was no PZC found with the ST method, even when the types and concentrations of the added electrolytes changed. However, when after KCl addition the equilibration time was prolonged 28 h, the PZC of birnessite, cryptomelane, and todorokite could be found and were 0.97, 1.74, and 3.39, respectively. The fact that the normal ST method failed for the Mn oxides is due to their low PZC, because at this low pH value, the oxides may start to dissolve. Compared with PT and RPT methods, the PST method is reliable, simple, and convenient. The PST approach seems also suitable for other similar colloid systems.

Innovative chemically bonded ionic liquids-based sol-gel coatings as highly porous, stable and selective stationary phases for solid phase microextraction.

In this work, two allyl-functionalised ionic liquids (ILs), 1-allyl-3-methylimidazolium hexafluorophosphate and 1-allyl-3-methylimidazolium bis(trifluoromethanesulphonyl)imide, were used as selective coating materials to prepare chemically bonded ILs-based organic-inorganic hybrid solid phase microextraction fibres. These fibres were prepared with the aid of γ-methacryloxypropyltrimethoxysilane as bridge using sol-gel method and free radical cross-linking technology. The underlying mechanisms of the sol-gel reaction were proposed, and the successful binding of these functional ILs to the sol-gel substrate was confirmed by Fourier transform infrared spectroscopy. These IL-based sol-gel coatings had porous surface structure, high thermal stability, a wide range of pH stability, strong solvent resistance and good coating preparation reproducibility. They also had high selectivity and sensitivity towards strong polar phenolic environmental estrogens (PEEs) and aromatic amines due to the strong electrostatic interactions, hydrogen bonding and π-π interactions provided by the special molecular structure of these imidazolium ILs. Moreover, their characteristics were somewhat different depending on the type of anions in the IL structure. The practical applicability of these IL-based sol-gel coatings was evaluated through the analysis of PEEs in two real water samples. The detection limits were quite low, varying from 0.0030 to 0.1248 μgL(-1). The linearity was very good in the range of 0.1 to 1000 μgL(-1) for most analytes, and the relative standard deviation values were below 6%. The relative recoveries were between 83.1 and 104.1% for lake water and between 89.1 and 97.1% for sewage drainage outlet water.

RELATIONSHIP BETWEEN Pb2+ ADSORPTION AND AVERAGE Mn OXIDATION STATE IN SYNTHETIC BIRNESSITES

The relationship between vacant Mn structural sites in birnessites and heavy-metal adsorption is a current and important research topic. In this study, two series of birnessites with different average oxidation states (AOS) of Mn were synthesized. One birnessite series was prepared in acidic media (49.6–53.6 wt.% Mn) and theother in alkalinemedia (50.0–56.2 wt.% Mn). Correlations between the Pb2+ adsorption capacity and the d110 interlayer spacing, the AOS by titration, and the release of Mn2+, H+, and K+ during adsorption of Pb2+ were investigated. The maximum Pb2+ adsorption by the birnessites synthesized in acidic media ranged from 1320 to 2457 mmol/kg with AOS values that ranged from 3.67 to 3.92. For birnessites synthesized in alkaline media, the maximum Pb2+ adsorption ranged from 524 to 1814 mmol/kg, with AOS values between 3.49 and 3.89. Birnessite AOS values and Pb2+ adsorption increased as the Mn content decreased. The maximum Pb2+ adsorption to the synthetic birnessites calculated from a Langmuir fit of the Pb adsorption data was linearly related to AOS. Birnessite AOS was positively correlated to Pb2+ adsorption, but negatively correlated to the d110 spacing. Vacant Mn structural sites in birnessite increased with AOS and resulted in greater Pb2+ adsorption. Birnessite AOS values apparently reflect the quantity of vacant sites which largely account for Pb2+ adsorption. Therefore, the Pb2+ adsorption capacity of birnessite is mostly determined by the Mn site vacancies, from which Mn2+, H+, and K+ released during adsorption were derived.

Characterization of Co-doped birnessites and application for removal of lead and arsenite.

Nanostructured Co-doped birnessites were successfully synthesized, and their application for the removal of Pb(2+) and As(III) from aquatic systems was investigated. Powder X-ray diffraction, chemical analysis, nitrogen physical adsorption, field emission scanning electron microscopy (FE-SEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the crystal structure, chemical composition, micromorphologies and surface properties of the birnessites. Doping cobalt into the layer of birnessite had little effect on its crystal structure and micromorphology. Both chemical and XPS analyses showed that the manganese average oxidation state (Mn AOS) decreased after cobalt doping. The Co dopant existed mainly in the form of Co(III)OOH in the birnessite structure. Part of the doped Co(3+) substituted for Mn(4+), resulting in the gain of negative charge of the layer and an increase in the content of the hydroxyl group, which accounted for the improved Pb(2+) adsorption capacity. The maximum capacity of Pb(2+) adsorption on HB, CoB5, CoB10 and CoB20 was 2538 mmol kg(-1), 2798 mmol kg(-1), 2932 mmol kg(-1) and 3146 mmol kg(-1), respectively. The total As(III) removal from solution was 94.30% for CoB5 and 100% for both CoB10 and CoB20, compared to 92.03% for undoped HB, by oxidation, adsorption and fixation, simultaneously.

Thermally stable ionic liquid-based sol-gel coating for ultrasonic extraction-solid-phase microextraction-gas chromatography determination of phthalate esters in agricultural plastic films.

A novel sol-gel-coated ionic liquid-based ([AMIM][N(SO(2)CF(3))(2)]-OH-TSO) fiber was successfully applied for the determination of phthalate esters (PAEs) in agricultural plastic films by ultrasonic extraction (UE) combined with solid phase microextraction-gas chromatography (SPME-GC) due to its high thermal stability, specific selectivity and extraction efficiency. The extractant for UE and the adsorption time for SPME were optimized to achieve higher extraction efficiency. The desorption temperature and time were also optimized to avoid the carryover effect of previous extraction, and ultimately improve the precision and accuracy of the method. The [AMIM][N(SO(2)CF(3))(2)]-OH-TSO fiber showed comparable, or even higher response to most of the investigated PAEs than the commercial PDMS, PDMS-DVB and PA fibers. The carryover problem, often encountered when using commercial fibers, had been eliminated when desorption was performed at 360°C for 8 min. The proposed SPME-GC method showed good linearity over three to four orders of magnitude, and low limits of detection ranged from 0.003 to 0.063 μg L(-1). The relative standard deviation values obtained were below 10%, and the recoveries were in the ranges of 90.2-111.4%. Some of the PAEs studied were detected at very high concentration in these agricultural plastic film samples, resulting in a potential risk of crop damage, environmental contamination and human health exposure.

Mechanism of Myo-inositol Hexakisphosphate Sorption on Amorphous Aluminum Hydroxide: Spectroscopic Evidence for Rapid Surface Precipitation

Inositol hexakisphosphates are the most abundant organic phosphates (OPs) in most soils and sediments. Adsorption, desorption, and precipitation reactions at environmental interfaces govern the reactivity, speciation, mobility, and bioavailability of inositol hexakisphosphates in terrestrial and aquatic environments. However, surface complexation and precipitation reactions of inositol hexakisphosphates on soil minerals have not been well understood. Here we investigate the surface complexation-precipitation process and mechanism of myo-inositol hexakisphosphate (IHP, phytate) on amorphous aluminum hydroxide (AAH) using macroscopic sorption experiments and multiple spectroscopic tools. The AAH (16.01 μmol m(-2)) exhibits much higher sorption density than boehmite (0.73 μmol m(-2)) and α-Al2O3 (1.13 μmol m(-2)). Kinetics of IHP sorption and accompanying OH(-) release, as well as zeta potential measurements, indicate that IHP is initially adsorbed on AAH through inner-sphere complexation via ligand exchange, followed by AAH dissolution and ternary complex formation; last, the ternary complexes rapidly transform to surface precipitates and bulk phase analogous to aluminum phytate (Al-IHP). The pH level, reaction time, and initial IHP loading evidently affect the interaction of IHP on AAH. In situ ATR-FTIR and solid-state NMR spectra further demonstrate that IHP sorbs on AAH and transforms to surface precipitates analogous to Al-IHP, consistent with the results of XRD analysis. This study indicates that active metal oxides such as AAH strongly mediate the speciation and behavior of IHP via rapid surface complexation-precipitation reactions, thus controlling the mobility and bioavailability of inositol phosphates in the environment.

Solid-State NMR Spectroscopic Study of Phosphate Sorption Mechanisms on Aluminum (Hydr)oxides

Sorption reactions occurring at mineral/water interfaces are of fundamental importance in controlling the sequestration and bioavailability of nutrients and pollutants in aqueous environments. To advance the understanding of sorption reactions, development of new methodology is required. In this study, we applied novel (31)P solid-state nuclear magnetic resonance (NMR) spectroscopy to investigate the mechanism of phosphate sorption on aluminum hydroxides under different environmental conditions, including pH (4-10), concentration (0.1-10 mM), ionic strength (0.001-0.5 M), and reaction time (15 min-22 days). Under these conditions, the NMR results suggest formation of bidentate binuclear inner-sphere surface complexes was the dominant mechanism. However, it was found that surface wetting caused a small difference. A small amount (<3%) of monodentate mononuclear inner-sphere surface complexes was observed in addition to the majority of bidentate binuclear surface complexes on a wet paste sample prepared at pH 5, which was analyzed in situ by a double-resonance NMR technique, namely, (31)P{(27)Al} rotational echo adiabatic passage double resonance (REAPDOR). Additionally, we found that adsorbents can substantially impact phosphate sorption not only on the macroscopic sorption capacity but also on their (31)P NMR spectra. Very similar NMR peaks were observed for phosphate sorbed to gibbsite and bayerite, whereas the spectra for phosphate adsorbed to boehmite, corundum, and γ-alumina were significantly different. All of these measurements reveal that NMR spectroscopy is a useful analytical tool for studying phosphorus chemistry at environmental interfaces.

Redox Reactions between Mn(II) and Hexagonal Birnessite Change Its Layer Symmetry

Birnessite, a phyllomanganate and the most common type of Mn oxide, affects the fate and transport of numerous contaminants and nutrients in nature. Birnessite exhibits hexagonal (HexLayBir) or orthogonal (OrthLayBir) layer symmetry. The two types of birnessite contain contrasting content of layer vacancies and Mn(III), and accordingly have different sorption and oxidation abilities. OrthLayBir can transform to HexLayBir, but it is still vaguely understood if and how the reverse transformation occurs. Here, we show that HexLayBir (e.g., δ-MnO2 and acid birnessite) transforms to OrthLayBir after reaction with aqueous Mn(II) at low Mn(II)/Mn (in HexLayBir) molar ratios (5-24%) and pH ≥ 8. The transformation is promoted by higher pH values, as well as smaller particle size, and/or greater stacking disorder of HexLayBir. The transformation is ascribed to Mn(III) formation via the comproportionation reaction between Mn(II) adsorbed on vacant sites and the surrounding layer Mn(IV), and the subsequent migration of the Mn(III) into the vacancies with an ordered distribution in the birnessite layers. This study indicates that aqueous Mn(II) and pH are critical environmental factors controlling birnessite layer structure and reactivity in the environment.