M Zhang

Impact of Suspended Inorganic Particles on Phosphorus Cycling in the Yellow River (China)

Phosphorus (P) in water and sediment in the Yellow River was measured for 21 stations from the source to the Bohai Sea in 2006-2007. The average total particulate matter (TPM) increased from 40 mg/L (upper reaches) to 520 mg/L (middle reaches) and 950 mg/L in the lower reaches of the river. The average dissolved PO4 concentration (0.43 μmol/L) was significantly higher than that in 1980s but lower than the world average level despite high nutrient input to the system. Much of the P input was removed by adsorption, which was due to the high TPM rather than the surface activity of the particles since they had low labile Fe and low affinity for P. The sediment was a sink for P in the middle to lower reaches but not in the upper to middle reaches. TPM has been reduced by more than an order of magnitude due to artificial dams operating over recent decades. Modeling revealed that TPM of 0.2-1 g/L was a critical threshold for the Yellow River, below which most of the phosphate input cannot be removed by the particles and may cause eutrophication. These findings are important for river management and land-ocean modeling of global biogeochemical P cycling.

XAFS study of starch-stabilized magnetite nanoparticles and surface speciation of arsenate

It has been shown that starch can effectively stabilize nanoscale magnetite particles, and starch-stabilized magnetite nanoparticles (SMNP) are promising for in situ remediation of arsenic-contaminated soils. However, a molecular level understanding has been lacking. Here, we carried out XAFS studies to bridge this knowledge gap. Fe K-edge XAFS spectra indicated that the Fe-O and Fe-Fe coordination numbers of SMNP were lower than those for bare magnetite particles, and these coordination numbers decreased with increasing starch concentration. The decrease in the average coordination number at elevated stabilizer concentration was attributed to the increase in the surface-to-volume ratio. Arsenic K-edge XAFS spectra indicated that adsorbed arsenate on SMNP consisted primarily of binuclear bidentate (BB) complexes and monodentate mononuclear (MM) complexes. More BB complexes (energetically more favorable) were observed at higher starch concentrations, indicating that SMNP not only offered greater adsorption surface area, but also stronger adsorption affinity toward arsenate.

Coordination structure of adsorbed Zn(II) at Water-TiO2 interfaces

The local structure of aqueous metal ions on solid surfaces is central to understanding many chemical and biological processes in soil and aquatic environments. Here, the local coordination structure of hydrated Zn(II) at water-TiO(2) interfaces was identified by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectroscopy combined with density functional theory (DFT) calculations. A nonintegral coordination number of average ∼4.5 O atoms around a central Zn atom was obtained by EXAFS analysis. DFT calculations indicated that this coordination structure was consistent with the mixture of 4-coordinated bidentate binuclear (BB) and 5-coordinated bidentate mononuclear (BM) metastable equilibrium adsorption (MEA) states. The BB complex has 4-coordinated Zn, while the monodentate mononuclear (MM) complex has 6-coordinated Zn, and a 5-coordinated adsorbed Zn was found in the BM adsorption mode. DFT calculated energies showed that the lower-coordinated BB and BM modes were thermodynamically more favorable than the higher-coordinated MM MEA state. The experimentally observed XANES fingerprinting provided additional direct spectral evidence of 4- and 5-coordinated Zn-O modes. The overall spectral and computational evidence indicated that Zn(II) can occur in 4-, 5-, and 6-oxygen coordinated sites in different MEA states due to steric hindrance effects, and the coexistence of different MEA states formed the multiple coordination environments.

Studies on the reaction pathway of arsenate adsorption at water-TiO2 interfaces using density functional theory

Reaction pathway information of transition states and intermediate species is crucial for understanding the adsorption mechanism of pollutants at mineral-water interfaces. However, it has been difficult to obtain such information using existing experiments. Here, the activation barriers, transition states, intermediate species and surface complexes of arsenate adsorption on TiO(2) surfaces were studied using DFT-based reaction pathway calculations. The results indicated that the bidentate binuclear (BB) adsorption structure was formed through a monodentate mononuclear (MM) metastable-equilibrium adsorption (MEA) state. A two-step adsorption mechanism was proposed on the basis of the detailed picture of bond breaking and bond formation during each reaction step. When the adjacent surface sites were occupied, the transform from MM mode to BB mode was greatly inhibited so that both MM and BB coexisted in the equilibrium adsorption sample. The BB complex was energetically more stable than the MM complex, and so, the adsorption irreversibility was fundamentally related to the ratio BB:MM in the final equilibrium state. This mechanism may also explain the initial concentration effect, where, for the given adsorption experiment of arsenate on TiO(2) under the same thermodynamic conditions, both equilibrium constants and the BB:MM ratio in equilibrium adsorption samples changed with the reaction kinetics.

Enhanced Phosphorus Locking by Novel Lanthanum/Aluminum–Hydroxide Composite: Implications for Eutrophication Control

Lanthanum (La) bearing materials have been widely used to remove phosphorus (P) in water treatment. However, it remains a challenge to enhance phosphate (PO4) adsorption capacity and La usage efficiency. In this study, La was coprecipitated with aluminum (Al) to obtain a La/Al-hydroxide composite (LAH) for P adsorption. The maximum PO4 adsorption capacities of LAH (5.3% La) were 76.3 and 45.3 mg P g-1 at pH 4.0 and 8.5, which were 8.5 and 5.3 times higher than those of commercially available La-modified bentonite (Phoslock, 5.6% La), respectively. P K-edge X-ray absorption near edge structure analysis showed that PO4 was preferentially bonded with Al under weakly acid conditions (pH 4.0), while tended to associate with La under alkaline conditions (pH 8.5). La LIII-edge extended X-ray absorption fine structure analysis indicated that PO4 was bonded on La sites by forming inner sphere bidentate-binuclear complexes and oxygen defects exhibited on LAH surfaces, which could be active adsorption sites for PO4. The electrostatic interaction, ligand exchange, and oxygen defects on LAH surfaces jointly facilitated PO4 adsorption but with varied contribution under different pH conditions. The combined contribution of two-component of La and Al may be an important direction for the next generation of commercial products for eutrophication mitigation.

Assembling structures and dynamics properties of perfluorooctane sulfonate (PFOS) at water-titanium oxide interfaces.

The surface-associated structures and growth modes of perfluorooctane sulfonate (PFOS) at water-rutile TiO2 interfaces were defined by molecular dynamics (MD) simulations. The results showed that a compact PFOS layer was generated at the rutile surfaces, and the assembling structures and dynamic profiles were crystal-face-dependent. PFOS molecules were attached to the (110) and (001) surfaces mainly by the sulfonate headgroups. A well-defined monolayer was formed on the (110) surface with the perfluorinated alkyl chains nearly perpendicular to the substrate, whereas the C-F chains were inclined at an angle (30-75°) and formed a hemicylinder-like configuration on the (001) surface. On the other hand, the perfluorinated amphiphiles interacted with the (100) plane through both the sulfonate headgroups (relatively strong electrostatic attraction) and the C-F tailgroups (weak van der Waals forces) and yielded an irregular assembling pattern. Water molecules were mostly concentrated more than 17.0 Å away from the solid surfaces and formed a continuous solvent layer, suggesting the super hydrophobicity of perfluorinated alkyl chains. A counterion-bridging mechanism suggested in surfactant adsorption was observed at the molecular scale, where the sulfonate headgroups were linked together by the potassium ions at the surfaces and caused the formation of surface aggregates.

Combined DFT and IR evidence on metastable-equilibrium adsorption of arsenate on TiO2 surfaces

Adsorption of arsenate on TiO(2) surfaces under the same total mass and thermodynamic conditions reached to different final equilibrium states when the reaction was conducted through different pathways. The microscopic structure for equilibrium adsorption samples were significantly affected by the way arsenate was added to the TiO(2) suspension (e.g. 1-batch or multi-batch). The As-OTi asymmetric stretching vibration of 3-batch samples shifted to lower wavenumbers by 15 cm(-1) than that of 1-batch samples. Combined analysis of ATR-FTIR spectroscopy and DFT calculation indicated that the change of reaction pathway altered the ratio of double-corner complex to single-corner complex and, hence, the real equilibrium state that is a mixture of the two surface complexes.

Binding mechanism of arsenate on rutile (110) and (001) planes studied using grazing-incidence EXAFS measurement and DFT calculation.

Characterization of contaminant molecules on different exposed crystal planes is required to conclusively describe its behavior on mineral surfaces. Here, the structural properties and relative stability of arsenate adsorbed on rutile TiO2 (110) and (001) surfaces were investigated using grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) spectra and periodic density functional theory (DFT) calculation. The combined results indicated that arsenate mainly formed inner-sphere bidentate binuclear (BB) and monodentate mononuclear (MM) complexes on both surfaces, but the orientational polar angles of arsenate on the (110) surface were commonly smaller than that on the (001) surface for the two adsorption modes. The DFT calculation showed that the (110) plane had a higher affinity toward arsenate than the (001) plane, suggesting that, for a given adsorption mode (i.e., MM or BB structure), a small polar angle was more favorable for arsenate stabilized on the rutile surfaces.

Environmentally persistent free radicals mediated removal of Cr(VI) from highly saline water by corn straw biochars

Heavy metal ions coexisting with salts in the contaminant water are difficult to remove due to the interference of salts. Herein, biochars were pyrolyzed by corn straw at different temperatures, aiming to remove Cr(VI) in the presence of salts. Results show that biochars had surprisingly selective adsorption of Cr(VI). X-ray photoelectron and X-ray absorption near edge spectra revealed that Cr(VI) was reduced to Cr(III). All the adsorption was conducted at pH ∼ 7, which differed from the previous studies that Cr(VI) could only be reduced at pH 2-4. Environmental persistent free radicals (EPFRs) on biochars were found to play the role in reducing Cr(VI) in neutral solutions, which was confirmed by electron spin resonance and free radical quenching. The biochar with EPFRs reveals a highly selective removal of Cr(VI), which has implications for the remediation of contaminated water. This work provides a new insight into biochars properties and potential environmental applications.

Pyrolysis Treatment of Chromite Ore Processing Residue by Biomass: Cellulose Pyrolysis and Cr(VI) Reduction Behavior

The pyrolysis treatment with biomass is a promising technology for the remediation of chromite-ore-processing residue (COPR). However, the mechanism of this process is still unclear. In this study, the behavior of pyrolysis reduction of Cr(VI) by cellulose, the main component of biomass, was elucidated. The results showed that the volatile fraction (VF) of cellulose, ie. gas and tar, was responsible for Cr(VI) reduction. All organic compounds, as well as CO and H2 in VF, potentially reduced Cr(VI). X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine-structure (EXAFS) spectroscopy confirmed the reduction of Cr(VI) to Cr(III) and the formation of amorphous Cr2O3. The remnant Cr(VI) content in COPR can be reduced below the detection limit (2 mg/kg) by the reduction of COPR particle and extension of reaction time between VF and COPR. This study provided a deep insight on the co-pyrolysis of cellulose with Cr(VI) in COPR and an ideal approach by which to characterize and optimize the pyrolysis treatment for COPR by other organics.