Role of interfacial electron transfer reactions on sulfamethoxazole degradation by reduced nontronite activating H2O2.

It has been documented that organic contaminants can be degraded by hydroxyl radicals (•OH) produced by the activation of H2O2 by Fe(II)-bearing clay. However, the interfacial electron transfer reactions between structural Fe(II) and H2O2 for •OH generation and its effects on contaminant remediation are unclear. In this study, we first investigated the relation between •OH generation sites and sulfamethoxazole (SMX) degradation by activating H2O2 using nontronite with different reduction extents. SMX (5.2-16.9 µmol/L) degradation first increased and then decreased with an increase in the reduction extent of nontronite from 22% to 62%, while the •OH production increased continually. Passivization treatment of edge sites and structural variation results revealed that interfacial electron transfer reactions between Fe(II) and H2O2 occur at both the edge and basal plane. The enhancement on basal plane interfacial electron transfer reactions in a high reduction extent rNAu-2 leads to the enhancement on utilization efficiencies of structural Fe(II) and H2O2 for •OH generation. However, the •OH produced at the basal planes is less efficient in oxidizing SMX than that of at edge sites. Oxidation of SMX could be sustainable in the H2O2/rNAu-2 system through chemically reduction. The results of this study show the importance role of •OH generation sites on antibiotic degradation and provide guidance and potential strategies for antibiotic degradation by Fe(II)-bearing clay minerals in H2O2-based treatments.

Characterization of Coprecipitates of As(III) and Fe(II) in the Presence of Phyllosilicate Nanoparticles.

Phyllosilicate nanoparticles play an important role in regulating the biogeochemical processes of Fe(II) and As(III) in paddy soils due to their high mobility and activity. In the present work, two prepared muscovite nanoparticles with different sizes (LNPs and SNPs) were used to investigate the effect of the size of phyllosilicate nanoparticles on the coprecipitation of Fe(II) and As(III) during oxidation process. The results showed that muscovite nanoparticles could significantly promote the removal of Fe(II) and As(III) during coprecipitation process. The formation of crystalline iron oxide and oxidation of As(III) tended to be suppressed by the two muscovite nanoparticles, and the suppression increased as muscovite nanoparticle size decrease. The findings of this study provide a contribution to understanding the roles of the natural phyllosilicate nanoparticles in regulating the biogeochemical processes of Fe and As elements in polluted paddy soils.

Decolorization of RhB dye by manganese oxides: effect of crystal type and solution pH.

BACKGROUND: Organic dye pollution in water has become a major source of environmental pollution. Mn(III/IV) oxides have attracted a great deal of attention to remove organic dye pollutants due to their unique structures and physicochemical properties. Numerous studies have reported the removal of dye by various Mn(III/IV) oxides through catalytic degradation and adsorption. The crystalline structures of manganese oxides and solution pH may exert substantial impact on the removal of dyes. However, few studies have focused on the oxidative degradation of RhB dye using Mn(III/IV) oxides with different crystal structures during a spontaneous reaction. In the present study, three manganese oxides with different crystal type (α-MnO2, ß-MnO2, and δ-MnO2) were prepared by refluxing process to decolorize RhB dye in various pH solutions. RESULTS: The results showed that the decolorization efficiencies of RhB for the three manganese oxides all increase with decrease solution pH. α-MnO2 exhibited highest activity and could efficiently degrade RhB at pH 2-6. The degradation of RhB by ß-MnO2 and δ-MnO2 could be observed at pH 2-3, and only little adsorption RhB on manganese oxides could be found at pH 4-6. The UPLC/MS analysis suggests that the decolorization of RhB by manganese oxides consists of three main stages: (1) cleavage of the ethyl groups from RhB molecular to form Rh; (2) further destruction of -COOH and -CNH2 from Rh to form the small molecular substances; (3) mineralization of the small molecular substances into CO2, H2O, NO3 (-) and NH4 (+). CONCLUSIONS: Overall, these results indicate that α-MnO2 may be envisaged as efficient oxidants for the treatment of organic dye-containing wastewater under acid conditions.

Fabrication and evaluation of Au-Pd core-shell nanocomposites for dechlorination of diclofenac in water.

Nanocomposites with core-shell structure usually exhibit excellent catalytic properties due to unique interfaces and synergistic effect among composites. In this study, Au-Pd bimetallic nanoparticles (NPs) with core-shell structure (Au-Pd cs) by using Au NPs as core and Pd as shell were successfully fabricated and, for the first time, were used to investigate the dechlorination of diclofenac (DCF) at H2 atmosphere in water at room temperature. The degradation products were studied as well by using HPLC/Q-ToF MS/MS. The operational factors such as pH and composition of the Au-Pd cs were also studied. The results showed that nearly 100% of DCF (30 mg L(-1), 50 mL, pH=7) was dechlorinated in 4.5 h by 10 mL of 56 mg L(-1) of Au-Pd cs. Ninety per cent of DCF was degraded in 6.5 h by the mixture of Au and Pd NPs. However, the individual Au NPs had no obvious effect in degrading DCF and the monometallic Pd NPs with comparable concentration only degraded less than 20% of DCF. Furthermore, the reaction mechanism of this catalytic process was studied in detail. It was found that the degradation was a second-order exponential reaction. The two main degradation products were obtained by cleaving the carbon-halogen bond of DCF and this made the degradation products more environmentally friendly.

Phytic acid inhibits Cr(VI) reduction on Fe(II)-bearing clay minerals: Changing reduction sites and electron transfer pathways.

The presence of organic phosphorus may influence the characteristics of Cr(VI) reduction and immobilization on Fe(II)-bearing clay minerals under anoxic conditions, as the organic phosphorus tends to bind strongly to clay minerals in soil. Herein, reduced nontronite (rNAu-2) was used to reduction of Cr(VI) in the presence of phytic acid (IHP) at neutral pH. With IHP concentration from 0 to 500 µM, Cr(VI) reduction decreased obviously (17.8%) within first 5 min, and then preferred to stagnate during 4-12 h (≥50 µM). After that, Cr(VI) was reduced continuously at a slightly faster rate. Density functional theory (DFT) calculations revealed that IHP primarily absorbed at the edge sites of rNAu-2 to form Fe-IHP complexes. X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), and Fourier transform infrared spectroscopy (FTIR) results demonstrated that IHP hindered the ingress of CrO42- into the interlayer space of rNAu-2 and impeded their reduction by trioctahedral Fe(II) and Al-Fe(II) at basal plane sites in the initial stage. Additionally, Fe(II) extraction results showed that IHP promoted the electron from interior transfer to near-edge, but hindered it further transfer to surface, resulting in the inhibition on Cr(VI) reduction at edge sites during the later stage. Consequently, IHP inhibits the reduction and immobilization of Cr(VI) by rNAu-2. Our study offers novel insights into electron transfer pathways during the Cr(VI) reduction by rNAu-2 with coexisting IHP, thereby improve the understanding of the geochemical processes of chromium within the iron cycle in soil.

Fe(II)-catalyzed phase transformation of Cd(II)-bearing ferrihydrite-kaolinite associations under anoxic conditions: New insights to role of kaolinite and fate of Cd(II).

Cadmium-bearing ferrihydrite-kaolinite associations (Cd-associations) are commonly found in cadmium-contaminated paddy soils in tropical and subtropical regions. In the presence of anaerobic conditions caused by flooding, the creation of Fe(II) can facilitate the transformation of ferrihydrite into secondary Fe (hydr)oxides, resulting in the redistribution of Cd. However, the role of kaolinite in iron oxides transformation and changes in Cd chemical species have largely not been determined. In this study, Cd-associations were prepared for reaction with Fe(II) under anoxic conditions. The results obtained from powder XRD and EXAFS indicated that the presence of kaolinite association noticeably hastened the transformation of ferrihydrite into crystalline goethite. Specific surface area and electrochemical analyses revealed that smaller particle sizes and higher reactivity of ferrihydrite within Cd-associations collaboratively contribute to the acceleration. Chemical analyses demonstrated a significant negative correlation between ferrihydrite-Fe and aqueous-Cd, and a significant positive correlation between crystalline-Fe and residual-Cd. HRTEM analyses indicated that a portion of the Cd was incorporated into the crystal lattices of lepidocrocite and goethite, with the majority of Cd being sequestered within goethite lattice. These findings provide new insights into the roles of clay minerals in the geochemical cycling of Fe and Cd in paddy soils under anoxic conditions.

Spatial distribution of arsenic and temporal variation of its concentration in rice.

• In order to gain insights into the transport and distribution of arsenic (As) in intact rice (Oryza sativa) plants and its unloading into the rice grain, we investigated the spatial distribution of As and the temporal variation of As concentration in whole rice plants at different growth stages. To the best of our knowledge, this is the first time that such a study has been performed. • Inductively coupled plasma mass spectroscopy (ICP-MS) and high-performance liquid chromatography (HPLC)-ICP-MS were used to analyze total As concentration and speciation. Moreover, synchrotron-based X-ray fluorescence (SXRF) was used to investigate in situ As distribution in the leaf, internode, node and grain. • Total As concentrations of vegetative tissues increased during the 2 wk after flowering. The concentration of dimethylarsinic acid (DMA) in the caryopsis decreased progressively with its development, whereas inorganic As concentration remained stable. The ratios of As content between neighboring leaves or between neighboring internodes were c. 0.6. SXRF revealed As accumulation in the center of the caryopsis during its early development and then in the ovular vascular trace. • These results indicate that there are different controls on the unloading of inorganic As and DMA; the latter accumulated mainly in the caryopsis before flowering, whereas inorganic As was mainly transported into the caryopsis during grain filling. Moreover, nodes appeared to serve as a check-point in As distribution in rice shoots.

Influence of structural Al species on Cd(II) capture by iron muscovite nanoparticles.

The isomorphous substitution in the structure of phyllosilicate minerals plays an important role in regulating of surface chemical properties. In this work, iron muscovite nanoparticles with various Al species were successfully prepared to explore the structural Fe and Al species on the capture of Cd(II) from solutions. The synthesized nanocrystals have irregular shapes with diameters of 10-50 nm. The incorporation of Al(III) into the iron muscovite nanostructure has slight effect on the species of Fe and the crystal phase of the products. The degree of Al(III) substituting Si(IV) in the tetrahedral sheets of the minerals obviously increased with increasing of Al doping levels. For the samples with low Al doping levels (5% and 10%), the adsorption capacity of the iron muscovite nanoparticles for Cd(II) increased slightly. With increasing of Al doping ratio to 15%, the obtained iron muscovite nanoparticles exhibited a maximal uptake of 41.4 mg g-1 for Cd(II), which is about two times that of the undoped samples (22.8 mg g-1). The solution pH had a slight effect on the Cd (II) capture at a wide pH range from 4 to 8. The adsorption of Cd(II) is very fast and reached a steady state within 5 min. Desorption results showed that the binding strength between Cd(II) and iron muscovite nanoparticles was obviously enhanced by incorporation of Al at a high level. The ion exchange and surface complexation are principal mechanisms in the Cd(II) capture by the iron muscovite nanomaterials with various structural Al species.

A general and facile method for improving carbon coat on magnetic nanoparticles with a thickness control.

A general and facile hydrothermal method was developed to improve carbon coating formation on the surface of magnetic nanoparticles from sucrose and hindering growth of pure carbon spheres by using ammonium acetate (CH3COONH4) as a structure guiding agent. The thickness of the carbon coating could be easily realized by adjusting the reaction time.

[Catalytic Degradation of Diclofenac Sodium over the Catalyst of 3D Flower-like alpha-FeOOH Synergized with H2O2 Under Visible Light Irradiation].

Three dimensional (3D) flower-like alpha-FeOOH nanomaterials were prepared by oil bath reflux method using FeSO4, urea, ethanol and water, and the products which were characterized by XRD, FT-IR and SEM techniques. The SEM images showed that the 3D flower-like samples consisted of nanorods with a length of 400-500 nm and a diameter of 40-60 nm. The catalytic performance of the samples was evaluated by catalytic degradation of diclofenac sodium using H2O2 as the oxidant under simulated visible light. The results showed that the as-prepared samples presented high efficient catalytic performances, and more than 99% of the initial diclofenac sodium (30 mg x L(-1)) was degraded in 90 min. A radical mechanism can be proposed for the catalytic degradation of diclofenac sodium solution.

The composite of nitrogen-doped anatase titania plates with exposed {001} facets/graphene nanosheets for enhanced visible-light photocatalytic activity.

Composite photocatalysts composed of nitrogen-doped anatase TiO2 plates with exposed {001} facets (NTS) and graphene nanosheets (G) were firstly synthesized by a facile one-pot hydrothermal process. The morphologies, structural properties, and photocatalytic activities of the resultant NTS/G composites were investigated in detail. Graphene nanosheets were demonstrated play three important roles in the NTS/G composites, as transporter of photo-excited electrons, extender of light absorption range and enhancer of adsorptive capacity, respectively. Due to the effective charge anti-recombination, the efficient utilization of the visible light and the high adsorptive capacity to target pollutants, the composites exhibited significant improvement in photocatalytic degradation of methylene blue under visible light irradiation. Based on the results, the mechanism of enhanced visible-light photocatalytic activity on NTS/G composites was proposed.

Fabrication of magnetic porous Fe-Mn binary oxide nanowires with superior capability for removal of As(III) from water.

Magnetic porous Fe-Mn binary oxide nanowires were successfully fabricated to efficient removal of As(III) from water. The adsorption capacity of the porous nanowires for As(III) obviously increased with increasing of manganese oxide in the composite, accompanying decrease of the saturation magnetization of the adsorbents. Magnetic porous Fe-Mn binary oxide nanowires with an initial Fe:Mn molar ratio of 1:3 exhibited the highest absorption capacity for As(III) and enable magnetic separation from water. The maximal adsorption capacity value is 171mgg(-1) at pH 7.0. In the initial pH range from 3 to 9, 200µgL(-1) of As(III) could be easily decreased to below 10µgL(-1) by the magnetic porous Fe-Mn binary oxide nanowires (0.05gL(-1)) within 75min, and the corresponding residual As was completely oxidized to less toxic As(V). The coexisting chloride, nitrate and sulfate had no significant effect on arsenic removal, whereas, phosphate and humic acid reduced the removal of As(III) by competing with arsenic species for adsorption sites. The resulting magnetic porous Fe-Mn binary oxide nanowires could be a promising adsorbent for As(III) removal from water.

One step solvothermal synthesis of functional hybrid γ-Fe2O3/carbon hollow spheres with superior capacities for heavy metal removal.

One-step hydrothermal method was developed to prepare hybrid γ-Fe2O3/carbon hollow spheres with a predominant orientation (111) plane of γ-Fe2O3 and rich oxygen-containing functional groups on carbon. The resulting functional hybrid exhibited extremely high adsorption capacities for toxic Pb(II) and Cr(VI) ions in solutions with easy magnetic separation. The ease of synthesis and low cost, coupled with the efficient and rapid removal of toxic heavy metal ions, make hybrid γ-Fe2O3/carbon hollow spheres an attractive adsorbent for the purification of waste and contaminated water.

Effects of salinity and humic acid on the sorption of Hg on Fe and Mn hydroxides.

The objective of this study was to investigate the influence of humic acid (HA) and salinity on adsorption of Hg on the amorphous and crystalline of iron and manganese hydroxides. The results show that the adsorption of Hg(2+) on Fe and Mn hydroxides was inhibited in marine system due to the formation of stable, nonsorbing aqueous HgCl(2) complexes in solution. Moreover, Cl(-) inhibited the Hg(2+) adsorption more severely on amorphous than crystalline hydroxides. The addition of HA inhibited Hg(2+) adsorption on Fe and Mn hydroxides in freshwater system might be attributed to the competition between Hg(2+) and HA on adsorption to Fe and Mn hydroxides. In contrast, the addition of HA promoted Hg(2+) adsorption on Fe and Mn hydroxides in the marine system, which might be due to the addition of humic acid resulted in the reaction between Cl(-) and HA, and therefore the reducing of Cl(-) promoted more Hg(2+) on Fe and Mn hydroxides. In addition, the influence of HA on Hg(2+) adsorption on Fe and Mn hydroxides are more visible for crystalline than amorphous hydroxides.

TiO2/activated carbon fibers photocatalyst: effects of coating procedures on the microstructure, adhesion property, and photocatalytic ability.

In order to more easily separate TiO(2) photocatalyst from the treated wastewater, TiO(2) film was immobilized on the surface of activated carbon fibers (ACFs) by employing two kinds of coating procedures, dip-coating, and hydrothermal treatment. The effects of coating procedures on microstructure of TiO(2)-coated ACFs (TiO(2)/ACFs), such as morphology, porous property, crystal structure, and light absorption characteristics were investigated in detail. The adhesion property between TiO(2) film and ACFs was evaluated by ultrasonic vibration, and the photocatalytic activity of TiO(2)/ACFs was tested by the photocatalytic decoloration of methylene blue solution. The results show that hydrothermal treatment presented many advantages to obtain high-performance TiO(2)/ACFs photocatalyst in comparison with dip-coating. Hydrothermal treatment could improve the binding property between TiO(2) films and ACFs, which endowed the as-obtained TiO(2)/ACFs photocatalyst with improved reusable performance, and TiO(2)/ACFs synthesized by hydrothermal treatment presented higher photocatalytic activity.

[Application of the island flap at the dorsum of the middle phalange with the pedicel of the digital proper artery].

OBJECTIVE: To explore a method for the treatment of the skin defects at the distal phalanges of 2-5th fingers. METHODS: The island flap at the dorsum of the middle phalange was designed with the pedicle of dorsal branches from the digital proper artery. When the flap was used to repair defect at finger pulp, the dorsal branch of the digital proper nerve in the flap was kept to be anastomosed to the digital proper nerve at the recipient finger. From Feb. 2005 to May. 2010, 54 cases with skin defects at the distal phalanges of 61 fingers were treated with the flap, including 35 defects at finger pulp and 26 defects at finger tip. RESULTS: The maximum size of defects and flaps was 2.2 cm x 2.5 cm and 2.4 cm x 2.7 cm, respectively. 61 flaps survived completely. Blister was happened in 3 flaps 2 days after operation, which healed spontaneously without necrosis. 54 cases were followed up for 5 to 22 months (average, 11 months). The flaps had good texture and color match with normal sensation (grade S4). The 2-point discrimination distance was 6-9 mm. The interphalangeal joint had normal movement. CONCLUSIONS: The island flap at the dorsum of the middle phalange is an ideal method for the skin defect at the distal phalange of finger.

[Relation between average oxidation state of Mn of birnessite and the amount of Pb2+ adsorbed].

Vacant sites in Mn oxides, commonly occur in soils, play an important role in their heavy metal adsorption behavior. The dependence of Pb2+ adsorption capacity for the synthesized birnessites and their d110-interplanar spacing on the respective Mn average oxidation state (AOS), and the relationship between Pb2+ adsorption and the Mn2+, H+, K+ released during adsorption were investigated. The results show that Mn AOS of birnessites apparently reflects their amount of vacant sites which largely account for the Pb2+ adsorption. Significant positive correlation between Pb2+ adsorption capacity and the Mn AOS of corresponding birnessites (r = 0.9779 > 0.6614, n = 14, alpha = 0.01), negative correlation between d110 spacing and the Mn AOS (r = -0.9035 < -0.6614, n = 14, alpha = 0.01), and significant positive correlation between Pb2+ adsorption and the Mn2+, H+, K+ released during adsorption(r = 0.9962 > 0.6614, n = 14, alpha = 0.01) are found. The vacant sites amount increases with Mn AOS for birnessites, which causes the increase of Pb2+ adsorption. Therefore, the Pb2+ adsorption capacity of birnessite is largely determined by the amount of vacant sites, from which Mn2+, H+, and K+ released during adsorption are mostly derived.