High-precision zinc isotopic characterization of twenty soil reference materials from China determined by MC-ICP-MS.

Zinc isotopic ratios serve as powerful tools for tracing biochemical cycling of metals at Earth's surface, including the distribution, transportation, and enrichment of zinc (Zn) in soil. To conduct such studies and enable inter-laboratory comparisons, high-precision Zn isotopic measurements require the use of soil reference materials (RMs). However, there have been limited reports on the high-precision Zn isotope ratios of soil RMs thus far. In this study, we have developed a two-step Zn chemical separation protocol utilizing Bio-Rad AG MP-1M resin columns. This method has demonstrated excellent reproducibility for measuring the external δ66Zn values (relative to JMC-Lyon) of standard soil reference materials over an extended time period, with a better than 0.06‰ (2SD) precision. Remarkably, this study is the first to report the Zn isotopic compositions of 20 soil reference materials from various soil types in China. With the exception of one sample obtained from a mining area, the Zn isotopic compositions of all the analyzed soil reference materials exhibit remarkable similarity, with an average δ66Zn value of 0.31 ± 0.12‰, which aligns closely with the values observed in igneous rocks. The exceptional sample, with a higher δ66Zn value of 0.61 ± 0.02‰, indicates potential contamination during mining activities.

Quantifying biodegradable organic matter in polluted water on the basis of coulombic yield.

Biodegradable organic matter (BOM) in polluted water plays a key role in various biological purification technologies. The five-day biochemical oxygen demand (BOD5) index is often used to determine the amount of BOM. However, standard BOD5 assays, centering on dissolved oxygen detection, have long testing times and often show severe deviation (error ≥ 15%). In the present study, the coulombic yield (Q) of a bio-electrochemical degradation process was determined, and a new index for BOM quantification was proposed. The Q value represents the quantity of transferred electrons from BOM to oxygen, and the corresponding index was defined as BOMQ. By revealing Q-BOM stoichiometric relationship, we were able to perform a BOMQ assay in a microbial fuel cell involved technical platform. Experimental results verified that 5-500mgL-1 of BOMQ toward artificial wastewater samples could be directly obtained without calibration in several to dozens of hours, leaving less than 5% error. Moreover, the BOMQ assay remained accurate and precise in a wide range of optimized operational conditions. A ratio of approximately 1.0 between the values of BOMQ and BOD5 toward artificial and real wastewater samples was observed. The rapidity, accuracy, and precision of the measurement results are supported by a solid theoretical foundation. Thus, BOMQ is a promising water quality index for quantifying BOM in polluted water.

[Study on the content and carbon isotopic composition of water dissolved inorganic carbon from rivers around Xi'an City].

In this study, the content and isotopic compositions of water dissolved inorganic carbon (DIC) from four typical rivers (Chanhe, Bahe, Laohe and Heihe) around Xi'an City were studied to trace the possible sources of DIC. The results of this study showed that the content of DIC in the four rivers varied from 0.34 to 5.66 mmol x L(-1) with an average value of 1.23 mmol x L(-1). In general, the content of DIC increased from the headstream to the river mouth. The delta13C(DIC) of four rivers ranged from -13.3 per thousand to -7.2 per thousand, with an average value of -10.1 per thousand. The delta13C(DIC) values of river water were all negative (average value of -12.6 per thousand) at the headstream of four rivers, but the delta13C(DIC) values of downstream water were more positive (with an average value of -9.4 per thousand). In addition, delta13C(DIC) of river water showed relatively negative values (the average value of delta13C(DIC) was -10.5 per thousand) near the estuary of the rivers. The variation of the DIC content and its carbon isotope suggested that the DIC sources of the rivers varied from the headstream to the river mouth. The negative delta13C(DIC) value indicated that the DIC may originate from the soil CO2 at the headstream of the rivers. On the other hand, the delta13C(DIC) values of river water at the middle and lower reaches of rivers were more positive, and it showed that soil CO2 produced by respiration of the C4 plants (like corn) and soil carbonates with positive delta13C values may be imported into river water. Meanwhile, the input of pollutants with low delta13C(DIC) values may result in a decrease of delta13C(DIC) values in the rivers. The study indicated that the DIC content and carbon isotope may be used to trace the sources of DIC in rivers around Xi'an City. Our study may provide some basic information for tracing the sources of DIC of rivers in the small watershed area in the Loess Plateau of China.

Kinetics of CH3S(-) reaction with in situ ferrate(VI) in aqueous alkaline solution.

This study introduced a new treatment process named "in situ ferrate(VI) oxidation (IFO)" in which odorous compounds such as CH3S(-) can be quickly degraded by in situ freshly generated ferrate(VI) through electrolysis in aqueous alkaline solution. Two kinetic models to describe the in situ ferrate(VI) generation and its reaction with CH3S(-) were established mathematically by considering three main reaction mechanisms of ferrate(VI) electrochemical generation, ferrate(VI) self-decomposition and CH3S(-) degradation in aqueous strong alkaline solution. The effects of three key factors: (i) NaOH concentration, (ii) applied current density, and (iii) initial CH3S(-) concentration on the performance of the IFO process were investigated by conducting three sets of experiments and the kinetic models were validated by fitting the experimental data. The goodness of the fittings demonstrated that the new models could well describe both the kinetics of ferrate(VI) generation reaction and CH3S(-) degradation reaction. The experimental results confirmed that the higher NaOH concentration and current density applied would be beneficial to the electrochemical generation of ferrate(VI) and also elimination of its self-decomposition, but the experiments also demonstrated an optimum NaOH concentration at 10M to achieve the best performance of CH3S(-) degradation reaction in such an IFO system.

Mesoporous zinc ferrite: synthesis, characterization, and photocatalytic activity with H2O2/visible light.

Mesoporous ZnFe(2)O(4) (meso-ZnFe(2)O(4)) was synthesized by a hydrothermal process in which cetyltrimethylammonium bromide (CTAB) participates in the reaction to produce nanocrystals. Synthesized ZnFe(2)O(4) was characterized by energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area, scanning electronic microscopy (SEM), transmission electron microscopy (TEM), and diffuse reflectance spectra (DRS). The meso-ZnFe(2)O(4) was resulted from the agglomeration of nanoparticles with size of 5-10nm. The photocatalytic activity of ZnFe(2)O(4) under visible light (λ>400 nm) was evaluated by the degradation of Acid Orange II (AOII) at different sintering temperatures, the amount of ZnFe(2)O(4), and the concentration of H(2)O(2). The photocatalytic degradation of AOII was almost complete within 2h in H(2)O(2)/visible light system. The high efficiency for AOII degradation was attributed to the strong absorption of ZnFe(2)O(4) in visible-light region and the generation of reactive OH by H(2)O(2) in the system. The involvement of OH in oxidizing AOII was examined by determining the photocurrent of ZnFe(2)O(4), [OH], and degradation rates using different scavengers. Organic compounds as intermediates of the degradation process were identified by LC/MS. Moreover, ZnFe(2)O(4) retained their degradation efficiencies for a series of repetitive batch runs, indicating the true photocatalytic process.

[Study on the inhibitory effect of RNA interference on replication of dengue virus].

To investigate the inhibitory effect of RNA interference (RNAi) on dengue virus I (DENV-1) replication. Small interfering RNA (siRNA) against the PreM gene of dengue virus was synthesized and transfected into C6/36 cells with liposome, which was then attacked by DENV-1 virus. The antiviral effect of siRNA was evaluated by cytopathic effect (CPE), the cell survival rate measured by MTT, and virus RNA quantified by real-time RT-PCR. The results showed that after 7 days post infection of dengue virus, the transfected C6/36 cells showed less CPE. The cell survival rate of the transfected C6/36 cells increased by 2.26 fold, and the amount of virus RNA in the transfected cells was reduced by about 97.54% as well. These findings indicated that the siRNA could effectively inhibit dengue virus RNA replication, and protect C6/36 cells from viral attack, indicating its potential role in prevention and treatment of dengue fever.

Comparison of the degradations of diphenamid by homogeneous photolysis and heterogeneous photocatalysis in aqueous solution.

In this work, the homogeneous and heterogeneous degradations of diphenamid (DPA) in aqueous solution were conducted by direct photolysis with UVC (254nm) and by photocatalysis with TiO(2)/UVA (350nm), and the experimental results were compared. It was found that the homogeneous photolysis by UVC irradiation alone was quite efficient to degrade DPA up to 100% after 360min, but was very inefficient to mineralize its intermediates in terms of dissolved organic carbon reduction of only 8%. In contrast, the heterogeneous photocatalysis with TiO(2)/UVA showed relatively a lower degree of DPA degradation (51%), but a higher degree of its mineralization (11%) after 360min. These results reveal that the photocatalysis process has relatively poor selectivity to degrade different compounds including various intermediates from the DPA degradation, which is beneficial to its mineralization. In addition, over 20 intermediates were identified by LC-MS and (1)H NMR analyses. Based on the identified intermediates, the reaction mechanisms and the detailed pathways of the DPA degradation by photolysis and photocatalysis were proposed, and are presented in this paper.

Effects of key reaction parameters on the reductive dechlorination of chloroform with Pd/Fe0 bimetal in aqueous solution.

In this study, bimetallic Pd/Fe(0) particles were synthesized and employed to reduce chloroform in aqueous solution. The investigation emphasized on the effects of some key reaction parameters including Pd/Fe(0) dosage, pH, oxidation-reduction potential (ORP) and presence of anions on the reductive dechlorination reaction. The experimental results showed that high Pd/Fe(0) dosage, low initial pH and low ORP benefited the reductive dechlorination of chloroform. The ORP values in the aqueous chloroform solution bubbled with different gases of N(2), O(2) and air varied significantly and the efficiency of chloroform degradation under different atmospheres followed an order from high to low as N(2) > air > O(2). The experiments also demonstrated that SO(4)(2 -) and NO(3)(-) ions inhibited the dechlorination reaction significantly, while H(2)PO(4)(-) ion had no significant influence on the dechlorination.

Bio-electro-Fenton process driven by microbial fuel cell for wastewater treatment.

In this study, we proposed a new concept of utilizing the biological electrons produced from a microbial fuel cell (MFC) to power an E-Fenton process to treat wastewater at neutral pH as a bioelectro-Fenton (Bio-E-Fenton) process. This process can be achieved in a dual-chamber MFC from which electrons were generated via the catalyzation of Shewanella decolorationis S12 in its anaerobic anode chamber and transferred to its aerated cathode chamber equipped with a carbon nanotube (CNT)/gamma-FeOOH composite cathode. In the cathode chamber, the Fenton's reagents including hydrogen peroxide (H(2)O(2)) and ferrous irons (Fe(2+)) were in situ generated. This Bio-E-Fenton process led to the complete decolorization and mineralization of Orange II at pH 7.0 with the apparent first-order rate constants, k(app) = 0.212 h(-1) and k(TOC) = 0.0827 h(-1), respectively, and simultaneously produced a maximum power output of 230 mW m(-2) (normalized to the cathode surface area). The apparent mineralization current efficiency was calculated to be as high as 89%. The cathode composition was an important factor in governing system performance. When the ratio of CNT to gamma-FeOOH in the composite cathode was 1:1, the system demonstrated the fastest rate of Orange II degradation, corresponding to the highest amount of H(2)O(2) formed.

Heterogeneous photodegradation of pentachlorophenol and iron cycling with goethite, hematite and oxalate under UVA illumination.

Heterogeneous photodegradation of pentachlorophenol (PCP) in the goethite (alpha-FeOOH) and hematite (alpha-Fe(2)O(3)) systems with oxalate under UVA illumination was investigated. The PCP degradation, dechlorination and detoxification, in terms of Microtox acute toxicity, were all achieved to the higher efficiency in the hematite suspension than in the goethite suspension. The optimal initial concentration of oxalic acid (C(ox)(0)) for the PCP degradation with goethite and hematite under the experimental conditions was found to be 1.2mM, since sufficient Fe(III) as Fe(C(2)O(4))(3)(3-) and Fe(II) as Fe(C(2)O(4))(2)(2-) can be formed at C(ox)(0)>or=1.2mM. The main intermediates of PCP degradation were identified by GC-MS, HPLC and IC analyses. It was found that the cycling process between Fe(III) and Fe(II) in both the goethite and hematite systems occurred more vigorously at the initial stage and gradually became gentle, while the rate of PCP photodegradation varied from fast to slow during the reaction time. Furthermore, the formation of H(2)O(2) during photoreaction was studied to explore its relationship with the photodegradation efficiency and the iron cycling process.

Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO2 suspensions.

BACKGROUND, AIM AND SCOPE: Photocatalytic oxidation using UV irradiation of TiO(2) has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e(-)(cb)) with electron holes (h(vb)(+)) on the irradiated TiO(2) surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO(4)(2-)) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO(2) photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e(-)(cb) and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate. MATERIALS AND METHODS: The paper reviews the published results of laboratory experiments designed to follow the photocatalytic degradation of selected contaminants of environmental significance and the influence of the experimental conditions (e.g. pH, reactant concentrations and dissolved oxygen). The specific compounds are as follows: ammonia, cyanate, formic acid, bisphenol-A, dibutyl- and dimethyl-phthalate and microcystin-LR. The principal focus in these studies has been on the rates of reaction rather than on reaction pathways and products. RESULTS: The presence of UV/TiO(2) accelerates the chemical reduction of ferrate, and the reduction rate decreases with pH owing to deprotonation of ferrate ion. For all the selected contaminant substances, the photocatalytic oxidation rate was greater in the presence of ferrate, and this was believed to be synergistic rather than additive. The presence of dissolved oxygen in solution reduced the degradation rate of dimethyl phthalate in the ferrate/photocatalysis system. In the study of microcystin-LR, it was evident that an optimal ferrate concentration exists, whereby higher Fe(VI) concentrations above the optimum leads to a reduction in microcystin-LR degradation. In addition, the rate of microcystin-LR degradation was found to be strongly dependent on pH and was greatest at pH 6. DISCUSSION: The initial rate of photocatalytic reduction under different conditions was analysed using a Langmuirian form. Decrease in rates in the presence of dissolved oxygen may be due to competition between oxygen and ferrate as electron scavengers and to non-productive radical species interactions. The reaction between ferrate(VI) and microcystins-LR in the pH range of 6.0-10.0 is most likely controlled by the protonated Fe(VI) species, HFeO(4)(-). CONCLUSIONS: The photocatalytic oxidation of selected, recalcitrant contaminants was found to be significantly greater in the presence of ferrate, arising from the role of ferrate in inhibiting the h(vb)(+)-e(-)(cb) pair recombination on TiO(2) surfaces and the corresponding generation of highly oxidative Fe(V) species. The performance of the ferrate/photocatalysis system is strongly influenced by the reaction conditions, particularly the pH and dissolved oxygen concentration, arising from the complex nature of the interactions between the catalyst and the solution. Overall, the treatment performance of the Fe(VI)-TiO(2)-UV system is generally superior to alternative chemical oxidation methods. RECOMMENDATIONS AND PERSPECTIVES: The formation of intermediate Fe(V) species in the photocatalytic reduction of ferrate(VI) requires confirmation, and a method involving electron paramagnetic resonance spectroscopy could be applied for this. The reactivity of Fe(V) with the selected contaminants is required in order to better understand the role of ferrate in the Fe(VI)-TiO(2)-UV oxidation system. To increase the practical utility of the system, it is recommended that future studies involving the photocatalytic oxidation of pollutants in the presence of ferrate(VI) should focus on developing modified TiO(2) surfaces that are photocatalytic under visible light conditions.

Elimination of sludge odor by oxidizing sulfur-containing compounds with ferrate(VI).

Sulfur-containing compounds are one kind of odorant found in sewage treatment works, composting plants, refuse storage and transfer, landfill sites, and associated with various industries. In the present research, the reaction kinetics of ferrate(VI) (Fe(VI)O4(-), Fe(VI)) with 2-mercaptobenzothiazole (MBT), thiosemicarbazide (NH2NHC(S)NH2, TSC), and thiourea dioxide (NH2C(SO2)NH2, TUDO) were studied under alkaline conditions. Stoichiometryof Fe(VI) oxidation with hydrogen sulfide (H2S), TSC, and methyl mercaptan (CH3SH) were determined at neutral and alkaline pH (7.0-11.0). Stoichiometric molar ratios ([Fe(VI):[S]) were determined to be 2.5, 2.0, and 4.6 for sulfide, TSC, and CH3SH, respectively, at pH 9.0. TUDO and methyl sulfonic acid (CH3SO3H) were identified to be the main intermediates of TSC and CH3SH reactions with Fe(VI), respectively, at pH 9.0, while sulfate was one of the final products. A reaction scheme is given to explain the intermediates and products formed in the CH3SH degradation by Fe(VI). Experiments were also conducted to evaluate the odor emission of digested sludge from sewage treatment works in terms of chemical concentration and also odor concentration affected by the Fe(VI) dose. The potential of using Fe(VI) to achieve odor control in sludge treatment is briefly discussed.

Microbial fuel cell with an azo-dye-feeding cathode.

Microbial fuel cells (MFCs) were constructed using azo dyes as the cathode oxidants to accept the electrons produced from the respiration of Klebsiella pneumoniae strain L17 in the anode. Experimental results showed that a methyl orange (MO)-feeding MFC produced a comparable performance against that of an air-based one at pH 3.0 and that azo dyes including MO, Orange I, and Orange II could be successfully degraded in such cathodes. The reaction rate constant (k) of azo dye reduction was positively correlated with the power output which was highly dependent on the catholyte pH and the dye molecular structure. When pH was varied from 3.0 to 9.0, the k value in relation to MO degradation decreased from 0.298 to 0.016 micromol min(-1), and the maximum power density decreased from 34.77 to 1.51 mW m(-2). The performances of the MFC fed with different azo dyes can be ranked from good to poor as MO>Orange I>Orange II. Furthermore, the cyclic voltammograms of azo dyes disclosed that the pH and the dye structure determined their redox potentials. A higher redox potential corresponded to a higher reaction rate.

Electrochemical evidences for promoted interfacial reactions: the role of Fe(II) adsorbed onto gamma-Al2O3 and TiO2 in reductive transformation of 2-nitrophenol.

This study was aimed at elucidating the role of adsorbed Fe(II) on minerals in the reductive transformation of 2-nitrophenol (2-NP) by using electrochemical methods. The studies of Fe(ll) adsorption and 2-NP reduction kinetics showed that the identity of minerals such as gamma-Al2O3 and TiO and the solution pH were crucial factors to determine the Fe(ll) adsorption behavior and to influence the rate constant (k) of 2-NP reduction. Furthermore, two electrochemical methods, cyclic voltammetry (CV) and electrochemical impedance spectrometry (EIS), were applied to characterize the Fe(II) reactivity with both the mineral-coated and mineral-free electrodes. The electrochemical evidence confirmed that the peak oxidation potential (Ep) of complex Fe(II) can be significantly affected by the solution pH;the enhanced reductive transformation of 2-NP can be related to the reduced Ep of surface-complex Fe(II) and the reduced charge transfer resistance (R(CT)) of the Fe(III)/Fe(II) couple. All these relationships were studied quantitatively. At pH 6.7, the measured Ep and R(CT) decreased in the order TiO2/GC < gamma-Al2O3/ GC < GC (Ep, 0.140 < 0.190 < 0.242 V; R(CT), 0.30 < 0.41 < 0.78 komega), while the 2-NP reduction on different minerals were in the order TiO2 > gamma-Al2O3 > nonmineral (k x 10-2, 7.91 > 0.64 > 0.077 min(-l)).

Degradation of n-butyl benzyl phthalate using TiO2/UV.

n-Butyl benzyl phthalate (BBP) has been classified as endocrine disrupting compound and priority pollutant. Effects of TiO(2) dosage, pH, initial BBP concentration and co-existing substances on the degradation of BBP by TiO(2)/UV process were investigated. The optimal TiO(2) dosage and pH value for the BBP degradation were 2.0gL(-1) and 7.0, respectively. The degradation rate of BBP by TiO(2)/UV process could be fitted pseudo-first-order kinetics. The effects of co-existing substances on the degradation rate of BBP revealed that some anions (such as BrO(3)(-), ClO(4)(-) and Cr(2)O(7)(2-)) could enhance BBP degradation, and other anions would restrain BBP degradation. The sequence of inhibition was PO(4)(3-)>CO(3)(2-)>NO(3)(-)>SO(4)(2-)>Cl(-). The cations K(+), Na(+), Mg(2+) and Ca(2+) had the restrained effect on the BBP degradation, and the effect of Ca(2+) was the strongest among four cations tested. The organic compounds acetone and methanol decreased the degradation rate of BBP. The major intermediates of BBP degradation were identified as mono-butyl phthalate, mono-benzyl phthalate and phthalic acid, and a primary degradation mechanism was proposed.

Effects of structure of anodic TiO(2) nanotube arrays on photocatalytic activity for the degradation of 2,3-dichlorophenol in aqueous solution.

In this study titanium dioxide nanotube (TNT) arrays were prepared by an anodic oxidation process with post-calcination. The morphology and structure of the TNT films were studied by field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of the TNT films was evaluated in terms of the degradation of 2,3-dichlorophenol in aqueous solution under UV light irradiation. The effects of the nanotube structure including tube length and tube wall thickness, and crystallinity on the photocatalytic activity were investigated in detail. The results showed that the large specific surface area, high pore volume, thin tube wall, and optimal tube length would be important factors to achieve the good performance of TNT films. Moreover, the TNT films calcined at 500 degrees C for 1h with the higher degree of crystallinity exhibited the higher photocatalytic activity than other TNT films calcined at 300 and 800 degrees C. Consequently, these results indicate that the optimization of TiO(2) nanotube structures is critical to achieve the high performance of photocatalytic reaction.

A new concept of desulfurization: the electrochemically driven and green conversion of SO2 to NaHSO4 in aqueous solution.

A new concept of desulfurization was developed by designing a series of electrochemical reactions to drive an SO2 absorption-and-conversion process in aqueous solution, hence the SO2 in gas was eventually converted to a valuable chemical of NaHSO4. A model experiment of chemically substantiating this concept includes two steps: (I) absorption of SO2 gas by aqueous solution and oxidation of the absorbed SO2 to SO4(2-) by air and (II) transformation of the SO4(2-) to NaHSO4. The experiment demonstrated that in Step I, the cathodic reduction of 02 from ambient air scavenged the H+ released due to the SO2 absorption and its further oxidation, which thereby were accelerated. Meanwhile H2O2 as a cathodic product further enhanced the SO2 oxidation. In Step II, the anodic oxidation of H2O supplied H+ and allowed the NaHSO4 formation through balances of electrons and mass. Thereafter, a pH range of 5.0-6.0 for the SO2 oxidation was optimized, and an electrochemically driven process for the SO2 conversion to NaHSO4 was proposed. Sustainability evaluation indicated that this concept complies with the principles of green chemistry and potentially enables the SO2 conversion from flue gas to NaHSO4 as a value-added process.

Heterogeneous photodegradation of pentachlorophenol with maghemite and oxalate under UV illumination.

The degradation of pentachlorophenol (PCP) in a heterogeneous system with maghemite (gamma-Fe2O3) and oxalate under UV illumination was investigated in this study. The results of adsorption experiments demonstrated competitive adsorption between PCP and oxalic acid on the surface of gamma-Fe2O3. The results of photodegradation experiments showed that the rate of PCP degradation strongly relied on the oxalic acid concentration and that an optimal tested initial concentration of oxalic acid (Cox(0)) of 0.8 mM was obtained under our experimental conditions. It was observed that a sufficient amount of oxalic acid can be adsorbed on the gamma-Fe2O3 to form various Fe(III)-oxalate complexes at Cox(o) = 0.8 mM. During the photoreaction, Fe(C2O4)2- and Fe(C2O4)3(3-) were found to be the dominant Fe(III)-oxalate complexes at different Cox(0), while Fe(C2O4)2(2-) was the dominant Fe(II)-oxalate complex at Cox(0) > or = 0.8 mM. The mechanism of H2O2 formation and consumption in the UV-irradiated gamma-Fe2O3/oxalate system was proposed and evaluated. Furthermore, six intermediates of PCP degradation were identified by GC/MS, HPLC, and IC analyses, respectively, and a possible pathway of PCP degradation in such a system was proposed.

AgNO3-lnduced photocatalytic degradation of odorous methyl mercaptan in gaseous phase: mechanism of chemisorption and photocatalytic reaction.

In this study, AgNO3 films prepared by a simple dip-coating method were used to remove gaseous methyl mercaptan (CH3SH) for odor control. The AgNO3 films were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy/energy-dispersive X-ray spectrometry(SEM/EDX), and X-ray photoelectron spectroscopy (XPS) before and after the reaction, and as- obtained products were identified by means of gas chromatography/mass spectrometry (GC/MS) and ion chromatography. The experiments demonstrated that the AgNO3 film can induce a quick chemisorption of gaseous CH3SH to form AgSCH3 and other intermediate products such as alpha-Ag2S, Ag4S2, and AgSH on its surface. Under UVA illumination, these sulfur products can be photocatalytically oxidized to AgSO3CH3 and Ag2SO4. Then AgSO3CH3 and Ag2SO4 will continue the chemisorption of gaseous CH3SH, similar to AgNO3, to form AgSCH3 again and release two final products, HSO3CH3 and H2SO4. Hence it is a AgNO3-induced photocatalytic reaction for odorous CH3SH degradation in gaseous phase. This fundamental research about the mechanism of chemisorption and photocatalytic reaction provides essential knowledge with potential to further develop a new process for gaseous CH3SH degradation in odor control.

Effects of dissolved oxygen, pH, and anions on the 2,3-dichlorophenol degradation by photocatalytic reaction with anodic TiO(2) nanotube films.

In this study, the highly-ordered TiO(2) nanotube (TNT) arrays on titanium sheets were prepared by an anodic oxidation method. Under UV illumination, the TNT films demonstrated the higher photocatalytic activity in terms of 2,3-dichlorophenol (2,3-DCP) degradation in aqueous solution than the conventional TiO(2) thin films prepared by a sol-gel method. The effects of dissolved oxygen (DO) and pH on the photocatalytic degradation of 2,3-DCP were investigated. The results showed that the role of DO in the 2,3-DCP degradation with the TNT film was significant. It was found that 2,3-DCP in alkaline solution was degraded and dechlorinated faster than that in acidic solution whereas dissolved organic carbon removal presented an opposite order in dependence of pH. In the meantime, some main intermediate products from 2,3-DCP degradation were identified by a (1)H NMR technique to explore a possible degradation pathway. A major intermediate, 2-chlororesorcinol, was identified from the 2,3-DCP decomposition as a new species compared to the findings in previous reports. Photocatalytic deactivation was also evaluated in the presence of individual anions (NO(3)(-), Cl(-), SO(4)(2-), and H(2)PO(4)(-)). The inhibition degree of photocatalytic degradation of 2,3-DCP caused by these anions can be ranked from high to low as SO(4)(2-)>Cl(-)>H(2)PO(4)(-)>NO(3)(-). The observed inhibition effect can be attributed to the competitive adsorption and the formation of less reactive radicals during the photocatalytic reaction.