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17 β -Estradiol (E2) is a natural steroidal estrogen essential for a variety of physiological functions in organisms. However, external E2, which is renowned for its potent biological effects, is also considered to be an endocrine-disrupting compound (EDC) capable of disturbing the normal operation of the endocrine system, even at nanogram-per-liter (ng/L) concentrations. Studies have revealed that medical and livestock wastewater can be contaminated with E2, which poses potential risks to human health. Currently, the primary method for detecting E2 relies on liquid chromatography-mass spectrometry, which is limited with regard to on-site or large-scale sample testing due to instrumental constraints. Herein, we developed a magnetic graphene oxide (MGO)/aptamer separating material. The MGO was synthesized by creating a water-in-oil microemulsion at 90 ℃, an agarose hydrogel to load the Fe 3 O 4 nanoparticles, and layered graphene oxide (GO). In contrast to conventional methods, such as chemical co-precipitation and solvothermal approaches, this method is more time-efficient and does not require high temperature or pressure. Moreover, the use of a physical encapsulation technique for enwrapping the Fe 3 O 4 nanoparticles and layered GO eliminates the need for chemical modification. This approach reduces the use of harmful chemicals, ensures complete loading, and results in highly efficient encapsulation. The MGO was characterized using Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM), as well as dynamic light scattering (DLS) and Zeta potential analyses, which revealed that the Fe 3 O 4 nanoparticles had been successfully loaded onto the GO to produce MGO particles mainly around 5 μm in size. Additionally, this study demonstrated that the aqueous MGO dispersion is highly stable. This substance was used to develop a fluorescent biosensor that uses a "turn-on" mechanism to rapidly and highly sensitively detect E2. MGO is capable of adsorbing a fluorescently labeled E2 aptamer (FAM-Apt) in solution, resulting in fluorescence quenching through fluorescence resonance energy transfer (FRET) between the fluorescent group and graphene. However, E2 preferentially binds to FAM-Apt, resulting in the FAM-Apt separating from the MGO in the presence of E2, thereby restoring fluorescence. The developed biosensor exhibits a robust linear correlation between relative fluorescence intensity and E2 mass concentration in the 1-1000 ng/mL range, and boasts a low detection threshold of 1 ng/mL. The use of MGO as an absorbent and fluorescence quencher led to an E2-detection limit that is two orders of magnitude lower than that of a GO-based sensor. This biosensor also outperforms other aptamer-based systems in terms of detection time, linear range, and sensitivity; it also demonstrates remarkable resilience toward various interfering ions and exhibits strong selectivity among structurally similar estrogen analogs. A range of ions commonly present in water samples were introduced into the reaction system at specific concentrations to gauge the impact of interfering ions on sensor performance. With the exception of Fe 3+ ions at 0.3 mg/L, which led to a lower fluorescence intensity, interfering ions were found to exhibit minimal effects. Biosensor specificity and selectivity were further scrutinized by introducing four estrogenic disruptors, including estriol (E3), 17 β -ethynylestradiol (EE2), estrone (E1), and bisphenol A (BPA), each at a mass concentration of 1 μg/mL under the same reaction conditions used to detect E2. The recovered relative fluorescence-signal values for E1 and E3 were determined to be 33% and 23% that of E2, respectively, while EE2 and BPA hardly elicited any fluorescence signal recovery, thereby highlighting the ability of the biosensor to precisely detect E2 with minimal interference from estrogen analogs. The efficacy of the MGO-FAM-Apt biosensor was subsequently validated by testing river-water samples containing known quantities of added E2, which yielded recoveries of between 91.0% and 110.0%, thereby affirming the reliability of this biosensor for use in practical applications. The developed sensor may be somewhat limited compared to liquid chromatography-high-resolution mass spectrometry in detection limit, but the developed biosensor is cost-effective, detects rapidly, and is capable of simultaneously analyzing multiple samples, making it suitable for on-site or large-scale E2 testing of environmental water samples.

Due to the aggravation of atmospheric nitrogen and sulfur deposition and the unreasonable application of fertilizer, soil acidification is becoming increasingly serious. In heavy metal-contaminated soils, acidification not only seriously affects fertility but also the effectiveness and sustainability of conventional passivation remediation materials such as biochar. The application of calcium fertilizer may improve soil acidification, alleviate the aging of biochar materials in soil, and improve its remediation ability to composite polluted soil. However, the mechanism of its effect is still unclear. Based on this, this study selected iron-manganese oxide （FM） and hickory cattails biochar （BC） to prepare biochar-ferromanganese composites （BFM） and conducted simulated acidification on it. Through characterization and an aqueous adsorption test, the changes in physicochemical properties and adsorption properties of the material after acidification were explored. Then, orthogonal tests were carried out to explore the effects of the combination of BFM and calcium fertilizer on soil pH and the availability of Cd and As under acidification conditions and to obtain the best combination scheme. The results showed that the optimal ratio of BC and FM in BFM was 7∶3 （quality ratio）, the removal rates of Cd（Ⅱ） and As（Ⅲ） were as high as 94.58% and 97.14%, respectively, and the adsorption capacities were 120.74 mg·g -1 and 129.29 mg·g -1 （solid-liquid ratio 1∶500）. After acidification treatment, the pore structure of BFM surface decreased, and the types and quantities of functional groups changed, resulting in the removal rates of Cd（Ⅱ） and As（Ⅲ） in aqueous solution decreasing by 73.97%-92.84% and 73.56%-93.61%, respectively. The combined application of calcium fertilizer and BFM could significantly increase soil pH, with an increase range of 3.06%-37.84%. The effect of increasing pH decreased with the increase in culture time and acidification degree. Compared with that in the blank control, the content of available Cd in soil was significantly reduced by 22.67%-97.78%. The content of available As in soil was generally stable. According to the effect curve analysis of the orthogonal test results, under the condition of weak acidification degree （pH=5.6）, the application of 2% supplemental amount with 2% silica-calcium fertilizer and 2% calcium-magnesium phosphate fertilizer had a good passivation effect on soil Cd. Under the condition of strong acidification degree （pH=4.0）, the application of 2% supplemental amount and 2% silica-calcium fertilizer had a good passivation effect on soil As. In summary, simulated acidification will affect the adsorption performance of BFM, and calcium fertilizer combined with it can increase soil pH, improve soil acidification, alleviate the aging of BFM in acidified soil, and improve its repair ability to heavy metal-polluted soil.

In this study, the effects of four types of amendments on effective Cd and Cd content in different parts of prickly ash soil and soil enzyme activity were studied, which provided scientific basis for acidification improvement of purple soil and heavy metal pollution control. A field experiment was conducted. Six treatments were set up:no fertilizer (CK), only chemical fertilizer (F), lime + chemical fertilizer (SF), organic fertilizer + chemical fertilizer (OM), biochar + chemical fertilizer (BF), and vinasse biomass ash + chemical fertilizer (JZ). Soil pH; available Cd (DTPA-Cd); Cd content in branches, leaves, shells, and seeds of Zanthoxylum; as well as the activities of catalase (S-CAT), acid phosphatase (S-ACP), and urease (S-UE) in different treatments were studied, and their relationships were clarified. The results showed following:① The two treatments of vinasse biomass ash + chemical fertilizer and lime + chemical fertilizer significantly increased soil pH ( P < 0.05) to 3.39 and 2.25 units higher than that in the control, respectively. Compared with that in the control treatment, the content of available Cd in soil under vinasse biomass ash + chemical fertilizer and lime + chemical fertilizer treatment decreased by 28.91 % and 20.90 %, respectively. ② The contents of Cd in leaves, shells, and seeds of Zanthoxylum were decreased by 31.33 %, 30.24 %, and 34.01 %, respectively. The Cd enrichment ability of different parts of Zanthoxylum was different, with the specific performances being leaves > branches > seeds > shells. Compared with that of the control, the enrichment coefficient of each part of Zanthoxylum treated with vinasse biomass ash + chemical fertilizer decreased significantly( P < 0.05)by 27.54 %-40.0 %. ③ The changes in catalase and urease activities in soil treated with amendments were similar. Compared with those in the control group, the above two enzyme activities were significantly increased by 191.26 % and 199.50 %, respectively, whereas the acid phosphatase activities were decreased by 16.45 %. Correlation analysis showed that soil available Cd content was significantly negatively correlated with soil pH value( P < 0.01), S-CAT and S-UE enzyme activities were significantly positively correlated with soil pH( P < 0.01), and the soil available Cd content was significantly negatively correlated ( P < 0.01); the S-ACP enzyme showed the complete opposite trends. The application of lime and vinasse biomass ash to acidic purple soil had the most significant effect on neutralizing soil acidity. It was an effective measure to improve acidic purple soil and prevent heavy metal pollution by reducing the effective Cd content in soil and improving the soil environment while inhibiting the absorption and transfer of Cd in various parts of Zanthoxylum.

Antibiotics are playing an increasingly important role in clinical antibacterial applications. However, their abuse has also brought toxic and side effects, drug-resistant pathogens, decreased immunity and other problems. New antibacterial schemes in clinic are urgently needed. In recent years, nano-metals and their oxides have attracted wide attention due to their broad-spectrum antibacterial activity. Nano-silver, nano-copper, nano-zinc and their oxides are gradually applied in biomedical field. In this study, the classification and basic properties of nano-metallic materials such as conductivity, superplasticity, catalysis, and antibacterial activities were firstly introduced. Secondly, the common preparation techniques, including physical, chemical and biological methods, were summarized. Subsequently, four main antibacterial mechanisms, such as cell membrane, oxidative stress, DNA destruction and cell respiration reduction, were summarized. Finally, the effect of size, shape, concentration and surface chemical characteristics of nano-metals and their oxides on antibacterial effectiveness and the research status of biological safety such as cytotoxicity, genotoxicity and reproductive toxicity were reviewed. At present, although nano-metals and their oxides have been applied in medical antibacterial, cancer treatment and other clinical fields, some issues such as the development of green preparation technology, the understanding of antibacterial mechanism, the improvement of biosafety, and the expansion of application fields, require further exploration.

A Fe-Mn oxide-microbe combined biochar (FM-DB) was prepared to simultaneously remove Cd(Ⅱ) and As(Ⅲ) contamination in an aqueous system. In the FM-DB, the best ratio of Fe-Mn oxide (FMBO) and carya cathayensis shell biochar (CCSB) was 3%+3%. The material had good acid resistance, mechanical strength, and mass transfer performance, and the maximum removal rates for Cd(Ⅱ) and As(Ⅲ) in the binary system were 77.29% and 99.94%, respectively. Characterization confirmed that the FM-DB was successfully prepared and had a rich functional group structure. The single-factor adsorption test results for Cd(Ⅱ) and As(Ⅲ) showed that the composite material had a certain adsorption capacity affected by initial pH, equilibration time, and initial concentration for Cd(Ⅱ) and As(Ⅲ) under different conditions. The adsorption isotherm and kinetic data indicated the adsorption equilibrium time for Cd(Ⅱ) and As(Ⅲ) was 3.5 h and 8 h, and the maximum capacity was 59.27 mg·g -1 and 84.73 mg·g -1 , respectively. The adsorption of Cd(Ⅱ) and As(Ⅲ) was mainly affected by the electron exchange, electron sharing, and complexation on the surface of the material. The whole adsorption process was a combination of single-layer adsorption and multi-layer adsorption on an uneven surface. The adsorption process was a multi-step process, including outer surface diffusion and inner particle diffusion. In addition, comparing the removal rate of composite materials in the single-component system and the binary system, a mutual promotion of adsorption between Cd(Ⅱ) and As(Ⅲ) was found under the binary system. In conclusion, oxide-microbe combined biochar could be an efficient adsorption material and was suitable for the remediation of aqueous system pollution caused by Cd(Ⅱ) and As(Ⅲ).

In this study, we synthesized Fe/Mn bimetallic oxide coated biochar sorbents by pyrolysis of wheat straw impregnated with ferric chloride and potassium permanganate and investigated their potential to adsorb nitrate in water. X-ray photoelectron spectroscopy and scanning electron microscopy analysis suggests that Fe(Ⅲ)/Mn(Ⅳ) bimetallic oxide particles emerge on the sorbents. The optimized sorbent could achieve a specific surface area of 153.116 m 2 ·g -1 and a point of zero charge of 9.76. Batch nitrate adsorption experiments were carried out to investigate the influence of various factors, such as sorbent dosage, initial solution pH, and co-existing anions. Results show that the sorbent maintained a high adsorption capacity of 75.40%-78.70% over a wide range of pH from 1.00 to 9.05, and the sorption mechanism was interpreted as ligand exchange. The effects of co-existing anions on the nitrate sorption followed the decreasing order of Cl - > SO 4 2- > PO 4 3- . Furthermore, the adsorption isotherms were well described by the Langmuir model, and the sorbent could exhibit a quite competitively high capacity of 37.3613 mg·g -1 for nitrate removal. In addition, the accordance of sorption kinetics with the pseudo-second order model implied that the sorption could be a multi-stage controlled chemical process. In addition, the thermodynamic parameters suggested that the sorption reaction could be a spontaneous and endothermic process. The results demonstrated that the Fe/Mn bimetallic oxide coated biochar could serve as a promising agent for nitrate removal from water.

Objective: To study the biological characteristics of new retrograde filling materials iRoot BP plus and iRoot FS., Methods: (1) The roots were cut into 3 mm in length, and the root canals were prepared to 1 mm in diameter, followed by being filled with iRoot BP plus, iRoot FS, or mineral trioxide aggregate (MTA). The specimens were immersed in simulated body fluid (SBF). The ability of mineralization in vitro was detected through three studies. First, the mineralization of specimens was analyzed through scanning electron microscope observations and energy dispersive X-ray spectrometer. Then, the pH of SBF was monitored using pH meter. (2) The extracts were gained by immersing blocks of iRoot BP plus, iRoot FS, and MTA (8 mm diameter and 2 mm height) into dulbecco's modified eagle medium (DMEM). The effects of the extracts on proliferation of MG63 cells were detected through MTT assay. The gene expression level of alkaline phosphatase (ALP) was analyzed by quantitative real-time PCR, and the expression of ALP activity was observed by ALP activity staining., Results: (1) The formation of minerals could be observed on the surfaces of iRoot BP plus, iRoot FS, and MTA at the end of 24 h, and there were more amounts of apatite aggregated after 14 days. The values of Ca/P ratios of apatites were 1.43, 1.39, and 1.51, respectively. (2) The pH of SBF could be raised to 8.09±0.07, 7.91±0.06, and 8.11±0.06, respectively, significantly higher than the blank. (3) The extracts of iRoot BP plus, iRoot FS, and MTA of dilutions of 1:5 and 1:10 presented no effect of proliferation of MG63 cells. (4) iRoot BP plus and iRoot FS could significantly up-regulated the levels of ALP messenger RNA expression, while there was no obvious difference in ALP staining among the iRoot BP plus, iRoot FS, MTA, and the blank., Conclusion: The present study shows that iRoot has displayed good mineralization capability in vitro and capability to promote differentiation and mineralization of MG63 cells, inferring that iRoot may have good bioactivity.

As one of the manganese oxides, which are easily generated and widely distributed in supergene environment, manganite participates in the oxidation of dissolvable sulfide (S²⁻), and affects the migration, transformation, and the fate of sulfides. In the present work, the redox mechanism was studied by determining the intermediates, and the influence of initial pH and oxygen atmosphere on the processes were studied. The chemical composition, crystal structures and micromorphologies were characterized by XRD, FTIR and TEM. The concentration of S²⁻ and its oxidation products were analyzed using spectrophotometer, high performance liquid chromatograph and ion chromatograph. The results indicated that elemental sulfur was formed as the major oxidation product of S²⁻ oxidation, and decreased pH could accelerate the oxidation rate of S²⁻ in the initial stage, however, there was no significant influence on final products. Elemental S could be further oxidized to S₂O₃²⁻ when the reaction system was bubbled with oxygen, and manganite exhibited excellent catalytic performance and chemical stability during the oxidation of dissolvable sulfide by oxygen. After reaction of more than 10 h, the crystal structure of manganite remained stable.

Hydrotalcites are not only considered as important absorbents in water treatment and but also widely used as super capacitor materials. In this study, NiAl metal oxide (NiAl-MMO) films, which were the calcined products of hydrotalcite-like compounds, were grown on the surface of a foam nickel by an in-situ growth method using a foam nickel substrate as the nickel source. The prepared NiAl-MMO films electrodes materials had stable electrochemical capability, remarkable electrochemical capacitor, and gave a highest specific capacitance of 667 F x g(-1). The desalination performance of material indicated high voltage and weakly alkaline solution were favored for desalination. A highest desalination efficiency was up to 58.17% when the initial concentration of Cl- was 0.003 mol x L(-1), the voltage value was 1.0 V and pH value was 8. The adsorption saturated electrodes could be rapidly regenerated with a desorption rate of 87.96% by electrodes reversion. This study provides a new choice for desalination in wastewater treatment.

To investigate the effect of pH on the oxidation of anilines by potassium permanganate, aniline and p-Chloroaniline were taken as the target contaminants, and the experiments were conducted under the condition with potassium permanganate in excess over a wide pH range. The reaction displayed remarkable autocatalysis, which was presumably ascribed to the formation of complexes by the in situ generated MnOx and the target contaminants on its surface, and thereby improved the oxidation rate of the target contaminants by permanganate. The reaction kinetics was fitted with the pseudo-first-order kinetics at different pH to obtain the pseudo-first-order reaction constants (k(obs)). The second-order rate constants calculated from permanganate concentration and k,b, increased with the increase of pH and reached the maximum near their respective pKa, after which they decreased gradually. This tendency is called parabola-like shaped pH-rate profile. The second-order rate constants between permanganate and anilines were well fitted by the proton transfer model proposed by us in previous work.

Filters are widely applied in drinking water treatment plants. Our previous study, which explored the asenic redox in a filter of drinking water plant treating underground water, found that As3+ could be oxidized to As5+ by biogenic manganese oxides, while As5+ could be reduced to As3+ by some microbial arsenic reductases in the biofilter system. This microbial competition could influence the system stability and treatment efficiency. To explore its mechanism, this study selected a manganese-oxidizing bacterial strain (Pseudomonas sp. QJX-1) and a arsenic-reducing strain (Brevibacterium sp. LSJ-9) to investigate their competitive relationship in nutrient acquisition and arsenic redox in the presence of Mn2+, As3+ or As5+ The results revealed that the concentration and valence of Mn and As varied with different reaction time; biological manganese oxides dominated the arsenic redox by rapidly oxidizing the As3+ in the existing system and the As3+ generated by arsenic reductase into As. PCR and RT-PCR results indicated that the arsenic reductase (arsC) was inhibited by the manganese oxidase (cumA). The expression of 16S rRNA in QJX-1 was two orders of magnitude higher than that in LSJ-9, which implied QJX-1 was dominant in the bacterial growth. Our data revealed that hydraulic retention time was critical to the valence of arsenic in the effluent of filter in drinking water treatment plant.

The mixture of V2O5-WO3/TiO2 catalyst and two kinds of Activated Carbons (AC) (AC-1: based on lignite; AC-2: based on coconut shell) was used to destroy gas phase PCDD/Fs with high concentration (9. 80 ng.m-3, evaluated by international toxic equivalence quantity (I-TEQ) under low thermal temperature (160°C) based on a dioxin generating system. After mixing with AC, removal efficiency (RE) and destruction efficiency (DE) of PCDD/Fs increased by 20% compared with only catalyst condition. In comparison with mixture of AC based on coconut shell, mixture of AC based on lignite had lower RE-values and higher DE-values. The adjustments of the ratio of catalyst and AC could cause the different degradation effects, and RE-values increased and DE-values decreased with increasing proportions of catalyst. When the volume fraction of oxygen was 0% in experimental atmosphere, catalyst could lose its activity and most PCDD/Fs were not oxidized but adsorbed by the mixture. RE and DE-values increased with increasing content of oxygen. The addition of ozone (concentration of 200 mg.m-3) could improve catalytic oxidation effects to a certain degree. However, ozone might react with AC, which could influence the lifetime of the mixture. Under 200°C, the mixture with proportion of AC: catalyst = 1:1 and in the present of 200 mg.m-3 ozone conditions, the highest RE and DE-value were obtained with 98. 0% and 94. 8% respectively, and the concentration of PCDD/Fs residual in off-gas was only 0. 51 ng.m-3 evaluated by I-TEQ.

The solidification/stabilization (S/S) of chromite ore processing residue (COPR) was performed using zero-valent iron (ZVI) and lime-activated ground granulated blast furnace slag (GGBFS). The degree of Cr immobilization was evaluated using the leaching procedure, mineral composition analysis and morphology analysis. Semi-dynamic leaching tests were implemented to investigate the potential for reusing the final treatment product as a readily available construction material. The results showed that after reduction, all of the S/S treated COPR samples met the pollution control limit of bricks and building block products (Chinese standard HJ/T 301-2007) produced with COPR for total Cr (0.3 mg x L(-1)), the compressive strength of all the S/S samples could meet the compressive strength standard (15 MPa) for producing clay bricks, and Cr existed as the specie that bound to Fe/Mn oxides in the S/S samples. At the same time, all of the S/S treated specimens tested were suitable for utilization at certain levels.

A novel rapid green one-step method was developed for the preparation of manganese modified diatomite (Mn-D) by treating roasted diatomite with an acidic permanganate solution. The effects of calcination temperature and mass ratio of KMnO4 and diatomite (p) on aniline removal efficiency of Mn-D were investigated. The removal kinetics and mechanism of aniline by Mn-D were also discussed. The results showed that when the optimal calcination temperature was 450 degrees C, p was 1.6, and the loading amounts of δ-MnO2 was 0.82 g x g(-1), Mn-D had a great performance for aniline removal, and more than 80% of aniline was adsorbed within 10 minutes, accompanied with the release of Mn2+. In acidic conditions, the adsorption process on Mn-D followed pseudo-second-order and was mainly controlled by intra-particle diffusion. The best fitting of the experimental adsorption data was given by the Freundlich equation. Gas chromatograph-mass spectrometer was applied to identify the reaction intermediates at different times, and azobenzene was found to be the main reaction intermediate in the degradation system. Based on the above observations, the possible degradation pathway of aniline by Mn-D was proposed.

The morphological structure and electrochemical properties of the electrode materials have direct impact on the electrosorption results. In this paper, Manganese dioxide ( MnO2) was composed on flexible carbon fiber paper ( CFP) via anodic electrodeposition technique to prepare the MnO2/CFP hybrid electrodes. The electrodes materials prepared showed stable electrochemical property, remarkable electrochemical capacitance, and the specific capacitance reached up to 360 F x g(-1). Electrosorption was conducted with this MnO2/CFP hybrid electrode to treat the waste water with an initial Pb2+ concentration of 6 mg x L(-1), and the effects of deposition time, initial pH, and voltage value on the electrosorption were investigated. It was shown that when the electrodeposition time was 500 s and the application of voltage value was 1.0 V, pH = 5.0, the best electroabsorption result was achieved. After 3 h electrosorption, the residual Pb2+ in the solution was lower than 0.01 mg x L(-1), and the removal efficiency could reach 99%. This study provides a new technology option for the removal of heavy metal ions in low concentrations in the waste water.

To evaluate the properties of solidifying volatile oil with graphene oxide, clove oil and zedoary turmeric oil were solidified by graphene oxide. The amount of graphene oxide was optimized with the eugenol yield and curcumol yield as criteria. Curing powder was characterized by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The effects of graphene oxide on dissolution in vitro and thermal stability of active components were studied. The optimum solidification ratio of graphene oxide to volatile oil was 1:1. Dissolution rate of active components had rare influence while their thermal stability improved after volatile oil was solidified. Solidifying herbal volatile oil with graphene oxide deserves further study.

Silver bismuth oxide(BSO) was prepared by a simple ion exchange-coprecipitation method with AgNO3 and NaBiO, .2H2O as raw materials, and then used to oxidatively degrade tetrabromobisphenol A(TBBPA). Effects of the molar ratio of Ag/Bi during BSO preparation and the BSO dosage on the degradation of TBBPA were investigated. The results showed that under the optimized conditions (i.e., the Ag/Bi molar ratio of 1:1, BSO dosage of 1 g x L(-1), 40 mg x L(-1) of TBBPA was completely degraded and the removal of total organic carbon achieved more than 80% within 7 min. The degradation intermediates of TBBPA were identified by ion chromatography, gas chromatograph-mass spectrometer and X-ray photoelectron spectroscopy. The degradation pathway of TBBPA included the debromination, the cleavage of tert-butyl group and the open epoxidation of benzene ring. Based on a quenching study of NaN3, singlet oxygen was proved to play a dominant role in the TBBPA degradation.

In this study, a Fe-La composite oxide nanoadsorbent was synthesized via a facile co-precipitation process. This adsorbent was well characterized with various techniques and its As (III) adsorption performance was investigated. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) analyses indicate that the Fe-La composite oxide is formed with nanoparticles (20-200 nm). X-ray powder diffraction (XRD) analysis shows that the Fe-La composite oxide is similar to the crystal structure of La (OH)3. The specific surface area of Fe-La composite oxide is 99. 3 m2 x g(-1) and the isoelectric point is 7.8. The prepared Fe-La composite oxide nanoadsorbent is effective for As(III) removal from water. The isotherm data is well fitted with the Langmuir model (R2 = 0.95) with a maximal As(III) adsorption capacity of 58.2 mg x g(-1) at pH 7.0. The adsorption of As(III) is very fast and over 80% of the equilibrium adsorption capacity is obtained within 240 min. Elovich model (R2 = 0.97) is more suitable to describe adsorption kinetic data. The As(III) adsorption is dependent on solution pH. The effect of coexisting anions on As(III) adsorption increases in the order of SO4(2-) < CO3(2-) < SiO3(2-) < PO4(3-).

Laponite clays composited with alumina, ceria and zirconia etc. were prepared using polyoxocations or simple metal ions as precursors, and then cobalt oxide was loaded onto them to obtain the catalysts. The results showed that compared with laponite clays, the as-prepared laponite had wide range of pore size distribution and increased pore volume. The pore volumes of laponite clays composited with alumina and ceria were more than 0.75 cm3 · g(-1). N2 isotherm type was maintained after Co3O4 loading, however, the N2 adsorption decreased with the increase of Co3 O4 loading, indicating the decrease of pore volume, which was caused by the blockage of metallic oxide/clay composites support. Furthermore, dispersion and catalytic performance of the catalysts were significantly influenced by the composited metallic elements. It was shown that according to the diffraction peak half-width of 311 crystal facet and scherrer equation, when the Co loading was 21.3% at laponite clays composited with Fe, Zr, Ce, Al, the average sizes of Co3O4 were 17.2, 16.0, 16.5 and 18.0 nm, respectively. Alumina composited clay with 21.3% Co loading showed high catalytic activity, the complete conversion temperature of benzene was 350°C. Among metallic oxide/laponite composites, the ZrO composited laponite with 21.3% Co loading exhibited the best catalytic performance, which could completely convert benzene at 310°C.

Redox conditions of the polluted paddy soil with exogenous As were simulated by redox reaction apparatus after flowing N2 and O2 applied with different forms of inorganic sulfur(CK-S0, elemental sulfur-S1 and sulfate-S2). Results showed that redox potential (Eh) was about -100 - -200 mV and the pH 7.0-8.0 and the pe + pH 4-7 in soil solution when flowed N2, and Eh about 200 mV and the pH 6.5-7.5 and pe + pH 9-12 when continuously flowed O2. Concentrations of the dissolved Fe in soil solution were in 1.2-1.6 mg x L(-1) either flowed N2 or O2, and the order of Fe concentrations was AsS0 treatment > AsS1 treatment > AsS2 treatment. Amounts of soil Fe oxide by HCl extraction from different treatments were 5 g · kg(-1) lower than the original soil [(21.4 ± 0.3) g · kg(-1)] when flowed N2, and it was in favor of the transformation of crystal Fe into amorphous iron and Fe2+. Activity of Fe oxides from different treatments increased comparing to that of the original soil (46. 8%), and the order of activity of Fe oxides was AsS2 treatment (49.4%) < AsS1 treatment (60%). Fe2+ in solution and FeS were oxidized into Fe3+, and hydrolysis of Fe3+ was produced into Fe(OH)3 precipitation when flowed O2. It increased the contents of acid-soluble and crystal Fe oxide, and the order of activity of Fe oxides was AsS1 (41.2%) treatment > AsS2 (36.1%) treatment. Concentrations of As in soil solution were in the order of AsS0 [(1.13 ± 0.04) mg · L(-1)] > AsS1 [(0.89 ± 0.01) mg L(- 1)] > AsS2 [ (0.77 ± 0.04 )mg · L(-1)] when flowed N2 and was AsS1 [(0.77 ± 0.01) mg · L(-1)] > AsS0 [(0.20 ± 0.09 ) mg · L(-1)] > AsS2 [(0.09 ± 0.01) mg · L(-1)] when flowed O2. The proportions of arsenic fractions followed the order of the residual phases (34.9%-41.4%) ≈ specifically-sorbed (37.4%-39.5%) > well-crystallized hydrous oxides of Fe/Mn (23.3%-25.6%) > non-specifically sorbed (2.4%-3.3%) > amorphous hydrous oxides of Fe/Mn (0.5%-0.8%) when flowed N2, and was the residual phases (30.8%-39.3%) specifically-sorbed (30.3%-34.7%) > well-crystallized hydrous oxides of Fe/Mn (26.0%-28.7%) > amorphous hydrous oxides of Fe/Mn (9.3%-10.7%) > non-specifically sorbed (0.5%-1.6%) when flowed O2. Arsenic from amorphous hydrous oxides of Fe/Mn raised about 9% by flowing O2 than by flowing N2. This could be the effect of the aging amorphous Fe/Mn on the transformation of As, and the increased activity of iron oxide under reducing conditions and enhanced mobility of Arsenic. Elemental surfer system could increase mobility of arsenic more than sulfate system which may decrease degree of activity of iron oxide.

Objective: To explore the apoptotic mechanism of human hepatic carcinoma cell line HepG2 induced by arsenic trioxide (As2O3)., Methods: The human hepatoma cell line HepG2 was treated with 0, 2.5, 5 and 10 micromol/L arsenic trioxide for 24 h. Cytotoxicity was tested by MTT assay (additional 25 and 50 micromol/L arsenic trioxide treatment groups), cellular apoptosis were detected by flow cytometry, reactive oxygen species (ROS) level were quantified by DCFH-DA fluorescent probe staining and glutathione content were measured by DTNB method with commercial kits. Western blot assay was used to detect the protein expression of gamma-glutamylcysteine synthetase (gamma-GCS, GCLC and GCLM subunits) and nuclear factor erythroid 2-related factor 2 (Nrf2)., Results: With the increase of arsenic trioxide concentration, cellular survival, glutathione content and gamma-GCS (GCLC and GCLM subunits) protein expression level decreased (P < 0.05); while cellular apoptotic rate, reactive oxygen species level and Nrf2 protein expression increased (P < 0.05)., Conclusion: Arsenic trioxide induces the apoptosis of human hepatoma cell line HepG2 through ROS induction, gamma-GCS expression inhibition and cellular glutathione content depletion.

A simple ultrasound-assisted co-precipitation method was developed to prepare magnetic Fe3O4/graphene oxide (Fe3O4/ GO) nanoparticles. The characterization with transmission electron microscope (TEM) indicated that the products possessed small particle size. The hysteresis loop of the dried Fe3O4/GO nanoparticles demonstrated that the sample had typical features of superparamagnetic material. Batch adsorption studies were carried out to investigate the effects of the initial pH of the solution, the dosage of adsorbent, the contact time and temperature on the adsorption of methylene blue. The results indicated that the composites prepared could be used over a broad pH range (pH 6-9). The adsorption process was very fast within the first 25 min and the equilibrium was reached at 180 min. The adsorption equilibrium and kinetics data fitted well with the Langmuir isotherm model and the pseudo-second-order kinetic model. The adsorption process was a spontaneous and endothermic process in nature. The composite exhibited fairly high adsorption capacity (196.5 mg.g-1) of methylene blue at 313 K. In addition, the magnetic composite could be effectively and simply separated by using an external magnetic field, and then regenerated by hydrogen peroxide and recycled for further use. The results indicated that the adsorbent had a potential in the application of the dye wastewater treatment.

Stabilization of Pb, Cd and Zn spiked soil by using lime-stabilized sewage sludge( LSS) as amendment was investigated in this study, and the effectiveness was evaluated by using leaching tests ( TCLP, SPLP and de-ionized water) and modified BCR sequential extraction procedure. The results of TCLP indicated that the concentrations of heavy metals in TCLP leachate reduced significantly with the increase of the mass percentage of the LSS and the leaching reduction rates were as high as 99. 54% for Zn, 99. 60% for Pb, 99. 85% for Cd at 40% of LSS addition. When evaluated by SPLP and de-ionized water leaching method, the concentrations of Zn and Pb in leachate decreased obviously at 10% and 20% of LSS additions, but subsequently increased at 30% and 40% because of redissolution of Zn and Pb at strong base condition. After pH value of LLS-stabilized soil was adjusted by ferrous sulfate and phosphoric acid for recovering soil plantation function, the pH value of the soil decreased effectively, in the meantime promoting the stabilization effectiveness of Pb and Zn. The BCR test revealed that compared with the spiked soil exchangeable proportion of Zn, Pb, Cd in the soil and the soils adjusted by ferrous sulfate obviously declined, which implied the migration for Pb, Cd and Zn of contaminated soil could be confined. This study results show that municipal LSS can be reused in the stabilization of heavy metal contaminated soils and physical and chemical properties of LLS-stabilized soil are improved for plantation.

Hydrotalcite-based MgAl mixed oxides were synthesized by urea hydrolysis and constant-pH coprecipitation methods, and characterized by means of X-ray diffraction (XRD) , thermal gravity analysis-differential thermal gravity (TG-DTG) , scanning electron microscope (SEM), N2-adsorption/desorption and CO2 temperature programmed desorption (CO2-TPD), and their adsorption performances for SO2 were also tested. It was found that MgAl mixed oxides prepared by coprecipitation method would facilitate the catalyst to maintain a high specific area (148. 1 m2.g-1) and more basic sites, which resulted in higher SO2 adsorption capacity and velocity. The SO2 adsorption capacity of the mixed oxides prepared by urea hydrolysis and constant-pH coprecipitation methods were 0.55 g.g-1and 0. 79 gg-1 respectively at 700 degreeC.

A bacterium with high manganese oxidizing activity was isolated from a biological manganese removal filter and named as H1. Based on its characteristics and the analysis of 16S rDNA sequence, the strain H1 belonged to the genus Aminobacter sp. and its manganese oxidizing ability had never been reported. In this paper, the microbiologic properties of the strain H1, the manganese oxidation mechanisms and characteristics of biogenic manganese oxides were investigated. The results showed that the maximal tolerant Mn concentration of strain H1 was 50 mmol x L(-1), and Mn(II) could be completely removed by strain H1 when the concentration was lower than 10 mmol x L(-1). Strain H1 could oxidize Mn2+ by both the production of manganese oxidizing activity factor and alkaline metabolites during growth, which were synthesized in the cell and then secreted into extracellular culture medium. During the oxidation process, the intermediate of soluble Mn(III) was detected. SEM showed that the biogenic manganese oxides were amorphous and poorly-crystalline, and it closely combined with bacteria. The components of the biogenic manganese oxides produced by strain H1 were identified as MnCO3, MnOOH, Mn3O4 and MnO2 by XRD, XPS and SEM-EDX.

We prepared silver nanoparticles/polyethyleneimine-reduction graphene oxide (AgNP/rGO-PEI) composite materials, and evaluated their quality performance in our center. Firstly, we prepared AgNP/rGO-PEI, and then analysed its stability, antibacterial activity, and cellular toxicity by comparing the AgNP/rGO-PEI with the silver nanoparticles (PVP/AgNP) modified by polyvinylpyrrolidone. We found in the study that silver nanoparticles (AgNP) distributed relatively uniformly in AgNP/rGO-PEI surface, silver nanoparticles mass fraction was 4.5%, and particle size was 6-13 nm. In dark or in low illumination light intensity of 3 000 lx meter environment (lux) for 10 days, PVP/AgNP aggregation was more obvious, but the AgNP/rGO-PEI had good dispersibility and its aggregation was not obvious; AgNP/rGO-PEI had a more excellent antibacterial activity, biological compatibility and relatively low biological toxicity. It was concluded that AgNP/rGO-PEI composite materials had reliable quality and good performance, and would have broad application prospects in the future.

Different forms of heavy metals in soil will produce different environmental effects, and will directly influence the toxicity, migration and bioavailability of heavy metals. This study used lime, fly ash, dried sludge, peanut shells as stabilizers in the treatment of heavy metals in mineral waste residues. Morphological analyses of heavy metal, leaching experiments, potted plant experiments were carried out to analyze the migration and transformation of heavy metals. The results showed that after adding stabilizers, the pH of the acidic mineral waste residues increased to more than neutral, and the organic matter content increased significantly. The main existing forms of As, Pb, and Zn in the mineral waste residues were the residual. The contents of exchangeable and organic matter-bound As decreased by 65.6% and 87.7% respectively after adding fly ash, dried sludge and peanut shells. Adding lime, fly ash and peanut shells promoted the transformation of As from the Fe-Mn oxide-bound to the carbonate-bound, and adding lime and fly ash promoted the transformation of Pb and Zn from the exchangeable, Fe-Mn oxide-bound, organic matter-bound to the residual. After the early stage of the stabilization treatment, the contents of As, Pb and Zn in the leachate had varying degrees of decline, and adding peanut shells could reduce the contents of As, Pb and Zn in the leachate further. Among them, the content of As decreased most significantly after treatment with fly ash, dried sludge and peanut shells, with a decline of 57.4%. After treatment with lime, fly ash and peanut shells, the content of Zn decreased most significantly, by 24.9%. The addition of stabilizers was advantageous to the germination and growth of plants. The combination of fly ash, dried sludge and peanut shell produced the best effect, and the Vetiveria zizanioides germination rate reached 76% in the treated wasted mineral residues.

Yangtze River raw water from Yangshupu Water Plant, Shanghai was studied in this paper for reduced formation potential of chlorination and chloramination disinfection by-products (DBPs) after pre-oxidation by three kinds of common pre-oxidants, whiich were potassium permanganate, chlorine and chlorine dioxide. Results of chlorination showed that removal effectiveness of all the selected oxidants on total chlorination DBPs was not significant, and the reduction percentages by ClO2, Cl2 and KMnO4 were 8.4%, 5.7% and 3.9%, respectively. The order of DBPs control effect was ClO2, > Cl2 > KMnO4. As to Yangtze River raw water in case of chlorine disinfection, using ClO2 as pre-oxidation agent showed relatively better effect on removal of DBPs. However, chloramination results demonstrated that impacts of the three preoxidants on DBPs formation potential were quite different, and the reduction percentages by ClO2 and KMnO4 were 18.1% and 4.1%, respectively, while pre-chlorination increased the potential by 12.3%. These results revealed that ClO2 had the highest removal effectiveness, meanwhile pre-chlorination should be avoided due to its notable increase in DBPs formation.

CuCeOx composite catalysts were synthesized via coprecipitation (COP-CuCeO,) and incipient impregnation (IMP-CuCeOx) methods, respectively. The physicochemical properties of the samples were characterized by XRD, low-temperature N2 sorption, H2-TPR and O2-TPD. The influences of reactant composition and concentration, reaction space velocity, O2 content, H2O concentration, and catalyst type on the oxidation behaviors of benzene, toluene, and n-hexane emitted from petrochemical industry were systematically investigated. In addition, the related kinetic parameters were model fitted. Compared with IMP-CuCeOx, COP-CuCeOx had well-dispersed active phase, better low-temperature reducibility, and more active surface oxygen species. The increase of reactant concentration was unfavorable for toluene oxidation, while the opposite phenomenon could be observed in n-hexane oxidation. The inlet concentration of benzene was irrelevant to its conversion under high oxidation rate. The introduction of benzene obviously inhibited the oxidation of toluene and n-hexane, while the presence of toluene had a positive effect on beuzene conversion. The presence of n-hexane could promote the oxidation of toluene, while toluene had a negative influence on e-hexane oxidation. Both low space velocity and high oxygen concentration were beneficial for the oxidation process, and the variation of oxygen content had negligible effect on n-hexane and henzene oxidation. The presence of H2O noticeably inhibited the oxidation of toluene, while significantly accelerated the oxidation procedure of henzene and n-hexane. COP-CuCeOx had superior catalytic performance for toluene and benzene oxidation, while IMP-CuCeOx showed higher n-hexane oxidation activity under dry condition. The oxidation behaviors under different conditions could be well fitted and predicted by the pseudo first-order kinetic model.

The effect of metal ions on elimination of 4-t-OP by synthetic delta-MnO2 suspension at pH 4.0 was studied. Experiments indicated that the removal of 4-t-OP by delta-MnO2 achieved 100% at reaction time of 150 min. However, the removal of 4-t-OP by delta-MnO2 was restrained when metal ions were added, and the higher concentration of metal ion was, the stronger the inhibition produced. Additionally, there were apparent differences among the inhibitory effect of the tested metal ions. Firstly, Pb2+ and Mn2+ had the strongest effect at pH 4.0, followed by the transition metal ions, then the alkaline earth ions, while the alkali metal ions had little influence on the removal of 4-t-OP by delta-MnO2. Also comparing the adsorption results of metal ions by delta-MnO2, Pb2+ showed the greatest attraction with delta-MnO2, and among the other metal ions, transition metal ions were adsorbed a little more strongly on delta-MnO2 than alkaline earth metal ions. Consequences showed that the inhibitory effects of metal ions were due to their occupying reactive sites on delta-MnO2 surface, which competed with 4-t-OP. Moreover, the dissimilar suppressions were contributed by the different adsorption capacities, surface structure change of MnO2 and the difference of free metal ion percentage in solution as well as metal ions radii.

A novel biomass columnar activated carbon was prepared from walnut shell and pyrolusite was added as a catalyst. The activated carbon prepared was used for flue gas desulphurization in a fixed-bed reactor with 16 g of activated carbon. The impact of operating parameters such as SO2 inlet concentration, space velocity, bed temperature, moisture content and O2 concentration on the desulfurization efficiency of activated carbon was investigated. The results showed that both the breakthrough sulfur capacity and breakthrough time of activated carbon decreased with the increase of SO2 inlet concentration within the range of 0.1% -0.3%. The breakthrough sulfur capacity deceased with the increase of space velocity, with optimal space velocity of 600 h(-1). The optimal bed temperature was 80 degrees C, and the desulfurization efficiency can be reduced if the temperature continue to increase. The presence of moisture and oxygen greatly promoted the adsorption of SO2 onto the activated carbon. The best moisture content was 10%. When the oxygen concentrations were between 10% and 13%, the desulfurization performance of activated carbon was the highest. Under the optimal operating conditions, the sulfur capacity of activated carbon was 252 mg x g(-1), and the breakthrough time was up to 26 h when the SO2 inlet concentration was 0.2%.

Experiments were carried out on laboratory-scale electrically heated tube furnace sewage sludge combustion with different adsorbents. Four solid adsorbents (calcium oxide, Alumina, fly ash and kaolin) were used to control the emission of heavy metals (Pb, Cd, Cu, Cr, Ni, Zn) during the sewage sludge incineration. The results showed that the heavy metals tended to be fixed and left over in the incineration bottom ash with the addition of calcium oxide, Alumina, fly ash and kaolin. With the increase of the solid adsorbent ratio, the residual rate of heavy metals in the bottom ash also increased. Incineration temperature had a great influence on the heavy metal adsorption effect of the solid adsorbent. The forms, melting point and boiling point of the heavy metals were found to be important factors that determined its volatility. There was huge difference in the inhibitory effect of different adsorbents on heavy metals migration. From the view of controlling heavy metal evaporation, the adsorbents kaolin and CaO were superior to the other adsorbents. The interaction between the active center of the solid adsorbent and the molecules of the heavy metal compounds depended on the distribution of these active sites and the chemical properties of the heavy metals.

Through concentrated application of lime, sewage sludge and lime + sewage sludge on the sloping top of the hilly woodlands, the restoration effects of the three soil amendments on the acidified soil of hilly woodland were studied. The results showed that: (1) Joint application of sewage sludge + lime can significantly (P < 0.05) decrease soil acidity, promote the rapid increase in soil organic matter and nitrogen content, increase soil cation exchange capacity, and effectively improve acidified soil. (2) Through natural diffusion mechanisms of surface and subsurface runoff, a large area of acidified soil of hilly woodlands can be restored by concentrated application of soil amendments on the sloping top of the hilly woodlands. (3) It is conducive to solve the pollution problems of the urban sewage sludge by using municipal sewage sludge to restore acidified soil, but only for the restoration of acidified soil of timber forest.

A series of MnO(x)/nano-TiO2 catalysts were prepared and their application in degradation of beta-naphthol by catalytic wet air oxidation (CWAO) was investigated. The catalysts preparation conditions, reaction conditions and its stability were tested. The catalysts had been characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) measurements. The results showed that the decrease of the COD removal for the degradation of beta-naphthol at high Mn loading was due to the aggregation of the highly dispersed Mn species and the formation of the correlated crystals. The decline of the COD removal at high calcination temperature was probably attributed to the weak electron transfer between Mn2O3 and MnO2 and the formation of the inactive Mn2O3. The COD removal had been falling slightly when the catalyst was used 6 times, and this was likely related to the decrease of the diffraction peaks. The catalyst had a high activity when the Mn loading (mass fraction) was 4% and the calcination temperature was 450 degrees C. The COD removal was up to 96.4% at 110 degrees C and 0.5 MPa with this catalyst. The COD removal of 92.4% could be obtained with the MnO(x)/nano-TiO2 catalyst was recycled 6 times. The Mn leaching at 50, 80, 110 and 150 degrees C were all less than 9.3 mg x L(-1) by means of Atomic Absorption Spectroscopy (AAS). The probable degradation pathway was proposed according to some publications.

The UV-Visible absorption spectrum of industrial wastewater was explored to introduce a substituting method determining the color of water, and to compare the decolorization efficacy of different disinfectants. The results show that the visible absorption spectrum(350-600 nm), instead of ultraviolet absorption spectrum, should be applied to characterize the color of wastewater. There is a good correlation between the features of visible absorption spectrum and the true color of wastewater. Both ozone and chlorine dioxide has a better decolorization performance than chlorine. However, the color of chlorine dioxide itself has a negative effect on decolorization. The changes in the features of visible absorption spectrum effectively reflect the variations in the color of wastewater after disinfection.

In situ immobilization of Pb and Cd in soil of two gardens in Golden Orchard of Chongqing was studied using soil ameliorants, which included eight treatments: control, quicklime, superphosphate, organic manure, quicklime + superphosphate, quicklime + organic manure, superphosphate + organic manure, and quicklime + superphosphate + organic manure. The results showed that all ameliorant treatments could decrease soil acidity in both the loquat garden and peach garden except the superphosphate treatment. Compared with the control, the soil pH in the two gardens increased by 0. 93 and 0. 79 with quicklime treatment for 120 d, respectively. Ameliorant treatments could decrease the bioavailability of Pb and Cd in the soil, and thus reduce the contents of Pb and Cd in the fruits. The available Pb contents in the soil of loquat garden and peach garden significantly decreased after the 150 d treatment with quicklime and superphosphate, by 3.46% and 3.56%, respectively, and the Pb contents in loquat and peach decreased by 18.3% and 14.44%, respectively. The available Cd content in the soil of loquat garden decreased by 10. 95% after the 150 d treatment with quicklime. The available Cd content in the soil of peach garden decreased by 7.09% after the 150 d treatment with quicklime, superphosphate and organic manure. Ameliorant treatments could further decrease the Cd content in loquat, and the Cd contents in loquat and peach decreased by 30.91% and 24.62% with quicklime treatment, respectively.

In order to reveal the sorption behavior of phenanthrene (PHE) on engineered nano-silica, batch equilibriums were conducted to study the effects of heating, solution pH, and heavy metal ion (Ni2+) on PHE sorption, and a site energy distribution model was used to analyze the changes of sorption behavior. The results demonstrated that the sorption isotherm of PHE could be fitted well by the Freundlich model. The sorption capacity of the original nano-silica (PNS) was enhanced by heating (heated nano-silica, HNS), with the Freundlich adsorption coefficient (lgK(F)) increasing from 1.48 to 2.43. The nonlinearity of sorption isotherm increased after heating. The sorption characteristics together with pore distribution and surface area analysis suggested that PHE sorption on nano-silica was a combination of pore-filing and surface sorption, with the microspores and mesopores of nano-silica playing a major role. While changes in solution pH did not show a significant effect on the sorption of PHE on PNS, the sorption of PHE on HNS decreased significantly with increasing pH, with IgK(F) reducing by 73.7% when pH increased from 4.0 to pH 8.0. The pH caused differences in sorption capacity could be mainly explained by zeta potentials of nanoparticles. High pH enhanced the charge of nanoparticles, and reduced the pore accessibility. The effect of Ni2+ on PHE sorption on HNS varied with its concentration. At low concentration (<5 mmol x L(-1)), Ni2+ suppressed PHE sorption, while at a higher concentration, NiZ2 enhanced the sorption of PHE at a lower concentration (50 microg x L(-1)), and the inhibition on the sorption of PHE at a higher concentration (500 microg x L(-1)) did not increase further. This complex pattern was a result of concurrence of multiple processes.

A novel lead dioxide electrodes co-doped with rare earth and polytetrafluoroethylene (PTFE) were prepared by the electrode position method and applied as anodes in sono-electrochemical oxidation for pharmaceutical wastewater degradation. The results showed that the APAP removal and the mineralization efficiency reached an obvious increase, which meant that the catalytic efficiency showed a significant improvement in the use of rare-earth doped electrode. The effects of process factors showed that the condition of the electrode had the best degradation efficiency with doped with Ce2O3 under electrolyte concentration of 14.2 g x L(-1), 49.58 W x cm(-2), 50 Hz, pH = 3, 71.43 mA x cm(-2). The APAP of 500 mg x L(-1) removal rate reached 92.20% and its COD and TOC values declined to 79.95% and 58.04%, the current efficiency reached 45.83% after degradation process for 2.0 h. The intermediates were monitored by the methods of GC-MS, HPLC, and IC. The main intermediates of APAP were p-benzoquinone, benzoic acid, acetic acid, maleic acid, oxalic acid, formic acid etc, and the final products were carbon dioxide and water. The goal of completely degradation of pollutant was achieved and a possible degradation way was proposed.

Fe-MnOx-CeO2/ZrO2 catalysts were prepared through impregnation method with nanometer ZrO2 as a carrier and used in selective catalytic reduction of NO with NH3 at low temperature. Effects of active component ratio and loading of promoter on the catalyst activity were investigated. The catalysts were characterized by means of XRD, SEM, EDS and BET. The effects of temperature, SO2 and H2O on NO conversion were studied and the results showed that in the absence of SO2 and H2O, the catalyst of 8% Fe-10% MnOx-CeO2/ZrO2 had good activity and stability as well as the NOx removal efficiency reached 85.23% at 120 degrees C and 92.0% at 180 degrees C. The presence of SO2 and H2O results in the catalyst deactivated. Properties of the catalyst on different reaction stages were characterized by FT-IR to study the inactivation mechanism of the catalyst. The results showed that the catalyst deactivation was due to the deposition of ammonium sulfate on the catalyst and the sulphation of the catalyst.

In this study, N-doped Ta2O5 samples which have strong absorption in visible domain, were prepared by the nitridation of Ta2O5 under NH4 flow and then added into photo-Fenton-like system to enhance Fe3+ reduction and atrazine degradation under visible light irradiation. The sample prepared at 700 degrees C under a NH3 flow rate of 0.3 L x min(-1) for 6 h showed the highest level of photocatalytic activity for Fe3+ reduction. The influence of various operational parameters such as the light intensity, input of N-doped Ta2O5, pH and initial concentrations of Fe3+, H2O2 and atrazine were investigated. And the changesof H2O2 during the degradation were measured to explain the effect of the operational parameters. The degradation ratio of atrazine reached 97% after 60 min irradiation by 500 W Xe lamp under the conditions of pH = 2.6, [atrazine]0 = 18 mg x L(-1), [H2O2]0 = 2.5 mmol x L(-1), [Fe3+]0 = 0.5 mmol x L(-1) and the input of N-doped Ta2O5 = 0.6 g x L(-1).

Ti-base lead dioxide electrodes (Ti/PbO2) doped with rare earth La, Ce were prepared by the electrode position. The surface morphology and crystal structure of the electrodes was analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD), the results showed that, microstructure and crystal orientation of electrode surface changed after doping rare earth La, Ce, which made the electrode surface more dense and uniform. The electrochemical properties of the electrodes were tested by linear sweeping (LS) and cyclic voltammogram (CV), the experimental results show that, La, Ce doping improved the electrode overpotential of oxygen evolution and the peak current density, promoted the catalytic performance of the electrode. Different doping amount of modified electrodes were used to degrade methylene blue simulative dyeing wastewater, the results showed that, electrodes doped La and Ce respectively 8.0 g x L(-1) and 5.0 g x L(-1) have the best degradation efficiency and catalytic activity, for example, the removal of MB and its COD respectively researches 83.85%, 79.95% and 79.18%, 76.21%. The possible degradation pathways and mechanisms were also discussed.

Graphene is a kind of atomic crystal with two-dimensional polycyclic aromatic hydrocarbons planes, which is of great concern in various fields. This paper reviews the latest development of graphene-based materials in biomedical research fields in the recent years, including in vitro and in vivo toxicity, drug loading, targeting controlled release, as well as photodynamic therapy. These researches validate that the graphene-based materials indicate promising prospects in the application to biomedicine.

Manganese oxide octahedral molecular sieves (OMS-2) for VOCs catalytic combustion were synthesized by refluxing method. The crystal structure, particle morphology, pore structure and H2-reduction ability were characterized by XRD, SEM, N2 adsorption-desorption and H2-TPR techniques. The catalytic activities of the OMS-2 calcined at different temperatures in benzene combustion and the stability of the sample calcined at 300 degrees C were evaluated. The results indicated that the effect of calcinations temperature on the surface characters of catalysts was remarkable. With higher calcination temperature, the samples showed lower surface area and pore volume, but larger average pore size. At the same time, high calcination temperature leaded to low activity. The benzene conversion of the sample calcined at 300 degrees C was 50% degrees C at 200 degrees C and 90% at 250 degrees C, respectively. The catalytic activity exhibited only 5% reduction after reaction at 260 degrees C for 70 h, which indicated that the as-made catalysts were very stable after calcination at 300 degrees C.

Co3O4 nanorods were fabricated by the low-temperature hydrothermal method. The Co3O4 nanorods were formed through adding a small amount of surfactants (Polyvinylpyrrolidone, referred to as PVP) and reacting at 95 degrees C. Controlling the reaction time of preparation and pH of the solution can affect the properties of Co3O4 nanorods. X-ray diffraction (XRD), transmission electron microscopy (TEM) proved the as-prepared samples were Co3O4 nanorods in cubic phase. Hydrogen temperature programmed reduction (H2-TPR) and nitrogen adsorption-desorption experiment results showed that the size and pore structure of Co3O4 nanorods could be affected by different reaction time and pH, and led to the difference in specific surface area. The catalytic properties of Co3O4 nanorods were examined by degradation of gaseous toluene. The results showed that conversion of toluene was affected under low temperature by Co3O4 nanorods, which were prepared by different reaction time and pH. When the temperature was below 260 degrees C, the catalyst prepared in alkaline condition had the highest activity. However, when the temperature was higher than 260 degrees C, the conversion of toluene was hot significantly different.

Adsorption characteristics of mineral surface for heavy metal ions are largely determined by the type and amount of surface adsorption sites. However, the effects of substructure variance in manganese oxide on the adsorption sites and adsorption characteristics remain unclear. Adsorption experiments and powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) were combined to examine the adsorption characteristics of Pb2+, Cu2+, Zn2+ and Cd2+ sequestration by birnessites with different Mn average oxidation state (AOS), and the Mn AOS dependent adsorption sites and adsorption characteristics. The results show that the maximum adsorption capacity of Pb2+, Cu2+, Zn2+ and Cd2+ increased with increasing birnessite Mn AOS. The adsorption capacity followed the order of Pb2+ > Cu2+ > Zn2+ > Cd2+. The observations suggest that there exist two sites on the surface of birnessite, i. e., high-binding-energy site (HBE site) and low-binding-energy site (LBE site). With the increase of Mn AOS for birnessites, the amount of HBE sites for heavy metal ions adsorption remarkably increased. On the other hand, variation in the amount of LBE sites was insignificant. The amount of LBE sites is much more than those of HBE sites on the surface of birnessite with low Mn AOS. Nevertheless, both amounts on the surface of birnessite with high Mn AOS are very close to each other. Therefore, the heavy metal ions adsorption capacity on birnessite is largely determined by the amount of HBE sites. On birnessite surface, adsorption of Cu2+, Zn2+, and Cd2+ mostly occurred at HBE sites. In comparison with Zn2+ and Cd2+, more Cu2+ adsorbed on the LBW sites. Pb2+ adsorption maybe occupy at both LBE sites and HBE sites simultaneously.

Phenol was selected as a model compound. Factors, such as Ca2+, tannic acid, dose of kaolinite, dose of manganese dioxide formed in situ and pH, were invested on phenol removal in the process of enhanced coagulation by manganese dioxide formed in situ. Results showed that the addition of Ca2+ is beneficial for phenol removal. In the range of Ca2+ varied from 0 to 1.0 mmol x L(-1), the efficiency of phenol removal was enhanced more than 10%. Tannic acid can enhance phenol removal significantly when they are coexisted in water. As tannic acid was added to 10 mg x L(-1), phenol removal can be increased about 30% and 50% in the process of coagulation by AlCl3 and enhanced coagulation by manganese dioxide formed in situ, respectively. The dose of coagulant can be reduced in the process of enhanced coagulation with the addition of manganese dioxide formed in situ. The point of 1 mg x L(-1) manganese dioxide formed in situ linked with 30 mg x L(-1) AlCl3 can have the same phenol removal efficiency as the addition of 50 mg x L(-1) AlCl3. In the range of pH varied from 5 to 9, phenol can be removed with the high efficiency in the process of enhanced coagulation by manganese dioxide formed in situ. While under the strong acid condition and strong basic condition, phenol has lower removal efficiency.

This paper discussed a recent study of mercury removal by gaseous hydrogen chloride over novel Ce doped low vanadium V2O5-WO3/TiO2 catalysts under a bench scale condition. The performances on Hg(0) removal over the catalyst were tested in simulated flue gas with 80-100 microg x m(-3) Hg(0), 8% O2, 10 x10(-6) HCl, 8% H2O, 800 x10(-6) SO2 and balanced with N2. Results showed that about 95% of Hg(0) could be removed. According to the characterization results, BET surface areas had not significant influence on catalytic performance. XPS results indicated that Ce4+ oxide was a mainly form in the catalysts surface, which was beneficial for Hg(0) removal reactions. Water vapor slightly inhibited Hg(0) removal efficiency, due to the competitive adsorption, however, SO2 promoted the oxidation reactions, resulting in higher removal efficiencies.

Acid birnessite was treated with Na4P2O7 at pH 2, 4, 5 respectively. After the treatments, the species and content of manganese ion in the complex solution, and the variation of average oxidation state (AOS) of Mn in birnessite, and the amount of adsorbed Pb2+ and released Mn2+, H+ during the Pb2+ adsorption were investigated. The results indicate that after acid birnessite, the AOS of Mn is 3.670 which is treated by Na4P2O7 at different pH, Mn( III) located in the layer edge and part of Mn(III) located in the interlayer are released to the solution through complexation with Na4P2O7. The content of Mn(III) in the structure of original birnessite is very low. Small amount of Mn(II), which accounts for 4.70%-7.46% in the molar percentage of total released Mn, is also released simultaneously. The AOS of Mn of birnessites after treatment increases to 3.783 (pH 2), 3.786 (pH 4), 3.824 (pH 5) respectively. While the crystal structure of birnessite does not change after treatment, the amount of Mn(III) located above or below vacant cation sites decreases, and the amount of H+ located above or below vacant cation sites goes up in the structure of birnessites. The amount of vacant cation sites responsible for Pb2+ adsorption increases, which lead to the increase of the maximum amount of adsorbed Pb2+. Additionally, the distribution of Mn(III) in the structure of acid birnessite is deduced. About one sixth of Mn(III) locates in the layer edge, and five sixths of Mn(III) locates in the interlayer and the non layer edge.

The Al2O3,which has large specific surface area and is used as carrier,was prepared by sol-gel method in this study. Series catalysts of MnOx, CeO2 plus MnOx supported on Al2O3 by isometric impregnation method. The SCR denitrification experimental conditions were as follows: NH3 as reductive agent, certain gas velocity and suitable ratio of gas mixed was setup. Furthermore, the experiments of BET, XRD and SEM were also carried out respectively in order to obtain physicochemical properties of the prepared catalysts. The experimental results showed that the loading of active component and calcination temperature made a big difference to the catalysts' performance. With appropriate addition of CeO2, MnOx/Al2O3 exhibits better activity and stability. For MnOx/Al2O3, the catalytic activity on NO was greatly influenced by its loaded content, and 7% MnOx/Al2O3 showed superior catalytic activity among the MnOx/Al2O3. The addition of CeO2 could greatly improve the dispersibility of MnOx on the carrier and increase its catalytic activity. The 4% CeO2 addition was the optimum loaded mass precent. Forthermore, 550 degrees C is the best calcination temperature, as MnOx formed different crystalline phases with temperature, at the same time, the addition of CeO2 could affect MnOx crystalline phase. The catalytic mechanism of SCR on NO was also discussed.

As one of the common manganese oxide minerals in supergene environment, cryptomelane affects the migration, transformation and environmental fate of sulfur in soil. In this work, oxidation process of sodium sulfide solution by cryptomelane was investigated without oxygen gas. The species and concentration of oxidation products of sulfide in solution were determined by spectrophotometry and ion chromatography, and the crystal structures and micro-morphologies of solid oxidation products of sulfide were characterized by XRD and SEM. The influence of solution temperature, pH value of solution, manganese average oxidation state (AOS) and the amount of added cryptomelane on the initial oxidation rate of S2- was studied. It was observed that the oxidation products of sulfide were S2O3(2-), SO3(2-), SO4(2-) and S, and S was the main one for that the total transformation rate of S2- to S2O3(2-), SO3(2-) and SO4(2-) was below 13.4%. The initial oxidation rate of S2- follows a pseudo-first-order law. Oxidation rate increased with elevating reaction temperature, decreasing pH value of solution and the increase of the amount of added mineral. The oxidation capacity of cryptomelane increased with the increase of Mn(III) content, and the initial oxidation rate constants (K(obs)) of S2- were 0.220 3 min(-1) and 0.1729 min(-1) when cryptomelane was applied with AOS about 3.81 and 3.98, respectively. During the redox process, cryptomelane was reduced to Mn(OH)2, which could be oxidized into Mn3O4, by O2 in air, and Mn3O4 was further transformed into MnOOH likely due to the reaction of surface-adsorbed water on manganese oxide and O2 and Mn3O4.