TiO2-Cu2O/蒙脱土复合光催化剂的制备与性能

以钠基蒙脱土（MMT）为载体,先采用溶胶-凝胶法将纳米TiO₂引入到MMT层间,再采用化学沉积法将纳米Cu₂O负载在TiO₂/MMT上,制备出TiO₂-Cu₂O/MMT纳米复合光催化剂。采用XRD、SEM、紫外-可见漫反射技术对催化剂进行了表征。以甲基橙为目标污染物,考察了催化剂的光催化性能。表征结果显示：TiO₂与Cu₂O均匀分布在MMT的表面与片层孔隙中;TiO₂-Cu₂O/MMT结合了TiO₂和Cu₂O的特性,拓宽了催化剂的光吸收范围。实验结果表明,在光源为可见光、初始甲基橙质量浓度为20 mg/L、光催化剂加入量为2 g/L的条件下,TiO₂-Cu₂O/MMT纳米复合光催化剂对甲基橙的光催化降解效果明显优于单一负载的Cu₂O/MMT和TiO₂/MMT,大幅提高了催化剂的光催化效率,反应300 min时TiO₂-Cu₂O/MMT对甲基橙溶液的脱色率达到93%。     

钛基金属氧化物电极的制备及性能

采用聚合物前驱体法制备了Ti/SnO₂-Sb₂O₃电极,再通过恒电流电沉积法制备了 Ti/SnO₂-Sb₂O₃/PbO₂和Ti/SnO₂-Sb₂O₃/MnO₂电极。采用SEM技术对3种金属氧化物电极表面的形貌进行了表征,并分别以3种电极为阳极进行了苯酚的电催化氧化实验。实验结果表明：电解时间为2.5 h时,Ti/SnO₂-Sb₂O₃电极、Ti/SnO₂-Sb₂O₃/PbO₂电极和Ti/SnO₂-Sb₂O₃/MnO₂电极对苯酚的降解率分别为85.9%,83.2%,44.6%;苯酚在3种电极上的电催化氧化反应均遵循一级反应动力学方程;苯酚在Ti/SnO₂-Sb₂O₃ 电极和Ti/SnO₂-Sb₂O₃/PbO₂电极上的反应速率较快,并具有较高的析氧电位;Ti/SnO₂-Sb₂O₃/PbO₂电极具有更好的耐腐蚀性和更长的使用寿命。     

纳米TiO2-石墨烯光催化剂的水热合成及其光催化性能

以钛酸四正丁酯和石墨为原料,通过水热法制备了锐钛矿型为主的纳米TiO2复合光催化剂（纳米TiO2-石墨烯）,并采用XRD,FTIR,FESEM,TEM技术对其进行了表征。通过紫外光照射降解溶液中的罗丹明B（RhB）研究了TiO2-石墨烯的光催化活性,分析了初始罗丹明B质量浓度、催化剂加入量、溶液pH和催化剂使用次数等影响降解效果的因素。实验结果表明：在初始RhB质量浓度为20 mg/L、溶液pH为7.10、催化剂加入量为1.000 g/L的条件下,紫外光照射30 min时,纳米TiO2-石墨烯对RhB的降解率高达98.69%,明显高于纳米TiO2的44.69%;纳米TiO2-石墨烯稳定性较强,可多次重复使用。     

铁氧化物复合氧化铝催化臭氧化过程中溴酸盐的生成控制

以市售活性炭、硅藻土和氧化铝小球为载体,考察了负载铁基活性组分对催化臭氧化过程中溴酸盐的控制情况,其中,铁基复合氧化铝小球体现出更好的溴酸盐还原特性和催化剂稳定性,证实催化剂中铁氧化物是溴酸盐得到有效控制的主要活性组分。进一步考察了铁基复合氧化铝小球催化臭氧化处理实际原水过程中对溴酸盐的生成控制,以及反应过程中溶解性有机碳（DOC）的去除情况。结果表明,与单独臭氧化相比,该催化剂既能有效去除水中的溶解性有机物,又能明显抑制溴酸盐的生成,反应50h,其活性并没有明显下降。催化剂失活主要归因于吸附位点数量的下降,可以通过负载铁氧化物来实现催化剂的再生。     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

Responses of a soil bacterium, Pseudomonas chlororaphis O6 to commercial metal oxide nanoparticles compared with responses to metal ions

The toxicity of commercially-available CuO and ZnO nanoparticles (NPs) to pathogenic bacteria was compared for a beneficial rhizosphere isolate, Pseudomonas chlororaphis O6. The NPs aggregated, released ions to different extents under the conditions used for bacterial exposure, and associated with bacterial cell surface. Bacterial surface charge was neutralized by NPs, dependent on pH. The CuO NPs were more toxic than the ZnO NPs. The negative surface charge on colloids of extracellular polymeric substances (EPS) was reduced by Cu ions but not by CuO NPs; the EPS protected cells from CuO NPs-toxicity. CuO NPs-toxicity was eliminated by a Cu ion chelator, suggesting that ion release was involved. Neither NPs released alkaline phosphatase from the cells’ periplasm, indicating minimal outer membrane damage. Accumulation of intracellular reactive oxygen species was correlated with CuO NPs lethality. Environmental deposition of NPs could create niches for ion release, with impacts on susceptible soil microbes.     

Arsenic release from arsenic-bearing Fe-Mn binary oxide: effects of E(h) condition

Ferric and manganese binary oxide (FMBO) has been successfully used to remediate arsenic-polluted river, but there still lacks sufficient data to evaluate its effects on environments. The release behaviors of iron (Fe), manganese (Mn), and arsenic (As) in different E_h ranges were investigated for As-bearing FMBO sediment after remediating As-polluted DaSha River by FMBO. Under high E_h range (+550 to +400 mV), slight dissolution of Fe and Mn, which corresponded to 12.2% and 25.6%, and less than 5% of As release were observed in 336 h. Under lower E_h range (+50 to −100 mV), elevated extent of the dissolution of Mn and Fe were observed, which corresponded to as high as 61.3% and 70.1%. Under such conditions, the dissolution rate of Mn was higher than that of Fe. Furthermore, from the established relationship of As release and the dissolution of Fe and Mn, the release of As seemed dominated by the dissolution of Fe. X-ray photoelectron spectroscopy (XPS) analysis demonstrated the release of Fe, Mn, As(III), and As(V) after sodium ascorbate-treatment, and the re-adsorption of As(V), as indicated from the increased binding energy of As 3d from 44.78 to 45.83 eV. Surface element composition analysis indicated significant decrease of Mn from 3.22% to 0.54%, slight increase of Fe from 12.45% to 13.67%, and elevated ratio of As from 0.11% to 0.32% accordingly. The main reactions of Fe and Mn dissolution and the pathways of As release under different E_h ranges were also proposed.     

Hydroxytyrosol, the phenolic compound of olive oil protects human PBMC against oxidative stress and DNA damage mediated by 2,3,7,8-TCDD

The protective effect of hydroxytyrosol (HT), a strong antioxidant compound from extra virgin olive oil, against TCDD induced toxicity was investigated in human peripheral blood mononuclear cells (PBMC). PBMC (1 × 10⁶ cells mL⁻¹) were divided into four groups and were incubated in a CO₂ incubator (5% CO₂) for 12 h with vehicle, TCDD (10 nM), TCDD + HT (10 nM + 100 μM) and HT alone (100 μM) respectively. To clarify the role of HT against TCDD induced cytotoxicity, oxidative stress and the levels of antioxidant enzymes were assessed. Incubation of PBMC with TCDD significantly decreased cell viability, catalase (CAT) and glutathione peroxidase (GPx) and increased the levels of superoxide dismutase (SOD), glutathione reductase (GR) and oxidative stress markers such as lipid peroxidation products (LPO), protein carbonyl content (PCC) and reactive oxygen species (ROS). Whereas, HT had an effective antioxidant property as observed by the increased cell viability, normalization of antioxidant enzymes and decreased levels of LPO, PCC and ROS in PBMC co-treated with HT and TCDD. Apoptosis detection and comet assay results shows that HT, by acting as an antioxidant, prevents the damage to DNA induced by TCDD. In addition light microscopic and histopathological observations revealed that the cells are apoptotic and degenerated during TCDD treatment, whereas cells showed intact morphology during co-treatment with HT. On the whole, the results reveal that HT exerts a promising antioxidant potential in protecting the PBMC against TCDD induced oxidative stress, which might be due to the presence of catechol moiety in its structure.     

Integrated analysis of the effects of agricultural management on nitrogen fluxes at landscape scale

The integrated modelling system INITIATOR was applied to a landscape in the northern part of the Netherlands to assess current nitrogen fluxes to air and water and the impact of various agricultural measures on these fluxes, using spatially explicit input data on animal numbers, land use, agricultural management, meteorology and soil. Average model results on NH₃ deposition and N concentrations in surface water appear to be comparable to observations, but the deviation can be large at local scale, despite the use of high resolution data. Evaluated measures include: air scrubbers reducing NH₃ emissions from poultry and pig housing systems, low protein feeding, reduced fertilizer amounts and low-emission stables for cattle. Low protein feeding and restrictive fertilizer application had the largest effect on both N inputs and N losses, resulting in N deposition reductions on Natura 2000 sites of 10% and 12%, respectively.     

ZnO/LixNi1-xO光催化降解甲基橙的研究

采用溶胶凝胶法制备LixNi1-xO和ZnO粉体,利用球磨法制备ZnO/LixNi1-xO复合粉体,以紫外光为光源,通过降解甲基橙,研究了锂掺杂及n-p复合对氧化镍的光催化性能影响。结果表明：当投放量为0.1 g/L,x≤0.075（摩尔分数）的锂掺杂氧化镍均比未掺杂氧化镍的光催化活性高。当锂掺杂摩尔分数为0.025,投放量为0.4 g/L时锂掺杂氧化镍的光催化活性最佳,甲基橙最高降解率达到93.1%。当ZnO/Li0.025Ni0.975O在质量比为1∶1,投放量为0.2 g/L时光催化活性最佳,甲基橙最高降解率达到98.1%。