The study of biological activity of transformation products of diclofenac and its interaction with chlorogenic acid

In the present work we compared the biological activity of DCF, 4′-OHDCF and 5-OHDCF as molecules of most biodegradation pathways of DCF and selected transformation products (2-hydroxyphenylacetic acid; 2,5-dihydroxyphenylacetic acid and 2,6-dichloroaniline) which are produced during AOPs, such as ozonation and UV/H₂O₂. We also examined the interaction of DCF with chlorogenic acid (CGA). CGA is commonly used in human diet and entering the environment along with waste mainly from the processing and brewing of coffee and it can be toxic for microorganisms included in activated sludge. In the present experiment the evaluation of following parameters was performed: E. coli K-12 cells viability, growth inhibition of E. coli K-12 culture, LC₅₀ and mortality of Chironomus aprilinus, genotoxicity, sodA promoter induction and ROS generation. In addition the reactivity of E. coli SM recA:luxCDABE biosensor strain in wastewater matrices was measured. The results showed the influence of DCF, 4′-OHDCF and 5-OHDCF on E. coli K-12 cells viability and bacteria growth, comparable to AOPs by-products. The highest toxicity was observed for selected, tested AOPs by-products, in comparison to the DCF, 4′-OHDCF and 5-OHDCF. Genotoxicity assay indicated that 2,6-dichloroaniline (AOPs by-product) had the highest toxic effect. The oxidative stress assays revealed that the highest level of ROS generation and sodA promoter induction were obtained for DCF, 4′-OHDCF and 5-OHDCF, compared to other tested compounds. We have also found that there is an interaction between chlorogenic acid and DCF, which resulted in increased toxicity of the mixture of the both compounds to E. coli K-12, comparable to parent chemicals. The strongest response of E. coli SM biosensor strain with recA:luxCDABE genetic construct in filtered treated wastewaters, comparable to control sample was noticed. It indicates, that E. coli SM recA:luxCDABE biosensor strains is a good tool for bacteria monitoring in wastewater environment. Due to toxicity and biological activity of tested DCF transformation products, there is a need to use additional wastewater treatment systems for wastewater contaminated with pharmaceutical residues.     

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N₂, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N₂ selectivity was impacted by the Brønsted acidity and the isolated Cu²⁺ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.     

电化学微传感器检测水中痕量铜离子

为改善微电极在阳极溶出伏安法检测重金属离子过程中低电流响应和低电催化能力的缺点,提出了一种在碳纤维微电极表面合成还原氧化石墨烯/纳米金材料制得还原氧化石墨烯纳米金修饰碳纤维微电极（rGO/AuNPs CFMEs）的方法.通过SEM表征,所制备的rGO/AuNPs CFMEs具有比表面积高、吸附能力强和催化活性好的特点,因此改性微电极适合作为方波阳极溶出伏安法（SWASV）测定水中铜离子（Cu²⁺）的工作电极.在构建微传感器测试水中痕量铜离子系统后,对pH值、电导率、富集时间和富集电位等检测条件进行了优化.在pH值为4,电导率为36.1S/m,富集时间为360s,富集电位为-1.2V的最佳条件下,铜的线性范围和检出限分别0~1.0μmol/L和2.4nmol/L.此外,微传感器的可重复性、长期稳定性以及选择性也得到了验证.     

CeO2形貌结构对催化湿式空气氧化苯酚性能的影响

采用水热法、沉淀法和溶胶凝胶法制备了3种不同形貌的CeO₂催化材料,并将其用于湿式空气氧化苯酚水溶液过程中,探讨了CeO₂形貌结构对催化湿式氧化苯酚水溶液性能的影响.采用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线衍射（XRD）、程序升温还原（TPR）等手段对CeO₂催化材料进行了表征.结果表明,水热法制备的CeO₂催化材料表现出较好催化性能,主要原因是水热法合成的CeO₂呈现交错的纳米棒状结构,主要暴露（220）晶面,且沿着（220）晶向生长.在反应温度为200℃、空气压力为2MPa、苯酚初始浓度500mg/L的条件下,最终（240min）COD的去除率为95.5%.     

氮掺杂二氧化钛负载钒磷氧催化氧化NO的实验研究

以VPO为活性组分,N掺杂TiO 2为载体,采用浸渍法制备了VPO/TiN催化剂,基于单因素实验研究了其对NO的选择性催化氧化(SCO)性能以及抗硫抗水性能。研究表明:当P/V为1/5、N/Ti为1、活性组分负载量为10%、焙烧温度为350℃时,催化剂的SCO活性最好,NO氧化率达到61%;光致发光光谱(PL)表征显示N掺杂TiO 2在催化剂表面形成的氧空位可增强催化剂对O 2的吸附;VPO/TiN催化剂抗硫抗水性能较强,反应后的催化剂表面未发现硫酸根的特征峰,水蒸气主要通过与NO竞争吸附占据活性位点来抑制催化剂的SCO活性。     

纤维增强气凝胶复合材料高温结构转变及热稳定性研究

目的研究高温受热条件下纳米复合隔热材料的结构转变特征及热稳定性。方法采用扫描电镜、X射线衍射仪、红外光谱仪及热重仪等检测方法。结果纤维增强气凝胶材料从室温到650℃存在连续的质量损失,从室温到放热前,质量损失为1.66%;365℃开始出现放热,温度升至398℃时达到峰值,整个放热过程对应质量损失约为1.3%;从435℃放热结束开始到650℃的质量损失为1.46%。经过400℃热处理后,试样比表面积从268m~2/g增加到437m~2/g;当试样热处理温度达到600℃时,试样的比表面积明显随之降低至198m~2/g。结论 SiO_2气凝胶复合材料以无定形结构为主,存在少量的二氧化钛晶体。在400℃左右,SiO_2气凝胶结构中硅甲基Si—CH_3发生氧化,产生明显的放热峰,之后硅羟基Si—OH之间发生缩聚反应,使600℃热处理后气凝胶中Si—O—Si网络骨架强度有所提高。未处理的纤维增强气凝胶材料试样上气凝胶纳米颗粒构成的块体较为良好地包裹在玻璃纤维表面,而经过600℃的高温热处理1 h后,块体气凝胶脱离了光滑的纤维表面,气凝胶纳米粒子发生收缩,致使材料比表面积下降。     

邻苯二甲酸二丁酯降解过程的单体同位素分析

研究对比了邻苯二甲酸二丁酯（DBP）在不同降解过程（水解、UV/H₂O₂光解、直接光解、过硫酸钾光氧化）中的碳、氢同位素组成变化、分馏特征及二维同位素（Δδ²H-Δδ¹³C）的相关性.水解反应中DBP分子产生了显著的碳同位素分馏,未发现氢同位素分馏,而且碳同位素富集因子ε_C为（-2.7±0.4）‰,表明DBP水解时发生C-O键断裂,氢原子不参与反应.而UV/H₂O₂光解和直接光解反应（pH值分别为2、7和10）中,DBP分子呈现了相似的二维同位素相关性Λ值[（9±2）~（11±2）],推测经历了相同的反应过程.过硫酸钾光氧化降解时,明显偏大的Λ值（31±3）说明反应可能发生C-H键断裂.结果表明：二维单体同位素分析（2D-CSIA）技术可以有效区分DBP的水解、光解、光氧化3种不同类型的降解过程,有助于分析其降解路径.     

Seasonal variation and size distribution of biogenic secondary organic aerosols at urban and continental background sites of China

Size-resolved biogenic secondary organic aerosols(BSOA) derived from isoprene and monoterpene photooxidation in Qinghai Lake, Tibetan Plateau(a continental background site) and five cities of China were measured using gas chromatography/mass spectrometry(GC/MS). Concentrations of the determined BSOA are higher in the cities than in the background and are also higher in summer than in winter. Moreover, strong positive correlations(R2= 0.44–0.90) between BSOA and sulfate were found at the six sites,suggesting that anthropogenic pollution(i.e., sulfate) could enhance SOA formation,because sulfate provides a surface favorable for acid-catalyzed formation of BSOA. Size distribution measurements showed that most of the determined SOA tracers are enriched in the fine mode( 3.3 μm) except for cis-pinic and cis-pinonic acids, both presented a comparable mass in the fine and coarse( 3.3 μm) modes, respectively. Mass ratio of oxidation products derived from isoprene to those from monoterpene in the five urban regions during summer are much less than those in Qinghai Lake region. In addition, in the five urban regions relative abundances of monoterpene oxidation products to SOA are much higher than those of isoprene. Such phenomena suggest that BSOA derived from monoterpenes are more abundant than those from isoprene in Chinese urban areas.     

萃取-催化氧化光度法测定生物体中H2O2含量研究

提出萃取-催化氧化光度法测定生物体中H2O2含量的新方法.用稀土催化H2O2产生羟基自由基以氧化二苯基碳酰二肼,生成红色二苯基碳酰腙,其最大吸收波长为563.0nm;当二苯基碳酰二肼浓度一定时,△A563与H2O2含量呈量效关系.在0～30μmol/L H2O2 含量范围内,该法能简单、快速、精确地测定生物样品中H2O2实际含量.     

Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

Catalytic wet air oxidation (CWAO) is one of the most promising technologies for pollution abatement. Developing catalysts with high activity and stability is crucial for the application of the CWAO process. The Mn/Ce complex oxide catalysts for CWAO of high concentration phenol-containing wastewater were prepared by coprecipitation. The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis. The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller (BET) analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry (ICP-AES). The results show that the catalysts have high catalytic activities even at a low temperature (80°C) and low oxygen partial pressure (0.5 MPa) in a batch reactor. The metallic ion leaching is comparatively low (Mn<6.577 mg/L and Ce<0.6910 mg/L, respectively) in the CWAO process. The phenol, COD_Cr, and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst (named CSP). The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater. Translated from Techniques and Equipment for Environmental Pollution Control, 2005, 6(2): 40–44 [译自: 环境污染治理技术与设备]