Treatability studies of naphthalene in soil,water and air with persulfate activated by iron(Ⅱ)

Chemical oxidation was applied to an artificially contaminated soil with naphthalene (NAP). Evaluation of NAP distribution and mass reduction in soil, water and air phases was carried out through mass balance. Evaluation of NAP distribution and mass reduction in soil, water and air phases was carried out through mass balance. The importance of the air phase analysis was emphasized by demonstrating how NAP behaves in a sealed system over a 4 hr reaction period. Design of Experiments method was applied to the following variables: sodium persulfate concentration [SP], ferrous sulfate concentration [FeSO₄], and pH. The system operated with a prefixed solid to liquid ratio of 1:2. The following conditions resulted in optimum NAP removal [SP] = 18.37 g/L, [FeSO₄] = 4.25 g/L and pH = 3.00. At the end of the 4 hr reaction, 62% of NAP was degraded. In the soil phase, the chemical oxidation reduced the NAP concentration thus achieving levels which comply with Brazilian and USA environmental legislations. Besides the NAP partitioning view, the monitoring of each phase allowed the variabilities assessment over the process, refining the knowledge of mass reduction. Based on NAP distribution in the system, this study demonstrates the importance of evaluating the presence of semi-volatile and volatile organic compounds in the air phase during remediation, so that there is greater control of the system as to the distribution and presence of the contaminant in the environment. The results highlight the importance of treating the contaminant in all its phases at the contaminated site.     

Effect of NOx and SO2 on the photooxidation of methylglyoxal: Implications in secondary aerosol formation

Methylglyoxal(CH_3COCHO,MG),which is one of the most abundant α-dicarbonyl compounds in the atmosphere,has been reported as a major source of secondary organic aerosol(SOA).In this work,the reaction of MG with hydroxyl radicals was studied in a 500 L smog chamber at(293±3) K,atmospheric pressure,(18±2)% relative humidity,and under different NOx and SO_2.Particle size distribution was measured by using a scanning mobility particle sizer(SMPS) and the results showed that the addition of SO_2 can promote SOA formation,while different NOx concentrations have different influences on SOA production.High NOx suppressed the SOA formation,whereas the particle mass concentration,particle number concentration and particle geometric mean diameter increased with the increasing NOx concentration at low NOx concentration in the presence of SO_2.In addition,the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO_2 and MG/OH/NOx/SO_2 reaction systems were detected by gas chromatography mass spectrometry(GC-MS) and attenuated total reflection fourier transformed infrared spectroscopy(ATR-FTIR) analysis.Two products,glyoxylic acid and oxalic acid,were detected by GC-MS.The mechanism of the reaction of MG and OH radicals that follows two main pathways,H atom abstraction and hydration,is proposed.Evidence is provided for the formation of organic nitrates and organic sulfate in particle phase from IR spectra.Incorporation of NOx and SO_2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.     

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.     

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。     

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.     

密封组合形式对结构密封性能影响研究

目的研究密封组合形式对结构密封性能的影响。方法开展密封性能试验,从密封形式、装配形式和涂覆形式的3种组合形式开展试验研究,找出结构密封性能影响因素,筛选密封最优组合形式。结果结构密封3种组成形式分别为有无贴合面的密封形式,干涉装配、湿装配形式,部分涂覆、全涂覆形式。开展2种应力水平下8种密封组合形式的密封性能试验,在保证密封工艺质量条件下,按照飞机结构和受载特点选取合理密封组合形式能有效提高结构密封性能。结论在飞机应力较高、不常拆的密封部位应选择贴合面密封、干涉装配、部分涂覆的密封组合形式,在飞机结构设计要求间隙装配、常拆卸的密封部位选择贴合面密封、湿装配、部分涂覆的密封组合形式。     

亚铵法制浆造纸厂中段废水处理技术分析研究

通过对采用两级气浮做预处理 ,生物硫化床串联接触氧化做深度处理的治理技术的分析研究 ,结合废水处理工程实例 ,说明了用两级串联气浮 +硫化床 +接触氧化工艺处理造纸中段水技术切实可靠 ,该治理工艺对处理亚铵法麦草制浆造纸中段废水有较强的针对性和可行性。