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%.     

8:2氟调聚羧酸在虾夷扇贝体内的蓄积、分布与转化

以虾夷扇贝（Patinopecten yessoensis）为受试生物,研究了8：2氟调聚羧酸（8：2FTCA）在虾夷扇贝不同组织（肝脏、鳃、性腺、外套膜、闭壳肌）中的蓄积、分布和生物转化特征.结果显示,8：2FTCA蓄积浓度最高的组织为肝脏,达峰值最快的组织为鳃.在8：2FTCA代谢过程中,检测到8：2氟调聚不饱和酸（8：2FTUCA）、7：3氟调聚羧酸（7：3FTCA）、全氟辛酸（PFOA）、全氟壬酸（PFNA）和全氟庚酸（PFHpA）5种代谢产物,其中7：3FTCA和PFOA为含量最丰富的2种代谢产物.它们主要分布在鳃和肝脏组织中,鳃和肝脏是8：2FTCA进行生物转化的主要器官,并且鳃组织中代谢产物的浓度最高.推测出虾夷扇贝体内8：2FTCA的生物转化路径,与虹鳟的生物转化行为相比,虾夷扇贝在代谢产物产量和半衰期上均有差异,说明水生生物的生物转化行为具有物种差异性.8：2FTCA在虾夷扇贝体内可转化为PFOA、PFNA和PFHpA等全氟烷基羧酸（PFCAs）,是虾夷扇贝体内PFCAs的一个间接来源.     

柴油机选择性催化还原捕集技术(SDPF)的研究现状与发展趋势

日益严格的柴油机排放法规使得其主要排放污染物氮氧化物（NO_x）和颗粒物（PM）限值进一步降低.目前去除NO_x的主要机外手段是选择性催化还原（SCR）技术,该技术通常在200℃以上才有良好的NO_x转化率,而在柴油机冷起动阶段,SCR入口的排气温度无法达到200℃,NO_x排放控制困难.尽管冷起动时间较短,但该阶段的NO_x排放量占比很高.在严格的排放法规要求下,冷起动阶段的NO_x排放控制日益受到关注.选择性催化还原捕集技术（SDPF）将SCR催化剂涂覆在壁流式颗粒捕集器（DPF）载体上,能够同时去除NO_x和PM.与SCR技术相比,SDPF更加靠近柴油机排气门,NO_x催化还原反应的温度得到有效提高.因此,SDPF成为了提高低温NO_x转化率的关键技术.本文从SDPF结构与原理、载体与催化剂、性能及影响因素、SDPF技术路线等四个方面展开综述.SDPF结构与原理方面,介绍了SDPF的基本结构和化学反应原理,并指出了该技术面临的主要挑战;SDPF载体与催化剂方面,阐述了常见的载体材料、SCR催化剂涂覆、载体结构参数设计和提高载体性能的膜技术,以及钒基、沸石基SCR催化剂的研究进展;SDPF性能及影响因素方面,对SDPF的碳烟氧化性能、NO_x还原性能、尿素混合性能和耐久性能进行了分析,需要重点优化碳烟氧化与NO_x还原之间的竞争性反应;SDPF技术路线方面,介绍了带有SDPF的后处理系统优化,尿素双喷技术、低温NO_x吸附、热管理等技术耦合SDPF能够进一步拓宽后处理系统的温度窗口,是满足未来超低排放法规的后处理技术发展趋势.     

Investigation on the urea deposit formation and thermal decomposition characteristics in the SCR aftertreatment system of a diesel engine

Selective catalytic reduction is the most efficient and reliable equipment for NOx control in current diesel engines. However, the issue of urea crystallization becomes increasingly serious with the implement of the new emissions standards. In this paper, urea deposit samples collected from engine test bed and tube furnace were characterized by thermogravimetric analysis and Fourier transform-infrared analysis to aid the comprehension of urea deposit formation. Moreover, thermogravimetric tests were conducted to disclose the effects of catalyst on the thermal decomposition processes of urea deposit. The results indicated that less temperature resistant species are formed in the engine test bed than in the tube furnace at conditions with the same temperatures. The main compositions in the World Harmonized Transient Cycle (WHTC) urea deposits are urea, cyanuric acid (CYA) and ammelide, implying that accelerating the decomposition of these species could prevent the accumulation of urea deposit. CuWTi, Cuβ and CuZSM catalysts could lead to increased yield of CYA during pure urea thermolysis. Cuβ, CuWTi and VWTi catalysts tend to promote the thermolysis of CYA while VWTi has the most significant catalytic effects on the thermal decomposition of ammelide and ammeline.     

Sediment quality assessment of Beasley Lake: bioaccumulation and effects of pesticides in Hyalella azteca

Beasley Lake is a Conservation Effects Assessment Program (CEAP) watershed in the intensively cultivated Mississippi Delta, USA. Lake sediment quality at three sites was evaluated in 2004 and 2008 for biological impairment and uptake (animal tissue pesticide residues) from 14 pesticides and three metabolites using Hyalella azteca (Saussure). Eleven pesticides and three metabolites were detected in sediment among the three sites in 2004 and all 17 compounds examined were detected among the three sites in 2008, with the herbicide atrazine having the greatest concentrations. Twenty-eight-day H. azteca survival and growth (mg w/w) indicated no survival effects at any site for either year, but growth impairment occurred in H. azteca exposed to sediments in 2004, whereas growth enhancement occurred in H. azteca exposed to sediments at one site in 2008. Pesticides observed in animal tissue pesticide residues occurred more frequently and in greater concentrations in 2004 compared with 2008. Thirteen pesticides were detected in animal tissue pesticide residues in 2004, with chlorpyrifos occurring in the greatest concentrations, and six pesticides were detected in 2008, with p,p′-DDT occurring in the greatest concentrations. H. azteca tissue pesticide residues of seven pesticides, two herbicides, three insecticides, one insecticide metabolite, and p,p′-DDT, were associated with growth.     

Total petroleum hydrocarbon burden in fish tissues from the Arabian Gulf

The levels of total petroleum hydrocarbons (TPH) and lipid contents have been reported for eight commercially important fish species from the Arabian Gulf. GC-FID has been used as quantification technique. Out of the species analyzed, Scarus ghabon showed the highest level of TPH (7.4 ± 3.2 µg g^?1) in the muscle tissue followed by Epinephelus tauvina (6.8 ± 3.6 µg g^?1). Except for E. microdon (4.8 ± 2.1 µg g^?1), all other fish species showed a similar level of TPH concentration. Significant correlations were obtained between lipid contents and TPH levels in the muscles of the fish. Body weight of the fish was also found to be strongly correlated with TPH concentration in the muscle tissue. There is a tendency of accumulating higher TPH in the winter season as compared to in the summer season.     

Characterisation of cobalt‐binding proteins in occupational cobalt exposuret†

In animal experimentations cobalt is found to be carcinogenic under conditions which are comparable with a possible exposure of human beings at the workplace.^1,2 Little is known about binding and distribution of incorporated cobalt in blood.

Blood, serum and plasma of workers occupationally exposed to cobalt were analyzed concerning cobalt‐binding. The samples were focused by preparative IEF in layers of granulated gels. The cobalt concentrations in the isolated fractions were measured with the aid of flameless atomic absorption spectrometry. The whole blood samples exhibit peaks with different sizes in the pH‐5‐ and ‐7‐range. The proportion of these peaks can change with individual samples. In serum and plasma cobalt is found only in the pH‐5‐range.

When separated by gelelectrophoresis under denaturating conditions the cobalt‐fractions in all blood, serum and plasma samples shows a similar protein pattern. Several proteins with different molecular weights are detected in the pH‐5‐fractions, whereas only hemoglobin is found in the pH‐7‐fractions. In agreement with these results is the refocusing in ultrathin‐layer of polyacrylamide. Heterogeneous protein patterns are demonstrated with the pH‐5‐fractions; the pH‐7‐fractions yield only the hemoglobin pattern.

In vivo cobalt is bound to plasma proteins‐perhaps‐albumin^3,4‐and hemoglobin. Till now the chemical structure of the binding is unknown.     

Enzymatic and cellular level effects of nickel∗

The effects of Ni on hepatic enzymes of tilapia, viz. acid‐ and alkaline phosphatases, catalase and glucose‐6‐phosphatase, both under in vivo and in vitro conditions reflected the following tendencies. In vivo conditions indicated maximal increase in activity for acid phosphatase at 3.00 ppm, equivalent to 28.5%, followed by a slight decrease and increase thereafter. As for alkaline phosphatase, gradual increase in activity was observed with maximal activity at 9 ppm of Ni, equivalent to 16.8%. Catalase demonstrated similar tendencies with maximal activity at 9.0 ppm, equivalent to 101.2%. In the case of glucose‐6‐phosphatase, the tendency was the reverse with maximal inhibition at 9.00 ppm, i.e. 41.9%. In contrast to in vivo conditions, in vitro systems indicated that all investigated enzymes were inhibited in the region of 4–10% except for catalase which demonstrated a slight increase by 5–6% in activity between concentrations of 10–15 ppm of Ni but thereafter continuous inhibitory effects prevailed.

At cellular level, exposure of tilapia to a lethal dose of 9 ppm of Ni indicated not much of an adverse effect except for a slight depletion in fat and glycogen content. In the case of mitochondria, they were normal and a few large secondary lysosomes were observed. In relation to the cell membrane no dramatic change was detected.     

钴负载MCM-41分子筛催化臭氧氧化水中氯代苯甲酸

通过水热法合成介孔分子筛MCM-41,采用等体积浸渍法制备了Co负载MCM-41分子筛催化剂(Co/MCM-41).小角X-射线粉末衍射(XRD)、紫外-可见漫反射光谱(UV-vis DRS)、N2吸附-脱附等温线及透射电镜(TEM)等对催化剂的成分、结构的表征结果显示,Co/MCM-41保持了纯硅MCM-41有序的介孔结构,钴元素以钴氧化物形式存在,比表面达到772 m.2g-1.将Co/MCM-41分子筛用于催化臭氧氧化水中对氯苯甲酸(p-CBA)的研究,结果表明,在优化条件下(2%负载量和25℃反应温度),催化剂的加入显著改善了TOC去除率,达到84.6%,是单独臭氧氧化的1.6倍.