Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag+/TiO2

Photocatalytic ozonation of phenol and oxalic acid （OA） was conducted with a Ag^＋/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag^＋ greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag＋ was easily reduced and deposited on the surface of Tit2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag^＋ can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.     

Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

利用淀粉/PCL共混物作为反硝化固体碳源和生物膜载体的研究

以双螺杆挤出机制备了淀粉聚己内酯(PCL,polycaprolactone)共混物(SPCL5),研究了其浸出性能及吸水性能,并在序批试验中研究了其作为反硝化固体碳源和生物膜载体的特性。结果表明,SPCL5颗粒前3 d浸出的有机物浓度较高,随后逐渐降至1.31 mgL。SPCL5颗粒吸水率在1 d左右达到饱和,约为30.97%。SPCL5可作为固体碳源用于去除低碳氮比(CN)水中的硝酸盐。以活性污泥接种时,SPCL5颗粒在1 d后就有显著的脱氮效果。驯化结束后,SPCL5颗粒的平均反硝化速率(以N计)为0.020 8 mg(g·h)。剪切力是影响反硝化速率的重要因素,转速从70 rmin提高至140 rmin时,平均反硝化速率提升近1倍,达到0.040 3 mg(g·h)。进水NO3-N浓度为15~50 mgL时对反硝化速率无显著影响,反硝化为零级反应。红外光谱结果表明利用后的共混物中淀粉和PCL均发生了降解。     

煤矿酸性矿井水的治理方法与探讨

煤矿酸性矿井水具有强腐蚀性,并含有多种重金属离子,直排对生态环境破坏严重。本文主要介绍了人工湿地法、微生物法与中和法处理酸性矿井水治理方法,并对目前国内技术最成熟、应用最广泛的石灰乳中和法进行了重点阐述和探讨。     

内分泌干扰物生物检测研究进展

介绍了发光细菌法、重组基因酵母法、免疫分析法、细胞增殖法、受体结合活性法、卵黄蛋白法、酵母双杂交法等几种环境中内分泌干扰物的生物检测技术及研究进展,并提出了展望。     

中亚热带马尾松林凋落物分解过程中的微生物与酶活性动态

采用凋落物原位分解法,研究了中亚热带马尾松林中马尾松、槲栎凋落叶单独及混合(自然质量比8∶2)分解过程中的微生物数量与酶活性动态.结果表明:①3类凋落物的年分解常数K的大小为:混合凋落物(0.94)>槲栎凋落物(0.86)>马尾松凋落物(0.67);②3类凋落物真菌数量和微生物数量均在夏季(135 d时)达到最大值,而此时细菌和放线菌数量最低;③3类凋落物纤维素酶活性、酸性磷酸酶活性均与凋落物干重剩余率呈显著正相关(P<0.05),而马尾松与混合型凋落物中的多酚氧化酶活性同凋落物干重剩余率呈极显著负相关(P<0.01);④微生物数量和多酚氧化酶活性均总体表现为槲栎凋落物>混合凋落物>马尾松凋落物,酸性磷酸酶活性多表现为槲栎凋落物最低,与分解常数K排列有一定的差异,说明凋落物分解是微生物和多种酶共同作用的结果.整体研究表明,凋落物质量和季节气候的差异显著影响微生物群落及其调控的生态过程,与纯马尾松凋落叶相比,针阔混合使微生物数量和多酚氧化酶活性显著提高,这可能是导致分解加快的重要原因.     

温带典型草原土壤总有机碳及溶解性有机碳对模拟氮沉降的响应

2008年5月～2011年10月,以内蒙古温带典型草原为研究对象,利用小区模拟控制试验,设置对照[0 g·(m2·a)-1]、低氮[5 g·(m2·a)-1]、中氮[10 g·(m2·a)-1]、高氮[20 g·(m2·a)-1]这4个净氮输入量处理,模拟研究了大气氮沉降水平变化对土壤总有机碳(TOC)以及溶解性有机碳(DOC)含量、年际变化及其垂直分布格局的影响,并分析了两者之间的关系.结果表明,除个别年份外,土壤TOC与DOC含量均随土壤深度增加而递减,4 a的连续施氮并未改变土壤TOC与DOC的垂直分布规律,但施氮降低了土壤TOC的垂直变异,增加了土壤DOC的垂直变异;施氮4 a对于草地表层0～20 cm土壤TOC与DOC含量的变化并未表现出显著影响(P>0.05).不同氮输入水平处理0～20 cm土层有机碳密度在3.9～5.6 kg·m-2之间变动,试验前两年不同氮处理0～20 cm土壤有机碳密度均低于对照或与对照接近,试验后两年,施氮对土壤总有机碳密度逐渐呈现出一定的促进作用,但与对照的差异仍不显著(P>0.05);不同处理0～20 cm土层DOC/TOC约为0.32%～1.09%,氮输入增加普遍降低了DOC在整个TOC中所占的比例;草地土壤TOC与DOC的变化呈显著正相关(P<0.01).不同处理草地土壤DOC随时间的变异均远大于TOC,与TOC相比,草地土壤DOC的变化更为迅速,是研究草地土壤碳库对氮沉降变化响应的重要敏感性指标.     

重庆主城区降水中重金属的分布特征及其沉降量

于2011年12月~2012年11月,在重庆主城区设置了3个采样点,利用湿沉降自动采样器收集降水样品,用ICP-MS对样品中13种重金属进行分析,并通过引入富集因子,研究了重庆主城区降水中重金属含量分布特征、污染水平及沉降量.结果表明,重庆主城区降水中大部分重金属元素的含量水平和年沉降量高于国内其他城市和国外一些地区,其中,Cd、Pb、As含量和沉降量分别为0.55μg·L-1和0.44 mg·(m2·a)-1、37.94μg·L-1和30.25 mg·(m2·a)-1、5.65μg·L-1和4.50mg·(m2·a)-1,相对较高.另外,重庆主城区降水中重金属含量和沉降量空间差异不大,但都有明显的季节差异,含量在秋季和冬季出现较大值,而沉降量在春季和夏季出现较大值.富集因子计算结果显示,多种重金属元素的富集因子相对较高,其中Cd和Se的富集因子分别为1 740和4 133,污染较为严重.     

东莞市大气亚微米粒子PM1及其中水溶性无机离子的污染特征

2011年8月—2012年7月期间,利用中流量(100 L·min-1)大气采样器对东莞市A和B两点(A:生活区,B:工业区)进行PM1、PM1~2.5、PM2.5~10采样,并定量分析颗粒物上F-、Cl-、NO-3、SO2-4、NH+4、Na+、K+、Ca2+、Mg2+等9种水溶性无机离子.分析结果显示,工业区B点的细粒子污染较生活区A点严重,B点PM1质量浓度年均值为48μg·m-3,其浓度是A点的1.2倍.A、B两点PM1对PM2.5和PM10的质量贡献率无明显差异,平均贡献率分别高达69%和45%.二次离子SO2-4、NO-3、NH+4及与燃烧行为有关的K+、Cl-等5种离子在细粒子PM1上富集,这5种离子对PM1质量的贡献率分别为18.82%~19.76%、4.98%~5.47%、3.98%~4.12%、2.03%~2.27%和3.39%~3.78%.而其他4种离子,Ca2+、Mg2+、F-和Na+积聚在粗粒子PM2.5~10上.PM10/PM2.5/PM1三种粒子中,PM1粒子酸性值AE/CE(阴离子当量浓度/阳离子当量浓度)比值和硫转化率SOR、氮转化率NOR值均是最高.     

基于物元分析的表层岩溶带“二元”水生态承载力评价

针对目前水生态承载力评价中信息屏蔽和主观性问题,该文以喀斯特典型分布区贵州省为例,在阐述表层岩溶带"二元"水生态承载力概念的基础上,构建表层岩溶带"二元"水生态承载力评价指标体系,结合物元分析法,对贵州省2007—2010年的表层岩溶带"二元"水生态承载力进行定量评价.研究结果表明:2007—2010年贵州省表层岩溶带"二元"水生态承载力等级都为"可承载",整体呈现出比较稳定的发展趋势,但是"可承载"水平并不稳定,不完全符合No2的标准."可承载"水平不稳定.贵州省表层岩溶带"二元"水生态承载力的主要提升因子是地表产流率、输沙模数、森林覆盖率、水资源利用率等8个,而单位面积地表水资源量、生态用水率、工业废水排放达标率、工业固体废物综合利用率以及城镇化率等9个成为制约贵州省表层岩溶带"二元"水生态承载力等级提升的因子.贵州省的表层岩溶带"二元"水生态承载力不仅关系到自身的社会、经济和生态安全也关系到下游的长江流域和珠江流域的水资源安全、生态安全以及环境建设.因此,应制定区域生态补偿措施,经济发达地区反哺经济落后地区,形成联动的共同保护生态环境脆弱区的水生态承载力的机制.为促进贵州省的水土资源开发利用和生态环境建设提供理论借鉴,并为类似地区的水生态承载力评价提供了一种新方法.