二氧化钛复合型催化剂制备及其微波辅助催化氧化甲苯性能

实验采用溶胶凝胶法和传统浸渍法制备了TiO2-分子筛复合载体及复合载体负载过渡金属与稀土元素催化剂,通过微波辅助催化氧化甲苯的性能实验考察其催化活性.结果表明,复合TiO2明显提高了载体结构的稳定性与耐温性,并使过渡金属铜(Cu)、锰(Mn)和稀土元素铈(Ce)等活性组分在催化剂表面的分散更均匀;在复合载体吸附、吸波性能与多相活性组分催化的共同作用下,Cu-Mn-Ce/TiO2-分子筛催化剂微波辅助催化氧化甲苯的完全燃烧温度仅为175℃,此时甲苯去除率可达99％;15 h的连续性实验表明,TiO2复合型催化剂具有良好的催化活性与稳定性.由催化剂表征分析结果可知,活性组分颗粒的均匀分布与铜、锰氧化物及铜锰尖晶石固溶物等活性相的存在促进了甲苯的催化氧化,锐钛矿型TiO2较高的电子迁移速率与催化剂孔径的增大均有助于甲苯的氧化降解.     

沉积物中雌激素及壬基酚、辛基酚、双酚A的测定

近些年来雌激素及烷基酚类化合物由于其对水生生物的内分泌干扰作用越来越受到广泛关注.沉积物作为环境中有机污染物的重要储存库,研究目标物在其中的浓度分布对于探明此类物质在环境中的迁移转化具有重要意义.但沉积物中基质组成复杂而雌激素又痕量存在,这增加了前处理的难度.本研究从雌激素及烷基酚类化合物的理化性质入手,采用碱液提取、液液萃取和LC-MS/MS分析测定沉积物样品中的雌激素及壬基酚、辛基酚、双酚A.结果表明,经过优化的方法对7种目标物的回收率介于61.9%～93.7%之间.该方法能有效去除沉积物中那些不溶于强碱和既溶于酸又溶于碱的有机污染物,同时操作简单、成本低,但回收率高、检出限低,可广泛适用于河流沉积物样品及土壤样品的前处理.     

Application of comprehensive two-dimensional gas chromatography with mass spectrometric detection for the analysis of selected drug residues in wastewater and surface water

Pharmaceutical residues have become tightly controlled environmental contaminants in recent years, due to their increasing concentration in environmental components. This is mainly caused by their high level of production and everyday consumption. Therefore there is a need to apply new and sufficiently sensitive analytical methods, which can detect the presence of these contaminants even in very low concentrations. This study is focused on the application of a reliable analytical method for the analysis of 10 selected drug residues, mainly from the group of non-steroidal anti-inflammatory drugs (salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen, and dicofenac), in wastewaters and surface waters. This analytical method is based on solid phase extraction, derivatization by N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and finally analysis by comprehensive two-dimensional gas chromatography with Time-of-Flight mass spectrometric detection (GC×GC- TOF MS). Detection limits ranged from 0.18 to 5 ng/L depending on the compound and selected matrix. The method was successfully applied for detection of the presence of selected pharmaceuticals in the Svratka River and in wastewater from the wastewater treatment plant in Brno-Modrice, Czech Republic. The concentration of pharmaceuticals varied from one to several hundreds of ng/L in surface water and from one to several tens of μg/L in wastewater.     

漆酶的逆胶束萃取条件优化的研究

研究了生物表面活性剂逆胶束体系萃取纯化漆酶的后萃的过程.在此逆胶束体系中,表面活性剂采用一种阴离子生物表面活性剂鼠李糖脂(rhamnolipid, RL),溶剂采用异辛烷.分别考察了4种不同离子种类(NaCl, NaBr, KCl和KBr)与不同浓度、4种不同助溶剂种类(正丁醇,正己醇,正庚醇及正辛醇)与不同比例、乙醇的含量以及温度对漆酶的后萃过程的影响.结果表明,0.25mol/L KCl或0.20mol/L KBr能够得到较好的萃取效果;在四种助溶剂中,正己醇(比例为0.5)和正庚醇(比例为0.5)效果比较好;乙醇加入量为9%效果最优;最适宜温度为35℃.在上述条件下,漆酶的酶活回收率和纯化倍数分别高达90%,4.7倍.电泳分析结果进一步证实了漆酶的纯化效果较好.研究证明鼠李糖脂逆胶束萃取酶类具有广阔的应用前景.     

Pb(II) removal from water using Fe-coated bamboo charcoal with the assistance of microwaves

Bamboo charcoal(BC) was used as starting material to prepare iron-modified bamboo charcoal(Fe-MBC) by its impregnation in FeCl 3 and HNO 3 solutions simultaneously,followed by microwave heating.The material can be used as an adsorbent for Pb(Ⅱ) contaminants removal in water.The composites were prepared with Fe molar concentration of 0.5,1.0 and 2.0 mol/L and characterized by means of N 2 adsorption-desorption isotherms,X-ray diffraction spectroscopy(XRD),scanning electron microscopy coupled with energy dispersive X-ray spectrometry(SEM-EDS),Fourier transform infrared(FT-IR) and point of zero charge(pH pzc) measurements.Nitrogen adsorption analyses showed that the BET specific surface area and total pore volume increased with iron impregnation.The adsorbent with Fe molar concentration of 2 mol/L(2Fe-MBC) exhibited the highest surface area and produced the best pore structure.The Pb(Ⅱ) adsorption process of 2Fe-MBC and BC were evaluated in batch experiments and 2Fe-MBC showed an excellent adsorption capability for removal Pb(Ⅱ).The adsorption of Pb(Ⅱ) strongly depended on solution pH,with maximum values at pH 5.0.The ionic strength had a significant effect on the adsorption at pH < 6.0.The adsorption isotherms followed the Langmuir isotherm model well,and the maximum adsorption capacity for Pb(Ⅱ) was 200.38 mg/g for 2Fe-MBC.The adsorption processes were well fitted by a pseudo second-order kinetic model.Thermodynamic parameters showed that the adsorption of Pb(Ⅱ) onto Fe-MBC was feasible,spontaneous,and exothermic under the studied conditions,and the ion exchange mechanism played an significant role.These results have important implications for the design of low-cost and effective adsorbents in the removal of Pb(Ⅱ) from wastewater.     

Determination of 4-tert-octylphenol in surface water samples of Jinan in China by solid phase extraction coupled with GC-MS

Octylphenols, considered as xenoestrogens, mainly exist as 4-tert-octylphenol (OP) in aquatic environments. The high stability and accumulation of OP in aquatic systems have caused endocrine disruption. The OP in surface water in Jinan, China was analyzed by gas chromatography-mass spectrometry (GC-MS) coupled with solid phase extraction (SPE). Water samples were extracted by SPE on a cartridge system containing C-18 as sorbent. To increase sensitivity and selectivity, OP was derivatized to 4-tert-octyl-phenoxy silane. With the use of phenanthrene-d10 as internal standard, the detection limit based on signal-to-noise ratio (S/N = 3) was 0.06 ng/mL. The average recovery was from 84.67% to 109.7%. The precision of the method given as the relative standard deviations (RSD) was within the range 6.24%-12.96%. In the target water samples, the concentrations of OP were as follows: 15.88-71.24 ng/L for Jinxiuchuan Reservoir, 3.850-26.68 ng/L for the city moat, 6.930-41.56 ng/L for Daming Lake, 66.03-474.2 ng/L for Xiaoqing River, 14.66-17.72 ng/L for the Yellow River, and 10.60-26.43 ng/L for Queshan Reservoir. The Xiaoqing River was seriously polluted due to the discharge of wastewater from Jinan. Jinxiuchuan Reservoir had a higher concentration of OP compared with the Yellow River and Queshan Reservoir, which is ascribed to the surrounding human activities. These data are reported for the first time, providing strong support for the control of OP pollution in Jinan.     

ABR反应器中COD/SO_4~(2-)值和硫酸盐负荷对SO_4~(2-)去除影响

利用厌氧折流板反应器,分别考察了反应器启动,及不同COD/SO42-比值和硫酸盐负荷对模拟废水中SO42-去除的影响。实验在(32±0.1)℃,pH为6.0⁶.5的条件下连续运行。结果表明:ABR经过约90 d的启动驯化阶段后,进水硫酸盐及COD浓度分别为1 500 mg/L和3 000 mg/L,水力停留时间为12 h条件下,硫酸盐去除率达到了92%。固定COD/SO42-比值为2.5时,随着进水SO42-浓度的增加(1 5006.5的条件下连续运行。结果表明:ABR经过约90 d的启动驯化阶段后,进水硫酸盐及COD浓度分别为1 500 mg/L和3 000 mg/L,水力停留时间为12 h条件下,硫酸盐去除率达到了92%。固定COD/SO42-比值为2.5时,随着进水SO42-浓度的增加(1 500³ 500 mg/L),SO42-去除率逐渐下降,最低为60%,相反SO42-去除速率随着硫酸盐浓度的增加而增加,最大为7.98 kg(/m3.d);维持恒定的硫酸盐浓度(1 500 mg/L),逐渐缩短水力停留时间以提高反应器中硫酸盐负荷,SO42-去除率呈现先上升后下降的复杂变化趋势,当水力停留时间为6 h时,SO42-去除率达到最大;随着COD/SO42-比值的提高,硫酸盐去除能力增强,且反应体系对硫酸盐负荷的耐受能力也逐渐增强。     

预富集技术在原子吸收光谱环境分析中的应用

原子吸收光谱法是分析环境水样中金属离子含量的有效方法之一。在测定时往往需要对样品进行前处理,然后再进行测定。文章介绍了近些年较新的一些分离富集技术在原子吸收光谱分析环境中金属离子时的应用,分析了离子交换树脂在样品中金属离子富集分离过程中的研究近况,评述了固相萃取、析相微萃取、单滴液滴微萃取、分散液液微萃取、离子液体萃取、浊点萃取等多种萃取方式在样品预富集中的应用进展,综述了活性炭、纳米粒子、淀粉、分子筛等吸附剂在富集环境水样中金属元素的应用现状,同时还对在线富集技术与流动注射分析技术联用在金属元素分析中的应用进展进行了评述。     

论环境自卫权

环境自卫权是环境权的组成部分,环境自卫权及随着环境权的确立而提出来的,环境权作为环境法的核心问题,近年来在国内外的理论界和立法上都有不同程度的反映,使得环境自卫权的实现也就不可避免的带有复杂性,除了必须具备的条件外,环境自卫权的实现还应当注意实施的手段及其相应性的标准,本文就环境自卫权的生成原因、界定、构成及其实现作了初步研究。     

某铅锌尾矿库周边地下水污染特征与评价

通过对西南某铅锌矿尾矿库周围地下水土壤重金属元素含量的测定,研究、评价该尾矿库及其周围的浅层和深层地下水重金属污染、迁移特征及规律,为该类尾矿库工程设计、地下水预防和防治提供科学依据。结果表明：尾矿库下游的浅层地下水的铅和锌超标,尾矿库上游浅层地下水和尾矿库南、东和西的深层岩溶水各重金属物均达到《地下水质量标准》（GB／T14848—93）III类标准要求。尾矿库周围浅层地下水铅、锌、砷等重金属浓度比同一位置的深层地下水的高。