有机物辛醇／水分配系数的计算方法：分子碎片常数法

辛醇／水分配系数是表征有机污染物环境行为的重要参数之一，本文应用于碎片常数计算了１３０余个有机化合物的辛醇／水分配系数对数值，通过计算值与实测值的比较发现，两者之间表现出相当好的一致性，其平均绝对误差为０．１３５，此外，还探讨了该方法应用于不同类型有机污染物时需要注意的问题。     

乌江干流中上游水电梯级开发水温累积效应

以乌江流域洪家渡库尾至乌江渡坝下的水电工程干扰典型段为研究区域，利用建坝前后的水温实测资料，采用建坝前天然水温和建坝后下泄水温比较法，对乌江干流梯级水库水温时空分布特征进行分析。研究结果表明：对天然水温改变最大的电站为洪家渡和乌江渡，前者是受水库水温结构自身影响，后者是梯级联合运行的结果；梯级联合运行使库区水温分层有所减弱，随着时间的推移或上游梯级电站的建成，电站下泄水温年变化过程趋于均化，与天然水温的延迟也越加明显；不同的水库水温结构对水温累积效应的影响也各不相同，稳定分层型水库对水温累积具有正效应，混合型水库具有负效应，过渡型水库处于两者之间，体现了梯级电站的水温累积影响，为研究减缓下泄低温水的对策措施提供依据和参考。     

Operating condition influences on PCDD/Fs emissions from sinter pot tests with hot flue gas recycling

This study was designed to clarify the influence of operating conditions on the formation and emissions of polychlorinated-pdibenzodioxins and dibenzofurans (PCDD/Fs) from a sintering process with hot flue gas recycling. A pilot scale sinter pot with simulated flue gas recycling was developed, and four key operational parameters, including temperature, oxygen content of the simulated waste flue gas, the coke rate of the sintering mixture, and the quicklime quality, were selected for exploring PCDD/Fs formation. The results showed that the temperature of the recycled flue gas had a major affect on PCDD/Fs formation, and a high temperature could significantly increase their formation during sintering. A clear linear correlation between the temperature of recycling flue gas and PCDD/Fs emission (r = 0.93) was found. PCDD/Fs could be reduced to a certain extent by decreasing the level of oxygen in the recycled flue gas, while sintering quality was unchanged. The coke rate had no significant influence on the formation of PCDD/Fs, but the quality of quicklime used in the sintering mixture could affect not only the amount of PCDD/Fs emissions but also the sintering productivity. Compared with a benchmark sinter pot test, PCDD/Fs emissions markedly decreased with improvements to quicklime quality. However, the reduction in PCDD/Fs emissions realized by using high-quality quicklime was limited by the temperature of the inlet gas. The highest reduction achieved was 51% compared with conventional quicklime when the temperature of the inlet gas was 150°C.     

A GFP-based bacterial biosensor with chromosomally integrated sensing cassette for quantitative detection of Hg(II) in environment

A mercury biosensor was constructed by integrating biosensor genetic elements into E. coli JM109 chromosome in a single copy number, using the attP/attB recombination mechanism of λphage. The genetic elements used include a regulatory protein gene (merR) along with operator/promoter (O/P) derived from the mercury resistance operon from pDU1358 plasmid of Serratia marcescens. The expression of reporter gene gfp is also controlled by merR/O/P. Integration of the construct into the chromosome was done to increase the stability and precision of the biosensor. This biosensor could detect Hg(II) ions in the concentration range of 100-1700 nmol/L, and manifest the result as the expression of GFP. The GFP expression was significantly different (P ≤ 0.05) for each concentration of inducing Hg(II) ions in the detection range, which reduces the chances of misinterpretation of results. A model using regression method was also derived for the quantification of the concentration of Hg(II) in water samples.     

pH-dependent leaching behaviour and other performance properties of cement-treated mixed contaminated soil

Portland cement has been widely used for stabilisation/solidification (S/S) treatment of contaminated soils. However, there is a dearth of literature on pH-dependent leaching of contaminants from cement-treated soils. This study investigates the leachability of Cu, Pb, Ni, Zn and total petroleum hydrocarbons (TPH) from a mixed contaminated soil. A sandy soil was spiked with 3000 mg/kg each of Cd, Cu, Pb, Ni and Zn, and 10,000 mg/kg of diesel, and treated with ordinary Portland cement (CEM I). Four different binder dosages, 5%, 10%, 15% and 20% (m/m) and different water contents ranging from 13%-19% dry weight were used in order to find a safe operating envelope for the treatment process. The pH-dependent leaching behaviour of the treated soil was monitored over an 84-day period using a 3-point acid neutralisation capacity (ANC) test. The monolithic leaching test was also conducted. Geotechnical properties such as unconfined compressive strength (UCS), hydraulic conductivity and porosity were assessed over time. The treated soils recorded lower leachate concentrations of Ni and Zn compared to the untreated soil at the same pH depending on binder dosage. The binder had problems with Pb stabilisation and TPH leachability was independent of pH and binder dosage. The hydraulic conductivity of the mixes was generally of the order, 10^-8 m/sec, while the porosity ranged from 26%-44%. The results of selected performance properties are compared with regulatory limits and the range of operating variables that lead to acceptable performance described.     

Efficiency and degradation products elucidation of the photodegradation of mefenpyrdiethyl in water interface using TiO2 P-25 and Hombikat UV100

The photodegradation of mefenpyrdiethyl (MFD), an herbicide safener, was investigated in aqueous suspensions by using Degussa P-25 and Hombikat UV100 titanium oxide under simulated sunlight irradiation. The effects of initial concentration of the herbicide, pH, catalysts and hydrogen peroxide doses as well as their combinations were studied and optimized. Accordingly, the kinetic parameters were determined and the effectiveness of the processes was assessed by calculating the rate constants. A pseudo first-order kinetics was observed. Under experimental conditions, the degradation rate constants were strongly influenced using P-25 and no noticeable effect was observed for Hombikat UV100. DFT calculations with B3LYP/6-311+G(2d,p)//B3LYP/6-31+G(d,p) level of theory were performed to check whether significant conformational changes occur when the charge state of the MFD substrate changes and whether these changes could play a role in the dependency of photodegradation rate constant on the studied pH. High resolution mass spectrometry (FT-ICR/MS) was implemented to identify the main degradation products.     

Seasonal trend of ambient PCDD/Fs in Tianjin City, northern China using active sampling strategy

The spatial concentrations, seasonal trends, profiles and congener pairs of ambient polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were investigated within a seasonally active sampling scheme during Jun 2008 and Jan 2009 in Tianjin City, northern China. The PCDD/F concentrations ranged 14.2-172 fg I-TEQ/m³ (average 69.3 fg I-TEQ/m³) in summer and (89.8-1.01) × 10³ fg I-TEQ/m³ (average 509 fg I-TEQ/m³) in winter, respectively, except for the E-waste dismantling site where much higher values were observed (1.04 × 10³ fg I-TEQ/m³ in summer and 7.123 × 10³ fg I-TEQ/m³ in winter). The results indicated a significantly seasonal trend with higher TEQ values in winter as compared with summer, which could be related to increased emission sources and seasonal variations of the atmospheric boundary layer height. 2,3,4,7,8-PeCDF was the dominant contributor to the total PCDD/F toxic equivalents, and 2,3,7,8-TCDD was detected at almost all the sampling sites in winter. Most of the similarly substituted PCDD/F congener pairs exhibited high correlations, suggesting that they might have similar environmental fate or sources. But different seasonal and spatial distributions of PCDD/F concentrations indicated that the emission sources might be intermittent.     

广州市不同功能区大气二噁英含量和分布特征研究

应用气相色谱-高分辨率质谱仪(GC-HRMS)对广州市秋冬季6个区域环境空气样品中的17种2,3,7,8-氯代二英含量进行了检测.结果表明,广州市各观测区域大气中二英毒性当量浓度范围为0.151～2.230pg.m-3,均值为0.418pg.m-3.各观测区域空气中二英毒性当量浓度分布存在一定的差异,本研究的背景区、居民住宅区和商业区二英毒性当量浓度较低且水平相近,分别为(0.294±0.099)、(0.305±0.115)、(0.308±0.102)pg.m-3.交通枢纽区、郊区和工业区二英毒性当量浓度相对较高,分别为(0.342±0.049)、(0.423±0.113)和(0.838±0.704)pg·m-3.广州市不同功能区二英毒性当量浓度呈现背景区<住宅区<商业区<交通枢纽区<郊区<工业区的分布特点.与2004年相比,广州市城区二英毒性当量浓度有所下降,郊区毒性当量浓度有所上升.     

Adsorption characteristics and mechanism of Cr （Ⅵ） on chitoan-yttrium porous microsphere

以壳聚糖和Y2（OH）5NO3为原料通过乳液交联法制备了壳聚糖-钇（Ch—Y）复合微球,通过扫描电镜、透射电镜、X射线衍射、红外光谱等方法对其表面形貌、结构进行了表征.探讨了溶液的pH值、反应时间、投加量、离子初始浓度对其吸附性能的影响.研究结果表明,壳聚糖-钇（Ch—Y）复合微球在pH值为3的酸性环境中对Cr（Ⅵ）保持了较高的吸附能力,吸附容量为52.39mg·g-1,其吸附行为符合Langmuir吸附等温模型;通过吸附机理的研究,发现壳聚糖-钇（Ch—Y）对Cr（Ⅵ）吸附是化学吸附静电吸附协同氧化Cr（Ⅵ）离子作用来实现的.