SPE-UPLC-MS/MS法测定地下水中多种农药残留

采用固相萃取超高效液相色谱串联质谱法(SPE-UPLC-MS/MS)同时测定地下水中涕灭威、克百威、2,4滴和五氯酚等4种农药残留,通过优化试验条件,使方法在10.0μg/L～200μg/L范围内线性良好,检出限为0.003μg/L～0.006μg/L.标准溶液低、中2个质量浓度水平的加标回收率为84.1％ ～98.8...     

Molecularly imprinted polymer for analysis of trace atrazine herbicide in water

A molecularly imprinted polymer (MIP) for atrazine was synthesized by non-covalent method. The binding capacity of MIP was 1.00 mg g^{? 1} polymer. The selectivity and recovery were investigated with various pesticides which are mostly, found in the environment, for both similar and different chemical structure of atrazine. The competitive recognition between atrazine and structurally similar compounds was evaluated and it was found that the system provided highest recovery and selectivity for atrazine while low recovery and selectivity were obtained for the other compounds. The highest recovery was obtained from MIP compared with non-imprinted polymer (NIP), a commercial C₁₈ and a granular activated carbon (GAC) sorbent. The method provided high recoveries ranged from 94 to 99% at two spiked levels with relative standard deviations less than 2%. The lower detection limit of the method was 80 ng L^{? 1}. This method was successfully applied for analysis of environmental water samples.     

Oxidative stress and genotoxicity of 1-methyl-3-octylimidazolium chloride on loach (Misgurnus anguillicaudatus)

This study was a preliminary step to evaluate the acute toxicity of 1-methyl-3-octylimidazolium chloride ([C₈mim]Cl) on loach (Misgurnus anguillicaudatus) by determining the effects on hepatic antioxidant enzyme activities and by the comet assay. The results showed that [C₈mim]Cl had acute toxicity at concentrations above 20 mg L^?1, inducing oxidative stress and genotoxicity on fish liver cells. In respect to enzyme activities, [C₈mim]Cl induced changes in the activities of superoxide dismutase, catalase, and glutathione content the livers of fish exposed at 20–80 mg L^?1. [C₈mim]Cl at the same exposure level caused a remarkable increase in malondialdehyde level. The comet assay indicated that [C₈mim]Cl at 20–80 mg L^?1 induced genotoxicity in liver cells. With increased exposure concentration and time, the two comet parameters trailing rate and tail moment were significantly increased, with significant differences (P < 0.05) observed between control group and each treatment group. The present study shows that ionic liquids can be a threat to the health of aquatic organism when accidentally released to aquatic ecosystems.     

Three-dimensional patterns of moisture, water repellency, bromide and pH in a sandy soil

Soil water repellency might lead to preferential flow of water and solutes through the unsaturated zone of soils. To study this process in a water repellent sandy field soil, a bromide tracer had been applied on a 2.2 m long and 0.4 m wide plot. The bromide application rate was 8 g/m², and the plot was sampled using 100 cm³ steel cylinders after 52 mm of rainfall in 12 days. A total of seven layers were sampled to a depth of 74 cm. Each layer was sampled at 240 locations in a 40 by 6 grid. All samples were used for the determination of soil water content, degree of actual and potential water repellency, bromide concentration and pH. The spatial distribution of these properties was visualized three-dimensionally and compared. The degree of water repellency, bromide concentration, and pH distribution bore close resemblance to the fingered flow induced soil water content distribution. The degree of potential water repellency was relatively low in places with such fingers. Actual water repellency occurred between the fingers at the dry spots. Bromide was not found, or only in very low concentrations, in such places. Bromide depth profiles clearly indicated the occurrence of diverging flow in the wetter subsoil. Most likely, manuring activities during the last decades resulted in relatively high pH values in the topsoil, and in the subsoil along the recurring fingered flow pathways.     

Hydrological and geochemical factors affecting leachate composition in municipal solid waste incinerator bottom ash: Part I: The hydrology of Landfill Lostorf, Switzerland

The objective of the investigation of the municipal solid waste incinerator (MSWI) bottom ash landfill, Landfill Lostorf, was to determine the residence time of water in the landfill and the flow paths through the landfill. Over a period of 22 months, measurements of rainfall, landfill discharge and leachate electrical conductivity were recorded and tracer experiments made. Over the yearly period 1995, approximately 50% of the incident rainfall was measured in the discharge. An analysis of single rain events showed that in winter, 90–100% of rainfall was expressed in the landfill discharge, whereas in summer months, the value was between 9 and 40% depending on the intensity of the rain event. The response to rainfall was rapid. Within 30–100 h, approximately 50% of water discharged in response to a rain event had left the landfill. The discharge was less than 4 l/min for approximately 50% of the measurement periods. Qualitative tracer studies with fluorescein, pyranine and iodide clearly showed the existence of preferential flow paths. This was further substantiated by quantitative tracer studies of single rain events using / ratios and electrical conductivity measurements. The proportion of rainwater passing directly through the landfill was found to be between 20 and 80% in summer months and around 10% in winter months. The difference has been ascribed to the water content in the landfill. The average residence time of the water within the landfill has been estimated to be roughly 3 years and this water is the predominant component in the discharge over a yearly period.     

改进测定水中氨氮分子吸收光谱法的试验研究

水中氨氮含量是反应水质状况的重要指标。文章对测定水中氨氮气相分子吸收光谱法(标准号HJ/T195-2005)进行了改进试验研究。第一,对氧化剂的配比进行了改进,使氨氮的测定范围扩展至100μg。第二,对标准HJ/T195-2005中直接使用亚硝酸钠标准溶液做标准曲线的处理方式也做了探讨。通过一系列对比实验认为,应用硫酸铵标准溶液做工作曲线更加准确合理。最后应用改进后的气相分子吸收光谱法和纳氏比色法或滴定法对多种实际废水样品进行同时测定。结果表明,改进后的气相分子吸收光谱法测定氨氮的范围更宽,灵敏度更高和准确度更好。     

氯代苯胺对斑马鱼的急性毒性的电性拓扑研究

基于拓扑理论计算了7种氯代苯胺分子的Kier和Hall的原子类型电性拓扑状态指数(E)f。通过多元线性回归和最佳变量子集回归方法建立了氯代苯胺对斑马鱼急性毒性(pLC5)0与其电性拓扑状态指数的最佳二元定量构效关系(QSAR)模型,其传统判定系数(R)2为0.978,逐一剔除法(LOO)的交互验证系数(Q)2为0.964。根据统计学观点,该模型具有良好的稳健性及预测能力,用该模型给出的估算值和实验值非常接近,优于相关文献的计算结果。从进入该QSAR模型的2个电性拓扑状态指数(E9,E2)6可见,所建的数学方程显示芳环内=C<及硝基中氮原子(=N≤)是影响其pLC50的主要结构因素。     

植物释放挥发性有机物(BVOC)向二次有机气溶胶(SOA)转化机制研究

利用自制玻璃生态罩,研究植物挥发性有机物（BVOC）的释放机制.在紫外光诱导条件下,BVOC经历一系列的光氧化反应,最终产生了二次有机气溶胶（SOA）.运用固相微萃取（SPME）和气相色谱-质谱联用（GC-MS）技术,对目标植物（驱蚊草）释放出的BVOC进行采样分析,共检测出7种主要化合物,其中主要为单萜类、倍半萜类、醇类和酮类物质.研究发现,在紫外光的照射下,这些BVOC可以发生光氧化反应转化为SOA.利用串联差分淌度分析仪（TDMA）测定SOA的粒径分布和SOA颗粒物的吸湿性.结果表明粒径范围大致是50～320 nm,吸湿性研究发现这些SOA具有吸湿性,生长因子可以从1.05增长到1.11.     

Study of metabolites from the degradation of polycyclic aromatic hydrocarbons (PAHs) by bacterial consortium enriched from mangrove sediments

The PAH metabolites produced during degradation of fluorene, phenanthrene and pyrene by a bacterial consortium enriched from mangrove sediments were analyzed using the on-fiber silylation solid-phase microextraction (SPME) combining with gas chromatography–mass spectrometry (GC–MS) method. Seventeen metabolites at trace levels were identified in different PAH degradation cultures based on the full scan mass spectra. In fluorene degradation cultures, 1-, 2-, 3- and 9-hydroxyfluorene, fluorenone, and phthalic acid were detected. In phenanthrene and pyrene degradation cultures, various common metabolites such as phenanthrene and pyrene dihydrodiols, mono-hydroxy phenanthrene, dihydroxy pyrene, lactone and 4-hydroxyphenanthrene, methyl ester, and phthalic acid were found. The detection of various common and novel metabolites demonstrates that SPME combining with GC–MS is a quick and convenient method for identification as well as monitoring the real time changes of metabolite concentrations throughout the degradation processes. The knowledge of PAH metabolic pathways and kinetics within indigenous bacterial consortium enriched from mangrove sediments contributes to enhance the bioremediation efficiency of PAH in real environment.     

Phytoremediation of Cadmium-Contaminated Soils by Rorippa globosa Using Two-Phase Planting (5 pp)

Background Phytoextraction of contaminated soils by heavy metals can provide a great promise of commercial development. Although there are more than 400 species of hyperaccumulators found in the world, phytoremediation technology is rarely applied in field practice for remedying contaminated soils, partially due to low biomass and long growth duration for most of discovered hyperaccumulating plants. In order to enhance the metal-removing efficiency in a year, the two-phase planting countermeasure of phytoextraction by harvesting anthesis biomass was investigated on the basis of the newly found Cd-hyperaccumulator Rorippa globosa (Turcz.) Thell. with 107.0 and 150.1 mg/kg of the Cd accumulation in stems and leaves, respectively, when soil Cd added was concentrated to 25.0 mg/kg. Methods The field pot-culture experiment was used to observe the distribution property of R. globosa aboveground biomass and to examine characteristics of accumulating Cd by the plant at different growth stages. The concentration of Cd in plants and soils was determined using atomic absorption spectrophotometry (AAS). Results and Discussion The results indicated that the total dry stem and leaf biomass of R. globosa harvested at the flowering phase was up to 92.3% of that at its full maturity and the concentration of Cd in stems and leaves harvested at the flowering phase was up to 73.8% and 87.7% of that at the mature phase, respectively. The Cd-removing ratio by shoots of R. globosa harvested at the flowering phase was up to 71.4% of that at the mature phase. It was also found, by observing the growth duration of R. globosa, that the frostless period at the experiment site was twice as long as the growth time from the seedling-transplanted phase to the flowering phase of the hyperaccumulator. Conclusion R. globosa could be transplanted into contaminated soils twice in one year by harvesting the hyperaccumulator at its flowering phase based on climatic conditions of the site and traits of the plant growth. In this sense, the extraction efficiency of Cd in shoots of R. globosa increased 42.8% compared to that of at its single maturity when the plant was transplanted into contaminated soils after it had been harvested at its flowering phase and the plant accumulated Cd from soil at the same extraction ratio at its second flowering phase. Thus, the method of anthesis biomass regulation by the two-phase planting is very significant to increase the Cd-removing efficiency by phytoremediation used in practice over the course of a year. Recommendation and Outlook As for some hyperaccumulators that the growth duration from the seedling-transplanted phase to the flowering phase are short and the concentrations of heavy metals accumulated in their shoots at the flowering phase are high, the efficiency of phytoremediation can greatly be improved using the method of the two-phase planting.