Determination of Chlorophenols in Sewage Sludge and Soil by High-Performance Liquid Chromatography–Tandem Mass Spectrometry with Ultrasonic-Assisted and Solid-Phase Extraction

Chlorophenols are a category of toxic pollutants that are ubiquitously present in the environment. This paper presents a reliable and feasible method for the determination of five chlorophenols in sewage sludge and soil using liquid chromatography–tandem mass spectrometry (LC-MS/MS). The pretreatment involved ultrasonic-assisted extraction and solid-phase extraction purification with hydrophilic–lipophilic balance cartridges. LC-MS/MS equipped with an electrospray ionization source operated in negative mode was used for detection, and multitude reaction monitoring mode was applied for data acquisition. The pretreatment and working conditions of LC-MS/MS were optimized to achieve satisfactory results. The intra-batch accuracies were 100.5–113.4% with relative standard deviations?≤?15.6% for the chlorophenols in sewage sludge and 71.3–102.7% with relative standard deviations?≤?14.0% for those in soil. The inter-batch accuracies were 86.1–100.5% (relative standard deviations?≤?33.6%) for sewage sludge samples and 70.5–112.5% (relative standard deviations?≤?28.2%) for soil samples, respectively. This method has been applied to the determination of chlorophenols in sewage sludge of wastewater treatment plants and soil collected from Guangzhou, China. Parachlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, and pentachlorophenol were detected in some sewage sludge samples, with concentrations from 0.51 to 13.20?ng/g. In addition, parachlorophenol, 2,3,4,6-tetrachlorophenol, and pentachlorophenol were found in all the soil samples with concentrations from 0.33 to 5.21?ng/g. The chromatographic behavior, on-filter adsorption behavior, and the relationship between optimal collision energies and degree of chlorination of the chlorophenols was investigated. This method will be conducive to environmental research focusing on pollution investigation of chlorophenols in the environment.     

THE REFORM OF TEACHING CONTENT FOR THE COURSE OF FOUNDATION SETTLEMENT

对地基土沉降计算的课程内容提出改革思路,从讨论土体固结度的角度展开,进而引出最终沉降量的计算,最终引出不同的试验方法和压缩性指标。新的教学思路将土力学固结沉降的基本理论与实践应用进行合理的区隔,既能保证基本理论的纯粹性、合理性,也不回避实践中土体复杂 性质对理论进一步发展和丰富所提出的挑战。     

横观各向同性饱和地基上中厚圆板的非轴对称振动

研究横观各向同性饱和土地基上中厚弹性圆板的非轴对称振动问题。基于横观各向同性饱和介质Biot波动方程的一般解,按混合边值问题建立了饱和地基与弹性中厚圆板非轴对称动力相互作用的对偶积分方程,并将对偶积分方程转化为易于计算的第二类Fredholm积分方程;采用数值方法求解该积分方程。数值算例结果表明,当h/a>0.05时,饱和半空间体上中厚度圆板在不同频率下的振动特性与相应频率下的刚性板的振动特性基本相同,当h/a<0.05时,板中心的位移将随h/a的减小而增大。     

剪切模量是幂函数的成层土的地震随机反应

基于改进的一维剪切梁模型，对剪切模量是其深度的某一幂函数的成层非均质土层，得到其稳态动力响应的封闭型解析表达式。首次证明了这种土层振型函数的正交性，然后利用随机振动理论，并基于基岩输入地震加速度的功率谱密度函数：白噪声谱和过滤白噪声谱。研究了该土层对地震的随机动力响应问题。计算结果表明，1)在基岩输入地震加速度的功率谱为白噪声谱的情况下，土层的最大期望反应均有别于过滤白噪声谱时的相应值；2)平稳输入与输出过高地估计了土层的随机响应。     

土壤与沉积物样品中多氯联苯总量的气相色谱-质谱法快速分析

建立了土壤和沉积物样品中多氯联苯总量的快速分析方法.样品经加速溶剂萃取,Bond ElutPCB SPE小柱净化后,采用气相色谱-质谱测定多氯联苯的总量,方法的平均回收率为84% ～106%,相对标准偏差为4.2% ～8.4%,多氯联苯总量的方法检出限为2.25 ng/g.该方法快速、灵敏、准确,适用于大部分土壤及沉积物样品中多氯联苯总量的快速筛查分析.     

Thermal analysis applied to the characterization of degradation in soil of polylactide: I. Calorimetric and viscoelastic analyses

An accelerated soil burial test has been performed on a commercial polylactide (PLA) for simulating non-controlled disposal. Degradation in soil promotes physical and chemical changes in polylactide properties, which can be characterized by Thermal Analysis techniques. Physical changes occurred in polylactide due to the degradation in soil were evaluated by correlating their calorimetric and viscoelastic properties. It is highly remarkable that each calorimetric scan offers specific and enlightening information. Degradation in soil affects the polylactide chains reorganization. A multimodal melting behavior is observed for buried PLA, degradation in soil also promotes the enlarging the lamellar thickness distribution of the population with bigger average size. Morphological changes due to degradation in soil lead to an increase in the free volume of the polylactide chains in the amorphous phase that highly affected the bulk properties. Thermal Analysis techniques provide reliable indicators of the degradation stage of polylactide induced by degradation in soil, as corroborated by molecular weight analysis.     

On‐line flow‐through extraction–preconcentration‐large volume injection‐RP LC for trace determination of pyrethroids in Slovak soil

A rapid micro‐analytical multiresidue method was developed for analysis of pyrethroids (kadethrin K, cypermethrin C and permethrin P) in soil micro‐sample (200 mg). It uses on‐line flow‐through extraction of soil micro‐samples (packed into a short glass column) with a methanol‐aqueous citric acid buffer mixture, successive on‐line SPE preconcentration of analytes from the extract and on‐line RP‐HPLC analysis with UV photometric detection. The separation of pyrethroids is performed on a Purospher RP‐18e column with methanol/water as mobile phase. Effects of sorbent placed at the bottom of a short column holding the soil sample and different kinds of on‐line SPE columns were tested. Besides, the influence of volume of the effluent on the pyrethroids recovery was also studied. Calibration curves were linear over the range assayed from 0.01 to 0.2 μg/mL with correlation coefficients of linear regression (least‐squares method) in the range 0.998–0.999. Recovery studies were carried out at 0.25–1.00 μg/g dry soil fortification level and obtained recoveries were for K 81–84%, C 56–59% and for P 58–63%. Achieved LOD (confidence band) of studied pyrethroids were for large‐volume injection (1 mL) 4.5 ng K, 3.7 ng C, 3.6 ng P or 27 ng/g K, 32 ng/g C and 29 ng/g P in dry soil “solid sampling HPLC”.     

The carbon versus mass diagram to visualize and exploit FTICR‐MS data of natural organic matter

A two‐dimensional diagram is proposed, in which the carbon number of each formula is plotted against its nominal mass, to visualize large sets of molecular formula data that can be derived from data generated by ultrahigh‐resolution Fourier transform ion cyclotron resonance‐MS. In such a carbon versus mass (CvM) diagram, each formula (C_cH_hO_o) is unambiguously described by c, its (nominal) mass and the parameter i = c + o. Calculations of chemically allowable formulas illustrate that organic molecules occupy only certain spaces in such a diagram. The extension of these spaces increases with molecular mass in x‐direction (hydrogenation) and y‐direction (oxygenation). The data sets of molecules determined in natural organic matter(NOM) occupy only a certain range of the allowable space. The intensity of the mass spectrometric signals can be included as the third dimension into a CvM diagram. Separate CvM diagrams can be plotted for NOM molecules that include different heteroatoms. The benefits of the CvM diagram are illustrated by application onto data sets of fulvic acids from riverine and marine origin, of secondary organic aerosol, including organosulfates and organonitrates, as well as of ozonation of fulvic acids. The CvM diagram is a useful tool to visualize the elemental regularities in NOM isolates as well as the differences between isolates. It may also be applicable to large sets of molecular formula data generated in other disciplines such as petroleum biogeochemistry or metabolomics. Copyright © 2010 John Wiley & Sons, Ltd.     

气相色谱法测定茶叶及土壤中的高效氯氟氰菊酯残留量

建立了气相色谱测定茶叶及土壤中高效氯氟氰菊酯残留量的分析方法。茶叶和土壤样品用正己烷提取,毛细管柱分离,气相色谱-电子捕获检测器(GC-ECD)检测。结果表明: 在高效氯氟氰菊酯添加量为0.02～2.00 mg/kg范围内,高效氯氟氰菊酯在鲜茶叶和土壤中的平均添加回收率分别为89.0%～94.1%和89.8%～94.7%,相对标准偏差(RSD, n=5)分别为3.0%～4.9%和2.5%～4.2%,方法的最低检出限(S/N=3)为0.002 mg/kg。采用该方法测定2.5%高效氯氟氰菊酯微乳剂在湖南长沙茶叶及土壤中的消解动态,其符合一级动力学消解模式,消解方程分别为y=3.1996e-0.3394x和y=0.1224e-0.1036x,相关系数分别为0.9956和0.9247。在茶叶中的半衰期为2.04 d,在土壤中的半衰期为6.69 d。该方法为湖南长沙地区茶叶种植科学合理地使用杀虫剂高效氯氟氰菊酯提供了依据。