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.     

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: Kinetics, isotherms and thermodynamics

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qm /SSA) and SSA-normalized adsorption coefficient (Kd /SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (△ G0 ) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (△ H0 ), G0 and free energy of adsorption (Ea ), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and K d /SSA or q m /SSA.     

Occurrence and distribution of hexabromocyclododecane in sediments from seven major river drainage basins in China

The concentrations and geographical distribution of hexabromocyclododecane (HBCD) were investigated in 37 composite surface sediments from seven major river drainage basins in China, including Yangtze River, Yellow River, Pearl River, Liaohe River, Haihe River, Tarim River and Ertix River. The detection frequency of HBCD was 54%, with the concentrations ranged from below limit of detection (LOD) to 206 ng/g dry weight. In general, the geographical distribution showed increasing trends from the upper reaches to the lower reaches of the rivers and from North China to Southeast China. Compared to other regions in the world, the average concentration of HBCD in sediments from Yangtze River drainage basin was at relatively high level, whereas those from other six river drainage basins were at lower or similar level. The highest HBCD concentration in sediment from Yangtze River Delta and the highest detection frequency of HBCD in Pearl River drainage basins suggested that the industrial and urban activities could evidently affect the HBCD distribution. HBCD diastereoisomer profiles showed that γ-HBCD dominated in most of the sediment samples, followed by α- and β-HBCD, which was consistent with those in the commercial HBCD mixtures. Further risk assessment reflected that the average inventories of HBCD were 18.3, 5.87, 3.92, 2.50, 1.77 ng/cm 2 in sediments from Pearl River, Haihe River, Tarim River, Yellow River and Yangtze River, respectively.     

天津近岸表层沉积物重金属和放射性核素分布特征

对渤海湾天津海域14个表层沉积物样品进行粒度、重金属和核素放射性活度测量,结果显示,沉积物组成以粉砂为主,其粒径在研究区横纵向上分别呈由南至北、由东至西逐渐变粗的分布特征.重金属元素含量为Cu:25.6~35.1mg/kg、Pb:44.1~67.7mg/kg、Zn:60~73.5mg/kg;210Pb活度为13.2~35.3Bq/kg,137Cs活度为0.05~1.28Bq/kg,重金属含量和放射性活度随粒径减小而增大,总体上呈由北至南逐渐增大的分布特征,在中部和南部分别呈由西北至东南和由西至东逐渐增大的分布特征.这主要是因为细颗粒组分对Cu、Pb、Zn、210Pb和137Cs的吸附作用大于粗颗粒组分,因此,其分布受渤海湾水流及其所导致的粒径变化所影响.     

Research on the evolvement of morphology of coking coal during the coking process

The evolvement of morphology and structure of the coal with different metamorphic degrees during coking process in the vertical furnace was investigated by infrared Image detector. Moreover, the temperature distribution in the radial direction and the crack formation were also studied in heating process. The results show that the amount of crack and the shrinkage level of char decrease with the coal rank rising. In addition, the initial temperature of crack formation for char increases with the coal rank rising.     

昆明市环境应急监测能力建设现状及对策建议

结合昆明市环境应急监测能力建设的现状,着重分析存在的主要问题,提出了相应的对策建议。     

陕西红碱淖湖底表层沉积物粒度特征

根据不同沉积环境的代表性和空间分布的均匀性原则,对陕西北部红碱淖湖泊表层沉积物进行了较为系统的采样和粒度分析。粒度分析结果显示,红碱淖湖泊表层底泥主要由三种沉积类型组成：湖心稳定的湖泊沉积、受入湖河流影响的河口及三角洲沉积、相对稳定的近岸沉积。粒度分布的多组分特征不仅指示了沉积物来源差异,还指示了其环境和沉积动力。平均粒径的空间分布特征可以指示湖泊底流的流向及动力特征。发现西部湖盆目前仍受入湖径流的影响,而东部湖盆则受入湖径流影响相对较弱。粒度揭示的湖泊底流特征,可以作为研究入湖污染物及其扩散规律的依据之一。     

基于时频分析的裂纹转子碰摩故障特征研究

为研究转子系统耦合故障特性,采用有限元方法建立了含有横向裂纹、转静碰摩的非线性转子动力学模型。首先研究了不同转速下裂纹、碰摩单一故障下转子系统的振动响应,其次研究了两种故障耦合情况下系统的振动响应特征。采用波形图、FFT谱图、瞬时频率和Hilbert-Huang时频谱(HHS)相结合的方法对故障转子振动信号进行了分析。分析结果表明:运用多种时频分析相结合的方法可以较为全面地了解转子的故障特征,裂纹转子在1/5、1/3临界转速时会发生较为明显的5X、3X谐波,且裂纹的产生会导致响应幅值增大,从而引起更为严重的碰摩。      

新泰市地表水水质评价与防治策略

新泰市地表水环境承载着城区供水、容纳排污、农田灌溉,其由柴汶河流域、金斗山水库、光明水库、东周水库水组成;依据2009--2012年监测数据,采用综合污染指数法、单因子类别法评价了柴汶河流域以及三个水源地的水质;水质评价内容包括：污染物浓度平均值、水污染因子分担率、污染指数、水库富营养化程度等;提出了切实可行的地表水环境防治策略。     

空白值校正法无汞快速测定地表水化学需氧量

探讨了K2Cr2O7在不同酸度的硫酸介质中的化学行为,确定9 mol/L H2SO4为K2Cr2O7法测定地表水COD的合理酸度。多种有机物消解试验及半年多地表水样跟踪检测,将消解回流时间从2小时缩短到30分钟之内是可行的。氯离子(Cl-)干扰可用生成AgCl沉淀和空白值校正的办法消除。此方法的检出下限是11mg/L,样品测定的加标回收率在96%～101%。此方法不仅缩短了回流时间、减少了汞带来的二次污染,从而实现无汞快速测定地表水COD。