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.     

Effects of physical and chemical characteristics of surface sediments in the formation of shallow lake algae-induced black bloom

Surface sediments are closely related to lake black blooms. The dissolved oxygen （DO） distribution and its penetration depth in surface sediments as well as the migration and transformation of redox sensitive elements such as Fe and S at the sediment-water interface are important factors that could influence the formation of the black bloom. In this study, dredged and undredged sediment cores with different surface properties were used to simulate black blooms in the laboratory. The Micro Profiling System was employed to explore features of the DO and ∑H2S distribution at the sediment-water interface. Physical and chemical characteristics in sediments and pore waters were also analyzed. The results showed that sediment dredging effectively suppressed the black blooms. In the undredged treatment, DO penetration depth was only 50 μm. Fe^2＋ concentrations, ∑H2S concentrations, and ∑H2S production rates were remarkably higher in surface sediments and pore waters compared to control and dredged treatments. Furthermore, depletion of DO and accumulation of Fe^2＋ and ∑H2S in surface sediments and pore waters provided favorable redox environments and necessary material sources for the blooms. The study results proved that physical and chemical characteristics in surface sediments are important factors in the formation of the black bloom, and could provide scientific guidance for emergency treatment and long-term pre-control of black blooms.     

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.     

Speciation of organic phosphorus in a sediment profile of Lake Taihu II. Molecular species and their depth attenuation

The understanding of organic phosphorus(P) dynamics in sediments requires information on their species at the molecular level,but such information in sediment profiles is scarce.A sediment profile was selected from a large eutrophic lake,Lake Taihu(China),and organic P species in the sediments were detected using solution phosphorus-31 nuclear magnetic resonance spectroscopy(31 P NMR) following extraction of the sediments with a mixture of 0.25 mol/L NaOH and 50 mmol/L EDTA(NaOH-EDTA) solution.The results showed that P in the NaOH-EDTA extracts was mainly composed of orthophosphate,orthophosphate monoesters,phospholipids,DNA,and pyrophosphate.Concentrations of the major organic P compound groups and pyrophosphate showed a decreasing trend with the increase of depth.Their half-life times varied from 3 to 27 years,following the order of orthophosphate monoesters > phospholipids DNA > pyrophosphate.Principal component analysis revealed that the detected organic P species had binding phases similar to those of humic acid-associated organic P(NaOH-NRP HA),a labile organic P pool that tends to transform to recalcitrant organic P pools as the early diagenetic processes proceed.This demonstrated that the depth attenuation of the organic P species could be partly attributed to their increasing immobilization by the sediment solids,while their degradation rates should be significantly lower than what were suggested in previous studies.     

不同类型湖泊沉积物中氮释放规律研究

通过对武汉市东湖子湖郭郑湖、庙湖以及南湖这3个不同类型的湖泊进行释氮模拟实验,结果表明:(1)在厌氧条件下,不同污染程度的湖泊中沉积物释氮作用均比较明显。为了抑制沉积物向上覆水释氮,控制湖泊富营养化,保持湖泊较高的溶解氧水平是必要的。(2)在厌氧条件下,高温对不同类型湖泊总氮和氨氮的释放均能起到促进作用。(3)沉积物与上覆水间污染物的浓度梯度越大,总氮和氨氮的释放速率与释氮量也越大,此时温度的影响不明显。(4)通过比较3类湖泊沉积物上覆水中总氮和氨氮两者的释放浓度可知,氨氮的释放贡献十分显著,因此控制氨氮的释放量对于控制湖泊氮释放量具有显著效果。     

城市排水系统沉积物特性研究

重点阐述了沉积物的来源和组成,沉积物的颗粒粒径、有机物含量(VSS/SS)、颗粒粘性和颗粒密度等物化性质,以及附着于沉积物上的金属污染物的相关特征。其粒度分布范围是D10为1.89～223.21μm,D50为12.38～437.30μm,D90为39.06～1 572.52μm;VSS/SS的范围是1%～38%;密度范围是1.80～2.47 g/cm3。金属污染物主要的附着对象是沉积物中的细小颗粒如生物膜上。以上沉积物性质对于解决排水系统的泥沙淤积问题以及水体污染的控制都具有重要意义。     

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。     

辽宁大伙房水库沉积物中有机氯农药和多氯联苯的分布、来源及风险评价

利用GC-MS测定24个大伙房水库表层沉积物中有机氯农药和多氯联苯含量,主要揭示水库沉积物中有机氯农药和多氯联苯的残留特征.结果表明,HCHs的含量为0.70～3.48 ng.g-1,均值为（1.58±0.71）ng.g-1;DDTs的含量为0.85～4.94ng.g-1,均值为（1.94±0.82）ng.g-1;PCBs的含量为1.46～3.52 ng.g-1,均值为（2.42±0.64）ng.g-1.γ-HCH、β-HCH、DDE、DDT和PCB28百分含量较高.高百分含量γ-HCH和DDT表明目前仍在使用的林丹和工业滴滴涕产品;β-HCH、DDE和PCB28可能来自土壤中农药和多氯联苯残留.水库上游污染物含量明显高于水库下游,同时污染物高值点主要集中在浑河河口,表明水库上游浑河河流搬运是水库沉积物中污染物的主要输入来源,并影响污染物在沉积物中的分布.生态风险评价结果表明,沉积物中DDTs和γ-HCH存在较高的生态风险;沉积物中PCBs残留尚未对周围环境造成不利影响.