Perfluorinated Surfactants in Surface and Drinking Waters (9 pp)

Background, Aim and Scope In this paper recent results are provided of an investigation on the discovery of 12 perfluorinated surfactants (PS) in different surface and drinking waters (Skutlarek et al. 2006 a, Skutlarek et al. 2006 b). In the last years, many studies have reported ubiquitous distribution of this group of perfluorinated chemicals, especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in the environment, particularly in wildlife animal and human samples (Giesy and Kannan 2001, Houde et al. 2006, Prevedouros et al. 2006). Perfluorinated surfactants (e.g. PFOS and PFOA) have shown different potentials for reproductory interference and carcinogenity in animal experiments as well as partly long half-lives in humans (Guruge et al. 2006, FSA UK 2006a, FSA UK 2006b, 3M 2005, OECD 2002, Yao and Zhong 2005). They possess compound-dependent extreme recalcitrance against microbiological and chemical degradation and, in addition, they show variable potentials for bioaccumulation in animals and humans (Houde et al. 2006). Materials and Methods: Surface and drinking water samples were collected from different sampling sites: - Surface waters: samples taken from the rivers Rhine, Ruhr, Moehne and some of their tributaries. Further samples were taken from the Rhine-Herne-Canal and the Wesel-Datteln-Canal. - Drinking waters: samples taken in public buildings of the Rhine-Ruhr area. After sample clean-up and concentration by solid-phase extraction, the perfluorinated surfactants were determined using HPLC-MS/MS. Results: All measured concentrations (sum of seven mainly detected components) in the Rhine river and its main tributaries (mouths) were determined below 100 ng/L. The Ruhr river (tributary of the Rhine) showed the highest concentration (94 ng/L), but with a completely different pattern of components (PFOA as major component), as compared with the other tributaries and the Rhine river. Further investigations along the Ruhr river showed remarkably high concentrations of PS in the upper reaches of the Ruhr river and the Moehne river (tributary of the Ruhr) (Ruhr: up to 446 ng/L, Moehne: up to 4385 ng/L). The maximum concentration of all drinking water samples taken in the Rhine-Ruhr area was determined at 598 ng/L with the major component PFOA (519 ng/L). Discussion: The surface water contaminations most likely stem from contaminated inorganic and organic waste materials (so-called 'Abfallgemisch'). This waste material was legally applied to several agricultural areas on the upper reaches of the Moehne. Perfluorinated surfactants could be detected in some suchlike soil samples. They contaminated the river and the reservoir belonging to it, likely by superficial run-off over several months or probably years. Downstream, dilution effects are held responsible for decreasing concentrations of PS in surface waters of the Moehne and the Ruhr river. In analogy to the surface water samples, PS (major component PFOA) can be determined in many drinking water samples of the Rhine-Ruhr area where the water supplies are mainly based on bank filtration and artificial recharge. Conclusions: The concentrations found in drinking waters decreased with the concentrations of the corresponding raw water samples along the flow direction of the Ruhr river (from east to west) and were not significantly different from surface water concentrations. This indicates that perfluorinated surfactants are at present not successfully removed by water treatment steps. Recommendations and Perspectives: Because of their different problematic properties (persistence, mobility, toxicity, bioaccumulation), the concentrations of specific perfluorinated surfactants and their precursors in drinking waters and food have to be minimised. Therefore, it is of utmost importance to take the initiative to establish suitable legal regulations (limitations/ban) concerning the production and use of these surfactants and their precursors. Furthermore, it is indispensable to protect water resources from these compounds. A discussion on appropriate limit values in drinking water and foodstuffs is urgently needed. Concerning the assumed soil contamination, the corresponding regulation (Bioabfall-Verordnung 1998 – Regulation on Organic Waste 1998) should be extended to allow the control of relevant organic pollutants.     

环境空气中痕量挥发性有机硫监测分析方法研究

采用预浓缩系统与GC MS联用,建立了环境空气中痕量挥发性有机硫的分析方法,该法用苏玛罐或Tedlar袋采集空气样品在预浓缩系统中经液氮于-160℃冷冻浓缩后,进入GC MS进行分析。甲硫醇、乙硫醇、甲硫醚、乙硫醚、二甲二硫的最低检出限分别为2 0、1 0、1 0、1 0、0 5μg m3。经6次的重复测定,其相对标准偏差小于9 0%。该方法已用于环境空气的测定,取得了令人满意的结果。     

TA-FTIR/MS用于硝酸铵及其混合物的热化学行为研究

为评价物料混合对危险化学品热化学行为的影响,采用热分析-红外/质谱联用技术(TA-FTIR/MS)研究硝酸铵、柠檬酸和蔗糖的混合物的热化学行为。通过对硝酸铵及其混合物的分解温度和分解过程中逸出气体的分析,发现硝酸铵、柠檬酸和蔗糖的混合物热分解温度分别降低至135℃和153℃,而硝酸铵与甲基纤维素的混合物分解温度与硝酸铵基本相同为201℃,且各混合体系的气相分解产物均有氮氧化物(NOX),H2O和CO2。结果表明,混合物受热后其中的硝酸铵首先分解为硝酸和氨气;酸性物质和还原性物质由于对硝酸的分解反应有催化作用,使得混合物的热稳定性下降。     

苔藓Lophozia ventricosa挥发油化学成分研究

采用水蒸气蒸馏法提取苔藓Lophozia ventricosa挥发油，用毛细管色谱法对挥发油进行了分析，采用归-化法确定各组分的相对含量，并用GC—MS联用技术对分离的化学成分进行鉴定．经计算机检索并结合文献调研，共鉴定出28个化合物，占挥发油总量的93．3％，其中含1个单萜、23个倍半萜（15个为含氧倍半萜）和1个二萜，主要成分为Maalioxide（45．6％）和Eudesma-4．（15），7（11）-dien-8-one（28．9％）．图2表1参12     

焦化废水中有机物在A1-A2-O系统各段的降解与转化

在厌氧酸化－缺氧－好氧（A1－A2－O）生物膜系统小试装置中处理焦化废水，以探讨有机物在各阶段的降解与转化情况。通过UV吸收光谱及GC／MS分析发现，上海焦化厂废水中的有机组分主要为：甲酚、苯酚、二甲酚等酚类化合物，及以喹啉、吲哚为代表的含氮杂环化合物，约占有机物总量的90％。经A1－A2－O生物膜系统处理后，大部分有毒有害难降解有机物得到了降解和转化。厌氧段中原有物质浓度的增加和新物质的生成，是厌氧酸化使部分有机物降解产生中间产物而造成；缺氧段使大部分有机物被完全降解或转化，还产生一些新的简单有机物，如卤代烃、酯类、醛类等；经好氧段反应后，有机物进一步降解和转化，部分被完全去除，在降解转化过程中又产生了一些中间产物和衍生物，如苯酚、羟基喹啉等。     

Two-site kinetic modeling of bacteriophages transport through columns of saturated dune sand

Breakthrough curves, on a semi-log scale, from tests in porous media with block-input of viruses, bacteria, protozoa and colloidal particles often exhibit a typical skewness: a rather slowly rising limb and a smooth transition of a declining limb to a very long tail. One-site kinetic models fail to fit the rising and declining limbs together with the tail satisfactorily. Inclusion of an equilibrium adsorption site does not seem to improve simulation results. This was encountered in the simulation of breakthrough curves from a recent field study on the removal of bacteriophages MS2 and PRD1 by passage through dune sand. In the present study, results of laboratory experiments for the study of this issue are presented. Breakthrough curves of salt and bacteriophages MS2, PRDI, and phiX174 in 1 D column experiments have been measured. One- and two-site kinetic models have been applied to fit and predict breakthrough curves from column experiments. The two-site model fitted all breakthrough curves very satisfactorily, accounting for the skewness of the rising limb as well as for the smooth transition of the declining limb to the tail of the breakthrough curve. The one-site model does not follow the curvature of the breakthrough tail, leading to an overestimation of the inactivation rate coefficient for attached viruses. Interaction with kinetic site 1 is characterized by relatively fast attachment and slow detachment, whereas attachment to and detachment from kinetic site 2 is fast. Inactivation of viruses and interaction with kinetic site 2 provide only a minor contribution to removal. Virus removal is mainly determined by the attachment to site 1. Bacteriophage phiX174 attached more than MS2 and PRD1, which can be explained by the greater electrostatic repulsion that MS2 and PRD1 experience compared to the less negatively charged phiX174.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, -thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².

The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, α-thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

水解酸化-缺氧法处理采油废水的污染物迁移降解试验研究

水解酸化．缺氧法对采油废水有较好的处理效果，采用GC／MS技术对水解酸化-缺氧法处理采油废水过程中污染物的迁移降解进行的研究表明：水解酸化段和缺氧段对采油废水中碳原子为C6-C9、分子量为100—140的有机物均有较好的降解能力。其中，在水解酸化段中酮类、芳烃得到较好的降解，缺氧段中酚类和醚类化合物降解明显。水解酸化-缺氧工艺对于采油废水中的甲苯和二甲苯具有较好的降解能力。     

Molecular characterization of effluent organic matter in secondary effluent and reclaimed water: Comparison to natural organic matter in source water

Municipal wastewater reclamation is becoming of increasing importance in the world to solve the problem of water scarcity. A better understanding of the molecular composition of effluent organic matter(Ef OM) in the treated effluents of municipal wastewater treatment plants(WWTPs) is crucial for ensuring the safety of water reuse. In this study, the molecular composition of Ef OM in the secondary effluent of a WWTP in Beijing and the reclaimed water further treated with a coagulation–sedimentation–ozonation process were characterized using a non-target Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) method and compared to that of natural organic matter(NOM) in the local source water from a reservoir. It was found that the molecular composition of Ef OM in the secondary effluent and reclaimed water was dominated by CHOS formulas, while NOM in the source water was dominated by CHO formulas. The CHO formulas of the three samples had similar origins. Anthropogenic surfactants were responsible for the CHOS formulas in Ef OM of the secondary effluent and were not well removed by the coagulation-sedimentation-ozonation treatment process adopted.