Identification of perfluoroalkyl acid sources in Swiss surface waters with the help of the artificial sweetener acesulfame

Anthropogenic perfluorinated compounds (PFCs), especially the perfluoroalkyl acids (PFAAs) are ubiquitously found in surface waters around the globe. Emissions from households, industries and also atmospheric transport/deposition are discussed as the possible sources. In this study, these sources are evaluated using Switzerland as the study area. Forty-four surface water locations in different rivers and an Alpine lake were investigated for 14 PFAAs, four precursors and acesulfame, an artificial sweetener used as a population marker. Concentrations of individual PFAAs were generally low, between 0.02 and 10 ng/L. Correlation analysis showed that some PFAAs concentrations correlated well with population and less with catchment area, indicating that emissions from population, i.e., from consumer products, is the most important source to surface waters in Switzerland. The correlation with the population marker acesulfame confirmed this observation but highlighted also a few elevated PFAA levels, some of which could be attributed to industrial emissions.     

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.     

不同侧压力系数下圆形巷道变形破裂规律分析

为研究侧压力系数对巷道周边岩体稳定性的影响,以一条深埋圆形巷道工程为背景,采用离散颗粒元软件PFC3D分析了5种侧压力系数下巷道周边岩体的应力差、位移、破裂分布模式和微裂纹数等,得到了圆形巷道周边岩体应力、变形和破裂随侧压力系数的变化规律。结果表明,1)随侧压力系数增大,巷道顶底部浅部岩体主应力差先增大后减小,深部岩体主应力差逐渐增大;而巷道两帮浅部岩体主应力差变化较小,深部岩体主应力差先减小后增大。这表明在相同埋深情况下,高侧压力系数不一定会对帮部岩体造成更大的破坏,但更容易使顶板产生高剪应力,不利于顶板岩体的稳定。2)侧压力系数越大,巷道顶板岩体竖向位移就越小,且其由拱顶往外平滑递减的规律性也越不明显,而帮部岩体水平位移变化规律与顶板岩体相反。3)巷道顶底部围岩在侧压力系数较大的情况下较易发生破裂,并随侧压力系数增大,其破裂范围越来越大;巷道两帮岩体则在不同侧压力系数下均会发生破裂,且其破裂范围随侧压力系数增大而略减小。4)不同侧压力系数下,巷道岩体总裂纹数都随开挖时间呈指数增长;且当巷道开挖完成后,岩体总裂纹数与侧压力系数呈抛物线关系。     

含裂隙岩石裂纹扩展与剪切特性的数值研究*

为研究直剪条件下含交叉裂隙岩石的裂纹扩展模式和剪切特性,基于PFC2D研究直剪条件下含裂隙岩石的裂纹扩展模式和剪切特性。研究结果表明:直剪过程可分4个阶段:Ⅰ初始平静阶段、Ⅱ裂纹单一扩展阶段、Ⅲ裂纹复杂扩展阶段、Ⅳ破坏阶段;法向应力越大,Ⅱ,Ⅲ阶段的裂纹扩展程度受到抑制;岩石中含单裂隙时,随裂隙角度α的增加,抗剪强度的变化趋势基本一致,遵循先降后增的规律;含交叉裂隙时,当主裂隙角度α=120°,150°时,抗剪强度随次裂隙角度β的增加呈先减小后增大的趋势,抗剪强度最小值均出现在β=30°;加固含裂隙岩体时,预防裂隙或者潜在破坏面两侧的岩体产生位移差,使其加固后成为1个稳固整体,是避免岩体产生裂纹导致破坏的重要手段。     

微涡旋絮凝-逆流气浮-纳滤集成工艺去除水中腐殖酸的研究之二——以聚合氯化铁(PFC)为絮凝剂

试验研究了微涡旋絮凝-逆流气浮-纳滤集成工艺去除水中腐殖酸的工艺特征和效果.试验结果表明,微涡旋絮凝-逆流气浮工艺去除水中腐殖酸时,在聚合氯化铁(PFC)的最佳投药点0.62 mmol·L-1(Fe3 )下,出水水质符合纳滤膜系统预处理单元的要求,而且该工艺需要PFC絮凝剂的量较低.该预处理系统与纳滤系统组合的集成工艺可以使水中的腐殖酸有机物浓度大大降低,且含TQ56-36FC型纳滤膜的流程1比含M-N1812A型纳滤膜的流程2效果好.前者出水的TOC值可达0.48 mg·L-1,CODMn值为0.64～0.69mg·L-1,UV254值为0,且有95%以上的脱盐率.后者出水的TOC值为0.61～1.00mg·L-1,CODMn值为0.72～0.97mg·L-1,UV254值为0～0.0109,脱盐率很低.另外,尽管保安过滤/活性炭预处理有利于纳滤膜出水水质的提高,但活性炭柱的存在也降低了纳滤膜对有机物的去除率.动态实验结果表明,该集成工艺在本试验中运行周期为72h.水中颗粒物粒度分布表明,原水、絮凝后和气浮出水中颗粒物粒度分布的中位直径(d50)分别为2～5 μm、21 μm和16μm;经过保安过滤器或保安过滤器/活性炭柱,水样中的颗粒物的d50为0到几个μm;经过纳滤膜后,出水基本无颗粒物.初步研究表明,微涡旋絮凝过程中投药量对絮体的分形维数有着显著影响.     

氧化法制备聚合氯化铁絮凝剂的氧化速率及其形态分布

采用氧化法制备聚合氯化铁絮凝剂，论述了不同亚铁溶液中氧化水解动力学、氧化过程PH值变化以及不同反应过程对聚合氯化铁形态分布的影响；结果表明，氯化亚铁溶液的氧化速率主要受溶液的含酸量和三价铁离子的水解聚合反应的协同效应的影响，当溶液酸量达到最低点时，亚铁氧化速度也将降至最慢；通过形态分布、稳定性及氧化速度的研究确定了制备聚合氯化铁的最佳条件。     

火灾引发超高层建筑非连续倒塌模拟研究

为了解超高层建筑发生火灾后变形特征及失稳后的非连续坍塌过程,掌握引起变形和坍塌的原因,将三维颗粒流软件(PFC3D)作为模拟平台,设置核心筒-框架结构的超高层建筑火灾区域,并模拟坍塌过程。在考虑钢筋和混凝土共同作用结果的基础上,提出火灾区域中构件属性设置方法及模拟步骤。分析得到造成建筑结构摆动的3种原因,一是火区位置不同导致上部结构对火区的压力不同,二是火区位置不同导致结构受到的约束不同,三是受热膨胀性使构件产生不同程度变形。结果表明:燃烧温度为500℃,3 h后建筑发生摆动,表现出对火区位置和燃烧时间敏感的特征。1 000℃下1 h内,建筑物首先发生破坏的是梁构件,然后是承重柱。即建筑一旦进入结构破坏阶段,坍塌将是迅速且不可逆的。     

Effect of dimethoate on the immune system of female mice

Abstract

The functional status of the immune system of female mice exposed to a single oral dose of dimethoate (16 mg / kg) was evaluated by assessing cell mediated and humoral immune responses, in addition to the effect of dimethoate on spleen and body weights after different time intervals. The data showed that dimethoate caused a time ‐ depended decrease in spleen weights in the absence of a change in body weights. The immunologic effect of dimethoate to female mice produced a dose‐dependent decrease in the number of the rosette forming cells (total and active erythrocyte rosette). The ability of splenocytes to proliferation in response to mitogens; phytohemagglutinin (PHA) for T cell and lipopolysaccharide (LPS) for B cell were significantly decreased at the different times. As compared to control, a significant decrease in serum total immunoglobulins (Ig) and IgM was found, while IgG was non‐significant deceased. Results of this study also revealed that dimethoate caused a significant decrease in the number of plaque forming cell (PFC / 10⁶ splenocytes) in a time dependent manner.     

Waste water treatment plants as sources of polyfluorinated compounds, polybrominated diphenyl ethers and musk fragrances to ambient air

To investigate waste water treatment plants (WWTPs) as sources of polyfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs) and synthetic musk fragrances to the atmosphere, air samples were simultaneously taken at two WWTPs and two reference sites using high volume samplers. Contaminants were accumulated on glass fiber filters and PUF/XAD-2/PUF cartridges, extracted compound-dependent by MTBE/acetone, methanol, or hexane/acetone and detected by GC-MS or HPLC-MS/MS. Total (gas + particle phase) concentrations ranged from 97 to 1004 pg m⁻³ (neutral PFCs), <MQL to 13 pg m⁻³ (ionic PFCs), 5781 to 482,163 pg m⁻³ (musk fragrances) and <1 to 27 pg m⁻³ (PBDEs) and were usually higher at WWTPs than at corresponding reference sites, revealing that WWTPs can be regarded as sources of musk fragrances, PFCs and probably PBDEs to the atmosphere. Different concentrations at the two WWTPs indicated an influence of WWTP size or waste water origin on emitted contaminant amounts.     

高浓度聚合氯化铁(PFC)中铁的形态分布与转化研究

以氯化铁和无水碳酸钠为原料,加入稳定剂W,采用共聚工艺,制备了稳定高浓度的聚合氯化铁(PFC)混凝剂.采用Fe-Ferron逐时络合比色法研究了PFC中铁的形态分布情况,考察了熟化时间、碱化度(B)及n(W)/n(Fe)(W/Fe摩尔比)对PFC中铁的形态分布的影响.研究结果表明,在PFC中,由于稳定剂W与铁的水解产物间的相互作用,使得铁的水解聚合形态分布及转化情况发生了变化.碱化度(B)、n(W)/n(Fe)和熟化时间均对铁的形态分布有重要的影响.