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.     

Titration Curves: A Useful Instrument for Assessing the Buffer Systems of Acidic Mining Waters (10 pp)

Background, Aims and Scope The acidification of mine waters is generally caused by metal sulfide oxidation, related to mining activities. These waters are characterized by low pH and high acidity due to strong buffering systems. The standard acidity parameter, the Base Neutralization Capacity (BNC) is determined by endpoint titration, and reflects a cumulative parameter of both hydrogen ions and all buffering systems, but does not give information on the individual buffer systems. We demonstrate that a detailed interpretation of titration curves can provide information about the strength of the buffering systems. The buffering systems are of importance for environmental studies and treatment of acidic mining waters. Methods Titrations were carried out by means of an automatic titrator using acidic mining waters from Germany and Canada. The curves were interpreted, compared with each other, to endpoint titration results and to elemental concentrations contained therein. Results and Discussion The titration curves were highly reproducible, and contained information about the strength of the buffer systems present. Interpretations are given, and the classification and comparison of acidic mining waters, by the nature and strength of their buffering systems derived from titration curves are discussed. The BNC-values calculated from the curves were more precise than the ones determined by the standard endpoint titration method. Due to the complex buffer mechanisms in acidic mining waters, the calculation of major metal concentrations from the shape of the titration curve resulted in estimates, which should not be confused with precise elemental analysis results. Conclusion Titration curves provide an inexpensive, valuable and versatile tool, by which to obtain sophisticated information of the acidity in acidic water. The information about the strength of the present buffer systems can help to understand and document the complex nature of acidic mining water buffer systems. Finally, the interpretation of titration curves could help to improve treatment measurements and the ecological understanding of these acidic waters.     

粉煤灰对水中酸性品红的吸附研究

以粉煤灰为吸附剂,研究了粉煤灰对酸性品红的吸附效果。选取了粒径、投加量、温度、时间、转速、染料浓度6个因素进行单因素实验,研究了各个因素对粉煤灰的影响,研究表明,粉煤灰对酸性品红的吸附效果很好,最高去除率可达99.63%;并且从热力学和动力学两方面对粉煤灰吸附酸性品红的过程进行拟合,结果表明,粉煤灰对酸性品红吸附的热力学过程比较符合模型Langmuir EXT1,动力学过程比较符合准一级吸附动力学方程Box Lucas1。     

广州市酸沉降对材料破坏的经济损失估算

大气中的酸性物质对材料的破坏是酸沉降经济损失中的重要部分。简要说明了材料损失的计算方法,并以2001年为基准年,选择了广州市作为代表性城市,运用材料损伤函数和材料使用寿命公式对建筑材料及自行车的经济损失进行了估算,使酸沉降的破坏作用达到定量化。     

伊宁市空气中硫酸盐化速率与二氧化硫相关性研究

对伊宁市1999-2002年空气中硫酸盐化速率和二氧化硫监测值进行回归分析,结果表明,二者之间存在显著的线性正相关关系,但对各年度回归方程斜率和截距进行统计检验,则表现出显著的差异。     

模糊数学原理在湿法磷酸过程风险评价中的应用

在建立安全评价指标体系基础上,采用层次分析法确定各因素的权重分配。运用模糊数学原理对湿法磷酸过程中的风险进行评价,最终得到其风险的模糊评价结果。结果表明,湿法磷酸过程中的风险为第5级,即风险小。     

草酸作用下海洋疏浚物中Cr的释放动力学研究

采用恒温振荡实验装置,系统研究了有机酸草酸降解海洋疏浚物中重金属Cr的动力学过程。结果表明,恒温振荡6 h后,浓度为0.05~0.4 mol/L的草酸可使Cr的释放百分率达到24%~44%。Cr的释放总体上可分为快速反应和慢速反应2个阶段,0~2 h为快反应阶段,解吸速率快,2~6 h后为慢反应阶段。草酸对Cr的释放动力学数据可用双常数方程很好的拟合,说明在草酸的存在下,疏浚物颗粒表面对Cr的释放可能更多表现出能量的不均匀性。温度升高时Cr的解吸量增加,反应速度加快,根据阿累尼乌斯公式估算出的活化能为26.53 kJ/mol。     

[HPMo][OTAC]2/SiO2的制备及其催化柴油氧化脱硫的研究

采用溶胶-凝胶法制备不同负载量的[HPMo][OTAC]2/SiO2,通过红外光谱、比表面积和孔结构分析对[HPMo][OTAC]2/SiO2进行表征,考察负载量、催化剂用量、氧化剂用量、反应温度和反应时间对模拟柴油脱硫效果的影响。结果表明,掺杂后的催化剂保持了Keggin结构,[HPMo][OTAC]2/SiO2在最佳反应条件下,苯并噻吩的脱除率达到48.3%,二苯并噻吩的脱除率达到67.2%。     

产酸脱硫反应器中碳硫比对群落生态特征的影响

通过产酸脱硫反应器处理高浓度含硫酸盐废水的连续流试验,从群落动态的角度研究碳硫比(COD/SO₄^2-)从4.2降低到2.0的过程中,pH值、氧化还原电位(ORP)、碱度(ALK)和末端产物(VFAs)组成、优势种群分布等群落生态特征的变化规律试验证明,在此过程中ORP和ALK提高,而pH值和VFAs中乙酸的分布比例降低,群落类型由高碳硫比稳定型转化为低碳硫比亚稳定型,但仍未改变乙酸型顶极群落的典型特征.     

不同分子量的腐殖酸存在下2种无机砷的生物毒性效应研究

水环境中天然有机质会与砷形成络合物,进而影响砷的迁移、转化和生物毒性。研究利用超滤方法将腐殖酸(humic acid, HA)分为5个不同分子量的组分,以大型溞为受试生物,探究了不同分子量HA存在下砷对大型溞的毒性效应。结果表明,不同分子量的HA均缓解了As(Ⅲ)和As(Ⅴ)对大型溞的氧化应激损伤和细胞膜损伤,并降低了砷对MT的诱导量。其中1～30 k Da的HA对砷的缓解效果最好,1 k Da的HA毒性缓解效果最差,可能的原因是HA与砷的络合增加溶液中络合态砷的含量,而络合态砷难以进入细胞并被生物利用。不同分子量的HA对砷毒性的缓解差异与其跟砷的络合比例不同有关。