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.     

PFOS前体物质(PreFOSs)降解菌的分离鉴定及其降解特性

从氟化工厂附近土壤中分离出1株能以全氟辛烷磺酸前体物质(Pre FOSs)为唯一碳源和能源生长的降解菌PF1,经形态观察及16S r DNA基因序列分析,初步鉴定该菌为生丝微菌属(Hyphomicrobium sp.).在温度为30℃、p H为7.0~7.2条件下,菌株PF1对全氟辛基磺酰胺(PFOSA)和N-乙基全氟辛基磺酰胺(N-Et FOSA)48 h降解率分别为14.6%和8.2%,对PFOS无降解能力.对降解产物进行检测和分析,结果表明PFOSA的降解产物为PFOS;N-Et FOSA能被降解生成PFOSA和PFOS,同时也产生少量的全氟辛基磺酰胺乙酸(FOSAA).由此推断Pre FOSs降解途径,在菌株PF1的作用下,PFOSA脱去氨基直接转化成PFOS.NEt FOSA主要有2种降解途径:(1)N-Et FOSA脱乙基产生PFOSA,PFOSA再进一步脱氨基生成PFOS,此为主要途径;(2)NEt FOSA中的N-乙基被氧化成乙酸基生成FOSAA,FOSAA进一步脱去乙酸基生成PFOSA,并最终脱氨基生成PFOS.     

Determination of polyfluoroalkyl compounds in water and suspended particulate matter in the river Elbe and North Sea, Germany

The distribution of polyfluoroalkyl compounds (PFCs) in the dissolved and particulate phase and their discharge from the river Elbe into the North Sea were studied. The PFCs quantified included C₄-C₈ perfluorinated sulfonates (PFSAs), 6:2 fluorotelomer sulfonate (6:2 FTS), C₆ and C₈ perfluorinated sulfinates (PFSiAs), C₄-C₁₂ perfluorinated carboxylic acids (PFCAs), perfluoro-3,7-dimethyl-octanoic acid (3,7m₂-PFOA), perfluorooctane sulfonamide (FOSA), and n-ethyl perfluroctane sulfonamidoethanol (EtFOSE). PFCs were mostly distributed in the dissolved phase, where perfluorooctanoic acid (PFOA) dominated with 2.9–12.5 ng/L. In the suspended particulate matter FOSA and perfluorooctane sulfonate (PFOS) showed the highest concentrations (4.0 ng/L and 2.3 ng/L, respectively). The total flux of ΣPFCs from the river Elbe was estimated to be 802 kg/year for the dissolved phase and 152 kg/year for the particulate phase. This indicates that the river Elbe acts as a source of PFCs into the North Sea. However, the concentrations of perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) in the North Sea were higher than that in the river Elbe, thus an alternative source must exist for these compounds.     

Selective sorption of perfluorooctane sulfonate on molecularly imprinted polymer adsorbents

Perfluorooctane sulfonate (PFOS), as a potential persistent organic pollutant, has been widely detected in water environments, and has become a great concern in recent years. PFOS is very stable and difficult to decompose using conventional techniques. Sorption may be an attractive method to remove it from water. In this study, the molecularly imprinted polymer (MIP) adsorbents were prepared through the polymerization of 4-vinylpyridine under different preparation conditions in order to remove perfluorooctane sulfonate (PFOS) from water. The MIP adsorbents using perfluorooctanoic acid (PFOA) as the template had good imprinting effects and could selectively remove PFOS from aqueous solution. The sorption behaviors including sorption kinetics, isotherms, and effect of pH, salt, and competitive anions were investigated. Experimental results showed that the sorption of PFOS on the MIP adsorbents was very fast, pH-dependent, and highly selective. The achieved fast sorption equilibrium within 1 h was attributed to the surface sorption on the fine adsorbents. The sorption isotherms showed that the sorption selectivity of PFOS on the MIP adsorbents decreased at high PFOS concentrations, which may be due to the double-layer sorption and the formation of PFOS micelles on the sorbent surface. The sorption of PFOS on the MIP adsorbents was mainly dominated by the electrostatic interaction between the protonated vinylpyridine on the adsorbent surface and the anionic PFOS. The prepared MIP adsorbents can potentially be applied in water and wastewater treatment for selective removal of PFOS.     

Sorption of Perfluorooctane sulfonate（PFOS） including its isomers on hydrargillite as a function of pH,humic substances and Na2SO4

Perfluorooctane sulfonate（PFOS） is a persistent organic pollutant（POP） and emergent contaminant that are widespread in the environment. Understanding the mechanisms controlling the distribution of PFOS and its isomers between hydrargillite and the water phase is important in order to study their redistribution and mobility in the environment. This study investigated the effects of pH, humic acid, fulvic acid and Na₂SO₄ on sorption of PFOS isomers to hydrargillite. A mixture...     

1,10-菲啰啉-全氟辛烷磺酸(PFOS)体系共振光散射法测定痕量镉(Ⅱ)

在pH 6.8 Britton-Robinson(BR)缓冲介质中,镉(Ⅱ)与1,10-菲啰啉(Phen)作用后与全氟辛烷磺酸(PFOS)形成离子缔合物,使体系的共振光散射信号显著增强.最大散射峰位于307.0 nm处,其增强散射信号强度与镉(Ⅱ)的浓度在6.0—342.5 ng·mL-1范围内呈线性关系,据此建立了测定镉(Ⅱ)含量的共振光散射分析方法,检出限(3!)为0.6 ng·mL-1,研究了反应产物的RLS光谱特征,适宜的反应条件和影响因素,考察了共存物质的影响.该方法用于自来水和实验室废水样中镉(Ⅱ)的测定,RSD≤4.4%.     

十二烷基磺酸钠(SDS)对刺参幼参的急性毒性

为探究表面活性剂对海洋棘皮动物的影响,测定了十二烷基磺酸钠(SDS)对刺参(Stichopus japonicas)幼参的急性毒性。结果显示,SDS对刺参幼参的72h-LC_(50)和96h-LC_(50)分别为15.03和10.89mg·L~(-1)。刺参幼参相对于常见的几种水生生物对SDS的敏感性较高,其生命周期较长,活动能力较弱,生活相对固定于一定的区域,因此,在监测海洋水体SDS污染时,刺参幼参是一种值得关注的生物。     

水中LAS的光催化氧化处理研究

本文研究了三聚磷酸钠（STPP）浓度变化和温度变化条件下,对水中直链十二烷基苯磺酸钠（LAS）光催化氧化降解的影响,并根据动力学研究的结果,充分说明了造成上述影响的原因。     

Fe3O4纳米磁性微粒对全氟辛烷磺酸盐的吸附

采用共沉淀法合成Fe3O4纳米磁性颗粒,用透射电子显微镜(TEM)、X射线衍射仪(XRD)以及振动样品磁强计(VSM)对Fe3O4纳米磁性颗粒的粒径、形貌和磁性进行表征并研究Fe3O4纳米磁性微粒对全氟辛磺酸盐的吸附。结果表明:在PFOS初始浓度4 mg/L,pH为3,反应时间24 h,Fe3O4纳米磁性微粒投加量1.25 g/L,对全氟辛磺酸盐去除率达到90%。Fe3O4纳米磁性微粒对PFOS的吸附符合Freundlich吸附方程。     

孕哺期全氟辛烷磺酸染毒对大鼠海马细胞钙稳态的影响

为了阐明孕哺期全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)染毒对大鼠及其仔鼠海马细胞钙稳态的影响,将妊娠Wistar大鼠30只,从妊娠第1天开始对实验组分别以72 mg·kg-1(low,L)、14.4 mg·kg-1(high,H)(以饲料中的PFOS计)的PFOS进行染毒至仔鼠生后3...