松花江水系江水中全氟辛烷磺酸和全氟辛酸污染现状调查

为阐明松花江江水中全氟辛烷磺酸(Perfluorooctane sulfonate,PFOS)、全氟辛酸(Perfluorooctanoic acid,PFOA)的污染现状,以及中国石油吉林石化双苯厂爆炸事件对松花江江水和哈尔滨市内饮用水中PFOS、PFOA浓度的影响,于2005-10-12至2005-10-16间采集嫩江吉林大安江段、第二松花江吉林扶余江段、第一松花江黑龙江肇源江段及哈尔滨江段江水样品共22份.在吉林石化爆炸事件后,于2005-11-24至2005-11-28间每日定时在固定地点采集松花江哈尔滨江段江水样品;于2005-11-23和2005-11-28分别采集哈尔滨市内饮用水样品.采用高效液相色谱/质谱联机法(HPLC/MS)检测样品中PFOS和PFOA.结果表明,松花江水体中普遍存在PFOS、PFOA污染.全部江水样品中PFOS和PFOA浓度范围分别为0.06～8.04ng·L-1和0.02～2.68 ng·L-1,几何平均值分别为1.214 ng·L-1和0.166 ng·L-1.松花江上游江段水中PFOS、PFOA浓度明显低于下游.流经哈尔滨市区时江水中PFOS和PFOA浓度逐渐升高.2005-11-26江水中PFOS浓度水平比2005-11-24江水浓度水平高5.8倍,而PFOA浓度未见变化.哈尔滨市内饮用水PFOS、PFOA平均浓度在2005-11-23停水前和2005-11-28恢复供水后未见差异.研究结果显示,松花江水体中普遍存在PFOS、PFOA污染;吉林石化公司爆炸事件后暂时性升高松花江江水中PFOS浓度,但未对哈尔滨市内饮用水中PFOS、PFOA的浓度产生影响.     

Effects of ZnO nanoparticles on perfluorooctane sulfonate induced thyroid-disrupting on zebrafish larvae

Perfluorooctane sulfonate(PFOS) and ZnO nanoparticles(nano-ZnO) are widely distributed in the environment.However,the potential toxicity of co-exposure to PFOS and nano-ZnO remains to be fully elucidated.The test investigated the effects of co-exposure to PFOS and nano-ZnO on the hypothalamic–pituitary–thyroid(HPT) axis in zebrafish.Zebrafish embryos were exposed to a combination of PFOS(0.2,0.4,0.8 mg/L) and nano-ZnO(50 mg/L)from their early stages of life(0–14 days).The whole-body content of TH and the expression of genes and proteins related to the HPT axis were analyzed.The co-exposure decreased the body length and increased the malformation rates compared with exposure to PFOS alone.Co-exposure also increased the triiodothyronine(T3) levels,whereas the thyroxine(T4)content remained unchanged.Compared with the exposure to PFOS alone,exposure to both PFOS(0.8 mg/L) and nano-ZnO(50 mg/L) significantly up-regulated the expression of corticotropin-releasing factor,sodium/iodidesymporter,iodothyronine deiodinases and thyroid receptors and significantly down-regulated the expression of thyroid-stimulating hormone,thyroglobulin(TG),transthyretin(TTR) and thyroid receptors.The protein expression levels of TG and TTR were also significantly down-regulated in the co-exposure groups.In addition,the expression of the thyroid peroxidase gene was unchanged in all groups.The results demonstrated that PFOS and nano-ZnO co-exposure could cause more serious thyroid-disrupting effects in zebrafish than exposure to PFOS alone.Our results also provide insight into the mechanism of disruption of the thyroid status by PFOS and nano-ZnO.     

全氟辛烷磺酸(PFOS)对半滑舌鳎肝脏细胞的毒性效应

为探究海洋环境中持久性有机污染物——全氟辛烷磺酸(PFOS)的生物毒性效应,以半滑舌鳎肝脏细胞(HTLC)为研究对象,将其暴露于含不同浓度PFOS的DMEM-F12培养基中,分别染毒24、48、72 h后,利用噻唑蓝比色法(MTT)和透射电镜实验评价PFOS的细胞毒性;同时测定活性氧自由基(ROS)和超氧化物歧化酶(SOD)活性来探讨PFOS对细胞的氧化损伤效应。结果发现,细胞活性随PFOS浓度升高呈先促进后抑制趋势,当PFOS浓度达到1 000%mol·L-1时细胞活性受到显著抑制(P0.01);电镜结果显示PFOS能引起与代谢相关的细胞器如线粒体、内质网等发生肿胀甚至破损;与对照组相比,ROS含量和SOD活性分别在20%mol·L-1、200%mol·L-1开始出现显著性差异(P0.05),证实在PFOS引起的氧化应激反应中SOD起到了清除自由基作用以维持细胞稳态。研究表明,PFOS对海洋鱼类细胞具有一定的生物毒性,能引起细胞产生氧化应激反应,并进一步破坏生物膜系统,从而导致细胞增殖和多种代谢途径受到抑制。     

Ecotoxicological effects of waterborne PFOS exposure on swimming performance and energy expenditure in juvenile goldfish (Carassius auratus)

The potential risks of perfluorooctane sulfonate (PFOS) are of increasing ecological concern. Swimming performance is linked to the fitness and health of fish. However, the impacts of PFOS on swimming performance remain largely unknown. We investigated the ecotoxicological effects of acute exposure to PFOS on the swimming performance and energy expenditure of juvenile goldfish (Carassius auratus). The fish were exposed to a range of PFOS concentrations (0, 0.5, 2, 8 and 32 mg/L) for 48 hr. The spontaneous swimming activity, fast-start swimming performance, critical swimming speed (Ucrit) and active metabolic rate (AMR) of the goldfish were examined after exposure to PFOS. PFOS exposure resulted in remarkable effects on spontaneous activity. Motion distance was reduced, and the proportion of motionless time increased with increasing concentrations of PFOS. However, no significant alterations in the fast-start performance-related kinematic parameters, such as latency time, maximum linear velocity, maximum linear acceleration or escape distance during the first 120 msec after stimulus, were observed after PFOS exposure. Unexpectedly, although PFOS exposure had marked influences on the swimming oxygen consumption rates and AMR of goldfish, the U crit of the goldfish was not significantly affected by PFOS. This may result in a noteworthy increase in the energetic cost of transport. The overall results indicate that, in contrast to spontaneous activity, underlying swimming capabilities are maintained in goldfish after short-term exposure to PFOS, but energy expenditure during the process of swimming is dramatically aggravated.     

全氟化工厂土芯中全氟化合物的分布规律

本文对全氟化合物(PFASs)生产工厂厂内及周边土芯样品中的PFASs进行了研究.PFASs浓度范围为1.19—1495 ng·g-1dw(干重),其中全氟辛基磺酸盐(PFOS)浓度在3个主要单体(全氟己基磺酸盐(PFHxS)、PFOS及全氟辛酸(PFOA))中处于最高水平.整体上,土芯中PFASs浓度由上到下呈下降趋势,其浓度与TOC呈正相关.在一个已经停产10年左右的生产企业周围土芯中仍然发现了较高浓度的PFASs,说明其在环境中存在着较强的持久性.     

Determination of C(5)-C(12) perfluoroalkyl carboxylic acids in river water samples in the Czech Republic by GC-MS after SPE preconcentration

A method employing solid phase extraction followed by gas chromatography-mass spectrometry with negative chemical ionization has been developed for determination of ultratrace concentrations of perfluoroalkyl carboxylic acids in river water. The effects of the experimental parameters, such as the pH, additions of NaCl and an ion-pairing agent (tetraethylammonium bromide) and the kind of the elution agent, on the efficiency of the test acid extraction have been studied. The analyte extraction recoveries and the limits of detection and determination have been found. The method developed has been tested on determinations of perfluoroalkyl carboxylic acids in the waters of the two largest Czech rivers, Vltava and Labe (Elbe). The best extraction results have been attained without any alteration of the sample pH, with an addition of tetrabutylammonium bromide (a concentration of 50 μg mL⁻¹ in the sample) and using methanol as the elution agent. Under these conditions, the recoveries of the test acids in the spiked real samples are within ranges from 60% to 104% and 53% to 111% for analyte concentration levels of 1.40 ng mL⁻¹ and 0.14 ng mL⁻¹, respectively, depending on the lengths of the perfluorinated chains of the acids. In general, the recovery decreases with increasing length of this chain. The method developed exhibits very low limits of detection and determination and the results are fully comparable with those obtained when using more expensive HPLC-MS/MS instrumentation. Typical values amount to tenths to tens of pg mL⁻¹ and units to one hundred pg mL⁻¹ for the limits of detection and determination, respectively; the measuring sensitivity increases with increasing length of the analyte chain. The analyzes of real samples from the Vltava and Elbe rivers have demonstrated that the results obtained are similar to the values published for contamination of the Elbe and other rivers in western and central Europe. The concentrations determined are of the order of units to tens of pg mL⁻¹ and the C₈-C₁₀ acids occur most often.     

Perfluorinated and chlorinated pollutants as predictors of demographic parameters in an endangered seabird

Despite global occurrence of several perfluorinated compounds (PFCs) the potential ecological effects of such substances on natural populations are not known. In endangered lesser black-backed gulls (Larus fuscus fuscus) on the Norwegian Coast, the blood concentrations of PFCs were as high as legacy organochlorines (OCs), and here we examined whether PFCs show associations similar to those of OCs to factors potentially affecting population growth, by evaluating relationships between contaminant concentrations and demographic parameters (reproductive performance and the probability of adults returning between breeding seasons). PFCs were not adversely associated with demographic parameters, while the most persistent OCs; notably PCB and p,p′-DDE, were adversely associated with early chick survival, and adult return rate. This study thus suggests that when the concentrations of PFCs and OCs are of similar magnitude in a gull population, OCs are more likely to cause adverse ecological effects.     

Perfluorinated compounds in whole fish homogenates from the Ohio, Missouri, and Upper Mississippi Rivers, USA

A method for the analysis of 10 perfluorinated compounds (PFCs) in whole fish homogenate is presented and applied to 60 fish samples collected from the Ohio, Missouri, and upper Mississippi Rivers in 2005. Method accuracy ranged between 86 and 125% with limits of quantitation between 0.2 and 10 ng/g wet weight. Intra- and inter-batch precision was generally ±20%. Perfluorooctane sulfonate (PFOS) was the predominant compound identified in these samples, contributing over 80% of total PFC composition in the fish from these rivers, with median PFOS concentrations of 24.4, 31.8, and 53.9 ng/g wet wt in the Missouri, Ohio, and Mississippi Rivers, respectively. Median PFOS levels were significantly (p = 0.01) elevated in piscivorous fish (88.0 ng/g) when compared with non-piscivorous fish (15.9 ng/g). The 10 samples with PFOS concentrations above 200 ng/g were broadly scattered across all three rivers, providing evidence of the widespread presence of this compound in these US waterways.     

倒置A2O污水处理厂PFOS和PFOA的浓度分布特征及其总量分析

为考察全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)在倒置A2O污水处理厂各工艺段的浓度分布规律与去除效率,采用固相萃取(SPE)和高效液相色谱-质谱联用(LC-MS/MS)技术,检测分析了北京市卢沟桥污水处理厂夏季和冬季各工艺段污水和污泥中PFOS和PFOA的浓度.结果显示,PFOS在污水与污泥中的浓度均大于PFOA;进水中PFOS和PFOA的浓度分别为113.9~160.6 ng·L-1和14.7~68.1 ng·L-1,出水中的浓度分别为60.1~232.6 ng·L-1和29.9~71.5 ng·L-1;PFOS和PFOA在倒置A2O工艺没有得到有效去除.同时发现,PFOS在污泥中的浓度随季节变化较大,且其在污泥中的分配比高于PFOA;PFOS的质量流在工艺流程的各阶段变化较大,而PFOA没有明显的变化和差别.进水中PFOS和PFOA的质量流经过污水处理厂处理后反而升高,有可能是由于前驱物质降解产生.