山东省典型湿地水体和沉积物中全氟辛烷羧酸(PFOA)和全氟辛烷磺酸(PFOS)的污染特征

全氟辛烷羧酸(perfluorooctanoic acid,PFOA)和全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)广泛存在于全球范围内的各种环境介质中,是全氟化合物中最典型的持久性有机污染物.为考察山东省典型湿地中PFOA和PFOS的浓度水平与空间分布特征,采用超高效液相色谱-串联质谱与WAX固相萃取相结合的方法,检测并系统分析了南四湖流域和东部沿海地区水和沉积物体系中PFOA和PFOS含量状况.研究结果表明,PFOA和PFOS在研究区域全部水样中均被检测出,浓度范围分别为10.49—84.6 ng·L~(-1)和0.49—25.4 ng·L~(-1);其中南四湖流域表层水中污染物的含量高于东部沿海地区,并且污染物浓度从下游到上游呈上升趋势.沉积物样品中PFOA和PFOS的浓度范围(干重)分别为0.09—2.76 ng·g~(-1)和0.17—5.25 ng·g~(-1),其空间分布趋势和水样中的大致相同.与国内外其他地区水和沉积物中PFOA和PFOS含量进行对比,山东省典型湿地中两种污染物的污染水平较高且PFOA污染更为严重.与PFOA相比,水和沉积物体系中PFOS的分配系数更高,并且不同区域间的分配系数存在差异.此外,本文采用熵值法对研究区域内两种污染物进行了初步风险评估,分析结果显示PFOA和PFOS对水生生物和野生鸟类可能存在一定的生态风险,且PFOS的风险较高,考虑到全氟化合物的生物累积性和食物链放大效应,应重视PFOA和PFOS的生态风险.     

台湾儿童血清全氟化合物与血脂关联的性别差异研究

目的:全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)是广泛应用于工业和生活领域的全氟化合物,在人体及环境介质中均可检出。近几年的流行病学研究表明儿童PFOS和PFOA的暴露水平与血脂水平具有相关性。本研究拟进一步研究血清全氟化合物水平与儿童血脂间关联的性别差异。方法:以台湾儿童为研究对象,分析血清中总胆固醇(TC)、高密度脂蛋白(HDL)、低密度脂蛋白(LDL)、甘油三脂(TG)等生化指标与PFOS和PFOA血清水平的相关性。结果:线性回归模型分析表明男生血清PFOS、PFOA水平与血脂水平具有显著相关性。当男生血清中ln-PFOS和ln-PFOA水平每增加1 ng·m L~(-1)时,TC含量分别增高0.51 mg·d L~(-1)(95%CI:0.30~0.72)和6.53 mg·d L~(-1)(95%CI:1.96~11.11),但在女生中则没有观察到血清PFOS和PFOA水平与TC的相关性。趋势分析结果显示,随着儿童血清中PFOS和PFOA水平的增加,男生和女生血脂的TC、LDL和TG含量呈增高趋势。结论:台湾儿童血清PFOS和PFOA水平与血脂水平存在正相关,且在男生中观察到的效应强于女生。     

全氟辛烷羧酸(PFOA)与全氟辛烷磺酸(PFOS)的细胞毒性效应

新型污染物全氟辛烷羧酸(PFOA)与全氟辛烷磺酸(PFOS)在全球范围内的各种环境介质中被广泛检出,对生态安全和人体健康造成威胁。利用MTT(噻唑蓝)法研究了PFOA/PFOS对人体细胞的毒性效应。结果表明,低剂量PFOA和PFOS对人体正常肝细胞增殖具有显著毒性,其3 d半数抑制浓度(IC50值)分别约为5和0.5μg·L-1。此外,PFOA和PFOS均对MCF-7细胞增殖表现出显著的非单调剂量-毒性效应,并且在环境浓度范围(0.6μg·L-1)内均可促进MCF-7细胞增殖,表现出潜在的类雌激素作用风险。     

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.     

高效液相/四极杆-飞行时间串联质谱法分析活性污泥中的全氟辛烷磺酸及全氟辛酸

采用固相萃取/高效液相/四极杆飞行时间串联质谱检测活性污泥中的全氟辛烷磺酸(PFOS)及全氟辛酸(PFOA).以甲醇-水(含5mmol·l-1醋酸铵,体积比60∶ 40-80∶ 20)为流动相,经高效液相分离,四极杆-飞行时间质谱检测PFOS m/z 499→80,PFOA m/z 369→169.方法的检出限:PFOS 1.0ngm·l-1;PFOA 2.0 ngm·l-1,方法的线性范围:PFOS 6-150 ngm·l-1;PFOA 10-180 ngm·l-1,方法回收率:PFOS 87%-105%,PFOA 81%-90%.用此方法分析了我国4个城市和地区活性污泥中的PFOS和PFOA.     

4种短链全氟化合物替代物在城市污水处理厂的污染特征研究

全氟辛烷羧酸(perfluorooctanoic acid,PFOA)和全氟辛烷磺酸(perfluorooctyl sulfonate,PFOS)等长链全氟化合物(perfluorinated compounds,PFCs)具有持久性、生物累积性和毒性,近年来发现一些短链PFCs具有相对较短的半衰期,可以成为PFOA和PFOS的替代品,这些物质包括C4和C6结构的PFCs,如全氟丁烷羧酸(perfluorobutanoic acid,PFBA)、全氟己烷羧酸(perfluorohexanoic acid,PFHx A)、全氟丁烷磺酸(perfluorobutyl sulfonate,PFBS)和全氟己烷磺酸(perfluorohexyl sulfonate,PFHx S)。为解析我国城市污水厂短链PFCs污染水平和地域分布特征,本研究调查了我国不同地区17座城市污水处理厂的进水、二沉出水和污泥中4种短链PFCs的分布和浓度水平。结果表明4种短链PFCs、PFOA和PFOS在17座污水厂进水中检出率均为100%(6种目标物单体浓度范围:0.19~274.72 ng·L-1);污泥中PFOS和PFOA检出率为100%(PFOS:2.08~72.31 ng·g-1,PFOA:1.03~24.81 ng·g-1),PFBA、PFHx A检出率为100%(0.60~3.33 ng·g-1),PFBS和PFHx S的检出率分别为42.11%和63.16%。在污水厂进水中,将PFOA和PFOS与其同类的短链PFCs浓度进行比较,发现短链PFCs分别相对于PFOA和PFOS的比例最高可达93.47%和94.57%。4种短链PFCs、PFOA和PFOS的地域分布差异明显,总浓度呈现出华东、华南地区高于西北、东北、华北地区的趋势,其中华东地区调查的污水处理厂浓度最高。污水厂4种短链替代物主要通过污水排放,不同污水厂的日排放总量(污泥和出水)为0.25~273.07 g·d-1,万吨水排放量范围为0.04~1.37 g。研究将为我国全氟化合物替代物污染和控制提供数据基础和科学依据。     

北京水源地鱼体全氟化合物的暴露水平及其健康风险

全氟化合物(PFASs)作为一类新型的有机污染物,因具有持久性、可长距离传输、生物蓄积性和生物毒性等POPs特性,近年来得到全世界的广泛关注。本文以北京市水源地(密云水库和官厅水库)为研究区域,采用固相萃取(SPE)前处理与高效液相色谱串联质谱联用(HPLC-MS/MS)相结合的方法,分析测定了鱼样品中包括全氟辛烷磺酸(PFOS)、全氟辛酸(PFOA)、全氟丁酸(PFBA)、全氟丁烷磺酸(PFBS)等在内的12种PFASs的含量。利用同位素法确定了不同种类鱼的营养级关系,研究不同营养级中的PFASs浓度及生物放大效应,重点对全氟辛烷磺酸(PFOS)与全氟辛酸(PFOA)的生态风险以及对人体的健康风险进行评价。结果表明:北京市水源地的鱼体中的PFASs存在不同程度的检出,其中,全氟辛烷磺酸(PFOS)、全氟辛酸(PFOA)、全氟壬酸(PFNA)、全氟癸酸(PFDA)、全氟十一酸(PFUdA)和全氟十二酸(PFDoA)的检出率均达到100%,PFASs总量浓度达1.70~14.32 ng·g~(-1) wet weight(w.w.),PFOS和长链全氟羧酸PFCAs是鱼体中的主要污染物。同位素鉴定水库鱼的营养级层次范围在2.11~4.10,且肉食性鱼类营养级大多高于杂食性鱼类,PFOS沿着食物链生物放大的过程与稳定碳氮同位素富集过程基本同步。此外,采用人均日摄入量法(average daily intake,ADI)评估得到PFOS与PFOA的风险值分别为1.16 ng·kg~(-1)·d~(-1)和0.31ng·kg~(-1)·d~(-1),整体低于人均每天可承受摄入量(tolerable daily intake,TDI),结果表明,北京水源地鱼体中PFOS和PFOA含量未达到对生态系统和人体健康具有风险的水平。     

全氟化合物在阳离子表面活性剂改性碳纳米管上的吸附

采用两种阳离子表面活性剂,四丁基溴化铵(TBA)及聚乙烯亚胺(PEI)对碳纳米管进行改性,并研究了全氟辛酸(PFOA)、全氟辛烷磺酸盐(PFOS)、全氟己烷磺酸盐(PFHxS)在改性碳纳米管上的吸附行为.研究结果显示,除PFOS在TBA修饰的碳纳米管(TBA-MWCNTs)上的吸附等温线呈线性外,全氟化合物在原碳纳米管(Pri-MWCNTs)、TBA-MWCNTs及PEI修饰的碳纳米管(PEI-MWCNTs)上的吸附均为非线性.吸附等温线可以用Freundlich及Langmuir模型拟合.与Pri-MWCNTs相比,PEI-MWCNTs的零电荷点(pHzpc)增加了6.2个单位,全氟化合物的吸附系数Kd值增加2—3倍;而TBA-MWCNTs的pHzpc增加了1.0个单位,PFOS在高平衡浓度下的Kd值增加了两倍.随着溶液pH值的降低,全氟化合物在Pri-MWCNTs和PEI-MWCNTs上的吸附量有所增加,而在TBA-MWCNTs上的吸附受pH值的影响不大.这说明疏水作用及静电作用是全氟化合物在Pri-MWCNTs和PEI-MWCNTs上吸附的主要机制,而疏水作用则为TBA-MWCNTs上吸附的主要机制.与单溶质体系相比,PFOS与PFOA同时存在时二者在PEI-MWCNTs上吸附的Kd值均有所减小,且PFOA的减小程度大于PFOS.PFOS在TBA-MWCNTs上吸附的Kd值在高浓度下几乎不受PFOA的影响.     

一次性餐盒材料中全氟辛酸和全氟辛烷磺酸沥出性研究

利用高效液相色谱-串联质谱检测方法对一次性餐盒材料中可沥出性全氟辛酸(PFOA)和全氟辛烷磺酸(PFPS)进行了研究.分别选取水、3%乙酸(W/W)、15%乙醇(V/V)和正己烷4种浸取液模拟餐盒材料在使用过程中可能接触到的水性、酸性、酒精类和油脂类条件.材料经4种溶液浸提后,浸取液用固相萃取净化和浓缩,目标分析物PFOA和PFOS采用内标法进行定量.研究表明,一次性餐盒材料在模拟条件下中有以PFOA为主的伞氟类化合物从材料中沥出,其中酸性环境对PFOA的浸取率最高(2296 ng·m~(-2)), 为其它3种方法的82.8倍;4种浸提条件下PFPS的沥出率都比较低,浓度仪为0.7 ng·m~(-2)-5.4 ng·m~(-2).     

全氟烷基化合物在人体肝脏中的富集特征及其与肝损伤的关系

全氟烷基化合物(polyfluoroalkyl substances,PFASs,F(CF_2)_n-R)是广泛用于生产生活中的有机污染物,研究发现PFASs的暴露会对人体造成危害.为分析人体肝脏中PFASs的富集特征,本研究采用高效液相色谱串联质谱(HPLC-MS/MS)的方法,对天津市31例肝癌患者肝脏中10种PFASs(全氟己烷磺酸PFHxS、全氟辛烷磺酸PFOS、全氟十二酸PFDoDA、全氟己酸PFHxA、全氟庚酸PFHpA、全氟十一酸PFUnDA、全氟壬酸PFNA、全氟癸酸PFDA、全氟辛酸PFOA、全氟戊酸PFPeA)进行检测分析.结果表明,PFOS、PFOA、PFNA、PFUnDA和PFHxS具有较高的检出率(80%);∑PFASs浓度范围为8.97—181.87 ng·g~(-1),其中PFOS的平均浓度最高(40.87 ng·g~(-1)),占∑PFASs的77%;∑PFASs的平均浓度在男性肝脏样品中(64.04 ng·g~(-1))与女性样品中(36.82 ng·g~(-1))存在显著性差异,PFHxS、PFOS和PFDA的浓度在性别上也均呈显著差异,PFOA的浓度与年龄呈显著负相关性.此外,PFOA和PFHpA的浓度分别与肝细胞损伤标志物ALT和GGT之间存在显著正相关性.本研究是国内首次对人体肝脏中PFASs的暴露分析,PFOS是肝脏的主要暴露物;PFASs对男性的暴露风险高于女性,且青年人群PFASs的暴露风险相对较高;另外,浓度水平进行分析,PFASs的暴露与人体肝脏损伤存在统计学关联.     

Treatment technologies for aqueous perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA)

Fluorochemicals (FCs) are oxidatively recalcitrant, environmentally persistent, and resistant to most conventional treatment technologies. FCs have unique physiochemical properties derived from fluorine which is the most electronegative element. Perfluorooctanesulfonate (PFOS), and perfluorooctanoate (PFOA) have been detected globally in the hydrosphere, atmosphere and biosphere. Reducing treatment technologies such as reverses osmosis, nano-filtration and activated carbon can remove FCs from water. However, incineration of the concentrated waste is required for complete FC destruction. Recently, a number of alternative technologies for FC decomposition have been reported. The FC degradation technologies span a wide range of chemical processes including direct photolysis, photocatalytic oxidation, photochemical oxidation, photochemical reduction, thermally-induced reduction, and sonochemical pyrolysis. This paper reviews these FC degradation technologies in terms of kinetics, mechanism, energetic cost, and applicability. The optimal PFOS/PFOA treatment method is strongly dependent upon the FC concentration, background organic and metal concentration, and available degradation time.     

Growth inhibition and DNA damage in the earthworm (Eisenia fetida) exposed to perfluorooctane sulphonate and perfluorooctanoic acid

An artificial soil method was applied to study the effects of perfluorooctane sulphonate (PFOS) and perfluorooctanoic acid (PFOA) on earthworms (Eisenia fetida). Survival, growth inhibition and damage to DNA of earthworms were detected after 14 d acute exposure. The 14 d-LC₅₀ of PFOS and PFOA was 478.0?mg·kg^?1 dw and 759.6?mg·kg^?1 dw, respectively, indicating that they were of low toxicity. Both PFOS and PFOA could significantly inhibit the growth of earthworms after 14 d exposure, and growth inhibition rates increased with the greater concentrations of PFOS or PFOA, showing a dose–response relationship (PFOS: r?=?0.951, P r?=?0.962, P?P?50 of PFOS was lower than that of PFOA, the growth inhibition rate of earthworm exposed to PFOS was higher than that exposed to PFOA at the same concentration level, and the median values of TL, CL and OTM in PFOS treatments were also higher than those in PFOA treatments. In conclusion, both these fluorine compounds were moderately toxic to earthworms, but the PFOS effect was greater than that of PFOA.     

Perfluoroalkane acids in human milk under the global monitoring plan of the Stockholm Convention on Persistent Organic Pollutants (2008–2019)

● Perfluorooctanesulfonic acid and perfluorooctanoic acid highest in human milk. ● All other perfluoroalkane substances had median values of zero (101 samples). ● Branched PFOS recommended to be analyzed separately from linear isomer. ● PFOS and PFOA showed differentiated regional and income distribution. ● Human health risk assessment values not yet available at global level. Within the global monitoring plan (GMP) established by article 16 of the Stockholm Convention on Persistent Organic Pollutants, perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) are recommended for analysis in core matrices to assess occurrence and changes geographically and with time. In 101 samples consisting of 86 national pools and 15 pools from States in Brazil obtained between 2008 and 2019, PFHxS was detected in 17% of the national pools and none in Brazil. PFOA and PFOS had a detection frequency of 100% and 92%, respectively. Other perfluoroalkane substances (PFAS) had either low detection frequencies and median values of zero (carboxylic acids C₄–C₁₁; except PFOA) or could not be quantified in any sample (sulfonic acids, C₄–C₁₀, and long-chain carboxylic acids, C₁₂–C₁₄). Correlation between PFOA and PFOS was moderately (r = 0.58). Whereas median values were almost identical (18.9 pg/g f.w. for PFOS; 18.6 pg/g f.w. for PFOA), PFOS showed larger ranges (< 6.2 pg/g f.w.–212 pg/g f.w.) than PFOA (< 6.2 pg/g f.w.–63.4 pg/g f.w.). It was shown that wealthier countries had higher PFOA concentrations than poorer countries. No difference in concentrations was found for samples collected in countries having or not having ratified the Stockholm Convention amendments to list PFOS or PFOA. The goal to achieve 50% decrease in concentrations within ten years was met by Antigua and Barbuda, Kenya, and Nigeria for PFOS and by Antigua and Barbuda for PFOA. In a few cases, increases were observed; one country for PFOS, four countries for PFOA.     

A review of spatial and temporal assessment of PFOS and PFOA contamination in China

The current state of concentrations of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in China is presented. While products that are known to degrade to either PFOS or PFOA have been used in China, concentrations in environmental media have been reported to be relatively low across China. Greater concentrations of PFOS and PFOA were observed in southern and eastern China than in other areas of China. Concentrations of PFOS and PFOA were relatively great in the Huangpu River, with concentrations of 20.5 ng l^?1 and 1590 ng l^?1, respectively. Surface waters of Dongguan and Shanghai were more contaminated by PFOS and PFOA than that of other cities. Dongguan was the only city in China in which PFOS value in surface water exceeded the water quality criterion, while PFOA concentration in Shanghai was 152 ng l^?1. Similar to other contaminants, point-source pollution was also the common pattern of PFOS and PFOA contamination. Concentrations of PFOS in human blood in China were relatively greater in China than other countries, with drinking water contamination given as the most likely source. Concentrations of PFOS in human blood have increased from the 1980s to the 2000s, while such a trend was not observed for PFOA.     

全氟化合物同分异构体的环境行为及毒性效应研究进展

以全氟辛烷磺酸盐(PFOS)和全氟辛烷羧酸(PFOA)为代表的全氟化合物(PFASs)是一类新型持久性有机污染物,目前已经在全球自然环境、野生生物及人群中广泛检出,其环境与健康问题已引起人们的高度重视。传统的电氟化法生产工艺使PFASs产品存在碳链同分异构体。这些PFAS的同分异构体可能具有不同的环境行为和毒理效应。随着分析方法的逐渐成熟,目前,国外的学者已经在该研究领域进行了一些探索性的研究,并取得了一定的进展,而我国在该领域的研究相对较少。以PFOS和PFOA为例,在介绍了PFAS同分异构体的来源、命名和世界各地生产厂家的异构体组成等基本信息的基础上,还系统介绍了环境介质中PFAS同分异构体的分析方法、环境迁移转化差异及源分析研究;生物和人体的生物累积性及毒理学差异等;并对目前存在的问题进行了讨论,为今后PFAS同分异构体的环境问题研究提供相应的参考。     

Decomposition of perfluorooctanoic acid by microwaveactivated persulfate: Effects of temperature, pH, and chloride ions

Microwave-hydrothermal treatment of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S₂O ₈ ^2? ) has been found effective. However, applications of this process to effectively remediate PFOA pollution require a better understanding on free-radical scavenging reactions that also take place. The objectives of this study were to investigate the effects of pH (pH = 2.5, 6.6, 8.8, and 10.5), chloride concentrations (0.01?C0.15 mol·L^?1), and temperature (60°C, 90°C, and 130°C) on persulfate oxidation of PFOA under microwave irradiation. Maximum PFOA degradation occurred at pH 2.5, while little or no degradation at pH 10.5. Lowering system pH resulted in an increase in PFOA degradation rate. Both high pH and chloride concentrations would result in more scavenging of sulfate free radicals and slow down PFOA degradation. When chloride concentrations were less than 0.04 mol·L^?1 at 90°C and 0.06 mol·L^?1 at 60°C, presence of chloride ions had insignificant impacts on PFOA degradation. However, beyond these concentration levels, PFOA degradation rates reduced significantly with an increase in chloride concentrations, especially under the higher temperature.     

Perfluorinated compounds in water and sediment from coastal regions of the northern Bohai Sea,China

Concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and other perfluorinated compounds (PFCs) were measured in water and sediment from coastal Bohai Bay and surrounding rivers flowing into the bay. Of the 15 PFCs measured, PFOS and PFOA were detected with the greatest frequency. Concentrations in water ranged from<0.2 to 31 ng·L^?1 and<1.0 to 82 ng·L^?1 for PFOS and PFOA, respectively. Concentrations of PFOS and PFOA in sediments ranged from<0.1 to 2.0 ng·g^?1 dw and<0.1 to 0.5 ng·g^?1 dw, respectively. Concentrations of PFCs in Bohai Bay were less than those observed in other areas in Asia, but greater concentrations of ∑PFCs were observed in the Dalin River with concentrations increasing from upstream to downstream, and the greatest concentrations in sediment were observed in tidal flats. The ratio of ∑PFCs in sediment and water indicated that sediment could serve as a significant sink for PFUnA.