云南省会泽县农田土壤中全氟化合物污染特征研究

为探究云南省会泽县农田土壤中全氟化合物(perfluorinated compounds,PFCs)的污染特征及其潜在来源,2015年6月采集云南省会泽县农田土壤42份,利用高效液相色谱-串联质谱仪(HPLC-MS/MS)分析了11种PFCs的含量水平。结果表明,云南省会泽县农田土壤中全氟己酸(perfluorohexanoic acid,PFHx A)、全氟庚酸(perfluoroheptanoic acid,PFHp A)和全氟己烷磺酸(perfluorohexane sulfonate,PFHx S)均未检出,其余8种PFCs(ΣPFCs)的平均含量水平为0.392 ng·g-1,含量范围为0.298~0.998ng·g-1。全氟辛酸(perfluorooctanoic acid,PFOA)和全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)是最主要的PFCs,相对百分含量范围为45.93%~81.86%,其平均含量水平分别为0.116 ng·g-1和0.120 ng·g-1。与国内其他地区土壤中PFCs的含量水平相比,云南省会泽县农田土壤中PFCs含量水平低于上海,与广州、深圳、东莞、安徽、中国东部农村等地区土壤中PFCs的含量相当。主成分分析结果表明,以全氟癸酸(perfluorodecanoic acid,PFDA)、全氟辛烷磺酸(PFOS)和全氟十三酸(perfluorotridecanoic acid,PFTr DA)为主要标志物的2个主成分可以解释云南省会泽县农田土壤中73%的ΣPFCs。工业活动、大气沉降及长距离传输为云南省会泽县农田土壤中PFCs的主要来源。     

室内灰尘中全氟化合物的污染状况与人体暴露水平评估

全氟化合物(perfluorinated compounds,PFCs)是一种广泛应用于工业生产及日常生活的持久性有机污染物。为考察室内灰尘中PFCs的污染水平与人体暴露情况,采用超高效液相色谱-串联质谱(UPLC-MS/MS)对上海市11个家庭、5个宿舍以及25个办公室的室内灰尘样本中的6种全氟化合物(全氟庚酸PFHp A、全氟辛酸PFOA、全氟壬酸PFNA、全氟丁烷磺酸PFBS、全氟己烷磺酸PFHx S、全氟辛烷磺酸PFOS)进行检测。结果表明,室内灰尘中的∑PFCs含量在5.6~1 489.1 ng·g-1的范围内,其中PFOA含量最高,占∑PFCs的60%以上;PFOA和PFBS检出率达到100%,PFHp A、PFNA、PFHx S、PFOS的检出率分别为97.6%、92.7%、90.2%和65.9%;灰尘中的PFHp A、PFNA、PFBS、PFOS和各个目标物之间均存在显著的正相关(P0.05);办公室灰尘中的PFCs总量要显著高于家庭灰尘中的PFCs(P0.05)。在人体对室内灰尘中PFCs暴露情况评估中发现,在各个年龄段的比较中,婴幼儿(5岁)通过灰尘直接摄入和皮肤吸收2种途径的PFCs日均暴露剂量都是最大的,比成人的暴露量高1~5倍;且其通过灰尘直接摄入的暴露量要高出通过皮肤吸收的暴露量。     

生产企业及周边环境中全氟化合物的污染特征

生产企业作为全氟化合物(perfluorinated compounds,PFCs)的直接来源地,现今被认为是PFCs污染的主要来源之一,同时其对周边环境具有更加直接而重大的影响。我国对生产企业周边环境中PFCs污染特性研究的报道较缺乏,补充丰富各地生产企业周边环境的PFCs污染特征,可为PFCs点源分析和污染溯源提供依据。以湖北省孝昌县某化工有限公司为典型生产企业,采集7个采样点的水体和土壤样品,分析典型地区环境介质中PFCs的污染现状与特征。结果显示,11种目标PFCs污染物在水体中有7种、土壤中有6种不同程度地检出,环境水体中PFCs的总浓度介于4.70~40.22μg·L-1,土壤中PFCs的总浓度介于58.22~2 075.60 ng·g-1之间。全氟辛基磺酸(PFOS)为典型行业周边水体和土壤中最主要的PFCs污染物,其次是水体中的全氟己基磺酸钾(PFHx S)、全氟丁烷磺酸钾(PFBS)和土壤中的全氟辛酸(PFOA)、全氟己基磺酸钾(PFHx S)。PFCs检出浓度的大小与采样点距典型企业的距离极其相关,距离与污染物总量之间呈显著负相关性,但周边环境中PFCs的种类和构成比,不受与点源之间距离的影响。     

全氟化合物对水生植物的生态效应研究Ⅰ——典型城市河道全氟化合物的暴露水平及植物富集特征

全氟化合物(perfluorinated compounds,PFCs)近年来得到国内外广泛关注,针对工业源排放区域的环境暴露、来源解析以及动物层面的生态效应有较多研究,但对于普遍存在于非工业源(生活源)的城市河道PFCs暴露及水生植物富集等研究较为缺乏。本研究选择位于北京北部东西贯通的城市河道——清河水体为对象,分析结果表明,清河水体中12种目标PFCs均有检出(总量最高为65.45 ng·L-1),并以全氟丁烷磺酸盐(perfluorobutane sulfonate,PFBS)为主(最高达45.63 ng·L-1);6种水生植物(篦齿眼子菜、黑藻、金鱼藻、芦苇、菖蒲及水葱)的富集物质均以全氟辛烷磺酸盐(perfluorooctane sulfonate,PFOS)和全氟辛酸(perfluorooctanoic acid,PFOA)为主,沉水植物中金鱼藻对于PFOS的蓄积效果优于黑藻及篦齿眼子菜,挺水植物中根部PFCs含量高于茎叶,根部PFOA及PFOS含量高于茎叶,但全氟丁酸(perfluorobutanoic acid,PFBA)含量茎叶则高于根部。整体来看,尽管芦苇、菖蒲和水葱3种挺水植物尚不能作为PFCs的超富集植物,但其根部对PFCs均有显著的吸收效果,具有一定的生态修复潜质;沉水植物中金鱼藻是北方自然河道的优势物种,且对PFOS具有显著的富集效应,因此有必要进一步探索其PFCs生物指示和生态修复功能。     

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.     

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。     

固相萃取-高效液相色谱串联质谱技术测定污水中的全氟化合物

以全氟辛烷羧酸(PFOA)和全氟辛烷磺酸(PFOS)为代表的全氟化合物(PFCs),在日用消费品和工业生产中被广泛使用,并可通过各种途径大量进入环境.在全球各类环境介质以及生物体中已经普遍检测到了PFCs的存在.目前有关水环境中PFCs的分布及归趋研究,主要针对PFOS和PFOA及其长链同系物.随着PFOS和PFOA的禁用,一系列短链同系物作为替代物质进入生产和应用领域,并最终进入环境.目前针对短链全氟化合物的分析方法报道的还较少.     

武汉地区水环境中全氟化合物污染水平及其分布特征

武汉作为中国氟化工行业的主要生产基地之一,其水环境中全氟及多氟类化合物(PFASs)污染情况对评估该地区水环境生态安全至关重要。采集了武汉城区10个污水处理厂进、出口污水和19个地表水样品,利用HPLC-ESI-MS/MS技术分析研究该区域水环境中PFASs污染水平及其分布特征。结果发现,武汉地区的污水和地表水样品中,PFASs污染均以短链同系物全氟丁酸(PFBA)和全氟丁基磺酸(PFBS)为主。污水处理厂进、出口污水中PFASs总浓度分别为11.8~12 700 ng·L~(-1)和19.1~9 970 ng·L~(-1)。在城区15个湖水样品中,PFASs总浓度为21.0~10 900 ng·L~(-1);在流经城区的4个江水样品中,PFASs总浓度为4.11~4.77 ng·L~(-1),比湖水样品中PFASs浓度水平低1~2个数量级。与污水中PFASs空间分布趋势一致,各湖泊水样中PFASs总体水平呈现汉口汉阳武昌的趋势,表明城市工业布局与人口密度程度直接影响城市PFASs污染空间分布。值得注意的是,与以往水环境中PFASs污染以全氟辛酸(PFOA)和全氟辛基磺酸(PFOS)为主不同,武汉地区水环境中PFASs污染以短链同系物为主,表明短链替代效应已经渐渐在中国化工领域出现,中国全氟行业在响应国际组织规范和建议的基础上做出了实质性进展。然而,对于短链PFASs的污染特征、迁移运输以及生态风险等科学问题,还需要更进一步的研究。     

全氟化合物在天津大黄堡湿地多介质分布研究

对天津市大黄堡湿地自然保护区内的水、底泥及生物样品的不同组织中的全氟化合物(PFCs)的污染水平进行了研究,分析了PFCs在水-底泥的分配系数,生物积累因子以及生物体内不同组织间的分配系数.水相中的PFCs以伞氟辛烷羧酸(PFOA)为主,浓度范嗣为24.8-48.2 ng·L-1,其次为伞氟辛烷磺酸(PFOS),浓度范...     

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。     

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.     

Thermal defluorination behaviors of PFOS,PFOA and PFBS during regeneration of activated carbon by molten salt

• New method of mineralizing PFCs was proposed. • Activated carbon was regenerated while mineralizing PFCs. • Molten NaOH has good mineralization effect on PFOS and PFBS. Current study proposes a green regeneration method of activated carbon (AC) laden with Perfluorochemicals (PFCs) from the perspective of environmental safety and resource regeneration. The defluorination efficiencies of AC adsorbed perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanesulfonate (PFBS) using three molten sodium salts and one molten alkali were compared. Results showed that defluorination efficiencies of molten NaOH for the three PFCs were higher than the other three molten sodium salts at lower temperature. At 700°C, the defluorination efficiencies of PFOS and PFBS using molten NaOH reached to 84.2% and 79.2%, respectively, while the defluorination efficiency of PFOA was 35.3%. In addition, the temperature of molten salt, the holding time and the ratio of salt to carbon were directly proportional to the defluorination efficiency. The low defluorination efficiency of PFOA was due to the low thermal stability of PFOA, which made it difficult to be captured by molten salt.The weight loss range of PFOA was 75°C–125°C, which was much lower than PFOS and PFBS (400°C–500°C). From the perspective of gas production, fluorine-containing gases produced from molten NaOH-treated AC were significantly reduced, which means that environmental risks were significantly reduced. After molten NaOH treatment, the regenerated AC had higher adsorption capacity than that of pre-treated AC.     

近岸海水中全氟化合物的液相色谱-离子阱质谱法测定

建立了利用高效液相色谱-电喷雾离子阱质谱(HPLC-ESI-IT-MS/MS)测定近岸海水中多种常见全氟化合物(PFCs)的分析方法.采用固相萃取法(SPE)对海水中的PFCs净化富集,用HPLC-ESI-IT-MS/MS多反应离子监测(MRM)模式对各组分(全氟己烷磺酸、全氟辛烷磺酸、全氟辛烷磺酰胺、全氟己酸、全氟庚酸、全氟辛酸、全氟壬酸、全氟癸酸、全氟十一酸、全氟十二酸)进行测定.在最佳实验条件下,采用基质匹配标准曲线法定量,以消除海水基质的影响,8种目标化合物的检出限介于0.50—1.00 ng·L-1,9种PFCs的回收率在71.0%—130.2%之间,能满足近岸海水中多种PFCs检测的要求.青岛沿岸表层海水样品测定结果显示,全部采样站点的海水样品中均检测到≥4种PFCs,说明青岛沿岸海水中已有一定程度的PFCs污染.     

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.     

Effect of co-existing organic compounds on adsorption of perfluorinated compounds onto carbon nanotubes

Co-existing organic compounds may affect the adsorption of perfluorinated compounds (PFCs) and carbon nanotubes in aquatic environments. Adsorption of perfluorooctane sulfonate (PFOS), perfluorooctane acid (PFOA), perfluorobutane sulfonate (PFBS), and perfluorohexane sulfonate (PFH_xS) on the pristine multi-walled carbon nanotubes (MWCNTs-Pri), carboxyl functionalized MWCNTs (MWCTNs-COOH), and hydroxyl functionalized MWCNTs (MWCNTs-OH) in the presence of humic acid, 1-naphthol, phenol, and benzoic acid was studied. Adsorption kinetics of PFOS was described well by the pseudo-second-order model and the sorption equilibrium was almost reached within 24 h. The effect of co-existing organic compounds on PFOS adsorption followed the decreasing order of humic acid>1-naphthol>benzoic acid>phenol. Adsorbed amounts of PFOS decreased significantly in the presence of co-existing or preloaded humic acid, and both adsorption energy and effective adsorption sites on the three MWCNTs decreased, resulting in the decrease of PFOS adsorption. With increasing pH, PFOS removal by three MWCNTs decreased in the presence of humic acid and phenol. The adsorbed amounts of different PFCs on the MWCNTs increased in the order of PFBSxS相似文献   

全氟烷基磺酸盐(PFOS)、全氟己烷磺酸盐(PFHS)和全氟丁烷磺酸盐(PFBS)对非洲爪蟾胚胎的发育毒性

全氟烷基磺酸盐(PFASs)在工业生产和生活中广泛应用,某些PFASs已成为环境中普遍的污染物。鉴于对动物和人类的潜在毒性,全氟辛烷磺酸盐(PFOS)已被禁用,由一些半衰期相对较短的短链PFASs(如全氟丁烷磺酸盐,PFBS)替代。虽然四碳的PFBS和六碳的全氟己烷磺酸盐(PFHS)已经广泛使用,但目前对其毒性及其机制的了解很少。通过检测发育毒性和致畸性的非洲爪蟾胚胎致畸试验(FETAX),得到PFOS、PFHS和PFBS半致死浓度(LC50),半致畸浓度(EC50)和最小抑制生长浓度(MCIG),比较研究了3种化合物的发育毒性。结果发现,PFOS的LC50、EC50和MCIG分别为51.46、108.20和35mg·L-1。PFHS和PFBS的LC50大于100mg·L-1,对胚胎形态和生长没有明显影响。PFASs暴露引起非洲爪蟾胚胎运动行为异常。FETAX结果表明,PFOS急性发育毒性明显大于PFHS和PFBS。     

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.