全氟化合物在碳纳米管上的吸附研究

研究了3种全氟化合物：全氟辛烷磺酸盐（PFOS）、全氟己烷磺酸盐（PFHxS）、全氟辛酸（PFOA）在原碳纳米管（Pri—MWCNTs）和氧化型碳纳米管（O—MWCNTs）上的吸附行为．研究结果显示,3种全氟化合物在两种碳管上的吸附均呈明显的非线性;全氟化合物的等温吸附曲线均符合Freundlich及Langmuir模...     

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.     

全氟辛酸在腐殖酸上的吸附平衡

本文以全氟辛酸(perfluorooctanoic acid, PFOA)作为目标污染物,讨论了腐殖酸(Humic Acid, HA)吸附PFOA的特性和机制.结果表明,吸附动力学实验进行24 h后,PFOA在腐殖酸上的吸附达到完全平衡,吸附动力学可以用拉格朗日二级动力学较好拟合(R~20.99),颗粒扩散模型的拟合结果表明,PFOA在腐殖酸上的吸附分为3个过程,其中颗粒内部扩散是主导吸附的主要因素;吸附等温线用Liner、Freundlich和Langmuir模型对实验数据进行拟合,结果显示Liner和Freundlich模型吸附效果较好,说明疏水分配作用主导了PFOA在HA上的吸附;pH值和离子强度对吸附有明显的影响,吸附量随着pH值和离子强度的增加而减小;疏水性分配、氢键作用可能是主导HA吸附PFOA的主要因素.因此,在考虑PFOA在环境中行为的时候,要考虑腐殖酸的影响.     

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.     

全氟辛烷磺酸盐(PFOS)对其它有机污染物在沉积物上吸附的影响

采用平衡振荡实验方法,研究了不同浓度的全氟辛烷磺酸盐(PFOS)对两种有机污染物(硝基苯和菲)在沉积物上吸附的影响.结果表明,单组分PFOS在沉积物上是非线性吸附;与其它有机污染物共存时,随着PFOS浓度的升高,硝基苯的吸附量先减少后增加,而菲的吸附量则先增加后减少.PFOS对其它有机污染物吸附的影响规律与有机污染物的...     

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.     

电絮凝法去除模拟废水中的PFOS和PFOA

由于全氟化合物(PFCs)具有持久性、生物富集性和多种毒性,近年来人们日益关注广泛存在于工业废水、生活污水、以及天然水体中的全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)污染.本研究通过周期换向电絮凝法对模拟废水中的PFOS和PFOA污染进行高效处理,并对处理条件和吸附机理进行深入探讨.鉴于其去除效果会受到不同因素的影响,为明确最优参数,本研究着眼于以下影响因素:电极材料、电流密度、pH值、电解质的浓度与种类、极板间距、换相时间、转速、污染物的初始浓度等,同时采用控制变量法研究不同条件下溶液中PFOS和PFOA的去除率.由实验结果可知,在使用Al-Zn电极、添加0.035 mol·L~(-1)的NaCl、电流密度调整为25 mA·cm~(-2)、初始pH值控制在7左右、电极间距为2 cm、换向时间为10 s、转速为600 r·min~(-1)的条件下,PFOS和PFOA的去除效果最佳.     

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。     

PFOS和PFOA的水生生物基准探讨及对中国部分水体生态风险的初步评估

全氟辛基磺酸盐(PFOS)和全氟辛酸盐(PFOA)是中国淡水环境中广泛存在的两种典型全氟类污染物,中国目前尚缺乏PFOS和PFOA的淡水水生生物基准值。收集PFOS和PFOA对中国本土水生生物的毒性数据,利用美国环境保护局推荐的物种敏感度排序法推算了这两种物质的水生生物基准,获得PFOS的急性和慢性基准阈值分别为32.9μg·L~(-1)和1.97μg·L~(-1),PFOA的急性和慢性基准阈值分别为46.1 mg·L~(-1)和5.46 mg·L~(-1),两者的基准阈值表现出数量级的差异。针对中国部分淡水水体中PFOS和PFOA的污染水平,采用商值法(RQ)评价了两种污染物的生态风险,结果表明,PFOS和PFOA尚未对中国淡水环境中水生生物产生风险,处于可以接受的程度。     

磁性双壁碳纳米管（m-DWCNTs）对水中全氟辛烷磺酸（PFOS）的吸附

本文以双壁碳纳米管(double-walled carbon nanotubes,DWCNTs)为基础材料，通过化学沉淀法制备了磁性双壁碳纳米管(magnetic double-walled carbon nanotubes,m-DWCNTs)，研究了pH和吸附剂投加量对全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)的吸附影响.采用扫描电镜(SEM)、傅里叶红外光谱(FTIR)、X射线衍射(XRD)和VSM对吸附前后的m-DWCNTs进行了观察，并进行了吸附动力学模型和等温线模型拟合.结果表明，磁化后的双壁碳纳米管包覆了铁的氧化物，出现了Fe₃O₄的特征衍射峰，具有超顺磁性，饱和磁化强度为66.07 emu·g^-1. m-DWCNTs对PFOS的吸附更符合准二级动力学方程(R²>0.95)和Langmuir等温吸附模型(R²>0.95).随着m-DWCNTs投加量的增加，吸附量逐渐降低，去除率逐渐升高.吸附量随着pH值的增加而逐渐降低，...     

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   

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.     

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。     

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.     

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.     

Perfluorocarboxylic acids (PFCAs) and perfluoroalkyl sulfonates (PFASs) in surface and tap water around Lake Taihu in China

Perfluorinated compounds (PFCs) are ubiquitously distributed in the environment mainly as perfluoro-carboxylic acids (PFCAs) and perfluoroalkyl sulfonates (PFASs). In this paper, six PFCAs and two PFASs were quantified in surface and tap water samples from 12 sites around Lake Taihu near Shanghai City in East China. Predominant PFCs were perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), of which the concentration ranges were 6.8–206 and 1.2–45 ng·L⁻¹, the geometric means were 35.3 and 9.4 ng·L⁻¹, and the median (quartile range) values were 31.4 (34.4) and 10.4 (10.7) ng·L⁻¹, respectively. Other PFCs were also detected but in much lower concentrations than PFOA. The sources of the PFCs were expected to be direct industrial discharges in the Lake Taihu area, and this area was also a possible source of PFCs contaminations in Shanghai district in the downstream. PFCs distributions were found different in the upstream, downstream and north part of Lake Taihu. Occurrences of PFCs in the tap water in Lake Taihu area indicated their exposure to the local people. A brief estimation of the environmental risks by PFCs implied no acute or immediate risks from PFCs to local human health, but chronic risks from PFOA in the tap water should be considered in the downstream regions.     

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.     

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.     

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.     

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。