Occurrence,Spatial Distribution,Sources and Risk Assessment of Per-and Polyfluoroalkyl Substances in Surface Sediments of the Yellow River Delta Wetland

Per-and polyfluoroalkyl substances(PFASs)are emerging persistent organic pollutants(POPs).In this study,47 surface sediment samples were collected from the Yellow River Delta wetland(YRDW)to investigate the occurrence,spatial distribution,potential sources,and ecological risks of PFASs.Twenty-three out of 26 targeted PFASs were detected in surface sediment samples from the YRDW,with totalΣ23PFASs concentrations ranging from 0.23 to 16.30 ng g^(-1) dw and a median value of 2.27 ng g^(-1) dw.Perfluorooctanoic acid(PFOA),perfluorobutanoic acid(PFBA)and perfluorooctanesulfonic acid(PFOS)were the main contaminants.The detection frequency and concentration of perfluoroalkyl carboxylic acids(PFCAs)were higher than those of perfluoroal-kanesulfonic acids(PFSAs),while those of long-chain PFASs were higher than those of short-chain PFASs.The emerging PFASs substitutes were dominated by 6:2 chlorinated polyfluoroalkyl ether sulfonic acid(6:2 Cl-PFESA).The distribution of PFASs is significantly influenced by the total organic carbon content in the sediments.The concentration of PFASs seems to be related to human activities,with high concentration levels of PFASs near locations such as beaches and villages.By using a positive matrix factorization model,the potential sources of PFASs in the region were identified as metal plating mist inhibitor and fluoropolymer manufacturing sources,metal plating industry and firefighting foam and textile treatment sources,and food packaging material sources.The risk assessment indicated that PFASs in YRDW sediments do not pose a significant ecological risk to benthic organisms in the region overall,but PFOA and PFOS exert a low to moderate risk at individual stations.

A Convenient Method of Polyfluoroalkyl-lactonization

A novel synthesis of polyfluoroalkyl substituted -butyrolactones from the reaction of polyfluoroalkyl iodides with 4-pentenoic acid initiated with sodium dithionite was realized in good yields.

STUDIES ON POLYHALOALKANES Ⅳ. THE REACTION OF POLYFLUOROALKYL IODIDES WITH SILVER(I) SALTS

The conversion of polyfluoroalkyl iodides into the corresponding carboxylic acids by the reaction with silver (I) salts is described.

SYNTHESES OF A NOVEL POLYFLUOROALKYL SUBSTITUTED 2-HYDROXYETHYL ACRYLATE AND ITS COPOLYMERS

Polyfluoroalkyl substituted 2-hydroxyethyl acrylate 6 was synthesized in six steps usingglycerol as a starting material. A preliminary investigation has been taken on the synthesisand characterization of copolymers of 6 and 2-hydroxyethyl methacrylate.

Distribution of per-and polyfluoroalkyl substances in blood,serum,and urine of patients with liver cancer and associations with liver function biomarkers

Studies have shown that per-and polyfluoroalkyl substances(PFASs)may be hepatotoxic in animals or humans.However,data on clinical epidemiology are very limited.In this study,21PFASs were determined in patients with liver diseases,with the highest median concentrations detected in the serum sample(26.7 ng/mL),followed by blood(10.7 ng/mL)and urine(5.02 ng/mL).Higher total PFAS concentrations were found in hepatocellular carcinoma(HCC)patients compared to non-HCC patients,with significant discrepancies in serum and blood samples.Besides,significant correlations were also found among PFAS concentrations and age,gender,body mass index(BMI),and liver function biomarkers levels.For example,PFAS concentrations are significantly higher in males than in females;Several serum PFASs concentrations increase with age and BMI,while the serum perfluorohexane sulfonic acid(PFHxS)concentrations are negatively correlated with age.In addition,multiple regression models adjusted for age,gender and BMI found that increased serum perfluorobutane sulfonic acid(PFBS),perfluoroheptane sulfonic acid(PFHpS)and perfluorohexylphosphonic acid(PFHxPA)conentrations are correlated with elevated alkaline phosphatase(ALP),aspartate aminotransferase(AST),and alpha-fetoprotein(AFP)(p<0.05).Our results provide epidemiological support for the future study on the potential clinical hepatotoxicity of PFAS.

Emergency of per-and polyfluoroalkyl substances in drinking water:Status,regulation,and mitigation strategies in developing countries

The detection of per-and polyfluoroalkyl substances(PFAS)in water presents a significant challenge for developing countries,requiring urgent attention.This review focuses on understanding the emergence of PFAS in drinking water,health concerns,and removal strategies for PFAS in water systems in developing countries.This review indicates the need for more studies to be conducted in many developing nations due to limited information on the environmental status and fate of PFAS.The health consequences of PFAS in water are enormous and cannot be overemphasized.Efforts are ongoing to legislate a national standard for PFAS in drinking water.Currently,there are few known mitigation efforts from African countries,in contrast to several developing nations in Asia.Therefore,there is an urgent need to develop economically viable techniques that could be integrated into largescale operations to remove PFAS from water systems in the region.However,despite the success achieved with removing long-chain PFAS from water,more studies are required on strategies for eliminating short-chain moieties in water.

Chlorinated Polyfluoroalkyl Ether Sulfonic Acids(Cl-PFESAs)Are Associated with Eye Diseases in Humans and Eye Toxicity in Zebrafish

Evidence from animal experiments has shown that chlorinated polyfluoroalkyl ether sulfonic acids(Cl-PFESAs)can induce vision dysfunction in zebrafish.However,environmental epidemiological evidence supporting this hypothesis remains limited.In our case−control study,samples collected from 270 individuals(135 controls and 135 cases)from the Isomers of C8 Health Project data were analyzed for Cl-PFESAs.We also repeated our analysis on zebrafish to support our findings in humans and to decipher the mechanism underlying Cl-PFESA eye toxicity.The serum levels of per-and polyfluoroalkyl substances(PFASs)and alternatives were significantly higher in the cases than in the controls.Higher serum Cl-PFESA levels were associated with greater odds of eye diseases,and the trend showed a statistically significant dose-dependent relationship.The Shapley additive explanations(SHAP)value indicated that 8:2 Cl-PFESA was the dominant eye disease risk factor among the 13 studied PFASs.In zebrafish experiments,Cl-PFESAs induced eye toxicity in adult zebrafish by oxidative damage and cell apoptosis.Compared to the control group,there was significantly reduced thicknesses of the inner plexiform layer(IPL),outer plexiform layer(OPL),and retinal tissue in the zebrafish exposed to Cl-PFESAs.Our study provides human clinical and animal experimental data,showing that exposure to PFASs increases the odds of the development of eye toxicity.

PFAS及含氟气体管控下环保绝缘气体研究与电力装备应用展望

全球气候变化背景下,SF6的使用将受到更严格的限制。以C_(4)F_(7)N和C_(5)F_(10)O等为代表的低全球变暖潜在值(global warming potential,GWP)、高绝缘强度气体得到了广泛关注,相关高压电气装备已在多个国家推广应用。然而随着2019年《斯德哥尔摩公约》的签署,世界多国逐步出台了针对全氟烷基和多氟烷基物质(polyfluoroalkylsubstances,PFAS)以及含氟气体限制使用的法规和标准,以美国和欧盟为代表的激进PFAS政策也间接导致3M公司计划于2025年底累计停产包括C_(4)F_(7)N、C_(5)F_(10)O在内的58种含氟物质。为此,该文深入剖析PFAS及含氟气体管控背景下环保绝缘气体与装备发展面临的挑战,阐述相关政策对我国气体绝缘装备低碳发展的影响,指出氟碳类环保绝缘气体的全生命周期管控标准的制定及应用监管规范化是目前的重要工作,并对新型绝缘气体分子设计方法、绝缘与放电理论、工程应用技术及产品研发等方面的未来发展进行展望,以期为我国环保电力装备研发及相关政策的制定提供参考。

固相萃取结合高效液相色谱-串联质谱测定胎便中14种全氟和多氟烷基化合物

全氟和多氟烷基化合物(PFASs)是一类人工合成的物质,由于其热稳定、疏水、疏油等优良性质而被广泛使用于生活和生产中.PFASs具有环境持久性、生物累积性、多种毒性等特性,且可以通过胎盘屏障进入到胎儿体内,进而对胎儿健康产生潜在危害.胎便中积累了妊娠期间暴露于胎儿的外源性化合物,可用于监测PFASs对胎儿的宫内暴露特征.本研究基于固相萃取结合高效液相色谱-串联质谱技术,建立了胎便中14种PFASs的分析方法.采用乙腈/水(9∶1,V/V)对0.2 g冻干胎便样品进行超声提取,提取液经Envi-carb和Oasis WAX小柱固相萃取,0.1%氨甲醇洗脱.以10 mmol·L^(−1)乙酸铵水溶液和乙腈作为流动相对目标化合物进行梯度洗脱,采用Acquity UPLC BEH C18色谱柱进行分离,基于多反应监测负离子模式采集,内标法定量.结果表明,在2、5、20 ng·g^(−1)的加标浓度下,14种PFASs的回收率为65%—149%,相对标准偏差为3%—22%,方法检出限(MDLs)为0.001—0.149 ng·g^(−1),方法定量限(MQLs)为0.003—0.495 ng·g^(−1).使用该方法测定了10个胎便样品,ΣPFASs浓度范围为<MDLs—2.49 ng·g^(−1).该方法操作简单、便捷、灵敏度高且定量准确,为系统性研究胎便中PFASs的赋存特征及暴露风险提供了技术基础.

质谱技术在食品及食品接触材料的典型有机污染物中的应用研究进展

食品及食品接触材料有机污染物种类繁多,给环境和消费者健康带来诸多影响。质谱技术具有灵敏度高、分析速度快等特点,在分析检测领域发挥着重要作用。本文主要介绍了液相色谱-质谱联用技术在近年来比较关注的全氟多氟化合物(PFASs)、双酚类化合物(BPs)、季铵盐类化合物(QACs)3类典型有机污染物中的应用研究进展,并对未来发展趋势进行了展望。

Polyfluoroalkylation of 2-Aminothiazoles： Unexpected sp3 C CI Substitution under Mild Conditions

An efficient, highly selective method for polyfluoroalkylation of 2-aminothiazole derivatives was described. Specifically, a di-polyfluoroalkylated derivative was produced when 2-amino-4-chloromethylthiazole was reacted with perfluoroalkyl iodides under very mild conditions.

地表水中全氟及多氟烷基化合物(PFASs)的污染现状研究进展

近年来,全氟及多氟烷基化合物(per-and polyfluoroalkyl substances,PFASs)的大量生产使用,使得其在自然水体中的浓度日益升高.由于PFASs的生物毒性及强稳定性,环境中的PFASs严重威胁到生态环境及人类健康.目前,多个国家及相关国际组织开始对地表水中的PFASs展开检测,但目前的监测基本属于点源监测,大范围、长时间维度的监测依然缺乏,从而无法准确揭示PFASs的时空赋存特征.本文概述了PFASs在地表水中的赋存水平,同时阐述了地表水环境中PFASs的水平分布和垂直分布特征,并揭示了地表水中PFASs污染水平与组成的时间变化规律,总结了影响PFASs污染的主要因素,对后续PFASs监测提出了建议,以期为准确评估水环境中PFASs的污染状况提供依据.

孕期全氟和多氟烷基化合物暴露与儿童注意缺陷/多动障碍关联性的系统综述和Meta分析

目的 通过Meta分析方法探究孕期暴露于全氟和多氟烷基化合物(Per-and Polyfluoroalkyl Substances, PFAS)与儿童发生注意缺陷/多动障碍(Attention deficit/hyperactivity disorder, ADHD)的关联性。方法 计算机检索PubMed、Embase、Web of Science、CNKI、Wan Fang Data和VIP数据库,纳入孕期PFAS暴露与ADHD风险关联的观察性研究,并利用纽卡斯尔—渥太华量表(Newcastle-Ottawa Scale, NOS)评估文献质量,采用R 4.2.1软件进行Meta分析。结果 总共纳入了10项合格文献,Meta分析结果显示,孕期暴露于PFHxS与儿童发展ADHD有关,高暴露相比于低暴露水平的OR(95%CI)=0.72(0.52, 1.00),其他暴露未发现关联性:PFOA、PFOS、PFNA和PFDA每升高1个ln单位,OR(95%CI)分别为1.23(0.98, 1.53)、1.23(0.93, 1.62)、1.36(0.83, 2.25)和1.10(0.71, 1.70)。亚组分析结果表明,学龄前儿童发生ADHD风险与其孕期PFAS和PFOS暴露相关:PFAS和PFOS每升高1个ln单位,OR(95%CI)分别为1.46(1.15, 1.85)和1.83 (1.16, 2.89)。结论 孕期暴露于PFHxS与儿童发生ADHD存在关联,未发现孕期暴露于PFOS、PFOS、PFDA和PFNA与ADHD发病有显著关联,学龄前儿童患ADHD的风险升高受孕期母亲血清PFAS浓度的潜在影响。

母乳中全氟及多氟烷基化合物污染水平及婴儿暴露风险评估

为探究母乳中全氟及多氟烷基化合物(PFASs)的污染水平及婴儿暴露风险,本研究依托2018-2021年湖北应城的出生队列,采用同位素稀释-高效液相色谱-串联质谱法测定了324名产妇母乳中23种PFASs的含量,使用多元线性回归分析人口学特征、饮食习惯对产妇母乳PFASs含量的影响,估算婴儿经母乳的PFASs每日摄入量并评估其暴露风险。结果表明,母乳中23种PFASs在0.2~100 ng/mL范围内线性关系良好,相关系数均大于0.992,检出限为5~42 pg/mL,定量限为15~126 pg/mL,回收率为65.6%~108.1%,相对标准偏差为1.6%~12.8%。全氟辛烷磺酸(PFOS)、全氟辛酸(PFOA)和全氟己烷磺酸(PFHxS)为主要污染物,检出率均高于80%,中位数分别为200.7、63.5和25.2 pg/mL,其余化合物检出率均低于45%。多元线性回归结果表明,产妇年龄大、腌制食品摄入频率高可能与母乳PFASs暴露水平增高有关,豆类食品摄入频率高可能与母乳PFASs暴露水平降低有关。婴儿经母乳PFOS、PFOA和PFHxS的每日估计摄入量中位数分别为25.1、7.9和3.2 ng/(kg5d),表明部分婴儿经母乳摄入的PFASs健康风险值得关注。

QuEChERS-超高效液相色谱-串联质谱分析鱼中13种全氟及多氟烷基化合物

全氟及多氟烷基化合物(PFASs)广泛存在于全球环境水体中,鱼类等水产品的摄入可能是人类接触PFASs的重要来源,因此亟需建立鱼类产品中PFASs的高效、准确分析技术。本研究以磁性纳米材料为净化吸附剂,基于QuEChERS方法,建立了鱼类产品中13种PFASs的超高效液相色谱-串联质谱(UHPLC-MS/MS)分析方法。实验分别考察了萃取溶剂类型、净化吸附剂(Fe_( 3)O_( 4)-TiO_( 2)和N-丙基乙二胺(PSA))用量对PFASs回收率的影响,确定了最佳样品前处理条件。采用Luna Omega C18色谱柱(100 mm×2.1 mm,1.6μm)进行分离,利用电喷雾电离(ESI)源,在多反应监测(MRM)模式下采集质谱数据,内标法定量。在优化的实验条件下,13种PFASs在0.01~50μg/L内具有良好的线性关系,相关系数(R)≥0.9973,检出限为0.001~0.023μg/L,定量限为0.003~0.078μg/L。在低、中、高3个加标水平(0.5、10、100μg/kg)下,13种PFASs的加标回收率为78.1%~118%,日内精密度为0.2%~11.1%,日间精密度为0.8%~8.7%。将该方法应用于实际样品分析,所有鱼样品中均有PFASs检出,分别为全氟辛酸、全氟辛基磺酸、全氟十一烷酸、全氟十二烷酸和全氟十三烷酸,各自的检出总含量为0.327~1.728μg/kg。本方法前处理过程简单且灵敏度高,适用于鱼类产品中PFASs的分析。

超高效液相色谱-串联质谱法快速测定人体血清中12种全氟烷基和多氟烷基物质的含量

传统和新型全氟烷基和多氟烷基物质(PFASs)是一类持久性有机污染物,由于其会对人类产生潜在的健康风险而引起越来越多的关注,因此提出了超高效液相色谱-串联质谱法同时测定血清中7种全氟羧酸类化合物、3种全氟磺酸类化合物和2种新型PFASs替代品[全氟(2-甲基-3-氧杂己酸)(HFPO-DA),6∶2氯代多氟醚基磺酸(6∶2 Cl-PFESA)]含量的方法。健康人血清样品经解冻后,加入混合内标溶液和体积比1∶1的乙腈-甲醇混合溶液,超声混匀后于-20℃冷冻1 h,于4℃高速离心,上清液经真空冷冻挥干后复溶于体积比的3∶7甲醇-水混合溶液中,冰浴中涡旋混匀、超声,于4℃高速离心后,上清液上机测定。12种PFASs在Phenomenex Kinetex F5色谱柱上以不同体积比的2 mmol·L^(-1)乙酸铵溶液和甲醇的混合液梯度洗脱分离,电喷雾离子源负离子模式电离,多反应监测模式检测,以胎牛血清为基质进行内标法定量。结果显示:12种PFASs质量浓度和内标的质量浓度比值与其峰面积比值均在一定范围内呈线性关系,检出限(3S/N)为0.005~0.01μg·L^(-1);在3个浓度水平进行加标回收试验,回收率为88.5%~112%,测定值的相对标准偏差(n=5)为0.20%~8.7%;方法用于20份健康人血清样品的分析,9种PFASs检出率为100%(包括一种新型PFASs替代品6∶2 Cl-PFESA)。

盐度对全氟和多氟烷基物质(PFAS)在海水-沉积物界面吸附行为的影响

模拟海水-沉积物环境,分析了不同盐度影响下5种全氟和多氟烷基物质(PFAS)含量变化,并解析了PFAS的吸附动力学和热力学等吸附行为.在设置的不同盐度实验组中,全氟辛烷磺酸(PFOS)在沉积物中的吸附能力强于相同碳氟链长度的全氟辛酸(PFOA),其中PFOS在沉积物中的吸附量大于其替代物9-氯十六氟-3-氧杂壬烷-1-磺酸钾(9Cl-PF3ONS);PFOA在沉积物中的吸附量大于其替代物六氟环氧丙烷二聚酸(HFPO-DA),而小于另一替代物六氟环氧丙烷三聚酸(HFPO-TA).PFAS的沉积物分配系数(Kd)与盐度呈正相关,随着盐度的升高,PFAS在沉积物中的吸附量随之增加.PFAS的吸附过程涉及了疏水和静电相互作用.

珠江广州段水体中全/多氟烷基化合物的空间和季节分布特征

全/多氟烷基化合物(PFASs)普遍存在于各环境介质中,因具有生物累积性、持久性和潜在毒性,已成为全球最受关注的新污染物之一。城市河流污染来源复杂,受周边功能区和季节影响大,PFASs等新污染物的河流污染特征仍需进一步研究。该文选择珠江广州段为研究区域,在2020年7月采集40个水样,探讨水相样品中16种PFASs的空间分布和季节差异特征。珠江广州段水体中PFASs的总浓度为(77.7±38.3) ng/L(17.9~164 ng/L),干流中PFASs的浓度普遍高于支流,且浓度从城市附近的中上游到接近河口的下游大幅降低。雨季水体中PFASs的浓度较旱季显著降低,其组成也有一定变化,全氟辛酸(PFOA)在旱季和雨季中均占比最大,但雨季中全氟丁烷磺酸(PFBS)、全氟辛烷磺酸(PFOS)、全氟己酸(PFHxA)占比增加,PFOA和全氟丁酸(PFBA)占比减少,短链PFASs占比略有上升,70%的采样点短链PFASs在雨季的占比高于旱季。该研究为评估环境水体中PFASs污染提供了基础数据。

生物体内全氟和多氟烷基物质迁移转化及毒性

总结了全氟和多氟烷基物质(PFASs)的来源,综述了PFASs在生物体内的迁移转化行为及影响因素,并利用文献计量学方法对近38年PFASs的毒性研究进行了热点分析.结果表明PFASs的结构、生物组织中的酶活性、蛋白含量以及环境中的有机质含量与PFASs在生物体内的迁移和富集能力密切相关.PFASs毒性研究主要聚焦于不同环境介质和器官的毒性效应差异,研究方向由对动植物的毒性评价转变为人体健康风险预测.在此基础上,从个体、器官、生化和分子水平总结了PFASs毒性效应,提出关于PFASs的多层级毒性效应研究是未来的发展趋势,尤其是利用定量构效关系阐明生物毒性的层级效应是值得提倡的方法之一.展望了未来有关PFASs研究的发展方向,为阐明新污染物环境行为及开展相关毒理研究提供思路.

基于紫外线的高级氧化或高级还原技术降解水中全氟或多氟烷基化合物

全氟或多氟烷基化合物(PFASs)是一类具有难降解性、生物蓄积性和潜在毒性的持久性有机污染物,广泛存在于各类环境介质中。水环境是PFASs最重要的归趋之一,然而水处理常规技术难以去除PFASs,近年来,基于紫外线的高级氧化或高级还原技术在PFASs的降解中表现出巨大的发展潜力和良好的应用前景。本文针对目前对于直接紫外光降解、紫外高级氧化技术和紫外高级还原技术降解PFASs的相关研究,重点从降解机理(包括活性物种产生机理和反应机理)、降解效率(包括降解率和脱氟率)和影响因素(包括光波长、pH、溶解氧、无机离子和腐殖酸等)三个维度对比了不同反应体系下PFASs的去除效能,并总结了基于紫外线的高级氧化或高级还原技术应用于去除实际水体中PFASs时需克服的难点,以期为该类技术在PFASs降解方面的发展提供参考。