氟表面活性剂和氟聚合物(V)——PFOS的短碳氟链替代品

主要介绍PFOS的短碳氟链替代品,分析短碳氟链产品作为替代品的可行性依据、性能和环境行为,进一步讨论短碳氟链替代品的研究进展和优化策略,并指出短碳氟链产品当前面临的问题。     

高效液相色谱-串联质谱法测定动物源性食品两种含氟污染物

目的 建立一种同时测定动物源性食品中全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)含量的高效液相色谱-串联质谱(HPLC-MS/MS)的分析方法。方法 从前处理过程和色谱条件两个方面进行优化,在不使用价格昂贵的同位素内标的情况下提取样品,流动相为0.1%甲酸水溶液和甲醇,采用多反应监测(MRM)模式进行分析检测,外标法定量。结果 PFOS和PFOA含量在0.1~60 ng/mL范围内线性良好,相关系数均大于0.997,PFOS和PFOA定量限(LOQ,以信噪比＞10计)分别为0.1 μg/kg,0.01 μg/kg,样品加标回收率 85%~110%之间,相对标准偏差(RSD)均＜10%。该方法被用于检测国家认监委组织的CNCA-23-03(2023)能力验证样品,能力验证结果为满意。结论 该方法前处理简单,且不使用价格昂贵的同位素内标,回收率高,精密度好,色谱峰分离效果佳,适用于动物源性食品中PFOS和PFOA的检测。     

PFOS类持久性有机污染物的检测技术研究进展

全氟辛烷磺酰基化合物（PFOS）具有很高的生物蓄积性和多种毒性,是目前最难降解的持久性有机污染物。全氟化合物独特的拒水拒油性,使其被广泛地应用于纺织、皮革、造纸等行业。由其造成的污染已经逐渐成为全球性的环境问题,随着欧盟等组织出台的关于对PFOS等物质禁令的颁布,这已经成为持久性有机污染物研究的又一热点,其分析检测技术和方法的相关研究也得到日益广泛的关注和重视。讨论了PFOS及相关全氟化合物的概况及其检测技术的研究进展,对当前各类检测技术存在的问题作了探讨。     

膜富集-高强UV/SO32-体系高效降解PFOS的研究

工业废水中全氟辛烷磺酸(PFOS)浓度低,直接应用化学法降解能耗较高。采用膜分离与UV/SO3^2-光降解的组合工艺对其进行处理,研究了此组合技术的处理效果,并考察了影响降解率的因素。结果表明,反渗透膜可有效富集PFOS溶液,高强UV/SO3^2-体系可高效降解该富集溶液。提高溶液初始pH、SO3^2-浓度、紫外光强,均有利于PFOS降解率的提高,而PFOS初始浓度的提高会降低其降解率。     

Efficient electrochemical decomposition of perfluorocarboxylic acids by the use of a boron-doped diamond electrode

The electrochemical decomposition of environmentally persistent perfluorooctanoic acid (PFOA) was achieved by the use of a boron-doped diamond (BDD) electrode. The PFOA decomposition follows pseudo-first-order kinetics, with an observed rate constant (k₁) of 2.4 × 10^− 2 dm³ h^− 1. Under the present reaction conditions, k₁ increased with increasing current density and saturated at values over 0.60 mA cm^− 2. Therefore, the rate-limiting step for the electrochemical decomposition of PFOA was the direct electrochemical oxidation at lower current densities. In the proposed decomposition pathway, direct electrochemical oxidation cleaves the C-C bond between the C₇F₁₅ and COOH in PFOA and generates a C₇F₁₅ radical and CO₂. The C₇F₁₅ radical forms the thermally unstable alcohol C₇F₁₅OH, which undergoes F⁻ elimination to form C₆F₁₃COF. This acid fluoride undergoes hydrolysis to yield another F⁻ and the perfluorocarboxylic acid with one less CF₂ unit, C₆F₁₃COOH. By repeating these processes, finally, PFOA was able to be totally mineralized to CO₂ and F⁻. Moreover, whereas the BDD surface was easily fluorinated by the electrochemical reaction with the PFOA solution, medium pressure ultraviolet (MPUV) lamp irradiation in water was able to easily remove fluorine from the fluorinated BDD surface.     

Exposure and effects assessment of persistent organohalogen contaminants in arctic wildlife and fish

Persistent organic pollutants (POPs) encompass an array of anthropogenic organic and elemental substances and their degradation and metabolic byproducts that have been found in the tissues of exposed animals, especially POPs categorized as organohalogen contaminants (OHCs). OHCs have been of concern in the circumpolar arctic for decades. For example, as a consequence of bioaccumulation and in some cases biomagnification of legacy (e.g., chlorinated PCBs, DDTs and CHLs) and emerging (e.g., brominated flame retardants (BFRs) and in particular polybrominated diphenyl ethers (PBDEs) and perfluorinated compounds (PFCs) including perfluorooctane sulfonate (PFOS) and perfluorooctanic acid (PFOA) found in Arctic biota and humans. Of high concern are the potential biological effects of these contaminants in exposed Arctic wildlife and fish. As concluded in the last review in 2004 for the Arctic Monitoring and Assessment Program (AMAP) on the effects of POPs in Arctic wildlife, prior to 1997, biological effects data were minimal and insufficient at any level of biological organization. The present review summarizes recent studies on biological effects in relation to OHC exposure, and attempts to assess known tissue/body compartment concentration data in the context of possible threshold levels of effects to evaluate the risks. This review concentrates mainly on post-2002, new OHC effects data in Arctic wildlife and fish, and is largely based on recently available effects data for populations of several top trophic level species, including seabirds (e.g., glaucous gull (Larus hyperboreus)), polar bears (Ursus maritimus), polar (Arctic) fox (Vulpes lagopus), and Arctic charr (Salvelinus alpinus), as well as semi-captive studies on sled dogs (Canis familiaris). Regardless, there remains a dearth of data on true contaminant exposure, cause-effect relationships with respect to these contaminant exposures in Arctic wildlife and fish. Indications of exposure effects are largely based on correlations between biomarker endpoints (e.g., biochemical processes related to the immune and endocrine system, pathological changes in tissues and reproduction and development) and tissue residue levels of OHCs (e.g., PCBs, DDTs, CHLs, PBDEs and in a few cases perfluorinated carboxylic acids (PFCAs) and perfluorinated sulfonates (PFSAs)). Some exceptions include semi-field studies on comparative contaminant effects of control and exposed cohorts of captive Greenland sled dogs, and performance studies mimicking environmentally relevant PCB concentrations in Arctic charr. Recent tissue concentrations in several arctic marine mammal species and populations exceed a general threshold level of concern of 1 part-per-million (ppm), but a clear evidence of a POP/OHC-related stress in these populations remains to be confirmed. There remains minimal evidence that OHCs are having widespread effects on the health of Arctic organisms, with the possible exception of East Greenland and Svalbard polar bears and Svalbard glaucous gulls. However, the true (if any real) effects of POPs in Arctic wildlife have to be put into the context of other environmental, ecological and physiological stressors (both anthropogenic and natural) that render an overall complex picture. For instance, seasonal changes in food intake and corresponding cycles of fattening and emaciation seen in Arctic animals can modify contaminant tissue distribution and toxicokinetics (contaminant deposition, metabolism and depuration). Also, other factors, including impact of climate change (seasonal ice and temperature changes, and connection to food web changes, nutrition, etc. in exposed biota), disease, species invasion and the connection to disease resistance will impact toxicant exposure. Overall, further research and better understanding of POP/OHC impact on animal performance in Arctic biota are recommended. Regardless, it could be argued that Arctic wildlife and fish at the highest potential risk of POP/OHC exposure and mediated effects are East Greenland, Svalbard and (West and South) Hudson Bay polar bears, Alaskan and Northern Norway killer whales, several species of gulls and other seabirds from the Svalbard area, Northern Norway, East Greenland, the Kara Sea and/or the Canadian central high Arctic, East Greenland ringed seal and a few populations of Arctic charr and Greenland shark.     

Adsorption of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) on alumina: influence of solution pH and cations

The persistent nature of perfluorochemicals (PFCs) has attracted global concern in recent years. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are the most commonly found PFC compounds, and thus their fate and transport play key roles in PFC distribution in the natural environment. As most solid phases in natural water contain alumina, an investigation of PFOS and PFOA adsorption behavior on alumina should prove useful in evaluating the environmental impact of this type of persistent pollutant. Systematic experiments were carried out in this study to investigate the adsorption behavior of PFOS and PFOA onto alumina. The results of adsorption kinetics on alumina show that it takes 48 h to reach equilibrium. The adsorption isotherms reveal maximum adsorption capacities of 0.252 μg/m² for PFOS and 0.157 μg/m² for PFOA at pH = 4.3, with the difference primarily due to their different functional groups. An increase in pH leads to a decrease in PFOS and PFOA adsorption on alumina, which may be attributed to the reduction in electrostatic interaction. The adsorption of both PFOS and PFOA decreases with an increase in ionic strength for all four types of cations (Na⁺, K⁺, Mg²⁺, and Ca²⁺), due to the compression of the electrical double layer. Furthermore, the results also indicate that both Ca²⁺ and Mg²⁺ can form bridges with PFOA anions in solution, whereas only PFOS can be bridged by Ca²⁺ due to the higher covalent nature of magnesium.     

Perfluorinated alkylated substances in the aquatic environment: An Austrian case study

Perfluorinated alkylated substances (PFAS) are of global interest due to their occurrence and persistency in the environment. This study includes surface waters and sediments for the analysis of eleven PFAS. The PFAS studied can be grouped in perfluoroalkyl carboxylates (PFCAs), perfluoroalkyl sulfonates (PFS) and perfluoroalkyl sulfonamides (PFSA). The two most important compounds are perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). These two substances showed the most significant values for surface water samples with maximum concentrations of 21 ng l⁻¹ for PFOA and 37 ng l⁻¹ for PFOS. Sediment samples from seven Austrian lakes and the river Danube were studied. Whereas PFSA and PFS were not detected in any sediment sample PFCAs were detected in most of the lake samples in concentrations up to 1.7 μg kg⁻¹ dry wt. PFOA, perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA) were detected in all Danube river sediment samples in concentrations varying from 0.1 up to 5.1 μg kg⁻¹ dry wt. For the various sampling points the proportional mass flows deriving from wastewater discharges were calculated. Whereas only up to 10% of the average flow is discharged wastewater up to more than 50% of the PFAS mass flows in the rivers can be attributed to wastewater discharges. Besides wastewater different other pathways as emissions from point sources, further degradation of precursor products, runoff from contaminated sites or surface runoff as well as dry and wet deposition have to be considered as relevant sources for PFAS contamination in surface waters.     

环保型之绿色含氟材料——没有PFOA的氟世界

介绍了PFOA、PFOS的特性、功能和应用领域,及其对人类的危害和在全球受到的限制。     

全氟辛烷磺酰基化合物(PFOS)分析研究进展

全氟辛烷磺酰基化合物(PFOS)是全球性持久性有毒污染物中危害最为严重的一种物质,其分析检测技术和方法的相关研究已经受到广泛的重视.综述了近年来PFOS的分析检测研究进展,并对当前研究中存在的问题做了探讨.