我国典型含PFOS/PFOSF废物处置技术可行性分析与建议

为促进我国全氟辛基磺酸及其盐类和全氟辛基磺酰氟(PFOS/PFOSF)的削减和逐步淘汰,防控环境风险,迫切需要对淘汰、废弃的含PFOS/PFOSF产品、副产物以及生产和使用过程中产生的含PFOS/PFOSF废物进行安全无害化处理处置. 调研和数据分析结果表明,2021年我国已停产PFOSF,2002—2020年我国PFOS/PFOSF的生产总量约为2 120 t. 我国典型含PFOS/PFOSF液态废物包括废弃消防泡沫、消防泡沫使用后收集的残液、废弃电镀镀液、工艺或清洗废水、废有机溶剂,以及固态/半固态废物有蒸(精)馏釜残、废水处理污泥、污染土壤、电镀滤渣、废吸附剂和过滤材料等. 目前针对液态废物,可行的PFOS/PFOSF非破坏处理技术主要有活性炭和树脂吸附、膜滤、混凝,可行的PFOS/PFOSF破坏处理技术有焚烧/水泥窑、超声降解和亚/超临界水处理技术,但在应用时都有一定的前置条件;针对固态/半固态废物,可行的PFOS/PFOSF非破坏处理技术包括稳定化和废物填埋,而焚烧/水泥窑是目前最为可行的PFOS/PFOSF破坏处理技术. 建议根据我国典型含PFOS/PFOSF废物的特点采取相应可行的处理处置技术,在应用成熟技术的同时,适当尝试采用亚/超临界水处理技术、超声降解技术以及其他较新的技术;对PFOS/PFOSF物质含量≥50 mg/kg的废物采用可行的破坏技术处置,对PFOS/PFOSF物质含量<50 mg/kg的废物经稳定化预处理后方可进入填埋场.      

我国PFOS的环境风险管理对策研究

PFOS在我国生产量不断增加,使用范围广泛,在整个生命周期中通过生产、销售、使用以及三废处理等过程排放到环境中,导致我国环境介质、野生动物和人体内均可检测到PFOS存在。为履行斯德哥尔摩公约,推动PFOS环境风险管理工作,本文分析了国际上已开展的PFOS风险管理措施,以及我国PFOS风险管理面临的形势和挑战,提出了我国PFOS风险管理的政策建议。     

基于环境风险的PFOS废物管理对策研究

PFOS是近来受到较多关注的一种持久性有机污染物(POPs)。斯德哥尔摩公约在我国生效后,我国不仅将面临PFOS的淘汰工作,还要解决历史库存和废物的处置和管理问题。为做好PFOS废物环境管理工作,本文分析了我国PFOS废物的现状,结合公约对于PFOS废物的管理要求,总结了我国开展PFOS废物管理面临的挑战,并提出相应的应对策略。     

1985~2019年中国全氟辛烷磺酰基化合物的动态物质流分析

全氟辛烷磺酰基化合物（PFOS）是一类具有持久性、生物累积性和毒性的化学品.揭示PFOS在较大时空范围内的流动、储存和释放规律,可为PFOS管理提供科学依据.本研究构建了1985~2019年中国PFOS的动态物质流模型,量化了流量、存量及环境释放量,并对结果进行了灵敏度和不确定性分析.结果表明,国内生产是中国PFOS主要的源,生产的PFOS多以终端产品形态流向国内市场,少数以原料形式出口;土壤和水体是中国PFOS主要的汇,释放到两者中的PFOS主要来自产品使用阶段,2019年达103 t.2000年前PFOS的总输入量和总输出量均相对较小,后逐步增加;2009年,相关公约的颁布使两者明显下降.2005年起,在用存量和环境释放量逐年增加,土地填埋存量自1985年起始终保持增长状态.含PFOS的废弃物的末端处理目前仍以土地填埋和焚烧等传统方式为主,但有向绿色处理方式转型的趋势.本研究结果可为健全我国PFOS管理提供基础数据和理论支持.     

PFOS/PFOA环境污染行为与毒性效应及机理研究进展

全氟辛烷磺酰基化合物（PFOS）和全氟辛酸（PFOA）是一类新型的持久性有机污染物（POPs）,近年来发现在环境系统中日益广泛分布,并在生物体内蓄积或发生致毒效应.本文首先从PFOS/PFOA在环境中的污染及其水平、在野生动物体内的暴露、对人体的暴露以及污染与暴露变化趋势等4个方面,分析了PFOS/PFOA最新的环境污染与生物暴露情况;从PFOS/PFOA在大气环境中的转运转化过程、在污水污泥中转运转化过程以及在生物体内的蓄积、代谢转化与降解过程等3个方面,阐述了PFOS/PFOA在环境中的迁移转化行为;还概述了最近几年在PFOS/PFOA所导致的生态效应及其可能的机理研究进展.最后,尝试性地提出了今后在PFOS/PFOA污染生态学方面的研究重点.     

危险化学品环境污染事故应急废物处理处置及全过程管理

危险化学品环境污染事故应急过程中产生的应急废物因受到危险化学品污染也会具有某些危险特性,但我国有关文件并未对应急废物的去向、最终处置等做出明确规定。在应急废物处理处置中,还存在处置能力弱,现有技术应用性不足,处理处置过程长、产生二次污染风险的时间长、环节多等问题。加强对危险化学品环境污染应急废物的管理是预防应急废物产生二次污染的重要保障。本文从应急废物处理处置单位的角度出发,提出加强危险化学品环境污染事故应急废物处理处置全过程管理,并对全过程管理中的重点工作进行了梳理。     

危险废物的处理处置措施研究

危险废物因具有毒性、易燃性、腐蚀性、反应性和感染性等多种危害特性,如果暴露于环境中将会对生态环境和人类健康造成很大威胁;所以及时而有效地处理处置危险废物意义极为重大.文章简要地介绍了危险废物的定义及其来源,并指出其对环境和人类造成的危害,总结了我国目前的危险废物处理处置技术的现状,根据我国危险废物污染防治的技术路线和技术政策,分析了危险废物的处置措施,系统地论述了常规危险废物的常用处置方法,从而揭示了我国在危险废物处理处置方面及管理方面的问题,并提出针对危险废物处理处置的对策与建议.     

全氟化合物处理技术的研究进展

全氟化合物(PFCs)具有生殖毒性、免疫毒性和神经毒性,是环境中新型难降解污染物。有效去除PFCs的工艺研究已成为目前环境友好处理处置技术领域的新热点。该文在概述PFCs特性与污染现状的基础上,较为全面地介绍了国内外学者对PFCs的处理技术,包括高级氧化法、物理法、光化学技术、电化学氧化法、生物法等处理处置方法,并就上述技术的降解率、动力学、降解机理、中间产物等方面进行论述。最后,对处理PFCs的未来研究方向与发展趋势提出了相应的建议。     

海水中Cu2+和Cr3+对PFOS在沉积物上吸附行为的影响规律

为了解重金属与全氟辛烷磺酸(PFOS)共存情况下,PFOS在沉积物上的吸附规律,本研究分别测定了在海水和淡水条件下添加不同浓度的Cu2+和Cr3+(0.5~50 mM)后,PFOS在沉积物上的吸附行为。结果表明,随着[Cu2+]的增加,PFOS在沉积物上的吸附能力和非线性均增强,且当溶液中PFOS浓度越低,增强作用越明显。与淡水相比,海水环境下该增强作用更为明显。随着[Cr3+]的增加,PFOS在沉积物上的吸附能力和非线性略有增强,且海水和淡水环境中增强作用几乎相同。对比发现,海水中Cu2+对PFOS在沉积物上的吸附增强效应比Cr3+更加明显。本文研究结果将有助于定量了解和预测PFOS和重金属复合污染情况下,PFOS在海水环境中的迁移规律,并为科学评价海洋环境中PFOS和重金属的生态风险及其总量控制提供技术支撑。     

城市生活污水污泥减量化和资源化研究概述

城市生活污泥产量日益增加,污泥处理问题也日严重。污泥的处理与处置已经成为了一个世界性的难题。传统的污泥处理方法如填埋、投海等都存在各自的问题,会对环境造成不同程度的影响。如何更优化地对污泥进行减量化和资源化将是今后污泥处理研究的重点。针对污泥处理过程中的环境问题和经济问题,介绍了近年来常用的污泥处理技术的研究现状和发展前景,对目前的污泥处理技术进行了理论分析和应用概述,为污泥的合理处理和处置提供参考。     

PFOS对太湖水体中典型鱼和食鱼鸟的次生毒性风险

全氟辛烷磺酰(PFOS)是我国环境中广泛存在的一种全氟类污染物,对生态环境存在潜在威胁.本文采用PFOS对我国食物链中鸟类与哺乳动物的毒性数据,根据欧盟现有化学物质风险评价技术指导文件,对PFOS的食物链的预测无效应浓度(PNEC经口)进行推导,并初步对我国太湖水生食物链进行次生毒性风险评价.结果表明,PFOS的次生毒性PNEC经口为0.04 mg·kg-1.PFOS太湖水体9种鱼和1种食鱼鸟的次生毒性风险商均小于1.根据本文收集的数据,PFOS对太湖水生食物链的次生毒性风险较小.该研究为我国PFOS的次生毒性风险评价提供科学依据.     

好氧颗粒污泥耐受PFOS的结构稳定性及微生物响应

以好氧颗粒污泥为接种污泥,通过全氟辛烷磺酸(PFOS)长期驯化实现耐PFOS颗粒的培养,考察不同驯化时期的污泥基本特性,并结合微生物群落演替过程、微生物表型分布以及功能途径的变化情况,以揭示其耐受机制.结果表明,好氧颗粒污泥经历解体、再形成和成熟3个阶段后可在PFOS暴露下稳定维持.驯化成熟后的好氧颗粒污泥表面丝状菌减少,并且被大量胞外聚合物(EPS)所包裹,结构更加致密.驯化期间颗粒污泥中存在大量抗性细菌以及维持颗粒稳定相关细菌,主要包括unclassified＿f＿＿Comamonadaceae、Defluviicoccus、Dongia、Rhodoplanes、Flavobacterium、Thauera、Azospira、Candidatus＿Competibacter、Azoarcus和norank＿f＿＿A4b,且部分菌属间存在显著的正相关性.群体感应途径和细菌趋化途径相关基因丰度在解体期上调,在颗粒形成和成熟期恢复至初始水平,说明细菌的群体感应效应和趋化性能够在颗粒应激过程中起重要作用.因此,好氧颗粒污泥可以通过特定菌群积极响应、促进细菌趋化作用和群体感应作用、提高EPS...     

Experimental and molecular dynamic simulation study of perfluorooctane sulfonate adsorption on soil and sediment components

Soil and sediment play a crucial role in the fate and transport of perfluorooctane sulfonate (PFOS) in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain unclear. This study experimentally isolated three major components in soil/sediment: humin/kerogen, humic/fulvic acid (HA/FA), and inorganic component after removing organics, and explored their contributions to PFOS adsorption using batch adsorption experiments and molecular dynamic simulations. The results suggest that the humin/kerogen component dominated the PFOS adsorption due to its aliphatic featureswhere hydrophobic effect and phase transfer are the primary adsorptionmechanism. Compared with the humin/kerogen, the HA/FA component contributed less to the PFOS adsorption because of its hydrophilic and polar characteristics. The electrostatic repulsion between the polar groups of HA/FA and PFOS anions was attributable to the reduced PFOS adsorption.When the soil organicmatterwas extracted, the inorganic component also plays a non-negligible role because PFOS molecules might form surface complexes on SiO₂ surface. The findings obtained in this study illustrate the contribution of organic matters in soils and sediments to PFOS adsorption and provided newperspective to understanding the adsorption process of PFOS on micro-interface in the environment.     

Experimental and molecular dynamic simulation study of perfluorooctane sulfonate adsorption on soil and sediment components

Soil and sediment play a crucial role in the fate and transport of perfluorooctane sulfonate(PFOS) in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain unclear. This study experimentally isolated three major components in soil/sediment: humin/kerogen, humic/fulvic acid(HA/FA), and inorganic component after removing organics, and explored their contributions to PFOS adsorption using batch adsorption experiments and molecular dynamic simulations. The results suggest that the humin/kerogen component dominated the PFOS adsorption due to its aliphatic features where hydrophobic effect and phase transfer are the primary adsorption mechanism.Compared with the humin/kerogen, the HA/FA component contributed less to the PFOS adsorption because of its hydrophilic and polar characteristics. The electrostatic repulsion between the polar groups of HA/FA and PFOS anions was attributable to the reduced PFOS adsorption. When the soil organic matter was extracted, the inorganic component also plays a non-negligible role because PFOS molecules might form surface complexes on SiO 2surface.The findings obtained in this study illustrate the contribution of organic matters in soils and sediments to PFOS adsorption and provided new perspective to understanding the adsorption process of PFOS on micro-interface in the environment.     

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.     

Effect of temperature on the sorption and desorption of perfluorooctane sulfonate on humic acid

Sorption and desorption of perfluorooctane sulfonate (PFOS) on humic acid at different temperatures were studied. It was found that the sorption process could be modeled with power kinetic equation very well, suggesting that diflusion predominated the sorption of PFOS on the humic acid. The sorption capacity was doubled when the temperature increased from 5 to 35°C, and thermodynamics parameters △G0 was calculated to be -7.11 to -5.04 kJ/mol, △H0 was 14.2 kJ/mol, and △S 0 was 69.5 J/(mol·K), indicating that the sorption was a spontaneous, endothermic, and entropy driven process. Desorption hysteresis occurred at all studied temperatures which suggested that humic acid may be an important sink of PFOS in the environment.     

Sorption of Perfluorooctane sulfonate（PFOS） including its isomers on hydrargillite as a function of pH,humic substances and Na2SO4

Perfluorooctane sulfonate（PFOS） is a persistent organic pollutant（POP） and emergent contaminant that are widespread in the environment. Understanding the mechanisms controlling the distribution of PFOS and its isomers between hydrargillite and the water phase is important in order to study their redistribution and mobility in the environment. This study investigated the effects of pH, humic acid, fulvic acid and Na₂SO₄ on sorption of PFOS isomers to hydrargillite. A mixture...     

维生素B12催化纳米零价铁仿生降解全氟辛磺酸

研究了维生素B₁₂（VB₁₂）催化纳米零价铁（nFe⁰）仿生还原降解工业级全氟辛磺酸（PFOS）.结果表明,VB₁₂催化nFe⁰不仅能够降解支链PFOS,而且也能够同时降解直链PFOS,这是首次报道直链PFOS的仿生还原降解.PFOS降解过程可用准一级动力学模型模拟,且升高温度有利于PFOS的还原降解去除和脱氟.超高效液相色谱-四级杆飞行时间质谱（UPLC-QTOF）定性分析表明,PFOS仿生降解产物包括4种全氟磺酸类（全氟碳链长度为C4~C7）、9种全氟羧酸类（全氟碳链长度为C2~C7、C10、C11和C13）和5种多氟代酸类（即H-全氟己酸、H-全氟庚酸、H-全氟辛酸、H₂-全氟辛酸和H-全氟辛磺酸）化合物.全氟磺酸类和全氟羧酸类化合物首次在VB₁₂仿生催化降解PFOS的产物之中检出,其中全氟十一烷酸（C10）、全氟十二烷酸（C11）和全氟十四烷酸（C13）等长链化合物第一次在降解PFOS过程中被发现.在降解样中检出的H-全氟烷烃（链长为C2~C7、C10、C11和C13）是否是PFOS的仿生降解产物,还有待进一步研究确认.