Effect of salinity and sediment characteristics on the sorption and desorption of perfluorooctane sulfonate at sediment-water interface

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl₂ concentration increased from 0.005 to 0.5 mol L⁻¹ at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl₂. Maximum irreversibility was found in the sorption systems with CaCl₂ in the concentration of 0.5 mol L⁻¹. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.     

表面活性剂对茭白生长影响及土壤残留分析

采用土培的试验方法,研究了在不同浓度阴离子表面活性剂——直链烷基苯磺酸钠(LAS)处理后,单季茭"美人茭"的生长、茭白叶片中叶绿素含量和抗氧化酶系统活性的变化情况,以及LAS在茭白叶片和土壤中的相对残留量.结果表明,10 mg.L-1、100 mg.L-1 LAS处理浓度对茭白的生长状态没有显著影响;1000 mg.L-1 LAS处理浓度下美人茭株高和最大叶宽均分别低于对照25.5%(p0.05)和27.0%(p0.05),处理过程中叶绿素总含量大幅下降.10 mg.L-1、100 mg.L-1 LAS处理浓度下美人茭的抗坏血酸过氧化物酶(APX)和过氧化氢酶(CAT)活性显著提高,1000 mg.L-1LAS处理浓度下美人茭的过氧化物酶(POD)活性受到严重的抑制.丙二醛(MDA)含量呈先上升后下降的趋势,并随着LAS处理浓度的升高而升高.茭白叶片中LAS残留量先下降后上升,10 mg.L-1处理浓度下美人茭叶片中LAS含量低;10和100mg.L-1处理浓度下土壤中LAS含量基本在0.1～0.5 mg.L-1之间,1000 mg.L-1处理浓度下土壤中LAS含量持续上升,达到2.0～3.0mg.L-1,且LAS含量在第28d比第7d时高54.0%(p0.05).与单纯的土壤环境相比,茭白-土壤系统能够更有效地降低土壤中LAS含量.     

Removal,distribution and plant uptake of perfluorooctane sulfonate (PFOS) in a simulated constructed wetland system

• PFOS was removed by soil adsorption and plant uptake in the VFCW. • Uptake of PFOS by E. crassipes was more than that of C. alternifolius. • PFOS in wastewater can inhibit the removal of nutrients. • Dosing with PFOS changed the soil microbial community in the VFCW. A vertical-flow constructed wetland (VFCW) was used to treat simulated domestic sewage containing perfluorooctane sulfonate (PFOS). The removal rate of PFOS in the domestic sewage was 93%–98%, through soil adsorption and plant uptake, suggesting that VFCWs can remove PFOS efficiently from wastewater. The removal of PFOS in the VFCW was dependent on soil adsorption and plant uptake; moreover, the percentage of soil adsorption was 61%–89%, and was higher than that of the plants uptake (5%–31%). The absorption capacity of Eichhornia crassipes (E. crassipes) (1186.71 mg/kg) was higher than that of Cyperus alternifolius (C. alternifolius) (162.77 mg/kg) under 10 mg/L PFOS, and the transfer factor of PFOS in E. crassipes and C. alternifolius was 0.04 and 0.58, respectively, indicating that PFOS is not easily translocated to leaves from roots of wetland plants; moreover, uptake of PFOS by E. crassipes was more than that of C. alternifolius because the biomass of E. crassipes was more than that of C. alternifolius and the roots of E. crassipes can take up PFOS directly from wastewater while C. alternifolius needs to do so via its roots in the soil. The concentration of 10 mg/L PFOS had an obvious inhibitory effect on the removal rate of total nitrogen, total phosphorus, chemical oxygen demand, and ammonia nitrogen in the VFCW, which decreased by 15%, 10%, 10% and 12%, respectively. Dosing with PFOS in the wastewater reduced the bacterial richness but increased the diversity in soil because PFOS stimulated the growth of PFOS-tolerant strains.     

泡沫分离法去除废水中的Cr(Ⅲ)离子

以绿色表面活性剂酪蛋白为起泡剂,采用间歇式泡沫分离法去除废水中高浓度Cr(Ⅲ)离子,考察了pH值、空气流量、酪蛋白的添加量、搅拌速度和装液体积5个因素对Cr(Ⅲ)离子去除率的影响。结果表明:当Cr(Ⅲ)离子初始浓度为100 mg·L-1、处理时间为1.5 h时,最佳分离工艺条件为pH=9.5、空气流量0.75 L·min-1、4 g·L-1的酪蛋白的添加量25 mL、搅拌速度800 r·min-1、装液体积1 500 mL,去除率可达99.78%;在最佳工艺条件下,用常规表面活性剂十二烷基苯磺酸钠(SDBS)代替酪蛋白进行对比实验,酪蛋白可以使废水中Cr(Ⅲ)离子去除率提高1.73%。酪蛋白是一种环境友好型物质,作为绿色生物表面活性剂适用于泡沫分离工艺中。     

真空紫外-亚硫酸盐法降解PFOS影响因素

通过试验,考察了亚硫酸盐浓度、pH值、全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)初始质量浓度及共存物质对真空紫外-亚硫酸盐法降解PFOS的影响.结果表明,亚硫酸盐浓度的增加有利于提高活性物种水合电子的量,PFOS降解率及脱氟率均随之提高,亚硫酸盐浓度从1 mmol·L~(-1)增加至20 mmol·L~(-1)时,PFOS降解率及脱氟率分别从45%及40%提高至97%及63%;随着原水pH值的升高,水合电子的生成量也随之增加,PFOS的降解率及脱氟率均提高,且脱氟率对pH值的变化更敏感;PFOS初始质量浓度的提高降低了PFOS的降解率及脱氟率,但PFOS的绝对降解量却大幅提高,当PFOS初始质量浓度从1 mg·L~(-1)提高至50 mg·L~(-1)时,PFOS在4 h内的降解量提高了约50倍,这主要是由于高污染物浓度条件下水合电子的利用率较高;Cl~-或HCO_3~-的存在对PFOS降解率影响较小,但对脱氟的影响较为明显,在试验研究的浓度范围内,PFOS脱氟率随Cl~-浓度的增加而提高,随HCO_3~-浓度的增加呈现先升高后降低的规律;腐殖酸的存在屏蔽了部分用于光化学反应的光,而且可以捕获体系的活性物种,从而降低了降解率及脱氟率.     

白腐菌对制浆黑液中硫酸盐木素的降解

研究了白腐菌对硫酸盐木素的降解作用和影响因素,结果发现,２种白腐菌对硫酸盐木素的降解能力不同,培养１０ｄ后,木云芝Ｌｕ－１１的降解率达到７４．５％,而黄孢原毛平革菌的降解率为６５．６％,分子量在１５００￣３０００ｋｄ之间的硫酸盐木素部分被降解最为明显,木云芝的降解产物只有一种主要组分,而黄孢原毛平革菌的降解产物有２种主要组分,培养条件如碳源,氮源、ｐＨ值和温度对白腐菌降解硫酸盐木素的作用有明显的影     

Comparative sorption and desorption behaviors of PFHxS and PFOS on sequentially extracted humic substances

The sorption and desorption behaviors of two perfluoroalkane sulfonates（PFSAs）, including perfluorohexane sulfonate（PFHx S） and perfluorooctane sulfonate（PFOS） on two humic acids（HAs） and humin（HM）, which were extracted from a peat soil, were investigated. The sorption kinetics and isotherms showed that the sorption of PFOS on the humic substances（HSs） was much higher than PFHx S. For the same PFSA compound, the sorption on HSs followed the order of HM 〉 HA2 〉 HA1. These suggest that hydrophobic interaction plays a key role in the sorption of PFSAs on HSs. The sorption capacities of PFSAs on HSs were significantly related to their aliphaticity, but negatively correlated to aromatic carbons,indicating the importance of aliphatic groups in the sorption of PFSAs. Compared to PFOS,PFHx S displayed distinct desorption hysteresis, probably due to irreversible pore deformation after sorption of PFHx S. The sorption of the two PFSAs on HSs decreased with an increase in p H in the solution. This is ascribed to the electrostatic interaction and hydrogen bonding at lower p H. Hydrophobic interaction might also be stronger at lower p H due to the aggregation of HSs.     

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暴露对肺癌细胞中信号通路的影响

为探讨全氟辛烷磺酸盐（PFOS）产生肺毒性的分子机制,采用细胞计数试剂盒（CCK-8）方法测定不同浓度PFOS对A549细胞活性的影响,并用二代测序方法测定PFOS暴露对A549细胞中miRNAs表达的影响,预测异常表达miRNAs的靶基因.通过生物信息学分析推断靶基因参与的信号通路及潜在的生物学功能.结果显示,低浓度PFOS（<00μmol/L）促进A549细胞增殖,高浓度PFOS抑制细胞增殖.暴露于300μmol/L PFOS中24h的A549细胞中108个miRNAs表达量显著上调,63个miRNAs表达量显著下调.差异表达miRNAs通过Ras、Rap1、HIF-1、ErbB和VEGF等信号通路参与细胞增殖、代谢和发育等生物学过程.这表明PFOS可通过影响细胞增殖和诱发炎症反应对肺造成威胁.     

环境中全氟辛基磺酸前体物好氧生物降解进展

目前,在土壤、大气、水体等各种环境介质中均检测到了全氟辛基磺酸（PFOS）及其前体物（PrePFOS）的存在.自然条件下,PrePFOS的非生物降解量可以忽略不计,其生物降解的途径和降解量是预测未来PFOS环境行为的基础.本文对PrePFOS在环境介质中的分布以及生物降解进行了综述.在所有的PrePFOS中,关于N-乙基全氟辛基磺酰胺乙醇（EtFOSE）的研究较深入,其在土壤、活性污泥、沉积物中的降解途径及PFOS产量均有报道,EtFOSE的降解速度及其PFOS产量与介质的理化性质、微生物群落结构密切相关,N-乙基全氟辛基磺酰胺乙酸（EtFOSAA）脱羧转化为N-乙基全氟辛基磺酰胺（EtFOSA）是EtFOSE转化为PFOS的主要限速步骤.最新关于EtFOSE在土壤中的好氧生物降解的研究首次提出全氟辛基磺酰胺乙酸（FOSAA）脱羧形成全氟辛基磺酰胺（FOSA）是EtFOSE转化成PFOS的另外一个可能的限速步骤.全氟辛基磷酸酯（DiSAmPAP）在沉积物中的半衰期>380d,其可能的降解途径是先降解为EtFOSE,之后降解为PFOS.最后,在已有研究基础上,提出目前PrePFOS研究存在的问题及今后的研究方向.