全氟辛烷磺酸盐(PFOS)对半滑舌鳎(Cynoglossus semilaevis)免疫相关基因表达的影响

为了解全氟辛烷磺酸盐(perfluorooctane sulfonate, PFOS)暴露对半滑舌鳎(Cynoglossus semilaevis)免疫功能的影响,在实验室条件下,运用RT-PCR方法分析了PFOS暴露对半滑舌鳎热休克蛋白hsp70、hsp90、C型凝集素(c-type lectin)和细胞色素c氧化酶(cytochrome c oxidase, cox)等4种免疫相关基因表达水平的影响。实验测定了上述4种基因在半滑舌鳎肝、鳃、肠及肌肉4种不同组织中随时间(0、24 h、48 h、96 h和7 d)的表达变化情况。结果表明,在4种组织中,hsp70基因的表达与对照相比为上调,其中,肝组织hsp70基因的表达量显著高于其他各组织,且表达高峰值的出现也早于其他各组织;hsp90基因在肝和鳃组织中表达量随时间不同而波动,在肠组织中表达上调,在肌肉中表达显著下调;c-type lectin基因表达量与对照组相比表达显著下调或无明显差异;cox基因在肝组织和肠组织中表达下调,在鳃和肌肉中表达上调。上述研究结果表明,PFOS能引起免疫相关基因的表达变化,对半滑舌鳎具有潜在的免疫毒性。肝组织中各免疫基因对PFOS胁迫的响应高于其他组织。本研究可为阐明全氟辛烷磺酸盐对半滑舌鳎的免疫毒性提供基础数据。     

直链烷基苯磺酸盐促进剩余污泥产生短链脂肪酸的研究

采用批试试验的方法研究了十二烷基苯磺酸钠(C12-LAS)对剩余污泥在厌氧发酵过程中产生的短链脂肪酸(SCFAs)的影响.结果表明,C12-LAS的投加极大地提高了剩余污泥厌氧发酵过程中的SCFAs产量.当C12-LAS加入量低于0.1g·g-1时,SCFAs产量随着C12-LAS加入量的增加而增加,然而,当C12-LAS加入量高于0.1g·g-1时,SCFAs产量反而有所降低.从污泥产酸量以及经济成本考虑,C12-LAS的最佳投加量为0.02g·g-1,此时剩余污泥的SCFAs最大产量出现在第6天.进一步的研究表明,C12-LAS不仅促使大量的碳水化合物和蛋白质脱离污泥颗粒并溶解到液相中,而且抑制了产甲烷菌的活性.尽管剩余污泥经历着酸化过程,但由于其释放出大量的NH4 -N,污泥在整个厌氧发酵过程中的pH值逐渐升高.     

Water solubility enhancements of PAHs by sodium castor oil sulfonate microemulsions

Water solubility enhancements of naphthalene( Naph), phenantherene(Phen) and pyrene(Py) in sodium castor oil sulfonate(SCOS) microemulsions were evaluated. The apparent solubilities of PAHs are linearly propertional to the concentrations of SCOS microemulsion, and the enhancement extent by SCOS solutions is greater than that by ordinary surfactants on the basis of weight solubilization ratio(WSR). ThelogKcm values of Naph, Phen, and Py are 3.13, 4.44 and 5.01 respectively, which are about the same as the logKow values. At 5000 mg/L of SCOS conccentration, the apparent solubilities are 8.80, 121, and 674 times as the intrinsic solubilities for Naph, Phen, and Py. The effects of inorganic ions and temperature on the solubilization of solutes are also investigated. The solubilization is improved with a moderate addition of Ca^2 , Na^ , NH4^ and the mixture of Na^ , K^ , Ca^2 , Mg^2 and NH4^ . WSR values are enhanced by 22.0% for Naph,23.4% for Phen, and 24.6% for Py with temperature increasing by 5~C. The results indicated that SCOS microemulsions improve the performance of the surfactant-enhanced remediation(SER) of soil, by increasing solubilities of organic pollutants and reducing the level of surfactant pollution and remediation expenses.     

温州近海海域海水及滩涂沉积物中PFOS和PFOA污染特征分析

为了解温州近海海域全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)的污染状况和特征,采用固相萃取/高效液相串联质谱检测法分析了采自乐清湾、瓯江口、西湾、飞云江口及洞头半屏岛的近海海水和滩涂沉积物中PFOS和PFOA污染水平。结果显示,温州近海海水普遍存在PFOS和PFOA污染,其中,PFOS的浓度范围为<1.0～31.36 ng/L,中位浓度为2.29 ng/L;PFOA的浓度范围为<1.0～23.66 ng/L,中位浓度为5.29 ng/L。滩涂沉积物样品中PFOS和PFOA的浓度范围(干重)分别为(<1.0～11.91)×10-9(中位浓度为3.60×10-9)和(1.84～34.01)×10-9(中位浓度为6.83×10-9)。温州近海海水中PFOS和PFOA的污染水平明显高于香港沿岸、中国南海海水、韩国沿岸海水和近海珠江三角洲,与大连湾的海水相当,海岸滩涂沉积物中的PFOS和PFOA浓度远高于珠江和黄浦江沉积物中的浓度。     

全氟辛烷磺酸(PFOS)对斑马鱼卵黄蛋白原mRNA水平的影响

为了研究环境低剂量全氟辛烷磺酸（perfluorooctane sulfonate,PFOS）对水生生物的内分泌干扰效应和可能的作用机制,测定了PFOS对斑马鱼（Brachydanio rerio）肝脏中卵黄蛋白原（vitellogenin,VTG）mRNA水平的影响.将斑马鱼暴露于4个PFOS的环境低剂量浓度组（0.1、1、10、100μg.L-1）中进行21d毒性试验,收集肝脏样品,提取RNA,采用荧光定量PCR（qRT-PCR）分别检测VTG1和VTG3的mRNA水平.结果表明：①PFOS暴露引起雄性斑马鱼肝脏VTG1和VTG3 mRNA水平升高,VTG1 mRNA水平升高与剂量呈正相关,在100μg.L-1暴露浓度处与对照组呈现显著性差异;VTG3的mRNA水平变化与剂量呈倒U型曲线,呈现典型的毒物刺激荷尔蒙效应,在10和100μg.L-1暴露浓度处与对照组呈现显著性差异;②PFOS暴露引起雌性斑马鱼肝脏中VTG1 mRNA水平升高,在10μg.L-1暴露浓度处与对照组呈现显著性差异,但在高浓度（10和100μg.L-1）处试验结果误差较大;VTG3 mRNA水平只在10μg.L-1暴露浓度处升高,但相比于对照组均没有显著性差异.试验结果表明PFOS暴露对斑马鱼的内分泌干扰作用明显,其毒性作用机制可能是类雌激素效应,而肝脏中VTG1和VTG3mRNA水平可能作为PFOS内分泌干扰效应评价的敏感生物标志物,但VTG1和VTG3 mRNA水平的响应曲线呈现基因亚型和性别差异.     

膨润土对复合污染中表面活性剂的吸附及机理

选取阳离子表面活性剂氯化十六烷基吡啶(CPC)、阴离子表面活性剂十二烷基苯磺酸钠(SDBS)及非离子表面活性剂Triton X-100(TX-100)为代表,研究了其在膨润土上的吸附行为,探讨了膨润土阳离子交换容量(CEC)、温度、盐度对CPC吸附的影响.结果表明,Na基膨润土对CPC的吸附性能最好,对SDBS基本无吸附,对TX-100的吸附介于两者之间.Na基膨润土对CPC的吸附是阳离子交换和疏水键缔合共同作用的结果,对TX-100的吸附主要是通过其与膨润土硅氧表面间的氢键作用,同时通过疏水键作用形成吸附双分子层;SDBS在Ca基膨润土上的吸附损失量先增大后减小,在1.5倍临界胶束浓度 (CMC)时达到极大值,主要机理是SDBS与膨润土中的Ca²⁺产生沉淀作用,而胶束具有再溶解沉淀的作用.膨润土对CPC的吸附量随着温度升高而降低,随着CEC的增大而增大,一定浓度NaCl的加入有利于其在膨润土上的吸附.     

沈阳市降雪中PFOS和PFOA污染现状调查

通过调查降雪中PFOS和PFOA的浓度,阐明了沈阳市大气中PFOS和PFOA的污染状况和污染规律.2006-02-06采集沈阳市区和郊区共计36个采样点的降雪样品,2006-02-25在其中5个采样点再次采集降雪样品.固相萃取融雪水中的PFOS和PFOA,利用LC-MS-SIM法测定样品中PFOS和PFOA浓度.全部样品中均检出PFOS和PFOA.2006-02-06降雪中PFOS和PFOA的浓度几何平均值分别为2.0 ng·L^-1（范围：0.4～46.2 ng·L^-1）和3.6 ng·L^-1（范围：1.6～22.4 ng·L^-1）,95%置信区间分别为1.5～2.8 ng·L^-1和3.1～4.2 ng·L^-1.PFOS和PFOA的最高浓度同时出现在郊区采样点朱尔屯,市中心区2种物质的浓度呈显著正相关.2006-02-25的5个采样点降雪中PFOS和PFOA的浓度几何平均值均为2.2 ng·L^-1.2次降雪中PFOS浓度差异不显著,2006-02-25降雪中PFOA浓度高于2006-02-06.结果表明,沈阳市区和郊区降雪中广泛存在PFOS和PFOA污染,局部区域可能存在共同的PFOS和PFOA污染来源;沈阳地区有较稳定的PFOS来源持续向大气中输送该类物质;PFOS和PFOA的环境行为可能不同.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Fe3O4纳米磁性微粒对全氟辛烷磺酸盐的吸附

采用共沉淀法合成Fe3O4纳米磁性颗粒,用透射电子显微镜(TEM)、X射线衍射仪(XRD)以及振动样品磁强计(VSM)对Fe3O4纳米磁性颗粒的粒径、形貌和磁性进行表征并研究Fe3O4纳米磁性微粒对全氟辛磺酸盐的吸附。结果表明:在PFOS初始浓度4 mg/L,pH为3,反应时间24 h,Fe3O4纳米磁性微粒投加量1.25 g/L,对全氟辛磺酸盐去除率达到90%。Fe3O4纳米磁性微粒对PFOS的吸附符合Freundlich吸附方程。     

厌氧-好氧接触氧化处理汽车脱脂废水研究

采用厌氧UASB-好氧接触氧化工艺对汽车脱脂废水进行连续处理实验研究。结果表明,在脱脂废水进水COD浓度为6 000 mg/L,厌氧水力停留时间为3.4 d,好氧水力停留时间为2.5 d条件下,COD总去除率平均为93%,厌氧段平均值为38%。厌氧段可以提高出水的可生化性,厌氧-好氧接触氧化工艺效果要明显优于好氧工艺。