雌激素在地下环境中的归宿及其生态调控

综述了环境中典型的结合态与游离态类固醇雌激素的来源、危害以及环境归趋,探讨了其在地下环境（土壤和浅层地下水系统）中的吸附、微生物降解等迁移转化过程及其影响因素,总结了常见的环境雌激素处理方法与危害控制措施.最后,针对目前环境中类固醇雌激素在包气带与浅层地下水中的穿透过程及其生态效应研究工作的基础上,对未来相关方面的研究进行了展望.     

三种微生物对铀的吸附行为研究

开展了酵母菌(真菌)、枯草芽孢杆菌(细菌)、小球藻(藻类)对水体中铀(Ⅵ)的吸附性能及机理研究.结果表明:3种微生物对铀都具有较好的吸附效果.酵母菌,小球藻,枯草芽孢杆菌对铀的最佳吸附率分别为97.19%、97.13%、98.03%;且最大吸附量分别达到341.2、356.5、512.5mgU/g(DW).3种微生物对铀的吸附过程和机理有所不同,酵母菌和小球藻符合Langmuir模型,枯草芽孢杆菌更适合Freundlich模型,吸附至12h,酵母菌表面逐渐出现铀和磷的片状结晶及含铀沉积物堆积,小球藻和枯草芽孢杆菌与铀(50mgU/L)作用后细胞出现明显变形,菌体表面未出现铀的结晶物.     

Nexus between polymer support and metal oxide nanoparticles in hybrid nanosorbent materials (HNMs) for sorption/desorption of target ligands

Metal oxide nanoparticles like hydrated ferric oxide (HFO) or hydrated zirconium oxide (HZrO) are excellent sorbents for environmentally significant ligands like phosphate, arsenic, or fluoride, present at trace concentrations. Since the sorption capacity is surface dependent for HFO and HZrO, nanoscale sizes offer significant enhancement in performance. However, due to their miniscule sizes, low attrition resistance, and poor durability they are unable to be used in typical plug-flow column setups. Meanwhile ion exchange resins, which have no specific affinity toward anionic ligands, are durable and chemically stable. By impregnating metal oxide nanoparticles inside a polymer support, with or without functional groups, a hybrid nanosorbent material (HNM) can be prepared. A HNM is durable, mechanically strong, and chemically stable. The functional groups of the polymeric support will affect the overall removal efficiency of the ligands exerted by the Donnan Membrane Effect. For example, the removal of arsenic by HFO or the removal of fluoride by HZrO is enhanced by using anion exchange resins. The HNM can be precisely tuned to remove one type of contaminant over another type. Also, the physical morphology of the support material, spherical bead versus ion exchange fiber, has a significant effect on kinetics of sorption and desorption. HNMs also possess dual sorption sites and are capable of removing multiple contaminants, namely, arsenate and perchlorate, concurrently.     

有机质官能团及微孔特性对疏水性有机污染物吸附的影响机制

作为重要的地质吸附剂,土壤/沉积物中的有机质是环境中疏水性有机污染物主要的汇.由于有机质的结构异质性,疏水性有机污染物一旦进入其中,会被吸附在不同的位点上,反应活性和生态风险进而会发生变化.对疏水性有机污染物在有机质上的吸附进行研究有助于了解其在环境中的分布,传输及生物有效性.本文就疏水性有机污染物在土壤/沉积物中的有机质上吸附的国内外研究进展进行了综述,讨论了重要有机质组分(腐殖质和碳黑)的结构和吸附作用差异性,重点分析了有机质的微孔特性和官能团对吸附的影响机制.     

畜禽养殖排放的雌激素对周边水体环境的影响

环境雌激素是一大类化学物质,它们能够干扰生物体内激素的合成、分泌、转运、活性等,或与生物体内激素结构相似而发挥激素作用,对生物体的生长、繁殖及行为产生不利影响。环境雌激素包括天然雌激素及人工合成类雌激素。随着国内畜禽养殖的规模与数量的不断扩大,养殖场成为了一个很大的环境雌激素的产生源,其环境风险应得到相应的重视。目前对畜禽养殖过程中环境雌激素的产生量以及雌激素进入环境后的迁移转化行为已有很多的研究,包括野外的调查与实验室内机理研究。畜禽养殖过程产生的大量雌激素进入环境后能够被土壤吸附及微生物降解。室内的静态平衡吸附实验、土柱迁移试验及降解研究均表明雌激素进入环境后绝大部分迅速被吸附到土壤颗粒或悬浮胶体、沉积物颗粒上,同时发生转化与生物降解,由此推断其对周边环境中的雌激素贡献很小。然而,野外调查结果却表明实际情况下雌激素的迁移性高于理论期望值。因此,畜禽养殖对周边环境中雌激素的贡献量的大小尚未明确。本论文综述了畜禽养殖过程中环境雌激素的排放情况,结合国内外的调查研究,阐述了畜禽养殖产生的环境雌激素在土壤及水体中的迁移与降解行为,探讨了影响准确评估畜禽养殖排泄物对周边水体中雌激素贡献大小的因子,并提出了今后应开展原位吸附与迁移的实验,重点考虑天然有机质及抗生素等共存物质对雌激素环境行为的影响,建立综合模型来估算不同时期养殖场对周围水环境雌激素的贡献量的建议。     

Characterization of interaction between different adsorbents and copper by simulation experiments using sediment-extracted organic matter from Taihu Lake,China

The complex capacity of different types of organic matters （OMs） for Cu was quantitatively studied by simulation experiments using different adsorbents prepared from the sediment in Taihu Lake. The free Cu was measured with ion selective electrode （ISE） and complex capacity was calculated using a conditional formation constant model. The result indicated that the complex capacity was 0.048 mmol·g-1, 0.009 and 0.005 mmol.g-1for raw sediment, sediment without DOM, sediment without insoluble organic matters but with DOM and sediment without OM. Insoluble organic matter played a major role in the sorption of Cu in sediment and it can adsorb most Cu from water column. In the solution, Cu mainly existed as a complex with DOM and the DOM-Cu complexation capacity was 327.87 mg. g-1. The change of TOC and pH indicated ion-exchange in the interaction between free Cu and DOM. When the Cu concentration in the experiment reached the complex capacity of DOM, precipitation was the major mechanism to remove Cu from water phase, which was observed from UV absorbance change of DOM, that is, its aromaticity increased while molecular weight decreased. The desorption result indi- cated that DOM was more capable of desorbing Cu from adsorbents without OM than adsorbent with OM. The desorbed quantity with DOM was 1.65, 1.78 and 2.25 times higher than that with water for adsorbents without OM, raw adsorbents （sediment） and adsorbents without DOM.     

二氧化钛颗粒的制备及其脱硫吸附性能

采用溶胶-凝胶法(Sol-gel)在不同烧结温度(340℃,440℃,540℃,640℃)下制备了4种多孔TiO₂颗粒,X射线衍射法(XRD)测得4种样品的晶相均为锐钛矿型.低温77K氮气吸附法计算4种样品的比表面积为79～124m²/g,平均孔径56.8～254.8 A.电子扫描电镜分析了样品的表面结构为多孔高孔隙率结构在固定床中对4种样品进行动态脱硫试验,试验结果表明烧结温度在540℃时制备的样品品质较好,每g TiO₂颗粒可吸附38.9mg的SO₂.以SG 540样品为例,研究了固定床中吸附温度,气相中SO2的浓度以及气体流速对其脱硫吸附性能的影响.与活性炭、沸石物理吸附剂比较,TiO₂颗粒具有较高的脱硫吸附能力.FTIR红外光谱分析法,结合加热脱附试验的结果,得知TiO₂颗粒吸附剂脱硫的机理主要是物理吸附.     

涕灭威在水体悬浮颗粒物上的吸附行为

通过静态吸附实验,探讨了氨基甲酸酯类农药涕灭威在水体悬浮颗粒物上的吸附规律.实验表明,25±1℃条件下,涕灭威在低浓度(0.2～1.5mg/L)时,在颗粒物上的吸附符合Langmuir等温吸附;在2.0～15mg/L用Freundlich吸附等温线描述更合理;在20～2000mg/L,涕灭威的吸附既可以用线性等温方程式也可以用Fre-undlich等温方程式来描述.并研究了阴离子表面活性剂SDBS和非离子表面活性剂TWEEN60存在下涕灭威的吸附等温线,以及悬浮颗粒物浓度、腐殖酸、pH、盐度及微生物对涕灭威在颗粒物上吸附行为的影响.     

海藻酸钠/锆@钙水凝胶的制备及其对磷的吸附研究

利用简便的方法制备了一种新型的海藻酸钠/锆@钙(SA/Zr@Ca)水凝胶材料,采用SEM、XRD对该材料进行了表征,并通过拟合吸附等温模型及吸附动力学模型,结合XPS和Zeta电位分析,研究了该材料对磷酸盐吸附的性能和机理.结果表明,该材料为非晶态的无定型材料.在溶液初始pH为2～7时,SA/Zr@Ca对磷酸盐(以PO...     

Determination and QSPR analysis of log Kow and log Koc for fluorine containing benzene derivatives

Octanol‐water partition coefficients (Kow) and soil organic carbon sorption coefficients (Koc) were determined for 14 fluorinated benzene derivatives. Quantitative structure‐property relationships were developed using molecular connectivity indices and quantum chemical parameters to analyze the most significant factors influencing these physico‐chemical properties of the compounds. The substitution by F in benzene derivatives has greater influence on Koc than on Kow.