FeCl3改性MOFs在低温下对Hg0的吸附性能

为提高吸附剂对Hg0（零价汞）的吸附效率,利用MOFs（金属有机框架）材料发达的孔隙结构和高比表面积（1 997.010 0 m2/g）,采用FeCl₃溶液浸渍改性,制备了吸附剂FeCl₃@MIL-101（Cr）用于脱除Hg0.在小型固定床反应器上考察了浸渍浓度、反应温度、氧含量等对Hg0去除的影响.结果表明:FeCl₃@MIL-101（Cr）在进口ρ（Hg0）为2×10-3 mg/L,c（FeCl₃）为0.2 mol/L,反应温度60℃,气体流速400 mL/min,φ（O₂）为1%的条件下,吸附穿透时间长达62 h,相应的吸附容量为14.27 mg/g.在此基础上,进一步利用BET（比表面积测试）、SEM（扫描电镜）-EDX（能量色散X射线光谱）、XRD（X射线衍射）、XPS（X射线光电子能谱）等常用表征手段研究了改性前后吸附剂的物理化学特性,证明了吸附剂FeCl₃@MIL-101（Cr）吸附零价汞是物理吸附与化学吸附共同作用的结果,含氯官能团在吸附Hg0过程中也发挥了相当大的作用,并且氧气可促进其吸附效果.最后,分析了其吸附机理.研究显示,该种吸附剂在低温条件下具有较为优良的脱汞性能,应用前景良好.      

天津市春季道路降尘PM2.5中重金属污染特征及健康风险评价

为研究天津市春季道路降尘PM_2.5中重金属污染特征及健康风险,于2015年3月22日-5月23日用降尘缸采集天津市主干道、次干道、支路、快速路道路两侧道路降尘样品,利用再悬浮系统将道路降尘中PM_2.5悬浮至滤膜上,并用电感耦合等离子体质谱仪（ICP-MS）测定了PM_2.5中7种重金属（Ni、Pb、Cd、As、Mn、Cu和Zn）的质量分数.结果表明:道路降尘PM_2.5中Ni、Pb、Cd、As、Mn、Cu和Zn质量分数平均值分别为37.05、82.50、1.73、25.65、380.18、201.08和736.43 mg/kg;I_geo（地累积指数）显示,Cd属于强污染,Zn和Cu属于中到强污染,Pb属于中度污染,As属于轻度污染,Ni和Mn属于无污染;健康风险评价显示,手-口摄入是道路降尘PM_2.5中重金属进入人体的主要途径,儿童的暴露剂量和非致癌风险均高于成人,总非致癌风险次序为As > Pb > Mn > Cu > Zn > Cd > Ni,其中儿童手-口途径As的暴露风险商（HQ_ing）及非致癌总风险（HI）均为1.23,大于限值（1）,对儿童存在非致癌风险;其他重金属非致癌总风险均低于限值,对人体无非致癌风险;道路降尘PM_2.5中Ni、As和Cd通过呼吸途径对人体均无致癌风险.      

温度对FBAR反应器的运行特性及古菌微生物群落影响

为探讨固定床厌氧反应器（FBAR）在不同温度下的运行特性及微生物群落变化,比较了高温（50℃）、中温（35℃）、低温（4℃）3个温度阶段反应器产甲烷特性及古菌群落变化.结果表明;绝对产气量由大至小依次为高（50℃）、中（35℃）、低温（4℃）,单位负荷产气量依次为中温（2.84L/OLR）,低温（2.5L/OLR）,高温（1.8L/OLR）;甲烷含量依次为低温（74.5%）、中温（63.5%）,高温（57.3%）,不同温度阶段对挥发性有机酸含量变化有一定的影响.克隆文库分析表明：不同温度条件下固定床厌氧反应器内部微生物群落的丰富性存在很大的差异.定量PCR分析表明：甲烷鬃毛菌是中温和高温反应器内的优势菌,低温4℃炭纤维载体和污泥中的优势菌都是甲烷微菌.从能耗、经济效益角度分析低温条件更适合沼气发酵,而主要是以嗜氢产甲烷菌代谢途径为主.     

于桥水库沉积物-水界面氮磷剖面特征及交换通量

于桥水库是天津市重要的饮用水源地,但近年来呈现富营养化加重趋势,而其内源负荷及污染分布特征尚不清楚.本研究利用Peeper(pore water equilibrium)技术获取沉积物-水界面氮磷剖面特征,分析于桥水库间隙水氮磷分布的空间差异;采集沉积物无扰动柱样分析沉积物中易释放态氮及磷的赋存特征,并利用原柱样静态培养法对其水土界面氮磷交换速率进行估算.结果表明:(1)沉积物中活性磷、氨氮、硝态氮和亚硝态氮的含量分别为0.5~6.5、0.5~10.9、2.2~16.2和0.05~0.6 mg·kg~(-1),在垂直方向随深度增加营养盐含量降低,而在空间分布上差异显著.(2)上覆水中PO_4~(3-)-P和NH_4~+-N质量浓度较低,间隙水中PO_4~(3-)-P和NH_4~+-N质量浓度远大于上覆水,表明于桥水库间隙水具有向上覆水体扩散营养盐的潜力.在垂直方向上间隙水中PO_4~(3-)-P和NH_4~+-N具有在0~5 cm快速增加,之后表现出逐渐降低的趋势.(3)静态释放结果表明,PO_4~(3-)-P和NH_4~+-N从沉积物间隙水扩散至上覆水中,其释放通量分别为1.1~13.3 mg·(m~2·d)~(-1)和20.6~250.5 mg·(m~2·d)~(-1);NO-3-N交换通量在-20.4~33.4 mg·(m~2·d)~(-1)之间,NO_2~--N交换通量在-7.4~0.4 mg·(m~2·d)~(-1)之间.PO_4~(3-)-P和NH_4~+-N为于桥水库主要的沉积物内源向上覆水释放营养盐,总体释放速率在空间上呈现南高北低、淋河口和水坝前较高的释放特征.与类似研究比较可知,于桥水库沉积物-水界面通量相对较高,表明沉积物是于桥水库上覆水营养盐的重要来源.     

桑沟湾溶解态铁的分布、季节变化及影响因素

采用催化动力学分光光度法对2011年4月、8月、10月和2012年1月桑沟湾溶解态铁（dissolved iron,DFe）的含量进行了测定。结果表明,桑沟湾4个季节DFe的平均值分别为3.8 ±0.7 nmol/L、3.3 ±1.8 nmol/L、2.6 ±1.0 nmol/L、1.8 ±0.6 nmol/L,存在明显的季节变化（t-test,p < 0.05,n=19）。桑沟湾DFe的平面分布主要呈现出河口和近岸浓度较高,随离岸距离的增加浓度逐渐降低的变化趋势。通过对桑沟湾周边河流、地下水DFe含量的分析及箱式模型的计算,结果表明桑沟湾海域DFe的主要来源包括河流、地下水的输入和大气沉降等;而其主要的汇为向黄海的输出以及养殖生物的吸收利用。DFe在桑沟湾的存留时间与大洋相比明显降低,可能与特殊的水文环境与养殖生物的吸收利用有关。     

典型近岸工程海域重金属Pb多相介质富集特性研究

以曹妃甸近岸工程海域的悬浮物及重金属污染物Pb为主要研究对象,采用趋势分析和多元统计相关分析方法,研究分析了6 a间悬浮物（水体中的悬浮物含量）、水相中的Pb含量和沉积相中的Pb含量的变化趋势及其相关关系,揭示重金属Pb在人为扰动因素影响下的演变规律与富集特性。趋势分析结果表明:随着悬浮物的增加与减少,研究区域水相中的Pb含量呈现出基本相同的增减规律,而沉积相中的Pb含量则呈现出相反的趋势。简单相关分析结果表明:悬浮物与水相之间呈较弱的正相关,悬浮物和沉积相之间呈较强的负相关,水相和沉积相之间呈较弱的负相关。偏相关与简单相关结果对比可知:水相和沉积相的变化最大,表明水相和沉积相受悬浮物影响较大;沉积相对悬浮物与水相之间的相关性影响弱之;悬浮物与沉积相之间的相关性变化不大,表明水相对于两者的影响较小。通过研究对于掌握工程海域重金属Pb的各相变化趋势与富集特性,具有重要的研究价值和实际意义,为近岸海域环境管理与工程建设提供指导。     

Activity maintenance of the excised branches and a case study of NO2 exchange between the atmosphere and P. nigra branches

The efficient maintenance of the activity of excised branches is the powerful guarantee to accurately determine gas exchange flux between the detached branches of tall trees and the atmosphere. In this study, the net photosynthetic rate(NPR) of the excised branches and branches in situ were measured simultaneously by using two photosynthetic instruments to characterize the activity of the excised branches of Phyllostachys nigra. The ratio of normalized NPR of excised branches to NPR in situ was used to assess the photosynthetic activity of detached branches. Based on photosynthetic activity, an optimal hydroponics protocol for maintaining activity of excised P. nigra branches was presented:1/8 times the concentration of Gamborg B5 vitamin mixture with p H = 6. Under the best cultivation protocol, photosynthetic activity of excised P. nigra branches could be maintained more than 90% within 6 hr in the light intensity range of 200–2000 μmol/(m2·sec) and temperature range of 13.4–28.7°C. The nitrogen dioxide(NO2) flux differences between in situ and in vitro branches and the atmosphere were compared using double dynamic chambers.Based on the maintenance method of excised branches, the NO2 exchange flux between the excised P. nigra branches and the atmosphere(from-1.01 to-2.72 nmol/(m2·sec) was basically consistent with between the branches in situ and the atmosphere(from-1.12 to-3.16 nmol/(m2 sec)) within 6 hr. Therefore, this study provided a feasible protocol for in vitro measurement of gas exchange between tall trees and the atmosphere for a period of time.     

Morphology, composition, and sources of individual aerosol particles at a regional background site of the YRD, China

Aerosol samples were collected at Lin'an, a background site of Yangtze River Delta(YRD).Morphology, size, composition, and mixing state of individual aerosol particles were characterized by transmission electron microscopy(TEM) coupled with energy dispersive X-ray spectroscopy(EDS), and the soluble ions of PM_(1.0) were studied by aerosol mass spectrometer(AMS). The daily average AMS mass concentrations of sulfate, nitrate, and ammonium were about 5.8, 8.6, and 5.6 μg/m~3, respectively. Individual aerosol particles were classified into seven types: S-rich, K-rich, organic matter(OM), soot, fly ash, metal, and mineral. S-rich particles were dominant in all size bins, and 51%(by number) of S-rich particles were internally mixed with other particles. The fraction of organic coating particles was 13.7% in morning, 25.2% in afternoon, and 11% in evening, suggesting that the strong photochemical process during afternoon produced more secondary organic aerosols(SOA) on the surface of inorganic particles. Fly ash and metal particles were abundant during the day, suggesting the influence of emissions from coal-fired power plants and steel plants. The results indicate that the intense industrial emissions in the YRD significantly transported to the background areas. PM_(2.5) concentration may be lower in background air than in urban air but complex mixing state of aerosol particles indicates that the long-range transported particles substantially influenced the background air quality.     

海泡石负载型纳米零价铁对水中Cu(Ⅱ)、Zn(Ⅱ)的去除研究

针对日益突出的水体重金属污染问题,采用液相还原法制备海泡石负载纳米零价铁(S-nZVI),并研究其对Cu(II)、Zn(II)的去除效果.同时,利用比表面积与孔径分析(BET)、透射电子显微镜(TEM)、X射线衍射(XRD)对制备出的材料进行表征,研究pH、S-nZVI投加量、重金属离子溶液初始浓度对去除率的影响,拟合S-nZVI材料去除Cu(II)、Zn(II)的动力学模型和吸附等温模型,并对反应后的S-nZVI进行回收及再生.结果表明,液相还原法可以成功制备出S-nZVI,且颗粒分布均匀.在60 min左右,S-nZVI对Cu(II)、Zn(II)的去除达到平衡.Cu(II)、Zn(II)的去除率随着pH值的升高而升高.当Cu(II)、Zn(II)溶液初始浓度为20 mg·L~(-1)时,最佳S-nZVI投加量分别为0.030、0.050 g,此时去除率分别为98.98%、98.97%.当Cu(II)浓度为90 mg·L~(-1)时,S-nZVI材料对Cu(II)的去除量最大,为127.57 mg·g~(-1);对Zn(II)来说,当浓度为110 mg·L~(-1)时去除量最大,为109.13 mg·g~(-1).去除过程符合准二级动力学模型和Langmuir吸附等温模型.S-nZVI可通过外加磁场进行回收,5次再生处理后其对Cu(II)、Zn(II)的去除率仍维持在96.84%、80.25%.实验结果显示,S-nZVI在废水除Cu(II)、Zn(II)领域具有很好的应用前景.     

Visible-light-driven photocatalytic inactivation of bacteriophage f2 by Cu-TiO2 nanofibers in the presence of humic acid

Pathogenic viruses in drinking water are great threats to public health. Visible-light-driven photocatalysis is a promising technology for virus inactivation. However, the existing photocatalytic antiviral research studies have mostly been carried out in single-component systems, neglecting the effect of natural organic matter, which exists widely in actual water bodies. In this paper, electrospun Cu-TiO₂ nanofibers were prepared as photocatalysts, and their photocatalytic antiviral performance in the presence of humic acid (HA) was comprehensively studied for the first time. The properties of the reaction mixture were measured during the reaction. In addition, the safety, reliability and stability of photocatalytic disinfection in the mixed system were evaluated. The results showed that the virus removal efficiency decreased with the increase of the HA concentration. The type of reaction solution, such as PBS buffer solution or water, did not affect the removal efficiency noticeably. Under acidic conditions, the electrostatic forces between photocatalysts and viruses were strengthened, leading to higher virus removal efficiency. As the reaction time went on, the pH value in the solution increased first and then tended to be stable, the conductivity remained stable, and the dissolved oxygen increased first and then decreased. The safety test showed that the concentration of Cu ions released into the solution was lower than specified by the international standards. No photoreactivation was observed, and the addition of HA significantly reduced the reutilization efficiency of the photocatalysts.