利用PARAFAC及SOM研究不同来源及粒径胶体的三维荧光光谱特征

利用三维荧光光谱法(3D-EEM)结合平行因子分析(PARAFAC)和自组织神经网络分析(SOM),解析了不同来源水体中不同粒径胶体的荧光特性,同时与挑峰法进行比较,以期寻找一种更好的分析天然胶体来源、粒径、荧光特性间关系的方法.基于PARAFAC模型,研究区水体中不同粒径胶体共解析出2个类腐殖质荧光峰(C1和C3)及3个类蛋白荧光峰(C2、C4和C5).其中,300 k Da~1μm分级胶体荧光强度最高,C1、C2、C3组分的荧光强度随粒径增大而增强,C4、C5组分的荧光强度随粒径增大而减弱.不同来源胶体(生活污水:进水和出水;农业污水:大盈和天恩桥;天然水体:吴淞口)的荧光强度变化大致规律为:吴淞口进水大盈天恩桥出水.SOM分析结果与PARAFAC一致,且可视化程度更高,但EEM-SOM模型存在输入变量多、兼具挑峰法缺点的问题.而PARAFAC-SOM模型不仅兼具了前两者的优点,还具有输入变量少、运行时间短、可靠性高等优点.同时,该模型还成功应用于胶体其他理化参数的分析(Parameters-SOM模型),使得前期工作结果系统性更强、更直观.因此,PARAFAC-SOM模型是相对较好的分析天然胶体来源、粒径、荧光特性间关系的方法.     

基于非对称流场流分离技术的纳米银分离监测方法

以纳米银(AgNPs)作为典型的纳米颗粒物,利用非对称流场流分离技术构建纳米颗粒物的分离监测方法。制备了柠檬酸盐稳定的AgNPs分散液,采用透射电镜、紫外可见分光光度计、Zeta电位分析仪对AgNPs分散液进行了表征。结果表明,AgNPs半径多数小于10 nm,最大吸收波长为400 nm,Zeta电位为-42.56 m V。采用非对称流场流分离仪对AgNPs进行粒径分离,得到UV-Vis信号谱图,并收集得到半径小于10 nm、10~30 nm、30~50 nm、50~70 nm、70~100nm范围的AgNPs颗粒,结合电感耦合等离子体质谱仪测定每个粒径范围内AgNPs的质量浓度。结果表明,该方法重现性良好,AgNPs在半径小于10 nm的范围内达到了UV-Vis吸收峰值,响应信号最高为0.022 5~0.027 5 V,表明半径小于10 nm的AgNPs浓度较高。半径小于10 nm、10~30 nm、30~50 nm、50~70 nm、70~100 nm范围内AgNPs的质量浓度分别为(1 021.86±61.74)μg/L、(323.23±45.83)μg/L、(72.90±32.14)μg/L、(44.64±9.28)μg/L、(39.12±5.04)μg/L,回收率为43.96%±0.84%。     

水体冻结过程中荧光物质的迁移转化研究

本研究利用荧光区域积分法考察了在水体冻结过程中,溶解性有机物(DOM)组分中荧光物质的迁移转化.同时,利用XAD树脂,将DOM分为3个部分:疏水性有机酸(HPO-A)、过渡亲水性有机酸(TPI-A)和亲水性有机物(HPI).结果表明,在水体冻结过程中,HPO-A、TPI-A和HPI的DOC浓度在水相中逐渐增加,而在冰相中先减少后增加,并且这3种DOM组分在冰、水两相间的分配系数排序为:HPITPI-AHPOA.在水体冻结过程中,水相中HPO-A和HPI的总累计荧光强度(ΦT,n)值,以及冰相中3种DOM组分的总ΦT,n值随冻结时间的变化趋势均为先降低后升高.在水体冻结过程中,水相中3种DOM组分的类腐殖酸荧光峰发生蓝移.冻融作用导致HPO-A和HPI的荧光性降低.与HPO-A和HPI相比,TPI-A的荧光性受冻融作用的影响相对较小.此外,在4类荧光物质中,冻融作用对DOM组分中的类富里酸荧光物质和类腐殖酸荧光物质的影响较显著.     

植物中锌同位素的研究进展

锌同位素是示踪植物中锌地球化学的重要手段,详细了解植物中锌同位素的分馏过程是探究其生物地球化学的关键。本文对目前研究程度较高的超富集植物、普通植物的锌同位素分馏成果进行了系统的总结,发现二者锌同位素分馏趋势基本一致,即相比于培养液或土壤的同位素组成,植物根部相对富集锌的重同位素,而植物地上部(如茎、叶等组织器官)相对富集锌的轻同位素。对于能够引起植物发生锌同位素分馏的因素归纳如下:(1)植物根部相对富集锌的重同位素,是土壤中锌的形态、根部对锌的吸收方式、细胞表面吸附共同作用的结果;(2)植物木质部对锌的向上运输,会随着传输距离的增加而使地上部组织器官相对富集锌的轻同位素;(3)大气沉降也可能导致叶片富集锌的轻同位素。     

南京市城市污泥和工业污泥中典型矿质元素含量和形态分布研究

采用三态连续提取法研究南京市部分城市污泥和工业污泥中典型矿质元素的含量和形态分布,为污泥资源化的合理利用提供科学参考.结果表明,污泥总体呈高有机质、高氮磷、低K的相似性,但其理化性质如阳离子交换容量(CEC)、pH等有差异.污泥中不同矿质元素含量差异也较大,Fe的浓度最高,其次是Mg、Zn;且不同污泥间同一矿质元素含量的差异也较大.各元素的形态分布有一定差异,Cu主要分布在可氧化态,其酸溶/交换态和可还原态的百分率很低;Zn三态分布均较高;Mg、Mn主要分布在酸溶/交换态;Fe主要分布在残渣态.但三种提取形态百分率之和除Fe外均超过50%.研究同时表明,城市污泥和工业污泥中矿质元素形态分布无显著性差异.     

Isolation and Identification of Antialgal Compounds from the Leaves of Vallisneria spiralis L. by Activity-Guided Fractionation (5 pp)

Background, Aims and Scope

Vallisneria spiralis Linn., a common, submerged macrophyte, is widely available in quiet waters of lakes, ponds, marshes and streams in Southeast Asia. V. spiralis plays a significant role not only in decreasing eutrophication of water body for its productivity, but also in inhibiting the growth of blue-green algae? The aim of the paper involves the isolation and identification of allelochemicals from extracts of V. spiralis by activity-guided fractionation and column chromatography.

Methods

Leaves of V. spiralis was washed free of debris, air-dried and refluxed in 95% EtOH. The extract was isolated using column chromatography and fractionation with antialgal activity. Potential allelochemicals were analyzed by high-resolution gas chromatography-mass spectrometry (HRGC-MS).

Results

Two fractions with strong antialgal activity were isolated using column chromatography and activity-guided fractionation from the extract of V. spiralis. 2-Ethyl-3-methylmaleimide, dihydroactinidiolide and 4-oxo-β-Ionone were identified in the first fraction, and 3-hydroxy-5,6-epoxy-β-ionone, loliolide, 6-hydroxy-3-oxo-α-ionone and an unknown compound in the second fraction. They had strong inhibitory effects on Microcystis aeruginosa Kütz.

Discussion

2-Ethyl-3-methylmaleimide is a byproduct of photooxidation of chlorophyll, and five other compounds identified were derivatives of β-carotene. HRGC-MS and derivatization technology were used to identify and confirm their molecular structures. The formula of the unknown compound was C16H19NO4. Metabolites of plant pigments had strong inhibitory activities on growth of algae.

Conclusions

Six compounds had been identified in V. spiralis, among them, 2-ethyl-3-methylmaleimide was the main allelochemical, and derivatives of ionone were also potential allelochemicals.

Recommendations and Perspective

. The results of our research could help us to study further mechanisms of inhibitory effect on algae and develop new potential antialgal substances.     

水体溶解性有机物的化学分级表征:原理与方法

综述了水体溶解性有机物(DOM)的化学分级表征法即树脂吸附分级法(RA)的研究与进展,同时基于该方法存在的一些问题结合我国典型水质体系,从树脂的选择、净化、分级的定义、水样过柱流速、水样树脂体积比的确定等方面进行了研究探讨,给出了完整的实验参数和操作方法.     

Size characterization of the associations between carbon nanotubes and humic acids in aqueous media by asymmetrical flow field-flow fractionation combined with multi-angle light scattering

This work focuses on the influence of humic acids (HAs) on the fate of carbon nanotubes (CNTs) in aqueous media. This influence was demonstrated by mixing CNT powder with HAs in aqueous solution in varying concentrations. The aqueous media containing HAs and CNTs were size-characterized by asymmetrical flow field-flow fractionation (AsFlFFF) coupled with multi-angle light scattering (MALS). This coupling yielded information concerning the size distribution of single- and multi-walled CNTs (SWCNTs and MWCNTs) and HAs under different physico-chemical conditions that can occur in environmental water. HAs can disperse individual CNTs in aqueous media. However, the difference in the physical structure between SWCNTs and MWCNTs leads to significant differences in the quantity of HA that can adsorb onto the nanotube surface and in the stability of the CNT/HA complex. Compared with MWCNTs, SWCNTs suspended in HAs are less affected by changing ionic strength with respect to stability and the amount suspended.     

Zinc distribution in soils amended with different kinds of sewage sludge

Sewage sludge (SS) can be applied to cropland to supply and recycle nutrients and organic carbon. Potentially toxic elements in the sludge, however, are of environmental concern. This study evaluates the changes in chemical speciation of Zn in three representative pristine soils of the Pampas Region, Argentina, measured with sequential extraction over a one-year period. Pure SS or SS containing 30% (DM) of its own incineration ash (AS) was applied to the soils at an application rate of 150Mgha(-1). Zn was sequentially fractionated into exchangeable, organically bound, inorganic and residual fractions. The application of the SS and AS amendments significantly increased Zn concentration in all soil fractions at each sampling date. At day 1, Zn was mainly found in the residual fraction. A year after the application of the amendments, redistribution towards the inorganic fraction was observed (41-76% of total Zn content). Zn found in exchangeable and inorganic fractions depended on soil pH rather than on the type of soil used. A negative and significant correlation was found between exchangeable Zn concentrations and soil pH (r=0.94), and a positive and significant correlation between inorganic Zn concentrations and soil pH (r=0.92). For each amended soil and sampling date, no significant differences were observed between SS or AS treatments for the exchangeable fraction. Moreover, the use of AS did not cause significant differences in Zn concentration in the other soil fractions compared to SS. Based on these results, land spreading of AS may be similar to SS diaposal in terms of Zn mobility.     

Evaluation of mixture effects in a crude extract of compost using the CALUX bioassay and HPLC fractionation

Potential synergistic interactions between polycyclic aromatic hydrocarbons in a household sewage sludge compost extract were investigated using the Dioxin-Responsive Chemical-Activated Luciferase gene eXpression (DR-CALUX) assay and reverse-phase high-performance liquid chromatography (RP-HPLC) fractionation. The biological activity of the crude extract was measured in vitro using the CALUX assay. The CALUX activity of the extract was as potent as 360-pg CALUX-TEQ (2,3,7,8-TCDD equivalent value) per g sample, this was 70 times above the WHO-TEQ value which was derived from chemical analyses of dioxins/furans and dioxin-like PCBs of the mixture. The CALUX activity pattern of the crude extract and the retention times of 26 polycyclic aromatic compounds (PACs), as determined by RP-HPLC on an octadecylsilica column, suggested that the dioxin-like compounds with the log K(OW) (n-octanol/water partition coefficient) values corresponding to 6.0-7.0 contributed highly to the whole activity. The CALUX activity of the crude extract was three times the sum of the CALUX activities of the RP-HPLC separated fractions. Mixture effects were assessed by co-exposure of each HPLC fraction and 2,3,7,8-TCDD to the cells. The four concentration levels of added 2,3,7,8-TCDD corresponded to the TEQ value in the original compost sample. The experimental CALUX activity was higher than the predicted CALUX activity for some fractions. It was demonstrated that some compounds in the compost sample interacted synergistically with 2,3,7,8-TCDD in terms of dioxin-like activity. This finding points out the necessity for detailed investigation of synergistic effects in environmental samples.