环境介质中铂族金属形态分析方法的研究进展

环境中铂族金属(PGMs)的赋存形态多样,形态分析对识别其生态风险具有十分重要的意义。本文综述了环境中3种主要铂族金属(铂、钯、铑)的形态分析方法,包括化学顺序提取、仪器联用技术及计算机模拟等,概述了这些方法的类型、特点及应用,同时阐述了它们存在的不足,并对未来发展方向进行了展望。化学顺序提取法普遍用于固相样品形态分析,当前研究中提出的提取条件和步骤多样,但不能很好地标准化;仪器联用技术在溶液元素形态分析上具有显著优势,毛细管电泳联用系统能够分离具有相同电泳能力的相似物质,但在分离能力和检出限方面不如液相色谱联用系统;计算机模拟则进一步拓展了形态分析的途径,能够实现复杂的形态计算。建议今后将多个方法进行结合,通过相互补充与完善,不断提高分析技术准确性。     

环境中人为来源的铂族元素及其迁移转化研究进展

铂族元素(PGEs)在汽车尾气催化转换器(VECs)、工业催化剂和制药学领域的广泛应用,致使PGEs尤其是铂(Pt)、钯(Pd)和铑(Rh)在某些区域已经成为新型环境污染物.由于环境样品中Pt/Pd、Pt/Rh与VECs中活性成分比例有较好的相关性,因此PGEs污染主要来源于应用了铂族金属的VECs.研究显示,过去的30年里,气溶胶、永生态系统(河水、雨水、地下水、海水、沉积物)、土壤、路尘和生物有机体等不同环境介质中PGEs浓度均显著增加.人们普遍认为铂族元素是惰性的,暴露于环境中的PGEs的健康风险很小,但PGEs毒性和生物可利用性的研究表明,在多种生物地球化学过程作用下,人为排放的PGEs易发生迁移,转化为毒性更大的形态,增加生物可利用性,通过食物链传递对人类产生潜在的健康风险.本文对不同环境介质中PGEs来源、分布及生物地球化学行为的最新成果进行了总结,认为PGEs人体健康风险标准制定、PGEs标准物质的研制、近海沉积物中PGEs的研究、PGEs对滩涂贝类的毒性、食物中PGEs的污染现状及人体健康风险评估等是今后PGEs研究的重要领域.     

海水反硝化细菌富集培养及性能研究

目的：建立一种海水反硝化细菌的富集培养方法,为海水反硝化微生物在实际应用中处理硝酸盐氮做基础工作。方法：选取污水处理厂缺氧池活性污泥,利用人工海水富集培养反硝化细菌。结果：经过25d,可以培养出反硝化速率为4.83mg/（gMLSS·h）、反硝化强度为110mg/（L·h）的海水反硝化细菌培养物。结论：该培养物可利用柠檬酸钠、葡萄糖、甲醇、乙醇、可溶性淀粉作为唯一碳源进行反硝化,其中以柠檬酸钠和乙醇作碳源时硝酸盐氮去除效果最佳,经过12h,去除率即可达到100%。pH在7～8范围内时,改变pH对去除率的影响不大,但当pH〈6时,去除率明显下降。温度在35℃时,去除效果最好,并且随着温度的降低,去除率也降低。     

二道坊河沉积物中重金属等元素富集特征的研究

以二道坊河沉积物为研究对象 ,采用相关与回归分析综合地研究了 1 4种元素在沉积物中的富集特征 .结果表明 :地球化学性质相近的元素 ,它们在沉积物中的相关系数大多达到了显著或极显著的水平 ;通过因子分析 ,求出了 4个主因子 ,它们代表沉积物中1 4种元素测定信息的 85% ,以第一、二主因子对应的特征向量为X、Y轴将 1 4个元素分成了 3类 ;建立了大部分元素与沉积物性质之间的多元回归方程 .     

绿色屋顶径流氮磷浓度分布及赋存形态

为了解绿色屋顶暴雨径流的氮磷浓度分布及赋存形态,在重庆大学构建了两种绿色屋顶,于2009年9月至2011年10月期间进行了绿色屋顶和对照屋面的暴雨径流水质监测。研究结果表明,绿色屋顶暴雨径流pH值在7.7左右,氨氮浓度满足地表水环境质量标准Ⅲ类标准;总氮、总磷、硝酸根的平均浓度分别为3.6—4.4 mg/L、0.17—0.28 mg/L和3.1—3.7 mg/L,均高于降雨雨水浓度;与对照屋面暴雨径流相比,同时期的绿色屋顶暴雨径流中总氮、氨氮和总磷浓度较低,而硝酸根、磷酸根浓度较高。绿色屋顶暴雨径流水质的季节差异明显,夏季污染物浓度较低,而春秋季节污染物浓度较高;总体上看,随绿色屋顶运行时间的延长,暴雨径流中总氮和硝酸根浓度逐渐降低,而总磷和磷酸盐浓度则呈现出一定的波动性。气象因素、降雨雨水水质与绿色屋顶暴雨径流水质的相关性分析表明,气温越高、前期干旱时间越长,越有利于绿色屋顶径流中氨氮浓度的降低;绿色屋顶径流中的总磷和氨氮主要来自降雨。研究结果为绿色屋顶的科学构建和城市暴雨径流管理提供了重要参考。     

潘大水库表层沉积物营养盐污染状况及赋存形态

潘家口-大黑汀水库(简称“潘大水库”)作为“引滦入津工程”的水源地,其水质状况直接关系到受水区饮水安全,是京津冀区域协同发展的重要影响因素.本研究基于2016年7月的调查,分析了沉积物中氮、磷和有机质的含量.结果表明: 潘大水库表层沉积物中总氮(TN)含量在1175.41～2415.67 mg·kg^-1(平均值为1648.71 mg·kg^-1),总磷(TP)含量在1773.25～3471.70 mg·kg^-1(平均值为2790.89 mg·kg^-1),有机质(OM)含量6.0%～25.3%(平均值为12.5%).在空间上,与上游的潘家口水库相比,处于下游的大黑汀水库TN含量与潘家口水库相近,TP含量略高.沉积物中氮主要以有机氮为主,磷主要以无机态的钙磷形态存在,有机质主要来源于外源性物质的输入.污染状况评价结果显示,潘大水库沉积物整体处于有机污染状态,且已达到严重污染的级别,可能会通过沉积物-水界面的营养交换对水环境改善产生潜在影响.     

南京栖霞山地区树木元素富集的初步研究

 本文用树木元素富集系数(T／S)来研究南京栖霞山铅锌多金属矿区树木—土壤系统中元素的富集特性。结果表明,树木对土壤中K、P二个元素的吸收基本与树种和开矿活动关系不大。黑松对Cr、Al,马尾松对Mn、Pb、Co、Ni、枫杨对P,刺槐对Mg、Na,Ti,栎对Zn、Ca、K、Fe、Sr、Ba、V,槐树对Cu均有最大的富集系数。黑松树龄对Co、K、Zn含量和Ca的富集系数有一定的影响。另外,Co—Ni、Sr—Ba的T／S曲线分别呈正相关,表现出这两组元素各自的地球化学共轭性。     

可食植物中砷赋存形态研究进展

砷是环境中普遍存在的一种化学元素,近年来日益严重的砷污染问题在世界范围内受到高度重视,我国目前已经成为世界卫生组织(WHO)列出的砷污染最严重的国家和地区之一.经口摄入是外界砷进入人体并累积产生生物毒性的主要途径.可食植物是人类饮食结构中不可缺少的部分,食品总砷含量并不能完全决定其毒性大小,砷的赋存形态与其生物毒性密切相关,无机砷已被确认为致癌物质.本文主要综述了不同种类可食植物中砷形态的分析方法,以及砷的主要赋存形态及其生物毒性.     

砷超富集植物中砷化学形态及其转化的EXAFS研究

通过同步辐射扩展X射线吸收精细结构(SR EXAFS)研究砷超富集植物大叶井口边草(Pteris nervosa)中砷的化学形态及其在植物体中的转化。结果表明,在大叶井口边草中砷主要与O配位,根部存在与谷胱苷肽(GSH)结合的砷,但是在羽叶中没有发现与GSH结合的砷,在NaAsO_2和Na_2HAsO_4处理中,植物根系的砷分别以As(Ⅲ)和As(Ⅴ)为主,但是在叶柄和羽叶中砷都以As(Ⅲ)的形态为主,植物根系吸收的As(Ⅴ)在向上转运的过程中具有向As(Ⅲ)转化的趋势,其转化过程主要发生在根部。实验证明,与GSH结合并不是大叶井口边草中砷解毒的主要机理,超富集植物可能具有与一般耐性植物不同的重金属解毒机制。     

砷超富集植物中砷化学形态及其转化的EXAFS研究

通过同步辐射扩展X射线吸收精细结构(SR EXAFS)研究砷超富集植物大叶井口边草(Pteris nervosa)中砷的化学形态及其在植物体中的转化. 结果表明, 在大叶井口边草中砷主要与O配位, 根部存在与谷胱苷肽(GSH)结合的砷, 但是在羽叶中没有发现与GSH结合的砷. 在NaAsO₂和Na₂HAsO₄处理中, 植物根系的砷分别以As(Ⅲ)和As(Ⅴ)为主, 但是在叶柄和羽叶中砷都以As(Ⅲ)的形态为主. 植物根系吸收的As(Ⅴ)在向上转运的过程中具有向As(Ⅲ)转化的趋势, 其转化过程主要发生在根部. 实验证明, 与GSH结合并不是大叶井口边草中砷解毒的主要机理, 超富集植物可能具有与一般耐性植物不同的重金属解毒机制.     

Survey of chemical speciation of trace elements using synchrotron radiation

Information concerning the chemical state of trace elements in biological systems generally has not been available. Such information for toxic elements and metals in metalloproteins could prove extremely valuable in the elucidation of their metabolism and other biological processes. The shielding of core electrons by binding electrons affect the energy required for creating inner-shell holes. Furthermore, the molecular binding and symmetry of the local environment of an atom affect the absorption spectrum in the neighborhood of the absorption edge. X-ray absorption near-edge structure (XANES) using synchrotron radiation excitation can be used to provide chemical speciation information for trace elements at concentrations as low as 10 ppm. The structure and position of the absorption curve in the region of an edge can yield vital data about the local structure and oxidation state of the trace element in question. Data are most easily interpreted by comparing the observed edge structure and position with those of model compounds of the element covering the entire range of possible oxidation states. Examples of such analyses will be reviewed.     

蒙药材多叶棘豆中五种微量元素的形态分析

本文采用水煎法对蒙药材多叶棘豆中微量元素进行提取,并分别用微孔滤膜分离技术、大孔吸附树脂柱分离法、萃取法等分离方法对水煎液中元素各形态进行分离。利用FAAS法测定了原药材以及水煎液各形态中Cu、Zn、Mn、Fe和Ca五种微量元素含量并进行了形态分析。分析结果表明,水煎液中五种元素的总提取率在41.7%～87.0%,残留率在9.1%～26.4%,可溶态百分率在16.6%～80.0%,可溶态中五种元素的有机态与无机态的比例为36.9%～250%;该测定方法对各元素的加标回收率在90.3%～113.7%。多叶棘豆水煎液可溶态中Zn、Mn、Fe、Ca元素是以亲水性有机结合形态为主,Cu元素以无机离子型为主,多种形态共存的复杂体系。     

Inorganic speciation of organotin(IV) cations in natural waters with particular reference to seawater

Abstract

This paper examines the inorganic complexing capacity of seawater, where chloride and sulfate ions are present in high concentration, towards mono- di- and tri-organotin(IV) cations which show a different trend of acidity, depending on cation charges, and a corresponding tendency to hydrolysis. By considering hydrolytic species and chloride and sulphate complex formation, a basic inorganic speciation model of organotins in synthetic seawater (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl^?, SO₄^2?) has been built up. The model has been extended to also consider interactions of organotins with carbonate and fluoride ions, which are other important components of seawater. Because of the strength of hydrolysis processes, the main complexes formed are in general mixed hydroxo-species. No species are formed by organotin cations and/or their hydroxo-species with fluoride owing to their very low concentration in fluoride, in comparison to the other components of seawater. In order to simplify calculations and to establish a cumulative inorganic binding capacity for seawater, we applied a chemical complexation model, according to which the major inorganic components of seawater are considered as a single salt BA.     

A survey of trace elements in pteridophytes

Concentration of 11 trace elements (Ca, Sc, Cr, Fe, Co, Zn, Rb, Cs, Ba, La, and Ce) in 96 pteridophytes (fern and fern ally species) was determined by instrumental neutron activation analysis to evaluate a concentration range for each element and also to find species characteristic in the uptake of trace elements. Asplenium trichomanes was found to accumulate Sc, Cr, and Co to the highest concentrations among 96 pteridophytes. The highest concentration of Ca and Zn was observed for Asplenium obscurum. The other Pteridophytes exhibited only one element whose concentration was the highest. A positive correlation was found between the concentrations of Fe and Sc, and also between the concentrations of Cr and Co. The remarkable accumulation of lanthanides (La and Ce) was observed mainly in diversifying genera (Polystichum and Dryopteris in Dryopteridaceae, Diplazium in Woodsiaceae, and Asplenium in Aspleniaceae).     

天门冬属九种药用植物的氨基酸和微量元素分析

百合科(Liliaceae)天门冬属(Asparagus (Tourn.)L.)植物具有悠久的药用历史,如天门冬(A.cochinchinesis (Lour) Merr.)早在汉代《神农本草经》中就被列为上品,具有滋阴、润燥、降火、止咳等功效。现代药理研究及临     

Essential trace elements in milk and blood serum of lactating donkeys as affected by lactation stage and dietary supplementation with trace elements

The aim of this trial was to study the concentration of zinc (Zn), iron (Fe), copper (Cu), manganese (Mn), selenium (Se), cobalt (Co) and iodine (I) in milk and blood serum of lactating donkeys, taking into account the effects of lactation stage and dietary supplementation with trace elements. During a 3-month period, 16 clinically healthy lactating donkeys (Martina-Franca-derived population), randomly divided into two homogeneous groups (control (CTL) and trace elements (TE)), were used to provide milk and blood samples at 2-week intervals. Donkeys in both groups had continuous access to meadow hay and were fed 2.5 kg of mixed feed daily, divided into two meals. The mixed feed for the TE group had the same ingredients as the CTL, but was supplemented with a commercial premix providing 163 mg Zn, 185 mg Fe, 36 mg Cu, 216 mg Mn, 0.67 mg Se, 2.78 mg Co and 3.20 mg I/kg mixed feed. The concentrations of Zn, Fe, Cu, Mn, Se, Co and I were measured in feeds, milk and blood serum by inductively coupled plasma-MS. Data were processed by ANOVA for repeated measures. The milk concentrations of all the investigated elements were not significantly affected by the dietary supplementation with TE. Serum concentrations of Zn, Fe, Cu Mn and Se were not affected by dietary treatment, but TE-supplemented donkeys showed significantly higher concentrations of serum Co (1.34 v. 0.69 μg/l) and I (24.42 v. 21.43 μg/l) than unsupplemented donkeys. The effect of lactation stage was significant for all the investigated elements in milk and blood serum, except for serum manganese. A clear negative trend during lactation was observed for milk Cu and Se concentrations (−38%), whereas that of Mn tended to increase. The serum Cu concentration was generally constant and that of Co tended to increase. If compared with data reported in the literature for human milk, donkey milk showed similarities for Zn, Mn, Co and I. Furthermore, this study indicated that, in the current experimental conditions, the mineral profile of donkey milk was not dependent on dietary TE supply.     

Content of trace elements and chromium speciation in Neem powder and tea infusions

Total concentrations of selected trace elements in Neem powder and in Neem tea were determined by inductively coupled plasma mass spectrometry (ICP-MS). The data revealed that despite high total concentrations of the potentially toxic elements Al and Ni in Neem powder, their amounts dissolved in Neem tea were low. Total concentrations of the other toxic elements Pb, As and Cd were also very low and do not represent a health hazard. In contrast, total concentrations of the essential elements Fe, Cu, Zn, Se Mo and Cr in Neem powder were high and also considerable in Neem tea. Consuming one cup of Neem tea (2 g per 200 mL of water) covers the recommended daily intakes for Cr and Se and represents an important source of Mo and Cu.Speciation analysis of Cr by high performance liquid chromatography (HPLC) coupled to ICP-MS with the use of enriched Cr isotopic tracers to follow species interconversions during the analytical procedure demonstrated that toxic Cr(VI) was not present either in Neem powder or in Neem tea. Its concentrations were below the limits of detection of the HPLC–ICP-MS procedure applied. The speciation analysis data confirmed that even Cr(VI) was added, it was rapidly reduced by the presence of antioxidants in Neem leaves. By the use of enriched Cr isotopic spike solutions it was also demonstrated that for obtaining reliable analytical data it is essential to apply the extraction procedures which prevent Cr species interconversions, or to correct for species transformation.     

Synthesis and spectral luminescent characteristics of the porphyrin complexes with the platinum group metals

The syntheses of complexes of natural and synthetic porphyrins with Pt, Pd, Rh, and Ru are reported. Their electronic absorption spectra, phosphorescence spectra, and lifetimes at room temperature both in the presence and in the absence of oxygen were studied. Variations in the nature of the central metal atom and in the substituents in pyrrol and phenyl rings allow the obtaining of metalloporphyrins phosphorescing at room temperature with various phosphorescence excitation and emission spectra.