地质样品中27项元素的粉末压片法x射线荧光光谱测定

本文报导了用x射线荧光光谱法—次粉末压片制样同时测定Na. Mg. Al. Si.P. S. K. Ca. Ti. V. Cr. Mn. Fe. Co. Ni. Cu. Zn. Rb. Sr. Y. Zr. Nb. Ba. Hf. Pb. Th. U等27项元素的快速分析方法。从理论上提出了新的基体效应学校正模式,首次引入了非荧光分析的物质(筒称NFAM)的新概念;并计算了理论α系数,使理论α系数在粉末压片法x射线荧光分析中获得了应用。本方法测定的对象可以是岩石,土壤和水系沉积物等地质样品。     

Element patterns in albatrosses and petrels: Influence of trophic position, foraging range, and prey type

We investigated the concentrations of 22 essential and non-essential elements among a community of Procellariiformes (and their prey) to identify the extent to which trophic position and foraging range governed element accumulation. Stable isotope analysis (SIA) was used to characterise trophic (δ¹⁵N) and spatial patterns (δ¹³C) among species. Few consistent patterns were observed in element distributions among species and diet appeared to be highly influential in some instances. Arsenic levels in seabird red blood cells correlated with δ¹⁵N and δ¹³C, demonstrating the importance of trophic position and foraging range for arsenic distribution. Arsenic concentrations in prey varied significantly across taxa, and in the strength of association with δ¹⁵N values (trophic level). In most instances, element patterns in Procellariiformes showed the clearest separation among species, indicating that a combination of prey selection and other complex species-specific characteristics (e.g. moult patterns) were generally more important determining factors than trophic level per se.     

Metals in biomass

Background, Aim and Scope

Metal ions generally share the ability/tendency of interacting with biological material by forming complexes, except possibly for the heavy alkali metals K, Rb and Cs. This is unrelated to the metals being either essential for sustaining life and its reproduction, apparently insignificant for biology, although perhaps undergoing bioconcentration or even being outright toxic, even at low admission levels. Yet, those different kinds of metal-biomass interactions should in some way depend on properties describing coordination chemistries of these very metals. Nevertheless, both ubiquitously essential metals and others sometimes used in biology should share these properties in numeric terms, since it can be anticipated that they will be distinguished from nonessential and/or toxic ones. These features noted above include bioconcentration, the involvement of metal ions such as Zn, Mg, Cu, Fe, etc. in biocatalysis as crucial components of metalloenzymes and the introduction of a certain set of essential metals common to (almost) all living beings (K, Mg, Mo, Mn, Fe, Cu and Zn), which occurred probably very early in biological evolution by ‘natural selection of the chemical elements’ (more exactly speaking, of the metallomes).

Materials and Methods

The approach is semiempirical and consists of three consecutive steps: 1) derivation of a regression equation which links complex stability data of different complexes containing the same metal ion to electrochemical data pertinent to the (replaced) ligands, thus describing properties of metal ions in complexes, 2) a graphical representation of the properties-two typical numbers c and x for each metal ion-in some map across the c/x-space, which additionally contains information about biological functions of these metal ions, i.e. whether they are essential in general (e.g. Mg, Mn, Zn) or, for a few organisms of various kinds (e.g. Cd, V), not essential (e.g. rare earth element ions) or even generally highly toxic (Hg, U). It is hypothesized that, if coordination properties of metals control their biological ‘feasibility’ in some way, this should show up in the mappings (one each for mono and bidentate-bonding ligands). 3) eventually, the regression equation produced in step 1) is inverted to calculate complex stabilities pertinent to biological systems: 3a) complex stabilities are mapped for ligands delivered to soil (-water) by green plants (e.g. citrate, malate) and fungi and, compared to their unlike selectivities and demands of metal use (photosynthesis taking place or not), 3b) the evolution of the metallome during late chemical evolution is reconstructed.

Results

These maps show some ‘window of essentiality’, a small, contrived range/area of c and x parameters in which essential metal ions gather almost exclusively. c and x thus control the possibility of a metal ion becoming essential by their influencing details of metal-substrate or (in cases of catalytic activities) metal-product interactions. Exceptions are not known to be involved in biocatalysis anyhow.

Discussion

Effects of ligands secreted, e.g. from tree roots or agaric mycelia to the soil on the respective modes (selectivities) of metal bioconcentration can be calculated by the equation giving complex stability constants, with obvious ramifications for a thorough, systematic interpretation of biomonitoring data. Eventually, alterations of C, N and P-compounds during chemical evolution are investigated — which converted CH₄ or CO₂, N₂ and other non-ligands to amino acids, etc., for example, with the latter behaving as efficient chelating ligands: Did they cause metal ions to accumulate in what was going to become biological matter and was there a selectivity, a positive bias in favour of nowessential metals (see above) in this process? Though there was no complete selectivity of this kind, neither a RNA world in which early ribozymes effected most of biocatalysis, nor a paleoatmosphere containing substantial amounts of CO could have paved the way to the present biochemistry and metallomes.

Conclusions

This way of reasoning provides a causal account for abundance distributions described earlier in the Biological System of Elements (BSE; Markert 1994, Fränzle &; Markert 2000, 2002). There is a pronounced change from chemical evolution, where but few transformations depended on metal ion catalysis to biology.

Recommendations and Perspectives

The application of this numerical approach can be used for modified, weighted evaluation of biomonitoring analytical data, likewise for the prediction of bioconcentration hazards due to a manifold of metal ions, including organometallic ones. This is relevant in ecotoxicology and biomonitoring. In combining apoproteins or peptides synthesized from scratch for purposes of catalysing certain transformations, the map and numerical approaches might prove useful for the selection of central ions which are even more efficient than the ‘natural’ ones, like for Co²⁺ in many Zn enzymes.

     

国际贸易中的环境要项

环境要素在流动性决定了国际间环境与贸易的紧密联系。随着世界快速的经济一体化，将环境要项纳入国际贸易的规范、条款已势在必行。文章分析了环境成本内在化和ＩＳＯ１４０００的实质，它们的内在联系及在国际贸易中的作用和影响，提出了将ＩＳＯ１４０００作为实施环境成本内在化的参照规则的合理、可行性。     

Effect of liming on the distribution of heavy metals in untreated industrial sewage sludge produced in Pakistan for the cultivation of <Emphasis Type="Italic">Sorghum bicolor</Emphasis> (L.)

The recycling of sewage sludge on agriculture land represents an alternative, advantageous, disposal of this waste material. The aim of the present study was to evaluate the feasibility of using industrial sewage sludge, produced in Pakistan, as a fertiliser. Agricultural soil amended with 25% (w/w) sewage sludge with or without lime treatment was used for growing a variety of sorghum (PARC-SS-1). The mobility of the heavy metals (HMs) (Cd, Cu, Cr, Ni, Pb and Zn) and metalloid (As) in the untreated industrial waste water sewage sludge (UIWS) samples were assessed by applying a modified BCR (Community Bureau of Reference) sequential extraction procedure. The single extraction procedure comprised of the application of mild extractant (CaCl₂) and water for the estimation of the proportion of easily soluble metal fractions. The precision and accuracy of BCR was evaluated by using a certified reference material of soil amended with sewage sludge BCR 483. The plant available metal contents, as extracted by the deionised water and 0.01 M CaCl₂ solution and exchangeable fraction of BCR sequential, decreased with lime application in the range of 10–44% for As, Cr, Ni, Pb and Zn, except in the cases of Cd and Cu, where their mobility was increased by 10% and 24%, respectively. Sludge amendment enhanced the dry weight yield of sorghum and the increase was more obvious after liming up to 25%. The uptake of HMs were lower in test samples (3.2–21.8%), except for Cu and Cd, which was higher (4%), while they were below the permissible limit of these metals. The present experiment demonstrates that liming was important in factors facilitating the growth of sorghum in sludge-amended soil.     

天津市颗粒物中元素化学特征及来源

2006年的8月—12月采集天津市PM2.5和PM10样品,分析了Na、Al等17种元素质量浓度及月变化特征,PM2.5中元素平均质量浓度为17.2μg/m3,占PM2.5的10.3%。微量元素Zn、Pb在PM10和PM2.5中含量较高,Cr、V、Ni、As等则在细粒子中有明显分布。用富集因子法分析发现,PM2.5中元素富集程度高于PM10。地壳元素除Ca外,均无明显富集,微量元素则呈现不同程度的富集,以Cd富集最为明显。颗粒物分析表明,土壤尘、燃煤、机动车尾气及化工行业是PM2.5中无机元素的主要来源。     

抚顺市PM10中元素分布特征及来源分析

为了确定抚顺市PM10中元素的浓度特征及其来源,于2006—2007年的采暖季、风沙季和非采暖季在抚顺市的6个采样点采集PM10样品,并用等离子体原子发射光谱法(ICP-AES)测定样品中Ti、Al、Mn、Mg、Ca、Na、K、Cu、Zn、As、Pb、Cr、Ni、Co、Cd、Fe、V等17种元素的含量。结果表明,Al、Mg、Ca、Na、K、Mn、Fe等地壳元素在17种元素中占有较大比重,全年平均达到97.0%。富集因子分析结果表明,Cu、Zn、Pb、Cr、Co、Cd等元素在各季和各采样点明显受到人为活动影响,是典型的污染元素。主因子分析结果显示,土壤风沙尘、建筑尘、燃煤尘、道路扬尘、机动车尾气排放、金属冶炼、锰、铜、钛工业源是抚顺市PM10中元素的主要来源。     

抚顺市大气颗粒物主要排放源的成分谱研究

抚顺市的5种大气颗粒物主要排放源中土壤风沙尘的特征元素为K,钢铁尘的特征元素为Fe,建筑水泥尘的特征元素为Ca,煤烟尘的特征元素为Ti。土壤风沙尘和扬尘中含量最高的元素为Al,煤烟尘中含量最高的元素为EC,钢铁尘中含量最高的元素为Fe,建筑水泥尘中含量最高的元素为Ca。     

Content, distribution and fate of 33 elements in sediments of rivers receiving wastewater in Hanoi, Vietnam

Untreated industrial and domestic wastewater from Hanoi city is discharged into rivers that supply water for various agricultural and aqua-cultural food production systems. The aim of this study was to assess the content, distribution and fate of 33 elements in the sediment and pore water of the main wastewater receiving rivers. The sediment was polluted with potentially toxic elements (PTEs) with maximum concentrations of 73 As, 427 Cd, 281 Cr, 240 Cu, 218 Ni, 363 Pb, 12.5 Sb and 1240 Zn mg kg(-1) d.w. Observed distribution coefficients (log(10) K(d,obs)) were calculated as the ratio between sediment (mg kg(-1) d.w.) and pore water (mg L(-1)) concentrations. Maxima log(10) K(d,obs) were >4.26 Cd, >6.60 Cu, 4.78 Ni, 7.01 Pb and 6.62 Zn. The high values show a strong PTE retention and indicate the importance of both sorption and precipitation as retention mechanisms. Sulphide precipitation was a likely mechanism due to highly reduced conditions.     

榆树市土壤元素地球化学特征及环境质量评价

为探讨榆树市土壤中各种元素的地球化学特征,利用GPS野外定点采取榆树市表层及深层土壤样品,采用XRF-X荧光光谱法测定土壤元素的组成及含量,运用SPSS和EXCELL2003软件对榆树市土壤元素地球化学特征进行分析。结果表明:研究区土壤必需的大量元素含量分布规律为Al>K>Ca>Mg>N>P;土壤必需的微量元素含量具有Fe>Mn>Zn>B>Cu>Mo的特征;土壤有益元素含量具有Si>Na>Ni>Co的区域特征;土壤健康元素含量具有F>I>Se的区域特征。运用内梅罗综合指数法计算土壤污染指数,查明营养元素丰缺状况。结果表明:研究区综合污染指数为0.66,总体上属于背景水平,符合一级土壤环境质量标准,适宜种植多种农作物。