宇宙环境中的某些化学问题

本文讨论了宇宙环境中的化学概况,特别是宇航环境化学和宇航适应问题。     

烷烃条件下CF2ClBr的紫外光解离机理研究

以气相色谱、红外光谱为主要分析手段,对气态ＣＦ２ＣｌＢｒ在ＣＲ２ＣｌＢｒ－Ｃ６Ｈ１２体系中的紫外光解离进行了研究,结果表明,在２５３．７ｎｍ紫外光照射下,该体系的主要光解产物为ＨＣＶＦ２Ｃｌ、ＨＢｒ以及Ｃ６Ｈ１２的聚合物,体系中ＣＦ２ＣｌＢｒ的解离近似精同缀反应,解离反应的速率常数为２．８７７×１０＾－６ｓ＾－１表观量子产率约０．１,基于此,对该光解反应的机理做了分析。     

氧化·热化学脱硫研究

热化学脱硫法因铵盐回收率低、产物不稳定,无法解决实用化问题。氧化热化学法应用超强脉冲电场产生高浓度、高能量的活性粒子,使SO₂在氧化过程中生成H₂SO₄,与NH3进行热化学反应,生成稳定的固体微粒（NH₄）₂SO₄,用电收尘器加以回收。脱除率、回收率可达90％左右,脱除1m³烟气中SO₂耗能为4Wh,实现了干法高效脱硫。一次投资大幅度减少,回收铵盐基本上抵消了药品费和电费。     

酸化模型及其发展趋势评述

本文将酸化模型分为指标评价模型、经验酸化模型和以湖泊－流域为基础的机理模型三大类。概述了几个典型的酸化模型的结构、对参数和过程的处理方法、存在的问题和应用范围并介绍了它们的一些具体应用。还以ＭＡＧＩＣ模型为例说明了酸化模型的发展及其趋势。作为模型的一个有机组成部分,本文还阐述了酸化模型的不确定性分析。     

重庆地下热水径流特征研究

重庆地下热水资源丰富,但对其径流特征缺乏研究,盲目开采致使许多温泉泉流量减小、水温降低,甚至断流、枯竭。为指导地下热水的科学开采,文章对重庆地下热水的常规化学组分及同位素组分特征进行了研究,分析了地下热水补给、径流条件,指出大气降水为其补给源,补给区在重庆以北大巴山及华莹山背斜华莹山和铜锣峡背斜北端的岩溶露头区,嘉陵江组(T1j)为其储水层,地下热水主要沿背斜T1j地层由北往南流,同一背斜地下热水由北到南为一个统一的热水系统。     

Is tree growth reduction related to direct foliar injuries or soil chemistry modifications?

In the context of intense emissions causing atmospheric pollution, tree growth reductions could be related to soil chemistry modifications or direct foliar injuries. To verify these hypotheses, mineral soils were sampled in an area (Murdochville, Canada) where previous studies had demonstrated that tree growth was impacted by smelter emissions and that forest floor lead concentrations could be used as a proxy for atmospheric pollutant depositions. Samples were analysed for Al, Pb (concentrations and isotope ratios), basic cations (Ca, K, P, and Mg) and Zr. Mass balance calculations were performed on soil profiles to assess vertical migration of elements. Pb concentrations in litter diminished gradually with distance from the smelter. The Pb isotope ratios in these organic soil layers were close to those measured in the Murdochville ores. These patterns were not encountered in mineral soil layers. Pb isotope ratios in these layers were close to those measured in uncontaminated geological materials, and Pb concentrations and basic cation depletions were not related to the proximity of the smelter. Growth reduction was closely associated with litter Pb concentrations, which were used as a proxy for atmospheric deposition, but was not correlated with any elemental concentration or cation depletion measured in mineral soil layers. Our overall results suggest that trees responded mainly to direct atmospheric emissions, which caused foliar damage, rather than to soil chemistry modifications.     

Relations of Habitat-Specific Algal Assemblages to Land Use and Water Chemistry in the Willamette Basin, Oregon

Benthic algal assemblages, water chemistry, and habitat were characterized at 25 stream sites in the Willamette Basin, Oregon, during low flow in 1994. Seventy-three algal samples yielded 420 taxa — mostly diatoms, blue-green algae, and green algae. Algal assemblages from depositional samples were strongly dominated by diatoms (76% mean relative abundance), whereas erosional samples were dominated by blue-green algae (68% mean relative abundance).Canonical correspondence analysis (CCA) of semiquantitative and qualitative (presence/absence) data sets identified four environmental variables (maximum specific conductance, % open canopy, pH, and drainage area) that were significant in describing patterns of algal taxa among sites. Based on CCA, four groups of sites were identified: streams in forested basins that supported oligotrophic taxa, such as Diatoma mesodon;small streams in agricultural and urban basins that contained a variety of eutrophic and nitrogen-heterotrophic algal taxa; larger rivers draining areas of mixed land use that supported planktonic, eutrophic, and nitrogen-heterotrophic algal taxa; and streams with severely degraded or absent riparian vegetation (> 75% open canopy) that were dominated by other planktonic, eutrophic, and nitrogen-heterotrophic algal taxa. Patterns in water chemistry were consistent with the algal autecological interpretations and clearly demonstrated relationships between land use, water quality, and algal distribution patterns.     

开发研制预防污染的绿色化学产品

文章叙述绿色化学在环境保护中的应用,绿色化学是一门从源头上彻底阻止污染的化学,简介了几种开发研制的对人类健康和环境安全的绿色化学产品及研究开发进展。     

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.

     

胶态水合二氧化锰絮凝粒子的结构形貌及其混凝机理

采用透射电镜技术观察了胶态水合二氧化锰絮凝粒子的结构形貌并采用Zeta电位测定仪对粒子的荷电特征进行了研究;利用红外光谱、XRD等技术对粒子的界面性质进行了表征;通过混凝试验考察了KMnO₄ 还原法制备的水合二氧化锰胶体对原水的混凝性能并探讨了混凝机理.结果表明,胶态水合二氧化锰粒子在去离子水和原水中荷负电,在去离子水中,粒子直径为10　nm并形成网状结构,有利于发挥吸附架桥作用;粒子具有丰富的表面羟基,比表面积为151.422　m²/g,为δ-MnO₂,表现出优良的吸附污染物的界面特性;较低投量的胶态水合二氧化锰表现出对原水的优良混凝效能和去除有机微污染的效能.