金属改性碳脱除PH3和H2S动力学及反应机理研究

为综合利用黄磷尾气中的CO,通过计算平均活化能和测定XPS、TG/DTA和氮吸附特性的方法,研究了Cu²⁺和某金属离子Mn⁺改性碳脱除PH₃和H₂S的动力学和反应机理问题。结果表明：H₂S在金属改性碳上反应时平均活化能为134.4 J/mol为-0.76级反应,PH₃在金属改性碳上反应时平均活化能为1 247.6 J/mol为-0.8级反应;减小改性碳粒径增加流量可以显著提高其脱除PH₃和H₂S的速率;XPS、TG/DTA和孔径分布分析证明,改性碳净化H₂S和PH₃是一个催化吸附过程,H₂S和PH₃首先与氧在改性碳表面进行催化氧化反应,然后生成S和P₂O₅沉积吸附在改性碳表面。     

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.

     

用煤矸石合成4A沸石分子筛处理氨氮废水

以煤矸石为原料,采用碱熔一水热法合成4A沸石分子筛。由于煤矸石中铝、硅主要以高岭土形式存在,其活化过程是合成4A沸石分子筛关键环节。为提高4A沸石分子筛钙离子的交换能力,增加对模拟废水氨氮的去除率,实验考察了碳酸钠与煤矸石质量比、活化温度、活化时间、晶化温度和晶化时间对4A沸石分子筛钙离子交换能力的影响,同时也考察了模拟废水的pH、4A沸石分子筛加入量及吸附时间对氨氮去除率的影响。结果表明,最佳工艺条件为,碳酸钠与煤矸石质量比为0．9、活化温度为800％、活化时间1．5h、晶化温度90％和晶化时间3h。合成4A沸石分子筛的钙离子交换能力为310mg／g,在pH为6的100mL模拟氨氮废水中加入6g4A沸石分子筛吸附40min后,废水中氨氮的去除率达到86％。通过最佳工艺条件合成4A沸石分子筛,在处理氨氮废水方面具有一定的应用前景。     

室内环境中化学污染物质测定法研究

室内环境中化学污染物质的测定是研究和解决室内环境问题的基础。本文以甲醛和挥发性有机化合物两种室内环境中的主要化学污染物质为例,介绍了目前世界各国采用的各种测定法及其动向,并探讨了测定时期、测定时间、采样点布置等有关问题,提出了一些看法供参考。     

环境有机质对FeS-水体系中林丹脱氯转化的影响

采用批处理方法,评价几种典型的环境有机质对缺氧或无氧FeS-水体系中,林丹非生物脱氯转化动力学的影响.测定了不同反应介质条件下,林丹的非生物脱氯转化速率和产物的分布.结果表明,反应体系中高浓度的表面活性剂对林丹的转化有明显的抑制作用,转化速率为对照体系的18%;萘醌对林丹转化的速率及其产物分布均没有明显的影响;加入25 mg/L胡敏酸可使林丹的转化速率提高1.29倍;加入2 mmol/L 2,2'-联吡啶明使林丹的转化速率提高2.2倍.研究表明,水生态环境中与FeS共存的有机物可能对有机氯污染物的自然衰减产生较大影响.     

光化学降解有机磷农药研究进展

光化学降解有机磷农药是一种高效、无二次污染的非生物转化过程,也是有机磷农药在环境中的主要降解途径.本文通过介绍光化学方法降解有机磷农药的基本原理、有机磷农药的主要光化学反应类型、光化学降解过程中光敏(猝灭)剂的作用及影响光化学反应的因素,分析了今后光化学降解有机磷农药研究中需要关注的问题,提出将有机磷农药的光催化氧化技术与其他方法相结合,研发高效、经济的新技术是今后农药残留降解技术研究的重点.     

德兴地区土壤重金属人为污染的地球化学评价

在系统采集德兴地区表层土壤样品的基础上,采用标准化方法确定了该区Cu、Pb、Zn、Cr、Cd、Hg、As的地球化学基线值,并采用富集因子对表层土壤的人为污染进行了地球化学评价.结果表明:1)土壤中7种重金属元素的基线值较江西省土壤背景值高;2)土壤中As、Hg、Cd、Cr、Pb、Zn的人为污染以轻微污染为主,Cu的人为污染为轻微污染和中度污染,人为污染的区域主要分布在德兴铜矿及其周边地区;3)土壤重金属污染源判别表明,Pb、Zn、Cd具有相似的来源,其污染与铅锌矿的采矿及冶炼活动有关,Cu的来源与德兴铜矿的采矿活动有关,其他重金属来源差异较大.     

Temporal variability in 20 chemical elements content of Parasol Mushroom (Macrolepiota procera) collected from two sites over a few years

Mature specimens of Parasol Mushroom were collected annually in the outskirts of the Siemiany (2000–2003) and Rafa (2001–2003) sites in the northern part of Poland to examine temporal variations and similarities in the composition of 20 chemical elements. Analysis was done under the same condition and using well-validated analytical methods. Elements were determined by inductively coupled plasma–atomic emission spectroscopy and cold vapour–atomic absorption spectroscopy (Hg). The ranges of Ag, Al, Ba, Ca, Cd, Co, Cu, Cr, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr and Zn concentrations in the caps of fruiting bodies were similar (p > 0.05; Mann-Whitney U test) for both geographically distant sites, and these specimens from Rafa were more contaminated with Pb (p < 0.05; Mann-Whitney U test). The annual collections of caps in the Siemiany site varied in Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, Hg, Na, Rb and Sr and contents (0.05 < p < 0.001), while they were similar in Cr, K, Mg, Mn, Ni, P, Pb and Zn (p > 0.05; Mann-Whitney U test). The annual collections of specimens from the Rafa site varied in contents of Ag, Al, Ba, Ca, Fe, Hg, K, Mg, Mn, P, Rb and Zn (p > 0.05), while they were similar in Cd, Co, Cr, Cu, Na, Ni, Pb and Sr (p < 0.05). The results of this study imply that metallic elements content of Parasol Mushroom collected at the same undisrupted sites, and hence keeping the same geochemical condition for mushroom development and fructification (the same stands and probably the same mycelia), can fluctuate over the years or the life-span of mycelium. Hence, when assessing the nutritional value of essential metallic elements and status of non-essential or toxic metallic elements in Parasol's Mushroom caps (and probably also of other mushrooms species) to man, the possible fluctuation in contents over time have to be taken into account.     

制浆厂污泥制备活性炭吸附剂

以制浆厂污泥为原料,采用ZnCl2法、H2SO4法和KOH法3种化学活化法制备活性炭吸附剂,并对产物吸附苯酚性能的影响因素进行比较分析.结果表明,采用ZnCl2法和H2SO4法制备的活性炭吸附剂的效果明显优于KOH法,ZnCl2法为最佳制备方法,在其最佳制备条件下(ZnCl2浓度3 mol/L,活化温度800℃,活化时间30 min,升温速率20℃/min)制得的活性炭比表面积可达到500.98 m2/g,得率为46.9％,对苯酚的去除率为70.4％.采用ZnCl2法和H2SO4法在最佳制备条件下可以制备孔径分布较宽,中孔结构发达的活性炭.     

有机物的结构——活性/性质定量关系及其在环境化学和环境毒理学中的应用

有机物结构-活性定量关系研究(QSAR,Quantitative Structure-Activity Relationship)用于环境化学和环境毒理学领域取得了引人注目的成功。有机污染物在环境中的行为,尤其在生物体内的富集和致毒是环境化学和环境毒理学的主要研究方向之一。QSAR法可以从已有的大量情报中最大量地提取有关环境污染物结构—活性关系进行深入的研究。