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131.
Nyberg Lars Lundström Ulla Söderberg Ulf Danielsson Rolf van Hees Patrick 《Water, Air, & Soil Pollution: Focus》2001,1(1-2):241-263
In 1994, a large survey of soil chemistry was undertaken in thecounty of Värmland in central Sweden (Lundström et al., 1998).The southern part of the county was affected by soilacidification whereas there were no such indications in thenorthern part. To investigate the influence of soil chemistryon the trees at the specific sites, the survey was continued byan analysis of needle chemistry (Norway spruce) which wasundertaken at 150 of the 180 sites, and of tree growth at 65 ofthe 180 sites. Growth was expressed as a ratio between expectedgrowth, estimated with a national, empirical growth model, andthe growth observed in the field. In statistical analyses,using rank correlation, PCA and PLS, there were only weakindications of an influence of soil chemistry on needlechemistry and on tree growth. A moderate correlation betweennitrogen and sulphur in needles was found, which wasinterpreted as an effect of deposition and of processes in thetree canopy. No obvious regional pattern of the growth ratiowas found, in contrast to the clear pattern of soilacidification. The statistical analysis could not with anycertainty point out any of the soil chemistry variables asespecially important for the tree growth ratio. 相似文献
132.
Radiation fog is an important modifier of atmosphericcompounds in the planetary boundary layer. In vegetated areas effects are especially pronounced due to the enlarged surface area. Besides affectingthe lower boundary of atmospheric models fog acts as amulti-phase reaction chamber leading to acid deposition. Here we present the 1-dimensional radiation fog modelCHEMIFOG_V to simulate regional radiation fogevents. The key feature of the fog model is thedetailed microphysics, where the aerosol/dropletspectrum is describedwith a joint 2-dimensional distribution, but also thedynamics, thermodynamics, and radiative transfer are calculated. Toinvestigate the interaction between fog and the biosphere amulti-layer vegetation module, including a soil module as well as a drydeposition module were coupled. Vegetation influences thedynamics, thermodynamics, and the radiation field of the lowestatmospheric layers. With CHEMIFOG_V, numerical case studieson dry and moist deposition processes on vegetation surfaces wereperformed. Hereby multi-phase chemistry and the processing of aerosolswere considered. The results show that the chemical composition of thedeposited fog droplets is mainly determined by the aerosol composition. Dry deposition fluxes are dependent on the incoming radiation and the leaves' surface conditions with respect to water coverage.Due to chemical aerosol processing and deposition, the aerosol spectrumis significantly modified in the planetary boundary layer. 相似文献
133.
E. Martínez J. Albaladejo A. Notario E. Jimnez 《Atmospheric environment (Oxford, England : 1994)》2000,34(29-30)
The atmospheric reaction of the methylthiyl radical (CH3S) with O3 was investigated as a function of temperature (259–381 K), in the pressure range of 25–300 Torr, using the technique of laser photolysis/laser-induced fluorescence. The resulting Arrhenius expression, with an uncertainty of ±2σ, was k1(T=259–381 K)=(1.02±0.30)×10−12 exp[(432±77) K/T] cm3 molecule−1 s−1. The obtained rate constant k1 was independent of pressure over the limited range employed. Our results are compared with the previous studies carried out, at single temperature and as a function of temperature, by different techniques. 相似文献
134.
利用量子化学计算气相中锌离子各种水合和水解形态的几何结构、电荷分布以及水合和水解反应的Gibbs自由能变和焓变.结果表明,除了水合锌离子外,锌离子各种水解络合物的配位数均小于6;对于深度水解产物Zn(OH)3^-和Zn(OH)4^2-,内层无水分子的键合.水合作用和水解作用互相抑制,水合作用阻碍了水解产物进一步水解(Zn(OH)2除外),水解作用使得水合变得困难.内层键合水分子数的增加降低了水合形态中Zn上的电荷,使得水解形态Zn上的电荷升高. 相似文献
135.
OH自由基降解二英OCDD的反应机理及动力学研究 总被引:1,自引:0,他引:1
采用量子化学计算研究了OH自由基降解八氯代二苯并对-二英(OCDD)的微观反应机理,计算分析了微观反应进程,结果表明该反应存在两条途径:①α-氯取代:1,4,6,9位置氯取代,该路径反应活化能较高,反应难以进行,并以中间产物积聚,无法使OCDD的毒性消失;②β-氯取代:2,3,7,8位置氯取代,该路径的反应能相对较低,且能使OCDD的毒性消失,是有效降解OCDD的主要途径.结合过渡态理论,计算获得动力学参数:反应活化能为8.32 kJ·mol-1(B3LYP/6-311G++(d,g)//B3LYP/6-31G(d)),阿仑尼乌斯表达式为k=1.29×1014exp(-1049.6/T)(cm3·mole-1·s-1).这与文献实验结果取得了很好的吻合,说明本文对OH自由基降解OCDD的反应机理及动力学研究是合理且可靠的.本文的计算结果可为催化氧化降解二英的进一步研究提供理论参考. 相似文献
136.
赣南小流域的水文地球化学特征和主要风化过程 总被引:17,自引:4,他引:13
对赣南花岗岩小流域进行采样、测试及分析,发现其河水含有较低的矿化度,水化学组成以Na ,Ca2 ,Cl-1和HCO-3为主,溶解性Si的含量明显较高,代表了典型硅酸盐地区河流的相应化学组成.通过Gibbs图分析,赣南流域大部分地区受大气降水的影响比较显著,"蒸发-浓缩"类型的小流域也较多.根据主成分分析和因子分析的结果,定量地估算了大气中CO2和三类岩石对河水中各种离子的贡献比例.与黄河相比,赣南流域受硅酸盐岩风化作用强烈,但主要影响因素仍是碳酸盐和蒸发盐岩,二者对赣南流域溶解质的贡献率分别为42.8%和29.2%,大气中CO2对河水溶解质的贡献率为21.4%,低于世界平均水平.主要风化反应以岩盐和方解石的溶解为主,Si/(Na* K)比值较低,说明风化反应在表生环境中进行,其产物是富含阳离子的次生矿物. 相似文献
137.
138.
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.139.
本文概略论述了20多年来我国环境化学的研究状况,就环境污染分析化学、环境污染化学、环境污染控制化学今后的研究趋势和重点研究方向提出了自己的看法。 相似文献
140.
J. V. Bonta C. R. Amerman W. A. Dick G. F. Hall T J. Harlukowicz A. C. Razem N. E. Smeck 《Journal of the American Water Resources Association》1992,28(3):577-596
ABSTRACT: A study was conducted over a six-year period in East-Central Ohio to determine the effects of surface mining and reclamation on physical watershed conditions and on ground-water hydrology in three ground-water zones in three small experimental watersheds. Mining disturbances in watersheds adjacent to the experimental sites affected ground-water levels in the undisturbed experimental watersheds prior to actual mining in the experimental sites. New subsurface flow paths, with different characteristics, formed during mining and reclamation. At all three sites mining dewatered the saturated zone above the underclay of the mined coal seam. Mining and reclamation affected ground-water levels below the mined coal seam in the middle and lower zones within at least two sites. Ground-water level recovery in the mined upper saturated zone was slow and irregular both temporally and spatially after reclamation. Hydraulic conductivities of postmining (Phase 3) spoil were generally greater than those of Phase 1 bedrock, but wide spatial variability was observed. Modelers need to be aware of the complexities of new flow paths and physical characteristics of subsurface flow media that are introduced by mining and reclamation, including destruction of the upper-zone clay. 相似文献