An Algorithm for the Determination of All Significant Pathways in Chemical Reaction Systems     

Ralph Lehmann 《Journal of Atmospheric Chemistry》2004,47(1):45-78

When the output of a complex chemical model is analysed, a typical topic isthe determination of pathways, i.e., reaction sequences, that produce ordestroy a chemical species of interest.A representative example is the investigation of catalytic ozone destruction cycles in the stratosphere.An algorithm for the automatic determination of pathways in any given reactionsystem is presented. Under the assumption that reaction rates are known, it finds all significant pathways, i.e., all pathways with a rate above a prescribed threshold.The algorithm forms pathways step by step, starting from single reactions.The chemical species in the system are consecutively considered as `branching points'.For every branching-point species, each pathway producing it is connected witheach pathway consuming it.Rates proportional to `branching probabilities' are calculated.Pathways with a rate that is smaller than a prescribed threshold arediscarded.If a newly formed pathway contains sub-pathways, e.g., null cycles, it is split into these simpler pathways.In order to demonstrate the performance of the algorithm, it has been applied to the determination of catalytic ozone destruction cycles and methaneoxidation pathways in the stratosphere.  相似文献   

Influence of water level fluctuation on the spatial dynamic of the water chemistry at Lake Fertõ/Neusiedler See     

Mria Dinka  Edit goston-Szab  rpd Berczik  Gyula Kutrucz 《Limnologica》2004,34(1-2):48

Lake Fertõ/Neusiedler See is a steppe lake situated on the Hungarian-Austrian border with a surface area of 309 km². It is an extremely shallow lake with regulated outflow. 54% of the whole lake and 85% of the Hungarian part (75 km²) is covered by reed. There are numerous reedless areas (inner ponds) of variable size within the reed belt, which is enmeshed with canals connecting the inner ponds with the open water areas. Fundamental differences were recorded in the water chemistry of the three water type areas, open water, canals and inner ponds. The degree of these differences is basically determined by the distance from the open water areas and the water level of the actual years. An extremely high, an average and an extremely low water level year was examined, in order to present the spatial and temporal differences in the water chemistry of the investigated water bodies. Differences due to the water level fluctuation between years in the three different water types are discussed on the basis of electrical conductivity, cation, and anion concentration changes of the water. Our results support the concept of high instability of Lake Fertõ and describe habitats with remarkable temporal and spatial variability. The high influence of water level on habitat conditions at different sites of the lake recommend a carefull water level regulation strategy.  相似文献   

Evidence for freeze–thaw events and their implications for rock weathering in northern Canada     

Kevin Hall 《地球表面变化过程与地形》2004,29(1):43-57

Discussions regarding weathering in cold environments generally centre on mechanical processes and on the freeze–thaw mechanism in particular. Despite the almost ubiquitous assumption of freeze–thaw weathering, unequivocal proof of interstitial rock water actually freezing and thawing is singularly lacking. Equally, many studies have used the crossing of 0 °C, or values close to that, as the basis for determining the number of ‘freeze–thaw events’. In order to assess the weathering regime at a site in northern Canada, temperatures were collected at the surface, 1 cm and 3 cm depth for sets of paving bricks, with exposures both vertical and at 45°, orientated to the four cardinal directions. Temperature data were collected at 1 min intervals for 1 year. These data provide unequivocal proof for the occurrence of the freezing and thawing of water on and within the rock (freeze–thaw events). The freeze event is evidenced by the exotherm associated with the release of latent heat as the water actually freezes. This is thought to be the ?rst record of such events from a ?eld situation. More signi?cantly, it was found that the temperature at which freezing occurred varied signi?cantly through the year and that on occasion the 1 cm depth froze prior to the rock surface. The change in freeze temperature is thought to be due to the chemical weathering of the material (coupled with on‐going salt inputs via the melting of snowfall), which, it is shown, could occur throughout the winter despite air temperatures down to ?30 °C. This ?nding regarding chemical weathering is also considered to be highly signi?cant. A number of thermal stress events were also recorded, suggesting that rock weathering in cold regions is a synergistic combination of various chemical and mechanical weathering mechanisms. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

化学腐蚀下砂岩三轴细观损伤机理及损伤变量分析   总被引：10，自引：4，他引：10  

陈四利  冯夏庭  周辉 《岩土力学》2004,25(9):1363-1367

利用CT识别技术对化学腐蚀下的砂岩进行了三轴加载全过程的即时扫描试验，得到了在不同级荷载作用下砂岩的压密、微裂纹萌生、扩展和破裂的CT图像和CT数，分析了砂岩损伤演化的细观机理。同时，建立了一个基于化学腐蚀影响和CT数的损伤变量模型。  相似文献   

磷对金刚石增强型硬质合金复合齿性能的影响     

刘晓阳  史晓亮  段隆臣  汤凤林 《煤田地质与勘探》2004,32(4):62-64

在金刚石增强型硬质合金复合齿基体中添加不同量红磷，可降低复合齿烧结温度，实现低温活化烧结。研究表明：添加0．3％(ωB)P的复合齿基体性能最好，采用化学镀Ni-P合金添加P和球磨添加0．1％P的方式，复合齿超硬部分的磨耗比和复合齿的抗冲击功优于单纯通过球磨添加0．3％P的超硬复合齿。为了实现金刚石增强型硬质合金复合齿的低温活化烧结，磷元素最优的添加方式是化学镀结合球磨的添加方式。  相似文献   

Mantle Xenoliths from the Southeastern Slave Craton: Evidence for Chemical Zonation in a Thick, Cold Lithosphere   总被引：7，自引：3，他引：7  

KOPYLOVA  M. G.; CARO  G. 《Journal of Petrology》2004,45(5):1045-1067

We present the first data on the petrology of the mantle lithosphereof the Southeastern (SE) Slave craton, Canada. These are basedon petrographic, mineralogical and geochemical studies of mantlexenoliths in Pipe 5034 of the Cambrian Gahcho Kué kimberlitecluster. Major types of mantle xenoliths include altered eclogite,coarse garnet or spinel peridotite, and deformed garnet peridotite.The peridotites belong to the low-temperature suite and formedat T=600–1300°C and P= 25–80 kbar in a thick(at least 220–250 km), cool lithosphere. The SE Slavemantle is cooler than the mantle of other Archaean cratons andthat below other terranes of the Slave craton. The thick lithosphereand the relatively cool thermal regime provide favourable conditionsfor formation and preservation of diamonds beneath the SE Slaveterrane. Similar to average Archaean mantle worldwide, the SESlave peridotite is depleted in magmaphile major elements andcontains olivine with forsterite content of 91–93·5.With respect to olivine composition and mode, all terranes ofthe Slave mantle show broadly similar compositions and are relativelyorthopyroxene-poor compared with those of the Kaapvaal and Siberiancratons. The SE Slave spinel peridotite is poorer in Al, Caand Fe, and richer in Mg than deeper garnet peridotite. Thegreater chemical depletion of the shallow upper mantle is typicalof all terranes of the Slave craton and may be common for thesubcontinental lithospheric peridotitic mantle in general. Peridotiticxenoliths of the SE Slave craton were impregnated by kimberliticfluids that caused late-stage recrystallization of primary clinopyroxene,spinel, olivine and spinel-facies orthopyroxene, and formationof interstitial clinopyroxene. This kimberlite-related recrystallizationdepleted primary pyroxenes and spinel in Al. The kimberliticfluid was oxidizing, Ti-, Fe- and K-rich, and Na-poor, and introducedserpentine, chlorite, phlogopite and spinel into peridotitesat P < 35 kbar. KEY WORDS: kimberlite xenolith; lithosphere; mantle terrane; chemical zoning; thermobarometry; Slave craton  相似文献   

Chemical forms of heavy metal contaminants in sediments of Miyun reservoir     

LIU Xiaoduan  XU Qing  GE Xiaoli  LIU Liu  WU Dianwei 《中国科学D辑(英文版)》2005,48(Z2)

The chemical forms, spatial distribution and sources of As, Hg, Cd, Pb and Zn in sediments of the Miyun reservoir were studied. The results of sequential extraction demonstrate that most of As, Pb and Zn were bound to the residual fraction, Hg was associated with the sulfide fraction while Cd was associated with the carbonate fraction and the residual fraction. On the vertical profiles the concentrations of the heavy metals in total and each fractions mostly decreased with increasing depths in sediments, suggesting that the heavy metals input from the upstream watershed increases yearly. Summation of the residual fraction, the sulfide fraction and the carbonate fraction accounts for 60.03%―85.60% of the total heavy metal contents in the sediments, which represent the geochemical background values of the elements and relate closely to soil erosion. Results of the main factor analysis show that most sediments of the reservoir come from the upstream soil erosion, the point source pollution and domestic waste. Moreover, the microbial activities taking place on the sediment-water interface are also one of the major factors to cause the increasing content of the organic matter fraction and the iron-manganese oxide fraction. Environmental change of the reservoir water could make the removability of the heavy metals increase, leading to the increase of their concentrations in pore water in sediments, and imperiling water quality of the reservoir.  相似文献   

An invariance in the carbazoles of petroleum     

张春明赵红静  胡伯良 《中国地球化学学报》2005,24(3):253-256

A remarkable invariance in the ratio of 1,3-dimethylcarbazole （DMC） to 1,6-DMC was discovered in crude oils from the Pearl River Mouth Basin, South China Sea. The remarkably invariant ratio is kept at a constant of about unity regardless of their concentrations, sources or maturities for the sampies. In combination with the molecular structures of 1,3- and 1,6-DMCs, the invariance might indicate that the nitrogen compounds share a common precursor with a skeleton of 1-methylcarbazole and are formed through methylation at C3 and C6 with an essentially identical rate.  相似文献   

Laser Ablation ICP-MS Developments and Trends for 2003     

Paul J. Sylvester 《Geostandards and Geoanalytical Research》2005,29(1):41-52

This annual review of laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) covers the year 2003. Significant advances were made in understanding laser-sample interactions. In particular, research defined the distribution of particle sizes produced by the interplay of laser wavelength, laser pulse width and the gas environment of ablation. A link between particle sizes and elemental and isotopic fractionation at both the ablation site and in the ICP was established. Experimental 15 7 nm and femtosecond laser systems were tested with promising results. The number of applications of LA-ICP-MS in geology and environmental Earth science continued to grow with particular interest in element concentration and isotope ratio profiling of materials, linking composition to time scales. In situ isotopic ratio measurements were increasingly made using multicollector magnetic sector ICP-MS instruments. Other applications of wide interest included bulk sampling of rocks and ores prepared as lithium borate glasses; low level analysis of platinum-group elements, rhenium and gold in sulfides, metal and silicates; in situ uranium-lead zircon geochronology; and melt and fluid inclusion analysis.  相似文献   

电子探针化学测年技术及其在地学中的应用   总被引：2，自引：0，他引：2  

郭国林潘家永  刘成东郭福生 《华东地质学院学报》2005,28(1):39-42

电子探针主要应用于固体无机材料的微区化学成分定量测定和表面形貌研究。近十年来电子探针化学测年技术发展迅速，并取得了丰富的研究成果。本文在简单介绍该技术发展历程后，进一步详细介绍该技术的基本原理、样品制备与分析、年龄计算方法等内容，最后讨论了该技术的优缺点，同时指出电子探针测年技术在地学中的具有广泛的应用前景。  相似文献