Kinetics of the reactions of Cl atoms with 2-buten-1-ol, 2-methyl-2-propen-1-ol, and 3-methyl-2-buten-1-ol as a function of temperature

The reactions of three structurally similar unsaturated alcohols, 2-buten-1-ol (crotyl alcohol), 2-methyl-2-propen-1-ol (MPO221) and 3-methyl-2-buten-1-ol (MBO321) with Cl atoms, have been investigated for the first time, using a 400 l Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID). The experiments were performed at atmospheric pressure and at temperatures between 255 and 298 K, in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions , , (in units of cm³ molecule⁻¹ s⁻¹). Finally, atmospheric lifetimes of those unsaturated alcohols with respect to OH, NO₃, O₃ and Cl have been calculated.     

The Origin of the Element Eu in Extremely Metal-poor Halo Stars

The fast neutron capture process (the r-process) occurs in the neutron-rich circumstance. However its concrete physical environment is not very clear. With recent progress in observations, many extremely metal-poor halo stars have been discovered. They have two characteristics: one is the overabundance of fast neutron elements with the relative abundance consistent with that of the sun; the other is that fast neutron element contents in stars at the same metal abundance have a very large dispersion. This provides a particular way to study the origin of the r-process. Simulation was used to study the galaxy's evolution process and the resulting dispersion of fast neutron nuclide contents in stars. The model of galaxy evolution obtained in this way not only contains spontaneous star formation in the gas region, but also includes the star formation excited by the supernova explosion. It is shown from our results that the supernovae at the low mass end should be the place producing the fast neutron nuclides. In addition, it is also shown that the non-uniformity of the galaxy evolution caused by the supernova explosion is not enough to explain the observed dispersion of fast neutron element contents in halo stars. This problem should be further studied.     

Metamorphic reactions in dry and aluminous granulites: a Perple_X <Emphasis Type="Italic">P–T</Emphasis> pseudosection analysis of the influence of effective reaction volume

In high-Mg, Al metapelites, monophase sapphirine corona occur around spinel–corundum aggregates in monomineralic cordierite layers, and bi-phase orthopyroxene–sillimanite aggregates replace locally warped sapphirine in polygonized cordierite aggregates. P–T phase topologies computed (Perple_X software) using compositions of cordierite-rich layers that host the reaction textures did not match the assemblages for the discontinuous reactions spinel + corundum + cordierite → sapphirine and sapphirine + cordierite → orthopyroxene + sillimanite. Instead, the reaction assemblages were reproduced using P–T pseudosection analysis for micro-domain reaction volumes estimated from compositions of product phases in the volume proportion they occur. The results are consistent with known phase relations deduced using Schreinmakers P–T grids. Apparently, the compositions of cordierite-rich layers that hosted the reaction textures were inadequate chemical proxies for determining P–T–X relations of phase-boundary controlled reactions influenced by compositions of the nearest-neighbor minerals in the proportion they react (effective composition), and not in the proportion they existed in the layer/bulk rock. In other words, P–T–X phase topologies and reconstructed P–T paths in dry and aluminous rocks may be best understood by thermodynamic modeling of reactions using effective reaction volume compositions rather than the bulk composition of the rock or the mineralogical layer that host the reaction textures.     

Mutual replacement reactions in alkali feldspars I: microtextures and mechanisms

Intracrystal microtextures formed by a process of mutual replacement in alkali feldspars record fluid–rock reactions that have affected large volumes of the Earth’s crust. Regular, ≤1 μm-scale ‘strain-controlled’ perthitic microtextures coarsen, by up to 10³, by a dissolution–reprecipitation process, producing microporous patch or vein perthites on scales >100 μm. We have developed earlier studies of such reactions in alkali feldspar cm-scale primocrysts in layered syenites from the Klokken intrusion, South Greenland. We present new hyperspectral CL, SEM images, and laser ICPMS analytical data, and discuss the mechanism of such replacement reactions. The feldspars grew as homogeneous sodic sanidines which unmixed and ordered by volume diffusion during cooling into the microcline field at ~450°C, giving regular, fully coherent ‘braid’ cryptoperthite. At ≤450°C the crystals reacted with a circulating post-magmatic aqueous fluid. The braid perthite behaved as a single reactant ‘phase’ which was replaced by two product phases, incoherent subgrains of low albite and microcline, with micropores at their boundaries. The driving force for the reactions was coherency strain energy, which was greater than the surface energy in the subgrain mosaic. The external euhedral crystal shapes and bulk major element composition of the primocrysts were unchanged but they became largely pseudomorphs composed of subgrains usually with the ‘pericline’ and ‘adularia’ habits (dominant {110} and subordinate {010} morphology) characteristic of low T growth. The subgrains have an epitactic relationship with parent braid perthite. Individual subgrains show oscillatory zoning in CL intensity, mainly at blue wavelengths, which correlates with tetrahedral Ti. Regular zoning is sometimes truncated by irregular, discordant surfaces suggesting dissolution, followed by resumption of growth giving regular zoning. Zones can be traced through touching subgrains, of both albite and microcline, for distances up to ~500 μm. At ≤340°C, the microcline subgrains underwent a third stage of unmixing to give straight lamellar film perthites with periodicities of ~1 μm, which with further cooling became semicoherent by the development of spaced misfit dislocations. Sub-grain growth occurred in fluid films that advanced through the elastically strained braid perthite crystals, which dissolved irreversibly. Braid perthite was more soluble than the strain-free subgrain mosaics which precipitated from the supersaturated solution. Some volumes of braid texture have sharp surfaces that suggest rapid dissolution along planes with low surface energies. Others have complex, diffuse boundaries that indicate a phase of coherent lamellar straightening by volume diffusion in response to strain relief close to a slowly advancing interface. Nucleation of strain-free subgrains was the overall rate-limiting step. To minimise surface energy subgrains grew with low energy morphologies and coarsened by grain growth, in fluid films whose trace element load (reflected in the oscillatory zoning) was dictated by the competitive advance of subgrains over a range of a few tens of mm. The cross-cutting dissolution surfaces suggest influxes of fresh fluid. Removal of feldspar to give 2 vol% porosity would require a feldspar:fluid ratio of ~1:26 (by wt). The late reversion to strain-controlled exsolution in microcline subgrains is consistent with loss of fluid above 340°C following depressurization of the intrusion. A second paper (Part II) describes trace element partitioning between the albite and microcline subgrains, and discusses the potential of trace elements as a low-T geothermometer. This paper and the Part II are dedicated in memory of J.V. Smith and W.L. Brown, both of whom died in 2007, in acknowledgement of their unrivalled contributions to the study of the feldspar minerals over more than half a century.     

Interplay between equilibrium and kinetics in prograde metamorphism of pelites: an example from the Nelson aureole, British Columbia

The distribution of metapelitic mineral assemblages in the Nelson aureole, British Columbia, generally conforms to what is predicted from phase equilibria. However, in detail, the sequence and spacing of isograds, mineral textures and mineral compositions and mineral chemical zoning do not. Two of the main disequilibrium features in the aureole are: (i) delay in the onset and progress of several reactions, i.e. overstepping in temperature; and (ii) unreactivity of staurolite and especially garnet porphyroblasts when they are reactants in prograde reactions. The thermal overstepping is ascribed to difficulty of nucleation of the product porphyroblasts and sluggishness of dissolution of porphyroblasts when they are reactants. The extent to which these kinetic barriers delay the onset of reaction is related to the reaction affinity of each reaction, defined herein as the Gibbs free‐energy difference between the thermodynamically stable, but not‐yet‐crystallized, products and the metastable reactants. For oversteps in temperature (ΔT), reaction affinity is, in turn, related to the difference in entropy (ΔS) between these two states through the relation A = ΔT * ΔS. Mineral reactions which release large quantities of H₂O, such as chlorite‐consuming reactions, have a higher entropy change per unit of temperature overstep, and therefore a higher reaction affinity, than those which release little or no H₂O, such as the chlorite‐free staurolite‐consuming reaction. Thermal overstepping is consequently expected to be less for the former than for the latter, as was estimated in the aureole where 0 to 30 °C overstepping was required for garnet, staurolite and andalusite growth from a muscovite + chlorite‐bearing precursor rock and ～70 °C overstepping was required for the growth of Al₂SiO₅ from a staurolite‐bearing, chlorite‐free precursor. In all cases, reaction progress was strongly influenced by the presence or absence of fluid, with presence of fluid lowering kinetic barriers to nucleation and growth and therefore the degree of thermal overstepping. Textural features of rocks from the nearly coincident garnet, staurolite and andalusite isograds are suggestive of a fluid‐catalysed ‘cascade effect’ in which reaction took place in a narrow temperature interval; several competing muscovite + chlorite‐consuming reactions, some metastable, appear to have occurred in parallel. Metamorphic reaction, fluid release and possibly fluid presence in general in the aureole were episodic rather than continuous, and in several cases well removed from equilibrium conditions. The extent to which these findings apply to regional metamorphism depends on several factors, a major one being enhanced deformation, which is expected to lower kinetic barriers to nucleation and growth.     

The δ13C–δ18O variations in marble in the Hida Belt,Japan

Marble has a great potential to understand a history of various geological events occurring during tectonic processes. In order to decode metamorphic–metasomatic records on C–O isotope compositions of marble at mid-crustal conditions, we conducted a C–O–Sr isotope study on upper amphibolite-facies marbles and a carbonate–silicate rock from the Hida Belt, which was once a part of the crustal basement of the East Asian continental margin. Carbon and oxygen isotope analyses of calcite from marbles (Kamioka area) and a carbonate–silicate rock (Wadagawa area) show a large variation of δ¹³C [VPDB] and δ¹⁸O [VSMOW] values (from −4.4 to +4.2 ‰ and +1.6 to +20.8 ‰, respectively). The low δ¹³C values of calcites from the carbonate–silicate rock (from −4.4 to −2.9 ‰) can be explained by decarbonation (CO₂ releasing) reactions; carbon–oxygen isotope modeling suggests that a decrease of δ¹³C strongly depends on the amount of silicate reacting with carbonates. The occurrence of metamorphic clinopyroxene in marbles indicates that all samples have been affected by decarbonation reactions. All δ¹⁸O values of calcites are remarkably lower than the marine-carbonate values. The large δ¹⁸O variation can be explained by the isotope exchange via interactions between marble, external fluids, and/or silicates. Remarkably low δ¹⁸O values of marbles that are lower than mantle value (~+5 ‰) suggest the interaction with meteoric water at a later stage. Sr isotope ratios (⁸⁷Sr/⁸⁶Sr = 0.707255–0.708220) might be close to their protolith values. One zircon associated with wollastonite in a marble thin-section yields a U–Pb age of 222 ± 3 Ma, which represents the timing of the recrystallization of marble, triggered by H₂O-rich fluid infiltration at a relatively high-temperature condition. Our isotope study implies that the upper amphibolite-facies condition, like the Hida Belt, might be appropriate to cause decarbonation reactions which can modify original isotope compositions of marble if carbonates react with silicates.     

长春地区白垩系地层地铁勘察参数的确定

白垩系砾岩及泥岩地层在长春地区普遍存在,但由于砾岩地层现场钻探难以取样进行室内土工试验,泥岩地层由于存在水稳性、膨胀性、崩解性等因素影响,砾岩和泥岩的承载力值、抗剪强度参数指标、渗透系数以及基床系数等参数多以经验数据评估方法为主,在合理准确确定相关参数的问题上存在较大分歧。通过对长春地区白垩系砾岩及泥岩进行原位平板载荷试验、浸水载荷试验以及现场原位剪切试验,获取砾岩、泥岩的承载力值、抗剪强度指标、渗透系数以及现场基床系数值等,为地铁建设工程地质问题分析及设计提供充足的地质依据。     

Reliability analysis of the induced damage for single-hole rock blasting

Rock explosion has always been a complex problem because neither rock characteristics nor explosion waves could be accurately estimated. As such, this imposes a high uncertainty on deterministic methodologies available for damage prediction. In this paper, by defining two damage zones around the blast hole, including crushed and cracked zones, a first-order reliability analysis (FORM) was adopted to address this issue. For this purpose, FORM was used in a double-loop algorithm, where the inner loop was responsible for converging the FORM, and the outer loop was assigned to feed the inner loop with new cases. Using such nested-loop algorithm, the probability of exceedance was calculated for any desired damage zone radius. The maximum effect of the involved parameters on the failure probability induced around the blast hole was additionally studied using a parametric reliability analysis. The results showed that the radii for crushed and cracked zones are limited to 0.5 and 4.2?m, respectively, so that the probability of going beyond these limits is less than 1%. Moreover, the analyses of decoupled explosions showed that increasing the gap between the explosion charge and wall of the borehole could severely reduce the failure probability; however, the maximum effect of decoupling ratio occurs in the small range of radii between 0.3?mm and 2.35?m.     

撞击事件诱发核反应热力学过程及其在事件地质学研究中的意义

摘要：从大规模撞击事件的基本动力学和热力学公式推导出发,讨论了白垩纪－第三纪界线（Ｋ／Ｔ界线）事件能量随时间的释放过程,并对发生热核聚变反应的条件进行了分析。最后,还对其可能的事件地质学意义进行了讨论．     

菱刈矿床矿脉群形成的构造环境

本文主要介绍菱刈矿床矿脉的赋存状态、裂隙体系分析、矿脉群赋存的构造环境。菱刈矿床属脉状浅成热液型金银矿床。矿床成因与裂隙系统的形成关系密切。矿脉群大致位于基底岩石(四万十层群)隆起的中央部位。