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。     

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。     

海洋平台隔水套管群桩性状的研究

海洋平台的隔水套管群桩与土共同作用研究是一个很复杂的课题,目前国内外研究资料甚少,因此在平台导管架设计中,一般不考虑隔水套管群桩承受水平力作用,这与实际不相符合。本文结合工程课题,在调查研究和模型试验的基础上,对隔水套管群桩在水平力作用下的工作性状与破坏机理、群桩的水平力及其主要影响因素、单桩与群桩情况下应力应变关系等方面进行较深入的研究;并提出砂土地基隔水套管群桩效应经验公式,弥补了现行计算方法的缺陷和不足。研究成果可供工程设计参考使用。     

Primary Product Distributions from the Reaction of OH with m-, p-Xylene, 1,2,4- and 1,3,5-Trimethylbenzene

A study was conducted to examine the OH-initiated degradation products of the four title compounds in the presence of sub-part-per-million levels of NO_x. The oxidation was conducted in a dynamic reactor to minimize the conversion of the aromatic compounds. The experiments were designed to represent reaction pathways that occur in the atmosphere at ambient NO₂ concentrations. A wide range of ring-retaining and ring-cleavage products having widely varying yields were measured during the study. For m-xylene, the major primary products observed (with molar yields) were methyl glyoxal (0.40), 4-oxo-2-pentenal (0.12), glyoxal (0.079), and m-tolualdehyde (0.049). For p-xylene, the major primary products were p-tolualdehyde (0.103), 2,5-dimethylphenol (0.13), cis-3-hexene-2,5-dione (0.176), trans-3-hexene-2,5-dione (0.045), 2-methyl-butenedial (0.071), glyoxal (0.394), and methylglyoxal (0.217). Several other reaction products were measured at yields less than 3%. The primary products for OH + 1,2,4-trimethylbenzene were found as follows: methylglyoxal (0.44), glyoxal (0.066), cis-3-hexene-2,5-dione (0.13), trans-3-hexene-2,5-dione (0.031), biacetyl (0.114), 3-methyl-3-hexene-2,5-dione (0.079), and 2-methyl-butenedial (0.045). Six other (ring retaining) products were measured at yields less than 3%. The primary products for OH + 1,3,5-trimethylbenzene were methylglyoxal (0.90), 3-methyl-5-methylidene-5(2H)-furanone (0.1), 3,5-dimethyl-3(2H)-2-furanone (0.1), 3,5-dimethyl-5(2H)-2-furanone biacetyl (0.08), and 2-methyl-4-oxo-2- pentenal (0.05). Three other products were detected at molar yields less than 5%. In some cases, the yields for the ring fragmentation products could only be based on calibrations from surrogate compounds. Yields for several of the unsaturated dicarbonyl compounds have not been reported previously while yields for methylglyoxal, glyoxal, and biacetyl are largely consistent with previous reports. Some of the primary furanone products are the identical to those reported as secondary products in aromatic systems.     

蒙皂石伊利石化反应机理和框架性行为模式

对珠江口盆地两口钻井95个泥质岩样粘土矿物X衍射分析资料的定量研究表明,若反应是以消耗蒙皂石为代价形成伊利石,则反应符合溶解-沉淀机理,但除此以外,蒙皂石还可以净溶解或新增伊利石层的方式加大I/S比。蒙皂石在渐进成岩过程中的框架性行为模式具有三级控制,按顺序分别由温度、基本离子成分和动力学因素控制特定温度段内蒙皂石行为过程的起始和终结、行为过程的方式和行为过程的速率和程度。渐进成岩过程中I/S比的变化主要与第三级控制有关,而游离状蒙皂石和伊-蒙混层粘土的含量变化则是第二三两级共同控制的结果。     

金属矿物的反应动力学与地球化学意义

概述了动力学实验的技术方法和金属矿物的反应动力学研究进展。动力学实验使用的三种基本化学反应装置是间歇反应器（ＢＲ）、活塞流反应器（ＰＦＲ）和混合流反应器（ＭＦＲ）,确定速率定律的数学方法包括积分法、微分法和混合法,以微分法中的初始速率法应用最广。目前主要研究了水溶液中黄铁矿氧化、黄铁矿和黄铜矿形成、晶质铀矿和磁铁矿溶解的速率定律和反应机理,发现：（１）酸性溶液中黄铁矿的氧化速率对Ｆｅ３＋和Ｏ２浓度呈分数依赖并受表面反应的控制;（２）低于３００℃时黄铁矿不能从溶液中直接成核,而需初始地通过ＦｅＳ先驱物的硫化生成,ＦｅＳ与Ｈ２Ｓ反应形成黄铁矿的速率方程为二级;（３）磁黄铁矿或黄铁矿与Ｃｕ２＋反应均可形成黄铜矿,前者经历了一系列准稳的Ｃｕ Ｆｅ硫化物的中间物,后者的速率方程为表观一级并受表面反应的控制;（４）酸性ｐＨ时磁铁矿的非线性溶解行为可采用表面反应扩散输运耦合的收缩核模型（ＳＣＭ）来描述。有关动力学实验成果完善和深化了对矿床中黄铁矿、黄铜矿的形成机理和风化壳中磁铁矿的稳定性等方面的认识。将来的实验研究将向更多的金属矿物和高温高压领域发展。     

Multi-stage pseudomorphic replacement of garnet during polymetamorphism: 2. Algebraic analysis of mineral assemblages

Chemical relationships among four metapelites have been studied by investigation of mineral and bulk chemistry data and by singular value decomposition analysis of single and composite assemblage matrices. Bulk rock compositions cluster close together in an AFM diagram, all within the intersection space defined by the four sample assemblages. The similarity of bulk compositions normalized on a silica-free, anhydrous basis indicates that sample chemistries differ mainly as a result of inhomogeneous distribution of quartz layers. The existence of mass balance relationships among samples indicates that assemblages also overlap in the Si–Ti–Al–Fe–Mg–Mn–Ca–Na–K multisystem. Analysis of single and composite matrices helps in defining possible mass balances linking sample mineral facies to one another during progressive contact metamorphism. The assemblage in sample A can form as the result of the model reaction 5.000  Ky+0.269 Grt+0.965 Bt+0.314 Pl=0.049 Ilm+1.115 Ms+0.849 Chl+0.306 St and react to assemblage B via reaction 0.97 Chl+0.52 Grt+0.66 Ms+0.14 Ilm+1.26  Ky=0.42 St+0.63 Bt+0.22 Pl coupled with the Ky→And transition. Assemblage B can transform into C by initial progress of Ky+Ilm+Chl+Grt+Ms=And+St+Bt+Pl followed by 0.142 Ilm+0.175 St+1.089 Chl+1.533 Ms+0.003 Grt=5.000 And+1.266 Bt+0.551 Pl Matrix analysis cannot satisfactorily model the C–D transition, because it predicts a net production of staurolite, which is in disagreement with petrographic evidence. All mass balances in the C–D composite matrix indicate net consumption of muscovite; this is integrated with the contrasting evidence of prograde pseudomorphs of muscovite after staurolite, observed in the nodules of sample D, within a model involving the progress of ionic reaction cycles.