基于分段副产物瞬时选择性的反应器网络综合

针对第三类反应体系的反应器网络综合问题,提出将串联反应以反应物到目的产物的反应步数为依据的新分段策略。通过比较不分段目的产物、不分段目的产物和中间产品、分段副产物和分段目的产物这四种不同的瞬时选择性,提出以分段副产物瞬时选择性为参数,以其对关键组分浓度或转化率的导数为依据选择各阶段最合适的反应器,以目的产物总选择性最大为目标采用遗传算法优化反应器网络。通过三个实例验证了本文所建立方法在解决复杂反应反应器网络综合问题的有效性,且本方法同样适用于简单反应体系。     

Controls on metamorphic equilibration: the importance of intergranular solubilities mediated by fluid composition

A dramatic demonstration of the role of intergranular solubility in promoting chemical equilibration during metamorphism is found in the unusual zoning of garnet in pelitic schist exposed at Harpswell Neck, Maine, USA. Many garnet crystals have irregular, patchy distributions of Mn, Cr, Fe and Mg in their inclusion‐rich interiors, transitioning to smooth, concentric zoning in their inclusion‐poor outer rims; in contrast, zoning of Ca and Y is comparatively smooth and concentric throughout. We re‐assess the disputed origin of these zoning features by examining garnet growth in the context of the thermal and structural history of the rocks, and by evaluating the record of fluid–rock interaction revealed in outcrop‐scale veining and fluid‐inclusion assemblages. The transition in the character of garnet zoning correlates with the onset of a synkinematic, simple‐shear‐dominated phase of garnet growth and with a shift in the composition of the intergranular fluid from CO₂‐rich to H₂O‐rich. Compositional variations in garnet are therefore best explained by a two‐stage growth history in which intergranular diffusive fluxes reflect differences in the concentration of dissolved species in these two contrasting fluids. Interiors of garnet crystals grew in the presence of a CO₂‐rich fluid, in which limited solubility for Mn and Cr (and perhaps Fe and Mg) produced patchy disequilibrium overprint zoning, while appreciable solubility for Ca and Y permitted their rock‐wide equilibration. Rims grew in the presence of an H₂O‐rich fluid, in which high intergranular concentrations for all elements except Cr enabled diffusion over length scales sufficient for rock‐wide equilibration. This striking example of partial chemical equilibrium during reaction and porphyroblast growth implies that thermal effects may commonly be subsidiary in importance to solubilities in the intergranular medium as determinants of length scales for metamorphic equilibration.     

Reaction softening by dissolution–precipitation creep in a retrograde greenschist facies ductile shear zone,New Hampshire,USA

We describe strain localization by a mixed process of reaction and microstructural softening in a lower greenschist facies ductile fault zone that transposes and replaces middle to upper amphibolite facies fabrics and mineral assemblages in the host schist of the Littleton Formation near Claremont, New Hampshire. Here, Na‐poor muscovite and chlorite progressively replace first staurolite, then garnet, and finally biotite porphyroblasts as the core of the fault zone is approached. Across the transect, higher grade fabric‐forming Na‐rich muscovite is also progressively replaced by fabric‐forming Na‐poor muscovite. The mineralogy of the new phyllonitic fault‐rock produced is dominated by Na‐poor muscovite and chlorite together with late albite porphyroblasts. The replacement of the amphibolite facies porphyroblasts by muscovite and chlorite is pseudomorphic in some samples and shows that the chemical metastability of the porphyroblasts is sufficient to drive replacement. In contrast, element mapping shows that fabric‐forming Na‐rich muscovite is selectively replaced at high‐strain microstructural sites, indicating that strain energy played an important role in activating the dissolution of the compositionally metastable muscovite. The replacement of strong, high‐grade porphyroblasts by weaker Na‐poor muscovite and chlorite constitutes reaction softening. The crystallization of parallel and contiguous mica in the retrograde foliation at the expense of the earlier and locally crenulated Na‐rich muscovite‐defined foliation destroys not only the metastable high‐grade mineralogy, but also its stronger geometry. This process constitutes both reaction and microstructural softening. The deformation mechanism here was thus one of dissolution–precipitation creep, activated at considerably lower stresses than might be predicted in quartzofeldspathic rocks at the same lower greenschist facies conditions.     

从平衡-封闭-静态转向非平衡-开放-动力学研究-热液矿床成因的若干新概念概述

热液金属矿床成因研究过程中,观测与实验始终是密切结合的。上世纪70年代,平衡热力学的实验数据的快速积累,使人们用热力学理论计算可以预测和反演矿石和岩石的成因。但是,没有矿物-水溶液的反应速率数据,又没有与流体力学的结合,搞清楚矿石成因是困难的。七、八十年代,开始研究矿物与水溶液的反应动力学实验。科学家们开始瞄准了从平衡-封闭-静态转向非平衡-开放-动力学研究的这个大方向。1992年我们建立地球化学动力学开放研究实验室。研究高温高压矿物与水反应速率,发现固液的开放体系的自组织现象。实验发现温度影响矿物的各个元素反应速率改变,发现在跨越水临界态时矿物与水反应速率涨落、在近临界的气-液两相不混溶区一些金属进入气相、超临界流体的氧化作用及特别的溶剂性能影响矿物溶解性质。实验证实:临界态区流体与矿石成因有关。水岩相互作用的反应动力学实验温度从低温到550度,揭示矿石的金属来源、迁移、金属与蚀变分带机制。一大批大于300度的矿物与水反应动力学实验在国际界是少有报道的。九十年代,超高压的科学发展,与同步辐射光源的技术进步的结合,使固体地球科学又迈向了地球深内部。我们发展了高温高压流体性质的原位直测(测量850℃水溶液)红外谱,发现深部流体的新性质:气液两相流体的新结构,在临界温度区(300~400℃),水分子氢键网络的破坏受压力影响不大(23MPa~3GPa),同时,出现水的高电导率。研发新仪器为开放-流动-非平衡的反应动力学实验与极端条件下物质性质的直接观测结合,在科学前沿领域开辟了创新道路。     

Reactivity of micas and cap-rock in wet supercritical CO2 with SO2 and O2 at CO2 storage conditions

Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO₂, O₂, and NOx, may be present in CO₂ streams from coal combustion sources. SO₂ and O₂ have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO₂ fluid may also come into contact with the base of cap-rock after CO₂ injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation.The first observation of mineral dissolution and precipitation on phyllosilicates and CO₂ storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO₂ reactions with industrial impurities SO₂ and O₂ at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO₂ containing SO₂, or SO₂ and O₂, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO₂ dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO₂ containing SO₂ or in pure supercritical CO₂. In the presence of SO₂, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was buffered by carbonate dissolution. Ca-sulfate, and Fe-bearing precipitates were observed post SO₂-CO₂ reaction, mainly centered on surface cracks and an illite rich illite-smectite precipitate quantified. Water saturated impure supercritical CO₂ was observed to have reactivity to rock-forming biotite, muscovite and phlogopite mineral separates. In the cap-rock core however carbonates and chlorite were the main reacting minerals showing the importance of assessing actual whole core.     

辽南金州拆离断层带中花岗质岩石的变形:显微构造、组构与年代学分析

花岗岩(脉)在中下地壳韧性剪切带中普遍发育,如何正确鉴别剪切带中剪切前、剪切期及剪切后花岗岩(脉)以及正确理解剪切过程中构造变形与岩浆作用之间的关系一直是一个重要课题。本文以辽南金州拆离断层带为研究对象,选取中部地壳伸展作用过程中具有不同变形表现的花岗岩(脉)开展宏观-微观构造观察、石英EBSD组构分析及锆石LA-ICP-MS年代学测试等工作,从而进一步丰富构造-岩浆关系判别准则。剪切前花岗岩(脉)多变形强烈且具有后期固态变形叠加在早期高温岩浆组构之上的特点,而剪切期的花岗岩由于侵位的时间不同,岩石的变形程度也会不同。剪切晚期侵入的岩脉遭受了较弱的晶内塑性变形,而剪切早期的岩脉可以显示岩浆流动或结晶后高温至中温固态变形。从组构特点上看,剪切前和剪切期花岗质岩石石英c轴组构大多表现为中高温组构叠加有低温组构的特点。剪切后的花岗质岩石仅发生微弱的晶内变形或未变形而显示低温或无规律的组构特征。对五个典型的样品进行年代学测试,其结果符合相应的期次划分类型。应用宏观构造、显微构造与组构分析,结合年代学测试综合分析,对于辽南变质核杂岩构造-岩浆活动性进行了精细划分,包括134~130Ma初始伸展阶段,130~115Ma峰期伸展与强烈岩浆活动阶段,以及115Ma前后伸展作用结束。     

阴山陆块武川石榴基性麻粒岩P-T条件及其变质时代:来自相平衡模拟与锆石U-Pb定年的约束

武川高级片麻岩地体中石榴基性麻粒岩的变质用与同位素年代学研究对于揭示阴山陆块新太古代构造演化过程具有十分重要的研究意义。它们主要以不规则透镜体或变形岩墙/岩脉群的形式赋存于新太古代晚期英云闪长质片麻岩或变质表壳岩系之中,并切割近南-北向的区域性片麻理。岩相学观察、矿物相转变分析与矿物化学研究表明,武川石榴基性麻粒岩保留了十分典型的高压麻粒岩相矿物:石榴石+单斜辉石+斜长石+角闪石+石英+铁-钛氧化物。其中,粗粒石榴石边部常发育微弱的扩散环带,表现为从幔部至边部,镁铝榴石组分不断减少,相应地铁铝榴石组分不断增加,而钙铝榴石与锰铝榴石组分基本不变,指示晚期冷却降温作用对石榴石成分产生一定影响。斜长石具有细粒包体型与粗粒基质型两种不同的类型,它们具有十分相似化学成分,均为An=35~45的中长石。在NCFMASHTO(Na_2O-CaO-FeO-MgO-Al_2O_3-SiO_2-H_2O-TiO_2-Fe_2O_3)体系下,利用THERM OCA LC 3.33软件,对两件石榴基性麻粒岩样品进行了相平衡模拟,模拟的峰期矿物组合为:石榴石+单斜辉石+斜长石+角闪石+石英+铁-钛氧化物,与岩相学观察十分一致。采用石榴石中最小x(g)Fe~(2 +)/(Fe~(2 +)+Mg))与斜长石是中最小ca(pl)(Ca/(Ca+Na))等值线,将本区石榴基性麻粒岩峰期高压麻粒岩相的温压条件限定在P=1.31~1.40GPa,T=770~840℃的范围内。LA-ICP-MS锆石U-Pb定年结果表明,两件石榴基性麻粒岩麻粒岩中发育的变质锆石分别记录了2517±6Ma(BT58-1,MSWD=0.66,n=21)与2512±16Ma(LH66-1,MSWD=0.26,n=42)的加权平均年龄,与阴山陆块其它新太古代岩石记录的约2500Ma变质年龄一致,被解释为本区石榴基性麻粒岩遭受高压麻粒岩相变质时代。结合本区其它新的研究资料,本文认为武川石榴基性麻粒岩形成可能与区内新太古代晚期造山作用有关。     

吉林白山刘家堡子狼洞沟金银矿床地球化学特征及成因探讨

通过对刘家堡子-狼洞沟金银矿床地质、成矿元素和同位素地球化学特征的分析和研究,发现矿区内近EW向和NE向断裂构造是主要容矿构造;最佳找矿元素前缘晕组合为As-Sb-Zn,矿上晕元素组合为Au-Ag-Pb-Hg,尾晕元素组合为Ni-Cu-Co;成矿作用中,古老基底中元古宙老岭群变质岩系为成矿提供了丰富的物质来源,而燕山期构造岩浆活动在提供成矿物质的同时还提供了热动力。刘家堡子-狼洞沟金银矿床应划属为与燕山晚期超浅成中酸性岩浆岩有关的中低温热液构造裂隙充填型金银矿床。     

元素分析仪-同位素比值质谱测量碳氮同位素比值最佳反应温度和进样量的确定

沉积有机质的碳氮稳定同位素值是进行古气候、古环境及生态系统研究不可或缺的主要研究手段,目前碳氮同位素主要利用元素分析仪-同位素比值质谱(EA-IRMS)系统来测定。EA-IRMS测定过程中的反应温度及样品进样量直接影响反应物在测试中的燃烧程度,从而影响测试数据的精度。本文利用EA-IRMS技术,以标准样品为参考,在不同转化温度下测试碳氮同位素值,研究保证测试精度的最佳反应温度条件;同时,通过分析不同含氮量样品的检测限,明确了样品含氮量与最低检测限之间的关系,确定了精确测定氮同位素值的最低进样量。结果表明:反应温度对测试精度有显著影响,在碳同位素测定时,将反应温度设定为900℃或以上时测试精度均能达到±0.2‰;氮同位素测定时,反应温度须设定为950℃时测试精度才能达到±0.3‰。实验得出样品含氮量与检测限之间的线性相关性为R2=0.873,开展氮同位素测定时可根据此关系来判断和控制进样量。     

压力对辉长岩矿物反应和部分熔融影响的实验研究

本文在高温高压条件下,开展了辉长岩矿物反应与部分熔融实验,利用偏光显微镜与扫描电镜对实验样品微观结构观察,研究实验中的新生矿物与熔体的分布;通过电子探针分析熔体成分特征。实验结果表明,在低压(300MPa)条件下,静压和塑性变形实验样品中,单斜辉石以固体反应方式生成橄榄石,在高压(1300MPa)塑性实验中所有实验样品都没有发现新生矿物颗粒,这与相图中低压条件下斜长石与橄榄石稳定共存,而高压下斜长石-辉石稳定共存相吻合。高压塑性变形条件下,单斜辉石和黑云母首先发生部分熔融,随着温度增高,斜长石逐渐参与熔融,熔体呈薄膜状分布在矿物颗粒边界,熔体成分依赖于参与熔融的矿物成分,表明出现的熔体为非平衡熔融结果。