Kinetics of the Gas-Phase Reactions of OH Radicals, NO3 Radicals and O3 with Three C7-Carbonyls Formed From The Atmospheric Reactions of Myrcene, Ocimene and Terpinolene

Rate constants for the gas-phase reactions of OH radicals, NO₃ radicals and O₃ with the C₇-carbonyl compounds 4-methylenehex-5-enal [CH₂=CHC(=CH₂)CH₂CH₂CHO], (3Z)- and (3E)-4-methylhexa-3,5-dienal [CH₂=CHC(CH₃)=CHCH₂CHO] and 4-methylcyclohex-3-en-1-one, which are products of the atmospheric degradations of myrcene, Z- and E-ocimene and terpinolene, respectively, have been measured at 296 ± 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained (in cm³ molecule^–1 s^–1 units) were: for 4-methylenehex-5-enal, (1.55 ± 0.15) × 10^–10, (4.75 ± 0.35) × 10^–13 and (1.46 ± 0.12) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3Z)-4-methylhexa-3,5-dienal: (1.61 ± 0.35) × 10^–10, (2.17 ± 0.30) × 10^–12, and (4.13 ± 0.81) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3E)-4-methylhexa-3,5-dienal: (2.52 ± 0.65) × 10^–10, (1.75 ± 0.27) × 10^–12, and (5.36 ± 0.28) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; and for 4-methylcyclohex-3-en-1-one: (1.10 ± 0.19) × 10^–10, (1.81 ± 0.35) × 10^–12, and (6.98 ± 0.40) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively. These carbonyl compounds are all reactive in the troposphere, with daytime reaction with the OH radical and nighttime reaction with the NO₃ radical being predicted to dominate as loss processes and with estimated lifetimes of about an hour or less.     

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.     

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。     

Reaction time scales for sulphate reduction in sediments of acidic pit lakes and its relation to in-lake acidity neutralisation

Sulphate reduction is a key reaction to remove acidity from water bodies affected by acid mine drainage. In this study, ³⁵SSO₄²⁻ reduction rates determined in sediments from a variety of acidic lignite pit lakes have been compiled. The rates decreased with pH and are strongly dependent on carbon substrate. The rates were fitted to a Monod model adapted to the specific conditions of acidic pit lakes (APL) sediments: i) sulphate reduction rate is independent from sulphate concentration due to the high concentration typically observed in APL systems (10–30 mM), ii) the observed pH dependency of sulphate reduction was accounted for by an inhibition function F_inihibt which considers the occurrence of low cell numbers of sulphate reducing bacteria at pH values < 4.75. Simulated steady-state sulphate reduction rates are predicting measured rates at carbon substrate concentrations of <10 μM. Estimated steady-state reaction time scales range between 2.4 h at pH 7 and 41 h at pH 3 at a carbon half-saturation constant of K_C−S = 100 μM and are increasing with increasing K_C−S values. Time scales at low pH are too long to allow for significant generation of alkalinity during the time of residence of groundwater passing through the top and hence most reactive zone of APL sediments which has important implications for the remediation of acidic pit lakes.     

微生物对地下水中萘的降解特性及动力学研究

针对我国东北某石油烃污染场地地下水中的萘污染,筛选出了Acinetobacter和Pseudomonas菌属的高效萘降解菌群。该菌群对萘的耐受性较高,且具有良好的乳化性,能够自动调节细胞表面疏水性和自聚集性。不同pH值、萘初始浓度、温度和菌接种量对萘降解效率的影响研究表明:最适菌群生长的pH范围为7.08.0;萘降解效率和速率在1.005.00 mg/L范围内与其初始浓度成正比;在1030 ℃温度范围内均表现出较高的萘降解效率。在此基础上,利用Guass、GuassAmp、LogNomal、Poisson和Pulse数学模型对萘的降解过程进行拟合,其降解速率更符合GuassAmp模型。通过将降解动力学模型中的常数与影响因素相关联,推导出了拟合度较高的多因素影响下的萘降解动力学方程。     

不同水温下儿茶素EGCG在黄颡鱼(Pelteobagrus vachelli)体内代谢动力学和肝消除研究

采用反相高效液相色谱-紫外检测法测定了黄颡鱼血浆、肝脏中儿茶素EGCG含量,并研究了不同水温(10℃和20℃)下EGCG在黄颡鱼体内代谢动力学和肝组织消除特征。结果表明,高温下黄颡鱼腹腔注射EGCG后体内吸收较快,T1/2ka为0.21h,T1/2α为2.07h,T1/2β为22.89h,AUC为5195.41μg·h/ml,Tp为0.95h,Cmax为257.75μg/ml;低温下分别为5.67h、9.53h、207.49h、17283.03μg·h/ml、12.56h和117.16μg/ml。同时在0.5、1、2、4、8、12、24、48、96h各时间点检测了肝脏组织中EGCG浓度,并计算得出高温下EGCG在肝组织中的T1/2β为24.15h,低温下肝组织中T1/2β为64.17h。对不同水温下代谢动力学和肝组织消除规律的研究表明,EGCG在黄颡鱼体内吸收、分布和消除速度与水温关系密切,高温下均较低温下迅速。     

中地壳的地球化学动力学和矿石成因

笔者重点进行了大于300℃——在近临界区至超临界区条件下的硅酸盐矿物与水反应动力学实验。矿物(钠长石Ab、透辉石Di、阳起石Act和磁铁矿Mt)的溶解反应动力学实验是使用流体通过叠层反应器的开放体系在25～400℃和22MPa下完成的。实验发现矿物在300℃至400℃范围,在跨越水临界点时出现反应速率的涨落。各种多金属氧化物硅酸盐与水反应时,各个元素溶解到溶液里的释放速率一般不一样,常称为一致溶解作用。但是,在近300℃变为一致溶解作用。实验发现在22MPa时硅酸盐矿物的最大溶解反应速率多是在300℃,如硅的最大释放速率是在300℃。其余元素如Na、K、Mg、Ca、Fe、Al等释放速率在<300℃22MPa时都高于硅的释放速率,在>300℃时硅的释放速率要高于其它元素的释放速率。确切地说,金属与氧之间的键的性质决定了它们(金属氧化物)与水之间反应速率。在一般情况下,Na-Obr,Ca-Obr,Mg-Obr,Al-Obr和Si-Obr的键桥(br),它们之间相对地由具有离子键性质逐步变为具有极性键的性质。由常温常压到亚临界区(300～374℃22MPa),再到大于临界点374℃、22MPa进入超临界区,水的性质随温度、压力变化。水由容易溶解离子键逐渐变为容易打破极性键。笔者还研究了黑钨矿、锡石(玄武岩、花岗闪长岩)与水在250～400℃条件下的反应动力学过程,得出了相同的结果。实验均发现在跨越水临界点时矿物(或岩石)与水反应的动力学涨落。这些实验结果可以用于说明中地壳上部的水/岩相互作用的特征。发生于中地壳的水、岩相互作用大多是在300～450℃和20～50MPa条件下进行的。各地区的地壳厚度不一,中地壳温度压力并不完全相同。模拟中地壳条件下水/岩相互作用实验,目的主要是研究矿物(或岩石)在300～450℃条件下反应动力学过程。已有热液矿床矿物流体包体数据表明:有一批矿床的主要矿石形成于300～500℃,低于NaCl H2O溶液临界线的条件。中地壳的流体处于由亚临界态跨越临界态,进入超临界流体太的演化过程。这种流体的性质变化会引起水/岩相互作用的反应动力学涨落和矿石大量沉淀。     

Methane emission from coal and associated strata samples

Summary This article discusses methods for providing a reliable forecast of the gas-dynamic behaviour of coal seams and adjacent strata. It shows that the ash content of carbonaceous materials determines their sorptive capacity (a universally applicable expression is presented for calculating the methane content of a sample) whilst the rate of methane desorption is a function of the degree of geological disturbance, i.e. the number and distribution of the macropores and fractures in the sample. This effect becomes less important as the sample ash content increases and effectively disappears above a certain value for high permeability materials.The quantity sorption-kinetic characteristic is shown to be a reliable means for quantifying methane emission behaviour. Large variations in coal sorption-kinetic characteristics are shown to occur over short distances as the geological structure of the seam changes, both vertically and horizontally. Consequently, sorption-kinetic characteristics may be used to predict the general level of methane emission from the seam and to quantify the risk of outburst inherent in disturbed areas of coal seams.     

旋转电极法研究盐类溶解─LiCl、NaCl、KCl在水中的溶解动力学

利用旋转盘装置结合离子选择电极研究了ＬｉＣｌ、ＮａＣｌ、ＫＣｌ在２０℃～３５℃水中溶解动力学，得到了溶解动力学方程．