地洼盆地砂岩铜矿床成矿作用的化学动力学和热力学研究     

谭凯旋 Kaixu.  T 《大地构造与成矿学》1996,20(3):229-237

对我国南方中新生代地洼盆地中的砂岩铜矿床进行了化学动力学与热力学的理论与实验研究。矿源岩中以辉铜矿和黄铜矿最有利于溶解和迁移，ＮａＣｌ对Ｃｕ的溶解和含矿流体的形成起了催化作用。溶液中Ｃｕ以络合物的形式迁移，其中以一价铜氯络合物为主；温度的降低和溶液中性化导致了络合物的失稳、分解和铜矿物的沉淀。铜矿物的化学动力学和热力学制约了砂岩铜矿中以辉铜矿为主及矿床分带的形成。  相似文献   

原油族组分成气的化学动力学模型及其标定   总被引：27，自引：2，他引：27       下载免费PDF全文

卢双舫  付晓泰 《地质学报》1997,71(4):367-373

利用等温密封热解实验技术及恒速升温热解实验与PY—GC分析技术的结合,本文分别建立并标定了原油中各族组分,即饱和烃、芳烃、非烃和沥青质成气的化学动力学模型。结果表明,原油中不同族组分成气的过程均可用平行一级反应描述,但不同组分在平均活化能及活化能分布上有明显的差异。各族组分在地史过程中成气的过程可由各自的化学动力学模型来描述。这将使原油成气过程的定量、动态描述成为可能。  相似文献   

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     

Jillian Baker  Janet Arey  Roger Atkinson 《Journal of Atmospheric Chemistry》2004,48(3):241-260

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.  相似文献   

Controls on metamorphic equilibration: the importance of intergranular solubilities mediated by fluid composition          下载免费PDF全文

W. D. Carlson  J. D. Hixon  J. M. Garber  R. J. Bodnar 《Journal of Metamorphic Geology》2015,33(2):123-146

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.  相似文献   

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     

张荣华  胡书敏  张雪彤 《地质学报》2016,90(9):2437-2453

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。  相似文献   

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

《Applied Geochemistry》2016

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.  相似文献   

微生物对地下水中萘的降解特性及动力学研究     

张晟瑀  张朦幻  王利刚  万玉玉 《地学前缘》2021,28(5):146-158

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。  相似文献   

阿拉尔河悬浮物对铀的吸附影响研究          下载免费PDF全文

钟翼  许建新  韩积斌  徐凯 《盐湖研究》2020,28(1):112-122

为了解阿拉尔河悬浮物对铀的吸附特性,通过静态吸附实验,研究了吸附时间、pH值、温度和铀初始浓度等因素对模拟含铀水中U(VI)去除率的影响,并从热力学和动力学方面对吸附过程进行了分析。结果表明,在T=25℃,溶液初始pH=7,接触时间为16 h时,悬浮物对铀的平衡吸附率最佳,为95.48%。随着铀初始浓度的增加,吸附量增加,但吸附率随之下降,升高温度有利于铀的吸附。铀在悬浮物上的吸附过程符合Langmuir等温吸附方程,说明悬浮物对铀为单分子层吸附,且化学吸附占主导地位。吸附动力学过程可用准二级吸附动力学模型描述,表明吸附主要受动力学控制,由两个以上步骤共同控制。FTIR和EDS分析结果表明,吸附过程中铀主要与悬浮物表面活性基团螯合并以表面络合吸附为主。吸附前后的能谱对比分析表明,吸附过程中存在离子交换行为。因此,悬浮物对铀的吸附机理是以表面络合吸附和离子交换为主、物理吸附为辅的混合吸附过程。  相似文献   

硒对华贵栉孔扇贝碱性磷酸酶的酶动力学及理化性质研究     

余群  王重刚  陈荣  郁昂  郑微云 《海洋科学》2008,32(10):56-61

探讨了微量硒(Se~(4+))对华贵栉孔扇贝(Chlamys nobilis(Reeve))碱性磷酸酶(AKP)的作用。以催化动力学原理研究了不同缓冲系统中微量硒时AKP的影响。结果表明,Se~(4+)对谈酶的作用与酶所处的环境有关。在0.05 mol/L Na_2CO_3-NaHCO_3(pH 9.0)缓冲溶液中Se~(4+)浓度小于12.5 mmol/L时呈现出激活作用;Se~(4+)浓度大于12.5 mmol/L时呈现出非竞争性的抑制作用,其抑制常数为6.81×10~(-2)mol/L。在0.05 mol/L Tris-HCl缓冲系统(pH 9.0)中,微量Se~(4+)对AKP具有强烈竞争性抑制作用,其抑制常数为3.79×10~(-1)mol/L。经紫外吸收光谱、荧光发射光谱和圆二色谱的实验表明,微量Se~(4+)与AKP作用后,该酶的构象已发生了变化。研究发现海水环境中若含有微量Se~(4+)(SeO_3~(2-)),可以促进扇贝AKP的水解。利于贝类的生长发育和外壳的形成,并有益于贝类的繁殖。  相似文献   

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     

葛建  刘洋  李明揆  赵进  韩宝瑜 《海洋与湖沼》2012,43(5):938-942

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。  相似文献