On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes     

Eric A. Betterton 《Journal of Atmospheric Chemistry》1993,17(4):307-324

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.  相似文献   

Kinetics of redox cycling of iron coupled with fulvic acid     

Yiwei Deng  Werner Stumm 《Aquatic Sciences - Research Across Boundaries》1993,55(2):103-111

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.  相似文献   

新疆第四纪盐类矿产的形成和控制因素——兼论“高山深盆”成盐模式   总被引：1，自引：0，他引：1  

王得林 《新疆地质》1993,(1)

根据袁见齐教授“高山深盆”成盐模式,探讨新疆天山对第四纪盐类矿床的形成和控制作用,阐述了天山地貌、气候、水文特征与盐类矿产的分布规律和特征。认为“高山深盆”并非一定是四周环山的深盆,可以是某一高山与其间深盆或两侧盆地的有机组合。高山的屏障作用造成了垂直的气候分带,在潮湿多雨的山区利于成盐组份的析出并迁移到干旱少雨的闭流深盆中,形成盐类矿床。  相似文献   

塔里木克拉通东北缘二叠纪镁铁质岩浆氧化物与硫化物成矿条件对比     

徐文博  张铭杰  包亚文  满毅  李思奥  王鹏 《地质学报》2022,96(12):4257-4274

塔里木克拉通东北缘坡北、磁海等地二叠纪幔源岩浆活动形成了镍钴硫化物矿床和铁钴氧化物矿床，两者赋矿镁铁 超镁铁岩体的年龄相近(290~260 Ma)，主、微量元素和Sr Nd Hf同位素组成相似，分配系数接近的微量元素比值分布于相同趋势线，揭示两者岩浆源区相同，可能为俯冲板片流体交代的亏损地幔或软流圈地幔。两类矿床镁铁 超镁铁质岩中Co与Ni含量正相关，Co主要富集在基性程度高的岩石中；块状硫化物与磁铁矿矿石中Co与Ni相关性差，Co和Ni具有不同的富集机制，Co热液富集作用明显。北山镁铁 超镁铁杂岩体是地幔柱相关软流圈上涌，诱发俯冲板片交代的亏损岩石圈地幔发生部分熔融，形成的高镁母岩浆演化过程中经历壳源混染、硫化物饱和富集镍钴形成铜镍钴硫化物矿床，富铁母岩浆氧逸度高、富水，岩浆分离结晶磁铁矿、叠加热液作用富集钴，形成铁钴氧化物矿床。  相似文献   

稀土矿床：基本特点与全球分布规律     

毛景文  宋世伟  刘敏  孟健寅 《地质学报》2022,96(11):3675-3697

本文介绍了全球稀土资源供需历史、现状和对未来的展望。从矿床成因视角切入，将稀土矿床分为内生和外生两大类型，其中内生稀土矿床包括碳酸岩型、碱性岩型、碱性岩型- 碳酸岩型、氧化铁铜金型、热液脉型，外生稀土矿床包括风化壳离子吸附型、沉积岩型、沉积矿产(煤矿、铝土矿和沉积磷矿)伴生型、砂矿和现代海洋底部含稀土的锰结核、结壳和软泥型。归纳总结了主要类型矿床的基本特点和时空分布；认为内生稀土矿床产出于四类构造环境，包括裂谷环境、碰撞后伸展环境、大陆碰撞环境和后俯冲伸展环境；从构造演化入手，探讨了在外生与内生地质过程中稀土元素的迁移和富集规律，建立了涵盖主要矿床类型的构造- 成矿模型。  相似文献   

深部矿产资源立体地球化学勘查方法技术体系     

史长义  王惠艳 《地质学报》2022,96(11):3705-3721

深部矿产资源的勘查是战略性矿产资源勘查的一个重要方面。找矿实践证明，化探方法技术在矿产勘查乃至深部找矿中发挥了重要的、不可或缺的作用。找矿工作的不断深入和找矿难度的不断加大，促使化探方法技术不断的发展和完善，在传统方法技术的基础上，研发出了许多新的方法技术。本文从方法论和系统论的角度出发，对现有的找寻深部隐伏矿盲矿的有效化探方法技术进行了系统的归纳和总结，提出了立体地球化学勘查方法技术体系的概念，将立体地球化学勘查方法技术划分为地面地球化学测量方法技术和地下地球化学测量方法技术，建立了深部矿产资源立体地球化学勘查方法技术体系。不同的方法技术有不同的优势和不同的适用条件，实际工作中应当根据不同的勘查阶段，不同的勘查目的和不同的地质地球化学条件选择不同的立体方法技术组合才能发挥出最大效益，取得最大效果。  相似文献   

中国南方离子吸附型稀土矿床成矿类型及其母岩控矿因素探讨     

付伟  赵芹  罗鹏  李佩强  陆济璞  周辉  易泽邦  许成 《地质学报》2022,96(11):3901-3923

传统认为中国南方的离子吸附型稀土矿床可划分为以“足洞式”为代表的重稀土型和以“河岭式”(或“花山式”)为代表的轻稀土型两种矿化类型。然而，近年来发现的许多矿床(如清溪、寨背和馒头山等)的赋矿风化壳中出现了轻稀土矿与重稀土矿并存现象，表现出特殊的“上轻下重”双层矿体结构。这指示了除重稀土型和轻稀土型之外，还存在着轻重稀土共生型的过渡类型。本研究通过对三种不同成矿类型的若干典型矿床系统对比，指出成矿类型的多样性与母岩性质密切相关，尤其是母岩的稀土元素地球化学和稀土载体矿物属性是制约成矿类型变化的关键因素。统计数据表明，从重稀土型→轻重稀土共生型→轻稀土型，成矿母岩的全岩稀土总量变化不大(ΣREY: 200×10-6~450×10-6→200×10-6~500×10-6→200×10-6~800×10-6)，但轻重稀土配分值出现较显著的区间性差异(ΣLREE/ΣHREY: 02~1→1~5→2~10)。与之同时，母岩中能为离子相稀土提供物源且具有重稀土配分属性的稀土副矿物类型和数量明显减少，这与全岩稀土元素地球化学特征中重稀土分量占比的降低趋势也互相匹配。该结果指示，以往认为重稀土配分母岩形成重稀土矿床、轻稀土配分母岩形成轻稀土矿床的传统观点需要外延，即一部分具有低度轻稀土配分属性(1＜ΣLREE/ΣHREY＜5)且含有丰富易风化稀土副矿物的母岩还可能形成轻重稀土共生型矿床，该认识可为今后离子吸附型稀土矿床勘查工作提供新的找矿依据。  相似文献   

High-resolution sequence stratigraphy of the Lower Triassic ‘Buntsandstein’ in the Netherlands and northwestern Germany     

Geluk  M.C.  Röhling  H.-G. 《Geologie en Mijnbouw》1997,76(3):227-246

Detailed log correlations of the largely fluvio-lacustrine Lower Triassic Buntsandstein (Late Permian-Early Anisian), carried out on 80 wells in the Dutch onshore and offshore areas, can be linked to northwest-German high-resolution sequence stratigraphy. The correlations show that cyclic sedimentation occurred in large parts of the basin. Seven 1st-order sequences are recognised, namely the Main Claystone, Rogenstein, Volpriehausen, Detfurth, Hardegsen, Solling and Lower Röt Sequences. They are overlain by the lower part of the Upper Röt–Lower Muschelkalk Sequence. Distinct sequence boundaries have been identified at the bases of four sequences: Volpriehausen, Detfurth, Solling and Upper Röt. The higher-order sequences consist of fining-upwards cycles with a thickness of up to tens of metres. The sequences are laterally persistent and have a characteristic expression on gamma-ray and sonic logs. In the Lower Buntsandstein, they display a uniform character throughout most of the area, with only minor differences in thickness or lithology. NNE-oriented lows and swells were formed during deposition of the Volpriehausen, Detfurth and Hardegsen Sequences. Uplift prior to the deposition of the Solling Sequence caused deep erosion on the swells in the basin and minor erosion in the lows. The high-resolution sequences probably represent alternating, relatively wet and dry climatic periods, with a periodicity of about 100 000 years. An analysis of the sequences suggests that their reduced thickness on the swells is mainly the effect of erosion. This is supported by analyses of the accumulation patterns and rates.  相似文献   

Sector collapse,sedimentation and clast population evolution at an active island-arc volcano: Stromboli,Italy   总被引：1，自引：0，他引：1  

P. Kokelaar  C. Romagnoli 《Bulletin of Volcanology》1995,57(4):240-262

Sciara del Fuoco is the subaerial part of a partially filled sector-collapse scar that extends to 700 m below sea level on Stromboli volcano. The collapse occurred <5000 years ago, involved 1.81 km³ of rock and is the latest of a series of major collapses on the north-west flank of Stromboli. A north-east trending arc-axial fault system channels magmas into the volcano and has caused tilting and/or downthrow to the north-west. The slope of the partial cone constructed between the lateral walls of the collapse scar acts as a channelway to the sea for most eruptive products. From 700 m below sea level and extending to >2200 m and >10 km from the shore to the NNW, a fan-shaped mounded feature comprises debris avalanche deposits (>4 km³) from two or more sector collapses. Volcaniclastic density currents originating from Sciara del Fuoco follow the topographic margin of the debris avalanche deposits, although overbank currents and other unconfined currents widely cover the mounded feature with turbidites. Historical (recorded) eruptive activity in Sciara del Fuoco is considerably less than that which occurred earlier, and much of the partial fill may have formed from eruptions soon after the sector collapse. It is possible that a mass of eruptive products similar to that in the collapse scar is dispersed as volcanogenic sediment in deep water of the Tyrhennian basin. Evidence that the early post-collapse eruptive discharge was greater than the apparent recent flux (2kg/s) counters suggestions that a substantial part of Stromboli's growth has been endogenous. The partial fill of Sciaria del Fuoco is dominated by lava and spatter layers, rather than by the scoria and ash layers classically regarded as main constituents of Strombolian (cinder) cones. Much of the volcanic slope beneath the vents is steeper than the angle of repose of loose tephra, which is therefore rapidly transported to the sea. Delicate pyroclasts that record the magmatic explosivity are selectively destroyed and diluted during sedimentary transport, mainly in avalanches and by shoreline wave reworking, and thus the submarine deposits do not record well the extent and diversity of explosive activity and associated clast-forming processes. Considerable amounts of dense (non-vesicular) fine sand and silt grains are produced by breakage and rounding of fragments of lava and agglutinate. The submarine extension of the collapse scar, and the continuing topographic depression to >2200 m below sea level, are zones of considerable by-passing of fine sand and silt, which are transported in turbidity currents. Evidently, volcanogenic sediments dispersed around island volcanoes by density currents are unlikely to record well the true spectrum and relative importance of clast-forming processes that occurred during an eruption. Marine sedimentary evidence of magmatic explosivity is particularly susceptible to partial or complete obliteration, unless there is a high rate of discharge of pyroclastic material into the sea.  相似文献   

Hamiltonian perturbation theory on a manifold     

Francesco Fassò 《Celestial Mechanics and Dynamical Astronomy》1995,62(1):43-69

This paper deals with Hamiltonian perturbation theory for systems which, like Euler-Poinsot (the rigid body with a fixed point and no torques), are degenerate and do not possess a global system of action-angle coordinates. It turns out that the usual methods of perturbation theory, which are essentially local being based on the construction of normal forms within the domain of a local coordinate system, are not immediately usable to study perturbations of these systems, since degeneracy makes impossible to control that the system does not fall into a singularity of the coordinates. To overcome this difficulty, we develop a global formulation of Hamiltonian perturbation theory, in which the normal forms are globally defined on the phase space manifold. The key for this study lies in the geometry of the fibration by the invariant tori of an integrable degenerate Hamiltonian system, which is described by some generalizations of the Liouville-Arnol'd theorem and is reviewed in the paper. As an application, we provide a global formulation of Nekhoroshev's theorem on the stability for exponentially long times.  相似文献