矿物光电子能量在地球早期生命起源与进化中的作用

地球早期生命起源的第一步是合成简单的有机化合物，但合成有机物所需能量来源问题长期困扰着学术界。早期地球上丰富的硫化物半导体矿物可将太阳光子转化为光电子，提供持续的能量来源。也正是由于矿物光电子能量较高，在非生物途径合成小分子有机物方面具有优势。其中半导体矿物自然硫转化太阳能产生的光电子能量，是目前所发现的最高的矿物光电子能量，不仅能直接还原CO2分子为甲酸物质，还可催化其他生命基础物质的合成。在全球陆地系统中暴露在阳光下的岩石/土壤表面普遍被一层铁锰氧化物“矿物膜”所覆盖，光照下含半导体矿物水钠锰矿的“矿物膜”产生原位、灵敏、长效的光电流，显示出优异的光电效应。生物光合作用中心Mn4CaO5在裂解水产氧过程中产生成分和结构类似水钠锰矿的结构中间体，地球早期“矿物膜”中水钠锰矿可能促进了锰簇Mn4CaO5与生物光合作用的起源与进化。早期地球半导体矿物为生命起源基本物质的合成提供直接能量来源，矿物光电子能量在地球早期生命起源与进化中起到了重要作用。     

矿物光电子能量在地球早期生命起源与进化中的作用

地球早期生命起源的第一步是合成简单的有机化合物,但合成有机物所需能量来源问题长期困扰着学术界。早期地球上丰富的硫化物半导体矿物可将太阳光子转化为光电子,提供持续的能量来源。也正是由于矿物光电子能量较高,在非生物途径合成小分子有机物方面具有优势。其中半导体矿物自然硫转化太阳能产生的光电子能量,是目前所发现的最高的矿物光电子能量,不仅能直接还原CO₂分子为甲酸物质,还可催化其他生命基础物质的合成。在全球陆地系统中暴露在阳光下的岩石/土壤表面普遍被一层铁锰氧化物“矿物膜”所覆盖,光照下含半导体矿物水钠锰矿的“矿物膜”产生原位、灵敏、长效的光电流,显示出优异的光电效应。生物光合作用中心Mn₄CaO₅在裂解水产氧过程中产生成分和结构类似水钠锰矿的结构中间体,地球早期“矿物膜”中水钠锰矿可能促进了锰簇Mn₄CaO₅与生物光合作用的起源与进化。早期地球半导体矿物为生命起源基本物质的合成提供直接能量来源,矿物光电子能量在地球早期生命起源与进化中起到了重要作用。     

地球系统中生物成因硫化物矿物:类型、形成机制及其与生命起源的关系

作为生物矿物一种十分重要的类型,生物成因硫化物矿物形成于多种海水和淡水环境中.它们是自然界硫和金属元素循环中的关键一环,并有可能在地球早期生命起源中扮演了重要的角色.现代环境中形成的生物成因硫化物矿物与多种生命过程有着十分密切的联系,微生物和大型生物均可直接或间接地影响生物成因硫化物矿物的形成.重点从生物成因硫化物矿物类型、参与生物矿化的有机体、生物成因硫化物矿物形成机制以及硫化物矿物与生命起源的关系等几个方面综述了生物成因硫化物矿物研究的最新进展.     

生命起源、早期演化阶段与海洋环境演变

近年的研究表明,地球生命可能起源于距今39~36亿年之间。除了碳元素以外,水、氮、氢、磷等元素也是生命起源的必备条件,黏土矿物和金属硫化物是有机质合成的重要催化剂,有热液活动的碱性热水环境是最有利生命发生的孵化场。自原核生物在约3.5 Ga出现之后,生命就一直表现为与环境的协同进化关系。大气圈氧化是地球史上最重大的地质事件之一,它不仅改变了地球表层环境条件、加速了表生地质过程和新矿物的产生,而且改变了海洋化学条件和元素循环。大气圈氧化事件的根本在于产氧蓝细菌的出现,元古宙中期海洋化学性质的整体转换也与微生物过程密切相关。新元古代多细胞生物的繁盛和末期后生动物的出现及其在寒武纪初期的快速多样化是生物圈演化的重大飞跃。这个过程也与海洋氧化增强及其导致的海洋化学变化密切相关,其中硫化水域消失和减弱以及海水中微营养元素可得性增加可能是重要因素,这也与微生物过程直接相关。     

煌斑岩—硫化物熔体液态不混溶作用的高温高压实验研究

本文以云南老王寨金矿区煌斑岩和黄铁矿为初始物,在1.5～3.0GPa、1162～1560℃条件下进行了煌斑岩—硫化物熔体液态不混溶作用实验。结果表明,煌斑岩硫化物熔体的液态不混溶作用可能发生于岩浆演化的早期（高压条件）,但如有硫存在,在岩浆演化的各个阶段（高压条件→低压条件）均可能出现煌斑岩硫化物熔体的液态不混溶作用;与煌斑岩熔体分离的硫化物熔体在温度场、压力场中作定向运移,逐渐聚集于相对低温、低压区;由于硫化物熔体的密度相对较大,因而与煌斑岩熔体之间出现明显的分层现象。     

关于生命起源中地质作用的几点新看法

通过有机分子合成，矿物特性、相关地质作用的研究，可以认为，矿物质在导致生命演化的基本化学反应过程中起着关键性作用，地幔流体与地壳中的对流热液是生命产出过程的重要舞台，整个岩石圈对生命的产出是个必不可少的因素，在远古地球环境中，适当的水，大气、岩矿及物化组合，一定能够引发高分子化合物的产生甚至是生命的诞生，为了揭开生命起源的奥秘，一方面要对远古环境进行充分的研究，正确了解生命产生的初始环境；另一方面，要通过实验模拟，找出恰当的水、气、岩矿及物化条件组合。     

铜、镍、铂族元素地球化学性质及其在幔源岩浆起源、演化和岩浆硫化物矿床研究中的意义

Ni、Cu和PGE具有不同于其他微量元素的特殊的地球化学性质,这些特殊的性质使得它们在幔源岩浆起源和演化以及岩浆硫化物矿床的成因研究中具有不可替代的作用。在S不饱和的条件下,Ni、Os、Ir和Ru具有相容元素的特性,而Cu和Pd是强不相容元素,因此,它们在玄武岩浆分离结晶过程中常常发生分异。一旦体系达到S饱和,这些元素则会强烈地进入硫化物熔浆,特别是PGE具有极高的硫化物熔浆/硅酸盐熔浆分配系数,极微量的硫化物熔离便可导致残余岩浆中PGE的显著亏损,因此,PGE是玄武岩浆硫化物熔离作用最敏感的示踪元素。硫化物熔离和成矿实质上是幔源岩浆特殊演化过程的结果,所以,Ni,Cu和PGE的特殊性质可用来探讨岩浆硫化物成矿的关键控制因素。Ni、Cu和PGE具有不同的单硫化物固溶体/硫化物熔浆分配系数,因此,它们也是硫化物熔浆结晶分异的重要示踪元素。本文试图从Ni、Cu和PGE地球化学性质和行为入手,并借助一些研究实例,对它们在幔源岩浆起源和演化以及岩浆硫化物矿床成因研究中的示踪意义进行系统介绍。     

氧化亚铁硫杆菌作用下形成的黄钾铁矾的SEM研究

黄钾铁矾是金属硫化物在酸性条件下氧化形成的主要次生矿物。很多研究表明,金属硫化物矿区广泛发育的氧化亚铁硫杆菌会影响金属硫化物的氧化分解和次生矿物的形成。为讨论氧化亚铁硫杆菌在黄钾铁矾形成过程中的作用,设计了两组平行实验制备黄钾铁矾：一种采用化学方法合成黄钾铁矾,另一种在相同条件下接种氧化亚铁硫杆菌合成黄钾铁矾。利用X-射线衍射仪(XRD)、扫描电子显微镜(SEM)和能谱分析仪(EDS)等技术对两种实验获得的黄钾铁矾进行定性分析和形貌观察。结果表明：在氧化亚铁硫杆菌充分繁殖的条件下,细菌的参与更利于黄钾铁矾的形成;Fe^2+的氧化速率可能是影响黄钾铁矾结晶的主要因素,氧化亚铁硫杆菌通过提高Fe^2+的供应速度促使黄钾铁矾快速结晶,细菌作用下形成的黄钾铁矾结晶程度好于纯化学方法制备的黄钾铁矾。     

华北中元古代硫化物黑烟囟发现的初步报道

海底黑烟囟为当代海洋地质调查的重要发现，对于揭示地史时期块状硫化物的成矿过程中以及生命起源具有重要意义。本文初步报道在冀东中元古代块状硫化物矿床中首次发现保存完好的黑烟囟构造，它们保留了成矿流体运移的通道构造，围绕通道构造还显示良好的矿物分带现象。完全可以与现代海底黑烟囟对比，黑烟囟的发现证明了该区硫化物矿床的形成与海底喷流过程密切相关。     

地外有机化合物

球粒陨石中的有机化合物起源于星际介质,是构成太阳星云的初始组分,并与其他物质一起吸积形成小行星和行星。在小行星内,有机质经历了不同程度的水蚀变和热变质作用。球粒陨石中的有机化合物尽管是非生命成因,但组成极为复杂,主要是类似于干酪根的大分子物质,以及少量可溶性有机物。大部分可溶有机分子也发现于地球生物圈,但前者可具有完全不同的H、C、N等同位素组成,这也是它们来源于地球之外的重要证据。星云中宇宙线和紫外线（UV）的辐射、小行星的热变质和水蚀变,是地外有机质演化的主要过程。球粒陨石中的有机质是地球生命起源的物质基础,是生命起源不可或缺的重要环节。同样重要的是,大量的火星探测表明,火星历史上有过满足生命存在的基本条件,而在火星陨石中还发现了一些生物活动相关的线索。未来很可能首先在火星上发现地外生命存在的证据。     

Assaying the catalytic potential of transition metal sulfides for abiotic carbon fixation

A suite of nickel, cobalt, iron, copper, and zinc containing sulfides are assayed for the promotion of a model carbon fixation reaction with relevance to local reducing environments of the early Earth. The assay tests the promotion of hydrocarboxylation (the Koch reaction) wherein a carboxylic acid is synthesized via carbonyl insertion at a metal-sulfide-bound alkyl group. The experimental conditions are chosen for optimal assay, i.e., high reactant concentrations and pressures (200 MPa) to enhance chemisorption, and high temperature (250°C) to enhance reaction kinetics. All of the metal sulfides studied, with the exception CuS, promote hydrocarboxylation. Two other significant reactions involve the catalytic reduction of CO to form a surface-bound methyl group, detected after nucleophilic attack by nonane thiol to form methyl nonyl sulfide, and the formation of dinonyl sulfide via a similar reaction. Estimation of the catalytic turnover frequencies for each of the metal sulfides with respect to each of the primary reactions reveals that NiS, Ni₃S₂, and CoS perform comparably to commonly employed industrial catalysts. A positive correlation between the yield of primary product to NiS and Ni₃S₂ surface areas provides strong evidence that the reactions are surface catalytic in these cases. The sulfides FeS and Fe_(1−x)S are unique in that they exhibit evidence of extensive dissolution, thus, complicating interpretation regarding heterogeneous vs. homogeneous catalysis. With the exception of CuS, each of the metal sulfides promotes reactions that mimic key intermediate steps manifest in the mechanistic details of an important autotrophic enzyme, acetyl-CoA synthase. The relatively high temperatures chosen for assaying purposes, however, are incompatible with the accumulation of thioesters. The results of this study support the hypothesis that transition metal sulfides may have provided useful catalytic functionality for geochemical carbon fixation in a prebiotic world (at least intially) devoid of peptide-based enzymes.     

Molybdenite in calcium-aluminum-rich inclusions in the Allende meteorite

The first observations of molybdenite in a meteorite have been made in two CaAl-rich inclusions in the Allende chondrite. The mineral occurs as single individuals completely enclosed in high Ni metal (62–64.5 wt. % Ni). The association with refractories is consistent with thermodynamic calculations which predict that Mo is a high temperature condensate even when nucleation constraints are imposed on the formation of a metal phase. Kinetic factors (including nucleation constraints) appear to have played an important role in the formation of molybdenite and the associated sulfides, magnetite and high nickel metal.     

Fe(Ⅱ)/铁氧化物表面结合铁系统还原有机污染物的研究进展

在土壤和沉积物的自然厌氧环境中,铁氧化物可被铁还原菌等微生物异化还原产生Fe(Ⅱ),形成的Fe(Ⅱ)/铁氧化物表面结合铁系统具有还原活性,可使有机污染物还原转化。综述了含卤和含硝基有机污染物的非生物还原转化过程和表面结合铁系统与有机污染物之间的界面反应机理,进而揭示了污染物在环境中的赋存状态和迁移转化规律;重点分析了影响该还原过程的因素,如铁氧化物类型、pH值、Fe(Ⅱ)与铁氧化物接触时间,以及过渡金属、腐殖酸等竞争因子对反应过程的影响。强化自然界中天然的Fe(Ⅱ)/铁氧化物表面结合铁系统在有机污染治理中的作用,在受污染环境修复领域具有广阔的应用前景。 [HT5H]关 键 词:[HT5K]     

Metasomatic alterations of olivine inclusions in the Budulan mesosiderite

Mesosiderites are thermal metamorphic breccias consisting of fragments of pyroxene-plagioclase rocks and FeNi metal. The silicate constituent of mesosiderites has a chemical and oxygen isotopic composition analogous to those of meteorites of the HED group: howardites, eucrites, and diogenites. The hypothesis currently most widely accepted for the genesis of mesosiderites is the impact mixing of the material of a differentiated asteroid and an iron meteorite. In contrast to many other classes of meteorites, mesosiderites exhibit no traces of metasomatic processes. The Budulan mesosiderite is the first meteorite of this type in which traces of metasomatism under the effect of an anhydrous fluid were detected. The metasomatic alterations are manifested as chemical zoning of olivine, aggregates of secondary minerals, and the mobilization and redeposition of iron and nickel in the form of metals and sulfides. These alterations were most probably caused by a reaction of olivine with S- and/or CO-bearing gases of endogenic or supergenic provenance. Traces of such metasomatic alterations were previously found in some meteorites and lunar rocks, and these processes could likely play a certain role in the differentiation of chondritic bodies.     

Sicilian serpentinite xenoliths containing abiotic organics with nanodiamond clusters as key model for prebiotic processes

Rock fragments from the deepest parts of a buried hydrothermal system belonging to the Mesozoic Tethys Ocean entered as xenoliths in a Miocenic diatreme,hence brought to the surface,in the Hyblean Plateau(Sicily).Some xenoliths consist of strongly serpentinized ultramafic rocks bearing blebs of abiotic organic matter,where clusters of amorphous carbon nanoparticles,including nanodiamonds,are immersed.Such an occurrence conjures up established hypotheses that diamond surfaces are suitable catalytic platforms stimulating the assemblage of complex bio-organic molecules relevant to the emergence of life on Earth.The appearance of bio-organic molecules under primitive Earth conditions is one of the major unsolved questions on the origin of life.Here we report new micro-Raman spectra on blebs of abiotic organic matter from a selected xenolith.Diamond bands were related to hydrogenated nanocrystalline diamonds,with size of nearly 1-1.6 nm,formed from organics at low pressures and temperatures.In particular,diamond surfaces can give rise to crystalline interfacial water layers that may have played a fundamental role in the early biosphere evolution as a good medium for rapidly transporting positive charges in the form of hydrated protons.Nowadays,proton gradients in alkaline hydrothermal vents along oceanic ridges are generally viewed as key pre-biotic factors.In general,serpentinites span the entire geological record,including prebiotic times.These hydrous ultramafic rocks often display evidence of abiotic carbon species,both organic and inorganic,including nanodiamonds,being also capable to give rise to chemiosmotic processes and proton gradients necessary to the organisms,such as the"Last Universal Common Ancestor"(LUCA),in the prebiotic Earth.     

Partitioning of copper and zinc in the sediments and porewaters of a high-elevation alkaline lake,east-central Arizona,U.S.A.

In Pacheta Lake, a high-elevation alkaline lake proximal to the smelting region of southern Arizona-New Mexico, concentrations of transition metal ions in pore waters and co-existing sediments were compared. Copper, Fe, Mn and Zn have been partitioned among operationally defined sediment solid phases (exchangeable sites, organic complexes, amorphous oxides, crystalline oxides, sulfides and residual silicates) and their concentrations in interstitial waters were measured. Concentrations are reported as a function of depth in the sediment column. The diagenetic environment is described and cycling mechanisms postulated for the above metals.Selective, sequential extraction of metals from lake sediments showed different binding mechanisms for Cu and Zn, the former most strongly associated with organic complexes, and the latter with iron oxyhydroxides. This difference has strong implications for selective metal remobilization under variable environmental conditions, both naturally and anthropogenically induced. Copper and zinc in porewaters were estimated to diffuse to overlying waters at 12.8 and 21.9 μg/cm²/a, respectively. These fluxes are large enough to account for observed concentrations of Cu and Zn in overlying waters. No sediment metal contamination was directly attributable to smelting activity. However, this study does document a flux from sediments, which have accumulated Cu and Zn, to overlying waters no longer receiving trace metal deposition from now inactive smelters.     

川东北飞仙关组鲕滩储层硫酸溶蚀的证据和模式探讨

川东北飞仙关组鲕滩储层的主要储集空间为溶蚀孔洞,主要由大气淡水溶蚀作用、有机酸溶蚀作用和硫酸溶蚀作用所形成。通过硫酸对灰岩和白云岩溶蚀实验、天然气中硫化氢含量与飞仙关组石膏厚度关系分析、天然气中硫同位素与地层中的硫同位素比较、方解石胶结物的阴离子分析等证据,首次提出了硫酸溶蚀在该储层形成中起很重要的作用。探讨了硫酸溶蚀形成储层的模式。     

Modifications in the solubility and precipitation behavior of various metals as a result of their interaction with sedimentary humic acid

The sedimentary humic acid or its acid-hydrolysate, consisting of various amino acids, was found effective in dissolving unusually large quantities of metals (up to 682 mg/g of organic matter) from their insoluble salts. The presence of humic acid in the reaction media which had favorable conditions for the precipitation of metals as carbonates, hydroxides or sulfides, prevented the formation of insoluble metal salts. Infrared analysis suggests that the metals added to various anionic systems and humic acid do not react with the anion. The most likely mechanism of reaction appears to be a complex formation between metals and organic matter which keeps the metal in solution.The enhanced solubility and consequent decrease in precipitation of metals under the influence of humic compounds, as evidenced in these studies should play a leading role in the accumulation of metals in sedimentary deposits.     

铜镍硫化物矿床的成矿机理新探

描述岩浆中铜、镍、钴、铁迁移富集新机制。铜、镍、钴、铁呈氢化物迁移至地壳浅部,氢被氧化成水,铜、镍、钴、铁被硫化成硫化物及硫砷化物富集成矿床。     

Iron-Molybdenum Isotopes and the Chemical Evolution of Ancient-Oceans

Iron(Fe) is abundant in nature while molybdenum(Mo) is the most abundant transition metal in seawater. Due to their high sensitivity to the redox state of the environment, the isotopic compositions of Fe and Mo as well as variations have been widely used to probe the redox conditions and the evolution of ancient ocean chemistry in favor of improved analytical techniques. Here, we summarized isotopic fractionation mechanisms and natural distribution of both iron and molybdenum isotopes, and further we summarized and partially reinterpreted the redox evolution of ancient oceans through time based on available Fe-Mo data compiled in this study. The process that causes the largest iron isotope fractionation is redox reaction and the iron in oxidation state is generally enriched in ⁵⁶Fe. Biotic and abiotic pyrite formations also produce a large Fe isotope fractionations. Isotopic fractionation of molybdenum in seawater is mainly caused by the adsorption process of dissolved Mo onto ferromanganese oxides or hydroxides in sediments. Fe-Mn (hydro)oxides tend to adsorb isotopically light molybdenum resulting in the isotopic composition of Mo in seawater heavier. However, the Mo sinks in euxinic settings cause almost no molybdenum isotope fractionation. The Fe Mo isotope isotopic records through geological timegenerally suggest similar ocean redox evolution: Oceans older than 2.3 Ga was mainly dominated by ferruginous condition, and there was a slight increase in oxygen content between 2.6 and 2.5 Ga. Earth’s surface was initially oxidized during 2.3 to 1.8 Ga, during which euxinic deposition of sulfide was elevated. Euxinic waters may have expanded greatly between 1.8 and 0.8 Ga, and after that, Earth’s surface had being gradually oxidized and the euxinic waters shrank substantially.Finally, suggestions are proposed for further work on the Fe-Mo isotope research in the context of ancient ocean chemistry.