地表“矿物膜”:地球“新圈层”

地球表层是一个极为复杂的开放系统,其中所充满的阳光、大气、水分、有机酸、无机酸/盐、矿物质和微生物等彼此之间无时无刻不在发生着人们尚未充分认识到的多种自然作用。本文采用环境矿物学、半导体物理学与光电化学等交叉学科研究手段,在我国南方红壤、西南喀斯特和西北戈壁等典型陆地生境中,发现直接暴露于太阳光下的土壤/岩石表面广泛发育有几十纳米到数百微米厚度的铁锰氧化物"矿物膜";详细研究了铁锰氧化物"矿物膜"中矿物组成及其精细结构特征,发现半导体性能优异的水钠锰矿普遍存在,其晶体结构中富含促进其光催化功能的稀土元素Ce。在这些生境中,矿物岩石表面所包覆的铁锰氧化物"矿物膜"总是朝着太阳光发育,岩石背面却不出现"矿物膜",揭示出太阳光照射下的地球陆地表面普遍存在的"矿物膜"与太阳光有着直接的响应关系。光电化学测试结果显示,天然"矿物膜"具有较好的日光响应性能,由其制成的电极在可见光照射下皆能产生明显的光电流,而不含铁锰氧化物矿物的岩石基质样品及石英、长石等矿物样品几乎不产生光电流,表明"矿物膜"光电流的产生主要与铁锰氧化物有关。进一步测得"矿物膜"中主要铁锰氧化物的禁带宽度均小于2. 5eV,证明其均为对可见光具有广泛而良好吸收的天然半导体矿物。以全球日光平均辐照强度100mW/cm~2计以及全球典型生境中"矿物膜"分布面积估算,全球"矿物膜"吸收太阳能等效为生物质能的最大量与2017年度全球糖类产量(1. 92亿吨)相当。铁锰氧化物"矿物膜"不仅存在于陆地地表,还存在于海洋透光层中。可以认为地表"矿物膜"是地球上分布最广的天然"太阳能薄膜",从功能上"矿物膜"相当于继地核、地幔和地壳之后的地球第四大圈层,事实上构成了地球"新圈层",也是地球在太阳光能量驱动下发生外营力地质作用的关键地带。在此基础上,本文提出从"矿物膜"中产生的矿物光电子与太阳光子和元素价电子共同组成了地表存在的三种主要能量形式的认识。深入探讨太阳光照射下地表多圈层交互作用界面上所发生的电子传递与能量转化的微观机制,有助于深刻理解地表"矿物膜"这一地球"新圈层"如何影响地球物质演化、生命起源进化与环境变化演变的宏观过程。     

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。     

天然矿物光电效应:矿物非经典光合作用

地球上生物因受到太阳光辐射作用而进化出结构精致的光合作用系统。太阳光辐射对地球表面广泛分布的无机矿物的影响与响应机制长期未被重视与理解。我们新发现的地表“矿物膜”转化太阳能系统,具有潜在的产氧固碳作用,体现出自然界中固有的矿物光电效应与非经典光合作用。本文在总结自然界中矿物光电子能量特征,特别是地表“矿物膜”特征及其光电效应性能的基础上,重点探讨铁锰氧化物矿物表现出的光电效应、产氧固碳作用与地质记录。提出矿物享有光电效应特性,地表“矿物膜”富含水钠锰矿、针铁矿、赤铁矿等天然半导体矿物,在日光辐射下具有稳定而灵敏的光电转换性能,产生矿物光电子能量;提出矿物拥有非经典光合作用的性能,自然界无机矿物转化太阳能系统类似生物光合作用吸收转化太阳能的产氧固碳系统,地表“矿物膜”光催化裂解水产氧作用及其转化大气和海洋二氧化碳为碳酸盐矿物作用,孕育出“矿物光合作用”;提出矿物具有促进生物光合作用的功能,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锰簇化合物结构体,初步认为水钠锰矿可能促使蓝细菌光合作用系统的起源,矿物影响与削弱水分子氢键以改变水的性质,可提高水的分解程度与光合作用效率,为进一步探索矿物促进生物光合作用机理提供科学技术突破的机遇。     

Natural mineral photoelectric effect: mineral non-classical photosynthesis

Under the ever-present solar radiation, photosynthetic organisms on Earth evolved structurally-sophisticated photosynthetic systems. However, little attention has been paid to the inherent impact of sunlight illumination on the inorganic minerals widespread on the Earth surface. We discovered for the first time the solar energy conversion system of the “mineral coatings” on the Earth's surface (aka“mineral membrane”), which exerts potential oxygen-production and carbon-sequestration functions on the Earth surface. Our finding shed a light on the photoelectric effect and non-classical photosynthesis involving natural semiconducting minerals. In this contribution, we studied the semiconducting property and photoelectron energy of typical minerals in the “mineral membrane”, focusing primarily on the photoelectric effect in and oxygen-production/carbon-sequestration function of ferromanganese oxides, as well as relevant geological records. We propose that birnessite, goethite and hematite, the semiconducting minerals commonly found in the “mineral membrane”, can perform sensitive and stable photon-to-electron conversion under solar radiation. The non-classical mineral photosynthetic function we put forth is as follows: Solar energy utilization by inorganic minerals resembles photosynthesis in regarding to oxygen evolution and carbon fixing, and the “mineral membrane” may take part in both photocatalytic water-oxidation reaction and transformation of atmospheric CO₂into marine carbonate. In addition, minerals might as well have promoted photosynthesis in photosynthetic organisms. During the water-oxidation reaction, the inorganic cluster Mn₄CaO₅of photosystem II cycles through redox intermediates that are analogous to birnessite both in structure and component. Thus, it is fair to postulate that birnessites could play a role in the initiation of the photosynthesis in cyanobacteria, as minerals could weaken the hydrogen bond strength and alter water properties, thus facilitating water oxidation and photosynthesis. This observation offers further insights into the molecular mechanism of mineral participation in photosynthesis in photosynthetic organisms.     

微生物所协同的天然金红石日光催化作用研究

本文揭示了自然界中可能存在的一种新的矿物和微生物交互作用形式,即微生物通过生物电化学作用参与到半导体 矿物的日光催化作用过程中。模拟日光光源下“产电”微生物与天然半导体矿物金红石交互实验结果显示,金红石的光催 化作用促进了矿物端元的反应速率,提高了电子在微生物和矿物之间的转移效率,使微生物电子传递链末端电子能量得到 提升。二者协同作用可提高微生物或半导体矿物单独作用时对污染物如Cr(Ⅵ)的还原处理效果。该研究为环境污染治理提 供了一种矿物与微生物协同作用新理念。     

化能自养型微生物利用太阳能途径的实验研究

针对自然界中天然半导体矿物和化能自养微生物之间的能量交换途径进行了详细的实验研究.半导体光电化学实验结果显示,天然半导体矿物在光照情况下产生的光生电子可将Fe3+还原为Fe2+,其中金红石光催化还原Fe3+的效率为12.5%,闪锌矿为7.86%,该过程通过天然半导体矿物的日光催化作用实现了太阳光能→电能→化学能的转化;控制电势的微生物电化学反应实验结果显示,化能自养型微生物A.f.菌的细胞增加量与外界电子传入而生成的Fe2+的量呈线性关系,且有外来电子传入实验组的A.f.生长量是无电子传入组的441%,该过程通过菌的生长代谢作用实现了化学能→生物质能的转化.进一步的光电化学和微生物电化学耦合实验结果证明,在太阳光和天然半导体矿物共同作用下,A.f.菌的对数生长期由无光时的36 h延长到72 h,同时细菌的生长在该能量转化过程中得到了明显促进.在天然闪锌矿催化条件下,有光条件的A.f.菌数量增加到无光条件的1.90倍;而在金红石催化条件下,有光条件的A.f.菌数量增加到无光条件的1.69倍.实验结果说明,在以天然半导体矿物为媒介的情况下,化能自养微生物可间接利用太阳能来获得自身的生长繁殖所需的能量,这一过程也实现了太阳光能→电能→化学能→生物质能的能量转化途径.     

微生物成矿

微生物对生命元素如碳、氮、硫、氧和金属离子的代谢作用能显著的改变微生物周边的外部环境和其内部环境。在一系列的生物地球化学过程中,微生物参与了矿产的沉积(生物成矿)或参与了矿石和岩石的溶解(生物风化)。生物成矿作用有两个途径：一个叫生物诱导成矿,通过这个过程,微生物分泌出代谢产物导致了之后的矿物颗粒的沉积;另一个叫生物控制成矿,在这个过程中,微生物在控制矿物成核和生长上起到了显著作用。微生物成因的矿物总体来说颗粒都很小和／或有着独特的同位素特征。最普遍的生物成因矿物有碳酸盐、硫化物和铁的氧化物。细胞表面和其分泌的胞外聚合物的结构可以为离子的浓缩、聚合和矿化提供模板,并起到重要作用。地球材料的仿生合成帮助我们了解了在人工条件下的生物成矿机制。此外,在地质环境中生物成因的矿物还可以作为一种生物信号,用来重建地球和其他行星的起源和演化。     

地表“矿物膜”中锐钛矿-β-胡萝卜素协同增强日光响应特性研究

为探究"矿物膜"中半导体矿物与光合色素间的日光响应协同作用,对采自安徽潜山市郊的"矿物膜"样品进行了矿物组成和色素组成分析。同步辐射X射线粉末衍射测定表明,样品富含锐钛矿、赤铁矿等半导体矿物;拉曼光谱证实其中存在地表广泛分布的光合色素:β-胡萝卜素。在此基础上开展锐钛矿-β-胡萝卜素协同增强日光响应模拟实验。合成锐钛矿电极并对其进行系统的矿物学表征,紫外-可见漫反射吸收谱计算其禁带宽度约为3.07 eV;莫特-肖特基计算得到的平带电位约为-0.16 V,载流子浓度约为3.25×1026 cm-3;光电化学测试结果显示其具有一定可见光光电转化能力。经β-胡萝卜素敏化处理后,锐钛矿电极平均光电流密度提升了400%,在425~550 nm间光吸收值提高,该波段位于日光辐射能量集中的波长范围内,且与β-胡萝卜素吸收范围吻合,表明二者间存在日光吸收及光电响应协同增强作用。     

Advances in the Semiconductor-Mediated Electron Transfer Mechanism at Microbe-Mineral Interface

The interaction between minerals and microbes is an important biogeochemical process in the earth surface system, which links the transformation of substances and energy exchange in different earth spheres, and also affects a series of important earth surface processes, including the formation and evolution of secondary minerals, nutrient cycling and environmental behaviors of pollutants. The previous studies on microbe-mineral interaction focused on the extracellular electron transfer, and the microbe-mediated dissolution, precipitation, mineralization of minerals. Because of semiconductor properties of the mineral, it plays a special role in the process of microbial extracellular electron transfer, which can also help to understand the mutual interaction between microbe and mineral from a new angle of view. The unique energy level structures and redox properties of semiconducting mineral lead to a great difference in the mechanism of microbe and mineral interaction. The latest research progresses in the mechanism of microbe-mineral interaction mediated by semiconducting mineral were reviewed from two aspects: driven by thermodynamics and light energy. Finally, the future development trends of the interaction between microbes and semiconductor minerals were prospected.     

地表“矿物膜”半导体矿物光电子调控微生物群落结构演化特性研究

矿物-微生物交互作用广泛参与地球表层系统物质循环与能量流动过程,深刻地影响着一系列重要的地表生物地球化学进程。近年来地表半导体矿物的相关研究,为矿物-微生物交互作用提供了崭新研究方向,揭示地表“日光-半导体矿物-微生物”系统电子传递过程及其环境效应,是地质微生物学交叉领域研究的核心科学问题之一。本研究从地表不同生境“矿物膜”出发,以光电化学技术证实喀斯特、红壤、岩石漆“矿物膜”在1 000 min长时间循环实验中平均光电流值约为5.4、3.4、3.2 μA/cm²,证实“矿物膜”良好日光响应特性且铁锰氧化物矿物在其中发挥核心作用。基于笔者前期研究所发现的“矿物膜”电活性菌富集且与半导体矿物分布呈正相关性这一现象,本文进一步构建模拟光电子红壤细菌群落系统,20天后细菌群落α多样性显著提升,研究证实细菌群落具有模拟光电子响应活性,且电极与溶液群落均具有演化方向性;16S rRNA测序分析表明模拟光电子作用下Shewanella、Pseudomonas、Streptococcus、Lactobacillus、Acinetobacter等电活性菌显著富集。综上,本文研究结果间接证实地表半导体矿物光电子可有效调控微生物群落结构并促进电活性菌在“矿物膜”中富集。     

Semiconducting Mineral Photocatalytic Regeneration of Fe2+ Promotes Carbon Dioxide Acquisition by Acidithiobacillus ferrooxidans

Chemoautotrophic organisms have once been excluded from the development of universally applicable CO2 fixation technology due to its low production yields of biomass. In this study, we used Acidithiobacillus ferrooxidans (A.f.) as a model chemoautotrophic microorganism to test the hypothesis that exogenetic photoelectrons from semiconducting mineral photocatalysis can enable the regeneration of Fe2+ that could be then used by A.f. and support its growth. In a simulated electrochemical system, where exogenetic electrons were provided by an electrochemical approach, an accelerated growth rate of A.f. was observed as compared with that in traditional batch cultivation. In a coupled system, where light-irradiated natural rutile provided the primary electron source to feed A.f., the bacterial growth rate as well as the subsequent CO2 fixation rate was demonstrated to be in a light-dependent manner. The sustaining flow of photogenerated electrons from semiconducting mineral to bacteria provided an inexhaustible electron source for chemoautotrophic bacteria growth and CO2 fixation. This finding might contribute to the development of novel effective CO2 fixation technology.     

Advances in the microbial mineralization of seafloor hydrothermal systems

Research on the biomineralization in modern seafloor hydrothermal systems is conducive to unveiling the mysteries of the early Earth’s history, life evolution, subsurface biosphere and microbes in outer space. The hydrothermal biomineralization has become a focus of geo-biological research in the last decade, since the introduction of the microelectronic technology and molecular biology technology. Microorganisms play a critical role in the formations of oxide/hydroxides (e.g. Fe, Mn, S and Si oxide/hydroxides) and silicates on the seafloor hydrothermal systems globally. Furthermore, the biomineralization of modern chemolithoautotrophic microorganisms is regarded as a nexus between the geosphere and the biosphere, and as an essential complement of bioscience and geology. In this paper, we summarize the research progress of hydrothermal biomineralization, including the biogenic minerals, the microbial biodiversity, and also the interactions between minerals and microorganisms. In the foreseeable future, the research on hydrothermal biomineralization will inspire the development of geosciences and biosciences and thus enrich our knowledge of the Earth’s history, life evolution and even astrobiology.© 2019 China Geology Editorial Office.     

西藏甲玛铜多金属矿硫同位素地球化学研究

西藏墨竹工卡县甲玛铜多金属矿床位于冈底斯成矿带东段,Cu、Mo、Pb+Zn、Au、Ag均达大型规模,并伴生Co、Bi、W、Ni等多金属矿化。黄铜矿、斑铜矿、辉钼矿、方铅矿、闪锌矿、黝铜矿、辉铜矿等硫化物为主要的矿石矿物,硫酸盐矿物以硬石膏为主,含矿岩浆岩以花岗斑岩、二长花岗斑岩和花岗闪长斑岩为主。通过对甲玛矿区主要硫化物和硬石膏的硫同位素分析,并结合前人研究,甲玛矿区硫化物的硫同位素δ34S值变化于13.6‰～+12.5‰,平均值1.33‰(样品数86)、硬石膏δ34S值+0.5‰～+1.8‰,平均值+1.13‰(样品数3)、岩浆岩δ34S值0.7‰～0.2‰,平均值0.5‰(样品数3),与岩浆硫δ34S值0±3‰一致。闪锌矿-方铅矿-黄铜矿矿物对的硫同位素地质温度计,显示成矿温度为408～433℃,说明其形成时硫同位素处于平衡状态。冈底斯成矿带上的驱龙等斑岩型矿床中硫化物和岩浆岩硫同位素,均具有δ34S值变化范围小,平均值接近0值,与岩浆硫特征一致的特点,反映了甲玛铜多金属矿床具有矽卡岩-斑岩型矿床硫同位素地球化学特征,硫以岩浆来源为主。     

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.     

Symmetry statistics of mineral species and the evolutionary dissymmetrization of mineral matter

A comprehensive statistical analysis of the symmetry of mineral species leads to a definite conclusion that rare minerals possess lower symmetry than abundant ones, so that the most stable minerals are characterized by higher symmetry. Since all recently discovered new minerals belong to rare and very rare species, their percentage is increasing and the mean symmetry index is decreasing with time. In other words, the average symmetry is gradually decreasing with the growing diversity of mineral species. In general, the irreversible process of rare mineral formation obeys the principle of minimum dissymmetrization. At the same time, the reduced symmetry indices strongly decrease on passing from cosmic materials (meteorites, lunar rocks) to the Earth’s solid substances and from the planetary interior (core, mantle) to the Earth’s crust. This trend of the planet’s evolution is related to the pronounced loss of entropy and increase in ordering of solid substances that compose the lithosphere. This is supplemented by the withdrawal of entropy from the solid to the upper liquid (oceans) and gaseous (atmosphere) shells of the Earth and farther to the surrounding space.     

红壤中微生物群落对半导体矿物日光催化作用的响应

本研究选取天然红壤作为研究对象,分析其中的含铁半导体矿物光催化作用对本源微生物群落结构的影响。采用聚 合酶链式反应/变性梯度凝胶电泳（PCR-DGGE）,研究了不同原始光照条件的红壤中微生物群落在外源电子作用下群落结 构的改变。DGGE图谱的主成分分析表明,两个不同原始光照环境的土壤样品的微生物群落结构由于原始环境的差异而不同： 原始环境为强光照的样品中微生物群落结构受外源电子影响较小;原始环境为弱光照的样品中微生物群落结构受外源电子 影响较大。这一群落结构改变的差异可能由于原始环境为强光照时半导体矿物光催化作用产生光生电子传递到环境中持续 影响周围的微生物群落,而原始弱光照环境中则缺少光生电子的作用。     

微生物影响硅酸盐矿物风化作用的模拟试验

研究了硅酸盐细菌对矿物的风化作用。选用土壤中常见的钾长石、伊利石等矿物作为细菌风化作用的对象,通过在含有矿物颗粒的无氮培养基中培养硅酸盐细菌,使其在培养液中与矿物颗粒发生相互作用,再取样并处理后进行电镜观察和X-射线衍射分析。电镜观察结果表明细菌对矿物试样表面确实发生了溶蚀作用,被细菌作用后的矿粉,颗粒浑圆,边缘模糊不清,表面呈凹凸不平状,矿物颗粒被大量的菌体物质所覆盖。用X-射线衍射分析检测到细菌对具不同晶体结构矿物的“选择性”破坏作用,在有多种矿物同时存在的情况下,细菌对较易分解的矿物破坏作用速度较快。结合矿物学与微生物学相关知识,初步分析了细菌培养液中细菌与矿物界面之间的相互作用以及土壤生态系统中矿物的生物风化作用过程。     

Accretion of Moon and Earth and the emergence of life.

The discrepancy between the impact records on the Earth and Moon in the time period, 4.0-3.5 Ga calls for a re-evaluation of the cause and localization of the late lunar bombardment. As one possible explanation, we propose that the time coverage in the ancient rock record is sufficiently fragmentary, so that the effects of giant, sterilizing impacts throughout the inner solar system, caused by marauding asteroids, could have escaped detection in terrestrial and Martian records. Alternatively, the lunar impact record may reflect collisions of the receding Moon with a series of small, original satellites of the Earth and their debris in the time period about 4.0-3.5 Ga. The effects on Earth of such encounters could have been comparatively small. The location of these tellurian moonlets has been estimated to have been in the region around 40 Earth radii. Calculations presented here, indicate that this is the region that the Moon would traverse at 4.0-3.5 Ga, when the heavy and declining lunar bombardment took place. The ultimate time limit for the emergence of life on Earth is determined by the effects of planetary accretion--existing models offer a variety of scenarios, ranging from low average surface temperature at slow accretion of the mantle, to complete melting of the planet followed by protracted cooling. The choice of accretion model affects the habitability of the planet by dictating the early evolution of the atmosphere and hydrosphere. Further exploration of the sedimentary record on Earth and Mars, and of the chemical composition of impact-generated ejecta on the Moon, may determine the choice between the different interpretations of the late lunar bombardment and cast additional light on the time and conditions for the emergence of life.     

太阳星云凝聚过程的岩石学模型：（1）球粒陨石的凝聚成因

建立类地行星区太阳星云凝聚过程的岩石学模型，对于合理解释陨石、地球和类地行星的成因关系，探讨地球起源和估算地球的整体成分都有着重要意义。本文中根据天体化学和太阳系演化学说关于太阳星云物理化学条件的基本分析，以及实验凝聚岩石学的研究结果，推断在太阳星云盘的类地行星区中可能有星云的气－固和气－液－固两种凝聚作用发生。通过对球粒陨石中球粒和基质矿物成分及结构构造特征的对比，论证了绝大多数球粒的气－液－固凝聚成因和基质的气－固凝聚成因，并讨论了球粒陨石各化学群的凝聚成因模式。