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.     

微生物电化学体系中金红石可见光还原降解偶氮染料的实验研究

利用双室微生物电化学装置对微生物和半导体矿物协同作用下偶氮类染料废水的还原脱色降解进行了系统的实验研究.不同光照条件及不同阴极电极材料的对比实验结果显示,偶氮染料甲基橙(MO)可作为终端电子受体直接从固体电极上获得电子被还原脱色;各对比实验中,在微生物催化与半导体矿物光催化协同作用条件下,MO还原脱色效率最高.电化学交流阻抗谱(EIS)的拟合结果显示金红石涂布阴极电极光照下极化内阻(Rp)为443.4 Ω,较无光条件下的1378 Ω显著降低,证明光照下金红石阴极的电子转移过程受其光催化作用的驱动.不同初始浓度下MO的生物-半导体催化还原反应符合准一级动力学模型,其反应速率随MO初始浓度降低而增加.通过对脱色产物的进一步分析,推测该实验中MO的还原脱色反应机制为: 阳极初始电子供体在微生物的催化作用下将电子通过阳极电极和外电路传递给阴极半导体矿物电极,进而在半导体矿物的光催化作用下通过光生电子还原终端电子受体MO,使MO中的偶氮键断裂,生成无色的联氨类衍生物.     

关键带中天然半导体矿物光电子的产生与作用

在地球上最不均匀和最复杂的区域——关键带这一极为复杂的开放系统中,矿物与微生物无时无刻不在发生着人们尚未充分认识到的自然作用。文中总结了作者十余年来在矿物与微生物交互作用研究领域,侧重在半导体矿物与微生物协同作用研究方向上所取得的研究成果,重点简述了自然界中半导体矿物特征、半导体矿物光电子特性、矿物光电子促进生命起源与演化、微生物利用矿物光电子——光电能微生物的发现以及土壤矿物光电子与微生物协同固碳作用等研究工作。矿物与微生物之间电子转移和能量流动是关键带中最为重要的动力机制之一,探讨关键带中大量存在的天然半导体矿物如何转化太阳能为化学能或者生物质能的微观作用,可为揭示关键带中多个圈层之间交互作用如何影响地球物质演化、生物进化与环境演变的宏观过程提供理论依据,充满着科学发现与理论突破的机遇。     

无机界矿物天然自净化功能之矿物光催化作用

在简述半导体光催化理论及TiO2多相光催化作用近30年研究现状的基础上，重点对国内外一直处于空白状态的天然含钒金红石光催化性能进行研究。天然含钒金红石中部分Ti^4 被V^5 包括Fe^3 、Cu^2 和Zn^2 等杂质离子替代可引起其晶格畸变与缺陷。机械粉碎到70～80μm后可使其晶胞膨胀0.33％，原位加热700～1100℃其晶胞可膨胀0．93％～2．13％，淬火改性其晶胞收缩0．01％～0．07％。受热改性其体相中V^5 向表面偏析。对晶格畸变的修复可表现为晶面重构和再结晶作用及微应力释放作用。粉碎的金红石对卤代烃三氯乙烯和四氯乙烯具有一定的降解效果而表现出良好的光催化活性。加热1000℃，金红石对卤代烃的降解率明显提高。淬火1000℃和1100℃，金红石对卤代烃的降解速度大大加快。而电子辐射金红石对三氯乙烯的降解率则明显降低。通过52种金属氧化物和金属硫化物半导体矿物的初步研究，发现大多数金属氧化物矿物产生光电子的波长范围是249～777nm，吸收光主要是可见光。而大多数金属硫化物矿物产生光电子的最大波长大于921nm，吸收光主要是红外光，充分表明无机界具有光催化功能的半导体在可见光条件下就可以产生光电子与空穴。系统开展无机界矿物光催化作用研究，对揭示地球生命过程和环境演化有着不可替代的作用，对氧化降解地球表层系统中有机污染物尤其是不能自行降解的持久性有机污染物有着至关重要的作用。     

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。     

黄海透光层悬浮半导体矿物组成及其促进微生物胞外电子传递过程初探

在地球上最为活跃的海洋透光层体系中,矿物-微生物交互作用的形式十分丰富。系统采集了黄海近海透光层水体样品,测试分析发现其中分布大量悬浮半导体矿物及微生物群落。通过电感耦合等离子质谱仪(ICP-MS)、环境扫描电子显微镜(ESEM)及配有的EDX能谱仪,从宏观到微区对悬浮颗粒矿物的化学元素组成进行了测试分析,发现其主要矿物组成元素为Si、O、Na、K、Ca、Al等,且含有较高含量的Mn、Fe、Ti等金属元素;通过X射线衍射光谱(XRD)、拉曼光谱(Raman)测试从整体到局部分析悬浮颗粒矿物的物相组成,发现其主要组成矿物为石英、钠长石、方解石、云母和绿泥石等,还有锐钛矿、金红石、板钛矿、针铁矿等铁、钛金属氧化物半导体矿物。通过16S rRNA高通量测序分析海水中主要微生物群落为Proteobacteria、Actinobacteria、Bacteroidetes、Planctomycetes、Woeseia、Fluviicola等,并通过构建双室反应体系对海水微生物与悬浮矿物间氧化还原作用及胞外电子传递过程进行了表征,结果显示增加海水悬浮矿物作为电子受体后,体系开路电压由330. 80 mV提升至426. 59 mV,提升比率达130%,最大输出功率由8. 376 9 mW/m^2提升至12. 096 8 mW/m^2,为原体系的1. 44倍。实验研究表明,海水透光层悬浮矿物能有效参与并促进微生物胞外电子传递过程,为后续深入研究基于电子能量传递利用的半导体矿物-微生物协同作用以及元素循环调控机制奠定初步基础。     

热处理天然金红石的微结构研究

利用粉晶X射线衍射(XRD)、透射电镜(TEM)等分析手段对在氩气气氛中加热、退火的天然金红石样品的微结构进行了研究.研究表明样品在热处理后,晶格发生膨胀,并且在900 ℃和1000 ℃的样品中出现了钛铁矿物相.钛铁矿也是一种天然半导体矿物,沿与金红石(010)面网成大约31°夹角的方向生长,与金红石形成了二元复合半导体.紫外漫反射实验结果表明热处理后,金红石中出现的钛铁矿相有效地促进了光催化效果.     

矿物光电子-微生物体系重金属离子价态调控及其环境效应研究进展

本文综述了典型污染区重金属离子赋存状态与环境风险评价、环境微生物多样性等环境质量因子的关系及其对土壤功能的影响;重点介绍了微生物源电子、半导体矿物光电子对重金属离子的价态调节双向控制;总结了电子穿梭体、空穴捕获剂等小分子有机物对光电子还原重金属离子的影响及机制,以及半导体矿物光电子、重金属价电子协同微生物对重金属离子的还原氧化效率与价态调控;分析了微生物及其表面基团对重金属离子的矿化与转化作用,以及微生物界面固定转化在土壤重金属污染修复中的作用。本综述可为进一步研究微生物和半导体矿物光电子协同作用对重金属离子的定向调节、电子转移途径、晶相转化机制提供指导,对深入探讨光-半导体矿物-重金属离子-微生物多相复杂体系的交互作用具有重要的环境学意义。     

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。     

矿物光电子能量及矿物与微生物协同作用

本文总结了天然半导体矿物光电子能量及矿物与微生物协同作用的最新研究成果,特别强调地表微生物、矿物和太阳光多元复杂体系中金属氧化物和金属硫化物半导体矿物的可见光激发光电子特征,阐述了矿物光电子能量利于地球早期生命起源与演化、促进化能自养和化能异养微生物生长代谢、调控矿物与微生物协同作用实现固碳作用。进而提出矿物光电子能有效地将二氧化碳还原为有机物质,可为生命起源提供有机物质基础的认识。     

Photoelectrons from Minerals and Microbial World

The Earth surface is a multiple open system. Semiconducting minerals, including most metal oxides and sulfides, absorb visible light of the solar spectrum. Microorganisms evolve varied pathways to get carbon and energy sources. It is obvious that the interaction among solar light, semiconducting minerals, photoelectron/photohole, organics, inorganics, valence electrons and microorganisms occurs continuously on our planet. In a recent study, Lu et al. (2012) presented evidence demonstrating solar energy mediated by semiconducting mineral photocatalysis, acting as energy source, promoted the growth of some non-photosynthetic bacteria and revealed that the ternary system of microorganisms, minerals and solar light has played a critical role in the history of life on our planet. In simulated system, under simulated solar light semiconducting minerals, such as metal oxides and metal sulfides, generates photoelectrons which could be used by non-phototrophic microorganisms to support their metabolisms. The growth of microorganism was closely related to photon quantity and energy, and the microorganism growth and mineral light absorption spectra were fitted well under different light wavelengths. The overall energy efficiency from photon to biomass was 0.13‰ to 1.9‰. Further studies revealed that in natural soil systems, semiconducting mineral photocatalysis could influence the microbial population. Solar energy utilization pathway by nonphototrophic microorganisms mediated by semiconducting mineral photocatalysis provides a new concept to evaluate the origin and evolution of life. Semiconducting minerals are ubiquitous on Earth’s surface and widely participate in redox reactions following photoelectron-photohole pairs excited by solar light. As photoholes can be easily scavenged by environmental reductive substances and microorganisms possess multiple strategies to utilize extracellular electrons, the highly reductive photoelectrons serve as potential energy source for microbial life. The discovery of this pathway extends our knowledge on the use of solar energy by nonphototrophic microorganisms, and provides important clues to evaluate life on the early Earth. Microorganisms, minerals and solar light constitute a complex but important ternary system through Earth history. The discovery of the novel energy conversion pathway in this system demonstrates how nonphototrophic microorganisms directly or indirectly utilized photoelectrons as the solar energy source. The fully comprehending of nonphototrophic bacteria solar energy utilization conducted by semiconducting minerals in present environment will greatly help us to better understand the energy transform mechanism among interfaces of lithosphere, pedosphere, hydrosphere and biosphere.     

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.     

Redistribution of HFSE elements during rutile replacement by titanite

Titanite growth at the expense of rutile during retrograde hydration of eclogite into amphibolite is a common phenomenon. We investigated an amphibolite sample from the Tromsø eclogite facies terrain in Northern Norway to gain insight into the trace element distribution between rutile and titanite during incomplete resorption of the rutile by titanite. Patchy compositional zoning of Al, Ti, and F in titanite relates to the presence of a fluid with variable Ti/Al and/or F during its growth. Laser ablation ICP–MS and electron microprobe data for high field strength elements (HFSE: Nb, Zr, Ta, and Hf) of rutile resorbed by titanite indicate a pronounced enrichment of these elements in the rim of a large single rutile crystal (~8 mm) and a systematic decrease towards uniform HFSE contents in the large core. HFSE contents of smaller rutile grains (~0.5 mm) and rutile inclusions (<100 μm) in the titanite overgrowth are similar or higher than in the rims of large rutile crystals. Element profiles from the rim inward demonstrate that HFSE enrichment in rutile is controlled by diffusion. HFSE ratios in diffusion-altered rutile show systematic variations compared with the uniform core composition of the large rutile. Modelling of Zr and Nb diffusion in rutile indicates that diffusion coefficients in rutile in fluid-dominated natural systems must be considerably higher than those determined experimentally at 1 bar in dry systems. Variations of HFSE contents in the newly formed titanite show no systematic spatial distribution. HFSE ratios in titanite and the rims of rutile are different, indicating different solid/fluid distribution coefficients in these minerals. Element fractionation by diffusion into the relict rutile and during fluid-mediated growth of new titanite could substantially change the HFSE budget of these minerals and could affect their use for geochemical tracing and other applications, such as Zr-based geothermobarometry.     

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。     

Redox-linked conformation change and electron transfer between monoheme c-type cytochromes and oxides

Electron transfer between redox active proteins and mineral oxides is important in a variety of natural as well as technological processes, including electron transfer from dissimilatory metal-reducing bacteria to minerals. One of the pathways that could trigger electron transfer between proteins and minerals is redox-linked conformation change. We present electrochemical evidence that mitochondrial cytochrome c (Mcc) undergoes significant conformation change upon interaction with hematite and indium-tin oxide (ITO) surfaces. The apparent adsorption-induced conformation change causes the protein to become more reducing, which makes it able to transfer electrons to the hematite conduction band. Although Mcc is not a protein thought to be involved in interaction with mineral surfaces, it shares (or can be conformed so as to share) some characteristics with multiheme outer-membrane cytochromes thought to be involved in the transfer of electrons from dissimilatory iron-reducing bacteria to ferric minerals during respiration. We present evidence that a 10.1 kDa monohoeme cytochrome isolated and purified from Acidiphilium cryptum, with properties similar to those of Mcc, also undergoes conformation change as a result of interaction with hematite surfaces.     

On the origin of oriented rutile needles in garnet from UHP eclogites

Although oriented rutile needles in garnet have been reported from several ultrahigh‐pressure (UHP) rocks and considered to be important UHP indicators, their crystallographic features including growth habit and lattice correspondences with garnet host have never been properly characterized. This paper presents a detailed analytical electron microscopic (AEM) study on evenly distributed oriented rutile needles in garnet of two eclogitic rocks from Sulu. Some garnet in one UHP diamondiferous quartzofeldspathic rock from the Saxonian Erzgebirge, and in one high‐pressure (HP) felsic granulite from Bohemia also contain a few unevenly distributed oriented rutile needles. They have also been studied for the purpose of comparison. Despite different distribution patterns, AEM revealed that all rutile needles are oriented along the 〈111〉 directions of garnet with their lateral sides surrounded by the {110} planes of garnet, and that the growth directions of most needles are close to the normal of the {101} planes of rutile. No other specific crystallographic orientation relationships between rutile and garnet host were observed, and there is no pyroxene associated with rutile, as necessitated by the precipitation reaction of rutile in garnet as previously proposed. A simple solid‐state precipitation scenario for the formation of the rutile needles in garnet in these two eclogitic rocks is not justified. Three alternative mechanisms are considered for the formation of oriented rutile needles: (i) the rutile needles may be inherited from precursor minerals; (ii) the rutile needles may be formed by a dissolution–reprecipitation mechanism; and (iii) the rutile needles may be formed by cleaving and healing of garnet with rutile deposition. None of these mechanisms can fully explain the observations, although the first one is less likely and the third one is preferred. This study presents an example where the presence of oriented/aligned inclusions in minerals does not necessarily imply a precipitation origin.     

天然黑钨矿可见光催化活性的实验研究

天然半导体矿物具有优良的日光催化特性。本研究选取天然钨酸盐作为研究对象,对武鸣、栗木、崇义3个不同矿区的天然黑钨矿进行了矿物学及光催化实验探究。利用X射线衍射、拉曼光谱、红外光谱、电子探针微区分析对天然样品的结构与成分进行分析,鉴定其主要矿物相为黑钨矿(Fe,Mn)[WO4],从武鸣、栗木到崇义矿区,Fe/Mn摩尔分数比从7.1、0.9到0.3依次降低。利用紫外可见漫反射测得武鸣、栗木、崇义地区样品禁带宽度分别为1.5、1.6和1.7eV,说明其具有良好的可见光响应。在pH为7的条件下用质量浓度为1g/L的样品对5mg/L的有机染料亚甲基蓝(MB)进行光催化实验(含0.01mol/L H2O2 ),结果表明武鸣地区黑钨矿实验组降解MB的效果最佳,3h后其效率分别是栗木、崇义地区样品的1.1倍和1.6倍。电子顺磁共振谱检测结果显示,反应过程中均产生氧化性羟自由基(·OH),其中效果最好的武鸣黑钨矿产生的·OH信号更强;不同自由基捕获实验证明·OH在光催化反应过程中起主要作用。进一步选取武鸣黑钨矿开展光催化降解机制研究,实验结果显示:光照下黑钨矿与H2O2共存的实验组对MB的脱色降解率可达99%(3h),只有黑钨矿的对照组降解7%的MB,只有H2O2 的对照组降解31%的MB;黑暗条件下,同时添加黑钨矿与H2O2的对照组对MB的去除率为34%。不同H2O2 浓度条件下黑钨矿降解MB符合准一级动力学方程,说明降解过程与催化剂含量无关,H2O2 更多的是充当电子受体。分析认为,不同产地黑钨矿日光催化效率与矿物铁含量呈正相关,与禁带宽度呈负相关,推测其反应机理是光催化与芬顿反应协同产生的·OH将MB氧化降解。本研究为开发利用天然矿物治理环境污染提出了新方法。