纳米矿物-水溶液界面过程

在地球环境中普遍存在的纳米矿物-水溶液界面对许多基本的地球化学过程都至关重要,因而是纳米地球化学的前沿核心研究领域.简要介绍了纳米矿物-水溶液界面领域的基本概念和近期研究进展.举例描述了纳米矿物团聚、吸附、溶解和化学反应等几个相互关联的主要过程,具体阐述了纳米矿物自身特征（如组成、结构、尺寸、形貌、表面保护剂等）以及环境介质条件（如pH、离子强度、化学反应物质、天然有机质浓度和组成、微生物、光辐射等）对纳米矿物-水溶液界面过程的影响规律和微观机制.针对本领域发展面临的机遇和挑战,为未来的研究方向提出了一些设想和建议.      

纳米尺度下的生物矿物和生物矿化:基于介晶的视角

纳米地质学的兴起和发展,促使地质工作者从纳米尺度重新认识固体地球物质,将对地球科学的各个领域产生广泛而深刻的影响.作为纳米地质学的重要分支,纳米矿物学也将走出传统矿物学只把矿物看成理想晶体点阵的局限,从纳米尺度深入探究矿物包括生物矿物在内的矿物结构与性质,突破口之一是介晶.介晶是一种特殊的结晶纳米结构,近年来得到了物理学家和化学家尤其是材料化学家越来越多的关注.介晶是非经典结晶过程产物,以纳米颗粒为基本构筑单元,具备纳米颗粒的性质和宏观尺寸.现已发现,许多生物矿物如脊椎动物骨骼和牙齿、贝壳珍珠层、蛋壳、海胆骨针、有孔虫和珊瑚等都具有介晶结构.因此,从纳米尺度和介晶角度重新理解生物矿化,有助于揭示生物矿物中纳米多级结构的成因机制,拓展纳米矿物学的科学内涵.首先介绍生物矿化和生物矿物的基本概念,之后对介晶的概念和结构特征进行阐述,最后介绍生物矿物中的介晶结构及介晶形成的典型机制,涉及有机基质辅助、物理场驱动、矿物桥或有机桥连接、空间限域、取向附集和晶面选择性分子作用等多种物理化学过程,有望进一步推动纳米矿物学的发展.      

环境矿物界面反应动力学

环境矿物界面反应动力学主要探讨地表中各种有毒、有害离子或分子与矿物表面之间的反应速率与反应机制。矿物表面存在一组化学活性很强的表面功能基，当它们与环境中毒害物质发生作用时，会因其极性、荷电性和Lewis酸碱性不同而表现出不同的作用力和反应速率，进而控制有毒、有害物质在大气、水体和沉积物中的赋存形态，稳定性及迁移转化速率。本文简要介绍了环境矿物界面反应动力学理论，并给出几个应用实例。     

企鹅贝珍珠层生物表界面ACC析出与相变及多级自组装生长

<正>珠母贝珍珠层生物矿化作用区别于一般无机矿物矿化的显著特征是,通过生物表界面处生物大分子(蛋白质、核酸、多糖等)基因的表达与诱导,从分子水平调控生物矿物前驱体(ACC)纳米球粒的析出与相变,从而使生物矿物具有特殊的生物矿化生长结构单元和高度有序的多级微观自组装生长结构和自组装方式。迄今,就发生在企鹅贝(Pteria penguin)珍珠层生物表界面处生物大分子的调控和生物矿物前驱体的相变规律,生物矿物多级微观自组装生长行为等生物矿化问题有待深化。     

生命活动中矿化作用的环境响应机制研究

生物矿化作用及其环境响应机制的研究,关键在于研究生命活动制约矿物形成、分解的机理及其环境响应机制,其内容主要包括生物矿化作用的机理、生物矿化作用的环境效应、生物矿化作用的调控理论和方法。可实现的研究目标是从多学科角度发展生物矿化作用的理论,阐明自然界中矿物－生物－重金属/POPs －水之间的相互作用机理与环境响应机制。有望揭示微生物控制重金属矿化的微观机制,提出微生物治理重金属污染原理;揭示半导体矿物－微生物协同作用降解POPs 机制,发展三元体系研究方法;揭示微生物促进多金属矿山硫化物分解机制,提出微生物分解矿物对生态环境影响的调控方法等。以促进地质生物学前沿交叉学科发展,形成未来环境污染防治重大新技术的科学基础。     

铁氧化物-微生物界面电子传递的分子机制研究进展

在地表环境中,铁氧化物矿物可以作为微生物胞外呼吸的终端电子受体/供体、电子储存介质或种间电子传递介质促进环境微生物的新陈代谢。本文介绍了矿物-微生物直接界面电子转移方式中,铁氧化物矿物与组成微生物跨膜电子传输链的细胞色素蛋白之间的氧化-还原反应机制及其影响因素,从分子水平刻画了微生物利用矿物进行胞外呼吸的过程,有助于深入理解微生物驱动的矿物转化和元素地球化学循环。     

千枚岩岩石微观破裂机理与断裂特征研究

岩石的宏观断裂与其内部微结构和微缺陷紧密相关,建立岩石微观破裂机理和宏观断裂之间更直观的联系是当今断裂力学的难题之一。本文以金沙江上游泥盆系中统中段的绢云母千枚岩与硅质板状千枚岩为研究对象,利用扫描电镜与力学试验等多种测试手段,通过对2种千枚岩岩石断口的微观形貌特征的研究,揭示了千枚岩岩石微观破裂形式、破裂机理与其矿物组成之间的联系。指出绢云母千枚岩岩石以沿晶面擦花的微观破裂形式为主,是典型的微观脆性剪断,而硅质板状千枚岩岩石既有沿晶断裂的拉断破裂,又存在切晶擦花的剪切微破裂形式,是属于拉、剪破裂并存的微观破裂机制。进一步结合岩石断裂的力学特征,分析千枚岩微观破裂与宏观断裂之间的联系。结果显示:千枚岩岩石在外力作用下的断裂形式与其微观破裂形式是可对应的。这一结论为建立起岩石微观破坏机制和宏观断裂特征的桥梁提供了依据,具有一定的理论意义。     

大气微纳米颗粒物界面反应与矿物协同演化意义

综述了大气气溶胶颗粒物的特征、颗粒物的界面反应与矿物协同演化意义;重点介绍了大气颗粒物粒径分布和矿物成分,以及常见有毒有害气体的界面反应产物特征与关键化学过程;总结了矿物颗粒在大气气溶胶形成过程中汇聚、调控、催化的作用,以及颗粒物与大气中SO₂、NO_x的协同反应机制;分析了微纳米颗粒对二次有机气溶胶形成的影响,以及大气矿物相颗粒界面反应产物组合及协同演化作用.可为进一步研究大气颗粒物与大气中痕量污染气体反应形成二次气溶胶进而影响大气化学组成的过程提供指导,对深入探讨大气矿物颗粒表面特性在复合污染物中多介质反应的微界面化学过程,矿物尘-污染物气溶胶体系在雾-霾形成、转换、新生粒子和阻断行为的复合作用具有重要的环境学意义.      

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。     

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。     

铝硅酸盐纳米矿物的地质意义和资源价值再认识

本文简析了三种典型铝硅酸盐纳米矿物(埃洛石、伊毛缟石和水铝英石)的结构和性质特点;探讨了它们在其典型赋存环境中对元素迁移和富集所起的作用和机理,包括风化淋积型稀土矿床中埃洛石对稀土元素赋存所起的作用,火山灰风化壤等体系中伊毛缟石和水铝英石对重金属离子、放射性元素、阴离子和有机碳迁移所起的作用等;还浅析了这三种特殊非金属矿物的工业应用的可能性和条件。     

纳米矿物在堆积型铝土矿床研究中的应用*

至少一维尺度上小于100ⁿm的矿物都属于纳米矿物的范畴,自然界中除了大量的人造纳米矿物之外,天然的纳米矿物分布也很广泛。随着透射电子显微镜(TEM)技术在地球科学中的应用,大量的天然纳米矿物在地壳表层和内部被发现。尤其是在矿田区域,与矿体相关的纳米矿物在各种介质中被发现,并且这些纳米矿物在矿床的研究中有着独特的作用。堆积型铝土矿床储量大,是铝土矿的重要来源。在堆积型铝土矿床中发育有大量的纳米矿物,矿石矿物也以纳米级晶体分布于矿床中,并且在纳米尺度上表现出结构和成分的变化,这些纳米矿物以及结构、成分的变化记录了铝土矿成矿过程的物理化学信息,为探究铝土矿的成因提供了独特的窗口。该综述总结了纳米矿物在研究堆积型铝土矿床中的优势,为研究堆积型铝土矿床的提供了新方法,为认识堆积型铝土矿的成因提供了新角度。     

Application of nanominerals in research on stacked bauxite deposits

Nanomineral is the mineral that is less than 100ⁿm at least one dimension. Aside from the man-made nanominerals,there is a large number of natural nanominerals. With the increasing application of transmission electron microscopy(TEM)in earth science,a large number of natural nanominerals have been discovered in the surface and interior of the Earth. Especially in ore deposit region,nanominerals related to ore bodies are found in various media,and these nanominerals play a unique role in the research of ore deposits. The stacked bauxite deposit is an important source of bauxite because of its large reserve. There are a large number of nanominerals distributed in stacked bauxite deposit,and these ore nanominerals distributed in the deposit in the form of nanocrystals. In addition,the ore minerals in stacked bauxite deposit display changes of the structure and composition in nanoscale. The nanominerals as well as the changes of structure and composition in nanoscale can record the physical and chemical information of bauxite mineralization process,providing a unique window to explore the genesis of the stacked bauxite deposit. This review summarizes the advantages of nanominerals in the research on the stacked bauxite deposit,providing a new method and a new perspective for the understanding of the genesis of bauxite deposit.     

Natural Fe-oxide and -oxyhydroxide nanoparticles: an EPR and SQUID investigation

Summary Magnetic hematite (α-Fe₂O₃) and goethite (α-FeOOH) nanoparticles, formed in the abandoned Libiola Mine (Liguria, Italy) as a result of Acid Mine Drainage (AMD) processes that involved sulfide-bearing rocks and sulfide-rich waste material, were investigated through the study of their magnetic properties in combination with electron paramagnetic resonance (EPR) spectroscopy. Both techniques revealed that the behaviour of the nanominerals involved was predominantly superparamagnetic. In contrast, the bulk antiferromagnetic behaviour of both hematite and goethite was substantially reduced. The observed magnetic properties reflected a great variability in the particle dimensions and confirmed that both nanominerals were the transformation products of a metastable amorphous species. Moreover, two peculiar phenomena were hypothesised: the transformation to hematite may occur before the coarsening of the amorphous transient and hematite and goethite can interconvert without intermediate crystallisation of metastable precursors. Goethite, in fact, appears to be formed as an alteration product of hematite, after a drastic change of the physico-chemical boundary conditions.     

从矿物粉晶表面反应性到矿物晶面反应性——以黄铁矿氧化行为的晶面差异性为例

地球系统中各种矿物相的物理化学反应大多是从矿物表面或界面开始的。要揭示矿物表面反应性的本质,就需要从控制其反应性的表面结构入手。由于实验条件的限制,绝大多数关于矿物表面物理化学性质的研究主要采用粉晶作为研究对象。尽管粉晶方法在研究诸如硅酸盐、碳酸盐溶解和沉淀结晶等过程中被普遍采用,但这种基于矿物粉晶的研究方法还是有一定的不足。因为形成粉晶的破碎研磨过程会导致晶体高能面的出现,高能面所具有的高活性可能会加速其反应过程,应用于地球化学反应的计算结果就可能高估了实际的地球化学反应速率。本研究以黄铁矿表面氧化反应的晶面差异性为例,从晶面结构制约反应性的角度出发,重新审视了黄铁矿氧化的相关问题,弥补了传统"粉晶研究"中对黄铁矿氧化速率和氧化机理认识的缺陷。黄铁矿宽范围的氧化速率实测值很可能是由不同晶面间较大的反应性差异导致;水在黄铁矿的氧化过程中同时扮演着传递电子的催化剂和反应物的角色,也是黄铁矿氧化反应速控步(rate-limiting step)的核心物质。这些认识首次明确了黄铁矿不同晶面反应性差异的重要性,并提示我们应将传统表面矿物学的研究推向更为精确的晶面矿物学水平。这一从晶面角度考察发生在矿物表面的地球化学反应的研究方法可为构建更为精确的地球化学模型提供理论基础。     

扫描电镜在粘土矿物研究中的应用

当前在粘土矿物研究中,扫描电镜已成为不可缺少的重要手段。它可以直接观察粘土样品原样,深入研究粘土矿物及其集合体的微观性状特征、矿物相互间的关系及转化等。这对于认识不同成因类型粘土矿物的形成条件,有着重要意义,也是其它研究手段无法代替的。     

Low-calcium garnet harzburgites from southern Africa: their relations to craton structure and diamond crystallization

Low-Ca garnet harzburgite xenoliths contain garnets that are deficient in Ca relative to those that have equilibrated with diopside in the iherzolite assemblage. Minor proportions of these harzburgites are of wide-spread occurrence in xenolith suites from the Kaapvaal craton and are of particular interest because of their relation to diamond host rocks. The harzburgite xenoliths are predominantly coarse but one specimen from Jagersfontein and another from Premier have deformed textures similar to those of high-temperature peridotites. Analyses for many elements in the harzburgites and associated iherzolites form concordant overlapping trends. On the average, however, the harzburgites are deficient in Si, Ca, Al and Fe but enriched in Mg and Ni relative to the lherzolites. Both the harzburgites and lherzolites are enstatite-rich with mg numbers [100.Mg/(Mg+Fe_total)] greater than 92 and in these respects differ markedly from residues generated by extraction of MORB. Equilibration temperatures and depths calculated for the harzburgites have the ranges 600–1,400°C and 50–200 km. Those of deepest origin overlap the interval between low-and high-temperature lherzolites that commonly is observed in temperature-depth plots for the Kaapvaal craton, suggesting that some harzburgites may be concentrated relative to lherzolites at the base of the lithosphere. The low-Ca harzburgites and lherzolite xenoliths have overlapping depths of origin, gradational bulk chemical characteristics and similar textures, and therefore both are believed to have formed as residues of Archaen melting events. The harzburgites differ from the lherzolites only in that they are more depleted. Garnets and associated minerals in harzburgite xenoliths differ from minerals of the same assemblage that are included in diamonds in that the latter are more Cr-rich, Mg-rich and Ca-poor. Coarse crystals of low-Ca garnet with the compositional characteristics of diamond inclusions commonly occur as disaggregated grains in diamondiferous kimberlites. Their host rocks are presumed to have been harzburgites and dunites. The differences in composition between the disaggregated grains that are similar to diamond inclusions and those comprising xenoliths imply some differences in origin. Possibly the disaggregated harzburgites with diamond-inclusion mineralogy have undergone repeated partial melting and depletion near the base of the lithosphere subsequent to their primary depletion and aggregation in the craton. Equilibration with magnesite may have reduced the Ca contents of their garnets and decomposition of the magnesite during eruption may have caused their disaggregation.     

Allende inclusions: volatile-element distribution and evidence for incomplete volatilization of presolar solids

Neutron activation data on 14 trace elements in Allende bulk samples and in fractions of spheroidal Ca-Al-rich inclusions show several distinct distribution patterns. Refractories Ir and Sc have high inclusion/bulk ratios and show little variation with depth. Manganese, Fe, Co, Ni, Ga, Cd and In have low inclusion/bulk ratios and decrease with increasing depth; their presence in the inclusions reflects matrix contamination. Sodium and other alkalies have high inclusion/bulk ratios (near 0.5) and decrease with increasing depth; their high concentration despite moderate volatility seems related to condensation reactions in which refractory Al-bearing minerals are reactants. Chromium, Zn, Ge and Au show patterns similar to those of the alkalies; this seems to indicate that refractory minerals are reactants in their condensation reactions, but thermodynamic support for this hypothesis has not been found.We propose that the large size of Allende spheroidal inclusions indicates an origin by incomplete vaporization of presolar solid matter followed by recondensation of refractories on a limited number of condensation nuclei. The low abundance of large refractory inclusions in ordinary and enstatite chondrites reflects complete vaporization of presolar solids at their formation locations; constraints on homogeneous nucleation resulted in the simultaneous condensation of refractories and olivine at these locations.Quadruplicate analyses of the Orgueil chondrite are in good agreement with previous determinations with the exception of small systematic differences in Au and Ir.     

Diamonds: time capsules from the Siberian Mantle

Diamonds are thought to be “time capsules” from the Earth's mantle. However, by themselves, consisting of nearly pure carbon, diamonds provide little geochemical information about their conditions of formation and the nature of their mantle hosts. This obstacle to studying the origin of diamonds and their hosts can be overcome by using two main approaches that focus on studying: (1) the rocks that contain diamonds, i.e., diamondiferous xenoliths; and (2) mineral inclusions within the diamonds, the time capsule's little treasures, if you will. Diamondiferous xenoliths, their diamonds, and mineral inclusions within the diamonds are the subject of this review, focusing on studies of samples from the Yakutian kimberlites in the Siberian Platform.Studies of diamondiferous eclogite xenoliths significantly enhance our understanding of the complex petrogenesis of this important group of rocks and their diamonds. Such studies involve various geochemical and petrological investigations of these eclogites, including major and trace-element, radiogenic as well as stable isotopic analyses of whole rocks and minerals. The results from these studies have clearly established that the Group A-C eclogites originate from subduction of ancient oceanic crust. This theory is probably applicable worldwide.Within the last several years, our research group at Tennessee has undertaken the systematic dissection (pull apart) of diamondiferous eclogites from Siberia, consisting of the following steps: (1) high-resolution computed X-ray tomography of the xenoliths to produce 3D images that relate the minerals of the xenoliths to their diamonds; (2) detailed dissection of the entire xenolith to reveal the diamonds inside, followed by characterization of the setting of the diamonds within their enclosing minerals; and (3) extraction of diamonds from the xenolith for further investigation of the diamonds and their inclusions. In this last step, it is important that the nature and relative positions of the diamond inclusions are carefully noted in order to maximize the number of inclusions that can be exposed simultaneously on one polished surface. In this modus operandi, cathodoluminescence imaging, plus FTIR/N aggregation and C/N isotopic analyses are performed on polished diamond surfaces to reveal their internal growth zones and the spatial relationship of the mineral inclusions to these zones.Knowledge gained by such detailed, albeit work-intensive, studies continues to add immensely to the constantly evolving models of the origin of diamonds and their host rocks in the Earth's mantle, as well as to lithospheric stability models in cratonic areas. Multiple lines of evidence indicate the ultimate crustal origin for the majority of mantle eclogites. Similar pieces of evidence, particularly from δ¹³C in P-type diamonds and δ¹⁸O in peridotitic garnets lead to the suggestion that at least some of the mantle peridotites, including diamondiferous ones, as well as inclusions in P-type diamonds, may have had a crustal protolith as well.     

Origins of authigenic minerals and their impacts on reservoir quality of tight sandstones: Upper Triassic Chang-7 Member,Yanchang Formation,Ordos Basin,China

Reservoir quality is critical for sweet-spot evaluation in tight sandstone plays, but few studies have focused on the origin of authigenic minerals in tight sandstones and their impact on reservoir quality. This study integrates petrographic analysis, carbon and oxygen isotopic data and mercury injection capillary pressure data of the Upper Triassic Chang-7 tight sand reservoir samples in the Ordos Basin, China to understand the origin of authigenic minerals and the impact of authigenic minerals on reservoir quality. Carbonate minerals, including calcite, ferroan calcite and dolomite, and kaolinite, are the major authigenic minerals in the Chang-7 sandstone. They were derived from the chemical diagenetic alteration of detrital feldspar and biotite, with the involvement of ions that are believed to be primarily from the connate water in interstitial pore space of the interbedded mudstones. Meteoric water and organic fluids from hydrocarbon generation may also have been involved in the alteration processes of the minerals in the Chang-7 tight sandstone. The origin of kaolinite indicates that the porosity was increased by dissolution of detrital grains, offsetting the porosity loss from burial compaction. Authigenic minerals appear to have a weak correlation with pore structure, suggesting that the pore structure of the Chang-7 tight sandstone is not only controlled by major authigenic minerals but also affected by other geological factors.