从生物矿化作用衍生出的有机矿化作用：地球生物学框架下重要的研究主题

早期"生物矿化作用"的概念,被定义为生物形成矿物的作用,并进一步分为生物控制和生物诱导两大类型。这个宽泛的概念,被修订为生物以生命活型(living form)影响矿物物质的沉淀作用;相应地,"生物矿物"是在严格的生物控制下、从局部环境中选择性地吸收元素并融合成具有生物功能构造的矿物。"有机矿化作用",则被定义为"与那些无生命活力的有机物质相关联的矿物形成作用"。与生物矿化作用相对应,有机矿化作用的产物被定义为"有机矿物",用来指那些通过有机聚合物、生物的和(或)非生物的有机化合物所导致的矿物沉淀作用,但是,有机矿物并非活着的细胞所直接形成。有机矿物与生物矿物的重要区别是,有机矿物没有被融合成受到生物严格控制的功能性构造。生物学家和化学家将生物矿化作用作为关注"生命体系中复杂的化学过程"的研究主题,超越了地质学范畴并使生物矿化作用的研究成为多学科关注的迷人领域,也大大促进了有机矿化作用的研究;考虑到有机矿物是沉积岩的重要组成,而且与生物的出现同步,还是潜在性的地外生命的遗迹,因此,从生物矿化作用衍生出的有机矿化作用的研究,自然就成为与生物矿化作用存在紧密关联的、地球生物学框架下又一个重要的研究主题     

海底蛇纹岩化伴生的碳酸盐岩研究进展

现代海洋环境中超基性岩广泛发生蛇纹岩化,导致富氢气(H2)和无机成因甲烷(CH4)的流体渗漏活动和化能自养生物群的发育,该过程常伴有自生碳酸盐岩和水镁石沉积的形成。本文综述了现代不同海洋环境(洋中脊、弧前泥火山与海沟等)与海底蛇纹岩化有关的碳酸盐岩的地质地球化学及标志性生物特征,介绍了自生碳酸盐岩及其中生物标志物研究无机成因CH4记录的研究现状以及古代蛇纹岩化相关的碳酸盐岩的地质地球化学特征,指出了该领域存在的关键问题以及研究重点。     

氨基酸作用下碳酸钙各种晶型自组装形貌的研究

生物矿化作用是指生物在生命活动中形成无机矿物的过程,它与传统地质意义上的矿化作用明显不同的是生物体内的有机质对矿物的晶型和晶向有严格的控制作用[1].碳酸钙是自然界分布最广泛的一类生物矿物.在生物体系中,碳酸钙常见的多型体有:方解石,文石,球文石,非晶质碳酸钙,水合碳酸钙等.     

生物膜脂参与的非晶碳酸钙形成和稳定

非晶碳酸钙(amorphous calcium carbonate,ACC)是碳酸钙矿物体系中极不稳定的矿物相。但由海鞘类动物的研究表明,ACC可作为碳酸钙晶体矿物的前驱体在生物体内稳定存在,并且这些生物成因的ACC常常是由膜包裹着的。文中选用生物膜的主要成分卵磷脂(PC)为主要矿化调节剂,通过调控与碳酸钙矿化过程密切相关的无机离子Mg2+的浓度,模拟生物膜表面碳酸钙矿化作用过程。在空气/水界面处的膜脂调控下合成出可在溶液中稳定存在数天的非晶碳酸钙。该结果有力地证明了在生物矿化过程中,除了受生物体中可溶性有机大分子调控外,生物膜可能对ACC的形成和稳定也有显著的调控作用。     

生物矿物材料及仿生材料工程

生物通过有机模板的作用，使无机晶体的结晶成核、形貌和晶体学定向受到严格的控制，从而形成性能优异的有机－无机复合材料（如骨和珍珠层）或纳米晶体材料（如趋磁细菌中的磁小体）等。通过对生物矿化的研究，认识到有机分子可以改变无机晶休的生长形貌和结构，因而提供了强大的工具用来设计和制造新的材料。目前已成功仿生合成了纳米晶体材料、仿生薄膜及薄膜涂层材料、中孔分子筛材料等。     

含水非晶碳酸钙的仿生矿化研究

生物成因矿物的形成过程通常是通过先沉积非晶前驱体,进而转变形成某一种结晶相的途径来实现的。对生物成因 碳酸钙而言,普遍认为其非晶的前驱体相是在生物有机大分子和无机离子共同作用下形成的。在阴离子柠檬酸根存在的情 况下,仿生合成了非晶碳酸钙（Amorphous calcium carbonate,ACC）,运用场发射扫描电子显微镜（FESEM）、X-射线衍射（XRD）、 傅里叶红外光谱（FTIR）和热重-差热分析（TG-DTA）等实验手段进行了分析并观测了非晶碳酸钙后续转变。结果显示, 多羧基的阴离子能够诱导形成非晶碳酸钙,并且这些非晶碳酸钙具有与生物成因非晶碳酸钙类似的组成。这可能指示与生 物矿化相关的生物大分子,特别是一些富含极性羧基大分子能够诱导碳酸钙矿物非晶态前驱体相的形成,同时也能暂时稳 定这些非晶前驱体相。     

安徽灵璧地区新元古代臼齿构造（徽亮晶）碳酸盐沉积及意义

微亮晶碳酸盐岩是一种发育在前寒武纪尤其是元古代的特殊类型碳酸盐岩,它在结构上与基质有明显区别,是由均一、等轴、多边形的微亮晶方解石组成,个体为5～15μm。安徽灵璧地区微亮晶碳酸盐岩按其成因可分为原地和异地两类。原地微亮晶主要分布于泥晶灰岩、粉屑泥晶灰岩、泥灰岩或泥岩中;异地微亮晶主要发育在粉屑灰岩或砾屑灰岩中。微亮晶碳酸盐岩的岩石学特征指示其形成并发育于稳定克拉通浅海潮下及环潮坪环境,特别是中浅缓坡向上变浅旋回的底部,风暴浪基面是其发育的最大深度。微亮晶碳酸盐岩作为一种具有全球性意义的沉积碳酸盐岩类,具有特定的时限分布范围,这对于提高前寒武纪地层对比精度具有重要意义。     

钙华体次生有机体系的界面结晶作用研究

本文总结了钙华体次生有机体系中生物群落特征和界面结晶行为,根据生物在碳酸盐沉积中的角色,将钙华体中次生有机体系的界面结晶矿化类型分为生物控制矿化沉积和生物诱导矿化沉积。分述了碳酸钙沉积矿化相关的五种生物代谢活动,讨论了生物胞外聚合物（EPS）对碳酸钙矿物晶型和形貌的影响。针对目前钙华研究中存在的问题,今后应深入研究生物体主要构成元素、生物小分子和生物体内部组织在钙华形成或退化中的作用,进一步厘清钙华体与次生有机体系的多界面溶化方式,为钙华保护修复及钙华退化治理措施提供科学依据。      

陆架边缘海沉积物有机碳矿化及其对海洋碳循环的影响

边缘海沉积物是海洋重要的碳储库,其内部的碳循环主要是由有机质矿化分解过程来驱动的。有机碳进入边缘海沉积物后,矿化分解为溶解无机碳(DIC)进入沉积物孔隙水并扩散到上层水柱,参与海洋系统碳循环;同时还有部分DIC与钙镁等离子结合形成自生碳酸盐,保存于沉积物碳库。从生物地球化学角度探讨有机质埋藏机制和效率,在此基础上重点综述沉积物硫酸盐还原、产甲烷和甲烷厌氧氧化过程的耦合机制,以及有机质矿化对自生碳酸盐形成的影响等方面的研究进展,以期加深对陆架边缘海沉积物在全球碳循环收支平衡中的作用及其气候环境效应的认识。     

渤海湾盆地东营凹陷沙河街组泥晶碳酸盐岩中的微生物沉积作用

东营凹陷古近系沙河街组发育纹层状泥晶碳酸盐,其产出与相邻泥、页岩中有机质含量之间存在较好相关性,但对其成因认识尚不明确。为了正确认识陆相湖泊环境中纹层状泥晶碳酸盐的成因机制,通过岩芯(619.65m)、薄片(NY1井9片,FY1井3片)观察、荧光显微镜(2片)、扫描电镜(10片)观察和地球化学分析对上述纹层状泥晶碳酸盐进行研究。观察发现纹层中存在纳米级球状和丝状碳酸盐矿物组构,与微生物活动导致其细胞外微环境物理化学条件改变而形成的胞外聚合物和丝状细菌十分相似。泥晶碳酸盐岩纹层有机-无机碳同位素对分析结果显示,无机碳同位素δ13 Ccarb值为2.1‰~4.8‰,有机碳同位素值为-27.9‰~-22.6‰,两者呈明显负相关。基于该结果提出单一碳库有机-无机碳同位素演化模式佐证泥晶碳酸盐的沉积作用与微生物活动之间存在直接联系。以上研究表明纹层状泥晶碳酸盐形成过程中受微生物活动的影响,为湖相环境中生物活动对碳酸盐矿物沉积作用的影响研究提供了重要的实例。     

Petrology of Lower Cretaceous carbonate mud mounds (Albian, N. Spain): insights into organomineralic deposits of the geological record

The process of organomineralization is increasingly well understood with respect to modern carbonate sediments accumulating adjacent to tropical reef atolls and reef caves. Mineralization related to non-living organic substrates results in autochthonous micrite production (‘automicrites’). ‘Automicrites’ are the main constructive element of Lower Cretaceous (Albian) carbonate mud mounds in northern Spain. These slope mud mounds occur within transgressive and early highstand system tracts encompassing several macrobenthic ecological zones. They are clearly separated from the biocalcifying carbonate factory (Urgonian carbonate platforms), in both space and time. Within these build-ups, most ‘automicrites’ were initially indurated and accreted to form a medium-relief growth framework. ‘Automicrites’ have a uniform, presumably high-Mg-calcite precursor mineralogy. They show an inorganic stable-isotope signature (?¹³C around +3·3‰) within the range of early marine cements, and skeletal compounds lacking major vital effects. Epifluorescence microscopy shows that they have facies-specific fluorescence, which is similar to skeletal compounds of Acanthochaetetes, but clearly different from allomicritic sediment and cements, which are mostly non-fluorescent. The EDTA-soluble intracrystalline organic fraction (SIOF) of Albian automicrites shows an amino acid spectrum that is similar to shallow subsurface samples from their modern counterparts. Gel electrophoresis of the SIOF demonstrates an exclusively acidic character, and a mean molecular size range between 20 and 30 kDa. Experiments in vitro (inhibition tests) indicate that the SIOF has a significant Ca²⁺-binding capacity. Fluorescence and chemical characteristics of SIOF point to a main substance class, such as humic and fulvic acids, compounds that form from pristine organic matter during early diagenesis. Biomarker analyses provide evidence for the crucial role of biodegradation by heterotrophic microorganisms, but no biomarker for cyanobacteria has been found. Primary sources of organic material should have been manifold, including major contributions by metazoans such as sponges. It is concluded that many carbonate mud mounds are essentially organomineralic in origin and that the resulting fabric of polygenetic muds (‘polymuds’) may represent ancestral metazoan reef ecosystems, which possibly originated during the Neoproterozoic.     

镁同位素示踪碳酸盐岩沉积—成岩过程

镁（Mg）作为主要的造岩元素及生物营养元素,是连接大陆、海洋和地球内部循环的重要纽带。碳酸盐岩作为Mg的主要储库,是全球Mg循环的重要组成环节,利用Mg同位素示踪碳酸盐岩沉积—成岩过程是有效反演深时海水Mg同位素组成（δ26Mg_海水）、恢复全球Mg循环的基本前提。近二十年来,Mg同位素在示踪碳酸盐岩沉积—成岩过程研究中取得了较大进展:1）不同类型碳酸盐矿物形成过程中的Mg同位素分馏及其影响因素的研究得到完善;2）建立了Mg同位素地球化学模型,对不同白云石化过程进行半定量—定量模拟;3）初步探索了利用Mg同位素反演早期成岩流体体系的方法。以上研究进展为利用碳酸盐岩恢复δ26Mg_海水奠定了理论基础,在选择有效的碳酸盐岩载体恢复δ26Mg_海水时,需充分考虑碳酸盐岩的沉积—成岩过程及其对Mg同位素组成的影响,并适当结合地球化学模型,消除沉积—成岩因素的影响,进而恢复δ26Mg_海水。     

海洋沉积物早期成岩作用研究进展

海洋沉积物的早期成岩作用是其沉积和埋藏过程中发生的一系列生物、物理和化学变化,其驱动力为有机质的降解,根据反应自由能大小,参与反应的氧化剂顺序为:O₂>NO3->Mn4+>Fe3+>SO42-。随着埋深增加,形成一系列氧化—还原化学带,并推动着海底沉积物中部分自生矿物的生成及C、N、S、Fe、Mn等元素的地球化学循环和同位素分馏。一系列有机质降解反应会改变原生沉积物中保存的地球化学信息,对古环境和古气候的研究具有重要意义。在早期成岩作用过程中,有机质降解产生的碳酸根离子和钙离子、亚铁离子结合会形成方解石、文石、菱铁矿等碳酸盐矿物。硫酸盐还原产生的还原态硫最终与亚铁离子形成黄铁矿。此外,目前常用于氧化还原环境重建的代用指标有:1）Fe组分;2）C_org/P比值;3）氧化还原敏感微量元素;4）Mo、U同位素。围绕海洋沉积物早期成岩作用中的矿物和元素地球化学行为,评述了早期成岩作用过程中有机质降解反应机制,探讨了反应进程中发生的元素地球化学循环和同位素分馏,以及相伴生的碳酸盐矿物和黄铁矿等自生矿物的形成机理。最后,总结了现有研究的不足,并对未来的研究方向进行了展望。     

柴达木盆地英西地区E32盐类矿物成因及油气地质意义

近年来,柴达木盆地英西地区渐新统E32获得了持续的重大勘探发现。基于岩心观察、系统的微观岩石学、矿物学以及地球化学分析,系统总结了柴达木盆地英西地区渐新统咸化湖盆中盐类矿物特征、成因及成藏作用：(1)英西地区渐新统E32 4种重要的盐类矿物包括石盐、硬石膏、钙芒硝以及天青石等,或聚集成为具有一定厚度的盐层,或以矿物颗粒形式赋存于基质碳酸盐岩中。上部的盐间油层组的盐层较厚,以石盐为主,下部的盐下油层组的盐层较薄,以石膏为主;(2)盐类矿物“低锰”的元素地球化学特征、与盐类矿物伴生的基质碳酸盐岩具有的“低温成因”的碳氧同位素地球化学特征、未见热液矿物发育的岩石学特征以及分布面积极广的平面展布特征均显示了盐类矿物为典型的咸化湖盆沉积型,而非热液卤水析出型;(3)“盐”在油气成藏过程中发挥着重要作用,包括盐类矿物对裂缝的充填和防止油气逸散的封堵作用、盐层因具有很高的毛管突破压力和塑性特征而具有良好的封盖作用、地层条件下促进白云岩次生孔隙发育的作用以及占据一定的储集空间的消极作用等。这一研究成果可为盐下湖相碳酸盐岩的油气勘探提供重要的指导作用。     

Questioning the microbial origin of automicrite in Ordovician calathid–demosponge carbonate mounds

Calathid–demosponge carbonate mounds are a feature of Early to Middle Ordovician shallow‐marine carbonate depositional environments of tropical to subtropical palaeolatitudes. These mounds contain an important amount of autochthonous non‐skeletal microcrystalline calcium‐carbonate (automicrite) conventionally considered microbial in origin. Here, the automicrite of calathid–demosponge carbonate mounds (Tarim Basin, north‐west China) is broken down into five distinct fabrics: an in situ peloidal–spiculiferous fabric (AM‐1), an in situ peloidal fabric (AM‐2), an aphanitic–microtubular fabric (AM‐3), a minipeloidal fabric (AM‐4) and a laminoid–cerebroid fabric (AM‐5). Type AM‐1 occurs with AM‐2 being succeeded by an assemblage of AM‐3 and AM‐4. Types AM‐4 and AM‐5 are separated by an erosional disconformity. A good correlation of fluorescence and cathodoluminescence of automicrites indicates that induced and supported organomineralization produced automicrite, probably via the permineralization of non‐living organic substrates adsorbing dissolved metal–humate complexes. Using a spreadsheet with six parameters and 17 characters, AM‐1 to AM‐4 turn out to be non‐microbial in origin. Instead, these automicrites represent relics of calcified metazoan tissues, such as siliceous sponges, non‐spiculate sponges or the basal attachment structures of stalked invertebrates. Fabric AM‐5 is a microbial carbonate but is post‐mound in origin forming a drape within a reefal framework established by AM‐4. The five automicritic fabrics, individually or as an assemblage, are a common element of Ordovician calathid–demosponge carbonate mounds in general. The reassessment of the origins of these automicritic fabrics holds consequences for understanding of the Great Ordovician Biodiversification Event in terms of community structure, reef ecology and reef evolution. Episodically, these fabrics are also present in other carbonate build‐ups stretching from the Neoproterozoic over the entire Phanerozoic Eon. The massive calcification of metazoan soft tissue (AM‐1 to AM‐4) characterizes episodes and conditions of enhanced marine calcification and might be of value to refine secular trends of p CO₂, Ca concentration and Mg/Ca ratio at the scale of individual sedimentary basins.     

桂中1井井中化探指标的异常特征和指示意义

井中化探作为一种新的油气监测和早期盆地勘查评价的地球化学技术越来越引起人们的关注,文章优选了酸解烃（SC1-SC4）、热释烃（RC1-RC4）、二维荧光（FL327、FL327、FL399）、后生碳酸盐（△C）和热释汞（Hg）等作为评价指标,通过对桂中1井各种化探指标的异常特征分析,表明区内存在油气生成潜力,并指出了其主要生油气层段和储油气层段。     

http://www.sciencedirect.com/science/article/pii/S1674987112000357

Field and remote sensing studies reveal that Au-bearing quartz±carbonate lodes in Romite deposit,in the extreme South Eastern Desert of Egypt,are controlled by NNE-striking shear zones that splay from the ca.660—550 Ma Hamisana Zone.Quartz in releasing bends with sinistral shear geometry and abundant boudinaged quartz-carbonate lodes with serrate ribboned fabrics suggest vein formation throughout a transpressive wrench system.Ubiquitous hydrothermal quartz,carbonate,and subordinate chlorite and sericite within the shear zones and as slivers in veins,indicate that gold deposition and hydrothermal alteration occurred under greenschist fades conditions.The Al（Ⅳ） in chlorite indicates a formation temperature of～300℃.comparable with temperatures estimated from arsenopyrite composition for grains intimately associated with gold in quartz veins. The new geological and geochemical data indicate that splays off the Hamisana Zone are potential gold exploration targets.Quartz veins along the high order（2nd or 3rd） structures of this crustal-scale shear zone are favorable targets.In the Romite deposit and in surrounding areas,a Au-As-Cu-Sb-Co-Zn geochemical signature characterizes mineralized zones,and particularly rock chips with>1000 ppm As and high contents of Cu,Zn,and Co target the better mineralized areas. The carbonateδ¹³C_pdb andδ¹⁸O_Smow isotope signatures preclude an organic source of the ore fluid,but metamorphic and magmatic sources are still valid candidates.The intense deformation and lack of magmatism in the deposit area argue for metamorphic dewatering of greenstone rocks as the most likely fluid source.The narrow ranges ofδ¹³C（-4.6‰to -3.1‰） andδ¹⁸O（11.9‰-13.7‰） in carbonate minerals in lodes imply a corresponding uniformity to the ambient temperature andδ¹³C_CO2(δ¹³C_∑C) of the ore fluids. The calculatedδ¹⁸Oh₂o values of 6.9‰—7.9‰for ore fluids,based onδ¹⁸O values of vein quartz further suggest a likely metamorphic origin.     

Calcareous crust (caliche) profiles and early subaerial exposure of Carboniferous carbonates, northeastern Kentucky

Sequences of laminated limestones found within thin Carboniferous carbonate strata of northeastern Kentucky were studied to determine their origin and palaeo-environmental significance. These laminated zones are strikingly similar to Holocene and Pleistocene surficial calcareous crusts (caliche) profiles that occur in various parts of the world. Carboniferous laminated carbonates are associated with shallow marine carbonate units, palaeokarst, and overlying palaeosol zones. A typical laminated profile ranges in thickness from 1 to 2 m and contains brecciated, light olive-grey to brown micrite that lacks distinctive bedding. Structures and textures common in most profiles include: (1) calcareous and silicious laminae (laminae form diffuse, alternating light and dark bands that generally parallel bedding but often fill fractures and vugs within the rocks); (2) particles (allochems, and micrite and microspar fragments) coated by brown microcrystalline calcite; (3) brecciated texture; (4) circular to elliptical fossil moulds (occur in sinuous patterns and fill fractures within the rocks); (5) large and small scale fracture patterns. Subaerial weathering and vadose diagenesis of carbonate mud banks or islands is suggested as a mechanism for the formation of these Carboniferous calcareous crust profiles. These ‘crusts’ formed by a combination of solution (karsting), brecciation, and soil development that transformed an exposed marine biomicrite (‘host’ rock) into a porous subsoil rubble. Laminated ‘crusts’ and coated particles developed as the result of dissolution and reprecipitation of CaCO₃ and SiO₃ from the soil and carbonate bedrock. Carboniferous laminated carbonates in northeastern Kentucky are often referred to as ‘algal limestones’ because of their superficial similarity to some modern and ancient algal structures. This study, however, reveals numerous characteristics that can only be explained by diagenesis in a subaerial environment.     

'Cap carbonates' and Neoproterozoic glacigenic successions from the Kimberley region, north-west Australia

The term ‘cap carbonate’ is commonly used to describe carbonate units associated with glacigenic deposits in Neoproterozoic successions. Attempts to use carbonate units as stratigraphic markers have been counfounded by inconsistent identification of ‘cap carbonates’ and a somewhat broad use of the term. Systematic sedimentological and geochemical analysis of carbonate rocks (mostly dolomite) associated with glacigenic deposits from the Neoproterozoic succession of the Kimberley region, north‐western Australia, shows that it is possible to characterize such units by their specific mineralogical, sedimentological, petrographic, geochemical and stratigraphic features. Hence, it is possible to differentiate true ‘cap carbonates’ from other carbonate units that are associated with glacigenic deposits. In the Kimberley successions two broad carbonate types are identified that reflect two stratigraphically distinct depositional realms. Carbonate rocks from the Egan Formation and Boonall Dolomite (the youngest carbonate units in the succession) are characterized by sedimentary components and features that are consistent with deposition on shallow platforms or shelves, analogous to Phanerozoic warm‐water carbonate platform deposits. In contrast, dolomite from the Walsh, Landrigan and Moonlight Valley Tillites preserves a suite of sedimentary and geochemical characteristics that are distinctly different from Phanerozoic‐like carbonate rocks; they are thin (ca 6 m), laterally persistent units of thinly laminated dolomicrite/dolomicrospar recording δ¹³C fluctuations from −1‰ to −5‰. These latter features are consistent with a ‘Marinoan‐style cap‐carbonate’ rock described from other Neoproterozoic successions. The similarity and broad distribution of these rocks in Australia, when considered within the context of genetic models suggesting a global oceanographic–atmospheric event, support their use as a lithostratigraphic marker horizon for the start of the Ediacaran Period at ca 635 Ma.     

乌努格吐山斑岩型铜（钼）矿床地球化学勘查指标

对乌努格吐山斑岩型铜钼矿床进行地球化学勘查指标研究,通过探讨47种元素在矿床中的富集、贫化等分布特征,结合蚀变、矿化分带等因素,筛选了斑岩型铜（钼）矿床的地球化学勘查指标。[KK（SiO2）＋KK（K2O）]/[KK（Al2O3）＋KK（Na2O）＋KK（CaO）＋KK（Fe2O3）＋KK（MgO）]、KK（K2O）/KK（Na2O）、KK（K2O）/KK（Rb）、CaO、MgO、Na2O等指标可以反映矿床的成矿环境,圈定矿床的蚀变范围及蚀变程度等;近矿指标Cu、Mo、Ge、W、Sn、F、Bi、S、Se、Hf等可以反映矿床的矿化程度、矿体产出位置等;远矿指标[KK（Pb）.KK（Zn）×1000]/[KK（Cu）.KK（Mo）]、[KK（As）.KK（Sb）.KK（Bi）]/[KK（Cu）.KK（Mo）]、[KK（Au）.KK（Ag）]/[KK（Cu）.KK（Mo）]、As、Au、Ag、Te等可以突出找矿范围和找矿目标。这些指标既为本地区寻找同类型矿床提供了技术支持,也拓宽了其他类型矿床的找矿思路。同时,应用对数累计频率散点图确定指标的异常上（下）限,为实现指标定量化提供了有效范例。