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作者简介:

李国欣,男,1971年生。硕士,教授级高级工程师,从事油气勘探开发管理与石油地质综合研究。E-mail:guoxinli@petrochina.com.cn。

通讯作者:

王建功,男,1969年生。博士,教授级高级工程师,主要从事沉积学、层序地层学和油气勘探研究。E-mail:wangjg@petrochina.com.cn。

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目录contents

    摘要

    为明确柴达木盆地西部地区新生界微生物碳酸盐岩微观结构及主要造岩矿物的成因机理,本文利用岩芯观察、薄片分析、扫描电镜及电子探针分析等实验测试方法,对南翼山地区上油砂山组微生物碳酸盐岩微观结构、矿物特征差异性及矿化作用开展研究。分析认为南翼山地区上油砂山组发育厚层泥晶碳酸盐岩,单层厚度3~5 m;局部发育薄层微生物碳酸盐岩,单层厚度以30~50 cm为主,单层最大厚度2 m。微生物碳酸盐岩类型以凝块石为主、局部发育叠层石,二者混合共生,通过扫描电镜在微生物碳酸盐岩中发现了大量钙化的细胞外聚合物(EPS)组构与少量微生物化石,为湖相微生物碳酸盐岩的形成提供了生物学证据。研究结果表明:① 微生物碳酸盐岩主要矿物类型为方解石,微观组构复杂、类型多样,包括球粒、团粒、菱面体以及片状结构等。球粒粒径分布范围50~80 nm。团粒由若干纳米级球粒聚合黏结形成,粒径为几微米至几十微米。片状方解石往往大小不等、形态各异,粒径通常为1~10 μm。② 发现大量钙化EPS组构及疑似微体化石,包括球状、杆状及丝状体。杆状体微生物化石直径约0.4 μm,长0.5~1 μm。丝状体微生物化石直径约0.3~0.5 μm,长1~2 μm。③ 方解石矿物的形成主要以有机矿化作用(或微生物诱导矿化作用)为主、生物矿化作用次之,其中,球粒方解石主要为有机矿化作用控制(或微生物诱导)形成。杆状和丝状体化石保持了微生物的形貌特征,分析认为可能由生物矿化作用控制形成。④ 凝块石中的球粒、卵球袋及团块的形成,可能由微生物膜及其所封闭的微生物菌落钙化形成,分析认为此类矿物可能与有机矿化作用具有相关性。

    Abstract

    In order to clarify the fabrics of Cenozoic microbial carbonate and the genetic mechanisms of main rock forming minerals in the Qaidam basin, the petrographic classification, fabric identification, difference analysis of mineral morphological characteristics and Org-mineralization and biomineralization of microbial carbonates were studied by using a large number of core observation, thin section analysis, scanning electron microscope and electron probe analysis, and other analysis methods, focusing on the microbial carbonates of Youshashan Formation in Nanyishan-Dafengshan area. The analysis shows that the Youshashan Formation in Nanyishan area is developed with the thick layer of argillaceous carbonate rocks, with the thickness of 3~5 m; and the thin layer of microbial carbonates, with the thickness of 30~50 cm, the maximum thickness of microbial carbonates is about 2 m. It is considered that the microbial carbonates of Youshashan Formation in this area are mainly thrombolites and locally developed stromatolites. They are mixed and symbiotic. A large number of microbial fossils are found in the microbial carbonates by scanning electron microscope, which provides biological evidence for the formation of lacustrine microbial carbonates. The results showed that: ① The main mineral type of microbial carbonates is calcite, with complex micro morphology and various types, including spherical, agglomerates, rhombohedron and flaky structures. The distribution range of spherical particle size is 50 ~ 80 nm. The agglomerates are formed by polymerization and adhesion of several nano-sized spherical particles, and the particle size is several microns to tens of microns. Flaky calcite often varies in size and shape, with particle sizes typically ranging from 1 to 10 μm. ② A large number of calcified EPS fabrics and suspected microfossils were found, including spherical, short rod and filamentous fossils. The sizes of rod-shaped microbial fossils is about 0.4 μm in diameter and 0.5~1 μm long. Filamentous microbial fossil is about 0.3~0.5 μm in diameter and 1~2 μm long. ③ The formation of calcite minerals is mainly influenced by organic mineralization (or microbial induced mineralization) and biological mineralization. Among them, spherical calcite is mainly microbial induced formation, and a small amount of spherical calcite may be microbial controlled formation. The short rod-shaped and filamentous fossils maintain the morphological characteristics of microorganisms, which are mainly formed by microbial-controlled mineralization. ④ The formation of spherulites, agglomerates and agglomerates in the thrombolites may be formed by the calcification of the microbial film and its enclosed microbial colonies. The analysis shows that such minerals may be related to organic mineralization.

  • 生物矿化作用是生物形成矿物的作用,是在生物的特定部位,在一定物理化学条件下,在生物有机物质的控制或影响下,将溶液中的离子转变为固相矿物的作用(戴永定等,1994),包括“生物诱导矿化作用”与“生物控制矿化作用”两种不同方式(Lowenstam,1981; 戴永定等,1994; Konhauser,2007)。为进一步区分活体生物和无生命活力的有机质对矿物质沉淀作用的影响,由“生物矿化作用”进一步衍生出“有机矿化作用”概念(梅冥相,2012)。“生物矿化作用”特指以生命活型(living form)影响矿物沉淀作用(Skinner et al.,2003; 梅冥相,2012),由生物体产生的矿物被称为生物矿物(Lowenstam,1981),其形成机制统称为生物矿化(Mann,1988; Lowenstam et al.,1989; Olszta et al.,2003)。“生物矿物”是指严格由生物控制、从局部环境选择性吸收元素合成具有生物功能构造的矿物(Mann,2001; Skinner et al.,2003)。“有机矿化作用”则指与无生命力的有机质相关联的矿物形成作用,通过有机聚合物、生物和(或)非生物的有机化合物所控制的矿物沉淀作用,所形成的矿物为“有机矿物”,与生物矿物的区别在于有机矿物没有形成受到生物严格控制的功能性构造(梅冥相,2012)。当然,还有一种特殊的有机矿物的形成过程被称之为“完全矿化作用”,特指生物处于死亡边缘、或是腐烂早期阶段,通过完全矿化作用产生并保存亚细胞级别的有机残余物,以及腐烂有机质存在成因关联的矿物,也称之为有机矿物。微生物驱动的完全矿化作用有利于生物软体的保存,也有利于生物硬体的化石化作用(Mann,2001; Boyce et al.,2001; Skinner et al.,2003; 梅冥相,2012)。与有机高分子相关的矿物沉淀作用不但发生在生物体内而成为典型的生物矿化作用过程,而且也发生在生物体外而成为典型的有机矿化作用过程(Addadi et al.,2003; Reitner,2004),严格界定生物矿物和有机矿物的界限,确实存在一定的困难。在矿物的形成过程中,很多情况下生物矿化作用与有机矿化作用过程是相互依存、共同发生的。

  • 以钙化作用为主的生物矿化作用和有机矿化作用,已取得了许多引人注目的研究进展(Addadi et al.,19922003; Reitner,2004; 徐旭荣等,2008; 梅冥相,2012)。自寒武纪(Knoll et al.,1999; Erwin et al.,2011)和奥陶纪(Stigall et al.,2020)海洋生物和藻类爆发以来,碳酸钙的生物矿化与有机矿化作用变得更为广泛,在碳循环中发挥了重要作用,在地质时间尺度上影响环境变化,反过来又受周围环境的影响(Ridgwell et al.,2005; Goldberg et al.,2011)。由于碳酸钙生物化石记录的持久性,为地球生命与环境的进化提供了主要历史档案(Gilbert et al.,2022)。微生物的媒介作用所致碳酸盐岩沉淀已引起广泛关注,包括海洋礁体、潮坪沉积、湖泊白化沉积、河流石灰华、热泉泉华以及洞穴壳。同样,包括陆上钙结石、其他壳膜、颗粒以及沉积胶结物等(Riding,2000)。微生物可以简单定义为微观尺度的生物,包括细菌(蓝细菌)、真菌、小型藻类以及原生动物(Brock et al.,1994; Riding,2000)。以叠层石为代表的微生物碳酸盐岩应归属于有机矿化作用的产物(Burn et al.,1987; Riding,2000; 梅冥相,2007),而具有生物活体功能性构造的生物矿物则由生物矿化作用控制形成。

  • 微生物碳酸盐岩内部结构的保存与早期矿化作用密切相关。除了捕获、黏结碳酸盐岩和碎屑颗粒的能力外,微生物群落还能够通过生物诱导(代谢活动催化的主动沉淀,如光合作用和硫酸盐还原)和生物影响(环境驱动的被动沉淀,如成核模板)过程促进碳酸盐岩的矿化(Dupraz et al.,2009)。微生物对极细颗粒(通常直径小于1 μm)矿物的沉淀起到重要作用,通过代谢与吸附两种方式影响矿化(Little et al.,1997)。微生物细胞壁、生物膜以及细胞外聚合物(EPS)为矿物沉淀提供场所(Riding,2000; Fowle et al.,2001)。光养异养型微生物(如蓝细菌)通过代谢作用可以释放O2,并析出H+在细胞壁与EPS中提供配位体并携带OH-、HCO-3,与溶液中的Ca2+、Mg2+、Fe2+通过吸附作用促进矿物沉淀。生物矿化作用和有机矿化作用均类似于无机化学反应,无论是被诱导还是被控制,都与无机矿物形成的热力学原理相同。微生物通过代谢作用可携带负电荷基团等产物,同时吸附溶液中的阳离子,在细胞表面能诱导非晶成核到弱结晶矿物形态的形成,就是无机化学反应。矿化作用需要消耗一定能量,主要是抵消固液分离表面潜在的排斥力,消除微生物细胞外水化层并提供有机配体,为矿物成核奠定基础,最终在新生核、水溶液以及成核底层形成新的界面(Konhauser,2007)。

  • 生物矿化作用和有机矿化作用中均有两个关键过程,分别是矿物成核与矿物生长,主要受控于溶液浓度。溶液浓度是矿物临界成核的前提条件,当溶液浓度达到过饱和,才能保证离子被持续吸附、沉淀于表面并促进矿物不断生长。反之,矿物生长便会停止(Stumm et al.,1996)。成核速率对临界核的大小也有重要影响,当溶液低于临界过饱和度值时成核速率非常慢,高于该值时成核增长速率非常快(Steefel et al.,1990)。最初形成的矿物相通常是无定形的,水化程度和溶解度高,缺乏稳定结构(Konhauser,2007)。生物矿化作用和有机矿化作用中常见的矿物类型是方解石(Pentecost et al.,1986; Schultze et al.,1994; Ferris,1995; Verrecchia et al.,1995; Riding,2000; Seong et al.,2000; Braissant et al.,2003),许多证据表明白云石也与微生物的矿化作用密切相关(Vasconcelos et al.,1995; Wright,1999; Warthmann et al.,2000)。

  • 柴达木盆地西部南翼山地区上油砂山组沉积时期湖盆演化为咸化湖泊,主要发育厚层湖相碳酸盐岩,并与薄层泥岩及粉细砂岩互层分布,总体表现为混积特征。湖相碳酸盐岩主体以厚层泥晶碳酸盐岩为主(王建功等,2018),单层厚度3~5 m,最大10 m。局部发育薄层微生物碳酸盐岩,并与泥晶碳酸盐岩、粉砂岩及泥岩互层分布。微生物碳酸盐岩单层厚度以30~50 cm为主,最大厚度2 m。南翼山地区微生物碳酸盐岩规模不大、单层厚度较小,但微生物碳酸盐岩及其相关颗粒灰岩等形成的岩相组合是重要的油气储集层,并发现了一定规模的油田(王建功等,2020a; Wang Jiangong et al.,2020)。国内外均发现了与之类似的油气田(匡立春等,2012; 周立宏等,2020)。

  • 南翼山地区上油砂山组湖相微生物碳酸盐岩以凝块石为主、局部发育叠层石及二者的共生层。微生物碳酸盐岩主要是“有机矿化作用”的产物(Burn et al.,1987; Riding,2000; 梅冥相,20072012),但不同岩石类型的微观结构、矿物组分、矿物结晶程度还存在一定的差异性。这些差异性与有机矿化作用或生物矿化作用的差异性密切相关。有关南翼山地区微生物碳酸盐岩的岩石分类、微观结构及储层特征与含油气性研究较多,但针对微生物碳酸盐岩的成因机理,特别是有关生物矿化作用和有机矿化作用的报道文献较少,研究相对薄弱。因此,本文围绕柴达木盆地南翼山地区新生界上油砂山组湖相微生物碳酸盐岩,开展微生物碳酸盐岩微观结构与主要造岩矿物特征研究。重点讨论生物矿化作用和有机矿化作用及主要矿物的成因机理,对于湖相微生物碳酸盐岩的成因机理、咸化湖泊沉积环境分析具有一定意义。

  • 1 地质概况

  • 柴达木盆地位于青藏高原北部,盆地以西部阿尔金走滑断裂、北部南祁连山冲断带、南部东昆仑山走滑冲断带为界。盆地面积12.1万km2,为内陆中、新生代山间地块盆地。柴达木盆地的沉积、构造演化主要经历了3个阶段(黄汉纯等,1989; 王建等,1996; 戴俊生等,2000):① 中生代柴达木盆地为伸展型盆地,盆地北部早期断陷、晚期拗陷,沉积了下、中侏罗统河湖相含煤建造和上侏罗统、白垩系红色陆相地层; ② 古新世—渐新世演化为坳陷型盆地,局部发育湖相沉积,其余大部分以冲积扇、洪泛平原等棕红色、杂色粗碎屑沉积为主。渐新世至中新世中期(E32—N21),发育咸化湖泊-盐湖沉积,为烃源岩与湖相碳酸盐岩储集层的主要发育期。中新世中—晚期至上新世,湖水逐渐变淡为半咸水,形成滨岸浅湖相沉积。上新世中—晚期(N22末—N23),气候更加干燥,盆地沉积中心向东迁移,湖水全面咸化,发育河流相与局部盐湖,河流沉积与石盐等蒸发岩混积伴生; ③ 新近纪末期到第四纪早期,印度板块向亚洲板块强烈碰撞,盆地受到强烈水平挤压,发生表成层褶皱,形成现今的构造格局。

  • 南翼山位于柴西坳陷西北部(图1a),主要以新生界沉积地层为主,发育路乐河组(E1+2)、下干柴沟组下段(E31)、下干柴沟组上段(E32)、上干柴沟组(N1)、下油砂山组(N21)、上油砂山组(N22)以及狮子沟组(N23)等多套地层(图1b)。渐新世至上新世(E32—N23)时期,柴西地区气候整体以干旱为主、间或潮湿,湖盆发生咸化。山前带发育河流—(扇)三角洲沉积体系,盆地内部发育咸化湖泊-盐湖沉积体系。咸化湖泊以湖相碳酸盐岩和蒸发岩为典型沉积,总体表现混积沉积特征(王建功等,2020a)。柴西地区新生代咸化湖泊-盐湖可划分为边缘与盆内沉积环境,边缘环境进一步划分为滨岸区、斜坡带及断阶带等亚环境(王建功等,2020b2020c)。上油砂山组沉积时期,南翼山地区位于咸化湖泊边缘缓坡带,以咸化湖泊浅水和沼泽环境为主(图1a),主要发育厚层湖相碳酸盐岩,并与薄层泥岩及粉细砂岩互层分布,总体表现为混积特征。以厚层泥晶碳酸盐岩为主,局部发育薄层微生物碳酸盐岩。微生物碳酸盐岩以凝块石为主,往往与厚层泥晶碳酸盐岩薄层的泥岩与粉砂岩互层分布。本文基于咸化湖盆斜坡与浅水沉积环境,重点围绕南冀山地区以薄互层为主的岩相组合,开展微生物碳酸盐岩微观结构、矿物结构特征与生物矿化作用和有机矿化作用研究。

  • 2 研究资料及方法

  • 本文研究的目的层段以上油砂山组(N22)和下油砂山组(N21)为主,部分兼顾下干柴沟组上段(E32)。研究资料包括目的层段的露头、岩芯及实验室分析化验资料。野外观察西岔沟露头剖面3条、观察描述南翼山、风西及跃进地区12口井的岩芯资料,重点描述南V16-6、南浅22-06、风西2-3等3口井的岩芯共420多米。重点依托中国石油集团公司油藏描述重点实验室开展实验测试分析,观察描述210个岩石薄片,选择其中10个薄片进行电子探针分析; 制作8个自然断面的镀金样品,并利用扫描电镜观察超微观矿物形貌特征; 利用50个微生物碳酸盐岩粉末样品开展X射线衍射(XRD)全岩分析; 利用30个阴极发光资料对不同矿物分布特征及不同期次成岩作用进行观察分析。

  • 图1 柴达木盆地西部地区咸化湖泊沉积相平面图(a)与综合柱状图(b)(据王建功等,2021 修改)

  • Fig.1 The sedimentary facies map (a) and comprehensive column (b) of saline lacustrine basin in west Qaidam basin (modified after Wang Jiangong et al., 2021)

  • (a)—上油砂山组(N22)沉积相平面图;(b)—柴西地区新生界综合柱状图

  • (a) —sedimentary facies map of Shangyoushashan Formation (N22) ; (b) —the cenozoic comprehensive histogram in west Qaidam basin

  • 充分利用露头、钻井、岩芯资料,编制沉积序列柱状图、建立岩相组合模式,分析微生物碳酸盐岩发育的沉积环境与主要控制因素。综合利用薄片(偏光显微镜型号为蔡司Axio Scope A1)、电子探针(仪器型号为SHINADZU 1720)、阴极发光(仪器型号为CITL CL8200 MK5)、X射线衍射(仪器型号为CuKa辐射九天衍射仪,λ=0.15406 nm)等资料揭示微生物碳酸盐岩的岩石类型、微观结构及主要矿物组分。充分利用扫描电镜(仪器型号为FEI Quanta450 FEG)揭示微生物碳酸盐岩的矿物形貌特征、分析矿化的EPS组构,利用能谱(EDS)分析EPS组构与主要矿物的元素组成。基于上述资料及实验测试技术,开展生物矿化作用与微晶矿物的成因机理研究,建立微生物碳酸盐岩结构成因模式。

  • 3 微生物碳酸盐岩特征

  • 3.1 岩石类型及宏观形态

  • 上油砂山组微生物碳酸盐岩往往与厚层泥晶碳酸盐岩、薄层泥岩与粉砂岩互层分布。岩芯剖面揭示微生物碳酸盐岩以凝块石为主,局部发育叠层石,二者往往混合共生(图2a)。凝块石宏观上以块状构造特征为主,可见团块、聚合粒、球粒等(图2b、c)。叠层石则发育微米级—毫米级的叠层构造,由明暗纹层组成。呈现柱状凸起、波状起伏等多种形态。混合共生的凝块石与叠层石往往交替发育,由内向外、自下而上呈现韵律性变化特征。丘状微生物碳酸盐岩由丘基、丘核及丘冠三个结构单元组成(图3)。丘基生长于泥晶碳酸盐岩中,由直径约为3 cm的富有机质凝块石组成; 丘核似花蕊,由富有机质凝块石构成; 丘冠由凝块石及其包裹的短柱状叠层石构成,根据颜色可分内外两层。内层富有机质,以暗色叠层石为主,外层以浅灰色叠层石为主。

  • 图2 柴西地区典型湖相微生物碳酸盐岩(叠层石与凝块石共生层,南V 16-2井,1797.30~1797.45 m)

  • Fig.2 The typical lacustrine microbialites revealed by polished core in the west Qaidam basin (the co-exist layer of stromatolite and thrombolite, well Nan V 16-2, 1797.30~1797.45 m)

  • (a)—长方体岩芯四个侧面拼接图;(b)—长方体岩芯顶部横切面;(c)—长方体岩芯底部横切面

  • (a) —the splicing diagram of four sides of cuboid core; (b) —the top cross section of cuboid core; (c) —the bottom cross section of cuboid core

  • 图3 柴西地区典型湖相微生物碳酸盐岩结构素描图

  • Fig.3 Sketch of the typical lacustrine microbialites in the west Qaidam basin

  • 3.2 主要矿物组分

  • 以凝块石与叠层石混合共生的微生物碳酸盐岩微观结构复杂、类型多样(图4)。凝块石主要由凝块(图4a)、聚合粒(图4b)以及球粒(图4c)构成。基质以泥晶碳酸盐为主、局部为亮晶碳酸盐。凝块、聚合粒及球粒周缘发育暗色有机质包壳,并黏结碳酸盐、长英质陆源碎屑颗粒以及黄铁矿与菱铁矿。指状叠层石纹层厚度为200~600 μm(图4d),具明暗交替特征。亮色层为方解石、石英等微小颗粒,暗色纹层为富有机质组分。基质也以泥晶碳酸盐为主、局部可见亮晶碳酸盐颗粒。叠层石内部也可见大量球粒以及粉末状黄铁矿。

  • 图4 柴西地区典型湖相微生物碳酸盐岩微观结构(样品为凝块石与叠层石共生层,来自南V16-2井,1797.3 m)

  • Fig.4 The internal texture of typical lacustrine microbialite revealed by thin section in the west Qaidam basin (the co-exist layer of stromatolite and thrombolite, well Nan V16-2, 1797.3 m)

  • (a)—凝块结构;(b)—包壳粒结构;(c)—球粒与凝块结构;(d)—叠层结构

  • (a) —clot fabric; (b) —coated particles fabric; (c) —peloids and clot fabric; (d) —laminated fabric

  • XRD揭示微生物碳酸盐岩的主要矿物组分为方解石和白云石,总体以方解石为主(表1)。其中,方解石的质量含量为35.1%~92.9%,平均57%; 白云石的质量含量为4.4%~52.4%,平均30.4%; 石英的质量含量为0.7%~38%,平均8.5%; 长石的质量含量为0.7%~10.1%,平均4.9%; 黏土矿物的质量含量为4.2%~25.7%,平均11.3%。另外,还有少量的赤铁矿、方沸石、硬石膏、菱镁矿与黄铁矿。XRD揭示微生物碳酸盐岩含有多种矿物组分,除了方解石与白云石之外,还有陆源碎屑的输送与其他矿物的混入,表明微生物碳酸盐岩具有混积特征。

  • 电子探针揭示微生物碳酸盐岩(凝块石为主)的内部球粒、聚合粒、团块或凝块的矿物组分基本相似(图5a,表2)。其中,主要矿物元素为CaO,质量含量为46.95%~59.43%; 次要矿物元素为MgO,质量含量为13.3%~36.01%。另外,还有少量的SiO2、FeO、Al2O3、Na2O、K2O,其质量含量分别为0.98%~16.41%、1.69%~13.3%、0.48%~3.27%、0.29%~0.53%、0.1%~0.35%。进一步表明微生物碳酸盐岩主要矿物组分以方解石和高镁方解石为主,局部为白云石,混合少量的黏土、石英、长石矿物以及微量的黄铁矿或菱铁矿。阴极发光照片揭示矿物组分混杂分布,方解石与少量的白云石以球粒和不规则团块为主,其周缘则由暗色的富有机质组分与吸附的黄铁矿等形成包壳(图5b)。

  • 表1 柴西地区微生物碳酸盐岩的X衍射全岩矿物

  • Table1 The main mineral contents in microbialites revealed by XRD in the west Qaidam basin

  • 图5 柴西地区微生物碳酸盐岩微观结构(凝块石)与矿物组分分布特征(南浅22-06,1199 m)

  • Fig.5 The microstructure fabric and mineral composition distribution characteristics of microbial carbonates in the west Qaidam basin (thrombolite, well Nanqian 22-06, 1199 m)

  • (a)—电子探针揭示微生物碳酸盐岩微观结构及矿物组分微区测样位置,① 聚合粒,② 粒间充填物,③ 球粒,④~⑤ 凝块;(b)—阴极发光揭示主要矿物分布特征(亮红色代表方解石、暗红色代表高镁方解石与灰黑色代表黏土矿物)

  • (a) —the microstructure of microbial carbonates and the micro-area sampling position reveled by electron probe, ① agglomerate particles, ② intergranular filling, ③ spherulite, ④~⑤ clots; (b) —the distribution characteristics of main minerals reveled by Cathodoluminescence (bright red represents calcite, dark red represents high magnesium calcite and gray black represents clay minerals)

  • 3.3 微观结构与矿物形貌

  • 微生物通过代谢与吸附作用两种方式影响矿化(Little et al.,1997),极细颗粒(通常直径小于1 μm)矿物的沉淀主要由生物诱导矿化作用控制形成。微生物碳酸盐岩中的这些矿物类型往往表现为无定形、非稳定的特征,属于结构型矿物晶体的过渡产物。其中,细胞外聚合物(EPS)为矿物沉淀提供重要场所(Riding,2000; Fowle et al.,2001),钙化以后成为EPS的主要组构。上油砂山组微生物碳酸盐岩矿物组分主要以方解石为主、局部为高镁方解石。扫描电镜揭示矿物结构与形貌特征复杂、类型多样。如南V16-2井钻遇的凝块石中,方解石类型,包括球粒、团粒(聚合粒)、片状以及菱面体等。球粒方解石粒径为纳米级,粒径主要分布于50~80 nm,往往附着于较大尺寸的方解石或其他矿物表面(图6a)。团粒(聚合粒)主要由若干纳米级球粒聚合黏接,形成较大的颗粒,粒径通常为几微米至几十微米(图6b)。片状方解石大小不等、形态各异,粒径通常为1~10 μm(图6c)。南浅22-06井钻遇的凝块石主要结构由聚合粒组成,表现为球体或椭球体。扫描电镜进一步揭示球体或椭球体内部仍然由一系列更小尺度的方解石矿物组成(图6d、e)。矿物形态包括球状、聚合体以及菱面体等。结构与矿物外貌特征与南V16-2井钻遇微生物碳酸盐岩的基本一致。另一种方解石表现为菱面体特征,粒径均小于1 μm。若干菱面体方解石拼接、镶嵌可形成较大粒径的连晶体(图6f),呈现蝶型晶体以及不规则连晶体特征,通常与纳米级球粒、聚合粒方解石共生。

  • 4 EPS组构与矿化作用

  • 4.1 EPS组构中的疑似微体化石

  • 上油砂山组微生物碳酸盐岩中发现大量钙化 EPS,钙化EPS组构中见大量疑似微体化石,通过对比其他盆地微生物碳酸盐岩中微体化石(Dupraz et al.,2004; Bontognali et al.,2008; Alessandra et al.,2010; Couradeau et al.,2012)以及现代微生物席中的活体蓝细菌(Peng Xiaotong et al.,2007),发现上油砂山组微生物碳酸盐岩中的EPS组构中存在疑似微体化石,其形貌特征与粒径均与活体蓝细菌具较高相似性,研究认为可能为蓝细菌钙化以后形成的微体化石。所发现的疑似微体化石包括短杆状与丝状体两类,前者比较常见、数量较多,后者数量相对较少。

  • 表2 电子探针揭示柴西地区微生物碳酸盐岩主要元素氧化物含量

  • Table2 The contents of main elements in microbial carbonates revealed by electron probe in the west Qaidam basin

  • 注:表中样点P1~P5分别对应图5a中的测试位置①~⑤。

  • 图6 扫描电镜揭示柴西地区凝块石中钙化EPS 组构及矿物特征

  • Fig.6 The calcified EPS fabric and main mineral characteristics in microbial carbonates revealed by SEM in the west Qaidam basin

  • (a)—纳米级球粒方解石,南V16-2井,1797.5 m;(b)—微米级聚合粒(团粒)方解石,南V16-2井,1797.5 m;(c)—微米级片状方解石,南V16-2井,1797.5 m;(d)—聚合粒外部形貌,南浅22-06井,1187.7 m;(e)—聚合粒内部结构(对应于d图黄色方框位置),南浅22-06井,1187.7 m;(f)—菱面体和不规则方解石连晶体(对应于e图黄色方框位置),南浅22-06井,1187.7 m

  • (a) —nano scale spheroidal calcite, well Nan V16-2, 1797.5 m; (b) —micron sized aggregate particles calcite, well Nan V16-2, 1797.5 m; (c) —micron scale flaky calcite, well Nan V16-2, 1797.5 m; (d) —external morphology of aggregate particles, well Nanqian 22-06, 1187.7 m; (e) —internal fabric of aggregate particles, well Nanqian 22-06, 1187.7 m; (f) —rhombohedra and irregular calcite, well Nanqian 22-06, 1187.7 m

  • 短杆状微体化石直径约0.4 μm,长0.5~1 μm(图7a、图8a),化石无论呈分散状或聚合粘连,均附着于较大矿物表面(图7a、图8a)。扫描电镜的EDS微区化学分析表明短杆状化石主要矿物为方解石,其主要成矿元素以C、Ca为主(图7b、c),另外还有Si、Al、Mg、K、Na。Ca元素含量普遍较高,其余元素含量变化较大。元素含量的差异性表明蓝细菌在矿化作用过程中对元素的吸附作用具有选择性,同时也反映了微环境水介质的地球化学特征差异性。C元素含量的差异性可能反映了蓝细菌死亡降解以及在矿化过程中残留有机质的含量变化(图8b、c)。

  • 图7 扫描电镜揭示柴西地区钙化EPS组构及疑似蓝细菌化石(短杆状)与对应的能谱图(样品为叠层石,来自南V16-2井,1797.3 m)

  • Fig.7 The calcified EPS fabric with a few suspected cyanobacteria fossils (short columnar) revealed by SEM and the corresponding EDS in the west Qaidam basin (the stromatolite, well Nan V16-2, 1797.3 m)

  • (a)—① 杆状蓝细菌疑似化石,② 杆状蓝细菌疑似化石,③ 方解石;(b)—图(a)中①点对应能谱图;(c)—图(a)中②点对应能谱图;(d)—图(a)中③点对应能谱图

  • (a) —① suspected bacilliform cyanobacteria fossils, ②—suspected bacilliform cyanobacteria fossils, ③ —calcite; (b) —the corresponding EDS of point ① in figure (a) ; (c) —the corresponding EDS of point ② in figure (a) ; (d) —the corresponding EDS of point ③ in figure (a)

  • 丝状体化石直径约0.3~0.5 μm,长1~2 μm(图8a、图9a),较完整的丝状体化石可以清楚地看到钙化的蓝细菌孢子,具有念珠藻的形貌与结构特征(图9a)。单体化石的一端通常附着于较大颗粒的方解石或石英颗粒表面(图8a、图9a),若干丝状体横向拼接、粘连,形成片状体以及不规则的方解石连晶复合体(图10)。扫描电镜EDS微区化学分析表明,丝体状化石的主要矿物也是方解石,主要成矿元素为C、Ca、Si、Al(图9b、c),以及少量的Mg、Fe、Na、K等。丝状体化石成矿元素的差异性,既反映了微生物矿化过程中对元素的差异吸附,也反映了水介质地球化学特征的差异性。

  • 图8 扫描电镜揭示柴西地区钙化EPS组构及疑似蓝细菌化石(短杆状体与丝状体)与对应的能谱图(样品为叠层石,来自南V16-2井,1797.3 m)

  • Fig.8 The calcified EPS fabric with a few suspected cyanobacteria fossils (short rods and filaments) revealed by SEM and the corresponding EDS in the west Qaidam basin (the stromatolite, well Nan V16-2, 1797.3 m)

  • (a)—① 丝状蓝细菌疑似化石,② 球状蓝细菌疑似化石,③ 方解石;(b)—图(a)中①点对应能谱图;(c)—图(a)中②点对应能谱图;(d)—图(a)中③点对应能谱图

  • (a) —① suspected filaments cyanobacteria fossils, ② suspected spherical cyanobacteria fossils, ③ calcite; (b) —the corresponding EDS of point ① in figure (a) ; (c) —the corresponding EDS of point ② in figure (a) ; (d) —the corresponding EDS of point ③ in figure (a)

  • 4.2 矿化作用与矿物结晶

  • 柴达木盆地南翼山地区上油砂山组微生物碳酸盐岩的主要矿物为方解石,方解石以微晶为主,并具有多种矿物结构类型,这些矿物均黏接、附着于EPS与微生物膜,钙化以后形成其结构组分。分析认为方解石的形成主要受有机矿化作用所控制或由生物诱导矿化作用形成。绝大多数纳米级球粒方解石可能为微生物诱导矿化作用形成,而部分具有明显微生物功能构造的矿物,如部分球粒方解石、短杆状与丝状微体化石的成因则可能由活体微生物直接参与,受生物矿化作用控制形成生物矿物。

  • 对比研究发现凝块石(图11a)与叠层石(图11b)的显微组构与超微观组构既有相似性,也有差异性。凝块石的显微组构包括球粒、聚合粒以及凝块结构; 在EPS组构中可见球粒与短杆状蓝细菌微体化石。叠层石的显微组构包括球粒、聚合粒以及叠层结构; 在EPS组构中既可见到球粒与短杆状蓝细菌微体化石,又可见到丝状体蓝细菌化石。因此,分析认为凝块石的形成过程中,生物矿化作用可能以球状蓝细菌为主,而在叠层石的形成过程中,生物矿化作用可能以球状蓝细菌和丝状蓝细菌共同作用为主。

  • 图9 扫描电镜揭示柴西地区钙化EPS组构及疑似蓝细菌化石(丝状体)与对应的能谱图(样品为叠层石,来自南V16-2井,1797.3 m)

  • Fig.9 The calcified EPS fabric with a few suspected cyanobacteria fossils (filaments) revealed by SEM and the corresponding EDS in the west Qaidam basin (the stromatolite, well Nan V16-2, 1797.3 m)

  • (a)—① 丝状蓝细菌疑似化石,② 方解石;(b)—图(a)中①点对应能谱图;(c)—图(a)中②点对应能谱图

  • (a) —① suspected filaments cyanobacteria fossils, ② calcite; (b) —the corresponding EDS of point ① in figure (a) ; (c) —the corresponding EDS of point ② in figure (a)

  • 图10 扫描电镜揭示柴西地区钙化EPS组构及丝状体化石拼接体

  • Fig.10 The calcified EPS fabric with filamentous fossil spliceosome revealed by SEM in the west Qaidam basin

  • (a)—样品为叠层石,来自南V16-2井,1797.3 m;(b)—样品为叠层石,来自南V16-2井,1797.3 m

  • (a) —the stromatolite, well Nan V16-2, 1797.3 m; (b) —the stromatolite, well Nan V16-2, 1797.3 m

  • 4.2.1 有机矿化作用与有机矿物

  • 上油砂山组微生物碳酸盐岩中的球粒方解石较常见,外形复杂、形态多样,包括球形、椭球形、棒球形以及不规则形等。粒径大小各异,主要介于100~500 nm之间,最小能识别出几十纳米的球粒方解石。少量球粒方解石具微生物外形特征,或由球形微生物控制形成,但绝大多数矿物则为有机矿化作用的产物,称之为有机矿物(Addadi et al.,2003; Reitner,2004; 梅冥相,2012)。微生物具有浮游和底栖两种生态习性,以底栖为主的微生物及其菌落附着于微生物席中,构成复杂的微生物生态系统。由微生物膜控制形成的微生物菌落是微生物生长发育的微环境,这些大小不等的微环境既可保护微生物并促进其生长发育,也是有机矿化作用及矿物成核与结晶的重要场所(图12a)。微生物菌落的矿化作用主要发生在底部的微生物席,随着微生物的死亡、降解与矿物结晶形成新的微生物席,新的微生物菌落则不断向上迁移至新的微生物席表面,不断循环叠加形成宏观微生物碳酸盐岩。因此,微生物席既为菌落提供生存环境,也为有机矿物的形成提供有利场所。

  • 图11 南翼山地区两类主要的微生物碳酸盐岩

  • Fig.11 Two main types of microbial carbonates in Nanyishan area

  • (a)—凝块石,岩芯资料来自南浅22-06井,1187.7 m;(b)—叠层石,岩芯资料来自南V16-2井,1797.3 m

  • (a) —thrombolite, well Nanqian 22-06, 1187.7 m; (b) —stromatolite, well Nan V16-2, 1797.3 m

  • 生物诱导作用产生矿物沉淀的过程就是“有机矿化作用”的一种重要形式,也就是通过微生物代谢活动产物与周围水环境相互作用而形成矿物的过程,矿化作用的主要场所发生在EPS。EPS往往附着于细胞壁或微生物膜,是微生物代谢过程中产生的一种黏液,主要成分除了含90%以上的水之外,还包括多糖、蛋白质及核酸等高分子有机质(Konhauser,2007)。EPS具有较强的黏结性,既能将细胞附着在界面,也能黏结水介质中的碎屑颗粒。有机矿物主要为大小不等的球粒或聚合粒方解石,往往包裹或镶嵌在钙化的EPS。在钙化的EPS表面发育一些微凸起,可能为方解石初期成核或无定形的方解石,构成钙化EPS组构(图12a、b)。EDS揭示不同矿物的元素含量具一定差异性(表3),钙化的EPS含有较高的C元素,其体积含量与质量含量分别达到33.66%和63.41%,表明有机质含量丰富(图12c); 球粒方解石与重结晶的高镁方解石中C元素含量逐渐下降,球粒方解石的C元素的体积含量与质量含量分别为28.36%和48.31%(图12d); 重结晶的高镁方解石C元素的体积含量与质量含量分别为10.57%和20.92%(图12-③),充分表明EPS钙化受有机矿化作用的影响明显,诱导成因的球粒方解石受有机矿化作用的影响逐步变小,重结晶矿物生长成较大矿物晶体的过程,更多受控于外部环境水介质的影响,其成因可能以化学作用为主。

  • 图12 扫描电镜揭示柴西地区钙化EPS组构与对应矿物能谱图(样品为叠层石,来自南V16-2,深度1797.5 m)

  • Fig.12 The calcified EPS fabric and the EDS of corresponding mineralsin the west Qaidam basin (the stromatolite, well Nan V16-2, 1797.5 m)

  • (a)—钙化的EPS组构:(b)—①钙化的EPS,②诱导成因的方解石球粒及聚合粒,③诱导成因的高镁方解石;(c)—图(b)中①点对应能谱图;(d)—图(b)中②点对应能谱图;(e)—图(b)中③点对应能谱图

  • (a) —calcified EPS fabric; (b) —① refers to calcified EPS, ② refers to calcite spherules and aggregate particles of induced origin, ③ refers to high magnesium calcite of induced origin; (c) —the corresponding EDS of point ① in figure (b) ; (d) —the corresponding EDS of point ② in figure (b) ; (e) —the corresponding EDS of point ③ in figure (b)

  • 生物诱导矿化作用主要由静电吸附作用控制,微生物细胞壁表面的官能团配位体、微生物膜和EPS均携带大量负电荷(HCO-3),通过吸附作用与水体中的金属阳离子(Ca2+、Mg2+)结合,发生化学反应形成方解石。微生物诱导矿化作用的典型特征是细胞对矿物没有任何明显的控制,而是细胞代谢诱导非晶成核到弱结晶矿物形态。水介质中pH值越高,细菌吸附的阴离子越多,其水化性和亲水性就也越强。矿物形成初期是自发形成临界核,溶液中离子或原子的浓度必须达到过饱和(Stumm et al.,1996)。最初的矿物相通常无定形、水化程度和溶解度较高,缺乏固有稳定结构(Nielson et al.,1971; Konhauser,2007)。之后,经过较长时间的矿化作用,矿物不断沉淀、生长,较小的纳米级球粒不断聚集成大粒径的团粒或聚合粒(图13a),无定形、水化程度较高的矿物相态不断结晶定形。矿物在结晶过程中,一方面小的晶体相互拼接、镶嵌不断变大; 另一方面围绕晶体周缘不断向外扩展,可识别出一系列环边缘的生长纹层(图13b),晶体不断生长呈片状、块状或不规则形态。矿物由无定形向结晶相转变、由小球粒粘连成聚合粒。晶体由小变大的生长过程中,主要依赖于水介质的离子浓度。因此,该过程更多的是一种化学反应过程,微生物的诱导作用可能变得越来越弱。

  • 表3 柴西地区扫描电镜EDS揭示钙化EPS及方解石矿物元素含量

  • Table3 The main mineral elements contents of calcified EPS and induced calcite reveled by EDS in the west Qaidam basin

  • 注:Au为测试中样品的镀金,不是矿物成矿元素; EDS能谱测试位置对应于图12b。

  • 图13 扫描电镜揭示柴西地区钙化EPS组构及纳米级球粒方解石聚合体(样品为叠层石,来自南V16-2,1797.5 m)

  • Fig.13 The calcified EPS fabric and nano-scale spherical calcite polymer revealed by SEM in the west Qaidam basin (the stromatolite, well Nan V16-2, 1797.5 m)

  • (a)—钙化EPS组构及纳米级球粒方解石聚合体;(b)—钙化EPS组构及纳米级球粒方解石聚合体,方解石生长环纹

  • (a) —the calcified EPS fabric and nano-scale spherical calcite; (b) —the calcified EPS fabric and nano-scale spherical calcite, growth ring pattern of calcite

  • 4.2.2 生物矿化作用与生物矿物

  • 上油砂山组微生物碳酸盐岩中发现大量短杆状与丝状体的疑似微体化石,保持了微生物的功能结构特征,分析认为有可能由微生物活体参与,由生物矿化作用控制形成(图7a、8a、9a、10a、10b),这些疑似微体化石又称之为生物矿物(Lowenstam,1981; 梅冥相,2012)。生物矿化作用过程完全被微生物控制,允许有机体沉淀矿物质,通过细胞质或细胞壁上有机基质直接参与钙化形成矿物质。蓝细菌内部有一个囊泡,作为方解石形成的位点。Ca2+从CaCO3饱和湖水中被动地通过Ca2+通道进入细胞质,HCO-3也被引入沉积囊泡中完成方解石的形成(Jong et al.,1997)。

  • 上油砂山组微生物碳酸盐岩中发现的短杆状与丝状体疑似微体化石含有较高的Ca、C和O元素,也含有一定量的Mg、Si、Al和Fe,但后者元素含量变化较大。反映了微生物或微生物群落外部环境水介质条件; 另外由微生物生态习性所决定,微生物细胞因某些生理目的而具有离子选择性,特定离子被引入其中、并控制其浓度,达到矿物饱和状态促进矿物质的形成(Konhauser,2007)。

  • 微生物的钙化作用多出现在活体阶段,往往与含多糖的微生物鞘密切相关(Merz-preiss,2000; Riding,2000),鞘的发育既对微生物起保护作用,又是微生物发生矿化作用的理想场所。Peng Xiaotong et al .(2007)研究中国华南现代热泉微生物席和蓝细菌的矿化作用,建立了蓝细菌的3种矿化机制模型:① 细胞壁外发育鞘及较厚的EPS,矿物微晶吸附在EPS并聚集成层形成矿化壳; ② 细胞壁外发育鞘,但无明显EPS,矿物微晶则沉淀在鞘的外表面形成矿化壳; ③ 细胞壁外既无鞘也无EPS,矿物微晶直接沉淀在细胞壁外表面。

  • 当蓝细菌等微生物处于死亡边缘或是腐烂早期阶段,通过“完全矿化作用”能够产生并保存亚细胞级别的有机残余物,这些残余物具有生物功能构造,类似于生物矿物,但并非是生物矿物,因与腐烂有机质存在成因关联,也称之为有机矿物。因此,严格界定生物矿物和有机矿物的界限,确实存在一定的困难(Addadi et al.,2003; Reitner,2004)。当蓝细菌死亡后细胞壁和鞘松散、破裂,Ca2+、Mg2+等元素离子进入细胞内、交代细胞质发生完全矿化。如果外部环境与水介质保持稳定,矿化后的蓝细菌化石形态保存完整,由于死亡的微生物在矿化作用过程中,随着环境的干燥、有机质的不断降解,细菌死亡后发生收缩、变形,其个体大小明显小于活体,因此发现的疑似蓝细菌化石一般较小(图7a、8a、9a)。观察现代蓝细菌的矿化样品中,发现细胞内部已被降解,或质壁分离,但仍然可观察到EPS的存在,表现出EPS较强的抗降解性(Léveillé et al.,2000)。这些残存的EPS携带大量黏液可以粘连钙化后的细菌化石,EPS继续矿化作用,可以促进多个细菌化石粘连、镶嵌,不断生长形成片状、块状或不规则的微体化石连晶(图10a、b)。特别对于一些并行成长的化石连晶,规则连晶体可能由有机矿化作用和生物矿化作用共同控制形成。尤其是一些微生物有手段控制矿物初始核的结构和方向,微生物的细胞结构比作矿化模板,它们官能团的组成和结构可以被动形成不同类型矿物成核的理想条件。然而,应该强调的是微生物只是用来增强过饱和溶液中的沉淀动力学,它们既不增加矿物的沉淀程度,也不促进欠饱和溶液中的沉淀(Fowle et al.,2001)。

  • 5 球粒和聚合粒与微生物膜的矿化作用

  • 5.1 球粒与聚合粒特征

  • 上油砂山组凝块石结构组分主要为团块与凝块(图14a、b),内部由一系列球粒、聚合粒组成,形成“卵球袋”结构特征(图14a)。“卵球袋”外部以钙化的富有机质包壳包裹,多个“卵球袋”相互粘连形成凝块石的基本结构。内部的球粒大小不同、形态各异、边界清晰。粒径分布为50~200 μm,形态包括球状、椭球状以及短柱状,颜色以灰黑色为主。主要矿物组分为方解石、有机质及大量黏土组分。具包壳与无包壳的球粒混杂共存(图15a),球粒间由大量亮晶方解石胶结。具包壳的球粒表现圈层结构特征,粒径为毫米级,外壳厚约20~50 μm。圈层结构由矿物组分的差异性决定,球粒内部以泥晶方解石为主,外壳则是泥晶白云石,内、外壳之间分布大量的黄铁矿微晶。电子探针揭示无包壳的球粒边缘不光滑、其周缘普遍包裹一层絮状物,厚约2~5 μm(图15b),矿物组分为方解石,分析认为或许为钙化的EPS及其死亡、降解后钙化的细菌有机质残体。

  • 图14 柴西地区凝块石中“卵球袋”及凝块结构特征

  • Fig.14 The characteristics of ovoid bag and clot fabric in thrombolite in the west Qaidam basin

  • (a)— “卵球袋”结构,南V16-2井,1788.58 m;(b)—凝块结构,南V16-2井,1789.02 m

  • (a) —the ovoid bag texture in thrombolite, well Nan V16-2, 1788.58 m; (b) —the internal clot texture in thrombolite, well Nan V 16-2, 1789.02 m

  • 图15 柴西地区凝块石中球粒结构特征

  • Fig.15 The structure characteristics of peloids in thrombolites in the west Qaidam basin

  • (a)—球粒,南浅22-06井,1201.5 m;(b)— 激光共聚焦揭示球粒结构特征,南浅22-06井,1201.5 m

  • (a) —morphological characteristics of various peloids, well Nanqian 22-06, 1201.5 m; (b) —peloids characteristics reveled by laser confocal, well Nanqian 22-06, 1201.5 m

  • 5.2 球粒与聚合粒的成因分析

  • 上油砂山组凝块石中卵球袋和球粒为重要的结构组分,其成因可能与微生物膜及其所封闭形成微生物群落密切相关(Nielson et al.,1997)。特别是一些结构性的泥晶包壳可能代表钙化生物膜,如一些泥晶球粒的包壳、聚合粒及团块外缘的泥晶壳套。微生物群落类似“卵球袋”(Krumbein,1983; Gerdes,1994),由微生物膜包裹细菌等微生物而形成。

  • 生物膜是由生存于EPS中的薄层细菌群落(厚度几十至几百微米)组成,附着于需水环境的基底(韩作振等,2009),或者包覆波状潮汐面最顶部的单个沉积颗粒,而产生“S”形纹理(Noffke et al.,2001; Bouougri et al.,2002)。生物膜可以在任何界面上发育,甚至是细胞聚集体本身形成的界面(Flemming,2019)。因生物膜通常是细菌种群和群落的亚毫米级薄膜,所分泌的EPS为微生物菌落提供稳定环境,促进代谢作用、并充当扩散屏障和吸附剂(Lawrence et al.,1994; Riding,2000),这是一种适应外部环境的生态习性。

  • 生物膜为微生物群落提供一个相对稳定、封闭的微环境。微生物群落大小不等、形态各异,是相对独立的生态系统。大的微生物群落内部又由若干微生物种群组成,多个微生物群落又通过生物膜依附于沉积物表面(Costerton et al.,1987; Corning,2002; Flemming et al.,2019),通过不断向上生长、聚集成层状微生物席(Characklis,1973; Geesey et al.,1989)。微生物席从定义上讲就是真正的生物膜(Neu,1994; Wingender,1999),是一个纹层状、繁盛在界面并呈网状结构以原核生物为主的微生物群落(Cohen,1989; Wachendörfer et al.,1994; Stolz,2000)。微生物通过代谢作用不断形成EPS,大量聚集并构成生物膜的重要组成部分。生物膜可能表现出结构异质性(Wolfaardt et al.,1994; Costerton et al.,1995; Decho,2000),为不规则的三维网络,具有20~40 μm规模的水流通道系统(Lawrence et al.,1991),吸收营养物质、排出氧气和废物。

  • 微生物群落的矿化作用发生在一个与外部环境相隔、相对独立的局部微环境,由于相对独立离子扩散受到一定程度限制,尽管外部条件对矿物形成不利,但相对封闭微环境的矿化作用影响较小。微生物及其群落通过代谢作用,引起微环境水介质碱性梯度的变化,促进矿物质沉淀(Konhauser,2007)。微生物膜及EPS是细菌生命代谢、金属离子吸附以及生物化学反应重要场所,也是生物矿化作用、矿物沉淀以及黏结黏土质碎屑颗粒的重要位置。微生物通过光合作用吸收CO2进行固碳,同时经过脱质子而形成HCO-3,所形成的黏性胞鞘能导致外界溶液碱性梯度变化,利于CaCO3沉淀,促进微生物钙化作用发生(Pentecost et al.,1986; Merz-preiss,2000; Riding,2000)。

  • 微生物群落是球粒、聚合粒矿化过程的基本单元,也可能对凝块与团块结构产生一定影响,为微生物席的生长、发育,以及微生物碳酸盐岩的形成起到重要作用。单细胞微生物和小规模的微生物种群钙化形成球粒,大的微生物群落及其内部种群钙化后形成卵球袋型聚合粒。另外,生物膜及其EPS分泌大量黏液,黏接陆源碎屑、黏土矿物与有机质组分(Absolom et al.,1983; Loosdrecht et al.,1990),构成球粒、聚合粒以及团块的包壳。球粒、聚合粒同样也是泥粒灰岩与粒泥灰岩的结构组分,通过激光剥离技术微区分析发现,其稀土元素配分模式与微生物碳酸盐岩基本一致,表明泥晶灰岩中球粒及聚合粒的成因与微生物群落具相关性,分析认为浮游小群落与微生物膜的矿化作用起到关键作用(王建功等,2021)。Riding(2000)也认为碳酸盐岩中大量的1~5 μm大小的泥晶颗粒,是微生物表面矿化、过饱和溶液的化学沉淀和侵蚀现有碳酸盐岩层等的综合作用的结果(Riding,2000)。

  • 电子探针背散射图像清楚地揭示,部分具包壳结构的球粒具有圈层结构,内部以泥晶方解石为主,外壳则是泥晶白云石,内、外壳之间分布大量的黄铁矿微晶(图16)。其形成过程及矿物结晶具有时间顺序,球粒内部的泥晶方解石形成之后,周缘环境的Ca2+浓度降低、Mg2+浓度逐渐达到饱和促进白云石包壳的形成。黄铁矿微晶的形成基本与内部方解石形成时间同步,因微生物代谢促进周缘水环境碱度升高,而微生物菌落的局部环境转变为酸性、厌氧、还原环境,在厌氧硫细菌的作用下促进不稳定的 Fe(OH)3分解,形成黄铁矿。

  • 图16 电子探针揭示柴西地区球粒结构及主要矿物的有序分布(跃灰101,3194.39 m)

  • Fig.16 The characteristics of peloids fabric and ordered distribution of main minerals revealed by electron probe in the west Qaidam basin (well Yuehui101, 3194.39 m)

  • 6 矿化作用的主要控制因素

  • 上油砂山组湖相微生物碳酸盐岩的内部结构类型复杂、多样,包括球粒、聚合球、团块以及纹层等。主要矿物组分是方解石和高镁方解石,晶体以微米级和纳米级为主。微晶形貌包括球状、团粒、片状、菱面体及不规则体等。也发现大量疑似微体化石,包括球状、杆状和丝状体。由生物膜控制形成的微生物群落既是微生物赖以生存的重要环境,也是有机质矿化与生物矿化作用的基本单元。分析认为矿化作用以及矿物形成主要由如下因素所控制。

  • (1)微生物群落以及生物膜和微生物席的形成(图17a)。生物膜和微生物席既为微生物的生态系统提供有效保障,又是生物矿化的有利场所。微生物席的形成主要归因于把生物膜和生物席特征化的细胞外聚合物质(EPS)(Decho,2000; Schieber et al.,2007; 梅冥相,20072014; Dupraz et al.,2009; Noffke,20092010),微生物席主要发育在水与坚硬底质之间的界面上(Cohen,1989),其纹层由相互作用的微生物群落(蓝细菌)发展而来。

  • (2)光养自养型微生物的呼吸与代谢作用(图17b)。微生物通过呼吸与代谢作用可以固定CO2,并经过脱质子而形成HCO-3,代谢作用排出代谢废物形成EPS。细胞壁、微生物膜与EPS携带大量的负电荷,通过静电作用吸附水介质中的金属阳离子,为矿物结晶成核提供有利场所。当微生物酶降解EPS时,阳离子被释放,碳酸盐矿物沉淀(Dupraz et al.,2005; Glunk et al.,2011)。EPS主要聚集于细胞外形成一种具黏结性的基质,附着于基底之上,能够为微生物提供物理和化学保护作用(梅冥相,2007; 韩作振等,2009)。

  • (3)微生物的矿化作用与矿物结晶(图17c)。由微生物诱导控制和直接参与控制两种方式。生物诱导矿化是通过微生物的代谢作用引起水介质环境pH升高,促进方解石的形成。单细胞微生物的矿化作用先发生在细胞壁,其次为内部的细胞质,通过微生物的直接控制形成生物化石。有机矿化作用主要在微生物席中发生,微生物群落向上生长并通过胞外聚合物(EPS)捕获、黏结和嵌入沉积物颗粒,沉淀新的矿物,并最终产生层状(叠层石)、凝块/非层状(凝块石)和同心(核形石)结构的微生物碳酸盐岩(Canfield et al.,1993; Wingender et al.,1999; Allison et al.,2000)。因此,微生物席在有机沉积矿床的发育中起着重要作用(Burne et al.,1987)。

  • 矿化作用与矿物析出是一个复杂而有序的过程,具有时间的先后及矿物结晶的有序性,受控于多种因素,既有主次作用、又相互交织。

  • (1)矿化作用的期次性与有序性。在微生物碳酸盐岩的形成过程中,有机质矿化作用为主体、生物矿化作用次之。微生物诱导矿化作用稍早于微生物控制矿化作用,单细胞矿化作用稍早于微生物群落矿化作用。因此,微生物群落的矿化顺序依次为单体细胞→微生物群落→外部环境。微生物的矿化序列与矿物形成过程依次为细胞壁→细胞质→细胞周缘; 泥晶方解石沉淀早于亮晶方解石结晶,混合矿物形成早于单一矿物形成。

  • (2)生物矿化具有生物、化学与物理作用的交替性与重叠性。由微生物直接参与、控制矿物成核的结构和方向以生物控制作用为主。但矿物沉淀、形成微体化石又是化学过程,表现为生物与化学的交织作用。微生物的呼吸、代谢作用固定CO2、析出H+,释放O2是生物化学过程; 产生EPS发生静电吸附、促进矿物沉淀是物理化学作用; 黏结碎屑颗粒是物理作用。微生物诱导成因的球粒、聚合粒方解石以化学作用为主、生物作用次之。无定形、非稳定态矿物向稳定态晶体的转化、晶体重结晶由小变大的过程,是物理与化学作用共同影响的结果。

  • 图17 有机矿化作用过程与矿物形成模式

  • Fig.17 The model of organic mineralization process and mineral crystal in the west Qaidam basin

  • (a)—微生物群落形成;(b)—微生物代谢作用,吸附与黏结;(c)—有机矿化作用与矿物结晶

  • (a) —microbial community formation; (b) —microbial metabolism, adsorption and bonding; (c) —organic mineralization and mineral crystallization

  • 7 结论

  • (1)柴达木盆地南翼山地区上油砂山组微生物碳酸盐岩主要以凝块石为主,局部发育叠层石,二者往往混合共生。主要矿物组分以方解石和高镁方解石为主。方解石的微观、超微观形貌特征复杂、类型多样。包括纳米级球粒、团粒(聚合粒)、菱面体与片状结构等。球粒方解石粒径范围为50~80 nm。团粒(聚合粒)主要由若干纳米级球粒聚合而成,粒径通常为几微米至几十微米。菱面体与片状方解石往往大小不等,粒径通常为1~10 μm。

  • (2)微生物碳酸盐岩中发现大量疑似微体化石,可能为蓝细菌化石,以杆状体和丝状体为主。杆状化石直径约0.4 μm,长0.5~1 μm; 丝状体化石直径约0.3~0.5 μm,长1~2 μm。化石均附着于较大颗粒表面,若干丝状体横向拼接、粘连,形成片状与不规则复合体。

  • (3)球粒方解石主要由有机矿化作用控制(微生物诱导矿化作用)形成,杆状体与丝状体可能由生物矿化作用控制形成。有机矿化作用和生物矿化作用与矿物析出是一个复杂而有序的过程,矿化作用具有期次性与有序性,生物、化学与物理作用的控制又具有交替性与重叠性。

  • (4)凝块石中卵球袋和球粒为重要的结构组分,由生物膜、微生物席及其微生物群落钙化形成。微生物膜所控制的微生物群落是球粒、聚合粒矿化过程的基本单元,也可能对凝块与团块的形成产生一定影响,对微生物席的生长、发育,以及微生物碳酸盐岩的形成起到重要作用。

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    • 梅冥相. 2007. 微生物碳酸盐岩分类体系的修订: 对灰岩成因结构分类体系的补充. 地学前缘, 5: 222~234.

    • 梅冥相. 2012. 从生物矿化作用衍生出来的有机矿化作用: 地球生物学框架下重要的研究主题. 地质论评, 58(5): 937~951.

    • 梅冥相. 2014. 微生物席的特征和属性: 微生物席沉积学的理论基础. 古地理学报, 16(3): 285~304.

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    • 王建功, 张永庶, 李翔, 徐丽, 石亚军, 黄叶秋, 王玉林, 管斌, 张世铭, 高妍芳. 2020a. 柴达木盆地西部渐新统纹理石沉积特征与原位成藏. 石油学报, 41(8): 940~959.

    • 王建功, 杨少勇, 李翔, 吴颜雄, 高妍芳, 马新民, 白亚东, 倪祥龙. 2020b. 柴达木盆地西部地区咸化湖泊微生物岩特征与差异分布. 中国矿业大学学报, 49(6): 1233~1249.

    • 王建功, 张道伟, 白亚东, 孙秀建, 李翔, 王爱萍, 张世铭, 易定红, 杨巍. 2020c. 柴西地区上油砂山组咸化湖沼沉积与微生物岩. 地质学报, 94(11): 3228~3248.

    • 王建功, 张永庶, 孙秀建, 李翔, 高妍芳, 龙国徽, 白亚东, 吴颜雄. 2021. 柴西地区新生界湖相碳酸盐颗粒结构多样性及成因. 中国矿业大学学报, 50(6): 1057~1075.

    • 徐旭荣, 蔡安华, 刘睿, 潘海华, 唐睿康. 2008. 生物矿化中的无定形碳酸钙. 化学进展, 20(1): 54~59.

    • 周立宏, 韩国猛, 马建英, 陈长伟, 杨飞, 张莉华, 周可佳, 陈双清, 杨帆, 董越崎, 周静. 2020. 歧口凹陷西南缘沙河街组一段下压段古环境特征与沉积模式. 石油学报, 41(6): 901~917.

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