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作者简介:

熊灿娟,女,1987年生,博士研究生,主要从事沉积矿产研究;E-mail: cjxiong0807@163.com。

通讯作者:

杨瑞东,男,1963年生,教授,主要从事沉积矿产研究;E-mail: rdyang@gzu.edu.cn。

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目录contents

    摘要

    磷矿作为重要的非金属矿产资源,广泛应用于农业、工业和环保等领域。滇东北地区位于扬子克拉通西南缘,是磷矿资源的集中分布区,其成矿作用的研究具有重要的学术价值和经济意义。本文在大量查阅相关文献资料的基础上,系统总结了滇东北寒武纪梅树村期磷矿床在成矿地质背景、物质来源及成矿机制方面的研究进展。研究普遍认为,滇东北磷矿床主要形成于浅海碳酸盐台地及台地凹陷盆地,但在不同矿床中,具体的沉积古地理位置和古环境特征表现出一定的差异性。关于成矿物质来源,主要有陆源物质、生物源磷、海水和深部热液等多种不同观点,而成矿机制主要包括生物成磷作用、海相热水沉积作用及上升洋流等。尽管已有大量研究对磷矿的成因进行了探讨,但仍有多种不同认识,成矿背景、物质来源及成矿机制等方面的争议依然存在,影响了区域成矿模式的构建。未来的研究应加强利用显微组构的原位分析,结合多种地球化学手段,深入探讨滇东北磷块岩的成因机制和古海洋环境,构建滇东北磷块岩的成矿模式;这不仅有助于磷矿资源的勘探与开发,也将对扬子克拉通成矿系统的研究发挥重要作用。

    Abstract

    Phosphorite, as a vital non-metallic mineral resource, is widely utilized in various fields, including agriculture, industry, and environmental protection. The northeastern Yunnan region, located on the southwestern margin of the Yangtze Craton, is a key area for the distribution of phosphorite resources. Consequently, research on its ore-forming processes holds significant academic and economic value. This review highlights the research progress on the metallogenic geological background, material sources, and ore-forming mechanisms of Cambrian Meishucun period phosphorite deposits in northeastern Yunnan. It is generally accepted that the phosphate deposits in northeastern Yunnan primarily formed in shallow marine carbonate platforms and platform sag basins. However, there remains ongoing debate regarding the specific depositional paleogeography and paleoenvironment. Several viewpoints exist concerning the sources of ore-forming materials, which include terrestrial materials, biogenic phosphorus, seawater, and deep-seated hydrothermal fluids. The main ore-forming mechanisms identified are biogenic phosphogenesis, marine hydrothermal deposition, and upwelling currents. Despite extensive studies on the genesis of phosphorite, no consensus has yet been reached. Controversies persist regarding the metallogenic background, material sources, and ore -forming mechanisms, which have hindered the development of regional metallogenic models. Future research should focus on in situ microstructural analysis combined with various geochemical methods to further explore the genesis mechanisms and paleo-oceanic environment of phosphorite in northeastern Yunnan. This will help establish a comprehensive metallogenic model for the region, contributing to phosphorite resource exploration and development, as well as advancing the study of the metallogenic system of the Yangtze Craton.

  • 磷矿作为全球重要的非金属矿产资源,广泛应用于农业、工业和环保等领域,其资源的合理开发与利用对于保障粮食安全和推动经济发展具有重要意义(刘美美,2015)。滇东北地区作为扬子克拉通西南缘的重要磷矿资源聚集区,其磷矿主要形成于寒武纪梅树村期,与震旦纪陡山沱期一起构成我国成磷作用的两个关键历史时期(曾允孚等,1989; 邓小林,2009; 韩豫川等,2012; 何义,2017; 岳维好,2022; 王畅等,2024)。

  • 近年来,关于滇东北磷矿的研究取得了显著进展,尤其是在古地理环境、物质来源及成矿机制方面。在古地理环境方面,尽管普遍认为磷矿形成于浅海碳酸盐台地及台地凹陷盆地,但不同学者对富矿位置的空间分布、沉积动力条件以及氧化还原环境等方面的认识仍有所不同(戈宏儒等,1983; 刘宝珺等,1987; 曾允孚等,1989; 东野脉兴,2001; 邓小林,2009; 岳维好,2012; 杨志鲜等,2016; LiMenghan,2020; Zheng Qin et al.,2022; 米云川等,2024)。关于成矿物质的来源,学者们提出了多种假说,包括陆源物质、生物来源、陆源与生物源混合、富磷海水、深部热液活动以及古陆风化和早期火山喷发物质等(刘宝珺等,1987; 东野脉兴,1992; 曾允孚等,1994; 陈永权等,2005; Halverson et al.,2009; Chen Jiyan et al.,2013; Liu Zeruiray and Zhou Meifu,2017; 苏旭楠等,2018; 曹金鑫等,2022; 秦欢等,2022)。成矿作用的理解同样不尽相同,主要包括生物成磷作用、海相热水沉积作用、上升洋流成矿作用和机械堆积作用等( 沈丽娟等,1987; 叶连俊,1989; 曾允孚等,1993; 陈其英等,1995; 东野脉兴,1996; 陈永权等,2005; 邓小林,2007; Li Da et al.,2009; 岳维好等,2012; Zhegallo,2016; 杨万涛,2017; Liu Zeruiray and Zhou Meifu,2017; 孟永龙,2018; 旭楠等,2023; 米云川等,2024)。尽管已有大量研究探讨滇东北磷矿的成因,但在具体的成矿古地理位置、物质来源及成矿机制等问题上仍未达成共识,相关研究仍存在诸多争议,至今尚缺乏一个系统而全面的成矿模式来解释其成矿过程,构建统一的成矿理论依然是当前研究的难点。

  • 随着镇雄羊场超大型磷矿的发现,该地区磷矿引发了广泛关注,加大了对滇东北磷矿成因的深入研究。因此,本综述将系统梳理滇东北地区早寒武世磷矿床的成矿背景、物质来源及成矿机制,并在此基础上探讨成矿模式及未来研究方向,旨在为完善成矿模式、优化勘探策略和促进磷矿资源的可持续利用提供科学依据与理论指导。

  • 1 成矿地质背景

  • 1.1 古地理

  • 扬子地区是我国最重要的磷矿分布区,而滇东北磷矿区则位于扬子克拉通的西南缘。晋宁运动奠定了扬子地区的基本构造格架:在早震旦世之前,元江—红河岩石圈断裂等深大断裂活动促使扬子克拉通整体隆升,使其从活动大陆边缘转为稳定克拉通。寒武纪时期,扬子克拉通进入稳定发展阶段,其周缘和内部深大断裂活动控制形成了多个隆起带和断陷盆地( 邓小林等,2009; 韩豫川等,2012; 岳维好,2022)。南北向的古断裂(如西昌—易门断裂、普渡河断裂和小江断裂)进一步控制了滇东北地区的古地理演化,形成了“二隆三洼” 的格局,即康滇和牛首山古陆的隆起区及其间的低洼区,包括硝滩-羊场、九龙-会泽、昆明-华宁等凹陷; 北东向受断裂的影响,自北西向南东形成雷波、镇雄、织金三个聚磷盆地,以及次级的同生沉降盆地、沉积凹陷(图1); 这一地理格局为磷矿的沉积提供了理想的古地理环境( 戈宏儒等,1983; 刘宝珺等,1987; 曾允孚等,1989; 东野脉兴,1996; 薛天星,2011; 岳维好,2012; 米云川,2021)。

  • 图1 上扬子地区寒武纪早期含磷盆地古地理图(据岳维好等,2022 修改)

  • Fig.1 Paleogeographic map of the Early Cambrian phosphorus-bearing basin in Upper Yangtze area (modified after Yue Weihao et al., 2022&)

  • 关于成矿的古地理位置,前人开展研究并取得了一定的认识。大多数学者一致认为,该区域受早期隆起和断陷构造的影响,磷块岩主要形成于浅海碳酸盐台地及台地凹陷盆地(季春生 1982; 邓小林,2009; 东野脉兴,2001; 岳维好,2012杨开军,2016),其中海湾、潟湖、台地或水下高地的边缘、水下洼地、岸外沙坝、浅滩、外陆架盆地的向陆一侧等成为工业磷块岩形成环境中不可缺少的重要因素(曾允孚等,1989; 东野脉兴,2001)。

  • 目前,对于滇东北地区磷矿沉积的古地理环境,主要存在海湾潮坪、海湾—潟湖—潮坪体系,以及台地或水下高地的边缘和水下洼地等几种认识。

  • 其中,关于海湾潮坪环境,一些研究认为,自晚震旦世以来,滇东北地区整体处于上扬子浅水碳酸盐台地的西部,北部为康滇古陆,南东为牛首山古陆,南西为滇中古陆,并与华南海、滇西海及青藏— 秦岭海相隔,构成了南西受古陆阻隔、北东方向与广海相通的相对封闭的海湾潮坪环境( 邓小林等,2007; 2009; 杨万涛等,2017; 孟永龙,2018; 岳维好,2012; 王文浩,2024)。随后,通过对寻甸大湾磷矿(杨泽刚等,2012; 苏旭楠,2018)、永善磷矿聚集区(刘建清等,2022)、镇雄羊场磷矿(岳维好,2022; 米云川,2024)、镇雄银厂湾磷矿(沈燕飞,2020)等矿床的研究,进一步支持这些矿体形成于海湾潮坪环境。区域内的水下隆起构造将该地区分隔为雷波— 永善、会东—巧家和东川—会泽三个次级海湾,被认为是磷质物质富集的有利空间(薛天星,2011)。然而,对于富矿的具体沉积位置认识略有差异,一些学者认为潮下浅滩及潮间带下部更有利于富矿的形成(邓小林等,2007; 2009; 苏旭楠,2018); 另一些则指出富矿场所主要为潮间带( 杨万涛等; 2017; 米云川,2024),尤其潮间带中部和下部(许善任; 1983); 而潮下 “台盆” 相带则沉积为贫的厚层磷块岩(杨万涛,2017)。沈燕飞等(2020)进一步指出,高能海湾的潮下浅滩,特别是受强水动力作用的潮间滩,是优质磷块岩矿床形成的重要环境。

  • 此外,也有观点认为,滇东北地区的磷块岩沉积环境整体涵盖了陆架至陆棚的海域,具备潮坪、潟湖和半封闭海湾的典型特征,沉积模式为海湾—潟湖—潮坪体系(常苏娟,2011; 韩豫川等,2012)。曾允孚等(1989)通过对昆明凹陷南段磷矿带的研究,得出磷块岩沉积于海湾—潟湖—潮坪体系中的结论。类似地,杨万涛等(2021)通过对位于东川会泽凹陷的沾益小米戛磷矿的研究,也认为该磷矿的沉积环境为海湾瀉湖潮坪环境。

  • 还有部分学者认为,滇东北地区磷矿整体的沉积环境位于台地或水下高地的边缘及水下洼地(戈宏儒等,1983; 何义等,2017)。同时,其他研究表明,川西—滇东地区的磷矿沉积环境整体位于浅海浪基面以上的陆缘坻、台地和浅海盆地等区域,特别是地形复杂的凹陷区( 东野脉兴,1996); 陈瑞红等(2021)对滇东昆阳磷矿的研究发现,该磷矿的含磷岩系主要也形成于这些环境中。

  • 综上所述,尽管现有研究普遍认为磷块岩主要形成于浅海碳酸盐台地及台地凹陷盆地,但不同矿床之间,富矿的具体沉积古地理位置仍存在差异。因此,针对不同磷矿床的古地理位置,未来应结合具体矿区特征,进一步开展古地理精细研究,以深入揭示磷矿成矿过程的内在机制,并为磷矿资源的勘查与开发提供坚实的理论基础。

  • 1.2 古环境

  • 1.2.1 古气候与古盐度

  • 在寒武纪早期,扬子克拉通西南缘处于低纬度(南北纬 18°之间)干旱炎热气候环境。大量研究表明,磷块岩的形成与这种气候条件密切相关。通过磷块岩与白云岩的共生关系,认为该地区磷矿是在干旱炎热的气候条件下形成的(曾允孚等,1989; 叶连俊,1989; 杨帆,2011; 邓小林,2009; 蒲心纯,1993; 岳维好,2012; 何义,2017; 米云川,20212024)。进一步的地球化学研究也提供了有力证据。秦欢等(2022)通过镇雄县羊场磷矿中磷块岩的 Sr/ Cu 比值(范围为 27.35~322.18)远大于 5. 0,表明这些磷块岩是在干旱气候条件下形成的。曹金鑫等(2022)的研究也得出了类似的结论,其对东川白龙潭磷矿磷块岩的 Al2O3 / MgO 比值(范围为 0. 04~1 1. 0,平均值为 4. 08)进行分析,同样确认了磷矿的形成与干旱气候密切联系。干旱炎热的气候条件不仅影响了磷矿的形成,还对磷及伴生元素的溶解和沉积过程产生了深远影响。在这种气候条件下,风化作用明显减弱,陆地物质的输入量显著减少,从而导致海水中的沉积速率变慢。然而,干旱条件下的高盐度环境,特别是在浅海陆架区域,进一步增强了磷和其他伴生元素(如 Fe、Mn、REE、Sr 和 U 等)的溶解度(叶连俊,1989; 邓小林,2009)。曹金鑫等(2022) 通过对白龙潭地区不同类型磷块岩的 100 ×MgO/ Al2O3 值(普遍大于 10)及 Sr/ Ba 值(3~10)分析,进一步证实这些磷块岩是在高盐度环境下沉积的。

  • 上述研究一致认为,磷块岩的形成与低纬度干旱炎热气候密切相关。该气候环境导致风化作用减弱、陆地物质输入减少,从而降低海水沉积速率; 同时,高盐度条件提高了磷及伴生元素的溶解度,显著影响磷矿的形成与沉积。

  • 1.2.2 水动力条件

  • 对于滇东北地区的沉积环境,杨永超等(2010) 通过分析宜良县浮占磷矿矿石中的球粒结构和陆源碎屑,认为磷矿形成于水动力较强的浅水高能环境。杨万涛等(2017)孟永龙(2018) 进一步通过磷块岩与陆源细碎屑岩的共生关系及鲕粒结构的特征,支持磷矿的高能环境形成模式。曹金鑫等(2022) 通过对白龙潭磷块岩的研究,发现该区磷矿具有明显的豆粒和球粒结构,磷块岩含大量碎屑,并且部分条带、条纹不平行,呈波状,以及较高的 Sr/ Ba 值,证实了其在水动力较强的浅水环境中形成。与此相对,季春生等(1982) 由该区大量水平层理、黑色有机岩及胶磷矿的出现,认为滇东北磷矿的沉积环境较为平静,形成于低能环境。而许善任等(1983)指出,磷矿的沉积环境既包括高能环境,也涉及低能环境,在高能环境中形成内碎屑和鲕粒结构,而低能环境则适合凝胶状磷矿的沉积。磷矿中深色富磷与浅色贫磷条带的交替现象,揭示了磷矿在高能与低能环境交替变化下的成矿过程。

  • 综上所述,不同学者对磷矿成矿的水动力条件存在一定分歧。一些研究认为磷矿主要形成于高能环境,而另一些则认为磷矿形成于低能环境,或是高能与低能环境交替作用的结果。结合滇东北地区矿石类型特征,磷块岩主要包括碎屑磷块岩、条带状磷块岩和泥晶质磷块岩等。其中,碎屑磷块岩通常形成于浅水且水动力较强的潮间环境,而条带状磷块岩和泥晶质磷块岩则多形成于深水且水动力较弱的潮下环境(图2)。此外,该地区磷块岩还发育有交错层理(丘状、单向)、平行层理、包卷层理、脉状复合层理、条纹条带构造,以及正粒序和反粒序等沉积构造,常见砾屑、撕裂状砾屑,并伴随粉屑及黄铁矿条带等特征(李向东等,2025),同时还有细菌、真菌、藻类等微生物以及小壳化石遗迹(东野脉兴,1992; 沈丽娟,1987)。交错层理(单向、丘状)表明水动力条件为持续且较强的单向或波动流(如潮流、风暴流); 平行层理形成于水流稳定且较强的浅水环境; 脉状复合层理则出现在水流强烈且波动的环境。砾屑和撕裂状砾屑的存在进一步证明水动力较强,足以侵蚀并搬运大颗粒沉积物,形成砾屑沉积和撕裂状碎屑。条纹条带构造及正粒序/ 反粒序反映了水动力环境的波动性与变化特征。条纹条带构造指示潮流或风暴的周期性作用,正粒序代表水动力逐渐减弱的沉积过程,而反粒序则与水动力逐渐增强的环境密切相关。微生物和小壳化石的发育表明沉积环境具有一定的稳定性,能够支持生物活动。微生物主要存在于水动力较弱的环境中,如瀉湖、礁区等浅水区,这些地方通常水流缓慢,有机质丰富。小壳化石则常见于水动力较强的环境,指示浅水、潮汐和波浪作用较强的环境,常见于潮间带等浅海域。粉屑的存在可能与微弱水动力条件的交替出现有关,表明水动力强弱变化频繁。黄铁矿条带则提示局部沉积环境中可能存在低氧甚至厌氧条件,通常与水动力较弱的静水环境或快速堆积有关,反映了成矿环境中的局部特征。因此,推测滇东北地区经历了多次海进海退过程,水动力条件呈现显著的多样性和波动性,磷矿的形成与浅水高能环境与深水低能环境的交替变化密切相关。

  • 1.2.3 古氧化还原

  • 关于滇东北地区磷块岩沉积时期的古氧化还原环境,研究表明,该区域不同磷块岩矿床的形成环境存在差异。

  • 针对昆阳磷矿,众多学者通过多种手段进行研究,包括利用 Ce 负异常特征、稀土元素富集与 Fe2O3 含量的正相关性、沉积相与地球化学特征的结合,以及氧化还原敏感元素(如 V、Ni、Cr、Mo、U)的分析等。这些研究结果均表明昆阳磷矿形成于氧化环境中(杨卫东等,1995; 杨帆等,2011; 严清高等,2018; 晁江琴等,2024)。此外,曹金鑫等(2022) 通过对白龙潭磷块岩中 V/ Cr 值和 Ce 负异常的分析,认为该磷矿同样沉积于氧化环境。陈瑞红等(2021)则通过研究寻甸大湾磷矿中的 Fe2O3 / FeO值,提出该矿床也形成于氧化环境。

  • 图2 滇东北梅树村期磷块岩沉积模式

  • Fig.2 Phosphorite sedimentary model of Meishucun period in northeast Yunnan

  • 然而,也有研究指出其他类型的沉积环境。秦欢等(2022) 通过对镇雄羊场磷矿的研究,发现其 w(V)/ [w(V)+w(Ni)]值大于 0.6,推断该矿床可能形成于还原性古海洋环境。杨万涛等(2017) 在东川金牛厂磷块岩中发现黄铁矿团块,表明该矿床可能在还原条件下形成。苏旭楠等(2018) 通过对寻甸大湾渔户村组磷矿的地球化学数据分析(如 Ni / Co 值大于 5、Th / U 值低于 2),得出该矿床可能形成于缺氧的还原环境。

  • 此外,次氧化环境的可能性也被提出。杨万涛等(2018)在对曲靖市沾益区小米戛磷矿渔户村组磷块岩的研究中发现,U 元素的高度富集、V/ Cr 值大于 2 以及显著的 Ce 负异常等特征,均表明该矿床成矿环境可能为次氧化环境。

  • 综上所述,滇东北磷矿的沉积环境可能同时存在氧化、还原和次氧化等多种环境类型。一些学者通过无机碳同位素、钼同位素、硫同位素等多种地球化学指标的研究,表明华南扬子地区在埃迪卡拉纪至早寒武世的海洋中存在明显的氧化还原分层结构( Zhu Maoyan et al.,2013; Qiao Wenlang et al.,2016; Li,2020; Zheng Qin et al.,2022; 熊轶伟等,2022)。 Wen Hanjie 等(2011) 通过分析云南梅树村期磷块岩的 δ 97Mo / 95Mo 同位素,提出华南早寒武世海洋继承了前寒武纪的氧化还原分层结构,表层为氧化环境,深层为还原环境。因此,该地区很可能存在氧化还原界面,且在该界面可能存在两种成磷机制(Pufahl and Groat,2017; Godet and Föllmi,2021)。在氧化条件下,二价铁( Fe2+)会被氧化成三价铁(Fe3+ ),进而形成具有强大吸附能力的羟基氧化铁,能够有效吸附水中溶解的磷酸盐(PO43-)。在还原环境中,三价铁(Fe3+)被还原为二价铁(Fe2+ ),导致已吸附的磷酸盐因铁的还原而被解吸,重新溶解并进入水体循环,进而与 Ca2+、F-等离子形成碳氟磷灰石,这是磷在沉积物中沉淀的主要机制(图4)。此外,有机物的降解在氧化还原界面也对磷的沉淀产生了一定影响。然而鉴于地球化学研究结论的多解性,未来还应加强基础地质研究( 张旗和原杰,2024),结合多指标联合分析的方法,深入探讨氧化还原分层结构与磷矿成因之间的关系,以便构建一个合理的成矿模式,并为科学预测该区域的成矿规律提供理论基础。

  • 2 成矿物质来源

  • 关于海相沉积磷块岩的成矿物质来源,主要存在几种不同的认识,包括陆源物质、生物来源、陆源与生物源、富磷海水、陆源及富磷海水、深部热液活动,以及古陆风化和早期火山喷发物质等(东野脉兴,1992; 李延河,1995; Liu Zeruiray and Zhou Meifu,2017; Godet and Föllmi,2021; Dodd et al.,2023; Fan Haifeng et al.,2024)。

  • 有学者认为,早寒武世滇东北地区的磷质主要来源于陆源风化物的输入( 夏学惠,1989; 杨卫东等,1995; 杨开军等,2016; 史雪飞,2017; 严清高等,2018; 曹金鑫等,2022; 晁江琴等,2024)。例如,杨卫东等(1995)通过对滇东早寒武世昆阳和海口磷矿含磷岩系的稀土元素分析,并结合 La / Yb—∑REE 图解,发现所有磷块岩样品的测试值均位于正常沉积岩区或正常沉积与碱性玄武岩的混合区,推测磷质来源于大陆母岩的风化作用,部分母岩可能为玄武岩。杨开军等(2016) 结合滇东梨树坪—下包包磷矿的矿化特点和沉积建造,进一步支持了这一观点。曹金鑫等(2022)通过对白龙潭磷矿的 Cr/ Zr 值(0.2~5. 0)和 δEu(小于 1)的分析,认为白龙潭磷块岩的磷质也来源于陆源风化。

  • 然而,也有学者认为磷块岩是一种特殊的生物岩,主要与生物活动相关,磷质微生物、藻类和小壳动物化石是其重要成分(东野脉兴,1992; 陈其英,1995),尤其是富含小壳化石的部分(吕俊,2021)。

  • 此外,另一些研究提出,磷矿的成矿物质来源于陆源碎屑与海洋生物的共同作用。富磷生物遗体与陆源碎屑共同沉积,形成了富磷的孔隙水和底层水,这些成为磷矿的直接来源(叶连俊,1989; 邓小林,2009; 何义,2017; 沈燕飞,2020; 陈瑞红和赵锴,2021)。陈瑞红等(2021)通过岩相学和地球化学的综合分析,指出昆阳磷矿的成矿物质源自陆源碎屑和海洋生物的共同作用。秦欢(2022) 通过滇东北羊场磷矿的地球化学分析,提出成矿物质来源的双重性,既包括陆源碎屑的输入,也受生物矿化的影响; 稀土元素、Sr 和 Pb 等的富集特征进一步支持了这一观点。

  • 另一些研究认为,滇东早寒武世磷矿的磷质主要由富磷的上升洋流带来(刘宝珺等,1987; 曾允孚等,1989; 曾允孚等,1994; Chen Jiyan et al.,2013)。刘宝珺等(1987)提出,扬子克拉通及邻区海域的频繁风暴活动引发了上升洋流,带来了富含磷的海水,这一过程为磷质的沉积提供了关键条件。上升洋流促进了藻类繁盛,加速了海洋磷循环,这种与大洋相通的浅水盆地起到了显著的聚磷作用,最终导致了该地区多个大型磷矿床的形成(曾允孚等,1994)。

  • 还有些研究提出磷矿的成矿物质可能来源于海相热水活动(陈永权等,2005; Li Da et al.,2009; Halverson et al.,2009; Liu Zeruiray and Zhou Meifu,2017; 杨万涛等,2021; 秦欢等,2022; 曹金鑫,2022)。此外,苏旭楠(2018)在对云南寻甸渔户村组磷矿物质来源的研究中提出,磷质主要源自陆源碎屑与海洋中富磷水团的沉积,这两者共同构成了该区磷矿形成的初始物质基础。甚至少数研究者认为,成矿物质主要来源于古陆风化和早期海底火山喷发物(常苏娟,2011)。

  • 由此可见,磷块岩的成矿物质来源仍存在诸多争议。国内外学者对海洋磷循环进行研究,认为海洋磷质的主要来源是陆源碎屑,地表径流、风力传输和地下径流是其重要的输入途径( Baturin,1982; Froelich et al.,1982; Föllmi,1996; Delaney,1998; Compton et al.,2000; 黄永健等,2005); 与陆源磷质相比,海底热液和火山活动对磷的贡献影响较小,即便是在海底火山活动带或热液喷口的富磷沉积物中,磷的来源主要是铁、锰氧化物吸附的海水磷质,而非热液提供的磷质( Baturin,1990; Ruttenberg,1992; Berner and Ruttenberg,1993)。而也有学者认为,虽然海底火山或热液活动在整个地质历史时期对大洋磷循环中的磷质输入有限,但在某些海底火山活动异常活跃的地史时段,显著影响了大洋磷循环过程(Wheat et al,1996)。综上所述,成矿物质来源可追溯至古陆,然而陆源风化的磷酸盐并非直接沉降,而是先聚集在深海中形成磷库。在磷块岩的沉积过程中,陆源风化物质的输入影响较小,成矿物质主要来自上升洋流携带的深海富磷水体—该水体中的磷溶解度是浅水水体的几十倍甚至上百倍(Kazakov,1937)。当这些深水水体进入浅水区时,由于压力、温度等条件的变化,磷开始沉淀。同时,磷块岩中富含大量化石,尤其是小壳动物的化石碎屑颗粒,这也表明生物成磷在磷矿形成过程中起到了重要作用。

  • 3 成矿机制

  • 3.1 生物成磷作用

  • “生物成磷” 是磷块岩成因的重要理论之一。虽然由生物遗体(如鸟粪化石、鱼骨化石)堆积形成的磷块岩含有一定磷,但这种磷块岩难以广泛分布或形成大规模矿床( Föllmi,1996; Filippelli,2011)。因此,普遍认为“生物成磷”是指生物作用通过富集和粘结海水中的磷质,间接促成磷块岩的沉积(朱士兴等,1983; 杨卫东等,1990; Arning et al.,2009; She et al.,2014; Cui Huan et al.,2016; Gao Lei et al.,2023)。

  • 相关研究表明,在早寒武世滇东北地区磷矿床的形成过程中,生物成磷作用也发挥了至关重要的作用,尤其是在磷质的富集与沉淀过程中,菌藻类等微生物以及小壳生物起到了显著贡献。刘宝珺等(1987)提出生物化学作用可能影响磷质的沉淀和富集,随后许多学者通过对滇东磷块岩中藻类化石的研究,进一步证实了菌藻类等微生物在磷质沉淀中的关键作用(沈丽娟等,1987; 曾允孚等,1993; 陈其英等,1995; 杨永超,2010)。东野脉兴( 19921996)认为,磷质藻类微生物及小壳动物化石是磷块岩的重要组成部分,磷块岩是一种特殊的生物岩。此外,田升平(2000)认为小壳动物和叠层石礁体的繁盛是磷质沉积和矿化的重要推动力,而邓小林等(2007)提出,生物和胶体化学作用共同促使磷质在潮坪环境中沉积形成凝胶状磷块岩,并在后续的水动力作用下进一步富集。后续多位学者也强调,生物不仅通过遗体直接磷化沉积成矿,还通过改变环境条件使磷质在适宜的条件下迁移、富集并沉淀(杨万涛,2017; 孟永龙,2018; 刘晓东等,2018; 沈燕飞,2020; 曹金鑫等,2022)。杨万涛等(2021)通过对小米戛渔户村组磷块岩的研究,认为生物成矿作用显著,其特征体现在 Ba、Cu、Pb、Zn 和 Sr 等生源性元素的高富集以及 V 和 Mo 的显著富集,均支持生物活动对磷矿床形成的积极贡献。

  • 图3 云南会泽马路磷矿中小壳动物化石壳体结构

  • Fig.3 Shell structure of fossilizedmicrozoans in the Malu phosphate mine in Huize, Yunnan

  • 生物成磷作用的过程主要体现在两个方面:首先,生物在生长过程中从海水和孔隙水中吸收磷质,随着其死亡,细菌分解有机质,导致部分磷质被释放并富集于孔隙水中(东野脉兴,1992; 孟永龙,2018; 苏旭楠,2018; 米云川,2024),进而在海洋环境变化中促使磷质结晶,形成碳氟磷灰石和细晶磷灰石等自生磷灰石矿物(Gómez-Peral et al.,2014; 黄天正等,2022)。其次,生物残骸中的磷质直接在成岩作用下固结,形成磷酸盐结核并逐渐堆积成矿,特别是小壳化石对磷矿成矿贡献很大( Zhegallo,2016; 杨万涛,2017; 孟永龙,2018; 曹金鑫等,2022; 彭柔等,2024)。

  • 综上所述,生物活动在磷矿床的形成中起着至关重要的作用,这些生物活动通过改变环境条件,促进了磷质的迁移与富集,为磷块岩的初步富集提供了关键机制。菌藻类等微生物和小壳生物通过吸收、富集和沉淀磷质以及将生物残骸磷化,推动了磷矿的形成; 另外,小壳化石的碎屑颗粒作为磷块岩的主要组分(吕俊,2021),进一步反映了生物在磷矿形成过程中的重要贡献。例如,云南会泽马路磷矿中存在磷酸盐化的小壳动物化石壳体结构(图3),表明滇东北地区磷矿的形成可能与生物活动密切相关。

  • 3.2 上升洋流成矿作用

  • 上升洋流成矿理论最早由 Kazakov( 1937) 提出,他认为富含 P2O5 的深层冷海水随洋流上升到浅海陆棚带,随着温度升高,压力降低,磷酸盐溶解度降低并通过无机化学方式沉淀下来。 20 世纪中期,Mekelvey 和 Sheldon 等进一步发展了该理论,指出在气候干旱的低纬度辐散洋流上升区域最适合磷的沉积和富集。这些地区在北半球多分布于大陆西岸和北岸,南半球则位于大陆西岸和南岸,因其连接浅海低缓陆地和深海盆地的独特成矿环境,极利于磷质的聚集。 Shen 等(2000)认为 Rodinia 超大陆的裂解伴随着海侵作用,促进了早寒武世大型矿床的成矿。一方面,海侵作用促进了大洋与浅水区之间的物质交换,将磷质带入浅水; 另一方面,它扩大了海水覆盖范围,创造了理想的成磷环境。同时,海侵推动了富营养上升流沿大陆边缘扩散,促进了磷块岩沉积和小壳无动物的多样化,为磷矿床的形成提供了有利条件。现代上升洋流活跃的区域,如纳米比亚海岸、智利—秘鲁海岸、加利福尼亚海湾和阿拉伯海等,均存在成磷事件( Föllmi,1996; Filippelli,20082011; Lumiste et al.,2021)。此外,地质历史时期世界各地磷块岩的成因,如中东和北非晚白垩世磷矿床(Baioumy et al.,2011; Abed et al.,2013)及阿根廷新元古代晚期两次成磷事件(Gómez-Peral et al,2014),均利用上升洋流成矿来解释,即上升洋流携带深部富磷海水进入浅水海岸,在生物化学作用或其他地球化学作用下使磷质在浅水海岸进一步聚集形成磷块岩沉积。然而,也有学者对上升洋流成矿作用提出质疑,认为非上升洋流海岸同样可形成富磷沉积。 Berner 和 Ruttenberg(1993)在两个无上升流的浅水海岸发现了磷灰石的沉积,认为 “Fe—氧化还原泵” 系统也能够促使磷块岩在非上升洋流海岸沉积(Nelson et al.,2010)。 Drummond 等(2015)进一步指出,前寒武纪的磷块岩成因可能并非如显生宙时期的成磷事件那样与上升洋流密切相关,Fe—氧化还原模式及海水分层模式对前寒武纪磷质沉积具有重要影响。

  • 针对滇东北地区梅树村期磷块岩沉积,众多学者同样采用上升洋流成矿的理论进行解释(戈宏儒,1983; 曾允孚,1989; 东野脉兴,19962001; 邓小林,2007; 杨泽刚等,2012; 岳维好等,2012; 米云川,2024)。然而,对于富磷海水来源的方向,不同学者有不同的观点:大多数学者认为该地区的洋流来源多样,主要来自华南海和滇青藏—秦岭海广海; 有的学者则认为洋流主要来自滇青藏海; 还有一些学者认为洋流的来源是华南海。例如,曾允孚等(1989) 通过对滇东地区磷矿的详细古地理分析,认为富磷海水主要来自南方(华南海)和西方(滇青藏海),其依据包括:矿层的贫富程度自西向东逐渐减弱,西区磷矿质量较高,主要为菌藻磷块岩和磷基砂屑磷块岩; 小壳化石的数量和个体大小在东西区存在显著差异,西区丰富且个体较大; 陆源碎屑的含量和成分成熟度差异显著,西区陆源碎屑较少且成分成熟度较高; 沉积环境分布显示西侧为浅滩潟湖区,东侧为潮坪区; 这些证据表明富磷海水自西向东逐渐供应。另一些学者对白龙潭磷矿(孟永龙,2018)、云南寻甸大湾磷矿(苏旭楠,2018)和云南镇雄县银厂湾磷矿(沈燕飞等,2020)进行的研究也表明,该地区的洋流主要来源于华南海和滇青藏海。对于近年来新发现的镇雄羊场超大型磷矿,多项研究认为上升洋流的方向主要来自华南海和滇青藏—秦岭海广海的富磷海水,这些海水分别从东南方向和西北方向侵入硝滩—羊场聚磷盆地,流速逐渐减缓,磷酸盐堆积从贫到富(米云川等,20212024; 岳维好等,2022; 杨淑胜等,2024)。此外,王登芳等(2016)通过分析云南和贵州寒武系底部磷块岩的古地理分布,认为牛首山半岛对磷块岩沉积影响深远。寒武纪早期,海水从西南的康滇岛链和东南海盆的洋流进入扬子克拉通,富含磷质的上升洋流在浅水区域沉积并在高能环境下改造,最终形成碎屑状磷块岩。然而,戈宏儒(1983)根据古构造条件推测,认为滇东早寒武世沉积时期的海水来源并非通过蒙自、开远海峡自南方进入,而是由西方通过滇青藏大洋流入该地区。其主要依据是地层中存在从北向南逐渐超覆的现象,且滇东梅树村期的地层随着超覆和缺失呈现由北到南的变化,西部的深大断裂与滇青藏大洋之间的联系为海水进入提供了通道。随后,东野脉兴(19962001)对滇东北地区的研究也表明,早寒武世梅树村期,来自西部滇青藏深海的上升洋流到达该陆缘坻,滞留下来携带的磷等营养物质,尤其在相对凹陷的地段形成了大规模的磷块岩沉积,并构成了富民华宁、会东—东川、马边—雷波、汉源—乐山和清平—绵竹等五个聚磷区。一些学者则认为,滇东北地区磷矿形成时洋流的方向主要来自华南海(刘宝珺,1987; 邓小林等,2007)。这一观点的依据是古地磁研究,认为华南海槽曾是深部富磷洋流的传输通道,这些洋流影响了上扬子海盆的水质及磷质沉积的形成,富磷的上升洋流通过华南海槽进入上扬子海盆,因温度升高、压力降低和 CO2 逸出,促进了磷质沉积并形成磷块岩(邓小林等,2007)。

  • 综上所述,在地质历史时期磷块岩形成中,上升洋流发挥着关键作用。然而,部分学者认为并非所有磷矿沉积都依赖于上升洋流,Fe—氧化还原泵等地球化学过程也可能促使磷矿沉积,这对上升洋流成矿理论提出了挑战。目前,对于滇东北地区磷矿床的成因大多通过上升洋流成矿理论加以解释,但洋流来源方向的争议较大,未来还需要进一步研究。

  • 3.3 机械成矿作用

  • 机械堆积成因最早由 Grabau(1919)提出,他发现磷酸盐沉积常与不整合面和钙质基岩有关,认为这些磷块岩是由残余堆积形成的。萨尔温(1952)进一步发展了机械堆积成矿说,指出北非晚白垩世至始新世的磷块岩是由“生成区”的磷质在机械作用下搬运至“堆积区”形成的矿床。东野(1980)认为,机械成矿作用常形成规模大且富集的海相磷块岩矿床,而化学、生物化学及交代作用形成的磷块岩,则常常不构成或不单独构成工业矿床。叶连俊等(1986)则认为,世界上所有沉积型工业磷块岩矿床均为物理富集的直接产物。其在研究昆阳、开阳、瓮安以及荆襄等矿区的泥晶磷块岩和球粒砂屑磷块岩两种矿石类型时发现,从泥晶结构矿石向球粒砂屑结构矿石演变的过程中,P2O5 含量逐步提高,呈现出持续纯化的趋势。同时指出,华南地区埃迪卡拉纪至早寒武世的磷块岩矿床也主要由机械沉积作用形成,初始富集的磷质沉积物在海洋环境变化以及波浪和潮汐等地质动力作用下进一步富集并沉积,最终形成高品位磷矿床(叶连俊等,1989)。有学者对以色列内盖夫地区两种类型的磷矿石进行了大量定量研究,发现在所有研究区域中,从原生磷块岩向改造磷块岩过渡的过程中均伴随着 P2O5 含量的富集(Levy et al.,2023)。尽管许多学者认为机械作用是促进磷矿再次富集的主要因素,但近期有学者通过对黔中地区(如遵义松林、瓮安、福泉、开阳等地)的原生磷矿石和改造磷矿石进行研究后指出,化学/ 生化富集是浓缩磷酸盐沉积物最有效的途径,可显著提高 P2O5 的品位(最高可达 38.8%); 相比之下,机械作用在 P2O5 含量进一步富集中的作用可能较为有限(Qi Liang et al.,2023)。

  • 对于滇东北地区,有些学者同样认为在磷块岩的形成和富集过程中机械成矿作用起到了关键作用,磷质最初由上升洋流带至潮坪海湾,在生物化学和胶体化学作用下沉积形成凝胶状磷块岩,随后在波浪、潮汐和风暴等动力作用下,凝胶状磷块岩被破碎、簸选、搬运,再次沉积,形成颗粒状磷块岩,最终实现了磷的再次富集(邓小林等,2007; 米云川等,2024)。本综述通过收集和整理滇东北地区白龙潭磷矿床及羊场磷矿床中,具有明显原始特征与经过机械作用改造后特征的磷块岩常量元素 P2O5 含量测试数据(见表1),对改造前后磷块岩的 P2O5 含量进行了对比分析。结果表明,在同一矿床中,改造后的磷块岩 P2O5 含量与原始磷块岩相比并未显著增加,且其变化趋势无明显规律。因此,推测机械作用对磷块岩中 P2O5 含量的富集作用较为有限。

  • 3.4 同沉积热水混合成因

  • 对于热水沉积作用,前人利用同位素、微量元素比值特征、稀土元素配分特征和流体包裹体地球化学特征等方法进行研究,认为热液也参与了磷矿化过程,热水活动提供了部分磷质来源(陈永权等,2005; Li Da et al.,2009; Halverson et al.,2009; Liu Zeruiray and Zhou Meifu,2017; 杨万涛等,2021; 秦欢等,2022; 曹金鑫,2022; 苏旭楠等,2018)。

  • 陈永权等(2005) 首次利用硅同位素分析云南省会泽县小壳化石中石英的来源,发现其 Si 同位素值(δ30 SiNBS-28 =-0.6‰~0.1‰)与基质石英相当,但显著低于寒武纪底部硅质岩的同位素特征(δ30 SiNBS-28 = 0.4‰~1.4‰),表明其具有热液成因特征。同样,Liu Zeruiray 和 Zhou Meifu(2017)对云南梅树村剖面中谊村段磷矿层的自生石英进行硅同位素分析( δ+ SiNBS-28 =-0.4‰),以及 Li Da 等(2009)在云南老林地区朱家菁组上部的中谊村段磷块岩中测得的碳同位素组成(δ13CV-PDB =-3.20‰~0‰),均表明热液流体对磷矿化过程有显著影响。 Halverson 等(2009)指出,尽管风化作用广泛,使大量陆源物质进入沉积环境,但强烈的热液活动仍然导致沉积物的锶同位素组成低于陆源输入水平。这些磷矿床的地球化学特征表明,在磷矿化过程中,海底热液能够提供部分磷质来源。

  • 表1 原始磷块岩与机械作用改造后的磷块岩中 P2O5 含量(%)

  • Table1 P2O5 content (%) in the original phosphorite and the phosphorite modified by mechanical action

  • 杨万涛等(2021)对云南沾益小米戛磷矿的 Sr/ Ba 比值(0.10~1.40)和 U/ Th 比值(1.35~4.15)分析,表明矿床形成过程中有热液活动的介入。同时,稀土元素配分中 Ce 的负异常和北美页岩标准化模式形状近于水平,进一步支持了这一观点。秦欢等(2022)对羊场磷矿磷块岩中的微量元素进行研究,得出 w(Th)/ w(U)比值很低(0. 02~0.17),由此认为羊场磷块岩具有热水沉积成因。类似地,曹金鑫等(2022)通过东川白龙潭磷块岩的 U/ Th 比值大于 1,且大部分样品在 lgw(U)-lgw(Th)图中位于热水沉积区,进一步验证了白龙潭磷块岩的热水沉积成因。

  • 苏旭楠等(2018) 通过分析云南寻甸大湾磷矿的 U/ Th 比值及 Fe—Mn—( Ni +Cu +Co)× 10 三角图,确认该矿床具有热水沉积特征。 U/ Th 比值大于1(范围为 0.53 至 2.69,均值为 1.7)表明该矿床受热水沉积的影响显著; 同时,Fe 和 Mn 的富集以及 Cu、Ni、Co 的相对缺失,进一步反映了热水环境下快速沉积的特征。

  • 综上所述,不少学者认为热水沉积在磷矿形成过程中起到了重要作用。然而,有学者研究认为,磷块岩地球化学特征显示的热水沉积现象,也有可能是源于上升洋流携带的富磷深水水团( 毛铁,2015)。在浅水区,由于物理化学条件的改变,磷质迅速沉淀,而深水水团与浅水环境之间的物质交换较为有限,导致磷块岩沉淀中地球化学指标主要反映了深水水团的地球化学特征,也即深海环境的地球化学特性,从而呈现出热水沉积的特征。

  • 4 成矿模式探讨

  • 关于磷块岩矿床的成因机制,仍存在较大争议,学术界目前主要提出生物成磷说、上升流成磷说、机械成矿作用及同沉积热水混合成因等不同观点。现有研究表明,磷矿的成因可能与富磷海水的直接沉淀、碳酸盐交代作用、微生物作用等过程密切相关,或是这些过程的相互作用和组合所致。因此,磷矿床的成因机制不应仅从某一方面进行单一探讨,也应综合考虑各类影响因素,未来也需要加强磷块岩显微组构微区分析研究工作,深入研究磷沉积过程及矿化作用的复杂性和多样性。

  • 综合上述研究内容,推测滇东北磷矿的成矿模式(图4)。

  • (1)磷质来源:成矿物质主要来源于上升洋流携带的深海富磷水体; 其次为生物,尤其是小壳生物。

  • (2)磷质富集与矿化过程:上升洋流将富磷海水从深部带到浅水区,在适宜的盐度和氧化还原条件下,磷质通过化学和生物化学过程形成凝胶状磷块岩。在此过程中,生物活动发挥了关键作用,菌藻类微生物和小壳动物,尤其是大量的小壳动物,通过吸收、沉淀和分解有机物,将海水中的磷质富集并固结成矿(东野脉兴,1996; 陈其英等,1995; 杨万涛等,2021; 吕俊,2021)。此外,研究表明,“ Fe—氧化还原泵”机制在磷矿的成矿过程中可能起到重要作用,通过 Fe2+在还原环境中的迁移及其在氧化环境下的沉淀,进一步促进磷质在氧化界面的集中,形成富磷矿物( Berner and Ruttenberg,1993; Nelson et al.,2010)。

  • 图4 滇东北梅树村期磷矿成矿模式图(据 Godet et al.,2021; 张亚冠,2019 修编)

  • Fig.4 Metallogenic model of the Meishucun period phosphate deposits in northeastern Yunnan (revised based on Godet et al., 2021; Zhang Yaguan, 2019&)

  • (3)磷块岩再沉积与成岩:磷块岩在沉积后经历了波浪、潮汐等水动力作用的破碎、冲刷和簸选,部分磷块岩颗粒被重新搬运至低洼区域进行再沉积(东野,1980; 邓小林等,2007; 董涛,2024)。随后的成岩作用进一步固结了这些沉积物,使磷矿床得以完整保存。

  • 5 结论与展望

  • 通过总结分析滇东北早寒武世梅树村期磷矿的相关研究,得出了以下几点结论:

  • (1)滇东北地区磷矿的成矿古地理环境一般认为形成于浅海碳酸盐台地及台地凹陷盆地,但具体位置仍有差异。结合该地区矿石类型特征,主要为碎屑磷块岩、条带状磷块岩和泥晶质磷块岩等,并且含有大量的生物,可以推测滇东北地区磷矿的主要沉积环境为浅海碳酸盐台地凹陷盆地。其中凹陷斜坡上部的潮间环境,沉积碎屑状磷块岩为主,斜坡下部的潮下环境,沉积条带状磷块岩、泥晶质磷块岩为主。属于低纬度干旱高盐度浅海环境,且氧化—还原界面附近最有利用磷沉淀。未来研究应进一步分析镇雄羊场、昭通大关等地是什么沉积环境、关键因素沉积巨厚磷块岩。

  • (2)滇东北地区磷矿的物质来源主要与深部富磷水团和小壳生物相关。富磷水团通过上升洋流进入浅水区,携带的磷质在适宜条件下沉淀,可能促进了磷矿的形成。小壳生物的生物作用也可能发挥了推动作用。未来需进一步研究滇东北磷矿与贵州织金、威宁地区磷矿之间成因关联性,分析滇黔寒武纪梅树村期磷矿成矿之间异同,完善梅树村期磷矿成矿理论。

  • (3)磷矿成矿机制主要包括生物成磷、上升洋流作用和机械成矿作用等,但对这些成因的理解仍存分歧,原因在于现有研究未能充分解释各成因在沉积与成岩中的相互作用,且缺乏磷酸盐组分微观结构的分析。因此,未来应除了从地球化学角度研究外,关注磷酸盐组分的微区成分、显微结构及沉积富集形态,利用先进技术揭示磷矿微观沉积过程,探讨不同成因之间的关系。特别是洋流方向的研究,需要进一步深入,同时与巨厚磷矿沉积区结合,分析大量磷矿沉积与上升洋流方向、持续时间等之间的关系。

  • (4)尽管大量研究为滇东北磷矿成矿模式提供了线索,也建立了各种类型成矿模式,但在成矿古地理位置、物质来源和成矿机制等方面仍未达成统一。因此,未来研究应在现有基础上,采用新方法,从成矿地质背景、物质来源、沉积作用和成岩作用等方面入手,进一步探索滇东北磷矿的成矿模式,并构建更加完善的成矿理论,这是未来研究的重点方向。

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