贵州瓮安陡山沱期球粒状磷块岩的生物成磷作用探讨<sup>&#x0002A;</sup>

doi:10.7605/gdlxb.2025.041

古地理学报 ›› 2025, Vol. 27 ›› Issue (2): 395-410. doi: 10.7605/gdlxb.2025.041

贵州瓮安陡山沱期球粒状磷块岩的生物成磷作用探讨^*

高川黔¹^,²(), 杨瑞东¹^,²(), 高军波¹^,², 彭柔¹^,², 李晓伟¹^,², 陈军¹^,², 陈吉艳¹^,²

1 贵州大学资源与环境工程学院,贵州贵阳 550025
2 贵州大学喀斯特地质资源与环境教育部重点实验室,贵州贵阳 550025

收稿日期:2024-09-01 修回日期:2024-11-19 出版日期:2025-04-01 发布日期:2025-04-01
作者简介:
高川黔,女,1999年生,硕士研究生,主要从事沉积矿产研究。E-mail: 1922521159@qq.com。
基金资助:
*国家重点研发计划项目(编号: 2023YFC2906604)、国家自然科学基金项目(编号: U23A2027)和贵州省地质勘查资金项目(编号: 2024-2号)联合资助

Study on biogenic phosphogenesis of spheroidal phosphorite from the Doushantuo Formation in Weng’an, Guizhou Province

GAO Chuanqian¹^,²(), YANG Ruidong¹^,²(), GAO Junbo¹^,², PENG Rou¹^,², LI Xiaowei¹^,², CHEN Jun¹^,², CHEN Jiyan¹^,²

1 College of Resources and Environmental Engineering,Guizhou University,Guiyang 550025,China
2 Key Laboratory of Karst Georesources and Environment,Ministry of Education,Guizhou University,Guiyang 550025,China

Received:2024-09-01 Revised:2024-11-19 Online:2025-04-01 Published:2025-04-01
About author:
GAO Chuanqian,born in 1999,is a masteral degree candidate. She is mainly engaged in sedimentary mineral research. E-mail: 1922521159@qq.com.
Supported by:
Co-funded by the National Key Research and Development Plan(No.2023YFC2906604),the National Natural Science Foundation of China(No. U23A2027)and the Fund Project of Guizhou Province Geology Exploration(No.2024-2)

摘要/Abstract

摘要：

贵州瓮安陡山沱组海相沉积型磷块岩矿床是新元古代末期成磷事件的典型代表之一,在磷矿层中保存大量的三维立体化石,包括藻类、疑源类、动物胚胎以及休眠卵等化石类型,显示出生物在磷富集成矿中的重要作用。以贵州瓮安穿岩洞陡山沱组上磷矿层底部的球粒状磷块岩为研究对象,通过对未经化学方法处理的球粒实体进行体视显微镜和电子显微镜观察膜壳和内部结构; 对样品薄片进行光学显微镜和电子显微镜观察其显微结构特征。同时利用电感耦合等离子体发射光谱(ICP-OES)、电感耦合等离子体质谱(ICP-MS)以及X射线荧光光谱仪(XRF), 测定球粒化石颗粒中主量与微量元素含量。研究表明,这些球粒状磷块岩主要由多细胞藻类、Megasphaera球状化石以及其他磷质微生物化石体组成,化石体的主要组成矿物为氟磷灰石。进一步探讨了微生物与成磷之间的关系,认为陡山沱晚期微生物的繁盛对磷沉淀富集成矿起着重要的作用。微生物不仅能吸附磷质进入细胞质、细胞核以及细胞壁中,死亡后磷酸盐化,形成磷块岩; 还可以通过改变沉积水体环境,促进海水中磷酸盐的化学沉积。

关键词: 球粒状磷块岩, 生物成磷作用, 陡山沱组, 瓮安, 贵州省

Abstract:

The marine sedimentary phosphate deposit of the Doushantuo Formation in Weng’an,Guizhou Province,is a typical representative of Late Neoproterozoic phosphate formation. This deposit preserves a diverse array of three-dimensional fossils,including algae,hypogenites,animal embryos,and dormant eggs,highlighting the crucial role of biological processes in phosphate enrichment and mineralization. This study focuses on the spheroidal phosphates found at the base of the upper phosphate layer of the Doushantuo Formation in Weng’an,Guizhou. The membrane shell and internal structure of untreated spheroidal solids were examined using stereomicroscopy and electron microscopy. The microstructures of thin sections were further analyzed through optical and electron microscopy. Additionally,the main and trace elements in the pelletal phosphorite were determined using Inductively Coupled Plasma Emission Spectroscopy(ICP-OES),Inductively Coupled Plasma Mass Spectrometry(ICP-MS),and X-ray fluorescence spectrometry(XRF). The results indicate that these spheroidal phosphates primarily consist of multicellular algae,Megasphaera spherical fossils,and other phosphatic microbial fossils,with fluorocarbon-fluorapatite as the dominant mineral component. The relationship between algal microorganisms and phosphate formation is explored,leading to the conclusion that the proliferation of algal microorganisms in the late Doushantuo period played a vital role in phosphate precipitation,enrichment,and mineralization. These microorganisms not only absorbed phosphate into their cytoplasm,nucleus,and cell walls during life but also contributed to phosphate formation after death. Furthermore, phosphate chemical deposition in seawater was likely enhanced by microbial activity, which altered the environmental conditions of the sedimentary water.

Key words: spheroidal phosphate, biophosphorization, Doushantuo Formation, Weng’an, Guizhou Province

高川黔, 杨瑞东, 高军波, 彭柔, 李晓伟, 陈军, 陈吉艳. 贵州瓮安陡山沱期球粒状磷块岩的生物成磷作用探讨^*[J]. 古地理学报, 2025, 27(2): 395-410.

GAO Chuanqian, YANG Ruidong, GAO Junbo, PENG Rou, LI Xiaowei, CHEN Jun, CHEN Jiyan. Study on biogenic phosphogenesis of spheroidal phosphorite from the Doushantuo Formation in Weng’an, Guizhou Province[J]. Journal of Palaeogeography（Chinese Edition）, 2025, 27(2): 395-410.

http://www.gdlxb.cn/CN/Y2025/V27/I2/395

图/表 13

图1 贵州瓮安穿岩洞陡山沱组沉积地质背景及剖面地层柱状图
a—扬子板块陡山沱沉积期古地理图(修改自Zhang et al., 2019);b—穿岩洞磷矿地质简图(修改自梁坤萍等,2022);c—穿岩洞陡山沱组地层柱状图及采样位置

Fig.1 Sedimentary geological background and stratigraphic column of the Doushantuo Formation at Chuanyandong,Weng’an,Guizhou Province

图2 贵州瓮安穿岩洞陡山沱组磷块岩上矿层底部磷块岩特征
a—碎屑状磷块岩中球粒状磷块岩夹层; b—球粒状磷块岩; c—球状生物化石颗粒

Fig.2 Characteristics of phosphate rock at bottom of upper layer of phosphate rock in the Doushantuo Formation at Chuanyandong,Weng’an,Guizhou Province

图3 贵州瓮安穿岩洞陡山沱组球粒状磷块岩中化石显微结构
a—呈球状、次球状的化石颗粒,单偏光; b—化石碎块,单偏光; c—球状化石生物结构,扫描电镜下背散射成像; d—球状化石内部链状生物结构,扫描电镜下背散射成像; e—球状化石内部球状结构,扫描电镜下二次电子成像; f—磷灰石矿物颗粒,扫描电镜下二次电子成像

Fig.3 Microstructure of fossils in the Doushantuo Formation spheroidal phosphate at Chuanyandong,Weng’an,Guizhou Province

图4 贵州瓮安穿岩洞陡山沱组球粒状磷块岩中球状化石膜壳显微结构
图片均为扫描电镜下二次电子成像; a—膜壳光滑无纹饰; b—膜壳具脑纹状纹饰; c—多层膜壳结构; d—为c的局部放大

Fig.4 Microstructure of spheroidal fossil membrane shell in the Doushantuo Formation spheroidal phosphate at Chuanyandong,Weng’an,Guizhou Province

图5 贵州瓮安穿岩洞陡山沱组球粒状磷块岩中胚胎化石显微结构
图片均为扫描电镜下背散射成像; a—胚胎化石; b—为a中局部放大,磷化细丝和小球体,红框中为组成磷化细丝的磷化小球体横截面,由放射状磷灰石组成

Fig.5 Microstructure of embryo fossils in the Doushantuo Formation spheroidal phosphate at Chuanyandong,Weng’an,Guizhou Province

图6 贵州瓮安穿岩洞陡山沱组球粒状磷块岩中多细胞藻类化石显微结构
图片均为扫描电镜下背散射成像图; a、b—多细胞藻化石碎片; c—保存完整的多细胞藻类化石; d、e—多细胞藻类化石中分化现象; f—为e中红色方框放大图,内部细胞质中保存有黄铁矿晶体

Fig.6 Microstructure of multicellular algae fossils in the Doushantuo Formation spheroidal phosphate at Chuanyandong,Weng’an,Guizhou Province

图7 贵州瓮安穿岩洞陡山沱球粒状磷块岩中多分体细胞和细胞岛显微结构
a、d图片为单偏光,其余图片均为扫描电镜下背散射成像; a、b、c—单体、二分体、四分体细胞; d—细胞岛结构; e—藻化石碎片; f—为e中红色方框放大图,细胞岛结构; g—为e中红色方框放大图,单体、二分体、四分体细胞

Fig.7 Microstructures of polymeric cells and cell islands in the Doushantuo Formation at Chuanyandong,Weng’an,Guizhou Province

图8 贵州瓮安穿岩洞陡山沱组球粒状磷块岩中藻类细胞“喷泉结构”
图片均为扫描电镜下背散射成像

Fig.8 “Fountain structure” of algal in the Doushantuo Formation spheroidal phosphate at Chuanyandong,Weng’an,Guizhou Province

图9 贵州瓮安穿岩洞陡山沱组球粒状磷块岩中Megasphaera球状化石显微结构
a—处于Parapandorna阶段的Megasphaera 化石; b—为a图中红色方框放大图,细胞核磷酸盐化呈不规则状; c—Megaclonophyus阶段的球状化石; d—“套娃”结构; e—Megaclonophyus阶段的球状化石; f—为e红色方框中放大图; 图d为单偏光,其余图片均为扫描电镜下背散射成像

Fig.9 Microstruture of Megasphaera spheroidal fossil in the Doushantuo Formation spheroidal phosphate at Chuanyandong,Weng’an,Guizhou Province

图10 贵州瓮安穿岩洞陡山沱组球粒状磷块岩中单体、二分体和四分体细胞化石显微结构
a、b为扫描电镜下背散射成像,c、d为单偏光

Fig.10 Microstructures of monads,diad and tetrad cells fossil in the Doushantuo Formation spheroidal phosphate at Chuanyandong,Weng’an,Guizhou Province

表1 贵州瓮安穿岩洞陡山沱组球粒状磷块岩主量元素含量(%)

Table1 Main element contents(%)of spheroidal phosphorite in the Doushantuo Formation at Chuanyandong,Weng’an,Guizhou Province

样品	P₂O₅	Al₂O₃	CaO	F	TFe₂O₃	K₂O	MgO	SiO₂	SO₃	CaO/P₂O₅
WAxb-0	34.10	0.22	47.00	2.70	0.07	0.04	0.28	8.89	0.82	1.38

表2 贵州瓮安穿岩洞陡山沱组球粒状磷块岩微量元素含量(10^-6)

Table2 Trace element contents (10^-6) of spheroidal phosphorite in the Doushantuo Formation at Chuanyandong, Weng’an, Guizhou Province

样品	As	Ba	Be	Cd	Cu	Co	Mn	Ni	Pb	Sb	Se	Sr	Th	U	V	Zn	Zr
WAxb-0	24.3	828	2.75	1.46	15.5	0.7	185	7.9	1.7	0.5	2	1235	0.23	3.28	3	231	10
地壳平均	1.8	425	2.8	0.2	55	25	950	75	12.5	0.2	0.05	375	9.6	2.7	135	70	165
碳酸盐岩平均	1	100			4	0.1	1100	20	20			610			20	20
现代海底磷块岩平均	27.5	350			2.8	0.1	13.8	10.5				2800			18.8	55.5

图11 贵州瓮安穿岩洞陡山沱组生物富磷模式

Fig.11 Model of biophosphorization in the Doushantuo Formation at Chuanyandong,Weng’an,Guizhou Province

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贵州瓮安陡山沱期球粒状磷块岩的生物成磷作用探讨^*

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