金的赋存状态与超常富集机制:胶东新城金矿载金黄铁矿纳米结构约束

doi:10.13745/j.esf.sf.2025.1.36

地学前缘 ›› 2026, Vol. 33 ›› Issue (2): 148-162.DOI: 10.13745/j.esf.sf.2025.1.36

• 战略矿产成因机制与金属富集 • 上一篇下一篇

金的赋存状态与超常富集机制:胶东新城金矿载金黄铁矿纳米结构约束

李瑞红¹(), 杨立强², 龙涛³, 袁士松¹^,^*(), 于皓丞², 邵兴坤¹, 肖雪¹

1.中国地质调查局廊坊自然资源综合调查中心, 河北廊坊 065000
2.中国地质大学(北京) 深时数字地球前沿科学中心/地质过程与矿产资源国家重点实验室, 北京 100083
3.中国地质科学院地质研究所, 北京 100037

收稿日期:2024-09-02 修回日期:2025-09-07 出版日期:2026-03-25 发布日期:2026-01-29
通信作者: *袁士松(1977—),男,博士,正高级工程师,主要从事金矿地质研究工工作。E-mail: yuanshisong@mail.cgs.gov.cn
作者简介:李瑞红(1989—),男,博士,高级工程师,硕士生导师,主要从事金矿地质与勘查研究工作。E-mail: lruihong@mail.cgs.gov.cn
基金资助:
国家自然科学基金项目(42002108);中国地质调查局地质调查项目(DD20240206802);中国地质调查局地质调查项目(DD20242942);中国地质调查局地质调查项目(DD20240013);国家重点研发计划项目(2023YFC2906900);廊坊中心燕赵山水基金项目(YZSSJJ202401-004)

Occurrence state and super-enrichment mechanism of gold: Constraint of the nanostructure of the Xincheng gold deposit in Jiaodong

LI Ruihong¹(), YANG Liqiang², LONG Tao³, YUAN Shisong¹^,^*(), YU Haocheng², SHAO Xingkun¹, XIAO Xue¹

1. Langfang Natural Resources Comprehensive Survey Center, China Geological Survey, Langfang 065000, China
2. Frontiers Science Center for Deep-time Digital Earth/State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Beijing), Beijing 100083, China
3. Institute of Geology, Chinese Academy of Geological Sciences, Beijing 100037, China

Received:2024-09-02 Revised:2025-09-07 Online:2026-03-25 Published:2026-01-29

摘要/Abstract

摘要：

巨量金的迁移成矿与超常富集机制是矿床学研究热点,载金黄铁矿纳米结构是揭示金赋存状态及约束纳米尺度金超常富集机制的关键。胶东新城金矿是典型的构造破碎带蚀变岩型金矿,并且其主矿体金平均品位较高,载金黄铁矿中金发生了显著的富集。本文通过详细的岩相学和矿相学研究,厘定了成矿期4种类型的黄铁矿。应用光学显微镜、扫描电子显微镜聚焦离子束、球差校正透射电子显微镜和三维原子探针技术方法组合,对其纳米结构进行了研究分析,揭示出:(1)载金黄铁矿内部发育大量塑性显微构造变形,主要有不连续斜列位错线、位错缠结、位错扭折带和孤立分布刃型位错等;(2)载金黄铁矿晶体[$\bar{2} $01]晶带轴电子衍射花样标定结果显示晶面间距最大为0.545 nm,最小为0.219 nm;(3)载金黄铁矿三维原子探针测试结果显示载金黄铁矿分子式为FeS_1.73,金原子均匀分布,发育银原子团簇;(4)载金黄铁矿中金原子在黄铁矿中均匀分布,含量约为2×10^-6,原子个数检测误差为4.25×10^-9。综上,载金黄铁矿纳米结构及其三维原子分布特征,反映了成矿过程中黄铁矿纳米结构畸变导致的晶体缺陷等微观结构变化对金元素迁移与富集过程在原子和纳米团簇尺度具有控制作用。

关键词: 载金黄铁矿, 显微构造变形, 纳米结构, 金赋存状态, 三维原子重建

Abstract:

The mechanisms enabling the transport and anomalous enrichment of gold at the nanoscale remain a research hotspot in economic geology. The microstructure of gold-hosting pyrite is key to understanding the occurrence of gold and constraining the processes leading to its extreme enrichment. The Xincheng gold deposit in Jiaodong is a typical altered rock-type deposit characterized by high-grade ores and significant gold enrichment within pyrite. Petrographic and mineralogical studies identified four types of ore-stage pyrite. To investigate their nanostructures, we employed a combination of focused ion beam-scanning electron microscopy (FIB-SEM), spherical aberration-corrected transmission electron microscopy (Cs-TEM), and atom probe tomography (APT). The results show that: (1) Pyrite hosts numerous plastic deformation features, including discontinuous dislocation lines, tangles, and deformation twins. (2) Electron diffraction patterns from the [$\bar{2} $01] zone axis of gold-bearing pyrite indicate interplanar spacings ranging from 0.219 nm to 0.545 nm. (3) Atom probe tomography (APT) indicates a non-stoichiometric pyrite composition approaching FeS_1.73. Gold is homogeneously distributed at the atomic scale, with a concentration of ~2 ppm and a detection sensitivity of 4.25 ppb, while silver forms discrete clusters. In summary, the nanoscale crystal defects (e.g., dislocations) generated by deformation in pyrite exert a primary control on the distribution and enrichment of gold, from the atomic scale to the cluster scale.

Key words: gold-bearing pyrite, microstructure deformation, nanostructure, occurrence state of gold, 3D atomic reconstruction

中图分类号:

李瑞红, 杨立强, 龙涛, 袁士松, 于皓丞, 邵兴坤, 肖雪. 金的赋存状态与超常富集机制:胶东新城金矿载金黄铁矿纳米结构约束[J]. 地学前缘, 2026, 33(2): 148-162.

LI Ruihong, YANG Liqiang, LONG Tao, YUAN Shisong, YU Haocheng, SHAO Xingkun, XIAO Xue. Occurrence state and super-enrichment mechanism of gold: Constraint of the nanostructure of the Xincheng gold deposit in Jiaodong[J]. Earth Science Frontiers, 2026, 33(2): 148-162.

图/表 13

图1 新城金矿四个热液成矿阶段黄铁矿类型及手标本照片 A-C—新城金矿成矿第Ⅰ阶段石英—黄铁矿阶段矿石手标本及I型黄铁矿(Py1);D-F—第Ⅱ阶段金-石英-黄铁矿阶段矿石手标本及II型细粒黄铁矿(Py2);G-I—第Ⅲ阶段金-石英-多金属硫化物阶段矿石手标本及III型黄铁矿(Py3);J-L—第Ⅳ阶段黄铁矿-碳酸盐阶段矿石手标本及IV型黄铁矿(Py4)。Q—石英;Py—黄铁矿;Ser—绢云母;Kf—钾长石;Cc—方解石;El—银金矿。

Fig.1 Photos of pyrite hand samples in four hydrothermal mineralization stages

图2 新城金矿热液黄铁矿中可见金的赋存状态 A—黄铁绢英岩;B—II型黄铁矿(Py2)分布特征;C-E—II型黄铁矿(Py2)中可见金分布特征;F—扫描电子显微镜下II型黄铁矿(Py2)FIB制样位置。Q—石英;Py—黄铁矿;Ser—绢云母;Gn—方铅矿;El—银金矿。

Fig.2 The occurrence of gold in hydrothermal pyrite

图3 新城金矿热液黄铁矿样品野外产出特征 A-C—新城金矿成矿第Ⅰ阶段黄铁矿-石英阶段I型黄铁矿(Py1)野外产出特征;D-F—第Ⅱ阶段金-石英-黄铁矿阶段II型黄铁矿(Py2)野外产出特征;G-I—第Ⅲ阶段金-石英-黄铁矿-多金属硫化物阶段III型黄铁矿(Py3)野外产出特征;J-L—第Ⅳ阶段黄铁矿-碳酸盐阶段IV型黄铁矿(Py4)野外产出特征。Q—石英;Py—黄铁矿;Ser—绢云母;Gn—方铅矿;Cp—黄铜矿;Sp—闪锌矿;Cc—方解石。

Fig.3 Field photo of hydrothermal pyrite samples

表1 不同成矿阶段热液黄铁矿样品采样位置

Table 1 Sampling locations of hydrothermal pyrite samples at different mineralization stages

成矿阶段	岩性	标高/m	采样位置	矿体编号	金品位/(g·t^-1)	质量/kg
Ⅰ	石英黄铁矿脉	-350	4144877,512225和-350151盘区	I号	3	10
Ⅱ	黄铁绢英岩	-350	4144961,512361和-350161盘区沿脉	I号	3	10
Ⅲ	多金属硫化物脉	-580	4145186,513364和-580177下盘采矿场	V号	3	10
Ⅳ	方解石脉	-320	4144414,512787和-320151-3盘区	I号	2	10

图4 高分辨率透射电子显微镜下载金热液黄铁矿显微构造变形特征 A—载金黄铁矿样品观测选区;B,C—不连续斜列位错线;D—位错缠结;E—位错扭折带;F-H—孤立刃型位错分布特征;I,J—载金黄铁矿与银金矿晶体接触关系;K,L—银金矿晶格特征(Py4)。Py—黄铁矿;El—银金矿。

Fig.4 The characteristics of microstructural deformation of gold-bearing hydrothermal pyrite obtained by high-resolution transmission electron microscopy

图5 球差校正透射电子显微镜下载金热液黄铁矿与金的显微结构特征 A—载金黄铁矿样品观测选区;B—载金黄铁矿与银金矿晶体界面;C-F—界面晶体析出与接触关系;G,H—黄铁矿与银金矿晶体界面局部共格生长;I—银金矿晶内析出相(纳米级金颗粒)。Py—黄铁矿;El—银金矿。

Fig.5 The characteristics of microstructure of hydrothermal pyrite and gold in gold solution obtained by Spherical aberration correction transmission electron microscopy

图6 载金热液黄铁矿与金的电子衍射花样及标定 A,B—银金矿电子衍射花样与标定;C,D—载金黄铁矿电子衍射花样与标定;E—载金黄铁矿与银金矿界面电子衍射花样;F—银金矿界面电子衍射花样。

Fig.6 Electron diffraction pattern and calibration of gold-bearing hydrothermal pyrite and gold

表2 载金热液黄铁矿与金的电子衍射花样参数统计

Table 2 Electron diffraction pattern parameter statistics of gold-bearing hydrothermal pyrite and gold

矿物类型	R₁	R₂	R₃	R₂/R₁	R₃/R₁	R₁^R₂	R₁^R₃	R₂^R₃	d₁	d₂	d₃	晶带轴
黄铁矿	1.834	4.125	4.559	2.249	2.486	90°	65.97°	24.13°	0.545	0.242	0.219	[$\bar{2} $01]
银金矿	4.184	6.931	8.084	1.657	1.932	90°	58.95°	31.05°	0.239	0.144	0.124	[1$\bar{2} $1]
黄铁矿	1.840	2.600	3.200	1.410	1.739	90°	35.57°	55.18°	0.540	0.39	0.310	[101]
银金矿	4.250	6.870	8.090	1.620	1.904	90°	31.60°	58.40°	0.235	0.146	0.124	[1$\bar{1} $2]

图7 球差校正透射电子显微镜下载金热液黄铁矿与金晶体结构 A—载金黄铁矿与银金矿晶体界面晶格变形;B—载金黄铁矿析出晶体结构及点缺陷原子分布;C—黄铁矿晶体内部晶格错断变形;D-F—析出相晶体形态与界面晶格变形偏转;G—黄铁矿晶内线缺陷特征与晶格畸变;H—黄铁矿晶内线缺陷、晶格变形特征;I—黄铁矿与银金矿界面析出晶体特征。Py—黄铁矿;El—银金矿。

Fig.7 Crystal Structure of gold-bearing hydrothermal pyrite and gold in gold obtained by spherical aberration correction transmission electron microscopy

图8 球差校正透射电子显微镜能谱扫面载金热液黄铁矿元素分布 Py—黄铁矿;El—银金矿。

Fig.8 Element distribution of gold-bearing hydrothermal pyrite scanned by energy spectrum of spherical aberration correction transmission electron microscopy

图9 原子探针重构载金热液黄铁矿三维空间原子分布图

Fig.9 Reconstruction of three-dimensional spatial atomic distribution of gold-bearing hydrothermal pyrite by atom probe

表3 载金热液黄铁矿三维原子探针测试结果统计表

Table 3 Statistical of test results of gold-bearing hydrothermal pyrite by 3D atom probe

原子类型	分解原子计数/个	原子含量/10^-6	原子计数误差
Fe	21 399 300	363 987.30	0.83×10^-6
S	36 927 725	628 115.06	0.76×10^-6
Au	116	2.00	4.25×10^-9
Ag	2 430	41.34	13.10×10^-9
Cu	2 018	34.34	45×10^-9
As	184	3.14	6.09×10^-9
Co	7 816	132.98	20.6×10^-9
Ni	109 882	1 869.03	94.8×10^-9
H	314 613	5 351.41	87.20×10^-9
O	26 501	450.82	0.62×10^-6
Cl	739	12.58	13×10^-9

图10 热液黄铁矿纳米结构自组织调节机制与金的富集关系(据文献[39,61]修改)

Fig.10 The relationship between crystal structure change of hydrothermal pyrite and gold enrichment. Modified after [39,61].

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金的赋存状态与超常富集机制:胶东新城金矿载金黄铁矿纳米结构约束

Occurrence state and super-enrichment mechanism of gold: Constraint of the nanostructure of the Xincheng gold deposit in Jiaodong

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