磷灰石年代学、地球化学特征对大厂矿田东矿带大幅楼脉状Sn-Zn矿床成矿作用的指示

doi:10.13745/j.esf.sf.2025.1.19

地学前缘 ›› 2026, Vol. 33 ›› Issue (2): 88-104.DOI: 10.13745/j.esf.sf.2025.1.19

• 战略矿产前沿分析与勘查技术 • 上一篇下一篇

磷灰石年代学、地球化学特征对大厂矿田东矿带大幅楼脉状Sn-Zn矿床成矿作用的指示

张宇¹^,²^,³(), 肖昌浩²^,³^,⁴^,⁵^,^*(), 于萍萍²^,³, 张闰峰⁵^,²^,³, 胡利娟²^,³

1.中国地质大学(北京) 地球科学与资源学院, 北京 100083
2.中国地质科学院地质力学研究所动力成岩成矿实验室, 北京 100081
3.自然资源部古地磁与古构造重建重点实验室, 北京 100081
4.中国地质科学院地质力学研究所深地探测与矿产勘查全国重点实验室, 北京 100094
5.桂林理工大学有色金属矿产勘查与资源高效利用省部共建协同创新中心, 广西桂林 541006

收稿日期:2024-07-28 修回日期:2025-02-12 出版日期:2026-03-25 发布日期:2026-01-29
通信作者: *肖昌浩(1986—),男,博士,研究员,主要从事矿田构造和矿床学研究。E-mail: xiaochanghao1986@126.com
作者简介:张宇(1997—),男,博士研究生,主要从事矿床学研究。E-mail: 3001220048@email.cugb.edu.cn
基金资助:
国家科技重大科技专项项目(2024ZD1001701);中国地质科学院基本科研业务费专项经费项目(DZLXJK202206);中国地质科学院基本科研业务费专项经费项目(DZLXJK202203);自然资源部古地磁与古构造重建重点实验室开放课题(KLPTR-08);中国地质调查局项目(DD20240127);中国地质调查局项目(DD20230344);广西重点研发计划项目(2024AB21027)

Tin mineralization of the Dafulou quartz vein-type Sn-Zn deposit, Dachang district: Constrained by the apatite geochronology and geochemical characteristics

ZHANG Yu¹^,²^,³(), XIAO Changhao²^,³^,⁴^,⁵^,^*(), YU Pingping²^,³, ZHANG Runfeng⁵^,²^,³, HU Lijuan²^,³

1. School of Earth Sciences and Resources, China University of Geosciences (Beijing), Beijing 100083,China
2. Laboratory of Dynamic Diagenesis and Metallogenesis, Institute of Geomechanics, Chinese Academy of Geological Sciences, Beijing 100081, China
3. Key Laboratory of Paleomagnetism and Tectonic Reconstruction, Ministry of Natural Resources, Beijing 100081, China
4. State Key Laboratory of Deep Earth and Mineral Exploration, Institute of Geomechanics, Chinese Academy of Geological Sciences, Beijing 100094, China
5. Collaborative Innovation Center for Exploration of Nonferrous Metal Deposits and Efficient Utilization of Resources by the Province and Ministry, Guilin University of Technology, Guilin 541006, China

Received:2024-07-28 Revised:2025-02-12 Online:2026-03-25 Published:2026-01-29

摘要/Abstract

摘要：

丹池成矿带是我国华南重要的锡多金属集中区域,大厂矿田锡多金属成矿与晚白垩世黑云母花岗岩(笼箱盖岩体)密切相关。然而,岩浆-热液演化过程中熔/流体化学性质、挥发分、体系氧逸度变化等尚不明确,从而限制了对大厂矿田锡多金属矿床锡富集机制和矿床成因的理解。笔者首次在大厂矿田东段大幅楼Sn-Zn矿床22-1号矿体中发现了与锡矿化密切相关的自形粗粒热液磷灰石,结合已有黑云母花岗岩、花岗斑岩脉中未蚀变岩浆磷灰石和蚀变磷灰石资料,利用岩浆-热液演化过程中熔/流体化学性质变化,系统探讨锡富集机制和矿床成因的关键科学问题,同时,建立利用磷灰石地球化学数据区分锡矿与其他成因类型矿床的新型综合图解,为找矿勘查提供指导。为此,笔者对大幅楼矿床热液磷灰石开展了精细矿相学研究、激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS) U-Pb定年、X射线荧光光谱(XPS)和电子探针(EPMA)主量成分分析工作。磷灰石矿相学结果表明,自形粗粒磷灰石(粒径为50~200 μm)主要与铁氧化物、锡石、钛铁矿和石英共生。电子背散射(BSE)图像和XPS面扫描分析下,磷灰石表面均一,不发育环带,Ca、P和F元素分布均匀。电子探针主量元素分析表明,磷灰石明显富F(含量为3.63%~4.47%),贫Cl(含量<0.036%),属于氟磷灰石。磷灰石原位U-Pb定年结果显示,大幅楼矿床热液磷灰石形成于(96.2±5.7)Ma。未蚀变岩浆磷灰石高F特征表明,大厂矿田初始岩浆相对富F,可有效降低岩浆固相线温度和黏度,延长岩浆演化过程,有利于Sn在残余熔体中富集。岩浆磷灰石低的As含量(含量为(1.15~7.18)×10^-6),以及大幅楼矿床流体包裹体中CH₄的大量出现,表明岩浆演化和大幅楼矿床热液成矿阶段,体系氧逸度( $f O 2$ )始终维持在较低水平。结合前人流体包裹体成分分析和测温结果,认为流体降温是导致大幅楼矿床锡石沉淀的主要原因,锡石与毒砂的氧化还原缓冲在锡石-硫化物阶段锡石沉淀过程中发挥了重要作用。华南典型锡矿和其他不同成因类型矿床磷灰石微量元素的主成分分析(PCA)和核密度估算(KDE)结果显示,锡矿相关磷灰石富集La、Ce、Pr、Sm、Gd、Dy、Yb和Y元素,可作为区分锡矿与其他成因类型矿床的判别标志。

关键词: 磷灰石U-Pb定年, 挥发分, 氧逸度变化, 大幅楼Sn-Zn矿床, 丹池成矿带

Abstract:

The Danchi fold-and-thrust belt is one of the most important tin polymetallic regions in South China. Tin polymetallic mineralization is closely linked to the Late Cretaceous biotite granite (the Longxianggai pluton) in the Dachang district, middle of the Danchi fold-and-thrust belt. However, the chemical compositions of melts and ore-forming fluids, volatiles, and oxygen fugacity ( $f O 2$ ) during the evolution of magmatic-hydrothermal process remain unclear. Fortunately, euhedral coarse-grained hydrothermal apatite associated with tin mineralization was identified in the No.22-1 orebody of the Dafulou Sn-Zn deposit, eastern segment of the Dachang district. Combined with previous geochemical data of unaltered magmatic apatite, hydrothermally altered apatite in biotite granite and granite porphyry dike. These materials provide an opportunity to investigate the geochemical properties of melts and ore-forming fluids, as well as their constraint on tin mineralization and ore genesis. At the same time, we attempt to establish a new comprehensive diagram to distinguish tin deposits from other deposit types, providing guidance for exploration. Herein, detailed mineralogical studies, laser ablation-inductively coupled plasma-mass (LA-ICP-MS) U-Pb dating, X-ray photoelectron spectroscopy (XPS) analyses, and electronic probe analyses (EPMA) were conducted on hydrothermal apatite of the Dafulou deposit. The mineralogical features of apatite from oxide stage show that euhedral coarse-grained apatite (50-200 μm) is intergrowth with Fe-oxides, cassiterite, ilmenite, and quartz. The apatite does not show any zoning in the electron backscatter images (BSE). Calcium, P, and F elements show the relative homogeneous distributions in apatite grains by X-ray mapping. EPMA suggest apatite is significantly enriched in F (3.63%-4.47%), but depleted in Cl (<0.036%). In situ U-Pb dating implies apatite formed at (96.2±5.7) Ma. The high F characteristics of unaltered magmatic apatite indicate the initial magma of the Longxianggai pluton is relatively F-rich, which effectively reduces the magmatic solidus temperature and viscosity, prolongs the process of magmatic evolution, and facilitates Sn enrichment in residual melts. The low As contents (1.15-7.18 ppm) of magmatic apatite, as well as the occurrence of CH₄ in fluid inclusions of the Dafulou deposit, indicate that the oxygen fugacity ( $f O 2$ ) were relatively low during the evolution of magma and the hydrothermal mineralization stage of the Dafulou deposit. Combined with previous fluid inclusion composition analysis and microthermometric results, we conclude that fluid cooling is the main trigger for cassiterite deposition and the redox buffering between cassiterite and arsenopyrite also plays an important role in cassiterite precipitation of the cassiterite-sulfides stage in the Dafulou Sn-Zn deposit. The results of principal component analysis (PCA) and kernel density estimation (KDE) of trace elements in apatite from typical tin deposits in South China and other deposit types show that the apatite associated with tin mineralizations is relatively enriched in La, Ce, Pr, Sm, Gd, Dy, Yb, and Y elements, which can be used to distinguish tin deposits from other deposit types.

Key words: apatite U-Pb dating, volatiles, oxygen fugacity, Dafulou Sn-Zn deposit, Danchi fold-and-thrust belt

中图分类号:

P597
P611.1

张宇, 肖昌浩, 于萍萍, 张闰峰, 胡利娟. 磷灰石年代学、地球化学特征对大厂矿田东矿带大幅楼脉状Sn-Zn矿床成矿作用的指示[J]. 地学前缘, 2026, 33(2): 88-104.

ZHANG Yu, XIAO Changhao, YU Pingping, ZHANG Runfeng, HU Lijuan. Tin mineralization of the Dafulou quartz vein-type Sn-Zn deposit, Dachang district: Constrained by the apatite geochronology and geochemical characteristics[J]. Earth Science Frontiers, 2026, 33(2): 88-104.

图/表 14

图1 右江盆地地质图(修改自文献[5]) A—古亚洲构造简图;B—研究区位置图;C—右江盆地地质简图和钨锡多金属矿床分布图。

Fig.1 Schematic geological map of the Youjiang Basin. Modified after [5].

图2 大厂矿田地质图(修改自文献[25]) A—丹池成矿带地质示意图;B—大厂矿田地质图和岩浆岩、矿床分布。

Fig.2 Schematic geological map of the Dachang tin district. Modified after [25].

图3 大幅楼Sn-Zn矿床21号、22号、22-1号和0号矿体剖面图(修改自文献[33])

Fig.3 Cross section of No. 21, 22, 22-1, and 0 orebodies in the Dafulou Sn-Zn deposit. Modified after [33].

图4 大幅楼矿床矿体、矿石特征和矿物组合 A—22-1号似层状矿体与围岩(泥灰岩)接触界线截然;B—块状硫化物矿石,其中自形锡石充填于石英晶洞中;C—网脉状锡石-磁黄铁矿-黄铁矿-方解石矿石;D—硫化物(磁黄铁矿和黄铁矿)-锡石组合(第二阶段)被锡石-石英脉(第三阶段)切穿;E—第一阶段矿物组合,自形-半自形锡石和钛铁矿等与铁氧化物共生;F,G—第二阶段矿物组合,其中图F显示自形-半自形锡石与磁黄铁矿、毒砂和石英共生,图G显示磁黄铁矿被铁闪锌矿、黝锡矿、黄铜矿、黄铁矿、石英和菱铁矿组合切穿并交代,其中铁闪锌矿颗粒中发育黄铜矿固溶体;H,I—第三阶段矿物组合,其中图H显示自形粗粒锡石与毒砂和石英共生,图I表明自形锡石颗粒内部发育针状磷灰石矿物包裹体。

Fig.4 Orebodies features and mineral assemblages of the Dafulou deposit

图5 大幅楼矿床矿物生成顺序图

Fig.5 Mineral paragenetic sequences of the Dafulou deposit

图6 氧化物阶段磷灰石岩相学特征 A—用于U-Pb定年的磷灰石显微照片和CL图像;B,C—BSE图像显示磷灰石与铁氧化物、钛铁矿、锡石和石英等共生;D-G—BSE、XPS面扫描结果显示磷灰石Ca、P和F元素分布均匀。

Fig.6 Petrographic characteristics of apatite from the oxides stage

表1 大幅楼矿床氧化物阶段磷灰石LA-ICP-MS U-Pb定年数据

Table 1 LA-ICP-MS U-Pb dating results of apatite from oxides stage in the Dafulou deposit, South China

分析点位	U-Th-Pb含量/10^-6			U-Th-Pb同位素比值
分析点位	总Pb	²³²Th	²³⁸U	²⁰⁷Pb/²⁰⁶Pb	2σ	²⁰⁷Pb/²³⁵U	2σ	²⁰⁶Pb/²³⁸U	2σ
DFL-06	3.40	9.79	0.27	0.700	0.034	266.128	38.704	2.807	0.399
DFL-07	4.70	48.85	0.52	0.709	0.036	153.016	15.093	1.622	0.156
DFL-11	4.39	45.97	0.54	0.710	0.042	148.934	12.849	1.555	0.116
DFL-12	4.41	35.44	0.28	0.740	0.047	284.540	30.062	2.907	0.318
DFL-13	3.03	19.53	3.07	0.684	0.052	26.872	5.579	0.283	0.056
DFL-15	2.73	8.04	4.44	0.692	0.045	17.344	3.497	0.186	0.037
DFL-16	7.02	0.30	0.07	0.743	0.038	1 449.135	500.288	14.419	5.040
DFL-17	4.41	11.76	3.41	0.697	0.038	149.025	44.722	1.498	0.442
DFL-19	4.04	5.65	1.86	0.708	0.059	80.020	14.022	0.822	0.140
DFL-22	16.38	21.27	10.43	0.688	0.024	29.785	2.878	0.314	0.028
DFL-23	7.35	13.27	36.83	0.507	0.030	3.336	0.199	0.048	0.002
DFL-25	5.71	16.67	22.31	0.548	0.033	6.808	1.314	0.082	0.013
DFL-26	3.83	19.76	42.02	0.354	0.020	1.328	0.071	0.028	0.001
DFL-28	9.81	18.27	8.23	0.674	0.029	20.523	1.341	0.223	0.013
DFL-32	6.06	27.06	5.76	0.707	0.034	33.326	6.556	0.342	0.068
DFL-34	15.55	24.35	22.73	0.645	0.033	11.663	1.090	0.129	0.011
DFL-35	5.33	12.10	9.76	0.635	0.035	9.133	0.557	0.106	0.006
DFL-36	8.52	8.38	7.58	0.669	0.030	18.860	2.115	0.207	0.022
DFL-37	6.51	25.65	30.75	0.519	0.020	3.575	0.226	0.050	0.002
DFL-39	9.35	14.49	21.75	0.606	0.026	7.179	0.625	0.086	0.006
DFL-40	9.54	37.88	8.84	0.660	0.029	31.734	5.945	0.345	0.063
DFL-41	13.85	22.56	11.97	0.660	0.028	19.167	1.376	0.213	0.014
DFL-42	18.78	7.70	23.98	0.626	0.029	12.908	1.939	0.144	0.019
DFL-45	14.30	55.75	5.47	0.722	0.032	59.932	6.525	0.610	0.068

图7 大幅楼矿床磷灰石T-W U-Pb年龄图

Fig.7 Tera-Wasserburg plots of apatite in the Dafulou deposit

表2 大幅楼矿床氧化物阶段磷灰石电子探针数据

Table 2 Electronic probe test results of apatite from oxides stage in the Dafulou deposit, South China

表3 丹池成矿带成矿年龄统计表

Table 3 Summarized of the metallogenic ages of the Danchi fold-and-thrust belt

矿田	矿床	方法	成矿年龄/Ma	参考文献
大厂	拉么	石英Rb-Sr	98.6±5.8	[29]
		辉钼矿Re-Os	90.0±1.1	[38]
		辉钼矿Re-Os	91.55±0.67	[25]
	铜坑-长坡	石英⁴⁰Ar-³⁹Ar	94.52±0.33	[39]
		长石⁴⁰Ar-³⁹Ar	91.4±2.9	[39]
		锡石U-Pb	95. 8±2. 6	[40]
		锡石U-Pb	91.5±2.3	[37]
		锡石U-Pb	91.13±0.61	[41]
		锡石U-Pb	89.46±0.47	[41]
		锡石U-Pb	89.76±0.44	[41]
	高峰	锡石U-Pb	93.0±1.4	[37]
		锡石U-Pb	91.2±1.8	[37]
		锡石U-Pb	92.7±2.2	[37]
		锡石U-Pb	92.5±4.4	[7]
		石英⁴⁰Ar-³⁹Ar	94.56±0.45	[39]
		石英Rb-Sr	93.4±7.9	[41]
	大幅楼	锡石U-Pb	91.3±7.3	[37]
	大幅楼	磷灰石U-Pb	96.2±5.7	本文
	灰乐	锡石U-Pb	94.5±5.0	[37]
	灰乐	锡石U-Pb	89.00±1.3	[42]
	亢马	锡石U-Pb	92.8±4.6	[37]
	亢马	石英Rb-Sr	94.1±2.7	[43]
北香		锡石U-Pb	90.6±4.5	[44]
五圩	箭猪坡	锡石U-Pb	90.2±3.1	[5]
	拔旺	锡石U-Pb	90.6±4.6	[5]
	拔旺	锡石U-Pb	93.1±4.8	[45]
		锡石U-Pb	85.3±6.3	[45]

图8 大厂矿田黑云母花岗岩、花岗斑岩脉中未蚀变岩浆磷灰石、蚀变磷灰石和大幅楼矿床热液磷灰石F-Cl和Cl-Cl/F二元图解(数据来自本文和文献[9-10,48])

Fig.8 Plots of F versus Cl, Cl versus Cl/F of unaltered magmatic apatite, hydrothermally altered apatite from biotite granite and granite porphyry dike, and hydrothermal apatite from the Dafulou deposit. Data were from this study and [9-10,48]. A—wF-wCl;B—wCl-Cl/F。

图9 大厂矿田磷灰石特征(修改自文献[10]) A—大幅楼矿床磷灰石演化模式图;B—大幅楼矿床塘丁组中沉积磷灰石;C—受热液流体改造的磷灰石与锡石、钛铁矿和铁氧化物共生;D—未蚀变岩浆磷灰石显示富F和低As特征;E—蚀变磷灰石表面粗糙,发育孔洞和独居石矿物包裹体。

Fig.9 Apatite characteristics of the Dachang ore district. Modified after [10].

图10 不同成因类型矿床磷灰石LA-ICP-MS微量元素主成分分析图解第一(PC1)-第二主成分(PC2)图和第三(PC3)-第四主成分(PC4)图(数据来自[9-10,16,48]和其中的参考文献) A—第一(PC1)-第二主成分(PC2)图;B—第三(PC3)-第四主成分(PC4)图。

Fig.10 Principal component analysis (PCA) of the LA-ICP-MS trace elements in apatite from different type deposits. PC1 vs. PC2, PC3 vs. PC4. Data were from [9-10,16,48] and their references.

图11 磷灰石微量元素散点图和核密度曲线(数据来源同图10) 图中核密度曲线代表不同成因类型矿床磷灰石微量元素在第三(PC3)-第四主成分(PC4)图中的主要分布范围。

Fig.11 Scatterplots and kernel density curves of apatite trace elements. The data source was the same as Fig.10.

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磷灰石年代学、地球化学特征对大厂矿田东矿带大幅楼脉状Sn-Zn矿床成矿作用的指示

Tin mineralization of the Dafulou quartz vein-type Sn-Zn deposit, Dachang district: Constrained by the apatite geochronology and geochemical characteristics

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