萤石矿床成因研究方法及发展趋势

张建芳; 陈浩然; 伍江涵; 王振; 张琨仑; 吕鹏瑞; 曹华文; 邹灏

doi:10.12401/j.nwg.2024055

萤石矿床成因研究方法及发展趋势

张建芳^1,,
陈浩然²,
伍江涵²,
王振¹,
张琨仑¹,
吕鹏瑞³,
曹华文²,
邹灏^{2, 4, ,}

1.
浙江省地质院，浙江杭州　310007
2.
成都理工大学地球与行星科学学院，四川成都　610059
3.
中国地质调查局西安地质调查中心/西北地质科技创新中心，陕西西安　710119
4.
油气藏地质及开发工程国家重点实验室，四川成都　610059

基金项目: 浙江省级基础性公益性战略性地质资金（省资2023019），四川省自然资源厅科研项目（KJ-2023-011），四川省自然科学基金杰出青年科学基金（23NSFJQ0162）和国家自然料学基金（42272129）联合资助。

详细信息

作者简介:
张建芳（1985−），男，硕士，高级工程师，主要从事矿床成因和矿产勘查工作。E−mail：zhjianfang@126.com

通讯作者:
邹灏（1986−），男，博士，教授，主要从事矿物学、岩石学、矿床学的教学和科研工作。E−mail：zouhao@cdut.edu.cn。

中图分类号: P578.3
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出版历程
- 收稿日期: 2024-05-01
- 修回日期: 2024-06-02
- 录用日期: 2024-06-02
- 网络出版日期: 2024-06-05
- 刊出日期: 2024-08-19

Review on the Progress of Genetic Research Methods of Fluorite Deposits

1.
Zhejiang Institute of Geosciences, Hangzhou 310007, Zhejiang, China
2.
College of Earth and Planet Sciences, Chengdu University of Technology, Chengdu 610059, Sichuan, China
3.
Xi’an Center of China Geological Survey / Northwest China Center of GeosciencesInnovation, Xi’an 710119, Shaanxi, China
4.
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Chengdu University of Technology, Chengdu 610059, Sichuan, China

摘要

摘要:
萤石是重要的战略性非金属矿产，深化其成因理论的研究至关重要。笔者对萤石矿床成因研究方法的进展进行综述，以期促进国内萤石矿床成因的深入研究，助力新一轮找矿突破战略行动。在对全球和中国的萤石矿床分布特征和成因类型进行归纳总结的基础上，重点从流体包裹体、成矿流体和物质来源、成矿年代学等方面综述了目前的主要研究现状和进展。总结了萤石的流体包裹体组合和单个流体包裹体原位成分分析技术，探讨了H-O-Sr-Ca-Nd同位素示踪物源，讨论了原位微量稀土元素对成矿过程的精细刻画等。笔者认为应该重点使用原位分析技术对流体包裹体和萤石成分进行测试，以便更精细的刻画成矿流体组分的演化过程。萤石Lu-Hf、U-Pb、Sm-Nd、（U-Th）/He和裂变径迹年代学不仅对精确获得含萤石的矿床成矿年龄至关重要，而且在矿产勘查中对矿床抬升剥蚀的正确认识也十分有必要。
- 萤石 /
- 成矿流体 /
- 成矿年代学 /
- LA-ICP-MS /
- 发展趋势
Abstract:
Fluorite is a strategically important nonmetallic mineral, the research on its genesis is of significant importance. This paper reviews the progress of genetic research methods in order to promote the in-depth study of the genesis of domestic fluorite deposits and make a contribution to a new round of prospecting breakthrough strategy. The distribution characteristics and genetic types of fluorite deposits worldwide and in China are summarized. Furthermore, the current status and progress of the main research methods in fluid inclusions, ore-forming fluids and material sources, and ore-forming geochronology are reviewed. The fluid inclusion assemblage and in-situ composition techniques of single fluid inclusion of fluorite are summarized, and the source of H-O-Sr-Ca-Nd isotope tracer and the fine reflection of in-situ trace rare earth elements on the mineralization process are discussed. The author proposes that the in-situ analysis technique should be employed to test the fluid inclusions and fluorite components, thereby enabling a more accurate description of the evolution process of ore-forming fluid components. The application of Lu-Hf, U-Pb, Sm-Nd, (U-Th)/He and fission track geochronology of fluorite is not only important for the accurate determination of the ore-forming age of fluorite-bearing deposits, but also necessary for the correct interpretation of deposit uplift and denudation in ore-forming exploration.
- fluorite /
- ore-forming fluid /
- metallogenic geochronology /
- LA-ICP-MS /
- Development trend

HTML全文

研究区南临祁连造山带，北接中亚造山带，其所处构造环境的特殊性对区域构造演化及板块运动有着重大意义。该地区岩浆演化期次及构造背景研究较为薄弱且存在较大争议，前人通过对合黎山地区五坝和张家窑岩体锆石U-Pb年代学及同位素地球化学特征研究，其年龄介于432～397 Ma，为中志留世—早泥盆世，认为阿拉善地块西南缘早古生代很可能受控于祁连造山带的构造演化，处于后碰撞拉伸环境（王增振等，2020）；通过对龙首山西山头窑地区三期岩体锆石U-Pb年代学研究，其年龄介于304.3～281.2 Ma，为晚石炭世—早二叠世，处于弧后洋盆闭合过程，是古亚洲洋向南俯冲的结果（董国强等，2022）；而强利刚等（2019)认为龙首山地壳在晚古生代处于拉伸的稳定阶段。对合黎山地区岩浆岩形成时代及构造环境研究存在重要意义。龙首山成矿带区内侵入岩发育广泛，主要为酸性、中酸性岩石，主要岩性以花岗岩、花岗闪长岩、英云闪长岩等为主（张甲民等，2017），前人对龙首山成矿带的研究工作主要以东段为主，且主要集中在早古生代（牛宇奔等，2018；刘文恒等，2019；王增振等，2020）。而不同构造环境下的侵入岩具有不同的地球化学特征及同位素特征，能有效反映其岩浆源区及构造演化等重要信息。笔者在前人工作基础上对该区花岗闪长岩开展了锆石U-Pb年代学、岩石地球化学及Lu-Hf同位素特征的研究，确定该岩体形成时代并探讨这些黑云母花岗闪长岩的成因问题及龙首山成矿带西南缘构造环境特征。

1. 区域地质概况

合黎山地处阿拉善地块龙首山成矿带西南缘，大地构造位置属于华北板块西南边缘（图1a）（谭文娟等，2012），北以龙首山北缘断裂与潮水中新生代断陷相邻（汤中立等，1999），南以南缘断裂与走廊过渡带分开。区内成矿条件有利（焦建刚等，2007）。龙首山成矿带是中国西北重要的铀成矿带（王承花，2010），同时中国著名的金川镍矿也位于该成矿带内（强利刚等，2019；张照伟等，2023）。

图 1 阿拉善地块大地构造简图（a）及罗城地区地质简图（b）

Figure 1. (a) Geostructural map of Alxa Block and (b) geological map of Luocheng Area

下载: 全尺寸图片幻灯片

区内地质构造复杂，次级构造发育，逆冲构造及伸展构造叠加，总体构造为NWW向（甘肃省地质局，1974），出露地层包括前震旦系龙首山群的角闪岩相–绿片岩相变质岩等中级区域变质岩系，其与上覆地层均为不整合接触；震旦系下统及中上统的云母石英片岩、变粒岩及变质砂岩、大理岩等为主的浅变质岩，其下统与中—上统之间多为断层接触；侏罗系青土井群的砂岩、砂砾岩等为主的陆源碎屑岩夹煤层，其与上覆地层及下伏地层均为不整合接触；白垩系以砂砾岩、泥岩等为主的碎屑岩；第三系以砾岩、含砾砂岩为主的沉积岩及第四系松散堆积物（图1b）。

测区内岩浆岩发育广泛，主要为酸性、中酸性岩石为主，侵入活动主要是在加里东中期及华力西期，以华力西期侵入岩最为发育，主要岩性以花岗岩、花岗闪长岩、英云闪长岩等为主，其中以花岗闪长岩出露最为广泛，其次为英云闪长岩。罗城岩体主要为花岗闪长岩发育，其中可见花岗岩、闪长岩呈脉状发育。区内五坝和张家窑岩体锆石U-Pb年代学年龄介于432～397 Ma，为中志留世—早泥盆世（王增振等，2020）；西山头窑地区岩体锆石U-Pb年代学年龄介于304.3～281.2 Ma，为晚石炭世—早二叠世。

2. 样品采集及岩石学特征

罗城岩体主要位于甘肃省高台县罗城镇北侧，其岩性主要为黑云母花岗闪长岩，野外岩体出露较为完整，笔者选取了合黎山地区高台县罗城幅的黑云母花岗闪长岩进行锆石U－Pb定年分析，共采集样品5件，其中岩石年龄同位素样品1件，并在岩石年龄同位素样品采集处配套采集岩石地球化学样品4件。样品采集地理坐标：E 99°43′39″，N 39°46′30″和E 99°41′43″，N 39°48′20″。为确保锆石数据准确性，样品均为未风化蚀变的新鲜岩石。

岩石新鲜面为灰白色，具半自形粒状结构，块状构造（图2a）。主要矿物及含量：斜长石（45%），石英（20%），碱性长石（15%），普通角闪石（15%），黑云母（5%）。斜长石粒径约0.30～1.30 mm，呈半形粒状、板状，具聚片双晶，表面浑浊，微裂隙发育，次生绢云母化，均匀分布。碱性长石粒径约0.20～1.10，呈半自形板状，具卡式双晶，少量分布。石英粒径约0.10～2.00 mm，呈他形粒状，波状消光，沿长石粒间分布。普通角闪石粒径约0.20～1.60 mm，呈他形柱状，黄褐色，截面呈菱面体状，具角闪石式解理，绿泥石化，沿长英质粒间定向分布。黑云母粒径约0.15～2.25 mm，呈鳞片状、片状，褐黄色-红褐色，沿长英质粒间定向分布。副矿物有磷灰石、绿帘石（图2b、图2c、图2d）。

图 2 黑云母花岗闪长岩手标本及镜下照片

a.黑云母花岗闪长岩手标本; (b，d).正交偏光镜下特征; c.单偏光镜下特征;Qtz.石英; Bt.黑云母; P1.斜长石; Kfs.钾长石; Hbl.角闪石

Figure 2. Biotite granodiorite hand specimen and microscopic photograph

下载: 全尺寸图片幻灯片

3. 样品分析方法

样品的锆石挑选、制靶、CL照相由西安瑞石地质科技有限公司完成，采用标准重矿物分离技术分选出重矿物，随后在双目镜下挑选出锆石颗粒，将不同特征的锆石颗粒粘在双面胶上，并用无色透明的环氧树脂固定，待其固化之后将表面抛光至锆石内部暴露。然后拍摄阴极发光图像、透射光图像和反射光图像，选取分析点位。

锆石U-Pb定年和Hf同位素组成分析在中国地质调查局西安地质调查中心岩浆作用成矿与找矿重点实验室完成。锆石U-Pb定年在LA-ICP-MS仪器上用标准测定程序进行，样品采用激光剥蚀等离子体质谱仪原位分析锆石微区的铀铅比值（²⁰⁶Pb/²³⁸U、²⁰⁷Pb/²³⁵U和²⁰⁷Pb/²⁰⁶Pb）（李艳广等，2015）并通过Glitter计算程序计算锆石的年龄及标准偏差；应用Isoplot（Ludwig, 2003）计算程序对锆石样品的²⁰⁶Pb/²³⁸U年龄和²⁰⁷Pb/²³⁵U年龄在谐和图上进行投图，并计算谐和年龄测点的加权平均值。

锆石Hf同位素组成运用Neptune型多接收电感耦合等离子体质谱仪和GeolasPro型激光剥蚀系统联用的方法完成（袁洪林等，2007），所选测试位置均与锆石U-Pb测点位置相近，测试束斑直径为32 μm，采用国际标准锆石91500进行监控和样品外部校正｡

主量元素和微量元素分析测试在中国地质调查局西安矿产资源调查中心完成，主量元素采用X荧光光谱仪进行分析，稀土和微量元素采用等离子质谱仪进行分析，测试结果见表1。

表 1 罗城黑云母花岗闪长岩主量元素（%）、微量元素（10⁻⁶）、稀土元素（10⁻⁶）分析结果表

Table 1. Analysis results of major elements （%）, trace elements (10⁻⁶) and rare earth elements (10⁻⁶) in Luocheng biotite granodiorite

样品编号	LCYT03	LCYT04	LCYT05	LCYT06
SiO₂	59.84	58.75	58.52	59.09
Al₂O₃	16.91	17.25	17.28	17.28
Fe₂O₃	7.13	7.82	7.55	7.61
CaO	6.33	6.70	6.93	6.68
MgO	3.13	3.38	3.53	3.34
K₂O	1.87	1.49	1.49	1.54
Na₂O	2.52	2.60	2.55	2.60
P₂O₅	0.13	0.15	0.15	0.15
TiO₂	0.68	0.74	0.77	0.75
MnO	0.13	0.14	0.14	0.14
LOI	1.03	0.74	0.85	0.60
总和	99.70	99.76	99.75	99.79
K₂O+Na₂O	4.40	4.09	4.04	4.15
K₂O/Na₂O	0.74	0.57	0.59	0.59
δ	1.15	1.06	1.05	1.07
A/NK	2.74	2.93	2.98	2.9
A/CNK	0.97	0.97	0.96	0.97
Rb	61.1	49.2	40.6	46.9
Th	3.37	4.58	5.70	8.46
U	0.79	0.72	0.74	0.75
Nb	4.48	4.76	4.64	4.64
Sr	376	429	413	403
Zr	84.3	112	88.6	118
Hf	2.34	2.79	2.23	2.97
F	454	320	663	360
Sn	＜1.80	＜1.80	＜1.80	＜1.80
Cr	12.9	17.6	14.1	14.1
Li	16.8	18.3	17.3	17.4
Be	0.76	0.87	0.86	0.79
V	166	186	180	174
Co	15.3	16.2	15.6	15.3
Ni	8.36	10.9	11.2	10.4
Ga	16.6	17.7	16.3	16.4
Cs	2.52	2.92	2.69	3.15
Ta	0.33	0.35	0.34	0.35
W	2.30	1.91	1.81	1.80
Bi	0.073	0.070	＜0.050	0.057
La	12.0	14.3	12.5	12.5
Ce	27.1	28.9	25.5	25.7
Pr	3.60	3.59	3.32	3.21
Nd	16.4	15.3	14.6	14.1
Sm	3.91	3.37	3.28	3.14
Eu	1.05	1.07	1.05	1.03
Gd	4.14	3.54	3.49	3.41
Tb	0.66	0.55	0.54	0.52
Dy	4.04	3.28	3.24	3.15
Ho	0.83	0.68	0.67	0.65
Er	2.54	2.03	2.02	1.95
Tm	0.36	0.29	0.29	0.28
Yb	2.33	1.88	1.87	1.84
Lu	0.36	0.30	0.30	0.29
Y	21.3	17.2	16.9	16.4
ΣREE	79.32	79.08	72.67	71.77
LREE	64.06	66.53	60.25	59.68
HREE	15.26	12.55	12.42	12.09
LREE/HREE	4.20	5.30	4.85	4.94
(La/Yb)_N	3.69	5.46	4.79	4.87
δEu	0.80	0.95	0.95	0.96
δCe	1.01	0.99	0.97	0.99

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4. 分析结果

4.1 锆石U-Pb定年分析

样品的锆石颗粒的CL图像（图3）显示所选的锆石为透明的自形晶体，为无色透明或浅黄色，大部分锆石结晶较好，短柱状晶形，阴极发光电子图像特征均显示出典型的岩浆结晶韵律环带结构。

图 3 锆石样品测点CL照片

Figure 3. CL photograph of the zircon sample

下载: 全尺寸图片幻灯片

本次所选锆石样品25颗，均为有效样品，黑云母花岗闪长岩锆石U-Pb分析测试结果见表2，锆石Th含量为34.81×10⁻⁶～129.66×10⁻⁶，U含量为52.88×10⁻⁶～147.36×10⁻⁶，Th/U值为0.55～0.97，均大于0.4，说明锆石为岩浆成因（吴元保等，2004）。锆石微量元素测试结果见表3，其显示出重稀土富集，相对亏损轻稀土元素的特征，显示典型的岩浆锆石成因特征（Hoskin，2000）。锆石谐和图反映出锆石U-Pb年龄数据分布比较集中且谐和程度较好（图4a），所有数据协和度均符合要求，证明数据均有效。通过数据分析得到²⁰⁶Pb/²³⁸U加权平均年龄为（289±3）Ma，（MSWD=0.57），代表岩浆结晶年龄（图4b）。

表 2 罗城花岗闪长岩（LCYT01）锆石LA-ICP-MS测年结果

Table 2. Zircon LA-ICP-MS dating results of Luocheng granodiorite (LCYT01)

测点号	含量（10⁻⁶）			Th/U	同位素比值								同位素年龄
测点号	Pb	Th	U	Th/U	²⁰⁷Pb/²⁰⁶Pb	±1δ	²⁰⁷Pb/²³⁵U	±1δ	²⁰⁶Pb/²³⁸U	±1δ	²⁰⁸Pb/²³²Th	±1δ	²⁰⁷Pb/²⁰⁶Pb	±1δ	²⁰⁷Pb/²³⁵U	±1δ	²⁰⁶Pb/²³⁸U	±1δ	²⁰⁸Pb/²³²Th	±1δ
LCYT001	15.96	79.28	81.67	0.97	0.05153	0.00423	0.32079	0.02551	0.04511	0.00102	0.01452	0.00048	264.4	177.81	282.5	19.61	284.5	6.28	291.3	9.56
LCYT002	14.25	47.28	72.22	0.65	0.05202	0.0046	0.32939	0.02827	0.04589	0.00108	0.01269	0.00063	286.1	189.7	289.1	21.59	289.2	6.68	255	12.64
LCYT003	12.04	34.81	63.55	0.55	0.0524	0.00697	0.32463	0.04227	0.0449	0.00134	0.01375	0.00088	302.7	277.82	285.5	32.4	283.2	8.26	276.1	17.48
LCYT004	19.92	93.99	98.06	0.96	0.04923	0.00498	0.31772	0.03138	0.04678	0.00114	0.01432	0.00059	158.7	220.85	280.1	24.18	294.7	7.05	287.5	11.7
LCYT005	11.37	41.91	57.97	0.72	0.0517	0.00762	0.33365	0.04817	0.04678	0.00152	0.01611	0.00095	272.2	306.78	292.4	36.67	294.7	9.39	323	18.95
LCYT006	16.79	80.92	85.36	0.95	0.05021	0.00438	0.31261	0.02651	0.04513	0.00103	0.01345	0.00049	204.9	190.68	276.2	20.51	284.6	6.35	270	9.73
LCYT007	27.09	129.66	147.36	0.88	0.05412	0.00356	0.342	0.0216	0.04582	0.00096	0.01384	0.00042	375.8	141.54	298.7	16.34	288.8	5.93	277.8	8.4
LCYT008	12.51	45.55	65.96	0.69	0.05029	0.0043	0.32015	0.0266	0.04616	0.00106	0.01535	0.00062	208.3	187.16	282	20.46	290.9	6.51	307.8	12.31
LCYT009	13.69	45.68	72.34	0.63	0.05153	0.00444	0.33081	0.02763	0.04656	0.00109	0.01519	0.00068	264.4	186.14	290.2	21.08	293.3	6.73	304.7	13.59
LCYT010	12.68	46.02	66.65	0.69	0.05115	0.00472	0.33038	0.0297	0.04685	0.00111	0.01457	0.00063	247.4	199.46	289.9	22.67	295.1	6.83	292.5	12.53
LCYT011	13.09	49.92	68.97	0.72	0.04792	0.00563	0.30937	0.03563	0.04682	0.00122	0.01473	0.00087	94.2	257.92	273.7	27.63	295	7.49	295.6	17.3
LCYT012	12.53	47.8	65.53	0.73	0.0521	0.00482	0.33683	0.03033	0.04689	0.00112	0.01606	0.00063	289.7	198	294.8	23.04	295.4	6.87	322	12.57
LCYT013	18.31	92.71	98.11	0.94	0.05178	0.0039	0.32956	0.02399	0.04618	0.001	0.01362	0.00044	275.6	163.56	289.2	18.32	291	6.19	273.3	8.78
LCYT014	19	93.38	105.35	0.89	0.05329	0.00398	0.3273	0.02358	0.04457	0.00099	0.01433	0.00046	340.9	160.32	287.5	18.04	281.1	6.09	287.6	9.21
LCYT015	15.16	51.53	80.72	0.64	0.04948	0.00412	0.30521	0.02472	0.04476	0.00098	0.01424	0.00055	170.8	183.56	270.5	19.23	282.3	6.06	285.7	11.06
LCYT016	14.01	55.43	76.33	0.73	0.0503	0.00537	0.30848	0.03208	0.04451	0.00118	0.01286	0.00065	209	229.96	273	24.9	280.7	7.27	258.2	12.91
LCYT017	11.3	45.88	60.72	0.76	0.05239	0.00499	0.33231	0.03079	0.04604	0.00115	0.01288	0.0006	302.4	203.45	291.3	23.47	290.1	7.1	258.6	11.9
LCYT018	16.38	73.42	88.24	0.83	0.05321	0.0037	0.3292	0.02201	0.0449	0.00096	0.01409	0.00044	337.7	149.52	289	16.81	283.2	5.92	282.7	8.81
LCYT019	15.81	76.58	80.92	0.95	0.05166	0.00378	0.32813	0.02317	0.0461	0.00099	0.01466	0.00044	270.4	159.18	288.1	17.72	290.6	6.07	294.2	8.75
LCYT020	13.2	53.42	68.41	0.78	0.05023	0.00423	0.31534	0.02582	0.04557	0.00103	0.0151	0.00054	205.7	184.61	278.3	19.93	287.3	6.36	302.9	10.68
LCYT021	10.77	36.85	52.88	0.70	0.05095	0.0044	0.32225	0.02702	0.04592	0.00105	0.01367	0.00064	238.6	187.4	283.6	20.75	289.4	6.46	274.3	12.67
LCYT022	13.95	47.61	68.78	0.69	0.05283	0.00388	0.34372	0.02436	0.04724	0.00102	0.01389	0.00055	321.3	157.94	300	18.41	297.6	6.25	278.8	10.94
LCYT023	23.03	103.73	117.27	0.88	0.05235	0.00313	0.33694	0.01926	0.04673	0.00094	0.01421	0.00041	300.6	130.55	294.9	14.63	294.4	5.77	285.2	8.1
LCYT024	16.81	56.88	85.69	0.66	0.05387	0.00347	0.34195	0.02113	0.04609	0.00095	0.01337	0.00048	365.6	138.52	298.6	15.99	290.5	5.83	268.4	9.65
LCYT025	14.8	67.05	76.38	0.88	0.05203	0.00384	0.33011	0.02359	0.04608	0.00099	0.01419	0.00047	286.8	160.34	289.7	18	290.4	6.11	284.8	9.33

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表 3 罗城花岗闪长岩锆石分析点位微量元素（10⁻⁶）测试结果

Table 3. Test results of trace elements (10⁻⁶) at zircon analysis points of Luocheng granodiorite

测点号	Nb	La	Ce	Pr	Nd	Sm	Eu	Gd	Tb	Dy	Ho	Er	Tm	Yb	Lu	Ta
LCYT001	1.10	0.06	8.23	0.05	0.23	0.49	1.28	27.74	0.78	107.27	40.27	181.12	35.88	339.17	66.63	0.28
LCYT002	0.49	0.04	6.69	0.03	2.07	3.33	0.40	11.13	8.82	67.14	26.56	126.02	27.32	290.78	57.98	0.24
LCYT003	0.61	0.00	6.26	0.02	0.49	2.64	0.29	7.43	4.65	45.16	17.35	87.13	19.02	192.36	38.24	0.27
LCYT004	0.63	0.06	9.25	0.08	0.44	0.69	1.15	25.90	3.00	112.88	44.64	196.44	39.56	377.09	71.61	0.26
LCYT005	0.55	0.00	6.42	0.03	1.79	4.98	0.36	8.45	9.99	40.51	19.27	87.53	19.76	189.52	37.30	0.23
LCYT006	0.52	0.01	9.03	0.05	0.63	1.34	0.91	24.92	3.67	102.58	38.80	175.98	35.30	323.64	65.73	0.28
LCYT007	0.46	0.02	17.04	0.11	1.55	2.65	0.85	24.04	6.96	113.49	45.17	206.58	43.34	418.84	82.25	0.41
LCYT008	1.37	0.00	7.31	0.03	1.49	3.08	0.46	10.50	8.69	50.85	20.86	97.32	21.63	218.50	42.57	0.30
LCYT009	0.53	0.04	7.76	0.02	0.67	1.58	0.24	7.99	4.06	43.08	18.56	85.81	19.58	193.52	36.74	0.31
LCYT010	0.65	0.00	7.39	0.03	0.40	1.28	0.24	11.38	3.43	52.67	20.97	98.21	22.28	213.94	42.28	0.26
LCYT011	0.67	0.01	7.65	0.05	0.44	2.14	0.43	11.65	4.08	54.24	22.14	101.02	21.59	221.82	41.65	0.21
LCYT012	0.58	0.24	7.21	0.07	0.73	1.88	0.48	9.62	4.43	51.70	20.95	100.70	22.19	222.33	43.83	0.39
LCYT013	3.01	0.01	9.21	0.08	1.56	2.82	0.95	24.93	3.94	113.56	45.37	198.15	41.36	399.32	71.97	0.38
LCYT014	0.66	0.01	9.65	0.07	1.79	3.63	1.15	28.87	9.60	117.65	44.48	198.85	41.00	392.05	76.11	0.34
LCYT015	0.58	0.00	8.44	0.02	2.16	4.68	0.33	10.50	9.83	52.88	20.95	100.98	22.47	230.32	44.42	0.31
LCYT016	0.74	0.00	7.73	0.04	0.49	1.29	0.40	12.46	4.08	61.43	26.20	120.97	26.57	261.96	52.64	0.38
LCYT017	0.73	0.00	6.93	0.02	0.87	2.13	0.43	12.06	5.04	54.07	23.41	106.05	23.33	232.88	44.25	0.33
LCYT018	0.84	0.01	8.09	0.06	0.57	1.82	0.83	20.89	4.58	92.58	36.57	172.39	35.31	347.52	67.40	0.29
LCYT019	0.61	0.00	8.04	0.06	1.53	3.32	0.97	26.28	7.25	103.33	41.09	175.93	36.48	349.56	66.29	0.23
LCYT020	0.47	0.00	7.31	0.02	1.72	5.06	0.39	14.22	8.78	63.23	24.83	115.49	25.21	238.91	45.30	0.22
LCYT021	0.57	0.01	5.70	0.02	0.69	1.87	0.53	10.94	5.15	53.16	21.38	104.62	22.91	221.56	45.69	0.30
LCYT022	0.53	0.04	6.60	0.03	0.27	1.73	0.46	12.33	3.89	67.24	25.79	122.86	27.12	273.00	52.93	0.28
LCYT023	0.70	0.04	9.56	0.09	0.57	1.92	1.18	27.41	5.00	122.96	49.00	227.37	46.39	456.07	89.13	0.38
LCYT024	1.14	0.04	8.63	0.02	1.85	4.19	0.28	9.30	10.49	48.68	20.06	95.23	20.74	214.10	41.88	0.34
LCYT025	1.12	0.02	7.63	0.07	1.41	2.91	1.04	22.23	4.01	93.47	36.23	160.65	34.00	327.88	65.05	0.25

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图 4 锆石样品U-Pb谐和图

Figure 4. U-Pb Concord diagram of zircon samples

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4.2 锆石Hf同位素特征

在LA-ICP-MS锆石U-Pb测年的基础上，对黑云母花岗闪长岩样品25颗锆石测点进行了锆石微区Hf同位素测定｡测点的数据分析结果（表4）｡¹⁷⁶Yb/¹⁷⁷Hf值介于0.012222351～0.042050552，¹⁷⁶Lu/¹⁷⁷Hf值介于0.00042471～0.001378472，均小于0.002，说明锆石在形成后具有很少的放射成因Hf的积累。因此，锆石¹⁷⁶Hf/¹⁷⁷Hf值可能代表该锆石形成时的¹⁷⁶Hf/¹⁷⁷Hf值（吴福元等，2007），¹⁷⁶Hf/¹⁷⁷Hf值介于0.282726048～0.282787588，εHf（t）值均为正值，介于+4.37～+6.88，平均为+5.6，通过锆石Hf同位素εHf（t）-U-Pb年龄t（Ma）图解（图5a），测点均落在球粒陨石–亏损地幔之间，反映其源区为年轻的幔源组分或新生地壳，Hf同位素一阶段模式年龄T_（DM1）分布范围为615.4～703.0 Ma，平均值为660.5 Ma，地壳模式年龄T_（DMC）分布范围为808.6～952.5 Ma，平均值为882.8 Ma，地壳模式年龄T_（DMC）较集中（图5b）｡

表 4 黑云母花岗闪长岩锆石Hf同位素分析结果

Table 4. Zircon Hf isotope analysis results of biotite granodiorite

分析点	t（Ma）	¹⁷⁶Yb/¹⁷⁷Hf	¹⁷⁶Lu/¹⁷⁷Hf	¹⁷⁶Hf/¹⁷⁷Hf	±2σ	Hf_i	εHf （0）	εHf （t）	±1σ	T（_DM1）	T（_DMC）	±1σ	f_Lu/Hf
LCYT01-01	284.5	0.018558653	0.000625497	0.282772262	0.0000194150	0.282769	0.079994272	6.14162	0.679525	634.4	846.8	0.06673	-0.9583
LCYT01-02	289.2	0.021350813	0.00072988	0.282742229	0.0000173343	0.282738	-0.982120012	5.16050	0.606701	676.8	910.5	0.065471	-0.95134
LCYT01-03	283.2	0.018541903	0.0006332	0.282761526	0.0000162177	0.282758	-0.299686693	5.73214	0.56762	649.0	871.0	0.062774	-0.95779
LCYT01-04	294.7	0.022088228	0.000738473	0.282787588	0.0000174089	0.282784	0.621999168	6.88254	0.609311	615.4	808.6	0.063449	-0.95077
LCYT01-05	294.7	0.016473205	0.000610408	0.282734375	0.0000178101	0.282731	-1.259864349	5.02445	0.623354	685.4	922.9	0.066228	-0.95931
LCYT01-06	284.6	0.03087808	0.00103004	0.282748701	0.0000169380	0.282743	-0.753226632	5.23386	0.59283	673.2	902.5	0.065308	-0.93133
LCYT01-07	288.8	0.019725731	0.000669661	0.282759209	0.0000166409	0.282756	-0.381620593	5.76427	0.582432	652.8	873.1	0.063558	-0.95536
LCYT01-08	290.9	0.025750031	0.000867335	0.282742988	0.0000180678	0.282738	-0.955258813	5.19757	0.632374	678.1	909.3	0.066791	-0.94218
LCYT01-09	293.3	0.021818077	0.00074069	0.282752659	0.0000170188	0.282749	-0.61326993	5.61588	0.595659	662.8	885.4	0.06456	-0.95062
LCYT01-10	295.1	0.031810315	0.001072333	0.282760072	0.0000185273	0.282754	-0.35109486	5.85224	0.648455	658.3	872.0	0.067113	-0.92851
LCYT01-11	295	0.032320695	0.00106083	0.282770029	0.0000187588	0.282764	0.001027859	6.20471	0.656558	644.5	850.3	0.066935	-0.92928
LCYT01-12	295.4	0.025753941	0.00084072	0.282744619	0.0000195056	0.28274	-0.897570925	5.35710	0.682698	675.5	902.8	0.068675	-0.94395
LCYT01-13	291	0.042050552	0.001378472	0.282744602	0.0000188351	0.282737	-0.898174811	5.15840	0.659227	684.9	911.5	0.069048	-0.9081
LCYT01-14	281.1	0.025917388	0.000895112	0.282777258	0.0000173229	0.282773	0.256671065	6.19473	0.606302	631.9	840.9	0.064172	-0.94033
LCYT01-15	282.3	0.012222351	0.00042471	0.282730661	0.0000185893	0.282728	-1.391186427	4.65946	0.650625	687.1	936.4	0.06705	-0.97169
LCYT01-16	280.7	0.026071795	0.00089378	0.282726048	0.0000187777	0.282721	-1.5543273	4.37430	0.65722	701.7	952.5	0.068661	-0.94041
LCYT01-17	290.1	0.026377494	0.000892334	0.282753361	0.0000177671	0.282749	-0.588435111	5.54265	0.621848	664.4	887.5	0.065933	-0.94051
LCYT01-18	283.2	0.024916918	0.000880457	0.282778938	0.0000203212	0.282774	0.316093287	6.30197	0.711244	629.4	835.9	0.068288	-0.9413
LCYT01-19	290.6	0.018210323	0.000633771	0.282781801	0.0000175364	0.282778	0.417339793	6.60951	0.613775	621.6	822.4	0.063668	-0.95775
LCYT01-20	287.3	0.01802085	0.000615423	0.282772775	0.0000170572	0.282769	0.098119936	6.22222	0.597003	633.5	843.9	0.06338	-0.95897
LCYT01-21	289.4	0.020384277	0.000718113	0.282742372	0.0000184710	0.282738	-0.9770409	5.17215	0.646485	676.4	909.9	0.067032	-0.95213
LCYT01-22	297.6	0.02594746	0.000881354	0.282760012	0.0000161587	0.282755	-0.353235735	5.94105	0.565556	655.2	868.5	0.063322	-0.94124
LCYT01-23	294.4	0.029427132	0.001014853	0.282726672	0.0000206482	0.282721	-1.532286504	4.66656	0.722688	703.0	944.4	0.071574	-0.93234
LCYT01-24	290.5	0.018539508	0.000641115	0.282769911	0.0000162977	0.282766	-0.003162189	6.18517	0.570421	637.8	848.5	0.062508	-0.95726
LCYT01-25	290.4	0.021881036	0.000749457	0.282741158	0.0000155788	0.282737	-1.019970646	5.14473	0.545259	678.6	912.3	0.063102	-0.95004

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图 5 罗城黑云母花岗闪长岩锆石ε_Hf（t）-t（Ma）图解（a）（据李良等，2018）和地壳模式年龄T_（DMC）统计直方图（b）

Figure 5. (a)Zircon_εHf(t)-t (Ma) diagram (According to LI Liang et al., 2018) and (b) crustal model age T_(DMC) statistical histogram (b) of Luocheng biotite granodiorite

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4.3 主量元素特征

合黎山地区罗城黑云母花岗闪长岩的主量元素分析结果见表1，其SiO₂含量介于58.52%～59.84%，Al₂O₃含量介于16.91%～17.28%。全碱含量Na₂O+K₂O介于4.04%～4.40%，相对富碱，Na₂O含量介于2.52%～2.60%，K₂O含量介于1.49%～1.87%，富钠贫钾。里特曼指数δ介于1.05～1.15。根据CIPW标准矿物计算（Le Maitre，1979），石英（Qtz）含量介于18.97%～20.69%，碱性长石（A）含量介于11.6%～14.66%，斜长石（Pl）含量介于47.86%～50.76%，在Q-A-P图解中（图6a），处在花岗闪长岩区域中。SiO₂-（Na₂O+K₂O-CaO）图解（图6b）反应岩石属于钙性系列。SiO₂-K₂O图解（图6c）反映岩石主体属于钙碱性系列。铝饱和指数A/CNK比较集中，介于0.96～0.97，A/NK介于2.74～2.98，在A/CNK-A/NK图解中（图6d），处在准铝质范围内。

图 6 罗城黑云母花岗闪长岩Q-A-P图解（a）（据Streckeisen, 1976）、SiO₂-（Na₂O+K₂O-CaO）图解（b）（据Peccerillo et al., 1976）、SiO₂-K₂O图解（c）（据Peccerillo et al., 1976）及A/NK-A/CNK图解（d）（据Maniar et al.，1989）

Figure 6. (a) Q-A-P diagram of Luocheng biotite granodiorite, (b) SiO₂- (Na₂O+K₂O-CaO) diagram, (c) SiO₂-K₂O diagram and (d) A/NK-A/CNK diagrams

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4.4 微量元素特征

合黎山地区罗城黑云母花岗闪长岩的稀土元素分析结果见表1，其稀土元素总量ΣREE在71.77×10⁻⁶～79.32×10⁻⁶之间，平均为75.71×10⁻⁶。LREE/HREE值在4.20～5.30之间，平均为4.82，相对富集轻稀土，亏损重稀土。（La/Yb）_N在3.69～5.46之间，平均为4.70，稀土元素球粒陨石标准化配分曲线图（图4a）中显示稀土元素为右倾型配分模式。δEu值在0.80～0.96之间，平均值为0.91，Eu具轻度负异常，说明在岩浆演化过程中有少量的斜长石分离结晶作用。

合黎山地区罗城黑云母花岗闪长岩的微量元素分析结果见表1，在微量元素原始地幔标准化蛛网图（图7b）上可见，岩石均相对富集Rb、Th、K等大离子亲石元素，亏损Nb、Ta、P、Ti等高场强元素。

图 7 罗城黑云母花岗闪长岩的稀土元素球粒陨石标准化配分曲线图（a）（据Taylor et al., 1985）和微量元素原始地幔标准化蛛网图（b）（据Sun et al., 1989）

Figure 7. (a) Normalized distribution curve of rare earth element chondrites and (b) Primitive mantle-normalized trace element diagrams of Luocheng biotite granodiorite

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5. 讨论

5.1 岩体成岩时代及岩石成因

合黎山地区罗城岩体锆石自形程度好，具有典型的岩浆结晶韵律环带结构（图5），且Th/U值均大于0.4，为典型的岩浆锆石（王新雨等，2023；李平等，2024），其锆石数据谐和度较高，²⁰⁶Pb/²³⁸U加权平均年龄为(289±3) Ma ，可代表岩浆结晶年龄，因此，合黎山地区罗城岩体形成于早二叠世。

合黎山地区罗城花岗闪长岩Ga含量为16.3×10⁻⁶~17.7×10⁻⁶，Al₂O₃含量为16.91%~17.28%，10000Ga/Al值为1.78~1.93，平均为1.84，小于A型花岗岩下限2.6（Whalen et al., 1987），在Zr-10000Ga/Al、Ce-10000Ga/Al、Y-10000Ga/Al图解（图8b、图8c、图8d）中，罗城岩体均投影在I＆S花岗岩区域，在K₂O-Na₂O图解（图8a）中，罗城岩体均处于I型花岗岩区域。根据岩石主量元素特征可知，罗城花岗闪长岩具有钙碱性、准铝质特征，其A/CNK比较集中，介于0.96～0.97，均小于1.1，与I型花岗岩一致（Chappell et al., 1992；李宏卫等，2021），且P₂O₅含量与SiO₂含量存在负线性关系，与I型花岗岩演化趋势一致（Wolf et al., 1994）。综合判断分析，罗城花岗闪长岩属于结晶分异I型花岗岩。

图 8 罗城黑云母花岗闪长岩K₂O-Na₂O图解（a）及Zr、Ce、Y-10000Ga图解（b、c、d）（据Whalen et al.，1987）

Figure 8. (a) K₂O-Na₂O and (b, c, d) Zr, Ce, Y-10000 Ga diagram of Luocheng biotite granodiorite

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5.2 岩浆起源及演化特征

I型花岗岩主要来源于板块边缘陆壳下部，可能与地壳岩石的部分熔融（徐克勤等，1982）､交代岩石圈地幔部分熔融（Jiang et al., 2006）等有关，罗城黑云母花岗闪长岩属于钙碱性系列，富集Rb、Th、K等大离子亲石元素和轻稀土元素，亏损Nb、Ta、P、Ti等高场强元素，指示岩体具有大陆地壳物质的参与，岩石Nb/Ta=13.25～13.65，平均值为13.52，接近大陆地壳Nb/Ta值（=10～14）。在判断源岩的C/MF-A/MF图解（图9a）中，显示岩体源岩可能为基性岩的部分熔融，岩石δEu值具轻度负异常，在0.80~0.96之间，平均值为0.91，说明在岩浆演化过程中有少量的斜长石分离结晶作用，在δEu-（La/Yb）_N图解中（图9b），样品投点均落在了壳源与壳幔混合源花岗岩区域，La/Ta值为35.71～40.86，大于起源于岩石圈地幔或受其混染岩浆La/Ta值的下限25，指示其为幔源或者壳幔混合源（Lassiter et al., 1997）｡

图 9 罗城黑云母花岗闪长岩C/MF-A/MF图解（a）（据Alther et al., 2000）及δEu-（La/Yb）_N图解（b）（据王钊飞等，2019）

Figure 9. (a) C/MF-A/MF diagram and (b) δEu-(La/Yb)_N diagram of Luocheng biotite granodiorite

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罗城黑云母花岗闪长岩锆石Hf二阶段模式年龄T_（DMC）分布范围为808.6～952.5 Ma，εHf（t）值介于+4.37～+6.88，通过锆石εHf（t）-U-Pb年龄t（Ma）图解（图7a），测点均落在球粒陨石–亏损地幔之间，反映其源区为年轻的幔源组分或具有新生地壳演化趋势（李金超等，2021）。

在野外工作中，在黑云母花岗闪长岩中发现暗色微细粒包体发育（图10），包体形态可见椭圆状、圆状、透镜状以及不规则状，大小差异较大，包体常具淬冷边，证明岩浆发生混合作用（王德滋等，2008；张建军等，2012）；Mg^#值可以指示壳源岩浆作用是否有幔源物质的参与，在地幔组分参与时，才能导致熔体的Mg^#值大于40（Rapp et al., 1995），岩石MgO含量介于3.13%～3.53%，Mg^#值介于0.64～0.66，明显高于40，表明岩体源岩明显具幔源岩浆加入。

图 10 罗城黑云母花岗闪长岩中暗色包体的形态

a. 椭圆状包体; b. 圆状包体; c. 透镜状包体; d. 不规则状包体

Figure 10. Field photos showing morphology of Luocheng biotite granodiorite

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基于上述讨论，罗城花岗闪长岩为壳源岩浆与幔源岩浆发生混合作用的产物，这种作用是由于地壳深部存在强烈的地幔岩浆底侵作用，导致新生地壳部分熔融并混入底侵的幔源物质。幔源的高温基性岩浆底侵，为其提供了少量物质来源，使岩石地球化学特征上既表现出壳源特征，也表现出幔源物质的信息。

5.3 构造背景

罗城黑云母花岗闪长岩富集Rb、Th、K等大离子亲石元素和轻稀土元素，亏损Nb、Ta、P、Ti等高场强元素，具有典型的岛弧岩浆岩特征（王秉璋等，2021），其形成与大洋板片俯冲消减作用有关。通过对黑云母花岗闪长岩构造背景判别，在Rb-（Y+Nb）（图11a）、Nb-Y（图11b）及Hf-Rb/30-3Ta（图11c）图解中，样品均落在火山弧花岗岩区域；在R₁-R₂（图11d）图解中，样品落在地幔分异花岗岩与碰撞前花岗岩交界区域。

图 11 花岗闪长岩构造背景判别Rb-（Y+Nb）（a）、Nb-Y（b）（据Pearce et al., 1984）、Hf-Rb/30-3Ta（c）（据Harris et al., 1986）图解及R1-R2（d）（据Batchelor et al., 1985）图解

① 地幔分异花岗岩；② 破坏性活动板块边缘 (板块碰撞前) 花岗岩；③ 板块碰撞后隆起期花岗岩；④ 晚造期花岗岩；⑤ 非造山区花岗岩；⑥ 同碰撞花岗岩；⑦造山期花岗岩

Figure 11. Identification of granodiorite structural background (a) Rb-(Y+Nb), (b) Nb-Y, (c) Hf-Rb/30-3Ta and (d) R1-R2 diagram

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罗城岩体位于龙首山造山带的西南缘大陆边缘活动带和祁连裂谷的发育构成了龙首山成矿带特定的构造环境（王承花，2010）。龙首山地区地壳演化自早古生代至中新生代经历了活动-稳定-再活动-再稳定-又活动的发展阶段，其在晚古生代处于稳定的拉张环境（强利刚等，2019），早古生代祁连造山带经历了北祁连洋向南俯冲，俯冲受阻，转为向北俯冲，引起北祁连岛弧与阿拉善陆块的碰撞，从而形成了一系列火山弧I型花岗岩（夏林圻等，2003；刘文恒等，2019；王增振等，2020）。罗城二叠纪黑云母花岗闪长岩指示其形成环境为岩浆弧，且R1-R2判别图解指示其形成环境为碰撞前消减花岗岩环境，说明在晚古生代该区还存在一期俯冲碰撞活动，与前人对龙首山晚石炭世—早二叠世西山头窑地区岩体处于弧后洋盆闭合过程，是古亚洲洋向南俯冲的结果（董国强等，2022）相吻合，同时与前人认为的北山地区二叠纪时期仍发生的俯冲–增生造山过程延续可至三叠纪（宋东方等，2018）存在相关性，而并非处于拉张稳定发展期（强利刚等，2019）。

6. 结论

（1）通过对罗城黑云母花岗闪长岩LA-ICP-MS锆石U-Pb测年得出，岩石锆石结晶年龄为(289±3) Ma ，属于早二叠世，指示了区域上华力西期的强烈构造岩浆事件。

（2）通过罗城黑云母花岗闪长岩岩相学、岩石地球化学及Hf同位素特征，岩体富集Rb、Th、K等大离子亲石元素和轻稀土元素，亏损Ba、Nb、Ta、P等高场强元素，属于准铝质钙碱性I型花岗岩，是由新生地壳部分熔融并混入底侵幔源物质的产物，指示了地壳深部强烈的地幔岩浆底侵作用。

（3）罗城黑云母花岗闪长岩地球化学特征指示其形成于碰撞前的消减花岗岩环境，结合龙首山地区构造演化历史，表明该区在晚古生代还存在一期俯冲碰撞，而并非一直处于拉张稳定发展期。

图 1 全球主要萤石矿床分布图（Hayes et al., 2017）

Figure 1. Distribution map of major fluorite deposits around the world

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图 2 中国主要萤石矿床分布图（王吉平等, 2014）

Figure 2. Distribution map of major fluorite deposits in China

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图 3 萤石矿床成因类型划分（Hayes et al., 2017）

a. 含氟或可能含氟的8种矿物或矿物群；b. 根据构造和岩浆组合对热液萤石矿床进行的简化分类

Figure 3. Genetic classification of fluorite deposit

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图 4 中国典型萤石矿床成因模式

a. 内蒙古赤峰地区与花岗岩岩浆热有关的萤石矿床构造背景（Pei et al., 2017）；b. 内蒙古赤峰地区与花岗岩岩浆热有关的萤石矿床成因模式图（Pei et al., 2017）；c、d. 浙江骨洞坑与次火山岩热液有关的断裂控矿的萤石矿床成因模式图（Fang et al., 2020）；e. 黔东北双河与热卤水热液有关的重晶石-萤石矿床成因模式图（李敏等，2021）；f. 扬子板块西缘碳酸盐岩地层中似层状产出的与铅锌矿床伴生的萤石矿床（Yu et al., 2022）

Figure 4. Genetic model of typical fluorite ore deposit in China

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1. 区域地质概况
2. 样品采集及岩石学特征
3. 样品分析方法
4. 分析结果
4.1 锆石U-Pb定年分析
4.2 锆石Hf同位素特征
4.3 主量元素特征
4.4 微量元素特征
5. 讨论
5.1 岩体成岩时代及岩石成因
5.2 岩浆起源及演化特征
5.3 构造背景
6. 结论

萤石矿床成因研究方法及发展趋势

作者简介: 张建芳（1985−），男，硕士，高级工程师，主要从事矿床成因和矿产勘查工作。E−mail：zhjianfang@126.com

通讯作者: 邹灏（1986−），男，博士，教授，主要从事矿物学、岩石学、矿床学的教学和科研工作。E−mail：zouhao@cdut.edu.cn。

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出版历程

Review on the Progress of Genetic Research Methods of Fluorite Deposits

1. 区域地质概况

2. 样品采集及岩石学特征

3. 样品分析方法

4. 分析结果

4.1 锆石U-Pb定年分析

4.2 锆石Hf同位素特征

4.3 主量元素特征

4.4 微量元素特征

5. 讨论

5.1 岩体成岩时代及岩石成因

5.2 岩浆起源及演化特征

5.3 构造背景

6. 结论

计量

出版历程

目录

1. 区域地质概况

2. 样品采集及岩石学特征

3. 样品分析方法

4. 分析结果

4.1 锆石U-Pb定年分析

4.2 锆石Hf同位素特征

4.3 主量元素特征

4.4 微量元素特征

5. 讨论

5.1 岩体成岩时代及岩石成因

5.2 岩浆起源及演化特征

5.3 构造背景

6. 结论

作者简介:
张建芳（1985−），男，硕士，高级工程师，主要从事矿床成因和矿产勘查工作。E−mail：zhjianfang@126.com

通讯作者:
邹灏（1986−），男，博士，教授，主要从事矿物学、岩石学、矿床学的教学和科研工作。E−mail：zouhao@cdut.edu.cn。