四川乌斯河铅锌矿床成矿流体特征及Ge富集物理化学条件

doi:10.19657/j.geoscience.1000-8527.2025.021

摘要/Abstract

摘要：

乌斯河大型铅锌矿床是川滇黔成矿带内典型的富锗(Ge)铅锌矿床,前人对其成矿流体特征及Ge的赋存状态、替代机制的研究有了深入的认识,但影响Ge富集的关键物理化学条件还不明确,限制了对Ge的富集机制的理解。为综合研究该矿床成矿流体与Ge的富集条件,进行了岩矿学分析、LA-ICP-MS测试、流体包裹体显微测温分析。认为该矿床中发育两个阶段的闪锌矿,LA-ICP-MS测试结果显示第Ⅰ 阶段闪锌矿中Ge含量(均值为221.0×10^-6)高于第 Ⅱ 阶段(均值为72.9×10^-6)。流体包裹体显微测温显示热液期各个阶段均一温度平均值分别为220℃、180℃,pH值相差不大,平均盐度w(NaCl_eq)分别为8.0%、5.9%,成矿压力分别为43×10⁵~283×10⁵ Pa、120×10⁵~236×10⁵ Pa。综合Ge的富集规律、赋存方式和成矿流体特征,结合热力学相图计算,得出第 Ⅰ 阶段闪锌矿中Ge的富集条件为:log $f O 2$ ≤-40.40,-15.75≤log $f S 2$ ≤-4.71,log[Zn]≥-14.36,log[Ge]≥-26.44;第 Ⅱ 阶段闪锌矿中Ge的富集条件为:log $f O 2$ ≤-44.28,-18.64≤log $f S 2$ ≤-5.78,log[Zn]≥-14.84,log[Ge]≥-28.19。研究认为硫逸度、氧逸度与离子活度是影响Ge富集的关键物理化学条件,并且高硫逸度和低氧逸度有利于Ge的富集,而离子活度是影响两阶段闪锌矿差异性富集Ge的主要原因。研究结果丰富了富Ge铅锌矿床的成矿理论,为Ge资源的勘探和综合利用提供了科学依据。

关键词: 铅锌矿床, Ge, 富集条件, 成矿流体特征, 热力学相图

Abstract:

The large-scale Wusihe lead-zinc deposit is a typical Ge-rich lead-zinc deposit in the Sichuan-Yunnan-Guizhou Metallogenic Belt.Although extensive prior research has been conducted on the characteristics of ore-forming fluids, as well as the occurrence and substitution mechanisms of Ge, the key physicochemical conditions controlling Ge enrichment remain unclear, which hinders a comprehensive understanding of its enrichment mechanisms. To address this, we performed petrological and mineralogical analyses, LA-ICP-MS analyses, and microthermometric analysis of fluid inclusions to systematically investigate the ore-forming fluids and Ge enrichment conditions of this deposit.Two stages of sphalerite development are identified in the deposit, corresponding to two mineralization stages: (Ⅰ) the quartz-sphalerite-pyrite-galena stage and (Ⅱ) the galena-pyrite-sphalerite-asphalt stage. LA-ICP-MS results show that the average Ge content in sphalerite from StageⅠis 221.0×10-6, which is higher than that from StageⅡ(72.9×10^-6). Microthermometric data of fluid inclusions indicate that the homogenization temperatures during the hydrothermal stages average 220 ℃ (StageⅠ) and 180 ℃(StageⅡ), respectively. The pH values of the two stages are comparable, with little variation. The average salinities, expressed as w(NaCl_eq), are 8.0% for StageⅠand 5.9% for Stage Ⅱ, indicating that the ore-forming fluids are of medium-low temperature and medium-low salinity. The ore-forming pressures are 43×10⁵-283×10⁵ Pa for StageⅠand 120×10⁵-236×10⁵ Pa for Stage Ⅱ.Based on the Ge enrichment patterns, its occurrence, ore-forming fluid characteristics, and thermodynamic phase diagram calculations, the Ge enrichment conditions in sphalerite are determined as follows: for StageⅠ, log $f O 2$ ≤-40.40, -15.75≤f_S2≤-4.71, log[Zn]≥-14.36, and log[Ge]≥-26.44; for StageⅡ, log $f O 2$ ≤-44.28, -18.64≤log $f S 2$ ≤-5.78, log[Zn]≥-14.84, and log[Ge]≥-28.19.The study suggests that sulfur fugacity, oxygen fugacity, and ion activity are the critical physicochemical factors affecting Ge enrichment. High sulfur fugacity and low oxygen fugacity are favorable for Ge enrichment, while ion activity is the main factor contributing to the differential Ge enrichment in sphalerite from the two stages. These findings enrich the metallogenic theory of Ge-rich lead-zinc deposits and provide a scientific basis for the exploration and comprehensive utilization of Ge resources.

Key words: lead-zinc deposit, Ge, enrichment condition, ore-forming fluid characteristics, thermodynamic phase diagram

中图分类号:

P618.2

孙世强, 陈翠华, 赖翔, 辜鹰, 赵文皓, 张海军, 马天祺, 陈宵杰, 宋志娇. 四川乌斯河铅锌矿床成矿流体特征及Ge富集物理化学条件[J]. 现代地质, 2025, 39(04): 931-946.

SUN Shiqiang, CHEN Cuihua, LAI Xiang, GU Ying, ZHAO Wenhao, ZHANG Haijun, MA Tianqi, CHEN Xiaojie, SONG Zhijiao. Characteristics of Ore-Forming Fluids and Physicochemical Conditions for Ge Enrichment in the Wusihe Lead-Zinc Deposit, Sichuan[J]. Geoscience, 2025, 39(04): 931-946.

图/表 17

图1 华南大地构造背景(a)及川滇黔铅锌矿成矿带区域地质图(b)(据文献[8]修改)

Fig.1 Tectonic setting of South China (a) and regional geological map of the Sichuan-Yunnan-Guizhou Pb-Zn metallogenic belt (b) (modified after Ref.[8])

图2 乌斯河矿床地质图(据文献[27]修改)

Fig.2 Geological map of the Wusihe Deposit (modified after reference[27])

图3 乌斯河矿床坑道、手标本及镜下照片 (a)呈层状分布的矿体;(b)脉状闪锌矿穿插早阶段闪锌矿;(c)层状矿石,分布大颗粒闪锌矿(Sp1),下方白云石分布着细脉闪锌矿(Sp2);(d)浸染状矿石;(e)小颗粒的Sp2交代颗粒较大Sp1和Py(反射光);(f)Sp1局部呈褐色,可见环带结构(透射光);(g)Sp2颜色较浅呈浅棕黄色(透射光);(h)Gn1包含Py,与后形成的Sp2呈包含结构(反射光);(i)Gn2受应力发育揉皱结构,与Sp2伴生(反射光);(j)Gn2与Bit沿Sp裂隙填充;Sp.闪锌矿;Py.黄铁矿;Gn.方铅矿;Ma.白铁矿;Qz.石英;Bit.沥青;Dol.白云石

Fig.3 Photos of tunnels, hand specimens and microscopic images from the Wusihe Deposit

图4 乌斯河矿床矿物生成顺序

Fig.4 Paragenetic sequence of minerals in the Wusihe deposit

表1 乌斯河矿床闪锌矿LA-ICP-MS实验结果(10-6)

Table 1 LA-ICP-MS analytical results of sphalerite from the Wusihe Deposit (10-6)

成矿阶段	样品编号	Mn	Fe	Cu	Ga	Ge	Ag	Cd
第Ⅰ阶段	WSH-10-1-(1)-1	59.5	27189	103.0	0.19	180.0	94.9	2863.0
	WSH-10-1-(1)-2	59.2	27225	101.0	1.21	148.0	84.3	2931.0
	WSH-10-1-(1)-3	65.3	27234	103.0	1.39	163.0	91.9	2954.0
	WSH-10-1-(1)-4	54.6	29176	115.0	0.47	155.0	95.7	3206.0
	WSH-10-1-(2)-1	50.5	14035	82.6	0.41	195.0	50.2	2714.0
	WSH-10-1-(2)-2	53.0	4385	33.6	0.29	110.0	30.1	3589.0
	WSH-3-1-(1)-1	10.7	6462	154.0	24.80	98.4	49.1	881.0
	WSH-3-1-(1)-2	6.58	4184	262.0	14.10	225.0	60.7	803.0
	WSH-2-(1)-1	39.7	21318	146.0	15.10	113.0	42.5	1556.0
	WSH-2-(1)-2	37.2	14776	147.0	19.10	118.0	40.1	1562.0
	WSH-2-(5)-1	16.4	12249	858.0	0.30	624.0	92.8	78.7
	WSH-2-(5)-2	11.3	10440	666.0	0.65	511.0	73.6	54.7
	WSH-2-(5)-3	24.5	9151	229.0	0.05	246.0	33.0	55.3
第Ⅱ阶段	WSH-10-1-(3)-1	5.86	1073	60.0	3.93	50.1	61.8	4618.0
	WSH-10-1-(3)-2	6.34	1437	240.0	0.59	169.0	95.7	3269.0
	WSH-3-1-(2)-1	41.80	6517	115.0	2.64	78.4	47.6	3786.0
	WSH-3-1-(2)-2	43.20	7807	79.0	4.70	77.7	52.6	3750.0
	WSH-2-1-(1)-1	-	361	411.0	12.19	204.0	78.4	1850.0
	WSH-2-1-(1)-2	-	534	163.0	0.69	109.0	53.8	1926.0
	WSH-2-1-(2)-2	2.77	1357	128.0	83.7	40.6	16.9	2839.0
	WSH-2-(2)-1	3.22	1059	64.1	17.5	7.90	61.7	7530.0
	WSH-2-(2)-2	3.58	1218	4.96	0.44	1.54	5.49	9062.0
	WSH-2-(3)-1	12.10	7560	96.0	36.1	53.1	39.7	1965.0
	WSH-2-(3)-2	13.90	6693	80.7	29.1	49.3	37.3	2009.0
	WSH-2-(4)-3	8.26	5620	85.6	28.2	35.8	34.8	1555.0
	WSH10-1-3	2.23	210	155.0	20.0	73.6	144.0	2568.0
	WSH3-1-4	80.60	4220	97.7	1.43	70.0	81.3	2766.0

图5 乌斯河矿床不同阶段闪锌矿的微量元素箱形图(10-6)

Fig.5 Box plots of trace elements in sphalerite from different stages of the Wusihe deposit (10-6)

图6 乌斯河矿床流体包裹体特征 (a)、(b)闪锌矿中L+V型次生包裹体(第一类);(c)、(d)闪锌矿中L+V型原生包裹体(第二类);(e)石英中L+V型负晶型原生包裹体(第一类);(f)石英中V+L型原生包裹体(第二类);(g)石英中L型包裹体沿长轴方向一致定向排列;(h)石英中孤立分布的L型负晶型原生包裹体;(i)、(j)白云石中呈群状分布的L+V型类负晶型原生包裹体(第一类);(k)、(l)白云石中L+V型次生包裹体(第一类)

Fig.6 Characteristics of fluid inclusions in the Wusihe Deposit

表2 热液期各成矿阶段流体包裹体显微测温数据

Table 2 Microthermometric data of fluid inclusions from each mineralization stage of the hydrothermal period

热液期成矿阶段	寄主矿物	测试个数	大小(μm)	均一相态	均一温度(℃)	冰点(℃)	盐度w(NaCl_eq)	pH
Ⅰ	闪锌矿	22	3~15	L	154.0~269.0	-9.8~-3.2	5.3~13.7	5.42~5.66
	石英	14	7~40	L	153.2~290.0	-7.1~-0.9	1.6~10.6	5.44~5.66
	白云石	18	3~13	L	150.1~254.2	-9.0~-2.3	3.9~12.8	5.44~5.66
Ⅱ	闪锌矿	17	3~15	L	144.6~210.8	-3.9~-0.8	1.4~6.3	5.47~5.70
	石英	14	6~40	L	160.0~236.9	-8.6~-1.5	2.6~12.4	5.46~5.63
	白云石	16	3~10	L	152.7~203.5	-9.4~-3.0	5.0~13.3	5.48~5.66

图7 流体包裹体均一温度直方图 (a)热液期第 Ⅰ 阶段,闪锌矿、石英和白云石中流体包裹体均一温度直方图;(b)热液期第 Ⅱ 阶段,闪锌矿、石英和白云石中流体包裹体均一温度直方图

Fig.7 Histograms of homogenization temperatures of fluid inclusions

图8 乌斯河矿床闪锌矿微量元素时间分辨率曲线

Fig.8 Time-resolved curves of trace elements in sphalerite from the Wusihe deposit

图9 乌斯河矿床闪锌矿微量元素含量对比图(川滇黔地区部分矿床数据引自文献[6][31]) WSH-Sp1,热液期第 Ⅰ 阶段闪锌矿;WSH-Sp2,热液期第 Ⅱ 阶段闪锌矿

Fig.9 Comparison of trace element contents in sphalerite from the Wusihe deposit (data of some deposits in the Sichuan-Yunnan-Guizhou region are cited from references [6] and [31])

图10 成矿流体的盐度与闪锌矿中Ge富集程度的关系(其它矿床的数据引自文献[41-48])

Fig.10 Relationship between salinity of ore-forming fluids and Ge enrichment in sphalerite (data from other deposits are cited from references [41-48])

表3 相关化学反应化学式

Table 3 Chemical formulas of relevant reactions

序号	反应方程式	序号	反应方程式
1	Ge+O₂=GeO₂	2	Ge+S₂=GeS₂
3	GeS₂+O₂=GeO₂+S₂	4	Zn+1/2O₂=ZnO
5	Zn+1/2S₂=ZnS	6	ZnS+1/2O₂=ZnO+1/2S₂
7	Pb+ 1/2O₂=PbO	8	3Pb+2O₂=Pb₃O₄
9	Pb+O₂=PbO₂	10	Pb+1/2S₂=PbS
11	PbS+1/2O₂=PbO+1/2S₂	12	3PbS+ 2O₂=Pb₃O₄+3/2S₂
13	PbS+O₂=PbO₂+1/2S₂	14	4S₂=S₈
15	3Fe+2O₂=Fe₃O₄	16	Fe₃O₄+1/2O₂=3Fe₂O₃
17	Fe+1/2S₂=FeS	18	FeS+1/2S₂=FeS₂
19	3FeS+2O₂=Fe₃O₄+3/2S₂	20	3FeS₂+2O₂=Fe₃O₄+3S₂
21	3FeS₂+3/2O₂=Fe₂O₃+2S₂

表4 不同温度下富Ge闪锌矿-方铅矿-黄铁矿沉淀的log f O 2-log f S 2

Table 4 log f O 2-log f S 2 for precipitation of Ge-rich sphalerite-galena-pyrite at different temperatures

温度(K)	413.15	453.15	493.15	533.15
log $f O 2$	log $f O 2$ ≤-48.17	log $f O 2$ ≤-44.28	log $f O 2$ ≤-40.40	log $f O 2$ ≤-37.56
log fS₂	-21.53≤log $f S 2$ ≤-6.84	-18.64≤log $f S 2$ ≤-5.78	-15.75≤log $f S 2$ ≤-4.71	-13.62≤log fS₂≤-3.94

表4 不同温度下富Ge闪锌矿-方铅矿-黄铁矿沉淀的log f O 2-log f S 2

Table 4 log f O 2-log f S 2 for precipitation of Ge-rich sphalerite-galena-pyrite at different temperatures

温度(K)	413.15	453.15	493.15	533.15
log $f O 2$	log $f O 2$ ≤-48.17	log $f O 2$ ≤-44.28	log $f O 2$ ≤-40.40	log $f O 2$ ≤-37.56
log fS₂	-21.53≤log $f S 2$ ≤-6.84	-18.64≤log $f S 2$ ≤-5.78	-15.75≤log $f S 2$ ≤-4.71	-13.62≤log fS₂≤-3.94

图11 不同温度下矿物的 log f O 2-log f S 2 相图蓝色实线为Zn的凝聚线;黄色实线为Pb的凝聚线;绿色实线为Fe的凝聚线;黑色实线为S的凝聚线;黄色区域为Ge;红色区域为GeS2;绿色区域为GeO2;Sp.闪锌矿; Spa.红锌矿; Py.黄铁矿; Po.磁黄铁矿; Mt.磁铁矿; Hm.赤铁矿; Gn.方铅矿; Li.铅黄; Pl.块黑铅矿; Mi.铅丹

Fig.11 log f O 2-log f S 2 phase diagrams of minerals at different temperatures

表5 相关化学反应方程式

Table 5 Relevant chemical reaction equations

序号	反应方程式	序号	反应方程式
1	H₂S=HS^-+H⁺	2	HS^-=S^2-+H⁺
3	Zn²⁺+H₂S=ZnS+2H⁺	4	Zn²⁺+HS^-=ZnS+H⁺
5	Zn²⁺+S^2-=ZnS	6	Ge⁴⁺+2H₂S=GeS₂+4H⁺
7	Ge⁴⁺+2HS^-=GeS₂+2H⁺	8	Ge⁴⁺+2S^2-=GeS₂
9	Ge(OH)₄+2H₂S= GeS₂+4H₂O	10	Ge(OH)₄+2HS^-= GeS₂+2H₂O+2OH^-
11	Ge(OH)₄+2S^2-= GeS₂+4OH^-	12	ZnC $l 4 2 -$ +H₂S= ZnS+4Cl^-+2H⁺
13	ZnC $l 4 2 -$ +HS^-= ZnS+4Cl^-+H⁺	14	ZnC $l 4 2 -$ +S^2-= ZnS+4Cl^-

表5 相关化学反应方程式

Table 5 Relevant chemical reaction equations

序号	反应方程式	序号	反应方程式
1	H₂S=HS^-+H⁺	2	HS^-=S^2-+H⁺
3	Zn²⁺+H₂S=ZnS+2H⁺	4	Zn²⁺+HS^-=ZnS+H⁺
5	Zn²⁺+S^2-=ZnS	6	Ge⁴⁺+2H₂S=GeS₂+4H⁺
7	Ge⁴⁺+2HS^-=GeS₂+2H⁺	8	Ge⁴⁺+2S^2-=GeS₂
9	Ge(OH)₄+2H₂S= GeS₂+4H₂O	10	Ge(OH)₄+2HS^-= GeS₂+2H₂O+2OH^-
11	Ge(OH)₄+2S^2-= GeS₂+4OH^-	12	ZnC $l 4 2 -$ +H₂S= ZnS+4Cl^-+2H⁺
13	ZnC $l 4 2 -$ +HS^-= ZnS+4Cl^-+H⁺	14	ZnC $l 4 2 -$ +S^2-= ZnS+4Cl^-

图12 不同温度下的pH-log[a]相图(引自文献[5]) 蓝色实线为Zn的凝聚线;红色实线为Ge的凝聚线;黑色实线为S的凝聚线;黑色虚线为Zn、Ge的凝聚线

Fig.12 pH-log[a] phase diagrams at different temperatures (cited from reference [5])

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