Characteristics of chlorites from the Haopinggou Ag–Au polymetallic deposit in the Xiong’ershan ore concentration area and its exploration implications
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摘要: 为理清蒿坪沟Ag-Au多金属矿床中多阶段矿化与热液蚀变之间的关系，文章选取与铅锌成矿阶段密切相关的绿泥石进行野外观察及电子探针分析。文章将蒿坪沟Ag-Au多金属矿床中的绿泥石分为3类：Ⅰ型分布在石英脉两侧的围岩中；Ⅱ型呈细粒、隐晶质填充于隐爆角砾岩基质；Ⅲ型与铅锌硫化物共生、或以蠕虫状广泛分布在石英颗粒间隙中。3种类型绿泥石均为斜绿泥石，并落在了铁镁绿泥石的范围内，指示其形成于偏还原的酸性环境中；在阳离子置换中，主要发生了Fe2+对Mg2+的置换，其余置换作用均不明显；3种绿泥石形成与镁铁质围岩关系密切。由校正后的绿泥石地质温度计估算出3种类型绿泥石的形成温度为196~239 ℃，属于中—低温热液蚀变范围。3类绿泥石与蒿坪沟Ag-Au多金属矿床银铅锌成矿阶段相匹配，对进一步找矿勘查具有重要意义。绿泥石化学特征表明岩浆热液参与了成矿流体的形成，绿泥石形成于熊耳山矿集区早白垩世大规模岩浆−成矿时期。Abstract:
Objective The Haopinggou Ag-Au polymetallic deposit is a typical intermediate-sulfidation epithermal deposit in the Xiong'ershan ore concentration area. Ag-Pb-Zn mineralization mainly occurs in steeply dipping veins and breccia matrix. The relationship between large-scale Pb-Zn mineralization and widely developed alteration minerals remains unclear. Methods In order to discuss chlorite's significance related to Pb-Zn mineralization, chlorite composition in the Haopinggou Ag-Au polymetallic deposit has been analyzed by field geological observation and electron microprobe analysis (EMPA) in this paper. Results Three types of chlorite were observed in the deposit, occurring in altered wall rocks (Type I), in(with) Pb-Zn sulfides (Type II), and in(with) the breccia matrix (Type III). All three types of chlorite are prochlorites and fall within the compositional range of Fe-rich chlorite, indicating that they could be formed in a partially reducing acidic environment. Fe2+ for Mg2+ is the primary substitution in chlorite lattice, suggesting a close association between chlorite formation and mafic wall rocks. Based on the corrected chlorite geothermometer, these chlorites formed under aluminum-saturated conditions in the medium to low-temperature range of 196-239℃. The temperatures of chlorites associated with mineralization (Types II and III) are higher than those in chlorites around quartz veins (Type I). It is believed that during the mineralization process, the hydrothermal fluids evolved from acidic to nearly neutral conditions as the temperature gradually decreased. The initial acidic environment facilitated interaction between water and rocks, promoting the dissolution of surrounding rocks and providing space for the further precipitation of metal sulfides. The evolution of ore fluid properties also corresponds to the deposition process of Ag-Pb-Zn. The genesis of chlorite in the deposit is well-correlated with the ore-forming and holds significant prospecting value. (1) Type I chlorites mainly develop on both sides of quartz veins, formed by the dissolution and metasomatism of basic wall rocks by ore-bearing hydrothermal fluids. Type I chlorite's Fe and Mg components are mostly derived from the wall rocks. Although this type does not contain mineralization, it can be used to trace veins. (2) Type III chlorites reflect the migration process of ore-bearing hydrothermal fluids carrying dissolved minerals (biotite/clinopyroxene), which precipitate with changes in the physicochemical environment. Type III chlorite's Fe and Mg components are mainly introduced by ore-bearing hydrothermal fluids. This type of chlorite fills the intergranular pore spaces between minerals and easily replaces minerals such as biotite and hornblende, exhibiting apparent mineral alteration features in hand specimens, which is beneficial for prospecting.(3) The formation mechanism of Type II chlorites includes the possibilities mentioned above. This type of chlorite is formed by complete dissolution and metasomatism of cement in ore-bearing hydrothermal fluids, forming fine-grained cryptocrystalline chlorite fillings in breccia rocks. Ore-bearing hydrothermal fluids and wall rocks both contribute Fe and Mg in the chlorites. Hand specimens of Type II chlorite are dark green, disseminated and filled in the matrix, making it easy to distinguish. The chemical characteristics of Type II chlorites are similar to those of chemical characteristics of granite-related deposits, implying the contribution of magmatic fluids to ore-forming fluids. Conclusion The Haopinggou Ag-Au polymetallic deposit contains three types of chlorites. Their chemical characteristics all reflect an acidic and reducing metallogenic environment. In cation exchange, the primary substitution is Fe for Mg, and other substitutions are insignificant. The effect of Fe/(Fe+Mg) must be eliminated in order to calculate the temperature of such deposits using chlorite geothermometers. The formation mechanism of the three chlorites is closely related to mafic wall rock, and their chemical properties suggest the involvement of magmatic fluids in ore-forming fluids. Significance These three types of chlorite are well-matched with intense Ag-Pb-Zn mineralization and can serve as key indicators for locating Pb-Zn veins. -
Key words:
- Polymetallic deposit /
- prospecting significance /
- Chlorite /
- EMPA /
- mineralization /
- Geochemistry /
- Xiong’ershan.
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图 1 华北克拉通南缘熊耳山矿集区地质简图（底图据Tian et al.，2023修改）
a—华北克拉通南缘在中国东部的位置；b—熊耳山矿集区大地构造简图及矿产分布图
Figure 1. Simplified geological map of the Xiong’ershan ore concentration area along the southern margin of the North China Craton（Base map modified after Tian et al., 2023）
(a) The inset showing the tectonic location of the southern margin of the North China Craton in eastern China; (b) Geological map of the Xiong’ershan ore concentration area, showing the distribution of the major deposits
图 2 蒿坪沟Ag-Au多金属矿床地质简图（底图据梁涛等，2015修改）
Figure 2. Geological map of the Haopinggou Ag-Au polymetallic deposit（Base map modified after Liang et al., 2015）
图 3 蒿坪沟Ag-Au多金属矿床勘探线剖面图（剖面位置见图2）
Figure 3. Representative cross-section of the Haopinggou Ag-Au polymetallic deposit (The position of the cross-section is shown in Fig. 2.)
图 4 蒿坪沟Ag-Au多金属矿床矿物共生序列（据Tian et al., 2023修改）
Figure 4. Paragenetic sequence of the Haopinggou Ag-Au polymetallic deposit（modified after Tian et al., 2023）
图 5 蒿坪沟Ag-Au多金属矿床绿泥石分布情况
Chl—绿泥石；Gn—方铅矿；Sp—闪锌矿；Py—黄铁矿；Ank—铁白云石a—铅锌矿脉两侧围岩绿泥石蚀变；b—石英脉两侧蚀变绿泥石；c—隐爆角砾岩基质中填充绿泥石与铁白云石；d—隐爆角砾岩中发生绿泥石蚀变的斑岩角砾
Figure 5. Distribution of chlorites in the Haopinggou Ag-Au polymetallic deposit
(a) Chlorite alteration of surrounding rocks on both sides of Pb-Zn veins; (b) Altered chlorites occurred on both sides of quartz veins; (c) Chlorites and ankerites filled in breccia matrix; (d) Chlorite-altered porphyry breccia Chl–chlorite; Gn–galena; Sp–sphalerite; Py–pyrite; Ank–ankerite
图 6 蒿坪沟Ag-Au多金属矿床绿泥石显微形态特征
Chl—绿泥石；Ser—绢云母；Gn—方铅矿；Qz—石英；Sp—闪锌矿；Py—黄铁矿；Cal—方解石a—发育于石英脉两侧的绿泥石（正交偏光）；b—隐爆角砾岩基质中填充的绿泥石（正交偏光）；c—与黄铁矿、闪锌矿共生的绿泥石（正交偏光+反射光）；d—填充在石英颗粒间隙的蠕虫状绿泥石（正交偏光）；e—背散射镜下绿泥石电子探针打点位置分布，可见绿泥石与绢云母共生；f—背散射镜下绿泥石电子探针打点位置分布
Figure 6. Representative photomicrographs of chlorite characteristics of the Haopinggou Ag-Au polymetallic deposit
(a) Chlorite developed on both sides of quartz veins (cross-polarized light); (b) Chlorite filled in breccia matrix (cross-polarized light); (c) Chlorite coexisting with pyrite and sphalerite (cross-polarized light+ reflected light) ; (d) Worm-like chlorite filling the interstices of quartz grains (cross-polarized light); (e) Backscattered electron images of the distribution of chlorite EMPA dots, showing coexistence with sericite; (f) Backscattered electron images of the distribution of chlorite EMPA dots Chl–chlorite; Ser–sericite; Gn–galena; Qz–quartz; Sp–sphalerite; Py–pyrite; Cal–calcite
图 7 蒿坪沟Ag-Au多金属矿床绿泥石化学性质图解
a—绿泥石Fe−Si图解（Deer et al.，1962）；b—绿泥石Al+□-Mg−Fe图解（Zane and Weiss，1998）；c—绿泥石Si−R2+图解（据刘燚平等，2016修改）
Figure 7. Chemical diagram of chlorite from the Haopinggou Ag-Au polymetallic deposit
(a) Fe vs. Si diagram of chlorite (Deer et al., 1962); (b) Al+□–Mg–Fe plot (Zane and Weiss, 1998); (c) Si vs. R2+ diagram (modified after Liu et al., 2016)
图 8 蒿坪沟Au-Ag多金属矿床绿泥石阳离子相关关系图（单位为a.p.f.u）
a—绿泥石AlⅥ-AlⅣ图解；b—绿泥石Fe2+-Mg2+图解；c—绿泥石Fe2+/(Fe2++Mg2+）-AlⅣ图解；d—绿泥石(Fe2++ AlⅥ）-Mg2+图解；e—绿泥石Mg2+-AlⅣ图解；f—绿泥石Si4+-Mg2+图解
Figure 8. Correlation of cations in chlorites from the Haopinggou Ag-Au polymetallic deposit（unit a.p.f.u）
(a) AlⅥ vs. AlⅣ diagram of chlorite; (b) Fe2+vs. Mg2+ diagram of chlorite; (c) Fe2+/(Fe2++Mg2+) vs. AlⅣ diagram of chlorite; (d) (Fe2++ AlⅥ) vs. Mg diagram of chlorite; (e) Mg2+ vs. AlⅣ diagram of chlorite; (f) Si4+ vs.Mg2+ diagram of chlorite
图 9 蒿坪沟Ag-Au多金属矿床绿泥石形成温度频数（N）分布直方图
a—绿泥石形成温度T1频数分布直方图；b—绿泥石形成温度T2频数分布直方图；c—绿泥石形成温度T3频数分布直方图
Figure 9. Hsitogram of formation temperatures of chlorites from the Haopinggou Ag-Au polymetallic deposit
(a) Hsitogram of formation T1 of chlorites; (b) Hsitogram of formation T2 of chlorites; Hsitogram of formation T3 of chlorites
图 10 绿泥石形成温度T与AlⅣ及Si4+相关性图解
a—绿泥石AlⅣ−T平均关系图解；b—绿泥石Si4+−T平均关系图解；c—绿泥石AlⅣ−T3关系图解；d—绿泥石Si4+ −T3关系图解
Figure 10. Correlation diagram of T vs. AlⅣ and Si4+
(a) AlⅣ vs. Taverage diagram of chlorite; (b) Si4+ vs. Taverage diagram of chlorite; (c) AlⅣ vs. T3 diagram of chlorite; (d)Si4+ vs. T3 diagram of chlorite
图 11 不同成因类型矿床中的绿泥石特征
不同矿床类型中的绿泥石投图区域：1—活动的地热系统；2—块状硫化物矿床（Kranidiotis and Maclean，1987）；3—热液铜（金）矿化带（Zane and Fyfe，1995）；4—与铜金矿化相关的绿泥石（Dora and Randive，2015）；5—云母石英岩中的绿泥石（Randive et al.，2015）；6—与花岗岩相关的矿床（Trumbull et al.，1996）；7—热液脉型矿床（Walshe，1986）a—绿泥石中Fe/（Fe+Mg）−（Si/Al）关系图解；b—绿泥石中Fe/（Fe+Mg）−AlⅣ关系图解（据周栋等，2018修改）
Figure 11. Chlorite characteristics in different genic types of deposits
(a) Fe/(Fe+Mg) vs. (Si/Al) diagram of chlorite; (b) Fe/(Fe+Mg) vs. AlⅣ diagram of chlorite (modified after Zhou et al., 2018) Data source: 1−active geothermal system; 2−massive sulfide deposit (Kranidiotis and Maclean, 1987); 3−hydrothermal mineralization zone (Zane and Fyfe, 1995); 4−Chlorites related to Cu-Au mineralization (Dora and Randive, 2015); 5−green-mica quartzites (Randive et al., 2015); 6−deposits associated with granite (Trumbull et al., 1996); 7−hydrothermal vein-type deposit (Walshe, 1986)
表 1 熊耳山矿集区蒿坪沟Ag-Au多金属矿床与康山金多金属矿床地质特征
Table 1. Geological characteristics of the Haopinggou Ag-Au polymetallic deposit and the Kangshan Au polymetallic deposit in the Xionger’ shan ore concentration area
矿床名称 蒿坪沟Ag-Au多金属矿床 康山金多金属矿床 矿床类型 岩浆热液型 岩浆热液型 大地构造位置 华北克拉通南缘、熊耳山矿集区西北部 华北克拉通南缘、熊耳山矿集区西南部 控矿构造 北东向陡倾断裂和局部隐爆角砾岩 北东向脆性断裂 成矿阶段及矿物组合（Li et al.，2013） 第一阶段：Qz-Sd-Mag-Elc 第一阶段：Qz-Py 第二阶段：Gn-Sp-Qz-Ank 第二阶段：Qz-Py-Ccp-Au 第三阶段：Qz-Cal-Fl 第三阶段：Gn-Sp-gold-Qz-Ank- — 第四阶段：Qz-Cal-Fl 成矿时代 热液独居石125~123 Ma（Tian et al.，2023） 热液独居石年龄为131 Ma（张哲铭等，2023） 流体特征及来源 含银硫化物来自蒿坪沟花岗岩体，表现为还原性的酸性流体（Li et al.，2016） 含金流体来自隐伏花岗岩体， 表现为相对弱酸性的还原环境；其成矿机制为流体沸腾，第三阶段主要成矿机制为流体混合（Zhang et al.，2020） 成矿温度（Li et al.，2013；徐进鸿，2021） — Qz-Py：322~359 ℃ Qz-Sd-Mag-Elc：217~349 ℃ Qz-Py-Ccp-Au：226~305 ℃（256~302 ℃） Gn-Sp-Qz-Ank：172~267 ℃（194~237 ℃） Gn-Sp-Au-Qz-Ank：185~246 ℃ Qz-Cal-Fl：116~205 ℃ Qz-Cal-Fl：130~221 ℃ 绿泥石分类 主要为铁镁绿泥石 富铁种属的绿泥石，围岩属于铁镁绿泥石，与矿化相关的绿泥石为铁绿泥石（周栋等，2018） 注：成矿温度为流体包裹体测温数据（Li et al.，2013；徐进鸿，2021），括号内为绿泥石EMPA数据所计算出T3温度 
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