Geochemical Characteristics and Metal Enrichment Rules of Black Shales in the Zhuxi Vanadium Ore Field, Eastern Guizhou
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摘要: 目前急需分析黔东注溪钒矿形成的环境、成矿的物质来源以及矿化富集规律，指导实际地质勘查工作.系统研究了注溪矿区内中洞、老屋基和坪哨3个典型岩性剖面中黑色岩含矿岩系及矿层的全岩主微量元素组成.结果表明，含矿岩系具有较高的SiO2、MnO、Ce/Ce*和Eu/Eu*值，而矿层则含相对较高的Al2O3、Fe2O3、TiO2、CaO、Na2O、K2O、P2O5、V2O5、REE、As、Cu、Pb、Zn、Mo、Ni、Ti、Cr、Rb、Sr、Th、U和V.含矿岩系与矿层的主微量地球化学特征显示注溪钒矿床的成矿物源具有一定程度陆源物质的输入，且在成矿阶段受到了热水作用及生物作用的影响.另外，由南至北各剖面的热水成矿作用逐渐减弱；含矿岩系及矿层沉积环境均属缺氧环境，其中坪哨剖面的矿层沉积环境的缺氧程度要高于其他剖面.因此，注溪钒矿床钒富集成矿主要受古环境的还原条件和热液活动的影响，其中还原环境对钒元素的富集成矿起主要作用.据此推测坪哨剖面矿层形成时的海水深度应最深，北矿段中洞剖面的最浅；喷流热水带来的V等大量多金属元素在喷口及其附近大规模成矿.Abstract: There is an urgent need to analyze the forming environment,the metal enrichment process and ore-forming rules of the Zhuxi vanadium ore field in eastern Guizhou Province. This paper systematically studies the major and trace element compositions of ore-bearing rocks and ore strata from three typical black shale sections in the ore field. The results show that ore-bearing rocks contain high contents/values of SiO2,MnO,Ce/Ce* and Eu/Eu*,while ore strata have higher concentrations of Al2O3,Fe2O3,TiO2,CaO,Na2O,K2O,P2O5,V2O5,REE,As,Cu,Pb,Zn,Mo,Ni,Ti,Cr,Rb,Sr,Th,U and V. The major and trace element geochemical characteristics of ore-bearing rocks and ores indicate that the ore-forming source of the Zhuxi vanadium ore field had a certain degree of continental material input,whilst both hydrothermal and biological processes played a significant role during the ore-forming process. In addition,the intensities of hydrothermal process decreased from southern to northern sections and the sedimentary environment of both ore-bearing rocks and ores was anoxic. The ores from the Pingshao lithological sections were formed in the most reducing environment than those from other sections. Therefore,the V enrichment and mineralization in the Zhuxi ore field has mainly been controlled by reducing paleoenvironment and hydrothermal activity,and the reducing environment has been more significant for V mineralization. It can be inferred that ores from the Pingshao section should have been deposited in the deepest seawater environment while the ores from northern Zhongdong section had the shallowest seawater level. Exhalative fluid brought abundant V and other metal elements depositing in the vent and adjacent areas,leading to the large-scale mineralization.
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图 1 贵州省寒武纪梅树村期岩相古地理简图
Fig. 1. Simplified Cambrian (Meishucun period) lithofacies paleogeographic map of the Guizhou Province
图 3 注溪钒矿区地层及矿层野外照片
a.陡山沱组与上覆留茶坡组呈整合接触关系；b.多金属层中的磷质结核；c.寒武系下统九门冲组的多金属层；d.多金属层与围岩产状一致
Fig. 3. Field photos of the ore-bearing strata and ores in the Zhuxi V ore field
图 4 注溪钒矿矿石构造与显微结构
a.层状构造；b.条纹状构造；c.不等晶结构；d.粉-微晶结构和缝合线构造
Fig. 4. Ore structures and microscopic textures in the Zhuxi V ore field
图 5 注溪钒矿含矿岩系与矿层主微量元素图解
Fig. 5. Plots for major and trace element compositions of ore-bearing rocks and ores from the Zhuxi V ore field
图 6 注溪钒矿各剖面含矿岩系与矿层主微量元素平均值变化
Fig. 6. Plots for average major and trace element compositions of ore-bearing rocks and ores from three lithological sections of the Zhuxi V ore field
图 7 注溪钒矿含矿岩系与矿层北美页岩标准化稀土配分模式图（a、b）与平均地壳标准化微量元素蛛网图（c、d）
标准化值分别据Haskin（1984）和Yaroshevsky（2006）
Fig. 7. North American shale-normalized REE patterns (a, b) and average crust-normalized trace elements patterns (c, d) for ore-bearing rocks and ores from the Zhuxi V ore field
图 8 注溪钒矿主微量元素图解
a.Al/(Al+Fe+Mn)-SiO2/Al2O3图解；b. SiO2/(K2O+Na2O)-MnO/TiO2图解，据Murray（1994）；c. Y-Ho图解；d. REE-La/Yb图解，据Allègre and Minster（1978）；e. Th-U图解，据Boström（1983）；f. Al2O3/(Al2O3+Fe2O3T)-Fe2O3T /TiO2图解, 据Murray（1994）
Fig. 8. Plots of major and trace elements for the Zhuxi V ore field
图 9 注溪钒矿矿化富集模式简图
据杨剑（2009）修改
Fig. 9. Cartoon-like profile of the mineralization enrichment patterns for the Zhuxi V ore field
表 1 注溪钒矿含矿岩系及矿石特征
Table 1. Characteristics of ore-bearing rocks and ores in the Zhuxi V ore field
岩石名称 矿物成分 结构构造 其他特征 硅质岩 主要矿物成分为硅质，含有少量的粘土矿物、粉砂质碎屑、有机质等.粉砂级碎屑主要成分为石英矿物屑. 硅质呈微-隐晶结构，晶体呈半自形-他形；粘土矿物呈不均匀分布，具有显微鳞片状结构，沿长轴方向定向性排列好. 石英矿物屑，呈次圆状-圆状零星分布，磨圆度和分选性均良好，碎屑矿物成熟度良好.有机质特征为污染状分布. 多金属层 岩性为灰绿色含黄铁矿含炭粘土质粉砂岩，含磷质结核.矿物成分有粉砂级陆源碎屑、粘土矿物、有机质和黄铁矿等.粉砂级陆源碎屑矿物成分以石英矿物屑为主. 粉砂状结构、层纹-条纹-条带状构造. 粉砂级陆源碎屑呈次圆状、圆状，呈层不均匀分布，具有良好的磨圆度和分选性，碎屑矿物成熟度较高.粘土矿物呈显微鳞片状晶体，层状分布.有机质呈层纹状不均匀分布.黄铁矿呈星散状分布，结晶颗粒大小为细-粉-微-隐晶级，粒度 < 0.25 mm，颗粒形态为半自形-他形，粒状晶体. 黑色炭质粉砂岩、炭质粘土岩 岩石矿物成分由陆源碎屑、有机质和泥质等组分组成，其中陆源碎屑成分以石英矿物屑为主. 粉砂质、泥质结构，层纹状、层状构造. 陆源碎屑呈不均匀层纹状分布，表现良好的磨圆度和分选性，呈次圆状、圆状. 
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