Distribution and Resources of Dispersed Metals in Pb-Zn Deposits of Qinling Orogenic Belt
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摘要: Ga、Ge、In等稀散金属对高科技发展及国防建设有着重要作用，被我国和美欧列为战略性关键矿产资源.铅锌矿床不仅是我国铅、锌有色金属的主要来源，同时蕴藏丰富的稀散金属资源.秦岭造山带是我国重要的铅锌资源产地，但其稀散金属研究较为薄弱，尚缺乏系统性的稀散金属资源评价工作.本研究选取秦岭造山带西秦岭和东秦岭地区19个代表性铅锌矿床为研究对象，利用LA-ICP-MS测定了不同矿床中闪锌矿微量元素组成并收集前人分析数据，揭示闪锌矿中稀散金属Ga、Ge、In、Cd的含量和赋存状态.研究结果显示，西秦岭地区铅锌矿床闪锌矿中Ga、Ge含量略高于东秦岭地区，其中冷水北沟矿床Ga平均含量最高（约210×10-6），锡铜沟矿床平均Ge含量最高（约145×10-6）.东秦岭地区铅锌矿床闪锌矿中In、Cd含量显著高于西秦岭，其中骆驼山矿床In平均含量最高（约304×10-6），破山矿床Cd平均含量最高（约7 186×10-6）.除少数矿床出现少量含Ge独立矿物以外，秦岭造山带铅锌矿床中Ga、Ge、In稀散金属主要以类质同象形式与Cu离子（个别矿床有Ag离子）共同替代Zn离子进入闪锌矿晶格.Cd则以直接替代Fe或与Fe共同替代Zn的方式进入闪锌矿晶格.结合本次研究结果和铅锌矿床锌资源量数据，利用矿物计算法开展秦岭造山带稀散金属资源评价.评价结果表明，秦岭造山带Ga资源分布不均匀，其中东秦岭冷水北沟矿床Ga资源量最高（约479 t）.Ge资源主要分布在西秦岭地区，其中洛坝矿床Ge资源量最高（约190 t）.In资源集中分布在东秦岭地区，其中骆驼山矿床In资源量最高（约450 t）.秦岭造山带Cd资源较为丰富，西秦岭厂坝-李家沟矿床Cd资源量高达2.18万t.本研究系统查明了秦岭造山带铅锌矿床中稀散金属的分布规律并进行了初步资源评价，对区域铅锌矿床中伴生稀散金属的综合利用有着重要的指导意义.Abstract: Dispersed metals such as gallium (Ga), germanium (Ge) and indium (In) play significant roles in high-tech development and national defense construction and have been classified as strategic and critical metals in China, USA and Europe. Pb-Zn deposits are not only the primary source of lead and zinc non-ferrous metals, but also rich in dispersed metal resources. The Qinling orogenic belt is an important Pb-Zn resource-producing area in China. Research on dispersed metals in the Pb-Zn deposits of this area is relatively weak, and there is a lack of systematic evaluation of dispersed metal resources. This study selected 19 representative Pb-Zn deposits in the West Qinling and East Qinling districts as the research objects. The trace element composition of sphalerite from different deposits determined using LA-ICP-MS with previous analytical data were summarized to reveal the contents and occurrences of dispersed metals Ga, Ge, In, and Cd. The research results indicate that the contents of Ga and Ge in sphalerite from Pb-Zn deposits in the West Qinling district are slightly higher than those in the East Qinling district. Among them, the Ga content in the Lengshuibeigou deposit is the highest (ave. ~210×10-6), and the Ge content in the Xitonggou deposit is the highest (ave. ~145×10-6) The contents of In and Cd in sphalerite from Pb-Zn deposits in the East Qinling district were significantly higher than those in the West Qinling district. Among them, the Luotuoshan deposit contains the highest In (ave. ~304×10-6) while the Poshan deposit contains the highest Cd (ave. ~7 186×10-6). With the exception of a few deposits that contained a small amount of independent Ge minerals, the dispersed metals Ga, Ge, In, and Cd in the Pb-Zn deposits of the Qinling orogenic belt mainly entered the sphalerite lattice in the form of isomorphism with Cu ions replacing Zn ions. Based on the results of this study and the zinc resource data of the deposits, the evaluation of dispersed metal resources in the Qinling orogenic belt was carried out using the mineral calculation method. The evaluation results demonstrate that the distribution of Ga resources in the Qinling orogenic belt is uneven. Among them, the Lengshuibeigou deposit in the East Qinling district has the highest Ga resources (~479 t). Ge resources are mainly distributed in the West Qinling district, with the Ge resource of the Luoba deposit being the highest (~190 t). In resources are concentrated in the East Qinling district, with the In resources of the Luotuoshan deposit being the highest (~450 t). The Cd resource in the Qinling orogenic belt is relatively abundant, with the Cd resources of the Changba-Lijiagou deposit reaching as high as 21 000 t. This study systematically identified the distribution patterns of dispersed metals Ga, Ge, In, and Cd in Pb-Zn deposits in the Qinling orogenic belt and conducted a preliminary resource evaluation, which holds significant guiding significance for the comprehensive utilization of associated dispersed metals in Pb-Zn deposits in the area.
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Key words:
- Qinling orogenic belt /
- Pb-Zn deposit /
- dispersed metals /
- resource evaluation /
- comprehensive utilization /
- mineralogy /
- ore deposit
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图 1 秦岭造山带构造分区及代表性铅锌矿床分布图(修编自Dong et al., 2011)
代表性铅锌矿床：1.厂坝-李家沟；2.邓家山；3.毕家山；4.洛坝；5.八方山-二里河；6.锡铜沟；7.关子沟；8.蒿坪沟；9.沙沟；10.冷水北沟；11.骆驼山；12.栾川银洞沟；13.中鱼库；14.西沟；15.王坪西沟；16.老代仗沟；17.内乡银洞沟；18.破山；19.汞洞冲
Fig. 1. Tectonic districts and distribution of representative Pb-Zn deposits in the Qinling orogenic belt (modified from Dong et al., 2011)
图 2 西秦岭地区铅锌矿床分布图(修编自Leach and Song, 2019)
Fig. 2. Distribution of Pb-Zn deposits in the West Qinling district (modified from Leach and Song, 2019)
图 3 东秦岭地区铅锌矿床分布图(修编自赵新福等，2019)
Fig. 3. Distribution of Pb-Zn deposits in the East Qinling district (modified from Zhao et al., 2019)
图 4 代表性矿床铅锌矿石标本及闪锌矿镜下照片
a~c.来自西秦岭地区厂坝-李家沟矿床；d，e.来自东秦岭地区骆驼山矿床.a.层状矿石，矿石中含有闪锌矿、黄铁矿、方铅矿、磁黄铁矿.b.反射光镜下照片，多金属硫化物共生，闪锌矿、磁黄铁矿、黄铁矿、黄铜矿共生.c.反射光镜下照片，闪锌矿与黄铁矿共生，闪锌矿表面干净，无污染.d.矽卡岩化矿石样品，闪锌矿呈透镜状、脉状产出，脉石矿物主要为石榴石.E：反射光镜下照片，闪锌矿表面干净，无污染，内部及边部含有石榴石矿物包体.Po.磁黄铁矿；Sp.闪锌矿；Gn.方铅矿；Py.黄铁矿；Grt.石榴子石；Ccp.黄铜矿；Cal.方解石；Qtz.石英
Fig. 4. Photographs of Pb-Zn ore specimens and microscopicgraphs of sphalerite minerals from representative deposits
图 5 秦岭造山带铅锌矿床闪锌矿中稀散金属Ga、Ge、In、Cd含量
Fig. 5. Contents of dispersed metals Ga, Ge, In and Cd in sphalerite of Pb-Zn deposits in the Qinling orogenic belt
图 6 秦岭造山带代表性铅锌矿床闪锌矿LA-ICP-MS时间剥蚀曲线
a.洛坝矿床（早期沉积变质期闪锌矿）；b.锡铜沟矿床（碳酸盐-硫化物脉矿石）；c.骆驼山矿床（粗粒闪锌矿）；d.冷水北沟铅锌矿床（含黄铜矿包裹体闪锌矿）
Fig. 6. LA-ICP-MS time spectrum of sphalerite of representative Pb-Zn deposits in the Qinling orogenic belt
图 7 秦岭造山带代表性铅锌矿床闪锌矿中微量元素二元图解
Fig. 7. Binary diagrams of trace elements of representative Pb-Zn deposits in the Qinling orogenic belt
a.Cu vs. Ga; b.Cu vs. Ge; c.Cu vs. In; d.Ag vs. Ga; e. Cu+Ag vs. Ge; f.Ag vs. In; g.Cd vs. Fe; h.Ag vs. Ga+Ge+In; i. Cu vs. Ga+Ge+In
图 8 锡铜沟铅锌矿床碳酸盐-硫化物脉矿石中含锗矿物
Arg.硫银锗矿；Bri.灰锗矿
Fig. 8. Germanium-bearing minerals in carbonate-sulfide vein ores of the Xitonggou Pb-Zn deposit
图 9 秦岭造山带代表性铅锌矿床Ga、Ge、In、Cd估算资源量
Fig. 9. Estimated metal resources of Ga, Ge, In and Cd of representative Pb-Zn deposits in the Qinling orogenic belt
图 10 秦岭造山带代表性铅锌矿床稀散金属评估资源量图
图中所标注的铅锌矿床为稀散金属Ga、Ge、In、Cd达到中型及以上规模，具体数据参考《DZT 0400-2022矿产资源储量规模划分标准》.其中骆驼山矿床In资源量为闪锌矿和黄铜矿中稀散金属In总和；底图据Dong et al.（2011）
Fig. 10. Map of estimated resources for dispersed metals in representative Pb-Zn deposits of the Qinling orogenic belt
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