Genesis of Cu-Sn Mineralization in the Shuangjianzishan Super-Large Silver Deposit, Inner Mongolia: Trace Element Constraints from Chalcopyrite and Cassiterite

The Shuangjianzishan silver polymetallic deposit is located in the copper–tin–lead–zinc–silver polymetallic metallogenic belt in the Southern Great Xing’an Range, with silver resources of more than 18,000 t, which is the largest silver polymetallic deposit in Asia. Early studies concluded that the Shuangjianzishan deposit is typically an epithermal Ag-Pb-Zn deposit that lacks a high-temperature mineralization stage. In recent years, with the deepening of research, a large amount of Cu-Sn mineralization has been found in the deep part of the Shuangjianzishan deposit, but it is less studied. The laser-ablation inductively coupled mass spectroscopy (LA-ICP-MS) technique is used to investigate the distribution and substitution of trace elements in chalcopyrite and cassiterite. In this paper, the trace element study of chalcopyrite and cassiterite from the Shuangjianzishan deposit reveals that Sn, In, As, Se, Sb, and Tl mainly exist in chalcopyrite in isomorphic form, while Pb, Bi, and Ni mainly exist in chalcopyrite in the form of mineral inclusions. The enrichment of the high-temperature elements Sn and Se in chalcopyrite, and the deficit of the middle- and low-temperature elements Ga, Sb, etc., reflect that the chalcopyrite in the Shuangjianzishan deposit was formed in a middle- and high-temperature environment, and it also indicates that the early ore-forming hydrothermal solution may be rich in Sn. Fe, In, Co, and Ni mainly exist in cassiterite in isomorphic form, and the content of W in cassiterite is high. There are two main forms, one is isomorphic and the other is wolframite inclusion. Cassiterite has Fe-rich and W-U-poor characteristics, indicating that cassiterite from the Shuangjianzishan deposit was formed under relatively oxidized conditions, and the relative enrichment of elements such as Fe, W, Zr, and Hf indicates that the temperature of cassiterite formation was high. The elemental content and inter-ionic coupling relationships suggest that the cassiterite from the Shuangjianzishan deposit may have an elemental replacement mechanism of W6+ + Fe2+ ↔ 2Sn4+ or Fe3+ + OH− ↔ Sn4+ + O2−. The trace elements in cassiterite of the Shuangjianzishan deposit are rich in Fe and Mn and depleted in Nb and Ta, according to the Fe-W diagram, and the tin mineralization of the Shuangjianzishan deposit belongs to cassiterite–sulfide-type tin mineralization. Chalcopyrite Co/Ni ratios >1 are consistent with the characteristics of chalcopyrite genesis in hydrothermal deposits.