Trace elements in sulfides from the Maozu Pb-Zn deposit, Yunnan Province, China: Implications for trace-element incorporation mechanisms and ore genesis

The Sichuan-Yunnan-Guizhou Pb-Zn metallogenic province (SYGMP) is an important region for Pb-Zn resources in China. However, considerable controversy remains as to whether the Pb-Zn deposits are Mississippi Valley Type (MVT). The Maozu deposit, a typical example of the carbonate-hosted Pb-Zn deposits in the SYGMP, occurs in the late Ediacaran Dengying Formation and its ore bodies are divided into three types: lower layer (LL), vein layer (VL), and upper layer (UL) ore bodies based on their spatial relationship. In this study, laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) was used to systematically analyze the trace-element compositions of sphalerite and galena in these three ore bodies. The results show that sphalerite is characterized by Cd and Ge enrichment; Fe, Mn, and Co depletion; and local In and Sn enrichment. Most of these elements likely appear as solid solutions in sphalerite and show a wide compositional variation, which is probably related to the medium- and low-temperature mixing of the ore-forming fluids. The local enrichment of In and Sn is likely attributed to the long-distance migration of ore-forming fluids through In-Sn-bearing volcaniclastic rocks. In vs. Sn and (Cu + Sb) vs. (Ag + Ge) show strong correlations and similar element distribution in the mapped images, indicating that these elements may be incorporated into sphalerite via a coupled substitution for Zn as 2In3+ + Sn4+ + 2☐ ↔ 5Zn2+ (☐ = vacancies) and 4(Cu+ + Sb3+) + (Ge4+ + 2Ag+) + 2☐ ↔ 13Zn2+. Galena is enriched in Ag and Sb with minor Cd and Se and depleted in Bi, and most of the elements may occur as solid solutions. Ag vs. Sb in galena displays a strong positive correlation, implying the coupled substitution of Ag+ + Sb3+ ↔ 2Pb2+. Notably, the majority of the trace-element concentrations gradually decrease in the order LL → UL except Fe, Co, Cu, and Ge, while Fe, In, and Sn in sphalerite and Ag and Sb in galena have the highest concentration in the VL, indicating that the VL is a secondary migration channel for the ore-forming fluids. Furthermore, the trace-element compositions of the sulfides in the Maozu Pb-Zn deposit are consistent with the typical MVT deposit (hosted in the carbonate sequence) but are markedly different from sedimentary exhalative (SEDEX), volcanogenic massive sulfide (VMS) and skarn-type deposits. Based on these results, as well as the geological and geochemical characteristics of the deposit, the Maozu Pb-Zn deposit is an MVT deposit.

Trace Element Contents in Sphalerite from the Nayongzhi Zn-Pb Deposit, Northwestern Guizhou, China: Insights into Incorporation Mechanisms, Metallogenic Temperature and Ore Genesis

The Nayongzhi Zn-Pb deposit, located in the southeastern margin of the Sichuan-Yunnan-Guizhou (S-Y-G) Zn-Pb metallogenic province, China, has been recently discovered in this region and has an estimated resource of 1.52 Mt of metal at average grades of 4.82 wt % Zn and 0.57 wt % Pb. The ore bodies are hosted in the Lower Cambrian Qingxudong Formation dolostone and occur as stratiform, stratoid and steeply dipping veins. The predominant minerals are sphalerite, galena, dolomite, calcite with minor pyrite, and barite. In this paper, the inductively coupled plasma mass spectrometry (ICP-MS) technique has been used to investigate the concentrations of Fe, Cd, Ge, Ga, Cu, Pb, Ag, In, Sn, Sb, Co and Mn in bulk grain sphalerite from the Nayongzhi deposit, in an effort to provide significant insights into the element substitution mechanisms, ore-forming temperature and genesis of the deposit. This study shows that those trace elements (i.e., Cd, In, Sn, Sb, Fe, Mn, Cu, Ga, Ge, Ag, and Co) are present in the form of isomorphism in sphalerite, and strong binary correlation among some elements suggests direct substitution as Zn2+↔Fe2+ and coupled substitutions as Zn2+↔Ga3+ + (Cu, Ag)+ and Zn2+↔In3+ + Sn3+ + □ (vacancy), despite there being no clear evidence for the presence of Sn3+. Sphalerite from the Nayongzhi deposit is enriched in Cd, Ge and Ga and depleted in Fe, Mn, In and Co, which is similar to that of the Mississippi Valley-type (MVT) deposit and significantly different from that of the Volcanogenic Massive Sulfide (VMS) deposit, Sedimentary-exhalative (Sedex) deposit, skarn, and epithermal hydrothermal deposit. Moreover, the ore-forming temperature is relatively low, ranging from 100.5 to 164.4 °C, as calculated by the GGIMFis geothermometer. Geological characteristics, mineralogy and trace element contents of sphalerite suggest that the Nayongzhi deposit is a MVT deposit. In addition, according to the geological characteristics, Ag content in sphalerite, and Pb isotope evidence, the Nayongzhi deposit is distinct from the deposits associated with the Indosinian Orogeny in S-Y-G Zn-Pb metallogenic province (e.g., Huize, Daliangzi, Tianbaoshan and Tianqiao deposits), thus, suggesting that multi-stage Zn-Pb mineralization may have occurred in this region.