Evolution of the Ore-Bearing Fluid of Alin Sb–Au Orebodies in Shuixie Cu–Co Orefield, SW China: Constraints on the Rare Earth Element and Trace Element Components of Auriferous Pyrite and Host Rock

The Shuixie Cu–Co polymetallic orefield, located in western Yunnan Province (southeastern margin of the Qinghai–Tibet Plateau), is renowned for its Cu–Co mineralization. A recent resource reassessment identified Sb–Au and Cu–Co–Bi (Sb–Au) orebodies as genetically associated with primary Cu–Co mineralization. The mineralization characteristics and microscopic observations indicate that gold mineralization in the Sb–Au orebodies follow a pulsating fluid injection model. The model includes four pulses: (1) euhedral gold-poor pyrite (PyI1) precipitation; (2) margin-parallel growth of gold-rich pyrite (PyI2) on PyI1; (3) continued growth of gold-rich pyrite (PyI3) along PyI2; and (4) outermost concentric gold-rich pyrite (PyI4) formation. This study examined gold-bearing pyrite in orebodies and host rocks. In situ laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) analysis of pyrite and inductively coupled plasma mass spectrometry (ICP–MS) whole-rock trace element analysis were conducted to track the ore-forming fluid evolution. Compared with CI chondrite, pyrites from all pulses were enriched in LREEs over HREEs. The pyrite REE distribution curves exhibited right-skewed patterns, reflecting LREE enrichment. The Hf/Sm, Nb/La, and Th/La ratios were generally below 1, indicating high-field-strength element depletion. These results suggest a Cl-rich, F-poor ore-forming fluid. The pyrite trace elements showed enrichment in the chalcophile elements (e.g., Cu and Pb) and exceptionally high Bi levels compared with the continental crust. The chalcophile elements (e.g., Zn and Cd) were depleted, whereas iron-group elements (e.g., Co) were enriched and Ni was depleted. The pyrite δCe values (0.87–1.28, mean = 1.01) showed weak anomalies, indicating a reducing ore-forming environment. The δEu values of pyrite during pulses 1 to 4 ranged widely, from 0.2–3.01 (mean of 1.17), 0.27–1.39 (0.6), and 0.41–1.40 (0.96) to 0.4–1.36 (0.84), respectively, suggesting an initial temperature decline and subsequent increase in the ore-forming fluid. Significant variations were found in the Y/Ho, Zr/Hf, and Nb/Ta ratios across pulses, indicating the potential involvement of high-temperature hydrothermal fluids or late-stage alteration during ore formation. The Y/Ho ratio of pyrite overlapped most closely with that of the continental crust of China, indicating a close relationship between the ore-forming fluids and the crust.