Geochemical Fingerprints of Magnetite in Yechangping Super-Large Mo-W Deposit, Western Henan, China: Constraints on Ore-Forming Evolution and Prospecting Implications

The Yechangping super-large porphyry–skarn deposit is a key component of the East Qinling molybdenum metallogenic belt, central China. Magnetite is widely developed across all mineralization stages of this deposit, yet its systematic geochemical evolution and prospecting significance remain poorly constrained. This study presents in situ major- and trace-element analyses of magnetite via electron probe microanalysis (EPMA), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and elemental mapping, to unravel the ore-forming hydrothermal evolution and establish reliable prospecting indicators. Four magnetite generations are identified based on petrography and paragenetic relationships: late skarn stage (Mt1), oxide stage (Mt2 and Mt3), and polymetallic sulfide stage (Mt4). Magnetite has total iron contents (TFeO, total Fe calculated as FeO) of 82.72–95.46 wt.% (values above the 93 wt.% stoichiometric limit of pure magnetite stem from minor oxidation), with dominant isovalent Fe3+ and Al3+ lattice substitution supported by a significant negative Fe–Al correlation. Systematic stage-dependent geochemical variations are observed: Mt1 has the highest Ti (mostly >1500 ppm), V and Cr, while Mt2–Mt4 show progressive Ti depletion (mostly <100 ppm), recording continuous cooling of the hydro-thermal system. V and Cr contents decrease markedly from Mt1 to Mt3, with secondary enrichment in Mt4; Mo concentrations peak in Mt2 (average 5.06 ppm), coupled with elevated chalcophile metalloid Te, As, Pb and Bi. Elemental mapping results show that K occurs as discrete hotspots, which may be mainly derived from feldspar microinclusions, rather than lattice substitution in magnetite. These geochemical fingerprints record a transition from high-temperature magmatic–hydrothermal fluids to late contact-metasomatic fluids, with evolving fluid–rock interaction and oxygen fugacity. Our results demonstrate that magnetite chemistry is a reliable tool for discriminating mineralization stages and vectoring prospecting targets in porphyry–skarn Mo–W systems.