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The Northwest quartz-pyrite-gold veins are situated 500 m east of the Lepanto fault in Mankayan, Luzon, Philippines. Most vein mineralization is hosted by the Lepanto metavolcanic basement rocks at an elevation between 700 and 1,050 m. The earliest stage, stage 1, is characterized by sphalerite + chalcopyrite + pyrite ± magnetite veins cutting the host rocks that were altered to chlorite + illite + epidote. Precious metal deposition started in stage 2 as electrum, native gold, and gold-silver tellurides deposited with pyrite, quartz, and carbonate. Deposition of gold and silver tellurides continued in stage 3a with abundant pyrite and tennantite-tetrahedrite solid solution intergrown with chalcopyrite, bornite, and minor sphalerite. The stage 3a veins and host-rock alteration are characterized by abundant muscovite and quartz, while the stage 3b veins and alteration consist of quartz, pyrophyllite, alunite, and dickite. Enargite and luzonite are the dominant sulfide minerals in stage 4, which are either disseminated in silicified host rock or within wide quartz veins. Lesser amounts of quartz and abundant pyrite with inclusions of enargite and luzonite were precipitated in stage 5. Microthermometry on fluid inclusions in quartz of stages 2, 3a, and 4 indicates boiling of the hydrothermal fluids. Bulk gas analysis on fluid inclusions in quartz shows that the stage 2 and 4 fluids had components derived from basaltic and andesitic magma, respectively. Fluids that formed stage 4 quartz were more diluted by meteoric water than the fluids that formed the stage 2 veins. Radiometric 40Ar/39Ar dating on alunite separated from the stage 3b advanced argillic alteration zone yielded 2.2 ± 0.1 Ma. Sulfur isotope compositions of the Northwest quartz-pyrite-gold deposit reveal a bulk δ34S of approximately 5‰, similar to the calculated value for the adjacent Far Southeast porphyry deposit. Calculated oxygen and hydrogen isotope ratios of the fluids of the Northwest quartz-pyrite-gold deposit stage 3b dickites are similar to those that formed the illite alteration in the Far Southeast porphyry deposit but are higher in δ18O when compared to the fluids that formed the kandites in the Lepanto enargite deposit. The northward cooling of mineralizing fluids previously reported in the Lepanto enargite deposit is not consistent with the mineralogic indications in the Northwest quartz-pyrite-gold deposit. These data indicate multiple mineralization events in the Mankayan district, which is one of the largest mineral districts in the western Pacific.

The overprinting episodes of porphyry-type and epithermal-type mineralization in the Mankayan District, northern Luzon, Philippines allow an investigation on variation of geochemical signatures with different alteration assemblages. Due to the multiple hydrothermal activities in Mankayan, some older porphyry-type deposits have been overprinted by acid-sulfate alteration that is commonly associated with high-sulfidation epithermal mineralization. In this study, we analyzed metavolcanic basement rocks and dioritic rocks that host porphyry-type mineralization in the Far Southeast deposit, Honeycomb prospect and Christine prospect, which all have near-neutral pH alteration assemblage of illite/muscovite + chlorite ± quartz. We compared their geochemical data with those of the Fatima porphyry deposit, which was overprinted by quartz + alunite ± kaolinite/dickite alteration. Furthermore, we also compared the geochemical data of the metavolcanic and dioritic rocks in the Carmen and Florence prospects hosting quartz-pyrite-gold and enargite veins which overprinted earlier porphyry-type mineralization. N-MORB-normalized multi-element diagrams show that the host rocks preserve negative anomalies of high field strength elements (HFSEs) that are typical of magmas generated in a supra-subduction zone setting. The non-mineralized metavolcanic and dioritic rocks show variable signature of the large ion lithophiles (LILEs), while the altered metavolcanic and dioritic rocks show a more consistent signature. Negative anomaly of Rb is associated with acid-sulfate alteration, while positive anomaly of Rb was observed in the dioritic rocks that have been altered by near-neutral pH fluids. Furthermore, acid-sulfate alteration significantly added LREEs and depleted HREEs compared to the near-neutral pH alteration. Mass changes in altered rocks were determined using the isocon technique. Mass changes are generally more pronounced in the acid-sulfate altered rocks compared to the near-neutral pH altered rocks. The metavolcanic rocks altered to quartz + alunite in Carmen and Florence significantly gained SiO2, Al2O3 and S, and lost Na2O, CaO, MgO and Fe2O3. The dioritic and metavolcanic rocks altered to chlorite + illite in the Far Southeast, Honeycomb, Christine and Fatima porphyry deposits lost SiO2 and Al2O3, while the concentrations of other elements remain relatively unchanged. The pH-dependence of the geochemical behavior of Rb in hydrothermal conditions was utilized to construct new molar element ratios that could differentiate the rocks that underwent K-metasomatism either under near-neutral pH or acidic conditions. The recognition of this behavior could be useful in a routine lithogeochemical analysis that is being used in exploration.