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The Archean Horne 5 deposit, located in the Rouyn-Noranda district in the southern Abitibi greenstone belt, Canada, contains a total resource of 172.4 t Au (5.6 Moz) from 112.7 Mt of ore grading at 1.53 g/t Au. The deposit is part of the Au-rich Horne volcanogenic massive sulfide (VMS) complex that also includes the past-producing Horne mine (i.e., the Upper and Lower H zones plus small subsidiary lenses) that yielded 325.4 t Au (10.5 Moz Au) from 53.7 Mt of ore grading at 6.06 g/t Au. Combined, the Horne mine and Horne 5 deposit contain ~500 t Au (16 Moz), making them the world’s single largest accumulation of VMS-related Au. The Horne 5 deposit consists of stacked lenses of massive to semimassive sulfides alternating with extensive zones of disseminated and stringer sulfides. The mineralization is hosted within thick accumulations of steeply dipping dacitic to rhyodacitic volcaniclastic units of transitional to calc-alkaline magmatic affinity. Dacitic-rhyodacitic synvolcanic units (lobes, sills, and/or domes) intrude the host succession, which is also crosscut by a series of post-ore mafic and younger intermediate to felsic feldspar ± quartz porphyry dikes. A broad and diffuse halo of distal sericite-chlorite-epidote alteration extends outboard of intensely sericite-altered zones proximal to the sulfide lenses. Gold is interpreted to be synvolcanic on the basis of Au-rich massive sulfide clasts in the volcaniclastic units, the presence of preserved Au-rich primary pyrite, Au zones limited to the sulfide envelope, crosscutting deformed but unaltered and barren dikes, and the absence of typical syndeformation, orogenic-style alteration and mineralization despite overprinting high-strain corridors and faults. Gold is spatially associated with pyrite, sphalerite, and chalcopyrite, and its distribution is largely controlled by the higher porosity and permeability of the volcaniclastic host rocks, which are interpreted to have facilitated hydrothermal fluid circulation in the subseafloor environment. Synvolcanic intrusions and fine-grained tuffs overlying auriferous zones also influenced the distribution of the mineralization by acting as cap rocks to ascending fluids. Evidence suggests that Au enrichment at the Horne 5 deposit is due to efficient transport and precipitation of Au in the subseafloor environment, a favorable geodynamic setting (transitional to calc-alkaline magmatism over thick crust), and possible input of magmatic fluids as suggested by high Te and Cu in the mineralization. Minor and very local remobilization of metals occurred in response to regional deformation and associated greenschist facies metamorphism. The detailed study of the Horne 5 deposit geology and a review of the available information on the Horne mine and recent 3-D modeling indicate that the Horne 5 deposit may have formed higher in the stratigraphy than the Upper and Lower H orebodies of the former Horne mine, which originally formed a single lens. Therefore, the Horne Au-rich VMS complex originally formed as a stacked system in which the Horne 5 deposit was deposited above the Upper and Lower H zones and not in a distal or lateral position as previously proposed, indicating that a robust hydrothermal system was responsible for the formation of the world’s largest Au-rich VMS complex.