The orogenic gold deposits of the Otago Schist, New Zealand, are enriched in a variety of trace elements including Au, As, Ag, Hg, W and Sb. We combine laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) traverses and images to show that detrital rutile is the most important host mineral for W in the subgreenschist facies rocks. Furthermore, the prograde metamorphic recrystallisation of detrital rutile to titanite releases significant amounts of W (potentially 0.41 g/tonne of rock). Scheelite development closely follows the progression of this W-liberating reaction. Scheelite micrograins form early within the fabric of the rock evolving to locally and regionally sourced scheelite-bearing veins. Scheelite from syn-metamorphic veins at Fiddlers Flat and Lake HAwea shows distinct differences in composition compared with scheelite from late-metamorphic veins at the Macraes Mine, the latter of which is enriched in REEs, Y and Sr. We suggest that the scheelite at Macraes became enriched due to the liberation of these elements during alteration of the Ca-silicate minerals epidote and titanite by the ore-forming fluid. These results are supportive of recent models for orogenic gold mineralisation in the Otago Schist, whereby prograde metamorphic recrystallisation of diagenetic or detrital metal-rich mineral phases (pyrite to pyrrhotite: Au, As, Ag, Hg and Sb; rutile to titanite: W) releases significant amounts of metals into the concurrently developing metamorphic fluids that can be subsequently focussed into regional structures and form significant tungsten-bearing orogenic gold deposits.