Blackhead Quarry exploits a small Miocene (~10 Ma) basanitic volcanic centre in the Dunedin Volcanic Group, New Zealand. Vesicles near the quarry top contain Ca- and Na-rich zeolites, abundant calcite and rare pyrite resulting from localized low-T hydrothermal alteration (<100°C). Mineral assemblages were characterized by EDS and laser Raman spectroscopy with the latter the most useful in determining the identity of fibrous zeolite species. Secondary mineral assemblages crystallized during final stages of lava cooling from aqueous solutions enriched in Ca, Na, K, Ba and (CO3)2− leached from surrounding calcareous rocks and basanite. Phillipsite-K (generation I) crystallized first (in some places directly on fresh basanite) followed by the Ca-rich zeolites, chabazite-Ca, calcian phillipsite-K (generation II), gismondine and thomsonite. Later Na-rich fluids crystallized gonnardite and natrolite, and finally calcite from late Ca-rich fluids. Zeolite composition is not reflected by morphology. For example, both phacolitic and pseudocubic chabazite are chabazite-Ca, and although all phillipsite crystals have a similar habit, their composition varies widely. Various lithologies comprising the Blackhead volcanic centre have unique secondary mineral paragenetic sequences controlled largely by the rock structure and solution chemistry.