The chlorite data presented are from four igneous complexes covering the compositional spectrum of igneous rocks (gabbro to granite) of orogenic and anorogenic settings. The four igneous complexes are; early orogenic gabbro-diorite-tonalite (D-T) suite, late orogenic granodiorite-adamellite (G-A) suite (both are calc-alkaline suites), high-alumina trondhjemite (TR), and anorogenic peralkaline granite (PGR).

Chlorites in these igneous rocks show characteristic compositional fields. The Mg vs Fe plot provides the best discriminant, as data points define three compositionally different groups. Phases in the PGR are Fe-rich, siliceous, interlayered chlorite-smectite (Fe/Mg = 8.6), and differ significantly from those in the calc-alkaline D-T and G-A rocks which are Mg-rich chlorites (Fe/Mg = 0.6–0.8). The X-ray diffraction data for the peralkaline granite samples show superlattice reflections at approximately 31 Å (air-dried) and 34 Å (ethylene glycollated), thus suggesting the presence of an expandable (smectite-like) component in this interlayered (chlorite-smectite) phyllosilicate phase. Chlorites in the peraluminous TR rocks contain Fe/Mg values intermediate between the other two types (Fe/Mg = 1.3). Tetrahedral Al (AlZ) values are remarkably low (0–0.5) in phyllosilicates in the PGR, but vary from 1.9–2.5 in chlorites from the other suites. Yet, these chlorite groups with their generally low AlZ values are distinct from the more stable (type IIb) metamorphic chlorites. Sedimentary chlorites are somewhat similar, in their low AlZ values and metastable structural type, to chlorites in igneous rocks.

In the calc-alkaline rocks, chlorite may have been formed at the expense of both biotite [biotite + 3M + 3H2O = chlorite + A], and calcic amphibole [2 Ca-amphibole + 6H2O + 5O2 + 1.8Al = 1 chlorite + 8SiO2 + A], where M = Fe, Mg, Al, and A = K, Na, Ca. The alteration of alkali amphibole in the peralkaline rocks may have produced interlayered chlorite-smectite via this reaction; [1 Na-amphibole + 7H2O + 2.5O2 + M = 1 chlorite-smectite + A]. The presence of such interlayered chlorite-smectite which typically form at low T (150–200°C) suggests that the region was not affected by any major reheating events, which is consistent with the nature of the feldspars.

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.