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The common serpentine-diopside matrix assemblage in volcaniclastic kimberlite (VK) at the Venetia Mine, South Africa is ascribed to a secondary origin, because of post-emplacement serpentinization and associated hydrothermal metamorphism. Volcaniclastic deposits with 20-30% porosity infill kimberlite pipes in the waning stages of kimberlite eruptions. Olivine macrocrysts are typically rimmed by talc and are pseudomorphed by lizardite, with minor magnetite. The fine matrix consists of mixtures of lizardite, chlorite, smectite, brucite, calcite, titanite and andradite, an assemblage which either pseudomorphed microcrysts or in-filled voids. Locally we recognize microcryst pseudomorphs rich in sub-microscopic mixtures of lizardite with smectite, and other microcryst pseudomorphs and void-filling matrix rich in chlorite and lizardite. Interstitial lizardite and associated phyllosilicates (brucite, smectite and chlorite) crystallized progressively from meteoric or hydrothermally derived pore waters, and Si 4+ and Mg 2+ released into the fluid phase during serpentinization of olivine macrocrysts. Radial-fibrous fringes of diopside microlites around crystals display void-filling textures because of unrestricted growth into pore spaces. Secondary diopside is attributed to Si 4+ , Mg 2+ and Ca 2+ cations released into the fluid phase by interaction with olivine, calcite and plagioclase in siliceous xenoliths. The paucity of primary, finegrained groundmass phases resistant to alteration, for example, perovskite and spinel, precludes an origin for the intergrain matrix as altered interstitial ash, glass or a late-stage kimberlite melt. Isovolumetric replacement of olivine results in a volume increase of 60% so that pore spaces in the original deposit can be easily filled up with serpentine. The source of Al 3+ to form chlorite and smectite is attributed to alteration of plagioclase in xenoliths which comprise 20-30 vol.% of the deposit. Titanite, hydro-andradite and second-generation diopside precipitate as hydrothermal minerals from calcium-bearing serpentinizing fluids in replacement reactions and as void-filling minerals. Consideration of mineral equilibria in the CaO-MgO-SiO 2 -H 2 O-CO 2 system constrains the common matrix assemblage of lizardite and diopside in X CO 2 )-T space. At 300 bar, the assemblage is stable only at temperatures below 370°C and X CO 2 < 0.01. This upper limit on temperature is well below the plausible solidus of ultrabasic magmas. Furthermore, the requirement of trace CO 2 in the fluid phase implies a post-emplacement external source rather than ÔautometamorphismÕ from kimberlite-derived fluids, because of high P CO 2 commonly inferred for kimberlite magmas.

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