Hydrothermal Rock-Fluid Interactions in 15-year-old Submarine Basaltic Tuff at Surtsey Volcano, Iceland

Basaltic tephra at Surtsey volcano, produced by 1963-1967 eruptions in the offshore SE Icelandic rift zone, record the complex interplay of factors that determine rates of palagonitization and crystallization of authigenic minerals in seafloor basalts worldwide. We investigate how formation of nanocrystalline clay mineral in fresh sideromelane glass influenced crystallization of mineral cements in submarine tuff from a 181 m core drilled in 1979. Synchrotron-based microdiffraction and microfluorescence maps (2x5 µm X-ray beam spot size) at beamline 12.3.2, Advanced Light Source, SEM-EDS compositional analyses, and fluid geochemical models compare processes in lapilli-sized glass fragments, vitric cementing matrix, and fine ash accretions. In lapilli at 137.9 m (100°C), nanocrystalline clay mineral in gel-palagonite has asymetric 14.9-12.6 Å (001) reflections, with Fe and Ti enrichment relative to Si, Al and Ca, compared with adjacent sideromelane. Neighboring fibro-palagonite has symmetric (001) and greater Fe and Ti enrichment. Al-tobermorite, a rare calcium-silicate-hydrate, crystallized in nearby vesicles. The 11.30-11.49 Å (002) interlayer and Ca/(Si+Al) ratio of 0.9-1.0 record release of Si, Al, and Ca in a chemical system relatively isolated from submarine hydrothermal fluid flow. In vitric matrix relatively open to fluid flow, however, phillipsite zeolite cement predominates. Al-tobermorite formed at 88.45 m (130°C) and 102.6 m (140°C), but is associated with fibro-palagonite and analcite, reflecting more rapid palagonitization, and changing cation solubility and pH at higher temperature. Tubular palagonite microstructures show nanocrystalline clay mineral with (001) preferred orientations that wrap around relict microchannels, produced perhaps through biogenic activity. Nanocrystalline clay mineral d-spacings suggest similarities with nontronite, but zeolite in palagonite diffraction patterns and 6-9 wt% MgO suggest a polycrystalline composite with smectite mineral precursor(s). Fifteen years after eruption, Al-tobermorite-zeolite assemblages varied with porosity, pH, and reactive rock mass/liquid volume ratio in submillimeter-scale hydrothermal environments. This initial phase of alteration is rarely preserved in older palagonitized rift zone basalts.