Composition of matrix glasses and melt inclusions of fallout tephra from ODP Hole 125-782A

We studied the systematics of Cl, F and H2O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ~400-4000 ppm and F ~70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (~6600-8600 ppm) and F (~780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H2O of basalt to andesite melt inclusions in plagioclase is estimated to range from ~2 to ~10 wt% H2O. The Izu magmas should be undersaturated in H2O and the halogens at their preferred levels of crystallization in the middle to lower crust (~3 to ~11 kbar, ~820° to ~1200°C). A substantial portion of the original H2O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H2O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H2O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94+/-0.25 wt%, F = 990+/-270 ppm and H2O = 25+/-7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (~77-129%). Conversely, H2O (~13-22% recycled at arc) and F (~4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H2O, the calculated percentage of Cl and H2O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (~37000 km), the global arc outflux of fluid-recycled Cl and H2O at subduction zones amounts to Cl ~2.9-3.8 mln ton/yr and H2O ~70-100 mln ton/yr, respectively - comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ~0.3-0.4 mln ton/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H2O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H2O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (~9.5), slab melting will still produce components with low Cl/F ratios (~0.9), similar to those characteristic of the upper continental crust (Cl/F ~0.3-0.9).

Boron contents and boron, carbon, and oxygen isotope data for ODP Sites 160-970 and 160-971

Products of two mud volcanoes from the distal part of the Mediterranean Ridge accretionary complex have been investigated regarding their B, C, and O stable isotope signatures. The mud breccias have been divided into mud matrix, lithified clasts, biogenic deposits, and authigenic cements and crusts related to fluid flow and cementation. Isotope geochemistry is used to evaluate the depth of mobilization of each phase in the subduction zone. B contents and isotope ratios of the mud and mud clasts show a general trend of B enrichment and decreasing d11B values with increasing consolidation (i.e., depth). However, the majority of the clast and matrix samples relate to moderate depths of mobilization within the wedge (1-2 km below seafloor). The carbonate cements of most of these clasts as well as the authigenic crusts, however, provide evidence for a deep fluid influence, probably associated with the décollement at 5-6 km depth. This interpretation is supported by d13C ratios of the crust, which indicate precipitation of C from thermogenic methane, and by the d11B ratios of pore-water samples of mud-breccia drill cores. Clams (Vesicomya sp.) living adjacent to fluid vents have d11B and d18O values corresponding to brines known in the area, which acted as the parent solution for shell precipitation. Such brines are most likely Miocene pore waters trapped at deep levels within the backstop to the accretionary prism, probably prior to desiccation of the Mediterranean in the Messinian (6-5 Ma). Combining all results, deep fluid circulation and expulsion are identified as the main processes triggering mud liquefaction and extrusion, whereas brines contribute only locally. Given the high B contents, mud extrusion has to be considered a major backflux mechanism of B into the hydrosphere.