Chemical composition of glass inclusions from ODP Holes 157-953C and 157-956B

We report S concentrations and relative proportions of (SO4)2- and S2- in OL- and CPX-hosted glass inclusions and in host glassy lapilli from Miocene basaltic hyaloclastites drilled north and south of Gran Canaria during ODP Leg 157. Compositions of glass inclusions and lapilli resemble those of subaerial Miocene shield basalts on Gran Canaria and comprise mafic to more evolved tholeiitic to alkali basalt and basanite (10.3-3.7 wt.% MgO, 44.5-56.9 wt.% SiO2). Glass inclusions fall into three groups based on their S concentrations: a high-sulfur group (1050 to 5810 ppm S), an intermediate-sulfur group (510 to 1740 ppm S), and a low-sulfur group (<500 ppm S). The most S-rich inclusions have the highest and nearly constant proportion of sulfur dissolved as sulfate determined by electron microprobe measurements of SKa peak shift. Their average S6+/S_total value is 0.75+/-0.09, unusually high for ocean island basalt magmas. The low-sulfur group inclusions have low S6+/S_total ratios (0.08+/-0.05), whereas intermediate sulfur group inclusions show a wide range of S6+/S_total (0.05-0.83). Glassy lapilli and their crystal-hosted glass inclusions with S concentrations of 50 to 1140 ppm S have very similar S6+/S_total ratios of 0.36+/-0.06 implying that sulfur degassing does not affect the proportion of (SO4)2- and S2- in the magma. The oxygen fugacities estimated from S6+/S_total ratios and from Fe3+/Fe2+ ratios in spinel inclusions range from NNO-1.1 to NNO+1.8. The origin of S-rich magmas is unclear. We discuss (1) partial melting of a mantle source at relatively oxidized fO2 conditions, and (2) magma contamination by seawater either directly or through magma interaction with seawater-altered Jurassic oceanic crust. The intermediate sulfur group inclusions represent undegassed or slightly degassed magmas similar to submarine OIB glasses, whereas the low-sulfur group inclusions are likely to have formed from magmas significantly degassed in near-surface reservoirs. Mixing of these degassed magmas with stored volatile-rich ones or volatile-rich magma replenishing the chamber filled by partially degassed magmas may produce hybrid melts with strongly varying S concentrations and S6+/S_total ratios.

Partial melting experiments on oceanic cumulated gabbros

We performed hydrous partial melting experiments at shallow pressures (0.2 GPa) under slightly oxidizing conditions (NNO oxygen buffer) on oceanic cumulate gabbros drilled by ODP (Ocean Drilling Program) cruises to evaluate whether the partial melting of oceanic gabbro can generate SiO2-rich melts with compositions typical of oceanic plagiogranites. The experimental melts of the low-temperature runs broadly overlap those of natural plagiogranites. At 940 °C, the normalized SiO2 contents of the experimental melts of all systems range between 60 and 61 wt%, and at 900 °C between 63 and 68 wt%. These liquids are characterized by low TiO2 and FeOtot contents, similar to those of natural plagiogranites from the plutonic section of the oceanic crust, but in contrast to Fe and Ti-rich low-temperature experimental melts obtained in MORB systems at ~950 °C. The ~1,500-m-long drilled gabbroic section of ODP Hole 735B (Legs 118 and 176) at the Southwest Indian Ridge contains numerous small plagiogranitic veins often associated with zones which are characterized by high-temperature shearing. The compositions of the experimental melts obtained at low temperatures match those of the natural plagiogranitic veins, while the compositions of the crystals of low-temperature runs correspond to those of minerals from high-temperature microscopic veins occurring in the gabbroic section of the Hole 735B. This suggests that the observed plagiogranitic veins are products of a partial melting process triggered by a water-rich fluid phase. If the temperature estimations for hightemperature shear zones are correct (up to 1,000 °C), and a water-rich fluid phase is present, the formation of plagiogranites by partial melting of gabbros is probably a widespread phenomenon in the genesis of the ocean crust.

Composition of melts and minerals from volcanic rocks of the Kuril-Kamchatka Arc

In this paper allivalites, coarse- and giant-textured olivine-anorthite rocks occurring as separate blocks in the eruption products of many volcanoes from the frontal part of the Kuril-Kamchatka Arc are under consideration. New data are reported on petrography, mineralogy, and composition of melt inclusions in minerals from ten allivalite samples collected at Ksudach, Ilinsky, Zavaritsky, Kudryavy, and Golovnin Volcanoes. Crystallization temperatures of allivalite minerals were estimated as 970-1080°C at melt water content of 3.0-3.5 wt % and oxygen fugacity NNO=1-2. Genetic connection was established between compositions of melt inclusions and interstitial glasses in allivalites and volcanic rocks. Cumulate nature of allivalites was demonstrated. Using mass balance calculations, degree of fractionation of primary melts during formation of cumulate layers was estimated for various volcanoes as 22-46%.

Geochemistry and oxidation state of Lau Basin basalts

The backarc glasses recovered during Ocean Drilling Program Leg 135 are unique among submarine tholeiitic glasses with respect to their oxygen fugacity and sulfur concentrations. Unlike mid-ocean-ridge basalt glasses, fO2 in these samples (inferred from ratios Fe3+/Fe2+) is high and variable, and S variations (90-1140 ppm) are not coupled with FeO concentration. Strong correlations occur between the alkali and alkaline-earth elements and both fO2 (positive correlations) and S concentrations (negative correlations). Correlations between fO2 and various trace elements are strongest for those elements with a known affinity for hydrous fluids (perhaps produced during slab dehydration), suggesting the presence of a hydrous fluid with high fO2 and high alkali and alkaline earth element concentrations in the Lau Basin mantle. Concentrations of S and fO2 are strongly correlated; high fO2 samples are characterized by low S in addition to high alkali and alkaline earth element concentrations. The negative correlations between S and these trace elements are not consistent with incompatible behavior of S during crystallization. Mass balance considerations indicate that the S concentrations cannot result simply from mixing between low-S and high-S sources. Furthermore, there is no relationship between S and other trace elements or isotope ratios that might indicate that the S variations reflect mixing processes. The S variations more likely reflect the fact that when silicate coexists with an S-rich vapor phase the solubility of S in the silicate melt is a function of fO2 and is at a minimum at the fO2 conditions recorded by these glasses. The absence of Fe-sulfides and the high and variable vesicle contents are consistent with the idea that S concentrations reflect silicate-vapor equilibria rather than silicate-sulfide equilibria (as in MORB). The low S contents of some samples, therefore, reflect the high fO2 of the supra-subduction zone environment rather than a low-S source component.

Petrology and geochemistry of sideromelane glass shards from Pleistocene as layers north and south of Gran Canaria

Major elements, S, F, Cl concentrations and relative proportions of S6+ to total S were analyzed with electron microprobe in sideromelane glass shards from Pleistocene volcaniclastic sediments drilled during ODP Leg 157. Glasses are moderately to strongly evolved and represent a spectrum from alkali basalt, basanite and nephelinite through hawaiite, mugearite and tephrite to phonolitic tephrite. Measured S6+/SumS (0.03±0.98) and calculated Fe2+/Fe3+ (2.5±5.8) ratios in the melt yield preeruptive redox conditions ranging from NNO-1.4 to NNO+2.1. The morphology of the glass shards, variations of S and Cl concentrations (0.010±0.127 wt% S, 0.018±0.129 wt% Cl), calculated preeruptive temperatures (1030±1200 °C) and oxygen fugacities suggest that glasses deposited even within the same ash layers have diverse origin and may have resulted from both submarine and subaerial eruptions. Most vesicle-free glasses are characterized by high concentrations of S and represent undegassed or slightly degassed submarine lavas, whereas vesiculated glasses with low concentrations of S and Cl are strongly degassed and can be ascribed to the eruptions in shallow water or on land. Sideromelane glass shards at Sites 953 are thought to have resulted from submarine eruptions northeast of Gran Canaria, glasses at Site 954 represent mostly volcaniclastic material of shallow water submarine and subaerial eruptions on Gran Canaria and Tenerife, and glasses deposited at Site 956 resulted from submarine or explosive eruptions on Tenerife.

Major and trace element concentration of melt inclusions from Zhupanovsky volcano, Kamchatka

The paper presents data on naturally quenched melt inclusions in olivine (Fo 69-84) from Late Pleistocene pyroclastic rocks of Zhupanovsky volcano in the frontal zone of the Eastern Volcanic Belt of Kamchatka. The composition of the melt inclusions provides insight into the latest crystallization stages (~70% crystallization) of the parental melt (~46.4 wt % SiO2, ~2.5 wt % H2O, ~0.3 wt % S), which proceeded at decompression and started at a depth of approximately 10 km from the surface. The crystallization temperature was estimated at 1100 ± 20°C at an oxygen fugacity of deltaFMQ = 0.9-1.7. The melts evolved due to the simultaneous crystallization of olivine, plagioclase, pyroxene, chromite, and magnetite (Ol: Pl: Cpx : (Crt-Mt) ~ 13 : 54 : 24 : 4) along the tholeiite evolutionary trend and became progressively enriched in FeO, SiO2, Na2O, and K2O and depleted in MgO, CaO, and Al2O3. Melt crystallization was associated with the segregation of fluid rich in S-bearing compounds and, to a lesser extent, in H2O and Cl. The primary melt of Zhupanovsky volcano (whose composition was estimated from data on the most primitive melt inclusions) had a composition of low-Si (~45 wt % SiO2) picrobasalt (~14 wt % MgO), as is typical of parental melts in Kamchatka and other island arcs, and was different from MORB. This primary melt could be derived by ~8% melting of mantle peridotite of composition close to the MORB source, under pressures of 1.5 ± 0.2 GPa and temperatures 20-30°C lower than the solidus temperature of 'dry' peridotite (1230-1240°C). Melting was induced by the interaction of the hot peridotite with a hydrous component that was brought to the mantle from the subducted slab and was also responsible for the enrichment of the Zhupanovsky magmas in LREE, LILE, B, Cl, Th, U, and Pb. The hydrous component in the magma source of Zhupanovsky volcano was produced by the partial slab melting under water-saturated conditions at temperatures of 760-810°C and pressures of ~3.5 GPa. As the depth of the subducted slab beneath Kamchatkan volcanoes varies from 100 to 125 km, the composition of the hydrous component drastically changes from relatively low-temperature H2O-rich fluid to higher temperature H2O-bearing melt. The geothermal gradient at the surface of the slab within the depth range of 100-125 km beneath Kamchatka was estimated at 4°C/km.