Chemical composition of altered volcanic rocks from ODP Sites 193-1188 and 193-1189

The conventional model of leaching volcanic rocks as a source of metals in a seafloor hydrothermal systems has been tested by examining the behavior of Pb and other trace elements during hydrothermal alteration. ODP Leg 193 drill sites 1188 (Snowcap) and 1189 (Roman Ruins) on Pual Ridge in the eastern Manus Basin offshore eastern Papua New Guinea provide a unique three-dimensional window into an active back-arc hydrothermal system. We investigate by means of a LA-ICP-MS microbeam technique the capacity of Pb to be leached from a host volcanic rock exposed to various types and intensities of alteration. Our results are in general agreement with previous studies that utilized bulk analytical techniques but provide a more detailed explanation of the processes. Fresh representative dacitic lavas from the Pual Ridge have an average whole rock Pb content of 5.2 ppm, an average interstitial glass Pb content of 5.6 ppm and an average plagioclase Pb content of 1.0 ppm. Altered matrix samples have highly variable Pb values ranging from 0 to 52.4 ppm. High Pb values in altered samples are associated with a low temperature chlorite and clay mineral assemblage, in some cases overprinted by a high temperature (up to 350°C) silica-rich "bleaching" alteration. Only the most highly altered matrix samples have REE patterns that differ from the fresh Pual Ridge dacite. This may represent either different lava histories or alteration characteristics that have affected normally immobile REEs. Altered samples with the highest Pb values have similar REE patterns to those of the local unaltered lavas. They are compositionally similar to typical Pual Ridge dacites indicating a genetic relationship between the main regional volcanic suite and the subseafloor hydrothermally altered, Pb-enriched material. Relative loss/gain for Pb between the analyzed altered samples and a calculated precursor show a maximum relative gain of 901%. Samples with relative Pb gain from both drill sites are associated with lower temperature alteration mineral assemblages characterized by pervasive chloritization. The related lower temperature (220-250°C) neutral to slightly acidic fluids have been ascribed by others to return circulation of hydrothermal fluids that did not interact with seawater. Because altered samples have a higher Pb content than the fresh precursor, leaching of fresh volcanic rocks cannot be the source of Pb in the hydrothermal systems.

Chemistry of volcanic ash from Celebes and Sulu Sea Basins

During Leg 124, off the Philippines, volcanic material was recovered in deep-sea sediments dating from the late Oligocene in the Celebes Sea Basin, and from the early Miocene in the Sulu Sea Basin. Chemical and petrological studies of fallout ash deposits are used to characterize volcanic pulses and to determine their possible origin. All of the glass and mineral compositions belong to medium-K and high-K calc-alkaline arc-related magmatic suites including high-Al basalts, pyroxene-hornblende andesites, dacites, and rhyolites. Late Oligocene and early Miocene products may have originated from the Sunda arc or from the Sabah-Zamboanga old Sulu arc. Late early Miocene Sulu Sea tuffs originated from the Cagayan arc, whereas early late Miocene fallout ashes are attributed to the Sulu arc. A complex magmatic production is distinguished in the Plio-Quaternary with three sequences of basic to acidic lava suites. Early Pliocene strata registered an important activity in both Celebes Sea and Sulu Sea areas, from the newly born Sangihe arc (low-alumina andesite series) and from the Sulu, Zamboanga, and Negros arcs (high-alumina basalt series and high-K andesite series). In the late Pliocene and the early Pleistocene, renewal of activity affects the Sangihe-Cotobato arc as well as the Sulu and Negros arcs (same magmatic distinctions). The last volcanic pulse took place in the late Pleistocene with revival of all the present arc systems.

Mineral composition of altered felsic volcanic rocks from ODP Site 193-1188 and Hole 193-1189A, PACMANUS field

This report presents short-wave infrared spectroscopic data acquired from both core and powdered samples collected during Ocean Drilling Program Leg 193, from Holes 1188A, 1188F, and 1189A, using a Portable Infrared Mineral Analyzer reflectance spectrometer. The distribution of alteration minerals detected using this method for each site is presented.

Chemical composition of glass inclusions of volcanic rocks from the Bonin Arc

The chemical composition of glass inclusions in phenocrystic plagioclase and pyroxene from Sites 792 and 793, drilled during Ocean Drilling Program Leg 126 in the Bonin Arc, is examined. Immiscible liquid, which is preserved as glass inclusions with unmixed textures in plagioclase, is observed in a high-magnesian andesite, which suggests an important role of liquid immiscibility in the fractionation of high-magnesian andesite. In other andesitic rocks (SiO2 = 57-60 wt%), such unmixed textures of glass inclusions in calcic plagioclase with a similar percentage of An (around 80%) is not found. The degree of fractionation and mixing of liquid are inferred from the glass composition in pyroxene.

Major and trace element composition of melts from the Gorely volcanic center, southern Kamchatka

Melt inclusions in olivine and plagioclase phenocrysts from rocks (magnesian basalt, basaltic andesite, andesite, ignimbrite, and dacite) of various age from the Gorely volcanic center, southern Kamchatka, were studied by means of their homogenization and by analyzing the glasses in 100 melt inclusions on an electron microprobe and 24 inclusions on an ion probe. The SiO2 concentrations of the melts vary within a broad range of 45-74 wt%, as also are the concentrations of other major components. According to their SiO2, Na2O, K2O, TiO2, and P2O5 concentrations, the melts are classified into seven groups. The mafic melts (45-53 wt% SiO2) comprise the following varieties: potassic (on average 4.2 wt% K2O, 1.7 wt% Na2O, 1.0 wt% TiO2, and 0.20 wt% P2O5), sodic (3.2% Na2O, 1.1% K2O, 1.1% TiO2, and 0.40% P2O5), and titaniferous with high P2O5 concentrations (2.2% TiO2, 1.1% P2O5, 3.8% Na2O, and 3.0% K2O). The melts of intermediate composition (53-64% SiO2) also include potassic (5.6% K2O, 3.4% Na2O, 1.0% TiO2, and 0.4% P2O5) and sodic (4.3% Na2O, 2.8% K2O, 1.3% TiO2, and 0.4% P2O5) varieties. The acid melts (64-74% SiO2) are either potassic (4.5% K2O, 3.6% Na2O, 0.7% TiO2, and 0.15% P2O5) or sodic (4.5% Na2O, 3.1% K2O, 0.7% TiO2, and 0.13% P2O5). A distinctive feature of the Gorely volcanic center is the pervasive occurrence of K-rich compositions throughout the whole compositional range (silicity) of the melts. Melt inclusions of various types were sometimes found not only in a single sample but also in the same phenocrysts. The sodic and potassic types of the melts contain different Cl and F concentrations: the sodic melts are richer in Cl, whereas the potassic melts are enriched in F. We are the first to discover potassic melts with very high F concentrations (up to 2.7 wt%, 1.19 wt% on average, 17 analyses) in the Kuriles and Kamchatka. The average F concentration in the sodic melts is 0.16 wt% (37 analyses). The melts are distinguished for their richness in various groups of trace elements: LILE, REE (particularly HREE), and HFSE (except Nb). All of the melts share certain geochemical features. The concentrations of elements systematically increase from the mafic to acid melts (except only for the Sr and Eu concentrations, because of active plagioclase fractionation, and Ti, an element contained in ore minerals). The paper presents a review of literature data on volcanic rocks in the Kurile-Kamchatka area in which melt inclusions with high K2O concentrations (K2O/Na2O > 1) were found. K-rich melts are proved to be extremely widespread in the area and were found on such volcanoes as Avachinskii, Bezymyannyi, Bol'shoi Semyachek, Dikii Greben', Karymskii, Kekuknaiskii, Kudryavyi, and Shiveluch and in the Valaginskii and Tumrok Ranges.

Sedimentological, petrographical and biostratigraphical characteristics of ODP Leg 190 volcanic ashes and siliceous claystones

Leg 190 was the first of a two-leg program across the Nankai accretionary prism and Trough, offshore Japan, aiming to evaluate existing models for prism evolution and to constrain syntectonic sedimentation, deformation styles, mechanical properties, and prism hydrology (Moore, Taira, Klaus, et al., 2001; Moore et al., 2001). More than 400 volcanic ash and siliceous claystone (altered ash) layers were penetrated and sampled during drilling of the six sites from two transects across the accretionary prism (Sites 1173-1178). In sites from the subducting Shikoku Basin (Sites 1173 and 1177) and in the trench axis (Site 1174), recognition of ash layers and diagenetically altered ashes was initially important in defining major lithostratigraphic units. However, it is clear that understanding the diagenesis of the volcanic ashes has considerable implications for prism evolution, mechanical properties, prism hydrology, geochemistry, and fluid flow in the accretionary prism and associated subducting sediments (cf. Masuda et al., 1996, doi 10.1346/CCMN.1996.0440402). Particle size, chemical composition, temperature, depth of burial, and time are all thought to be factors that may affect volcanic ash diagenesis and preservation (Kuramoto et al., 1992, doi:10.2973/odp.proc.sr.127128-2.235.1992; Underwood et al., 1993, doi:10.2973/odp.proc.sr.131.137.1993). The overall aim of this research is to evaluate factors influencing volcanic ash diagenesis in the Nankai Trough area. This data report presents just the results of the sedimentological and petrographic analysis of the volcanic ashes and siliceous claystones from Sites 1173, 1174, and 1177. It is anticipated that when the results of additional geochemical analysis of these lithologies is available a more meaningful evaluation of factors influencing volcanic ash alteration will be possible.

Geochemistry of volcanic rocks of ODP Holes 126-792E and 126-793B

The Izu-Bonin forearc basement volcanic rocks recovered from Holes 792E and 793B show the same phenocrystic assemblage (i.e., plagioclase, two pyroxenes, and Fe-Ti oxides ±olivine), but they differ in the crystallization sequence and their phenocryst chemistry. All the igneous rocks have suffered low-grade hydrothermal alteration caused by interaction with seawater. As a result, only clinopyroxenes, plagioclases, and oxides have preserved their primary igneous compositions. The Neogene olivine-clinopyroxene diabasic intrusion (Unit II) recovered from Hole 793B differs from the basement basaltic andesites because it lacks Cr-spinels and contains abundant titanomagnetites (Usp38.5-46.4) and uncommon FeO-rich (FeO = 29%) spinels. It displays petrological and geochemical similarities to the Izu Arc volcanoes and, thus, can be considered as related to Izu-Bonin Arc magmatic activity. The titanomagnetites (Usp28.5-33) in the calc-alkaline andesitic fragments of the Oligocene volcaniclastic breccia in Hole 793B (Unit VI) represent an early crystallization phase. The Plagioclase phenocrysts enclosed in these rocks show oscillatory zoning and are less Ca-rich (An78.6-67.8) than the plagioclase phenocrysts of the diabase sill and the basement basaltic andesites. Their clinopyroxenes are Fe-rich augites (Fs ? 19.4; FeO = 12%) and thus, differ significantly from the clinopyroxenes of the Hole 793B arc-tholeiitic igneous rocks. The 30-32 Ma porphyritic, two-pyroxene andesites recovered from Hole 792E are very similar to the andesitic clasts of the Neogene breccia recovered in Hole 793B (Unit VI). Both rocks have the same crystallization sequence, and similar chemistry of the Fe-Ti oxides, clinopyroxenes, and plagioclases: that is, Ti-rich (Usp25.5-30.4) magnetites, Fe-rich augites, and intensely oscillatory zoned plagioclases with bytownitic cores (An86-63) and labradorite rims (An73-68). They display a calc-alkaline differentiation trend (Taylor et al., this volume). So, the basement highly porphyritic andesites recovered at Hole 792E, and the Hole 793B andesitic clasts of Unit VI show the same petrological and geochemical characteristics, which are that of calc-alkaline suites. These Oligocene volcanic rocks represent likely the remnants of the Izu-Bonin normal arc magmatic activity, before the forearc rifting and extension. The crystallization sequence in the basaltic andesites recovered from Hole 793B is olivine-orthopyroxene-clinopyroxene-plagioclase-Fe-Ti oxides, indicating a tholeiitic differentiation trend for these volcanic rocks. Type i is an olivine-and Cr-spinel bearing basaltic andesite whereas Type ii is a porphyritic pyroxene-rich basaltic andesite. The porphyritic plagioclase-rich basaltic andesite (Type iii) is similar, in most respects, to Type ii lavas but contains plagioclase phenocrysts. The last, and least common lava is an aphyric to sparsely phyric andesite (Type iv). Cr-spinels, included either in the olivine pseudomorphs of Type i lavas or in the groundmass of Type ii lavas, are Cr-rich and Mg-rich. In contrast, Cr-spinels included in clinopyroxenes and orthopyroxenes (Types i and ii lavas) show lower Cr* and Mg* ratios and higher aluminium contents. Orthopyroxenes from all rock types are Mg-rich enstatites. Clinopyroxenes display endiopsidic to augitic compositions and are TiO2 and Al2O3 depleted. All the crystals exhibit strong zoning patterns, usually normal, although, reverse zoning patterns are not uncommon. The plagioclases show compositions within the range of An90-64. The Fe-Ti oxides of the groundmass are TiO2-poor (Usp16-17). The Hole 793B basaltic andesites show, like the Site 458 bronzites from the Mariana forearc, intermediate features between arc tholeiites and boninites: (1) Cr-spinel in olivine, (2) presence of Mg-rich bronzite, Ca-Mg-rich clinopyroxenes, and Ca-plagioclase phenocrysts, and (3) transitional trace element depletion and epsioln-Nd ratios between arc tholeiites and boninites. Thus, the forearc magmatism of the Izu-Bonin and Mariana arcs, linked to rifting and extension, is represented by a depleted tholeiitic suite that displays boninitic affinities.