Geochemistry and mineralogy of variably altered dacite volcanic rocks from ODP Leg 193 sites, PACMANUS field

A geochemical, mineralogical, and isotopic database comprising 75 analyses of Ocean Drilling Program (ODP) Leg 193 samples has been prepared, representing the variable dacitic volcanic facies and alteration types observed in drill core from the subsurface of the PACMANUS hydrothermal system (Table T1. The data set comprises major elements, trace and rare earth elements (REE), various volatiles (S, F, Cl, S, SO4, CO2, and H2O), and analyses of 18O and 86Sr/87Sr for bulk rock and mineral separates (anhydrite). Furthermore, normative mineral proportions have been calculated based on the results of X-ray diffraction (XRD) analysis (Table T2) using the SOLVER function of the Microsoft Excel program. Several of the samples analyzed consist of mesoscopically distinctive domains, and separate powders were generated to investigate these hand specimen-scale heterogeneities. Images of all the samples are collated in Figure F1, illustrating the location of each powder analyzed and documenting which measurements were performed.

Appendix A. Whole-rock major, trace and rare earth element analyses of the Ulubey volcanics, Appendix B. Analytical standards and detection limits for analyses

Collisional and post-collisional volcanic rocks in the Ulubey (Ordu) area at the western edge of the Eastern Pontide Tertiary Volcanic Province (EPTVP) in NE Turkey are divided into four suites; Middle Eocene (49.4-44.6 Ma) aged Andesite-Trachyandesite (AT), Trachyandesite-Trachydacite-Rhyolite (TTR), Trachydacite-Dacite (TD) suites, and Middle Miocene (15.1 Ma) aged Trachybasalt (TB) suite. Local stratigraphy in the Ulubey area starts with shallow marine environment sediments of the Paleocene-Eocene time and then continues extensively with sub-aerial andesitic to rhyolitic and rare basaltic volcanism during Eocene and Miocene time, respectively. Petrographically, the volcanic rocks are composed primarily of andesites/trachyandesites, with minor trachydacites/rhyolites, basalts/trachybasalts and pyroclastics, and show porphyric, hyalo-microlitic porphyric and rarely glomeroporphyric, intersertal, intergranular, fluidal and sieve textures. The Ulubey (Ordu) volcanic rocks indicate magma evolution from tholeiitic-alkaline to calc-alkaline with medium-K contents. Primitive mantle normalized trace element and chondrite normalized rare earth element (REE) patterns show that the volcanic rocks have moderate light rare earth element (LREE)/heavy rare earth element (HREE) ratios relative to E-Type MORB and depletion in Nb, Ta and Ti. High Th/Yb ratios indicate parental magma(s) derived from an enriched source formed by mixing of slab and asthenospheric melts previously modified by fluids and sediments from a subduction zone. All of the volcanic rocks share similar incompatible element ratios (e.g., La/Sm, Zr/Nb, La/Nb) and chondrite-normalized REE patterns, indicating that the basic to acidic rocks originated from the same source. The volcanic rocks were produced by the slab dehydration-induced melting of an existing metasomatized mantle source, and the fluids from the slab dehydration introduced significant large ion lithophile element (LILE) and LREE to the source, masking its inherent HFSE-enriched characteristics. The initial 87Sr/86Sr (0.7044-0.7050) and eNd (-0.3 to +3.4) ratios of the volcanics suggest that they originated from an enriched lithospheric mantle source with low Sm/Nd ratios. Integration of the geochemical, petrological and isotopical with regional and local geological data suggest that the Tertiary volcanic rocks from the Ulubey (Ordu) area were derived from an enriched mantle, which had been previously metasomatized by fluids derived from subducted slab during Eocene to Miocene in collisional and post-collisional extension-related geodynamic setting following Late Mesozoic continental collision between the Eurasian plate and the Tauride-Anatolide platform.

Geochemistry of ODP Leg 135 vitrophyric rhyolite samples

In-situ proton-microprobe analyses are presented for glasses, plagioclases, pyroxenes, olivines, and spinels in eleven samples from Sites 834-836, 839, and 841 (vitrophyric rhyolite), plus a Tongan dacite. Elements analyzed are Mn, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Pb, and Sn (in spinels only). The data are used to calculate two sets of partition coefficients, one set based on the ratio of element in mineral/element in coexisting glass. The second set of coefficients, thought to be more robust, is corrected by application of the Rayleigh fractionation equations, which requires additional use of modal data. Data are presented for phenocryst core-rim phases and microphenocryst-groundmass phases from a few samples. Comparison with published coefficients reveals an overall consistency with those presented here, but with some notable anomalies. Examples are relatively high Zr values for pyroxenes and abnormally low Mn values in olivines and clinopyroxenes from Site 839 lavas. Some anomalies may reflect kinetic effects, but interpretation of the coefficients is complicated, especially in olivines from Sites 836 and 839, by possible crystal-liquid disequilibrium resulting from mixing processes.

Geochemistry of igneous rock samples of ODP Site 125-786

A morphologically complex igneous basement was penetrated at Leg 125 Site 786 beneath approximately 100 m of Eocene-Pleistocene sediments at 31°52.45 'N, 141°13.59'E in a 3082-m water depth. The site is located on the forearc basement high (FBH) of the Izu-Bonin (Ogasawara) Arc. In the broadest terms, the sequence in Hole 786B consists of a basal sheeted dike complex, heavily mineralized in places, with overlying pillow lavas giving way to a complex and repeated sequence of interlayered volcanic breccias and lava flows with some thin sedimentary intervals. The sequence has been further cut by dikes or sills, particularly of high-Ca and intermediate-Ca boninite, and is locally strongly sheared by faulting. The whole basement has been covered with middle Eocene-early Pleistocene sediments. A monomict breccia forms the shallowest portion of Hole 786B and a polymict breccia having Mn-oxide-rich clast coatings and matrix forms the deepest part of Hole 786A (-100-160 mbsf). The basement is tectonized in some places, and a mineralized stockwork is present in the deepest part of Hole 786B. A wide variety of rock types form this basement, ranging from mafic to silicic in character and including high-, intermediate-, and low-Ca boninites, intermediate- and low-Ca bronzite andesites, andesite, dacite, and rhyolite groups. Intragroup and intergroup relationships are complicated in detail, and several different upper mantle source(s) probably were involved. A significant role for orthopyroxene-clinopyroxene-plagioclase fractionation is indicated in the mafic-intermediate groups, and the most probable complementary cumulates should be noritic gabbros. Many overall similarities but some subtle differences are noted between the igneous basement at Site 786 and the subaerial outcrops of the FBH to the south in the type boninite locality of Chichijima. Both suites were derived by hydrous melting of a relatively shallow, refractory (harzburgitic) upper mantle source. These Bonin forearc basement rocks are similar in many respects to those of Eocene-Oligocene age now forming the forearc of the Marianas at Leg 60 Site 458 and on Guam. In sharp distinction, the geochemistry of the Eocene-Pleistocene ash sequences overlying the Bonin FBH must have been derived from a very different upper mantle source, implying considerable across-strike differences in sub-arc mantle composition.

Investigations on volcanic rocks in sediment core CRP-3 from the Ross Sea, Antarctica

The petrography, mineralogy and geochemistry of volcanic and subvolcanic rocks in CRP-3 core have been examined in detail in order to characterise and to compare them with volcanic and subvolcanic rocks cropping out in the Victoria Land area, and to define the clast provenance or to establish possible volcanic activity coeval with deposition. Clasts with sizes ranging from granule to boulder show geochemical and mineralogical features comparable with those of Ferrar Supergroup rocks. They display a subalkaline affinity and compositions ranging from basalts to dacite. Three different petrographic groups with distinct textural and grain size features (subophitic, intergranular-intersertal, and glassy-hyalopilitic) are recognised and are related to the emplacement/cooling mechanism. In the sand to silt fraction, the few glass shards that have been recognised are strongly altered: however chemical analyses show they have subalkalic magmatic affinity. Mineral compositions of the abundant free clinopyroxene grains found in the core, are less affected by alteration processes, and indicate an origin from subalkaline magmas. This excludes the presence, during the deposition of CRP-3 rocks of alkaline volcanic activity comparable with the McMurdo Volcanic Group. Strong alteration of the magmatic body intruded the Beacon sandstones obliterates the original mineral assemblage. Geochemical investigations confirm that intrusion is part of the Ferar Large Igneous Province.

Pebbles and carbonate nodules Legs 56-57 Holes

At all DSDP Leg 56 drilling sites, exotic pebbles occur commonly, throughout the cores. Chips of carbonate nodules occur only at Site 434 on the lower inner trench wall. Both exotic pebbles and carbonate nodule chips sometimes tend to be concentrated at particular levels of cores. Exotic pebbles are generally well rounded and consist of various rock types, such as dacite, andesite, basalt, tuff, gabbro, granodiorite, metaquartzite, biotite hornfels, lithic wacke, mudstone, etc., of which dacite occurs commonly at all the sites. Almost all pebbles at Site 436 and most at Sites 434 and 435 may have been rafted by ice. Some at the latter sites may have been derived by down-slope slumping. Carbonate nodules consist of microcrystalline dolomite, manganoan calcite, and siderite; CaCO3 content ranges from 22 to 65 per cent. They are also generally characterized by a high content of P2O5. The nodules are commonly rich in diatom remains, some of which indicate that the nodules are autochthonous. Some nodules contain abundant glass shards, with a modal refractive index of 1.499, almost identical to shards in the surrounding mud and ooze. These facts suggest that the carbonate nodules may have been formed diagenetically, in situ. This may throw light on problems of the formation of carbonate nodules in ancient "geosynclinal" sediments. It is also very important to point out that these carbonate nodules were formed within sediment deposited well below the CCD.

Geochemistry at DSDP Hole 57-439

Dating of a hornblende concentrate by the 40Ar/39Ar method gives an age of 23.4±5.5 m.y. for a dacite boulder from conglomerate in Deep Sea Drilling Project Hole 439. The conglomerate clasts range up to 1 meter in diameter and are nearly monolithologic, suggesting that a nearby former volcano erupted the dacite. The dacite is only 90 km landward from the Japan Trench, whereas modern trench-related volcanoes lie at least 120 km from their trenches. The dacite locality is on strike with and is probably an extension of a magmatic arc on the island of Hokkaido that crosses the Kuril arc at an angle of 65° and which was active 16 to 36 m.y. ago. The part of the former arc landward from the Kuril arc argues against an origin from a leaking subduction zone or from subduction of an active spreading ridge. The part seaward both from the Kuril and Japan arcs weakens an explanation based on migration of a trench-trenchtrench triple junction. The magmatic rocks probably formed along a middle-Tertiary plate boundary that had stepped seaward from a more-landward Cretaceous position. Later, the boundary stepped farther seaward at the Kuril arc and landward again at the Japan arc. If so, the present Japan subduction zone must have consumed most of the strata that had accumulated between it and the earlier trench.

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.

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.

Zeolite and silica diagenesis and sandstone petrography at DSDP Sites 57-438 and 57-439

We detected authigenic clinoptilolites in two core samples of tuffaceous, siliceous mudstone in the lower Miocene section of Hole 439. They occur as prismatic and tabular crystals as long as 0.03 mm in various voids of dissolved glass shards, radiolarian shells, calcareous foraminifers, and calcareous algae. They are high in alkalies, especially Na, and in silica varieties. There is a slight difference in composition among them. The Si : (Al+ Fe3+) ratio is highest (4.65) in radiolarian voids, intermediate (4.34) in dissolved glass voids, and lowest (4.26) in voids of calcareous organisms. This difference corresponds to the association of authigenic silica minerals revealed by the scanning electron microscope: There are abundant opal-CT lepispheres in radiolarian voids, low cristobalite and some lepispheres in dissolved glass voids, and a lack of silica minerals in the voids of calcareous organisms. Although it contains some silica from biogenic opal and alkalies from trapped sea water, clinoptilolite derives principally from dissolved glass. Although they are scattered in core samples of Quaternary through lower Miocene diatomaceous and siliceous deposits, acidic glass fragments react with interstitial water to form clinoptilolite only at a sub-bottom depth of 935 meters at approximately 25°C. Analcimes occur in sand-sized clasts of altered acidic vitric tuff in the uppermost Oligocene sandstones. The analcimic tuff clasts were probably reworked from the Upper Cretaceous terrain adjacent to Site 439. Low cristobalite and opal-CT are found in tuffaceous, siliceous mudstone of the middle and lower Miocene sections at Sites 438 and 439. Low cristobalite derives from acidic volcanic glass and opal-CT from biogenic silica. Both siliceous organic remains and acidic glass fragments occur in sediments from the Quaternary through lower Miocene sections. However, the shallowest occurrence is at 700 meters subbottom in Hole 438A, where temperature is estimated to be 21°C. The d(101) spacing of opal-CT varies from 4.09 to 4.11 Å and that of low cristobalite from 4.04 to 4.06 Å. Some opal-CT lepispheres are precipitated onto clinoptilolites in the voids of radiolarian shells at a sub-bottom depth of 950 meters in Hole 439. Sandstone interlaminated with Upper Cretaceous shale is chlorite- calcite cemented and feldspathic. Sandstones in the uppermost Oligocene section are lithic graywacke and consist of large amounts of lithic clasts grouped into older sedimentary and weakly metamorphosed rocks, younger sedimentary rocks, and acidic volcanic rocks. The acidic volcanic clasts probably originated from the volcanic high, which supplied the basal conglomerate with dacite gravels. The older sedimentary and weakly metamorphosed rocks and green rock correspond to the lithologies of the lower Mesozoic to upper Paleozoic Sorachi Group, including the chert, limestone, and slate in south-central Hokkaido. However, the angular shape and coarseness of the clasts and the abundance of carbonate rock fragments indicate a nearby provenance, which is probably the southern offshore extension of the Sorachi Group. The younger sedimentary rocks, including mudstone, carbonaceous shale, and analcime-bearing tuff, correspond to the lithologies of the Upper Cretaceous strata in south-central Hokkaido. Their clasts were reworked from the southern offshore extension of the strata. Because of the discontinuity of the zeolite zoning due to burial diagenesis, an overburden several kilometers thick must have been denuded before the deposition of sediments in the early Oligocene.

Geochemistry of boninite and harzburgite of ODP Leg 125 basement samples

Holes drilled into the volcanic and ultrabasic basement of the Izu-Ogasawara and Mariana forearc terranes during Leg 125 provide data on some of the earliest lithosphere created after the start of Eocene subduction in the Western Pacific. The volcanic basement contains three boninite series and one tholeiite series. (1) Eocene low-Ca boninite and low-Ca bronzite andesite pillow lavas and dikes dominate the lowermost part of the deep crustal section through the outer-arc high at Site 786. (2) Eocene intermediate-Ca boninite and its fractionation products (bronzite andesite, andesite, dacite, and rhyolite) make up the main part of the boninitic edifice at Site 786. (3) Early Oligocene intermediate-Ca to high-Ca boninite sills or dikes intrude the edifice and perhaps feed an uppermost breccia unit at Site 786. (4) Eocene or Early Oligocene tholeiitic andesite, dacite, and rhyolite form the uppermost part of the outer-arc high at Site 782. All four groups can be explained by remelting above a subduction zone of oceanic mantle lithosphere that has been depleted by its previous episode of partial melting at an ocean ridge. We estimate that the average boninite source had lost 10-15 wt% of melt at the ridge before undergoing further melting (5-10%) shortly after subduction started. The composition of the harzburgite (<2% clinopyroxene, Fo content of about 92%) indicates that it underwent a total of about 25% melting with respect to a fertile MORB mantle. The low concentration of Nb in the boninite indicates that the oceanic lithosphere prior to subduction was not enriched by any asthenospheric (OIB) component. The subduction component is characterized by (1) high Zr and Hf contents relative to Sm, Ti, Y, and middle-heavy REE, (2) light REE-enrichment, (3) low contents of Nb and Ta relative to Th, Rb, or La, (4) high contents of Na and Al, and (5) Pb isotopes on the Northern Hemisphere Reference Line. This component is unlike any subduction component from active arc volcanoes in the Izu-Mariana region or elsewhere. Modeling suggests that these characteristics fit a trondhjemitic melt from slab fusion in amphibolite facies. The resulting metasomatized mantle may have contained about 0.15 wt% water. The overall melting regime is constrained by experimental data to shallow depths and high temperatures (1250? C and 1.5 kb for an average boninite) of boninite segregation. We thus envisage that boninites were generated by decompression melting of a diapir of metasomatized residual MORB mantle leaving the harzburgites as the uppermost, most depleted residue from this second stage of melting. Thermal constraints require that both subducted lithosphere and overlying oceanic lithosphere of the mantle wedge be very young at the time of boninite genesis. This conclusion is consistent with models in which an active transform fault offsetting two ridge axes is placed under compression or transpression following the Eocene plate reorganization in the Pacific. Comparison between Leg 125 boninites and boninites and related rocks elsewhere in the Western Pacific highlights large regional differences in petrogenesis in terms of mantle mineralogy, degree of partial melting, composition of subduction components, and the nature of pre-subduction lithosphere. It is likely that, on a regional scale, the initiation of subduction involved subducted crust and lithospheric mantle wedge of a range of ages and compositions, as might be expected in this type of tectonic setting.

(Supplemet S1) Silicon oxide and Potassium + Sodium oxide from the PACManus hydrothermal area

This study presents a systematic analysis and interpretation of autonomous underwater vehicle-based microbathymetry combined with remotely operated vehicle (ROV) video recordings, rock analyses and temperaturemeasurements within the PACManus hydrothermal area located on Pual Ridge in the Bismarck Sea of eastern Manus Basin. The data obtained during research cruise Magellan-06 and So-216 provides a framework for understanding the relationship between the volcanism, tectonismand hydrothermal activity. PACManus is a submarine felsic vocanically-hosted hydrothermal area that hosts multiple vent fields locatedwithin several hundredmeters of one another but with different fluid chemistries, vent temperatures and morphologies. The total area of hydrothermal activity is estimated to be 20,279m**2. Themicrobathymetrymaps combinedwith the ROV video observations allow for precise high-resolution mapping estimates of the areal extents of hydrothermal activity.We find the distribution of hydrothermal fields in the PACManus area is primarily controlled by volcanic features that include lava domes, thick andmassive blocky lava flows, breccias and feeder dykes. Spatial variation in the permeability of local volcanic facies appears to control the distribution of venting within a field.We define a three-stage chronological sequence for the volcanic evolution of the PACManus based on lava flow morphology, sediment cover and lava SiO2 concentration. In Stage-1, sparsely to moderately porphyritic dacite lavas (68-69.8 wt.% SiO2) erupted to form domes or cryptodomes. In Stage-2, aphyric lava with slightly lower SiO2 concentrations (67.2-67.9 wt.% SiO2) formed jumbled and pillowed lava flows. In the most recent phase Stage-3, massive blocky lavaswith 69 to 72.5wt.% SiO2were erupted throughmultiple vents constructing a volcanic ridge identified as the PACManus neovolcanic zone. The transition between these stages may be gradual and related to progressive heating of a silicic magma following a recharge event of hot, mantle-derived melts.