Novel sol–gel preparation of (P2O5)0.4–(CaO)0.25–(Na2O)X–(TiO2)(0.35−X) bioresorbable glasses (X = 0.05, 0.1, and 0.15)

Quaternary phosphate-based glasses in the P2O5–CaO–Na2O–TiO2 system with a fixed P2O5 and CaO content of 40 and 25 mol% respectively have been successfully synthesised via sol–gel method and bulk, transparent samples were obtained. The structure, elemental proportion, and thermal properties of stabilised sol–gel glasses have been characterised using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), 31P nuclear magnetic resonance (31P NMR), titanium K-edge X-ray absorption near-edge structure (XANES), fourier transform infrared (FTIR) spectroscopy, and differential thermal analysis (DTA). The XRD results confirmed the amorphous nature for all stabilized sol–gel derived glasses. The EDX result shows the relatively low loss of phosphorus during the sol–gel process and Ti K-edge XANES confirmed titanium in the glass structure is in mainly six-fold coordination environment. The 31P NMR and FTIR results revealed that the glass structure consist of mainly Q1 and Q2 phosphate units and the Ti4+ cation was acting as a cross-linking between phosphate units. In addition DTA results confirmed a decrease in the glass transition and crystallisation temperature with increasing Na2O content. Ion release studies also demonstrated a decrease in degradation rates with increasing TiO2 content therefore supporting the use of these glasses for biomedical applications that require a degree of control over glass degradation. These sol–gel glasses also offer the potential to incorporate proactive molecules for drug delivery application due to the low synthesis temperature employed.

Chemical composition of Late Cenozoic volcanic and volcaniclastic deposits from the western Woodlark Basin area, SW Pacific

Tephra fallout layers and volcaniclastic deposits, derived from volcanic sources around and on the Papuan Peninsula, form a substantial part of the Woodlark Basin marine sedimentary succession. Sampling by the Ocean Drilling Program Leg 180 in the western Woodlark Basin provides the opportunity to document the distribution of the volcanically-derived components as well as to evaluate their chronology, chemistry, and isotope compositions in order to gain information on the volcanic sources and original magmatic systems. Glass shards selected from 57 volcanogenic layers within the sampled Pliocene-Pleistocene sedimentary sequence show predominantly rhyolitic compositions, with subordinate basaltic andesites, basaltic trachy-andesites, andesites, trachy-andesites, dacites, and phonolites. It was possible to correlate only a few of the volcanogenic layers between sites using geochemical and age information apparently because of the formation of strongly compartmentalised sedimentary realms on this actively rifting margin. In many cases it was possible to correlate Leg 180 volcanic components with their eruption source areas based on chemical and isotope compositions. Likely sources for a considerable number of the volcanogenic deposits are Moresby and Dawson Strait volcanoes (D'Entrecasteaux Islands region) for high-K calc-alkaline glasses. The Dawson Strait volcanoes appear to represent the source for five peralkaline tephra layers. One basaltic andesitic volcaniclastic layer shows affinities to basaltic andesites from the Woodlark spreading tip and Cheshire Seamount. For other layers, a clear identification of the sources proved impossible, although their isotope and chemical signatures suggest similarities to south-west Pacific subduction volcanism, e.g. New Britain and Tonga- Kermadec island arcs. Volcanic islands in the Trobriand Arc (for example, Woodlark Island Amphlett Islands and/or Egum Atoll) are probable sources for several volcaniclastic layers with ages between 1.5 to 3 Ma. The Lusancay Islands can be excluded as a source for the volcanogenic layers found during Leg 180. Generally, the volcanogenic layers indicate much calc-alkaline rhyolitic volcanism in eastern Papua since 3.8 Ma. Starting at 135 ka, however, peralkaline tephra layers appear. This geochemical change in source characteristics might reflect the onset of a change in geotectonic regime, from crustal subduction to spreading, affecting the D'Entrecasteaux Islands region. Initial 143Nd/144Nd ratios as low as 0.5121 and 0.5127 for two of the tephra layers are interpreted as indicating that D'Entrecasteaux Islands volcanism younger than 2.9 Ma occasionally interacted with the Late Archean basement, possibly reflecting the mobilisation of the deep continental crust during active rift propagation.

Geochemistry of Atlantis Massif crust

The Atlantis Massif (Mid-Atlantic Ridge, 30°N) is an oceanic core complex marked by distinct variations in crustal architecture, deformation and metamorphism over distances of at least 5 km. We report Sr and Nd isotope data and Rare Earth Element (REE) concentrations of gabbroic and ultramafic rocks drilled at the central dome (IODP Hole 1309D) and recovered by submersible from the southern ridge of the massif that underlie the peridotite-hosted Lost City Hydrothermal Field. Systematic variations between the two areas document variations in seawater penetration and degree of fluid-rock interaction during uplift and emplacement of the massif and hydrothermal activity associated with the formation of Lost City. Homogeneous Sr and Nd isotope compositions of the gabbroic rocks from the two areas (87Sr/86Sr: 0.70261-0.70429 and epsilon-Nd: +9.1 to +12.1) indicate an origin from a depleted mantle. At the central dome, serpentinized peridotites are rare and show elevated seawater-like Sr isotope compositions related to serpentinization at shallow crustal levels, whereas unaltered mantle isotopic compositions preserved in the gabbroic rocks attest to limited seawater interaction at depth. This portion of the massif remained relatively unaffected by Lost City hydrothermal activity. In contrast, pervasive alteration and seawater-like Sr and Nd isotope compositions of serpentinites at the southern wall (87Sr/86Sr: 0.70885-0.70918; epsilon-Nd: -4.7 to +11.3) indicate very high fluid-rock ratios (~20 and up to 10**6) and enhanced fluid fluxes during hydrothermal circulation. Our studies show that Nd isotopes are most sensitive to high fluid fluxes and are thus an important geochemical tracer for quantification of water-rock ratios in hydrothermal systems. Our results suggest that high fluxes and long-lived serpentinization processes may be critical to the formation of Lost City-type systems and that normal faulting and mass wasting in the south facilitate seawater penetration necessary to sustain hydrothermal activity.

Representative analyses of garnet, plagioclase, orthopyroxene, ilmenite, hornblende and biotite for pre-tectonic mafic and metapelitic rocks in Gjelsvikfjella

A metamorphic petrological study, in conjunction with recent precise geochronometric data, revealed a complex P-T-t path for high-grade gneisses in a hitherto poorly understood sector of the Mesoproterozoic Maud Belt in East Antarctica. The Maud Belt is an extensive high-grade, polydeformed, metamorphic belt, which records two significant tectono-thermal episodes, once towards the end of the Mesoproterozoic and again towards the late Neoproterozoic/Cambrian. In contrast to previous models, most of the metamorphic mineral assemblages are related to a Pan-African tectono-thermal overprint, with only very few relics of late Mesoproterozoic granulite-facies mineral assemblages (M1) left in strain-protected domains. Petrological and mineral chemical evidence indicates a clockwise P-T-t path for the Pan-African orogeny. Peak metamorphic (M2b) conditions recorded by most rocks in the area (T = 709-785 °C and P = 7.0-9.5 kbar) during the Pan-African orogeny were attained subsequent to decompression from probably eclogite-facies metamorphic conditions (M2a). The new data acquired in this study, together with recent geochronological and geochemical data, permit the development of a geodynamic model for the Maud Belt that involves volcanic arc formation during the late Mesoproterozoic followed by extension at 1100 Ma and subsequent high-grade tectono-thermal reworking once during continent-continent collision at the end of the Mesoproterozoic (M1; 1090-1030 Ma) and again during the Pan-African orogeny (M2a, M2b) between 565 and 530 Ma. Post-peak metamorphic K-metasomatism under amphibolite-facies conditions (M2c) followed and is ascribed to post-orogenic bimodal magmatism between 500 and 480 Ma.

Chemical and mineral composition of rocks from the Philippine Sea

The book is devoted to geology of the Philippine Sea floor. This region is studied most extensively among other marginal seas of the Pacific Ocean. Rocks of the sedimentary and basalt layers within this sea have been studied during five legs of D/S Glomar Challenger. International geological expedition on board R/V Dmitry Mendeleev carried out according to the Project ''Ophiolites of Continents and Comparable Rocks of the Ocean Floor''obtained unique collection of rocks from the second and third layers of the ocean crust in the Philippine Sea. The book provides detailed petrographic and geochemical description of igneous and sedimentary formations from the Philippine Sea and compares them with rocks of the continental ophiolite association. An analysis of structure and history of the ocean crust formation in the region is based on all known geological information. The main periods of tectonic movement activation and nature of their manifestations within the sea are shown.

Data on the biogeochemical cycle of methane in the ocean

Geological, mineralogical and microbiological aspects of the methane cycle in water and sediments of different areas in the oceans are under consideration in the monograph. Original and published estimations of formation- and oxidation rates of methane with use of radioisotope and isotopic methods are given. The role of aerobic and anaerobic microbial oxidation of methane in production of organic matter and in formation of authigenic carbonates is considered. Particular attention is paid to processes of methane transformation in areas of its intensive input to the water column from deep-sea hydrothermal sources, mud volcanoes, and cold methane seeps.

Chemical composition of bottom sediments and sedimentary rocks from the Pilippine Sea

Data on chemical composition of bottom sediments from some polygons in the Philippine Sea are reported. Areal and vertical variability of major and trace element contents in bottom sediments is analyzed for clarifying sedimentation features and diagenetic migration of the elements in the upper part of the sedimentary sequence.

Quarternary tephra layers in sediment cores from the Bellingshausen Sea and Scotia Sea

The Southern Ocean is a region of the world's ocean which is fundamental to the generation of cold deep ocean water which drives the global therrno-haline circulation. Previous investigations of deep-sea sediments south of the Polar Front have been significantly constrained by the lack of a suitable correlation and dating technique. In this study, deep-sea sediment cores from the Bellingshausen, Scotia and Weddell seas have been investigated for the presence of tephra layers. The major oxide and trace element composition of glass shards have been used to correlate tephra isochrons over distances in excess of 600 km. The source volcanoes for individual tephra layers have been identified. Atmospheric transport distances greater than 1500 km for >32 pm shards are reported. One megascopic tephra is identified and correlated across 7 sediment drifts on the continental rise in the Bellingshausen Sea. Its occurrence in a sedimentary unit that has been biostratigraphically dated to delta 18O substage 5e identifies it as a key regional marker horizon for that stage. An unusual bimodal megascopic ash layer erupted from Deception Island, South Shetland Islands, has been correlated between 6 sediment cores which form a 600 km NE-SW transect from the central Scotia Sea to Jane Basin. This megascopic ash layer has been 14C dated at c. 10,670 years BP. It represents the last significant input of tephra into the Scotia Sea or Jane Basin from that volcano and forms an important early Holocene marker horizon for the region. Five disseminated tephras can be correlated to varying extents across the central Scotia Sea cores. Together with the megascopic tephra they form a tephrostratigraphic framework that will greatly aid palaeoclimatic, palaeoenvironrnental and palaeoceanographic investigations in the region.

Basalt analyses from different DSDP Holes in the Mozambique Basin and Ridge and from the Southwest Indian Ridge

Basalts from DSDP Sites 248, 249, 250 and 251 in the southwestern Indian Ocean formed in a complex tectonic region affected by the separation of Africa and South America. The different ages and variable geochemical features of these DSDP basalts probably reflect this tectonic complexity. For example, Site 251 on the flanks of the Southwest Indian Ridge is represented by normal MORB which probably originated at the Southwest Indian Ridge. Site 250 in the Mozambique Basin includes an older incompatible- element enriched unit which may represent basalt associated with the Prince Edward Fracture Zone; the upper unit is normal MORB. Basalts at Site 248 also in the Mozambique Basin are geochemically very unlike MORB and have strong continental affinities; they are also comparable in age to some of the continental Karroo basalts. They appear to be related to a subcontinental mantle source or to contamination by continental basement associated with the tectonic elevation of the Mozambique Ridge. Basalts from Site 249 on the Mozambique Ridge are relatively weathered but appear to be normal MORB. Their age, location, and composition are consistent with their origin at an early Cretaceous rift which has been postulated to have separated the Falkland Plateau from the Mozambique Ridge.

Composition of melt inclusions and age of zircons of plagiogneisses from the Kola Superdeep Borehole

A comprehensive study of melt inclusions and SHRIMP dating of zircons from trondhjemite gneisses of the sequence VIII from the Kola Superdeep Borehole has revealed presence of old primary magmatic crystals with age up to 2887+/-15 Ma. This is not consistent with the previous view, according to which the oldest zircons from the Archean Complex in SG-3 are products of granulite metamorphism. Primary magmatic zircons of early generation (from 2887 to 2842 Ma) formed in deep-seated magma chambers during partial crystallization of CO2-saturated trondhjemite estimates on duration of generation of tonalite-trondhjemite-granite melts through partial melting of mafic rocks.

Major and trace elements and Nd and Sr isotope geochemistry of basalts at DSDP Leg 74 Holes

Basement intersected in Holes 525A, 528, and 527 on the Walvis Ridge consists of submarine basalt flows and pillows with minor intercalated sediments. These holes are situated on the crest and mid- and lower NW flank of a NNW-SSE-trending ridge block which would have closely paralleled the paleo mid-ocean ridge. The basalts were erupted approximately 70 Ma, a date consistent with formation at the paleo mid-ocean ridge. The basalt types vary from aphyric quartz tholeiites on the Ridge crest to highly Plagioclase phyric olivine tholeiites on the flank. These show systematic differences in incompatible trace element and isotopic composition, and many element and isotope ratio pairs form systematic trends with the Ridge crest basalts at one end and the highly phyric Ridge flank basalts at the other. The low 143Nd/144Nd (0.51238) and high 87Sr/86Sr (0.70512) ratios of the Ridge crest basalts suggest derivation from an old Nd/Sm and Rb/Sr enriched mantle source. This isotopic signature is similar to that of alkaline basalts on Tristan da Cunha but offset by somewhat lower 143Nd/144Nd values. The isotopic ratio trends may be extrapolated beyond the Ridge flank basalts (which have 143Nd/144Nd of 0.51270 and 87Sr/86Sr of 0.70417) in the direction of typical MORB compositions. These isotopic correlations are equally consistent with mixing of depleted and enriched end-member melts or partial melting of an inhomogeneous, variably enriched mantle source. However, observed Zr-Ba-Nb-Y interelement relationships are inconsistent with any simple two-component model of magma mixing or partial melting. They also preclude extensive involvement of depleted (N-type) MORB material or its mantle sources in the petrogenesis of Walvis Ridge basalts.

The geochemistry, mineralogy, and petrology of basalts at DSDP Leg 59 Holes

Legs 59 and 60 of the International Phase of Oceanic Drilling (IPOD) were designed to study the nature and history of volcanism of the active Mariana arc, its currently spreading inter-arc basin (the Mariana Trough), and the series of inactive basins and intervening ridges that lie to the west. The older basins and ridges were drilled during Leg 59 as the first part of a transect of single-bit holes drilled in each major basin and ridge. The eastern part of the transect - the technically active region - was drilled during Leg 60. The evolution of island-arc volcanos and magma genesis associated with lithospheric subduction remain some of the most complex petrologic problems confronting us. Many types of source material (mantle, oceanic crust, continental crust) and an unusually wide range of possible physical conditions at the time of magma genesis must be identified even before the roles of partial melting and subsequent magma fractionation, mixing, and contamination can be assessed.

Geochemistry of the Japan Trench sediments at DSDP Legs 56-57 Holes

The main objective of this investigation was to study distribution of main chemical constituents and several minor elements in sediment sections drilled during DSDP Legs 56 and 57 in the Japan Trench, in order to infer geochemical features of different lithologic types of sediments, and to find out how the geochemistry is associated with major lithologic constituents, such as terrigenous detrital matter, clay, volcanic ash, and biogenic particles. The geochemical data may help to indicate the nature of the sediments and to interpret sedimentation processes. The analyzed samples seem to be representative of most lithologic units, sub-units, and sediment types drilled at all sites on both legs, except for some shallow-water deposits at Sites 438 and 439. We analyzed bulk-sediment composition by X-ray fluorescence (Kuzmina and Turanskaya) and routine wet-chemical methods (Mikhailov); amorphous SiO2, extracted in a boiling sodium carbonate solution (Analythical Laboratory, P. P. Shirshov Institute of Oceanology); Cr, Zn, Cu, Ni, Co, and Al by atomic absorption (Gordeev); and Sn, Pb, Zn, Cu, Ni, Co, Cr, V, B, and Ag by quantitative spectrographic analyses in both bulk samples and granulometric fractions (Mikhailov). In addition, Fe, Ti, Mn, and CaCO3 have been determined in selected samples by routine wet-chemical methods (Analytical Laboratory, P. P. Shirshov Institute of Oceanology). Murdmaa was responsible for interpretation of the results.

Geochemistry and minerals at DSDP Legs 68-70 Holes

The compositions of natural glasses and phenocrysts in basalts from Deep Sea Drilling Project Sites 501, 504, and 505, near the Costa Rica Rift, constitute evidence for the existence of a periodically replenished axial magma chamber that repeatedly erupted lavas of remarkably uniform composition. Magma compositions were affected by three general components: (1) injected magmas carrying (in decreasing order of abundance) Plagioclase, olivine, and chrome-spinel phenocrysts (spinel assemblage); (2) injected magmas carrying Plagioclase, clinopyroxene, and olivine phenocrysts, but no spinel (clinopyroxene assemblage); and (3) moderately evolved hybrids in the magma chamber itself. The compositions of the injected phenocrysts and minerals in glomerocrysts are as follows: Plagioclase - An85-94; olivine - Fo87-89; clinopyroxene - high Cr2O3 (0.7-1.1%), endiopside (Wo42En51Fs7), and aluminous chromian spinel (Cr/Cr + Al = 0.3). These minerals resemble those thought to occur in upper mantle sources (9 kbars and less) of ocean-ridge basalts and to crystallize in magmas near those sources. In the magma chamber, more sodic Plagioclase (An79-85), less magnesian olivine (Fo81-86) and low-Cr2O3 (0.1-0.4%) clinopyroxene formed rims on these crystals, grew as other phenocrysts, and formed cumulus segregations on the walls and floors of the magma chamber. In the spinel-assemblage magmas, magnesiochromite (Cr/Cr + Al = 0.4-0.5) also formed. Some cumulus segregations were later entrained in lavas as xenoliths. The glass compositions define 16 internally homogeneous eruptive units, 13 of which are in stratigraphic order in a single hole, Hole 504B, which was drilled 561.5 meters into the ocean crust. These units are defined as differing from each other by more than analytical uncertainty in one or more oxides. However, many of the glass groups in Hole 504B show virtually no differences in TiO2 contents, Mg/Mg + Fe2+, or normative An/An + Ab, all of which are sensitive indicators of crystallization differentiation. The differences are so small that they are only apparent in the glass compositions; they are almost completely obscured in whole-rock samples by the presence of phenocrysts and the effects of alteration. Moreover, several of the glass units at different depths in Hole 504B are compositionally identical, with all oxides falling within the range of analytical uncertainty, with only small variations in the rest of the suite. The repetition of identical chemical types requires (1) very regular injection of magmas into the magma chamber, (2) extreme similarity of injected magmas, and (3) displacement of very nearly the same proportion of the magmas in the chamber at each injection. Numerical modeling and thermal considerations have led some workers to propose the existence of such conditions at certain types of spreading centers, but the lava and glass compositions at Hole 504B represent the first direct evidence revealed by drilling of the existence of a compositionally nearly steady-state magma chamber, and this chapter examines the processes acting in it in some detail. The glass groups that are most similar are from clinopyroxene-assemblage lavas, which have a range of Mg/Mg + Fe2"1" of 0.59 to 0.65. Spinel-assemblage basalts are less evolved, with Mg/Mg + Fe2+ of 0.65 to 0.69, but both types have nearly identical normative An/An + Ab (0.65-0.66). However, the two lava types contain megacrysts (olivine, Plagioclase, clinopyroxene) that crystallized from melts with Mg/Mg + Fe2+ values of 0.70 to 0.72. Projection of glass compositions into ternary normative systems suggests that spinel-assemblage magmas originated deeper in the mantle than clinopyroxene-assemblage magmas, and mineral data indicate that the two types followed different fractionation paths before reaching the magma chamber. The two magma types therefore represent neither a low- nor a high-pressure fractionation sequence. Some of the spinel-assemblage magmas may have had picritic parents, but were coprecipitating all of the spinel-assemblage phenocrysts before reaching the magma chamber. Clinopyroxene-assemblage magmas did not have picritic parents, but the compositions of phenocrysts suggest that they originated at about 9 kbars, near the transition between plagioclase peridotite and spinel peridotite in the mantle. Two glass groups have higher contents of alkalis, TiO2, and P2O5 than the others, evidently as a result of the compositions of mantle sources. Eruption of these lavas implies that conduits and chambers containing magmas from dissimilar sources were not completely interconnected on the Costa Rica Rift. The data are used to draw comparisons with the East Pacific Rise and to consider the mechanisms that may have prevented the eruption of ferrobasalts at these sites.

Geochemistry of basement basaltic rocks of ODP Hole 131-808C

Major- and trace-element analyses, mineral chemistry, and Sr-Nd isotopic determinations were obtained on representative igneous rocks drilled from the Nankai accretionary complex (Site 808) during Ocean Drilling Program Leg 131. For the first time, the oceanic basement of the subducting plate below an accretionary prism has been reached. The Nankai Trough basement was encountered at a depth of 1289.9 mbsf and a total of 37.1 m of igneous rocks, middle Miocene (15.6 Ma) in age, was penetrated. Two main lithological units have been distinguished from the top downward; sill-like rocks (Unit I: Cores 105, 106, 107) and pillow lavas (Unit II: Core 108). Basalts are predominantly nonvesicular, hypocrystalline, aphyric to slightly phyric with intersertal to intergranular textures. Alteration is generally slight to moderate. All the basaltic rocks are cut by ramifying veins of varying widths. Secondary mineral assemblages (including vein fillings) are typical of submarine alteration and zeolite to low greenschist facies metamorphism. The order of crystallization of primary minerals is: olivine, plagioclase, clinopyroxene. This, together with mineral chemistry, characterized by forsteritic olivine (Fo 84-85), highly anorthitic Plagioclase (up to An 90), and in particular the composition of clinopyroxene, are typical of normal mid-ocean ridge basalts (MORB). In terms of Zr/Y (2.9-3.8) and Zr/Nb (21-58), all the analyzed samples plot in the normal MORB field. The chondrite-normalized REE patterns confirm the close affinity with normal MORB type (LaN/SmN: 0.6-0.8). Note that such magmatism does not reveal any evidence of subduction-related geochemical components. The 87Sr/86Sr isotopic ratios range from 0.70339 in pillow lavas to 0.70317 in the least-altered basalts of sill units (ratios reduced to 0.70265-0.70271 by HC1 2.5 N hot leaching), whereas 143Nd/144Nd ratios are 0.51314-0.51326. These values conform with those of normal MORB. Stratigraphy, petrography, and geochemistry of the basaltic rocks recovered at Site 808 appear very similar to those from the Shikoku Basin basement (particularly Sites 442 and 443, DSDP Leg 58), analogously identified as normal MORB.