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.

Geochemistry of ODP Leg 135 basalts

Cr-spinels in cores drilled during Ocean Drilling Program Leg 135 exhibit wide variations in composition and morphology that reflect complex petrogenetic histories. These Cr-spinels are found within basaltic lava flows that erupted in north-trending sub-basins within the Lau Basin backarc. Cr-spinels from Sites 834 and 836 occur as euhedral groundmass grains and inclusions in plagioclase, and range up to 300 ?m in size. These Cr-spinels are similar in composition, morphology, and mode of occurrence to Cr-spinels found within depleted, N-type mid-ocean-ridge basalts (N-MORB), reflecting similar crystallization conditions and host lava composition to N-MORB. Their compositional range is relatively narrow, with Cr/(Cr + Al + Fe3+) (Cr#) and Mg/(Mg + Fe2+) (Mg#) varying from 0.38 to 0.48 and 0.56 to 0.72, respectively; like Cr-spinels from N-MORB, they contain low amounts of TiO2 (0.37%-1.05%) and Fe3+/(Cr + Al + Fe3+) (Fe3+#; <0.11). In contrast, Cr-spinels from Site 839 have much higher Cr# at a given Mg#, with Cr# varying from 0.52 to 0.76 and Mg# varying from 0.27 to 0.75. These Cr-spinels are similar in composition to those from primitive, boninitic or low-Al2O3 arc basalts, sharing their low TiO2 and Fe3+# (typically below 0.35% and 0.1, respectively for spinel grain interiors). Site 839 Cr-spinels occur as small (to 50 µm) euhedra within strongly zoned olivine or as unusually large (to 3 mm), euhedral to subhedral megacrysts. These megacrysts are strongly zoned in Mg#, but they display little zoning in Cr#, providing evidence of strong compositional disequilibria with the host melt. The magnesian cores of the megacrysts crystallized from primitive, near-primary melts derived from harzburgitic or highly depleted lherzolitic sources, and they provide evidence that the Site 839 spinel-bearing lavas were derived by the mixing of melt with a Mg# of 0.75-0.80 and evolved, Cr-spinel barren melt with a Mg# < 0.6 shortly before eruption.

Chemical composition of ultrabasites and composing minerals from the Tonga Trench

A petrologic-geochemical study (petrochemistry, contents of siderophile and certain lithophile elements, composition of rock-forming silicates and accessory chrome spinels) of ultrabasic rocks dredged from the arc side in the northern end of the Tonga deep-sea trench has been carried out. The ultrabasites included harzburgites and dunites. Peridotites show clearly manifested material characteristics of ultrabasic relicts strongly depleted in low-temperature basaltic components. It is suggested that they have arose in the high degree of partial melting (about 30%) of a matrix mantle source of the lherzolite type. Great similarity of the rocks studied with ultrabasites of many ophiolites that are widespread in folded belts indicates that young island arcs are among the most likely geodynamic environments of ophiolite generation.

Geochemistry of ODP Hole 135-839B lavas

Four petrographic lava types occur, ranging from aphyric to moderately phyric clinopyroxene-olivine tholeiitic basalts (Unit 1); olivine-clinopyroxene picritic basalts, sparsely to strongly olivine-phyric (Unit 3-type); olivine-clinopyroxene basalts (clinopyroxene dominant) (Unit 4); and moderately to strongly phyric two-pyroxene-plagioclase basaltic andesites (Unit 9-type). The olivine phyric lavas contain forsteritic olivines (extending to Fo92), and very magnesian Cr-rich spinels similar to those occurring in boninitic lavas. The basaltic andesites are mineralogically and petrographically indistinguishable from the modern Tofua Arc basaltic andesites, one notable feature being the highly calcic cores in plagioclase phenocrysts (up to An95). The forsteritic olivines, the Cr-spinels, and the calcic plagioclases are unlikely to have been precipitated in the lava compositions in which they occur, and are thought to have been incorporated from highly primitive melts by way of mixing processes (as advocated by Allan, this volume). Notwithstanding the evidence for mixing, the major element chemistries of the Unit 1- and Unit 9-type lavas are shown to be consistent with the derivation of the Unit 9-type basaltic andesites by means of fractional crystallization, through magmas of similar chemistry to Unit 1. Some trace element discrepancies in the modeling, and the relative volcanic stratigraphy of Site 839, however, preclude a direct liquid line of descent between the actual recovered units. Trace element data as well as TiO2 and Na2O data clearly illustrate the arc-like affinities of the magmas, with strong highfield-strength element depletion and large-ion-lithophile element enrichment. The abundance patterns are very close to those of the Tofua and Kermadec arc magmas, and also Valu Fa. Pb-, Sr-, and Nd-isotopic compositions indicate closest affinities with a "Pacific" MORB source, apparently characteristic of the western, older part of the Lau Basin. A subduction-related isotopic contribution is, however, inferred. The sources of the Site 839 magmas are thus inferred to be similar to, but less depleted geochemically, than those of the modern Tofua Arc magmas. The Site 839 sequence is interpreted as an older remnant of a volcanic construct of the "proto-Tofua arc", originally developed adjacent to the Tonga Ridge. Opening of the eastern Lau Basin, because of southward migrating propagators, has split and isolated the sequence, leaving it stranded within the modern Lau Basin.

Geochemistry of Qeqertaa xenoliths

This study presents electron microprobe data for dunite xenoliths from a lamprophyre dyke located on the island of Qeqertaa, West Greenland. The minimum age of this dyke is Palaeoproterozoic and it experienced amphibolite facies metamorphism and deformation during that era. The samples consist of nearly 200 xenoliths with a size range of 0.5-8 cm. These dunite xenoliths have olivine Mg#, that range from 80.3 to 94.6 (n = 579) with a mean of 92.6. Orthopyroxene is found in three xenoliths and garnet in five others. The latter suggests the depth of the Qeqertaa xenolith suite to be near the diamond stability-field, which is substantiated by the finding of diamonds in bulk samples of the Qeqertaa dyke. This further indicates the presence of a lithospheric mantle domain dominated by high-Mg# dunite to this depth in Palaeoproterozoic time. Cr-rich spinel, in the 0.1-0.2 mm size range, is found within and between olivine grains in individual xenoliths. These Cr-spinels yield Fe-Mg exchange temperatures of 400-600°C. However, the presence of intermediate spinel compositions spanning the lower temperature solvus suggests that equilibration temperatures were >550°C. Fe3+#, expressed as 100xFe3+/(Fe3++Al+Cr)), is shown to be a useful parameter in order to screen for altered spinel (Fe3+#>10) with disturbed Mg# and Cr#. The screened spinel data (Fe3+#<10) show a distinctly different trend in terms of spinel Cr# versus Mg#, compared to unmetamorphosed xenoliths in Tertiary lavas and dikes from Ubekendt Ejland and Wiedemann Fjord, respectively, also located within the North Atlantic craton. This difference likely reflects amphibolite facies metamorphic resetting of the Qeqertaa xenolith suite by Fe-Mg exchange. Given the similarity of the Qeqertaa xenolith suite with the Ubekendt and Wiedemann suites, in terms of their olivine Mg# and spinel Cr# distribution, high-Mg# dunite is likely to be an important component of the subcontinental lithospheric mantle beneath the North Atlantic craton and appears to have spanned a vertical distance of at least 150 km in this region, even during the Palaeoproterozoic.

Major elements oxides and mineralogy of primary minerals in ODP Hole 195-1201D basalts

The basement cored at Site 1201 (west Philippine Basin) during Ocean Drilling Program Leg 195 consists of a 91-m-thick sequence of basalts, mostly pillow lavas and perhaps one sheet lava flow, with a few intercalations of hyaloclastite and interpillow sedimentary material. Hydrothermal alteration pervasively affected the basalt sequence, giving rise to a variety of secondary minerals such as K-Fe-Mg-clay minerals, oxyhydroxides and clay minerals mixtures, natrolite group zeolites, analcite, alkali feldspar, and carbonate. The primary minerals of pillow and sheet basalts that survived the intense hydrothermal alteration were investigated by electron microprobe with the aim of characterizing their chemical composition and variability. The primary minerals are mostly plagioclase, ranging in composition from bytownite through labradorite to andesine, chromian-magnesian-diopside, and spinels, both Ti magnetite (partially maghemitized) and chromian spinel. Overall, the chemical features of the primary minerals of Site 1201 basalts correspond to the primitive character of the bulk rocks, suggesting that the parent magma of these basalts was a mafic tholeiitic magma that most likely only suffered limited fractional crystallization and crystallized at high temperatures (slightly below 1200°C) and under increasing fO2 conditions. The major element composition of clinopyroxene suggests a backarc affinity of the mantle source of Site 1201 basement.

Abundance of planktic foraminiferal species in sediments at DSDP Sites 10-95, 77-536, and 77-540

Over most of the Gulf of Mexico and Caribbean a hiatus is present between the lower upper Maastrichtian and lowermost Tertiary deposits; sedimentation resumed ~200 ka (upper zone Pla) after the K-T boundary. Current-bedded volcaniclastic sedimentary rocks at Deep Sea Drilling Project (DSDP) Sites 536 and 540, which were previously interpreted as impact-generated megawave deposits of K-T boundary age, are biostratigraphically of pre-K-T boundary age and probably represent turbidite or gravity-How deposits. The top 10 to 20 cm of this deposit at Site 536 contains very rare Micula prinsii, the uppermost Maastrichtian index taxon, as well as low values of Ir (0.6 pbb) and rare Ni-rich spinels. These indicate possible reworking of sediments of K-T boundary age at the hiatus. Absence of continuous sediment accumulation across the K-T boundary in the 16 Gulf of Mexico and Caribbean sections examined prevents their providing evidence of impact-generated megawave deposits in this region. Our study indicates that the most complete trans-K-T stratigraphic records may be found in onshore marine sections of Mexico, Cuba, and Haiti. The stratigraphic records of these areas should be investigated further for evidence of impact deposits.

Geochemistry of ODP Leg 125 peridotites

Ocean Drilling Program Leg 125 recovered serpentined harzburgites and dunites from a total of jive sites on the crests and flanks of two serpen finite seamounts, Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc. These are some of the first extant forearc peridotites reported in the literature and they provide a window into oceanic, supra-subduction zone (SSZ) mantle processes. Harzbutrgites from both seamounts are very refractory with low modal clinopyroxene (<4%), chrome-rich spinels (cx-number = 0.40-0.80), very low incompatible element contents, and (with the exception of amphibole-bearing samples) U-shaped rare earth element (REE) profiles with positive Eu anomalies. Both sets of peridotites have olivine-spinel equilibration temperatures that are low compared with abyssal peridotites, possibly because of water-assisted diffusional equilibration in the SSZ environment However, other features indicate that the harzburgites from the two seamounts have very different origins. Harzburgites from Conical Seamount are characterized by calculated oxygen fugacities between FMQ (fayalite- magnetite- quartz) - 1.1 (log units) and FMQ + 0.4 which overlap those of mid-ocean ridge basalt (MORB) peridotites. Dunites from Conical Seamotmt contain small amounts of clinopyroxene, orthopyroxene and amphibole and are light REE (LREE) enriched. Moreover; they are considerably more oxidized than the harzburgites to which they are spatially related, with calculated oxygen fugacities of FMQ -0.2 toFMQ + 1.2. Using textural and geochemical evidence, we interpret these harzburgites as residual MORB mantle (from 15 to 20 % fractional melting) which has subsequently been modified by interaction with boninitic melt ivithin the mantle wedge, and these dunites as zones of focusing of this melt in which pyroxene has preferentially been dissolved from the harzbutgite protolith. In contrast, harzburgites from Torishima Forearc Seamount give calculated oxygen fugacities between FMQ + 0.8 and FMQ + l.6, similar to those calculated for other subduction-zone related peridotites and similar to those calculated for the dunites (FMQ + 1.2 to FMQ + 1.8) from the same seamount. In this case, we interpret both the harzburgites and dunites as linked to mantle melting (20-25 % fractional melting) in a supra-subduction zone environment The results thus indicate that the forearc is underlain by at least two types of mantle lithosphere, one being trapped or accreted oceanic lithosphere, the other being lithosphere formed by subduction-related melting. They also demonstrate that both types of mantle lithosphere may have undergone extensive interaction with subduction-derived magmas.

Petrology and relict mineralogy of serpentinites at DSDP Leg 84 Holes

Eleven serpentine samples from DSDP Leg 84 and four serpentinized ultramafic samples from Costa Rica and Guatemala were described and their relict mineral compositions measured by electron microprobe to try to determine the origin of the Leg 84 serpentinites and their relationship to the ultramafic rocks of the onshore ophiolites. The Leg 84 samples comprise more than 90% secondary minerals, principally serpentine, with hematitic and opaque oxides, and minor talc and smectites. Four distinct textural types can be identified according to the distribution of opaque phases and smectite. Remnants of spinel, olivine, orthopyroxene, and clinopyroxene occur variously in the samples; spinal occurs in all the samples. Textural evidence suggests that the serpentinites were originally clinopyroxene-bearing harzburgites. Relict mineral compositions are refractory and relatively uniform: olivine, Fo90.6-90.9; orthopyroxene, En90-91; clinopyroxene, Wo47 En50 Fs3; spinels, Cr/Cr + Al = 0.4-0.6. 567A-29-2, 30-35 cm has slightly more magnesian olivines (Fo92) and orthopyroxene, and more aluminous spinels (Cr/Cr + Al = 0.3). These compositions are similar to those inferred for refractory upper-mantle materials and also fall within the range of compositions for relict minerals in abyssal peridotites. They could be of oceanic origin. The onshore samples include serpentinites, a clinopyroxene-bearing harzburgite, and a clinopyroxenite. They too have magnesium-rich silicate assemblages, but relative to the drilled samples have more iron-rich olivines (Fogo) and more aluminous and sodic pyroxenes; spinels which are clearly relicts are very aluminum-rich (Cr/Cr + Al = 0.1-0.25). These samples are most likely mantle materials, but significantly less depleted. Their relationship to the drilled samples is unclear. Serpentinites were the most common basement materials recovered during Leg 84, and there appears to be a bimodal assemblage (basalt/diabase and serpentine) of igneous rocks sampled from the trench slope. Diapirism of serpentine throughout the trench slope and forearc is suggested as an explanation for this distribution of samples.

Chemistry of peridotites from ODP 109-670A

During Leg 109 of the Ocean Drilling Program, about 100 m of serpentinized peridotites were drilled on the western wall of the M.A.R. axial rift valley, 45 km south of the Kane Fracture Zone. The present study reports petrological and mineralogical data obtained from 29 small pieces of these ultramafic rocks, including about 60% serpentinized harzburgites, 26% serpentinized lherzolites, 14% serpentinized dunites, and one sample of olivine websterite. Modal analyses show that all these rocks are plagioclase-free four-phase peridotites equilibrated in the spinel lherzolite facies. The estimated average modal composition of the sample set is about 80% olivine, 14% opx, 5% cpx, and 1% spinel, that is, a cpx-poor lherzolite. The well developed porphyroclastic structures and mineralogical characteristics of these rocks indicate their affinity with the group of residual mantle tectonites, among the abyssal peridotites. Features typical of magmatic cumulates are lacking. The high contents in Al2O3 of the cpx (average 5.4%) and of the opx (average 4.3%) porphyroclasts, the low Cr# of the spinels (average 22.9%), and the rather high content in modal cpx (about 5%), indicate a moderate percentage of melting, of the order of 10%-15%. Site 670 peridotites plot close to the least depleted mantle rocks collected in the oceans in most diagrams used to define the average trend of the ocean-floor peridotites. Microprobe traverses across the cores of the exsolved opx and cpx porphyroclasts permitted the recalculation of the magmatic compositions of these pyroxenes: the 'primitive' opx were equilibrated at about 1300°C, probably at the end of the main melting episodes, whereas the 'primitive' cpx show lower equilibration temperatures, at about 1200°C, reflecting a more complex thermal history. The subsolidus evolution is well recorded, from 1200°C to about 950CC, by the exsolved pyroxenes and the olivine and spinel phases. Unusually high blocking temperatures, close to 1000°C, indicate that the peridotite body was cooled very rapidly between 1000°C and the beginning of serpentinization. Oxygen fugacities, calculated for 10 kb and at the blocking temperatures indicated by the olivine/spinel geothermometer, are close to the usual fugacities calculated in oceanic peridotites and basalts (of the order of 10**-10 to 10**-11, on the QFM buffer). Site 670 peridotites have compositions close to those of the peridotites collected in the Kane Fracture Zone area, and obviously belong to the moderately depleted mantle peridotites which characterize abyssal peridotites collected away from mantle plumes and oceanic islands. In particular, they differ from the highly residual harzburgites collected along the M.A.R. over the Azores bulge.

Geochemistry of DSDP Hole 86-577B samples

THE chemical, mineralogical and isotopic characteristics of deposits at the Cretaceous/Tertiary (K/T) boundary are suggestive of a large impact event, the prime candidate (Sharpton et al., 1992, doi:10.1038/359819a0) being the Chicxulub crater in Yucatan, Mexico. Spinel-bearing spherules, which may be associated with such impacts, have been reported (Smit and Romein, 1985, doi:10.1016/0012-821X(85)90019-6) at several K/T boundary sites worldwide, but their origin is still uncertain. We have examined the spinel-bearing material recovered from K/T boundary deposits at site 577 in the Pacific Ocean (Heath et al., 1985, doi:10.2973/dsdp.proc.86.104.1985) and find two distinct populations of particles: spherules with dendritic spinel textures dispersed throughout the grains and irregularly shaped fragments with spinels essentially confined to the rim. The morphology and composition of the particles are characteristic of melted and partially melted meteoritic ablation debris, but their location is difficult to reconcile with an impact on the Yucatan peninsula, some 10,000 km away. We suggest instead that the spinel-bearing particles at site 577 are derived from the impact of a 2-km asteroid in the Pacific Ocean, and that several accretionary events of this type are required to explain the global distribution of spinel-bearing spherules at the K/T boundary.

Geochemistry of peridotites from ODP Leg 125 diapiric serpentinites

Refractory spinel peridotites were drilled during Leg 125 from two diapiric serpentinite seamounts: Conical Seamount in the Mariana forearc (Sites 778-780) and Torishima Forearc Seamount (Sites 783-784) in the Izu-Ogasawara forearc. Harzburgite is the predominant rock type in the recovered samples, with subordinate dunite; no lherzolite was found. The harzburgite is diopside-free to sparsely diopside-bearing, with modal percentages of diopside that range from 0% to 2%. Spinels in the harzburgites are chrome-rich (Cr/[Cr + Al] = 0.38-0.83; Fe3+/[Fe3+ + Cr + Al] = 0.01-0.07). Olivine and orthopyroxene are magnesian (Mg# = 0.92). Discrete diopsides reveal extreme depletion of light rare earth elements. Primary hornblende is rare. The bulk major-element chemistry shows low average values of TiO2 (trace), Al2O3 (0.55%) and CaO (0.60%), but high Mg# (0.90). These rocks are more depleted than the abyssal peridotites from the mid-oceanic ridge. They are interpreted as residues of extensive partial melting (= 30%), of which the last episode was in the mantle wedge, probably associated with the generation of incipient island-arc magma, including boninite and/or arc-tholeiite. These depleted peridotites probably represent the residues of melting within mantle diapirs that developed within the mantle wedge.

Whole rock and Cr-rich spinel geochemistry of ODP Legs 152 and 163 and DSDP Hole 38-338 samples

Coring during Ocean Drilling Program and Deep Sea Drilling Project Legs 163, 152, 104, 81, and 38 recovered sequences of altered basalt from North Atlantic seaward-dipping reflector sequences (SDRS) erupted during the initial rifting of Greenland from northern Europe and likely associated with excessive mantle temperatures caused by an impacting mantle plume head. Cr-rich spinel is found abundantly as inclusions and groundmass crystals within the olivine-rich lavas of Hole 917A (Leg 152) cored into the Southeast Greenland SDRS, but only rarely as inclusions within plagioclase in the lavas of the Vøring Plateau SDRS, and it is absent from other cored SDRS lavas from the Rockall Plateau and Southeast Greenland. Eruptive melt compositions determined from inferred, thermodynamically-defined, spinel-melt exchange equilibria indicate that the most primitive melts represented by Hole 917A basalts have Mg/(Mg + Fe2+) at least as high as 0.70 and approach near-primary mantle melt compositions. In contrast, Cr-rich spinels from Hole 338 (Leg 38) lavas on the Vøring Plateau SDRS give evidence for melt with Mg/(Mg + Fe2+) only as high as 0.64. This study underlines that primitive melts similar to those from Hole 917A comprise only a small fraction of the eruptive North Atlantic SDRS melts, and that most SDRS basalts were, in fact, too evolved to have precipitated Cr-rich spinel, with true melt Mg/(Mg + Fe2+) likely below 0.60. The evolved nature of the SDRS basalts implies large amounts of fractionation at the base of the crust or deep within it, consistent with seismic results that indicate an abnormally thick Layer 3 underlying the SDRS.

Estudio teórico de propiedades termodinámicas y optoelectronicas de nuevos materiales fotovoltaicos de banda intermedia = Theoretical study of thermodynamic and optoelectronic properties of new intermediate band photovoltaic materials

Los materiales de banda intermedia han atraido la atención de la comunidad científica en el campo de la energía solar fotovoltaica en los últimos años. Sin embargo, con el objetivo de entender los fundamentos de las células solares de banda intermedia, se debe llevar a cabo un estudio profundo de la características de los materiales. Esto se puede hacer mediante un modelo teórico usando Primeros Principios. A partir de este enfoque se pueden obtener resultados tales como la estructura electrónica y propiedades ópticas, entre otras, de los semiconductores fuertemente dopados y sus precursores. Con el fin de desentrañar las estructuras de estos sistemas electrónicos, esta tesis presenta un estudio termodinámico y optoelectrónico de varios materiales fotovoltaicos. Específicamente se caracterizaron los materiales avanzados de banda intermedia y sus precursores. El estudio se hizo en términos de caracterización teórica de la estructura electrónica, la energética del sistema, entre otros. Además la estabilidad se obtuvo usando configuraciones adaptadas a la simetría del sistema y basado en la combinatoria. Las configuraciones de los sitios ocupados por defectos permiten obtener información sobre un espacio de configuraciones donde las posiciones de los dopantes sustituidos se basan en la simetría del sólido cristalino. El resultado puede ser tratado usando elementos de termodinámica estadística y da información de la estabilidad de todo el espacio simétrico. Además se estudiaron otras características importantes de los semiconductores de base. En concreto, el análisis de las interacciones de van der Waals fueron incluidas en el semiconductor en capas SnS2, y el grado de inversión en el caso de las espinelas [M]In2S4. En este trabajo además realizamos una descripción teórica exhaustiva del sistema CdTe:Bi. Este material de banda-intermedia muestra características que son distintas a las de los otros materiales estudiados. También se analizó el Zn como agente modulador de la posición de las sub-bandas prohibidas en el material de banda-intermedia CuGaS2:Ti. Analizándose además la viabilidad termodinámica de la formación de este compuesto. Finalmente, también se describió el GaN:Cr como material de banda intermedia, en la estructura zinc-blenda y en wurtztite, usando configuraciones de sitios ocupados de acuerdo a la simetría del sistema cristalino del semiconductor de base. Todos los resultados, siempre que fue posible, fueron comparados con los resultados experimentales. ABSTRACT The intermediate-band materials have attracted the attention of the scientific community in the field of the photovoltaics in recent years. Nevertheless, in order to understand the intermediate-band solar cell fundamentals, a profound study of the characteristics of the materials is required. This can be done using theoretical modelling from first-principles. The electronic structure and optical properties of heavily doped semiconductors and their precursor semiconductors are, among others, results that can be obtained from this approach. In order to unravel the structures of these crystalline systems, this thesis presents a thermodynamic and optoelectronic study of several photovoltaic materials. Specifically advanced intermediate-band materials and their precursor semiconductors were characterized. The study was made in terms of theoretical characterization of the electronic structure, energetics among others. The stability was obtained using site-occupancy-disorder configurations adapted to the symmetry of the system and based on combinatorics. The site-occupancy-disorder method allows the formation of a configurational space of substitutional dopant positions based on the symmetry of the crystalline solid. The result, that can be treated using statistical thermodynamics, gives information of the stability of the whole space of symmetry of the crystalline lattice. Furthermore, certain other important characteristics of host semiconductors were studied. Specifically, the van der Waal interactions were included in the SnS2 layered semiconductor, and the inversion degree in cases of [M]In2S4 spinels. In this work we also carried out an exhaustive theoretical description of the CdTe:Bi system. This intermediate-band material shows characteristics that are distinct from those of the other studied intermediate-band materials. In addition, Zn was analysed as a modulator of the positions of the sub-band gaps in the CuGaS2:Ti intermediate-band material. The thermodynamic feasibility of the formation of this compound was also carried out. Finally GaN:Cr intermediate-band material was also described both in the zinc-blende and the wurtztite type structures, using the symmetry-adapted-space of configurations. All results, whenever possible, were compared with experimental results.

Modes of occurrence and geochemistry at DSDP Holes 69-505A and 69-505B

The compositions of chrome spinels of Costa Rica Rift basalts from Deep Sea Drilling Project Site 505 vary depending on their occurrences as (1) inclusions in olivine crystals, (2) inclusions in Plagioclase crystals, and (3) isolated crystals in variolitic or glassy samples. The variations are a consequence of (1) changes of melt compositions as crystallization proceeds, and (2) contrasting behavior of olivine and Plagioclase in competition with spinels for Al and Mg. Some spinels have skeletal rims compositionally less magnesian than mineral cores; however, the cores do not appear to be xenocrysts, unlike some texturally similar spinels in Mid-Atlantic Ridge basalts.