Silicate mineralogy of basalts at DSDP Leg 54 Holes

Basalts drilled from the East Pacific Rise, OCP Ridge, and Siqueiros fracture zone during Leg 54 are texturally diverse. Dolerites are equigranular at Sites 422 and 428 and porphyritic, with phenocrysts of plagioclase (An69.73) and Ca-rich clinopyroxene (Ca42Mg48Fe10) at Site 427. The East Pacific Rise lavas and some of those from the OCP Ridge are fine-grained and porphyritic. The majority of the large crystals are clustered skeletal glomerocrysts of plagioclase An64-77), together with olivine (Fo80-87), Ca-rich clinopyroxene, or both. Euhedral phenocrysts of plagioclase, together with olivine, Carich clinopyroxene, and Cr-Al spinel in some cases, occur in most of the fine-grained lavas. These phenocrysts are small (maximum dimension <1 mm in all but one sample), sparse (combined modal amount <1% in all samples), and distinctive from the megacrysts which characterize many ocean-floor lavas. In two East Pacific Rise lavas, zoned plagioclase (An83 cores) is the sole phenocryst phase. In other porphyritic lavas from all the main East Pacific Rise and OCP Ridge units drilled during Leg 54, the plagioclase phenocrysts contain cores of bytownite (An79-87) surrounded by more-sodic feldspar (An67-77). Core/rim relationships vary from continuous normal zoning, through discontinuous zoning, to extensive resorption of the calcic cores in some samples. The compositions of the plagioclase calcic cores are systematically related to those of the glomerophyric plagioclase and olivine in the lavas containing them. Furthermore, only one compositional population of calcic cores occurs in each rock. The possible causes of these relationships are far from clear. Magma mixing, although superficially applicable, is inconsistent with important aspects of the phenocryst mineralogy of these particular lavas. A more satisfactory model to explain both phenocryst zoning and rapid glomerocryst growth immediately before extrusion may be constructed by postulating influx of water into the upwelling magmas within Layer 3 of the oceanic crust beneath the East Pacific Rise, and subsequent loss of part of this water during effervescence within feeder dykes between Layer 3 and the ocean floor. It is shown that this model is fully consistent with published data on water and carbon dioxide contents and ratios in the pillow-margin glasses, vesicles, and phenocryst inclusions of ocean-floor basalts. The evidence for the precipitation of plagioclase- dominated crystalline assemblages from these magmas in the upper part of Layer 3 is concordant with recent geophysically based modeling of the structure of the East Pacific Rise. Calcium-rich clinopyroxenes in dolerites from the OCP Ridge and Siqueiros fracture zone show radial, oscillatory, and sector-zoning. In Sample 428A-5-2 (Piece 5a), the compositional trends resulting from this zoning closely resemble those of the pyroxenes in some lunar lavas. The controls on crystallization of interstitial pigeonite - epitaxial upon augite - in this rock are discussed. Both sector-zoning of the augite and nucleation of pigeonite within microvolumes of magma with a low Ca(Mg + Fe) ratio appear to be important factors.

Petrology and isotope characteristics of basalts from ODP Hole 111-504B

Petrography and isotope geochemical characteristics of H, O, S, Sr, and Nd have been described for basalts recovered from Hole 504B during Leg 111 of the Ocean Drilling Program. The petrographic and chemical features of the recovered basalts are similar to those obtained previously (DSDP Legs 69, 70, and 83); they can be divided into phyric (plagioclase-rich) and aphyric (Plagioclase- and clinopyroxene-rich) basalts and show low abundances of TiO2, Na2O, K2O, and Sr. This indicates that the basalts belong to Group D, comprising the majority of the upper section of the Hole 504B. The diopside-rich nature of the clinopyroxene phenocrysts and Ca-rich nature of the Plagioclase phenocrysts are also consistent with the preceding statement. The Sr and Nd isotope systematics (average 87Sr/86Sr = 0.70267 ± 0.00007 and average 143Nd/144Nd = 0.513157 ± 0.000041) indicate that the magma sources are isotopically heterogeneous, although the analyzed samples represent only the lowermost 200-m section of Hole 504B. The rocks were subjected to moderate hydrothermal alteration throughout the section recovered during Leg 111. Alteration is limited to interstices, microfractures, and grain boundaries of the primary minerals, forming chlorite, actinolite, talc, smectite, quartz, sphene, and pyrite. In harmony with the moderate alteration, the following alteration-sensitive parameters show rather limited ranges of variation: H2O = 1.1 ±0.2 wt%, dD = - 38 per mil ± 4 per mil, d180 = 5.4 per mil ± 0.3 per mil, total S = 562 ± 181 ppm, and d34S = 0.8 per mil ± 0.3 per mil. Based on these data, it was estimated that the hydrothermal fluids had dD and d180 values only slightly higher than those of seawater, the water/rock ratios were as low as 0.02-0.2, and the temperature of alteration was 300°-400°C. Sulfur exists predominantly as pyrite and in minor quantities as chalcopyrite. No primary monosulfide was detected. This and the d34S values of pyrite (d34S = 0.8 per mil) suggest that primary pyrrhotite was almost completely oxidized to pyrite by reaction with hydrothermal fluids containing very little sulfate.

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 of basalts from DSDP Hole 66-487

Basaltic rocks recovered at the Middle America Trench area off Mexico are typical plagioclase-olivine phyric abyssal tholeiites containing less than 0.2 wt.% K2O. Phenocrysts of plagioclase and olivine usually make up the aggregate. Plagioclase phenocrysts are Ca-rich and up to An90. Olivine phenocrysts, which are always attached to plagioclase phenocrysts, are magnesian, Fo88 to Fo89, and contain 0.2 to 0.3 wt. % of NiO. Plagioclase phenocrysts contain numerous glass inclusions with the Mg/Mg+Fe atomic ratio of 0.70 to 0.73, which is distinctly higher than the same ratio of the bulk rock (0.62-0.63). Olivine of Fo88 to Fo89 is equilibrated with the liquid with an Mg/Mg+Fe atomic ratio of about 0.7, assuming the KDMg-Fe between liquid and olivine of 0.3. Small droplets of glass within glass inclusions in plagioclase are more enriched in K2O and volatiles than the host glass. This enrichment may have been caused by the extraction of Al2O3 as plagioclase from the trapped liquid and implies its immiscibility. Aggregates of plagioclase with small amounts of olivine may have been floated from more primitive magma with an Mg/Mg+Fe atomic ratio of about 0.7, judging from the chemical characteristics mentioned above. Flotation must have occurred at relatively high pressure. Large crystals of plagioclase and smaller crystals of olivine are xenocryst rather than phenocryst. Parental magma of Leg 66 basalt was high-MgO olivine tholeiite.

Geochemistry and mineralogy of ultramafic rocks from conical seamount

The Mariana arc-trench system, the easternmost of a series of backarc basins and intervening remnant arcs that form the eastern edge of the Philippine Sea Plate, is a well-known example of an intraoceanic convergence zone. Its evolution has been studied by numerous investigators over nearly two decades (e.g., Kang, 1971; Uyeda and Kanamori, 1979; LaTraille and Hussong, 1980; Fryer and Hussong, 1981; Mrosowski et al., 1982; Hussong and Uyeda, 1981; Bloomer and Hawkins, 1983; Karig and Ranken, 1983; McCabe and Uyeda, 1983; Hsui and Youngquist, 1985; Fryer and Fryer, 1987; Johnson and Fryer, 1988; Johnson and Fryer, 1989; Johnson et al., 1991). The Mariana forearc has undergone extensive vertical uplift and subsidence in response to seamount collision, to tensional and rotational fracturing associated with adjustments to plate subduction, and to changes in the configuration of the arc (Hussong and Uyeda, 1981; Fryer et al., 1985). Serpentine seamounts, up to 2500 m high and 30 km in diameter, occur in a broad zone along the outer-arc high (Fryer et al., 1985; Fryer and Fryer, 1987). These seamounts may be horsts of serpentinized ultramafic rocks or may have been formed by the extrusion of serpentine muds. Conical Seamount, one of these serpentine seamounts, is located within this broad zone of forearc seamounts, about 80 km from the trench axis, at about 19°30'N. The seamount is approximately 20 km in diameter and rises 1500 m above the surrounding seafloor. Alvin submersible, R/V Sonne bottom photography, seismic reflection, and SeaMARC II studies indicate that the surface of this seamount is composed of unconsolidated serpentine muds that contain clasts of serpentinized ultramafic and metamorphosed mafic rocks, and authigenic carbonate and silicate minerals (Saboda et al., 1987; Haggerty, 1987; Fryer et al., 1990; Saboda, 1991). During Leg 125, three sites were drilled (two flank sites and one summit site) on Conical Seamount to investigate the origin and evolution of the seamount. Site 778 (19°29.93'N, 146°39.94'E) is located in the midflank region of the southern quadrant of Conical Seamount at a depth of 3913.7 meters below sea level (mbsl) (Fig. 2). This site is located in the center of a major region of serpentine flows (Fryer et al., 1985, 1990). Site 779 (19°30.75'N, 146°41.75'E), about 3.5 km northeast of Site 778, is located approximately in the midflank region of the southeast quadrant of Conical Seamount, at a depth of 3947.2 mbsl. This area is mantled by a pelagic sediment cover, overlying exposures of unconsolidated serpentine muds that contain serpentinized clasts of mafic and ultramafic rocks (Fryer et al., 1985, 1990). Site 780 (19°32.5'N, 146°39.2'E) is located on the western side of Conical Seamount near the summit, at a depth of 3083.4 mbsl. This area is only partly sediment covered and lies near active venting fields where chimney structures are forming (Fryer et al., 1990).

Composition of sulfide minerals of ODP Hole 209-1268A

This paper presents sulfide mineral occurrence, abundance, and composition in samples from hydrothermally altered peridotite and gabbro recovered during Ocean Drilling Program (ODP) Leg 209 from south of the 15°20'N Fracture Zone on the Mid-Atlantic Ridge at Site 1268. Most of the sulfide minerals occur in veins and halos around veins in serpentinized peridotite. The only sulfide phases reported that occur in proximity to gabbro are those associated with a mafic intrusion into serpentinized peridotite. Sulfide mineral species change predictably downsection but are perturbed coincident with a breccia interpreted to be generated by intrusion of a gabbroic magma. The general downhole trend suggests sulfide mineral precipitation in conditions with decreasing sulfur and oxygen fugacity. Sulfide minerals that indicate precipitation at relatively higher sulfur and oxygen fugacity occur in the central core of the intrusion breccia. Sphalerite makes a fleeting appearance in the sulfide mineral assemblage in samples from the lower part of the intrusion breccia. Strongly contrasting pyrite compositions suggest at least two episodes of pyrite precipitation, but there is no clear morphological distinction between phases. Heazelwoodite, tentatively identified in shipboard examinations, could not be confirmed in this study.

Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

Petrology and origin of basalts at DSDP Hole 66-487

The volcanism of Central America, according to current theory (Pichler and Weyl, 1973; Stoiber and Carr, 1974; Hey, 1977), is related to the subduction of the Cocos Plate under the North American lithospheric plate and the melting of ocean crust material in the subduction zone (Green and Ringwood, 1968; Dickinson, 1970, Fitton, 1971). Since Cocos Plate subduction occurs at the rate of more than 7 cm/y. (Hey et al., 1977), basalts underlying upper Miocene sediments of the Middle America Trench outer slope, penetrated in Hole 487 (Fig. 1) during Leg 66 (Moore et al., 1979), should have formed far from their present position if current theory is accurate. Present manifestations of basaltic magmatism in adjacent areas of the Pacific derive from the axial part of the East Pacific Rise, the Galapagos spreading center, and transform fracture zones. The question arises: Are there analogs of the Middle America Trench basalts among magmatic cock associated with these modern features, or do the trench basalts have some other origin?

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.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

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.

Grain size, mineral and chemical compositions of modern deposits fron the northern Caspian Sea and the Volga River delta

Comprehensive investigations revealed that modern deposits in the northern Caspian Sea involve terrigenous sands and aleurites with admixture of detritus and intact bivalve shells, including coquina. Generally, these deposits overlay dark grayish viscous clays. Similar geological situation occurs in the Volga River delta; however, local deposits are much poorer in biogenic constituents. Illite prevails among clay minerals. In coarse aleurite fraction (0.100-0.050 mm) heavy transparent minerals are represented mostly by epidotes, while light minerals - mostly by quartz and feldspars. Sedimentary material in the Volga River delta is far from completely differentiated into fractions due to abundant terrigenous inflows. Comparatively better grading of sediments from the northern Caspian Sea is due to additional factors such as bottom currents and storms. When passing from the Volga River delta to the northern Caspian Sea, sediments are enriched in rare earth elements (except Eu), Ca, Au, Ni, Se, Ag, As, and Sr, but depleted in Na, Rb, Cs, K, Ba, Fe, Cr, Co, Sc, Br, Zr, ??, U, and Th. Concentrations of Zn remain almost unchanged. Sedimentation rates and types of recent deposits in the northern Caspian Sea are governed mainly by abundant runoff of the Volga River.