Magnetic properties, grain sizes and minerals at DSDP Site 83-504B

Twenty-seven samples from the Leg 83 section of Hole 504B have been investigated using magnetic, optical, and electron optical methods. The primary magnetic mineral to crystallize was titanomagnetite of approximate composition Fe2.4Ti0.6O4 (TM60), but none survives, nor is there evidence of titanomaghemite produced by oxidation of TM60. The average measured magnetic properties can be interpreted in terms of magnetite, Fe3O4, having average grain size of <1 µm and present in average volume concentration of - 0.5%. The intensity of the natural remanent magnetization (NRM) of the rocks could also be accounted for as being a thermoremanence carried by this mineral. Although the heterogeneity of the titanomagnetite grains could be detected optically, the texture of the intergrown phases is poorly developed. In some samples from the massive units of the lower part of the section, trellis patterns were visible. The Fe3O4 present in the intergrowths is too intimately mixed with the other intergrown phases to be revealed by electron microprobe analysis that simply returns the bulk composition of the intergrowth (oxidized TM60). The path by which the mineral assemblage evolved from TM60 to an Fe304-containing intergrowth, under the temperature and pressure conditions obtaining in the Leg 83 section, makes interesting speculation. Deuteric oxidation, maghemitization/inversion, or some hypothetical low-temperature/high-pressure oxidation by a leaching-of-iron process may all play roles.

Hydrous and anhydrous pyrolysis of DSDP Leg 75 kerogens

The aliphatic hydrocarbon distributions obtained from the natural bitumens of three Leg 75 sediments were compared using computerised gas chromatography-mass spectrometry (C-GC-MS). The kerogens isolated from these sediments were heated in sealed tubes at 330°C using the techniques of hydrous (i.e. heating kerogen in the presence of water) and anhydrous pyrolysis (i.e. heating dry kerogen alone). These experiments were then repeated at a lower temperature (280°C). At 330°C, under anhydrous conditions, considerable destruction of biomarkers in the ancient kerogens (i.e. pre-Tertiary) occurred, whereas with water present significant amounts of hopanes were obtained. However, with more recent kerogens (which contain larger amounts of chemically bound water), both anhydrous and hydrous pyrolysis gave a similar suite of biological markers, in which long chain acyclic isoprenoids (C40) are significant components. Lowering the temperature of pyrolysis to 280°C yielded biological markers under both hydrous and anhydrous conditions for all kerogens. n-Alkenes were not detected in any of the pyrolysates; however, a single unknown triterpene was discovered in several of the hydrous and anhydrous pyrolysates. The results tentatively indicate that the chief value to petroleum research of kerogen hydrous pyrolysis lies in its ability to increase the yield of pyrolysate. High temperature hydrous pyrolysis (280-330°C), under high pressure (2000 psi), does not appear to mimic natural conditions of oil generation. However, this study does not take into account whole rock pyrolysis.

(Table 1) Compressional-wave and shear-wave velocities and elastic constants from DSDP Legs 69 and 70

Shear-wave and compressional-wave velocities of 26 basalt samples collected at Site 504 during Deep Sea Drilling Project Legs 69 and 70 were measured at elevated confining pressures. The young basalts have higher velocities than average DSDP basalts, because of their lack of alteration. Measurements of sample porosity are combined with laboratory and in situ velocity measurements to yield estimates of total crustal porosity: 13% at the top of Layer 2, and very low porosity below a depth of 2.0 km.

Geochemistry on rocks from Shackleton Range

During the GEISHA expedition (Geologische Expedition in die Shackleton Range 1987/88), the Pioneers Escarpment was visited and sampled extensively for the first time. Most of the rock types encountered represent amphibolite facies metamorphics, but evidence for granulite facies conditions was found in cores of garnet. These conditions must have been at least partly reached during the peak of metamorphism. For the Pioneers Escarpment a varicolored succession of sedimentary and bimodal volcanic origin is typical. It comprises: quartzites muscovite quartzite, sericite quartzite, fuchsite quartzite, garnet-quartz schists etc.; pelites: mica schists and plagioclase or plagioclase-microcline gneisses, aluminous schists; marls and carbonates: grey meta-limestones, carbonaceous quartzites, but also pure white, often fine-grained, saccharoidal marble, or a variety of tremolite marble, olivine (forsterite) marble, diopside-clinopyroxene-tremolite marble, etc.; basic volcanic rocks: amphibole fels, amphibolite schist, garnet amphibolite, and acidic to intermediate volcanic rocks: garnet-biotite schist, epidote-biotite-plagioclase gneiss, microcline gneiss. These rocks are considered to be a supracrustal unit, called the Pioneers Group. In the easternmost parts of the Pioneers Escarpment, e.g. at Vindberget, nonmetamorphic shales, sandstones and greywackes crop out, which are cover rocks of possibly Jurassic age. These metasediments, which represent a quartz-pelite-carbonate (QPC) association, indicate that deposition took place on a stable shelf, i.e. on the submerged rim of a craton. Marine shallow-water sedimentation including marls and aluminous clays form the protoliths. The volcanics may be part of a bimodal volcanics-arkose-conglomerate (BVAC) association. Geochemical analyses support the assumption of volcanic protoliths. This is demonstrated especially by the elevated amounts of the immobile, incompatible high-field-strength elements (HFSE) Nb, Ta, Ti, Y, and Zr encountered in some of the gneisses. Microscopic investigation suggests the existence of ortho-amphibolites. This is confirmed by the geochemistry. A bimodal volcanic association is evident. The amphibolites plot in both the tholeiite and calc-alkaline fields. The acidic volcanics are mainly rhyolitic. The sediments and volcanics were subjected to conditions of 10-11 kbar and 600°C during the peak of metamorphism, i.e. granulite facies metamorphism, which can be deduced from the Fe mole ratios of 0.71-0.73 in the garnet cores. Due to the relatively low temperatures, no anatectic melting took placc. The rims of the garnets show a Fe mole ratio of 0.84-0.86, and the coexisting mineral association garnet-biotite-staurolite-kyanite indicate amphibolite facies. The thermobarometry shows P-T conditions of 5-6 kbar and 570-580°C for this stage. The metamorphic history indicates deep burial at depths down to 35 km (subduction?) i.e. high pressure metamorphism, followed by pressure release due to uplift associated with retrograde metamorphism. This may have happened during a pre-Ross metamorphic event or orogeny. The Ross Orogeny at about 500 Ma probably just led to the weak greenschist facies overprint that is evident in the rocks of the Pioneers Group. Finally, sedimentation resumed in the area of the present Shackleton Range, or at least in the eastern part of the Pioneers Escarpment, probably when detritus from erosion of the basement (Read Group and Pioneers Group) was deposited, forming sandstones and greywackes of possibly Jurassic age. There is no indication that these sediments belong to the former Turnpike Bluff Group.

Geochemistry of subducted volcaniclastic sediments from Mariana arc magmas

The phase relations of natural volcaniclastic sediments from the west Pacific Ocean were investigated experimentally at conditions of 3-6 GPa and 800-900 °C with 10 wt.% added H2O (in addition to ~ 10 wt.% structurally-bound H2O) to induce hydrous melting. Volcaniclastic sediments are shown to produce a sub-solidus assemblage of garnet, clinopyroxene, biotite, quartz/coesite and the accessory phases rutile ± Fe-Ti oxide ± apatite ± monazite ± zircon. Hydrous melt appears at temperatures exceeding 800-850 °C, irrespective of pressure. The melt-producing reaction consumes clinopyroxene, biotite and quartz/coesite and produces orthopyroxene. These phase relations differ from those of pelagic clays and K-bearing mid ocean ridge basalts (e.g. altered oceanic crust) that contain phengite, rather than biotite, as a sub-solidus phase. Despite their relatively high melt productivity, the wet solidus for volcaniclastic sediments is found to be higher (825-850 °C) than other marine sediments (700-750 °C) at 3 GPa. This trend is reversed at high-pressure conditions (6 GPa) where the biotite melting reaction occurs at lower temperatures (800-850 °C) than the phengite melting reaction (900-1000 °C). Trace element data was obtained from the 3 GPa run products, showing that partial melts are depleted in heavy rare earth elements (REE) and high field strength elements (HFSE), due to the presence of residual garnet and rutile, and are enriched in large ion lithophile elements (LILE), except for Sr and Ba. This is in contrast to previous experimental studies on pelagic sediments at sub-arc depths, where Sr and Ba are among the most enriched trace elements in glasses. This behavior can be partly attributed to the presence of residual apatite, which also host some light REE in our supra-solidus residues. Our new experimental results account for a wide range of trace element and U-series geochemical features of the sedimentary component of the Mariana arc magmas, including imparting a substantial Nb anomaly to melts from an anomaly-free protolith.

Seismic velocities and elastic properties of gabbroic rocks from ODP Hole 118-735B

The nearly continuous recovery of 0.5 km of generally fresh, layer 3 gabbroic rocks at Hole 735B, especially near the bottom of the section, presents scientists an unusual opportunity to study the detailed elastic properties of the lower oceanic crust. Extending compressional-wave and density shipboard measurements at room pressure, Vp and Vs were measured at pressures from 20 to 200 MPa using the pulse transmission method. All of the rocks exhibit significant increases in velocity with increasing pressure up to about 150 MPa, a feature attributed to the closing of microcrack porosity. Measured velocities reflect the mineralogical makeup and microstructures acquired during the tectonic history of Hole 735B. Most of the undeformed and unaltered gabbros are approximately 65:35 plagioclase/clinopyroxene rocks plus olivine or oxide minerals, and the observed densities and velocities are fully consistent with the Voigt-Reuss-Hill (VRH) averages of the component minerals and their proportions. Depending on their olivine content, the predominant olivine gabbros at 200 MPa have average Vp = 7.1 ± 0.2 km/s, Vs = 3.9 ± 0.1 km/s, and grain densities of 2.95 ± 0.5 g/cm3. The less abundant iron-titanium (Fe-Ti) oxide gabbros average Vp = 6.75 ± 0.15 km/s, Vs = 3.70 ± 0.1 km/s, and grain densities of 3.22 ± 0.05 g/cm3, reflecting the higher densities and lower velocities of oxide minerals compared to olivine. About 30% of the core is plastically deformed, and the densities and directionally averaged velocities of these shear-zone tectonites are generally consistent with those of the gabbros, their protoliths. Three sets of observations indicate that the shear-zone metagabbros are elastically anisotropic: (1) directional variations in Vp, both vertical and horizontal and with respect to foliation and lineation; (2) discrepancies among Vp values for the horizontal cores and the VRH averages of the component minerals and their mineral proportions, suggesting preferred crystallographic orientations of anisotropic minerals; and (3) variations of Vs of up to 7%, with polarization directions parallel and perpendicular to foliation. Optical inspection of thin sections of the same samples indicates that plagioclase feldspar, clinopyroxene, and amphibole typically display crystallographic-preferred orientations, and this, plus the elastic anisotropy of these minerals, suggests that preferred orientations are responsible for much of the observed anisotropy, particularly at high pressure. Alteration tends to be localized to brittle faults and brecciated zones, and typical alteration minerals are amphibole and secondary plagioclase, which do not significantly change the velocity-density relationships.

Geochemistry and radiogenic isotopes of ODP Hole 157-953C lavas

The Canary Island primitive basaltic magmas are thought to be derived from an HIMU-type upwelling mantle containing isotopically depleted (NMORB)-type component having interacted with an enriched (EM)-type component, the origin of which is still a subject of debate. We studied the relationships between Ni, Mn and Ca concentrations in olivine phenocrysts (85.6-90.0 mol.% Fo, 1,722-3,915 ppm Ni, 1,085-1,552 ppm Mn, 1,222-3,002 ppm Ca) from the most primitive subaerial and ODP Leg 157 high-silica (picritic to olivine basaltic) lavas with their bulk rock Sr-Nd-Pb isotope compositions (87Sr/86Sr = 0.70315-0.70331, 143Nd/144Nd = 0.51288-0.51292, 206Pb/204Pb = 19.55-19.93, 207Pb/204Pb = 15.60-15.63, 208Pb/204Pb = 39.31-39.69). Our data point toward the presence of both a peridotitic and a pyroxenitic component in the magma source. Using the model (Sobolev et al., 2007, Science Vol 316) in which the reaction of Si-rich melts originated during partial melting of eclogite (a high pressure product of subducted oceanic crust) with ambient peridotitic mantle forms olivine-free reaction pyroxenite, we obtain an end member composition for peridotite with 87Sr/86Sr = 0.70337, 143Nd/144Nd = 0.51291, 206Pb/204Pb = 19.36, 207Pb/204Pb = 15.61 and 208Pb/204Pb = 39.07 (EM-type end member), and pyroxenite with 87Sr/86Sr = 0.70309, 143Nd/144Nd = 0.51289, 206Pb/204Pb = 20.03, 207Pb/204Pb = 15.62 and 208Pb/204Pb = 39.84 (HIMU-type end member). Mixing of melts from these end members in proportions ranging from 70% peridotite and 30% pyroxenite to 28% peridotite and 72% pyroxenite derived melt fractions can generate the compositions of the most primitive Gran Canaria shield stage lavas. Combining our results with those from the low-silica rocks from the western Canary Islands (Gurenko et al., 2009, doi:10.1016/j.epsl.2008.11.013), at least four distinct components are required. We propose that they are (1) HIMU-type pyroxenitic component (representing recycled ocean crust of intermediate age) from the plume center, (2) HIMU-type peridotitic component (ancient recycled ocean crust stirred into the ambient mantle) from the plume margin, (3) depleted, MORB-type pyroxenitic component (young recycled oceanic crust) in the upper mantle entrained by the plume, and (4) EM-type peridotitic component from the asthenosphere or lithosphere above the plume center.

Experimental petrology of basement basaltic rocks from ODP Leg 127/128 samples

The relatively fresh basement basaltic rocks cored at Sites 794 and 797 during ODP Legs 127 and 128 show compositional variations suggesting the following: (1) the aphyric rocks might be differentiated from compositional equivalents of the aphyric sample with the lowest FeO*/MgO (Sample 127-797C-12R-4, 35-37 cm); and (2) the plagioclase-phyric rocks (i.e., another constituent of the basement basaltic rocks from the sites) may be derivatives from the same parents; in this case, however, crystallized plagioclase was not effectively removed. Melting experiments were conducted for Sample 127-797C-12R-4, 35-37 cm, and the differentiation processes for the basement basaltic rocks were assessed. The high-pressure melting-phase relation can not account for the compositional variation of the aphyric rocks, suggesting that the variation was developed at relatively low pressure where olivine and plagioclase fractionation was followed by Ca-rich clinopyroxene fractionation. The density of Sample 127-797C-12R-4,35-37 cm, is comparable to that of plagioclase at some depth, but at still relatively low pressure, making it possible that the liquidus plagioclase was retained in the successive liquids to produce the plagioclase-phyric rocks. According to backtrack calculation assuming the olivine maximum fractionation, Sample 127-797C-12R-4, 35-37 cm, was differentiated from primary picritic high-Al basalt magma. The estimated primary magma composition was experimentally proved to coexist with harzburgite mantle at about 14 kbar, suggesting relatively shallow production (approximately 40-50 km below surface) of the rifting-related primary magma.

(Table 1) Stable carbon isotope record and total nitrogen concentration in ODP Hole 175-1085B sediments

Variations in the strength of coastal upwelling in the South East Atlantic Ocean and summer monsoonal rains over South Africa are controlled by the regional atmospheric circulation regime. Although information about these parameters exists for the last glacial period, little detailed information exists for older time periods. New information from ODP Site 1085 for Marine Isotope Stages (MIS) 12-10 shows that glacial-interglacial productivity trends linked to upwelling variability followed a pattern similar to the last glacial cycle, with maximums shortly before glacial maxima, and minimums shortly before glacial terminations. During the MIS-11/10 transition, several periodic oscillations in productivity and monsoonal proxies are best explained by southwards shifts in the southern sub-tropical high-pressure cells followed by abrupt northwards shifts. Comparison to coeval sea-surface temperature measurements suggests that these monsoonal cycles were tightly coupled to anti-phased hemispheric climate change, with an intensified summer monsoon during periods of Northern (Southern) Hemisphere cooling (warming). The timing of these events suggests a pacing by insolation over precession periods. A lack of similar regional circulation shifts during the MIS-13/12 transition is likely due to the large equatorwards shift in the tropical convection zone that occurred during this extreme glaciation.

Geochemistry of selected minerals at DSDP Leg 65 Holes

The majority of the basalts drilled on Leg 65 in the Gulf of California are aphyric to sparsely phyric massive flows ranging in average thickness between 5 meters in the upper part of the sections in Holes 483 and 483B, where they are interlayered with sediment, and 14 meters in Hole 485A, where interlayered sediments constitute more than half of the section. Massive flows interlayered with pillows are generally less than 4 meters thick. The pillow lavas recovered are more phyric (up to 15 modal%) and contain two to three generations of plagioclase and olivine ± clinopyroxene. Plagioclase generally exceeds 60% of any given phenocryst assemblage. Resorbed olivine, clinopyroxene, and plagioclase megacrysts may reflect a high-pressure stage, the phenocrysts crystallizing in the main magma chamber and the skeletal microphenocrysts in dikes. Precise measurements of length/width ratios of different phenocryst types and compositions show low aspect ratios and large crystal volumes for early crystals and high ratios and low volumes for late crystals grown under strong undercooling conditions. The minerals examined show wide ranges in composition: in particular, plagioclase ranges from An92 to An36; clinopyroxene ranges from Ca41Mg51Fe8 in the cores of phenocrysts to Ca40**36 Mg45**49Fe15**20 in the groundmass; and olivine ranges from Fo86 to Fo81. The wide range in mineral compositions, together with evidence of disequilibrium based on textures and comparisons of glass and mineral compositions, indicate complex crystallization histories involving both polybaric crystal fractionation and magma mixing.

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.

(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.

Conglomerate and sandstone petrography at DSDP Hole 58-445

Conglomerates and sandstones in lithologic unit V at DSDP Site 445 comprise lithic clasts, detrital minerals, bioclasts, and authigenic minerals. The lithic clasts are dominantly plagioclase-phyric basalt and microdolerite, followed by plagioclase-clinopyroxene-phyric basalt, aphyric basalt, chert, and limestone. A small amount of hornblende schist occurs. Detrital minerals are dominantly plagioclase, augite, titaniferous augite, olivine, green to pale-brown hornblende, and dark-brown hornblende, with subordinate chromian spinel, epidote, ilmenite, and magnetite, and minor amounts of diopside, enstatite, actinolite, and aegirine-augite. Bioclasts are Nummulites boninensis, Asterocyclina sp. cf. A. penuria, and some other larger foraminifers. Correlation of cored and dredged samples indicates that the Daito Ridge is mainly composed of igneous, metamorphic, ultramafic, and sedimentary rocks. The igneous rocks are mafic (probably tholeiitic) and alkalic. The metamorphic rocks are hornblende schist, tremolite schist, and diopside-chlorite schist. The ultramafic rocks are alpinetype peridotites. Mineralogical data suggest that there were two metamorphic events in the Daito Ridge. The older one was intermediate- to high-pressure metamorphism. The younger one was contact metamorphism caused by a Paleocene volcanic event, possibly related to the beginning of spreading of the west Philippine Basin. The ultramafic rocks suffered from the same contact metamorphism. During the Eocene, exposed volcanic and metamorphic rocks on the uplifted Daito Ridge may have supplied pebble clasts to the surrounding coast and shallow sea bottom. The steep slope offshore may have caused frequent slumping and transportation of the pebble clasts and shallow-water benthic organisms into deeper water, forming the conglomerates and sandstones treated here.

Chemical and isotopic compositions of zircons from amphibolites of the Kamchatksky Cape Peninsula

The paper reports the first data on geochemistry and U-Pb SHRIMP geochronology of zircons from garnet amphibolites whose fragments are hosted by the sole of the ophiolite complex of the Kamchatsky Cape, eastern Kamchatka. The zircons compose homogeneous sampling, have relatively small sizes, are anhedral, have no oscillatory zoning, and possess practically no inclusions. Chemical and photoluminescent characteristics of the zircons testify to their metamorphic genesis. U-Pb SHRIMP dates of the zircons (81.4+/-9.6 Ma) indicate that metamorphism of the amphibolite complex took place in Campanian, Late Cretaceous. These dates seem to correspond to the peak of high-pressure metamorphism, which is thought to be related to origin of an ophiolite complex of the suprasubduction type and its uplift within the Kronotsky Island arc.