Geochemistry of Pliocene-Pleistocene volcanic sands of ODP Site 136-842

Several distinct, thin (2-7 cm), volcanic sand layers ("ashes") were recovered in the upper portions of Holes 842A and 842B. These holes were drilled 320 km west of the island of Hawaii on the outer side of the arch that surrounds the southern end of the Hawaiian chain. These layers are Pliocene to Pleistocene in age, graded, and contain fresh glass and mineral fragments (mainly olivine, plagioclase, and clinopyroxene) and tests of Pleistocene to Eocene radiolarians. The glass fragments are weakly vesicular and blocky to platy in shape. The glass and olivine fragments from individual layers have large ranges in composition (i.e, larger than expected for a single eruption). These features are inconsistent with an explosive eruption origin for the sands. The only other viable mechanism for transporting these sands hundreds of kilometers from their probable source, the Hawaiian Islands, is turbidity currents. These currents were probably related to several of the giant debris slides that were identified from Gloria sidescan images around the islands. These currents would have run over the ~500-m-high Hawaiian Arch on their way to Site 842. This indicates that the turbidity currents were at least 325 m thick. Paleomagnetic and biostratigraphic data allow the ages of the sands to be constrained and, thus, related to particular Hawaiian debris flows. These correlations were checked by comparing the compositions of the glasses from the sands with those of glasses and rocks from islands with debris flows directed toward Site 842. Good correlations were found for the 110-ka slide from Mauna Loa and the ~1.4-Ma slide from Lanai. The correlation with Kauai is poor, probably because the data base for that volcano is small. The low to moderate sulfur content of the sand glasses indicates that they were derived from moderately to strongly degassed lavas (shallow marine or subaerially erupted), which correlates well with the location of the landslide scars on the flanks of the Hawaiian volcanoes. The glass sands may have been formed by brecciation during the landslide events or spallation and granulation as lava erupted into shallow water.

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.

Chemical composition of glass inclusions from ODP Holes 157-953C and 157-956B

We report S concentrations and relative proportions of (SO4)2- and S2- in OL- and CPX-hosted glass inclusions and in host glassy lapilli from Miocene basaltic hyaloclastites drilled north and south of Gran Canaria during ODP Leg 157. Compositions of glass inclusions and lapilli resemble those of subaerial Miocene shield basalts on Gran Canaria and comprise mafic to more evolved tholeiitic to alkali basalt and basanite (10.3-3.7 wt.% MgO, 44.5-56.9 wt.% SiO2). Glass inclusions fall into three groups based on their S concentrations: a high-sulfur group (1050 to 5810 ppm S), an intermediate-sulfur group (510 to 1740 ppm S), and a low-sulfur group (<500 ppm S). The most S-rich inclusions have the highest and nearly constant proportion of sulfur dissolved as sulfate determined by electron microprobe measurements of SKa peak shift. Their average S6+/S_total value is 0.75+/-0.09, unusually high for ocean island basalt magmas. The low-sulfur group inclusions have low S6+/S_total ratios (0.08+/-0.05), whereas intermediate sulfur group inclusions show a wide range of S6+/S_total (0.05-0.83). Glassy lapilli and their crystal-hosted glass inclusions with S concentrations of 50 to 1140 ppm S have very similar S6+/S_total ratios of 0.36+/-0.06 implying that sulfur degassing does not affect the proportion of (SO4)2- and S2- in the magma. The oxygen fugacities estimated from S6+/S_total ratios and from Fe3+/Fe2+ ratios in spinel inclusions range from NNO-1.1 to NNO+1.8. The origin of S-rich magmas is unclear. We discuss (1) partial melting of a mantle source at relatively oxidized fO2 conditions, and (2) magma contamination by seawater either directly or through magma interaction with seawater-altered Jurassic oceanic crust. The intermediate sulfur group inclusions represent undegassed or slightly degassed magmas similar to submarine OIB glasses, whereas the low-sulfur group inclusions are likely to have formed from magmas significantly degassed in near-surface reservoirs. Mixing of these degassed magmas with stored volatile-rich ones or volatile-rich magma replenishing the chamber filled by partially degassed magmas may produce hybrid melts with strongly varying S concentrations and S6+/S_total ratios.

Petrographic and chemical characteristics of abyssal tholeiites at DSDP Leg 63 Holes

Tholeiitic basalts were obtained from basaltic basement ranging in age from 6 to 17 m.y. on IPOD/DSDP Leg 63. The main rock types encountered at all sites but 473 are basaltic pillow lavas. Although many of these pillow basalts are highly or moderately altered, fresh glass is usually present. At Site 473, we recovered coarse-grained, massive basalts; no clearly defined pillowed forms were observed. Phenocrysts or microphenocrysts present in the Leg 63 basalts are Plagioclase and clinopyroxene at Site 469; olivine, Plagioclase, and spinel at Site 470; and olivine, Plagioclase, and clinopyroxene at Sites 472 and 473. Olivines of the basalts from Holes 470A and 472 (Fo85-88) are generally more magnesian than those of the Hole 473 basalts (Fo77-81). Also, plagioclases of Holes 470A and 472 basalts (An70-85) are generally more calcic than those of Holes 469 and 473 basalts (An66-72). Geochemical study of the Leg 63 basalts indicates that in all cases they are large-ion-lithophile (LIL) element depleted tholeiites like typical abyssal tholeiites. In particular, they are very similar in composition to those described from the eastern Pacific, although the degree of iron enrichment found in the Leg 63 basalts is not as extensive as in basalts from the Galapagos spreading center. Hence, the geochemical evidence of the Leg 63 basalts is compatible with their formation at a spreading center. Compositional variations in Leg 63 basalts from any single drill hole is small. Major and trace element data indicate that the samples from Holes 469 and 473 are more fractionated in chemical composition than are the samples from Holes 470A and 472; this compositional variation may be largely ascribed to differences in the extent of shallow-level fractional crystallization of similar parental magma. The Hole 472 samples, however, show a LIL element character distinct from the other Leg 63 samples.

Chemical composition of rocks and minerals from the ophiolite complex in the Hunter Fracture Zone

A collection of dredge samples from the Hunter Fracture Zone includes holocrystalline massive and cumulose basic and ultrabasic rocks and volcanites of the ophiolite complex: from basalts to rhyolites. The ultrabasic rocks are largely serpentinized harzburgites and lherzolites; their relict mineralogy is typical of peridotite considered to be the refractory residue of partial melting of the mantle. Cumulate textured ultramafic rocks probably are related to the cumulate gabbro and granodiorite rather than to the residual mantle material. The gabbroic rocks are dominantly cumulate textured Pl-Opx-Cpx±Ol gabbronorite and Pl-Cpx±Ol gabbros; the mineral features of these rocks are the result of their crystallization at moderate pressure (in a moderate level magma chamber). The massive Pl-Cpx±Ol gabbros are less common. Green and brown-green Ca-amphibole has partially or totally replaced the clinopyroxene in many samples. There is an overlap in mineral chemistry between the cumulate rocks and the Opx-Cpx-Pl volcanic rocks and boninites. It is interpreted as an indication that the cumulate rocks were co-genetic with Opx-Cpx-Pl volcanic rocks and that they both constitute remnants of an island arc volcanic-plutonic series. The petrologic evidence indicates that ophiolite gabbroic rocks were derived from an island-arc rather than from a mid-ocean ridge.

Chemistry of gabbroic rocks from ODP Hole 118-735B

Gabbroic rocks and their late differentiates recovered at Site 735 represent 500 m of oceanic layer 3. The original cooling of a mid-ocean ridge magma chamber, its penetration by ductile shear zones and late intrusives, and the subsequent penetration of seawater through a network of cracks and into highly permeable magmatic hydrofracture horizons are recorded in the metamorphic stratigraphy of the core. Ductile shear zones are characterized by extensive dynamic recrystallization of primary phases, beginning in the granulite facies and continuing into the lower amphibolite facies. Increasing availability of seawater during dynamic recrystallization is reflected in depletions in 18O, increasing abundance of amphibole of variable composition and metamorphic plagioclase of intermediate composition, and more complete coronitic or pseudomorphous static replacement of magmatic minerals. Downcore correlation of synkinematic assemblages, bulk-rock oxygen isotopic compositions, and vein abundance suggest that seawater is introduced into the crust by way of small cracks and veins that mark the end of the ductile phase of deformation. This "deformation-enhanced" metamorphism dominates the upper 180 and the lower 100 m of the core. In the lower 300 m of the core, mineral assemblages of greenschist and zeolite facies are abundant within or adjacent to brecciated zones. Leucocratic veins found in these zones and adjacent host rock contain diopside, sodic plagioclase, epidote, chlorite, analcime, thomsonite, natrolite, albite, quartz, actinolite, sphene, brookite, and sulfides. The presence of zircon, Cl-apatite, sodic plagioclase, sulfides, and diopside in leucocratic veins having local magmatic textures suggests that some of the veins originated from late magmas or from hydrothermal fluids exsolved from such magmas that were subsequently replaced by (seawater-derived) hydrothermal assemblages. The frequent association of these late magmatic intrusive rocks within the brecciated zones suggests that they are both artifacts of magmatic hydrofracture. Such catastrophic fracture and hydrothermal circulation could produce episodic venting of hydrothermal fluids as well as the incorporation of a magmatically derived hydrothermal component. The enhanced permeability of the brecciated zones produced lower temperature assemblages because of larger volumes of seawater that penetrated the crust. The last fractures were sealed either by these hydrothermal minerals or by late carbonate-smectite veins, resulting in the observed low permeability of the core.

Geochemistry of boninite and harzburgite of ODP Leg 125 basement samples

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

Composition of bottom sediments from the Mediterranean Sea off Syria

An investigation of recent bottom sediments between the Cyprus Island and the Syrian seacoast during Cruise 27 of R/V Vityaz-2 (1993) gave comprehensive field data significantly complementing our understanding of the sedimentation process in this part of the Mediterranean Sea. Mineralogical and geochemical indicators testify to different input into sedimentation of the Syrian and Nile River sources. The Nile River plays a leading role in terrigenous sedimentation in the southeastern Mediterranean Sea, especially in deep-sea areas. In contrast, contribution of weathering products of basalts and ophiolites from the Syrian drainage area (hornblende, monoclinic and rhombic pyroxenes, olivine, spinel, palagonite, and epidote) are particularly detectable in sediments of the near-coast zone. During Late Quaternary contribution of terrigenous material both from the Syrian and Nile sources was irregular in time.

(Table 7) Representative electron microprobe analyses for natroalunite and larger FeOx spheroids of experiment ADSU6

Acid-sulfate alteration of basalt by SO2-bearing volcanic vapors has been proposed as one possible origin for sulfate-rich deposits on Mars. To better define mineralogical signatures of acid-sulfate alteration, laboratory experiments were performed to investigate alteration pathways and geochemical processes during reaction of basalt with sulfuric acid. Pyroclastic cinders composed of phenocrysts including plagioclase, olivine, and augite embedded in glass were reacted with sulfuric acid at 145 °C for up to 137 days at a range of fluid : rock ratios. During the experiments, the phenocrysts reacted rapidly to form secondary products, while the glass was unreactive. Major products included amorphous silica, anhydrite, and Fe-rich natroalunite, along with minor iron oxides/oxyhydroxides (probably hematite) and trace levels of other sulfates. At the lowest fluid : rock ratio, hexahydrite and an unidentified Fe-silicate phase also occurred as major products. Reaction-path models indicated that formation of the products required both slow dissolution of glass and kinetic inhibitions to precipitation of a number of minerals including phyllosilicates and other aluminosilicates as well as Al- and Fe-oxides/oxyhydroxides. Similar models performed for Martian basalt compositions predict that the initial stages of acid-sulfate alteration of pyroclastic deposits on Mars should result in formation of amorphous silica, anhydrite, Fe-bearing natroalunite, and kieserite, along with relict basaltic glass. In addition, analysis of the experimental products indicates that Fe-bearing natroalunite produces a Mössbauer spectrum closely resembling that of jarosite, suggesting that it should be considered an alternative to the component in sulfate-rich bedrocks at Meridiani Planum that has previously been identified as jarosite.

Chemical analysis of ash layers in ODP Leg 104 holes

Numerous fresh ash layers comprise about 0.3% by volume of Neogene to Holocene sediments drilled at Leg 104 Sites 642 and 643 (Vøring Plateau, North Atlantic). Median grain sizes of the ashes are about 100 /µm and maximum grain sizes range up to 1200 µm. Rhyolitic pumice shards dominate, with minor bubble wall shards. Basaltic shards are poorly vesicular and blocky or round. Phenocrystic plagioclase, zircon, and clinopyroxene occur in the rhyolitic, plagioclase, and clinopyroxene phenocrysts and basaltic lithics in the basaltic tephra. Quartz, amphibole, clinozoisite, and rutile are interpreted as xenocrysts. All ash layers are well-sorted and represent distal fallout from major explosive eruptions. Most ashes are rhyolitic (high-K and low-K) in composition, some are bimodal (tholeiitic and rhyolitic). Early Miocene tephra is dominantly basaltic. Iceland is inferred to be the likely source region for most ashes. Late Miocene high-K rhyolites may have originated from the K-rich Jan Mayen magmatic province. One Quaternary layer with biotite and alkali feldspar phenocrysts may have been derived from Jan Mayen Island. Four individual Pliocene to Holocene ash layers from Sites 642 and 643 can be correlated fairly well. Upper Miocene layers are tentatively correlated as a sequence between Sites 642 and 643. Average calculated layer frequencies are about three layers/m.y. through the Pliocene and Pleistocene and five to eight layers per m.y. through the middle and late Miocene, suggesting rather continuous volcanic activity in the North Atlantic. Episodic magmatic activity during Neogene epochs in this part of the North Atlantic, as postulated in the literature, cannot be confirmed.

Lithologic and geochemical composition of samples from the Circum Superior Belt, North America

The ca. 1880 Ma Circum-Superior Large Igneous Province (LIP) consists of a number of discontinuous segments known to cover a significant portion of the margin of the Superior Province craton in North America. New geochemical and isotopic data from western segments of this LIP support a common origin for the these segments and suggest that magmatism in the Lake Superior region may have been fed through the ~ 600 km long Pickle Crow dyke from a source north of the Fox River Belt in northeastern Manitoba. The Fox River Belt, Pickle Crow dyke and sections of the Hemlock Formation in the Lake Superior region possess trace element signatures which are similar to those of more recent oceanic plateaux. The Hemlock Formation displays a heterogeneous geochemical signature. This chemical heterogeneity can in part be explained by lithospheric contamination and possibly by source heterogeneity. The tectonomagmatic setting in which these igneous rocks were formed could have involved a mantle plume. Evidence supporting a plume origin includes high MgO volcanic rocks, high calculated degrees of partial melting and geochemical signatures similar to those of oceanic plateaux.