Composition of palygorskite-rich and montmorillonite-rich zeolite-containing sediments from DSDP Sites 164 and 196

Cretaceous, Tertiary, and Quaternary sediments from Deep Sea Drilling Project Sites 164 and 196 (13°12' N, 161°31' W and 30°07' N, 148°34' E, respectively) were analyzed for major chemical elements and mineralogy. Sediments from these sites contain large proportions of authigenic minerals: mainly palygorskite, clinoptilolite and chert in the Cretaceous, and montmorillonite, phillipsite and chert in the Tertiary. The montmorillonite-phillipsite assemblage is thought to be derived from volcanic ash or glass, and the palygorskite-clinoptilolite assemblage is thought to be derived by reaction of biogenic silica with volcanic ash or glass or with montmorillonite and phillipsite. Both assemblages have generally moderate Ti/Al ratios, ranging from 0.026 to 0.047, so most of the palygorskite, clinoptilolite, montmorillonite and phillipsite could not be derived in situ from alteration of basaltic material. Plagioclase compositions suggest that the volcanic precursors were silicic or intermediate, but it is also possible that the sediments have been extensively fractionated by redistribution from nearby seamounts. Available data on other Late Cretaceous sediments in the Pacific were analyzed. Clinoptilolite and chert are present nearly everywhere where palygorskite is abundant; phillipsite is rare where palygorskite is abundant. It is suggested that increased water temperatures during the Cretaceous increased reaction rates and determined the alteration products.

Geochemistry of Indian Ocean tephra and Afro-Arabian lavas

Widespread silicic pyroclastic eruptions of the Oligocene Afro-Arabian flood volcanic province (ignimbrites and airfall tuffs) produced up to 20% of the total flood volcanic stratigraphy (>6*10**4 km**3). Volumes of individual ignimbrites and tuffs exposed on land range from ~150 to >2000 km**3 and eight major units (15-100 m thick) were erupted in <2 Myr, placing these amongst the largest-magnitude silicic pyroclastic eruptions on Earth. They are compositionally distinctive time-stratigraphic markers which were deposited as co-ignimbrite ashfall deposits on a near-global scale around the time of the Oi2 cooling anomaly at ~30 Ma. Two ignimbrites from the lower part of the flood volcanic succession in Yemen have been correlated to: (a) the conjugate rifted margin of Ethiopia (>500 km distant); and (b) to two deep sea ash layers sampled by ODP Leg 115 in the Indian Ocean ~2700 km to the southeast. This correlation is based on whole rock analyses of silicic units for isotope ratios (Pb, Nd) and rare earth element compositions, in conjunction with novel in situ Pb isotope laser ablation multicollector inductively coupled plasma mass spectroscopy analysis of groundmass and glass shards. Compositional diversity preserved on the scale of individual ash shards in these deep sea tephra layers record chemical heterogeneity present in the silicic magma chambers that is not evident in the welded on-land deposits. Ages of the ash layers can be established by correlation to precisely dated on-land ignimbrites, and current evidence suggests that while these eruptions may have exacerbated already changing climatic conditions, they both marginally post-date the Oi2 global cooling anomaly.

Geochemistry of the gabbroic lithosphere in IODP Holes 304-U1309D and 305-U1309D

IODP Hole U1309D (Atlantis Massif, Mid-Atlantic Ridge 30°N) is the second deepest hole drilled into slow spread gabbroic lithosphere. It comprises 5.4% of olivine-rich troctolites (~ > 70% olivine), possibly the most primitive gabbroic rocks ever drilled at mid-ocean ridges. We present the result of an in situ trace element study carried out on a series of olivine-rich troctolites, and neighbouring troctolites and gabbros, from olivine-rich intervals in Hole U1309D. Olivine-rich troctolites display poikilitic textures; coarse-grained subhedral to medium-grained rounded olivine crystals are included into large undeformed clinopyroxene and plagioclase poikiloblasts. In contrast, gabbros and troctolites have irregularly seriate textures, with highly variable grain sizes, and locally poikilitic clinopyroxene oikocrysts in troctolites. Clinopyroxene is high Mg# augite (Mg# 87 in olivine-rich troctolites to 82 in gabbros), and plagioclase has anorthite contents ranging from 77 in olivine-rich troctolites to 68 in gabbros. Olivine has high forsterite contents (82-88 in olivine-rich troctolites, to 78-83 in gabbros) and is in Mg-Fe equilibrium with clinopyroxene. Clinopyroxene cores and plagioclase are depleted in trace elements (e.g., Ybcpx ~ 5-11 * Chondrite), they are in equilibrium with the same MORB-type melt in all studied rock-types. These compositions are not consistent with the progressively more trace element enriched (evolved) compositions expected from olivine rich primitive products to gabbros in a MORB cumulate sequence. They indicate that clinopyroxene and plagioclase crystallized concurrently, after melts having the same trace element composition, consistent with crystallization in an open system with a buffered magma composition. The slight trace element enrichments and lower Cr contents observed in clinopyroxene rims and interstitial grains results from crystallization of late-stage differentiated melts, probably indicating the closure of the magmatic system. In contrast to clinopyroxene and plagioclase, olivine is not in equilibrium with MORB, but with a highly fractionated depleted melt, similar to that in equilibrium with refractory oceanic peridotites, thus possibly indicating a mantle origin. In addition, textural relationships suggest that olivine was in part assimilated by the basaltic melts after which clinopyroxene and plagioclase crystallized (impregnation). These observations suggest a complex crystallization history in an open system involving impregnation by MORB-type melt(s) of an olivine-rich rock or mush. The documented magmatic processes suggest that olivine-rich troctolites were formed in a zone with large magmatic transfer and accumulation, similar to the mantle-crust transition zone documented in ophiolites and at fast spreading ridges.

Spherules and basement analyses from DSDP Hole 5-32

Lower Miocene basaltic glass spherules from DSDP Site 32 pelagic sediments in the eastern Pacific are compositionally diverse, and new analyses and interpretations have been added to those of earlier workers. The spherules are of titanian ferrobasalt which is compositionally similar to highly evolved abyssal basalts and to some oceanic island eruptives, and they were most likely shaped during intense lava fountaining during a number of separate eruptions. These eruptions tapped distinct but related magma batches in terms, for example, of distinctively high TiO2 and FeO* contents. Their age overlaps that of some of the eruptions of the Columbia River Plateau Basalts, but they are compositionally distinct from most of the latter basalts. Although about 15 m.y. old, they show little alteration. The low chlorine and sulfur contents compared to those of abyssal ferrobasalts are consistent with degassing prior to quenching during subaerial eruptions, and rule out production of the spherules by submarine fountaining. Lava fountaining alone is insufficient to account for the distance of about 100 km from even the closest possible seamount source. Instead, large phreatomagmatic eruption columns reaching at least 15 km and including lava fountaining immediately after the initial explosion are required. Alternatively, and deemed less likely, is their deposition by turbidites derived from Pioneer Seamount.

(Table 1) Sulfur isotopes and sulfur content at DSDP Leg 64 Holes

Hydrothermal pyrite samples from Holes 477, 477A, and 478 have sulfur isotope values ranging from about 10 to 11 per mil. Samples with negative sulfur isotope values generally have low sulfide sulfur contents and reflect mixed bacterial and hydrothermal sulfur sources. At higher sulfur contents, the hydrothermal component predominates, producing positive isotope values. Hydrothermal sulfide derives from reduction of seawater sulfate and may contain a significant basaltic component. Hydrothermal anhydrite is restricted to a narrow zone beneath a dolerite sill at Site 477 and, because of partial sulfate reduction in the circulating waters, has isotopic values (23.5-25 per mil), heavier than seawater.

Mineralogy micromorphology, and geochemistry at DSDP Site 89-585

At Site 585 of Deep Sea Drilling Project Leg 89 more than 500 m of volcaniclastic to argillaceous middle-Late Cretaceous sediments were recovered. Analyses by X-ray diffraction (bulk sediment and clay fraction), transmission electron microscopy, molecular and atomic absorption, and electron microprobe were done on Site 585 samples. We identify four successive stages and interpret them as the expression of environments evolving under successive influences: Stage 1, late Aptian to early Albian - subaerial and proximal volcanism, chiefly expressed by the presence of augite, analcite, olivine, celadonite, small and well-shaped transparent trioctahedral saponite, Al hydroxides, Na, Fe, Mg, and various trace elements (Mn, Ni, Cr, Co, Pb, V, Zn, Ti). Stage 2, early to middle Albian - submarine and less proximal volcanic influence, characterized by dioctahedral and hairy Mg-beidellites, a paucity of analcite and pyroxenes, the presence of Mg and K, and local alteration of Mg-smectites to Mg-chlorites. Stage 3, middle Albian to middle Campanian - early marine diagenesis, marked by the development of recrystallization from fleecy smectites to lathed ones (all of alkaline Si-rich Fe-beidellite types), by the development of opal CT and clinoptilolite, and by proximal to distal volcanic influences (Na parallel to Ti, K). Local events consist of the supply of reworked palygorskite during the Albian-Cenomanian, and the recurrence of proximal volcanic activity during the early Campanian. Stage 4, late Campanian to Maestrichtian - development of terrigenous supply resulting from the submersion of topographic barriers; this terrigenous supply is associated with minor diagenetic effects and is marked by a clay diversification (beidellite, illite, kaolinite, palygorskite), the rareness of clay recrystallizations, and the disappearance of volcanic markers.

Silicic tephras in ODP Legs 151, 152, and 162

A 6-m.y.-long composite marine record of explosive silicic volcanism from five Ocean Drilling Program sites in the subpolar North Atlantic was compared with several marine records of global and local paleoclimate proxies (benthic d18O and ice-rafted debris records). Coarsening and high frequency of occurrence of Icelandic tephras were recorded in 3.6-3 Ma sediments, suggesting that these tephras were dispersed farther from the source by enhanced westerly winds over the subpolar North Atlantic. The 40Ar/39Ar ages were determined by laser probe on K-feldspar and biotite phenocrysts of tephras that were erupted from the Jan Mayen volcanic system. Compared to the tuned paleomagnetic age model, the 40Ar/39Ar dating (0.618+/-0.007 Ma to 4.90+/-0.05 Ma) yields a new age model that postdates by 155 k.y. the inception of ice rafting on the Iceland Plateau during the cold marine isotope stage M2 (i.e., 3.3-3.14 Ma).

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.

Geochemistry of ash and pumice of ODP Hole 132-810C

Air-fall volcanic ash and pumice were recovered from 22 intervals in upper Miocene-Pleistocene nannofossil oozes cored in Hole 810C on Shatsky Rise, northwest Pacific. Shatsky Rise is near the eastern limit of ash falls produced by explosive volcanism in arc systems in northern Japan and the Kuriles, more than 1600 km away. Electron probe analyses establish that the ash beds and pumice pebbles are andesitic to rhyolitic in composition, and belong to both tholeiitic and high-alumina lineages similar to tephra from Japanese volcanoes. High-speed winds in the polar-front and subtropical jets are evidently what propelled the ash for such a distance. The pumice arrived by flotation, driven from the same directions by winds, waves, and currents. It is not ice-rafted debris from the north. One thick pumice bed probably was deposited when a large pumice mat passed over Shatsky Rise. Far more abundant ash occurs in sediments cored at DSDP Sites 578 through 580, about 500 km west of Shatsky Rise. Most of the ash and pumice at Shatsky Rise can be correlated with specific ash beds at 1, 2, or all 3 of these sites by interpolating to precisely determined magnetic reversal sequences in the cores. Most of the correlations are to thick ash layers (5.7 +/- 3.0 cm) at one or more sites. These must represent extremely large eruptions that spread ash over very wide areas. Whereas several of the thicker correlative ashes fell from elongate east-trending plumes directed from central Japan, the majority of them - dating from about 2 Ma - came from the North Honshu and Kurile arc systems to the northwest. This direction probably was in response to both long-term and seasonal fluctuations in the location and velocity of the polar-front jet, and to more vigorous winter storm fronts originating over glaciated Siberia.

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.

(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.