Geochemistry and mineralogy of Eocene-Oligocene sediments of IODP Hole 302-M0002A

In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~430 m composite depth). While the Neogene part of the record is characterized by grayish-yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene-Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene-Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.

(Table 3) Run conditions and phase relations and proportions during cooling rate experiments on ODP Interval 163-989B-10R-7,55-59

Equilibrium melting and controlled cooling experiments were undertaken to constrain the crystallization and cooling histories of tholeiitic basalts recovered by the Ocean Drilling Program drilling of Site 989 on the Southeast Greenland continental margin. Isothermal experiments conducted at 1 atm. and at the fayalite-magnetite-quartz buffer using lava sample Section 163-989B-10R-7 yielded the equilibrium appearance sequence with decreasing temperature: olivine at 1184 ± 2ºC; plagioclase at 1177ºC ± 5ºC; augite at 1167 ± 5ºC; and pigeonite at 1113 ± 12ºC. In controlled cooling experiments using the same starting composition and cooling rates between 10ºC/hr and 2000ºC/hr, we find a significant temperature delay in the crystallization of olivine, plagioclase, and augite (relative to the equilibrium appearance temperature); pigeonite does not form under any dynamic crystallization conditions. Olivine exhibits the largest suppression in appearance temperature (e.g., 30º for 10ºC/hr and >190º at 100ºC/hr), while plagioclase shows the smallest (~10ºC at 10ºC/hr; 30ºC at 100ºC/hr, and ~80ºC at 1000ºC/hr). These results are in marked contrast to those obtained on lunar basalts, which generally show a large suppression of plagioclase crystallization and modest suppression of olivine crystallization with an increased cooling rate. The results we report agree well with the petrography of lavas recovered from Site 989. Furthermore, the textural analysis of run products, representing a large range of cooling rates and quench temperatures (1150ºC to 1000ºC), provide a framework for evaluating cooling conditions necessary for glass formation, rates of plagioclase growth, and kinetic factors governing plagioclase growth morphology. Specifically, we use these insights to interpret the textural and mineralogical features of the unusual compound flow recovered at Site 989. We concluded from the analysis that this flow most likely records multiple breakouts from a distal tube at an abrupt break in slope, possibly a fault scarp, resulting in the formation of a lava fan delta. This interpretation implies that normal faulting of the oldest lava sequences (lower and, possibly, middle series) preceded eruption of Site 989 lavas.

Rb-Sr isotope systematics and Sr/Ca-Ba/Ca ratios at DSDP Hole 89-462A

Four samples of Nauru Basin basalts (Cores 94 to 109 of Hole 462A, sub-bottom depth 1077-1209 m) have 87Sr/86Sr ratios in the range 0.7037 to 0.7038, which is distinctly higher than the ratios of N-type MORB. The Rb contents of the samples are depleted in comparison with those of MORB and ocean-island basalts. These chemical and isotopic characteristics are identical to those of the basalts previously drilled during Leg 61 (Cores 75 to 90 of Hole 462A), and are explained in terms of inhomogeneity of the source region in the mantle or later alteration effects. Sr/Ca-Ba/Ca systematics of 15 samples from Cores 462A-94 to 462A-109 and 14 samples from Cores 462A-75 to 462A-90 suggest that the Nauru Basin basalts are derived from a mantle peridotite by 20 to 30% partial melting with subsequent Plagioclase crystallization.

Geochemistry and stable isotopes of peridotites of ODP Hole 103-637A

A ridge of strongly serpentinized, plagioclase-bearing peridotite crops out at the boundary between the Atlantic oceanic crust and the Galicia continental margin (western Spain). These peridotites, cored at Hole 637A (ODP Leg 103) have been mylonitized at high-temperature, low-pressure conditions and under large deviatoric stress during their uplift (Girardeau et al., 1988, doi:10.2973/odp.proc.sr.103.135.1988). After this main ductile deformation event, the peridotite underwent a polyphase metamorphic static episode in the presence of water, with the crystallization of Ti- and Cr-rich pargasites at high-temperature (800°-900°C) interaction with a metasomatic fluid or alkaline magma. Introduction of water produced destabilization of the pyroxenes and the subsequent development of hornblendes and tremolite at temperatures decreasing from 750° to 350°C. The main serpentinization of the peridotite occurred at a temperature below 300°C, and possibly around 50°C, as a consequence of the introduction of a large amount of seawater, which is suggested by stable isotope (d18O and SD) data. Finally, calcite derived from seawater precipitated in late-formed fractures or locally pervasively impregnated the peridotite at low temperature (~10°C).

Igneous geochemistry of OP Leg 126 samples

Major element, trace element, and radiogenic isotope compositions of samples collected from Ocean Drilling Program Leg 126 in the Izu-Bonin forearc basin are presented. Lavas from the center of the basin (Site 793) are high-MgO, low-Ti, two-pyroxene basaltic andesites, and represent the products of synrift volcanism in the forearc region. These synrift lavas share many of the geochemical and petrographic characteristics of boninites. In terms of their element abundances, ratios, and isotope systematics they are intermediate between low-Ti arc tholeiites from the active arc and boninites of the outer-arc high. These features suggest a systematic geochemical gradation between volcanics related to trench distance and a variably depleted source. A basement high drilled on the western flank of the basin (Site 792) comprises a series of plagioclase-rich two-pyroxene andesites with calc-alkaline affinities. These lavas are similar to calc-alkaline volcanics from Japan, but have lower contents of Ti, Zr, and low-field-strength elements (LFSE). Lavas from Site 793 show inter-element variations between Zr, Ti, Sr, Ni, and Cr that are consistent with those predicted during crystallization and melting processes. In comparison, concentrations of P, Y, LFSE, and the rare-earth elements (REE) are anomalous. These elements have been redistributed within the lava pile, concentrating particularly in sections of massive and pillowed flows. Relative movement of these two-element groupings can be related to the alteration of interstitial basaltic andesite glass to a clay mineral assemblage by a post-eruptive process. Fluid-rock interaction has produced similar effects in the basement lavas of Site 792. In this sequence, andesites and dacites have undergone a volume change related to silica mobility. As a result of this process, some lithologies have the major element characteristics of basaltic andesite and rhyolite, but can be related to andesitic or dacitic precursors by silica removal or addition.

Primary mineralogy of ODP Leg 115 basalts

Basement rocks were recovered at four sites on Leg 115 along the Reunion hotspot track in the western Indian Ocean. Plate tectonic reconstructions indicate that the drilled structures formed in three different volcanic environments. Sites 706 and 713 from the eastern side of the Saya de Malha Bank and the northern end of the Chagos Bank, respectively, are on a large volcanic platform analogous to Iceland on the Mid-Atlantic Ridge. Lavas at Site 707 on the northwestern side of the Saya de Malha Bank erupted during the early stages of rifting of the Seychelles from India. Basalts from Site 715 were erupted onto an isolated oceanic island that was distant from ocean ridges and continents much as Reunion Island is today. Many of the rocks were examined in thin section and found to be primarily augite-plagioclase basalts with minor olivine and rare opaque oxides. Site 715 is unusual in that it contains a variety of basalts including olivine-rich and aphyric Fe-Ti basalts. At each of the four sites the rocks were grouped into chemical types (units) on the basis of ship- board bulk-rock analyses and at least one thin section from each chemical unit was analyzed by electron microprobe. The plagioclase and augite chemistry reflects the bulk-rock chemistry and, in general, these minerals were in equilibrium with their host magmas at the time the basalts were quenched. Olivine was rarely preserved, but where it is still present it also appears to have crystallized in equilibrium with the host magma. At three of the drill sites plagioclase phenocrysts or megacrysts that crystallized from a primitive magma are also present. The one site (715) that does not contain these primitive plagioclase phenocrysts is also the site that appears to have been influenced the least by ocean- ridge or Deccan-type magmas. Site 715, furthermore, has a mineralogy that is dominated by olivine as compared with the plagioclase-rich lavas of the other sites.

Holocene sedimentation in the Strait of Otranto, Mediterranean Sea

An extensive radiograph study of 24 undisturbed, up to 206-cm long box and gravity cores from the western part of the Strait of Otranto revealed a great variety of primary bedding structures and secondary burrowing features. The regional distribution of the sediments according to their structural, textural, and compositional properties reflects the major morphologic subdivisions of the strait into shelf, slope, and trough bottom (e.g., the bottom of the northern end of the Corfu-Kephallinia Trough, which extends from the northeastern Ionian Sea into the Strait of Otranto): (1) The Apulian shelf (0 to -170m) is only partly covered by very poorly sorted, muddy sands without layering. These relict(?) sands are rich in organic carbonate debris and contain glauconite and reworked (?Pleistocene) ooids. (2) The slope sediments (-170 to -1,000 m) are poorly sorted, sandy muds with a high degree of burrowing. One core (OT 5) is laminated and shows slump structures. An origin of these slumped sediment masses from older deposits higher on the slope was inferred from their abnormal compaction, color, texture, organic content, and mineral composition. (3) Cores from the northern end of the Corfu-Kephallinia Trough (-980 to -1,060 m) display a few graded sand layers, 2-5 cm (maximum 30 cm) thick with parallel and ripple-cross-laminations, deposited by oceanic bottom or small-scale turbidity currents. They are intercalated with homogeneous lutite. (4) Hemipelagic sediments prevail in the more southerly part of the Corfu-Kephallinia Trough and on the "Apulian-Ionian Ridge", the southern submarine extension of the Apulian Peninsula. Below a core depth of 160 cm, these cores have a laminated ("varved") zone, representing an Early Holocene (Boreal-Atlanticum) "stagnation layer" (14C age approximately 9,000 years). The terrigenous components of the surface sediments as well as those of the deeper sand layers can be derived from the Apulian shelf and the Italian mainland (Cretaceous Apulian Plateau and Gargano Mountains, southern Apennines, volcanic province of the Monte Vulture). Indicated by the heavy mineral glaucophane, a minor proportion of the sedimentary material is probably of Alpine origin. If this portion is considered to be first-cycle clastic material it reaches the Strait of Otranto after a longitudinal transport of 700 km via the Adriatic Sea. The lack of phyllosilicates in the coarse- to medium-grained shelf samples might be explained by the activity of the "Apulian Current" (surface velocities up to 4 knots) which in the past possibly has affected the bottom almost down to depths of the shelf edge. The percentage of planktonic organisms, and also the plankton: benthos ratio in the sediments is a useful indicator for bathymetry (depth zonation).

Sedimentary mineralogy of argillaceous sediments at DSDP Legs 56-57 Holes

Mineral assemblages of DSDP Holes 436 and 438A and the upper section of Hole 439 (871.5-911.0 m sub-bottom) resemble each other and are composed of montmorillonite (probably a small portion of montmorillonite/illite mixed-layer clays), illite, chlorite, kaolinite, quartz, plagioclase, hornblende, calcite, dolomite, siderite, gypsum, pyrite, and halite. In the middle section of Hole 439 (933.5-1041.0 m), clinoptilolite is also found. In the lower section of Hole 439 (1077.5-1150.0 m), montmorillonite is not confirmed, and clinoptilolite and mixed-layer illite are found. These assemblages, which also contain detrital kaolinite, are generally found in sediments from brackish-water environments. At Site 439, more than 1000 meters of sediment might have been removed by erosion at the base.

Geochemistry of the lower sheeted dike complex of ODP Holes 137-504B and 140-504B

Sixty-three samples representing 379 m of sheeted dikes from Deep Sea Drilling Project/Ocean Drilling Program Site 504B have been analyzed for major and selected trace elements by X-ray fluorescence. The samples range from microcrystalline aphyric basalts to moderately phyric (2%-10% phenocrysts) diabase that are typically multiply saturated with plagioclase, olivine, and clinopyroxene, in order of relative abundance. All analyzed samples are classified as Group D compositions with moderate to slightly elevated compatible elements (MgÆ-value = 0.65% ± 0.03%; Al2O3 = 15.5% ± 0.8%; CaO = 13.0% ± 0.3%; Ni = 114 ± 29 ppm), and unusually depleted levels of moderate to highly incompatible elements (Nb < 1 ppm; Zr = 44 ± 7 ppm; Rb < 0.5 ppm; Ba ~ 1 ppm; P2O5 = 0.07% ± 0.02%). These compositions are consistent with a multistage melting of a normal ocean ridge basaltic mantle source followed by extensive fractionation of olivine, plagioclase, and clinopyroxene. Leg 140 aphyric to sparsely phyric (0%-2% phenocrysts) basalts and diabases are compositionally indistinguishable from similarly phyric samples at higher levels in the hole. An examination of the entire crustal section, from the overlying volcanics through the sheeted dikes observed in Leg 140, reveals no significant trends indicating the enrichment or depletion of Costa Rica Rift Zone source magmas over time. Similarly, significant trends toward increased or decreased differentiation cannot be identified, although compositional patterns reflecting variable amounts of phenocryst addition are apparent at various depths. Below ? 1700 mbsf to the bottom of the Leg 140 section, there is a broadly systematic pattern of Zn depletion with depth, the result of high-temperature hydrothermal leaching. This zone of depletion is thought to be a significant source of Zn for the hydrothermal fluids depositing metal sulfides at ridge-crest hydrothermal vents and the sulfide-mineralization zone, located in the transition between pillow lavas and sheeted dikes. Localized zones of intense alteration (60%-95% recrystallization) are present on a centimeter to meter scale in many lithologic units. Within these zones, normally immobile elements Ti, Zr, Y, and rare-earth elements are strongly depleted compared with "fresher" samples centimeters away. The extent of compositional variability of these elements tends to obscure primary igneous trends if the highly altered samples are not identified or removed. At levels up to 40% (or possibly 60%) recrystallization, Ti, Zr, and Y retain their primary signatures. Although the mechanisms are unclear, it is possible that these intense alteration zones are a source of Y and rare-earth elements for the typically rare-earth-element-enriched hydrothermal vent fluids of mid-ocean ridges.

Minerals of bulk and fine-grained (2 µm) samples from DSDP Leg 60

A bulk-sediment and clay-fraction X-ray diffraction study of samples from Deep Sea Drilling Project Leg 60 shows an abundance of the following minerals: plagioclase feldspar, zeolite, smectite, Fe-Mg chlorite, attapulgite, and serpentine. Amorphous compounds are also abundant. The variations in abundance of the different components correspond to episodes of volcanic activity through time. Deposits from periods of great activity are composed of sediments very rich in amorphous matter and in "primary" minerals (e.g., plagioclase feldspars). During relatively quiet periods, clay minerals and zeolites predominate.

Major-oxides and trace-elements at DSDP Hole 78-543A

Four chemically distinct basalts were cored in 44 m of basement penetration at Deep Sea Drilling Project Site 543, in Upper Cretaceous crust just seaward of the deformation front of the Barbados Ridge and north of the Tiburon Rise. All four types are moderately fractionated abyssal tholeiites. The four types have different magnetic inclinations, all of reversed polarity, suggesting eruption at different times which recorded secular variation of the earth's magnetic field. Extensive replacement of Plagioclase by K-feldspar has occurred at the top of the basalts, giving analyses with K2O contents up to 5 %. The earliest stages of alteration were dominantly oxidative, resulting in fractures lined with celadonite and dioctahedral smectite, and pervasive replacement of olivine and most intersertal glass with iron hydroxides and green clay minerals. Latef, non-oxidative alteration resulted in formation of olive-green clays and pyrite veins in a portion of the rocks. Basalts affected by this alteration actually lost K2O (to abundances lower than in adjacent fresh basalt glasses), and gained MgO (to abundances higher than in the glasses). Finally, fractures and interpillow voids were lined with calcite, sealing in much fresh glass. Oxygen-isotope measurements on the calcite indicate that this occurred at 12 to 25C. Either altering fluids were warm or the basalts had become buried with a considerable thickness of sediments, such that temperatures increased until a conductive thermal gradient was established, when the veining occurred.

Chemical and isotopic compositions of rocks and minerals from the Palenyi Island, Por'ya Guba (Bay), White Sea

Hypersthene-garnet-sillimanite-quartz enclaves were studied in orthopyroxene-plagioclase and orthopyroxene-clinopyroxene crystalline schists and gneisses from shear zones exposed in the Palenyi Island within the Early Proterozoic Belomorian Mobile Belt. Qualitative analysis of mineral assemblages indicates that these rocks were metamorphosed to the granulite facies (approximately 900°C and 10-11 kbar). Oxygen isotopic composition was determined in rock-forming minerals composing zones of the enclaves of various mineral and chemical composition. Closure temperatures of the isotopic systems obtained by methods of oxygen isotopic thermometry are close to values obtained with mineralogical geothermometers (garnet-orthopyroxene and garnet-biotite) and correspond to the high-temperature granulite facies (860-900°C). Identified systematic variations in d18O values were determined in the same minerals from zones of different mineral composition. Inasmuch as these zones are practically in contact with one another, these variations in d18O cannot be explained by primary isotopic heterogeneity of the protolith. Model calculations of the extent and trend of d18O variations in minerals suggest that fluid-rock interaction at various integral fluid/rock ratios in discrete zones was the only mechanism that could generate the zoning. This demonstrates that focused fluid flux could occur in lower crustal shear zones. Preservation of high-temperature isotopic equilibria of minerals testifies that the episode of fluid activity at the peak of metamorphism was very brief.

Petrology and geochemistry of the Izu-Bonin Forearc tephras

Numerous marine tephra layers cored at Sites 792 and 793 in the Izu-Bonin forearc region offer additional information about the timing and spatial characteristics of arc volcanism and the evolution of island arcs. Explosive volcanism along the Izu-Bonin Arc, with maxima just before rifting of the arc at ~40 and 5-0 Ma, produced black and white tephras of variable grain sizes and chemical compositions. Most of the tephras belong chemically to low-K and low-alkali tholeiitic rock series with a few tephra of the high-K and alkalic rock series. Most of the tephras (low-K series) were derived from the Izu-Bonin Arc, although a few were produced far to the west of the Izu-Bonin Arc (e.g., from the Ryukyu Arc). Black tephras may have come from nearby sources, such as Aogashima, Sumisu, and Torishima islands. The high-K series of tephras, within the sediments younger than 3 Ma, may reflect thickening of the island-arc crust.

Geochemistry of lavas from the Lau-Tonga arc and back-arc system

Detailed comparison of mineralogy, and major and trace geochemistry are presented for the modern Lau Basin spreading centers, the Sites 834-839 lavas, the modern Tonga-Kermadec arc volcanics, the northern Tongan boninites, and the Lau Ridge volcanics. The data clearly confirm the variations from near normal mid-ocean-ridge basalt (N-MORB) chemistries (e.g., Site 834, Central Lau Spreading Center) to strongly arc-like (e.g., Site 839, Valu Fa), the latter closely comparable to the modern arc volcanoes. Sites 835 and 836 and the East Lau Spreading Center represent transitional chemistries. Bulk compositions range from andesitic to basaltic, but lavas from Sites 834 and 836 and the Central Lau Spreading Center extend toward more silica-undersaturated compositions. The Valu Fa and modern Tonga-Kermadec arc lavas, in contrast, are dominated by basaltic andesites. The phenocryst and groundmass mineralogies show the strong arc-like affinities of the Site 839 lavas, which are also characterized by the existence of very magnesian olivines (up to Fo90-92) and Cr-rich spinels in Units 3 and 6, and highly anorthitic plagioclases in Units 2 and 9. The regional patterns of mineralogical and geochemical variations are interpreted in terms of two competing processes affecting the inferred magma sources: (1) mantle depletion processes, caused by previous melt extractions linked to backarc magmatism, and (2) enrichment in large-ion-lithophile elements, caused by a subduction contribution. A general trend of increasing depletion is inferred both eastward across the Lau Basin toward the modern arc, and northward along the Tongan (and Kermadec) Arc. Numerical modeling suggests that multistage magma extraction can explain the low abundances (relative to N-MORB) of elements such as Nb, Ta, and Ti, known to be characteristic of island arc magmas. It is further suggested that a subduction jump following prolonged slab rollback could account for the initiation of the Lau Basin opening, plausibly allowing a later influx of new mantle, as required by the recognition of a two-stage opening of the Lau Basin.