Trace element geochemistry of zircons frim in situ ocean lithoshere

We characterize the textural and geochemical features of ocean crustal zircon recovered from plagiogranite, evolved gabbro, and metamorphosed ultramafic host-rocks collected along present-day slow and ultraslow spreading mid-ocean ridges (MORs). The geochemistry of 267 zircon grains was measured by sensitive high-resolution ion microprobe-reverse geometry at the USGS-Stanford Ion Microprobe facility. Three types of zircon are recognized based on texture and geochemistry. Most ocean crustal zircons resemble young magmatic zircon from other crustal settings, occurring as pristine, colorless euhedral (Type 1) or subhedral to anhedral (Type 2) grains. In these grains, Hf and most trace elements vary systematically with Ti, typically becoming enriched with falling Ti-in-zircon temperature. Ti-in-zircon temperatures range from 1,040 to 660°C (corrected for a TiO2 ~ 0.7, a SiO2 ~ 1.0, pressure ~ 2 kbar); intra-sample variation is typically ~60-15°C. Decreasing Ti correlates with enrichment in Hf to ~2 wt%, while additional Hf-enrichment occurs at relatively constant temperature. Trends between Ti and U, Y, REE, and Eu/Eu* exhibit a similar inflection, which may denote the onset of eutectic crystallization; the inflection is well-defined by zircons from plagiogranite and implies solidus temperatures of ~680-740°C. A third type of zircon is defined as being porous and colored with chaotic CL zoning, and occurs in ~25% of rock samples studied. These features, along with high measured La, Cl, S, Ca, and Fe, and low (Sm/La)N ratios are suggestive of interaction with aqueous fluids. Non-porous, luminescent CL overgrowth rims on porous grains record uniform temperatures averaging 615 ± 26°C (2SD, n = 7), implying zircon formation below the wet-granite solidus and under water-saturated conditions. Zircon geochemistry reflects, in part, source region; elevated HREE coupled with low U concentrations allow effective discrimination of ~80% of zircon formed at modern MORs from zircon in continental crust. The geochemistry and textural observations reported here serve as an important database for comparison with detrital, xenocrystic, and metamorphosed mafic rock-hosted zircon populations to evaluate provenance.

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.

Triassic marine ostracodes of the Australian Margin

Sixty-five species of benthic ostracodes have been discovered in the Triassic sediments of Ocean Drilling Program Leg 122, drilled on the northwestern margin of Australia. Known species were found in the samples studied from the upper Norian-Rhaetian at Holes 759B and 760B and from the Rhaetian at Holes 761C, 764A, and 764B. A large part of material of the recovered ostracodes belong to taxa that are related to ostracodes described in the Tethyan province. Seven species are known from northwestern Europe and five from Iran. Ogmoconcha and Rhombocythere, which are stratigraphically important genera in northern Europe, extend into the Tethyan province. Species of Ogmoconcha are present in Holes 760B, 764A, and 764B. The highly ornate baidiids of the Alpine Tethyan province are dominant in Hole 761C. The affinities with the fauna of Iran noted by Kristan-Tollmann are corroborated by the presence of the genera Mostlerella, Hiatobairdia, and other bairdiids.

Geochemistry of Cretaceous sediments from Argo and Gascoyne Abyssal Plains

The accumulation of organic matter, ferrous and pyrite iron, and the ratios of organic carbon/total sulfur and organic carbon/total phosphorus in the Lower Cretaceous sediments from the Argo and Gascoyne abyssal plains have been used as indicators of both the source and reactivity of organic matter in the sediments and the depositional environment. Total sulfur, used as an indicator of pyrite sulfur, is more abundant in sediments from the Gascoyne Abyssal Plain than in those from the Argo Abyssal Plain. Sulfur positively correlates with TOC at both sites (although poorly at the Argo Abyssal Plain site, R = 0.48), with an extension of the line of best-fit through the origin, indicating that pyrite (TOC <2 wt%) is diagenetic and deposited from normal marine conditions. The average ratio of C/S for samples of TOC <2 wt% is 5.4 at Argo Abyssal Plain (compared to the modern normal marine value of 2.8) indicating deposition of organic matter probably of mixed terrestrial and oxidized marine sources that is unreactive to the sulfate-reducing bacteria. One sample from the Aptian sediments is rich in TOC (5.1 wt%) and has a C/S ratio of 0.5. The average C/S ratio in Gascoyne Abyssal Plain sediments is 0.8 (R = 0.97), which indicates the formation of abundant pyrite in addition to burial and preservation of relatively fresh organic matter that is reactive to the sulfate-reducing bacteria. Organic carbon to phosphorus ratios (C/P) in the sediments indicate preferential remobilization of organic carbon over phosphorus with increasing water depth. Estimates of the degree of pyritization (DOP) increase with increasing TOC at both sites, indicating iron is not limiting and pyrite is formed diagenetically. The one sample with a TOC content of 5.1 wt%, from the Argo Abyssal Plain near the Barremian-Aptian boundary, is composed mostly of framboidal pyrite, finely laminated and not bioturbated, and hence may have been deposited during a brief period of anoxia in the overlying waters.

Geochemistry of Early Cretaceous basaltic rocks from ODP Sites 123-765 and 123-766

The Early Cretaceous basaltic rocks obtained from Sites 765 and 766 in the eastern Indian Ocean floor were mostly iron-rich normal mid-ocean ridge basalts (N-MORB), which were derived from a depleted mantle source having strongly light rare earth element (LREE)-depleted rare-earth patterns and a high titanium/zirconium (Ti/Zr) ratio. Basaltic rocks in the upper part of the Site 765 basement section include megacrysts and gabbroic fragments of widely varying mineral chemistry. These megacrysts range from An90 plagioclase, including highly magnesian basaltic glass coexisting with augite of Mg# (= 100 Mg/[Fe+Mg]) at 85, to An50 plagioclase coexisting with hypersthene. This varying mineralogy of megacrysts and gabbroic fragments indicates that a considerable degree of fractional crystallization took place in the magma chamber. The unusual negative correlation between incompatible elements (e.g., TiO2) and FeO*/MgO observed among Site 765 basement basalts and fresh volcanic glasses suggest source-mantle heterogeneity in terms of FeO*/MgO. Strontium isotope ratios (87Sr/86Sr) of the basaltic rocks from both sites are between 0.7027 and 0.7033 and are comparable to those of mid-Indian Ocean ridge basalts (MIORB). The basalt pebbles encountered in the sedimentary section may have been transported from the basement highs nearer the Australian continent and include basaltic compositions ranging from primitive N-MORBs to evolved enriched (E)-MORBs. Their mantle source was not as depleted as that of the basement basalts. These rocks may be the products of earlier volcanism that took place during the rifting of the Australian continent.

Strontium isotope ratios and concentrations in fossil fish teeth

We analyzed 87Sr/86Sr ratios in foraminifera, pore fluids, and fish teeth for samples ranging in age from Eocene to Pleistocene from four Ocean Drilling Program sites distributed around the globe: Site 1090 in the Cape Basin of the Southern Ocean, Site 757 on the Ninetyeast Ridge in the Indian Ocean, Site 807 on the Ontong-Java Plateau in the western equatorial Pacific, and Site 689 on the Maud Rise in the Southern Ocean. Sr isotopic ratios for dated foraminifera consistently plot on the global seawater Sr isotope curve. For Sites 1090, 757, and 807 Sr isotopic values of the pore fluids are generally less radiogenic than contemporaneous seawater values, as are values for fossil fish teeth. In contrast, pore fluid 87Sr/86Sr values at Site 689 are more radiogenic than contemporaneous seawater, and the corresponding fish teeth also record more radiogenic values. Thus, Sr isotopic values preserved in fossil fish teeth are consistently altered in the direction of the pore fluid values; furthermore, there is a correlation between the magnitude of the offset between the pore fluids and the seawater curve, and the associated offset between the fish teeth and the seawater curve. These data suggest that the hydroxyfluorapatite of the fossil fish teeth continues to recrystallize and exchange Sr with its surroundings during burial and diagenesis. Therefore, Sr chemostratigraphy can be used to determine rough ages for fossil fish teeth in these cores, but cannot be used to fine-tune age models. In contrast to the Sr isotopic system, our Nd concentration data, combined with published isotopic and rare earth element data, suggest that fish teeth acquire Nd during early diagenesis while they are still in direct contact with seawater. The concentrations of Nd acquired at this stage are extremely high relative to the concentrations in surrounding pore fluids. As a result, Nd isotopes are not altered during burial and later diagenesis. Therefore, fossil fish teeth from a variety of marine environments preserve a reliable and robust record of deep seawater Nd isotopic compositions from the time of deposition.

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 ferromanganese deposits from the Wombat Plateau

Ferromanganese crusts, nodules, and ferromanganese-rich sediments were recovered on the Wombat Plateau, northwest Australian continental margin, by dredging during Bureau of Mineral Resources cruise 56 of Rig Seismic and by drilling during ODP Leg 122 of JOWES Resolution. We report here the chemistry and mineralogy of the ferromanganese crusts, nodules, and associated ferromanganese-rich sediments. The ferromanganese deposits from the ODP sites are up to 40 cm thick and probably formed in Late Cretaceous to Eocene times. Those from outcrops usually formed in several phases, and their age is unconstrained except that the substrates are Mesozoic. The samples were recovered from present-day water depths of 2000-4600 m, on the Wombat Plateau adjacent to the Argo Abyssal Plain. Both the nodules and crusts are primarily vernadite (delta-MnO2) and are chemically and mineralogically similar, and not dissimilar from ferromanganese deposits found elsewhere on Australian and other marginal plateaus. They are markedly different from most deep-sea deposits. The only crystalline iron phase identified within the ferromanganese deposits is goethite. Concentrations of metals of potential economic interest are generally low compared to those from vernadite-rich seamount crusts and nodules and from abyssal nodules from areas of high resource potential in the Pacific Ocean. Maximum metal values reach 0.55% Co, 0.58% Ni, and 0.20% Cu in deposits containing 4.8% to 30.9% Fe and 4.4% to 21.1% Mn.

Geochemistry and isotopic composition of gabbros from ODP Hole 118-375B

Gabbros drilled from the shallow (720 m) east wall of the Atlantis II transform on the Southwest Indian Ridge (SWIR; 32°43.40', 57°16.00') provide the most complete record of the stratigraphy and composition of the oceanic lower crust recovered from the ocean basins to date. Lithologies recovered include gabbro, olivine gabbro, troctolite, trondhjemite, and unusual iron-titanium (FeTi) oxide-rich gabbro containing up to 30% FeTi oxides. The plutonic rock sequence represents a tholeiitic fractionation trend ranging from primitive magmas having Mg numbers of 67 to 69 that fractionated troctolites, to highly evolved liquids that crystallized two-pyroxene, FeTi oxide-rich gabbros and, ultimately, trondhjemite. Isotopic compositions of unaltered Leg 118 gabbros are distinct from Indian Ocean mid-ocean ridge basalts (MORB) in having higher 143Nd/144Nd (0.51301-0.51319) and lower 206Pb/204Pb values (17.35-17.67); 87Sr/86Sr values (0.7025-0.7030) overlap those of SWIR basalts, but are generally lower than MORBs from the Southeast Indian Ridge or the Rodrigues Triple Junction. More than one magma composition may have been introduced into the magma chamber during its crystallization history, as suggested by the higher 87Sr/86Sr, 206Pb/204Pb, and lower 143Nd/144Nd values of chromium-rich olivine gabbros from the bottom of Hole 735B. Whole-rock gabbro and plagioclase mineral separate 87Sr/86Sr values are uniformly low (0.7027-0.7030), irrespective of alteration and deformation. By contrast, 87Sr/86Sr values for clinopyroxene (0.7025-0.7039) in the upper half of Hole 735B are higher than coexisting plagioclase and reflect extensive replacement of clinopyroxene by amphibole. Hydrothermal veins and breccias have elevated 87Sr/86Sr values (0.7029-0.7035) and indicate enhanced local introduction of seawater strontium. Oxygen- and hydrogen-isotope results show that secondary amphiboles have uniform dD values of -49 to -54 per mil and felsic hydrothermal veins range from -46 to - 77 per mil. Oxygen-isotope data for secondary amphibole and visibly altered gabbros range to low values (+1.0-+5.5 per mil), and O-isotope disequilibrium between coexisting pyroxene and plagioclase pairs from throughout the stratigraphic column indicates that seawater interacted with much of the gabbro section, but at relatively low water/rock ratios. This is consistent with the persistence of low 87Sr/86Sr values, even in gabbros that were extensively deformed and altered.

Stable Oxygen and carbon isotope record of benthic foraminifera of ODP Leg 121 holes

Oxygen and carbon isotopic records have been developed for the Cenozoic carbonate oozes of Sites 752, 754, 756, and 757 based on the analysis of monospecific benthic foraminifers. The intent of this report is to provide a basic isotopic stratigraphy for use in other paleoceanographic studies. The oxygen isotope record displays the enrichments associated with cooling or ice volume buildup at the Eocene/Oligocene boundary, in the middle Miocene, and in the upper Pliocene. The carbon isotopic record contains the Chron 16 enrichment in the lower Miocene and the Chron 6 depletion in the uppermost Miocene.

Stable isotope ratios of foraminifera from various DSDP/ODP sites

The equator to high southern latitude sea surface and vertical temperature gradients are reconstructed from oxygen isotope values of planktonic and benthic foraminifers for the following five time intervals: late Paleocene, early Eocene, early middle Eocene, late Eocene, and early Oligocene. Paleotemperatures are calculated using standard oxygen isotope/temperature equations with adjustments to account for (1) variations in sea water delta18O related to changes in global ice volume over time and (2) latitudinal gradients in surface water delta18O. These reconstructions indicate that sea-surface temperatures (SST) of the Southern Oceans in the early Eocene were as high as 15°C, whereas temperatures during the late Paleocene and early middle Eocene reached maximum levels of 10°-12°C. By the late Eocene and early Oligocene high latitude SST had declined to 6 and 4°C, respectively. For most of the early Paleogene, low latitude sub-tropical temperatures remained constant and well within the range of Holocene temperatures (24°-25°C) but by the late Eocene and early Oligocene declined to values in the range of 18° to 22°C. The late Paleogene apparent decline in tropical temperatures, however, might be artificial because of dissolution of near-surface foraminifera tests which biased sediment assemblages toward deeper-dwelling foraminifera. Moreover, according to recent plate reconstructions, it appears that the majority of sites upon which the late Eocene and early Oligocene tropical temperatures were previously established were located either in or near regions likely to have been influenced by upwelling. Global deepwater temperature on average paralleled southern ocean SST for most of the Paleogene. We speculate based on the overall timing and character of marine sea surface temperature variation during the Paleogene that some combination of both higher levels of greenhouse gases and increased heat transport was responsible for the exceptional high-latitude warmth of the early Eocene.

Geochemistry of ODP Hole 121-752A

The present study involves the analysis and interpretation of geochemical data from a suite of sediment samples recovered at ODP Hole 752A. The samples encompass the time period that includes the lithospheric extension and uplift of Broken Ridge, and they record deposition below and above the mid-Eocene angular unconformity that denotes this uplift. A Q-mode factor analysis of the geochemical data indicates that the sediments in this section are composed of a mixture of three geochemical end members that collectively account for 94.2% of the total variance in the data. An examination of interelement ratios for each of these end members suggests that they represent the following sedimentary components: (1) a biogenic component, (2) a volcanogenic component, and (3) a hydrothermal component. The flux of the biogenic component decreases almost thirtyfold across the Eocene unconformity. This drastic reduction in the deposition of biogenic materials corresponds to the almost complete disappearance of chert layers, diatoms, and siliceous microfossils and is coincident with the uplift of Broken Ridge. The volcanogenic component is similar in composition to Santonian ash recovered at Hole 755A on Broken Ridge and is the apparent source of the Fe-stained sediment that immediately overlies the angular unconformity. This finding suggests that significant amounts of Santonian ash were subaerially exposed, weathered, and redeposited and is consistent with data that suggest that the vertical uplift of Broken Ridge was both rapid and extensive. The greatest flux of hydrothermal materials is recorded in the sediments immediately below the angular unconformity. This implies that the uplift of Broken Ridge was preceded by a significant amount of rifting, during which faulting and fracturing of the lithosphere led to enhanced hydrothermal circulation. This time sequence of events is consistent with (but not necessarily diagnostic of) the passive model of lithospheric extension and uplift.

Isotope oxygen record for ODP sediments from the Exmouth Plateau

A new composite d18O record, generated from calcareous fine-fraction and bulk sediments from the Exmouth Plateau, details long-term Cretaceous climatic change at mid-latitudes in the Southern Hemisphere. Assessment of new and previously published d18O data indicates that a mid-Cretaceous global climatic optimum was achieved sometime between the time of the Cenomanian-Turonian boundary and the middle Turonian, when surface-ocean paleotemperatures were the highest of the past 115 m.y. Periods of cooling and warming that reversed the general patterns were superimposed on long-term Aptian-Turonian warming and Turonian-Maastrichtian cooling trends, respectively. Extrapolation of Southern Hemisphere paleotemperature trends to Maastrichtian paleotemperature data from a low-latitude Pacific guyot implies that maximum mid-Cretaceous low-latitude paleotemperatures could have been in excess of 33°C.