Major and trace element analyses of ODP Leg 120 volcanic rocks (Table 1)

Widespread Lower Cretaceous magmatism occurred along the Indian-Australian/Antarctic margins, and in the juvenile Indian Ocean, during the rifting of eastern Gondwana. The formation of this magmatic province probably began around 120-130 Ma with the eruption of basalts on the Naturaliste Plateau and at Bunbury, western Australia. On the northeast margin of India, activity began around 117 Ma with the Rajmahal continental basalts and associated lamprophyre intrusions. The formation of the Kerguelen Plateau in the Indian Ocean began no later than 114 Ma. Ultramafic lamprophyres (alnoites) were emplaced in the Prince Charles Mountains near the Antarctic continental margin at ~ 110 Ma. These events are considered to be related to a major mantle plume, the remnant of which is situated beneath the region of Kerguelen and Heard islands at the present day. Geochemical data are presented for each of these volcanic suites and are indicative of complex interactions between asthenosphere-derived magmas and the continental lithosphere. Kerguelen Plateau basalts have Sr and Nd isotopic compositions lying outside the field for Indian Ocean mid-ocean ridge basalts (MORB) but, with the exception of Site 738 at the southern end of the plateau, within the range of more recent hotspot basalts from Kerguelen and Heard Islands. However, a number of the plateau tholeiites are characterized by lower 206Pb/204Pb ratios than are basalts from Kerguelen Island, and many also have anomalously high La/Nb ratios. These features suggest that the source of the Kerguelen Plateau basalts suffered contamination by components derived from the Gondwana continental lithosphere. An extreme expression of this lithospheric signature is shown by a tholeiite from Site 738, suggesting that the southernmost part of the Kerguelen Plateau may be underlain by continental crust. The Rajmahal tholeiites mostly fall into two distinct geochemical groups. Some Group I tholeiites have Sr and Nd isotopic compositions and incompatible element abundances, similar to Kerguelen Plateau tholeiites from Sites 749 and 750, indicating that the Kerguelen-Heard mantle plume may have directly furnished Rajmahal volcanism. However, their elevated 207Pb/204Pb ratios indicate that these magmas did not totally escape contamination by continental lithosphere. In contrast to the Group I tholeiites, significant contamination is suggested for Group II Rajmahal tholeiites, on the basis of incompatible element abundances and isotopic compositions. The Naturaliste Plateau and the Bunbury Basalt samples show varying degrees of enrichment in incompatible elements over normal MORB. The Naturaliste Plateau samples (and Bunbury Basalt) have high La/Nb ratios, a feature not inconsistent with the notion that the plateau may consist of stretched continental lithosphere, near the ocean-continent divide.

(Table DR1) Trace element contents in basalts from ODP Hole 33-317A

Numerous large igneous provinces formed in the Pacific Ocean during Early Cretaceous time, but their origins and relations are poorly understood. We present new geochronological and geochemical data on rocks from the Manihiki Plateau and compare these results to those for other Cretaceous Pacific plateaus. A dredged Manihiki basalt gives an 40Ar-39Ar age of 117.9+/-3.5 Ma (2 sigma), essentially contemporaneous with the Ontong Java Plateau ~2500 km to the west, and the possibly related Hikurangi Plateau ~3000 km to the south. Drilled Manihiki lavas are tholeiitic with incompatible trace element abundances similar to those of Ontong Java basalts. These lavas may result from high degrees of partial melting during the main eruptive phase of plateau formation. There are two categories of dredged lavas from the Danger Islands Troughs, which bisect the plateau. The first is alkalic lavas having strong enrichments in light rare earth and large-ion lithophile elements; these lavas may represent late-stage activity, as one sample yields an 40Ar-39Ar age of 99.5+/-0.7 Ma. The second category consists of tholeiitic basalts with U-shaped incompatible element patterns and unusually low abundances of several elements; these basalts record a mantle component not previously observed in Manihiki, Ontong Java, or Hikurangi lavas. Their trace element characteristics may result from extensive melting of depleted mantle wedge material mixed with small amounts of volcaniclastic sediment. We are unaware of comparable basalts elsewhere.

Trace element concentrations in zircons from ODP Holes 147-894G and 153-923A

The trace element compositions of Hadean zircons have been used in two ways to argue for the existence of Hadean continental crust. One argument is based on low crystallization temperatures of Hadean zircons that have been determined using a novel geothermometer based on the Ti content of zircons in equilibrium with rutile. The second argument is based on using the trace element abundances in zircons to calculate their parental melt compositions, especially the rare earth elements. Here we demonstrate that zircons that grow from a melt formed by basalt differentiation at modern mid-ocean ridges cannot be unambiguously distinguished from Hadean zircons on either of these grounds. Thus, we conclude that the trace element compositions of Hadean zircons are permissive of models that do not include the generation of continental crust in the Hadean.

Description and chemical composition of ferromanganese encrustations and deposits in the Atlantic Ocean from R/V Atlantis II cruises 20, 42, 60, 85; R/V Chain cruise 35; R/V Knorr cruise 61 and RRS Shackleton cruise 75/1 stations

Chemical and mineralogical compositions of ferromanganese oxide coatings on rocks dredged from the New England Seamounts, the Sierra Leone Rise and the Mid-Atlantic Ridge near the Equator have been determined in an investigation of regional differences in Atlantic ferromanganese deposits. Most encrustations are clearly of hydrogenous origin, consisting mainly of todorokite and delta MnO2, but several recovered from the equatorial fracture zones may be hydrothermal accumulations. Differences in the chemistry of the water column and in growth rates of the ferromanganese coatings may be important in producing this regional contrast in composition. Fine-scale changes in element abundances within the encrustations indicate that the nature of the substrate has little influence on compositional variations.

Petrology and geochemistry of oceanic intraplate sheet-flow basalts at DSDP Hole 89-462A

Reentry of Hole 462A during Leg 89 resulted in the penetration of a further 140 m of basalt sheet-flows similar to those found during Leg 61 at the same site. Twelve volcanic units (45 to 56) were recognized, comprising a series of rapidly extruded, interlayered aphyric and poorly clinopyroxene-plagioclase-olivine phyric, nonvesicular basalts. All exhibit variable, mild hydration and oxidation, relative to fresh oceanic basalts, produced under reducing, low-CO2-activity conditions within the zeolite facies. Secondary assemblages are dominated by smectites, zeolites, and pyrite, produced by low-temperature reaction with poorly oxygenated seawater. No systematic mineralogical or chemical changes are observed with depth, although thin quenched units and more massive hypocrystalline units exhibit slightly different alteration parageneses. Chemically, the basalts are olivine- and quartz-normative tholeiites, characterized by low incompatible-element abundances, similar to mildly enriched MORB (approaching T-type), with moderate, chrondite-normalized, large-ionlithophile- element depletion patterns and generally lower or near-chrondritic ratios for many low-distribution-coefficient (KD) element pairs. In general, relative to cyclic MORB chemical variation, they are uniform throughout, although 3 chemical megagroups and 22 subgroups are recognized. It is considered that the megagroups represent separate low-pressure-fractionated systems (olivine + Plagioclase ± clinopyroxene), whereas minor variations within them (subgroups) indicate magma mixing and generation of near-steady-state conditions. Overall, relatively minor fractionation coupled with magma mixing produced a series of compositionally uniform lavas. Parental melts were produced by similar degrees of partial melting, although the source may have varied slightly in LIL-element content.

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.

Geochemistry of dikes and lavas from the north wall of the Hess Deep Rift

An investigation of ~1-m.y.-old dikes and lavas from the north wall of the Hess Deep Rift (2°15'N, 101°30'W) collected during Alvin expeditions provides a detailed view of the evolution of fast spreading oceanic crust. The study area encompasses 25 km of an east-west flow line, representing ~370,000 years of crustal accretion at the East Pacific Rise. Samples analyzed exhibit depleted incompatible trace element abundances and ratios [(La/Sm)N < 1]. Indices of fractionation (MgO), and incompatible element ratios (La/Sm, Nb/Ti) show no systematic trends along flow line. Rather, over short (<4 m) and long (~25 km) distances, significant variations are observed in major and trace element concentrations and ratios. Modeling of these variations attests to the juxtaposition of dikes of distinct parental magma compositions. These findings, combined with studies of segmentation of the subaxial magma chamber and lateral magma transport in dikes along rift-dominated systems, suggest a more realistic model of the magmatic system underlying the East Pacific Rise relative to the commonly assumed twodimensional model. In this model, melts from a heterogeneous mantle feed distinct portions of a segmented axial magma reservoir. Dikes emanating from these distinct reservoirs transport magma along axis, resulting in interleaved dikes and host lavas with different evolutionary histories. This model suggests the use of axial or flow line lava compositions to infer the evolution of axial magma chambers should be approached with caution because dikes may never erupt lava or may transport magma significant distances along axis and erupt lavas far from their axial magma chamber of origin.

Geochemistry and isotopes at DSDP Leg 80 Holes

Thirty-eight samples from DSDP Sites 549 to 551 were analyzed for major and minor components and trace element abundances. Multivariate statistical analysis of geochemical data groups the samples into two major classes: an organic-carbon- rich group (> 1% TOC) containing high levels of marine organic matter and certain trace elements (Cu, Zn, V, Ni, Co, Ba, and Cr) and an organic-carbon-lean group depleted in these components. The greatest organic and trace metal enrichments occur in the uppermost Albian to Turanian sections of Sites 549 to 551. Carbon-isotopic values of bulk carbonate for the middle Cenomanian section of Site 550 (2.35 to 2.70 per mil) and the upper Cenomanian-Turonian sections of Sites 549 (3.35 to 4.47 per mil) and 551 (3.13 to 3.72 per mil) are similar to coeval values reported elsewhere in the region. The relatively heavy d13C values from Sites 549 and 551 indicate that this interval was deposited during the global "oceanic anoxic event" that occurred at the Cenomanian/Turonian boundary. Variation in the d18O of bulk carbonate for Section 550B-18-1 of middle Cenomanian age suggests that paleosalinity and/or paleotemperature variations may have occurred concurrently with periodic anoxia at this site. Climatically controlled increases in surface-water runoff may have caused surface waters to periodically freshen, resulting in stable salinity stratification

(Table 1) Geochemistry of basalts of Nauru Basin

Leg 61 of the Deep Sea Drilling Project (DSDP) was concerned with drilling a single continuously cored multiple re-entry hole at site 462 in the Central Nauru Basin (Fig. 1). Preliminary results of this drilling, which penetrated more than 1 km beneath the sea floor, were presented earlier. One major result was the discovery of a late Cretaceous off-ridge volcanic/intrusive complex of basaltic composition and great thickness (>500 m). We now present trace element abundance data for these basalts. Results of the drilling provide further support for a relatively long-lived thermal and magmatic event in the late Cretaceous resulting in voluminous and widespread magmatism in the central and western Pacific consistent with earlier suggestions. The trace element data show that most of the rocks produced during this event have trace element characteristics intermediate between those of normal and transitional mid-ocean ridge basalts (N- and T-type MORB) and different from Hawaiian basalts. These results indicate that basalts which are depleted in light rare earth elements (LREE) relative to the heavy REE may, in certain conditions, be erupted as voluminous intra-plate eruptions far from active ridge crests.

Geochemistry of DSDP Leg 65 basalts

Leg 65 of the Deep Sea Drilling Project successfully recovered basalts from four sites in the mouth of the Gulf of California, thus completing a transect begun during Leg 64 from the continental margin of Baja California to the east side of the East Pacific Rise (EPR). Sixty-three whole-rock samples from Sites 482, 483, and 485 have been analyzed by X-ray fluorescence techniques, and a further eleven samples by instrumental neutron-activation techniques, in order to assess magma variability within and between sites. Although the major element compositions and absolute hygromagmatophile (HYG) element abundances are quite variable, all of the basalts are subalkaline tholeiites exhibiting strong more-HYG element (e.g., Rb, La, Nb, Ta) depletion (LaN/YbN ~ 0.4; Nb/Zr ~ 0.02; Ba/Zr ~ 0.23; Th/Hf ~ 0.05). These ratios, together with La/Ta ratios of 20 and Th/Ta ratios of 1.25, demonstrate that the Leg 65 basalts resemble the depleted "N-type" ocean ridge basalts recovered from the Mid-Atlantic Ridge (MAR) at 22 °N and other sections of the EPR. Zr/Ti, Zr/Y, and La/Yb ratios increase with increasing fractionation. It is clear that the basalts recovered from Sites 482, 483, and 485 were all derived from a compositionally similar source and that the compositional differences observed between lithological units can be explained by varying degrees of open system fractional crystallization (magma mixing) in subridge magma chambers. The basaltic rocks recovered from Site 474 near the margin of Baja California, and Sites 477, 478, and 481 in the Guaymas Basin, all drilled during Leg 64, have consistently higher Th/Hf, La/Sm, Zr/Ti, and Zr/Y ratios and higher absolute Sr contents than the Leg 65 basalts. While some of these variations may be explained by different conditions of partial melting, it is considered more likely that the mantle source underlying the Guaymas Basin is chemically distinct from that feeding the EPR at the mouth of the Gulf. These source variations probably reflect the complex tectonic setting of the Gulf of California, the magmas formed at the inception of spreading and in the central part of the Gulf containing a minor but significant component of sub-continental (calc-alkaline) material.

Chemical composition of volcanic glass of some tephra layers in Northeastern Pacific Ocean

Five widespread upper Cenozoic tephra layers that are found within continental sediments of the western United States have been correlated with tephra layers in marine sediments in the Humboldt and Ventura basins of coastal California by similarities in major-and trace-element abundances; four of these layers have also been identified in deep-ocean sediments at DSDP sites 34, 36, 173, and 470 in the northeastern Pacific Ocean. These layers, erupted from vents in the Yellowstone National Park area of Wyoming and Idaho (Y), the Cascade Range of the Pacific Northwest (C), and the Long Valley area, California (L), are the Huckleberry Ridge ash bed (2.0 Ma, Y), Rio Dell ash bed (ca. 1.5 Ma, C), Bishop ash bed (0.74 Ma, L), Lava Creek B ash bed (0.62 Ma, Y), and Loleta ash bed (ca. 0.4 Ma, C). The isochronous nature of these beds allows direct comparison of chronologic and climatic data in a variety of depositional environments. For example, the widespread Bishop ash bed is correlated from proximal localities near Bishop in east-central California, where it is interbedded with volcanic and glacial deposits, to lacustrine beds near Tecopa, southeastern California, to deformed on-shore marine strata near Ventura, southwestern California, to deep-ocean sediments at site 470 in the eastern Pacific Ocean west of northern Mexico. The correlations allow us to compare isotopic ages determined for the tephra layers with ages of continental and marine biostratigraphic zones determined by magnetostratigraphy and other numerical age control and also provide iterative checks for available age control. Relative age variations of as much as 0.5 m.y. exist between marine biostratigraphic datums [for example, highest occurrence level of Discoaster brouweri and Calcidiscus tropicus (= C. macintyrei)], as determined from sedimentation rate curves derived from other age control available at each of several sites. These discrepancies may be due to several factors, among which are (1) diachronism of the lowest and highest occurrence levels of marine faunal and floral species with latitude because of ecologic thresholds, (2) upward reworking of older forms in hemipelagic sections adjacent to the tectonically active coast of the western United States and other similar analytical problems in identification of biostratigraphic and magnetostratigraphic datums, (3) dissolution of microfossils or selective diagenesis of some taxa, (4) lack of precision in isotopic age calibration of these datums, (5) errors in isotopic ages of tephra beds, and (6) large variations in sedimentation rates or hiatuses in stratigraphic sections that result in age errors of interpolated datums. Correlation of tephra layers between on-land marine and deep-ocean deposits indicates that some biostratigraphic datums (diatom and calcareous nannofossil) may be truly time transgressive because at some sites, they are found above and, at other sites, below the same tephra layers.

Geochemistry of ODP Hole 135-841B

Two igneous rock units were recovered at Site 841. More than 200 m of island-arc rhyolites, rhyolitic tuffs, lapilli tuffs, and pumice breccias, divided into five units, compose the basement at the site. These rhyolitic volcanics are late middle Eocene or older and formed part of a subaerial rhyolitic volcano. These low-K rhyolites were produced by fractional crystallization of a more mafic arc-tholeiitic lava or by dehydration melting of lower crustal arc tholeiites. The Site 841 basement rocks are similar in composition to high-SiO2 lavas in the Eocene basement on 'Eua and crystallized from depleted island-arc-tholeiitic basalts like those exposed on 'Eua. No evidence is present in the rhyolites, or in the clasts enclosed within them, for boninite series magmas at Site 841. The Site 841 rhyolitic complex bears no resemblance to Cretaceous rhyolites from the Lord Howe Rise, which are enriched in K and incompatible elements. The volcanic rocks at Site 841 are part of a widely distributed Eocene volcanic episode that marked the earliest phases of subduction in the Tonga region; they are not part of an older crustal fragment. The second igneous sequence is a series of basaltic dikes and sills that intruded Miocene sediments. These basalts have trace element abundances and ratios identical to upper Miocene lavas from the Lau Ridge. The Site 841 basalts do not have any geochemical characteristics that suggest they were generated by unusual thermal conditions in the shallow sub-forearc mantle. They are most reasonably interpreted as intrusions fed by basement dikes propagated from the associated active arc. No evidence for local serpentinite exposures, like those that are common in the Mariana forearc, was found at Site 841. The results from Site 841 provide strong support for hypotheses of forearc evolution that have been advanced for the Izu-Bonin-Mariana system.

Geochemistry of basaltic rocks from ODP Site 129-801

Middle Jurassic basaltic lavas obtained from Site 801 in the western Pacific Pigafetta Basin represent ocean crust from the oldest segment of the present-day Pacific Ocean. A composite 131 m section shows the basement to be composed of an upper alkalic basalt sequence (about 157 Ma) with ocean island basalt chemical features and a lower tholeiitic basalt sequence (about 167 Ma) with typical normal-type mid-ocean ridge basalt features. The basalt sequences are separated by a quartz-cemented, yellow goethite hydrothermal deposit. Most basalts are altered to some degree and exhibit variable, low-grade smectite-celadonite-pyrite-carbonate-zeolite assemblages developed under a mainly hydrated anoxic environment. Oxidation is very minor, later in development than the hydration assemblages, and largely associated with the hydrothermal deposit. The tholeiitic normal-type mid-ocean ridge basalt has characteristically depleted incompatible element patterns and all compositions are encompassed by recent mid-ocean ridge basalt from the East Pacific Rise. Chemically, the normal-type mid-ocean ridge basalt is divided into a primitive plagioclase-olivine +/- spinel phyric group (Mg* = 72-60) and an evolved (largely) aphyric group of olivine tholeiites (Mg* = 62-40). Both groups form a single comagmatic suite related via open-system fractionation of initial olivine-spinel followed by olivine-plagioclase-clinopyroxene. The alkalic ocean island basalt are largely aphyric and display enriched incompatible element abundances within both relatively primitive olivine-rich basalts and evolved olivine-poor hawaiites related via mafic fractionation. In gross terms, the basement lithostratigraphy is a typical mid-ocean ridge basalt crust, generated at a spreading center, overlain by an off-axis seamount with ocean island basalt chemical characters.

(Table 2) Geochemistry of glasses at DSDP Leg 54 Holes

The compositions of 45 natural basalt glasses from nine dredge stations and six Deep Sea Drilling Project Leg 54 sites near 9°N on the East Pacific Rise have been determined by electron microprobe. These comprise 19 distinct chemical groups. Seventeen of these fall in the range of the eastern Pacific tholeiite suite, which is characterized by marked enrichment in FeO*, TiO2, K2O, and P2O5 as CaO, MgO, and Al2O3 all decrease. Based on trace elements, an estimated 50-75 per cent fractionation of plagioclase, clinopyroxene, and olivine is required to produce ferrobasalts from parental olivine tholeiites. Additional chemical variations occur which require source heterogeneities, differences in the degree of melting, different courses of shallow fractionation, or magma mixing to explain. Glass compositions from within the Siqueiros fracture zone are mostly less fractionated than those from the flanks of the Rise, and show chemical differences which require variations in the depth of melting or highpressure fractionation to explain. Some of them could not be parental to East Pacific Rise flank ferrobasalts. Two remaining glass groups, from dredge hauls atop a ridge and a seamount, respectively, have distinctly higher K2O, P2O5, and TiO2 as well as lower CaO/Al2O3 and SiO2 at corresponding values of MgO than the tholeiite suite. These abundances, and whole-rock Y/Zr, Ce/Y, Nb/Zr, and isotopic abundances indicate that these basalts had a deeper, less depleted mantle source than the Rise tholeiite suite. Trace element abundances preclude the "ridge" basalt type from being a hybrid between the "seamount" basalt type and any East Pacific Rise tholeiite so far analyzed. The East Pacific Rise glasses from 9°N compare very closely to glasses dredged and drilled elsewhere on the East Pacific Rise. However, glass compositions from Site 424 on the Galapagos Rift drilled during Leg 54, as well as glasses and basalts dredged from the Galapagos and Costa Rica rifts, indicate that a greater degree of melting prevailed along much of the Galapagos Spreading Center than anywhere along the East Pacific Rise.

Age model and elemental data of DSDP Holes 48-401 and 80-549

A growing body of geologic evidence suggests that emplacement of the North Atlantic Igneous Province (NAIP) played a major role in global warming during the early Paleogene as well as in the transient Paleocene-Eocene thermal maximum (PETM) event. A ~5 million year record of major and trace element abundances spanning 56 to 51 Ma at Deep Sea Drilling Project Sites 401 and 549 confirms that the majority of NAIP volcanism occurred as subaerial flows. Thus the trace element records provide constraints on the nature and scope of the environmental impact of the NAIP during the late Paleocene-early Eocene interval. Subaerial volcanism would have injected mantle CO2 directly into the atmosphere, resulting in a more immediate increase in atmospheric greenhouse gas abundances than CO2 input through submarine volcanism. The lack of significant hydrothermalism contradicts recently proposed mechanisms for thermally destabilizing methane hydrate reservoirs during the PETM. Any connection between NAIP volcanism and PETM warming had to occur through the atmosphere.