Element concentrations, and Sr and Os isotope ratios of DSDP Leg 92 metalliferous carbonates

The Os concentration and isotopic composition of metalliferous carbonates deposited on the East Pacific Rise over the past 28 Ma are reported with complimentary Sr isotope data. Variations in the Os isotopic composition of these samples are interpreted as a record of past changes in the Os isotopic composition of seawater. These results are consistent with isotopic analyses of leachable Os in pelagic clays which have also been interpreted as a record of the 187Os/186Os ratio of seawater through time (Pegram et al., 1992, doi:10.1016/0012-821X(92)90132-F). The metalliferous carbonate record clearly shows that seawater Os and Sr isotope systems are partially decoupled from one another over the past 28 Ma. Accelerated weathering of ancient organic-rich sediments is suggested as a possible mechanism to account for this decoupling and the rapid increase in the 187Os//186Os ratio of seawater over the past 15 Ma. This rapid increase suggests that the seawater Os record can potentially be used as a stratigraphic tool in some Neogene marine deposits.

(Table 2) Weight percent organic carbon from ODP Site 138-847

As the length of marine cores increases and sampling intervals decrease, the need for rapid and inexpensive means of determining sediment composition has become apparent. In this study we examine one potentially useful technique for assessing compositional changes in marine cores, diffuse reflectance spectrophotometry. We examined near-ultraviolet, visible, and near-infrared reflectance spectra from five data sets. Each data set consists of calibration samples and test samples. The calibration samples' spectra were related to a sediment component using multiple linear regression. The resulting regression or calibration equations were then evaluated using the test samples. Calibration equations were written relating spectra to several sediment components incduding carbonate (Atlantic and east Pacific Rise ODP Site 847), organic carbon content (Atlantic and east Pacific Rise), and opal content (east Pacific Rise). The correlation coefficients for the regression equations ranged from a high of 0.99 for carbonate and opal at ODP Site 847 to a low of 0.97 for Atlantic carbonate indicating that spectral variations are highly correlated to sediment composition. All of the equations include a substantial number of variables from shorter visible and longer near ultraviolet wavelengths suggesting that these wavelengths are especially important for devices designed specifically to scan marine cores. Although equations for estimating organic and carbonate content appear independent of other sediment components, the opal equation is strongly dependent on carbonate content indicating that opal concentration is correlated to carbonate content. Tests of the calibration equations indicated that all our equations reasonably estimate the pattern of changes, either down core or in surface sediments. Where our spectral estimates have difficulty is with absolute values, frequently over or underestimating observed values by a substantial amount. Within these limitations diffuse reflectance spectrophotometry can be a useful tool for characterizing marine cores and as our understanding of the relationship between spectra and mineralogy improves so will estimates of absolute values.

Contents and accumulation rates of the rare earth and some other elements in metalliferous sediments from DSDP Hole 92-598

The sediments recovered during DSDP Leg 92 (Site 598) include a complete 16 m.y. record of hydrothermal sedimentation along the western flank of the East Pacific Rise at 19°S. Fifty samples from this sediment column were analyzed to test the hypothesis that the REE composition of the hydrothermal component is primarily acquired via scavenging from seawater. Site 598 provides an ideal sample suite for this purpose: the sediments are lithologically "simple," primarily consisting of a mixture of hydrothermal materials and biogenous carbonates; the composition of the hydrothermal component is essentially constant through space and time; and the sediments have undergone minimal diagenetic alteration. The following observations suggest the above-stated hypothesis is true. The Ce anomaly as well as key indices of light and heavy REE behavior all show that the REE pattern of hydrothermal sediments approaches that of seawater with increasing paleodistance from the rise crest. Moreover, shale-normalized REE patterns are similar to that of seawater, varying only in absolute REE content: the REE content increases with distance from the paleo-rise crest and exhibits a pronounced increase in sediments deposited below the paleolysocline. Based on significant correlative relationships between paleodistance from the rise crest and both the concentration and mass accumulation rates (MARs) of REEs and Fe, we conclude the REEs in the hydrothermal component are derived from the interaction of seawater and Fe in the hydrothermal plume.

Chemical composition of bottom sediments along the Transpacific section

Distribution of Fe, Mn, Ti, Cu, Ni, Co, V, Cr, Mo, As in bottom sediments of a section from the Hawaiian Islands to the coast of Mexico. In the surface layer and isochronic layers of sediments from biogenic-terrigenous sediments of the Mexico coast to pelagic red clays of the Northeast Basin contents of all studied elements increase, and more sharply for mobile ones - Mn, Mo, Cu, Ni, Co, As. In near Hawaii sediments rich in coarsely fragmented volcanic-terrigenous and pyroclastic material of basalt composition enriched in Ti, Fe, Cr, V, P contents of these elements in surface sediments and in sediment mass increase and contents of Mn, Mo, Ni, Co, Cu, As (for the same reason) decrease compared to red clays. An area of hemipelagic and transition sediments is identified; these sediments have much higher contents of Mn, Fe, Cu, Ni, Mo, As, (Ba) than red clays and similar sediments of the Northwest Pacific Ocean. This is due to hydrothermal activity in the tectonically active zone at the northern extension of the East Pacific Rise. Similar character of distribution of the elements in the surface layer and in the isochrone layers of bottom sediments along the most part of the section is shown. Similarity between distribution of the elements in sediments of the western and the eastern parts of the Transpacific section is established.

Geochemistry and minerals at DSDP LEg 58 Holes

Leg 58 successfully recovered basalt at Sites 442, 443, and 444, in the Shikoku Basin, and at Site 446 in the Daito Basin. Only at Site 442 did penetration reach unequivocal oceanic layer 2; at the other sites, only off-axis sills and flows were sampled. Petrographic observations indicate that back-arc basalts from the Shikoku Basin, with the exception of the kaersutite-bearing upper sill at Site 444, are mineralogically similar to basalts being erupted at normal mid-ocean ridges. However, the Shikoku Basin basalts are commonly very vesicular, indicating a high volatile content in the magmas. Site 446 in the Daito Basin penetrated a succession of 23 sills which include both kaersutite-bearing and kaersutite-free basalt varieties. A total of 187 samples from the four sites has been analyzed for major and trace elements using X-ray-fluorescence techniques. Chemically, the basalts from Sites 442 and 443 and the lower sill of Site 444 are subalkaline tholeiites and resemble N-type ocean-ridge basalts found along the East Pacific Rise and at 22° N on the Mid-Atlantic Ridge (MAR), although they are not quite as depleted in certain hygromagmatophile (HYG) elements. They do not show any chemical affinities with island-arc tholeiites. The basalts from Site 446 and from the upper sill at Site 444 show alkaline and tholeiitic tendencies, and are enriched in the more-HYG elements; they chemically resemble enriched or E-type basalts and their differentiates found along sections of the MAR (e.g., 45°N) and on ocean islands (e.g., Iceland and the Azores). Most of the intra-site variation may be attributed to crystal settling within individual massive flows and sills, to high-level fractional crystallization in sub-ridge magma chambers, or, where there is evidence of a long period of magmatic quiescence between units, to batch partial melting. However, the basalts from Sites 442 and 443 and from the lower sill at Site 444 cannot easily be related to those from Site 446 and the upper sill at Site 444, and it is possible that the different basalt types were derived from chemically distinct mantle sources. From comparison of the Leg 58 data with those already available for other intra-oceanic back-arc basins, it appears that the mantle sources giving rise to back-arc-basin basalts are chemically as diverse as those for mid-ocean ridges. In addition, the high vesicularity of the Shikoku Basin basalts supports previous observations that the mantle source of back-arc-basin basalts may be contaminated by a hydrous component from the adjacent subduction zone.

Velocity-density systematics for basalts at DSPD Leg 54 Holes

Precise velocity and density measurements at atmospheric and elevated pressures have been obtained on basalts drilled in 13 holes during Leg 54. The vp-sigma data show systematics which are controlled by the degree of crystallinity (or conversely, glassiness), microstructure, and original mineralogy and chemistry. Extensively fractionated basalts with marked iron enrichment produce anomalously low measured velocities at densities above 2.90 g/cm**3. Also, the effective in situ pressure acting on Leg 54 basalts is less than hydrostatic, and perhaps close to zero. At zero effective pressure, the measured velocities average 2.5 km/s higher than East Pacific Rise upper crustal velocities determined by seismic refraction. This implies that the in situ velocities are undoubtedly a result of the highly fragmented nature of East Pacific Rise crust.

Elemental and stable isotopic composition of some metalliferous and pelagic sediments at DSDP Leg 70 Holes

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at subsurface depths of about 2 to 20 meters; Mn-oxide material is limited to the upper 2 meters of the mounds. The nontronite forms intervals of up to a few meters' thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major element composition between nontronites from varying locations within the mounds, with adjacent granules from a given sample having very similar compositions; (2) individual granules show little internal variation in composition. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of Eh and composition during nontronite formation. Mn-oxide crusts have very low Fe contents, a feature characteristic of rapidly deposited Mn-oxide crusts formed under hydrothermal influences. The rare-earth element (REE) abundances of the nontronites are generally extremely low, totalling less than several ppm. Two samples have the negatively Ce anomaly typical of authigenic precipitates formed relatively rapidly from seawater. A Mn-oxide crust sample has low REE contents, typical of Mn-oxide crusts formed under hydrothermal influences, but no negative Ce anomaly. A sample of unusual Mn-Fe-oxide mud has relatively high REE concentrations and a seawater-type pattern; both of these features are also found for metalliferous sediments from the East Pacific Rise. The oxygen and hydrogen isotopic composition of the nontronites define a restricted field within a d18O-dD plot. In manganiferous sediments, d18O and dD appear to decrease with increase in the Mn-oxide content of the sediment. From the d18O values of the nontronites, formation temperatures in the range of about 20-30°C have been estimated. By comparison, temperatures of up to 11.5 °C at a 9-meter depth have been directly measured within the mounds (Corliss et al., 1979), and heat-flow data suggest present basement/sediment interface temperatures of 15-25°C. In a plot of Fe + Mn vs. d18O, the Mn-oxide crust and Mn-Fe-ooze plot near the tie-lines for authigenic Mn nodules and silicate phases, implying that they have formed in isotopic equilibrium with seawater at or close to bottom-water temperatures.

Composition of dikes and lavas from the Pito Deep Rift

The northwest trending walls of the Pito Deep Rift (PDR), a tectonic window in the southeast Pacific, expose in situ oceanic crust generated ?3 Ma at the superfast spreading southern East Pacific Rise (SEPR). Whole rock analyses were performed on over 200 samples of dikes and lavas recovered from two ~8 km**2 study areas. Most of the PDR samples are incompatible-element-depleted normal mid-ocean ridge basalts (NMORB; (La/Sm)N < 1.0) that show typical tholeiitic fractionation trends. Correlated variations in Pb isotope ratios, rare earth element patterns, and ratios of incompatible elements (e.g., (Ce/Yb)N) are best explained by mixing curves between two enriched and one depleted mantle sources. Pb isotope compositions of most PDR NMORB are offset from SEPR data toward higher values of 207Pb/204Pb, suggesting that an enriched component of the mantle was present in this region in the past ?3 Ma but is not evident today. Overall, the PDR crust is highly variable in composition over long and short spatial scales, demonstrating that chemically distinct lavas and dikes can be emplaced within the same segment over short timescales. However, the limited spatial distribution of high 206Pb/204Pb samples and the occurrence of relatively homogeneous MgO compositions (ranging <2.5 wt %) within a few of the individual dive transects (over distances of ~1 km) suggests that the mantle source composition evolved and magmatic temperatures persisted over timescales of tens of thousands of years. The high degree of chemical variability between pairs of adjacent dikes is interpreted as evidence for along-axis transport of magma from chemically distinct portions of the melt lens. Our findings suggest that lateral dike propagation occurs to a significant degree at superfast spreading centers.

Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.

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.

Nannofossil biostratigraphy of ODP Hole 206-1256B sediments

Site 1256 of Ocean Drilling Program Leg 206 to the Guatemala Basin on the eastern flank of the East Pacific Rise yielded a near-complete, middle Miocene-Quaternary carbonate-rich section that provides an opportunity to study low-latitude biostratigraphic and paleoceanographic events. The sedimentary sequence in Hole 1256B has been zoned using calcareous nannofossils according to the biostratigraphic schemes by Martini of 1971 (modified by Martini and Müller in 1986) and Okada and Bukry of 1980. The nannofossil assemblage is characteristic of the low latitudes, with abundant Gephyrocapsa, Discoaster, and Sphenolithus, and is in general moderately to well preserved, depending on nannofossil abundance and the presence of diatoms. Age estimates for the first occurrence and last occurrence of Reticulofenestra rotaria were derived from biostratigraphy and magnetostratigraphy independently and assigned to 7.18 and 6.32 Ma, respectively. Linear sedimentation rates, calculated using 28 nannofossil datums and age estimates, are high in the middle Miocene, decrease from the late Miocene to the Pliocene, then increase upsection. The abrupt drop in carbonate mass accumulation rates during the early late Miocene is referred to as the "carbonate crash." This pattern reflects (1) the long-trend decrease of productivity as the site moves away from the upwelling system at the equatorial divergence as well as (2) fluctuation in the chemistry of the bottom waters associated with production of the North Atlantic Bottom Water and ventilation via the Panama Gateway. A basement age of 14.5 Ma was obtained by extrapolating the 39.1-m/m.y. rate in the middle Miocene to the basement at 250.7 meters below seafloor, and is consistent with the ~15-Ma age of the oceanic crust estimated from marine magnetic anomalies. Reworked nannofossils and lithologic changes were used to unravel postdepositional history, and three episodes were recognized, one of which in the latest Miocene can be widely correlated.

(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.