Geochemistry of volcaniclastites of the western Pacific Ocean

Samples collected from the coarse basal portions of mid-Cretaceous volcaniclastic turbidites from the Mariana and Pigafetta basins are remarkably similar in terms of the petrographic and chemical features of their igneous clasts and bulk rock composition. Clasts of magmatic origin are dominated by glassy vesicular shards, variably phyric, holocrystalline basalts, and crystal fragments (olivine, clinopyroxene, plagioclase, amphibole, and biotite). The composition of the pyroxenes and amphiboles are typical of those found in differentiated hydrous alkali basalts. The bulk chemical composition of the volcaniclastites (based on stable incompatible elements and their ratios in highly vitric samples) is characteristic of alkali basalts found in within-plate oceanic eruptive environments. Miocene volcaniclastites from Site 802 are broadly similar to the Cretaceous samples in terms of clast type and bulk composition, and have also been derived from an oceanic alkali basalt source. The chemistry of the Miocene volcaniclastites differ, however, in having distinctive Zr/Y and Zr/Nb ratios and a more restricted chemical composition. The magmatic products of nearly emergent seamounts within the western Pacific basins appears to have been dominated by alkali basalt volcanism during the mid-Cretaceous and also the Miocene. The highly vitric nature of the Cretaceous and Miocene volcaniclastites, together with the morphology and vesicularity of their shards, suggests that they are the reworked (via mass flow) products of hyaloclastite accumulations produced in a shallow-water eruptive environment, such as that adjacent to nearly emergent seamounts or ocean islands. The association of ooids, reefal debris, and, in rare cases, woody material with the volcaniclastites supports their shallow-water derivation.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.

Geochemistry of Cretaceous sills and lava flows of ODP Holes 129-800A and 129-802A

On the basis of their respective eruptive environments and chemical characteristics, alkalic dolerite sills from the northern Pigafetta Basin (Site 800) and tholeiitic pillow lavas from the Mariana Basin (Site 802) sampled during Ocean Drilling Program Leg 129 are considered to represent examples of the widespread mid-Cretaceous volcanic event in the western Pacific. Both groups of basic rocks feature mild, low-grade, anoxic smectite-celadonite-carbonate-pyrite alteration; late-stage oxidation is very limited in extent, with the exception of the uppermost sill unit at Site 800. The aphyric and nonvesicular Site 800 alkalic dolerite sills are all well-evolved mineralogically and chemically, being mainly of hawaiite composition, and are similar to ocean island basalts. They are characterized by high contents of incompatible elements (for example, 300-400 ppm Zr), well-fractionated rare earth element patterns ([La/Yb]N 18-21) and HIMU isotopic characters. They probably represent deep-sea, lateral, intrusive off-shoots from nearby seamounts of similar age. The olivine-plagioclase +/- clinopyroxene phyric tholeiitic pillow lavas and thin flows of Site 802 are nonvesicular and quench-textured throughout. Relative to normal-type mid-ocean ridge basalt, they are enriched in large-ion-lithophile elements, exhibit flat (unfractionated) rare earth element patterns and have distinctive (lower) Zr/Nb, Zr/Ta, La/Ta, and Hf/Th ratios. Overall they are compositionally and isotopically similar to the mid-Cretaceous tholeiites of the Nauru basin and the Ontong-Java and Manihiki plateaus. The Site 802 tholeiites differ from the thickened crustal segments of the oceanic plateaus, however, in apparently representing only a thin veneer over the local basement in an off-axis environment.

Fission track analyses of ODP Hole 129-800A samples

Four models of fission track annealing in apatite are compared with measured fission track lengths in samples from Site 800 in the East Mariana Basin, Ocean Drilling Program Leg 129, given an independently determined temperature history. The temperature history of Site 800 was calculated using a one-dimensional, compactive, conductive heat flow model assuming two end-member thermal cases: one for cooling of Jurassic ocean crust that has experienced no subsequent heating, and one for cooling of Cretaceous ocean crust. Because the samples analyzed were only shallowly buried and because the tectonic history of the area since sample deposition is simple, resolution of the temperature history is high. The maximum temperature experienced by the sampled bed is between 16°-21°C and occurs at 96 Ma; temperatures since the Cretaceous have dropped in spite of continued pelagic sediment deposition because heat flow has continued to decay exponentially and bottom-water temperatures have dropped. Fission tracks observed within apatite grains from the sampled bed are 14.6 +/- 0.1 µm (1 sigma) long. Given the proposed temperature history of the samples, one unpublished and three published models of fission track annealing predict mean track lengths from 14.8 to 15.9 µm. These models require temperatures as much as 40°C higher than the calculated paleotemperature maximum of the sampled bed to produce the same degree of track annealing. Measured and predicted values are different because annealing models are based on extrapolation of high temperature laboratory data to geologic times. The model that makes the closest prediction is based on the greatest number of experiments performed at low temperature and on an apatite having composition closest to that of the core samples.