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.

Chemical composition and age of magmatic rocks from the underwater Hokkaido Rise

Geological and geophysical investigations carried out within the Hokkaido Rise showed that intrusives composing outcrops of the crystalline basement on the ocean floor form a continuous series from monzonites and diorite-monzonites to granites with prevalence of granodiorites with stable mineralogical association: biotite - hornblende - K-feldspar. Acidic volcanic rocks are characterized by a similar mineralogical association with almost complete absence of plagioclase-pyroxene species. It seems that the Hokkaido Rise, as well as the marginal oceanic Zenkevich swell as a whole are not primary oceanic structural formations and have undergone a complex and long history of geological development with intense orogenic movements that occurred in Middle Cretaceous and preceded subalkaline basalt outpouring during postorogenic subsidence of the Earth crust.

Petrological and geochemical characteristics of DSDP Hole 37-334 gabbroic cumulates (Table 1)

The gabbronoritic cumulates drilled at DSDP Site 334 (Mid-Atlantic Ridge off the FAMOUS area) are neither crystallization products of the associated basalts, nor from any MORB composition documented along ocean ridges. Their parent melts are richer in SiO2 than MORB at a given MgO content, as attested by the crystallization sequence starting with an olivine+calcic and sub-calcic pyroxene assemblages. These melts are issued from a source highly depleted in incompatible elements, likely residual peridotite left after MORB extraction. To understand the role of water in the genesis of these lithologies whose occurrence in a mid-ocean ridge setting is rather puzzling, we performed a geochemical study on clinopyroxene separates following an analytical protocol able to remove the effects of water rock interactions post-dating their crystallization. Accordingly, the measured isotopic signatures can be used to trace magma sources. We find that Site 334 clinopyroxenes depart from the global mantle correlation: normal MORB values for the 143Nd/ 144Nd ratio (0.51307-0.51315) are associated to highly radiogenic 87Sr / 86Sr (0.7034-0.7067) ratios. This indicates that the parent melts of Site 334 cumulates are issued from a MORB source but that seawater contamination occurred at some stage of their genesis. The extent of contamination, traced by the Sr isotopic signature, is variable within all cumulates but more developed for gabbronorites sensus stricto, suggesting that seawater introduction was a continuous process during all the magmatic evolution of the system, from partial melting to fractional crystallization. Simple masse balance calculations are consistent with a contaminating agent having the characters of a highly hydrated (possibly water saturated) silica-rich melt depleted in almost all incompatible major, minor and trace elements relative to MORB. Mixing in various proportions of contaminated melts similar to the parent melts of Site 334 cumulates with MORB can account for part of the variability in the Sr isotopic signature of oceanic basalts, among other to the short wavelength isotopic "noise" superimposed on regional trends. We conclude that seawater introduction into residual peridotite at shallow depth beneath mid-ocean ridges can lead mantle rocks and their melts to follow complex P-T-fH2O paths that mimic petrogenetic contexts classically attributed to subduction zone environments, like the production of boninitic-andesitic magmas.

Sample descriptions, d-spacing and geochemistry at DSDP Holes 68-501 and 69-504B

Mössbauer analyses were conducted on a sample of saponite selected from DSDP Leg 69 basalt core. The sample was initially placed within a nitrogen-purged container on-board Glomar Challenger approximately three hours after recovery, where it remained until analysis. The Mössbauer data revealed an original, in situ Fe2O3/FeO ratio of 0.46, with both Fe**2+ and Fe**3+ in octahedral coordination. With controlled exposure to air under ambient laboratory storage conditions, the proportion of Fe**3+ increased from an original 30% to 51% over a period of about 11.5 months. The Fe**3+ thus produced remained in octahedral coordination, and no observable changes occurred in the physical appearance of the sample.

Chemistry and boron isotope ratios of Izu arc front volcanic rocks

The process of fluid release from the subducting slab beneath the Izu arc volcanic front (Izu VF) was examined by measuring B concentrations and B isotope ratios in the Neogene fallout tephra (ODP Site 782A). Both were measured by secondary ion mass spectrometry, in a subset of matrix glasses and glassy plagioclase-hosted melt inclusions selected from material previously analyzed for major and trace elements (glasses) and radiogenic isotopes (Sr, Nd, Pb; bulk tephra). These tephra glasses have high B abundances (~10-60 ppm) and heavy delta11B values (+4.5? to +12.0?), extending the previously reported range for Izu VF rocks (delta11B, +7.0? to +7.3?). The glasses show striking negative correlations of delta11B with large ion lithophile element (LILE)/Nb ratios. These correlations cannot be explained by mixing two separate slab fluids, originating from the subducting sediment and the subducting basaltic crust, respectively (model A). Two alternative models (models B and C) are proposed. Model B proposes that the inverse correlations are inherited from altered oceanic crust (AOC), which shows a systematic decrease of B and LILE with increasing depth (from basaltic layer 2A to layer 3), paralleled by an increase in delta11B (from ~ +1? to +10? to +24?). In this model, the contribution of sedimentary B is insignificant (<4% of B in the Izu VF rocks). Model C explains the correlation as a mixture of a low-delta11B (~ +1?) 'composite' slab fluid (a mixture of metasediment- and metabasalt-derived fluids) with a metasomatized mantle wedge containing elevated B (~1-2 ppm) and heavy delta11B (~ +14?). The mantle wedge was likely metasomatized by 11B-rich fluids beneath the outer forearc, and subsequently down dragged to arc front depths by the descending slab. Pb-B isotope systematics indicate that, at arc front depths, ~ 53% of the B in the Izu VF is derived from the wedge. This implies that the heavy delta11B values of Izu VF rocks are largely a result of fluid fractionation, and do not reflect variations in slab source provenance (i.e. subducting sediment vs. basaltic crust). Since the B content of the peridotite at the outer forearc (7-58 ppm B, mean 24 +/- 16 ppm) is much higher than beneath the arc front (~1-2 ppm B), the hydrated mantle wedge must have released a B-rich fluid on its downward path. This 'wedge flux' can explain (1) the across-arc decrease in B and delta11B (e.g. Izu, Kuriles), without requiring a progressive decrease in fluid flux from the subducting slab, and (2) the thermal structure of volcanic arcs, as reflected in the B and delta11B variations of volcanic arc rocks.

Age and chemical composition of dredged igneous rocks from the Vityaz Ridge, Pacific slope of the Kuril Island Arc

Original results of igneous rock studies are presented. The rocks were dredged during a marine expedition (cruise 37 of R/V Akademik M.A. Lavrent'ev in August-September, 2005) in the region of the submarine Vityaz Ridge and the Kuril Arc outer slope. Several age complexes (Late Cretaceous, Eocene, Late Oligocene, Miocene, and Pliocene-Pleistocene) are recognizable on the Vityaz Ridge. These complexes are characterized by a number of common geochemical features since all of them represent formations of island arc calc-alkali series. At the same time, they also have individual features reflecting different geodynamic settings. The outer slope of the Kuril Arc demonstrates submarine volcanism. Pliocene-Pleistocene volcanic rocks dredged here are similar to volcanites of the Kuril-Kamchatka Arc frontal zone.

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.

Chemical composition and K-Ar age of rocks from the northern Sea of Japan

The Middle Paleozoic complex consists of terrigenous and volcanogenic materials metamorphized in greenschist facies. Clastic rocks have arkosic composition and are formed by alteration of basalts and metamorphic rocks. Metaeffusives were formed from basaltoid products of oceanic tholeiite magma indicating that underwater rise structures of the northern Sea of Japan were emplaced on the oceanic crust.

Chemical composition of rhyolites of ODP Site 103-639

Holes 639E and 639F were drilled along the western slope of a tilted fault block in an attempt to recover complete syn- and pre-rift stratigraphic sections and continental basement. Both holes ended in an apparent talus pile or conglomerate that includes cobbles of altered rhyolitic rock. Three small pieces of rhyolite (comprising about 20 cm of sample) were recovered from the bottoms of Holes 639E and 639F in the core catchers of the deepest cores. This note presents geochemical data from these rhyolitic rocks. Also recovered were quartz sandstones, graywackes, metasandstones, and quartz breccias. This assemblage of continentally derived 'basement' material was overlain by mudstones, limestones, and crystalline dolomites (see 'Site 639' chapter; Shipboard Scientific Party, 1987, doi:10.2973/odp.proc.ir.103.110.1987).

Chemical composition of celadonite-glauconite minerals and cristobalite from altered oceanic basalts of DSDP Hole 49-407

Features of associations of newly formed minerals in Oligocene basalts from the Reykjanes Ridge (DSDP Hole 407), which consist in wide development of celadonite-glauconite group minerals, as well as saponite, cristobalite and specific Fe-Si formations is shown. Detailed mineralogical and geochemical characteristics of these newly formed minerals are reported. It is firstly shown that at underwater alteration of basalts not only celadonite can be generated, but also glauconite. Dependence of secondary mineral composition from petrochemical features of original basalts and from their permeability is revealed. It is concluded that complexes of secondary minerals formed during alteration of basalts with similar petrochemical characteristics in the ocean and on the continent are different.

Chemistry and fluid inclusions of the sheeted dike comples of ODP Holes 137-504B and 140-504B

Fluid inclusions in variably altered diabase recovered from Ocean Drilling Program Legs 137 and 140 at Hole 504B, Costa Rica Rift, exhibit fluid salinities up to 3.7 times that of seawater values (11.7 wt% NaCl equivalent) and exhibit uncorrected homogenization temperatures of 125°C to 202°C. The liquid-dominated inclusions commonly are entrapped in zones of secondary plagioclase and may be primary in origin. Fluid salinities are similar to compositions of fluids venting on the seafloor (0.4-7.0 wt% NaCl) and overlap with those measured in metabasalt samples recovered from near the Kane Fracture Zone on the Mid-Atlantic Ridge and from the Troodos ophiolite, Cyprus. The salinity variations may reflect hydration reactions involving formation of secondary mineral assemblages under rock-dominated conditions, which modify the ionic strength of hydrothermal fluids by consuming or liberating water and chloride ion. Rare CO2-CH4-bearing inclusions, subjacent to zones where talc after olivine becomes an important secondary mineral phase (1700 mbsf), may have formed due to local interaction of seawater and olivine at low water to rock ratios. Corrected average fluid inclusion homogenization temperatures exhibit a gradient from 159°C at a depth of 1370 mbsf to 183°C at a depth of 1992 mbsf and are in apparent equilibrium with the present conductive downhole temperatures. These data indicate that fluid inclusions may be used to estimate downhole temperatures if logging data are unavailable. The compositional and thermal evolution of the diabase-hosted fluids may reflect late-stage, off-axis circulation and conductive heating of compositionally modified seawater in the sheeted dike complex at Hole 504B.

Geochemistry and Fe/(Ti + Ti), x, Curie temperature, and oxidation parameter z at DSDP Hole 597C

Electron microprobe and thermomagnetic analyses of selected basalt samples from Hole 597C were performed. The main purpose of this work was to investigate and estimate the degree of oxidation of the samples using the ratios of Fe to Ti and the Curie temperatures obtained from thermomagnetic curves. The results show that the magnetic properties of samples from Hole 597C change at a sub-bottom depth of 100 m, and that low-temperature and high-temperature oxidation processes prevailed above and below 100 m, respectively.

Geochemistry, minerals and b-parameter at DSDP Leg 70 Holes

Clay minerals recovered from the Galapagos hydrothermal mounds (Holes 506C, 507D, and 509B) are mainly iron-rich nontronite-like minerals enriched in potassium. Nontronites from Hole 509B show a distinct tendency to become micaceous toward the lower beds of clay sediments. Mn-crusts consist mainly of todorokite or a mixture of todorokite and nontronite. Minerals of clay and Mnrich sediments in the mounds originated from hydrothermal solutions of uncertain origin. Pelagic oozes from hydrothermal mounds and from areas between mounds (Hole 506D) consist mainly of calcite. In the carbonate beds on or near the hydrothermal mounds an admixture of smectite is often found.

Geochemistry of microtektites from Victoria Land Transantarctic Mountains

We extended the petrographic and geochemical dataset for the recently discovered Transantarctic Mountain microtektites in order to check our previous claim that they are related to the Australasian strewn field. Based on color and composition, the 465 microtektites so far identified include two groups of transparent glass spheres less than ca. 800 µm in diameter: the most abundant pale-yellow, or normal, microtektites, and the rare pale-green, or high-Mg, microtektites. The major element composition of normal microtektites determined through electron microprobe analysis is characterized by high contents of silica (SiO2 = 71.5 ± 3.6 (1 sigma) wt%) and alumina (Al2O3 = 15.5 ± 2.2 (1 sigma) wt%), low total alkali element contents (0.50-1.85 wt%), and MgO abundances <6 wt%. The high-Mg microtektites have a distinctly higher MgO content >10 wt%. Transantarctic Mountain microtektites contain rare silica-rich (up to 93 wt% SiO2) glassy inclusions similar to those found in two Australasian microtektites analyzed here for comparison. These inclusions are interpreted as partially digested, lechatelierite-like inclusions typically found in tektites and microtektites. The major and trace element (by laser ablation - inductively coupled plasma - mass spectrometry) abundance pattern of the Transantarctic Mountain microtektites matches the average upper continental crust composition for most elements. Major deviations include a strong to moderate depletion in volatile elements including Pb, Zn, Na, K, Rb, Sr and Cs, as a likely result of severe volatile loss during the high temperature melting and vaporization of crustal target rocks. The normal and high-Mg Transantarctic Mountain microtektites have compositions similar to the most volatile-poor normal and high-Mg Australasian microtektites reported in the literature. Their very low H2O and B contents (by secondary ion mass spectrometry) of 85 ± 58 (1 sigma) ?g/g and 0.53 ± 0.21 ?g/g, respectively, evidence the extreme volatile loss characteristically observed in tektites. The Sr and Nd isotopic compositions of multigrain samples of Transantarctic Mountain microtektites are 87Sr/86Sr ~ 0.71629 and 143Nd/144Nd ~ 0.51209, and fall into the Australasian tektite compositional field. The Nd model age calculated with respect to the chondritic uniform reservoir (CHUR) is TNdCHUR ~ 1.1 Ga, indicating a Meso-Proterozoic crustal source rock, as was derived for Australasian tektites as well. Coupled with the Quaternary age from the literature, the extended dataset presented in this work strengthens our previous conclusion that Transantarctic Mountain microtektites represent a major southward extension of the Australasian tektite/microtektite strewn field. Furthermore, the significant depletion in volatile elements (i.e., Pb, B, Na, K, Zn, Rb, Sr and Cs) of both normal and high-Mg Transantarctic Mountain microtektites relative to the Australasian ones provide us with further confirmation of a possible relationship between high temperature-time regimes in the microtektite-forming process and ejection distance.

Chemistry of very young basalts from ODP Hole 106-648B

Basalts in Hole 648B, located in the rift valley of the Mid-Atlantic Ridge at 23°N in crust estimated to be less than 100,000 years old, are mainly fresh, but small amounts of secondary phases are found on fracture surfaces and in alteration halos within the rocks. The halos are defined by dark bands 1-4 mm thick that have developed parallel to fracture surfaces or pillow margins and which in some cases have migrated some centimeters into the rock. The dark bands are the principal locus of secondary phases. The secondary phases are olive-green and yellow protoceladonites, of composition and structure intermediate between celadonite and iron-rich saponite, red (Mn-poor) to opaque (Mn-rich) iron oxyhydroxides, mixtures of protoceladonite and iron oxyhydroxide, and rare manganese oxides. These phases occur mainly as linings or fillings of open spaces in the basalt within the dark bands. Sulfides and intersertal glass are the only primary phases that can be seen to have been altered. Where dark bands have migrated into the rock, the rock behind the advancing band is almost devoid of secondary phases, implying redissolution. The potassium and magnesium in the secondary phases could have been supplied from ambient seawater. The aluminum in the protoceladonites must have been derived from local reaction of intergranular glass. The source of iron and silica could have been intergranular glass or low temperature mineralizing solutions of the type responsible for the formation of deposits of manganese oxides and iron oxyhydroxides and silicates on the seafloor.