Geochemistry of Pleistocene volcanic rocks in the Mariana Forearc

Geophysical surveys of the Mariana forearc, in an area equidistant from the Mariana Trench and the active Mariana Island Arc, revealed a 40-m-deep graben about 13 km northwest of Conical Seamount, a serpentine mud volcano. The graben and its bounding horst blocks are part of a fault zone that strikes northwest-southeast beneath Conical Seamount. One horst block was drilled during Leg 125 of the Ocean Drilling Program (Site 781). Three lithologic units were recovered at Site 781: an upper sedimentary unit, a middle basalt unit, and a lower sedimentary unit. The upper unit, between 0 and 72 mbsf, consists of upper Pliocene to Holocene diatomaceous and radiolarian-bearing silty clay that grades down into vitric silty clay and vitric clayey silt. The middle unit is a Pleistocene vesicular, porphyritic basalt, the top of which corresponds to a high-amplitude reflection on the reflection profiles. The lower unit is a middle to upper (and possibly some lower) Pliocene vitric silty clay and vitric clayey silt similar to the lower part of the upper unit. The thickness of the basalt unit can only be estimated to be between 13 and 25 m because of poor core recovery (28% to 55%). The absence of internal flow structures and the presence of an upper glassy chilled zone and a lower, fine-grained margin suggest that the basalt unit is either a single lava flow or a near-surface sill. The basalt consists of plagioclase phenocrysts with subordinate augite and olivine phenocrysts and of plagioclase-augite-olivine glomerocrysts in a groundmass of plagioclase, augite, olivine, and glass. The basalt is an island arc tholeiite enriched in large-ion-lithophile elements relative to high-field-strength elements, similar to the submarine lavas of the southern arc seamounts. In contrast, volcanic rocks from the active volcanoes on Pagan and Agrigan islands, 100 km to the west of the drill site, are calc-alkaline. The basalt layer, the youngest in-situ igneous layer reported from the Izu-Bonin and Mariana forearcs, is enigmatic because of its location more than 100 km from the active volcanic arc. The sediment layers above and below the basalt unit are late Pliocene in age (about 2.5 Ma) and normally magnetized. The basalt has schlierenlike structures, reverse magnetization, and a K-Ar age of 1.68±0.37 Ma. Thus, the basalt layer is probably a sill fed by magma intruded along a fault zone bounding the horst and graben in the forearc. The geochemistry of the basalt is consistent with a magma source similar to that of the active island arc and from a mantle source above the subducting Pacific plate.

Carbon, boron and oxygen isotope ratios of sediments from the Moresby Seamount

We report results from boron, carbon and oxygen stable isotope analyses of faulted and veined rocks recovered by scientific ocean drilling during ODP Leg 180 in the western Woodlark Basin, off Papua New Guinea. In this area of active continental extension, crustal break-up and incipient seafloor spreading, a shallow-dipping, seismically active detachment fault accommodates strain, defining a zone of mylonites and cataclasites, vein formation and fluid infiltration. Syntectonic microstructures and vein-fill mineralogy suggest frictional heating during slip during extension and exhumation of Moresby Seamount. Low carbon and oxygen isotope ratios of calcite veins indicate precipitation from hydrothermal fluids (delta13C PDB down to -17?; delta18O PDB down to -22?) formed by both dehydration and decarbonation. Boron contents are low (<7 ppm), indicating high-grade metamorphic source rock for the fluids. Some of the delta11B signatures (17-35?; parent solutions to calcite vein fills) are low when compared to deep-seated waters in other tectonic environments, likely reflecting preferential loss of 11B during low-grade metamorphism at depth. Pervasive devolatilization and flux of CO2-rich fluids are evident from similar vein cement geochemistry in the detachment fault zone and splays further updip. Multiple rupture-and-healing history of the veins suggests that precipitation may be an important player in fluid pressure evolution and, hence, seismogenic fault movement.

Mg/Ca variability in Globigerinoides ruber tests

Laser ablation inductively coupled plasma-mass spectrometry microanalysis of fossil and live Globigerinoides ruber from the eastern Indian Ocean reveals large variations of Mg/Ca composition both within and between individual tests from core top or plankton pump samples. Although the extent of intertest and intratest compositional variability exceeds that attributable to calcification temperature, the pooled mean Mg/Ca molar values obtained for core top samples between the equator and >30°S form a strong exponential correlation with mean annual sea surface temperature (Mg/Ca mmol/mol = 0.52 exp**0.076SST°C, r**2 = 0.99). The intertest Mg/Ca variability within these deep-sea core top samples is a source of significant uncertainty in Mg/Ca seawater temperature estimates and is notable for being site specific. Our results indicate that widely assumed uncertainties in Mg/Ca thermometry may be underestimated. We show that statistical power analysis can be used to evaluate the number of tests needed to achieve a target level of uncertainty on a sample by sample case. A varying bias also arises from the presence and varying mix of two morphotypes (G. ruber ruber and G. ruber pyramidalis), which have different mean Mg/Ca values. Estimated calcification temperature differences between these morphotypes range up to 5°C and are notable for correlating with the seasonal range in seawater temperature at different sites.

Geochemistry of ODP Leg 125 peridotites

Ocean Drilling Program Leg 125 recovered serpentined harzburgites and dunites from a total of jive sites on the crests and flanks of two serpen finite seamounts, Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc. These are some of the first extant forearc peridotites reported in the literature and they provide a window into oceanic, supra-subduction zone (SSZ) mantle processes. Harzbutrgites from both seamounts are very refractory with low modal clinopyroxene (<4%), chrome-rich spinels (cx-number = 0.40-0.80), very low incompatible element contents, and (with the exception of amphibole-bearing samples) U-shaped rare earth element (REE) profiles with positive Eu anomalies. Both sets of peridotites have olivine-spinel equilibration temperatures that are low compared with abyssal peridotites, possibly because of water-assisted diffusional equilibration in the SSZ environment However, other features indicate that the harzburgites from the two seamounts have very different origins. Harzburgites from Conical Seamount are characterized by calculated oxygen fugacities between FMQ (fayalite- magnetite- quartz) - 1.1 (log units) and FMQ + 0.4 which overlap those of mid-ocean ridge basalt (MORB) peridotites. Dunites from Conical Seamotmt contain small amounts of clinopyroxene, orthopyroxene and amphibole and are light REE (LREE) enriched. Moreover; they are considerably more oxidized than the harzburgites to which they are spatially related, with calculated oxygen fugacities of FMQ -0.2 toFMQ + 1.2. Using textural and geochemical evidence, we interpret these harzburgites as residual MORB mantle (from 15 to 20 % fractional melting) which has subsequently been modified by interaction with boninitic melt ivithin the mantle wedge, and these dunites as zones of focusing of this melt in which pyroxene has preferentially been dissolved from the harzbutgite protolith. In contrast, harzburgites from Torishima Forearc Seamount give calculated oxygen fugacities between FMQ + 0.8 and FMQ + l.6, similar to those calculated for other subduction-zone related peridotites and similar to those calculated for the dunites (FMQ + 1.2 to FMQ + 1.8) from the same seamount. In this case, we interpret both the harzburgites and dunites as linked to mantle melting (20-25 % fractional melting) in a supra-subduction zone environment The results thus indicate that the forearc is underlain by at least two types of mantle lithosphere, one being trapped or accreted oceanic lithosphere, the other being lithosphere formed by subduction-related melting. They also demonstrate that both types of mantle lithosphere may have undergone extensive interaction with subduction-derived magmas.

Osmium, and stable carbon and oxygen isotope record accross the PETM

In the latest Paleocene an abrupt shift to more negative d13C values has been documented at numerous marine and terrestrial sites (Bralower et al., 1997, doi:10.1130/0091-7613(1997)025<0963:HRROTL>2.3.CO;2; Cramer et al., 1999; Kaiho et al., 1996, doi:10.1029/96PA01021; Kennett and Stott, 1991, doi:10.1038/353225a0; Koch et al., 1992, doi:10.1038/358319a0; Stott et al., 1996; Thomas and Shackleton, 1996, doi:10.1144/GSL.SP.1996.101.01.20; Zachos et al., 1993). This carbon isotope event (CIE) is coincident with oxygen isotope data that indicate warming of surface waters at high latitudes of nearly 4°-6°C (Kennett and Stott, 1991, doi:10.1038/353225a0) and more moderate warming in the subtropics (Thomas et al., 1999, doi:10.1029/1999PA900031). Here we report 187Os/188Os isotope records from the North Atlantic and Indian Oceans which demonstrate a >10% increase in the 187Os/188Os ratio of seawater coincident with the late Paleocene CIE. This excursion to higher 187Os/188Os ratios is consistent with a global increase in weathering rates. The inference of increased chemical weathering during this interval of unusual warmth is significant because it provides empirical evidence supporting the operation of a feedback between chemical weathering rates and warm global climate, which acts to stabilize Earth's climate (Walker et al., 1981). Estimates of the duration of late Paleocene CIE (Bains et al., 1999, doi:10.1126/science.285.5428.724; Bralower et al., 1997, doi:10.1130/0091-7613(1997)025<0963:HRROTL>2.3.CO;2; Norris and Röhl, 1999, doi:10.1038/44545; Röhl et al., 2000, doi:10.1130/0091-7613(2000)28<927:NCFTLP>2.0.CO;2) in conjunction with the Os isotope data imply that intensified chemical weathering in response to warm, humid climates can occur on timescales of 104-105 years. This interpretation requires that the late Paleocene thermal maximum Os isotope excursion be produced mainly by increased Os flux to the ocean rather than a transient excursion to higher 187Os/188Os ratios in river runoff. Although we argue that the former is more likely than the latter, we cannot rule out significant changes in the 187Os/188Os ratio of rivers.

Rare earth elements in standard samples of ocean Fe-Mn nodules and crusts

Contents of rare earth elements (REE) in standard samples of Fe-Mn nodules (SDO-5, 6), Fe-Mn crust (SDO-7), and red clay (SDO-9) have been determined by ICP-MS and instrumental neutron activation analysis. Reproducibility of ICP-MS was 5-6%. These results are discussed and compared with other data. It has been found that distribution of REE in the standard samples of ocean Fe-Mn ores and red clay is highly homogenous.

Geochemistry of sediments beneath the Tonga-Kermadec arc

The fate of subducted sediment and the extent to which it is dehydrated and/or melted before incorporation into arc lavas has profound implications for the thermo-mechanical nature of the mantle wedge and models for crustal evolution. In order to address these issues, we have undertaken the first measurements of 10Be and light elements in lavas from the Tonga-Kermadec arc and the sediment profile at DSDP site 204 outboard of the trench. The 10Be/9Be ratios in the Tonga lavas are lower than predicted from flux models but can be explained if (a) previously estimated sediment contributions are too high by a factor of 2-10, (b) the top 1-22 m of the incoming sediment is accreted, (c) large amounts of sediment erosion are proposed, or (d) the sediment component takes several Myr longer than the subducting plate to reach the magma source region beneath Tonga. The lavas form negative Th/Be-Li/Be arrays that extend from a depleted mantle source composition to lower Th/Be and Li/Be ratios than that of the bulk sediment. Thus, these arrays are not easily explained by bulk sediment addition and, using partition coefficients derived from experiments on the in-coming sediment, we show that they are also unlikely to result from fluid released during dehydration of the sediment (or altered oceanic crust). However, partial melts of the dehydrated sediment residue formed at ~800 °C during the breakdown of amphibole +/- plagioclase and in the absence of cordierite have significantly lowered Th/Be ratios. The lava arrays can be successfully modelled as 10-15% partial melts of depleted mantle after it has been enriched by the addition of 0.2-2% of these partial melts. Phase relations suggest that this requires that the top of the subducting crust reaches temperatures of ~800 °C by the time it attains ~ 80 km depth which is in excellent agreement with the results of recent numerical models incorporating a temperature-dependent mantle viscosity. Under these conditions the wet basalt solidus is also crossed yet there is no recognisable eclogitic signal in the lavas suggesting that on-going dehydration or strong thermal gradients in the upper part of the subducting plate inhibit partialmelting of the altered oceanic crust.

Composition and age of ores and bottom sediments accumulated within and near the Rainbow hydrothermal field

Results of direct geological and geochemical observations of the modern Rainbow hydrothermal field (Mid-Atlantic Ridge, 36°14'N; 33°54'W) carried out from the deep-sea manned Mir submersibles during Cruises 41 and 42 of the R/V Akademik Mstislav Keldysh in 1998-1999 and data of laboratory studies of collected samples are under consideration in the paper. The field lacks neovolcanic rocks and the axial part of the rift is filled in with a serpentinite protrusion. In this field there occur metalliferous sediments, as well as active and relict sulfide edifices composed of sulfide minerals; pyrrhotite, chalcopyrite, isocubanite, sphalerite, marcasite, pyrite, bornite, chalcosine, digenite, magnetite, anhydrite, rare troilite, wurtzite, millerite, and pentlandite have been determined. Sulfide ores are characterized by concentric-zoned textures. During in situ measurements during 35 minutes temperature of hydrothermal fluids was varying within a range from 250 to 350°C. Calculated chemical and isotopic composition of hydrothermal fluid shows elevated concentrations of Cl, Ni, Co, CH4, and H2. Values of d34S of H2S range from +2.4 to +3.1 per mil, of d13C of CH4 from -15.2 to -11.2 per mil, and d13C of CO2 from +1.0 to -4.0 per mil. Fluid inclusions are homogenized at temperatures from 140 to 360°C, whereas salinity of the fluid varies from 4.2 to 8.5 wt %. d34S values of sulfides range from +1.3 to +12.5 per mil. 3He/4He ratio in mineral-forming fluid contained in the fluid inclusions from sulfides of the Rainbow field varies from 0.00000374 to 0.0000101. It is shown that hydrothermal activity in the area continues approximately during 100 ka. It is assumed that the fluid and sulfide edifices contain components from the upper mantle. A hypothesis of phase separation of a supercritical fluid that results in formation of brines is proposed. Hydrothermal activity is related to the tectonic, not volcanic, phase of the Mid-Atlantic Ridge evolution.

Geochemistry of tephra from the Taupo Volcanic Zone

The Taupo Volcanic Zone (TVZ), central North Island, New Zealand, is the most frequently active Quaternary rhyolitic system in the world. Silicic tephras recovered from Ocean Drilling Programme Site 1123 (41°47.16'S, 171°29.94'W; 3290 m water depth) in the southwest Pacific Ocean provide a well-dated record of explosive TVZ volcanism since ~1.65 Ma. We present major, minor and trace element data for 70 Quaternary tephra layers from Site 1123 determined by electron probe microanalysis (1314 analyses) and laser ablation inductively coupled plasma mass spectrometry (654 analyses). Trace element data allow for the discrimination of different tephras with similar major element chemistries and the establishment of isochronous tie-lines between three sediment cores (1123A, 1123B and 1123C) recovered from Site 1123. These tephra tie-lines are used to evaluate the stratigraphy and orbitally tuned stable isotope age model of the Site 1123 composite record. Trace element fingerprinting of tephras identifies ~4.5 m and ~7.9 m thick sections of repeated sediments in 1123A (49.0-53.5 mbsf [metres below seafloor]) and 1123C (48.1-56.0 mbsf), respectively. These previously unrecognised repeated sections have resulted in significant errors in the Site 1123 composite stratigraphy and age model for the interval 1.15-1.38 Ma and can explain the poor correspondence between d18O profiles for Site 1123 and Site 849 (equatorial Pacific) during this interval. The revised composite stratigraphy for Site 1123 shows that the 70 tephra layers, when correlated between cores, correspond to ~37-38 individual eruptive events (tephras), 7 of which can be correlated to onshore TVZ deposits. The frequency of large-volume TVZ-derived silicic eruptions, as recorded by the deposition of tephras at Site 1123, has not been uniform through time. Rather it has been typified by short periods (25-50 ka) of intense activity bracketed by longer periods (100-130 ka) of quiescence. The most active period (at least 1 event per 7 ka) occurred between ~1.53 and 1.66 Ma, corresponding to the first ~130 ka of TVZ rhyolitic magmatism. Since 1.2 Ma, ~80% of tephras preserved at Site 1123 and the more proximal Site 1124 were erupted and deposited during glacial periods. This feature may reflect either enhanced atmospheric transport of volcanic ash to these sites (up to 1000 km from source) during glacial conditions or, more speculatively, that these events are triggered by changes in crustal stress accumulation associated with large amplitude sea-level changes. Only 8 of the ~37-38 Site 1123 tephra units (~20%) can be found in all three cores, and 22 tephra units (~60%) are only present in one of the three cores. Whether a tephra is preserved in all three cores does not have any direct relationship to eruptive volume. Instead it is postulated that tephra preservation at Site 1123 is 'patchy' and influenced by the vigorous nature of their deposition to the deep ocean floor as vertical density currents. At this site, at least 5 cores would need to have been drilled within a proximity of 10's to 100's of metres of each other to yield a >99% chance of recovering all the silicic tephras deposited on the ocean surface above it in the past 1.65 Ma.

Rare earth and other chemical element contents and partitions in bottom sediments, micronodules, and nodules from the bioproductive zone of the Pacific Ocean

Concentrations and compositions of rare earth elements (REE) in three micronodule fractions (50-250, 250-500, and >500 ?m), coexisting macronodules, and host sediments were studied. Samples were collected at three sites (Guatemala Basin, Peru Basin, and northern equatorial Pacific) located in elevated bioproductivity zones of surface waters. Influence of micronodule size is dominant for REE compositions and subordinate for REE concentrations. For example, Ce concentration inversely correlates with micronodule size and drops to the lowest value in macronodules and host sediments. Decrease of Ce concentration is generally accompanied by Mn/Fe increase in micro- and macronodules. Hence, the role of diagenetic source of material directly correlates with micronodule sizes. Contribution of the diagenetic source is maximal for macronodules. REE composition distinctions for micronodules and macronodules can be attributed to variations of hydrogenic iron oxyhydroxides and diagenetic (hydrothermal) iron hydroxophosphates that are the major REE carriers in ferromanganese ore deposits. Relationship and general trend in chemistry of coexisting macronodules suggest that they can represent products of the initial stage of nodule formation.