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.

Major and trace element abundances of igneous rocks from DSDP Site 37-334

REE abundances in gabbros and peridotites from Site 334 of DSDP Leg 37 show that these rocks are cumulates produced by fractional crystallization of a primitive oceanic tholeiite magma. They may be part of a layered oceanic complex. The REE distributions in the residual liquids left after such a fractionation are similar to those of incompatible element-depleted oceanic tholeiites. The REE data indicate that the basalts which overlie the gabbro-peridotite complex, are not genetically related to plutonic rocks.

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.

Synergistic effects of pCO2 and iron availability on nutrient consumption ratio of the Bering Sea phytoplankton community

Little is known concerning the effect of CO2 on phytoplankton ecophysiological processes under nutrient and trace element-limited conditions, because most CO2 manipulation experiments have been conducted under elements-replete conditions. To investigate the effects of CO2 and iron availability on phytoplankton ecophysiology, we conducted an experiment in September 2009 using a phytoplankton community in the iron limited, high-nutrient, low-chlorophyll (HNLC) region of the Bering Sea basin . Carbonate chemistry was controlled by the bubbling of the several levels of CO2 concentration (180, 380, 600, and 1000 ppm) controlled air, and two iron conditions were established, one with and one without the addition of inorganic iron. We demonstrated that in the iron-limited control conditions, the specific growth rate and the maximum photochemical quantum efficiency (Fv/Fm) of photosystem (PS) II decreased with increasing CO2 levels, suggesting a further decrease in iron bioavailability under the high-CO2 conditions. In addition, biogenic silica to particulate nitrogen and biogenic silica to particulate organic carbon ratios increased from 2.65 to 3.75 and 0.39 to 0.50, respectively, with an increase in the CO2 level in the iron-limited controls. By contrast, the specific growth rate, Fv/Fm values and elemental compositions in the iron-added treatments did not change in response to the CO2 variations, indicating that the addition of iron canceled out the effect of the modulation of iron bioavailability due to the change in carbonate chemistry. Our results suggest that high-CO2 conditions can alter the biogeochemical cycling of nutrients through decreasing iron bioavailability in the iron-limited HNLC regions in the future.

Major and rare earth element composition of ODP Site 191-1179 sediments, northwest Pacific

Depth profiles of major element and rare earth element (REE) abundances in sediment samples (mainly siliceous ooze and clay) recovered from Holes 1179B and 1179C at Site 1179, Ocean Drilling Program Leg 191 (41.4°N, 159.6°E) were determined. The oxidation states of Mn and Ce were determined by X-ray absorption near-edge structure. Some geochemical indicators were tested, including the MnO/TiO2 ratios, a bivariate diagram of La/Ce vs. Al2O3/(Al2O3+Fe2O3), and other discrimination diagrams. The oxidation state of Mn is reduced Mn(II) in the depth profile below 0.60 meters below seafloor (mbsf), which is consistent with relatively low and high abundances of Mn in the sediments and pore waters, respectively. It is possible that the diagenetic effect on the oxidation state and abundance of Mn makes it difficult for the MnO/TiO2 ratio to reflect the depositional environment. The normalized ratio of La and Ce does not change very much with depth, suggesting that the diagenetic effect does not affect the REE signature in the sediments. On the diagram of La/Ce vs. Al2O3/(Al2O3+Fe2O3), the sediments studied here plot at the boundary of the pelagic and continental margin fields. This suggests that continental material has contributed to the sediment to some degree, even though Site 1179 is in a pelagic region of the northwestern Pacific Ocean, >1600 km from Japan.

Mineral composition and major element oxides of gabbros from ODP Hole 179-1105A, southwest Indian Ridge

Hole 1105A penetrated 158 m of gabbros at a site offset 1.3 km east-northeast from Hole 735B on the Atlantis Bank near the Atlantis II Fracture Zone. A total of 118 m of dominantly medium- to coarse-grained intercalated Fe-Ti oxide gabbro and olivine gabbro was recovered from Hole 1105A that shows many petrographic features similar to those recovered from the upper part of Hole 735B. The main rock types are distinguished based on the constituent cumulus phases, with the most primitive gabbros consisting of olivine, plagioclase, and clinopyroxene. The inferred crystallization order is subsequently Fe-Ti oxides (ilmenite and titanomagnetite), followed by orthopyroxene, then apatite, and finally biotite. Orthopyroxene appears to replace olivine in a narrow middle interval. The magmatic evolution is likewise reflected in the mineral compositions. Plagioclase varies from An66 to An28. Olivine varies from Fo78 to Fo35. The gap in olivine crystallization occurs between Fo46 and Fo40 and coincides approximately with the appearance of orthopyroxene (~En50). The clinopyroxenes show large compositional variation in Mg/(Mg + Fe total) from 0.84 to 0.51. The nonquadrilateral cations of clinopyroxene similarly show large variations with Ti increasing for the olivine gabbros and decreasing for the Fe-Ti oxide gabbros with the decrease in Mg/(Mg + Fe total). The apatites are mainly flourapatites. The compositional variation in the gabbros is interpreted as a comagmatic suite resulting from fractional crystallization. Pyroxene geothermometry suggests equilibration temperatures from 1100°C and below. The coexisting Fe-Ti oxide minerals indicate subsolidus equilibration temperatures from 900°C for olivine gabbros to 700°C for the most evolved apatite-bearing gabbros. The cryptic variation in the olivine gabbros defines two or three lenses, 40 to 60 m thick, each characterized by a distinct convex zoning with a lower segment indicating upward reverse fractionation, a central maximum, and an upper segment showing normal fractionation. The Fe-Ti oxide gabbros show cryptic variations independent of the host olivine gabbros and reveal a systematic upward normal fractionation trend transgressing host olivine gabbro boundaries. Forward fractional crystallization modeling, using a likely parental magma composition from the Atlantis II Fracture Zone (MgO = 7.2 wt%; Mg/[Mg + Fe2+] = 0.62), closely matches the compositions of coexisting olivine, plagioclase, and clinopyroxene. This modeling suggests cosaturation of olivine, plagioclase, and clinopyroxene from 1155°C and the addition of Fe-Ti oxides from 1100°C. The liquid line of descent initially shows increasing FeO with moderately increasing SiO2. After saturation of Fe-Ti oxides, the liquid strongly decreases in FeO and TiO2 and increases in SiO2, reaching dacitic compositions at ~10% liquid remaining. The calculations indicate that formation of olivine gabbros can be accounted for by <65% fractionation and that only the residual 35% liquid was saturated in Fe-Ti oxides. The modeling of the solid fractionation products shows that both the olivine gabbro and the Fe-Ti oxide gabbros contain very small amounts of trapped liquid (<5%). The implications are that the gabbros represent crystal mush that originated in a recharging and tapping subaxial chamber. Compaction and upward melt migration in the crystal mush appear to have been terminated with relatively large amounts of interstitial liquid remaining in the upper parts of the cumulate mush. This termination may have been caused by tectonic disturbances, uplift, and associated withdrawal of magma into the subaxial dike and sill system. Prolonged compaction and cooling of the trapped melt in the mush formed small differentiated bodies and lenses by pressure release migration and crystallization along syntectonic channels. This resulted in differentiation products along lateral and vertical channelways in the host gabbro that vary from olivine gabbro, to Fe-Ti oxide gabbro, gabbronorite, and apatite gabbros and show large compositional variations independent of the host olivine gabbros.

Bulk calcite minor element composition of ODP Leg 130 samples

We investigated minor element ratios (Sr/Ca and Mg/Ca) in bulk sediment samples from Sites 803-807 using a recently optimized sample treatment protocol for calcium-carbonate-rich sediments consisting of sequential reductive and ion exchange treatments. We evaluated this protocol relative to bulk sediment leaching using samples from Sites 804 and 806, the two end-member sites in the depth transect, reporting as well Mn/Ca and Fe/Ca ratios for sediments from these two sites processed by means of both methods. The Sr/Ca ratios were only slightly affected by the sample treatment, with an average reduction of 6%-7% caused primarily by the ion exchange step. The reductive sample treatment, designed to be effective at removing Mn-rich oxyhydroxides, has a major effect on Mg/Ca ratios, with up to 50% reduction, whereas little effect occurred in ion exchange alone on Mg/Ca ratios. The Mn/Ca and Fe/Ca ratios were not consistently offset by the sample treatment, and these ratios do not appear to be representative of calcite geochemistry reflecting either ocean history or diagenetic overprinting. Celestite solubility appears to be an important control on interstitial water Sr concentrations in these sites, and it must be considered when constructing Sr mass balance models of calcite recrystallization. Calcite Sr/Ca ratios (range 1-2 mmol/mol) are similar from site to site when plotted vs. age, with a pattern comparable to that for well-preserved foraminifer tests over the past 40 Ma. Interstitial water Mg and Ca gradients appear to reflect basement character and the intensity of alteration; they can vary substantially over a small area. Calcite Mg/Ca ratios (range 1.5-4.5 mmol/mol) differ from site to site, with generally higher ratios for sites at a shallower water depth. Increasing calcite Mg/Ca ratios correlate with decreasing Sr/Ca ratios in the treated samples. No consistent pattern exists for calcite Mg/Ca ratios vs. age or depth, nor is any direct correlation to interstitial water Mg/Ca ratios present.

Element concentrations and isotopic composition of tholeiite and whole rocks samples from the east Mariana Basin

Studies of seafloor magnetic anomaly patterns suggest the presence of Jurassic oceanic crust in a large area in the western Pacific that includes the East Mariana, Nauru and Pigafetta Basins. Sampling of the igneous crust in this area by the Deep Sea Drilling Program (DSDP) and the Ocean Drilling Program (ODP) allows direct evaluation of the age and petrogenesis of this crust. ODP Leg 129 drilled a 51 m sequence of basalt pillows and massive flows in the central East Mariana Basin. 40Ar/39Ar ages determined in this study for two Leg 129 basalts average 114.6 +/- 3.2 Ma. This age is in agreement with the Albian-late Aptian paleontologic age of the overlying sediments, but is distinctively younger than the Jurassic age predicted by magnetic anomaly patterns in the basin. Compositionally, the East Mariana Basin basalts are uniformly low-K tholeiites that are depleted in highly incompatible elements compared to moderately incompatible ones, which is typical of mid-ocean ridge basalts (MORB) erupted near hotspots. The Sr, Nd and Pb isotopic compositions of the tholeiites (87Sr/86Sr init = 0.70360-0.70374; 143Nd/144Nd init = 0.512769-0.512790; 206Pb/204Pb meas = 18.355-18.386) also overlap with some Indian Ocean Ridge MORB, although they are distinct from the isotopic compositions of Jurassic basalts drilled in the Pigafetta Basin, the oldest Pacific MORB. The isotopic compositions of the East Mariana Basin tholeiites are also similar to those of intraplate basalts, and in particular, to the isotopic signature of basalts from the nearby Ontong Java and Manihiki Plateaus. The East Mariana Basin tholeiites also share many petrologic and isotopic characteristics with the oceanic basement drilled in the Nauru Basin at DSDP Site 462. In addition, the new 110.8 +/- 1.0 Ma 40Ar/39Ar age for two flows from the bottom of Site 462 in the Nauru Basin is indistinguishable from the age of the East Mariana Basin flows. Thus, while magnetic anomaly patterns predict that the igneous basement in the Nauru and East Mariana Basins is Jurassic in age, the geochemical and chronological results discussed here suggest that the basement formed during a Cretaceous rifting event within the Jurassic crust. This magmatic and tectonic event was created by the widespread volcanism responsible for the genesis of the large oceanic plateaus of the western Pacific.

Mineralogy and major element oxide composition of sediments from ODP Hole 172-1063D

Dansgaard-Oeschger (D-O) cycles in sediment at Site 1063 are characterized by distinct fluctuations in physical properties. Stadials are marked by low bulk density and interstadials by high bulk density. Compressional (P-)wave velocity is in phase with bulk density over some but not all depth intervals. Four of the D-O cycles straddling the oxygen isotope Stage 4/5 boundary have been studied in detail to understand the origin of the physical properties changes. Sediment on the Bermuda Rise is comprised of three main components: calcite, aluminosilicate minerals, and biogenic silica. Calcite concentrations vary from 1% to 43% of bulk sediment and are highest during interstadials. Aluminosilicate concentrations vary from 52% to 92% of bulk sediment and are highest during stadials. The major element ratios Al2O3/TiO2 and K2O/Al2O3 show increases across bulk density cycles, suggesting a change in the composition of aluminosilicates. This interpretation is supported by mineralogical analyses, which show a subtle change in clay composition. Biogenic silica concentrations vary from 0% to 23% of bulk sediment and are also highest during stadials. However, the abundance of silica varies significantly from one D-O cycle to another. Silt and fine sand abundance also increase during the first of the four stadials. This coarsening of sediment coincides with the increase in biogenic silica. The low grain density and high porosity associated with biogenic silica result in intervals of low bulk-sediment density. The abundance of biogenic silica closely matches P-wave velocity, suggesting that silica imparts a greater rigidity to the sediment.

Major and trace element composition of sepentine muds and metabasic rocks of ODP Leg 195 and Leg 125 sites

New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.