Chemistry of minerals from amphibole-chlorite veins of ODP Site 209-1270

We examined small-scale shear zones in drillcore samples of abyssal peridotites from the Mid-Atlantic Ridge. These shear zones are associated with veins consisting of chlorite + actinolite/tremolite assemblages, with accessory phases zircon and apatite, and they are interpreted as altered plagiogranite melt impregnations, which originate from hydrous partial melting of gabbroic intrusion in an oceanic detachment fault. Ti-in-zircon thermometry yields temperatures around 820°C for the crystallization of the evolved melt. Reaction path modeling indicates that the alteration assemblage includes serpentine of the adjacent altered peridotites. Based on the model results, we propose that formation of chlorite occurred at higher temperatures than serpentinization, thus leading to strain localization around former plagiogranites during alteration. The detachment fault represents a major pathway for fluids through the oceanic crust, as evidenced by extremely low d18O of altered plagiogranite veins (+3.0-4.2 per mil) and adjacent serpentinites (+ 2.6-3.7 per mil). The uniform oxygen isotope data indicate that fluid flow in the detachment fault system affected veins and adjacent host serpentinites likewise.

Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

Geochemistry and oxygen and iron isotope ratios of mafic rocks

Recycling of oceanic crust into the deep mantle via subduction is a widely accepted mechanism for creating compositional heterogeneity in the upper mantle and for explaining the distinct geochemistry of mantle plumes. The oxygen isotope ratios (d18O) of some ocean island basalts (OIB) span values both above and below that of unmetasomatised upper mantle (5.5 ± 0.4 per mil) and provide support for this hypothesis, as it is widely assumed that most variations in d18O are produced by near-surface low-temperature processes. Here we show a significant linear relationship between d18O and stable iron isotope ratios (d57Fe) in a suite of pristine eclogite xenoliths. The d18O values of both bulk samples and garnets range from values within error of normal mantle to significantly lighter values. The observed range and correlation between d18O and d57Fe is unlikely to be inherited from oceanic crust, as d57Fe values determined for samples of hydrothermally altered oceanic crust do not differ significantly from the mantle value and show no correlation with d18O. It is proposed that the correlated d57Fe and d18O variations in this particular eclogite suite are predominantly related to isotopic fractionation by disequilibrium partial melting although modification by melt percolation processes cannot be ruled out. Fractionation of Fe and O isotopes by removal of partial melt enriched in isotopically heavy Fe and O is supported by negative correlations between bulk sample d57Fe and Cr content and bulk sample and garnet d18O and Sc contents, as Cr and Sc are elements that become enriched in garnet- and pyroxene-bearing melt residues. Melt extraction could take place either during subduction, where the eclogites represent the residues of melted oceanic lithosphere, or could take place during long-term residence within the lithospheric mantle, in which case the protoliths of the eclogites could be of either crustal or mantle origin. This modification of both d57Fe and d18O by melting processes and specifically the production of low-d18O signatures in mafic rocks implies that some of the isotopically light d18O values observed in OIB and eclogite xenoliths may not necessarily reflect near-surface processes or components.

Net primary productivity, POC export, Th234 and U238 activities and abundance of autotrophs during U.S.C.G.C. Healy cruises HLY0802 and HLY0803

Seasonal patterns in the partitioning of phytoplankton carbon during receding sea ice conditions in the eastern Bering Sea water column are presented using rates of 14C net primary productivity (NPP), phototrophic plankton carbon content, and POC export fluxes from shelf and slope waters in the spring (March 30-May 6) and summer (July 3-30) of 2008. At ice-covered and marginal ice zone (MIZ) stations on the inner and middle shelf in spring, NPP averaged 76 ± 93 mmol C/m**2/d, and in ice-free waters on the outer shelf NPP averaged 102 ± 137 mmol C/m**2/d. In summer, rates of NPP were more uniform across the entire shelf and averaged 43 ± 23 mmol C/m**2/d over the entire shelf. A concomitant shift was observed in the phototrophic pico-, nano-, and microplankton community in the chlorophyll maximum, from a diatom dominated system (80 ± 12% autotrophic C) in ice covered and MIZ waters in spring, to a microflagellate dominated system (71 ± 31% autotrophic C) in summer. Sediment trap POC fluxes near the 1% PAR depth in ice-free slope waters increased by 70% from spring to summer, from 10 ± 7 mmol C/m**2/d to 17 ± 5 mmol C/m**2/d, respectively. Over the shelf, under-ice trap fluxes at 20 m were higher, averaging 43 ± 17 mmol C/m**2/d POC export over the shelf and slope estimated from 234Th deficits averaged 11 ± 5 mmol C/m**2/d in spring and 10 ± 2 mmol C/m**2/d in summer. Average e-ratios calculated on a station-by-station basis decreased by ~ 30% from spring to summer, from 0.46 ± 0.48 in ice-covered and MIZ waters, to 0.33 ± 0.26 in summer, though the high uncertainty prevents a statistical differentiation of these data.

Bulk sedimentology from Sites M0002 and M0004 of the ACEX (Exp302) expedition to the Arctic Ocean

Except for a few discontinuous fragments of the Late Cretaceous/Early Cenozoic climate history and depositional environment, the paleoenvironmental evolution of the pre-Neogene central Arctic Ocean was virtually unknown prior to the IODP Expedition 302 (Arctic Ocean Coring Expedition - ACEX) drilling campaign on Lomonosov Ridge in 2004. Here we present detailed organic carbon (OC) records from the entire ca. 200 m thick Paleogene OC-rich section of the ACEX drill sites. These records indicate euxinic "Black Sea-type" conditions favorable for the preservation of labile aquatic (marine algae-type) OC occur throughout the upper part of the early Eocene and the middle Eocene, explained by salinity stratification due to freshwater discharge. The superimposed short-term ("Milankovitch-type") variability in amount and composition of OC is related to changes in primary production and terrigenous input. Prominent early Eocene events of algae-type OC preservation coincide with global d13C events such as the PETM and Elmo events. The Elmo d13C Event has been identified in the Arctic Ocean for the first time.

Chemistry of hot waters sampled from basaltic basement at DSDP Hole 83-504B

Seawater that has been altered by reaction with basaltic basement has been sampled from Deep Sea Drilling Project Hole 504B, located on 5.9-m.y.-old crust on the southern flank of the Costa Rica Rift. Fourteen water samples have been collected on Legs 69, 70, and 83, both before and after renewed drilling on the latter two legs, at temperatures from 69 to 133°C and pressures from 390 to 425 bars. The water sampled prior to renewed drilling on Leg 83 had occupied the hole for nearly 2 yr. since it was last flushed with surface seawater at the end of Leg 70. Despite some contamination by seawater during sampling, the composition of two of these waters has been determined by using nitrate as a tag for the contaminant. Both the 80 and 115°C waters have seawater chlorinity, but have lost considerable Mg, Na, K, sulfate, and 02, and have gained Ca, alkalinity, Si, NH3 and H2S. The loss of sulfate is due to anhydrite precipitation, as indicated by the d34S value of the remaining dissolved sulfate. The 87Sr/86Sr ratio has been lowered to 0.7086 for the 80°C water and 0.7078 for the 115°C water, whereas the Sr concentration is nearly unchanged. The changes in major element composition relative to seawater are also larger for the 115°C water, indicating that the basement formation water at this site probably varies in composition with depth. Based on their direction relative to seawater, the compositional changes for the 80 and 115°C waters do not complement the changes inferred for the altered rocks from Hole 504B, suggesting that the bulk composition of the altered rocks, like their mineralogy, is largely unrelated to the present thermal and alteration regime in the hole. The exact nature of the reacted seawaters cannot be determined yet, however. During its 2 yr. residence in the hole, the surface seawater remaining at the end of Leg 70 would have reacted with the wall rocks and exchanged with their interstitial formation waters by diffusion and possibly convection. How far these processes have proceeded is not yet certain, although calculations suggest that diffusion alone could have largely exchanged the surface seawater for interstitial water. The d18O of the samples is indistinguishable from seawater, however, and the d14C of the 80°C sample is similar to that of ocean bottom water. Although the interpretation of these species is ambiguous, that of tritium should not be. Tritium analyses, which are in progress, should clarify the nature of the reacted seawaters obtained from the hole.

Geochemistry of oceanic crust of the Cocos Plate

New geochemical data from the Cocos Plate constrain the composition of the input into the Central American subduction zone and demonstrate the extent of influence of the Galápagos Hotspot on the Cocos Plate. Samples include sediments and basalts from Ocean Drilling Program (ODP) Site 1256 outboard of Nicaragua, gabbroic sills from ODP Sites 1039 and 1040, tholeiitic glasses from the Fisher Ridge off northwest Costa Rica, and basalts from the Galápagos Hotspot Track outboard of Central Costa Rica. Site 1256 basalts range from normal to enriched MORB in incompatible elements and have Pb and Nd isotopic compositions within the East Pacific Rise MORB field. The sediments have similar 206Pb/204Pb and only slightly more radiogenic 207Pb/204Pb and 208Pb/204Pb isotope ratios than the basalts. Altered samples from the subducting Galápagos Hotspot Track have similar Nd and Pb isotopic compositions to fresh Galápagos samples but have significantly higher Sr isotopic composition, indicating that the subduction input will have a distinct geochemical signature from Galápagos-type mantle material that may be present in the wedge beneath Costa Rica. Gabbroic sills from Sites 1039 and 1040 in East Pacific Rise (EPR) crust show evidence for influence of the Galápagos Hotspot ?100 km beyond the morphological hotspot track.