Hydrochemistry measured on water bottle samples during METEOR cruise M60/5

We compare alkalinity and total dissolved inorganic carbon (DIC) measurements made during the Transient Tracers in the Ocean, North Atlantic Study (TTO-NAS) in 1981 with modern measurements from a TTO reoccupation cruise in 2004 (M60/5). We find that the TTO-NAS alkalinity values are 3.6 ± 2.3 µmol/kg higher than modern alkalinity data tied to Certified Reference Materials. The TTO-NAS DIC values re-calculated from original alkalinity and discrete-pCO2 data using currently accepted constants are 3.8 µmol/kg higher than those reported in the revised TTO data set. This difference is reduced to 0.7 µmol/kg when our suggested correction to the TTO-NAS alkalinity is applied. These re-calculated DIC values are 2.4 µmol/kg too low relative to contemporaneous measurements made by the vacuum extraction/manometric Certified method. Application of this correction brings the TTO data into almost perfect agreement with modern measurements for slowly-ventilated deep water of the eastern Atlantic.

DNA alignment and Bayesian trees of partial sequences of COI, COIII and the haemocyanin functional unit f-g of 28 octopod species

Background: Octopods have successfully colonised the world's oceans from the tropics to the poles. Yet, successful persistence in these habitats has required adaptations of their advanced physiological apparatus to compensate impaired oxygen supply. Their oxygen transporter haemocyanin plays a major role in cold tolerance and accordingly has undergone functional modifications to sustain oxygen release at sub-zero temperatures. However, it remains unknown how molecular properties evolved to explain the observed functional adaptations. We thus aimed to assess whether natural selection affected molecular and structural properties of haemocyanin that explains temperature adaptation in octopods. Results: Analysis of 239 partial sequences of the haemocyanin functional units (FU) f and g of 28 octopod species of polar, temperate, subtropical and tropical origin revealed natural selection was acting primarily on charge properties of surface residues. Polar octopods contained haemocyanins with higher net surface charge due to decreased glutamic acid content and higher numbers of basic amino acids. Within the analysed partial sequences, positive selection was present at site 2545, positioned between the active copper binding centre and the FU g surface. At this site, methionine was the dominant amino acid in polar octopods and leucine was dominant in tropical octopods. Sites directly involved in oxygen binding or quaternary interactions were highly conserved within the analysed sequence. Conclusions: This study has provided the first insight into molecular and structural mechanisms that have enabled octopods to sustain oxygen supply from polar to tropical conditions. Our findings imply modulation of oxygen binding via charge-charge interaction at the protein surface, which stabilize quaternary interactions among functional units to reduce detrimental effects of high pH on venous oxygen release. Of the observed partial haemocyanin sequence, residue 2545 formed a close link between the FU g surface and the active centre, suggesting a role as allosteric binding site. The prevalence of methionine at this site in polar octopods, implies regulation of oxygen affinity via increased sensitivity to allosteric metal binding. High sequence conservation of sites directly involved in oxygen binding indicates that functional modifications of octopod haemocyanin rather occur via more subtle mechanisms, as observed in this study.

(Table 1) H2O and CO2 contents in submarine basaltic glasses from Ontong Java Plateau

The Ontong Java Plateau in the western Pacific is anomalous compared to other oceanic large igneous provinces in that it appears to have never formed a large subaerial plateau. Paleoeruption depths (at 122 Ma) estimated from dissolved H2O and CO2 in submarine basaltic glass pillow rims vary from ~1100 m below sea level (mbsl) on the central part of the plateau to 2200-3000 mbsl on the northeastern edge. Our results suggest maximum initial uplift for the plateau of 2500-3600 m above the surrounding seafloor and 1500+/-400 m of postemplacement subsidence since 122 Ma. Our estimates of uplift and subsidence for the plateau are significantly less than predictions from thermal models of oceanic lithosphere, and thus our results are inconsistent with formation of the plateau by a high-temperature mantle plume. Two controversial possibilities to explain the anomalous uplift and subsidence are that the plateau (1) formed as a result of a giant bolide impact, or (2) formed from a mantle plume but has a lower crust of dense garnet granulite and/or eclogite; neither of these possibilities is fully consistent with all available geological, geophysical, and geochemical data. The origin of the largest magmatic event on Earth in the past 200 m.y. thus remains an enigma.

The effects of elevated CO2 on the growth and toxicity of field populations and cultures of the saxitoxin-producing dinoflagellate, Alexandrium fundyense

The effects of coastal acidification on the growth and toxicity of the saxitoxin-producing dinoflagellate Alexandrium fundyense were examined in culture and ecosystem studies. In culture experiments, Alexandrium strains isolated from Northport Bay, New York, and the Bay of Fundy, Canada, grew significantly faster (16-190%; p < 0.05) when exposed to elevated levels of PCO2 ( 90-190 Pa=900-1900 µatm) compared to lower levels ( 40 Pa=400 µatm). Exposure to higher levels of PCO2 also resulted in significant increases (71-81%) in total cellular toxicity (fg saxitoxin equivalents/cell) in the Northport Bay strain, while no changes in toxicity were detected in the Bay of Fundy strain. The positive relationship between PCO2 enrichment and elevated growth was reproducible in natural populations from New York waters. Alexandrium densities were significantly and consistently enhanced when natural populations were incubated at 150 Pa PCO2 compared to 39 Pa. During natural Alexandrium blooms in Northport Bay, PCO2 concentrations increased over the course of a bloom to more than 170 Pa and were highest in regions with the greatest Alexandrium abundances, suggesting Alexandrium may further exacerbate acidification and/or be especially adapted to these acidi-fied conditions. The co-occurrence of Alexandrium blooms and elevated PCO2 represents a previously unrecognized, compounding environmental threat to coastal ecosystems. The ability of elevated PCO2 to enhance the growth and toxicity of Alexandrium indicates that acidification promoted by eutrophication or climate change can intensify these, and perhaps other, harmful algal blooms.

Physical, geochemical and magnetic properties of several ODP Leg 192 sites, Ontong Java Plateau

In this manuscript, we present the results of a physical properties investigation carried out on basaltic cores recovered from the four Leg 192 basement sites, focusing on the relationship between physical properties and alteration in basalts. Variations in physical properties in the Leg 192 basement sites closely resemble each other and reflect the amount of alteration and vein formation in the basement basalts. P-wave velocities, magnetic susceptibilities, and densities for the dense massive basalts are higher than those of more altered and heavily veined basalts. Porosity-dependent alteration is observed at Leg 192 basement sites: P-wave velocity displays a general decrease with increasing loss on ignition and potassium content. These trends are consistent with trends documented for typical alteration of oceanic crust and suggest that basalt alteration is largely responsible for the variation of the physical properties exhibited by rocks at Leg 192 basement sites. Our physical property data support the conclusion that only low-temperature seawater-mediated alteration occurred in the lava flows of the Ontong Java Plateau (OJP). This lack of higher-temperature hydrothermal alteration is consistent with the idea that the OJP basement sites are far from their eruptive vents.

CaCO3 size distribution in surface sediments

Lysocline reconstructions play an important role in scenarios purporting to explain the lowered atmospheric CO2 content of glacial time. These reconstructions are based on indicators such as the CaCO3 content, the percent of coarse fraction, the ratio of fragments to whole foraminifera shells, the ratio of solution-susceptible to solution-resistant species, and the ratio of coarse to fine CaCO3. All assume that changes with time in the composition of the input material do not bias the result. However, as the composition of the input material does depend on climate, none of these indicators provides an absolute measure of the extent of dissolution. In this paper we evaluate the reliability of the ratio of >63 µm CaCO3 to total CaCO3 as a dissolution indicator. We present here results that suggest that in today's tropics this ratio appears to be determined solely by CO3= ion concentration and water depth (i.e., the saturation state of bottom waters). This finding offers the possibility that the size fraction index can be used to reconstruct CO3= ion concentrations for the late Quaternary ocean to an accuracy of ±5 µmol/kg.

Oxygen isotopes and hydrocarbon composition of gas hydrate and hydrate water from ODP Leg 165 sites

Ocean Drilling Program (ODP) Leg 164 recovered a number of large solid gas hydrate from Sites 994, 996, and 997 on the Blake Ridge. Sites 994 and 997 samples, either nodular or thick massive pieces, were subjected to laboratory analysis and measurements to determine the structure, molecular and isotopic composition, thermal conductivity, and equilibrium dissociation conditions. X-ray computed tomography (CT) imagery, X-ray diffraction, nuclear magnetic resonance (NMR), and Raman spectroscopy have revealed that the gas hydrates recovered from the Blake Ridge are nearly 100% methane gas hydrate of Structure I, cubic with a lattice constant of a = 11.95 ± 0.05 angström, and a molar ratio of water to gas (hydration number) of 6.2. The d18O of water is 2.67 per mil to 3.51 per mil SMOW, which is 3.5-4.0 heavier than the ambient interstitial waters. The d13C and dD of methane are -66 per mil to -70 per mil and -201 per mil to -206 per mil, respectively, suggesting that the methane was generated through bacterial CO2 reduction. Thermal conductivity values of the Blake Ridge hydrates range from 0.3 to 0.5 W/(m K). Equilibrium dissociation experiments indicate that the three-phase equilibrium for the specimen is 3.27 MPa at 274.7 K. This is almost identical to that of synthetic pure methane hydrate in freshwater.

Paleomagnetic and biostratigraphic properties and datums of ODP Leg 173 and Leg 149 sites

We have conducted an integrated paleomagnetic and biostratigraphic study on the Cenozoic sedimentary sequences of the southern Iberia Abyssal Plain margin, focusing on Ocean Drilling Program (ODP) Sites 897, 898, 900, 1067, 1068, and 1069. Reliable magnetostratigraphy from these six sites is presented in this paper. Sedimentary sections from Holes 897C, 898A, 900A, 1067A, 1068A, and 1069A have recorded a pattern of magnetic polarity reversals that correlates well with the known magnetic polarity timescale for the past 56 m.y. The polarity patterns from the Pliocene-Pleistocene turbidite sequence at the Leg 149 sites show that a reliable magnetostratigraphy can be established from the early Pliocene to Holocene, including the Gilbert/Gauss boundary (3.58 m.y.) through the Matuyama/Brunhes boundary (0.78 m.y.). On the basis of distinct intervals of magnetic reversal zones and biostratigraphic datums, five magnetozones (C21n-C25n) can be recognized at the three Leg 173 sites that range from middle Eocene to late Paleocene in age. The magnetostratigraphy of the Iberia sections allows the determination of sedimentation rates and better constraints on the timing of deformation. Combining the age and average inclination information available from the magnetostratigraphy, we also present paleolatitudes vs. time for the Iberia drill sites.

Calcareous nannofossil stratigraphy, mass accumulation rates and bulk density of sediments from ODP Leg 173 sites

Drilling on the Iberia Abyssal Plain during Ocean Drilling Program Leg 173 allowed us to recover Upper Cretaceous through Paleocene sediments at Sites 1068 and 1069 and only upper Paleocene sediments at Site 1067, which expands considerably the Upper Cretaceous to Paleocene record for this region. Of these three sites, Site 1068 recovered uppermost Cretaceous sediments as well as the most complete Paleocene record, whereas Site 1067 yielded only uppermost Paleocene sediments (Zone CP8). Site 1069 provided a rather complete upper Campanian through Maastrichtian section but a discontinuous Paleocene record. After a detailed calcareous nannofossil biostratigraphy was documented in distribution charts, we calculated mass accumulation rates for Holes 1068A and 1069A. Sediments in Hole 1068A apparently record the final stages of burial of a high basement block by turbidity flows. Accumulation rates through the Upper Cretaceous indicate relatively high rates, 0.95 g/cm**2/k.y., but may be unreliable because of the lack of datum points and/or possible hiatuses. Accumulation rates in the Paleocene section of Hole 1068A fluctuated every few million years from lower (~0.35 g/cm**2/k.y.) to higher rates (~0.85 g/cm**2/k.y.) until the latest Paleocene, when rates increased to an average of ~2.0 g/cm**2/k.y. Mass accumulation rates for the Upper Cretaceous in Hole 1069A indicate a steady rate of ~0.60 g/cm**2/k.y. from 75 to 72 Ma. There may have been one or more hiatuses between 72 and 68 Ma (combined Zone CC24 through Subzone CC25b), as indicated by the very low accumulation rate of 0.15 g/cm**2/k.y. The Paleocene section of Hole 1069A does not show the same continuous record, which may result from fluctuations in the carbonate compensation depth and poor recovery (average = 40%). Zones CP4 and CP5 are missing within a barren interval; this and numerous other barren intervals affect the precision of the nannofossil zonation and calculation of mass accumulation rates. However, in spite of these missing zones, mass accumulation rates do not seem to indicate the presence of hiatuses as the rates for this barren interval average ~1.0 g/cm**2/k.y. This study set out to test the hypothesis that a reliable biostratigraphic record could be constructed from sediments derived from turbidity flows deposited below the carbonate compensation depth. As illustrated here, not only could a reliable biostratigraphic record be determined from these sediments, but sedimentation and mass accumulation rates could also be determined, allowing inferences to be drawn concerning the sedimentary history of this passive margin. The reliability of this record is confirmed by independent verification by the establishment of a magnetostratigraphy for the same cores.