(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Oxygen and hydrogen isotopes measured in the Northeast Atlantic

Only a few studies have examined the variation of oxygen and hydrogen isotopes of seawater in NE Atlantic water masses, and data are especially sparse for intermediate and deep-water masses. The current study greatly expands this record with 527 d18O values from 47 stations located throughout the mid- to low-latitude NE Atlantic. In addition, dD was analyzed in the 192 samples collected along the GEOTRACES North Atlantic Transect GA03 (GA03_e=KN199-4) and the 115 Iberia-Forams cruise samples from the western and southern Iberian margin. An intercomparison study between the two stable isotope measurement techniques (cavity ring-down laser spectroscopy and magnetic-sector isotope ratio mass spectrometry) used to analyze GA03_e samples reveals relatively good agreement for both hydrogen and oxygen isotope ratios. The surface (0-100 m) and central (100-500 m) water isotope data show the typical, evaporation related trend of increasing values equatorward with the exception for the zonal transect off Cape Blanc, NW Africa. Off Cape Blanc, surface water isotope signatures are modified by the upwelling of fresher Antarctic Intermediate Water (AAIW) that generally has isotopic values of 0.0 to 0.5 per mil for d18O and 0 to 2 per mil for dD. Along the Iberian margin the Mediterranean Outflow Water (MOW) is clearly distinguished by its high d18O (0.5-1.1 per mil) and dD (3-6 per mil) values that can be traced into the open Atlantic. Isotopic values in the NE Atlantic Deep Water (NEADW) are relatively low (d18O: -0.1 to 0.5 per mil; dD: -1 to 4 per mil) and show a broader range than observed previously in the northern and southern convection areas. The NEADW is best observed at GA03_e Stations 5 and 7 in the central NE Atlantic basin. Antarctic Bottom Water isotope values are relatively high indicating modification of the original Antarctic source water along the flow path. The reconstructed d18O-salinity relationship for the complete data set has a slope of 0.51, i.e., slightly steeper than the 0.46 described previously by Pierre et al. (1994, J. Mar. Syst. 5 (2), 159-170.) for the tropical to subtropical Northeast Atlantic. This slope decreases to 0.46 for the subtropical North Atlantic Central Water (NACW) and the MOW and to 0.32 for the surface waters of the upper 50 m. The dD-salinity mixing lines have estimated slopes of 3.01 for the complete data, 1.26 for the MOW, 3.47 for the NACW, and 2.63 for the surface waters. The slopes of the d18O-dD relationship are significantly lower than the one for the Global Meteoric Water Line with 5.6 for the complete data set, 2.30 for the MOW, 4.79 for the NACW, and 3.99 for the surface waters. The lower slopes in all the relationships clearly reflect the impact of the evaporation surplus in the subtropics.

Major, trace and rare earth element concentration of ODP Site 210-1277 basalts, Newfoundland margin

Drilling of the distal Newfoundland margin at Ocean Drilling Program Site 1277 recovered part of the transition between exhumed sub-continental mantle lithosphere and normal mid-ocean-ridge basalt (N-MORB) volcanism perhaps related to the initiation of seafloor spreading, which may have occurred near the Aptian/Albian boundary, coincident with the final separation of subcontinental mantle lithosphere. Subcontinental mantle lithosphere was recovered near the crest of a basement high, the Mauzy Ridge. This ridge lies near magnetic Anomaly M1 and is inferred to be of Barremian age. The recovered section is dominated by serpentinized spinel harzburgite, with subordinate dunite and minor gabbroic intrusives, and it includes inferred high-temperature ductile shear zones. The serpentinite is capped by foliated gabbro cataclasite that is interpreted as the product of a major seafloor extensional detachment. The serpentinized harzburgite beneath is highly depleted subcontinental mantle lithosphere that was exhumed to create new seafloor within the ocean-continent transition zone. After inferred removal of overlying brittle crust, the detachment was eroded, producing multiple mass flows that were dominated by clasts of serpentinite and gabbro in a lithoclastic and calcareous matrix. Basaltic lavas were erupted spasmodically, mainly as sheet flows, with subordinate lava breccia, hyaloclastite, and possible pillow lava. The sedimentary-volcanic succession and the exhumed mantle lithosphere experienced later high-angle extensional fracturing and probably faulting. Extensional fissures opened incrementally and were filled with silt-sized carbonate, basalt-derived clastic sediment, and hyaloclastite, forming neptunian dykes and geopetal structures. Chemical analysis of representative basalts for major elements and trace elements were made using a high-precision, high-accuracy X-ray fluorescence method (utilizing increased count times) and by whole-rock inductively coupled plasma-mass spectrometry that yielded additional evidence for rare earth elements. The analyses indicate N-MORB to slightly enriched compositions. The MORB was produced by relatively high degree melting of a fertile mantle source that differed strongly from the cored serpentinized peridotites. The basalts exhibit a distinct negative Nb anomaly on MORB-normalized plots that can be explained by prior extraction of melt from upper mantle that had previously been affected by subduction, possibly during closure of the Iapetus or Rheic oceans. In the proposed interpretation, mantle lithosphere was exhumed to the seafloor and experienced mass wasting to form serpentinite-rich mass flows. The interbedded MORB records the beginning of a transition to "normal" seafloor spreading. This interpretation takes into account drilling results from the Iberia-Galicia margin and the Jurassic Alps-Apennines.

Ar and U-Th-Pb age determinations for minerals from ODP Holes of ODP Legs 173 and 210

We report U-Pb and 39Ar-40Ar measurements on plutonic rocks recovered from the Ocean Drilling Program (ODP) Legs 173 and 210. Drilling revealed continental crust (Sites 1067 and 1069) and exhumed mantle (Sites 1070 and 1068) along the Iberia margin and exhumed mantle (Site 1277) on the conjugate Newfoundland margin. Our data record a complex igneous and thermal history related to the transition from rifting to seafloor spreading. The results show that the rift-to-drift transition is marked by a stuttering start of MORB-type magmatic activity. Subsequent to initial alkaline magmatism, localized mid-oceanic ridge basalts (MORB) magmatism was again replaced by basin-wide alkaline events, caused by a low degree of decompression melting due to tectonic delocalization of deformation. Such "off-axis" magmatism might be a common process in (ultra-) slow oceanic spreading systems, where "magmatic" and "tectonic" spreading varies in both space and time.

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.