Geochemistry of ODP Site 162-907, North Atlantic

A geochemical analysis is conducted on hemipelagic sediments at ODP Leg 162, Site 907, North Atlantic. On the basis of major and minor element concentrations, the sequence is divided into five units. Geochemical data reveal that the sediments originated from two specific source areas, i.e., continental icerafted debris (IRD) and Icelandic basalt. In the upper part (lithological units I and II, 0 to 63.1 meters below sea floor (mbsf)), sediments were derived from continental IRD, whereas in the lower part, sediments (lithological units III, IV, and V, below 63.1 mbsf) comprise mixture of continental IRD and minor supply from the Icelandic basalt. The ratio of TiO2/Al2O3 to SiO2 content and the Th to Ti/Al molar ratio clearly provide a key to discriminate provenances. The change in source area is most likely related to the oceanographic and climatic evolution in the North Atlantic since the middle Miocene. Biogenic fossil-barren intervals (Units II and V) are considered as a consequence of dissolution caused by oceanic circulation. The timing of IRD initiation confers with that of geochemical analysis. Total organic carbon to total nitrogen (C/N) ratio shows a striking variation in the entire core. The C/N ratios exceed 10 below approximately 196 mbsf (lithological unit V) with a gradual downward increase. This suggests that terrigenous organic matters have been supplied from the neighboring continents. The total organic carbon to total sulfur (C/S) ratio also shows such possibility as well as diagenetic changes in Units IV and V. The carbonate-barren intervals presented in Units II and V, and intermittently in Units III and IV are interpreted as a consequence of dissolution effect related with climatic variation and deep-water circulation. Additional low surface productivity was considerable.

Argon composition and new combined chronologies of ODP Sites 185-1149 and 191-1179

Despite the different scientific objectives of Legs 185 and 191, the sedimentary sections recovered from Sites 1149 and 1179 are the two most complete sections recovered from the northwestern Pacific Basin by either the Deep Sea Drilling Project (DSDP) (i.e., Legs 6, 20, 32, and 86) or ODP (i.e., Legs 185 and 191). During Leg 185, a complete sedimentary section (410 m) and an additional 133 m of highly altered volcanic basement were recovered. The Miocene to Pleistocene section (i.e., upper ~150 m) recovered from Site 1149 includes lithostratigraphic Unit I (0-118.2 meters below sea floor [mbsf]) and Subunit IIA (118.2-149.5 mbsf) of Plank, Ludden, Escutia, et al. (2000, doi:10.2973/odp.proc.ir.185.2000) and consists of ash- and biogenic silica- bearing clay, radiolarian-bearing clay, silt-bearing clay, ash-bearing siliceous ooze, and diatomaceous clay, with numerous discrete volcanic ash layers (Plank, Ludden, Escutia, et al., 2000, doi:10.2973/odp.proc.ir.185.2000). During Leg 191, a near-continuous 375-m-thick sedimentary section was recovered in addition to 100 m of basaltic basement. The upper 221.5 m of the sedimentary section at Site 1179 (i.e., within lithostratigraphic Unit I of Kanazawa, Sager, Escutia et al. [2001, doi:10.2973/odp.proc.ir.191.2001]) consists of upper Miocene to Pleistocene clay- and radiolarian-bearing diatom ooze containing numerous discrete ash layers. The presence of discrete ash layers within the Miocene to Pleistocene sedimentary section at both Site 1149 and 1179 provides a unique opportunity to conduct 40Ar/39Ar ash chronology to refine the excellent magnetostratigraphic records (based on the scale of Berggren et al., 1995) obtained shipboard from both sites (Plank, Ludden, Escutia, et al., 2000, doi:10.2973/odp.proc.ir.185.2000; Kanazawa, Sager, Escutia, et al., 2001, doi:10.2973/odp.proc.ir.191.2001).In this data report we present the analytical results from the 40Ar/39Ar incrementally heated analyses and provide a new combined late Miocene to Pleistocene 40Ar/39Ar and magnetostratigraphic chronology for the northwestern Pacific.

(Table A1) Chemical composition of abyssal peridotites from ODP Hole 153-920

The compatibility of vanadium (V) during mantle melting is a function of oxygen fugacity (fO2): at high fO2's, V becomes more incompatible. The prospects and limitations of using the V content of peridotites as a proxy for paleo-fO2 at the time of melt extraction were investigated here by assessing the uncertainties in V measurements and the sensitivity of V as a function of degree of melt extracted and fO2. V-MgO and V-Al2O3 systematics were found to be sensitive to fO2 variations, but consideration of the uncertainties in measurements and model parameters indicates that V is sensitive only to relative fO2 differences greater than ~2 log units. Post-Archean oceanic mantle peridotites, as represented by abyssal peridotites and obducted massif peridotites, have V-MgO and -Al2O3 systematics that can be modeled by 1.5 GPa melting between FMQ - 3 and FMQ - 1. This is consistent with fO2's of the mantle source for mid-ocean ridge basalts (MORBs) as determined by the Fe3+ activity of peridotitic minerals and basaltic glasses. Some arc-related peridotites have slightly lower V for a given degree of melting than oceanic mantle peridotites, and can be modeled by 1.5 GPa melting at fO2's as high as FMQ. However, the majority of arc-related peridotites have V-MgO systematics overlapping that of oceanic mantle peridotites, suggesting that although some arc mantle may melt under slightly oxidizing conditions, most arc mantle does not. The fact that thermobarometrically determined fO2's in arc peridotites and lavas can be significantly higher than that inferred from V systematics, suggests that V retains a record of the fO2 during partial melting, whereas the activity of Fe3+ in arc peridotitic minerals and lavas reflect subsequent metasomatic overprints and magmatic differentiation/emplacement processes, respectively. Peridotites associated with middle to late Archean cratonic mantle are characterized by highly variable V-MgO systematics. Tanzanian cratonic peridotites have V systematics indistinguishable from post-Archean oceanic mantle and can be modeled by 3 GPa partial melting at ~FMQ - 3. In contrast, many South African and Siberian cratonic peridotites have much lower V contents for a given degree of melting, suggesting at first glance that partial melting occurred at high fO2's. More likely, however, their unusually low V contents for a given degree of melting may be artifacts of excess orthopyroxene, a feature that pervades many South African and Siberian peridotites but not the Tanzanian peridotites. This is indicated by the fact that the V contents of South African and Siberian peridotites are correlated with increases in SiO2 content, generating data arrays that cannot be modeled by partial melting but can instead be generated by the addition of orthopyroxene through processes unrelated to primary melt depletion. Correction for orthopyroxene addition suggests that the South African and Siberian peridotites have V-MgO systematics similar to those of Tanzanian peridotites. Thus, if the Tanzanian peridotites represent the original partial melting residues, and if the South African and Siberian peridotites have been modified by orthopyroxene addition, then there is no indication that Archean cratonic mantle formed under fO2's significantly greater than that of modern oceanic mantle. Instead, the fO2's inferred from the V systematics in these three cratonic peridotite suites are within range of modern oceanic mantle. This also suggests that the transition from a highly reducing mantle in equilibrium with a metallic core to the present oxidized state must have occurred by late Archean times.

Halogene concentrations and iodine isotopic composition in pore water on Hydrare Ridge, Cascadia continental margin

We report iodine and bromine concentrations in a total of 256 pore water samples collected from all nine sites of Ocean Drilling Program Leg 204, Hydrate Ridge. In a subset of these samples, we also determined iodine ages in the fluids using the cosmogenic isotope 129I (T1/2 = 15.7 Ma). The presence of this cosmogenic isotope, combined with the strong association of iodine with methane, allows the identification of the organic source material responsible for iodine and methane in gas hydrates. In all cores, iodine concentrations were found to increase strongly with depth from values close to that of seawater (0.0004 mM) to concentrations >0.5 mM. Several of the cores taken from the northwest flank of the southern summit show a pronounced maximum in iodine concentrations at depths between 100 and 150 meters below seafloor in the layer just above the bottom-simulating reflector. This maximum is especially visible at Site 1245, where concentrations reach values as high as 2.3 mM, but maxima are absent in the cores taken from the slope basin sites (Sites 1251 and 1252). Bromine concentrations follow similar trends, but enrichment factors for Br are only 4-8 times that of seawater (i.e., considerably lower than those for iodine). Iodine concentrations are sufficient to allow isotope determinations by accelerator mass spectrometry in individual pore water samples collected onboard (~5 mL). We report 129I/I ratios in a few samples from each core and a more complete profile for one flank site (Site 1245). All 129I/I ratios are below the marine input ratio (Ri = 1500x10**-15). The lowest values found at most sites are between 150 and 250x10**-15, which correspond to minimum ages between 40 and 55 Ma, respectively. These ages rule out derivation of most of the iodine (and, by association, of methane) from the sediments hosting the gas hydrates or from currently subducting sediments. The iodine maximum at Site 1245 is accompanied by an increase in 129I/I ratios, suggesting the presence of an additional source with an age younger than 10 Ma; there is indication that younger sources also contribute at other sites, but data coverage is not yet sufficient to allow a definitive identification of sources there. Likely sources for the older component are formations of early Eocene age close to the backstop in the overriding wedge, whereas the younger sources might be found in recent sediments underlying the current locations of the gas hydrates.