Iodine ages of pore water at Hydrate Ridge, Cascadian continental margin

Hydrate Ridge off the coast of Oregon, USA, is a prime example for gas hydrate occurrences in active margin settings. It is part of the Cascadia Margin and was the focus of Ocean Drilling Program (ODP) Leg 204, which successfully recovered fluids from nine sites from the southern part of the ridge. Iodide concentrations in pore fluids associated with gas hydrates are strongly enhanced, by factors up to 5000 compared to seawater, which allows the use of this biophilic element as tracer for organic source regions. We applied the cosmogenic isotope 129I (T1/2=15.7 Ma) system to determine the age of the organic source formation responsible for the iodide enrichment. In all sites at ODP Leg 204, 129I/I ratios were found to decrease with depth to values around 250x10**-15, corresponding to minimum ages of 40 Ma, but in several sites, maxima in the 129I/I ratios point to the local addition of young iodide. The results indicate that a large amount of iodide was derived from deep accreted sediments of Eocene age, and that additional source regions provide iodide of Late Miocene age. The presence of old iodide in the pore waters suggests that fluid pathways are open to allow transport over large distances into the gas hydrate fields. The strong correlation between iodide and methane in hydrate fields coupled with the similarity in transport parameters in aqueous solutions suggests that a large fraction of methane in gas hydrates also has old sources and is transported into the present locations from source regions of Eocene age.

Sedimentology of surface samples from the Weddell Sea, Antarctica

Mineralogical and granulometric properties of glacial-marine surface sediments of the Weddell Sea and adjoining areas were studied in order to decipher spatial variations of provenance and transport paths of terrigenous detritus from Antarctic sources. The silt fraction shows marked spatial differences in quartz contents. In the sand fractions heavy-mineral assemblages display low mineralogical maturity and are dominated by garnet, green hornblende, and various types of clinopyroxene. Cluster analysis yields distinct heavy-mineral assemblages, which can be attributed to specific source rocks of the Antarctic hinterland. The configuration of modern mineralogical provinces in the near-shore regions reflects the geological variety of the adjacent hinterland. In the distal parts of the study area, sand-sized heavy minerals are good tracers of ice-rafting. Granulometric characteristics and the distribution of heavy-mineral provinces reflect maxima of relative and absolute accumulation of ice-rafted detritus in accordance with major iceberg drift tracks in the course of the Weddell Gyre. Fine-grained and coarse-grained sediment fractions may have different origins. In the central Weddell Sea, coarse ice-rafted detritus basically derives from East Antarctic sources, while the fine-fraction is discharged from weak permanent bottom currents and/or episodic turbidity currents and shows affinities to southern Weddell Sea sources. Winnowing of quartz-rich sediments through intense bottom water formation in the southern Weddell Sea provides muddy suspensions enriched in quartz. The influence of quartz-rich suspensions moving within the Weddell Gyre contour current can be traced as far as the continental slope in the northwestern Weddell Sea. In general, the focusing of mud by currents significantly exceeds the relative and absolute contribution of ice-rafted detritus beyond the shelves of the study area.

(Table 1) Concentrations of CaCO3 and organic carbon, organic matter atomic C/N ratios and delta13C values of sediment samples from Site DSDP 594

CaCO3 and total organic carbon concentrations, organic matter C/N and carbon isotope ratios, and sediment accumulation rates in late Quaternary sediments from DSDP Site 594 provide information about glacial-interglacial variations in the delivery of organic matter to the Chatham Rise offshore of southeastern New Zealand. Low C/N ratios and nearly constant organic delta13C values of ?23? indicate that marine production dominates organic matter supply in both glacial and interglacial times during oxygen isotope stages 1 through 6 (0-140 ka) and 17 through 19 (660-790 ka). Increased organic carbon mass accumulation rates in isotope stages 2, 4, 6, and 18 record enhanced marine productivity during glacial maxima. Excursions of organic delta13C values to ca. ?29? in portions of isotope stage 2 suggest that the local concentration of dissolved CO2 was occasionally elevated during the last glacial maximum, probably as a result of short periods of lowered sea-surface temperature. Dilution of carbonates by clastic continental sediment generally increases at this location during glacial maxima, but enhanced delivery of land-derived organic matter does not accompany the increased accumulation of clastic sediments.

Figure 2. Downcore variations of total diatom concentration in core MD02-2529

The modern eastern equatorial Pacific (EEP) is a major natural source for atmospheric carbon dioxide and is thought to be connected to high-latitude ocean dynamics by oceanic teleconnections on glacial-interglacial timescales. A wealth of sedimentary records aiming at reconstructing last Quaternary changes in primary productivity and nutrient utilization have been devoted to understanding those linkages between the EEP and other distant oceanic areas. Most of these records are, however, clustered in the pelagic EEP cold tongue, with comparatively little attention devoted to coastal areas. Here we present downcore measurements of the composition and concentration of the diatom assemblage together with opal (biogenic silica) concentration at site MD02-2529 recovered in the coastal Panama Basin. Piston core MD02-2529, collected in an area affected by a multitude of processes, provides evidence for strong variations in diatom production at the millennial timescale during the last glacial cycle. The maxima in total diatom concentration occurred during the early marine isotopic stage (MIS) 4 as well as during the MIS 4/3 transition and MIS 3. Rapid changes in diatom concentrations during the MIS 3 mimics Bond cycles as independently recorded by the SSS estimation derived from planktonic foraminifera from the same core. Such patterns indicate a clear linkage between diatom production in the coastal EEP and rapid climate changes in the high-latitude North Atlantic. In parallel, the long-term succession of the diatom community from coastal diatoms, predominantly thriving during MIS 5 and 4, towards pelagic diatoms, dominant during MIS 3 and 2, points to a long-term change in the surface hydrology. During Heinrich Events, diatoms strongly reduced their production, probably due to enhanced stratification in the upper water column. After the last glacial maximum, diatom production and valve preservation strongly decreased in response to the advection of nutrient (H2SiO4)-depleted, warmer water masses. Our high-resolution record highlights how regional climatic processes can modulate rapid changes in siliceous primary production as triggered by wind-induced local upwelling, indicating that millennial climatic variability can overtake other prominent hydrological processes such as those related to silicic acid leakage.

Sedimentology of the Rio Grande Rise area

Surface sediment samples and three gravity cores from the eastern terrace of the Vema Channel, the western flank of the Rio Grande Rise, and the Brazilian continental slope were investigated for physical properties, grain size, and clay mineral composition. Discharge of the Rio Doce is responsible for kaolinite enrichments on the slope south of 20° and at intermediate depths of the Rio Grande Rise. The long-distance advection of kaolinite with North Atlantic Deep Water from lower latitudes is of minor importance as evidenced by low kaolinite/chlorite ratios on the Mid-Atlantic Ridge. Cyclic variations of kaolinite/chlorite ratios in all our cores, with maxima in interglacials, are attributed to low-and high-latitude forcing of paleoclimate on the Brazilian mainland and the related discharge of the Rio Doce. A long-term trend toward more arid and 'glacial' conditions from 1500 ka to present is superimposed on the glacial-interglacial cyclicity.

(Table 1) Age and sedimentation rates of Pleistocene/Holocene sequences at DSDP Sites 86-580 and 94-611

The recovery from the North Atlantic (Site 611) of a continuous Pleistocene sedimentary record with a siliceous microfaunal component made it possible to compare the high-latitude abundance pattern of the radiolarian species Cycladophora davisiana in the Atlantic with that produced from analyses of a high-latitude record (Site 580) from the northwest Pacific. Previous studies had shown that the late Pleistocene (0-0.45 Ma) abundance variations of this species in these high-latitude regions were similar. Cycladophora davisiana maxima in the North Atlantic record reach abundance levels three to four times higher than C. davisiana maxima registered in sediments from the northwest Pacific site. This difference in magnitude of abundance peaks is most likely an effect of the more northerly location of Site 611 (53°N) compared with that of Site 580 (42°N), since high-latitude time-slice studies have shown a direct relationship between increasing latitude and C. davisiana abundance. Discontinuous preservation of radiolarians in sediments from North Atlantic Site 611 allows only tentative correlation of the North Atlantic and northwest Pacific C. davisiana abundance curves. These correlations are confined to those portions of the cores where ages are tightly constrained by magnetic boundaries, and to intervals with comparable sedimentation rates.

Planktonic foraminiferal abundances and stable isotope ratios in middle Miocene sediments of the North Atlantic and the southwestern Pacific

A three-fold expansion of the Antarctic ice sheet at 13.60, 12.82, and 11.60 Ma has been inferred from delta18O maxima analyzed in planktonic and benthic foraminiferal tests, although accompanying changes in sea surface temperature have not been detailed. We present estimated changes in middle Miocene surface-water temperatures based on analysis of delta18O in planktonic foraminifera collected at mid-latitude Deep Sea Drilling Project sites in the North Atlantic and South Pacific oceans. We also identify periods of ice-sheet growth based on comparisons of benthic and planktonic foraminiferal delta18O values. Our results indicate: (1) a distinct cooling of the sea surface from 13.6 to 13.5 Ma immediately following a peak in ice volume at 13.6 Ma, (2) a cooling of the sea surface during a period of increasing ice volume from 13.2 to 13.0 Ma, and (3) a development of the Antarctic ice sheet during a period of cooling of the sea surface centered at 11.6 Ma.

Stable carbon and oxygen isotope ratios of planktonic and benthic foraminifera from ODP Site 162-982 in the North Atlantic

Changes in the intermediate water structure of the North Atlantic were reconstructed using benthic foraminiferal delta13C at Ocean Drilling Program (ODP) site 982 for the past 1.0 Myr. During most terminations of the late Pleistocene, melting of icebergs and low-salinity surface waters caused production of Glacial North Atlantic Intermediate Water to cease, resulting in decreased ventilation of the middepth North Atlantic. Poor ventilation of intermediate water masses lasted well into some interglacial stages until upper North Atlantic Deep Water (NADW) production resumed under full interglacial conditions. The magnitude of benthic delta13C minima and ice-rafted debris maxima at terminations at site 982 generally match the degree of glacial suppression of NADW inferred from site 607. These processes may be related and controlled by the spatial and seasonal extent of sea ice cover during glaciations in the Nordic Seas.

Dissolved iron measured along surface transects of the CARUSO-EISENEX experiment

Measurements of Fe(II) and H2O2 were carried out in the Atlantic sector of the Southern Ocean during EisenEx, an iron enrichment experiment. Iron was added on three separate occasions, approximately every 8 days, as a ferrous sulfate (FeSO4) solution. Vertical profiles of Fe(II) showed maxima consistent with the plume of the iron infusion. While H2O2 profiles revealed a corresponding minima showing the effect of oxidation of Fe(II) by H2O2, observations showed detectable Fe(II) concentrations existed for up to 8 days after an iron infusion. H2O2 concentrations increased at the depth of the chlorophyll maximum when iron concentrations returned to pre-infusion concentrations (<80 pM) possibly due to biological production related to iron reductase activity. In this work, Fe(II) and dissolved iron were used as tracers themselves for subsequent iron infusions when no further SF6 was added. EisenEx was subject to periods of weak and strong mixing. Slow mixing after the second infusion allowed significant concentrations of Fe(II) and Fe to exist for several days. During this time, dissolved and total iron in the infusion plume behaved almost conservatively as it was trapped between a relict mixed layer and a new rain-induced mixed layer. Using dissolved iron, a value for the vertical diffusion coefficient Kz=6.7±0.7 cm**2/s was obtained for this 2-day period. During a subsequent surface survey of the iron-enriched patch, elevated levels of Fe(II) were found in surface waters presumably from Fe(II) dissolved in the rainwater that was falling at this time. Model results suggest that the reaction between uncomplexed Fe(III) and O2? was a significant source of Fe(II) during EisenEx and helped to maintain high levels of Fe(II) in the water column. This phenomenon may occur in iron enrichment experiments when two conditions are met: (i) When Fe is added to a system already saturated with regard to organic complexation and (ii) when mixing processes are slow, thereby reducing the dispersion of iron into under-saturated waters.

Middle Miocene isotope stratigraphy and paleoceanographic evolution of the northwest and southwest Australian margins (Wombat Plateau and Great Australian Bight)

The benthic stable isotope record from ODP Site 761 (Wombat Plateau, NW Australia, 2179.3 m water depth) documents complete recovery of the middle Miocene delta13C excursion corresponding to the climatic optimum and subsequent expansion of the East Antarctic Ice Sheet. The six main delta13C maxima of the "Monterey Excursion" between 16.4 and 13.6 Ma and the characteristic stepped increase in delta18O between 14.5 and 13.9 Ma are clearly identified. The sedimentary record of the shallower ODP Sites 1126 and 1134 [Great Australian Bight (GAB), SWAustralia, 783.8 and 701 m water depth, respectively] is truncated by several unconformities. However, a composite benthic stable isotope curve for these sites provides a first middle Miocene bathyal record for southwest Australia. The delta18O and delta13C curves for Sites 1126 and 1134 indicate a cooler, better-ventilated water mass at ~700 m water depth in the Great Australian Bight since approximately 16 Ma. This cooler and younger water mass probably originated from a close southern source. Cooling of the bottom water at ~16 Ma started much earlier than at other sites of equivalent paleodepths in the central and western parts of the Indian Ocean. At Site 761, the delta18O curve shows an excellent match with the global sea level curve between ~11.5 and 15.1 Ma, and thus closely reflects changes in global ice volume. Prior to 15.1 Ma, the mismatch between the delta18O curve and the sea level curve indicates that delta18O fluctuations are mainly due to changes in bottom water temperature.