Sulphur geochemistry of interstitial waters and squeeze cake samples of ODP Leg 181 sites

Seventy-nine interstitial water samples from six sites (Ocean Drilling Program Sites 1119-1124) from the southwestern Pacific Ocean have been analyzed for stable isotopes of dissolved sulfate (34S), along with major and minor ions. Sulfate from the interstitial fluids (34S values between +20.7 and +57.5 vs. the Vienna-Canyon Diablo troilite standard) was enriched in 34S with respect to modern seawater (34S +20.6), indicating that differing amounts of microbial sulfate reduction took place at all investigated sites. Microbial sulfate reduction was found at all sites, the intensity depending on the availability of organic matter, which is controlled by paleosedimentation conditions (e.g., sedimentation rate and presence of turbidites). In addition, total reduced inorganic sulfur (essentially pyrite) as a product of microbial sulfate reduction was quantified in selected sediments from Site 1119.

Sediment geochemistry of ODP Leg 127 sites

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the final preserved chemistry of Japan Sea sediments are evaluated by investigating the rare earth element (REE), major element, and trace element concentrations in 59 squeeze-cake whole-round and 27 physical-property sample residues from Sites 794, 795, and 797, cored during ODP Leg 127. The most important variation in sedimentary chemical composition is the increase in SiO2 concentration through the Pliocene diatomaceous sequences, which dilutes most other major and trace element components by various degrees. This biogenic input is largest at Site 794 (Yamato Basin), moderately developed at Site 797 (Yamato Basin), and of only minor importance at Site 795 (Japan Basin), potentially reflecting basinal contrasts in productivity with the Yamato Basin recording greater biogenic input than the Japan Basin and with the easternmost sequence of Site 794 lying beneath the most productive waters. There are few systematic changes in solid-phase chemistry resulting from the opal-A/opal-CT or opal-CT/quartz silica phase transformations. Most major and trace element concentrations are controlled by the aluminosilicate fraction of the sediment, although the effects of diagenetic silica phases and manganese carbonates are of localized importance. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the upper Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. SumREE at Site 795 also is affiliated strongly with aluminosilicate phases and yet is diluted only slightly by siliceous input. At Site 797, SumREE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. Ce/Ce* profiles at all three sites increase essentially monotonically with depth and record progressive diagenetic LREE fractionation. The observed Ce/Ce* increases are not responding to changes in the paleoceanographic oxygenation state of the overlying water, as there is no independent evidence to suggest the proper oceanographic conditions. Ce/Ce* correlates slightly better with depth than with age at the two Yamato Basin sites. The downhole increase in Ce/Ce* at Sites 794 and 797 is a passive response to the diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and Lan/Ybn suggests that other processes mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column and that an additional ~38% is recycled at or near the seafloor. Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply buried interstitial waters.

Seal census raw data during POLARSTERN expedition ANT-XV/3 (PS48)

The density, species composition, and possible change in the status of pack ice seals within the Weddell Sea were investigated during the 1997/1998 summer cruise of the RV "Polarstern" (ANT-XV/3, PS48). Comparisons were made with previous surveys in the Weddell Sea where it was assumed that all seals were counted in a narrow strip on either side oft he ship or aircraft. A total of 15 aerial censuses were flown during the period 23 January - 7 March 1998 in the area bounded by 07°08' and 45°33' West longitude. The censused area in the eastern Weddell Sea was largely devoid of pack ice while a well circumscribed pack ice field remained in the western Weddell Sea. A total of 3,636 (95.4 %) crabeater seals, 21 (0.5 %) Ross seals, 45 (1.2 %) leopard seals and 111 (2.9 %) Weddell seals were observed on the pack ice during a total of 1,356.57 linear nautical miles (244.2 nm) of transect line censused. At a mean density of 21.16 1/nm**2 over an area of 244.2 nm, it is the highest densities on record for crabeater seals, density of up to 411.7 1/nm**2 being found in small areas. The overall high densities of seals (30.18 1/nm**2) recorded for the eastern Weddell Sea (27.46 1/nm**2, 0.27 1/nm**2, and 0.66 1/nm**2 for crabeater, leopard and Weddell seals respectively) is a consequence of the drastically reduced ice cover and the inverse relationship that exists between cover and seal densities. Ross seal densities (0.08 1/nm**2) were the lowest on record fort the area. It is suggested that seals largely remain within the confines of the pack ice despite seasonal and annual changes in its distribution. Indications are that in 1998 the El Niño has manifested itself in the Weddell Sea, markedly influencing the density and distribution of pack ice seals.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Distribution, density and abundance of Antarctic ice seals off Queen Maud Land and the eastern Weddell Sea

The Antarctic Pack Ice Seal (APIS) Program was initiated in 1994 to estimate the abundance of four species of Antarctic phocids: the crabeater seal Lobodon carcinophaga, Weddell seal Leptonychotes weddellii, Ross seal Ommatophoca rossii and leopard seal Hydrurga leptonyx and to identify ecological relationships and habitat use patterns. The Atlantic sector of the Southern Ocean (the eastern sector of the Weddell Sea) was surveyed by research teams from Germany, Norway and South Africa using a range of aerial methods over five austral summers between 1996-1997 and 2000-2001. We used these observations to model densities of seals in the area, taking into account haul-out probabilities, survey-specific sighting probabilities and covariates derived from satellite-based ice concentrations and bathymetry. These models predicted the total abundance over the area bounded by the surveys (30°W and 10°E). In this sector of the coast, we estimated seal abundances of: 514 (95 % CI 337-886) x 10**3 crabeater seals, 60.0 (43.2-94.4) x 10**3 Weddell seals and 13.2 (5.50-39.7) x 10**3 leopard seals. The crabeater seal densities, approximately 14,000 seals per degree longitude, are similar to estimates obtained by surveys in the Pacific and Indian sectors by other APIS researchers. Very few Ross seals were observed (24 total), leading to a conservative estimate of 830 (119-2894) individuals over the study area. These results provide an important baseline against which to compare future changes in seal distribution and abundance.