(Table 1) Redox potential and chemical element contents in CaCO3 and amorphous silica free matter in surface layer bottom sediments of the Pacific Ocean from Hawaiian Islands to Mexico coast

Distribution of Fe, Mn, P, Ti, Cu, Ni, Co, V, Cr, W, Mo, and As in the surface sediment layer on the section from the Hawaiian Islands to the coast of Mexico (Mexico section) is studied. Contents of all studied elements increase from biogenic-terrigenous sediments off the coast of Mexico to pelagic red clays of the Northeast Basin, and more sharply for mobile elements - Mn, Mo, Cu, Ni, Co, and As. In near Hawaii sediments rich in coarsely fragmented volcanic-terrigenous and pyroclastic material of basaltic composition with high contents of Ti, Fe, V, Cr, W, and P, contents of these elements increase sharply, and contents of Mn, Mo, Ni, Co, and Cu for the same reason decrease sharply in comparison with red clay. Abnormally high contents of Mn, Mo, Cu, Ni, Co, and As in the upper layer of hemipelagic and transition sediments of the Mexico section result from diagenetic redistribution and their accumulation on the surface. Processes of diagenetic redistribution in hemipelagic and transition sediment mass of the Mexico section are more rapid than in similar sediments of the Japan section due lower sedimentation rates and higher initial concentrations of Mn. Basic similarity of element distribution regularities in sediments of Japan and Mexico sections is shown.

Age models, color measurements, and calculated sea surface temperatures of sediment cores from the Bering Sea and the Sea of Okhotsk

Past changes in North Pacific sea surface temperatures and sea-ice conditions are proposed to play a crucial role in deglacial climate development and ocean circulation but are less well known than from the North Atlantic. Here, we present new alkenone-based sea surface temperature records from the subarctic northwest Pacific and its marginal seas (Bering Sea and Sea of Okhotsk) for the time interval of the last 15 kyr, indicating millennial-scale sea surface temperature fluctuations similar to short-term deglacial climate oscillations known from Greenland ice-core records. Past changes in sea-ice distribution are derived from relative percentage of specific diatom groups and qualitative assessment of the IP25 biomarker related to sea-ice diatoms. The deglacial variability in sea-ice extent matches the sea surface temperature fluctuations. These fluctuations suggest a linkage to deglacial variations in Atlantic meridional overturning circulation and a close atmospheric coupling between the North Pacific and North Atlantic. During the Holocene the subarctic North Pacific is marked by complex sea surface temperature trends, which do not support the hypothesis of a Holocene seesaw in temperature development between the North Atlantic and the North Pacific.

(Table 1) Water column biogenic silica concentrations and Si isotopic composition during Marion Dufresne cruise MD166 off South Africa

Southern Ocean biogeochemical processes have an impact on global marine primary production and global elemental cycling, e.g. by likely controlling glacial-interglacial pCO2 variation. In this context, the natural silicon isotopic composition (d30Si) of sedimentary biogenic silica has been used to reconstruct past Si-consumption:supply ratios in the surface waters. We present a new dataset in the Southern Ocean from a IPY-GEOTRACES transect (Bonus-GoodHope) which includes for the first time summer d30Si signatures of suspended biogenic silica (i) for the whole water column at three stations and (ii) in the mixed layer at seven stations from the subtropical zone up to the Weddell Gyre. In general, the isotopic composition of biogenic opal exported to depth was comparable to the opal leaving the mixed layer and did not seem to be affected by any diagenetic processes during settling, even if an effect of biogenic silica dissolution cannot be ruled out in the northern part of the Weddell Gyre. We develop a mechanistic understanding of the processes involved in the modern Si-isotopic balance, by implementing a mixed layer model. We observe that the accumulated biogenic silica (sensu Rayleigh distillation) should satisfactorily describe the d30Si composition of biogenic silica exported out of the mixed layer, within the limit of the current analytical precision on the d30Si. The failures of previous models (Rayleigh and steady state) become apparent especially at the end of the productive period in the mixed layer, when biogenic silica production and export are low. This results from (1) a higher biogenic silica dissolution:production ratio imposing a lower net fractionation factor and (2) a higher Si-supply:Si-uptake ratio supplying light Si-isotopes into the mixed layer. The latter effect is especially expressed when the summer mixed layer becomes strongly Si-depleted, together with a large vertical silicic acid gradient, e.g. in the Polar Front Zone and at the Polar Front.

Distribution of organic carbon in surface sediments covered during SONNE cruise SO184

Sediments were sampled and oxygen profiles of the water column were determined in the Indian Ocean off west and south Indonesia in order to obtain information on the production, transformation, and accumulation of organic matter (OM). The stable carbon isotope composition (d13Corg) in combination with C/N ratios depicts the almost exclusively marine origin of sedimentary organic matter in the entire study area. Maximum concentrations of organic carbon (Corg) and nitrogen (N) of 3.0% and 0.31%, respectively, were observed in the northern Mentawai Basin and in the Savu and Lombok basins. Minimum d15N values of 3.7 per mil were measured in the northern Mentawai Basin, whereas they varied around 5.4 per mil at stations outside this region. Minimum bottom water oxygen concentrations of 1.1 mL L**1, corresponding to an oxygen saturation of 16.1%, indicate reduced ventilation of bottom water in the northern Mentawai Basin. This low bottom water oxygen reduces organic matter decomposition, which is demonstrated by the almost unaltered isotopic composition of nitrogen during early diagenesis. Maximum Corg accumulation rates (CARs) were measured in the Lombok (10.4 g C m**-2 yr**-1) and northern Mentawai basins (5.2 g C m**-2 yr**-1). Upwelling-induced high productivity is responsible for the high CAR off East Java, Lombok, and Savu Basins, while a better OM preservation caused by reduced ventilation contributes to the high CAR observed in the northern Mentawai Basin. The interplay between primary production, remineralisation, and organic carbon burial determines the regional heterogeneity. CAR in the Indian Ocean upwelling region off Indonesia is lower than in the Peru and Chile upwellings, but in the same order of magnitude as in the Arabian Sea, the Benguela, and Gulf of California upwellings, and corresponds to 0.1-7.1% of the global ocean carbon burial. This demonstrates the relevance of the Indian Ocean margin off Indonesia for the global OM burial.

Surface sediment samples from several fore-arc basins west and southwest of the Indonesian Archipelago, analyzed by planktonic foraminifera, stable oxygen and carbon isotopic signals and opal and CaCO3 contents in bulk sediment

A total of 69 surface sediment samples from several fore-arc basins located west and southwest of the Indonesian Archipelago was analyzed with respect to the faunal composition of planktonic foraminifera, the stable oxygen and carbon isotopic signal of a surface-dwelling (Globigerinoides ruber) and a thermocline-dwelling (Neogloboquadrina dutertrei) species, and the opal and CaCO3 contents in bulk sediment. Our results show that the distribution pattern of opal in surface sediments corresponds well to the upwelling-induced chlorophyll concentration in the upper water column and thus, represents a reliable proxy for marine productivity in the coastal upwelling area off S and SW Indonesia. Present-day oceanography and marine productivity are also reflected in the tropical to subtropical and upwelling assemblages of planktonic foraminifera in the surface sediments, which in part differ from previous studies in this region probably due to different coring methods and dissolution effects. The average stable oxygen isotopic values (d18O) of G. ruber in surface sediments vary between 2.9 per mill and 3.2 per mill from basin to basin and correspond to the oceanographic settings during the SE monsoon (July-October) off west Sumatra, whereas off southern Indonesia, they reflect the NW monsoon (December-March) or annual average conditions. The d18O values of N. dutertrei show a stronger interbasinal variation between 1.6 per mill and 2.2 per mill and correspond to the upper thermocline hydrology in July-October. In addition, the difference between the shell carbon isotopic values (d13C) of G. ruber and N. dutertrei (Delta d13C) appears to be an appropriate productivity recorder only in the non-upwelling areas off west Sumatra. Consequently, joint interpretation of the isotopic values of these species is distinctive for different fore-arc basins W and SW of Indonesia and should be considered in paleoceanographic studies.

Diatoms on the lower surface of Arctic sea ice and hydrochemical parameters in the water-ice layer

Morphology, ecology, range and species composition of diatom algae mass accumulations that are biotypically associated with the lower surface of Arctic sea ice are discussed. Materials were obtained by skindivers in the Central Arctic Basin at drift stations SP-23 in August 1977 and SP-22 in July 1980.

Biogenic silica in the coastal plume of the Mississippi River

The surface distributions of dissolved silicic acid, chlorophyll and diatom abundance were measured in the plume of the Mississippi River and adjacent waters during spring (late April and early May 1993) and summer (July 1992). In spring, the time of maximum river flow, there was an intense diatom bloom with a mean diatom abundance of 1.5 x 10**7 cells/l, more than an order of magnitude higher than in summer. Mixing curves of silicic acid concentration ([Si(OH)4]) versus salinity indicate that biological uptake within the river plume removed >99% of the Si(OH)4 supplied by the river in spring and 80 to 95% in summer. In spring [Si(OH)4] was occasionally depleted to <0.2 µM-among the lowest values ever reported from the ocean-with extensive depletion to >=0.5 µM over the shelf. In summer [Si(OH)4] was less severely depleted; the lowest measured was 0.93 µM and all others were >=2.4 µM. 30Si kinetic experiments were performed during both spring and summer to measure the degree to which the rate of Si uptake by the natural diatom assemblages was limited in situ by substrate availability. In spring the dependence of the specific uptake rate (V) on extracellular [Si(OH)4] conformed much more closely to the Michaelis-Menten saturation function than has been observed in past studies. Strong dependence of V on [Si(OH)4] was observed throughout the most Si(OH)4-depleted (<0.5 µM) region, where V was limited to 12 to 45% of the diatom assemblages' maximum uptake rate (Vmax). Half-saturation concentrations for Si uptake (Ks) averaged 0.85 uM (range = 0.48 to 1.71; n = 7) in spring, with the lowest values equal to the lowest previously reported for natural diatom assemblages. There was only 1 station in summer where V was limited by [Si(OH)4], and at that station Ks was 5.3 µM-quite high in comparison with previous studies. At stations where V was limited by [Si(OH)4], in both spring and summer, Chaetoceros spp. were numerically dominant; where there was no Si limitation other diatoms, usually Skeletonema costatum, dominated. The data thus indicate strong Si limitation in spring, with diatom assemblages well adapted to low [Si(OH)4], but little or no Si limitation in summer. Historical data suggest that coastal Si(OH)4 depletion and Si limitation may be recent phenomena in the northern Gulf of Mexico, resulting from increasing [NO3-] and decreasing [Si(OH)4] in the Mississippi River during the past 30 to 50 yr.

Composition of surface layer bottom sediments from the Kem' River estuary, White Sea

Based on grain-size, mineralogical and chemical analyses of samples collected in cruises of R/V Ekolog (Institute of Northern Water Problems, Karelian Research Centre of RAS, Petrozavodsk) in 2001 and 2003 regularities of chemical element distribution in surface layer bottom sediments of the Kem' River Estuary in the White Sea were studied. For some toxic elements labile and refractory forms were determined. Correlation analysis was carried out and ratios Me/Al were calculated as proxies of terrigenous contribution. Distribution of such elements as Fe, Mn, Zn, Cr, Ti was revealed to be influenced by natural factors, mainly by grain size composition of bottom sediments. These metals have a tendency for accumulation in fine-grained sediments with elevated organic carbon contents. Distribution of Ni is different from one of Fe, Mn, Zn, Cr, Ti. An assumption was made that these distinctions were caused by anthropogenic influence.

Biomarkers in surface sediments from the Ob and Yenisei estuaries and the southern Kara Sea

Organic-geochemical bulk parameter (Total organic carbon contents, C/N ratios and d13Corg values), biogenic opal and biomarkers (n-alkanes, fatty acids, sterols and amino acids) were determined in surface sediments from the Ob and Yenisei estuaries and the adjacent southern Kara Sea. Maximum TOC contents were determined in both estuaries, reaching up to 3 %. Relatively high C/N ratios around 10, light d13Corg values of -26.5 per mil (Yenisei) and -28 to -28.7 per mil (Ob), and maximum concentrations of long-chain n-alkanes of up to about 10 µg/g Sed clearly show the predominance of terrigenous organic matter in the sediments from the estuaries. Towards the open Kara Sea, all p arameters indicate a decrease in terrigenous organic carbon. Brassicasterol as well as the short-chain n-alkanes parallel this trend, suggesting that these biomarkers are probably also related to a terrigenous (fresh-water phytoplankton) source. Amino acid spectra show characteristic trends from the Yenisei Estuary to the open Kara Sea revealing increasing state of degradation. Sedimentary organic matter in the Yenisei Estuary is relatively less degraded compared to the Ob Estuary and the open Kara Sea.

(Table 2) Integrated concentration, production and dissolution of silica in the water column of the southern Pacific

An intense diatom bloom developed within a strong meridional silicic acid gradient across the Antarctic Polar Front at 61°S, 170°W following stratification of the water column in late October/early November 1997. The region of high diatom biomass and the silicic acid gradient propogated southward across the Seasonal Ice Zone through time, with the maximum diatom biomass tracking the center of the silicic acid gradient. High diatom biomass and high rates of silica production persisted within the silicic acid gradient until the end of January 1998 (ca. 70 d) driving the gradient over 500 km to the south of its original position at the Polar Front. The bloom consumed 30 to >40 µM Si(OH)4 in the euphotic zone between about 60 and 66°S leaving near surface concentrations <2.5 µM and occasionally <1.0 µM in its wake. Integrated biogenic silica concentrations within the bloom averaged 410 mmol Si/m**2 (range 162-793 mmol Si/m**2). Average integrated silica production on two consecutive cruises in December 1997 and January 1998 that sampled the bloom while it was well developed were 27.5±6.9 and 22.6±20 mmol Si/m**2/d, respectively. Those levels of siliceous biomass and silica production are similar in magnitude to those reported for ice-edge diatom blooms in the Ross Sea, Antarctica, which is considered to be among the most productive regions in the Southern Ocean. Net silica production (production minus dissolution) in surface waters during the bloom was 16-21 mmol Si/m**2/d, which is sufficient for diatom growth to be the cause of the southward displacement of the silicic acid gradient. A strong seasonal change in silica dissolution : silica production rate ratios was observed. Integrated silica dissolution rates in the upper 100-150 m during the low biomass period before stratification averaged 64% of integrated production. During the bloom integrated dissolution rates averaged only 23% of integrated silica production, making 77% of the opal produced available for export to depth. The bloom ended in late January apparently due to a mixing event. Dissolution : production rate ratios increased to an average of 0.67 during that period indicating a return to a predominantly regenerative system. Our observations indicate that high diatom biomass and high silica production rates previously observed in the marginal seas around Antarctica also occur in the deep ocean near the Polar Front. The bloom we observed propagated across the latitudinal band overlying the sedimentary opal belt which encircles most of Antarctica implying a role for such blooms in the formation of those sediments. Comparison of our surface silica production rates with new estimates of opal accumulation rates in the abyssal sediments of the Southern Ocean, which have been corrected for sediment focusing, indicate a burial efficiency of <=4.6% for biogenic silica. That efficiency is considerably lower than previous estimates for the Southern Ocean.

Composition of surface layer bottom sediments from the Chukchi Sea

Abundance of noble metals and bulk chemical composition have been studied in bottom sediments of the Chukchi Sea. Distribution of noble metals and their correlation with major and trace elements in the sediments have been analyzed using multicomponent statistics. It was established that average contents of noble metals in the bottom sediments of the Chukchi Sea significantly exceed those both in shelf terrigenous sediments and stratisphere. Osmium and iridium enrich mixed and pelitic sediments relative to shallow-water sediments and their influx is presumably determined by erosion of coastal and bottom unconsolidated deposits. High Ag, Ru, Au, and Pt contents were identified in clayey sediments enriched in biogenic elements in the some areas of the Southern Chukchi plain (Chukchi Sea) confined to intersection zones of submeridional and sublatitudinal structures of the graben-rift system, which formed in Mesozoic and activated in Late Cenozoic.

Production of biogenic silica during the EBENE cruise, Equatorial Pacific

During the EBENE cruise (November 1996), distributions of biogenic silica concentration and production rates were investigated in the surface waters of the equatorial Pacific (180°W, from 8°S to 8°N), with particular emphasis on the limitation of the biogenic silica production by ambient silicic acid concentrations. Integrated over the depth of the euphotic layer, concentrations of biogenic silica and production rates were maximum at the Equator (8.0 and 2.6 mmol/m**2/d) and decreased more or less symmetrically polewards. Contribution of diatoms to the new production was estimated indirectly, comparing biogenic silica production rates and available data of new and export production in the same area. This comparison shows that new production in the equatorial area could mostly be sustained by diatoms, accounting for the major part of the exported flux of organic carbon. Kinetics experiments of silicic acid enrichment were performed. Half saturation constants were 1.57 µM at 3°S and 2.42 µM at the Equator close to the ambient concentrations. The corresponding Vmax values for Si uptake were 0.028/h at 3°S and 0.052/h at the equator. Experiments also show that in situ rates were restricted to 13-78% of Vmax, depending on ambient silicic acid concentrations. This work provides the first direct evidence that the rate of Si uptake by diatom populations of the equatorial Pacific is limited by the ambient concentration of silicic acid. However, such Si limitation might not be sufficient in itself to explain the low diatom growth rates observed, and additional limitation is suggested. One hypothesis that is consistent with the results of Fe limitation studies is that Fe and Si limitations may interact, rather than just being a mutually exclusive explanation for the HNLC character of the system.