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.

Distribution of deep-sea foraminifera in surface sediments east of New Zealand

Paleobathymetric assessments of fossil foraminiferal faunas play a significant role in the analysis of the paleogeographic, sedimentary, and tectonic histories of New Zealand's Neogene marine sedimentary basins. At depths >100 m, these assessments often have large uncertainties. This study, aimed at improving the precision of paleodepth assessments, documents the present-day distribution of deep-sea foraminifera (>63 µm) in 66 samples of seafloor sediment at 90-700 m water depth (outer shelf to mid-abyssal), east of New Zealand. One hundred and thirty-nine of the 465 recorded species of benthic foraminifera are new records for the New Zealand region. Characters of the foraminiferal faunas which appear to provide the most useful information for estimating paleobathymetry are, in decreasing order of reliability: relative abundance of common benthic species; benthic species associations; upper depth limits of key benthic species; and relative abundance of planktic foraminifera. R mode cluster analysis on the quantitative census data of the 58 most abundant species of benthic foraminifera produced six species associations within three higher level clusters: (1) calcareous species most abundant at mid-bathyal to outer shelf depths (<1000 m); (2) calcareous species most abundant at mid-bathyal and greater depths (>600 m); (3) agglutinated species mostly occurring at deep abyssal depths (>3000 m). A detrended correspondence analysis ordination plot exhibits a strong relationship between these species associations and bathymetry. This is manifest in the bathymetric ranges of the relative abundance peaks of many of the common benthic species (e.g., Abditodentrix pseudothalmanni 500-2800 m, Bolivina robusta 200-650 m, Bulimina marginata f. marginata 20-600 m, B. marginata f. aculeata 400-3000 m, Cassidulina norvangi 1000-4500 m, Epistominella exigua 1000-4700 m, and Trifarina angulosa 10-650 m), which should prove useful in paleobathymetric estimates. The upper depth limits of 28 benthic foraminiferal species (e.g., Fursenkoina complanata 200 m, Bulimina truncana 450 m, Melonis affinis 550 m, Eggerella bradyi 750 m, and Cassidulina norvangi 1000 m) have potential to improve the precision of paleobathymetric estimates based initially on the total faunal composition. The planktic percentage of foraminiferal tests increases from outer shelf to upper abyssal depths followed by a rapid decline within the foraminiferal lysocline (below c. 3600 m). A planktic percentage <50% is suggestive of shelf depths, and >50% is suggestive of bathyal or abyssal depths above the CCD. In the abyssal zone there is dramatic taphonomic loss of most agglutinated tests (except some textulariids) at burial depths of 0.1-0.2 m, which negates the potential usefulness of these taxa in paleobathymetric assessments.

Benthic foraminiferal assemblages in surface sediments of the Elbe estuary

Two foraminiferal assemblages are observed in surface sediments of the Elbe estuarv. an Elphidium excavatum assemblaae and an Ahmonia/Protelphidium assemblage. They are the result of test-size sorting in accordance to the grain size of the sediments. These assemblages of mainly empty tests differ basically from the living population, which is dominated exclusively by E. excavatum. The average test size is decreasing when advancing from the Open sea into the estuary and the living fauna disappears near the entrance of the Kiel Canal. In the dead assemblage the diversity is distinctively higher and the average test size varies with the grain size of the sediment. The assemblages found in plankton tows are nearly identical with those in corresponding bottom samples. This indicates the distribution pattern to be caused by transport in currents (mainly in suspension). This type of foraminiferal assemblages characterize macro- and mesotidal estuaries and might indicate a high tidal range when observed in sediments of fossil estuaries.

Distribution of diatoms in surface sediments and some limnological characteristics of studied lakes in the Siberian arctic

The investigation of the species composition and ecology of diatoms of modern bottom sediments in water bodies of arctic polygonal tundra in three subregions of North Yakutiya has been carried out. As a result, 161 taxons of diatoms were determined; the determinant role of the depth, conductivity, pH of the water, and geographic latitude in their distribution was confirmed, and two complexes of species with respect to the leading abiotic factors were distinguished. The diatoms of the first complex prefer shallow water bodies of high latitudes with neutral and slightly alkaline water and relatively high conductivity. The second complex is confined to the water bodies of lower latitudes with small conductivity, as well as neutral and slightly acidic water.

Palynology and dinoflagellate counts of surface sediments, and sea surface conditions, of sites in the North Pacific

Palynological analyses were performed on 53 surface sediment samples from the North Pacific Ocean, including the Bering and Okhotsk Seas (37-64°N, 144°E-148°W), in order to document the relationships between the dinocyst distribution and sea-surface conditions (temperatures, salinities, primary productivity and sea-ice cover). Samples are characterized by concentrations ranging from 18 to 143816 cysts/cm**3 and the occurrence of 32 species. A canonical correspondence analysis (CCA) was carried out to determine the relationship between environmental variables and the distribution of dinocyst taxa. The first and second axes represent, respectively, 47% and 17.8% of the canonical variance. Axis 1 is positively correlated with all parameters except to the sea-ice and primary productivity in August, which are on the negative side. Results indicate that the composition of dinocyst assemblages is mostly controlled by temperature and that all environmental variables are correlated together. The CCA distinguishes 3 groups of dinocysts: the heterotrophic taxa, the genera Impagidinium and Spiniferites as well as the cyst of Pentapharsodinium dalei and Operculodinium centrocarpum. Five assemblage zones can be distinguished: 1) the Okhotsk Sea zone, which is associated to temperate and eutrophic conditions, seasonal upwellings and Amur River discharges. It is characterized by the dominance of O. centrocarpum, Brigantedinium spp. and Islandinium minutum; 2) the Western Subarctic Gyre zone with subpolar and mesotrophic conditions due to the Kamchatka Current and Alaska Stream inflows. Assemblages are dominated by Nematosphaeropsis labyrinthus, Pyxidinopsis reticulata and Brigantedinium spp.; 3) the Bering Sea zone, depicting a subpolar environment, influenced by seasonal upwellings and inputs from the Anadyr and Yukon Rivers. It is characterized by the dominance of I. minutum and Brigantedinium spp.; 4) the Alaska Gyre zone with temperate conditions and nutrient-enriched surface waters, which is dominated by N. labyrinthus and Brigantedinium spp. and 5) the Kuroshio Extension-North Pacific-Subarctic Current zone characterized by a subtropical and oligotrophic environment, which is dominated by O. centrocarpum, N. labyrinthus and warm taxa of the genus Impagidinium. Transfer functions were tested using the modern analog technique (MAT) on the North Pacific Ocean (= 359 sites) and the entire Northern Hemisphere databases ( = 1419 sites). Results confirm that the updated Northern Hemisphere database is suitable for further paleoenvironmental reconstructions, and the best results are obtained for temperatures with an accuracy of +/-1.7 °C.

Carbonate system of surface sediments from the South Pacific

B/Ca ratios in Cibicides mundulus and Cibicides wuellerstorfi have been shown to correlate with the degree of calcite saturation in seawater (D[CO32-]). In the South Pacific, a region of high importance in the global carbon cycle, these species are not continuously present in down-core records. Small numbers of epibenthic foraminifera in samples present an additional challenge, which can be overcome by using laser ablation-inductively coupled-mass spectrometry (LA-ICP-MS). We present a laser ablation based core-top calibration for Cibicides cf. wuellerstorfi, a C. wuellerstorfi morphotype that is abundant in the South Pacific and extend the existing global core top calibration for C. mundulus and C. wuellerstorfi to this region. B/Ca in C. cf. wuellerstorfi are linearly correlated with D[CO32-] and possibly display a higher sensitivity to calcite saturation changes than C. wuellerstorfi. Trace element profiles through C. wuellerstorfi and C. mundulus reveal an intra-shell B/Ca variation of ±36% around the mean shell value. Mg/Ca and B/Ca display opposite trends along the shell. Both phenomena likely result from ontogenetic effects. Intra-shell variability equals intra-sample variability, mean sample B/Ca values can thus be reliably calculated from averaged spot results of single specimen. In the global B/Ca-D[CO32-] range, we observe an inverse relationship between water mass age and D[CO32-].

Mg/Ca and Sr/Ca ratios of Hoeglundina elegans from surface sediments

Core top samples from Atlantic (Little Bahama Banks (LBB)) and Pacific (Hawaii and Indonesia) depth transects have been analyzed in order to assess the influence of bottom water temperature (BWT) and aragonite saturation levels on Mg/Ca and Sr/Ca ratios in the aragonitic benthic foraminifer Hoeglundina elegans. Both the Mg/Ca and Sr/Ca ratios in H. elegans tests show a general decrease with increasing water depth. Although at each site the decreasing trends are consistent with the in situ temperature profile, Mg/Ca and Sr/Ca ratios in LBB are substantially higher than in Indonesia and Hawaii at comparable water depths with a greater difference observed with increasing water depth. Because we find no significant difference between results obtained on "live" and "dead" specimens, we propose that these differences are due to primary effects on the metal uptake during test formation. Evaluation of the water column properties at each site suggests that in situ CO3 ion concentrations play an important role in determining the H. elegans Mg/Ca and Sr/Ca ratios. The CO3 ion effect is limited, however, only to aragonite saturation levels ([DeltaCO3]aragonite) below 15 µmol/kg. Above this level, temperature exerts a dominant effect. Accordingly, we propose that Mg/Ca and Sr/Ca in H. elegans tests can be used to reconstruct thermocline temperatures only in waters oversaturated with respect to the mineral aragonite using the following relationships: Mg/Ca = (0.034 ± 0.002)BWT + (0.96 ± 0.03) and Sr/Ca = (0.060 ± 0.002)BWT + (1.53 ± 0.03) (for [DeltaCO3]aragonite > 15 µmol/kg). The standard error associated with these equations is about ±1.1°C. Reconstruction of deeper water temperatures is complicated because in undersaturated waters, changes in Mg/Ca and Sr/Ca ratios reflect a combination of changes in [CO3] and BWT. Overall, we find that Sr/Ca, rather than Mg/Ca, in H. elegans may be a more accurate proxy for reconstructing paleotemperatures.

Distribution and stable isotopic compositions of hydrogen and carbon of plant-wax derived n-C29 and -C31 alkanes in terrestrial, coastal and offshore surface sediments

Reconstructing terrestrial water budgets is of prime importance for understanding past climate and environment. To shed more light on how plant-wax derived n-alkanes may be used for this purpose we investigated the distribution and stable isotopic compositions of hydrogen (dD) and carbon (d13C) of plant-wax derived n-C29 and -C31 alkanes in terrestrial, coastal and offshore surface sediments in relation to hydrology along a NW-SE transect east of the Italian Apennines from the Po River to the Eastern Gulf of Taranto. The plant wax average chain length increases southward and may relate to increasing temperature and/or aridity. The plant wax dD of the terrestrial and coastal samples also increases southward and mainly reflects changes in the dD of precipitation. The d13C of plant waxes is primarily interpreted in terms of C3 vegetation changes rather than varying contributions by C4 plants. The plant wax d13C-dD composition of the Po River and Apennine rivers differs considerably from that in southern Italy, and suggests a mainly southern source for plant waxes in marine sediments of the Gulf of Taranto. This calibration provides a basis for the reconstruction of past changes in the Italian water balance and n-alkane source areas.

Organic compounds and bitumen in surface sediments from the Pechora Bay

Detailed geochemical investigations of bottom sediments in the Pechora Bay were carried out under a monitoring regime. The regional geochemical background is characterized. Organic matter of sediments is found to be clastic, formed under the influence of Pechora River run-off, and determined by genetic and lithofacial factors. An application of geochemical methodology is suggested for estimating hydrocarbon contamination of bottom sediments. As an example consequences of the accidental Usinsky oil spill are studied. They are based on analysis of composition of molecular markers. It is shown that increasing technogenic impact on Pechora Bay sediments is fixed only at molecular level and is not disastrous.

Geochemical analysis of surface sediments along the Portuguese Margin

Twenty-nine surface samples from the Portuguese shelf, recovered offshore from the mouths of the Ave, Douro, Lis and Mira rivers, were analysed using ICP-OES for selected major and trace elements, after total dissolution. Organic carbon, carbonate content and grain size were also determined. Five evaluation tools have been applied in order to compare the three study areas and to evaluate sediment geochemistry and other sediment compositional variability in the acquired samples: (1) empirical methods based on comparison with standard reference criteria, e.g. the NOAA sediment quality guidelines, (2) normalisation ratios using a grain-size proxy element, (3) "Gradient Method", plotting contaminant vs. organic matter or Al, (4) definition of a regional geochemical baseline from a compiled database, and (5) enrichment factors. The evaluation of element and component associations indicates differences related both to the onshore drainage areas and to the environmental shelf setting. Despite the considerable variability in total metal contents indicated by our results, the sediment metal composition is largely of natural origin. Metal enrichments observed in the Mira area are associated with the drainage of mineralised areas rich in Cu, Pb, Zn, Fe and Mn. The near absence of human impact on shelf sediments, despite the vicinity to urban areas with high industrialisation levels, such as the Ave-Douro and Lis areas, is attributed to effective trapping in the estuaries and coastal zones, as well dilution with less contaminated sediments shelf sediments and removal with fine fractions due to grain-size sorting. The character of the contaminated sediments transported to these shelf areas is further influenced by grain-size sorting as well as by dilution with less contaminated marine sediments. The results obtained individually by the different methods complement each other and allow more specific interpretations.

Stable isotope record of planktic foraminifera sampled by plankton haul and in surface sediments off North-West Africa

Foraminifera shells from modern sediments document the hydrography of the coastal upwelling region off Northwest-Africa (12-35° N) through the stable isotopic composition of their shells. Oxygen isotopes in planktonic foraminifers reflect sea surface temperatures (SST) during the main growing season of the differnt species: Globigerinoides ruber (pink and white) and G. sacculifer delineate the temperatures of the summer, Globorotalia inflata and Pulleniatina obliquiloculata those of the winter. Oxygen isotopes on Globigerina bulloides document temperature ranges of the upwelling seasons. d18O values in planktonic foraminifera from plankton hauls resemble those from the surface sediment samples, if the time of the plankton collection is identical with that of the main growing season of the species. The combined isotopic record of G. ruber (white) and G. inflata clearly reveals the latitudinal variations of the annual mean SST. The deviation of the d18O values from both species from their common mean is a scale for the seasonality, i.e. the maximum temperature range within one year. Thus in the summer upwelling region (north of 25° N) seasonality is relatively low, while it becomes high in the winter upwelling region south of 20° N. Furthermore, the winter upwelling region is characterized by relatively high d18O values - indicating low temperatures - in G. bulloides, the region of summer upwelling by relatively low d180 values compared with the constructed annual mean SST. Generally, carbon isotopes from the plankton hauls coincide with those from sediment surface samples. The enrichment of 13C isotopes in foraminifers from areas with high primary production can be caused by the removal of 12C from the total dissolved inorganic carbon during phytoplankton blooms. It is found that carbon isotopes from plankton hauls off Northwest-Africa are relatively enriched in 13C compared with samples from the western Atlantic Ocean. Also shells of G. ruber (pink and white) from upwelling regions are enriched in the heavier isotope compared with regions without upwelling. In the sediment, the enrichement of 13C due to high primary production can only be seen in G. bulloides from the high fertile upwelling region south of 20° N. North of this latitude values are relatively low. An enrichment of 12C is observed in shells of G. ruber (pink), G. inflata and P. obliquiloculata from summer-winter- and perennial upwelling regions respectively. Northern water masses can be distinguished from their southern counterparts by relatively high oxygen and carbon values in the "living" (=stained) benthic foraminifera Uvigerina sp. and Hoeglundina elegans. A tongue of the Mediterranean Outflow water can be identified far to the south (20° N) by 13C-enriched shells of these benthic foraminifera. A zone of erosion (15-25° N, 300-600 m) with a subrecent sediment surface can be mapped with the help of oxygen isotopes in "dead" benthic specimens. Comparison of d18O values in aragonitic and calcitic benthic foraminifers does not show a differential influence of temperature on the isotopic composition in the carbonate. However, carbon isotopes reflect slightly differences under the influence of temperature.