Fractional abundance and indices for brGDGTs and crenarchaeol in dust samples, surface water samples and surface sediment samples

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids produced by soil bacteria and occur in near coastal marine sediments as a result of soil organic matter input. Their abundance relative to marine-derived crenarchaeol, quantified in the BIT index, generally decreases offshore. However, in distal marine sediments, low relative amounts of brGDGTs can often still be observed. Sedimentary in situ production as well as dust input have been suggested as potential, though as yet not well constrained, sources. In this study brGDGT distributions in dust were examined and compared with those in distal marine sediments. Dust was sampled along the equatorial West African coast and brGDGTs were detected in most of the samples, albeit in low abundance. Their degree of methylation and cyclisation, expressed in the MBT' (methylation index of branched tetraethers) and DC (degree of cyclisation) indices, respectively, were comparable with those for African soils, their presumed source. Comparison of DC index values for brGDGTS in global soils, Congo deep-sea river fan sediments and dust with those of distal marine sediments clearly showed, however, that distal marine sediments had significantly higher values. This distinctive distribution is suggestive of sedimentary in situ production as a source of brGDGTs in marine sediments, rather than dust input. The presence of in situ produced brGDGTs in marine sediments means that caution should be exercised when applying the MBT'-CBT palaeothermometer to sediments with low BIT index values, i.e. < 0.1, based on our dataset.

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.

Geochemistry of pore fluids and bulk solids of ODP Site 195-1200, South Chamorro Seamount

At the South Chamorro Seamount in the Mariana subduction zone, geochemical data of pore fluids recovered from Ocean Drilling Program Leg 195 Site 1200 indicate that these fluids evolved from dehydration of the underthrusting Pacific plate and upwelling of fluids to the surface through serpentinite mud volcanoes as cold springs at their summits. Physical conditions of the fluid source at 27 km were inferred to be at 100°-250°C and 0.8 GPa. The upwelling of fluid is more active near the spring in Holes 1200E and 1200A and becomes less so with increasing distance toward Hole 1200D. These pore fluids are depleted in Cl and Br, enriched in F (except in Hole 1200D) and B (up to 3500 µM), have low 11B (16-21), and have lower than seawater Br/Cl ratios. The mixing ratios between seawater and pore fluids is calculated to be ~2:1 at shallow depth. The F, Cl, and Br concentrations, together with B concentrations and B isotope ratios in the serpentinized igneous rocks and serpentine muds that include ultramafic clasts from Holes 1200A, 1200B, 1200D, 1200E, and 1200F, support the conclusion that the fluids involved in serpentinization originated from great depths; the dehydration of sediments and altered basalt at the top of the subducting Pacific plate released Cl, H2O, and B with enriched 10B. Calculation from B concentrations and upwelling rates indicate that B is efficiently recycled through this nonaccretionary subduction zone, as through others, and may contribute the critical missing B of the oceanic cycle.

Geochemical composition of surface sediments in the Trondheimsfjord, central Norway

High sedimentation rates in fjords provide excellent possibilities for high resolution sedimentary and geochemical records over the Holocene. As a baseline for an improved interpretation of geochemical data from fjord sediment cores, this study aims to investigate the inorganic/organic geochemistry of surface sediments and to identify geochemical proxies for terrestrial input and river discharge in the Trondheimsfjord, central Norway. Sixty evenly distributed surface sediment samples were analysed for their elemental composition, total organic carbon (Corg), nitrogen (Norg) and organic carbon stable isotopes (d13Corg), bulk mineral composition and grain size distribution. Our results indicate carbonate marine productivity to be the main CaCO3 source. Also, a strong decreasing gradient of marine-derived organic matter from the entrance towards the fjord inner part is consistent with modern primary production data. We show that the origin of the organic matter as well as the distribution of CaCO3 in Trondheimsfjord sediments can be used as a proxy for the variable inflow of Atlantic water and changes in river runoff. Furthermore, the comparison of grain size independent Al-based trace element ratios with geochemical analysis from terrigenous sediments and bedrocks provides evidence that the distribution of K/Al, Ni/Al and K/Ni in the fjord sediments reflect regional sources of K and Ni in the northern and southern drainage basin of the Trondheimsfjord. Applying these findings to temporally well-constrained sediment records will provide important insights into both the palaeoenvironmental changes of the hinterland and the palaeoceanographic modifications in the Norwegian Sea as response to rapid climate changes and associated feedback mechanisms.

Geochemistry of pockmark sediments from the inner Oslofjord

Pockmarks are geological features that are found on the bottom of lakes and oceans all over the globe. Some are active, seeping oil or methane, while others are inactive. Active pockmarks are well studied since they harbor specialized microbial communities that proliferate on the seeping compounds. Such communities are not found in inactive pockmarks. Interestingly, inactive pockmarks are known to have different macrofaunal communities compared to the surrounding sediments. It is undetermined what the microbial composition of inactive pockmarks is and if it shows a similar pattern as the macrofauna. The Norwegian Oslo Fjord contains many inactive pockmarks and they are well suited to study the influence of these geological features on the microbial community in the sediment. Here we present a detailed analysis of the microbial communities found in three inactive pockmarks and two control samples at two core depth intervals. The communities were analyzed using high-throughput amplicon sequencing of the 16S rRNA V3 region. Microbial communities of surface pockmark sediments were indistinguishable from communities found in the surrounding seabed. In contrast, pockmark communities at 40 cm sediment depth had a significantly different community structure from normal sediments at the same depth. Statistical analysis of chemical variables indicated significant differences in the concentrations of total carbon and non-particulate organic carbon between 40 cm pockmark and reference sample sediments. We discuss these results in comparison with the taxonomic classification of the OTUs identified in our samples. Our results indicate that microbial surface sediment communities are affect by the water column, while the 40 cm communities are affect by local conditions within the sediment.

Water chemistry, and pigments and geochemistry of sediments from northern Victoria Land lakes

Total concentrations of algal pigments, organic C, C, N, P and S were determined in surface sediments from the littoral zone of 21 lakes in ice-free areas of northern Victoria Land (Antarctica) with different climatic and environmental conditions. Concentrations of major ions and nutrients were also determined in water samples from the same lakes. The latter samples had extremely variable chemical compositions; however, all the lakes resulted oligotrophic. Pigment concentrations in surface sediments were comparable to those reported for other Antarctic lakes and lower than those in oligotrophic lakes at lower latitudes. Cyanophyta, Chlorophyta and Bacillariophyta were the main taxa identified. These taxa correspond to those reported in previous microscopy-based studies on Antarctic phytoplankton and phytobenthos. Discriminant Function Analysis and Canonical Correspondence Analysis of data indicate that the distribution of pigments in these Victoria Land lakes depends mainly on their geographical location (particularly the distance from the sea) and nutrient status.

Geochemistry and isotopes at DSDP Hole 79-546

At Site 546, below the Mazagan Escarpment at a water depth of 4 km, 36 m of salt rock was cored from the top of one of a field of salt domes. The core was studied by thin section and a variety of geochemical procedures. The salt rock contains 0.1 to 3% carnallite and lesser amounts of sylvite and polyhalite, which with the corresponding high level of bromide place it within the potash evaporite facies. The bromide profile is of a dominantly marine evaporite deposited in moderately shallow brine which, however, was not repeatedly desiccated. A mineralogical argument suggests that the brine surface was not below sea level. An average of about 5% elastics, with dispersed anhydrite, darken the salt rock to deep shades of red, brown, and gray green. Most of the included materials are in highly deformed boudins or dispersions in the salt rock that has also undergone cataclasis in a subsequent, probably tectonic, deformation. The salt rock is slightly deficient in anhydrite, and the usual separate beds and laminae of anhydrite are virtually absent. Stable isotope ratios of sulfur and oxygen in the sulfate are clearly derived from sea water of Permian to Scythian age, in contrast to the late Triassic or Early Jurassic age of evaporites onshore in Morocco and Portugal and the corresponding evaporites offshore Maritime Canada. In contrast to those evaporites off the axis of Atlantic rifting, the salt at Site 546 may have been deposited in a very early central rift fed by marine waters from Tethys through the Gibraltar or South Atlas fracture zones.

Site characteristics, sediment geochemistry and pigment concentration of northern Victoria Land lakes

Antarctic ice-free areas contain lakes and ponds that have interesting limnological features and are of wide global significance as early warning indicators of climatic and environmental change. However, most limnological and paleolimnological studies in continental Antarctica are limited to certain regions. There are several ice-free areas in Victoria Land that have not yet been studied well. There is therefore a need to extend limnological studies in space and time to understand how different geological and climatic features affect the composition and biological activity of freshwater communities. With the aim of contributing to a better limnological characterization of Victoria Land, this paper reports data on sedimentary pigments (used to identify the main algal taxa) obtained through a methodology that is more sensitive and selective than that of previous studies. Analyses were extended to 48 water bodies in ice-free areas with differing lithology, latitude, and altitude, and with different morphometry and physical, chemical, and biological characteristics in order to identify environmental factors affecting the distribution and composition of freshwater autotrophic communities. A wider knowledge of lakes in a limnologically important region of Antarctica was obtained. Cyanophyta was found to be the most important algal group, followed by Chlorophyta and Bacillariophyta, whereas latitude and altitude are the main factors affecting pigment distribution.

Alkenone-derived UK'37 data and sea surface temperatures (SST) of sediment cores from the Gulf of Taranto (Italy)

Auxiliary data include one file with alkenone-derived UK'37 data and sea surface temperatures (SST). On these data Figs. 7 and 8 of the manuscript are based. The SST are derived from UK'37 by using the transfer function: SST = 29.876 UK'37 - 1.334 of Conte et al. (2006). The data are against the ages (in A.D.) of samples derived from cores GT91-1 (39[deg]59'23"N, 17[deg]45'25"E), GT89-3 and GT90-3 (both 39[deg]45'43"N, 17[deg]53'55"E ). Also included are composite records for UK'37 and SST. For creating the composite records, GT-89-3 was taken as reference core. In the overlapping period the GT89-3 data seem in general lower than the GT91-1 data. To accommodate for this in the composite record, the average difference (0.0343 UK'37 units; equivalent to 1.023 [deg]C) was subtracted from the GT91-1 record. Hereafter, for each depth in the overlapping interval the respective values (UK'37 or SST) of GT89-3 and GT91-1 were averaged. We have also averaged with 16 additional alkenone measurements, from 1793 to 1851, performed in the GT90-3 core.

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.

Geochemistry of tropical Atlantic sediments of Marine Isotope Stage 4

Antarctic Intermediate Water (AAIW) and Subantarctic Mode Water (SAMW) are the main conduits for the supply of dissolved silicon (silicic acid) from the deep Southern Ocean (SO) to the low-latitude surface ocean and therefore have an important control on low-latitude diatom productivity. Enhanced supply of silicic acid by AAIW (and SAMW) during glacial periods may have enabled tropical diatoms to outcompete carbonate-producing phytoplankton, decreasing the relative export of inorganic to organic carbon to the deep ocean and lowering atmospheric pCO2. This mechanism is known as the "silicic acid leakage hypothesis" (SALH). Here we present records of neodymium and silicon isotopes from the western tropical Atlantic that provide the first direct evidence of increased silicic acid leakage from the Southern Ocean to the tropical Atlantic within AAIW during glacial Marine Isotope Stage 4 (~60-70 ka). This leakage was approximately coeval with enhanced diatom export in the NW Atlantic and across the eastern equatorial Atlantic and provides support for the SALH as a contributor to CO2 drawdown during full glacial development.