Long chain 1,13- and 1,15-diols in surface sediments ans SST reconstruction for sediment core GeoB6518-1

Although commonly reported in marine and freshwater environments, little is known about the biological sources of long chain alkyl 1,13- and 1,15-diols, and factors controlling their distributions. Here we analyzed the occurrence and distribution of these lipids in a comprehensive set of marine surface sediments and compare their distributions with environmental conditions like sea surface temperature (SST), salinity and nutrient concentrations. Fractional abundances of the C28 1,13-, C30 1,13- and C30 1,15-diols show a strong correlation with SST and based on these results, we propose the Long chain Diol Index (LDI), which expresses the C30 1,15-diol abundance relative to those of C28 1,13-, C30 1,13- and C30 1,15-diols. The LDI shows a strong linear correlation with SST (LDI = 0.033 × SST + 0.095; R2 = 0.969, n = 162) over a temperature range of -3 to 27 °C. Long chain diol distributions in sediments from the South Atlantic close to the Congo River outflow (West Africa) provided a 43 kyr LDI SST record. This record reflects several known climatic events and shows similarities with an alkenone-derived SST record obtained using the same suite of sediments, both in trend and in terms of absolute SST. This confirms the potential of the LDI as a proxy for palaeo-SST reconstruction.

Biomass and stable isotope composition of plankton in five size fractions along a zonal transect (24°N) from the Canary Islands to Florida in January-March 2011

The spatial variability of biomass and stable isotopes in plankton size fractions in the upper 200 m was studied in a high spatial resolution transect along 24°N from Canary Islands to Florida (January - March 2011) during Leg 8 of the Malaspina-2010 expedition (http://www.expedicionmalaspina.es) to determine nitrogen and carbon sources. Plankton samples were collected by vertical tows of a microplankton net (40 mm mesh size) and a mesoplankton net (200 mm mesh size) through the upper 200 m of the water column. Sampling was between 10:00 and 16:00 h GMT. Plankton was separated into five size fractions (40 - 200, 200 - 500, 500 - 1000, 1000 - 2000 and > 2000 mm) by gentle filtration of the samples by a graded series of nylon sieves (2000, 1000, 500, 200 and 40 mm). Large gelatinous organisms were removed before filtration. Aliquots for each size fraction were collected on pre-weighed glass-fibre filters, dried (60°C, 48 h) and stored in a desiccator before determination of biomass (dry weight), carbon and nitrogen content and natural abundance of stable carbon and nitrogen isotopes ashore. Vertical advection of waters predominated in lateral zones while the central Atlantic (30-70°W) was characterized by a strong stratification and oligotrophic surface waters. Plankton biomass was low in the central zone and high in both eastern and western sides, with most of the variability due to either large (>2000 µm) and small plankton (<500 µm). Carbon isotopes reflected mainly the advection the deep water in lateral zones. Stable nitrogen isotopes showed a nearly symmetrical spatial distribution in all fractions, with the lowest values (delta15N <1per mill) in the central zone, and were inversely correlated to carbon stable isotopes (delta13C) and to the abundance of the nitrogen-fixer Trichodesmium. Diazotrophy was estimated to account for >50% of organic nitrogen in the central zone, and even >30% in eastern and western zones. The impact of diazotrophy increased with the size of the organisms, supporting the wide participation of all trophic levels in the processing of recently fixed nitrogen. These results indicate that atmospheric sources of carbon and nitrogen prevail over deep water sources in the subtropical North Atlantic and that the zone influenced by diazotrophy is much larger than reported in previous studies.

Evaluation of long chain 1,14-alkyl diols in marine sediments as indicators for upwelling and temperature

Long chain alkyl diols form a group of lipids occurring widely in marine environments. Recent studies have suggested several palaeoclimatological applications for proxies based on their distributions, but also revealed uncertainties about their applicability. Here we evaluate the use of long chain 1,14-alkyl diol indices for reconstruction of temperature and upwelling conditions by comparing index values, obtained from a comprehensive set of marine surface sediments, with environmental factors like sea surface temperature (SST), salinity and nutrient concentrations. Previous cultivation efforts indicated a strong effect of temperature on the degree of saturation and the chain length distribution of long chain 1,14-alkyl diols in Proboscia spp., quantified in the diol saturation index (DSI) and diol chain length index (DCI), respectively. However, values of these indices in surface sediments show no relationship with annual mean SST of the overlying water. It remains unknown what determines the DSI, although our data suggests that it may be affected by diagenesis, while the relationship between temperature and DCI may be different for different Proboscia species. In addition, contributions of algae other than Proboscia diatoms may affect both indices, although our data provide no direct evidence for additional long chain 1,14-alkyl diol sources. Two other indices using the abundance of 1,14-diols vs. 1,13-diols and C30 1,15-diols have previously been applied as indicators for upwelling intensity at different locations. The geographical distribution of their values supports the use of 1,14 diols vs. 1,13 diols [C28 + C30 1,14-diols]/[(C28 + C30 1,13-diols) + (C28 + C30 1,14-diols)] as a general indicator for high nutrient or upwelling conditions.

Stable nitrogen and carbon isotopes of plankton samples and selected copoepods around the Iberan Peninsula 2001-2004

The structure and variability of pelagic food webs along the north and northwestern shelf of the Iberian Peninsula were analysed using natural abundance of nitrogen stable isotopes of plankton and pelagic consumers. Plankton composition was mainly studied in size-fractionated samples, but also the isotopic signatures of three copepod species, as representative of primary consumers, were considered. Several fish species were included as planktivorous consumers, with special attention to sardine (Sardina pilchardus). Finally, top pelagic consumers were represented by the common dolphin (Delphinus delphis). The relationship between trophic position and body size implies large variability in the ratio of predator to prey sizes, likely because widespread omnivory and plankton consumption by relatively large predators. Planktivorous species share a common trophic position, suggesting potential competition for food, and low nitrogen isotope enrichment between prey and consumers suggest nutrient limitation and recycling at the base of the food web. Both experimental and field evidences indicate that the muscle of sardine integrates fish diet over seasonal periods and reflects the composition of plankton from large shelf areas. The low mobility of sardines during periods of low population size is consistent with differential isotopic signatures found in shelf zones characterised by upwelling nutrient inputs.

Stable C and N isotopes and percent C as well as N composition of plankton from the North Atlantic

Elemental C and N percent composition and natural abundance of stable C and N isotopes of plankton species and/or size-fractions collected in several cruises on the N Atlantic Ocean from Greenland to Norway and around Iceland. Determinations included key copepod and krill species. Lipid extraction was performed in some samples to determine carbón isotope depletion factors.

Long chain diols and diol indices of surface sediments of the Iberian Atlantic margin

Long chain diols are lipids that have gained interest over the last years due to their high potential to serve as biomarkers and diol indices have been proposed to reconstruct upwelling conditions and sea surface temperature (SST). However, little is known about the sources of the diols and the mechanisms impacting their distribution. Here we studied the factors controlling diol distributions in the Iberian Atlantic margin, which is characterized by a dynamic continental shelf under the influence of upwelling of nutrient-rich cold deep waters, and fluvial input. We analyzed suspended particulate matter (SPM) of the Tagus river, marine SPM and marine surface sediments along five transects off the Iberian margin, as well as riverbank sediments and soil from the catchment area of the Tagus river. Relatively high fractional abundances of the C32 1,15-diol (normalized with respect to the 1,13- and 1,15-diols) were observed in surface sediments in front of major river mouths and this abundance correlates strongly with the BIT index, a tracer for continental input of organic carbon. Together with an even higher fractional abundance of the C32 1,15-diol in the Tagus river SPM, and the absence of long chain diols in the watershed riverbank sediments and soils, we suggest that this long chain diol is produced in-situ in the river. Further support for this hypothesis comes from the small but distinct stable carbon isotopic difference of 1.3? with the marine C28 1,13-diol. The 1,14-diols are relatively abundant in surface sediments directly along the northern part of the coast, close to the upwelling zone, suggesting that Diol Indices based on 1,14-diols would work well as upwelling tracers in this region. Strikingly, we observed a significant difference in stable carbon isotopic composition between the monounsaturated C30:1 1,14- and the saturated C28 1,14-diol (3.8±0.7 per mil), suggesting different sources, in accordance with their different distributions. In addition, the Long chain Diol Index (LDI), a proxy for sea surface temperature, was applied for the surface sediments. The results correlate well with satellite SSTs offshore but reveal a significant discrepancy with satellite-derived SSTs in front of the Tagus and Sado rivers. This suggests that river outflow might compromise the applicability of this proxy.

(Table 1) Water chemistry of groundwater and snow samples from three sites in Ontario, Canada

Snow samples collected from hand-dug pits at two sites in Simcoe County, Ontario, Canada were analysed for major and trace elements using the clean lab methods established for polar ice. Potentially toxic, chalcophile elements are highly enriched in snow, relative to their natural abundance in crustal rocks, with enrichment factor (EF) values (calculated using Sc) in the range 107 to 1081 for Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, Te, and Zn. Relative to M/Sc ratios in snow, water samples collected at two artesian flows in this area are significantly depleted in Ag, Al, Be, Bi, Cd, Cr, Cu, Ni, Pb, Sb, Tl, V, and Zn at both sites, and in Co, Th and Tl at one of the sites. The removal from the waters of these elements is presumably due to such processes as physical retention (filtration) of metal-bearing atmospheric aerosols by organic and mineral soil components as well as adsorption and surface complexation of ionic species onto organic, metal oxyhydroxide and clay mineral surfaces. In the case of Pb, the removal processes are so effective that apparently ''natural'' ratios of Pb to Sc are found in the groundwaters. Tritium measurements show that the groundwater at one of the sites is modern (ie not more than 30 years old) meaning that the inputs of Pb and other trace elements to the groundwaters may originally have been much higher than they are today; the M/Sc ratios measured in the groundwaters today, therefore, represent a conservative estimate of the extent of metal removal along the flow path. Lithogenic elements significantly enriched in the groundwaters at both sites include Ba, Ca, Li, Mg, Mn, Na, Rb, S, Si, Sr, and Ti. The abundance of these elements can largely be explained in terms of weathering of the dominant silicate (plagioclase, potassium feldspar, amphibole and biotite) and carbonate minerals (calcite, dolomite and ankerite) in the soils and sediments of the watershed. Arsenic, Mo, Te, and especially U are also highly enriched in the groundwaters, due to chemical weathering: these could easily be explained if there are small amounts of sulfides (As, Mo, Te) and apatite (U) in the soils of the source area. Elements neither significantly enriched nor depleted at both sites include Fe, Ga, Ge, and P.