Chemical characterization and quantification of the brown algal storage compound laminarin

In search of a meaningful stress indicator for Fucus vesiculosus we found that the often used quantitative determination procedures for the polysaccharide laminarin (beta-1,3-glucan) result in different kind of problems, uncertainties and limitations. This chemical long-term storage form of carbon enables perennial brown algae in seasonally fluctuating ecosystems to uncouple growth from photosynthesis. Because of this high ecological relevance a reliable and precise method for determination and quantification of laminarin is needed. Therefore, a simple, cold water extraction method coupled to a new quantitative liquid chromatography-mass spectrometrical method (LC-MS) was developed. Laminarin was determined in nine out of twelve brown algal species, and its expected typical molar mass distribution of 2000-7000 Da was confirmed. Furthermore, laminarin consisted of a complex mixture of different chemical forms, since fifteen chemical laminarin species with distinct molecular weights were measured in nine species of brown algae. Laminarin concentrations in the algal tissues ranged from 0.03 to 0.86% dry weight (DW). The direct chemical characterization and quantification of laminarin by LC-MS represents a powerful method to verify the biochemical and ecological importance of laminarin for brown algae. Single individuals of Laminaria hyperborea, L. digitata, Saccharina latissima, F. serratus, F. vesiculosus, F. spiralis, Himanthalia elongata, Cystoseira tamariscifolia, Pelvetia canaliculata, Ascophyllum nodosum, Halidrys siliquosa and Dictyota dichotoma were collected in fall (18.11.2013) during spring low tide from the shore of Finavarra, Co. Clare, west coast of Ireland (53° 09' 25'' N, 09° 06' 58'' W). After sampling, the different algae were immediately transported to the lab, lyophilized and sent to the University of Rostock. Laminarin was extracted with cold ultrapure water from the algal samples. Before extraction they were ground to < 1 mm grain size with an analytical mill (Ika MF 10 Basic). The algal material (approx. 1.5 g DW) was extracted in ultrapure water (8 mL) on a shaker (250 rpm) for 5 h. After the addition of surplus ultrapure water (4 mL) and shaking manually, 1 mL of the sample was filter centrifuged (45 µm) at 14,000 rpm (Hettich Mikro 22 R). The slightly viscous supernatant was free of suspended material and converted into a microvial (300 µL) for further analysis. The extracts were analyzed using liquid chromatography-mass spectrometry (LC-MS) analysis (LTQ Velos Pro ion trap spectrometer with Accela HPLC, Thermo Scientific). Laminarin species were separated on a KinetexTM column (2.6 µm C18, 150 x 3 mm). The mobile phase was 90 % ultrapure water and 10 % acetonitrile, run isocratically at a flow rate of 0.2 mL min-1. MS was working in ESI negative ion mode in a mass range of 100 - 4000 amu. Glucose contents were determined after extraction using high-performance liquid chromatography (HPLC). Extracted samples were analyzed in an HPLC (SmartLine, Knauer GmbH) equipped with a SUPELCOGELTM Ca column (30 x 7,8 mm without preColumn) and RI-detector (S2300 PDA S2800). Water was used as eluent at a flow rate of 0.8 mL min-1 at 75 °C. Glucose was quantified by comparison of the retention time and peak area with standard solutions using ChromGate software. Mannitol was extracted from three subsamples of 10-20 mg powdered alga material (L. hyperborea, L. digitata, S. latissima, F. serratus, F. vesiculosus, F. spiralis, H. elongata, P. canaliculata, A. nodosum, H. siliquosa) and quantified, following the HPLC method described by Karsten et al. (1991). For analyzing carbon and nitrogen contents, dried algal material was ground to powder and three subsamples of 2 mg from each alga thalli were loaded and packed into tin cartridges (6×6×12 mm). The packages were combusted at 950 °C and the absolute contents of C and N were automatically quantified in an elemental analyzer (Elementar Vario EL III, Germany) using acetanilide as standard according to Verardo et al. (1990).

Trace metal concentration and age model of ODP Hole 165-1002C sediments

Titanium and iron concentration data from the anoxic Cariaco Basin, off the Venezuelan coast, can be used to infer variations in the hydrological cycle over northern South America during the past 14,000 years with subdecadal resolution. Following a dry Younger Dryas, a period of increased precipitation and riverine discharge occurred during the Holocene 'thermal maximum'. Since ~5400 years ago, a trend toward drier conditions is evident from the data, with high-amplitude fluctuations and precipitation minima during the time interval 3800 to 2800 years ago and during the 'Little Ice Age'. These regional changes in precipitation are best explained by shifts in the mean latitude of the Atlantic Intertropical Convergence Zone (ITCZ), potentially driven by Pacific-based climate variability. The Cariaco Basin record exhibits strong correlations with climate records from distant regions, including the high-latitude Northern Hemisphere, providing evidence for global teleconnections among regional climates.

Pollen profile and age determination of sediment core Schwanengrabenrinne, Brandenburg, Germany

In der Döberitzer Heide nördlich von Potsdam wurden vegetationsgeschichtliche Untersuchungen durchgeführt. Das Untersuchungsgebiet befindet sich im östlichen Teil der Nauener Platte, die bisher vegetationsgeschichtlich weitgehend unerforscht war. In sechs verschiedenen Mooren wurden acht Bohrungen niedergebracht. Die Bohrkerne wurden stratigraphisch und pollenanalytisch untersucht und für die Radiocarbondatierung beprobt. Die Pollendiagramme ermöglichen die Rekonstruktion der Vegetationsentwicklung der terrestrischen Standorte und der Moore in der Döberitzer Heide in den letzten 14.000 Jahren. Neben einer Revision der Gliederungsprinzipien der spätglazialen Vegetationsentwicklung Brandenburgs und einer vergleichenden Betrachtung der Moorentwicklung in der Döberitzer Heide wurde besonderes Augenmerk auf die Geschichte des Döberitzer Lindenwaldes gerichtet, der einen Sonderfall in der brandenburgischen Vegetation darstellt. Die Untersuchungen boten die Möglichkeit, die Ursachen seiner Entstehung zu klären, Aussagen zu den Perspektiven seiner Entwicklung zu treffen und mögliche Entwicklungspotentiale von Lindenwäldern im Land Brandenburg aufzuzeigen.

Age determination of sediment cores from the continental shelf and slope off North-West Africa

Three sediment cores from the continental shelf and slope off NW Africa (Banc d'Arguin; 52 m, 665 m and 973 m water depth) have been investigated by means of a coarse fraction analysis. The two shallower cores have been deposited during less than 10,000 years, the deeper one during the last 36,000 years. The Holocene sedimentation ( 4000 years) in the deeper part of core 79 the edge of the Banc d'Arguin is strongly influenced by reworking of Late Glacial dune sands and biogenic particles from shallower ware (<40 m), as well as eroding current influence. A decrease in grain size of silicate material and a decrease in lateral supply, correlated to a doubling of accumulation rates in the upper part of the core, indicates a more autochthonous sedimentation with less sorting influence in the youngest Holocene. The depth of provenance of the allochttonous material can be assumed in 100-300 m water depth as indicated by various biogenous particles. Small amounts of shallow water particles in the autochthonous layers indicate a supplay from shallow water, which probably occured b ythe mechanism of "particle by particle supply". None of the three cores indicates upwelling influence, although occanographers found intense upwelling in the area of the Banc d'Arguin. The Holocene climate in that area probably has been arid, small variations in terrigenous matter composition and grain size in the Early Holocene might be due to decreased wind strength or to an increase in rain fall. The Peak Glacial section (14,000-22,000 y. B.P.) of the deepest core 88 indicates a very much intensified eolian silt supply and an additional bottom supply of quartz sand In the interval 22,000-36,000 y. B.P. wind strength decreased, but probably no increase in humidity occurred. So this area in about 19° 40' N had an arid climate in the Late Holocene and in the Peak Glacial. The fragmentation of planktonic foraminifers and the abundance of aragonitic tests of pteropods in core 88 indicate an Early Holocene (8330 y. B.P.) preservation spike. Two minima in fragmentation correlated to maxima in pteropod content at about 15,700 and 21,000 y. B.P. are correlated to maxima in shallow water supply and thus do not reflect preservation conditions, but only lateral supply from the carbonate dissolution minimum zone in about 300 m water depth.

Foraminiferal assemblages of the Mackenzie-Beaufort Sea Slope and Amundsen Gulf

Two cores, one from the Beaufort Sea Slope at 1000 m water depth (core 750) and one from the Amundsen Gulf at 426 m (core 124), were collected to help determine paleo-ice cover in the Holocene and late glacial of this area. Site 750 is particularly sensitive to changes in paleo-ice cover because it rests beneath the present ice margin of the permanent Arctic ice pack. Core 124 was sampled just in front of the former glacier that moved out into the Amundsen Gulf and started to recede about 13 ka B.P. Both cores have a strong occurrence of calcareous foraminifera in the upper few centimeters, but these disappear throughout most of the Holocene, suggesting more open water in that time period than present. In the sediments representing the end of the last glacial period (dated at ~11,500-14,000 calibrated years B.P. (cal B.P.)) a calcareous fauna with an abundant planktic foraminiferal fauna suggests a return to almost permanent ice cover, much like the central Arctic today. Together with the foraminifera there was also abundant ice-rafted debris (IRD) in both cores between 12,000 cal B.P. and ~14,000 cal B.P., but those units are of different ages between cores, suggesting different events. The IRD in both cores appears to have the same magnetic and chemical signals, but their origins cannot be determined exactly until clay mineralogy is completed. There is abundant organic debris in both cores below the IRD units: the organics in core 750 are very diffuse and not visually identifiable, but the organic material in core 124 is clearly identifiable with terrestrial root fragments; these are 14C dated at over 37,000 years B.P. This is a marine unit as it also has glacial front foraminifera in the sediment with the organic debris that must have been originating from subglacial streams. The seismic and multibeam data both indicate glaciers did not cross the core 124 site.

Tab. 1: Radiocarbon ages of the late Pleistocene and early Holocene of Mecklenburg-Vorpommern and surrounding areas

Several geoscientific projects in the last decade led to a marked increase of radiocarbon dates in Mecklenburg-Vorpommern and in neighbouring areas. The studies were mostly focussed on the genesis of the Baltic Basin and the last termination. In this Paper, a regional collection of 271 radiocarbon dates of the late Pleistocene and early Holocene (ca. 50,000-8,000 14C yr BP) is presented. The dates were calibrated, correlate, and assessed with regard to their credibility. The evaluation of the data is focussed on problems of regional palaeogeography. The age of the last Weichselian deglaciation (deglaciation after the Mecklenburg Advance) is assumed to be around 14,000 14C yr BP through radiocarbon dates from the Pomeranian Bay. This data is ca. 1,000 years older compared to former views. On the other hand, the database allows the dating of late Pleistocene basin sequences from the Baltic coast, This indicates three stratigraphic units for basin areas 0-15 m above sea level - glaciolacustrine sedimentation in the late Pleniglacial, lacustrine and telmatic sedimentation as well as soil formation in the early Lateglacial and Alleroed and aeolian sedimentation in the Younger Dryas. The Younger Dryas in the huge Mecklenburg Bay-Darss Basin NE of Rostock is characterised by lacustrine sedimentation ca. 20 m below sea level ("Baltic Ice Lake"), and by aeolian sedimentation above sea level.

Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.

Shapefile of the survey tracks of 'Mosaic 02' at the Regab pockmark (Northern Congo Fan)

The Regab pockmark is a large cold seep area located 10 km north of the Congo deep sea channel at about 3160 m water depth. The associated ecosystem hosts abundant fauna, dominated by chemosynthetic species such as the mussel Bathymodiolus aff. boomerang, vestimentiferan tubeworm Escarpia southwardae, and vesicomyid clams Laubiericoncha chuni and Christineconcha regab. The pockmark was visited during the West African Cold Seeps (WACS) cruise with RV Pourquoi Pas? in February 2011, and a 14,000-m**2 high-resolution videomosaic was constructed to map the most populated area and to describe the distribution of the dominant megafauna (mussels, tubeworms and clams). The results are compared with previous published works, which also included a videomosaic in the same area of the pockmark, based on images of the BIOZAIRE cruise in 2001. The 10-year variation of the faunal distribution is described and reveals that the visible abundance and distribution of the dominant megafaunal populations at Regab have not changed significantly, suggesting that the overall methane and sulfide fluxes that reach the faunal communities have been stable. Nevertheless, small and localized distribution changes in the clam community indicate that it is exposed to more transient fluxes than the other communities. Observations suggest that the main megafaunal aggregations at Regab are distributed around focused zones of high flux of methane-enriched fluids likely related to distinct smaller pockmark structures that compose the larger Regab pockmark. Although most results are consistent with the existing successional models for seep communities, some observations in the distribution of the Regab mussel population do not entirely fit into these models. This is likely due to the high heterogeneity of this site formed by the coalescence of several pockmarks. We hypothesize that the mussel distribution at Regab could also be controlled by the occurrence of zones of both intense methane fluxes and reduced efficiency of the anaerobic oxidation of methane possibly limiting tubeworm colonization.

Skeletal density of Porites

Paleotemperature estimates based on coral Sr/Ca have not been widely accepted because the reconstructed glacial-Holocene shift in tropical sea-surface temperature (~4-6°C) is larger than that indicated by foraminiferal Mg/Ca (~2-4°C). We show that corals over-estimate changes in sea-surface temperature (SST) because their records are attenuated during skeletogenesis within the living tissue layer. To quantify this process, we microprofiled skeletal mass accumulation within the tissue layer of Porites from Australasian coral reefs and laboratory culturing experiments. The results show that the sensitivity of the Sr/Ca and d18O thermometers in Porites will be suppressed, variable, and dependent on the relationship between skeletal growth rate and mass accumulation within the tissue layer. Our findings help explain why d18O-SST sensitivities for Porites range from -0.08 per mil/°C to -0.22 per mil/°C and are always less than the value of -0.23 per mil/°C established for biogenic aragonite. Based on this observation, we recalibrated the coral Sr/Ca thermometer to determine a revised sensitivity of -0.084 mmol/mol/°C. After rescaling, most of the published Sr/Ca-SST estimates for the Indo-Pacific region for the last ~14,000 years (-7°C to +2°C relative to modern) fall within the 95% confidence envelope of the foraminiferal Mg/Ca-SST records. We conclude that two types of calibration scales are required for coral paleothermometry; an attenuated Porites-specific thermometer sensitivity for studies of seasonal to interannual change in SST and, importantly, the rescaled -0.084 mmol/mol/°C Sr/Ca sensitivity for studies of 20th-century trends and millennial-scale changes in mean SST. The calibration-scaling concept will apply to the development of transfer functions for all geochemical tracers in corals.

Pollen and macrofossils profiles and age determination from the Pittsburg Basin in the lowlands of south-central Illinois

Pollen and macrofossil evidence for the nature of the vegetation during glacial and interglacial periods in the regions south of the Wisconsinan ice margin is still very scarce. Modern opinions concerning these problems are therefore predominantly derived from geological evidence only or are extrapolated from pollen studies of late Wisconsinan deposits. Now for the first time pollen and macrofossil analyses are available from south-central Illinois covering the Holocene, the entire Wisconsinan, and most probably also Sangamonian and late Illinoian time. The cores studied came from three lakes, which originated as kettle holes in glacial drift of Illinoian age near Vandalia, Fayette County. The Wisconsinan ice sheet approached the sites from the the north to within about 60 km distance only. One of the profiles (Pittsburg Basin) probably reaches back to the late Illinoian (zone 1), which was characterized by forests with much Picea. Zone 2, most likely of Sangamonian age, represents a period of species-rich deciduous forests, which must have been similar to the ones that thrive today south and southeast of the prairie peninsula. During the entire Wisconsinan (14C dates ranging from 38,000 to 21,000 BP) thermophilous deciduous trees like Quercus, Carya, and Ulmus occurred in the region, although temporarily accompanied by tree genera with a more northerly modern distribution, such as Picea, which entered and then left south-central Illinois during the Woodfordian. Thus it is evident that arctic climatic conditions did not prevail in the lowlands of south-central Illinois (about 38°30' lat) during the Wisconsinan, even at the time of the maximum glaciation, the Woodfordian. The Wisconsinan was, however, not a period of continuous forest. The pollen assemblages of zone 3 (Altonian) indicate prairie with stands of trees, and in zone 4 the relatively abundant Artemisia pollen indicates the existence of open vegetation and stands of deciduous trees, Picea, and Pinus. True tundra may have existed north of the sites, but if so its pollen rain apparently is marked by pollen from nearby stands of trees. After the disappearance of Pinus and Picea at about 14,000 BP (estimated!), there developed a mosaic of prairies and stands of Quercus, Carya, and other deciduous tree genera (zone 5). This type of vegetation persisted until it was destroyed by cultivation during the 19th and 20th century. Major vegetational changes are not indicated in the pollen diagram for the late Wisconsinan and the Holocene. The dating of zones 1 and 2 is problematical because the sediments are beyond the14C range and because of the lack of stratigraphic evidence. The zones dated as Illinoian and Sangamonian could also represent just a Wisconsinan stadial and interstadial. This possibility, however, seems to be contradicted by the late glacial and interglacial character of the forest vegetation of that time.