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).

Chronostratigraphy of sediment core CRP-3 from the Ross Sea, Antarctica

An 823 m thick glaciomarine Cenozoic section sitting unconformably on the Lower Devonian Beacon Supergroup was recovered in CRP-3. This paper reviews the chronostratigraphical constraints for the Cenozoic section. Between 3 and 480.27 mbsf 23 unconformity bounded cycles of sediment were recorded. Each unconformity is thought to represent a hiatus of uncertain duration. Four magnetozones have been recognised from the Cenozoic section. The record is complex with several 'tiny wiggles'' recorded throughout. Biostratigraphical or Sr ages, which could be used to link these magnetozones to the magnetic polarity time scale are restricted to the upper 190 m of sediment. Two diatom datums (Cavitatus jouseanus at 48.9 mbsf and Rhizosolenica antarctica at 68.60 mbsf), together with five Sr-isotope dates derived from molluscan fragments taken from between 10.88 and 190.29 mbsf indicate an early Oligocene (c. 31 Ma) age for this interval. The appearance of a new species of the bivalve ?Adamussium at about 325 mbsf, suggests that the Oligocene age can be extended down to this level. This confirms that the dominantly reversed magnetozone (RI), recorded down to about 340 mbsf, is Chron C12r. The ages imply high sedimentation rates and only minimal time gaps at the sequence boundaries. Below 340 mbsf there are no independent datums to guide the correlation of the magnetozones to the magnetic polarity time scale. However, the absence of in situ dinocysts attributable to Transantarctic Flora, if not a result of environmental control, limits the age of the base of the hole to between c. 33.5 and 35 Ma.

Geochemistry on Holocene sediments from the Mediterranean

The enhanced accumulation of organic matter in Eastern Mediterranean sapropels and their unusually low d15N values have been attributed to either enhanced nutrient availability which led to elevated primary production and carbon sequestration or to enhanced organic matter preservation under anoxic conditions. In order to evaluate these two hypothesis we have determined Ba/Al ratios, amino acid composition, N and organic C concentrations and d15N in sinking particles, surface sediments, eight spatially distributed core records of the youngest sapropel S1 (10-6 ka) and older sapropels (S5, S6) from two locations. These data suggest that (i) temporal and spatial variations in d15N of sedimentary N are driven by different degrees of diagenesis at different sites rather than by changes in N-sources or primary productivity and (ii) present day TOC export production would suffice to create a sapropel like S1 under conditions of deep-water anoxia. This implies that both enhanced TOC accumulation and d15N depletion in sapropels were due to the absence of oxygen in deep waters. Thus preservation plays a major role for the accumulation of organic-rich sediments casting doubt on the need of enhanced primary production for sapropel formation.

Turbulent flux and meteorological measurements during ARCTEX-2006 campaign

This dataset present result from the DFG- funded Arctic-Turbulence-Experiment (ARCTEX-2006) performed by the University of Bayreuth on the island of Svalbard, Norway, during the winter/spring transition 2006. From May 5 to May 19, 2006 turbulent flux and meteorological measurements were performed on the monitoring field near Ny-Ålesund, at 78°55'24'' N, 11°55'15'' E Kongsfjord, Svalbard (Spitsbergen), Norway. The ARCTEX-2006 campaign site was located about 200 m southeast of the settlement on flat snow covered tundra, 11 m to 14 m above sea level. The permanent sites used for this study consisted of the 10 m meteorological tower of the Alfred Wegener Institute for Polar- and Marine Research (AWI), the international standardized radiation measurement site of the Baseline Surface Radiation Network (BSRN), the radiosonde launch site and the AWI tethered balloon launch sites. The temporary sites - set up by the University of Bayreuth - were a 6 m meteorological gradient tower, an eddy-flux measurement complex (EF), and a laser-scintillometer section (SLS). A quality assessment and data correction was applied to detect and eliminate specific measurement errors common at a high arctic landscape. In addition, the quality checked sensible heat flux measurements are compared with bulk aerodynamic formulas that are widely used in atmosphere-ocean/land-ice models for polar regions as described in Ebert and Curry (1993, doi:10.1029/93JC00656) and Launiainen and Cheng (1995). These parameterization approaches easily allow estimation of the turbulent surface fluxes from routine meteorological measurements. The data show: - the role of the intermittency of the turbulent atmospheric fluctuation of momentum and scalars, - the existence of a disturbed vertical temperature profile (sharp inversion layer) close to the surface, - the relevance of possible free convection events for the snow or ice melt in the Arctic spring at Svalbard, and - the relevance of meso-scale atmospheric circulation pattern and air-mass advection for the near-surface turbulent heat exchange in the Arctic spring at Svalbard. Recommendations and improvements regarding the interpretation of eddy-flux and laser-scintillometer data as well as the arrangement of the instrumentation under polar distinct exchange conditions and (extreme) weather situations could be derived.

Composition and age of rocks from the King's Trough and Palmer Ridge

This paper presents results of studies of rocks sampled during Cruise 19 of R/V Akademik Mstislav Keldysh with the Mir submersibles in the Atlantic Ocean (slopes of the King's Trough and Palmer Ridge). Based on these materials and published data two stages of magmatism and evolution in the region are distinguished: 1) formation of a mid-ocean ridge in the rift zone (68-32 Ma); 2) development of intraplate volcanism during movement of the plate over a "hot spot" (32-0 Ma).

Concentration of trace elements in samples of sea water determined by use of two methods of concentrating

A device and a specific procedure for simultaneous concentration of trace ele¬ments from sea water by co-precipitating them in precipitate of magnesium hydroxide obtained by electrolytic alkalization of samples in a two-chamber electrolyzer are described. Analyses of sea water samples for zinc, iron, copper, nickel and lead demonstrate that the method produces a thousand-fold concentration and gives results that agree well with those obtained by extractive concentration using diethyldithiocarbamate and 8-hydroxyquinoline in chloroform. Extracts were analyzed by flame atomic absorption. Correlation coefficients of results obtained with use of these two methods of concentration were 0.76-0.87 for zinc, iron, and copper at confidence levels of 0.05-0.07. Average zinc and iron concentrations determined by the method differed by less than 10%.

Amino acid data of catchment and sediment core samples of four Indian lakes

In the present study, we report the results of comprehensive amino acid (AA) analyses of four Indian lakes from different climate regimes. We focus on the investigation of sediment cores retrieved from the lakes but data of modern sediment as well as vascular plant, soil, and suspended particulate matter samples from individual lakes are also presented. Commonly used degradation and organic matter source indices are tested for their applicability to the lake sediments, and we discuss potential reasons for possible limitations. A principal component analysis including the monomeric AA composition of organic matter of all analysed samples indicates that differences in organic matter sources and the environmental properties of the individual lakes are responsible for the major variability in monomeric AA distribution of the different samples. However, the PCA also gives a factor that most probably separates the samples according to their state of organic matter degradation. Using the factor loadings of the individual AA monomers, we calculate a lake sediment degradation index (LI) that might be applicable to other palaeo-lake investigations.