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).

Gravity potential spherical harmonic series

Time variable gravity fields, reflecting variations of mass distribution in the system Earth is one of the key parameters to understand the changing Earth. Mass variations are caused either by redistribution of mass in, on or above the Earth's surface or by geophysical processes in the Earth's interior. The first set of observations of monthly variations of the Earth gravity field was provided by the US/German GRACE satellite mission beginning in 2002. This mission is still providing valuable information to the science community. However, as GRACE has outlived its expected lifetime, the geoscience community is currently seeking successor missions in order to maintain the long time series of climate change that was begun by GRACE. Several studies on science requirements and technical feasibility have been conducted in the recent years. These studies required a realistic model of the time variable gravity field in order to perform simulation studies on sensitivity of satellites and their instrumentation. This was the primary reason for the European Space Agency (ESA) to initiate a study on ''Monitoring and Modelling individual Sources of Mass Distribution and Transport in the Earth System by Means of Satellites''. The goal of this interdisciplinary study was to create as realistic as possible simulated time variable gravity fields based on coupled geophysical models, which could be used in the simulation processes in a controlled environment. For this purpose global atmosphere, ocean, continental hydrology and ice models were used. The coupling was performed by using consistent forcing throughout the models and by including water flow between the different domains of the Earth system. In addition gravity field changes due to solid Earth processes like continuous glacial isostatic adjustment (GIA) and a sudden earthquake with co-seismic and post-seismic signals were modelled. All individual model results were combined and converted to gravity field spherical harmonic series, which is the quantity commonly used to describe the Earth's global gravity field. The result of this study is a twelve-year time-series of 6-hourly time variable gravity field spherical harmonics up to degree and order 180 corresponding to a global spatial resolution of 1 degree in latitude and longitude. In this paper, we outline the input data sets and the process of combining these data sets into a coherent model of temporal gravity field changes. The resulting time series was used in some follow-on studies and is available to anybody interested.

A time-slice study in Heinrich Stadial 1 and Mid Holocene sediment cores off northern Senegal

Sediment dynamics in limnic, fluvial and marine environments can be assessed by granulometric and rock-magnetic methodologies. While classical grain-size analysis by sieving or settling mainly bears information on composition and transport, the magnetic mineral assemblages reflect to a larger extent the petrology and weathering conditions in the sediment source areas. Here, we combine both methods to investigate Late Quaternary marine sediments from five cores along a transect across the continental slope off Senegal. This region near the modern summer Intertropical Convergence Zone is particularly sensitive to climate change and receives sediments from several aeolian, fluvial and marine sources. From each of the investigated five GeoB sediment cores (494-2956 m water depth) two time slices were processed which represent contrasting climatic conditions: the arid Heinrich Stadial 1 (~ 15 kyr BP) and the humid Mid Holocene (~ 6 kyr BP). Each sediment sample was split into 16 grain-size fractions ranging from 1.6 to 500 µm. Concentration and grain-size indicative magnetic parameters (susceptibility, SIRM, HIRM, ARM and ARM/IRM) were determined at room temperature for each of these fractions. The joint consideration of whole sediment and magnetic mineral grain-size distributions allows to address several important issues: (i) distinction of two aeolian sediment fractions, one carried by the north-easterly trade winds (40-63 µm) and the other by the overlying easterly Harmattan wind (10-20 µm) as well as a fluvial fraction assigned to the Senegal River (< 10 µm); (ii) identification of three terrigenous sediment source areas: southern Sahara and Sahel dust (low fine-grained magnetite amounts and a comparatively high haematite content), dust from Senegalese coastal dunes (intermediate fine-grained magnetite and haematite contents) and soils from the upper reaches of the Senegal River (high fine-grained magnetite content); (iii) detection of partial diagenetic dissolution of fine magnetite particles as a function of organic input and shore distance; (iv) analysis of magnetic properties of marine carbonates dominating the grain-size fractions 63-500 µm.

The sulphate component in aerosol samples over the Noth Atlantic Ocean (Tab. 1)

The size distribution of sulphate containing particles over the North Atlantic was determined for particles with radii larger than 0.18 µm. It is compared with the size distributions of the total aerosol, the hygroscopic and the insoluble parts in the maritime aerosol. From mass concentrations of sulphate and sodium, it can be concluded that only a fraction of sulphate originates from the ocean. The sulphate mass distribution separated into its sea salt sulphate and excess sulphate components is compared with a continental distribution.

Isotope record and major element chemistry of intestitial waters of ODP Leg 104 sites

The variations in major elements and isotope composition (87Sr/86Sr, delta18O, deltaD) of interstitial waters in Leg 104 sediments is most probably caused by the alteration of volcanic matter. A reaction scheme where volcanic glass reacts with pore-water magnesium and potassium to form trioctahedral smectite, phillipsite, and chert is proposed. Model calculations demonstrate that the pore waters may evolve their negative 6180 signatures without recourse to unreasonably large amounts of volcanic detritus or external sources.

Planktonic foraminiferas in bottom sediments and Late Quaternary paleotemperatures of surface waters in the North Tropical Atlantic

Distribution of planktonic foraminiferal tests was studied in 15 Upper Quaternary sediment cores from the continental slope of Africa, the Canary and Cape Verde basins, and slopes of the Mid-Atlantic Ridge. In all the cores substantial variations were found in relationship between foraminiferal planktonic species reflecting fluctuations of mean annual temperatures of surface waters. Temperature difference in temperatures between present time and that of the maximum of the stadial of the last continental glaciation glacial stadial (about 18,000 yrs ago) ranges from 8.5°C in the Canary upwelling region to minimum values of 2.0°C in the central part of the ocean, i.e. the southern part of the subtropical gyre. Temperature difference the Holocene optimum and 18,000 yrs ago ranges from 10°C to 3°C. Age estimates are supported by radiocarbon dates.

Planktonic and benthic foraminiferal abundances in ODP Holes 133-819A and 133-821A

To reveal changes in the oceanic environment on the continental slope adjacent to the Great Barrier Reef, east of Cairns (NE Australia), planktonic and benthic foraminiferal abundances were counted and planktonic percentages (P/B ratios) were determined in sediments from two sites. Counts of planktonic and benthic specimens per gram of sediment over the last glacial/interglacial cycle at the shallowest Site 821, located in a water depth of 212 m just below the core of Subtropical Lower Water, show high abundances in the last glacial compared with the Holocene interglacial. We interpret the apparent increase in abundances during the last glacial as mainly a consequence of fluctuations in the intensity of flow of Subtropical Lower Water along the outer shelf edge and upper slope. During the lowstand in sea level, the increased flow winnowed the sediments, concentrating the foraminiferal skeletons. The P/B ratios are low throughout, with the highest values occurring during the Holocene interglacial and glacial stage 2. This suggests that some upwelling might have occurred during glacial stage 2. The relatively deeper water Site 819 is located in 565.2 m of water in a zone of mixing between Subtropical Lower Water and Antarctic Intermediate Water. The studied record at this site represents middle to upper Quaternary sediments, but it was interrupted by a hiatus just above stage 15 (Alexander et al., this volume); stages 7 through 13 are missing. Below the hiatus (isotopic stages 15 through 21), the foraminiferal abundances are low, while above the hiatus, the highest abundances occur in isotopic stage 6. In addition, a major change in the P/B ratio occurs across the unconformity. Below the hiatus, the ratios are low and resemble the values of the top of Site 821; but above it, ratios rapidly fluctuate, with a tendency for high values during glacial periods. We interpret the changes across the hiatus as having been caused by a shift in the position of the mixing zone between subsurface Subtropical Lower Water and Antarctic Intermediate Water. The mixing zone of these watermasses was farther down the slope in isotopic stages 15 through 21. This is indicated by the low P/B ratios, similar to the values found in the top of Site 821, which presently is bathed in subtropical waters. Above the hiatus, the influence of Antarctic Intermediate Water increased, as inferred from the high P/B ratios.

Stable isotope ratios of foraminifera from last glacial-interglacial sediments of the southern high latitudes

A set of numerical equations is developed to estimate past sea surface temperatures (SST) from fossil Antarctic diatoms. These equations take into account both the biogeographic distribution and experimentally derived silica dissolution. The data represent a revision and expansion of a floral data base used previously and includes samples resulting from progressive opal dissolution experiments. Factor analysis of 166 samples (124 Holocene core top and 42 artificial samples) resolved four factors. Three of these factors depend on the water mass distribution (one Subantarctic and two Antarctic assemblages); factor 4 corresponds to a 'dissolution assemblage'. Inclusion of this factor in the data analysis minimizes the effect of opal dissolution on the assemblages and gives accurate estimates of SST over a wide range of biosiliceous dissolution. A transfer function (DTF 166/34/4) is derived from the distribution of these factors versus summer SST. Its standard error is +/- 1°C in the -1 to +10 °C summer temperature range. This transfer function is used to estimate SST changes in two southern ocean cores (43°S and 55°S) which cover the last climatic cycle. The time scale is derived from the changes in foraminiferal oxygen and carbon isotopic ratios. The reconstructed SST records present strong analogies with the air temperature record over Antarctica at the Vostok site, derived from changes in the isotopic ratio of the ice. This similarity may be used to compare the oceanic isotope stratigraphy and the Vostok time scale derived from ice flow model. The oceanic time scale, if taken at face value, would indicate that large changes in ice accumulation rates occurred between warm and cold periods.

Carbonate sedimentology of the Propeller Mound, Northeast Atlantic

High resolution studies from the Propeller Mound, a cold-water coral carbonate mound in the NE Atlantic, show that this mound consists of >50% carbonate justifying the name "carbonate mound". Through the last ~300,000 years approximately one third of the carbonate has been contributed by cold-water corals, namely Lophelia pertusa and Madrepora oculata. This coral bound contribution to the carbonate budget of Propeller Mound is probably accompanied by an unknown portion of sediments buffered from suspension by the corals. However, extended hiatuses in Propeller Mound sequences only allow the calculation of a net carbonate accumulation. Thus, net carbonate accumulation for the last 175 kyr accounts for only <0.3 g/cm2/kyr, which is even less than for the off-mound sediments. These data imply that Propeller Mound faces burial by hemipelagic sediments as has happened to numerous buried carbonate mounds found slightly to the north of the investigated area.