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).

Chemical composition and isotopic ratios of basic lavas from Iceland and the surrounding ocean floor

Major and trace dement data are used to establish the nature and extent of spatial and temporal chemical variations in basalts erupted in the Iceland region of the North Atlantic Ocean. The ocean floor samples are those recovered by legs 38 and 49 of the Deep Sea Drilling Project. Within each of the active zones on Iceland there are small scale variations in the light rare earth elements and ratios such as K/Y: several central complexes and their associated fissure swarms erupt basalts with values of K/Y distinct from those erupted at adjacent centres; also basalts showing a wide range of immobile trace element ratios occur together within single vertical sections and ocean floor drill holes. Although such variations can be explained in terms of the magmatic processes operating on Iceland they make extrapolations from single basalt samples to mantle sources underlying the outcrop of the sample highly tenuous. 87Sr/86Sr ratios measured for 25 of the samples indicate a total range from 0.7028 in a tholeiite from the Reykjanes Ridge to 0.7034 in an alkali basalt from Iceland and are consistent with other published ratios from the region. A positive correlation between 87Sr/86Sr and Ce/Yb ratios indicates the existence of systematic isotopic and elemental variations in the mantle source region. An approximately fivefold variation in Ce/Yb ratio observed in basalts with the same 87Sr/86Sr ratio implies that different degrees and types of partial melting have been involved in magma genesis from a single mantle composition. 87Sr/86Sr ratios above 0.7028, Th/U ratios close to 4 and La/Ta ratios close to 10 distinguish most basalts erupted in this part of the North Atlantic Ocean from normal mid-ocean ridge basalt (N-type MORB) - although N-type MORB has been erupted at extinct spreading axes just to the north and northeast of Iceland as well as the presently active Iceland-Jan Mayen Ridge. Comparisons with the hygromagmatophile element and radiogenic isotope ratios of MORB and the estimated primordial mantle indicate that the mantle sources producing Iceland basalts have undergone previous depletion followed by more recent enrichment events. A veined mantle source region is proposed in preference to the mantle plume model to explain the chemical variations.

Chemical composition and sulfur-isotope ratios in DSDP Legs 69-and 70

As part of the geochemical-petrological study of basalts recovered from DSDP Hole 504B (Leg 70) on the southern flank of the Costa Rica Rift, we investigated specially the relationships between the distribution and isotopic composition of sulfur of scattered and vein sulfides on the one hand, and the observed pattern and processes of secondary alterations on the other. The following groups of observations are essential: (1) variations in the contents and isotopic composition of sulfur of different forms of sulfides are clearly interrelated and are observed solely in porous horizons established on the basis of detailed geophysical experiments; (2) the enrichment of sulfides in the light sulfur isotope decreases from the upper to the lower horizons, and within horizons in the direction of the less-altered rock; (3) the increase of d34S values of scattered sulfides in individual permeable zones parallels a decrease in the degree of iron oxidation in the contents of crystallization water, and in the concentrations of Mg, K, and Li in the rock.

Physico-chemical characteristics and ikaite content of brine and ice samples taken during SIPEX and DDU campaigns in East Antarctica, 2007

Calcium carbonate precipitation in sea ice is thought to potentially drive significant CO2 uptake by the ocean. However, little is known about the quantitative spatial and temporal distribution of CaCO3 within sea ice, although it is hypothesized that high quantities of dissolved organic matter and/or phosphate (common in sea ice) may inhibit its formation. In this quantitative study of hydrous calcium carbonate as ikaite, sea ice cores and brine samples were collected from pack and land fast sea ice between September and December 2007 during two expeditions, one in the East Antarctic sector and the other off Terre Adélie. Samples were analysed for CaCO3, salinity, dissolved organic carbon/nitrogen, inorganic phosphate, and total alkalinity. No relationship between these parameters and CaCO3 precipitation was evident. Ikaite was found mostly in the uppermost layers of sea ice with maximum concentrations of up to 126 mg ikaite per litre melted sea ice being measured, although both the temporal and horizontal spatial distributions of ikaite were highly heterogeneous. The precipitate was also found in the snow on top of the sea ice at some of the sampling locations.

Chemical composition and age of metamorphic rocks from the Khavyven Highland, Eastern Kamchatka

Metamorphic rocks of the Khavyven Highland in eastern Kamchatka were determined to comprise two complexes of metavolcanic rocks that have different ages and are associated with subordinate amounts of metasediments. The complex composing the lower part of the visible vertical section of the highland is dominated by leucocratic amphibole-mica (+/-garnet) and epidote-mica (+/-garnet) crystalline schists, whose protoliths were andesites and dacites and their high-K varieties of island-arc calc-alkaline series. The other complex composing the upper part of the vertical section consists of spilitized basaltoids transformed into epidote-amphibole and phengite-epidote-amphibole green schists, which form (together with quartzites, serpentinized peridotites, serpentinites, and gabbroids) a sea-margin ophiolitic association. High LILE concentrations, high K/La, Ba/Th, Th/Ta, and La/Nb ratios, deep Ta-Nb minima, and low (La/Yb)_N and high 87Sr/86Sr ratios of the crystalline schists of the lower unit are demonstrated to testify to their subduction nature and suggest that their protolithic volcanics were produced in the suprasubduction environment of the Ozernoi-Valaginskii (Achaivayam-Valaginskii) island volcanic arc of Campanian-Paleogene age. The green schists of the upper unit show features of depleted MOR tholeiitic melts and subduction melts, which cause the deep Ta-Nb minima, and low K/La and 87Sr/86Sr ratios suggesting that the green schists formed in a marginal basin in front of the Ozernoi-Valaginskaya island arc. Recently obtained K-Ar ages in the Khavyven Highland vary from 32.4 to 39.3 Ma and indicate that metamorphism of the protolithic rocks occurred in Eocene under effect of collision and accretion processes of the arc complexes of the Ozernoi-Valaginskii and Kronotskii island arcs with the Asian continent and the closure of forearc oceanic basins in front of them. The modern position of the collision suture that marks the fossil subduction zone of the Ozernoi-Valaginskii arc and is spatially restricted to the buried Khavyven uplift in the Central Kamchatka Depression characterized by well-pronounced linear gravity anomalies.