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).

Physico-chemical parameters of sediment core PG1972-1 (09-Tik-03) from a Tundra Lake, Northeastern Siberia

Thermokarst lakes in the Siberian Arctic contain sediment archives that can be used for paleoenvironmental inference. Until now, however, there has been no study from the inner Lena River Delta with a focus on diatoms. The objective of this study was to investigate how the diatom community in a thermokarst lake responded to past limnogeological changes and what specific factors drove variations in the diatom assemblage. We analysed fossil diatom species, organic content, grain-size distribution and elemental composition in a sediment core retrieved in 2009 from a shallow thermokarst lake in the Arga Complex, western Lena River Delta. The core contains a 3,000-year record of sediment accumulation. Shifts in the predominantly benthic and epiphytic diatom species composition parallel changes in sediment characteristics. Paleoenvironmental and limnogeological development, inferred from multiple biological and sedimentological variables, are discussed in the context of four diatom zones, and indicate a strong relation between changes in the diatom assemblage and thermokarst processes. We conclude that limnogeological and thermokarst processes such as lake drainage, rather than direct climate forcing, were the main factors that altered the aquatic ecosystem by influencing, for example, habitat availability, hydrochemistry, and water level.

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 characterization of dissolved organic compounds from coastal sea surface microlayers (Baltic Sea, Germany)

The physicochemical properties of the sea surface microlayer (SML), i.e. the boundary layer between the air and the sea, and its impact on air-sea exchange processes have been investigated for decades. However, a detailed description about these processes remains incomplete. In order to obtain a better chemical characterization of the SML, in a case study three pairs of SML and corresponding bulk water samples were taken in the southern Baltic Sea. The samples were analyzed for dissolved organic carbon and dissolved total nitrogen, as well as for several organic nitrogen containing compounds and carbohydrates, namely aliphatic amines, dissolved free amino acids, dissolved free monosaccharides, sugar alcohols, and monosaccharide anhydrates. Therefore, reasonable analytical procedures with respect to desalting and enrichment were established. All aliphatic amines and the majority of the investigated amino acids (11 out of 18) were found in the samples with average concentrations between 53 ng/l and 1574 ng/l. The concentrations of carbohydrates were slightly higher, averaging 2900 ng/l. Calculation of the enrichment factor (EF) between the sea surface microlayer and the bulk water showed that dissolved total nitrogen was more enriched (EF: 1.1 and 1.2) in the SML than dissolved organic carbon (EF: 1.0 and 1.1). The nitrogen containing organic compounds were generally found to be enriched in the SML (EF: 1.9-9.2), whereas dissolved carbohydrates were not enriched or even depleted (EF: 0.7-1.2). Although the investigated compounds contributed on average only 0.3% to the dissolved organic carbon and 0.4% to the total dissolved nitrogen fraction, these results underline the importance of single compound analysis to determine SML structure, function, and its potential for a transfer of compounds into the atmosphere.

Physico-chemical parameters of sediment core PG1975-1 (09-Tik-05) from a Tundra Lake, Northeastern Siberia

The relationships between thermokarst activity, limnogeological processes and climate change in the Siberian Arctic are not well understood. The objective of this paper is to identify the factors controlling the patterns of deposition, using grain size distribution, organic content, elemental composition and mineralogical composition of a 137-cm long sediment core with a maximum age of ~10.9 cal. kyr BP from Lake El'gene-Kyuele in the tundra of northeastern Siberia. Eight fine sand layers are attributed to depositional events associated with thaw slump activity acting upon orthogonally oriented patterns of ice-wedge networks in the ice-rich permafrost on the NW margin of the lake catchment. Sr/Rb ratios, which correspond to the total feldspar and illite content, serve as high-resolution grain size proxies. The Br content relates to the total organic carbon content, and the Fe/Mn ratio reflects the degree of oxidisation. Our results indicate a relationship between repeated phases of fine sand input and retrogressive thaw slumping dependent on hydroclimate variability and orthogonally oriented ice-wedge networks within the catchment.

Chemical characterization of marine sub-micrometer aerosol particles during the MERIAN cruise MSM18/3 from the Cape Verde island Sao Vicente to Gabun (Atlantic Ocean)

Sub-micron marine aerosol particles (PM1) were collected during the MERIAN cruise MSM 18/3 between 22 June 2011 and 21 July 2011 from the Cape Verde island Sao Vicente to Gabun crossing the tropical Atlantic Ocean and passing equatorial upwelling areas. According to air mass origin and chemical composition of the aerosol particles, three main regimes could be established. Aerosol particles in the first part of the cruise were mainly of marine origin, in the second part was marine and slightly biomass burning influenced (increasing tendency) and in the in last part of the cruise, approaching the African mainland, biomass burning influences became dominant. Generally aerosols were dominated by sulfate (caverage = 1.99 µg/m**3) and ammonium ions (caverage = 0.72 µg/m**3) that are well correlated and slightly increasing along the cruise. High concentrations of water insoluble organic carbon (WISOC) averaging 0.51 µg/m**3 were found probably attributed to the high oceanic productivity in this region. Water soluble organic carbon (WSOC) was strongly increasing along the cruise from concentrations of 0.26 µg/m**3 in the mainly marine influenced part to concentrations up to 3.3 µg/m**3 that are probably caused by biomass burning influences. Major organic constituents were oxalic acid, methansulfonic acid (MSA) and aliphatic amines. MSA concentrations were quite constant along the cruise (caverage = 43 ng/m**3). While aliphatic amines were more abundant in the first mainly marine influenced part with concentrations of about 20 ng/m**3, oxalic acid showed the opposite pattern with average concentrations of 12 ng/m**3 in the marine and 158 ng/m**3 in the biomass burning influenced part. The alpha dicarbonyl compounds glyoxal and methylglyoxal were detected in the aerosol particles in the low ng/m**3 range and followed oxalic acid closely. MSA and aliphatic amines accounted for biogenic marine (secondary) aerosol constituents whereas oxalic acid and the alpha dicarbonyl compounds were believed to result mainly from biomass burning. N-alkane concentrations increased along the cruise from 0.81 to 4.66 ng/m**3, PAHs and hopanes were abundant in the last part of the cruise (caverage of PAHs = 0.13 ng/m**3, caverage of hopanes = 0.19 ng/m**3). Levoglucosan was identified in several samples of the last part of the cruise in concentrations around 2 ng/m**3, pointing to (aged) biomass burning influences. The investigated organic compounds could explain 9.5% of WSOC in the mainly marine influenced part (dominating compounds: aliphatic amines and MSA) and 2.7% of WSOC in the biomass burning influenced part (dominating compound: oxalic acid) of the cruise.

Gas production during the pyrolysis and gasification of biological and physico-chemical sludges from oil refinery

Pyrolysis and gasification of two different sludges coming from a Spanish refinery have been performed at different experimental conditions. A physico-chemical (PC) and a biological (BIO) sludge have been studied. Runs at different heating rates (approx. 4 and 10 K/s) and with different contact time between gases and decomposed sludge have been performed. In general, the ratio H2/CO is higher in pyrolytic runs. The highest ratio is obtained in the pyrolysis at low heating rate and parallel flow, using both sludges. The maximum emission of CO, i.e. the worst combustion conditions, is given in the runs where contact time is minimized and at high heating rates.