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.

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).

Characterization of sorbed volatile hydrocarbons from the Peru margin

Bacterial and thermogenic hydrocarbons are present in the sorbed-gas fraction of Peru margin sediments. At Ocean Drilling Program (ODP) Sites 681, 682, 684, and 686, bacterial gases are restricted to the early diagenetic zones, where dissolved sulfate has been exhausted and methanogenesis occurs. Methane migrating into the sulfate zone at Sites 681, 684, 686, and possibly 682, has been consumed anaerobically by methanotrophs, maintaining the low concentrations and causing an isotope shift in d13C(CH4) to more positive values. Significant amounts of C2+ hydrocarbons occur at the shelf Sites 680/681, 684, and 686/687, where these hydrocarbons may be associated with hypersaline fluids. There is evidence at Site 679 that sorbed C2+ hydrocarbons may also have been transported by hypersaline fluids. This characteristic C2+ hydrocarbon signature in the sorbed-gas fractions of sediments at Site 679 is not reflected in data obtained using the conventional "free-," "canned-," or "headspace-gas" procedures. The molecular and isotope compositions of the sorbed-gas fraction indicate that this gas may have a thermogenic source and may have spilled over with the hypersaline fluids from the Salaverry Basin into the Lima Basin. These traces of thermogenic hydrocarbon gases are over-mature (about 1.5% Ro) and are discordant with the less-mature sediments in which they are found. This observation supports the migration of these hydrocarbons, possibly from continental sources. Sorbed-gas analyses may provide important geochemical information, in addition to that of the free-gases. Sorbed-gases are less sensitive to activities in the interstitial fluids, such as methanogenesis and methanotrophy, and may faithfully record the migration of hydrocarbons associated with hypersaline fluids.

Characterization of diagenetic fluids at ODP Site 103-639

Site 639, drilled during Leg 103 of the Ocean Drilling Program, penetrated an Upper Jurassic to Lower Cretaceous carbonate platform on a tilted fault block along the Galicia margin off the northwest Iberian Peninsula. The carbonate platform is composed primarily of a sequence of dolomite overlying limestone. Samples were analyzed for mineral chemistry, stable isotope geochemistry, fluid inclusion microthermometry, and volatile contents and by dolomite pyrolysis mass spectrometry for trace sulfate minerals. The dolomite recovered from the Galicia margin at Site 639 formed during shallow burial from sulfate-bearing, hypersaline brines at slightly elevated temperatures. The light oxygen isotopic signatures of the dolomite are interpreted as the result of the evaporative loop and slightly elevated temperatures during dolomite formation or from reequilibration at higher temperatures during deeper burial. The hypersalinity is interpreted to be associated with a nearby, shallow restricted basin that formed during rifting of the Iberian margin from Newfoundland. The dolomitization of the platform is therefore a by-product of the rifting.

Geotechnical engineering characterization of sediments at DSDP Leg 72 Holes

The hydraulic piston coring device (HPC-15) allows recovery of deep ocean sediments with minimal disturbance. The device was used during Leg 72 of the Deep Sea Drilling Project (DSDP) aboard the Glomar Challenger. Core samples were recovered from bore holes in the Rio Grande Rise in the southwest Atlantic Ocean. Relatively undisturbed sediment cores were obtained from Holes 515A, 516, 517, and 518. The results of shipboard physical property measurements and on-shore geotechnical laboratory tests on these cores are presented in this chapter. A limited number of 0.3 m cores were obtained and used in a series of geotechnical tests, including one-dimensional consolidation, direct shear, Atterburg limit, particle size analysis, and specific gravity tests. Throughout the testing program, attention was focused on assessment of sample disturbance associated with the HPC-15 coring device. The HPC-15 device limits sample disturbance reasonably well in terrigenous muds (clays). However, sample disturbance associated with coring calcareous sediments (nannofossil-foraminifer oozes) is severe. The noncohesive, granular behavior of the calcareous sediments is vulnerable to severe disturbance, because of the design of the sampling head on the device at the time of Leg 72. A number of modifications to the sampling head design are recommended and discussed in this chapter. The modifications will improve sample quality for testing purposes and provide longer unbroken core samples by reducing friction between the sediment column and the sampling tool.

Geochemical characterization of black shales from the Tarfaya Basin

Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting changes in the quantity and quality of the organic matter. High TOC contents (up to 18wt%) and hydrogen indices between 400 and 800 (mgHC/gTOC) indicate hydrogen-rich organic matter (Type I-II kerogen) which qualifies these laminated black shale sequences as excellent oil-prone source rocks. Low Tmax values obtained from Rock-Eval pyrolysis (404-425 MC) confirm an immature to early mature level of thermal maturation. Organic petrological studies indicate that the kerogen is almost entirely composed of bituminite particles. These unstructured organic aggregates were most probably formed by intensive restructuring of labile biopolymers (lipids and/or carbohydrates), with the incorporation of sulphur into the kerogen during early diagenesis. Total lipid analyses performed after desulphurization of the total extract shows that the biomarkers mostly comprise short-chain n-alkanes (C16-C22) and long-chain (C25-C35) n-alkanes with no obvious odd-over-even predominance, together with steranes, hopanoids and acyclic isoprenoids. The presence of isorenieratane derivatives originating from green sulphur bacteria indicates that dissolved sulphide had reached the photic zone at shallow water depths (~100m) during times of deposition. These conditions probably favoured intensive sulphurization of the organic matter. Flash pyrolysis GC-MS analysis of the kerogen indicates the aliphatic nature of the bulk organic carbon. The vast majority of pyrolysis products are sulphur-containing components such as alkylthiophenes, alkenylthiophenes and alkybenzothiophenes. Abundant sulphurization of the Tarfaya Basin kerogen resulted from excess sulphide and metabolizable organic matter combined with a limited availability of iron during early diagenesis. The observed variability in the intensity of OM sulphurization may be attributed to sea level-driven fluctuations in the palaeoenvironment during sedimentation.

Characterization of late Campanian and Maastrichtian planktonic foraminiferal depth habitats and vital activities based on stable isotopes

Depth habitats of 56 late Cretaceous planktonic foraminiferal species from cool and warm climate modes were determined based on stable isotope analyses of deep-sea samples from the equatorial Pacific DSDP Sites 577A and 463, and South Atlantic DSDP Site 525A. The following conclusions can be reached: Planoglobulina multicamerata (De Klasz) and Heterohelix rajagopalani (Govindan) occupied the deepest plankton habitats, followed by Abathomphalus mayaroensis (Bolli), Globotruncanella havanensis (Voorwijk), Gublerina cuvillieri Kikoine, and Laeviheterohelix glabrans (Cushman) also at subthermocline depth. Most keeled globotruncanids, and possibly Globigerinelliodes and Racemiguembelina species, lived at or within the thermocline layer. Heterohelix globulosa (Ehrenberg) and Rugoglobigerina, Pseudotextularia and Planoglobulina occupied the subsurface depth of the mixed layer, and Pseudoguembelina species inhabited the surface mixed layer. However, depth ranking of some species varied depending on warm or cool climate modes, and late Campanian or Maastrichtian age. For example, most keeled globotruncanids occupied similar shallow subsurface habitats as Rugoglobigerina during the warm late Campanian, but occupied the deeper thermocline layer during cool climatic intervals. Two distinct types of "vital effect" mechanisms reflecting photosymbiosis and respiration effects can be recognized by the exceptional delta13C signals of some species. (1) Photosymbiosis is implied by the repetitive pattern of relatively enriched delta13C values of Racemiguembelina (strongest), Planoglobulina, Rosita and Rugoglobigerina species, Pseudoguembelina excolata (weakest). (2) Enriched respiration 12C products are recognized in A. mayaroensis, Gublerina acuta De Klasz, and Heterohelix planata (Cushman). Isotopic trends between samples suggest that photosymbiotic activities varied between localities or during different climate modes, and may have ceased under certain environmental conditions. The appearance of most photosymbiotic species in the late Maastrichtian suggests oligotrophic conditions associated with increased water-mass stratification.

Age and petrographic characterization of volcanic ash from ODP Leg 198 and Leg 126 sites

In this study of volcanic ash retrieved from Shatsky Rise during Ocean Drilling Program Leg 198, the texture and composition of the volcanic components (glass and crystals) were used to fingerprint ash layers for detailed correlation. Correlations among ash layers in holes drilled at the same site as well as between sites, including sites on different parts (highs) of the rise, were tested. Although high-to-high correlations failed, intrahigh correlations were more successful. Our data suggest a significantly different source for some pyroclastic debris, especially at Site 1208, possibly associated with pumice rafts carried northward from the Izu-Bonin arc by the Kuroshio Current. Other ashes are consistent with rhyolitic to dacitic air fall ash from Asian arc volcanoes. We were not able to texturally distinguish between air fall ash and pumice-raft fallout but suspect that the latter is associated with higher percentages of vesiculated ash components, as we demonstrate occur in more proximal Izu-Bonin pyroclastic deposits.

Working on a baseline for the Kongsfjorden food web: production and properties of macroalgal particulate organic matter (POM), supplementary material

Macroalgae, in particular kelps, produce a large amount of biomass in Kongsfjorden, which is to a great extent released into the water in an annual cycle. As an example, the brown alga Alaria esculenta loses its blade gradually, 3 ± 0.8 % of the blade area per day (August 2012), thereby adding to the pool of particulate organic matter (POM) in the fjord. Upon release small thallus pieces are "aging" in that they are prone to leaching and serving as substrate for microorganisms, thus turning into palatable food for suspension and bottom feeders. In order to define a macroalgal baseline for the Kongsfjorden food web, stable isotopes d14C and d15N were measured in individuals of A. esculenta, Saccharina latissima and Laminaria digitata directly sampled after collection and in artificially produced POM (aPOM) of A. esculenta that was allowed to age under experimental conditions. In aPOM from this species sampled in August 2012 the C/N ratios decreased between d1 and d8 of a 14-day culture period in parallel to the fading photosynthetic activity of the algal fragments as demonstrated by use of an Imaging-PAM. Microscopic observations of the aPOM in August 2012 and 2013 revealed the frequent occurrence of small brown algal endo- and epiphytes. First feeding experiments with Mysis oculata (Mysids) and Hiatella arctica (Bivalves) showed that these species can ingest macroalgal POM. The importance of kelp-derived POM for the food web is subject of the current research.

Web-based Biodiversity Citizen Science Database (assembled 2012)

The collective impact of humans on biodiversity rivals mass extinction events defining Earth's history, but does our large population also present opportunities to document and contend with this crisis? We provide the first quantitative review of biodiversity-related citizen science to determine whether data collected by these projects can be, and are currently being, effectively used in biodiversity research. We find strong evidence of the potential of citizen science: within projects we sampled (n = 388), ~1.3 million volunteers participate, contributing up to US Dollar 2.5 billion in-kind annually. These projects exceed most federally-funded studies in spatial and temporal extent, and collectively they sample a breadth of taxonomic diversity. However, only 12% of the 388 projects surveyed obviously provide data to peer-reviewed scientific articles, despite the fact that a third of these projects have verifiable, standardized data that are accessible online. Factors influencing publication included project spatial scale and longevity and having publically available data, as well as one measure of scientific rigor (taxonomic identification training). Because of the low rate at which citizen science data reach publication, the large and growing citizen science movement is likely only realizing a small portion of its potential impact on the scientific research community. Strengthening connections between professional and non-professional participants in the scientific process will enable this large data resource to be better harnessed to understand and address global change impacts on biodiversity.

Microsedimentological characterization as indicators of sedimentary processes and climate changes during Lateglacial at Laguna Potrok Aike, Santa Cruz, Argentina

Palaeoclimatic and paleoenvironmental high latitude records in the Southern Hemisphere are scarce compared to the northern counterpart. However, understanding global evolution of environmental systems during sudden climate changes is inseparable from an equivalent knowledge of both Hemispheres. In this context, a high-resolution study of lacustrine sediments from Laguna Potrok Aike, Santa Cruz province, Patagonia, Argentina, was conducted for the Lateglacial period using concurrent X-Ray Fluorescence (XRF) and Scanning electron microscope analyses. Peaks of Ca/Si and Mn, and occurrences of the green alga Phacotus lenticularis have been interpreted as variations in ventilation of the water column from 13.6 to 11.1 ka cal. BP. During this interval, mild climate conditions during the Younger Dryas are characterized by relatively weak westerlies favouring the formation of a stratified water body as indicated by preserved manganese and Ca/Si peaks and high Total Organic Carbon (TOC) values. In this environment, water in the epilimnion can reach sufficiently high temperature to allow P. lenticularis to grow. Colder conditions are marked by peaks in Ca without P. lenticularis and occur during the Antarctic Cold Reversal (ACR). In this Lateglacial interval, micropumices were also detected in large amount. Image analysis of thin sections allowed the counting and size measurement of detrital particles and micropumices separately. Micropumices significantly influence the iron and titanium content, hence preventing to use them as proxies of detrital input in this interval.

delta 13C, delta 15N and delta 34S of temperate eelgrass food web in the western Baltic Sea

Simultaneous triple stable isotope analysis of carbon, nitrogen and sulphur was employed to study the temporal variation in the food web of a subtidal eelgrass (Zostera marina) bed in the western Baltic Sea. Samples of three potential food sources: eelgrass, epiphytes and seston, as well as consumer species were collected biweekly from March through September 2011. Temporal variation of stable isotope signatures was observed in primary producers and consumer species. However, variation within a species, particularly omnivores, often exceeded variation over time. The high degree of omnivory among the generalist feeders in this eelgrass community allows for generalist feeders to flexibly switch food sources, thus enhancing food web stability. As coastal systems are subject to seasonal changes, as well as alterations related to human disturbance and climate, these food webs may retain a certain resilience due to their plentiful omnivores.