Culture conditions, mass spectrometric measurements and acclimation carbonate chemistry

- A combined increase in seawater [CO2] and [H+] was recently shown to induce a shift from photosynthetic HCO3- to CO2 uptake in Emiliania huxleyi. This shift occurred within minutes, whereas acclimation to ocean acidification (OA) did not affect the carbon source. - To identify the driver of this shift, we exposed low- and high-light acclimated E. huxleyi to a matrix of two levels of dissolved inorganic carbon (1400, 2800 lmol kg-1) and pH (8.15, 7.85) and directly measured cellular O2, CO2 and HCO3 fluxes under these conditions. - Exposure to increased [CO2] had little effect on the photosynthetic fluxes, whereas increased [H+] led to a significant decline in HCO3- uptake. Low-light acclimated cells overcompensated for the inhibition of HCO3- uptake by increasing CO2 uptake. High-light acclimated cells, relying on higher proportions of HCO3- uptake, could not increase CO2 uptake and photosynthetic O2 evolution consequently became carbon-limited. - These regulations indicate that OA responses in photosynthesis are caused by [H+] rather than by [CO2]. The impaired HCO3- uptake also provides a mechanistic explanation for lowered calcification under OA. Moreover, it explains the OA-dependent decrease in photosynthesis observed in high-light grown phytoplankton.

Th-U ages of a stalagmite from the Kleegruben Cave (Table 1)

A mass-spectrometric uranium-series dated stalagmite from the Central Alps of Austria provides unprecedented new insights into high-altitude climate change during the peak of isotope stage 3. The stalagmite formed continuously between 57 and 46 kyr before present. A series of 'Hendy tests' demonstrates that the outer parts of the sample show a progressive increase of both stable C and O isotope values. No such covariant increase was detected within the axial zone. This in conjunction with other observations suggests that the continuous stable oxygen isotope profile obtained from the axial zone of the stalagmite largely reflects the unaltered isotopic composition of the cave drip water. The delta18O record shows events of high delta18O values that correlate remarkably with Interstadials 15 (a and b), 14 and 12 identified in the Greenland ice cores. Interstadial 15b started rapidly at 55.6 kyr and lasted ~300 yr only, Interstadial 15a peaked 54.9 kyr ago and was even of shorter duration (~100 yr), and Interstadial 14 commenced 54.2 kyr ago and lasted ~3000 yr. This stalagmite thus represents one of the first terrestrial archives outside the high latitudes which record precisely dated Dansgaard-Oeschger (D/O) events during isotope stage 3. Provided that rapid D/O warmings occurred synchronously in Greenland and the European Alps, the new data provide an independent tool to improve the GRIP and GISP2 chronologies.

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).

Geochemistry and isotopic ratios of samples obtained during R/V Akademik Nikolaj Strakhov cruise ANS24

New petrological and geochemical data were obtained for basalts recovered during cruise 24 of the R/V "Akademik Nikolay Strakhov" in 2006. These results significantly contributed to the understanding of the formation of tholeiitic magmatism at the northern end of the Knipovich Ridge of the Polar Atlantic. Dredging was performed for the first time both in the rift valley and on the flanks of the ridge. It showed that the conditions of magmatism have not changed since at least 10 Ma. The basalts correspond to slightly enriched tholeiites, whose primary melts were derived at the shallowest levels and were enriched in Na and depleted in Fe (Na-TOR type). The most enriched basalts are typical of the earlier stages of the opening and were found on the flanks of the ridge in its northernmost part. Variations in the ratios of Sr, Nd, and Pb isotopes and lithophile elements allowed us to conclude that the primary melts generated beneath the spreading zone of the Knipovich Ridge were modified by the addition of the enriched component that was present both in the Neogene and Quaternary basalts of Spitsbergen Island. Compared with the primitive mantle, the extruding magmas were characterized by positive Nb and Zr anomalies and a negative Th anomaly. The formation of primary melts involved melting of the metasomatized depleted mantle reservoir that appeared during the early stages of opening of the Norwegian-Greenland Basin and transformation of the paleo-Spitsbergen Fault into the Knipovich spreading ridge, which was accompanied by magmatism in western Spitsbergen during its separation from the northern part of Greenland.

Ages and stable isotope ratios from speleothem calcite from Cold Water Cave, Iowa

High-precision uranium-thorium mass spectrometric chronology and 18O-13C isotopic analysis of speleothem calcite from Cold Water Cave in northeast Iowa have been used to chart mid-Holocene climate change. Significant shifts in d18O and d13C isotopic values coincide with well-documented Holocene vegetation changes. Temperature estimates based on 18O/16O ratios suggest that the climate warmed rapidly by about 3°C at 5900 years before present and then cooled by 4°C at 3600 years before present. Initiation of a gradual increase in ?d13C at 5900 years before present suggests that turnover of the forest soil biomass was slow and that equilibrium with prairie vegetation was not attained by 3600 years before present.

Hydrocarbons in hydrothermal sulfides from the Rainbow Hydrothermal Field

The Rainbow Hydrothermal Field (36°N, Mid-Atlantic Ridge) is one of three presently known fields related to serpentinization of ultramafic rocks accompanied by formation of hydrogen- and methane rich solutions. Gas chromatographic and molecular gas chromatographic - mass spectrometric investigations of sulfide ores and sediments from this field confirmed predominantly biological nature of bitumoids related to high-temperature transformation of biomass of the hydrothermal biological community. At the same time ores of the Rainbow field contain significant amounts of compounds that are not directly related to biogenic synthesis. This fact suggests possibility of abiogenic synthesis of methane and even complex hydrocarbons during serpentinization of ultramafic rocks.

Non-isoprenoidal intact polar lipids, isoprenoidal and non-isoprenoidal core lipids, isoprenoidal intact polar lipids of the Black Sea site GeoB15105 sampled during Meteor cruise M84/1 in February 2011

This PhD thesis focused on the analysis and application of microbial membrane lipids as biomarkers in marine sediments. Existing protocols for lipid extraction from marine sediments and biomass were modified. In addition, recent protocols based on high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS) as well as state-of-the-art mass spectrometric analysis by quadrupole time-of-flight (MSqTOF) and the triple quadrupole (MSQQQ) mass spectrometer were used to investigate matrix effects and evaluate the reliability of quantitative analysis in marine environmental samples. The improved lipid extraction and quantification were used to analyze Black Sea water column and sediments samples to a depth of 8 meters from site GeoB 15105 taken during cruise M84/1 (DARCSEAS) with R/V Meteor to apply lipid analysis in benthic bio systems. With this component specific differentiation between planktonic and benthic lipid signature we assessed possible lipid sources. Here, this high detail lipid fingerprinting allowed us to observe changes in the head group and lipid core structures of the intact polar lipids according to the geochemical zonation.

Minerals and geochemistry abundance and occurance, as well as K-Ar determinations for DSDP Site 92-597 basalts

Preliminary studies of hydrothermally altered massive basalts formed at the fast-spreading Mendoza Rise and recovered from DSDP Holes 597B and 597C indicate the presence of three secondary mineral assemblages which formed in the following order: (1) trioctahedral chlorite and talc, (2) goethite and smectite, and (3) calcite and celadonite. The sequential precipitation of these mineral assemblages denotes high water:rock ratios and time-varying conditions of temperature (early >200°C to late <30°C) and state of oxidation (early nonoxidative to late oxidative). A decrease in the relative proportion of oxidative mineral assemblages with depth to 70 m in Site 597 basement indicates a zone of oxidative alteration that became shallower with time as the deeper, more constricted fracture systems were filled by secondary mineralization. In this report we present the first results of the K-Ar dating of celadonite formation age; celadonite formation reflects end-stage hydrothermal alteration in Site 597 basement. Three celadonite dates obtained from Site 597 samples include 13.1 ± 0.3 m.y. from 17 m basement depth (Hole 597B), 19.9 ± 0.4 m.y. from 18 m basement depth (Hole 597C), and 19.3 ± 1.6 m.y. from 60 m basement depth (Hole 597C). The age of host rock crystallization (28.6 m.y.) and the K-Ar dates of celadonite formation establish that hydrothermal alteration in the upper 70 m of Site 597 basement continued for at least 10 m.y. and possibly as long as 16 m.y. after basalt crystallization at the ridge crest. Assuming a half-spreading rate of 55 km/m.y., we calculate that hydrothermal circulation was active in shallow basement at a distance of at least 550 km off ridge crest and possibly as far as 1000 km off ridge crest.

Physical properties and geochemistry at DSDP Leg 70 Holes

Ashes occurring both as distinct layers and mixed with pelagic sediments of the hydrothermal mounds lying south of the Galapagos Rift are mainly rhyolitic and basaltic. The ashes, of rhyolitic to intermediate composition, appear to belong to a calc-alkalic series and were probably derived from Plinian eruptions in Ecuador or Colombia. Basaltic ashes are made of nonvesicular sideromelane spalling shards and are of tholeiitic composition. They probably were derived locally from fault scarps. Most rhyolitic and basaltic glass shards studied are fresh except for hydration of the rhyolitic shards. Some shards are severely altered, however. Basaltic ash may be more common in pelagic sediments deposited near accretion zones and may be a source of silica and other elements released during diagenesis

Metallic Fluence Monitors and J-value standards

Utilizing the neutron-irradiation parameter J is one of the major uncertainties in 40Ar/39Ar dating. The associated error of the individual J-value for a sample of unknown age depends on the accuracy of the age of the geological standards, the fast-neutron fluence distribution in the reactor and the distances between standards and samples during irradiation. While it is generally assumed that rotating irradiation evens out radial neutron fluence gradients, we observed axial and radial variations of the J-values in sample irradiations in the rotating channels of two reactors. To quantify them, we included three-dimensionally distributed metallic fast- (Ni) and thermal- (Co) neutron fluence monitors in three irradiations and geological age standards in three more. Two irradiations were carried out under Cd-shielding in the FRG1 reactor in Geesthacht, Germany, and four without Cd-shielding in the LVR-15 reactor in Rez, Czech Republic. The 58Ni(nf,p)58Co activation reaction and ?-spectrometry of the 811 keV peak associated with the subsequent decay of 58Co to 58Fe allow to calculate the fast-neutron fluence. The fast-neutron fluences at known positions in the irradiation container correlate with the J-values determined by mass-spectrometric 40Ar/39Ar measurements of the geological age standards. Ra-dial neutron fluence gradients are up to 1.8 %/cm in FRG1 and up to 2.2 %/cm in LVR-15; the corre-sponding axial gradients are up to 5.9 and 2.1 %/cm. We conclude that sample rotation might not al-ways suffice to meet the needs of high-precision dating and gradient monitoring can be crucial.