212 resultados para capillary gas chromatography-mass spectrometric detection with selective ion monitoring


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The ocean off NW Africa is the second most important coastal upwelling system with a total annual primary production of 0.33 Gt of carbon per year (Carr in Deep Sea Res II 49:59-80, 2002). Deep ocean organic carbon fluxes measured by sediment traps are also fairly high despite low biogenic opal fluxes. Due to a low supply of dissolved silicate from subsurface waters, the ocean off NW Africa is characterized by predominantly carbonate-secreting primary producers, i.e. coccolithophorids. These algae which are key primary producers since millions of years are found in organic- and chlorophyll-rich zooplankton fecal pellets, which sink rapidly through the water column within a few days. Particle flux studies in the Mauretanian upwelling area (Cape Blanc) confirm the hypothesis of Armstrong et al. (Deep Sea Res II 49:219-236, 2002) who proposed that ballast availability, e.g. of carbonate particles, is essential to predict deep ocean organic carbon fluxes. The role of dust as ballast mineral for organic carbon, however, must be also taken into consideration in the coastal settings off NW Africa. There, high settling rates of larger particles approach 400 m day**-1, which may be due to a particular composition of mineral ballast. An assessment of particle settling rates from opal-production systems in the Southern Ocean of the Atlantic Sector, in contrast, provides lower values, consistent with the assumptions of Francois et al. (Global Biogeochem Cycles 16(4):1087, 2002). Satellite chlorophyll distributions, particle distributions and fluxes in the water column off NW Africa as well as modelling studies suggest a significant lateral flux component and export of particles from coastal shelf waters into the open ocean. These transport processes have implications for paleo-reconstructions from sediment cores retrieved at continental margin settings.

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Although long-range atmospheric transport has been described as the predominant mechanism for exposing polar regions to persistent organic pollutants (POPs), recent studies have suggested that bird activity can also contribute substantially to contaminant levels in some environments. However, because the species so far reported have all been migratory, it has not been demonstrated conclusively whether locally elevated contamination represents transport from lower latitudes by the migrating birds or, alternatively, redistribution and concentration of contaminants that were already present in the high-latitude environments. The present study demonstrates, for the first time, that several POPs are present in elevated concentrations in an environment frequented by a non-migratory species (Adelie penguins) that spends its entire life in the Antarctic. Levels of POPs, such as p,p'-DDE, hexachlorobenzene (HCB), chlordanes (CHLs) and polychlorinated biphenyls (PCBs), were 10 to 100-fold higher in soil samples from penguin colonies than from reference areas. This significant difference is likely related to local penguin activity, such as a higher abundance of guano and the presence of bird carcasses. This hypothesis is also supported by a higher percentage of persistent congeners (PCB 99, 118, 138 and 153) in the soil from the colonies compared to the reference areas. This profile of PCB congeners closely matched profiles seen in penguin eggs or penguin blood.

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Methyl iodide (CH3I), bromoform (CHBr3) and dibromomethane (CH2Br2), which are produced naturally in the oceans, take part in ozone chemistry both in the troposphere and the stratosphere. The significance of oceanic upwelling regions for emissions of these trace gases in the global context is still uncertain although they have been identified as important source regions. To better quantify the role of upwelling areas in current and future climate, this paper analyzes major factors that influenced halocarbon emissions from the tropical North East Atlantic including the Mauritanian upwelling during the DRIVE expedition. Diel and regional variability of oceanic and atmospheric CH3I, CHBr3 and CH2Br2 was determined along with biological and meteorological parameters at six 24 h-stations. Low oceanic concentrations of CH3I from 0.1-5.4 pmol/L were equally distributed throughout the investigation area. CHBr3 of 1.0-42.4 pmol/L and CH2Br2 of 1.0-9.4 pmol/L were measured with maximum concentrations close to the Mauritanian coast. Atmospheric mixing rations of CH3I of up to 3.3, CHBr3 to 8.9 and CH2Br2 to 3.1 ppt above the upwelling and 1.8, 12.8, respectively 2.2 ppt at a Cape Verdean coast were detected during the campaign. While diel variability in CH3I emissions could be mainly ascribed to oceanic non-biological production, no main driver was identified for its emissions in the entire study region. In contrast, oceanic bromocarbons resulted from biogenic sources which were identified as regional drivers of their sea-to-air fluxes. The diel impact of wind speed on bromocarbon emissions increased with decreasing distance to the coast. The height of the marine atmospheric boundary layer (MABL) was determined as an additional factor influencing halocarbon emissions. Oceanic and atmospheric halocarbons correlated well in the study region and in combination with high oceanic CH3I, CHBr3 and CH2Br2 concentrations, local hot spots of atmospheric halocarbons could solely be explained by marine sources. This conclusion is in contrast with previous studies that hypothesized the occurrence of elevated atmospheric halocarbons over the eastern tropical Atlantic mainly originating from the West-African continent.

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Sediments of upwelling regions off Namibia, Peru, and Chile contain dense populations of large nitrate-storing sulfide-oxidizing bacteria, Thiomargarita, Beggiatoa, and Thioploca. Increased contents of monounsaturated C16 and C18 fatty acids have been found at all stations studied, especially when a high density of sulfide oxidizers in the sediments was observed. The distribution of lipid biomarkers attributed to sulfate reducers (10MeC16:0 fatty acid, ai-C15:0 fatty acid, and mono-O-alkyl glycerol ethers) compared to the distribution of sulfide oxidizers indicate a close association between these bacteria. As a consequence, the distributions of sulfate reducers in sediments of Namibia, Peru, and Chile are closely related to differences in the motility of the various sulfide oxidizers at the three study sites. Depth profiles of mono-O-alkyl glycerol ethers have been found to correlate best with the occurrence of large sulfide-oxidizing bacteria. This suggests a particularly close link between mono-O-alkyl glycerol ether-synthesizing sulfate reducers and sulfide oxidizers. The interaction between sulfide-oxidizing bacteria and sulfate-reducing bacteria reveals intense sulfur cycling and degradation of organic matter in different sediment depths.

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Optimum conditions were selected for chromatographic separation of model mixtures of C12-C40 n-alkanes. For one of samples of hydrothermal deposits extraction conditions of hydrocarbons were studied and a sample preparation procedure was selected. The procedure was proposed to determine n-alkanes in samples of hydrothermal deposits by means of gas chromatography - mass spectrometry (GC-MS). Detection limit for n-alkanes was 3x10**-9 to 10**-8% depending on components. On the basis of the proposed procedure composition of n-alkanes was studied in samples of hydrothermal deposits collected at the Mid-Atlantic Ridge (Broken Spur, Lost City, and Rainbow hydrothermal fields). Analyses showed that samples contained C14-C35 n-alkanes. Concentrations of the n-alkanes were rather low and varied from 0.002 to 0.038 µg/g. Hypotheses concerning genesis of identified n-alkanes were offered.

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First videographic indication of an Antarctic cold seep ecosystem was recently obtained from the collapsed Larsen B ice shelf, western Weddell Sea (Domack et al., 2005). Within the framework of the R/V Polarstern expedition ANTXXIII-8, we revisited this area for geochemical, microbiological and further videographical examinations. During two dives with ROV Cherokee (MARUM, Bremen), several bivalve shell agglomerations of the seep-associated, chemosynthetic clam Calyptogena sp. were found in the trough of the Crane and Evans glacier. The absence of living clam specimens indicates that the flux of sulphide and hence the seepage activity is diminished at present. This impression was further substantiated by our geochemical observations. Concentrations of thermogenic methane were moderately elevated with 2 µM in surface sediments of a clam patch, increasing up to 9 µM at a sediment depth of about 1 m in the bottom sections of the sediment cores. This correlated with a moderate decrease in sulphate from about 28 mM at the surface down to 23.4 mM, an increase in sulphide to up to 1.43 mM and elevated rates of the anaerobic oxidation of methane (AOM) of up to 600 pmol cm**-3 d**-1 at about 1 m below the seafloor. Molecular analyses indicate that methanotrophic archaea related to ANME-3 are the most likely candidates mediating AOM in sediments of the Larsen B seep.

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The solvent-extractable organic fractions of sediment samples from six Ocean Drilling Program Leg 117 sites were investigated by gas chromatography and gas chromatography-mass spectrometry. Sediments deposited in the Indus Fan (Site 720) as well as Miocene sediments from the Owen Ridge (Sites 722 and 731) contain almost exclusively organic matter of terrigenous origin. The organic matter in sediments from the Oman Margin (Sites 723, 725, and 728) and in the Pliocene/Pleistocene sections from the Owen Ridge is mainly of a marine origin with variable admixtures of terrigenous material. In these latter samples strong variations of the lipid composition and distribution are noted. However, the interpretation of the relation to potential biological sources is hampered by a lack of information on the possible lipid composition of appropriate organisms.

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The amount, type, and thermal maturation of organic matter in sediments from two DSDP holes in the South Atlantic (Leg 72) were investigated. Isolated kerogens were studied by microscopy, and nonaromatic hydrocarbons were characterized by capillary gas chromatography. Organic carbon values are low in all samples and range between 0.05 and 0.21% in Hole 515B (Brazil Basin) and only between 0.02 and 0.10% in Hole 516F (Rio Grande Rise). The organic matter is predominantly terrigenous, mixed with some unicellular marine algae; it is severely oxidized in most samples. N-alkane distributions are usually dominated by long-chain wax alkanes with odd-over-even carbon number predominance; when the marine organic matter is relatively more abundant, however, significant amounts of n-alkanes are centered upon n-C17. The organic matter is not mature enough in any sample to generate appreciable amounts of hydrocarbons.

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Twenty-four sediment samples from DSDP Holes 605 (Leg 93) and 613 (Leg 95) on the New Jersey continental rise were analyzed by pyrolysis-gas chromatography. Twelve of these samples were also analyzed by pyrolysis-gas chromatography/mass spectrometry. The degree of preservation of sediment organic matter, as determined by these techniques, helped to distinguish slumped sediments from sediments that have not moved from their original place of deposition. Total levels of pyrolyzable organic material, as determined from pyrolysis-gas chromatography, were low in sediments that were not slumped, indicating that the organic material is highly degraded. Nitrogen- and oxygen-containing compounds were the primary compounds detected by gas chromatography/mass spectrometry (GCMS) analysis of the pyrolyzate of non-slumped sediments. Smaller amounts of aromatic compounds and branched alkanes were also present in some of these samples. In contrast, slumped sediments showed larger amounts of pyrolyzable organic matter, as determined from pyrolysis-gas chromatography, and better preservation of alkyl chains in the sediment organic matter, as suggested by the presence of n-alkanes in GCMS analysis of the pyrolyzate. Better preservation of the organic matter in slumped sediments can be attributed to more moderate bioturbation by bottom-dwelling organisms at the original deposition site.

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During the past decades, remarkable changes in sea-surface temperature (SST) and sea-ice extent have been observed in the marginal seas of the subarctic Pacific. However, little is known about natural climate variability at millennial time scales far beyond instrumental observations. Geological proxy records, such as those derived from marine sediments, offer a unique opportunity to investigate millennial-scale natural climate variability of the Artic and subarctic environments during past glacial-interglacial cycles. Here we provide reconstructions of sea-ice variability inferred from IP25 (Ice Proxy with 25 carbon atoms) sea-ice biomarker and SST fluctuations based on alkenone unsaturation index (UK'37) of the subarctic Pacific realm between 138 and 70 ka. Warmest sea-surface conditions were found during the early Eemian interglacial (128 to 126 ka), exceeding modern SSTs by ~2 °C. The further North Pacific climate evolu- tion is marked by pronounced oscillations in SST and sea-ice extent on millennial time scales, which correspond remarkably well to short-term temperature oscillations known from Green- land and the North Atlantic. These results imply a common forcing, which seems to be closely coupled to dynamics of the Atlantic meridional overturning circulation. However, immediate propagation of such climate fluctuations far beyond the North Atlantic basin suggests a rapid circumpolar coupling mechanism probably acting through the atmosphere, a prerequisite to explain the apparent synchronicity of remote climatic reorganizations in the subarctic Pacific.

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