Intercomparison of Two Hydroxyl Radical Measurement Techniques at the Atmosphere Simulation Chamber SAPHIR     

Eric Schlosser  Birger Bohn  Theo Brauers  Hans-Peter Dorn  Hendrik Fuchs  Rolf Häseler  Andreas Hofzumahaus  Frank Holland  Franz Rohrer  Lutz Olaf Rupp  Manfred Siese  Ralf Tillmann  Andreas Wahner 《Journal of Atmospheric Chemistry》2007,56(2):187-205

At the atmosphere simulation chamber SAPHIR in Jülich both Laser-Induced Fluorescence Spectroscopy (LIF) and Long-Path Differential Optical Laser Absorption Spectroscopy (DOAS) are operational for the detection of OH radicals at tropospheric levels. The two different spectroscopic techniques were compared within the controlled environment of SAPHIR based on all simultaneous measurements acquired in 2003 (13 days). Hydroxyl radicals were scavenged by added CO during four of these days in order to experimentally check the calculated precisions at the detection limit. LIF measurements have a higher precision (σ= 0.88×10⁶ cm^–3) and better time resolution (Δt = 60 s), but the DOAS method (σ= 1.24×10⁶ cm^–3, Δt = 135 s) is regarded as primary standard for comparisons because of its good accuracy. A high correlation coefficient of r = 0.95 was found for the whole data set highlighting the advantage of using a simulation chamber. The data set consists of two groups. The first one includes 3 days, where the LIF measurements yield (1 – 2) ×10⁶ cm^–3 higher OH concentrations than observed by the DOAS instrument. The experimental conditions during these days are characterized by increased NO_x concentration and a small dynamic range in OH. Excellent agreement is found within the other group of 6 days. The regression to the combined data of this large group yields unity slope without a significant offset.  相似文献   

Assessing the reliability of the modified three-component spatial autocorrelation technique   总被引：3，自引：0，他引：3  

Andreas Köhler  Matthias Ohrnberger  Frank Scherbaum  Marc Wathelet  Cecile Cornou 《Geophysical Journal International》2007,168(2):779-796

  相似文献   

Phytoplankton response to climate changes in Lake Baikal during the Holocene and Kazantsevo Interglacials assessed from sedimentary pigments     

Susanne Fietz  Andreas Nicklisch  Hedi Oberhänsli 《Journal of Paleolimnology》2007,37(2):177-203

Lake Baikal, an ancient pristine lake in Siberia, has accumulated sediment deposits that span 25 million years. These deposits have the potential to provide a long-term record of climate changes and their interaction with the ecology of the lake. In order to investigate whether sedimentary phytoplankton pigments could be used to reconstruct past changes in total phytoplankton abundance and productivity, we compared the spatial variability in sedimentary pigment distributions in Holocene cores from three separate regions of the lake; Vidrino in the south, Posolski on Selenga Delta and Continent Ridge in the north. Furthermore, we present the first continuous sedimentary pigment and organic carbon sequence of the Kazantsevo interglacial (roughly a time equivalent to the European Eemian, and Marine Isotopic Stage MIS5e) at a resolution of approximately 150 years. Results of the spatial study showed marked differences in the sediment pigment deposition. Lowest chlorophyll a plus its degradation products versus organic carbon ratios (Chlas/TOC) indicating lowest production, but highest variability with time (indicating strongest climatic oscillations) were found at Continent Ridge. The study of sedimentary pigments deposited during the last two interglacial periods at Continent Ridge showed Chlas/TOC ratios 50–1000 times higher during the Kazantsevo Interglacial compared to the glacial periods, whereas the TOC content was only five times higher, thus indicating the significance of the Chlas/TOC ratio for the reconstruction of the phytoplankton abundance and productivity. Strong oscillations occurred during the Kazantsevo Interglacial within centennial time scales. Chlorophyllb plus its degradation products provided additional information on the past development of Chlorophyceae. Highest Chlas/TOC ratios were found during the early Holocene at approximately 9 kyr BP. Indications of short phytoplankton production maxima were also found during the late Atlantic (6 kyr BP) and at the Subboreal/Subatlantic transition (3 kyr BP). From this we conclude that sedimentary chlorophyll a is a reliable indicator of phytoplanktonic response to climate changes and may serve for␣validation of future climate scenarios in continental regions.  相似文献   

Long cores from small lakes—recovering up to 100 m-long lake sediment sequences with a high-precision rod-operated piston corer (Usinger-corer)     

Jens Mingram  Jörg F. W. Negendank  Achim Brauer  Dieter Berger  Andreas Hendrich  Michael Köhler  Hartmut Usinger 《Journal of Paleolimnology》2007,37(4):517-528

We present a unique, versatile piston corer for recovering continuous lake and bog sediment sequences with superior accuracy and quality. The main components of the system and their function are described, with special focus on measures for obtaining long, continuous lake sediment sections up to a current maximum length of 95 m. Examples of lake sediment profiles obtained with this system from different climatic zones are presented.  相似文献   

Methane and carbon dioxide adsorption–diffusion experiments on coal: upscaling and modeling     

Andreas Busch  Yves Gensterblum  Bernhard M. Krooss  Ralf Littke 《International Journal of Coal Geology》2004,60(2-4):151-168

Numerical modelling of the processes of CO₂ storage in coal and enhanced coalbed methane (ECBM) production requires information on the kinetics of adsorption and desorption processes. In order to address this issue, the sorption kinetics of CO₂ and CH₄ were studied on a high volatile bituminous Pennsylvanian (Upper Carboniferous) coal (VR_r=0.68%) from the Upper Silesian Basin of Poland in the dry and moisture-equilibrated states. The experiments were conducted on six different grain size fractions, ranging from <0.063 to 3 mm at temperatures of 45 and 32 °C, using a volumetric experimental setup. CO₂ sorption was consistently faster than CH₄ sorption under all experimental conditions. For moist coals, sorption rates of both gases were reduced by a factor of more than 2 with respect to dry coals and the sorption rate was found to be positively correlated with temperature. Generally, adsorption rates decreased with increasing grain size for all experimental conditions.Based on the experimental results, simple bidisperse modelling approaches are proposed for the sorption kinetics of CO₂ and CH₄ that may be readily implemented into reservoir simulators. These approaches consider the combination of two first-order reactions and provide, in contrast to the unipore model, a perfect fit of the experimental pressure decay curves. The results of this modeling approach show that the experimental data can be interpreted in terms of a fast and a slow sorption process. Half-life sorption times as well as the percentage of sorption capacity attributed to each of the two individual steps have been calculated.Further, it was shown that an upscaling of the experimental and modelling results for CO₂ and CH₄ can be achieved by performing experiments on different grain size fractions under the same experimental conditions.In addition to the sorption kinetics, sorption isotherms of the samples with different grain size fractions have been related to the variations in ash and maceral composition of the different grain size fractions.  相似文献   

Determination of bioavailable Fe(III) content in column experiments with the reactive tracer phosphate     

Frank Dethlefsen  Rainer Meckenstock  Malte K. Veehmayer  Andreas Dahmke 《Environmental Geology》2004,46(6-7):896-904

Different methods were compared to evaluate the oxidation capacity of ferric iron in column studies. The specific adsorption of the reactive tracer phosphate on the Fe(III) oxide surface was used as an alternative approach to determine the oxidation capacity utilizing the linear correlation between the long-term extent of Fe(III) reduction and the specific surface area of the oxide. Although a low crystalline form of ferric iron (two-line ferrihydrite) was used as electron acceptor and toluene as a carbon source, only 31 and 24% respectively of the total iron was reduced by Geobacter metallireducens in parallel experiments. The results of the phosphate tracer tests were in good agreement with the Fe(III) that was actually reduced and the microbially oxidized toluene. The oxidation capacity of ferric iron is therefore overestimated by the chemical extraction methods, which completely dissolve the ferrihydrite and neglect surface-dependent limitations.  相似文献   

Formation of Fe(III)-minerals by Fe(II)-oxidizing photoautotrophic bacteria     

Andreas Kappler 《Geochimica et cosmochimica acta》2004,68(6):1217-1226

It has been suggested that Fe(II)-oxidizing photoautotrophic bacteria may have catalyzed the precipitation of an ancient class of sedimentary deposits known as Banded Iron Formations. In order to evaluate this claim, it is necessary to define and understand this process at a molecular level so that putative Fe-isotope “biosignatures” in ancient rocks can be interpreted. In this report, we characterize the substrates and products of photoautotrophic Fe(II)-oxidation by three phylogenetically distinct Fe(II)-oxidizing bacteria. In every case, dissolved Fe(II) is used as the substrate for oxidation, and there is no evidence for active dissolution of poorly soluble Fe(II)-minerals by biogenic organic ligands. Poorly crystalline Fe(III) (hydr)oxide mineral phases are initially precipitated, and as they age, rapidly convert to the crystalline minerals goethite and lepidocrocite. Although the precipitates appear to associate with the cell wall, they do not cover it entirely, and precipitate-free cells represent a significant portion of the population in aged cultures. Citrate is occasionally detected at nanomolar concentrations in all culture fluids, whereas an unknown organic molecule is always present in two out of the three bacterial cultures. Whether these molecules are released by the cell to bind Fe(III) and prevent the cell from encrustation by Fe(III) (hydr)oxides is uncertain, but seems unlikely if we assume Fe(II)-oxidation occurs at the cell surface. In light of the energetic requirement the cell would face to produce ligands for this purpose, and given the local acidity metabolically generated in the microenvironment surrounding Fe(II)-oxidizing cells, our results suggest that Fe(III) is released in a dissolved form as an inorganic aqueous complex and/or as a colloidal aggregate prior to mineral precipitation. The implication of these results for the interpretation of Fe-isotope fractionation measured for this class of bacteria (Croal et al., 2004) is that equilibrium processes involving free biological ligands do not account for the observed fractionation.  相似文献   

On the Exchange of NO3 Radicals with Aqueous Solutions: Solubility and Sticking Coefficient     

Karin Thomas  Andreas Volz-Thomas  Djuro Mihelcic  Herman G. J. Smit  Dieter Kley 《Journal of Atmospheric Chemistry》1998,29(1):17-43

The exchange of NO₃ radicals with the aqueous-phase was investigated at room temperature (293 K) in a series of wetted denuders. From these experiments, the uptake coefficient of NO₃ was determined on 0.1 M NaCl solutions and was found to be (NO₃) 2 × 10^-3 in good agreement with recent studies. The Henry coefficient of NO₃ was estimated to be K_H(NO₃) = 1.8 M · atm^-1, with a (2) uncertainty of ±3 M · atm^-1. From the upper limit for the Henry coefficient (K_H = 5 M · atm^-1) and available thermodynamic data, the redox potential of dissolved NO₃/NO ₃ ^– is estimated to be in the range of 2.3 to 2.5 V. This range is at the lower boundary of earlier estimates. The results are discussed in the light of a recent publication. Based on our data and a model of the transport and chemistry in the liquid film, an upper limit is derived for the product of the Henry coefficient K_H and the rate coefficient k ₁₀ of the potential reaction NO₃ + H₂O HNO₃ + OH. For K_H = 0.6 M · atm^-1, we find k ₁₀ < 0.05 s^-1 · atm^-1, i.e., about 100 times smaller than what was suggested by Rudich and co-workers. Because of its small solubility, heterogeneous removal of NO₃ is only important under conditions where the dissolved NO₃ is removed quickly from equilibrium, for example by reactions with Cl^– or HSO ₃ ^– ions in the liquid-phase. Otherwise, heterogenous removal should mainly proceed via N₂O₅.  相似文献   

Rifting-related volcanism in an oceanic post-collisional setting: the Tabar–Lihir–Tanga–Feni (TLTF) island chain, Papua New Guinea     

Andreas Stracke  Ernst Hegner 《Lithos》1998,45(1-4):545-560

The Tabar–Lihir–Tanga–Feni (TLTF) volcanic island chain occurs in a zone of lithospheric extension superimposed on a post-collisonal tectonic setting along the Pacific and Indo-Australian plates northeast of Papua New Guinea. We present geochemical and Sr, Nd, and Pb isotope data for volcanic rocks from these islands and three recently discovered seamounts located at Lihir island. Major element data document an alkalic affinity of the sample suite and trachybasalts as the predominant rock type. Negative Nb-anomalies in extended trace element patterns, enrichment of the light rare earth elements, and Ce/Pb ratios of about 4 are typical of the values in calc alkaline island arc volcanics and support an origin from subduction-modified mantle. ⁸⁷Sr/⁸⁶Sr ratios of 0.7037 to 0.7044 and _Nd values of +5.6 to +6.8 indicate that the upper mantle evolved with a time-integrated depletion in LREE, however, not as severe as that recorded in basalts from the East Pacific Rise. Variable ⁸⁷Sr/⁸⁶Sr ratios at less variable ¹⁴³Nd/¹⁴⁴Nd ratios suggest that ⁸⁷Sr/⁸⁶Sr ratios of the melts were modified by secondary processes, such as assimilation of seawater Sr from crustal rocks. The Pb isotope ratios are uniform, moderately radiogenic (²⁰⁶Pb/²⁰⁴Pb ca. 18.7 to 18.8), and similar to those reported for the active Mariana arc. Elevated ²⁰⁷Pb/²⁰⁴Pb ratios relative to Pacific MORB suggest melting of small amounts of subducted sediments (ca. 1–2 wt.%). An important control of subducted sediment on the chemistry of the melts can also be inferred from the ratios of highly incompatible trace elements (e.g., Th, U, Pb, La, and Nb). Additional mantle enrichment by subduction derived fluids is reflected in high values of highly incompatible trace element ratios between fluid mobile (e.g., Ba) and fluid immobile elements (e.g., Th, Nb). The results of this study document that the chemical composition of igneous rocks from post-collisional tectonic settings are strongly influenced by previous plate tectonics. This conclusion implies that the information conveyed by tectonic discrimination diagrams for these rocks must be interpreted with care.  相似文献   

Crustal residence history and garnet Sm–Nd ages of high-grade metamorphic rocks from the Windmill Islands area,East Antarctica     

Andreas Möller  Nicholas J. Post  Bas J. Hensen 《International Journal of Earth Sciences》2002,91(6):993-1004

Nd whole-rock data from the Windmill Islands area yield early Proterozoic to middle Archaean Nd model ages. These crustal residence times are consistent with regional correlations with other parts of Antarctica (Bunger Hills, Denman Glacier area) and the Albany-Fraser Orogen of south-western Australia during the Mid-Proterozoic and thus support reconstructions with a continuous Mid-Proterozoic orogen in these areas. The new Nd isotope data provide strong evidence that no age boundary exists between the higher- and lower-grade parts of the Windmill Islands area, and that the metamorphic complex represents a single terrane with a common crustal history. The data support the notion of a time-link between the occurrence of intrusive charnockites (C-type magmas) and high-grade metamorphism. The magmatic rocks and orthogneisses in the area are interpreted to have a mixed source consisting of older crustal components, i.e. older sediments (ca. 3.2-2.6 Ga) and a younger mafic component (ca. 1.9 Ga). Two garnet Sm-Nd isochrons yield ages of 1156ᆥ Ma and 1137DŽ.5 Ma and are identical to SHRIMP U-Pb results on monazite from these samples. A garnet Sm-Nd age of 1123ᆡ Ma for the Ford granite is significantly younger than the SHRIMP U-Pb zircon age for this sample. The difference relates to the different closure temperature of each isotopic system and is thus interpreted as initial cooling after granulite facies metamorphism.  相似文献