Measurements of peroxyacetylnitrate in the marine boundary layer over the Atlantic

The atmospheric concentration of peroxyacetylnitrate (PAN) was measured during a cruise of the R.S. Polarstern from Bremerhaven (Germany) to Rio Grande do Sul (Brazil) in September/ October 1988. The measurements were made in-situ by a combination of electron capture gaschromatography with a cryogenic preconcentration step. The theoretical lower limit of detection (3) was 0.4 ppt. The mixing ratios of PAN varied by more than three orders of magnitude from 2000 ppt in the English Channel to less than 0.4 ppt south of the Azores (38° N). South of 35° N, PAN levels were below the detection limit, except at 30–31° S off the eastern coast of South America. Here, PAN mixing ratios of 10 to 100 ppt were detected in continentally influenced air masses. Detectable levels of PAN were mostly observed in air masses of continental or high northern origin. Changes in the wind directions were usually associated with substantial changes in the PAN mixing ratios.     

Web-cam’s potential for collaborative activities in the Earth sciences

We report here our experiences from using easily acquired web-cam components for collaborative ventures in the Earth sciences. We have used a variety of hardware and different software. We demonstrate from various locations in the U.S.A. the feasibility of using web-cam in multitudinous activities, relevant for conducting research and knowledge dissemination. We summarize the quality of the connections from the various combinations of communicating parties. Today, web-cams can be utilized as an economical and viable means of point-to-point communication in the Earth science community. Greater bandwidth is sorely needed for activities such as multi-party conferencing on the present internet network. We propose that web-cam can be readily deployed as a web-service for facilitating collaborative research over the GRID infrastructure, using the middleware Narada-Brokering. Web-cam will play an important role in the emerging field of geoinformatics.     

Sulfur isotope fractionation during growth of sulfate-reducing bacteria on various carbon sources

Stable sulfur isotope fractionation during microbial sulfate reduction is a potential tool to estimate sulfate reduction rates at field sites. However, little is known about the influence of the utilized carbon source on the magnitude of sulfur isotope fractionation. To investigate this effect, both a pure culture (strain PRTOL1) and enrichment cultures from a petroleum hydrocarbon (PHC)-contaminated aquifer were used and grown in batch cultures on various carbon sources with an initial sulfate concentration of 1 mmol/L. As sole carbon sources the PHC components naphthalene, 1,3,5-trimethylbenzene, and heating oil (enrichment culture) and the organic acids acetate, pyruvate, benzoate, and 3-phenylpropionate (enrichment culture and PRTOL1) were used. Sulfate reduction rates of all cultures ranged from 6 ± 1 nmol cm⁻³ d⁻¹ (enrichment culture grown on 1,3,5-trimethylbenzene) to 280 ± 6 nmol cm⁻³ d⁻¹ (enrichment culture grown on pyruvate). Cell-specific sulfate reduction rates ranged from 1.1 × 10⁻¹⁴ mol cell⁻¹ d⁻¹ (PRTOL1 grown on pyruvate) to 1.5 × 10⁻¹³ mol cell⁻¹ d⁻¹ (PRTOL1 grown on acetate). Sulfur isotope enrichment factors (ε) for the enrichment culture ranged from 16.1‰ (3-phenylpropionate) to 34.5‰ (1,3,5-trimethylbenzene) and for PRTOL1 from 30.0‰ (benzoate) to 36.0‰ (pyruvate). Cultures of PRTOL1 always showed higher ε values than the enrichment culture when grown on the same carbon source due to culture-specific properties. Higher ε values were obtained when the enrichment culture was grown on PHC components than on organic acids. No relationship between ε values and cell-specific sulfate reduction rate existed when all data were combined. When comparing the magnitude of ε values determined in this laboratory study with ε values measured at contaminated and uncontaminated field sites, it becomes evident that a multitude of factors influences ε values at field sites and complicates their interpretation. The results of this study help us assess some of the general parameters that govern the magnitude of ε in sulfate-reducing environments.     

A model for oxygen and sulfur isotope fractionation in sulfate during bacterial sulfate reduction processes

We present a model of bacterial sulfate reduction that includes equations describing the fractionation relationship between the sulfur and the oxygen isotope composition of residual sulfate (δ³⁴S_{SO4_residual}, δ¹⁸O_{SO4_residual}) and the amount of residual sulfate. The model is based exclusively on oxygen isotope exchange between cell-internal sulfur compounds and ambient water as the dominating mechanism controlling oxygen isotope fractionation processes. We show that our model explains δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} patterns observed from natural environments and from laboratory experiments, whereas other models, favoring kinetic isotope fractionation processes as dominant process, fail to explain many (but not all) observed δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} patterns. Moreover, we show that a “typical” δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} slope does not exist. We postulate that measurements of δ³⁴S_{SO4_residual} and δ¹⁸O_{SO4_residual} can be used as a tool to determine cell-specific sulfate reduction rates, oxygen isotope exchange rates, and equilibrium oxygen isotope exchange factors. Data from culture experiments are used to determine the range of sulfur isotope fractionation factors in which a simplified set of equations can be used. Numerical examples demonstrate the application of the equations. We postulate that, during denitrification, the oxygen isotope effects in residual nitrate are also the result of oxygen isotope exchange with ambient water. Consequently, the equations for the relationship between δ³⁴S_{SO4_residual}, δ¹⁸O_{SO4_residual}, and the amount of residual sulfate could be modified and used to calculate the fractionation-relationship between δ¹⁵N_{NO3_residual}, δ¹⁸O_{NO3_residual}, and the amount of residual nitrate during denitrification.     

Luminescence dating of ice‐marginal deposits in northern Germany: evidence for repeated glaciations during the Middle Pleistocene (MIS 12 to MIS 6)

The exact number, extent and chronology of the Middle Pleistocene Elsterian and Saalian glaciations in northern Central Europe are still controversial. This study presents new luminescence data from Middle Pleistocene ice‐marginal deposits in northern Germany, giving evidence for repeated glaciations during the Middle Pleistocene (MIS 12 to MIS 6). The study area is located in the Leine valley south of the North German Lowlands. The data set includes digital elevation models, high‐resolution shear wave seismic profiles, outcrop and borehole data integrated into a 3D subsurface model to reconstruct the bedrock relief surface. For numerical age determination, we performed luminescence dating on 12 ice‐marginal and two fluvial samples. Luminescence ages of ice‐marginal deposits point to at least two ice advances during MIS 12 and MIS 10 with ages ranging from 461±34 to 421±25 ka and from 376±27 to 337±21 ka. The bedrock relief model and different generations of striations indicate that the older ice advance came from the north and the younger one from the northeast. During rapid ice‐margin retreat, subglacial overdeepenings were filled with glaciolacustrine deposits, partly rich in re‐worked Tertiary lignite and amber. During MIS 8 and MIS 6, the study area may have been affected by two ice advances. Luminescence ages of glaciolacustrine delta deposits point to a deposition during MIS 8 or early MIS 6, and late MIS 6 (250±20 to 161±10 ka). The maximum extent of both the Elsterian (MIS 12 and MIS 10) and Saalian glaciations (MIS 8? and MIS 6) approximately reached the same position in the Leine valley and was probably controlled by the formation of deep proglacial lakes in front of the ice sheets, preventing a further southward advance.     

Characterization of fluid inclusions from mineralized pegmatites of the Damara Belt,Namibia: insight into late-stage fluid evolution and implications for mineralization

Mineralogy and Petrology - Mineralized NYF and LCT pegmatites occur throughout the northeast-trending Neoproterozoic Damara Belt, Namibia. Mineralization in the pegmatites varies geographically,...     

A study of presolar material in hydrated lithic clasts from metal-rich carbonaceous chondrites

We report on the investigation of presolar grain inventories of hydrated lithic clasts in three metal-rich carbonaceous chondrites from the CR clan, Acfer 182 (CH3), Isheyevo (CH3/CB_b3), and Lewis Cliff (LEW) 85332 (C3-un), as well as the carbon- and nitrogen-isotopic compositions of the fine-grained clast material. Eleven presolar silicate grains as well as nine presolar silicon carbide (SiC) grains were identified in the clasts. Presolar silicate abundances range from 4 to 22 parts per million (ppm), significantly lower than in pristine meteorites and interplanetary dust particles (IDP), and comparable to recent findings for CM2s and CR2 interchondrule matrix. SiC concentrations lie between 9 and 23 ppm, and are comparable to the values for CI, CM, and CR chondrites. The results of our investigation suggest similar alteration pathways for the clast material, the interchondrule matrix of the CR2 chondrites, and the fine-grained fraction of CM2 chondrites. Fine-grained matter of all three meteorites contains moderate to high ¹⁵N-enrichments (~50‰ ≤ δ¹⁵N ≤ ~1600‰) compared to the terrestrial value, indicating the presence of primitive organic material. We observed no correlation between ¹⁵N-enrichments and presolar dust concentrations in the clasts. This is in contrast to the findings from a suite of primitive IDPs, which display in several cases enhanced bulk ¹⁵N/¹⁴N ratios and high presolar grain abundances of several hundred or even thousand ppm. The bulk ¹⁵N/¹⁴N ratios of the clasts are comparable to the range for primitive IDPs, suggesting a nitrogen carrier less susceptible to destruction by aqueous alteration than silicate stardust.     

Flow dynamics,sedimentation and erosion of glacial lake outburst floods along the Middle Pleistocene Scandinavian Ice Sheet (northern central Europe)

During the Middle Pleistocene late Saalian glaciation of northern central Europe numerous pro‐glacial lakes formed along the southwestern margin of the Scandinavian Ice Sheet. Little is known about the drainage history of these lakes, the pathways of glacial lake outburst floods and their impacts on erosion, sedimentation and landscape evolution. This study investigated the impact of the late Saalian Weser and Münsterland Lake (Germany) outburst floods. In particular, we reconstructed the routing and flow dynamics of the lake outburst flood and analysed the flood related sediments. We employed one‐dimensional hydraulic modelling to calculate glacial lake outburst flood hydrographs. We modelled the flow pathway and local flow conditions along the pathway based on the boundary conditions of two different hydrographs and two different ice‐margin positions. The modelling results were compared with geomorphological and sedimentological field data in order to estimate the magnitude and impact of the flood on erosion and sedimentation. Two major lake drainage events are reconstructed for the study area, during which approximately 90–50 km³ of water was released. Modelling results indicate that the lake outburst floods created a high‐energy flood wave with a height of 35–50 m in confined valley areas that rapidly spread out into the Lower Rhine Embayment eventually flowing into the North Sea basin. The sedimentary record of the outburst floods comprises poorly sorted coarse‐grained gravel bars, long‐wavelength bedforms and sandy bedforms deposited by supercritical and subcritical flows. Some parts of the sandy flood deposits are rich in reworked mammoth bones or mammoth and horse teeth, pointing to reworking of older fluvial sediments, hydraulic concentration and subsequent re‐sedimentation of vertebrate remains. These deposits are preserved in sheltered areas or at high elevations, well above the influence of postglacial fluvial erosion. The flood‐related erosional features include up to 80‐m‐deep scour pools, alluvial channels and streamlined hills.     

Computational methods for fitting statistical distribution models of multi-site binding equilibria

Statistical distribution models of multi-site binding equilibria have potential applicability in the study of acid-base and metal complexation chemistry of humic substances in soils, sediments, and natural waters. A mathematical derivation is presented for the general continuous model for the case of proton binding; computational methods are described for fitting numerically the parameters in such models. Among models considered are those based on nontruncated, truncated, and bimodal (mixed) distributions. Specific emphasis is placed on Gaussian distribution models.     

Measurements of tropospheric OH concentrations: A comparison of field data with model predictions

Using long path UV absorption spectroscopy we have measured OH concentrations close to the earth's surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×10⁶ to 3.2×10⁶ cm^-3. Simultaneously we measured the concentrations of O₃, H₂O, NO, NO₂, CH₄, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O₃ and NO₂. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NO _x concentrations. It is argued that additional, so far unidentified. HO _x loss reactions must be responsible for that discrepancy.