Modelling nitrogen and oxygen isotope fractionation during denitrification in a lacustrine redox-transition zone

The stable isotope composition (δ¹⁵N and δ¹⁸O) of nitrate was measured during Summer 1999 in the anaerobic hypolimnion of eutrophic Lake Lugano (Switzerland). Denitrification was demonstrated by a progressive nitrate depletion coupled to increasing δ¹⁵N and δ¹⁸O values for residual nitrate. Maximum δ¹⁵N and δ¹⁸O values amounted to 27.2 and 15.7‰, respectively.¹⁵N and ¹⁸O enrichment factors for denitrification (ε) were estimated using a closed-system model and a dynamic diffusion-reaction model. Using the Rayleigh equation (closed-system approach), we obtained ε values of −11.2 and −6.6‰ for nitrogen and oxygen, respectively. The average ε values derived using the diffusion-reaction model were determined to be −20.7 ± 3.8 for nitrogen and −11.0 ± 1.7 for oxygen. Both N and O isotope fractionation appeared to be lower when denitrification rates where high, possibly in association with high organic carbon availability. In addition, variations in the isotope effects may be attributed to the variable importance of sedimentary denitrification having only a small isotope effect on the water column. The combined measurement of N and O isotope ratios in nitrate revealed that coupled nitrification-denitrification in the open-water was of minor importance. This is the first study of nitrogen and oxygen isotope effects associated with microbial denitrification in a natural lake. Moreover, this study confirms the high potential of δ¹⁸O of nitrate as a valuable biogeochemical tracer in aquatic systems, complementing nitrate δ¹⁵N.     

Intercomparison of Stratospheric Chemistry Models under Polar Vortex Conditions

Several stratospheric chemistry modules from box, 2-D or 3-D models, have been intercompared. The intercomparison was focused on the ozone loss and associated reactive species under the conditions found in the cold, wintertime Arctic and Antarctic vortices. Comparisons of both gas phase and heterogeneous chemistry modules show excellent agreement between the models under constrained conditions for photolysis and the microphysics of polar stratospheric clouds. While the mean integral ozone loss ranges from 4–80% for different 30–50 days long air parcel trajectories, the mean scatter of model results around these values is only about ±1.5%. In a case study, where the models employed their standard photolysis and microphysical schemes, the variation around the mean percentage ozone loss increases to about ±7%. This increased scatter of model results is mainly due to the different treatment of the PSC microphysics and heterogeneous chemistry in the models, whereby the most unrealistic assumptions about PSC processes consequently lead to the least representative ozone chemistry. Furthermore, for this case study the model results for the ozone mixing ratios at different altitudes were compared with a measured ozone profile to investigate the extent to which models reproduce the stratospheric ozone losses. It was found that mainly in the height range of strong ozone depletion all models underestimate the ozone loss by about a factor of two. This finding corroborates earlier studies and implies a general deficiency in our understanding of the stratospheric ozone loss chemistry rather than a specific problem related to a particular model simulation.     

Fast space-domain evaluation of geodetic surface integrals

Geodetic surface integrals play an important role in the numerical solution of geodetic boundary-value problems. In many cases they can be evaluated using fast methods in the frequency domain (FFT). However, this is not possible in general, because the domain of integration may be non-trivial (as is the surface of the Earth), the kernel function may not be of convolution type, or the data distribution may be heterogeneous. Therefore, fast evaluation strategies are also required in the space domain. They are more difficult to design because only one property is left where a more or less fast evaluation strategy can be built upon: the potential type of the kernel function. Consequently, the idea is not to replace well-established frequency domain techniques, but to supplement them. Our approach to this problem goes in two directions: (1) we use advanced cubature methods where the integration nodes automatically densify in the vicinity of the evaluation points; (2) we use powerful computer hardware, namely MIMD computers with distributed memory. This enables us to evaluate geodetic surface integrals of any practical complexity in reasonable time and accuracy. This is shown in a numerical example. Received: 7 May 1996 / Accepted:17 March 1997     

Putting Japanese investment in Europe in its place

Summary Research on Japanese economic activity in Europe concentrates almost exclusively on investment in manufacturing. However, this paper demonstrates that this emphasis both underestimates the longevity of Japanese direct investment in Europe and also grossly underdefines the importance of services. Not only does Japanese direct investment have a much longer history in Europe than is usually recognized but also—and perhaps more significantly—the bulk of that investment is not in manufacturing production per se but in a variety of circulation services. Using establishment-level data, this paper shows that the spatial manifestation of these circulation services is very different from that of manufacturing production.     

Three-dimensional Rayleigh hysteresis of oriented core samples from the German Continental Deep Drilling Program: susceptibility tensor, Rayleigh tensor, three-dimensional Rayleigh law

Rayleigh hysteresis, as defined by the well-known Rayleigh relations, has been observed not only when magnetization of pyrrhotite-bearing KTB-samples is measured in parallel to a weak dc magnetic field, but also in experiments where field and measuring directions have been adjusted strictly perpendicularly to each other. Nine-tupels of independent Rayleigh hysteresis loops could thus be compiled. Their characteristic coefficients X ^ijk of initial susceptibility together with the Rayleigh loss coefficients α^jk have been proved to determine completely the samples' weak-field magnetic anisotropy. Interpreting the coefficient matrices ( X ^ijk) and (α^jk) as the tensor of initial susceptibility and the Rayleigh tensor, respectively, generalization of the isotropic Rayleigh relations in terms of corresponding tensor relationships has been suggested for the anisotropic case. Application to the KTB samples showed 3-D Rayleigh hysteresis measurements to be an excellent tool for rock magnetic analysis in terms of ore content and crystalline texture. In particular, a magnetocrystalline double texture of the basal planes of pyrrhotite precipitates and their [1120] directions of easy magnetization have been clearly detected. Surprisingly, the welt-known theorem α= const. X ²_I, formulated by Néel (1942) for the isotropic case, has been found to hold true even in tensor generalization (α_jk) = const ( X ²_jk). To reach sufficient resolution for the measurements performed, a sensitive vibrating coil magnetometer (VCM) has been developed.     

The replacement of anthophyllite by jimthompsonite: a model for hydration reactions in biopyriboles

Anthophyllite crystals found in ultramafic lenses of the Lepontine Alps (Switzerland) contain coherent, submicroscopic intergrowths of ordered and disordered biopyribole polysomes. The chain width distributions of disordered polysomes were analyzed using high resolution transmission electron microscopy (HRTEM). Chains wider than triple were interpreted as intermediate products in the transformation of anthophyllite to the triple chain silicate jimthompsonite. The concentration of individual chain types is strongly correlated with the reaction progress. Based on observed zipper terminations and the transformation rules given by Veblen and Buseck (1980) a scheme of possible reaction paths leading from anthophyllite to jimthomp sonite is proposed. The reaction scheme and a simple kinetic model for elementary reactions allow modeling of the observed chain width distributions. The model suggests that the complex reaction paths involving steps with increasing and decreasing chain width are more important in the formation of jimthompsonite than the direct transformation from anthophyllite. The wide chains (>triple) occurring as intermediate products of the multi-step paths are structurally closer to talc than jimthompsonite. The back-transformation of these wide chains to triple chains is, therefore, a strong argument that jimthompsonite is a stable phase and not only a metastable intermediate product in the transformation of anthophyllite to talc. Received: 8 July 1996 / Accepted: 13 December 1996     

ASPI experiment: measurements of fields and waves on board the INTERBALL-1 spacecraft

The plasma-wave experiment ASPI (analysis of spectra of plasma waves and instabilities) on board the INTERBALL spacecraft is a combined wave diagnostics experiment. It performs measurements of the DC and AC magnetic field vector by flux-gate and searchcoil sensors, the DC and AC electric field vector by Langmuir double probes and the plasma current by Langmuir split probe. Preliminary data analysis shows the low noise levels of the sensors and the compatibility of new data with the results of previous missions. During several months of in-orbit operation a rich collection of data was acquired, examples of which at the magnetopause and plasma sheet are presented in second part of the paper.     

An Algorithm for the Determination of All Significant Pathways in Chemical Reaction Systems

When the output of a complex chemical model is analysed, a typical topic isthe determination of pathways, i.e., reaction sequences, that produce ordestroy a chemical species of interest.A representative example is the investigation of catalytic ozone destruction cycles in the stratosphere.An algorithm for the automatic determination of pathways in any given reactionsystem is presented. Under the assumption that reaction rates are known, it finds all significant pathways, i.e., all pathways with a rate above a prescribed threshold.The algorithm forms pathways step by step, starting from single reactions.The chemical species in the system are consecutively considered as `branching points'.For every branching-point species, each pathway producing it is connected witheach pathway consuming it.Rates proportional to `branching probabilities' are calculated.Pathways with a rate that is smaller than a prescribed threshold arediscarded.If a newly formed pathway contains sub-pathways, e.g., null cycles, it is split into these simpler pathways.In order to demonstrate the performance of the algorithm, it has been applied to the determination of catalytic ozone destruction cycles and methaneoxidation pathways in the stratosphere.