Reformulated O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic ‘absolute’ carbon and oxygen isotope ratios

Mass-spectrometric stable isotope measurements of CO₂ use molecular ion currents at mass-to-charge ratios m/z 44, 45 and 46 to derive the elemental isotope ratios n(¹³C)/n(¹²C) and n(¹⁸O)/n(¹⁶O), abbreviated ¹³C/¹²C and ¹⁸O/¹⁶O, relative to a reference. The ion currents have to be corrected for the contribution of ¹⁷O-bearing isotopologues, the so-called ‘¹⁷O correction’. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing ¹³C/¹²C (¹³R), ¹⁷O/¹⁶O (¹⁷R) and ¹⁸O/¹⁶O (¹⁸R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO₂ generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H₃PO₄ at 25 °C (VPDB-CO₂). I find , ¹⁸R_VSMOW/10⁻⁶ = 2005.20 ± 0.45, ¹³R_VPDB-CO2/10^-6= 11124 ± 45, and ¹⁸R_VPDB-CO2/10^-6=2088.37±0.90. I also rephrase the calculation scheme for the ¹⁷O correction completely in terms of relative isotope ratio differences (δ values). This reveals that only ratios of isotope ratios (namely, ¹⁷R/¹³R and ¹³R¹⁷R/¹⁸R) are required for the ¹⁷O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative ¹³C/¹²C difference, but not for¹⁸O/¹⁶O. Even though inter-laboratory differences can be corrected for by a common ‘ratio assumption set’ and/or normalisation, the ultimate accuracy of the ¹⁷O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between ¹⁷O/¹⁶O and ¹⁸O/¹⁶O isotope ratios. For highest accuracy in the ¹³C/¹²C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that allows direct measurement of ¹³R¹⁷R/¹⁸R.     

Deep-seated gravitational slope deformations and their influence on consequent mass movements (case studies from the highest part of the Czech Carpathians)

Gravitational spreading of mountain ridges displays primary disequilibrium of flysch mountain areas of the Czech Carpathians. The progression of various types of mass movements is a product of long-term ridge disintegration and is predisposed by the geological structure of the area and the upper Tertiary-Quaternary morphogenesis of the mountain area. Deep-seated slope deformations are spatially interconnected by the occurrence of some other types of slope deformations (e.g. debris flows, debris slides, slumps, rock avalanches, etc.), which pose a considerable risk for the existence of human society. An important causative factor in these dynamically developing hazardous processes is, among other factors, the way in which land has been used in the last three centuries. Therefore, the occurrence of various types of slope deformations is studied in terms of their relation to deep-seated gravitational deformations and in terms of other limiting factors (structural geological, morphological and climatic factors, manmade impacts, etc.). The paper presents several case studies of slope deformations (Velká Čantoryje Mt, Lysá hora Mt, Ropice Mt and Smrk Mt) in the area of the Outer Carpathians within the territory of the Czech Republic and also adverts to some consequences in terms of the socioeconomic structure of the landscape.     

Application of the Single-Bubble Airgun Technique for OBS-Data Acquisition Across the Jan Mayen Ridge,North Atlantic

A 140 km long wide-angle seismic profile has been acquired by use of 6 Ocean Bottom Seismographs across the Jan Mayen Ridge, North Atlantic. The profile was acquired twice; once with a traditionally tuned standard source and secondly with a somewhat smaller source tuned on the first bubble pulse. Analysis of the frequency content of the data reveals that the single-bubble source within the 10-15 Hz frequency range generates a signal with a level about 5 db above that of the standard source. These differences can partly be related to differences in airgun depth. The higher output level for these frequencies enables the single-bubble source to resolve intra-crustal structures with a higher degree of certainty, when compared to the data acquired by use of the standard source array. The standard source seems to generate slightly more energy for frequencies around 6 Hz, probably due to the use of a large 1200 in/sup3 gun in this array. These low frequencies a re of importance for mapping of lower crustal and upper mantle structures, and it is recommended that this is taken into account when seismic sources for mapping of deep crustal and upper mantle structures are designed.     

Sheet flow and suspension of sand in oscillatory boundary layers

after revisionTime-dependent measurements of flow velocities and sediment concentrations were conducted in a large oscillating water tunnel. The measurements were aimed at the flow and sediment dynamics in and above an oscillatory boundary layer in plane bed and sheet-flow conditions. Two asymmetric waves and one sinusoidal wave were imposed using quartz sand with D₅₀ = 0.21 mm. A new electro-resistance probe with a large resolving power was developed for the measurement of the large sediment concentrations in the sheet-flow layer. The measurements revealed a three layer transport system consisting of a pick-up/deposition layer, an upper sheet flow layer and a suspension layer.In the asymmetric wave cases the total net transport was directed “onshore” and was mainly concentrated in the thin sheet flow layer (< 0.5 cm) at the bed. A small net sediment flux was directed “offhore” in the upper suspension layer. The measured flow velocities, sediment concentrations and sedimenl fluxes showed a good qualitative agreement with the results of a (numerical) 1DV boundary-layer flow and transport model. Although the model did not describe all the observed processes in the sheet-flow and suspension layer, the computational results showed a reasonable agreement with measured net transport rates in a wide range of asymmetric wave conditions.     

A new method for the generation of second-order random waves

In order to prevent the generation of spurious free sub- and superharmonics of random waves in a laboratory channel, the control signal for the wave board has to be derived according to a higher-order wave theory. An expression for this control signal has been derived with the perturbation method of multiple scales. It is much less complex and requires less computation time than the expressions obtained from the full second-order theory. The new method for second-order subharmonics was verified experimentally for waves with bichromatic and continuous first-order spectra. The data were analysed with the complex-harmonic principal-component analysis to reduce the influence of noise.     

Tropical Marine Fungi*

Abstract. Marine Ascomycetes, Basidiomycetes and Deuteromycetes were collected in tropical and subtropical regions (Australia, Belize, Fiji, Hawaii, Marshall Islands, Mexico, New Zealand, Palau, Thailand), and the known range of distribution for these fungi was extended. Exclusively tropical are 27 taxa, 9 are probably restricted to the tropics also, and 11 are cosmopolitan. Distribution maps are given for 5 taxa. New species (4), varieties (3), and combinations (2) of Ascomycetes are proposed, and keys to the taxa of Halosarpheia and Lulworthia are presented. Most of the species are decomposers of mangrove parts or of detritus in sandy beaches. Nine new host plants were found. Marine Ascomycetes were discovered for the first time living in shells of foraminifera.     

Circulation and Brackish Water Dispersal in a Coastal Lagoon of Southwest Taiwan

Modest observations and numerical experiments were conducted to investigate circulation and brackish water dispersal in a coastal lagoon southwest of Taiwan. The Chi-Ku Lagoon, partially shielded from the sea by a string of sandbar barriers with two entrances among them, receives modest and episodic runoff from Chi-Ku Stream. Flood and ebb tidal streams entering and leaving the two entrances are found to converge and diverge in a flow stagnation area inside the lagoon. Under weak wind conditions, brackish water is preferentially retained in the flow stagnation area. Besides the observations, scenario runs using a three-dimensional numerical model also indicate strong modulation by monsoon winds. Both summer southwest monsoon and winter northeast monsoon reduce brackish water retention; the latter is found to be more effective. This revised version was published online in August 2006 with corrections to the Cover Date.