Sorption of Np(V) and Np(IV) onto kaolinite: Effects of pH,ionic strength,carbonate and humic acid

The sorption of Np(V) and Np(IV) onto kaolinite has been studied in the absence and presence of humic acid (HA) in a series of batch equilibrium experiments under different experimental conditions: [Np]₀: 1.0 × 10^-6 or 1.0 × 10^-5 M, [HA]₀: 0 or 50 mg/L, I: 0.01 or 0.1 M NaClO₄, solid to liquid ratio: 4 g/L, pH: 6–11, anaerobic or aerobic conditions, without or with carbonate. The results showed that the Np(V) sorption onto kaolinite is affected by solution pH, ionic strength, Np concentration, presence of carbonate and HA. In the absence of carbonate, the Np(V) uptake increased with pH up to ∼96% at pH 11. HA further increased the Np(V) sorption between pH 6 and 9 but decreased the Np(V) sorption between pH 9 and 11. In the presence of carbonate, the Np(V) sorption increased with pH and reached a maximum of 54% between pH 8.5 and 9. At higher pH values, the Np(V) sorption decreased due to the presence of dissolved neptunyl carbonate species with a higher negative charge that were not sorbed onto the kaolinite surface which is negatively charged in this pH range. HA again decreased the Np(V) uptake in the near-neutral to alkaline pH range due to formation of aqueous neptunyl humate complexes. The decrease of the initial Np(V) concentration from 1.0 × 10⁻⁵ M to 1.0 × 10⁻⁶ M led to a shift of the Np(V) adsorption edge to lower pH values. A higher ionic strength increased the Np(V) uptake onto kaolinite in the presence of carbonate but had no effect on Np(V) uptake in the absence of carbonate.     

Reconstructing ancient topography through erosion modelling

One of the main aims of geomorphology is to understand how geomorphic processes change topography over long time scales. Over the last decades several landscape evolution models have been developed in order to study this question. However, evaluation of such models has often been very limited due to the lack of necessary field data. In this study we present a topography based hillslope erosion and deposition model that is based on the WATEM/SEDEM model structure and works on a millennial time scale. Soil erosion, transport and deposition are calculated using slope and unit contributing area. The topography is iteratively rejuvenated by taking into account modelled erosion and deposition rates, thereby simulating topographic development backwards in time. A first attempt has been made to spatially evaluate the model, using detailed estimates for historical soil erosion and sediment deposition volumes, obtained from an augering campaign in a small catchment in the Belgian Loess Belt. The results show that the model can simulate realistic soil redistribution patterns. However, further research is necessary in order to deal with artificial flaws that cause routing problems and significantly influence results. Common problems and issues related to this type of backward modelling are also discussed.     

Schmelzgleichgewichte zur Klärung des Augitproblems

In synthetic melts was investigated the substitution of Na⁺, Al³⁺ and Fe³⁺ in the crystal lattice of several CaSIO₃-MgSiO₃-Fe²⁺SiO₃-pyroxenes by means of microanalytical-, X-ray- and optical methods. A considerable mutual influence of these ions could be observed. Optical and X-ray methods are not sufficient for the determination of smaller components in mixed crystals. By combining them with the chemical analysis the partly known system diopside-jadeite could be set right. Further more some other systems seem to contain mixed crystals instead of the pure compounds as was suggested formerly. The methods used in determing the maximum solubility to the present date proved to be insufficient. As a better way the extrapolation of solidus curves is proposed. The influence of larger quantities of Fe³⁺ in Si⁴⁺-position upon the diopside lattice was investigated as well as the problem of the immiscibility gap between pigeonites and augites. Rhombic enstatite was for the first time synthetically prepared from a melt.      

Genetically meaningful decomposition of grain-size distributions

All spatio-temporal grain-size patterns in sediments can be characterized by a mathematical representation of (un)mixing. This implies that an inverse model of (un)mixing would be ideally suited to obtain genetically meaningful interpretations of observed grain-size distributions (GSDs). GSDs are therefore often decomposed into theoretical end members by parametric curve-fitting procedures. Many researchers have been tempted to use goodness-of-fit measures as a means of justifying such decompositions in the absence of generic process-based models of end-member GSDs. A critical examination of parametric curve fitting through a series of numerical experiments shows that the goodness-of-fit of an approximation may be a poor guide to its genetic significance. The genetic interpretation of GSDs is a poorly constrained problem that cannot be solved without taking into account the geological context of GSDs, which may be captured by the covariance structure of grain-size classes across a series of GSDs sampled in a contiguous area. Curve-fitting methods cannot exploit this geological context, which explains why the geological relevance of curve-fitting results obtained in black-box mode is questionable. The desired genetic interpretation of GSDs can be obtained by applying the end-member-modelling algorithm EMMA to a series of GSDs simultaneously. Many end-member GSDs estimated by EMMA do not conform to one of the popular theoretical GSD models. Consequently, parametric curve fitting with theoretical distributions is more likely to obscure than to reveal the existence of genetically significant grain-size populations in sediments, especially if such populations are present in small proportions.     

Modelling the long‐term sediment trap efficiency of small ponds

A numerical model (sediment trap efficiency for small ponds—STEP) is developed to simulate sediment deposition in small ponds (i.e. <1 ha) and to calculate the sediment trap efficiency (STE). The algorithms are kept simple to allow the model to simulate larger time periods (i.e. several years). Eight runs with an experimental pond were executed to test the model. The STEP model produces reasonable predictions of STE as well as the shape and magnitude of the effluent sediment concentration graph. The model efficiency of STEP for the prediction of STE equals 0·38 and the root mean square error equals 4·7%. Similar models, such as DEPOSITS and CSTRS, were inefficient in predicting the experimental results. The STEP model was used to simulate the long‐term (33 years) STE of small retention ponds in central Belgium using 10‐min rainfall data. For a typical pond (1000 m²) with a catchment area of 25 ha, annual STE can vary from 58 to 100%, with a long‐term STE of only 68%. Copyright © 2001 John Wiley & Sons, Ltd.     

A primordial feature at the scale of superclusters of galaxies

We investigate a spatially flat cold dark matter model (with the matter density parameter     with a primordial feature in the initial power spectrum. We assume that there is a bump in the power spectrum of density fluctuations at wavelengths     , which corresponds to the scale of superclusters of galaxies . There are indications for such a feature in the power spectra derived from redshift surveys and also in the power spectra derived from peculiar velocities of galaxies. We study the mass function of clusters of galaxies, the power spectrum of the cosmic microwave background (CMB) temperature fluctuations, the rms bulk velocity and the rms peculiar velocity of clusters of galaxies. The baryon density is assumed to be consistent with the big bang nucleosynthesis value. We show that with an appropriately chosen feature in the power spectrum of density fluctuations at the scale of superclusters, the mass function of clusters, the CMB power spectrum, the rms bulk velocity and the rms peculiar velocity of clusters are in good agreement with the observed data.     

Metamictisation of natural zircon: accumulation versus thermal annealing of radioactivity-induced damage

Annealing of the radiation damage generated in !-decay events is a common phenomenon in natural zircons. We have studied relationships between radiation damage, age and radionuclide content of natural zircons on a micro-scale. The degree of metamictisation was estimated by means of confocal laser-Raman spectroscopic measurements. Raman band broadening in well-ordered to moderately metamict zircons that have not experienced significant healing of the radiation damage since the time of their growth, shows a nearly linear dependence on the !-fluence. This dependence is proposed as a calibration line for examining unknown zircons in order to consider complete or incomplete damage storage, which may contribute to the understanding of the low-T thermal history of their host rocks. Seven examples for the application are presented. Radiation damage may anneal heterogeneously, with preferred re-ordering in more damaged micro-areas. Results suggest that single point defects do not anneal continuously over geologic periods of time but are, in contrast, a comparably stable type of radiation damage. In contrast to recrystallisation processes, structural recovery due to simple thermal annealing is not necessarily connected with loss of radiogenic Pb. The most prominent example for this are concordant zircons from Sri Lanka. Although they are excellent standards for U-Pb dating, Sri Lankan zircons should not be used as standards for structural radiation damage. The experimental work is completed by Monte Carlo simulations of !-decay events in zircon.     

Sulphur Enrichment in Organic Matter of Eastern Mediterranean Sapropels: A Study of Sulphur Isotope Partitioning

Sulphur isotope compositions and S/C ratios of organic matter were analysed in detail by combustion-isotope ratio monitoring mass spectrometry (C-irmMS) in eastern Mediterranean sediments containing three sapropels of different ages and with different organic carbon contents (sapropel S1 in core UM26, formed from 5–9 ka ago with a maximum organic carbon content of 2.3 wt%; sapropel 967 from ODP Site 160-967C, with an age of 1.8 Ma and a maximum organic carbon content of 7.4 wt%; and sapropel 969 from ODP Site 160-969E, with an age of 2.9 Ma and a maximum organic carbon content of 23.5 wt%). Sulphur isotopic compositions (34S) of the organic matter ranged from -29.5 to +15.8 and the atomic S/C ratio was 0.005 to 0.038. The organic sulphur in the sediments is a mixture of sulphur derived from (1) incorporation of 34S-depleted inorganic reduced sulphur produced by dissimilatory microbial sulphate reduction; and (2) biosynthetic sulphur with an isotopic signature close to seawater sulphate. The calculated biosynthetic fraction of organic sulphur in non-sapropelic sediments ranges from 68–87%. The biosynthetic fraction of the organic sulphur of the sapropels (60–22%) decreases with increasing organic carbon content of the sapropels. We propose that uptake of reduced sulphur into organic matter predominantly took place within sapropels where pyrite formation was iron-limited and thus an excess of dissolved sulphide was present for certain periods of time. Simultaneously, sulphide escaped into the bottom water and into sediments below the sapropels where pyrite formation occurred.