Assessment of alternative adsorption models and global sensitivity analysis to characterize hexavalent chromium loss from soil to surface runoff

We investigate our ability to assess transfer of hexavalent chromium, Cr(VI), from the soil to surface runoff by considering the effect of coupling diverse adsorption models with a two‐layer solute transfer model. Our analyses are grounded on a set of two experiments associated with soils characterized by diverse particle size distributions. Our study is motivated by the observation that Cr(VI) is receiving much attention for the assessment of environmental risks due to its high solubility, mobility, and toxicological significance. Adsorption of Cr(VI) is considered to be at equilibrium in the mixing layer under our experimental conditions. Four adsorption models, that is, the Langmuir, Freundlich, Temkin, and linear models, constitute our set of alternative (competing) mathematical formulations. Experimental results reveal that the soil samples characterized by the finest grain sizes are associated with the highest release of Cr(VI) to runoff. We compare the relative abilities of the four models to interpret experimental results through maximum likelihood model calibration and four model identification criteria (i.e., the Akaike information criteria [AIC and AIC_C] and the Bayesian and Kashyap information criteria). Our study results enable us to rank the tested models on the basis of a set of posterior weights assigned to each of them. A classical variance‐based global sensitivity analysis is then performed to assess the relative importance of the uncertain parameters associated with each of the models considered, within subregions of the parameter space. In this context, the modelling strategy resulting from coupling the Langmuir isotherm with a two‐layer solute transfer model is then evaluated as the most skilful for the overall interpretation of both sets of experiments. Our results document that (a) the depth of the mixing layer is the most influential factor for all models tested, with the exception of the Freundlich isotherm, and (b) the total sensitivity of the adsorption parameters varies in time, with a trend to increase as time progresses for all of the models. These results suggest that adsorption has a significant effect on the uncertainty associated with the release of Cr(VI) from the soil to the surface runoff component.     

Muon density measurements with the KASCADE central detector

Frequency distributions of local muon densities in high-energy extensive air showers (EAS) are presented as signature of the primary cosmic ray energy spectrum in the knee region. Together with the gross shower variables like shower core position, angle of incidence, and the shower sizes, the KASCADE experiment is able to measure local muon densities for two different muon energy thresholds. The spectra have been reconstructed for various core distances, as well as for particular subsamples, classified on the basis of the shower size ratio N_μ/N_e. The measured density spectra of the total sample exhibit clear kinks reflecting the knee of the primary energy spectrum. While relatively sharp changes of the slopes are observed in the spectrum of EAS with small values of the shower size ratio, no such feature is detected at EAS of large N_μ/N_e ratio in the energy range of 1–10 PeV. Comparing the spectra for various thresholds and core distances with detailed Monte Carlo simulations the validity of EAS simulations is discussed.