Understanding the time‐varying importance of different uncertainty sources in hydrological modelling using global sensitivity analysis

Simulations from hydrological models are affected by potentially large uncertainties stemming from various sources, including model parameters and observational uncertainty in the input/output data. Understanding the relative importance of such sources of uncertainty is essential to support model calibration, validation and diagnostic evaluation and to prioritize efforts for uncertainty reduction. It can also support the identification of ‘disinformative data’ whose values are the consequence of measurement errors or inadequate observations. Sensitivity analysis (SA) provides the theoretical framework and the numerical tools to quantify the relative contribution of different sources of uncertainty to the variability of the model outputs. In traditional applications of global SA (GSA), model outputs are aggregations of the full set of a simulated variable. For example, many GSA applications use a performance metric (e.g. the root mean squared error) as model output that aggregates the distances of a simulated time series to available observations. This aggregation of propagated uncertainties prior to GSA may lead to a significant loss of information and may cover up local behaviour that could be of great interest. Time‐varying sensitivity analysis (TVSA), where the aggregation and SA are repeated at different time steps, is a viable option to reduce this loss of information. In this work, we use TVSA to address two questions: (1) Can we distinguish between the relative importance of parameter uncertainty versus data uncertainty in time? (2) Do these influences change in catchments with different characteristics? To our knowledge, the results present one of the first quantitative investigations on the relative importance of parameter and data uncertainty across time. We find that the approach is capable of separating influential periods across data and parameter uncertainties, while also highlighting significant differences between the catchments analysed. Copyright © 2016 The Authors. Hydrological Processes. Published by John Wiley & Sons Ltd.     

Regional dynamical downscaling with CCLM over East Asia

Inspired by the framework of the Coordinated Regional Climate Downscaling Experiment (CORDEX), the hindcast (1971–2000) and projection (2021–2050) simulations based on a resolution of $0.44^\circ$ over the East Asia domain are performed with the regional climate model COSMO-CLM (CCLM). The simulations are driven by ERA-40 reanalysis data and output of the global climate model ECHAM5. This is the first time that the CCLM is adapted and evaluated for the East Asia Monsoon region; the setup is considered a starting point for further improvements in this region by the CCLM community. The evaluation results show that the CCLM is able to reasonably capture the climate features in this region, especially the monsoon dynamics on small scales. However, total precipitation in the northern part of the domain, over the Tibetan Plateau, and over east Indonesia has a pronounced wet bias. The projected climate change under the A1B scenario indicates an overall annual surface temperature increase of 1–2 K, but no significant precipitation changes.     

Experimental study of the aragonite to calcite transition in aqueous solution

The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200 °C using single inorganic aragonite crystals as a starting material. The initial saturation state and the total [Ca²⁺]:[CO₃²⁻] ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy.Experiments using carbonate solutions prepared with water enriched in ¹⁸O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of ¹⁸O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the ¹⁸O distribution in the calcite replacement. An activation energy of 109 kJ/mol was calculated for the exchange of oxygen isotopes between [C¹⁶O₃²⁻]_aq and [H₂¹⁸O] and the time for oxygen isotope exchange in the fluid at 200 °C was estimated at ∼0.9 s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution-reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.     

Uptake of Eu(III) by 11 Å tobermorite and xonotlite: A TRLFS and EXAFS study

The uptake of Eu(III) by crystalline calcium silicate hydrate (C-S-H) phases 11 Å tobermorite and xonotlite has been investigated by the combined use of time-resolved laser fluorescence spectroscopy (TRLFS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Eu(III) doped tobermorite and xonotlite samples with varying metal loading (0.4, 7 and 35 μmol Eu/g solid phase) and reaction time (1-570 days) were investigated. The structural environment of Eu(III) taken up by tobermorite and xonotlite was found to depend on both parameters.At high Eu(III) loading (7 μmol Eu/g solid phase), TRLFS data indicated presence of three Eu(III) species with different fluorescence lifetimes after 1 day reaction time. The emission lifetimes deduced for the different species correspond to ∼4.7, ∼1 and 0 water molecules in the first coordination sphere, thus suggesting the presence of one surface species forming an inner-sphere surface complex and two species incorporated in the crystal structure. After longer contact times (90 days, 570 days), the surface species was not observed. At the lower Eu(III) loading (0.4 μmol Eu/g solid phase) and reaction times between 1 and 310 days only two Eu(III) species with ∼1-2 and 0 water molecules were detected, corresponding to Eu(III) being incorporated in the crystal structure. The results from EXAFS showed that the distances between Eu(III) and neighboring Ca and Si atoms in Eu(III) doped tobermorite increase after prolonged reaction time. Furthermore, the number of neighboring Ca and Si atoms was found to increase with time. This study demonstrates that binding into the structure of 11 Å tobermorite and xonotlite is the dominant mode of Eu(III) immobilization after long reaction time. This finding is essential for an overall assessment of the safe disposal of actinides in deep geological repositories for radioactive waste, as incorporation into the crystal structure suggests long-term immobilization in the repository environment.     

Formation of kyanite–quartz veins of the Alpe Sponda,Central Alps,Switzerland: implications for Al transport during regional metamorphism

In this study, we have investigated the formation of quartz–kyanite veins of the Alpe Sponda, Central Alps, Switzerland. We have integrated field observations, fluid inclusion and stable isotope data and combined this with numerical geochemical modeling to constrain the chemical processes of aluminum transport and deposition. The estimated P–T conditions of the quartz–kyanite veins, based on conventional geothermometry (garnet–biotite, white mica solvus and quartz–kyanite oxygen isotope thermometry) and fluid inclusion data, are 550 ± 30°C at 5.0 ± 0.5 kbar. Geochemical modeling involved construction of aqueous species predominance diagrams, calculation of kyanite and quartz solubility, and reaction–path simulations. The results of the modeling demonstrate that (1) for the given chemical composition of the vein-forming fluids mixed Al–Si aqueous species are dominant in transporting Al, and that (2) fluid cooling along a small temperature gradient coupled with a pH decrease is able to explain the precipitation of the quartz–kyanite assemblages in the proportions that are observed in the Alpe Sponda veins. We conclude that sufficient amounts of Al can be transported in typical medium- to high-grade regional metamorphic fluids and that immobile behavior of Al is not very likely in advection–dominanted fluid–rock systems in the upper and middle crust.     

Voigt profile fitting to quasar absorption lines: an analytic approximation to the Voigt–Hjerting function

The Voigt–Hjerting function is fundamental in order to correctly model the profiles of absorption lines imprinted on the spectra of bright background sources by intervening absorbing systems. In this work, we present a simple analytic approximation to this function in the context of absorption-line profiles of intergalactic H  i absorbers. Using basic calculus tools, we derive an analytic expression for the Voigt–Hjerting function that contains only fourth-order polynomial and Gaussian functions. In connection with the absorption coefficient of intergalactic neutral hydrogen, this approximation is suitable for modelling Voigt profiles with an accuracy of 10⁻⁴ or better for an arbitrary wavelength baseline, for column densities up to   N _H I= 10 ²² cm⁻²  , and for damping parameters   a ≲ 10⁻⁴  , that is, the entire range of parameters characteristic to all Lyman transitions arising in a variety of H  i absorbing systems such as Lyman α (Lyα) forest clouds, Lyman limit systems and damped Lyα systems. We hence present an approximation to the Voigt–Hjerting function that is both accurate and flexible to implement in various types of programming languages and machines, and with which Voigt profiles can be calculated in a reliable and very simple manner.