Carbon dioxide in silicate melts: A molecular dynamics simulation study

We have performed a series of molecular dynamics simulations aimed at the evaluation of the solubility of CO₂ in silicate melts of natural composition (from felsic to ultramafic). In making in contact within the simulation cell a supercritical CO₂ phase with a silicate melt of a given composition, we have been able to evaluate (i) the solubility of CO₂ in the P-T range 1473-2273 K and 20-150 kbar, (ii) the density change experienced by the CO₂-bearing melt, (iii) the respective concentrations of CO₂ and species in the melt, (iv) the lifetime and the diffusivity of these species and (v) the structure of the melt around the carbonate groups. The main results are the following:(1) The solubility of CO₂ increases markedly with the pressure in the three investigated melts (a rhyolite, a mid-ocean ridge basalt and a kimberlite) from about ∼2 wt% CO₂ at 20 kbar to ∼25 wt% at 100 kbar and 2273 K. The solubility is found to be weakly dependent on the melt composition (as far as the present compositions are concerned) and it is only at very high pressure (above ∼100 kbar) that a clear hierarchy between solubilities occurs (rhyolite < MORB < kimberlite). Furthermore at a given pressure the calculated solubility is negatively correlated with the temperature.(2) In CO₂-saturated melts, the proportion of carbonate ions is positively correlated with the pressure at isothermal condition and is negatively correlated with the temperature at isobaric condition (and vice versa for molecular CO₂). Furthermore, at fixed (P, T) conditions the proportion of carbonate ions is higher in CO₂-undersaturated melts than in the CO₂-saturated melt. Although the proportion of molecular CO₂ decreases when the degree of depolymerization of the melt increases, it is still significant in CO₂-saturated basic and ultrabasic compositions at high temperatures. This finding is at variance with experimental data on CO₂-bearing glasses which show no evidence of molecular CO₂ as soon as the degree of depolymerization of the melt is high (e.g. basalt). These conflicting results can be reconciled with each other by noticing that a simple low temperature extrapolation of the simulation data predicts that the proportion of molecular CO₂ in basaltic melts might be negligible in the glass at room temperature.(3) The carbonate ions are found to be transient species in the liquid phase, with a lifetime increasing exponentially with the inverse of the temperature. Contrarily to a usual assumption, the diffusivity of carbonate ions into the liquid silicate is not vanishingly small with respect to that of CO₂ molecules: in MORB they differ from each other by a factor of ∼6 at 1473 K and only a factor of ∼2 at 2273 K. Although the bulk diffusivity of CO₂ is governed primarily by the diffusivity of CO₂ molecules, the carbonate ions contribute significantly to the diffusivity of CO₂ in depolymerized melts.(4) Concerning the structure of the CO₂-bearing silicate melt, the carbonate ions are found to be preferentially associated with NBO’s of the melt, with an affinity for NBOs which exceeds that for BOs by almost one order of magnitude. This result explains why the concentration in carbonate ions is positively correlated with the degree of depolymerization of the melt and diminishes drastically in fully polymerized melts where the number of NBO’s is close to zero. Furthermore, the network modifier cations are not randomly distributed in the close vicinity of carbonate groups but exhibit a preferential ordering which depends at once on the nature of the cation and on the melt composition. However at the high temperatures investigated here, there is no evidence of long lived complexes between carbonate groups and metal cations.     

Balloon-borne observations of mid-latitude stratospheric water vapour: comparisons with HALOE and MLS satellite data

We present here in situ measurements obtained between 1991 and 2011 in outer-vortex conditions by the ELHYSA balloon-borne frost-point hygrometer. The frost-point hygrometer profiles are used for comparisons with the satellite data from version 19 (v19) and version 3.3 (v3.3) of the HALogen Occultation Experiment (HALOE) and the Microwave Limb Sounder (MLS) respectively. Potential Vorticity mapping is applied to all data sets to remove contributions of transient tropical intrusions and polar vortex air masses and hence ensure consistent comparisons between the balloon and satellite observations. Our selected balloon in situ observations are too sparse to directly infer mid-latitude stratospheric time series for continuous comparisons with HALOE and MLS records or derive water vapour trends but can be used to validate the satellite data. A mean difference of ?0.83?±?1.58 % (?0.04?±?0.07 ppmv) is obtained between HALOE v19 data and the balloon frost-point observations (with respect to HALOE) over the 30–80 hPa altitude range. The hygrometer-HALOE differences appear time-dependent as already presented in the literature. The mean difference reaches 2.80?±?0.96 % (0.13?±?0.04 ppmv) for MLS v3.3, with MLS systematically wetter than the balloon data reflecting a systematic bias between both datasets. We use our balloon data as reference to provide some information about the HALOE-MLS difference. From post-2000 ELHYSA-HALOE and ELHYSA-MLS comparisons, we find a HALOE-MLS difference matching the expected bias, with MLS v3.3 6.60?±?2.80 % (0.27?±?0.11 ppmv) wetter than HALOE v19. From the results obtained from our balloon-satellite data comparisons, we finally discuss the issue about merging the HALOE and MLS data sets to provide stratospheric water vapour trends.     

Evaluation of the regional climate model ALADIN to simulate the climate over North America in the CORDEX framework

In this study, an ensemble of four multi-year climate simulations is performed with the regional climate model ALADIN to evaluate its ability to simulate the climate over North America in the CORDEX framework. The simulations differ in their driving fields (ERA-40 or ERA-Interim) and the nudging technique (with or without large-scale nudging). The validation of the simulated 2-m temperature and precipitation with observationally-based gridded data sets shows that ALADIN performs similarly to other regional climate models that are commonly used over North America. Large-scale nudging improves the temporal correlation of the atmospheric circulation between ALADIN and its driving field, and also reduces the warm and dry summer biases in central North America. The differences between the simulations driven with different reanalyses are small and are likely related to the regional climate model’s induced internal variability. In general, the impact of different driving fields on ALADIN is smaller than that of large-scale nudging. The analysis of the multi-year simulations over the prairie and the east taiga indicates that the ALADIN 2-m temperature and precipitation interannual variability is similar or larger than that observed. Finally, a comparison of the simulations with observations for the summer 1993 shows that ALADIN underestimates the flood in central North America mainly due to its systematic dry bias in this region. Overall, the results indicate that ALADIN can produce a valuable contribution to CORDEX over North America.     

Evaluation of regional climate simulations for air quality modelling purposes

In order to evaluate the future potential benefits of emission regulation on regional air quality, while taking into account the effects of climate change, off-line air quality projection simulations are driven using weather forcing taken from regional climate models. These regional models are themselves driven by simulations carried out using global climate models (GCM) and economical scenarios. Uncertainties and biases in climate models introduce an additional “climate modeling” source of uncertainty that is to be added to all other types of uncertainties in air quality modeling for policy evaluation. In this article we evaluate the changes in air quality-related weather variables induced by replacing reanalyses-forced by GCM-forced regional climate simulations. As an example we use GCM simulations carried out in the framework of the ERA-interim programme and of the CMIP5 project using the Institut Pierre-Simon Laplace climate model (IPSLcm), driving regional simulations performed in the framework of the EURO-CORDEX programme. In summer, we found compensating deficiencies acting on photochemistry: an overestimation by GCM-driven weather due to a positive bias in short-wave radiation, a negative bias in wind speed, too many stagnant episodes, and a negative temperature bias. In winter, air quality is mostly driven by dispersion, and we could not identify significant differences in either wind or planetary boundary layer height statistics between GCM-driven and reanalyses-driven regional simulations. However, precipitation appears largely overestimated in GCM-driven simulations, which could significantly affect the simulation of aerosol concentrations. The identification of these biases will help interpreting results of future air quality simulations using these data. Despite these, we conclude that the identified differences should not lead to major difficulties in using GCM-driven regional climate simulations for air quality projections.     

Numerical Simulations of the Microscale Heterogeneities of Turbulence Observed on a Complex Site

We simulate the microscale heterogeneities of turbulent variables observed at a complex site for different wind directions. The atmospheric computational fluid dynamics (CFD) results are compared with an ensemble of 36 months of data collected at the experimental site SIRTA “Site Instrumental de Recherche par Télédétection Atmosphérique”, located near Paris (France) in a semi-urban environment. The experimental data show that the normalized turbulent kinetic energy (TKE) k/U ² (where k is TKE and U is the wind speed) at 10-m height, for two different locations, is highly dependent on wind direction and strongly influenced by trees. These measurements show a strong increase of the normalized TKE downstream of the forest canopies with a large variability within the 36-month period in part due to the variation of the tree foliage. The numerical simulations are carried out using the CFD code Code_Saturne with the standard k?ε closure, in neutral stratification. The buildings are taken into account explicitly in the mesh and the forested areas are modelled with two approaches: the classical roughness wall law and a drag porosity. A comparison has been performed between the calculated values and the median of measured values of the normalized TKE and the normalized friction velocity, for each wind sector of 10°. A very good agreement is obtained with the drag porosity model, whereas the classical roughness law leads to a strong underestimation downstream of the forested areas. However, this large improvement of the results using the drag porosity model can only be obtained with a refinement of the grid, especially in forested areas, and an accurate land-use map.     

A comparison of downscaling techniques in the projection of local climate change and wheat yields

This study aims to evaluate the performance of two mainstream downscaling techniques: statistical and dynamical downscaling and to compare the differences in their projection of future climate change and the resultant impact on wheat crop yields for three locations across New South Wales, Australia. Bureau of Meteorology statistically- and CSIRO dynamically-downscaled climate, derived or driven by the CSIRO Mk 3.5 coupled general circulation model, were firstly evaluated against observed climate data for the period 1980–1999. Future climate projections derived from the two downscaling approaches for the period centred on 2055 were then compared. A stochastic weather generator, LARS-WG, was used in this study to derive monthly climate changes and to construct climate change scenarios. The Agricultural Production System sIMulator-Wheat model was then combined with the constructed climate change scenarios to quantify the impact of climate change on wheat grain yield. Statistical results show that (1) in terms of reproducing the past climate, statistical downscaling performed better over dynamical downscaling in most of the cases including climate variables, their mean, variance and distribution, and study locations, (2) there is significant difference between the two downscaling techniques in projected future climate change except the mean value of rainfall across the three locations for most of the months; and (3) there is significant difference in projected wheat grain yields between the two downscaling techniques at two of the three locations.     

Hollow Cylinder Tests on Boom Clay: Modelling of Strain Localization in the Anisotropic Excavation Damaged Zone

Boom Clay is extensively studied as a potential candidate to host underground nuclear waste disposal in Belgium. To guarantee the safety of such a disposal, the mechanical behaviour of the clay during gallery excavation must be properly predicted. In that purpose, a hollow cylinder experiment on Boom Clay has been designed to reproduce, in a small-scale test, the Excavation Damaged Zone (EDZ) as experienced during the excavation of a disposal gallery in the underground. In this article, the focus is made on the hydro-mechanical constitutive interpretation of the displacement (experimentally obtained by medium resolution X-ray tomography scanning). The coupled hydro-mechanical response of Boom Clay in this experiment is addressed through finite element computations with a constitutive model including strain hardening/softening, elastic and plastic cross-anisotropy and a regularization method for the modelling of strain localization processes. The obtained results evidence the directional dependency of the mechanical response of the clay. The softening behaviour induces transient strain localization processes, addressed through a hydro-mechanical second grade model. The shape of the obtained damaged zone is clearly affected by the anisotropy of the materials, evidencing an eye-shaped EDZ. The modelling results agree with experiments not only qualitatively (in terms of the shape of the induced damaged zone), but also quantitatively (for the obtained displacement in three particular radial directions).     

The application of an innovative inverse model for understanding and predicting landslide movements (Salazie cirque landslides,Reunion Island)

The prediction of landslide movement acceleration is a complex problem, among others identified for deep-seated landslides, and represents a crucial step for risk assessment. Within the scope of this problem, the objective of this paper is to explore a modelling method that enables the study of landslide function and facilitates displacement predictions based on a limited data set. An inverse modelling approach is proposed for predicting the temporal evolution of landslide movement based on rainfall and displacement velocities. Initially, the hydrogeology of the studied landslides was conceptualised based on correlative analyses. Subsequently, we applied an inverse model with a Gaussian-exponential transfer function to reproduce the displacements. This method was tested on the Grand Ilet (GI) and Mare-à-Poule-d’Eau (HB) landslides on Reunion Island in the Indian Ocean. We show that the behaviour of landslides can be modelled by inverse models with a bimodal transfer function using a Gaussian-exponential impulse response. The cumulative displacements over 7 years of modelling (2 years of calibration period for GI, and 4 years for HB) were reproduced with an RMSE above 0.9. The characteristics of the bimodal transfer function are directly related to the hydrogeological functioning demonstrated by the correlative analyses: the rapid reaction of a landslide can be associated with the effect of a preferential flow path on groundwater level variations. Thus, this study shows that the inverse model using a Gaussian-exponential transfer function is a powerful tool for predicting deep-seated landslide movements and for studying how they function. Beyond modelling displacements, our approach effectively demonstrates its ability to contribute relevant data for conceptualising the sliding mechanisms and hydrogeology of landslides.     

Constitutive analysis of the mechanical anisotropy of Opalinus Clay

This paper aims to analyse the anisotropic features of behaviour of Opalinus Clay using the theory of plastic multi-mechanisms. The results of triaxial tests conducted with different load levels and directions showed that the mechanical behaviour of this shale is cross-anisotropic. The stiffer samples are those in which the loading direction is parallel to the bedding plane. This indicates that the preconsolidation stress depends on the orientation of the load with respect to the fabric of Opalinus Clay. It is proposed to interpret the observed cross-anisotropy with an elastoplastic model based on four plastic strain mechanisms that may be successively mobilised depending on the loading direction. The predicted stress–strain responses vary according to the directions of the space as a result of the hardening process, depending on the number of plastic strain mechanisms that have been mobilised. The numerical predictions show overall good agreement with the experimental data in terms of deviatoric stress versus axial strain, demonstrating that multi-mechanism plasticity is a suitable constitutive tool for the interpretation of the mechanical anisotropy of this shale.