Liquid-Liquid Equilibrium of Deep Eutectic Solvent-Aromatic-Aliphatic Ternary Systems: Experimental Study with COSMO Model Predictions

Common solvents used for aromatic extraction from aliphatics typically degrade into toxic compounds, while green alternatives perform poorly compared to the state-of-the-art solvents. Deep eutectic solvents (DES) are a novel solvent type made of hydrogen bond donors (HBD) and hydrogen bond acceptors (HBA). DES have been applied in various applications, including advanced separations. In this study, DES were studied experimentally and using the Conductor-like Screening Model (COSMO) to separate benzene from cyclohexane as model compounds for an aromatic:aliphatic system. Both equilibrium and kinetic studies were performed to determine the liquid liquid equilibrium (LLE) and mass transfer rate for the DES-based separation. Selected HBAs including tetrabutylammonium bromide (N4444Br), tetrahexylammonium bromide (N6666Br), choline chloride (ChCl), and methyltriphenylphosphonium bromide (METPB) were paired with HBDs including ethylene glycol (EG) and glycerol (Gly). COSMO was used, with adjustments to reflect DES specific interactions, to predict the liquid-liquid equilibrium (LLE). COSMO results showed that ChCl and N6666Br-based DES extracted too little benzene or too much cyclohexane, respectively, to be considered for experimental evaluation. Overall, the COSMO model predictions for LLE of EG-based DES were very accurate, with root-mean-square deviations (RMSD) below 1% for both N4444Br:EG and METPB:EG. The glycerol systems were less accurately modeled, with RMSD’s of 4% for N4444Br:Gly and 6% for METPB:Gly. The lower accuracy of glycerol system predictions fmay be due to limitations in COSMO for handling glycerol’s influence on polarizability in the DES that is not seen in EG-based DES. Mass transfer kinetics were determined experimentally for DES and the results were fit to a first order kinetics model. METPB:Gly had the highest mass transfer coefficient at 0.180 min−1, followed by N4444Br:EG at 0.143 min−1. N4444Br:Gly and METPB:EG had the lowest mass transfer coefficients at 0.096 min−1 and 0.084 min−1, respectively. It was found that mass transfer rate was not directly related to maximum benzene solubility, as N4444Br:EG and METPB:Gly had the highest and lowest benzene removal, respectively, but had similar mass transfer coefficients.

Evaluating the Urban Canopy Scheme TERRA_URB in the COSMO Model for Selected European Cities

<p>Nowadays, cities are the preferred location for more than half of the human population and the places where major human-perceived climate change impacts occur. In an increasingly urbanized world, it is essential to represent such areas adequately in Numerical Weather Prediction (NWP) models, not only to correctly forecast air temperature, but also the human heat stress and the micro-climate phenomena induced by the cities. Among them, the best known is the Urban Heat Island (UHI) effect, which refers to the significantly higher temperatures experienced by a metropolitan area than its rural surroundings. Currently, the COSMO model employs a zero-order urban description, which is unable to correctly reproduce the UHI effect: cities are simply represented as natural lands with increased surface roughness length and reduced vegetation cover. However, the reproduction of the urban climate features in NWP and regional climate models is possible with the use of the so-called urban canopy models, that are able to parameterize the interaction between the urbanized surface and the overlying atmosphere. In this context, a new bulk parameterization scheme, TERRA_URB (TU), has been developed within the COSMO Consortium. TU offers an intrinsic representation of urban physics: the effect of buildings, streets and other man-made layers on the surface-atmosphere interaction is described by parameterizing the impervious water balance, translating the 3D urban-canopy parameters into bulk parameters with the Semi-empirical Urban canopy parameterization (SURY) and using the externally calculated anthropogenic heat flux as additional heat source. In this work, we present high-resolution simulations with the TU scheme, for different European cities, Turin, Naples and Moscow. An in-depth evaluation and verification of the performances of the recent COSMO version with TU scheme and new implemented physical parameterizations, such the ICON-like surface-layer turbulence scheme and the new formulation of the surface temperature, have been carried out. The validation concerned the 2-meter temperature and was performed for 1- or 2-week selected periods over the 3 European cities characterized by different environment and climate, namely the Moscow megacity in Russia and Turin and Naples in Italy. Even if the three domains are morphologically different, the results follow a common behavior. In particular, the activation of TERRA_URB provides a substantial improvement in capturing the UHI intensity and improving air temperature forecasts in urban areas. Potential benefits in the model performance also arise from a new turbulence scheme and the representation of skin-layer temperature (for vegetation). Our model framework provides promising perspectives for enhancing urban climate modelling, although further investigations are needed.</p>

Evaluating the Urban Canopy Scheme TERRA_URB in the COSMO Model for Selected European Cities

The increase in built surfaces constitutes the main reason for the formation of the Urban Heat Island (UHI), that is a metropolitan area significantly warmer than its surrounding rural areas. The urban heat islands and other urban-induced climate feedbacks may amplify heat stress and urban flooding under climate change and therefore to predict them correctly has become essential. Currently in the COSMO model, cities are represented by natural land surfaces with an increased surface roughness length and a reduced vegetation cover, but this approach is unable to correctly reproduce the UHI effect. By increasing the model resolution, a representation of the main physical processes that characterize the urban local meteorology should be addressed, in order to better forecast temperature, moisture and precipitation in urban environments. Within the COSMO Consortium a bulk parameterization scheme (TERRA_URB or TU) has been developed. It parametrizes the effects of buildings, streets and other man-made impervious surfaces on energy, moist and momentum exchanges between the surface and atmosphere, and additionally accounts for the anthropogenic heat flux as a heat source from the surface to the atmosphere. TU implements an impervious water-storage parameterization, and the Semi-empirical Urban canopy parametrization (SURY) that translates 3D urban canopy into bulk parameters. This paper presents evaluation results of the TU scheme in high-resolution simulations with a recent COSMO model version for selected European cities, namely Turin, Naples and Moscow. The key conclusion of the work is that the TU scheme in the COSMO model reasonably reproduces UHI effect and improves air temperature forecasts for all the investigated urban areas, despite each city has very different morphological characteristics. Our results highlight potential benefits of a new turbulence scheme and the representation of skin-layer temperature (for vegetation) in the model performance. Our model framework provides perspectives for enhancing urban climate modelling, although further investigations in improving model parametrizations, calibration and the use of more realistic urban canopy parameters are needed.

Reforecast of the November 1994 flood in Piedmont using ERA5 and COSMO model: an operational point of view

The scope of this work is to assess the progresses made in the warning alert system of Piedmont since the 1994 flood. We used the COSMO model at high horizontal resolution forced by ERA5 re-forecast to simulate the November 1994 event, performing also a simple sensitivity test regarding the parameterization of convection. We compared the results with the original forecast and with the available observations, in order to understand how the emission of the alert would have been affected using the current operational system.

Large impact of tiny model domain shifts for the Pentecost 2014 mesoscale convective system over Germany

The mesoscale convective system (MCS) that affected Germany at Pentecost 2014 (9 June 2014) was one of the most severe for decades. However, the predictability of this system was very low as the operational deterministic and ensemble prediction systems completely failed to predict the event with more than a 12 h lead time. We present hindcasts of the event using the COnsortium for Small-scale MOdeling (COSMO) model at a convection-permitting (2.8 km) resolution on a large (1668 km×1807 km) domain. Using this large domain allowed us to successfully simulate the whole life cycle of the system originating from the French Atlantic coast. However, even with the large domain, the predictability of the MCS is low. Tiny changes to the model domain produced large changes in the MCS, removing it completely from some simulations. To demonstrate this we systematically shifted the model domain by just one grid point in eight different directions, from which three did not simulate any convection over Germany. Our analysis shows that there were no important differences in domain-averaged initial conditions or in the preconvective environment ahead of the convective system. The main reason that one-third of these seemingly identical initial conditions fail to produce any convection over Germany seems to be the proximity of the track of the initial convective system to the coast and colder sea surface. The COSMO model simulates small horizontal displacements of the precursors of the MCS which then determine if the cells dissipate close to the sea or reach a favorable area for convective development over land and further evolve into an MCS. This study demonstrates the potentially huge impact of tiny model domain shifts on forecasting convective processes in this case, which suggests that the sensitivity to similarly small initial-condition perturbations could be a helpful indicator of days with low predictability and should be evaluated across other cases, models, and weather regimes.

High-resolution simulations with COSMO model including TERRA_URB TERRA_URB parameterization for the representation of Urban Heat Islands over South Italy

In this work, some preliminary numerical simulations with the COSMO model including TERRA_URB parameterization have been performed. In particular, this work concerns simulations over a small domain located in southern Italy, in order to test the capabilities of the model in reproducing the main climate features of Urban Heat Islands over this area. Model evaluation has been performed in terms of 2 m temperature in an urban area and in a rural one, in order to highlight the behaviour of the parameterization in different contexts. Numerical results encourage further investigation and development of urban parameterization in very high-resolution configuration of limited area models and specifically of COSMO, to improve the representation of the maximum daily values of temperature and diurnal cycle especially in urban, but also in rural areas. Furthermore a better parameter tuning is still required for this specific test case.

Validity of the hydrostatic approximation at convection-resolving scales: Diagnostic analysis and model intercomparison

<div>The increasing availability of computing power allows the use of kilometer-scale convection-resolving weather and climate models for operational forecasts. One of the open questions at these scales concerns the validity of the hydrostatic approximation, which assumes that vertical accelerations are small compared to the balancing forces of gravity and the vertical pressure gradient. This assumption is valid as long as the ratio of vertical to horizontal length scales of motion is small. Results from previous studies suggest that the horizontal resolution at which the hydrostatic approximation becomes invalid is highly dependent on the particular model, model configuration, and case setup.</div><div> </div><div>While most of the previous studies have been conducted with an idealized setup, this work will concentrate on a real-world case. To this end, a few summer days with strong convection over complex terrain in Europe are simulated with the nonhydrostatic regional Consortium for Small-scale Modelling (COSMO) model with horizontal resolutions ranging from 12 km to 275 m. To assess the validity of the hydrostatic approximation, we developed a hydrostatic reconstruction technique and diagnose the vertical wind using the hydrostatic set of equations. The diagnosed values are then compared to the actual nonhydrostatic up- and downdrafts with a statistical analysis of vertical wind speed frequencies for the different resolutions.</div><div> </div><div>Results suggest that the diagnosed hydrostatic vertical velocities are very similar to the nonhydrostatic vertical velocities up to horizontal resolutions of 1 km and thus the use of the hydrostatic approximations at these scales still seems to be a valid option.</div><div> </div><div> <div>Furthermore, the study contains an intercomparison of precipitation and vertical winds produced by the nonhydrostatic COSMO model and the hydrostatic Integrated Forecast System (IFS) from ECMWF for the same case. The intercomparison supports the previous findings that at resolutions of ∼2 km and ∼4 km the effect of the hydrostatic approximation is negligible. The results also show that a small enough timestep size is essential in order to properly resolve the high vertical velocities associated with convection.</div> </div>