Atomistic modeling of dopant segregation in alpha-alumina ceramics: Coverage dependent energy of segregation and nominal dopant solubility

Microstructural control is a key aspect in producing ceramics with tailored properties and is often achieved by using dopants in a rather empirical fashion. Atomic scale simulations could provide much needed insight but the long-standing challenge of linking simulation results on isolated grain boundaries to those measured in real ceramics needs to be resolved. Here a novel Monte-Carlo simulation method based on a microstructural model in combination with energies obtained from atomic scale energy minimization is presented. This approach allows, for the first time, the prediction of the nominal solubility of dopants (Y, La and Mg) in a ceramic purely from theory. Results compare well with segregation/precipitation data as a function of grain size, found in the literature. The method can therefore be used in developing experimental guidelines for the effective use of dopants in ceramic production, thus accelerating the development of novel materials required for innovative applications

Sensitivity of feedback effects in CBMZ/MOSAIC chemical mechanism

To investigate the impact of the aerosol effects on meteorological variables and pollutant concentrations two simulations with the WRF-Chem model have been performed over Europe for year 2010. We have performed a baseline simulation without any feedback effects and a second simulation including the direct as well as the indirect aerosol effect. The paper describes the full configuration of the model, the simulation design, special impacts and evaluation. Although low aerosol particle concentrations are detected, the inclusion of the feedback effects results in an increase of solar radiation at the surface over cloudy areas (North-West, including the Atlantic) and decrease over more sunny locations (South-East). Aerosol effects produce an increase of the water vapor and decrease the planet boundary layer height over the whole domain except in the Sahara area, where the maximum particle concentrations are detected. Significant ozone concentrations are found over the Mediterranean area. Simulated feedback effects between aerosol concentrations and meteorological variables and on pollutant distributions strongly depend on the aerosol concentrations and the clouds. Further investigations are necessary with higher aerosol particle concentrations. WRF-Chem variables are evaluated using available hourly observations in terms of performance statistics. Standardized observations from the ENSEMBLE system web-interface were used. The research was developed under the second phase of Air Quality Model Evaluation International Initiative (AQMEII). WRF-Chem demonstrates its capability in capturing temporal and spatial variations of the major meteorological variables and pollutants, except the wind speed over complex terrain. The wind speed bias may affect the accuracy in the chemical predictions (NO2, SO2). The analysis of the correlations between simulated data sets and observational data sets indicates that the simulation with aerosol effects performs slightly better. These results indicate potential importance of the aerosol feedback effects and an urgent need to further improve the representations in current atmospheric models to reduce uncertainties at all scales

The human equilibrative nucleoside transporter 1 mediates in vitro cytarabine sensitivity in childhood acute myeloid leukaemia

Cytarabine (ara-C) is the most effective agent for the treatment of acute myeloid leukaemia (AML). Aberrant expression of enzymes involved in the transport/metabolism of ara-C could explain drug resistance. We determined mRNA expression of these factors using quantitative-real-time-PCR in leukemic blasts from children diagnosed with de novo AML. Expression of the inactivating enzyme pyrimidine nucleotidase-I (PN-I) was 1.8-fold lower in FAB-M5 as compared to FAB-M1/2 (P=0.007). In vitro sensitivity to deoxynucleoside analogues was determined using the MTT-assay. Human equilibrative nucleoside transporter-1 (hENT1) mRNA expression and ara-C sensitivity were significantly correlated (rp=−0.46; P=0.001), with three-fold lower hENT1 mRNA levels in resistant patients (P=0.003). hENT1 mRNA expression also seemed to correlate inversely with the LC50 values of cladribine (rp=−0.30; P=0.04), decitabine (rp=−0.29; P=0.04) and gemcitabine (rp=−0.33; P=0.02). Deoxycytidine kinase (dCK) and cytidine deaminase (CDA) mRNA expression seemed to correlate with in vitro sensitivity to gemcitabine (rp=−0.31; P=0.03) and decitabine (rp=0.33; P=0.03), respectively. The dCK/PN-I ratio correlated inversely with LC50 values for gemcitabine (rp=−0.45, P=0.001) and the dCK/CDA ratio seemed to correlate with LC50 values for decitabine (rp=−0.29; 0.04). In conclusion, decreased expression of hENT1, which transports ara-C across the cell membrane, appears to be a major factor in ara-C resistance in childhood AML

Revisiting the Local Scaling Hypothesis in Stably Stratified Atmospheric Boundary Layer Turbulence: an Integration of Field and Laboratory Measurements with Large-eddy Simulations

The `local scaling' hypothesis, first introduced by Nieuwstadt two decades ago, describes the turbulence structure of stable boundary layers in a very succinct way and is an integral part of numerous local closure-based numerical weather prediction models. However, the validity of this hypothesis under very stable conditions is a subject of on-going debate. In this work, we attempt to address this controversial issue by performing extensive analyses of turbulence data from several field campaigns, wind-tunnel experiments and large-eddy simulations. Wide range of stabilities, diverse field conditions and a comprehensive set of turbulence statistics make this study distinct

Modelling chemistry in the nocturnal boundary layer above tropical rainforest and a generalised effective nocturnal ozone deposition velocity for sub-ppbv NOx conditions

Measurements of atmospheric composition have been made over a remote rainforest landscape. A box model has previously been demonstrated to model the observed daytime chemistry well. However the box model is unable to explain the nocturnal measurements of relatively high [NO] and [O3], but relatively low observed [NO2]. It is shown that a one-dimensional (1-D) column model with simple O3 -NOx chemistry and a simple representation of vertical transport is able to explain the observed nocturnal concentrations and predict the likely vertical profiles of these species in the nocturnal boundary layer (NBL). Concentrations of tracers carried over from the end of the night can affect the atmospheric chemistry of the following day. To ascertain the anomaly introduced by using the box model to represent the NBL, vertically-averaged NBL concentrations at the end of the night are compared between the 1-D model and the box model. It is found that, under low to medium [NOx] conditions (NOx <1 ppbv), a simple parametrisation can be used to modify the box model deposition velocity of ozone, in order to achieve good agreement between the box and 1-D models for these end-of-night concentrations of NOx and O3. This parametrisation would could also be used in global climate-chemistry models with limited vertical resolution near the surface. Box-model results for the following day differ significantly if this effective nocturnal deposition velocity for ozone is implemented; for instance, there is a 9% increase in the following day’s peak ozone concentration. However under medium to high [NOx] conditions (NOx > 1 ppbv), the effect on the chemistry due to the vertical distribution of the species means no box model can adequately represent chemistry in the NBL without modifying reaction rate constants

Evaluating the capability of regional-scale air quality models to cature the vertical distribution of pollutants

This study is conducted in the framework of the Air Quality Modelling Evaluation International Initiative (AQMEII) and aims at the operational evaluation of an ensemble of 12 regional-scale chemical transport models used to predict air quality over the North American (NA) and European (EU) continents for 2006. The modelled concentrations of ozone and CO, along with the meteorological fields of wind speed (WS) and direction (WD), temperature (T), and relative humidity (RH), are compared against high-quality in-flight measurements collected by instrumented commercial aircraft as part of the Measurements of OZone, water vapour, carbon monoxide and nitrogen oxides by Airbus In-service airCraft (MOZAIC) programme. The evaluation is carried out for five model domains positioned around four major airports in NA (Portland, Philadelphia, Atlanta, and Dallas) and one in Europe (Frankfurt), from the surface to 8.5 km. We compare mean vertical profiles of modelled and measured variables for all airports to compute error and variability statistics, perform analysis of altitudinal error correlation, and examine the seasonal error distribution for ozone, including an estimation of the bias introduced by the lateral boundary conditions (BCs). The results indicate that model performance is highly dependent on the variable, location, season, and height (e.g. surface, planetary boundary layer (PBL) or free troposphere) being analysed. While model performance for T is satisfactory at all sites (correlation coefficient in excess of 0.90 and fractional bias ≤ 0.01 K), WS is not replicated as well within the PBL (exhibiting a positive bias in the first 100 m and also underestimating observed variability), while above 1000 m, the model performance improves (correlation coefficient often above 0.9). The WD at NA airports is found to be biased in the PBL, primarily due to an overestimation of westerly winds. RH is modelled well within the PBL, but in the free troposphere large discrepancies among models are observed, especially in EU. CO mixing ratios show the largest range of modelled-to-observed standard deviations of all the examined species at all heights and for all airports. Correlation coefficients for CO are typically below 0.6 for all sites and heights, and large errors are present at all heights, particularly in the first 250 m. Model performance for ozone in the PBL is generally good, with both bias and error within 20%. Profiles of ozone mixing ratios depend strongly on surface processes, revealed by the sharp gradient in the first 2 km (10 to 20 ppb km−1). Modelled ozone in winter is biased low at all locations in the NA, primarily due to an underestimation of ozone from the BCs. Most of the model error in the PBL is due to surface processes (emissions, transport, photochemistry), while errors originating aloft appear to have relatively limited impact on model performance at the surface. Suggestions for future work include interpretation of the model-to-model variability and common sources of model bias, and linking CO and ozone bias to the bias in the meteorological fields. Based on the results from this study, we suggest possible in-depth, process-oriented and diagnostic investigations to be carried out next

MEGAPOLI: concept of multi-scale modelling of megacity impact on air quality and climate

The EU FP7 Project MEGAPOLI: "Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation" (http://megapoli.info) brings together leading European research groups, state-of-the-art scientific tools and key players from non-European countries to investigate the interactions among megacities, air quality and climate. MEGAPOLI bridges the spatial and temporal scales that connect local emissions, air quality and weather with global atmospheric chemistry and climate. The suggested concept of multi-scale integrated modelling of megacity impact on air quality and climate and vice versa is discussed in the paper. It requires considering different spatial and temporal dimensions: time scales from seconds and hours (to understand the interaction mechanisms) up to years and decades (to consider the climate effects); spatial resolutions: with model down- and up-scaling from street- to global-scale; and two-way interactions between meteorological and chemical processes

Seasonal ozone vertical profiles over North America using the AQMEII3 group of air quality models: model inter-comparison and stratospheric intrusions

This study evaluates simulated vertical ozone profiles produced in the framework of the third phase of the Air Quality Model Evaluation International Initiative (AQMEII3) against ozonesonde observations in North America for the year 2010. Four research groups from the United States (US) and Europe have provided modeled ozone vertical profiles to conduct this analysis. Because some of the modeling systems differ in their meteorological drivers, wind speed and temperature are also included in the analysis. In addition to the seasonal ozone profile evaluation for 2010, we also analyze chemically inert tracers designed to track the influence of lateral boundary conditions on simulated ozone profiles within the modeling domain. Finally, cases of stratospheric ozone intrusions during May–June 2010 are investigated by analyzing ozonesonde measurements and the corresponding model simulations at Intercontinental Chemical Transport Experiment Ozonesonde Network Study (IONS) experiment sites in the western United States. The evaluation of the seasonal ozone profiles reveals that, at a majority of the stations, ozone mixing ratios are underestimated in the 1–6&thinsp;km range. The seasonal change noted in the errors follows the one seen in the variance of ozone mixing ratios, with the majority of the models exhibiting less variability than the observations. The analysis of chemically inert tracers highlights the importance of lateral boundary conditions up to 250&thinsp;hPa for the lower-tropospheric ozone mixing ratios (0–2&thinsp;km). Finally, for the stratospheric intrusions, the models are generally able to reproduce the location and timing of most intrusions but underestimate the magnitude of the maximum mixing ratios in the 2–6&thinsp;km range and overestimate ozone up to the first kilometer possibly due to marine air influences that are not accurately described by the models. The choice of meteorological driver appears to be a greater predictor of model skill in this altitude range than the choice of air quality model.</p

Assessment of the MACC reanalysis and its influence as chemical boundary conditions for regional air quality modeling in AQMEII-2

The Air Quality Model Evaluation International Initiative (AQMEII) has now reached its second phase which is dedicated to the evaluation of online coupled chemistry-meteorology models. Sixteen modeling groups from Europe and five from North America have run regional air quality models to simulate the year 2010 over one European and one North American domain. The MACC re-analysis has been used as chemical initial (IC) and boundary conditions (BC) by all participating regional models in AQMEII-2. The aim of the present work is to evaluate the MACC re-analysis along with the participating regional models against a set of ground-based measurements (O3, CO, NO, NO2, SO2, SO42−) and vertical profiles (O3 and CO). Results indicate different degrees of agreement between the measurements and the MACC re-analysis, with an overall better performance over the North American domain. The influence of BC on regional air quality simulations is analyzed in a qualitative way by contrasting model performance for the MACC re-analysis with that for the regional models. This approach complements more quantitative approaches documented in the literature that often have involved sensitivity simulations but typically were limited to only one or only a few regional scale models. Results suggest an important influence of the BC on ozone for which the underestimation in winter in the MACC re-analysis is mimicked by the regional models. For CO, it is found that background concentrations near the domain boundaries are rather close to observations while those over the interior of the two continents are underpredicted by both MACC and the regional models over Europe but only by MACC over North America. This indicates that emission differences between the MACC re-analysis and the regional models can have a profound impact on model performance and points to the need for harmonization of inputs in future linked global/regional modeling studies