Transport and Helfand moments in the Lennard-Jones fluid. II. Thermal Conductivity

The thermal conductivity is calculated with the Helfand-moment method in the Lennard-Jones fluid near the triple point. The Helfand moment of thermal conductivity is here derived for molecular dynamics with periodic boundary conditions. Thermal conductivity is given by a generalized Einstein relation with this Helfand moment. We compute thermal conductivity by this new method and compare it with our own values obtained by the standard Green-Kubo method. The agreement is excellent.Comment: Submitted to the Journal of Chemical Physic

Transport and Helfand moments in the Lennard-Jones fluid. I. Shear viscosity

We propose a new method, the Helfand-moment method, to compute the shear viscosity by equilibrium molecular dynamics in periodic systems. In this method, the shear viscosity is written as an Einstein-like relation in terms of the variance of the so-called Helfand moment. This quantity, is modified in order to satisfy systems with periodic boundary conditions usually considered in molecular dynamics. We calculate the shear viscosity in the Lennard-Jones fluid near the triple point thanks to this new technique. We show that the results of the Helfand-moment method are in excellent agreement with the results of the standard Green-Kubo method.Comment: Submitted to the Journal of Chemical Physic

Viscosity in the escape-rate formalism

We apply the escape-rate formalism to compute the shear viscosity in terms of the chaotic properties of the underlying microscopic dynamics. A first passage problem is set up for the escape of the Helfand moment associated with viscosity out of an interval delimited by absorbing boundaries. At the microscopic level of description, the absorbing boundaries generate a fractal repeller. The fractal dimensions of this repeller are directly related to the shear viscosity and the Lyapunov exponent, which allows us to compute its values. We apply this method to the Bunimovich-Spohn minimal model of viscosity which is composed of two hard disks in elastic collision on a torus. These values are in excellent agreement with the values obtained by other methods such as the Green-Kubo and Einstein-Helfand formulas.Comment: 16 pages, 16 figures (accepted in Phys. Rev. E; October 2003

4D-Var Assimilation of MIPAS chemical observations: ozone and nitrogen dioxide analyses

International audienceThis paper discusses the global analyses of stratospheric ozone (O3) and nitrogen dioxide (NO2) obtained by the Belgian Assimilation System for Chemical Observations from Envisat (BASCOE). Based on a chemistry transport model (CTM) and the 4-dimensional variational (4D-Var) method, BASCOE has assimilated chemical observations of O3, NO2, HNO3, N2O, CH4 and H2O, made between July 2002 and March 2004 by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard the European Space Agency (ESA) Environment Satellite (ENVISAT). This corresponds to the entire period during which MIPAS was operating at its nominal resolution. Our analyses are evaluated against assimilated MIPAS data and independent HALOE (HALogen Occultation Experiment) and POAM-III (Polar Ozone and Aerosol Measurement) satellite data. A good agreement is generally found between the analyses and these datasets, in both cases within the estimated error bars of the observations. The benefit of data assimilation is also evaluated using a BASCOE free model run. For O3, the gain from the assimilation is significant during ozone hole conditions, and in the lower stratosphere. Elsewhere, the free model run is within the MIPAS uncertainties and the assimilation does not provide significant improvement. For NO2, the gain from the assimilation is realized through most of the stratosphere. Using the BASCOE analyses, we estimate the differences between MIPAS data and independent data from HALOE and POAM-III, and find results close to those obtained by classical validation methods involving only direct measurement-to-measurement comparisons. Our results extend and reinforce previous MIPAS data validation efforts by taking account of a much larger variety of atmospheric states and measurement conditions. This study discusses possible further developments of the BASCOE data assimilation system; these concern the horizontal resolution, a better filtering of NO2 observations, and the photolysis calculation near the lid of the model. The ozone analyses are publicly available via the PROMOTE project http://www.gse-promote.org)

The vertical transport of methane from different potential emission types on Mars

The contrasting evolutionary behavior of the vertical profile of methane from three potential release scenarios is analysed using a global circulation model with assimilated temperature profiles. Understanding the evolving methane distribution is essential for interpretation of future retrievals of the methane vertical profile taken by instruments on the ExoMars Trace Gas Orbiter spacecraft. We show that at methane release rates constrained by previous observations and modelling studies, discriminating whether the methane source is a sustained or instantaneous surface emission requires at least ten sols of tracking the emission. A methane source must also be observed within five to ten sols of the initial emission to distinguish whether the emission occurs directly at the surface or within the atmosphere via destabilization of metastable clathrates. Assimilation of thermal data is shown to be critical for the most accurate back-tracking of an observed methane plume to its origin

A simple framework for modelling the photochemical response to solar spectral irradiance variability in the stratosphere

The stratosphere is thought to play a central role in the atmospheric response to solar irradiance variability. Recent observations suggest that the spectral solar irradiance (SSI) variability involves significant time-dependent spectral variations, with variable degrees of correlation between wavelengths, and new reconstructions are being developed. In this paper, we propose a simplified modelling framework to characterise the effect of short term SSI variability on stratospheric ozone. We focus on the pure photochemical effect, for it is the best constrained one. The photochemical effect is characterised using an ensemble simulation approach with multiple linear regression analysis. A photochemical column model is used with interactive photolysis for this purpose. Regression models and their coefficients provide a characterisation of the stratospheric ozone response to SSI variability and will allow future inter-comparisons between different SSI reconstructions. As a first step in this study, and to allow comparison with past studies, we take the representation of SSI variability from the Lean (1997) solar minimum and maximum spectra. First, solar maximum-minimum response is analysed for all chemical families and partitioning ratios, and is compared with past studies. The ozone response peaks at 0.18 ppmv (approximately 3%) at 37 km altitude. Second, ensemble simulations are regressed following two linear models. In the simplest case, an adjusted coefficient of determination <span style="border-top: 1px solid #000; color: #000;">R</span><sup>2</sup> larger than 0.97 is found throughout the stratosphere using two predictors, namely the previous day's ozone perturbation and the current day's solar irradiance perturbation. A better accuracy (<span style="border-top: 1px solid #000; color: #000;">R</span><sup>2</sup> larger than 0.9992) is achieved with an additional predictor, the previous day's solar irradiance perturbation. The regression models also provide simple parameterisations of the ozone perturbation due to SSI variability. Their skills as proxy models are evaluated independently against the photochemistry column model. The bias and RMS error of the best regression model are found smaller than 1% and 15% of the ozone response, respectively. Sensitivities to initial conditions and to magnitude of the SSI variability are also discussed

Explanation for the increase in high altitude water on Mars observed by NOMAD during the 2018 global dust storm

The Nadir and Occultation for MArs Discovery (NOMAD) instrument on board ExoMars Trace Gas Orbiter (TGO) measured a large increase in water vapor at altitudes in the range of 40‐100 km during the 2018 global dust storm on Mars. Using a three‐dimensional general circulation model, we examine the mechanism responsible for the enhancement of water vapor in the upper atmosphere. Experiments with different prescribed vertical profiles of dust show that when more dust is present higher in the atmosphere the temperature increases and the amount of water ascending over the tropics is not limited by saturation until reaching heights of 70‐100 km. The warmer temperatures allow more water to ascend to the mesosphere. Photochemical simulations show a strong increase in high‐altitude atomic hydrogen following the high‐altitude water vapor increase by a few days

Water Vapor Vertical Profiles on Mars in Dust Storms Observed by TGO/NOMAD

It has been suggested that dust storms efficiently transport water vapor from the near‐surface to the middle atmosphere on Mars. Knowledge of the water vapor vertical profile during dust storms is important to understand water escape. During Martian Year 34, two dust storms occurred on Mars: a global dust storm (June to mid‐September 2018) and a regional storm (January 2019). Here we present water vapor vertical profiles in the periods of the two dust storms (Ls = 162–260° and Ls = 298–345°) from the solar occultation measurements by Nadir and Occultation for Mars Discovery (NOMAD) onboard ExoMars Trace Gas Orbiter (TGO). We show a significant increase of water vapor abundance in the middle atmosphere (40–100 km) during the global dust storm. The water enhancement rapidly occurs following the onset of the storm (Ls~190°) and has a peak at the most active period (Ls~200°). Water vapor reaches very high altitudes (up to 100 km) with a volume mixing ratio of ~50 ppm. The water vapor abundance in the middle atmosphere shows high values consistently at 60°S‐60°N at the growth phase of the dust storm (Ls = 195°–220°), and peaks at latitudes greater than 60°S at the decay phase (Ls = 220°–260°). This is explained by the seasonal change of meridional circulation: from equinoctial Hadley circulation (two cells) to the solstitial one (a single pole‐to‐pole cell). We also find a conspicuous increase of water vapor density in the middle atmosphere at the period of the regional dust storm (Ls = 322–327°), in particular at latitudes greater than 60°S

Martian Ozone Observed by TGO/NOMAD‐UVIS Solar Occultation: An Inter‐Comparison of Three Retrieval Methods

The NOMAD‐UVIS instrument on board the ExoMars Trace Gas Orbiter has been investigating the Martian atmosphere with the occultation technique since April 2018. Here, we analyze almost two Mars Years of ozone vertical distributions acquired at the day‐night terminator. The ozone retrievals proved more difficult than expected due to spurious detections of ozone caused by instrumental effects, high dust content, and very low values of ozone. This led us to compare the results from three different retrieval approaches: (a) an onion peeling method, (b) a full occultation Optimal Estimation Method, and (c) a direct onion peeling method. The three methods produce consistently similar results, especially where ozone densities are higher. The main challenge was to find reliable criteria to exclude spurious detections of O3, and we finally adopted two criteria for filtering: (a) a detection limit, and (b) the Δχ2 criterion. Both criteria exclude spurious O3 values especially near the perihelion (180° < Ls < 340°), where up to 98% of ozone detections are filtered out, in agreement with general circulation models, that expect very low values of ozone in this season. Our agrees well with published analysis of the NOMAD‐UVIS data set, as we confirm the main features observed previously, that is, the high‐altitude ozone peak around 40 km at high latitudes. The filtering approaches are in good agreement with those implemented for the SPICAM/MEx observations and underline the need to evaluate carefully the quality of ozone retrievals in occultations

Expected Performances of the NOMAD/ExoMars instrument

NOMAD (Nadir and Occultation for MArs Discovery) is one of the four instruments on board the ExoMars Trace Gas Orbiter, scheduled for launch in March 2016. It consists of a suite of three high-resolution spectrometers – SO (Solar Occultation), LNO (Limb, Nadir and Occultation) and UVIS (Ultraviolet and Visible Spectrometer). Based upon the characteristics of the channels and the values of Signal-to-Noise Ratio obtained from radiometric models discussed in [Vandaele et al., Optics Express, 2015] and [Thomas et al., Optics Express, 2015], the expected performances of the instrument in terms of sensitivity to detection have been investigated. The analysis led to the determination of detection limits for 18 molecules, namely CO, H2O, HDO, C2H2, C2H4, C2H6, H2CO, CH4, SO2, H2S, HCl, HCN, HO2, NH3, N2O, NO2, OCS, O3. NOMAD should have the ability to measure methane concentrations <25 parts per trillion (ppt) in solar occultation mode, and 11 parts per billion in nadir mode. Occultation detections as low as 10 ppt could be made if spectra are averaged [Drummond et al., Planetary Space and Science, 2011]. Results have been obtained for all three channels in nadir and in solar occultation