Estimating relationships between air mass origin and chemical composition

Observations of a chemical at a point in the atmosphere typically show sudden transitions between episodes of high and low concentration. Often these are associated with a rapid change in the origin of air arriving at the site. Lagrangian chemical models riding along trajectories can reproduce such transitions, but small timing errors from trajectory phase errors dramatically reduce the correlation between modeled concentrations and observations. Here the origin averaging technique is introduced to obtain maps of average concentration as a function of air mass origin for the East Atlantic Summer Experiment 1996 (EASE96, a ground-based chemistry campaign). These maps are used to construct origin averaged time series which enable comparison between a chemistry model and observations with phase errors factored out. The amount of the observed signal explained by trajectory changes can be quantified, as can the systematic model errors as a function of air mass origin. The Cambridge Tropospheric Trajectory model of Chemistry and Transport (CiTTyCAT) can account for over 70% of the observed ozone signal variance during EASE96 when phase errors are side-stepped by origin averaging. The dramatic increase in correlation (from 23% without averaging) cannot be achieved by time averaging. The success of the model is attributed to the strong relationship between changes in ozone along trajectories and their origin and its ability to simulate those changes. The model performs less well for longer-lived chemical constituents because the initial conditions 5 days before arrival are insufficiently well known.

Can carbon surface oxidation shift the pore size distribution curve calculated from Ar, N(2) and CO(2) adsorption isotherms? Simulation results for a realistic carbon model

Using the virtual porous carbon model proposed by Harris et al, we study the effect of carbon surface oxidation on the pore size distribution (PSD) curve determined from simulated Ar, N(2) and CO(2) isotherms. It is assumed that surface oxidation is not destructive for the carbon skeleton, and that all pores are accessible for studied molecules (i.e., only the effect of the change of surface chemical composition is studied). The results obtained show two important things, i.e., oxidation of the carbon surface very slightly changes the absolute porosity (calculated from the geometric method of Bhattacharya and Gubbins (BG)); however, PSD curves calculated from simulated isotherms are to a greater or lesser extent affected by the presence of surface oxides. The most reliable results are obtained from Ar adsorption data. Not only is adsorption of this adsorbate practically independent from the presence of surface oxides, but, more importantly, for this molecule one can apply the slit-like model of pores as the first approach to recover the average pore diameter of a real carbon structure. For nitrogen, the effect of carbon surface chemical composition is observed due to the quadrupole moment of this molecule, and this effect shifts the PSD curves compared to Ar. The largest differences are seen for CO2, and it is clearly demonstrated that the PSD curves obtained from adsorption isotherms of this molecule contain artificial peaks and the average pore diameter is strongly influenced by the presence of electrostatic adsorbate-adsorbate as well as adsorbate-adsorbent interactions.

Normal mode Rossby waves and their effects on chemical composition in the late summer stratosphere

During past MANTRA campaigns, ground-based measurements of several long-lived chemical species have revealed quasi-periodic fluctuations on time scales of several days. These fluctuations could confound efforts to detect long-term trends from MANTRA, and need to be understood and accounted for. Using the Canadian Middle Atmosphere Model, we investigate the role of dynamical variability in the late summer stratosphere due to normal mode Rossby waves and the impact of this variability on fluctuations in chemical species. Zonal wavenumber 1, westward travelling waves are considered with average periods of 5, 10 and 16 days. Time-lagged correlations between the temperature and nitrous oxide, methane and ozone fields are calculated in order to assess the possible impact of these waves on the chemical species. Using Fourier-wavelet decomposition and correlating the fluctuations between the temperature and chemical fields, we determine that variations in the chemical species are well-correlated with the 5- and 10-day waves between 30 and 60 km, although the nature of the correlations depend strongly on altitude. Interannual variability of the waves is also examined.