-
This paper presents a procedure for performing and optimizing inversions for DOAS tomography and its application to measurement data. DOAS tomography is a new technique to determine 2- and 3-dimensional concentration fields of air pollutants or other trace gases by combining differential optical absorption spectroscopy (DOAS) with tomographic inversion techniques. Due to the limited amount of measured data, the resulting concentration fields are sensitive to the inversion process. Therefore detailed error estimations are needed to determine the quality of the reconstruction. In this paper we compare different row acting methods for the inversion, present a procedure for optimizing the parameters of the reconstruction process and propose a way to estimate the error-fields by numerical studies. The procedure was applied to data from the motorway emission campaign BAB II. Two dimensional NO<sub>2</sub> cross sections at right angles to the motorway could be reconstructed qualitatively well at different meteorological situations. Additionally we present error fields for the reconstructions which show the problems and skills of the used measurement setup. Numerical studies on an improved setup for future motorway campaigns show, that DOAS tomography is able to produce high quality concentration maps.
-
Meteors are an important source for (a) the metal atoms of the upper atmosphere metal layers and (b) for condensation nuclei, the existence of which are a prerequisite for the formation of noctilucent cloud particles in the polar mesopause region. For a better understanding of these phenomena, it would be helpful to know accurately the annual and diurnal variations of meteor rates. So far, these rates have been little studied at polar latitudes. Therefore we have used the 33 MHz meteor radar of the ALOMAR observatory at 69° N to measure the meteor rates at this location for two full annual cycles. This site, being within 3° of the Arctic circle, offers in addition an interesting capability: The axis of its antenna field points (almost) towards the North ecliptic pole once each day of the year. In this particular viewing direction, the radar monitors the meteoroid influx from (almost) the entire ecliptic Northern hemisphere. <P style="line-height: 20px;"> We report on the observed diurnal variations (averaged over one month) of meteor rates and their significant alterations throughout the year. The ratio of maximum over minimum meteor rates throughout one diurnal cycle is in January and February about 5, from April through December 2.3±0.3. If compared with similar measurements at mid-latitudes, our expectation, that the amplitude of the diurnal variation is to decrease towards the North pole, is not really borne out. <P style="line-height: 20px;"> Observations with the antenna axis pointing towards the North ecliptic pole showed that the rate of deposition of meteoric dust is substantially larger during the Arctic NLC season than the annual mean deposition rate. The daylight meteor showers of the Arietids, Zeta Perseids, and Beta Taurids supposedly contribute considerably to the June maximum of meteor rates. We note, though, that with the radar antenna pointing as described above, all three meteor radiants are close to the local horizon but all three radiants were detected.
-
The room temperature kinetics of gas-phase ozone loss via heterogeneous interactions with thin alumina films has been studied in real-time using 254nm absorption spectroscopy to monitor ozone concentrations. The films were prepared from dispersions of fine alumina powder in methanol and their surface areas were determined by an in situ procedure using adsorption of krypton at 77K. The alumina was found to lose reactivity with increasing ozone exposure. However, some of the lost reactivity could be recovered over timescales of days in an environment free of water, ozone and carbon dioxide. From multiple exposures of ozone to the same film, it was found that the number of active sites is large, greater than 1.4x10<sup>14</sup> active sites per cm<sup>2</sup> of surface area or comparable to the total number of surface sites. The films maintain some reactivity at this point, which is consistent with there being some degree of active site regeneration during the experiment and with ozone loss being catalytic to some degree. The initial uptake coefficients on fresh films were found to be inversely dependent on the ozone concentration, varying from roughly 10<sup>-6</sup> for ozone concentrations of 10<sup>14</sup> molecules/cm<sup>3</sup> to 10<sup>-5</sup> at 10<sup>13</sup> molecules/cm<sup>3</sup>. The initial uptake coefficients were not dependent on the relative humidity, up to 75%, within the precision of the experiment. The reaction mechanism is discussed, as well as the implications these results have for assessing the effect of mineral dust on atmospheric oxidant levels.
-
A thermal volatility technique is used to provide indirect information about the chemical composition of the aerosol involved in cirrus cloud formation. The fraction of particles that disappears after being heated to 125°C is termed volatile and the fraction that disappears between 125 and 250°C is termed semi-volatile. Particles that still remain after being heated to 250°C make up the non-volatile fraction. The thermal composition of residual particles remaining from evaporated cirrus crystals is presented and compared to interstitial aerosol particles (non-activated particles in between the cirrus crystals) for two temperature regimes (cold: T< -38°C, warm: -38≤T< -23°C), based on in-situ observations. The observations were conducted in cirrus clouds in the Southern Hemisphere (SH) and Northern Hemisphere (NH) midlatitudes during the INCA project. In the cold temperature regime, the non-volatile fraction of the residual particles was typically in the range 10 to 30% in the NH and 30 to 40% in the SH. In the warm temperature regime, the non-volatile residual fraction was typically 10 to 30% (NH) and 20 to 40% (SH). At high crystal number densities the non-volatile fraction in both temperature regimes was even higher: in the range of 30 to 40% (NH) and 40 to 50% (SH). The semi-volatile fraction was typically less than 10% in both hemispheres, causing the volatile fraction to essentially be a complement to the non-volatile fraction. In terms of the fractioning into the three types of particles, the SH cold case is clearly different compared to the other three cases (the two warm cases and the cold NH case), which share many features. In the NH data the distribution of different particle types does not seem to be temperature dependent. In all the cases, the non-volatile fraction is enriched in the residual particles compared to the fractions observed for the interstitial particles. This enrichment corresponds to about 15 (NH) and 30 (SH) percent units in the two cold cases and to 15-25 (NH) and 25-35 (SH) percent units in the two warm cases. In the NH cold case, there is a clear relation between the fractions observed in the interstitial particles and what is observed in the residual particles. The observed large fractions of non-volatile particles show that particles forming ice crystals are not entirely made up of water-soluble sulfate particles.
-
In May 2003, severe forest fires in southeast Russia resulted in smoke plumes extending widely across the Northern Hemisphere. This study combines satellite data from a variety of platforms (Moderate Resolution Imaging Spectroradiometer (MODIS), Sea-viewing Wide Field-of-view Sensor (SeaWiFS), Earth Probe Total Ozone Mapping Spectrometer (TOMS) and Global Ozone Monitoring Experiment (GOME)) and vertical aerosol profiles derived with Raman lidar measurements with results from a Lagrangian particle dispersion model to understand the transport processes that led to the large haze plumes observed over North America and Europe. The satellite images provided a unique opportunity for validating model simulations of tropospheric transport on a truly hemispheric scale. Transport of the smoke occurred in two directions: Smoke travelling northwestwards towards Scandinavia was lifted over the Urals and arrived over the Norwegian Sea. Smoke travelling eastwards to the Okhotsk Sea was also lifted, it then crossed the Bering Sea to Alaska from where it proceeded to Canada and was later even observed over Scandinavia and Eastern Europe on its way back to Russia. Not many events of this kind, if any, have been observed, documented and simulated with a transport model comprehensively. The total transport time was about 17 days. We compared transport model simulations using meteorological analysis data from both the European Centre for Medium-Range Weather Forecast (ECMWF) and the National Center for Environmental Prediction (NCEP) in order to find out how well this event could be simulated using these two datasets. Although differences between the two simulations are found on small scales, both agree remarkably well with each other and with the observations on large scales. On the basis of the available observations, it cannot be decided which simulation was more realistic.
-
The age of firn air in Antarctica at pore close-off depth is only known for a few specific sites where firn air has been sampled for analyses. We present a model that calculates the age of firn air at pore close-off depth for the entire Antarctic continent. The model basically uses four meteorological parameters as input (surface temperature, pressure, accumulation rate and wind speed). Using parameterisations for surface snow density, pore close-off density and tortuosity, in combination with a density-depth model and data of a regional atmospheric climate model, distribution of pore close-off depth for the entire Antarctic continent is determined. The deepest pore close-off depth was found for the East Antarctic Plateau near 72° E, 82° S, at 150±15 m (2σ). A firn air diffusion model was applied to calculate the age of CO<sub>2</sub> at pore close-off depth. The results predict that the oldest firn gas (CO<sub>2</sub> age) is located between Dome Fuji, Dome Argos and Vostok at 43° E, 78° S being 148±23 (1σ or 38 for 2σ) years old. At this location an atmospheric trace gas record should be obtained. In this study we show that methyl chloride could be recorded with a predicted length of 125 years as an example for trace gas records at this location. The longest record currently available from firn air is derived at South Pole, being 80 years. <P style="line-height: 20px;"> Sensitivity tests reveal that the locations with old firn air (East Antarctic Plateau) have an estimated uncertainty (2σ) for the modelled CO<sub>2</sub> age at pore close-off depth of 30% and of about 40% for locations with younger firn air (CO<sub>2</sub> age typically 40 years). Comparing the modelled age of CO<sub>2</sub> at pore close-off depth with directly determined ages at seven sites yielded a correlation coefficient of 0.90 and a slope close to 1, suggesting a high level of confidence for the modelled results in spite of considerable remaining uncertainties.
-
The aim of this paper is to compare two different modelling systems and to evaluate their ability to simulate high values of ozone concentration in typical summer episodes which take place in the north of Spain near the metropolitan area of Barcelona. As the focus of the paper is the comparison of the two systems, we do not attempt to improve the agreement by adjusting the emission inventory or model parameters. <P style="line-height: 20px;"> The first model, or forecasting system, is made up of three modules. The first module is a mesoscale model (MASS). This provides the initial condition for the second module, which is a nonlocal boundary layer model based on the transilient turbulence scheme. The third module is a photochemical box model (OZIPR), which is applied in Eulerian and Lagrangian modes and receives suitable information from the two previous modules. The model forecast is evaluated against ground base stations during summer 2001. The second model is the MM5/UAM-V. This is a grid model designed to predict the hourly three-dimensional ozone concentration fields. The model is applied during an ozone episode that occurred between 21 and 23 June 2001. Our results reflect the good performance of the two modelling systems when they are used in a specific episode.
-
The kinetics of uptake of gaseous N<sub>2</sub>O<sub>5</sub> on submicron aerosols containing NaCl and natural sea salt have been investigated in a flow reactor as a function of relative humidity (<i>RH</i>) in the range 30-80% at 295±2K and a total pressure of 1bar. The measured uptake coefficients, γ, were larger on the aerosols containing sea salt compared to those of pure NaCl, and in both cases increased with increasing <i>RH</i>. These observations are explained in terms of the variation in the size of the salt droplets, which leads to a limitation in the uptake rate into small particles. After correction for this effect the uptake coefficients are independent of relative humidity, and agree with those measured previously on larger droplets. A value of γ=0.025 is recommended for the reactive uptake coefficient for N<sub>2</sub>O<sub>5</sub> on deliquesced sea salt droplets at 298K and <i>RH</i>>40%.
-
In the present paper, we have calculated the outgoing longwave radiation at the top of the atmosphere (OLR at TOA) using a deterministic radiation transfer model, cloud data from ISCCP-D, and atmospheric temperature and humidity data from NCEP/NCAR reanalysis, for the seventeen-year period 1984-2000. We constructed anomaly time-series of the OLR at TOA, as well as of all of the key input climatological data, averaged in the tropical region between 20°N and 20°S. We compared the anomaly time-series of the model calculated OLR at TOA with that obtained from the ERBE S-10N (WFOV NF edition 2) non-scanner measurements. The model results display very similar seasonal and inter-annual variability as the ERBS data, and indicate a decadal increase of OLR at TOA of 1.9±0.2Wm<sup>-2</sup>/decade, which is lower than that displayed by the ERBS time-series (3.5±0.3Wm<sup>-2</sup>). Analysis of the inter-annual and long-term variability of the various parameters determining the OLR at TOA, showed that the most important contribution to the observed trend comes from a decrease in high-level cloud cover over the period 1984-2000, followed by an apparent drying of the upper troposphere and a decrease in low-level cloudiness. Opposite but small trends are introduced by a decrease in low-level cloud top pressure, an apparent cooling of the lower stratosphere (at the 50mbar level) and a small decadal increase in mid-level cloud cover.
-
A unique halocarbon dataset has been obtained using the Australian high altitude research aircraft, the Grob G520T Egrett, during May-June 2000 with GC instrument (DIRAC), which has been previously deployed on balloon platforms. The halocarbon data generally shows a good anticorrelation with ozone data obtained simultaneously from commercial sensors. On 5 June 2000, at 380K, the Egrett entered a high latitude tongue of air over the U.K. CFC-11 and O<sub>3</sub> data obtained on the flight show evidence of this feature. The dataset has been used, in conjunction with a 3D chemical transport model, to infer ozone depletion encountered in the midlatitude lower stratosphere during the flight. We calculate that ozone is depleted by 20% relative to its winter value in the higher latitude airmass. A suite of ozone loss tracers in the model have been used to track ozone depletion according to location relative to the vortex and chemical cycle responsible. The model, initialised on 9 December, indicates that 50% of the total chemical ozone destruction encountered in June in the middle latitudes occurred in the 90-70°N equivalent latitude band and that 70% was due to halogen chemistry.
