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Cloud radiative forcing is a very important concept to understand what kind of role the clouds play in climate change with thermal effect or albedo effect. In spite of that much progress has been achieved, the clouds are still poorly described in the climate models. Due to the complex aerosol-cloud-radiation interactions, high surface albedo of snow and ice cover, and without solar radiation in long period of the year, the Arctic strong warming caused by increasing greenhouse gases (as most GCMs suggested) has not been verified by the observations. In this study, we were dedicated to quantify the aerosol effect on the Arctic cloud radiative forcing by Northern Aerosol Regional Climate Model (NARCM). Major aerosol species such as Arctic haze sulphate, black carbon, sea salt, organics and dust have been included during our simulations. By inter-comparisons with the Atmospheric Radiation Measurement (ARM) data, we find surface cloud radiative forcing (SCRF) is −22 W/m<sup>2</sup> for shortwave and 36 W/m<sup>2</sup> for longwave. Total cloud forcing is 14 W/m<sup>2</sup> with minimum of −35 W/m<sup>2</sup> in early July. If aerosols are taken into account, the SCRF has been increased during winter while negative SCRF has been enhanced during summer. Our estimate of aerosol forcing is about −6 W/m<sup>2</sup> in the Arctic.
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In this work, existing and modified activity coefficient models are examined in order to assess their capabilities to describe the properties of aqueous solution droplets relevant in the atmosphere. Five different water-organic-electrolyte activity coefficient models were first selected from the literature. Only one of these models included organics and electrolytes which are common in atmospheric aerosol particles. In the other models, organic species were solvents such as alcohols, and important atmospheric ions like NH<sub>4</sub><sup>+</sup> could be missing. The predictions of these models were compared to experimental activity and solubility data in aqueous single electrolyte solutions with 31 different electrolytes. <P style="line-height: 20px;"> Based on the deviations from experimental data and on the capabilities of the models, four predictive models were selected for fitting of new parameters for binary and ternary solutions of common atmospheric electrolytes and organics. New electrolytes (H<sup>+</sup>, NH<sub>4</sub><sup>+</sup>, Na<sup>+</sup>, Cl<sup>-</sup>, NO<sub>3</sub><sup>-</sup> and SO<sub>4</sub><sup>2-</sup>) and organics (dicarboxylic and some hydroxy acids) were added and some modifications were made to the models if it was found useful. All new and most of the existing parameters were fitted to experimental single electrolyte data as well as data for aqueous organics and aqueous organic-electrolyte solutions. Unfortunately, there are very few data available for organic activities in binary solutions and for organic and electrolyte activities in aqueous organic-electrolyte solutions. This reduces model capabilities in predicting solubilities. <P style="line-height: 20px;"> After the parameters were fitted, deviations from measurement data were calculated for all fitted models, and for different data types. These deviations and the calculated property values were compared with those from other non-electrolyte and organic-electrolyte models found in the literature. Finally, hygroscopic growth factors were calculated for four 100 nm organic-electrolyte particles and these predictions were compared to experimental data and to predictions from other models. <P style="line-height: 20px;"> All of the newly fitted models show good agreement with experimental water activity data in binary and ternary solutions. One of the models is for activities of non-electrolytes only, but the other three models show quite small deviations from measured electrolyte activities. Because there were not enough experimental data for organic and electrolyte activities, some models show bigger deviation for mutual deliquescence relative humidities of organic-electrolyte particles, but calculated growth factors for liquid droplets are quite close to the experimental data. Even in cases with somewhat bigger deviations, the results can be considered satisfactory, because they were calculated based mainly on the predictive properties of the models.
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Organic compounds emitted in the atmosphere are oxidized in complex reaction sequences that produce a myriad of intermediates. Although the cumulative importance of these organic intermediates is widely acknowledged, there is still a critical lack of information concerning the detailed composition of the highly functionalized secondary organics in the gas and condensed phases. The evaluation of their impacts on pollution episodes, climate, and the tropospheric oxidizing capacity requires modelling tools that track the identity and reactivity of organic carbon in the various phases down to the ultimate oxidation products, CO and CO<sub>2</sub>. However, a fully detailed representation of the atmospheric transformations of organic compounds involves a very large number of intermediate species, far in excess of the number that can be reasonably written manually. This paper describes (1) the development of a data processing tool to generate the explicit gas-phase oxidation schemes of acyclic hydrocarbons and their oxidation products under tropospheric conditions and (2) the protocol used to select the reaction products and the rate constants. Results are presented using the fully explicit oxidation schemes generated for two test species: n-heptane and isoprene. Comparisons with well-established mechanisms were performed to evaluate these generated schemes. Some preliminary results describing the gradual change of organic carbon during the oxidation of a given parent compound are presented.
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The objective of this work was to develop and assess an automatic procedure to generate reduced chemical schemes for the atmospheric photooxidation of volatile organic carbon (VOC) compounds. The procedure is based on (i) the development of a tool for writing the fully explicit schemes for VOC oxidation (see companion paper Aumont et al., 2005), (ii) the application of several commonly used reduction methods to the fully explicit scheme, and (iii) the assessment of resulting errors based on direct comparison between the reduced and full schemes. <P style="line-height: 20px;"> The reference scheme included seventy emitted VOCs chosen to be representative of both anthropogenic and biogenic emissions, and their atmospheric degradation chemistry required more than two million reactions among 350000 species. Three methods were applied to reduce the size of the reference chemical scheme: (i) use of operators, based on the redundancy of the reaction sequences involved in the VOC oxidation, (ii) grouping of primary species having similar reactivities into surrogate species and (iii) grouping of some secondary products into surrogate species. The number of species in the final reduced scheme is 147, this being small enough for practical inclusion in current three-dimensional models. Comparisons between the fully explicit and reduced schemes, carried out with a box model for several typical tropospheric conditions, showed that the reduced chemical scheme accurately predicts ozone concentrations and some other aspects of oxidant chemistry for both polluted and clean tropospheric conditions.
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This paper describes a broadband cavity ringdown spectrometer and its deployment during the 2002 North Atlantic Marine Boundary Layer Experiment (NAMBLEX) to measure ambient concentrations of NO<sub>3</sub>, N<sub>2</sub>O<sub>5</sub>, I<sub>2</sub> and OIO at the Mace Head Atmospheric Research Station, Co. Galway, Ireland. The effective absorption path lengths accessible with the spectrometer generally exceeded 10 km, enabling sensitive localised ``point" measurements of atmospheric absorbers to be made adjacent to the other instruments monitoring chemically related species at the same site. For the majority of observations, the spectrometer was used in an open path configuration thereby avoiding surface losses of reactive species. A subset of observations targeted the N<sub>2</sub>O<sub>5</sub> molecule by detecting the additional NO<sub>3</sub> formed by the thermal dissociation of N<sub>2</sub>O<sub>5</sub>. In all cases the concentrations of the atmospheric absorbers were retrieved by fitting the differential structure in the broadband cavity ringdown spectra using a methodology adapted from long path differential optical absorption spectroscopy. The uncertainty of the retrieval depends crucially on the correct treatment and fitting of the absorption bands due to water vapour, a topic that is discussed in the context of analysing broadband cavity ringdown spectra. The quality of the measurements and the retrieval method are illustrated with representative spectra acquired during NAMBLEX in spectral regions around 660 nm (NO<sub>3</sub> and N<sub>2</sub>O<sub>5</sub>) and 570 nm (I<sub>2</sub> and OIO). Typical detection limits were 1 pptv for NO<sub>3</sub> in an integration time of 100 s, 4 pptv for OIO and 20 pptv for I<sub>2</sub> in an integration time of 10 min. Additionally, the concentrations of atmospheric water vapour and the aerosol optical extinction were retrieved in both spectral regions. A companion paper in this issue presents the time series of the measurements and discusses their significance for understanding the variability of short lived nitrogen and iodine compounds in the marine boundary layer.
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A Lagrangian Stochastic Model for the two-particles dispersion, aiming at simulating the pollutant concentration fluctuations, is presented. Three model versions (1-D, 2-D and 3-D) are tested. Firstly the ability of the model to reproduce the two-particle statistics in a homogeneous isotropic turbulence is discussed, comparing the model results with theoretical predictions in terms of the probability density function (PDF) of the particles separation and its statistics. Then, the mean concentration and its fluctuations are considered and the results presented. The influence of the PDF of the particle separation on the concentration fluctuations is shown and discussed. We found that the separation PDF in the inertial subrange is not gaussian and this fact influences the predicted concentration fluctuations.
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The impact of the direct radiative effect of the aerosol particles on the calculation of the photolysis rates and consequently on the atmospheric chemistry in regional smoke clouds due to biomass burning over the Amazon basin is addressed in this work. It explores a case study for 19 September 2002 at LBA-RACCI-SMOCC (The Large-Scale Biosphere-Atmosphere experiment in Amazonia – Radiation, Cloud, and Climate Interactions – Smoke, Aerosols, Clouds, Rainfall and Climate) pasture site in SW Amazonia. The Tropospheric Ultraviolet Visible radiation model (TUV) version 4.2, (Madronich et al., 1987) is used for the photolysis rates calculation considering the layer aerosol optical depth from the Coupled Aerosol Tracer Transport model to the Brazilian Regional Atmospheric Modeling System (CATT-BRAMS) (Freitas et al., 2005). A dynamical aerosol model (Procópio et al., 2003) is included in the radiative transfer model to take into account the high temporal variability of the aerosol optical thickness. This methodology is tested by comparing modeled and measured clear sky solar irradiances. The results show a good agreement with measured PAR radiation values. The actinic flux attenuation, for AOT (500 nm) values around 1.94, decreases the photolysis rates by about 70% in the presence of near-ground smoke aerosol and above the smoke layer the photolysis process tends to increase by about 40%. A simulation of the ozone production is carried out using a one-dimensional photochemical box model and comparisons with observation are shown.
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We apply the NASA Goddard Trajectory Model to data from a series of ozonesondes to derive ozone loss rates in the lower stratosphere for the AASE-2/EASOE mission (January-March 1992) and for the SOLVE/THESEO 2000 mission (January-March 2000) in an approach similar to Match. Ozone loss rates are computed by comparing the ozone concentrations provided by ozonesondes launched at the beginning and end of the trajectories connecting the launches. We investigate the sensitivity of the Match results to the various parameters used to reject potential matches in the original Match technique. While these filters effectively eliminate from consideration 80% of the matched sonde pairs and >99% of matched observations in our study, we conclude that only a filter based on potential vorticity changes along the calculated back trajectories seems warranted. Our study also demonstrates that the ozone loss rates estimated in Match can vary by up to a factor of two depending upon the precise trajectory paths calculated for each trajectory. As a result, the statistical uncertainties published with previous Match results might need to be augmented by an additional systematic error. The sensitivity to the trajectory path is particularly pronounced in the month of January, for which the largest ozone loss rate discrepancies between photochemical models and Match are found. For most of the two study periods, our ozone loss rates agree with those previously published. Notable exceptions are found for January 1992 at 475K and late February/early March 2000 at 450K, both periods during which we generally find smaller loss rates than the previous Match studies. Integrated ozone loss rates estimated by Match in both of those years compare well with those found in numerous other studies and in a potential vorticity/potential temperature approach shown previously and in this paper. Finally, we suggest an alternate approach to Match using trajectory mapping. This approach uses information from all matched observations without filtering and uses a two-parameter fit to the data to produce robust ozone loss rate estimates. As compared to loss rates from our version of Match, the trajectory mapping approach produces generally smaller loss rates, frequently not statistically significantly different from zero, calling into question the efficacy of the Match approach.
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An assimilated data base of total column ozone measurements from satellites has been used to generate a set of indicators describing attributes of the Antarctic ozone hole for the period 1979 to 2003, including (i) daily measures of the area over Antarctica where ozone levels are below 150 DU, below 220 DU, more than 30% below 1979 to 1981 norms, and more than 50% below 1979 to 1981 norms, (ii) the date of disappearance of 150 DU ozone values, 220 DU ozone values, values 30% below 1979 to 1981 norms, and values 50% below 1979 to 1981 norms, for each year, (iii) daily minimum total column ozone values over Antarctica, and (iv) daily values of the ozone mass deficit based on a O<sub>3</sub><220 DU threshold. The assimilated data base combines satellite-based ozone measurements from 4 Total Ozone Mapping Spectrometer (TOMS) instruments, 3 different retrievals from the Global Ozone Monitoring Experiment (GOME), and data from 4 Solar Backscatter Ultra-Violet (SBUV) instruments. Comparisons with the global ground-based Dobson spectrophotometer network are used to remove offsets and drifts between the different data sets to produce a global homogeneous data set that combines the advantages of good spatial coverage of satellite data with good long-term stability of ground-based measurements. One potential use of the derived indices is detection of the expected recovery of the Antarctic ozone hole. The suitability of the derived indicators to this task is discussed in the context of their variability and their susceptibility to saturation effects which makes them less responsive to decreasing stratospheric halogen loading. It is also shown that if the corrections required to match recent Earth Probe TOMS measurements to Dobson measurements are not applied, some of the indictors are affected so as to obscure detection of the recovery of the Antarctic ozone hole.
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Limb scattering retrievals of atmospheric minor constituent profiles require highly accurate knowledge of the tangent heights during the measurements. The limb scattering measurements of the Scanning Imaging Absorption spectroMeter for Atmospheric CartograpHY (SCIAMACHY) on Envisat are affected by tangent height errors of up to 2 km. This contribution provides a summary of the temporal and spatial variation of the SCIAMACHY limb pointing errors during the first three years of the SCIAMACHY mission. The tangent height errors are retrieved from the limb measurements in the UV-B spectral range. A seasonal modulation of the monthly mean tangent height offsets is identified with amplitudes of 800m (220m) before (after) the improvement of the Envisat orbit propagator model in December 2003. Even after the December 2003 orbit model improvement a constant offset component of about 1km is present. Furthermore, pointing discontinuities are identified that coincide with the daily updates of the on-board orbit propagator model. In order to reduce the errors in ozone profile retrievals caused by pointing errors to less than 5%, the tangent heights have to be known to within 250m.
