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Comparison of CMAM simulations of carbon monoxide (CO), nitrous oxide (N2O), and methane (CH4) with observations from Odin/SMR, ACE-FTS, and Aura/MLS

Simulations of CO, N2O and CH4 from a coupled chemistry-climate model (CMAM) are compared with satellite measurements from Odin Sub-Millimeter Radiometer (Odin/SMR), Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), and Aura Microwave Limb Sounder (Aura/MLS). Pressure-latitude cross-sections and seasonal time series demonstrate that CMAM reproduces the observed global CO, N2O, and CH4 distributions quite well. Generally, excellent agreement with measurements is found between CO simulations and observations in the stratosphere and mesosphere. Differences between the simulations and the ACE-FTS observations are generally within 30%, and the differences between CMAM results and SMR and MLS observations are slightly larger. These differences are comparable with the difference between the instruments in the upper stratosphere and mesosphere. Comparisons of N2O show that CMAM results are usually within 15% of the measurements in the lower and middle stratosphere, and the observations are close to each other. However, the standard version of CMAM has a low N2O bias in the upper stratosphere. The CMAM CH4 distribution also reproduces the observations in the lower stratosphere, but has a similar but smaller negative bias in the upper stratosphere. The negative bias may be due to that the gravity drag is not fully resolved in the model. The simulated polar CO evolution in the Arctic and Antarctic agrees with the ACE and MLS observations. CO measurements from 2006 show evidence of enhanced descent of air from the mesosphere into the stratosphere in the Arctic after strong stratospheric sudden warmings (SSWs). CMAM also shows strong descent of air after SSWs. In the tropics, CMAM captures the annual oscillation in the lower stratosphere and the semiannual oscillations at the stratopause and mesopause seen in Aura/MLS CO and N2O observations and in Odin/SMR N2O observations. The Odin/SMR and Aura/MLS N2O observations also show a quasi-biennial oscillation (QBO) in the upper stratosphere, whereas, the CMAM does not have QBO included. This study confirms that CMAM is able to simulate middle atmospheric transport processes reasonably well.
Variable CCN formation potential of regional sulfur emissions

Aerosols are short lived so their geographical distribution and impact on climate depends on where they are emitted. Previous model studies have shown that the mass of sulfate aerosol produced per unit sulfur emission (the sulfate burden potential) and the associated direct radiative forcing vary regionally because of differences in meteorology and photochemistry. Using a global model of aerosol microphysics, we show that the total number of aerosol particles produced per unit sulfur emission (the aerosol number potential) has a different regional variation to that of sulfate mass. The aerosol number potential of N. American and Asian emissions is calculated to be a factor of 3 to 4 times greater than that of European emissions, even though Europe has a higher sulfate burden potential. Pollution from N. America and Asia tends to reach higher altitudes than European pollution so forms more new particles through nucleation. Regional differences in particle production and growth mean that sulfur emissions from N. America and E. Asia produce 50 nm diameter cloud condensation nuclei up to 70% more efficiently than Europe. For 80 nm diameter CCN, N. America and Europe produce CCN 2.5 times more efficiently than E. Asia. The impact of regional sulfur emissions on particle concentrations is also much more widely spread than the impact on sulfate mass, due to efficient particle production in the free troposphere during long range transport. These results imply that regional sulfur emissions will have different climate forcing potentials through changes in cloud drop number.
Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow

Atmospheric hydroperoxides (ROOH) were measured at Summit, Greenland (72.97° N, 38.77° W) in summer 2003 (SUM03) and spring 2004 (SUM04) and South Pole in December 2003 (SP03). The two dominant hydroperoxides were H2O2 and CH3OOH (from here on MHP) with average (±1σ) mixing ratios of 1448 (±688) pptv, 204 (±162) and 278 (±67) for H2O2 and 578 (±377) pptv, 139 (±101) pptv and 138 (±89) pptv for MHP, respectively. In early spring, MHP dominated the ROOH budget and showed night time maxima and daytime minima, out of phase with the diurnal cycle of H2O2, suggesting that the organic peroxide is controlled by photochemistry, while H2O2 is largely influenced by temperature driven exchange between the atmosphere and snow. Highly constrained photochemical box model runs yielded median ratios between modeled and observed MHP of 52%, 148% and 3% for SUM03, SUM04 and SP03, respectively. At Summit firn air measurements and model calculations suggest a daytime sink of MHP in the upper snow pack, which decreases in strength through the spring season into the summer. Up to 50% of the estimated sink rates of 1–5×1011 molecules m−3 s−1 equivalent to 24–96 pptv h−1 can be explained by photolysis and reaction with the OH radical in firn air and in the quasi-liquid layer on snow grains. Rapid processing of MHP in surface snow is expected to contribute significantly to a photochemical snow pack source of formaldehyde (CH2O). Conversely, summer levels of MHP at South Pole are inconsistent with the prevailing high NO concentrations, and cannot be explained currently by known photochemical precursors or transport, thus suggesting a missing source. Simultaneous measurements of H2O2, MHP and CH2O allow to constrain the NO background today and potentially also in the past using ice cores, although it seems less likely that MHP is preserved in firn and ice.
Multi-scale model analysis of boundary layer ozone over East Asia

This study employs the regional Community Multiscale Air Quality (CMAQ) model to examine seasonal and diurnal variations of boundary layer ozone (O3) over East Asia. We evaluate the response of model simulations of boundary layer O3 to the choice of chemical mechanisms, meteorological fields, boundary conditions, and model resolutions. Data obtained from surface stations, aircraft measurements, and satellites are used to advance understanding of O3 chemistry and mechanisms over East Asia and evaluate how well the model represents the observed features. Satellite measurements and model simulations of summertime rainfall are used to assess the impact of the Asian monsoon on O3 production. Our results suggest that summertime O3 over Central Eastern China is highly sensitive to cloud cover and monsoonal rainfall over this region. Thus, accurate simulation of the East Asia summer monsoon is critical to model analysis of atmospheric chemistry over China. Examination of hourly summertime O3 mixing ratios from sites in Japan confirms the important role of diurnal boundary layer fluctuations in controlling ground-level O3. By comparing five different model configurations with observations at six sites, the specific mechanisms responsible for model behavior are identified and discussed. In particular, vertical mixing, urban chemistry, and dry deposition depending on boundary layer height strongly affect model ability to capture observed behavior. Central Eastern China appears to be the most sensitive region in our study to the choice of chemical mechanisms. Evaluation with TRACE-P aircraft measurements reveals that neither the CB4 nor the SAPRC99 mechanisms consistently capture observed behavior of key photochemical oxidants in springtime. However, our analysis finds that SAPRC99 performs somewhat better in simulating mixing ratios of H2O2 (hydrogen peroxide) and PAN (peroxyacetyl nitrate) at flight altitudes below 1 km. The high level of uncertainty associated with O3 production in Central Eastern China poses a major problem for regional air quality management. This highly polluted, densely populated region would greatly benefit from comprehensive air quality monitoring and the development of model chemical mechanisms appropriate to this unique atmospheric environment.
Applying the Condensation Particle Counter Battery (CPCB) to study the water-affinity of freshly-formed 2–9 nm particles in boreal forest

Measurements on the composition of nanometer-sized atmospheric particles are the key to understand which vapors participate in the secondary aerosol formation processes. Knowledge on these processes is crucial in assessing the climatic effects of secondary aerosol formation. We present data of >2 nm particle concentrations and their water-affinity measured with the Condensation Particle Counter Battery (CPCB) at a boreal forest site in Hyytiälä, Finland, during spring 2006. The data reveal that during new particle formation events, the smallest particles activate for growth at clearly smaller sizes in water than in butanol vapor. However, even at 2–4 nm, there are days when the particles seem to be less hygroscopic than ammonium sulfate or sulfuric acid, which are often referred to as the most likely compounds present in atmospheric nucleation. This observation points to the possible presence of water-soluble organics, even at the very first steps on particle formation. The water-affinity of the particles decreases with size, indicating that the vapors that participate in the first steps of the particle formation and growth are more hygroscopic than the vapors contributing to the later stages of the growth. This suggests that the relative role of less hygroscopic organics in atmospheric particle growth increases as a function of particle size.
Source apportionment of elevated wintertime PAHs by compound-specific radiocarbon analysis

Natural abundance radiocarbon analysis facilitates distinct source apportionment between contemporary biomass/biofuel (14C "alive") versus fossil fuel (14C "dead") combustion. Here, the first compound-specific radiocarbon analysis (CSRA) of atmospheric polycyclic aromatic hydrocarbons (PAHs) was demonstrated for a set of samples collected in Lycksele, Sweden a small town with frequent episodes of severe atmospheric pollution in the winter. Renewed interest in using residential wood combustion (RWC) means that this type of seasonal pollution is of increasing concern in many areas. Five individual/paired PAH isolates from three pooled fortnight-long filter collections were analyzed by CSRA: phenanthrene, fluoranthene, pyrene, benzo[b+k]fluoranthene and indeno[cd]pyrene plus benzo[ghi]perylene; phenanthrene was the only compound also analyzed in the gas phase. The measured Δ14C for PAHs spanned from −138.3&permil; to 58.0&permil;. A simple isotopic mass balance model was applied to estimate the fraction biomass (fbiomass) contribution, which was constrained to 71–87% for the individual PAHs. Indeno[cd]pyrene plus benzo[ghi]perylene had an fbiomass of 71%, while fluoranthene and phenanthrene (gas phase) had the highest biomass contribution at 87%. The total organic carbon (TOC, defined as carbon remaining after removal of inorganic carbon) fbiomass was estimated to be 77%, which falls within the range for PAHs. This CSRA data of atmospheric PAHs established that RWC is the dominating source of atmospheric PAHs to this region of the boreal zone with some variations among RWC contributions to specific PAHs.
Hydration increases the lifetime of HSO5 and enhances its ability to act as a nucleation precursor – a computational study

Recent experimental findings indicate that HSO5 radicals may play a key role in the nucleation of atmospheric SO2 oxidation products. HSO5 radicals are metastable intermediates formed in the SO2 oxidation process, and their stability and lifetime are, at present, highly uncertain. Previous high-level computational studies have predicted rather low stabilities for HSO5 with respect to dissociation into SO3+HO2, and have predicted the net reaction HSO3+OH→SO3+HO2 to be slightly exothermal. However, these studies have not accounted for hydration of HSO5 or its precursor HSO3. In this study, we have estimated the effect of hydration on the stability and lifetime of HSO5 using the advanced quantum chemical methods CCSD(T) and G3B3. We have computed formation energies and free energies for mono- and dihydrates of OH, HSO3, HSO5, SO3 and HO2, and also reanalyzed the individual steps of the HSO3+O2→HSO5→SO3+HO2 reaction at a higher level of theory than previously published. Our results indicate that hydration is likely to significantly prolong the lifetime of the HSO5 intermediate in atmospheric conditions, thus increasing the probability of reactions that form products with more than one sulfur atom. Kinetic modeling indicates that these results may help explain the experimental observations that a mixture of sulfur-containing products formed from SO2 oxidation by OH radicals nucleates much more effectively than sulfuric acid taken from a liquid reservoir.
Impact of stratospheric intrusions and intercontinental transport on ozone at Jungfraujoch in 2005: comparison and validation of two Lagrangian approaches

The particle dispersion model FLEXPART and the trajectory model LAGRANTO are Lagrangian models which are widely used to study synoptic-scale atmospheric air flows such as stratospheric intrusions (SI) and intercontinental transport (ICT). In this study, we focus on SI and ICT events particularly from the North American planetary boundary layer for the Jungfraujoch (JFJ) measurement site, Switzerland, in 2005. Two representative cases of SI and ICT are identified based on measurements recorded at Jungfraujoch and are compared with FLEXPART and LAGRANTO simulations, respectively. Both models well capture the events, showing good temporal agreement between models and measurements. In addition, we investigate the performance of FLEXPART and LAGRANTO on representing SI and ICT events over the entire year 2005 in a statistical way. We found that the air at JFJ is influenced by SI during 19% (FLEXPART) and 18% (LAGRANTO), and by ICT from the North American planetary boundary layer during 13% (FLEXPART) and 12% (LAGRANTO) of the entire year. Through intercomparsion with measurements, our findings suggest that both FLEXPART and LAGRANTO are well capable of representing SI and ICT events if they last for more than 12 h, whereas both have problems on representing short events. For comparison with in-situ observations we used O3 and relative humidity for SI events. As parameters to trace ICT events we used a combination of NOy/CO and CO, however these parameters are not specific enough to distinguish aged air masses by their source regions. Moreover, a sensitivity study indicates that the agreement between models and measurements depends significantly on the threshold values applied to the individual control parameters. Generally, the less strict the thresholds are, the better the agreement between models and measurements. Although the dependence of the agreement on the threshold values is appreciable, it nevertheless confirms the conclusion that both FLEXPART and LAGRANTO are well able to capture SI and ICT events with duration longer than 12 h.
A multimethodological approach to study the spatial distribution of air pollution in an Alpine valley during wintertime

In order to investigate the spatial distribution of air pollutants in the Inn valley (Tyrol, Austria) during wintertime, a joint field campaign of the three research projects ALPNAP (Monitoring and Minimisation of Traffic-Induced Noise and Air Pollution Along Major Alpine Transport Routes), INNAP (Boundary Layer Structure in the Inn Valley during high Air Pollution) and INNOX (NOx-structure in the Inn Valley during High Air Pollution) was carried out in January/February 2006. In addition to continuous ground based measurements, vertical profiles of various air pollutants and meteorological parameters were obtained on six selected days. For in-situ investigations, a tethered balloon was used to analyse the lowest atmospheric layers, 0–500 m above the valley bottom (a.v.b.), and a research aircraft sampled at 150–2200 m a.v.b. An aircraft equipped with an aerosol backscatter lidar performed nadir measurements at 3000 m a.v.b. Combined results from a typical day show a strongly polluted layer up to about 125 m a.v.b. in the morning. Around midday concentrations on the valley floor decrease indicating some vertical air exchange despite thermally stable conditions. Strong vertical and horizontal gradients with enhanced pollution levels along the sunny side of the valley up to 1300 m a.v.b. were observed in the afternoon. This vertical mixing due to thermally or dynamically driven slope winds reduces the concentration of air pollutants at the bottom of the valley and causes the formation of elevated pollution layers.
An emission inventory of sulfur from anthropogenic sources in Antarctica

This paper presents first results of a comprehensive emission inventory of chemical species from anthropogenic activities (power generation, vehicles, ships and aircraft) in Antarctica, covering the 2004–2005 period. The inventory is based on estimated emission rates of fuel consumption provided by some of the Antarctic research stations. Since the emission sources have different modes of operation and use a variety of fuel, the emission flux rate of chemical species is calculated by multiplying the fuel consumption value with the density of fuel and appropriate emission factors. A separate inventory is prepared for each anthropogenic emission source in Antarctica. Depending on the type of operation, emission rates of SO2, and BC (Black Carbon, from shipping only) have been calculated using the above technique. However, only results of SO2 emissions from each source are presented here. Emission inventory maps of SO2 depicting the track/path taken by each mobile source are shown. The total annual SO2 is 158 Mg from power generation and vehicle operations, 3873 Mg from ships and 56 Mg from aircraft for 2004–2005 and these values undergo strong seasonality following the human activity in Antarctica. Though these figures are small when compared to the emissions at most other regions of the world, they are an indication that human presence in Antarctica leads to at least local pollution. The sources are mainly line and point sources and thus the local pollution potentially is relatively strong.