bluuebunny/crossref_metadata_2025 huggingface dataset:
Statistical properties of cloud lifecycles in cloud-resolving models
Authors: Plant R. S.
Published: April 2010

Abstract. A new technique is described for the analysis of cloud-resolving model simulations, which allows one to investigate the statistics of the lifecycles of cumulus clouds. Clouds are tracked from timestep to timestep within the model run. This allows for a very simple method of tracking, but one which is both comprehensive and robust. An approach for handling cloud splits and mergers is described which allows clouds with simple and complicated time histories to be compared within a single framework. This is found to be important for the analysis of an idealized simulation of radiative-convective equilibrium, in which the moist, buoyant updrafts (i.e., the convective cores) were tracked. Around half of all such cores were subject to splits and mergers during their lifecycles. For cores without any such events, the average lifetime is 30 min, but events can lengthen the typical lifetime considerably.
Oxidation capacity of the city air of Santiago, Chile
Authors: Elshorbany Y. F. , Kurtenbach R. , Wiesen P. , Lissi E. , Rubio M. , Villena G. , Gramsch E. , Rickard A. R. , Pilling M. J. , Kleffmann J.
Published: April 2010

Abstract. The oxidation capacity of the highly polluted urban area of Santiago, Chile has been evaluated during a summer measurement campaign carried out from 8–20 March 2005. The hydroxyl (OH) radical budget was evaluated employing a simple quasi-photostationary-state model (PSS) constrained with simultaneous measurements of HONO, HCHO, O3, NO, NO2, j(O1D), j(NO2), 13 alkenes and meteorological parameters. In addition, a zero dimensional photochemical box model based on the Master Chemical Mechanism (MCMv3.1) has been used to estimate production rates and total free radical budgets, including OH, HO2 and RO2. Besides the above parameters, the MCM model has been constrained by the measured CO and volatile organic compounds (VOCs) including alkanes and aromatics. Both models simulate the same OH concentration during daytime indicating that the primary OH sources and sinks included in the simple PSS model predominate. Mixing ratios of the main OH radical precursors were found to be in the range 0.8–7 ppbv (HONO), 0.9–11 ppbv (HCHO) and 0–125 ppbv (O3). The alkenes average mixing ratio was ~58 ppbC accounting for ~12% of the total identified non-methane hydrocarbons (NMHCs). During the daytime (08:00 h–19:00 h), HONO photolysis was shown to be the most important primary OH radical source comprising alone ~55% of the total initial production rate, followed by alkene ozonolysis (~24%) and photolysis of HCHO (~16%) and O3 (~5%). The calculated average and maximum daytime OH production rates from HONO photolysis was 1.7 ppbv h−1 and 3.1 ppbv h−1, respectively. Based on the experimental results a strong photochemical daytime source of HONO is proposed. A detailed analysis of the sources of OH radical precursors has also been carried out.
Hydration of the lower stratosphere by ice crystal geysers over land convective systems
Authors: Khaykin S. , Pommereau J.-P. , Korshunov L. , Yushkov V. , Nielsen J. , Larsen N. , Christensen T. , Garnier A. , Lukyanov A. , Williams E.
Published: April 2010

Abstract. The possible impact of deep convective overshooting over land has been explored by six simultaneous soundings of water vapour, particles and ozone in the lower stratosphere next to Mesoscale Convective Systems (MCSs) during the monsoon season over West Africa in Niamey, Niger in August 2006. The water vapour measurements were carried out using a fast response FLASH-B Lyman-alpha hygrometer. The high vertical resolution observations of the instrument show the presence of accumulation of enhanced water vapour layers between the tropopause at 370 K and the 420 K level. Most of these moist layers are shown connected with overshooting events occurring upwind as identified from satellite IR images over which the air mass probed by the sondes passed during the three previous days. In the case of a local overshoot identified by echo top turrets above the tropopause by the MIT C-band radar also in Niamey, tight coincidence was found between enhanced water vapour, ice crystal and ozone dip layers indicative of fast uplift of tropospheric air across the tropopause. The water vapour mixing ratio in the enriched layers exceeds frequently by 1–3 ppmv the average 6 ppmv saturation ratio at the tropopause and by up to 7 ppmv in the extreme case of local storm in coincidence with the presence of ice crystals. The presence of such layers strongly suggests hydration of the lower stratosphere by geyser-like injection of ice particles over overshooting turrets. The pile-like increase of water vapour up to 19 km seen by the high-resolution hygrometer during the season of maximum temperature of the tropopause, suggests that the above hydration mechanism may contribute to the summer maximum moisture in the lower stratosphere. If this interpretation is correct, hydration by ice geysers across the tropopause might be an important contributor to the stratospheric water vapour budget.
Sensitivity of aerosol optical thickness and aerosol direct radiative effect to relative humidity
Authors: Bian H. , Chin M. , Rodriguez J. M. , Yu H. , Penner J. E. , Strahan S.
Published: April 2010

Abstract. We present a sensitivity study of the effects of spatial and temporal resolution of atmospheric relative humidity (RH) on calculated aerosol optical thickness (AOT) and the aerosol direct radiative effects (DRE) in a global model. We carry out different modeling experiments using the same aerosol fields simulated in the Global Modeling Initiative (GMI) model at a resolution of 2° latitude by 2.5° longitude, using time-averaged fields archived every three hours by the Goddard Earth Observation System Version 4 (GEOS-4), but we change the horizontal and temporal resolution of the relative humidity fields. We find that, on a global average, the AOT calculated using RH at a 1°×1.25° horizontal resolution is 11% higher than that using RH at a 2°×2.5° resolution, and the corresponding DRE at the top of the atmosphere is 8–9% and 15% more negative (i.e., more cooling) for total aerosols and anthropogenic aerosol alone, respectively, in the finer spatial resolution case. The difference is largest over surface escarpment regions (e.g. >200% over the Andes Mountains) where RH varies substantially with surface terrain. The largest zonal mean AOT difference occurs at 50–60° N (16–21%), where AOT is also relatively larger. A similar impact is also found when the time resolution of RH is increased. This increase of AOT and aerosol cooling with the increase of model resolution is due to the highly non-linear relationship between RH and the aerosol mass extinction efficiency (MEE) at high RH (>80%). Our study is a specific example of the uncertainty in model results highlighted by multi-model comparisons such as AeroCom, and points out one of the many inter-model differences that can contribute to the overall spread among models.
Real-time secondary aerosol formation during a fog event in London
Authors: Dall'Osto M. , Harrison R. M. , Coe H. , Williams P.
Published: April 2010

Abstract. A fog event was monitored with state-of-the art real-time aerosol mass spectrometers in an urban background location in London (England) during the REPARTEE-I experiment. Specific particle types rich in hydroxymethanesulphonate (HMS) were found only during the fog event. Formation of inorganic and organic secondary aerosol was observed as soon as fog was detected and two different mechanisms are suggested to be responsible for the production of two different types of aerosol. Nitrate aerosol is produced in the liquid phase within the droplet. Contrary to previous studies, the formation of HULIS was observed on interstitial particles rather than evaporated fog droplets, suggesting heterogeneous formation mechanisms depending on parameters other than the water content and not fully understood. Not only are secondary aerosol constituents produced during the fog event, but the primary aerosol is observed to be processed by the fog event, dramatically changing its chemical properties.
A case study of ozone production, nitrogen oxides, and the radical budget in Mexico City
Authors: Wood E. C. , Herndon S. C. , Onasch T. B. , Kroll J. H. , Canagaratna M. R. , Kolb C. E. , Worsnop D. R. , Neuman J. A. , Seila R. , Zavala M. , Knighton W. B.
Published: April 2010

Abstract. Observations at a mountain-top site within the Mexico City basin are used to characterize ozone production and destruction, nitrogen oxide speciation and chemistry, and the radical budget, with an emphasis on a stagnant air mass observed on one afternoon. The observations compare well with the results of recent photochemical models. An ozone production rate of ~50 ppbv/h was observed in a stagnant air mass during the afternoon of 12 March 2006, which is among the highest observed anywhere in the world. Approximately half of the ozone destruction was due to the oxidation of NO2. During this time period ozone production was VOC-limited, deduced by a comparison of the radical production rates and the formation rate of NOx oxidation products (NOz). For [NOx]/[NOy] values between 0.2 and 0.8, gas-phase HNO3 typically accounted for less than 10% of NOz and accumulation-mode particulate nitrate (NO3(PM1)−) accounted for 20%–70% of NOz, consistent with high ambient NH3 concentrations. The fraction of NOz accounted for by the sum of HNO3(g) and NO3(PM1)− decreased with photochemical processing. This decrease is apparent even when dry deposition of HNO3 is accounted for, and indicates that HNO3 formation decreased relative to other NOx "sink" processes during the first 12 h of photochemistry and/or a significant fraction of the nitrate was associated with the coarse aerosol size mode. The ozone production efficiency of NOx on 11 and 12 March 2006 was approximately 7 on a time scale of one day. A new metric for ozone production efficiency that relates the dilution-adjusted ozone mixing ratio to cumulative OH exposure is proposed.
Mixing processes and exchanges in the tropical and the subtropical UT/LS
Authors: James R. , Legras B.
Published: April 2010

Abstract. Both in situ measurements and satellite observations indicate evidence of mixing in the upper troposphere (UT) and the lower-stratosphere (LS). In this study, the measurements performed during the Pre-AVE and Costa-Rica AVE campaigns are analysed with diffusive back-trajectories to assess mixing properties in the tropical and the subtropical UT/LS. A description of cross-tropopause pathways and mixing time scales is provided. In the subtropics, Troposphere-Stratosphere mixing processes are found to differ in the vicinity of the tropopause and at higher altitudes. Below 350 K, a mixing line observed during Pre-AVE is shown to result from fast and local cross-tropopause irreversible exchange, involving two initially distant air masses with distinct chemical compositions. For measurements located above 350 K, mixing of the tropospheric air in the subtropical stratosphere occurs over a period of a month, the origins of the tropospheric source being localised in the tropical UT and the tropical boundary layer. In the tropics, quantitative reconstructions of CO and O3 profiles above 360 K are obtained for one month back-trajectories calculations, pointing out that long term mixing is essential to determine the chemical composition in the tropical ascent. In particular, the existence of two-way meridional irreversible exchanges between 360 and 450 K is found to export tropical air in the subtropical stratosphere and to entrain old stratospheric air in the tropical ascent. Mean age of air calculated with a Lagrangian model is shown to be in agreement with the CO2 observations.
Sensitivity of aerosol and cloud effects on radiation to cloud types: comparison between deep convective clouds and warm stratiform clouds over one-day period
Authors: Lee S. S. , Donner L. J. , Phillips V. T. J.
Published: April 2010

Abstract. Cloud and aerosol effects on radiation in two contrasting cloud types, a deep mesoscale convective system (MCS) and warm stratocumulus clouds, are simulated and compared. At the top of the atmosphere, 45–81% of shortwave cloud forcing (SCF) is offset by longwave cloud forcing (LCF) in the MCS, whereas warm stratiform clouds show the offset of less than ~20%. 28% of increased negative SCF is offset by increased LCF with increasing aerosols in the MCS at the top of the atmosphere. However, the stratiform clouds show the offset of just around 2–5%. Ice clouds as well as liquid clouds play an important role in the larger offset in the MCS. Lower cloud-top height and cloud depth, characterizing cloud types, lead to the smaller offset of SCF by LCF and the offset of increased negative SCF by increased LCF at high aerosol in stratocumulus clouds than in the MCS. Supplementary simulations show that this dependence of modulation of LCF on cloud depth and cloud-top height is also simulated among different types of convective clouds.
Estimating surface CO2 fluxes from space-borne CO2 dry air mole fraction observations using an ensemble Kalman Filter
Authors: Feng L. , Palmer P. I. , Bösch H. , Dance S.
Published: April 2010

Abstract. We have developed an ensemble Kalman Filter (EnKF) to estimate 8-day regional surface fluxes of CO2 from space-borne CO2 dry-air mole fraction observations (XCO2) and evaluate the approach using a series of synthetic experiments, in preparation for data from the NASA Orbiting Carbon Observatory (OCO). The 32-day duty cycle of OCO alternates every 16 days between nadir and glint measurements of backscattered solar radiation at short-wave infrared wavelengths. The EnKF uses an ensemble of states to represent the error covariances to estimate 8-day CO2 surface fluxes over 144 geographical regions. We use a 12×8-day lag window, recognising that XCO2 measurements include surface flux information from prior time windows. The observation operator that relates surface CO2 fluxes to atmospheric distributions of XCO2 includes: a) the GEOS-Chem transport model that relates surface fluxes to global 3-D distributions of CO2 concentrations, which are sampled at the time and location of OCO measurements that are cloud-free and have aerosol optical depths <0.3; and b) scene-dependent averaging kernels that relate the CO2 profiles to XCO2, accounting for differences between nadir and glint measurements, and the associated scene-dependent observation errors. We show that OCO XCO2 measurements significantly reduce the uncertainties of surface CO2 flux estimates. Glint measurements are generally better at constraining ocean CO2 flux estimates. Nadir XCO2 measurements over the terrestrial tropics are sparse throughout the year because of either clouds or smoke. Glint measurements provide the most effective constraint for estimating tropical terrestrial CO2 fluxes by accurately sampling fresh continental outflow over neighbouring oceans. We also present results from sensitivity experiments that investigate how flux estimates change with 1) bias and unbiased errors, 2) alternative duty cycles, 3) measurement density and correlations, 4) the spatial resolution of estimated flux estimates, and 5) reducing the length of the lag window and the size of the ensemble. At the revision stage of this manuscript, the OCO instrument failed to reach its orbit after it was launched on 24 February 2009. The EnKF formulation presented here is also applicable to GOSAT measurements of CO2 and CH4.
The impact of weather and atmospheric circulation on O3 and PM10 levels at a rural mid-latitude site
Authors: Demuzere M. , Trigo R. M. , Vila-Guerau de Arellano J. , van Lipzig N. P. M.
Published: April 2010

Abstract. In spite of the strict EU regulations, concentrations of surface ozone and PM10 often exceed the pollution standards for the Netherlands and Europe. Their concentrations are controlled by (precursor) emissions, social and economic developments and a complex combination of meteorological actors. This study tackles the latter, and provides insight in the meteorological processes that play a role in O3 and PM10 levels in rural mid-latitudes sites in the Netherlands. The relations between meteorological actors and air quality are studied on a local scale based on observations from four rural sites and are determined by a comprehensive correlation analysis and a multiple regression (MLR) analysis in 2 modes, with and without air quality variables as predictors. Furthermore, the objective Lamb Weather Type approach is used to assess the influence of the large-scale circulation on air quality. Keeping in mind its future use in downscaling future climate scenarios for air quality purposes, special emphasis is given to an appropriate selection of the regressor variables readily available from operational meteorological forecasts or AOGCMs (Atmosphere-Ocean coupled General Circulation Models). The regression models perform satisfactory, especially for O3, with an (R2 of 57.0% and 25.0% for PM10. Including previous day air quality information increases significantly the models performance by 15% (O3) and 18% (PM10). The Lamb weather types show a seasonal distinct pattern for high (low) episodes of average O3 and PM10 concentrations, and these are clear related with the meteorology-air quality correlation analysis. Although using a circulation type approach can provide important additional physical relations forward, our analysis reveals the circulation method is limited in terms of short-term air quality forecast for both O3 and PM10 (R2 between 0.12 and 23%). In summary, it is concluded that the use of a regression model is more promising for short-term downscaling from climate scenarios than the use of a weather type classification approach.
The CO2 inhibition of terrestrial isoprene emission significantly affects future ozone projections
Authors: Young P. J. , Arneth A. , Schurgers G. , Zeng G. , Pyle J. A.
Published: April 2010

Abstract. Simulations of future tropospheric composition often include substantial increases in biogenic isoprene emissions arising from the Arrhenius-like leaf emission response and warmer surface temperatures, and from enhanced vegetation productivity in response to temperature and atmospheric CO2 concentration. However, a number of recent laboratory and field data have suggested a direct inhibition of leaf isoprene production by increasing atmospheric CO2 concentration, notwithstanding isoprene being produced from precursor molecules that include some of the primary products of carbon assimilation. The cellular mechanism that underlies the decoupling of leaf photosynthesis and isoprene production still awaits a full explanation but accounting for this observation in a dynamic vegetation model that contains a semi-mechanistic treatment of isoprene emissions has been shown to change future global isoprene emission estimates notably. Here we use these estimates in conjunction with a chemistry-climate model to compare the effects of isoprene simulations without and with a direct CO2-inhibition on late 21st century O3 and OH levels. The impact on surface O3 was significant. Including the CO2-inhibition of isoprene resulted in opposing responses in polluted (O3 decreases of up to 10 ppbv) vs. less polluted (O3 increases of up to 10 ppbv) source regions, due to isoprene nitrate and peroxy acetyl nitrate (PAN) chemistry. OH concentration increased with relatively lower future isoprene emissions, decreasing methane lifetime by ~7 months (6.6%). Our simulations underline the large uncertainties in future chemistry and climate studies due to biogenic emission patterns and emphasize the problems of using globally averaged climate metrics (such as global radiative forcing) to quantify the atmospheric impact of reactive, heterogeneously distributed substances.
Assessing temporal clear-sky errors in assimilation of satellite CO2 retrievals using a global transport model
Authors: Corbin K. D. , Denning A. S. , Parazoo N. C.
Published: April 2010

Abstract. The Orbiting Carbon Observatory (OCO) and the Greenhouse gases Observing SATellite (GOSAT) will make global observations of the total column dry-air mole fraction of atmospheric CO2 (XCO2) starting in 2008. Although satellites have global coverage, XCO2 retrievals will be made only a few times each month over a given location and will only be sampled in clear conditions. Modelers will use XCO2 in atmospheric inversions to estimate carbon sources and sinks; however, if satellite measurements are used to represent temporal averages, modelers may incur temporal sampling errors. We investigate these errors using a global transport model. Temporal sampling errors vary with time and location, exhibit spatially coherent patterns, and are greatest over land and during summer. These errors often exceed 1 ppm and must be addressed in a data assimilation system by correct simulation of synoptic CO2 variations associated with cloud systems.
Comparison of CMAM simulations of carbon monoxide (CO), nitrous oxide (N2O), and methane (CH4) with observations from Odin/SMR, ACE-FTS, and Aura/MLS
Authors: Jin J. J. , Semeniuk K. , Beagley S. R. , Fomichev V. I. , Jonsson A. I. , McConnell J. C. , Urban J. , Murtagh D. , Manney G. L. , Boone C. D. , Bernath P. F. , Walker K. A. , Barret B. , Ricaud P. , Dupuy E.
Published: April 2010

Abstract. 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.
Multi-scale model analysis of boundary layer ozone over East Asia
Authors: Lin M. , Holloway T. , Oki T. , Streets D. G. , Richter A.
Published: April 2010

Abstract. 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.
Hydration increases the lifetime of HSO5 and enhances its ability to act as a nucleation precursor – a computational study
Authors: Kurtén T. , Berndt T. , Stratmann F.
Published: April 2010

Abstract. 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
Authors: Cui J. , Sprenger M. , Staehelin J. , Siegrist A. , Kunz M. , Henne S. , Steinbacher M.
Published: April 2010

Abstract. 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.
Exploring the differences in cloud properties observed by the Terra and Aqua MODIS Sensors
Authors: Meskhidze N. , Remer L. A. , Platnick S. , Negrón Juárez R. , Lichtenberger A. M. , Aiyyer A. R.
Published: April 2010

Abstract. The aerosol-cloud interaction in different parts of the globe is examined here using multi-year statistics of remotely sensed data from two MODIS sensors aboard NASA's Terra (morning) and Aqua (afternoon) satellites. Simultaneous retrievals of aerosol loadings and cloud properties by the MODIS sensor allowed us to explore morning-to-afternoon variation of liquid cloud fraction (CF) and optical thickness (COT) for clean, moderately polluted and heavily polluted clouds in different seasons. Data analysis for seven-years of MODIS retrievals revealed strong temporal and spatial patterns in morning-to-afternoon variation of cloud fraction and optical thickness over different parts of the global oceans and the land. For the vast areas of stratocumulus cloud regions, the data shows that the days with elevated aerosol abundance were also associated with enhanced afternoon reduction of CF and COT pointing to the possible reduction of the indirect climate forcing. A positive correlation between aerosol optical depth and morning-to-afternoon variation of trade wind cumulus cloud cover was also found over the northern Indian Ocean, though no clear relationship between the concentration of Indo-Asian haze and morning-to-afternoon variation of COT was established. Over the Amazon region during wet conditions, aerosols are associated with an enhanced convective process in which morning shallow warm clouds are organized into afternoon deep convection with greater ice cloud coverage. Analysis presented here demonstrates that the new technique for exploring morning-to-afternoon variability in cloud properties by using the differences in data products from the two daily MODIS overpasses is capable of capturing some of the major features of diurnal variations in cloud properties and can be used for better understanding of aerosol radiative effects.
Inter-comparison of four different carbon monoxide measurement techniques and evaluation of the long-term carbon monoxide time series of Jungfraujoch
Authors: Zellweger C. , Hüglin C. , Klausen J. , Steinbacher M. , Vollmer M. , Buchmann B.
Published: April 2010

Abstract. Despite the importance of carbon monoxide (CO) for the overall oxidative capacity of the atmosphere, there is still considerable uncertainty in ambient measurements of CO. To address this issue, an inter-comparison between four different measurement techniques was made over a period of two months at the high-alpine site Jungfraujoch (JFJ), Switzerland. The measurement techniques were Non-dispersive Infrared Absorption (NDIR), Vacuum UV Resonance Fluorescence (VURF), gas chromatographic separation with a mercuric oxide reduction detector (GC/HgO), and gas chromatographic separation followed by reduction on a nickel catalyst and analysis by a flame ionization detector (GC/FID). The agreement among all techniques was better than 2% for one-hourly averages, which confirmed the suitability of the NDIR method for CO measurements even at remote sites. The inter-comparison added to the validation of the 12-year record (1996–2007) of continuous CO measurements at JFJ. To date this is one of the longest time series of continuous CO measurements in the free troposphere over Central Europe. This data record was further investigated with a focus on trend analysis. A significant negative trend was observed at JFJ showing a decrease of 21.4±0.3% over the investigated period, or an average annual decrease of 1.78%/yr (2.65±0.04 ppb/yr). These results were compared with emission inventory data reported to the Long-range Transboundary Air Pollution (LRTAP) Convention. It could be shown that long range transport significantly influences the CO levels observed at JFJ, with air masses of non-European origin contributing at least one third of the observed mole fractions.
Negatively charged nanoparticles produced by splashing of water
Authors: Tammet H. , Hõrrak U. , Kulmala M.
Published: April 2010

Abstract. The production of splashing-generated balloelectric intermediate ions was studied by means of mobility spectrometry in the atmosphere during the rain and in a laboratory experiment simulating the heavy rain. The partial neutralization of intermediate ions with cluster ions generated by beta rays suppressed the space charge of intermediate ions but preserved the shape of the mobility distribution. The balloelectric ions produced from the waterworks water of high TDS (Total Dissolved Solids) had about the same mobilities as the ions produced from the rainwater of low TDS. This suggests that the balloelectric ions can be considered as singly charged water nanoparticles. By different measurements, the diameter mode of these particles was 2.2–2.7 nm, which is close to the diameter of 2.5 nm of the Chaplin's 280-molecule magic icosahedron superclusters. The measurements can be explained by a hypothesis that the pressure of saturated vapor over the nanoparticle surface is suppressed by a number of magnitudes due to the internal structure of the particles near the size of 2.5 nm. The records of the concentration bursts of balloelectric ions in the atmosphere are formally similar to the records of the nucleation bursts but they cannot be qualified as nucleation bursts because the particles are not growing but shrinking.
Temperature and humidity dependence of secondary organic aerosol yield from the ozonolysis of β-pinene
Authors: von Hessberg C. , von Hessberg P. , Pöschl U. , Bilde M. , Nielsen O. J. , Moortgat G. K.
Published: April 2010

Abstract. The temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of β-pinene was studied in a flow reactor at 263 K–303 K and 1007 hPa under dry and humid conditions (0% and 26%–68% relative humidity, respectively). The observed SOA yields reached maximum values of 0.18–0.39 at high particle mass concentrations (Mo). Under dry conditions, the measurement data showed an overall increase in SOA yield with inverse temperature, but significant oscillatory deviations from the predicted linear increase with inverse temperature (up to 50% at high Mo) was observed. Under humid conditions the SOA yield exhibited a linear decrease with inverse temperature. For the atmospherically relevant concentration level of Mo=10 μg m−3 and temperature range 263 K–293 K, the results from humid experiments in this study indicate that the SOA yield of β-pinene ozonolysis may be well represented by an average value of 0.15 with an uncertainty estimate of ±0.05. When fitting the measurement data with a two-product model, both the partitioning coefficients (Kom,i) and the stoichiometric yields (αi) of the low-volatile and semi-volatile model species were found to vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are strongly dependent on temperature and the presence of water vapour. In fact, the oscillatory positive temperature dependence observed under dry conditions and the negative temperature dependence observed under humid conditions indicate that the SOA yield is governed much more by the temperature and humidity dependence of the involved chemical reactions than by vapour pressure temperature dependencies. We suggest that the elucidation and modelling of SOA formation need to take into account the effects of temperature and humidity on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products.
Gas/particle partitioning of water-soluble organic aerosol in Atlanta
Authors: Hennigan C. J. , Bergin M. H. , Russell A. G. , Nenes A. , Weber R. J.
Published: April 2010

Abstract. Gas and particle-phase organic carbon compounds soluble in water (e.g., WSOC) were measured simultaneously in Atlanta throughout the summer of 2007 to investigate gas/particle partitioning of ambient secondary organic aerosol (SOA). Previous studies have established that, in the absence of biomass burning, particulate WSOC (WSOCp) is mainly from secondary organic aerosol (SOA) production. Comparisons between WSOCp, organic carbon (OC) and elemental carbon (EC) indicate that WSOCp was a nearly comprehensive measure of SOA in the Atlanta summertime. WSOCp and gas-phase WSOC (WSOCg) concentrations both exhibited afternoon maxima, indicating that photochemistry was a major route for SOA formation. An additional nighttime maximum in the WSOCg concentration indicated a dark source for oxidized organic gases, but this was not accompanied by detectable increases in WSOCp. To study SOA formation mechanisms, WSOC gas/particle partitioning was investigated as a function of temperature, RH, NOx, O3, and organic aerosol mass concentration. No clear relationship was observed between temperature and partitioning, possibly due to a simultaneous effect from other temperature-dependent processes. For example, positive temperature effects on emissions of biogenic SOA precursors and photochemical SOA formation may have accounted for the observed similar proportional increases of WSOCp and WSOCg with temperature. Relative humidity data indicated a linear dependence between partitioning and predicted fine particle liquid water. Lower NOx concentrations were associated with greater partitioning to particles, but WSOC partitioning had no visible relation to O3 or fine particle OC mass concentration. There was, however, a relationship between WSOC partitioning and the WSOCp concentration, suggesting a compositional dependence between partitioning semi-volatile gases and the absorbing organic aerosol. Combined, the overall results suggest two dominant SOA formation processes in urban Atlanta during summer. One was the photochemical production of SOA from presumably biogenic precursors that increased with the onset of sunrise and peaked in the afternoon. The other, which showed no apparent diurnal pattern, involved the partitioning of semi-volatile gases to liquid water, followed by heterogeneous reactions. The co-emission of water vapor and biogenic VOCs from vegetation may link these processes.
Tropospheric NO2 column densities deduced from zenith-sky DOAS measurements in Shanghai, China, and their application to satellite validation
Authors: Chen D. , Zhou B. , Beirle S. , Chen L. M. , Wagner T.
Published: April 2010

Abstract. Zenith-sky scattered sunlight observations using differential optical absorption spectroscopy (DOAS) technique were carried out in Shanghai, China (31.3° N, 121.5° E) since December 2006. At this polluted urban site, the measurements provided NO2 total columns in the daytime. Here, we present a new method to extract time series of tropospheric vertical column densities (VCDs) of NO2 from these observations. The derived tropospheric NO2 VCDs are important quantities for the estimation of emissions and for the validation of satellite observations. Our method makes use of assumptions on the relative NO2 height profiles and the diurnal variation of stratospheric NO2 VCDs. The main error sources arise from the uncertainties in the estimated stratospheric slant column densities (SCDs) and the determination of tropospheric NO2 air mass factor (AMF). For a polluted site like Shanghai, the accuracy of our method is conservatively estimated to be <25% for solar zenith angle (SZA) lower than 70°. From simultaneously performed long-path DOAS measurements, the NO2 surface concentrations at the same site were observed and the corresponding tropospheric NO2 VCDs were estimated using the assumed seasonal NO2 profiles in the planetary boundary layer (PBL). By making a comparison between the tropospheric NO2 VCDs from zenith-sky and long-path DOAS measurements, it is found that the former provides more realistic information about total tropospheric pollution than the latter, so it's more suitable for satellite data validation. A comparison between the tropospheric NO2 VCDs from ground-based zenith-sky measurements and SCIAMACHY was also made. Satellite validation for a strongly polluted area is highly needed, but exhibits also a great challenge. Our comparison shows good agreement, considering in particular the different spatial resolutions between the two measurements. Remaining systematic deviations are most probably related to the uncertainties of satellite data caused by the assumptions on aerosol properties as well as the layer heights of aerosols and NO2.
Parameterizing the competition between homogeneous and heterogeneous freezing in cirrus cloud formation – monodisperse ice nuclei
Authors: Barahona D. , Nenes A.
Published: April 2010

Abstract. We present a parameterization of cirrus cloud formation that computes the ice crystal number and size distribution under the presence of homogeneous and heterogeneous freezing. The parameterization is very simple to apply and is derived from the analytical solution of the cloud parcel equations, assuming that the ice nuclei population is monodisperse and chemically homogeneous. In addition to the ice distribution, an analytical expression is provided for the limiting ice nuclei number concentration that suppresses ice formation from homogeneous freezing. The parameterization is evaluated against a detailed numerical parcel model, and reproduces numerical simulations over a wide range of conditions with an average error of 6±33%. The parameterization also compares favorably against other formulations that require some form of numerical integration.
Inferring ozone production in an urban atmosphere using measurements of peroxynitric acid
Authors: Spencer K. M. , McCabe D. C. , Crounse J. D. , Olson J. R. , Crawford J. H. , Weinheimer A. J. , Knapp D. J. , Montzka D. D. , Cantrell C. A. , Hornbrook R. S. , Mauldin III R. L. , Wennberg P. O.
Published: April 2010

Abstract. Observations of peroxynitric acid (HO2NO2) obtained simultaneously with those of NO and NO2 provide a sensitive measure of the ozone photochemical production rate. We illustrate this technique for constraining the ozone production rate with observations obtained from the NCAR C-130 aircraft platform during the Megacity Initiative: Local and Global Research Observations (MILAGRO) intensive in Mexico during the spring of 2006. Sensitive and selective measurements of HO2NO2 were made in situ using chemical ionization mass spectrometry (CIMS). Observations were compared to modeled HO2NO2 concentrations obtained from the NASA Langley highly-constrained photochemical time-dependent box model. The median observed-to-calculated ratio of HO2NO2 is 1.18. At NOx levels greater than 15 ppbv, the photochemical box model underpredicts observations with an observed-to-calculated ratio of HO2NO2 of 1.57. As a result, we find that at high NOx, the ozone production rate calculated using measured HO2NO2 is faster than predicted using accepted photochemistry. Inclusion of an additional HOx source from the reaction of excited state NO2 with H2O or reduction in the rate constant of the reaction of OH with NO2 improves the agreement.
Assessing the regional impacts of Mexico City emissions on air quality and chemistry
Authors: Mena-Carrasco M. , Carmichael G. R. , Campbell J. E. , Zimmerman D. , Tang Y. , Adhikary B. , D'allura A. , Molina L. T. , Zavala M. , García A. , Flocke F. , Campos T. , Weinheimer A. J. , Shetter R. , Apel E. , Montzka D. D. , Knapp D. J. , Zheng W.
Published: April 2010

Abstract. The impact of Mexico City (MCMA) emissions is examined by studying its effects on air quality, photochemistry, and on ozone production regimes by combining model products and aircraft observations from the MILAGRO experiment during March 2006. The modeled influence of MCMA emissions to enhancements in surface level NOx, CO, and O3 concentrations (10–30% increase) are confined to distances <200 km, near surface. However, the extent of the influence is significantly larger at higher altitudes. Broader MCMA impacts (some 900 km Northeast of the city) are shown for specific outflow conditions in which enhanced ozone, NOy, and MTBE mixing ratios over the Gulf of Mexico are linked to MCMA by source tagged tracers and sensitivity runs. This study shows that the "footprint" of MCMA on average is fairly local, with exception to reactive nitrogen, which can be transported long range in the form of PAN, acting as a reservoir and source of NOx with important regional ozone formation implications. The simulated effect of MCMA emissions of anthropogenic aerosol on photochemistry showed a maximum regional decrease of 40% in J[NO2→NO+O], and resulting in the reduction of ozone production by 5–10%. Observed ozone production efficiencies are evaluated as a function of distance from MCMA, and by modeled influence from MCMA. These tend to be much lower closer to MCMA, or in those points where modeled contribution from MCMA is large. This research shows that MCMA emissions do effect on regional air quality and photochemistry, both contributing large amounts of ozone and its precursors, but with caveat that aerosol concentrations hinder formation of ozone to its potential due to its reduction in photolysis rates.