bluuebunny/crossref_metadata_2025 huggingface dataset:
A product study of the isoprene+NO3 reaction
Authors: Perring A. E. , Wisthaler A. , Graus M. , Wooldridge P. J. , Lockwood A. L. , Mielke L. H. , Shepson P. B. , Hansel A. , Cohen R. C.
Published: April 2010

Abstract. Oxidation of isoprene through reaction with NO3 radicals is a significant sink for isoprene that persists after dark. The main products of the reaction are multifunctional nitrates. These nitrates constitute a significant NOx sink in the nocturnal boundary layer and they likely play an important role in formation of secondary organic aerosol. Products of the isoprene+NO3 reaction will, in many locations, be abundant enough to affect nighttime radical chemistry and to persist into daytime where they may represent a source of NOx. Product formation in the isoprene + NO3 reaction was studied in a smog chamber at Purdue University. Isoprene nitrates and other hydrocarbon products were observed using Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and reactive nitrogen products were observed using Thermal Dissociation–Laser Induced Fluorescence (TD-LIF). The organic nitrate yield is found to be 65±12% of which the majority was nitrooxy carbonyls and the combined yield of methacrolein and methyl vinyl ketone (MACR+MVK) is found to be ∼10%. PTR-MS measurements of nitrooxy carbonyls and TD-LIF measurements of total organic nitrates agreed well. The PTR-MS also observed a series of minor oxidation products which were tentatively identified and their yields quantified These other oxidation products are used as additional constraints on the reaction mechanism.
Source apportionment of PM2.5 in Seoul, Korea
Authors: Heo J.-B. , Hopke P. K. , Yi S.-M.
Published: April 2010

Abstract. PM2.5 samples were collected at a centrally located urban monitoring site in Seoul, Korea, every third day from March 2003 to December 2006 and analyzed for their chemical constituents. Sources were identified using positive matrix factorization (PMF). A total of 393 samples were obtained during the sampling period, and 20 chemical species were measured. Nine PM2.5 source categories were identified providing physically realistic profiles and interesting insights into the source contributions to the ambient mass concentrations. The major contributors of PM2.5 were secondary nitrate (20.9%), secondary sulfate (20.5%), gasoline-fueled vehicles (17.2%), and biomass burning (12.1%), with lesser contributions from diesel emissions (8.1%), soil (7.4%), industry (6.7%), road salt and two-stroke vehicles (5.1%), and aged sea salt (2.2%). PM2.5 levels in Seoul were influenced by both local urban activities and regional-scale transport. Conditional probability function (CPF) results identified possible source directions of local sources such as motor vehicles (gasoline and diesel), industry, and road salt. Potential source contribution function (PSCF) results showed that possible source areas contributing to the elevated secondary particle concentrations (sulfate and nitrate) in Seoul to be the major industrial areas in China.
Sources and transport of Δ14C in CO2 within the Mexico City Basin and vicinity
Authors: Vay S. A. , Tyler S. C. , Choi Y. , Blake D. R. , Blake N. J. , Sachse G. W. , Diskin G. S. , Singh H. B.
Published: April 2010

Abstract. Radiocarbon samples taken over Mexico City and the surrounding region during the MILAGRO field campaign in March 2006 exhibited an unexpected distribution: (1) relatively few samples (23%) were below the North American free tropospheric background value (57±2‰) despite the fossil fuel emissions from one of the world's most highly polluted environments; and (2) frequent enrichment well above the background value was observed. Correlate source tracer species and air transport characteristics were examined to elucidate influences on the radiocarbon distribution. Our analysis suggests that a combination of radiocarbon sources biased the "regional radiocarbon background" above the North American value thereby decreasing the apparent fossil fuel signature. Likely sources include the release of 14C-enhanced carbon from bomb 14C sequestered in plant carbon pools via the ubiquitous biomass burning in the region as well as the direct release of radiocarbon as CO2 from other "hot" sources. Plausible perturbations from local point "hot" sources include the burning of hazardous waste in cement kilns; medical waste incineration; and emissions from the Laguna Verde Nuclear Power Plant. These observations provide insight into the use of Δ14CO2 to constrain fossil fuel emissions in the megacity environment, indicating that underestimation of the fossil fuel contribution to the CO2 flux is likely wherever biomass burning coexists with urban emissions and is unaccounted for as a source of the elevated CO2 observed above local background. Our findings increase the complexity required to quantify fossil fuel-derived CO2 in source-rich environments characteristic of megacities, and have implications for the use of Δ14CO2 observations in evaluating bottom-up emission inventories and their reliability as a tool for validating national emission claims of CO2 within the framework of the Kyoto Protocol.
Quantifying atmospheric nitrate formation pathways based on a global model of the oxygen isotopic composition (Δ17O) of atmospheric nitrate
Authors: Alexander B. , Hastings M. G. , Allman D. J. , Dachs J. , Thornton J. A. , Kunasek S. A.
Published: April 2010

Abstract. The oxygen isotopic composition (Δ17O) of atmospheric nitrate is a function of the relative abundance of atmospheric oxidants (O3, ROx=OH+HO2+RO2) and the formation pathway of nitrate from its precursor NOx (=NO+NO2). Coupled observations and modeling of nitrate Δ17O can be used to quantify the relative importance of chemical formation pathways leading to nitrate formation and reduce uncertainties in the budget of reactive nitrogen chemistry in the atmosphere. We present the first global model of atmospheric nitrate Δ17O and compare with available observations. The largest uncertainty for calculations of nitrate Δ17O is the unconstrained variability in the Δ17O value of tropospheric ozone. The model shows the best agreement with a global compilation of observations when assuming a Δ17O value of tropospheric ozone equal to 35‰ and preferential oxidation of NOx by the terminal oxygen atoms of ozone. Calculated values of annual-mean nitrate Δ17O in the lowest model layer (0–200 m above the surface) vary from 7‰ in the tropics to 41‰ in the polar-regions. The global, annual-mean tropospheric inorganic nitrate burden is dominated by nitrate formation via NO2+OH (76%), followed by N2O5 hydrolysis (18%) and NO3+DMS/HC (4%). Calculated nitrate Δ17O is sensitive to the relative importance of each nitrate formation pathway, suggesting that observations of nitrate Δ17O can be used to quantify the importance of individual reactions (e.g. N2O5 hydrolysis) leading to nitrate formation if the Δ17O value of ozone is known.
Multi-species inversion of CH4, CO and H2 emissions from surface measurements
Authors: Pison I. , Bousquet P. , Chevallier F. , Szopa S. , Hauglustaine D.
Published: April 2010

Abstract. In order to study the spatial and temporal variations of the emissions of greenhouse gases and of their precursors, we developed a data assimilation system and applied it to infer emissions of CH4, CO and H2 for one year. It is based on an atmospheric chemical transport model and on a simplified scheme for the oxidation chain of hydrocarbons, including methane, formaldehyde, carbon monoxide and molecular hydrogen together with methyl chloroform. The methodology is exposed and a first attempt at evaluating the inverted fluxes is made. Inversions of the emission fluxes of CO, CH4 and H2 and concentrations of HCHO and OH were performed for the year 2004, using surface concentration measurements of CO, CH4, H2 and CH3CCl3 as constraints. Independent data from ship and aircraft measurements and satellite retrievals are used to evaluate the results. The total emitted mass of CO is 30% higher after the inversion, due to increased fluxes by up to 35% in the Northern Hemisphere. The spatial distribution of emissions of CH4 is modified by a decrease of fluxes in boreal areas up to 60%. The comparison between mono- and multi-species inversions shows that the results are close at a global scale but may significantly differ at a regional scale because of the interactions between the various tracers during the inversion.
Long-term changes in UT/LS ozone between the late 1970s and the 1990s deduced from the GASP and MOZAIC aircraft programs and from ozonesondes
Authors: Schnadt Poberaj C. , Staehelin J. , Brunner D. , Thouret V. , De Backer H. , Stübi R.
Published: April 2010

Abstract. We present ozone measurements of the Global Atmospheric Sampling Program (GASP) performed from four commercial and one research aircraft in the late 1970s to compare them with respective measurements of the ongoing MOZAIC project. Multi-annual averages of UT/LS ozone were built using the aircraft data sets (1975–1979 and 1994–2001), and long-term changes between the 1970s and 1990s were derived by comparison. The data were binned relative to the dynamical tropopause to separate between UT and LS air masses. LS data were analysed using equivalent latitudes. In the UT, pronounced increases of 20–40% are found over the Middle East and South Asia in the spring and summer seasons. Increases are also found over Japan, Europe, and the eastern parts of the United States depending on season. LS ozone over northern mid- and high latitudes was found to be lower in the 1990s compared to the 1970s in all seasons of the year. In addition, a comparison with long-term changes deduced from ozonesondes is presented. The early 1970s European Brewer-Mast (BM) sonde data agree with GASP within the range of uncertainty (UT) or measured slightly less ozone (LS). In contrast, the 1990s BM sensors show consistently and significantly higher UT/LS ozone values than MOZAIC. This unequal behaviour of aircraft/sonde comparisons in the 1970s and 1990s leads to differences in the estimated long-term changes over Europe: while the comparison between GASP and MOZAIC indicates ozone changes of −5% to 10% over Europe, the sondes suggest a much larger increase of 10%–35% depending on station and season, although statistical significance is not conclusive due to data sample limitations. In contrast to the BM sondes, the Electrochemical Cell (ECC) sonde at Wallops Island, USA, measured higher UT ozone than both GASP and MOZAIC. Hence, long-term changes from GASP/MOZAIC agree within the range of uncertainty with the changes deduced from Wallops Island.
Characterization of volatile organic compounds (VOCs) in Asian and north American pollution plumes during INTEX-B: identification of specific Chinese air mass tracers
Authors: Barletta B. , Meinardi S. , Simpson I. J. , Atlas E.  L. , Beyersdorf A. J. , Baker A. K. , Blake N. J. , Yang M. , Midyett J. R. , Novak B. J. , McKeachie R. J. , Fuelberg H. E. , Sachse G. W. , Avery M. A. , Campos T. , Weinheimer A. J. , Rowland F. S. , Blake D. R.
Published: April 2010

Abstract. We present results from the Intercontinental Chemical Transport Experiment – Phase B (INTEX-B) aircraft mission conducted in spring 2006. By analyzing the mixing ratios of volatile organic compounds (VOCs) measured during the second part of the field campaign, together with kinematic back trajectories, we were able to identify five plumes originating from China, four plumes from other Asian regions, and three plumes from the United States. To identify specific tracers for the different air masses we characterized their VOC composition and we compared their background levels with those obtained during the 2004 INTEX-A mission. The Chinese and other Asian air masses were significantly enhanced in carbonyl sulfide (OCS) and methyl chloride (CH3Cl), while all CFC replacement compounds were elevated in US plumes, particularly HFC-134a. Although elevated mixing ratios of Halon-1211 were measured in some Chinese plume samples, several measurements at background levels were also observed. After analyzing the VOC distribution and correlations within the Chinese pollution plumes and applying principal component analysis (PCA), we suggest the use of a suite of species, rather than a single gas, as specific tracers of Chinese air masses (namely OCS, CH3Cl, 1,2-dichloroethane, ethyl chloride, and Halon-1211). In an era of constantly changing halocarbon usage patterns, this suite of gases best reflects new emission characteristics from China.
Characterization of organic ambient aerosol during MIRAGE 2006 on three platforms
Authors: Gilardoni S. , Liu S. , Takahama S. , Russell L. M. , Allan J. D. , Steinbrecher R. , Jimenez J. L. , De Carlo P. F. , Dunlea E. J. , Baumgardner D.
Published: April 2010

Abstract. Submicron atmospheric aerosol particles were collected during the Megacity Initiative: Local and Global Research Observation (MILAGRO) in March 2006 at three platforms located in the Mexico City urban area (at the Mexico City Atmospheric Monitoring System building – SIMAT), at about 60 km south-east of the metropolitan area (Altzomoni in the Cortes Pass), and on board the NCAR C130 aircraft. Organic functional group and elemental composition were measured by FTIR and XRF. The average organic mass (OM) concentration, calculated as the sum of organic functional group concentrations, was 9.9 μg m−3 at SIMAT, 6.6 μg m−3 at Altzomoni, and 5.7 μg m−3 on the C130. Aliphatic saturated C-C-H and carboxylic acid COOH groups dominated OM (more than 60%) at the ground sites. On the C130, a non-acid carbonyl C=O, carboxylic acid COOH, and amine NH2 groups were observed in concentrations above detection limit only outside the Mexico City basin. From the elemental composition of SIMAT samples, we estimated the upper bound of average contribution of biomass burning to the organic carbon (OC) as 33–39%. The average OM/OC ratio was 1.8 at SIMAT, 2.0 at Altzomoni, and 1.6–1.8 on the C130. On the aircraft, higher OM/OC ratios were measured outside of the Mexico City basin, north of the urban area, along the city outflow direction. The average carboxylic acid to aliphatic saturated ratio at SIMAT reflected a local increase of oxidized functional group concentration in aged particles.
Long term particle size distribution measurements at Mount Waliguan, a high-altitude site in inland China
Authors: Kivekäs N. , Sun J. , Zhan M. , Kerminen V.-M. , Hyvärinen A. , Komppula M. , Viisanen Y. , Hong N. , Zhang Y. , Kulmala M. , Zhang X.-C. ,   Deli-Geer, Lihavainen H.
Published: April 2010

Abstract. Particle number size distributions in size range 12–570 nm were measured continuously at Mount Waliguan, a remote mountain-top station in inland China. The station is located at the altitude of 3816 m a.s.l., and some 600–1200 m above the surrounding area. The measurement period lasted from September 2005 to May 2007. The measurements were verified with independent CPC measurements at the same site. The average particle concentration in ambient conditions was 2030 cm−3, which is higher than the values measured at similar altitude in other regions of the world. On average, the Aitken mode contributed to roughly half of the particle number concentration. The concentrations were found to be higher during the summer than during the winter. The diurnal variation was also investigated and a clear pattern was found for the nucleation mode during all seasons, so that the nucleation mode particle concentration increased in the afternoon. The same pattern was visible in the Aitken mode during the summer, whereas the accumulation mode did not show any level of diurnal pattern during any season. Excluding the nucleation mode, the average day-time particle concentrations were not significantly higher than those measured at night-time, indicating no systematic pattern of change between planetary boundary layer conditions and free troposphere conditions. In air masses coming from east, the number concentration of particles was higher than in other air masses, which indicates that the air mass might be affected anthropogenic pollution east of the station. Also other factors, such as active new-particle formation, keep aerosol number concentrations high in the area.
In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007: implications for gas- and particle-phase chemistry
Authors: Bouvier-Brown N. C. , Goldstein A. H. , Gilman J. B. , Kuster W. C. , de Gouw J. A.
Published: April 2010

Abstract. We quantified ambient mixing ratios of 9 monoterpenes, 6 sesquiterpenes, methyl chavicol, the oxygenated terpene linalool, and nopinone using an in-situ gas chromatograph with a quadrupole mass spectrometer (GC-MS). These measurements were a part of the 2007 Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) at Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. To our knowledge, these observations represent the first direct in-situ ambient quantification of the sesquiterpenes α-bergamotene, longifolene, α-farnesene, and β-farnesene. From average diurnal mixing ratio profiles, we show that α-farnesene emissions are dependent mainly on temperature whereas α-bergamotene and β-farnesene emissions are temperature- and light-dependent. The amount of sesquiterpene mass quantified above the canopy was small (averaging a total of 3.3 ppt during the day), but nevertheless these compounds contributed 7.6% to the overall ozone-olefin loss rate above the canopy. Assuming that the monoterpene-to-sesquiterpene emission rate in the canopy is similar to that observed in branch enclosure studies at the site during comparable weather conditions, and the average yield of aerosol mass from these sesquiterpenes is 10–50%, the amount of sesquiterpene mass reacted within the Blodgett Forest canopy alone accounts for 6–32% of the total organic aerosol mass measured during BEARPEX. The oxygenated monoterpene linalool was also quantified for the first time at Blodgett Forest. The linalool mass contribution was small (9.9 ppt and 0.74 ppt within and above the canopy, respectively), but it contributed 1.1% to the total ozone-olefin loss rate above the canopy. Reactive and semi-volatile compounds, especially sesquiterpenes, significantly impact the gas- and particle-phase chemistry of the atmosphere at Blodgett Forest and should be included in both biogenic volatile organic carbon emission and atmospheric chemistry models.
Interannual variability of long-range transport as seen at the Mt. Bachelor observatory
Authors: Reidmiller D. R. , Jaffe D. A. , Chand D. , Strode S. , Swartzendruber P. , Wolfe G. M. , Thornton J. A.
Published: April 2010

Abstract. Interannual variations in background tropospheric trace gases (such as carbon monoxide, CO) are largely driven by variations in emissions (especially wildfires) and transport pathways. Understanding this variability is essential to quantify the intercontinental contribution to US air quality. We investigate the interannual variability of long-range transport of Asian pollutants to the Northeast Pacific via measurements from the Mt. Bachelor Observatory (MBO: 43.98° N, 121.69° W; 2.7 km a.s.l.) and GEOS-Chem chemical transport model simulations in spring 2005 vs. the INTEX-B campaign during spring 2006. Measurements of CO at MBO were significantly enhanced during spring 2005 relative to the same time in 2006 (the INTEX-B study period); a decline in monthly mean CO of 41 ppbv was observed between April 2005 and April 2006. A backtrajectory-based meteorological index shows that long-range transport of CO from the heavily industrialized region of East Asia was significantly greater in early spring 2005 than in 2006. In addition, spring 2005 was an anomalously strong biomass burning season in Southeast Asia. Data presented by Yurganov et al. (2008) using MOPITT satellite retrievals from this area reveal an average CO burden anomaly (referenced to March 2000–February 2002 mean values) between October 2004 through April 2005 of 2.6 Tg CO vs. 0.6 Tg CO for the same period a year later. The Naval Research Laboratory's global aerosol transport model, as well as winds from NCEP reanalysis, show that emissions from these fires were efficiently transported to MBO throughout April 2005. Asian dust transport, however, was substantially greater in 2006 than 2005, particularly in May. Monthly mean aerosol light scattering coefficient at 532 nm (σsp) at MBO more than doubled from 2.7 Mm−1 in May 2005 to 6.2 Mm−1 in May 2006. We also evaluate CO interannual variability throughout the western US via Earth System Research Laboratory ground site data and throughout the Northern Hemisphere via MOPITT and TES satellite observations. Both in the Northeast Pacific and on larger scales, we reveal a significant decrease (from 2–21%) in springtime maximum CO between 2005 and 2006, evident in all platforms and the GEOS-Chem model. We attribute this to (a) anomalously strong biomass burning in Southeast Asia during winter 2004 through spring 2005, and (b) the transport pattern in March and April 2006 which limited the inflow of Asian pollution to the lower free troposphere over western North America.
Comparison of conventional Lagrangian stochastic footprint models against LES driven footprint estimates
Authors: Markkanen T. , Steinfeld G. , Kljun N. , Raasch S. , Foken T.
Published: April 2010

Abstract. In this study we introduce a comparison method for footprint model results by evaluating the performance of conventional Lagrangian stochastic (LS) footprint models that use parameterised flow field characteristics with results of a Lagrangian trajectory model embedded in a large eddy simulation (LES) framework. The two conventional models follow the particles backward and forward in time while the trajectories in LES only evolve forward in time. We assess their performance in two unstably stratified boundary layers at observation levels covering the whole depth of the atmospheric boundary layer. We present a concept for footprint model comparison that can be applied for 2-D footprints and demonstrate that comparison of only cross wind integrated footprints is not sufficient for purposes facilitating two dimensional footprint information. Because the flow field description among the three models is most realistic in LES we use those results as the reference in the comparison. We found that the agreement of the two conventional models against the LES is generally better for intermediate measurement heights and for the more unstable case, whereas the two conventional flux footprint models agree best under less unstable conditions. The model comparison in 2-D was found quite sensitive to the grid resolution.
Modeling of secondary organic aerosol yields from laboratory chamber data
Authors: Chan M. N. , Chan A. W. H. , Chhabra P. S. , Surratt J. D. , Seinfeld J. H.
Published: April 2010

Abstract. Laboratory chamber data serve as the basis for constraining models of secondary organic aerosol (SOA) formation. Current models fall into three categories: empirical two-product (Odum), product-specific, and volatility basis set. The product-specific and volatility basis set models are applied here to represent laboratory data on the ozonolysis of α-pinene under dry, dark, and low-NOx conditions in the presence of ammonium sulfate seed aerosol. Using five major identified products, the model is fit to the chamber data. From the optimal fitting, SOA oxygen-to-carbon (O/C) and hydrogen-to-carbon (H/C) ratios are modeled. The discrepancy between measured H/C ratios and those based on the oxidation products used in the model fitting suggests the potential importance of particle-phase reactions. Data fitting is also carried out using the volatility basis set, wherein oxidation products are parsed into volatility bins. The product-specific model is most likely hindered by lack of explicit inclusion of particle-phase accretion compounds. While prospects for identification of the majority of SOA products for major volatile organic compounds (VOCs) classes remain promising, for the near future empirical product or volatility basis set models remain the approaches of choice.
PM10 data assimilation over Europe with the optimal interpolation method
Authors: Tombette M. , Mallet V. , Sportisse B.
Published: April 2010

Abstract. This paper presents experiments of PM10 data assimilation with the optimal interpolation method. The observations are provided by BDQA (Base de Données sur la Qualité de l'Air), whose monitoring network covers France. Two other databases (EMEP and AirBase) are used to evaluate the improvements in the analyzed state over January 2001 and for several outputs (PM10, PM2.5 and chemical composition). The method is then applied in operational-forecast conditions. It is found that the assimilation of PM10 observations significantly improves the one-day forecast of total mass (PM10 and PM2.5), whereas the improvement is non significant for the two-day forecast. The errors on aerosol chemical composition are sometimes amplified by the assimilation procedure, which shows the need for chemical data. Since the observations cover a limited part of the domain (France versus Europe) and since the method used for assimilation is sequential, we focus on the horizontal and temporal impacts of the assimilation and we study how several parameters of the assimilation system modify these impacts. The strategy followed in this paper, with the optimal interpolation, could be useful for operational forecasts. Meanwhile, considering the weak temporal impact of the approach (about one day), the method has to be improved or other methods have to be considered.
Ozone mixing ratios inside tropical deep convective clouds from OMI satellite measurements
Authors: Ziemke J. R. , Joiner J. , Chandra S. , Bhartia P. K. , Vasilkov A. , Haffner D. P. , Yang K. , Schoeberl M. R. , Froidevaux L. , Levelt P. F.
Published: April 2010

Abstract. We have developed a new technique for estimating ozone mixing ratio inside deep convective clouds. The technique uses the concept of an optical centroid cloud pressure that is indicative of the photon path inside clouds. Radiative transfer calculations based on realistic cloud vertical structure as provided by CloudSat radar data show that because deep convective clouds are optically thin near the top, photons can penetrate significantly inside the cloud. This photon penetration coupled with in-cloud scattering produces optical centroid pressures that are hundreds of hPa inside the cloud. We combine measured column ozone and the optical centroid cloud pressure derived using the effects of rotational-Raman scattering to estimate O3 mixing ratio in the upper regions of deep convective clouds. The data are obtained from the Ozone Monitoring Instrument (OMI) onboard NASA's Aura satellite. Our results show that low O3 concentrations in these clouds are a common occurrence throughout much of the tropical Pacific. Ozonesonde measurements in the tropics following convective activity also show very low concentrations of O3 in the upper troposphere. These low amounts are attributed to vertical injection of ozone poor oceanic boundary layer air during convection into the upper troposphere followed by convective outflow. Over South America and Africa, O3 mixing ratios inside deep convective clouds often exceed 50 ppbv which are comparable to mean background (cloud-free) amounts and are consistent with higher concentrations of injected boundary layer/lower tropospheric O3 relative to the remote Pacific. The Atlantic region in general also consists of higher amounts of O3 precursors due to both biomass burning and lightning. Assuming that O3 is well mixed (i.e., constant mixing ratio with height) up to the tropopause, we can estimate the stratospheric column O3 over clouds. Stratospheric column ozone derived in this manner agrees well with that retrieved independently with the Aura Microwave Limb Sounder (MLS) instrument and thus provides a consistency check of our method.
Evaluation of CLaMS, KASIMA and ECHAM5/MESSy1 simulations in the lower stratosphere using observations of Odin/SMR and ILAS/ILAS-II
Authors: Khosrawi F. , Müller R. , Proffitt M. H. , Ruhnke R. , Kirner O. , Jöckel P. , Grooß J.-U. , Urban J. , Murtagh D. , Nakajima H.
Published: April 2010

Abstract. 1-year data sets of monthly averaged nitrous oxide (N2O) and ozone (O3) derived from satellite measurements were used as a tool for the evaluation of atmospheric photochemical models. Two 1-year data sets, one solar occultation data set derived from the Improved Limb Atmospheric Spectrometer (ILAS and ILAS-II) and one limb sounding data set derived from the Odin Sub-Millimetre Radiometer (Odin/SMR) were employed. Here, these data sets are used for the evaluation of two Chemical Transport Models (CTMs), the Karlsruhe Simulation Model of the Middle Atmosphere (KASIMA) and the Chemical Lagrangian Model of the Stratosphere (CLaMS) as well as for one Chemistry-Climate Model (CCM), the atmospheric chemistry general circulation model ECHAM5/MESSy1 (E5M1) in the lower stratosphere with focus on the Northern Hemisphere. Since the Odin/SMR measurements cover the entire hemisphere, the evaluation is performed for the entire hemisphere as well as for the low latitudes, midlatitudes and high latitudes using the Odin/SMR 1-year data set as reference. To assess the impact of using different data sets for such an evaluation study we repeat the evaluation for the polar lower stratosphere using the ILAS/ILAS-II data set. Only small differences were found using ILAS/ILAS-II instead of Odin/SMR as a reference, thus, showing that the results are not influenced by the particular satellite data set used for the evaluation. The evaluation of CLaMS, KASIMA and E5M1 shows that all models are in agreement with Odin/SMR and ILAS/ILAS-II. Differences are generally in the range of ±20%. Larger differences (up to −40%) are found in all models at 500±25 K for N2O mixing ratios greater than 200 ppbv, thus in air masses of tropical character. Generally, the largest differences were found for the tropics and the lowest for the polar regions. However, an underestimation of polar winter ozone loss was found both in KASIMA and E5M1 both in the Northern and Southern Hemisphere.
Tropospheric water vapour above Switzerland over the last 12 years
Authors: Morland J. , Collaud Coen M. , Hocke K. , Jeannet P. , Mätzler C.
Published: April 2010

Abstract. Integrated Water vapour (IWV) has been measured since 1994 by the TROWARA microwave radiometer in Bern, Switzerland. Homogenization techniques were used to identify and correct step changes in IWV related to instrument problems. IWV from radiosonde, GPS and sun photometer (SPM) was used in the homogenisation process as well as partial IWV columns between valley and mountain weather stations. The average IWV of the homogenised TROWARA time series was 14.4 mm over the 1996–2007 period, with maximum and minimum monthly average values of 22.4 mm and 8 mm occurring in August and January, respectively. A weak diurnal cycle in TROWARA IWV was detected with an amplitude of 0.32 mm, a maximum at 21:00 UT and a minimum at 11:00 UT. For 1996–2007, TROWARA trends were compared with those calculated from the Payerne radiosonde and the closest ECMWF grid point to Bern. Using least squares analysis, the IWV time series of radiosondes at Payerne, ECMWF, and TROWARA showed consistent positive trends from 1996 to 2007. The radiosondes measured an IWV trend of 0.45±0.29%/y, the TROWARA radiometer observed a trend of 0.39±0.44%/y, and ECMWF operational analysis gave a trend of 0.25±0.34%/y. Since IWV has a strong and variable annual cycle, a seasonal trend analysis (Mann-Kendall analysis) was also performed. The seasonal trends are stronger by a factor 10 or so compared to the full year trends above. The positive IWV trends of the summer months are partly compensated by the negative trends of the winter months. The strong seasonal trends of IWV on regional scale underline the necessity of long-term monitoring of IWV for detection,understanding, and forecast of climate change effects in the Alpine region.
Comment on "Comparisons with analytical solutions from Khvorostyanov and Curry (2007) on the critical droplet radii and supersaturations of CCN with insoluble fractions" by Kokkola et al. (2008)
Authors: Khvorostyanov V. I. , Curry J. A.
Published: April 2010

Abstract. Analytical solutions for the critical radii and supersaturations of the cloud condensation nuclei (CCN) with insoluble fractions were derived by Khvorostyanov and Curry (2007, hereafter KC07). These solutions generalize Köhler's solutions for an arbitrary soluble fraction of CCN, and have two limiting cases: large soluble fraction (Köhler's original solution); and a new "low soluble fraction" limit. Similar solutions were found subsequently by Kokkola et al. (2008, hereafter Kok08); however, Kok08 used the approximation of an ideal and dilute solution, while KC07 used more accurate assumptions that account for nonideality of solutions. Kok08 found a large discrepancy with KC07 in the critical supersaturations. It is shown that the major discrepancy with KC07 found in Kok08 was caused by the simple mistake in Kok08, where comparison was made not with the general solution from KC07, but with the Köhler's solution or with some unknown quantity, not even with the "low soluble fraction" limit. If general solutions from the two works are compared, the equations from Kok08 mostly repeat the equations from KC07, except that Kok08 use the ideal dilute solution approximation. If the mistake in Kok08 is corrected, then the differences in the critical radii and supersaturations do not exceed 16–18%, which characterizes the errors of the ideal dilute solution approximation. If the Kok08 scheme is modified following KC07 to account for the non-ideality of solution, then the difference with KC07 does not exceed 0.4–1%.
Satellite observations and model simulations of tropospheric NO2 columns over south-eastern Europe
Authors: Zyrichidou I. , Koukouli M. E. , Balis D. S. , Katragkou E. , Melas D. , Poupkou A. , Kioutsioukis I. , van der A R. , Boersma F. K. , van Roozendael M. , Richter A.
Published: April 2010

Abstract. Satellite observations of nitrogen dioxide (NO2) tropospheric columns over south-eastern Europe are analyzed to study the characteristics of the spatial and temporal variability of pollution in the area. The interannual variability of the tropospheric NO2 columns is presented over urban, rural and industrial locations based on measurements from four satellite instruments, GOME/ERS-2, SCIAMACHY/Envisat, OMI/Aura and GOME-2/MetOp spanning a period of over twelve years. The consistency between the different datasets over the area is investigated. Two operational algorithms for the retrieval of tropospheric NO2 are considered, the one developed jointly by the Royal Netherlands Meteorological Institute and Belgian Institute for Space Astronomy and the one developed by the University of Bremen. The tropospheric NO2 columns for the area under study have been simulated for the period 1996–2001 with the Comprehensive Air Quality Model (CAMx) and are compared with GOME measurements. Over urban and industrial locations the mean tropospheric NO2 columns range between 3 and 7.0×1015 molecules/cm2, showing a seasonal variability with a peak to peak amplitude of about 6.0×1015 molecules/cm2, while the background values over rural sites are close to 1.1×1015 molecules/cm2. Differences in the overpass time and spatial resolution of the different satellites, as well as differences in the algorithms, introduce significant differences in the estimated columns however the correlation between the different estimates is higher than 0.8. It is found that the model simulations reveal similar spatial patterns as the GOME observations, a result which is consistent with both algorithms. Although the model simulations show a mean bias of −0.1×1015 molecules/cm2 under clean conditions, the modeled temporal correlation of 0.5 is poor in absence of biogenic and biomass burning emissions.
Evaluating simulated primary anthropogenic and biomass burning organic aerosols during MILAGRO: implications for assessing treatments of secondary organic aerosols
Authors: Fast J. , Aiken A. C. , Allan J. , Alexander L. , Campos T. , Canagaratna M. R. , Chapman E. , DeCarlo P. F. , de Foy B. , Gaffney J. , de Gouw J. , Doran J. C. , Emmons L. , Hodzic A. , Herndon S. C. , Huey G. , Jayne J. T. , Jimenez J. L. , Kleinman L. , Kuster W. , Marley N. , Russell L. , Ochoa C. , Onasch T. B. , Pekour M. , Song C. , Ulbrich I. M. , Warneke C. , Welsh-Bon D. , Wiedinmyer C. , Worsnop D. R. , Yu X.-Y. , Zaveri R.
Published: April 2010

Abstract. Simulated primary organic aerosols (POA), as well as other particulates and trace gases, in the vicinity of Mexico City are evaluated using measurements collected during the 2006 Megacity Initiative: Local and Global Research Observations (MILAGRO) field campaigns. Since the emission inventories, transport, and turbulent mixing will directly affect predictions of total organic matter and consequently total particulate matter, our objective is to assess the uncertainties in predicted POA before testing and evaluating the performance of secondary organic aerosol (SOA) treatments. Carbon monoxide (CO) is well simulated on most days both over the city and downwind, indicating that transport and mixing processes were usually consistent with the meteorological conditions observed during MILAGRO. Predicted and observed elemental carbon (EC) in the city was similar, but larger errors occurred at remote locations since the overall CO/EC emission ratios in the national emission inventory were lower than in the metropolitan emission inventory. Components of organic aerosols derived from Positive Matrix Factorization of data from several Aerodyne Aerosol Mass Spectrometer instruments deployed both at ground sites and on research aircraft are used to evaluate the model. Modeled POA was consistently lower than the measured organic matter at the ground sites, which is consistent with the expectation that SOA should be a large fraction of the total organic matter mass. A much better agreement was found when modeled POA was compared with the sum of "primary anthropogenic" and "biomass burning" components derived from Positive Matrix Factorization (PMF) on most days, especially at the surface sites, suggesting that the overall magnitude of primary organic particulates released was reasonable. However, simulated POA from anthropogenic sources was often lower than "primary anthropogenic" components derived from PMF, consistent with two recent reports that these emissions are underestimated. The modeled POA was greater than the total observed organic matter when the aircraft flew directly downwind of large fires, suggesting that biomass burning emission estimates from some large fires may be too high.
Measurements of total and tropospheric ozone from IASI: comparison with correlative satellite, ground-based and ozonesonde observations
Authors: Boynard A. , Clerbaux C. , Coheur P.-F. , Hurtmans D. , Turquety S. , George M. , Hadji-Lazaro J. , Keim C. , Meyer-Arnek J.
Published: April 2010

Abstract. In this paper, we present measurements of total and tropospheric ozone, retrieved from infrared radiance spectra recorded by the Infrared Atmospheric Sounding Interferometer (IASI), which was launched on board the MetOp-A European satellite in October 2006. We compare IASI total ozone columns to Global Ozone Monitoring Experiment-2 (GOME-2) observations and ground-based measurements from the Dobson and Brewer network for one full year of observations (2008). The IASI total ozone columns are shown to be in good agreement with both GOME-2 and ground-based data, with correlation coefficients of about 0.9 and 0.85, respectively. On average, IASI ozone retrievals exhibit a positive bias of about 9 DU (3.3%) compared to both GOME-2 and ground-based measurements. In addition to total ozone columns, the good spectral resolution of IASI enables the retrieval of tropospheric ozone concentrations. Comparisons of IASI tropospheric columns to 490 collocated ozone soundings available from several stations around the globe have been performed for the period of June 2007–August 2008. IASI tropospheric ozone columns compare well with sonde observations, with correlation coefficients of 0.95 and 0.77 for the [surface–6 km] and [surface–12 km] partial columns, respectively. IASI retrievals tend to overestimate the tropospheric ozone columns in comparison with ozonesonde measurements. Positive average biases of 0.15 DU (1.2%) and 3 DU (11%) are found for the [surface–6 km] and for the [surface–12 km] partial columns respectively.
Tula industrial complex (Mexico) emissions of SO2 and NO2 during the MCMA 2006 field campaign using a mobile mini-DOAS system
Authors: Rivera C. , Sosa G. , Wöhrnschimmel H. , de Foy B. , Johansson M. , Galle B.
Published: April 2010

Abstract. The Mexico City Metropolitan Area (MCMA) has presented severe pollution problems for many years. There are several point and mobile emission sources inside and outside the MCMA which are known to affect air quality in the area. In particular, speculation has risen as to whether the Tula industrial complex, located 60 km northwest of the MCMA has any influence on high SO2 levels occurring on the northern part of the city, in the winter season mainly. As part of the MILAGRO Field Campaign, from 24 March to 17 April 2006, the differential vertical columns of sulfur dioxide (SO2) and nitrogen dioxide (NO2) were measured during plume transects in the neighborhood of the Tula industrial complex using mobile mini-DOAS instruments. Vertical profiles of wind speed and direction obtained from pilot balloons and radiosondes were used to calculate SO2 and NO2 emissions. According to our measurements, calculated average emissions of SO2 and NO2 during the field campaign were 384±103 and 24±7 tons day−1, respectively. The standard deviation of these estimations is due to actual variations in the observed emissions from the refinery and power plant, as well as to the uncertainty in the wind fields at the exact time of the measurements. Reported values in recent inventories were found to be in good agreement with calculated emissions during the field campaign. Our measurements were also found to be in good agreement with simulated plumes.
The simulation of the Antarctic ozone hole by chemistry-climate models
Authors: Struthers H. , Bodeker G. E. , Austin J. , Bekki S. , Cionni I. , Dameris M. , Giorgetta M. A. , Grewe V. , Lefèvre F. , Lott F. , Manzini E. , Peter T. , Rozanov E. , Schraner M.
Published: April 2010

Abstract. While chemistry-climate models are able to reproduce many characteristics of the global total column ozone field and its long-term evolution, they have fared less well in simulating the commonly used diagnostic of the area of the Antarctic ozone hole i.e. the area within the 220 Dobson Unit (DU) contour. Two possible reasons for this are: (1) the underlying Global Climate Model (GCM) does not correctly simulate the size of the polar vortex, and (2) the stratospheric chemistry scheme incorporated into the GCM, and/or the model dynamics, results in systematic biases in the total column ozone fields such that the 220 DU contour is no longer appropriate for delineating the edge of the ozone hole. Both causes are examined here with a view to developing ozone hole area diagnostics that better suit measurement-model inter-comparisons. The interplay between the shape of the meridional mixing barrier at the edge of the vortex and the meridional gradients in total column ozone across the vortex edge is investigated in measurements and in 5 chemistry-climate models (CCMs). Analysis of the simulation of the polar vortex in the CCMs shows that the first of the two possible causes does play a role in some models. This in turn affects the ability of the models to simulate the large observed meridional gradients in total column ozone. The second of the two causes also strongly affects the ability of the CCMs to track the observed size of the ozone hole. It is shown that by applying a common algorithm to the CCMs for selecting a delineating threshold unique to each model, a more appropriate diagnostic of ozone hole area can be generated that shows better agreement with that derived from observations.
Analysing spatio-temporal patterns of the global NO2-distribution retrieved from GOME satellite observations using a generalized additive model
Authors: Hayn M. , Beirle S. , Hamprecht F. A. , Platt U. , Menze B. H. , Wagner T.
Published: April 2010

Abstract. With the increasing availability of observational data from different sources at a global level, joint analysis of these data is becoming especially attractive. For such an analysis – oftentimes with little prior knowledge about local and global interactions between the different observational variables at hand – an exploratory, data-driven analysis of the data may be of particular relevance. In the present work we used generalized additive models (GAM) in an exemplary study of spatio-temporal patterns in the tropospheric NO2-distribution derived from GOME satellite observations (1996 to 2001) at global scale. We focused on identifying correlations between NO2 and local wind fields, a quantity which is of particular interest in the analysis of spatio-temporal interactions. Formulating general functional, parametric relationships between the observed NO2 distribution and local wind fields, however, is difficult – if not impossible. So, rather than following a model-based analysis testing the data for predefined hypotheses (assuming, for example, sinusoidal seasonal trends), we used a GAM with non-parametric model terms to learn this functional relationship between NO2 and wind directly from the data. The NO2 observations showed to be affected by wind-dominated processes over large areas. We estimated the extent of areas affected by specific NO2 emission sources, and were able to highlight likely atmospheric transport "pathways". General temporal trends which were also part of our model – weekly, seasonal and linear changes – showed to be in good agreement with previous studies and alternative ways of analysing the time series. Overall, using a non-parametric model provided favorable means for a rapid inspection of this large spatio-temporal NO2 data set, with less bias than parametric approaches, and allowing to visualize dynamical processes of the NO2 distribution at a global scale.