bluuebunny/crossref_metadata_2025 huggingface dataset:
Aerosol model selection and uncertainty modelling by adaptive MCMC technique
Authors: Laine M. , Tamminen J.
Published: April 2010

Abstract. We present a new technique for model selection problem in atmospheric remote sensing. The technique is based on Monte Carlo sampling and it allows model selection, calculation of model posterior probabilities and model averaging in Bayesian way. The algorithm developed here is called Adaptive Automatic Reversible Jump Markov chain Monte Carlo method (AARJ). It uses Markov chain Monte Carlo (MCMC) technique and its extension called Reversible Jump MCMC. Both of these techniques have been used extensively in statistical parameter estimation problems in wide area of applications since late 1990's. The novel feature in our algorithm is the fact that it is fully automatic and easy to use. We show how the AARJ algorithm can be implemented and used for model selection and averaging, and to directly incorporate the model uncertainty. We demonstrate the technique by applying it to the statistical inversion problem of gas profile retrieval of GOMOS instrument on board the ENVISAT satellite. Four simple models are used simultaneously to describe the dependence of the aerosol cross-sections on wavelength. During the AARJ estimation all the models are used and we obtain a probability distribution characterizing how probable each model is. By using model averaging, the uncertainty related to selecting the aerosol model can be taken into account in assessing the uncertainty of the estimates.
Lightning activity in Brazilian thunderstorms during TROCCINOX: implications for NOx production
Authors: Huntrieser H. , Schumann U. , Schlager H. , Höller H. , Giez A. , Betz H.-D. , Brunner D. , Forster C. , Pinto O. , Calheiros R.
Published: April 2010

Abstract. During the TROCCINOX field experiment in January and February 2005, the contribution of lightning-induced nitrogen oxides (LNOx) from tropical and subtropical thunderstorms in Southern Brazil was investigated. Airborne trace gas measurements (NO, NOy, CO and O3) were performed up to 12.5 km with the German research aircraft Falcon. During anvil penetrations in selected tropical and subtropical thunderstorms of 4 and 18 February, NOx mixing ratios were on average enhanced by 0.7–1.2 and 0.2–0.8 nmol mol−1 totally, respectively. The relative contributions of boundary layer NOx (BL-NOx) and LNOx to anvil-NOx were derived from the NOx-CO correlations. On average ~80–90% of the anvil-NOx was attributed to LNOx. A Lightning Location Network (LINET) was set up to monitor the local distribution of cloud-to-ground (CG) and intra-cloud (IC) radiation sources (here called "strokes") and compared with lightning data from the operational Brazilian network RINDAT (Rede Integrada Nacional de Detecção de Descargas Atmosféricas). The horizontal LNOx mass flux out of the anvil was determined from the mean LNOx mixing ratio, the horizontal outflow velocity and the size of the vertical cross-section of the anvil, and related to the number of strokes contributing to LNOx. The values of these parameters were derived from the airborne measurements, from lightning and radar observations, and from a trajectory analysis. The amount of LNOx produced per LINET stroke depending on measured peak current was determined. The results were scaled up with the Lightning Imaging Sensor (LIS) flash rate (44 flashes s−1) to obtain an estimate of the global LNOx production rate. The final results gave ~1 and ~2–3 kg(N) per LIS flash based on measurements in three tropical and one subtropical Brazilian thunderstorms, respectively, suggesting that tropical flashes may be less productive than subtropical ones. The equivalent mean annual global LNOx nitrogen mass production rate was estimated to be 1.6 and 3.1 Tg a−1, respectively. By use of LINET observations in Germany in July 2005, a comparison with the lightning activity in mid-latitude thunderstorms was also performed. In general, the same frequency distribution of stroke peak currents as for tropical thunderstorms over Brazil was found. The different LNOx production rates per stroke in tropical thunderstorms compared with subtropical and mid-latitude thunderstorms seem to be related to the different stroke lengths (inferred from comparison with laboratory data and observed lengths). In comparison, the impact of other lightning parameters as stroke peak current and stroke release height was assessed to be minor. The results from TROCCINOX suggest that the different vertical wind shear may be responsible for the different stroke lengths.
Do supersonic aircraft avoid contrails?
Authors: Stenke A. , Grewe V. , Pechtl S.
Published: April 2010

Abstract. The impact of a potential future fleet of supersonic aircraft on contrail coverage and contrail radiative forcing is investigated by means of simulations with the general circulation model ECHAM4.L39(DLR) including a contrail parameterization. The model simulations consider air traffic inventories of a subsonic fleet and of a combined fleet of sub- and supersonic aircraft for the years 2025 and 2050, respectively. In case of the combined fleet, part of the subsonic fleet is replaced by supersonic aircraft. The combined air traffic scenario reveals a reduction in contrail cover at subsonic cruise levels (10 to 12 km) in the northern extratropics, especially over the North Atlantic and North Pacific. At supersonic flight levels (18 to 20 km), contrail formation is mainly restricted to tropical regions. Only in winter is the northern extratropical stratosphere above the 100 hPa level cold enough for the formation of contrails. Total contrail coverage is only marginally affected by the shift in flight altitude. The model simulations indicate a global annual mean contrail cover of 0.372% for the subsonic and 0.366% for the combined fleet in 2050. The simulated contrail radiative forcing is most closely correlated to the total contrail cover, although contrails in the tropical lower stratosphere are found to be optically thinner than contrails in the extratropical upper troposphere. The global annual mean contrail radiative forcing in 2050 (2025) amounts to 24.7 mW m−2 (9.4 mW m−2) for the subsonic fleet and 24.2 mW m−2 (9.3 mW m−2) for the combined fleet. A reduction of the supersonic cruise speed from Mach 2.0 to Mach 1.6 leads to a downward shift in contrail cover, but does not affect global mean total contrail cover and contrail radiative forcing. Hence the partial substitution of subsonic air traffic leads to a shift of contrail occurrence from mid to low latitudes, but the resulting change in contrail-induced climate impact is almost negligible.
Intra-community spatial variability of particulate matter size distributions in Southern California/Los Angeles
Authors: Krudysz M. , Moore K. , Geller M. , Sioutas C. , Froines J.
Published: April 2010

Abstract. Ultrafine particle (UFP) number concentrations vary significantly on small spatial and temporal scales due to their short atmospheric lifetimes and multiplicity of sources. To determine UFP exposure gradients within a community, simultaneous particle number concentration measurements at a network of sites are necessary. Concurrent particle number size distribution measurements aid in identifying UFP sources, while providing data to investigate local scale effects of both photochemical and physical processes on UFP. From April to December 2007, we monitored particle number size distributions at 13 sites within 350 m–11 km of each other in the vicinity of the Ports of Los Angeles and Long Beach using Scanning Mobility Particle Sizers (SMPS). Typically, three SMPS units were simultaneously deployed and rotated among sites at 1–2 week intervals. Total particle number concentration measurements were conducted continuously at all sites. Seasonal and diurnal number size distribution patterns are complex, highly dependent on local meteorology, nearby PM sources, and times of day, and cannot be generalized over the study area nor inferred from one or two sampling locations. Spatial variation in particle number size distributions was assessed by calculating the coefficient of divergence (COD) and correlation coefficients (r) between site pairs. Results show an overall inverse relationship between particle size and CODs, implying that number concentrations of smaller particles (<40 nm) differ from site to site, whereas larger particles tend to have similar concentrations at various sampling locations. In addition, variations in r values as a function of particle size are not necessarily consistent with corresponding COD values, indicating that using results from correlation analysis alone may not accurately assess spatial variability.
Attribution of projected changes in summertime US ozone and PM2.5 concentrations to global changes
Authors: Avise J. , Chen J. , Lamb B. , Wiedinmyer C. , Guenther A. , Salathé E. , Mass C.
Published: April 2010

Abstract. The impact that changes in future climate, anthropogenic US emissions, background tropospheric composition, and land-use have on summertime regional US ozone and PM2.5 concentrations is examined through a matrix of downscaled regional air quality simulations, where each set of simulations was conducted for five months of July climatology, using the Community Multi-scale Air Quality (CMAQ) model. Projected regional scale changes in meteorology due to climate change under the Intergovernmental Panel on Climate Change (IPCC) A2 scenario are derived through the downscaling of Parallel Climate Model (PCM) output with the MM5 meteorological model. Future chemical boundary conditions are obtained through downscaling of MOZART-2 (Model for Ozone and Related Chemical Tracers, version 2.4) global chemical model simulations based on the IPCC Special Report on Emissions Scenarios (SRES) A2 emissions scenario. Projected changes in US anthropogenic emissions are estimated using the EPA Economic Growth Analysis System (EGAS), and changes in land-use are projected using data from the Community Land Model (CLM) and the Spatially Explicit Regional Growth Model (SERGOM). For July conditions, changes in chemical boundary conditions are found to have the largest impact (+5 ppbv) on average daily maximum 8-h (DM8H) ozone. Changes in US anthropogenic emissions are projected to increase average DM8H ozone by +3 ppbv. Land-use changes are projected to have a significant influence on regional air quality due to the impact these changes have on biogenic hydrocarbon emissions. When climate changes and land-use changes are considered simultaneously, the average DM8H ozone decreases due to a reduction in biogenic VOC emissions (−2.6 ppbv). Changes in average 24-h (A24-h) PM2.5 concentrations are dominated by projected changes in anthropogenic emissions (+3 μg m−3), while changes in chemical boundary conditions have a negligible effect. On average, climate change reduces A24-h PM2.5 concentrations by −0.9 μg m−3, but this reduction is more than tripled in the Southeastern US due to increased precipitation and wet deposition.
Transport mechanisms for synoptic, seasonal and interannual SF6 variations and "age" of air in troposphere
Authors: Patra P. K. , Takigawa M. , Dutton G. S. , Uhse K. , Ishijima K. , Lintner B. R. , Miyazaki K. , Elkins J. W.
Published: April 2010

Abstract. We use an atmospheric general circulation model (AGCM) driven chemistry-transport model (ACTM) to simulate the evolution of sulfur hexafluoride (SF6) in the troposphere. The model results are compared with continuous measurements at 6 sites over 71° N–90° S. These comparisons demonstrate that the ACTM simulations lie within the measurement uncertainty over the analysis period (1999–2006) and capture salient features of synoptic, seasonal and interannual SF6 variability. To understand transport timescales of SF6 within the troposphere, transport times of air parcels from the surface to different regions of the troposphere ("age") are estimated from a simulation of an idealized tracer. The age estimation error and its sensitivity to the selection of reanalysis meteorology for ACTM nudging or the tracer transport by deep cumulus convection as represented in the model are discussed. Monthly-mean, 2-box model exchange times (τex) are calculated from both the observed and simulated SF6 time series at the 6 observing sites and show favorable agreement, suggesting that the ACTM adequately represents large-scale interhemispheric transport. The simulated SF6 variability is further investigated through decomposition of the mixing ratio time-tendency into advective, convective, and vertical diffusive components. The transport component analysis illustrates the role of each process in SF6 synoptic variability at the site level and provides insight into the seasonality of τex.
Monte Carlo simulations of two-component drop growth by stochastic coalescence
Authors: Alfonso L. , Raga G. B. , Baumgardner D.
Published: April 2010

Abstract. The evolution of two-dimensional drop distributions is simulated in this study using a Monte Carlo method. The stochastic algorithm of Gillespie (1976) for chemical reactions in the formulation proposed by Laurenzi et al. (2002) was used to simulate the kinetic behavior of the drop population. Within this framework, species are defined as droplets of specific size and aerosol composition. The performance of the algorithm was checked by a comparison with the analytical solutions found by Lushnikov (1975) and Golovin (1963) and with finite difference solutions of the two-component kinetic collection equation obtained for the Golovin (sum) and hydrodynamic kernels. Very good agreement was observed between the Monte Carlo simulations and the analytical and numerical solutions. A simulation for realistic initial conditions is presented for the hydrodynamic kernel. As expected, the aerosol mass is shifted from small to large particles due to collection process. This algorithm could be extended to incorporate various properties of clouds such several crystals habits, different types of soluble CCN, particle charging and drop breakup.
The effects of experimental uncertainty in parameterizing air-sea gas exchange using tracer experiment data
Authors: Asher W. E.
Published: April 2010

Abstract. It is not practical to measure air-sea gas fluxes in the open ocean for all conditions and areas of interest. Therefore, in many cases fluxes are estimated from measurements of air-phase and water-phase gas concentrations, a measured environmental forcing function such as wind speed, and a parameterization of the air-sea transfer velocity in terms of the environmental forcing function. One problem with this approach is that when direct measurements of the transfer velocity are plotted versus the most commonly used forcing function, wind speed, there is considerable scatter, leading to a relatively large uncertainty in the flux. Because it is known that multiple processes can affect gas transfer, it is commonly assumed that this scatter is caused by single-forcing function parameterizations being incomplete in a physical sense. However, scatter in the experimental data can also result from experimental uncertainty (i.e., measurement error). Here, results from field and laboratory results are used to estimate how experimental uncertainty contributes to the observed scatter in the measured fluxes and transfer velocities as a function of environmental forcing. The results show that experimental uncertainty could explain half of the observed scatter in field and laboratory measurements of air-sea gas transfer velocity.
Uncertainty in global CCN concentrations from uncertain aerosol nucleation and primary emission rates
Authors: Pierce J. R. , Adams P. J.
Published: April 2010

Abstract. The indirect effect of aerosols on climate is highly uncertain and limits our ability to assess anthropogenic climate change. The foundation of this uncertainty is uncertainty in the number of cloud condensation nuclei (CCN), which itself stems from uncertainty in aerosol nucleation, primary emission and growth rates. In this paper, we use a global general circulation model with aerosol microphysics to assess how the uncertainties in aerosol nucleation, emission and growth rates affect our prediction of CCN(0.2%) concentrations. Using several nucleation rate parameterizations that span six orders of magnitude of globally averaged nucleation rates, the tropospheric average CCN(0.2%) concentrations vary by 17% and the boundary layer average vary by 12%. This sensitivity of tropospheric average CCN(0.2%) to the nucleation parameterizations increases to 33% and 20% when the total primary emissions are reduced by a factor of 3 and the SOA condensation rates are increased by a factor of 3.5, respectively. These results show that it is necessary to better understand global nucleation rates when determining CCN concentrations. When primary emissions rates are varied by a factor of 3 while using a binary nucleation parameterization, tropospheric average CCN(0.2%) concentrations also vary by 17%, but boundary layer average vary by 40%. Using the fastest nucleation rate parameterization, these changes drop to 3% and 22%, respectively. These results show the importance of reducing uncertainties in primary emissions, which appear from these results to be somewhat more important for CCN than the much larger uncertainties in nucleation. These results also show that uncertainties in nucleation and primary emissions are more important when sufficient condensable material is available to grow them to CCN sizes. The percent change in CCN(0.2%) concentration between pre-industrial times and present day does not depend greatly on the nucleation rate parameterization used for our base case scenarios; however, because other factors, such as primary emissions and SOA, are uncertain in both time periods, this may be a coincidence.
Modelled radiative forcing of the direct aerosol effect with multi-observation evaluation
Authors: Myhre G. , Berglen T. F. , Johnsrud M. , Hoyle C. R. , Berntsen T. K. , Christopher S. A. , Fahey D. W. , Isaksen I. S. A. , Jones T. A. , Kahn R. A. , Loeb N. , Quinn P. , Remer L. , Schwarz J. P. , Yttri K. E.
Published: April 2010

Abstract. A high-resolution global aerosol model (Oslo CTM2) driven by meteorological data and allowing a comparison with a variety of aerosol observations is used to simulate radiative forcing (RF) of the direct aerosol effect. The model simulates all main aerosol components, including several secondary components such as nitrate and secondary organic carbon. The model reproduces the main chemical composition and size features observed during large aerosol campaigns. Although the chemical composition compares best with ground-based measurement over land for modelled sulphate, no systematic differences are found for other compounds. The modelled aerosol optical depth (AOD) is compared to remote sensed data from AERONET ground and MODIS and MISR satellite retrievals. To gain confidence in the aerosol modelling, we have tested its ability to reproduce daily variability in the aerosol content, and this is performing well in many regions; however, we also identified some locations where model improvements are needed. The annual mean regional pattern of AOD from the aerosol model is broadly similar to the AERONET and the satellite retrievals (mostly within 10–20%). We notice a significant improvement from MODIS Collection 4 to Collection 5 compared to AERONET data. Satellite derived estimates of aerosol radiative effect over ocean for clear sky conditions differs significantly on regional scales (almost up to a factor two), but also in the global mean. The Oslo CTM2 has an aerosol radiative effect close to the mean of the satellite derived estimates. We derive a radiative forcing (RF) of the direct aerosol effect of −0.35 Wm−2 in our base case. Implementation of a simple approach to consider internal black carbon (BC) mixture results in a total RF of −0.28 Wm−2. Our results highlight the importance of carbonaceous particles, producing stronger individual RF than considered in the recent IPCC estimate; however, net RF is less different. A significant RF from secondary organic aerosols (SOA) is estimated (close to −0.1 Wm−2). The SOA also contributes to a strong domination of secondary aerosol species for the aerosol composition over land. A combination of sensitivity simulations and model evaluation show that the RF is rather robust and unlikely to be much stronger than in our best estimate.
HOCl chemistry in the Antarctic Stratospheric Vortex 2002, as observed with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS)
Authors: von Clarmann T. , Glatthor N. , Ruhnke R. , Stiller G. P. , Kirner O. , Reddmann T. , Höpfner M. , Kellmann S. , Kouker W. , Linden A. , Funke B.
Published: April 2010

Abstract. In the 2002 Antarctic polar vortex enhanced HOCl mixing ratios were detected by the Michelson Interferometer for Passive Atmospheric Sounding both at altitudes of around 35 km (1000 K potential temperature), where HOCl abundances are ruled by gas phase chemistry and at around 18–24 km (475–625 K), which belongs to the altitude domain where heterogeneous chlorine chemistry is relevant. At altitudes of 33 to 40 km polar vortex HOCl mixing ratios were found to be around 0.14 ppbv as long as the polar vortex was intact, centered at the pole, and thus received relatively little sunlight. This is the altitude region where in midlatitudinal and tropic atmospheres peak HOCl mixing ratios significantly above 0.2 ppbv (in terms of daily mean values) are observed. After deformation and displacement of the polar vortex in the course of a major warming, ClO-rich vortex air was more exposed to sunlight, where enhanced HOx abundances led to largely increased HOCl mixing ratios (up to 0.3 ppbv), exceeding typical midlatitudinal and tropical amounts significantly. The HOCl increase was preceded by an increase of ClO. Model runs could reproduce these measurements only when the Stimpfle et al. (1979) rate constant for the reaction ClO+HO2→HOCl+O2 was used but not with the current JPL recommendation. At an altitude of 24 km, HOCl mixing ratios of up to 0.15 ppbv were detected. This HOCl enhancement, which is already visible in 18 September data, is attributed to heterogeneous chemistry, which is in agreement with observations of polar stratospheric clouds. The measurements were compared to a model run where no polar stratospheric clouds appeared during the observation period. The fact that HOCl still was produced in the model run suggests that a significant part of HOCl was generated from ClO rather than directly via heterogeneous reaction. Excess ClO, lower ClONO2 and earlier loss of HOCl in the measurements are attributed to ongoing heterogeneous chemistry which is not reproduced by the model. On 11 October, polar vortex mean daytime mixing ratios were only 0.03 ppbv.
Secondary Organic Aerosol Formation from Acetylene (C2H2): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase
Authors: Volkamer R. , Ziemann P. J. , Molina M. J.
Published: April 2010

Abstract. The lightest Non Methane HydroCarbon (NMHC), i.e., acetylene (C2H2) is found to form secondary organic aerosol (SOA). Contrary to current belief, the number of carbon atoms, n, for a NMHC to act as SOA precursor is lowered to n=2 here. The OH-radical initiated oxidation of C2H2 forms glyoxal (CHOCHO) as the highest yield product, and >99% of the SOA from C2H2 is attributed to CHOCHO. SOA formation from C2H2 and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosols, mild acidification with sulphuric acid (SA, 3<pH<4), and relative humidity (10<RH<90%). The rate of SOA formation is found enhanced by several orders of magnitude in the photochemical system. The SOA yields (YSOA) ranged from 1% to 24% and did not correlate with the organic mass portion of the seed, but increased linearly with liquid water content (LWC) of the seed. For fixed LWC, YSOA varied by more than a factor of five. Water soluble organic carbon (WSOC) photochemistry in the liquid water associated with internally mixed inorganic/WSOC seed aerosols is found responsible for this seed effect. WSOC photochemistry enhances the SOA source from CHOCHO, while seeds containing amino acids (AA) and/or SA showed among the lowest of all YSOA values, and largely suppress the photochemical enhancement on the rate of CHOCHO uptake. Our results give first evidence for the importance of heterogeneous photochemistry of CHOCHO in SOA formation, and identify a potential bias in the currently available YSOA data for other SOA precursor NMHCs. We demonstrate that SOA formation via the aqueous phase is not limited to cloud droplets, but proceeds also in the absence of clouds, i.e., does not stop once a cloud droplet evaporates. Atmospheric models need to be expanded to include SOA formation from WSOC photochemistry of CHOCHO, and possibly other α-dicarbonyls, in aqueous aerosols.
Attribution of aerosol light absorption to black carbon, brown carbon, and dust in China – interpretations of atmospheric measurements during EAST-AIRE
Authors: Yang M. , Howell S. G. , Zhuang J. , Huebert B. J.
Published: April 2010

Abstract. Black carbon, brown carbon, and mineral dust are three of the most important light absorbing aerosols. Their optical properties differ greatly and are distinctive functions of the wavelength of light. Most optical instruments that quantify light absorption, however, are unable to distinguish one type of absorbing aerosol from another. It is thus instructive to separate total absorption from these different light absorbers to gain a better understanding of the optical characteristics of each aerosol type. During the EAST-AIRE (East Asian Study of Tropospheric Aerosols: an International Regional Experiment) campaign near Beijing, we measured light scattering using a nephelometer, and light absorption using an aethalometer and a particulate soot absorption photometer. We also measured the total mass concentrations of carbonaceous (elemental and organic carbon) and inorganic particulates, as well as aerosol number and mass distributions. We were able to identify periods during the campaign that were dominated by dust, biomass burning, fresh (industrial) chimney plumes, other coal burning pollution, and relatively clean (background) air for Northern China. Each of these air masses possessed distinct intensive optical properties, including the single scatter albedo and Ångstrom exponents. Based on the wavelength-dependence and particle size distribution, we apportioned total light absorption to black carbon, brown carbon, and dust; their mass absorption efficiencies at 550 nm were estimated to be 9.5, 0.5 (a lower limit value), and 0.03 m2/g, respectively. While agreeing with the common consensus that black carbon is the most important light absorber in the mid-visible, we demonstrated that brown carbon and dust could also cause significant absorption, especially at shorter wavelengths.
Vertical advection and nocturnal deposition of ozone over a boreal pine forest
Authors: Rannik Ü. , Mammarella I. , Keronen P. , Vesala T.
Published: April 2010

Abstract. Night-time ozone deposition for a Scots pine forest in Southern Finland was studied at the SMEAR II measurement station by evaluating the turbulent eddy covariance (EC), storage change and vertical advection fluxes. Similarly to night-time carbon dioxide flux, the eddy-covariance flux of ozone was decreasing with turbulence intensity (friction velocity), and storage change of the compound did not compensate the reduction (well-known night-time measurement problem). Accounting for vertical advection resulted in invariance of ozone deposition rate on turbulence intensity. This was also demonstrated for carbon dioxide, verified by independent measurements of NEE by chamber systems. The result highlights the importance of advection when considering the exchange measurements of any scalar. Analysis of aerodynamic and laminar boundary layer resistances by the model approach indicated that the surface resistance and/or chemical sink strength was limiting ozone deposition. The possible aerial ozone sink by known fast chemical reactions with sesquiterpenes and NO explain only a minor fraction of ozone sink. Thus the deposition is controlled either by stomatal uptake or surface reactions or both of them, the mechanisms not affected by turbulence intensity. Therefore invariance of deposition flux on turbulence intensity is expected also from resistance and chemical sink analysis.
Concentrations of higher dicarboxylic acids C5–C13 in fresh snow samples collected at the High Alpine Research Station Jungfraujoch during CLACE 5 and 6
Authors: Winterhalter R. , Kippenberger M. , Williams J. , Fries E. , Sieg K. , Moortgat G. K.
Published: April 2010

Abstract. Samples of freshly fallen snow were collected at the high alpine research station Jungfraujoch (Switzerland) in February and March 2006 and 2007, during the Cloud and Aerosol Characterization Experiments (CLACE) 5 and 6. In this study a new technique has been developed and demonstrated for the measurement of organic acids in fresh snow. The melted snow samples were subjected to solid phase extraction and resulting solutions analysed for organic acids by HPLC-MS-TOF using negative electrospray ionization. A series of linear dicarboxylic acids from C5 to C13 and phthalic acid, were identified and quantified. In several samples the biogenic acid pinonic acid was also observed. In fresh snow the median concentration of the most abundant acid, adipic acid, was 0.69 μg L−1 in 2006 and 0.70 μg L−1 in 2007. Glutaric acid was the second most abundant dicarboxylic acid found with median values of 0.46 μg L−1 in 2006 and 0.61 μg L−1 in 2007, while the aromatic acid phthalic acid showed a median concentration of 0.34 μg L−1 in 2006 and 0.45 μg L−1 in 2007. The concentrations in the samples from various snowfall events varied significantly, and were found to be dependent on the back trajectory of the air mass arriving at Jungfraujoch. Air masses of marine origin showed the lowest concentrations of acids whereas the highest concentrations were measured when the air mass was strongly influenced by boundary layer air.
Atmospheric tracers during the 2003–2004 stratospheric warming event and impact of ozone intrusions in the troposphere
Authors: Liu Y. , Liu C. X. , Wang H. P. , Tie X. X. , Gao S. T. , Kinnison D. , Brasseur G.
Published: April 2010

Abstract. We use the stratospheric/tropospheric chemical transport model MOZART-3 to study the distribution and transport of stratospheric O3 during the remarkable stratospheric sudden warming event observed in January 2004 in the northern polar region. A comparison between observations by the MIPAS instrument on board the ENVISAT spacecraft and model simulations shows that the evolution of the polar vortex and of planetary waves during the warming event plays an important role in controlling the spatial distribution of stratospheric ozone and the downward ozone flux in the lower stratosphere and upper troposphere (UTLS) region. Compared to the situation during the winter of 2002–2003, lower ozone concentrations were transported from the polar region to mid-latitudes, leading to exceptional large areas of low ozone concentrations outside the polar vortex and "low-ozone pockets" in the middle stratosphere. The unusually long-lasting stratospheric westward winds (easterlies) during the 2003–2004 event greatly restricted the upward propagation of planetary waves, causing the weak transport of ozone-rich air originated from low latitudes to the middle polar stratosphere (30 km). The restricted wave activities led to a reduced extratropical downward ozone flux from the lower stratosphere to the lowermost stratosphere (or from the "overworld" into the "middleworld"), especially over East Asia. Consequently, during wintertime (15 December~15 February), the total downward ozone transport on 100 hPa surface by the descending branches of Brewer-Dobson circulation over this region was about 10% lower during the 2003–2004 event. Meanwhile, the extratropical total cross-tropopause ozone flux (CTOF) was also reduced by ~25%. Compared to the cold 1999–2000 winter, the vertical CTOF in high latitudes (60°~90° N) increased more than 10 times during the two warming winters, while the vertical CTOF in mid-latitudes (30°~60° N) decreased by 20~40%. Moreover, during the two warming winters, the meridional CTOF caused by the isentropic transport associating with the enhanced wave activity also increased and played an important role in the total extratropical CTOF budget.
Chemistry and transport of pollution over the Gulf of Mexico and the Pacific: spring 2006 INTEX-B campaign overview and first results
Authors: Singh H. B. , Brune W. H. , Crawford J. H. , Flocke F. , Jacob D. J.
Published: April 2010

Abstract. Intercontinental Chemical Transport Experiment-B (INTEX-B) was a major NASA (Acronyms are provided in Appendix A.) led multi-partner atmospheric field campaign completed in the spring of 2006 (http://cloud1.arc.nasa.gov/intex-b/). Its major objectives aimed at (i) investigating the extent and persistence of the outflow of pollution from Mexico; (ii) understanding transport and evolution of Asian pollution and implications for air quality and climate across western North America; and (iii) validating space-borne observations of tropospheric composition. INTEX-B was performed in two phases. In its first phase (1–21 March), INTEX-B operated as part of the MILAGRO campaign with a focus on observations over Mexico and the Gulf of Mexico. In the second phase (17 April–15 May), the main INTEX-B focus was on trans-Pacific Asian pollution transport. Multiple airborne platforms carrying state of the art chemistry and radiation payloads were flown in concert with satellites and ground stations during the two phases of INTEX-B. Validation of Aura satellite instruments (TES, OMI, MLS, HIRDLS) was a key objective within INTEX-B. Satellite products along with meteorological and 3-D chemical transport model forecasts were integrated into the flight planning process to allow targeted sampling of air parcels. Inter-comparisons were performed among and between aircraft payloads to quantify the accuracy of data and to create a unified data set. Pollution plumes were sampled over the Gulf of Mexico and the Pacific several days after downwind transport from source regions. Signatures of Asian pollution were routinely detected by INTEX-B aircraft, providing a valuable data set on gas and aerosol composition to test models and evaluate pathways of pollution transport and their impact on air quality and climate. This overview provides details about campaign implementation and a context within which the present and future INTEX-B/MILAGRO publications can be understood.
Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry
Authors: Altieri K. E. , Turpin B. J. , Seitzinger S. P.
Published: April 2010

Abstract. Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Elemental compositions of 552 unique molecular species were determined in the mass range 50–500 Da in the rainwater. Four main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO) only, sulfur (S) containing CHOS compounds, nitrogen (N) containing CHON compounds, and S- and N- containing CHONS compounds. Organic acids commonly identified in precipitation were detected in the rainwater. Within the four main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitrooxy-organosulfates were assigned based on elemental formula comparisons. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA) formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.
Intercomparison of ammonia measurement techniques at an intensively managed grassland site (Oensingen, Switzerland)
Authors: Norman M. , Spirig C. , Wolff V. , Trebs I. , Flechard C. , Wisthaler A. , Schnitzhofer R. , Hansel A. , Neftel A.
Published: April 2010

Abstract. As part of a field campaign in the framework of the NitroEurope project, three different instruments for atmospheric ammonia (NH3) measurements were operated side-by-side on a managed grassland site in Switzerland: a modified Proton Transfer Reaction Mass Spectrometer (PTR-MS), a GRadient of AErosol and Gases Online Registrator (GRAEGOR), and an Automated Ammonia Analyzer (AiRRmonia). The modified PTR-MS approach is based on chemical ionization of NH3 using O2+ instead of H3O+ as ionizing agent, GRAEGOR and AiRRmonia measure NH4+ in liquids after absorption of gaseous NH3 in a rotating wet-annular denuder and through a gas permeable membrane, respectively. Bivariate regression slopes using uncorrected data from all three instruments ranged from 0.78 to 0.97 while measuring ambient NH3 levels between 2 and 25 ppbv during a 5 days intercomparison period. Correlation coefficients r2 were in the range of 0.79 to 0.94 for hourly average mixing ratios. Observed discrepancies could be partly attributed to temperature effects on the GRAEGOR calibration. Bivariate regression slopes using corrected data were >0.92 with offsets ranging from 0.22 to 0.58 ppbv. The intercomparison demonstrated the potential of PTR-MS to resolve short-time NH3 fluctuations which could not be measured by the two other slow-response instruments. During conditions favoring condensation in inlet lines, the PTR-MS underestimated NH3 mixing ratios, underlining the importance of careful inlet designs as an essential component for any inlet-based instrument.
Influence of modelled soil biogenic NO emissions on related trace gases and the atmospheric oxidizing efficiency
Authors: Steinkamp J. , Ganzeveld L. N. , Wilcke W. , Lawrence M. G.
Published: April 2010

Abstract. The emission of nitric oxide (NO) by soils (SNOx) is an important source of oxides of nitrogen (NOx=NO+NO2) in the troposphere, with estimates ranging from 4 to 21 Tg of nitrogen per year. Previous studies have examined the influence of SNOx on ozone (O3) chemistry. We employ the ECHAM5/MESSy atmospheric chemistry model (EMAC) to go further in the reaction chain and investigate the influence of SNOx on lower tropospheric NOx, O3, peroxyacetyl nitrate (PAN), nitric acid (HNO3), the hydroxyl radical (OH) and the lifetime of methane (τCH4). We show that SNOx is responsible for a significant contribution to the NOx mixing ratio in many regions, especially in the tropics. Furthermore, the concentration of OH is substantially increased due to SNOx, resulting in an enhanced oxidizing efficiency of the global troposphere, reflected in a ~10% decrease in τCH4 due to soil NO emissions. On the other hand, in some regions SNOx has a negative feedback on the lifetime of NOx through O3 and OH, which results in regional increases in the mixing ratio of NOx despite lower total emissions in a simulation without SNOx. In a sensitivity simulation in which we reduce the other surface NOx emissions by the same amount as SNOx, we find that they have a much weaker impact on OH and τCH4 and do not result in an increase in the NOx mixing ratio anywhere.
Emissions of volatile organic compounds inferred from airborne flux measurements over a megacity
Authors: Karl T. , Apel E. , Hodzic A. , Riemer D. D. , Blake D. R. , Wiedinmyer C.
Published: April 2010

Abstract. Toluene and benzene are used for assessing the ability to measure disjunct eddy covariance (DEC) fluxes of Volatile Organic Compounds (VOC) using Proton Transfer Reaction Mass Spectrometry (PTR-MS) on aircraft. Statistically significant correlation between vertical wind speed and mixing ratios suggests that airborne VOC eddy covariance (EC) flux measurements using PTR-MS are feasible. City-median midday toluene and benzene fluxes are calculated to be on the order of 14.1±4.0 mg/m2/h and 4.7±2.3 mg/m2/h, respectively. For comparison the adjusted CAM2004 emission inventory estimates toluene fluxes of 10 mg/m2/h along the footprint of the flight-track. Wavelet analysis of instantaneous toluene and benzene measurements during city overpasses is tested as a tool to assess surface emission heterogeneity. High toluene to benzene flux ratios above an industrial district (e.g. 10–15 g/g) including the International airport (e.g. 3–5 g/g) and a mean flux (concentration) ratio of 3.2±0.5 g/g (3.9±0.3 g/g) across Mexico City indicate that evaporative fuel and industrial emissions play an important role for the prevalence of aromatic compounds. Based on a tracer model, which was constrained by BTEX (BTEX– Benzene/Toluene/Ethylbenzene/m, p, o-Xylenes) compound concentration ratios, the fuel marker methyl-tertiary-butyl-ether (MTBE) and the biomass burning marker acetonitrile (CH3CN), we show that a combination of industrial, evaporative fuel, and exhaust emissions account for >87% of all BTEX sources. Our observations suggest that biomass burning emissions play a minor role for the abundance of BTEX compounds in the MCMA (2–13%).
Energetic particle precipitation in ECHAM5/MESSy1 – Part 1: Downward transport of upper atmospheric NOx produced by low energy electrons
Authors: Baumgaertner A. J. G. , Jöckel P. , Brühl C.
Published: April 2010

Abstract. The atmospheric chemistry general circulation model ECHAM5/MESSy1 has been extended by processes that parameterise particle precipitation. Several types of particle precipitation that directly affect NOy and HOx concentrations in the middle atmosphere are accounted for and discussed in a series of papers. In the companion paper, the ECHAM5/MESSy1 solar proton event parametrisation is discussed, while in the current paper we focus on low energy electrons (LEE) that produce NOx in the upper atmosphere. For the flux of LEE NOx into the top of the model domain a novel technique which can be applied to most atmospheric chemistry general circulation models has been developed and is presented here. The technique is particularly useful for models with an upper boundary between the stratopause and mesopause and therefore cannot directly incorporate upper atmospheric NOx production. The additional NOx source parametrisation is based on a measure of geomagnetic activity, the Ap index, which has been shown to be a good proxy for LEE NOx interannual variations. HALOE measurements of LEE NOx that has been transported into the stratosphere are used to develop a scaling function which yields a flux of NOx that is applied to the model top. We describe the implementation of the parametrisation as the submodel SPACENOX in ECHAM5/MESSy1 and discuss the results from test simulations. The NOx enhancements are shown to be in good agreement with independent measurements. Ap index data is available for almost one century, thus the parametrisation is suitable for simulations of the recent climate.
Dual-wavelength aerosol vertical profile measurements by MAX-DOAS at Tsukuba, Japan
Authors: Irie H. , Kanaya Y. , Akimoto H. , Iwabuchi H. , Shimizu A. , Aoki K.
Published: April 2010

Abstract. We present vertical profiles of the aerosol extinction coefficient retrieved from ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements at Tsukuba, Japan (36.1° N, 140.1° E), from November 2006 to March 2007. Retrievals utilizing absorption by the oxygen collision complex O4 are first made at two wavelengths, 354 and 476 nm. A robust assessment of the MAX-DOAS aerosol data is then made using coincident lidar measurements throughout the period. Agreement between aerosol extinction coefficients measured by MAX-DOAS and the lidar tends to be better at the longer wavelength and at lower altitudes. At 476 nm, the best agreement, to within 30%, is found at altitudes of 0–1 km, confirming results from a literature assessment for a two-month measurement period. These findings are supported by comparisons between aerosol optical depths derived from MAX-DOAS and sky radiometer measurements and are further explained by differences in the altitude-dependent measurement sensitivity to the aerosol extinction coefficient between 354 and 476 nm. Thus, uncertainty in MAX-DOAS aerosol measurements is well quantified and characterized, providing a basis for quantitative studies using MAX-DOAS measurements.
Mainz Isoprene Mechanism 2 (MIM2): an isoprene oxidation mechanism for regional and global atmospheric modelling
Authors: Taraborrelli D. , Lawrence M. G. , Butler T. M. , Sander R. , Lelieveld J.
Published: April 2010

Abstract. We present an oxidation mechanism of intermediate size for isoprene (2-methyl-1,3-butadiene) suitable for simulations in regional and global atmospheric chemistry models, which we call MIM2. It is a reduction of the corresponding detailed mechanism in the Master Chemical Mechanism (MCM v3.1) and intended as the second version of the well-established Mainz Isoprene Mechanism (MIM). Our aim is to improve the representation of tropospheric chemistry in regional and global models under all NOx regimes. We evaluate MIM2 and re-evaluate MIM through comparisons with MCM v3.1. We find that MIM and MIM2 compute similar O3, OH and isoprene mixing ratios. Unlike MIM, MIM2 produces small relative biases for NOx and organic nitrogen-containing species due to a good representation of the alkyl and peroxy acyl nitrates (RONO2 and RC(O)OONO2). Moreover, MIM2 computes only small relative biases with respect to hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), methanol (CH3OH), formaldehyde (HCHO), peroxy acetyl nitrate (PAN), and formic and acetic acids (HCOOH and CH3C(O)OH), being always below ≈6% in all NOx scenarios studied. Most of the isoprene oxidation products are represented explicitly, including methyl vinyl ketone (MVK), methacrolein (MACR), hydroxyacetone and methyl glyoxal. MIM2 is mass-conserving with respect to carbon, including CO2 as well. Therefore, it is suitable for studies assessing carbon monoxide (CO) from biogenic sources, as well as for studies focused on the carbon cycle. Compared to MIM, MIM2 considers new species like acetaldehyde (CH3CHO), propene (CH2=CHCH3) and glyoxal (CHOCHO) with global chemical production rates for the year 2005 of 7.3, 9.5 and 33.8 Tg/yr, respectively. Our new mechanism is expected to substantially improve the results of atmospheric chemistry models by representing many more intermediates, that are transported and deposited, which allows us to test model results with many more new measurements. MIM2 allows regional and global models to easily incorporate new experimental results on the chemistry of organic species.